CN115449100B - High-pressure-resistant phosphorus-containing polymer electrolyte film, and preparation method and application thereof - Google Patents
High-pressure-resistant phosphorus-containing polymer electrolyte film, and preparation method and application thereof Download PDFInfo
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- CN115449100B CN115449100B CN202211200031.2A CN202211200031A CN115449100B CN 115449100 B CN115449100 B CN 115449100B CN 202211200031 A CN202211200031 A CN 202211200031A CN 115449100 B CN115449100 B CN 115449100B
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 138
- 239000011574 phosphorus Substances 0.000 title claims abstract description 138
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 56
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 42
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 42
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 230000032683 aging Effects 0.000 claims abstract description 23
- 239000012266 salt solution Substances 0.000 claims abstract description 23
- 239000002002 slurry Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000006259 organic additive Substances 0.000 claims abstract description 11
- -1 nickel cobalt aluminum-lithium Chemical compound 0.000 claims abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 8
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 5
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005696 Diammonium phosphate Substances 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 239000006012 monoammonium phosphate Substances 0.000 claims description 3
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims 1
- 239000007774 positive electrode material Substances 0.000 abstract description 7
- NCZYUKGXRHBAHE-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] NCZYUKGXRHBAHE-UHFFFAOYSA-K 0.000 abstract description 3
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 abstract description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 17
- 229910001416 lithium ion Inorganic materials 0.000 description 17
- 239000007784 solid electrolyte Substances 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- FLAFBICRVKZSCF-UHFFFAOYSA-N [Li].[Co]=O.[Li] Chemical compound [Li].[Co]=O.[Li] FLAFBICRVKZSCF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 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 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
Classifications
-
- 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
-
- 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
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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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—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
- 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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- 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
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/43—Compounds containing sulfur bound to nitrogen
- C08K5/435—Sulfonamides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- 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
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Abstract
The invention provides a high-pressure-resistant phosphorus-containing polymer electrolyte film, and a preparation method and application thereof, wherein the method comprises the following steps: mixing a polymer with an organic solvent, heating and stirring to obtain a polymer solution; mixing lithium salt and a phosphorus-containing organic additive, standing and aging to obtain a phosphorus-containing lithium salt solution; mixing the two solutions, heating and stirring, performing ultrasonic defoaming, and aging in a constant-temperature water bath to obtain phosphorus-containing polymer electrolyte slurry; the phosphorus-containing polymer electrolyte slurry is prepared into a film, and the solvent is removed to obtain the high-pressure-resistant phosphorus-containing polymer electrolyte film. The high-pressure-resistant phosphorus-containing polymer electrolyte film has high room temperature ionic conductivity, high electrochemical stability window and high interface compatibility. The high-voltage-resistant phosphorus-containing polymer electrolyte film can be matched with a high-voltage positive electrode material, has excellent electrochemical stability, and is suitable for high-voltage nickel cobalt manganese-lithium metal batteries, lithium cobaltate-lithium metal batteries, lithium manganate-lithium metal batteries, nickel cobalt aluminum-lithium metal batteries and lithium iron phosphate-lithium metal batteries.
Description
Technical Field
The invention belongs to the technical field of solid electrolytes, and particularly relates to a high-pressure-resistant phosphorus-containing polymer electrolyte film, and a preparation method and application thereof.
Background
The energy density of the lithium ion battery is limited by the currently selectable anode and cathode electrode materials, so that the further improvement of the energy density of the lithium ion battery faces great difficulty. Therefore, the development of a lithium ion battery with high energy density, which is safe to use, has become an urgent problem to be solved in the field of energy storage.
The lithium metal (theoretical capacity 3860 mAh/g) is used as the negative electrode of the lithium ion battery, so that the energy density of the lithium ion battery can be effectively improved, and the lithium ion battery has a very large application prospect. However, the lithium metal battery uses flammable and explosive liquid organic electrolyte, and is easy to cause safety problems related to thermal runaway. Meanwhile, the capacity loss of the lithium ion battery is accelerated by the severe side reaction of the liquid organic electrolyte and the anode-cathode interface. However, the use of a polymer solid electrolyte can solve the above-mentioned safety problems of lithium metal batteries on the one hand; on the other hand, the lithium metal battery has simple preparation process and easy mass production, and meanwhile, the polymer solid electrolyte has unique structural strength and tensile property, so that the lithium metal battery meets the performance requirements of high energy density, safety, stability and the like.
The polymer solid electrolyte reported at present mainly comprises a polyether system, a polyacrylonitrile system, a polycarbonate system, polyvinylidene fluoride and a copolymer system which mainly comprise polyethylene oxide and a derivative polymer thereof, has the advantages of good flexibility, easiness in chemical modification and the like, but has the problems of low lithium ion conductivity, weak electrochemical stability, poor compatibility with commercial common high-voltage positive electrode materials and the like at room temperature.
Accordingly, there is a need for improvement and development in the art.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a high-pressure-resistant phosphorus-containing polymer electrolyte film, and a preparation method and application thereof, and aims to solve the problem that the existing polymer electrolyte film is poor in compatibility with commercial common high-pressure positive electrode materials.
In a first aspect, the present invention provides a method for preparing a high pressure resistant, phosphorus containing polymer electrolyte membrane, comprising the steps of:
mixing a polymer and an organic solvent, and performing first heating and stirring to obtain a polymer solution;
Mixing lithium salt and a phosphorus-containing organic additive, and standing and aging to obtain a phosphorus-containing lithium salt solution;
mixing the polymer solution with the phosphorus-containing lithium salt solution, performing second heating and stirring, and then performing ultrasonic defoaming and constant-temperature water bath aging to obtain phosphorus-containing polymer electrolyte slurry;
and preparing the phosphorus-containing polymer electrolyte slurry into a film, and removing the solvent to obtain the high-pressure-resistant phosphorus-containing polymer electrolyte film.
Alternatively, the polymer is selected from two of polyethylene oxide, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, polypropylene carbonate.
Optionally, the organic solvent is at least one selected from N, N-dimethylformamide, N-methylpyrrolidone, acetonitrile, tetrahydrofuran, acetone and ethanol.
Optionally, the mass ratio of the polymer to the organic solvent is 1: (0.1-1000).
Optionally, the lithium salt is at least one selected from lithium hexafluorophosphate, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (oxalato) borate, lithium perchlorate and lithium trifluoromethanesulfonate.
Optionally, the phosphorus-containing organic aid is selected from one or two of monoammonium phosphate, diammonium phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, dimethyl methyl phosphate and diethyl ethyl phosphate.
Optionally, the mass ratio of the lithium salt to the phosphorus-containing organic auxiliary agent is 1: (0.1-10).
Optionally, the mass ratio of the polymer solution to the lithium salt solution containing phosphorus is 1: (0.001-1), wherein the mass ratio of the polymer to the organic solvent is 1: (0.1-1000), wherein the mass ratio of the lithium salt to the phosphorus-containing organic auxiliary agent is 1: (0.1-10).
Optionally, the temperature of the first heating and stirring is higher than the melting point of the polymer, and the time of the first heating and stirring is 2-10h.
Optionally, the standing and ageing time is 4-48 hours.
Optionally, the temperature of the second heating and stirring is 45-70 ℃, and the time of the second heating and stirring is 1-4h;
The temperature of the ultrasonic defoaming and the constant-temperature water bath aging is 45-70 ℃ and the time is 0.5-2h.
Optionally, the step of removing the solvent is performed under air, vacuum or an inert atmosphere.
Optionally, the conditions for removing the solvent include: the time is 1-48h, and the temperature is 20-200 ℃.
In a second aspect, the invention provides a high-pressure-resistant phosphorus-containing polymer electrolyte film prepared by the preparation method.
Alternatively, the high pressure resistant phosphorus containing polymer electrolyte film has a thickness of 1 to 1000 μm.
In a third aspect, the present invention provides the use of a high pressure resistant phosphorus containing polymer electrolyte membrane as described above in a lithium metal battery.
The beneficial effects are that: the high-pressure-resistant phosphorus-containing polymer electrolyte film prepared by the preparation method provided by the invention has high room-temperature ionic conductivity, high electrochemical stability window and high interface compatibility. The high-voltage-resistant phosphorus-containing polymer electrolyte film prepared by the invention can be matched with a high-voltage positive electrode material, has excellent electrochemical stability, and is suitable for high-voltage nickel cobalt manganese-lithium metal batteries, lithium cobaltate-lithium metal batteries, lithium manganate-lithium metal batteries, nickel cobalt aluminum-lithium metal batteries and lithium iron phosphate-lithium metal batteries.
Drawings
FIG. 1 is an SEM sectional view of a high pressure resistant, phosphorus-containing polymer electrolyte membrane prepared in example 1.
Fig. 2 is an SEM morphology of the high pressure resistant phosphorus containing polymer electrolyte membrane prepared in example 1.
FIG. 3 is an EIS impedance chart of the high pressure resistant phosphorus-containing polymer electrolyte film prepared in example 1.
FIG. 4 is an LSV graph of the high-pressure resistant phosphorus-containing polymer electrolyte film prepared in example 1.
Fig. 5 is a CV graph of the high voltage resistant phosphorus containing polymer electrolyte film prepared in example 1 assembled into a nickel cobalt manganese 811-lithium metal battery.
Fig. 6 is a high-voltage long-cycle chart of the high-voltage resistant phosphorus-containing polymer electrolyte film prepared in example 1 assembled into a nickel cobalt manganese 811-lithium metal battery.
Detailed Description
The present invention will be described in further detail below in order to make the objects, technical solutions and effects of the present invention more clear and definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
At present, polymer electrolytes can only meet the requirements of commercial application under specific conditions, and the comprehensive performance of the polymer electrolytes needs to be improved. Based on the above, it is important to modify the polymer electrolyte, and it is important to control the production cost by fully utilizing the additive. Therefore, the embodiment develops a novel polymer solid electrolyte, perfects the preparation process of the polymer solid electrolyte, can be matched with the current commercial high-voltage positive electrode material, and has high room temperature ion conductivity, high electrochemical stability window and high interface compatibility.
Specifically, the embodiment of the invention provides a preparation method of a high-pressure-resistant phosphorus-containing polymer electrolyte film, which comprises the following steps:
S1, mixing a polymer and an organic solvent, and performing first heating and stirring to obtain a polymer solution;
S2, mixing lithium salt and a phosphorus-containing organic additive, and standing and aging to obtain a phosphorus-containing lithium salt solution;
S3, mixing the polymer solution with the phosphorus-containing lithium salt solution, performing second heating and stirring, and then performing ultrasonic defoaming and constant-temperature water bath aging to obtain phosphorus-containing polymer electrolyte slurry;
S4, preparing the phosphorus-containing polymer electrolyte slurry into a film, and removing the solvent to obtain the high-pressure-resistant phosphorus-containing polymer electrolyte film.
In the embodiment, the polymer solution and the phosphorus-containing lithium salt solution are respectively prepared first, and then the two solutions are mixed, and the solution is prepared by adopting the method, so that the phosphorus-containing organic additive can be uniformly dispersed in the phosphorus-containing polymer electrolyte slurry, the mechanical property and the electrochemical stability of the prepared phosphorus-containing polymer electrolyte film are improved, and meanwhile, the prepared phosphorus-containing polymer electrolyte film has excellent high-pressure resistance, and the interface stability of the phosphorus-containing polymer electrolyte film and the anode and the cathode of the lithium metal battery is improved. The inventors found that both the lithium salt and the phosphorus-containing organic additive have excellent compatibility, and the phosphorus-containing organic additive is more conducive to dissociation of the lithium salt due to its higher Gutmann donor number, so that the lithium salt has excellent solubility in the phosphorus-containing organic additive, so that the lithium salt and the phosphorus-containing organic additive are formulated into a phosphorus-containing lithium salt solution. And mixing the phosphorus-containing lithium salt solution with the polymer solution prepared in addition, so that the phosphorus-containing organic aid can be uniformly dispersed in the phosphorus-containing polymer electrolyte slurry, and the function of the phosphorus-containing organic aid can be fully exerted. Specifically, the phosphorus-containing organic auxiliary agent can improve the ionic conductivity of lithium ions in the phosphorus-containing polymer electrolyte film, is beneficial to uniform transmission of lithium ions in the electrolyte and at the interface between the electrolyte and the anode and the cathode, and improves the cycling stability of the full battery. In addition, the addition amount of the phosphorus-containing organic auxiliary agent is small, so that the production cost is reduced, and the method has high economical efficiency.
In addition, in the embodiment, after the polymer solution and the phosphorus-containing lithium salt solution are mixed, the uniformly dispersed and transparent phosphorus-containing polymer electrolyte slurry without bubbles can be obtained by the methods of ultrasonic defoaming and constant-temperature water bath aging after the polymer solution and the phosphorus-containing lithium salt solution are heated and stirred uniformly. The embodiment adopts the homogenization operation method, so that the internal microstructure uniformity of the finally prepared phosphorus-containing polymer electrolyte film can be improved, the internal compactness of the phosphorus-containing polymer electrolyte film is improved, and the film thickness is reduced.
The phosphorus-containing polymer electrolyte film prepared by the method can be matched with the current commercial high-voltage positive electrode material, and has high room-temperature ionic conductivity, high electrochemical stability window and high interface compatibility.
In one embodiment, step S1 specifically includes: mixing the polymer and the organic solvent, and stirring by first heating to obtain a polymer solution with uniform dispersion.
In one embodiment, the polymer is selected from two of polyethylene oxide, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, polypropylene carbonate, and the like, but is not limited thereto. The polymer electrolyte reported at present adopts a single polymer system, and the comprehensive performance of the polymer electrolyte needs to be improved. The inventor finds that two polymers can respectively play a synergistic role of a polymer skeleton and lithium ion transmission, for example, polyvinylidene fluoride forms the polymer skeleton by thermal polymerization of linear olefin, the polymer skeleton has excellent mechanical properties, and the coordination of ether oxygen bond and lithium ion in polyethylene oxide can accelerate the lithium ion transmission, so that the phosphorus-containing polymer electrolyte film prepared by mixing the polyvinylidene fluoride and the polyethylene oxide according to a certain proportion has better mechanical properties and electrochemical properties.
The mass ratio of the polymer serving as a framework to the polymer serving as lithium ion migration can be controlled at 1: (0.1-2) to give a phosphorus-containing polymer electrolyte film excellent in both mechanical properties and electrochemical properties.
In one embodiment, the organic solvent is selected from at least one of N, N-dimethylformamide, N-methylpyrrolidone, acetonitrile, tetrahydrofuran, acetone, ethanol, and the like, but is not limited thereto.
In one embodiment, the mass ratio of the polymer to the organic solvent is 1:
(0.1-1000)。
In one embodiment, the temperature of the first heated agitation is above the melting point of the polymer.
In one embodiment, the first heating and stirring time is 2-10 hours, such as 2 hours, 5 hours, 10 hours, etc.
In one embodiment, step S2 specifically includes: mixing lithium salt and phosphorus-containing organic aid, standing and aging to obtain polymer solution with uniform dispersion.
In one embodiment, the lithium salt is at least one selected from lithium hexafluorophosphate, lithium bistrifluoromethane sulfonyl imide, lithium bisfluoro oxalato borate, lithium perchlorate, lithium trifluoromethane sulfonate, and the like, but is not limited thereto.
In one embodiment, the phosphorus-containing organic additive is selected from one or two of monoammonium phosphate, diammonium phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, dimethyl methyl phosphate, diethyl ethyl phosphate, and the like, but is not limited thereto.
In one embodiment, the mass ratio of the lithium salt to the phosphorus-containing organic auxiliary agent is 1:
(0.1-10)。
in one embodiment, the time for the resting and aging is from 4 to 48 hours, such as 4 hours, 5 hours, 8 hours, 15 hours, 24 hours, 48 hours, etc.
In one embodiment, step S3 specifically includes: and mixing the polymer solution with the phosphorus-containing lithium salt solution, performing second heating and stirring, and then performing ultrasonic defoaming and constant-temperature water bath aging to obtain the transparent and bubble-free phosphorus-containing polymer electrolyte slurry with uniform dispersion.
In one embodiment, the mass ratio of the polymer solution to the phosphorus-containing lithium salt solution is 1: (0.001-1), wherein the mass ratio of the polymer to the organic solvent is 1: (0.1-1000), wherein the mass ratio of the lithium salt to the phosphorus-containing organic auxiliary agent is 1: (0.1-10). The film preparation time can be effectively shortened by controlling the addition amount of the organic solvent. The quality of the phosphorus-containing organic additive is regulated and controlled, so that the high-concentration phosphorus-containing lithium salt solution is prepared, the lithium ion coordination environment can be regulated, and the lithium salt can be fully dissociated, thereby promoting the uniform transmission of lithium ions. Within the above range, the obtained phosphorus-containing polymer electrolyte slurry can be made to exhibit a uniform transparent texture.
In one embodiment, the temperature of the second heating and stirring is 45-70 ℃, and the time of the second heating and stirring is 1-4 hours, such as 1 hour, 2 hours, 4 hours, etc.;
The temperature of the ultrasonic defoaming and the constant-temperature water bath aging is 45-70 ℃, such as 45 ℃, 60 ℃, 70 ℃ and the like, and the time is 0.5-2h, such as 0.5h, 1h, 2h and the like.
In one embodiment, step S4 specifically includes: and preparing the uniformly dispersed phosphorus-containing polymer electrolyte slurry into a film, and removing the solvent to obtain the ultrathin compact high-pressure-resistant phosphorus-containing polymer electrolyte film. Wherein the film forming method is selected from one of electrostatic spinning, knife coating, spin coating, pouring, spraying and the like, but is not limited thereto.
In one embodiment, the conditions for removing the solvent include: the time is 1-48h, and the temperature is 20-200 ℃.
In one embodiment, the step of removing the solvent is performed under air, vacuum, or an inert atmosphere (e.g., nitrogen atmosphere, argon atmosphere, etc.).
When the step of removing the solvent is performed under vacuum, the prepared phosphorus-containing polymer electrolyte film can have a three-dimensional porous structure, and the later doping modification of the phosphorus-containing polymer electrolyte film is facilitated.
When the step of removing the solvent is performed in an inert atmosphere, the prepared phosphorus-containing polymer electrolyte film has compact ultrathin characteristics, and is beneficial to improving the compatibility of the phosphorus-containing polymer electrolyte film and an anode-cathode interface.
The embodiment of the invention provides a high-pressure-resistant phosphorus-containing polymer electrolyte film prepared by adopting the preparation method.
In one embodiment, the high pressure resistant, phosphorus containing polymer electrolyte film has a thickness of 1 to 1000 μm. In the embodiment, the thickness of the high-voltage resistant phosphorus-containing polymer electrolyte film is controlled to be 1-1000 mu m by adjusting the technological parameters, so that the impedance of a battery body and the interface impedance are reduced, and the energy density of the lithium metal battery is improved.
In one embodiment, the high pressure resistant, phosphorous containing polymer electrolyte film has a thickness of 5 to 100 μm, such as 40 μm, 67.5 μm, 98 μm. The high-pressure-resistant phosphorus-containing polymer electrolyte film with the thickness can ensure high energy density and mechanical property stability of the lithium metal battery.
The embodiment of the invention provides an application of the high-voltage-resistant phosphorus-containing polymer electrolyte film in a lithium metal battery.
The high-voltage-resistant phosphorus-containing polymer electrolyte film is matched with a high-voltage positive electrode material, has excellent electrochemical stability, and is suitable for at least one of a high-voltage nickel cobalt manganese-lithium metal battery, a lithium cobalt oxide-lithium metal battery, a lithium manganate-lithium metal battery, a nickel cobalt aluminum-lithium metal battery and a lithium iron phosphate-lithium metal battery.
In one embodiment, the high-pressure-resistant phosphorus-containing polymer electrolyte film can be applied to at least one of a soft package lamination type, a soft package winding type, a button cell type, a square aluminum shell winding type, a cylindrical winding type and the like, and provides a new idea for commercialized application of solid polymer electrolytes.
The invention is further illustrated by the following specific examples.
Example 1
A preparation method of a high-pressure-resistant phosphorus-containing polymer electrolyte film comprises the following steps:
0.5g of polyethylene oxide and 0.5g of polyvinylidene fluoride-hexafluoropropylene are dissolved in 10mL of N, N-dimethylformamide, and the mixture is heated and stirred for 5 hours at 60 ℃ until the polymer is completely dissolved, so as to obtain a polymer solution;
Respectively mixing 5.36g of lithium bistrifluoromethane sulfonyl imide and 5.00g of triethyl phosphate, standing and aging for 12 hours to prepare uniform and transparent lithium salt solution containing phosphorus;
Adding 0.5mL of phosphorus-containing lithium salt solution into the polymer solution, heating and stirring for 2h until the solution is uniformly mixed; then, through ultrasonic defoaming and a water bath aging method at the constant temperature of 60 ℃ for 1h, the uniformly dispersed transparent bubble-free phosphorus-containing polymer electrolyte slurry is obtained;
and (3) scraping the phosphorus-containing polymer electrolyte slurry by a 500 mu m scraper, and putting the slurry into a vacuum oven for drying at 60 ℃ for 24 hours to obtain the high-pressure-resistant phosphorus-containing polymer electrolyte film. The thickness of the obtained high-pressure-resistant phosphorus-containing polymer electrolyte film was 67.5 μm, and the electrochemical stability window was 5.20V.
Fig. 1 is an SEM cross-sectional view of the high-pressure resistant phosphorus-containing polymer electrolyte membrane prepared in example 1, and it is understood from fig. 1 that the thickness of the phosphorus-containing polymer electrolyte membrane is only 67.5 μm, and that the reduction of the thickness of the phosphorus-containing polymer electrolyte membrane contributes to the improvement of the energy density of the full cell.
Fig. 2 is an SEM morphology of the high pressure resistant phosphorus containing polymer electrolyte film prepared in example 1, and it can be seen from fig. 2 that the uniform three-dimensional porous morphology contributes to uniform and rapid migration of lithium ions.
FIG. 3 is an EIS impedance chart of the high-voltage resistant phosphorus-containing polymer electrolyte film prepared in example 1, wherein the room-temperature ionic conductivity of the phosphorus-containing polymer electrolyte film obtained by calculation according to impedance values reaches 7.9X10 -4 S/cm, and the conditions of normal operation of a full cell at room temperature are met.
FIG. 4 is an LSV graph of the high-pressure resistant phosphorus-containing polymer electrolyte film prepared in example 1, and as can be seen from FIG. 4, the electrochemical stability window of the prepared phosphorus-containing polymer electrolyte film reaches 5.20V.
Fig. 5 is a CV graph of the high voltage resistant phosphorus containing polymer electrolyte film prepared in example 1 assembled into a nickel cobalt manganese 811-lithium metal battery, and it is apparent from fig. 5 that significant redox peaks occur in the ultra-high voltage range of 2.8-4.7V.
Fig. 6 is a high-voltage long-cycle chart of the high-voltage resistant phosphorus-containing polymer electrolyte film prepared in example 1 assembled into a nickel cobalt manganese 811-lithium metal battery, and as can be seen from fig. 6, 300 stable cycles are realized under the room temperature condition in the ultra-high voltage range of 2.8-4.7V, and the capacity retention rate is as high as 90.4%.
Example 2
A preparation method of a high-pressure-resistant phosphorus-containing polymer electrolyte film comprises the following steps:
0.5g of polyethylene oxide and 0.5g of polyvinylidene fluoride are dissolved in 10mL of acetonitrile, heated and stirred at 60 ℃ for 5 hours until the polymer is completely dissolved, and a polymer solution is obtained;
respectively mixing 3.75g of lithium hexafluorophosphate and 5g of triethyl phosphate, standing and aging for 12 hours to prepare uniform and transparent lithium salt solution containing phosphorus;
Adding 0.5mL of phosphorus-containing lithium salt solution into the polymer solution, heating and stirring for 2h until the solution is uniformly mixed; then, through ultrasonic defoaming and a water bath aging method at the constant temperature of 60 ℃ for 1h, the uniformly dispersed transparent bubble-free phosphorus-containing polymer electrolyte slurry is obtained;
And forming a film from the phosphorus-containing polymer electrolyte slurry by a pouring method, and then heating and drying the film for 48 hours at 40 ℃ in an air atmosphere to obtain the high-pressure-resistant phosphorus-containing polymer electrolyte film. The thickness of the obtained high-pressure-resistant phosphorus-containing polymer electrolyte film is 98 mu m, and the electrochemical stability window is 5.04V.
Example 3
A preparation method of a high-pressure-resistant phosphorus-containing polymer electrolyte film comprises the following steps:
Dissolving 0.5g of polyvinylidene fluoride and 0.5g of polyvinylidene fluoride-hexafluoropropylene in 10mL of N, N-dimethylformamide, heating and stirring for 5h at 65 ℃ until the polymer is completely dissolved, and obtaining a polymer solution;
Mixing 1.35g of lithium perchlorate and 5g of trimethyl phosphate, standing and aging for 24 hours to prepare uniform and transparent lithium salt solution containing phosphorus;
Adding 0.5mL of phosphorus-containing lithium salt solution into the polymer solution, heating and stirring for 2h until the solution is uniformly mixed; then, through ultrasonic defoaming and a water bath aging method at the constant temperature of 60 ℃ for 1h, the uniformly dispersed transparent bubble-free phosphorus-containing polymer electrolyte slurry is obtained;
The phosphorus-containing polymer electrolyte slurry is scraped by a 250 mu m scraper, and then is heated and dried for 48 hours at 60 ℃ under vacuum condition, so as to obtain the high-pressure-resistant phosphorus-containing polymer electrolyte film. The thickness of the obtained high-pressure-resistant phosphorus-containing polymer electrolyte film is 40 mu m, and the electrochemical stability window is 4.85V.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (4)
1. The preparation method of the high-pressure-resistant phosphorus-containing polymer electrolyte film is characterized in that the high-pressure-resistant phosphorus-containing polymer electrolyte film is prepared from the following raw materials: a polymer, an organic solvent, a lithium salt and a phosphorus-containing organic auxiliary agent;
the polymer is selected from two of polyethylene oxide, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile and polypropylene carbonate;
The organic solvent is at least one selected from N, N-dimethylformamide, N-methylpyrrolidone, acetonitrile, tetrahydrofuran, acetone and ethanol;
the lithium salt is at least one selected from lithium hexafluorophosphate, lithium bistrifluoromethane sulfonyl imide, lithium bistrifluorooxalato borate, lithium perchlorate and lithium trifluoromethane sulfonate;
the phosphorus-containing organic aid is one or two selected from monoammonium phosphate, diammonium phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, dimethyl methyl phosphate and diethyl ethyl phosphate;
the preparation method of the high-pressure-resistant phosphorus-containing polymer electrolyte film comprises the following specific steps:
mixing a polymer and an organic solvent, and performing first heating and stirring to obtain a polymer solution;
Mixing lithium salt and a phosphorus-containing organic additive, and standing and aging to obtain a phosphorus-containing lithium salt solution;
mixing the polymer solution with the phosphorus-containing lithium salt solution, performing second heating and stirring, and then performing ultrasonic defoaming and constant-temperature water bath aging to obtain phosphorus-containing polymer electrolyte slurry;
preparing the phosphorus-containing polymer electrolyte slurry into a film, and removing a solvent to obtain the high-pressure-resistant phosphorus-containing polymer electrolyte film;
The mass ratio of the polymer solution to the phosphorus-containing lithium salt solution is 1: (0.001-1), wherein the mass ratio of the polymer to the organic solvent is 1: (0.1-1000), wherein the mass ratio of the lithium salt to the phosphorus-containing organic auxiliary agent is 1: (0.1-10);
The temperature of the first heating and stirring is higher than the melting point of the polymer, and the time of the first heating and stirring is 2-10h;
the standing and ageing time is 4-48h;
the temperature of the second heating and stirring is 45-70 ℃, and the time of the second heating and stirring is 1-4h;
The temperature of the ultrasonic defoaming and the constant-temperature water bath aging is 45-70 ℃ and the time is 0.5-2h;
the step of removing the solvent is performed under air, vacuum or inert atmosphere;
The conditions for removing the solvent include: the time is 1-48h, and the temperature is 20-200 ℃.
2. A high pressure resistant, phosphorus containing polymer electrolyte membrane prepared by the method of claim 1.
3. The high pressure resistant, phosphorus-containing polymer electrolyte membrane of claim 2 wherein the high pressure resistant, phosphorus-containing polymer electrolyte membrane has a thickness of 1-1000 μm.
4. Use of the high-voltage resistant phosphorus-containing polymer electrolyte film according to claim 2 or 3 in lithium metal batteries.
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