A solid-liquid hybrid battery and its preparation method

Abstract

This invention provides a solid-liquid hybrid battery and its preparation method. The preparation method includes the following steps: (1) assembling a positive electrode, a negative electrode, and a solid electrolyte membrane to obtain a battery cell; (2) injecting an in-situ solidified electrolyte into the battery cell obtained in step (1) for solidification to obtain the solid-liquid hybrid battery. By combining a solid electrolyte membrane with an in-situ solidified electrolyte, this invention can effectively reduce the content of combustible electrolyte inside the battery, thereby improving the intrinsic safety of the battery cell; furthermore, by combining in-situ solidification technology, the electrolyte inside the battery cell is transformed into a gel electrolyte. When thermal runaway occurs in the battery cell, the electrolyte in the gel electrolyte will absorb some heat as it breaks free from the polymer network, thereby reducing the internal temperature of the battery and further improving its safety performance.

Description

Technical Field

[0001] This invention belongs to the field of solid-liquid hybrid battery technology, and relates to a solid-liquid hybrid battery and its preparation method. Background Technology

[0002] Compared to other types of batteries such as lead-acid and nickel-cadmium batteries, lithium-ion batteries have advantages such as high specific capacity, high operating voltage, fast charging speed, wide operating temperature range, long cycle life, small size, and light weight. Currently, they are widely used in mobile phones, laptops, power tools, and other fields, and their application scope is becoming increasingly broad, making it a major development direction for major battery manufacturers.

[0003] Currently, lithium-ion batteries possess advantages such as high voltage, high specific energy, numerous cycle times, and long storage time. They are widely used not only in portable electronic devices such as mobile phones, digital cameras, and laptops, but also in large and medium-sized electric equipment such as electric vehicles, electric bicycles, and power tools. Therefore, the requirements for the self-discharge and safety performance of lithium-ion batteries are becoming increasingly stringent.

[0004] The safety performance of ternary lithium batteries has always been a major concern in the industry. With the development of ternary lithium batteries in the power battery market, people are paying increasing attention to their safety performance. From an energy density perspective, ternary materials have an absolute advantage over lithium iron phosphate and lithium manganese oxide, but their safety performance remains a major obstacle to their large-scale application. Large-capacity pure ternary lithium batteries often fail safety tests such as nail penetration and overcharge, which is why large-capacity batteries are generally mixed with lithium manganese oxide.

[0005] Currently, there are several solutions to improve the safety performance of ternary materials: 1. Selecting ternary materials with the optimal safety ratio. As the nickel content in ternary materials increases, material stability decreases, leading to poorer safety performance. The current mainstream ternary nickel-cobalt-manganese ratio with the best safety is 1:1:1, but its energy density is low and cannot meet the high energy density requirements of power batteries. 2. Surface coating of ternary materials. CN 11290325A discloses a method for improving the safety performance of ternary materials through elemental doping and surface coating. This paper dops aluminum, zirconium, and fluorine into ternary materials and coats the surface with a layer of zirconium hydrogen phosphate and boron compounds. This solution can effectively solve the gas generation problem of cathode materials and improve safety performance. It also ensures good conductivity and structural stability of the material, guaranteeing the normal release of electrochemical performance. However, ternary materials are novel materials developed from doping processes. Adding other elements to ternary materials not only has unknown effects on their electrochemical performance but also places higher demands on the manufacturing process. Increased costs limit the application of ternary materials in power batteries, and the coating process affects product consistency. Therefore, this approach is difficult to implement on a large scale. Single-crystal ternary materials, similar to lithium cobalt oxide primary particles, offer significantly improved safety performance. Micron-sized primary particles have a more complete layered structure and excellent material stability, thus improving both cycle performance and safety. Increasing the primary particle size reduces the specific surface area, decreasing the contact area between the material and the electrolyte, thereby reducing the risk of thermal runaway.

[0006] Besides optimizing ternary materials, the safety performance of other materials in the battery system must also be ensured through proper coordination. For example, high-boiling-point and flash-point flame-retardant additives, such as organophosphorus and fluorophosphates, can be added to the electrolyte. Ceramic separators can also be used, increasing the thickness of the separator substrate and coating, and new high-temperature resistant non-woven materials can be employed. However, the development of flame-retardant electrolytes is currently slow; insufficient flame-retardant additives will not provide a flame-retardant effect, while excessive addition will reduce cell performance. When ternary lithium batteries experience thermal runaway, the organic electrolyte is the primary source of combustion. If the electrolyte content is not reduced or its properties are not fundamentally altered, the safety hazard of thermal runaway remains.

[0007] CN105322228A discloses a high-safety flame-retardant lithium-ion battery electrolyte. The electrolyte contains electrolyte lithium salt, various cyclic carbonates, linear carbonates, film-forming additives, and flame-retardant additives. The amount of film-forming additives added is 0.1-3% of the total weight of the electrolyte. The flame-retardant additives include phosphorus-based and halogen-based additives, and the total amount of flame-retardant additives added is 1-25%. However, the addition of flame retardants to the electrolyte still poses a safety hazard of thermal runaway.

[0008] Therefore, improving battery safety performance is a technical problem that urgently needs to be solved. Summary of the Invention

[0009] The purpose of this invention is to provide a solid-liquid hybrid battery and its preparation method. This invention combines a solid electrolyte membrane with an in-situ solidified electrolyte, effectively reducing the content of combustible electrolyte inside the battery, thereby improving the intrinsic safety of the cell. Furthermore, by combining in-situ solidification technology, the electrolyte inside the cell is transformed into a gel electrolyte. When thermal runaway occurs in the cell, the electrolyte in the gel electrolyte, detached from the polymer network, absorbs some heat, thereby reducing the internal temperature of the battery and further improving its safety performance.

[0010] To achieve this objective, the present invention adopts the following technical solution:

[0011] In a first aspect, the present invention provides a method for preparing a solid-liquid hybrid battery, the method comprising the following steps:

[0012] (1) Assemble the positive electrode, negative electrode and solid electrolyte membrane to obtain the battery cell;

[0013] (2) In-situ solidified electrolyte is injected into the cell described in step (1) for solidification to obtain the solid-liquid hybrid battery.

[0014] This invention combines a solid electrolyte membrane with an in-situ solidified electrolyte to effectively reduce the content of flammable electrolytes inside the battery, thereby improving the intrinsic safety of the cell. Furthermore, the in-situ solidification technology transforms the electrolyte inside the cell into a gel electrolyte. When thermal runaway occurs in the cell, the electrolyte in the gel electrolyte breaks free from the polymer network and absorbs some heat, thus lowering the internal temperature of the battery, further enhancing its safety performance, and reducing production costs.

[0015] In this invention, if conventional organic electrolyte is injected into the battery cell, thermal runaway will occur after the battery cell is punctured for 0.2-0.5 hours, resulting in minimal improvement in safety performance.

[0016] Compared to ordinary liquid lithium-ion batteries, the solid-liquid hybrid battery provided by this invention has excellent safety performance advantages. The battery cells made based on this design can pass various safety tests such as needle penetration, hot box, extrusion, and overcharge, and the electrical performance of this design is no weaker than that of ordinary liquid lithium-ion batteries.

[0017] In this invention, the preparation methods of the positive electrode and the negative electrode can be carried out using conventional techniques.

[0018] Preferably, after the in-situ solidified electrolyte is injected into the battery cell in step (2), it is left to stand.

[0019] In this invention, allowing the electrolyte to stand after injection ensures that the precursor of the in-situ solidified electrolyte uniformly wets the internal components of the battery cell.

[0020] Preferably, the settling time is ≥24h, such as 24h, 25h, 26h, 28h, 30h, 32h, 34h, 35h, 38h, 40h, 42h, 45h, or 48h.

[0021] In this invention, an excessively short settling time leads to insufficient wetting of the electrolyte inside the cell, increased interfacial impedance, and severe lithium plating, preventing the cell from fully realizing its electrical performance. During cycling, the battery's coulombic efficiency is low, resulting in a rapid decrease in capacity retention. Regarding rate performance, due to the high interfacial impedance, lithium-ion transport within the cell is difficult, leading to a significant reduction in rate performance.

[0022] Preferably, the curing temperature in step (2) is 60 to 80°C, such as 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C, 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, or 80°C.

[0023] Preferably, the curing time in step (2) is 3 to 12 hours, such as 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours.

[0024] Preferably, the amount of in-situ solidified electrolyte injected in step (2) is 30-50%, such as 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, or 50%.

[0025] In this invention, as is known to those skilled in the art, exemplarily, taking a 3g / Ah lithium-ion battery as an example, the amount of in-situ solid electrolyte added is 0.9–1.5 g / Ah. In this invention, insufficient injection will prevent the formation of a uniform interface modification layer at the solid / solid interface, hindering lithium-ion transport within the cell and significantly reducing battery performance; while excessive injection will result in an excessively high content of flammable organic electrolyte inside the battery, severely impacting battery safety. When the battery is used in extreme environments, high liquid content is more likely to cause thermal runaway, posing a risk of gas expansion and explosion.

[0026] Preferably, the positive electrode active material in the positive electrode sheet includes monocrystalline positive electrode material and / or polycrystalline positive electrode material, and is preferably monocrystalline positive electrode material.

[0027] The solid-liquid hybrid battery provided in this invention exhibits superior performance for monocrystalline cathode materials. While typical ternary monocrystalline materials cannot pass the nail penetration test, this invention achieves 100% pass. It is also more suitable for high-energy-density (350Wh / Kg) high-nickel ternary monocrystalline materials, improving battery safety without reducing cell energy density. In contrast, polycrystalline cathode materials have incomplete layered structures, resulting in poor material stability and a higher susceptibility to decomposition and thermal runaway at high temperatures. Furthermore, polycrystalline ternary materials have a larger specific surface area and higher surface activity; side reactions upon contact with the electrolyte can damage the material's structure, further reducing safety performance. Therefore, the solid-liquid hybrid battery provided in this invention significantly improves safety performance for monocrystalline cathode materials.

[0028] Preferably, the preparation method of the in-situ solidified electrolyte includes:

[0029] The in-situ solidified electrolyte is obtained by mixing the liquid electrolyte, monomer and initiator.

[0030] Preferably, the monomer comprises any one or a combination of at least two of the following: acrylate organic compounds, vitamin C, polyethylene glycol, acrylate organic compounds, or epoxy organic compounds.

[0031] Preferably, the initiator includes any one or a combination of at least two of azo initiators, organic peroxide initiators, inorganic oxide initiators, or redox initiators.

[0032] Preferably, the solid electrolyte membrane in step (1) includes any one or a combination of at least two of the following: polymer solid electrolyte membrane, organic / inorganic composite electrolyte membrane, oxide electrolyte membrane, or sulfide electrolyte membrane.

[0033] As a preferred technical solution, the preparation method includes the following steps:

[0034] (1) Assemble the positive electrode, negative electrode and solid electrolyte membrane to obtain the battery cell;

[0035] (2) Inject in-situ solidified electrolyte into the cell described in step (1), let it stand for no less than 24 hours, and then solidify it at 60-80°C for 3-12 hours to obtain the solid-liquid hybrid battery;

[0036] The amount of in-situ solidified electrolyte injected is 30-50%, and the positive electrode active material in the positive electrode sheet is a single-crystal positive electrode material;

[0037] The preparation method of the in-situ solidified electrolyte includes:

[0038] The in-situ solidified electrolyte is obtained by mixing the liquid electrolyte, monomer and initiator.

[0039] In a second aspect, the present invention also provides a solid-liquid hybrid battery, which is prepared by the method for preparing a solid-liquid hybrid battery as described in the first aspect.

[0040] Compared with the prior art, the present invention has the following beneficial effects:

[0041] This invention combines a solid electrolyte membrane with an in-situ solidified electrolyte to effectively reduce the content of flammable electrolytes inside the battery, thereby improving the intrinsic safety of the cell. Furthermore, the in-situ solidification technology transforms the electrolyte inside the cell into a gel electrolyte. When thermal runaway occurs in the cell, the electrolyte in the gel electrolyte breaks free from the polymer network and absorbs some heat, thus lowering the internal temperature of the battery and further enhancing its safety performance. The battery provided by this invention has a needle penetration pass rate of over 80%, a hot box pass rate of over 90%, an extrusion pass rate of over 80%, a 1C / 1C cycle performance of over 844@80% at 25°C, a 3C discharge capacity retention rate of over 88.56%, and a 60°C high-temperature storage capacity recovery rate of over 94.66%. Furthermore, by selecting a single-crystal cathode material and controlling the liquid injection volume, the needle penetration pass rate is over 100%, the hot box pass rate is over 100%, the extrusion pass rate is over 100%, the 1C / 1C cycle performance of over 912@80% at 25°C, the 3C discharge capacity retention rate is over 89.73%, and the 60°C high-temperature storage capacity recovery rate is over 97.07%. Attached Figure Description

[0042] Figure 1 This is a schematic diagram of the battery provided in Example 1 after undergoing a needle penetration test.

[0043] Figure 2 This is a schematic diagram of the battery provided in Comparative Example 1 after undergoing a nail penetration test. Detailed Implementation

[0044] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0045] Example 1

[0046] This embodiment provides a solid-liquid hybrid battery, and the preparation method of the solid-liquid hybrid battery is as follows:

[0047] First, a positive electrode, a negative electrode, a solid electrolyte membrane, and an in-situ solidified electrolyte are prepared.

[0048] Positive electrode sheet: NCM811 single crystal material, conductive carbon black, carbon nanotubes and polyvinylidene fluoride are mixed in a mass ratio of 95:1.5:1:2.5, NMP is added, homogenized, and uniformly coated on both sides of aluminum foil. After drying, rolling and cutting, the positive electrode sheet is obtained.

[0049] Negative electrode sheet: Graphite, silicon suboxide, conductive carbon black, styrene-butadiene rubber and sodium carboxymethyl cellulose are mixed in a mass ratio of 86:8:2.5:2:1.5, water is added, homogenized, and coated evenly on both sides of copper foil. After drying, rolling and cutting, the negative electrode sheet is obtained.

[0050] Solid electrolyte membrane: Lithium lanthanum zirconium oxide and LiTFSI and N,N-dimethylformamide are mixed, then polyvinylidene fluoride is added, and the mixture is stirred at room temperature for 12 hours. The mixture is then cast, peeled, wound up, and slit to obtain a polymer electrolyte membrane.

[0051] In-situ solid electrolyte: Methyl methacrylate and azobisisobutyronitrile are added to an organic electrolyte (1M LiPF6 / EC+EMC) and mixed to obtain an in-situ solid electrolyte;

[0052] (1) Single-crystal ternary positive electrode sheet, negative electrode sheet, and solid electrolyte membrane are stacked into a core using a Z-shaped stacking machine to obtain a battery cell:

[0053] (2) The cell is passed through a tab welding machine, soft pack side sealing and top sealing, and then an in-situ solidified electrolyte is injected. After standing for 24 hours, it is cured at 65°C for 8 hours and pre-sealed to obtain the solid-liquid hybrid battery. The amount of in-situ solidified electrolyte injected is 50%.

[0054] Example 2

[0055] The difference between this embodiment and Embodiment 1 is that in this embodiment, the ternary single crystal material is NCM523, the amount of in-situ cured electrolyte injected is 40%, the curing temperature is 80℃, the curing time is 3h, and the standing time is 36h.

[0056] The remaining preparation methods and parameters are consistent with those in Example 1.

[0057] Example 3

[0058] The difference between this embodiment and Embodiment 1 is that the amount of in-situ solidified electrolyte injected in this embodiment is 30%.

[0059] The remaining preparation methods and parameters are consistent with those in Example 1.

[0060] Example 4

[0061] The difference between this embodiment and Embodiment 1 is that the amount of in-situ solidified electrolyte injected in this embodiment is 20%.

[0062] The remaining preparation methods and parameters are consistent with those in Example 1.

[0063] Example 5

[0064] The difference between this embodiment and Embodiment 1 is that the amount of in-situ solidified electrolyte injected in this embodiment is 60%.

[0065] The remaining preparation methods and parameters are consistent with those in Example 1.

[0066] Example 6

[0067] The difference between this embodiment and Embodiment 1 is that the cathode material in this embodiment is ternary polycrystalline NCM811.

[0068] The remaining preparation methods and parameters are consistent with those in Example 1.

[0069] Comparative Example 1

[0070] This comparative example provides a liquid lithium-ion battery, in which the positive electrode, negative electrode and organic electrolyte are consistent with those in Example 1, and the separator is a ceramic separator (PP substrate with an aluminum oxide layer coated on the surface).

[0071] The preparation method is as follows:

[0072] (1) The positive electrode, negative electrode, and ceramic separator are stacked into a core using a Z-shaped stacking machine to obtain a battery cell:

[0073] (2) The cell is subjected to tab welding, soft-pack battery side sealing, and top sealing. Then, electrolyte is injected, vacuum standing for 60 seconds, and pre-sealing is performed. After standing at 25℃ for 24 hours, formation is performed at 45℃. After formation, vacuuming and secondary sealing are performed to obtain the required cell.

[0074] Comparative Example 2

[0075] This comparative example provides a battery, the difference from Comparative Example 1 being that the electrolyte is replaced with the in-situ solidified electrolyte of Example 1.

[0076] In the preparation method, after injecting the in-situ solidified electrolyte, the solidification is carried out according to the solidification conditions in Example 1.

[0077] Comparative Example 3

[0078] The difference between this comparative example and Example 1 is that in this comparative example, the in-situ solidified electrolyte is directly replaced with the organic electrolyte in Example 1, without the need for solidification.

[0079] The remaining preparation methods and parameters are consistent with those in Example 1.

[0080] Comparative Example 4

[0081] The difference between this comparative example and Comparative Example 1 is that the cathode material in this comparative example is ternary polycrystalline NCM523.

[0082] The remaining preparation methods and parameters are consistent with those of Comparative Example 1.

[0083] Figure 1 A schematic diagram of the battery provided in Example 1 after undergoing a needle penetration test is shown (the numbers 1234 in the figure are just battery labels and have no special meaning). Figure 2 A schematic diagram of the battery provided in Comparative Example 1 after undergoing a nail penetration test is shown; from Figure 1 and Figure 2 The comparison shows that the battery cell in Example 1 did not catch fire or swell after being punctured, and its safety performance was greatly improved. In contrast, the battery cell in Comparative Example 1 caught fire after being punctured, and produced a large amount of black smoke, posing a significant safety hazard.

[0084] Comparative Example 5

[0085] The difference between this comparative example and Comparative Example 2 is that the cathode material in this comparative example is ternary polycrystalline NCM523.

[0086] The remaining preparation methods and parameters are consistent with those of Comparative Example 2.

[0087] Comparative Example 6

[0088] The difference between this comparative example and Comparative Example 3 is that the cathode material in this comparative example is ternary polycrystalline NCM523.

[0089] The remaining preparation methods and parameters are consistent with those of Comparative Example 3.

[0090] Among them, Comparative Examples 1-3 are compared with Example 1, and Comparative Examples 4-6 are compared with Example 6.

[0091] The batteries provided in Examples 1-6 and Comparative Examples 1-6 were subjected to safety and electrochemical performance tests, including: 1C / 1C cycling at 25°C, rate performance (discharge capacity retention test at 3C current), and high-temperature storage (storage at 60°C for 30 days, cell capacity retention measured). The characteristics of the batteries are shown in Table 1, the test results of safety performance are shown in Table 2, and the test results of electrochemical performance are shown in Table 3.

[0092] Table 1

[0093]

[0094]

[0095] Table 2

[0096]

[0097]

[0098] Table 3

[0099]

[0100]

[0101] Note: For example, 940@80% means that after 940 cycles, the capacity retention rate will be below 80%.

[0102] As can be seen from Tables 1, 2 and 3, both the needle penetration pass rate and extrusion pass rate of the battery are improved regardless of whether the cathode material is monocrystalline or polycrystalline. However, the safety performance of the battery is improved more significantly when the cathode material is monocrystalline.

[0103] As can be seen from the data results in Example 1 and Comparative Examples 1-3, the solid-liquid hybrid battery provided by the present invention has greatly improved its safety performance, and for batteries with single-crystal cathode materials, the cycle performance of the battery is also maintained with minimal loss.

[0104] As can be seen from the data results of Example 6 and Comparative Examples 4-6, although the safety performance of the battery with polycrystalline cathode material has been improved to a certain extent, its cycle performance has been severely compromised.

[0105] The data results from Examples 1 and 6 show that the solid-liquid hybrid battery provided by the present invention is more suitable for monocrystalline cathode materials. For polycrystalline cathode materials, while the safety performance is improved when combined with the solid-liquid hybrid battery provided by the present invention, the polycrystalline material has more pores and will absorb a large amount of electrolyte, resulting in the inability to build a good in-situ solidification modification layer at the interface, which hinders lithium-ion transport, reduces coulombic efficiency, and has a significant impact on its cycle performance.

[0106] The data results from Examples 1, 4, and 5 show that if the amount of in-situ solidified electrolyte injected is too small, it is not conducive to building a good modification layer at the interface, resulting in a decrease in electrical performance, such as a significant decrease in cycle life and rate capability. On the other hand, if the amount injected is too large, it will lead to a decrease in the safety performance of the cell. Under extreme usage conditions, the cell may still catch fire or explode, which could be a major safety accident.

[0107] The data results from Example 1 and Comparative Example 3 show that, compared with organic electrolytes, the in-situ solidified electrolyte in this invention can absorb some of the heat and gel when the battery generates a large amount of heat, thereby slowing down the heating rate of the cell, avoiding further thermal runaway, and greatly improving the safety performance of the battery.

[0108] In summary, this invention, by combining a solid electrolyte membrane with an in-situ solidified electrolyte, can effectively reduce the content of flammable electrolytes inside the battery, thereby improving the intrinsic safety of the cell. Furthermore, by combining in-situ solidification technology, the electrolyte inside the cell is transformed into a gel electrolyte. When thermal runaway occurs in the cell, the electrolyte in the gel electrolyte, detached from the polymer network, absorbs some heat, thereby reducing the internal temperature of the battery and further improving its safety performance. The battery provided by this invention has a needle penetration pass rate of over 80%, a hot box pass rate of over 90%, an extrusion pass rate of over 80%, a 1C / 1C cycle performance of over 844@80% at 25°C, a 3C discharge capacity retention rate of over 88.56%, and a 60°C high-temperature storage capacity recovery rate of over 94.66%. Furthermore, by selecting a single-crystal cathode material and controlling the liquid injection volume, the needle penetration pass rate is over 100%, the hot box pass rate is over 100%, the extrusion pass rate is over 100%, the 1C / 1C cycle performance of over 912@80% at 25°C, the 3C discharge capacity retention rate is over 89.73%, and the 60°C high-temperature storage capacity recovery rate is over 97.07%.

[0109] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A method for preparing a solid-liquid hybrid battery, characterized in that, The preparation method includes the following steps: (1) A battery cell is obtained by assembling a positive electrode, a negative electrode and a solid electrolyte membrane; the solid electrolyte membrane includes any one or a combination of at least two of organic / inorganic composite electrolyte membrane, oxide electrolyte membrane or sulfide electrolyte membrane; (2) Mix the liquid electrolyte, monomer and initiator to obtain the in-situ solidified electrolyte; inject the in-situ solidified electrolyte into the cell described in step (1), let it stand for no less than 24 hours, and obtain the solid-liquid hybrid battery after solidification; The positive electrode active material in the positive electrode sheet is NCM811 single crystal material; The injection volume of the in-situ solidified electrolyte is 30-50%.

2. The method for preparing a solid-liquid hybrid battery according to claim 1, characterized in that, The monomers include any one or a combination of at least two of the following: acrylate organic compounds, vitamin C, polyethylene glycol, acrylate organic compounds, or epoxy organic compounds.

3. The method for preparing a solid-liquid hybrid battery according to claim 1, characterized in that, The initiator includes any one or a combination of at least two of azo initiators, organic peroxide initiators, inorganic oxide initiators, or redox initiators.

4. The method for preparing a solid-liquid hybrid battery according to claim 1, characterized in that, The curing temperature is 60~80℃ and the time is 3~12h.

5. A solid-liquid hybrid battery, characterized in that, The solid-liquid hybrid battery is prepared by the method for preparing a solid-liquid hybrid battery as described in any one of claims 1-4.

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