WO2017126855A1 - Électrode positive de batterie au lithium-air ayant un film de prévention de réaction secondaire sur lequel un catalyseur métallique est partiellement introduit, batterie au lithium-air la comprenant et son procédé de fabrication - Google Patents

Électrode positive de batterie au lithium-air ayant un film de prévention de réaction secondaire sur lequel un catalyseur métallique est partiellement introduit, batterie au lithium-air la comprenant et son procédé de fabrication Download PDF

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WO2017126855A1
WO2017126855A1 PCT/KR2017/000535 KR2017000535W WO2017126855A1 WO 2017126855 A1 WO2017126855 A1 WO 2017126855A1 KR 2017000535 W KR2017000535 W KR 2017000535W WO 2017126855 A1 WO2017126855 A1 WO 2017126855A1
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lithium
oxide
air battery
carbon
positive electrode
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English (en)
Korean (ko)
Inventor
이동욱
류병국
한재성
채종현
양두경
조은경
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LG Chem Ltd
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LG Chem Ltd
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Priority to CN201780003170.7A priority Critical patent/CN108028392B/zh
Priority to JP2018500714A priority patent/JP6494854B2/ja
Priority to US15/743,387 priority patent/US10505203B2/en
Priority to EP17741621.1A priority patent/EP3316366B1/fr
Priority claimed from KR1020170007064A external-priority patent/KR102024899B1/ko
Publication of WO2017126855A1 publication Critical patent/WO2017126855A1/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H01M4/8668—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H01M4/8673—Electrically conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8817—Treatment of supports before application of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8689—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • 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.
  • 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.
  • 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).
  • cathode a metal fuel electrode
  • anode an oxygen air electrode
  • metal ions are formed due to oxidation of the metal anode, and the generated metal ions move across the electrolyte to the oxygen cathode.
  • oxygen cathode the outside oxygen is dissolved in the electrolyte inside the cavity of the oxygen anode and reduced.
  • 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.
  • lithium-air batteries are environmentally friendly and can provide improved safety than lithium-ion batteries.
  • Electrolyte system anode structure, good air cathode catalyst, type of carbon support, oxygen pressure, etc. same.
  • Oxide electrode Li (s) ⁇ Li + + + e -
  • 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.
  • 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.
  • 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.
  • 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.
  • the present invention provides a lithium-air battery comprising the positive electrode.
  • 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.
  • 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.
  • FIG. 1 is a schematic cross-sectional image of a lithium-air battery of the present invention.
  • Example 2 is data comparing the charge and discharge curves of Example 1 and Comparative Examples 1 and 2 according to the present invention.
  • Example 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the side reaction product is physically blocked between the carbon-based conductive material 20 and the electrolyte 400.
  • 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.
  • ITO indium tin oxide
  • ITO in
  • transparent conductive oxides 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.
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • Touch panels heat mirrors
  • organic electroluminescence devices OLEDs
  • LCDs liquid crystal displays
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the kind is not particularly limited, and any binder known in the art may be used.
  • 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.
  • PVDF polyvinylidene fluoride
  • 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.
  • 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.
  • 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.
  • the coating may be dried for 12 to 36 hours in a vacuum oven heated to 100 ⁇ 150 °C.
  • 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.
  • 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.
  • 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.
  • the method 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • FIG. 1 schematically shows a cross-sectional structure of a lithium-air battery according to an embodiment of the present invention.
  • the positive electrode, the negative electrode and the electrolyte may be applied to those known in the art.
  • the thickness of the positive electrode 100 is not particularly limited, but may be preferably 10 ⁇ 100 ⁇ m, more preferably the thickness of the positive electrode May be 20 to 60 ⁇ m.
  • 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.
  • 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.
  • the lithium compound may be tin oxide (SnO 2 ), titanium nitrate (TiN), or recon.
  • 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 ⁇ m 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 ⁇ m.
  • 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.
  • 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.
  • 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.
  • the electrolyte 400 is a non-aqueous electrolyte containing an ionizable lithium salt and an organic solvent.
  • 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.
  • 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.
  • 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.
  • Step 1 Coating the positive electrode active material on the porous current collector
  • NMP N-methylpyrrolidone
  • 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.
  • 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.
  • 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.
  • the anode prepared in Step 3 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.
  • 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.
  • 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.
  • 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.
  • CNT carbon-based conductive material
  • 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.
  • 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.
  • 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.
  • EV electric vehicle
  • HEV hybrid electric vehicle
  • PHEV plug-in hybrid electric vehicle

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Abstract

La présente invention concerne une électrode positive d'une batterie au lithium-air ayant un film de prévention de réaction secondaire sur lequel un catalyseur métallique est partiellement introduit, et son procédé de fabrication. Plus spécifiquement, la présente invention concerne une électrode positive d'une batterie au lithium-air ayant un film de prévention de réaction secondaire, et son procédé de fabrication, un catalyseur métallique étant introduit partiellement et de façon sporadique sur une surface de cette dernière. La batterie au lithium-air selon la présente invention supprime les réactions secondaires dans une matière active d'électrode positive et une interface d'électrolyte, ce qui permet de réduire efficacement les surtensions lorsqu'elle est chargée, ne provoque pas de décomposition électrolytique, et améliore la durée de vie de cycle.
PCT/KR2017/000535 2016-01-20 2017-01-16 Électrode positive de batterie au lithium-air ayant un film de prévention de réaction secondaire sur lequel un catalyseur métallique est partiellement introduit, batterie au lithium-air la comprenant et son procédé de fabrication Ceased WO2017126855A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201780003170.7A CN108028392B (zh) 2016-01-20 2017-01-16 具有部分引入金属催化剂的副反应阻止层的锂-空气电池的正极、具有所述正极的锂-空气电池及其制造方法
JP2018500714A JP6494854B2 (ja) 2016-01-20 2017-01-16 金属触媒が部分導入された副反応防止膜を有するリチウム−空気電池の正極、これを含むリチウム−空気電池及びこの製造方法
US15/743,387 US10505203B2 (en) 2016-01-20 2017-01-16 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
EP17741621.1A EP3316366B1 (fr) 2016-01-20 2017-01-16 Électrode positive de batterie au lithium-air ayant un film de prévention de réaction secondaire sur lequel un catalyseur métallique est partiellement introduit, batterie au lithium-air la comprenant et son procédé de fabrication

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20160006885 2016-01-20
KR10-2016-0006885 2016-01-20
KR10-2017-0007064 2017-01-16
KR1020170007064A KR102024899B1 (ko) 2016-01-20 2017-01-16 금속 촉매가 부분 도입된 부반응 방지막을 가지는 리튬-공기전지의 양극, 이를 포함하는 리튬-공기전지 및 이의 제조방법

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WO2017126855A1 true WO2017126855A1 (fr) 2017-07-27

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009181901A (ja) * 2008-01-31 2009-08-13 Ohara Inc 固体電池
KR20140030482A (ko) * 2012-08-30 2014-03-12 한국과학기술연구원 리튬 공기 이차전지용 양극, 그 제조 방법 및 이를 이용한 리튬 공기 이차전지
KR20140039755A (ko) * 2012-09-25 2014-04-02 현대자동차주식회사 리튬공기전지 양극용 복합산화물 촉매, 이를 포함한 리튬공기전지용 양극 및 리튬공기전지
KR20140052139A (ko) * 2012-10-19 2014-05-07 한양대학교 산학협력단 리튬 공기 전지용 양극, 이의 제조방법 및 이를 포함하는 리튬 공기 전지
KR20150031213A (ko) * 2013-09-13 2015-03-23 주식회사 엘지화학 리튬 공기 전지용 양극 및 그의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009181901A (ja) * 2008-01-31 2009-08-13 Ohara Inc 固体電池
KR20140030482A (ko) * 2012-08-30 2014-03-12 한국과학기술연구원 리튬 공기 이차전지용 양극, 그 제조 방법 및 이를 이용한 리튬 공기 이차전지
KR20140039755A (ko) * 2012-09-25 2014-04-02 현대자동차주식회사 리튬공기전지 양극용 복합산화물 촉매, 이를 포함한 리튬공기전지용 양극 및 리튬공기전지
KR20140052139A (ko) * 2012-10-19 2014-05-07 한양대학교 산학협력단 리튬 공기 전지용 양극, 이의 제조방법 및 이를 포함하는 리튬 공기 전지
KR20150031213A (ko) * 2013-09-13 2015-03-23 주식회사 엘지화학 리튬 공기 전지용 양극 및 그의 제조방법

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