Lithium metal solid-state battery and preparation method thereof

文档序号：211689 发布日期：2021-11-05 浏览：6次中文

阅读说明：本技术 一种金属锂固态电池及其制备方法 (Lithium metal solid-state battery and preparation method thereof ) 是由李新禄王雲锴于 2021-08-03 设计创作，主要内容包括：本发明公开了一种金属锂固态电池,包括正极、无机-聚合物复合电解质层以及负极,无机-聚合物复合电解质层置于正极和负极之间,无机-聚合物复合电解质层的组分包括聚合物单体、锂盐、有机溶剂、引发剂以及无机粉体。本发明的金属锂固态电池以环状聚合物单体为聚合物前驱体,将引发剂掺入正极浆料中,经加热原位聚合和热压锂金属负极,得到一体化无隔膜固态电池。(The invention discloses a metal lithium solid-state battery which comprises a positive electrode, an inorganic-polymer composite electrolyte layer and a negative electrode, wherein the inorganic-polymer composite electrolyte layer is arranged between the positive electrode and the negative electrode, and the inorganic-polymer composite electrolyte layer comprises polymer monomers, lithium salt, an organic solvent, an initiator and inorganic powder. The metal lithium solid-state battery of the invention takes a cyclic polymer monomer as a polymer precursor, an initiator is doped into the anode slurry, and the integrated diaphragm-free solid-state battery is obtained by heating in-situ polymerization and hot pressing of the lithium metal cathode.)

1. A lithium metal solid state battery, characterized in that the lithium metal solid state battery comprises: the lithium ion battery comprises a positive electrode, an inorganic-polymer composite electrolyte layer and a negative electrode, wherein the inorganic-polymer composite electrolyte layer is arranged between the positive electrode and the negative electrode, and the components of the inorganic-polymer composite electrolyte layer comprise a polymer monomer, lithium salt, an organic solvent, an initiator and inorganic powder.

2. The lithium metal solid state battery according to claim 1, wherein the inorganic powder is a solid state electrolyte material that is a mixture of one or more of a sulfide solid state electrolyte material, a garnet solid state electrolyte material, a perovskite solid state electrolyte material, a NASICON solid state electrolyte material, a halide solid state electrolyte material, and derivatives thereof; the sulfide solid state electrolyte material is: li₁₀GeP₂S₁₂(LGPS)、Li₁₀SnP₂S₁₂、Li₆PS₅Cl or Li_9.6P₃S₁₂One or more of the following; the garnet type solid electrolyte material comprises: li₇La₃Zr₂O₁₂、Li_7- _xLa₃Zr₂O_12-x、Li_7-xLa₃Zr_2-xNb_xO₁₂、Li_7-xLa₃Zr_2-xTa_xO₁₂(X ═ 0.2 to 0.8) by mixing; the perovskite type solid electrolyte material is as follows: li_3xLa_2/3-xTiO₃(X＝0.1～0.15)、Li_3/8Sr_7/16Ta_3/4Zr_1/4O₃Or Li_3/8Sr_7/16Ta_3/4Hf_1/4O₃One or more of the following; the NASICON type solid electrolyte material is as follows: LiM (PO)₄)₃Wherein M is selected from Na⁺、Nb⁵⁺、Ta⁵⁺、Ti4⁺、Ge⁴⁺、Zr⁴⁺、Sn⁴⁺、Nb⁴⁺、Hf⁴⁺、Al³⁺、Cr³⁺、Ga³⁺、Fe³⁺、Sc³⁺、In³⁺、Y³⁺、La³⁺、Mg²⁺、Zn²⁺、Cu²⁺、Co²⁺、Mn²⁺、Fe²⁺At least one of; the halide solid state electrolyte material is: li₃OX or Li₃MX₆(X ═ F, Cl, Br or I, M ═ Y, In, Mg, Si or Zr) In a mixture of two or more.

3. The lithium metal solid-state battery according to claim 2, wherein the inorganic powder has an average particle diameter of 50nm to 10um and an ionic conductivity of 10^-3～10^-5S/cm, the thickness of the inorganic-polymer composite electrolyte layer is 2 um-20 um.

4. The lithium metal solid state battery according to claim 1, wherein the lithium salt is one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium bistrifluoromethanesulfonylimide, lithium difluoroborate, LiBOB, lithium difluorooxalato borate, lithium difluorophosphate, or lithium oxalato phosphate; the organic solvent is one of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether or tetrahydrofuran.

5. The lithium metal solid state battery according to claim 1, wherein the polymer monomer is one of ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate, vinylene carbonate, butyrolactone, 1, 3-dioxolane, 4-methyl-1, 3-dioxolane, or 2-methyl-1, 3-dioxolane;

when the polymer monomer is ethylene carbonate, the initiator is 1, 2-propylene glycol, diethylene glycol, KOH, ethylene glycol or monoethylene glycol, and the weight ratio of the polymer monomer to each initiator is respectively as follows: (10: 1), (1.2: 1), (1.5:1), (1.2: 1);

when the polymer monomer is propylene carbonate, the initiator is diethylene glycol, benzenediol or phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, and the weight ratio of the polymer monomer to each initiator is respectively as follows: (100: 1 or 2.5: 1), (19: 1), (100: 1);

when the polymer monomer is butylene carbonate, the initiator is 2-bromomethyl propionate, and the weight ratio of the polymer monomer to the initiator is as follows: (30: 1);

when the polymer monomer is fluoroethylene carbonate, the initiator is stannous isooctanoate, and the weight ratio of the polymer monomer to the initiator is as follows: (100: 1);

when the polymer monomer is vinylene carbonate, the initiator is K₂S₂O₈Or NaHSO₃The weight ratio of the polymer monomer to each initiator is respectively as follows in sequence: (10: 1), (20: 1);

when the polymer monomer is butyrolactone, the initiator is benzyl alcohol, and the weight ratio of the polymer monomer to the initiator is as follows: (100: 1);

when the polymer monomer is 1, 3-dioxolane, 4-methyl-1, 3-dioxolane or 2-methyl-1, 3-dioxolane, the initiator is trioxymethylene, LiPF₆、M(CF₃SO₃) Or M (OTf)₃(M ═ Al, In, Zn, Bi, Mg, Sn), the weight ratios of the polymer monomer to each of the initiators In the stated order being: (8: 2), (13: 1) (200: 1), and (200: 1).

6. The lithium metal solid-state battery according to claim 5, wherein the inorganic-polymer composite electrolyte layer comprises the following components in a mass ratio: the ratio of the polymer monomer to the inorganic powder is 1:6, the weight ratio of the organic solvent to the polymer monomer is 15 (1-225), and the concentration of the lithium salt relative to the organic solvent is 1-5 moL/L.

7. The lithium metal solid-state battery according to claim 6, wherein the method of manufacturing the lithium metal solid-state battery comprises the steps of:

the method comprises the following steps: mixing lithium salt, an organic solvent, a polymer monomer and inorganic powder, fully stirring, and carrying out ultrasonic treatment for 1-6 hours to form a uniform suspension with a certain viscosity;

step two: mixing the positive electrode slurry with an initiator, coating the mixture on aluminum foil paper, and drying the aluminum foil paper at the temperature of 80-120 ℃ for 4-6 hours to form a positive electrode plate, wherein the compaction density is 3.2-3.5 g/cm²；

Step three: uniformly coating the suspension liquid in the step one on the positive plate prepared in the step two, horizontally placing the positive plate in a vacuum environment at 40-80 ℃, soaking for 2-6 hours, and then placing the positive plate in a condition of 60-100 ℃ for in-situ polymerization for 6-20 hours to obtain an integrated composite electrolyte positive electrode;

step four: and (4) covering the negative electrode on the electrolyte side of the integrated composite electrolyte positive electrode obtained in the third step, and heating and rolling in vacuum to obtain the lithium metal all-solid-state battery.

8. The method of manufacturing a lithium metal solid-state battery according to claim 7, wherein the positive electrode and the negative electrode each include a current collector; the anode slurry is LiFePO₄、LiCoO₂、Li(Ni_0.5Co_0.2Mn_0.3)O₂、Li(Ni_0.6Co_0.2Mn_0.2)O₂、Li(Ni_0.8Co_0.1Mn_0.1)O₂Or Li (Ni)_0.9Co_0.05Mn_0.05)O₂One of (1); the negative electrode is an ultrathin metal lithium/copper composite belt, and the thickness of the negative electrode is 5-10 um.

9. The method of manufacturing a lithium metal solid state battery according to claim 7, wherein the method is characterized in thatThe vacuum degree of vacuum heating rolling in the fourth step is 10^-4～10^-2Mpa, temperature of 150-180 deg.C, and pressure of 50-100 Mpa.

10. The method for manufacturing a lithium metal solid state battery according to claim 7, wherein the second step and the third step are both performed under an inert gas condition, and the inert gas is one or more of nitrogen, argon and helium.

Technical Field

The invention relates to the technical field of novel solid-state batteries, in particular to a lithium metal solid-state battery and a preparation method thereof.

Background

All-solid-state batteries based on solid electrolytes suffer from excessive interfacial resistance and obstruction of ion transport due to electrolyte/electrode interface problems during application, thereby affecting battery performance, such as swelling, powdering, dendrites, and short-circuiting. Since the solid electrolyte has no fluidity and cannot be fully contacted with the electrode, the uneven contact can cause holes and gaps between the solid electrolyte and the electrode, the gaps prevent lithium ions from diffusing at the interface, the interface impedance is increased, and the uneven distribution of current is caused while the polarization degree is larger.

Therefore, there is an urgent need to provide a solid-state lithium metal battery and a method for preparing the same, which are simple in process, easy in raw material availability, and suitable for large-scale industrial production, so as to solve the above problems.

Disclosure of Invention

The invention aims to solve the technical problem that a metal lithium solid-state battery and a preparation method thereof are provided aiming at the problem that the full contact with an electrode cannot be realized due to the fact that a solid electrolyte does not have fluidity.

The lithium metal solid-state battery includes: the lithium ion battery comprises a positive electrode, an inorganic-polymer composite electrolyte layer and a negative electrode, wherein the inorganic-polymer composite electrolyte layer is arranged between the positive electrode and the negative electrode, and the components of the inorganic-polymer composite electrolyte layer comprise a polymer monomer, lithium salt, an organic solvent, an initiator and inorganic powder.

The inorganic powder is a solid electrolyte material, and the solid electrolyte material is one or a mixture of a sulfide solid electrolyte material, a garnet solid electrolyte material, a perovskite solid electrolyte material, an NASICON solid electrolyte material, a halide solid electrolyte material and derivatives thereof; the sulfide solid state electrolyte material is: li₁₀GeP₂S₁₂(LGPS)、Li₁₀SnP₂S₁₂、Li₆PS₅Cl or Li_9.6P₃S₁₂One or more of the following; the garnet type solid electrolyte material comprises: li₇La₃Zr₂O₁₂、Li_7-xLa₃Zr₂O_12-x、Li_7-xLa₃Zr_2-xNb_xO₁₂、Li_7-xLa₃Zr_2-xTa_xO₁₂(X ═ 0.2 to 0.8) by mixing; the perovskite type solid electrolyte material is as follows: li_3xLa_2/3-xTiO₃(X＝0.1～0.15)、Li_3/8Sr_7/16Ta_3/4Zr_1/4O₃Or Li_3/8Sr_7/16Ta_3/4Hf_1/4O₃One or more of the following; the NASICON type solid electrolyte material is as follows: LiM (PO)₄)₃Wherein M is selected from Na⁺、Nb⁵⁺、Ta⁵⁺、Ti4⁺、Ge⁴⁺、Zr⁴⁺、Sn⁴⁺、Nb⁴⁺、Hf⁴⁺、Al³⁺、Cr³⁺、Ga³⁺、Fe³⁺、Sc³⁺、In³⁺、Y³⁺、La³⁺、Mg²⁺、Zn²⁺、Cu²⁺、Co²⁺、Mn²⁺、Fe²⁺At least one of; the halide solid state electrolyte material is: li₃OX or Li₃MX₆(X ═ F, Cl, Br or I, M ═ Y, In, Mg, Si or Zr) In a mixture of two or more.

Wherein the average particle diameter of the inorganic powder is 50 nm-10 um, and the ionic conductivity is 10^-3～10^-5S/cm, and the thickness of the inorganic-polymer composite electrolyte layer is 2 um-20 um.

Wherein the lithium salt is one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium bistrifluoromethanesulfonylimide, lithium difluoroborate, LiBOB, lithium difluorooxalato borate, lithium difluorophosphate or lithium oxalato phosphate; the organic solvent is one of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether or tetrahydrofuran.

Wherein the polymer monomers are: one of ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate, vinylene carbonate, butyl lactone, 1, 3-dioxolane, 4-methyl-1, 3-dioxolane or 2-methyl-1, 3-dioxolane;

when the polymer monomer is butylene carbonate, the initiator is 2-bromomethyl propionate, and the weight ratio of the polymer monomer to the initiator is as follows: (30: 1);

when the polymer monomer is fluoroethylene carbonate, the initiator is stannous isooctanoate, and the weight ratio of the polymer monomer to the initiator is as follows: (100: 1);

when the polymer monomer is butyrolactone, the initiator is benzyl alcohol, and the weight ratio of the polymer monomer to the initiator is as follows: (100: 1);

Wherein the inorganic-polymer composite electrolyte layer comprises the following components in percentage by mass: the ratio of the polymer monomer to the inorganic powder is 1:6, the weight ratio of the organic solvent to the polymer monomer is 15 (1-225), and the concentration of the lithium salt relative to the organic solvent is 1-5 moL/L.

A preparation method of a lithium metal solid-state battery comprises the following steps:

step two: the positive electrode slurry is mixed with the initiatorMixing the agents, coating the mixture on aluminum foil paper, drying the aluminum foil paper for 4 to 6 hours at the temperature of 80 to 120 ℃ to form a positive pole piece, wherein the compaction density is 3.2 to 3.5g/cm²；

Wherein the positive electrode and the negative electrode both comprise current collectors; the anode slurry is LiFePO₄、LiCoO₂、Li(Ni_0.5Co_0.2Mn_0.3)O₂、Li(Ni_0.6Co_0.2Mn_0.2)O₂、Li(Ni_0.8Co_0.1Mn_0.1)O₂Or Li (Ni)_0.9Co_0.05Mn_0.05)O₂One of (1); the negative electrode is an ultrathin metal lithium/copper composite belt, and the thickness of the negative electrode is 5-10 um.

Wherein the vacuum degree of the vacuum heating rolling in the fourth step is 10^-4～10^-2Mpa, temperature of 150-180 deg.C, and pressure of 50-100 Mpa.

Wherein, the first step to the fourth step are all prepared under the condition of inert gas, and the inert gas is one or a mixture of nitrogen, argon and helium.

The embodiment of the invention has the following beneficial effects:

the invention has simple process, takes the cyclic polymer monomer as the polymer precursor, mixes the initiator into the anode slurry, heats the initiator and the cyclic polymer monomer in the secondary coating composite electrolyte layer for in-situ polymerization, and then carries out hot pressing on the lithium metal cathode to form the integrated solid battery without the diaphragm; the in-situ polymerization is different from the common mixed precursor liquid polymerization, after the composite electrolyte mixed liquid containing the polymer monomer fully soaks the anode, the compound electrolyte mixed liquid and the initiator generate ring-opening polymerization in gaps, and a composite electrolyte phase is formed after chain growth reaction, so that an electrode/electrolyte interface with excellent performance is formed, and the gel electrolyte after the monomer polymerization can be filled in gaps among inorganic fillers to form the composite electrolyte phase, so that the method has the following advantages: the interface resistance is reduced; the poor interface reaction of the solid electrolyte and the anode is inhibited; the toughness of the solid electrolyte is improved; the composite electrolyte network constructed in situ between the anode material and the cathode material can effectively buffer the volume change in charge and discharge, so that the stability of the battery is improved; compared with the traditional battery preparation process, the battery construction mode is simple and effective, and provides a prospect and a foundation for realizing the production of the integrated solid-state battery.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a charge-discharge curve of a 2Ah lithium metal all-solid-state battery prepared in example one;

fig. 2 is a cycle electrical curve of a 2Ah lithium metal all solid state battery prepared in example one.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The present invention provides a lithium metal solid-state battery comprising: the lithium ion battery comprises a positive electrode, an inorganic-polymer composite electrolyte layer and a negative electrode, wherein the inorganic-polymer composite electrolyte layer is arranged between the positive electrode and the negative electrode, and the components of the inorganic-polymer composite electrolyte layer comprise a polymer monomer, lithium salt, an organic solvent, an initiator and inorganic powder.

The thickness of the inorganic-polymer composite electrolyte layer is 2 um-20 um.

The inorganic powder is a solid electrolyte material, and the solid electrolyte material is one or a mixture of a sulfide solid electrolyte material, a garnet solid electrolyte material, a perovskite solid electrolyte material, an NASICON solid electrolyte material, a halide solid electrolyte material and derivatives thereof; the sulfide solid state electrolyte material is: li₁₀GeP₂S₁₂(LGPS)、Li₁₀SnP₂S₁₂、Li₆PS₅Cl or Li_9.6P₃S₁₂One or more of the following; the garnet type solid electrolyte material comprises: li₇La₃Zr₂O₁₂、Li_7-xLa₃Zr₂O_12-x、Li_7-xLa₃Zr_2-xNb_xO₁₂、Li_7-xLa₃Zr_2-xTa_xO₁₂(X ═ 0.2 to 0.8) by mixing; the perovskite type solid electrolyte material is as follows: li_3xLa_2/3-xTiO₃(X＝0.1～0.15)、Li_3/8Sr_7/16Ta_3/4Zr_1/4O₃Or Li_3/8Sr_7/16Ta_3/4Hf_1/4O₃One or more of the following; the NASICON type solid electrolyte material is as follows: LiM (PO)₄)₃Wherein M is selected from Na⁺、Nb⁵⁺、Ta⁵⁺、Ti⁴⁺、Ge⁴⁺、Zr⁴⁺、Sn⁴⁺、Nb⁴⁺、Hf⁴⁺、Al³⁺、Cr³⁺、Ga³⁺、Fe³⁺、Sc³⁺、In³⁺、Y³⁺、La³⁺、Mg²⁺、Zn²⁺、Cu²⁺、Co²⁺、Mn²⁺、Fe²⁺At least one of; the halide solid state electrolyte material is: li₃OX or Li₃MX₆(X ═ F, Cl, Br or I, M ═ Y, In, Mg, Si or Zr) In a mixture of two or more. The average particle diameter of the inorganic powder is 50nm to 10um and the ionic conductivity of 10^-3～10^-5S/cm. Wherein the lithium salt is one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium bistrifluoromethanesulfonylimide, lithium difluoroborate, LiBOB, lithium difluorooxalato borate, lithium difluorophosphate or lithium oxalato phosphate; the organic solvent is one of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether or tetrahydrofuran.

The polymer monomer is one of ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate, vinylene carbonate, butyl lactone, 1, 3-dioxolane, 4-methyl-1, 3-dioxolane or 2-methyl-1, 3-dioxolane.

When the polymer monomer is ethylene carbonate, the initiator is 1, 2-propylene glycol, diethylene glycol, KOH, ethylene glycol or monoethylene glycol, and the weight ratio of the initiator to the ethylene carbonate is respectively as follows: (10: 1), (1.2: 1), (1.5:1), (1.2: 1), and (1.2: 1).

When the polymer monomer is propylene carbonate, the initiator is diethylene glycol, benzenediol or phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, and the weight ratio of the initiator to the propylene carbonate is respectively as follows: (100: 1 or 2.5: 1), (19: 1), (100: 1).

When the polymer monomer is butylene carbonate, the initiator is 2-bromomethyl propionate, and the weight ratio of the initiator to the butylene carbonate is as follows: (30:1).

When the polymer monomer is fluoroethylene carbonate, the initiator is stannous isooctanoate, and the weight ratio of the stannous isooctanoate to the fluoroethylene carbonate is as follows: (100:1).

When the polymer monomer is vinylene carbonate, the initiator is K₂S₂O₈Or NaHSO₃The weight ratio of the ethylene carbonate to the vinylene carbonate is respectively as follows: (10: 1) and (20: 1).

When the polymer monomer is butyl lactone, the initiator is benzyl alcohol, and the weight ratio of the benzyl alcohol to the butyl lactone is as follows: (100:1).

When the polymer monomer is 1, 3-dioxolane, 4-methyl-1, 3-dioxolane or 2-methyl-1, 3-dioxolane, the initiator is trioxymethylene or LiPF₆、M(CF₃SO₃) Or M (OTf)₃(M ═ Al, In, Zn, Bi, Mg, Sn), In a weight ratio to the polymer monomer: (8: 2), (13: 1) (200: 1), and (200: 1).

In the metal lithium solid-state battery, the mass ratio of each component in the inorganic-polymer composite electrolyte layer is as follows: the ratio of the polymer monomer to the inorganic powder is 1:6, the weight ratio of the organic solvent to the polymer monomer is 15 (1-225), and the concentration of the lithium salt relative to the organic solvent is 1-5 moL/L.

A preparation method of a lithium metal solid-state battery comprises the following steps:

step four: covering the negative electrode on the electrolyte side of the integrated composite electrolyte positive electrode obtained in the third step, and heating and rolling in vacuum to obtain the lithium metal all-solid-state battery, wherein the vacuum degree of the vacuum heating and rolling is 10^-4～10^-2Mpa, temperature of 150-180 deg.C, and pressure of 50-100 Mpa.

And step two and step three are both prepared under the condition of inert gas, and the inert gas is one or a mixture of nitrogen, argon and helium.

Example 1

A preparation method of a lithium metal solid-state battery comprises the following steps:

1. dissolving lithium bistrifluoromethanesulfonylimide as lithium salt into an organic solvent of ethylene glycol dimethyl ether (DME) with the concentration of 2moL/L to form an electrolyte solution, adding a 4-methyl-1, 3-dioxolane polymer monomer (the weight ratio of the organic solvent to the monomer is 2/3) material into the electrolyte solution, fully stirring, and adding Li with the particle size of 50nm₇La_2.875Y_0.125Zr₂O₁₂Adding an inorganic filler (the mass ratio of the polymer monomer to the inorganic split filler is 2:3) into the mixed solution, fully stirring, and carrying out ultrasonic treatment for 3 hours to obtain a uniform suspension with a certain viscosity.

2. In an inert gas atmosphere in Li (Ni)_0.6Co_0.2Mn_0.2)O₂Adding an initiator Al (CF) into the positive electrode slurry₃SO₃)₃(the weight ratio of the polymer monomer to the initiator is 200:1) is fully stirred, the mixture is evenly mixed and coated on aluminum foil paper, the mixture is dried for 6 hours at the temperature of 80 ℃, and the compaction density is 3.2g/cm²And obtaining the composite positive plate.

3. And (3) uniformly coating the suspension liquid obtained in the step (1) on the composite positive plate prepared in the step (2) in an inert gas atmosphere, horizontally placing in a vacuum environment at 45 ℃, soaking for 2 hours, and then placing the composite positive plate under the condition of 80 ℃ for in-situ polymerization for 18 hours to obtain the integrated composite electrolyte positive electrode.

4. Covering the electrolyte side of the integrated composite electrolyte anode obtained in the step 3 with an ultrathin metal lithium/copper cathode sheet with the thickness of 10um, and carrying out vacuum heating and rolling with the vacuum degree of 10^-2Mpa, temperature 150 ℃, pressure 50Mpa, finally obtaining the lithium metal all-solid-state battery.

Example 2