CN104285331A - High-voltage lithium secondary battery - Google Patents
High-voltage lithium secondary battery Download PDFInfo
- Publication number
- CN104285331A CN104285331A CN201480001219.1A CN201480001219A CN104285331A CN 104285331 A CN104285331 A CN 104285331A CN 201480001219 A CN201480001219 A CN 201480001219A CN 104285331 A CN104285331 A CN 104285331A
- Authority
- CN
- China
- Prior art keywords
- lithium secondary
- secondary battery
- polymer electrolyte
- gel polymer
- chemical formula
- 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.)
- Pending
Links
Classifications
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection 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
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection 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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Provided is a lithium secondary battery and a method for manufacturing same, and the lithium secondary battery comprises: a positive pole; a negative pole; a separator; and a gel polymer electrolyte, wherein the gel polymer electrolyte comprises an acrylate polymer, and charge voltage of the battery is within the range of 4.3V to 5.0V. A high-voltage lithium secondary battery according to the present invention has superior capacity properties at high voltages at or above 4.3V.
Description
Technical field
The present invention relates to a kind of high pressure lithium secondary battery, more specifically, relate to a kind of high pressure lithium secondary battery comprising gel polymer electrolyte, described gel polymer electrolyte comprise there is the monomer of 2 to 6 acrylate groups and the charging voltage of battery in the scope of 4.3V to 5.0V.
Background technology
Recently, in the development of electronics industry, information and telecommunications industry, the portability of electronic device, miniaturization, lighting and high performance trend increase fast.Therefore, need the energy source be used as by high performance lithium secondary electron in these portable electronic devices, and this needs are growing.Secondary cell, it is Reusability by discharge and recharge, is the significant energy source for the mobile electronic device of information and communication, electric motor car or motor vehicle.
Particularly, the performance due to these products depends on the battery as critical component, and thus the demand of consumer to high-capacity battery is growing.Along with the demand increased battery capacity, the exploitation of high-voltage battery system becomes trend.
For the lithium secondary battery of routine, charge under charging voltage is 3.0V to 4.2V.Therefore, be engaged in the research for obtaining more energy capacity aspect, described research is undertaken by using the high pressure (4.3V to 5.0V) higher than above-mentioned voltage.
But, for using in the battery of conventional negative pole and positive pole using carbonate group non-aqueous solvent as electrolyte, during owing to charging under higher than the conventional charge electromotive force of 4.2V, oxidability increases, and along with carrying out charging and discharging circulation,, the decomposition reaction of electrolyte can be there is in the degradation of negative pole and positive pole.Therefore, life characteristic reduces fast.
For LiCoO
2as the situation of the positive electrode active materials of routine, due to hot property when it under high pressure uses and chemical property improper, thus need to make improvements.
Summary of the invention
Technical problem
The invention provides a kind of high pressure lithium secondary battery, described high pressure lithium secondary battery has life characteristic and the capacity characteristic of the excellence under the high pressure of 4.3V to 5.0V.
Technical scheme
For solving above-mentioned problem, the invention provides a kind of lithium secondary battery, described lithium secondary battery comprises: positive pole; Negative pole; Barrier film; And gel polymer electrolyte, wherein, described gel polymer electrolyte comprises acrylate based polyalcohol; And the charging voltage of described battery is in the scope of 4.3V to 5.0V.
In addition, of the present inventionly provide a kind of method preparing lithium secondary battery, described method comprises the steps:
Electrode assemblie is inserted in battery case, the barrier film that described electrode assemblie comprises positive pole, negative pole and is placed between described positive pole and negative pole;
Composition for the preparation of gel polymer electrolyte is injected battery case, and makes described composition be polymerized generation gel polymer electrolyte;
Wherein, the described composition for the preparation of gel polymer electrolyte comprises electrolyte solvent, ionizable lithium salts and the monomer containing 2 to 6 acrylate groups.
Invention effect
Even if the lithium secondary battery of one embodiment of the invention its also there is when charging under the high pressure of more than 4.3V excellent life characteristic and capacity characteristic.
The cutline of accompanying drawing
Fig. 1 is the figure of battery capacity when illustrating that lithium secondary battery prepared by embodiment 1 and embodiment 2 and comparative example 1 and comparative example 2 charges under the high pressure of 4.3V.
Embodiment
Hereinafter, in order to more clearly understand the present invention, will be for a more detailed description to the present invention.
Should be understood that vocabulary used in the specification and claims and term should not be construed as the implication defined in common dictionary.Should also be understood that the implication that described vocabulary and term should suitably can define vocabulary and term based on inventor is interpreted as having the implication consistent with technical conceive of the present invention with best interpretations principle of the present invention.
The lithium secondary battery of embodiment of the present invention is high pressure lithium secondary battery, and it comprises positive pole (cathode); Negative pole (anode); Barrier film; And gel polymer electrolyte, wherein, described gel polymer electrolyte comprises acrylate based polyalcohol; And the charging voltage of described battery is in the scope of 4.3V to 5.0V.
Described gel polymer electrolyte generates by a kind of polymerization of the composition for the preparation of gel polymer electrolyte, and the described composition for the preparation of gel polymer electrolyte comprises electrolyte solvent, ionizable lithium salts and the monomer containing 2 to 6 acrylate groups.
The described monomer containing 2 to 6 acrylate groups is preferably branched monomer, such as, can be and be selected from the following mixture of any one or more: double trimethylolpropane tetraacrylate, Dipentaerythritol Pentaacrylate and dipentaerythritol acrylate.
The described composition for the preparation of gel polymer electrolyte can comprise the monomer of 0.1 % by weight to 10 % by weight, preferably 0.5 % by weight to 5 % by weight, based on the total weight of the composition for the preparation of gel polymer electrolyte.
In addition, according to one embodiment of the invention, the ionizable lithium salts be included in described electrolyte such as can be and is selected from the following mixture of any one or more: LiPF
6, LiBF
4, LiSbF
6, LiAsF
6, LiClO
4, LiN (C
2f
5sO
2)
2, LiN (CF
3sO
2)
2, CF
3sO
3li, LiC (CF
3sO
2)
3and LiC
4bO
8.But, the present invention is not limited thereto.
In addition, be usually used in and all unrestrictedly can be used as electrolyte solvent of the present invention for any electrolyte solvent in the electrolyte of lithium secondary battery, and such as ether, ester, acid amides, linear carbonates or cyclic carbonate ester can be used alone or in conjunction with two or more use.
In these materials, comprise cyclic carbonate ester, linear carbonates or the carbonate products as its mixture representativity.The instantiation of cyclic carbonate ester can comprise and is selected from the following mixture of any one or more: ethylene carbonate (EC), propylene carbonate (PC), carbonic acid 1,2-Aden ester, carbonic acid 2,3-Aden ester, carbonic acid 1, the sub-pentyl ester of 2-, carbonic acid 2,3-sub-pentyl ester, ethenylidene carbonic ester and halide thereof or wherein two or more mixture.In addition, for the instantiation of linear carbonates, representativity ground uses and is selected from any one following linear carbonates: dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), ethyl methyl carbonate (EMC), methyl propyl ester (MPC) and carbonic acid ethylpropyl (EPC) or wherein two or more mixture.But, the present invention is not limited thereto.
Specifically, in described carbonate group electrolyte solvent, owing to being high viscosity organic solvent as the propylene carbonate of cyclic carbonate ester and ethylene carbonate and there is high-k, thus propylene carbonate and the ethylene carbonate lithium salts that can dissociate well in electrolyte.Therefore, propylene carbonate and ethylene carbonate can preferably be used.Due to after above-mentioned cyclic carbonate ester is mixed with suitable ratio with linear carbonates such as methyl ethyl carbonate, diethyl carbonate and the dimethyl carbonate of low viscosity low-k, the electrolyte with high conductivity can be prepared, thus can preferably use.
In addition, for the ester in described electrolyte solvent, can use and be selected from any one or more following mixtures: methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, gamma-butyrolacton, gamma-valerolactone, γ-hexalactone, σ-valerolactone and 6-caprolactone.But, the present invention is not limited thereto.
According to one embodiment of the invention, the composition for gel polymer electrolyte also can comprise polymerization initiator, and common polymerization initiator as known in the art all can be used as described polymerization initiator.
The limiting examples of described polymerization initiator comprises organic peroxide or hydroperoxides, such as benzoyl peroxide (benzoyl peroxide), acetyl peroxide (acetyl peroxide), dilauroyl peroxide (dilauryl peroxide), di-tert-butyl peroxide (di-tert-butyl peroxide), t-butyl peroxy-2-ethyl-hexanoate (t-butyl peroxy-2-ethyl-hexanoate), cumyl hydroperoxide (cumylhydroperoxide) and hydrogen peroxide (hydrogen peroxide), and comprise azo-compound, such as 2,2'-azo two (2-cyanobutane), 2,2'-azo two (methylbutyronitrile), 2,2'-azo two (isobutyronitrile) (AIBN) and 2,2'-azo two (methyl pentane nitrile) (AMVN).But, the present invention is not limited thereto.
Described polymerization initiator decomposes by the heat in battery and generates free radical, and gel polymer electrolyte can be generated with the described monomer containing 2 to 6 acrylate groups by radical polymerization, described decomposition is such as carried out without limitation at 30 DEG C to 100 DEG C, or can carry out under room temperature (5 DEG C to 30 DEG C).
In addition, the consumption of described polymerization initiator can be 0.01 % by weight to 2 % by weight, based on the total weight of the composition for the preparation of gel polymer electrolyte.If the consumption of polymerization initiator is greater than 2 % by weight, then there is the process gelation of to inject in battery for the preparation of the composition of gel polymer electrolyte too fast, maybe may have the shortcoming that unreacted polymerization initiator remains and performance in the later stage to battery has a negative impact.Comparatively speaking, if the consumption of polymerization initiator is less than 0.01 % by weight, then there is the problem that gelation possibly cannot be carried out completely.
The electrolyte of one embodiment of the invention, except comprising said components, also optionally comprises other additives known in the art.
In addition, according to embodiment of the present invention, the present invention can provide a kind of method preparing lithium secondary battery, and described method comprises the steps: electrode assemblie to insert in battery case, the barrier film that described electrode assemblie comprises positive pole, negative pole and is placed between described positive pole and negative pole; Composition for the preparation of gel polymer electrolyte is injected battery case, and makes described composition be polymerized generation gel polymer electrolyte; Wherein, the described composition for the preparation of gel polymer electrolyte comprises electrolyte solvent, ionizable lithium salts and the monomer containing 2 to 6 acrylate groups.
According to one embodiment of the invention, described gel polymer electrolyte generates according to conventional method polymerization known in the art by making the above-mentioned composition for the preparation of gel polymer electrolyte.Such as, described electrolyte is by generating in the inner polymerization of the original position (in-situ) for the preparation of the composition of polymer dielectric of secondary cell.
According to a preferred embodiment of the invention, described method comprises the steps: that electrode assemblie inserts in battery case by (a), and described electrode assemblie is formed by positive pole, negative pole and the barrier film be placed between described positive pole and negative pole; (b) composition for the preparation of gel polymer electrolyte is injected described battery case, and make described composition be polymerized generation gel polymer electrolyte.
Home position polymerization reaction in lithium secondary battery is undertaken by thermal polymerization.In the case, required polymerization time can be about 2 minutes to 12 hours, and thermal polymerization temperature can be 30 DEG C to 100 DEG C.
At the end of the gelation process undertaken by this polymerization reaction, generate gel polymer electrolyte, and the described gelatin polymer useful liquid electrolyte homogeneous impregnation generated thus, in described liquid electrolyte, electrolytic salt is dissolved in electrolyte solvent.
The electrode of the lithium secondary battery of one embodiment of the invention is prepared by conventional method known in the art.Such as, by electrode active material and solvent, and the adhesive used if desired, conductive agent and dispersant, and stir to prepare slurry slurry, to suppress with the current-collector of described slurry slurry metallizing material and to the described current-collector being coated with the metal material of slurry slurry subsequently and dry, thus prepare electrode.
According to one embodiment of the invention, if compound can use under the high voltage of 4.3V to 5.0V, and reversibly insert/discharge lithium for lithium, then all can be used as the positive electrode active materials being included in described positive pole, and do not impose any restrictions.
Specifically, described positive electrode active materials can comprise and is selected from the following combination oxide of any one or more: sharp brilliant lithium transition-metal oxide, and it is have the hexagon stratiform rock salt body structure of high capacity characteristics, olivine structural and cube structure; V
2o
5; TiS and MoS.
More specifically, positive electrode active materials such as can comprise the compound that any one is selected from chemical formula 1-3, or wherein two or more mixtures.
< chemical formula 1>
Li [Li
xni
aco
bmn
c] O
2(wherein, 0<x≤0.3,0.3≤c≤0.7,0<a+b<0.5 and x+a+b+c=1);
< chemical formula 2>
LiMn
2-xm
xo
4(wherein, M is that more than one are selected from following element: Ni, Co, Fe, P, S, Zr, Ti and Al, and 0<x≤2);
< chemical formula 3>
Li
1+
aco
xm
1-xaX
4(wherein, M is that more than one are selected from following element: Al, Mg, Ni, Co, Mn, Ti, Ga, Cu, V, Nb, Zr, Ce, In, Zn and Y, X is that more than one are selected from following element: O, F and N, and A is P, S or its complex element, 0≤a≤0.2 and 0.5≤x≤1).
Described positive electrode active materials preferably can meet 0.4≤c≤0.7 in chemical formula 1 and the condition of 0.2≤a+b<0.5, and can comprise any one and be selected from following material: LiNi
0.5mn
1.5o
4, LiCoPO
4and LiFePO
4or wherein two or more mixture.
In the negative pole of one embodiment of the invention, lithium can be supplied to insert and discharge the material with carbon element of lithium ion, lithium metal, silicon or tin usually all to can be used as negative active core-shell material.Such as, preferably can use material with carbon element, and low crystalline carbon and high crystalline carbon all can be used as material with carbon element.The representative example of low crystalline carbon can be soft carbon and hard carbon, and the coke that the representative example of high crystalline carbon can derive for native graphite, kish (Kish graphite), RESEARCH OF PYROCARBON, mesophase pitch-based carbon fibers, mesophase-carbon micro-beads, mesophase pitch and high temperature sintering carbon such as oil or coal tar pitch.
By by adhesive and solvent and normally used conductive agent and dispersant stir and prepare slurry if desired.Then, described positive pole and/or negative pole is prepared by applying current-collector with described slurry and carry out compacting to the current-collector through coating.
Various binder polymer all can be used as adhesive, and described binder polymer is Kynoar-hexafluoropropylene copolymer (PVDF-co-HEP), Kynoar, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethene, polyethylene, polypropylene, polyacrylate, Ethylene-Propylene-Diene monomer (EPDM), sulfonated epdm, styrene butadiene rubbers (SBR), fluorubber and various copolymer such as.
In addition, common porous polymer film as conventional separator can be used as barrier film separately or in a laminated manner, the porous polymer film of described Conventional porous film such as being prepared by polyolefin based polymer, described polyolefin based polymer is such as Alathon, Noblen, ethylene/butylene copolymers, ethylene/hexene copolymer and ethylene/methyl acrylate copolymer.In addition, Conventional porous adhesive-bonded fabric can be used, the adhesive-bonded fabric such as formed by high melting glass fiber or pet fiber.But the present invention is not limited thereto.
The shape of the lithium secondary battery of one embodiment of the invention is not particularly limited, and can be cylindrical, prismatic, bag (pouch) shape or coin (coin) shape that use tank.
Hereinafter, the present invention will be described in detail by specific embodiment.But the present invention can give different forms and should not be construed as and be confined to proposed embodiment herein.And these exemplary embodiments provide to fully explain the present invention to those skilled in the art.
Embodiment
Hereinafter, in further detail the present invention will be described by embodiment and test example.But, the present invention is not limited thereto.
Embodiment 1
< is for the preparation of the composition > preparing gel polymer electrolyte
By by LiPF
6be dissolved in the non-aqueous eletrolyte solvent containing composition and prepare electrolyte, to obtain the LiPF of 1M
6concentration, in described composition, the volume ratio of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) is 1:2.By adding 5 weight portion double trimethylolpropane tetraacrylate and the 0.25 weight portion t-butyl peroxy-2-ethyl-hexanoate as polymerization initiator for the preparation of the composition preparing gel polymer electrolyte, based on 100 weight portion electrolyte meters.
< prepares coin shape secondary cell >
prepare positive pole
Prepare cathode mix slurry in the following way: using 94 % by weight as the Li [Li of positive electrode active materials
0.29ni
0.14co
0.11mn
0.46] O
2, 3 % by weight add the METHYLPYRROLIDONE (NMP) as solvent as the carbon black and 3 % by weight of conductive agent as the Kynoar (PVdF) of adhesive.Aluminium as cathode collector (Al) film thick with described cathode mix slurry coating about 20 μm is also dry, and subsequently described Al film is carried out roll-in, to prepare positive pole.
prepare negative pole
Prepare negative electrode mix slurry in the following way: add the NMP as solvent as the carbon dust, 3 % by weight of negative active core-shell material as the PVdF and 1 % by weight of adhesive as the carbon black of conductive agent using 96 % by weight.Copper as anode collector (Cu) film thick with described negative electrode mix slurry coating about 10 μm is also dry, and subsequently described Cu film is carried out roll-in, to prepare negative pole.
prepare battery
The barrier film assembled battery using described positive pole, negative pole and formed by polypropylene, polyethylene/polypropylene (PP/PE/PP) three layers, and the described composition for the preparation of gel polymer electrolyte is injected the battery assembled.Then, by the described battery assembled was prepared secondary cell to 30 minutes in 2 minutes with 80 DEG C of heating in a nitrogen atmosphere.
Embodiment 2
Prepare secondary cell in the same manner as in Example 1, difference is, in the process of the composition for the preparation of gel polymer electrolyte of preparation embodiment 1, uses two seasons pentanediol five acrylate replacement double trimethylolpropane tetraacrylate.
Comparative example 1
Prepare secondary cell in the same manner as in Example 1, difference is, in the process of the composition for the preparation of gel polymer electrolyte of preparation embodiment 1, do not use double trimethylolpropane tetraacrylate and tert-butyl peroxide-2--ethyl-hexanoate.
Comparative example 2
Prepare secondary cell in the same manner as in Example 1, difference is, in the process of the positive pole of preparation embodiment 1, uses LiCoO
2as positive electrode active materials.
Test example
At 55 DEG C, the secondary cell (battery capacity: 4.3mAh) of preparation in embodiment 1 and embodiment 2 and comparative example 1 and comparative example 2 is charged to the voltage of 4.3V under the constant current of 0.7C.Then, secondary cell charged under the constant voltage of 4.3V and stop charging when charging current is 0.215mA.By battery standing after 10 minutes, under the constant current of 0.5C to battery discharge to the voltage of 3.0V.Described charging and discharging repeats 30 circulations, then measures battery capacity.Measurement result is shown in Figure 1.
Specifically, with reference to figure 1, also do not carrying out about 5 circulation times, the capacity of embodiment 1 and embodiment 2 and comparative example 1 and comparative example 2 is near one another.But after the about the 5th circulation, the capacity of comparative example 1 and comparative example 2 declines rapidly.Especially, for use LiCoO
2as the comparative example 2 of positive electrode active materials, its capacity significantly declines after the 5th circulation, and its capacity is carrying out 30 circulation times close to 0mAh.By contrast, even if the 30th circulation under high pressure of embodiment 1 and embodiment 2 also has high power capacity, and the high power capacity had is more than 2 to 4 times of the capacity of comparative example 1 and comparative example 2.
Therefore, after being appreciated that charge under the high pressure of 4.3V the 30th circulation, the battery capacity of embodiment 1 and preparation in embodiment 2 and comparative example 1 are compared with the capacity of the battery prepared in comparative example 2 and are significantly improved.
Industry utilizability
Even if the lithium secondary battery due to one embodiment of the invention charges under the high pressure of more than 4.3V also still have excellent life characteristic and capacity characteristic, therefore it is suitable as secondary cell.
Claims (16)
1. a lithium secondary battery, described lithium secondary battery comprises:
Positive pole; Negative pole; Barrier film; And gel polymer electrolyte, wherein, described gel polymer electrolyte comprises acrylate based polyalcohol; And the charging voltage of described battery is in the scope of 4.3V to 5.0V.
2. lithium secondary battery according to claim 1, is characterized in that,
Described gel polymer electrolyte generates by making composition be polymerized, and described composition comprises electrolyte solvent, ionizable lithium salts and the monomer containing 2 to 6 acrylate groups.
3. lithium secondary battery according to claim 1, is characterized in that,
Described positive pole comprises positive electrode active materials, and described positive electrode active materials is selected from the compound of chemical formula 1-3 or wherein two or more mixtures:
< chemical formula 1>
Li [Li
xni
aco
bmn
c] O
2(wherein, 0<x≤0.3,0.3≤c≤0.7,0<a+b<0.5 and x+a+b+c=1);
< chemical formula 2>
LiMn
2-xm
xo
4(wherein, M is that more than one are selected from following element: be selected from Ni, Co, Fe, P, S, Zr, Ti and Al, and 0<x≤2);
< chemical formula 3>
Li
1+aco
xm
1-xaX
4(wherein, M is that more than one are selected from following element: Al, Mg, Ni, Co, Mn, Ti, Ga, Cu, V, Nb, Zr, Ce, In, Zn and Y, X is that more than one are selected from following element: O, F and N, and A is P, S or its complex element, 0≤a≤0.2 and 0.5≤x≤1).
4. lithium secondary battery according to claim 3, is characterized in that,
Described positive electrode active materials can meet 0.4≤c≤0.7 in chemical formula 1 and the condition of 0.2≤a+b<0.5, and for any one is selected from following material: LiNi
0.5mn
1.5o
4, LiCoPO
4and LiFePO
4or wherein two or more mixture.
5. lithium secondary battery according to claim 2, is characterized in that,
Described monomer is selected from any one or its two or more mixture in double trimethylolpropane tetraacrylate, Dipentaerythritol Pentaacrylate and dipentaerythritol acrylate.
6. lithium secondary battery according to claim 2, is characterized in that,
The content of described monomer is 0.1 % by weight to 10 % by weight, based on the total weight of the composition for the preparation of gel polymer electrolyte.
7. lithium secondary battery according to claim 2, is characterized in that,
Described lithium salts is be selected from the following mixture of any one or more: LiPF
6, LiBF
4, LiSbF
6, LiAsF
6, LiClO
4, LiN (C
2f
5sO
2)
2, LiN (CF
3sO
2)
2, CF
3sO
3li, LiC (CF
3sO
2)
3and LiC
4bO
8.
8. lithium secondary battery according to claim 2, is characterized in that,
Described electrolyte solvent is linear carbonates, cyclic carbonate ester or its bond.
9. lithium secondary battery according to claim 8, is characterized in that,
Described linear carbonates comprises and is selected from the following mixture of any one or more: dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, methyl propyl ester and carbonic acid ethylpropyl.
10. lithium secondary battery according to claim 8, is characterized in that,
Described cyclic carbonate ester comprises and is selected from the following mixture of any one or more: ethylene carbonate, propylene carbonate, carbonic acid 1,2-Aden ester, carbonic acid 2, the sub-pentyl ester of 3-Aden ester, carbonic acid 1,2-, carbonic acid 2,3-sub-pentyl ester, vinylene carbonate and halide thereof.
11. lithium secondary batteries according to claim 1, is characterized in that,
Described negative pole comprises carbon material negative pole active material.
12. 1 kinds of methods preparing lithium secondary battery, described method comprises the steps:
Electrode assemblie is inserted in battery case, the barrier film that described electrode assemblie comprises positive pole, negative pole and is placed between described positive pole and negative pole; With
Composition for the preparation of gel polymer electrolyte is injected battery case, and makes described composition be polymerized generation gel polymer electrolyte;
Wherein, the described composition for the preparation of gel polymer electrolyte comprises electrolyte solvent, ionizable lithium salts and the monomer containing 2 to 6 acrylate groups.
13. methods according to claim 12, is characterized in that,
The described composition for the preparation of gel polymer electrolyte also comprises polymerization initiator.
14. methods according to claim 12, is characterized in that,
Carry out in the described temperature range being aggregated in 30 DEG C to 100 DEG C.
15. methods according to claim 12, is characterized in that,
Described monomer is selected from the mixture of any one or more of double trimethylolpropane tetraacrylate, Dipentaerythritol Pentaacrylate and dipentaerythritol acrylate.
16. methods according to claim 12, is characterized in that,
Described positive pole comprises positive electrode active materials, and described positive electrode active materials is selected from any one or wherein two or more mixtures in the compound of chemical formula 1-3:
< chemical formula 1>
Li [Li
xni
aco
bmn
c] O
2(wherein, 0<x≤0.3,0.3≤c≤0.7,0<a+b<0.5 and x+a+b+c=1);
< chemical formula 2>
LiMn
2-xm
xo
4(wherein, M is that more than one are selected from following element: be selected from Ni, Co, Fe, P, S, Zr, Ti and Al, and 0<x≤2);
< chemical formula 3>
Li
1+aco
xm
1-xaX
4(wherein, M is that more than one are selected from following element: Al, Mg, Ni, Co, Mn, Ti, Ga, Cu, V, Nb, Zr, Ce, In, Zn and Y, X is that more than one are selected from following element: O, F and N, and A is P, S or its complex element, 0≤a≤0.2 and 0.5≤x≤1).
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2013-0009336 | 2013-01-28 | ||
| KR20130009336 | 2013-01-28 | ||
| KR1020140009646A KR101641763B1 (en) | 2013-01-28 | 2014-01-27 | High voltage lithium secondary battery |
| KR10-2014-0009646 | 2014-01-27 | ||
| PCT/KR2014/000796 WO2014116084A1 (en) | 2013-01-28 | 2014-01-28 | High-voltage lithium secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104285331A true CN104285331A (en) | 2015-01-14 |
Family
ID=51744708
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480001219.1A Pending CN104285331A (en) | 2013-01-28 | 2014-01-28 | High-voltage lithium secondary battery |
Country Status (5)
| Country | Link |
|---|---|
| JP (2) | JP6274453B2 (en) |
| KR (1) | KR101641763B1 (en) |
| CN (1) | CN104285331A (en) |
| BR (1) | BR112014017467B8 (en) |
| TW (1) | TWI546998B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111542962A (en) * | 2018-04-27 | 2020-08-14 | 株式会社Lg化学 | Lithium secondary battery and method for manufacturing same |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101797295B1 (en) | 2014-10-02 | 2017-11-13 | 주식회사 엘지화학 | Gel polymer electrolyte and lithium secondary battery comprising the same |
| WO2016053041A1 (en) * | 2014-10-02 | 2016-04-07 | 주식회사 엘지화학 | Gel polymer electrolyte and lithium secondary battery containing same |
| KR102093965B1 (en) | 2016-11-21 | 2020-03-26 | 주식회사 엘지화학 | Lithium-sulfur battery |
| KR102255536B1 (en) | 2017-11-30 | 2021-05-25 | 주식회사 엘지에너지솔루션 | Composition for gel polymer electrolyte, gel polymer electrolyte and lithium secondary battery comprising the same |
| CN111430780B (en) * | 2020-04-28 | 2023-03-28 | 孚能科技(赣州)股份有限公司 | Electrolyte raw material composition, electrolyte, lithium ion secondary battery and preparation method thereof |
| CN111816925B (en) * | 2020-08-14 | 2022-11-29 | 中南大学 | Solid-state battery and preparation method thereof |
| CN113839096B (en) * | 2021-08-20 | 2024-02-27 | 深圳市本征方程石墨烯技术股份有限公司 | Preparation method of electrolyte, lithium ion battery and preparation method of lithium ion battery |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1601803A (en) * | 2003-09-24 | 2005-03-30 | 三星Sdi株式会社 | Polymer electrolyte compsn. for rechargable Li cell and rechargable Li cell of using same |
| US20050227150A1 (en) * | 2004-04-07 | 2005-10-13 | Weibing Xing | In situ thermal polymerization method for making gel polymer lithium ion rechargeable electrochemical cells |
| CN101188282A (en) * | 2006-03-20 | 2008-05-28 | 日立麦克赛尔株式会社 | Nonaqueous secondary battery and its using method |
| CN101563808A (en) * | 2006-12-21 | 2009-10-21 | 株式会社Lg化学 | Gel polymer electrolyte composition, gel polymer electrolyte and electrochemical device comprising the same |
| KR20100099994A (en) * | 2009-03-04 | 2010-09-15 | 주식회사 엘지화학 | Electrolyte comprising eutectic mixture and electrochemical device containing the same |
| CN102544456A (en) * | 2010-12-14 | 2012-07-04 | 苏州大学 | Cathode material of secondary battery and preparation method thereof as well as anode and secondary battery |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000188129A (en) * | 1998-12-22 | 2000-07-04 | Hitachi Maxell Ltd | Polymer electrolyte battery |
| JP5013386B2 (en) * | 2000-11-17 | 2012-08-29 | 日立マクセルエナジー株式会社 | Positive electrode active material for non-aqueous secondary battery and non-aqueous secondary battery using the same |
| JP2003068137A (en) * | 2001-08-23 | 2003-03-07 | Nippon Kayaku Co Ltd | Resin composition for polymer solid electrolyte, polymer solid electrolyte and polymer battery |
| US20030104282A1 (en) * | 2001-11-15 | 2003-06-05 | Weibing Xing | In situ thermal polymerization method for making gel polymer lithium ion rechargeable electrochemical cells |
| JP2007039266A (en) * | 2005-08-02 | 2007-02-15 | Sumitomo Metal Mining Co Ltd | Manufacturing method of lithium-manganese-nickel complex oxide and positive electrode active material for non-aqueous electrolyte secondary cell |
| KR100866764B1 (en) * | 2006-09-25 | 2008-11-03 | 주식회사 엘지화학 | Non-aqueous electrolyte and electrochemical device comprising the same |
| KR101173200B1 (en) * | 2008-08-05 | 2012-08-10 | 주식회사 엘지화학 | Method of preparing gel polymer electrolyte secondary battery and Gel polymer electrolyte secondary battery |
-
2014
- 2014-01-27 KR KR1020140009646A patent/KR101641763B1/en active IP Right Grant
- 2014-01-28 BR BR112014017467A patent/BR112014017467B8/en active IP Right Grant
- 2014-01-28 JP JP2015523036A patent/JP6274453B2/en active Active
- 2014-01-28 TW TW103103224A patent/TWI546998B/en active
- 2014-01-28 CN CN201480001219.1A patent/CN104285331A/en active Pending
-
2017
- 2017-10-25 JP JP2017206639A patent/JP6504550B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1601803A (en) * | 2003-09-24 | 2005-03-30 | 三星Sdi株式会社 | Polymer electrolyte compsn. for rechargable Li cell and rechargable Li cell of using same |
| US20050227150A1 (en) * | 2004-04-07 | 2005-10-13 | Weibing Xing | In situ thermal polymerization method for making gel polymer lithium ion rechargeable electrochemical cells |
| CN101188282A (en) * | 2006-03-20 | 2008-05-28 | 日立麦克赛尔株式会社 | Nonaqueous secondary battery and its using method |
| CN101563808A (en) * | 2006-12-21 | 2009-10-21 | 株式会社Lg化学 | Gel polymer electrolyte composition, gel polymer electrolyte and electrochemical device comprising the same |
| KR20100099994A (en) * | 2009-03-04 | 2010-09-15 | 주식회사 엘지화학 | Electrolyte comprising eutectic mixture and electrochemical device containing the same |
| CN102544456A (en) * | 2010-12-14 | 2012-07-04 | 苏州大学 | Cathode material of secondary battery and preparation method thereof as well as anode and secondary battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111542962A (en) * | 2018-04-27 | 2020-08-14 | 株式会社Lg化学 | Lithium secondary battery and method for manufacturing same |
| CN111542962B (en) * | 2018-04-27 | 2023-10-24 | 株式会社Lg新能源 | Lithium secondary battery and method for manufacturing same |
Also Published As
| Publication number | Publication date |
|---|---|
| BR112014017467A8 (en) | 2017-07-04 |
| JP2015522932A (en) | 2015-08-06 |
| BR112014017467A2 (en) | 2017-06-13 |
| JP6274453B2 (en) | 2018-02-07 |
| BR112014017467B8 (en) | 2023-03-21 |
| JP6504550B2 (en) | 2019-04-24 |
| TWI546998B (en) | 2016-08-21 |
| JP2018049835A (en) | 2018-03-29 |
| TW201448318A (en) | 2014-12-16 |
| KR20140097025A (en) | 2014-08-06 |
| BR112014017467B1 (en) | 2021-08-03 |
| KR101641763B1 (en) | 2016-07-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2905831B1 (en) | Cathode additive for high-capacity lithium secondary battery | |
| CN106797053B (en) | Gel polymer electrolyte and lithium secondary battery including it | |
| CN104285331A (en) | High-voltage lithium secondary battery | |
| CN104380516B (en) | Composition for gel polymer electrolyte and lithium secondary battery comprising the same | |
| KR20180083272A (en) | Non-aqueous electrolyte solution and lithium secondary battery comprising the same | |
| JP5723778B2 (en) | Non-aqueous electrolyte for lithium secondary battery and lithium secondary battery provided with the same | |
| JP2005505117A (en) | Lithium ion secondary battery or battery, and its protection circuit, electronic device, and charging device | |
| EP2790260B1 (en) | Composition for gel polymer electrolyte and lithium secondary battery comprising same | |
| CN103597648B (en) | Non-aqueous electrolyte and use its lithium secondary battery | |
| CN105453327A (en) | Non-aqueous electrolyte and lithium secondary battery comprising same | |
| CN104969403A (en) | Non-aqueous electrolytic solution and lithium secondary battery comprising same | |
| CN102210046A (en) | Lithium secondary battery containing a non-aqueous electrolytic solution | |
| CN104604014A (en) | Non-aqueous electrolyte and lithium secondary battery comprising same | |
| KR20170086876A (en) | Charging and discharging method for lithium secondary battery | |
| CN104285330B (en) | Lithium secondary battery | |
| KR20200020169A (en) | Electrolyte for lithium secondary battery | |
| KR101651143B1 (en) | Lithium secondary battery having improved cycle life | |
| US10170791B2 (en) | High-voltage lithium secondary battery | |
| CN112687956A (en) | Non-aqueous electrolyte of lithium battery and lithium ion battery based on same | |
| EP3975305A1 (en) | Method for manufacturing secondary battery | |
| KR100859628B1 (en) | Prismatic lithium rechargeable battery including polymer anhydrous electrolytes, and thereof method | |
| CN112713308A (en) | Non-aqueous electrolyte and lithium ion battery based on same | |
| KR102275863B1 (en) | ELECTRODE FOR LiTHIUM SECONDARY BATTERY AND SECONDARY BATTERY COMPRISING THE SAME |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150114 |
|
| RJ01 | Rejection of invention patent application after publication |