WO2017126855A1 - Positive electrode of lithium-air battery having side reaction prevention film to which metal catalyst is partially introduced, lithium-air battery having same, and manufacturing method therefor - Google Patents

Abstract

The present invention relates to a positive electrode of a lithium-air battery having a side reaction prevention film to which a metal catalyst is partially introduced, and a manufacturing method therefor. More specifically, the present invention relates to a positive electrode of a lithium-air battery having a side reaction prevention film, and a manufacturing method therefor, wherein a metal catalyst is partially and sporadically introduced to a surface thereof. The lithium-air battery according to the present invention suppresses side reactions in a positive electrode active material and electrolyte interface, and thereby can effectively reduce overvoltage when charged, does not cause electrolyte decomposition, and improves cycle lifetime.

Description

A cathode of a lithium-air battery having a side reaction prevention film partially introduced with a metal catalyst, a lithium-air battery comprising the same, and a method of manufacturing the same

This application claims the benefit of priority based on Korean Patent Application No. 10-2016-0006885 dated January 20, 2016 and Korean Patent Application No. 10-2017-0007064 dated January 16, 2017. All content disclosed in the literature is included as part of this specification.

The present invention relates to a cathode of a lithium-air battery having a side reaction prevention film in which a metal catalyst is partially introduced on a surface thereof, and a manufacturing method thereof.

Metal-air batteries use metals such as lithium (Li), zinc (Zn), aluminum (Al), magnesium (Mg), iron (Fe), calcium (Ca) and sodium (Na) as metal anodes And oxygen in the air as the positive electrode active material. In addition, the metal-air battery generates electricity by reacting metal ions of the negative electrode with oxygen, and unlike the conventional secondary battery, it is not necessary to have a positive electrode active material in the battery in advance, so that the weight can be reduced. In addition, a large amount of negative electrode material can be stored in the container, which can theoretically show a large capacity and high energy density.

The metal-air battery is composed of a metal fuel electrode (cathode) and an oxygen air electrode (anode). During discharge, metal ions are formed due to oxidation of the metal anode, and the generated metal ions move across the electrolyte to the oxygen cathode. In the oxygen cathode, the outside oxygen is dissolved in the electrolyte inside the cavity of the oxygen anode and reduced.

Among metal-air batteries, in particular, lithium-air batteries generally include a negative electrode capable of occluding / discharging lithium ions, a positive electrode including a redox catalyst of oxygen using oxygen in air as a positive electrode active material, and between the positive electrode and the negative electrode. Is provided with a lithium ion conductive medium. The theoretical energy density of lithium-air cells is more than 3000 Wh / kg, which corresponds to approximately 10 times the energy density of lithium-ion cells. In addition, lithium-air batteries are environmentally friendly and can provide improved safety than lithium-ion batteries.

Important factors that determine the electrochemical characteristics of lithium-air battery include electrolyte system, anode structure, good air cathode catalyst, type of carbon support, oxygen pressure, etc. same.

Scheme 1

Oxide ^{electrode: Li (s) ↔ Li +} + e -

Cathode: 4Li + O ₂ → 2Li ₂ OV = 2.91 V

2Li + O ₂ → Li ₂ O ₂ V = 3.10 V

That is, during discharge, lithium generated from the negative electrode meets oxygen gas of the positive electrode to generate lithium oxide, and oxygen is reduced (Oxygen Reduction Reaction: ORR) to generate oxygen anions. In contrast, lithium oxide is reduced during charging and oxygen gas is generated as oxygen is oxidized (Oxygen Evolution Reaction: OER).

The solid lithium oxide formed during discharging does not dissolve well in an organic solvent but exists as a solid oxide and accumulates at a reaction site of a carbon electrode as an anode, thereby blocking the channel of oxygen and inhibiting diffusion of oxygen. In other words, it prevents contact between oxygen and lithium ions and prevents pores of carbon, which is a positive electrode, making it difficult to form lithium oxide, making capacity development difficult and deteriorating characteristics of a secondary battery. In addition, charge transfer is inhibited due to side reaction deposits during charging, and thus high resistance and high voltage are formed, resulting in battery degradation due to electrolyte decomposition reactions.

[Technical Document] Korean Unexamined Patent Publication No. 2015-0022095 "Anode Material for Metal Air Battery and Metal Air Battery Including the Same"

As described above, the solid lithium oxide and the side reaction deposits of the lithium-air battery increase the overvoltage during charging to reduce the charge / discharge energy efficiency and cause the decomposition of the solvent in the electrolyte, which is mainly a defect of the surface of the carbon-based conductive material. It occurs at (Defect). Metal or metal oxide catalysts are mainly used to prevent such reactions, but still do not solve the problem.

Accordingly, an object of the present invention is to provide a lithium-known battery in which charge overvoltage is reduced and cycle life is improved by fundamentally blocking an interface between a carbon-based conductive material and an electrolyte.

In order to achieve the above object, the present invention is a carbon-based conductive material coated on one surface of the porous current collector; A side reaction prevention film coated on the surface of the carbon-based conductive material; And a metal catalyst sporadically introduced into the surface of the side reaction prevention film, wherein the side reaction prevention film is a conductive metal oxide.

In another aspect, the present invention provides a lithium-air battery comprising the positive electrode.

In addition, the present invention comprises the steps of: i) coating a carbon-based conductive material on the porous current collector; ii) depositing an anti-reaction film on the surface of the carbon-based conductive material; And iii) introducing a metal catalyst into the side reaction prevention film, wherein the side reaction prevention film includes a conductive metal oxide.

The lithium-air battery according to the present invention suppresses side reactions at the surface of the conductive carbon and the electrolyte, and thus does not cause decomposition of the electrolyte, thereby stabilizing for a long time, thereby improving cycle life. In addition, the overvoltage is effectively reduced by the catalyst particles additionally supported on the surface of the side reaction prevention film, and thus has an effect of suppressing the decomposition of the electrolyte due to the high voltage.

1 is a schematic cross-sectional image of a lithium-air battery of the present invention.

2 is data comparing the charge and discharge curves of Example 1 and Comparative Examples 1 and 2 according to the present invention.

3 is data comparing the cycle capacity of Example 1 and Comparative Examples 1 and 2 according to the present invention.

The present invention is intended to block the contact with the electrolyte by coating the surface of the carbon-based conductive material of the positive electrode active material with an anti-reaction film, and to introduce a metal catalyst to promote the redox reaction of oxygen.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. These drawings belong to one embodiment for explaining the present invention and may be implemented in various different forms, not limited to this specification. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and similar reference numerals are used for similar parts throughout the specification. In addition, the size and relative size of the components shown in the drawings are not related to the actual scale, may be reduced or exaggerated for clarity of description.

In this specification, the numerical range shown using "-" shows the range which includes the numerical value described before and after "-" as minimum value and the maximum value, respectively. In addition, in this specification, "combination of these" means, unless otherwise specified, by mixing or combining two or more as a single element, or applying each of them as a separate element, the above application Regardless of form, each combination is considered to be one species.

Anode for Lithium-Air Battery

1 is a schematic cross-sectional view of a lithium-air battery according to the present invention, which will be described in more detail with reference to the cathode 100, the cathode 200, a separator 300 interposed therebetween, and an electrolyte 400. In the lithium-air battery comprising a), the positive electrode 100 is a porous current collector (10); A carbon-based conductive material 20 coated on one surface of the porous current collector 10; A side reaction prevention film 30 coated on the surface of the carbon-based conductive material 20; And a metal catalyst 40 is sporadically introduced into the surface of the side reaction prevention film 30.

In the present invention, the introduction of the metal catalyst 40 is led by the electrostatic attraction or van der Waals attraction between the side reaction prevention layer 30 and the metal catalyst 40 and is buried by the side reaction prevention layer 30. It means a supported or coated state.

The porous current collector 10 of the present invention is a porous current collector having gas permeability, preferably porous carbon pulp, porous carbon paper, in addition to foamed metal, metal fiber, porous metal Porous three-dimensional current collectors, nonwoven fabrics, and the like, such as (Porous metal), etched metal, and uneven metals. In addition, a plurality of pores may exist inside the carbon-based conductive material 20, and these pores increase the permeability of air containing oxygen, thereby increasing the number of active sites, large pore volumes, and high specific ratios. Since it has a high specific surface area, it is desirable to provide an anode reaction site.

In the present invention, the carbon-based conductive material 20 is a particle or structure having a size of nano units, and it is preferable to use a porous carbon powder or a carbon structure having a large specific surface area and high electrical conductivity, for example, graphite or activated carbon. It is preferable to include one selected from the group consisting of carbon black, carbon fiber, carbon nanostructure, and combinations thereof, but is not limited thereto.

In particular, the carbon-based conductive material 20 is coated using the conductive metal oxide as the side reaction prevention layer 30 in the present invention, and the side reaction product is physically blocked between the carbon-based conductive material 20 and the electrolyte 400. To suppress sedimentation. In the case of modifying the surface by coating with such a conductive metal oxide, the low resistance of the interface in addition to the interface reaction with the electrolyte contributes to the performance of the battery.

The conductive metal oxide according to the present invention is indium tin oxide (ITO), indium zinc oxide (IZO, Indium Zinc Oxide), antimony tin oxide (ATO, Antimony Tin Oxide), fluoride tin oxide (FTO, Fluoro Tin Oxide) ), Aluminum zinc oxide (AZO), magnesium indium oxide (Magnesium Indium Oxide), gallium zinc oxide (GZO), gallium indium oxide (Galliumm Indium Oxide), indium-gallium-zinc oxide (IGZO) , Indium Gallium Zinc Oxide), Niobium-Strontium-Titanium Oxide (Nb-STO, Niobium Strontium Titanium Oxide), Indium Cadmium Oxide, BZO (Boron Zinc Oxide), SZO (SiO ₂ -ZnO), Indium Oxide (In ₂ O ₃ ) and combinations thereof, and may include one selected from the group consisting of a combination thereof. Preferably, indium tin oxide (ITO) or indium zinc oxide (IZO) is applied.

Among the conductive metal oxides, transparent conductive oxides (TCOs) having a wide bandgap, low resistance, and high transmittance in the visible region, such as indium tin oxide (ITO) or indium zinc oxide (IZO), are solar cells. ), Touch panels, heat mirrors, organic electroluminescence devices (OLEDs), and liquid crystal displays (LCDs), which have a conductivity similar to that of metals, even though they are metal oxides. Since it is possible to completely cover the carbon defect part and physically block the electrolyte 400, it is most preferable as the side reaction prevention film 30 of the present invention.

In addition, the thickness of the side reaction prevention film 30 is preferably in the range of 5 ~ 30 nm, if less than 5 nm there is a risk that the carbon-based conductive material 20 is exposed to the electrolyte 400, if more than 30 nm This is because it is difficult to support a large amount of discharge products (for example, Li ₂ O ₂ ) by changing the structure of the fine pores of the carbon-based conductive material 20 and reducing the size.

As the metal catalyst 40 of the present invention, it is preferable to use a known metal or metal compound capable of weakening or breaking the bond of lithium oxide (Li ₂ O ₂ or Li ₂ O) generated during discharge. For example, the metal catalyst 40 may include ruthenium (Ru), palladium (Pd), platinum (Pt), gold (Au), nickel (Ni), copper (Cu), silver (Ag), zinc (Zn), and lead ( Pb), cadmium (Cd), tin (Sn), titanium (Ti) and alloys thereof, oxides, sulfides or selenides thereof, preferably ruthenium oxide (RuO ₂ ) is applied.

The metal catalyst 40 is to be included in 10 to 50 parts by weight with respect to 100 parts by weight of the carbon-based conductive material 20, the metal catalyst 40 is that the average particle diameter of 1 to 10 nm to use the present invention It is desirable to secure the effect according to.

Manufacturing method of positive electrode for lithium air battery

The positive electrode for a lithium-air battery having the components as described above comprises the steps of: i) coating a carbon conductive material on the porous current collector; ii) depositing a conductive metal oxide as an anti-reaction film on a surface thereof to include the carbon conductive material; And iii) can be prepared through the step of introducing a metal catalyst to the side reaction prevention film, it will be described in detail for each step below.

First, a carbon conductive material is coated on the porous current collector. The carbon-based conductive material and the binder are mixed at a weight ratio of 9: 1 to 7: 3, respectively, and dispersed in a solvent to form a slurry composition, and then coated on a porous current collector and dried.

The binder serves to bond the carbon-based conductive material and to fix them to the current collector. In the present invention, the kind is not particularly limited, and any binder known in the art may be used. For example, one type selected from the group consisting of an acrylic binder, a fluororesin binder, a rubber binder, a cellulose binder, a polyalcohol binder, a polyolefin binder, a polyimide binder, a polyester binder, a silicone binder, and a combination thereof may be used. More specifically, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF) and copolymers or celluloses thereof may be applied, and more preferably polyvinylidene fluoride (PVDF: poly vinylidene fluoride) may be used.

The solvent for forming the slurry may be water or an organic solvent, the organic solvent in the group consisting of isopropyl alcohol, N-methylpyrrolidone (N-Methyl-2-pyrrolidone: NMP), acetone and combinations thereof It is possible to apply the selected one.

Next, a conductive metal oxide is deposited on the entire surface of the porous current collector to include the coated carbon-based conductive material to form an anti-reaction film.

There is no limitation on the method of coating on the porous substrate, for example, doctor blade coating, dip coating, gravure coating, slit die coating, spin coating Coating may be performed by coating, comma coating, bar coating, reverse roll coating, screen coating, cap coating, or the like.

In addition, after the coating, it may be dried for 12 to 36 hours in a vacuum oven heated to 100 ~ 150 ℃. Through the drying step, the solvent contained in the slurry is evaporated, thereby facilitating binding force between the carbon-based conductive material and the current collector, and simultaneously dispersing and bonding the carbon-based conductive material to the inner frame of the porous current collector.

Next, a conductive metal oxide is deposited on the entire surface of the porous current collector to include the coated carbon-based conductive material to form an anti-reaction film. Preferably, at least one selected from the above-described conductive metal oxides is dry deposited on the carbon-based conductive material coated porous current collector, and may be deposited by, for example, a sputtering or thermal vapor deposition method.

More specifically, it can be deposited by ion beam sputtering, DC sputtering, RF-sputtering, or thermal evaporation deposition, and this method is characterized by high deposition rate at room temperature and There is a release of non-toxic gas, ease of operation, safety, etc., and it is possible to deposit on a large-area substrate. In addition, such a method is not only easy to control the thickness of the side reaction prevention film, but also inexpensive compared to atomic layer deposition (ALD), and has the advantage of producing a relatively even deposition surface.

Next, a metal catalyst is introduced into the side reaction prevention film to prepare a lithium-air battery positive electrode. The method of introducing the metal catalyst into the side reaction prevention film is not limited. For example, after the carbon-based conductive material coated with the prepared side reaction prevention film is immersed in a beaker containing a metal precursor, the metal is repeatedly immersed in distilled water. It is possible to introduce oxides. Metal oxides can be introduced through a simple process of obtaining metal cations in a beaker containing the metal precursors and obtaining oxygen anions in distilled water.

The positive electrode manufactured through the above process is easily introduced into a lithium-air battery to fundamentally block contact between the electrolyte and the carbon-based conductive material.

Lithium-air battery

The present invention, as shown in Figure 1, the anode 100; Cathode 200; Provided is a lithium-air battery having a separator 300 interposed therebetween and an electrolyte solution 400 impregnated therebetween. Lithium-air battery according to an embodiment of the present invention includes a separator provided on at least one surface of the porous coating layer according to the above-described embodiments, it may have a conventional configuration and components of the metal-air battery. At this time, the one surface on which the carbon-based conductive material 20, the side reaction prevention film 30, and the metal catalyst 40 of the porous current collector 10 is formed on the positive electrode 100 is preferably disposed to be impregnated in the electrolyte 400. .

When the lithium air battery is driven, side reactions of the electrodes 100 and 200 are caused by the electrolyte 400 in contact with the electrodes. In other words, a material of lithium carbonate or lithium carboxylate is produced by reacting with lithium ions and a solvent in the electrolyte, which causes deterioration of battery characteristics. The side reaction occurs mainly at the anode 100 rather than at the cathode 200. Accordingly, in the present invention, the side reaction prevention layer 30 and the metal catalyst 40 are disposed to be impregnated in the electrolyte solution 400 to suppress side reactions occurring in the anode 100 or to promote decomposition of the generated reactants. In addition, it exhibits the effect of improving the electrochemical reactivity of the metal catalyst 40 itself, as a result of increasing the battery capacity of the lithium-air battery and at the same time improve the cycle characteristics.

1 schematically shows a cross-sectional structure of a lithium-air battery according to an embodiment of the present invention. At this time, the positive electrode, the negative electrode and the electrolyte may be applied to those known in the art.

Lithium-air battery of the present invention applies the above-described positive electrode 100, the thickness of the positive electrode 100 is not particularly limited, but may be preferably 10 ~ 100㎛, more preferably the thickness of the positive electrode May be 20 to 60 μm.

According to one embodiment of the invention, the negative electrode active material of the negative electrode 200 may be selected from the group consisting of lithium metal, lithium metal-based alloys, lithium compounds and lithium intercalation (Intercalation) material.

In particular, the lithium metal-based alloy, for example, an alloy of lithium with one or more materials selected from the group consisting of Na, K, Rb, Cs, Fr, Be, Ma, Ca, Sr, Ba, Ra, Al and Sn The lithium compound may be a material that reacts with lithium ions to reversibly form a lithium-containing compound. For example, the lithium compound may be tin oxide (SnO ₂ ), titanium nitrate (TiN), or recon. In addition, the lithium intercalating material means a material capable of reversibly intercalating or deintercalating lithium ions, and may be, for example, crystalline carbon, amorphous carbon, or a mixture thereof.

The thickness of the cathode 200 is not particularly limited, but may be 50 μm or more. The upper limit of the thickness of the cathode is not particularly limited, but thicker is better. In consideration of the possibility of commercialization, the thickness of the cathode may be 50 ~ 500㎛.

A conventional separator 300 may be interposed between the anode 100 and the cathode 200. The separator 300 has a function of physically separating the electrode, and can be used without particular limitation as long as it is used as a conventional separator, and in particular, has a low resistance to ion migration of the electrolyte, and an excellent electrolyte-moisture capability. Do.

In addition, the separator 300 enables transport of lithium ions between the positive electrode and the negative electrode while separating or insulating the positive electrode 100 and the negative electrode 200 from each other. The separator 300 may be made of a porous and nonconductive or insulating material. The separator may be an independent member such as a film or a coating layer added to the anode and / or the cathode.

Specifically, a porous polymer film made of a polyolefin-based polymer such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / methacrylate copolymer may be used alone. It may be used as a lamination or or a conventional porous non-woven fabric, for example, a non-woven fabric made of glass fibers, polyethylene terephthalate fibers of high melting point, etc. may be used, but is not limited thereto.

According to one embodiment of the invention, the electrolyte 400 is a non-aqueous electrolyte containing an ionizable lithium salt and an organic solvent. For example, the solvent of the non-aqueous electrolyte solution is carbonate such as ethylene carbonate (EC), propylene carbonate (PC), chain carbonate such as diethylene carbonate, 1,2-dioxane (1 Ethers such as 2,2-Dioxane), nitriles such as acetonitrile (AN), and amides may be used, but are not limited thereto. One or more of these can be used in combination.

The lithium salt may be LiPF _{6 ,} LiBF ₄ , LiSbF ₆ , LiAsF ₆ , LiN (SO ₂ C ₂ F ₅ ) ₂ , Li (CF ₃ SO ₂ ) ₂ N, LiC ₄ F ₉ SO ₃ , LiClO ₄ , LiAlO ₂ , LiAlCl ₄ , LiF, LiBr, LiCl, LiI and LiB (C ₂ O ₄ ) ₂ , LiCF ₃ SO ₃ , LiN (SO ₂ CF ₃ ) ₂ (Li-TFSI), LiN (SO ₂ C ₂ F ₅ ) ₂ and LiC (SO ₂ CF _3), but it may use one or two or more selected from the group consisting of _3, and the like. The concentration of the lithium salt can be used within the range of 0.1 ~ 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 form of the lithium-air battery according to the present invention is not limited, and may be, for example, coin, flat, cylindrical, horn, button, sheet or stacked. It is also possible to apply to large batteries such as electric vehicles. In addition, the lithium-air battery according to the present invention can be used for both the metal primary battery and the metal secondary battery. The present invention can also be applied to large batteries used in electric vehicles. In addition, it is also possible to manufacture a battery module comprising a lithium-air battery according to the present invention as a unit cell.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are not intended to limit the scope of the present invention, which will be construed as to help the understanding of the present invention.

<Example 1>

Step 1. Coating the positive electrode active material on the porous current collector

To 0.8 g of carbon-based conductive material (CNT), 1.695 g of kf1100 in which binder (PVDF) was dissolved in N-methylpyrrolidone (NMP) solvent was added. The primary slurry was prepared to be 2. Thereafter, an additional 25 g of N-methylpyrrolidone (NMP) was added to prepare a second slurry that can be coated. The secondary slurry was used for blade coating on carbon paper. After coating it was dried for at least 24 hours in a vacuum oven previously heated to 120 ℃.

Step 2. Side reaction prevention coating

A sputtering process was used to coat the indium tin oxide (ITO) layer as a side reaction prevention layer. The deposition process was performed at room temperature, and proceeded to have a thickness of about 10 nm in an argon (Ar) atmosphere.

Step 3. Introduction of metal catalyst

A ruthenium precursor solution was prepared to introduce a ruthenium oxide catalyst. A precursor solution in which ruthenium chloride (RuCl ₂ ) was dissolved in distilled water to have a concentration of 10 mM in a beaker was prepared. In another beaker, the same amount of distilled water was prepared and heated to 60 ° C.

In Step 2, the anode-coated anode was coated in an aqueous solution containing ruthenium ions and immersed in distilled water heated to 60 ° C. for 15 seconds and 30 seconds, and then taken out five times. Since oxygen anions are supported from distilled water, no separate washing procedure is included. The positive electrode for lithium-air battery into which the metal catalyst was introduced was dried in a vacuum oven previously heated to 120 ° C. for at least 24 hours.

Step 4. Lithium-Air Battery Manufacturing

Using the anode prepared in Step 3, it was assembled in the form of a coin cell (Gin box) in a glove box of argon (Ar) atmosphere. The coin cell was assembled by putting a positive electrode, a glass fiber, a lithium negative electrode, a gasket, a stainless steel coin, a spring, and a top plate in order to the stainless steel perforated bottom plate. Tetraethylene glycol dimethyl ether (TEGDME) in which 1 M LiTFSI was dissolved was used.

Comparative Example 1

A lithium-air battery was manufactured by the same method as in Example 1 (except Step 2 and Step 3) using the cathode coated with only a carbon-based conductive material.

Comparative Example 2

A lithium-air battery was manufactured in the same manner as in Example 1 (except Step 2), by using a cathode coated with ruthenium oxide as a metal catalyst on the carbon-based conductive material of Example 1.

Experimental Example 1

The completed coin cell was subjected to a discharge and charge experiment in an oxygen atmosphere of 1 atm. Discharge and charge experiments were conducted at a discharge / charge rate of 0.3 C / 0.1 C based on a capacity of 1,000 mAh / g relative to the weight of carbon. Comparison of charge and discharge curves and cycle capacities of a lithium-air battery using a carbon-based conductive material (CNT) anode, an anode carrying a side reaction prevention film, and a catalyst layer is shown in FIGS. 2 and 3.

Looking at the charge and discharge curve of Figure 2, the lithium-air battery of Example 1 has a lower voltage than the lithium-air battery of Comparative Example 1, it can be seen that the overvoltage is reduced, compared to Comparative Example 2 somewhat overvoltage Was measured high, but this appeared to be negligible. In addition, the cycle capacity curve of FIG. 3 shows that the discharge capacity of Comparative Example 1 is greatly reduced when 30 cycles are progressed, while Comparative Example 2 is greatly reduced before proceeding with 20 cycles, while the discharge capacity of Example 1 is 50 cycles. It was confirmed to maintain the initial state until progress.

Although preferred embodiment 1 of the present invention has 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 present invention.

The battery pack including the lithium-sulfur battery is an electric vehicle (EV), a hybrid electric vehicle (HEV), a plug-in hybrid electric vehicle (PHEV), power Can be used as a power source for storage.

Claims (11)

1. Porous current collectors;

   A carbon-based conductive material coated on one surface of the porous current collector;

   A side reaction prevention film coated on the surface of the carbon-based conductive material; And

   And a metal catalyst sporadically introduced into the surface of the side reaction prevention film.

   The side reaction prevention film is a lithium-air battery positive electrode, characterized in that it comprises a conductive metal oxide.
2. The method of claim 1,

   The conductive metal oxide may be indium tin oxide, indium zinc oxide, antimony tin oxide, tin fluoride oxide, aluminum zinc oxide, magnesium indium oxide, zinc gallium oxide, gallium indium oxide, indium gallium zinc oxide, niobium-strontium-titanium oxide And an indium cadmium oxide, BZO, SZO, indium oxide, and a combination thereof.
3. The method of claim 1,

   The thickness of the side reaction prevention film is a lithium-air battery positive electrode, characterized in that 5 ~ 30 nm.
4. The method of claim 1,

   The carbon-based conductive material is a cathode for a lithium-air battery, characterized in that it comprises one selected from the group consisting of graphite, activated carbon, carbon black, carbon fiber, carbon nanostructures and combinations thereof.
5. The method of claim 1,

   The metal catalyst is ruthenium, palladium, platinum, gold, nickel, copper, silver, zinc, lead, cadmium, tin, titanium and alloys thereof, oxides, sulfides or selenides thereof, the cathode for a lithium-air battery.
6. The method of claim 1,

   The metal catalyst is a positive electrode for a lithium-air battery, characterized in that contained in 10 to 50 parts by weight based on 100 parts by weight of the carbon-based conductive material.
7. The method of claim 1,

   The average particle diameter of the metal catalyst is a lithium-air battery positive electrode, characterized in that 1 to 10 nm.
8. In the positive electrode manufacturing method for a lithium-air battery,

   i) coating a carbon-based conductive material on the porous current collector;

   ii) depositing an anti-reaction film on the surface of the carbon-based conductive material; And

   iii) introducing a metal catalyst into the side reaction prevention film;

   The side reaction prevention film is a positive electrode manufacturing method for a lithium-air battery, characterized in that it comprises a conductive metal oxide.
9. The method of claim 8,

   The deposition of step ii) is a method for producing a cathode for a lithium-air battery, characterized in that performed by sputtering or thermal vapor deposition.
10. The method of claim 8,

    The conductive metal oxide may be indium tin oxide, indium zinc oxide, antimony tin oxide, tin fluoride oxide, aluminum zinc oxide, magnesium indium oxide, zinc gallium oxide, gallium indium oxide, indium gallium zinc oxide, niobium-strontium-titanium oxide And an indium cadmium oxide, BZO, SZO, indium oxide, and a combination thereof.
11. Lithium cathode; anode; In a lithium-air battery comprising a separator and an electrolyte interposed therebetween,

    The positive electrode is a lithium-air battery, characterized in that the positive electrode for a lithium-air battery of any one of claims 1 to 7.

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