All-solid-state lithium battery and preparation method therefor

Abstract

An all-solid-state lithium battery and a preparation method therefor. Li3PO4 is used as a raw material of a solid electrolyte LiPON layer and a positive electrode active material C@LiFePO4 layer, a LiPON layer is prepared by means of magnetron sputtering, and before the raw material of the C@LiFePO4 layer is deposited by means of magnetron sputtering, a Li3PO4 nano thin layer tightly connected to the LiPON layer is deposited on the LiPON layer in advance by means of sputtering, and the Li3PO4 nano thin layer participates in the reaction in a high-temperature sintering stage, to induce a high-temperature solid-state generated C@LiFePO4 active material layer to be tightly combined with the solid electrolyte LiPON layer, so that a crack structure between solid-solid interfaces can be avoided, thereby obviously improving the interface impedance of the all-solid-state lithium battery, and significantly improving the performance of the battery.

Description

All-solid-state lithium battery and preparation method thereof Technical Field

[0001] The present invention relates to the technical field of lithium battery energy storage, and in particular to an all-solid-state lithium battery and a preparation method thereof. Background Art

[0002] All-solid-state lithium batteries use solid electrolytes and do not have leakage problems. They have the advantages of high temperature resistance, non-flammability, and non-volatility, so they have high safety and are suitable for multiple application scenarios such as power storage and automotive power batteries. The development of all-solid-state batteries is an important direction for future battery technology and is of great significance to the further development of battery technology.

[0003] LiPON electrolyte has good stability and low electronic conductivity (<10 -12 S / cm), a wide electrochemical window (5.5V), and low preparation costs make it the most widely used solid electrolyte in all-solid-state thin-film lithium batteries. Furthermore, LiPON's excellent stability makes it highly compatible with lithium metal, facilitating the preparation of all-solid-state lithium batteries. Compared with liquid lithium batteries, the main obstacle to the commercialization of all-solid-state lithium batteries lies in the serious interface problems between the solid electrolyte and the positive and negative electrodes, especially the solid-solid interface between the positive electrode and the solid electrolyte. This results in high internal resistance of solid-state batteries and the susceptibility to dendrite formation during cycling. Changes in the interfacial phase can lead to stress accumulation, resulting in the formation and expansion of cracks, interface delamination, and a reduction in the overall physical connectivity between particles and components, ultimately causing rapid degradation of battery performance and poor cycle life.

[0004] Summary of the Invention

[0005] To solve the above technical problems, the present invention provides a method for preparing an all-solid-state lithium battery, which comprises the following steps: (1) using Li3PO4 as a target material, fixing a substrate and the target material on a fixing table in a magnetron sputtering chamber, adjusting the distance between the substrate and the target material, and evacuating the sputtering chamber;

[0006] (2) nitrogen is introduced into the vacuum sputtering chamber, and then magnetron sputtering is performed to deposit a LiPON film layer on the substrate;

[0007] (3) After magnetron sputtering, the substrate is cooled to room temperature, the sputtering chamber is evacuated, argon gas is introduced into the evacuated sputtering chamber, and magnetron sputtering is started again to deposit a 100-500 nm thick Li3PO4 thin layer on one side of the LiPON film layer to obtain a Li3PO4 / LiPON / substrate material;

[0008] (4) maintaining the argon atmosphere, using a Li3PO4 target, a Fe2O3 target, and a carbon target for simultaneous co-sputtering to deposit a composite material layer on the Li3PO4 thin layer to obtain a composite material layer / Li3PO4 / LiPON / substrate material;

[0009] (5) separating the substrate from the composite material layer / Li3PO4 / LiPON / substrate material, placing the composite material layer / Li3PO4 / LiPON in a sintering device, and calcining it at a high temperature in an argon atmosphere to obtain a C@LiFePO4 / LiPON thin film material;

[0010] (6) After the C@LiFePO4 / LiPON thin film material is cooled to room temperature, the C@LiFePO4 / LiPON thin film material is fixed as a substrate on a fixed table in a magnetron sputtering chamber, evacuated and then introduced with argon gas, and a conductive aluminum layer current collector is deposited on one side of the C@LiFePO4 film layer using an aluminum target by magnetron sputtering to obtain a conductive aluminum layer / C@LiFePO4 / LiPON material;

[0011] (7) The conductive aluminum layer / C@LiFePO4 / LiPON material is placed in an argon-filled glove box, and molten metal lithium is evenly dripped onto the surface of one side of the LiPON. After cooling, pressure is applied to the metal lithium side to flatten the metal lithium layer, and the battery core multilayer material is compressed, and then the battery core multilayer material is encapsulated in a battery casing to obtain the all-solid-state lithium battery.

[0012] Furthermore, the purity of the target materials used in the present invention is greater than or equal to 99.9%.

[0013] Furthermore, the substrate material in step (1) is any one of silicon wafer, carbon paper, or carbon fiber cloth; and the distance between the substrate and the target material is 5-10 cm.

[0014] Furthermore, the flow rate of the nitrogen gas in step (2) is 5-20 sccm; the power of the magnetron sputtering is 1-10 W / cm 2 , the sputtering time is 16-24h.

[0015] Furthermore, the flow rate of the argon gas in step (3) is 5-20 sccm; the power of the magnetron sputtering is 1-10 W / cm 2 , the sputtering time is 3-6h.

[0016] Furthermore, the power of the three target materials, Li3PO4 target, Fe2O3 target and carbon target, for simultaneous sputtering in step (4) is 1-5 W / cm 2 , 1-10W / cm 2 , 3-8W / cm 2The co-sputtering time is 12-24 hours; the molar ratio of Li3PO4 and Fe2O3 in the composite material layer is 2:3.

[0017] Furthermore, the high-temperature calcination in step (5) is a two-stage sintering; the heating rate of the first stage sintering is 3-5°C / min, the sintering temperature is 350-500°C, and the heat preservation is 3-6h; the heating rate of the second stage sintering is 5-10°C / min, the sintering temperature is 600-900°C, and the heat preservation is 6-12h.

[0018] Furthermore, the flow rate of the argon gas in step (6) is 10-20 sccm; the power of the magnetron sputtering is 5-10 W / cm 2 , the sputtering time is 12-24h.

[0019] Furthermore, the pressure applied in step (7) is to apply a pressure of 5-10 MPa on one side of the metal lithium layer using a polyimide plate. Another object of the present invention is to provide an all-solid-state lithium battery, which is prepared by the above preparation method.

[0020] The beneficial effects of the present invention are as follows:

[0021] The present invention uses Li3PO4 as a raw material for preparing both the solid electrolyte LiPON and the positive electrode active material LiFePO4 of an all-solid-state lithium battery. The solid electrolyte LiPON is obtained by magnetron sputtering deposition in a nitrogen atmosphere. Before depositing the raw material of LiFePO4 on the surface of the LiPON, a thin layer of Li3PO4 with a thickness of 100-500nm is intentionally deposited by magnetron sputtering. Li3PO4 itself is a raw material of LiPON. The thin layer is tightly connected to the surface of the LiPON layer and participates in the reaction during the high-temperature sintering stage, inducing the C@LiFePO4 active material layer generated in the high-temperature solid phase to be tightly combined with the solid electrolyte LiPON layer, avoiding a crack structure between the solid-solid interface, thereby significantly improving the interface impedance of the all-solid-state lithium battery and remarkably improving the battery performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1(a) is a SEM cross-sectional view of a C@LiFePO4 / LiPON thin film material of a comparative example of the present invention;

[0023] FIG1( b ) is a SEM cross-sectional view of the C@LiFePO4 / LiPON thin film material of Example 1 of the present invention.

[0024] FIG2 is a graph showing the cycle performance of lithium solid-state batteries according to Example 1 of the present invention and the comparative example.

[0025] FIG3 is an EIS graph of the lithium solid-state batteries of Example 1 of the present invention and the comparative example after activation.

[0026] Among them, 1-solid electrolyte LiPON layer, 2-C@LiFePO4 layer. DETAILED DESCRIPTION

[0027] The present invention is further described below with reference to Examples and Comparative Examples.

[0028] Example 1

[0029] Li3PO4 with a purity of greater than or equal to 99.9% was used as a target material. The substrate silicon wafer and the target material were fixed on a fixing table in a magnetron sputtering chamber. The distance between the substrate and the target material was adjusted to 10 cm. The sputtering chamber was evacuated to a pressure of less than 1×10 -4 Pa, nitrogen was introduced into the vacuum sputtering chamber at a flow rate of 10 sccm, and then magnetron sputtering was performed. The power of magnetron sputtering was 10 W / cm 2 , the sputtering time is 16h, and the LiPON film layer is deposited on the substrate;

[0030] After the sputtering is completed, the chamber is cooled to room temperature and the pressure is evacuated to less than 1×10 -4 Pa, then argon gas was introduced into the vacuum sputtering chamber at a flow rate of 10 sccm, and magnetron sputtering was started again. The power of magnetron sputtering was 5 W / cm 2 , the sputtering time is 6h, and a 250nm thick Li3PO4 thin layer is deposited on one side of the LiPON film layer to obtain Li3PO4 / LiPON / substrate material;

[0031] Maintaining the argon atmosphere, using Li3PO4 target, Fe2O3 target and carbon target with purity greater than or equal to 99.9%, the three targets were respectively 2 , 1W / cm 2 and 5W / cm 2 The composite material layer is deposited on the Li3PO4 thin layer at a power of 1000 nm and co-sputtered for 24 h to obtain a composite material layer / Li3PO4 / LiPON / substrate material; the substrate in the composite material layer / Li3PO4 / LiPON / substrate material is separated, the composite material layer / Li3PO4 / LiPON is placed in a muffle furnace, and calcined in a high temperature two-step manner in an argon atmosphere, wherein the first stage is sintered at a heating rate of 5°C / min to 350°C and kept warm for 6 h, and the second stage is sintered at a heating rate of 10°C / min to 750°C and kept warm for 12 h to obtain a C@LiFePO4 / LiPON thin film material;

[0032] After the C@LiFePO4 / LiPON thin film material is cooled to room temperature, the C@LiFePO4 / LiPON thin film material is fixed as a substrate on a fixed table in a magnetron sputtering chamber, and vacuum is evacuated to a pressure of less than 1×10 -4 Pa, and then argon gas was introduced at a flow rate of 10 sccm, and a conductive aluminum layer current collector was deposited on one side of the C@LiFePO4 film layer using an aluminum target by magnetron sputtering. The power of the magnetron sputtering was 10 W / cm 2 , the sputtering time is 18h, and a conductive aluminum layer / C@LiFePO4 / LiPON material is obtained; the conductive aluminum layer / C@LiFePO4 / LiPON material is placed in a glove box filled with argon, and molten metal lithium is evenly dripped onto the surface of one side of LiPON. After cooling, a pressure of 5MPa is applied to the metal lithium side to flatten the metal lithium layer, and the battery core multilayer material is compressed, and then the battery core multilayer material is encapsulated in a battery casing to obtain the all-solid-state lithium battery of Example 1.

[0033] Example 2

[0034] Li3PO4 with a purity of greater than or equal to 99.9% was used as a target material. The substrate carbon paper and the target material were fixed on a fixing table in a magnetron sputtering chamber. The distance between the substrate and the target material was adjusted to 5 cm. The sputtering chamber was evacuated to a pressure of less than 1×10 -4 Pa, nitrogen was introduced into the vacuum sputtering chamber at a flow rate of 20 sccm, and then magnetron sputtering was performed. The power of magnetron sputtering was 1 W / cm 2 , the sputtering time is 24h, and the LiPON film layer is deposited on the substrate;

[0035] After the sputtering is completed, the chamber is cooled to room temperature and the pressure is evacuated to less than 1×10 -4 Pa, then argon gas was introduced into the vacuum sputtering chamber at a flow rate of 5 sccm, and magnetron sputtering was started again. The power of magnetron sputtering was 1 W / cm 2 , the sputtering time is 3h, and a 100nm thick Li3PO4 thin layer is deposited on one side of the LiPON film layer to obtain Li3PO4 / LiPON / substrate material;

[0036] Maintaining the argon atmosphere, using Li3PO4 target, Fe2O3 target and carbon target with purity greater than or equal to 99.9%, the three targets were respectively 2 , 5W / cm 2 and 8W / cm 2The composite material layer / Li3PO4 / LiPON / substrate material is deposited on the Li3PO4 thin layer at a power of 180 nm and co-sputtered for 18 h, and the composite material layer is deposited on the Li3PO4 thin layer to obtain a composite material layer / Li3PO4 / LiPON / substrate material; the substrate in the composite material layer / Li3PO4 / LiPON / substrate material is separated, and the composite material layer / Li3PO4 / LiPON is placed in a muffle furnace and subjected to high-temperature two-step calcination in an argon atmosphere, wherein the first stage is sintered at a heating rate of 5°C / min, the temperature is increased to 350°C, and the temperature is kept for 6 h, and the second stage is sintered at a heating rate of 5°C / min, the temperature is increased to 600°C, and the temperature is kept for 12 h, to obtain a C@LiFePO4 / LiPON thin film material;

[0037] After the C@LiFePO4 / LiPON thin film material is cooled to room temperature, the C@LiFePO4 / LiPON thin film material is fixed as a substrate on a fixed table in a magnetron sputtering chamber, and vacuum is evacuated to a pressure of less than 1×10 -4 Pa, and then argon gas was introduced at a flow rate of 20 sccm, and a conductive aluminum layer current collector was deposited on one side of the C@LiFePO4 film layer using an aluminum target by magnetron sputtering. The power of the magnetron sputtering was 5 W / cm 2 , the sputtering time is 24h, and a conductive aluminum layer / C@LiFePO4 / LiPON material is obtained; the conductive aluminum layer / C@LiFePO4 / LiPON material is placed in a glove box filled with argon, and molten metal lithium is evenly dripped onto the surface of one side of LiPON. After cooling, a pressure of 5MPa is applied to the metal lithium side to flatten the metal lithium layer, and the battery core multilayer material is compressed, and then the battery core multilayer material is encapsulated in a battery casing to obtain the all-solid-state lithium battery of Example 2.

[0038] Example 3

[0039] Li3PO4 with a purity of greater than or equal to 99.9% was used as a target material. The substrate carbon fiber cloth and the target material were fixed on a fixing table in a magnetron sputtering chamber. The distance between the substrate and the target material was adjusted to 10 cm. The sputtering chamber was evacuated to a pressure of less than 1×10 -4 Pa, nitrogen was introduced into the vacuum sputtering chamber at a flow rate of 5 sccm, and then magnetron sputtering was performed. The power of magnetron sputtering was 5 W / cm 2 , the sputtering time is 18h, and the LiPON film layer is deposited on the substrate;

[0040] After the sputtering is completed, the chamber is cooled to room temperature and the pressure is evacuated to less than 1×10 -4 Pa, then argon gas was introduced into the vacuum sputtering chamber at a flow rate of 20 sccm, and magnetron sputtering was started again. The power of magnetron sputtering was 10 W / cm 2, the sputtering time is 4h, and a 500nm thick Li3PO4 thin layer is deposited on one side of the LiPON film layer to obtain Li3PO4 / LiPON / substrate material;

[0041] Maintaining the argon atmosphere, using Li3PO4 target, Fe2O3 target and carbon target with purity greater than or equal to 99.9%, the three targets were respectively 2 、10W / cm 2 and 3W / cm 2 The composite material layer / Li3PO4 / LiPON / substrate material is deposited on the Li3PO4 thin layer at a power of 1000 nm and co-sputtered for 12 h, and the composite material layer is deposited on the Li3PO4 thin layer to obtain a composite material layer / Li3PO4 / LiPON / substrate material; the substrate in the composite material layer / Li3PO4 / LiPON / substrate material is separated, and the composite material layer / Li3PO4 / LiPON is placed in a muffle furnace and calcined in an argon atmosphere in a high temperature two-step manner, wherein the first stage is sintered at a heating rate of 3°C / min to 500°C and kept at this temperature for 3 h, and the second stage is sintered at a heating rate of 10°C / min to 900°C and kept at this temperature for 6 h, to obtain a C@LiFePO4 / LiPON thin film material;

[0042] After the C@LiFePO4 / LiPON thin film material is cooled to room temperature, the C@LiFePO4 / LiPON thin film material is fixed as a substrate on a fixed table in a magnetron sputtering chamber, and vacuum is evacuated to a pressure of less than 1×10 -4 Pa, and then argon gas was introduced at a flow rate of 20 sccm, and a conductive aluminum layer current collector was deposited on one side of the C@LiFePO4 film layer using an aluminum target by magnetron sputtering. The power of the magnetron sputtering was 10 W / cm 2 , the sputtering time is 12h, and a conductive aluminum layer / C@LiFePO4 / LiPON material is obtained; the conductive aluminum layer / C@LiFePO4 / LiPON material is placed in a glove box filled with argon, and molten metal lithium is evenly dripped onto the surface of one side of LiPON. After cooling, a pressure of 10MPa is applied to the metal lithium side to flatten the metal lithium layer, and the battery core multilayer material is compressed, and then the battery core multilayer material is encapsulated in a battery casing to obtain the all-solid-state lithium battery of Example 3.

[0043] Comparative Example

[0044] Li3PO4 with a purity of greater than or equal to 99.9% was used as a target material. The substrate silicon wafer and the target material were fixed on a fixing table in a magnetron sputtering chamber. The distance between the substrate and the target material was adjusted to 10 cm. The sputtering chamber was evacuated to a pressure of less than 1×10 -4 Pa, nitrogen was introduced into the vacuum sputtering chamber at a flow rate of 10 sccm, and then magnetron sputtering was performed. The power of magnetron sputtering was 10 W / cm2 , the sputtering time is 16h, and the LiPON film layer is deposited on the substrate;

[0045] After the sputtering is completed, the chamber is cooled to room temperature and the pressure is evacuated to less than 1×10 -4 Pa, and then argon gas was introduced into the vacuum sputtering chamber at a flow rate of 10 sccm;

[0046] The three targets, Li3PO4 target, Fe2O3 target and carbon target, with purity greater than or equal to 99.9%, were used. 2 , 1W / cm 2 and 5W / cm 2 The LiPON film layer is co-sputtered at a power of 1000 nm and the co-sputtering time is 24 h, and a composite material layer is deposited on the LiPON film layer to obtain a composite material layer / LiPON / substrate material; the substrate in the composite material layer / LiPON / substrate material is separated, and the composite material layer / LiPON is placed in a muffle furnace and subjected to high-temperature two-step calcination in an argon atmosphere, wherein the first stage is sintered at a heating rate of 5°C / min, the temperature is increased to 350°C, and the temperature is kept for 6 h, and the second stage is sintered at a heating rate of 10°C / min, the temperature is increased to 750°C, and the temperature is kept for 12 h, to obtain a C@LiFePO4 / LiPON thin film material;

[0047] After the C@LiFePO4 / LiPON thin film material is cooled to room temperature, the C@LiFePO4 / LiPON thin film material is fixed as a substrate on a fixed table in a magnetron sputtering chamber, and vacuum is evacuated to a pressure of less than 1×10 -4 Pa, and then argon gas was introduced at a flow rate of 10 sccm, and a conductive aluminum layer current collector was deposited on one side of the C@LiFePO4 film layer using an aluminum target by magnetron sputtering. The power of the magnetron sputtering was 10 W / cm 2 , the sputtering time is 18h, and a conductive aluminum layer / C@LiFePO4 / LiPON material is obtained; the conductive aluminum layer / C@LiFePO4 / LiPON material is placed in a glove box filled with argon, and molten metal lithium is evenly dripped onto the surface of one side of LiPON. After cooling, a pressure of 5MPa is applied to the metal lithium side to flatten the metal lithium layer, and the battery core multilayer material is compressed, and then the battery core multilayer material is encapsulated in a battery casing to obtain a comparative example all-solid-state lithium battery.

[0048] Battery test experiment

[0049] The charge and discharge cut-off voltage of the lithium solid-state batteries of Examples 1-3 and the comparative example is 3.0-4.2V, constant current charge and discharge are adopted, the activation current is 0.1C, and the charge and discharge cycle current is 0.2C.

[0050] The frequency range of the EIS impedance test is 0.01 Hz-100 kHz, and the AC signal amplitude is 10 mV.

[0051] The test results are shown in Table 1 below:

[0052] Table 1

[0053] From the comparison of Figures 1(a) and 1(b) of the specification, it can be seen that in Example 1, a thin layer of Li3PO4 is pre-deposited before the composite material layer is deposited on the surface of the solid electrolyte LiPON. Compared with the comparative example in which the composite material layer is directly deposited on the LiPON layer, the C@LiFePO4 / LiPON thin film material obtained by high-temperature sintering has a tighter and smoother solid-solid interface connection. Combined with the test results data in Table 1, it can be seen that compared with the comparative example, the interfacial impedance of the battery after activation is smaller and the long-cycle stability is better, while the comparative example battery fails after about 25 charge and discharge cycles.

Claims

1. A method for preparing an all-solid-state lithium battery, characterized in that: The steps include: (1) Using Li3PO4 as a target material, fixing a substrate and the target material on a fixing table in a magnetron sputtering chamber, adjusting the distance between the substrate and the target material, and evacuating the sputtering chamber; (2) nitrogen is introduced into the vacuum sputtering chamber, and then magnetron sputtering is performed to deposit a LiPON film layer on the substrate; (3) After magnetron sputtering, the substrate is cooled to room temperature, the sputtering chamber is evacuated, argon gas is introduced into the evacuated sputtering chamber, and magnetron sputtering is started again to deposit a 100-500 nm thick Li3PO4 thin layer on one side of the LiPON film layer to obtain a Li3PO4 / LiPON / substrate material; (4) maintaining the argon atmosphere, using a Li3PO4 target, a Fe2O3 target and a carbon target for simultaneous co-sputtering, depositing a composite material layer on the Li3PO4 thin layer, and obtaining a composite material layer / Li3PO4 / LiPON / substrate material; (5) separating the substrate from the composite material layer / Li3PO4 / LiPON / substrate material, placing the composite material layer / Li3PO4 / LiPON in a sintering device, and calcining at a high temperature in an argon atmosphere to obtain a C@LiFePO4 / LiPON thin film material; (6) After the C@LiFePO4 / LiPON thin film material is cooled to room temperature, the C@LiFePO4 / LiPON thin film material is fixed as a substrate on a fixed table in a magnetron sputtering chamber, evacuated and then introduced with argon gas, and a conductive aluminum layer current collector is deposited on one side of the C@LiFePO4 film layer by magnetron sputtering using an aluminum target to obtain a conductive aluminum layer / C@LiFePO4 / LiPON material; (7) placing the conductive aluminum layer / C@LiFePO4 / LiPON material in a glove box filled with argon gas, uniformly dripping molten metal lithium onto the surface of one side of LiPON, applying pressure on the metal lithium side after cooling to flatten the metal lithium layer, and compressing the battery cell multilayer material, and then encapsulating the battery cell multilayer material in a battery casing to obtain the all-solid-state lithium battery.

2. The preparation method according to claim 1, characterized in that The purity of the target materials used is greater than or equal to 99.9%.

3. The preparation method according to claim 1, characterized in that: In step (1), the substrate material is any one of silicon wafer, carbon paper, or carbon fiber cloth; the distance between the substrate and the target material is 5-10 cm.

4. The preparation method according to claim 1, characterized in that: The flow rate of the nitrogen gas in step (2) is 5-20 sccm; the power of the magnetron sputtering is 1-10 W / cm 2 , the sputtering time is 16-24h.

5. The preparation method according to claim 1, characterized in that: The flow rate of the argon gas in step (3) is 5-20 sccm; the power of the magnetron sputtering is 1-10 W / cm 2 , the sputtering time is 3-6h.

6. The preparation method according to claim 1, characterized in that: The power of the three targets of Li3PO4 target, Fe2O3 target and carbon target for simultaneous sputtering in step (4) is 1-5W / cm 2 , 1-10W / cm 2 , 3-8W / cm 2 The co-sputtering time is 12-24 hours; the molar ratio of Li3PO4 and Fe2O3 in the composite material layer is 2:

3.

7. The preparation method according to claim 1, characterized in that: The high temperature calcination in step (5) is a two-stage sintering; the heating rate of the first stage sintering is 3-5°C / min, the sintering temperature is 350-500°C, and the insulation time is 3-6h; the heating rate of the second stage sintering is 5-10°C / min, the sintering temperature is 600-900°C, and the insulation time is 6-12h.

8. The preparation method according to claim 1, characterized in that: The flow rate of the argon gas in step (6) is 10-20 sccm; the power of the magnetron sputtering is 5-10 W / cm 2 , the sputtering time is 12-24h.

9. The preparation method according to claim 1, characterized in that: The pressure applied in step (7) is to use a polyimide plate to load a pressure of 5-10 MPa on one side of the metal lithium layer.

10. An all-solid-state lithium battery, characterized in that: The all-solid-state lithium battery is prepared by any one of the preparation methods described in claims 1 to 9.

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