Spider web-like polymer electrolyte membrane, preparation method thereof and fast-charging solid-state battery

Abstract

The invention discloses a cobweb-like polymer electrolyte membrane, a preparation method thereof and a fast-charging solid-state battery. The cobweb-like polymer electrolyte membrane comprises a porous base membrane and cobweb-like polymer electrolyte filled in the porous base membrane. A porous base membrane is used for adsorbing a polymer precursor solution, a cobweb-like polymer is constructed through a polymerization reaction of a double-polymerization-site monomer and a multi-arm cross-linking agent in the precursor solution, the polymerization degree is regulated and controlled to change a coordination microenvironment of ether oxygen bonds and lithium ions, lithium ion conduction is promoted, and the room-temperature ionic conductivity gt is achieved; 4 mS cm < 1 >; the cobweb-like polymer is favorable for enhancing the oxidation resistance and the electrochemical stability window gt; 5 V; the lithium symmetric battery can stably operate for 800 hours under the electroplating / stripping capacity of 0.2 mAh cm < 2 >, the capacity retention rate of an LFPLi battery after 1000 cycles at 5 DEG C is 88%, the capacity retention rate of an NCM811Li battery after 800 cycles at 10 DEG C is 64%, the NCM811Li battery can stably circulate for 500 cycles at 1 DEG C, and the lithium symmetric battery has the industrialization prospect of rapid charging and discharging.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of solid-state electrolyte membrane for solid-state lithium battery, and particularly relates to a spider-web-like polymer electrolyte membrane, a preparation method thereof and a fast-charging solid-state battery. BACKGROUND

[0002] With the consensus of 'decarbonization' gradually strengthening in the global range, lithium ion batteries become one of the key pivots for realizing the transition from fossil fuels to renewable energy such as wind energy and solar energy. Lithium ion batteries are not only the cornerstone of portable electronic devices such as smart phones and notebook computers, but also the heart of new energy vehicles, and the popularization of pure electric vehicles and plug-in hybrid electric vehicles completely depends on the progress of lithium ion battery technology. At the same time, lithium ion batteries are also the key to large-scale energy storage of renewable energy such as solar energy and wind energy. However, the traditional liquid lithium ion battery has the safety risks of easy leakage and easy combustion of electrolyte, and it is difficult to meet the demand of high energy density. Compared with this, the solid-state lithium ion battery can realize high energy density while maintaining high safety, and it has become a major trend in the development of lithium batteries in the future.

[0003] The solid-state electrolyte membrane has the problems of low ion conductivity at room temperature, narrow electrochemical stability window and large impedance of electrolyte-electrode interface, and cannot meet the demand of charging and discharging at a high current density. Research and development of a new type of solid-state electrolyte membrane with high ion conductivity and high electrochemical stability window play an important role in realizing fast charging of solid-state lithium ion batteries. SUMMARY

[0004] The present application proposes to construct a spider-web-like polymer electrolyte membrane through in-situ polymerization reaction of double-polymerization-site monomers and multi-arm crosslinking agents, and provides a preparation method and a formula which can adjust the spider-web-like structure, optimize the lithium ion coordination microenvironment, improve the ion conductivity and electrochemical stability, and realize fast charging of solid-state batteries.

[0005] One of the purposes of the present application is to provide a spider-web-like polymer electrolyte membrane, which adjusts the lithium ion and ether oxygen bond coordination microenvironment through different spider-web-like structures, improves the ion conductivity, and can improve the oxidation resistance of the electrolyte, limit the anion migration, reduce the concentration polarization, and reduce the side reactions at the electrode interface, so as to help the fast charging of solid-state batteries with high ion conductivity and high electrochemical stability.

[0006] The second purpose of the present application is to provide a preparation method of a spider-web-like polymer electrolyte membrane. The method fills a polymer precursor solution in a porous base film, and then obtains a spider-web-like polymer electrolyte membrane through in-situ polymerization reaction of double-polymerization-site monomers and multi-arm crosslinking agents in the polymer precursor solution.

[0007] The third object of the present application is to provide a fast-charging solid-state lithium battery based on a spider-web-like polymer electrolyte membrane, which improves the fast-charging performance of the battery.

[0008] To achieve the above object, the present application provides the following technical solutions. A spider-web-like polymer electrolyte membrane includes a porous base membrane, the base membrane is filled with a spider-web-like polymer electrolyte, the polymer electrolyte includes a spider-web-like polymer, a lithium salt and a plasticizer; the spider-web-like polymer is obtained by in-situ polymerization reaction of a double-polymerization-site monomer and a multi-arm crosslinking agent. The polymer solid-state electrolyte limits anions through a network structure, promotes lithium salt dissociation, improves ionic conductivity, reduces interface side reactions, and improves the oxidation resistance and electrochemical stability window of the electrolyte.

[0009] Further, the double-polymerization-site monomer includes one or more of dimethyl acrylate-1,4-butanediol, diphenyl methane 4,4'-diisocyanate, N,N'-methylene bisacrylamide, triethylene tetramine, p-divinylbenzene, polyethylene glycol diglycidyl ether, hexamethylene diisocyanate, polyethylene glycol diacrylate, 4-vinyl-1-cyclohexene-1,2-epoxy, allyl glycidyl ether, divinyl cyclohexene dioxide, glycidyl methacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, neopentyl glycol diglycidol, 1,4-butanediol diglycidyl ether, glycidyl propargyl ether, 1,6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, tiglic acid leaf alcohol ester, neopentyl glycol diglycidyl ether, 1,6-hexanediol dimethacrylate, 1,6-hexanediol diacrylate, bisphenol A diglycidyl ether, 1,4-bis[(glycidyl oxygen) methyl] cyclohexane, 4-hydroxybutyl acrylate glycidyl ether, 1,6-heptadiene, 1,6-divinyl perfluorohexane, and 1,6-bis(acryloyloxy)-2,2,3,3,4,4,5,5-octafluorohexane.

[0010] Further, the multi-arm crosslinker includes one or more of vinyltrimethoxysilane, 3- aminopropyltriethoxysilane, N-(β-aminoethyl-γ-aminopropyl)methyldimethoxysilane, vinyltriethoxysilane, (3-mercaptopropyl)trimethoxysilane, γ- methacryloxypropyltrimethoxysilane, pentaerythritol tetraacrylate, trimethylolpropane triglycidyl ether, N-phenyl-γ-aminopropyltrimethoxysilane, pentaerythritol triacrylate, 3-(isobutyryloxy)propyltrimethoxysilane, methacryloyloxymethyltrimethoxysilane, (3-acryloyloxypropyl)tris(trimethylsiloxy)silane, 3- acryloyloxypropylmethyldimethoxysilane, glycidyloxypropylcage polysilsesquioxane, 3- glycidyloxypropyltrimethoxysilane, (3-chloropropyl)trimethoxysilane, allyltrimethoxysilane, acetyloxypropyltrimethoxysilane, trimethoxy(3,3,3-trifluoropropyl)silane, pentaerythritol glycidyl ether, (3-methacryloyloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane, 3-[(2,3)-epoxypropoxy]propylmethyldimethoxysilane, isocyanuric acid triglycidyl ester, tris(2-acryloyloxyethyl)isocyanurate, triallyl isocyanurate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triallyl ether, tetra(3-mercaptopropionic acid) pentaerythritol ester, and glycerol triglycidyl ether.

[0011] Further, the porous base film includes one or more of a commercialized separator, a spin film, a phase inversion film, and a modified porous film of the commercialized separator, the spin film, or the phase inversion film.

[0012] Further, the commercialized separator includes one or more of a polypropylene film (PP), a polyethylene film (PE), aluminum oxide (AAO), glass fiber, cellulose, and cellulose acetate; and the spin film or the phase inversion film includes one or more of a spin film or a phase inversion film of cellulose, cellulose acetate, polyacrylonitrile, polyvinylidene-hexafluoropropylene, polyvinylidene fluoride, polyimide, polyetherimide, polyvinyl alcohol, polyvinylpyrrolidone, polymethyl methacrylate, polyvinyl chloride, and polybenzimidazole.

[0013] Further, the lithium salt includes one or more of lithium hexafluorophosphate, lithium difluorophosphate, lithium perchlorate, lithium bis(trifluoromethanesulfonyl)imide, lithium bisfluorosulfonylimide, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium bisoxalate borate, and lithium difluorooxalate borate.

[0014] Further, the lithium salt is a mixture of one or more of lithium bisfluorosulfonylimide, lithium tetrafluoroborate, lithium hexafluorophosphate, and lithium difluorooxalate borate and one or more of lithium difluorophosphate, lithium perchlorate, lithium bis(trifluoromethanesulfonyl)imide, and lithium bisoxalate borate.

[0015] Further, the plasticizer includes one or more of ethylene carbonate, dimethyl carbonate, fluoroethylene carbonate, diethyl carbonate, ethylene glycol dimethyl ether, butanedinitrile, hexanedinitrile, methyl ethyl carbonate, vinylene carbonate, methyl ethyl carbonate, ionic liquid, polyethylene glycol dimethyl ether, methyl propionate, fluoroacetonitrile, propylene carbonate, vinyl ethylene carbonate, bisfluoroethylene carbonate, methyl acetate, ethyl propionate, butyl acetate, ethyl butyrate, propyl propionate, triphenyl phosphite, difluoroethyl acetate, trimethyl phosphate, ethylene sulfite, dimethyl methylphosphonate, and methyl methane disulfonate.

[0016] The application also provides a preparation method of the spider-web-like polymer electrolyte membrane, which includes uniformly mixing a double-polymerization-site monomer, a multi-arm crosslinking agent, a lithium salt, and a plasticizer to obtain a polymer precursor solution, dropping the polymer precursor solution onto a porous base membrane, and obtaining the spider-web-like polymer electrolyte membrane through a polymerization reaction.

[0017] Further, the mass ratio of the double-polymerization-site monomer to the multi-arm crosslinking agent is 1:0.01 to 1:10.

[0018] Further, the mass ratio of the lithium salt to the double-polymerization-site monomer is 0.01:1 to 10:1.

[0019] Further, the mass ratio of the plasticizer to the double-polymerization-site monomer is 0.02:1 to 20:1.

[0020] Further, the polymer precursor solution further includes a polymerization initiator, which includes one or more of di-t-butyl peroxide, potassium persulfate, ammonium persulfate, 2,2-azobis isobutyronitrile, lithium difluoro(oxalato)borate, boron trifluoride, dibenzoyl peroxide, lithium hexafluorophosphate, lithium tetrafluoroborate, aluminum trifluoromethanesulfonate, AlCl3, TiCl4, SnCl4, ZnCl2, SbCl5, MgCl2, Al(OTf)3, and Sn(Oct)2; and the mass ratio of the polymerization initiator to the double-polymerization-site monomer is 0.001:1 to 1:1.

[0021] Further, the polymerization method includes one or more of cationic ring-opening polymerization, anionic ring-opening polymerization, radical polymerization, electrochemical polymerization, thermal polymerization, gamma-ray-initiated polymerization, gel factor-initiated polymerization, and light-initiated polymerization.

[0022] Further, the mixing is stirring mixing, and the stirring time is 1 to 50 h.

[0023] Further, the polymerization reaction temperature is 30 to 250 ℃, and the polymerization time is 0.01 to 100 h.

[0024] The application also provides a fast-charging solid-state battery, comprising the spider-web-like polymer electrolyte film, a positive electrode and a negative electrode.

[0025] Further, the positive electrode comprises LiFePO4, LiNi 0.5 Co 0.2 Mn 0.3 O2, LiNi 0.6 Co 0.2 Mn 0.2 O2, LiNi 0.8 Co 0.1 Mn 0.1 O2, LiNi 0.9 Co 0.05 Mn 0.05 O2, LiNi 0.6 Co 0.1 Mn 0.3 O2, LiCoO2, xLi2MnO3·(1-x)LiMnO2, Li4Ti5O 12 , LiMn2O4, LiMn x Fe 1-x PO4, LiNi x Co y Al2O2, sulfur carbon and sulfur materials; and the negative electrode comprises one or more of lithium metal, graphite, hard carbon and silicon-carbon composite negative electrode materials.

[0026] The application has the following beneficial effects: The spider-web-like polymer electrolyte film of the application effectively limits the migration of anions, regulates the coordination microenvironment of lithium ions and ether oxygen, improves the ionic conductivity >4 mS cm –1 , and can improve the oxidation resistance of the electrolyte, the electrochemical stability window >5 V, reduce the side reactions at the electrode interface, and the high ionic conductivity and high electrochemical stability help the fast charging of the solid-state battery.

[0027] The spider-web-like polymer electrolyte film of the application is simple to prepare, high in operability, low in cost, strong in production compatibility, easy to scale up for large-scale production, and has good industrialization prospects.

[0028] The fast-charging solid-state battery based on the spider-web-like polymer electrolyte film shows excellent electrochemical performance. The ionic conductivity is >4 mS cm –2 at 0.2 mA h cm –2The solid-state LFP||Li battery has a capacity retention rate of 88% after 1000 cycles at 5 C and a capacity retention rate of 64% after 800 cycles at 10 C; the solid-state NCM811||Li battery has an initial discharge specific capacity of 130.9 mAh g –1 at 1 C, and a stable cycle of 500 cycles. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 is a schematic diagram of a spider-web-like polymer; Figure 2 are optical photographs of the PASE-1 solid-state electrolyte prepared in Example 1 (a), the PASE-2 solid-state electrolyte prepared in Example 2 (b), the PASE-0 solid-state electrolyte prepared in Example 3 (c), and the solid-state electrolyte without multi-arm crosslinking agent prepared in Comparative Example 1 (d), respectively.

[0030] Figure 3 are electrochemical impedance spectrograms of the solid-state electrolyte membranes tested at 30 °C, wherein PASE-1, PASE-2, and PASE-0 are spider-web-like solid-state electrolyte membranes prepared in Examples 1-3, respectively.

[0031] Figure 4 are linear sweep voltammetry curves of the solid-state electrolyte membranes, wherein PASE-1, PASE-2, and PASE-0 are spider-web-like solid-state electrolyte membranes prepared in Examples 1-3, respectively.

[0032] Figure 5 are constant current charge-discharge diagrams of lithium symmetric batteries assembled using the solid-state electrolyte membranes, wherein PASE-1, PASE-2, and PASE-0 are spider-web-like solid-state electrolyte membranes prepared in Examples 1-3, respectively.

[0033] Figure 6 are long cycle stability performance diagrams of LFP||Li solid-state batteries assembled using the solid-state electrolyte membranes at 5 C, wherein PASE-1, PASE-2, and PASE-0 are spider-web-like solid-state electrolyte membranes prepared in Examples 1-3, respectively.

[0034] Figure 7 are long cycle stability performance diagrams of LFP||Li solid-state batteries assembled using the solid-state electrolyte membranes at 10 C, wherein PASE-1, PASE-2, and PASE-0 are spider-web-like solid-state electrolyte membranes prepared in Examples 1-3, respectively.

[0035] Figure 8Long cycle stability performance chart of NCM811||Li solid-state battery assembled using solid electrolyte membrane at 1 C, wherein PASE-2 is a spider-web-like solid electrolyte membrane prepared in Example 2, and PASE-0 is a spider-web-like solid electrolyte membrane prepared in Example 3. DETAILED DESCRIPTION

[0036] The specific experimental schemes of the present application will be described in detail below in conjunction with specific examples, but the present application is not limited to the listed examples. If not otherwise specified, the methods are all conventional methods, and the raw materials and instruments used can be purchased on the market. Example 1

[0037] (1) Preparation of porous base membrane Polyacrylonitrile (PAN) was dissolved in N,N-dimethylformamide (DMF) to prepare a uniform yellowish viscous spinning solution, and the mass ratio of PAN to DMF was 1:15. The solution was heated and stirred at 70 ℃ for 11 h. The electrospinning was performed under the conditions of a voltage of 20 kV, a jetting speed of 0.02 mm min –1 , and a receiving distance of 20 cm to obtain a white fiber membrane, i.e., a PAN porous base membrane.

[0038] (2) Preparation of spider-web-like solid electrolyte membrane Allyl glycidyl ether (AGE), a multi-arm crosslinking agent pentaerythritol tetraacrylate (PETEA), a plasticizer (the mass ratio of ethylene carbonate:dimethyl carbonate:fluoroethylene carbonate was 2:3:3), and a lithium salt (the mass ratio of lithium bis(trifluoromethanesulfonyl)imide: lithium difluoro(oxalato)borate was 7:1) were mixed and stirred at room temperature for 6 h, and the mass ratio of AGE:PETEA:plasticizer:lithium salt was 1:0.25:1.5:0.65. Then, a polymerization initiator 2,2-azobisisobutyronitrile (AIBN) was added to form a polymerization precursor solution, and the mass ratio of AIBN to AGE was 0.07:1. The polymerization precursor solution was added dropwise to the PAN porous base membrane prepared in step (1), and was transferred into a 50 ℃ blast oven for heating for 4 h to occur in-situ polymerization to obtain a spider-web-like solid electrolyte membrane, which was denoted as PASE-1.

[0039] (3) Assembly of solid-state lithium metal battery According to the mass ratio of lithium iron phosphate LiFePO4, conductive carbon black Super P and polyvinylidene fluoride PVDF is 8:1:1, after being weighed and placed in a mortar for grinding for 20 min, N-methyl pyrrolidone NMP is added, and the slurry is formed after stirring at room temperature for 12 h, and then scraped on a carbon-coated aluminum foil, and placed in a 70 ℃ air oven for drying for 24 h, and cut into positive electrode round pieces. In an argon atmosphere glove box, PAN porous base film is cut into 19 mm round pieces, and a CR2025 type button lithium metal battery is assembled according to the order of positive electrode piece, PAN porous base film, dropwise addition of the above-mentioned liquid polymerization precursor liquid, lithium metal piece, gasket and spring piece, and a solid-state lithium metal battery based on a spider web-like solid-state electrolyte membrane is obtained after polymerization. Example 2

[0040] The experimental process of Example 2 is the same as that of Example 1, except that the mass ratio of lithium bis-trifluoromethanesulfonimide to lithium difluoro(oxalato)borate is 7:2, and the prepared spider web-like solid-state electrolyte membrane is denoted as PASE-2. Example 3

[0041] The experimental process of Example 3 is the same as that of Example 1, except that the mass ratio of lithium bis-trifluoromethanesulfonimide to lithium difluoro(oxalato)borate is 7:0, and the prepared spider web-like solid-state electrolyte membrane is denoted as PASE-0.

[0042] Comparative Example 1 The experimental process of Comparative Example 1 is the same as steps (1) and (2) of Example 1, except that no multi-arm crosslinking agent PETEA is added, and it cannot be polymerized into a solid state.

[0043] In order to more clearly illustrate the modification results of the embodiments of the present application, the drawings required to be used in the embodiment description will be briefly introduced as follows.

[0044] Figure 1 is a schematic diagram of the spider web-like polymer, which is obtained by in-situ polymerization reaction of a double polymerization site monomer and a multi-arm crosslinking agent.

[0045] Figure 2 are an optical photograph of the PASE-1 solid-state electrolyte prepared in Example 1 (a), an optical photograph of the PASE-2 solid-state electrolyte prepared in Example 2 (b), and an optical photograph of the PASE-0 solid-state electrolyte prepared in Example 3 (c). Figures (a-c) show that the solid-state electrolytes prepared in Examples 1-3 are solid states, and figure (d) shows that the electrolyte in Comparative Example 1 cannot be polymerized into a solid state.

[0046] Figure 3Electrochemical impedance spectra of solid-state electrolyte membranes tested at 30 °C, wherein PASE-1, PASE-2, PASE-0 are the spider-web-like solid-state electrolyte membranes prepared in Examples 1-3, respectively. The ionic conductivity of Example 1 is calculated to be 4.2 mS cm −1 , the ionic conductivity of Example 2 is 4.1 mS cm −1 , and the ionic conductivity of Example 3 is 4.9 mS cm −1 .

[0047] Figure 4 Linear sweep voltammograms of solid-state electrolyte membranes, wherein PASE-1, PASE-2, PASE-0 are the spider-web-like solid-state electrolyte membranes prepared in Examples 1-3, respectively. The electrochemical stability window of PASE-1 is 5.02 V, the electrochemical stability window of PASE-2 is 5.14 V, and the electrochemical stability window of PASE-0 is 4.7 V.

[0048] Figure 5 Constant current charge-discharge curves of lithium symmetric batteries assembled using solid-state electrolyte membranes, wherein PASE-1, PASE-2, PASE-0 are the spider-web-like solid-state electrolyte membranes prepared in Examples 1-3, respectively. Li|PASE-1|Li, Li|PASE-2|Li, and Li|PASE-0|Li are stable for 450 h, 800 h, and 550 h, respectively, at a plating / stripping capacity of 0.2 mAh cm −2 and a current density of 0.2 mA cm −2 .

[0049] Figure 6 Long cycle stability performance of LFP||Li solid-state batteries assembled using solid-state electrolyte membranes at 5 C, wherein PASE-1, PASE-2, PASE-0 are the spider-web-like solid-state electrolyte membranes prepared in Examples 1-3, respectively. The discharge specific capacity of LFP|PASE-1|Li is 66.1 mAh g –1 after 1000 cycles, and the capacity retention rate is 52%; the initial discharge specific capacity of LFP|PASE-2|Li is 109.7 mAh g –1 , the discharge specific capacity is 97 mAh g –1 after 1000 cycles, and the capacity retention rate is 88.4%; the discharge specific capacity of LFP|PASE-0|Li is 57.7 mAh g –1 after 1000 cycles, and the capacity retention rate is 42%.

[0050] Figure 7The long cycle stability performance chart of LFP||Li solid-state battery assembled using solid-state electrolyte film at 10 C, wherein PASE-1, PASE-2, PASE-0 are the spider-web-like solid-state electrolyte films prepared in Examples 1-3, respectively. The capacity retention rate of LFP|PASE-1|Li after 800 cycles is 57%; the discharge specific capacity of LFP|PASE-2|Li after 800 cycles is 73.5 mAh g –1 , and the capacity retention rate is 64%; the discharge specific capacity of LFP|PASE-0|Li after 400 cycles is 88 mAh g -1 , and the capacity retention rate is 80%; Figure 8 The long cycle stability performance chart of NCM811||Li solid-state battery assembled using solid-state electrolyte film at 1 C, wherein PASE-2 is the spider-web-like solid-state electrolyte film prepared in Example 2, and PASE-0 is the spider-web-like solid-state electrolyte film prepared in Example 3. The initial discharge specific capacity of NCM811|PASE-2|Li battery at 1 C is 130.9 mAh g –1 , and after 500 cycles, the initial discharge specific capacity of NCM811|PASE-0|Li battery at 1 C is 116 mAh g -1 , and after 500 cycles.

[0051] The above only describes the preferred embodiments of the present application, although the description is detailed and specific, but this cannot be understood as a limitation on the scope of the present application. For those skilled in the art, any modification, equivalent replacement, improvement, etc. within the scope of the present application without departing from the technical scope of the present application, all belong to the technical solution content of the present application, and still belong to the protection scope of the present application.

Claims

1. A spider web-like polymer electrolyte membrane, characterized in that: The invention includes a porous base membrane filled with a spiderweb-like polymer electrolyte, the polymer electrolyte comprising a spiderweb-like polymer, a lithium salt, and a plasticizer; the spiderweb-like polymer is obtained through in-situ polymerization of a monomer with two polymerization sites and a multi-arm crosslinking agent.

2. The spiderweb-like polymer electrolyte membrane as described in claim 1, characterized in that: The monomers at the dual polymerization sites include 1,4-butanediol dimethacrylate, 4,4'-diphenylmethane diisocyanate, N,N'-methylenebisacrylamide, triethylenetetramine, p-divinylbenzene, polyethylene glycol diglycidyl ether, hexamethylene diisocyanate, polyethylene glycol diacrylate, 4-vinyl-1-cyclohexene-1,2-epoxy, allyl glycidyl ether, vinylcyclohexene dioxide, glycidyl methacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, neopentyl glycol diglycidyl ether, and 1,4-butanediol diglycidyl ether. One or more of the following: glyceryl ether, glycidyl propargyl ether, 1,6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, tebufenozyl ester, neopentyl glycol diglycidyl ether, 1,6-hexanediol dimethacrylate, 1,6-hexanediol diacrylate, bisphenol A diglycidyl ether, 1,4-bis[(glycidoxy)methyl]cyclohexane, 4-hydroxybutylacrylate glycidyl ether, 1,6-heptadiene, 1,6-divinylperfluorohexane, and 1,6-bis(acryloyloxy)-2,2,3,3,4,4,5,5-octafluorohexane.

3. The spiderweb-like polymer electrolyte membrane as described in claim 1, characterized in that: The multi-arm crosslinking agent includes vinyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(β-aminoethyl-γ-aminopropyl)methyldimethoxysilane, vinyltriethoxysilane, (3-mercaptopropyl)trimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, pentaerythritol tetraacrylate, trimethylolpropane triglycidyl ether, N-phenyl-γ-aminopropyltrimethoxysilane, pentaerythritol triacrylate, 3-(isobutenoyloxy)propyltrimethoxysilane, methacryloyloxymethyltrimethoxysilane, (3-acryloyloxypropyl)tri(trimethylsiloxy)silane, 3-acryloyloxypropylmethyldimethoxysilane, glycidyl etheroxypropyl cage-like polysilsesquioxane, 3- One or more of the following: glycidyloxypropyltrimethoxysilane, (3-chloropropyl)trimethoxysilane, allyltrimethoxysilane, acetoxypropyltrimethoxysilane, trimethoxy(3,3,3-trifluoropropyl)silane, pentaerythritol glycidyl ether, (3-methacryloyloxy-2-hydroxypropoxy)propylbis(trimethylsilyloxy)methylsilane, 3-[(2,3)-epoxypropoxy]propylmethyldimethoxysilane, triglycidyl isocyanurate, tri(2-acryloyloxyethyl)isocyanurate, triallyl isocyanurate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triallyl ether, pentaerythritol tetrakis(3-mercaptopropionic acid) ester, and glycerol triglycidyl ether.

4. The spiderweb-like polymer electrolyte membrane as described in claim 1, characterized in that: The porous base membrane includes one or more of commercially available membranes, spun membranes, phase inversion membranes, and modified porous membranes thereof; and / or, The lithium salt includes one or more of lithium hexafluorophosphate, lithium difluorophosphate, lithium perchlorate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium tetrafluoroborate, lithium dioxalate borate, and lithium difluorooxalate borate; and / or, The plasticizer includes one or more of the following: ethylene carbonate, dimethyl carbonate, fluoroethylene carbonate, diethyl carbonate, ethylene glycol dimethyl ether, succinic acid, adiponitrile, methyl ethyl carbonate, vinylene carbonate, methyl ethyl carbonate, ionic liquid, polyethylene glycol dimethyl ether, methyl propionate, fluoroacetonitrile, propylene carbonate, vinyl ethylene carbonate, difluoroethylene carbonate, methyl acetate, ethyl propionate, butyl acetate, ethyl butyrate, propyl propionate, triphenyl phosphite, difluoroethyl acetate, trimethyl phosphate, vinyl sulfite, dimethyl methylphosphonate, and methane disulfonate.

5. The spiderweb-like polymer electrolyte membrane as described in claim 4, characterized in that: The lithium salt is one or more of lithium difluorosulfonylimide, lithium tetrafluoroborate, lithium hexafluorophosphate, and lithium difluorooxalate borate, mixed with one or more of lithium difluorophosphate, lithium perchlorate, lithium bis(trifluoromethanesulfonylimide), and lithium dioxalate borate.

6. A method for preparing a spiderweb-like polymer electrolyte membrane according to any one of claims 1-5, characterized in that: The process involves uniformly mixing a monomer with two polymerization sites, a multi-arm crosslinking agent, a lithium salt, and a plasticizer to obtain a polymer precursor solution, then dropping the polymer precursor solution onto a porous base membrane, and finally obtaining a spider web-like polymer electrolyte membrane through a polymerization reaction.

7. The method for preparing a spider web-like polymer electrolyte membrane as described in claim 6, characterized in that: The mass ratio of the dual-polymerization-site monomer to the multi-arm crosslinking agent is 1:0.01 to 1:10; and / or, The mass ratio of the lithium salt to the monomer at the dual polymerization site is 0.01:1 to 10:1; and / or, The mass ratio of the plasticizer to the monomer at the two polymerization sites is 0.02:1 to 20:

1.

8. The method for preparing a spider web-like polymer electrolyte membrane as described in claim 6, characterized in that: The polymer precursor solution further includes a polymerization initiator, which includes one or more of the following: di-tert-butyl peroxide, potassium persulfate, ammonium persulfate, 2,2-azobisisobutyronitrile, lithium difluorooxalate borate, boron trifluoride, benzoyl peroxide, lithium hexafluorophosphate, lithium tetrafluoroborate, aluminum trifluoromethanesulfonate, AlCl3, TiCl4, SnCl4, ZnCl2, SbCl5, MgCl2, Al(OTf)3, and Sn(Oct)2; the mass ratio of the polymerization initiator to the monomer at the two polymerization sites is 0.001:1 to 1:1; and / or, The polymerization method includes one or more of the following: cationic ring-opening polymerization, anionic ring-opening polymerization, free radical polymerization, electrochemical polymerization, thermal polymerization, gamma-ray initiated polymerization, gel factor initiated polymerization, and photoinitiated polymerization.

9. A fast-charging solid-state battery, characterized in that: It includes the spiderweb-like polymer electrolyte membrane, positive electrode, and negative electrode as described in claim 1.

10. A fast-charging solid-state battery as described in claim 9, characterized in that: The positive electrode includes LiFePO4 and LiNi. 0.5 Co 0.2 Mn 0.3 O2, LiNi 0.6 Co 0.2 Mn 0.2 O2, LiNi 0.8 Co 0.1 Mn 0.1 O2, LiNi 0.9 Co 0.05 Mn 0.05 O2, LiNi 0.6 Co 0.1 Mn 0.3 O2, LiCoO2, xLi2MnO3 · (1-x)LiMnO2, Li4Ti5O 12 LiMn2O4, LiMn x Fe 1-x PO4, LiNi x Co y One or more of Al2O2, sulfur-carbon, and sulfur materials; the negative electrode includes one or more of lithium metal, graphite, hard carbon, and silicon-carbon composite negative electrode materials.

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