Sodium ion solid electrolyte and preparation method and application thereof

Abstract

The invention belongs to the technical field of solid-state batteries, and provides a sodium ion solid-state electrolyte as well as a preparation method and application thereof. The sodium ion solid electrolyte comprises a polymer matrix, a sodium 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 sodium 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 sodium-ion battery comprising the sodium-ion solid electrolyte and a manufacturing device of the solid-state sodium-ion battery. The sodium 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 sodium 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 sodium-ion solid electrolytes, their preparation methods, and applications. Background Technology

[0002] With the booming development of the new energy market, traditional sodium-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 sodium-ion solid electrolytes mainly include oxide, sulfide, and halide sodium-ion solid electrolytes and polymer sodium-ion solid electrolytes. However, these sodium-ion solid electrolytes still encounter many problems in practical applications that need to be solved. For example, sulfide sodium-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 sodium-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 sodium-ion solid electrolytes cannot be used on a large scale due to poor compatibility with the negative electrode and easy hydrolysis. Polymer sodium-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 sodium-ion solid electrolyte, thus hindering sodium 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 a sodium-ion solid electrolyte, its preparation method, and its application, 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 sodium-ion solid electrolyte is provided, comprising a polymer matrix, a sodium 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 sodium salt comprises at least one of sodium bis(trifluoromethanesulfonyl)imide (NaTFSI), sodium difluorooxalate borate (NaDFOB), sodium hexafluorophosphate (NaPF6), sodium tetrafluoroborate (NaBF4), sodium bis(oxalate)borate (NaBOB), sodium bis(fluorosulfonyl)imide (NaFSI), sodium trifluoromethanesulfonate (NaTf), sodium difluorophosphate (NaPO2F2), sodium nitrate (NaNO3), sodium perchlorate (NaClO4), sodium chloride (NaCl), sodium iodide (NaI), and sodium bromide (NaBr).

[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, sodium 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 sodium 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 sodium salts through Lewis acid or pore confinement effects, weakening the electrostatic attraction between sodium ions and anions, thereby increasing the sodium ion transport number.

[0019] In one embodiment, the sodium-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 sodium ion solid electrolyte is provided, comprising the following steps:

[0029] S1: Mixing sodium salt and polar organic compound yields 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 sodium ion solid electrolyte.

[0032] In one embodiment, the sodium 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 sodium ion solid electrolyte film is 10–120 μm.

[0041] According to a third aspect of this disclosure, a solid-state sodium-ion battery is provided, comprising a positive electrode, a negative electrode, and the aforementioned sodium-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 sodium iron phosphate, sodium nickel cobalt aluminum oxide, sodium nickel manganese cobalt oxide, and sodium-rich manganese layered oxide (Na). 1+x [NiMnCo] 1-x At least one of O2, sodium cobaltate, and sodium manganate.

[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-sodium-treated silicon suboxide, silicon carbide (SiC), sodium, aluminum-silicon alloy, sodium-indium alloy, sodium-tin alloy, and sodium-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 sodium-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 sodium-ion solid electrolyte composed of a polymer matrix, polymer monomers, a eutectic mixture (prepared from a mixture of sodium 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 sodium-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 sodium-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 sodium-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 sodium ion transfer number is achieved in the sodium-ion solid electrolyte. Due to its high sodium ion transfer number, the sodium-ion solid electrolyte effectively inhibits sodium 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-pressing integrated device for solid-state batteries were developed, solving the problem of electrode stress failure under low stacking pressure. Integrating the self-supporting sodium-ion solid electrolyte membrane into the fabrication of rolled solid cylindrical batteries expands the commercial application potential of long-cycle solid sodium 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 sodium-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 sodium 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 sodium-ion solid electrolyte with high sodium-ion mobility, a certain degree of flexibility, and strong compatibility with both positive and negative electrodes. This elastic sodium-ion solid electrolyte weakens the interaction between sodium ions and anions in the sodium salt through the chemical synergy between the anion acceptor and the eutectic mixture, significantly enhancing the dissociation of the sodium salt. Furthermore, the anion acceptor coordinates with anions in the sodium salt through Lewis acid or pore confinement effects, weakening the electrostatic attraction between sodium ions and anions, thereby increasing the sodium ion transport number. Simultaneously, the high sodium-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 sodium salt, ensuring the long-term cycle stability of the battery. In addition, a simple and rapid large-scale production of the electrolyte membrane 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 sodium batteries.

[0070] The sodium-ion solid electrolyte proposed in this disclosure includes a polymer matrix, a sodium salt, a polar organic compound, a polymer monomer, and an anion acceptor; the polymer monomer includes 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] Sodium salts include at least one of the following: sodium bis(trifluoromethanesulfonyl)imide (NaTFSI), sodium difluorooxalate borate (NaDFOB), sodium hexafluorophosphate (NaPF6), sodium tetrafluoroborate (NaBF4), sodium bis(oxalate)borate (NaBOB), sodium bis(fluorosulfonyl)imide (NaFSI), sodium trifluoromethanesulfonate (NaTf), sodium difluorophosphate (NaPO2F2), sodium nitrate (NaNO3), sodium perchlorate (NaClO4), sodium chloride (NaCl), sodium iodide (NaI), and sodium bromide (NaBr).

[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 prepared a sodium-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 NaTFSI 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 sodium 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 sodium-ion solid electrolyte, as detailed below:

[0085] (1) Under an argon atmosphere, 2.4 mol of N-ethylacetamide and 0.5 mol of NaTFSI 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 sodium 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 sodium-ion solid electrolyte, as detailed below:

[0090] (1) Under an argon atmosphere, 2.4 mol of N-ethylacetamide and 0.4 mol of NaTFSI 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 sodium 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 sodium-ion solid electrolyte, as detailed below:

[0095] (1) Under an argon atmosphere, 2.4 mol of N-ethylacetamide and 0.3 mol of NaTFSI 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 sodium 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 sodium-ion solid electrolyte, as detailed below:

[0100] (1) Under an argon atmosphere, 2.4 mol of N-ethylacetamide and 0.7 mol of NaTFSI 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 sodium 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 sodium-ion solid electrolyte, as detailed below:

[0105] (1) Under an argon atmosphere, 2.4 mol of N-ethylacetamide and 0.8 mol of NaTFSI 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 sodium 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 sodium-ion solid electrolyte, as detailed below:

[0110] (1) Under an argon atmosphere, 2.4 mol of N-ethylacetamide and 0.9 mol of NaTFSI 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 sodium 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 sodium-ion solid electrolyte, as detailed below:

[0115] (1) Under an argon atmosphere, 2.4 mol of N-ethylacetamide and 0.95 mol of NaTFSI 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 sodium 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 sodium-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 NaTFSI 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 sodium 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 sodium-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 NaTFSI 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 sodium 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 sodium-ion solid electrolyte, which differs from Example 1 in that it prepared a halide sodium-ion solid electrolyte. Details are as follows:

[0130] Na3InCl6 and PTFE were added to a mortar at a mass ratio of 96:4, mixed evenly, and rolled to obtain a sodium halide ion solid electrolyte with a thickness of 10 μm.

[0131] Test case

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

[0133] (1) NaNi with a mass ratio of 96:2:2 0.33 Fe 0.33 Mn 0.33 O2, VGCF and PVDF 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 sodium metal sheet was used as the negative electrode; (3) a sodium metal sheet was used as the negative electrode sheet. Figure 6 The all-solid-state battery core continuous roll winding integrated forming apparatus shown in the figure places the sodium-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 permeate and occupy the internal pores of the porous electrode. Then, it is heated and cured at 60°C for 12 hours. Finally, after electrode tab welding and vacuum sealing, NaNi is obtained. 0.33 Fe 0.33 Mn 0.33 O2||Na all-solid-state sodium-ion battery.

[0134] A solid-state sodium-ion battery was prepared using the sodium-ion solid electrolyte prepared in Comparative Example 3. The specific steps are as follows:

[0135] (1) NaNi with a mass ratio of 96:2:2 0.33 Fe 0.33 Mn 0.33 O2, Na3InCl6, VGCF and PVDF 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: (2) Sodium metal sheet was used as the negative electrode; (3) The sodium ion solid electrolyte prepared in Comparative Example 3 was directly placed between the negative and positive electrode sheets and stacked and bonded. After electrode tab welding and vacuum sealing, NaNi was obtained. 0.33 Fe 0.33 Mn 0.33 O2∣Na3InCl6∣Na All-solid-state sodium-ion battery.

[0136] 1. Tensile strength test: The sodium-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 sodium-ion solid electrolyte was obtained by assembling a symmetrical cell with a steel sheet as the blocking electrode and measuring the electrochemical impedance spectroscopy 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. 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 of the solid polymer electrolyte membrane. b This represents the total impedance of the electrolyte (Ω).

[0140] 3. Ion transport number test: The sodium ion transport number of the sodium-ion solid electrolyte was determined by combining AC impedance and current polarization. First, the initial interfacial impedance R of the sodium-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 sodium ion transport number formula:

[0141] T Na + =I s [ΔV-I 0 R ct 0 ] / I 0 [ΔV-I s R ct s ].

[0142] 4. Electrical performance test: The sodium-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-cells were charged at a constant current of 0.1C to 4.20V, charged at a constant voltage to 0.05C, and discharged at a constant current of 0.1C to 2.0V.

[0143] 5. Discharge capacity and cycle performance:

[0144] Cyclic tests were conducted on the all-solid-state sodium-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, comparing Examples 1-8, the ionic conductivity of the eutectic mixture reaches its maximum value when the molar ratio of NMA:NaTFSI is 4:1 (Example 1). As the sodium salt concentration decreases, the degree of sodium salt dissociation increases, leading to higher ionic conductivity in the eutectic mixture. However, excessively low sodium salt ratios result in lower ionic conductivity due to lower carrier concentration. Comparing Example 1 with Comparative Examples 1 and 2, the pure second monomer exhibits excellent tensile properties 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 properties of the soft phase (second monomer polymer) and the strength of the hard phase (first monomer polymer).

[0150] Example 1 introduces a sodium-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. This solves the problem of electrode stress failure under low stacking pressure and achieves good cycle stability of the all-solid-state sodium-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 sodium-ion solid-state electrolyte, characterized by, The sodium ion solid-state electrolyte comprises a polymer matrix, a sodium salt, a polar organic compound, a polymer monomer, and an anion receptor; the polymer monomer comprises a first monomer and a second monomer.

2. The sodium-ion solid-state electrolyte of claim 1, wherein, The polymer matrix comprises 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 sodium salt comprises at least one of sodium bis(trifluoromethanesulfonyl)imide, sodium difluoro(oxalato)borate, sodium hexafluorophosphate, sodium tetrafluoroborate, sodium bis(oxalato)borate, sodium bis(fluorosulfonyl)imide, sodium triflate, sodium difluorophosphate, sodium nitrate, sodium perchlorate, sodium chloride, sodium iodide, and sodium bromide; Preferably, the polar organic compound comprises at least one of N-methylacetamide, N-ethylacetamide, 2-methylpropanamide, 1-methyl-3-propylimidazolium, triethylene glycol dimethyl ether, lactic acid, triethanolamine, glycerol, and urea; Preferably, the molar ratio of the sodium salt to the polar organic compound is 1:(1-10).

3. The sodium-ion solid-state electrolyte of claim 1, wherein, The first monomer comprises at least one of acrylamide and a derivative thereof; Preferably, the second monomer comprises at least one of dimethyl acrylamide and a derivative thereof; Preferably, the molar ratio of the first monomer to the second monomer is (0.3-5):1; Preferably, the anion receptor comprises at least one of tris(pentafluorophenyl)borane, fluoroalkylborate, trimethyl borate, phenyl boronic acid derivative, boron trifluoride diethyl ether complex, borate crosslinker, polyvinyl alcohol borate, tris(pentafluorophenyl)boron, boronic acid methacrylate copolymer, polystyrene sulfonate, polypyrrolidone derivative, CC3 type porous organic cage, fluorinated covalent organic framework, boron-doped porous organic cage, and triazine-based covalent organic framework.

4. The sodium-ion solid-state electrolyte of claim 1, wherein, The sodium ion solid-state electrolyte further comprises a plasticizer, a crosslinking agent, an initiator, and a solvent; The plasticizer comprises at least one of fluoroethylene carbonate, butanedinitrile, polyethylene glycol dimethyl ether, dibutyl phthalate, trifluoroethoxyethane, and ionic liquid; The crosslinking agent comprises at least one of N,N'-methylenebisacrylamide, polyethylene glycol diacrylate, trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, polyethylene glycol dimethacrylate, divinylbenzene, triallylamine, bisacryloyl cystamine, triacryloyl hexahydro-1,3,5-triazine, and pentaerythritol tetraacrylate; The initiator comprises at least one of 2,2-azobis(isobutyronitrile), 4-methylbenzophenone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-hydroxy-2-methylpropiophenone, benzoin dimethyl ether, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and lithium phenyl-2,4,6-trimethylbenzoylphosphinate. The solvent comprises at least one of anhydrous acetonitrile, N-methyl pyrrolidone, cyclohexane, toluene, xylene, acetonitrile, dichloromethane, dimethyl sulfoxide, dimethyl formamide, acetone, tetrahydrofuran, chloroform, dimethylacetamide; Preferably, the molar ratio of the polymer monomer to the cross-linking 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 cross-linking agent to the initiator is (0.5-3):

1.

5. The method of producing the sodium-ion solid-state electrolyte according to any one of claims 1 to 4, characterized by, The method comprises the following steps: S1: mixing a sodium salt and a polar organic compound to obtain a eutectic mixture; S2: mixing a polymer matrix, a first monomer, a second monomer, and an anion acceptor with the eutectic mixture to obtain a precursor solution; S3: after coating the precursor solution on a substrate, solidifying and drying to obtain the sodium ion solid-state electrolyte.

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

7. A solid-state sodium-ion battery, characterized by, The solid-state sodium ion battery comprises a positive electrode, a negative electrode, and the sodium ion solid-state electrolyte according to any one of claims 1-4.

8. The solid-state sodium-ion battery of claim 7, wherein, The positive electrode comprises, in terms of mass percentage, 90-96% of a positive electrode active main material, 0-5% of a positive electrode conductive agent, and 0-5% of a positive electrode binder; The positive electrode active main material comprises at least one of sodium iron phosphate, sodium nickel cobalt aluminate, sodium nickel manganese cobaltate, sodium-rich manganese-based layered oxide, sodium cobaltate, and sodium manganate; The positive electrode conductive agent comprises at least one of VGCF, carbon black, acetylene black, ketjen black, carbon nanotube, and graphene; The positive electrode binder comprises at least one of polyvinylidene fluoride, polytetrafluoroethylene, polyvinylidene fluoride-hexafluoropropylene, polypropylene, polyethylene, and polyimide.

9. The solid-state sodium-ion battery of claim 7, wherein, The negative electrode comprises, in terms of mass percentage, 90-96% of a negative electrode active main material, 0-5% of a negative electrode conductive agent, and 0-5% of a negative electrode binder; The negative electrode active main material comprises at least one of artificial graphite, natural graphite, silicon, silicon monoxide, pre-sodiumized silicon monoxide, silicon-carbon material, sodium, aluminum-silicon alloy, sodium-indium alloy, sodium-tin alloy, and sodium-aluminum alloy; The negative electrode conductive agent comprises at least one of VGCF, carbon black, acetylene black, ketjen black, carbon nanotube, and graphene; The negative electrode binder includes at least one of sodium hydroxymethyl cellulose, carboxymethyl cellulose, methyl cellulose, butyl benzene latex, polyacrylic acid, acrylic copolymer, cyclodextrin, butyl benzene rubber, butyl nitrile rubber, hydrogenated butyl nitrile rubber, polymethyl methacrylate, styrene-butadiene block copolymer, styrene-ethylene-butylene-styrene block copolymer, and polyisobutylene.

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

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