USRE33306E - Secondary battery or cell with improved rechargeability - Google Patents
Secondary battery or cell with improved rechargeability Download PDFInfo
- Publication number
- USRE33306E USRE33306E US07/254,966 US25496688A USRE33306E US RE33306 E USRE33306 E US RE33306E US 25496688 A US25496688 A US 25496688A US RE33306 E USRE33306 E US RE33306E
- Authority
- US
- United States
- Prior art keywords
- cell
- secondary battery
- lithium
- carbonaceous material
- active material
- 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.)
- Expired - Lifetime
Links
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 48
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 39
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- 239000006183 anode active material Substances 0.000 claims abstract description 22
- 239000006182 cathode active material Substances 0.000 claims abstract description 19
- 238000000197 pyrolysis Methods 0.000 claims abstract description 19
- 239000011368 organic material Substances 0.000 claims abstract description 17
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 10
- 150000003624 transition metals Chemical class 0.000 claims abstract description 10
- 150000001786 chalcogen compounds Chemical class 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- -1 polyethylene Polymers 0.000 claims description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229920001568 phenolic resin Polymers 0.000 claims description 11
- 239000005011 phenolic resin Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000011295 pitch Substances 0.000 claims description 7
- 150000001299 aldehydes Chemical class 0.000 claims description 6
- 230000005611 electricity Effects 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- 150000002170 ethers Chemical class 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 238000002441 X-ray diffraction Methods 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims description 3
- 150000004770 chalcogenides Chemical class 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 3
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- 229940079593 drug Drugs 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 239000010408 film Substances 0.000 claims description 2
- 239000007849 furan resin Substances 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 229920005735 poly(methyl vinyl ketone) Polymers 0.000 claims description 2
- 229920001197 polyacetylene Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
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- 229920002480 polybenzimidazole Polymers 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920000131 polyvinylidene Polymers 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 229910013350 LiBCl4 Inorganic materials 0.000 claims 1
- 229910001290 LiPF6 Inorganic materials 0.000 claims 1
- 238000007599 discharging Methods 0.000 claims 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims 1
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 claims 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 10
- OXMIDRBAFOEOQT-UHFFFAOYSA-N 2,5-dimethyloxolane Chemical compound CC1CCC(C)O1 OXMIDRBAFOEOQT-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 6
- 150000004292 cyclic ethers Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000011888 foil Substances 0.000 description 4
- 239000003077 lignite Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- BHHSIMAZIRFUBT-UHFFFAOYSA-N [Li].FP(=O)=O Chemical compound [Li].FP(=O)=O BHHSIMAZIRFUBT-UHFFFAOYSA-N 0.000 description 3
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A secondary battery or cell with improved rechargeability is obtained by combination of (A) a cathode active material comprising a chalcogen compound of a transition metal, (B) an electrolyte comprising an organic solvent having dissolved therein a lithium salt and (C) an anode active material comprising lithium metal in electrical contact with an electrically conductive carbonaceous material which is a pyrolysis residue of an organic material such as synthetic high polymers. The anode active material can be formed in situ within the battery, by self discharge of lithium metal into the carbonaceous material. The battery or cell is of excellent properties, such as stability or flatness of discharge voltage and electric capacity.
Description
1. Field of the Invention
This invention relates to a secondary battery or cell, and particularly to a lithium cell containing nonaqueous electrolytes.
2. Description of the Prior Art
Recently, a secondary battery or cell, wherein a conjugated pyrolysis residue of a high polymer is used as a cathode and/or an anode, has been proposed [Japanese Laid-open Pat. No. 93176/1983].
One of the major problems limiting the successful development of rechargeable versions of lithium batteries is the nature of the lithium dendritic deposits during the charging mode of such batteries.
It is an object of the present invention to eliminate dendritic growth of lithium during the discharge-charge cycles in a lithium battery or cell.
As another object, this invention provides a secondary battery or cell having improved stability or flatness of discharge voltage and capacity.
It is still another object of the invention to provide a secondary battery or cell with an improved rechargeability or high discharge voltage, high energy density and large electric capacity in spite of little volumetric capacity.
A further object of this invention is to provide a secondary battery which is economical due to its use of easily obtainable active anode materials.
Briefly, these and other objects of the present invention, which will become more readily apparent below have been attained broadly by a secondary battery or cell with improved rechargeability, which comprises:
(A) a cathode active material comprising a chalcogen compound of a transition metal,
(B) an electrolyte comprising an organic solvent having dissolved therein a lithium salt, and
(C) an anode active material comprising lithium metal in electrical contact with an electrically conductive substantially amorphous carbonaceous material which is a pyrolysis residue of an organic material.
The nature, objects and advantages of the invention will be more fully understood from the following description of a preferred embodiment shown by way of example in the accompanying drawing FIG. 1. FIG. 1 is a schematic cross sectional view of a cell in accordance with the invention.
Suitable electrically conductive carbonaceous materials, used in electrical contact with lithium metal as anode active material in accordance with the present invention, include pyrolysis residues of organic materials, such as synthetic high polymers, natural high polymers, pitches, coals and the like. Suitable examples of these organic polymers are those used as precursor or raw materials for carbon and graphite fibers as described, for instance, in "CARBON AND GRAPHITE FIBERS Manufacture and Applications" (edited by Marshal Sittig, published by Noyes Data Corp. 1980).
Suitable synthetic high polymers include, for example, polyacrylonitrile, polyvinyl chloride, polyvinylidene, chloride, polyvinyl alcohol, polybutadiene, polyethylene, polymethylvinylketone, polyphenylenes (such as p-polyphenylene), polystyrene, polyacetylenes, polyarylacetylenes (such as polyphenylchloroacetylene), polyimides (such as polyoxydiphenylenepyrromellitic imide, polybenzoxazole imide, polyimidazopyrroloneimide, polyamidoimides, polyhydrazidoimide), polyamides, polybenzimidazoles, polysemicarbazides, polybenzoxadinones, epoxy resins, furan resins and phenolic resins.
Examples of suitable natural high polymers are wood, coconut shells, cellulosic materials (such as cellulose, regenerated cellulose, cellulose acetates and the like), starch, protein, wool, lignin and rubber.
These synthetic and natural high polymers may have a wide range of molecular weight. In general, the molecular weight (number average) of these polymers is at least 5000, preferably 10,000-1,000,000 or higher.
Exemplary of suitable pitches are petroleum pitch, coal tar pitch, wood tar pitch and rosin pitch.
Illustrative of coals are lignite, brown coal, subbituminous coal, bituminous coal and anthracite.
Among the organic materials, preferred are polyarylacetylenes and phenolic resins.
Illustrative of suitable polyarylacetylenes are those having repeating units of the following general formula (1): ##STR1## wherein X is Cl or methyl, and Y is H, Cl or methyl.
Suitable examples of arylacetylene monomers constituting the repeating units of the formula (1) include phenylacetylenes, such as 1-phenylpropyne; and halophenylacetylenes, such as 1-chloro-2-tolylacetylene, 1-chloro-2-chlorophenylacetylene, 1-chlorophenylpropyne and the like; as well as mixtures of two or more of them. Among these, preferred are halophenylacetylenes, particularly 1-chloro-2-phenylacetylene.
Polyarylacetylenes may include, if necessary, other repeating units than the repeating units of the formula (1). Suitable comonomers constituting the other repeating units include alkyl acetylenes, such as mono-alkyl(C1 -C20)acetylenes and di-alkyl(C1 -C20 and C1 -C5)acetylenes. Illustrative of these acetylenes are 1-alkynes, such as t-butyl acetylene, t-pentyl acetylene, 4-methyl-1-pentyne, and 1-hexyne; 2-alkynes such as 2-hexyne, 2-octyne and 2-decyne, and mixtures of two or more of them.
In these copolymers composed of repeating units of the formula (1) and of alkyl acetylene, the content of the units of formula (1) is preferably at least 50%, more preferably at least 80% by weight based on the weight of the total monomer units.
Aryl acetylene polymers can be obtained by the methods described in "Polymer Bulletin", Vol. 2, page 823-827 (1980), and "Polymer Journal", Vol. 11, page 813(1979) and Vol. 13, page 301 (1981).
Arylacetylene polymers are light yellow or white solids, and usually have number-average molecular weight of at least about 5,000 (measured by osmometry), preferably about 10,000-about 1,000,000.
Suitable phenolic resins include polycondensation products of phenols with aldehydes or aldehyde precursors (such as formaldehyde, acetoaldehyde, furfural, paraformaldehyde and formal), in the presence of acidic catalysts (such as oxalic acid, hydrochloric acid) to form novolak resins or in the presence of alkaline catalysts (such as ammonia) to form resol resins. Examples of suitable phenols are phenol, resorcinol; mono- and di-alkyl phenols, such as o-, m- and p-cresols, xylenols, p-isopropylphenol, t-butylphenol and p-octylphenol; and aryl phenols, such as p-phenylphenol, 2-hydroxyphenyl-2-propylphenol and the like.
Exemplary of such phenolic resins are phenol-formalin resins, cresol-formalin resins, phenol-furfural resins, resorcinol-formalin resins, and the like; as well as modified phenolic resins, such as tercondensation polymers of phenols, aldehydes (such as formalin) and natural resins (such as drying oils, rosins and the like), etherified phenolic resins obtained by acidic etherification of methylol radicals of resols with monohydric alcohols (such as butanol).
The polycondensation degree of phenolic resins is preferably at least 5. Uncured resins may be used (precondensates), as well as cured resins.
Pyrolysis residues of the organic materials used in this invention, can be produced by known pyrolysis methods. Pyrolysis or carbonization is ordinarily performed by heating or thermal treatment of the abovementioned organic materials in an atmosphere of inert gas, such as nitrogen, to a temperature sufficiently high to bring about substantially complete thermal decomposition of noncarbon constituents of the organic material, which temperature is not so high as to bring about substantial graphitization of the resulting pyrolyzed or carbonized material. The temperature of the thermal treatment is generally about 300° to about 1700° C., preferably about 500° to about 1500° C.; and the heating period is ordinarily 1 to 50 hours, preferably 2 to 20 hours. The heating temperature may be raised stepwise, for example, by heating to a temperature of 300° to 600° C. for 0.5-10 hours, followed by an increase to a temperature of 600° to 1500° C. for 1-10 hours.
Pyrolysis residues used in the invention, may be activated pyrolyzed residues, for example, those activated by steam activation, drug activation and other activation methods (such as partial oxidation by heating in air, carbon dioxide gas or chlorine gas). Examples of suitable activated pyrolyzed residues include activated charcoals, obtained by activating by conventional methods, pyrolyzed residues of a natural high polymer (such as wood, coconut shell, sawdust, lignin, cattle bone and blood) and coals (such as peat, lignite, brown coal). Activated charcoals are described in "ENCYCLOPAEDIA CHIMICA" Vol. 2, page 437-438, published by Kyoritsu Shuppan Co., Japan (1963), and Kirk-Othmer "ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY" Vol. 2, page 149-158 published by John Wiley & Sons, Inc. (1963).
Pyrolysis residues (including those which are activated), used in the present invention, may be in the form of film, fiber, fabrics (woven fabric and non-woven fabric), thin plate and powder.
These carbonaceous materials (pyrolysis residues) are usually porous and preferably have a density of at most 1.8 g/cm3. These materials have high electrical conductivity of usually at least 10-5 mho/cm, preferably at least 10-3 mho/cm, and exhibit a substantially amorphous X-ray diffraction pattern. [Natural graphites and artificial graphites made by heating at high temperature (such as 2500° to 4500° C.) and having a predominant X-ray diffraction pattern characteristic of graphite cannot be used for the anode active materials of the present invention.]
The anode active material (C) used in this invention comprises lithium metal in electrical contact with an electrically conductive carbonaceous material (pyrolysis residue). Electrical contact of the carbonaceous material with lithium metal may be accomplished, for example, by direct mounting of lithium metal on the surface of the carbonaceous material.
The cathode active material (A) in this invention comprises a chalcogen compound of a transition metal. Suitable transition metals include, for example, metals of Groups IB-VII and Group VIII of the long form periodic table, such as titanium, vanadium, chromium, manganese, cobalt, copper, iron, niobium and molybdenum. Examples of the chalcogen compounds are chalcogenides, such as oxides, sulfides and selenides, of the above-mentioned metals. Illustrative examples of suitable chalcogenides are: oxides such as TiO2, Cr3 O8, V2 O5, MnO2, LiCoO2, CuO and MoO3 ; sulfides such as TiS2, VS2, Cr0.5 V0.5 S2, CuCo2 S4, FeS and MoS3 ; and selenides such as VSe2 and NbSe3. Among these, preferred are MnO2 and V2 O5.
Cathode active materials are generally used in the form of molded items. For example, a powder of cathode active materials or a mixture thereof with binders (such as polytetrafluoroethylene, polyethylene, polystyrene) can be sintered within a mold under pressure to form molded pieces.
The electrolyte (B) employed in the invention comprises an organic solvent having dissolved therein a lithium salt. Examples of suitable organic solvents are esters, ethers, oxazolidinones, amides, nitriles, aldehydes and ketones as described below, as well as mixtures of two or more of them.
(a-1) alkylene carbonates, such as ethylene carbonate, propylene carbonate and the like;
(a-2) lactones, such as gamma-butyrolactone and the like;
(a-3) other esters, including alkyl carboxylates, such as methyl and ethyl formates, acetates, butyrates and the like.
Among those, propylene carbonate is preferred.
(b-1) non-cyclic ethers, including dialkyl ethers, such as t-butyl methyl ether, t-butyl ethyl ether, di-isopropyl ether and diethyl ether, and ethers derived from ethylene glycol and polyethylene glycols, such as 1,2-dimethoxyethane, diethyleneglycol dimethyl ether and the like;
(b-2) cyclic ethers, such as tetrahydrofuran, 2-methyltetrahydofuran 2,5-dimethyltetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, pyrans, dihydropyran, tetrahydropyran and the like.
Among these, preferred are 2,5-dimethyltetrahydrofuran, t-butyl methyl ether and t-butyl ethyl ether.
3-substituted 2-oxazolidinones, including 3-alkyl-2-oxazolidinones, such as 3-methyl-2-oxazolidinone and 3-ethyl-2-oxazolidinone; 3-cycloalkyl-2-oxazolidinones, such as 3-cyclohexyl-2-oxazolidinone; 3-aralkyl-2-oxazolidinones, such as 3-benzyl-2-oxazolidinone; and 3-aryl-2-oxazolidinones, such as 3-phenyl-2-oxazolidinone.
Among these, preferred are 3-alkyl-2-oxazolidinones, particularly 3-methyl-2-oxazolidinone.
dialkyl-substituted amides, such as N,N-dimethylformamide, N,N-dimethylacetamide and the like; and closely related amide like compounds, such as N,N-dimethyl methyl carbamate and tetramethylurea.
such as acetonitrile, propionitrile, benzonitrile and the like.
such as acetaldehyde, acetone and the like.
Among these organic solvents, are preferred propylene carbonate and mixtures thereof with ethers (particularly 2,5-dimethyltetrahydrofuran, t-butyl methyl ether and t-butyl ethyl ether) [Volume ratio: preferably 1/9 to 9/1, more preferably 2/8 to 8/2].
Suitable lithium salts useful for electrolyte include, for example, lithium perchlorate (LiClO4), lithium borofluoride (LiBF6), lithium borochloride (LiBCl6), lithium arsenofluoride (LiAsF6), lithium phosphofluoride (LiPF6), lithium aluminate chloride (LiAlCl4), lithium halides, such as lithium fluoride (LiF), lithium chloride (LiCl), lithium bromide (LiBr) and lithium iodide (LiI), and lithium trifluoromethane sulfonate, and the like.
The electrolyte (B) generally contains the lithium salt in an amount of 0.1 to 5 mole/l, preferably 0.5 to 3 mole/l.
The electrolyte (B) can be produced by dissolving lithium salts into organic solvents by any known methods, for instance, by mixing them optionally under heating and stirring.
Among preferred electrolytes are the following:
(1) solutions of lithium perchlorate in mixed solvents of propylene carbonate and cyclic ethers,
(2) solutions of lithium phosphofluoride in mixed solvents of 3-substituted-2-oxazolidinone and cyclic ethers, and
(3) solutions of lithium trifluoromethane sulfonate in mixed solvents of 3-substituted-2-oxazolidinone and cyclic ethers.
The secondary battery or cell according to the present invention may be used for discharge with or without being allowed to stand after preparation of the cell.
In the case where the cell is allowed to stand, a reversible complex comprising the carbonaceous material containing lithium is formed spontaneously and the complex acts as the anode active material. By electrically contacting lithium metal with the carbonaceous material within the cell according to the present invention, the lithium metal is consumed by self-discharge and automatically contained into the carbonaceous material to form the anode active material in situ within the cell. For example, when a cell of this invention, containing manganese dioxide as the cathode active material and having an initial open circuit voltage of 3.3 V, is allowed to stand in a dark room for a week, the lithium metal is completely consumed to form a reversible complex comprising the carbonaceous material containing lithium and shows an open circuit voltage of about 3.0 V.
The above-mentioned self discharge reaction can be illustrated by the following equation:
Carbonaceus material+Li→Carbonaceous material-Li Complex
Electromotive reactions in the cell of the invention can be shown in the following equations: ##STR2##
In the case where the cell is used without allowing it to stand, the reversible complex comprising the carbonaceous material containing lithium is not yet completely formed, and both the complex and lithium metal act as the anode active material.
In the battery or cell of the present invention, the electrical capacity of the anode active material depends upon the quantity of electrically reversible lithium contained in the carbonaceous material.
The electrical capacity of the cathode material is ordinarily 1 to a 1.5 times, preferably equal to that of the anode active material.
Lithium metal is preferably used in an amount such that it provides about half of the total capacity of the cathode active material and the anode active material.
This invention will be described with reference to a preferred embodiment which is shown by way of example in FIG. 1.
The battery shown in FIG. 1 comprises: a cathode container (1) serving as the cathode terminal of the battery; a metal net (2) for collecting electricity; a cathode (3) comprising said cathode active material (A); a separator (4) containing said electrolyte (B); a gasket (5); said carbonaceous material (6), in electrical contact with lithium metal (7), as the anode active material (C); a metal net (8) for collecting electricity; and an anode container (9) which serves as the anode terminal of the battery.
The battery according to the invention can be produced for example, as follows: Onto the bottom of the cathode container (1) the metal net (2) and then the molded cathode (3), comprising the cathode active material (A) are placed and pressed to bond the cathode (3) to the container (1) interposing the metal net (2). Then, the separator (4) containing the electrolyte (B) is put on the cathode (3), followed by inserting the angle gasket (5) along the wall of the cathode container (1). After the carbonaceous material (6) mounted with lithium metal (7) is pressed to bond to the anode container (9) interposing the metal net (8) between (7) and (9), this anode assembly is put on the above mentioned separator (4) followed by bending the opening part of the anode container (9) inside for tight sealing.
In the battery of this invention, the lithium metal (7) may be inserted into any part of the anode side of the battery as long as the lithium metal (7) is in electrical contact with the carbonaceous material (6). For example, the lithium metal (7) may be inserted between the carbonaceous material (6) and the metal net (8).
Batteries or cells, containing the anode active material comprising lithium metal in electrical contact with the amorphous carbonaceous material according to the present invention, can effectively inhibit deposition on dendritic crystals of lithium in the anode side during repeated discharge-charge cycles, and exhibit high voltage, excellent stability or flatness of discharge voltage high energy density and large electric capacity, in spite of small volumetric capacity.
In addition, batteries or cells of the invention can be produced easily, the anode active material being formed in situ by self discharge of lithium metal electrically contacted with the carbonaceous material, and are therefore economically advantageous as compared with those produced by using lithium metal-containing anode active materials prepared beforehand.
Having generally described the invention, a more complete understanding can be obtained by reference to certain specific examples, which are included for purposes of illustration only and are not intended to be limiting unless otherwise specified.
Into a quartz tube, were placed 43 g of powdered poly(1-chloro-2phenyl acetylene) and the tube was heated to 500° C. within 2 hours under N2 gas flow, the temperature being maintained for 1 hour. Then, the temperature was raised to 800° C. within 90 minutes, followed by maintaining the temperature for 3 hours to pyrolyze the polymer. After cooling under N2 gas flow, 26.3 g of black powder of pyrolyzed poly(1-chloro-2phenyl acetylene) was obtained.
Two g of this powder and 0.02 g of polyethylene granules were well mixed and packed into a mold to form a plate of 1 mm thickness under a pressure of 400 kg/cm2 G, and the plate was cut into a disk (6') of 16 mm diameter and 100 mg weight.
Separately, 130 mg of a cathode active material (3') which was formed by molding a mixture of manganese dioxide, acetylene black and polytetrafluoroethylene, was pressed so as to bond to a cathode container (1') of stainless steel, interposing an electron collecting metal net (2') between (3') and the bottom of (1').
Then, a glass mat separator (4'), having been immersed in with an organic electrolyte solution of lithium perchlorate in propylene carbonate having a concentration of 1 mole/l, was put on the cathode material (3'), followed by filling a proper gasket (5') into the opening of (1').
Onto 100 mg of the above-mentioned: (6') was mounted 8 mg of lithium metal foil (7'), and the mounted disk (6') was bonded to a stainless steel anode container (9'), interposing an electron collecting metal net (8').
The bonded anode was put on the separator (4'), and then the opening part of the cathode container (1') was bent to inside for tight sealing.
In this example, the lithium foil (7') was set to exist between the pyrolyzed residue (6') and the separator (4').
The initial open circuit voltage of this battery was 3.3 V, and after the battery was allowed to stand in dark room for a week, the open circuit voltage was 3.0 V. After carrying out a cycle test involving repeating 5 hours discharge and 5 hours charge at a constant current of 1 mA, the battery showed excellent charge and discharge properties with complete reversibility even after 200 cycles.
Immediately after producing a battery by repeating EXAMPLE 1, the battery was discharged at a constant current of 1 mA to 1.5 V cut-off voltage. The discharge capacity thus obtained was 25 mAH. Thereafter, a cycle test involving of repeating 5 hours discharge and 5 hours charge at a constant current of 1 mA, was carried out. The battery also showed excellent charge and discharge properties with complete reversibility even after 200 cycles.
EXAMPLE 1 was repeated except that the pyrolyzed residue obtained by heating a phenolic resin at 800° C. was used instead of the pyrolyzed residue of poly(1-chloro-2-phenylacetylene), and vanadium pentoxide was used instead of manganese dioxide. In this example, the pyrolyzed phenolic resin, the lithium metal foil and the cathode active material were used in amounts of 100 mg, 7.5 mg and 220 mg, respectively. In this case, the lithium foil was inserted between the pyrolyzed residue and the electron collecting nickel net of the anode.
The initial open circuit voltage was 3.4 V and the open circuit voltage after one week standing was 3.1 V. After carrying out cycle test involving repeating 10 hours discharge and 10 hours charge at a constant current of 1 mA, the battery showed excellent charge and discharge properties with complete reversibility even after 100 cycles.
EXAMPLE 1 was repeated except that a charcoal of coconut shells was used instead of the pyrolyzed poly (1-chloro-2-phenylacetylene), and 1 mole/l solution from lithium phosphofluoride in an equal volume mixture of propylene carbonate and 2,5-dimethyltetrahydrofuran was used as the electrolyte solution instead of the lithium perchlorate solution.
The initial open circuit voltage was 3.3 V, and open circuit voltage after 2 weeks standing was 2.98 V. After carrying out cycle test involving repeating 5 hours discharge and 5 hours charge at a constant current of 2 mA, the battery showed excellent charge and discharge properties with complete reversibility even after 100 cycles.
EXAMPLE 1 was repeated except that graphite was used instead of the pyrolyzed poly(1-chloro-2-phenylacetylene).
The initial open circuit voltage was 3.3 V, and the open circuit voltage after one week standing was 2.0 V. After 5 hours discharge at a constant current of 1 mA, charging was attempted at the same current density, but this trial resulted in a failure.
Claims (15)
1. A secondary battery or cell with improved rechargeability, which comprises:
(A) a cathode active material comprising a chalcogen compound of a transition metal,
(B) an electrolyte comprising a organic solvent having dissolved therein a lithium salt, and
(C) an anode active material comprising lithium metal in electrical contact with an electrically conductive substantially amorphous carbonaceous material having a conductivity of at least 10-5 mho/cm and a density of at most 1.8 g/cm3,
said carbonaceous material being a pyrolysis residue formed by heating at least one organic material selected from the group consisting of synthetic high polymers, natural high polymers, pitches and coals, in an inert atmosphere to a temperature ranging from about 300° C. to 1500° C.,
wherein said anode material is formed in situ within the secondary battery or cell, by self discharge of lithium metal into said carbonaceous material.
2. The secondary battery or cell of claim 1, wherein said organic material is at least one synthetic high polymer selected from the group consisting of polyacrylonitrile, polyvinyl chloride, polyvinylidene choride, polyvinyl alcohol, polybutadiene, polyethylene, polymethyl vinyl ketone, polyphenylene, polystyrene, polyacetylenes, polyarylacetylenes, polyimides, polyamides, polybenzimidazoles, polysemicarbazides, polybenzoxadinones, epoxy resins, furan resins and phenolic resins.
3. The secondary battery or cell of claim 1, wherein said organic material is at least one synthetic high polymer selected from the group consisting of polyarylacetylenes and phenolic resins.
4. The secondary battery or cell of claim 1, wherein said organic material is at least one synthetic high polymer selected from the group consisting of polyarylacetylenes having repeating units of the general formula: ##STR3## wherein X is Cl or methyl, and Y is H, Cl or methyl.
5. The secondary battery or cell of claim 1, wherein said pyrolysis residue is formed by heating the organic material in an inert atmosphere to a temperature sufficiently high to bring about substantially complete thermal decomposition of noncarbon constituents of the organic material.
6. The secondary battery or cell of claim 1, wherein said carbonaceous material is an activated pyrolysis residue of the organic material.
7. The secondary battery or cell of claim 1, wherein said pyrolysis residue is activated by steam activation, drug activation, or partial oxidation.
8. The secondary battery or cell of claim 1, wherein said pyrolysis residue is in the form of film, fiber, fabric, thin plate or powder.
9. The secondary battery or cell of claim 1, wherein the transition metal is selected from the group consisting of metals of Groups IB-VII and Group VIII of the long form periodic table.
10. The secondary battery or cell of claim 1, wherein said chalogen compound is a chalcogenide of at least one transition metal selected from the group consisting of titanium, vanadium, chromium, manganese, cobalt, copper, iron, niobium and molybdenum.
11. The secondary battery or cell of claim 1, wherein said organic solvent is at least one selected from the group consisting of esters, ethers, ketones, aldehydes, nitriles and amides.
12. The secondary battery or cell of claim 1, wherein the lithium salt is selected from the group consisting of LiClO4, LiPF6, lithium trifluoromethane sulfonate, LiCl, LiBr, LiI, LiAsF6, LiBF4, LiBCl4 and LiAlCl4.
13. The secondary battery or cell of claim 1, which comprises:
(1) a cathode container with an opening,
(2) a first metal net for collecting electricity situated on an inner surface of said container,
(3) said cathode active material (A) placed on top of said first metal net,
(4) a separator containing said electrolyte (B) placed on top of said cathode active material,
(5) a gasket placed so as to maintain the position of the previously recited elements,
(6) said carbonaceous material placed on top of said separator, in electrical contact with
(7) said lithium metal as anode active material (C),
(8) a second metal net for collecting electricity situated on top of said carbonaceous material, and
(9) an anode container having said anode active material situated onto an inner surface, placed into the opening of said cathode container. .Iadd.
14. A secondary battery or cell with improved rechargeability, which comprises:
(A) a cathode active material comprising a chalogen compound of a transition metal,
(B) an electrolyte comprising a organic solvent having dissolved therein a lithium salt, and
(C) an anode active material comprising lithium metal in electrical contact with an electrically conductive substantially amorphous carbonaceous material having a conductivity of at least 10-5 mho/cm,
said carbonaceous material being a pyrolysis residue formed by heating at least one organic material selected from the group consisting of synthetic high polymers, natural high polymers, pitches and coals, in an inert atmosphere to a temperature ranging from about 300° C. to 1500° C.,
wherein said anode material is formed in situ within the secondary battery or cell, by self discharge of lithium metal into said carbonaceous material. .Iaddend. .Iadd.15. The secondary battery or cell of claim 14, which comprises:
(1) a cathode container with an opening,
(2) a first metal net for collecting electricity situated on an inner surface of said container,
(3) said cathode active material (A) placed on top of said first metal net,
(4) a separator containing said electrolyte (B) placed on top of said cathode active material,
(5) a gasket placed so as to maintain the position of the previously recited elements,
(6) said carbonaceous material placed on top of said separator, in electrical contact with
(7) said lithium metal as anode active material (C),
(8) a second metal net for collecting electricity situated on top of said carbonaceous material, and
(9) an anode container having said anode active material situated onto an inner surface, placed into the opening of said cathode container.
.Iaddend. .Iadd.16. A secondary battery or cell with improved rechargeability, which comprises:
(A) a cathode active material comprising a chalcogen compound of a transition metal,
(B) an electrolyte comprising an organic solvent having dissolved therein a lithium salt, and
(C) an anode comprising an electrically conductive substantially amorphous carbonaceous material having a conductivity of at least 10-5 mho/cm containing lithium therein, said carbonaceous material being a pyrolysis residue formed by heating at least one organic material selected from the group consisting of synthetic high polymers, natural high polymers, pitches and coals, in an inert atmosphere to a temperature ranging from about 300° C. to about 1500° C.,
wherein said lithium is intercalated into said carbonaceous material upon charging the cell and said lithium is deintercalated from said carbonaceous material upon discharging the cell. .Iaddend. .Iadd.17. The secondary battery or cell of claim 14, wherein said carbonaceous material has a density of at most 1.8 g/cm3, the density being a bulk density. .Iaddend. .Iadd.18. A secondary battery or cell with improved rechargeability, which comprises:
(A) a cathode active material comprising a chalcogen compound of a transition metal,
(B) an electrolyte comprising an organic solvent having dissolved therein a lithium salt, and
(C) an anode comprising an electrically conductive carbonaceous material having a conductivity of at least 10-5 mho/cm containing lithium therein, said carbonaceous material being substantially free from an X-ray diffraction characteristic of graphite, said carbonaceous material being a pyrolysis residue formed by heating at least one organic material selected from the group consisting of synthetic high polymers, natural high polymers, pitches and coals, in an inert atmosphere to a temperature ranging from about 300° C. to about 1500° C.,
wherein electromotive reactions proceed at the anode side according to the following equations: ##STR4##
Applications Claiming Priority (2)
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JP59091455A JPH0789483B2 (en) | 1984-05-07 | 1984-05-07 | Secondary battery |
JP59-91455 | 1984-05-07 |
Related Parent Applications (1)
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US06/709,397 Reissue US4615959A (en) | 1984-05-07 | 1985-03-07 | Secondary battery or cell with improved rechargeability |
Publications (1)
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USRE33306E true USRE33306E (en) | 1990-08-21 |
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US06/709,397 Ceased US4615959A (en) | 1984-05-07 | 1985-03-07 | Secondary battery or cell with improved rechargeability |
US07/254,966 Expired - Lifetime USRE33306E (en) | 1984-05-07 | 1988-10-07 | Secondary battery or cell with improved rechargeability |
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US06/709,397 Ceased US4615959A (en) | 1984-05-07 | 1985-03-07 | Secondary battery or cell with improved rechargeability |
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US5162176A (en) * | 1991-01-19 | 1992-11-10 | Varta Batterie Aktiengesellschaft | Electrochemical secondary element |
US5270134A (en) * | 1991-06-28 | 1993-12-14 | Advanced Energy Technologies Inc. | Non-aqueous secondary lithium battery |
WO1997005667A1 (en) * | 1995-07-31 | 1997-02-13 | Varta Batterie Aktiengesellschaft | Lithium ion cell |
US6303249B1 (en) * | 1996-06-28 | 2001-10-16 | Kureha Kogaku Kogyo Kabushiki Kaisha | Carbonaceous electrode material for secondary battery and process for production thereof |
WO1998004009A1 (en) * | 1996-07-19 | 1998-01-29 | Motorola Inc. | High volumetric capacity electrodes and electrochemical cells using same |
US5776635A (en) * | 1996-09-16 | 1998-07-07 | Wilson Greatbatch Ltd. | Ternary solvent nonaqueous organic electrolyte for alkali metal electrochemical cells |
US5843393A (en) * | 1997-07-28 | 1998-12-01 | Motorola, Inc. | Carbon electrode material for electrochemical cells and method of making same |
US5972537A (en) | 1997-09-02 | 1999-10-26 | Motorola, Inc. | Carbon electrode material for electrochemical cells and method of making same |
US6071649A (en) | 1997-10-31 | 2000-06-06 | Motorola, Inc. | Method for making a coated electrode material for an electrochemical cell |
US6294292B1 (en) * | 1998-07-14 | 2001-09-25 | Asahi Glass Company Ltd. | Secondary power source |
US6761744B1 (en) | 1999-07-16 | 2004-07-13 | Quallion Llc | Lithium thin film lamination technology on electrode to increase battery capacity |
US20030134204A1 (en) * | 2001-11-05 | 2003-07-17 | Hong Gan | Highly conductive and stable nonaqueous electrolyte for lithium electrochemical cells |
US6844115B2 (en) | 2001-11-05 | 2005-01-18 | Wilson Greatbatch Technologies, Inc. | Highly conductive and stable nonaqueous electrolyte for lithium electrochemical cells |
US8445137B1 (en) | 2002-11-27 | 2013-05-21 | Quallion Llc | Primary battery having sloped voltage decay |
US20060123631A1 (en) * | 2004-12-15 | 2006-06-15 | Andrew Szczepanowski | Shaving razors and razor cartridges |
US7681320B2 (en) * | 2004-12-15 | 2010-03-23 | The Gillette Company | Shaving razors and razor cartridges |
US20060183024A1 (en) * | 2005-02-17 | 2006-08-17 | Kenichi Suzuki | Battery |
US7732097B2 (en) * | 2005-02-17 | 2010-06-08 | Sony Corporation | Battery |
US7820328B1 (en) * | 2006-07-27 | 2010-10-26 | Greatbatch Ltd. | Electrochemical cell electrode with improved particle-to-particle contact and method of manufacturing |
US20110207000A1 (en) * | 2006-09-07 | 2011-08-25 | Jow T Richard | Nitrile additive for non-aqueous electrolyte rechargeable electrochemical cells |
US20090148773A1 (en) * | 2007-12-06 | 2009-06-11 | Ener1, Inc. | Lithium-ion secondary battery cell, electrode for the battery cell, and method of making the same |
Also Published As
Publication number | Publication date |
---|---|
US4615959A (en) | 1986-10-07 |
JPH0789483B2 (en) | 1995-09-27 |
JPS60235372A (en) | 1985-11-22 |
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