[go: up one dir, main page]

CN1558463A - Preparation method of in-situ thermal crosslinking of fluorine-containing gel electrolyte material and preparation method of polymer lithium-ion battery - Google Patents

Preparation method of in-situ thermal crosslinking of fluorine-containing gel electrolyte material and preparation method of polymer lithium-ion battery Download PDF

Info

Publication number
CN1558463A
CN1558463A CNA2004100160365A CN200410016036A CN1558463A CN 1558463 A CN1558463 A CN 1558463A CN A2004100160365 A CNA2004100160365 A CN A2004100160365A CN 200410016036 A CN200410016036 A CN 200410016036A CN 1558463 A CN1558463 A CN 1558463A
Authority
CN
China
Prior art keywords
fluorine
electrolyte
acrylate
lithium
electrolyte 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.)
Pending
Application number
CNA2004100160365A
Other languages
Chinese (zh)
Inventor
杨清河
邱玮丽
马晓华
付延鲍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fudan University
Original Assignee
Fudan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fudan University filed Critical Fudan University
Priority to CNA2004100160365A priority Critical patent/CN1558463A/en
Publication of CN1558463A publication Critical patent/CN1558463A/en
Pending legal-status Critical Current

Links

Classifications

    • 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

Landscapes

  • Secondary Cells (AREA)

Abstract

The invention provides a method of making fluorine-containing gel state electrolyte material and polymeric lithium ion cells by employing in-situ thermal cross bonding process, wherein fluorine-containing acrylic ester material is used as monomer, and double functional group acrylic acid ester containing polyethylene glycol or triple functional group acrylic acid ester containing polyethylene glycol are used as cross linking agent, the making process comprises injecting the miscible liquid comprising monomer, cross linking agent, thermal initiation agent and lithium ion electrolyte salt solution into the core of lithium ion cells, heating the cell to result in-situ thermal chemical cross-linking for the two acrylic esters, whereby the acrylic ester copolymer network bundles the solution in the electrolyte, forming the gel state electrolyte material with stabilized physical and chemical properties.

Description

The in-situ heat cross bonding preparation method of fluoride gel attitude electrolyte and the preparation method of polymer Li-ion battery thereof
Technical field
The invention belongs to the fluoride gel attitude electrolyte of polymer Li-ion battery and the manufacture method of battery thereof.
Background technology
Can produce the liquid electrolyte lithium ion battery in a large number both at home and abroad at present, the liquid electrolyte lithium ion battery adopts the organic bath liquid that contains lithium salts, and its composition is mainly by ethylmethyl carbonate (ethylmethyl carbonate (EMC), C 4H 8O 3), ethylene carbonate (ethylenecarbonate (EC), C 3H 4O 3), diethyl carbonate (diethyl carbonate (DEC), C 5H 10O 3), dimethyl carbonate (dimethyl carbonate (DMC), C 3H 6O 3), propene carbonate (propylenecarbonate (PC), C 4H 6O 3) and vinylene carbonate (vinylene carbonate (VC), C 3H 2O 3) wait organic solvent and various inorganic lithium salt such as LiCF 3SO 3, LiN (CF 3SO 2) 2, LiC (CF 3SO 2) 3, LiPF 6, LiBF 4, LiAsF 6And LiClO 4Deng the solution that is mixed with is electrolyte solution.These lithium salt solutions provide conductivity near 10 for lithium ion battery -2The electrolyte solution of S/cm has satisfied the requirement that lithium ion battery hangs down internal resistance, high charge-discharge magnification.The weak point of liquid lithium ionic cell be adopted volatile, inflammable, easily flow thereby the organic solution of easy to leak, if improper use, might cause danger such as leakage, corrosion and burning, so the liquid electrolyte lithium ion battery adopts all generally metal material to make shell to improve fail safe.Adopt at present aluminum-plastic composite material softer packing technique to prepare that liquid lithium ionic cell also exists leakage and the problem of flatulence took place between the storage life.
The polymer Li-ion battery of a new generation is tried hard in the advantage that keeps the liquid electrolyte lithium ion battery, overcome above-mentioned shortcoming, the representative of this respect is with the invention (U.S.patent5 of Bellcore company, 540,741) usefulness vinylidene difluoride-hexafluoropropylene copolymer (PVDF-HFP) is the perforated membrane technology (physical crosslinking method) and the gel state electrolyte material technology (US patents 5603982) (Chemical Crosslinking Methods) of material, and these technology are wrapped in liquid electrolyte in polymer micro or the network.Polymer Li-ion battery has been simplified the battery case packing, make large tracts of land, ultrathin type, lithium ion battery different and high-energy-density become possibility, and be used for portable electric appts of new generation in a large number as energy source device, but the expensive polymer dielectric film manufacturing process that needs complex process in this kind battery production process becomes the technical bottleneck of making polymer Li-ion battery.
The fluoro containing polymers network configuration is the characteristics that the electrolyte of gel state has stable electrochemical property, but fluoro containing polymers network parcel electrolyte ability is relatively poor, and solution leakage can take place longer-term storage.
The macromolecule network that contains the polyethylene glycol multi-functional acrylate has the ability of good parcel electrolyte, the network bonds chalaza that forms with chemical bond has good temperature stability, can keep the electrolyte long term storage behind the gel and the problem of solution leakage does not take place.
Fluorinated acrylate monomer, contain and form the electrolytical mixed liquor precursor of fluoride gel attitude after polyethylene glycol multi-functional acrylate crosslinking agent and thermal initiator are dissolved in lithium ion battery electrolyte solution commonly used, heating make monomer in this mixed liquor and crosslinking agent realize crosslinked after, copolymer networks parcel electrolyte forms the gel polymer electrolyte material, it has the characteristics of stable physical property and stable electrochemical property concurrently, is applicable to the needs of gel state electrolyte polymer Li-ion battery.
Summary of the invention
The objective of the invention is to obtain a kind of prepare simple, technology is convenient, overcome the preparation method of not enough fluoride gel attitude electrolyte such as current electrolysis matter liquid seepage, volatilization, the degassing.
The objective of the invention is to develop a kind of manufacture method of using the polymer Li-ion battery of above-mentioned fluoride gel attitude electrolyte.
The present invention is monomer with the fluorinated acrylate, is crosslinking agent with the multi-functional acrylate who contains polyethylene glycol, forms mixed liquor after monomer, crosslinking agent and thermal initiator are dissolved in electrolyte solution.Above-mentioned mixed liquor is injected lithium ion battery cell, this mixed liquor has good flowability before polymerization, the battery battery core that contains this mixed liquor by heating makes monomer and crosslinking agent generation thermochemical crosslinking on the throne in cell body, electrolyte solution then is wrapped in the copolymer networks, forms the gel state electrolyte material of physics and stable electrochemical property and makes fluorine-containing gel state electrolyte polymer Li-ion battery simultaneously.
It is monomer that the present invention adopts fluorinated acrylate, and the multi-functional acrylate who contains polyethylene glycol is crosslinking agent, and the thermal polymerization temperature is 60-80 ℃, and the time is 60-180 minute.The polymer that thermal polymerization forms possesses three-dimensional net structure, and the gained gel rubber system has big electrolyte solution to contain ability and stable temperature characterisitic.Gained gel polymer electrolyte material keeps the characteristics of liquid lithium ion electrolyte solution high conductivity, and by regulating the amount of monomer and crosslinking agent, the gel state electrolyte conductivity of electrolyte materials when making 25 ℃ is greater than 4 * 10 -3S/cm, and the conductivity subzero 20 ℃ the time is greater than 1 * 10 -3S/cm, gel polymer electrolyte fusing point (T simultaneously m) be higher than 85 ℃, the safety problem that has overcome liquid electrolyte lithium ion battery electrolyte solution easy to leak, volatile, easy flatulence and brought thus.
The fluorinated acrylate monomer that the present invention adopts comprises:
Structural formula is H 2C=C (R 1) CO 2R 2Compound, R wherein 1The structure of group is H or CH 3R 2Unit structure is CH 2CH 2(CF 2) mCF 3, CH 2(CF 2) mCF 3, CH 2(CF 2) mCHF 2, CH 2CH 2(CF 2) mCF (CF 3) 2, CH 2CF 2CH (F) CF 3Deng, m=0-9.Fluorinated acrylate monomer weight accounts for the 2-25Wt% of electrolyte mixed liquor total weight.
Multi-functional acrylate's crosslinking agent that the present invention adopts comprise contain polyethylene glycol two, the acrylate of trifunctional.
Acrylate cross linked dose the structural formula that contains the difunctional of polyethylene glycol is: H 2C=C (R 1) CO 2(CH 2CH 2O) n-R-(CH 2CH 2O) n, OCC (R 1)=CH 2, R wherein 1The structure of group is H or CH 3The structure of R group is (CH 2CH 2O) m, SiH 2, Si (CH 3) 2Or Si (OCH 3) 2n＝0-10，n’＝0-10，m＝0-10。
Acrylate cross linked dose of difunctional that contains polyethylene glycol also can have phenyl ring, and its structural formula is:
[H 2C=C (R 1) CO 2(CH 2CH 2O) nC 6H 4] 2C (CH 3) 2, R wherein 1The structure of group is H or CH 3, n=0-10, C 6H 4Be phenyl ring.
The structural formula that contains trifunctional group acrylate's crosslinking agent of polyethylene glycol is:
[CH 2=C (R 1) CO 2(CH 2CH 2O) nCH 2] 3CR, wherein R 1The structure of group is H or CH 3, the value of n is between 0-15, and the structure of R group is CH 3Or C 2H 5
Above multi-functional acrylate's crosslinking agent weight accounts for the 2-15Wt% of electrolyte mixed liquor total weight.
Fluorinated acrylate monomer of the present invention as:
H 2C=C (CH 3) CO 2CH 2CF 3(HFC-143a ylmethyl acrylate, Trifluoroethylmethacrylate), H 2C=CHCO 2CH 2CF 3(HFC-143a base acrylate, Trifluoroethylacrylate), H 2C=C (CH 3) CO 2CH 2CF 2CHF 2(tetrafluoropropane ylmethyl acrylate, Tetrfluoropropyl methacrylate), H 2C=CHCO 2CH 2CF 2CHF 2(tetrafluoropropane base acrylate, Tetrfluoropropyl acrylate), H 2C=C (CH 3) CO 2CH 2CF 2CF 3(pentafluoropropane ylmethyl acrylate, Pentafluoropropyl methacrylate), H 2C=CHCO 2CH 2CF 2CF 3(pentafluoropropane base acrylate, Pentafluoropropyl acrylate), H 2C=C (CH 3) CO 2CH (CF 3) 2(the different propyl methacrylate of hexafluoro, Hexafluoroisopropyl methacrylate), H 2C=C (CH 3) CO 2CH 2CF 2CH (F) CF 3(hexafluoro butane ylmethyl acrylate, Hexafluorobutylmethacrylate), H 2C=CHCO 2CH 2CF 2CH (F) CF 3(hexafluoro butane base acrylate, Hexafluorobutyl acrylate), H 2C=C (CH 3) CO 2CH 2CF 2CF 2CF 3(seven fluorine butane group methacrylates, Heptafluorobutyl metharcylate), H 2C=CHCO 2CH 2CF 2CF 2CF 3(seven fluorine butane group acrylate, Heptafluorobutyl arcylate), H 2C=C (CH 3) CO 2CH 2CH 2(CF 2) 6CF (CF 3) 2(ten hexafluoros-(trifluoromethyl) decyl methacrylate, Hexadecafluoro-(trifluoromethyl) decyl methacrylate), H 2C=CHCO 2CH 2CH 2(CF 2) 6CF (CF 3) 2(ten hexafluoros-(trifluoromethyl) decyl acrylate, Hexadecafluoro-(trifluoromethyl) decyl acrylate), H 2C=C (CH 3) CO 2CH 2(CF 2) 7CHF 2(ten hexafluoro nonyl methacrylates, Hexadecafluorononyl methacrylate), H 2C=CHCO 2CH 2CH 2(CF 2) 7CHF 2(ten hexafluoro nonyl acrylate, Hexadecafluorononyl acrylate), H 2C=C (CH 3) CO 2CH 2CH 2(CF 2) 7CF 3(17 fluorine decyl methacrylates, Heptadecafluorodecyl methacrylate), H 2C=CHCO 2CH 2CH 2(CF 2) 7CF 3(17 fluorine decyl acrylate, Heptadecafluorodecyl acrylate), H 2C=C (CH 3) CO 2CH 2CH 2(CF 2) 9CF 3(21 fluorine dodecyl methyl acrylate, Heneicosafluorododecyl methacrylate) and H 2C=CHCO 2CH 2CH 2(CF 2) 9CF 3(21 fluorine dodecyl acrylate, Heneicosafluorododecyl acrylate) etc.
Bifunctional acrylate's crosslinking agent of polyethylene glycol of the present invention is as H 2C=CHCO 2(CH 2CH 2O) 1OCCH=CH 2(glycol diacrylate, ethylene glycoldiacrylate), H 2C=C (CH 3) CO 2(CH 2CH 2O) 1OCC (CH 3)=CH 2(ethylene glycol dimethacrylate, ethylene glycol dimethacrylate), H 2C=CHCO 2(CH 2CH 2O) 2OCCH=CH 2(diethylene glycol diacrylate, Di (ethylene glycol) diacrylate), H 2C=C (CH 3) CO 2(CH 2CH 2O) 2OCC (CH 3)=CH 2(diethylene glycol dimethylacrylate, Di (ethylene glycol) dimethacrylate), H 2C=CHCO 2(CH 2CH 2O) 3OCCH=CH 2(triethylene glycol diacrylate, Tri (ethylene glycol) diacrylate), H 2C=C (CH 3) CO 2(CH 2CH 2O) 3OCC (CH 3)=CH 2(triethylene glycol dimethylacrylate, Tri (ethylene glycol) dimethacrylate), H 2C=CHCO 2(CH 2CH 2O) 4OCCH=CH 2(tetraethylene glycol diacrylate, Tetra (ethylene glycol) diacrylate), H 2C=C (CH 3) CO 2(CH 2CH 2O) 4OCC (CH 3)=CH 2(TEG dimethylacrylate, Tetra (ethylene glycol) dimethacrylate), H 2C=CHCO 2(CH 2CH 2O) nOCCH=CH 2(polyethyleneglycol diacrylate, Poly (ethyleneglycol) diacrylate, n=5-20), H 2C=C (CH 3) CO 2(CH 2CH 2O) nOCC (CH 3)=CH 2(polyethylene glycol dimethacrylate, Poly (ethylene glycol) dimethacrylate, n=5-20).
Acrylate cross linked dose of difunctional that contains polyethylene glycol and phenyl ring is:
(H 2C=CHCO 2(CH 2CH 2O) nC 6H 4) 2C (CH 3) 2(bisphenol-A ethoxyquin (1 EO/phenol) diacrylate, Bisphenol A ethoxylate (1 EO/phenol) diacrylate), (H 2C=CHCO 2(CH 2CH 2O) nC 6H 4) 2CH 2(bisphenol-A ethoxyquin (2 EO/phenol) diacrylate, Bisphenol Aethoxylate (2 EO/phenol) diacrylate), (H 2C=C (CH 3) CO 2(CH 2CH 2O) nC 6H 4) 2C (CH 3) 2(bisphenol-A ethoxyquin (2 EO/phenol) dimethylacrylate, Bisphenol A ethoxylate (2 EO/phenol) dimethacrylate), (H 2C=CHCO 2(CH 2CH 2O) nC 6H 4) 2C (CH 3) 2(bisphenol-A ethoxyquin (4 EO/phenol) diacrylate, BisphenolA ethoxylate (4 EO/phenol) diacrylate), (H 2C=C (CH 3) CO 2(CH 2CH 2O) nC 6H 4) 2C (CH 3) 2(bisphenol-A ethoxyquin (4 EO/phenol) dimethylacrylate, Bisphenol A ethoxylate (4 EO/phenol) dimethacrylate), (H 2C=C (CH 3) CO 2(CH 2CH 2O) nC 6H 4) 2C (CH 3) 2(bisphenol-A ethoxyquin (15 EO/phenol) dimethylacrylate, Bisphenol A ethoxylate (15 EO/phenol) dimethacrylate) etc.
The trifunctional group acrylate's crosslinking agent that contains polyethylene glycol of the present invention as:
Ethoxyquin trimethylolpropane triacrylate (Trimethylolpropane ethoxylate (EO/OH) Triacrylate (1 EO/OH-TMPTA), ethoxyquin trimethylolpropane triacrylate (Trimethylolpropane ethoxylate (EO/OH) Triacrylate (7/3 EO/OH-TMPTA) and ethoxyquin trimethylolpropane triacrylate (Trimethylolpropane ethoxylate (EO/OH) Triacrylate (14/3 EO/OH-TMPTA) etc.
The thermal initiator that is used for preparing the gel electrolyte polymerization reaction is a free radical polyaddition reaction thermal initiator commonly used, can be: dibenzoyl peroxide ((C 6H 5CO 2) 2, BPO), peroxidating two (o-methyl-benzene formyl) ((CH 3C 6H 4CO 2) 2), acetyl peroxide isobutyryl (CH 3CO-O-O-COCH (CH 3) 2), di-isopropyl peroxydicarbonate (((CH 3) 2CHOCO 2) 2), di-cyclohexylperoxy di-carbonate ((C 6H 11OCO 2) 2), peroxy dicarbonate two (4-tert-butyl group cyclohexyl) (((CH 3) 3CC 6H 10OCO 2) 2) and the peroxidating pivalic acid tert-butyl ester ((CH 3) 3C-CO-O-O-C (CH 3) 3), azodiisobutyronitrile ((CH 3(CH 3) C (CN) N) 2, AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) ((CH 3) 2CHCH 2(CH 3) C (CN) N) 2) etc.Thermal initiator weight accounts for the 0.1-3Wt% of electrolyte mixed liquor total weight.
The liquid lithium ion electrolyte salt solution is: 1M LiPF 6, EC/DEC=1/1 (W/W), 1MLiPF 6, EC/DEC/VC=1/1/0.1 (W/W/W), 1M LiPF 6, EC/DMC=1/1 (W/W), 1MLiPF 6, EC/DMC/VC=1/1/0.1 (W/W/W), 1M LiPF 6, EC/PC=1/1 (W/W), 1MLiPF 6, EC/PC/VC=1/1/0.1 (W/W/W), 1M LiPF 6, EC/DEC/PC=1/1/1 (W/W/W), 1M LiPF 6, EC/DEC/PC/VC=1/1/1/0.1 (W/W/W/W), 1M LiPF 6, EC/DEC/DMC=1/1/1 (W/W/W), 1M LiPF 6, EC/DEC/DMC/VC=1/1/1/0.1 (W/W/W/W); 1M LiPF 6, EC/DMC/EMC=1/1/1 (W/W/W), 1MLiPF 6, EC/DMC/EMC/VC=1/1/1/0.1 (W/W/W/W).
Above-mentioned reactant feed, promptly each components contents of mixed liquor of compositions such as monomer, crosslinking agent, initator, lithium-ion electrolyte salting liquid is as follows:
Fluorinated acrylate monomer: 2-25Wt%;
The multi-functional acrylate's crosslinking agent that contains polyethylene glycol: 2-15Wt%;
Thermal initiator: 0.1-3Wt%;
Liquid lithium ion electrolyte salt solution: 70-95Wt%.
Above-mentioned fluorinated acrylate monomer and contain polyethylene glycol multi-functional acrylate crosslinking agent and be dissolved in and form gel state electrolyte mixed liquor precursor behind the electrolyte solution, copolymerization does not take place in room temperature in mixed liquor below 25 ℃, and maintenance low-viscosity in the quite a long time is arranged, help mixed liquor and evenly injected battery.The mixed liquor that monomer, crosslinking agent, initator, lithium-ion electrolyte salting liquid are formed injects by the vacuum liquid-injection equipment in the battery container of the lithium ion battery cell that is made of positive pole band, negative pole band and diaphragm material, and the heating battery housing makes this mixed liquor generation cross-linking reaction form fluoride gel attitude electrolyte and makes polymer Li-ion battery simultaneously.
The thermal polymerization temperature is better in 65-75 ℃ of scope, has promptly both guaranteed the formation of gel, and the side reaction of having avoided high temperature to cause has again simultaneously guaranteed the performance of product.
Polymer Li-ion battery packing forms of the present invention can be column type, flat box-shaped, thin slice shape or other polymorphic structure, is convenient to the use of various complete machines.
Battery container material of the present invention is aluminium foil-plastics multilayer complex films.
The combining structure form of inside battery anode electrode band, barrier film and negative electrode band can adopt coiling form or lamination form.It is two-sided that cathode film is applied to aluminium foil, and positive electrode active materials is lithium and cobalt oxides (LiCoO 2), lithium manganese oxide (LiMn 2O 4) or lithium-cobalt-nickel oxide (LiNi xCo 1-xO 2, x=0-1), conductive agent is acetylene black or electrically conductive graphite powder, binding agent is the mixture of polyvinylidene fluoride (PVDF) or polyvinylidene fluoride (PVDF) and polyacrylate.It is two-sided that negative electrode film is applied to Copper Foil, and negative active core-shell material is carbosphere (MCMB), Delanium or the mixture of the two, and conductive agent is an acetylene black, and binding agent is the mixture of polyvinylidene fluoride (PVDF) or polyvinylidene fluoride (PVDF) and polyacrylate.
Battery diaphragm adopts the nonwoven fabrics or the perforated membrane of polypropylene (PP), polyethylene (PE) or vinylidene difluoride-hexafluoropropylene copolymer material such as (PVDF-HPF), thickness 10-25 micron, and preferably thickness is at the 10-15 micron, and porosity is greater than 35%.
The inventive method preparation method is simple, and technological requirement is convenient.Because monomer in the inventive method, crosslinking agent, electrolyte solution, initator are as the precursor of gel state electrolyte mixed liquor, therefore very at room temperature mixed liquor has good flowability in the long duration, is suitable for making in the automation electrolyte solution perfusion equipment of battery using.Conductivity during 25 ℃ of gel state electrolyte materials that the inventive method is made is greater than 4 * 10 -3S/cm, and the conductivity subzero 20 ℃ the time is greater than 1 * 10 -3S/cm, gel polymer electrolyte fusing point (T simultaneously m) be higher than 85 ℃, make battery have low internal resistance and high specific energy density, the adverse consequences that it has been avoided electrolyte solution seepage, volatilization, flatulence effectively and has brought thus has a good application prospect.
Embodiment
Example 1 in-situ heat cross bonding legal system is equipped with the manufacture method 1 of fluoride gel attitude electrolyte and polymer Li-ion battery
HFC-143a ylmethyl acrylate (H 2C=C (CH 3) CO 2CH 2CF 3): 10Wt%;
Ethylene glycol dimethacrylate (H 2C=C (CH 3) CO 2(CH 2CH 2O) 1OCC (CH 3)=CH 2): 3Wt%;
Dibenzoyl peroxide ((C 6H 5CO 2) 2, BPO): 0.25Wt%;
Electrolyte solution, 1M liPF 6, EC/DEC/VC=1/1/0.1 (W/W/W): 86.75Wt%.
Under dry environment (relative humidity is lower than 2%) and room temperature situation, by above-mentioned percentage by weight preparation mixed liquor.Mixed liquor should become transparence and good flowability is arranged, adopt vacuum impregnation, the mixed liquor injection is contained the battery cell body of (battery contains anodal band, negative pole band, barrier film and positive and negative lug), make positive electrode, negative material and barrier film absorb mixed liquor, follow the thermal polymerization of carrying out on the throne, polymerization temperature 65-75 ℃, time 60-180 minute, mobile liquid electrolyte was transformed into gel state electrolyte and makes the gel state electrolyte polymer Li-ion battery thus.
Example 2 in-situ heat cross bonding legal systems are equipped with the manufacture method 2 of fluoride gel attitude electrolyte and polymer Li-ion battery
Tetrafluoropropane ylmethyl acrylate (H 2C=C (CH 3) CO 2CH 2CF 2CHF 2): 8Wt%;
Triethylene glycol dimethylacrylate (CH 2=C (CH 3) CO 2(CH 2CH 2O) 3OCC (CH 3)=CH 2): 3Wt%;
Azodiisobutyronitrile ((CH 3(CH 3) C (CN) N) 2, AIBN): 0.3Wt%;
Electrolyte solution, 1M liPF 6, EC/DEC=1/1 (W/W): 88.7Wt%.
Under dry environment (relative humidity is lower than 2%) and room temperature situation, by above-mentioned percentage by weight preparation mixed liquor.Mixed liquor should become transparence and good flowability is arranged, adopt vacuum impregnation, the mixed liquor injection is contained the battery cell body of (battery contains anodal band, negative pole band, barrier film and positive and negative lug), make positive electrode, negative material and barrier film absorb mixed liquor, then carry out thermal polymerization on the throne, polymerization temperature 65-75 ℃, time 60-180 minute, mobile liquid electrolyte was transformed into gel state electrolyte and makes the gel state electrolyte polymer Li-ion battery thus.
Example 3 in-situ heat cross bonding legal systems are equipped with the manufacture method 3 of fluoride gel attitude electrolyte and polymer Li-ion battery
Pentafluoropropane ylmethyl acrylate (H 2C=C (CH 3) CO 2CH 2CF 2CF 3): 10wt%;
Ethoxyquin trimethylolpropane triacrylate (7/3 EO/OH TMPTA): 2.25Wt%;
Peroxy dicarbonate two (4-tert-butyl group cyclohexyl) (((CH 3) 3CC 6H 10OCO 2) 2): 0.25Wt%;
Electrolyte solution, 1M liPF 6, EC/DEC/DMC=1/1/1 (W/W/W): 87.5Wt%.
Under dry environment (relative humidity is lower than 2%) and room temperature situation, by above-mentioned percentage by weight preparation mixed liquor.Mixed liquor should become transparence and good flowability is arranged, adopt vacuum impregnation, the mixed liquor injection is contained the battery cell body of (battery contains anodal band, negative pole band, barrier film and positive and negative lug), make positive electrode, negative material and barrier film absorb mixed liquor, then carry out thermal polymerization on the throne, polymerization temperature 65-75 ℃, time 60-180 minute, mobile liquid electrolyte was transformed into gel state electrolyte and makes the gel state electrolyte polymer Li-ion battery thus.
Example 4 in-situ heat cross bonding legal systems are equipped with the manufacture method 4 of fluoride gel attitude electrolyte and polymer Li-ion battery
The different propyl methacrylate of hexafluoro (H 2C=C (CH 3) CO 2CH (CF 3) 2): 8Wt%:
Bisphenol-A ethoxyquin (4 EO/phenol) dimethylacrylate: 4Wt%:
Azodiisobutyronitrile ((CH 3(CH 3) C (CN) N) 2, AIBN): 0.3Wt%:
Electrolyte solution, 1M liPF 6, EC/DEC/DMC/VC=1/1/1/0.1 (W/W/W/W): 87.7Wt%.
Under dry environment (relative humidity is lower than 2%) and room temperature situation, by above-mentioned percentage by weight preparation mixed liquor.Mixed liquor should become transparence and good flowability is arranged, adopt vacuum impregnation, the mixed liquor injection is contained the battery cell body of (battery contains anodal band, negative pole band, barrier film and positive and negative lug), make positive electrode, negative material and barrier film absorb mixed liquor, then carry out thermal polymerization on the throne, polymerization temperature 65-75 ℃, time 60-180 minute, mobile liquid electrolyte was transformed into gel state electrolyte and makes the gel state electrolyte polymer Li-ion battery thus.
Example 5 in-situ heat cross bonding legal systems are equipped with the manufacture method 5 of fluoride gel attitude electrolyte and polymer Li-ion battery
Hexafluoro butane base acrylate (H 2C=CHCO 2CH 2CF 2CH (F) CF 3): 8Wt%:
Bisphenol-A ethoxyquin (15 EO/phenol) dimethylacrylate: 3.5Wt%:
Peroxy dicarbonate two (4-tert-butyl group cyclohexyl) (((CH 3) 3CC 6H 10OCO 2) 2): 0.5Wt%;
Electrolyte solution, 1M liPF 6, EC/DMC/EMC/VC=1/1/1/0.1 (W/W/W/W): 88Wt%;
Under dry environment (relative humidity is lower than 2%) and room temperature situation, by above-mentioned percentage by weight preparation mixed liquor.Mixed liquor should become transparence and good flowability is arranged, adopt vacuum impregnation, the mixed liquor injection is contained the battery cell body of (battery contains anodal band, negative pole band, barrier film and positive and negative lug), make positive electrode, negative material and barrier film absorb mixed liquor, then carry out thermal polymerization on the throne, polymerization temperature 65-75 ℃, time 60-180 minute, mobile liquid electrolyte was transformed into gel state electrolyte and makes the gel state electrolyte polymer Li-ion battery thus.

Claims (11)

1、一种含氟凝胶态电解质材料的在位热交联制备方法，其特征是以含氟丙烯酸酯为单体，含聚乙二醇的双官能团或三官能团丙烯酸酯为交联剂，把单体、交联剂、热引发剂、锂离子电解质盐溶液组成的电解质混合液注入锂离子电池电芯中，通过在位热化学交联方法使两种丙烯酸酯共聚，电解质中的溶液反应时包裹于丙烯酸酯共聚物网络中，制得含氟凝胶态电解质材料，在位聚合60-80℃温度，时间60-180分钟。1. A preparation method for in-situ thermal crosslinking of a fluorine-containing gel state electrolyte material, which is characterized in that a fluorine-containing acrylate is used as a monomer, and a difunctional or trifunctional acrylate containing polyethylene glycol is used as a crosslinking agent. Inject the electrolyte mixture composed of monomer, cross-linking agent, thermal initiator and lithium-ion electrolyte salt solution into the lithium-ion battery cell, and copolymerize the two acrylates by in-situ thermochemical cross-linking method, and the solution in the electrolyte reacts Wrapped in the acrylate copolymer network to prepare fluorine-containing gel state electrolyte material, the temperature is 60-80 ℃ for in-situ polymerization, and the time is 60-180 minutes. 2、根据权利要求1所述的含氟凝胶态电解质材料的在位热交联制备方法，其特征是含氟丙烯酸酯单体是：结构式为H2C＝C(R1)CO2R2的化合物，其中R1基团的结构为H或CH3；R2结构为CH2CH2(CF2)mCF3、CH2(CF2)mCF3、CH2(CF2)mCHF2、CH2CH2(CF2)mCF(CF3)2、CH2CF2CH(F)CF3，m＝0-9，含氟丙烯酸酯单体重量占电解质混合液总重量的2-25Wt％。2. The in-situ thermal crosslinking preparation method of fluorine-containing gel electrolyte material according to claim 1, characterized in that the fluorine-containing acrylate monomer is: the structural formula is H 2 C=C(R 1 )CO 2 R 2 , wherein the structure of R 1 group is H or CH 3 ; the structure of R 2 is CH 2 CH 2 (CF 2 ) m CF 3 , CH 2 (CF 2 ) m CF 3 , CH 2 (CF 2 ) m CHF 2 , CH 2 CH 2 (CF 2 ) m CF(CF 3 ) 2 , CH 2 CF 2 CH(F)CF 3 , m=0-9, the weight of the fluorine-containing acrylate monomer accounts for the total weight of the electrolyte mixture 2-25 wt%. 3、根据权利要求1所述的含氟凝胶态电解质材料的在位热交联制备方法，其特征是以含聚乙二醇的双官能团丙烯酸酯为交联剂，含聚乙二醇的双官能团丙烯酸酯交联剂的结构式为：3. The in-situ thermal cross-linking preparation method of fluorine-containing gel state electrolyte material according to claim 1, characterized in that the cross-linking agent is a difunctional acrylate containing polyethylene glycol, and the polyethylene glycol-containing The structural formula of the bifunctional acrylate crosslinking agent is: H2C＝C(R1)CO2(CH2CH2O)nCOC(R1)＝CH2，其中R1基团的结构为H或CH3，n＝1-20，含聚乙二醇的双官能团丙烯酸酯交联剂重量占电解质混合液总重量的2-15Wt％。H 2 C=C(R 1 )CO 2 (CH 2 CH 2 O) n COC(R 1 )=CH 2 , wherein the structure of R 1 group is H or CH 3 , n=1-20, including polyethylene The weight of the bifunctional acrylate crosslinking agent of diol accounts for 2-15wt% of the total weight of the electrolyte mixture. 4、根据权利要求1所述的含氟凝胶态电解质材料的在位热交联制备方法，，其特征是含聚乙二醇的双官能团的丙烯酸酯交联剂带有苯环，其结构式为：4. The in-situ thermal crosslinking preparation method of fluorine-containing gel state electrolyte material according to claim 1, characterized in that the bifunctional acrylate crosslinking agent containing polyethylene glycol has a benzene ring, and its structural formula for: [H2C＝C(R1)CO2(CH2CH2O)nC6H4]2C(CH3)2，其中R1基团的结构为H或CH3，n＝1-10，C6H4为苯环。[H 2 C=C(R 1 )CO 2 (CH 2 CH 2 O) n C 6 H 4 ] 2 C(CH 3 ) 2 , wherein the structure of the R 1 group is H or CH 3 , n=1- 10, C 6 H 4 is a benzene ring. 5、根据权利要求1所述的含氟凝胶态电解质材料的在位热交联制备方法，其特征是含聚乙二醇的三官能团丙烯酸酯交联剂的结构式为：5. The preparation method of in-situ thermal crosslinking of fluorine-containing gel state electrolyte material according to claim 1, characterized in that the structural formula of the polyethylene glycol-containing trifunctional acrylate crosslinking agent is: (CH2＝C(R1)CO2(CH2CH2O)nCH2)3CR，其中R1基团的结构为H或CH3，n的值在1-15之间，R基团的结构为CH3或C2H5。(CH 2 ＝C(R 1 )CO 2 (CH 2 CH 2 O) n CH 2 ) 3 CR, wherein the structure of the R 1 group is H or CH 3 , the value of n is between 1-15, and the R group The structure of the group is CH 3 or C 2 H 5 . 6、根据权利要求1所述的含氟凝胶态电解质材料的在位热交联制备方法，其特征是凝胶态电解质的反应物原料，即单体、交联剂、引发剂、锂离子电解质盐溶液组成的电解质混合液各物质组分的百分比含量(wt％)如下：6. The in-situ thermal crosslinking preparation method of fluorine-containing gel state electrolyte material according to claim 1, characterized in that the reactant raw materials of the gel state electrolyte are monomers, crosslinking agents, initiators, lithium ions The percentage content (wt %) of each material component of the electrolytic mixed liquid that electrolytic salt solution is formed is as follows: 含氟丙烯酸酯单体：2-25；Fluorinated acrylate monomer: 2-25; 含聚乙二醇的双或三官能团丙烯酸酯交联剂：2-15；Di- or tri-functional acrylate crosslinking agent containing polyethylene glycol: 2-15; 热引发剂：0.1-3；Thermal initiator: 0.1-3; 液态锂离子电解质盐溶液：70-95。Liquid lithium ion electrolyte salt solution: 70-95. 7、根据权利要求1所述的含氟凝胶态电解质材料的在位热交联制备方法，其特征是在位聚合温度是65-75℃。7. The preparation method of in-situ thermal crosslinking of fluorine-containing gel electrolyte material according to claim 1, characterized in that the in-situ polymerization temperature is 65-75°C. 8、根据权利要求1所述的含氟凝胶态电解质材料的聚合物锂离子电池的制备方法，其特征是单体、交联剂、引发剂、锂离子电解质盐溶液组成的混合液通过真空注液设备注入由正极带、负极带及隔膜材料构成的锂离子电池电芯的电池壳体内，加热电池壳体使该混合液发生交联反应形成含氟凝胶态电解质材料并同时制得聚合物锂离子电池。8. The method for preparing a polymer lithium-ion battery containing fluorine-containing gel electrolyte material according to claim 1, characterized in that the mixed solution composed of monomer, cross-linking agent, initiator and lithium-ion electrolyte salt solution is passed through a vacuum The liquid injection equipment injects into the battery case of the lithium-ion battery cell composed of the positive electrode tape, the negative electrode tape and the diaphragm material, and heats the battery case to cause the mixed liquid to undergo a cross-linking reaction to form a fluorine-containing gel state electrolyte material and simultaneously obtain a polymerized Lithium-ion battery. 9、根据权利要求8所述的含氟凝胶态电解质材料的聚合物锂离子电池的制备方法，其特征是锂离子电池封装成圆柱型或扁平方块型或薄片型，电芯的正负极组合结构是卷绕式或迭层式。9. The method for preparing a polymer lithium-ion battery containing fluorine-containing gel state electrolyte material according to claim 8, characterized in that the lithium-ion battery is packaged into a cylindrical shape or a flat block shape or a sheet shape, and the positive and negative electrodes of the battery cell are The combined structure is winding or laminated. 10、根据权利要求8所述的含氟凝胶态电解质材料的聚合物锂离子电池的制备方法，其特征是电池隔膜是聚丙烯、聚乙烯或偏二氟乙烯-六氟丙烯共聚物材料制作的无纺布或多孔膜，厚度10-25微米。10. The method for preparing polymer lithium-ion batteries containing fluorine-containing gel electrolyte materials according to claim 8, wherein the battery separator is made of polypropylene, polyethylene or vinylidene fluoride-hexafluoropropylene copolymer materials A non-woven fabric or porous film with a thickness of 10-25 microns. 11、根据权利要求10所述的含氟凝胶态电解质材料的聚合物锂离子电池的制备方法，其特征是电池隔膜厚度是10-15微米。11. The method for preparing a polymer lithium-ion battery containing fluorine gel electrolyte material according to claim 10, characterized in that the thickness of the battery diaphragm is 10-15 microns.
CNA2004100160365A 2004-01-29 2004-01-29 Preparation method of in-situ thermal crosslinking of fluorine-containing gel electrolyte material and preparation method of polymer lithium-ion battery Pending CN1558463A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNA2004100160365A CN1558463A (en) 2004-01-29 2004-01-29 Preparation method of in-situ thermal crosslinking of fluorine-containing gel electrolyte material and preparation method of polymer lithium-ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNA2004100160365A CN1558463A (en) 2004-01-29 2004-01-29 Preparation method of in-situ thermal crosslinking of fluorine-containing gel electrolyte material and preparation method of polymer lithium-ion battery

Publications (1)

Publication Number Publication Date
CN1558463A true CN1558463A (en) 2004-12-29

Family

ID=34351663

Family Applications (1)

Application Number Title Priority Date Filing Date
CNA2004100160365A Pending CN1558463A (en) 2004-01-29 2004-01-29 Preparation method of in-situ thermal crosslinking of fluorine-containing gel electrolyte material and preparation method of polymer lithium-ion battery

Country Status (1)

Country Link
CN (1) CN1558463A (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101807717A (en) * 2010-04-20 2010-08-18 诺莱特科技(苏州)有限公司 Gel electrolyte, preparation method thereof, battery using gel electrolyte and preparation method thereof
CN102522589A (en) * 2011-12-16 2012-06-27 浙江大东南集团有限公司 Novel gel polymer electrolyte with interpenetrating network structure and preparation method and application thereof
CN105811007A (en) * 2016-06-06 2016-07-27 北京师范大学 Electrolyte gel, lithium-sulfur battery and method for preparing electrolyte gel
CN107078339A (en) * 2014-10-21 2017-08-18 日本电气株式会社 Secondary cell and its manufacture method
CN107768716A (en) * 2016-08-15 2018-03-06 通用汽车环球科技运作有限责任公司 Gel electrolyte and its predecessor
CN109326822A (en) * 2018-11-05 2019-02-12 珠海光宇电池有限公司 A kind of preparation method and lithium ion battery of all solid state fluoropolymer electrolyte film
CN109546205A (en) * 2018-06-13 2019-03-29 上海大学 Using the preparation method of the lithium ion battery of organo-mineral complexing gel polymer electrolyte
CN109671978A (en) * 2018-12-20 2019-04-23 苏州大学 A kind of high voltage withstanding solid polymer electrolyte, preparation method and applications
CN113054241A (en) * 2021-03-04 2021-06-29 湖南立方新能源科技有限责任公司 Solid-state lithium battery and preparation method thereof
CN113087856A (en) * 2019-12-23 2021-07-09 通用汽车环球科技运作有限责任公司 Gelling agents for forming gel electrolytes and methods relating thereto
CN118888838A (en) * 2024-09-03 2024-11-01 江苏正力新能电池技术股份有限公司 Flame retardant gel electrolyte, battery and preparation method thereof

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101807717A (en) * 2010-04-20 2010-08-18 诺莱特科技(苏州)有限公司 Gel electrolyte, preparation method thereof, battery using gel electrolyte and preparation method thereof
CN102522589A (en) * 2011-12-16 2012-06-27 浙江大东南集团有限公司 Novel gel polymer electrolyte with interpenetrating network structure and preparation method and application thereof
CN107078339A (en) * 2014-10-21 2017-08-18 日本电气株式会社 Secondary cell and its manufacture method
CN107078339B (en) * 2014-10-21 2019-12-17 日本电气株式会社 Secondary battery and method for manufacturing same
CN105811007A (en) * 2016-06-06 2016-07-27 北京师范大学 Electrolyte gel, lithium-sulfur battery and method for preparing electrolyte gel
CN105811007B (en) * 2016-06-06 2019-08-27 北京师范大学 Electrolyte gel, lithium-sulfur battery and preparation method
US10326166B2 (en) 2016-08-15 2019-06-18 GM Global Technology Operations LLC Gel electrolytes and precursors thereof
CN107768716A (en) * 2016-08-15 2018-03-06 通用汽车环球科技运作有限责任公司 Gel electrolyte and its predecessor
CN107768716B (en) * 2016-08-15 2020-12-08 通用汽车环球科技运作有限责任公司 Gel electrolyte and precursor thereof
CN109546205A (en) * 2018-06-13 2019-03-29 上海大学 Using the preparation method of the lithium ion battery of organo-mineral complexing gel polymer electrolyte
CN109326822A (en) * 2018-11-05 2019-02-12 珠海光宇电池有限公司 A kind of preparation method and lithium ion battery of all solid state fluoropolymer electrolyte film
CN109326822B (en) * 2018-11-05 2020-11-17 珠海冠宇电池股份有限公司 Preparation method of all-solid fluoropolymer electrolyte membrane and lithium ion battery
CN109671978A (en) * 2018-12-20 2019-04-23 苏州大学 A kind of high voltage withstanding solid polymer electrolyte, preparation method and applications
CN109671978B (en) * 2018-12-20 2022-02-11 苏州大学 High-voltage-resistant solid polymer electrolyte, preparation method and application thereof
CN113087856A (en) * 2019-12-23 2021-07-09 通用汽车环球科技运作有限责任公司 Gelling agents for forming gel electrolytes and methods relating thereto
CN113054241A (en) * 2021-03-04 2021-06-29 湖南立方新能源科技有限责任公司 Solid-state lithium battery and preparation method thereof
CN118888838A (en) * 2024-09-03 2024-11-01 江苏正力新能电池技术股份有限公司 Flame retardant gel electrolyte, battery and preparation method thereof
CN118888838B (en) * 2024-09-03 2024-12-31 江苏正力新能电池技术股份有限公司 Flame-retardant gel electrolyte, battery and preparation method thereof

Similar Documents

Publication Publication Date Title
CN113258132B (en) Solid electrolyte, preparation method thereof and solid battery
CN1324728C (en) Lithium secondary cell of electrolyte decomposition being inhibited and preparing process thereof
CN1152086C (en) Process for preparing gel-state lithium ion polymer as electrolyte and bettery
JP2019204765A (en) Method for manufacturing all-solid lithium ion battery
CN110556586A (en) Polymeric organic-inorganic composite solid electrolyte and in-situ assembled all-solid-state battery
CN103633367B (en) A kind of gel polymer electrolyte and polymer Li-ion battery and preparation method thereof
WO2021052363A1 (en) Polymer lithium secondary battery and in-situ preparation method therefor
CN111533851A (en) Preparation method of polymer electrolyte and application of polymer electrolyte in all-solid-state battery
WO2016133279A1 (en) Gel polymer electrolyte, method for preparing same, and electrochemical device comprising same
JP2011171096A (en) Nonaqueous electrolyte battery
CN1930703A (en) Separator coated with electrolyte-miscible polymer and electrochemical device using the same
CN1917274A (en) Electrolyte compound of multilayer gel, and prepartion method for applied to lithium ion battery
CN117080530B (en) A lithium metal battery and its preparation method and battery pack
CN110048158A (en) A kind of in-situ polymerization ELECTRODE WITH BILAYER POLYMERIC object dielectric film and its preparation method and application
CN103000956A (en) Manufacturing method of lithium ion battery containing gel electrolyte
CN1295724A (en) Method of making polymer electrolyte electrochemical cells
JP5187720B2 (en) Lithium ion polymer battery
CN101250276A (en) Preparation method of modified diaphragm for polymer lithium-ion battery
CN103035943A (en) Polymer electrolyte additive and gel polymer cell using same
JP6116029B2 (en) Gel electrolyte and polymer secondary battery using the same
CN1558463A (en) Preparation method of in-situ thermal crosslinking of fluorine-containing gel electrolyte material and preparation method of polymer lithium-ion battery
CN102206420A (en) Composition for battery diaphragm, battery diaphragm and lithium-ion secondary battery
JP5105807B2 (en) Lithium polymer battery
CN103151563A (en) Polymer cell and preparation method thereof
CN1229816C (en) Polymer gel electrolyte, lithium battery using the polymer gel electrolyte, and method for producing the electrolyte and battery

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication