KR101394128B1 - High ionic conductive ceramics film and fabrication method of the same and all-solid-state secondary battery using the same - Google Patents

Abstract

The present invention relates to a novel solid electrolyte membrane having a high ionic conductivity, a method for producing the same, and a full solid secondary battery using the same.
A solid electrolyte membrane according to the present invention is a solid electrolyte membrane sandwiched between a cathode layer and a cathode layer, comprising: a plurality of lithium ion exchange resins having a particle size of at least 1 탆; And an electron barrier layer formed at least between the plurality of lithium ions and the particles.

Description

TECHNICAL FIELD [0001] The present invention relates to a solid electrolyte membrane having a high ionic conductivity, a method for producing the same, and a full solid secondary battery using the same. [0002]

The present invention relates to a solid electrolyte membrane, and more particularly, to a solid electrolyte membrane having a novel structure having high ion conductivity, a method for producing the same, and a full solid secondary battery using the same.

Since the lithium ion secondary battery has a large electrochemical capacity, a high operating potential and an excellent charge / discharge cycle characteristic, it can be used for portable information terminals, portable electronic devices, small-sized power storage devices for household use, motorcycles, electric vehicles, hybrid electric vehicles Is increasing. With the spread of such applications, improvement of safety and high performance of lithium ion secondary batteries are required.

Conventional lithium ion secondary batteries are liable to be ignited when they are exposed to water in the air due to the use of a liquid electrolyte, thereby posing a problem of stability. This stability problem is becoming more and more important as electric cars become more visible.

Recently, all solid-state secondary batteries using a solid electrolyte made of an inorganic material, which is a nonflammable material, have been actively studied for the purpose of improving safety. All solid secondary batteries are attracting attention as a next generation secondary battery in terms of stability, high energy density, high output, long life, simplification of manufacturing process, enlargement / compactification of battery, and low cost.

The solid secondary battery is composed of a positive electrode layer / a solid electrolyte layer / a negative electrode layer. Of these, the solid electrolyte of the solid electrolyte layer requires a high ion conductivity and a low electronic conductivity.

Solid electrolytes satisfying these requirements include sulfides, oxides, and the like. And of the _{LLT (Li 3x La 2 / (} 3x) TiO 3) based, such as _{LLZ (Li 7 La 3 Zr 2} O 12) well known to Step oxide, all of which are relatively low, the grain boundary resistance due to the high total conductivity It is attracting attention as a promising material.

However, when the LLT or LLZ solid electrolyte is manufactured with a thin film or a thick film, there is a problem that the ion conductivity is markedly reduced to 1/100 of that of the bulk material. Therefore, a novel structure of an oxide-based solid electrolyte capable of securing a high ion conductivity even in the form of a film is required.

A prior art related to the present invention is Korean Patent Registration No. 10-1027898 (registered on Mar. 31, 2011), which discloses a solid electrolyte layer having a laminated structure of a positive electrode / solid electrolyte layer / A lithium ion secondary battery, and a lithium ion secondary battery.

It is an object of the present invention to provide an oxide solid electrolyte membrane having a novel structure having a high ion conductivity and to provide a pre-solid secondary battery having a novel structure having a high ion conductivity by employing this solid electrolyte membrane.

Another object of the present invention is to provide a process for producing an oxide solid electrolyte membrane having a novel structure having a high ion conductivity.

According to an aspect of the present invention, there is provided a solid electrolyte membrane interposed between an anode layer and a cathode layer, the solid electrolyte membrane comprising: a plurality of lithium ion batteries having a particle size of at least 1 m; And an electron barrier layer formed at least between the plurality of lithium ions and the particles.

According to another aspect of the present invention, there is provided a method of manufacturing a solid electrolyte membrane, the method comprising: (a) forming a plurality of lithium ions having a particle size of at least 1 탆, Or a cathode layer; And (b) forming an electron barrier layer between at least a plurality of lithium ions and the particles.

According to another aspect of the present invention, there is provided a full-solid-state secondary battery including a cathode layer, a cathode layer, and a solid electrolyte layer interposed between the anode layer and the cathode layer, A plurality of lithium ion exchange resins and particles having a size of 1 mu m or more; And an electron barrier layer formed at least between the plurality of lithium ions and the particles.

The solid electrolyte membrane according to the present invention is a novel structure including a plurality of lithium ion batteries having a size of at least 1 탆 and an electron barrier layer between the particles and the particles, It can have a high ionic conductivity.

In addition, Li _3x La ₂ film solid electrolyte of the present invention _{/ (3x) TiO 3 (0} <x≤2, LLT) or _{Li 7 La 3 Zr 2 O 12} (LLZ) oxide material, or 5 wt% or less Of all lithium ion solid electrolytes as well as the LLZ oxide material to which Al ₂ O ₃ is added can be used and high ionic conductivity of the bulk material can be adopted as it is.

All of the solid secondary batteries employing the solid electrolyte membrane of this novel structure can be used for electric vehicles as well as for electronic devices because the batteries can be secured with high performance and high performance.

Also, according to the present invention, it is possible to easily produce a solid electrolyte membrane having a novel structure having a high ion conductivity by using an existing method.

1 is a cross-sectional view showing a solid electrolyte membrane according to the present invention.
2 is a process flow chart for explaining a solid electrolyte membrane production method according to an embodiment of the present invention.
3 and 4 are process sectional views for explaining a solid electrolyte membrane production method according to FIG.
5 and 6 are process plan views for explaining a solid electrolyte membrane manufacturing method according to FIG.
7 is a cross-sectional view schematically showing a pre-solid secondary battery that can be manufactured using the solid electrolyte membrane according to the present invention.
FIG. 8 is a graph showing the relationship between the Li ₇ La ₃ Zr ₂ O ₁₂ - Ion conductivity of 1 wt% Al ₂ O ₃ ceramics.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving them will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings. However, it should be understood that the present invention is not limited to the embodiments disclosed herein but may be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art. Is provided to fully convey the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout the specification.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, an oxide solid electrolyte membrane having a high ionic conductivity according to the present invention, a method for producing the oxide solid electrolyte membrane, and a whole solid secondary battery using the oxide solid electrolyte membrane will be described in detail.

1 is a cross-sectional view showing a solid electrolyte membrane according to the present invention.

1, a solid electrolyte membrane 120 according to the present invention includes a plurality of lithium ion exchange membranes 121 having a particle size of at least 1 탆 and at least a plurality of lithium ion exchange membranes 121 formed between the ion exchange membranes 121 And an electron barrier layer 123. For the sake of convenience, lithium ion batteries and particles are described below as particles.

Here, the particle 121 is an oxide material, for example, Li _3x La _{2 / (3x),} TiO ₃ (0 <x≤2) (hereinafter referred to as LLT) or _{Li 7 La 3 Zr 2 O 12} ( hereinafter , LLZ) series material. The particles 121 to be used are not particularly limited as long as they have a function as a lithium ion solid electrolyte.

These LLT and LLZ are the most widely known oxide solid electrolytes and have a high ionic conductivity of about 10 ^-4 S / cm or more. Accordingly, when the particles 121 are formed of either LLT or LLZ, the ion conductivity of the solid electrolyte membrane 120 can be further improved.

On the other hand, the particles 121 may be composed of LLT or LLZ to which 5% by weight or less, more preferably 0.5 to 5% by weight, of Al ₂ O ₃ is added. In this case, the particles 121 may be LLZ or LLZ to which Al ₂ O ₃ is added.

Here, Al ₂ O ₃ has an effect of improving the ion conductivity of the particles 121 due to the formation of lithium vacancies while Al ^{3 +} ions are substituted for Li ⁺ sites. By the addition of Al ₂ O ₃ , the crystal structure of LLZ is changed to a cubic structure.

At this time, when Al ₂ O ₃ is added to LLZ in an amount less than 0.5% by weight, the effect of improving ionic conductivity may be insufficient. On the other hand, when added to LLZ in an amount exceeding 5% by weight, Can be lowered.

The particles 121 are interposed between the anode layer (not shown) and the cathode layer 110 to provide a path for lithium ion migration therebetween. The size of the particles 121 is at least 1 탆 And more preferably in the range of 1 m to 200 m.

When the particles 121 have a particle size of less than 1 mu m, it may be difficult to provide sufficient migration path of lithium ions between the anode layer and the cathode layer 110, while having a particle size exceeding 200 mu m , It may be difficult to make the solid electrolyte membrane 120 thinner.

The filling ratio of the particles 121 is represented by the value calculated by the following formula 1 and may have an area of the particles 121 with respect to the area of the solid electrolyte membrane 120. The higher the area of the particles 121, the higher the filling rate. The area of the particles 121 can ensure a higher filling rate when particles of various sizes are mixed rather than particles of the same size.

Since the packing ratio of the particles 121 and the ionic conductivity of the solid electrolyte membrane 120 are as shown in the following formula 2, when a high packing ratio is secured by mixing particles of various sizes, It is possible to maximize the effect of providing the migration path of the lithium ions of the particles 121 between the cathode layer 110 and the cathode layer 110.

[Formula 1]

Filling ratio of particles = [area of particles] / [area of solid electrolyte membrane]

[Formula 2]

Ionic conductivity of solid electrolyte membrane = ion conductivity of particles x packing ratio of particles

If the filling ratio of the particles 121 is less than 1%, it is similar to the ion conductivity of the solid electrolyte layer 120, which may make it difficult to provide a sufficient path of lithium ions between the anode layer and the cathode layer 110 . On the other hand, if the filling ratio of the particles 121 exceeds 95%, it may be difficult to make the solid electrolyte membrane 120 thin, and the manufacture of the electron barrier layer 123 may be restricted.

The plurality of particles 121 are formed such that a part of each of the particles 121 is buried in the cathode layer 110 and the particles 121 serve to prevent shorting between the anode layer and the cathode layer 110 Can also be performed.

The electron barrier layer 123 is formed using an electron-insulating material and is formed in an exposed portion of the cathode layer 110 between the particles 121 and the particles 121 to isolate the anode layer and the cathode layer 110 from each other .

The electron barrier layer 123 may be formed of any one of lithium ion solid electrolyte foil / thick film, for example, LLT or LLZ. In this case, the ion conductivity of the solid electrolyte membrane 120 can be further improved.

The electron barrier layer 123 may be formed to have a thickness of at least 1 탆, more preferably in the range of 1 탆 to 20 탆. A uniform insulating film may not be formed when the electron barrier layer 123 is formed to a thickness of 1 탆 or less, and a lithium ion migration path is not sufficient when the electron barrier layer 123 is manufactured to a thickness of 20 탆 or more. It can cause deterioration.

On the other hand, the electron barrier layer 123 may be composed of LLT or LLZ to which Al ₂ O ₃ is added in an amount of 5 wt% or less, more preferably 0.5 wt% to 5 wt% or less. In this case, the electron barrier layer 123 may be a LLZ the LLT or Al ₂ O ₃ was added.

As in the case of the particles 121, Al ₂ O ₃ has the effect of improving ion conductivity of the electron barrier layer 123 due to the formation of Li vacancies while substituting Al ^{3 +} ions for Li ⁺ The addition of ₂ O ₃ changes the crystal structure of LLZ to a cubic structure. In this case, the reason for the content of Al ₂ O ₃ added to the LLZ is also the same as that described in the particle 121, and thus a duplicated description will be omitted.

As described above, the solid electrolyte membrane 120 according to the present invention is a novel solid electrolyte membrane comprising a plurality of particles 121 having a particle size of at least 1 탆 and an electron barrier layer 123 formed between at least the particles 121 Structure.

The solid electrolyte membrane 120 of this novel structure is characterized in that it provides a path of lithium ions through a plurality of particles 121 having a size of at least 1 탆 and is about 60 times larger than that of a conventional flat type LIPON membrane The ion conductivity of about 6 x 10 &lt; ^-5 &gt; S / cm.

In addition, the solid electrolyte membrane 120 according to the present invention is chemically stable since it has a high ionic conductivity as well as a solid oxide.

The ionic conductivity of the solid electrolyte membrane 120 according to the present invention is determined by the filling ratio of the particles 121 as shown in Equation 2, and in the range of 0.5 wt% to 5 wt% of Al ₂ O ₃ When the added LLZ is used as the particles, it may have an ion conductivity in the range of 3 × 10 ^-6 S / cm to 2.8 × 10 ^-4 S / cm. However, the solid electrolyte membrane 120 of the present invention does not limit the material of the particles 121 to the LLT and LLZ series materials, and when the solid electrolyte material having higher ion conductivity is used, The ionic conductivity of the electrolyte membrane 120 is determined.

In FIG. 1, the particles 121 and the electron barrier layer 123 are formed of different materials, but they may be formed of the same material.

1, the electron barrier layer 123 of the solid electrolyte layer 120 is formed between the plurality of particles 121. However, the present invention is not limited thereto, and an electron barrier layer 123 123 may also be formed on the particles 121 as well.

2 is a process flow chart for explaining a solid electrolyte membrane production method according to an embodiment of the present invention.

Referring to FIG. 2, the method for manufacturing a solid electrolyte membrane according to an exemplary embodiment of the present invention includes a step of forming a cathode layer (S210), a step of injecting a part of particles into a cathode layer (S220), and an step of forming an electron barrier layer .

FIGS. 3 and 4 are cross-sectional views for explaining the method of manufacturing the solid electrolyte membrane according to FIG. 2, and FIGS. 5 and 6 are process plan views for explaining the method for manufacturing the solid electrolyte membrane according to FIG. Hereinafter, a method for manufacturing a solid electrolyte membrane according to an embodiment of the present invention will be described in detail with reference to FIGS. 2 to 6. FIG.

Referring to FIGS. 2, 3 and 5, in the step of preparing the cathode layer 310 (S210), a cathode layer 310 for forming all the solid secondary batteries is provided.

The cathode layer 310 is not particularly limited as long as it has a function as a cathode. As the cathode layer 310, a material used for a conventional solid secondary battery using lithium may be used. For example, the negative electrode layer 310 may be made of a negative electrode material mixed with a negative electrode active material Li ₄ Ti ₅ O ₁₂ and a solid electrolyte LiGe _{0 .25} P _{0 .75} S ₄ . An LLT or an LLZ oxide, or an LLZ oxide added with 5% by weight or less of Al ₂ O ₃ may be used as the solid electrolyte of the cathode layer 310. The cathode layer 310 may further include conductors such as acetylene black, ketjen black, carbon fiber, and conductive metal to improve conductivity.

Alternatively, a lithium foil, an indium foil, a tin foil, a mixture of two materials among them, or the like may be used as the cathode layer 310.

Next, a portion of each of the plurality of particles 321 having a particle size of at least 1 탆 or more, more preferably 1 탆 to 200 탆 in the partial embedding step (S220) of the particles 321 in the cathode layer 310, Layer 310 as shown in FIG.

Particularly, it is possible to embed a part of the particles 321 in the cathode layer 310 by using various methods to be described later.

First, a particle 321 having a particle size of at least 1 탆 is formed on the cathode layer 310 such as a lithium foil, an indium foil, a tin foil, and a mixture of two of them. Followed by spraying and pressing.

At this time, as a method of spraying the particles 321, a powder coating method and a spin coating method can be used. One of these methods may be used alone, or two or more of them may be used in combination.

Second, it is performed using a conventional tape casting method.

In the tape casting method, particles 321 are densely arranged on a usual adhesive tape (not shown), and then an adhesive tape (not shown) with the particles 321 attached is placed on the cathode layer 310 And an adhesive tape (not shown) having particles 321 attached thereto is pressed on the cathode layer 310. Thereby, a part of the particles 321 can be embedded in the cathode layer 310.

On the other hand, after the pressing, the adhesive tape must be removed. In this case, the adhesive tape can be heat-treated at a temperature of 300 ° C to 500 ° C or dissolved by dissolving the adhesive tape in a solvent. At this time, if the heat treatment temperature is out of the above-mentioned range, care must be taken since the removal of the adhesive tape may be insufficient, or other cathode layer 310 or particles 321 may be damaged.

Third, particles can be physically directly injected and buried using an aerosol deposition method or the like.

In this case, due to the physical force applied to the particles 321, a part of the particles 321 is embedded in the cathode layer 310 without performing a pressing process unlike the other methods described above.

At this time, it is preferable that the aerosol deposition is carried out with the particle moving speed in the range of 0.1 to 300 m / s. If the particle moving speed is less than 0.1 m / s, the physical force applied to the particle 321 is too weak, so that it may be difficult for the particle 321 to be buried in the cathode layer 310. On the contrary, when the particle moving speed exceeds 300 m / s, all of the particles 321 are buried in the cathode layer 310 so that the particles 321 do not provide a path of lithium ions to the anode layer, It may not be able to perform the role of preventing it. Therefore, it is preferable to maintain the particle moving speed in the above-mentioned range.

In all of the above methods, all of the lithium ion solid electrolytes can be used as the particles 321. In addition, particles 321 having a particle size of at least 1 mu m, more preferably in the range of 1 mu m to 200 mu m can be used. In addition, the cathode layer 310 can be filled with the particles 321 of 1% to 95%. The reasons for defining such particles 321 forming material, size, and filling factor are the same as those described with reference to FIG. 1, so duplicate descriptions are omitted.

In the electron barrier layer formation step S230, an electron barrier layer 323 is formed in the exposed portion of the cathode layer 310 between at least a plurality of particles 321. [

For example, the electron barrier layer 323 may include a plurality of particles 321 by using an LLT or LLZ oxide material, or an LLZ oxide material to which 5% by weight or less of Al ₂ O ₃ is added by an aerosol deposition method or a spin coating method, As shown in FIG.

It goes without saying that the electron barrier layer 323 may be formed on the particles 321 as well as the exposed portions of the cathode layer 310 between the particles 321 and the particles 321 in this process.

However, it should be understood that other methods of embedding a part of the particles 321 in the cathode layer 310 may also be used.

A portion of the plurality of particles 321 is embedded in the cathode layer 310. Alternatively, a cathode layer (not shown) may be used instead of the cathode layer 310, It may be the same as that of the anode layer 710, and thus it will be omitted.

As described above, the solid electrolyte membrane manufacturing method according to the present invention has an advantage that a solid electrolyte membrane having a novel structure and high ion conductivity can be easily manufactured using existing methods.

7 is a cross-sectional view schematically showing a pre-solid secondary battery that can be manufactured using the solid electrolyte membrane according to the present invention.

7, a pre-solid-state secondary battery 700 according to the present invention includes a cathode layer 710, a cathode layer 720, and a solid electrolyte layer (not shown) interposed between the anode layer 710 and the cathode layer 720 730).

The anode layer 710 is not particularly limited as long as it has a function as an anode. As the anode layer 710, a material used for a conventional solid secondary battery using lithium can be used. For example, the anode layer 710 may be made of a mixture of a cathode active material LiCoO ₂ and a solid electrolyte LiGe _{0 .25} P _{0 .75} S ₄ as a cathode mixture. Further, an LLT or an LLZ oxide, or an LLZ oxide to which 5% by weight or less of Al ₂ O ₃ is added may be used as the solid electrolyte of the anode layer 710. The anode layer 710 may further contain conductors such as acetylene black, ketjen black, carbon fiber, and conductive metal to improve conductivity.

The cathode layer 720 is not particularly limited as long as it has a function as a cathode. As the cathode layer 720, a material used in a conventional solid secondary battery using lithium may be used. For example, the negative electrode layer 720 may be made of a negative electrode material mixed with a negative electrode active material Li ₄ Ti ₅ O ₁₂ and a solid electrolyte LiGe _0.25 P _0.75 S ₄ . Further, an LLT or LLZ oxide, or an LLZ oxide to which 5% by weight or less of Al ₂ O ₃ is added may be used as the solid electrolyte of the cathode layer 720. The negative electrode layer 720 may further contain conductors such as acetylene black, ketjen black, and carbon fibers to improve conductivity. Alternatively, a lithium foil, an indium foil, a tin foil, a mixture of two materials among them, or the like may be used as the cathode layer 720.

The solid electrolyte membrane 730 is characterized in that the solid electrolyte membrane 730 is composed of a plurality of lithium ion batteries having a particle size of at least 1 mu m and an electron barrier layer 733 formed between the particles 731 and the plurality of particles 731, And an ionic conductivity in the range of 10 ^-6 S / cm to 2.8 10 ^-4 S / cm.

The solid electrolyte membrane 730 described above can use the solid electrolyte membrane 120 of FIG. 1, and the materials and method of forming the particles 731 and the electron barrier layer 733 are shown in FIGS. 1, 4, and 5 And may be the same as the particle 121 and the electron barrier layer 123 described in the first embodiment.

As described above, the all-solid-state secondary battery 700 according to the present invention can have a high ion conductivity by employing the oxide solid electrolyte membrane 730 having a novel structure having a high ion conductivity according to the present invention. As a result, it is possible to improve the stability of the battery as well as to improve the performance thereof, so that it can be applied not only to electronic devices but also to electric vehicles.

Example

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.

Example 1 . LLZ  + 1 wt% Al ₂ O ₃ solid Electrolyte membrane  Produce

1% by weight Al ₂ O ₃ having a particle size of 100 μm The added Li ₇ La ₃ Zr ₂ O ₁₂ (LLZ) particles were sprayed onto a negative electrode layer made of tin foil and pressed at a pressure of 300 kg / cm ² using a press machine. Thereafter, an LLT thick film was formed in the cathode layer exposed portion between the particles by an aerosol deposition method, and LLZ - A solid electrolyte membrane of 1 wt% Al ₂ O ₃ ceramics was prepared.

Property evaluation

The ion conductivity of the solid electrolyte membrane prepared in Example 1 was measured and analyzed using complex impedance spectroscopy, which is shown in FIG.

FIG. 8 is a graph showing the relationship between the content of Li ₇ La ₃ Zr ₂ O ₁₂ - Ion conductivity of 1 wt% Al ₂ O ₃ ceramics.

Referring to FIG. 8, it was confirmed that Example 1 made of the novel LLZ-1 weight% Al ₂ O ₃ ceramics had an ion conductivity of about 6.37 × 10 ^-5 S / cm. This means that the filling rate is about 21% to 32%.

This value is about 60 times higher than the ion conductivity of a general solid electrolyte membrane. The ionic conductivity of LIPON solid electrolyte membranes used in industry today is generally known to be about 10 ^-6 S / cm. As a result, it was confirmed that the solid electrolyte membrane of the novel structure according to the present invention had high ionic conductivity.

Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. These changes and modifications may be made without departing from the scope of the present invention. Accordingly, the scope of the present invention should be determined by the following claims.

110, 310, 720: cathode layer 120: solid electrolyte membrane
121, 321, 731: Particles 123, 323, 733: Electronic barrier layer
700: entire solid secondary battery 710: anode layer

Claims (27)

A solid electrolyte membrane interposed between a cathode layer and a cathode layer,
_{Li 3x La 2 / (3x)} TiO 3 (0 <X≤2) Or Li ₇ La ₃ Zr ₂ O ₁₂ and has a particle size of at least 1 μm or more; And
Between at least two particles and all of the plurality of _{lithium, Li 3x La 2 / (3x} ) TiO 3 (0 <X≤2) Or an oxide selected from Li ₇ La ₃ Zr ₂ O ₁₂ .
delete delete The method according to claim 1,
The size of the lithium ion and the particle is
Wherein the solid electrolyte layer has a thickness of 1 占 퐉 to 200 占 퐉.
The method according to claim 1,
The charging rate of the lithium ion and the particle is
The solid electrolyte membrane according to claim 1, which is represented by the following formula (1).
[Formula 1], filling rate of particles = [area of particles] / [area of solid electrolyte membrane]
The method according to claim 1,
The lithium ion and the particles
Further comprising Al ₂ O ₃ in an amount of 5 wt% or less based on the Li ₇ La ₃ Zr ₂ O ₁₂ .
The method according to claim 1,
The electron barrier layer
Further comprising Al ₂ O ₃ in an amount of 5 wt% or less based on the Li ₇ La ₃ Zr ₂ O ₁₂ .
The method according to claim 1,
The thickness of the electron barrier layer
And the thickness of the solid electrolyte layer is 1 占 퐉 to 20 占 퐉.
_{(a) Li 3x La 2 /} (3x) TiO 3 (0 <X≤2) Or Li ₇ La ₃ Zr ₂ O ₁₂ , and forming a plurality of lithium ions, each having a particle size of at least 1 μm, in the anode layer or the cathode layer in such a manner that a part of each of the particles is embedded ; And
_{(b) Li 3x La 2 /} (3x) between at least a plurality of lithium all over the particles, TiO ₃ (0 <X≤2) Or Li ₇ La ₃ Zr ₂ O ₁₂ to form an electron barrier layer.
10. The method of claim 9,
The step (a)
A step of spraying the plurality of lithium ions and particles on the anode layer or the cathode layer, and a step of pressing the injected particles.
11. The method of claim 10,
The injection of the lithium ions and the particles
A powder coating method, or a spin coating method.
10. The method of claim 9,
The step (a)
Wherein the solid electrolyte membrane is formed using a tape casting method.
13. The method of claim 12,
After the tape casting,
And removing the adhesive tape to remove the adhesive tape.
14. The method of claim 13,
Wherein the adhesive tape is heat treated at a temperature of 300 ° C to 500 ° C or is dissolved by a solvent dissolving the adhesive tape to remove the solid electrolyte film.
10. The method of claim 9,
The step (a)
Wherein the plurality of lithium ions are physically directly injected and embedded into the plurality of lithium ions by using an aerosol deposition method.
16. The method of claim 15,
The lithium ion and the particles
Wherein the solid electrolyte membrane has a particle moving speed of 0.1 m / s to 300 m / s.
delete delete 10. The method of claim 9,
The size of the lithium ion and the particle is
Wherein the solid electrolytic film has a thickness of from 1 mu m to 200 mu m.
10. The method of claim 9,
The charging rate of the lithium ion and the particle is
(1), and is 1% to 95%.
[Formula 1], filling rate of particles = [area of particles] / [area of solid electrolyte membrane]
10. The method of claim 9,
The electron barrier layer
Wherein the solid electrolyte layer is formed by a powder coating method or a spin coating method.
A cathode layer, and a solid electrolyte layer interposed between the anode layer and the cathode layer,
Wherein the solid electrolyte membrane comprises a plurality of lithium ion exchange resins having a particle size of at least 1 탆; And at least electron barrier layer of the plurality of lithium formed between all the particles; including, but the lithium all over the particles, and _{Li 3x La 2 / (3x)} TiO 3 (0 <X≤2) Or Li ₇ La ₃ Zr ₂ O ₁₂ is formed from an oxide selected from the electron barrier layer is _{Li 3x La 2 / (3x)} TiO 3 (0 <X≤2) Or an oxide selected from Li ₇ La ₃ Zr ₂ O ₁₂ .
delete delete 23. The method of claim 22,
The charging rate of the lithium ion and the particle is
(1), and is 1% to 95%.
[Formula 1], filling rate of particles = [area of particles] / [area of solid electrolyte membrane]
23. The method of claim 22,
The lithium ion and the particles
Further comprising Al ₂ O ₃ in an amount of 5 wt% or less based on the Li ₇ La ₃ Zr ₂ O ₁₂ .
23. The method of claim 22,
The electron barrier layer
Further comprising Al ₂ O ₃ in an amount of 5 wt% or less based on the Li ₇ La ₃ Zr ₂ O ₁₂ .

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