Lithium ion solid electrolyte as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of solid-state batteries, and provides a lithium-ion solid-state electrolyte and a preparation method and application thereof. The lithium ion solid electrolyte comprises a polymer matrix, a lithium salt, a polar organic compound, a polymer monomer (comprising a first monomer and a second monomer) and an anion acceptor. The preparation method comprises the following steps: mixing a lithium salt and a polar organic compound to obtain a eutectic mixture; mixing a polymer matrix, a first monomer, a second monomer and an anion acceptor with the eutectic mixture to obtain a precursor solution; and coating a substrate with the precursor solution, curing and drying. The invention also discloses a solid-state lithium ion battery comprising the lithium-ion solid-state electrolyte and a manufacturing device of the solid-state lithium ion battery. The lithium ion solid electrolyte disclosed by the invention is high in room-temperature ionic conductivity, excellent in tensile strength, tensile elongation and high in breaking strength and incombustibility, and the lithium ion transference number is increased; therefore, the battery has long-term cycle stability, and the problem of electrode stress failure under low stacking pressure is solved.

Description

Technical Field

[0001] This disclosure relates to the field of solid-state battery technology, and in particular to lithium-ion solid electrolytes, their preparation methods, and applications. Background Technology

[0002] With the booming development of the new energy market, traditional lithium-ion batteries containing organic liquid electrolytes can no longer meet the increasingly urgent demands for high energy density and safety. Solid-state batteries, due to their high energy density and high safety, have received much attention from the industry in recent years. Currently, the most prominent lithium-ion solid electrolytes mainly include oxide, sulfide, halide lithium-ion solid electrolytes and polymer lithium-ion solid electrolytes. However, these lithium-ion solid electrolytes still encounter many problems in practical applications that need to be solved. For example, sulfide lithium-ion solid electrolytes have a narrow voltage window, are prone to side reactions at the electrode interface, and are very sensitive to air / moisture, making them unstable in such environments; oxide lithium-ion solid electrolytes have a high Young's modulus, low room temperature ionic conductivity, and high interfacial impedance due to differences in contact with electrode materials; halide lithium-ion solid electrolytes cannot be used on a large scale due to poor compatibility with the negative electrode and easy hydrolysis. Polymer lithium-ion solid electrolytes (such as PEO-based) have limitations in practical applications due to their low room temperature conductivity and poor oxidation resistance (difficult to match high-voltage positive electrodes). Meanwhile, the practical application of solid-state batteries is currently hampered by other technical issues, including the need for extremely high stacking pressure. Reducing the operating pressure typically leads to a decrease in the cycle stability of solid-state batteries. The main reason is that without sufficient external pressure, the repeated expansion and contraction of the active material can loosen the contact between the active material and the lithium-ion solid electrolyte, thus hindering lithium-ion transport and causing cycle capacity decay. However, providing such high stacking pressure in practical applications presents significant challenges; the addition of extra pressurization equipment greatly reduces the battery's energy density and increases production costs. Summary of the Invention

[0003] This disclosure provides lithium-ion solid electrolytes, their preparation methods, and applications, in order to at least solve the above-mentioned technical problems existing in the prior art.

[0004] According to a first aspect of this disclosure, a lithium-ion solid electrolyte is provided, comprising a polymer matrix, a lithium salt, a polar organic compound, a polymer monomer, and an anion acceptor; said polymer monomer comprises a first monomer and a second monomer.

[0005] In one embodiment, the polymer matrix includes at least one of polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polyethylene oxide (PEO, Mw = 600,000 to 1,000,000), poly(methyl methacrylate) (PMMA), poly(vinyl acetate) (PVAc), polyvinylidene fluoride (PVDF), and polyacrylonitrile (PAN).

[0006] In one embodiment, the molar ratio of the polymer monomer to the polymer matrix is ​​(0.2-5):1.

[0007] Specifically, the molar amount of the polymer monomer is the total molar amount of the first monomer and the second monomer.

[0008] In one embodiment, the lithium salt includes at least one of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium difluorooxalate borate (LiDFOB), lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium bis(oxalate)borate (LiBOB), lithium bis(fluorosulfonyl)imide (LiFSI), lithium trifluoromethanesulfonate (LiTf), lithium difluorophosphate (LiPO2F2), lithium nitrate (LiNO3), lithium perchlorate (LiClO4), lithium chloride (LiCl), lithium iodide (LiI), and lithium bromide (LiBr).

[0009] In one embodiment, the polar organic compound includes at least one selected from N-methylacetamide (NMA), N-ethylacetamide (NEA), 2-methylpropionamide, 1-methyl-3-propylimidazolium, triethylene glycol dimethyl ether, lactic acid, triethanolamine, glycerol, and urea.

[0010] Specifically, lithium salts and polar organic compounds can form eutectic mixtures that are liquid at room temperature through strong interactions (Lewis acid-base interactions), with the melting point of the eutectic mixture being much lower than that of the individual components.

[0011] In one embodiment, the molar ratio of the lithium salt to the polar organic compound is 1:(1 to 10).

[0012] In one embodiment, the first monomer includes at least one of acrylamide (AM) and its derivatives.

[0013] In one embodiment, the acrylamide derivative is selected from... At least one of them.

[0014] In one embodiment, the second monomer includes at least one of dimethylacrylamide (DMAM) and its derivatives.

[0015] In one embodiment, the dimethacrylamide derivative is selected from... At least one of them.

[0016] In one embodiment, the molar ratio of the first monomer to the second monomer is (0.3-5):1.

[0017] In one embodiment, the anion acceptor includes at least one of tris(pentafluorophenyl)borane (TPFPB), fluoroalkyl borates (such as (C6H3F)2B(C6H5F2)), trimethyl borate, phenyl borate derivatives (such as phenyl borate ester), boron trifluoride diethyl ether complex (BF3·OEt2), borate ester crosslinking agents (such as pentaerythritol borate ester), polyvinyl alcohol borate ester, tris(pentafluorophenyl)boron (B(C6F5)3), methacrylate borate copolymer, polystyrene sulfonate (PSS), polypyrrolidone (PVP) derivatives, CC3 type porous organic cages (POCs), fluorinated covalent organic frameworks (F-COF), boron-doped porous organic cages (B-POC), and triazine covalent organic frameworks (CTF-1).

[0018] Specifically, anion acceptors can coordinate with anions in lithium salts through Lewis acid or pore confinement effects, weakening the electrostatic attraction between lithium ions and anions, thereby increasing the lithium ion transference number.

[0019] In one embodiment, the lithium-ion solid electrolyte further includes a plasticizer, a crosslinking agent, an initiator, and a solvent.

[0020] Specifically, the plasticizer includes at least one of fluoroethylene carbonate (FEC), succinic anionyl nitrile (SN), polyethylene glycol dimethyl ether (PEGDME), dibutyl phthalate (DBP), trifluoroethoxyethane (TFEO), and ionic liquids (such as EMIM, TFSI).

[0021] Specifically, the crosslinking agent includes at least one of N,N'-methylenebisacrylamide (MBA), polyethylene glycol diacrylate (PEGDA), trimethylolpropane triacrylate (TMPTA), 1,6-hexanediol diacrylate (HDDA), pentaerythritol triacrylate (PETRA), polyethylene glycol dimethacrylate (PEGDMA), divinylbenzene (DVB), triallylamine (TAA), bisacryloylcysteine ​​(BAC), triacryloylhexahydro-1,3,5-triazine (TAT), and pentaerythritol tetraacrylate.

[0022] Specifically, the initiator includes at least one of 2,2-azobisisobutyronitrile (AIBN), 4-methylbenzophenone (MBP), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, 2-hydroxy-2-methylphenylacetone, benzoin dimethyl ether, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and lithium phenyl-2,4,6-trimethylbenzoylphosphonate.

[0023] Specifically, the solvent includes at least one of anhydrous acetonitrile (ACN), N-methylpyrrolidone (NMP), cyclohexane, toluene, xylene, acetonitrile, dichloromethane, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), acetone, tetrahydrofuran, chloroform, and dimethylacetamide (DMAc).

[0024] In one embodiment, the molar ratio of the polymer monomer to the crosslinking agent is (0.5-4):1.

[0025] Specifically, the molar amount of the polymer monomer is the total molar amount of the first monomer and the second monomer.

[0026] In one embodiment, the ratio of the total molar amount of the polymer monomer and the polymer matrix to the molar amount of the solvent is (1-25):1.

[0027] In one embodiment, the molar ratio of the crosslinking agent to the initiator is (0.5-3):1.

[0028] According to a second aspect of this disclosure, a method for preparing the above-mentioned lithium-ion solid electrolyte is provided, comprising the following steps:

[0029] S1: A lithium salt and a polar organic compound are mixed to obtain a eutectic mixture;

[0030] S2: Mix the polymer matrix, the first monomer, the second monomer, and the anion acceptor with the eutectic mixture to obtain a precursor solution;

[0031] S3: After coating the precursor liquid onto the substrate, cure and dry it to obtain the lithium-ion solid electrolyte.

[0032] In one embodiment, the lithium salt and the polar organic compound are mixed at 20–40°C for 0.1–10 h.

[0033] In one embodiment, step S2 involves mixing the polymer matrix, the first monomer, the second monomer, the anion acceptor, the plasticizer, the crosslinking agent, the initiator, and the solvent with the eutectic mixture to obtain the precursor solution.

[0034] In one embodiment, the mixing temperature in step S2 is 20–40°C, and the mixing time is 0.1–15 h.

[0035] In one embodiment, the substrate in step S3 is a polytetrafluoroethylene (PTFE) film.

[0036] In one embodiment, the moving speed during coating in step S3 is 0.1 to 10 m / min.

[0037] In one embodiment, step S3 uses ultraviolet light irradiation for curing, wherein the wavelength of the ultraviolet light is 100-385 nm and the irradiation time is 5-8 min.

[0038] In one embodiment, the drying temperature in step S3 is 75–120°C.

[0039] In one embodiment, steps S1 to S3 are all performed under an argon atmosphere or a nitrogen atmosphere.

[0040] In one embodiment, the thickness of the lithium-ion solid electrolyte film is 10–120 μm.

[0041] According to a third aspect of this disclosure, a solid-state lithium-ion battery is provided, comprising a positive electrode, a negative electrode, and the aforementioned lithium-ion solid electrolyte.

[0042] In one embodiment, the positive electrode comprises, by weight percentage, 90-96% of the positive electrode active material, 0-5% of the positive electrode conductive agent, and 0-5% of the positive electrode binder.

[0043] Typically, but not limitingly, the mass percentage of the positive electrode active material can be 90%, 91%, 92%, 93%, 94%, 95%, or 96%, or any value within the range of 90% to 96%.

[0044] Typically, but not limitingly, the mass percentage of the positive conductive agent can be 1%, 2%, 3%, 4%, or 5%, or any value in the range of 0 to 5%.

[0045] Typically, but not limitingly, the mass percentage of the positive electrode binder can be 1%, 2%, 3%, 4%, or 5%, or any value in the range of 0 to 5%.

[0046] In one embodiment, the positive electrode active material includes lithium iron phosphate, lithium nickel cobalt aluminum oxide (NCA), lithium nickel manganese cobalt oxide (NCM), and lithium-rich manganese-based crystalline oxide (Li). 1+x [NiMnCo] 1-x At least one of O2, LMR-NMC, lithium cobalt oxide (LCO), and lithium manganese oxide (LMO).

[0047] In one embodiment, the positive electrode conductive agent includes at least one of VGCF, carbon black, acetylene black, Ketjen black, carbon nanotubes, and graphene.

[0048] In one embodiment, the positive electrode binder includes at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinylidene fluoride hexafluoropropylene, polypropylene, polyethylene, and polyimide.

[0049] In one embodiment, the negative electrode comprises, by weight percentage, 90-96% of the negative electrode active material, 0-5% of the negative electrode conductive agent, and 0-5% of the negative electrode binder.

[0050] Typically, but not limitingly, the mass percentage of the negative electrode active material can be 90%, 91%, 92%, 93%, 94%, 95%, or 96%, or any value within the range of 90% to 96%.

[0051] Typically, but not limitingly, the mass percentage of the negative electrode conductive agent can be 1%, 2%, 3%, 4%, or 5%, or any value in the range of 0 to 5%.

[0052] Typically, but not limitingly, the mass percentage of the negative electrode binder can be 1%, 2%, 3%, 4%, or 5%, or any value in the range of 0 to 5%.

[0053] In one embodiment, the negative electrode active material includes at least one of artificial graphite, natural graphite, silicon (Si), silicon suboxide (SiO), pre-lithiated silicon suboxide, silicon carbide (SiC), lithium, aluminum-silicon alloy, lithium-indium alloy, lithium-tin alloy, and lithium-aluminum alloy.

[0054] In one embodiment, the negative electrode conductive agent includes at least one of VGCF, carbon black, acetylene black, Ketjen black, carbon nanotubes, and graphene.

[0055] In one embodiment, the negative electrode binder includes at least one of sodium carboxymethyl cellulose, carboxymethyl cellulose, methyl cellulose, styrene-butadiene latex, polyacrylic acid, acrylic copolymers, cyclodextrin, styrene-butadiene rubber (SBR), nitrile rubber (NBR), hydrogenated nitrile rubber (HNBR), polymethyl methacrylate (PMMA), styrene-butadiene block copolymer (SBS), styrene-ethylene-butene-styrene block copolymer (SEBS), and polyisobutylene (PIB).

[0056] According to the fourth aspect of this disclosure, an apparatus for manufacturing the aforementioned solid-state lithium-ion battery is provided, comprising a positive electrode feeding and unwinding device, a negative electrode unwinding device, a solid electrolyte separator unwinding device, and a core winding and pressing device.

[0057] According to one possible implementation of this disclosure, at least the following beneficial effects are achieved:

[0058] This disclosure presents a self-supporting elastic lithium-ion solid electrolyte composed of a polymer matrix, polymer monomers, a eutectic mixture (prepared from a mixture of lithium salt and polar organic compounds), and anion acceptors. The ratio of the first monomer polymer (hard phase, polymerized from the first monomer) and the second monomer polymer (soft phase, polymerized from the second monomer) in the lithium-ion solid electrolyte is controlled to combine the tensile strength of the soft phase (second monomer polymer) and the strength of the hard phase (first monomer polymer) in the polymer. Furthermore, the first monomer, second monomer, and polymer matrix undergo copolymerization and crosslinking under the action of a crosslinking agent, achieving good mechanical stability of the lithium-ion electrolyte membrane through an interwoven network structure. The introduction of the eutectic mixture, characterized by low volatility, non-flammability, excellent electrochemical stability, and low viscosity, improves the ionic conductivity and safety of the lithium-ion solid electrolyte while avoiding the volatility disadvantage of traditional organic liquid electrolytes. By introducing a certain amount of anion acceptors into the polymerization system, a high lithium-ion transfer number is achieved in the lithium-ion solid electrolyte. Due to its high lithium-ion transfer number, the lithium-ion solid electrolyte effectively inhibits lithium dendrite growth. Furthermore, a simple and rapid large-scale production process for electrolyte membranes was achieved through photo-initiated polymerization. A roll-to-roll processable, self-supporting solid electrolyte membrane and a roll-forming integrated device for solid-state batteries were developed, solving the problem of electrode stress failure under low stacking pressure. Integrating the self-supporting lithium-ion solid electrolyte membrane into the fabrication of rolled solid cylindrical batteries expands the commercial application potential of long-cycle solid-state lithium batteries.

[0059] It should be understood that the description in this section is not intended to identify key or essential features of the embodiments of this disclosure, nor is it intended to limit the scope of this disclosure. Other features of this disclosure will become readily apparent from the following description. Attached Figure Description

[0060] The above and other objects, features, and advantages of this disclosure will become readily apparent from the following detailed description of exemplary embodiments, taken in conjunction with the accompanying drawings. Several embodiments of this disclosure are illustrated in the drawings by way of example and not limitation, in which:

[0061] In the accompanying drawings, the same or corresponding reference numerals indicate the same or corresponding parts.

[0062] Figure 1 A schematic diagram of the structure of the polar organic compound in this disclosure is shown;

[0063] Figure 2 A schematic diagram of the structure of the first monomer in this disclosure is shown;

[0064] Figure 3 A schematic diagram of the structure of the second monomer in this disclosure is shown;

[0065] Figure 4 A schematic diagram of the process for preparing lithium-ion solid electrolytes in Embodiment 1 of this disclosure is shown;

[0066] Figure 5 A schematic diagram of the molecular design and preparation process of the lithium-ion solid electrolyte in Embodiment 1 of this disclosure is shown;

[0067] Figure 6 A schematic diagram of the structure of the all-solid-state battery core continuous roll winding integrated forming device according to a specific embodiment of the present disclosure is shown. Detailed Implementation

[0068] To make the objectives, features, and advantages of this disclosure more apparent and understandable, the technical solutions in the embodiments of this disclosure will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of this disclosure, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this disclosure without creative effort are within the scope of protection of this disclosure.

[0069] This disclosure presents a multifunctional elastic lithium-ion solid electrolyte with high lithium-ion mobility, a certain degree of flexibility, and strong compatibility with both positive and negative electrodes. This elastic lithium-ion solid electrolyte weakens the interaction between lithium ions and anions in the lithium salt through the chemical synergy between the anion acceptor and the eutectic mixture, significantly enhancing the dissociation of the lithium salt. Furthermore, the anion acceptor coordinates with anions in the lithium salt through Lewis acid or pore confinement effects, weakening the electrostatic attraction between lithium ions and anions in the lithium salt, thereby increasing the lithium-ion transference number. Simultaneously, the high lithium-ion mobility effectively alleviates concentration polarization and dendrite growth in the battery, and effectively suppresses the corrosion of the Al current collector by anions in the lithium salt, ensuring the long-term cycle stability of the battery. In addition, a simple and rapid large-scale production of the electrolyte is achieved through photo-initiated polymerization. A roll-to-roll processable self-supporting solid electrolyte membrane and a solid-state battery winding and rolling integrated device are developed, solving the problem of electrode stress failure under low stacking pressure. Integrating the self-supporting elastic lithium-ion solid electrolyte membrane into the manufacturing of wound solid cylindrical batteries broadens the commercial application potential of long-cycle solid-state lithium batteries.

[0070] The lithium-ion solid electrolyte disclosed herein comprises a polymer matrix, a lithium salt, a polar organic compound, a polymer monomer, and an anion acceptor; the polymer monomer comprises a first monomer and a second monomer.

[0071] The polymer matrix includes at least one of polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polyethylene oxide (PEO, Mw = 600,000 to 1,000,000), poly(methyl methacrylate) (PMMA), poly(vinyl acetate) (PVAc), polyvinylidene fluoride (PVDF), and polyacrylonitrile (PAN).

[0072] Lithium salts include at least one of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium difluorooxalate borate (LiDFOB), lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium bis(oxalate)borate (LiBOB), lithium bis(fluorosulfonyl)imide (LiFSI), lithium trifluoromethanesulfonate (LiTf), lithium difluorophosphonate (LiPO2F2), lithium nitrate (LiNO3), lithium perchlorate (LiClO4), lithium chloride (LiCl), lithium iodide (LiI), and lithium bromide (LiBr).

[0073] Polar organic compounds include at least one of N-methylacetamide (NMA), N-ethylacetamide (NEA), 2-methylpropionamide, 1-methyl-3-propylimidazolium, triethylene glycol dimethyl ether, lactic acid, triethanolamine, glycerol, and urea. The structures of each compound are as follows: Figure 1 As shown.

[0074] The first monomer includes at least one of acrylamide (AM) and its derivatives, the structures of which are as follows: Figure 2 As shown.

[0075] The second monomer includes at least one of dimethylacrylamide (DMAM) and its derivatives, the structures of which are as follows: Figure 3 As shown.

[0076] Anion acceptors include at least one of tris(pentafluorophenyl)borane (TPFPB), fluoroalkyl borates (such as (C6H3F)2B(C6H5F2)), trimethyl borate, phenyl borate derivatives (such as phenyl borate esters), trifluoroboron diethyl ether complexes (BF3·OEt2), borate ester crosslinking agents (such as pentaerythritol borate esters), polyvinyl borate esters, tris(pentafluorophenyl)boron (B(C6F5)3), methacrylate borate copolymers, polystyrene sulfonate (PSS), polypyrrolidone (PVP) derivatives, CC3 type porous organic cages (POCs), fluorinated covalent organic frameworks (F-COF), boron-doped porous organic cages (B-POC), and triazine covalent organic frameworks (CTF-1).

[0077] The following examples illustrate this in detail.

[0078] Example 1

[0079] This embodiment prepares a lithium-ion solid electrolyte, the flowchart of which is shown below. Figure 4 As shown in the diagram, the design schematic is as follows: Figure 5 As shown, the details are as follows:

[0080] (1) Under an argon atmosphere, 2.4 mol of N-ethylacetamide and 0.6 mol of LiTFSI were poured into a 500 mL glass beaker and stirred at 25 °C for 45 min to mix evenly and form a eutectic mixture.

[0081] (2) 0.5 mol of anhydrous acetone solvent, 4.8 mol of polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), 0.1 mol of plasticizer FEC, 0.5 mol of tris(pentafluorophenyl)borane (TPFPB) as an anion acceptor, 4.8 mol of acrylamide (AM), 1.2 mol of dimethylacrylamide (DMAM), 3 mol of crosslinking agent N,N'-methylenebisacrylamide and 1.6 mol of photoinitiator 2-hydroxy-2-methylphenylacetone were added to the above eutectic mixture and stirred at 30°C for 12 h to form a homogeneous precursor solution.

[0082] (3) The above homogeneous precursor solution was coated onto a polytetrafluoroethylene film substrate and then cured under ultraviolet light (365nm) for 6 minutes. The film thickness was controlled to be 10μm by a doctor blade. Then, it was dried at 75℃ to obtain the lithium-ion solid electrolyte. The entire processing environment was an argon atmosphere, and the oxygen content was controlled to be <0.1ppm and the water content to be <0.1ppm.

[0083] Example 2

[0084] This embodiment prepares a lithium-ion solid electrolyte, as detailed below:

[0085] (1) Under an argon atmosphere, 2.4 mol of N-ethylacetamide and 0.5 mol of LiTFSI were poured into a 500 mL glass beaker and stirred at 25 °C for 45 min to mix evenly and form a eutectic mixture.

[0086] (2) 0.5 mol of anhydrous acetone solvent, 4.8 mol of polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), 0.1 mol of plasticizer FEC, 0.5 mol of tris(pentafluorophenyl)borane (TPFPB) as an anion acceptor, 4.8 mol of acrylamide (AM), 1.2 mol of dimethylacrylamide (DMAM), 3 mol of crosslinking agent N,N'-methylenebisacrylamide and 1.6 mol of photoinitiator 2-hydroxy-2-methylphenylacetone were added to the above eutectic mixture and stirred at 30°C for 12 h to form a homogeneous precursor solution.

[0087] (3) The above homogeneous precursor solution was coated onto a polytetrafluoroethylene film substrate and then cured under ultraviolet light (365nm) for 6 minutes. The film thickness was controlled to be 10μm by a doctor blade. Then, it was dried at 75℃ to obtain the lithium-ion solid electrolyte. The entire processing environment was an argon atmosphere, and the oxygen content was controlled to be <0.1ppm and the water content to be <0.1ppm.

[0088] Example 3

[0089] This embodiment prepares a lithium-ion solid electrolyte, as detailed below:

[0090] (1) Under an argon atmosphere, 2.4 mol of N-ethylacetamide and 0.4 mol of LiTFSI were poured into a 500 mL glass beaker and stirred at 25 °C for 45 min to mix evenly and form a eutectic mixture.

[0091] (2) 0.5 mol of anhydrous acetone solvent, 4.8 mol of polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), 0.1 mol of plasticizer FEC, 0.5 mol of tris(pentafluorophenyl)borane (TPFPB) as an anion acceptor, 4.8 mol of acrylamide (AM), 1.2 mol of dimethylacrylamide (DMAM), 3 mol of crosslinking agent N,N'-methylenebisacrylamide and 1.6 mol of photoinitiator 2-hydroxy-2-methylphenylacetone were added to the above eutectic mixture and stirred at 30°C for 12 h to form a homogeneous precursor solution.

[0092] (3) The above homogeneous precursor solution was coated onto a polytetrafluoroethylene film substrate and then cured under ultraviolet light (365nm) for 6 minutes. The film thickness was controlled to be 10μm by a doctor blade. Then, it was dried at 75℃ to obtain the lithium-ion solid electrolyte. The entire processing environment was an argon atmosphere, and the oxygen content was controlled to be <0.1ppm and the water content to be <0.1ppm.

[0093] Example 4

[0094] This embodiment prepares a lithium-ion solid electrolyte, as detailed below:

[0095] (1) Under an argon atmosphere, 2.4 mol of N-ethylacetamide and 0.3 mol of LiTFSI were poured into a 500 mL glass beaker and stirred at 25 °C for 45 min to mix evenly and form a eutectic mixture.

[0096] (2) 0.5 mol of anhydrous acetone solvent, 4.8 mol of polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), 0.1 mol of plasticizer FEC, 0.5 mol of tris(pentafluorophenyl)borane (TPFPB) as an anion acceptor, 4.8 mol of acrylamide (AM), 1.2 mol of dimethylacrylamide (DMAM), 3 mol of crosslinking agent N,N'-methylenebisacrylamide and 1.6 mol of photoinitiator 2-hydroxy-2-methylphenylacetone were added to the above eutectic mixture and stirred at 30°C for 12 h to form a homogeneous precursor solution.

[0097] (3) The above homogeneous precursor solution was coated onto a polytetrafluoroethylene film substrate and then cured under ultraviolet light (365nm) for 6 minutes. The film thickness was controlled to be 10μm by a doctor blade. Then, it was dried at 75℃ to obtain the lithium-ion solid electrolyte. The entire processing environment was an argon atmosphere, and the oxygen content was controlled to be <0.1ppm and the water content to be <0.1ppm.

[0098] Example 5

[0099] This embodiment prepares a lithium-ion solid electrolyte, as detailed below:

[0100] (1) Under an argon atmosphere, 2.4 mol of N-ethylacetamide and 0.7 mol of LiTFSI were poured into a 500 mL glass beaker and stirred at 25 °C for 45 min to mix evenly and form a eutectic mixture.

[0101] (2) 0.5 mol of anhydrous acetone solvent, 4.8 mol of polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), 0.1 mol of plasticizer FEC, 0.5 mol of tris(pentafluorophenyl)borane (TPFPB) as an anion acceptor, 4.8 mol of acrylamide (AM), 1.2 mol of dimethylacrylamide (DMAM), 3 mol of crosslinking agent N,N'-methylenebisacrylamide and 1.6 mol of photoinitiator 2-hydroxy-2-methylphenylacetone were added to the above eutectic mixture and stirred at 30°C for 12 h to form a homogeneous precursor solution.

[0102] (3) The above homogeneous precursor solution was coated onto a polytetrafluoroethylene film substrate and then cured under ultraviolet light (365nm) for 6 minutes. The film thickness was controlled to be 10μm by a doctor blade. Then, it was dried at 75℃ to obtain the lithium-ion solid electrolyte. The entire processing environment was an argon atmosphere, and the oxygen content was controlled to be <0.1ppm and the water content to be <0.1ppm.

[0103] Example 6

[0104] This embodiment prepares a lithium-ion solid electrolyte, as detailed below:

[0105] (1) Under an argon atmosphere, 2.4 mol of N-ethylacetamide and 0.8 mol of LiTFSI were poured into a 500 mL glass beaker and stirred at 25 °C for 45 min to mix evenly and form a eutectic mixture.

[0106] (2) 0.5 mol of anhydrous acetone solvent, 4.8 mol of polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), 0.1 mol of plasticizer FEC, 0.5 mol of tris(pentafluorophenyl)borane (TPFPB) as an anion acceptor, 4.8 mol of acrylamide (AM), 1.2 mol of dimethylacrylamide (DMAM), 3 mol of crosslinking agent N,N'-methylenebisacrylamide and 1.6 mol of photoinitiator 2-hydroxy-2-methylphenylacetone were added to the above eutectic mixture and stirred at 30°C for 12 h to form a homogeneous precursor solution.

[0107] (3) The above homogeneous precursor solution was coated onto a polytetrafluoroethylene film substrate and then cured under ultraviolet light (365nm) for 6 minutes. The film thickness was controlled to be 10μm by a doctor blade. Then, it was dried at 75℃ to obtain the lithium-ion solid electrolyte. The entire processing environment was an argon atmosphere, and the oxygen content was controlled to be <0.1ppm and the water content to be <0.1ppm.

[0108] Example 7

[0109] This embodiment prepares a lithium-ion solid electrolyte, as detailed below:

[0110] (1) Under an argon atmosphere, 2.4 mol of N-ethylacetamide and 0.9 mol of LiTFSI were poured into a 500 mL glass beaker and stirred at 25 °C for 45 min to mix evenly and form a eutectic mixture.

[0111] (2) 0.5 mol of anhydrous acetone solvent, 4.8 mol of polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), 0.1 mol of plasticizer FEC, 0.5 mol of tris(pentafluorophenyl)borane (TPFPB) as an anion acceptor, 4.8 mol of acrylamide (AM), 1.2 mol of dimethylacrylamide (DMAM), 3 mol of crosslinking agent N,N'-methylenebisacrylamide and 1.6 mol of photoinitiator 2-hydroxy-2-methylphenylacetone were added to the above eutectic mixture and stirred at 30°C for 12 h to form a homogeneous precursor solution.

[0112] (3) The above homogeneous precursor solution was coated onto a polytetrafluoroethylene film substrate and then cured under ultraviolet light (365nm) for 6 minutes. The film thickness was controlled to be 10μm by a doctor blade. Then, it was dried at 75℃ to obtain the lithium-ion solid electrolyte. The entire processing environment was an argon atmosphere, and the oxygen content was controlled to be <0.1ppm and the water content to be <0.1ppm.

[0113] Example 8

[0114] This embodiment prepares a lithium-ion solid electrolyte, as detailed below:

[0115] (1) Under an argon atmosphere, 2.4 mol of N-ethylacetamide and 0.95 mol of LiTFSI were poured into a 500 mL glass beaker and stirred at 25 °C for 45 min to mix evenly and form a eutectic mixture.

[0116] (2) 0.5 mol of anhydrous acetone solvent, 4.8 mol of polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), 0.1 mol of plasticizer FEC, 0.5 mol of tris(pentafluorophenyl)borane (TPFPB) as an anion acceptor, 4.8 mol of acrylamide (AM), 1.2 mol of dimethylacrylamide (DMAM), 3 mol of crosslinking agent N,N'-methylenebisacrylamide and 1.6 mol of photoinitiator 2-hydroxy-2-methylphenylacetone were added to the above eutectic mixture and stirred at 30°C for 12 h to form a homogeneous precursor solution.

[0117] (3) The above homogeneous precursor solution was coated onto a polytetrafluoroethylene film substrate and then cured under ultraviolet light (365nm) for 6 minutes. The film thickness was controlled to be 10μm by a doctor blade. Then, it was dried at 75℃ to obtain the lithium-ion solid electrolyte. The entire processing environment was an argon atmosphere, and the oxygen content was controlled to be <0.1ppm and the water content to be <0.1ppm.

[0118] Comparative Example 1

[0119] This comparative example prepared a lithium-ion solid electrolyte. The difference from Example 1 is that no second monomer was added in this comparative example. Details are as follows:

[0120] (1) Under an argon atmosphere, 2.4 mol of N-ethylacetamide and 0.6 mol of LiTFSI were poured into a 500 mL glass beaker and stirred at 25 °C for 45 min to mix evenly and form a eutectic mixture.

[0121] (2) 0.5 mol of anhydrous acetone solvent, 4.8 mol of polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), 0.1 mol of plasticizer FEC, 0.5 mol of tris(pentafluorophenyl)borane (TPFPB) as an anion acceptor, 4.8 mol of acrylamide (AM), 3 mol of crosslinking agent N,N'-methylenebisacrylamide and 1.6 mol of photoinitiator 2-hydroxy-2-methylphenylacetone were added to the above eutectic mixture and stirred at 30°C for 12 h to form a homogeneous precursor solution.

[0122] (3) The above homogeneous precursor solution was coated onto a polytetrafluoroethylene film substrate and then cured under ultraviolet light (365nm) for 6 minutes. The film thickness was controlled to be 10μm by a doctor blade. Then, it was dried at 75℃ to obtain the lithium-ion solid electrolyte. The entire processing environment was an argon atmosphere, and the oxygen content was controlled to be <0.1ppm and the water content to be <0.1ppm.

[0123] Comparative Example 2

[0124] This comparative example prepared a lithium-ion solid electrolyte, which differs from Example 1 in that the first monomer was not added. Details are as follows:

[0125] (1) Under an argon atmosphere, 2.4 mol of N-ethylacetamide and 0.6 mol of LiTFSI were poured into a 500 mL glass beaker and stirred at 25 °C for 45 min to mix evenly and form a eutectic mixture.

[0126] (2) 0.5 mol of anhydrous acetone solvent, 4.8 mol of polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), 0.1 mol of plasticizer FEC, 0.5 mol of tris(pentafluorophenyl)borane (TPFPB) as an anion acceptor, 1.2 mol of dimethylacrylamide (DMAM), 3 mol of crosslinking agent N,N'-methylenebisacrylamide and 1.6 mol of photoinitiator 2-hydroxy-2-methylphenylacetone were added to the above eutectic mixture and stirred at 30°C for 12 h to form a homogeneous precursor solution.

[0127] (3) The above homogeneous precursor solution was coated onto a polytetrafluoroethylene film substrate and then cured under ultraviolet light (365nm) for 6 minutes. The film thickness was controlled to be 10μm by a doctor blade. Then, it was dried at 75℃ to obtain the lithium-ion solid electrolyte. The entire processing environment was an argon atmosphere, and the oxygen content was controlled to be <0.1ppm and the water content to be <0.1ppm.

[0128] Comparative Example 3

[0129] This comparative example prepared a lithium-ion solid electrolyte, which differs from Example 1 in that it prepared a halide lithium-ion solid electrolyte. Details are as follows:

[0130] Li3InCl6 and PTFE were added to a mortar at a mass ratio of 96:4, mixed evenly, and rolled to obtain a halide lithium-ion solid electrolyte with a thickness of 10 μm.

[0131] Test case

[0132] Solid-state lithium-ion batteries were prepared using the lithium-ion solid-state electrolytes prepared in Examples 1-8 and Comparative Examples 1-2. The specific steps are as follows:

[0133] (1) NCM811, VGCF, and PVDF in a mass ratio of 96:2:2 were added to N-methylpyrrolidone (NMP), mixed to form a slurry, and then coated onto carbon-coated aluminum foil. The mixture was then vacuum-dried at 92°C for 18 hours to obtain the positive electrode sheet; (2) a lithium metal sheet was used as the negative electrode; (3) using... Figure 6 The all-solid-state battery core continuous roll winding integrated molding device shown places the lithium-ion solid electrolyte prepared in Examples 1-8 or Comparative Examples 1-2 directly between the above-mentioned negative and positive electrode sheets, allowing the solid electrolyte to penetrate and occupy the internal pores of the porous electrode, and then heats and solidifies at 60°C for 12 hours. Finally, after electrode tab welding and vacuum sealing, the NCM811||Li all-solid-state lithium-ion battery is obtained.

[0134] Solid-state lithium-ion batteries were prepared using the lithium-ion solid-state electrolyte prepared in Comparative Example 3. The specific steps are as follows:

[0135] (1) NCM811, Li3InCl6, VGCF and PVDF in a mass ratio of 96:2:2 were added to N-methylpyrrolidone (NMP), mixed to form a slurry, and then coated onto carbon-coated aluminum foil. After the NMP evaporated naturally, it was vacuum dried at 92°C for 18 hours to obtain the positive electrode sheet. (2) A lithium metal sheet was used as the negative electrode. (3) The lithium-ion solid electrolyte prepared in Comparative Example 3 was directly placed between the negative and positive electrode sheets and stacked and bonded. After tab welding and vacuum sealing, the NCM811|Li3InCl6|Li all-solid-state lithium-ion battery was obtained.

[0136] 1. Tensile strength test: The lithium-ion solid electrolytes prepared in Examples 1-8 and Comparative Examples 1-3 were subjected to tensile stress-strain tests. To prepare samples for tensile testing, a homogeneous precursor solution was poured into a dumbbell-shaped polytetrafluoroethylene mold with effective dimensions of 16×4×2mm, followed by UV polymerization for 5min, with the tensile deformation rate set at 100mm / min.

[0137] 2. Ionic Conductivity Test: The ionic conductivity of the lithium-ion solid electrolyte was obtained by electrochemical impedance spectroscopy (EIS) measurements on an electrochemical workstation at a frequency range of 0.1 Hz to 10 MHz, an amplitude of 10 mV, and a temperature of 25 °C, using a symmetrical battery with a steel sheet as the blocking electrode. The calculation formula is as follows:

[0138] σ=L / (R b ·S)

[0139] Where S represents the effective contact area (cm²) between the electrolyte and the occluded electrode. 2 L represents the thickness (cm) of the solid polymer electrolyte membrane, and R represents the thickness (cm) of the solid polymer electrolyte membrane. b This represents the total impedance of the electrolyte (Ω).

[0140] 3. Ion transference number test: The lithium-ion transference number of the lithium-ion solid electrolyte was determined by combining AC impedance and current polarization. First, the initial interfacial impedance R of the lithium-ion batteries prepared in Examples 1-8 and Comparative Examples 1-3 was tested. ct 0 Then, the battery current was measured at a constant voltage ΔV (10mV in this test) to obtain the current change curve. The initial current was I. 0 After stabilization, it becomes I. s Finally, the impedance R was tested in the steady state. ct s The frequency range is from 1000 kHz to 0.1 Hz. Calculated according to the lithium-ion transport number formula:

[0141] t Li + =I s [ΔV-I 0 R ct 0 ] / I 0 [ΔV-I s R ct s ].

[0142] 4. Electrical performance test: The lithium-ion solid electrolytes prepared in Examples 1-8 and Comparative Examples 1-3 were used to prepare cells for charge and discharge tests: the mold half-cell was charged at a constant current of 0.1C to 4.25V, charged at a constant voltage to 0.05C, and discharged at a constant current of 0.1C to 0.05V.

[0143] 5. Discharge capacity and cycle performance:

[0144] Cyclic tests were conducted on the all-solid-state lithium-ion batteries prepared in Examples 1-8 and Comparative Examples 1-3. At a temperature of 25±2°C, the batteries were first charged at 0.1C or a specified current to a termination voltage of 4.25V, with a cutoff current of 0.01C, and then allowed to rest for 30 minutes. The second step involved discharging at 0.1C to a final discharge voltage of 0.05V, recording the discharge capacity, and allowing the batteries to rest for 30 minutes. The cycle of steps one and two was repeated for 500 cycles to test the battery's cycle performance. All tests were conducted under a specific stacking pressure (50 kPa) load condition.

[0145] The test results are shown in Table 1.

[0146] Table 1

[0147]

[0148]

[0149] Table 1 shows that, compared with Examples 1-8, the ionic conductivity of the eutectic mixture reaches its maximum value when the molar ratio of NMA:LiTFSI is 4:1 (Example 1). As the lithium salt concentration decreases, the degree of lithium salt dissociation increases, resulting in higher ionic conductivity of the eutectic mixture. However, excessively low lithium salt ratios lead to lower ionic conductivity due to lower carrier concentrations. Comparing Example 1 with Comparative Examples 1 and 2, the pure second monomer exhibits excellent tensile strength but low fracture strength. The low fracture strength is due to the lack of interchain interactions, as the second monomer polymer is miscible with the eutectic mixture, resulting in highly solvated molecular chains. The pure first monomer polymer exhibits extremely low elongation at break and high fracture strength. Copolymerizing the first monomer polymer (hard phase) and the second monomer polymer (soft phase) at a molar ratio of 4:1 results in a polymer that combines the tensile strength of the soft phase (second monomer polymer) and the strength of the hard phase (first monomer polymer).

[0150] Example 1 introduces a lithium-ion solid electrolyte with high room temperature ionic conductivity and good tensile properties into the internal structure of a porous electrode, and achieves tight bonding with the active material particles inside the electrode, thereby solving the problem of electrode stress failure under low stacking pressure and realizing good cycle stability of the all-solid-state lithium-ion battery under low stacking pressure or even without external pressure.

[0151] It should be understood that the various forms of processes shown above can be used to rearrange, add, or delete steps. For example, the steps described in this disclosure can be executed in parallel, sequentially, or in different orders, as long as the desired result of the technical solution of this disclosure can be achieved, and this is not limited herein.

[0152] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature. In the description of this disclosure, "a plurality of" means two or more, unless otherwise explicitly specified.

[0153] The above description is merely a specific embodiment of this disclosure, but the scope of protection of this disclosure is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this disclosure should be included within the scope of protection of this disclosure. Therefore, the scope of protection of this disclosure should be determined by the scope of the claims.

Claims

1. A lithium-ion solid electrolyte, characterized in that, The lithium-ion solid electrolyte comprises a polymer matrix, a lithium salt, a polar organic compound, a polymer monomer, and an anion acceptor; the polymer monomer comprises a first monomer and a second monomer.

2. The lithium-ion solid electrolyte according to claim 1, characterized in that, The polymer matrix includes at least one of polyvinylidene fluoride-hexafluoropropylene copolymer, polyethylene oxide, poly(methyl methacrylate), poly(vinyl acetate), polyvinylidene fluoride, and polyacrylonitrile; Preferably, the molar ratio of the polymer monomer to the polymer matrix is ​​(0.2-5):1; Preferably, the lithium salt comprises at least one of lithium bis(trifluoromethanesulfonyl)imide, lithium difluorooxalate borate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis(oxalate)borate, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium nitrate, lithium perchlorate, lithium chloride, lithium iodide, and lithium bromide. Preferably, the polar organic compound includes at least one selected from N-methylacetamide, N-ethylacetamide, 2-methylpropionamide, 1-methyl-3-propylimidazolium, triethylene glycol dimethyl ether, lactic acid, triethanolamine, glycerol, and urea. Preferably, the molar ratio of the lithium salt to the polar organic compound is 1:(1 to 10).

3. The lithium-ion solid electrolyte according to claim 1, characterized in that, The first monomer includes at least one of acrylamide and its derivatives; Preferably, the second monomer comprises at least one of dimethacrylamide and its derivatives; Preferably, the molar ratio of the first monomer to the second monomer is (0.3-5):1; Preferably, the anion acceptor comprises at least one of tris(pentafluorophenyl)borane, fluoroalkyl borate, trimethyl borate, phenylboronic acid derivative, boron trifluoride diethyl ether complex, borate ester crosslinking agent, polyvinyl borate, tris(pentafluorophenyl)boron, methacrylate borate copolymer, polystyrene sulfonate, polypyrrolidone derivative, CC3 type porous organic cage, fluorinated covalent organic framework, boron-doped porous organic cage, and triazine covalent organic framework.

4. The lithium-ion solid electrolyte according to claim 1, characterized in that, The lithium-ion solid electrolyte also includes plasticizers, crosslinking agents, initiators, and solvents; The plasticizer includes at least one of fluoroethylene carbonate, succinic anion, polyethylene glycol dimethyl ether, dibutyl phthalate, trifluoroethoxyethane, and ionic liquid. The crosslinking agent includes at least one of N,N'-methylenebisacrylamide, polyethylene glycol diacrylate, trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, polyethylene glycol dimethacrylate, divinylbenzene, triallylamine, bisacryloylcysteine, triacryloylhexahydro-1,3,5-triazine, and pentaerythritol tetraacrylate. The initiator includes at least one of 2,2-azobisisobutyronitrile, 4-methylbenzophenone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, 2-hydroxy-2-methylphenylacetone, benzoin dimethyl ether, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and lithium phenyl-2,4,6-trimethylbenzoylphosphonate. The solvent includes at least one of anhydrous acetonitrile, N-methylpyrrolidone, cyclohexane, toluene, xylene, acetonitrile, dichloromethane, dimethyl sulfoxide, dimethylformamide, acetone, tetrahydrofuran, chloroform, and dimethylacetamide; Preferably, the molar ratio of the polymer monomer to the crosslinking agent is (0.5-4):1; Preferably, the ratio of the total molar amount of the polymer monomer and the polymer matrix to the molar amount of the solvent is (1-25):1; Preferably, the molar ratio of the crosslinking agent to the initiator is (0.5-3):

1.

5. The method for preparing the lithium-ion solid electrolyte according to any one of claims 1 to 4, characterized in that, Includes the following steps: S1: A lithium salt and a polar organic compound are mixed to obtain a eutectic mixture; S2: Mix the polymer matrix, the first monomer, the second monomer, and the anion acceptor with the eutectic mixture to obtain a precursor solution; S3: After coating the precursor liquid onto the substrate, cure and dry it to obtain the lithium-ion solid electrolyte.

6. The preparation method according to claim 5, characterized in that, The lithium salt and the polar organic compound are mixed at 20–40°C for 0.1–10 h; Preferably, in step S2, the polymer matrix, the first monomer, the second monomer, the anion acceptor, the plasticizer, the crosslinking agent, the initiator, and the solvent are mixed with the eutectic mixture to obtain the precursor solution; Preferably, the mixing temperature in step S2 is 20–40°C, and the mixing time is 0.1–15 h. Preferably, step S3 uses ultraviolet light irradiation for curing, wherein the wavelength of the ultraviolet light is 100-385 nm and the irradiation time is 5-8 min; Preferably, the drying temperature in step S3 is 75–120°C.

7. A solid-state lithium-ion battery, characterized in that, The solid-state lithium-ion battery includes a positive electrode, a negative electrode, and a lithium-ion solid electrolyte as described in any one of claims 1 to 4.

8. The solid-state lithium-ion battery according to claim 7, characterized in that, The positive electrode comprises, by weight percentage, 90-96% positive electrode active material, 0-5% positive electrode conductive agent and 0-5% positive electrode binder; The positive electrode active material includes at least one of lithium iron phosphate, lithium nickel cobalt aluminum oxide, lithium nickel manganese cobalt oxide, lithium-rich manganese base oxide, lithium cobalt oxide, and lithium manganese oxide. The positive electrode conductive agent includes at least one of VGCF, carbon black, acetylene black, Ketjen black, carbon nanotubes, and graphene. The positive electrode binder includes at least one of polyvinylidene fluoride, polytetrafluoroethylene, polyvinylidene fluoride hexafluoropropylene, polypropylene, polyethylene, and polyimide.

9. The solid-state lithium-ion battery according to claim 7, characterized in that, The negative electrode comprises, by weight percentage, 90-96% of the negative electrode active material, 0-5% of the negative electrode conductive agent and 0-5% of the negative electrode binder; The negative electrode active material includes at least one of the following: artificial graphite, natural graphite, silicon, silicon suboxide, pre-lithiated silicon suboxide, silicon carbide, lithium, aluminum-silicon alloy, lithium-indium alloy, lithium-tin alloy, and lithium-aluminum alloy. The negative electrode conductive agent includes at least one of VGCF, carbon black, acetylene black, Ketjen black, carbon nanotubes, and graphene. The negative electrode binder includes at least one of sodium hydroxymethyl cellulose, carboxymethyl cellulose, methyl cellulose, styrene-butadiene latex, polyacrylic acid, acrylic copolymers, cyclodextrin, styrene-butadiene rubber, nitrile rubber, hydrogenated nitrile rubber, polymethyl methacrylate, styrene-butadiene block copolymer, styrene-ethylene-butene-styrene block copolymer, and polyisobutylene.

10. The apparatus for manufacturing a solid-state lithium-ion battery according to any one of claims 7 to 9, characterized in that, The manufacturing apparatus includes a positive electrode feeding and unwinding device, a negative electrode unwinding device, a solid electrolyte separator membrane unwinding device, and a core winding and pressing device.

Images