CN114069037A - Gel polymer electrolyte, preparation method and application thereof, solid-state lithium battery and preparation method thereof - Google Patents
Gel polymer electrolyte, preparation method and application thereof, solid-state lithium battery and preparation method thereof Download PDFInfo
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- CN114069037A CN114069037A CN202110931372.6A CN202110931372A CN114069037A CN 114069037 A CN114069037 A CN 114069037A CN 202110931372 A CN202110931372 A CN 202110931372A CN 114069037 A CN114069037 A CN 114069037A
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- nanofiber membrane
- lithium
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 63
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000002121 nanofiber Substances 0.000 claims abstract description 109
- 239000012528 membrane Substances 0.000 claims abstract description 107
- 239000002243 precursor Substances 0.000 claims abstract description 52
- 239000011245 gel electrolyte Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 29
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 25
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 25
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 25
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 25
- 238000011065 in-situ storage Methods 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- -1 lithium tetrafluoroborate Chemical compound 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 26
- 229910003002 lithium salt Inorganic materials 0.000 claims description 18
- 159000000002 lithium salts Chemical class 0.000 claims description 18
- 239000000835 fiber Substances 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 16
- 239000006184 cosolvent Substances 0.000 claims description 15
- 239000003792 electrolyte Substances 0.000 claims description 13
- 238000011068 loading method Methods 0.000 claims description 13
- 238000004806 packaging method and process Methods 0.000 claims description 13
- 229910000831 Steel Inorganic materials 0.000 claims description 12
- 239000010959 steel Substances 0.000 claims description 12
- 239000004642 Polyimide Substances 0.000 claims description 11
- 239000012300 argon atmosphere Substances 0.000 claims description 11
- 239000012752 auxiliary agent Substances 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- 229920001721 polyimide Polymers 0.000 claims description 11
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 6
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 5
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000004697 Polyetherimide Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004954 Polyphthalamide Substances 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 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
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920001601 polyetherimide Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 229920006375 polyphtalamide Polymers 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 45
- 238000003756 stirring Methods 0.000 description 17
- 238000009987 spinning Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000010041 electrostatic spinning Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical class O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical class CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Chemical class 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 230000010412 perfusion Effects 0.000 description 4
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001523 electrospinning Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- ZHDTXTDHBRADLM-UHFFFAOYSA-N hydron;2,3,4,5-tetrahydropyridin-6-amine;chloride Chemical group Cl.NC1=NCCCC1 ZHDTXTDHBRADLM-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 125000006091 1,3-dioxolane group Chemical group 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000004438 eyesight Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Images
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
-
- 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
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a gel polymer electrolyte, a preparation method and application thereof, a solid-state lithium battery and a preparation method thereof, and belongs to the technical field of lithium ion battery materials. The invention adopts an in-situ polymerization method to load the liquid gel electrolyte precursor solution on the nanofiber membrane, and the nanofiber membrane has the advantages of high porosity, high liquid absorption rate, good flexibility and good thermal stability, and can ensure that the gel polymer electrolyte and the polymer electrolyte are mixedThe positive and negative pole pieces of the lithium battery are in full contact, so that the interface compatibility is improved, the interface impedance is reduced, and the ionic conductivity of the solid-state lithium battery is further improved. The invention uses polymer nanofiber membranes or SiO2The nanofiber membrane supports the gel electrolyte, so that the thermal stability and the ionic conductivity of the gel electrolyte can be improved, and the prepared solid-state lithium battery has the characteristics of high ionic conductivity and high stability of charge-discharge and cycle performance.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a gel polymer electrolyte, a preparation method and application thereof, a solid-state lithium battery and a preparation method thereof.
Background
Lithium ion batteries have attracted attention because of their advantages of high specific energy, long service life, high and relatively stable operating voltage, and are currently used in electronic devices such as mobile phones, computers, and cameras. The traditional lithium ion battery mostly uses electrolyte, has higher ionic conductivity and charge-discharge efficiency, but the electrolyte is easy to leak, has strong corrosivity, is inflammable and explosive, and has great potential safety hazard. Therefore, people transfer the eyesight to the all-solid-state battery, the safety and stability of the all-solid-state battery are obviously improved, the cycle life is longer, but the interface compatibility of the all-solid-state electrolyte is poor, the impedance is high, the room-temperature ionic conductivity is low, and the use requirement of the battery is difficult to meet. The gel electrolyte (GPE) has the advantages of both the electrolyte and the all-solid-state electrolyte, the safety is improved, the interface compatibility is better than that of the all-solid-state electrolyte, and the ionic conductivity is correspondingly improved. Therefore, gel electrolyte solid state batteries are currently one of the most promising new generation of high performance energy storage devices. However, the gel electrolyte supported by the polypropylene diaphragm prepared by the traditional methods (such as extraction method and phase transfer method) has poor interface contact with positive and negative electrode plates, low ionic conductivity and poor thermal stability of the battery, thereby resulting in poor battery charge and discharge performance.
Disclosure of Invention
The invention aims to provide a gel polymer electrolyte, a preparation method and application thereof, a solid-state lithium battery and a preparation method thereof, and the lithium battery constructed by the prepared gel polymer electrolyte has excellent charge and discharge performance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a gel polymer electrolyte, which comprises the following steps:
loading the precursor solution of the gel electrolyte on the nanofiber membrane, and carrying out in-situ polymerization to obtain the gel polymer electrolyte;
the nanofiber membrane is a polymer nanofiber membrane or SiO2A nanofiber membrane.
Preferably, the gel electrolyte precursor solution comprises a lithium salt, a polymer monomer and an auxiliary agent; the lithium salt comprises at least one of lithium tetrafluoroborate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium bistrifluoromethanesulfonimide, lithium difluorooxalato borate and lithium hexafluorophosphate; the polymer monomer comprises methyl methacrylate, polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride or 1,3 dioxolane; the auxiliary agent comprises a cosolvent and/or an initiator, wherein the cosolvent comprises at least one of ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dipropyl carbonate, propylene carbonate and ethylene glycol dimethyl ether; the initiator comprises an azo initiator, and the azo initiator comprises azobisisobutyronitrile, azobisisoheptonitrile or dimethyl azobisisobutyrate.
Preferably, the mass ratio of the lithium salt, the polymer monomer and the auxiliary agent is (0.2-1.5): (1-1.2): 0.5-4); the mass ratio of the cosolvent to the initiator is (1.8-2.2) to (0.01-0.02).
Preferably, the polymer nanofiber membrane comprises a polyimide nanofiber membrane, a polyethylene nanofiber membrane, a polypropylene nanofiber membrane, a polyphthalamide ether sulfone ketone nanofiber membrane, a polyetherimide nanofiber membrane, a polyethylene terephthalate nanofiber membrane or a polymetaphenylene diamide nanofiber membrane; the SiO2The diameter of a single fiber in the nanofiber membrane is 200-400 nm, and the diameter of a single fiber in the polymer nanofiber membrane is 200-300 nm.
Preferably, the loading mode comprises dripping or dipping; the load capacity of the gel electrolyte precursor solution on the nanofiber membrane is 20-30 mu L/cm2。
Preferably, the temperature of the in-situ polymerization is 20-60 ℃, and the time is 10-24 h.
The invention provides a gel polymer electrolyte prepared by the preparation method in the technical scheme, which comprises a nanofiber membrane substrate and a gel electrolyte embedded in the nanofiber membrane substrate; the nanofiber membrane is a polymer nanofiber membrane or SiO2A nanofiber membrane.
The invention provides application of the gel polymer electrolyte in the technical scheme in preparation of a solid lithium battery.
The invention provides a solid-state lithium battery, and the electrolyte of the solid-state lithium battery is the gel polymer electrolyte in the technical scheme.
The invention provides a preparation method of the solid-state lithium battery in the technical scheme, which comprises the following steps:
sequentially stacking and packaging the positive electrode shell, the positive electrode plate, the gel polymer electrolyte, the negative electrode plate, the steel plate, the elastic sheet and the negative electrode shell in an argon atmosphere to obtain a solid lithium battery;
or, sequentially stacking the positive electrode shell, the positive electrode plate, the nanofiber membrane, the negative electrode plate, the steel sheet, the elastic sheet and the negative electrode shell in sequence under the argon atmosphere, loading the gel electrolyte precursor solution on the nanofiber membrane, carrying out in-situ polymerization, and packaging to obtain the solid-state lithium battery.
The invention provides a preparation method of a gel polymer electrolyte, which comprises the following steps: loading the precursor solution of the gel electrolyte on the nanofiber membrane, and carrying out in-situ polymerization to obtain the gel polymer electrolyte; the nanofiber membrane is a polymer nanofiber membrane or SiO2A nanofiber membrane. According to the invention, an in-situ polymerization method is adopted, and the liquid gel electrolyte precursor solution is loaded on the nanofiber membrane, and the nanofiber membrane has the advantages of high porosity, high liquid absorption rate, good flexibility and good thermal stability, so that the gel polymer electrolyte can be fully contacted with positive and negative pole pieces of a lithium battery, the interface compatibility is improved, the interface impedance is reduced, and the ionic conductivity of the solid-state lithium battery is further improved.
The invention uses polymer nanofiber membranes or SiO2Nanofiber membrane supportThe gel electrolyte can improve the thermal stability and the ionic conductivity of the gel electrolyte, so that the prepared solid-state lithium battery has the characteristics of high ionic conductivity and high stability of charge-discharge and cycle performance.
The gel polymer electrolyte prepared by the invention can automatically gel at room temperature, other complex processes are not needed, the cost is effectively reduced, the risks of easy leakage and explosion of the traditional electrolyte and the like are reduced, and the safety of the solid-state lithium battery can be improved.
Drawings
Fig. 1 is a diagram illustrating a process for preparing a solid lithium battery according to examples 1 and 2;
fig. 2 is a diagram of a gelled solution of the gel electrolyte precursors prepared in examples 1 and 2;
FIG. 3 is SiO prepared in example 12SEM image of nanofiber membrane;
fig. 4 is a graph showing impedance curves of the solid lithium batteries prepared in examples 1 and 2;
fig. 5 is a diagram of the gelled electrolyte precursor solutions prepared in examples 3 and 4;
FIG. 6 is an SEM image of a PI nanofiber membrane prepared in example 3;
FIG. 7 is a graph showing the impedance profile of a lithium solid state battery prepared in example 3;
fig. 8 is a graph showing charge and discharge characteristics of the solid lithium battery prepared in example 3.
Detailed Description
The invention provides a preparation method of a gel polymer electrolyte, which comprises the following steps:
loading the precursor solution of the gel electrolyte on the nanofiber membrane, and carrying out in-situ polymerization to obtain the gel polymer electrolyte;
the nanofiber membrane is a polymer nanofiber membrane or SiO2A nanofiber membrane.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
The invention loads the precursor solution of the gel electrolyte on the nanofiber membrane. In the present invention, the gel electrolyte precursor solution preferably includes a lithium salt, a polymer monomer, and an auxiliary agent; the lithium salt preferably comprises at least one of lithium tetrafluoroborate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium bistrifluoromethanesulfonimide, lithium difluorooxalato borate and lithium hexafluorophosphate; when the lithium salt is one of the above, the ratio of the lithium salts of different types is not particularly limited, and any ratio may be used.
In the present invention, the polymer monomer preferably includes methyl methacrylate, polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, or 1,3 dioxolane.
In the invention, the auxiliary agent preferably comprises a cosolvent and/or an initiator, and the cosolvent preferably comprises at least one of ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dipropyl carbonate, propylene carbonate and ethylene glycol dimethyl ether; when the cosolvent is a plurality of the cosolvent, the proportion of different cosolvent is not specially limited, and any proportion can be adopted; when the cosolvent is two of the above, the mass ratio of any two cosolvents is preferably (1-1.5): 1-1.5, and more preferably (1-1.3): 1-1.3.
In the present invention, the initiator preferably includes an azo-type initiator, and the azo-type initiator preferably includes azobisisobutyronitrile, azobisisoheptonitrile, or dimethyl azobisisobutyrate. In the invention, when the auxiliary agent is preferably a cosolvent and an initiator, the mass ratio of the cosolvent to the initiator is preferably (1.8-2.2): 0.01-0.02), and more preferably (1.9-2.1): 0.015.
In the invention, the mass ratio of the lithium salt, the polymer monomer and the auxiliary agent is preferably (0.2-1.5): 1-1.2): 0.5-4, and more preferably (0.5-1.09): 1.05-1.1): 1.0-3.0.
The preparation process of the precursor solution of the gel electrolyte is not specially limited, and the precursor solution of the gel electrolyte can be obtained by uniformly stirring and mixing the lithium salt, the polymer monomer and the auxiliary agent in the pure argon atmosphere according to the process well known in the art. The stirring speed and time are not particularly limited in the present invention, and the materials can be uniformly mixed according to the process well known in the art.
In the invention, the nanofiber membrane is a polymer nanofiber membrane or SiO2A nanofiber membrane; the polymer nanofiber membrane preferably comprises a polyimide nanofiber membrane, a polyethylene nanofiber membrane, a polypropylene nanofiber membrane, a polyphthalamide ether sulfone ketone nanofiber membrane, a polyetherimide nanofiber membrane, a polyethylene terephthalate nanofiber membrane or a polymetaphenylene diamide nanofiber membrane. In the invention, the diameter of a single fiber in the polymer nanofiber membrane is preferably 200-300 nm. The preparation process of the polymer nanofiber membrane is not particularly limited in the invention, and the polymer nanofiber membrane can be prepared by an electrostatic spinning method well known in the art.
In the present invention, the method for preparing the polyimide nanofiber membrane preferably comprises: performing electrostatic spinning on the polyimide spinning solution precursor sol to obtain a fiber membrane precursor; and carrying out thermal imidization on the fiber film precursor to obtain the polyimide nanofiber film.
In the present invention, the preparation process of the polyimide spinning solution precursor sol preferably includes: and mixing and stirring the anhydride and the ether for 10-30 min, adding diamine in batches in equal amount under the stirring condition, and continuously stirring for 6-7 h to obtain the precursor sol of the polyimide spinning solution. In the present invention, the diamine is preferably N, N-dimethylformamide or N, N-dimethylacetamide; the acid anhydride is preferably pyromellitic dianhydride; the ether is preferably 4, 4-diaminodiphenyl ether. The process of adding the anhydride in batches in equal amount is not specially limited, and the batch times can be adjusted according to actual requirements. The stirring process is not particularly limited in the present invention, and the materials can be uniformly mixed according to a process well known in the art.
In the invention, before use, the anhydride is preferably dried in a vacuum oven for 3-12 h; the temperature for drying is not particularly limited in the present invention, and drying may be performed at a temperature well known in the art.
In the invention, the molar ratio of the ether to the acid anhydride is preferably 1 (1-1.5), and more preferably 1 (1.2-1.3); the dosage of the diamine is preferably selected to ensure that the solid content of the precursor sol of the polyimide spinning solution is 18-30%.
In the present invention, the conditions of the electrospinning preferably include: the direct current voltage is 15-30 KV, the perfusion speed is 0.5-1.2 mL/h, the receiving distance is 15-20 cm, the spinning temperature is 20-45 ℃, and the spinning humidity is 20-50%.
In the invention, the temperature of the thermal imidization is preferably 300 ℃, the time is preferably 6-8 h, and the heating rate of heating to the temperature of the thermal imidization is preferably 2-10 ℃/min, and more preferably 5-8 ℃/min.
In the present invention, the SiO2The preparation process of the nanofiber membrane preferably comprises the following steps: mixing SiO2Performing electrostatic spinning on the precursor solution, and calcining the obtained precursor nanofiber membrane in air atmosphere to obtain SiO2A nanofiber membrane.
In the present invention, the SiO2The precursor solution is preferably prepared from ethyl silicate compounds, water, acid compounds and alcohol compounds; the preparation process is not particularly limited in the present invention, and the preparation can be carried out according to the required ratio by the process well known in the art. In the invention, the mass ratio of the ethyl silicate compound, the water, the acid compound and the alcohol compound is preferably (0.8-1.2): (0.006-0.01): 1.6-2.4), and more preferably 1:1:0.01: 2. The specific types of the ethyl silicate compounds, water, acid compounds and alcohol compounds are not particularly limited, and SiO well known in the art is selected2The precursor solution can be used in any corresponding type.
In the embodiment of the invention, the ethyl silicate compound is tetraethyl orthosilicate; the acid compound is phosphoric acid; the alcohol compound is a polyvinyl alcohol aqueous solution with the mass concentration of 10%; the mass ratio of the water to the ethyl silicate compound to the acid compound to the alcohol compound is 1:1:0.01: 2.
In the present invention, the SiO2The conditions for electrospinning the precursor solution preferably include: keeping the temperature at 25 ℃ and the relative humidity at 30-50%,the perfusion speed is 1-1.5 mL/h, and the voltage is 18-22 kV; the distance between the receiving device and the spinning nozzle is 18cm, and the rotating speed of the receiving device is 50 r/min.
In the invention, the calcination process preferably comprises the steps of heating from 30 ℃ to 200 ℃ at a heating rate of 5-7 ℃/min, then heating to 600-800 ℃, and keeping the temperature for 60-120 min.
In the present invention, the SiO2The diameter of a single fiber in the nanofiber membrane is preferably 200-400 nm.
In the present invention, the manner of the supporting preferably includes dropping or dipping; the preferable load capacity of the gel electrolyte precursor solution on the nanofiber membrane is 20-30 mu l/cm2More preferably 25. mu.l/cm2. The dropping rate and the impregnation process are not particularly limited in the present invention, and the above loading amount can be achieved by dropping or impregnating according to the process well known in the art.
In the invention, the in-situ polymerization temperature is preferably 20-60 ℃, and the time is preferably 10-24 h; when the polymer monomer is 1,3 dioxolane, the temperature of the in-situ polymerization is preferably 20-35 ℃.
The invention provides a gel polymer electrolyte prepared by the preparation method in the technical scheme, which comprises a nanofiber membrane substrate and a gel electrolyte embedded in the nanofiber membrane substrate; the nanofiber membrane is a polymer nanofiber membrane or SiO2A nanofiber membrane.
The invention provides application of the gel polymer electrolyte in the technical scheme in preparation of a solid lithium battery.
The invention provides a solid-state lithium battery, and the electrolyte of the solid-state lithium battery is the gel polymer electrolyte in the technical scheme. In the present invention, the positive electrode material for the solid-state lithium battery is preferably lithium cobaltate, lithium manganate or lithium iron phosphate. The present invention is not limited to any particular structure of the solid-state lithium battery, and any button solid-state battery or soft-package solid-state lithium battery known in the art may be used.
The invention provides a preparation method of the solid-state lithium battery in the technical scheme, which comprises the following steps:
sequentially stacking and packaging the positive electrode shell, the positive electrode plate, the gel polymer electrolyte, the negative electrode plate, the steel plate, the elastic sheet and the negative electrode shell in an argon atmosphere to obtain a solid lithium battery;
or, sequentially stacking the positive electrode shell, the positive electrode plate, the nanofiber membrane, the negative electrode plate, the steel sheet, the elastic sheet and the negative electrode shell in sequence under the argon atmosphere, loading the gel electrolyte precursor solution on the nanofiber membrane, carrying out in-situ polymerization, and packaging to obtain the solid-state lithium battery.
The process of stacking and packaging the positive electrode shell-positive electrode plate-gel polymer electrolyte-negative electrode plate-steel plate-shrapnel-negative electrode shell in sequence is not particularly limited, and the stacking and packaging can be carried out by using a packaging machine according to the process well known in the art.
The invention has no special limitation on the sequential stacking process of the positive electrode shell, the positive electrode plate, the nanofiber membrane, the negative electrode plate, the steel sheet, the shrapnel and the negative electrode shell, and the stacking can be carried out according to the process well known in the field; the process of loading the precursor solution of the gel electrolyte on the nanofiber membrane for in-situ polymerization is the same as the process of preparing the gel polymer electrolyte, and is not described herein again.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, the types of batteries used in assembly in button solid state lithium batteries were: 2025 battery case, 16.2mm 1mm steel sheet, 15.4mm 1.1mm shrapnel, the diameters of lithium iron phosphate positive plate and lithium negative plate are both 13.5mm, the battery assembly sequence is that the positive plate case, lithium iron phosphate positive plate and electrolyte are placed in turn, then the lithium negative plate, steel sheet, shrapnel and negative plate case are placed in turn, and the button battery is assembled.
Example 1
At room temperatureDissolving phosphoric acid in deionized water and tetraethyl orthosilicate, fully mixing, stirring for 8 hours, mixing the obtained solution with a polyvinyl alcohol solution with the mass concentration of 10%, and stirring for 8 hours to obtain SiO2The precursor solution comprises 5g, 0.05g and 10g of deionized water, tetraethyl orthosilicate, phosphoric acid and 10% polyvinyl alcohol solution in a mass ratio of 1:1:0.01: 2; subjecting the SiO2Performing electrostatic spinning on the precursor solution, and applying a constant-temperature thermal field of 25 ℃ in a spinning interval, wherein the electrostatic spinning parameters are as follows: the relative humidity is 45 percent, the perfusion speed is 1mL/h, the voltage is 20kv, the distance between the receiving device and the spinning nozzle is 18cm, and the rotating speed of the receiving device is 50r/min, thus obtaining the SiO2A precursor fiber film; subjecting the SiO2Placing the precursor fiber film in air atmosphere, calcining, heating from 30 ℃ to 200 ℃ at a heating rate of 6 ℃/min, heating to 800 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 120min to obtain SiO2A nanofiber membrane;
adding methyl methacrylate into a mixed solution of ethylene carbonate and diethyl carbonate in a glove box filled with argon, adding lithium salt (lithium bis (trifluoromethanesulfonylimide)) into the obtained mixed solution, taking out the mixed solution, stirring until the lithium salt is completely dissolved, adding 2, 2-azobisisobutyronitrile, and stirring for 15min to obtain a gel electrolyte precursor solution, wherein the mass of the lithium salt, the mass of the methyl methacrylate, the mass of the ethylene carbonate, the mass of the diethyl carbonate and the mass of the 2, 2-azobisbutyronitrile are respectively 1g:1g:1g:1g:0.01 g;
in a glove box filled with argon, 40. mu.l of the gel electrolyte precursor solution was added dropwise to SiO placed in a petri dish using a pipette2On the nanofiber membrane so that the loading amount was 22. mu.l/cm2And standing for 24 hours at normal temperature (25 ℃) to obtain the gel polymer electrolyte.
The gel polymer electrolyte is cut into the size of the button type solid lithium battery diaphragm, and the cut gel polymer electrolyte is used to replace the diaphragm and electrolyte in the battery to assemble the solid lithium battery as shown in the method (a) in figure 1.
Example 2
Preparation of SiO by the method of example 12A nanofiber membrane;
adding methyl methacrylate into a mixed solution of ethylene carbonate and diethyl carbonate in a glove box filled with argon, adding lithium salt (lithium bis (trifluoromethanesulfonylimide)) into the mixed solution, taking out and stirring until the lithium salt is completely dissolved, adding 2, 2-azobisbutyronitrile, and stirring for 15min to obtain a gel electrolyte precursor solution, wherein the mass of the lithium salt, the mass of the methyl methacrylate, the mass of the ethylene carbonate, the mass of the diethyl carbonate and the mass of the 2, 2-azobisbutyronitrile are respectively 1.2g:1g:1g:1g:0.02 g;
as shown in (b) of FIG. 1, in a glove box filled with argon, lithium iron phosphate positive plate-SiO was used2The order of the nanofiber membrane and the lithium negative plate is that the gel electrolyte precursor solution is dropwise added to SiO2On the nanofiber membrane so that the loading amount was 22. mu.l/cm2And standing the assembled battery for 24 hours at normal temperature (25 ℃) to obtain the solid lithium battery.
Example 3
Preparing a PI nanofiber membrane by adopting an electrostatic spinning method: putting pyromellitic dianhydride into a vacuum oven to be dried for 8 hours, mixing and stirring 7.2g N, N-dimethylformamide and 1.34g of 4, 4-diaminodiphenyl ether for 30 minutes, adding the dried 1.46g of pyromellitic dianhydride into the obtained mixture in equal amount and times under the condition of continuous stirring, and continuously stirring for 6 hours to obtain a polyimide spinning solution precursor sol with the solid content of 28%; and (2) performing electrostatic spinning on the polyimide spinning solution precursor sol, wherein the electrostatic spinning conditions are as follows: the direct current voltage is 28KV, the perfusion speed is 0.8mL/h, the receiving distance is 18cm, the spinning temperature is 25 ℃, and the spinning humidity is 45%, so that a fiber membrane precursor is obtained; carrying out thermal imidization on the fiber film precursor for 6h at 300 ℃, heating to the thermal imidization temperature at the heating rate of 2 ℃/min to obtain a PI nanofiber film, and cutting the PI nanofiber film into PI diaphragms which are suitable for the size of button solid lithium batteries by using a slicing machine;
1.3319g of 1, 3-Dioxolane (DOL) and 1.0831g of ethylene glycol dimethyl ether were mixed under a pure argon atmosphere, and 0.7177g of lithium bistrifluoromethanesulfonimide (LiTFSI) and 0.3798g of lithium hexafluorophosphate (LiPF) were sequentially added to the resulting mixture6) Stirring and mixing uniformly to obtain a precursor solution of the gel electrolyte;
placing the positive electrode shell, the lithium iron phosphate positive plate and the PI diaphragm in sequence under the pure argon atmosphere, and dropwise adding 40 mu L of gel electrolyte precursor solution to the PI diaphragm by using a liquid-transferring gun to enable the loading capacity to be 30 mu L/cm2And sequentially placing a lithium negative plate, a steel sheet, an elastic sheet and a negative shell to assemble the button cell, standing for 12 hours at room temperature, and packaging by using a packaging machine to obtain the solid-state lithium battery.
Example 4
Preparing a PI nanofiber membrane according to the method of the embodiment 3, and cutting the PI nanofiber membrane into a PI diaphragm with the size suitable for a button cell by using a slicer;
1.3319g of 1, 3-Dioxolane (DOL) and 1.0831g of ethylene glycol dimethyl ether (DME) were mixed under a pure argon atmosphere, and 0.7177g of lithium bistrifluoromethanesulfonimide (LiTFSI) and 0.3798g of lithium hexafluorophosphate (LiPF) were sequentially added to the resulting mixture6) Stirring and mixing uniformly to obtain a precursor solution of the gel electrolyte; under the atmosphere of pure argon, immersing the precursor solution of the gel electrolyte into a PI nanofiber membrane, and standing at room temperature for 12 hours to form a gel polymer electrolyte;
and (3) sequentially placing the positive plate shell, the lithium iron phosphate (LFP) positive plate, the gel polymer electrolyte, the Li negative plate, the steel sheet, the elastic sheet and the negative plate shell in a pure argon atmosphere to assemble the button cell, and packaging by using a packaging machine to obtain the solid-state lithium battery.
Characterization and Performance testing
1) The physical diagrams after gelation of the gel electrolyte precursor solutions prepared in examples 1 and 2 are shown in fig. 2, wherein a represents example 1, and b represents example 2; as can be seen from fig. 2, the gel electrolyte precursor solutions of examples 1 and 2 can be formed into a gel state.
2) For SiO prepared in example 12SEM test is carried out on the nanofiber membrane, and the obtained result is shown in figure 3; as shown in FIG. 3, SiO2The diameter of a single fiber of the nanofiber membrane is 200-400 nm, and the fiber is uniform in evenness.
3) For the solids prepared in example 1 and example 2The lithium battery was subjected to impedance testing, and the results are shown in fig. 4. As can be seen from fig. 4, the impedance of the battery is small, indicating that the ionic conductivity is high. According to fig. 4, the ion conductivities of the solid lithium batteries prepared in examples 1 and 2 were calculated, and the formula of the ion conductivity was σ ═ L/(R ×) and L was the gel polymer electrolyte thickness (100 μm); s is the area of the gel polymer electrolyte, the diameter is 13.5mm, and the ionic conductivity of the solid lithium battery prepared in example 1 is calculated to be 6.354X 10-3S/m, the ionic conductivity of the lithium solid state battery prepared in example 2 was 9.406X 10-3And S/m indicates that the prepared solid-state lithium battery has small interface impedance.
4) Fig. 5 shows the physical diagrams of the gel electrolyte precursor solutions prepared in examples 3 and 4 after gelation, wherein a represents example 3 and b represents example 4; as can be seen from fig. 5, the gel electrolyte precursor solutions of examples 3 and 4 can be formed into a gel state.
5) SEM testing of the PI nanofiber membrane prepared in example 3 gave the results shown in fig. 6; as can be seen from FIG. 6, the fibers in the PI nanofiber membrane are well straightened and are uniform, and the diameter of each fiber is 200-300 nm.
6) The impedance test was performed on the solid lithium battery prepared in example 3 using the electrochemical workstation, and the obtained result is shown in fig. 7, and as can be seen from fig. 7, the impedance of the lithium battery was about 100 Ω, and from the impedance curve, the ionic conductivity was calculated, and the formula of the ionic conductivity was σ ═ L/(R × S), and L was the gel polymer electrolyte thickness (100 μm); s is the area of the gel polymer electrolyte, the diameter is 13.5mm, and the ion conductivity is calculated to be 6.99 multiplied by 10-3S/m。
7) The electrical performance of the solid-state lithium battery prepared in example 3 was tested using the novyi battery test system, and the battery parameters, namely, 16mg of active material, a nominal specific capacity of 170mAh/g, a first step charge-discharge rate of 0.1C, a second step charge-discharge rate of 0.2C, were set, and the results are shown in fig. 8; as can be seen from fig. 8, the charge/discharge specific capacity of the battery was relatively stable, slightly decreased, and the charging efficiency was stable and maintained at 98% or more.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a gel polymer electrolyte is characterized by comprising the following steps:
loading the precursor solution of the gel electrolyte on the nanofiber membrane, and carrying out in-situ polymerization to obtain the gel polymer electrolyte;
the nanofiber membrane is a polymer nanofiber membrane or SiO2A nanofiber membrane.
2. The method of claim 1, wherein the gel electrolyte precursor solution comprises a lithium salt, a polymer monomer, and an auxiliary agent; the lithium salt comprises at least one of lithium tetrafluoroborate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium bistrifluoromethanesulfonimide, lithium difluorooxalato borate and lithium hexafluorophosphate; the polymer monomer comprises methyl methacrylate, polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride or 1,3 dioxolane; the auxiliary agent comprises a cosolvent and/or an initiator, wherein the cosolvent comprises at least one of ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dipropyl carbonate, propylene carbonate and ethylene glycol dimethyl ether; the initiator comprises an azo initiator, and the azo initiator comprises azobisisobutyronitrile, azobisisoheptonitrile or dimethyl azobisisobutyrate.
3. The method according to claim 1, wherein the mass ratio of the lithium salt, the polymer monomer and the auxiliary agent is (0.2-1.5): (1-1.2): (0.5-4); the mass ratio of the cosolvent to the initiator is (1.8-2.2) to (0.01-0.02).
4. The method of claim 1, wherein the polymeric nanofiber membrane comprises a polyimide nanofiber membrane, a polyethylene nanofiber membrane, a polypropylene nanofiber membraneAn alkene nanofiber membrane, a polyphthalamide ether sulfone ketone nanofiber membrane, a polyetherimide nanofiber membrane, a polyethylene terephthalate nanofiber membrane or a polymetaphenylene diamide nanofiber membrane; the SiO2The diameter of a single fiber in the nanofiber membrane is 200-400 nm, and the diameter of a single fiber in the polymer nanofiber membrane is 200-300 nm.
5. The production method according to claim 1, wherein the manner of supporting includes dropping or dipping; the load capacity of the gel electrolyte precursor solution on the nanofiber membrane is 20-30 mu L/cm2。
6. The preparation method according to claim 1, wherein the in-situ polymerization temperature is 20-60 ℃ and the time is 10-24 h.
7. The gel polymer electrolyte prepared by the preparation method of any one of claims 1 to 6, which comprises a nanofiber membrane substrate and a gel electrolyte embedded in the nanofiber membrane substrate; the nanofiber membrane is a polymer nanofiber membrane or SiO2A nanofiber membrane.
8. Use of the gel polymer electrolyte of claim 7 in the manufacture of a lithium solid state battery.
9. A solid state lithium battery characterized in that an electrolyte of the solid state lithium battery is the gel polymer electrolyte of claim 7.
10. A method of making a solid state lithium battery as claimed in claim 9, comprising the steps of:
sequentially stacking and packaging the positive electrode shell, the positive electrode plate, the gel polymer electrolyte, the negative electrode plate, the steel plate, the elastic sheet and the negative electrode shell in an argon atmosphere to obtain a solid lithium battery;
or, sequentially stacking the positive electrode shell, the positive electrode plate, the nanofiber membrane, the negative electrode plate, the steel sheet, the elastic sheet and the negative electrode shell in sequence under the argon atmosphere, loading the gel electrolyte precursor solution on the nanofiber membrane, carrying out in-situ polymerization, and packaging to obtain the solid-state lithium battery.
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| CN114583257A (en) * | 2022-03-17 | 2022-06-03 | 东华大学 | Gel electrolyte precursor solution, integrated gel solid-state lithium battery and preparation method thereof |
| CN115020641A (en) * | 2022-05-11 | 2022-09-06 | 五邑大学 | Lithium metal negative plate and preparation method and application thereof |
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| CN108281705A (en) * | 2018-01-25 | 2018-07-13 | 中国科学院过程工程研究所 | Modified Nano SiO2Particle, preparation method and nano fibrous membrane, gel electrolyte and lithium metal battery comprising it |
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| CN104393336A (en) * | 2014-11-13 | 2015-03-04 | 湘潭大学 | Nano composite fiber-reinforced gel polymer electrolyte and preparation method thereof |
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