High-voltage polymer-based solid-state battery based on thermodynamic and dynamic regulation and control

Abstract

The invention relates to a high-voltage solid-state polymer battery based on thermodynamic and dynamic regulation and control as well as a preparation method and application thereof. The high-voltage solid-state polymer battery comprises a positive electrode, a negative electrode and a solid-state polymer electrolyte, the solid-state polymer electrolyte is of a double-layer structure and comprises a positive-electrode-side solid-state polymer electrolyte and a negative-electrode-side solid-state polymer electrolyte; the negative electrode side solid polymer electrolyte comprises a polymer, a first metal salt and an inorganic filler; the positive electrode side solid polymer electrolyte comprises an oligomer and a second metal salt; the working temperature of the solid polymer electrolyte is 40-60 DEG C; according to the high-voltage solid-state polymer battery, electrolyte ion conduction, electrode interface stability and electrode material structure stability are regulated and controlled through thermodynamic and dynamic regulation and control, so that the solid-state battery has excellent cycle performance and high-voltage stability; the invention provides a new thought for the development of high-energy-density and high-safety solid-state batteries.

Description

Technical Field

[0001] This invention relates to the field of solid-state polymer battery technology, and more particularly to a high-voltage polymer-based solid-state battery based on thermodynamic and kinetic regulation. Background Technology

[0002] Solid-state polymer batteries (SSBs) are considered a core direction for next-generation energy storage technology due to their high energy density and high safety. However, polymer-based solid-state batteries are prone to problems such as cathode structure degradation, electrolyte oxidative decomposition, and lithium dendrite growth at high voltages (≥4.3V), leading to a sharp decline in battery cycle life and limiting their commercialization.

[0003] Existing technologies mostly focus on optimizing single materials (such as improving ionic conductivity or mechanical strength), lacking systematic research on the synergistic effects of thermodynamics (such as phase transitions and interfacial stability) and kinetics (such as ion migration and interfacial reaction rates), making it difficult to achieve both high voltage performance and long cycle life. Temperature, as a key parameter affecting battery performance, has not yet had its comprehensive effects on the thermodynamic stability and kinetic processes of electrodes, electrolytes, and interfaces fully investigated. Summary of the Invention

[0004] This invention provides a high-voltage polymer-based solid-state battery based on thermodynamic and kinetic regulation, its preparation method, and its application. By designing a bilayer solid-state polymer electrolyte and optimizing the operating temperature, the thermodynamic stability and kinetic processes of each component of the battery are systematically regulated, significantly improving the cycle performance under high voltage.

[0005] In a first aspect, embodiments of the present invention provide a high-voltage solid-state polymer battery based on thermodynamic and kinetic regulation, the high-voltage solid-state polymer battery comprising: a positive electrode, a negative electrode, and a solid polymer electrolyte;

[0006] The solid polymer electrolyte has a bilayer structure, comprising: a positive electrode side solid polymer electrolyte and a negative electrode side solid polymer electrolyte;

[0007] The negative electrode side solid polymer electrolyte comprises: a polymer, a first metal salt, and an inorganic filler;

[0008] The positive electrode side solid polymer electrolyte comprises: an oligomer and a second metal salt;

[0009] The solid polymer electrolyte is formed by coating the surface of the solid negative electrode side solid polymer electrolyte with a molten positive electrode side solid polymer electrolyte;

[0010] The solid polymer electrolyte operates at a temperature of 40°C to 60°C. Within this temperature range, the ion conduction kinetics of the solid polymer electrolyte are controlled based on thermodynamics and kinetics, thereby controlling the interfacial stability between the positive electrode and the solid polymer electrolyte, and the interfacial stability between the negative electrode and the solid polymer electrolyte.

[0011] Preferably, the solid polymer electrolyte has an ionic conductivity of 1.0 × 10⁻⁶ at 40°C. -4 S / cm~1.0×10 -2 S / cm;

[0012] The lithium-ion or sodium-ion transport number of the solid polymer electrolyte is 0.5 to 0.9.

[0013] Preferably, the polymer comprises one or more of the following: polyether polymers, polycarbonate polymers, and polyacrylate polymers; the molecular weight of the polymer is 100,000 g / mol to 1,000,000 g / mol; specifically, the polymer comprises one or more of the following: polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol monomethyl ether (PEGME), polyethylene glycol dimethyl ether (PEGDME), polyethylene carbonate (PEC), polypropylene carbonate (PPC), polytrimethylene carbonate (PTMC), polycaprolactone (PCL), polyvinyl chloride (PVC), polydiethyl carbonate (PDEC), polymethyl methacrylate (PMA), polymethyl methacrylate (PMMA), ethyl polyacrylate (PEA), polyethyl methacrylate (PEMA), and polybutyl acrylate (PBA);

[0014] The mass ratio of the first metal salt to the polymer is 5%-50%; the first metal salt includes: a first lithium salt or a first sodium salt; the first lithium salt includes one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium dioxalate borate, lithium difluorooxalate borate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and lithium dioxoborate; the first sodium salt includes one or more of sodium hexafluorophosphate, sodium hexafluorophosphate, sodium tetrafluoroborate, sodium perchlorate, sodium trifluoromethanesulfonate, sodium bis(trifluoromethanesulfonyl)imide, sodium borate, and sodium dioxoborate.

[0015] The inorganic filler has a mass ratio of 1% to 80% to the polymer; the inorganic filler includes one or more of the following: alumina, silicon dioxide, titanium dioxide, zirconium dioxide, magnesium oxide, barium titanate, molecular sieve, montmorillonite, garnet oxide, NASICON oxide, perovskite oxide, lithium thiogermanium phosphate sulfide, lithium phosphate sulfide, lithium aluminum phosphate, lithium titanium phosphate, and lithium halide metal salts.

[0016] Preferably, the oligomer includes one or more of the following: polyether oligomers, polycarbonate oligomers, and polyacrylate oligomers; the molecular weight of the oligomer is 200 g / mol to 5000 g / mol; specifically, the oligomer includes one or more of the following: polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol monomethyl ether (PEGME), polyethylene glycol dimethyl ether (PEGDME), polyethylene carbonate (PEC), polypropylene carbonate (PPC), polytrimethylene carbonate (PTMC), polycaprolactone (PCL), polyvinyl chloride (PVC), polydiethyl carbonate (PDEC), polymethacrylate (PMA), polymethyl methacrylate (PMMA), polyethyl methacrylate (PEA), polyethyl methacrylate (PEMA), and polybutyl acrylate (PBA);

[0017] The mass ratio of the second metal salt to the oligomer is 5%-50%; the second metal salt includes: a second lithium salt or a second sodium salt; the second lithium salt includes one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium dioxalate borate, lithium difluorooxalate borate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and lithium dioxalate borate; the second sodium salt includes one or more of sodium hexafluorophosphate, sodium hexafluorophosphate, sodium tetrafluoroborate, sodium perchlorate, sodium trifluoromethanesulfonate, sodium bis(trifluoromethanesulfonyl)imide, sodium borate, and sodium dioxalate borate.

[0018] Preferably, the active material of the positive electrode includes: spinel-structured lithium nickel manganese oxide, lithium-rich manganese-based materials, olivine-structured lithium manganese phosphate, high-voltage lithium cobalt oxide, nickel-rich layered oxide, and spinel-type LiNi. 0.92 Co 0.04 Mn 0.04 O2, spinel-type LiNi 0.5 Mn 1.5 O4 derivatives, lithium-rich spinel composites, high-voltage sodium ferric sulfate, NASICON-type sodium vanadium phosphate, P2-type layered transition metal oxides, Cu-doped O3-type layered oxides, polyanionic cathode materials, Prussian blue analogs, polyanionic phosphates, Zn-doped P-type layered oxides, magnesium-rich NASICON-type cathode materials, high-potential fluorophosphates, spinel transition metal-doped LiMnO4. x Mn 2-x One or more of O4; wherein M includes one or more of Co, Cr, Ni, Fe, and Cu;

[0019] The active material of the negative electrode includes: lithium metal or sodium metal.

[0020] Secondly, embodiments of the present invention provide a method for preparing the high-voltage solid-state polymer battery described in the first aspect above, the method comprising:

[0021] The preparation of a negative electrode side solid polymer electrolyte includes: dissolving a polymer, a first metal salt and an inorganic filler in an organic solvent, stirring evenly to form a negative electrode solid electrolyte slurry, coating the negative electrode solid electrolyte slurry onto one side of a polyester film, drying it and then hot pressing it to obtain a negative electrode side solid polymer electrolyte.

[0022] The preparation of a positive electrode side solid polymer electrolyte includes: mixing an oligomer and a second metal salt and heating the mixture to make the oligomer a molten liquid, stirring the mixture evenly to make the second metal salt uniformly dispersed in the oligomer, thereby obtaining a liquid positive electrode side solid polymer electrolyte.

[0023] Assembling a high-voltage solid-state polymer battery includes: coating one side of the solid polymer electrolyte on the negative electrode side with the solid polymer electrolyte on the positive electrode side to obtain a solid polymer electrolyte; attaching the other side of the solid polymer electrolyte on the negative electrode side to the side of the negative electrode containing negative electrode active material; attaching the solid polymer electrolyte on the positive electrode side to the side of the positive electrode containing positive electrode active material; and assembling to obtain a high-voltage solid-state polymer battery.

[0024] Preferably, the polymer comprises one or more of the following: polyether polymers, polycarbonate polymers, and polyacrylate polymers; the molecular weight of the polymer is 100,000 g / mol to 1,000,000 g / mol; specifically, the polymer comprises one or more of the following: polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol monomethyl ether (PEGME), polyethylene glycol dimethyl ether (PEGDME), polyethylene carbonate (PEC), polypropylene carbonate (PPC), polytrimethylene carbonate (PTMC), polycaprolactone (PCL), polyvinyl chloride (PVC), polydiethyl carbonate (PDEC), polymethyl methacrylate (PMA), polymethyl methacrylate (PMMA), ethyl polyacrylate (PEA), polyethyl methacrylate (PEMA), and polybutyl acrylate (PBA);

[0025] The mass ratio of the first metal salt to the polymer is 5%-50%; the first metal salt includes: a first lithium salt or a first sodium salt; the first lithium salt includes one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium dioxalate borate, lithium difluorooxalate borate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and lithium dioxoborate; the first sodium salt includes one or more of sodium hexafluorophosphate, sodium hexafluorophosphate, sodium tetrafluoroborate, sodium perchlorate, sodium trifluoromethanesulfonate, sodium bis(trifluoromethanesulfonyl)imide, sodium borate, and sodium dioxoborate.

[0026] The mass ratio of the inorganic filler to the polymer is 1%-80%; the inorganic filler includes one or more of the following: alumina, silicon dioxide, titanium dioxide, zirconium dioxide, magnesium oxide, barium titanate, molecular sieve, montmorillonite, garnet oxide, NASICON oxide, perovskite oxide, lithium thiogermanium phosphate sulfide, lithium phosphate sulfide, lithium aluminum phosphate, lithium titanium phosphate, and lithium halide metal salts.

[0027] The solvent includes one or more of the following: deionized water, dichloromethane, dichlorobenzene, xylene, dimethyl sulfoxide, chloroform, tetrahydrofuran, toluenecyclohexanone, methanol, toluene, ethanol, acetonitrile, ethyl acetate, diethyl ether, acetone, n-hexane, cyclohexane, cyclohexanone, n-heptane, hexafluoroisopropanol, N-methylpyrrolidone, N,N-dimethylformamide, benzene, chlorophenol, 1,4-dioxane, pyridine, and petroleum ether.

[0028] The stirring time is 12 to 24 hours; the drying temperature is 50°C to 80°C; the hot pressing temperature is 80°C to 120°C, and the pressure is 5 MPa to 10 MPa.

[0029] Preferably, the oligomer includes one or more of the following: polyether oligomers, polycarbonate oligomers, and polyacrylate oligomers; the molecular weight of the oligomer is 200 g / mol to 5000 g / mol; specifically, the oligomer includes one or more of the following: polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol monomethyl ether (PEGME), polyethylene glycol dimethyl ether (PEGDME), polyethylene carbonate (PEC), polypropylene carbonate (PPC), polytrimethylene carbonate (PTMC), polycaprolactone (PCL), polyvinyl chloride (PVC), polydiethyl carbonate (PDEC), polymethacrylate (PMA), polymethyl methacrylate (PMMA), polyethyl methacrylate (PEA), polyethyl methacrylate (PEMA), and polybutyl acrylate (PBA);

[0030] The mass ratio of the second metal salt to the oligomer is 5%-50%; the second metal salt includes: a second lithium salt or a second sodium salt; the second lithium salt includes one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium dioxalate borate, lithium difluorooxalate borate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and lithium dioxalate borate; the second sodium salt includes one or more of sodium hexafluorophosphate, sodium hexafluorophosphate, sodium tetrafluoroborate, sodium perchlorate, sodium trifluoromethanesulfonate, sodium bis(trifluoromethanesulfonyl)imide, sodium borate, and sodium dioxalate borate; the solid content in the negative electrode solid electrolyte slurry is 0.01 g / mL to 0.5 g / mL;

[0031] The heating temperature is 100℃~130℃, and the heating time is 1~3 hours; the stirring time is 0.5 hours~24 hours.

[0032] Preferably, the active material of the positive electrode includes: spinel-structured lithium nickel manganese oxide, lithium-rich manganese-based materials, olivine-structured lithium manganese phosphate, high-voltage lithium cobalt oxide, nickel-rich layered oxide, and spinel-type LiNi. 0.92 Co 0.04 Mn 0.04 O2, spinel-type LiNi 0.5 Mn 1.5 O4 derivatives, lithium-rich spinel composites, high-voltage sodium ferric sulfate, NASICON-type sodium vanadium phosphate, P2-type layered transition metal oxides, Cu-doped O3-type layered oxides, polyanionic cathode materials, Prussian blue analogs, polyanionic phosphates, Zn-doped P-type layered oxides, magnesium-rich NASICON-type cathode materials, high-potential fluorophosphates, spinel transition metal-doped LiMnO4. x Mn 2-x One or more of O4; wherein M includes one or more of Co, Cr, Ni, Fe, and Cu;

[0033] The active material of the negative electrode includes: lithium metal or sodium metal.

[0034] Thirdly, embodiments of the present invention provide an application of the high-voltage solid-state polymer battery described in the first aspect, wherein the high-voltage solid-state polymer battery is used in electric vehicles or energy storage devices.

[0035] This invention provides a high-voltage polymer-based solid-state battery, along with its preparation method and application, which has the following beneficial effects:

[0036] (1) This invention provides a method for preparing a high-voltage polymer-based solid-state battery. First, a solid negative-side solid polymer electrolyte (AS-SSPE) containing a high molecular weight polymer, inorganic filler, and metal salt is prepared. Then, a positive-side solid polymer electrolyte containing a low molecular weight oligomer and metal salt is coated onto the AS-SSPE surface to obtain solid polymer solid electrolytes (SSPEs). Next, the other side of the negative-side solid polymer electrolyte is bonded to the side of the negative electrode containing negative electrode active material, and the positive-side solid polymer electrolyte is bonded to the side of the positive electrode containing positive electrode active material. This assembly yields a high-voltage solid polymer battery. This high-voltage solid polymer battery can be assembled into a coin cell or a pouch cell using a layered padding system to meet the energy density requirements of different energy storage devices. This preparation method is simple and easy to operate.

[0037] (2) By designing a double-layer solid polymer electrolyte (DL-SSPE) and optimizing the operating temperature, this invention systematically regulates the thermodynamic stability and kinetic processes of each component of the battery, thereby significantly improving the cycle performance under high pressure.

[0038] The solid polymer electrolyte prepared in the embodiments of the present invention has high ionic conductivity and cation transference number, and can improve other electrochemical properties by thermodynamic and kinetic regulation while ensuring the cation transference number.

[0039] (3) A high-voltage solid polymer battery based on thermodynamic and kinetic regulation, which is assembled with a positive electrode and a negative electrode containing the solid polymer electrolyte provided by the present invention in accordance with conventional methods. The high-voltage solid polymer battery includes, but is not limited to, any one of all-solid-state lithium metal battery and all-solid-state sodium metal battery.

[0040] High-voltage solid polymer batteries containing the solid polymer electrolyte provided by the present invention exhibit high high-voltage cycle performance, indicating that the solid polymer electrolyte of the present invention performs excellently in terms of ion transport capability and battery cycle stability.

[0041] This invention analyzes the degradation mechanism of high-voltage polymer-based solid-state batteries (SSBs), identifying temperature as a key factor influencing both thermodynamics and kinetics. Systematic studies show that temperature kinetically affects the surface energy and interfacial electrochemical stability of solid polymer electrolytes (SSBs), thermodynamically influences the chemical stability of SSBs, and affects the structural stability of electrode materials through thermodynamic and kinetic pathways. This invention provides a methodological framework for analyzing battery failure in solid-state polymer batteries (SSBs) from a thermodynamic and kinetic perspective. We emphasize the crucial role of temperature in high-temperature polymer-based SSBs, similar to the importance of pressure in sulfide-based SSBs, thus providing valuable insights for the development of polymer-based SSB technology.

[0042] The solid polymer electrolyte provided in this invention has broad applicability. Besides being compatible with commonly used cathode materials with narrow voltage ranges, it can also be well-matched with high-voltage cathode materials and metal anodes. High-voltage polymer-based solid-state batteries (button cells or pouch cells) assembled using the solid polymer electrolyte provided in this invention can achieve stable cycling, which is of great significance for promoting the widespread application of solid-state batteries in electric vehicles, energy storage systems, and other fields. Attached Figure Description

[0043] Figure 1 This is a summary diagram of the transport mechanism of the high-voltage polymer-based solid-state battery based on thermodynamic and kinetic regulation, as presented in this invention.

[0044] Figure 2 This is a schematic diagram of the battery structure and thermodynamic and kinetic influence mechanism of a high-voltage polymer-based solid-state battery based on thermodynamic and kinetic regulation, provided in an embodiment of the present invention.

[0045] Figure 3 This is a flowchart of the preparation method of a high-voltage polymer-based solid-state battery based on thermodynamic and kinetic regulation provided in the embodiments of the present invention.

[0046] Figure 4 This is the preparation process of the bilayer solid polymer electrolyte in Example 1 of the present invention.

[0047] Figure 5 This is a test curve of the ionic conductivity of the solid polymer electrolyte in the high-voltage polymer-based solid-state battery prepared according to thermodynamic and kinetic regulation in Example 1 of the present invention.

[0048] Figure 6 The lithium-ion transference number of the solid polymer electrolyte in the high-voltage polymer-based solid-state battery prepared by thermodynamic and kinetic regulation in Example 1 and Comparative Example 1 of this invention is measured at 40°C and 60°C.

[0049] Figure 7 The redox potentials of the solid polymer electrolyte in the high-voltage polymer-based solid-state battery prepared in Example 1 of this invention at 40°C and 60°C are shown.

[0050] Figure 8 The solid polymer electrolyte Li is used in high-voltage polymer-based solid-state batteries prepared in Examples 1 and 1 of this invention, based on thermodynamic and kinetic regulation. + and TFSI - Mean square displacement at 40℃ and 60℃; Li at 40℃ and 60℃ + With TFSI - The radial distribution function and coordination number between oxygen in ethylene oxide and oxygen in polyoxyethylene.

[0051] Figure 9 These are Fourier transform infrared spectra of the solid polymer electrolytes of high-voltage polymer-based solid-state batteries prepared in Examples 1 and 1 of the present invention, based on thermodynamic and kinetic regulation, used to analyze the structure of the ethylene oxide unit in AS-SSPE-Li.

[0052] Figure 10 These are charge-discharge curves of the all-solid-state lithium metal battery (LCO|DL-SSPE-Li|Li) prepared using lithium cobalt oxide in Example 1 and Comparative Example 1 of the present invention, with a charge-discharge cutoff voltage range of 3.0V-4.3V, and cycle curves.

[0053] Figure 11 These are charge-discharge curves of the all-solid-state lithium metal battery (LCO|DL-SSPE-Li|Li) prepared using lithium cobalt oxide in Example 1 and Comparative Example 1 of the present invention, with a charge-discharge cutoff voltage range of 3.0V-4.45V, and a cycle curve.

[0054] Figure 12 The average coulombic efficiency of the all-solid-state lithium metal battery (LCO|DL-SSPE-Li|Li) prepared using lithium cobalt oxide in Examples 1 and Comparative Example 1 of this invention is measured in the voltage ranges of 3.0-4.3V and 3.0-4.45V.

[0055] Figure 13 The leakage current of the all-solid-state lithium metal battery (LCO|DL-SSPE-Li|Li) prepared using lithium cobalt oxide in Example 1 and Comparative Example 1 of this invention was measured under constant voltage float charge at 4.2V, 4.3V, 4.4V, 4.5V and 4.6V.

[0056] Figure 14 This invention compares the electrochemical performance of the all-solid-state lithium metal battery (LCO|DL-SSPE-Li|Li) prepared using lithium cobalt oxide in Example 1 of this invention with other all-solid-state lithium metal batteries based on polyethylene oxide in other studies, involving various materials such as NCM811, NCM83, and NCM622.

[0057] Figure 15 This is an optical photograph of the solid polymer electrolyte of the high-voltage polymer-based solid-state battery based on thermodynamic and kinetic regulation prepared in Example 1 of the present invention (the size of the solid polymer electrolyte is 100cm×8cm×0.0075cm).

[0058] Figure 16 The present invention provides the charge-discharge voltage curves and cycle performance of the LCO|DL-SSPE-Li|Li monolayer soft-pack battery prepared in Example 1 of this invention.

[0059] Figure 17 These are the safety test results of the LCO|DL-SSPE-Li|Li monolayer soft-pack battery prepared in Example 1 of this invention.

[0060] Figure 18 These are optical photographs and three-dimensional reconstructed images of the LCO|DL-SSPE-Li|Li multilayer pouch cells prepared in Example 1 of this invention, showing a good multilayer stacked structure.

[0061] Figure 19 This diagram illustrates the evolution of the Li / SSPEs interface in the Li|AS-SSPE-Li|Li symmetric cell prepared in Example 1 of this invention at 40°C and 60°C. Specifically, it shows the electrochemical impedance spectroscopy spectra and corresponding relaxation time distributions when the cells are left to stand at 40°C and 60°C.

[0062] Figure 20 This diagram shows the evolution of the Li / SSPEs interface in the Li|AS-SSPE-Li|Li symmetric battery prepared in Example 1 of this invention at 40℃ and 60℃. Specifically, it shows the electrochemical impedance spectroscopy spectra and corresponding relaxation time distributions during cycling at 40℃ and 60℃.

[0063] Figure 21 The Li|AS-SSPE-Li|Li symmetric cell prepared in Example 1 of this invention achieves a speed of 0.05 mA / cm². -2 The current density cycling is 0.05 mA / cm². -2 Voltage curve at that time.

[0064] Figure 22 These are the EIS spectra of the Li|AS-SSPE-Li|Li symmetric cell prepared in Example 1 of this invention after 70 and 650 cycles.

[0065] Figure 23 These are high-angle annular dark-field images of the LCO structure in the LCO|DL-SSPE-Li|Li battery prepared in Example 1 of this invention at 40℃ and 60℃.

[0066] Figure 24 The voltage curves and differential electrochemical mass spectrometry data at 40°C and 60°C of the LCO|DL-SSPE-Li|Li battery prepared in Example 1 of this invention are shown, illustrating the gas production situation.

[0067] Figure 25 The results are X-ray tomography three-dimensional reconstructions of the electrode / SSPEs interface after 10 cycles of the LCO|DL-SSPE-Li|Li battery prepared in Example 1 of this invention.

[0068] Figure 26This is a schematic diagram of the reaction mechanism of the LCO|DL-SSPE-Li|Li battery prepared in Example 1 of the present invention during operation at 40℃ and 60℃.

[0069] Figure 27 This is a flowchart of the high-voltage polymer-based solid-state battery and its preparation method based on thermodynamic and kinetic regulation provided in Embodiment 2 of the present invention.

[0070] Figure 28 This is the O3-NaNi assembled in Embodiment 2 of the present invention. 1 / 3 Fe 1 / 3 Mn 1 / 3 O2

[0071] Charge and discharge voltage and cycle performance of (NFM333)|DL-SSPE-Na|Na batteries.

[0072] Figure 29 The charge / discharge voltage and cycle performance of the Na3V2(PO4)3(NVP)|DL-SSPE-Na|Na battery assembled in Embodiment 2 of the present invention are described. Detailed Implementation

[0073] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0074] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments.

[0075] This invention provides a high-voltage solid-state polymer battery based on thermodynamic and kinetic regulation. The high-voltage solid-state polymer battery includes a positive electrode, a negative electrode, and a solid polymer electrolyte.

[0076] The solid polymer electrolyte in the high-voltage solid polymer battery has an ionic conductivity of 1.0 × 10⁻⁶ at 40 °C. -4 S / cm~1.0×10 -2 S / cm can be any value within this range, for example: 1.0 × 10 -4 S / cm, 2.0×10 - 4 S / cm, 3.0×10 -4 S / cm, 4.0×10 -4 S / cm, 5.0×10 -4 S / cm, 6.0×10 -4 S / cm, 7.0×10-4 S / cm, 8.0×10 -4 S / cm, 9.0×10 -4 S / cm, 1.0×10 -3 S / cm, 2.0×10 -3 S / cm, 3.0×10 -3 S / cm, 4.0×10 -3 S / cm, 5.0×10 -3 S / cm, 6.0×10 -3 S / cm, 7.0×10 -3 S / cm, 8.0×10 -3 S / cm, 9.0×10 -3 S / cm, 1.0×10 -2 S / cm, etc., but not limited to the listed values; other unlisted values ​​within this range also apply.

[0077] The cation transference number (including lithium ion or sodium ion) of the solid polymer electrolyte in high-voltage solid polymer batteries is 0.5 to 0.9, and can be any value within this range, such as 0.5, 0.6, 0.7, 0.8, 0.9, etc., but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0078] Specifically, the solid polymer electrolyte (SSPE) in the high-voltage solid polymer battery based on thermodynamic and kinetic regulation has a bilayer structure. The operating temperature of the solid polymer electrolyte is 40℃~60℃, and it can be any temperature value within this range, such as 40℃, 45℃, 50℃, 55℃, 60℃, etc., but it is not limited to the listed temperature values. Other unlisted temperatures within this temperature range are also applicable.

[0079] This invention regulates the ion conduction kinetics of solid polymer electrolytes within a temperature range of 40℃ to 60℃ by temperature control, thereby regulating the interfacial stability between the positive electrode and the solid polymer electrolyte, the interfacial stability between the negative electrode and the solid polymer electrolyte, and optimizing the structural stability of the positive electrode active material or the negative electrode active material.

[0080] Solid polymer electrolytes include: positive electrode side solid polymer electrolyte (CS-SSPE) and negative electrode side solid polymer electrolyte (AS-SSPE); CS-SSPE and AS-SSPE constitute a double-layer solid polymer electrolyte (DL-SSPE), wherein CS-SSPE is bonded to the positive electrode side containing positive electrode active material, and AS-SSPE is bonded to the negative electrode side containing negative electrode active material.

[0081] The negative electrode side solid polymer electrolyte comprises: polymer, first metal salt, and inorganic filler;

[0082] The solid polymer electrolyte on the positive electrode side includes: oligomer and second metal salt.

[0083] Solid polymer electrolytes are formed by coating a molten solid polymer electrolyte on the surface of a solid polymer electrolyte on the negative electrode side with a solid polymer electrolyte on the positive electrode side. AS-SSPE uses a high molecular weight polymer to obtain a fully solid solid polymer electrolyte on the negative electrode side, while CS-SSPE uses a low molecular weight oligomer to obtain a molten liquid electrolyte. Coating this electrolyte onto the solid polymer electrolyte on the negative electrode side effectively improves interfacial contact, reduces the interfacial impedance between the electrode and the solid electrolyte, and thus facilitates better ion transport.

[0084] The polymer and oligomers both include one or more of the following: polyether polymers, polycarbonate polymers, and polyacrylate polymers. The difference between the polymer and the oligomer lies in their molecular weight; the polymer has a molecular weight of 100,000 g / mol to 1,000,000 g / mol, while the oligomer has a molecular weight of 200 g / mol to 5,000 g / mol. In a preferred embodiment, the polymer and oligomer can be organic compounds of the same type but different molecular weights. This ensures that the transport pathways between AS-SSPE and CS-SSPE remain unchanged due to differences in the repeating unit structure, thus improving ionic conductivity.

[0085] The polymers or oligomers specifically include one or more organic compounds selected from the following: polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol monomethyl ether (PEGME), polyethylene glycol dimethyl ether (PEGDME), polyethylene carbonate (PEC), polypropylene carbonate (PPC), polytrimethylene carbonate (PTMC), polycaprolactone (PCL), polyvinyl chloride (PVC), polydiethyl carbonate (PDEC), polymethyl methacrylate (PMA), polymethyl methacrylate (PMMA), polyethyl methacrylate (PEA), polyethyl methacrylate (PEMA), and polybutyl methacrylate (PBA). The specific structural formulas of these organic compounds are shown below. PVC has two types: PVC1 and PVC2. In the structural formula, n ≥ 1, and different n values ​​indicate different molecular weights of the polymers or oligomers.

[0086]

[0087] The mass ratio of the first metal salt to the polymer is 5%-50%, and can be any value within this range, such as 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, etc., but is not limited to the listed values. Other unlisted values ​​within this range are also applicable. The first metal salt includes: a first lithium salt or a first sodium salt. The first lithium salt includes one or more of the following: lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium dioxalate borate, lithium difluorooxalate borate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and lithium dioxalate borate. The first sodium salt includes one or more of the following: sodium hexafluorophosphate, sodium hexafluorophosphate, sodium tetrafluoroborate, sodium perchlorate, sodium trifluoromethanesulfonate, sodium bis(trifluoromethanesulfonyl)imide, sodium borate, and sodium dioxalate borate.

[0088] The mass ratio of inorganic filler to polymer is 1%-80%, and can be any value within this range, such as: 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, etc., but is not limited to the listed values; other unlisted values ​​within this range are also applicable. Inorganic fillers include: alumina (Al2O3), silicon dioxide (SiO2), titanium dioxide (TiO2), zirconium dioxide (ZrO2), magnesium oxide (MgO), barium titanate (BaTiO3), molecular sieves (e.g., zeolite), montmorillonite (layered silicates), and garnet-type oxides (e.g., lithium lanthanum zirconium oxide Li7La3Zr2O). 12 ), NASICON-type oxides (e.g., lithium aluminum titanium phosphate Li), 1.3 Al 0.3 Ti 1.7 (PO4)3), perovskite oxides (e.g., lithium lanthanum titanium oxide Li) 0.33 La 0.55 TiO3), lithium thiogermanium phosphate sulfide (Li 10 GeP2S 12 One or more of the following: lithium phosphorus sulfide (Li3PS4), lithium aluminum phosphate (LiAlPO4), lithium titanium phosphate (LiTi2(PO4)3), and lithium halide metal salts (e.g., Li3YCl6, Li3InCl6).

[0089] The mass ratio of the second metal salt to the oligomer is 5%-50%, and can be any value within this range, such as 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, etc., but is not limited to the listed values; other unlisted values ​​within this range are also applicable. The second metal salt includes: a second lithium salt or a second sodium salt. The second lithium salt includes one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium dioxalate borate, lithium difluorooxalate borate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and lithium dioxoborate, preferably two. The second sodium salt includes one or more of sodium hexafluorophosphate, sodium hexafluorophosphate, sodium tetrafluoroborate, sodium perchlorate, sodium trifluoromethanesulfonate, sodium bis(trifluoromethanesulfonyl)imide, sodium borate, and sodium dioxoborate, preferably two.

[0090] The active materials for the aforementioned cathode include: spinel-structured lithium nickel manganese oxide (LiNi). 0.5 Mn 1.5 Lithium-rich manganese-based materials (Li2MnO3), lithium manganese phosphate with olivine structure (LiMPO4), high-voltage lithium cobalt oxide (LiCoO2), nickel-rich layered oxides (e.g., LiNi) 0.9 Co 0.1 O2), spinel-type LiNi 0.92 Co 0.04 Mn 0.04 O2, spinel-type LiNi 0.5 Mn 1.5 O4-derived materials (e.g., LiTiMnO4, LiCrMnO4), lithium-rich spinel composites (e.g., Li 1+n A w Ni 0.5+x Co 0.2+y Mn 0.3+z O2, where 0.05≤n≤0.3, 0≤w≤0.05, -0.1≤x≤0.1, 0≤y≤0.1, 0≤z≤0.15, and A is at least one of Al, Mg, Ti, Cr, Ni, Fe, Cu, and La), high-voltage sodium ferric sulfate (Na2Fe(SO4)3), NASICON-type sodium vanadium phosphate (Na3V2(PO4)3), and P2-type layered transition metal oxides (chemical formula P2-Na) 0.66 Ni 0.33x Zn x Mn 0.67O2 (where 0≤x≤0.1), Cu-doped O3-type layered oxides (Na) 0.9 Cu 0.22 Fe 0.07 Mn 0.48O2Polyanionic cathode materials, Prussian blue analogues, polyanionic phosphates, Zn-doped P-type layered oxides, magnesium-rich NASICON-type cathode materials, high-potential fluorophosphates, and spinel transition metal-doped LiMnO4. x Mn 2-x O4 (where M is at least one of Co, Cr, Ni, Fe, and Cu, and 0 ≤ x ≤ 0.5) or one or more of these;

[0091] The active materials for the aforementioned negative electrode include: lithium metal or sodium metal.

[0092] The ionic conductivity of the solid polymer electrolyte of this invention is obtained by measuring AC impedance spectroscopy. Specifically, the process involves: first, directly cutting all-solid AS-SSPE using a manual slicer equipped with a 16.2mm diameter punch; then coating the surface of the cut AS-SSPE with liquid CS-SSPE to form a solid polymer electrolyte (i.e., a double-layer solid electrolyte); sandwiching the solid electrolyte disc between two stainless steel blocking electrodes; covering with a spring clamp; and assembling a coin cell test battery. The battery is placed in a high-low temperature (humid heat) test chamber, and the temperature is slowly increased from 0°C to 80°C, with tests performed every 5°C. Before each temperature measurement, the battery is allowed to stand at that temperature for 2 hours to reach thermodynamic equilibrium. The test frequency range of the electrochemical workstation is set to 4MHz~100mHz, and the amplitude is set to 5mV.

[0093] The formula for calculating ionic conductivity (σ, unit S / cm) is: σ = L / (S·R), where L is the thickness (cm) of the solid polymer electrolyte and S is the area (cm²) of the solid polymer electrolyte. 2 R is the ohmic resistance (Ω) measured by electrochemical impedance spectroscopy.

[0094] The ion transference number (including lithium-ion transference number or sodium-ion transference number) of the solid polymer electrolyte of this invention is also tested using an electrochemical workstation. During DC polarization testing, the polarization voltage is set to 10 mV, and the test duration is 20 hours. Electrochemical Impedance Spectroscopy (EIS) tests are performed before and after the DC polarization test, with the test frequency range set to 4 MHz to 100 mHz and the amplitude set to 5 mV. When testing the lithium-ion transference number, the lithium metal symmetric battery is placed in a high-low temperature (damp heat) test chamber and left to stand at 80°C for 12 hours to allow a stable interface to form between the polymer electrolyte and the electrode before testing.

[0095] Taking lithium-ion transference number as an example, lithium-ion transference number (t) Li + The formula for calculating ) is: In the formula, ΔV is the applied polarization voltage of 10mV, I0 is the initial current (A), and I s Let R be the steady-state current (A), R0 be the initial impedance of the electrolyte-electrode interface (Ω), and Rb be the current. s Let Rb0 be the steady-state electrolyte resistance (Ω), and Rb0 be the initial electrolyte resistance (Ω). s The impedance (Ω) at the electrolyte-electrode interface is given. The method for calculating the sodium ion transport number is the same as that for calculating the lithium ion transport number.

[0096] The inventors discovered that by increasing the lithium salt concentration and promoting its full dissociation, thereby increasing the carrier concentration, ion conduction efficiency can be optimized. Furthermore, by rationally adding inorganic fillers (e.g., controlling the filler volume fraction and surface properties) and regulating polymer crystallinity, an inorganic filler-polymer interface phase or a permeated active filler phase can be constructed, forming a rapid ion transport channel. Additionally, by designing block copolymers, the polymer crystallinity can be reduced, the proportion of amorphous regions increased, and chain segment mobility enhanced, thus promoting ion transport. Through these three improvements, the ion conductivity can reach 10⁻⁶. -3 S / cm~10 -2 S / cm.

[0097] The following is combined with Figure 1 and Figure 2 The battery structure of the high-voltage polymer-based solid-state battery based on thermodynamic and kinetic regulation provided in the embodiments of the present invention is analyzed, as well as the thermodynamic and kinetic influence mechanisms.

[0098] A review of the transport mechanisms in high-voltage polymer-based solid-state batteries, as shown in the figure. Figure 1 As shown, the thermodynamic and kinetic formulas and the English text in the figure will be introduced first:

[0099] Formula ① in the figure, ΔG=ΔH–TΔS, means: Gibbs free energy change = enthalpy change - temperature × entropy change.

[0100] Formula ② in the figure: σ²=A²e R (T-T0) means: Stress 1 = Coefficient 1 × Exponential term (Activation energy / Gas constant × Temperature).

[0101] Formula ③ in the figure: σ1=A1e -Ea / RT Representation: Reaction rate constant = Pre-exponential factor × Exponential term (Activation energy / Gas constant × Temperature).

[0102] Formula ④ in the figure: σ²=A²e R (T-T0) means: Stress 2 = Coefficient 2 × Exponent (Gas constant × (Temperature - Initial temperature)).

[0103] Formula ⑤ in the figure This means that the rate of change of potential with temperature is equal to the entropy change, which is 4 × Faraday constant.

[0104] In the diagram, Eq.1 indicates the application of formula ①, Eq.2 indicates the application of formula ②, Eq.3-4 indicate the application of formulas ③ and ④, and Eq.5 indicates the application of formula ⑤.

[0105] This invention analyzes high-voltage polymer-based solid-state batteries containing solid polymer electrolytes using the aforementioned thermodynamic and kinetic formulas. Temperature control within the range of 40℃ to 60℃ regulates the ion conduction kinetics of the solid polymer electrolyte, thereby optimizing the interfacial stability between the positive electrode and the solid polymer electrolyte, the interfacial stability between the negative electrode and the solid polymer electrolyte, and the structural stability of the positive or negative electrode active materials.

[0106] Thermodynamics refers to thermodynamics; Kinetics refers to kinetics; Temperature (T) refers to temperature (T); Solid-state polymer electrolyte refers to a solid polymer electrolyte; Electrolyte composition refers to electrolyte decomposition; Rocksalt-like refers to a rock-salt-like structure; Spinel refers to a spinel structure; Stable interface refers to a stable interface; Suppression of electrolyte decomposition refers to the suppression of electrolyte decomposition; Sufficient ionic conductivity refers to sufficient ionic conductivity; Severe electrolyte decomposition refers to severe electrolyte decomposition; Lithium dendrite refers to lithium dendrites; Higher ionic conductivity refers to higher ionic conductivity; CO2 refers to carbon dioxide; O2 refers to oxygen; LiCoO2 refers to lithium cobalt oxide; Lithium metal refers to lithium metal. Figure 1 Legend reference Figure 2 Legendary illustration.

[0107] Appendix Figure 1 Taking solid-state lithium metal batteries (SSLMBs) with LiCoO2 as the cathode material as an example, through... Figure 1As can be seen, the ion transport based on thermodynamic and kinetic regulation at 40℃ and 60℃ are illustrated (see figure). In SSLMBs, the stability of the cathode structure, the ion transport and stability at the electrode / solid-state polymer electrolyte (SSPE) interface, and the ion transport and electrochemical window of the SSPEs (involving thermodynamic and kinetic regulation) jointly affect the cycle performance. The performance differs at different temperatures: at 40℃, although lithium-ion transport kinetics are relatively slow, good interfacial contact can meet the requirements, and the wide electrochemical window and high mechanical strength suppress interfacial side reactions, promoting uniform lithium metal deposition; the catalytic degradation reaction at the cathode / SSPE interface is inhibited by both thermodynamics and kinetics, resulting in less gas generation. However, at 60℃, the side reactions at the anode / SSPE interface intensify, and lithium dendrite growth is difficult to suppress; the cathode / SSPE interface generates a large amount of oxygen and carbon dioxide, hindering ion transport and leading to a significant decrease in battery capacity.

[0108] The present invention provides a schematic diagram of the battery structure and thermodynamic and kinetic influence mechanism of a high-voltage polymer-based solid-state battery based on thermodynamic and kinetic regulation, as shown in the embodiments of the present invention. Figure 2 As shown, the legend and English text in the figure are explained as follows: Thermodynamics-kinetics refers to thermodynamics and kinetics; Structural stability of delithiated electrode (related to state of charge and temperature) refers to the structural stability of the delithiated electrode (related to state of charge and temperature); the lithium metal oxide used is LiMO2; anion refers to anion; Li + This refers to lithium ions; SP refers to conductive additives; polymer refers to polymers; Kinetics refers to kinetics; Cationic conductivity of solid-state electrolytes (related to temperature) represents the cationic conductivity of solid-state electrolytes (related to temperature); Electrochemical stability (related to state of charge and temperature) represents electrochemical stability (related to state of charge and temperature); Thermodynamics refers to thermodynamics; Electrochemical window (related to temperature) represents the electrochemical window (related to temperature); Cationic conductivity of wetting layer (related to temperature) represents the cationic conductivity of the wetting layer (related to temperature). Figure 2Formula reference Figure 1 Explanation.

[0109] This invention provides a method for preparing the above-mentioned high-voltage solid-state polymer battery, such as... Figure 3 As shown, the specific steps include:

[0110] Step S1, preparing the negative electrode side solid polymer electrolyte, includes: dissolving the polymer, the first metal salt and the inorganic filler in an organic solvent, stirring evenly to form a negative electrode solid electrolyte slurry, coating the negative electrode solid electrolyte slurry onto one side of a polyester film, drying and then hot pressing to obtain the negative electrode side solid polymer electrolyte.

[0111] The polymer includes one or more of the following: polyether polymers, polycarbonate polymers, and polyacrylate polymers; the molecular weight of the polymer is between 100,000 g / mol and 1,000,000 g / mol, and can be any value within this range, such as 100,000 g / mol, 200,000 g / mol, 300,000 g / mol, 400,000 g / mol, 500,000 g / mol, 600,000 g / mol, 700,000 g / mol, 800,000 g / mol, 900,000 g / mol, 1,000,000 g / mol, etc., but is not limited to the listed values. Other values ​​not listed within this range also apply; the polymers specifically include one or more of the following: polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol monomethyl ether (PEGME), polyethylene glycol dimethyl ether (PEGDME), polyethylene carbonate (PEC), polypropylene carbonate (PPC), polytrimethylene carbonate (PTMC), polycaprolactone (PCL), polyvinyl chloride (PVC), polydiethyl carbonate (PDEC), polymethyl methacrylate (PMA), polymethyl methacrylate (PMMA), polyethyl methacrylate (PEA), polyethyl methacrylate (PEMA), and polybutyl acrylate (PBA);

[0112] The mass ratio of the first metal salt to the polymer is 5%-50%; the first metal salt includes: a first lithium salt or a first sodium salt; the first lithium salt includes one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium dioxalate borate, lithium difluorooxalate borate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and lithium dioxoborate; the first sodium salt includes one or more of sodium hexafluorophosphate, sodium hexafluorophosphate, sodium tetrafluoroborate, sodium perchlorate, sodium trifluoromethanesulfonate, sodium bis(trifluoromethanesulfonyl)imide, sodium borate, and sodium dioxoborate.

[0113] The mass ratio of inorganic filler to polymer is 1%-80%; the inorganic filler includes: alumina (Al2O3), silicon dioxide (SiO2), titanium dioxide (TiO2), zirconium dioxide (ZrO2), magnesium oxide (MgO), barium titanate (BaTiO3), molecular sieves (e.g., zeolite), montmorillonite (layered silicates), and garnet-type oxides (e.g., lithium lanthanum zirconium oxide Li7La3Zr2O). 12 ), NASICON-type oxides (e.g., lithium aluminum titanium phosphate Li), 1.3 Al 0.3 Ti 1.7 (PO4)3), perovskite oxides (e.g., lithium lanthanum titanium oxide Li) 0.33 La 0.55 TiO3), lithium thiogermanium phosphate sulfide (Li 10 GeP2S 12 One or more of the following: lithium phosphorus sulfide (Li3PS4), lithium aluminum phosphate (LiAlPO4), lithium titanium phosphate (LiTi2(PO4)3), and lithium halide metal salts (e.g., Li3YCl6, Li3InCl6);

[0114] Solvents include one or more of the following: deionized water, dichloromethane, dichlorobenzene, xylene, dimethyl sulfoxide, chloroform, tetrahydrofuran, toluenecyclohexanone, methanol, toluene, ethanol, acetonitrile, ethyl acetate, diethyl ether, acetone, n-hexane, cyclohexane, cyclohexanone, n-heptane, hexafluoroisopropanol, N-methylpyrrolidone, N,N-dimethylformamide, benzene, chlorophenol, 1,4-dioxane, pyridine, and petroleum ether.

[0115] The stirring time is 12 to 24 hours. The stirring method is conventional. For example, the mixture formed by dissolving the polymer, the first metal salt and the inorganic filler in the organic solvent can be placed in a mixer and stirred. The speed is not limited. The goal is to form a uniformly mixed negative electrode solid electrolyte slurry.

[0116] The drying temperature is 50℃~80℃; the hot pressing temperature is 80℃~120℃, and the pressure is 5MPa~10MPa;

[0117] The solid polymer electrolyte on the negative electrode side is solid and has a thickness between 20 μm and 200 μm.

[0118] Step S2, preparing the positive electrode side solid polymer electrolyte, includes: mixing the oligomer and the second metal salt and heating to make the oligomer a molten liquid, stirring evenly to make the second metal salt uniformly dispersed in the oligomer, and obtaining a liquid positive electrode side solid polymer electrolyte.

[0119] The oligomers include one or more of the following: polyether oligomers, polycarbonate oligomers, and polyacrylate oligomers; the molecular weight of the oligomers is 200 g / mol to 5000 g / mol, and can be any value within this range, such as: 200 g / mol, 500 g / mol, 1000 g / mol, 1500 g / mol, 2000 g / mol, 2500 g / mol, 3000 g / mol, 3500 g / mol, 4000 g / mol, 4500 g / mol, 5000 g / mol, etc., but not limited to the listed values; other values ​​within this range are also included. The listed values ​​also apply; the oligomers specifically include one or more of the following: polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol monomethyl ether (PEGME), polyethylene glycol dimethyl ether (PEGDME), polyethylene carbonate (PEC), polypropylene carbonate (PPC), polytrimethylene carbonate (PTMC), polycaprolactone (PCL), polyvinyl chloride (PVC), polydiethyl carbonate (PDEC), polymethyl methacrylate (PMA), polymethyl methacrylate (PMMA), ethyl methacrylate (PEA), polyethyl methacrylate (PEMA), and polybutyl acrylate (PBA);

[0120] The mass ratio of the second metal salt to the oligomer is 5%-50%; the second metal salt includes: a second lithium salt or a second sodium salt; the second lithium salt includes one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium dioxalate borate, lithium difluorooxalate borate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and lithium dioxalate borate; the second sodium salt includes one or more of sodium hexafluorophosphate, sodium hexafluorophosphate, sodium tetrafluoroborate, sodium perchlorate, sodium trifluoromethanesulfonate, sodium bis(trifluoromethanesulfonyl)imide, sodium borate, and sodium dioxalate borate; the solid content in the negative electrode solid electrolyte slurry is 0.01 g / mL to 0.5 g / mL;

[0121] The heating temperature is 100℃~130℃, and the time is 1~3 hours;

[0122] Generally, when preparing the positive electrode side solid polymer electrolyte, the oligomer is mixed with a second metal salt, and then heated to melt the oligomer and the second metal salt into a uniform viscous liquid, which is then coated onto the surface of the negative electrode side solid polymer electrolyte. In an optional scheme, if the melting point of the oligomer and / or the second metal is too high to meet the melting conditions, a small amount of organic solvent can be added to dissolve it, and then coated onto the surface of the negative electrode side solid polymer electrolyte. After the organic solvent is evaporated and removed, the positive electrode side solid polymer electrolyte is obtained, and then the positive electrode is covered on the positive electrode side solid polymer electrolyte.

[0123] Step S3, assembling a high-voltage solid-state polymer battery, includes: coating one side of the negative electrode solid-state polymer electrolyte with the positive electrode solid-state polymer electrolyte to obtain a solid-state polymer electrolyte; attaching the other side of the negative electrode solid-state polymer electrolyte to the side of the negative electrode containing the negative electrode active material; attaching the positive electrode solid-state polymer electrolyte to the side of the positive electrode containing the positive electrode active material; and assembling to obtain a high-voltage solid-state polymer battery.

[0124] The coating method is a conventional method, such as, but not limited to, any one of brush coating, roller coating, gravure coating, and blade coating; the thickness of the solid polymer electrolyte coated on the side of the negative electrode side is in the range of 2μm to 50μm.

[0125] Alternatively, a high-voltage solid polymer battery (i.e., a pouch cell) can be obtained by stacking the positive electrode, solid polymer electrolyte, and negative electrode in multiple layers using conventional methods.

[0126] The cathode is prepared using conventional methods, or commercially available cathodes from solid-state batteries can be directly selected. The active materials for the cathode include: spinel-structured lithium nickel manganese oxide (LiNi). 0.5 Mn 1.5 Lithium-rich manganese-based materials (Li2MnO3), lithium manganese phosphate with olivine structure (LiMPO4), high-voltage lithium cobalt oxide (LiCoO2), nickel-rich layered oxides (e.g., LiNi) 0.9 Co 0.1 O2), spinel-type LiNi 0.92 Co 0.04 Mn 0.04 O2, spinel-type LiNi 0.5 Mn 1.5 O4-derived materials (e.g., LiTiMnO4, LiCrMnO4), lithium-rich spinel composites (e.g., Li 1+n AwNi 0.5+x Co 0.2+y Mn 0.3+z O2), high-voltage sodium ferric sulfate (Na2Fe(SO4)3), NASICON-type sodium vanadium phosphate (Na3V2(PO4)3), P2-type layered transition metal oxides (P2-Na 0.66 Ni 0.33x Zn x Mn 0.67O2 Cu-doped O3-type layered oxides (Na) 0.9 Cu 0.22 Fe 0.07 Mn 0.48O2Polyanionic cathode materials, Prussian blue analogues, polyanionic phosphates, Zn-doped P-type layered oxides, magnesium-rich NASICON-type cathode materials, high-potential fluorophosphates, and spinel transition metal-doped LiMnO4. x Mn 2-x O4 (where M is at least one of Co, Cr, Ni, Fe, Cu) or one or more of these; when the high-voltage solid polymer battery is a solid lithium battery, the active material of the positive electrode is the above-mentioned lithium-ion-containing positive electrode active material; when the high-voltage solid polymer battery is a solid sodium battery, the active material of the positive electrode is the above-mentioned sodium-ion-containing positive electrode active material.

[0127] The negative electrode is prepared using conventional methods. The active material of the negative electrode includes: metallic lithium or metallic sodium, or commercially available lithium or sodium sheets. When the high-voltage solid polymer battery is a solid lithium battery, the active material of the negative electrode is metallic lithium. When the high-voltage solid polymer battery is a solid sodium battery, the active material of the negative electrode is metallic sodium.

[0128] The solid polymer electrolyte based on thermodynamic and kinetic regulation of the present invention is assembled with a positive electrode and a negative electrode according to conventional methods to form a high-voltage solid polymer battery. The solid battery includes, but is not limited to, any one of all-solid-state lithium metal batteries and all-solid-state sodium metal batteries.

[0129] The application of the high-voltage solid polymer battery prepared by the method of this invention based on thermodynamic and kinetic regulation can be used in electric vehicles or energy storage devices.

[0130] Because the high-voltage solid polymer battery based on thermodynamic and kinetic regulation provided in this invention has the characteristics of high-voltage stability and long cycle life, it can meet the requirements of electric vehicles or energy storage devices for high energy density and safety performance.

[0131] To better understand the technical solution provided by this invention, the following examples illustrate the preparation process and characteristics of the high-voltage solid-state polymer battery based on thermodynamic and kinetic regulation.

[0132] Example 1

[0133] This embodiment provides a method for preparing a high-voltage solid-state polymer battery based on thermodynamic and kinetic regulation. The specific steps are as follows:

[0134] 1) Preparation of AS-SSPE:

[0135] PEO (600000 g / mol, 8 g), LiTFSI (1 g), and LLZTO (2 g) were dissolved in 100 mL of anhydrous acetonitrile and stirred for 24 hours to disperse evenly. The mixture was then coated onto one side of a 50 μm thick polyester film and dried at 60 °C for 12 hours. Finally, it was hot-pressed at 100 °C (8 MPa) to obtain AS-SSPE with a total thickness of 100 μm.

[0136] 2) Preparation of CS-SSPE:

[0137] PEGDME (2000 g / mol, 5 g), LiTFSI (0.6 g), and LiDFOB (0.4 g) were mixed and heated at 120 °C for 1 hour to completely liquidify the PEGDME. The mixture was then heated and stirred for 2 hours to uniformly disperse LiTFSI and LiDFOB within the PEGDME, forming a solid polymer electrolyte on the positive electrode side (CS-SSPE). The molar ratio of PEO monomer to lithium ions [EO]:[Li + = 12:1.

[0138] Preparation of solid polymer electrolyte: CS-SSPE was brush-coated onto the surface of AS-SSPE to a thickness of 20 μm, forming a solid polymer electrolyte (i.e., a bilayer solid electrolyte). The specific preparation process is as follows: Figure 4 As shown.

[0139] 3) Basic electrochemical tests:

[0140] Ionic conductivity was tested for AS-SSPE, CS-SSPE, and the bilayer solid electrolyte. The testing method for the bilayer solid electrolyte was as described above. The testing method for AS-SSPE alone was the same as for the bilayer solid electrolyte, except that the solid AS-SSPE was cut into 16.2mm diameter discs and then assembled into coin cells using the same method. For CS-SSPE alone, liquid CS-SSPE was brushed between two stainless steel blocking electrodes, covered with a spring clamp, and then assembled into a coin cell for testing. The ionic conductivity test results for AS-SSPE, CS-SSPE, and the bilayer solid electrolyte are shown in the appendix. Figure 5 The horizontal axis represents temperature (superscript unit: °C (degrees Celsius), subscript unit: K). -1 (Reciprocal of Kelvin)), the vertical axis represents ionic conductivity (unit: S / cm), through Figure 5 It can be seen that the ionic conductivity of the bilayer electrolyte is the best in the measured temperature range. The test data are detailed in Table 1.

[0141] The migration number test method is as described above. In this embodiment, the lithium-ion migration number at 40°C is shown in the figure as AS-SSPE-Li-40°C. (See attached figure.) Figure 6 The horizontal axis represents time (in seconds), and the vertical axis represents current (in μA). See Table 1 for detailed test data.

[0142] Electrochemical window testing, the redox curves of this example at 40℃ and Comparative Example 1 at 60℃ are shown in the appendix. Figure 7 The x-axis represents voltage (V) and the y-axis represents current (μA). The specific electrochemical window testing method is as follows: using linear sweep voltammetry (LSV), a disc (Φ16.2 mm) of AS-SSPE prepared in this example is placed on a lithium metal sheet (Φ12 mm). The other side of the AS-SSPE is coated with CS-SSPE to form a solid polymer electrolyte. Two stainless steel gaskets and a spring clamp are then placed on top, and a coin cell is assembled. When testing the oxidation and reduction potentials of the solid polymer electrolyte to lithium metal, the battery containing lithium metal as a reference electrode is placed in a high and low temperature (humid heat) test chamber and left to stand at 40°C and 60°C for 12 hours respectively to allow a stable interface to form between the solid polymer electrolyte and the electrode before testing. The CHI600E electrochemical workstation from Shanghai Chenhua Instrument Co., Ltd. was used. The scan rate was set to 0.1 mV / s. The voltage was scanned from 2.5 V to 6.0 V to detect the antioxidant capacity of the solid polymer electrolyte. The voltage was scanned from 2.5 V to 0 V to detect the reducing capacity of the solid polymer electrolyte.

[0143] 4) Molecular dynamics simulation:

[0144] Solid polymer electrolyte Li based on thermodynamic and kinetic regulation for high-voltage polymer-based solid-state batteries + and TFSI - Mean square displacement at 40℃ and 60℃; Li at 40℃ and 60℃ + With TFSI - The radial distribution function and coordination number between oxygen in ethylene oxide and oxygen in polyoxyethylene are shown in the appendix. Figure 8 ,in, Figure 8 (a) A comparative analysis of Li + and TFSI - The diffusion coefficients of both ions increased significantly when the temperature rose to 60℃. A higher diffusion coefficient indicates faster movement of the surface ions within the system, which leads to changes in the coordination structure of Li and O. The higher the coordination degree of the EO units in PEO, the better the oxidative stability of PEO. We hypothesize that Li... +The coordination between PEO and Li+ tends to saturate at lower temperatures. However, as the temperature increases, the flexibility of the PEO molecule significantly increases, weakening the adsorption of Li+. Consequently, the g(r) values ​​and CN values ​​of Li+ and EO units are relatively high at 40℃. Simultaneously, the g(r) values ​​and CN values ​​between Li+ and TFSI- decrease at 40℃ (see Appendix). Figure 8 (bc).

[0145] 5) Structural characterization:

[0146] Fourier transform infrared spectra of solid polymer electrolytes in high-voltage polymer-based solid-state batteries based on thermodynamic and kinetic regulation are attached. Figure 9 The horizontal axis in the graph represents the wave number (unit: cm). -1 The vertical axis represents peak intensity (in au), used to analyze the structure of the ethylene oxide unit in AS-SSPE-Li, 1054 cm⁻¹. -1 1062cm -1 and 1117cm -1 The peak area at 1070 cm⁻¹ is defined as the coordinated EO unit, while 1070 cm⁻¹ is defined as the peak area at 1070 cm⁻¹. -1 Up to 1106cm -1 and 1131cm -1 The peak area at 40℃ is defined as the free EO unit. The ratio of the peak area of ​​coordinated EO units to that of free EO units is 66.9%, which is 16.3% higher than that at 60℃, proving that the electrolyte kinetics are better at 40℃.

[0147] 6) Assembly of button cells:

[0148] A lithium cobalt oxide positive electrode is prepared using high-voltage lithium cobalt oxide as the positive electrode material, and a commercial lithium sheet is used as the lithium metal negative electrode. The lithium metal negative electrode, a double-layer solid electrolyte, and then the lithium cobalt oxide positive electrode are stacked in sequence. The solid polymer electrolyte (AS-SSPE) on the negative electrode side is attached to the negative electrode, and the solid polymer electrolyte (CS-SSPE) on the positive electrode side is attached to the positive electrode. The resulting assembly forms a 2032 coin cell (lithium cobalt oxide all-solid-state lithium metal battery).

[0149] The preparation method of the lithium cobalt oxide cathode is as follows: First, the positive electrode active material lithium cobalt oxide, polyvinylidene fluoride, and conductive additive carbon black Super-P are dissolved in 1-methyl-2-pyrrolidone solvent to form a positive electrode slurry. This slurry is then coated into an electrode sheet uniformly coated on an aluminum current collector using a coating machine. The electrode sheet is then formed by a small stamping machine and dried in a vacuum oven at 45°C for later use.

[0150] 7) Button cell cycle performance test:

[0151] Testing was conducted on an all-solid-state lithium metal battery (LCO|DL-SSPE-Li|Li):

[0152] Using a blue electric shock tester, the lithium cobalt oxide all-solid-state lithium metal battery was charged and discharged at a rate of 0.1C for two weeks, followed by 780 cycles at a rate of 0.5C. The charge and discharge cutoff voltage range was 3.0V-4.3V, and the operating temperature was 40℃ and 60℃. The charge and discharge curves were tested and are shown in the attached figure. Figure 10 As can be seen, at 40℃, the circulation capacity retention rate after 300 cycles is 89.3%, and after 780 cycles, the circulation capacity retention rate is 80.3%; at 60℃, the circulation capacity retention rate after 300 cycles is 77.6%.

[0153] Using a blue electric shock tester, the lithium cobalt oxide all-solid-state lithium metal battery was charged and discharged at a rate of 0.1C for two weeks, followed by 780 cycles at a rate of 0.5C. The charge and discharge cutoff voltage range was 3.0V-4.45V, and the operating temperature was 40℃ and 60℃. The charge and discharge curves were tested and are shown in the attached figure. Figure 11 The charge-discharge curves at 40℃ and 60℃ are shown below. Figure 11 (a) and Figure 11 As shown in (b), the horizontal axis represents capacity (mAh / g), and the vertical axis represents voltage (V); the cycle performance curve is shown in the figure. Figure 11 As shown in (c), the horizontal axis represents the number of cycles, and the vertical axis represents the cycle capacity (mAh / g) and coulombic efficiency (%), respectively. It can be seen that at 40°C, the cycle capacity retention rate is 95.1% after 70 cycles, 81.8% after 400 cycles, and 77.4% after 550 cycles; at 60°C, the cycle capacity retention rate is 61.0% after 300 cycles.

[0154] The average coulombic efficiency (Average CE, %) of LCO|DL-SSPE-Li|Li coin cells in the voltage ranges of 3.0-4.3V and 3.0-4.45V is shown in the appendix. Figure 12 The test data is detailed in Table 1.

[0155] The leakage current of the LCO|DL-SSPE-Li|Li button cell during constant voltage float charging measurements at 4.2V, 4.3V, 4.4V, 4.5V, and 4.6V is shown in the appendix. Figure 13 The horizontal axis represents time (in hours, h), and the vertical axis represents current (mA) and voltage (V). (The last part, "with attached...", appears to be a typo and can be omitted.) Figure 13Electrochemical float charge tests of the LCO|DL-SSPE-Li|Li battery were conducted at 40℃ and 60℃, with a voltage range of 4.2-4.6V. At 4.2V, 4.3V, and 4.4V, the self-discharge current was below 4μA at both temperatures, with a slightly lower current value at 40℃. However, at 60℃, the self-discharge current slightly increased to 6.2μA at 4.5V and then sharply increased to 33.8μA at 4.6V, indicating severe self-discharge behavior, consistent with the accelerated capacity decay observed at 4.45V.

[0156] This embodiment compares the electrochemical performance of all-solid-state lithium metal batteries based on polyethylene oxide with other studies, involving various materials such as NCM811, NCM83, and NCM622, as shown in the appendix. Figure 14 This invention demonstrates that the high-voltage PEO-based solid-state lithium metal battery exhibits superior long-cycle performance, outperforming most recent results reported in the existing literature. At 4.45V, the LCO||Li battery achieves up to 550 cycles; at 4.30V, it reaches 800 cycles. The optimized battery performs best at 40°C, exhibiting the lowest capacity decay rate per cycle, and has a higher cutoff voltage than conventional high-temperature systems (60°C) reported in previous studies. Notably, these excellent performance indicators even surpass those of batteries operating at 30°C, highlighting the superior electrochemical stability of this invention.

[0157] 7) Cycle performance of pouch batteries

[0158] An optical photograph (100cm × 8cm × 0.0075cm) of the solid polymer electrolyte in the high-voltage polymer-based solid-state battery prepared in Example 1 of this invention based on thermodynamic and kinetic regulation is shown below. Figure 15 This solid polymer electrolyte can be used to prepare monolithic and stacked pouch cells.

[0159] Using lithium cobalt oxide as the positive electrode material, the high-voltage polymer-based solid electrolyte based on thermodynamic and kinetic regulation prepared in Example 1, and the lithium metal negative electrode assembled into an LCO|DL-SSPE-Li|Li monolayer pouch cell, the charge-discharge voltage curves and cycle performance of the pouch cell under the preferred operating condition of 40°C are shown in the appendix. Figure 16 (a) and appendix Figure 16 (b) It can be seen that the capacity retention rate of the LCO|DL-SSPE-Li|Li single-layer soft pack battery after 300 cycles is 83.6%.

[0160] A series of safety tests were conducted on the aforementioned single-layer pouch battery LCO|DL-SSPE-Li|Li, including voltage tests using a multimeter on the pouch battery after bending, folding, and cutting. The results showed that the pouch battery did not catch fire or explode, and the voltage did not change significantly. (See attached image.) Figure 17 .

[0161] Based on the single-layer pouch cell test results, a multi-layer pouch cell LCO|DL-SSPE-Li|Li was further assembled. Three-dimensional reconstruction images obtained using X-ray tomography showed a good multi-layer stacked structure. A schematic diagram of the structure is attached. Figure 18 The figure shows 15 cathodes, 30 solid polymer electrolytes, and 16 lithium foils. The 3mm in the figure represents the scale of the X-ray tomography scan.

[0162] 8) Assemble a lithium-lithium symmetric battery Li|AS-SSPE-Li|Li and test its performance:

[0163] A lithium-lithium symmetric battery, Li|AS-SSPE-Li|Li, was assembled. The evolution of the Li / SSPEs interface in the symmetric battery at 40℃ and 60℃ was investigated. The electrochemical impedance spectra and corresponding relaxation time distributions of the cells after standing at 40℃ and 60℃ are shown in the appendix. Figure 19 (a) and appendix Figure 19 (b) via appendix Figure 19 As can be seen, at 40℃, the battery's contact resistance (RC) remained almost unchanged, while the peak integral of the interfacial resistance (RSEI) gradually increased, and the peak position shifted towards a longer relaxation time, indicating a reduced transport response of lithium ions through the solid electrolyte interface (SEI). This suggests that a stable SEI can form at 40℃ and persist for up to 10 days. However, at 60℃, after one day, RC remained stable, but the RSEI showed an abnormal increase, followed by a continuous decrease until it stabilized over the next five days.

[0164] Electrochemical impedance spectroscopy (EIS) spectra and their corresponding relaxation time distributions during cycling at 40°C and 60°C are shown in the appendix. Figure 20 (a) and attached figure (b), with appendix Figure 20The results show that at 40°C, the contact resistance (RC) remains constant, and the relative surface area resistance (RSEI) reaches its maximum after 20 cycles, then gradually decreases until the 70th cycle. Notably, the time constant of RSEI remains stable throughout the cycling process, indicating that lithium-ion transport through the SEI remains stable during lithium plating / stripping. It is likely that the SEI forms in the first 20 cycles, after which the battery enters a slow activation process. At 60°C, RC changes little, and RSEI reaches its maximum after 10 cycles, then rapidly decreases until it reaches a steady state.

[0165] Symmetrical cells were tested at 40℃ and 60℃, respectively, at an amplification rate of 0.05 mA·cm⁻¹. -2 The current density was used for charge-discharge cycles, and the capacity of each cycle was 0.05 mAh·cm³. -2 The recorded voltage versus time or capacity curves are shown in the appendix. Figure 21 The horizontal axis represents the cycle time (in hours, h), and the vertical axis represents the voltage (in voltage, V). (The last part, "thanks to the attached...", appears to be a separate, unrelated sentence fragment.) Figure 21 As can be seen, at 40℃, the Li|AS-SSPE-Li|Li battery initially exhibited an overpotential of 67mV, which gradually increased to 71mV and stabilized at 63mV; at 60℃, the battery showed an overpotential of 15mV and the curve showed more fluctuations during cycling, indicating that the mechanical strength of the electrolyte at 60℃ was insufficient to suppress the growth of lithium dendrites.

[0166] EIS spectra of the symmetrical cells after 70 and 650 cycles at 40°C and 60°C, respectively, are attached. Figure 22 The horizontal and vertical axes represent the real and imaginary parts of the impedance, respectively, in ohms. Figure 22 This indicates that after 650 cycles, the battery impedance at 40°C decreased compared to after 70 cycles; however, at 60°C, the battery impedance showed a sharp increase. This phenomenon clearly demonstrates that high-temperature environments significantly exacerbate the side reactions between polyethylene oxide and lithium metal.

[0167] 9) Failure Mechanism Characterization

[0168] High-angle annular dark-field images of the LCO structure in the LCO|DL-SSPE-Li|Li battery prepared at 40℃ and 60℃ using spherical aberration electron microscopy are attached. Figure 23 .in Figure 23 The English definitions recorded in the text are: Spinel (for spinel type); Layer (for layered structure); Rocksalt-like (for rock-salt-like type), with appendix. Figure 23The surface structure of LCO after cycling was shown. LCO particles cycled at 40℃ effectively retained their layered structure, exhibiting only a rock-salt-like phase of approximately 1 nm. In contrast, LCO particles cycled at 60℃ showed significant surface structure degradation, exhibiting spinel and rock-salt-like phases of 3–8 nm. (The text then abruptly shifts to a different topic: ...through attached...) Figure 23 This indicates that, under highly delithiated conditions, high-angle annular dark-field scanning transmission electron microscopy confirmed the accelerated structural degradation of LCO at high temperatures.

[0169] Differential electrochemical mass spectrometry (DEMS) was used to test gas production in the battery. Voltage curves and DEMS data of the LCO|DL-SSPE-Li|Li battery at 40℃ and 60℃ were prepared, showing the gas production situation. (See attached figure.) Figure 24 As can be seen, carbon dioxide (CO2) was produced by the battery at both temperatures as the charging voltage increased (>4.2V), which is attributed to the degradation of SSPEs. However, the CO2 production rate accelerated significantly at 60°C, indicating that the SSPEs underwent more rapid decomposition. Notably, a significant amount of oxygen (O2) was detected at 60°C, while no O2 was detected at 40°C. Therefore, increasing the temperature provides a greater thermodynamic driving force for the generation of oxygen vacancies, leading to the loss and release of oxygen.

[0170] X-ray tomography was used to test the interface changes of the assembled battery. The three-dimensional reconstruction results of the electrode / SSPE interface of the LCO|DL-SSPE-Li|Li battery after 10 cycles are shown in the appendix. Figure 25 .

[0171] Based on the above analysis, Appendix Figure 26 All possible variations of LCO|DL-SSPE-Li|Li batteries at 40℃ and 60℃ are summarized.

[0172] in, Figure 26The English definitions recorded in the text are as follows: Lithium metal refers to lithium metal; Suppression of electrolyte decomposition refers to the suppression of electrolyte decomposition; Stable interface refers to a stable interface; Sufficient ionic conductivity refers to sufficient ionic conductivity; Solid-state polymer electrolyte refers to a solid polymer electrolyte; Severe electrolyte decomposition refers to severe electrolyte decomposition; Lithium dendrite refers to lithium dendrites; Higher ionic conductivity refers to higher ionic conductivity; Electrolyte decomposition refers to electrolyte decomposition; Rocksalt-like refers to rock-salt-like type; Spinel refers to spinel type.

[0173] According to the appendix Figure 26 It is evident that although lithium-ion transport kinetics are relatively slow at 40°C, with a well-established interfacial contact, the lithium-ion transport kinetics can still meet the requirements and exhibit a high lithium-ion transference number. Furthermore, a wider electrochemical window (thermodynamically), enhanced mechanical strength, and suppressed interfacial side reactions (kinetically) allow for more uniform lithium metal deposition at 40°C. More significantly, at the cathode / solid polymer electrolyte interface, the catalytic degradation reaction is significantly suppressed thermodynamically and kinetically with decreasing temperature, resulting in less gas production.

[0174] In contrast, at a high temperature of 60°C, the side reactions at the negative electrode / solid polymer electrolyte interface are more severe, failing to effectively suppress lithium dendrite growth. Simultaneously, a large amount of oxygen and carbon dioxide are generated at the positive electrode / solid polymer electrolyte interface, hindering ion transport and leading to a significant decrease in battery capacity.

[0175] In summary, through the analysis of the degradation mechanism of high-temperature polymer-based solid-state batteries, temperature was identified as the key factor mainly influencing thermodynamics and kinetics. Systematic studies show that temperature kinetically affects the surface energy and interfacial electrochemical stability of solid polymer electrolytes (SSPEs), thermodynamically affects the chemical stability of SSPEs, and influences the structural stability of electrode materials through thermodynamic and kinetic pathways.

[0176] At 40°C, the LCO|DL-SSPE-Li|Li coin cell exhibited a high capacity retention of 81.8% after 400 cycles within a voltage range of 3.0-4.45V. This Example 1 provides a methodological framework for analyzing battery failure in polymer-based SSBs from a thermodynamic and kinetic perspective. It emphasizes the crucial role of temperature in high-temperature polymer-based SSBs, similar to the importance of pressure in sulfide-based SSBs, thus providing valuable insights for the development of polymer-based SSB technology.

[0177] Comparative Example 1

[0178] The AS-SSPE, CS-SSPE, and bilayer solid electrolyte prepared in Example 1, as well as the assembled batteries (coin cells and lithium-lithium symmetric cells), were tested at 60°C as Comparative Example 1. The test diagrams at 60°C in the accompanying drawings of Example 1 are test diagrams of Comparative Example 1.

[0179] The ionic conductivity and cation migration of the solid polymer electrolyte in Comparative Example 1 at 60°C were tested, and the test data are detailed in Table 1. The test data for the ionic conductivity and cation transference number of the solid polymer electrolyte in Comparative Example 1 at 60°C, as well as the cycle capacity retention and average coulombic efficiency of the coin cell at 60°C, are detailed in Table 1.

[0180] Example 2

[0181] This embodiment provides a method for preparing high-pressure solid polymer electrolytes based on thermodynamic and kinetic regulation. The specific steps are as follows:

[0182] 1) Preparation of AS-SSPE:

[0183] PEO (600000 g / mol, 8 g), NaTFSI (1 g), and LLZTO (2 g) were dissolved in 100 mL of anhydrous acetonitrile and stirred for 24 hours to disperse evenly. The solution was then coated onto one side of a 50 μm thick polyester film, dried at 60 °C for 12 hours, and then hot-pressed at 100 °C (8 MPa) to obtain AS-SSPE with a total thickness of 100 μm. The preparation process is detailed in the appendix. Figure 27 .

[0184] 2) Preparation of CS-SSPE:

[0185] PEGDME (2000 g / mol, 5 g), NaTFSI (0.6 g), and NaDFOB (0.4 g) were mixed and heated at 120 °C for 1 hour to completely liquidify the PEGDME. The mixture was then heated and stirred for 2 hours to uniformly disperse NaTFSI and NaDFOB within the PEGDME, forming a solid polymer electrolyte on the positive electrode side (CS-SSPE). The molar ratio of PEO monomer to lithium ions was controlled as [EO]:[Li+ The ratio is 12:1; the preparation process is shown in the appendix. Figure 27 .

[0186] Preparation of solid polymer electrolyte: CS-SSPE was brush-coated onto the surface of AS-SSPE to a thickness of 20 μm, forming a solid polymer electrolyte (i.e., a bilayer solid electrolyte). The specific preparation process is as follows: Figure 27 As shown.

[0187] 3) The basic electrochemical tests are the same as those in Example 1. The ionic conductivity and cation migration of the solid polymer electrolyte in this example are tested at 40°C. The test data are detailed in Table 1.

[0188] 4) Assembly of button cells:

[0189] The assembly method is the same as that of the button cell in Example 1. This example uses a high-voltage O3-NaNi battery. 1 / 3 Fe 1 / 3 Mn 1 / Using 3O2 (NFM333) as the positive electrode and commercially available sodium sheet as the sodium negative electrode, the sodium negative electrode and the bilayer solid electrolyte prepared in this embodiment are stacked in sequence, and then the NFM333 positive electrode is stacked on top to assemble a 2032 coin cell (NFM333|DL-SSPE-Na|Na). In this case, the solid polymer electrolyte (AS-SSPE) on the negative electrode side is attached to the sodium negative electrode, and the solid polymer electrolyte (CS-SSPE) on the positive electrode side is attached to the NFM333 positive electrode. Then, using Na3V2(PO4)3 as the positive electrode (NVP positive electrode), and commercially available sodium sheet as the sodium negative electrode, the sodium negative electrode and the bilayer solid electrolyte prepared in this embodiment are stacked in sequence, and then the NVP positive electrode is stacked on top to assemble a 2032 coin cell (NVP|DL-SSPE-Na|Na). In this case, the solid polymer electrolyte (AS-SSPE) on the negative electrode side is attached to the sodium negative electrode, and the solid polymer electrolyte (CS-SSPE) on the positive electrode side is attached to the NVP positive electrode.

[0190] The preparation methods for NFM333 and NVP cathodes are as follows: First, the cathode active material O3-NaNi is prepared... 1 / 3 Fe 1 / 3Mn 1 / 3 O2 and Na3V2(PO4)3 are dissolved in 1-methyl-2-pyrrolidone solvent with polyvinylidene fluoride and conductive additive carbon black Super-P to form a positive electrode slurry. This slurry is then coated onto an aluminum current collector using a coating machine to form electrode sheets, which are then processed into electrode sheets by a small stamping machine and dried in a vacuum oven at 45°C for later use.

[0191] 5) Button cell cycle performance test:

[0192] Testing was conducted on the NFM333 all-solid-state sodium metal battery (NFM333|DL-SSPE-Na|Na):

[0193] Using a blue-light tester, the NFM333 all-solid-state sodium metal battery was charged and discharged at a rate of 0.1C for two weeks, followed by cycling at a rate of 0.2C. The charge / discharge cutoff voltage range was 2.0V-4.0V, and the preferred operating temperature was 40℃. The charge / discharge curves and cycle curves of the battery are shown in the appendix. Figure 28 (a) and appendix Figure 28 (b) When matched with the NFM333 type cathode, the discharge specific capacity at 0.1C is 126.68 mAh / g, and at 0.2C it is 111.26 mAh / g. The capacity retention rate after 95 cycles is 84.5%. Under these temperature optimization conditions, the high-voltage all-solid-state sodium metal battery exhibits excellent electrochemical cycling performance. The cycle capacity retention rate and average coulombic efficiency test data are detailed in Table 1.

[0194] Testing of the NVP all-solid-state sodium metal battery (NVP|DL-SSPE-Na|Na):

[0195] Using a blue electrode tester, the batteries were charged and discharged at a rate of 0.1C for two weeks, followed by 2000 cycles at a rate of 0.5C. The charge / discharge cutoff voltage range was 2.5V-3.8V, and the optimal operating temperature was 40℃. The charge / discharge curves and cycle curves of the NVP all-solid-state sodium metal battery were tested and are shown in the appendix. Figure 29 (a) and appendix Figure 29 (b). After 2000 cycles at 0.5C, NVP|DL-SSPE-Na|Na exhibited long-term cycling stability with a capacity retention rate of up to 83.2%. The cycle capacity retention rate and average coulombic efficiency test data are detailed in Table 1.

[0196] Comparative Example 2

[0197] Comparative Example 2 is a test conducted at 60°C using the AS-SSPE, CS-SSPE, and bilayer solid electrolyte prepared in Example 2, as well as the assembled coin cell. The test diagrams at 60°C in the accompanying drawings of Example 2 are test diagrams for Comparative Example 2.

[0198] The ionic conductivity and cation migration of the solid polymer electrolyte in Comparative Example 2 at 60°C were tested, and the test data are detailed in Table 1. The test data for the ionic conductivity and cation transference number of the solid polymer electrolyte in Comparative Example 2 at 60°C, as well as the cycle capacity retention and average coulombic efficiency of the two coin cells at 60°C, are detailed in Table 1.

[0199] Table 1 summarizes the test data for Examples 1-2 and Comparative Examples 1-2:

[0200]

[0201] The comparison of test data in Table 1 clearly shows that Example 1 outperforms Comparative Example 1 in terms of capacity retention across different voltage ranges. In the 3V-4.3V voltage range, Example 1 maintained 80.3% capacity retention after 780 cycles, while Comparative Example 1 maintained only 77.6% after 300 cycles. In the 3V-4.45V voltage range, Example 1 maintained 77.4% capacity retention after 550 cycles, while Comparative Example 1 maintained only 61.0% after 70 cycles. This indicates that the battery in Example 1, after optimizing the kinetics and thermodynamics, can better maintain its capacity and reduce capacity decay during long-term cycling.

[0202] In terms of cation transference number, the cation transference number of Example 1 is 0.68, which is significantly higher than that of Comparative Example 1 (0.45). Cation transference number reflects the migration ability of ions in the electrolyte. A higher cation transference number means that ions can be transported between the positive and negative electrodes more efficiently during battery charging and discharging, which helps to improve the charging and discharging efficiency and overall performance of the battery.

[0203] Regarding coulombic efficiency, Example 1 also demonstrated advantages under different cycle counts and voltage ranges. The coulombic efficiency reached 99.9% after 780 cycles at 3V-4.3V and 99.6% after 550 cycles at 3V-4.45V, both higher than the coulombic efficiency of Comparative Example 1 under the same conditions. Higher coulombic efficiency indicates less irreversible loss during charging and discharging, and thus higher energy utilization efficiency.

[0204] Significant differences were also observed between Example 2 and Comparative Example 2. In the 2.0V-4.0V voltage range, Example 2 maintained 84.5% capacity retention after 95 cycles, while Comparative Example 2 maintained 80.5% after 50 cycles. In the 2.5V-3.8V voltage range, Example 2 maintained 83.2% capacity retention after 2000 cycles, while Comparative Example 2 maintained only 66.0% after 1000 cycles. The cation transference number of Example 2 was 0.72, higher than that of Comparative Example 2 (0.41), and the coulombic efficiency of Example 2 was also higher than that of Comparative Example 2 at different cycle numbers and voltage ranges.

[0205] The data comparison above shows that the high-voltage polymer-based solid-state battery obtained using the solid polymer electrolyte prepared according to the embodiments of the present invention has significant advantages. The improvements in properties such as ionic conductivity, cation transport number, and cycle capacity retention indicate that the solid polymer electrolyte of the present invention exhibits superior performance in ion transport capability and battery cycle stability.

[0206] This invention analyzes the degradation mechanism of high-temperature polymer-based solid-state batteries, identifying temperature as a key factor influencing both thermodynamics and kinetics. Systematic research shows that temperature kinetically affects the surface energy and interfacial electrochemical stability of solid polymer electrolytes (SSPEs), thermodynamically influences the chemical stability of SSPEs, and affects the structural stability of electrode materials through both thermodynamic and kinetic pathways.

[0207] This invention provides a methodological framework for analyzing battery failure in polymer-based solid-state batteries (SSBs) from a thermodynamic and kinetic perspective. It emphasizes the crucial role of temperature in high-temperature polymer-based SSBs, similar to the importance of pressure in sulfide-based SSBs, thus providing valuable insights for the development of polymer-based SSB technology. Furthermore, the solid-state polymer electrolyte of this invention has broad applicability, matching not only commonly used cathode materials with narrow voltage ranges but also high-voltage cathode materials and metal anodes. Coin cells and pouch cells assembled using this electrolyte achieve stable cycling, which is significant for promoting the widespread application of solid-state batteries in electric vehicles, energy storage systems, and other fields.

[0208] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A high-voltage solid-state polymer battery based on thermodynamic and kinetic regulation, characterized in that, The high-voltage solid-state polymer battery includes: a positive electrode, a negative electrode, and a solid polymer electrolyte; The solid polymer electrolyte has a bilayer structure, comprising: a positive electrode side solid polymer electrolyte and a negative electrode side solid polymer electrolyte; The negative electrode side solid polymer electrolyte comprises: a polymer, a first metal salt, and an inorganic filler; The positive electrode side solid polymer electrolyte comprises: an oligomer and a second metal salt; The solid polymer electrolyte is formed by coating the surface of the solid negative electrode side solid polymer electrolyte with a molten positive electrode side solid polymer electrolyte; The solid polymer electrolyte operates at a temperature of 40°C to 60°C. Within this temperature range, the ion conduction kinetics of the solid polymer electrolyte are controlled based on thermodynamics and kinetics, thereby controlling the interfacial stability between the positive electrode and the solid polymer electrolyte, and the interfacial stability between the negative electrode and the solid polymer electrolyte.

2. The high-voltage solid-state polymer battery according to claim 1, characterized in that, The solid polymer electrolyte has an ionic conductivity of 1.0 × 10⁻⁶ at 40 °C. -4 S / cm~ 1.0×10 -2 S / cm; The lithium-ion or sodium-ion transport number of the solid polymer electrolyte is 0.5 to 0.

9.

3. The high-voltage solid-state polymer battery according to claim 1, characterized in that, The polymer includes one or more of the following: polyether polymers, polycarbonate polymers, and polyacrylate polymers; the molecular weight of the polymer is 100,000 g / mol to 1,000,000 g / mol; specifically, the polymer includes one or more of the following: polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol monomethyl ether (PEGME), polyethylene glycol dimethyl ether (PEGDME), polyethylene carbonate (PEC), polypropylene carbonate (PPC), polytrimethylene carbonate (PTMC), polycaprolactone (PCL), polyvinyl chloride (PVC), polydiethyl carbonate (PDEC), polymethyl methacrylate (PMA), polymethyl methacrylate (PMMA), polyethyl methacrylate (PEA), polyethyl methacrylate (PEMA), and polybutyl acrylate (PBA); The mass ratio of the first metal salt to the polymer is 5%-50%; the first metal salt includes: a first lithium salt or a first sodium salt; the first lithium salt includes one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium dioxalate borate, lithium difluorooxalate borate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and lithium dioxoborate; the first sodium salt includes one or more of sodium hexafluorophosphate, sodium hexafluorophosphate, sodium tetrafluoroborate, sodium perchlorate, sodium trifluoromethanesulfonate, sodium bis(trifluoromethanesulfonyl)imide, sodium borate, and sodium dioxoborate. The inorganic filler has a mass ratio of 1% to 80% to the polymer; the inorganic filler includes one or more of the following: alumina, silicon dioxide, titanium dioxide, zirconium dioxide, magnesium oxide, barium titanate, molecular sieve, montmorillonite, garnet oxide, NASICON oxide, perovskite oxide, lithium thiogermanium phosphate sulfide, lithium phosphate sulfide, lithium aluminum phosphate, lithium titanium phosphate, and lithium halide metal salts.

4. The high-voltage solid-state polymer battery according to claim 1, characterized in that, The oligomers include one or more of the following: polyether oligomers, polycarbonate oligomers, and polyacrylate oligomers; the molecular weight of the oligomers is 200 g / mol to 5000 g / mol; specifically, the oligomers include one or more of the following: polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol monomethyl ether (PEGME), polyethylene glycol dimethyl ether (PEGDME), polyethylene carbonate (PEC), polypropylene carbonate (PPC), polytrimethylene carbonate (PTMC), polycaprolactone (PCL), polyvinyl chloride (PVC), polydiethyl carbonate (PDEC), polymethyl methacrylate (PMA), polymethyl methacrylate (PMMA), polyethyl methacrylate (PEA), polyethyl methacrylate (PEMA), and polybutyl acrylate (PBA); The mass ratio of the second metal salt to the oligomer is 5%-50%; the second metal salt includes: a second lithium salt or a second sodium salt; the second lithium salt includes one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium dioxalate borate, lithium difluorooxalate borate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and lithium dioxalate borate; the second sodium salt includes one or more of sodium hexafluorophosphate, sodium hexafluorophosphate, sodium tetrafluoroborate, sodium perchlorate, sodium trifluoromethanesulfonate, sodium bis(trifluoromethanesulfonyl)imide, sodium borate, and sodium dioxalate borate.

5. The high-voltage solid-state polymer battery according to claim 1, characterized in that, The active materials of the positive electrode include: spinel-structured lithium nickel manganese oxide, lithium-rich manganese-based materials, olivine-structured lithium manganese phosphate, high-voltage lithium cobalt oxide, nickel-rich layered oxides, and spinel-type LiNi. 0.92 Co 0.04 Mn 0.04 O2, spinel-type LiNi 0.5 Mn 1.5 O4 derivatives, lithium-rich spinel composites, high-voltage sodium ferric sulfate, NASICON-type sodium vanadium phosphate, P2-type layered transition metal oxides, Cu-doped O3-type layered oxides, polyanionic cathode materials, Prussian blue analogs, polyanionic phosphates, Zn-doped P-type layered oxides, magnesium-rich NASICON-type cathode materials, high-potential fluorophosphates, spinel transition metal-doped LiMnO4. x Mn 2-x One or more of O4; wherein M includes one or more of Co, Cr, Ni, Fe, and Cu; The active material of the negative electrode includes: lithium metal or sodium metal.

6. A method for preparing a high-voltage solid-state polymer battery according to any one of claims 1-5, characterized in that, The preparation method includes: The preparation of a negative electrode side solid polymer electrolyte includes: dissolving a polymer, a first metal salt and an inorganic filler in an organic solvent, stirring evenly to form a negative electrode solid electrolyte slurry, coating the negative electrode solid electrolyte slurry onto one side of a polyester film, drying it and then hot pressing it to obtain a negative electrode side solid polymer electrolyte. The preparation of a positive electrode side solid polymer electrolyte includes: mixing an oligomer and a second metal salt and heating the mixture to make the oligomer a molten liquid, stirring the mixture evenly to make the second metal salt uniformly dispersed in the oligomer, thereby obtaining a liquid positive electrode side solid polymer electrolyte. Assembling a high-voltage solid-state polymer battery includes: coating one side of the solid polymer electrolyte on the negative electrode side with the solid polymer electrolyte on the positive electrode side to obtain a solid polymer electrolyte; attaching the other side of the solid polymer electrolyte on the negative electrode side to the side of the negative electrode containing negative electrode active material; attaching the solid polymer electrolyte on the positive electrode side to the side of the positive electrode containing positive electrode active material; and assembling to obtain a high-voltage solid-state polymer battery.

7. The preparation method according to claim 6, characterized in that, The polymer includes one or more of the following: polyether polymers, polycarbonate polymers, and polyacrylate polymers; the molecular weight of the polymer is 100,000 g / mol to 1,000,000 g / mol; specifically, the polymer includes one or more of the following: polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol monomethyl ether (PEGME), polyethylene glycol dimethyl ether (PEGDME), polyethylene carbonate (PEC), polypropylene carbonate (PPC), polytrimethylene carbonate (PTMC), polycaprolactone (PCL), polyvinyl chloride (PVC), polydiethyl carbonate (PDEC), polymethyl methacrylate (PMA), polymethyl methacrylate (PMMA), polyethyl methacrylate (PEA), polyethyl methacrylate (PEMA), and polybutyl acrylate (PBA); The mass ratio of the first metal salt to the polymer is 5%-50%; the first metal salt includes: a first lithium salt or a first sodium salt; the first lithium salt includes one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium dioxalate borate, lithium difluorooxalate borate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and lithium dioxoborate; the first sodium salt includes one or more of sodium hexafluorophosphate, sodium hexafluorophosphate, sodium tetrafluoroborate, sodium perchlorate, sodium trifluoromethanesulfonate, sodium bis(trifluoromethanesulfonyl)imide, sodium borate, and sodium dioxoborate. The mass ratio of the inorganic filler to the polymer is 1%-80%; the inorganic filler includes one or more of the following: alumina, silicon dioxide, titanium dioxide, zirconium dioxide, magnesium oxide, barium titanate, molecular sieve, montmorillonite, garnet oxide, NASICON oxide, perovskite oxide, lithium thiogermanium phosphate sulfide, lithium phosphate sulfide, lithium aluminum phosphate, lithium titanium phosphate, and lithium halide metal salts. The solvent includes one or more of the following: deionized water, dichloromethane, dichlorobenzene, xylene, dimethyl sulfoxide, chloroform, tetrahydrofuran, toluenecyclohexanone, methanol, toluene, ethanol, acetonitrile, ethyl acetate, diethyl ether, acetone, n-hexane, cyclohexane, cyclohexanone, n-heptane, hexafluoroisopropanol, N-methylpyrrolidone, N,N-dimethylformamide, benzene, chlorophenol, 1,4-dioxane, pyridine, and petroleum ether. The stirring time is 12 to 24 hours; the drying temperature is 50°C to 80°C; the hot pressing temperature is 80°C to 120°C, and the pressure is 5 MPa to 10 MPa.

8. The preparation method according to claim 6, characterized in that, The oligomers include one or more of the following: polyether oligomers, polycarbonate oligomers, and polyacrylate oligomers; the molecular weight of the oligomers is 200 g / mol to 5000 g / mol; specifically, the oligomers include one or more of the following: polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol monomethyl ether (PEGME), polyethylene glycol dimethyl ether (PEGDME), polyethylene carbonate (PEC), polypropylene carbonate (PPC), polytrimethylene carbonate (PTMC), polycaprolactone (PCL), polyvinyl chloride (PVC), polydiethyl carbonate (PDEC), polymethyl methacrylate (PMA), polymethyl methacrylate (PMMA), polyethyl methacrylate (PEA), polyethyl methacrylate (PEMA), and polybutyl acrylate (PBA); The mass ratio of the second metal salt to the oligomer is 5%-50%; the second metal salt includes: a second lithium salt or a second sodium salt; the second lithium salt includes one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium dioxalate borate, lithium difluorooxalate borate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and lithium dioxalate borate; the second sodium salt includes one or more of sodium hexafluorophosphate, sodium hexafluorophosphate, sodium tetrafluoroborate, sodium perchlorate, sodium trifluoromethanesulfonate, sodium bis(trifluoromethanesulfonyl)imide, sodium borate, and sodium dioxalate borate; the solid content in the negative electrode solid electrolyte slurry is 0.01 g / mL to 0.5 g / mL; The heating temperature is 100℃~130℃, and the heating time is 1~3 hours; the stirring time is 0.5 hours~24 hours.

9. The preparation method according to claim 6, characterized in that, The active materials of the positive electrode include: spinel-structured lithium nickel manganese oxide, lithium-rich manganese-based materials, olivine-structured lithium manganese phosphate, high-voltage lithium cobalt oxide, nickel-rich layered oxides, and spinel-type LiNi. 0.92 Co 0.04 Mn 0.04 O2, spinel-type LiNi 0.5 Mn 1.5 O4 derivatives, lithium-rich spinel composites, high-voltage sodium ferric sulfate, NASICON-type sodium vanadium phosphate, P2-type layered transition metal oxides, Cu-doped O3-type layered oxides, polyanionic cathode materials, Prussian blue analogs, polyanionic phosphates, Zn-doped P-type layered oxides, magnesium-rich NASICON-type cathode materials, high-potential fluorophosphates, spinel transition metal-doped LiMnO4. x Mn 2-x One or more of O4; wherein M includes one or more of Co, Cr, Ni, Fe, and Cu; The active material of the negative electrode includes: lithium metal or sodium metal.

10. An application of the high-voltage solid-state polymer battery according to any one of claims 1-5, characterized in that, The high-voltage solid polymer battery is used in electric vehicles or energy storage devices.

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