CN115332608A - Composite solid electrolyte membrane and preparation method and application thereof - Google Patents
Composite solid electrolyte membrane and preparation method and application thereof Download PDFInfo
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- CN115332608A CN115332608A CN202210863614.7A CN202210863614A CN115332608A CN 115332608 A CN115332608 A CN 115332608A CN 202210863614 A CN202210863614 A CN 202210863614A CN 115332608 A CN115332608 A CN 115332608A
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- 239000012528 membrane Substances 0.000 title claims abstract description 141
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 90
- 239000002131 composite material Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000011159 matrix material Substances 0.000 claims abstract description 59
- 229920000642 polymer Polymers 0.000 claims abstract description 59
- 150000004820 halides Chemical class 0.000 claims abstract description 32
- 239000003792 electrolyte Substances 0.000 claims abstract description 25
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 23
- 229920005597 polymer membrane Polymers 0.000 claims abstract description 7
- 239000005518 polymer electrolyte Substances 0.000 claims description 31
- 229910003002 lithium salt Inorganic materials 0.000 claims description 26
- 159000000002 lithium salts Chemical class 0.000 claims description 26
- 229920006254 polymer film Polymers 0.000 claims description 26
- -1 lithium hexafluoroarsenate Chemical compound 0.000 claims description 18
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 230000001681 protective effect Effects 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 239000004745 nonwoven fabric Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 229910021617 Indium monochloride Inorganic materials 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 claims description 3
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 19
- 210000001787 dendrite Anatomy 0.000 abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 12
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 239000008151 electrolyte solution Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 36
- 239000007787 solid Substances 0.000 description 12
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 5
- 239000004626 polylactic acid Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000747 poly(lactic acid) Polymers 0.000 description 4
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229920001893 acrylonitrile styrene Polymers 0.000 description 2
- 229920003180 amino resin Polymers 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000033366 cell cycle process Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910001502 inorganic halide Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Conductive Materials (AREA)
- Secondary Cells (AREA)
Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a composite solid electrolyte membrane and a preparation method and application thereof. The composite solid electrolyte membrane of the present invention includes a polymer matrix and a solid electrolyte membrane disposed thereon, the solid electrolyte membrane including a polymer membrane and a halide membrane disposed in a stack. The composite solid electrolyte membrane adopts a polymer matrix with excellent toughness, elasticity and strength as a supporting structure, the solid electrolyte membrane is arranged on the surface of the polymer matrix to provide lithium ion conductivity, and the addition of the halide membrane can be matched with the polymer matrix to form a composite compact membrane with low porosity, inhibit the growth of lithium dendrites and simultaneously be beneficial to Li dendrite growth + The rapid transmission of the electrolyte solution can promote the cycle multiplying power of the battery in a high-temperature environment, so that the formed composite solid electrolyte membrane has the advantages of good toughness, good elasticity, high strength, good thermal stability and high ionic conductivity, and further can improve the performance of the electrolyte solutionThe safety and charge-discharge performance of the solid-state battery are improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a composite solid electrolyte membrane and a preparation method and application thereof.
Background
Lithium Ion Batteries (LIBs) have the advantages of high energy density, low self-discharge rate, wide use temperature, long cycle life, environmental friendliness, no memory effect, etc., and have thus been rapidly developed over the last decade. Current lithium ion batteries achieve high energy density by using organic liquid electrolytes and special additives to increase the battery voltage, but this may pose serious safety problems. With the development of new energy power battery technology, the traditional liquid battery can not meet the use requirements of consumers more and more, and the lithium battery technology is developing towards the requirements of high safety and high energy density. The development of large-scale energy storage systems such as electric vehicles and power grids is accelerated by the appearance of all-solid-state lithium ion batteries (ASSLBs), and therefore, the development of all-solid-state lithium ion batteries with high energy density and high safety becomes a future development trend of the industry.
The key technology of the all-solid-state lithium ion battery as a novel battery energy storage technology is that solid electrolytes (SSEs) eliminate inflammable liquid organic electrolytes in the original lithium ion battery, and the safety and the volume energy density are improved through more effective packaging. Although a great deal of research is now being conducted to propose the use of fast ion-conducting solids such as sulfides, oxides and phosphates in solid-state batteries, these batteries exhibit the disadvantages of poor mechanical properties, low energy density cycling, and the like. With the research of all-solid-state lithium ion batteries getting deeper, polymer electrolytes are gradually becoming a new favorite for research and development. Although the polymer is easy to prepare into a thin film, the film strength is low, the polymer electrolyte is easy to generate an interface problem of electrochemical and mechanical degradation with a positive electrode material, in addition, the polymer electrolyte film is easy to be pierced by lithium dendrites in the cell cycle process and is not high-temperature resistant, and when the voltage exceeds 4V in a high-temperature environment, the polymer electrolyte micro-groups are easy to be oxidized, so that the activity is reduced. Therefore, in the prior art, the ionic conductivity of the polymer electrolyte is improved by adding a plasticizer, but the mechanical property of the membrane is reduced, so that the polymer electrolyte brings potential safety hazards to the all-solid-state battery. Furthermore, some polymer-inorganic composite electrolyte membranes, such as polymer-oxide, polymer-sulfide and other forms of composite electrolyte membranes, are disclosed in the prior art, but the prior art also has the defect of poor mechanical strength of the membranes, so that the application of the membranes in all-solid-state lithium ion batteries cannot be improved. Therefore, it is important to develop a novel composite solid electrolyte membrane to improve the safety and charge-discharge performance of the all-solid battery.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is that the safety and the charge and discharge performance of the all-solid battery are not good due to the poor mechanical strength of the existing polymer electrolyte membrane, and further, a composite solid electrolyte membrane is provided to improve the electrochemical characteristics of the polymer electrolyte membrane at the lithium metal cathode, improve the mechanical strength, the thermal stability and the electrochemical performance of the polymer electrolyte membrane, and ensure that the all-solid battery realizes high safety and high charge and discharge performance.
The invention also provides a method for preparing the composite solid electrolyte membrane and a solid battery comprising the composite solid electrolyte membrane.
The purpose of the invention is realized by the following technical scheme:
in one aspect, the present invention provides a composite solid electrolyte membrane. According to an embodiment of the present invention, the composite solid electrolyte membrane includes a polymer matrix and a solid electrolyte membrane disposed on the polymer matrix, the solid electrolyte membrane including a polymer film and a halide film disposed in a stack.
The composite solid electrolyte membrane provided by the invention adopts the polymer matrix with excellent toughness, elasticity and strength as a support structure, the solid electrolyte membrane is arranged on the surface of the polymer matrix to provide lithium ion conductivity, and the halide membrane can be matched with the polymer matrix to form a compact membrane with low porosity, so that the growth of lithium dendrites is inhibited, and the composite solid electrolyte membrane is also beneficial to Li + The rapid transmission of the electrolyte promotes the cycling power of the battery in a high-temperature environment, so that the formed composite solid electrolyte membrane has the advantages of good toughness, good elasticity, high strength, good thermal stability and high ionic conductivity, and the safety, charging and discharging of the solid battery can be improvedAnd (4) electrical property.
In some embodiments of the invention, the halide membrane is disposed proximate to the polymer matrix, the solid electrolyte membrane being disposed on one side of the polymer matrix; in other embodiments of the present invention, the solid electrolyte membrane may also be disposed on both sides of the polymer matrix.
In some embodiments of the present invention, the raw material composition of the polymer film includes a polymer electrolyte and a lithium salt, and the mass ratio of the polymer electrolyte to the lithium salt is 1 to 20:1, preferably 1 to 5:1. the addition of lithium salt in a proper proportion can improve the ionic conductivity of the composite solid electrolyte membrane.
Optionally, the polymer electrolyte is at least one of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyvinyl alcohol, polycarbonate, polyacrylonitrile, polyvinylpyrrolidone, polyethylene glycol, polyethylene oxide, and polymethyl methacrylate.
Preferably, the polymer electrolyte is prepared by mixing 1-2 parts by mass: 1-3 of polyethylene glycol and polyethylene oxide, thereby improving the film-forming toughness of the polymer film and further improving the film strength.
Optionally, the lithium salt is at least one of lithium bis (trifluoromethyl) sulfonyl imide, lithium bis (fluoro) sulfonyl imide, lithium trifluoro methyl sulfonyl imide, lithium bis (oxalate) borate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium chloride, lithium hexafluorophosphate and lithium perchlorate.
Optionally, the polymer film has a thickness of 2 to 50 μm, preferably 5 to 30 μm. This can improve the toughness and strength of the polymer film.
In some embodiments of the invention, the polymer matrix has a porosity of 30 to 80% and a thickness of 2 to 40 μm. Thus, the toughness, elasticity, and strength of the composite solid electrolyte membrane can be improved.
Optionally, the polymer matrix is at least one of a nonwoven fabric, a fibrous membrane, a meltblown, a porous separator. Thus, the toughness, elasticity, and strength of the composite solid electrolyte membrane can be improved.
Optionally, the material of the polymer matrix is at least one of polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyoxymethylene, polyamide, polycarbonate, polylactic acid, polymethyl methacrylate, acrylonitrile-styrene copolymer, polybutylene terephthalate, phenolic resin, and amino resin.
In some embodiments of the invention, the halide film has a thickness of 5 to 40 μm. This can improve the ion conductivity of the composite solid electrolyte membrane.
Optionally, the raw material of the halide film is Li 3 InCl 6 、Li 3 YbCl 6 、Li 3 YCl 6 、Li 3 ScCl 6 、Li 3 GaCl 6 At least one of (a).
In another aspect, the present invention also provides a method for preparing the above composite solid electrolyte membrane, comprising the steps of:
mixing the polymer electrolyte, the lithium salt and an organic solvent under a protective atmosphere to obtain slurry, coating the slurry to form a film, drying the film in the protective atmosphere, and then drying the film in vacuum to obtain the polymer film;
the polymer film, the raw material for the halide film, the polymer matrix are stacked and pressed into a film.
In some embodiments of the present invention, the mass ratio of the polymer electrolyte to the organic solvent is 1:15 to 25, preferably 1:15 to 20.
Optionally, the organic solvent is at least one of methyl formamide, acetonitrile, cyclohexanone, heptane, N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide, and N, N-dimethylacetamide.
In some embodiments of the invention, the temperature of the drying in the protective atmosphere is 20 to 30 ℃ and the time is 2 to 72 hours, preferably 4 to 24 hours.
Optionally, the temperature of the vacuum drying is 30-80 ℃, preferably 40-60 ℃, and the time of the vacuum drying is 4-72 hours, preferably 12 hours.
In some embodiments of the invention, the pressing temperature is 30 to 150 ℃ and the pressure is 1 to 10MPa.
In still another aspect, the present invention also provides a solid-state battery comprising the composite solid electrolyte membrane according to the above or a composite solid electrolyte membrane obtained by the above method for producing a composite solid electrolyte membrane.
The solid-state battery provided by the invention adopts the polymer matrix with excellent toughness, elasticity and strength as the support structure of the diaphragm, the solid-state electrolyte membrane is arranged on the surface of the polymer matrix to provide lithium ion conductivity, and the halide membrane can be matched with the polymer matrix to ensure that the composite membrane forms a compact membrane with low porosity, thereby inhibiting the growth of lithium dendrites and being beneficial to Li dendrites + The rapid transmission of the electrolyte promotes the cycling power of the battery in a high-temperature environment, so that the formed composite solid electrolyte membrane has the advantages of good toughness, good elasticity, high strength, good thermal stability and high ionic conductivity, and the safety and the charge and discharge performance of the solid battery can be improved.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. the invention provides a composite solid electrolyte membrane, which comprises a polymer matrix and a solid electrolyte membrane arranged on the polymer matrix, wherein the solid electrolyte membrane comprises a polymer membrane and a halide membrane which are arranged in a laminated manner. The composite solid electrolyte membrane provided by the invention adopts a polymer matrix with excellent toughness, elasticity and strength as a supporting structure, the solid electrolyte membrane is arranged on the surface of the polymer matrix to provide lithium ion conductivity, and the addition of the halide membrane can be matched with the polymer matrix, so that the composite membrane forms a compact membrane with low porosity, thereby inhibiting the growth of lithium dendrites and being beneficial to Li dendrites + The rapid transmission of the electrolyte promotes the cycling power of the battery in a high-temperature environment, so that the formed composite solid electrolyte membrane has the advantages of good toughness, good elasticity, high strength, good thermal stability and high ionic conductivity, and the safety and the charge and discharge performance of the solid battery can be improved.
2. The method for preparing the composite solid electrolyte membrane provided by the invention has the advantages of simple and convenient process, rapidness, environmental friendliness and suitability for large-scale production.
3. The solid-state battery provided by the invention adopts the polymer matrix with excellent toughness, elasticity and strength as the support structure of the diaphragm, the solid-state electrolyte membrane is arranged on the surface of the polymer matrix to provide lithium ion conductivity, and the halide membrane can be matched with the polymer matrix to ensure that the composite membrane forms a compact membrane with low porosity, thereby inhibiting the growth of lithium dendrites and being beneficial to Li dendrites + The rapid transmission of the electrolyte promotes the cycling power of the battery in a high-temperature environment, so that the formed composite solid electrolyte membrane has the advantages of good toughness, good elasticity, high strength, good thermal stability and high ionic conductivity, and the safety and the charge and discharge performance of the solid battery can be improved.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
In one aspect, the present invention provides a composite solid electrolyte membrane. According to an embodiment of the present invention, the composite solid electrolyte membrane includes a polymer matrix and a solid electrolyte membrane disposed on the polymer matrix, the solid electrolyte membrane including a polymer membrane and a halide membrane disposed in a stack.
According to an embodiment of the present invention, there is provided a composite solid electrolyte membraneThe polymer matrix with excellent toughness, elasticity and strength is used as a supporting structure, the solid electrolyte membrane is arranged on the surface of the polymer matrix to provide lithium ion conductivity, and the halide membrane can be matched with the polymer matrix to ensure that the composite membrane forms a compact membrane with low porosity, thereby inhibiting the growth of lithium dendrites and being beneficial to Li dendrite growth + The rapid transmission of the electrolyte promotes the cycle multiplying power of the battery in a high-temperature environment, so that the formed composite solid electrolyte membrane has the advantages of good toughness, good elasticity, high strength, good thermal stability and high ionic conductivity, and the safety and the charge and discharge performance of the solid battery can be further improved.
In some embodiments of the present invention, the halide film is disposed adjacent to the polymer matrix, so that on one hand, the ionic conductivity of the composite solid electrolyte can be improved, and on the other hand, because the elasticity of the inorganic halide film is less than that of the organic polymer film and the polymer matrix, the halide film is sandwiched between the polymer film and the polymer matrix, so that while the halide and the polymer form a dense film, the inorganic layer can be protected by the organic flexible layer, and the halide film is prevented from being broken at a high temperature or under a certain mechanical strength, which affects the interface stability of the battery.
According to actual needs, a person skilled in the art can select to arrange the solid electrolyte membrane on one side or two sides of the polymer matrix, and when the solid electrolyte membrane is arranged on two sides of the polymer matrix, the solid electrolyte membrane can better fill or penetrate through gaps of the polymer matrix in the compounding process, so that electrolytes on two sides of the composite membrane are more uniformly distributed, the uniformity of the conductivity of each part of the large-area composite membrane is facilitated, and the short circuit caused by lithium dendrites due to the fact that the local conductivity and the texture are uneven is avoided.
In some embodiments of the present invention, the raw material composition of the polymer film includes a polymer electrolyte and a lithium salt, and the mass ratio of the polymer electrolyte to the lithium salt is 1 to 20:1, preferably 1 to 5:1. the addition of lithium salt can improve the ionic conductivity of the composite solid electrolyte membrane. The inventors found that if the mass ratio of the polymer electrolyte to the lithium salt is too high, i.e., the ratio of the lithium salt is small, good lithium ion transfer capability is not provided, resulting in a poor conductivity of the electrolyte membrane itself, while if the mass ratio of the polymer electrolyte to the lithium salt is too low, i.e., the lithium salt is excessive, the lithium salt is precipitated after the membrane is dried, resulting in a waste of resources and causing difficulty in dispersion of the slurry.
Optionally, the polymer electrolyte is at least one of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyvinyl alcohol, polycarbonate, polyacrylonitrile (PAN), polyvinylpyrrolidone, polyethylene glycol (PEG), polyethylene oxide (PEO), and polymethyl methacrylate.
Preferably, the polymer electrolyte is prepared by mixing 1-2 parts by mass: 1-3 of polyethylene glycol and polyethylene oxide, thereby improving the film-forming toughness of the polymer film and further improving the film strength.
Optionally, the lithium salt is at least one of lithium bis (trifluoromethyl) sulfonyl imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiFSI), lithium trifluoro methyl sulfonyl imide, lithium bis (oxalato) borate (LiBOB), lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium chloride, lithium hexafluorophosphate, lithium perchlorate. Optionally, the polymer film has a thickness of 2 to 50 μm, preferably 5 to 30 μm. This can improve the toughness and strength of the polymer film.
In some embodiments of the invention, the polymer matrix has a porosity of 30 to 80% and a thickness of 2 to 40 μm. Thus, the toughness, elasticity, and strength of the composite solid electrolyte membrane can be improved. The inventors found that if the porosity is too low, it is not favorable for ions on both sides of the electrolyte membrane to pass through, and if the porosity is too high, the support strength of the matrix becomes poor, and the function of enhancing the membrane strength cannot be effectively achieved; if the polymer matrix is too thin, the matrix is easily damaged at high temperature and high pressure, the production cost of the too thin polymer matrix is high, and if the polymer matrix is too thick, the lithium ion channel paths on the two sides of the electrolyte membrane are too long, which is not favorable for exerting the electrochemical performance.
Optionally, the polymer matrix is at least one of a nonwoven fabric, a fibrous membrane, a meltblown, a porous separator. Thus, the toughness, elasticity, and strength of the composite solid electrolyte membrane can be improved.
Optionally, the polymer matrix is made of at least one of Polyethylene (PE), polypropylene (PP), polystyrene, polyvinyl chloride, polyoxymethylene, polyamide, polycarbonate, polylactic acid (PLA), polymethyl methacrylate, acrylonitrile-styrene copolymer, polybutylene terephthalate, phenolic resin, and amino resin.
In some embodiments of the invention, the halide film has a thickness of 5 to 40 μm. Thereby, the ion conductivity of the composite solid electrolyte membrane can be improved.
Optionally, the raw material of the halide film is Li 3 InCl 6 、Li 3 YbCl 6 、Li 3 YCl 6 、Li 3 ScCl 6 、Li 3 GaCl 6 At least one of (a).
The inventors have found that if the solid electrolyte membrane (i.e., the total thickness of the polymer membrane and the halide membrane) is too thin, it is difficult to prepare a composite electrolyte membrane that meets the basic requirements, and if the solid electrolyte membrane is too thick, the composite electrolyte membrane becomes thicker overall, the ion transfer path increases, the cell impedance increases, and the mass becomes too large, which is also not conducive to improving the cell energy density.
In another aspect, the present invention also provides a method for preparing the above composite solid electrolyte membrane, comprising the steps of:
s1, mixing the polymer electrolyte, the lithium salt and an organic solvent to obtain slurry under a protective atmosphere, wherein the organic solvent can dissolve both the polymer electrolyte and the lithium salt, optionally, the organic solvent is at least one of methyl formamide, acetonitrile, cyclohexanone, heptane, N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide, and the mass ratio of the polymer electrolyte to the organic solvent is 1:15 to 25, preferably 1: 15-20, thus not only ensuring the full dissolution of the polymer electrolyte and the lithium salt, but also ensuring the complete volatilization of the organic solvent.
S2, coating the slurry to form a film, drying the film in a protective atmosphere, and then drying the film in vacuum to obtain the polymer film. In this step, the slurry may be applied to the support material, dried, and then separated to obtain the polymer film. The specific type of the support material is not particularly limited as long as the release after drying of the polymer film of the present application can be achieved, and for example, the support material may be a polytetrafluoroethylene sheet or a release paper. In some embodiments of the invention, the temperature of the drying in the protective atmosphere is 20 to 30 ℃ and the time is 2 to 72 hours, preferably 4 to 24 hours. Because lithium salt is easy to hydrolyze, and the requirement of drying and dewatering on temperature is high, which can affect PEO, the lithium salt is dried in a protective atmosphere to volatilize redundant organic solvent, and then further heated and dewatered in vacuum, so as to achieve the purpose of thorough drying. The temperature of the vacuum drying is 30-80 ℃, preferably 40-60 ℃, the time of the vacuum drying is 4-72 hours, preferably 12 hours, and the vacuum drying can be carried out under the vacuum degree of-0.1-10 MPa, so that the drying effect can be achieved, and the polymer film cannot be adversely affected.
And S3, overlapping the polymer film, the raw material of the halide film and the polymer matrix and pressing the polymer film and the raw material of the halide film into a film at certain temperature and pressure. In some embodiments of the invention, the pressing is at a temperature of 30 to 150 ℃ and a pressure of 1 to 10MPa.
It should be noted that, in the above preparation method, the mixing ratio of the polymer electrolyte and the lithium salt and the respective species, the thickness of the polymer film, the thickness, porosity and species of the polymer matrix, and the thickness and species of the halide film are equal to the above description, and will not be described again here. Since lithium salt is easily hydrolyzed by water, it is necessary to operate under a protective atmosphere, and the protective gas may be an inert gas such as nitrogen or argon.
In still another aspect, the present invention also provides a solid-state battery comprising the composite solid electrolyte membrane according to the above or a composite solid electrolyte membrane obtained by the above method for producing a composite solid electrolyte membrane.
The solid-state battery provided by the invention adopts the polymer matrix with excellent toughness, elasticity and strength as the support structure of the diaphragm, the solid-state electrolyte membrane is arranged on the surface of the polymer matrix to provide lithium ion conductivity, and the halide membrane can be matched with the polymer matrix to ensure that the composite membrane forms low poresCompact film of porosity to inhibit the growth of lithium dendrites and also to favor Li + The rapid transmission of the electrolyte promotes the cycle multiplying power of the battery in a high-temperature environment, so that the formed composite solid electrolyte membrane has the advantages of good toughness, good elasticity, high strength, good thermal stability and high ionic conductivity, and the safety and the charge and discharge performance of the solid battery can be further improved.
The lithium iron phosphate composite material, the preparation method and the application thereof provided by the present invention will be described in detail with reference to specific embodiments.
Example 1
The preparation method of the composite solid polymer film provided in this example is as follows:
under the protection of argon atmosphere, 33.6g of acetonitrile, 0.4g of polyethylene glycol, 0.2g of lithium bistrifluoromethylsulfonyl imide and 0.8g of polyethylene oxide are weighed and uniformly mixed to obtain a slurry with the solid material mass concentration of 4%, wherein the mass ratio of the polyethylene glycol to the polyethylene oxide is 1.
The slurry obtained above was coated to form a film, which was first dried under argon at room temperature for 8 hours, and then further dried in a vacuum environment at 50 ℃ for 12 hours to obtain a polymer film having a thickness of 5 μm.
Lamination of Li to Polymer films 3 ScCl 6 Laminating non-woven fabric (PP/PLA/PE), and coating Li on the polymer film 3 ScCl 6 The non-woven fabric is pressed under the conditions of 60 ℃ and 2MPa to obtain the composite solid electrolyte membrane SPE PEG-PEO-LiTFSI /Li 3 ScCl 6 Film/nonwoven. Wherein the thickness of the non-woven fabric is 10 μm, the porosity is 50%, and Li 3 ScCl 6 The film thickness was 15 μm.
Examples 2 to 10, composite solid electrolyte membranes were prepared by adjusting the mass ratio of polyethylene glycol and polyethylene oxide, the mass ratio of lithium bis (fluorosulfonyl) imide salt and polyethylene oxide, and the type of halide membrane on the basis of example 1.
Examples 11 to 12 composite solid electrolyte membranes were prepared by adjusting the kind of lithium salt in addition to example 1.
Example 13 a composite solid electrolyte membrane was prepared by adjusting the kind of polymer membrane on the basis of example 1.
Example 14 a composite solid electrolyte membrane was prepared by adjusting the kind of polymer matrix on the basis of example 1.
Comparative example 1
A composite solid electrolyte membrane SPE was obtained in the same manner as in example 1 except that the slurry contained no polyethylene glycol PEO-LiTFSI /Li 3 ScCl 6 Film/nonwoven.
Comparative example 2
A composite solid electrolyte membrane SPE was obtained in the same manner as in example 1 except that the electrolyte membrane contained no nonwoven fabric PEG-PEO-LiTFSI /Li 3 ScCl 6 And (3) a film.
Comparative example 3
A composite solid electrolyte membrane SPE was obtained in the same manner as in example 1 except that the electrolyte membrane did not contain a halide film PEG-PEO-LiTFSI Non-woven fabric.
Test example
The composite solid electrolyte membranes prepared in the above examples 1 to 14 and comparative examples 1 to 3 were subjected to impedance analysis tests to obtain ion conductivity values of the electrolytes. The specific test process is as follows: and (3) tabletting the composite solid electrolyte membrane, then loading the tabletted composite solid electrolyte membrane into a mold sleeve at the temperature of 60 ℃, pressurizing, carrying out alternating current impedance spectroscopy test by using an impedance analyzer, and calculating the ionic conductivity of the electrolyte material according to the impedance value. The composite solid electrolyte membrane was used as an electrolyte layer of a sulfide all-solid-state lithium metal negative electrode mold battery and subjected to a charge and discharge test at 60 ℃ at 0.1C (1c = 180ma/g), and the test results are shown in table 1.
TABLE 1
As can be seen from table 1, in the examples of the present invention, when the PEG to PEO mass ratio is 1 3 ScCl 6 Film, and Li salt is LiTFSI, the composite solid electrolyte membrane SPE prepared PEG-PEO-LiTFSI /Li 3 ScCl 6 The film/non-woven fabric (compounded by PP/PLA/PE) has the highest conductivity, the specific capacity of 100 circles of charge and discharge at 0.1 ℃ is the highest, and the retention rate reaches 91%. PEG and Li can be comparatively analyzed by combining with comparative examples 1 to 3 3 ScCl 6 The introduction of the membrane and non-woven fabric (compounded by PP/PLA/PE) can effectively improve the electrochemical characteristics of the composite solid electrolyte membrane.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A composite solid electrolyte membrane comprising a polymer matrix and a solid electrolyte membrane disposed on the polymer matrix, characterized in that the solid electrolyte membrane comprises a polymer membrane and a halide membrane disposed in a stack.
2. The composite solid electrolyte membrane according to claim 1, wherein the solid electrolyte membrane is disposed on one or both sides of the polymer matrix; and/or, the halide film is disposed proximate to the polymer matrix.
3. The composite solid electrolyte membrane according to claim 1 or 2, wherein the raw material composition of the polymer membrane includes a polymer electrolyte and a lithium salt, and the mass ratio of the polymer electrolyte to the lithium salt is 1 to 20:1, preferably 1 to 5:1;
optionally, the polymer electrolyte is at least one of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyvinyl alcohol, polycarbonate, polyacrylonitrile, polyvinylpyrrolidone, polyethylene glycol, polyethylene oxide and polymethyl methacrylate, and preferably the mass ratio of polyethylene glycol to polyethylene oxide is 1-2;
optionally, the lithium salt is at least one of lithium bis (trifluoromethyl) sulfonyl imide, lithium bis (fluoro) sulfonyl imide, lithium trifluoro methyl sulfonyl imide, lithium bis (oxalate) borate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium chloride, lithium hexafluorophosphate and lithium perchlorate;
optionally, the polymer film has a thickness of 2 to 50 μm, preferably 5 to 30 μm.
4. The composite solid electrolyte membrane according to claim 1 or 2, characterized in that the porosity of the polymer matrix is 30 to 80% and the thickness is 2 to 40 μm;
optionally, the polymer matrix is at least one of a nonwoven fabric, a fibrous membrane, a meltblown, a porous separator.
5. The composite solid electrolyte membrane according to claim 1 or 2, characterized in that the thickness of the halide film is 5 to 40 μm;
optionally, the raw material of the halide film is Li 3 InCl 6 、Li 3 YbCl 6 、Li 3 YCl 6 、Li 3 ScCl 6 、Li 3 GaCl 6 At least one of (a).
6. A method of producing a composite solid electrolyte membrane according to any one of claims 1 to 5, characterized by comprising the steps of:
mixing the polymer electrolyte, the lithium salt and an organic solvent under a protective atmosphere to obtain slurry, coating the slurry to form a film, drying the film in the protective atmosphere, and then drying the film in vacuum to obtain the polymer film;
the polymer film, the raw material for the halide film, the polymer matrix are stacked and pressed into a film.
7. The method of producing a composite solid electrolyte membrane according to claim 6, characterized in that the mass ratio of the polymer electrolyte to the organic solvent is 1:15 to 25, preferably 1:15 to 20;
optionally, the organic solvent is at least one of methyl formamide, acetonitrile, cyclohexanone, heptane, N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide, and N, N-dimethylacetamide.
8. The method for producing a composite solid electrolyte membrane according to claim 6, characterized in that the temperature of drying in the protective atmosphere is 20 to 30 ℃ for 2 to 72 hours, preferably 4 to 24 hours;
optionally, the temperature of the vacuum drying is 30-80 ℃, preferably 40-60 ℃, and the time of the vacuum drying is 4-72 hours, preferably 12 hours.
9. The method for producing a composite solid electrolyte membrane according to any one of claims 6 to 8, characterized in that the pressing temperature is 30 to 150 ℃ and the pressure is 1 to 10MPa.
10. A solid-state battery comprising the composite solid-state electrolyte membrane according to any one of claims 1 to 5 or the composite solid-state electrolyte membrane produced by the method for producing a composite solid-state electrolyte membrane according to any one of claims 6 to 9.
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