KR20170071185A - Sputtering apparatus for conformal deposition and method of forming conformal electrolyte film of three dimensional secondary battery - Google Patents

Abstract

A sputtering apparatus for conformal deposition and a method for manufacturing an isoelectric electrolyte membrane of a three-dimensional secondary battery using the same are disclosed. The disclosed sputtering apparatus includes a high frequency pipe disposed between a target support and a substrate holder in a chamber and including at least one turn and hollowed to allow gas to flow therein and having a plurality of discharge holes to discharge the gas. A high-frequency power source is connected to the high-frequency pipe, and an inlet for supplying the gas is formed at one end.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a sputtering apparatus for conformal deposition, and a method for fabricating a conformal electrolyte membrane of a three-dimensional secondary battery using the same.

The present invention relates to a sputtering apparatus for conformal deposition and a method for manufacturing an isoelectric membrane of a three-dimensional secondary battery using the same.

Lithium secondary batteries are rapidly expanding in demand with the development of next-generation clean energy vehicles such as smart phones, notebook personal computers, and electric vehicles (EVs).

Lithium secondary batteries have a higher voltage and a higher energy density per unit weight than nickel-cadmium batteries and nickel-hydrogen batteries, and their demand is increasing. Lithium oxide is mainly used as the positive electrode active material of the lithium battery, and graphite is mainly used as the negative electrode active material of the lithium battery.

In such lithium batteries, research is underway to further improve the energy density and rapid charge-discharge characteristics. The improvement of the energy density can increase the capacity of the lithium battery, and the improvement of the rate characteristic can increase the charge / discharge speed of the lithium battery.

The three-dimensional lithium secondary battery can increase the charging capacity per unit area by increasing the facing area between the positive electrode and the negative electrode by forming the positive electrode and the negative electrode in the vertical direction. A solid electrolyte membrane may be formed between the anode and the cathode. When a solid electrolyte membrane is formed on a three-dimensional anode having a large aspect ratio by a chemical vapor deposition method (CVD), a reduction reaction may be caused by NH ₃ , which is a nitrogen source, on the surface of the anode. Further, since the deposition temperature is as high as about 300 DEG C or higher, it is difficult to apply the CVD method when the anode structure is formed of a polymer material.

In the case of forming the solid electrolyte film by the sputtering method, the step coverage may be poor since the element sputtered by the target is applied with the linearity on the three-dimensional cathode active material layer.

A hollow high frequency pipe having discharge holes formed between a target and a substrate (anode) is disposed by depositing an electrolyte membrane on an anode having a large aspect ratio by a sputtering method to further form a nitrogen plasma so as to scatter sputtered atoms passing through the high frequency pipe And a chemical reaction between the atoms and the nitrogen plasma is promoted.

And a method of manufacturing an electrolyte membrane of a three-dimensional secondary battery using the sputtering apparatus.

A sputtering apparatus for conformal deposition according to an embodiment

A chamber in which a predetermined internal space is formed and inlets for supplying a first gas are formed;

A target support for supporting the target within the chamber;

A substrate holder facing the target support in the chamber, on which an object to be deposited is mounted;

A high frequency pipe disposed between the target support and the substrate holder in the chamber, the high frequency pipe including at least one turn and hollowed to allow the second gas to flow therein and having a plurality of discharge holes to discharge the second gas;

A first high frequency power source for applying a first high frequency voltage between the target support and the substrate holder; And

And a second high frequency power source for applying a second high frequency voltage to the high frequency pipe.

And a magnet disposed below the target supporter to form a magnetic field on the target mounted on the target supporter.

The high-frequency pipe may form a band that is larger than the diameter of the target in a form surrounding the target mounted on the target support in plan view.

Each of the plurality of discharge holes of the high-frequency pipe may have a diameter of about 0.1 to 1 mm.

An inlet for supplying the source may be formed at one end of the high-frequency pipe.

Wherein the first gas and the second gas each comprise nitrogen,

The first high frequency voltage causes the first gas to generate a first nitrogen plasma and the argon plasma, and the second high frequency voltage allows the second gas to generate a second nitrogen plasma.

A method for manufacturing a solid electrolyte of a three-dimensional secondary battery according to an embodiment includes:

Disposing a cathode current collector having a plurality of anodes on the substrate holder so that the plurality of anodes face the target support;

Disposing a target made of a Li-P-O based solid electrolyte on the target support;

Supplying nitrogen and argon gas into the chamber, applying the first high frequency voltage to form a first nitrogen plasma and an argon plasma, and sputtering elements from the target;

Emitting nitrogen-containing gas from a plurality of discharge holes of the high-frequency pipe and applying the second high-frequency voltage to form a second nitrogen plasma inside the high-frequency pipe; And

And chemically bonding the atoms sputtered from the target with the nitrogen ions in the second nitrogen plasma to deposit an electrolyte membrane on the surface of the anode.

The anode is _{LiCoO 2, LiMnO 2, LiNiO 2} , LiFePO 4, LiMnPO 4, LiMn 2 O 4 Or the like.

The electrolyte membrane may be formed to a thickness of 1 to 5 mu m.

Wherein the solid electrolyte membrane is a first solid electrolyte membrane having a first thickness,

Forming a second solid electrolyte membrane having a second thickness larger than the first thickness on the first solid electrolyte membrane by a chemical vapor deposition method on the resultant product on which the first solid electrolyte membrane is formed.

The first thickness may be 0.05 to 0.5 탆, and the second thickness may be 1 to 5 탆.

The second solid electrolyte film forming step may be performed in a chamber different from the chamber.

The nitrogen-containing gas may include N ₂ , N ₂ -O ₂ , NH ₃ , N _x O _y Or the like.

The anode may have an aspect ratio of 10: 1 or greater.

The sputtering apparatus for conformal deposition of the embodiment includes a high-frequency pipe between the target support and the substrate holder. The gas is supplied into the high-frequency pipe, and the gas is discharged to form a separate plasma to chemically react the plasma with the sputtering element And the plasma generated by the application of the high frequency voltage can scatter the sputtering particles and chemical bonds passing through the high frequency pipe and deposit the conformal coating on the structure mounted on the substrate holder.

According to the method for manufacturing an electrolyte membrane of a three-dimensional secondary battery according to an embodiment, an isoelectric membrane can be formed on the surface of anodes having a high aspect ratio.

According to another embodiment of the present invention, a thin first electrolyte film is formed on the surface of a cathode of a three-dimensional secondary battery by a sputtering method, and then a second electrolyte having a relatively thick thickness is deposited on the first electrolyte film by chemical vapor deposition A film can be formed to increase the deposition rate of the electrolyte membrane.

1 is a cross-sectional view showing an example of a third dimensional secondary battery manufactured by the manufacturing method according to the embodiment.
2 is a schematic view showing an example of a sputtering apparatus according to an embodiment.
3 is a view showing an example of a high-frequency pipe according to an embodiment.
4 is a cross-sectional view showing an example of a structure in which an electrolyte membrane is mounted on the surface of a substrate holder of the sputtering apparatus of FIG.
5A to 5C are cross-sectional views illustrating a method of manufacturing a three-dimensional secondary battery using a sputtering apparatus for conformal deposition according to an embodiment.
6 is a cross-sectional view illustrating a method of forming an electrolyte film according to another embodiment.

Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. In this process, the thicknesses of the layers or regions shown in the figures are exaggerated for clarity of the description. The embodiments described below are merely illustrative, and various modifications are possible from these embodiments.

In the following, what is referred to as "upper" or "upper"

FIG. 1 is a cross-sectional view showing an example of a third-dimensional secondary battery 100 manufactured by the manufacturing method according to the embodiment.

Referring to FIG. 1, a plurality of anodes 120 are formed on a cathode collector 110 perpendicularly to a cathode collector 110. An electrolyte membrane 130, a cathode 140 and an anode collector 150 are sequentially formed on the anode 120 on the anode current collector 110. The electrolyte membrane 130 is formed so as to cover the surface of the anodes 120 and the surface of the anode current collector 110 exposed between the anodes 120. The cathode 140 may be formed to cover the trench formed in the electrolyte membrane 130 between the anodes 120. The anode 120 may have an aspect ratio of 10: 1 or greater. For example, the anode 120 may have an aspect ratio of 20: 1.

The embodiment is not limited thereto. The cathode 140 may be formed to cover the electrolyte membrane 130 to a predetermined thickness uniformly, or may be formed on the cathode 140. The anode current collector 150 on the cathode 140 may be formed in parallel with the cathode current collector 110. The embodiment is not limited thereto. The anode current collector 150 may be omitted.

The anode 120 may be made of only a cathode active material. The anode 120 may be formed by sintering a cathode active material powder and a cathode forming material including a binder and a plasticizer. During the sintering process, the binder and the plasticizer may be volatilized, thereby obtaining the anode 120 made of only the cathode active material.

The anode current collector 110 may be made of a conductive metal material such as Cu, Au, Pt, Ag, Zn, Al, Mg, Ti, Fe, Co, Ni, Ge, The anode current collector 110 may be formed in the form of a flat flattened plate. The thickness of the positive electrode collector 110 may be approximately 1 mu m to 15 mu m.

The anode 120 may be made of a lithium-transition metal oxide. The transition metal may include at least one of cobalt (Co), nickel (Ni), manganese (Mn), and iron (Fe). For example, the anode 120 may be made of lithium cobalt oxide (LiCoO ₂ ), LiMnO ₂ , LiNiO ₂ , LiFePO ₄ , LiMnPO ₄ , LiMn ₂ O ₄ .

The anode 120 according to the embodiment may be formed to a thickness of about 5 to 30 占 퐉. The electrolyte membrane 130 may be formed as a solid. For example, Lithium phosphorous oxynitride (LiPON).

The cathode 140 may be formed of lithium. The thickness of the cathode 140 may be approximately 50 nm to 40 占 퐉.

The anode current collector 150 may be in the form of a foil. The anode current collector 150 may include at least one metal selected from the group consisting of, for example, copper, stainless steel, nickel, aluminum, and titanium.

The electrolyte membrane 130 may be formed by a physical vapor deposition method or a chemical vapor deposition method. When the electrolyte membrane 130 is formed by chemical vapor deposition, the surface of the anode can be reduced by NH ₃ , which is a nitrogen source. When the electrolyte membrane 130 is formed by sputtering with a conventional sputtering apparatus, it is difficult to uniformly form an electrolyte membrane.

 Embodiments provide an apparatus for forming an electrolyte membrane having a uniform thickness over a three-dimensional anode.

2 is a schematic view showing an example of a sputtering apparatus 200 according to an embodiment.

2, a sputtering apparatus 200 includes a target support 220 for supporting a target T disposed in a chamber 210, a substrate holder 220 for supporting a substrate S for depositing particles from the target T, A plasma is formed between the substrate holder 230 and the target supporter 220 and the substrate holder 230 so as to surround the passage through which the particles from the target T pass and to scatter the particles, And a high-frequency pipe 240 that provides nitrogen that undergoes a chemical reaction. The chamber 210 is formed with an inlet 211 for injecting sputtering gas such as nitrogen or argon and an outlet 212 for discharging the gas in the chamber 210 to the outside. The gas introduced into the chamber 210 is converted into a plasma to be used to discharge the element of the target T, and the nitrogen gas can react with the elements from the target T.

3 is a view showing an example of the high frequency pipe 240 according to the embodiment.

Referring to FIG. 3, the high-frequency pipe 240 includes at least one turn. 3 shows a high frequency pipe 240 which is illustratively turned two times. A high frequency voltage is applied to the high frequency pipe 240. The high frequency pipe 240 is a hollow pipe and at least one end of the high frequency pipe 240 is formed with an inlet 241 through which a nitrogen source is supplied from the outside of the chamber 210. The high-frequency pipe 240 is arranged in a circular strip shape, and a plurality of discharge holes 245 are formed on the inner side facing each other. The other end of the high-frequency pipe 240 may be clogged or the discharge port 242 may be formed.

The nitrogen source supplied from the inlet 241 is discharged to the inside through a plurality of discharge holes 245. The nitrogen source forms a nitrogen plasma by the high frequency voltage supplied to the high frequency pipe 240. Nitrogen sources include N ₂ , N ₂ -O ₂ , NH ₃ , N _x O _y Or the like.

The high frequency pipe 240 is arranged in a circular band shape having a diameter larger than the diameter of the target T and the diameter of the substrate S. [ For example, the target T and the substrate S may have a diameter of 6 inches, and the high-frequency pipe 240 may be formed in the shape of a circular band of 8 to 10 inches in diameter. In the plan view, the high-frequency pipe 240 can be arranged to surround the target T. [ Each of the plurality of discharge holes 245 may be formed to have a size of approximately 0.1 mm to 1 mm.

A magnet 250 may be formed in the target support 220. The magnet 250 may include a first magnet 251 formed at the center of the target support 220 and a circular second magnet 252 formed along the edge of the target support 220. The first magnet 251 and the second magnet 252 face each other with a different polarity toward the target support 220. For example, the first magnet 251 may have an S pole and the second magnet 252 may have an N pole directed toward the target support 220. The magnet 250 may form a magnetic field on the surface of the target T to increase the ion density and increase the release rate of the sputtering particles.

A first RF power supply 261 is connected between the substrate holder 230 and the target support 220 and a second RF power supply 262 is connected to the RF pipe 240.

4 is a cross-sectional view showing an example of a structure in which an electrolyte membrane is mounted on a surface of a substrate holder 230 of the sputtering apparatus 200 of FIG. The same reference numerals are used for components substantially the same as those of FIG. 1, and a detailed description thereof will be omitted.

Referring to FIG. 4, the aspect ratio of the anode 120 of the three-dimensional secondary battery (see 100 in FIG. 1) may be about 10 or more. For example, the aspect ratio of the anode 120 may be 20. The anode holder 120 is disposed on the substrate holder 230 so as to be in contact with the anode current collector 110 and the anode 120 protrudes toward the target T.

An electrolyte membrane 130 is formed on the anode 120. The electrolyte membrane 130 may be formed as a solid. For example, Lithium phosphorous oxynitride (LiPON). The electrolyte membrane 130 may be formed by a physical vapor deposition method or a chemical vapor deposition method.

However, when the electrolyte membrane 130 is formed by a chemical vapor deposition method, a reduction reaction may occur at the surface of the anode 130 by a nitrogen source, such as NH ₃ . As a result, the characteristics of the three-dimensional secondary battery can be deteriorated.

When the electrolyte membrane 130 is performed in a conventional sputtering apparatus, since the aspect ratio of the anodes 120 is large and the plasma particles have a directivity when flying toward the anodes 120, (Not shown). As a result, the conformality of the electrolyte membrane 130 is lowered, the reaction of the electrodes becomes uneven, and when the electrolyte membrane 130 is partially deposited on the sidewalls of the anode, a negative electrode may be formed and short- have.

In the sputtering apparatus 200 according to the embodiment, Li, P, and O elements are sputtered from the surface of the Li-PO based target T by the first RF power supply 261 and the plasma and proceed toward the substrate holder 230. On the other hand, the nitrogen supplied into the inlet 211 of the reaction chamber 210 forms a nitrogen plasma near the target T, and a part thereof can serve as a sputtering. The nitrogen plasma thus formed is referred to as a first nitrogen plasma. Elements sputtered from the target T may chemically react with a part of the first nitrogen plasma to form LiPON, which is a composition of the electrolyte membrane 130. In addition, LiPON and some elements pass through the high-frequency pipe 240. At this time, when a high frequency voltage is supplied from the second high frequency power source 262 and nitrogen containing gas is supplied from the inlet 241 of the high frequency pipe 240, the nitrogen containing gas is discharged from the plurality of discharge holes 245, . This can be referred to as a second nitrogen plasma. The sputtered elements and partially formed LiPON molecules may be scattered by a second nitrogen plasma. The second nitrogen plasma chemically reacts with the elements scattered in the high-frequency pipe 240 to form LiPON. The LiPON proceeds toward the substrate holder 230 and is deposited on the surface of the anode 120 to form an electrolyte membrane 130. Alternatively, when the sputtered elements are deposited on the anode surface, it is possible to react with the surrounding nitrogen ions to form LiPON. The nitrogen-containing gas may include N ₂ , N ₂ -O ₂ , NH ₃ , N _x O _y Or the like.

The electrolyte membrane 130 formed by the sputtering according to the embodiment has good conformability due to the scattering action of the high frequency pipe 240 described above. In addition, the chemical reaction of nitrogen with Li-PO elements can be increased by the action of the second nitrogen plasma. 5A to 5C are cross-sectional views illustrating a method of manufacturing a three-dimensional secondary battery using the sputtering apparatus 200 for conformal deposition according to an embodiment.

Referring to FIG. 5A, a three-dimensional structure anode is prepared. 5A is a perspective view of FIG. 4 and shows a three-dimensional structure anode composed of a cathode current collector 330 and anode plates 313. FIG.

Referring to FIG. 5B, an electrolyte membrane 340 is formed on the cathode current collector 330 to cover the anode plates 313. In order to form the electrolyte membrane 340, the target T is placed on the support table 220 in the chamber 210 of the sputtering apparatus (100 of FIG. 2). The target (T) may be made of a Li-PO-based material. For example, the target (T) may be made of Li ₃ PO ₄ . And the cathode current collector 330 on which the cathode plates 313 are disposed is mounted on the substrate holder 230. At this time, the anode plates 313 are directed toward the target T.

Nitrogen and argon gas may be introduced through the inlet 211 of the chamber 210. The process pressure in the chamber 210 is maintained at 10-50 mTorr, and the process temperature may be room temperature. Argon gas can increase the sputtering yield because of its large atomic mass compared to nitrogen.

Also, a nitrogen source is injected into the inlet 241 of the high-frequency pipe 240. Nitrogen sources include N ₂ , N ₂ -O ₂ , NH ₃ , N _x O _y Or the like.

The first high-frequency power source 261 and the second high-frequency power source 262 apply the first high-frequency voltage and the second high-frequency voltage, respectively.

The argon gas introduced into the chamber 210 becomes a plasma state to sputter the target T to discharge the Li, P, O element from the target T, and the nitrogen gas becomes a plasma state to become the first nitrogen plasma. The first nitrogen plasma may chemically react with a portion of the Li, P, O elements to form LiPON (lithium phosphorus oxynitride) molecules. That is, the composition of the electrolyte membrane 340 can be obtained. The Li, P, O element and LiPON emitted from the target T advance in the direction of the substrate holder 230.

At this time, the Li, P, and O elements and LiPON pass through the high-frequency pipe 240. The nitrogen source discharged from the discharge holes 245 of the high-frequency pipe 240 forms a second nitrogen plasma by the second high-frequency voltage. The Li, P, O element and LiPON passing through the high-frequency pipe 240 are scattered by the second nitrogen plasma. These second nitrogen plasma and some Li, P, O elements can chemically react to form LiPON.

Since the Li, P, and O elements and LiPON that have passed through the high frequency pipe 240 have diffraction characteristics while being directed toward the anodes 313, they are uniformly deposited on the surface of the anode plates 313 to form an electrolyte film 340 do. By adjusting the sputtering time, the electrolyte membrane 340 may be formed to a thickness of 1 탆 to 5 탆.

Referring to FIG. 5C, a cathode 350 is formed on the electrolyte film 340. Here, the cathode 350 may be formed to fill the space between the electrolyte films 340. The cathode 350 may include, but is not limited to, lithium. The cathode 350 can be formed, for example, by depositing lithium on the electrolyte membrane 340 by evaporation or by filling the molten lithium between the anode plates 313. However, the present invention is not limited thereto, and the cathode 350 may be formed by other methods.

Next, the cathode current collector 360 is formed on the cathode 350 to complete the three-dimensional secondary battery 300. The anode current collector 360 may include, for example, Cu, but is not limited thereto. The embodiment is not limited thereto. The anode current collector 360 may be omitted.

According to the embodiment, since the high-frequency pipe for supplying the nitrogen gas between the target and the substrate holder is used as compared with the normal sputtering method, the electrolyte membrane on the surface of the anode having the large aspect ratio due to the diffraction of the sputtered elements by the second plasma So that it is uniformly formed.

6 is a cross-sectional view illustrating a method of forming an electrolyte film according to another embodiment. The same reference numerals are used for the same constituent elements as those described in Figs. 5A to 5C, and a detailed description thereof will be omitted.

Referring to FIG. 6, a first electrolyte layer 341 is formed on the anodes 313 on the cathode current collector 330. The first electrolyte layer 341 may be formed in the same manner as the electrolyte layer 340 described with reference to FIG. 5B, but may have a thickness of 0.05 μm to 0.5 μm. The first electrolyte membrane 341 can prevent the surface of the anode from being reduced when the electrolyte membrane is formed in the conventional chemical vapor deposition method.

Next, a second electrolyte film 342 is formed on the first electrolyte film 341. The second electrolyte membrane 342 may be formed in the same composition as the first electrolyte membrane 341. A structure in which the first electrolyte film 341 is formed is placed in another chemical vapor deposition chamber (not shown) to form the second electrolyte film 342. [

Next, a precursor for forming the second electrolyte film 342 is supplied into the chemical vapor deposition chamber to form a second electrolyte film 342 having a thickness of approximately 1 mu m to 5 mu m. As the precursor, lithium dipivaloylmethane (Li (DPM), Li (C ₁₁ H ₁₉ O ₂ )) and triethyl phosphate (TEP, (C ₂ H ₅ ) ₃ PO ₄ ) can be used and NH ₃ can be used as nitriding gas. The embodiment is not limited thereto. A method of manufacturing a LiPON electrolyte membrane by a chemical vapor deposition method is well known, and a detailed description thereof will be omitted.

If the sputtering chamber 210 is designed to be capable of chemical vapor deposition, a separate chamber may not be used.

The following method of forming the cathode 350 and the anode current collector 360 may be used, and a detailed description thereof will be omitted.

According to the embodiment, the first electrolyte layer is formed on the surface of the anode to serve as a protective film for the anode which prevents the reduction reaction. As the second electrolyte membrane is formed in two steps, the formation time of the electrolyte membrane can be reduced, and the manufacturing cost and the process time of the electrolyte membrane can be reduced, compared with a method of forming the electrolyte membrane only by the sputtering method.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, and that various changes and modifications may be made without departing from the scope of the invention. Accordingly, the true scope of protection of the present invention should be determined only by the appended claims.

200: sputtering apparatus 210: chamber
211: inlet 212: outlet
220: target support 230: substrate holder
240: high frequency pipe 250: magnet
261, 262: high-frequency power source T: target
S: substrate

Claims (14)

A chamber in which a predetermined internal space is formed and inlets for supplying a first gas are formed;
A target support for supporting the target within the chamber;
A substrate holder facing the target support in the chamber, on which an object to be deposited is mounted;
A high frequency pipe disposed between the target support and the substrate holder in the chamber, the high frequency pipe including at least one turn and hollowed to allow the second gas to flow therein and having a plurality of discharge holes to discharge the second gas;
A first high frequency power source for applying a first high frequency voltage between the target support and the substrate holder; And
And a second high frequency power source for applying a second high frequency voltage to the high frequency pipe. The method according to claim 1,
And a magnet disposed within the target support to form a magnetic field over the target mounted on the target support. The method according to claim 1,
Wherein the high-frequency pipe forms a circular band which is larger than the diameter of the target in a form surrounding the target mounted on the target support in plan view. The method according to claim 1,
Wherein each of the plurality of discharge holes of the high-frequency pipe has a diameter of about 0.1 to 1 mm. The method according to claim 1,
And an inlet for supplying the source is formed at one end of the high-frequency pipe. The method according to claim 1,
Wherein the first gas and the second gas each comprise nitrogen,
Wherein the first gas generates a first nitrogen plasma by the first high frequency voltage and the second gas generates a second nitrogen plasma by the second high frequency voltage. A method of manufacturing a solid electrolyte of a three-dimensional secondary battery using the sputtering apparatus according to claim 1,
Disposing a cathode current collector having a plurality of anode plates disposed on the substrate holder such that the plurality of anode plates face the target support;
Disposing a target made of a Li-PO-based solid electrolyte on the target support;
Supplying nitrogen and argon gas into the chamber, applying the first high frequency voltage to form an argon plasma and a first nitrogen plasma, and sputtering the elements from the target;
Emitting nitrogen-containing gas from a plurality of discharge holes of the high-frequency pipe and applying the second high-frequency voltage to form a second nitrogen plasma inside the high-frequency pipe; And
And chemically bonding atoms sputtered from the target with nitrogen ions in the second nitrogen plasma to form an electrolyte membrane on the surface of the anode. 8. The method of claim 7,
The anode is _{LiCoO 2, LiMnO 2, LiNiO 2} , LiFePO 4, LiMnPO 4, LiMn 2 O 4 ≪ / RTI > 8. The method of claim 7,
Wherein the electrolyte membrane is formed to a thickness of 1 to 5 占 퐉. 8. The method of claim 7,
Wherein the solid electrolyte membrane is a first solid electrolyte membrane having a first thickness,
Forming a second solid electrolyte membrane having a second thickness greater than the first thickness on the first solid electrolyte membrane by a chemical vapor deposition method on the resultant product on which the first solid electrolyte membrane is formed. 11. The method of claim 10,
Wherein the first thickness is 0.05 to 0.5 탆 and the second thickness is 1 to 5 탆. The method according to claim 10, wherein the second solid electrolyte film forming step comprises:
Wherein the chamber is in a different chamber than the chamber. 8. The method of claim 7,
The nitrogen-containing gas may include N ₂ , N ₂ -O ₂ , NH ₃ , N _x O _y ≪ / RTI > 8. The method of claim 7,
Wherein the anode has an aspect ratio of 10: 1 or greater.

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