A method for preparing a negative electrode, the negative electrode itself, and a solid-liquid hybrid battery containing the negative electrode.

Abstract

This invention relates to a method for preparing a negative electrode, the negative electrode itself, and a solid-liquid hybrid battery containing the negative electrode. The method for preparing the negative electrode includes the following steps: pressing a lithium sheet onto a copper foil; sequentially subjecting the surface of the metallic lithium to multi-stage, segmented nitrogen treatment, with each stage involving an increasing temperature and a treatment time of 30 to 90 minutes; and cooling and allowing it to stand after each stage of treatment to form a multi-layered gradient lithium nitride protective layer. Through this preparation method, a gradient lithium nitride protective layer with progressively increasing density and elasticity from the inside out can be formed on the surface of the negative electrode. This structure significantly reduces stress concentration and mismatch risk, suppresses microcracks and interface cracking, reduces the rate of increase in interfacial impedance, and improves long-term cycle stability and safety.

Description

Technical Field

[0001] This application relates to the field of battery materials technology, specifically to a method for preparing a negative electrode, the negative electrode, and a solid-liquid hybrid battery containing the negative electrode. Background Technology

[0002] With the widespread application of lithium-ion batteries in high-energy-density fields such as new energy vehicles and high-end energy storage, higher requirements are being placed on battery safety and cycle life. Lithium metal anodes, due to their extremely high theoretical capacity and low potential, are considered an ideal choice for next-generation high-energy-density batteries. However, the high interfacial impedance between lithium metal and the solid electrolyte makes them prone to interfacial microcracks and ruptures during cycling, becoming a major bottleneck limiting performance improvement and large-scale application.

[0003] In lithium metal batteries, reducing interfacial impedance and improving interfacial stability are crucial for achieving efficient energy conversion and long cycle life. Existing technologies mostly employ a single-structure lithium nitride protective layer, but due to the significant difference in thermal expansion coefficients between the lithium nitride and the bulk lithium metal, volume changes during thermal cycling or charge-discharge processes can easily lead to interfacial microcracks and ruptures, causing a rapid increase in interfacial impedance and consequently affecting battery performance and lifespan.

[0004] Therefore, how to effectively buffer the interfacial stress caused by the difference in thermal expansion coefficients between lithium metal and lithium nitride protective layer, suppress interfacial microcracks and cracking, reduce interfacial impedance, and improve cycle stability and safety has become a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0005] To address the aforementioned technical problems, this application provides a method for preparing a negative electrode, a negative electrode, and a solid-liquid hybrid battery containing the negative electrode.

[0006] The first aspect of this application provides a method for preparing a negative electrode, characterized by comprising the following steps: a) Press lithium sheets onto copper foil; b) The surface of metallic lithium is subjected to multi-stage nitrogen treatment in sequence, with the temperature of each stage increasing and the treatment time of each stage ranging from 30 to 90 minutes. After each stage of treatment, the surface is cooled and allowed to stand to form a multi-layered gradient structure of lithium nitride protective layer.

[0007] Through the above process, the multi-stage nitrogen treatment employs progressively increasing temperatures and a segmented reaction method, allowing the reaction between nitrogen and the lithium metal surface to proceed gradually. In the initial low-temperature stage, the reaction rate between nitrogen and lithium metal is low, resulting in a lithium nitride layer with low crystallinity, a relatively loose and elastic structure, which is beneficial for achieving good mechanical matching with the lithium metal bulk and buffering volume changes and stress during charging, discharging, and thermal cycling. As the treatment temperature gradually increases, the reaction rate between surface nitrogen and lithium accelerates, and the resulting lithium nitride layer gradually becomes denser, with increased crystallinity and elastic modulus, forming a dense outer protective layer with high barrier properties. During the multi-stage treatment process, cooling and settling are performed after each stage of treatment, which helps release thermal stress and promotes the gradual transition of the interlayer structure, avoiding stress concentration and interface mismatch caused by a single high-temperature treatment. Ultimately, a multi-layered gradient lithium nitride protective layer is formed with gradually increasing density and elasticity from the inside out, achieving a continuous transition in thermal expansion coefficient and elastic modulus. This effectively suppresses microcracks and interface cracking, reduces the rate of interface impedance growth, and improves the cycle life and safety of solid-liquid hybrid batteries.

[0008] Furthermore, the multi-stage segmented nitrogen treatment consists of 3-6 stages, with each stage having a treatment temperature of 35°C to 60°C.

[0009] Furthermore, the nitrogen gas has a purity of 99.999% or higher and a flow rate of 2 m / s to 6 m / s.

[0010] Furthermore, the thickness of the lithium sheet is 20-80 μm.

[0011] Furthermore, the thickness of the copper foil is 15-30 μm.

[0012] A second aspect of this application provides a negative electrode prepared using the above-described method. The negative electrode has a multi-layered gradient lithium nitride protective layer on its surface, which effectively improves the interfacial stability and cycle performance of the solid-liquid hybrid battery.

[0013] A third aspect of this application provides a solid-liquid hybrid battery, including a positive electrode, the aforementioned negative electrode, a solid electrolyte membrane, and an electrolyte.

[0014] Furthermore, the solid electrolyte membrane comprises a solid electrolyte and a base membrane, wherein the solid electrolyte is Li. 1.3 Al 0.3 Ti 1.7 A mixture of (PO4)3 ceramic and PEO in a mass ratio of 90:10 to 99:1.

[0015] Furthermore, the electrolyte is a 1 mol / L LiPF6 electrolyte, and the solvent is a mixed solvent of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate in a volume ratio of 1:1:1.

[0016] Furthermore, the positive electrode comprises at least one of lithium iron phosphate, lithium manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, and lithium cobalt oxide.

[0017] The present invention has the following beneficial effects: By forming a multi-layered gradient lithium nitride protective layer through multi-stage segmented nitrogen treatment, the impedance growth rate at the lithium metal anode-electrolyte interface can be significantly reduced, thereby improving the battery's cycle life and coulombic efficiency.

[0018] The gradient structure of the lithium nitride protective layer achieves a continuous transition in thermal expansion coefficient and elastic modulus, effectively mitigating volume changes and stress concentration during charging and discharging, suppressing interfacial microcracks and cracking, and improving long-term cycle stability and safety.

[0019] The negative electrode preparation method of the present invention is simple and has strong applicability. The obtained negative electrode can be widely used in various positive electrode and solid-liquid hybrid battery systems, and has good industrialization prospects. Detailed Implementation

[0020] To facilitate understanding of this application, a more complete description will be provided below. This application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of this application.

[0021] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature. In the description of the application, "multiple" means at least two, such as two, three, etc., unless otherwise explicitly specified. In the description of this application, "several" means at least one, such as one, two, etc., unless otherwise explicitly specified.

[0022] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0023] In some preferred embodiments, the present invention provides a method for preparing a negative electrode, comprising the following steps: First, lithium sheets are pressed onto copper foil; then, the surface of the metallic lithium is subjected to multi-stage nitrogen treatment, with the temperature increasing in each stage and the treatment time ranging from 30 to 90 minutes. After each stage of treatment, the surface is cooled and allowed to stand, so as to form a multi-layered gradient lithium nitride protective layer on the surface of the lithium sheet.

[0024] For example, the multi-stage segmented nitrogen treatment can be 3, 4, 5, or 6 stages; the treatment temperature for each stage can be any one of 35℃, 40℃, 45℃, 50℃, 55℃, or 60℃, or a temperature range between any two values; the treatment time for each stage can be 30 minutes, 40 minutes, 50 minutes, 60 minutes, 70 minutes, 80 minutes, or 90 minutes, or a time range between any two values.

[0025] In some preferred embodiments, after each processing stage, the electrode sheet must be removed, allowed to cool naturally to room temperature, and then left to stand for 5-15 minutes. This cooling and standing process ensures that the lithium nitride layer gradually changes after stress release and structural adjustment, forming a gradient structure with progressively increasing density and elasticity from the inside out. Throughout the cooling and standing process, the electrode sheet must be kept under a nitrogen protective atmosphere to prevent oxidation and moisture contamination.

[0026] In some preferred embodiments, the nitrogen gas has a purity of 99.999% or higher and a flow rate of 2 m / s to 6 m / s. For example, the nitrogen flow rate can be 2 m / s, 4 m / s, 6 m / s, or any range between two values, which can ensure the density and uniformity of the lithium nitride protective layer and effectively suppress oxidation and impurity introduction.

[0027] In some preferred embodiments, the thickness of the lithium sheet is 20-80 μm. For example, the thickness of the lithium sheet can be 20 μm, 40 μm, 60 μm, 80 μm, or any range between two values, to meet the energy density and mechanical strength requirements of different battery designs.

[0028] In some preferred embodiments, the thickness of the copper foil is 15-30 μm. For example, the copper foil thickness can be 15 μm, 20 μm, 25 μm, 30 μm, or any range between two values, to improve the current collector strength and overall structural stability of the negative electrode.

[0029] In some preferred embodiments, the present invention also provides a negative electrode prepared by the above-described method, which has a lithium nitride protective layer with a multi-layer gradient structure on its surface, and can effectively improve the interface stability and cycle performance of the solid-liquid hybrid battery.

[0030] In some preferred embodiments, the present invention also provides a solid-liquid hybrid battery, comprising a positive electrode, the aforementioned negative electrode, a solid electrolyte membrane, and an electrolyte.

[0031] In some preferred embodiments, the solid electrolyte membrane comprises a solid electrolyte and a base membrane.

[0032] Furthermore, the solid electrolyte can be Li 1.3 Al 0.3 Ti 1.7 A mixture of (PO4)3 ceramic and PEO in a mass ratio of 90:10 to 99:1, for example, 95:5. The base film can be a polypropylene film or a polyethylene film.

[0033] In some preferred embodiments, the electrolyte is a 1 mol / L LiPF6 electrolyte, and the solvent is a mixed solvent of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate in a volume ratio of 1:1:1.

[0034] In some preferred embodiments, the positive electrode may contain at least one of lithium iron phosphate, lithium manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, and lithium cobalt oxide. The negative electrode of the present invention is applicable to a variety of positive electrode systems.

[0035] Example 1: This example provides a negative electrode and its preparation method, and applies it to the assembly of a solid-liquid hybrid battery.

[0036] I. Raw Materials and Pretreatment for Anode Preparation In this embodiment, lithium wafers (purity ≥99.9%, purchased from Tianjin Zhongneng Lithium Industry) were selected as the negative electrode active material. Lithium wafers with a thickness of 50 μm were used in an Ar atmosphere glove box environment (O2 and H2O both <1 ppm). To ensure the lithium wafer surface was clean and free of impurities, the entire operation was conducted inside the glove box to prevent the lithium wafer from contacting air or moisture, which could lead to oxidation or corrosion.

[0037] Next, electronic-grade copper foil (15 μm thick, purchased from Putailai) was prepared. The surface of the copper foil was first ultrasonically cleaned with anhydrous ethanol for 10 minutes to remove oil and impurities, and then dried with argon gas. The treated copper foil was laid flat on the worktable inside the glove box, and the lithium sheet was evenly pressed onto one side of the copper foil. A pressure of 200 kPa was applied to ensure that the lithium sheet and copper foil were tightly bonded without bubbles or wrinkles. The pressed lithium-copper composite electrode was then cut into 20 mm × 30 mm electrode sheets using a cutting knife for later use.

[0038] II. Multi-stage segmented nitrogen treatment to form a gradient lithium nitride protective layer The cut lithium metal electrodes are laid flat inside the quartz boat, ensuring that the electrodes do not overlap. The quartz boat is then placed into the reaction zone of the tubular furnace, connected to a high-purity nitrogen gas source (99.999% purity), and the nitrogen flow rate is adjusted to 4 m / s.

[0039] The multi-stage, segmented nitrogen treatment process is as follows: First stage: Set the target temperature of the tube furnace to 35℃, with a heating rate of 5℃ / min, and hold the temperature for 30 minutes after reaching the target temperature. After the treatment, remove the quartz boat, allow it to cool naturally to room temperature, and let it stand for 5 minutes.

[0040] Second stage: The electrode sheet is put back into the tube furnace and heated to 40°C at a heating rate of 5°C / min, and held at that temperature for 30 minutes. After processing, it is allowed to cool naturally to room temperature and then left to stand for 5 minutes.

[0041] Third stage: Heat to 45℃ at a rate of 5℃ / min and hold at that temperature for 40 minutes. Allow to cool naturally to room temperature and let stand for 5 minutes.

[0042] Fourth stage: Increase the temperature to 50℃ at a rate of 5℃ / min and hold for 60 minutes. Allow to cool naturally to room temperature and let stand for 5 minutes.

[0043] Fifth stage: Increase the temperature to 55℃ at a rate of 5℃ / min and hold for 60 minutes. Allow to cool naturally to room temperature and let stand for 5 minutes.

[0044] Stage 6: Increase the temperature to 60℃ at a rate of 5℃ / min and hold for 90 minutes. After treatment, allow to cool naturally to room temperature and let stand for 5 minutes.

[0045] After each processing stage, the electrode sheet must be removed, allowed to cool naturally to room temperature, and left to stand. This ensures that the lithium nitride layer gradually changes after stress release and structural adjustment, forming a gradient structure with progressively increasing density and elasticity from the inside out. Throughout the nitrogen treatment process, the electrode sheet is kept under a high-purity nitrogen protective atmosphere to prevent oxidation and moisture contamination.

[0046] After processing, the electrode sheets should be immediately transferred to an anhydrous and oxygen-free glove box for storage to prevent moisture and oxygen in the air from damaging the lithium nitride protective layer.

[0047] III. Assembly of Solid-Liquid Hybrid Batteries The aforementioned negative electrode is used in the assembly of a solid-liquid hybrid battery. The positive electrode is made of LiNi. 0.8 Co 0.1 Mn 0.190g of O2 active material, 2g of conductive carbon black, and 3g of PEO-PVDF binder were added to 150 mL of anhydrous tetrahydrofuran and stirred for 2 hours. After the slurry was uniform, it was coated on both sides of an aluminum foil with a thickness of 20 μm. It was dried at 120℃ for 2 hours, rolled to a thickness of 120 μm, and cut into 20 mm × 30 mm electrode sheets.

[0048] The solid electrolyte is Li 1.3 Al 0.3 Ti 1.7 (PO4)3 ceramic powder and PEO (polyethylene oxide) were mixed at a mass ratio of 95:5, heated and stirred at 100°C for 30 minutes, and coated on both sides of a 12μm thick polypropylene membrane using a coating method, with a single-sided thickness of 2.5μm. After cooling and curing, the mixture was cut into sheets to obtain a solid electrolyte membrane.

[0049] The electrolyte was 1 mol / L LiPF6 dissolved in a mixed solvent of EC, DMC and EMC in a volume ratio of 1:1:1. The solution was stirred thoroughly to dissolve the solution, filtered to remove impurities, and ultrasonically degassed for 10 minutes.

[0050] In an Ar atmosphere glove box, the positive electrode, solid electrolyte membrane, and negative electrode are stacked sequentially. The above-mentioned electrolyte is injected into the spaces between the positive electrode and the solid electrolyte, and between the negative electrode and the solid electrolyte, respectively, at a volume of 10 μL / cm³. 2 The batteries are heat-sealed with aluminum-plastic film to obtain sealed finished batteries. The batteries are then left to stand for 12 hours before use.

[0051] Example 2: Preparation of negative electrodes with different lithium sheet and copper foil thicknesses and battery assembly This embodiment is based on Example 1, except that the thickness of the lithium metal sheet is adjusted to 80 μm and the thickness of the copper foil is adjusted to 20 μm. The other raw materials, equipment and operating steps are the same as in Example 1.

[0052] Example 3: Preparation of negative electrode with three-stage nitrogen treatment and battery assembly This embodiment employs a three-stage nitrogen treatment process, highlighting the variation in the number of treatment stages.

[0053] In an Ar atmosphere glove box, a 50 μm thick lithium metal sheet is pressed onto a 15 μm copper foil and cut into 20 mm × 30 mm electrodes.

[0054] The multi-stage nitrogen treatment process is as follows: First stage: Heat to 35℃ at a heating rate of 5℃ / min, hold at that temperature for 60 minutes, and then let cool and stand for 5 minutes. Second stage: Heat to 45℃ at a heating rate of 5℃ / min, hold at the temperature for 60 minutes, and let cool and stand for 5 minutes. Third stage: Heat to 55℃ at a heating rate of 5℃ / min, hold at that temperature for 60 minutes, and then let cool and stand for 5 minutes.

[0055] Nitrogen gas purity was 99.999%, flow rate was 4 m / s. All other operations were the same as in Example 1. After the negative electrode treatment was completed, it was immediately transferred to an anhydrous and oxygen-free glove box for storage. The battery assembly, positive electrode, solid electrolyte membrane, and electrolyte preparation and assembly sequence were all the same as in Example 1.

[0056] Example 4: Anode preparation and battery assembly at different nitrogen flow rates This embodiment is based on Embodiment 1, but the nitrogen flow rate is adjusted to 2 m / s, and the other parameters are the same as in Embodiment 1.

[0057] Example 5: Anode preparation and battery assembly with different processing times This embodiment is based on Embodiment 1, but the nitrogen treatment time for each stage is adjusted to 40 minutes, while the other parameters are the same as in Embodiment 1.

[0058] Example 6: Preparation of negative electrodes with different copper foil thicknesses and battery assembly This embodiment is based on Embodiment 1, but the copper foil thickness is adjusted to 30 μm, and the other parameters are the same as in Embodiment 1.

[0059] Example 7: Preparation of negative electrodes with different lithium sheet thicknesses and battery assembly This embodiment is based on Embodiment 1, but the thickness of the lithium metal is adjusted to 20 μm, and the other parameters are the same as in Embodiment 1.

[0060] Example 8: Anode preparation and battery assembly with different number of processing stages This embodiment employs a four-stage nitrogen treatment process.

[0061] A 50 μm thick lithium metal sheet was pressed onto a 15 μm copper foil and cut into 20 mm × 30 mm electrode sheets. The multi-stage nitrogen treatment process consisted of four stages, with temperatures of 35℃, 40℃, 50℃, and 60℃, and a treatment time of 60 minutes for each stage, followed by a 5-minute cooling and settling period. The remaining operations were the same as in Example 1.

[0062] Example 9: Anode fabrication and battery assembly with different processing temperature combinations This embodiment uses a three-stage nitrogen treatment with temperatures of 40°C, 50°C, and 60°C, and each stage lasts for 90 minutes.

[0063] A 50 μm thick lithium metal sheet was pressed onto a 15 μm copper foil and cut into 20 mm × 30 mm electrode sheets. The multi-stage nitrogen treatment process consisted of three stages, with temperatures of 40℃, 50℃, and 60℃, and a treatment time of 90 minutes for each stage, followed by a 5-minute cooling and settling period. The remaining operations were the same as in Example 1.

[0064] Comparative Example 1: No multi-stage segmented nitrogen treatment was used. This comparative example did not employ multi-stage nitrogen treatment; instead, it was treated with nitrogen at 50°C for 310 minutes. Other raw materials, equipment, and operating procedures were the same as in Example 1. After treatment, the negative electrode was immediately transferred to an anhydrous and oxygen-free glove box for storage. Battery assembly was the same as in Example 1.

[0065] Comparative Example 2: Single High-Temperature Treatment This comparative example uses 60°C for processing in stages one through six, with other raw materials, equipment, and operating procedures being the same as in Example 1. After processing, the negative electrode sheet is immediately transferred to an anhydrous and oxygen-free glove box for storage. Battery assembly is the same as in Example 1.

[0066] Comparative Example 3: No nitrogen treatment was performed. This comparative example did not undergo any nitrogen treatment. In an Ar atmosphere glove box, a 50 μm thick lithium metal sheet was directly pressed onto a 15 μm copper foil, cut into 20 mm × 30 mm electrode sheets, and immediately transferred to an anhydrous and oxygen-free glove box for storage. The battery assembly was the same as in Example 1.

[0067] Interfacial impedance testing: The interfacial impedance of the assembled solid-liquid hybrid battery was measured using AC impedance spectroscopy. The testing instrument was a Bio-Logic VMP3 multichannel electrochemical workstation, with a frequency range set from 0.01 Hz to 1 MHz and an AC perturbation amplitude of 5 mV. The test temperature was 25℃, and the battery was allowed to stand for 12 hours before testing. The initial value of the interfacial impedance and its change after cycling were obtained by fitting a Nyquist plot.

[0068] Cycle performance testing: The battery's cycle life was tested using a constant current charge-discharge tester. The test rate was 1C, with a charging cut-off voltage of 4.2 V and a discharging cut-off voltage of 2.5 V. The capacity of the first cycle, the capacity after 100 cycles, and the capacity retention were recorded. Coulombic efficiency and impedance were also monitored. The test environment temperature was 25℃.

[0069] Table 1 Test results of the examples and comparative examples All embodiments employed a multi-stage, segmented nitrogen treatment process to form a multi-layered gradient lithium nitride protective layer. Test results showed that the interfacial impedance growth rate of Examples 1-9 was less than 3.6% / 100 cycles, the capacity retention rate after 100 cycles was higher than 91.5%, and the coulombic efficiency was close to 99%. Comparative Examples 1 and 2, which did not employ multi-stage segmented treatment or only used a single temperature for segmented treatment, showed a significantly increased impedance growth rate, decreased capacity retention rate, and decreased coulombic efficiency. Comparative Example 3, which did not undergo nitrogen treatment, exhibited the worst performance and a significantly shortened cycle life. This is because the density and elasticity of the lithium nitride protective layer gradually increase from the inside out, enabling a continuous transition in the coefficient of thermal expansion and elastic modulus between the lithium metal and the lithium nitride protective layer. This gradient structure significantly reduces stress concentration and mismatch risks, suppresses microcracks and interfacial cracking, reduces the rate of interfacial impedance growth, and improves long-term cycle stability and safety.

[0070] Different embodiments vary in parameters such as the number of processing stages, temperature, flow rate, and thickness of lithium sheet or copper foil, but their overall performance is superior to the comparative example. Some embodiments (such as Example 7, where the lithium sheet is thinner) have slightly lower capacity retention, but are still significantly better than the comparative example, indicating that the multi-stage segmented nitrogen treatment has strong universality.

[0071] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0072] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A method for producing a negative electrode, characterized by, The method comprises the following steps: a) pressing a lithium sheet onto a copper foil; b) sequentially performing multi-stage segmented nitrogen treatment on the surface of the lithium metal, with the temperature of each stage increasing, each stage being treated for 30-90 minutes, and cooling and standing after each stage of treatment to form a multi-layer gradient lithium nitride protective layer.

2. The method for producing a negative electrode according to claim 1, characterized by, The multi-stage segmented nitrogen treatment is 3-6 stages, and the temperature of each stage is 35-60℃.

3. The method for producing a negative electrode according to claim 1, wherein The purity of the nitrogen is 99.999% or higher, and the flow rate is 2-6 m / s.

4. The method for producing a negative electrode according to claim 1, wherein The thickness of the lithium sheet is 20-80 μm.

5. The method of producing a negative electrode according to claim 1, wherein The thickness of the copper foil is 15-30 μm.

6. A negative electrode characterized by comprising: The negative electrode is prepared using the preparation method of any one of claims 1-5.

7. A solid-liquid hybrid battery, characterized by, The battery comprises a positive electrode, a negative electrode according to claim 6, a solid electrolyte membrane, and an electrolyte.

8. The solid-liquid hybrid battery of claim 7, wherein, The solid electrolyte film includes a solid electrolyte and a base film, the solid electrolyte being Li 1.3 Al 0.3 Ti 1.7 A mixture of (P04)3ceramic and PEO in a mass ratio of 90:10 to 99:

1.

9. The solid-liquid hybrid battery of claim 7, wherein, The electrolyte is a 1 mol / L LiPF6 electrolyte, and the solvent is a mixed solvent of ethylene carbonate, dimethyl carbonate, and methyl ethyl carbonate at a volume ratio of 1:1:

1.

10. The solid-liquid hybrid battery of claim 7, wherein, The positive electrode comprises at least one of lithium iron phosphate, lithium manganate, lithium nickel cobalt manganate, lithium nickel cobalt aluminate, and lithium cobaltate.

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