KR102456770B1 - Method of manufacturing a solid electrolyte layer and cathode composite layer containing a sulfide-based solid electrolyte and all-solid electrolyte cell comprising the same - Google Patents

Abstract

The present invention provides a method for manufacturing a solid electrolyte layer and a positive electrode composite layer comprising a sulfide-based solid electrolyte, and an all-solid-state battery comprising the same, comprising the steps of: preparing a sulfide-based solid electrolyte; preparing a slurry including the sulfide-based solid electrolyte, a binder, and a solvent; forming a membrane by applying the slurry to the porous support so that the slurry is impregnated and supported into the pores of the porous support; It is a technical gist to include the step of drying and pressing the membrane to obtain a solid electrolyte layer and a positive electrode composite layer. Thereby, a binder is mixed with a sulfide-based solid electrolyte to make a slurry, and flexibility is increased by combining with a porous support that supports the slurry, and the effect of preventing the solid electrolyte from being broken by impact or repeated contraction and expansion can be obtained. .

Description

Method of manufacturing a solid electrolyte layer and cathode composite layer containing a sulfide-based solid electrolyte and all-solid electrolyte cell comprising the same the same}

The present invention relates to a method for manufacturing a solid electrolyte layer and a positive electrode composite layer comprising a sulfide-based solid electrolyte, and an all-solid-state battery comprising the same, and more particularly, to a slurry by mixing a binder with a sulfide-based solid electrolyte, and Method for manufacturing a solid electrolyte layer and a positive electrode composite layer containing a sulfide-based solid electrolyte, which increases flexibility by bonding with a supporting porous support and can prevent the solid electrolyte from being broken by impact or repeated contraction and expansion, and an electrode comprising the same It relates to solid-state batteries.

Secondary batteries have been mainly applied to small fields such as mobile devices and notebook computers, but recently their application direction has been extended to medium and large fields, mainly energy storage systems (ESS) or electric vehicles (EVs). It is expanding to fields requiring high energy and high output. In the case of these medium and large-sized secondary batteries, unlike the small ones, the operating environment such as temperature and shock is harsh, and since more batteries must be used, it is necessary to secure safety along with excellent performance or an appropriate price. Since most of the currently commercialized secondary batteries use an organic liquid electrolyte in which lithium salt is dissolved in an organic solvent, there is a potential risk of ignition and explosion, including leakage.

Therefore, recently, development of an all-solid-state battery has been made. The all-solid-state battery is a battery using a non-flammable inorganic solid electrolyte and has thermal stability compared to a lithium secondary battery using a conventional combustible organic liquid electrolyte. This 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 prior art for all-solid-state batteries, suitable processes for mass production include 'Korean Intellectual Property Office Registration Patent No. 10-1506833 slurry, a method for manufacturing a solid electrolyte layer, a method for manufacturing an electrode active material layer, and a manufacturing method for an all-solid-state battery' The same slurry coating method is being developed.

There are oxide-based solid electrolytes and sulfide-based solid electrolytes, but since oxide-based solid electrolytes have a high heat treatment temperature of 400° C. or higher, heat treatment after manufacturing the electrode and electrolyte layer is impossible. use material. When a sulfide-based solid electrolyte is used as a material for the solid electrolyte, a heat treatment process must be performed in order to obtain a material with high ionic conductivity. Therefore, the prior art includes the steps of preparing a slurry containing a sulfide-based solid electrolyte material of crystalline or glass-ceramic prepared through a heat treatment process, and forming a coating film for forming a solid electrolyte layer with the slurry and a step of drying the solid electrolyte layer by drying the coating film.

However, such a solid electrolyte has a problem in that when lithium ions are charged and discharged into the solid electrolyte, the solid electrolyte is broken while repeating contraction and expansion.

Korean Intellectual Property Office Registered Patent No. 10-1506833 Korean Intellectual Property Office Registered Patent No. 10-1460113 Korean Patent Office Laid-Open Patent No. 10-2014-0073400

Therefore, an object of the present invention is to make a slurry by mixing a binder with a sulfide-based solid electrolyte, to increase flexibility by combining it with a porous support that supports the slurry, and to prevent the solid electrolyte from being broken by impact or repeated contraction and expansion. An object of the present invention is to provide a method for manufacturing a solid electrolyte layer and a positive electrode composite layer comprising a sulfide-based solid electrolyte, and an all-solid-state battery including the same.

The above object comprises the steps of preparing a sulfide-based solid electrolyte; preparing a slurry including the sulfide-based solid electrolyte, a binder, and a solvent; forming a membrane by applying the slurry to the porous support so that the slurry is impregnated and supported into the pores of the porous support; It is achieved by a method for manufacturing a solid electrolyte layer and a positive electrode composite layer comprising a sulfide-based solid electrolyte, characterized in that it includes the step of drying and pressing the membrane to obtain a solid electrolyte layer and a positive electrode composite layer.

Here, the binder is polyamide-imide (PAI), polyimide (PI), polyamide (PA), polyamic acid, polyethylene oxide (PEO), polystyrene (polystyrene, PS), PEP-MNB (poly(ethylene-co-propyleneco-5-methylene-2-norbornene)), PVDF (polyvinylidene fluoride), PVDF-HFP (poly(vinylidene fluoride-co-hexafluoropropylene)), PS -NBR (polystyrene nitrile-butadiene rubber), PMMA-NBR (poly(methacrylate) nitrile-butadiene rubber) and mixtures thereof, or the sulfide-based solid electrolyte is LPSCl (Li-P-S-Cl)-based solid electrolyte And, the binder is PEP-MNB (poly(ethylene-co-propyleneco-5-methylene-2-norbornene)), and it is preferable to use heptane as the solvent.

In addition, the binder is included in an amount of 0.1 to 10% by weight based on 100% by weight of the total slurry, and the slurry includes: a solid electrolyte slurry including the sulfide-based solid electrolyte and a binder; A positive electrode composite slurry comprising the sulfide-based solid electrolyte, a binder, a conductive material and a positive electrode active material, wherein the solid electrolyte layer is prepared through the solid electrolyte slurry, and the positive electrode composite layer is prepared through the positive electrode composite slurry desirable.

The porous support is preferably formed with a porosity of 10 to 95% by volume, and the porosity is reduced to 5 to 10% by volume by drying and compression, and the porous support is 20 to 10% by volume by drying and compression. It is preferable to become a thickness of 350 micrometers.

The above object also includes a current collector; a positive electrode composite layer formed on the current collector and having an amorphous, crystalline or amorphous-crystalline sulfide-based solid electrolyte having a size of 0.1 to 10 μm, a binder, a conductive material, and an active material supported on a porous support; It is also achieved by an all-solid-state battery, which is stacked on top of the positive electrode composite layer and includes a solid electrolyte layer in which a sulfide-based solid electrolyte having a size of 0.1 to 10 μm and a binder are supported on a porous support.

Here, the porosity of the membrane is preferably 10% by volume or less.

According to the above-described configuration of the present invention, a slurry is made by mixing a binder with a sulfide-based solid electrolyte, and flexibility is increased by combining with a porous support supporting the slurry, and the solid electrolyte is prevented from being broken by impact or repeated contraction and expansion. possible effects can be obtained.

1 is a flowchart of a method for manufacturing a solid electrolyte layer and a positive electrode composite layer according to an embodiment of the present invention;
2 is a graph showing the battery operation of the all-solid-state battery prepared in Examples,
3 is an impedance graph measuring lithium ion conductivity of a sulfide-based membrane including a porous support;
4 is a photograph of a membrane including a porous support,
5 is a graph showing the operation of a sulfide-based all-solid-state battery composed of a positive electrode composite positive electrode including a sulfide solid electrolyte and a sulfide-based membrane including a porous support using a slurry.

Hereinafter, a method for manufacturing a solid electrolyte layer and a positive electrode composite layer including a sulfide-based solid electrolyte according to the present invention and an all-solid-state battery including the same will be described in detail with reference to the drawings.

The all-solid-state battery of the present invention includes a current collector and an amorphous, crystalline or amorphous-crystalline sulfide-based solid electrolyte having a size of 0.1 to 10 μm, a binder, a conductive material and an active material formed on the top of the current collector, supported on a porous support. It includes a positive electrode composite layer, and a solid electrolyte layer stacked on top of the positive electrode composite layer, in which a sulfide-based solid electrolyte having a size of 0.1 to 10 μm and a binder are supported on a porous support. In addition to this, a negative electrode composite layer may be further included, and a current collector laminated with a current collector - a positive electrode composite layer - a solid electrolyte layer - a negative electrode composite layer - a current collector can be obtained. Here, it is preferable to use PEP-MNB (poly(ethylene-co-propyleneco-5-methylene-2-norbornene)) as the binder, but is not limited thereto.

Among them, as a method for preparing the solid electrolyte layer and the positive electrode composite layer, as shown in FIG. 1 , first, a sulfide-based solid electrolyte is prepared (S1).

An amorphous, crystalline or amorphous-crystalline LPSCl (Li-PS-Cl)-based solid electrolyte is prepared. Here, the LPSCl-based solid electrolyte may be formed of an argyrodite phase including amorphous. In some cases, the LPSI (Li-PSI)-based solid electrolyte may be included instead of the LPSCl-based solid electrolyte. The raw material of the solid electrolyte is composed of a combination of Li ₂ S, P ₂ S ₅ , LiCl, and LiI powder, and a solid electrolyte is prepared through dry milling or wet milling, and pulverizing it to have a small diameter through pulverization. will go through In the method for producing a solid electrolyte from the raw material of the solid electrolyte and pulverizing the solid electrolyte, it is preferable to mix the zirconia ball with the solid electrolyte and then rotate the zirconia ball to go through the manufacturing and grinding process. not limited

Here, the solid electrolyte can be selected from amorphous, crystalline, or amorphous-crystalline. In the case of amorphous, since it consists of particles with a smaller diameter than crystalline, the solid electrolyte layer can be made thin, and in the case of crystalline solid electrolyte, compared to amorphous Although the particle diameter is large, it has the advantage of excellent conductivity. Therefore, it is possible to select an amorphous, crystalline, or amorphous-crystalline solid electrolyte depending on the intended use of the all-solid-state battery.

crystal structure lithium ion conductivity
(S/cm) LPSCl_ball mill
(synthetic state) amorphous + crystalline 1.51×10 ^-3 After synthesis of LPSCl_ball mill
Heat treatment (550℃, 5h) crystalline 1.92×10 ^-3 After synthesis of LPSCl_ball mill
wet ball milling amorphous + crystalline 1.62×10 ^-4

Table 1 compares the lithium ion conductivity according to whether the amorphous LPSCl powder is amorphous, crystallized, or refined.

A slurry containing a sulfide-based solid electrolyte is prepared (S2).

A slurry is prepared by mixing a binder, a conductive material, and a solvent with the amorphous, crystalline, or amorphous-crystalline sulfide-based solid electrolyte obtained in step S1. In the case of a solid electrolyte slurry forming the solid electrolyte layer, it consists of a sulfide-based solid electrolyte, a binder, and a solvent. . Here, the positive active material may be an active material used in a typical secondary battery or an active material surface-treated to reduce chemical reactivity with a sulfide-based solid electrolyte without limitation.

Here, the binder is applicable to both the solid electrolyte slurry and the positive electrode composite slurry, and these binders are polyamide-imide (PAI), polyimide (PI), polyamide (PA), and polyamic acid (polyamic acid). acid), polyethylene oxide (PEO), polystyrene (PS), PEP-MNB (poly(ethylene-co-propyleneco-5-methylene-2-norbornene)), PVDF (polyvinylidene fluoride), PVDF-HFP (poly(vinylidene fluoride-co-hexafluoropropylene)), PS-NBR (polystyrene nitrile-butadiene rubber), PMMA-NBR (poly(methacrylate)nitrile-butadiene rubber), and mixtures thereof. Among them, PEP-MNB (poly(ethylene-co-propyleneco-5-methylene-2-norbornene)) is used as the most suitable binder.

The binder is preferably contained in an amount of 0.1 to 10% by weight of the total 100% by weight of the solid electrolyte slurry or the positive electrode composite slurry. When the binder content is less than 0.1% by weight, the solid electrolyte may be broken while repeating contraction and expansion due to charging and discharging of lithium ions. In addition, when it exceeds 10% by weight, the amount of the solid electrolyte to be added is reduced by the amount of the binder, thereby reducing charge/discharge performance.

In addition, the solvent that dissolves the binder and mixes the solid electrolyte and the binder evenly is toluene, xylene, dodecane, butylbutyrate, heptane, alcohol in which the binder is dissolved. (alcohol) and mixtures thereof are preferably selected, and among them, heptane is most suitable.

In addition, the conductive material included in the cathode composite slurry is active carbon, carbon nanotube, carbon fiber, graphene, graphite, carbon black. , acetylene black, ketjen black (KR), super P, may be selected from the group consisting of metal nanowires, metal nanopowders, and mixtures thereof.

bookbinder wt% sulfide solid electrolyte menstruum coatability PEPMNB 2 LPSCl or LPSI heptane ○

Table 2 confirms the coating properties of the solid electrolyte slurry in which the sulfide-based solid electrolyte (SSE) and the binder are mixed. The coating properties were confirmed. As can be seen from Table 2, it can be confirmed that the coating is smoothly performed without affecting the coating property even if the binder is added.

bookbinder wt% sulfide solid electrolyte cathode active material menstruum coatability PEPMNB 2 LPSCl or LPSI NCM622 heptane ○

Table 3 confirms the coating properties of the positive electrode composite slurry containing the NCM ₆₂₂ positive electrode active material together with the solid electrolyte and the binder. can

A membrane is formed by applying the slurry to the porous support (S3).

A membrane is formed by applying the slurry to the porous support so that the slurry obtained through step S2 is impregnated and supported into the pores of the porous support. That is, a positive electrode composite slurry or a solid electrolyte slurry can be selected and applied to the porous support. Here, it is preferable to use a doctor blade method as a method for applying the slurry.

The porous support having many pores may have a porosity of 10 to 95% by volume, and the higher the porosity, the greater the amount of slurry impregnated therein. When the porosity is less than 10% by volume, the slurry cannot be impregnated inside and remains outside, and when the porosity exceeds 95% by volume, the volume of the porous support itself is too small compared to the pores, so the porous support maintains its shape can't do it

The material of such a porous support is polyethylene (polyetlyene), polyvinylidene fluoride (PVDF), PVDF-HFP (poly(vinylidene fluoride-co-hexafluoropropylene), polyamide-imide (PAI), polyimide It is preferably selected from the group consisting of polyimide (PI), polyamide (PA), polyamic acid, polytelrafluoro ethylene (PTFE), and mixtures thereof. In addition, it contains PEO or lithium salt. Before complexing an interfacial coating layer such as PEO with a sulfide-based solid electrolyte, it may be thinly coated on the support in advance.

The slurry is applied to the porous support one or more times so that the materials contained in the slurry are absorbed into the porous support, and the number of times of application of the slurry can be adjusted as desired according to the amount impregnated in the porous support.

The membrane is dried and compressed to obtain a solid electrolyte layer and a positive electrode composite layer (S4).

After drying the membrane coated with the slurry on a porous support, it is compressed to obtain a solid electrolyte layer and a positive electrode composite layer having high structural density. In the case of the drying process, it may be naturally dried at room temperature without performing a separate heat treatment, but if necessary, heat treatment at 50 to 300° C. under vacuum or an inert atmosphere may be performed to increase lithium ion conductivity. Also, the drying process and the pressing process may be performed as separate steps, or drying and pressing may be performed at once.

In the process of compressing the membrane, the porosity of the membrane can be reduced by compressing the membrane at a pressure of 10 to 500 MPa to perform structural densification. Compression of the membrane may be performed one or more times depending on the desired porosity. Preferably, the membrane has a porosity of 10% by volume or less, and when the porosity of the membrane exceeds 10% by volume, the conductivity may decrease due to poor connection between the materials present therein.

It is preferable that the thickness of the finally formed membrane is 20 to 350 μm. If the thickness of the membrane is less than 20 μm, it does not contain sufficient slurry inside, and if it exceeds 350 μm, the thickness of the membrane is too thick, so The volume of the solid-state battery may increase.

bookbinder wt% sulfide solid electrolyte menstruum coatability Lithium ion conductivity (S/cm) PEPMNB One LPSCl or LPSI heptane ○ 2.30×10 ^-4

Table 4 shows the coating properties on the porous support and the lithium ion conductivity of the membrane including the porous support, and it can be seen that the coating property is excellent and the ionic conductivity is high.

In addition, in some cases, the steps of preparing a slurry containing a sulfide-based solid electrolyte (S2), applying the slurry to a porous support to form a membrane (S3), and drying and compressing the membrane (S4) are repeatedly performed. It may be used to form a solid electrolyte layer and a positive electrode composite layer.

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

<Example>

First, to obtain an amorphous-crystalline LPSCl (Li ₂ SP ₂ S ₅ -LiCl) solid electrolyte, Li ₂ S, P ₂ S ₅ LiCl powder was quantified and put into an 80 ml ball mill reaction vessel, and zirconia with a diameter of 10 mm Put 15 zirconia balls together. Then, high-energy dry ball milling was performed at 600 rpm for 20 hours (net time) to obtain LPSCl amorphous-crystalline powder. At this time, in order to prevent excessive temperature rise of the reaction vessel, the reaction was repeated for 30 minutes and then paused for 20 minutes.

In order to reduce the particle size of the obtained amorphous solid electrolyte, a solid electrolyte pulverization process is performed. For pulverizing the solid electrolyte, 2 g of the amorphous solid electrolyte powder is mixed with 16 ml of heptane, 2 ml of dibutyl ether, and a diameter of 3 mm. The amorphous-crystalline solid electrolyte particles were finely pulverized by ball milling at 150 rpm for 10 hours using a zirconia ball of After the amorphous-crystalline solid electrolyte particle pulverized powder thus obtained was recovered, an amorphous-crystalline solid electrolyte powder was obtained through washing, separation from liquid, vacuum drying at room temperature and vacuum drying at 180°C.

The procedure for preparing 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 _{LiZrO 3} or LiNbO ₃ LiNi _0.6 Mn _0.2 Co _{0.2 O 2} positive electrode active material coated to a thickness of several to tens of nm, _the solid electrolyte is amorphous-crystalline LPSCl, and the conductive material is super P Alternatively, VGCF and PEPMNB as the binder are used to prepare a slurry in which they are mixed with heptane in a weight ratio of 70:25:3:2.

Then, the slurry for the positive electrode composite is applied to the porous support and impregnated into the porous support to prepare a membrane. After the prepared membrane is laminated on top of an aluminum current collector, it is then heat treated (dried) at 80° C. for 12 hours under vacuum or atmosphere, and then a pressure of 200 to 350 MPa is applied to prepare a positive electrode composite layer.

The slurry for a solid electrolyte is applied and impregnated on a porous support to prepare a membrane, and the membrane is again stacked on top of the previously prepared positive electrode composite layer, which is then heat treated and compressed. In some cases, the positive electrode composite membrane and the solid electrolyte membrane may be laminated first, and then compression may be performed through heat treatment and pressure at the same time. This process can be repeated several times in some cases to produce a good membrane.

Here, an experiment cell was prepared using a lithium-indium alloy counter electrode. The test cell consists of a positive electrode composite layer/solid electrolyte layer/lithium-indium alloy counter electrode, in detail, a positive electrode composite layer including LPSCl sulfide-based solid electrolyte, NCM ₆₂₂ , and a binder/LPSCl sulfide-based solid electrolyte and a binder. This is an experimental cell with a solid electrolyte layer/lithium-indium alloy indium counter electrode. Here, the sulfide-based solid electrolyte is an amorphous-crystalline solid electrolyte of LPSCl, and preferably has a particle size of 0.1 to 10 μm. At this time, instead of the counter electrode, a lithium-indium alloy counter electrode, an anode composite layer prepared by using a negative active material for lithium ion batteries such as graphite and mixing with a solid electrolyte in the same manner as the positive electrode composite, or an indium/lithium, lithium metal alloy electrode is used. battery can be manufactured.

2 is a graph showing the battery operation of the all-solid-state battery prepared in Examples, and it is possible to confirm charge/discharge performance with high energy density by preparing a positive electrode composite layer and a solid electrolyte layer to which a PEPMNB binder is added.

3 is an impedance graph measuring the lithium ion conductivity of a sulfide-based membrane including a porous support. Li ₆ PS ₅ Cl: PEPMNP = 99: 1 by weight ratio of heptane slurry and polyethylene as a porous support. This is an impedance graph. When the lithium ion conductivity of the sulfide-based membrane including the porous support is calculated using the resistance value obtained from this graph, the lithium ion conductivity is about 2.30×10 ⁻⁴ S/cm.

FIG. 4 is a photograph of a membrane including a porous support. A free-standing membrane consisting of a slurry mixed with a porous support made of polyethylene and a sulfide solid electrolyte Li ₆ PS ₅ Cl : PEPMNP = 99 : 1 by weight was 200 to 350 MPa. It is manufactured by pressing.

5 is a graph showing the operation of a sulfide-based all-solid-state battery composed of a positive electrode composite positive electrode including a sulfide solid electrolyte and a sulfide-based membrane including a porous support using a slurry. The positive electrode composite was prepared using a slurry composed of LiNbO-coated NCM ₆₂₂ , Li ₆ PS ₅ Cl, VGCF, and PEPMNB. For the battery structure, LiNbO ₃ -coated NCM ₆₂₂ / porous support was pressed at a pressure of 200 to 350 MPa to form a Li-In alloy counter electrode and a battery. It can be seen from the graph that the all-solid-state battery of the present invention has excellent charge/discharge performance.

Therefore, in manufacturing the solid electrolyte layer and the positive electrode composite layer, it is advantageous to obtain a uniform mixed electrode to use an amorphous solid electrolyte having a small particle size of the crystalline or amorphous-crystalline solid electrolyte. In addition, the amorphous particles having a small particle size help to minimize the voids and maximize the contact between the constituent materials of the solid electrolyte layer or the electrode composite layer even when the solid electrolyte layer or the electrode composite layer is compressed.

As described above, when a solid electrolyte layer and a positive electrode composite layer are prepared using a membrane impregnated with a slurry through the present invention, and this is applied to an all-solid-state battery, a binder is mixed with a sulfide-based solid electrolyte and the solid electrolyte is contracted and expanded by repeated contraction and expansion. The effect of preventing breakage can be obtained.

Claims (9)

In the method for manufacturing a solid electrolyte layer and a positive electrode composite layer comprising a sulfide-based solid electrolyte,
preparing an amorphous-crystalline sulfide-based solid electrolyte;
preparing a slurry including the sulfide-based solid electrolyte, a binder, and a solvent;
forming a membrane by applying the slurry to the porous support so that the slurry is impregnated and supported into the pores of the porous support having a porosity of 10 to 95% by volume;
Drying and compressing the membrane to obtain a solid electrolyte layer and a positive electrode composite layer,
The slurry is
a solid electrolyte slurry including the sulfide-based solid electrolyte and a binder; and a positive electrode composite slurry including the sulfide-based solid electrolyte, a binder, a conductive material and a positive electrode active material; wherein the solid electrolyte layer is prepared through the solid electrolyte slurry and the positive electrode composite layer is prepared through the positive electrode composite slurry,
The binder is
polyamide-imide (PAI), polyimide (PI), polyamide (PA), polyamic acid, polyethylene oxide (PEO), polystyrene (PS), PEP-MNB(poly(ethylene-co-propyleneco-5-methylene-2-norbornene)), PVDF(polyvinylidene fluoride), PVDF-HFP(poly(vinylidene fluoride-co-hexafluoropropylene)), PS-NBR(polystyrene nitrile- butadiene rubber), PMMA-NBR (poly(methacrylate)nitrile-butadiene rubber), and a mixture thereof,
The drying is performed by heat treatment at 50 to 300° C. under vacuum or an inert atmosphere, and the compression is compressed at a pressure of 200 to 350 MPa, and the porosity of the membrane is reduced to 10% by volume or less by the drying and compression. A method for manufacturing a solid electrolyte layer and a positive electrode composite layer comprising a sulfide-based solid electrolyte, characterized in that.
delete The method of claim 1,
The sulfide-based solid electrolyte is LPSCl (Li-PS-Cl)-based solid electrolyte, the binder is PEP-MNB (poly (ethylene-co-propyleneco-5-methylene-2-norbornene)), and the solvent is heptane ( heptane), a method for manufacturing a solid electrolyte layer and a positive electrode composite layer comprising a sulfide-based solid electrolyte. The method of claim 1,
The binder is a solid electrolyte layer and a cathode composite layer manufacturing method comprising a sulfide-based solid electrolyte, characterized in that 0.1 to 10% by weight of the total 100% by weight of the slurry.

delete delete The method of claim 1,
The method of manufacturing a solid electrolyte layer and a positive electrode composite layer comprising a sulfide-based solid electrolyte, characterized in that the porous support has a thickness of 20 to 350 μm by drying and pressing. In the all-solid-state battery,
a current collector;
Including; a membrane formed on the upper portion of the current collector;
The membrane is
a positive electrode composite layer in which an amorphous-crystalline sulfide-based solid electrolyte having a size of 0.1 to 10 μm, a binder, a conductive material, and an active material are supported on a porous support;
A solid electrolyte layer stacked on top of the positive electrode composite layer, in which an amorphous-crystalline sulfide-based solid electrolyte having a size of 0.1 to 10 μm and a binder are supported on a porous support;
The binder is
polyamide-imide (PAI), polyimide (PI), polyamide (PA), polyamic acid, polyethylene oxide (PEO), polystyrene (PS), PEP-MNB(poly(ethylene-co-propyleneco-5-methylene-2-norbornene)), PVDF(polyvinylidene fluoride), PVDF-HFP(poly(vinylidene fluoride-co-hexafluoropropylene)), PS-NBR(polystyrene nitrile- butadiene rubber), PMMA-NBR (poly(methacrylate)nitrile-butadiene rubber), and a mixture thereof,
The all-solid-state battery, characterized in that the membrane has a porosity of 10% by volume or less by drying by performing heat treatment at 50 to 300° C. under vacuum or an inert atmosphere, and by pressing at a pressure of 200 to 350 MPa .
delete

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