Modified inorganic solid electrolyte, preparation method thereof and all-solid-state lithium ion battery

Abstract

The invention provides a modified inorganic solid electrolyte, a preparation method thereof and an all-solid-state lithium ion battery, and belongs to the technical field of all-solid-state lithium ion battery manufacturing. The modified inorganic solid electrolyte is of a core-shell structure, an inner core is made of an inorganic solid electrolyte, a shell is made of a metal borate substance, and the modified inorganic solid electrolyte can effectively solve the problem that the air stability of the inorganic solid electrolyte is poor, so that the corresponding all-solid-state lithium ion battery has relatively excellent cycle performance.

Description

Technical Field

[0001] The present application relates to the technical field of all-solid-state lithium-ion battery manufacturing, and in particular to a modified inorganic solid electrolyte and a preparation method thereof, and an all-solid-state lithium-ion battery. Background Art

[0002] In existing technologies, all-solid-state electrolytes have garnered widespread attention due to their advantages, including high safety, high energy density, long cycle life, and a wide temperature range. However, inorganic solid electrolytes within all-solid-state electrolytes still face some challenges in their application. For example, both sulfide and halide solid electrolytes suffer from poor air stability (resulting in a decrease in ionic conductivity), which in turn leads to poor cycling performance of the corresponding batteries. Summary of the Invention

[0003] The purpose of this application is to provide a modified inorganic solid electrolyte and its preparation method and an all-solid-state lithium-ion battery, which can effectively improve the problem of poor air stability of inorganic solid electrolytes, so that the corresponding all-solid-state lithium-ion battery has relatively excellent cycle performance.

[0004] The embodiment of the present application is implemented as follows: In a first aspect, an embodiment of the present application provides a modified inorganic solid electrolyte, which has a core-shell structure, wherein the inner core is made of an inorganic solid electrolyte and the outer shell is made of a metal borate.

[0005] In the above technical solution, the surface of the inorganic solid electrolyte core material has a shell layer made of metal borate. Compared with inorganic solid electrolytes, metal borate has more ideal air stability. The use of metal borate to coat the inorganic solid electrolyte can effectively improve the air stability of the inorganic solid electrolyte, so that its ionic conductivity is always maintained at a more ideal level; at the same time, the coating and isolation of the inorganic solid electrolyte by metal borate can also improve the problem of side reactions that are prone to occur after the inorganic solid electrolyte is in direct contact with the active material (specifically, sulfide solid electrolytes are prone to harmful interfacial side reactions after direct contact with active materials, especially high-voltage positive electrodes and lithium metal negative electrodes; after halide solid electrolytes are in direct contact with lithium metal, the metal elements in the halide solid electrolyte are easily reduced to form metal elements, and after direct contact with the high-voltage positive electrode, redox reactions are easily generated during the charge and discharge process, resulting in the destruction of the structural integrity of the positive electrode), so that the corresponding all-solid-state lithium-ion battery has relatively excellent cycle performance.

[0006] In some optional embodiments, the metal borate is selected from at least one of FeBO3, Zn3(BO3)2, Mn3(BO3)2, Co3(BO3)2 and Li3BO3.

[0007] In the above technical solution, the inorganic solid electrolyte is coated with the above-mentioned type of metal borate, which can more effectively improve the air stability of the inorganic solid electrolyte, so that the corresponding all-solid-state lithium-ion battery has better cycle performance.

[0008] In some optional embodiments, the thickness of the shell is 0.1-1000 nm; optionally, the thickness of the shell is 0.5-20 nm.

[0009] In the above technical solution, limiting the thickness of the shell within the above range can better take into account the air stability and ionic conductivity of the modified inorganic solid electrolyte; further, limiting the thickness of the shell within the range of 0.5~20 nm can better take into account the air stability and ionic conductivity of the modified inorganic solid electrolyte.

[0010] In some optional embodiments, the inorganic solid electrolyte is selected from at least one of a sulfide solid electrolyte and a halide solid electrolyte.

[0011] In the above technical solution, the coating layer provided in the embodiment of the present application can be well adapted to sulfide solid electrolytes and halide solid electrolytes.

[0012] In some optional embodiments, the inorganic solid electrolyte is a sulfide solid electrolyte, and the material of the sulfide solid electrolyte is Li6PS5Cl; or / and, the inorganic solid electrolyte is a halide solid electrolyte, and the material of the halide solid electrolyte is Li3InCl6.

[0013] In the above technical solution, the coating layer provided in the embodiment of the present application can be well adapted to Li6PS5Cl and Li3InCl6.

[0014] In a second aspect, an embodiment of the present application provides a method for preparing a modified inorganic solid electrolyte as provided in the embodiment of the first aspect, using atomic layer deposition technology to generate metal borates on the surface of the inorganic solid electrolyte to form a modified inorganic solid electrolyte with a core-shell structure.

[0015] In the above technical solution, atomic layer deposition technology is used to form a metal borate shell on the surface of the inorganic solid electrolyte, so that the prepared shell has the advantages of relatively uniform thickness, high density and high coverage rate of the core.

[0016] In some optional embodiments, the step of generating metal borate on the surface of the inorganic solid electrolyte using atomic layer deposition technology to form a modified inorganic solid electrolyte having a core-shell structure includes: S1: placing an inorganic solid electrolyte in a reaction chamber of an atomic layer deposition device, wherein the reaction chamber is in a vacuum state and the temperature is maintained at 50~400°C; S2: transporting a gaseous metal compound into the reaction chamber for sealing treatment so that the gaseous metal compound is adsorbed on the surface of the inorganic solid electrolyte to form a first precursor layer; S3: transporting a gaseous B-containing compound into the reaction chamber for sealing treatment so that the gaseous B-containing compound reacts with the first precursor layer to form a second precursor layer; S4: transporting a gaseous oxygen source into the reaction chamber for sealing treatment so that the gaseous oxygen source and the second precursor layer react to form a metal borate; S5: repeating steps S2~S4 multiple times to form a modified inorganic solid electrolyte with a core-shell structure; optionally, repeating steps S2~S4 10~40 times.

[0017] In the above technical solution, the preparation is carried out according to the above process, and a metal borate shell layer with relatively uniform thickness, high density and high coverage of the core can be formed on the surface of the inorganic solid electrolyte core; wherein, the temperature of the reaction chamber is maintained within the above range so that the various gaseous raw materials always remain in a gaseous state before reaching the surface of the core and participating in the reactions at various stages, thereby facilitating the full reaction of the various gaseous raw materials; further, steps S2 to S4 are repeated 10 to 40 times so that the prepared shell has a more suitable thickness, thereby enabling the prepared modified inorganic solid electrolyte to have both relatively ideal air stability and ionic conductivity.

[0018] In some optional embodiments, the step of transporting the gaseous metal compound into the reaction chamber for sealing treatment so that the gaseous metal compound forms a first precursor layer on the surface of the inorganic solid electrolyte includes: S21: transporting the gaseous metal compound into the reaction chamber for sealing treatment, wherein the pulse gas pressure for transporting the gaseous metal compound is 100-600 mTorr and the sealing treatment time is 0.5-5 min, so that the gaseous metal compound forms a first precursor layer on the surface of the inorganic solid electrolyte; S22: purging the reaction chamber with an inert gas to remove the residual gaseous metal compound in the reaction chamber; S23: repeating steps S21-S22 multiple times; optionally, repeating steps S21-S22 4-6 times.

[0019] In the above technical solution, a first precursor layer is formed on the surface of the inorganic solid electrolyte through repeated deposition. During each deposition process, the pulse pressure for delivering the gaseous metal compound and the sealing treatment time are respectively limited to the above-mentioned ranges, so that the gaseous metal compound can be relatively saturated on the entire surface of the core, that is, a first precursor layer with good coating integrity is formed. Furthermore, by repeating steps S21 and S22 4 to 6 times, it is possible to better balance the coating integrity, uniformity, and coating efficiency of the first precursor layer on the core surface.

[0020] In some optional embodiments, the step of delivering the gaseous B-containing compound into the reaction chamber for sealing treatment so that the gaseous B-containing compound reacts with the first precursor layer to form the second precursor layer includes: S31: transporting the gaseous B-containing compound into the reaction chamber for sealing treatment, wherein the pulse gas pressure for transporting the gaseous B-containing compound is 100-600 mTorr and the sealing treatment time is 0.5-5 min, so that the gaseous B-containing compound reacts with the first precursor layer to generate a second precursor layer; S32: purging the reaction chamber with an inert gas to remove the gaseous B-containing compound remaining in the reaction chamber and the gaseous by-products generated by the reaction; S33: repeating steps S31-S32 multiple times; optionally, repeating steps S31-S32 4-6 times.

[0021] In the above technical solution, by repeatedly feeding the gaseous B-containing compound, and during each delivery process, controlling the pulse pressure and sealing time of the gaseous B-containing compound within the aforementioned ranges, the gaseous B-containing compound is relatively fully loaded onto the entire surface of the first precursor layer and reacts with it, thereby forming a second precursor layer with improved coating integrity. Furthermore, by repeating steps S31 and S32 four to six times, the second precursor layer can achieve a good balance between coating integrity, uniformity, and coating efficiency on the core surface.

[0022] In some optional embodiments, the step of delivering a gaseous oxygen source into a reaction chamber for a closed treatment so that the gaseous oxygen source and the second precursor layer react to form a metal borate comprises: S41: delivering a gaseous oxygen source into a reaction chamber for sealing treatment, wherein the pulse gas pressure of delivering the gaseous oxygen source is 100-600 mTorr and the sealing treatment time is 0.5-5 min, so that the gaseous oxygen source and the second precursor layer react to form metal borate; S42: purging the reaction chamber with an inert gas to remove the residual gaseous oxygen source in the reaction chamber and the gaseous by-products generated by the reaction; S43: repeating steps S41-S42 multiple times; optionally, repeating steps S41-S42 4-6 times.

[0023] In the above technical solution, by repeatedly supplying a gaseous oxygen source, and during each delivery process, limiting the pulse pressure of the gaseous oxygen source and the sealing treatment time to the aforementioned ranges, the gaseous oxygen source is relatively saturated over the entire surface of the second precursor layer and reacts with it, thereby forming a metal borate shell layer with good coating integrity. Furthermore, by repeating steps S41 and S42 4 to 6 times, the integrity, uniformity, and coating efficiency of the metal borate shell layer on the core surface can be well balanced.

[0024] In some optional embodiments, the material of the gaseous metal compound is selected from ZnEt2, Zn(OAc)2, MnTp2, Mn(EtCp)2, Fe(acac)3, Fe( t BuAMD)2, Li(OtBu) and CoTp2; optionally, the material of the gaseous metal compound is selected from at least one of ZnEt2, Fe(acac)3 and Li(OtBu).

[0025] In the above technical solution, the above-mentioned types of raw materials are selected to form the corresponding metal lithium borate shell layer, which has the advantages of easy availability of raw materials, high reaction activity and high purity of the prepared corresponding metal lithium borate shell layer.

[0026] In some optional embodiments, the material of the gaseous B-containing compound is selected from at least one of B(OMe)3, B(OiPr)3 and B2H6; optionally, the material of the gaseous metal compound is selected from at least one of B(OMe)3 and B2H6.

[0027] In the above technical solutions, the embodiments of the present application are applicable to a wide variety of gaseous B-containing compounds, and can provide a wide variety of feasible implementation plans, thereby facilitating the promotion and application of the technical solutions provided in the embodiments of the present application.

[0028] In some optional embodiments, the material of the gaseous oxygen source is selected from at least one of oxygen and ozone.

[0029] In the above technical solutions, the embodiments of the present application are applicable to a wide variety of gaseous B-containing compounds, and can provide a wide variety of feasible implementation plans, thereby facilitating the promotion and application of the technical solutions provided in the embodiments of the present application.

[0030] In a third aspect, an embodiment of the present application provides an all-solid-state lithium-ion battery, which includes a positive electrode sheet, a solid electrolyte membrane and a negative electrode sheet, and the solid electrolyte membrane is located between the positive electrode sheet and the negative electrode sheet; wherein, at least one of the positive electrode sheet, the solid electrolyte membrane and the negative electrode sheet includes the modified inorganic solid electrolyte provided in the embodiment of the first aspect.

[0031] In the above technical solution, the functional unit (at least one of the positive electrode sheet, solid electrolyte membrane and negative electrode sheet) in the all-solid-state lithium-ion battery includes the modified inorganic solid electrolyte provided by the embodiment of the first aspect. Since the modified inorganic solid electrolyte has relatively ideal air stability and is not prone to side reactions after contact with the active material, the corresponding all-solid-state lithium-ion battery has relatively excellent cycle performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following is a brief introduction to the drawings required for use in the embodiments. It should be understood that the following drawings only show certain embodiments of the present application and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other relevant drawings can be obtained based on these drawings without creative work.

[0033] Figure 1 This is a process flow chart of a method for preparing a modified inorganic solid electrolyte provided in an embodiment of the present application. DETAILED DESCRIPTION

[0034] To make the purpose, technical solutions and advantages of the examples of the present application clearer, the technical solutions in the examples of the present application will be described clearly and completely below. Where specific conditions are not specified in the examples, conventional conditions or conditions recommended by the manufacturer are used. Where the manufacturer of the reagents or instruments is not specified, they are all conventional products that can be purchased commercially.

[0035] It should be noted that “and / or” in this application, such as “Feature 1 and / or Feature 2”, refers to three situations: “Feature 1” alone, “Feature 2” alone, or “Feature 1” plus “Feature 2”.

[0036] In addition, in the description of this application, unless otherwise specified, the "multiple" in "one or more" means two or more; the range of "value a~value b" includes the two end values ​​"a" and "b", and the "unit of measurement" in "value a~value b+unit of measurement" represents the "unit of measurement" of both "value a" and "value b".

[0037] The following is a detailed description of a modified inorganic solid electrolyte, a preparation method thereof, and an all-solid-state lithium-ion battery according to an embodiment of the present application.

[0038] In a first aspect, an embodiment of the present application provides a modified inorganic solid electrolyte, which has a core-shell structure, wherein the inner core is made of an inorganic solid electrolyte and the outer shell is made of a metal borate.

[0039] In the present application, the surface of the inorganic solid electrolyte core material has a shell layer made of metal borate. Compared with inorganic solid electrolytes, metal borate has more ideal air stability. The use of metal borate to coat the inorganic solid electrolyte can effectively improve the air stability of the inorganic solid electrolyte, so that its ionic conductivity is always maintained at a more ideal level; at the same time, the coating and isolation of the inorganic solid electrolyte by the metal borate can also improve the problem of side reactions that are prone to occur after the inorganic solid electrolyte is in direct contact with the active material (specifically, sulfide solid electrolytes are prone to harmful interfacial side reactions after direct contact with active materials, especially high-voltage positive electrodes and lithium metal negative electrodes; after halide solid electrolytes are in direct contact with lithium metal, the metal elements in the halide solid electrolyte are easily reduced to form metal elements, and after direct contact with the high-voltage positive electrode, redox reactions are easily generated during the charge and discharge process, resulting in the destruction of the structural integrity of the positive electrode), so that the corresponding all-solid-state lithium-ion battery has relatively excellent cycle performance.

[0040] It should be noted that the reasons for the poor air stability of inorganic solid electrolytes are: for sulfide solid electrolytes, their poor air stability is reflected in their sensitivity to water and oxygen in the air. During the preparation, transportation and use, they are easily exposed to water and oxygen, resulting in side reactions and decomposition, which leads to a decrease in ionic conductivity; for halide solid electrolytes, their poor air stability is reflected in their sensitivity to water in the air. During the preparation, transportation and use, they are easily decomposed by absorbing moisture, which leads to a decrease in ionic conductivity.

[0041] It should be emphasized that metal borates themselves have the advantage of a wide electrochemical window. After being coated with inorganic solid electrolytes, they can also enable the corresponding modified inorganic solid electrolytes to better take into account both high-voltage positive electrodes and low-voltage negative electrodes, which also helps to improve the cycle performance of the corresponding batteries.

[0042] As an example, the metal borate is selected from at least one of FeBO3, Zn3(BO3)2, Mn3(BO3)2, Co3(BO3)2 and Li3BO3.

[0043] In this embodiment, the inorganic solid electrolyte is coated with the above-mentioned type of metal borate, which can more effectively improve the air stability of the inorganic solid electrolyte, so that the corresponding all-solid-state lithium-ion battery has better cycle performance.

[0044] As an example, the thickness of the shell is 0.1~1000 nm, such as but not limited to a thickness of at least one of 0.1 nm, 0.5 nm, 1 nm, 5 nm, 10 nm, 50 nm, 100 nm, 200 nm, 400 nm, 800 nm and 1000 nm, or a range value between any two of them.

[0045] In this embodiment, limiting the thickness of the outer shell to the above range can better balance the air stability and ionic conductivity of the modified inorganic solid electrolyte.

[0046] As an example, the thickness of the shell is 0.5~20 nm, such as but not limited to a thickness of at least one of 0.5 nm, 0.8 nm, 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 17 nm, 18 nm, 19 nm and 20 nm, or a range value between any two of the thicknesses.

[0047] In this embodiment, the thickness of the shell is limited to the range of 0.5 to 20 nm, which can better balance the air stability and ionic conductivity of the modified inorganic solid electrolyte.

[0048] As an example, the inorganic solid electrolyte is selected from at least one of a sulfide solid electrolyte and a halide solid electrolyte.

[0049] In this embodiment, the coating layer provided in the embodiment of the present application can be well adapted to the sulfide solid electrolyte and the halide solid electrolyte.

[0050] It should be noted that the types of sulfide solid electrolytes and halide solid electrolytes are not limited and can be set according to conventional selection in the field. For example, the sulfide solid electrolyte is selected from Li3PS4, Li 10 GeP2S 12 , Li6PS5Br, Li6PS5I and Li6PS5Cl; the halide solid electrolyte is selected from at least one of Li3InCl6, Li3ScCl6, Li2ZrCl6 and Li3YCl6.

[0051] As an example, the inorganic solid electrolyte is a sulfide solid electrolyte, and the material of the sulfide solid electrolyte is Li6PS5Cl; or / and, the inorganic solid electrolyte is a halide solid electrolyte, and the material of the halide solid electrolyte is Li3InCl6.

[0052] In this embodiment, the coating layer provided in the embodiment of the present application can be well adapted to Li6PS5Cl and Li3InCl6.

[0053] It should be noted that any structural or functional units not specifically described or limited in the modified inorganic solid electrolyte may be arranged according to conventional selections in the art.

[0054] In a second aspect, an embodiment of the present application provides a method for preparing a modified inorganic solid electrolyte as provided in the embodiment of the first aspect, using atomic layer deposition technology to generate metal borates on the surface of the inorganic solid electrolyte to form a modified inorganic solid electrolyte with a core-shell structure.

[0055] In the present application, atomic layer deposition technology is used to form a metal borate shell on the surface of an inorganic solid electrolyte, so that the prepared shell has advantages such as relatively uniform thickness, high density and high coverage rate of the core.

[0056] As an example, the steps of generating metal borate on the surface of an inorganic solid electrolyte using atomic layer deposition technology to form a modified inorganic solid electrolyte having a core-shell structure include: S1. Placing an inorganic solid electrolyte in a reaction chamber of an atomic layer deposition device, wherein the reaction chamber is in a vacuum state and the temperature is maintained at 50-400°C (for example, but not limited to, a temperature in the range of at least one of 50°C, 100°C, 150°C, 200°C, 250°C, 300°C, 350°C and 400°C, or a range between any two thereof); S2. Transporting a gaseous metal compound into the reaction chamber for sealing treatment so that the gaseous metal compound is adsorbed on the surface of the inorganic solid electrolyte to form a first precursor layer; S3. Transporting a gaseous B-containing compound into the reaction chamber for sealing treatment so that the gaseous B-containing compound reacts with the first precursor layer to form a second precursor layer; S4. Transporting a gaseous oxygen source into the reaction chamber for sealing treatment so that the gaseous oxygen source reacts with the second precursor layer to form a metal borate; S5. Repeating steps S2-S4 multiple times to form a modified inorganic solid electrolyte having a core-shell structure.

[0057] It should be noted that in step S1, the vacuum degree in the reaction chamber can be set according to conventional selections in the art, for example, the vacuum degree can be (1-10)×10 −5 mTorr, for example but not limited to, the vacuum degree can be 1×10 −5 mTorr, 2×10 −5 mTorr, 4×10 −5 mTorr, 6×10 −5 mTorr, 8×10 −5 mTorr and 10×10 −5 A range of values ​​between at least one or any two of mTorr.

[0058] In this embodiment, the preparation is carried out according to the above process, and a metal borate shell layer with relatively uniform thickness, high density and high coverage of the inner core can be formed on the surface of the inorganic solid electrolyte inner core; wherein, the temperature of the reaction chamber is maintained within the above range so that the various gaseous raw materials always remain in a gaseous state before reaching the surface of the inner core and participating in the reaction at each stage, thereby facilitating the full reaction of the various gaseous raw materials.

[0059] As an example, steps S2 to S4 are repeated 10 to 40 times, for example but not limited to, any one of 10, 20, 30 and 40 times or a range between any two of them.

[0060] In this embodiment, steps S2 to S4 are repeated 10 to 40 times so that the prepared shell has a relatively suitable thickness, and thus the prepared modified inorganic solid electrolyte can have relatively ideal air stability and ionic conductivity.

[0061] It should be noted that at the beginning of the first cycle, since there is no coating layer on the surface of the inorganic solid electrolyte core, the first precursor layer formed is directly coated on the surface of the inorganic solid electrolyte core. However, after the first cycle, since the surface of the inorganic solid electrolyte core already has metal borate, from the beginning of the second cycle, the first precursor layer formed will be coated on the surface of the metal borate formed in the previous cycle, and this cycle will eventually produce a metal borate shell layer of the target thickness.

[0062] As an example, the step of transporting the gaseous metal compound into the reaction chamber for sealing treatment so that the gaseous metal compound forms a first precursor layer on the surface of the inorganic solid electrolyte includes: S21: transporting the gaseous metal compound into the reaction chamber for sealing treatment, wherein the pulse gas pressure of the gaseous metal compound is 100-600 mTorr (for example, but not limited to, the pulse gas pressure is any one of 100 mTorr, 150 mTorr, 200 mTorr, 250 mTorr, 300 mTorr, 350 mTorr, 400 mTorr, 450 mTorr, 500 mTorr, 550 mTorr, and 600 mTorr, or a range between any two of them), and the sealing treatment time is 0.5-5 min (for example, but not limited to, the time is any one of 0.5 min, 1 min, 1.5 min, 2 min, 2.5 min, 3 min, 3.5 min, 4 min, 4.5 min, and 5 min, or a range between any two of them), so that the gaseous metal compound forms a first precursor layer on the surface of the inorganic solid electrolyte; S22: The reaction chamber is purged with an inert gas to remove the residual gaseous metal compounds in the reaction chamber; S23 Steps S21 to S22 are repeated multiple times.

[0063] In this embodiment, a first precursor layer is formed on the surface of the inorganic solid electrolyte by repeated deposition, and in each deposition process, the pulse gas pressure for delivering the gaseous metal compound and the time of the sealing treatment are respectively limited within the above-mentioned ranges, so that the gaseous metal compound can be more saturatedly loaded on the entire surface of the inner core, thereby forming a first precursor layer with good coating integrity.

[0064] As an example, steps S21 to S22 are repeated 4 to 6 times.

[0065] In this embodiment, steps S21 to S22 are repeated 4 to 6 times, which can better balance the coating integrity, uniformity and coating efficiency of the first precursor layer on the core surface.

[0066] As an example, the step of using an inert gas to purge the reaction chamber to remove residual gaseous metal compounds in the reaction chamber in S22 includes: S221: delivering an inert gas into a vacuum reaction chamber, wherein the pulsed gas pressure of the delivered inert gas is 6000-9000 mTorr (for example, but not limited to, the pulsed gas pressure is any one of 6000 mTorr, 6300 mTorr, 6600 mTorr, 6900 mTorr, 7200 mTorr, 7500 mTorr, 7800 mTorr, 8100 mTorr, 8400 mTorr, 8700 mTorr, and 9000 mTorr, or a range between any two of them); S222: evacuating the reaction chamber to remove the inert gas in the reaction chamber; S223: repeating steps S221-S222 multiple times.

[0067] It should be noted that in step S221, if the reaction chamber is already in a vacuum state, there is no need to perform vacuuming in advance; if the reaction chamber is not in a vacuum state, it is necessary to perform vacuuming in advance, and the specific process can be adaptively adjusted according to actual conditions.

[0068] It should be noted that, in the step of vacuuming, the vacuum degree in the reaction chamber is maintained consistent with the vacuum degree in step S1.

[0069] In this embodiment, by repeatedly purging the reaction chamber with an inert atmosphere and limiting the pulse pressure of the inert gas delivered each time to within the above range, the gaseous metal compounds remaining in the reaction chamber and some gaseous impurities that may be generated can be effectively removed.

[0070] As an example, steps S221 to S222 are repeated 3 to 5 times.

[0071] In this embodiment, steps S221 - S222 are repeated 3-5 times, which can more thoroughly remove the gaseous metal compounds remaining in the reaction chamber.

[0072] As an example, the step of transporting the gaseous B-containing compound into a reaction chamber for sealing treatment so that the gaseous B-containing compound reacts with the first precursor layer to form the second precursor layer includes: S31: transporting a gaseous B-containing compound into the reaction chamber for a sealing treatment, wherein a pulse gas pressure of the gaseous B-containing compound is 100-600 mTorr (for example, but not limited to, a pulse gas pressure of any one of 100 mTorr, 150 mTorr, 200 mTorr, 250 mTorr, 300 mTorr, 350 mTorr, 400 mTorr, 450 mTorr, 500 mTorr, 550 mTorr, and 600 mTorr, or a range between any two of the pulse gas pressures), and the sealing treatment time is 0.5-5 min (for example, but not limited to, a time of any one of 0.5 min, 1 min, 1.5 min, 2 min, 2.5 min, 3 min, 3.5 min, 4 min, 4.5 min, and 5 min, or a range between any two of the pulse gas pressures), so that the gaseous B-containing compound reacts with the first precursor layer to form a second precursor layer; S32: The reaction chamber is purged with an inert gas to remove the gaseous B-containing compound remaining in the reaction chamber and the gaseous by-products generated by the reaction; S33 Steps S31 to S32 are repeated multiple times.

[0073] In this embodiment, the gaseous B-containing compound is repeatedly input multiple times, and in each delivery process, the pulse gas pressure of the gaseous B-containing compound and the time of the sealing treatment are limited to the above-mentioned ranges, so that the gaseous B-containing compound can be relatively saturatedly loaded on the entire surface of the first precursor layer and react with it to form a second precursor layer with better coating integrity.

[0074] As an example, steps S31 to S32 are repeated 4 to 6 times.

[0075] In this embodiment, steps S31 to S32 are repeated 4 to 6 times, which can better balance the coating integrity, uniformity and coating efficiency of the second precursor layer on the core surface.

[0076] It should be noted that step S32 can be performed with reference to step S22.

[0077] As an example, the step of delivering a gaseous oxygen source into a reaction chamber for a closed treatment so that the gaseous oxygen source reacts with the second precursor layer to form a metal borate includes: S41: delivering a gaseous oxygen source into the reaction chamber for a sealing treatment, wherein a pulse gas pressure of the gaseous oxygen source is 100-600 mTorr (for example, but not limited to, the pulse gas pressure is any one of 100 mTorr, 150 mTorr, 200 mTorr, 250 mTorr, 300 mTorr, 350 mTorr, 400 mTorr, 450 mTorr, 500 mTorr, 550 mTorr, and 600 mTorr, or a range between any two thereof), and the sealing treatment time is 0.5-5 min (for example, but not limited to, any one of 0.5 min, 1 min, 1.5 min, 2 min, 2.5 min, 3 min, 3.5 min, 4 min, 4.5 min, and 5 min, or a range between any two thereof), so that the gaseous oxygen source reacts with the second precursor layer to generate a metal borate; S42: The reaction chamber is purged with an inert gas to remove the residual gaseous oxygen source and the gaseous by-products generated by the reaction in the reaction chamber; S43 Steps S41 to S42 are repeated multiple times.

[0078] In this embodiment, the gaseous oxygen source is repeatedly input multiple times, and in each delivery process, the pulse gas pressure of the gaseous oxygen source and the time of the sealing treatment are limited to the above-mentioned ranges, so that the gaseous oxygen source can be relatively saturatedly loaded on the entire surface of the second precursor layer and react with it to form a metal lithium borate shell layer with good coating integrity.

[0079] As an example, steps S41 to S42 are repeated 4 to 6 times.

[0080] In this embodiment, steps S41 to S42 are repeated 4 to 6 times, which can better balance the coating integrity, uniformity and coating efficiency of the metal borate shell layer on the core surface.

[0081] It should be noted that step S42 can be performed with reference to step S22.

[0082] As an example, the material of the gaseous metal compound is selected from ZnEt2, Zn(OAc)2, MnTp2, Mn(EtCp)2, Fe(acac)3, Fe( t At least one of BuAMD)2, Li(OtBu) and CoTp2.

[0083] As an example, the material of the gaseous metal compound is selected from at least one of ZnEt2, Fe(acac)3 and Li(OtBu).

[0084] In this embodiment, the above-mentioned types of raw materials are selected to form the corresponding metal lithium borate shell layer, which has the advantages of easy availability of raw materials, high reaction activity and high purity of the prepared corresponding metal lithium borate shell layer.

[0085] As an example, the material of the gaseous B compound is selected from at least one of B(OMe)3, B(OiPr)3 and B2H6.

[0086] As an example, the material of the gaseous metal compound is selected from at least one of B(OMe)3 and B2H6.

[0087] In this embodiment, the embodiments of the present application are applicable to a wide variety of gaseous B-containing compounds, and can provide a wide variety of feasible implementation plans, thereby facilitating the promotion and application of the technical solutions provided in the embodiments of the present application.

[0088] As an example, the material of the gaseous oxygen source is selected from at least one of oxygen and ozone.

[0089] In this embodiment, the embodiments of the present application are applicable to a wide variety of gaseous B-containing compounds, and can provide a wide variety of feasible implementation plans, thereby facilitating the promotion and application of the technical solutions provided in the embodiments of the present application.

[0090] It should be noted that the gaseous oxygen source can be a single type of gas or a mixed gas mixed with an inert gas. When the gaseous oxygen source is a mixed gas (for example, the gaseous oxygen source is a mixed gas of oxygen and nitrogen, wherein the volume proportion of oxygen is 50%), the pulse gas pressure when delivering the gaseous oxygen source is the partial pressure of oxygen. Specifically, if the pulse gas pressure for delivering the gaseous oxygen source mixture is set to 200 mTorr (the partial pressure of oxygen), the mixed gas should be delivered at 400 mTorr.

[0091] It should be noted that any process or step not specifically described or limited in the preparation process of the modified inorganic solid electrolyte may be arranged according to conventional selection in the art.

[0092] As an example, the process flow chart of the preparation method of the modified inorganic solid electrolyte is shown in FIG. Figure 1 .

[0093] In a third aspect, an embodiment of the present application provides an all-solid-state lithium-ion battery, which includes a positive electrode sheet, a solid electrolyte membrane and a negative electrode sheet, and the solid electrolyte membrane is located between the positive electrode sheet and the negative electrode sheet; wherein, at least one of the positive electrode sheet, the solid electrolyte membrane and the negative electrode sheet includes the modified inorganic solid electrolyte provided in the embodiment of the first aspect.

[0094] In the present application, the functional unit (at least one of the positive electrode sheet, solid electrolyte membrane and negative electrode sheet) in the all-solid-state lithium-ion battery includes the modified inorganic solid electrolyte provided by the first embodiment. Since the modified inorganic solid electrolyte has relatively ideal air stability and is not prone to side reactions after contact with the active material, the corresponding all-solid-state lithium-ion battery has relatively excellent cycle performance.

[0095] It should be noted that each functional unit in the all-solid-state lithium-ion battery can be configured according to conventional selections in the art and is not specifically limited in the embodiments of the present application.

[0096] As an example, the positive electrode sheet includes NCM622 (positive electrode active material), super-P (conductive agent), CNT (conductive agent), Li6PS5Cl (sulfide solid electrolyte) and PVDF (binder) in a mass ratio of 87:1.5:0.3:10:1.2; the negative electrode sheet includes graphite (negative electrode active material), conductive carbon black (conductive agent), Li6PS5Cl (sulfide solid electrolyte), sodium carboxymethyl cellulose (binder) and styrene-butadiene rubber (binder) in a mass ratio of 85.6:2:10:1.2:2.2.

[0097] In other possible implementations, Li6PS5Cl (sulfide solid electrolyte) can be completely replaced with Li3InCl6 (halide solid electrolyte); similarly, the types and amounts of other functional components in the positive and negative electrodes can also be adaptively adjusted.

[0098] It should be noted that the solid electrolytes of the positive electrode sheet and the negative electrode sheet can be either one of them using the modified inorganic solid electrolyte provided in the embodiment of the present application, or both of them using the modified inorganic solid electrolyte provided in the embodiment of the present application, and can be adaptively adjusted according to actual needs.

[0099] The features and performance of the present application are further described in detail below with reference to the embodiments.

[0100] Example 1 The present invention provides a method for preparing an all-solid-state lithium-ion battery, comprising the following steps: (1) Preparation of modified inorganic solid electrolytes S1 Place 1 kg of Li6PS5Cl in the reaction chamber of the atomic layer deposition equipment, where the reaction chamber is in a vacuum state (vacuum degree is 7.5×10 −5 mTorr) and the temperature was maintained at 200°C.

[0101] S2 transports gaseous diethyl zinc (ZnEt2) into the reaction chamber for sealing treatment, so that the gaseous metal compound is adsorbed on the surface of the inorganic solid electrolyte to form a first precursor layer. Specifically, the pulse gas pressure of the gaseous diethyl zinc is 300 mTorr, and the sealing treatment is 1 minute after the transport. This standard is repeated 5 times; and after each completion, the reaction chamber needs to be purged once with an inert gas to remove the residual gaseous diethyl zinc that has not been adsorbed. The standard is: first vacuum the reaction chamber, then transport an inert gas (nitrogen) into the reaction chamber, and then vacuum the reaction chamber again. Among them, the pulse gas pressure of the inert gas is 8500 mTorr. In the vacuum treatment step, the vacuum degree in the reaction chamber is consistent with the vacuum degree in step S1.

[0102] S3 transports gaseous trimethoxyboron (B(OMe)3) into the reaction chamber for sealing treatment, so that the gaseous B-containing compound reacts with the first precursor layer on the surface of the inorganic solid electrolyte to form a second precursor layer. Specifically, the pulse gas pressure for transporting the gaseous trimethoxyboron is 300 mTorr, and the sealing treatment is 1 minute after transporting. This standard is repeated 5 times; and after each treatment, the reaction chamber needs to be purged once with an inert gas to remove the residual gaseous trimethoxyboron that has not been adsorbed. The standard is: first vacuum the reaction chamber, then transport an inert gas (nitrogen) into the reaction chamber, and then vacuum the reaction chamber again. Among them, the pulse gas pressure for transporting the inert gas is 8500 mTorr. In the vacuum treatment step, the vacuum degree in the reaction chamber is consistent with the vacuum degree in step S1.

[0103] S4: Gaseous oxygen is transported into the reaction chamber to react with the gaseous oxygen and the second precursor layer to generate metal borate. Specifically, the pulse pressure of the gaseous oxygen is 300 mTorr, and the reaction is sealed for 1 minute after the transport. This standard is repeated 5 times. Moreover, after each reaction, the reaction chamber needs to be purged once with an inert gas to remove unreacted residual gaseous oxygen. The standard is: first, the reaction chamber is vacuumed, and then an inert gas (nitrogen) is transported into the reaction chamber, and then the reaction chamber is vacuumed again. The pulse pressure of the inert gas is 8500 mTorr. During the vacuum treatment step, the vacuum degree in the reaction chamber is consistent with the vacuum degree in step S1.

[0104] S5: Repeat steps S2 to S4 18 times to form a modified inorganic solid electrolyte having a core-shell structure, wherein the shell thickness is 1.15 nm.

[0105] (2) Preparation of all-solid-state lithium-ion batteries Preparation of positive electrode sheet: NCM622 (positive electrode active material), super-P (conductive agent), CNT (conductive agent), the coated sulfide solid electrolyte prepared in step (1) and PVDF (binder) were stirred and mixed with N-methylpyrrolidone (NMP) in a vacuum mixer in a mass ratio of 87:1.5:0.3:10:1.2 to obtain positive electrode sheet slurry; the positive electrode sheet slurry was evenly coated on both sides of the aluminum foil (thickness 13 μm) current collector, and the positive electrode sheet was obtained after drying, cold pressing and die-cutting.

[0106] Negative electrode sheet preparation: Graphite (negative electrode active material), conductive carbon black (conductive agent), uncoated sulfide solid electrolyte, sodium carboxymethyl cellulose (binder) and styrene-butadiene rubber (binder) were mixed with deionized water in a vacuum mixer in a mass ratio of 85.6:2:10:1.2:2.2 to obtain a negative electrode sheet slurry; the negative electrode sheet slurry was evenly coated on both sides of the copper foil (thickness 8 μm) current collector, and the negative electrode sheet was obtained after drying, cold pressing and die-cutting.

[0107] A 20 μm-thick sulfide solid electrolyte membrane (composed of Li6PS5Cl and a binder in a mass ratio of 98:2) was placed between the positive and negative electrode sheets, and a bare cell was prepared by stacking the sheets. The bare cell was then placed in a packaging bag made of an aluminum-plastic film composite material and packaged to obtain a dry cell. The dry cell was baked to remove water to reduce the water content to less than 250 ppm. The dry cell then underwent isostatic pressing, sealing, standing, formation, degassing packaging, and capacity division to obtain a soft-pack all-solid-state lithium-ion battery.

[0108] Example 2 The embodiment of the present application provides a method for preparing an all-solid-state lithium-ion battery, which differs from Example 1 only in that: all gaseous diethyl is replaced by gaseous Fe(acac)3, that is, the material of the formed metal lithium borate is replaced by Zn3(BO3)2 to FeBO3 to form a modified inorganic solid electrolyte with a core-shell structure, and the corresponding shell thickness is 1.19 nm.

[0109] Example 3 The embodiment of the present application provides a method for preparing an all-solid-state lithium-ion battery, which differs from Example 1 only in that: all gaseous trimethoxyboron is replaced by gaseous B2H6 to form a modified inorganic solid electrolyte with a core-shell structure, and the corresponding shell thickness is 1.12 nm.

[0110] Comparative Example 1 The comparative example of the present application provides a method for preparing an all-solid-state lithium-ion battery, which differs from Example 1 only in that: in step (1), no coating layer is formed on the surface of Li6PS5Cl, that is, there is no metal borate shell on the surface of Li6PS5Cl in the positive electrode sheet.

[0111] Example 4 This embodiment of the present application provides a method for preparing an all-solid-state lithium-ion battery, which differs from Example 1 only in that: In step (1), all 1 kg of Li6PS5Cl is replaced with Li3InCl6, that is, the sulfide solid electrolyte core is replaced with a halide solid electrolyte core to form a modified inorganic solid electrolyte with a core-shell structure, wherein the shell thickness is 1.11 nm.

[0112] In step (ii), NCM622 (positive electrode active material), super-P (conductive agent), CNT (conductive agent), uncoated halide solid electrolyte and PVDF (binder) are stirred and mixed with N-methylpyrrolidone (NMP) in a vacuum mixer in a mass ratio of 87:1.5:0.3:10:1.2 to obtain a positive electrode slurry; graphite (negative electrode active material), conductive carbon black (conductive agent), the coated halide solid electrolyte prepared in step (i), sodium carboxymethyl cellulose (binder) and styrene-butadiene rubber (binder) are stirred and mixed with deionized water in a vacuum mixer in a mass ratio of 85.6:2:10:1.2:2.2 to obtain a negative electrode slurry.

[0113] In step (2), the material used for the solid electrolyte membrane is changed from Li6PS5Cl to Li3InCl6.

[0114] Example 5 The embodiment of the present application provides a method for preparing an all-solid-state lithium-ion battery, which differs from Example 4 only in that: all the gaseous diethyl is replaced by gaseous Fe(acac)3, that is, the material of the formed metal lithium borate is replaced by Zn3(BO3)2 to FeBO3 to form a modified inorganic solid electrolyte with a core-shell structure, and the corresponding shell thickness is 1.09 nm.

[0115] Example 6 The embodiment of the present application provides a method for preparing an all-solid-state lithium-ion battery, which differs from Example 1 only in that: all gaseous trimethoxyboron is replaced by gaseous B2H6 to form a modified inorganic solid electrolyte with a core-shell structure, and the corresponding shell thickness is 1.14 nm.

[0116] Comparative Example 2 The comparative example of the present application provides a method for preparing an all-solid-state lithium-ion battery, which differs from Example 4 only in that: in step (1), no coating layer is formed on the surface of Li6PS5Cl, that is, there is no metal borate shell on the surface of Li3InCl6 in the negative electrode sheet.

[0117] Test example 1. Air stability test of solid electrolyte Examples 1-3 and Comparative Example 1, Examples 4-6 and Comparative Example 2 were divided into two groups according to the solid electrolyte material, and then the air stability of the solid electrolyte samples prepared in step (1) was tested respectively, and the test results were statistically summarized in Table 1.

[0118] The test steps for air stability are as follows: The lithium ion conductivity of the solid electrolyte powder was tested before and after being exposed to moisture with a relative humidity of 5% for 24 hours, and the retention rate of the lithium ion conductivity was calculated.

[0119] Table 1

[0120] It should be noted that in Table 1, the ionic conductivity retention rate of Comparative Example 1 and Comparative Example 2 is 0. This is because there is no coating layer on the internal surface of the solid electrolyte, and the reaction activity of the material is high, resulting in severe decomposition of the material after exposure to moisture with a relative humidity of 5% for 24 hours.

[0121] Referring to Table 1, the test results of Examples 1-3 and Comparative Example 1, and Examples 4-6 and Comparative Example 2 show that the provision of a metal borate shell outside the inorganic solid electrolyte core results in a more stable lithium ion conductivity in air than the provision of no shell, i.e., superior air stability.

[0122] 2. Cycle performance test of all-solid-state lithium-ion batteries Examples 1-3 and Comparative Example 1, Examples 4-6 and Comparative Example 2 were divided into two groups according to the solid electrolyte material, and then the cycle performance of each battery sample in the two groups of samples was tested respectively, and the test results were statistically summarized in Table 2.

[0123] Among them, the test parameters of the battery cycle performance are as follows: the obtained all-solid-state lithium-ion battery is subjected to a charge and discharge cycle test, with a charging current of 0.8 A, a cut-off voltage of 4.9 V, a discharge current of 0.8 A, a cut-off voltage of 2.5 V, and a test environment temperature of 25°C. The number of cycles when the battery capacity decays to 80% is counted.

[0124] Table 2

[0125] Referring to Table 2, the test results of Examples 1 to 3 and Comparative Example 1, and Examples 4 to 6 and Comparative Example 2 show that the all-solid-state lithium-ion battery with a shell layer of metal lithium borate material outside the inner core of the inorganic solid electrolyte has better cycle performance than the battery without a shell layer.

[0126] The embodiments described above are part of the embodiments of the present application, rather than all of the embodiments. The detailed description of the embodiments of the present application is not intended to limit the scope of the present application for protection, but merely represents selected embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

Claims

1. A modified inorganic solid electrolyte, characterized in that: The modified inorganic solid electrolyte is a core-shell structure, wherein the core is made of inorganic solid electrolyte and the shell is made of metal borate.

2. The modified inorganic solid electrolyte according to claim 1, characterized in that The metal borate is selected from at least one of FeBO3, Zn3(BO3)2, Mn3(BO3)2, Co3(BO3)2 and Li3BO3.

3. The modified inorganic solid electrolyte according to claim 1, wherein The thickness of the shell is 0.1 to 1000 nm; Optionally, the shell has a thickness of 0.5-20 nm.

4. The modified inorganic solid electrolyte according to any one of claims 1 to 3, characterized in that The inorganic solid electrolyte is selected from at least one of a sulfide solid electrolyte and a halide solid electrolyte.

5. The modified inorganic solid electrolyte according to claim 4, characterized in that The inorganic solid electrolyte is a sulfide solid electrolyte, and the material of the sulfide solid electrolyte is Li6PS5Cl; Or / and, the inorganic solid electrolyte is a halide solid electrolyte, and the material of the halide solid electrolyte is Li3InCl6.

6. A method for preparing a modified inorganic solid electrolyte according to any one of claims 1 to 5, characterized in that: Atomic layer deposition technology is used to generate metal borate on the surface of the inorganic solid electrolyte to form the modified inorganic solid electrolyte with a core-shell structure.

7. The preparation method according to claim 6, characterized in that The step of using atomic layer deposition technology to generate metal borate on the surface of the inorganic solid electrolyte to form the modified inorganic solid electrolyte with a core-shell structure includes: S1. Placing an inorganic solid electrolyte in a reaction chamber of an atomic layer deposition apparatus, wherein the reaction chamber is in a vacuum state and the temperature is maintained at 50-400° C.; S2: transporting the gaseous metal compound into the reaction chamber for sealing treatment, so that the gaseous metal compound is adsorbed on the surface of the inorganic solid electrolyte to form a first precursor layer; S3: transporting the gaseous B-containing compound into the reaction chamber for sealing treatment, so that the gaseous B-containing compound reacts with the first precursor layer to form a second precursor layer; S4: delivering a gaseous oxygen source into the reaction chamber for sealing treatment, so that the gaseous oxygen source reacts with the second precursor layer to generate the metal borate; S5: Repeat steps S2 to S4 multiple times to form the modified inorganic solid electrolyte having a core-shell structure; Optionally, steps S2 to S4 are repeated 10 to 40 times.

8. The preparation method according to claim 7, characterized in that The step of transporting the gaseous metal compound into the reaction chamber for sealing treatment so that the gaseous metal compound forms a first precursor layer on the surface of the inorganic solid electrolyte includes: S21: transporting a gaseous metal compound into the reaction chamber for sealing treatment, wherein the pulse gas pressure of the gaseous metal compound is 100-600 mTorr and the sealing treatment time is 0.5-5 min, so that the gaseous metal compound forms a first precursor layer on the surface of the inorganic solid electrolyte; S22: purging the reaction chamber with an inert gas to remove the gaseous metal compound remaining in the reaction chamber; S23 repeats steps S21 to S22 multiple times; Optionally, steps S21-S22 are repeated 4-6 times.

9. The preparation method according to claim 7, characterized in that The step of transporting the gaseous B-containing compound into the reaction chamber for sealing treatment so that the gaseous B-containing compound reacts with the first precursor layer to form the second precursor layer includes: S31: delivering a gaseous B-containing compound into the reaction chamber for a sealing treatment, wherein the pulse gas pressure of delivering the gaseous B-containing compound is 100-600 mTorr and the sealing treatment time is 0.5-5 min, so that the gaseous B-containing compound reacts with the first precursor layer to form a second precursor layer; S32: purging the reaction chamber with an inert gas to remove the gaseous B-containing compound remaining in the reaction chamber and gaseous byproducts generated by the reaction; S33 repeats steps S31 to S32 multiple times; Optionally, steps S31-S32 are repeated 4-6 times.

10. The preparation method according to claim 7, characterized in that The step of delivering a gaseous oxygen source into the reaction chamber for sealing treatment so that the gaseous oxygen source reacts with the second precursor layer to form the metal borate comprises: S41: delivering a gaseous oxygen source into the reaction chamber for sealing treatment, wherein the pulse pressure of the gaseous oxygen source is 100-600 mTorr and the sealing treatment time is 0.5-5 minutes, so that the gaseous oxygen source reacts with the second precursor layer to generate the metal borate; S42: purging the reaction chamber with an inert gas to remove the residual gaseous oxygen source and gaseous byproducts generated by the reaction in the reaction chamber; S43 repeats steps S41-S42 multiple times; Optionally, steps S41-S42 are repeated 4-6 times.

11. The preparation method according to any one of claims 7 to 10, characterized in that The material of the gaseous metal compound is selected from ZnEt2, Zn(OAc)2, MnTp2, Mn(EtCp)2, Fe(acac)3, Fe( t At least one of BuAMD)2, Li(OtBu) and CoTp2; Optionally, the material of the gaseous metal compound is selected from at least one of ZnEt2, Fe(acac)3 and Li(OtBu).

12. The preparation method according to any one of claims 7 to 10, characterized in that The material of the gaseous B-containing compound is selected from at least one of B(OMe)3, B(OiPr)3 and B2H6; Optionally, the material of the gaseous metal compound is selected from at least one of B(OMe)3 and B2H6.

13. The preparation method according to any one of claims 7 to 10, characterized in that The material of the gaseous oxygen source is selected from at least one of oxygen and ozone.

14. An all-solid-state lithium-ion battery, characterized in that: The all-solid-state lithium-ion battery comprises a positive electrode sheet, a solid electrolyte membrane and a negative electrode sheet, wherein the solid electrolyte membrane is located between the positive electrode sheet and the negative electrode sheet; Wherein, at least one of the positive electrode sheet, the solid electrolyte membrane and the negative electrode sheet comprises the modified inorganic solid electrolyte according to any one of claims 1 to 5.

Images