KR20210137263A - All-solid state composite electrode based on metal support and method of manufacturing thereof and all-solid state secondary battery including the same - Google Patents

Abstract

Disclosed are a metal support-based all-solid-state composite electrode, a method for manufacturing the same, and an all-solid-state secondary battery having the same, wherein a metal support is used instead of a conductive agent to secure electrical conductivity, and an electrode active material and a solid electrolyte are complexed through high-temperature compression sintering to secure interfacial stability in a composite electrode. A method for manufacturing a metal support-based all-solid-state composite electrode according to the present invention includes the steps of: preparing the metal support; applying the electrode active material and a solid electrolyte composite solution on the metal support; and high-temperature compression sintering the metal support coated with the electrode active material and the solid electrolyte composite solution.

Description

Metal support-based all-solid-state composite electrode, manufacturing method thereof, and all-solid-state secondary battery having same

The present invention relates to a metal support-based all-solid-state composite electrode, a method for manufacturing the same, and an all-solid-state secondary battery having the same, and more particularly, to secure electrical conductivity by using a metal support instead of a conductive agent, and to obtain an electrode active material through high-temperature compression sintering The present invention relates to a metal support-based all-solid-state composite electrode capable of securing interfacial stability in a composite electrode by complexing a solid electrolyte with a composite electrode, a method for manufacturing the same, and an all-solid-state secondary battery having the same.

Unlike the electrode (liquid-solid) of the conventional lithium secondary battery, the electrode of the all-solid-state secondary battery is formed of the electrode active material and the solid electrolyte solid-solid interface, so it is important to have high stability (low resistance) at the interface.

Conventional all-solid-state battery electrodes have a thin-film structure to secure interfacial stability with a solid electrolyte, but all-solid-state secondary batteries having such a thin-film structure are limited in order to be used in various fields with low capacity.

Recently, in order to solve this problem, many studies have been conducted to increase the electrode active material of the all-solid-state secondary battery. However, when the electrode active material is increased through simple compounding, the content of the solid electrolyte and the conductive agent in the all-solid-state electrode is reduced. As a result, there was a problem in that the performance was deteriorated due to a decrease in safety and mechanical strength at the interface between the solid electrolyte and the electrode active material as well as a decrease in ionic and electrical conductivity of the electrode.

As a related prior document, there is Republic of Korea Patent Publication No. 10-2014-0073719 (published on Jun. 17, 2014), which discloses a method for manufacturing an all-solid-state battery having flexibility to minimize contact resistance of a solid-state electrolyte with an electrode. is described.

An object of the present invention is to secure electrical conductivity by using a metal support instead of a conductive agent, and by compounding an electrode active material and a solid electrolyte through high-temperature compression sintering, a metal support-based all-solid-state composite that can secure interfacial stability in a composite electrode An electrode, a method for manufacturing the same, and an all-solid-state secondary battery having the same are provided.

A metal support-based all-solid-state composite electrode manufacturing method according to an embodiment of the present invention for achieving the above object comprises the steps of preparing a metal support; applying an electrode active material and a solid electrolyte composite solution on the metal support; and high-temperature compression sintering of the metal support coated with the electrode active material and the solid electrolyte composite solution.

The metal support has a plate structure or a mesh structure, and has a thickness of 0.1 to 2 mm.

At this time, the metal support uses a metal material including at least one selected from Ni, NiCo, Cu, Al, and SUS.

Each of the electrode active material and the solid electrolyte is disposed on or inside the metal support.

The electrode active material is LiCoO ₂ , LiNiO ₂ , LiNi ₂ O ₄ , LiMn ₂ O ₄ , LiMnO ₂ , LiFePO ₄ , LiCoPO ₄ , Li(Ni _1-xy Mn _x Co _y )O ₂ (where 0 < x ≤ 2) , 0 < y ≤ 2), LiNi _x Co _y Al _z O ₂ and LiNi _0.5 Mn _1.5 O _{4 At} least one selected from the group consisting of.

In addition, the solid electrolyte is one selected from Li-La-MO-based (where M is any one of Co, B, Zr, Mn, Ni, and P), Li-BO, Li-PO, and Li-S. includes more than one species.

In addition, the electrode active material and the solid electrolyte are preferably added in a weight ratio of 5: 1 to 1: 3.

The high-temperature compression sintering is performed by any one method selected from hot press and spark plasma sintering.

Here, the high-temperature compression sintering is preferably carried out at 600 ~ 750 ℃ conditions.

A metal support-based all-solid-state composite electrode according to an embodiment of the present invention for achieving the above object includes a metal support; an electrode active material coated on the metal support; and a solid electrolyte coated on the metal support and mixed with the electrode active material.

The metal support has a plate structure or a mesh structure, and has a thickness of 0.1 to 2 mm.

At this time, the metal support uses a metal material including at least one selected from Ni, NiCo, Cu, Al, and SUS.

The electrode active material is LiCoO ₂ , LiNiO ₂ , LiNi ₂ O ₄ , LiMn ₂ O ₄ , LiMnO ₂ , LiFePO ₄ , LiCoPO ₄ , Li(Ni _1-xy Mn _x Co _y )O ₂ (where 0 < x ≤ 2) , 0 < y ≤ 2), LiNi _x Co _y Al _z O ₂ and LiNi _0.5 Mn _1.5 O _{4 At} least one selected from the group consisting of.

In addition, the solid electrolyte is one selected from Li-La-MO-based (where M is any one of Co, B, Zr, Mn, Ni, and P), Li-BO, Li-PO, and Li-S. includes more than one species.

An all-solid-state secondary battery having a metal support-based all-solid-state composite electrode according to an embodiment of the present invention for achieving the above object includes a first electrode that is an all-solid-state composite electrode; an electrolyte layer disposed on the first electrode; and a second electrode disposed on the electrolyte layer.

In addition, the all-solid-state battery may include a current collector disposed under the first electrode; an insulator surrounding and protecting side surfaces of the current collector, the first electrode, the solid electrolyte layer, and the second electrode; a first cap covering lower portions of the current collector and the insulator; and a second cap covering upper portions of the second electrode and the insulator.

The present invention secures the electrical conductivity in the all-solid-state composite electrode by using a metal support when forming the all-solid-state composite electrode, and combines the electrode active material and the solid electrolyte with the metal support through high-temperature compression sintering to improve interfacial stability in the composite electrode. be able to improve

In addition, the present invention can greatly increase the mechanical strength of the all-solid-state composite electrode by using a metal support having a plate structure or a mesh structure.

In addition, the present invention can secure the mobility of lithium ions and electrons in the all-solid-state composite electrode through the solid electrolyte and the metal support in the composite electrode when the metal support-based all-solid-state composite electrode is formed.

In addition, the present invention can have a high energy density because the electrode active material can be further increased by using the metal support, and is manufactured in a form in which the electrode active material and the solid electrolyte are compressed on the metal support through high-temperature compression sintering, so that the metal Interfacial stability between the support and the electrode active material and the solid electrolyte may be improved.

As a result, the present invention can improve the mechanical strength and electrode stability of the all-solid-state secondary battery, and by further expanding the possibility of maintaining the performance for a long time, it is possible to secure the external competitiveness of related industries.

1 is a cross-sectional view showing an all-solid-state secondary battery according to an embodiment of the present invention.
2 is an enlarged cross-sectional view of part A of FIG. 1;
3 is a cross-sectional view showing an enlarged portion B of FIG.
4 and 5 are enlarged plan views of the metal support of FIG. 3 .
6 is a process flowchart illustrating a method for manufacturing a metal support-based all-solidity composite electrode according to an embodiment of the present invention.
7 is a graph showing the electrochemical property measurement results of the all-solid-state secondary battery to which the electrode prepared according to Example 1 is applied.

Advantages and features of the present invention, and methods for achieving them, will become apparent with reference to the embodiments described below in detail in conjunction with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but will be embodied in various different forms, only this embodiment allows the disclosure of the present invention to be complete, and common knowledge in the technical field to which the present invention belongs It is provided to fully inform the possessor of the scope of the invention, and the present invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout.

Hereinafter, with reference to the accompanying drawings, a metal support-based all-solid-state composite electrode according to a preferred embodiment of the present invention, a manufacturing method thereof, and an all-solid-state secondary battery having the same will be described in detail as follows.

1 is a cross-sectional view illustrating an all-solid-state secondary battery according to an embodiment of the present invention, and FIG. 2 is an enlarged cross-sectional view of part A of FIG. 1 .

1 and 2 , an all-solid-state secondary battery 800 according to an embodiment of the present invention includes a first electrode 100 , an electrolyte layer 200 , and a second electrode 300 .

The first electrode 100 may be used as an anode. In this case, the first electrode 100 includes a metal support, an electrode active material, and a solid electrolyte. A detailed configuration of the first electrode 100 will be described later.

The electrolyte layer 200 is disposed on the first electrode 100 . In this case, a ceramic-based solid electrolyte or an organic solid electrolyte may be used as the electrolyte layer 200 . As the ceramic solid electrolyte, one selected from Li-La-MO-based (where M is any one of Co, B, Zr, Mn, Ni, and P), Li-BO, Li-PO, and Li-S More than one species may be used. Examples of the organic solid electrolyte include a lithium salt in at least one selected from polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphoric acid ester polymers, poly agitation lysine, polyester sulfide, polyvinyl alcohol, and polyvinylidene fluoride. A mixture of may be used.

The second electrode 300 is disposed on the electrolyte layer 200 . This second electrode 300 may be used as a cathode. In this case, the second electrode 300 may be formed of a material containing lithium. That is, the second electrode 300 may be formed using at least one selected from lithium metal, lithium alloy, lithium oxide, and lithium compound. As the lithium alloy, a metal alloy selected from the group consisting of lithium and Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Al and Sn may be used. In addition, the lithium compound is a material capable of reversibly forming a lithium-containing compound by reacting with lithium ions, for example, tin (Sn), tin oxide (SnO ₂ ), silicon (Si), silicon oxide (SiO ₂ ), titanium nitrates and the like.

In addition, the all-solid-state secondary battery 800 according to the embodiment of the present invention may further include a current collector 400 , an insulator 500 , a first cap 600 , and a second cap 700 .

The current collector 400 is disposed under the first electrode 100 . As the current collector 400, a general metal thin film may be used, and specifically, any one metal thin film selected from Cu, Ni, Li, SUS, Al, and the like may be used.

The insulator 500 surrounds and protects the sides of the current collector 400 , the first electrode 100 , the electrolyte charge 200 , and the second electrode 300 . The insulator 400 may be used without particular limitation as long as it has insulating properties, and as an example, a PET (polyethylene terephthalate) material may be used.

The first cap 600 covers the lower portions of the current collector 400 and the insulator 500 , and the second cap 700 covers the second electrode 300 and the upper portions of the insulator 500 . Each of the first and second caps 600 and 700 may be made of a stainless steel (SUS) material coated with Au, but is not limited thereto.

Hereinafter, the metal support-based all-solid-state composite electrode, which is the first electrode, will be described in more detail with reference to the accompanying drawings.

FIG. 3 is an enlarged cross-sectional view of part B of FIG. 2 , and FIGS. 4 and 5 are plan views showing enlarged views of the metal support of FIG. 3 , which will be described in conjunction with FIG. 2 .

As shown in FIGS. 2 and 3 , the first electrode, the metal support-based all-solid-state composite electrode 100 , includes a metal support 120 , an electrode active material 140 , and a solid electrolyte 160 .

The metal support 120 does not use a conventional powder-type conductive agent, but a structure made of a metal material having excellent rigidity.

As shown in FIG. 4 , the metal support 120 may have a mesh structure having a plurality of pores. Also, the metal support 120 may have an integrated plate structure, as shown in FIG. 5 .

As described above, in the present invention, by using the metal support 120 , which is a metal structure having a mesh structure or a plate structure, it is possible to secure the strength and rigidity of the all-high-performance composite electrode 100 , so that it can have excellent mechanical properties. To this end, it is preferable to use at least one selected from among Ni, NiCo, Cu, Al, and stainless steel (SUS) as a material of the metal support 120 .

The metal support 120 is compressed through high-temperature compression sintering in a state in which the electrode active material 140 and the solid electrolyte 160 are coated. Due to the sintering effect through the high-temperature compression process, the thickness of the composite electrode including the final sintered metal support 120 is reduced to 50% or less.

In this case, the final thickness of the metal support 120 may preferably have a thickness of 0.1 to 2 mm, and a thickness of 1 to 300 μm may be presented as a more preferable range.

When the final thickness of the metal support 120 is less than 0.1 μm, it is difficult to secure the mechanical strength of the composite electrode 100 as well as the amount of the electrode active material 140 in the composite electrode 100 is small, so that the capacity of the battery is reduced. may be lowered. Conversely, when the final thickness of the metal support 120 exceeds 2 mm, the amount of the electrode active material 140 is greater than that of the metal support 120 acting as a conductor in the composite electrode 100, so that the composite electrode 100 has electricity. It may be difficult to secure conductivity as well as difficulty in securing interfacial stability.

The electrode active material 140 is LiCoO ₂ , LiNiO ₂ , LiNi ₂ O ₄ , LiMn ₂ O ₄ , LiMnO ₂ , LiFePO ₄ , LiCoPO ₄ , Li(Ni _1-xy Mn _x Co _y )O ₂ (where 0 < x ≤ 2, 0 < y ≤ 2), LiNi _x Co _y Al _z O ₂ and LiNi _0.5 Mn _1.5 O _{4 At} least one selected from the group consisting of.

The solid electrolyte 160 is one selected from Li-La-MO-based (where M is any one of Co, B, Zr, Mn, Ni, and P), Li-BO, Li-PO, and Li-S-based. It may include more than one species.

Here, the electrode active material 140 and the solid electrolyte 160 are mixed in a solvent, coated on the metal support 120 , and compressed through high-temperature compression sintering. Each of the electrode active material 140 and the solid electrolyte 160 is disposed on the surface or inside of the metal support 120 by compression by the high-temperature compression sintering.

Here, the electrode active material 140 and the solid electrolyte 160 are preferably added in a weight ratio of 5:1 to 1:3. As described above, in the present invention, by strictly controlling the content ratio of the electrode active material 140 and the solid electrolyte 160 within the above range, it is possible to secure a high energy density by increasing the content of the electrode active material 140 .

The metal support-based composite electrode 100 according to the embodiment of the present invention described above can improve mechanical strength by using the metal support 120 without a conductive agent, and excellent electrical conductivity can be secured when applied to an all-solid-state secondary battery can be done

In addition, since the metal support-based composite electrode 100 according to an embodiment of the present invention is manufactured in a form in which the electrode active material 140 and the solid electrolyte 160 are compressed to the metal support 120 through high-temperature compression sintering, the metal support body Interfacial stability between 120 and the electrode active material 140 and the solid electrolyte 160 may be improved.

As a result, since the present invention can improve the interfacial stability between the solid electrolyte 160, the electrode active material 140, and the metal support 120 in the all-solid-state composite electrode 100, the mechanical strength and capacity of the all-solid-state secondary battery can be kept stable.

This will be described in more detail through a method for manufacturing a metal support-based all-solid-state composite electrode according to an embodiment of the present invention.

6 is a process flowchart illustrating a method for manufacturing a metal support-based all-solidity composite electrode according to an embodiment of the present invention.

As shown in FIG. 6 , the method for manufacturing a metal support-based all-solid-state composite electrode according to an embodiment of the present invention includes a metal support preparation step (S210), an electrode active material and a solid electrolyte composite solution application step (S220), and a high-temperature compression sintering step (S230).

Metal support preparation

In the metal support preparation step ( S210 ), a metal support having a plate structure or a mesh structure is prepared.

The metal support is made of a metal material having a plate structure or a mesh structure having excellent rigidity, unlike the conventional conductive material. For this, it is preferable to use at least one selected from Ni, NiCo, Cu, Al, and stainless steel (SUS) as the material of the metal support.

Application of electrode active material and solid electrolyte composite solution

In the step of applying the electrode active material and the solid electrolyte composite solution ( S220 ), the electrode active material and the solid electrolyte composite solution are applied on the metal support.

In this step, any one method selected from spray coating, ultra ultrasonic spray coating, comma coating, bar coating, etc. may be used for application, but is not limited thereto. Therefore, any method capable of uniformly coating the metal support may be used without limitation.

In this case, the electrode active material and the solid electrolyte are preferably added in a weight ratio of 5: 1 to 1: 3. As described above, in the present invention, by strictly controlling the content ratio of the electrode active material and the solid electrolyte within the above range, it is possible to secure a high energy density by increasing the content of the electrode active material.

Here, the electrode active material and the solid electrolyte composite solution may be prepared by mixing the electrode active material and the solid electrolyte in a solvent and stirring.

The electrode active material is LiCoO ₂ , LiNiO ₂ , LiNi ₂ O ₄ , LiMn ₂ O ₄ , LiMnO ₂ , LiFePO ₄ , LiCoPO ₄ , Li(Ni _1-xy Mn _x Co _y )O ₂ , where 0 < x ≤ 2, 0 < y ≤ 2), LiNi _x Co _y Al _z O ₂ and LiNi _0.5 Mn _1.5 O _{4 At} least one selected from the group consisting of.

The solid electrolyte comprises at least one selected from Li-La-MO-based (where M is any one of Co, B, Zr, Mn, Ni, and P), Li-BO, Li-PO, and Li-S. may include

In addition, as the solvent, at least one selected from NMP (N-methyl-2-pyrrolidone), water, alcohol, xylene, toluene, and the like may be used.

high temperature compression sintering

In the high-temperature compression sintering step (S230), the high-temperature compression sintering of the metal support coated with the electrode active material and the solid electrolyte composite solution is performed.

In this step, the high-temperature compression sintering is preferably performed by any one method selected from hot press and spark plasma sintering.

By such high-temperature compression sintering, the solvent in the electrode active material and the solid electrolyte composite solution is volatilized and removed. In addition, each of the electrode active material and the solid electrolyte is disposed on the surface or inside of the metal support by compression by high-temperature compression sintering.

High-temperature compression sintering for manufacturing the composite electrode is preferably performed at 600 ~ 750 °C conditions. When the high-temperature compression sintering temperature is less than 600° C., since the temperature is low, sintering may not be performed properly. Conversely, when the high-temperature compression sintering temperature exceeds 750° C., the structure of the electrode active material applied to the composite electrode is changed, so that it cannot function as the electrode active material, which is not preferable.

The metal support-based all-solidity composite electrode manufactured by the above-described methods (S210 to S230) can secure electrical conductivity while having excellent mechanical strength by using a metal support instead of a conductive agent.

In addition, the metal support-based all-solidity composite electrode manufactured by the method according to the embodiment of the present invention can improve interfacial stability in the composite electrode by compounding the electrode active material and the solid electrolyte through high-temperature compression sintering.

As described so far, the present invention secures electrical conductivity in the all-solid-state composite electrode by using a metal support when forming the all-solid-state composite electrode, and complexes the electrode active material and the solid electrolyte on the metal support through high-temperature compression sintering. It is possible to improve the interfacial stability in the composite electrode.

In addition, the present invention can greatly increase the mechanical strength of the all-solid-state composite electrode by using a metal support having a plate structure or a mesh structure.

In addition, the present invention can secure the mobility of lithium ions and electrons in the all-solid-state composite electrode through the solid electrolyte and the metal support in the composite electrode when the metal support-based all-solid-state composite electrode is formed.

In addition, the present invention can have a high energy density because the electrode active material can be further increased by using the metal support, and is manufactured in a form in which the electrode active material and the solid electrolyte are compressed on the metal support through high-temperature compression sintering, so that the metal Interfacial stability between the support and the electrode active material and the solid electrolyte may be improved.

As a result, the present invention can improve the mechanical strength and electrode stability of the all-solid-state secondary battery, and by further expanding the possibility of maintaining the performance for a long time, it is possible to secure the external competitiveness of related industries.

In addition, the all-solid-state secondary battery using the metal support-based all-solid-state electrode according to an embodiment of the present invention can establish a basic technology for a next-generation secondary battery.

As a result, the possibility of practical application of these technologies can be further expanded due to the localization of the performance of the all-solid-state secondary battery and related materials, and thus the external competitiveness of related industries can be secured.

Example

Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, this is presented as a preferred example of the present invention and cannot be construed as limiting the present invention in any sense.

Content not described here will be omitted because it can be technically inferred sufficiently by a person skilled in the art.

1. Manufacturing of all-solid-state composite electrode

Example 1

A metal support made of Al having a mesh structure and a thickness of 5 μm was prepared.

Next, on both sides of the metal support, _{50 g of the electrode active material LiCoO 2} and 100 g of the solid electrolyte Li ₇ La ₃ Zr ₂ O ₁₂ were mixed in 200 ml of absolute ethanol, and the electrode active material and the solid electrolyte composite solution were stirred and coated in a spray coating method. .

Next, the metal support coated with the electrode active material and the solid electrolyte composite solution was put into a hot press, and then high-temperature compression sintered at 600° C. for 1 minute to prepare an all-solid-state composite electrode.

Here, the metal support was compressed to a final thickness of 1.5 μm by high-temperature compression sintering.

Example 2

A metal support made of Al having a plate structure and having a thickness of 30 μm was prepared.

Next, on both sides of the metal support, _{50 g of the electrode active material LiCoO 2} and 100 g of the solid electrolyte Li ₇ La ₃ Zr ₂ O ₁₂ were mixed in 200 ml of absolute ethanol, and the electrode active material and the solid electrolyte composite solution were stirred and coated in a spray coating method. .

Next, the metal support coated with the electrode active material and the solid electrolyte composite solution was put into a hot press, and then high-temperature compression sintered at 680° C. for 50 seconds to prepare an all-solid-state composite electrode.

Here, the metal support was compressed to a final thickness of 12.5 μm by high-temperature compression sintering.

Example 3

A metal support made of Al having a plate structure and having a thickness of 100 μm was prepared.

Next, on both sides of the metal support, _{50 g of the electrode active material LiCoO 2} and 100 g of the solid electrolyte Li ₇ La ₃ Zr ₂ O ₁₂ were mixed in 200 ml of absolute ethanol, and the electrode active material and the solid electrolyte composite solution were stirred and coated in a spray coating method. .

Next, the metal support coated with the electrode active material and the solid electrolyte composite solution was put into a hot press, and then high-temperature compression sintered at 700° C. for 40 seconds to prepare an all-solid-state composite electrode.

Here, the metal support was compressed to a final thickness of 31.6 μm by high-temperature compression sintering.

Example 4

A metal support made of Al having a mesh structure and a thickness of 2 mm was prepared.

Next, on both sides of the metal support, _{50 g of the electrode active material LiCoO 2} and 100 g of the solid electrolyte Li ₇ La ₃ Zr ₂ O ₁₂ were mixed in 200 ml of absolute ethanol, and the electrode active material and the solid electrolyte composite solution were stirred and coated in a spray coating method. .

Next, the metal support coated with the electrode active material and the solid electrolyte composite solution was put into a hot press, and then high-temperature compression sintered at 640° C. for 70 seconds to prepare an all-solid-state composite electrode.

Here, the metal support was compressed to a final thickness of 296.8 µm by high-temperature compression sintering.

Example 5

On both sides of the metal support, _{70 g of the electrode active material LiCoO 2} and 100 g of the solid electrolyte Li ₇ La ₃ Zr ₂ O ₁₂ were mixed in 200 ml of absolute ethanol, and the electrode active material and the solid electrolyte composite solution were used, except for using Example 1 An all-solid-state composite electrode was prepared in the same manner.

Comparative Example 1

A metal support made of Al having a mesh structure and a thickness of 10 mm was prepared.

Next, on both sides of the metal support, _{50 g of the electrode active material LiCoO 2} and 100 g of the solid electrolyte Li ₇ La ₃ Zr ₂ O ₁₂ were mixed in 200 ml of absolute ethanol, and the electrode active material and the solid electrolyte composite solution were stirred and coated in a spray coating method. .

Next, the metal support coated with the electrode active material and the solid electrolyte composite solution was put into a hot press, and then high-temperature compression sintered at 650° C. for 1 minute to prepare an all-solid-state composite electrode.

Here, the metal support was compressed to a final thickness of 3.5 mm by high-temperature compression sintering.

2. Physical property evaluation

Table 1 shows the results of measuring the electrochemical properties of the all-solid-state secondary batteries to which the all-solid-state composite electrodes prepared according to Examples 1 to 5 and Comparative Example 1 are applied. 7 is a graph showing the results of measuring the electrochemical properties of the all-solid-state secondary battery to which the all-solid-state composite electrode prepared according to Example 1 is applied.

[Table 1]

As shown in Table 1, it can be seen that the all-solid-state secondary battery to which the metal support-based all-solid-state composite electrode prepared according to Examples 1 to 5 is applied exhibits a capacity of ^{2.0 mAh/cm -2 or more.}

In particular, as shown in FIG. 7 , the all-solid-state secondary battery to which the metal support-based all-solid-state composite electrode prepared according to Example 1 was applied ^{exhibited a capacity of 2.5 mAh/cm -2} and thus it was confirmed that it had the best physical properties.

On the other hand, it was confirmed that the all-solid-state secondary battery to which the all-solid-state composite electrode manufactured according to Comparative Example 1 was applied did not satisfy the ^{target value of 2.0 mAh/cm -2 or more.} This is considered to be due to the decrease in electrical conductivity due to the increase in the amount of the electrode active material due to the formation of the metal support to an excessive thickness. In addition, it is judged that the capacity of the all-solid-state secondary battery is reduced due to the decrease in interfacial stability in the all-solid-state composite electrode based on the metal support.

In the above, the embodiments of the present invention have been mainly described, but various changes or modifications can be made at the level of those skilled in the art to which the present invention pertains. Such changes and modifications can be said to belong to the present invention as long as they do not depart from the scope of the technical spirit provided by the present invention. Accordingly, the scope of the present invention should be judged by the claims described below.

800: all-solid-state battery 100: first electrode
120: electrode active material 140: solid electrolyte
160: conductive agent 200: electrolyte layer
300: second electrode 400: current collector
500: insulator 600: first cap
700: second cap

Claims (16)

preparing a metal support;
applying an electrode active material and a solid electrolyte composite solution on the metal support; and
high-temperature compression sintering of the metal support coated with the electrode active material and the solid electrolyte composite solution;
Metal support-based all-solid-state composite electrode manufacturing method comprising a.
According to claim 1,
The metal support
A metal support-based all-solid-state composite electrode manufacturing method, characterized in that it has a plate structure or a mesh structure and has a thickness of 0.1 to 2 mm.
According to claim 1,
The metal support
A method for manufacturing a metal support-based all-solid-state composite electrode, characterized in that a metal material containing at least one selected from Ni, NiCo, Cu, Al and SUS is used.
According to claim 1,
Each of the electrode active material and the solid electrolyte
A metal support-based all-solid-state composite electrode manufacturing method, characterized in that it is disposed on the surface or inside of the metal support.
According to claim 1,
The electrode active material is
LiCoO ₂ , LiNiO ₂ , LiNi ₂ O ₄ , LiMn ₂ O ₄ , LiMnO ₂ , LiFePO ₄ , LiCoPO ₄ , Li(Ni _1-xy Mn _x Co _y )O ₂ , where 0 < x ≤ 2, 0 < y ≤ 2), LiNi _x Co _y Al _z O ₂ and LiNi _0.5 Mn _1.5 O ₄ Metal support-based all-solid-state composite electrode manufacturing method, characterized in that it comprises at least one selected from the group consisting of.
According to claim 1,
The solid electrolyte is
Li-La-MO-based (where M is any one of Co, B, Zr, Mn, Ni, and P), Li-BO-based, Li-PO-based, Li-S-based containing at least one selected from the group consisting of Method for manufacturing a metal support-based all-solid-state composite electrode, characterized in that.
According to claim 1,
The electrode active material and the solid electrolyte are
A method for manufacturing a metal support-based all-solid-state composite electrode, characterized in that it is added in a weight ratio of 5: 1 to 1: 3.
According to claim 1,
The high-temperature compression sintering is
A method of manufacturing a metal support-based all-solid-state composite electrode, characterized in that it is carried out by any one method selected from hot press and spark plasma sintering.
According to claim 1,
The high-temperature compression sintering is
A method for manufacturing a metal support-based all-solid-state composite electrode, characterized in that carried out at 600 ~ 750 ℃ conditions.
metal support;
an electrode active material coated on the metal support; and
a solid electrolyte coated on the metal support and mixed with the electrode active material;
A metal support-based all-solid-state composite electrode comprising a.
11. The method of claim 10,
The metal support
A metal support-based all-solid-state composite electrode having a plate structure or a mesh structure, and having a thickness of 0.1 to 2 mm.
11. The method of claim 10,
The metal support
A metal support-based all-solid-state composite electrode, characterized in that it uses a metal material comprising at least one selected from Ni, NiCo, Cu, Al and SUS.
11. The method of claim 10,
The electrode active material is
LiCoO ₂ , LiNiO ₂ , LiNi ₂ O ₄ , LiMn ₂ O ₄ , LiMnO ₂ , LiFePO ₄ , LiCoPO ₄ , Li(Ni _1-xy Mn _x Co _y )O ₂ , where 0 < x ≤ 2, 0 < y ≤ 2), LiNi _x Co _y Al _z O ₂ and LiNi _0.5 Mn _1.5 O ₄ A metal support-based all-solid-state composite electrode comprising at least one selected from the group consisting of.
11. The method of claim 10,
The solid electrolyte is
Li-La-MO-based (where M is any one of Co, B, Zr, Mn, Ni, and P), Li-BO-based, Li-PO-based, Li-S-based containing at least one selected from the group consisting of A metal support-based all-solid-state composite electrode.
A first electrode which is an all-solid-state composite electrode according to any one of claims 10 to 14;
an electrolyte layer disposed on the first electrode; and
a second electrode disposed on the electrolyte layer;
All-solid-state secondary battery having a metal support-based all-solid-state composite electrode comprising a.
16. The method of claim 15,
The all-solid-state battery is
a current collector disposed under the first electrode;
an insulator surrounding and protecting side surfaces of the current collector, the first electrode, the solid electrolyte layer, and the second electrode;
a first cap covering lower portions of the current collector and the insulator; and
a second cap covering upper portions of the second electrode and the insulator;
An all-solid-state secondary battery having a metal support-based all-solid-state composite electrode further comprising a.

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