CN116745958A

CN116745958A - Solid electrolyte membrane based on porous frame, method for manufacturing same, and all-solid battery including same

Info

Publication number: CN116745958A
Application number: CN202280007523.1A
Authority: CN
Inventors: 李永琦; 姜锡勋; 金道桓; 金东贤; 卢永晙; 宋枝勋; 安珍赫; 李镕敏; 张恩光; 赵国泳; 崔会柱; 河会珍
Original assignee: Electronics and Telecommunications Research Institute ETRI; Industry University Cooperation Foundation IUCF HYU; Daegu Gyeongbuk Institute of Science and Technology; LG Energy Solution Ltd
Current assignee: Electronics and Telecommunications Research Institute ETRI; Industry University Cooperation Foundation IUCF HYU; Daegu Gyeongbuk Institute of Science and Technology; LG Energy Solution Ltd
Priority date: 2021-02-19
Filing date: 2022-02-18
Publication date: 2023-09-12

Abstract

The present invention provides a solid electrolyte membrane comprising: a porous frame comprising a metal or polymeric material; solid electrolyte particles that cover both surfaces of the porous frame and fill the pores of the porous frame; and a binder located between the solid electrolyte particles.

Description

Solid electrolyte membrane based on porous frame, method for manufacturing same, and all-solid battery including same

Technical Field

The present disclosure relates to a solid electrolyte membrane based on a porous frame, a method of manufacturing the same, and an all-solid battery including the solid electrolyte membrane based on the porous frame.

Background

Lithium ion batteries are an energy storage device having high energy density and stable output performance, and are variously applied to mobile information technology of Electric Vehicles (EV) and Energy Storage Systems (ESS). However, lithium ion batteries use organic electrolytes having a high risk of ignition and operate in a high voltage range, and fire accidents may occur due to unexpected behavior. Further, in recent years, the secondary battery industry is rapidly shifting from small secondary batteries such as power sources for portable devices to medium-sized and large secondary batteries such as electric vehicles and energy storage systems, so that stability problems become more serious.

In order to secure stability of the lithium ion battery, various methods are being applied. Among them, the development of solid electrolytes has become the biggest problem in recent years. When a ceramic-based solid electrolyte having a separator function is used, the structure of the battery is simplified, there is no risk of electrolyte leakage, ignition and explosion, and the use of high-voltage electrodes is not limited due to the excellent electrochemical stability of the electrolyte. Further, since lithium metal, the theoretical capacity of which is 10 times or more that of a commercially available graphite material, can be used as a typical anode material, the electrolyte can be extended to an electrolyte for a lithium air battery or a lithium sulfur battery, and thus, the energy density of mass and volume can be remarkably improved.

Disclosure of Invention

Technical problem to be solved

The present disclosure provides a thin film solid electrolyte membrane, a method of manufacturing the same, and an all-solid battery including the thin film solid electrolyte membrane.

Technical proposal

Embodiments of the inventive concept provide a solid electrolyte membrane including: a porous frame comprising a metal or polymeric material; solid electrolyte particles that cover both surfaces of the porous frame and fill the pores of the porous frame; and a binder located between the solid electrolyte particles.

In an embodiment of the inventive concept, a method of manufacturing a solid electrolyte membrane includes: stirring a mixture including solid electrolyte particles and a binder, disposing the mixture on a surface of a porous frame, and compressing the porous frame on which the mixture is disposed, wherein the porous frame includes a metal or a polymer material, and the solid electrolyte particles and the binder cover both surfaces of the porous frame and fill pores of the porous frame.

In an embodiment of the inventive concept, an all-solid battery includes a positive electrode, a negative electrode, and a solid electrolyte, wherein the solid electrolyte may be a solid electrolyte membrane.

Effects of the invention

According to the inventive concept, the solid electrolyte membrane has a thickness and mechanical strength similar to those of a typical commercially available separator. Thus, the solid electrolyte membrane can be used for deformation and pressing, such as bending or rolling, at any time, and the solid electrolyte membrane is easily allowed to have a large area. Further, when the battery is manufactured, an additional pressurizing condition is relaxed, and the structure of the battery is simplified, so that the manufacturing process cost of the battery is reduced.

According to the inventive concept, unlike typical commercially available separators, the solid electrolyte membrane itself has lithium ion conductivity properties. Thus, the solid electrolyte membrane exhibits ion conductivity properties that are close to those of an electrolyte system including a separator and a liquid electrolyte.

The effects to be obtained by the present invention are not limited to the above-described effects, and other effects not mentioned will be clearly understood by those skilled in the art from the above description.

Drawings

Fig. 1 is a schematic perspective view illustrating a porous frame-based solid electrolyte membrane according to some embodiments of the inventive concept.

Fig. 2 and 3 are cross-sectional views illustrating a solid electrolyte membrane based on a porous frame according to some embodiments of the inventive concept.

Fig. 4 is a plan view illustrating a porous frame-based solid electrolyte membrane according to some embodiments of the inventive concept.

Fig. 5 is a flowchart for describing a method for manufacturing a porous frame-based solid electrolyte membrane according to some embodiments of the inventive concept.

Fig. 6 is a cross-sectional view schematically illustrating an all-solid battery including a solid electrolyte membrane based on a porous frame according to some embodiments of the inventive concept.

Fig. 7 is a graph showing the room temperature ion conductivity performance of the solid electrolyte membrane of each of experimental examples 1 to 8 and comparative example 1.

Fig. 8 is a graph showing initial specific capacitance of a single cell based on a solid electrolyte membrane and specific capacitance holding performance according to service life according to each of experimental examples 9 to 16 and comparative example 2.

Detailed Description

In order to facilitate a full understanding of the configuration and effect of the inventive concept, preferred embodiments of the inventive concept will be described with reference to the accompanying drawings. However, the inventive concept is not limited to the embodiments set forth below, and may be embodied in various forms and may be modified in many alternative forms. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the inventive concept to those skilled in the art to which the inventive concept pertains. In the drawings, elements are shown exaggerated from their actual sizes for convenience of description, and the proportion of each element may be exaggerated or reduced.

Fig. 1 is a schematic perspective view illustrating a porous frame-based solid electrolyte membrane according to some embodiments of the inventive concept. Fig. 2 and 3 are cross-sectional views illustrating a solid electrolyte membrane based on a porous frame according to some embodiments of the inventive concept.

Referring to fig. 1 to 3, the solid electrolyte membrane 100 may include a porous frame 10, solid electrolyte particles 20, and a binder 30.

The porous frame 10 may comprise a metal or polymeric material. The porous frame 10 may include: holes 40 penetrating the inside of the porous frame 10. The holes 40 may be empty spaces extending from the upper surface 50a of the porous frame to the lower surface 50b thereof. The holes 40 may be provided in the porous frame 10 in a plurality, and the plurality of holes 40 may be provided spaced apart from each other. The thickness t1 of the porous frame 10 may be 1um to 200um.

The porous frame 10 may comprise a polymeric material. As an example, the polymeric material may include at least one of the following: polyethylene (PE), polypropylene (PP), cellulose, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyacrylonitrile (PAN), polystyrene (PS), polyvinylchloride (PVC), polycarbonate (PC), polymethyl methacrylate (PMMA), nylon, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), copolymers of vinylidene fluoride and hexafluoropropylene (PVDF-HFP), polyimide (PI), polyisoimide (PEI), liquid crystal polymer film (LCP), polyoxymethylene (POM), polysiloxane, acrylonitrile-butadiene-styrene (ABS), epoxy resin, phenolic resin, polysulfone (PSF), polyethersulfone (PEs) or Polyetherketone (PEEK). When the porous frame 10 includes a polymer material, the porous frame 10 may be in the form of a film made of the polymer material.

The porous frame 10 may include a metal material. As an example, the metal material may include at least one of the following: cu, al, ni, stainless steel (SUS), ti, zn or Mg. The porous frame 10 may be in the form of a foil made of a metallic material.

When the porous frame 10 includes a metal material, it may be provided that: an insulating layer 90 covering both surfaces 50 of the porous frame 10 and the inner surfaces of the pores 40. The insulating layer 90 may reduce occurrence of short circuits or leakage currents in the battery, and may improve adhesion of the solid electrolyte particles 20 to the porous frame 10. The thickness t2 of the insulating layer 90 may be 10nm to 10um, and may be smaller than the thickness t1 of the porous frame 10.

The insulating layer 90 may include a metal oxide film. As an example, the metal oxide film may include at least one of: copper oxide (CuO), aluminum oxide (Al) ₂ O ₃ ) Nickel oxide (NiO, ni) ₂ O ₃ Or NiO ₂ ) Iron oxideFeO、Fe ₂ O ₃ Or Fe (Fe) ₃ O ₄ ) Titanium oxide (TiO) ₂ ) Zinc oxide (ZnO) or magnesium oxide (MgO).

The solid electrolyte particles 20 may cover both surfaces 50 of the porous frame 10 and may fill the pores 40 of the porous frame 10. The solid electrolyte particles 20 may include a lithium ion conductive material. As an example, the lithium ion conductive material may include at least one of the following: NASICON-based electrolytes (LATP, LAGP), oxide-based electrolytes (garnet structure LLZO, perovskite LLTO), sulfide-based electrolytes (LPS, LPSCl), or polymer electrolytes (electrolytes without solvent-based and gel).

The binder 30 may be disposed between the solid electrolyte particles 20. The composition ratio of the solid electrolyte particles 20 and the binder 30 may be (by weight) 20:80 to 99:1. When the composition ratio of the binder 30 is higher than the numerical range set forth above, the ion conductivity of the solid electrolyte membrane 100 may be reduced. When the composition ratio of the binder 30 is lower than the above-mentioned numerical range, the adhesion of the solid electrolyte particles 20 to the porous frame 10 may be reduced.

Referring to fig. 4, the hole 40 may be circular. When the holes 40 are circular, the diameter D1 of the holes 40 may be 0.1um to 50000um, and the distance D2 from the center of the hole 40 to the center of the nearest neighboring hole 40 may be 0.15um to 75000um.

Hereinafter, a method for manufacturing a solid electrolyte membrane based on a porous frame according to the inventive concept will be described.

Referring to fig. 1 and 5, a method for manufacturing a solid electrolyte membrane according to an embodiment of the inventive concept may include: stirring the mixture S1 including the solid electrolyte particles 20 and the binder 30, disposing the mixture S2 on the surface of the porous frame 10, and compressing the porous frame 10S3 on which the mixture is disposed. The porous frame 10 may comprise a metal or polymeric material. The solid electrolyte particles 20 and the binder 30 may cover both surfaces of the porous frame 10, and may fill the pores 40 of the porous frame 10.

According to some embodiments, the mixture may further comprise a co-solvent. In this case, the method for manufacturing the solid electrolyte membrane may include: wet processing (wet process) is performed using the mixture.

Hereinafter, a method for manufacturing a solid electrolyte membrane based on wet processing will be described in more detail.

The mixture comprising solid electrolyte particles 20 and binder 30 may also comprise a co-solvent. As an example, the adhesive 30 may include at least one of the following: butadiene rubber, fluororubber, nitrile rubber, hydrogenated nitrile rubber, styrene butadiene rubber, styrene-butadiene-styrene, styrene-ethylene-butadiene-styrene, acrylated styrene-butadiene rubber, acrylonitrile-butadiene-styrene copolymer, polytetrafluoroethylene, polyvinylidene fluoride, copolymer of vinylidene fluoride and hexafluoropropylene, polyvinyl chloride, polyacrylonitrile, polymethyl methacrylate, polyacrylate, polyethylene, polypropylene, polyethylene oxide, polyimide, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polyether ether ketone, or tetrafluoroethylene. As an example, the co-solvent may include at least one of the following: hexane, heptane, nonane, decane, benzene, toluene, xylene, anisole, cyclohexanone, methyl ethyl ketone, tetrahydrofuran, N-methylpyrrolidone, hexamethylphosphoramide, dioxane, tetramethylurea, triethyl phosphate, trimethyl phosphate, dimethylformamide, dimethyl sulfoxide or dimethylacetamide.

Hereinafter, as an example of a method for manufacturing a solid electrolyte membrane based on wet processing, the step S2 of disposing the mixture on the surface of the porous frame 10 may include: the mixture is directly coated on both surfaces 50 of the porous frame 10 and on the inner surfaces of the pores 40.

Hereinafter, as another example of the method for manufacturing a solid electrolyte membrane based on wet processing, the method for manufacturing a solid electrolyte membrane may further include: after step S1 of stirring the mixture including the solid electrolyte particles 20 and the binder 30, the mixture is cast and the co-solvent of the mixture is dried to manufacture a solid electrolyte thin film. In this case, the step S2 of disposing the mixture on the surface of the porous frame 10 may include: a solid electrolyte membrane is laminated on both surfaces 50 of the porous frame 10 and on the inner surfaces of the pores 40.

According to other embodiments, the mixture may not include a co-solvent. In this case, the method for manufacturing the solid electrolyte membrane may include: dry processing is performed using the mixture.

Hereinafter, a method for manufacturing a solid electrolyte membrane based on dry processing will be described in more detail.

The method for manufacturing a solid electrolyte membrane based on dry processing may further include: after stirring the mixture including the solid electrolyte particles 20 and the binder 30, an aprotic solvent or a nonpolar solvent is added to the mixture. During stirring, the temperature may be 25 ℃ to 100 ℃.

As an example, the adhesive 30 may include at least one of the following: polytetrafluoroethylene, polyvinylidene fluoride, copolymers of vinylidene fluoride and hexafluoropropylene, copolymers of vinylidene fluoride and trifluoroethylene, or terpolymers of vinylidene fluoride, trifluoroethylene and chlorotrifluoroethylene.

Aprotic or nonpolar solvents have low boiling points and can therefore be readily volatilized. As an example, the aprotic solvent or the nonpolar solvent may include at least one of the following: hexane, benzene, toluene, xylene, cyclohexanone or methyl ethyl ketone. The mixture to which the aprotic solvent or the nonpolar solvent is added may temporarily exhibit fluidity. The composition ratio of the mixture and the aprotic solvent or the nonpolar solvent may be (by weight) 1:0.05 to 1:2. When the composition ratio of the aprotic solvent or the nonpolar solvent is higher than the numerical range set forth above, the fluidity of the mixture to which the aprotic solvent or the nonpolar solvent is added is high, so that the thickness of the solid electrolyte membrane 100 may not be easily controlled. When the composition ratio of the aprotic solvent or the nonpolar solvent is lower than the numerical range set forth above, the fluidity of the mixture to which the aprotic solvent or the nonpolar solvent is added is low, so that the mixture may not be easily handled.

Hereinafter, as an example of a method for manufacturing a solid electrolyte membrane based on dry processing, the step S2 of disposing the mixture on the surface of the porous frame 10 may include: the mixture to which the aprotic solvent or the nonpolar solvent is added is directly coated on both surfaces 50 of the porous frame 10 and the inner surfaces of the pores 40.

Hereinafter, as another example of the method for manufacturing a solid electrolyte membrane based on dry processing, the method for manufacturing a solid electrolyte membrane may further include: after step S1 of stirring the mixture including the solid electrolyte particles 20 and the binder 30, the mixture to which the aprotic solvent or the nonpolar solvent is added is cast and cooled to manufacture a solid electrolyte thin film. The step S2 of disposing the mixture on the surface of the porous frame 10 may include: a solid electrolyte membrane is laminated on both surfaces 50 of the porous frame 10 and on the inner surfaces of the pores 40.

Referring to fig. 6, the all-solid battery may include a positive electrode 110, a negative electrode 120, and a solid electrolyte membrane, and the solid electrolyte membrane may be any one of the above-described solid electrolyte membranes 100.

Fig. 7 is a graph showing the room temperature ion conductivity performance of the solid electrolyte membrane of each of experimental examples 1 to 8 and comparative example 1. Hereinafter, experimental examples 1 to 8 and comparative example 1 will be described in detail.

Experimental example 1

A solid electrolyte membrane is manufactured by wet processing in which LPSCl is used as solid electrolyte particles and nitrile rubber (NBR) is used as a binder. The porous frame is composed of nickel, and the circular holes are arranged at regular intervals. The solid electrolyte membrane was manufactured such that the average diameter of the pores was 200um, the interval between the pores was 760um, and the porosity of the frame was 23%, and the thickness of the frame was 10um. For the purpose of insulation by surface oxidation treatment, niO oxide layers with a thickness of 25nm were formed on both surfaces. A mixture was prepared in which LPSCl (sulfur silver germanium ore) and NBR were dissolved in a 1:1 by weight composition ratio in a co-solvent of xylene/cyclohexanone mixture. The concentration of cyclohexanone in the xylene solvent was 40%. The mixture was coated on one surface of the porous frame and dried at room temperature, and then the mixture was coated again on the opposite side of the porous frame and dried at room temperature to manufacture a solid electrolyte membrane having both surfaces coated. Thereafter, the solid electrolyte membrane was compressed, and finally, a solid electrolyte membrane having a thickness of 25um was manufactured. Blocking electrodes (SUS/solid electrolyte membrane/SUS) were applied to both surfaces of the manufactured solid electrolyte membrane, and ion conductivity of the solid electrolyte membrane was calculated by impedance measurement at room temperature.

(Experimental example 2)

Unlike experimental example 1, the mixture was cast on a polytetrafluoroethylene sheet and then dried at room temperature to manufacture a solid electrolyte thin film. The same process as in experimental example 1 was performed except that a solid electrolyte thin film was applied to both surfaces of the nickel porous frame to manufacture a solid electrolyte thin film by lamination at 40 ℃.

(Experimental example 3)

The solid electrolyte membrane was produced by wet processing in which LPSCl was used as the solid electrolyte particles and PTFE particles were used as the binder in a weight ratio of 98:2. The average diameter of the PTFE particles was 10. Mu.m. The mixture of LPSCl and PTFE particles was continuously stirred and melted at 40 ℃ to form a liquid mixture. After that, methyl Ethyl Ketone (MEK) was added so that the composition ratio of the mixture and MEK (aprotic solvent or nonpolar solvent) was 1:0.3 by weight, and a solid electrolyte membrane was produced by coating and room temperature drying treatment in the same manner as in experimental example 1.

(Experimental example 4)

A liquid mixture (whose viscosity was controlled with MEK) was produced in the same manner as in experimental example 3, and a solid electrolyte membrane was produced by lamination treatment under the same conditions as in experimental example 2.

(Experimental example 5)

The same processing as in experimental example 1 was performed except that LPSCl and NBR were applied in a composition ratio of 99:1 by weight.

(Experimental example 6)

The same processing as in experimental example 2 was performed except that LPSCl and NBR were applied in a composition ratio of 99:1 by weight.

(Experimental example 7)

The same processing as in experimental example 3 was performed except that LPSCl and PTFE were applied in a composition ratio of 99:1 by weight.

(Experimental example 8)

The same processing as in experimental example 4 was performed except that LPSCl and PTFE were applied in a composition ratio of 99:1 by weight.

Comparative example 1

The LPSCl solid electrolyte particles were pressurized to 500MPa to produce solid electrolytes in the form of particles having a thickness of 400um and a diameter of 1.2 cm. Blocking electrodes (SUS/solid electrolyte/SUS) were applied to both surfaces of the manufactured solid electrolyte, and ion conductivity of the solid electrolyte was calculated by impedance measurement at room temperature.

Referring to fig. 7, it can be observed that: the ion conductivity of each of experimental examples 1 to 8 as a solid electrolyte in a film form was close to that of comparative example 1 as a typical solid electrolyte in a particle form. This is probably because lithium ions move only within the porous structure, and thus, loss of ion conductivity is minimized due to a simple and short movement path. Therefore, the solid electrolyte in the form of a film of each of experimental examples 1 to 8 has the advantage of being thinner and larger due to the high tensile strength of the porous frame, while maintaining the similar level of ion conductivity, as compared to comparative example 1.

Fig. 8 is a graph showing initial specific capacitance of a single cell based on a solid electrolyte membrane and specific capacitance holding performance according to service life according to each of experimental examples 9 to 16 and comparative example 2. Hereinafter, experimental examples 9 to 16 and comparative example 2 will be described in detail.

(Experimental example 9)

Individual cells (single cells) of all-solid-state batteries to which a solid electrolyte membrane was applied were manufactured. As the negative electrode, a lithium foil of 50um thickness laminated on a copper current collector was used. The positive electrode active material NCM622, the solid electrolyte LPSCl, and NBR and the conductive additive (carbon black, super-P) were mixed in a weight ratio of 80:10:5:5, and the mixture was dissolved in a xylene co-solvent and stirred to prepare a slurry. The slurry was coated on an aluminum current collector and rolled to finally manufacture a positive electrode having a thickness of 30 um. The solid electrolyte membrane manufactured in experimental example 1 was interposed between two electrodes to manufacture a soft-packed cell (2 cm×2 cm). Separate JIG is applied to maintain compression on both surfaces of the pouch cell. The pouch cell is connected to a charger/discharger, and CC-CV/CC charging/discharging is performed under a cut-off condition of 3.0 to 4.3V and a current condition of C/5.

(Experimental example 10)

The same processing as in experimental example 9 was performed except that the solid electrolyte membrane of experimental example 2 was applied.

(Experimental example 11)

The same processing as in experimental example 9 was performed except that the solid electrolyte membrane of experimental example 3 was applied.

(Experimental example 12)

The same processing as in experimental example 9 was performed except that the solid electrolyte membrane of experimental example 4 was applied.

Experimental example 13

The same processing as in experimental example 9 was performed except that the solid electrolyte membrane of experimental example 5 was applied.

(Experimental example 14)

The same processing as in experimental example 9 was performed except that the solid electrolyte membrane of experimental example 6 was applied.

(Experimental example 15)

The same processing as in experimental example 9 was performed except that the solid electrolyte membrane of experimental example 7 was applied.

(Experimental example 16)

The same processing as in experimental example 9 was performed except that the solid electrolyte membrane of experimental example 8 was applied.

Comparative example 2

A single cell to which the LPSCl solid electrolyte particles of comparative example 1 were applied was manufactured. As the negative electrode, a lithium foil of 50um thickness laminated on a copper current collector was used. The positive electrode active material NCM622, solid electrolyte LPSCl and conductive additive (carbon black, super-P) were mixed in a weight ratio of 70:25:5, and the mixture was pressurized to 500MPa to produce a positive electrode in the form of particles having a thickness of 450um and a diameter of 1.2 cm. The solid electrolyte particles manufactured in comparative example 1 were inserted between two electrodes and into a pressurized JIG to form a pressurized battery. The pressurized battery except for its terminal is again placed in a sealed container to block contact with moisture and air. The pressurized battery is connected to a charger/discharger, and CC-CV/CC charging/discharging is performed under a cut-off condition of 3.0 to 4.3V and a current condition of C/5.

Referring to fig. 8, it can be observed that: the individual cell of each of experimental examples 9 to 16 to which the solid electrolyte membrane was applied had excellent initial specific capacitance as compared to the initial specific capacitance of the individual cell of comparative example 2 to which the typical solid electrolyte membrane in the form of particles was applied. Furthermore, it can be observed that: even when charge/discharge was repeated 500 times, the specific capacitance of the single cell of each of experimental examples 9 to 16 was larger than that of comparative example 2, so that it could be confirmed that: experimental examples 9 to 16 have excellent specific capacitance holding performance according to service life, compared to comparative example 2.

Embodiments of the present invention have been described with reference to the accompanying drawings. However, the present invention may be embodied in other specific forms without changing its technical spirit or essential characteristics. Accordingly, it should be understood that the above-described embodiments are illustrative in all respects, rather than restrictive.

Claims

1. A solid electrolyte membrane comprising:

a porous frame comprising a metal or polymeric material;

solid electrolyte particles that cover both surfaces of the porous frame and fill pores of the porous frame; and

a binder located between the solid electrolyte particles.

2. The solid electrolyte membrane according to claim 1, wherein the porous frame has a thickness of 1um to 200um.

3. The solid electrolyte membrane according to claim 1, wherein the porous frame comprises a metal, and the solid electrolyte membrane further comprises an insulating layer covering both surfaces of the porous frame and inner surfaces of the pores.

4. The solid electrolyte membrane according to claim 3, wherein a thickness of the insulating layer is smaller than a thickness of the porous frame.

5. The solid electrolyte membrane according to claim 4, wherein the thickness of the insulating layer is 10nm to 10um.

6. The solid electrolyte membrane according to claim 3, wherein the insulating layer comprises a metal oxide thin film.

7. The solid electrolyte membrane according to claim 1, wherein a composition ratio of the solid electrolyte particles and the binder is 20:80 to 99:1 by weight.

8. The solid electrolyte membrane according to claim 1, wherein the holes are circular, the holes have a diameter of 0.1um to 50000um, and a distance from a center of the holes to a center of a nearest neighboring hole is 0.15um to 75000um.

9. A method for manufacturing a solid electrolyte membrane, the method comprising:

stirring a mixture comprising solid electrolyte particles and a binder;

disposing the mixture on a surface of a porous frame; and

compressing a porous frame provided with said mixture,

wherein:

the porous frame comprises a metal or polymeric material; and is also provided with

The solid electrolyte particles and the binder cover both surfaces of the porous frame and fill pores of the porous frame.

10. The method of claim 9, wherein the mixture further comprises a co-solvent, wherein the co-solvent comprises at least one of: hexane, heptane, nonane, decane, benzene, toluene, xylene, anisole, cyclohexanone, methyl ethyl ketone, tetrahydrofuran, N-methylpyrrolidone, hexamethylphosphoramide, dioxane, tetramethylurea, triethyl phosphate, trimethyl phosphate, dimethylformamide, dimethyl sulfoxide, or dimethylacetamide.

11. The method of claim 10, wherein disposing the mixture on a surface of the porous frame comprises: the mixture is directly coated on both surfaces of the porous frame and the inner surfaces of the pores.

12. The method of claim 10, further comprising:

casting the mixture; and

drying the co-solvent of the mixture to produce a solid electrolyte film,

wherein disposing the mixture on the surface of the porous frame comprises: the solid electrolyte membrane is laminated on both surfaces of the porous frame and the inner surfaces of the pores.

13. The method of claim 9, further comprising: adding an aprotic solvent or a nonpolar solvent to the mixture after stirring the mixture including the solid electrolyte particles and the binder, wherein the aprotic solvent or the nonpolar solvent includes at least one of: hexane, benzene, toluene, xylene, cyclohexanone, or methyl ethyl ketone.

14. The method of claim 13, wherein the composition ratio of the mixture and the aprotic solvent or the nonpolar solvent is 1:0.05 to 1:2 by weight.

15. The method of claim 14, wherein disposing the mixture on a surface of the porous frame comprises: the mixture to which the aprotic solvent or the nonpolar solvent is added is directly coated on both surfaces of the porous frame and the inner surfaces of the pores.

16. The method of claim 14, further comprising:

casting a mixture to which the aprotic solvent or the nonpolar solvent is added; and

cooling the mixture to produce a solid electrolyte film,

17. An all-solid battery comprising:

a positive electrode;

a negative electrode; and

a solid electrolyte, wherein the solid electrolyte is the solid electrolyte membrane according to any one of claims 1 to 8.