KR102193945B1 - Method of manufacturing a solid electrolyte layer and electrode composite layer containing a sulfide-based solid electrolyte - Google Patents

Abstract

The present invention provides a method for producing a solid electrolyte layer and an electrode composite layer including a sulfide-based solid electrolyte, and an all-solid-state battery comprising the same, comprising: preparing a sulfide-based amorphous solid electrolyte; Preparing a slurry containing the sulfide-based amorphous solid electrolyte; The technical summary is to include the step of crystallizing a solid electrolyte by applying the slurry to a current collector, followed by heat treatment and compression. Accordingly, the dispersion, density, and ionic conductivity characteristics between solid electrolyte particles and between solid electrolyte particles and active material particles are improved by crystallizing amorphous into crystalline or glass-crystalline through heat treatment and compression after applying amorphous solid electrolyte to the current collector. I can make it.

Description

Method of manufacturing a solid electrolyte layer and electrode composite layer containing a sulfide-based solid electrolyte}

The present invention relates to a method of manufacturing a solid electrolyte layer including a sulfide-based solid electrolyte and an electrode composite layer, and more particularly, after applying a solid electrolyte in an amorphous state to a current collector, heat treatment and compression to make amorphous or free -A method of manufacturing a solid electrolyte layer containing a sulfide-based solid electrolyte and an electrode composite layer capable of improving dispersion, density, and ionic conductivity properties between solid electrolyte particles and between solid electrolyte particles and active material particles by crystallization into crystalline will be.

Secondary batteries have been mainly applied to small-sized fields such as mobile devices and notebook computers, but in recent years, the direction of application has been expanded to mid-to-large-sized fields, mainly energy storage systems (ESS) or electric vehicles (EV). It is expanding to fields that require high energy and high output in relation to such. Unlike small-sized secondary batteries, the operating environment such as temperature and impact is severe, and since more batteries must be used, it is necessary to ensure safety along with excellent performance or an appropriate price. Since most of the secondary batteries currently commercialized use an organic liquid electrolyte in which a lithium salt is dissolved in an organic solvent, there is a potential risk of ignition and explosion, including leakage.

Therefore, in recent years, development of an all-solid-state battery is being made, and the all-solid-state battery is a battery that uses a non-flammable inorganic solid electrolyte, and has thermal stability compared to a lithium secondary battery that uses a conventional combustible organic liquid electrolyte. It has the advantage of being high. An all-solid-state battery generally has a stacked structure of a negative electrode current collector layer, a negative electrode composite layer, a solid electrolyte layer, a positive electrode composite layer, and a positive electrode current collector layer. Among the conventional technologies for such an all-solid-state battery, processes suitable for mass production include'Korean Intellectual Property Office Registration Patent No. 10-1506833 slurry, a method of manufacturing a solid electrolyte layer, a method of manufacturing an electrode active material layer, and a method of manufacturing an all-solid-state battery' The same slurry application technique is being developed. Solid electrolytes include oxide and sulfide, but oxide-based solid electrolytes have a high heat treatment temperature of 400°C or higher, so heat treatment is impossible after the electrode and electrolyte layers are prepared. Therefore, in the manufacturing method of the present invention, as described in the prior art, Use ingredients. When the sulfide-based solid electrolyte is used as a material of the solid electrolyte, a heat treatment process must be performed to obtain a material having high ionic conductivity. Therefore, in the prior art, a slurry containing a crystalline or glass-ceramic sulfide-based solid electrolyte material manufactured through a heat treatment process is prepared, and a coating film for forming a solid electrolyte layer is formed from the slurry. It consists of a coating step and a step of drying the solid electrolyte layer by drying the coating film.

However, when a crystalline or glass-crystalline sulfide-based solid electrolyte is applied as an electrolyte, coarsening of particles occurs in the heat treatment process to obtain a sulfide-based solid electrolyte material having high ion conductivity. Therefore, in order to prepare the slurry, an additional process of pulverizing the slurry is required, but there is a problem in that the ionic conductivity of the solid electrolyte is lowered in the pulverization process.

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

Accordingly, an object of the present invention is to apply a solid electrolyte in an amorphous state to a current collector, and then crystallize the amorphous into crystalline or glass-crystalline through heat treatment and compression, thereby dispersing between solid electrolyte particles and between solid electrolyte particles and active material particles. Also, it is to provide a method of manufacturing a solid electrolyte layer and an electrode composite layer including a sulfide-based solid electrolyte capable of improving ionic conductivity characteristics.

The above object is dry milling, wet milling, dissolution mixing of raw materials of amorphous solid electrolytes such as Li ₂ S, P ₂ S ₅ , LiX (X is any one element selected from Cl, Br, and I group). Or preparing a sulfide-based amorphous solid electrolyte by a method such as dough mixing; Preparing a slurry containing the sulfide-based amorphous solid electrolyte; It is achieved by a method for producing a solid electrolyte layer including a sulfide-based solid electrolyte and an electrode composite layer comprising the step of crystallizing the solid electrolyte by applying the slurry to a current collector, followed by heat treatment and compression.
Here, the sulfide-based amorphous solid electrolyte is a solid electrolyte having an ionic 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, Here, _x , _y , _z are positive constants, X is Cl, Br, any one element selected from group I, for example, Li ₇ P ₂ S ₈ I, Li ₆ PS ₅ Cl) It is desirable.
In addition, the sulfide-based amorphous solid electrolyte is LPSX (Li _x P _y S _z X, where _x , _y , _z are positive constants, X is any one element selected from Cl, Br, and I group) In the solid electrolyte of the composition, LGPS (Li ₁₀ GeP ₂ S ₁₂ ) or LPS (Li ₇ P ₃ S ₁₁ )-based crystalline or glass-crystalline solid electrolyte is contained in an amount of 1 to 50% by weight, or the sulfide-based amorphous solid electrolyte Silver, LPSX (Li _x P _y S _z X, where _x , _y , _z are positive constants, X is Cl, Br, any one element selected from group I) in a solid electrolyte of lithium (Li ), phosphorus (P), sulfur (S), chlorine (Cl), bromine (Br), iodine (I) other elements other than it is preferably contained in an amount of 1 to 10% by weight, the sulfide-based amorphous solid electrolyte , It is preferable to have a particle size of 0.1 to 10㎛.
In addition, the slurry is a solid electrolyte slurry consisting of the sulfide-based amorphous solid electrolyte, a binder, and a solvent, and an electrode composite slurry consisting of the sulfide-based amorphous solid electrolyte, a binder, a conductive material, an electrode active material, and a solvent. In the step of crystallizing, the electrode composite slurry is applied, heat treated, and compressed to form an electrode composite layer, and the solid electrolyte slurry is applied to the top of the electrode composite layer, followed by heat treatment and compression to form a solid electrolyte layer. desirable.
In the step of crystallizing the solid electrolyte, it is preferable to perform heat treatment at 140 to 250° C. and compression at a pressure of 10 to 500 MPa.
The above object is also a current collector; A negative electrode composite layer and a positive electrode composite layer comprising a sulfide-based crystalline or glass-crystalline solid electrolyte 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. An electrode composite layer made of; It is laminated on the top of the electrode composite layer and comprises a sulfide-based crystalline solid electrolyte crystallized from a sulfide-based amorphous solid electrolyte having a size of 0.1 to 10 μm or a solid electrolyte layer including a glass-crystalline solid electrolyte and a binder, and the current collector -The positive electrode composite layer-the solid electrolyte layer-the negative electrode composite layer-the current collector is laminated and formed by an all-solid-state battery.

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According to the configuration of the present invention described above, the dispersion degree between the solid electrolyte particles and between the solid electrolyte particles and the active material particles by crystallizing the amorphous into crystalline or glass-crystalline through heat treatment and compression after applying a solid electrolyte in an amorphous state to a current collector. , It is possible to obtain the effect of improving the density and ion conductivity characteristics.

1 is a flow chart of a method for manufacturing 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 an amorphous and glass-crystalline solid electrolyte in a slurry,
3 is a graph showing a phase change according to temperature after heat treatment of an amorphous solid electrolyte,
4 is a graph showing ionic conductivity according to temperature after heat treatment of an amorphous solid electrolyte,
5 is a graph showing the charging and discharging results of all-solid-state batteries manufactured through Examples and Comparative Examples.

Hereinafter, a method of manufacturing a solid electrolyte layer including a sulfide-based solid electrolyte and an electrode composite layer according to the present invention will be described in detail with reference to the drawings.
The all-solid-state battery of the present invention includes a current collector and a sulfide-based crystalline or glass-crystalline solid electrolyte 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. 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 μm and laminated on the electrode composite layer and the electrode composite layer consisting of a negative electrode composite layer and a positive electrode composite layer including It is made of a solid electrolyte layer including, and is formed by stacking a current collector-a positive electrode composite layer-a solid electrolyte layer-a negative electrode composite layer-a current collector.
As shown in FIG. 1, first, a sulfide-based amorphous solid electrolyte is prepared (S1).
Sulfide-based amorphous solid electrolyte is dry milling, wet milling, and dissolution of raw materials of amorphous solid electrolytes such as Li ₂ S, P ₂ S ₅ , and LiX (X is any one element selected from Cl, Br, and I group). It is prepared by a method such as mixing or kneading, and refers to a solid electrolyte in an amorphous state that is not crystalline or glass-crystalline. Preferred sulfide-based amorphous solid electrolyte is LPSX (Li _x P _y S _z X, where _x , _y , _z are positive constants, X is any one element selected from Cl, Br, and I group) when crystallized. For example, a solid electrolyte having a composition of Li ₇ P ₂ S ₈ I, Li ₆ PS ₅ Cl) is preferred, but is not limited thereto. When the sulfide-based solid electrolyte is crystalline or glass-crystalline rather than amorphous, the problem of increasing the particle size during the crystallization process occurs, making it difficult to apply uniformly during slurry preparation, and it is difficult to uniformly disperse even when mixed with an active material. In contrast, the amorphous sulfide-based solid electrolyte has a smaller particle size than that of crystalline or glass-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 μm.

A slurry containing a sulfide-based amorphous solid electrolyte is prepared (S2).
A slurry is prepared by mixing a sulfide-based amorphous solid electrolyte in an amorphous state without any other treatment with a solvent in which a binder is dissolved. The solid electrolyte slurry that forms the solid electrolyte layer consists of a sulfide-based amorphous solid electrolyte, a binder, and a solvent, and in the case of the electrode composite slurry forming the electrode composite layer, a positive electrode active material or a negative electrode active material, a sulfide-based amorphous solid electrolyte , It can be formed by adding a conductive material to a binder, a solvent. Here, the positive electrode active material or the negative electrode active material may be an active material used in a general secondary battery, or an active material surface-treated to reduce chemical reactivity with a sulfide-based solid electrolyte may be used without limitation.
Binders are polyamide-imide (PAI), polyimide (PI), polyamide (PA), polyamic acid, polyethylene oxide (PEO), PEPMNB (poly(ethylene)). -co-propylene-co-5-methylene-2-norbornene)), polyviylidene fluoride (PVDF), PVDF-HFP (poly(vinylidene fluoride-co-hexafluoropropylene), NBR (nitrile-butadiene rubber)) , PS-NBR (polystyrene nitrile-butadiene rubber), PMMA-NBR (poly(methacrylate) nitrile-butadiene rubber), and mixtures thereof are preferably selected from the group consisting of, but are not limited to, and are included in the electrode composite slurry. The conductive material is active carbon, carbon nanotube, carbon fiber, graphene, graphite, carbon black, acetylene black, It may be selected from the group consisting of ketjen black (KR), super P, metal nanowires, and mixtures thereof.

After applying the slurry, the solid electrolyte is crystallized by heat treatment and compression (S3).
After applying the electrode composite slurry to the current collector, heat treatment and compression are applied to form an electrode composite layer, and a solid electrolyte slurry is applied on the top of the electrode composite layer, followed by heat treatment and compression to form a solid electrolyte layer. Here, the solid electrolyte contained in the solid electrolyte layer and the electrode composite layer is crystallized from amorphous to crystalline or glass-crystalline by heat treatment and compression. That is, a conductive metal current collector is prepared and an electrode composite slurry is applied thereto. The slurry is coated with a thin film of 10 to 500 µm on the top of the current collector, and then dried. Then, the electrode composite slurry and the metal current collector are pressurized and heat treated at a temperature of 140 to 250°C at which the binder is not decomposed or deformed at a pressure of 10 to 500 MPa. A more preferable heat treatment temperature is 140 to 200°C. These conditions apply equally to the production of the solid electrolyte layer.
In order to form the solid electrolyte layer and the electrode composite layer, crystallization must be performed at a temperature that can minimize the melting or deformation of the binder. If the heat treatment temperature is less than 140℃, the solid electrolyte does not crystallize properly and exceeds 250℃. Deformation of the binder may occur. In general, LGPS (Li ₁₀ GeP ₂ S ₁₂ )-based solid electrolyte, which is a solid electrolyte exhibiting high ionic conductivity of 10 ^-2 S/cm or more, has a crystallization temperature of 400° C. or higher, and has a level of 10 ^-3 to 10 ^-2 S/cm. It is known that the solid electrolyte in LPS (Li ₇ P ₃ S ₁₁ ) showing ionic conductivity is crystallized at a temperature exceeding 250°C. Therefore, as a crystal phase that can be used in the solid electrolyte layer and the electrode composite layer of the present invention, LPSX (Li _x P _y S _z X, where, it shows a lithium ion conductivity of 10 ^-4 to 10 ^-2 S/cm between 200 and 250 °C) _x , _y , _z are positive constants, X is a solid electrolyte having a composition of any one element selected from Cl, Br, and I groups, for example Li ₇ P ₂ S ₈ I, Li ₆ PS ₅ Cl) Can be used. More preferably, it is preferable to select a crystalline or glass-crystalline solid electrolyte having the highest ionic conductivity at a heat treatment temperature of 200° C. or less as the material.
In addition, in order to increase the ionic conductivity of the amorphous LPSX solid electrolyte, a solid electrolyte may be prepared by mixing crystalline or glass-crystalline LGPS and LPS solid electrolyte powders. If this is described in detail, LGPS in the solid electrolyte of the composition of LPSX (Li _x P _y S _z X, where _x , _y , _z are positive constants, X is any one element selected from Cl, Br, and I group) (Li ₁₀ GeP ₂ S ₁₂ ) or LPS (Li ₇ P ₃ S ₁₁ )-based crystalline or glass-crystalline solid electrolyte is mixed to contain 1 to 50% by weight. In addition, the sulfide-based amorphous solid electrolyte is LPSX (Li _x P _y S _z X, where _x , _y , _z are positive constants, X is any one element selected from Cl, Br, and I group) And in the solid electrolyte selected from the group consisting of mixtures thereof, 1 to 10% by weight of other elements except lithium (Li), phosphorus (P), sulfur (S), chlorine (Cl), bromine (Br), and iodine (I) It is also possible to use those contained as.

A solid electrolyte layer with improved ionic conductivity of lithium ions can be prepared by minimizing the voids of the solid electrolyte layer and minimizing the interfacial resistance between the solid electrolyte particles according to the high plastic deformation rate of the amorphous particles. In addition, a solvent in which an electrode active material, a conductive material, and a binder are dissolved together with an amorphous solid electrolyte is applied to the current collector to form a 10 to 500 μm thin film like the solid electrolyte layer, and then dried, pressurized, and heat treated to increase the density of the electrode layer. , An electrode composite layer having improved ionic conductivity of the solid electrolyte and the contact property between the solid electrolyte and the electrode active material can be prepared. Here, as for the electrode composite layer, a positive electrode composite layer is formed when the electrode active material included in the slurry is a positive electrode active material, and a negative electrode composite layer is formed if the negative electrode active material is a negative electrode active material.
Hereinafter, embodiments of the present invention will be described in more detail.

<Example>
LPSI consisting of 80 (0.75Li ₂ S·0.25P ₂ S ₅ )·20LiI composition, which is a sulfide-based material capable of crystallization from a solid electrolyte having high ion conductivity at a temperature of 200°C or less, was selected.
First, 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 put into a ball mill reaction vessel filled with 8 g of heptane and zirconia balls having a diameter of 5 mm. ) High energy wet ball milling was performed at 500 rpm with 53 g to obtain a heptane solution in which solid electrolyte powder was dispersed. At this time, 10 to 80 times were repeated in a manner of stopping for 30 minutes after operation for 30 minutes to prevent excessive temperature rise of the reaction vessel. The amorphous solid electrolyte powder can be obtained by drying the dispersion solution at 100° C. for 1 hour.
The procedure for manufacturing an all-solid-state battery test cell using the amorphous solid electrolyte powder prepared in this way is as follows. First, the positive electrode composite layer is a LiNi _0.6 Mn _0.2 Co _0.2 O ₂ positive electrode active material coated with 10 nm of LiNbO ₃ , the solid electrolyte is amorphous LPSI, the conductive material is super P, the binder is PEPMNB, and these are 70:25:2.5:2.5 by weight. A slurry mixed with heptane is prepared. Then, the slurry was applied to an aluminum (Al) current collector, dried, and compressed to prepare a positive electrode composite layer. Then, the solid electrolyte layer was prepared by coating and drying a heptane slurry in which amorphous LPSI and a binder were dispersed on the positive electrode composite layer.
The thus prepared positive electrode composite layer/solid electrolyte layer was simultaneously compressed at a pressure of 200 MPa and then heat-treated at 180° C., and an indium counter electrode was attached to prepare a test cell. At this time, by using a negative electrode active material for lithium ion batteries such as graphite instead of the counter electrode, and using a negative electrode composite layer or a lithium metal electrode prepared by mixing with a solid electrolyte in the same manner as a positive electrode composite, an all-solid battery, not a test cell, can be manufactured. .
On the other hand, in Comparative Example, an electrode composite layer and a solid electrolyte layer were prepared by applying a glass-crystalline LPSI solid electrolyte first heat-treated at 180° C. in the same manner as in the method of manufacturing the positive electrode composite layer and the solid electrolyte layer of the Example. After that, it was compressed at 200 MPa and then attached to an indium counter electrode without separate heat treatment to prepare an experimental cell.

2 is a comparative analysis of particle size according to crystallization by re-dispersing the amorphous LPSI powder prepared by the wet ball mill reaction and the glass-crystalline LPSI powder heat-treated at 180° C. in a mixed solvent of dibutyl ether and heptane. I did it. Through this, it can be seen that the amorphous LPSI powder mainly has a particle size of 0.1 to 10 µm, whereas the glass-crystalline LPSI powder has a particle size of 0.1 to 100 µm, so that the size is larger than that of the amorphous LPSI powder. In particular, it can be seen that the D(0.5) particle size increased by about 2 times and the D(0.9) particle size by about 4 times during the crystallization step. Therefore, in preparing the solid electrolyte layer and the electrode composite layer, it is advantageous to use an amorphous solid electrolyte having a particle size smaller than that of a crystalline or glass-crystalline solid electrolyte to obtain a uniform mixed electrode. In addition, amorphous particles having a small particle size help to minimize voids and interfaces even when compressing a solid electrolyte layer or an electrode composite layer.
Figure 3 is amorphous LPSI dispersed in heptane 100 ℃, 160 ℃, 180 ℃, 200 ℃, 250 ℃, dried for 1 hour in an argon (Ar) atmosphere at a temperature of 300 ℃, and determined while varying the heat treatment temperature The formation of the phase was observed. Heat treatment was performed for 3 hours each in an argon atmosphere. At 100℃, 160℃, 180℃ and 200℃ below 200℃, the phases of Phase I and Phase II appear. In the case of Phase II, the lithium ion conductivity of the Li ₇ P ₂ S ₈ I phase is 3×10 ^-4 S/cm. Known as. In contrast, at 250℃, it can be seen that the Phase I phase completely disappears and the Phase III phase appears.
4 is a graph showing the measurement of the lithium ion conductivity according to the heat treatment temperature according to the temperature, and it can be seen that the solid electrolyte layer heat-treated at 160° C. exhibits the highest ionic conductivity. This is related to the Phase I phase appearing between 140 to 200°C in FIG. 3, and it can be seen that the lithium ion conductivity is rapidly lowered by the Phase III phase at 250°C or higher. Therefore, it can be seen that the LPSI composition used in this 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. where no melting or deformation of the binder occurs.
5 is an evaluation of the characteristics of an all-solid-state battery by varying the charging and discharging rates of the positive electrode composite layer and the solid electrolyte layer prepared by the method of the example and the method of the comparative example, respectively, with respect to the indium counter electrode. It is a graph. The capacity was expressed as a relative value to the first cycle charging capacity of the examples, and the rate was tested as rate 1 <rate 2 <rate 3. Comparing this, it can be seen that a battery having superior initial capacity and charge/discharge rate characteristics was manufactured in the experimental cell of the Example compared to the experimental cell of the Comparative Example.

In the case of a solid electrolyte layer in a conventional method, in general, a crystalline or glass-crystalline solid electrolyte powder having a high ionic conductivity of lithium was mixed with a solvent in which a binder was dissolved, coated with a thin film of tens to hundreds of µm, and dried. In addition, in the case of a conventional electrode composite layer, a negative electrode active material or a positive electrode active material, a crystalline or glass-crystalline solid electrolyte, and a conductive material were mixed with a solvent in which a binder was dissolved, coated with a thin film of tens to hundreds of micrometers, and dried. . When the solid electrolyte layer and the electrode composite layer are formed through such a method, the uniformity is poor due to the large particle size of the crystalline or glass-crystalline solid electrolyte, and the dispersibility and density are poor, so the capacity of the battery decreases, and high efficiency characteristics are not obtained. Has a problem. In contrast, in the case of the present invention, a solid electrolytic coating layer and an electrode composite layer are formed using an amorphous solid electrolyte, and amorphous is crystallized into crystalline or glass-crystalline through heat treatment and pressurization. In this case, an amorphous solid electrolyte with a small particle size is applied to the current collector in a slurry state, thereby improving the dispersion and density between the solid electrolyte particles and between the solid electrolyte particles and the active material particles, and the resulting solid electrolyte layer and electrode composite layer are highly ionic. It may have conductivity, and may have increased capacity and high efficiency characteristics of a battery including the same.

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Claims (10)

In the method for producing a solid electrolyte layer and an electrode composite layer comprising a sulfide-based solid electrolyte,
Non-glass-crystalline LPSX (Li _x P _y S _z X, where _x , _y , _z are positive constants, X is Cl, Br, any one element selected from group I) composition of 0.1 to 10 Preparing a sulfide-based amorphous solid electrolyte having a particle size of µm;
A slurry is prepared by mixing the sulfide-based amorphous solid electrolyte in an amorphous state without any other treatment with a solvent in which a binder is dissolved, wherein the slurry comprises a solid electrolyte slurry consisting of the sulfide-based amorphous solid electrolyte, a binder, and a solvent, and the An electrode composite slurry comprising a sulfide-based amorphous solid electrolyte, a binder, a conductive material, an electrode active material, and a solvent;
After applying the electrode composite slurry, heat treatment and compression are applied to form an electrode composite layer, and the solid electrolyte slurry is applied on the top of the electrode composite layer, followed by heat treatment and compression to form a solid electrolyte layer, at 140 to 250°C. A method for producing a solid electrolyte layer and an electrode composite layer comprising a sulfide-based solid electrolyte, comprising: heat treatment and pressing at a pressure of 10 to 500 MPa. The method of claim 1,
The sulfide-based amorphous solid electrolyte,
A method of producing a solid electrolyte layer and an electrode composite layer comprising a sulfide-based solid electrolyte, characterized in that it is a solid electrolyte having an ionic conductivity of 10 ^-4 to 10 ^-2 S/cm upon crystallization. delete The method of claim 1,
The sulfide-based amorphous solid electrolyte,
LGPS (Li ₁₀ GeP) in a solid electrolyte of LPSX (Li _x P _y S _z X, where _x , _y , _z are positive constants, X is any one element selected from Cl, Br, and I group) ₂ S ₁₂ ) or LPS (Li ₇ P ₃ S ₁₁ )-based crystalline or glass-crystalline solid electrolyte containing 1 to 50% by weight of a solid electrolyte layer and electrode composite layer comprising a sulfide-based solid electrolyte Method of manufacturing. The method of claim 1,
The sulfide-based amorphous solid electrolyte,
Lithium (Li) in a solid electrolyte of LPSX (Li _x P _y S _z X, where _x , _y , _z are positive constants, X is any one element selected from Cl, Br, and group I), A solid electrolyte containing a sulfide-based solid electrolyte, characterized in that it contains 1 to 10% by weight of other elements excluding phosphorus (P), sulfur (S), chlorine (Cl), bromine (Br), and iodine (I) Method for producing a layer and an electrode composite layer. delete delete delete delete delete

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