CA2134052A1 - Nonaqueous secondary battery - Google Patents

Nonaqueous secondary battery

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Publication number
CA2134052A1
CA2134052A1 CA002134052A CA2134052A CA2134052A1 CA 2134052 A1 CA2134052 A1 CA 2134052A1 CA 002134052 A CA002134052 A CA 002134052A CA 2134052 A CA2134052 A CA 2134052A CA 2134052 A1 CA2134052 A1 CA 2134052A1
Authority
CA
Canada
Prior art keywords
electrode active
active material
compound
negative electrode
secondary battery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA002134052A
Other languages
French (fr)
Inventor
Yoshio Idota
Masayuki Mishima
Yukio Miyaki
Tadahiko Kubota
Tsutomu Miyasaka
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP5264995A external-priority patent/JPH07122274A/en
Priority claimed from JP00776094A external-priority patent/JP3498345B2/en
Priority claimed from JP6026745A external-priority patent/JPH07235293A/en
Priority claimed from JP6066422A external-priority patent/JPH07249409A/en
Application filed by Individual filed Critical Individual
Publication of CA2134052A1 publication Critical patent/CA2134052A1/en
Abandoned legal-status Critical Current

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581Chalcogenides or intercalation compounds thereof
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/058Construction or manufacture
    • H01M10/0587Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/026Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027Negative electrodes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00Electrolytes
    • H01M2300/0017Non-aqueous electrolytes
    • H01M2300/0025Organic electrolyte
    • H01M2300/0028Organic electrolyte characterised by the solvent
    • H01M2300/0037Mixture of solvents
    • H01M2300/004Three solvents
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1391Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00Primary cells; Manufacture thereof
    • H01M6/04Cells with aqueous electrolyte
    • H01M6/06Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • H01M6/10Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with wound or folded electrodes

Abstract

ABSTRACT OF THE DISCLOSURE
A nonaqueous secondary battery comprising a positive electrode active material, a negative electrode active material, and a lithium salt is disclosed, in which the negative electrode active material contains (1) a compound capable of intercalating and deintercalating lithium comprising an atom of the group IIIB, IVB or VB of the periodic table, (2) an amorphous compound containing at least two atoms selected from the elements of the groups IIIB, IVB, and VB of the periodic table, (3) a compound capable of intercalating and deintercalating lithium containing at least one of the atoms of the group IIIB, IVB, and VB of the periodic table and fluorine, or (4) a compound of the metal of the group IIIB, IVB or VB of the periodic table, Zn, or Mg which is capable of intercalating and deintercalating lithium. The nonaqueous secondary battery of the invention exhibits improved charge and discharge characteristics and improved safety.

Description

-- ~ 1 3 4 0 ~ 2 . . ~. ~....
NONAQUEOUS SECONDARY BATTERY
' ',.'''' ',, ~''~' '`',' FI~LD OF THE INVh'NTION
This invention relates to a nonaqueous secondary ;
battery having improved charge and discharge cycle characteristics and improved safety.
BACKGROUND OF THE INVENTION
Negative electrode active materials for nonaqueous secondary batteries typically include metallic lithium and -~
lithium alloys. The problem associated with these active ~ `~
materials is that metallic lithium grows dendritically during `"; `
charging and discharging to cause an internal short circuit, `
involving a danger of ignition because of high activity of the dendritical metal E~ se. To solve the problem, a calcined carbonaceous material capable of intercalating and c~
deintercalating lithium has recently been put to practical ;
use. However, since the carbonaceous material has electrical conductivity by itself, metallic lithium is sometimes " ~ ;
precipitated on the carbonaceous material at the time of an overcharge or a rapid charge. It evenkually follows that lithium grows dendritically thereon. This problem has been dealt with by;altering a charger or reducing the amount of ; `
the positive electrode ac~ive material to prevent an overcharge. Where the latter solution is adopted, however, - -the limited amount of the active material leads to a limited discharge capacity. Further, khe carbonaceous material has a :'', ''.`,.`', .... ', ~ ~,. "-......
, .:,,, . ~

:"
3 ~

~ ;- ': .relatively low density and therefore a low capacity per unit volume. Thus, the discharge capacity is limited by both the . ~:
amount of the active material and the capacity per unit :~.
volume.
In addition to metallic lithium, lithium alloys and the above-mentioned carbonaceous material, negative electrode active materials so far proposed include TiS2 and LiTiS2 which are capable of intercalating and deintercalating lithium tU.S. Patent 3,983,476); transition metal oxides .
having a rutile structure, such as WO2 (U.S. Patent :-4,198,476), spinel compounds, such as Li~Fe(Fe2)O4 (JP-A-58- . `
220362, the term "JP-A~ as used herein means an "unexamined published Japanese patent application"); a electrochemically ~ .
synthesized lithium compound of Fe2O3 (U.S. Patent ~ ``
4,464,447); a lithium compound of Fe2O3 (JP-A-3-112070); NbzO5 ~ :
(JP-B-62-59412 (the term "JP-B~' as used herein means an ; ~ `
"examined published Japanese patent application") and JP-A-2 82447); FeO, Fe2O3, Fe3O4, CoO, C23, and Co3O4 (JP-A-3- ~ .
291862); amorphous V2O5 (JP-A-4-223061); and transition metal .::.
oxides having their basic crystal structure changed by intercalation of a lithium ion (EP 567149). Any of these `~
" ~ ~ ~
known compounds has a high oxidation-reduction potential, .
failing to provide a nonaqueous secondary battery having a discharge potential as high as 3 V and a high capacity.
.SnO2 or Sn compounds are used as an acti~e material of lithium batteries as in Lil.03CoOgsSnO.o4oz as a secondary ~ ~ .
~;' ' ', ~ ` ` 2 ~ 3 ~ a ~ 2 .. .. . . ,~ ., ~, battery positive electrode active material (EP 86-106301);
SnO2-added V2O5 as a secondary battery positive electrode active material (JP-A-2-158056); SnO2-added a-Fe203 (preferred SnO2 content: 0.5 to 10 mol%) as a secondary battery negative -~
electrode active material (JP-A-62-219465); and SnO2 as a primary battery positive electrode active material (Denki `~
Kaqaku oyobi Koayo Butsuri Kagaku, Vol. 46, No. 7, p. 407 ~ ;
(1978)). With reference to the use of SnO2 or Sn compounds ,,~
as an electrochromic electrode, it is known that SnO2 is capable of reversible intercalation of an Li ion (see Journal "`
of Electrochemical Society, Vol. 140, No. 5, L81 (1993) and that a film comprising InO2 doped with 8 mol% of Sn (i.e., IT0) is capable of reversible intercalation of an Li ion (see Solid State Ionics, Vols. 28-30, p. 1733 (1988)). However, ~ -the electrode useul in an electrochromic system should be ... ,. . ~
transparent, the active material is used in the form of a thin film formed by, for example, vacuum evaporation, and the "~
electrode usually works at a considerably low current differing from the practical range of batteries. For `;
example, Solid State Ionics, suPra, shows a working current ~ -~
of 1 ~A to 30 ~A/cm2 as an experimental example. ``~
,..~. '.,-.
Known positive electrode active materials include spinel compounds disclosed in JP-B-4-30146 and cobalt oxide disclosed in JP-B-63-59507.
It is possible to combine these positive electrode active materials with an oxide mainly comprising Sn as a `
. - ... .
- 3 - ~:~
-'' ~"'' . .'''';' .
,.: ... .
~..~, .: ';' ',,, 1 3 ~

negative electrode active material t~ provide a nonaqueous secondary battery having a high discharge potential, a high capacity, improved charge and discharge cycle characteristics, and increased safety. Yet, the charge and discharge cycle characteristics are still unsatisfactory as described above, and it has been keenly demanded to further ~ `
improve charge and discharge cycle characteristics. ~ `~
SUMMARY OF THE INVENTION
An object of the present invention is to provide a nonaqueous secondary battery having improved charge and discharge cycle characteristics~ a high discharge potential, -a high discharge capacity, and increased safety. ~
The above object of the present invention is ~;
accomplished by a nonaqueous secondary battery comprising a positive electrode active material, a negative electrode ~
active material, and a lithium salt, in which (1) the ; ; i negative electrode actiYe material contains at least one -. ~ .
compound capable of intercalating and deintercalating lithium ~
mainly comprising an atom of the group IIIB, IVB or VB of the ;
periodic table, (2) the negative electrode active material mainly comprises an amorphous compound containing at least ! I two'atoms selected from the elements of the groups IIIB, IVB, and VB of the periodic table, (3) the negative electrQde active material is a compound capable of intercalating and ;~
deintercalating lithium containing at least one of the atoms -of the group IIIB, IVB, and VB of the periodic table and .
1 3 ~ 0 ~ 2 ':`~-';.```'.

fluorine, or (4) the negative electrode active material contains at least one compound of the atom of the group IIIB, ~ `r',~
IVB or VB of the periodic table, Zn, or Mg which is capable of intercalating and deintercalating lithium. ~ `"'~
BRIEF DESCRIPTION OF THE DRAWING ` ' ``~' Fig. 1 is the X-ray diffraction pattern of compound D-1-A prepared in Synthesis Example D-1. ~-Fig. 2 is a cross section of a coin battery prepared in Examples, wherein 1 indicates a negative electrode sealing plate, 2 indicates a negative electrode active material mixture pellet, 3 indicates a separator, 4 indica~es a positive electrode active material mixture pellet, 5 ;
indicates a collector, 6 indicates a positive electrode case, and 7 indicates a gasket. `
Fig. 3 is a cross section o~ a cylindrical battery `
prepared in Examples, wherein 8 indicates a positive electrode sheet, 9 indicates a negative electrode sheet, 10 `
indicates a separator, 11 indicates a battery case, 12 ;` `
indicates a battery cover, 13 indicates a gasket, and 14 indicates a safety valve.
DETAILED DESCRIPTION OF THE INVENTION
The terminology "negative electrode active material ~-precursor~' as used herein is explained below. The inventors have found that SnO having an a-PbO structure, SnO2 having a rutile structure, and the like do not act by themselves as a ~;
negative electrode active material of a secondary battery but - 5 ~

;-`` ~134~!~2 change their crystal structure on intercalation of lithium to act as a reversible negative electrocle active material. That is, the charge and discharge efficiency of the first cycle is as low as about 80% or 60~. Thus, the starting material, such as a-PbO-structure SnO or rutile-structure SnO2, namely, ~. ., .-. .;
a compound before lithium intercalation is called a "negative ~ -.: , , :
electrode active material precursor".
The negative electrode active material according to ; -~
the present invention can be obtained by electrochemically intercalating a lithium ion into, for example, an oxide, an `~
active material precursor. Lithium ion intercalation is conducted until the basic structure of the oxide is changed ~ ~ "
., .
(for example, until the X-ray diffraction pattern changes) `
and also until the thus changed basic structure of the Li~ ~
.. ~.... ,. ~
ion-containing oxide undergoes substantially no change during ~
. , ~ . .
charging and discharging (for example, the X-ray diffraction pattern does not change substantially). The change in basLc structure means change from a certain crystal structure to a -. .
different crystal structure or from a crystal structure to an amorphous structure.
Where the compound represented by formulae (I) to (V) of~the present invention described in later is used as a negative electrode active material precursor, it was found that intercalation of lithium does not cause reduction of the respective metal (an alloy with lithium~. This can be ~ ~;
confirmed from the fact that (1) observation under a --. . . .
- 6 - ~

1 3 ~ 2 transmission electron microscope reveals no precipitation of a metal (especially no precipitation of a dendrite), (2) the -potential of lithium intercalation/deintercalation via a metal is different from that of the oxide, and (3) the `~
lithium deintercalation loss with respect to lithium intercalation in SnO was about 1 equivalent, which does not ~`
agree with a loss of 2 equivalents in the case where metallic tin is generated. Since the potential of an oxide is similar `;' to that of a currently employed calcined carbonaceous ` ;
compound, it is assumed that the bonding state of lithlum is ``~
neither mere ionic bonding nor mere metallic bonding, ; ;~
similarly to a calcined carbonaceous compound. ~ccordingly, ;` ; `~
the negative electrode active material of the present ; ~;.`
invention is obviously different from conventional lithium ; `` `
alloys.
It is preferable that the active material precursor "
which can be used in the present invention is substantially ;~
amorphous at the time of battery assembly (before lithium ion ;
intercalation). The term ~substantially amorphous~' as used herein means that an X-ray diffraction pattern using CuKa rays shows a broad scattering band with peaks between 20 and -4do in terms of 2~ and may contain diffraction assigned to a crystalline structure. `
The maximum intensity of the peaks assigned to the -' crystalline structu:re appearing between 2~=40 and 70 is ~ ;
preferably not higher than 500 times, still preferably not - 7 ~
.` .'"' ::

~3~05~

higher than 100 times, still more preferably not higher than 5 times, the intensity of the peak of the broad scattering band appearing between 2~=20~ and 40. It is the most preferred that the pattern exhibits no crystalline diffraction spectrum.
Also, it is preferred that the active material precursor is substantially amorphous at the time of intercalating lithium ion. `
In the present invention, either the active material precursor or the active material can be used as a negative electrode. Hereinafter, cases are met in which they are represented as an acti~e material.
The metals of the groups IIIB to VB of the periodic table which can be used in the present invention include B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, As, Sb, and Bi, preferably B, Al, Si, Ge, Sn, Pb, P, As, Sb, and Bi, still preferably Al, Si, Ge, Sn, Pb, As, and Sb or B, Al, Si, Ge, Sn, and P. ~ ;
Examples of the negative electrode active material according to the present invention include GeO, GeOz, SnO, SiO, SnO2, PbO, PbO2, Pb203, Pb304, Sb203, Sb204, Sb205, Bi203, Bi204, and Bi206, and non-stoichiometrical compounds of these ~
oxides. ` i I ! ;
Preferred of them are SnO, SnO2, GeO, and GeO2, with SnO and SnO2 being particularly preferred. a-PbO-structure SnO, rutile-structure SnO2, GeO, and rutile-structure GeO2 `~
are preferred, with a-PbO-structure SnO and rutile-structure '.,'','''~,`..''''''.;''"' ~ 1 3 4 ~ 5 2 SnO2 being particularly preferred. .
Still preferred negative elec:trode active materials ` .
are represented by formula (I)~

MlM2M4 (I) .`.

wherein M1 and M2, which are different from each other, each .. ;~
represent at least one of Si, Ge, Sn, Pb, P, B, Al, As, and : :
Sb, preferably at least one of Si, Ge, Sn, Pb, P, B, Al, and : . ...... ...... ;
Sb, still preferably at least one of Si, Ge, Sn, Pb, P, B, ` ` ............ `.
and Al; M4 represents at least one of O, S, Se, and Te, preferably at least one of O and S, still preferably 0; p ~ `
represents a number exceeding 0 and not exceeding 10, ~ ~;
generally from 0 001 to 10, preferably from 0.01 to 5, still .;
preferably from 0.01 to 2; and q represents a number of from 1 to 50, preferably 1 to 26, still preferably 1.02 to 6. .;;
Also, preferred are those of formula (I) in which and M2 are different from each o~her; Ml represents at least ~ : ~
one of Ge, Sn, Pb, Sb, and Bi; M2 represents a$ least one ~ ~-atom of the groups IIIB, IVB, and VB of the periodic table .
~exclusive of Ge, Sn, Pb, Sb, and Bi when Ml represents each of these); p represents a number of from 0.001 to l; and M4 ~ . . .:,:
and q have the same meanings as defined in formula (I) above.
The valency of Ml or M2 in formula (I) is not ~; ;
particularly limited and may be either a single valency or a ; .;- ;
mixed valency. The M2 to Ml ratio may vary continuously .. . ..
_ g _ ','., .':, .

2 : `

within a range of from more than 0 up to 10 molar -equivalents. The amount of M4, represented by q in formula (I), continuously varies accordingly.
Of the compounds of formula (I), preferred are those in which M1 is Sn, i.e., compounds represented by formula (II):
' SnM3~Ms (II) wherein M3 represents at least one of Si, Ge, Pb, P, B, Al, As, and Sb, preferably at least one of Si, Ge, Pb, P, B, Al, and Sb, still preferably at least one of Si, Ge, Pb, P, B, and Al; M5 represents at least one of O and S, preferably O;
p represents a number exceeding 0 and not exceeding 10, generally from 0.001 to 10, preferably from O.Ol to 5, more preferably a number of from 0.01 to 1.5, still preferably from 0.7 to 1.5; and q represents a number of from 1.0 to 50, preferably from 1.0 to 26, still preferably from 1.02 to 6.
Still preferred of the compounds represented by formula (II) are those represented by formula (III)~

wherein M3 is as defined above, preferably Si; r represents a number of exceeding 0 and not exceeding 5.0, generally from ~-0.01 to 5.0, preferably a number of from 0.01 to 1.5, still -- 10 - '~
.. .,-~
... ,...i, ..
.,: : ~ -: :::, -, . -: . ~ . -,: .
;~' ~

i 2 .,,,,'. ~,.'~ ' preferably from 0.7 to 1.5; and s represents a nu~ber of from 1.0 to 26, preferably from 1.02 to 6.

Examples of the compounds represented by formula ~II) ~ ;

or ~III) are SnSiO.0lO1 02, SnGeO.0lOl.02, SnPb0.0lOl.02, SnPO.0lOl.025r ~ -SnBo.oll.ols~ SnAl0.0ll.0l5, SnSiO.0102.02~ SnGeO.0lO2.02~ SnPbO.0102.02~

SnP0.0lo2.o25l SnB0.0lo2.ol5~ SnSi0.05Ol.l, SnGe0.05Ol.l, SnPb0.05Ol.l, ~ ;

SnPO.05Ol.l25, SnBO.05Ol.075r SnSiO.05O2.l, SnGeO.05O2.l, SnPbO.05O2.l~ ;
SnPo.osO2.l2s, SnBo.oso2.o7s~ SnSiO.l0l.2, SnGeO.l0l.2, SnPbO.l0l.2, , ~
SnPO.l0~.25, SnBO,l0l.l5, SnSiO.l02.2, SnGeO.l02.2, SnPbO.l02.2, , ,. ~
SnPO.l02.25, SnBO.l02,l5, SnsiO.2ol.4~ SnGeO.2Ol.4, SnPbO.201.4~ SnPO,20l, SnB0 2Ol3, SnSi0.2O2 4, SnGeO.2O2 4, SnPb0 2O2 4, SnP0 2O2 5, SnBO.2O2.3, SnSiq.30l.6, SnGeO.30l,6, SnPbO.30l.6, SnPO.30l.75, SnBO.30l.45, SnSiO.302.6, SnGeO.302.6, SnPbO,302.6, SnPO,302.75, SnBO.302.45, ' .. ~,, .'' SnSi0.7O2.4, SnGe0.7O2.4, SnPb0.7O2.4, SnPO.7O2.75, SnB0.7O2.05~ ;~
SnSi0.8O2 6, SnGe0 3O26, SnPb0.8O2.6, SnP0.8O3, SnBO.8O2.2~ SnSiO3, SnGeO3, SnPbO3, SnPO3.5, SnBO2.5, SnSil.2O3.4, SnGel.2O3.4, ;
SnPbl.203.4, SnPl.204, Snl3l,202..3, SnSil.504, SnGel.504, SnPbl.504, SnPl.5O4,75, SnBl.5O3.25, SnSi2O5, SnGe2O5, SnPb2O5, SnP2O6, SnB2O4, ; -SnSi2O6, SnGe2O6, SnPb2O6, SnP2O7, SnB2O5, SnSiS3, SnSiSe3, `
SnSiTe3, SnPS3.5, SnPSe3.5, SnPTe3.5, SnBS2.5, SnBSe2.5, SnBTe2.5, SnP0,8O3, SnBO.8O2.2, and SnSiO.25Bo3.
The valency of Sn and M3 in formula (II) or (III) is not particularly limited and may be a single valency or a mixed valency. The ratio of M3 to Sn in the compound of formula (II) may vary continuously within a range of from -13~0~2 0.01 to 10 molar equivalents. Accordingly, the amount of M5, represented by q in formula (II), varies continuously.
Similarly, the ratio of M3 to Sn in the compound of formula (III) may vary continuously within a range of from 0.01 to 5.0 molar equivalents. Accordingly, the amount of oxygen, represented by s in formula (III), varies continuously.
Of the compounds of formula (III), preferred are ` .
those represented by formula (IV)~
' ~' SnSitPuM6v08 (IV) Of the compounds of formula (IV), preferred are those represented by formula (V)~

SnSi~PuAl~M7u08 (V) ::: .: ,: .,.:
, :::: .: ,:
In formulae (IV) and (V), M6 represents at least one of Ge, . ..
B, Al, and Pb, preferably at least one of Ge, Al, and B, ;.. :
still preferably Al; M7 represents at least one of Ge, B, and P; t represents a number exceeding 0 and not exceeding 2.0 . .
(preferably not exceeding 1.5), generally from 0.01 to 2.0, .~
preferably from 0.01 to 1.5; u represents a number of from ~:;; ;:
0.01 to 4.0, preferably from 0.01 to 3.5; v represents a .,. :-, - .:
number exceedlng 0 and not exceeding 2.0 (preferably not ;:
exceeding 1.5), generally from 0.01 to 2.0, preferably from -:
0.01 to 1.5; w represents a number exceeding 0 to not :~; .:

:" , .~.... :,...

- ~13~0~2 ~

, ', ~ '-:'`
exceeding 2.0, generally from 0.01 to 2.0; and s represents a number of from 1.0 to 26, preferably from 1.02 to 10.
Specific but non-limiting examples of the oxides -~
.~. .. ,, :~
represented by formula (IV) or (V) are SnSiO.25BO.2PO.203, ~ ~
SnSiO.5BO.2PO.203, SnSiO.9PO.l02.25, SnsiO.8po.2o3.l~ SnSio.7Po.302.7s/ - ~' ' SnSiO.5PO,503.2s, SnSiO.3PO.703.35, SnSiO.2PO.803.4, SnSiO.5PO.l02.25, SnSiO.~GeOlPo~gP3.65~ SnSiO.2GeO.lPO.703.3s~ Snsio.6Geo~4Po.lO~.~s~
SnSiO.6GeO.2PO.203.l, SnSiO.7GeO.lPO.203.l, SnSiO.~GeO.lPO.~03.05, ; `'-''"
SnSiO.8GeO.lPO.303.55, SnSiGeO.lPO.lP3.45, SnSiGeO.2PO.2P3.9, '' .' ,~ ..
5nSiGeO.lPO.2P3.7, SnSiO.lAlO.~PO.903.6, Snsio.3Alo.lpo.7o3.s~
SnSiO.6Al0.3PO.l02.9, SnSiO.6Al0.2PO.203~ SnSiO.6AlO.lPO.303.1~
SnSiO.8AlO.lpo.lo3~ SnSiO.8AlO.lPO.203.25~ SnSiO.8Al0.2PO.203.4, SnSiO.7Al0.2PO.303.45, SnSiO.4Al0.2PO.603.6, SnSiAl0.2PO.403.5, SnSiA1O,lPO.l03.4, SnSiAl0,2PO,203,8, SnSiAlo,lPO,203.65, SnSiO,IBO,lPo~9o3~6r SnSiO,3BO,lPO,703,5, SnSiO.6BO.3PO.l02.~, .
SnSiO.6BO,2PO,203, SnSiO.6BO.lPO.303.l~ SnSiO.8BO.lPO.l0 SnSiO.8BO.lPO.303.5, SnSiBO.lPO.l03.4, SnSiBO.2PO.203.~, SnSiBO.lPO.203.65 SnSiO.lPbO.IPo.903.6, SnSiO.3PbO.lPO.703.5, SnSiO.6PbO.3PO.102.9/
SnSiO.6PbO.2PO.203, SnSiO.6PbO.lPO.303.l, SnSiO.8PbO.lPO.103/ .,;';
SnSiO.8PbO.lPO.303.5, SnSiPbO.lPO.l03.4, SnSiPbO.2PO.203.8, SnSiPbO.lPO.~03.65, SnPAl0.l03.65, SnpAlo.3o3.ssl SnPo.sAl0.l03.ls~

SnPo.sAl0~3o2~4s~ SnPO.5Al0.l02.4, and SnPO.jAl0.302.7. The valency of ~ i Sn and M6 are not particularly limited and may be a single valency or a mixed valency. The ratio of M6 to Sn may vary continuously within a range of from O to 2 molar equivalents, ;~ `` 2 1 3 ~

and the amount of oxygen continuously varies accordingly.
Additional examples of the compounds represented by formulae ~I) to (V) are shown below.
SnSiO.lGeO~PbO.1o2.6~ SnSiO.zGeO.loz.6r SnSiO.2PbO.lO2.6, ~ ;

SnGeO.2SiO.lO2.6, SnPbO.2SiO.lo2~6~ SnGeO,2PbO.~O2.6, SnPbO.2GeO.102.6r SnSiO.gGeO,l03, SnSiO.8GeO.2O3, Snsio.5Geo.so3~ SnSiO.gPbO.103 SnSiO.8PbO.2O3, SnSiO.5PbO.503, SnGeO.9SiO.l03, ~n5eO.8SiO.203~
SnPbO.gSiO.1O3, SnPbO.8SiO.2O3, Snsio.sGeo.lpbo.lo3~ SnPo.sGeo 13.45r SnPO.8GeO.203.4~ Snpo.5Geo.5o3.2sl Snpo.spbo.lo3.4s~ Snpo.spbo.2o;.4r SnPo.5PbO.5o3.25~ SnGeO.gPO.~o3.o5~ SnGeo.spo.2o3.l~ SnPbO.gPO.103.05r ";~
SnPbO.8PO.203.1, SnPO.8GeO.~pbo.lo3.4~ SnBo.sGeo.lo2.ss~ SnBO.8GeO.202.6~
SnBO.5GeO.502.75, SnBo~9pbo.~o2.ss~ SnBo~8pbo.2o2.6r SnBo.spbo.so2.7sr `, ~, ,;, ''. , SnGeO.gBO.~02.95, SnGeO.8BO.202.9, SnPbO.gBO.~02.95, SnPbO.8BO.202.9, .. ;.;~
SnBO,8GeO,lPbO,I02.6, SnSiO.25Bo.2po.~o3~ Snsio.sBo.2Po.203r ,`'., ,.' ', SnSiO~9Alo~lo2.95~ Snsio.5Alo.o5o2.75r SnSiO.5Al0.l02.l5, SnSiO.5AlO.502.75r ,,, ,. ,.~, SnSiO.~Al0.302.85, SnSiAl0.203.3, Snsio.5Bo.o5o2.75~ Snsio.sBo~loz.lsr ~`~,'`', SnSiO.5BO.502.75, SnSiO.7Bo.3O2.45~ SnSiO.gBO.l02.95, SnSiBO.203.3, .;,~,,"";~"~, SnSiO.5PbO.O5O2.75, SnSiO.5PbO.lO2.~5, SnSiO.5PbO.502.75, SnSiO.7PbO.302.45, j... ,,..".... ,.:
SnSiO.gPbO,~02,95, SnSiPbO,203,3, SnSiO.~GeO.~PO.903.65, ~',;/~``.`:';', SnSiO.2GeO.~PO.703.35, SnsiQ.6Geo.4po.~o3.2s~ SnSiO.6GeO.2PO.203.1r .,.. '.. '.:`.. ;.,.', SnSiO.7GeO.lPO.203.l~ SnSiO.gGeo.~po.~o3.os~ Snsio.sGeo.lpo.3o3.ss~

SnSiGeO.lPO.~03.45, SnSiGeO.2PO.203.9, SnSiGeO.lPO.203.7, . ,~
SnSiO.8GeO.IAlQ.lo2.95~ Snsio.8Geo.lBo.lo2.ss~ SnSiO.8GeO.lSbO.1~2.95r ,'.~.,;j~.... ~,.,.,;~
SnSiO.8Geo.lIno.~o2.9s~ Snsio.gGeo.~pbo.~o2.ssi SnSiO.8BO.lA10.102.9r '""'''-''' ~ '`
SnSi2,aSbO~AlO2,9, SnP~I0~03 65, SnPAl0~0, 95, SnPO,~ O~ ~5, =~

3 ~ 0 ~ 2 SnPO.8Al0.3o2.45f SnP0,5Al0,l02,4, SnP0.5Al0.302.7, Pbsio.0ll.02/ - -PbGeO.0l0~.02, PbSio.o~o2.o2~ PbGeO.0lO2.02~ Pbpo.olol.o25~ PbBo.olol.olsr PbP0,0l2.025, PbGe0.0l2.015t Pbsio.osl.l~ PbGeo.osl.l~ Pbsio.os2.
PbGeO.05O2.l, PbPo.o5ol.l25~ PbBo~o5ol~o7sl Pbpo.oso2.l2s~ PbBo.osz.07s~
PbSio.lO2,2, PbGe0,l02.2, PbSio.~0l.2, PbGe0.l0l.2, PbPo.l02.2s/
PbBo.lO2.l5, PbPo.lOl.25, PbBo.lOl,l5, Pbsio.2o2.4~ PbGeO.202.4~ . . ..
Pb5io.2Ol.4, PbGeO.20l.4, Pbpo.2o2.5~ PbBo.2o~3~ PbPo.20l.s~ PbBo.2l.3~ `.
PbSio.3O2.6, PbGeO.302.6, Pbsio.3ol.6~ PbGeO.30~.6~ PbPo.302.7s~ ~, PbBo.32.4s, PbPo.30l.7sr PbBo.3l.4s~ PbSiO.2GeO.102.6~ PbGeO.2SiO.102.6~ :.-PbP0.2GeO.lO2 7, PbGe0,2P0.lO2,65, PbBO.2GeO.l02.5~ PbGe0.2BO.l02.55, ;~
.
PbSio,702,4, PbGeO,702.4, PbPo.7O2.75, PbBo.7o2.o5~ Pbsio.s2.6 PbGe0.802.6, PbPo.8O3, PbBo,802.2, PbSiO3, PbGeO3, PbPO3.5, PbBO2.5, PbSiO.9GeO,I03, PbSiO,8GeO,203, PbSiO,5t:eO,503, PbPo~gGeo.lo3~45r . , PbPo.sGeo.203.4~ PbPo.sGeo.sO3.2s, PbBo.sGeo.l2.6s, PbBo.sGeo.22.6 PbB0,5Ge0,so2.75r PbGe0.9Si0,l03, PbGe0,8SiO,203, PbGeO,9PO.l03.05, PbGeO.8PO.203.l, PbGeO.9BO.l02.95, PbGeO.8BO.202.9, PbSil.504, PbGel.504, PbPl,504,75~ PbBl.5O3.25, PbGe205, PbSi206, PbGe206, PbP207, PbB205, GeSi0.0lO~.02, GeSiO.0lO2 02~ GeSiO.050l,l, GeSiO,0502,l, GeSi0,l0l2, GeSiO,l02.2, GeSiO,20l.4, GeSiO,202.4, GeSiO.30l,6, GeSiO.302,6, , GeSiO,502, GeSiO,503, GeSi0.702.4, GeSiO.703.4, GeSiO3, GeSiO4, GeSil,504, GeSil,505, GePO,0l0l~025r Gepo~olo2~o2s~ GePo.osOl.lzsr GeP0,05O2.l25, GeP0l0l.25, GePO.~02.25, GePO.20l.5, GePO.202.5, GeP0.30l.75, GeP0.302.75, GePO.502.25, GePO.503 25, GePO.702.7s, GePO703 75, ~ePO3 5, GePO4,5, GePl,504.75, Gepl.so5.75~ GeBo.olol~ols~ GeBo.0lo2.ols~
GeBO.050l.075, GeBO.0502.075, GeBO.l0l.l5, GeBO.l02.l5, GeBO.20l.3, ;
~'~' "''' ' 15 - ~

13~0!.)2 , ,, GeBO.202.3, GeBo~3ol~45r GeBO,302.4sr GeBO.50l.75, GeBO.50z.75, GeBO.702.05, GeBO.7O3.05, GeBO2.5, GeBO3.5, GeBl.5O3.25 and GeBI.5O4.25.
The use of any of the compounds repre~ented by formulae (I) to (V) as a main negative electrode active material affords a nonaqueous secondary battery having `~
excellent charge and discharge cycle characteristics, a high `
discharge potential, a high capacity and high safety. ;
The pronouncedly excellent effects of the present ` ``
invention come from the use of a compound containing Sn in ~ `~
which Sn is present with divalency. The valency of Sn can be determined through chemical titration, for example, according ~ i```~
to the method described in Physics and ChemistrY of Glasses, ~`` ;;
Vol. 8, No. 4, p. 165 (1967). It is also decided from the Xnight shift in the solid nuclear magnetic resonance spectrum ;~ ;;
of Sn. For example, in broad-line NMR measurement, metallic Sn (zero valent Sn) shows a peak in an extremely low magnetic ~;
field in the vicinity of 7000 ppm with reference to Sn(CH3)4, whereas the peak of SnO (divalent Sn) appears around 100 ppm, and that of SnO2 (tetravalent Sn) appears around -600 ppm. `
Like this, the Knight shift largely depends on the valency of -~ "'~?,"~j,,`
Sn, the center metal, with the ligands being the same. ~he `
valency can thus be determined by the peak position obtained by ll9Sn-NMR analysis.
The negative electrode active material of the present invention may contain various compounds, such as compounds of the ~roup IA elements (e.g., Li, Na, K, Rb, and Cs), .

~.,, ,,,. i ,:

',:: :' ~,, transition metals (e.g., Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Agl lanthanoid metals, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg), the group IIA elements (e.g., Be, Mg, Ca, Sr, Ba), and the group VIIB elements (e.g., F, Cl, Br, I). Further, it may also contain dopants of various compounds (e.g., compounds of Sb, In, Nb) for improving electrical conductivity. The addition amount thereof is preferably 0 to 20 mol%.
The compounds of formulae (I) to (V) can be : ., synthesized by either a calcination method or a solution ~-method. `
For instance, the calcination method is conducted by calcining a mixed compound of M1 compound and M2 compound ~where Ml and M2, which are different from each other, each represent Si, Ge, Sn, Pb, P, B, Al, As, Sb). ~i The tin compounds include SnO, SnO2, Sn2O3, Sn3O4, Sn7O~3-H2O~ Sn8l5~ stannous hydroxide, stannic oxyhydroxide, stannic acid, stannous oxalate, stannous phosphate, orthostannic acid, metastannic acid, parastannic acid, ~ ;
. , .1. , ..:
stannous fluoride, stannic fluoride, stannous chloride, ~
: ~ . . :.,~ .:
stannic chloride, stannous bromide, stannic bromide, stannous ~ ~`
! ' iodide, stannic iodide, tin selenide, tin telluride, stannous pyrophosphate, tin phosphite, stannous sulfate, stannic ~ ;~
sulfate.
The silicon compounds include SiO2, SiO, organic silicon halide compounds such as silicon tetrachloride, : . ~.: : :: :

~ ....:
'. . .:. ` -' 3 ~ ~ ~ 2 ;: ~

" ~. . ,., ~, silicon, tetrafluoride, trichloromethylsilane, ~ ;
dimethyldichlorosilane and tetraethhylsilane, alkoxysilance compounds such as tetramethoxysilane and tetraethoxysilane, and hydroxysilane compounds such as trichlorohydroxysilane.
The germanium compounds include GeO2, GeO, germanium :~ ~
tetrachloride, and alkoxy germanium compounds such as ` : `
germanium tetramethoxide and germanium tetraethoxide.
The lead compounds include PbO2, PbO, Pb203, Pb304, `~
PbCl2, lead chlorate, lead perchlorate, lead nitrate, lead ` ;
carbonate, lead formate, lead acetate, lead tetraacetate,`~
lead tartrate, lead diethoxide, lead di(isopropoxide). ;. r, The phosphorus compound includes phosphorus ` `~
pentoxide, phosphorus oxychloride, phosphorous pentachloride, :,. - -phosphorus trichloride, phosphorous tribromide, trimethylphosphate, triethyl phosphate, tripropyl phosphate, stannous pyr~phosphate, and boron phosphate.
The boron compound includes boron sesquioxide, boron trichloride, boron tribromide, boron carbide, boric acid, trimethyl borate, triethyl borate, tripropyl borate, tributyl ; `
borate, boron phosphide, and boron phosphate.
The aluminum compound includes aluminum oxide (a~
~ , . ,.: .
alumina or ~-alumina), aluminum silicate, aluminum tri- ` ~.
isopropoxide, aluminum tellurite, aluminum chloride, aluminum ~ ~
boride, aluminum phosphide, aluminum phosphate, aluminum `
lactate, aluminum borate, aluminum sulfide, and aluminum . ::~
sulfate.

: "~
,:, - , ", -: ` 21~34~3 -The antimony compound includes antimony tribromide, antimony trichloride, diantimony trioxide, and triphenylantimony.
Calcination is carried out preferably at a rate of temperature rise of 4~ to 2000C/min, still preferably 6 to 2000Ctmin, most preferably 10 to 2û00C/min; at a calcination temperature of 250 to 1500C, still preferably 350 to 1500C, most preferably S00 to 1500C; for a period ~;
of 0.01 to 100 hours, still preferably 0.5 to 70 hours, most preferably 1 to 20 hours. After calcination, the system is cooled at a rate of temperature drop of 2 to 107C/min, still preferably 4 to 107C/min, still more preferably 6 to 107C/min, most preferably 10 to 107C/min. `
The term "rate of temperature rise" as used herein means an average rate of temperature rise from 50%
calcination temperature (C) up to 80% calcination temperature (C), and the term "rate of temperature drop~ as used herein means an average rate of temperature drop from 80% calcination temperature (C) to 50~6 calcination temperature (C).
Cooling of the calcined product may be effected `
either withini a calcining furnace or out of the furnace, for :
example, by pouring the product into water. Super-quenching methods described in Ceramics Processinq, p. 217, Gihodo (1987), such as a gun method, a Hammer-Anvil method, a slap method, a gas atomizing method, a plasma spxay method, a - 19 - ..... ~;.'' ~ c~ ~'3 2 ; ;~

centrifugal quenching method, and a melt drag method, can also be used. Further, cooling may be conducted by a single roller method or a twin-roller method described in New Glass Handbook, p. 172, Maruzen ~1991). Where the material melts `~
during calcination, the calcined product may be withdrawn ~ `
continuously while feeing the raw materials. The molten ~ `
liquid is preferably stirred during calcination.
The calcining atmosphere preferably has an oxygen ~ ` ~`,'~!" '`'~" ,'`' content of not more than 100% by volume, preferably not more than 20% by volume, more preferably not more than 5% by "`~
volume. An inert gas atmosphere is still preferred. Inert -gas includes nitrogen, argon, helium, krypton, and xenon.
The compound of formulae (I) to (V) preferably has an average particle si.ze of from 0.1 to 60 ~m. The calcined ;
product can be ground to size by means of well-known grinding machines or classifiers, such as a mortar, a ball mill, a .. : . ~ ;
sand mill, a vibration ball mill, a satellite ball mill, a planetary ball mill, a spinning air flow type jet mill, and a sieve. If necessary, wet grinding using water or an organic solvent, such as methanol, may be conducted. The grinds are - ~
preferably classified to obtain a desired particle size `-either by dry or wet classification by means of a sieve, an ~`
air classifier, etc.
According to one of the embodiments of the present invention in which the negative electrode active material is ~
an oxide containing fluorine, the fluorine in the negative -- 20 - ~-. ~ .'; ~-:'' ".' ', ' '',''."'.'`',''.~

? 2,13~2 electrode active material strengthens the structure and chemical stability of a compound oxide. In particular, fluorine in an amorphous oxide is effective to further enhance the amorphous properties thereby improving the electrochemical structural stability. -Specific examples of the fluorine-containing negative electrode active material or a precursor thereof are -;`GeFO.zO0.9, GeF~.2O1.~, SnFc.2oo.9, SnFo.2ol.s~ SnsiFo.4o2.s~ PbFo.4l.s~
PbFo.2Ol.9, Pb2Fo.2O2 9, Pb3Fo.4O3.8, Sb2Fo.2o2.sr Sh2Fo.2o3.st Sb2Fo.24.st ~i2Fo.43.~i, Bi2Fo.43.s~ and Bi2Fo.2o4.9~ and non-stoichiometrical compounds or compound oxides thereof.
Preferred of these fluorine-containing negative `
electrode active materials are fluorine-containing SnO, SnO2, ~`
GeO, GeO2, and SnSiO3, with fluorine-containing SnSiO3 being still preferred. Fluorine-containing and amorphous SnO, SnO2, GeO, GeO2, and SnSiO3 are particularly preferred. ; i A preferred fluorine content in the fluorine- -containing negative electrode active material is from 10 to . ~ .
100 mol%, particularly 20 to 50 mol%, based on the total amount of the metal elements in the active material.
The F-containing negative electrode active materials - ~ -preferably include those represented by formula SnxSiFyO
(0.2 < x ~ 1.0; 0 < y < 2; 2.2 < z ~ 3). The F-containing compound oxide may be crystalline or amorphous but is preferably amorphous.
The F-containing negative electrode active material ,, ~ ',' ~ ~' "' ~ ~ 3 ~ ~ ~ 2 precursor mainly comprising Sn can be synthesized by calcining a mixture of the above-mentioned tin oxide and -~
fluorine compound in air or an inert gas at a high temperature.
In the case of adding another metal or metals, a- ~~
mixture of the tin compound, the fluorine compound, and an oxide of another metal or metals is calcined. For example, ", ~ .
fluorine-containing SnSiO3 can be synthesized by calcining a ~ -~
. -; ,,,, ~ .. ~
mixture of SnO, SnF2, and SiO2 in an inert gas at 200 to 1200C, preferably 500 to 1100C. `; `~;
For obtaining an amorphous (glassy) active material, the calcined product is ~uenched at a cooling rate of 1.5 to ;``
100C/min, preferably 5 to 20C/min. ; `
The fluorine-containing negative electrode active; ~`
material precursor can also be synthesized by co- ~ `f pre~ipitation in a solution (co-precipitation method). In this case, an acidic or alkaline aqueous solution containing, ` ~-for example a salt of the group IIIB, IVB, or VB element is neutralized in the presence of a fluoride ion to form a fluorine-containing compound hydroxide or a fluorine-containing compound oxide. ` `~
The negative electrode active material precursors containing other metals can also be synthesized by the above- - -described calcination method or co-precipitation method.
,.:,.: ,~ ~ ".
The positive electrode active material which can be ~ ~-used in the present invention may be a transition metal oxide . ~ :. ~ -.
~,~ ., ~ . :.

213~!( S2 capable o~ reversibly intercalating and deintercalating a lithium ion but is preferably a lithium-containing transition metal oxide. -~
L.ithium-containing transition metal oxides which can be used as a positive electrode active material include, for preference, lithium-containing oxides of Ti, V, Cr, Mn, Fe, ;~`~
Co, Ni, Cu, Mo or W. The oxide may contain other alkali metals (the group IA and IIA elements) in addition to Li and/or other elements such as Al, Ga, In, Ge, Sn, Pb, Sb, Bi, ;
Si, P, B, etc. The ratio of these additional elements is ;~
preferably up to 30 mol%, still preferably up to 10 mol%, based on the transition metal.
Preferred of the Li-containing transition metal oxides as a positive electrode active material are those ~- ;
prepared from a mixture of a lithium compound and at least one compound of a transition metal selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mo, and W at a lithium compound/total transition metal compounds molar ratio of 0.3 to 2.2.
Still preferred are those prepared from a mixture of a lithium compound and at least one compound of a transition metal selected from V, Cr, Mn, Fe, Co, and Ni at a lithium compound/total transition metal compounds molar ratio of from 0.3 to 2.2.
The most preferred are those represented by formula ~;
Li~QOy (Q represents at least one transition metal selected from Co, Mn, Ni, V, and Fe; x is from 0.2 to 1.2; and y is ~
, ~, ,~,.
- 23 ~

b ~ 1 3 ~ ~ 5 2 . ~.
from 1.4 to 3). Q may contain, in addition to a transition . . ...
metal, other metals~ such as Al, Ga, In, Ge, Sn, Pb, Sb, Bi, Si, P, B, etc. The ratio of the other metals is preferably up to 30 mol% based on the total transition metals.
Suitable examples of the lithium-containing metal oxide positive electrode active material which can be ~ ~`
preferably used in the present invention are LiXCoO2, LiXNio2, ; ~
LixMnO2~ LixCo~Nil-a2~ LiXCobVI-b2~ LiXCbFel-b2~ l'ixMn24~
LiXMnCCO2-CO4~ LixMncNi2-co4~ LixMncv2-coz~ LixMncFe2-co4~ a mixture ` -`
~f LixMn2O4 and MnO2, a mixture of Li2xMnO3 and MnO2, a mixture ~ .., ~, .....
of LixMn2O4, Li2xMnO3, and MnO2 ~wherein x = 0.2 to 1.2; a =
0.1 to 0.9; b = 0.8 to 0.98; c = 1.6 to 1.96; and z = 2.01 to `~ ~ :
5). `:.`;.
Preferred examples of the lithium-containing metal .
oxide positive electrode active materials are LixCoO2, ~ ...
LiXNiO2, LixMnO2, LixCo~Ni 1-~2~ ~ixCobV1bOz, Li~CobFe1bOz, LixMn2O4, .. ; ~.
LiXMncco2coh~ LixMhcNi2-co4~ LixMncv2-co4~ and LixMncFe2-co4 (wherein ~ .
x = 0.7 to 1.2; a = 0.1 to 0.9; b = 0.8 to 0.98; c = 1.6 to ::~
1.96; z = 2.01 to 2.3). ` .
Still preferred of the lithium-containing metal oxide positive electrode active materials are LixCoO2, LiXNiO2, , ~ . .. , ,-;.
LixMnO2, LixCoaNilaO2, LixMn2O4, and LixCobVlbOz (wherein x = 0.7 to 1.2; a = 0.1 to O.g; b = 0.9 to 0.98; and z = 2.01 to :~
2.3). ~. .
The most preferred are Lixcoo~ LixNi2~ LiXMnO2~
LixCoaNil~O2, LixMn2O4, and LixCobVlbOz (wherein x = 0.7 to 1.2;

~ .

- ~
~13~0~2 a = 0.1 to 0.9; b = 0.9 to 0.98, and z = 2.02 to 2.3).
The value x in the above formulae is the value before commencement of charging and discharging and varies with a charge and a discharge.
According to another embodiment of the present invention, a spinel type manganese-containing oxide is used as a positive electrode active material. Spinel type oxides have a spinel structure represented by formula A(B23O4, in which the oxygen anions are aligned in cubic closest packing and occupy part of the faces and apexes of a tetrahedron and an octahedron. The unit cell is composed of 8 molecules, and oxygen occupies 32e positions in the Fd3m space. The unit cells occupy the lattice spacing of 64 octahedrons at three crystallographically non-equivalent positions, 8al 8b, and 48f. In this spinel structure, cations B are positioned at the lattice spacing sites of the 16d octahedrons (the vacant octahedron site is 16c), and cations A are positioned at the ;
lattice spacing sites of the 8a tetrahedrons. Each 8a octahedron shares the face with the adjoining 4 vacant 16c octahedrons thereby to provide passageways through which cations A diffuse (e.g., 8a ~ 16c ~ 8a ~ 16c). On the other ;;
hand, each 8b tetrahedron shares the face with the 16d octahedron formed of cations B, resulting in energy disadvantage to cations~ occupation. The 48f tetrahedron ~ ~ -shares the face with both the 16d and 16c octahedrons.
According to the distribution of cations A, A(B2)O4 is called ,'.',',' .'.' ,:.''.'.",'~"'.,' . . :-;. ,.~..

--- 2 1 3 ~ V ~

a normal spinel structure, and B(AB)04 is called an inverse~
spinel structure. Axsy(AlxBly~o4r an intermediate structure between a normal spinel and an inverse-spinel, is also called a spinel. ;
. . . ,: -Manganese oxides having a normal spinel structure ~ ;
typically include LiMn204, which serves as a positive electrode active material. In this structure, a half of the ;~
Mn cations are trivalent, with the another half being tetravalent. ~-MnO2, also known as an active material, is ;
regarded to have a spinel structuxe with defects, derived by ; -removing lithium from LiMn204, in which all the Mn cations ~ ` ;
are tetravalent, as described in U.S. Patent 4,246,253. The manganese oxide positive electrode active materials which can ,~ ,. ..
be used in khe present invention include all of those having a normal spinel structure, those having an inverse-spinel , . :~
structure, those having a defect-free structure, and those having a non-stoichiometrical spinel structure with defects.
Suitable Li-containing manganese oxides having a spinel structure which can be used in the present invention -~
include those represented by general formula Li~+x[Mn2y~0 .. . ~
(O < x < 1.7; 0 ~ y < 0.7). Such compounds include Li4Mn50lz (or Li[Lil/3Mn5/3]04). In addition, the following compounds are also included under the scope covered by the above . ~ ..
general formula ~structural formulae include those represented by multiplying the general formula by an integer or a decimal):
,,'~; .' :'"; ', ;.

. : ..

... , . ,. . . . .... ,, .. , ,,.~,,.. ~ .. ~ .

~ 213~0~2 ;,' `,',',` !

Li4Mn409, LiMnO2 (or Li2Mn204), Li2MnO3, Li5Mn409, and Li4Mn50~2 Suitable Li-containing manganese oxides having a spinel structure which can be used as a positive electrode active material in the prr~sent invention further include those represented by general formula Lil-x[Mn2-y]4 (0 < x < 1.0; 0 ~ y < 0.5). Preferred of them are those represented by qeneral formula Li~[Mn2y]04 (0.20 < x < 1.0;
O < y < 0.2), such as Li2Mn50l~ (or Li~x[Mn2y]04 (x = 0.273; y = 0.182)), which is a non-stoichiometrical spinel compound disclosed in JP-A~4-240117; and those represented by general formula Li~x[Mn2y]04 ~0 < x ~ 0.20; 0 < y < 0.4), such as ~
Li2Mn409. In addition, the following compounds are also :~.
included under the scope covered by the above formula `
Li1x[Mn2y]o4 (stxuctural formulae include those represented by multiplying the general formula by an integer or a decimal)~
Li4Mnl6.5035, Li2Mn750l6, and LiO.7MnO4 The above-mentioned spinel type manganese oxides as a positive electrode active material can be obtained by reacting~a lithium salt and a manganese salt or a manganese ~ ~
oxide in a solid phase at a high temperature according to a .. .
known method. In using lithium carbonate and manganese dioxide as starting materials, calcination is carried out at 350 to 900C, preferably 350 to 500C, for 8 to 48 hours. . .``
In using lithium nitrate having a low melting point (261C) . ,~,.. ....... ...

~ ~13~a2 `,, "~ . ' :' '~

as a lithium salt, calcination is carried out at 300 to . .
900C, preferably 300 to 500C. Manganese oxides to be used - -include ~-MnO2, electrolytically prepared MnO2 tEMD~
chemically prepared MnO2 (CMD), and a mixture thereof.
Lithium-manganese double oxides (e.g., Li2Mn4Og) may also be used as a lithium material. In this case, the Li-Mn double ~ ;
oxide is mixed with a manganese material, e.g., manganese .....
dioxide, and calcined at 350 to 500C. ;
The spinel type manganese oxide may be doped with one .
or more of other transition metal elements, typical elements, ~ ~:
and rare earth elements to form a compound oxide. Preferred dopants are transition metal elements, such as Co, Ni, Ti, V, Zr, Nb, Mo, W, and Fe.
The positive electrode active materials which can be .: .
used in the present invention also include manganese oxide compounds having a hollandite skeleton structure as disclosed in JP-A-4-270125, which are regarded as having the above- ~-described general formulae with part or most part (e.g., 95%
or more) of Li cations thereof being substituted with other cations, e.g., H, K, Na, and ammonium ions. Hollandite type ;
compounds in which Li cations are substituted with H can easily be obtained by, for example, treating an Li-Mg double oxide represented by the above general formula with an acid at a high temperature to remove Li.
The positive electrode active materials can be ~-synthesized by mixing a lithium compound and a transition 2 1 ~ 2 metal compound, followed by calcination or by reacting these materials in a solution. The former calcination method is preferred.
Calcination is carried out at a calcination temperature selected from the range :in which at least part of the mixed compounds may be decomposed and melted, for example, from 250 to 2000C, preferably from 350 to 1500C, for 1 to 72 hours, preferably 2 to 20 hours. Prior to calcination, the mixture is preferably pre-calcined at 250 ~ ;~
~o 900C. Mixing of the raw materials may be either dry blending or wet blending. If desired, calcination may be followed by annealing at 200 to 900C. ~;
The calcination atmosphere is not limited and may be an oxidizing atmosphere or a reducing atmosphere. For example, calcination can be performed in air, a prepared gas ;
having an arbitrary oxygen concentration, hydrogen, carbon ~ -~
monoxide, nitrogen, argon, helium, krypton, xenon, or carbon dioxide. ; ~ ``
In the synthesis of positive electrode active ; ``
materials, chemical intercalation of a lithium ion into a '!`,"",'."~.`.-,,.,`transition metal oxide is preferably achieved by reacting metalllic lithium, a lithium alloy or butyl lithium with the transitlon metal oxide. j~`
While not limiting, the positive electrode active material to be used in the present invention preferably has an average particle size of from 0.1 to 50 ~m and a BET ~ -,. . ... ..

'~; . -.`,. ~ ' ' ,', "''"" ~"

~3~2 . ``;

specific surface area of from 0.01 to 50 m2/g. An a~ueous solution (supernatant liquid) of S g of a positive electrode -~
active material in 100 ml of distilled water preferably has a : :
pH of 7 to 12.
The resulting positive electxode active material can " ~;
be ground to size by means of well-known grinding machines or `.~;
classifiers, such as a mortar, a ball mill, a vibration ball mill, a vibration mill, a satellite ball mill, a planetary ball mill, a spinning air flow type jet mill, and a sieve. ~ -If desired, the positive electrode active material : :
obtained by calcination may be washed with water, an aqueous .
acid solution, an aqueous alkali solution or an organic : ;
solvent before use. .
A preferred combination of a negative electrode active material and a positive electrode active material is a combination of a compound of formula (I) as a negative electrode active material and Lixcoo2~ LixNio2~ LiXCoaNilaO2, LixMnOz, LixMn2O4, or LixCobVl_bOz ( X = O . 7 to 1.2; a = 0.1 to ;~
0.9; b = 0.9 to 0.98; and z = 2.02 to 2.3) as a positive ~: .
electrode active material, still preferably a combination of a compound of formula (III) and Lixcoo2~ LixNio2r LiXCo~Ni~aO2, : -.:, ; ~
LixMnO2, LixMn2O4, or LiXCobV~bO8 (x = 0.7 to 1.2; a = 0.1 to -~
0.9; b = 0.9 to 0.98; and z = 2.02 to 2.3) as a positive ~;~
electrode active material, most preferably a combination of a i ~.
compound of formula (IV) as a negative electrode active material and LixCoO2, LiXNiO2, LixCoaNi~aO2, LixMnO2, LixMn2O4, or r ~ 1 3 ~

LixCobVI_bOz (X = O . 7 to 1.2; a = 0.1 to 0.9; b = 0.9 to 0.98; ;and z = 2.02 to 2.3) as a positive electrode active material.
Further, preferred is a combination of a compound of formula (I) as a negative electrode active material and Li4Mn409, LiMnO2, Li2Mn204, Li2MnO3, Li~Mn409, Li4Mn50l2, Li4Mnl6503s, Li2Mn7.50l6 or LiO.7Mn204.
Such combinations of active materials afford a nonaqueous secondary battery having excellent charge and ; ;
discharge cycle characteristics, a high discharge potential, and a high capacity.
Lithium is intercalated into a compound represented "
by any of formulas (I) to (V) in an amount of from 1 to 20``~ "~
equivalents, preferably from 3 to 10 equivalents.
The ratio of a positive electrode active material to `
a negativa electrode act.ive material is decided according to ` `~
the above-mentioned equivalent amount. It is preferable to use a positive electrode active material in an amount based on the calculated ratio multiplied by 0.5 to 2. Where any ;`
other substance than a positive electrode active material,`~
e.g., metallic lithium, a lithi m alloy or butyl lithiu , is `
used as a lithium source, the amount of a positive electrode - ~`~
active material to be used is decided in conformity with the equivalent amount of deintercalated lithium of the negative -~
electrode active material. In this case, too, the ratio based~on the equivalent amount is preferably multiplied by i 9 ~ ~

Negative electrode active materials which may be used ;
in combination with the negative electrode active material of the present invention include me~allic lithium, lithium alloys (e.g., alloys with Al, Al-Mn, Al-Mg, Al-5n, Al-In or ~l-Cd), and calcined carbonaceous compounds capable of ~ ;;
intercalating and deintercalating a lithium ion or metallic lithium.
The purpose of the combined use of metallic lithium or a lithium alloy is to intercalate lithium into a compound mainly comprising an oxide of formula (I) to (V) within a cell but not to utilize the dissolution-precipitation ~
reaction of metallic lithium, etc. as an electrode reaction. ~;;
An electrode material mixture which can be used in .
the present invention comprises the above-described active -material, a conducting agent, a binder, a filler, and so `
forth.
The conducting agent may be any electron-conducting material which undergoes no chemical change in an assembled ;
battery. Suitable conducting agents include natural graphite tscale graphite, flake graphite, lumpy graphite, etc.), artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, metal powders (e.g., copper, nickel, aluminum or silver powder) r metallic fibers, polyphenylene derivatives, and mixtures of two or more thereof. A
combination of graphite and acetylene black is particularly ~ ;
preferred. ~ ~
,, .,:'..
- 32 ~

13~52 ~.
The conducting agent is preferably used in an amount of from 1 to 50% by weight, still pr~eferably from 2 to 30% by ~ ~
weight, based on the total weight of the active material ;`~. `;
mixture. Carbon or graphite is preflerably used in an amount of from 2 to 15% by weight.
The binder includes polysaccharides, thermoplastic ;
resins, and rubbery polymers; such as starch, polyvinyl ~ `
alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, ~`
regenerated cellulose, diacetyl cellulose, polyvinyl `;
, ~' .,. .,1, .' .,~ ',. . . .
chloride, polyvinyl pyrrolidone, tetrafluoroethylene, polyvinylidene f luoride, polyethylene, polypropylene, `~
ethylene-propylene-diene terpolymers (EPDM), sulfonated EPDM, `~
styrene-butadiene rubbers, polybutadiene, fluorine rubbers, ~ ;
polyethylene oxide, and mixtures of two or more thereof. In using a compound having a functional group reactive with lithium, such as a polysaccharide, it is preferable to ` ~ :
deactivate the functional group by addition of a compound having an isocyanate group. The binder is used in an amount of 1 to 50% by weight, preferably 2 to 30% by weight, based ~`i` ~"
on the total weight of the active material mixture. `~
In particular, polymers having a decomposition temperature of not lower than 300C are preferred as a binder for the negative electrode active material of the present invention. Such polymers include polyethylene, polypropylene, epoxy resins, polyester resins, and fluorine resins, with fluorine resins being preferred. The term ~ `
.' : .. ` . ,, ~
- 33 - ;~

, . ,. ~ ,. . .

-` ~13~2 :

"fluorine resin" is used herein as a seneral term for polymers having a carbon-fluorine bond in the molecule thereof as specified in JIS K6900 "Glossary of Terms Used in Plastic Industry~
Suitable examples of the fluorine resins are shown below.
(A-l) Polytetrafluoroethylene (PTFE) ~ ~
(A-2) Polyvinylidene fluoride (PVDF) ~; ;
(A-3) Tetrafluoroethylene-hexafluoropropylene copolymer (FEP) (A-4) Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) (A-5) Vinylidene fluoride-hexafluoropropylene copolymer (A-6) Vinylidene fluoride-chlorotrifluoroethylene copolymer (A-7) Ethylene-tetrafluoroethylene copolymer (ETFE resin) (A-8) Polychlorotrifluoroethylene (PCTFE) ;
(A-9) Vinylidene fluoride-pentafluoropropylene copolymer (A-lO) Propylene-tetrafluoroethylene copolymer (A-11~ Ethylene-chlorotrifluoroethylene copolymer (ECTFE) (A-12) Vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer (A-li3) Vinylidene fluoride-perfluoromethyl vinyl ether-tetrafluoroethylene copolymer Copolymer resins comprising anothier ethylenically unsaturated monomer in addition to the above-mentioned monomers are also useful. Specific but non-limiting examples _ 34 - ~
. -- ,:, .
':' . -:.

- - ~13~52 :::

, . - . . . ~
of copolymerizable unsaturated monomers include acrylic . ...: ~
esters, methacrylic esters, vinyl acetate, acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, butadiene, styrene, N-vinylpyrrolidone, N-vinylpyridine, glycidyl methacrylate, hydroxyethyl methacrylate, and methyl vinyl ether. ;~
The binder resins can be obtained by any of solution polymerization, emulsion polymerization, suspension . ,,: -polymerization, and gaseous phase polymerization, and the polymer may be any of random polymers, graft polymers, and ` : ~ `
block polymers.
The above-mentioned binder resin may be used in combination with one or more other polymers, such as carboxymethyl cellulose, sodium polyacrylate, hydroxyethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, ` `
polyethylene oxider and alginic acid. i~
The binder is preferably used in an amount of from ~`
0.5 to 30~ by weight based on the negative electrode active `
material.
The filler to be used in the present invention is not `~
particularly limited as long as it is a fibrous material undergoing no chemical change in an assembled battery.
Suitable fillers include fibers of polyolefins (e.g., ~ ~ `
polypropylene or po:Lyethylene), glass fiber, and carbon -fiber. While not limiting, the filler is preferably used in .. , ., .. ~ ~
: . . , ,: . ~, ., - 35 ~

, ,~ , ,; ",......

~13~2 :

an amount of up to 30D6 by weight based on the total weight of ~he active material mixture~
The nonaqueous electrolytic solution which can be used in the nonaqueous secondary battery of the present invention consists o at least one oxç~anic solvent and at least one lithium salt soluble in the solvent. Suitable organic solvents include aprotic solvents, such as propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ~-butyrolactone, 1, 2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1, 3-dioxolane, formamide, ~ `
dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl f ormate, methyl acetate, methyl propionate, ethyl propionate, phosphoric triesters, trimethoxymethane, dioxolane derivatives, sulfolane, 3-methyl-2-oxazolidinone, propylene carbonate derivatives, tetrahydrof uran derivatives, ethyl ether, and 1, 3-propanesultone. ~rhese solvents may be used either individually or in combination of two or more ~
thereof. Suitable lithium salts soluble in these solvents ~ `
include LiCl04, LiBF6, LiPF6, LiCF3S03, LiCF3C02, LiAsF6, LiSbF6, LiBloCllo, lower aliphatic lithium carboxylates, LiAlCl4, LiCl, LiBr, LiI, chloroboran lithium, and lithium tetraphenylborate. These lithium salts may be used either individually or in combination of two or more thereof . In particular, a solution of LiCF3S03, LiCl04, LiBF4 and/or LiPF6 in a mixed solvent of propylene carbonate or ethylene _ 35 -- . - : , . i :
:,, " ~ "" i ;",", ~, " ., ":, ~

~ 1 3 ~

carbonate and 1,2-dimethoxyethane and/or diethyl carbonate is a preferred electrolytic solution.
The amount of the electrolytic solution to be used in --a battery is not particularly limited and can be selected ~ "
according to the amounts of the positive and negative electrode active materials or the size of the battery. - ~ ~
The concentration of the supporting electrolyte is ; ` ~;
preferably from 0.2 to 3 mols per liter of the electrolytic solution. ``;~
In addition to electrolytic solutions, inorganlc or organic solid electrolytes may also be employed. `~
Examples of suitable inorganic solid electrolytes `~
include a lithium nitride, a lithium halide, and a lithium `~ ~
oxyacid salt. Among them preferred are Li3N, LiI, Li5NI2, ~ ` `
Li3N-LiI-LiOH, LiSiO4, LiSiO4-LiI-LiOH, xLi3PO4-(l-x)Li4SiO4, Li2SiS3, and phosphorus sulfide compounds. " ~`
Examples of suitable organic solid electrolytes include polyethylene oxide derivatives or polymers containing the same (see JP-A-63-135447), polypropylene oxide derivatives or polymers containing the same, polymers containing an ionizing group ~see JP-A-62-254302, JP-A-62 254303, and JP-A-63-193954), a mixture of a polymer containing an ionizing group and the above-mentioned aprotic electrolytic solution (see U.S. Patents 4,792,504 and 4,83U,939, JP-A-62-22375, JP-A-62-22376, JP-A-63-22375, JP-A- .
.: . ~, `. ::`,, .
63-22776, and JP-A-1-95117)/ and phosphoric ester polymers : ~' . ' ' ', ' ' - 37 - `~
'~' '. `',:,",,' ' `
`': ' . "' :~':

2~3~2 (see JP-A-61-256573). A combination of polyacrylonitrile and an electrolytic solution (see JP-A-62-278774) and a combination of an organic solid electrolyte and an inorganic solid electrolyte (see JP-A-60-1768) are also known.
As a separator, an insulating thin film having high ion permeability and prescribed mechanical strength is used.
A sheet or nonwoven fabric made of an olefin polymer (e.g., ~ ;
polypropylene), glass fiber or polyethylene is usually ~-employed for their organlc solvent resistance and hydrophobic properties. The pore size of the separator is selected from the range generally used for batteries, e.g., from 0.01 to 10 ~m. The thickness of the separator is selected from the `;
range generally used for batteries, e.g., from 5 to 300 ~m. ~`
For the purpose of improving charge and discharge `
characteristics, the electrolytic solution may contain other ~ ``
compounds, such as pyridine (see JP-A-49-108525), triethyl phosphite (see JP-A-47-4376), triethanolamine (see JP-A-52-72425), a cyclic ether (see JP-A-57-152684), ethylenediamine ~`
(see JP-A-58-87777), n-glyme (see JP-A-58-87778), hexaphosphoric acid triamide (see JP-A-58-87779), a ~ ;
nitrobenzene derivative (see JP-A-58-214281), sulfur (see JP-A-59-8280), a quinoneimine dye (see Jp-A-59-68l84j~ an N-substituted oxaæolidinone and an N,N'-substituted imidazolidinone (see JP-A-59-154778), an ethylene glycol dialkyl ether (see JP-A-59-205167), a quaternary ammonium salt (see JP-A-60-30065), polyethylene glycol (see JP-A-60- -~13~2 41773), pyrrole (see JP-A-60-79677), 2-methoxyethanol (see JP-A-60-89075), A~C~3 (see JP-A-61-88466), a monomer providing a conductive polymeric active material (see JP-A- .
61-161673), triethylenephosphoramide (see JP-A~61-208758), a trialkylphosphine (JP-A-62-80976), morpholine (see JP-A-62- :
80977j, an aryl compound having a carbonyl group (see JP-A-62-86673), hexamethylphosphoric triamide and a 4-alkylmorpholine (see JP-A-62-217575), a bicyclic tertiary -amine (see JP-A-62-217578), an oil (see JP-A-62-287580), a quaternary phosphonium salt (see JP-A-63-121268), and a tertiary sulfonium salt (see JP-A-63-121269).
In order to make the electrolytic solution . ~ , . ~ :.:;
incombustible, a halogen-containing solvent, such as carbon tetrachloride or trifluorochloroethylene, may be added to the . :~
electrolytic solution (see JP-A-48-36632). In order to make ; . ~.
the electrolytic solution resistant to high-temperature .~
preservation, car~onic acid gas may be incorporated thereto ~;` .
(see JP-A-59-134567). ~ ~-The positive or negative electrode active material .... .....
mixture may contain an electrolytic solution or an electrolyte. For example, it is known to add the above- . :
mentiioned ion~conductive polymer or nitromethane (see JP-A-48-36633) or an electrolytic solution (see JP-A-57-12487) to ~ ;
the active material mixture. ; .... ;;
The surface of the positive electrode active material . ;:
may be modified by treating with an esterification agent (see ~:~
: '. ~.', - 39 ~
' ~ ' :' `'.' ' "- '~""'~ ",' 2~3~0~

JP-A-55-163779), a chelating agent (see JP-A-55-163780), a .
conducting high polymer (see JP-A-58-1631ZB8 and JP-A-59~
14274), polyethylene oxide (see JP-A-60-97561), and the like.
The surface of the negative electrode active material may also be modified by, for example, providing a layer comprising an ion-conductive polymier or polyacetylene (see JP-A-58-111276) or treating with ~iC~ (see JP-A-58-142771). -~
A collector for an active material may be made of any electron-conducting substance which undergoes no chemical change in an assembled battery. Suitable materials of a collector for the positive electrode include stainless steel, nickel, aluminum, titanium, calcined caxbon; and aluminum or . ~. . .
stainless steel with its surface treated with carbon, nickel, ` `
titanium or silver. Suitable materials of a collector for the negative electrode include stainless steel, nickel, copper, titanium, aluminum, calcined carbon; copper or stainless steel with its surface treated with carbon, nickel, titanium or silver; and an A~-Cd alloy. These materlals may be subjected to surface oxidation. The collector may have a variety of fo~mis, such as a foil, a film, a sheet, a net, a punched sheet, a lath, a porous body, a foamed body, a - ~;
fibrous body, and so on. While not Iimiting, the thickness of the collector is from 1 to 500 ~m.
The battery according to the present invention may have any shape, such as a coin shape, a button shape, a sheet shape, a cylindrical shape, and an angular shape.

,., ' 2 1 3 ~ ~ ~ 2 ~.
i - , , A coin-shaped or button-shaped battery is generally produced by compressing a positive or negative active .......
material mixture into a pellet having prescribed thickness and diameter according to the size of the battery. A sheet, cylindrical or angular battery is generally produced by coating a collector with a positive or negative active ~ "
material mixture, followed by drying and compressing. The thickness, length or width of the coating layer are decided according to the size of the battery. In particular, the dry thickness (thickness after compression) is preferably ~ ~`
selected fxom the range 1 to 2000 ~m. `` ~`
The application of the nona~ueous secondary battery -of the present invention is not particularly limited. For ` `
example, it is useful in electronic e~uipment, such as ;
notebook-size colo.r or monochromatic personal computers, pen . . .
input personal computers, pocket-size (palmtop) personal COmputQrS~ notebook-size word processors, pocket-size word ``~
processors, electron book players, pocket phones, wireless ; `;
extentions of key telephone sets, pagers, handy terminals, portable facsimiles, portable copying machines, portable printers, headphone stereos, video cameras, liquid crystal TV
setsl, handy cleaners, portable CD, mini disk systems, electrical shavers, machine translation systems, land mobile ;~
radiotelephones, transceivers, electrical tools, portable ;;
calculators, memory cards, tape recorders, radios, backup powers, and so on; automobiles, electrically-powered - 41 - ~ ~
,.,,, ~ .,:

vehicles, motors, lights, toys, family ~home) computers, load -~
conditioners, irons, watches, stroboscopic lamps, cameras, `
medical equipment (e.g., pacemakers, hearing aids, and massaging machines); military equipment; and spacecraft equipment. The nonaqueous secondary battery of the present invention may be used in combination with solar batteries.
The present invention will now be illustrated in greater detail with reference to Examples, but the present ;~
invention should not be construed as being limited thereto. `~
All the percents are by weight unless otherwise indicated.
SnO, GeO, GeO2, PbO, PbO2, Pb2O3, Pb304, Sb2O3, Sb2O4, Bi2O3, LiCoO2 F LiNiO2, LiMn2O4 used in Examples are commercially available ones.
Preparation of SnO~:
S~(OH)4 synthesized from SnCl4 and NaOH was calcined in air at 400C for 4 hours to obtain SnO2, and the resulting SnO2 was ground in a mortar to an average primary particle size of about 0.05 ~m (rutile structure).
Preparation--of LiCo.s~.o~22.o7o A mixture of Li2CO3, CoC03, and NH4VO3 was calcined at 900C for 6 hours, followed by grinding in a mortar. - `
EXAMPLE A~
In order to examine how close the negative electrode active material of the present invention is to metallic lithium, an average potential of lithium deintercalation with reference to Li-Al (80%-20%) and its capacity were measured. ;~

-~ 2 1 3 ~ ~ ~ 2 A coin lithium battery having the structure shown in Fig. 2 was assembled in a dry box (dew point: -40 to -70C;
dry air) using the following materials. ;
Electrode~
A negative electrode active material mixture consisting of 82~ of each of the negative electrode active material precursors shown in Table A-l, 8% of flake graphite `
and 4% of acetylene black as conducting agents, and 6% of polyvinylidene fluoride as a binder was compression molded ~ `~
into a pellet of 13 mm in diameter and 22 mg in weight. ~ :
Before use, the pellet wa~ dried in the above-described dry . ;
box by means of a far infrared heater at 150C for 3 hours. ~ ` ;
Counter Electrode-An Li-Al (80%-20%) pellet of 15 mm in diameter and 100 mg in weight.
Collector~
A 80 ~m thick net of SUS316 was welded to each of a ~ ;
positive electrode case and a negative electrode case. ~ ` :
Electrolytic Solution~
20~ ~1 of a 1 mol/Q solution of LiPF6 in a 2:2:6 (by ~ `
volume) mixed solvent of ethylene carbonate, butylene carbonate and'dimethyl carbonate.
SeParator: -A finely porous polypropylene sheet and polypropylene nonwoven fabric impregnated with the electrolytic solution. ; ~ -~

~:' :' ~,",,.,".;.,,,,. ~ .

- ~13~0~2 . ~ ,.
' .
The resulting lithium battery was subjected to a charge and discharge test under conditions of a constant current density of 0.75 mA/cm2, a cut-off voltage of 1.3 V in charging, and a cut-off voltage of 0.2 in discharging. All the tests were started with intercalation of lithium into the ~ ::
compound of the present invention. The results obtained are shown in Table A-l.
Symbols used in Table A-1 and Tables A-2 to A-8 hereinafter given have the following meanings:
(a) ... negative electrode active ma$erial precursor of the present invention (b) ... lithium deintercalation capacity in the first cycle (mAh/g-negative electrode active material precursor) (c) ... average potential (V) of lithium ~; .
deintercalation . . :
(d) ... cycle characteristics [(lithium `~
deintercalation capacity in the 10th cycle -lithium deintercalation capacity in the 1st cycle)/lithium deintercalation capacity in the 1st cycle] . -~
(e) .I. discharge capacity in the 1st cycle (mAh/ml- ~ ;
cylindrical battery volume) ... ~
.' " ~ " , ',' .
- 44 - ,.~

i~ ~ 1 3 ~ ~ ~ 2 ., ~. .. ..- ..
TABLE A~
Run No. ,a) (b) (c) (d! -(mAh/g) (V) 1 SnO 540 0.62 0.06 2 SnO2 499 0.67 0.05 3 GeO 358 0.65 0.02 4 GeO2 259 0.68 -0.29 ~, PbO 309 0.58 0.55 6 PbO2 283 0.62 0.53 7 Pb2O3301 0.60 0.57 , ;
8 Pb304296 0.59 0-57 9 Sb2O3358 1.10 0.02 Sb2O4222 1.10 _0.lB ~ -11 Bi2O3345 0.88 0.63 -EXAMPLE A-2 ;~
A coin battery was prepared in the same manner as in ` ;~-Example A-l, except for using the following counter ;~
electrode. ~ ;
A positive electrode active material mixture ~ ~ ;
consisting of 82% of LiCoO2, 8% of flake graphite, 4% of -;
acetylene black, and 6~ of tetrafluoroethylene was ~-compression molded to obtain a pellet of 13 mm in diameter.
The weight of the pellet was decided according to the lithium intercalation capacity of the negative electrode active material precursor. The charge capacity of LiCoO2 was 213407~ I

170 mAh/g. Before assembly, the pellet was dried in the same manner as in Example A-l.
The resulting lithium battery was subjected to a charge and discharge test under conditions of a constant current density of 0.75 mA/cm2, a cut-off voltage of 4.3 V in charging, and a cut-off voltage of 2.7 V in discharging. All the tests were started with charging. The results obtained are shown in Table A-2. ~-Run No. (a! (bl (c! (d) (mAh/g) (V) 1 SnO 485 3.52 0.08 2 SnO2 443 3.48 0.07 ` ~'``
3 GeO 320 3.50 0.03 ~` `
4 GQ2 229 3.46 -0.15 `~
PbO 286 3.56 0.48 6 PbO2 261 3.52 0.55 7 Pb2O3275 3.50 0.49 Pb304279 3.54 0.49 9 Sb2O3320 3.04 0.04 ` `:
Sb2O4195 3.05 -0.02 11 Bi2O3302 3.27 0.65 In order to examine the influences of the calcination temperature in the synthesis of a negative electrode active ; ~ ;~
material, the same test as in Run No. 2 of Example A-1 was '','."' '' ,'.~,.,''. "' 2 -::
.~.
conducted, except for varying the ca:Lcination temperature for the synthesis of SnO2 as shown in Table A-3. The results obtained are shown in Table A-3.
TABLE A-3 ;
Run Calcination ;
No.Tem~erature !b ! (c) (d !
(C) (mAh/g) (V) ;~ ;~
1 300 499 0.68 0.05 2 500 515 0.6~ 0.06 `
3 600 597 0.69 0.11 ;--4 700 595 0-69 0.09 In order to examine the effect of addition of P
and/or Sb to SnO2 as a negative electrode active material, ;
the same test as in Run No. 2 of Example A-l was conducted, except for using Sb (10 mol%)-added SnO2, P (10 mol%)~added SnO2, or Sb + P (10 mol% in total)-added SnO2 as a negative electrode active material precursor. The calcination of the raw material was conducted in air at 700C, 300C or 700C, respectively, for 4 hours. The results obtained are shown in Table A-4.
For addition of Sb, SbCl5 or Sb2O3 was added at the time of synthesizing Sn(OH)4. Since SbCl5 and Sb2O3 gave substantially the same test results, the results of SbC15 addition are shown. For addition of P, P2O5 was added at the time of synthèsizing Sn(OH)4. In experiments using Sb-SnO2, reduction of the amount of the conducting agents produced no ~ 1 3 ~

difference in test results so that the results obtained in ~
.. . .
using a negative electrode active material mixture comprising 91% of the negative electrode active material precursor, 3%
of acetylene black, and 6% of polyvinylidene fluoride are ;~
shown in Table A-4.
TA~LE A-4 : ~
Run No. Additive (b! (c~ (d) (mAh/g) ~V) 1 none 499 0.68 0.05 2 Sb 575 0.76 0.11 ``
3 P 387 0.72 O.G6 4 Sb ~ P 538 0.72 0.09 The same test as in Run No. 1 of Example A-2 was , `~;
: , ~:., . ,.:;
conducted, except for using each of the positive electrode active materials shown in Table A-5. The charging and discharging conditions were 4.3 to 2.7 V. The results obtained are shown in Table A-5.
TABLE A-5 ;i-Positive Run Electrode ;- ~i No. Active Material(b ! (c! (d) ~
~mAh/g) (V) j l ; `
1 LiCoO2 485 3.52 0.08 2 LiNiO2 522 3.43 0.07 3LlCo.ssVo.osO2.0 473 3~53 0.06 '.,',,!',~
4 LiNn2O4 392 3.56 0.09 .,... :~,.

A mixture of 86~ of SnO or SnO2 as a negative electrode active material precursor, 6% of flake graphite, and 3% of acetylene black was mixed with 4% of an aqueous dispersion of a styrene-butadiene rubber and 1~ of carboxymethyl cellulose as binders. The mixture was kneaded using water as a medium to prepare a slurry. The slurry was extrusion coated on both sides of a 18 ~m thick copper foil ;~
and, after drying, compressed by calendering. The compressed sheet was cut to a prescribed size to prepare a 124 ~m thick negative electrode sheet.
A mixture of 87% of LiCoO2 as a positive electrode active material, 6~ of flake graphite, 3~ of acetylene black, and, as binders, 3% of an aqueous dispersion of polytetrafluoroethylene and 1% of sodium polyacrylate was -;~
,: -~ . . .
kneaded with water, and the resulting slurry was applied on ~-both sides o~ a 20 ~m thick aluminum foil, dried, compressed, and cut to size in the same manner as described above to ~;
prepaxe a 220 ~m thick positive electrode sheet.
A nickel or aluminum lead was connected by spot welding to the end of the negative electrode sheet or ~he positive electrode sheet, respectively. Both the electrode sheets with a lead were dried at 150C for 2 hours in dry air having a dew point of not higher than -40C.
Dried positive electrode ~heet (8), finely porous polypropylene film separator (Cell Guard 2400) (10), dried ~

- 49 - ~ ~-. ~ - : .

2 1 3 4 0 ~ 2 negative electrode sheet (9), and separator (10) were laminated in this order and rolled up by means of a winder.
. .: , . . .
The roll was put in cylindrical open-top battery case (11) made of nickel-plated iron which also served as a negative electrode terminal, and a 1 mol/~ LiPF6 solution in ;~
a 2:2:6 (by volume) mixture of ethylene carbonate, butylene `~
carbonate, and dimethyl carbonate was poured into the case. ;
Battery cover (12) having a positive electrode terminal was fitted into the top of case (11) via gasket (13) to prepare a ' -cylindrical battexy. Positive electrode terminal (12) and positive electrode sheet (8) were previously connected ` ;;~`
through a lead ter inal, and battery case (11) and negative `` ;~
electrode sheet (9) were connected in the same way. ``~ t:` ` '';"
The cross section of the thus assembled cylindrical ~ ~`
battery is shown in Fig. 3. Numeral (14) is a safety valve. ` ;`i~
. .; . .
The charging and discharging conditions were 4.3 to 2.7 V and ;~
1 mA/cm2. The results obtained are shown in Table A-6.

Run TABLE A-6 No. (b! - (c) (d) (e~
(mAh/g) (V) (mAh/ml) l 460 3.54 0.04 357 COMPARATIVE EXAMPLE A- 1 ~;. ' An electrode pellet was prepared in the same manner as in Run No. 1 of Example A-1 excep~ for replacing the compound as a negative electrode active material with rutile type WO2 or spinel type Fe3Ob. The same charge and discharge ., . . ~ .

~. 213~2 , .':

test as in Example A-2 was conducted. The results obtained are shown in Table A-7.

RunComparative No.ComPound _(b ! (c) ~d) (mAh/g) (V) l NO2 163 3.21 0.15 2 Fe2O3 109 3.16 0.44 The coin battery prepared in Run No. 1 of Example A~
was tested in the same manner as in Example A-l, except for changing the current density for lithium intercalation to O.38 mA/cm2. The results are shown in Table A-8.

Current Run Density for Li No.Intercalation(b) (c) (d) (mAh/g) (V) 1 0.38 233 0.68 0.82 A coin battery was prepared in the same manner as in Example A-2, except for using SnO or SnO2 as a negative electrode active material precursor. Fifty batteries for ~ `-ea~chjnegativejelectrode active material were tested by , repeating charging and discharging 20 times at a current . :. :.,.:, density of 5 mA/cm2 and then disassembled. The negative electrode pellet was taken out to 60% RH air and observed ~hether spontaneous ignition would occur.
''- ~"~..: ''''"
- 51 ~

213~52 For comparison, the same test was conducted, except -;
for using a pellet ~15 mm in diameter; 100 mg in weight) of ~; ;~ ` ;
an Li-Al alloy as a negative electrode active material.
On comparing Examples A-l to A-6 with Comparative -~
Example A-l, it was proved that the hatteries using the compounds according to the present invention have a high~, ;
discharge potential, satisfactory charge and discharge cycle characteristics, and a high discharge capacity.
Further, the negative electrode active material precursors of the present invention have a higher pellet density than that of a calcined carbonaceous material (1.1 to ; ~ ` `
1.4). In particular, SnO or SnO2 has a pellet density of 3.0 to 3.5, which is about 2 to 3 times that of the latter, and '~
al~o has about 2.5 times as high discharge capacity per unit ; ~
weight as the latter. Because the molecular weight per `
equivalent of the former is twice that of the latter, it is seen that the discharge capacity per volume of the negative electrode active material according to the present invention is about 4 times that of the calcined carbonaceous makerial.
As a result of the safety test in Example A-7 and Comparative Example A-3, neither the SnO pellet nor the SnO2 peliet ignited, whereas 32 out of 50 negative electrode pellets of Comparative Example A-3 spontaneously ignited. It ~ - -is thus seen that the compounds of the present invention are - -of high safety. - ~
.. ..~ . ....

- ., ;. ", -:;

- ~13~ 2 As demonstrated above, the use of an Li-containing -transition metal oxide as a positive electrode active material and an oxide mainly comprising at least one of the group IIIB, IVB and VB metals as a negative electrode active material provides a safe nonaqueous secondary battery having a high discharge potential, a high discharge capacity, and satisfactory charge and discharge cyc~e characteristics.
SYNTHESIS EXAMPLE B~1 Tin monoxide (13.5 g) and silicon dioxide (6.0 g) were dry blended, put in an alumina crucible, heated up to 1000C at a rate of 10C/min in an argon atmosphere, calcined at that temperature for 12 hours, cooled to room temperature at a rate of 6C/min, and taken out of the calcination furnace to obtain SnSiO3. The calcined product was coarsely ground and urther pulverized in a jet mill to an average `~ ;
particle size of 5 ~m (hereinafter designated as compound B~
1-A).
In the same manner, the following compounds were synthesized starting with the stoichiometric amounts of the ;
respective raw materials.
SnGeO3 (compound B-l-B) I i .
SnPbO3 (compound B-l-C) SnSiO.9GeO.l03 (compound B-l-D) SnSiO.gPbO.lO3 (compound B-l-E) ~ ~
SnSiO.5GeO.503 (compound B-1-F~ ~-SnSiO.5PbO.503 (compound B-l-G) ~ ~ 3 ~ ~ 5 ~

SnGeO.9PbO.Io3 (compound B-1-H) ~.
SnSiO.7O2.4 (compound B~
SnSil.zO3.4 (compound B-l-J) ~:
, ~ ~
SnSil.5O4 (compound B-l-K) PbSiO3 (compound B-1-h) PbGeO3 (compound B-1-M) ~ ...... `
PbSiO.9Ge0lO3 (compound B-l~N) ; ~n SYNTHESIS EXAMPLE B-2 ~;~ "; .. `
Tin monoxide (13.5 g) and silicon dioxide (6.0 g) `.~.``. ;~.~`
were dry blended, put in an alumina crucible, heated up to `~
1000C at a rate of 10C/min in an argon atmosphere, calcined at that temperature for 12 hours, and spread on a stainless ~`i```;~``"``
steel foil in an argon atmosphere for quenching. The ., :.~ ~ . .
resulting product was coarsely ground and further pulverized i ~; ..;.. .:
in a ~et mill to obtain SnSiO3 having an average particle .~
size of 5 ~m (hereinafter designated as compound B-2-A). ~. .

Tin dioxide (15.1 g) and silicon dioxide (0.6 g) were ;~
dry blended, put in an alumina crucible, calcined at 1000C ;~
for 12 hours in air, cooled to room temperature, and taken out of the calcination furnace to obtain SnSiO.~02.2. The --.
càlcined prodùct was pulverized in a jet mill to an average particle size of 4 ~m (hereinafter designated as compound 3-A)-' ", , '.',~,~.~
- 54 - ~

'". .' ..
" ..~, In the same manner, the following compounds were synthesiz~d starting with the stoichiometric amounts of the respective raw materials. - ;
SnSiO.3O2.6 (compound B-3-B) SnGeO.lO2.2 ~compound B-3-C) SnGeO,3O2.6 ~compound B-3-D) SnPbO.lO2.2 ~compound B-3-E) ~ -SnPbO.lO2.6 ~compound B-3-F) SnSiO.lGeO.IO2.4 ~compound B-3-G) SnSiO.lPbO.lO2.4 (compound B-1-H) SnSiO.0lO2.02 (compound B-3-I) -~
SnSil.5O5 (compound B-3-J?
SnSi2O6 (compound B-3-K) PbSio.lO2.2 (compound B-3-L) `~
PbGeO,3O2,6 (compound B-3-M) GeSiO,lO2,2 (compound B-3-N) GeSiO,3O2.6 ~compound B-3-O) ;
SYNTHESIS EXAMPLE B-4 ~ ~ -Tin monoxide (13.5 g) and silicon dioxide (0.6 g) `
were dry blended, put in an alumina crucible, calcined at 350C for 6 hours in an argon atmosphere, cooled to room temperature, and taken out of the calcination furnace to obtain SnSiO.lOl.2. The calcined product was pulverized in a jet mill to an average particle size of 2 ~m (compound B-4-A). -', ~

- ~ 13 ~ 0 2 : ~ ~

In the same manner, the following compounds were -synthesized starting with the stoichiometric amounts of the ~i`
respective raw materials. ~ :
SnSiO.0lO1.02 (compound B-4-B) SnGeO.~0~.2 (compound B-4-C) SnPbO.~0~.2 (compound B-4-D) PbSio.050~.~ (compound B-4-E) PbGeO.~Ol.l (compound B-4-F) ; ~;~
GeSiO3 (compound B-4-G) EXAMPLE B-1 `~
:.~ -; . :.-A coin lithium battery having the structure shown in : `~

Fig. 2 was assembled in a dry box (dry air; dew point: -40`~

to -~0C) using the following materials.

Electrode `~;

A negative electrode active material mixture ,` `~`
~ ., ,,. . ,.:~ ` ..
consisting of 82% of each of compounds B-l-A to N synthesized in Synthesis Example B-l, 8~ of flake graphite and 4% of `~
acetylene black as conducting agents, and 6% of ~ ~
polyvinylidene fluoride as a binder was compression molded to ;
obtain a negative electrode pellet of 13 mm in diameter and ~ ;
2~ mg in weight. Before use, the pellet was dried in the~i -above-described dry box by means of a far infrared heater at ,~
150C for 3 hours. ~

'," - '. . -", - 56 - ` ;

~;

~ X 13 ~ 2 ~ ~

Counter Electrode: -A positive electrode active material mixture consisting of 82% of LiCoOz as a positive electrode active ~-material, 8% of flake qraphite, 4% of acetylene black, and 6%
of tetrafluoroethylene was compr~ssion molded to obtain a pellet of 13 mm in diameter. The weight of the pellet was decided according to the lithium intercalation capacity of the negative electrode active materiaI precursor, and the ~
charge capacity of LiCoO2 was 170 mAh/g. Before use, the -;
pellet was dried in the same dry box as used above at 150C - i .
for 3 hours by means of a far infrared heater.
Collector:
A 80 ~m thick net of SUS316 was welded to each of the positive electrode case and the negative electrode case.
ElectrolYtic Solution:
200 ~1 of a 1 mol/Q solution of LiPF6 in a 2:2:6 (by -volume) mixture of ethylene carbonate, butylene carbonate and dimethyl carbonate.
SeParator:
A finely porous polypropylene sheet and polypropylene ~
nonwoven fabric impregnated with the electrolytic solution. `;
The rèsulting lithium battery was subjected to a charge and discharge test under conditions of a constant current density of 0.75 mA/cm2, a cut-off voltage of 4.3 V in charging, and a cut~off voltage of 2.7 V in discharging. All the tests were started with charging. The results obtained '; :-- 57 - ~

r ~ I 2 1 3 ~ 2 are shown in Table B~
Symbols used in Table B-l and Tables B-2 to B-7 hereinafter described have the following meanings~
(a) ... negative electrode active material of the `
present invention (b) ... discharge capacity of the first cycle (mAh/g- - ..m. ~`~
negative electrode active material) . - ~.
~c) ... average discharge potential (V) ~ ~ -(d) ... cycle characteristics (the number of the `~
cycles at which the discharge capacity was reduced to 60% of that of the first cycle) `~
, ' ''' '~''`

`'~''. '. ,:'',',~,'', .`''`'''.`"`,' ` ;''' -,, ` "' ".'-.... `' '',',,..:.

..' ~' '~'` ~'''''''''.
:~ ~"` '`.`'' - 58 - ~ ~

',~ ~; ' ) 2 ; ' . , .: , TABLE B-1 :
~un No. (a! (b! lc) -~d! : .
~mAh/g) (V)(cycles) - -1 B-1-A 488 3.51 327 :. :
2 B-1-B 448 3.54 289 3 B-l-C 495 3.35 305 4 B-1-D 468 3.56 295 B-l-E 483 3.39 317 :, 6 B-1-F 465 3.55 3~1 7 B-1-G 506 3.40 330 ~:
8 B-l-H 440 3.50 267 ~:
9 B-1-I 425 3.48 213 B-l-J 449 3.52 252 11 B-l-K 437 3.50 167 ;
12 B-1-L 415 3.21 239 13 B-1-M 389 3.25 248 14 B-1-N 378 3.22 . 182 The results in Table B-1 reveal that the negative :
electrode active material according to the present invention . .
provides a nonaqueous secondary battery having excellent charge and discharge cycle characteristics, a high discharqe :~ :
potential, and a high capacity.

A coin battery was prepared and tested in the same manner as in Run No. 1 of Example B-1, except for replacing compound B-l-A as a negative electrode active material with _ 59 _ ~;''~'~',.. `',';
''''' ;'".''`''"' - 2 1 3 ~ ~ ~ 2 "",,.,.-compound B-2-A synthesized in Synthesis Example B-2. The results obtained are shown in Table B-2. ~"
TABLE B--2 . :
Run No. (a~ ~ ! ( c ) _ ( d) `~
(mAh/g) (V) (cycles) l B-2-A 521 3.52 351 ~;
It is seen that the battery using the negative - . ".
electrode active material obtained by calcination followed by . " ;:-~
quenching exhibits further improved charge and discharge . ;.
cycle characteristics with a high discharge potential and a . :
.: ~ .: ..: .....
high capacity. . :.
EXAMPLE B-3 .~ `` .-.
Coin batteries were prepared and tested in the same manner as in Example B-l, except for replacing the compound ~ ;
B-1 as a negative electrode active material with each of compounds B-3-A to B-3-O synthesized in Synthesis Example B- : `.
3. The results o.btained are shown in Table B-3. `:~ .. ;

:~ ,` .~. ., .: ':
' ''~ '''.'' '' ;~

~ . . ~ , ' ', ''' ;'. ~"-~ ~13~952 ~ :~

TABLE B- 3 ;
Run No. ta~ (b! ~c) (d) .
(mAh/g) (V) (cycles) 1 B-3-A 442 3.50 186 2 B - 3-B 448 3.5~ 185 3 B-3-C 458 3.53 166 4 B-3-D 472 3.51 158 B-3-E 481 3.47 161 6 B-3-F 482 3.42 159 7 B-3-G 463 3.55 177 8 B-3-H 468 3.44 180 9 B-3-I 440 3.48 155 `
B-3-J 42i8 3.54 137 ~ -11 B- 3 -K 444 3.55 142 12 B-3-L 485 3.34 141 13 B- 3 -M 401 3.38 155 14 B-3-N 417 3.62 170 ~-3-O 394 3.65 127 It can be seen that the battery using the negative electrode active material according to the present inYention have excellent charge and discharge cycle characteristics, a ~` :
i highi discharge potential, and a high capacity.
: EXAMPLE B-4 Coin batteries were prepared and tested in the same `... : :~
manner as in Example B-1, except for replacing the compound ...-~.
. ~.; ,~ ,., B-l as a negative electrode active material with each cf . .. ::;

1 3 ~ 0 ~

: "... .....

compounds B-4-A to B~4-G synthesized in Synthesis Example B~
4. The results obtained are shown in Table B-4. ';;:,'.. ~-TABLE B-4 ,:,'',.~
Run ,.:, .:.
No. (a) (b! (c! ~d! , -~
~mAh/g) (V) ~cycles) 1 B-4-A 485 3.53 127 -2 B-4-B 487 3.53 113 3 B-4-C 472 3.55 141 '~ ;"
4 B-4-D 492 3.49 155 ~ '?' B-4-E 445 3.32 106 ;~
6 B-4-F 428 3.28 116 :',,`,;~
7 B-5-G 418 3.33 112 It can be seen that the battery using the negative ;'~
electrode active material according to the pres,ent invention ' '.~
has excellent charge and discharge cycle characteristics, a ,~''` ; ' high discharge potential, and a high capacity. .:.
CONPARATIVE EXAMPLE B-l ,'~
' A coin battery was prepared and tested in the same manner as in Example B-l, except for replacing the compound B-l as a negative electrode active material with SnO2 or SnO. .` ;,,; .
The results obtained are shown in Table B-5. '~

~ ~" ,-,: ::'.

- 62 ~
'' ''..:,'" '' `'' 13~2 , .

Run No. (a) (b! (C! (d) (mAh/g) ~V) (cycles) 1 SnO2443 3.48 85 2 SnO 483 3.53 73 It is seen that the use of the tin compound oxide according to the present invention as a negative electrode `
active material provides a battery superior to that using SnO2 or SnO in terms of charge and discharge cycle ~;~
characteristics and capacity.
COMPARATIVE EXAMPLE ~-2 A coin battery was prepared and tested in the same `~
manner as in Example B-l, except for replacing the compound `
B-l as a negative electrode active material with WO2 or Fe203. ;~ ;
The results obtained are shown in Table B-6. `;~

Run (a) [b~ (c! fd) ` i;
(mAh/g) (V) (cycles) `;i i^
1 WO2 1~3 3.21 42 i 2 Fe203109 3.16 13 ~ ~
It is apparent that the use of the tin compound oxide 'S"~.".` ~ "~., according to the present~invention as a negativa electrode ; i active~material provides a battery superior to that using WO2 ;;~
or~Fe203 in ter s of~all of charge and discharge cycle ,`,;:
characterLstics, discharge potential, and capacity.

, .-,' ' -;.

1 3 ~ ~ ~ 2 ;~

A coin battexy was prepared and tested in the same ~ ~ ~
~ .,,. ;
manner as in Run No. 1 of Example B-l, except for replacing i ~
LiCoO2 as a positive electrode active material with LiNiO2, ~ ~ ;
LiCoO.95VO.0~O2.07 or LiMn2O4. The results obtained are shown in - ~
Table B-7. ~ `:
TABLE B-7 ~, Positive Run Electrode No. Active Material(b! -- (c! ~d!
(mAih/g) (V) (cycles) ;~ `
1 LiCoO2 488 3.51 327 2 LiNiO2 492 3.41 ~30 3LiCoO,95V0.05O2.0 480 3.50 385 4 LiMn2O4 470 3.55 323 It is seen that the battery according to the present ~`
invention is excellent in all of charge and discharge cycle ~;
characteristics, discharge potential, and discharge capacity ~
regardless of which of the above positive electrode active ~;
materials is used. ~-EXAMiPLE B-6 ;~
A mixture of 86% of compound B-l-A synthesized in ;
Synthesis Example B-l as a negative electrode active material, 6% of f}ake graphite, and 3~ of acetylene black was ;
mixed with 4% of an aqueous dispersion of a styrene-butadiene rubber and 1% of carboxymethyl cellulose as binders. The mixture was kneaded together with water to prepare a slurry.

.

p ~3~52 The slurry was extrusion coated on both sides of a 18 ~m thick copper foil and, after drying/ compressed by ~ -calendaxing. The compressed sheet was cut to a prescribed ~;~
size to prepare a 124 ~m thick negat:ive electrode sheet.
A mixture of 87% of LiCoO2 as a positive electrode active material, 6% of flake graphite, 3~ of acetylene black, and, as binders, 3% of an aqueous dispersion of polytetrafluoroethylene and 1~ of sodium polyacxylate was .,-kneaded with water, and the resulting slurry was applied on :,. - .-,, :
both sides of a 20 ~m thick aluminum foil, dried, compressed, ~;` `
and cut to size in the same manner as described above to ;`
prepare a 220 ~m thick positive electrode sheet.
A nickel or aluminum lead was connected by spot ,; .. ~ . ;.. ..
welding to the end of the negative electrode sheet or the . ~
positive electrode sheet, respectively. Both the electrode ~;
sheets with a lead were dried at 150C for 2 hours in dry air `~ `` `"
having a dew point of not higher than -40C. - ;
Dried positive electrode sheet (8), finely porous ``;
polypropylene film separator (Cell Guard 2400) (10), dried negative electrode sheet (9), and separator (10) were laminated in this order and rolled up by means of a winder.
The rolI was put in cylindrical open-top battery case ,. ~ . ~ . ~, .
(11) made of nickel-plated iron which also served as a negative electrode terminal, and a 1 mol/Q LiPF6 solution in a 2:2:6 (by volume) mixture of ethylene carbonate, butylene carbonate, and dimethyl carbonate was poured into the case.

Battery cover (12) with a positive electrode terminal was fitted into the top of ca~e~ p ~a gasket (13) to prepare a ~ ~
cylindrical battery. Positive electrode terminal (12) and ~ -positive electrode sheet ~8) were previously connected via a ~ ~
lead terminal, and bat~ery case (11) and negative electrode ~`
sheet (9) were connected in the same way.
The cross ~ection of the thus assembled cylindrical battery is shown in Fig. 3. Numeral (14) is a safety valve.
The battery was subjected to a charge and discharge test ~-under conditions of 4.3 to 2.7 V and 1 mA/cm2. The results obtained are shown in Table B-8. In Table B-8, symbol (e) means a discharge capacity per ml of a C size battery.
TABLE B-8 -~

Run No. (b! (c) ~d! ( (mAh/g) (V) (cycles) (mAh/ml) 1 490 3.54 550 360 . . .
EXAMPLE B-8 AND CONPARATIVE EXAMPLE B-3 - ;
~, Fifty coin batteries were prepared in the same manner as in Run No. 1 of Example B-1 and subjected to a safety test in the same manner as in Example A-7. As a result, none of them ignited.
For comparison, the same test was conducted, except for using a pellet (15 mm in diameter; 100 mg in weight) prepared by using an Li-Al (80~-20~) alloy as a negative electrode active material. As a result, 32 out of 50 ignited. ~
: ` ~`::

.::: ~

': , '~.'"' -" 21 3~2 ~:

It can be seen from these results that the nonaqueous secondary battery according to the present invention is of high safety.
As described above! the nonaqueous secondary battery ;~
of the present invention in which an Li-containing transition ; ;
metal oxide is used as a positive electrode active material `
and at least one specific compound oxide as a negative ;~
electrode active material exhibits a high discharge ~ `-potential, a high discharge capacity, excellent charge and discharge cycle characteristics, and high safety.
. ~. . ~, In the following Examples, SnO, GeO, GeO2, SiO2, PbO, PbO2, Pb2O3, Pb304, Sb2O3, Sb2O4, Bi2O3, WO2 (comparative), and `` ` ;;
Fe2O3 (comparative) used as a negative electrode active ;;;~ ~ ;
material are commercially available ones.

Tin chloride and sodium hydroxide were reacted in an aqueous solution to precipitate Sn(OH)4. The precipitate was ~;
calcined in air at 400C for 4 hours to synthesize rutile ~ ;
type SnO2, which was ground in a mortar to an average primary particle size of about 0.05 ~m.

; i Lithium carbonate (7.3 g) and tin dioxide i(l5.1 y) were dry blended, put in an aluminum crucible, and calcined in air at 1000C for 12 hours. After the calcination, the product was cooled to room temperature to obtain Li2SiO3.
In the same manner, Li2GeO3, Li2PbO3, Li3BiO4, Li3SbO4, ~ 0~

~13~0~2 ' "' LizZnOz, Li3InO3r Li2ZnSn2O6, Li2MgSn2O6, LiO.ISnO2.05, Li4SnO4, Li6SnOs, and Li8SnO6 were prepared using stoichiometrical amounts of the respective starting materials. ~ -Lithium acetate dihydrate (10.2 g) and tin monoxide -~
(13.5 g) were dry blended, put in a porcelain crucible, calcined in an argon atmosphere at 350C for 24-hours, and cooled to room temperature to synthesize Li2SnO2. The product was pulverized in a jet mill to an average particle ;
size of 2.5 ~m.
In the same manner, Li0.lSnO1.05, Li6SnO4, and Li8SnO
were synthesized using stoichiometrical amounts of the respective starting materials.
SYNTHESIS EXAMiPLE C-4 Silicon dioxide (2.60 g) and tin monoxide (1.16 g) ;`~
were dry blended, put in an alumina crucible, calcined in air at 1000C fox 12 hours, and rapidly cooled to room ;~
temperature to synthesize amorphous and glassy SiSnO3.

, Lithium carbonate (2.26 g), tricobalt tetroxide ` ;
(5.0 g), and germanium dioxide (0.19 g) were dry blended and calcined in air at 900C for 18 hours to synthesize crystalline LiCoGe0.03Oz. Average particle size: 4 ~m.

,: , Lithium car~onate (2.26 g), tricobalt tetroxide (5.0 g), and zirconium dioxide (0.16 g) were dry blended, and ;

- 68 ~

13 ~ ~ ~ 2 .. ` ,. ~. ..~, ..
.. . "~., .
calcined in air at 900C for 18 hour~i to synthesize ~
crystalline LiCoZrO.02O2. ~verage particle size: 5 ~m. ` ~-Lithium carbonate (2.26 g), t;ricobalt tetroxide ~`-(5.0 g), germanium dioxide (0.13 g), and zirconium dioxide ~0.16 g) wexe dry blended, and calcined in air at 900C for 18 hours to synthesize crystalline LiCoGeO.02ZrO.02o2~ Average ``~
particle size: 4 ~m. ~ `
In the same manner, LiCoGeO.08O2, LiCoGeO.06O2 LiCoZrO.06O2, LiCoZrO.08O2, LiCoTiO.08O2, and LiCoTiO.03O2 were synthesized as a positive electrode active material by using ,~ '!"~
stoichiometrical amounts of the respective starting materials.
SYNTHESIS EXAMPLE C-8 `~ ;
Lithium carbonate (2.26 g) and tricobalt tetroxide (5.0 g) were dry blended and calcined in air at 900C for 18 hours to synthesize crystalline LiCoO2. Average particle size: 5 ~m.

Lithium carbonate (1.20 g) and manganese dioxide (5.92 g) were dry blended and calcined in air at 800C for 12 hours to synthesize crystalline LiMn2O4. Average particle -- -size: 3 ~m. ^

Lithium carbonate (2.26 g), tricobalt tetroxide (2.50 g), and nickel oxide (2.29 g) were dry blended and - ~~

~ . " . ~ ~:
'~

; ? ~J ~ 2 calcined in air at 800C for 20 hours to synthesize crystalline LiNio5CoO.5O2. Average particle size: 7 ~m.
EXAMPLE C-1 :
A coin battery was assembled using the following materials.
Electrode: . ::
A negative electrode active material mixture consisting of 82~ of a negative electrode active material precursor showmi in Table C-1, 8% of flake graphite and 4~ of acetylene black as conducting agents, and 6% of polyvinylidene fluoride as a binder was compression molded into a pellet of 13 mm in diameter and 22 mg in weight. ~ ...
Before use, the pellet was dried in a dry box (dry air; dew point: -40 to -70C) by means of a far infrared heater at 150C for about 3 hours.
Counter Electrode:
.:
A positive electrode active material mixture ~ ;`.
consisting of 82~ of a positive electrode active material shown in Table C-l, 8% of flake graphite and 4% of acetylene - .
black as conducting agents, and 6% of tetrafluoroethylene as a binder was compression molded into a pellet of 13 mm in diametér and lllO mg in weight. Before use, the pellet`was dried under the same conditions as used for the negative electrode pellet.
Collector~
A 80 ~m thick net of SUS316 was welded to each of the ' ~' ",'"'' `'.,.
70 ~
..~ . ~ . . "~. .

~ 1 3 ~L O ~ 2 , ;. ~. .. ,~
, .. ~. ; ` , positive case and the negative case.
Electrolytic Solution ;~
200 ~l of a 1 mol/~ solution of LiPF6 in a 2:2:6 (by ~ ~
volume) mixed solvent of ethylene carbonate, butylene ;~ -carbonate and dimethyl càrbonate. ; -Separator~
A finely porous polypropylene sheet and polypropylene nonwoven fabric impregnated with the electrolytic solution.
The resulting lithium battery was ~ubjected to a `
charge and discharge test under conditions of a constant current density of 0.75 mA/cm2, a cut-off voltage of 4.3 V in charging, and a cut-off voltage of 2.7 V in discharging. All the tests were started with intercalation of lithium into the . .
negative electrode active material pxecursor of the present `~
invention. While more than lO0 kinds of coin batteries were ;`
prepared and tested using a variety of combinations of a -. ~,"; . .
negative electrode ackive material and a positive electrode ; ~`

active material, the typical results are shown in Table C~
; . ,-., ., : ~ . ..
It should therefore be understood that the combination of a negative electrode active material and a positive electrode - ;
active material which can be used in the present invention `~
are not limitied to those shown in the Table. -, ":, , ;-, ...'.....

", ' ': :.'; ,' ' '' -,: ~ " ~. ,,, .:
:,.~ ' :,'.,:, - 71 ~
.' i ''~,' '.,' ' ','''.' ' 0 ~ 2 PositiveNegative Discharge ElectrodeElectrodeAverageCapacity Cycle .~ .-Active Active Dischargeat the Charac- -. .
MaterialMaterial Potential2nd CYcleteristics* . :~
(V), (mAh/g) , ,, ,;
Compari~on: `
LiCoO2 WO2 3.20 160 0.15 LiMn2O4 WO2 3.15 145 0.16 LiNio.5Coo.5o2 wo2 3.15 140 0.16 LiCoO2 SnO 3.52 480 0.08 LiC002 SnO2 3.52 470 0.07 LiMn2o4 SnO 3.50 390 0.09 LiNiO.5Co.sO2 SnO 3.48 360 0.09 `~
LiCoOz SnSiO3 3.50 460 0.04 LiCoO2 Li2SnO3 3.50 440 0.06 LiCoO2 GeO2 3.46 229 -0.10 `~
Invention:
~iCoGe0.03O2 SnO 3.55 490 0.05 LicoGeo.o6o2 SnO 3.55 482 0.06 LicoGeo.o8o2 SnO 3.53 482 0.06 LiCoZrO.0202 SnO 3.55 515 0~05 LiColZrO~06O2SnO 3.55 505 ~ 0.06 Licozro.o8o2 SnO 3.53 500 0.06 LlcoGeo.o3Q2SnSiO3 3.55 482 0.03 LicoGeo.o3o2Li2SnO3 3.55 450 05 LicoGeo.o3o2GeO2 3.48 255 -0.10 - 72 - ~ ~ ;
~:

-`` ~13~0~2 TABLE C-1 (cont'd~

Positive Negative Discharge Electrode Electrode Average Capacity Cycle Active Active Discharge at the Charac~
MaterialMaterial Potential 2nd CYcle teristics~
(V) (mAh/g) Licozro.o2o2 SnSiO3 3.55 490 0.03 LiCoZrO.02O2 Li2SnO3 3.55 460 0.05 LiCoZrO.02O2 GeO2 3.50 265 _0.10 LiCoGe0.o2zro~o~o25nSiO3 3.55 485 0.03 -`
LiCoGe0.o2zro.o2o2Li2SnO3 3-55 455 0.04 ~`
LiCoTi0.03O2 SnO 3.55 482 0.06 `~
LiCOTio.oaO2 SnO 3.54 480 0.05 .
LiCoGeO.o3o2 SnO2 3.54 475 0.05 `` "~
LiCoGe0.03O2 Li2SnO~ 3.55 490 0.05 LicoGeo.o3o2 Li2MgSn2O6 3.54 485 0.06 Note: * (Discharge capacity of the 10th cycle - discharge capacity of the 1st cycle)/discharge capacity of ` ~.~r~ "
the 1st cycle ``~
SYNTHESIS EXAMPLE C-11 `.` .`
Li2CO3 and MnO2 were mixed at a molar ratio of about .:
1:4, and the mixture was calcined in air at 400C for 12 hours to synthesize a spinel type lithium-manganese oxide '.~ '"'".,,",.',' "'' having the composition of Li2Mn4O9 (or LiO.89Mnl.78O4) according ;; ~
to the present invention. An oxide of the same composition .. : ` , could also be synthesized by calcining a 1:4 (by mole) mixtur~ of Li2CO3 and MnCO3 in air at 430C for 5 hours.

'' ' '''~;'1''.

2 ~ ~-Li2CO3 and ~nO2 were mixed at a molar ratio of about 0.35:2, and the mixture was calcined in air at 450C
for 12 hours to synthesize a spinel l:ype lithium-manganese oxide having the composition of LiO.7~n2O4 according to the present invention. `~

Li2Mn4O9 synthesized in Synthesis Example 11 and MnO2 were mixed at an Li:Mn atomic ratio of about 2:5, and the mixture was calcined in air at 250C for 24 hours t synthesize a spinel type lithium-manganese oxide having the `~
composition of Li2Mn5O11 according to the present invention. ~;~
SYNTHESIS EX~PLE C-14 Li2CO3 and ~-MnO2 were mixed at an Li:Mn molar ratio `
of about 4:5, and the mixture was calcined in air at 430C ~;
for 12 hours to synthesize a lithium-manganesa oxide having the composition of Li4Mn5OI2 ~or Lil.33Mnl.67O4) according to the ~ ~ ;
present invention.

Li4Mn5Ol2 synthesized in Synthesis Example C-14 and EMD were mixed at a molar ratio of about 1:10, and ~he mixture was calcined in air at 400C for 40 hours to synthesize a lithium-manganese oxide having the composition of LiO.5Mnl.88O4. Alterna~ively, the same compound could be obtained by mixing Li4Mn5Ol2 with CMD instead of EMD at a molar ratio of 1:10 and calcining the mixture at 400C for ~

- 74 - ~ -''`` ' ' 3 . . . .

24 hours. ;~`~
SYNTHESIS EXAMPLE C-l6 Li4Mn5O1~ synthesized in Synthesis Example C-14 and MnO2 were mixed at a molar ratio of about l:12, and the mixture was calcined in air at 400C for 12 hours to synthesize a lithium-manganese oxide having the composition ``-of LiO.46Mn189O4 according to the present invention. ' :, The manganese oxides synthesized in Synthesis - ~
Examples C-ll to C-16 are represented by Li2O(MnO2)~ in which ,~ ''~'`"';"-`!`''"``' x falls within a range of 2 to 9.

A positive electrode pellet (active material content~
16.4 mg) and a negative electrode pellet (active material '`'''`"` '``'""':'?
content: 85 mg) were prepared in the same manner as in Example C-l, except for using the active materials shown in , Table C-2. ~ - , A 80 ~m thick net of SUS316 as a collector was ~ -welded to each of positive and negative cases. :
As an electrolyt1c solution, 25~ ~l of a l mol/Q
so1ution of LiPF6 in a l:l (by volume) mixed solvent of ;
ethylene carbonate and diethylene carbonate was infiltrated into a separator composed of a finely porous polypropylene sheet and polypropylene nonwoven fabric. The positive electrode pellet and the negative electrode pellet was set on the respective collector, and the positive electrode case and the negative electrode case we.re fitted to each other with :~ ' `.' ' "

! . ' ' ' . '~
' ~ .. ,"'~.

3 ~ 0 ~ 2 - , ~
the separator therebetween in a dry box to prepare a coin lithium battery.
The resulting lithium battery was subjected to a charge and discharge test under conditions of a constant current density of 0.75 mA/cm2~ a cut-off voltage of 4.3 V in :
charging, and a cut-off voltage of 2.7 V in discharging. All :~
., :.
the tests were started from charging. The results obtained ;
are shown in Table C-2. In the Table, "discharge capacity~
. .. - .
means the capacity per unit weight of the negative electrode active material up to the time when the discharge was terminated at 1.8 V, and "capacity cycle characteristics~
means the number of cycles required for the discharqe .
capacity to be reduced to 60% of the initial discharge capacity. ;

,.".:

~ . . . .-: ;: ., . .~ :;

r` 2 1 3 ~ O ~ 2 ~'"'''' ""`"' '"' Positive ~egative Discharge Capacity Electrode ElectrodeCapacity Average Cycle ,~
Ac~ive Active of the Discharge Charac~
Material _ Material2nd Cvcle Potential teristics (m~h/g) (V) ~cycles~
Comparison~
LiMn2O4 WO2 170 3 15 40 Lio.46Mnl.s9o4 WO2 180 3.20 50 LiMn204 SnO2 410 3.45 130 ~ ;
LiMn204 SnO 4 30 3.45 120 LiMn2O4 Li2SnO3 420 3.4S 125 ~ `
LiMn204 5nSiO3 425 3.46 135 ;
Invention:
Li2Mn5Oll SnO2 430 3.50 130 Li2Mnsoll SnO 450 3.50 122 ~ ~`
Li~Mn5Oll Li2SnO3 440 3.50 130 Li2MnsOll SnSiO3 445 3.52 135 Li2~5n40g SnO 445 3 - 50 120 Lio.46Ml.ssO4 SnO 455 3.50 120 Lio.sMnl.88o4 SnO 450 3.50 120 Lio.38Mnl.9o4 SnO 460 3.50 120 ,. . . ~
~Li2Mn4Og ~SnSiO3 440 3.52 ; 150 Lio.46Mnl.sso4 SnSiO3 450 3.52 155 Lio.5Mnl.sso4 SnSiO3 445 3.53 150 Lio~3gMnl.so4 SnSiO3 455 3.52 155 Lio.46Mnl~89o4 Li2SnO3 435 3.50 145 ,;~, :':',-,;

--~ 2 1 3 ~
, TABLE C-2 tcont'd.~
Positive Negative Discharge Capacity :. ; .Electrode Electrode Capacity Average Cycle : ~
Active Activeof the Discharge Charac- ~ :
Material Material2nd CYcle Potential teristics (mAh/g~ (V) (cycles) ;~
Li0,43Mhl,ssO4 Li2SnO3 440 3.50 145 Lio~5Mnnsso4 Li2SnO2 450 3.50 140 Li2Mn5O~1 GeOz 250 3.40 200 Li0.46Mn~.89O4 GeO2 270 3.40 210 The results in Table C-2 prove that the lithium ion nona~ueous secondary batteries prepared from a combination of . :.. :.. ;
the negative electrode active material according to the present invention and a spinel type lithium-manganese double ..
oxide as a positive electrode active material are superior in . -.
discharge capacity and cycle characteristics to conventional ;. ; `.
batteries using a combination of a metal oxide type negative .. ~
electrode active material and a manganese oxide as a positive ~ ~ i electrode active material. ~;.`
The negative electrode active material according to the present invention can be obtained by electrochemically .
intercalating lithium ions into an oxide (a negative electrode active material precursor). The lithium ;~ ~ ;
intercalation is effected until the basic structure of the precursor is changed (for example, until the X-ray ;~
diffraction pattern changes) and also until the thus ahanged .~ .
basic structure of ~he Li ion-containing oxide undergoes `~
substantially no change during charging and discharging ~for ^` 2 ~L 3 ~

example, the X-ray diffraction pattern of the Li-containing ~ ~
oxide does not change substantially)O The change in basic -structure means change from a certain crystal structure to a different crystal structure or from a crystal structure to an amorphous structure. ~
The lithium nonaqueous secondary batteries in which ~-an oxide of a metal selected from the group IIIB, IVB and VB
elements is used as a negative electrode active material and a compound oxide containing cobalt and a metal selected from the group IIIB, IVB and VB elements or a spinel type lithium-. '. :
manganese compound oxide is used as a positive electrode active material have a high discharge capacity and a high charging and discharging efficiency as well as high safety and satisfactory cycle ch~racteristics owing to the ` ~ ;~
properties of the negative electrode active material. In ~ ;
addition, use of inexpensive manganese brings about an economical advantage.
SYNTHESIS EXAMPLE D~
Tin monoxide (13.5 g) and silicon dioxide (6.0 g) were dry blended, put in an alumina crucible, heated up to 1000C at a rate of 15C/min in an argon atmosphere, calcined at that temperaturè for 12 hours, cooled to room temperature at a rate ~f 10C~min, and taken out of the calcination furnace to obtain SnSiO3. The calcined product was ;~
pulverized in a jet mill to an avexage particle size of 4.5 ~m ~hereinafter designated as compound D-1-A~.

13~2 , ...: :.`
The X-ray diffraction pattern (CuK~ rays) of compound .; ~
D-1-A is shown in Fig. 1. The pattern shows a broad peak ;~ :;.;
centered at about 28 (2~) with no diffraction assigned to crystal properties between 40 and 70 (2~).
The following compounds were also synthesized in the same manner as described above using stoichiometrical amounts ;.
of the respective starting materials. The X-ray diffraction pattern (CuK~ rays) of these compounds similarly exhibited a . ``:
broad scattering band with its peak between 20 and 40 (2 ~he diffraction intensity of the peak of the broad scattering ..
band appearing between 20 and 40 (2~) is taken as A, and the strongest intensity of any diffraction line assigned to ;.` ~.
crystal properties which may appear between 40 and 70 (2~
is taken as B (B = 0 where no diffraction assigned to crystal -`.`
properties occurs). The B/A value is shown together with the ;:~ -compound number. .~
SnGeO3 (compound D-l-B; B~A = 0) " .
SnSiO.8P0.1O3 tcompound D-1-C; B/A = 0) `;,-~
SnSiO.gGeO.lO3 (compound D-l-D; B/A = 0) m~ :;i SnSiO.gPbO.lO3 (compound D-l-E; B/A = 0) ' ` ' " f'` ' SnSiO.5GeO.6O3 (compound D-l-F; B/A = 0) `~

SnSiO.5PbO.5O3 (compound D-l-G; B/A = 0.3) SnGeO.gPb0.lo3 (compound D-l-H; B/A = 0) SnSiO.aOz.4 (compound D-l-I; B/A = 0.1) SnSil.2O3.4 (compound D-l-J; B/A = 0) SnSi~.504 ( compound D-l-K; B/A = 0) ~ ~

- 80 - , ~ ~"

2 1 3 ~ ~ ~ 2 PbSiO3 (compound D-1-L; B/A = 0) PbGeO3 (compound D-l-M; B/A =0) PbSi0.9Ge0.1O3 (compound D-1-N; B/A = 0) SnPO3.5 (compound D-l-O; B/A = 0) SnBO2.5 (compound D-l-P; B/A = 0) .
SnSi0.9O2.8 (compound D-1-Q; B/A = 0) SYNTHESIS EXAMPLE D-2 .`
Tin monoxide (1.35 g) and silicon dioxide (0.6 g) were dry blended, put in an alumina crucible, heated up to ~ -1000C at a rate of 15C/min in an argon atmosphere, calcined , at that temperature for 10 hours, and quenched by spreading `
on a stainless steel foil in an argon atmosphere. The calcined product (SnSiO3) was coarsely ground and then pulverized in a jet mill to an average particle size of 3.5 ~m (hereinafter designated as compound D-2-A). The B/A
ratio in the X-ray diffraction pattern was 9.5.

Tin dioxide (15.1 g) and silicon dioxide (0.6 g) were dry blended, put in an alumina crucible, calcined at 1200C
for 10 hours, cooled to room temperature, and taken out of the furnace to obtain SnSiO.lO2.2. The calcined product was pulverized in a jet mill to an average particle size of 4 ~m (hereinafter designa~ed as compound D-3-A). The B/A ratio in ~ ~ `
the X-ray diffraction pattern was 0. --In the same manner as above, the following compounds were synthesized using stoichiometrical amounts of the ~ :~

. - . .
. ,,.: ~-''' ' , ',` ~

~13~5~

respective starting materials.

SnSiO.3O2.8 ~compound D-3-B; B/A = 2.4) ; ~ -SnGeO.IO2.2 (compound D-3-C; B/A = 7.4) ~ ;
SnGeO.3O2.6 (compound D-3-D; B/A = 4.7) SnPbO.IO2.2 (compound D-3-E, B/A = 7.5) SnPbO.lO2.8 (compound D-3-F; B/A = 16.5) SnSiO.lGeO.lO2.4 (compound D-3-G; B/A = 9.5) ~;; ' SnSiO.1PbO.lO2.4 (compound D-3-H; B/A = 29.1) SnSiO.0lO2.02 tcompound D-3-I; B/A = 7.1) SnSil.3O5 (compound D-3-J; B/A = 0) `
SnSi2O6 (compound D-3-K; B/A = 0) PbSio.lO2.2 (compound D-3-L; B/A = 5.3) PbGeO3O2.6 (compound D-3-M; B/A = 2.3) ``~ "```
GeSiO.IO22 (compound D-3-N; B/A = 0) GeSiO2O26 (compound D-3-O; ~/A = 0) ~ ` `

5nPo32.7s (compound D-3-P; B/A = 1.4) SnB0.3O2.45 (compound D-3-Q; B/A = 6.4) SYNTHESIS EXAMPLE D-4 .
Tin monoxide (13.5 g3, 4.8 g of silicon dioxide, and 1.42 g of diphosphorus pentoxide, each weighed in dry air having a dew point of -50C, were dry blended in a ball mill ` i `
in the same dry air. The mixture was put in an alumina crucible, heated to 1100C at a rate of 10C/min in an argon atmosphere, calcined at that temperature for 10 hours, and ;
cooled to room temperature at a rate of 8. 3C/min to obtain a f~
, . -, ~ , , ,, ~ ... .......

~ 2 . ~, glassy compound. The compound was pulverized in a jet mill and air-classified to obtain compound D-4-A having an average particle size of 4 ~m. The B/A ratio in the X-ray diffraction pattern was 0.
In the same manner as described above, the following compounds were synthesized using stoichiometrical amounts of the respective starting materials ~Al2O3 and Sb2O3 were used as an Al source and an Sb source, respectively).
SnSiO.9P0.lO3.05 (compound D-4-B; B/A = 0) SnSiO7P0.9O3.l5 (compound D-4-C; B/A = 0) SnSiO.5P0.5O3.25 (compound D-4-D; B/A = 0) SnSiO.2P0.8O3.4 (compound D-4-E; B/A = 0) SnSiO.~P0.lSbO.I03 (compound D-~-F; B/A = 0.5) `~
SYNTHESIS EXAMPLE D-5 j ~
Tin monoxide ~10.78 g~, 3.6 g of silicon dioxide, ~ ;
4.11 g of stannous pyrophosphate, and 2.1 g of germanium dioxide were dry blended in a ball mill. The mixture was put in an alumina crucible, heated to 1100C at a rate of 10C/min in an argon atmosphere, and calcined at that temperature for 10 hours. The calcined product was quenched by pouring into water in an argon atmosphere to obtain a glassy compound. The compound was wèt ground in a ball mill using water as a grinding medium, and the slurry was passed through a sieve of 25 ~m to remove coarse particles. Water was removed by decantation, and the solid was dried at 150C
for 1 hour to obtain compound D-5-A having an average ~
' . .
- 83 - ~

.~1 3 ~ ~S2 particle size of 3.l ~m. The B/A ratio in the X-ray diffraction pattern was 0.
In the same manner as described above, the following compounds were synthesized using stoichiometrical amounts of -the respective starting materials. Al2O3 was used as an "
aluminum source.
SnSiO,7GeO1PO.2O3.1 (compound D-5-B; B/A = 0) SnSiO.6GeO.4P0.13.25 (compound D-5-C; B/A = O) ` -`
SnSiO.2GeO.1P0.7O3.3s (compound D-5-D; B/A = 0) ' SnSiO.8P0.lAlO.lO3 (compound D-5-E; B/A = O) ~ i`.. i~

SnSio.sPo.2Alo.1O3.2s (compound D-5-F; B/A = O) ~ ;":
SnSiO.6P0.1AlO.3O2.9 (compound D-5-G; B/A = O) ` `.~ ``;~.`
SnSiO.6PO.3AlO.1O3.1 (compound D-5-H; B/A = O) `~
SnSiO.3P0.~AlO.1O3.5 (compound D-5-I; B/A = 1.5) ~ ;."```:~
SnSiO.8PO.2O3.1 (compound D-5-J; B/A = O) SnSiO.6PO.4AlO.2O3.5 (compound D-5-K; B/A = 0) -SnSiO.1PO.gAlO.lo3.6 (compound D-5-L; B/A = O) SnSiO.8AlO.2P0.2O3.4 (compound D-5-M; B/A = O) SnSiO.7AlO.2PO.3P3.45 (compound D-5-N; B/A = O) SnSiO.4AlO.2P0.6O3.6 (compound D-5-0; B/A = O) SnPAlO.1O3.65 (compound D-5-P; B/A = O) -` :
EXAMPLE D-l `j, A coin-shaped nonaqueous battery having the structure ~ "
shown in Fig. 2 was assembled in a dry box (dew point~ -40 to -70C; dry air) using the following materials. ~;
"~,'` '." .","'.'.' - 84 - , ,.~ ','''' ''.,~

~ ~3~2 Electrode:
-A negative elec~rode active material mixtureconsisting of 82% of each of compounds D-1-A to D-l-Q
synthesized in Synthesis Example D-1, 8% of flake graphite -and 4% of acetylene black as conducting agents, and 6% of polyvinylidene fluoride as a binder was compression molded ; ~;
into a pellet of 13 mm in diameter and 22 mg in wei~ht. : ~-. ~, .
Before use, the pellet was dried in the above-described dry ;~

box by means of a far infrared heater at 150C for 3 hours. ;~

Counter Electrode: -A positive electrode active material mixture `
., ;. ,.
onsisting of 82~ of LiCoO2 as a positive electrode active material, 8% of flake graphite, 4% of acetylene black, and 6%
of tet.rafluoroethylene was compression molded to obtain a ~;
pellet of 13 mm in diameter (the weight was decided according `~
to the lithium intercalation capacity of the compound D~
The charge capacity of LiCoO2 was 170 mAh/g. Before use, the pellet was dried in the same dry box as used above at 150C
for 3 hours by means of a far infrared heater.
Collector~
A 80 ~m thick net of SUS316 was welded to each of the positive case and the negative case.
ElectrolYtic Solution:
200 ~l of a 1 mol/Q solution of LiPF6 in a 2:2:6 (by volume) mixed solvent of ethylene carbonate, butylene carbonate and dimethyl carbonate.

Se~arator~
A ~inely porous polypropylene sheet and polypropylene .
nonwoven fabric impregnated with the electrolytic solution. ;~
The resulting nonaqueous battery was subjected to a charge and discharge test under cond:itions of a constant '`~
current density of 0.75 mA/cm2 and a voltage between 4.3 V ;~
and 2.7 V. All the tests were started with charging. The results obtained are shown in Table D~
Symbols used in Table D-1 and Tables D-2 to D~10 " ~
hereinafter shown have the following meanings~
(a) ... negative electrode active material of the present invention `.
(b) ... discharge capacity of the first cycle (mAh/g- "`~
negative electrode active material) ~:
(c) ... average discharge potential (V) (d) ... cycle characteristics (the number of cycles , i at which the discharge capacity was reduced to 60% of the initial discharge capacity).

~ ,, j ,, .,,. ~

.- ... ::
. . . -,.,. . :, - :;
:, ,' '' ":`

- 86 ~

. - .. ~ . "

.
3 ~ ~ ~ 2 TABLE D~
Run No. (a) (b) (c)_ (d) (mAh/g) (V) (cycles) 1D-1-A493 3.S0 335 2D-1-B452 3.52 296 .
3D-1-C498 3.30 311 4D-1-D470 3.59 300 5D-l-E484 3.40 296 6D-1-F451 3.59 304 `~ `
7D-l-G430 3.45 224 8D-1-H428 3.53 268 9D-1-I501 3.47 207 10D-l-J 453 3.47 311 11D-l-K 451 3.50 268 :~
12D-l-L 421 3.29 246 -13D-1-M 395 3.21 262 14D-1-N 380 3.27 290 15D-l-O 462 3.54 302 -16D-l-P 472 3.55 288 17D-1-Q 498 3.44 305 ;:
It is seen from these results that the negative ~' electrode active material according to the present invention ~.
~ ~ provides a nonaqueous secondary battery having excellent -:~
; charge and discharge cycle characteristics with a high : discharge potential and a high capacity.
EXAMPLE D-2 .- - .
. ~. :',:
- 87 - . ' :~ ~

~, % ~ 3 L~

A coin battery was prepared and tested in the same manner as in Example D-1, except for using compound D-2-A
synthesized in Synthesis Example D-2 as a negative electrode active material. The results obtained are shown in Table D- ;~
2.

Run `~
No. (a! (b! ~c!- (d! ` :
(mAh/g) (V)(cycles) ~r" ~""~"~ ~, 1 D-2-A 544 3.5 377 It is seen ~hat the battery using the negative -~
electrode active material obtained by calcination followed by '.!~;''`' '` ~`~` ~' quenching exhibits further improved charge and discharge `
cycle characteristics with a high discharge potential and a ;;
high capacity. ;~
EXAMPLE D-3 ~ ~ .
Coin batteries were prepared and tested in the same manner as in Example D-l, except for replacing the compound D-l with each of compounds D-3-A to D-3-Q synthesized in ;~
Synthesis Example D-3 as a negative electrode active material. The results obtained are shown in Table D-3.
.: .~' ,.' -~. ,' :. ",;

'- '~', ,';',." .;:

213~2 I : ~

Run No . ( a ) ( b ! ~c ! ( d ) (mAh/g~ (V) (cycles) : : ~ :
1 D- 3 -A 449 3.48 196 2 D-3-B 453 3.51 197 3 D-3-C 459 3.51 177 4 D-3-D 478 3.53 163 D-3-E 487 3.45 169 6 D-3-F 489 3.48 164 7 D-3-G 471 3.51 182 8 D-3-H 475 3.42 155 9 D-3-I 448 3.44 197 D-3-J 43i 3.50 255 11 D-3-K 409 3.51 251 12 D-3-L 492 3.38 189 13 D-3-M 409 3.42 202 14 D-3-N 421 3.61 279 D-3-O 401 3.68 288 16 D-3-P 457 3.40 212 17 D-3-Q 463 3.41 211 . : ~ ., , ~
It can be seen that the batteries using the negative electrode act`ive material according to the present invention ~.~ :
have excellent charge and discharge cycle characteristics, a high discharge potential, and a high capacity. ;~
COYPARATIVE EXAMPLE D~
. A coin battery was prepared and tested in the same manner as in Example D-l, except for using, as a negative electrode active material, SnO2 or SnO. The SnO2 and SnO
used here showed no broad scattering band assigned to : `~
amorphous properties in its X-ray diffractometry using CuKa rays. The results obtained are shown in Table D-4.
TABLE D-4 . .
Run No. ~al tb) (c! (d) mAh/g) (V) (cycles) :. .
1 SnO2 443 3.48 8S : .;
2 SnO 483 3.53 73 It is apparent that the use of the tin compound oxide :` .
according to the present invention as a negative electrode ` .
active material provides a battery superior to that using SnO2 or SnO in terms of charge and discharge cycle .;
characteristics and capacity.
COMPARATIVE EXAMPLE D-2 .
A coin battery was prepared and tested in the same manner as in Example D-1, except for using, as a negative electrode active material, Fe203, amorphous VzO5 ~ or LiCoVO4. .`` ;
The results obtained are shown in Table D-5. ;:~

; .' ,'. .,'"`
: ,~. . ..

, .'' .~ ' ,- .~."

_ 90 -' " '' ':

3~52 TAB~E D-S
Run No.A (a) (b) - ~c! td) - .
~mAh/g) (~) (cycles) 1 Fe2O3 109 3.16 13 ~:
2 V2Os 82 2.83 82 3 LiCoO4 256 2.91 102 It is seen that the battery using the tin compound oxide according to the present invention as a negative electrode active material is superior to that using Fe2O3, amorphous V2O5, or LiCoVO4 in terms of charge and discharge .
cycle characteristics, discharge potential, and discharge ;
capacity.
EXAMPLE D-4 ~.
A coin nonaqueous secondary battery was prepared and .
. . .... ..
te~ted in the same manner as in Run No. 1 of Example D-l, except or replacing LiCoO2 with each of the positive : -electrode active materials shown in Table D-6. The results ;~
obtained are shown in Table D-6.

,,~ ;,;.' '.,.
.. ... ........
- .'.'. ~

- 9 1 - .. . . .
.,~, " . . " ,: :,,, . ~.,~,: ,.

2 ~ ::
~ "

TABLE D-6 ~
., ~
Positive RunElectrode :
No. Active Ma erial(b~ ( c !Ld ! -~ .
(mAh/g) (~)(cycles) -1LiCoO2 493 3-5 335 2LiNiO2 497 3.39 340 3LiCO095Vo.osO2.0 485 3.49 390 4LiMn204 474 3-54 329 5LiMnO2 505 3.31 330 -It is seen that the negative electrode active material of the present invention provides a nonaqueous secondary battery excellent in all of charge and discharge `
cycle characteristics, discharge potential, and discharge capacity regardless of which of these positive electrode `~
active materials is used.

A mixture of 86% of compound D-1-A synthesized in Synthesis Example D-l as a negative electrode active `
material, 6~ of flake graphite, and 3% of acetylene black was mixed with 4% of an aqueous dispersion of a styrene-butadiene ~-rubber and 1~ of carboxymethyl cellulose as binders. The mixture was Xneaded together with water to prepare a slurry.
The slurry was extrusion coated on both sides of a 18 ~m thick copper foil and, after drying, compressed by calendaring. The compressed sheet was cut to a prescribed size to prepare a 124 ~m thick negative electrode sheet.

. ., ~ .
- 92 - ; ~ ~

h lL 3 ~ ~ ~ 2 A mixture of 87~ of LiCoO2 as a positive electrode active material, 6% of flake graphite, 3% of acetylene black, and, as binders, 3~ of an aqueous dispersion of polytetrafluoroethylene and 1~ of soclium polyacrylate was kneaded with water, and the resulting slurry was applied on both sides of a 20 ~m thick aluminum foil, dried, compressed, and cut to size in the same manner as described above to prepare a 220 ~m thick positive electrode sheet.
A nickel or aluminum lead was connected by spot ; ;
welding to the end of the negative electrode sheet or the positive electrode sheet, respectively. Both the electrode sheets with a lead were dried at 150C for 2 hours in dry air ~ ;
having a dew point of not higher than -40C. ;
Dried positive electrode sheet (8), finely porous polypropylene film separator (Cell Guard 2400t (10), dried ~
negative electrode sheet (9), and separator (10) were ` `
laminated in this order and rolled up by means of a winder. `;~
The roll was put in cylindrical open-top battery case ~ ~
(11) made of nickel-plated iron which also served as a ~ ;
negative electrode terminal, and a 1 mol/Q LiPF6 solution in -`
a 2:2:6 (by volume) mixture of ethylene carbonate, butylene carbonate, and dimethyl carbonate was poured into the case. - ;;;
Battery cover (12) with a positive electrode ter inal was fitted into the top of case (11) via gasket (13) to prepare a ` ;
cylindrical battery. Positive electrode terminal (12) and ~ ~`
positive electrode sheet (8) were previously connected via a - 93 - -~

q,~ ~

~ ~L 3 ~ ~ ~i 2 ! ~ :

lead terminal, and battery case (11) and negative electrode sheet (9) were connected in the same way.
--~ ,., :, The cross section of the thus assembled cylindrical ~ -battery is shown in Fig. 3. Numeral (14) is a safety valve.
The resulting battery was tested in the same manner as in , ::
Example D-l. The results obtained are shown in Table D-7. ;~
In Table D-7, symbol (e) means a discharge capacity per ml o~
a C size battery.

Run -No. (b! (c) Id) (e) (mAh/g) (V)(cycles) (mAh/ml) ; ;
1 4g8 3.56 570 366 ;~;
EXAMPLE D-6 AND COMPARATIVE_EXAMPLE D-3 ;~
Fifty coin batteries were prepared in the same manner as in Example D-l using each o compounds D-1-A to Q
synthesized in Synthesis Example D-1, compounds D-4-A to F
synthesized in Synthesis Example D-4, and compound D-5-A to P
synthesized in Synthesis Example D-5 as a negative electrode `
active material and subiected to a sa~ety test in the same manner as in Example A-7. As a result none of them ignited.
For comparison, the same test was conducted, except for using a pellet (15 mm in diameter; 100 mg in weight) of an Li-Al (80%-20%) alloy as a negative electrode active material. As a result, 32 out of 50 ignited.
It can be seen from these results that the nonaqueous secondary battery according to the present invention are of i, ' '. '~

high safety. ~ ::
COMPARATIVE EXAMPI.E D-4 SnSiO3 (compound D-1-A) synthesized in Synthesis Example D-l was heat treated at 700C for 2 hours and cooled . , ':
to room temperature to obtain ~rystalline SnSiO3. The X-ray ~':
diffraction pattern of the product showed no peak assigned to ''~,;
amorphous properties. A coin battery was prepared and tested.'~
in the same manner as in Example D-1, except for using the ;'.~
thus prepared crystalline SnSiO3 as a negative electrode .;;-":'.,.',, active material. The results of the charge and discharge ' ';.. ,'~
test are shown in Table D-8. ;~
TABLE D-8 :'; , Run .;~
No. ,._,,(a) (b) (c) (d! . :~
(mAh~g) (V) (cycles) ",.. ,.~',, `;.
1 SnSiO3 , 441 3.48 95 `,'.; '.`.".',.'~'.:~`.'.. ",' (crystalline) ,` ..'.', It can be seen that the nonaqueous secondary battery .'~''',.'~`,;
prepared by using the amorphous tin compound oxide of the ",'-,.,'"~.',; .,'present invention as a negative electrode active material is "~';.,, .'.'~.;,.'superior in charge and discharge cycle characteristics and ,',;','~
capacity to that prepared by using a crystalline tin compound '~
oxi~e. ~ ,.",",. - ", - EXAMPLE D-7 .
A coin battery was prepared and tested in the same .,,.,~
manner as in Run No. 1 of Example D-l, except for replacing ,'.`
compou~d D-1-A as a negative electrode active materLal with .~

', '' , ' ~ ?~ 2 .
-. .. ' .:
~: . - -each of compounds D-4-A to F synthesized in Synthesis Example D-4 and compounds D-5-A to P synthes:ized in Synthesis Example D-5. The results of the charge and discharge test are shown :~
in Table D-9.

" "' : ' -;.;~..;~.

`"` '~''~'`'.

, ~ . ", ` ~.

~.

~ ~" ''';'~

: . .. .
. . -:, ~,' '''' ' ' ', -"' -:.. :, ~; :

. ' "'~.:

~13~0~
. . ~`.
"''`: "

Run No. (a! (b! ~c) ( (mAh/g) (V)(cycles) ; ~-1 D-4-A 500 3.50 350 2 D-4-B 495 3.51 344 3 D-4-C 515 3.51 367 4 D-4-D 516 3.50 359 D-4-E 510 3.49 348 - 6 D-4-F 520 3.53 370 7 D-5-A 540 3.51 376 8 D-5-B 545 3.48 374 9 D-5-C 535 3.51 378 D-5-D 540 3.52 374 11 D-5-E 545 3.51 385 12 D-5-F 550 3.52 390 13 D-5-G 555 3.51 365 14 D-5-H 557 3.51 368 D-5-I 548 3.52 388 D-5-J 510 3.52 354 17 D-5-~ 555~ 3.52 378 - 18 D-5-L 550 3.51 355 19' ~D-5-M 560 3.51 387 D-5-N 558 3.51 373 - 21 D-5-O 557 3.51 383 22 D-5-P 562 3.52 372 The results prove that the negative electrode active ~ . . . ~: , 3~2 :-:
!

materials which can be used in the pxesent invention provide a nonaqueous secondary battery with excellent charge and discharge cycle characteristics, a h:igh discharge potential, , ~ . .
and a high capacity. It is also seen that batteries using a P-containing compound as a negative electrode active material are particularly excellent in charge and discharge cycle ;~ ~ .
characteristics.
EXAMPLE D-8 : ~ :
A coin battery was prepared and tested in the same manner as in Example D-4, except for replacing compound D-1 A
as a negative electrode active material with each of `
compounds D-4-A to F synthesized in Synthesis Example D-4 and compounds D-5-A to P synthesized in Synthesis Example D-5.
The results of the charge and discharge test are shown in Table D-10. In Table D-10, symbol (e) has the same meaning ~ ~
as in Table D-7. . .... .
: ' - ';;:
....
- ~ :
.......

"; ;`.'~

- .

': ~; .

. .
.. .
~ "'. ' ' ., :~;
' ' ', ,:'~ '' ~ ~ ~ 4 ~ ~ 2 - ... .. -.

. ~ , .",...

Run No . ( ~ ~ _ ( b ~ ( c ~ - ( d ) ( e L
(mAh/g ) (~V) ( cycles ) (mAh/ml ) - ~ ;; -1 D-4-A 502 3.56 570 368 2 D-4 -B 498 3.57 560 366 3 D-4-C 518 3.57 575 381 4 D-4-D 518 3.55 580 380 D-4-E 511 3.55 568 376 6 D-4-F 522 3.57 581 381 7 D-5-A 543 3.58 580 399 8 D-5-B 549 3.54 581 403 9 D-5-C 540 3.57 584 397 D-5-D 543 3.58 582 399 11 D- 5 -E 551 3.56 591 405 12 D-5-F 553 3.56 593 406 13 D-5-~ 560 3.56 574 412 14 D-5-H 562 3.57 577 413 D-5-I 553 3.57 595 406 16 D-5-J 512 3.57 573 376 17 D-5-K 557 3.56 592 409 18 D- 5 -L 553 3.56 570 406 19 D-5-M 562 3.55 596 413 ~''" ' . ', . ', ~, ' ,~
D-5-N 560 3.56 590 412 ~ ~ -21 D-5-O 559 3.56 594 411 22 D-5-P 561 - 3.56 584 413 As described above, the use of an Li-containing `
;~ "",....
_ g g _ .". ~ " . ,.
" , , ;~ ;,~ ,.

transition metal oxide as a positive electrode active material and at least one specific compound oxide as a negative electrode active material affords a nonaqueous secondary battery having a high discharge potential, a high discharge capacity and excellent charge and discharge cycle characteristics.
SnO, GeO2, and PbO2 used in the following Examples are commercially available ones.
SYNTHESIS EXAMPLE E~
A uniform rnixture of SnO and SnF2 at a molar ratio of -~ :
o . 9 n .1, totally weighing 20 g, was calcined in an argon atmosphere at 950C for 6 hours and cooled to room temperature over a period of 2 hours to obtain SnF0,2OO,g. The calcined product was ground in a grinding machine and sieved ; .
to obtain a powdered negative electrode active material .: :
precursor having an average particle size of about 10 ~m.

A uniform mixture of SnO, SiO2, and SnF2 at a molar ..
ratio of 0.8:1.0:0.2, totally weighing 20 g, was calcined in .~
an argon atmosphere at 1000C for 6 hours and cooled to room :~ ~:
temperature over a period of 2 hours to obtain glassy amorphous SnSiFO4O2.8 as a yellow solid. The calcined product was ground in a grinding machine and sieved to obtain a ;. . .
powdered negative electrode active material precursor having .
an average particle size of about 5 ~m.
Alternatively, a 5% acidic aqueous solution - 100 ~

-: ~13 A ~ ~ 2 , , ~

containing SnCl2 and SiCl4 at a molar ratio of 0.8:1.0 was neutralized with aqueous ammonia while stirring. The `~ -stirring was continued for an additional period of 4 hours while keeping at 80 to 90C, and the thus formed precipitate -was collected by filtration and dried in vacuo at 200DC for 24 hours to obtain SnO.8SiOz.8 as a yellow powder. The powder was mixed with SnF2 at a molar ratio of 1:0.2. A 20 g portion of the mixture was heat treated at 100QC for 1 hour in an argon atmosphere to obtain glassy amorphous SnSiF04O2.
as a yellow solid.

A uniform mixture of SnO, SiO2, SnF2, and GeO2 at a `
molar ratio of 0.8:1.0:0.2:0.1, totally weighing 20 g, was ;
calcined in an argon atmosphere at 1000C for 6 hours and ~ `
cooled to room temperature over a period of 2 hours to obtain ~ `
glassy amorphous SnSiGe0.lFO4O3.0 as a yellow solid. The ~ -calcined product was ground in a grinding machine and sieved to obtain a powdered negative electrode active material precursor having an average particle size of about 6 ~m.` ~ `~
In the same manner as described above but using stoichiometrical amounts of the respective raw materials, SnSiTiOlFO.4O3.0, SnSiAlO.lFO.4O3.0, SnSiFe0.lF0.4O~O, and SnSiZnOlFO.4O3.0 were synthesized.

A uniform mixture of SnO, GeO2, and SnF2 at a molar `
ratio of 0.8:1.0:0.2, totally weighing 20 g, was calcined in ~

- 101 - , `'"`";' ' -, ,' :-'`"~' '''.' :. ,... :..

an argon atmosphere at 1000C for 6 hours and cooled to room temperature over a period of 2 hours to obtain glassy amorphous SnGeFO4O2.3 as a yellow solid. The calcined product ;
was ground in a grinding machine and sieved to obtain a powdered negative electrode active material precursor having an average particle size of about 4 um. ~-;
SYNTHESIS EXAMPLE E--5 :
A uniform mixture of SnO, PbO2, and SnF2 at a molar ratio of 0f.8:1.0:0.2, totally weighing 20 g, was calcined in :~
an axgon atmosphere at 1000C for 6 hours and cooled to room ~:
temperature over a period of 2 hours to obtain an amorphous : :~
solid, SnPbFO.4O2.8. The calcined product was ground in a grinding machine and sieved to obtain a powdered negative ~`, `.
electrode active material precursor having an average . ~:
particle size of about 8 f~m. ~ ~
SYNTHESIS EXAMPLE E-6 ` ` `
A dry mixture of 2.26 g of lithium carbonate, 5.0 g .
of tricobalt tetroxide, and 0.16 g of zirconium dioxide was -:
calcined in air at 900C for 18 hours to synthesize crystalline LiCoZr0.02O2 as a positive electrode active material. The resulting product was ground to obtain a brown powder having an average particle size of 5 f~m. ~;

A dry mixture of 1.20 g of lithium carbonate and :
5.92 g of manganese dioxide was calcined in air at 1300C for 12 hours to synthesize crystalline LiMn2O4 as a positive electrode active material. Average particle size: 3 ~m. i `

Electrode:
A negative electrode active material mixture ~``-i;
consisting of 82% of each of the negative electrode active material precursors shown in Table E-1, 8% of flake graphite and 4% of acetylene black as conducting agents, and 6~ of polyvinylidene fluoride as a binder was compression molded `
into a pellet of 13 mm in diameter and 22 mg in weight. For " `-i~
comparative negative electrode active materials, coke (LCP-u, produced by Nippon Steel Chemical Co., ~td.) and rutile type WO2 were used.
Counter Electrode~
A positive electrode active material mixture consisting of 82% of each of the positive electrode active ~ `~
material~ shown in Table E-1, 8% of flake graphite, 4% of acetylene black, and 6% of tetrafluoroethylene was compression molded to obtain a pellet of 13 mm in diameter and 110 mg in weight.
The negative electrode pellet and the positive electrode pellet w~re dried in a dry box (dir air; dew point: i -40 to -70C) at 150C for about 3 hours by means of a far infrared heater.
, -, , :,~,.:
Collector~
: . . . - .: .:
A 80 ~m thick net of SUS316 was welded to each of a ;
positive case and a negative case.
,: ~'~'', - 103 - ~
: .

`~ 21~0~
. . . , ~ , .. . ,`
Electrolvtic Solution:
200 ~1 of a 1 mol/Q solution of LiPF6 in a 2:2:6 (by volume) mixed solvent of ethylene carbonate, butylene carbonate and dimethyl carbonate.
Separator~
A finely porous polypropylene sheet and polypropylene nonwoven fabric impregnated with the electrolytic solution.
The positive electrode case and the negative -electrode case were fitted to each other to prepare a coin `
lithium battery. ~-....
- The resulting coin battery was subjected to a charge and discharge test under conditions of a constant current density of 0.75 mA/cm2, a cut-off voltage of 4.3 V in charging, and a cut-off voltage of 2.7 V in discharging. All the tests were started with lithium intercalation into the negative electrode active material precursor. While more than 50 kinds of coin batteries were prepared and tested using a variety of combinations of a negative electrode active material and a positive electrode active material, only the typical results are shown in Table E-l. It should ;
therefore be understood that the combination of a negative electrode active~material and a positive electrode active material which can be used in the present invention is not limited to those shown in Table E-l. ;

~ : .
- 104 - ~ ~

' ~ ' "~

TABLE ~
PositiveNegative Discharge ElectrodeElectrode Average Capacity Cycle ` ~ ~
Active Active Discharge at the Charac- ~ ` -MaterialMaterial Potentia:L 2nd CYcleteristics~
(V) (mAh/g ) ,~",, ",, ~
Comparison:
Licozro.o2o2 coke 3.40 180 0.10 . : .-: :.
LiCoZrO.02O2 W02 3.20 160 0.15 t.iMn204 coke 3.3 170 0.12 LiMn204 W02 3.10 140 0.17 Invention~
LiCoZrO.o2o2 SnF0.2OO.9 3 - 53 450 0.07 LiCoZ~0.0202 SnSiF0.402.8 3 - 55 420 0.04 LiCoZrO.o2o2 5nSiFl.0O2.5 3-55 410 0.05 LiCoZrO.0202 SnsiGeo.lFo.4o33.56 430 0 - 04 Licozro~o2o2 SnSiAlo.lFo.4O33.56 420 0.03 LiCoZrO,02O2 SnsiTio~lFo.4o33.56 420 0.03 . - .. -: :
Licozro.o2o2SnSiZnO.lF0.4O3 3.55 410 0.04 LiCoZrO.02O2SnSiFeO.lF0.4O3 3.54 410 0.05 LiCoZro.o2o3SnGeF0,4O2.s 3.50 450 0.06 LiCoZrO~o2o3SnPbF0.4O2.8 3.50 400 0.08 -LiMn204SnFO.200.93.50 ; 430 O.08, .
LiMn204SnSiF0.402.8 3.51 400 0.07 LiMn;!04SnSiGeo.lFo.403 3.51 400 0.08 -LiMn204SnSiAlO,lF0,403 3.52 410 0.05 ~
LiMn2b4SnSiTio.lFo.4O3 3.52 400 0.05 - :

- 105 - ; ```

~-` 213A0~2 LiMn204 SnGeFO.402.8 3-45 420 0.08 Note: * (Discharge capacity of the 10th cycle - discharge - .
capacity of the 1st cycle)/discharge capacity of the 1st cycle :
It is obvious from the results in Table E-1 that the ~
nonaqueous secondary batteries using the negative electrode ~ . .
active material according to the present invention are superior in discharge capacity and cycle characteristics to `~
those using conventional negative electrode active-materials. ~: .
According to the present invention, the use of an :;
oxide containing the group IIIB, IVB or VB metal and fluorine ;~
furnishes a nonaqueous secondary battery having a high ~; .
discharge capacity and satisfactory charge and discharge :
cycle characteristics.
Compared wLth the conventional batteries using coke or W02 as a negative electrode active material, the .
non~queous secondary batteries of the present invention have a higher average discharge potential by 0.1 to 0.35 V.
Further, the discharge capaclty, measured at the 2nd cycle, of the batteries of the present invention is at least double : .
that of the conventional ones. Therefore, the batteries of .~ :
the present invention are very effective in the applications ...........
requiring high power.
While the invention has been described in detail and with reference to speci~ic examples thereof, it will be apparent to one skilled in the art that various changes and - - 106 - .

~ ~L 3 ~ ~ ~ 2 modifications can be made therein without departing from the .
spirit and scope thereof. ,.
' `"''''`"`';''"'`''``
`'.:' ,'; ~.' ...., ~ . . ..

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Claims (20)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A nonaqueous secondary battery comprising a positive electrode active material, a negative electrode active material, and a lithium salt, wherein said negative electrode active material contains at least one compound capable of intercalating and deintercalating lithium mainly comprising an atom of the group IIIB, IVB or VB of the periodic table.
2. A nonaqueous secondary battery comprising a positive electrode active material, a negative electrode active material, and a lithium salt, wherein said negative electrode active material mainly comprises an amorphous compound containing at least two atoms selected from the elements of the groups IIIB, IVB, and VB of the periodic table.
3. A nonaqueous secondary battery comprising a positive electrode active material, a negative electrode active material, and a lithium salt, wherein said negative electrode active material is a compound capable of intercalating and deintercalating lithium containing at least one of the atoms of the group IIIB, IVB, and VB of the periodic table and fluorine.
4. A nonaqueous secondary battery comprising a positive electrode active material, a negative electrode active material, and a lithium salt, wherein said negative electrode active material contains at least one compound of the atom of the group IIIB, IVB or VB of the periodic table, Zn, or Mg which is capable of intercalating and deintercalating lithium.
5. A nonaqueous secondary battery as claimed in claims 1 to 4, wherein the atom of the group IIIB, IVB and VB
of the periodic table is selected from the group consisting of AL, Si, Ge, Sn, Pb, As, and Sb.
6. A nonaqueous secondary battery as claimed in any of claims 1 to 4, wherein said negative electrode active material is a compound which is amorphous at the time of intercalating lithium ion.
7. A nonaqueous secondary battery as claimed in any of claims 1 to 4, wherein said negative electrode active material is a compound which is amorphous at the time of assembling a battery.
8. A nonaqueous secondary battery as claimed in any of claims 1 to 4, wherein said negative electrode active material mainly comprises a compound represented by formula (I):

M1M2M4 (I) wherein M1 and M2, which are different from each other, each represent at least one of Si, Ge, Sn, Pb, P, B, Al, As, and Sb; M4 represents at least one of O, S, Se, and Te; p represents a number of from 0.001 to 10; and q represents a number of from 1.00 to 50.
9. A nonaqueous secondary battery as claimed in any of claims 1 to 4, wherein said negative electrode active material mainly comprises a compound represented by formula (I):

M1M2pM4q (I) wherein M1 and M2 are different from each other, M1 represents at least one of Ge, Sn, Pb, Sb, and Bi; M2 represents at least atom of the groups IIIB, IVB, and VB of the periodic table; M4 represents at least one of O, S, Se, and Te; p represents a number of from 0.001 to 1; and q represents a number of from 1.00 to 50.
10. A nonaqueous secondary battery as claimed in any of claims 1 to 4, wherein said negative electrode active material mainly comprises a compound represented by formula (II):

SnM3pM5q (II) wherein M3 represents at least one of Si, Ge, Pb, P, B, Al, As, and Sb; M5 represents at least one of O and S; p represents a number of from 0.001 to 10; and q represents a number of from 1.00 to 50.
11. A nonaqueous secondary battery as claimed in any of claims 1 to 4, wherein said negative electrode active material mainly comprises a compound oxide represented by formula (III):

SnM3rOs (III) wherein M3 represents at least one of Si, Ge, Pb, P, B, Al, and As; r represents a number of from 0.01 to 5.0; and s represents a number of from 1.0 to 26.
12. A nonaqueous secondary battery as claimed in any of claims 1 to 4, wherein said negative electrode active material mainly comprises a compound oxide represented by formula represented by formula (IV):

SnSitPuM6vOs (IV) M6 represents at least one of Ge, B, Al, and Pb; t represents a number of from 0.01 to 2.0; u represents a number of from 0.01 to 4.0; v represents a number of from 0.01 to 2.0; and s represents a number of from 1.0 to 26.
13. A nonaqueous secondary battery as claimed in any of claims 1 to 4, wherein said negative electrode active material mainly comprises a compound oxide represented by formula (V):

SnSitPuAlvM7wOs (V) wherein M7 represents at least one of Ge, B, and Pb; t represents a number of from 0.01 to 2.0; u represents a number of from 0.01 to 4.0; v represents a number of from 0 to 2.0; w represents a number of from 0.01 to 2.0; and s represents a number of from 1.0 to 26.
14. A nonaqueous secondary battery as claimed in any of claims 1 to 4, wherein said negative electrode active material is obtained by a calcination method consisting of heating at a rate of temperature rise of 4° to 2000°C/min, maintaining at 250° to 1500°C for 0.01 to 100 hours, and cooling at a rate of temperature drop of 2° to 107°C/min.
15. A nonaqueous secondary battery as claimed in any of claims 1 to 4, wherein said negative electrode active material is obtained by a calcination method consisting of heating at a rate of temperature rise of 10° to 2000°C/min, maintaining at 250° to 1500°C for 0.01 to 100 hours, and cooling at a rate of temperature drop of 2° to 107°C/min.
16. A nonaqueous secondary battery as claimed in any of claims 1 to 4, wherein said positive electrode active material is a lithium-containing transition metal oxide.
17. A nonaqueous secondary battery as claimed in any of claims 1 to 4, wherein said positive electrode active contains at least one compound represented by formula LixQOy, wherein Q represents at least one transition metal selected from Co, Mn, Ni, V, and Fe; x is from 0.2 to 1.2; and y is from 1.4 to 3.
18. A nonaqueous secondary battery as claimed in any of claims 1 to 4, wherein said positive electrode active contains at least one compound selected from LixCoO2, LixNiO2, LixMnO2, LixCoaNil-aO2, LixCobVl-bbOz, LiXCobFel_bO2, LixMn2O4, LixMncCo2-cO4, LixMnCNi2-cO4, LixMncV2-cO4, and LixMncFe2-cO4 (wherein x = 0.7 to 1.2; a = 0.1 to 0.9; b = 0.8 to 0.98; c = 1.6 to 1.96; z = 2.01 to 2.3).
19. A nonaqueous secondary battery as claimed in any of claims 1 to 4, wherein said positive electrode active material is a lithium-containing manganese compound having a spinel structure and a stoichiometric or non-stoichiometric composition.
20. A nonaqueous secondary battery as claimed in any of claims 1 to 4, wherein lithium is intercalated in an amount of from 1 to 20 equivalents.
CA002134052A 1993-10-22 1994-10-21 Nonaqueous secondary battery Abandoned CA2134052A1 (en)

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
JP5264995A JPH07122274A (en) 1993-10-22 1993-10-22 Nonaqueous secondary battery
JPHEI-5-264995 1993-10-22
JPHEI-6-7760 1994-01-27
JP00776094A JP3498345B2 (en) 1994-01-27 1994-01-27 Non-aqueous secondary battery
JPHEI-6-26745 1994-02-24
JP6026745A JPH07235293A (en) 1994-02-24 1994-02-24 Nonaqueous electrolyte secondary battery
JPHEI-6-30206 1994-02-28
JP3020694 1994-02-28
JP6066422A JPH07249409A (en) 1994-03-11 1994-03-11 Nonaqueous electrolyte secondary battery
JPHEI-6-66422 1994-03-11

Publications (1)

Publication Number Publication Date
CA2134052A1 true CA2134052A1 (en) 1995-04-23

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US (3) US5618640A (en)
EP (3) EP0651450B1 (en)
CA (1) CA2134052A1 (en)
DE (3) DE69415769D1 (en)

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Publication number Priority date Publication date Assignee Title
USH1721H (en) * 1996-09-20 1998-04-07 Moli Energy (1990) Limited Aqueous rechargeable battery
US6143216A (en) * 1997-10-10 2000-11-07 3M Innovative Properties Company Batteries with porous components
US6171723B1 (en) 1997-10-10 2001-01-09 3M Innovative Properties Company Batteries with porous components
US6203944B1 (en) 1998-03-26 2001-03-20 3M Innovative Properties Company Electrode for a lithium battery
US6436578B2 (en) 1998-03-26 2002-08-20 3M Innovative Properties Company Electrode compositions with high coulombic efficiencies
US6255017B1 (en) 1998-07-10 2001-07-03 3M Innovative Properties Co. Electrode material and compositions including same
US6428933B1 (en) 1999-04-01 2002-08-06 3M Innovative Properties Company Lithium ion batteries with improved resistance to sustained self-heating

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EP0814522A3 (en) 1999-05-12
EP0814522B1 (en) 2006-03-29
DE69434684T2 (en) 2006-12-07
US5965293A (en) 1999-10-12
DE69415769D1 (en) 1999-02-18
DE69434683D1 (en) 2006-05-18
EP0651450B1 (en) 1999-01-07
US5780181A (en) 1998-07-14
EP0814523A3 (en) 1999-05-12
US5618640A (en) 1997-04-08
DE69434684D1 (en) 2006-05-18
EP0814523A2 (en) 1997-12-29
EP0814522A2 (en) 1997-12-29
EP0651450A1 (en) 1995-05-03
DE69434683T2 (en) 2006-12-07
EP0814523B1 (en) 2006-03-29

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