A solid-state battery and its in-situ polymerization preparation method

Abstract

This invention relates to the field of batteries, specifically to an in-situ polymerization preparation method for solid-state batteries. The method involves injecting an electrolyte into a battery casing containing a battery cell, followed by encapsulation and in-situ polymerization. The battery cell comprises a positive electrode, a separator, and a negative electrode sequentially laminated together. The separator comprises a base film and a modified layer pre-formed on the surface of the base film. The modified layer comprises modifier A, modifier B, and a binder. Modifier A comprises at least one of LiPF6, LiBF4, LiBOB, and LiClO4; modifier B comprises at least one of AlF3, SbF5, LiCl, and LiBr; the weight ratio of modifier A to B is 0.05–5:1. The electrolyte comprises a basic electrolyte and dissolved olefin-containing polymeric monomers. This invention can effectively improve the performance of solid-state batteries.

Description

Technical Field

[0001] This invention relates to the field of batteries, and more specifically to the field of solid-state battery technology. Background Technology

[0002] Energy is a vital material foundation for developing the national economy and improving people's living standards, and it is also a crucial factor directly influencing economic development. Since the beginning of the 21st century, problems such as resource shortages, environmental pollution, and the greenhouse effect caused by traditional energy utilization methods have become increasingly prominent. Improving the energy structure and developing efficient and clean new energy sources has become a global consensus. Lithium-ion batteries have gained popularity due to their superior performance, including safety, environmental friendliness, high specific energy, and excellent electrochemical performance. Currently used lithium-ion batteries employ liquid electrolytes, which have drawbacks such as electrolyte leakage and flammability during use. To ensure the safety and stability of batteries during use, the development direction of lithium-ion batteries is gradually shifting towards solid-state batteries.

[0003] In-situ solidification of liquid electrolytes within the battery reduces free solvent molecules, improving battery safety. It also mitigates the problems of poor solid-solid interface contact and high charge transfer impedance associated with solid electrolytes, making it a highly compatible technology with existing battery manufacturing processes. Current in-situ gel electrolyte preparation typically involves the introduction of highly reactive azo and peroxide initiators. While these initiators offer good initiation effects and wide applicability, their rapid polymerization processes can lead to excessively large polymer molecular weights and monomer residues. Furthermore, the highly reactive free radicals remaining from the initiator during polymerization can persist in the electrolyte system, participating in electrode reactions and reducing battery cycle stability.

[0004] In summary, there is an urgent need in this field to develop a simple and efficient in-situ polymerization method for preparing solid-state lithium batteries. The preparation of solid-state lithium-ion batteries with high energy density and cycle stability has always been a hot research topic in this field. Summary of the Invention

[0005] In view of the problems faced by existing solid-state batteries, the primary objective of this invention is to provide an in-situ polymerization preparation method for solid-state batteries, aiming to prepare a solid-state battery with excellent stability and safety.

[0006] A second objective of this invention is to provide a solid-state battery prepared by the aforementioned method.

[0007] Existing in-situ gel electrolyte preparation methods typically involve the introduction of highly reactive azo and peroxide initiators. While these initiators offer good initiation performance and wide applicability, the rapid polymerization process they initiate can easily result in polymers with excessively large molecular weights and monomer residues. Furthermore, the highly reactive free radicals remaining from the initiator during the polymerization process can persist in the electrolyte system, participating in electrode reactions and causing a decrease in battery cycle stability. To address these industry problems, this invention provides the following solution:

[0008] An in-situ polymerization preparation method for solid-state batteries involves injecting an electrolyte into a battery casing containing a battery cell, followed by encapsulation and in-situ polymerization. The battery cell comprises a positive electrode, a separator, and a negative electrode sequentially laminated together. The separator comprises a base film and a modified layer pre-cured on the surface of the base film. The modified layer comprises a modifier A, a modifier B, and a binder.

[0009] The modifier A includes at least one of LiPF6, LiBF4, LiBOB, and LiClO4.

[0010] The modifier B includes at least one of AlF3, SbF5, LiCl, and LiBr;

[0011] The weight ratio of modifiers A and B is 0.05 to 5:1;

[0012] The electrolyte includes a base electrolyte and olefin-containing polymeric monomers dissolved therein.

[0013] This invention innovatively demonstrates that pre-curing a modified layer containing modifiers A and B in the stated weight ratio on the surface of a separator, and then using the pre-cured modifiers A and B to synergistically induce the surface solid-phase in-situ polymerization of the olefin-containing polymer monomers, can unexpectedly improve the structure of the polymerization, improve the conduction pathways and rates of active ions, and help to synergistically improve the electrochemical performance of the battery.

[0014] In this invention, the synergistic combination of the components and proportions of the modifiers A and B, and their pre-curing on the membrane surface, are key to synergistically inducing in-situ polymerization of olefin-containing monomers and improving performance.

[0015] Preferably, modifier A includes LiPF6. Modifier B is preferably AlF3 and / or SbF5. Studies have found that the combination of the preferred modifiers A and B helps to further improve their synergistic effect, and helps to further improve the electrochemical performance of solid-state batteries in conjunction with the aforementioned ratio and pre-curing process.

[0016] The study also found that, with the combined synergistic effect of modifiers A and B, further coordination of their ratio and content control can help to further synergistically regulate the behavior of in-situ polymerization of olefin monomers and improve the electrochemical performance of the prepared solid-state battery.

[0017] Preferably, the weight ratio of modifier A to modifier B is 0.1 to 1:1; more preferably, it is 0.1 to 0.8:1.

[0018] In this invention, the adhesive is a polymeric component capable of adhering modifier A and modifier B to each other on the surface of the base film, preferably at least one of PVDF, PAA, PMMA, and PTFE;

[0019] In this invention, the amount of binder in the modified layer is not particularly required, as long as it is sufficient to allow modifiers A and B to adhere to the base film in advance. For example, the weight percentage of binder in the modified layer is less than or equal to 15 wt.%, and more preferably 5 to 10 wt.%.

[0020] In this invention, the base membrane can be a conventional polymer membrane material in the industry, such as at least one of polypropylene, polyethylene, and glass fiber.

[0021] The thickness of the modified layer can be adjusted as needed. For example, the thickness of the modified layer is 5 to 20 μm, and more specifically, it can be 5 to 15 μm.

[0022] Preferably, the modified layer is disposed on the positive electrode side. That is, the modified layer is laminated onto the surface of the base film near the positive electrode.

[0023] In this invention, the modified layer is a solid-phase layered material containing modifiers A and B, which is adhered to the surface of the base film by the binder. The modifiers can be prepared using conventional slurry coating methods. For example, in this invention, modifiers A and B, along with the binder, are pre-slurried and coated onto the base film, followed by curing (drying), thus pre-forming the modified layer on the surface of the separator. This invention has found that the combined use of modifiers A and B with the pre-forming method helps improve the subsequent in-situ polymerization behavior of monomers, thereby synergistically improving the electrochemical performance of solid-state batteries.

[0024] In this invention, the monomer can be any monomer known in the industry capable of forming a solid electrolyte. For example, the polymerizable monomer is at least one compound having the structural formula of Formula 1.

[0025]

[0026] Formula 1

[0027] R1, R2, R3, and Y are individually H, alkenyl, alkyl, or alkyl with substituents, wherein the substituent is at least one of aryl, halogen, alkenyl, alkoxy, or ester; A is O or NR; and R is H or alkyl. In this invention, the alkyl group is, for example, a C1-C6 alkyl group. Considering material cost and effectiveness, in the monomer, further, R1 is H or a C1-C3 alkyl group, and R2 and R3 are H. A is O; and Y is H or a C1-C3 alkyl group.

[0028] In this invention, the basic electrolyte comprises an organic solvent and a conductive lithium salt;

[0029] Preferably, the organic solvent is an ester solvent, and more preferably includes, but is not limited to, at least one of methyl acrylate, ethyl acrylate, methyl 2-methacrylate and ethyl 2-methacrylate.

[0030] The conductive lithium salts include, but are not limited to, at least one of LiPF6, LiBF4, LiClO4, LiAsF6, LiCF3SO3, and LiN(CF3SO2)2.

[0031] Preferably, in the electrolyte, the concentration of conductive lithium salt is 0.1-5M, and the amount of polymeric monomer added is 1.5%-10% of the mass of the base electrolyte, more preferably 3-6wt%.

[0032] In this invention, there are no special requirements for the material type of the positive electrode and the negative electrode. They can be any component known in the industry that can be used in solid-state batteries, or any structure known in the industry.

[0033] For example, the positive electrode sheet includes a positive current collector and a positive electrode material containing a positive active material loaded on its surface;

[0034] Preferably, the positive electrode active material includes, but is not limited to, lithium-containing active materials or sodium-containing active materials;

[0035] Preferably, the lithium-containing active material includes LiCoO2, LiNiO2, LiMn2O4, LiFePO4, Li3V2(PO4)3, Li3V3(PO4)3, LiVPO4F, Li2CuO2, Li5FeO4, TiS2, V2S3, FeS, FeS2, TiO2, Cr3O8, V2O5, MnO2, LiCo x Ni 1-x O2, LiCo x Ni 1-x-y Al y O2, LiFe p Mn q X 1-p-qO4, Li 1+s L 1－p－q M p N q O2 and LiYS r One or more of the following: wherein 0≤x≤1, 0≤y≤1, 0≤p≤1, 0≤q≤1, 0≤p+q≤1, 0.1≤s≤0.2, 1≤r≤2.5; X is at least one of Al, Mg, Ga, Cr, Co, Ni, Cu, Zn or Mo; L, M, N are each independently at least one of Li, Co, Mn, Ni, Fe, Al, Mg, Ga, Ti, Cr, Cu, Zn, Mo, F, I, S and B; and Y is at least one of Ti, Fe, Ni, Cu and Mo.

[0036] The negative electrode sheet is an active metal foil or a supported negative electrode sheet. The supported negative electrode sheet includes a current collector and a negative electrode material containing a negative electrode active material composited on its surface. The metal foil is, for example, a lithium foil or other metal negative electrode material. The negative electrode active material includes at least one of lithium metal, sodium metal, carbon materials, oxides of transition metals, alloy materials, silicon materials and other silicon-containing materials, lithium-containing transition metal nitrides, and lithium titanate materials.

[0037] In this invention, there are no special requirements for the conditions of in-situ polymerization. For example, when the temperature is higher, the in-situ polymerization time can be shortened, and when the temperature is lower, the polymerization time can be extended. Considering the preparation effect and performance, the temperature of the in-situ polymerization stage is 40-80℃, and more preferably 60-75℃. The in-situ polymerization time can be 1-24h, and more preferably 5-15h.

[0038] The present invention also provides a solid-state battery prepared by the in-situ polymerization method described above.

[0039] In this invention, thanks to the combination of the special preparation processes, the in-situ polymerization behavior can be controlled, and solid-state batteries with special components and structures can be obtained. Moreover, the solid-state batteries prepared by this method can exhibit excellent performance.

[0040] In this invention, the solid-state battery is an all-solid-state or solid-state-like battery;

[0041] Preferably, the solid-state battery is a solid-state lithium-ion battery, a solid-state lithium metal battery, or a solid-state sodium-ion battery.

[0042] The beneficial effects of this invention are as follows:

[0043] This invention innovatively demonstrates that pre-forming a modified layer containing modifiers A and B on the surface of a separator, and then using the pre-formulated modifiers A and B to synergistically induce the surface solid-phase in-situ polymerization of the olefin-containing polymer monomers, can unexpectedly improve the structure of the polymerization, improve the conduction pathways and rates of active ions, and help to synergistically improve the electrochemical performance of the battery.

[0044] The in-situ polymerizable solid-state lithium battery provided by this invention can prepare and assemble high-capacity, stable batteries while ensuring that the traditional lithium-ion battery preparation process remains unchanged, which can greatly save the production cost of solid-state batteries. Attached Figure Description

[0045] Figure 1 SEM images of the surface (a) and cross-section (b) of the modified diaphragm in Example 1;

[0046] Figure 2 This is a diagram illustrating the effect of gel formation using a composite system of modifier A and modifier B in Example 1.

[0047] Figure 3 The graph shows the battery cycle performance of the system used in Example 1.

[0048] Figure 4 The image shows the effect of gel formation using only modifier A in Comparative Example 1. Detailed Implementation

[0049] The following examples are intended to further illustrate the content of the present invention, rather than to limit the scope of protection of the claims of the present invention.

[0050] The solid-state battery of the present invention can be based on existing in-situ polymerization by pre-curing modifiers A and B on the separator, and then contacting it with an electrolyte containing olefin monomers for in-situ polymerization. Based on the combined interfacial polymerization mode synergistically induced by modifiers A and B, the polymerization behavior can be controlled, the structural stability of the battery and the ion and electron conduction can be improved, and the performance of the solid-state battery can be improved.

[0051] The solid-state battery preparation steps of the present invention include:

[0052] (1): Modifiers A and B and binder are slurried with solvents such as NMP, then coated on the diaphragm base film, dried and cured, and modifiers A and B are pre-cured on the base film.

[0053] (2) Assemble the battery in the order of positive electrode, separator, negative electrode, electrolyte injection, and encapsulation; the electrolyte added during the electrolyte injection stage includes an electrolyte with acrylic monomers.

[0054] In the examples described in this invention, the positive electrode sheet and the modified separator are prepared by a coating method, and the solvent used for the slurry formation in the coating method can be NMP. The ratio of the modifier additives A / B and the binder is by weight.

[0055] In the following cases, unless otherwise stated, the electrolyte is a basic electrolyte with added acrylic monomer, and the basic electrolyte is 1M LiPF6 dissolved in EC:DEC:EMC in a volume ratio of 1:1:1.

[0056] In this invention, the room temperature is, for example, 20–30°C.

[0057] The following specific embodiments of the present invention are, for example:

[0058] Example 1:

[0059] Positive electrode: LiNi 0.6 Co 0.2 Mn 0.2 O2, used as the positive electrode active material, is coated with acetylene black and PVDF in an 8:1:1 ratio to form a positive electrode sheet, ensuring the LiNi... 0.6 Co 0.2 Mn 0.2 The surface density of O2 is 27-28 mg / cm³. 2 Dry before use.

[0060] Pre-fabricated diaphragm: Modifier A (LiPF6 in this case), modifier B (AlF3 in this case), and binder (PVDF in this case) are uniformly mixed in a ratio of 1:8:1 to form a slurry. This slurry is then coated onto one surface of a polypropylene diaphragm to a thickness of 6 μm, and subsequently dried before use. The surface and cross-sectional morphology of the modified diaphragm are shown below. Figure 1 As shown.

[0061] Polymer electrolyte: Based on the weight of the base electrolyte, add 5 wt% methyl 2-methacrylate to the base electrolyte and mix thoroughly;

[0062] Assembly: The battery was assembled in the following order: positive electrode, separator (modified layer (coating of modifier AB) near the positive electrode), lithium anode, electrolyte injection (injection of polymerized electrolyte), and encapsulation. The resulting battery was then left to stand at room temperature for 12 hours, followed by heating at 70°C for 1 hour. The effect of using the A and B composite to initiate gelation is as follows: Figure 2 As shown, this demonstrates that a structurally stable gel can be formed under the influence of these two factors. At room temperature, when the positive electrode material is discharged at a constant current of 1C, as... Figure 3 As shown, the specific capacity can still be maintained at 155mAh / g after 300 cycles, demonstrating good cycling performance.

[0063] Example 2: Modifying Modifier A

[0064] Compared with Example 1, the only difference is that the component of modifier A is changed to LiBF4, while the component of modifier B remains unchanged. Other operations and parameters are the same as in Example 1.

[0065] At room temperature, when the cathode material is discharged at a constant current of 1C, the specific capacity can still be maintained at 138mAh / g after 300 cycles, demonstrating good cycling performance.

[0066] Example 3: Modifying Modifier A

[0067] Compared with Example 1, the only difference is that the component of modifier A is changed to LiBOB (lithium dioxolane borate), while the component of modifier B remains unchanged. Other operations and parameters are the same as in Example 1.

[0068] At room temperature, when the cathode material is discharged at a constant current of 1C, the specific capacity can still be maintained at 135mAh / g after 300 cycles, demonstrating good cycling performance.

[0069] Example 4: Modifying Modifier B

[0070] Compared with Example 1, the only difference is that the component of modifier B is changed to SbF5, while the component of modifier A remains unchanged. Other operations and parameters are the same as in Example 1.

[0071] At room temperature, when the cathode material is discharged at a constant current of 1C, the specific capacity can still be maintained at 152mAh / g after 300 cycles, demonstrating good cycling performance.

[0072] Example 5: Changing the ratio of modifiers A and B and PVDF

[0073] Compared with Example 1, the only difference is that the ratio of modifiers A and B and binder (PAA) is changed. Modifier A, modifier B and binder are mixed evenly in a ratio of 4:5.5:0.5 to form a slurry. Other operations and parameters are the same as in Example 1.

[0074] At room temperature, when the cathode material is discharged at a constant current of 1C, the specific capacity can still be maintained at 150mAh / g after 300 cycles, demonstrating good cycling performance.

[0075] Example 6:

[0076] Compared with Example 1, the only difference is that the structures of the positive electrode, negative electrode and acrylate monomer are changed. The positive electrode is LiFePO4 with the same areal loading, the negative electrode is graphite, and the acrylate monomer is methyl acrylate. Other operations and parameters are the same as in Example 1.

[0077] At room temperature, when the cathode material is discharged at a constant current of 1C, the specific capacity can still be maintained at 133mAh / g after 300 cycles, demonstrating good cycling performance.

[0078] Comparative Example 1: Single Modifier A:

[0079] Compared to Example 1, the only difference is that modifier B is omitted, and its missing amount is made up with modifier A, that is, the weight ratio of modifier A to PVDF is 9:1. Other operations and parameters are the same as in Example 1.

[0080] like Figure 4 The figure shows the gelation effect of a single modifier A. It can be seen that the system still has a certain degree of fluidity, and the gel structure is unstable. At room temperature, when the cathode material is discharged at a constant current of 1C, the specific capacity can still be maintained at 120mAh / g after 300 cycles, but the cycle stability decreases.

[0081] Comparative Example 2: Single Modifier B:

[0082] Compared to Example 1, the only difference is that modifier A is omitted, and its missing amount is made up with modifier B, that is, the weight ratio of modifier B to PVDF is 9:1. Other operations and parameters are the same as in Example 1.

[0083] At room temperature, when the cathode material is discharged at a constant current of 1C, the specific capacity can still be maintained at 56mAh / g after 200 cycles, indicating poor cycle stability.

[0084] Comparative Example 3: Not pre-cured on the diaphragm:

[0085] Compared to Example 1, the only difference is that modifiers A and B were not pre-coated onto the separator; instead, equal amounts of modifiers A and B and the monomer were added to the base electrolyte. The separator used in the battery assembly stage was the base membrane (polypropylene separator) of Example 1 without a pre-modified layer. Other operations and parameters were the same as in Example 1, and the steps were as follows:

[0086] Selecting LiNi 0.6 Co 0.2 Mn 0.2 O2, used as the positive electrode active material, is coated with acetylene black and PVDF in an 8:1:1 ratio to form a positive electrode sheet, ensuring the LiNi... 0.6 Co 0.2 Mn 0.2 The surface density of O2 is 27-28 mg / cm³. 2The battery was dried before use. 5 wt% methyl 2-methacrylate was added to the base electrolyte and mixed thoroughly. Equal amounts of modifiers A and B (LiPF6 to AlF3 in a 1:8 ratio, totaling 5% of the base electrolyte weight) from Example 1 were added. The battery was assembled in the following order: positive electrode, separator (base film), negative electrode, electrolyte injection (additive modifier AB - monomer base electrolyte), and encapsulation. The resulting battery was then left to stand at room temperature for 12 hours, followed by heating at 70°C for 1 hour. At room temperature with a 1C constant current discharge using the positive electrode material, the specific capacity remained at 80 mAh / g after 300 cycles, indicating poor cycle stability.

[0087] Comparative Example 4:

[0088] Compared with Example 1, the only difference is that modifier A is replaced with LiTFSI, and the other operations and parameters are the same as in Example 1.

[0089] At room temperature, when the cathode material is discharged at a constant current of 1C, the specific capacity remains at 104 mAh / g after 300 cycles, but the cycle stability decreases.

[0090] Comparative Example 5:

[0091] Compared with Example 1, the only difference is that modifier B is replaced with POCl3, and the other operations and parameters are the same as in Example 1.

[0092] At room temperature, when the cathode material is discharged at a constant current of 1C, the specific capacity is only 47mAh / g after 100 cycles, and the cycle stability decreases.

[0093] Comparative Example 6:

[0094] Compared with Example 1, the only difference is that the ratio of modifiers A, B and PVDF is 8:1:1, and the other operations and parameters are the same as in Example 1.

[0095] At room temperature, when the cathode material is discharged at a constant current of 1C, the specific capacity remains at 105mAh / g after 300 cycles, but the cycle stability decreases.

Claims

1. A method for in-situ polymerization preparation of a solid-state battery, comprising injecting an electrolyte into a battery casing containing a battery cell, followed by encapsulation and in-situ polymerization; wherein the battery cell comprises a positive electrode sheet, a separator, and a negative electrode sheet sequentially laminated; characterized in that, The diaphragm includes a base membrane and a modified layer pre-formed on the surface of the base membrane; the modified layer includes modifier A, modifier B and binder; The modifier A includes at least one of LiPF6, LiBF4, LiBOB, and LiClO4. The modifier B includes at least one of AlF3, SbF5, LiCl, and LiBr; The weight ratio of modifiers A and B is 0.05~5:1; The electrolyte includes a basic electrolyte and olefin-containing polymeric monomers dissolved therein; The basic electrolyte comprises an organic solvent and a conductive lithium salt; the organic solvent is an ester solvent. The conductive lithium salt includes at least one of LiPF6, LiBF4, LiClO4, LiAsF6, LiCF3SO3, and LiN(CF3SO2)2.

2. The in-situ polymerization preparation method for solid-state batteries as described in claim 1, characterized in that, The weight ratio of modifier A to modifier B is 0.1 to 1:

1.

3. The in-situ polymerization preparation method for solid-state batteries as described in claim 2, characterized in that, The weight ratio of modifier A to modifier B is 0.1~0.8:

1.

4. The in-situ polymerization preparation method for solid-state batteries as described in claim 1, characterized in that, The adhesive is a polymeric component capable of adhering modifier A and modifier B to each other on the surface of the base film.

5. The in-situ polymerization preparation method for solid-state batteries as described in claim 4, characterized in that, The adhesive is at least one of PVDF, PAA, PMMA, and PTFE.

6. The in-situ polymerization preparation method for solid-state batteries as described in claim 4, characterized in that, In the modified layer, the binder accounts for less than or equal to 15 wt.% by weight.

7. The in-situ polymerization preparation method for solid-state batteries as described in claim 6, characterized in that, In the modified layer, the binder accounts for 5 to 10 wt.% by weight.

8. The in-situ polymerization preparation method for solid-state batteries as described in claim 1, characterized in that, The base film material is at least one of polypropylene, polyethylene, and glass fiber.

9. The in-situ polymerization preparation method for solid-state batteries as described in claim 1, characterized in that, The thickness of the modified layer is 5~20μm.

10. The in-situ polymerization preparation method for solid-state batteries as described in claim 1, characterized in that, The modified layer is disposed on the positive electrode side.

11. The in-situ polymerization preparation method for solid-state batteries as described in claim 1, characterized in that, The polymerizable monomer is at least one compound having the structural formula of Formula 1: Formula 1 R1, R2, R3, and Y are individually H, alkenyl, alkyl, or alkyl with substituents, wherein the substituent is at least one of aryl, halogen, alkenyl, alkoxy, or ester; A is O or NR; and R is H or alkyl.

12. The in-situ polymerization preparation method for solid-state batteries as described in claim 1, characterized in that, In the basic electrolyte, the organic solvent includes at least one of methyl acrylate, ethyl acrylate, methyl 2-methacrylate, and ethyl 2-methacrylate.

13. The in-situ polymerization preparation method for solid-state batteries as described in claim 1, characterized in that, In the electrolyte, the concentration of conductive lithium salt is 0.1~5M, and the polymeric monomer is 1.5%~10% of the mass of the base electrolyte.

14. The in-situ polymerization preparation method for solid-state batteries as described in claim 1, characterized in that, The positive electrode sheet includes a positive current collector and a positive electrode material containing a positive active material loaded on its surface; The positive electrode active material includes lithium-containing active materials or sodium-containing active materials; The lithium-containing active materials include LiCoO2, LiNiO2, LiMn2O4, LiFePO4, Li3V2(PO4)3, Li3V3(PO4)3, LiVPO4F, Li2CuO2, Li5FeO4, and LiCo. x Ni 1-x O2, LiCo x Ni 1-x-y Al y O2, LiFe p Mn q X 1-p-q O4, Li 1+ s L 1－p－q M p N q O2 and LiYS r One or more of the following: 0≤x≤1, 0≤y≤1, 0≤p≤1, 0≤q≤1, 0≤p+q≤1, 0.1≤s≤0.2, 1≤r≤2.5; X is at least one of Al, Mg, Ga, Cr, Co, Ni, Cu, Zn or Mo; L, M, N are each independently at least one of Li, Co, Mn, Ni, Fe, Al, Mg, Ga, Ti, Cr, Cu, Zn, Mo, F, I, S and B; and Y is at least one of Ti, Fe, Ni, Cu and Mo.

15. The in-situ polymerization preparation method for solid-state batteries as described in claim 1, characterized in that, The negative electrode sheet is an active metal foil or a supported negative electrode sheet. The supported negative electrode sheet includes a current collector and a negative electrode material containing a negative electrode active material composited on its surface. The negative electrode active material includes at least one of lithium metal, sodium metal, carbon materials, oxides of transition metals, alloy materials, silicon materials and other silicon-containing materials, lithium-containing transition metal nitrides, and lithium titanate materials.

16. The in-situ polymerization preparation method for solid-state batteries according to any one of claims 1 to 15, characterized in that, The temperature during the in-situ polymerization stage is 40~80℃.

17. The in-situ polymerization preparation method for solid-state batteries as described in claim 16, characterized in that, The in-situ polymerization time is 1~24h.

18. A solid-state battery prepared by the in-situ polymerization method according to any one of claims 1 to 17.

19. The solid-state battery as claimed in claim 18, characterized in that, The solid-state battery mentioned is an all-solid-state or solid-state-like battery.

20. The solid-state battery as claimed in claim 19, characterized in that, The solid-state battery mentioned is a solid-state lithium-ion battery, a solid-state lithium metal battery, or a solid-state sodium-ion battery.

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