A centrifugal stress-assisted charging and discharging method and apparatus for extending the lifespan of solid-state batteries

Abstract

This invention discloses a centrifugal stress-assisted charging and discharging method and apparatus for extending the lifespan of solid-state batteries, belonging to the field of secondary batteries. The key feature is the application of centrifugal stress during the charging and discharging process of the solid-state battery. The solid-state battery contains an elastomer material, and the centrifugal device includes a motor, a transmission mechanism, and a solid-state battery mounting slot. The centrifugal stress is generated by the motor rotating the battery around a central axis via the transmission mechanism. When fixing the solid-state battery in the centrifugal device, the direction of active ion transport during charging and discharging must be perpendicular to the direction of the centrifugal force. The centrifugal stress applied to the battery elastomer generates tensile stress perpendicular to the electrode surface, causing the elastomer to stretch. This leads to adaptive filling of the pores at the electrode / electrolyte interface, which helps repair contact damage to the electrodes or the electrode / electrolyte interface caused during charging and discharging, thereby extending battery life and increasing battery energy density.

Description

Technical Field

[0001] This invention relates to a charging and discharging method for a secondary battery, and particularly to the application of centrifugal stress during charging and discharging of a solid-state battery and the battery's cycle life, belonging to the field of battery technology. Background Technology

[0002] Lithium metal anodes, with their lowest reduction potential and extremely high theoretical specific capacity, are considered the "ideal anode" in lithium battery systems. All-solid-state lithium batteries, with their higher energy density, superior safety, and stability, are considered the best platform for fully realizing the potential of lithium metal anodes. Despite the promising application prospects of all-solid-state lithium metal batteries, their commercialization still faces significant challenges. According to publicly available data, conventional liquid ternary lithium batteries can achieve a cycle life of over 1500 cycles, and lithium iron phosphate batteries can even exceed 2000 cycles, while planned mass-produced all-solid-state lithium metal batteries currently only achieve 700-800 cycles. Among these challenges, interface failure in all-solid-state lithium metal batteries has become a key bottleneck restricting their development. During discharge, severe porosity appears at the lithium anode interface. When the number and size of these pores reach a certain value, defects within the solid electrolyte (such as grain boundaries and cracks) exacerbate the growth of lithium dendrites. To solve the problem of ion transport failure caused by porosity in all-solid-state lithium metal batteries, research institutions worldwide are actively seeking solutions. In all-solid-state lithium metal batteries, pressurization is an effective and widely used strategy to solve the interfacial contact problem. Its core principle is to increase the physical contact area between the solid electrolyte and the electrodes through mechanical pressure, thereby reducing interfacial impedance, suppressing side reactions, and improving battery performance. Toyota's early all-solid-state battery prototypes used external pressurization, reaching pressures of up to 5 MPa. However, this method increases battery size and weight, making commercialization difficult. Several other institutions have also used similar pressurization methods, but without satisfactory results. Furthermore, while high pressure can improve ion transport and interfacial contact, it can lead to electrolyte fragmentation, electrode deformation, and accelerated lithium dendrite growth; low pressure requires a significant increase in the electrolyte ratio in the electrodes to maintain contact, but the high density of the solid electrolyte severely reduces energy density. This contradiction is even more pronounced in large-scale battery manufacturing.

[0003] Compared to liquid lithium-ion batteries, solid-state batteries suffer from hindered ion transport due to the lack of a transport medium similar to a liquid electrolyte. Patent 2025118025891 proposes a charging and discharging method and apparatus to extend the lifespan of solid-state batteries, finding that applying centrifugal force can improve battery life. However, because the centrifugal force on transported lithium ions is relatively small, a larger centrifugal force is required when the interface porosity is large. Elastomers have significant elasticity, and adding elastomers to solid-state batteries can partially buffer damage occurring at the battery interface. Furthermore, experimental studies on solid-state batteries containing elastomers under centrifugal force revealed tens to hundreds of MPa of tens of Pascals of tens of Pascals of internal stress generated perpendicular to the centrifugal force direction, far exceeding the internal stress of tens of Pascals along the centrifugal force direction. Therefore, this invention proposes a centrifugal stress-assisted solid-state battery charging and discharging method with an elastomer. Utilizing tens to hundreds of MPa of tensile stress generated perpendicular to the centrifugal force direction, a large tensile strain is generated in the elastomer positioned between the electrode and the electrolyte. This allows the elastomer to adaptively and precisely fill the interfacial pores, significantly reducing the transport resistance of active ions at the electrode / electrolyte interface. This enables the active ions to deposit uniformly on the metal negative electrode, suppressing the infiltration growth of metal dendrites in the solid electrolyte module, reducing overvoltage, and thus better preventing battery short circuits. This improves the cycle stability and safety of solid-state batteries, accelerating their application in energy storage and power batteries. Summary of the Invention

[0004] The main objective of this invention is to provide a charging and discharging method and apparatus that uses centrifugal stress to assist in repairing contact damage at the solid-solid interface and extend battery cycle life. During charging and discharging, both the positive and negative electrode layers continuously expand and contract in volume. This volume change causes contact damage such as pores at the electrode / electrolyte interface, leading to dendrite growth and rapid degradation of battery cycle life. Compared to traditional charging and discharging methods, this invention proposes charging and / or discharging the battery in a centrifugal device. By adjusting the orientation of the battery or battery pack within the centrifugal device, a large tensile strain is generated along the direction perpendicular to the battery's electrode surface. This causes the elastomer in the solid-state battery to adaptively fill the interface pores under the drive of tensile stress, thereby reducing the transport impedance of active ions at the solid-solid interface. This solves the problem of ion transport obstruction and rapid degradation of battery cycle life caused by interface pores, extending the cycle life of solid-state metal batteries and battery packs, and thus overcoming the shortcomings of existing technologies. To achieve the aforementioned objective, the technical solution adopted by this invention includes: a centrifugal stress-assisted charging and discharging method and apparatus for extending the life of a solid-state battery, characterized in that: the charging and discharging process of the solid-state battery includes an operation process of applying centrifugal stress to the battery, wherein the centrifugal stress is a tensile stress generated by the battery rotating around a central axis in a direction perpendicular to the centrifugal force, wherein the electrodes of the solid-state battery, and / or the electrolyte, and / or the electrode-electrolyte interface contain an elastomer material, wherein the centrifugal stress-assisted charging and discharging method includes any one of the following methods for applying centrifugal stress during battery charging, and / or during battery discharging, and / or between battery discharging and charging, wherein the apparatus of the centrifugal stress-assisted charging and discharging method includes any one of the following: a centrifugal device and an electrical device, and / or the centrifugal device and a charging device installed together, wherein the operation steps of the centrifugal stress-assisted solid-state battery charging and discharging method include: (1) designing and manufacturing a centrifugal stress-assisted charging and discharging method according to requirements. The device is required to coordinate the control of centrifugation and charging / discharging operations; (2) a solid battery containing an elastomer on the electrode, and / or electrolyte, and / or electrode / electrolyte interface is used as the battery for centrifugation stress-assisted charging and discharging; (3) the battery is fixed or installed in the centrifugation device, requiring that the direction of centrifugation force is not parallel to the direction of active ion transport during charging and / or discharging; (4) a centrifugation stress-assisted charging and discharging method is set, requiring that the battery and centrifuge be fixed together when centrifugation stress is applied, that the battery be connected to the charging pile when charging, that the battery be connected to the electrical equipment when discharging, that the battery and centrifugation device and charging pile are connected separately when centrifugation force is applied and charging are performed simultaneously, and that the battery and centrifugation device and electrical equipment are connected separately when centrifugation force is applied and discharging are performed simultaneously; (5) the parameters for applying centrifugation stress and the parameters for charging or discharging the battery are set, and the charging, or discharging, or charging and centrifugation stress application, or discharging and centrifugation stress application of the battery are started. Further,The aforementioned ability to coordinate the centrifugation and charging / discharging operations refers to the simultaneous transmission of commands via a mode under the same communication protocol, uploading these commands to the battery testing control software and centrifugation operation control software to initiate the battery charging / discharging process. Further, the requirement that the direction of active ion transport during charging and / or discharging is not parallel to the direction of centrifugal force during battery installation means that the centrifuge's central axis is parallel to the electrode surface of the battery's electrode layer, and the angle θ between the vertical direction of the battery's electrode surface and the direction of centrifugal force is 45°≤θ≤90°. (This is repeated twice in the original text.) Furthermore, the requirement that the direction of active ion transport during charging and / or discharging is not parallel to the direction of centrifugal force when the battery is installed in the centrifugal device means that when the battery is installed, the rotation axis of the centrifuge is parallel to the electrode surface of the electrode layer in the battery or in the same plane, and the direction perpendicular to the electrode surface in the battery is perpendicular to the direction of centrifugal force. Furthermore, the requirement that the centrifugal device is fixed together with the electrical device and / or the centrifugal device is fixed together with the charging equipment means that the device for the centrifugal stress-assisted charging and discharging method includes any of the following: the centrifugal device is installed on the electrical device, or the centrifugal device is installed on the charging equipment, or the centrifugal device, the electrical device, and the charging equipment are installed together, or components of the centrifugal device are respectively installed on the electrical device and the charging equipment. The centrifugal device includes a motor, a transmission mechanism that rotates the battery around its central axis, and battery mounting slots arranged in a certain orientation thereon. Furthermore, the centrifugal device components being installed on the power-consuming device and the charging device respectively means that the centrifugal device is disassembled into a centrifugal component consisting of a motor and a centrifugal component consisting of a transmission mechanism and a battery mounting slot, which are respectively installed on the charging device and the power-consuming device. The centrifugal component consisting of the motor is installed together with the charging pile, and the centrifugal component consisting of the transmission mechanism and the battery mounting slot and the solid-state battery are installed on the power-consuming device. The steps of the centrifugal stress-assisted charging and discharging method are as follows: During charging, the motor in the centrifugal charging pile is fixed to the central shaft in the transmission mechanism of the power-consuming device through a rigid connector or a flexible connector, and / or the charging device in the centrifugal charging pile is connected to the battery of the power-consuming device through a conductive ring. The parameters for battery charging and the parameters for applying centrifugal stress are set for charging and / or applying centrifugal stress. After charging is completed, the motor component and the charging component of the centrifugal charging pile are removed from the power-consuming device. During discharging, the battery and the power-consuming device are connected. Furthermore, the centrifugal stress-assisted charging and discharging method includes applying centrifugal stress between discharging and charging, not applying centrifugal stress during charging and discharging, or applying centrifugal stress during charging and not applying centrifugal stress during discharging, or not applying centrifugal stress during charging and applying centrifugal stress during discharging.Alternatively, centrifugal stress may be applied during charging or discharging. Further, the centrifugal stress application parameters are: the rotational speed ω of the motor-driven battery around the central axis is 100–10000 rpm, the distance between the battery and the central axis is 5–100 cm, the applied centrifugal stress is 0.01–50 MPa, and the centrifugal stress application time is 1–60 minutes per cycle. Further, the elastomeric material in the solid-state battery includes any one of the following: elastomeric material disposed between the electrodes and the electrolyte of the solid-state battery, and / or elastomeric material between particles in the electrodes, and / or elastomeric material between particles in the electrolyte, and / or elastomeric material between particles in the electrodes and the electrolyte. Further, the elastomer in the solid-state battery comprises an elastomer material, a plastic crystal, and a lithium salt, wherein the elastomer material contains 50-100 wt%, the plastic crystal contains 0-50 wt%, and the lithium salt contains 0-10 wt%; the elastomer material includes polyether copolymers or blends, polyolefin copolymers or blends, polyurethane copolymers or blends, polyamide copolymers or blends, polysiloxane copolymers or blends, polyacrylate copolymers or blends, polycarbonate copolymers or blends, fluorinated copolymers or blends, and borate copolymers or blends. The copolymer or blend is any one of the following: a blend, a gel-type copolymer, or a blend; the polyolefin copolymer or blend includes any one of polybutadiene, modified polybutadiene, hydrogenated polybutadiene, styrene-ethylene-butene-styrene block copolymer (SEBS), polystyrene-polyisoprene-polystyrene block copolymer (SIS), ethylene propylene diene monomer (EPDM), maleic anhydride-grafted POE, and fluorinated modified POE; the polyacrylate copolymer or blend includes ethyl polyacrylate, butyl polyacrylate, and polyethylene glycol diacrylate type copolymer. The polyether copolymer or blend comprises any one of the following: vinyl chloride copolymer (PEGDA-PVC), methacrylate-type polyethylene glycol methyl ether acrylate copolymer (PMMA-PEGMEA), butyl acrylate-based polydimethylsiloxane (PBA-PDMS), and acrylate-based polydimethylsiloxane (PAA-PDMS), wherein the polyether copolymer or blend includes polyethylene oxide (PEO), PVDF-HFP / PEO, polyether-type polypropylene carbonate copolymer (PPC-PEO), and polyether-type polycaprolactone copolymer (PCL-P). The fluorinated copolymer or blend comprises any one of the following: EO, polyether-type styrene-butadiene-styrene copolymer (SBS-PEO), and polyether-type polyurethane copolymer (PU-PEO); the fluorinated copolymer or blend comprises any one of the following: PTFE modified elastomer, perfluoropolyether, polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), and fluorinated polymer; and the polysiloxane copolymer or blend comprises any one of the following: polydimethylsiloxane (PDMS), fluorosilicone rubber, polyborosiloxane, epoxy-based siloxane, and polyionic liquid polysiloxane.The polyamide copolymers or blends include any one of polyimide (PI), sulfonated polyimide, polyamide amine (PAMAM), polyamide imide (PAI), polyamide epoxy resin (NAEPE), and polyamide-polyether block copolymer (TPAE). The polyurethane copolymers or blends include any one of polyether TPU, fluorinated TPU, polycarbonate polyurethane (PCPU), fluorinated PU / ionic liquid, graphene / PU, phthalic anhydride modified polyurethane, and polyethylene glycol polyurethane (PEG-PU). The borate ester copolymers or blends include any one of epoxy resin-borate ester and cellulose nanocrystal / borate ester composites. The gel copolymers or blends include PVA-based gels, PAN-based organic gels, silicone elastomer gels, and PVDF-HFP / COF composite gels. The material comprises any one of the following: gel, PEO / PMMA interpenetrating network gel, and PAMPS / PAAM dual network gel; the plasticized crystal comprises any one of succinic anionyl (SN), butoxyacetonitrile (SGN), pentaerythritol tetraacetate, N-ethyl-N-methylpyridine di(fluorosulfonyl)imide or N,N-dimethyltetrafluoroborate pyridine, triethylmethyl difluorosulfonylimide, N,N-diethyl-N-methyl-N-(n-propyl)trifluoromethylammonium trifluoroborate, and solid electrolyte; the lithium salt comprises any one of LiTFSI, LiClO4, LiPF6, LiAsF6, LiBF4, LiAlCl4, LiSCN, LiTaF6, LiSnF6, LiGeF6, lithium heteropolyacid salts, LiCF3SO3 and its derivatives, LiN(SO2CF3)2 and its derivatives, and Li2S. xThe solid-state battery comprises any one or a mixture of two or more of the following: lithium salts containing organic polysulfides, fluorine-containing organic lithium salts, or phosphorus-containing organic lithium salts. Further, the all-solid-state battery includes any one of the following: all-solid-state lithium batteries, all-solid-state sodium batteries, all-solid-state lithium-sulfur batteries, all-solid-state sodium-sulfur batteries, and all-solid-state fluorine-ion batteries; the active ions transported in the solid-state battery include any one of lithium ions, sodium ions, and fluorine ions; the negative electrode material of the all-solid-state battery includes any one of metallic lithium, metallic sodium, metallic silicon, metallic silicon / carbon, and metallic phosphorus; the positive electrode active material includes lithium nickel cobalt manganese oxide (NCM), lithium nickel oxide (LNO), lithium manganese oxide (LMO), lithium nickel manganese oxide (LNMO), lithium cobalt oxide (LCO), or lithium nickel cobalt aluminum oxide (NCA) and lithium iron phosphate (LFP). At least one of Na3V2(PO4)3(NVP) and sulfur; the current collector includes at least one of copper, aluminum, nickel, and stainless steel; the inorganic solid electrolyte includes lithium lanthanum zirconium oxide (LLZO), lithium lanthanum zirconium tantalum oxide (LLZTO), lithium lanthanum zirconium niobium oxide (LLZNO), lithium gallium lanthanum zirconium oxide (LGLZO), lithium titanium aluminum phosphate (LATP), lithium germanium aluminum phosphate (LAGP), lithium germanium vanadium oxide (LGVO), lithium germanium phosphorus sulfur (LGPS), and perovskite ABO3, wherein A is one or more of Ca, Sr, and La, and B is one or more of Al and Ti; the sulfide electrolyte includes Li3PS4, Li 5.5 PS 4.5 Cl 1.5 Li7P3S 11 Li 11 GeP2S 12 Li6PS5Cl, Li7P2S8I, Li 1o SnP2S 12 and Li 3.25 Ge 0.25 P 0.75 At least one of S4; the organic solid electrolyte comprises a lithium salt that conducts lithium ions and any one or more combinations of polyether, polyvinyl alcohol, polyethylene oxide, polypropylene oxide, polytetrafluoroethylene, polysiloxane, polyimide, polyurethane, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol formal, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinyl butyral, polyvinyl chloride, sodium carboxymethyl cellulose, and derivatives of perfluorosulfonic acid; the lithium salt comprises LiClO4, LiPF6, LiAsF6, LiBF4, LiAlCl4, LiSCN, LiTaF6, LiSnF6, LiGeF6, lithium heteropolyacid salts, LiCF3SO3 and its derivatives, LiN(SO2CF3)2 and its derivatives, Li2S xThe organic solid electrolyte comprises any one or a mixture of two or more of the following: lithium salts of organic polysulfides, fluorine-containing organic lithium salts, or phosphorus-containing organic lithium salts; and / or, the organic solid electrolyte further comprises molecular sieves, MOF, COF, SiO2, Al2O3, MgO, ZnO, and MnO. x Cu x O, ZrO2, TiO x Ti x C yThe mixture comprises any one or more of BaTiO3, LiAlO2, and lithium fast ion conductors. Further, the method of applying centrifugal stress after discharge and before charging, without applying centrifugal stress during charging and discharging, refers to applying centrifugal stress after discharge and before charging. The operation process is as follows: after discharge and before charging, the battery containing the elastomer is fixed on the centrifugal device, so that the direction perpendicular to the stacked layers in the solid-state battery is perpendicular to the direction of the centrifugal force. The rotation speed ω of the centrifugal device is set to 100–5000 rpm, the distance between the battery and the central axis is 10–50 cm, the applied centrifugal stress is 0.05–20 MPa, and the centrifugal stress application time is 1–60 minutes per cycle. The centrifugal stress application begins. Then connect the positive and negative terminals of the battery to the charging station for charging, and then connect the positive and negative terminals of the battery to the electrical device for discharging; the solid-state battery includes any one of solid-state lithium battery, solid-state sodium battery, solid-state fluorine-ion battery, solid-state lithium-sulfur battery, and solid-state sodium-sulfur battery; the negative electrode of the solid-state battery includes any one of metallic lithium, metallic sodium, metallic silicon, metallic silicon / carbon, and metallic phosphorus; the solid electrolyte material includes surface-coated or uncoated inorganic solid electrolyte and / or organic solid electrolyte; the elastomer in the solid-state battery includes elastomer material, plastic crystal, and lithium salt, which... The elastomer material contains 50-80 wt%, the plastic crystals 20-50 wt%, and lithium salt ≤5 wt%; the elastomer material includes any one of polyether copolymers or blends, polyolefin copolymers or blends, polyurethane copolymers or blends, polyamide copolymers or blends, polysiloxane copolymers or blends, polyacrylate copolymers or blends, polycarbonate copolymers or blends, fluorinated copolymers or blends, borate copolymers or blends, and gel copolymers or blends; the plastic crystals include succinate (SN), butoxyacetonitrile (SGN), pentaerythritol tetraacetate, and N... -Ethyl-N-methylpyridine di(fluorosulfonyl)imide or N,N-dimethyltetrafluoroborate pyridine, triethylmethyldifluorosulfonylimide, N,N-diethyl-N-methyl-N-(n-propyl)trifluoromethylammonium trifluoroborate; the lithium salt includes LiTFSI, LiClO4, LiPF6, LiAsF6, LiBF4, LiAlCl4, LiSCN, LiTaF6, LiSnF6, LiGeF6, heteropolyacid lithium salts, LiCF3SO3 and its derivatives, LiN(SO2CF3)2 and its derivatives, Li2S xThe method involves applying centrifugal stress during charging but not during discharging. This means that there is no centrifugal stress during discharging, and charging is performed in a device that generates centrifugal stress. The operation is as follows: during charging, the positive and negative terminals of the battery are connected to the charging pile. Then, the battery containing the elastic body is fixed on the centrifugal device, ensuring that the direction perpendicular to the electrode layer in the solid-state battery is perpendicular to the direction of the centrifugal force, and that the electrode layer is parallel to or in the same plane as the central axis of rotation. During charging, the rotation speed ω of the centrifugal device is 100–5000 rpm, and the distance between the battery and the central axis of rotation is 5–50 cm. The force is 0.05–20 MPa, and the centrifugal stress application time is 1–60 minutes / cycle. The solid-state battery includes any one of solid-state lithium battery, solid-state sodium battery, solid-state fluorine-ion battery, solid-state sodium-sulfur battery, and solid-state lithium-sulfur battery. The negative electrode of the solid-state battery includes any one of metallic lithium, metallic sodium, metallic silicon, metallic silicon / carbon, and metallic phosphorus. The solid electrolyte material includes inorganic solid electrolyte with or without surface coating, and / or organic solid electrolyte. The elastomer in the solid-state battery includes elastomer material, plastic crystal, and lithium salt, wherein the elastomer material contains 50%–20% lithium salt. 80 wt%, 20-50 wt% of plasticized crystals, and ≤5 wt% of lithium salts; the elastomer material includes any one of polyether copolymers or blends, polyolefin copolymers or blends, polyurethane copolymers or blends, polyamide copolymers or blends, polysiloxane copolymers or blends, polyacrylate copolymers or blends, polycarbonate copolymers or blends, fluorinated copolymers or blends, borate copolymers or blends, and gel copolymers or blends; the plasticized crystals include succinate (SN), butoxyacetonitrile (SGN), pentaerythritol tetraacetate, and N-ethyl-N-methyl The lithium salt comprises any one of the following: pyridine di(fluorosulfonyl)imide or pyridine N,N-dimethyltetrafluoroborate, triethylmethyldifluorosulfonylimide, N,N-diethyl-N-methyl-N-(n-propyl)trifluoromethylammonium trifluoroborate, and solid electrolytes; the lithium salt comprises LiTFSI, LiClO4, LiPF6, LiAsF6, LiBF4, LiAlCl4, LiSCN, LiTaF6, LiSnF6, LiGeF6, lithium heteropolyacid salts, LiCF3SO3 and its derivatives, LiN(SO2CF3)2 and its derivatives, and Li2S. xThe mixture of any one or more of the following: lithium salts of organic ionic polysulfides, fluorine-containing organic lithium salts, or phosphorus-containing organic lithium salts. Furthermore, the method of applying centrifugal stress during charging but not during discharging refers to charging without centrifugal stress, while discharging is performed on a centrifugal device. The operation process is as follows: During discharging, the positive and negative terminals of the battery are first connected to the electrical device. Then, the battery containing the elastomer is solidified on the centrifugal device, with the direction perpendicular to the stacked layers perpendicular to the direction of centrifugal force, and the electrode layers parallel to or in the same plane as the central axis. During discharging, the rotation speed ω of the centrifugal device is 100–5000 rpm, the distance between the battery and the central axis is 5–50 cm, the applied centrifugal stress is 0.05–20 MPa, and the application time is 1–60 minutes per cycle. The solid-state battery includes any one of solid-state lithium batteries, solid-state sodium batteries, solid-state lithium-sulfur batteries, solid-state fluorine-ion batteries, and solid-state sodium-sulfur batteries. The negative electrode of the solid-state battery may include, but is not limited to, any one of metallic lithium, metallic sodium, metallic silicon, metallic silicon / carbon, and metallic phosphorus. The solid electrolyte material includes surface coatings. The solid-state battery may contain an inorganic solid electrolyte or an uncoated solid electrolyte, and / or an organic solid electrolyte. The elastomer in the solid-state battery comprises an elastomer material, a plastic crystal, and a lithium salt, wherein the elastomer material contains 50–80 wt%, the plastic crystal 20–50 wt%, and the lithium salt ≤5 wt%. The elastomer material includes polyether copolymers or blends, polyolefin copolymers or blends, polyurethane copolymers or blends, polyamide copolymers or blends, polysiloxane copolymers or blends, polyacrylate copolymers or blends, and poly... The lithium salt comprises any one of the following: carbonate copolymers or blends, fluorinated copolymers or blends, borate copolymers or blends, and gel copolymers or blends; the lithium salt includes LiTFSI, LiClO4, LiPF6, LiAsF6, LiBF4, LiAlCl4, LiSCN, LiTaF6, LiSnF6, LiGeF6, lithium heteropolyacid salts, LiCF3SO3 and its derivatives, LiN(SO2CF3)2 and its derivatives, and Li2S. xThe mixture of any one or more of the following: lithium salts of organic ionic polysulfides, fluorine-containing organic lithium salts, or phosphorus-containing organic lithium salts. Furthermore, the method of applying centrifugal stress during battery discharge and charging refers to the discharge and charging process being carried out on a centrifugal device. The operation process is as follows: during discharge and charging, the solid-state battery containing an elastomer is fixed on the centrifugal device, so that the direction perpendicular to the stacked layers is perpendicular to the direction of centrifugal force, and the surface of the electrode layer is parallel to or in the same plane as the central axis of rotation. During charging and discharging, the rotation speed ω of the centrifugal device is set to 100-5000 rpm, the distance between the battery and the central axis of rotation is 5-50 cm, the centrifugal stress is applied to 0.05-20 MPa, and the centrifugal stress is applied for 1-60 minutes / cycle, and centrifugal stress-assisted charging and discharging begins. The solid-state battery includes any one of all-solid-state lithium battery, all-solid-state sodium battery, all-solid-state fluorine-ion battery, all-solid-state lithium-sulfur battery, and all-solid-state sodium-sulfur battery. The negative electrode of the solid-state battery includes any one of metallic lithium, metallic sodium, metallic silicon, metallic silicon / carbon, and metallic phosphorus. The solid electrolyte material includes inorganic solid electrolyte with or without surface coating, and / or organic solid electrolyte. The elastomer in the solid-state battery comprises an elastomer material, a plastic crystal, and a lithium salt, wherein the elastomer material contains 50-80 wt%, the plastic crystal 20-50 wt%, and the lithium salt ≤5 wt%; the elastomer material comprises any one of polyether copolymers or blends, polyolefin copolymers or blends, polyurethane copolymers or blends, polyamide copolymers or blends, polysiloxane copolymers or blends, polyacrylate copolymers or blends, polycarbonate copolymers or blends, fluorinated copolymers or blends, borate copolymers or blends, and gel copolymers or blends; the plastic crystal comprises succinate (SN) and butoxyacetonitrile (SGN). The lithium salt comprises any one of the following: pentaerythritol tetraacetate, N-ethyl-N-methylpyridine di(fluorosulfonyl)imide or N,N-dimethyltetrafluoroborate pyridine, triethylmethyldifluorosulfonylimide, N,N-diethyl-N-methyl-N-(n-propyl)trifluoromethylammonium trifluoroborate, and solid electrolytes; the lithium salt comprises LiTFSI, LiClO4, LiPF6, LiAsF6, LiBF4, LiAlCl4, LiSCN, LiTaF6, LiSnF6, LiGeF6, lithium heteropolyacid salts, LiCF3SO3 and its derivatives, LiN(SO2CF3)2 and its derivatives, and Li2S. x The mixture of any one or more of the following: lithium salts of organic ionic polysulfides, fluorine-containing organic lithium salts, or phosphorus-containing organic lithium salts.

[0005] To address the rapid performance degradation of solid-state batteries caused by the volume expansion of electrodes during charging and discharging, this invention provides a charging and discharging method and apparatus that uses centrifugal stress to suppress dendrite growth and extend the cycle life of solid-state batteries. Its advantages and beneficial effects are as follows:

[0006] (1) Centrifugal motion generates tensile stress inside the solid-state battery. Large tensile stress can cause tearing of components within the battery, affecting its performance. Different materials have different tensile strengths; inorganic electrolytes, polymer electrolytes, and elastomers all have tensile strengths exceeding tens of megapascals, while the stretching and contraction of elastomers only requires tensile stresses of a few thousand to a few megapascals. Furthermore, theoretical and experimental studies have shown that tensile stresses of several to tens of megapascals can be generated in the direction perpendicular to the centrifugal force during centrifugal motion. This invention utilizes the tensile stress generated by centrifugation and, through the design of the solid-state battery structure, invents a new method suitable for charging and discharging solid-state batteries and a device for generating centrifugal stress. By setting an elastomer layer on the electrodes, and / or electrolyte, and interface of a solid-state battery, tensile strain is generated within the elastomer under the tensile stress generated by centrifugation. This allows the elastomer to adaptively fill the pores, significantly reducing the transport resistance of active ions at the interface. This enables the active ions to be uniformly deposited on the metal anode, suppressing the infiltration growth of metal dendrites in the solid electrolyte module, reducing overvoltage, and thus better preventing battery short circuits. This improves the cycle stability and safety of solid-state batteries, accelerating the application of all-metal solid-state batteries, especially solid-state metal lithium batteries and sodium batteries, in energy storage and power batteries.

[0007] (2) In addition, solid-state batteries with silicon as the negative electrode also suffer from contact damage. The volume change of the silicon negative electrode during charging and discharging is greater than 300%. The current limited solution is to use silicon / carbon negative electrodes instead of silicon negative electrodes to reduce the volume change of the electrode during charging and discharging. However, the specific capacity of the negative electrode will be greatly reduced at the same time. This invention utilizes charging and / or discharging in a centrifugal device. Introducing an elastomer into the electrode of the solid-state battery helps to buffer the volume change of the electrode during charging and discharging. Centrifugal stress helps to repair the interface contact damage caused by the shrinkage of the negative electrode layer due to discharge, and accelerates the application of silicon negative electrodes in all-solid-state metal batteries.

[0008] (3) Furthermore, in lithium-sulfur batteries, both the lithium anode and the sulfur cathode undergo significant volume changes during charging and discharging. Sulfur expands considerably during charging and discharging, leading to mechanical instability of the cathode. This instability disrupts the conductive network of the cathode, the contact between the sulfur active material and the electrolyte, increases the battery's internal resistance, and reduces overall charging and discharging efficiency. During charging and discharging in a centrifugal device, the elastomer, through adaptive pore filling, helps repair interfacial contact damage caused by the shrinkage of active materials in the electrodes, such as pores, accelerates ion transport at the cathode and anode interface, reduces interfacial impedance, and thus extends the cycle life of the lithium-sulfur metal battery and battery pack. Therefore, introducing an elastomer at the electrode and / or electrolyte interface helps buffer the volume changes of the electrodes during charging and discharging. With the assistance of centrifugal stress, it can simultaneously repair contact damage caused by volume changes at the cathode, anode, and their interface, rapidly improving the performance of the lithium-sulfur metal solid-state battery. Attached Figure Description

[0009] Figure 1 A schematic diagram showing the relationship between the electrode surface direction and the centrifugal force direction of a solid-state battery containing an elastomer negative electrode, where 101-current collector, 102-elastomer negative electrode, 103-solid electrolyte, 104-positive electrode, 105-current collector, 106-rotation center axis, 107-centrifugal force direction, 108-electrode surface direction, and 109-battery casing.

[0010] Figure 2 A schematic diagram showing the relationship between the electrode surface direction and the centrifugal force direction of a solid-state battery containing an elastomer positive electrode, where 201-current collector, 202-metallic negative electrode, 203-solid electrolyte, 204-elastomer positive electrode, 205-current collector, 206-rotation center axis, 207-centrifugal force direction, 208-electrode surface direction, and 209-battery casing.

[0011] Figure 3 A schematic diagram showing the relationship between the electrode surface orientation and the centrifugal force direction of a solid-state battery containing an elastomeric electrolyte, where 301-current collector, 302-metallic negative electrode, 303-elastomeric solid-state electrolyte, 304-positive electrode, 305-current collector, 306-rotation center axis, 307-centrifugal force, 308-electrode surface orientation, and 309-battery casing.

[0012] Figure 4 A schematic diagram showing the relationship between the electrode surface direction and the centrifugal force direction in a solid-state battery with an elastomer positioned at the negative electrode / electrolyte interface. In the diagram, 401 is the current collector, 402 is the metallic negative electrode, 403 is the elastomer, 404 is the electrolyte, 405 is the positive electrode, 406 is the current collector, 407 is the rotation center axis, 408 is the centrifugal force direction, 409 is the electrode surface direction, and 410 is the battery casing.

[0013] Figure 5 A schematic diagram showing the relationship between the electrode surface direction and the centrifugal force direction in a solid-state battery with an elastomer positioned at the positive electrode / electrolyte interface. In the diagram, 501 is the current collector, 502 is the metal negative electrode, 503 is the electrolyte, 504 is the elastomer, 505 is the positive electrode, 506 is the current collector, 507 is the rotation center axis, 508 is the centrifugal force direction, 509 is the electrode surface direction, and 510 is the battery casing.

[0014] Figure 6 A schematic diagram showing the relationship between the electrode surface direction and the centrifugal force direction of a solid-state battery with elastomers used to define the positive, negative, and electrolyte interfaces. In the diagram, 601 is the current collector, 602 is the metal negative electrode, 603 is the elastomer, 604 is the solid electrolyte, 605 is the elastomer, 606 is the positive electrode, 607 is the current collector, 608 is the rotation center axis, 609 is the centrifugal force direction, 610 is the electrode surface direction, and 611 is the battery casing.

[0015] Figure 7A schematic diagram showing the relationship between the electrode surface direction and the centrifugal force direction of a solid-state battery with elastomers respectively disposed at the positive and negative electrode / electrolyte interfaces. Wherein 701-current collector, 702-metal negative electrode, 703-elastomer, 704-solid electrolyte, 705-elastomer positive electrode, 706-current collector, 707-rotation center axis, 708-centrifugal force direction, 709-electrode surface direction, 710-battery casing.

[0016] Figure 8 A schematic diagram showing the relationship between the electrode surface direction and the centrifugal force direction of a solid-state battery with an elastomer positioned at the interface between the negative electrode and the positive electrode / electrolyte. Wherein 801-current collector, 802-elastic metal negative electrode, 803-solid electrolyte, 804-elastic body, 805-positive electrode, 806-current collector, 807-rotation center axis, 808-centrifugal force direction, 809-electrode surface direction, 810-battery casing.

[0017] Figure 9 A schematic diagram of a centrifugal stress-assisted solid-state battery charging device, where 901 is the solid-state battery, 902 is the transmission mechanism, 903 is the rotating shaft, 904 is the motor, and 905 is the charging pile.

[0018] Figure 10 Schematic diagram of a centrifugal stress-assisted solid-state battery charging device, where 1001-solid-state battery, 1002-transmission mechanism, 1003-rotating shaft, 1004-motor, 1005-charging pile, 1006-centrifugal connection port.

[0019] Figure 11 A schematic diagram of a centrifugal stress-assisted solid-state battery discharge device, where 1101 is the solid-state battery, 1102 is the transmission mechanism, 1103 is the rotating shaft, 1104 is the motor, and 1105 is the electrical device.

[0020] Figure 12 Schematic diagram of a centrifugal stress-assisted solid-state battery charging device, where 1201-solid-state battery, 1202-transmission mechanism, 1203-rotating shaft, 1204-motor, 1205-charging pile, 1206-electrical device.

[0021] Figure 13 Cycle life of solid-state batteries subjected to centrifugal stress-assisted charge-discharge, wherein (a) θ = 90°, б = 3 MPa, t = 20 minutes / cycle, (b) θ = 90°, б = 0.05 MPa, t = 20 minutes / cycle, (c) θ = 90°, б = 0.01 MPa, t = 20 minutes / cycle, (d) θ = 45°, б = 3 MPa, t = 20 minutes / cycle, (e) θ = 90°, б = 30 MPa, t = 20 minutes / cycle. Detailed Implementation

[0022] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention. Therefore, the following detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention.

[0023] In the following description of this invention, the term "a~b" means greater than or equal to a and less than or equal to b. For example, the rotational speed ω is a~b revolutions per minute, which means a≤ω≤b; the included angle θ is a~b, which means a≤θ≤b.

[0024] In the following description of this invention, the term "and / or" is used to describe the relationship between associated objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, B existing alone, and A and B existing simultaneously. A and B can be singular or plural.

[0025] The centrifugal stress described in this invention is tensile stress perpendicular to the centrifugal force direction, not the centrifugal force itself. The magnitude of the tensile stress generated by centrifugal motion is related to the direction of the centrifugal force. The magnitude (σ) of the tensile stress perpendicular to the centrifugal force direction (i.e., the linear velocity direction) is proportional to the square of the linear velocity and the density of the material. When the centrifuge speed is 100–10000 rpm and the radius is 5–100 cm, a tensile stress of 0.005–100 MPa can be generated perpendicular to the centrifugal force direction. Its magnitude can reach several hundred megapascals, while the tensile stress along the centrifugal force direction is only a few to tens of pascals—a huge difference. This invention utilizes the tensile stress generated perpendicular to the centrifugal force direction as the driving force for repairing battery interface damage.

[0026] Different materials have different tensile strengths. Inorganic electrodes and electrolytes can generally withstand tens to hundreds of megapascals of tensile stress, polymer electrolytes and elastomers can withstand several to tens of megapascals of tensile stress, and micron-sized metal anode films can withstand tens of megapascals of tensile stress, while their alloys, such as Li-B and Li-In alloys, can withstand tens of megapascals of tensile stress. This invention selects a tensile stress between 0.005 and 30 MPa as the auxiliary tensile stress for battery charging and discharging. This value is less than the tensile strength of the battery elements and the elastomers included in the battery, ensuring the safety of the solid-state battery during charging and discharging in a centrifugal device.

[0027] Elastomers are reversible or viscoelastic materials that exhibit large strain under stress. The elastomers described in this invention include pure elastomers and elastomers with added plastic crystals, lithium salts, and additives. The tensile strength and ionic conductivity of the elastomer can be adjusted by adding plastic crystals and lithium salts to the elastomer material. Unlike electrodes and electrolytes, elastomers can produce large tensile deformations under the same tensile stress, with deformations exceeding 100%. This invention employs a centrifugal stress-assisted adaptive elastomer as the ion transport medium in the battery. Centrifugal stress is used to regulate the adaptive filling of the elastomer at the electrode / electrolyte interface, unblocking ion transport at the interface and thereby extending the battery's cycle life.

[0028] Methods for setting elastomeric materials in solid-state batteries include any one or a combination of elastic buffer layers set between the electrodes and electrolyte, elastomeric materials between particles in the electrodes, elastomeric materials between particles in the electrolyte, and elastomeric materials between particles in the electrodes and electrolyte. Since the tensile stress generated perpendicular to the centrifugal force direction (i.e., the linear velocity direction) is the greatest during centrifugal motion, the direction of active ion transport must be in the direction of the linear velocity of the centrifugal motion when the battery is installed in a centrifugal device. The centrifugal stress along the active ion transport direction is greatest when the electrode surface direction is perpendicular to the centrifugal force direction. Figure 1 This diagram illustrates the relationship between the electrode surface orientation and the centrifugal force direction in a solid-state battery containing an elastomer negative electrode. The current collector 101, the elastomer-containing metal negative electrode 102, the solid electrolyte 103, the positive electrode 104, the current collector 105, and the battery casing 109 are all shown. 106 is the rotation axis, and both the current collector and the electrode surface are perpendicular to the plane of the paper. 108 represents the electrode surface orientation, and the angle θ between it and the centrifugal force direction 107 is: 60 < θ ≤ 90°, with 90° being preferred. The tensile stress is greatest when θ = 90°. Figure 2 This diagram illustrates the relationship between the electrode surface orientation and the centrifugal force direction in a solid-state battery containing an elastomer positive electrode. The current collector 201, metal negative electrode 202, solid electrolyte 203, elastomer-containing positive electrode 204, current collector 205, and battery casing 209 are shown. 206 is the rotational axis of the centrifugal device, and both the current collector and the electrode layer surfaces are perpendicular to the plane of the paper. 208 represents the electrode surface orientation, and the angle θ between it and the centrifugal force direction 207 is: 60 < θ ≤ 90°, with 90° being preferred. Figure 3 This diagram illustrates the relationship between the electrode surface orientation and the centrifugal force direction in a solid-state battery containing an elastomer solid electrolyte. The current collector 301, metal negative electrode 302, elastomer solid electrolyte 303, positive electrode 304, current collector 305, and battery casing 309 are shown. 306 is the rotational axis of the centrifugal device, and both the current collector and the electrode layer surfaces are perpendicular to the plane of the paper. 308 represents the electrode surface orientation, and the angle θ between it and the centrifugal force direction 307 is: 60 < θ ≤ 90°, with 90° being preferred. Figure 4This diagram illustrates the relationship between the electrode surface orientation and the centrifugal force direction in a solid-state battery where an elastomer buffer layer is positioned at the negative electrode / electrolyte interface. The components include a current collector 401, a metal negative electrode 402, an elastomer layer 403, a solid electrolyte 404, a positive electrode 405, a current collector 406, and a battery casing 410. 407 is the rotation axis, and both the axis and the electrode layer surface are perpendicular to the plane of the paper. 409 represents the electrode surface orientation, and the angle θ between this orientation and the centrifugal force direction 408 is 60° < θ ≤ 90°, with 90° being preferred. Figure 5 This diagram illustrates the relationship between the direction of the electrode surface and the direction of centrifugal force in a solid-state battery where an elastomer buffer layer is positioned at the positive electrode / electrolyte interface. The components include a current collector 501, a metal negative electrode 502, a solid electrolyte 503, an elastomer layer 504, a positive electrode 505, a current collector 506, and a battery casing 510. 507 is the rotation axis, and both the axis and the surface of the electrode layer are perpendicular to the plane of the paper. 509 represents the direction of the electrode surface, and the angle θ between this direction and the centrifugal force direction 508 is 60° < θ ≤ 90°, with 90° being preferred. Figure 6 This diagram illustrates the relationship between the electrode surface orientation and the centrifugal force direction in a solid-state battery containing an elastomer buffer layer disposed at the interfaces of the positive, negative, and electrolyte electrodes. 601-current collector, 602-negative electrode, 603-elastomer, 604-solid electrolyte, 605-elastomer, 606-positive electrode, 607-current collector, 611-battery casing. 608 is the motor shaft, and both its surface and the electrode layer surface are perpendicular to the paper. 610 represents the electrode surface orientation, and the angle θ between it and the centrifugal force direction 609 is: 60 < θ ≤ 90°, where 90° is preferred. Figure 7 This diagram illustrates the relationship between the electrode surface direction and the centrifugal force direction in a solid-state battery where an elastomer buffer layer is positioned in the positive electrode and at the negative electrode / electrolyte interface. The components include a current collector 701, a metal negative electrode 702, an elastomer layer 703, a solid electrolyte 704, an elastomer-containing positive electrode 705, a current collector 706, and a battery casing 710. 707 is the rotation axis, and both the axis and the surface of the electrode layer are perpendicular to the paper. 709 represents the electrode surface direction, and the angle θ between this direction and the centrifugal force direction 708 is 60° < θ ≤ 90°, with 90° being preferred. Figure 8 This diagram illustrates the relationship between the direction of the electrode surface and the direction of centrifugal force in a solid-state battery where an elastomer buffer layer is positioned in the negative electrode and at the positive electrode / electrolyte interface. The battery consists of a current collector 801, an elastomer-containing metal negative electrode 802, a solid electrolyte 803, an elastomer layer 804, a positive electrode 805, a current collector 806, and a battery casing 810. 807 is the rotation axis, and both the axis and the surface of the electrode layer are perpendicular to the plane of the paper. 809 represents the electrode surface direction, and the angle θ between this angle and the centrifugal force direction 808 is: 60 < θ ≤ 90°, where 90° is preferred.

[0029] In addition, the charging and discharging methods on the centrifugal device include any one of the following: applying centrifugal force between charging and discharging, applying centrifugal force during charging and not applying centrifugal force during discharging, not applying centrifugal force during charging and applying centrifugal force during discharging, or applying centrifugal force during charging and applying centrifugal force during discharging. Figure 9 This is a schematic diagram of a centrifugal stress-assisted solid-state battery charging device, where 901 is the solid-state battery, 902 is the transmission mechanism, 903 is the central rotating shaft, 904 is the motor, and 905 is the charging pile. The operation process, which applies centrifugal force during charging and does not apply centrifugal force during discharging, is as follows: Before charging begins, the stacked battery 901 can... Figure 1-8 One of the installation requirements is to fix it in Figure 9 The battery 901 and the charging pile 905 are connected to the transmission mechanism 902 of the rotating device. Then, the charging and centrifuge parameters are set to charge the device. Figure 10 This is a schematic diagram of a centrifugal stress-assisted solid-state battery separate charging device, where 1001 is the solid-state battery, 1002 is the transmission mechanism, 1003 is the central rotating shaft, 1004 is the motor, 1005 is the charging pile, and 1006 is the centrifugal interface. The centrifuge is divided into two parts: the transmission mechanism, solid-state battery, and electrical device are fixed together, while the motor and charging pile are fixed together. The operation process, which applies centrifugal force during charging and does not apply centrifugal force during discharging, is as follows: the stacked battery 1001 can... Figure 1-8 One of the installation requirements is to fix it in Figure 10 The rotating device is connected to the transmission mechanism 1002. During charging, the battery 1001 and the charging pile 1005 are connected, and the motor 1004 is connected to the transmission mechanism 1002 via the centrifugal interface 1006. Then, the charging and centrifuge parameters are set to charge the device. Figure 11 This is a schematic diagram of a centrifugal stress-assisted solid-state battery discharge device, where 1101 is the solid-state battery, 1102 is the transmission mechanism, 1103 is the central rotating shaft, 1104 is the motor, and 1105 is the electrical device. The operation process, which involves charging without applying centrifugal force and discharging with centrifugal force, is as follows: the stacked battery 1101 can... Figure 1-8 One of the installation requirements is to fix it in Figure 11 The rotating device is connected to the transmission mechanism 1102. During discharge, the battery 1101 and the electrical device 1105 are connected, and then the discharge and centrifugal stress parameters are set to discharge. Figure 12 This is a schematic diagram of a centrifugal stress-assisted solid-state battery charging and discharging device, where 1201 is the solid-state battery, 1202 is the transmission mechanism, 1203 is the central rotating shaft, 1204 is the motor, 1205 is the charging pile, and 1206 is the electrical device. The operation process of applying centrifugal force during charging and discharging is as follows: the solid-state battery 1201... Figure 1-8 The installation requirements of any of them must be installed in Figure 12In the centrifugal device shown, during charging, the battery 1201 and the charging pile 1205 are connected, and then the centrifugal stress parameters and charging parameters are set for charging; during discharging, the battery 1201 and the power device 1206 are connected, and then the centrifugal stress parameters and discharging parameters are set to start discharging.

[0030] This invention employs charge-discharge testing in a centrifuge apparatus. Figure 12 The charging and discharging method shown herein allows the device to be used for research on centrifugal stress-assisted charging and discharging in different modes. In some specific embodiments, charging and discharging test results for installation parameters and centrifugal stress parameters are disclosed. The elastomer in the solid-state battery can be, but is not limited to, any one or more of the following: positive electrode layer, electrolyte layer, negative electrode layer, negative electrode and electrolyte interface layer, and positive electrode and electrolyte interface layer. The angle θ between the electrode surface direction and the centrifugal force direction can be, but is not limited to, any one of 45°≤θ≤90°. The electrode rotation speed can be, but is not limited to, any one of 100–10000 rpm, preferably 500–4000 rpm. The centrifugal stress can be, but is not limited to, 0.01–50 MPa, preferably 0.05–10 MPa. In practical applications, the centrifugal stress is first pre-set based on the yield strength of the elastomer material; preferably, the pre-set value of the centrifugal stress is less than 80% of the elastomer's yield strength. Then, the parameters for centrifugal stress-assisted charging and discharging of the solid-state battery containing the elastomer are further determined experimentally. The test apparatus used in Examples 1-12 of this embodiment (such as...) Figure 12 The rotation radius is set to 25 cm, and the magnitude of its centrifugal stress is calculated from the rotation angular velocity and radius. Figure 13 Cyclic performance of LiNbO3-NCM811||LSPSC1||Li-In all-solid-state batteries under centrifugal stress-assisted charge-discharge conditions: (a) θ=90°, б=3MPa, t=20 min / cycle; (b) θ=90°, б=0.05MPa, t=20 min / cycle; (c) θ=90°, б=0.01MPa, t=20 min / cycle; (d) θ=45°, б=3MPa, t=20 min / cycle; (e) θ=90°, б=30MPa, t=20 min / cycle.

[0031] The solid-state battery described in this invention is either a single cell or a battery pack, and is a solid-state battery containing an elastomer. In some specific embodiments, the elastomer of the solid-state metal battery may include, but is not limited to, any one of a pure elastomer and an elastomer composed of an elastomer material, a plastic crystal, and a lithium salt, wherein the elastomer contains 50-70 wt%, the plastic crystal 30-50 wt%, and the lithium salt ≤5 wt%; the elastomer material includes polyether copolymers or blends, polyolefin copolymers or blends, polyurethane copolymers or blends, polyamide copolymers or blends, polysiloxane copolymers or blends, polyacrylate copolymers or blends, polycarbonate copolymers or blends, and fluorine-based copolymers or blends. The copolymer or blend, borate ester copolymer or blend, gel copolymer or blend; in some specific embodiments, methacrylate-polyethylene glycol methyl ether acrylate copolymer (PMMA-PEGMEA), polyether-type polypropylene carbonate copolymer (PPC-PEO), polyether-type polycaprolactone copolymer (PCL-PEO), PVDF-HFP / PEO, polyether-type styrene-butadiene-styrene copolymer (SBS-PEO), and polyether-type polyurethane copolymer (PU-PEO) are listed as elastomers, but are not limited thereto.

[0032] When centrifugal force is applied, the tensile stress generated by the elastic layer at the interface under centrifugal stress is between 0.05 and 10 MPa. Within the elastic strain range of the elastomer, the elastomer at the interface is expanded and fills the pores at the electrode / electrolyte interface, such as... Figure 1-8 The centrifugal stress acts on the elastic layer of the solid-state battery; therefore, solid-state batteries containing elastomers are all within the scope of protection of this invention. In some specific embodiments, the solid-state metal battery may include, but is not limited to, any of the following: solid-state lithium-ion batteries, solid-state sodium-ion batteries, solid-state lithium-sulfur batteries, solid-state sodium-sulfur batteries, and solid-state fluorine-ion batteries. Examples include, for instance, NCM811||LSPSCl||Li-In solid-state lithium batteries, SON-μSi||LSPSCl||NMC811 silicon anode solid-state lithium batteries, Na3V2(PO4)3-rGO||NLZSP-NBO(3wt%)||Na solid-state sodium batteries, Na||PEO-NaPF6[|Na3V2(PO4)3 solid-state sodium batteries, and P-SP-Sb-LPSC. 1.5 ||LPSC 1.5 ||LCO phosphorus anode solid-state lithium battery, S-SP||LSiPSI||Li solid-state lithium-sulfur battery, SPAN||Li6PS5Cl 0.5 Br 0.5 ||Li solid-state lithium-sulfur batteries and Na||PEO-NaTFSI-ZnCo-MOF||S-SP solid-state sodium-sulfur batteries, but not limited to these.

[0033] Currently reported commercial solid-state batteries have a cycle life of at most a few hundred cycles, with very few exceeding 2000 cycles. At 2000 cycles, the battery life can reach over 10 years. Therefore, in this invention, battery cycle life is characterized by the battery capacity retention rate after 2000 cycles. Table 1 lists the charge-discharge test results of the batteries in Examples 1-12 in a centrifugal apparatus. Examples 1-5 mainly characterize the effects of centrifugal force parameters and battery mounting orientation on battery life, such as the angle between the vertical direction of the electrode surface and the direction of centrifugal force, and the magnitude of centrifugal stress. Examples 6-12 list the charge-discharge performance tests of different solid-state batteries in a centrifugal apparatus, including all-solid-state metal batteries and solid-state metal-sulfur batteries.

[0034] The comparative examples and embodiments of the present invention use the same battery manufacturing process, differing only in the elastomer, charging / discharging method, and apparatus. In some embodiments, the preparation methods for the electrodes and electrolytes may include, but are not limited to, wet and dry methods. The following will further explain and illustrate this technical solution, its implementation process, and its principles:

[0035] Comparative Example 1

[0036] Comparative Example 1 is an NCM811||LSPSC1||Li-In all-solid-state battery. In Comparative Example 1, NCM811 active material, Super-P conductive carbon black, and polyvinylidene fluoride (PVDF) binder were first mixed in a heated mortar at a weight ratio of 85:10:5, and then subjected to high-speed shearing and rolling to obtain an NCM811 single-sided positive electrode sheet using a composite aluminum foil current collector. Then, a 5nm thick LiNbO3 protective film was grown on the NCM811 single-sided positive electrode sheet using atomic layer deposition, resulting in a LiNbO3-coated NCM811 single-sided positive electrode sheet. Additionally, LSPSC1 (Li... 10 Si 0.3 PS 6.7 Cl 1.8 LiNbO3-NCM811||LSPSC1||LiIn solid-state battery was prepared by repeatedly hot-rolling a mixture of LiNbO3-coated NCM811 positive electrode, LSPSC1 solid-state electrolyte membrane, Li-In negative electrode, and copper foil in a heated mortar at a weight ratio of 99.5:0.5. The mixture was then used for battery assembly. A pressure of 350 MPa was applied and maintained for 5 minutes to complete the assembly of the all-solid-state battery, LiNbO3-NCM811||LSPSC1||LiIn. The assembled battery was fixed with a steel frame and charged and discharged under a pressure of 150 MPa. Under 3C high-current conditions, the initial capacity reached 170.0 mAh g. -1 After 500 cycles, the capacity retention rate is as high as 94.5%.

[0037] Example 1

[0038] The preparation method of the NCM811||LSPSC1||LiIn solid-state battery in Example 1 is basically the same as that of the comparative examples above. The difference is that in Example 1, an elastomer composed of PPC-PEO, SN, and LiTFSI with contents of 60%, 35%, and 5% respectively is set between the electrolyte and the negative electrode, and it is required that... Figure 12 Solid-state battery charging and discharging were performed in a centrifuge apparatus. The PPC-PEO elastomer was prepared using a solution blending method, where PPC-PEO, SN, and LiTFSI were mixed and dissolved in acetonitrile at a weight ratio of 60:35:5, and then vacuum dried at 80°C to allow the solvent to evaporate and form a film. First, a LiNbO3-coated NCM811 positive electrode, an LSPSC1 solid electrolyte membrane, a PPC-PEO elastomer membrane, and a Li-In negative electrode were sequentially added to a pressure mold. Copper foil was placed as a current collector, and a pressure of 10 MPa was applied and maintained for 5 minutes to complete the assembly of the all-solid-state battery LiNbO3-NCM811||LSPSC1||LiIn. Figure 4 The diagram shows the relationship between the electrode surface direction and the centrifugal force direction of a solid-state battery with an elastomer at the interface between the negative electrode and the electrolyte. The angle θ between the vertical direction of the electrode surface and the centrifugal stress is adjusted to 90°. The battery is then installed... Figure 12 The battery was charged and discharged using a centrifugal device. A charging mode was employed where centrifugal force was applied during charging but not during discharging. The charging station was connected to the positive and negative terminals of the battery. During charging, the motor speed in the centrifugal device was set to 1000–4000 rpm, the radius to be 25 cm, the centrifugal tensile stress to be 3 MPa, and the centrifugal stress application time to be 20 minutes per cycle. During discharging, no centrifugal force was applied. Based on this charging and discharging process, battery performance was tested. The results showed that under 3C high-current conditions, the initial capacity could reach 190.5 mAh / g. -1 After 2000 cycles, the capacity retention rate reached 98.5%, as shown in the results. Figure 13 (a).

[0039] Example 2

[0040] Example 3 also relates to the study of LiNbO3-NCM811||LSPSC1||LiIn single-cell batteries. The fabrication method is the same as in Example 1, except that the charge / discharge parameters in Example 2 are as follows: during battery installation, the angle between the electrode surface direction and the centrifugal force direction is 90°. The centrifugal tensile stress during charging is set to 0.05 MPa, and the centrifugal stress application time is 20 minutes / cycle; during discharging, no centrifugal force is applied. The test results using the above charge / discharge process show that under 3C high current conditions, the initial capacity can reach 188.6 mAh g. -1 After 2000 cycles, the capacity retention rate reached 76.8%, as shown in the results. Figure 13 (b)

[0041] Example 3

[0042] Example 3 also relates to the study of a LiNbO3-NCM811||LSPSC1||LiIn single-cell battery. The fabrication method is the same as in Example 1, except that the charge / discharge parameters for Example 3 are as follows: during battery installation, the angle between the electrode surface direction and the centrifugal force direction is 90°. During charging, the centrifugal tensile stress is set to 0.01 MPa, and the centrifugal stress application time is 20 minutes / cycle; during discharging, no centrifugal force is applied. Tests were conducted according to the above charge / discharge process, and the results showed that under 3C high-current conditions, the initial capacity can reach 189.0 mAh / g. -1 After 2000 cycles, the capacity retention rate reached 69.4%, as shown in the results. Figure 13 (c)

[0043] Example 4

[0044] Example 4 also relates to the study of a LiNbO3-NCM811||LSPSCl||LiIn single-cell battery. The fabrication method is the same as in Example 1, except that the charge / discharge parameters for Example 4 are as follows: during battery installation, the angle between the electrode surface direction and the centrifugal force direction is 90°. The centrifugal tensile stress is set to 30 MPa during charging, and the centrifugal stress application time is 20 minutes per cycle; during discharging, no centrifugal force is applied. Tests were conducted according to the above charge / discharge process, and the results showed that under 3C high-current conditions, the initial capacity can reach 188.0 mAh / g. -1 After 2000 cycles, the capacity retention rate reached 49.5%, as shown in the results. Figure 13 (e).

[0045] Example 5

[0046] Example 5 also relates to the study of a LiNbO3-NCM811||LSPSCl||LiIn single-cell battery. The fabrication method is the same as in Example 1, except that the charge / discharge parameters in Example 5 are as follows: during battery installation, the angle between the electrode surface direction and the centrifugal force direction is 45°. The centrifugal tensile stress is set to 3 MPa during charging, and the centrifugal stress application time is 20 minutes per cycle; during discharging, no centrifugal force is applied. The test results using the above charge / discharge process show that under 3C high current conditions, the initial capacity can reach 189.3 mAh g. -1 After 2000 cycles, the capacity retention rate reached 56.8%, as shown in the results. Figure 13 (d)

[0047] Example 6

[0048] Example 6 is a SON-μSi||LSPSC1||NMC811 all-solid-state battery with silicon as the negative electrode. In the preparation of the SON-μSi||LSPSC1||NMC811 all-solid-state battery in this comparative example, the SON-μSi negative electrode sheet is composed of Si and SiOx (0 < x < 1), which is formed by oxidizing nanosilicon in oxygen to form nanosilicon with a surface coating of silicon monoxide, and then repeatedly hot-rolling to obtain, and is used for battery assembly. The NCM811 positive electrode film is composed of NCM811, LSPSCl (Li 10 Si 0.3 PS 6.7 Cl 1.8 ), VGCF and PTFE are mixed in a heated mortar at a weight ratio of 70:20:3:0.5 respectively, and repeatedly hot-rolled to obtain. The solid-state electrolyte film is composed of LSPSCl (Li 10 Si 0.3 PS 6.7 Cl 1.8 ) and PTFE are mixed in a heated mortar at a mass ratio of 99.5:0.5 to form a thin sheet. Subsequently, the solid-state electrolyte film is repeatedly hot-rolled to the required thickness and stamped into a suitable size for battery assembly. In the pressure die, the SON-μSi negative electrode material, LSPSC1 solid-state electrolyte, and the positive electrode material NCM811 are sequentially added, and a copper foil is placed as the current collector. An external pressure of 350 MPa is applied and maintained for 5 minutes to complete the assembly of the all-solid-state battery SON-μSi||LSPSC1||NMC811. The assembled battery is charged and discharged under a high current condition of 2C, and the initial capacity can reach 180 mAhg -1 . After 500 long cycles, the capacity retention rate of the battery can still reach 81%. After 1000 cycles, the capacity retention rate is 78%.

[0049] The preparation method of the SON-μSi||LSPSCl||NMC811 solid-state battery in Example 6 is basically the same as that of the comparative example, except that 60wt% PMMA-PEGMEA + 35wt% SN + 5wt% LiTFSI elastomer is provided in the negative electrode, and the solid-state battery of this invention is charged in a centrifuge device. The silicon negative electrode containing the elastomer is prepared by solution casting. PMMA-PEGMEA, SN and LiTFSI are weighed in a weight ratio of 60:35:5 and dried. First, PMMA-PEGMEA is dissolved in acetonitrile solvent, then SN and LiTFSI lithium salt are added, and finally, 50% by mass of silicon monoxide-coated nano-silicon powder is added. After mixing evenly, the solution is poured into a mold to form a film, and then dried at 60°C. In a pressure mold, a SON-μSi negative electrode containing PMMA-PEGMEA elastomer, an LSPSC1 solid electrolyte, and an NCM811 positive electrode are sequentially added. Copper foil is placed as a current collector, and a pressure of 10 MPa is applied externally and maintained for 5 minutes to complete the assembly of the all-solid-state battery SON-μSi||LSPSC1||NMC811. Then, according to... Figure 1 In the negative electrode, the relationship between the electrode surface direction and the centrifugal force direction of the solid-state battery with the elastomer is set. The angle θ between the electrode surface direction and the centrifugal force is adjusted to 90°, and the battery is installed... Figure 12 The device was used for centrifugation. A charging / discharging mode was selected where centrifugal force was applied during charging and not during discharging. During charging, the charging station was connected to the positive and negative terminals of the battery, the centrifugal tensile stress was set to 5 MPa, and the centrifugal stress was applied for 30 minutes per cycle; during discharging, no centrifugal force was applied. The test results using the above charging / discharging process were as follows: the initial charge capacity at a 2C rate was 190 mAh·g. -1 At a 2C rate, it can be stably cycled for 2000 cycles with a capacity retention of approximately 95.5%, as shown in Table 1.

[0050] Example 7

[0051] This embodiment is a Na3V2(PO4)3-rGO||NLZSP-NBO(3wt%)||Na solid-state battery with sodium metal as the negative electrode. The preparation method of the comparative example is as follows: the NLZSP-NBO(3wt%) solid electrolyte sheet is made from Na… 3.3 La 0.3 Zr 1.7 Si2PO 12To prepare the Na3V2(PO4)3 positive electrode, 3wt% Na2B4O7(NBO) sintering aid was added to (NLZSP) powder. After uniform mixing, the mixture was kept at 900℃ and 50MPa pressure in a graphite mold for 8 hours. The Na3V2(PO4)3 positive electrode was prepared by uniformly mixing Na3V2(PO4)3 powder with 1% polytetrafluoroethylene (PTFE) binder and 1% rGO conductive agent, and then repeatedly rolling it with aluminum foil current collector. In a pressure mold, the Na3V2(PO4)3-rGO positive electrode, NLZSP-NBO (3wt%) solid electrolyte, and sodium metal negative electrode were added sequentially. A copper foil current collector was placed on top, and an external pressure of 150MPa was applied and maintained for 5 minutes to complete the assembly of the all-solid-state battery Na3V2(PO4)3-rGO||NLZSP-NBO(3wt%)||Na. The comparative charge-discharge test results showed that under 1C high current conditions, the initial capacity could reach 115mAhg. -1 After 200 cycles, the capacity retention rate is as high as 91%.

[0052] The preparation method of the Na3V2(PO4)3-rGO||NLZSP-NBO||Na solid-state battery in Example 7 is basically the same as the preparation method of the comparative examples above. The difference is that the Na3V2(PO4)3-rGO||NLZSP-NBO||Na solid-state metallic sodium battery in Example 5 of this invention is charged and discharged in the following ways: Figure 12 The process was carried out in a centrifuge apparatus, using a 70wt% PU-PEO + 25wt% SN + 5wt% LiTFSI elastomer, positioned at the interface between the negative electrode and the electrolyte. The elastomer was prepared using a solution casting method. PU-PEO, SN, and LiTFSI were weighed in a weight ratio of 70:25:5 and dried. PU-PEO was first dissolved in acetonitrile solvent, then SN and LiTFSI lithium salt were added and mixed thoroughly. The solution was then poured into a mold to form a film, which was then dried at 60-80℃. In a pressure mold, a Na3V2(PO4)3-rGO positive electrode, NLZSP-NBO (3wt%) solid electrolyte, PU-PEO elastomer, and sodium metal negative electrode were sequentially added, followed by a copper foil current collector. A pressure of 10MPa was applied externally and maintained for 5 minutes to complete the assembly of the all-solid-state battery Na3V2(PO4)3-rGO||NLZSP-NBO(3wt%)||Na. Figure 4 The diagram shown illustrates the relationship between the electrode surface direction and the centrifugal force direction of a solid-state battery with an elastomer at the interface between the negative electrode and the electrolyte. The angle θ between the electrode surface direction and the centrifugal force is adjusted to 90°, and the battery is then installed... Figure 12The battery was charged and discharged using a centrifugal device. A charging mode was employed where centrifugal force was applied during charging but not during discharging. The charging station was connected to the positive and negative terminals of the battery. During charging, the centrifugal tensile stress was set to 2 MPa, and the stress was applied for 60 minutes per cycle. During discharging, no centrifugal force was applied. Based on this charging and discharging process, battery performance was tested. The test results showed that under a 1C high-current condition, the initial capacity reached 117 mAh / g. -1 After 2000 cycles, the capacity retention rate reached 97.5%, as shown in Table 1.

[0053] Example 8

[0054] Example 8 is a Na||PEO-NaPF6||Na3V2(PO4)3 all-solid-state battery with sodium metal as the negative electrode. Unlike Example 7, its electrolyte is a PEO-NaPF6 polymer electrolyte. The preparation method for the comparative example is as follows: The Na3V2(PO4)3 positive electrode sheet was prepared by mixing Na3V2(PO4)3, Super P, and polyacrylic acid in a mortar at a weight ratio of 7:2:1. A suitable amount of NMP solvent was then added, and the mixture was ground for 30 minutes to obtain a uniform Na3V2(PO4)3 positive electrode slurry. This slurry was then evenly coated onto the surface of aluminum foil using a scraper and baked in a vacuum drying oven at 60°C for 24 hours. The PEO-NaPF6 polymer solid electrolyte sheet was prepared using a solution casting method, with PEO and NaPF6 mixed in a ratio of EO / Na... + A mixture with a molar ratio of 20 / 1 was added, and anhydrous acetonitrile was added. The mixture was then stirred at 50°C for 10 hours. The resulting homogeneous solution was poured into a polytetrafluoroethylene (PTFE) mold and allowed to stand in a glove box for 24 hours to allow the acetonitrile solvent to evaporate naturally. The resulting polymer film was then rapidly transferred to an oven and vacuum dried at 55°C for 24 hours to completely remove the acetonitrile solvent. Finally, the dried polymer film was transferred to a glove box for later use. In a pressure mold, Na3V2(PO4)3 positive electrode material, PEO-NaPF6 solid electrolyte, and sodium metal negative electrode were added sequentially. Aluminum foil was placed as the current collector. A pressure of 370 MPa was applied externally and maintained for 5 minutes to complete the assembly of the all-solid-state battery Na||PEO-NaPF6||Na3V2(PO4)3. Comparative charge-discharge tests were conducted at 80°C, and the test results showed that the initial discharge specific capacity was 115 mAh g⁻¹. -1 After 200 cycles at a 5C rate, the capacity retention was 85%, as shown in Table 1.

[0055] The preparation method of the Na||PEO-NaPF6||Na3V2(PO4)3 solid-state battery in Example 8 is basically the same as that of the comparative examples above. The difference is that the charging and discharging of the Na||PEO-NaPF6||Na3V2(PO4)3 all-solid-state metallic sodium battery of the present invention is carried out in a centrifuge device, and a 60wt% PCL-PEO+35wt% SN+5wt% LiTFSI elastomer is placed between the electrolyte and the negative electrode. The 60wt% PCL-PEO+35wt% SN+5wt% LiTFSI elastomer is prepared by solution blending. PCL-PEO, SN and LiTFSI are mixed and dissolved in acetonitrile at a weight ratio of 60:35:5, and dried under vacuum at 60-80℃. After the solvent evaporates, a film is formed. In a pressure mold, Na3V2(PO4)3 positive electrode material, PEO-NaPF6 solid electrolyte, PCL-PEO elastomer, and sodium metal negative electrode sheet are added sequentially. Aluminum foil is placed as a current collector, and a pressure of 10 MPa is applied externally and maintained for 5 minutes to complete the assembly of the all-solid-state battery Na||PEO-NaPF6||Na3V2(PO4)3. Figure 4 The diagram shown illustrates the relationship between the electrode surface direction and the centrifugal force direction of a solid-state battery with an elastomer at the interface between the negative electrode and the electrolyte. The angle θ between the electrode surface direction and the centrifugal force is adjusted to 90°, and the battery is then installed... Figure 12 On a centrifuge apparatus. The centrifugal stress-assisted charge / discharge method was used, applying centrifugal force during discharge and not applying centrifugal force during charging. The centrifugal tensile stress during discharge was set to 2 MPa, and the centrifugal stress application time was 12 minutes / cycle. The results showed that under 5C high current conditions at 85℃, the initial capacity could reach 120.0 mAh g. -1 After 2000 cycles, the capacity retention rate is as high as 90.5%, as shown in Table 1.

[0056] Example 9

[0057] This embodiment uses P-SP-Sb-LPSC with metallic phosphorus as the negative electrode. 1.5 ||LPSC 1.5 ||LCO all-solid-state metal battery. In its comparative example, P / SP-Sb-LPSC 1.5 ||LPSC 1.5 The preparation method of LCO all-solid-state battery is as follows: The phosphorus-based negative electrode film is composed of phosphorus-SuperP-Sb and LPSC in a mass ratio of 1:1. 1.5 (Li 5.5 PS 4.5 Cl 1.5The mixture is prepared by adding 1% PTFE by mass and repeatedly rolling the mixture. The LCO positive electrode film is obtained by uniformly mixing LiCoO2 (LCO) positive electrode material powder with 1% PTFE binder by mass and repeatedly rolling the mixture. LCO positive electrode material and LPSC are added sequentially to a pressure mold. 1.5 Solid electrolyte, pre-lithiated P-SP-Sb-LPSC 1.5 The negative electrode material was subjected to an external pressure of 200 MPa for 5 minutes to complete the assembly of the all-solid-state battery. The battery was tested at 60°C and 40 MPa, and the results showed an initial charge capacity of 177 mAh·g at a 5C rate. -1 The first-cycle coulomb efficiency is 86%; it can cycle stably for 500 cycles at a 5C rate with a capacity retention of approximately 80%.

[0058] In Example 9, P / SP-Sb-LPSC 1.5 ||LPSC 1.5 The preparation method of LCO solid-state batteries is basically the same as that of the comparative examples above, except that the P / SP-Sb-LPSC method of this invention is different. 1.5 ||LPSC 1.5 The LCO all-solid-state metal battery charging and discharging were performed in a centrifuge apparatus. PMMA-PEGMEA, SN, and LiTFSI were weighed in a weight ratio of 60:35:5, dried, and PMMA-PEGMEA was first dissolved in acetonitrile solvent. Then, lithium salts SN and LiTFSI were added, and finally, phosphorus-SuperP-Sb and LPSC, prepared in a 1:1 ratio and accounting for more than 50% of the total mass, were added. 1.5 (Li 5.5 PS 4.5 Cl 1.5 The mixture is thoroughly mixed, then poured into a mold to form a film, which is then dried at 60°C. LCO cathode material and LPSC are then added sequentially to the pressure mold. 1.5 Solid electrolyte, pre-lithiated P-SP-Sb-LPSC 1.5 The negative electrode elastomer membrane is subjected to an external pressure of 10 MPa and held for 5 minutes to complete the assembly of the all-solid-state battery. According to... Figure 1 The diagram shown illustrates the relationship between the electrode surface direction and the centrifugal force direction of a solid-state battery with an elastomer in the negative electrode. The angle θ between the electrode surface direction and the centrifugal force is adjusted to 90°. The battery is then installed... Figure 12 The centrifugal device was used. The centrifugal stress-assisted charge / discharge method applied centrifugal force during both charging and discharging. The centrifugal tensile stress was set to 1 MPa during both charging and discharging, and the application time was 12 minutes per cycle. The battery test results using this charge / discharge process were as follows: the initial charge capacity at 5C rate was 180 mAh·g.-1 The first-cycle coulomb efficiency is 86%; it can be stably cycled for 2000 cycles at a 5C rate with a capacity retention of approximately 94.9%, as shown in Table 1.

[0059] Example 10

[0060] Comparative Example 10 is an S-SP||LSiPSI||Li all-solid-state lithium-sulfur battery with lithium as the anode and sulfur as the cathode. In this comparative example, the preparation method of the S-SP||LSiPSI||Li all-solid-state battery is as follows: The sulfur-based cathode film is obtained by mixing S-Super P and LSiPSI electrolyte at a mass ratio of 1:1, adding 1% PTFE by mass, and repeatedly rolling the mixture after thorough mixing. Li anode material, LSiPSI solid electrolyte, and S-SP cathode are sequentially added to a pressure mold, and copper foil is placed as the current collector. A pressure of 200 MPa is applied externally and maintained for 5 minutes to complete the assembly of the S-SP||LSiPSI||Li all-solid-state battery. Under a high current of 1C, the initial capacity can reach 1069.5 mAh g⁻¹. -1 After 300 cycles, the capacity is 409.8 mAhg. -1 The retention rate was as high as 38.2%.

[0061] The preparation method of the S-SP||LSiPSI||Li all-solid-state lithium-sulfur battery in Example 10, with lithium as the negative electrode and sulfur as the positive electrode, is basically the same as that of the comparative examples above. The difference is that the charging and discharging of the S-SP||LSiPSI||Li all-solid-state lithium-sulfur battery of this invention is carried out in a centrifuge device, and a 60wt% SBS-PEO + 35wt% SN + 5wt% LiTFSI elastomer is placed between the electrolyte and the negative electrode. The 60wt% SBS-PEO + 35wt% SN + 5wt% LiTFSI elastomer is prepared by solution blending. SBS-PEO, SN and LiTFSI are mixed and dissolved in acetonitrile at a weight ratio of 60:35:5, and then vacuum dried at 60-80°C to evaporate the solvent and form a film. In a pressure mold, Li anode material, SBS-PEO elastomer, LSiPSI solid electrolyte, SBS-PEO elastomer, and S-SP cathode are added sequentially. Copper foil is placed as a current collector. A pressure of 10 MPa is applied externally and maintained for 5 minutes to complete the assembly of the all-solid-state battery S-SP||LSiPSI||Li. During installation, according to... Figure 6 The diagram shown illustrates the relationship between the electrode surface direction and the centrifugal force direction of a solid-state battery with an elastomer at the electrode-electrolyte interface. The angle θ between the electrode surface direction and the centrifugal force is adjusted to 90°, and the battery is then installed... Figure 12The centrifuge apparatus was used. The centrifugal stress-assisted charge / discharge method involved applying centrifugal force during charging but not during discharging. The centrifugal tensile stress during charging was set to 1 MPa, and the stress application time was 60 minutes per cycle. The battery charge / discharge test results in the centrifuge apparatus showed that, under a 1C high current condition, the initial capacity could reach 1070 mAh / g. -1 After 2000 cycles, the capacity retention rate reached 91.5%, as shown in Table 1.

[0062] Example 11

[0063] This embodiment uses lithium as the negative electrode and sulfur as the positive electrode in SPAN||Li6PS5Cl. 0.5 Br 0.5 ||Li-based all-solid-state lithium-sulfur battery. In this comparative example, SPAN||Li6PS s Cl 0.5 Br 0.5 The preparation method of Li-based all-solid-state battery is as follows: The SPAN composite cathode film is composed of sulfur-polyacrylonitrile (SPAN) and Li6PS in a mass ratio of 5:4:1. s Cl 0.5 Br 0.5 Electrolyte and Ketjen Black conductive carbon are mixed in a mortar, and 1% PTFE (by mass) is added. After thorough mixing, the mixture is repeatedly rolled to obtain Li6PS5Cl. 0.5 Br 0.5 The electrolyte membrane is made of Li6PS5Cl 0.5 Br 0.5 The mixture was prepared by mixing PTFE and Li6PS5Cl at a mass ratio of 99.5:0.5 in a heated mortar and cold-pressing it into sheets under a pressure of 180 MPa. Li anode material, Li6PS5Cl, was then added sequentially to the pressure mold. 0.5 Br 0.5 Solid electrolyte, SPAN composite positive electrode membrane, copper foil placed as current collector, external pressure of 200MPa and maintained for 5 minutes to complete the all-solid-state battery SPAN||Li6PS5Cl 0.5 Br 0.5 Assembly of Li. SPAN tested under 3C conditions. ||Li6PS5Cl 0.5 Br 0.5 The initial discharge specific capacity of the Li-based all-solid-state lithium battery is 1317.4 mAh g. -1 After 1000 cycles, the reversible discharge specific capacity is 468.5 mAhg. -1 Capacity retention rate: 35%.

[0064] In Example 11, SPAN||Li6PS was used with lithium as the negative electrode and sulfur as the positive electrode. s Cl 0.5 Br0.5 The preparation method of the all-solid-state lithium-sulfur battery is basically the same as that of the comparative example above, except that the present invention uses lithium as the negative electrode and sulfur as the positive electrode in the SPAN||Li6PS5Cl 0.5 Br 0.5 The Li-based all-solid-state lithium-sulfur battery was charged and discharged in a centrifuge apparatus. 60 wt% PPC-PEO + 35 wt% SN + 5 wt% LiTFSI elastomer were placed at the interfaces of the electrolyte and anode, and the electrolyte and cathode, respectively. The PPC-PEO elastomer was prepared using a solution blending method, where PPC-PEO, SN, and LiTFSI were mixed and dissolved in acetonitrile at a weight ratio of 60:35:5, and then vacuum dried at 60-80℃ to allow the solvent to evaporate and form a film. Li anode material, PPC-PEO elastomer, and Li6PS5Cl were then added sequentially to a pressure mold. 0.5 Br 0.5 Solid-state electrolyte, PPC-PEO elastomer, SPAN composite positive electrode film, copper foil placed as current collector, external pressure of 10MPa and maintained for 5 minutes to complete the all-solid-state battery SPAN||Li6PS5Cl 0.5 Br 0.5 Assembly of Li. The procedure is as follows: during installation, according to... Figure 6 The diagram shown illustrates the relationship between the electrode surface direction and the centrifugal force direction of a solid-state battery with an elastomer at the electrode-electrolyte interface. The angle θ between the electrode surface direction and the centrifugal force is adjusted to 90°, and the battery is then installed... Figure 12 The centrifuge apparatus was used. The centrifugal stress-assisted charge-discharge method involved applying centrifugal force during charging but not during discharging. The centrifugal tensile stress during charging was set to 1 MPa, and the stress was applied for 20 minutes per cycle. Following this method, the battery was charged and discharged in the centrifuge apparatus. The results showed that under 3C high-current conditions, the initial capacity could reach 1350 mAh / g. -1 After 2000 cycles, the capacity retention rate reached 92.5%, as shown in Table 1.

[0065] Example 12

[0066] This embodiment describes a Na||PEO-NaTFSI-ZnCo-MOF||S-SP all-solid-state sodium-sulfur battery with sodium as the negative electrode and sulfur as the positive electrode. In this comparative example, the preparation method of the Na||PEO-NaTFSI-ZnCo-MOF||S-SP all-solid-state battery is as follows: The sulfur-based negative electrode film is obtained by mixing sulfur and Super P at a mass ratio of 70:30, adding 1% PTFE by mass, mixing thoroughly, and then repeatedly rolling. The PEO-NaTFSI-ZnCo-MOF electrolyte is prepared by mixing PEO and NaTFSI at a molar ratio of 55:40:5, adding 8wt% ZnCo-MOF, and then mixing the resulting mixture thoroughly with acetonitrile solvent. The mixture is then baked at 60°C for 24 hours to obtain the PEO-NaTFSI-ZnCo-MOF solid electrolyte elastomer membrane. A sodium anode sheet, a PEO-NaTFSI-ZnCo-MOF solid electrolyte elastomer, and a S-SP cathode material were sequentially added to a pressure mold. An external pressure of 20–200 MPa was applied to complete the assembly of the all-solid-state battery. During charging, at 60°C, the Na||PEO-NaTFSI-ZnCo-MOF||S-SP based on the PEO-NaTFSI-ZnCo-MOF electrolyte exhibited an initial discharge capacity of up to 1030.5 mAh g⁻¹ at 2C. -1 At a 2C rate, the mAh / g value after 80 cycles is 352.4 mAh / g. -1 The capacity retention rate is as high as 60.29%.

[0067] The preparation method of the Na||PEO-NaTFSI-ZnCo-MOF||S-SP all-solid-state sodium-sulfur battery in Example 12, with sodium as the negative electrode and sulfur as the positive electrode, is basically the same as that of the comparative example above. The difference is that the charging and discharging of the Na||PEO-NaTFSI-ZnCo-MOF||S-SP all-solid-state lithium-sulfur battery of the present invention, with sodium as the negative electrode and sulfur as the positive electrode, is carried out in a centrifugal device. A 60wt% PVDF-HFP / PEO + 35wt% SN + 5% LiTFSI elastomer is placed at the interface between the electrolyte and the electrode. The 60wt% PVDF-HFP / PEO + 35wt% SN + 5wt% LiTFSI elastomer is prepared by solution blending. PVDF-HFP / PEO, SN and LiTFSI are mixed and dissolved in acetonitrile at a weight ratio of 60:35:5, and then vacuum dried at 60-80℃ to evaporate the solvent and form a film. In a pressure mold, a negative electrode sodium metal sheet, PVDF-HFP / PEO elastomer, PEO-NaTFSI-ZnCo-MOF solid electrolyte, PVDF-HFP / PEO elastomer, and positive electrode material S-SP are added sequentially. A pressure of 10 MPa is then applied externally to complete the assembly of the all-solid-state battery. The operation process is as follows: during installation, according to... Figure 6The diagram shown illustrates the relationship between the electrode surface direction and the centrifugal force direction of a solid-state battery with an elastomer in the negative electrode. The angle θ between the electrode surface direction and the centrifugal force is adjusted to 90°. The battery is then installed... Figure 12 On the centrifuge device. The centrifugal stress-assisted charge-discharge method uses centrifugal force applied during charging and no centrifugal force applied during discharging. The centrifugal tensile stress during charging is set to 1 MPa, and the centrifugal stress application time is 30 minutes / cycle; the test results according to the above charge-discharge process are: the initial charge capacity at 2C rate is 1050 mAh / g. -1 It can cycle stably for 2000 cycles at a 2C rate with a capacity retention of approximately 93.6%, as shown in Table 1.

[0068] The test results from the above embodiments show that placing an elastomer at the location of significant volume change during battery charging and discharging, aided by centrifugal stress, can repair interfacial contact damage between the electrode and electrolyte at the negative electrode solid-solid interface, thereby extending battery life. For all-solid-state metal batteries, only the contact damage at the negative electrode interface needs to be repaired; therefore, an elastomer design is sufficient at the interface between the negative electrode and electrolyte or within the negative electrode to improve battery life. However, for metal-sulfur batteries, it is necessary to simultaneously improve ion conduction at both the positive and negative electrodes. Solid-state metal-sulfur batteries require simultaneous repair of contact damage between the positive sulfur electrode and the metal negative electrode; therefore, both the positive sulfur electrode and the lithium metal / electrolyte interface require elastomer-assisted charging and discharging design.

[0069] The examples listed in Embodiments 1-12 are merely illustrative, and the above descriptions are only preferred embodiments of this application. Their purpose is to help understand the method and core ideas of this application, and to demonstrate that charging and discharging in a centrifugal device can prevent dendrite growth during charging and extend cycle life. It should be noted that due to the limitations of written expression, and the objective existence of an infinite number of specific structures, those skilled in the art can make various improvements, modifications, or variations without departing from the principles of this application, and can also combine the above-mentioned technical features in an appropriate manner. These improvements, modifications, variations, or combinations, or the direct application of the inventive concept and technical solution to other situations without modification, should all be considered within the scope of protection of this application.

[0070] Table 1. Charge-discharge performance of solid-state batteries in centrifuge apparatus

[0071]

Claims

1. A centrifugal stress-assisted charging and discharging method and apparatus for extending the lifespan of solid-state batteries, characterized in that: The charging and discharging process of a solid-state battery includes the operation of applying centrifugal stress to the battery. The centrifugal stress is the tensile stress generated by the battery rotating around its central axis in the direction perpendicular to the centrifugal force. The electrodes, and / or electrolyte, and / or electrode-electrolyte interface of the solid-state battery contain elastomeric materials. The centrifugal stress-assisted charging and discharging method includes any one of the following methods for applying centrifugal stress during battery charging, and / or during battery discharging, and / or between battery discharging and charging. The apparatus for the centrifugal stress-assisted charging and discharging method includes any one of the following: a centrifugal device and an electrical device are installed together, and / or a centrifugal device and a charging device are installed together. The operation steps of the centrifugal stress-assisted solid-state battery charging and discharging method include: (1) selecting an apparatus for the centrifugal stress-assisted charging and discharging method according to requirements, which is required to coordinate the control of the centrifugal operation and the charging and discharging operation process; (2) (2) Use solid batteries containing elastomers on electrodes, and / or electrolytes, and / or electrode / electrolyte interfaces as batteries for centrifugal stress-assisted charging and discharging; (3) Fix or install the battery in a centrifugal device, requiring that the direction of centrifugal force is not parallel to the direction of active ion transport during charging and / or discharging; (4) Set a centrifugal stress-assisted charging and discharging method, requiring that the battery and centrifuge be fixed together when centrifugal stress is applied, that the battery be connected to the charging pile when charging, that the battery be connected to the electrical equipment when discharging, that the battery, centrifugal device and charging pile be connected separately when centrifugal force is applied and charging are performed simultaneously, and that the battery, centrifugal device and electrical equipment be connected separately when centrifugal force is applied and discharging are performed simultaneously; (5) Set the parameters for applying centrifugal stress and the parameters for charging or discharging the battery, and start charging, or discharging, or charging and applying centrifugal stress, or discharging and applying centrifugal stress.

2. The centrifugal stress-assisted charging and discharging method and apparatus for extending the lifespan of solid-state batteries according to claim 1, characterized in that: The aforementioned ability to coordinate and control the centrifugation and charging / discharging processes refers to the process of sending commands via a mode under the same communication protocol, uploading them to the battery testing control software and the centrifugation operation control software, and initiating the battery charging / discharging operation.

3. The centrifugal stress-assisted charging and discharging method and apparatus for extending the life of solid-state batteries according to claim 1, characterized in that: The requirement that the direction of active ion transport during charging and / or discharging of the battery is not parallel to the direction of centrifugal force means that the central axis of the centrifuge is parallel to the electrode surface of the electrode layer in the battery or is in the same plane as the electrode surface, and the angle θ between the vertical direction of the electrode surface in the battery and the direction of centrifugal force is: 45°≤θ≤90°.

4. The centrifugal stress-assisted charging and discharging method and apparatus for extending the lifespan of solid-state batteries according to claim 1, characterized in that: The requirement that the direction of active ion transport during charging and / or discharging of the battery is not parallel to the direction of centrifugal force when the battery is installed in the centrifugal device means that the vertical direction of the electrode surface in the battery is perpendicular to the direction of centrifugal force, and the angle θ between the central axis of the centrifuge and the vertical direction of the electrode surface of the electrode layer in the battery is: 45°≤θ≤90°.

5. The centrifugal stress-assisted charging and discharging method and apparatus for extending the life of solid-state batteries according to claim 1, characterized in that: The requirement that the direction of active ion transport during charging and / or discharging of the battery is not parallel to the direction of centrifugal force means that when the battery is installed, the rotation axis of the centrifuge is parallel to the electrode surface of the electrode layer in the battery or in the same plane, and the direction perpendicular to the electrode surface in the battery is perpendicular to the direction of centrifugal force.

6. The centrifugal stress-assisted charging and discharging method and apparatus for extending the life of solid-state batteries according to claim 1, characterized in that: The centrifugal device and the electrical device, and / or the centrifugal device and the charging device being fixed together means that the device of the centrifugal stress-assisted charging and discharging method includes any one of the following: the centrifugal device is installed on the electrical device, or the centrifugal device is installed on the charging device, or the centrifugal device, the electrical device, and the charging device are installed together, or the components of the centrifugal device are respectively installed on the electrical device and the charging device. The centrifugal device includes a motor, a transmission mechanism that rotates the battery around a central axis, and battery mounting slots arranged in a certain orientation thereon.

7. The centrifugal stress-assisted charging and discharging method and apparatus for extending the lifespan of solid-state batteries according to claim 6, characterized in that: The centrifugal device's components being installed on the power-consuming device and the charging device respectively means that the centrifugal device is disassembled into a centrifugal component consisting of a motor and a centrifugal component consisting of a transmission mechanism and a battery mounting slot, which are respectively installed on the charging device and the power-consuming device. The centrifugal component consisting of the motor is installed together with the charging pile, while the centrifugal component consisting of the transmission mechanism and the battery mounting slot and the solid-state battery are installed on the power-consuming device. The steps of its centrifugal stress-assisted charging and discharging method are as follows: During charging, the motor in the centrifugal charging pile is fixed to the central shaft in the transmission mechanism of the power-consuming device through a rigid connector or a flexible connector, and / or the charging device in the centrifugal charging pile is connected to the battery of the power-consuming device through a conductive ring. The parameters for battery charging and the parameters for applying centrifugal stress are set for charging and / or applying centrifugal stress. After charging is completed, the motor component and the charging component of the centrifugal charging pile are removed from the power-consuming device. During discharging, the battery and the power-consuming device are connected.

8. The centrifugal stress-assisted charging and discharging method and apparatus for extending the life of solid-state batteries according to claim 1, characterized in that: The centrifugal stress-assisted charging and discharging method includes any one of the following: applying centrifugal stress between discharging and charging, not applying centrifugal stress during charging and discharging, applying centrifugal stress during charging and not applying centrifugal stress during discharging, not applying centrifugal stress during charging and applying centrifugal stress during discharging, or applying centrifugal stress during charging and also applying centrifugal stress during discharging.

9. The centrifugal stress-assisted charging and discharging method and apparatus for extending the life of solid-state batteries according to claim 1, characterized in that: The centrifugal stress application parameters are as follows: the rotational speed ω of the motor-driven battery around the central axis is 100 to 10,000 revolutions per minute, the distance between the battery and the central axis is 5 to 100 centimeters, the applied centrifugal stress is 0.01 to 30 MPa, and the centrifugal stress application time is 1 to 60 minutes per cycle.

10. The centrifugal stress-assisted charging and discharging method and apparatus for extending the life of solid-state batteries according to claim 1, characterized in that: The elastomeric material in the solid-state battery includes any one of the following: an elastomeric material disposed between the electrodes and the electrolyte of the solid-state battery, and / or an elastomeric material between particles in the electrodes, and / or an elastomeric material between particles in the electrolyte, and / or an elastomeric material between particles in the electrodes and the electrolyte.

11. The centrifugal stress-assisted charging and discharging method and apparatus for extending the life of solid-state batteries according to claim 1, characterized in that: The elastomer in the solid-state battery comprises an elastomer material, a plastic crystal, and a lithium salt, wherein the elastomer material contains 50-100 wt%, the plastic crystal contains 0-50 wt%, and the lithium salt contains 0-10 wt%. The elastomer material includes polyether copolymers or blends, polyolefin copolymers or blends, polyurethane copolymers or blends, polyamide copolymers or blends, polysiloxane copolymers or blends, polyacrylate copolymers or blends, polycarbonate copolymers or blends, and fluorine-based copolymers or blends. The copolymer or blend is selected from any one of the following: system-type copolymer or blend, borate ester-type copolymer or blend, and gel-type copolymer or blend; the polyolefin-type copolymer or blend includes any one of polybutadiene, modified polybutadiene, hydrogenated polybutadiene, styrene-ethylene-butene-styrene block copolymer (SEBS), polystyrene-polyisoprene-polystyrene block copolymer (SIS), ethylene propylene diene monomer (EPDM), maleic anhydride-grafted POE, and fluorinated modified POE.The polyacrylate copolymers or blends include any one of ethyl polyacrylate, butyl polyacrylate, polyethylene glycol diacrylate type polyvinyl chloride copolymer (PEGDA-PVC), methacrylate-polyethylene glycol methyl ether acrylate copolymer (PMMA-PEGMEA), butyl acrylate-polydimethylsiloxane (PBA-PDMS), and acrylate-based polydimethylsiloxane (PAA-PDMS). The polyether copolymers or blends include polyethylene oxide (PEO), PVDF-HFP / PEO, polyether-type polypropylene carbonate copolymer (PPC-PEO), polyether-type polycaprolactone copolymer (PCL-PEO), and polyether-type styrene-butadiene-styrene. The copolymer or blend is selected from any one of SBS-PEO and polyether-type polyurethane copolymer (PU-PEO). The fluorinated copolymer or blend includes any one of PTFE-modified elastomer, perfluoropolyether, polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), and fluorinated polymers. The polysiloxane copolymer or blend includes any one of polydimethylsiloxane (PDMS), fluorosilicone rubber, polyborosiloxane, epoxy-based siloxane, and polyionic liquid polysiloxane. The polyamide copolymer or blend includes polyimide (PI), sulfonated polyimide, polyamide amine (PAMAM), polyamide-imide (PAI), polyamide epoxy resin (NAEPE), and polyamide-polyether block copolymer. The copolymer (TPAE) is any one of the following: the polyurethane copolymer or blend includes any one of polyether-type TPU, fluorinated TPU, polycarbonate-type polyurethane (PCPU), fluorinated PU / ionic liquid, graphene / PU, phthalic anhydride-modified polyurethane, and polyethylene glycol-polyurethane (PEG-PU); the borate ester copolymer or blend includes any one of epoxy resin-borate ester and cellulose nanocrystal / borate ester composite; the gel copolymer or blend includes any one of PVA-based gel, PAN-based organic gel, silicone elastomer gel, PVDF-HFP / COF composite gel, PEO / PMMA interpenetrating network gel, and PAMPS / PAAM dual network gel. The described plastic crystal includes any one of succinate (SN), butoxyacetonitrile (SGN), pentaerythritol tetraacetate, N-ethyl-N-methylpyridine di(fluorosulfonyl)imide or N,N-dimethyltetrafluoroborate pyridine, triethylmethyl difluorosulfonylimide, N,N-diethyl-N-methyl-N-(n-propyl)trifluoromethylammonium trifluoroborate, and solid electrolytes; the described lithium salt includes LiTFSI, LiClO4, LiPF6, LiAsF6, LiBF4, LiAlCl4, LiSCN, LiTaF6, LiSnF6, LiGeF6, heteropolyacid lithium salts, LiCF3SO3 and its derivatives, LiN(SO2CF3)2 and its derivatives, and Li2S; x The mixture of any one or more of the following: lithium salts of organic ionic polysulfides, fluorine-containing organic lithium salts, or phosphorus-containing organic lithium salts.

12. The centrifugal stress-assisted charging and discharging method and apparatus for extending the life of solid-state batteries according to claim 1, characterized in that: The all-solid-state battery includes any one of the following: all-solid-state lithium battery, all-solid-state sodium battery, all-solid-state lithium-sulfur battery, all-solid-state sodium-sulfur battery, and all-solid-state fluorine-ion battery; the active ions transported in the solid-state battery include any one of lithium ions, sodium ions, and fluorine ions; the negative electrode material of the all-solid-state battery includes any one of metallic lithium, metallic sodium, metallic silicon, metallic silicon / carbon, and metallic phosphorus; the positive electrode active material includes lithium nickel cobalt manganese oxide (NCM), lithium nickel oxide (LNO), lithium manganese oxide (LMO), lithium nickel manganese oxide (LNMO), lithium cobalt oxide (LCO), or lithium nickel cobalt aluminum oxide (NCA), lithium iron phosphate (LFP), and N2O. At least one of a3V2(PO4)3(NVP) and sulfur; the current collector includes at least one of copper, aluminum, nickel, and stainless steel; the inorganic solid electrolyte includes lithium lanthanum zirconium oxide (LLZO), lithium lanthanum zirconium tantalum oxide (LLZTO), lithium lanthanum zirconium niobium oxide (LLZNO), lithium gallium lanthanum zirconium oxide (LGLZO), lithium titanium aluminum phosphate (LATP), lithium germanium aluminum phosphate (LAGP), lithium germanium vanadium oxide (LGVO), lithium germanium phosphorus sulfur (LGPS), and perovskite-type ABO3, wherein A is one or more of Ca, Sr, and La, and B is one or more of Al and Ti; the sulfide electrolyte includes Li3PS4, Li 5.5 PS 4.5 Cl 1.5 Li7P3S 11 Li 11 GeP2S 12 Li6PS5Cl, Li7P2S8I, Li 10 SnP2S 12 and Li 3.25 Ge 0.25 P 0.75 At least one of S4; the organic solid electrolyte comprises a lithium salt that conducts lithium ions and any one or more combinations of polyether, polyvinyl alcohol, polyethylene oxide, polypropylene oxide, polytetrafluoroethylene, polysiloxane, polyimide, polyurethane, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol formal, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinyl butyral, polyvinyl chloride, sodium carboxymethyl cellulose, and derivatives of perfluorosulfonic acid; the lithium salt comprises LiClO4, LiPF6, LiAsF6, LiBF4, LiAlCl4, LiSCN, LiTaF6, LiSnF6, LiGeF6, lithium heteropolyacid salts, LiCF3SO3 and its derivatives, LiN(SO2CF3)2 and its derivatives, Li2S x The organic solid electrolyte comprises any one or a mixture of two or more of the following: lithium salts of organic polysulfides, fluorine-containing organic lithium salts, or phosphorus-containing organic lithium salts; and / or, the organic solid electrolyte further comprises molecular sieves, MOF, COF, SiO2, Al2O3, MgO, ZnO, and MnO. x Cu x O, ZrO2, TiO x Ti x C y Any one or a mixture of two or more of BaTiO3, LiAlO2, and lithium fast ion conductors.

13. The centrifugal stress-assisted charging and discharging method and apparatus for extending the life of solid-state batteries according to claim 1, characterized in that: The method of applying centrifugal stress after discharge and before charging, without applying centrifugal stress during charging and discharging, refers to applying centrifugal stress after discharge and before charging. The operation process is as follows: After discharge and before charging, fix the battery containing the elastomer on the centrifugal device, ensuring that the direction perpendicular to the stacked layers in the solid-state battery is perpendicular to the direction of the centrifugal force. Set the rotation speed ω of the centrifugal device to 100–5000 rpm, the distance between the battery and the central axis of rotation to 10–50 cm, the applied centrifugal stress to 0.05–10 MPa, and the centrifugal stress application time to 1–60 minutes per cycle. Begin applying the centrifugal stress, and then... The battery's positive and negative terminals are connected to a charging station for charging, and then the battery's positive and negative terminals are connected to the electrical device for discharging. The solid-state battery includes any one of solid-state lithium batteries, solid-state sodium batteries, solid-state fluorine-ion batteries, solid-state lithium-sulfur batteries, and solid-state sodium-sulfur batteries. The negative electrode of the solid-state battery includes any one of metallic lithium, metallic sodium, metallic silicon, metallic silicon / carbon, and metallic phosphorus. The solid electrolyte material includes surface-coated or uncoated inorganic solid electrolytes and / or organic solid electrolytes. The elastomer in the solid-state battery includes elastomer materials, plastic crystals, and lithium salts, wherein the elastomer... The elastomer material contains 50-80 wt%, the plastic crystals 20-50 wt%, and lithium salt ≤5 wt%; the elastomer material includes any one of polyether copolymers or blends, polyolefin copolymers or blends, polyurethane copolymers or blends, polyamide copolymers or blends, polysiloxane copolymers or blends, polyacrylate copolymers or blends, polycarbonate copolymers or blends, fluorinated copolymers or blends, borate copolymers or blends, and gel copolymers or blends; the plastic crystals include succinate (SN), butoxyacetonitrile (SGN), pentaerythritol tetraacetate, N- Ethyl-N-methylpyridine di(fluorosulfonyl)imide or N,N-dimethyltetrafluoroborate pyridine, triethylmethyldifluorosulfonylimide, N,N-diethyl-N-methyl-N-(n-propyl)trifluoromethylammonium trifluoroborate; the lithium salt includes LiTFSI, LiClO4, LiPF6, LiAsF6, LiBF4, LiAlCl4, LiSCN, LiTaF6, LiSnF6, LiGeF6, lithium heteropolyacid salts, LiCF3SO3 and its derivatives, LiN(SO2CF3)2 and its derivatives, Li2S x The mixture of any one or more of the following: lithium salts of organic ionic polysulfides, fluorine-containing organic lithium salts, or phosphorus-containing organic lithium salts.

14. The centrifugal stress-assisted charging and discharging method and apparatus for extending the life of solid-state batteries according to claim 1, characterized in that: The method of applying centrifugal stress during charging and not applying centrifugal stress during discharging refers to the absence of centrifugal stress during discharging, while charging is carried out in a device that generates centrifugal stress. The operation process is as follows: During charging, the positive and negative terminals of the battery are connected to the charging station. Then, the battery containing the elastic body is fixed on the centrifugal device, ensuring that the direction perpendicular to the electrode layer in the solid-state battery is perpendicular to the direction of the centrifugal force, and that the electrode layer is parallel to or in the same plane as the central axis of rotation. During charging, the rotation speed ω of the centrifugal device is 100–5000 rpm, the distance between the battery and the central axis of rotation is 5–50 cm, and the applied centrifugal stress is 0. The centrifugal stress is applied at a pressure of 0.05–10 MPa for 1–60 minutes per cycle. The solid-state battery includes any one of solid-state lithium batteries, solid-state sodium batteries, solid-state fluorine-ion batteries, solid-state sodium-sulfur batteries, and solid-state lithium-sulfur batteries. The negative electrode of the solid-state battery includes any one of metallic lithium, metallic sodium, metallic silicon, metallic silicon / carbon, and metallic phosphorus. The solid electrolyte is made of inorganic solid electrolyte with or without surface coating, and / or organic solid electrolyte. The elastomer in the solid-state battery includes an elastomer material, a plastic crystal, and a lithium salt, wherein the elastomer material contains 50–80% lithium salt. wt%, plastic crystal 20-50wt%, lithium salt ≤5wt%; the elastomer material includes any one of polyether copolymers or blends, polyolefin copolymers or blends, polyurethane copolymers or blends, polyamide copolymers or blends, polysiloxane copolymers or blends, polyacrylate copolymers or blends, polycarbonate copolymers or blends, fluorinated copolymers or blends, borate copolymers or blends, and gel copolymers or blends; the plastic crystal includes succinate (SN), butoxyacetonitrile (SGN), pentaerythritol tetraacetate, and N-ethyl-N-methylpyridine. The lithium salt comprises any one of the following: pyridine di(fluorosulfonyl)imide or N,N-dimethyltetrafluoroborate pyridine, triethylmethyldifluorosulfonylimide, N,N-diethyl-N-methyl-N-(n-propyl)trifluoromethylammonium trifluoroborate, and solid electrolytes; the lithium salt comprises LiTFSI, LiClO4, LiPF6, LiAsF6, LiBF4, LiAlCl4, LiSCN, LiTaF6, LiSnF6, LiGeF6, lithium heteropolyacid salts, LiCF3SO3 and its derivatives, LiN(SO2CF3)2 and its derivatives, and Li2S. x The mixture of any one or more of the following: lithium salts of organic ionic polysulfides, fluorine-containing organic lithium salts, or phosphorus-containing organic lithium salts.

15. The centrifugal stress-assisted charging and discharging method and apparatus for extending the life of solid-state batteries according to claim 1, characterized in that: The method described, which allows for charging without applying centrifugal stress but discharging with it, refers to charging without centrifugal stress and discharging performed on a centrifugal device. The operation is as follows: During discharge, the positive and negative terminals of the battery are first connected to the electrical device. Then, the battery containing the elastomer is solidified on the centrifugal device, with the direction perpendicular to the stacked layers perpendicular to the direction of centrifugal force, and the electrode layers parallel to or in the same plane as the central axis. During discharge, the centrifugal device rotates at a speed ω of 100–5000 rpm, the distance between the battery and the central axis is 5–50 cm, the applied centrifugal stress is 0.05–10 MPa, and the application time is 1–60 minutes per cycle. The solid-state battery includes any one of solid-state lithium batteries, solid-state sodium batteries, solid-state lithium-sulfur batteries, solid-state fluorine-ion batteries, and solid-state sodium-sulfur batteries. The negative electrode of the solid-state battery may include, but is not limited to, any one of metallic lithium, metallic sodium, metallic silicon, metallic silicon / carbon, and metallic phosphorus. The solid electrolyte material may be surface-coated or uncoated. The solid-state battery is coated with an inorganic solid electrolyte and / or an organic solid electrolyte. The elastomer in the solid-state battery comprises an elastomer material, a plastic crystal, and a lithium salt, wherein the elastomer material contains 50–80 wt%, the plastic crystal 20–50 wt%, and the lithium salt ≤5 wt%. The elastomer material includes polyether copolymers or blends, polyolefin copolymers or blends, polyurethane copolymers or blends, polyamide copolymers or blends, polysiloxane copolymers or blends, polyacrylate copolymers or blends, and polycarbonate copolymers or blends. Ester-type copolymers or blends, fluorinated copolymers or blends, borate ester-type copolymers or blends, and gel-type copolymers or blends; the lithium salt includes LiTFSI, LiClO4, LiPF6, LiAsF6, LiBF4, LiAlCl4, LiSCN, LiTaF6, LiSnF6, LiGeF6, lithium heteropolyacid salts, LiCF3SO3 and its derivatives, LiN(SO2CF3)2 and its derivatives, and Li2S x The mixture of any one or more of the following: lithium salts of organic ionic polysulfides, fluorine-containing organic lithium salts, or phosphorus-containing organic lithium salts.

16. The centrifugal stress-assisted charging and discharging method and apparatus for extending the life of solid-state batteries according to claim 1, characterized in that: The method of applying centrifugal stress during battery discharge and charging refers to the discharge and charging process being carried out on a centrifugal device. The operation process is as follows: during discharge and charging, the solid-state battery containing an elastomer is fixed on the centrifugal device, so that the direction perpendicular to the stacked layers is perpendicular to the direction of centrifugal force, and the surface of the electrode layer is parallel to or in the same plane as the central axis of rotation. During charging and discharging, the rotation speed ω of the centrifugal device is set to 100-5000 rpm, the distance between the battery and the central axis of rotation is 5-50 cm, the centrifugal stress is applied to 0.05-10 MPa, and the centrifugal stress is applied for 1-60 minutes / cycle, and centrifugal stress-assisted charging and discharging begins. The solid-state battery includes any one of all-solid-state lithium battery, all-solid-state sodium battery, all-solid-state fluorine-ion battery, all-solid-state lithium-sulfur battery, and all-solid-state sodium-sulfur battery. The negative electrode of the solid-state battery includes any one of metallic lithium, metallic sodium, metallic silicon, metallic silicon / carbon, and metallic phosphorus. The solid electrolyte material includes inorganic solid electrolyte with or without surface coating, and / or organic solid electrolyte. The elastomer in the solid-state battery comprises an elastomer material, a plastic crystal, and a lithium salt, wherein the elastomer material contains 50-80 wt%, the plastic crystal 20-50 wt%, and the lithium salt ≤5 wt%; the elastomer material comprises any one of polyether copolymers or blends, polyolefin copolymers or blends, polyurethane copolymers or blends, polyamide copolymers or blends, polysiloxane copolymers or blends, polyacrylate copolymers or blends, polycarbonate copolymers or blends, fluorinated copolymers or blends, borate copolymers or blends, and gel copolymers or blends; the plastic crystal comprises succinate (SN) and butoxyacetonitrile (SGN). The lithium salt comprises any one of the following: pentaerythritol tetraacetate, N-ethyl-N-methylpyridine di(fluorosulfonyl)imide or N,N-dimethyltetrafluoroborate pyridine, triethylmethyldifluorosulfonylimide, N,N-diethyl-N-methyl-N-(n-propyl)trifluoromethylammonium trifluoroborate, and solid electrolytes; the lithium salt comprises LiTFSI, LiClO4, LiPF6, LiAsF6, LiBF4, LiAlCl4, LiSCN, LiTaF6, LiSnF6, LiGeF6, lithium heteropolyacid salts, LiCF3SO3 and its derivatives, LiN(SO2CF3)2 and its derivatives, and Li2S. x The mixture of any one or more of the following: lithium salts of organic ionic polysulfides, fluorine-containing organic lithium salts, or phosphorus-containing organic lithium salts.

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