WO2011136551A2

WO2011136551A2 - Lithium-air battery

Info

Publication number: WO2011136551A2
Application number: PCT/KR2011/003067
Authority: WO
Inventors: 선양국; 정훈기
Original assignee: 한양대학교 산학협력단
Priority date: 2010-04-27
Filing date: 2011-04-27
Publication date: 2011-11-03
Also published as: WO2011136551A3

Abstract

Provided is a lithium-air battery comprising: a positive electrode including a current collector and a positive electrode active material layer which is located on the current collector and includes a positive electrode active material; a negative electrode including a negative electrode active material; and an electrolyte, wherein the positive electrode active material includes lithium peroxide (Li₂O₂), lithium oxide (Li₂O), lithium hydroxide (LiOH), or a combination thereof, and the negative electrode active material includes a lithium alloy, a material which can be doped or undoped with lithium, a transitional metal oxide, or a combination thereof.

Description

Lithium air battery

The present disclosure relates to a lithium air battery.

Lithium air batteries, which are recently developed as a power source for portable electronic devices and electric vehicles, exhibit a significantly higher energy density than lithium ion batteries as they are brought into contact with air, and thus have advantages of miniaturization and light weight. to be.

The lithium air battery is used by injecting an electrolyte solution into a battery cell including a positive electrode including a positive electrode active material for oxidizing and reducing lithium and a negative electrode including a negative electrode active material capable of intercalating and deintercalating lithium.

Lithium metal is mainly used as the negative electrode active material, which causes a rapid explosion reaction when it comes in contact with moisture and rapidly oxidizes when it comes in contact with air, and loses its activity.

One aspect of the present invention is to provide a lithium air battery that can be commercialized and large-sized with improved stability.

One aspect of the present invention is a positive electrode including a current collector and a positive electrode active material layer disposed on the current collector and including a positive electrode active material; A negative electrode including a negative electrode active material; And an electrolyte solution, and the positive electrode active material includes lithium peroxide (Li ₂ O ₂ ), lithium oxide (Li ₂ O), lithium hydroxide (LiOH), or a combination thereof, and the negative electrode active material is an alloy of lithium metal, lithium It provides a lithium air battery comprising a material that can be dope and undoped, a transition metal oxide or a combination thereof.

The cathode active material layer may further include a conductive material including a carbonaceous material, a metal powder, a metal fiber, or a combination thereof, and the carbonaceous material may include natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, Carbon fibers, carbon nanotubes or a combination thereof may be included.

The cathode active material layer may further include a catalyst, wherein the catalyst is tricobalt tetraoxide (Co ₃ O ₄ ), manganese dioxide (MnO ₂ ), cerium dioxide (CeO ₂ ), platinum (Pt), gold (Au), silver ( Ag), ferric trioxide (Fe ₂ O ₃ ), triiron tetraoxide (Fe ₃ O ₄ ), nickel monoxide (NiO), copper oxide (CuO), perovskite-based catalysts, or combinations thereof. And, the catalyst may be included in 1 to 50% by weight based on the total amount of the positive electrode active material layer.

The cathode active material may be included in an amount of 5 to 50 wt% based on the total amount of the cathode active material layer.

The alloy of the lithium metal is lithium and Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, Sn or combinations thereof It may include an alloy of a metal containing, the material that can be doped and undoped lithium, Si, Si containing alloys, Si-C composites, SiO _x (0 <x <2), Sn, Sn containing alloys, Sn-C composite, SnO ₂ or a combination thereof, and the transition metal oxide may include vanadium oxide, lithium vanadium oxide, titanium oxide or a combination thereof.

The lithium air battery may include a swazelok type, a coin form, or a pouch form.

Other details of aspects of the invention are included in the following detailed description.

It is possible to implement a lithium air battery that can be commercialized and large in size by improving stability.

1 is a graph showing charge and discharge characteristics of a lithium air battery according to Example 1;

2 is a graph showing charge and discharge characteristics of the lithium air battery according to Example 2. FIG.

3 is a graph showing charge and discharge characteristics of a lithium air battery according to Comparative Example 1. FIG.

4 is a graph showing charge and discharge characteristics of a lithium air battery according to Comparative Example 2. FIG.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Unless stated otherwise in the present specification, when a part such as a layer, a film, an area, or a plate is "on" another part, it is not only when the other part is "right over" but also when there is another part in the middle. Include. On the contrary, when a part is "just above" another part, there is no other part in the middle.

According to an embodiment, a lithium air battery includes a battery cell including a positive electrode, a negative electrode facing the positive electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte solution impregnating the positive electrode, the negative electrode, and the separator. do.

The positive electrode includes a current collector and a positive electrode active material layer formed on the current collector. The positive electrode active material layer includes a positive electrode active material.

The current collector may be aluminum (Al), nickel (Ni), iron (Fe), titanium (Ti), stainless steel, etc., but is not limited thereto. Examples of the shape of the current collector include a foil shape, a plate shape, a mesh (or grid) shape, a foam (or sponge) shape, and the like, and among these, a foam (or sponge) shape excellent in current collection efficiency may be mentioned. .

Lithium peroxide (Li ₂ O ₂ ), lithium oxide (Li ₂ O), lithium hydroxide (LiOH) or a combination thereof may be used as the cathode active material, and among them, lithium peroxide (Li ₂ O ₂ ) may be used. Can be. During charging, the positive electrode active material such as Li ₂ O ₂ is decomposed to generate lithium ions, which move to the negative electrode, and when the discharge occurs, the positive electrode active material such as Li ₂ O ₂ is improved, thereby improving stability of the lithium air battery. can do.

The cathode active material may be included in an amount of 5 to 50 wt% based on the total amount of the cathode active material layer. When the positive electrode active material is included in the content range, it is possible to implement a stable lithium air battery during charging and discharging.

The cathode active material layer may further include at least one of a conductive material, a catalyst, and a binder.

The conductive material is used to impart conductivity to the electrode. Any conductive material may be used as long as it is an electron conductive material without causing chemical change in the battery. Specific examples of the conductive material may include a carbon-based material, a metal powder, a metal fiber, or a combination thereof. The carbonaceous material may have a porous structure and a large specific surface area. Examples of the carbon-based material may include natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, carbon nanotube, or a combination thereof. As the metal powder and the metal fiber, a metal such as copper, nickel, aluminum, or silver may be used. Moreover, you may use together 1 type, or 1 or more types of conductive materials, such as a polyphenylene derivative.

The conductive material may be included in an amount of 30 to 50 wt% based on the total amount of the cathode active material layer. When the conductive material is included in the content range, it is possible to implement a stable lithium air battery during charging and discharging.

The catalyst is supported on the conductive material and serves to help the decomposition of the cathode active material, and specific examples thereof include tricobalt tetraoxide (Co ₃ O ₄ ), manganese dioxide (MnO ₂ ), cerium dioxide (CeO ₂ ), and platinum (Pt). , Gold (Au), silver (Ag), ferric trioxide (Fe ₂ O ₃ ), triiron tetraoxide (Fe ₃ O ₄ ), nickel monoxide (NiO), copper oxide (CuO), perovskite catalyst Or a combination thereof.

The catalyst may be included in an amount of 1 to 50 wt% based on the total amount of the cathode active material layer. When the catalyst is included in the content range, it is possible to implement a stable lithium air battery during charging and discharging as the cathode active material is smoothly decomposed.

The binder adheres positively to the positive electrode active material particles, and also adheres the positive electrode active material to the current collector, and specific examples thereof include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, Carboxylated polyvinylchloride, polyvinylfluoride, polymers including ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber , Acrylated butadiene rubber, epoxy resin, nylon, and the like, but is not limited thereto.

The binder may be included in an amount of 5 to 30 wt% based on the total amount of the cathode active material layer. When the binder is included in the content range, it is possible to implement a stable lithium air battery during charging and discharging.

The positive electrode is designed by exposing to air when manufacturing a lithium air battery. As the positive electrode is exposed to air, oxygen generated by the decomposition of the positive electrode active material may escape to the outside of the battery, thereby preventing the electrolyte from being oxidized due to the generated oxygen. In addition, when a small spark occurs, it can be exploded due to oxygen, which can be prevented, and can also prevent the volume expansion of the battery due to oxygen.

The negative electrode includes a current collector and a negative electrode active material layer formed on the current collector. The negative electrode active material layer includes a negative electrode active material.

The current collector may be copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam (foam), copper foam, a polymer substrate coated with a conductive metal, or a combination thereof, but is not limited thereto.

The negative electrode active material may be an alloy of lithium metal, a material capable of doping and undoping lithium, a transition metal oxide, or a combination thereof. When manufacturing a lithium air battery according to an embodiment using the negative electrode active material it can significantly increase the stability compared to the case of using lithium metal.

As the alloy of the lithium metal, lithium and Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, Sn, or a combination thereof Alloys of the metals including can be used.

Examples of materials capable of doping and undoping lithium include Si, Si-C composites, SiO _x (0 <x <2), and Si-Y alloys (wherein Y is an alkali metal, an alkaline earth metal, and a group 13 to 16 element). , Transition metals, rare earth elements or combinations thereof, not Si), Sn, Sn-C composites, SnO ₂ , Sn-Y alloys (wherein Y is an alkali metal, an alkaline earth metal, an element of Group 13-16, a transition metal) , Rare earth elements or combinations thereof, and not Sn), and at least one of these and SiO ₂ may be mixed and used. As the element Y, Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, Se, Te, Po, or a combination thereof is mentioned.

When the negative electrode active material is used in a lithium air battery, it has a higher theoretical capacity than the carbon-based material, and the theoretical density is also higher than that of the carbon-based material, thereby making it possible to manufacture a lithium air battery having an excellent energy density.

Among the negative electrode active materials, a material capable of doping and undoping the lithium may be used, and more preferably, a Si-C composite or a Sn-C composite may be used. When the negative electrode active material is used in a lithium air battery, it is possible to manufacture a lithium air battery having a lower voltage band and having a large energy density due to relatively high capacity and stable life characteristics.

The transition metal oxide may include vanadium oxide, lithium vanadium oxide, titanium oxide, or a combination thereof, but is not limited thereto.

The negative active material may be included in an amount of 30 to 95 wt% based on the total amount of the negative electrode active material layer. When the negative electrode active material is included in the content range, it is possible to implement a stable lithium air battery during charging and discharging.

The negative electrode active material layer may further include at least one of a conductive material and a binder.

The conductive material is used to impart conductivity to the electrode. Any conductive material may be used as long as it is an electron conductive material without causing chemical change in the battery. Specific examples of the conductive material include carbon-based materials, metal powders and metal fibers, or a combination thereof. The carbonaceous material may include natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, or a combination thereof, and the metal powder and metal fiber may be metals such as copper, nickel, aluminum, silver, and the like. It may be used. Moreover, you may use together 1 type, or 1 or more types of conductive materials, such as a polyphenylene derivative.

The conductive material may be included in an amount of 1 to 50 wt% based on the total amount of the anode active material layer. When the conductive material is included in the content range, it is possible to implement a stable lithium air battery during charging and discharging.

The binder may be included in an amount of 3 to 30 wt% based on the total amount of the anode active material layer. When the binder is included in the content range, it is possible to implement a stable lithium air battery during charging and discharging.

The positive electrode and the negative electrode are prepared by mixing each active material, conductive material and binder in a solvent to prepare an active material composition, and applying the composition to a current collector. The positive electrode is designed by exposing to air when manufacturing a lithium air battery.

Since such an electrode manufacturing method is well known in the art, detailed description thereof will be omitted. N-methylpyrrolidone may be used as the solvent, but is not limited thereto.

The separator may be a single film or a multilayer film, for example, may be made of polyethylene, polypropylene, polyvinylidene fluoride, or a combination thereof.

The electrolyte may be a solid electrolyte or a liquid electrolyte.

As the solid electrolyte, polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyvinylidene fluoride, or a combination thereof may be used.

As the liquid electrolyte, a non-aqueous organic solvent can be used.

The non-aqueous organic solvent serves as a medium through which ions involved in the electrochemical reaction of the cell can move. The non-aqueous organic solvent may be selected from carbonate, ester, ether, ketone, alcohol and aprotic solvents.

Examples of the carbonate solvent include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), and ethylpropyl carbonate ( ethylpropyl carbonate (EPC), methylethyl carbonate (MEC), ethylmethyl carbonate (EMC), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate , BC) and the like can be used.

In addition, the ester solvent may be, for example, methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, decanolide, valerolactone, and merol. Valonolactone, caprolactone, and the like may be used. As the ether solvent, for example, dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, and the like may be used. As the ketone solvent, cyclohexanone may be used. Can be. In addition, ethyl alcohol, isopropyl alcohol, etc. may be used as the alcohol solvent.

In addition, the non-aqueous organic solvent may use tetraethylene glycol dimethyl ether, ethylene glycol dimethacrylate, polyethylene glycol, polyethylene glycol dialkyl ether, polyalkyl glycol dialkyl ether, or a combination thereof.

The non-aqueous organic solvents may be used alone or in combination of one or more, and the mixing ratio in the case of mixing one or more may be appropriately adjusted according to the desired battery performance.

The electrolyte solution may include a lithium salt.

The lithium salt is a substance that dissolves in the non-aqueous organic solvent, acts as a source of lithium ions in the battery to enable operation of the lithium air battery, and promotes the movement of lithium ions between the positive electrode and the negative electrode. .

Specific examples of the lithium salt include LiPF ₆ , LiBF ₄ , LiSbF ₆ , LiAsF ₆ , LiN (SO ₃ C ₂ F ₅ ) ₂ , LiC ₄ F ₉ SO ₃ , LiClO ₄ , LiAlO ₂ , LiAlCl ₄ , LiN (C _x F _{2x + 1} SO ₂ ) (C _y F _{2y + 1} SO ₂ ), where x and y are natural numbers, LiCl, LiI, LiB (C ₂ O ₄ ) ₂ (lithium bis (oxalato) ) borate; LiBOB), or a combination thereof.

The concentration of the lithium salt is preferably used within the range of about 0.1M to about 2.0M. When the concentration of the lithium salt is included in the above range, since the electrolyte has an appropriate conductivity and viscosity, it can exhibit excellent electrolyte performance, and lithium ions can move effectively.

The lithium air battery may be manufactured in the form of a swazelok, or may be manufactured in the form of a coin, a pouch, or the like.

The following presents specific embodiments of the present invention. However, the examples described below are merely for illustrating or explaining the present invention in detail, and thus the present invention is not limited thereto.

In addition, the description is not described herein, so those skilled in the art that can be sufficiently technically inferred, the description thereof will be omitted.

(리튬 공기 전지 제작)(Lithium air battery production)

실시예 1Example 1

To a solution of 28 mmol of resorcinol (Aldrich) and 120 mmol of formaldehyde (37% aqueous solution, Aldrich), sodium carbonate and resorcinol are added in a molar ratio of 45: 100 and mixed. The mixed solution is mixed at 75 ° C. for 1 hour, and then the gelled mixture is aged at room temperature for 24 hours. The aged mixture is washed with water and ethanol to remove sodium carbonate. The resulting structure was immersed in a tributylphenyltin (Aldrich) solution for one day, and then heat-treated at 700 ° C. for 2 hours in an Ar atmosphere to prepare a Sn-C composite.

The prepared Sn-C composite powder, polyvinylidene fluoride (PVDF) and carbon black (super P) were mixed at a weight ratio of 80:10:10, respectively, and dispersed in N-methyl-2-pyrrolidone to prepare a negative electrode active material. Prepare the layer composition. After casting the negative electrode active material layer composition on a copper foil, the cast electrode is dried in an oven at 100 ℃ for 2 hours, and vacuum dried for 12 hours or more to prepare a negative electrode.

Lithium peroxide (Li ₂ O ₂ ), polyvinylidene fluoride (PVDF) and carbon black (super P) were mixed at a weight ratio of 45:10:45, respectively, dispersed in N-methyl-2-pyrrolidone to give a positive electrode. An active material layer composition is prepared. After casting the cathode active material layer composition on an aluminum mesh, the cast electrode was dried in an oven at 100 ° C. for 2 hours, and vacuum dried for 12 hours or more to prepare a cathode.

Swagelok type lithium air battery is fabricated using the prepared separator of the cathode and anode and the porous polyethylene membrane (Celgard 3501, Celgard 3501). At this time, the anode is manufactured to have a hole in order to pass oxygen well. An electrolyte solution in which LiPF ₆ is dissolved at a concentration of 1 M is injected into a mixed solution having a mixing volume ratio of 3: 7 between ethylene carbonate (EC) and dimethyl carbonate (DMC) between the positive electrode and the negative electrode.

실시예 2Example 2

Si powder of 100 nm size and natural graphite powder of 5 μm size are mixed in a weight ratio of 30:70, which is mixed in a tetrahydrofuran solution. 33 parts by weight of pitch are mixed with respect to 100 parts by weight of the mixed solution, followed by ball milling for 12 hours. The mixed solution was dried in a vacuum oven at 100 ° C. for 6 hours, and then heat-treated at 1000 ° C. for 5 hours in an Ar atmosphere to prepare a Si-C composite.

The prepared Si-C composite powder, carbon black (super P), carboxymethylcellulose and styrene-butadiene rubber were mixed with water in a weight ratio of 85: 5: 3.3: 6.7, respectively, to prepare a negative electrode active material layer composition. After casting the negative electrode active material layer composition on a copper foil, the cast electrode is dried in an oven at 100 ℃ for 2 hours, and vacuum dried for 12 hours or more to prepare a negative electrode.

Lithium peroxide (Li _₂ O _2), polyvinylidene fluoride (PVDF), and carbon black (super P) were mixed each in a weight ratio of 45:10:45, N- methyl-pyrrolidone and dispersed in the positive An active material layer composition is prepared. After casting the cathode active material layer composition on an aluminum mesh, the cast electrode was dried in an oven at 100 ° C. for 2 hours, and vacuum dried for 12 hours or more to prepare a cathode.

비교예 1Comparative Example 1

Lithium peroxide (Li ₂ O ₂ ), polyvinylidene fluoride (PVDF) and carbon black (super P) were mixed at a weight ratio of 45:10:45, respectively, dispersed in N-methyl-2-pyrrolidone to give a positive electrode. An active material layer composition was prepared. The cathode active material layer composition was coated on a current collector of nickel foam to prepare a cathode after drying and rolling.

Artificial graphite (MCMB), polyvinylidene fluoride (PVDF) and carbon black (super P) were mixed in a weight ratio of 92: 5: 3, respectively, and dispersed in N-methyl-2-pyrrolidone to form a negative electrode active material layer composition Was prepared. The negative electrode active material layer composition was coated on a copper foil having a thickness of 15 μm to prepare a negative electrode after drying and rolling.

Swagelok type lithium air battery is fabricated using the prepared separator of the cathode and anode and the porous polyethylene membrane (Celgard 3501, Celgard 3501). At this time, the anode is manufactured to have a hole in order to pass oxygen well. The electrolyte is prepared by injecting an electrolyte solution in which LiPF ₆ is dissolved at a concentration of 1 M into a mixed solution having a mixing volume ratio of 3: 7 between ethylene carbonate (EC) and dimethyl carbonate (DMC) between the positive electrode and the negative electrode.

비교예 2Comparative Example 2

In Comparative Example 1, the catalyst MnO ₂ (5 parts by weight based on 100 parts by weight of carbon black) supported on lithium peroxide (Li ₂ O ₂ ), polyvinylidene fluoride (PVDF), and carbon black (super P) was respectively 45:10. A lithium air battery was manufactured in the same manner as in Comparative Example 1, except that the positive electrode was prepared by mixing at a weight ratio of: 45.

실험예 1: 리튬 공기 전지의 전기화학성능 평가Experimental Example 1 Evaluation of Electrochemical Performance of Lithium Air Battery

In order to evaluate the electrochemical performance of the lithium air battery, the charge and discharge characteristics of the lithium air battery according to Examples 1 and 2 and Comparative Examples 1 and 2 manufactured above were evaluated and the results are shown in FIGS. 1 to 4.

The lithium air battery of Example 1 was placed in a chamber filled with oxygen, and then charged and discharged once under a current condition of 10 mA / g at 1.2 to 4.5 V. In addition, the lithium air battery of Example 2 was once charged and discharged at a current condition of 5 mA / g at 2.0 to 4.5V. In addition, the lithium air batteries of Comparative Examples 1 and 2 were once charged and discharged at a current condition of 10 mA / g at 2.0 to 4.1 V.

1 is a graph showing the charge and discharge characteristics of the lithium air battery according to Example 1, Figure 2 is a graph showing the charge and discharge characteristics of the lithium air battery according to Example 2, Figure 3 is lithium air according to Comparative Example 1 4 is a graph showing charge and discharge characteristics of a battery, and FIG. 4 is a graph showing charge and discharge characteristics of a lithium air battery according to Comparative Example 2. FIG.

Referring to FIGS. 1 to 4, according to the exemplary embodiment of using lithium peroxide (Li ₂ O ₂ ) as the positive electrode active material and Sn-C composite as the negative electrode active material, lithium peroxide (Li as a positive electrode active material) _In Example 2 using ₂ O ₂ ) and using the Si-C composite as the negative electrode active material, it can be confirmed that the charge and discharge characteristics are superior to those of Comparative Examples 1 and 2 using the carbon-based compound as the negative electrode active material. .

From this it can be seen that the stability of the lithium air battery according to the embodiment is excellent.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of the invention.

Claims

A positive electrode including a current collector and a positive electrode active material layer disposed on the current collector and including a positive electrode active material;

A negative electrode including a negative electrode active material; And

Including an electrolyte solution,

The positive electrode active material includes lithium peroxide (Li 2 O 2 ), lithium oxide (Li 2 O), lithium hydroxide (LiOH) or a combination thereof,

The anode active material includes an alloy of lithium metal, a material capable of doping and undoping lithium, a transition metal oxide, or a combination thereof.

Lithium air battery.
The method of claim 1,

The cathode active material layer further comprises a conductive material comprising a carbon-based material, metal powder, metal fiber or a combination thereof.
The method of claim 2,

The carbonaceous material is natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, carbon nanotubes or a combination thereof.
The method of claim 1,

The cathode active material layer further comprises a catalyst.
The method of claim 4, wherein

The catalyst is tricobalt tetraoxide (Co 3 O 4 ), manganese dioxide (MnO 2 ), cerium dioxide (CeO 2 ), platinum (Pt), gold (Au), silver (Ag), ferric trioxide (Fe 2 O 3 ), trioxide A lithium air battery comprising iron (Fe 3 O 4 ), nickel monoxide (NiO), copper oxide (CuO), perovskite-based catalyst, or a combination thereof.
The method of claim 4, wherein

The catalyst is a lithium air battery containing 1 to 50% by weight based on the total amount of the positive electrode active material layer.
The method of claim 1,

The positive electrode active material is a lithium air battery containing 5 to 50% by weight based on the total amount of the positive electrode active material layer.
The method of claim 1,

The alloy of the lithium metal is lithium and Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, Sn or a combination thereof. A lithium air battery comprising an alloy of a metal to contain.
The method of claim 1,

The materials capable of doping and undoping lithium include Si, Si-containing alloys, Si-C composites, SiO x (0 <x <2), Sn, Sn-containing alloys, Sn-C composites, SnO 2, or combinations thereof. A lithium air battery comprising a.
The method of claim 1,

The transition metal oxide is vanadium oxide, lithium vanadium oxide, titanium oxide or a combination thereof.
The method of claim 1,

The lithium air battery is a swage (swagelok) type, coin type or pouch form of a lithium air battery.