All-solid-state lithium battery and preparation method thereof

Abstract

An all-solid-state lithium battery and its preparation method. Li3PO4 is used as the raw material for the solid electrolyte LiPON layer and the cathode active material C@LiFePO4 layer. The LiPON layer is prepared by magnetron sputtering. Before sputtering and depositing the raw materials of the C@LiFePO4 layer, a thin layer of Li3PO4 nanoparticles that is tightly connected to the LiPON layer is pre-sputtered and deposited on the LiPON layer. The Li3PO4 nanoparticle thin layer participates in the reaction during the high-temperature sintering stage, inducing the C@LiFePO4 active material layer formed by high-temperature solid phase reaction to be tightly combined with the solid electrolyte LiPON layer, which can avoid the crack structure between the solid-solid interfaces, thus significantly improving the interfacial impedance of the all-solid-state lithium battery and significantly enhancing the battery performance.

Description

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, have no leakage problems, and have the advantages of high temperature resistance, non-flammability, and non-volatility. Therefore, 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 a low preparation cost make it the most widely used solid electrolyte in all-solid-state thin-film lithium batteries. In addition, the excellent stability of LiPON makes it compatible with Li metal, which is conducive to 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 contact between the positive electrode and the solid electrolyte, which causes the internal resistance of the solid-state battery to be high, and dendrites are easily generated during the cycle. The change of the interface phase will cause stress accumulation, resulting in the formation and expansion of cracks, interface stratification, and the reduction of the overall physical connectivity between particles and components, which ultimately causes the battery performance to decay rapidly and the cycle life to be poor. Summary of the invention

[0004] In order 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:

[0005] (1) Use Li 3 PO 4 As a target material, a substrate and the target material are fixed on a fixing table in a magnetron sputtering chamber, a distance between the substrate and the target material is adjusted, and the sputtering chamber is evacuated;

[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 film 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 LiPON film on one side of the film. 3 PO 4 Thin layer, get Li 3 PO 4 / LiPON / substrate material;

[0008] (4) Keep the argon atmosphere and use Li 3 PO 4 Target, Fe 2 O 3 The three target materials of Li 3 PO 4 The composite material layer is deposited on the thin layer to obtain the composite material layer / Li 3 PO 4 / LiPON / substrate material;

[0009] (5) Separation of composite material layer / Li 3 PO 4 / LiPON / substrate material in the substrate, the composite material layer / Li 3 PO 4 / LiPON is placed in a sintering device and calcined at high temperature in an argon atmosphere to obtain C@LiFePO 4 / LiPON thin film materials;

[0010] (6) Wait for the C@LiFePO 4 After the C@LiFePO / LiPON thin film material is cooled to room temperature, 4 The / LiPON thin film material is fixed as a substrate on a fixed table in a magnetron sputtering chamber, and argon gas is introduced after vacuuming. An aluminum target is used and magnetron sputtering is performed on C@LiFePO 4 A conductive aluminum layer current collector is deposited on one side of the film layer to obtain a conductive aluminum layer / C@LiFePO 4 / LiPON materials;

[0011] (7) The conductive aluminum layer / C@LiFePO 4 The / 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 cell multilayer material is compressed, and then the battery cell multilayer material is encapsulated in a battery casing to obtain the all-solid-state lithium battery.

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

[0013] Furthermore, in step (1), the substrate material 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] Further, in step (4), Li 3 PO 4 Target, Fe 2 O 3 The power of the three target materials, target and carbon target, for simultaneous sputtering is 1-5W / cm 2 , 1-10W / cm 2 , 3-8W / cm 2 The co-sputtering time is 12-24h; Li 3 PO 4 and Fe 2 O 3 The molar ratio 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 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.

[0018] Furthermore, in step (6), the flow rate of the argon gas 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 use a polyimide plate to load a pressure of 5-10 MPa on one side of the metal lithium layer.

[0020] Another object of the present invention is to provide an all-solid-state lithium battery, which is prepared by the above-mentioned preparation method.

[0021] The beneficial effects of the present invention are as follows:

[0022] The present invention adopts Li 3 PO 4 At the same time, it can be used as the solid electrolyte LiPON and the positive electrode active material LiFePO for preparing all-solid-state lithium batteries 4 The solid electrolyte LiPON was obtained by magnetron sputtering deposition in a nitrogen atmosphere, and LiFePO was deposited on the surface of LiPON. 4 Before the raw materials are prepared, a layer of Li with a thickness of 100-500 nm is intentionally deposited by magnetron sputtering.3 PO 4 Thin layer, Li 3 PO 4 It is the 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 high-temperature solid-phase generation of C@LiFePO 4 The active material layer is tightly combined with the solid electrolyte LiPON layer to avoid the crack structure between the solid-solid interface, thereby significantly improving the interface impedance of the all-solid-state lithium battery and significantly improving the battery performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 (a) is C@LiFePO of the comparative example of the present invention 4 / SEM cross-sectional view of LiPON thin film material;

[0024] Figure 1 (b) is C@LiFePO of Example 1 of the present invention 4 / SEM cross-sectional image of LiPON thin film material.

[0025] Figure 2 The graphs are the cycle performances of lithium solid-state batteries of Example 1 of the present invention and the comparative example.

[0026] Figure 3 1 and 2 are EIS graphs of the lithium solid-state batteries of Example 1 of the present invention and the comparative example after activation.

[0027] Among them, 1-solid electrolyte LiPON layer, 2-C@LiFePO 4 layer. DETAILED DESCRIPTION

[0028] The present invention is further described below with reference to examples and comparative examples.

[0029] Example 1

[0030] Use Li with a purity of 99.9% or more 3 PO 4 As a target material, a substrate silicon wafer and the target material are fixed on a fixing table in a magnetron sputtering chamber, the distance between the substrate and the target material is adjusted to 10 cm, and the sputtering chamber is evacuated to a pressure 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;

[0031] After the sputtering is completed, the chamber is cooled to room temperature and then the sputtering chamber is evacuated to a pressure less than 1×10 -4Pa, 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 Li layer is deposited on one side of the LiPON film. 3 PO 4 Thin layer, get Li 3 PO 4 / LiPON / substrate materials;

[0032] Keep the argon atmosphere, use Li with a purity greater than or equal to 99.9% 3 PO 4 Target, Fe 2 O 3 The three targets were 1W / cm 2 , 1W / cm 2 and 5W / cm 2 The power of the co-sputtering was 24 hours. 3 PO 4 The composite material layer is deposited on the thin layer to obtain the composite material layer / Li 3 PO 4 / LiPON / substrate material; separation composite material layer / Li 3 PO 4 / LiPON / substrate material, the composite material layer / Li 3 PO 4 / LiPON was placed in a muffle furnace and calcined in an argon atmosphere in two steps. The first stage was sintered at a heating rate of 5°C / min to 350°C and kept warm for 6h. The second stage was sintered at a heating rate of 10°C / min to 750°C and kept warm for 12h to obtain C@LiFePO 4 / LiPON thin film materials;

[0033] Wait for the C@LiFePO 4 After the C@LiFePO / LiPON thin film material is cooled to room temperature, 4 The LiPON thin film material is fixed as a substrate on a fixed table in a magnetron sputtering chamber and evacuated to a pressure less than 1×10 -4 Pa, and then argon was introduced at a flow rate of 10 sccm, and an aluminum target was used to deposit C@LiFePO by magnetron sputtering. 4 A conductive aluminum layer current collector is deposited on one side of the film layer, and the power of magnetron sputtering is 10W / cm 2 , the sputtering time is 18h, and the conductive aluminum layer / C@LiFePO is obtained 4 / LiPON material; the conductive aluminum layer / C@LiFePO4 The / LiPON material is placed in a glove box filled with argon, and molten metal lithium is evenly dripped on the surface of one side of the LiPON. After cooling, a pressure of 5 MPa is applied to the metal lithium side to flatten the metal lithium layer, and the battery cell multilayer material is compressed, and then the battery cell multilayer material is encapsulated in a battery casing to obtain the all-solid-state lithium battery of Example 1.

[0034] Example 2

[0035] Use Li with a purity of 99.9% or more 3 PO 4 As a target material, the substrate carbon paper and the target material are fixed on a fixing table in a magnetron sputtering chamber, the distance between the substrate and the target material is adjusted to 5 cm, and the sputtering chamber is evacuated to a pressure 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;

[0036] After the sputtering is completed, the chamber is cooled to room temperature and then the sputtering chamber is evacuated to a pressure 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 Li layer is deposited on one side of the LiPON film. 3 PO 4 Thin layer, get Li 3 PO 4 / LiPON / substrate material;

[0037] Keep the argon atmosphere, use Li with a purity greater than or equal to 99.9% 3 PO 4 Target, Fe 2 O 3 The three targets were 5W / cm 2 , 5W / cm 2 and 8W / cm 2 The power of the co-sputtering was 18 hours. 3 PO 4 The composite material layer is deposited on the thin layer to obtain the composite material layer / Li 3 PO 4 / LiPON / substrate material; separation composite material layer / Li 3 PO 4 / LiPON / substrate material in the substrate, the composite material layer / Li3 PO 4 / LiPON was placed in a muffle furnace and calcined in an argon atmosphere in two steps. The first stage was sintered at a heating rate of 5°C / min to 350°C and kept at this temperature for 6h. The second stage was sintered at a heating rate of 5°C / min to 600°C and kept at this temperature for 12h to obtain C@LiFePO 4 / LiPON thin film materials;

[0038] Wait for the C@LiFePO 4 After the C@LiFePO / LiPON thin film material is cooled to room temperature, 4 The LiPON thin film material is fixed as a substrate on a fixed table in a magnetron sputtering chamber and evacuated to a pressure less than 1×10 -4 Pa, and then argon was introduced at a flow rate of 20 sccm, and an aluminum target was used to deposit C@LiFePO by magnetron sputtering. 4 A conductive aluminum layer current collector is deposited on one side of the film layer, and the power of magnetron sputtering is 5W / cm 2 , the sputtering time is 24h, and the conductive aluminum layer / C@LiFePO 4 / LiPON material; the conductive aluminum layer / C@LiFePO 4 The / LiPON material is placed in a glove box filled with argon, and molten metal lithium is evenly dripped on the surface of one side of the LiPON. After cooling, a pressure of 5 MPa is applied to the metal lithium side to flatten the metal lithium layer, and the battery cell multilayer material is compressed, and then the battery cell multilayer material is encapsulated in a battery casing to obtain the embodiment 2 all-solid-state lithium battery.

[0039] Example 3

[0040] Use Li with a purity of 99.9% or more 3 PO 4 As a target material, the substrate carbon fiber cloth and the target material are fixed on a fixing table in a magnetron sputtering chamber, the distance between the substrate and the target material is adjusted to 10 cm, and the sputtering chamber is evacuated to a pressure 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;

[0041] After the sputtering is completed, the chamber is cooled to room temperature and then the sputtering chamber is evacuated to a pressure 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 2The sputtering time is 4h, and a 500nm thick Li layer is deposited on one side of the LiPON film. 3 PO 4 Thin layer, get Li 3 PO 4 / LiPON / substrate material;

[0042] Keep the argon atmosphere, use Li with a purity greater than or equal to 99.9% 3 PO 4 Target, Fe 2 O 3 The three targets were 5W / cm 2 、10W / cm 2 and 3W / cm 2 The power of the co-sputtering was 12 hours. 3 PO 4 The composite material layer is deposited on the thin layer to obtain the composite material layer / Li 3 PO 4 / LiPON / substrate material; separation composite material layer / Li 3 PO 4 / LiPON / substrate material, the composite material layer / Li 3 PO 4 / LiPON was placed in a muffle furnace and calcined in an argon atmosphere in two steps. The first stage was sintered at a heating rate of 3°C / min to 500°C and kept at this temperature for 3 h. The second stage was sintered at a heating rate of 10°C / min to 900°C and kept at this temperature for 6 h to obtain C@LiFePO 4 / LiPON thin film materials;

[0043] Wait for the C@LiFePO 4 After the C@LiFePO / LiPON thin film material is cooled to room temperature, 4 The LiPON thin film material is fixed as a substrate on a fixed table in a magnetron sputtering chamber and evacuated to a pressure less than 1×10 -4 Pa, and then argon was introduced at a flow rate of 20 sccm, and an aluminum target was used to deposit C@LiFePO by magnetron sputtering. 4 A conductive aluminum layer current collector is deposited on one side of the film layer, and the power of magnetron sputtering is 10W / cm 2 , the sputtering time is 12h, and the conductive aluminum layer / C@LiFePO 4 / LiPON material; the conductive aluminum layer / C@LiFePO 4The / LiPON material is placed in a glove box filled with argon, and molten metal lithium is evenly dripped on the surface of one side of the LiPON. After cooling, a pressure of 10 MPa is applied to the metal lithium side to flatten the metal lithium layer, and the battery cell multilayer material is compressed, and then the battery cell multilayer material is encapsulated in a battery casing to obtain the all-solid-state lithium battery of Example 3.

[0044] Comparative Example

[0045] Use Li with a purity of 99.9% or more 3 PO 4 As a target material, a substrate silicon wafer and the target material are fixed on a fixing table in a magnetron sputtering chamber, the distance between the substrate and the target material is adjusted to 10 cm, and the sputtering chamber is evacuated to a pressure 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;

[0046] After the sputtering is completed, the chamber is cooled to room temperature and then the sputtering chamber is evacuated to a pressure less than 1×10 -4 Pa, and then argon gas was introduced into the vacuum sputtering chamber at a flow rate of 10 sccm;

[0047] Use Li with a purity of 99.9% or more 3 PO 4 Target, Fe 2 O 3 The three targets were 1W / cm 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, 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, the composite material layer / LiPON is placed in a muffle furnace, and a high-temperature two-step calcination is performed in an argon atmosphere, the first stage of sintering is heated to 350°C at a heating rate of 5°C / min and kept warm for 6 h, the second stage of sintering is heated to 750°C at a heating rate of 10°C / min and kept warm for 12 h, and C@LiFePO is obtained. 4 / LiPON thin film materials;

[0048] Wait for the C@LiFePO 4 After the C@LiFePO / LiPON thin film material is cooled to room temperature, 4 The LiPON thin film material is fixed as a substrate on a fixed table in a magnetron sputtering chamber and evacuated to a pressure less than 1×10-4 Pa, and then argon was introduced at a flow rate of 10 sccm, and an aluminum target was used to deposit C@LiFePO by magnetron sputtering. 4 A conductive aluminum layer current collector is deposited on one side of the film layer, and the power of magnetron sputtering is 10W / cm 2 , the sputtering time is 18h, and the conductive aluminum layer / C@LiFePO is obtained 4 / LiPON material; the conductive aluminum layer / C@LiFePO 4 The / 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 the LiPON. After cooling, a pressure of 5 MPa is applied to the metal lithium side to flatten the metal lithium layer, and the battery cell multilayer material is compressed, and then the battery cell multilayer material is encapsulated in a battery casing to obtain a comparative all-solid-state lithium battery.

[0049] Battery test experiment

[0050] 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.

[0051] The frequency range of EIS impedance test is 0.01Hz-100kHz, and the AC signal amplitude is 10mV.

[0052] The test results are shown in Table 1 below:

[0053] Table 1

[0054] Battery interface internal resistance / Ω <![CDATA[Specific capacity of battery after 500 cycles / mAh·g -1 > Example 1 99.2 120.3 Example 2 102.6 117.6 Example 3 103.1 115.3 Comparative Example 479.5 -

[0055] Attached to the instruction manual Figure 1 From the comparison between (a) and 1(b), it can be seen that before the composite material layer is deposited on the surface of the solid electrolyte LiPON, Li 3 PO 4 In Example 1 of the thin layer, compared with the comparative example of directly depositing the composite material layer on the LiPON layer, the C@LiFePO 4 / LiPON thin film material, the connection of the solid-solid interface is tighter and smoother, and combined with the test result data in Table 1, it can be seen that the embodiment has a smaller interface impedance after battery activation than the comparative example, and has better long cycle stability, 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, It is characterized in that The steps include: (1) Use Li 3 PO 4 As a target material, a substrate and the target material are fixed on a fixing table in a magnetron sputtering chamber, a distance between the substrate and the target material is adjusted, and the sputtering chamber is evacuated; (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 film 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 LiPON film on one side of the film. 3 PO 4 Thin layer, get Li 3 PO 4 / LiPON / substrate material; (4) Keep the argon atmosphere and use Li 3 PO 4 Target, Fe 2 O 3 The three target materials of Li 3 PO 4 The composite material layer is deposited on the thin layer to obtain the composite material layer / Li 3 PO 4 / LiPON / substrate material; (5) Separation of composite material layer / Li 3 PO 4 / LiPON / substrate material in the substrate, the composite material layer / Li 3 PO 4 / LiPON is placed in a sintering device and calcined at high temperature in an argon atmosphere to obtain C@LiFePO 4 / LiPON thin film materials; (6) Wait for the C@LiFePO 4 After the C@LiFePO / LiPON thin film material is cooled to room temperature, 4 The / LiPON thin film material is fixed as a substrate on a fixed table in a magnetron sputtering chamber, and argon gas is introduced after vacuuming. An aluminum target is used and magnetron sputtering is performed on C@LiFePO 4 A conductive aluminum layer current collector is deposited on one side of the film layer to obtain a conductive aluminum layer / C@LiFePO 4 / LiPON materials; (7) The conductive aluminum layer / C@LiFePO 4 The / LiPON material is placed in a glove box filled with argon gas, 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 cell multilayer material is compressed, and then the battery cell multilayer material is encapsulated in a battery casing to obtain the all-solid-state lithium battery.

2. The preparation method according to claim 1, It is 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, It is 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, It is 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, It is 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, It is characterized in that In step (4), Li 3 PO 4 Target, Fe 2 O 3 The power of the three target materials, target and carbon target, for simultaneous sputtering is 1-5W / cm 2 , 1-10W / cm 2 , 3-8W / cm 2 The co-sputtering time is 12-24h; Li 3 PO 4 and Fe 2 O 3 The molar ratio is 2:

3.

7. The preparation method according to claim 1, It is 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, It is 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, It is 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, It is 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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