KR20180057135A - Method of manufacturing a solid electrolyte layer and electrode composite layer containing a sulfide-based solid electrolyte and all-solid electrolyte cell comprising the same - Google Patents

Abstract

The present invention relates to a solid electrolyte layer containing a sulfide-based solid electrolyte, a method for producing an electrode composite layer, and an all-solid battery including the same. To this end, the method comprises the following steps: preparing a sulfide-based amorphous solid electrolyte; producing slurry comprising the sulfide-based amorphous solid electrolyte; and applying the slurry to a collector, conducting heat treatment and compression, so as to crystallize the solid electrolyte. By undergoing the heat treatment and compression after application the amorphous solid electrolyte to the collector for crystallization from an amorphous state to crystalline or glass-crystalline state, it is possible to improve a degree of dispersion, compactness, and ionic conductivity among solid electrolyte particles, solid electrolyte particle, and active material particles.

Description

METHOD FOR MANUFACTURING SOLID ELECTROLYTE LAYER AND ELECTRODE COMPOSITE LAYER COMPRISING SULFIDE-BASED SOLID ELECTROLYTE AND PROFIBUS FOR THE PRE-SOLID BATTERY CONTAINING SOLDER SOLID ELECTRODE AND ELECTRODE COMPOSITE LAYER the same}

The present invention relates to a solid electrolyte layer containing a sulfide-based solid electrolyte and a method for producing the same, and more particularly to a method for manufacturing a solid electrolyte layer comprising a sulfide-based solid electrolyte, Based solid electrolyte capable of improving the degree of dispersion, compactness and ionic conductivity between the solid electrolyte particles and between the solid electrolyte particles and the active material particles by crystallizing the amorphous into crystalline or free-crystalline state through the solid electrolyte layer and the electrode To a process for producing a composite layer and to an all-solid-state cell comprising the same.

The secondary battery has been mainly applied to a small-sized field such as a mobile device or a notebook computer. However, recently, the application of the secondary battery has been expanding into a medium- and large-sized field, and an energy storage system (ESS) And the like are being expanded to fields requiring high energy and high output. Unlike a small-sized and medium-sized secondary battery, operating environments such as temperature and impact are not only severe but also require a large number of batteries. Therefore, it is necessary to ensure safety with good performance and reasonable prices. Most commercialized secondary batteries use an organic liquid electrolyte in which a lithium salt is dissolved in an organic solvent, which poses a potential risk of ignition and explosion including leakage.

Therefore, all-solid-state batteries are being developed in recent years. Batteries using non-combustible inorganic solid electrolytes as compared with lithium secondary batteries using conventional combustible organic liquid electrolytes have a higher thermal stability Is high. The precharge cell generally has a laminated structure of an anode current collector layer, a cathode electrode composite layer, a solid electrolyte layer, a cathode electrode composite layer, and a cathode collector layer. Examples of suitable processes for mass production of such prior solid-state batteries include 'Slurry, a method for producing a solid electrolyte layer, a method for producing an electrode active material layer, and a method for manufacturing an all-solid battery', Korean Registered Patent No. 10-1506833 A technique of the same slurry application method is being developed. The solid electrolyte has an oxide system and a sulfide system. However, since the oxide-based solid electrolyte has a high heat treatment temperature of 400 ° C or more, and thus the electrode and the electrolyte layer can not be heat-treated after the production, Materials are used. When a sulfide-based solid electrolyte is used as a solid electrolyte material, a heat treatment process must be performed to obtain a material having a high ion conductivity. Accordingly, the prior art processes include preparing a slurry containing a crystalline or glass-ceramic sulfide-based solid electrolyte material prepared through a heat treatment process, and forming a coating film for forming a solid electrolyte layer with the slurry And drying the solid electrolyte layer by drying the coating film.

However, when the crystalline or free-crystalline sulfide-based solid electrolyte is applied to the electrolyte, coarsening of the particles occurs in the heat treatment process to obtain a sulfide-based solid electrolyte material having a high ion conductivity. Therefore, there is a problem in that the ion conductivity of the solid electrolyte is lowered in the undifferentiation process.

Korea Intellectual Property Office Registration No. 10-1506833 Korea Patent Office Registration No. 10-1460113 Korean Patent Application Publication No. 10-2014-0073400

Accordingly, an object of the present invention is to provide a method of manufacturing a semiconductor device, which comprises applying a solid electrolyte in an amorphous state to a collector, and then crystallizing the amorphous material into crystalline or free-crystalline state through heat treatment and compression to obtain a dispersion degree between solid electrolyte particles and active material particles, A solid electrolyte layer including a sulfide-based solid electrolyte capable of improving ionic conductivity, and a method for producing the electrode composite layer, and a pre-solid battery including the same.

The above-mentioned object is achieved by a method for producing amorphous solid electrolyte raw materials such as Li ₂ S, P ₂ S ₅ and LiX (X = Cl, Br, I) by dry milling, wet milling, Preparing a solid electrolyte; Preparing a slurry comprising the sulfide-based amorphous solid electrolyte; And a step of crystallizing the solid electrolyte by applying the slurry to a current collector, followed by heat treatment and compression, to thereby obtain a solid electrolyte layer and an electrode composite layer containing the sulfide-based solid electrolyte.

Here, the sulfide-based amorphous solid electrolyte is a solid electrolyte having an ion conductivity of 10 ^-4 to 10 ^-2 S / cm through crystallization, and the sulfide-based amorphous solid electrolyte is LPSX (Li _x P _y S _z X, X = Cl, Br, I such as Li ₇ P ₂ S ₈ I, Li ₆ PS ₅ Cl).

The sulfide-based amorphous solid electrolyte can be prepared by mixing LGPS (Li ₁₀ GeP ₂ S ₁₂ ) or LPS (Li ₇ P ₃ S) with a solid electrolyte having a composition of LPSX (Li _x P _y S _z X, X = Cl, of the composition, or contain a crystalline solid electrolyte of 1 to 50% by weight or, the sulfide-based amorphous solid _{electrolyte, LPSX (Li x P y S} z x, x = Cl, Br, I) - 11) based crystalline or glass It is preferable that the solid electrolyte contains 1 to 10% by weight of elements other than lithium (Li), phosphorus (P), sulfur (S), chlorine (Cl), bromine (Br) and iodine (I) The sulfide-based amorphous solid electrolyte preferably has a particle size of 0.1 to 10 mu m.

Also, the slurry is an electrode composite slurry comprising the solid electrolyte slurry composed of the sulfide-based amorphous solid electrolyte, the binder and the solvent, and the sulfide-based amorphous solid electrolyte, the binder, the conductive material, the electrode active material and the solvent, The step of crystallizing is a step of forming an electrode composite layer by applying the electrode composite slurry, followed by heat treatment and pressing, applying the solid electrolyte slurry to the upper part of the electrode composite layer, followed by heat treatment and pressing to form a solid electrolyte layer desirable.

The step of crystallizing the solid electrolyte is preferably performed by heat treatment at 140 to 250 ° C and a pressure of 10 to 500 MPa.

The above-described object is also achieved by a method of manufacturing a semiconductor device, A negative electrode composite layer and a positive electrode composite layer formed on the current collector and including a sulfide-based crystalline or crystallized free-crystalline solid electrolyte from a sulfide-based amorphous solid electrolyte having a size of 0.1 to 10 μm, a binder, a conductive material, and an active material An electrode composite layer; And a solid electrolyte layer stacked on the electrode composite layer and including a sulfide-based crystalline solid electrolyte or a free-crystalline solid electrolyte and a binder crystallized from a sulfide-based amorphous solid electrolyte having a size of 0.1 to 10 탆, The positive electrode composite layer, the solid electrolyte layer, the negative electrode composite layer, and the current collector.

According to the constitution of the present invention described above, the amorphous state is crystallized in the crystalline or free-crystalline state by applying the solid electrolyte in the amorphous state to the current collector, followed by the heat treatment and the compression, thereby improving the dispersion between the solid electrolyte particles and the active- , Compactness, and ionic conductivity can be obtained.

1 is a flowchart of a method for producing a solid electrolyte layer and an electrode composite layer according to an embodiment of the present invention,
2 is a graph showing the particle size distribution of amorphous and free-crystalline solid electrolytes in a slurry,
3 is a graph showing a phase change according to temperature after heat treatment of an amorphous solid electrolyte,
FIG. 4 is a graph showing ionic conductivity according to temperature after heat treatment of an amorphous solid electrolyte, and FIG.
FIG. 5 is a graph showing the charge and discharge results of all the solid-state batteries manufactured through Examples and Comparative Examples.

Hereinafter, the solid electrolyte layer including the sulfide-based solid electrolyte according to the present invention and the method for producing the electrode composite layer and the pre-solid battery including the same will be described in detail with reference to the drawings.

A total cell of the present invention includes a collector, a sulfide-based crystalline or glass-crystalline solid electrolyte formed on the collector and crystallized from a sulfide-based amorphous solid electrolyte having a size of 0.1 to 10 μm, a binder, a conductive material, and an active material And a binder-crystalline or glass-crystalline solid electrolyte layered on the electrode composite layer and crystallized from a sulfide-based amorphous solid electrolyte having a size of 0.1 to 10 탆, and a binder- And a laminate of a current collector-positive electrode composite layer-solid electrolyte layer-negative electrode composite layer-current collector.

As shown in FIG. 1, first, a sulfide-based amorphous solid electrolyte is prepared (S1).

Sulfide amorphous solid electrolytes are prepared by a method such as dry milling, wet milling, melt mixing, or kneading of raw materials for amorphous solid electrolytes such as Li ₂ S, P ₂ S ₅ and LiX (X = Cl, Br, I) , ≪ / RTI > crystalline or non-free-crystalline amorphous solid electrolyte. The preferred sulfide amorphous solid electrolyte is preferably a solid electrolyte having a composition of LPSX (Li _x P _y S _z X, X = Cl, Br, I, for example Li ₇ P ₂ S ₈ I, Li ₆ PS ₅ Cl) But is not limited thereto. When a non-amorphous crystalline or free-crystalline sulphide-based solid electrolyte is used, the problem of increasing the particle size in the crystallization process occurs, making it difficult to apply uniformly in the preparation of the slurry and uniform dispersion in mixing with the active material. On the other hand, the amorphous sulfide-based solid electrolyte has a smaller particle size than that of crystalline or free-crystalline, which is advantageous for uniform application and uniform dispersion. Here, the sulfide-based amorphous solid electrolyte is preferably present in a particle size of 0.1 to 10 mu m.

Thereby preparing a slurry containing a sulfide-based amorphous solid electrolyte (S2).

The amorphous state of the sulfide amorphous solid electrolyte without any other treatment is mixed with the solvent in which the binder is dissolved to prepare a slurry. In the case of the solid electrolyte slurry constituting the solid electrolyte layer, in the case of the electrode composite slurry for forming the electrode composite layer, the positive electrode active material or the negative electrode active material, the sulfide-based amorphous solid electrolyte , A binder, and a solvent. Here, the cathode active material or the anode active material may be an active material used in a conventional secondary battery, or may be any surface-treated active material to reduce chemical reactivity with a sulfide-based solid electrolyte.

The binder may be a polyamide-imide (PAI), a polyimide (PI), a polyamide (PA), a polyamic acid, a polyethylene oxide (PEO) polyvinylidene fluoride (PVDF), polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP), nitrile-butadiene rubber (NBR) , Butadiene rubber (PS-NBR), poly (methacrylate) nitrile-butadiene rubber (PMMA-NBR), and mixtures thereof. The conductive material may be selected from the group consisting of active carbon, carbon nanotube, carbon fiber, graphene, graphite, carbon black, acetylene black, Ketjen black (KR), super P, metal nanowires and mixtures thereof It may be selected from the group consisting of.

After the slurry is applied, the solid electrolyte is crystallized by heat treatment and compression (S3).

Electrode composite slurry is applied to a current collector, followed by heat treatment and compression to form an electrode composite layer. A solid electrolyte slurry is coated on the electrode composite layer, followed by heat treatment and compression to form a solid electrolyte layer. Here, the solid electrolyte included in the solid electrolyte layer and the electrode composite layer is crystallized from amorphous to crystalline or free-crystalline by heat treatment and compression. That is, a conductive metal current collector is prepared and the electrode composite slurry is coated on the slurry. The slurry is coated on the current collector with a thin film having a thickness of 10 to 500 μm and dried. Then, the slurry is pressed and heat-treated at a pressure of 10 to 500 MPa at 140 to 250 DEG C, at which the binder is not decomposed or deformed, and the electrode composite slurry and the metal current collector. More preferably, the heat treatment temperature is 140 to 200 占 폚. These conditions are equally applied to the production of the solid electrolyte layer.

In order to form the solid electrolyte layer and the electrode composite layer, crystallization should be performed at a temperature at which the melting or deformation of the binder can be minimized. When the heat treatment temperature is less than 140 ° C, the solid electrolyte is not crystallized properly. Deformation of the binder may occur. Generally, LGPS (Li ₁₀ GeP ₂ S ₁₂ ) -based solid electrolyte, which is a solid electrolyte exhibiting a high ionic conductivity of 10 ^-2 S / cm or more, has a crystallization temperature of 400 ° C or more and a lithium concentration of 10 ^-3 to 10 ^-2 S / cm It is known that the solid electrolyte on the LPS (Li ₇ P ₃ S ₁₁ ) representing the ionic conductivity is also crystallized at a temperature exceeding 250 ° C. Therefore, the crystal phases that can be used for the solid electrolyte layer and the electrode composite layer of the present invention include LPSX (Li _x P _y S _z X, where X represents lithium ion conductivity) of from 10 ^-4 to 10 ^-2 S / Cl, Br, I, for example, Li ₇ P ₂ S ₈ I, Li ₆ PS ₅ Cl) can be used. More preferably a crystalline or free-crystalline solid electrolyte exhibiting the highest ionic conductivity at a heat treatment temperature of 200 DEG C or lower.

The solid electrolyte may also be prepared by mixing crystalline or glass-crystalline LGPS and LPS solid electrolyte powder to enhance the ionic conductivity of the amorphous LPSX solid electrolyte. Specifically, LGPS (Li ₁₀ GeP ₂ S ₁₂ ) or LPS (Li ₇ P ₃ S ₁₁ ) -based crystalline or glassy material is added to a solid electrolyte having a composition of LPSX (Li _x P _y S _z X, X = Cl, - 1 to 50% by weight of the crystalline solid electrolyte. This, as well as sulfide-based amorphous solid electrolyte, LPSX (Li _x P _y S _z X, X = Cl, Br, I), and lithium (Li) with the selected solid electrolyte from the group consisting of its mixture, phosphorus (P), sulfur 1 to 10% by weight of other elements other than chlorine (S), chlorine (Cl), bromine (Br) and iodine (I) may be used.

It is possible to manufacture a solid electrolyte layer in which the ion conductivity of lithium ions is improved by minimizing the pore size of the solid electrolyte layer and minimizing the interfacial resistance between the solid electrolyte particles according to the high plastic strain of the amorphous particles. A solvent in which an electrode active material, a conductive material and a binder are melted is coated on a current collector together with an amorphous solid electrolyte to form a thin film having a thickness of 10 to 500 탆 like the solid electrolyte layer. The thin film is then dried, pressurized and heat- , An ionic conductivity of the solid electrolyte and an electrode composite layer having improved contact properties between the solid electrolyte and the electrode active material can be produced. Here, the electrode composite layer has a cathode composite layer when the electrode active material contained in the slurry is a cathode active material, and a cathode composite layer when the anode active material is a cathode active material.

Hereinafter, embodiments of the present invention will be described in more detail.

<Examples>

LPSI consisting of a composition of 80 (0.75Li ₂ S · 0.25P ₂ S ₅ ) · 20LiI which is a sulfide-based material capable of being crystallized into a solid electrolyte having a high ionic conductivity at a temperature of 200 ° C or less was selected.

In order to obtain an amorphous LPSI solid electrolyte, ₂ g of Li ₂ S, P ₂ S ₅ and LiI powder according to the above composition were placed in a ball mill reaction vessel filled with 8 g of heptane, and a zirconia ball having a diameter of 5 mm ) And ball milling at 500 rpm with high-energy wet ball milling to obtain a heptane solution in which the solid electrolyte powder was dispersed. At this time, in order to prevent the excessive rise of the temperature of the reaction vessel, 30 minutes of operation and 30 minutes of rest were repeated 10 to 80 times. The amorphous solid electrolyte powder can be obtained by drying the dispersion solution at 100 DEG C for 1 hour.

The procedure of manufacturing the all-solid-state battery test cell using the amorphous solid electrolyte powder produced in this way is as follows. First, LiNi _{0 .6} anode composite layer is a LiNbO ₃ 10nm coating Mn _{0 .2} Co _{0 .2} O ₂ and the positive electrode active material, the solid electrolyte is an amorphous LPSI, super conductive material P, the binder is 70 to them PEPMNB: 25 : 2.5: 2.5 in heptane to prepare a slurry. The slurry was then applied to an aluminum (Al) current collector, dried and pressed to produce a positive electrode composite layer. The solid electrolyte layer was prepared by applying an amorphous LPSI and a binder-dispersed heptane slurry on the positive electrode composite layer and drying the same.

The thus prepared positive electrode composite layer / solid electrolyte layer was simultaneously pressed at a pressure of 200 MPa, heat-treated at 180 ° C, and an indium counter electrode was attached to produce a test cell. At this time, all the solid cells other than the test cell can be manufactured by using the anode composite layer or the lithium metal electrode prepared by mixing the anode active material for lithium ion battery such as graphite with the solid electrolyte in the same manner as the anode composite .

On the other hand, in the comparative example, an electrode composite layer and a solid electrolyte layer were prepared by applying the glass-crystalline LPSI solid electrolyte, which was first heat-treated at 180 ° C, in the same manner as in the preparation of the positive electrode composite layer and the solid electrolyte layer in Example. Thereafter, the test cell was pressed with 200 MPa and mounted with an indium counter electrode without any heat treatment.

FIG. 2 is a graph comparing the particle size of the amorphous LPSI powder prepared by the wet ball milling reaction and the free-crystalline LPSI powder heat-treated at 180 ° C in a mixed solvent of dibutyl ether and heptane It is. As a result, the amorphous LPSI powder has a particle size of 0.1 to 10 μm, whereas the free-crystalline LPSI powder has a particle size of 0.1 to 100 μm, which is larger than the amorphous LPSI powder. Particularly, in the crystallization step, the D (0.5) particle size increased about twice and the D (0.9) particle size increased four times. Therefore, in producing the solid electrolyte layer and the electrode composite layer, it is advantageous to use an amorphous solid electrolyte having a smaller particle size than the crystalline or free-crystalline solid electrolyte to obtain a uniform mixed electrode. In addition, amorphous particles with small particle sizes also help to minimize voids and interfaces when compressing solid electrolyte layers or electrode composite layers.

FIG. 3 is a graph showing the results obtained by drying amorphous LPSI dispersed in heptane at 100 ° C., 160 ° C., 180 ° C., 200 ° C., 250 ° C. and 300 ° C. in an argon atmosphere for 1 hour, . The heat treatment was carried out under argon atmosphere for 3 hours each. Phase I and phase II phases are observed at 100 ° C, 160 ° C, 180 ° C and 200 ° C, which are below 200 ° C. In phase II, the lithium ion conductivity is 3 × 10 ^-4 S / cm at the Li ₇ P ₂ S ₈ I phase . In contrast, Phase I phase completely disappears and Phase III phase appears at 250 ° C.

FIG. 4 is a graph showing the measurement of lithium ion conductivity according to temperature according to the heat treatment temperature. It can be seen that the solid electrolyte layer heat-treated at 160 ° C. exhibits the highest ion conductivity. This is related to the Phase I phase occurring at 140 to 200 ° C in FIG. 3, and the lithium ion conductivity is rapidly lowered by phase III phase above 250 ° C. Therefore, it can be seen that the LPSI composition used in the present embodiment can be used as a solid electrolyte capable of improving ionic conductivity through heat treatment at a low temperature of 140 to 200 ° C at which the melting or deformation of the binder does not occur.

FIG. 5 is a graph showing the results of evaluating the characteristics of all solid-state batteries with different charging / discharging speeds for the indium counter electrode and the positive electrode composite layer and the solid electrolyte layer, respectively, produced by the method of the embodiment and the comparative example Graph. The capacity was expressed relative to the first cycle charge capacity of the example and the rate was tested at rate 1 <rate 2 <rate 3. Comparing the results, it can be seen that a cell having excellent initial capacity and charge / discharge ratio characteristics is produced in the experimental cell of the embodiment as compared with the experimental cell of the comparative example.

In the conventional method, in the case of the solid electrolyte layer, a crystalline or glass-crystalline solid electrolyte powder having a high lithium ion conductivity is generally mixed with a solvent in which the binder is dissolved, and then coated with a thin film of several tens to several hundreds of micrometers and dried. Further, in the case of the conventional electrode composite layer, the negative electrode active material, the cathode active material, the crystalline or the free-crystalline solid electrolyte, and the conductive material are mixed with a solvent in which the binder is dissolved, coated with a thin film of several tens to several hundreds of micrometers, . When the solid electrolyte layer and the electrode composite layer are formed through such a method, the uniformity is lowered due to the crystalline or free-crystalline solid electrolyte having a large particle size, the dispersibility and the density are not good, and the capacity of the battery is decreased, There is a problem. In contrast, in the case of the present invention, the amorphous solid electrolyte is used to form a solid electrolytic layer and an electrode composite layer, and the amorphous is crystallized into crystalline or free-crystalline by heat treatment and pressurization. In this case, the amorphous solid electrolyte having a small particle size is applied to the current collector in a slurry state, thereby improving the dispersion and compactness between the solid electrolyte particles and between the solid electrolyte particles and the active material particles. Thus, the solid electrolyte layer and the electrode composite layer, Conductivity, and can have a capacity increase and high efficiency characteristics of the battery including the same.

Claims (10)

A solid electrolyte layer comprising a sulfide-based solid electrolyte and a method for producing an electrode composite layer,
Preparing a sulfide-based amorphous solid electrolyte;
Preparing a slurry comprising the sulfide-based amorphous solid electrolyte;
And a step of applying the slurry to a current collector, followed by heat treatment and pressing to crystallize the solid electrolyte, wherein the solid electrolyte layer and the electrode composite layer are formed. The method according to claim 1,
The sulfide-based amorphous solid electrolyte may contain,
Wherein the solid electrolyte layer is a solid electrolyte having an ion conductivity of 10 &lt; ^-4 &gt; to 10 &lt; ^-2 &gt; S / cm upon crystallization. The method according to claim 1,
The sulfide-based amorphous solid electrolyte may contain,
_{LPSX (Li x P y S z} X, X = Cl, Br, I) sulfide-based method of manufacturing a solid electrolyte layer and electrode composite layer comprising a solid electrolyte, characterized in that composition. The method according to claim 1,
The sulfide-based amorphous solid electrolyte may contain,
(Li ₁₀ GeP ₂ S ₁₂ ) or LPS (Li ₇ P ₃ S ₁₁ ) -based crystalline or free-crystalline solid electrolyte is added to a solid electrolyte having a composition of LPSX (Li _x P _y S _z X, X = Cl, Br, Based on the total weight of the solid electrolyte layer and the electrode composite layer, and 1 to 50% by weight of the solid electrolyte layer containing the sulfide-based solid electrolyte. The method according to claim 1,
The sulfide-based amorphous solid electrolyte may contain,
(Li), phosphorus (P), sulfur (S), chlorine (Cl), bromine (Br), and iodine (L) in a solid electrolyte having a composition of LPSX (Li _x P _y S _z X, I) is contained in an amount of 1 to 10% by weight based on the total weight of the solid electrolyte layer and the electrode composite layer. The method according to claim 1,
The sulfide-based amorphous solid electrolyte may contain,
Wherein the solid electrolyte layer comprises a sulfide-based solid electrolyte having a particle size of 0.1 to 10 占 퐉. The method according to claim 1,
Wherein the slurry is an electrode composite slurry comprising the solid electrolyte slurry comprising the sulfide-based amorphous solid electrolyte, the binder and the solvent, and the sulfide-based amorphous solid electrolyte, the binder, the conductive material, the electrode active material and the solvent A solid electrolyte layer containing an electrolyte and a method for producing the electrode composite layer. 8. The method of claim 7,
The step of crystallizing the solid electrolyte comprises:
Wherein the solid electrolyte layer is formed by applying the slurry of the electrode composite material, followed by heat treatment and compression to form an electrode composite layer, applying the solid electrolyte slurry to the upper portion of the electrode composite layer, A solid electrolyte layer comprising a solid electrolyte and a method for producing the electrode composite layer. The method according to claim 1,
The step of crystallizing the solid electrolyte comprises:
Wherein the solid electrolyte layer comprises a sulfide-based solid electrolyte, and the solid electrolyte layer and the electrode complex layer are press-bonded at a temperature of 140 to 250 ° C under a pressure of 10 to 500 MPa. In all solid state batteries,
The whole house;
A negative electrode composite layer and a positive electrode composite layer formed on the current collector and including a sulfide-based crystalline or crystallized free-crystalline solid electrolyte from a sulfide-based amorphous solid electrolyte having a size of 0.1 to 10 μm, a binder, a conductive material, and an active material An electrode composite layer;
And a solid electrolyte layer stacked on the electrode composite layer and including a sulfide-based crystalline or glass-crystalline solid electrolyte and a binder crystallized from a sulfide-based amorphous solid electrolyte having a size of 0.1 to 10 탆,
Wherein the current collector, the positive electrode composite layer, the solid electrolyte layer, the negative electrode composite layer, and the current collector are laminated.

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