Anode materials for solid-state batteries and their preparation methods; solid-state batteries

Abstract

This invention provides an anode material for solid-state batteries, its preparation method, and a solid-state battery. The anode material comprises linear carbon nanomaterials and silicon nanowires, with the linear carbon nanomaterials and silicon nanowires interwoven to form a three-dimensional network structure. The silicon nanowires comprise 90-99% by weight, and the linear carbon nanomaterials comprise 1-10% by weight. Based on this, this invention effectively solves the problems of solid-solid interface separation of the active material / solid electrolyte caused by volume expansion during lithium intercalation in silicon-based anodes, which damages the carrier pathway at the interface and leads to severe electrode polarization; and the problems of internal stress generated by volume expansion during lithium intercalation in silicon-based anodes, causing damage to the electrode structure and deteriorating long-cycle stability.

Description

Technical Field

[0001] This invention relates to the field of solid electrolyte technology, and more specifically, to a negative electrode material for solid-state batteries, its preparation method, and solid-state batteries. Background Technology

[0002] Silicon, as a lithium-ion battery anode material, boasts a specific capacity as high as 4200 mAh / g. Compared to graphite (0.1V) and lithium metal anodes, which are unstable at the sulfide interface, silicon has a lithium intercalation potential of 0.4V. This can alleviate interfacial side reactions to some extent while achieving a higher open-circuit voltage, which is beneficial for realizing high-energy-density and high-safety solid-state batteries. However, silicon-based solid-state anodes still have the following problems in application: 1. During lithium intercalation, the volume expansion of silicon-based anodes leads to solid-solid interface separation of the active material / solid electrolyte, damaging the carrier pathway at the interface and causing severe electrode polarization; 2. During lithium intercalation, the volume expansion of silicon-based anodes generates internal stress, causing damage to the electrode structure and deteriorating long-cycle stability. Therefore, it is necessary to provide a new anode material to improve the above problems. Summary of the Invention

[0003] The main objective of this invention is to provide a negative electrode material for solid-state batteries and its preparation method, as well as a solid-state battery, to solve the following problems existing in the application of silicon-based solid-state negative electrodes in the prior art: 1. During the lithium intercalation process of silicon-based negative electrodes, the volume expansion causes separation of the active material / solid electrolyte solid-solid interface, which damages the carrier pathway at the interface and causes severe electrode polarization; 2. During the lithium intercalation process of silicon-based negative electrodes, the volume expansion generates internal stress, which damages the electrode structure and reduces long-cycle stability.

[0004] To achieve the above objectives, according to one aspect of the present invention, a negative electrode material for solid-state batteries is provided. The negative electrode material includes linear carbon nanomaterials and silicon nanowires, wherein the linear carbon nanomaterials and silicon nanowires are interwoven to form a three-dimensional network structure; wherein the weight content of silicon nanowires is 90-99%, and the weight content of linear carbon nanomaterials is 1-10%.

[0005] Furthermore, the linear carbon nanomaterials are carbon nanotubes and / or carbon nanofibers.

[0006] Furthermore, the aspect ratio of the silicon nanowires is 20 to 200:1, preferably 20 to 100:1; the aspect ratio of the linear carbon nanomaterials is 20 to 500:1, preferably 200 to 400:1.

[0007] Furthermore, the porosity of the negative electrode material is 40–80%.

[0008] Furthermore, in the anode material, the weight content of silicon nanowires is 95-99%, and the weight content of linear carbon nanomaterials is 1-5%.

[0009] To achieve the above objectives, according to one aspect of the present invention, a method for preparing the aforementioned negative electrode material for solid-state batteries is provided. The method includes: drying and sintering a dispersion containing linear carbon nanomaterials and SiXz powder to obtain a preform; using the preform as a cathode active material and graphite as an anode active material, electrolyzing the preform in an electrolytic cell filled with electrolyte to obtain the negative electrode material for solid-state batteries; wherein, X represents O, S, C or N, 0 < z ≤ 2; the linear carbon nanomaterials are carbon nanotubes and / or carbon nanofibers; the weight ratio of the linear carbon nanomaterials to the SiXz powder is 1:(20-200); and during electrolysis, the electrolysis current density is 500-1500 A / m.

[0010] Furthermore, the electrolysis process is carried out at a temperature of 700–1000°C.

[0011] Furthermore, SiX z The powder is spherical and / or near-spherical in shape, and SiX z The average particle size of the powder is less than 100 nm.

[0012] Furthermore, during the sintering process, the sintering temperature is 900–1200℃, the sintering time is 1–5 hours, and the sintering atmosphere is an inert gas.

[0013] According to another aspect of the present invention, a solid-state battery is provided, comprising a solid electrolyte and the aforementioned negative electrode material, or a negative electrode material prepared by the aforementioned preparation method.

[0014] By applying the technical solution of this invention, this invention effectively solves the problems of solid-solid interface separation of active material / solid electrolyte caused by volume expansion during lithium intercalation of silicon-based anodes, which damages the carrier pathway at the interface and causes severe electrode polarization; and the problems of internal stress generated by volume expansion during lithium intercalation of silicon-based anodes, which damages the electrode structure and deteriorates long-cycle stability. Attached Figure Description

[0015] The accompanying drawings, which form part of this application, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings:

[0016] Figure 1 The SEM image of the negative electrode material in Embodiment 3 of the present invention is shown. Detailed Implementation

[0017] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other. The present invention will now be described in detail with reference to the accompanying drawings and embodiments.

[0018] As described in the background section of this invention, existing silicon-based solid anodes have the following problems in application: 1. During the lithium intercalation process, the volume expansion of the silicon-based anode causes separation of the solid-solid interface of the active material / solid electrolyte, which damages the carrier pathway at the interface and causes severe electrode polarization; 2. During the lithium intercalation process, the volume expansion of the silicon-based anode generates internal stress, which damages the electrode structure and reduces long-cycle stability.

[0019] To address this issue, this application provides a negative electrode material for solid-state batteries, comprising linear carbon nanomaterials and silicon nanowires, wherein the linear carbon nanomaterials and silicon nanowires are interwoven to form a three-dimensional network structure; wherein the weight content of silicon nanowires is 90-99%, and the weight content of linear carbon nanomaterials is 1-10%.

[0020] In the anode material of this invention, one-dimensional silicon-based silicon nanowires and one-dimensional conductive linear carbon nanomaterials interweave and fully contact each other to form a three-dimensional network structure, thereby giving the anode material a macroscopically porous structure. This porous structure provides space for the volume expansion of the silicon-based material, mitigating the volume expansion during lithium insertion / extraction and thus preventing damage to the electrode structure caused by volume expansion. Simultaneously, both the one-dimensional silicon-based silicon nanowires and the one-dimensional conductive linear carbon nanomaterials possess high mechanical strength, thereby improving the mechanical properties of the anode material. This further alleviates electrode structure damage that occurs during long-term battery cycling, thus improving the battery's cycle performance and significantly enhancing its cycle stability.

[0021] In particular, in the aforementioned negative electrode material of this application, the weight content of silicon nanowires is 90-99%, and the weight content of carbon material is 1-10%. Thus, when this negative electrode material is subsequently applied to solid-state batteries (such as solid-state batteries containing sulfide electrolytes), the battery can exhibit excellent cycle stability. However, when the weight content of silicon nanowires is less than 90%, the cycle stability of the aforementioned solid-state battery will decrease.

[0022] Based on this, the present invention effectively solves the problems of solid-solid interface separation of active material / solid electrolyte caused by volume expansion during lithium intercalation of silicon-based anodes, which damages the carrier pathway at the interface and causes severe electrode polarization; and the problems of internal stress generated by volume expansion during lithium intercalation of silicon-based anodes, which damages the electrode structure and deteriorates long-cycle stability.

[0023] In some optional embodiments, the negative electrode material contains: 99% silicon nanowires and 1% linear carbon nanomaterials by weight; 98% silicon nanowires and 2% linear carbon nanomaterials by weight; 97% silicon nanowires and 3% linear carbon nanomaterials by weight; 96% silicon nanowires and 4% linear carbon nanomaterials by weight; 95% silicon nanowires and 5% linear carbon nanomaterials by weight; 94% silicon nanowires and 6% linear carbon nanomaterials by weight; 93% silicon nanowires and 7% linear carbon nanomaterials by weight; 92% silicon nanowires and 8% linear carbon nanomaterials by weight; 91% silicon nanowires and 9% linear carbon nanomaterials by weight; and 90% silicon nanowires and 10% linear carbon nanomaterials by weight.

[0024] To further improve the cycle stability of solid-state batteries, in a preferred embodiment, the aspect ratio of the silicon nanowires is 20–200:1, preferably 20–100:1, such as 50:1, 60:1, 70:1, 80:1, 90:1, or 100:1. The aspect ratio of the linear carbon nanomaterials is 20–500:1; preferably 200–400:1, such as 200:1, 250:1, 300:1, 350:1, or 400:1.

[0025] In a preferred embodiment, the porosity of the negative electrode material is 40-80%. This effectively mitigates the volume expansion of the silicon-based material during lithium insertion / extraction, thereby preventing damage to the electrode structure and significantly improving the cycle stability of the battery. More preferably, the porosity of the negative electrode material is 50-70%.

[0026] To further improve the cycle stability of the battery, the weight content of silicon nanowires in the negative electrode material is 95-99%, and the weight content of linear carbon nanomaterials is 1-5%.

[0027] The present invention also provides a method for preparing the aforementioned anode material for solid-state batteries, the method comprising: preparing a mixture of wire-like carbon nanomaterials and SiX z The powder dispersion is dried and sintered to obtain a preform. Using the preform as the cathode active material and graphite as the anode active material, the preform is electrolyzed in an electrolyte-filled electrolytic cell to obtain a negative electrode material for solid-state batteries. Here, X represents O, S, C, or N, and 0 < z ≤ 2; linear nano-carbon materials and SiX z The powder weight ratio is 1:(20~200); during electrolysis, the electrolysis current density is 500~1500A / m.

[0028] In the specific electrolysis process described above, SiX z The powder undergoes a reduction reaction and rapidly grows along the lower-energy crystal planes to form silicon nanowires. These silicon nanowires intertwine and fully contact with carbon materials to form a three-dimensional network structure, resulting in a porous structure in the anode material. This porous structure provides space for the volume expansion of the silicon-based material, mitigating the volume expansion during lithium insertion / extraction and thus preventing damage to the electrode structure. It is important to note that if the electrolysis current density is below the aforementioned range, silicon nanowires cannot be formed, and therefore the aforementioned three-dimensional network structure cannot be obtained.

[0029] Meanwhile, both the aforementioned one-dimensional silicon-based silicon nanowires and one-dimensional conductive linear carbon nanomaterials possess high mechanical strength, thereby improving the mechanical properties of the anode material. This can further alleviate the electrode structure damage that occurs during long-term battery cycling, thus improving the battery's cycle performance and significantly enhancing its cycle stability.

[0030] In particular, in the above-mentioned preparation method of this application, carbon materials and SiX z The powder weight ratio is 1:(20-200). Thus, the resulting anode material contains 90-99% silicon nanowires and 1-10% linear carbon nanomaterials by weight. This allows the anode material to exhibit excellent cycle stability when subsequently applied to solid-state batteries (such as those with sulfide electrolytes). SiX z If the amount of powder is too low and the amount of carbon material is too high, on the one hand, the silicon nanowires cannot be formed as well as the three-dimensional network structure can not be obtained, and on the other hand, the cycle stability of the solid-state battery will be greatly reduced.

[0031] Based on this, the present invention effectively solves the problems of solid-solid interface separation of active material / solid electrolyte caused by volume expansion during lithium intercalation of silicon-based anodes, which damages the carrier pathway at the interface and causes severe electrode polarization; and the problem of internal stress generated by volume expansion during lithium intercalation of silicon-based anodes, which damages the electrode structure and deteriorates long-cycle stability. In addition, the preparation method is pollution-free, uses readily available raw materials, requires inexpensive equipment, and is easy to produce continuously, making it more promising for industrial application.

[0032] In some alternative embodiments, the electrolysis current density during the above electrolysis process is further preferably 800 to 1500 A / m, for example, 800 A / m, 900 A / m, 1000 A / m, 1100 A / m, 1200 A / m, 1300 A / m, 1400 A / m or 1500 A / m.

[0033] Furthermore, linear carbon nanomaterials and SiX z The weight ratio of the powder is 1:(20-200), for example, it can be 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90, 1:100, 1:120, 1:140, 1:160, 1:180 or 1:200.

[0034] Furthermore, this invention does not specifically limit the type of electrolyte in the electrolytic cell; those skilled in the art can choose any conventional molten electrolyte. In some exemplary embodiments, the electrolyte may be selected from one or more of molten CaCl2, molten BaCl2, molten LiCl, molten AlCl3, molten CsCl, molten NaCl, molten KCl, or molten SrCl2. This invention also does not specifically limit the solvent in the above dispersion; those skilled in the art can choose any conventional solvent, such as anhydrous ethanol.

[0035] In a preferred embodiment, those skilled in the art can first disperse the linear carbon nanomaterials in a solvent, and then add SiX to the system. z The powder is used to form the aforementioned dispersion. Based on this, in the subsequent electrolysis process, SiX z After the powder undergoes a reduction reaction, it can grow silicon nanowires in situ more effectively. These silicon nanowires and carbon materials (carbon nanotubes and / or carbon nanofibers) intertwine and come into full contact to form a three-dimensional network structure with superior structural properties.

[0036] In a preferred embodiment, the electrolysis treatment temperature is 700–1000°C, for example, 700°C, 800°C, 900°C, or 1000°C. Based on this, SiX z Powder can more efficiently grow silicon nanowires with suitable aspect ratios, allowing them to more fully interweave and contact with carbon fibers to form a three-dimensional network structure. This results in superior porous structure performance of the anode material, leading to better cycle stability of the battery. Electrolysis temperatures above this range are energy-intensive and generate numerous side reactions; temperatures below this range result in insufficient electrolyte dissolution or high viscosity, leading to lower electrolysis efficiency. Furthermore, the electrolysis time can be adjusted based on the electrolysis current density and the amount of material to be electrolyzed. For example, the amount of electricity required to electrolyze 50g of silicon dioxide is fixed; a higher current density results in a shorter electrolysis time, and a lower current density requires a longer electrolysis time. Shorter electrolysis times lead to incomplete electrolysis, while longer electrolysis times may result in side reactions.

[0037] To further obtain high-performance silicon nanowires, thereby achieving anode materials with superior structural properties and ultimately batteries with better cycle stability, SiX is preferred.z The powder is spherical and / or near-spherical in shape, SiX z The average particle size of the powder is less than 100 nm, preferably 10 to 50 nm, for example, 10 nm, 20 nm, 30 nm, 40 nm or 50 nm.

[0038] To further obtain anode materials with excellent performance and stability, the preferred sintering process involves a sintering temperature of 900–1200℃, a sintering time of 1–5 h, and an inert gas atmosphere. Based on this, the material is sintered before electrolysis to obtain a porous preform. This preform, in the subsequent electrolysis process, can yield anode materials with superior structural properties.

[0039] This invention also provides a solid-state battery, comprising a sulfide electrolyte and the aforementioned negative electrode material, or a negative electrode material prepared by the aforementioned preparation method. For the reasons stated above, the solid-state battery of this invention exhibits excellent cycle stability.

[0040] In one optional embodiment, after the electrolysis is completed, those skilled in the art can sequentially soak the electrolysis products on the cathode in dilute hydrochloric acid (80-90% by mass), clean them by filtration with deionized water, clean them by filtration with anhydrous ethanol, and then vacuum dry them to obtain the negative electrode material. Subsequently, those skilled in the art can further mix the negative electrode material with a solid electrolyte (e.g., one or more of sulfide electrolyte, halide electrolyte, oxide electrolyte, or polymer electrolyte) and a binder (e.g., one or more of styrene-butadiene block polymer, styrene-butadiene block polymer, styrene-butadiene rubber, or butadiene rubber) at a weight ratio of 50-90:10-50:2-5 to obtain a slurry. This slurry is then coated onto a supporting conductive substrate (e.g., copper foil), dried at 60-100°C for 3-10 hours, and then stamped to obtain a negative electrode sheet with a diameter of 6-9 mm. Finally, those skilled in the art can further assemble the negative electrode sheet using conventional methods to obtain a solid-state battery.

[0041] The present application will be further described in detail below with reference to specific embodiments, which should not be construed as limiting the scope of protection claimed in the present application.

[0042] Example 1

[0043] 42.4g of silica powder (average particle size of 30nm) and 0.2g of carbon fiber (average aspect ratio of 300:1) were mixed evenly in anhydrous ethanol and dried at 70℃ for 10h. The dried material was then sintered at 1000℃ for 2h under a nitrogen atmosphere to obtain the preform.

[0044] The aforementioned preform was combined with a conductive cathode current collector (SiO2 / C) to form the cathode, a graphite rod was used as the anode, and molten CaCl2 was used as the electrolyte. Electrolysis was carried out in an argon atmosphere at 850°C with an electrolytic current density of 800 A / m for 6.0 h. After electrolysis, the electrolysis product was sequentially soaked in dilute hydrochloric acid, washed with deionized water, washed with anhydrous ethanol, and then vacuum dried to obtain the negative electrode material.

[0045] In anode materials, the aspect ratio of silicon nanowires is 20 to 100:1.

[0046] The porosity of the negative electrode material is 50-70%.

[0047] The aforementioned negative electrode material was uniformly mixed with a sulfide electrolyte (a sulfide solid electrolyte with a sulfide-germanium sulfide structure) and a conductive agent (VGCF) at a mass ratio of 50:50:3 to obtain a mixed slurry. This mixed slurry was then coated onto copper foil, dried at 100°C for 3 hours, and stamped into a 9mm diameter sheet. Finally, a solid-state battery was assembled from this sheet, and its electrochemical performance was tested.

[0048] Example 2

[0049] The only difference from Example 1 is that the amount of silica powder used is 41.9g and the amount of carbon fiber used is 0.4g.

[0050] In anode materials, the aspect ratio of silicon nanowires is 20 to 100:1.

[0051] The porosity of the negative electrode material is 50-70%.

[0052] Example 3

[0053] The only difference from Example 1 is that the amount of silica powder used is 41.5g; and the amount of carbon fiber used is 0.6g.

[0054] In anode materials, the aspect ratio of silicon nanowires is 20 to 100:1.

[0055] The porosity of the negative electrode material is 50-70%.

[0056] Figure 1 The SEM image of the negative electrode material in Embodiment 3 of the present invention is shown.

[0057] Example 4

[0058] The only difference from Example 1 is that the amount of silica powder used is 41.1g; and the amount of carbon fiber used is 0.8g.

[0059] In anode materials, the aspect ratio of silicon nanowires is 20 to 100:1.

[0060] The porosity of the negative electrode material is 50-70%.

[0061] Example 5

[0062] The only difference from Example 1 is that the amount of silica powder used is 40.6g; and the amount of carbon fiber used is 1.0g.

[0063] In anode materials, the aspect ratio of silicon nanowires is 20 to 100:1.

[0064] The porosity of the negative electrode material is 50-70%.

[0065] Example 6

[0066] The only difference from Example 3 is that the carbon fiber is replaced with 0.6g of carbon nanotubes.

[0067] In anode materials, the aspect ratio of silicon nanowires is 20 to 100:1.

[0068] The porosity of the negative electrode material is 50-70%.

[0069] Example 7

[0070] The only difference from Example 1 is that the amount of silica powder used is 39.8g; the amount of carbon fiber used is 1.4g; and the electrolysis time is 5.5h.

[0071] In anode materials, the aspect ratio of silicon nanowires is 20 to 100:1.

[0072] The porosity of the negative electrode material is 50-70%.

[0073] Example 8

[0074] The only difference from Example 1 is that the amount of silica powder used is 38.5g; the amount of carbon fiber used is 2.0g; and the electrolysis time is 5.5h.

[0075] In anode materials, the aspect ratio of silicon nanowires is 20 to 100:1.

[0076] The porosity of the negative electrode material is 60-70%.

[0077] Example 9

[0078] The only difference from Example 1 is that the electrolysis current density is 500 A / m and the electrolysis time is 10.0 h.

[0079] In anode materials, the aspect ratio of silicon nanowires is 20–50:1.

[0080] The porosity of the negative electrode material is 50-60%.

[0081] Example 10

[0082] The only difference from Example 1 is that the electrolysis current density is 1500 A / m and the electrolysis time is 4.0 h.

[0083] In anode materials, the aspect ratio of silicon nanowires is 80–100:1.

[0084] The porosity of the negative electrode material is 60-70%.

[0085] Comparative Example 1

[0086] The only difference from Example 1 is that the amount of silica powder used is 25.7g; the amount of carbon fiber used is 8.0g; and the electrolysis time is 4.0h.

[0087] The main product of silicon dioxide reduction is silicon nanoparticles, which are distributed among the carbon fibers. The diameter of these silicon nanoparticles ranges from 20 to 300 nm.

[0088] Comparative Example 2

[0089] (1) Weigh a certain amount of silicon nanoparticles and carbon nanotubes at a silicon-to-carbon mass ratio of 97:1, mix them evenly in a solvent, and dry them by blowing air to obtain a two-dimensional silicon-based composite material.

[0090] (2) The two-dimensional silicon-based composite material was mixed with sulfide electrolyte and conductive agent at a ratio of 50:50:3 using a homogenizer for 30 minutes. The mixed slurry was then coated on copper foil and dried at 100°C for 3 hours. A thin sheet with a diameter of 9 mm was then stamped. Finally, a solid-state battery was assembled and its electrochemical performance was tested.

[0091] Comparative Example 3

[0092] The only difference from Example 1 is that the electrolysis current density is 200 A / m and the electrolysis time is 24.0 h.

[0093] The main product of silicon dioxide reduction is silicon nanoparticles, which are distributed among the carbon fibers. The diameter of the silicon nanoparticles ranges from 100 to 300 nm.

[0094] Performance characterization:

[0095] The electrochemical performance of the above-mentioned embodiments and comparative examples was tested using a Blue Electric charge-discharge tester, and the test results are shown in Table 1.

[0096] Table 1

[0097]

[0098]

[0099] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for producing a negative electrode material for a solid-state battery, characterized by, The preparation method comprises: A dispersion liquid containing a wire-like carbon material and SiX z The dispersion liquid of the powder is dried and then sintered to obtain a preform; electrolyzing the preform in an electrolytic cell filled with electrolyte to obtain the negative electrode material for the solid-state battery, taking the preform as a cathode active material and taking graphite as an anode active material; wherein X represents O, S, C or N, 0 < z < 2; the linear nanocarbon material is carbon nanotube and / or nanocarbon fiber; the linear nanocarbon material and the SiX z The weight ratio of the powder is 1: (20-200). In the electrolysis process, the electrolysis current density is 500-1500 A / m. The negative electrode material comprises linear nanocarbon material and silicon nanowires, and the linear nanocarbon material and the silicon nanowires are interwoven to form a three-dimensional network structure; wherein, The weight content of the silicon nanowires is 90-99%, and the weight content of the linear nanocarbon material is 1-10%.

2. The production method according to claim 1, characterized by, The processing temperature of the electrolysis is 700-1000 DEG C.

3. The method of claim 1, wherein, The SiX z The shape of the powder is spherical and / or spheroidal, and the SiX z The average particle size of the powder is less than 100 nm.

4. The method of claim 1, wherein, In the sintering process, the sintering temperature is 900-1200 DEG C, the sintering time is 1-5 h, and the sintering atmosphere is inert gas.

5. The preparation method according to claim 1, characterized in that, The linear nanocarbon material is carbon nanotube and / or nanocarbon fiber.

6. The method of claim 1, wherein, The aspect ratio of the silicon nanowires is 20-200:

1.

7. The production method according to claim 6, wherein The aspect ratio of the silicon nanowires is 20-100:

1.

8. The preparation method according to claim 5, characterized in that, The aspect ratio of the linear nanocarbon material is 20-500:

1.

9. The production method according to claim 8, characterized by, The aspect ratio of the linear nanocarbon material is 200-400:

1.

10. The method of claim 5, wherein, The porosity of the negative electrode material is 40-80%.

11. The method of claim 1, wherein, In the negative electrode material, the weight content of the silicon nanowires is 95-99%, and the weight content of the linear nanocarbon material is 1-5%.

12. A solid state battery, characterized by The solid-state battery comprises a solid-state electrolyte and a negative electrode material prepared by the preparation method in any one of claims 1-11.

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