CN113839099A - Preparation method of high-performance all-solid-state lithium ion battery - Google Patents
Preparation method of high-performance all-solid-state lithium ion battery Download PDFInfo
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- CN113839099A CN113839099A CN202111121492.6A CN202111121492A CN113839099A CN 113839099 A CN113839099 A CN 113839099A CN 202111121492 A CN202111121492 A CN 202111121492A CN 113839099 A CN113839099 A CN 113839099A
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- lithium ion
- polymer electrolyte
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- ion battery
- state lithium
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 80
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical group O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 24
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 17
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 17
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 15
- 239000002033 PVDF binder Substances 0.000 claims description 13
- 238000005266 casting Methods 0.000 claims description 13
- -1 organo montmorillonite Chemical compound 0.000 claims description 13
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims description 12
- 159000000002 lithium salts Chemical class 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910017059 organic montmorillonite Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- JRONPIZRZBBOBR-UHFFFAOYSA-N chlorine perchlorate Chemical compound ClOCl(=O)(=O)=O JRONPIZRZBBOBR-UHFFFAOYSA-N 0.000 claims 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 12
- 239000010410 layer Substances 0.000 description 10
- 230000005012 migration Effects 0.000 description 9
- 238000013508 migration Methods 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 238000010586 diagram Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 6
- 239000004926 polymethyl methacrylate Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
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- 230000001351 cycling effect Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 3
- 229910000159 nickel phosphate Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- JYNTUIIZRRKCJZ-UHFFFAOYSA-N ClCl(=O)(=O)=O Chemical compound ClCl(=O)(=O)=O JYNTUIIZRRKCJZ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
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- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- AFYAQDWVUWAENU-UHFFFAOYSA-H nickel(2+);diphosphate Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O AFYAQDWVUWAENU-UHFFFAOYSA-H 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
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- 229920001523 phosphate polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
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- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- 238000006479 redox reaction Methods 0.000 description 1
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- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
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- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
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- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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Abstract
A preparation method of a high-performance all-solid-state lithium ion battery relates to a preparation method of a high-performance all-solid-state lithium ion battery. The invention aims to solve the problem of low conductivity of the all-solid-state lithium ion battery diaphragm prepared by the existing method. According to the inventionThe method comprises the following steps: firstly, preparing a polymer electrolyte precursor solution; secondly, preparing a polymer electrolyte precursor liquid monomer; thirdly, preparing polymer electrolyte precursor liquid monomer through polymerization; fourthly, preparing the polymer electrolyte of the all-solid-state lithium ion battery; and fifthly, assembling the battery. The ionic conductivity of the all-solid-state lithium ion battery diaphragm prepared by the method reaches 1.1 multiplied by 10-‑3S·cm‑1And the safety performance of the lithium ion battery is greatly improved, and the lithium ion battery also has the advantages of high specific charge/discharge capacity, stable cycle performance, safe and simple operation and the like, and is suitable for large-scale preparation and commercial application. The invention is applied to the field of all-solid-state lithium ion batteries.
Description
Technical Field
The invention relates to a method for preparing all-solid-state lithium ion battery polymer electrolyte.
Background
Commercial lithium ion batteries still face safety issues due to the presence of electrolytes that are prone to fire and leakage hazards. Meanwhile, the development of the conventional liquid lithium ion battery also encounters a bottleneck due to the growth of lithium dendrites. Therefore, flammable electrolytes are a major obstacle to overcome, and a contradiction between high energy density and high safety needs to be solved. Solid polymer-based lithium ion batteries have therefore attracted considerable attention for their high safety. However, their low ionic conductivity, poor mechanical properties and insufficient cycle life limit their practical applications. Wu et al select nickel phosphate (VSB-5) nanorods as filler to prepare a novel polyethylene oxide/LiTFSI/nickel phosphate polymer electrolyte. The ionic conductivity of the polymer electrolyte is up to 4.83 x 10-5S·cm-1The electrochemical stability is as high as 4.13V. The increase in ionic conductivity is attributed to the interaction between nickel phosphate and polyethylene oxide-LiTFSI, which can reduce crystallinity (z.wu, z.xie, a.yoshida, j.wang, t.yu, z.wang, x.hao, a.abudula, g.guan, j.colloid Interface sci.565(2020) 110-. The Xushi adopts a self-assembled polyethylene oxide @ silicon dioxide three-dimensional network structure composite polymer electrolyte, and due to a rigid-flexible coupling structure of strong Lewis acid base and weak hydrogen bonds, silicon dioxide nano particles are uniformly dispersed into polyethylene oxide, so that the crystallinity of the polyethylene oxide can be remarkably reduced, and the ionic conductivity is enhanced (1.1 multiplied by 10)-4S·cm-1) And high interfacial stability between electrolyte and electrode (z.xu, t.yang, x.chu, h.su, z.wang, n.chen, b.gu, h.zhang, w.ding, h.zhang, w.yang, ACS appl.mater.interfaces 12 (2. Yang)020)10341-10349.). However, the problems of large interfacial resistance, poor battery performance at low temperature, low ionic conductivity and the like still exist in the large-scale production of the solid-state lithium ion battery, and the like are still solved.
Disclosure of Invention
The invention aims to solve the problem that the diaphragm of the all-solid-state lithium ion battery prepared by the existing method has low ionic conductivity, and provides a preparation method of the all-solid-state lithium ion battery with high performance.
The invention relates to a preparation method of a high-performance all-solid-state lithium ion battery, which comprises the following steps:
pretreatment of polymer electrolyte precursor solution
Respectively dissolving poly (vinylidene fluoride-hexafluoropropylene) copolymer, polyvinylidene fluoride and organic montmorillonite in a mass ratio of 5:1: 1-4: 3:2 by using an organic solvent N, N-dimethylformamide, uniformly stirring at room temperature, and mixing the uniformly stirred solutions;
preparation of polymer electrolyte precursor liquid monomer
Mixing methyl methacrylate: poly (vinylidene fluoride-hexafluoropropylene) copolymer, polyvinylidene fluoride, organo montmorillonite: adding lithium salt into the uniform solution obtained in the step one according to the mass ratio of 20:1: 3-35: 9:20, and stirring at room temperature to obtain a uniform light yellow solution;
thirdly, polymerization of polymer electrolyte precursor liquid monomer
Adding an initiator into the light yellow solution obtained in the step two, and carrying out prepolymerization for 10-30 min under heating conditions to obtain a precursor solution;
preparation of four-phase and all-solid-state lithium ion battery polymer electrolyte
Casting the precursor solution obtained in the third step on a glass plate by adopting a solution casting method, drying the glass plate for 2 to 4 hours in vacuum at the temperature of 75 to 95 ℃ to obtain a light yellow polymer electrolyte film, and slicing the film for later use after cooling to room temperature;
fifth, the battery assembly
And D, assembling the negative electrode shell, the polymer electrolyte film obtained in the step four, the lithium sheet, the foamed nickel and the positive electrode shell in a glove box filled with argon in sequence to obtain the high-performance all-solid-state lithium ion battery.
The organic montmorillonite in the step one is modified montmorillonite.
The modified montmorillonite aims to increase the interlayer spacing of montmorillonite, facilitate the migration of lithium ions among montmorillonite layers, change the hydrophilicity among montmorillonite layers, enhance the dispersibility of montmorillonite in an organic solvent and increase the interface and the interface energy to form an active site in the migration of lithium ions. The basic structural unit of montmorillonite is a sheet of aluminous octahedron sandwiched between two sheets of silicon-oxygen tetrahedron, which form a layered structure by sharing oxygen atoms. The surfaces of the sheets have excessive negative charges, so that the montmorillonite sheets can absorb cations, lithium ions in the lithium ion battery can be absorbed between layers, montmorillonite is a hydrophilic microenvironment which is not beneficial to lipophilic monomer and polymer insertion, organic parts in the organically modified montmorillonite are left between the layers, the interlayer spacing of the montmorillonite can be increased by the modified montmorillonite, the hydrophilicity of the montmorillonite layers is changed into hydrophobicity, the dispersity of the montmorillonite in an organic solvent is enhanced, channels for lithium ions to be transmitted through polymer blocks, montmorillonite layers and polymer blocks are erected, the interface area in a polymer electrolyte is increased, the interface energy is improved, active sites for lithium ion migration are increased, and the lithium ions are easy to migrate in the solid electrolyte, so that the conductivity and the migration number of the lithium ions are improved.
Further, the lithium salt added in the second step is one of perchloric acid chloride, lithium bistrifluoromethanesulfonimide, lithium tetrafluoroborate, lithium hexafluorophosphate and lithium hexafluoroarsenate.
The perchloric acid chloride, the lithium bis (trifluoromethanesulfonyl) imide, the lithium tetrafluoroborate, the lithium hexafluorophosphate and the lithium hexafluoroarsenate have higher electrochemical stability and conductivity, so that consumed lithium ions can be continuously supplemented in the polymer electrolyte, and the long-term stable circulation of the battery is promoted.
Further, after the lithium salt is added in the step two, the stirring time is controlled to be 4-8 h.
The time is controlled here to ensure that the lithium salt is completely dissolved and does not precipitate during use, insufficient stirring time may result in insufficient dissolution of the lithium salt, and excessively long stirring time may result in precipitation of the lithium salt.
Further, the initiator in the third step is one of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide and isophenylhydroperoxide.
Azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide and isophenylhydroperoxide are unstable molecules and easily form free radicals, and the free radicals can induce the polymerization of methyl methacrylate monomers.
Further, the initiator in the third step accounts for 0.03-0.06% of the total mass of the light yellow polymer electrolyte mixed in the second step, and the prepolymerization temperature is 70-100 ℃.
The polymerization degree of methyl methacrylate monomers is insufficient due to too low quality of benzoyl peroxide, a film cannot be formed in the drying process, and the polymerization degree of the methyl methacrylate monomers is too high due to excessive benzoyl peroxide, so that the methyl methacrylate monomers are solidified in the prepolymerization process and cannot be poured into a film.
Further, when the polymer electrolyte film is prepared by the casting method in the fourth step, the polymer electrolyte film needs to be stood for defoaming in advance.
The defoaming of stewing in advance prevents to dry in-process film breakage, and the precursor liquid that does not defoam in advance can form great defect in bubble department at the film forming process, leads to the waste of experiment failure and medicine.
The invention has the following beneficial effects:
the invention adopts a solution casting method to prepare the all-solid-state lithium ion battery diaphragm by using the compatibility of three insoluble phases as a matrix, and mainly inspects the influence of the polymethyl methacrylate polymerized by the methyl methacrylate on the morphology of a polymer electrolyte membrane and the electrochemical performance of a lithium ion battery, including ionic conductivity, specific charge-discharge capacity, cycle efficiency and cycle stability. The ion conductivity of the all-solid-state lithium ion battery diaphragm prepared by using methyl methacrylate polymerization as a matrix casting method reaches 1.1 multiplied by 10 ═ sigma-3 S cm-1And a new way is opened up for the all-solid-state lithium ion battery with high performance and high safety.
The polyvinylidene fluoride has poor ionic conductivity, but has close arrangement among molecular chains, stronger hydrogen bonds and good toughness, and the poly (vinylidene fluoride-hexafluoropropylene) copolymer has higher density pores and better electrochemical stability, but has higher cost and poor mechanical strength, which can just neutralize the rigidity of the polyvinylidene fluoride to ensure that the polymer electrolyte keeps soft, the methyl methacrylate added in the step two can be used as a solubilizer to be fully contacted and uniformly mixed with other two matrixes and the filler, and then carrying out polymerization treatment on methyl methacrylate, wherein the three substances are combined and compatible, so that the toughness and mechanical strength of the polymer electrolyte can be enhanced to the greatest extent, the cycle performance of the battery can be improved, the lithium dendritic crystal generated in the battery cycle process can be prevented from puncturing the diaphragm to cause fire, and the safety of the solid polymer electrolyte film is improved.
Through electrochemical tests, we compare with the similar materials reported at present, and the results are as follows:
the ionic conductivity and initial specific discharge capacity of the all-solid-state polymer electrolyte are superior to those of the currently reported polymer electrolytes (ACS Applied Materials & Interfaces, 2018)), (ACS Omega,2019,4(1):95-103.), (ChemElectrochem,2020,7(5): 1213-;
the existing all-solid-state lithium ion battery has the problems of low ionic conductivity and rapid capacity attenuation, and is difficult to realize commercial production, and the all-solid-state polymer electrolyte can accelerate the dissociation of lithium salt and allow lithium ions to stably migrate under the help of the layered structure of organic montmorillonite and a large amount of Lewis acid centers. The invention adopts the solution casting method to prepare the polymer electrolyte membrane, because the surface tension of each substance in the polymer electrolyte is different, a large number of interfaces are generated, the interface of a modified montmorillonite layer with high specific surface area is formed, the poly (vinylidene fluoride-hexafluoropropylene) copolymer has a low glass transition temperature of-55 degrees and is far lower than that of a homopolymer, the transmission of lithium ions in the poly (vinylidene fluoride-hexafluoropropylene) copolymer follows the Allen-nius formula, the poly (vinylidene fluoride-hexafluoropropylene) copolymer has good conductivity, because the poly (vinylidene fluoride-hexafluoropropylene) copolymer has high fluidity and is easily inserted into the montmorillonite layer to form a lithium ion channel of a polymer block-modified montmorillonite layer-polymer block, the polyvinylidene fluoride is easily fused with the poly (vinylidene fluoride-hexafluoropropylene) copolymer, and the modified montmorillonite can be introduced into the poly (vinylidene fluoride-hexafluoropropylene) copolymer, polymethyl methacrylate is a main matrix material for bearing the materials, which can improve the self-supporting performance of electrolyte and provide a template for montmorillonite, poly (vinylidene fluoride-hexafluoropropylene) copolymer embedded in layers and polyvinylidene fluoride, so that the modified montmorillonite, poly (vinylidene fluoride-hexafluoropropylene) copolymer, polyvinylidene fluoride and polymethyl methacrylate which wrap and introduce montmorillonite into block polymer are mutually compatible and cooperate to generate a multi-fold, multi-pore morphology and multi-dimensional interface beneficial to lithium ion migration, a lithium ion channel for lithium ion transmission through polymer blocks, montmorillonite layers and polymer blocks is erected, the interface area in polymer electrolyte is increased, the interface energy is improved, the transmission active site of lithium ions is increased, and the ultrahigh ion conductivity is obtained, but also has the advantages of simple and safe operation and suitability for large-scale preparation and commercial application.
Drawings
FIG. 1 is an infrared spectrum of a polymer electrolyte prepared by a method for preparing a high-performance all-solid-state lithium ion battery;
FIG. 2 is an SEM image of a polymer electrolyte prepared by a preparation method of a high-performance all-solid-state lithium ion battery;
FIG. 3 is an XRD (X-ray diffraction) pattern of a polymer electrolyte prepared by a preparation method of a high-performance all-solid-state lithium ion battery;
FIG. 4 is a diagram of the impedance of a polymer electrolyte prepared by a method for preparing a high-performance all-solid-state lithium ion battery;
FIG. 5 is an Arrhenius diagram of a polymer electrolyte prepared by a method for preparing a high-performance all-solid-state lithium ion battery;
FIG. 6 is a constant current polarization curve diagram of an all-solid-state lithium ion battery prepared by a high-performance all-solid-state lithium ion battery preparation method;
FIG. 7 is a multiplying power diagram of an all-solid-state lithium ion battery prepared by a preparation method of a high-performance all-solid-state lithium ion battery;
FIG. 8 is a cyclic voltammogram of an all-solid-state lithium ion battery prepared by a high-performance all-solid-state lithium ion battery preparation method;
FIG. 9 is a graph of specific capacity versus voltage cycled at 0.5C for a comparative example of the present invention;
FIG. 10 is a graph of efficiency versus specific capacity for a comparative example of the present invention cycled at 0.5C;
fig. 11 is a cyclic specific capacity-voltage curve diagram of an all-solid-state lithium ion battery prepared by a high-performance all-solid-state lithium ion battery preparation method at 0.5C;
fig. 12 is a graph of efficiency-specific capacity at 0.5C for an all-solid-state lithium ion battery prepared by a high-performance all-solid-state lithium ion battery preparation method.
Fig. 13 is a comparison graph of electrochemical tests performed on an all-solid-state lithium ion battery prepared by the method for preparing a high-performance all-solid-state lithium ion battery according to example 1 and similar materials reported so far.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples.
Experimental medicine
Experimental medicine
| Name of instrument | Model number | Manufacturer of the product |
| Analytical balance | FC-204 | Shanghai sperm balance |
| Magnetic stirrer | CL-200 | GONGYI CITY YUHUA INSTRUMENT Co.,Ltd. |
| Vacuum green drying box | ZK-82BB | Shanghai laboratory Instrument plant Ltd |
| And type battery sealing machine | MSK-110 | SHENZHEN KEJINGSTAR TECHNOLOGY Ltd. |
| Pole piece punching machine | MSK-T10 | SHENZHEN KEJINGSTAR TECHNOLOGY Ltd. |
| LAND battery test system | CT2001A | Jinnuo electronics, Inc., Wuhan City |
| X-ray emission instrument | X′Pert PRO | Dutch sodium Panacidae Co Ltd |
| Electrochemical workstation | CHI760E | Shanghai Chenghua Instrument Co., Ltd |
| Scanning electron microscope | FEI sisirion200 | FEI Co. |
| Vacuum glove box | ZKX | Nanjing university instrument |
| Thermogravimetric analyzer | TGA/SDTA 851e | Mettlertolido Co Ltd |
Comparative example: this comparative example was prepared according to the following procedure:
firstly, preprocessing a polymer electrolyte precursor solution, respectively dissolving poly (vinylidene fluoride-hexafluoropropylene) copolymer, polyvinylidene fluoride and organic montmorillonite in a mass ratio of 5:1: 1-4: 3:2 by using an organic solvent N, N-dimethylformamide, stirring uniformly at room temperature, and mixing the uniformly stirred solution;
preparation of polymer electrolyte precursor liquid monomer
Mixing methyl methacrylate: poly (vinylidene fluoride-hexafluoropropylene) copolymer, polyvinylidene fluoride, organo montmorillonite: adding lithium salt into the uniform solution obtained in the step one according to the mass ratio of 20:1: 3-35: 9:20, and stirring at room temperature to obtain a uniform light yellow solution;
preparation of polymer electrolyte of three-phase all-solid-state lithium ion battery
And casting the uniform viscous solution obtained in the step two on a glass plate by adopting a solution casting method, drying the glass plate for 2-4 hours in vacuum at the temperature of 80-100 ℃ to obtain a light yellow polymer electrolyte film, and slicing the film for later use after cooling to room temperature.
Example 1: the preparation method of the high-performance all-solid-state lithium ion battery of the embodiment is to prepare the battery according to the following steps:
pretreatment of polymer electrolyte precursor solution
Respectively dissolving 0.4g of poly (vinylidene fluoride-hexafluoropropylene) copolymer, 0.1g of polyvinylidene fluoride and 0.1g of organic montmorillonite in an organic solvent N, N-dimethylformamide, stirring uniformly at room temperature, and mixing the uniformly stirred solutions;
preparation of polymer electrolyte precursor liquid monomer
Adding 5.4g of methyl methacrylate and 1g of lithium salt into the uniform solution obtained in the first step, and stirring at room temperature to obtain a uniform light yellow solution;
thirdly, polymerization of polymer electrolyte precursor liquid monomer
Adding an initiator into the light yellow solution obtained in the second step, and carrying out prepolymerization for 30min under the heating condition to obtain a precursor solution;
preparation of four-phase and all-solid-state lithium ion battery polymer electrolyte
Casting the precursor solution obtained in the third step on a glass plate by adopting a solution casting method, drying the glass plate for 2 hours in vacuum at the temperature of 80 ℃ to obtain a light yellow polymer electrolyte film, and slicing the film for later use after cooling to room temperature;
fifth, the battery assembly
And D, assembling the negative electrode shell, the polymer electrolyte film obtained in the step four, the lithium sheet, the foamed nickel and the positive electrode shell in a glove box filled with argon in sequence to obtain the high-performance all-solid-state lithium ion battery.
Performance characterization of the above examples and comparative examples
1) Infrared spectroscopy (FTIR) test. The change condition of the functional groups of each component of the polymer electrolyte is tested by infrared spectroscopy (FT-IR, Avatar 370), before testing, the polymer electrolyte film is cut into pieces, mixed with potassium bromide and ground, pressed into a wafer and put into an infrared spectrometer for testing.
2) Scanning Electron Microscope (SEM) testing. And (3) observing the surface appearance of the polymer electrolyte by adopting a Scanning Electron Microscope (SEM), wherein the model of the FEI silicon 200 instrument is 0.2-30 kV in accelerating voltage and 20kV in resolution, drying the prepared sample, adhering the sample on a sample seat coated with conductive adhesive, and testing after spraying gold.
3) X-ray diffraction analysis (XRD) test. The influence of the added components on the crystallinity of a polymer electrolyte system is tested by X-ray diffraction analysis (XRD), the model of the instrument is X' Pert PRO, the parameters are voltage 45kV, current 40mA, diffraction angle scanning range is 10-90 degrees, and scanning speed is 5 degrees s-1Before testing, the dried sample is uniformly spread on a glass slide and then placed on a sample table for testing.
4) And (5) testing interface impedance. And testing the interface impedance of the polymer electrolyte film and the electrode by adopting an electrochemical impedance spectrum to judge the stability of the electrolyte-electrode interface, wherein the model of an electrochemical workstation is CHI760E, the frequency is 0.01-100000Hz, and a lithium symmetrical battery is assembled for testing.
5) And (5) constant current polarization test. Testing the interface stability of the polymer electrolyte and the electrode by a constant current polarization method, and passing voltage-timeJudging the contact quality between the polymer electrolyte and the lithium electrode interface by the intercurve, wherein the instrument model is LAND battery test system CT2001A, and the current density is 0.05mA cm-2The battery assembly mode is a lithium symmetrical battery.
6) And (5) testing charge and discharge. The specific charge-discharge capacity, the charge-discharge efficiency, the voltage platform and the like of the battery in the circulation process are obtained through the charge-discharge test of the battery, the instrument model is LAND battery test system CT2001A, the voltage is set to be 2.6V-4.0V, the current multiplying power is 0.5C, and the polymer electrolyte is assembled into the lithium iron phosphate half battery for testing.
7) And (4) cyclic voltammetry testing. The charging and discharging potentials of the battery and the stability of the internal oxidation-reduction reaction are judged by cyclic voltammetry, the model of an electrochemical workstation is CHI760E, the test parameters are 2.6V-4.5V of voltage, and the scanning rate is 0.0005 V.s-1And the testing time is 38000s, and the polymer electrolyte is assembled into a lithium iron phosphate half-cell for testing.
FIG. 1 is an infrared spectrogram of 1150cm of polymer electrolyte prepared by the method of example 1-1、1240cm-1And 1729cm-1Corresponds to the characteristic absorption peak of C-O, C ═ O of the polymer electrolyte membrane, 1600cm-1The disappearance of the characteristic absorption peak of C ═ C and the appearance of the characteristic peak of C — O indicate that the methyl methacrylate monomer was successfully polymerized into polymethyl methacrylate in the presence of benzoyl peroxide as the initiator.
Fig. 2 is an SEM image of the polymer electrolyte prepared by the method for preparing the high-performance all-solid-state lithium ion battery of example 1, which shows that the polymer electrolyte membrane has a pore structure and a uniform spherical packing structure, and the pores are dense and uniform, which indicates that the poly (vinylidene fluoride-hexafluoropropylene) copolymer, polyvinylidene fluoride, and polymethyl methacrylate three phases are under different surface tensions to disperse the filler well, make the system more uniform, and facilitate the migration of lithium ions, so that the ion conductivity reaches σ 1.1 × 10-3 S cm -110 higher than the conductivity of solid polymer electrolytes known in the prior art-4Left and right (1、 F.Zeng,Y.Y.Sun,B.Hui,Y.Z.Xia,Y.H.Zou,X.L.Zhang,D.J.Yang.ACS Applied Materials And Interfaces,2020,12(39):43805-43812.2、Z.W.Qiu,C.Liu,J.Xin,Q.Wang,J.J.Wu,W.L. Wang,J.J.Zhou,Y.Liu,B.K.Guo,S.Q.Shi.ACS Sustainable Chemistry&Engineering,2019, 7(11):03158.)。
The crystallinity of the polymer electrolyte prepared by the method of example 1 of fig. 3 is significantly reduced compared to that of the polymer electrolyte of the comparative example. The diffraction peak at 20 ° 2 θ decreased in intensity and was similar in shape to the steamed bun peak. The reduction of the crystallinity is beneficial to ion migration, so that the ionic conductivity is greatly improved.
Fig. 4 is an impedance diagram of a polymer electrolyte prepared by the method for preparing a high-performance all-solid-state lithium ion battery of example 1, and it can be seen from the ac impedance of the symmetrical battery that the interfacial impedance of the example is lower than that of the comparative example, ensuring that the battery has high ionic conductivity and capacity retention.
Fig. 5 is an arrhenius diagram of the polymer electrolyte prepared by the method for preparing the high-performance all-solid-state lithium ion battery in example 1, wherein a change curve of the conductivity with the temperature reflects that the polymer electrolyte shows an amorphous state at 25-125 ℃. Therefore, the polymer electrolyte follows the arrhenius equation even in a low temperature region. Examples the activation energy of the polymer electrolyte was 14.061 kJ. mol-1While the comparative example polymer electrolyte had an activation energy of 11.073 kJ. mol-1. Both of them reach relatively low activation energy, which is beneficial to lithium ion migration.
Fig. 6 is a constant current polarization curve of the all-solid-state lithium ion battery prepared by the preparation method of the high-performance all-solid-state lithium ion battery of example 1, and the result shows that the symmetrical batteries of the two methods can stably circulate for 200 hours. The polarization curve of the example is smoother, the polarization voltage (. apprxeq.0.07V) is much smaller than that of the comparative example (. gtoreq.0.10V). The polymer electrolyte of the invention keeps good contact with the electrode interface, has less side reaction and good interface stability.
FIG. 7 shows a high performance of example 1The rate chart of the all-solid-state lithium ion battery prepared by the preparation method of the all-solid-state lithium ion battery is used for observing the discharge specific capacity of the battery when the battery is cycled at 0.1C, 0.2C, 0.5C, 1C, 2C, 5C and 0.1C. As can be seen from the figure, the specific discharge capacity of the battery under different multiplying powers is 154.9 mAh.g-1、155.6mAh·g-1、 149.7mAh·g-1、143.1mAh·g-1、130.9mAh·g-1、25.3mAh·g-1And 160.2mAh · g-1. When the battery returns to the 0.1C cycle again, the discharge specific capacity is kept stable and is recovered to the initial state, which indicates that the cycling stability of the battery is good.
Fig. 8 is a cyclic voltammetry curve of the all-solid-state lithium ion battery prepared by the preparation method of the high-performance all-solid-state lithium ion battery of example 1, where an oxidation peak is 3.82V and a reduction peak is 3.0V. The coincidence degree of the cyclic voltammogram of five cycles is very high, which indicates that the polymer electrolyte has good cyclic performance.
FIG. 9 is a specific capacity-voltage curve of the comparative example at 0.5C with an initial discharge specific capacity of 102.9mAh g-1The specific discharge capacity after 100 cycles is 47.0mAh g-1The capacity of the battery decays rapidly during the first 100 cycles, and the cycle is unstable.
Fig. 10 is an efficiency-specific capacity curve of the comparative example cycled at 0.5C, with large fluctuation in coulombic efficiency during cycling, indicating poor cycling stability of the cell, although the cell remained essentially stable.
FIG. 11 is a specific capacity-voltage curve of 0.5C cycle of the all-solid-state lithium ion battery prepared by the method of example 1, with an initial specific discharge capacity of 138.8mAh g-1The specific discharge capacity after 100 cycles is 147.4mAh g-1Compared with the results of the comparative example, the battery of the present invention was able to be cycled for a long period of time, maintaining stable specific charge and discharge capacities.
Fig. 12 is an efficiency-specific capacity curve of the all-solid-state lithium ion battery prepared by the preparation method of the high-performance all-solid-state lithium ion battery of example 1 at 0.5C, and the coulomb efficiency is stably maintained at 100% during a 100-cycle process. The polymer electrolyte added with azodiisobutyronitrile has better cycle performance than that of the polymer electrolyte not added, the solid electrolyte prepared from unpolymerized methyl methacrylate is dried and heated in vacuum, the methyl methacrylate is evaporated, and the matrix is solidified to form the solid electrolyte, but the assembled battery has structural collapse after being charged and discharged for many times, because the self-supporting performance of the polymer electrolyte lacking the polymethyl methacrylate is poor, the structures of the electrolyte and the interface are subjected to dynamic evolution, interface peeling and interface impedance surge under the action of lithium ion migration and an electric field, and the specific charge and discharge capacity is more quickly attenuated in the cycle process.
Claims (7)
1. A preparation method of a high-performance all-solid-state lithium ion battery is characterized by comprising the following steps:
pretreatment of polymer electrolyte precursor solution
Respectively dissolving poly (vinylidene fluoride-hexafluoropropylene) copolymer, polyvinylidene fluoride and organic montmorillonite in a mass ratio of 5:1: 1-4: 3:2 by using an organic solvent N, N-dimethylformamide, uniformly stirring at room temperature, and mixing the uniformly stirred solutions;
preparation of polymer electrolyte precursor liquid monomer
Mixing methyl methacrylate: poly (vinylidene fluoride-hexafluoropropylene) copolymer, polyvinylidene fluoride, organo montmorillonite: adding lithium salt into the uniform solution obtained in the step one according to the mass ratio of 20:1: 3-35: 9:20, and stirring at room temperature to obtain a uniform light yellow solution;
thirdly, polymerization of polymer electrolyte precursor liquid monomer
Adding an initiator into the light yellow solution obtained in the step two, and carrying out prepolymerization for 10-30 min under heating conditions to obtain a precursor solution;
preparation of four-phase and all-solid-state lithium ion battery polymer electrolyte
Casting the precursor solution obtained in the third step on a glass plate by adopting a solution casting method, drying the glass plate for 2 to 4 hours in vacuum at the temperature of 75 to 95 ℃ to obtain a light yellow polymer electrolyte film, and slicing the film for later use after cooling to room temperature;
fifth, the battery assembly
And D, assembling the negative electrode shell, the polymer electrolyte film obtained in the step four, the lithium sheet, the foamed nickel and the positive electrode shell in a glove box filled with argon in sequence to obtain the high-performance all-solid-state lithium ion battery.
2. The method for preparing a high-performance all-solid-state lithium ion battery according to claim 1, wherein the organic montmorillonite is modified montmorillonite in the step one.
3. The method of claim 1, wherein the lithium salt added in step two is one of chlorine perchlorate, lithium bistrifluoromethanesulfonimide, lithium tetrafluoroborate, lithium hexafluorophosphate and lithium hexafluoroarsenate.
4. The method for preparing a high-performance all-solid-state lithium ion battery according to claim 1 or 3, wherein the stirring time is controlled to be 4-8 hours after the lithium salt is added in the second step.
5. The method according to claim 1, wherein the initiator in step three is one of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, and isophenylhydroperoxide.
6. The method for preparing a high-performance all-solid-state lithium ion battery according to claim 1 or 5, wherein the mass of the initiator in the third step is 0.03-0.06% of the total mass of the pale yellow polymer electrolyte mixed in the second step, and the prepolymerization temperature is 70-100 ℃.
7. The method according to claim 1, wherein the polymer electrolyte film is prepared by casting in the fourth step, and the polymer electrolyte film is allowed to stand for defoaming.
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| CN114497713B (en) * | 2022-02-15 | 2024-03-26 | 蜂巢能源科技(无锡)有限公司 | Fluorine-containing solid electrolyte and preparation method and application thereof |
| CN116683041A (en) * | 2023-08-04 | 2023-09-01 | 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) | Preparation method and application of in-situ polymerization self-supporting solid electrolyte membrane |
| CN116683041B (en) * | 2023-08-04 | 2023-12-01 | 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) | Preparation method and application of in-situ polymerization self-supporting solid electrolyte membrane |
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