CN114075083A - Sulfide electrolyte membrane, preparation method thereof and solid-state battery - Google Patents

Sulfide electrolyte membrane, preparation method thereof and solid-state battery Download PDF

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CN114075083A
CN114075083A CN202010796448.4A CN202010796448A CN114075083A CN 114075083 A CN114075083 A CN 114075083A CN 202010796448 A CN202010796448 A CN 202010796448A CN 114075083 A CN114075083 A CN 114075083A
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sulfide electrolyte
fiber fabric
inorganic fiber
electrolyte membrane
sulfide
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不公告发明人
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Evergrande New Energy Technology Shenzhen Co Ltd
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Evergrande New Energy Technology Shenzhen Co Ltd
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Abstract

The invention belongs to the technical field of solid-state batteries, and particularly relates to a sulfide electrolyte membrane, a preparation method thereof and a solid-state battery. The sulfide electrolyte is placed on the inorganic fiber fabric, and is loaded on the surface of the inorganic fiber fabric and/or in the pores of the inorganic fiber fabric through tabletting treatment and sintering treatment, so that the inorganic fiber fabric can bind the sulfide electrolyte in a micro area, the contact interface between sulfide electrolyte particles is changed from a point contact interface to a surface contact interface, and the contact area is increased; meanwhile, the sulfide electrolyte and the inorganic fiber fabric form a uniform, compact and flexible sulfide electrolyte membrane together through sintering treatment, and the problems that the sulfide electrolyte is easy to pulverize and difficult to transfer are solved.

Description

Sulfide electrolyte membrane, preparation method thereof and solid-state battery
Technical Field
The invention belongs to the technical field of solid-state batteries, and particularly relates to a sulfide electrolyte membrane and a preparation method thereof, and a solid-state battery.
Background
Most of commercialized lithium ion batteries adopt organic liquid as an electrolyte system, but the organic liquid electrolyte has the potential safety hazard of easy leakage, volatilization and even explosion. The solid electrolyte does not contain liquid components, can effectively avoid leakage due to the safety problem of the solid electrolyte, also has higher mechanical strength, and when the battery is assembled, the solid electrolyte can replace electrolyte and a diaphragm, so that the battery structure is simplified, and the solid electrolyte is expected to replace the traditional liquid electrolyte.
The solid electrolyte material may be divided into a crystalline solid electrolyte and an amorphous solid electrolyte according to a physical structure, wherein the amorphous solid electrolyte mainly includes an oxide electrolyte and a sulfide electrolyte. The oxide electrolyte has a lithium ion conductivity of 10-4s/cm, the components have good binding force, and can be prepared into glass ceramic sheets or films by high-temperature sintering, melting and other technological methods, such as: li6.75La3Zr1.75Ta0.25O12(LLZTO)、Li1.5Al0.5Ge1.5P3O12(lag), however, these glass-ceramic sheets or films all have a problem of being thick and difficult to apply to a high energy density solid-state battery.
Compared with oxide electrolyte, the sulfide electrolyte has higher lithium ion conductivity rate, and the lithium ion conductivity rate is 10- 2s/cm, but sulfide electrolyte has a problem of easy fracture due to its high brittleness, and the contact interface of sulfide electrolyte powder is often point-to-point contact, and the contact interface of each powder particle is small, and has a defect of many pores, so that it is difficult to prepare a transferable sulfide electrolyte film. The existing application mode is that sulfide electrolyte and high molecular polymer are mixed, pulped, coated, transferred and loaded on a positive electrode or a negative electrode plate, and then the mixture is subjected to heat treatment to enter the next process of preparing the solid-state battery. Therefore, how to prepare the transferable sulfide electrolyte film is a problem which needs to be solved urgently at present.
Disclosure of Invention
The invention aims to provide a sulfide electrolyte membrane, a preparation method thereof and a solid-state battery, and aims to solve the technical problems that the existing sulfide electrolyte membrane is easy to break and difficult to support a transferable sulfide electrolyte thin film.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a sulfide electrolyte membrane, which comprises the following steps:
providing a sulfide electrolyte and an inorganic fiber fabric;
and placing the sulfide electrolyte on the inorganic fiber fabric, and performing tabletting treatment and sintering treatment to obtain the sulfide electrolyte membrane.
Further, the inorganic fiber fabric is porous quartz fiber cloth or aluminum oxide fiber cloth.
Further, the thickness of the inorganic fiber fabric is 10 μm to 200 μm.
Furthermore, the porosity of the inorganic fiber fabric is more than 80%, and the pore diameter of the open pore is 200 mu m-5 mm.
Further, the temperature of the sintering treatment is 230-260 ℃.
Further, the time of the sintering treatment is 2min-30 min.
Further, the sulfide electrolyte is selected from Li2S-SiS2、LiX-Li2S-SiS2、Li2S-P2S5、LiX-Li2S-P2S5Wherein X is a halogen element.
The present invention provides a sulfide electrolyte membrane, which comprises a sulfide electrolyte and an inorganic fiber fabric, wherein the sulfide electrolyte is loaded on the surface of the inorganic fiber fabric and/or in the pores of the inorganic fiber fabric.
Further, the inorganic fiber fabric is porous quartz fiber cloth or aluminum oxide fiber cloth.
Further, the thickness of the sulfide electrolyte membrane is 20 μm to 200 μm.
Further, the thickness of the inorganic fiber fabric is 20-200 μm; and/or the inorganic fiber fabric has a porosity of 80% or more and an open pore diameter of 200 μm to 5 mm.
In still another aspect, the present invention provides a solid-state battery comprising the sulfide electrolyte membrane produced by the above-described sulfide electrolyte membrane production method, or the above-described sulfide electrolyte membrane.
According to the preparation method of the sulfide electrolyte membrane, the sulfide electrolyte is placed on the inorganic fiber fabric, and is subjected to tabletting treatment and sintering treatment, so that the sulfide electrolyte is loaded on the surface of the inorganic fiber fabric and/or in the pores of the inorganic fiber fabric. Firstly, the inorganic fiber fabric has a larger specific surface area and is used as a supporting material of sulfide electrolyte, the network skeleton structure of the inorganic fiber fabric has non-fluidity, and the sulfide electrolyte can be bound in a micro area, so that the contact interface between sulfide electrolyte particles is changed from a point contact interface to a surface contact interface, the contact area is improved, and the defect of more pores is overcome; secondly, the inorganic fiber fabric is inert and does not react with sulfide electrolyte, and the problems of combustion, melting, toxic gas generation and the like caused by heating can be avoided in the sintering process; finally, through sintering treatment, the sulfide electrolyte and the inorganic fiber fabric jointly form a uniform, compact and flexible sulfide electrolyte membrane, and the problems that the sulfide electrolyte is easy to pulverize and difficult to transfer are solved.
In the sulfide electrolyte membrane provided by the invention, the sulfide electrolyte is loaded on the surface of the inorganic fiber fabric and/or in the pores of the inorganic fiber fabric. The inorganic fiber fabric has a larger specific surface area and is used as a supporting material of the sulfide electrolyte, and the network skeleton structure of the inorganic fiber fabric has non-fluidity, so that the sulfide electrolyte can be bound in a micro area, the contact interface between sulfide electrolyte particles is changed from a point contact interface to a surface contact interface, the contact area is increased, and the defect of more pores is overcome; and the inorganic fiber fabric is inert, does not react with sulfide electrolyte and has good stability. The sulfide electrolyte membrane provided by the invention is uniform and compact, has certain flexibility, has the advantages of no powder falling and convenience in transferring and assembling the solid-state battery, is beneficial to realizing large-scale production, and has good application prospect and market value.
The solid-state battery provided by the invention comprises the sulfide electrolyte membrane, and the sulfide electrolyte membrane loads the sulfide electrolyte which is originally in powder shape on the surface of the inorganic fiber fabric and/or in the pores of the inorganic fiber fabric, so that the advantages of no powder falling and more convenient assembly of the solid-state battery by transfer are achieved, and the solid-state battery comprising the sulfide electrolyte membrane also has the advantages of convenient assembly and contribution to realizing large-scale production.
Drawings
FIG. 1 is a schematic view of an inorganic fiber fabric used in examples of the present invention;
FIG. 2 is a schematic view of a sulfide electrolyte membrane obtained by an example of the invention;
FIG. 3 is a photograph of a ball-milled mixture of a sulfide electrolyte raw material in an experimental example of the present invention;
FIG. 4 is a photograph of a ball-milled mixture of a sulfide electrolyte raw material after a sintering process in an experimental example of the present invention.
Detailed Description
In order to make the objects, technical solutions and technical effects of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described, and the embodiments described below are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention. Those whose specific conditions are not specified in the examples are carried out according to conventional conditions or conditions recommended by the manufacturer; the reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the present invention, the term "and/or" describing an association relationship of associated objects means that there may be three relationships, for example, a and/or B, may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the description of the present invention, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that the weight of the related components mentioned in the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, it is within the scope of the disclosure that the content of the related components is scaled up or down according to the embodiments of the present invention. Specifically, the weight described in the embodiments of the present invention may be a unit of mass known in the chemical field such as μ g, mg, g, kg, etc.
In addition, unless the context clearly uses otherwise, an expression of a word in the singular is to be understood as including the plural of the word. The terms "comprises" or "comprising" are intended to specify the presence of stated features, quantities, steps, operations, elements, portions, or combinations thereof, but are not intended to preclude the presence or addition of one or more other features, quantities, steps, operations, elements, portions, or combinations thereof.
The embodiment of the invention provides a preparation method of a sulfide electrolyte membrane, which comprises the following steps:
s1, providing a sulfide electrolyte and an inorganic fiber fabric;
and S2, placing the sulfide electrolyte on an inorganic fiber fabric, and performing tabletting treatment and sintering treatment to obtain the sulfide electrolyte membrane.
According to the preparation method of the sulfide electrolyte membrane, the sulfide electrolyte is placed on the inorganic fiber fabric, and is subjected to tabletting treatment and sintering treatment, so that the sulfide electrolyte is loaded on the surface of the inorganic fiber fabric and/or in the pores of the inorganic fiber fabric. Firstly, the inorganic fiber fabric has a larger specific surface area and is used as a supporting material of sulfide electrolyte, the network skeleton structure of the inorganic fiber fabric has non-fluidity, and the sulfide electrolyte can be bound in a micro area, so that the contact interface between sulfide electrolyte particles is changed from a point contact interface to a surface contact interface, the contact area is improved, and the defect of more pores is overcome; secondly, the inorganic fiber fabric is inert and does not react with sulfide electrolyte, and the problems of combustion, melting, toxic gas generation and the like caused by heating can be avoided in the sintering process; finally, through sintering treatment, the sulfide electrolyte and the inorganic fiber fabric jointly form a uniform, compact and flexible sulfide electrolyte membrane, and the problems that the sulfide electrolyte is easy to pulverize and difficult to transfer are solved.
Specifically, in S1, the sulfide electrolyte has high conductivity, but is brittle and easily pulverized, and it is difficult to form the sulfide electrolyte into a sheet or film form, so that commercially available sulfide electrolytes are all powders, which makes battery assembly inconvenient. In some embodiments, the sulfide electrolyte is selected from Li2S-SiS2、Li2S-P2S5、LiX-Li2S-SiS2、LiX-Li2S-P2S5Wherein, X is a halogen element, and the specific proportion can be adjusted according to the actual situation so as to improve the cost performance of the obtained sulfide electrolyte membrane.
The sulfide electrolyte provided by the embodiment of the invention can be directly purchased and can also be obtained by mixing and ball-milling raw materials of the sulfide electrolyte. In some embodiments, a small amount of an inert liquid solvent, such as heptane, is also added to the sulfide electrolyte feedstock to facilitate ball milling and dispersion of the feedstock particles.
The inorganic fiber fabric has a plurality of pores formed by a certain weave structure, and the shape of the pores can be the same or different, as shown in figure 1. The inorganic fiber fabric has inertia and high temperature resistance, can not react with sulfide electrolyte, and can avoid the problems of combustion, melting, toxic gas generation and the like during high-temperature sintering treatment. In some embodiments, the inorganic fiber fabric is a porous quartz fiber cloth or an alumina fiber cloth. Porous stoneThe quartz fiber cloth is woven by taking quartz fiber as a raw material according to a certain weave structure (plain weave, twill weave, satin weave and the like). Wherein the quartz fiber is an inorganic fiber prepared from high-purity quartz or natural crystal, and has a diameter of several micrometers to tens of micrometers, and SiO2The content of the active component reaches more than 99.9 percent. The quartz fiber keeps the high temperature resistance, the electrical insulation performance, the ablation resistance and the thermal shock resistance of solid quartz, and the porous quartz fiber cloth prepared by taking the quartz fiber as the raw material has the advantages of higher surface through hole rate, good flexibility, high mechanical strength and high retention rate at high temperature. The aluminum oxide fiber cloth also has the advantages of no reaction with sulfide electrolyte, low cost and wide source.
In some embodiments, the inorganic fiber fabric with the thickness of 10 μm to 200 μm is selected, which is beneficial to obtain a sulfide electrolyte membrane with a thinner thickness, so as to improve the conductivity of the sulfide electrolyte membrane and avoid the problem of high resistance caused by an excessively thick inorganic fiber fabric.
In some embodiments, the inorganic fiber fabric with the porosity of more than 80% and the open pore diameter of 200 μm to 5mm is selected, and the appropriate porosity and open pore diameter can enable the inorganic fiber fabric to reduce the resistance of the sulfide electrolyte as much as possible while providing support for the sulfide electrolyte so as to improve the electrical conductivity of the obtained sulfide electrolyte membrane.
S2, placing the sulfide electrolyte on an inorganic fiber fabric, tabletting to improve the density of the sulfide electrolyte, sintering to form an integral body between sulfide electrolyte particles, and increasing the bonding force between the sulfide electrolyte and the inorganic fiber fabric, so that the obtained sulfide electrolyte membrane has good integrity. In some embodiments, the manner of disposing the sulfide electrolyte on the inorganic fiber fabric may be specifically employed in various ways. Such as coating the sulfide electrolyte on the surface of the inorganic fiber fabric, in such a manner that the thickness of the resulting sulfide electrolyte membrane can be easily controlled; or placing the inorganic fiber fabric in a module with a preset size and shape, wherein the module is made of inert inorganic materials such as aluminum oxide or quartz glass and the like so as to avoid reaction with sulfide electrolyte, and the module can be used as a substrate in the subsequent sintering treatment process; and then the sulfide electrolyte is placed on the inorganic fiber fabric, and at the moment, the module exists below the inorganic fiber fabric, so that the sulfide electrolyte is concentrated at the position of the module, the mode is favorable for subsequent tabletting treatment, and the sulfide electrolyte in the obtained sulfide electrolyte membrane is more compact.
The sulfide electrolyte was placed on an inorganic fiber fabric, which was then subjected to a tabletting treatment using a tabletting device. The embodiment of the invention has no particular limitation on the specific selection of the tabletting device, and the hydraulic press and the like can be selected according to the actual situation. In some embodiments, since the material of the tabletting device is mostly metal-containing and is easy to react with the sulfide electrolyte, it is necessary to separate the sulfide electrolyte from the metal of the tabletting device by using a part made of an inert inorganic material, such as a bottom plate of a workbench for placing the sulfide electrolyte and the inorganic fiber fabric, a part for applying pressure to the sulfide electrolyte and the inorganic fiber fabric, a side plate for limiting, and the like, so as to improve the performance of the obtained sulfide electrolyte membrane. Taking a vertical hydraulic press as an example, a module made of inert inorganic material is placed below a workbench, then an inorganic fiber fabric with sulfide electrolyte is placed above the module, a pressure maintaining block made of inert inorganic material is placed on the top of the module, and meanwhile, limiting frames made of inert inorganic material are arranged on two sides of the workbench. In the case where the material facing the sulfide electrolyte in the member to which pressure is applied is an inert inorganic material, the pressure maintaining block may not be used.
In the pressed sheet obtained by pressing treatment, sulfide electrolyte and inorganic fiber fabric are combined preliminarily, sulfide electrolyte particles are located on the surface of the inorganic fiber fabric under the action of pressure, and some particles are located in pores of the inorganic fiber fabric, but the combination between the sulfide electrolyte particles and the inorganic fiber fabric is not tight enough, so that the requirements of the transportation and assembly processes cannot be met. Therefore, after the tabletting treatment, the obtained pressed sheet is sintered to sinter the sulfide electrolyte particles into a whole, improve the binding force between the sulfide electrolyte and the inorganic fiber fabric and improve the compactness of the obtained sulfide electrolyte membrane, and the obtained sulfide electrolyte membrane is shown in figure 2. As can be seen from fig. 2, a sulfide electrolyte is bonded to both the surface and the pores of the inorganic fiber fabric. In some embodiments, in order to further increase the compactness of the obtained sulfide electrolyte membrane, a module made of an inert inorganic material may be used as a substrate in the sintering process, and a pressure maintaining block made of an inert inorganic material may be placed on top of the pressed sheet and co-placed in a sintering apparatus for sintering.
In some embodiments, the sintering device is a microwave sintering device. The sulfide electrolyte is a microwave sensitive material, the bulk temperature of the sulfide electrolyte can rapidly rise when the sulfide electrolyte is irradiated by microwaves, meanwhile, the inert inorganic material also belongs to a heat-vibration-resistant and high-temperature-resistant material, and a module substrate and a pressure maintaining block made of the material can be transmitted through the microwaves when the module substrate and the pressure maintaining block are irradiated by the microwaves.
In some embodiments, the sintering temperature is controlled between 230 ℃ and 260 ℃. By optimizing the sintering temperature, the sulfide electrolyte and the inorganic fiber fabric can form a compact and complete sulfide electrolyte membrane, and the influence of an excessively high sintering temperature on the performance of the sulfur compound electrolyte can be avoided. Specifically, typical, but not limiting, sintering temperatures are 230 ℃, 235 ℃, 240 ℃, 245 ℃, 250 ℃, 255 ℃, 260 ℃.
In some embodiments, the sintering time is 2min to 30 min. By optimizing the sintering treatment time, the sulfide electrolyte and the inorganic fiber fabric can form a compact and complete sulfide electrolyte membrane, and the problems of structural deformation of the obtained sulfide electrolyte membrane and the like caused by overlong sintering treatment time can be avoided. Specifically, typical, but not limiting, sintering times are 2min, 5min, 10min, 15min, 20min, 25min, 30 min.
Accordingly, the embodiment of the invention also provides a sulfide electrolyte membrane, which comprises a sulfide electrolyte and an inorganic fiber fabric, wherein the sulfide electrolyte is loaded on the surface of the inorganic fiber fabric and/or in the pores of the inorganic fiber fabric.
In the sulfide electrolyte membrane provided by the embodiment of the invention, the sulfide electrolyte is loaded on the surface of the inorganic fiber fabric and/or in the pores of the inorganic fiber fabric. The inorganic fiber fabric has a larger specific surface area and is used as a supporting material of the sulfide electrolyte, and the network skeleton structure of the inorganic fiber fabric has non-fluidity, so that the sulfide electrolyte can be bound in a micro area, the contact interface between sulfide electrolyte particles is changed from a point contact interface to a surface contact interface, the contact area is increased, and the defect of more pores is overcome; and the inorganic fiber fabric is inert, does not react with sulfide electrolyte and has good stability. The sulfide electrolyte membrane provided by the invention is uniform and compact, has certain flexibility, has the advantages of no powder falling and convenience in transferring and assembling the solid-state battery, is beneficial to realizing large-scale production, and has good application prospect and market value.
The sulfide electrolyte and the inorganic fiber fabric in the sulfide electrolyte membrane provided in the embodiment of the present invention are as described in the foregoing method for preparing the sulfide electrolyte membrane, and are not described herein again.
The thickness of the sulfide electrolyte membrane is 20-200 mu m, and the electrolyte membrane using the thickness range still has the anti-cracking or anti-puncturing performance according to the requirements of assembling the solid-state battery, so that the safety performance of the obtained solid-state battery can be improved.
Accordingly, the present invention also provides a solid-state battery comprising the sulfide electrolyte membrane produced by the above-described sulfide electrolyte membrane production method, or the above-described sulfide electrolyte membrane.
The solid-state battery provided by the embodiment of the invention comprises the sulfide electrolyte membrane, and the sulfide electrolyte membrane loads the sulfide electrolyte which is originally in powder form on the surface of the inorganic fiber fabric and/or in the pores of the inorganic fiber fabric, so that the advantages of no powder falling and more convenient assembly of the solid-state battery by transfer are achieved, and the solid-state battery comprising the sulfide electrolyte membrane also has the advantages of convenient assembly and contribution to realizing large-scale production.
In order to make the details and operation of the above-described embodiment of the present invention clearly understood by those skilled in the art and to make the progress of the sulfide electrolyte membrane, the method of manufacturing the same, and the solid-state battery of the embodiment of the present invention remarkably manifest, the above-described technical solution is exemplified by a plurality of examples below.
Example 1
The present embodiment provides a method for producing a sulfide electrolyte membrane, including the steps of:
(11) under the inert atmosphere environment, adopting sulfide electrolyte Li7P3S11Ball-milling raw materials of sulfide electrolyte for several hours in an inert atmosphere, taking out the milled mixture, placing it on a porous quartz fiber cloth having a thickness of 20 μm and an open pore diameter of 0.20mm, and placing the porous quartz fiber cloth in advance at a predetermined size of 10X 10cm2Vibrating the aluminum oxide module to make sulfide electrolyte particles compact, and applying pressure by using a hydraulic machine to obtain a pressed sheet;
(12) and (3) taking an aluminum oxide module as a substrate, placing a pressing sheet on the aluminum oxide module, placing a pressure maintaining block on the top of the pressing sheet, sintering in a microwave oven at the sintering temperature of 230 ℃ for 10 minutes, then keeping the pressure and cooling, and disassembling the module to obtain the transferable sulfide electrolyte membrane without powder falling.
Example 2
(21) Under the inert atmosphere environment, adopting sulfide electrolyte Li6PS5Cl, ball-milling the raw material of the sulfide electrolyte for several hours in an inert atmosphere, taking out the milled mixture, placing it on a porous quartz fiber cloth having a thickness of 40 μm and an open pore diameter of 0.25mm, and placing the porous quartz fiber cloth in advance at a predetermined size of 10X 10cm2Vibrating in a quartz glass module with the shape and size to enable sulfide electrolyte particles to be compact, and then applying pressure by using a hydraulic press to obtain a pressed sheet;
(22) and (3) taking an aluminum oxide module as a substrate, placing a pressing sheet on the aluminum oxide module, placing a pressure maintaining block on the top of the pressing sheet, sintering in a microwave oven at the sintering temperature of 230 ℃ for 8 minutes, then keeping the pressure and cooling, and disassembling the module to obtain the transferable sulfide electrolyte membrane without powder falling.
Examples of the experiments
Operating in inert atmosphere environment and adopting sulfide electrolyte raw material Li2S、P2S5Proportioning Li7P3S11And filled into a quartz glass vessel (as shown in fig. 3), and heated in a microwave oven for 8 minutes, and the resultant sintered product is shown in fig. 4.
Comparing the sulfide electrolyte before and after heating through fig. 3 and fig. 4, it can be seen from fig. 1 that the mixture obtained by ball milling is light yellow sandy powder; it can be seen from fig. 2 that, after the heating treatment by the microwave oven, the color of the sulfide electrolyte becomes dark, the powder is seen to be in a bulk shape through the quartz glass bottle, no obvious adhesive is left on the wall of the quartz glass vessel, and the bonding force of sulfide electrolyte particles can be improved through the sintering treatment, so that the sulfide electrolyte is more compact.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. A method for producing a sulfide electrolyte membrane, characterized by comprising the steps of:
providing a sulfide electrolyte and an inorganic fiber fabric;
and placing the sulfide electrolyte on the inorganic fiber fabric, and performing tabletting treatment and sintering treatment to obtain the sulfide electrolyte membrane.
2. The production method for a sulfide electrolyte membrane according to claim 1, wherein the inorganic fiber fabric is a porous quartz fiber cloth or an alumina fiber cloth.
3. The production method for a sulfide electrolyte membrane according to claim 1, wherein the thickness of the inorganic fiber fabric is 10 μm to 200 μm.
4. The method for producing a sulfide electrolyte membrane according to claim 1, wherein the inorganic fiber fabric has a porosity of 80% or more and an open pore diameter of 200 μm to 5 mm.
5. The production method for a sulfide electrolyte membrane according to any one of claims 1 to 4, wherein the temperature of the sintering treatment is 230 ℃ to 260 ℃; and/or
The sintering treatment time is 2min-30 min.
6. The production method for a sulfide electrolyte membrane according to any one of claims 1 to 4, wherein the sulfide electrolyte is selected from Li2S-SiS2、LiX-Li2S-SiS2、Li2S-P2S5、LiX-Li2S-P2S5Wherein X is a halogen element.
7. A sulfide electrolyte membrane, characterized in that the sulfide electrolyte membrane comprises a sulfide electrolyte and an inorganic fiber fabric, and the sulfide electrolyte is supported on the surface of the inorganic fiber fabric and/or in the pores of the inorganic fiber fabric.
8. The sulfide electrolyte membrane according to claim 7, wherein the inorganic fiber fabric is a porous quartz fiber cloth or an alumina fiber cloth.
9. The sulfide electrolyte membrane according to claim 7, wherein the thickness of the sulfide electrolyte membrane is 20 μm to 200 μm; and/or
The thickness of the inorganic fiber fabric is 20-200 μm; and/or
The inorganic fiber fabric has a porosity of more than 80% and an opening pore diameter of 200 μm-5 mm.
10. A solid-state battery comprising the sulfide electrolyte membrane produced by the method for producing a sulfide electrolyte membrane according to any one of claims 1 to 6, or the sulfide electrolyte membrane according to any one of claims 7 to 9.
CN202010796448.4A 2020-08-10 2020-08-10 Sulfide electrolyte membrane, preparation method thereof and solid-state battery Pending CN114075083A (en)

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