CN101814628B - Hyperbranched polyester lithium ion battery gel electrolyte and preparation method thereof - Google Patents
Hyperbranched polyester lithium ion battery gel electrolyte and preparation method thereof Download PDFInfo
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- CN101814628B CN101814628B CN2009102140621A CN200910214062A CN101814628B CN 101814628 B CN101814628 B CN 101814628B CN 2009102140621 A CN2009102140621 A CN 2009102140621A CN 200910214062 A CN200910214062 A CN 200910214062A CN 101814628 B CN101814628 B CN 101814628B
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- 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
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- 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
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- 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
Abstract
The invention relates to a hyperbranched polyester lithium ion battery gel electrolyte and a preparation method thereof. The gel electrolyte is formed by mixed liquor prepared from 5-30 percent by mass of hyperbranched photopolymer resin, 5-25 percent by mass of cross-linking agent, 1-10 percent by mass of initiator, 20-50 percent by mass of plasticizer, 20-50 percent by mass of lithium salt and the like by using a radiation crosslinking method or a heating crosslinking method and the like. In the invention, the hyperbranched structure of a hyperbranched polyester can effectively prevent chain segments from being crystallized, whereas the molecular conformation similar to a spheric shape can increase the free volume of the polyester; bigger space and fewer -COO- and ether bond structures among branch points of the hyperbranched polyester have very strong interreaction with oxygen in the carbonic ester plasticizer, and therefore, a large amount of liquid electrolyte can be contained, and the gel electrolyte has very high dissolving capacity on salts, which is beneficial to ionic migration and the increase of electrical conductivity so that a lithium ion battery prepared from the hyperbranched polyester lithium ion battery gel electrolyte has long service life, small internal resistance, better specific energy, simple preparation process and no pollution.
Description
Technical field
The invention relates to the gel electrolyte that lithium ion battery is used, particularly have hyperbranched polyester lithium ion battery gel electrolyte that the lithium ion battery of high ionic conductance, suitable mechanical strength, pliability, pore structure and chemistry and electrochemical stability uses and preparation method thereof.
Background technology
The technological core of polymer Li-ion battery is to adopt polymer substrate as electrode and electrolytical skeleton structure, and the liquid electrolyte molecule is fixed therein, thereby electrode and electrolyte inside have high ionic conductivity.The key technology of polymer Li-ion battery is the preparation polymer dielectric, requires polymer dielectric to have high ionic conductance, suitable mechanical strength, pliability and chemistry and electrochemical stability etc.
Polymer substrate is that the development of solid electrolyte is broadly divided into 3 stages: 1. pure solid polymer electrolyte; 2. gel polymer electrolyte; 3. plural gel polymer dielectric.Pure solid polymer electrolyte does not contain any organic liquid, is solid solvent with the polymer only, and conductivity at room temperature has only 10
-8The order of magnitude of S/cm, the application in lithium ion battery is restricted.Gel polymer electrolyte is that plasticizer and lithium salts are formed by polymer, micromolecule solvent, has gathered the pliability of solid and the characteristics that liquid is prone to diffusion, is widely used.Gel polymer electrolyte has overcome liquid electrolyte and has been prone to generate combustible material and leakage defect at electrode surface, makes the design of battery freer.The existence of micromolecule solvent; Make gel polymer electrolyte have solvent migration property; Volatility is big, electrochemical stability and thermal stability are relatively poor, and ionic conductivity is relatively low, and mechanical strength is low; Deficiencies such as electrolyte and electrode interface poor stability, thereby have the people to propose plural gel polymer dielectric and porous gel polymer dielectric.These two kinds of electrolyte are the modifications to gel polymer electrolyte; Two kinds of method of modifying commonly used at present are to add electrochemistry inert filler and the hole density that increases polymer dielectric film; To increase ionic conductivity, to improve mechanical strength, improve the stability of electrolyte and electrode interface.
In recent years, the researcher has prepared the gel polymer electrolyte of following several types through methods such as blend, crosslinked, copolymerization and inorganic filler blend.
1, polyethylene glycol oxide system
Polyoxyethylene olefinic ether compound, its conduction is mainly accomplished by the sub-chain motion of amorphous area, itself electrolytic salt is had solvation, can be applicable to the preparation of polymer dielectric, but room-temperature conductivity is low.In order to improve this shortcoming, people have attempted multiple improving one's methods, and mainly contain crosslinked, blend and copolymerization etc.Someone adds crosslinking agent in the polyethylene glycol oxide oligomer; Utilize initiated polymerizations such as ultraviolet light, heat, light and electron beam irradiation; Make its generation crosslinked; Form a kind of network-like big molecule, reduced the solubility of linear polyethylene glycol oxide in organic plasticizer, and improved storage capacity electrolyte solution.From present research situation, the conductivity of polyoxyethylene thiazolinyl gel polymer electrolyte approaches liquid electrolyte, but mechanical strength has much room for improvement.
2, polymethacrylates system
Polymethyl methacrylate is as the basis material of gel polymer electrolyte; Owing in its construction unit a carbonyl side group is arranged; With the oxygen in the carbonates plasticizer very strong interaction is arranged; Therefore can contain a large amount of liquid electrolytes, and polymethacrylates series gel electrolyte there is interface stability preferably to lithium electrode, low with the interface impedance of metal lithium electrode.But polymethyl methacrylate base gel polymer electrolyte mechanical strength is lower, structural stability is relatively poor, Li
+Transference number of ions is on the low side, and its cation transport number generally is no more than 0.5, is difficult to fully contact with electrode, has influenced its further application.
3, Kynoar system
Kynoar is a kind of crystalline polymer, and the C-F group on the macromolecular chain is that very strong electronics shrinks group, and the Kynoar base polymer electrolyte has higher anti-anodic oxidation ability.This polymer serondary lithium battery function admirable that gel-type Kynoar-hexafluoropropylene copolymer electrolyte is processed can satisfy the needs of equipment such as the mobile phone that develops towards little, the in light weight portability direction of volume, portable type Communication Equipment, notebook computer.Compound through polymer and polymer, inorganic matter and organic plasticizer can be improved the room-temperature conductivity of polymer dielectric effectively, improves the state of interface of electrode/electrolyte, and can keep certain mechanical strength.And present topmost problem is to compare with liquid electrolyte, and this electrolyte conductivity at room temperature also is not very high, and the performance that discharges and recharges repeatedly also awaits improving.
4, polyacrylonitrile system
The polyacrylonitrile based gel electrolyte is to study gel-form solid polymer electrolyte comparatively widely.In the polyacrylonitrile strand because of the oxygen-free atom; And a little less than contained nitrogen-atoms and the lithium ion effect; And the dispersion that the lithium salts in the polyacrylonitrile system gel electrolyte, solvent all can reach molecular level forms homogeneous phase, thereby transport number is big than the polyethylene glycol oxide system, can reach 0.5.Because contain strong polar group-CN on the polyacrylonitrile chain, poor with the metal lithium electrode compatibility, gel electrolyte film and lithium electrode interface passivation phenomenon are serious.Simultaneously, the crystallinity of polyacrylonitrile is strong, and when temperature rose, electrolyte was separated out, from and become liquid electrolyte.Therefore, must carry out modification, the method for modification is generally copolymerization and crosslinked.
Summary of the invention
The objective of the invention is in order to remedy the deficiency that prior art exists; A kind of hyperbranched polyester lithium ion battery gel electrolyte and preparation method thereof is provided, and this gel electrolyte has high ionic conductance, suitable mechanical strength, pliability, pore structure and chemistry and electrochemical stability.
For realizing the foregoing invention purpose; The technical scheme that the present invention takes is: this hyperbranched polyester lithium ion battery gel electrolyte: by mass percent 5%～30% hyperbranched photopolymer resin; The mixed liquor that 5%～25% crosslinking agent, 1%～10% initator, 20%～50% plasticizer, 20%～50% lithium salts etc. form forms through methods such as crosslinking with radiation or heat cross-linkings.
Said hyperbranched photopolymer resin is passed through A
2+ B
3Method is synthetic; Its concrete synthetic method is following: with hydroxyl value is that 2 or 3 polyalcohol or polyethers and carboxyl number are that 3 or 2 polyacid or acid anhydrides are reactant; Carboxyl or anhydride reaction through hydroxyl groups and polyacid; Synthesis of super branched polyester, utilize the monomer that has epoxy radicals and double bond structure in peripheral carboxyl of this polymer molecule and the molecular structure as: the epoxy reaction synthetic molecules periphery in the GMA contains the hyperbranched photopolymer of unsaturated group.
Said polyalcohol comprises ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene-glycol, various molecular weight polyethylene glycol, propane diols, DPG, tripropylene glycol, glycerine, trimethylolpropane.
Said polyacid comprises terephthalic acid (TPA), phthalic acid, succinic acid, adipic acid and the binary acid with following structure:
Or ternary acid with following structure:
Said acid anhydrides comprises succinic anhydride, maleic acid anhydride, phthalic anhydride, trimellitic anhydride and the acid anhydrides with following structure:
Said monomer with epoxy radicals and double bond structure is like GMA, allyl glycidyl ether, and the compound with following structure:
A: have＞group of C=C＜structure
Said hyperbranched photopolymer resin is a standard with the polystyrene, adopts gel osmoticing chromatogram analysis, and molecular weight is at 500～2000g/mol, and molecule chain end contains hydroxyl and following building stone:
A: have＞group of C=C＜structure
Said crosslinking agent comprises acrylic acid ester, methacrylate, vinylacetate, vinyl ethers etc., allyl glycidyl ether, ethoxy ethoxy ethoxy acrylic acid ester, ethoxy ethoxy ethyl propylene acid esters, the ring trimethylolpropane dimethoxym ethane acrylic acid ester of simple function group; Also comprise difunctionality and trifunctional acrylic acid ester etc.; Like tripropylene glycol diacrylate, ethoxyquin 1; 6-hexanediyl ester, third oxidation 1,6-hexanediyl ester, propylene glycol diacrylate, ethoxyquin propylene glycol diacrylate, Macrogol 200 diacrylate, PEG400 diacrylate, Macrogol 600 diacrylate, trimethylolpropane triacrylate, trimethylol-propane trimethacrylate etc.
Said initator comprises, as: benzoyl peroxide, cumyl peroxide, di-t-butyl peroxide, dilauroyl peroxide, peroxidized t-butyl perbenzoate, the peroxidating trimethylacetic acid tert-butyl ester, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate, azodiisobutyronitrile, ABVN etc.
Said lithium salts comprises: lithium perchlorate LiClO
4, lithium bromide LiBr, lithium chloride L iCl, lithium iodide LiI, lithium rhodanate LiSCN, LiBF4 LiBF
4, LiFePO 4 LiFePO
4, hexafluoroarsenate lithium LiAsF
6Deng.
Said plasticizer comprises: gamma-butyrolacton, ethylene carbonate, propene carbonate, dimethyl carbonate, methyl ethyl carbonate, 1, and 2-propane diols carbonic ester, polyethylene glycol etc., or multiple above-mentioned plasticizer mixes the mixed liquor that obtains by a certain percentage.
A kind of preparation method of hyperbranched polyester lithium ion battery gel electrolyte: be prepared into lithium ion battery cell after the hyperbranched photopolymer resin of mass percent 5%～30%, 5%～25% crosslinking agent, 1%～10% initator, 20%～50% plasticizer, 20%～50% lithium salts etc. are mixed; Lithium ion battery cell with preparation in the baking oven slowly was warming up to 30～45 ℃ of polymerizations about 24 hours; Be warming up to the interior polymerization of 60～80 ℃ of scopes again and carry out heat cross-linking about 24 hours; Or under the normal temperature; At energy is the crosslinking electron beam irradiation of 0.15～0.35MeV, or under the normal temperature with
60Crosslinking with radiation is carried out in Co gamma-radiation source, and preparation forms the network polymers gel electrolyte.
Advantage of the present invention:
The present invention proposes to prepare lithium ion battery gel electrolyte with hyper-branched polyester; Be because dissaving polymer has the molecular conformation of almost spherical; Its free volume is relatively large; Do not have crystalline polamer, simultaneously, between the side chain in bigger space and the hyper-branched polyester oxygen in a large amount of-COO-group and diether linkage structure and the carbonates plasticizer very strong interaction is arranged; Therefore can contain a large amount of liquid electrolytes; And make hyper-branched polyester stronger solvability arranged to salt, help the migration of ion and the raising of conductivity, thereby make lithium ion battery gel electrolyte have high ionic conductance, suitable mechanical strength, pliability, pore structure and chemistry and electrochemical stability.
Hyperbranched polyester lithium ion battery gel electrolyte of the present invention; Can effectively prevent the crystallization of segment because of the highly branched structure of dissaving polymer; And the molecular conformation of almost spherical can increase the free volume of polymer, and bigger space and the oxygen in more-COO-and diether linkage structure and the carbonates plasticizer have very strong interaction between the dissaving polymer branch point, therefore can contain a large amount of liquid electrolytes; And make it stronger solvability arranged to salt; And help the migration of ion and the raising of conductivity, make that the lithium ion battery that is prepared by hyperbranched polyester lithium ion battery gel electrolyte has extended cycle life, internal resistance is little, and have specific energy preferably; And the preparation process is simple, and is pollution-free.
Description of drawings
Fig. 1 is the infrared spectrogram of GMA of the present invention, hyper-branched polyester resin and hyperbranched photopolymer;
Fig. 2 is hyper-branched polyester resin and the hyperbranched photopolymer thermal analysis curue that the present invention synthesizes.
Embodiment
Embodiment:
One, hyperbranched photopolymer resin is synthetic:
The mass percent of raw material and proportioning
1,2,4-trimellitic anhydride 40.0～70.0%
Ethylene glycol 10.0～40.0%
GMA 5.0～30.0%
MEHQ 1.0～5.0%
N, dinethylformamide 5.0～20.0%
Technology:
With 1,2,4-trimellitic anhydride, ethylene glycol, N, dinethylformamide add in the four-hole bottle; Water knockout drum is installed, under stirring and nitrogen protection, is warming up to and makes the trimellitic anhydride dissolving about 110 ℃; Be warming up to 170～180 ℃ of reactions 16 hours gradually, obtain hyper-branched polyester, synthetic polymer is cooled to below 70 ℃; Add GMA and polymerization inhibitor MEHQ, under agitation, be warming up to 85～95 ℃ of reactions 2～3 hours; Constant to acid number, be cooled to less than 50 ℃ of dischargings, obtain hyperbranched photopolymer.It is to precipitate in 1: 1 the methanol/water solution that synthetic polymer solution under agitation is added drop-wise to volume ratio, and isolated polymer is used acetone solution again.And the deposition that uses the same method, separate, so purifying is 3 times, (pressure 0.08kPa, 30 ℃) dry hyperbranched photopolymer that obtained being used for lithium ion battery gel electrolyte in 24 hours in the decompression baking oven.
The infrared analysis of figure one shows 1730～1780cm
-1There is not C-O stretching vibration absworption peak in the acid anhydrides in the place, explains that trimellitic anhydride and ethylene glycol fully react; Hyper-branched polyester and hyperbranched photopolymer infrared spectrum analysis are compared, and hyperbranched photopolymer is at 1620cm
-1There is the stretching vibration absworption peak of C=C in the place, simultaneously at 3482cm
-1Place-OH stretching vibration absworption peak obviously strengthens than hyper-branched polyester, explains that GMA has been introduced on the hyper-branched polyester molecular resin.Figure two hot analysis results show that in 160 ℃, synthetic hyperbranched photopolymer is stable, does not have weightlessness basically; Slight weightlessness is arranged between 160～370 ℃, and temperature is seriously weightless during greater than 370 ℃; And hyper-branched polyester is stable in 160 ℃, does not have weightlessness basically; Slight weightlessness is arranged between 160～350 ℃; Serious weightless greater than 350 ℃; Explain hyper-branched polyester and hyperbranched photopolymer at 300 ℃ with interior its better heat stability; Its thermal stability does not have to change basically behind the peripheral introducing of the hyperbranched polymer molecule GMA, and the hyperbranched photopolymer that obtains has stability preferably.
Two, the preparation of hyperbranched polyester lithium ion battery gel electrolyte:
The mass percent of raw material and proportioning
Hyperbranched photopolymer resin 5.0%～30.0%
Macrogol 600 diacrylate 5.0%～25.0%
Benzoyl peroxide 1.0%～10.0%
Gamma-butyrolacton+dimethyl carbonate 20.0%～50.0%
Lithium perchlorate 20.0%～50.0%
Preparation technology:
At N
2In the environment; Behind hyperbranched photopolymer resin, Macrogol 600 diacrylate, benzoyl peroxide, gamma-butyrolacton+dimethyl carbonate and lithium perchlorate mixed dissolution; Be prepared into lithium ion battery cell; Lithium ion battery cell with preparation in the baking oven slowly was warming up to 30～45 ℃ of polymerizations about 24 hours, was warming up to the interior polymerization of 60～80 ℃ of scopes again and carried out heat cross-linking about 24 hours, obtained the lithium ion battery cell that is formed by hyperbranched polyester lithium ion battery gel electrolyte.Also can electric core be used electron beam crosslinking, irradiation dose 5～20kGy.
Prepared its detailed performance characteristics of lithium ion battery of the hyperbranched polyester lithium ion battery gel electrolyte that is formed by embodiment is following:
1, cycle life:＞500 times;
2, internal resistance:＜50 milliohms
3, overcharge 1C * 12V; Do not fire not quick-fried
4, acupuncture: do not fire not quick-fried
5, heavy impact: do not fire not quick-fried
6, extruding: do not fire not quick-fried
7, high temperature, 85 ℃ * 4 hours: expanding, it was qualified to fill
8, thermal shock, 150 ℃ * 30min: do not fire not quick-fried
9, peeling force between barrier film and positive/negative plate: qualified
10, specific energy: 415Wh/L.
Claims (5)
1. hyperbranched polyester lithium ion battery gel electrolyte; It is characterized in that: the mixed liquor by mass percent 5%～30% hyperbranched photopolymer resin, 5%～25% crosslinking agent, 1%～10% initator, 20%～50% plasticizer and 20%～50% lithium salts form forms said gel electrolyte through crosslinking with radiation or heat cross-linking method;
Said hyperbranched photopolymer resin is passed through A
2+ B
3Method is synthetic; Its concrete synthetic method is following, is that 2 polyalcohol and carboxyl number are that 3 polyacid is a reactant with hydroxyl value, or is that 3 polyalcohol and carboxyl number are that 2 polyacid is a reactant with hydroxyl value; Through the carboxyl reaction of hydroxyl groups and polyacid, synthesis of super branched polyester; The hyperbranched photopolymer resin of utilizing peripheral carboxyl of synthetic hyperbranched poly ester molecule and the epoxy reaction synthetic molecules periphery in the GMA to contain unsaturated group; Said hyperbranched photopolymer resin is a standard with the polystyrene, adopts gel osmoticing chromatogram analysis, and molecular weight is at 500～2000g/mol, and molecule chain end contains hydroxyl and methacryloxy;
Crosslinking agent is methacrylate, vinylacetate, vinyl ethers, allyl glycidyl ether, ethoxy ethoxy ethyl propylene acid esters, ring trimethylolpropane dimethoxym ethane acrylic acid ester, tripropylene glycol diacrylate, ethoxyquin 1; 6-hexanediyl ester, third oxidation 1,6-hexanediyl ester, propylene glycol diacrylate, ethoxyquin propylene glycol diacrylate, Macrogol 200 diacrylate, PEG400 diacrylate, Macrogol 600 diacrylate, trimethylolpropane triacrylate or trimethylol-propane trimethacrylate;
Initator is benzoyl peroxide, cumyl peroxide, di-t-butyl peroxide, dilauroyl peroxide, peroxidized t-butyl perbenzoate, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate, azodiisobutyronitrile or ABVN;
Plasticizer is gamma-butyrolacton, ethylene carbonate, propene carbonate, dimethyl carbonate, methyl ethyl carbonate, 1, and 2-propane diols carbonic ester, polyethylene glycol or multiple above-mentioned plasticizer mix the mixed liquor that obtains by a certain percentage.
2. according to the said hyperbranched polyester lithium ion battery gel electrolyte of claim 1, it is characterized in that: said hydroxyl value is that 2 polyalcohol is ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene-glycol, various molecular weight polyethylene glycol, propane diols, DPG or tripropylene glycol; Said hydroxyl value is that 3 polyalcohol is glycerine or trimethylolpropane.
3. according to the said hyperbranched polyester lithium ion battery gel electrolyte of claim 1, it is characterized in that: said carboxyl number is that 2 polyacid is terephthalic acid (TPA), phthalic acid, succinic acid or adipic acid.
4. according to the said hyperbranched polyester lithium ion battery gel electrolyte of claim 1, it is characterized in that: said lithium salts is lithium perchlorate LiClO
4, lithium bromide LiBr, lithium chloride LiCl, lithium iodide LiI, lithium rhodanate LiSCN, LiBF4 LiBF
4, LiFePO 4 LiFePO
4, or hexafluoroarsenate lithium LiAsF
6
5. method for preparing hyperbranched polyester lithium ion battery gel electrolyte as claimed in claim 1; The hyperbranched photopolymer resin of mass percent 5%～30%, 5%～25% crosslinking agent, 1%～10% initator, 20%～50% plasticizer and 20%～50% lithium salts are mixed back preparation lithium ion battery cell; In the baking oven lithium ion battery cell of preparation slowly is warming up to 30～45 ℃ of polymerizations and was warming up in 60～80 ℃ of scopes polymerization in 24 hours again and carried out heat cross-linking in 24 hours, or under the normal temperature energy be under crosslinking electron beam irradiation or the normal temperature of 0.15～0.35MeV with
60Crosslinking with radiation is carried out in Co gamma-radiation source, and preparation forms the network polymers gel electrolyte.
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| CN102360951B (en) * | 2011-06-20 | 2012-10-31 | 华东师范大学 | Micro-branched polymer gel electrolyte and preparation method thereof |
| CN102616764B (en) * | 2011-10-10 | 2014-04-02 | 山东科技大学 | Preparation method of porous LiFePO4 powder |
| CN104167563B (en) * | 2014-08-15 | 2016-05-11 | 北京理工大学 | A kind of composite solid electrolyte film, preparation method and application |
| KR101648465B1 (en) | 2015-02-17 | 2016-08-16 | 주식회사 제낙스 | Gel polymer electrolyte, method for manufacturing the same, and electrochemical device including the same |
| CN105655636B (en) * | 2016-04-08 | 2019-07-23 | 山东海帝新能源科技有限公司 | One kind having cellular network architecture gel electrolyte and preparation method thereof |
| CN106410269A (en) * | 2016-04-12 | 2017-02-15 | 中国科学院大学 | All-solid-state composite polymer electrolyte and preparation method thereof |
| CN105762403A (en) * | 2016-04-12 | 2016-07-13 | 中国科学院大学 | All-solid-state lithium-ion battery based on topological-structured polymer electrolyte |
| CN106129468A (en) * | 2016-07-15 | 2016-11-16 | 天津大学 | A kind of preparation method of single-ion polymer gel electrolyte materials |
| CN107819150B (en) * | 2017-08-07 | 2020-02-14 | 天津金牛电源材料有限责任公司 | Lithium ion battery gel electrolyte and preparation method thereof |
| US10998578B2 (en) * | 2017-08-18 | 2021-05-04 | GM Global Technology Operations LLC | Electrolyte membrane |
| CN110117417B (en) * | 2018-02-07 | 2021-03-26 | 比亚迪股份有限公司 | Polymer electrolyte membrane, preparation method thereof and lithium ion battery |
| CN109301316B (en) * | 2018-09-28 | 2020-12-08 | 苏州清陶新能源科技有限公司 | Organic-inorganic composite electrolyte, preparation method thereof and application thereof in solid lithium ion secondary battery |
| DE102020101137A1 (en) * | 2019-02-01 | 2020-08-06 | GM Global Technology Operations LLC | ELECTROLYTE MEMBRANES |
| CN113130982B (en) * | 2019-12-30 | 2023-06-06 | 北京卫蓝新能源科技有限公司 | Preparation method of high-liquid-retention electrolyte and application of high-liquid-retention electrolyte in lithium battery |
| CN111430790A (en) * | 2020-03-03 | 2020-07-17 | 蜂巢能源科技有限公司 | Semi-solid electrolyte and preparation method and application thereof |
| CN112467201B (en) * | 2020-11-25 | 2022-06-21 | 华南理工大学 | All-solid-state high-strength aliphatic polyurethane flexible electrolyte and preparation method thereof |
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| CN101220170A (en) * | 2007-09-30 | 2008-07-16 | 江苏科技大学 | Production method for polyolefin membrane support gel rubber polymer electrolyte |
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