Metal oxide modified SSE surface electrolyte sheet and anode-free solid-state lithium battery

Abstract

The present invention provides an electrolyte sheet with a metal oxide modified SSE surface and a negative electrode-free solid-state lithium battery, by constructing ZnO on the surface of the solid electrolyte (SSE) using industrially available Zn / Cd vapor. x / CdO x Interface layer, after assembling the negative electrode-free solid-state battery, first charge it to make ZnO x / CdO x Lithium is deposited on the interface, and then the battery is heated to make ZnO x / CdO x The interface reacts with lithium to form a Zn+Li2O / Cd+Li2O ion / electron mixed conductor interface layer MCI. MCI can significantly improve the compatibility of the SSE and current collector interface in solid-state batteries. The preparation process is mainly divided into two steps. The first step is the evaporation of low-boiling-point metals, and their condensation and oxidation on the surface of SSE; the second step is the assembly of the anode-free solid-state battery and the in-situ conversion of the oxide interface layer. Compared with the unmodified anode-free solid-state battery, the anode-free solid-state battery with in-situ generated interface layer in the present invention has significantly improved electrochemical performance. At the same time, the raw materials of this process are widely available, which will promote the large-scale production of low-cost, high-energy-density anode-free solid-state batteries.

Description

Technical Field

[0001] The present invention belongs to the technical field of battery interface material design, and in particular relates to an electrolyte sheet with a metal oxide modified SSE surface and a negative electrode-free solid-state lithium battery. Background Art

[0002] Compared to traditional commercial lithium-ion batteries based on liquid electrolytes, solid-state batteries offer the following advantages: 1) Solid-state batteries replace liquid electrolytes with solid electrolytes, significantly reducing the risk of thermal runaway; 2) The electrochemical window of solid-state batteries can reach over 5V, higher than that of liquid lithium batteries (4.2V), allowing for the use of high-energy cathodes, significantly increasing theoretical energy density; 3) Solid-state batteries can simplify packaging and cooling systems, further reducing battery weight in limited space, and increasing volumetric energy density by over 70% compared to liquid lithium batteries (graphite anodes), reaching 500Wh / kg. Furthermore, the recent rise of anode-free batteries, which eliminate the use of anodes and further improve battery energy density, is considered the ultimate goal of lithium batteries. Therefore, combining the concepts of solid-state batteries and anode-free batteries to construct a stable anode-free solid-state battery is expected to achieve the holy grail of both high battery safety and high energy density.

[0003] However, since the oxide solid electrolyte replaces the liquid electrolyte, the contact interface between the current collector and the solid electrolyte of the negative electrode-free battery changes from a solid|liquid interface to a solid|solid interface, resulting in poor contact of the solid electrolyte with the current collector. In addition, the interfacial double layer between the current collector and the solid electrolyte causes a higher interface resistance at the solid|solid interface, resulting in Li + Conduction is blocked and a large amount of "dead lithium" is generated. Therefore, in practice, anode-free solid-state lithium batteries still face problems such as poor rate performance, short cycle life, and rapid battery performance degradation. Therefore, developing a method for constructing an interface functional layer between the solid electrolyte and the current collector to improve contact, and designing a matching anode-free solid-state battery preparation method, can improve the cycle life of anode-free solid-state batteries and accelerate their commercial application. Summary of the Invention

[0004] In order to solve the problem of poor interface contact between solid electrolyte and current collector, the present invention provides an electrolyte sheet with metal oxide modified SSE surface and a negative electrode-free solid-state lithium battery. The electrolyte sheet with metal oxide modified SSE surface adopts industrially readily available Zn and Cd vapor to deposit and oxidize on the oxide solid electrolyte to construct an oxidized interface layer (ZnO x , CdO x ), and then used to assemble a negative electrode-free solid-state lithium battery. After charging to a certain depth, the original oxide interface layer will be lithium-ionized, that is, the interface layer will become a mixture of metallic lithium and oxide (Li+ZnO x、 Li+CdO x ), and then the battery is heated at medium temperature, and the interface layer is transformed into a mixture of Li+Li2O+Zn / Li+Li2O+Cd ions and electrons. The characteristics of ion-electron co-conduction make the sites of Li nucleation in subsequent charging more uniform. In addition, the metal Li softened during the medium-temperature heating process will act as a binder to enable full contact between the current collector and the solid electrolyte.

[0005] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0006] The method for preparing an electrolyte sheet with a metal oxide modified SSE surface comprises the following steps:

[0007] Step 1: The oxide solid electrolyte (SSE) powder is subjected to high-energy ball milling to reduce its particle size. The ball-milled SSE powder and a 20% mass fraction aprotic solution of an organic lithium compound are placed in a grinding jar in a mass ratio of 100:5-20 and ground thoroughly to ensure the densification of the subsequent sintering electrolyte and reduce the entry of low-boiling-point vapor into the grain boundaries of the SSE in subsequent experiments;

[0008] Step 2: Pour the mixed powder obtained in step 1 into a cylindrical mold with an inner diameter of 16 mm and cold press at a pressure of 10-40 MPa for 3-10 minutes, then perform programmed temperature sintering in a muffle furnace, and place the obtained dense SSE sheet in an anhydrous isopropanol / ethanol solution for ultrasonic treatment and drying;

[0009] Step 3: Place a certain mass of low-boiling-point metal flakes / particles (Zn foil / Cd pellets) in the middle of a tube furnace. Place the SSE sheet obtained in Step 2 at the outlet of the tube furnace. In an argon atmosphere, heat the tube furnace to a certain temperature so that the low-boiling-point metal flakes / particles can generate steam in the middle of the tube furnace. The steam can condense on the solid electrolyte sheet at the outlet, forming an SSE@low-boiling-point metal interface modification layer.

[0010] Step 4: Place the SSE sheet with preliminary surface modification obtained in step 3 in a muffle furnace for medium-temperature oxidation to oxidize the surface Zn / Cd into ZnO x / CdO x Finally, the electrolyte sheet (SSE@ZnO x / CdO x ).

[0011] In step 1, the solid electrolyte is A3B2(XO4)3 (A = Ga, Mg, Y, La or other rare earth elements; B = Al, Fe, Ga, Ge, Mn, Ni or V), ATiO3 (A = Ca, Sr, Ba), Li 1+x Al x Ti2-x (PO4)3, etc., the organic lithium compound is one or more of lithium acetoacetate, tert-butyl lithium, lithium citrate, n-butyl lithium, dilithium phthalocyanine, lithium difluorooxalatoborate, and the solvent of the aprotic solution is one or more of hexamethylphosphoric triamide, dimethylformamide, acetonitrile, and dimethyl sulfoxide.

[0012] In step 2, the programmed temperature rise is divided into two stages. The first stage has a heating rate of 2 to 5°C / min, a sintering temperature of 300°C to 700°C, and a sintering time of 1 to 4 hours. The second stage has a heating rate of 1 to 5°C / min, a sintering temperature of 900°C to 1400°C, and a sintering time of 3 to 15 hours.

[0013] In step three, the mass ratio of Zn foil / Cd particles to SSE is 0.2-5:1, the heating rate of the tubular furnace is 2-8°C / min, the holding temperature is 400-700°C for Zn foil and 500-700°C for Cd particles, and the holding time is 0.5-3h.

[0014] In step 4, the heating rate of the muffle furnace is 1-5°C / min, the holding temperature is: SSE@Zn 200-400°C, SSE@Cd 100-300°C, and the holding time is 1-4h.

[0015] The preparation method of a negative electrode-free solid-state lithium battery comprises the following steps:

[0016] Step 1: uniformly mix the low-voltage positive electrode and the high-voltage positive electrode materials in a mass ratio of 1:0.2-1, and fully stir the mixed positive electrode with carbon black and NMP solution containing a high-temperature resistant binder in a mass ratio of 9:0.6:0.4 to obtain a mixed positive electrode slurry. The positive electrode slurry is evenly coated on an aluminum foil current collector with a thickness of 80-150 μm, dried in a vacuum drying oven at 120°C for 10-20 hours, and cut into discs with a diameter of 14 mm;

[0017] In step 1, the low-voltage positive electrode material is one or more of LiFePO4, V2O5, FeF3, FeS2, and MoS2, and the high-voltage positive electrode material is one or more of LiMnPO4, LiCoO2, Li2Mn 2-x Ni x O4, xLi2MnO3·(1-x)LiMO2 (M=Ni, Mn, Co), LiNi 1-x-y Co x Mn y O2, wherein the high temperature resistant binder is one or more of styrene-butadiene rubber, polyacrylic acid, carboxymethyl cellulose, and polyurethane.

[0018] Step 2: Lay a 16mm diameter copper foil current collector disc on the side of the solid electrolyte with the oxide functional layer. Apply a pressure of 2-5 MPa at 300-600°C for 2-5 minutes to ensure good contact between the interface layer and the copper foil. Then, place the hybrid positive electrode sheet obtained in step 1 on the side without the oxide interface layer and assemble the battery.

[0019] Step 3: Charge the assembled battery to 4.2V. + It will be deposited in the form of metallic lithium between the current collector and the oxide interface layer. The charged battery is placed in an oven at 180-260°C for 1-3 hours. During this process, the interface layer is transformed into a mixture of Li+Li2O+Zn / Li+Li2O+Cd ions and electrons. The softened deposited lithium will build a uniform lithium ion and electron path between the solid electrolyte and the current collector. The battery is then discharged to 2.5V to obtain a negative electrode-free solid-state battery. The optimal operating voltage range is set to 2.5-3.7V (during the preparation of the battery, the high-voltage positive electrode is first charged to 4.2V to provide additional lithium source for the formation of Li2O in the interface layer, and the low-voltage positive electrode acts as the main active material in the subsequent 2.5-3.7V cycle).

[0020] The beneficial effects of the present invention compared to the prior art are:

[0021] (1) The Zn and Cd steam used in the present invention are widely available and inexpensive. For example, domestic Zn and Cd refineries produce a large amount of Zn and Cd steam. The interface modification strategy described in the present invention can be coupled with such industries to promote resource utilization and industrial integration.

[0022] (2) ZnO x / CdO x The Zn+Li2O / Cd+Li2O layer produced by high-temperature reaction with lithium is an ion / electron mixed conductor interphase (MCI) with fast ion transport characteristics. The discretely distributed Zn / Cd atoms in the MCI layer break the relatively long-range ordered crystal structure, forming more grain boundaries and polycrystalline regional defects, ensuring the rapid conduction of lithium ions in the interface layer. The weak electronic conductivity provides a migration electric field as a driving force for the migration of lithium ions in the interface layer, which is of great value for directional guidance of lithium ion transport.

[0023] (3) The present invention can regulate the thickness of the interface layer by controlling the deposition time and the concentration of Zn and Cd vapor. In addition, the Zn+Li2O / Cd+Li2O MCI layer has a uniform lithium flux, which can inhibit dead lithium and avoid premature degradation of the negative electrode-free solid-state battery.

[0024] (4) The idea of in-situ generation of the MCI layer after assembling the battery in the present invention enables the negative electrode-free solid-state battery to have significantly reduced impedance, which will promote technological progress in the field of negative electrode-free solid-state batteries. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 Schematic diagram of the preparation of LLZTO@Zn / Cd;

[0026] Figure 2 LLZTO@ZnO x / CdO x Schematic diagram of the preparation of the preliminary interface modification layer;

[0027] Figure 3 LLZTO@ZnO prepared in Examples 1 and 2 x / CdO x Digital image of the preliminary interface modification layer;

[0028] Figure 4 Impedance diagrams of negative electrode-free solid-state batteries prepared for Examples 1 and 2 and Comparative Example 1. DETAILED DESCRIPTION

[0029] The technical solution of the present invention is further described below with reference to the accompanying drawings and embodiments, but is not limited thereto. Any modification or equivalent replacement of the technical solution of the present invention that does not depart from the spirit and scope of the technical solution of the present invention should be included in the scope of protection of the present invention.

[0030] Example 1:

[0031] This embodiment performs a two-step construction method for a functional interface layer between a solid electrolyte and a current collector and prepares a negative electrode-free solid-state lithium battery according to the following steps:

[0032] Step 1: Preliminary construction of the functional interface layer between the solid electrolyte and the current collector to obtain an electrolyte sheet with metal oxide modified SSE surface;

[0033] (1) The solid electrolyte LLZTO powder was subjected to high-energy ball milling to reduce its particle size. The ball-milled LLZTO powder and a 20% by mass fraction of lithium acetoacetate in hexamethylphosphoramide solution were placed in a grinding jar in a mass ratio of 100:10 to fully grind to ensure the densification of the electrolyte in the subsequent sintering;

[0034] (2) The mixed powder obtained in step (1) was poured into a cylindrical mold with an inner diameter of 16 mm and cold pressed at a pressure of 10 MPa for 5 min. The mixture was then heated to 400°C in a muffle furnace at a heating rate of 2°C / min and maintained for 1 h. The mixture was then heated to 1100°C at a heating rate of 3°C / min and maintained for 9 h. The resulting dense LLZTO sheet was placed in an anhydrous isopropanol / ethanol solution for ultrasonic treatment and drying.

[0035] (3) Figure 1 As shown, a certain mass of Zn foil is placed in the middle of a tube furnace, and the LLZTO sheet obtained in step (2) is placed at the outlet of the tube furnace. In an argon atmosphere, the tube furnace is heated to 600°C at a heating rate of 5°C / min and kept warm for 1 hour, so that the Zn foil can generate steam in the middle of the tube furnace, and the steam can condense on the solid electrolyte sheet at the outlet to form LLZTO@Zn, wherein the mass ratio of Zn foil to LLZTO is 3:1;

[0036] (4) Figure 2 As shown in the figure, the LLZTO@Zn sheet obtained in step (3) was placed in a muffle furnace, heated to 300°C at a heating rate of 2°C / min and kept warm for 3h to oxidize the Zn on the surface into ZnO. x , and finally obtain LLZTO@ZnO x (See digital image Figure 3 ).

[0037] Step 2: Preparation of anode-free solid-state battery and in-situ construction of the second functional interface layer;

[0038] (1) LiFePO4 and Li2MnO3 were uniformly mixed in a mass ratio of 1:0.4, and the mixed positive electrode, carbon black, and NMP solution containing styrene-butadiene rubber binder were fully stirred in a mass ratio of 9:0.6:0.4 to obtain a mixed positive electrode slurry. The positive electrode slurry was uniformly coated on an aluminum foil current collector with a thickness of 100 μm, dried in a vacuum drying oven at 120°C for 12 h, and cut into discs with a diameter of 14 mm;

[0039] (2) The 16 mm diameter copper foil current collector disc is connected to the LLZTO with ZnO x The interface layer was laminated to one side of the copper foil, and a pressure of 3 MPa was applied at 500 ° C for 3 min to ensure good contact between the interface layer and the copper foil. x Place the mixed positive electrode sheet obtained in step (1) on one side of the layer and assemble the battery;

[0040] (3) The assembled battery is first charged to 4.2V, and then placed in an oven at 240°C for 1 hour. During this process, the interface layer is in situ transformed into a mixed interface layer of Li+Li2O+Zn ions and electrons. The softened deposited lithium will build a uniform lithium ion and electron path between the solid electrolyte and the current collector. The battery is then discharged to 2.5V to obtain a negative electrode-free solid-state battery. Figure 4 This is the impedance diagram of a solid-state battery without a negative electrode. It can be seen that the interface layer constructed in two steps has significantly reduced impedance.

[0041] Example 2:

[0042] The difference between this embodiment and Example 1 is that a different low boiling point metal (Cd) is used:

[0043] Step 1: Preliminary construction of the functional interface layer between the solid electrolyte and the current collector to obtain an electrolyte sheet with metal oxide modified SSE surface;

[0044] (1) The ball-milled LLZTO powder and a 20% by mass fraction lithium acetoacetate hexamethylphosphoramide solution were placed in a grinding jar in a mass ratio of 100:10 and fully ground;

[0045] (2) pouring the mixed powder obtained in step (1) into a cylindrical mold with an inner diameter of 16 mm and cold pressing at a pressure of 10 MPa for 5 min, then heating it to 400°C in a muffle furnace at a heating rate of 2°C / min and holding it for 1 h, then heating it to 1100°C at a heating rate of 3°C / min and holding it for 9 h;

[0046] (3) Figure 1 As shown, a certain mass of Cd particles are placed in the middle of a tube furnace, and the LLZTO sheet obtained in step (2) is placed at the outlet of the tube furnace. In an argon atmosphere, the tube furnace is heated to 500°C at a heating rate of 5°C / min and kept warm for 1 hour to form LLZTO@Cd, wherein the mass ratio of Cd particles to LLZTO is 4:1;

[0047] (4) Figure 2 As shown, the LLZTO@Cd sheet obtained in step (3) was placed in a muffle furnace, heated to 200°C at a heating rate of 2°C / min and kept warm for 2h to oxidize the Cd on the surface to CdO x , and finally obtain LLZTO@CdO x (See digital image Figure 3 ).

[0048] Step 2: Preparation of anode-free solid-state battery and in-situ construction of the second functional interface layer;

[0049] (1) LiFePO4 and Li2MnO3 were uniformly mixed in a mass ratio of 1:0.4, and the mixed positive electrode, carbon black, and NMP solution containing styrene-butadiene rubber binder were fully stirred in a mass ratio of 9:0.6:0.4 to obtain a mixed positive electrode slurry. The positive electrode slurry was uniformly coated on an aluminum foil current collector with a thickness of 100 μm, dried in a vacuum drying oven at 120°C for 12 h, and cut into discs with a diameter of 14 mm;

[0050] (2) Place a 16 mm diameter copper foil current collector disc on the LLZTO with CdO x The interface layer was laminated to one side of the copper foil, and a pressure of 3 MPa was applied at 500 ° C for 3 min to ensure good contact between the interface layer and the copper foil. xPlace the mixed positive electrode sheet obtained in step (1) on one side of the layer and assemble the battery;

[0051] (3) The assembled battery is first charged to 4.2V, and the charged battery is placed in an oven at 240°C for 1 hour. During this process, the interface layer is in situ transformed into a mixed interface layer of Li+Li2O+Zn ions and electrons. The battery is then discharged to 2.5V to obtain a negative electrode-free solid-state battery.

[0052] Comparative Example 1:

[0053] The difference between this comparative example and Examples 1 and 2 is that no interface layer is constructed between the solid electrolyte and the current collector:

[0054] (1) The ball-milled LLZTO powder and a 20% by mass fraction lithium acetoacetate hexamethylphosphoramide solution were placed in a grinding jar in a mass ratio of 100:10 and fully ground;

[0055] (2) pouring the mixed powder obtained in step (1) into a cylindrical mold with an inner diameter of 16 mm and cold pressing at a pressure of 10 MPa for 5 min, then heating it to 400°C in a muffle furnace at a heating rate of 2°C / min and holding it for 1 h, then heating it to 1100°C at a heating rate of 3°C / min and holding it for 9 h;

[0056] (3) LiFePO4, carbon black, and NMP solution containing styrene-butadiene rubber binder were fully stirred in a mass ratio of 9:0.6:0.4 to obtain a mixed positive electrode slurry. The positive electrode slurry was evenly coated on an aluminum foil current collector with a thickness of 100 μm, dried in a vacuum drying oven at 120°C for 12 h, and cut into discs with a diameter of 14 mm.

[0057] (4) A 16 mm diameter copper foil current collector disc was laminated to one side of the LLZTO, and a pressure of 3 MPa was applied at 500°C for 3 min. Then, the mixed positive electrode sheet obtained in step (3) was placed on the other side and the battery was assembled to obtain a negative electrode-free solid-state battery without an interface modification layer.

Claims

1. A method for preparing an electrolyte sheet with a metal oxide modified SSE surface, characterized in that: The following steps are involved: Step 1: The oxide solid electrolyte SSE powder is subjected to high-energy ball milling, and the ball-milled SSE powder and a 20% mass fraction aprotic solution of an organic lithium compound are placed in a grinding jar in a mass ratio of 100:5-20 and ground thoroughly; Step 2: Pour the mixed powder obtained in step 1 into a cylindrical mold with an inner diameter of 16 mm and cold press at a pressure of 10-40 MPa for 3-10 min. Then, perform programmed temperature sintering in a muffle furnace. The obtained dense SSE sheet is placed in an anhydrous isopropanol / ethanol solution for ultrasonic treatment and drying. Step 3: Place the Zn foil / Cd pellets in the middle of a tube furnace, and place the SSE sheet obtained in step 2 at the outlet of the tube furnace. In an argon atmosphere, heat the tube furnace to a temperature where the low-boiling-point metal sheet / particles can generate steam in the middle of the tube furnace. The steam can condense on the solid electrolyte sheet at the outlet, forming an SSE@low-boiling-point metal interface modification layer. The mass ratio of Zn foil / Cd pellets to SSE is 0.2-5:1, the heating rate of the tube furnace is 2-8 °C / min, the holding temperature is 400-700 °C for Zn foil and 500-700 °C for Cd pellets, and the holding time is 0.5-3 h. Step 4: Place the SSE sheet with preliminary surface modification obtained in step 3 in a muffle furnace for medium-temperature oxidation. The heating rate of the muffle furnace is 1-5 °C / min, the holding temperature is: SSE@Zn 200-400 °C, SSE@Cd 100-300 °C, and the holding time is 1-4 h; oxidize the surface Zn / Cd to ZnO x / CdO x Finally, the electrolyte sheet with metal oxide modified SSE surface was obtained, namely SSE@ZnO x / CdO x .

2. The method for preparing an electrolyte sheet having a metal oxide modified SSE surface according to claim 1, characterized in that: In step 1, the oxide solid electrolyte is one or more of the following: A3B2(XO4)3, A = Ga, Mg, Y, or rare earth elements; B = Al, Fe, Ga, Ge, Mn, Ni or V; ATiO3, A = Ca, Sr, Ba; Li 1+x Al x Ti 2-x (PO4)3; The organic lithium compound is one or more of lithium acetoacetate, tert-butyl lithium, lithium citrate, n-butyl lithium, dilithium phthalocyanine, and lithium difluorooxalatoborate; The solvent of the aprotic solution is one or more of hexamethylphosphoric triamide, dimethylformamide, acetonitrile and dimethyl sulfoxide.

3. The method for preparing an electrolyte sheet having a metal oxide modified SSE surface according to claim 1, wherein: In step 2, the programmed temperature rise is divided into two stages. In the first stage, the heating rate is 2~5℃ / min, the sintering temperature is 300℃~700℃, and the sintering time is 1~4 h. In the second stage, the heating rate is 1~5℃ / min, the sintering temperature is 900℃~1400℃, and the sintering time is 3~15 h.

4. The electrolyte sheet with metal oxide modified SSE surface is characterized by: Obtained by the preparation method according to any one of claims 1 to 3.

5. The use of the electrolyte sheet with metal oxide modified SSE surface according to claim 4, characterized in that: Used to prepare negative electrode-free solid-state lithium batteries.

6. A method for preparing a negative electrode-free solid-state lithium battery, characterized in that: The following steps are involved: Step 1: Evenly mix the low-voltage positive electrode and high-voltage positive electrode materials in a mass ratio of 1:0.2~1, and fully stir the mixed positive electrode with carbon black and NMP solution containing a high-temperature resistant binder in a mass ratio of 9:0.6:0.4 to obtain a mixed positive electrode slurry. The positive electrode slurry is evenly coated on an aluminum foil current collector with a thickness of 80~150 μm, dried in a vacuum drying oven at 120°C for 10~20 h, and cut into discs with a diameter of 14 mm; Step 2: Lay a 16 mm diameter copper foil current collector disc on the side of the electrolyte sheet with the metal oxide modified SSE surface as described in claim 4 having an oxide functional layer, apply a pressure of 2 to 5 MPa at 300 to 600 ° C for 2 to 5 minutes to ensure good contact between the interface layer and the copper foil, and then place the hybrid positive electrode sheet obtained in step 1 on the side without the oxide interface layer and assemble the battery; Step 3: Charge the assembled battery to 4.2V. + It will be deposited in the form of metallic lithium between the current collector and the oxide interface layer. The charged battery is placed in an oven at 180~260 ℃ for 1~3 hours. During this process, the interface layer is transformed into a mixture of Li+Li2O+Zn / Li+Li2O+Cd ions and electrons. The softened deposited lithium will build a uniform lithium ion and electron path between the solid electrolyte and the current collector. The battery is then discharged to 2.5 V to obtain a negative electrode-free solid-state battery. The optimal operating voltage range is set to 2.5~3.7 V.

7. The method for preparing a negative electrode-free solid-state lithium battery according to claim 6, characterized in that: In step 1, the low-voltage positive electrode material is one or more of LiFePO4, V2O5, FeF3, FeS2, and MoS2; the high-voltage positive electrode material is one or more of the following: LiMnPO4; LiCoO2; Li2Mn 2−x Ni x O4; xLi2MnO3·(1-x)LiMO2, M=Ni, Mn, Co; LiNi 1−x− y Co x Mn y O2; The high temperature resistant adhesive is one or more of styrene-butadiene rubber, polyacrylic acid, carboxymethyl cellulose, and polyurethane.

8. A negative electrode-free solid-state lithium battery, characterized in that: Obtained by the preparation method according to claim 6 or 7.

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