Positive electrode, negative electrode, all-solid-state battery, and method for manufacturing same

Abstract

The present application provides a positive electrode, which comprises a positive electrode current collector and a positive electrode material, wherein the positive electrode material comprises a positive electrode active material, an inorganic glassy solid electrolyte, a conductive aid, and a binder, wherein the inorganic glassy solid electrolyte has the following chemical formula: DA x O y Cl z wherein D is Li or Na; A is selected from one or more of B, Al, Fe, Ga, In, As, Sb, Mo, and Bi; 0.2≤x≤3, 0

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of electrochemical energy storage. Specifically, the present application relates to a positive electrode, a negative electrode, an all-solid-state battery and a preparation method thereof. BACKGROUND

[0002] In recent years, the demand for electric vehicles is growing worldwide, leading to an increasing demand for high energy density, high safety and cost-effective energy storage devices. Replacing the flammable organic electrolyte in existing lithium-ion battery and sodium-ion battery technologies with solid electrolytes is considered the best way to eliminate battery safety hazards and break through the energy density bottleneck of existing batteries.

[0003] The current mainstream lithium-ion battery solid electrolyte is mainly divided into three categories: oxide ceramic, sulfide and PEO polymer solid electrolyte. Sulfide and PEO polymer solid electrolyte have good processing performance due to easy deformation, which is beneficial to large-scale industrial production. However, they are also prone to oxidative decomposition at high voltage and are not compatible with high-voltage positive electrodes, which greatly limits the improvement of battery energy density. Oxide ceramic solid electrolyte has good high-voltage resistance and can be compatible with high-voltage positive electrode materials. However, it is hard and brittle, has poor processing performance, and has the problems of small contact area and large interface impedance with positive electrode material particles.

[0004] At present, there is an urgent need for an inorganic glassy solid electrolyte with excellent processing performance (easy deformation) and high-voltage resistance, as well as a solid-state battery with excellent processing performance and excellent interface contact. SUMMARY

[0005] The purpose of the present application is to provide an all-solid-state battery with low cost and without using any solvent, which has the characteristics of negligible grain boundary resistance, low melting temperature and high viscoelasticity. The all-solid-state battery of the present application can achieve good contact between different interfaces by pressurization or heating melting.

[0006] The above purpose of the present application is achieved by the following technical solutions.

[0007] In a first aspect, the present application provides a positive electrode comprising a positive electrode current collector and a positive electrode material, wherein the positive electrode material comprises a positive electrode active material, an inorganic glassy solid electrolyte (SSE), a conductive aid and a binder, and the inorganic glassy solid electrolyte has the following chemical formula: DA x O y Cl z wherein D is Li or Na; A is selected from one or more of B, Al, Fe, Ga, In, As, Sb, Mo and Bi; 0.2≤x≤3, 0<y≤3, 0<z≤9 and the molar fraction of D is less than 0.5.

[0008] Preferably, in the positive electrode of the present application, the positive electrode active material is selected from one or more of oxide layered materials and polyanion positive electrode materials.

[0009] Preferably, in the positive electrode of the present application, the conductive additive is selected from one or more of KB, Super-P, acetylene black, CNT and rGO.

[0010] Preferably, in the positive electrode of the present application, the binder is selected from one or more of PVDF, PTFE, NaAlg, CMC, SBR and PAA.

[0011] The inorganic glassy solid electrolyte of the present application can be prepared by the preparation method in patent application No. 202110334157.8 and patent application No. 202110334142.1, the disclosure of which is incorporated herein by reference in its entirety.

[0012] In a second aspect, the present application provides a method for preparing the positive electrode of the present application, comprising the following steps:

[0013] (1) mixing the positive electrode active material particles, the conductive additive, the inorganic glassy solid electrolyte and the binder uniformly, and then preparing the positive electrode material press sheet by calendering method;

[0014] (2) attaching the positive electrode material press sheet to the positive electrode current collector to prepare the positive electrode.

[0015] In a third aspect, the present application provides a negative electrode, comprising a negative electrode current collector and a negative electrode material, wherein the negative electrode material comprises a negative electrode active material, an inorganic glassy solid electrolyte, a conductive additive and a binder, wherein the inorganic glassy solid electrolyte has the following chemical formula: DA x O y Cl z , wherein D is Li or Na; A is selected from one or more of B, Al, Fe, Ga, In, As, Sb, Mo and Bi; 0.2≤x≤3, 0

[0016] Preferably, in the negative electrode of the present application, the negative electrode active material is selected from one or more of carbon-based materials, alloy-based materials, oxide layered materials and polyanion-based materials.

[0017] Preferably, in the negative electrode of the present application, the conductive additive is selected from one or more of KB, Super-P, acetylene black, CNT and rGO.

[0018] Preferably, in the negative electrode according to the present application, the binder is selected from one or more of PVDF, PTFE, NaAlg, CMC, SBR and PAA.

[0019] In a fourth aspect, the present application provides a method for preparing the negative electrode according to the present application, comprising the following steps:

[0020] (1) mixing the negative electrode active material particles, the conductive additive, the inorganic glassy solid electrolyte and the binder uniformly, and then preparing a negative electrode material sheet by calendering the mixture;

[0021] (2) attaching the negative electrode material sheet to a negative electrode current collector to prepare the negative electrode.

[0022] In a specific embodiment of the present application, the electrode active material particles (positive electrode active material particles or negative electrode active material particles) are first mixed uniformly with the conductive additive by grinding, then the inorganic glassy solid electrolyte is added to the mixture of the electrode active material and the conductive additive and mixed uniformly again by grinding, and then the binder is added thereto and mixed uniformly, and the resulting product is a dry-mixed electrode, and finally the mixed electrode is prepared into an electrode material sheet of a certain thickness by a calendering process, and the electrode active material particles in the electrode material sheet are embedded in the ion and electron conductive network constructed by the solid electrolyte and the conductive additive, as shown in the following schematic diagram: Figure 1

[0023] In a fifth aspect, the present application provides an all-solid-state battery comprising the positive electrode according to the present application, an inorganic glassy solid electrolyte, and a negative electrode, wherein the inorganic glassy solid electrolyte has the following chemical formula: DA x O y Cl z wherein D is Li or Na; A is selected from one or more of B, Al, Fe, Ga, In, As, Sb, Mo and Bi; 0.2≤x≤3, 0

[0024] Preferably, in the all-solid-state battery according to the present application, the negative electrode is the negative electrode according to the present application.

[0025] Preferably, the all-solid-state battery according to the present application further comprises an oxide ceramic solid electrolyte close to the negative electrode side.

[0026] Preferably, the all-solid-state battery according to the present application further comprises a sulfide solid electrolyte close to the negative electrode side.

[0027] Preferably, the all-solid-state battery according to the present application further comprises a PEO polymer solid electrolyte close to the negative electrode side.

[0028] ​In view of the fact that the processing performance (easy deformation) and high voltage resistance of the mainstream lithium ion battery solid electrolyte are incompatible, the inorganic glassy solid electrolyte of the present application, which has the high voltage resistance of the oxide ceramic positive electrode and the excellent processing performance (easy deformation and flexibility) of the polymer and sulfide, can be used in combination on the positive electrode side of the three mainstream solid electrolyte batteries to solve the positive electrode side interface problem of the all-solid-state lithium ion battery.

[0029] In a sixth aspect, the present application provides a method for preparing the all-solid-state battery of the present application, comprising the following steps:

[0030] (1) The inorganic glassy solid electrolyte is made into a micron-level solid electrolyte film by a calendering method; wherein the inorganic glassy solid electrolyte has the following chemical formula: DA x O y Cl z , wherein D is Li or Na; A is selected from one or more of B, Al, Fe, Ga, In, As, Sb, Mo and Bi; 0.2≤x≤3, 0

[0031] (2) The solid electrolyte film is placed between the negative electrode and the positive electrode of the present application, and is pressurized and heated to the melting point of the solid electrolyte film, so that the solid electrolyte completely infiltrates the positive electrode and the negative electrode, and then cooled to obtain the all-solid-state battery.

[0032] In a specific embodiment of the present application, since the inorganic glassy solid electrolyte of the present application has obvious viscoelasticity and flexibility similar to high polymer plastic at a temperature higher than 50°C and lower than the melting temperature, it can be processed like high polymer plastic at this temperature range, and a micron-level solid electrolyte film is made by a calendering method. The solid electrolyte film is placed between the positive electrode and the negative electrode with current collector, pressurized (>1MPa) and heated to the melting point of the solid electrolyte, and the positive electrode and the negative electrode are completely infiltrated by the electrolyte to form good interface contact, and then cooled to obtain the all-solid-state battery. In a specific embodiment of the present application, for electrode materials that are not suitable for heating, the heating process can be directly removed and directly pressurized (>1MPa), and since the inorganic glassy solid electrolyte of the present application has excellent viscoelasticity and negligible grain boundary resistance, it can also form good interface contact with the electrode under the condition of only pressurization.

[0033] The solid electrolyte of the present application has a melting temperature lower than 250℃, while all the anti-perovskite solid electrolytes have a melting temperature higher than 250℃ (see Yiran Xiao et al., Electrolyte melt infiltration for scalable manufacturing of inorganic all-solid-state lithium-ion batteries, 2021, DOI: 10.1038 / s41563-021-00943-2), which makes the solid electrolyte of the present application have some advantages as described above.

[0034] In a seventh aspect, the present application provides a method for preparing the all-solid-state battery of the present application, comprising the following steps:

[0035] (1) uniformly dispersing an inorganic glassy solid electrolyte powder or an inorganic glassy solid electrolyte film on the surface of the positive electrode of the present application; wherein the inorganic glassy solid electrolyte has the following chemical formula: DA x O y Cl z wherein D is Li or Na; A is selected from one or more of B, Al, Fe, Ga, In, As, Sb, Mo and Bi; 0.2≤x≤3, 0<y≤3, 0<z≤9 and the molar proportion of D is less than 0.5;

[0036] (2) attaching an oxide ceramic solid electrolyte sheet to the side of the inorganic glassy solid electrolyte powder or the inorganic glassy solid electrolyte film, and then heating to the melting temperature of the inorganic glassy solid electrolyte powder or the inorganic glassy solid electrolyte film to make the solid electrolyte completely infiltrate the positive electrode and the oxide ceramic solid electrolyte sheet, and then cooling;

[0037] (3) attaching a negative electrode to the oxide ceramic solid electrolyte sheet side of the product obtained in step (2), i.e. obtaining an all-solid-state battery.

[0038] In a specific embodiment of the present application, when the inorganic glassy solid electrolyte of the present application is used in combination with an oxide solid electrolyte, since the oxide electrolyte is relatively brittle, the interface attachment of the two solid electrolytes cannot be achieved by pressurization, but should be achieved by heating and melting. First, a layer of the inorganic glassy solid electrolyte powder or film of the present application is uniformly dispersed on the surface of the positive electrode of the present application, then an oxide solid electrolyte sheet is attached to the inorganic glassy solid electrolyte powder or film, and the temperature is raised to the melting temperature of the solid electrolyte, the solid electrolyte of the present application and the oxide solid electrolyte sheet form good infiltration and interface contact, and then cooled to room temperature.

[0039] The oxide ceramic solid electrolyte in the prior art has good high-voltage resistance and can be compatible with high-voltage cathode materials, but it has high hardness and brittleness, poor processability, and the problems of small contact area and large interface impedance with the cathode material particles (see Chengwei Wang et al., Garnet-Type Solid-State Electrolytes: Materials, Interfaces, and Batteries, 2020, DOI: 10.1021 / acs.chemrev.9b00427).

[0040] The inventors of the present application unexpectedly found that the inorganic glassy solid electrolyte of the present application can be used in combination with the oxide ceramic solid electrolyte in the prior art, so that the solid-state battery of the present application has good processability (easy deformation) and high-voltage resistance (4.5V).

[0041] In an eighth aspect, the present application provides a method for preparing the all-solid-state battery of the present application, comprising the following steps:

[0042] (1) preparing a micron-level solid electrolyte film by calendering the inorganic glassy solid electrolyte; wherein the inorganic glassy solid electrolyte has the following chemical formula: DA x O y Cl z wherein D is Li or Na; A is selected from one or more of B, Al, Fe, Ga, In, As, Sb, Mo and Bi; 0.2≤x≤3, 0<y≤3, 0<z≤9 and the molar fraction of D is less than 0.5;

[0043] (2) laminating and pressing the cathode of the present application with the solid electrolyte film and heating to the melting point of the solid electrolyte film, so that the solid electrolyte fully infiltrates the cathode, and then cooling;

[0044] (3) uniformly dispersing sulfide solid electrolyte powder or sulfide solid electrolyte film on the solid electrolyte film side of the product obtained in step (2), and then pressing to tightly laminate the sulfide solid electrolyte powder or sulfide solid electrolyte film to the solid electrolyte film side;

[0045] (4) laminating the anode to the sulfide solid electrolyte side of the product obtained in step (3), thereby obtaining the all-solid-state battery.

[0046] In a specific embodiment of the present application, when the inorganic glassy solid-state electrolyte of the present application is used in combination with a sulfide solid-state electrolyte, a micron-sized inorganic glassy solid-state electrolyte film is first prepared using a calendering process, and then the solid-state electrolyte film is attached to and pressed (>1 MPa) against the positive electrode of the present application and heated to 80-100°C, thereby forming a positive electrode with a layer of solid-state electrolyte film on its surface; and then a sulfide solid-state electrolyte film or sulfide solid-state electrolyte powder is attached to the side of the solid-state electrolyte film and then pressed (>1 MPa).

[0047] The sulfide solid-state electrolyte in the prior art has good processability due to its easy deformation, which is beneficial to large-scale industrial production. However, it also has the problems of easy oxidation and decomposition at high voltage and incompatibility with high-voltage positive electrodes, which greatly limits the improvement of battery energy density. The oxidation resistance potential of the sulfide solid-state electrolyte is generally not more than 2.5-2.7 V (see Yihan Xiao et al., Understanding interface stability in solid-state batteries, Nature Reviews Materials, 10.1038 / s41578-019-0157-5, (2019)). If it exceeds 2.7 V, the sulfide solid-state electrolyte will undergo obvious electrolyte decomposition, which makes it face serious decomposition problems when applied to high-voltage positive electrode materials (4.2 V).

[0048] The inventors of the present application unexpectedly found that the use of the inorganic glassy solid-state electrolyte of the present application in combination with the sulfide solid-state electrolyte in the prior art can make the solid-state battery of the present application have good processability (easy deformation) and high-voltage resistance (4.5 V), and the all-solid-state battery of the present application can stably operate for more than 1000 cycles when the charge cutoff voltage is 4.3 V.

[0049] In a ninth aspect, the present application provides a method for preparing the all-solid-state battery of the present application, which comprises the following steps:

[0050] (1) micron-sized solid-state electrolyte film is prepared from inorganic glassy solid-state electrolyte by calendering method; wherein the inorganic glassy solid-state electrolyte has the following chemical formula: DA x O y Cl z wherein D is Li or Na; A is selected from one or more of B, Al, Fe, Ga, In, As, Sb, Mo and Bi; 0.2≤x≤3, 0<y≤3, 0<z≤9 and the molar fraction of D is less than 0.5;

[0051] (2) pressing the solid electrolyte thin film and the PEO polymer solid electrolyte thin film together and optionally heating to the melting temperature of the solid electrolyte thin film and optionally cooling to obtain a composite electrolyte thin film with the two solid electrolyte thin films closely adhered to each other;

[0052] (3) placing the composite electrolyte thin film between the anode and the cathode of any one of claims 1-2, wherein the cathode side adheres to the solid electrolyte thin film side of the composite electrolyte thin film and the anode side adheres to the PEO polymer solid electrolyte thin film side of the composite electrolyte thin film, and then pressing and optionally heating to the melting temperature of the solid electrolyte thin film and optionally cooling to allow the composite electrolyte thin film to completely infiltrate the cathode and the anode, thereby obtaining a full solid-state battery.

[0053] In a specific embodiment of the present application, when the inorganic glassy solid electrolyte of the present application is used in combination with the PEO polymer solid electrolyte, a micron-sized inorganic glassy solid electrolyte thin film is first prepared using a calendering process, and then the solid electrolyte thin film is pressed (>1 MPa) and heated to 80-100°C with the PEO solid electrolyte thin film, thereby forming a composite electrolyte thin film with the two solid electrolyte thin films closely adhered to each other.

[0054] The PEO polymer solid electrolyte in the prior art has good processability due to its easy deformation, which is beneficial for large-scale industrial production. However, it also has the problems of easy oxidative decomposition at high voltage and incompatibility with high-voltage cathodes, which greatly limits the improvement of battery energy density. The oxidation resistance potential of the PEO polymer solid electrolyte is generally not more than 4V (see Rusong Chen et al., Approaching Practically Accessible Solid-State Batteries: Stability Issues Related to Solid Electrolytes and Interfaces, DOI: 10.1021 / acs.chemrev.9b00268, (2019)).

[0055] The inventors of the present application unexpectedly found that the use of the inorganic glassy solid electrolyte of the present application in combination with the PEO polymer solid electrolyte in the prior art can make the solid-state battery of the present application have both good processability (easy deformation) and high-voltage resistance (4.5V).

[0056] The present application has the following beneficial effects:

[0057] (1) The inorganic solid electrolyte of the present application has a low melting temperature of about 50-250°C. The inorganic solid electrolyte of the present application has a high room temperature ionic conductivity of 10 -5-10 -2 S / cm, preferably 10 -3 -10 -2 S / cm, which is close to the conductivity of liquid organic electrolyte, which makes the solid electrolyte of the present application extremely advantageous in the application of high-rate all-solid-state batteries. The inorganic solid electrolyte of the present application is amorphous structure, which has flexibility and viscosity (changes with temperature, the closer to the melting temperature, the stronger the flexibility and viscoelasticity). On the other hand, the grain boundary resistance of the electrolyte of the present application is very low, which makes the electrolyte of the present application directly pressurized to form a high-quality interface contact, compatible with the assembly process of sulfide solid electrolyte batteries. More importantly, the inorganic solid electrolyte of the present application has a high oxidation potential of about 4.5V. In addition, the inorganic solid electrolyte of the present application is not sensitive to air atmosphere. Specifically, the solid electrolyte of the present application is resistant to air corrosion, and has no obvious absorption of moisture and oxidation, no decomposition products are generated, and its performance is not sensitive to air atmosphere, which makes the solid electrolyte of the present application can be stored and operated in air, which is conducive to large-scale industrial production.

[0058] (2) The all-solid-state battery based on the solid electrolyte of the present application is low in cost and does not use any solvent. The all-solid-state battery of the present application can realize good contact of different interfaces by pressurization or heating melting. BRIEF DESCRIPTION OF DRAWINGS

[0059] Hereinafter, the embodiments of the present application will be described in detail with reference to the accompanying drawings, in which:

[0060] Figure 1 Preparation flowchart of the electrode of a specific embodiment of the present application;

[0061] Figure 2 Charge-discharge curve of the all-solid-state battery Li4Ti5O 12 / LiAl 1.3 O 1.1 Cl 2.7 / NCM523 of Example 1 of the present application;

[0062] Figure 3 Cycle performance graph of the all-solid-state battery Li4Ti5O 12 / LiAl 1.3 O 1.1 Cl 2.7 / NCM523 of Example 1 of the present application;

[0063] Figure 4 Charge-discharge curve of the all-solid-state battery NaTi2(PO4)3 / NaAl 1.4 O 1.1 Cl3 / Na3(VOPO4)2F of Example 2 of the present application;

[0064] Figure 5 Cycle performance plot for the all-solid-state battery NaTi2(PO4)3 / NaAl 1.4 O 1.1 Cl3 / Na3(VOPO4)2F of Example 2 of the present invention;

[0065] Figure 6 All-solid-state battery Li / PEO-LiTFSI / LiAl 1.3 O 1.1 Cl 2.7 / NCM523 of Example 3 of the present invention;

[0066] Figure 7 All-solid-state battery Li / PEO-LiTFSI / LiAl 1.3 O 1.1 Cl 2.7 / NCM523 of Example 3 of the present invention;

[0067] Figure 8 All-solid-state battery Na / PEO-NaTFSI / NaAl 1.4 O 1.1 Cl3 / Na3(VOPO4)2F of Example 4 of the present invention;

[0068] Figure 9 All-solid-state battery Na / PEO-NaTFSI / NaAl 1.4 O 1.1 Cl3 / Na3(VOPO4)2F of Example 4 of the present invention;

[0069] Figure 10 All-solid-state battery Li / Li6PS5Cl / LiGa 0.4 In 0.7 Sb 0.04 O 1.05 Cl 2.32 / NCM622 of Example 5 of the present invention;

[0070] Figure 11 All-solid-state battery Li / Li6PS5Cl / LiGa 0.4 In 0.7 Sb 0.04 O 1.05 Cl 2.32 / NCM622 of Example 5 of the present invention;

[0071] Figure 12 All-solid-state battery Na / Na3SbS4 / NaGa 0.3In 0.7 Sb 0.04 O 1.05 Cl 2.02 Charge-discharge curve of Na3(VOPO4)2F;

[0072] Figure 13 Full solid-state battery Na / Na3SbS4 / NaGa 0.3 In 0.7 Sb 0.04 O 1.05 Cl 2.02 Cycle performance graph of Na3(VOPO4)2F;

[0073] Figure 14 Full solid-state battery Li / LLZTO / LiAl 1.25 As 0.09 O 1.18 Cl 2.66 Charge-discharge curve of NCM811;

[0074] Figure 15 Full solid-state battery Li / LLZTO / LiAl 1.25 As 0.09 O 1.18 Cl 2.66 Cycle performance graph of NCM811;

[0075] Figure 16 Full solid-state battery Na / NASICON / NaAl 1.59 As 0.12 O 1.25 Cl 3.63 Charge-discharge curve of Na3(VOPO4)2F;

[0076] Figure 17 Full solid-state battery Na / NASICON / NaAl 1.59 As 0.12 O 1.25 Cl 3.63 Cycle performance graph of Na3(VOPO4)2F;

[0077] Figure 18 XRD crystal diffraction data graph of solid electrolyte LiAl 1.3 O 1.1 Cl 2.7 of the present application embodiment 1. DETAILED DESCRIPTION

[0078] The application will be further described in detail below with reference to the specific embodiments, and the examples given are only for the purpose of illustrating the application, but not for limiting the scope of the application.

[0079] The inorganic glassy solid electrolyte of the following embodiments of the application can be prepared by the preparation method in the patent application with the application number 202110334157.8 or the application number 202110334142.1. In a specific embodiment of the application, the inorganic glassy lithium ion solid electrolyte of the application can be prepared by the following method, which comprises the following steps:

[0080] DCl, MaCl m and Mb2O n After the powders are uniformly mixed, heat to a temperature higher than the boiling point of MbCl n to obtain the inorganic glassy lithium ion solid electrolyte DMa x1 Mb x2 O y Cl z , i.e. DA x O y Cl z , wherein 3≤m≤6, 3≤n≤6, 0

[0081] D is Li or Na;

[0082] Ma and Mb are the same or different and each is independently selected from one or more of B, Al, Fe, Ga, In, As, Sb, Mo and Bi;

[0083] 0.2≤x≤3, 0

[0084] Preferably, in a specific embodiment of the application, the inorganic glassy lithium ion solid electrolyte of the application can be prepared by the following method, which comprises the following steps:

[0085] (1) uniformly mix DCl and MaCl m , and then heat to melt MaCl m , and further react to form DMa q Cl qm+1 uniform melt, wherein 0

[0086] (2) after the DMa q Cl qm+1 is ground into powder, mix the powder with Mb2O n , and then heat the uniformly mixed powder to a temperature higher than the boiling point of MbCl nThe boiling point is used to prepare the inorganic glassy lithium-ion solid electrolyte DMa x1 Mb x2 O y Cl z , that is, DA x O y Cl z , where 3 ≤ m ≤ 6, 3 ≤ n ≤ 6, 0 < x1 ≤ 3, 0 < x2 ≤ 3 and 0.2 ≤ x1 + x2 ≤ 3; among them,

[0087] D is Li or Na;

[0088] Ma and Mb are the same or different and each independently selected from one or more of B, Al, Fe, Ga, In, As, Sb, Mo and Bi; 0.2 ≤ x ≤ 3, 0 < y ≤ 3, 0 < z ≤ 9 and the molar ratio of D is less than 0.5.

[0089] Example 1

[0090] Using LiAl 1.3 O 1.1 Cl 2.7 The solid electrolyte is assembled with the anode active material being lithium titanate (Li4Ti5O 12 ), and the cathode active material being NCM523 all-solid-state battery. First, press the Li4Ti5O Figure 1 anode material tablet and the NCM523 cathode material tablet in the order shown, where the conductive additive is CNT and the binder is PTFE, and the mass ratio of the active material: SSE: CNT: PTFE is 70:20:5:5. Then press and bond the anode and cathode material tablets onto the stainless steel foil current collector. Subsequently, place the LiAl 12 O 1.3 O 1.1 Cl 2.7 solid electrolyte film between the Li4Ti5O 12 anode and the NCM523 cathode, apply a pressure of 10 MPa and heat up to 80 °C and hold for 5 minutes. Subsequently, obtain the all-solid-state Li4Ti5O 12 / LiAl 1.3 O 1.1 Cl 2.7 / NCM523 battery. This battery operates at 60 °C, and its electrochemical performance is as shown in Figure 2 and Figure 3 .

[0091] Example 2

[0092] Using NaAl 1.4 [[ID=​A solid-state battery is assembled using Cl3 as the solid electrolyte, with sodium titanium phosphate (NaTi2(PO4)3) as the negative electrode active material and Na3(VOPO4)2F as the positive electrode active material. First, according to... Figure 1 The following sequence was used to fabricate NaTi2(PO4)3 anode material sheets and Na3(VOPO4)2F cathode material sheets, respectively. CNT was used as the conductive additive, PTFE as the binder, and the mass ratio of active material:SSE:CNT:PTFE was 70:20:5:5. The cathode and anode material sheets were then pressurized and bonded onto a stainless steel foil current collector. Subsequently, NaAl, prepared using a calendering method, was... 1.4 O 1.1 A Cl3 solid electrolyte film was placed between the NaTi2(PO4)3 negative electrode and the Na3(VOPO4)2F positive electrode, and a pressure of 10 MPa was applied and the temperature was raised to 80 °C and held for 5 minutes, thus obtaining an all-solid-state NaTi2(PO4)3 / NaAl. 1.4 O 1.1 Cl3 / Na3(VOPO4)2F battery. This battery operates at 60℃, and its electrochemical performance is as follows: Figure 4 and Figure 5 As shown.

[0093] Example 3

[0094] Using LiAl 1.3 O 1.1 Cl 2.7 A combination of solid electrolyte and PEO-LiTFSI solid electrolyte was used to assemble an all-solid-state battery with metallic Li as the negative electrode and NCM523 as the positive electrode active material. First, according to... Figure 1 The NCM523 positive electrode material was fabricated in the sequence shown, with CNT as the conductive additive, PTFE as the binder, and an active material:SSE:CNT:PTFE mass ratio of 70:20:5:5. The positive electrode material was then pressed and bonded onto a stainless steel foil current collector, followed by LiAl prepared using a calendering method. 1.3 O 1.1 Cl 2.7 A solid electrolyte film was bonded to one side of a PEO-LiTFSI solid electrolyte film, and a pressure of 10 MPa was applied while the temperature was raised to 80°C and held for 5 minutes to obtain a composite electrolyte film. This composite electrolyte film was then placed between the Li anode and the NCM523 cathode (the cathode side being adjacent to the LiAl). 1.3 O 1.1 Cl 2.7 (Solid electrolyte layer bonding), pressurized at 10 MPa and heated to 80 °C for 5 minutes, then all-solid-state Li / PEO-LiTFSI / LiAl was obtained. 1.3 O 1.1 Cl 2.7 / NCM523 battery. This battery was operated at 60 °C and the electrochemical performance is shown in Figure 6 and Figure 7

[0095] Example 4

[0096] NaAl 1.4 O 1.1 Cl3 solid electrolyte and PEO-NaTFSI solid state electrolyte were used in combination to assemble a full solid-state battery with metal Na as the negative electrode and Na3(VOPO4)2F as the positive electrode active material. First, Na3(VOPO4)2F positive electrode material pellets were made in the order shown in Figure 1 , where the conductive additive was CNT and the binder was PTFE, and the mass ratio of active material : SSE : CNT : PTFE was 70 : 20 : 5 : 5. Then the positive electrode material pellets were pressed and attached to a stainless steel foil current collector, and then a NaAl 1.4 O 1.1 Cl3 solid electrolyte film was attached to one side of the PEO-NaTFSI solid state electrolyte film and was pressed at 10 MPa and heated to 80 °C for 5 minutes, resulting in a composite electrolyte film. Then the composite electrolyte film was placed between a Na negative electrode and a Na3(VOPO4)2F positive electrode (with the positive electrode side attached to the NaAl 1.4 O 1.1 Cl3 solid electrolyte layer), and was pressed at 10 MPa and heated to 80 °C for 5 minutes, resulting in a full solid-state Na / PEO-NaTFSI / NaAl 1.4 O 1.1 Cl3 / Na3(VOPO4)2F battery. This battery was operated at 60 °C and the electrochemical performance is shown in Figure 8 and Figure 9

[0097] Example 5

[0098] LiGa 0.4 In 0.7 Sb 0.04 O 1.05 Cl 2.32 solid electrolyte and Li6PS5Cl solid state electrolyte were used in combination to assemble a full solid-state battery with metal Li as the negative electrode and NCM622 as the positive electrode active material. First, NCM622 positive electrode material pellets were made in the order shown in Figure 1 , where the conductive additive was CNT and the binder was PTFE, and the mass ratio of active material : SSE : CNT : PTFE was 70 : 20 : 5 : 5. Then the positive electrode material pellets were pressed and attached to a stainless steel foil current collector, and then a LiGa 0.4 In 0.7 Sb​​0.04 O 1.05 Cl 2.32 The solid electrolyte thin film is attached to the surface of the positive electrode and is pressed at 10 MPa and heated to 80°C for 5 minutes to obtain a LiGa 0.4 In 0.7 Sb 0.04 O 1.05 Cl 2.32 The solid electrolyte thin film is attached to the surface of the positive electrode. Then a thin layer of Li6PS5Cl solid electrolyte powder is placed between the positive electrode and the Li negative electrode, and is pressed at 10 MPa for 5 minutes to obtain a full solid-state Li / Li6PS5Cl / LiGa 0.4 In 0.7 Sb 0.04 O 1.05 Cl 2.32 / NCM622 battery. This battery is operated at 60°C, and the electrochemical performance is as shown in Figure 10 and Figure 11 .

[0099] Example 6

[0100] NaGa 0.3 In 0.7 Sb 0.04 O 1.05 Cl 2.02 The solid electrolyte and Na3SbS4 solid electrolyte are used in combination, and a full solid-state battery is assembled with a metal Na negative electrode and a Na3(VOPO4)2F positive electrode active material. First, a Na3(VOPO4)2F positive electrode material tablet is prepared in the order shown in Figure 1 , in which the conductive additive is CNT, the binder is PTFE, and the mass ratio of active material:SSE:CNT:PTFE is 70:20:5:5. Then the positive electrode material tablet is attached to the surface of a stainless steel foil current collector under pressure, and then a NaGa 0.3 In 0.7 Sb 0.04 O 1.05 Cl 2.02 The solid electrolyte thin film is attached to the surface of the positive electrode and is pressed at 10 MPa and heated to 80°C for 5 minutes to obtain a NaGa 0.3 In 0.7 Sb 0.04 O 1.05 Cl 2.02 The solid electrolyte thin film is attached to the surface of the positive electrode. Then a thin layer of Na3SbS4 solid electrolyte powder is placed between the positive electrode and the Na negative electrode, and is pressed at 10 MPa for 5 minutes to obtain a full solid-state Na / Na3SbS4 / NaGa 0.3 In 0.7 Sb 0.04 O1.05 Cl 2.02 / Na3(VOPO4)2F battery. This battery was operated at 60 °C and the electrochemical performance is shown in Figure 12 and Figure 13 .

[0101] Example 7

[0102] LiAl 1.25 As 0.09 O 1.18 Cl 2.66 Solid electrolyte and LLZTO solid state electrolyte were used in combination to assemble a full solid state battery with metal Li as anode and NCM811 as cathode active material. First, NCM811 cathode material pellets were made in the order shown in Figure 1 , where the conductive additive was CNT and the binder was PTFE, with the mass ratio of active material : SSE : CNT : PTFE being 70 : 20 : 5 : 5. Then the cathode material pellets were pressed and attached to a stainless steel foil current collector, followed by covering a thin layer of LiAl 1.25 As 0.09 O 1.18 Cl 2.66 solid electrolyte powder and heated to melt (130 °C), followed by attaching a LLZTO ceramic sheet to the surface with a thin layer of liquid LiAl 1.25 As 0.09 O 1.18 Cl 2.66 electrolyte. The liquid LiAl 1.25 As 0.09 O 1.18 Cl 2.66 electrolyte would completely infiltrate and connect the LLZTO ceramic sheet to the cathode material, followed by cooling to room temperature to obtain a full solid state Li / LLZTO / LiAl 1.25 As 0.09 O 1.18 Cl 2.66 / NCM811 battery. This battery was operated at 60 °C and the electrochemical performance is shown in Figure 14 and Figure 15 .

[0103] Example 8

[0104] NaAl 1.59 As 0.12 O 1.25 Cl 3.63 Solid electrolyte and NASICON solid state electrolyte were used in combination to assemble a full solid state battery with metal Na as anode and Na3(VOPO4)2F as cathode active material. First, Na3(VOPO4)2F cathode material pellets were made in the order shown in Figure 1Na3(VOPO4)2F cathode material pellets were fabricated in the order shown, where the conductive additive was CNT and the binder was PTFE, and the mass ratio of active material : SSE : CNT : PTFE was 70 : 20 : 5 : 5. The cathode material pellets were then pressed and attached to a stainless steel foil current collector, and a thin layer of NaAl 1.59 As 0.12 O 1.25 Cl 3.63 solid electrolyte and heated to melt (160 °C), and then a NASICON ceramic pellet was attached to the surface with a thin layer of liquid NaAl 1.59 As 0.12 O 1.25 Cl 3.63 electrolyte, the liquid NaAl 1.59 As 0.12 O 1.25 Cl 3.63 electrolyte would completely wet out and connect the NASICON ceramic pellet to the cathode material, and then the temperature was reduced to room temperature to obtain a full solid state Na / NASICON / NaAl 1.59 As 0.12 O 1.25 Cl 3.63 / Na3(VOPO4)2F battery. This battery was operated at 60 °C, and the electrochemical performance was as shown in Figure 16 and Figure 17 shown.

Claims

1. A positive electrode comprising a positive electrode current collector and a positive electrode material, wherein, The positive electrode material includes a positive electrode active material, an inorganic glassy solid electrolyte, a conductive aid, and a binder, wherein the inorganic glassy solid electrolyte has the following chemical formula: DA x O y Cl z wherein D is Li or Na; A is selected from one or more of B, Al, Fe, Ga, In, As, Sb, Mo, and Bi; 0.2≤x≤3, 0<y≤3, 0<z≤9, and the molar proportion of D is less than 0.

5.

2. The positive electrode according to claim 1, wherein The positive active material is selected from one or more of oxide layered materials and polyanion positive materials.

3. The positive electrode according to claim 1, wherein The conductive additive is selected from one or more of KB, Super-P, acetylene black, CNT and rGO.

4. The positive electrode according to claim 1, wherein The binder is selected from one or more of PVDF, PTFE, NaAlg, CMC, SBR and PAA.

5. A method for preparing the positive electrode of any one of claims 1-4, comprising the following steps: (1) mixing the positive active material particles, the conductive additive, the inorganic glassy solid electrolyte and the binder uniformly, and then preparing a positive electrode material press sheet by calendering method; (2) attaching the positive electrode material press sheet to a positive electrode current collector to prepare the positive electrode.

6. A negative electrode comprising a negative electrode current collector and a negative electrode material, wherein, The negative electrode material includes a negative electrode active material, an inorganic glassy solid electrolyte, a conductive aid, and a binder, wherein the inorganic glassy solid electrolyte has the following chemical formula: DA x O y Cl z , wherein D is Li or Na; A is selected from one or more of B, Al, Fe, Ga, In, As, Sb, Mo, and Bi; 0.2≤x≤3, 0<y≤3, 0<z≤9, and the molar proportion of D is less than 0.

5.

7. The negative electrode according to claim 6, wherein The negative active material is selected from one or more of carbon-based materials, alloy-based materials, oxide layered materials and polyanion-based materials.

8. The negative electrode according to claim 6, wherein The conductive additive is selected from one or more of KB, Super-P, acetylene black, CNT and rGO.

9. The negative electrode according to claim 6, wherein The binder is selected from one or more of PVDF, PTFE, NaAlg, CMC, SBR and PAA.

10. A method for preparing the negative electrode of any one of claims 6-9, comprising the following steps: (1) mixing the negative active material particles, the conductive additive, the inorganic glassy solid electrolyte and the binder uniformly, and then preparing a negative electrode material press sheet by calendering method; (2) attaching the negative electrode material press sheet to a negative electrode current collector to prepare the negative electrode.

11. An all-solid-state battery comprising the positive electrode of any one of claims 1-4, an inorganic glassy solid electrolyte, and a negative electrode, wherein the inorganic glassy solid electrolyte has the following chemical formula: DA x O y Cl z wherein, D is Li or Na; A is selected from one or more of B, Al, Fe, Ga, In, As, Sb, Mo and Bi; 0.2≤x≤3, 0<y≤3, 0<z≤9 and the molar proportion of D is less than 0.

5.

12. The all-solid-state battery according to claim 11, wherein The negative electrode is the negative electrode of any one of claims 6-9.

13. The all-solid-state battery of claim 11, further comprising an oxide ceramic solid electrolyte proximate to the negative electrode side.

14. The all-solid-state battery of claim 11, further comprising a sulfide solid electrolyte proximate to the negative electrode side.

15. The all-solid-state battery of claim 11, further comprising a PEO polymer solid electrolyte proximate to the negative electrode side.

16. A method for preparing the all-solid-state battery of any one of claims 11-12, comprising the following steps: (1) micron-scale solid electrolyte thin films are made from inorganic glassy solid electrolytes by calendering; wherein the inorganic glassy solid electrolytes have the following chemical formula: DA x O y Cl z wherein, D is Li or Na; A is selected from one or more of B, Al, Fe, Ga, In, As, Sb, Mo and Bi; 0.2≤x≤3, 0<y≤3, 0<z≤9 and the molar proportion of D is less than 0.5; (2) placing the solid electrolyte film between the negative electrode and the positive electrode of any one of claims 1-2, pressurizing and heating to the melting point of the solid electrolyte film, so that the solid electrolyte completely infiltrates the positive electrode and the negative electrode, and then cooling to prepare the all-solid-state battery.

17. A method for preparing the all-solid-state battery of claim 13, comprising the following steps: (1) The positive electrode described in any one of claims 1 to 4 has an inorganic glassy solid electrolyte powder uniformly dispersed on the surface thereof or an inorganic glassy solid electrolyte thin film attached thereto; wherein the inorganic glassy solid electrolyte has the following chemical formula: DA x O y Cl z wherein, D is Li or Na; A is selected from one or more of B, Al, Fe, Ga, In, As, Sb, Mo and Bi; 0.2≤x≤3, 0 (2) The oxide ceramic solid electrolyte sheet is attached to the inorganic glassy solid electrolyte powder side or the inorganic glassy solid electrolyte film side, and then heated to the melting point of the inorganic glassy solid electrolyte powder or the inorganic glassy solid electrolyte film to allow the solid electrolyte to completely infiltrate the positive electrode and the oxide ceramic solid electrolyte sheet, and then cooled; (3) The negative electrode is attached to the oxide ceramic solid electrolyte sheet side of the product obtained in step (2), thereby obtaining a full solid-state battery.

18. A method for preparing the full solid-state battery of claim 14, comprising the following steps: (1) micron-scale solid electrolyte thin films are made from inorganic glassy solid electrolytes by calendering; wherein the inorganic glassy solid electrolytes have the following chemical formula: DA x O y Cl z wherein, D is Li or Na; A is selected from one or more of B, Al, Fe, Ga, In, As, Sb, Mo and Bi; 0.2≤x≤3, 0 (2) The positive electrode of any one of claims 1-4 is attached to the solid electrolyte film and pressed and heated to the melting point of the solid electrolyte film to allow the solid electrolyte to completely infiltrate the positive electrode, and then cooled; (3) The sulfide solid electrolyte powder is uniformly dispersed on the solid electrolyte film side of the product obtained in step (2), or the sulfide solid electrolyte film is attached to the solid electrolyte film side, and then pressed to allow the sulfide solid electrolyte powder or the sulfide solid electrolyte film to tightly attach to the solid electrolyte film side; (4) The negative electrode is attached to the sulfide solid electrolyte side of the product obtained in step (3), thereby obtaining a full solid-state battery.

19. A method for preparing the full solid-state battery of claim 15, comprising the following steps: (1) micron-scale solid electrolyte thin films are made from inorganic glassy solid electrolytes by calendering; wherein the inorganic glassy solid electrolytes have the following chemical formula: DA x O y Cl z wherein, D is Li or Na; A is selected from one or more of B, Al, Fe, Ga, In, As, Sb, Mo and Bi; 0.2≤x≤3, 0 (2) The solid electrolyte film is attached to the PEO polymer solid electrolyte film and pressed, and optionally heated to the melting point of the solid electrolyte film and optionally cooled, to obtain a composite electrolyte film in which two solid electrolyte films are tightly attached; (3) The composite electrolyte film is placed between the negative electrode and the positive electrode of any one of claims 1-4, wherein the positive electrode side is attached to the solid electrolyte film side of the composite electrolyte film, and the negative electrode side is attached to the PEO polymer solid electrolyte film side of the composite electrolyte film, and then pressed, and optionally heated to the melting point of the solid electrolyte film and optionally cooled, to allow the composite electrolyte film to completely infiltrate the positive electrode and the negative electrode, thereby obtaining a full solid-state battery.

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