KR102402004B1 - Manufacturing Method of solid electrolyte with specific pattern - Google Patents

Abstract

The present invention relates to a process for the preparation of certain types of solid electrolytes. A method of manufacturing a specific type of solid electrolyte according to an embodiment of the present invention comprises the steps of: (a) generating a precursor solution including a precursor material; (b) impregnating a guide member of a specific shape in the precursor solution; (c) drying the impregnated guide member; and (d) heat-treating the dried guide member to generate the solid electrolyte of the specific type from the dried guide member.

Description

Manufacturing method of solid electrolyte with specific pattern

The present invention relates to a method for manufacturing a solid electrolyte, and more particularly, to a method for manufacturing a solid electrolyte having a specific shape.

In a secondary battery, metal ions (eg, lithium ions, sodium ions) move from the positive electrode to the negative electrode during charging, and metal ions move from the negative electrode to the positive electrode during discharging. In this case, the solid electrolyte between the anode part and the cathode part should facilitate the transfer of metal ions and maintain an electrically insulating state. Accordingly, secondary batteries include various materials and designs, and secondary batteries requiring high induced current efficiency use a solid electrolyte separator. Therefore, there is a need to manufacture a solid electrolyte in consideration of economy and versatility, but research results on this are still insufficient.

[Patent Document 1] Korean Patent No. 10-0294467

The present invention was created to solve the above problems, and an object of the present invention is to provide a method for manufacturing a solid electrolyte of a specific type.

Another object of the present invention is to provide a method for manufacturing a solid electrolyte in the form of a guide member by heat-treating a guide member impregnated in a precursor solution.

Objects of the present invention are not limited to the objects mentioned above, and other objects not mentioned will be clearly understood from the description below.

In order to achieve the above objects, a method for manufacturing a solid electrolyte of a specific type according to an embodiment of the present invention includes the steps of: (a) generating a precursor solution including a precursor material; (b) impregnating a guide member of a specific shape in the precursor solution; (c) drying the impregnated guide member; and (d) heat-treating the dried guide member to generate the solid electrolyte of the specific type from the dried guide member.

In an embodiment, the step (a) may include dissolving the precursor material in an ethanol solvent to generate the precursor solution.

In an embodiment, the step (d) may include thermally decomposing the guide member by heat-treating the dried guide member at a first temperature.

In an embodiment, the step (d) may include heat-treating the dried guide member at the first temperature to shrink the precursor material included in the guide member into the specific shape.

를 포함할 수 있다. In an embodiment, the first temperature is 500 to 600

may include

In an embodiment, the step (d) comprises the steps of heat-treating the precursor material shrunk in the specific shape at a second temperature, sintering the precursor material shrunk in the specific shape to produce a solid electrolyte of the specific shape; may include

를 포함할 수 있다. In an embodiment, the second temperature is 900 to 1100

may include

Specific details for achieving the above objects will become clear with reference to the embodiments to be described in detail below in conjunction with the accompanying drawings.

However, the present invention is not limited to the embodiments disclosed below, it may be configured in various different forms, and those of ordinary skill in the art to which the present invention belongs ( Hereinafter, "a person skilled in the art") is provided to fully inform the scope of the invention.

According to an embodiment of the present invention, a solid electrolyte having a specific shape may be manufactured by sintering a precursor material, which has only been sintered in the form of a simple pellet, into a specific shape.

According to an embodiment of the present invention, when a solid electrolyte that selectively passes only ions such as Li and Na is manufactured in the shape of various guide members, various battery systems such as a flexible battery and a thin film battery can be applied to

In addition, according to an embodiment of the present invention, mass production of a solid electrolyte may be possible if only a guide member having a desired shape is used as a precursor manufactured in the form of a solution.

The effects of the present invention are not limited to the above-described effects, and potential effects expected by the technical features of the present invention will be clearly understood from the following description.

1 is a diagram illustrating a method of manufacturing a specific type of solid electrolyte according to an embodiment of the present invention.
2A is a diagram illustrating a precursor solution according to an exemplary embodiment of the related art.
2B is a diagram illustrating a precursor solution according to an embodiment of the present invention.
3 is a diagram illustrating a manufacturing process of a specific type of solid electrolyte according to an embodiment of the present invention.
Figure 4a is a view showing a guide member according to an embodiment of the present invention.
4B is a view illustrating a precursor solution impregnated with a guide member according to an embodiment of the present invention.
4C is a diagram illustrating a solid electrolyte according to an embodiment of the present invention.
5A is a diagram illustrating a sintering process of a solid electrolyte according to an embodiment of the present invention.
5B is a diagram illustrating a solid electrolyte for each heat treatment temperature according to an embodiment of the present invention.
5C is a view showing various types of solid electrolytes according to an embodiment of the present invention.
6A is a diagram illustrating an XRD analysis graph according to an embodiment of the present invention.
6B to 6E are diagrams illustrating various types of solid electrolytes according to an embodiment of the present invention.
7 is a diagram illustrating an ionic conductivity graph of a solid electrolyte according to an embodiment of the present invention.

Since the present invention can have various changes and can have various embodiments, specific embodiments are illustrated in the drawings and described in detail.

Various features of the invention disclosed in the claims may be better understood upon consideration of the drawings and detailed description. The apparatus, methods, preparations, and various embodiments disclosed herein are provided for purposes of illustration. The disclosed structural and functional features are intended to enable those skilled in the art to specifically practice the various embodiments, and are not intended to limit the scope of the invention. The disclosed terms and sentences are for the purpose of easy-to-understand descriptions of various features of the disclosed invention, and are not intended to limit the scope of the invention.

In describing the present invention, if it is determined that a detailed description of a related known technology may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted.

Hereinafter, a method for manufacturing a specific type of solid electrolyte according to an embodiment of the present invention will be described.

1 is a diagram illustrating a method of manufacturing a specific type of solid electrolyte according to an embodiment of the present invention.

Referring to FIG. 1 , step S101 is a step of generating a precursor solution including a precursor material. In one embodiment, the precursor material may be dissolved in an ethanol solvent to form a precursor solution.

For example, the precursor material may be placed in an ethanol solvent and stirred to produce a transparent precursor solution. Also, for example, the precursor material may include a ceramic precursor material.

Step S103 is a step of impregnating the guide member of a specific shape in the precursor solution. In one embodiment, the precursor solution may be impregnated with a specific type of guide member for one or more days.

Here, the guide member may be referred to as a template or a term having an equivalent technical meaning. For example, the guide member may include a carbon fiber template.

Step S105 is a step of drying the impregnated guide member. In one embodiment, the impregnated guide member may be dried in the air.

Step S107 is a step of heat-treating the dried guide member to generate the solid electrolyte of the specific type from the dried guide member. For example, the solid electrolyte may include a ceramic solid electrolyte.

In an embodiment, the dried guide member may be heat-treated at a first temperature to thermally decompose the guide member.

를 포함할 수 있다. 즉, 특정 형태로 전구체 물질의 결정상이 생성될 수 있다. In an embodiment, the dried guide member may be heat-treated at a first temperature to shrink the precursor material included in the guide member to a specific shape. Here, the first temperature is 500 to 600

may include That is, a crystalline phase of the precursor material may be generated in a specific form.

를 포함할 수 있다. In an embodiment, the precursor material shrunk to a specific shape may be heat treated at a second temperature to sinter the precursor material shrunk to a specific shape to generate a solid electrolyte of a specific shape. Here, the second temperature is 900 to 1100

may include

That is, according to an embodiment of the present invention, a solid electrolyte material having a complex composition may be sintered according to a desired shape.

In addition, according to an embodiment of the present invention, the conventional ceramic solid electrolyte is produced only in the form of fragile pellets, so the application range is not wide. can

2A is a diagram illustrating a precursor solution according to an exemplary embodiment of the related art. 2B is a diagram illustrating a precursor solution according to an embodiment of the present invention.

Referring to FIG. 2A , the conventional LATP ceramic precursor solution may include a precursor solution used in the conventional solid-state synthesis or water-based synthesis method. In this case, the powder that has settled after mixing the precursor may be dried and then sintered.

9H₂O 및 Ti(OC₄H₉)₄를 물(H₂O)과 혼합하여 생성될 수 있다. For example, conventional LATP ceramic precursor solutions are LiCl, NH ₄ H ₂ PO ₄ , Al(NO ₃ ) ₃

9H ₂ O and Ti(OC ₄ H ₉ ) ₄ may be produced by mixing water (H ₂ O).

Referring to FIG. 2B , in the case of the precursor solution according to the present invention, a precursor material completely soluble in an ethanol solvent among precursors including each element may be used. In this case, since the precursor solution is completely dissolved in the ethanol solvent, the precursor solution according to the present invention can be directly used in the liquid phase.

For example, the precursor solution according to the present invention may be prepared by dissolving LiCl, AlCl ₃ , C ₃ H ₉ O ₄ P and Ti(C ₃ H ₅ O) ₄ in an ethanol solvent.

3 is a diagram illustrating a manufacturing process 300 of a specific type of solid electrolyte according to an embodiment of the present invention.

Referring to FIG. 3 , the manufacturing process 300 of a specific type of solid electrolyte may include an impregnation process 310 , a thermal decomposition process 320 , and a sintering process 330 .

In the impregnation process 310 , a guide member having a specific shape may be impregnated with the precursor solution. For example, referring to FIG. 4A , the guide member may have various shapes, such as a strand shape, a fabric shape, and a woven shape, but is not limited thereto. Also, referring to FIG. 4B , a precursor solution impregnated with such a guide member can be identified. Thereafter, the impregnated guide member may be dried.

In the thermal decomposition process 320 , the dried guide member may be heat treated at a first temperature to thermally decompose the guide member. In this case, as the guide member is thermally decomposed, the precursor material included in the guide member may be contracted into a specific shape.

In the sintering process 330 , the precursor material shrunk in a specific shape is heat-treated at a second temperature, and as illustrated in FIG. 4C , the precursor material shrunk in a specific shape is sintered to generate a solid electrolyte of a specific shape.

That is, according to an embodiment of the present invention, the solid electrolyte may be generated in a specific shape of the guide member through a heat treatment process such as the thermal decomposition process 320 and the sintering process 330 .

5A is a diagram illustrating a sintering process of a solid electrolyte for each heat treatment temperature according to an embodiment of the present invention. 5B is a diagram illustrating a solid electrolyte for each heat treatment temperature according to an embodiment of the present invention. 5C is a view showing various types of solid electrolytes according to an embodiment of the present invention.

로 2시간 동안 열처리하여 수분을 제거할 수 있다.Referring to FIG. 5A , the guide member impregnated in the precursor solution is 150

Moisture can be removed by heat treatment for 2 hours.

로 4시간 동안 열처리하여 가이드 부재를 열분해시킬 수 있다.In addition, the guide member

The guide member can be thermally decomposed by heat treatment for 4 hours.

로 4시간 동안 열처리하고, 950 내지 1100

로 열처리하여 수축된 전구체 물질을 소결시킬 수 있다. Thereafter, as the precursor material included in the guide member is shrunk in the form of the guide member through thermal decomposition, the contracted precursor material is

Heat treatment for 4 hours, 950 to 1100

The shrunken precursor material can be sintered by heat treatment with a furnace.

In this case, referring to FIG. 5B , it can be confirmed that the guide member is thermally decomposed according to each heat treatment temperature, and a solid electrolyte is generated in the same manner as in the specific shape of the guide member. In addition, referring to FIG. 5C , the guide member may have various shapes such as a strand shape, a fabric shape, and a cloth shape, but is not limited thereto.

6A is a diagram illustrating an XRD analysis graph according to an embodiment of the present invention. 6B to 6E are diagrams illustrating solid electrolyte images according to an embodiment of the present invention.

이상으로 소결한 후, XRD 분석을 통해 특정 형태로 전구체 물질의 LATP 결정상이 확인됨을 확인할 수 있다. 6A to 6E , 1000

After sintering as described above, it can be confirmed that the LATP crystal phase of the precursor material in a specific form is confirmed through XRD analysis.

In this case, it can be confirmed that the sintered LATP ceramic is sintered in the same shape as the carbon-based guide member. Even if the cross-sectional image and the 3D structure image are checked, it can be confirmed that the sintered LATP ceramic is sintered in the same shape as the carbon-based guide member, and Li ⁺ ion transport channels are created.

7 is a diagram illustrating an ionic conductivity graph of a solid electrolyte according to an embodiment of the present invention.

Referring to FIG. 7 , it can be seen that the solid electrolyte prepared according to an embodiment of the present invention not only has the same shape as the guide member, but also maintains the ionic conductivity of the ceramic solid electrolyte in terms of performance. That is, the shape of the solid electrolyte according to the present invention can be adjusted while maintaining the electrochemical characteristics.

In one embodiment, the ceramic solid electrolyte of the present invention may be composed of various materials suitable as electrolytes for lithium and ions, but is not limited thereto.

For example, the lithium ion conductive ceramic solid electrolyte is a NASICON-type (Li _1.3 Al _0.3 Ti _1.7 (PO ₄ ) ₃ , a mixture thereof with LAGP, etc. and other ion doping types thereof), LLTO-type (Li _3x La _2/3-x TiO ₃ etc.), LISICON-type (Li ₁₄ ZnGe ₄ O ₁₆ etc.), Composite-type (LiI-Al ₂ O ₃ etc.), LiPON (Li _2.88 PO _3.73 N _0.14 , Li ₃ PO _3.3 N _0.5 , etc.), Thio-LISICON type (Li ₁₀ GeP ₂ S ₁₂ , Li ₁₀ SnP ₂ S ₁₂ , Li ₂ S`30P ₂ S ₅ etc.), Garnet type (Li ₆ La ₂ BaTa ₂ O ₁₂ , Li ₇ La ₃ Zr ₂ O ₁₂ , etc.) and other lithium ion selective permeable ceramic solid electrolytes.

-Al₂O₃), NaPS₄ 계열(정방 위상(tetragonal phase) NaPS₄, 입방 위상(cubic phase) NaPS₄ 등과 이의 혼합 및 타 이온 도핑 류) 및 기타 소듐 이온 선택 투과성 세라믹 고체전해질을 포함할 수 있다. In addition, for example, the sodium ceramic solid electrolyte is a NASICON-based material (Na _1+x Zr ₂ P _3-x Si _x O ₁₂ , 0< x <3 and a doping material, NaMM'(PO ₄ ) ₃ , M or M' = Na+, V3+, Nb3+, Ta3+, ..), beta-Alumina (

-Al ₂ O ₃ ), NaPS ₄ series (tetragonal phase NaPS ₄ , cubic phase NaPS ₄ and mixtures thereof and other ion doping types) and other sodium ion selective permeable ceramic solid electrolytes have.

The above description is merely illustrative of the technical spirit of the present invention, and various changes and modifications may be made by those skilled in the art without departing from the essential characteristics of the present invention.

Accordingly, the embodiments disclosed in the present specification are not intended to limit the technical spirit of the present invention, but to illustrate, and the scope of the present invention is not limited by these embodiments.

The protection scope of the present invention should be interpreted by the claims, and all technical ideas within the scope equivalent thereto should be understood to be included in the scope of the present invention.

300: solid electrolyte manufacturing process
310: impregnation process
320: pyrolysis process
330: sintering process

Claims (7)

generating a precursor solution comprising a precursor material;
impregnating the precursor solution with a specific type of guide member;
drying the impregnated guide member;
heat-treating the dried guide member at a first temperature to shrink the precursor material included in the guide member into the specific shape; and
heat-treating the precursor material shrunk into the specific shape at a second temperature to sinter the precursor material shrunk to the specific shape to produce a solid electrolyte of the specific shape;
containing,
A method for preparing a specific type of solid electrolyte.
According to claim 1,
The step of generating the precursor solution comprises:
dissolving the precursor material in an ethanol solvent to produce the precursor solution;
containing,
A method for preparing a specific type of solid electrolyte.
According to claim 1,
The shrinking step is
thermally decomposing the guide member by heat-treating the dried guide member at a first temperature;
containing,
A method for preparing a specific type of solid electrolyte.
delete According to claim 1,
The first temperature is 500 to 600

containing,
A method for preparing a specific type of solid electrolyte.
delete According to claim 1,
The second temperature is 900 to 1100

containing,
A method for preparing a specific type of solid electrolyte.

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