Aromatic ether-based polymer quasi-solid electrolyte membrane, in-situ preparation method and fast-charging solid-state battery thereof

Abstract

This invention belongs to the technical field of quasi-solid-state electrolyte membranes for lithium metal batteries and solid-state lithium batteries, disclosing an aromatic ether-based polymer quasi-solid-state electrolyte membrane, an in-situ preparation method, and a fast-charging solid-state battery thereof. The quasi-solid-state electrolyte membrane comprises a porous base membrane and a cross-linked polymer electrolyte filled within the porous base membrane, forming a three-dimensional cross-linked polymer network containing aromatic ring structures through an in-situ polymerization reaction. The quasi-solid-state electrolyte membrane of this invention exhibits excellent electrochemical performance. At 1 mA h cm⁻¹ ‑2 and 1 mA cm ‑2 Under the electroplating / stripping capacity and current density, the solid-state LFP||Li battery can operate stably for more than 200 hours. After 1800 cycles at 15 C, the capacity retention rate is 86.78%, and after 2000 cycles at 20 C, the capacity retention rate is 83.1%.

Description

Technical Field

[0001] This invention belongs to the technical field of quasi-solid-state electrolyte membranes for lithium metal batteries and solid-state lithium batteries, and relates to an aromatic ether-based polymer quasi-solid-state electrolyte membrane, an in-situ preparation method, and a fast-charging solid-state battery thereof. Background Technology

[0002] With the rapid development of new energy vehicles, portable electronic devices, and large-scale energy storage technologies, lithium-ion batteries and lithium metal batteries are facing higher requirements for energy density, safety, and fast charge / discharge performance. Traditional liquid lithium batteries use a large amount of volatile and flammable organic liquid electrolytes, which pose safety hazards such as leakage, combustion, and even thermal runaway under high voltage, high temperature, or mechanical abuse conditions, making it difficult to further meet the development needs of high-safety energy storage devices.

[0003] Replacing traditional liquid electrolytes and separators with solid or quasi-solid electrolytes is considered an important way to improve the safety and energy density of lithium batteries. Among them, polymer-based solid electrolytes have attracted widespread attention due to their advantages such as good flexibility, strong interface adaptability, simple processing technology, and high compatibility with existing battery manufacturing processes. However, existing polymer quasi-solid electrolytes still have problems such as insufficient ion conductivity, high electrode / electrolyte interface impedance, low lithium-ion transference number, and severe concentration polarization at high rates, which limit their application in fast-charging lithium metal batteries.

[0004] In polyether electrolytes, the etheroxy groups can coordinate with lithium ions, which is beneficial for lithium salt dissociation and lithium ion conduction. However, traditional linear polyether systems often lack mechanical strength and are prone to problems such as liquid phase component migration, increased interfacial side reactions, and uneven lithium deposition during cycling. Constructing cross-linked polymer networks can improve the structural stability and liquid phase retention of electrolyte membranes, but relying solely on cross-linked networks is insufficient to fully control the local solvation structure and interfacial migration kinetics of lithium ions. Therefore, developing a quasi-solid-state electrolyte membrane that combines local coordination environment control, a stable three-dimensional network structure, and good interfacial compatibility is of great significance for achieving high-safety and high-rate lithium metal batteries. Summary of the Invention

[0005] This invention addresses the problems of insufficient ion conductivity, poor interfacial stability, and severe concentration polarization under fast charging conditions in existing polymer quasi-solid-state electrolyte membranes. It proposes an aromatic ether-based crosslinked polymer quasi-solid-state electrolyte membrane, an in-situ preparation method, and a lithium metal battery. This quasi-solid-state electrolyte membrane is formed by in-situ ring-opening polymerization of aromatic ether monomers and multi-arm crosslinking agents to create a three-dimensional crosslinked polymer network containing aromatic ring structures and ether oxygen coordination sites. The aromatic rings and ether oxygen groups synergistically regulate the local coordination environment of lithium ions, promoting lithium ion conduction. The three-dimensional crosslinked network improves the structural stability and liquid phase component retention of the electrolyte membrane, and to some extent restricts anion migration, reducing concentration polarization and electrode interface side reactions, thereby improving the cycle stability and rate performance of the lithium metal battery.

[0006] One objective of this invention is to provide an aromatic ether-based crosslinked polymer quasi-solid electrolyte membrane. The quasi-solid electrolyte membrane comprises a porous base membrane and a crosslinked polymer electrolyte filled within the porous base membrane. The crosslinked polymer electrolyte is formed by in-situ polymerization of a polymer precursor solution, which comprises an aromatic ether monomer, a multi-arm crosslinking agent, a lithium salt, and a plasticizer.

[0007] A second objective of this invention is to provide an in-situ preparation method for an aromatic ether-based crosslinked polymer quasi-solid electrolyte membrane. A polymer precursor solution is obtained by mixing an aromatic ether monomer, a multi-arm crosslinking agent, a lithium salt, a plasticizer, and a polymerization initiator or catalyst. This precursor solution is then added dropwise, impregnated, or injected into a porous base membrane, and the aromatic ether-based crosslinked polymer quasi-solid electrolyte membrane is formed through in-situ polymerization.

[0008] A third objective of this invention is to provide a lithium metal battery based on the quasi-solid-state electrolyte membrane of the aromatic ether-based crosslinked polymer. The lithium metal battery includes a positive electrode, a negative electrode, and the quasi-solid-state electrolyte membrane, wherein the negative electrode comprises lithium metal, and the positive electrode comprises one or more of lithium iron phosphate, lithium cobalt oxide, nickel-cobalt-manganese ternary materials, nickel-cobalt-aluminum materials, lithium-rich manganese-based materials, or sulfur-based positive electrode materials.

[0009] The technical solution of this invention: An aromatic ether-based polymer quasi-solid electrolyte membrane includes a porous base membrane and a crosslinked polymer electrolyte filled in the porous base membrane; the crosslinked polymer electrolyte is formed by in-situ polymerization of a polymer precursor solution, the polymer precursor solution including an aromatic ether monomer, a multi-arm crosslinking agent, a lithium salt and a plasticizer, or the polymer precursor solution including an aromatic ether monomer, a multi-arm crosslinking agent, a lithium salt, a plasticizer and a polymerization initiator.

[0010] The aromatic ether monomer is one or a mixture of two or more of the following: phenyl glycidyl ether, benzyl glycidyl ether, tolyl glycidyl ether, naphthyl glycidyl ether, bisphenol A diglycidyl ether, resorcinol diglycidyl ether, 2-ethoxyphenyl glycidyl ether, 2-(4-methoxyphenyl)ethylene oxide, 9,9-bis(4-hydroxyphenyl)fluorene diglycidyl ether, 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether, 4-acetoxystyrene, 2-phenoxyethyl acrylate, and 4-methoxystyrene.

[0011] The multi-arm crosslinking agent is vinyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, vinyltriethoxysilane, (3-mercaptopropyl)trimethoxysilane, γ-aminopropyltriethoxysilane, pentaerythritol tetraacrylate, pentaerythritol triacrylate, N-phenyl-γ-aminopropyltrimethoxysilane, 3-(isobutenoyloxy)propyltrimethoxysilane, methacryloyloxymethyltrimethoxysilane, (3-acryloyloxypropyl)tri(trimethylsiloxy)silane, 3-acryloyloxypropylmethyldimethoxysilane, 3-glycidyl... One or more of the following: oleyloxypropyltrimethoxysilane, (3-chloropropyl)trimethoxysilane, allyltrimethoxysilane, acetoxypropyltrimethoxysilane, trimethoxy(3,3,3-trifluoropropyl)silane, (3-methacryloyloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane, 3-[(2,3)-epoxypropoxy]propylmethyldimethoxysilane, triglycidyl isocyanurate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triallyl ether, pentaerythritol tetrakis(3-mercaptopropionic acid) ester, and glycerol triglycidyl ether.

[0012] The polymerization initiator is one or a mixture of two or more of the following: 2,2-azobisisobutyronitrile, lithium dioxaborate, 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, aromatic ether monomer, and multi-arm crosslinking agent is 0.001:1:0.01 to 1:1:10.

[0013] The lithium salt is one or a mixture of two or more of lithium hexafluorophosphate, lithium difluorophosphate, lithium perchlorate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium tetrafluoroborate, lithium dioxalateborate, and lithium difluorooxalateborate. The molar ratio of lithium salt to polymer initiator is 1:0.01 to 1:1.

[0014] The plasticizer is one or a mixture of two 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; the mass ratio of plasticizer, aromatic ether monomer, and multi-arm crosslinking agent is 0.02:1:0.01 to 20:1:10.

[0015] The porous base membrane is one or more of the following: commercially available polyolefin membranes, glass fiber membranes, cellulose-based porous membranes, polymer-spun membranes, polymer phase inversion membranes, or modified porous membranes. Specifically, the commercially available polyolefin membranes include one or more of the following: polypropylene membranes, polyethylene membranes, polypropylene / polyethylene composite membranes, and polypropylene / polyethylene / polypropylene multilayer composite membranes. The cellulose-based porous membranes include one or two of the following: cellulose membranes and cellulose acetate membranes. The polymer-spun membranes or polymer phase inversion membranes are porous membranes formed from one or more of the following: polyacrylonitrile, polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride, polyimide, polyetherimide, polyvinyl alcohol, polyvinylpyrrolidone, polyethersulfone, perfluorosulfonic acid resin, polymethyl methacrylate, polytetrafluoroethylene, and polyvinyl chloride.

[0016] The polymer precursor solution may also contain one of the following: 1,3-dioxolane DOL, tetrahydrofuran (THF), 2-methyltetrahydrofuran, tetrahydropyran, 3-methyloxetane, 1,3-dioxane, 1,3,5-trioxane, 2-methyl-1,3-dioxolane, and 2-ethyl-1,3-dioxolane, with the addition amount in a mass ratio of 0.1:1 to 20:1 to the aromatic ether monomer.

[0017] An in-situ preparation method for an aromatic ether-based polymer quasi-solid electrolyte membrane includes the following steps: Aromatic ether monomers, crosslinking agents, lithium salts, and plasticizers are stirred evenly and then dropped onto a porous base membrane. An aromatic ether polymer quasi-solid electrolyte membrane is obtained through in-situ polymerization.

[0018] Aromatic ether monomers, crosslinking agents, lithium salts, plasticizers, and polymerization initiators are stirred evenly and then dropped onto a porous base membrane to obtain an aromatic ether polymer quasi-solid electrolyte membrane through in-situ polymerization.

[0019] The stirring time is 1 to 50 hours.

[0020] The in-situ polymerization reaction is carried out at a temperature of 30~150 ℃ for a time of 0.01~50 h.

[0021] A fast-charging solid-state battery based on an aromatic ether-based polymer quasi-solid-state electrolyte membrane includes an aromatic ether-based polymer quasi-solid-state electrolyte membrane, a positive electrode, and a negative electrode; 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 Al2O2, sulfur carbon, or a mixture of two or more of sulfur; the negative electrode includes one of lithium metal, graphite, hard carbon, or silicon-carbon composite negative electrode materials.

[0022] The beneficial effects of this invention are: The aromatic ether-based crosslinked polymer quasi-solid electrolyte membrane of the present invention introduces aromatic ring structures and ether oxygen coordination sites through aromatic ether monomers, which can regulate the local coordination environment of lithium ions and promote the migration of lithium ions in the polymer network.

[0023] This invention constructs a three-dimensional cross-linked polymer network using a multi-arm cross-linking agent, thereby improving the structural stability, liquid phase component retention, and interfacial compatibility of the quasi-solid electrolyte membrane, and reducing electrolyte component flow and interfacial inhomogeneity during cycling.

[0024] The three-dimensional cross-linked polymer network formed by this invention can, to a certain extent, restrict anion migration, reduce concentration polarization, reduce side reactions at the electrode interface, and promote uniform lithium-ion deposition, thereby improving the cycle stability and rate performance of lithium metal batteries.

[0025] The preparation method of the present invention is simple. Quasi-solid electrolyte membranes can be obtained by in-situ polymerization after adding, wetting or injecting a precursor solution. It has the advantages of strong process operability, good compatibility with existing lithium battery preparation processes and potential for large-scale preparation.

[0026] This invention discloses an aromatic ether-based crosslinked polymer quasi-solid-state electrolyte membrane, its in-situ preparation method, and its fast-charging solid-state battery, exhibiting excellent electrochemical performance. At 1 mA h cm⁻¹ -2 and 1 mA cm -2 Under the electroplating / stripping capacity and current density, the solid-state LFP||Li battery can operate stably for more than 200 hours. After 1800 cycles at 15 C, the capacity retention rate is 86.78%, and after 2000 cycles at 20 C, the capacity retention rate is 83.1%. Attached Figure Description

[0027] Figure 1 The electrochemical impedance spectroscopy and calculated ionic conductivity of the P-TAD solid electrolyte membrane prepared in Example 1 were tested at 30 °C, where TAD is comparative example 1 and M-TAD is comparative example 2. Figure 2 LSV curve of P-TAD solid electrolyte membrane prepared in Example 1, where TAD is comparative example 1 and M-TAD is comparative example 2; Figure 3 The constant current charge-discharge diagrams are shown for lithium symmetric batteries assembled using the P-TAD solid electrolyte membrane prepared in Example 1, where TAD is comparative example 1 and M-TAD is comparative example 2. Figure 4 The graph shows the long-term cycling stability of the LFP||Li solid-state battery assembled using the P-TAD solid electrolyte membrane prepared in Example 1 at 15 C, where TAD is comparative example 1 and M-TAD is comparative example 2. Figure 5 The graph shows the long-term cycling stability of the LFP||Li solid-state battery assembled using the P-TAD solid electrolyte membrane prepared in Example 1 at 20 C, where TAD is comparative example 1 and M-TAD is comparative example 2. Detailed Implementation

[0028] The specific embodiments of the present invention will be further described below with reference to the accompanying drawings and technical solutions.

[0029] Example 1 (1) Preparation of solid electrolyte membranes of aromatic ether-based crosslinked polymers; 0.06 g phenyl glycidyl ether (PGE), 0.06 g triglycidyl isocyanate (TGIC), 0.18 g 1,3-dioxolane (DOL), 0.35 g ethylene glycol dimethyl ether (DME), 0.10 g fluoroethylene carbonate (FEC), 0.2 g lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and 0.15 g lithium difluorooxalate borate (LiDFOB) were mixed and stirred at room temperature for 6 h. The mixture was then dropped onto a polypropylene / polyethylene / polypropylene multilayer composite membrane and heated in a 60 °C oven for 24 h to obtain a polymer solid electrolyte membrane, denoted as P-TAD.

[0030] (2) Assembly of solid-state lithium metal batteries; Weigh out lithium iron phosphate (LiFePO4), conductive carbon black (Super P), and polyvinylidene fluoride (PVDF) in a mass ratio of 8:1:1, grind them in a mortar for 20 min, then add N-methylpyrrolidone (NMP) and stir at room temperature for 12 h to form a slurry. Coat the slurry onto carbon-coated aluminum foil, dry it in a 70 ℃ forced-air oven for 24 h, and cut it into positive electrode discs. Battery assembly was carried out in an argon-atmospheric glove box. Polypropylene / polyethylene / polypropylene multilayer composite membranes were cut into 19 mm discs. The positive electrode (or lithium metal), polypropylene / polyethylene / polypropylene multilayer composite membranes, liquid in-situ polymerization precursor solution (a mixture of phenyl glycidyl ether PGE, triglycidyl isocyanate TGIC, 1,3-dioxane DOL, plasticizer ethylene glycol dimethyl ether DME, fluoroethylene carbonate FEC, lithium salt bis(trifluoromethanesulfonyl)imide LiTFSI and lithium difluorooxalate borate LiDFOB), lithium metal, gaskets, and springs were assembled into CR2025 coin-type lithium metal batteries. After heating and polymerization, solid-state lithium metal batteries were obtained.

[0031] Example 2 Unlike Example 1, the aromatic ether monomer phenyl glycidyl ether (PGE) in Example 1 was replaced with benzyl glycidyl ether; the multi-arm crosslinking agent triglycidyl isocyanurate (TGIC) was replaced with 3-glycidyloxypropyltrimethoxysilane; the lithium salts lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium difluorooxalate borate (LiDFOB) were replaced with lithium bis(fluorosulfonyl)imide (LiFSI) and lithium difluorooxalate borate (LiDFOB); the plasticizer 1,3-dioxolane (DOL) was replaced with 2-methyltetrahydrofuran; and the porous base membrane was replaced with a PE membrane. The masses of benzyl glycidyl ether, 3-glycidyloxypropyltrimethoxysilane, LiFSI, LiDFOB, 2-methyltetrahydrofuran, ethylene glycol dimethyl ether (DME), and fluoroethylene carbonate (FEC) were 0.05 g, 0.03 g, 0.18 g, 0.06 g, 0.20 g, 0.35 g, and 0.45 g, respectively. g and 0.10 g. After stirring at room temperature for 6 h, the mixture was dropped onto a PE separator and then transferred to a 50 ℃ forced-air oven for in-situ polymerization for 8 h to obtain a silane crosslinked aromatic ether polymer quasi-solid-state electrolyte membrane. The remaining battery assembly method was the same as in Example 1.

[0032] Example 3 Unlike Example 1, the aromatic ether monomer phenyl glycidyl ether (PGE) in Example 1 was replaced with 2-phenoxyethyl acrylate, the multi-arm crosslinking agent triglycidyl isocyanate (TGIC) was replaced with pentaerythritol tetraacrylate, the polymerization initiator was replaced with 2,2-azobisisobutyronitrile, the lithium salt was replaced with lithium hexafluorophosphate (LiPF6) and lithium difluorooxalate borate (LiDFOB), the plasticizer was replaced with ethylene carbonate (EC), dimethyl carbonate (DMC), and fluoroethylene carbonate (FEC), and the porous base membrane was replaced with polyacrylonitrile (PAN) spun membrane; wherein the masses of 2-phenoxyethyl acrylate, pentaerythritol tetraacrylate, 2,2-azobisisobutyronitrile, LiPF6, LiDFOB, EC, DMC, and FEC were 0.08 g, 0.04 g, 0.005 g, 0.12 g, 0.04 g, 0.20 g, 0.25 g, and 0.08 g, respectively. After stirring at room temperature for 10 h, the mixture was dropped onto a PAN spinning membrane and then transferred to a 70 ℃ forced-air oven for in-situ polymerization for 6 h to obtain an ester-crosslinked aromatic ether polymer quasi-solid-state electrolyte membrane. The remaining battery assembly method was the same as in Example 1.

[0033] Example 4 Unlike Example 1, the aromatic ether monomer phenyl glycidyl ether (PGE) in Example 1 was replaced with resorcinol diglycidyl ether, the multi-arm crosslinking agent triglycidyl isocyanurate (TGIC) was replaced with glycerol triglycidyl ether, the polymerization initiator was replaced with boron trifluoride, the lithium salt was replaced with lithium tetrafluoroborate (LiBF4) and lithium dioxalate borate (LiBOB), the plasticizer 1,3-dioxolane (DOL) was replaced with tetrahydrofuran (THF), and the porous base membrane was replaced with a glass fiber membrane. The masses of resorcinol diglycidyl ether, glycerol triglycidyl ether, boron trifluoride, LiBF4, LiBOB, THF, propylene carbonate (PC), and fluoroethylene carbonate (FEC) were 0.06 g, 0.04 g, 0.004 g, 0.10 g, 0.04 g, 0.25 g, 0.25 g, and 0.06 g, respectively. After stirring at room temperature for 4 hours, the mixture was dropped onto a glass fiber membrane and then transferred to an 80 °C forced-air oven for in-situ polymerization for 10 hours to obtain a quasi-solid-state electrolyte membrane of ether-crosslinked aromatic ether polymer. The remaining battery assembly method was the same as in Example 1.

[0034] Example 5 Unlike Example 1, the aromatic ether monomer phenyl glycidyl ether (PGE) in Example 1 was replaced with 4-methoxystyrene, the multi-arm crosslinking agent triglycidyl isocyanurate (TGIC) was replaced with 3-(isobutenoyloxy)propyltrimethoxysilane, the polymerization initiator was replaced with benzoyl peroxide, the lithium salt was replaced with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium bis(fluorosulfonyl)imide (LiFSI), the plasticizer was replaced with succinic acid, adiponitrile, and fluoroethylene carbonate (FEC), and the porous base membrane was replaced with a PVDF-HFP porous membrane; the masses of 4-methoxystyrene, 3-(isobutenoyloxy)propyltrimethoxysilane, benzoyl peroxide, LiTFSI, LiFSI, succinic acid, adiponitrile, and FEC were 0.07 g, 0.035 g, 0.006 g, 0.14 g, 0.05 g, 0.30 g, 0.15 g, and 0.05 g, respectively. g. After stirring at room temperature for 12 h, the mixture was dropped onto a PVDF-HFP porous membrane and then transferred to a 90 ℃ forced-air oven for in-situ polymerization for 5 h to obtain a silane-crosslinked aromatic ether polymer quasi-solid-state electrolyte membrane. The remaining battery assembly method was the same as in Example 1.

[0035] Example 6 Unlike Example 1, the aromatic ether monomer phenyl glycidyl ether (PGE) in Example 1 was replaced with naphthyl glycidyl ether; the multi-arm crosslinking agent triglycidyl isocyanate (TGIC) was replaced with ethoxylated trimethylolpropane triacrylate; the polymerization initiator was replaced with 2,2-azobisisobutyronitrile; the lithium salt was replaced with lithium perchlorate (LiClO4) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI); the plasticizer 1,3-dioxolane (DOL) was replaced with 1,3-dioxane; and the porous base membrane was replaced with a polyimide porous membrane. The masses of naphthyl glycidyl ether, ethoxylated trimethylolpropane triacrylate, 2,2-azobisisobutyronitrile, LiClO4, LiTFSI, 1,3-dioxane, ethyl methyl carbonate (EMC), and fluoroethylene carbonate (FEC) were 0.04 g, 0.05 g, 0.004 g, 0.05 g, and 0.14 g, respectively. The amounts were 0.22 g, 0.32 g, and 0.08 g. After stirring at room temperature for 8 h, the mixture was dropped onto a polyimide porous membrane and then transferred to a 60 °C forced-air oven for in-situ polymerization for 18 h to obtain an ester-crosslinked aromatic ether polymer quasi-solid-state electrolyte membrane. The remaining battery assembly method was the same as in Example 1.

[0036] Example 7 Unlike Example 1, the aromatic ether monomer phenyl glycidyl ether (PGE) in Example 1 was replaced with bisphenol A diglycidyl ether, the multi-arm crosslinking agent triglycidyl isocyanurate (TGIC) was replaced with pentaerythritol triallyl ether, the polymerization initiator was replaced with lithium tetrafluoroborate, the lithium salt was replaced with lithium bisfluorosulfonyl imide (LiFSI) and lithium tetrafluoroborate (LiBF4), the plasticizer was replaced with polyethylene glycol dimethyl ether, difluoroethyl acetate, and fluoroethylene carbonate (FEC), and the porous base membrane was replaced with a polyethersulfone porous membrane. The masses of bisphenol A diglycidyl ether, pentaerythritol triallyl ether, lithium tetrafluoroborate, LiFSI, LiBF4, polyethylene glycol dimethyl ether, difluoroethyl acetate, and FEC were 0.06 g, 0.03 g, 0.005 g, 0.16 g, 0.04 g, 0.30 g, 0.18 g, and 0.06 g, respectively. After stirring at room temperature for 20 h, the mixture was dropped onto a polyethersulfone porous membrane and then transferred to a 110 ℃ forced-air oven for in-situ polymerization for 2 h to obtain a quasi-solid-state electrolyte membrane of ether-crosslinked aromatic ether polymer. The remaining battery assembly method was the same as in Example 1.

[0037] Example 8 Unlike Example 1, the aromatic ether monomer phenyl glycidyl ether (PGE) in Example 1 was replaced with 9,9-bis(4-hydroxyphenyl)fluorene diglycidyl ether, the multi-arm crosslinking agent triglycidyl isocyanurate (TGIC) was replaced with N-phenyl-γ-aminopropyltrimethoxysilane, the polymerization initiator was replaced with AlCl3, the lithium salt was replaced with lithium difluorophosphate (LiPO2F2) and lithium bis(trifluoromethanesulfonylimide) (LiTFSI), the plasticizer 1,3-dioxolane (DOL) was replaced with 3-methyloxetane, and the porous base membrane was replaced with a cellulose porous membrane; the masses of 9,9-bis(4-hydroxyphenyl)fluorene diglycidyl ether, N-phenyl-γ-aminopropyltrimethoxysilane, AlCl3, LiPO2F2, LiTFSI, 3-methyloxetane, trimethyl phosphate, and fluoroethylene carbonate (FEC) were 0.05 g, 0.04 g, and 0.003 g, respectively. The amounts of the mixture were 0.04 g, 0.16 g, 0.20 g, 0.30 g, and 0.06 g. After stirring at room temperature for 24 h, the mixture was dropped onto a porous cellulose membrane and then transferred to a 120 °C oven for in-situ polymerization for 1 h to obtain a silane-crosslinked aromatic ether polymer quasi-solid-state electrolyte membrane. The remaining battery assembly method was the same as in Example 1.

[0038] Comparative Example 1 PGE is not added to the precursor solution. The rest of the composition, battery assembly method and testing method are the same as in Example 1, and it is referred to as TAD.

[0039] Comparative Example 2 The phenyl glycidyl ether (PGE) in the precursor solution was replaced with glycidyl methyl ether (MGE). Otherwise, the composition, battery assembly method, and testing methods were the same as in Example 1, and it was referred to as M-TAD.

[0040] To more clearly illustrate the modified results of the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below.

[0041] Figure 1 The ionic conductivity of the P-TAD polymer electrolyte membrane prepared in Example 1 was tested at 30 °C, where TAD is comparative example 1 and M-TAD is comparative example 2. The calculated ionic conductivity of Example 1 was 1.12 mS / cm. -1 The ionic conductivity of Comparative Example 1 and Comparative Example 2 were 0.27 mS / cm, respectively. -1 0.50 mS cm -1 Figure 2 The image shows the LSV curve of the P-TAD solid electrolyte membrane prepared in Example 1, where TAD is comparative example 1 and M-TAD is comparative example 2. The electrochemical stability window of Example 1 was improved to 5.7 V.

[0042] Figure 3 The image shows the constant current charge-discharge curves of a lithium-ion symmetric battery assembled using the P-TAD solid electrolyte membrane prepared in Example 1, where P-TAD is Example 1, TAD is Comparative Example 2, and M-TAD is Comparative Example 3. Example 1 was charged at 1 mAh cm⁻¹. -2 and 1 mAcm -2 The sample exhibited stable cycling performance exceeding 200 h at electroplating / stripping capacity and current density, compared to 150 h for Comparative Example 1 and less than 50 h for Comparative Example 2. The performance of the sample was superior to that of the comparative examples.

[0043] Figure 4 The graph shows the long-cycle performance of a solid-state LFP||Li battery assembled using the P-TAD solid electrolyte membrane prepared in Example 1 at 15 C charge-discharge. TAD is used for Comparative Example 1, and M-TAD is used for Comparative Example 2. The performance of the LFP||Li battery at 15 C is as follows: Comparative Example 1 has a discharge specific capacity of 50.8 mAh g after 1000 cycles. -1 The capacity retention rate was 71.8%; after 1000 cycles, the discharge specific capacity of Comparative Example 2 was 63.46 mAh g. -1 The capacity retention rate was 61.76%, after which the capacity decreased sharply; however, the initial discharge specific capacity of Example 1 was 87.57 mAh g. -1 After 1800 cycles, the discharge specific capacity is 76 mAh g. -1 The retention rate was 86.78%, which was significantly better than that of control groups 1 and 2.

[0044] Figure 5 The graph shows the long-term cycling performance of a solid-state LFP||Li battery assembled using the P-TAD solid electrolyte membrane prepared in Example 1 at 20 C charge-discharge. TAD is used for comparative example 1, and M-TAD for comparative example 2. The LFP / P-TAD / Li battery has a discharge specific capacity of 65.7 mAh g⁻¹ after 2000 cycles at 20 C. -1 The retention rate was 83.1%; compared to Comparative Example 1, the discharge specific capacity after 2000 cycles was only 37.7 mAh g. -1 Comparative Example 2 showed a discharge specific capacity of only 47.6 mAh g after 2000 cycles. -1 .

[0045] The above description is merely a preferred embodiment of the present invention. Although the description is detailed and specific, it should not be construed as limiting the scope of the present invention. For those skilled in the art, any modifications, equivalent substitutions, improvements, or other variations made within the spirit and principles of the present invention without departing from its technical scope are considered to have remained within the protection scope of the present invention.

[0046] The above results indicate that the aromatic ether-based crosslinked polymer quasi-solid-state electrolyte membrane prepared in Example 1 exhibits superior ion conductivity, interfacial stability, and rate cycling performance. This is because the aromatic ring and ether oxygen structure in PGE can synergistically regulate the local coordination environment of lithium ions, weakening the strong interaction between lithium ions and solvent molecules, and promoting lithium ion migration in the electrolyte membrane. Simultaneously, after participating in in-situ ring-opening polymerization, PGE, together with the crosslinking agent, forms a stable three-dimensional polymer network, which is beneficial for improving the structural stability of the electrolyte membrane and enhancing the electrode / electrolyte interface contact. Comparative Example 1, without the addition of PGE, lacks the regulatory effect of the aromatic ether structure on the lithium ion coordination environment, resulting in insufficient ion transport and interfacial stability in the electrolyte membrane. Comparative Example 2, replacing PGE with MGE without the aromatic ring, still provides ether oxygen sites, but lacks the regulatory effect of the aromatic ring on the local solvation structure, resulting in weaker lithium ion migration kinetics and interfacial reaction stability, thus exhibiting greater polarization and poorer cycling stability.

Claims

1. A quasi-solid-state electrolyte membrane based on an aromatic ether polymer, characterized in that, The aromatic ether-based polymer quasi-solid electrolyte membrane includes a porous base membrane and a crosslinked polymer electrolyte filled in the porous base membrane; the crosslinked polymer electrolyte is formed by in-situ polymerization of a polymer precursor solution, which includes an aromatic ether monomer, a multi-arm crosslinking agent, a lithium salt, and a plasticizer, or the polymer precursor solution includes an aromatic ether monomer, a multi-arm crosslinking agent, a lithium salt, a plasticizer, and a polymerization initiator.

2. The aromatic ether-based polymer quasi-solid-state electrolyte membrane according to claim 1, characterized in that, The aromatic ether monomer is one or a mixture of two or more of the following: phenyl glycidyl ether, benzyl glycidyl ether, tolyl glycidyl ether, naphthyl glycidyl ether, bisphenol A diglycidyl ether, resorcinol diglycidyl ether, 2-ethoxyphenyl glycidyl ether, 2-(4-methoxyphenyl)ethylene oxide, 9,9-bis(4-hydroxyphenyl)fluorene diglycidyl ether, 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether, 4-acetoxystyrene, 2-phenoxyethyl acrylate, and 4-methoxystyrene.

3. The aromatic ether-based polymer quasi-solid-state electrolyte membrane according to claim 2, characterized in that, The multi-arm crosslinking agent is vinyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, vinyltriethoxysilane, (3-mercaptopropyl)trimethoxysilane, γ-aminopropyltriethoxysilane, pentaerythritol tetraacrylate, pentaerythritol triacrylate, N-phenyl-γ-aminopropyltrimethoxysilane, 3-(isobutenoyloxy)propyltrimethoxysilane, methacryloyloxymethyltrimethoxysilane, (3-acryloyloxypropyl)tri(trimethylsiloxy)silane, 3-acryloyloxypropylmethyldimethoxysilane, 3-glycidyl... One or more of the following: oleyloxypropyltrimethoxysilane, (3-chloropropyl)trimethoxysilane, allyltrimethoxysilane, acetoxypropyltrimethoxysilane, trimethoxy(3,3,3-trifluoropropyl)silane, (3-methacryloyloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane, 3-[(2,3)-epoxypropoxy]propylmethyldimethoxysilane, triglycidyl isocyanurate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triallyl ether, pentaerythritol tetrakis(3-mercaptopropionic acid) ester, and glycerol triglycidyl ether.

4. The aromatic ether-based polymer quasi-solid-state electrolyte membrane according to claim 3, characterized in that, The polymerization initiator is one or a mixture of two or more of the following: 2,2-azobisisobutyronitrile, lithium dioxaborate, 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, aromatic ether monomer, and multi-arm crosslinking agent is 0.001:1:0.01 to 1:1:

10.

5. The aromatic ether-based polymer quasi-solid-state electrolyte membrane according to claim 4, characterized in that, The lithium salt is one or a mixture of two or more of lithium hexafluorophosphate, lithium difluorophosphate, lithium perchlorate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium tetrafluoroborate, lithium di(oxalate)borate, and lithium di(fluorooxalate)borate; wherein the molar ratio of lithium salt to polymer initiator is 1:0.01 to 1:

1.

6. The aromatic ether-based polymer quasi-solid-state electrolyte membrane according to claim 5, characterized in that, The plasticizer is one or a mixture of two 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; the mass ratio of plasticizer, aromatic ether monomer, and multi-arm crosslinking agent is 0.02:1:0.01 to 20:1:

10.

7. The aromatic ether-based polymer quasi-solid-state electrolyte membrane according to claim 6, characterized in that, The porous base membrane is one or more of the following: polyolefin membrane, glass fiber membrane, cellulose porous membrane, polymer spun membrane, polymer phase inversion membrane, or modified porous membrane. The polyolefin membrane includes one or more of the following: polypropylene membrane, polyethylene membrane, polypropylene / polyethylene composite membrane, and polypropylene / polyethylene / polypropylene multilayer composite membrane. The cellulose porous membrane includes one or two of the following: cellulose membrane and cellulose acetate membrane. The polymer spun membrane or polymer phase inversion membrane is a porous membrane formed from one or more of the following: polyacrylonitrile, polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride, polyimide, polyetherimide, polyvinyl alcohol, polyvinylpyrrolidone, polyethersulfone, perfluorosulfonic acid resin, polymethyl methacrylate, polytetrafluoroethylene, and polyvinyl chloride.

8. The aromatic ether-based polymer quasi-solid-state electrolyte membrane according to claim 7, characterized in that, The polymer precursor solution also contains one of the following: 1,3-dioxolane DOL, tetrahydrofuran (THF), 2-methyltetrahydrofuran, tetrahydropyran, 3-methyloxetane, 1,3-dioxane, 1,3,5-trioxane, 2-methyl-1,3-dioxolane, and 2-ethyl-1,3-dioxolane, with the addition amount in a mass ratio of 0.1:1 to 20:1 to the aromatic ether monomer.

9. A method for in-situ preparation of an aromatic ether-based polymer quasi-solid electrolyte membrane, characterized in that, Includes the following steps: Aromatic ether monomers, crosslinking agents, lithium salts, and plasticizers are stirred for 1-50 h until homogeneous, then dropped onto a porous base membrane, and an aromatic ether polymer quasi-solid electrolyte membrane is obtained through in-situ polymerization. Aromatic ether monomers, crosslinking agents, lithium salts, plasticizers, and polymerization initiators are stirred for 1-50 h until homogeneous, and then dropped onto a porous base membrane to obtain an aromatic ether polymer quasi-solid electrolyte membrane through in-situ polymerization. The in-situ polymerization reaction is carried out at a temperature of 30~150 ℃ for a time of 0.01~50 h.

10. A fast-charging solid-state battery based on an aromatic ether-based polymer quasi-solid-state electrolyte membrane, characterized in that, This fast-charging solid-state battery includes an aromatic ether-based polymer quasi-solid-state electrolyte membrane, a positive electrode, and a negative electrode; 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 Al2O2, sulfur carbon, or a mixture of two or more of sulfur; the negative electrode includes one of lithium metal, graphite, hard carbon, or silicon-carbon composite negative electrode materials.

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