WO2017007203A1 - 루테늄산화물과 망간산화물의 복합체로 구성된 1차원의 다결정 튜브 구조를 가지는 리튬 -공기전지용 촉매 및 그 제조방법 - Google Patents
루테늄산화물과 망간산화물의 복합체로 구성된 1차원의 다결정 튜브 구조를 가지는 리튬 -공기전지용 촉매 및 그 제조방법 Download PDFInfo
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- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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- D01D5/0007—Electro-spinning
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- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
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- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/20—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of cyclic compounds with one carbon-to-carbon double bond in the side chain
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- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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- 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
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- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8857—Casting, e.g. tape casting, vacuum slip casting
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- H—ELECTRICITY
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- 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
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/16—Physical properties antistatic; conductive
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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
- H01M4/02—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
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- H—ELECTRICITY
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- 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
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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
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8673—Electrically conductive fillers
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- 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
- Catalyst for lithium-air battery having a one-dimensional polycrystalline tube structure composed of a complex of ruthenium oxide and manganese oxide, and a method of manufacturing the same
- the present invention relates to a catalyst for a lithium-air battery having a one-dimensional polycrystalline tube structure composed of a complex of ruthenium oxide and manganese oxide, and a method of manufacturing the same. More specifically, a ruthenium oxide-manganese oxide having a core fiber-shell shell-like nanotube structure or a double-walled flute double tube structure.
- a catalyst for a lithium-air battery comprising a composite tube structure and a method of manufacturing the same.
- Lithium-air batteries are attracting attention as promising next-generation energy storage devices due to their theoretical energy density and eco-friendliness that are more than 10 times higher than conventional lithium-silver batteries.
- oxygen in the air is used as a cathode (or anode) reaction fuel
- lithium metal is used as a cathode
- the weight of the battery is not only light, and theoretical energy is not enough even when compared to gasoline fuel at the present time.
- the driving principle of a lithium-air battery is that oxygen in the air meets lithium ions in the electrolyte to form a solid lithium oxide during the discharge process on the cathode (Oxygen Reduction Reaction, 0 2 (g) + 2Li + + 2e " -> Li 2 0 2 (s)) and decomposes again to oxygen and lithium ions during the charging process (Oxygen Evolution Reaction, Li 2 0 2 (s)-> 0 2 (g) + 2Li + + 2e ⁇ ).
- the activity of the catalyst depends on various factors such as manufacturing method, surface structure, crystallinity, oxidation number, specific surface area, etc.In this process, the development of nanostructures to enhance the activity of the catalyst and the good reaction properties such as 0ER and 0R Research to find catalyst materials is also being done.
- the present invention relates to a core tube-shell shell-like nanotube structure or
- the present invention relates to a catalyst for a lithium-air battery including a ruthenium oxide-manganese oxide composite tube structure having a multi-walled complex double tube structure.
- the technical problem to be achieved by the present invention is excellent in the activity of 0ER and 0RR catalyst to minimize energy loss during charging and discharging, and to provide a high-efficiency lithium-air battery cathode catalyst and a method for manufacturing the lithium ion-air battery significantly improved life characteristics It is.
- the catalyst for lithium-air battery having a one-dimensional polycrystalline tube structure composed of a composite of ruthenium oxide and manganese oxide proposed in the present invention, the core-shell shell-shaped nanotube structure and the back wall Ruthenium oxide-manganese oxide composite having at least one or more polycrystalline tube structure selected from the hybrid double tube structure, the ruthenium oxide-manganese oxide composite may be used as a catalyst for the cathode.
- the ruthenium oxide in the ruthenium oxide-manganese oxide composite may be Ru0 2 .
- the manganese oxide in the ruthenium oxide-manganese oxide composite may be one selected from Mn 2 0 3 and Mn 0 2 , or a manganese oxide in which the two phases are mixed with each other.
- the core is a nanofiber structure ruthenium oxide is located and the shell is a tube-shaped shell structure manganese oxide is positioned, Pores are present between the core fiber and the shell shell may have a nanotube structure in which the core and the shell are separated from each other.
- pores between the core fiber and the shell shell may be unevenly distributed, such that the core fiber and the shell shell are locally mixed.
- the core nanofibers may have a diameter in the range of 10 to 500 nm, and the diameter of the nanotubes constituting the shell shell may have a diameter in the range of 15 to 1000 nm. have.
- the double-walled common double-tube structure is not divided into core fibers and shells because phase separation does not occur, and has the double-walled structure consisting of an inner tube and an outer tube, and the inner tube and the outer rib are ruthenium oxide. And manganese oxide may be mixed with each other to form a complex and uniformly complex.
- the double wall shaped common double tube structure may have a structure in which the inner wall and the outer wall are not locally separated.
- the double wall shaped common double tube structure has the double wall shape consisting of an inner tube and an outer tube, the diameter of the inner rib includes a diameter in the range of 10 to 500 nm, and the diameter of the outer tube is 15 It may include a diameter in the range of ⁇ 1000 nm.
- the thickness of the shell outer wall of the core fiber-shell shell-shaped nanotube structure and the thickness of the outer wall and inner wall of the double wall-shaped common double tube structure may include a range of 1 to 100 nm.
- the catalyst manufacturing method for a lithium-air battery having a one-dimensional polycrystalline tube structure composed of a composite of ruthenium oxide and manganese oxide proposed in the present invention, a ruthenium precursor and a manganese precursor in a solvent in which the polymer is dissolved Melting to prepare an electrospinning solution; Synthesizing the polymer composite nanofibers containing the ruthenium precursor and the manganese precursor by using the electrospinning solution in the electrospinning solution; Sintering the polymer composite nanofiber to form a ruthenium oxide-manganese oxide composite having the polycrystalline tube structure; And forming a slurry using the ruthenium oxide-manganese oxide composite, casting to form an air electrode, and forming a catalyst for a lithium-air battery.
- the step of forming the ruthenium oxide-manganese oxide composite, the core fiber-shell shell nanotube structure of the core fiber-shell shell which undergoes the sintering process through the low temperature rising rate during the high temperature heat treatment and the sintering process through the high temperature raising rate At least one of the wall-shaped common double tube structures may be selected to form the ruthenium oxide-manganese oxide composite having the polycrystalline tube structure.
- At least one of the core fiber-shell shell-shaped nanotube structure and the double-walled common double-tube structure is selected to form the ruthenium oxide-manganese oxide composite.
- PTFE Polytetrafluoroethylene, PTFE
- an adhesive comprising at least one or more, and coating on a current collector to form the cathode;
- a catalyst for the lithium one air battery including the cathode and the lithium cathode, the electrolyte, the separator, and the gas diffusion layer.
- the relative weight ratio of the ruthenium precursor and the manganese precursor may be selected in the range of 50:50 to 10:90.
- the step of preparing the electrospinning solution dimethylformamide, phenol, acetone, toluene, tetrahydrofuran, distilled water or ethane, methanol, propanol, butane, isopropanol, alcohol-based solvents such as alcohol group Heterogeneous solvents with a difference in boiling point above 20 ° C can be used in the range of 10:90 to 90:10 weight ratios of high boiling point solvent and low boiling point solvent.
- the low temperature increase rate includes a range of 0.1 ⁇ 3 ° C / min
- the high temperature increase rate may include a range of 3 ⁇ 10 0 C / min.
- the forming of the lithium-air battery catalyst may include 1 to 50% by weight of the catalyst for lithium-air battery, 50 to 90% by weight of the conductive material, and 1 to 10% by weight of the adhesive.
- An air cell cathode catalyst can be provided.
- FIG. 1 is a flowchart illustrating a method for preparing a lithium-air battery catalyst having a one-dimensional polycrystalline tube structure composed of a composite of ruthenium oxide and manganese oxide according to an embodiment of the present invention.
- FIG. 2 is a view showing a nanofiber including a ruthenium precursor and a manganese precursor according to an embodiment of the present invention.
- FIG. 3 is a view showing ruthenium oxide and manganese oxide having a core fiber-shell shell-shaped nanotube structure according to an embodiment of the present invention.
- FIG. 4 is a view showing a ruthenium oxide x cobalt oxide having a nanotube structure of the core fiber-shell shell shape according to an embodiment of the present invention.
- FIG. 5 is a view showing a ruthenium oxide-manganese oxide having a double-walled common double tube structure according to an embodiment of the present invention.
- FIG. 6 illustrates a double wall shaped double tube structure according to an embodiment of the present invention. Is a diagram showing ruthenium oxide-manganese oxide.
- FIG. 7 is a graph showing an initial layer, a discharge curve according to an embodiment of the present invention.
- FIG. 9 is a graph showing the time-dependent voltage change of the lithium-air battery cathode according to an embodiment of the present invention.
- lithium-air containing a catalyst for a lithium-air battery and a catalyst including a ruthenium oxide-manganese oxide composite tube structure having a core fiber-shell shell-shaped nanotube structure or a double-walled common double tube structure The battery cathode manufacturing method is described in Examples 1 and 2.
- a cathode for a lithium-air battery without a catalyst was prepared.
- the cathode containing the catalyst had remarkably improved 0ER and 0RR catalytic activity and excellent life characteristics.
- FIG. 1 shows a method for preparing a lithium-air battery catalyst having a one-dimensional polycrystalline tube structure composed of a composite of ruthenium oxide and manganese oxide according to an embodiment of the present invention. I am a flow chart.
- a method for preparing a lithium-air battery catalyst including a ruthenium oxide-manganese oxide composite tube structure having a core fiber-shell shell-shaped nanotube structure or a double-walled common double tube structure will be described in detail. Can be.
- step (S10) it is possible to prepare an electrospinning solution by dissolving ruthenium precursor and manganese precursor in a solvent in which the polymer is dissolved.
- the electrospinning solution may be selected from the relative weight ratio of the ruthenium precursor and the manganese precursor in the range of 1:99 to 99: 1, for example, in the range of 50:50 to 10:90.
- the electrospinning solution has a boiling point in a group consisting of dimethylformamide, phenol, acetone, toluene, tetrahydrofuran, distilled water or ethane, methane, propanol, butanol, isopropane and alcohol solvents such as alcohols.
- Heterogeneous solvents with a difference of more than 20 ° C can be used in the range of 10: 90 to 90: 10 weight ratio of high boiling solvent and low boiling solvent.
- the metal precursors used are salts comprising the metals described above, for example acetates, chlorides, acetylacetonates, nitrates, mesosides, oxoxides, secondary compounds, isopropoxides, sulfides, oxytriiso It may be any one or two or more mixed salts selected from metal salts in the form of propoxide, (ethyl or cetylethyl) nucleus sanoate, butanoate, ethylamide, amide and the like.
- the electrospinning solution should contain a polymer for electrospinning
- the ruler gives a viscosity to the spinning solution to form a fibrous phase during spinning, and can control the structure of the spun fiber by compatibility with the precursor for forming metals and metal oxides.
- PVP polyvinylpyridine
- the polymer may have an average molecular weight (Mw) of 100,000-1,500,000 g / mol.
- Mw average molecular weight
- the weight average molecular weight of the polymer may be 500,000-1,300,000 g / mol in order to maintain the shape of the metal oxide nanofiber obtained through the electrospinning and high temperature heat treatment process.
- the polymer is not particularly limited as long as it satisfies the above average molecular weight.
- polyvinylacetate (PVAc) polyvinylpyridone (PW) ⁇ polyvinyl alcohol (PVA), polyethylene oxide (PE0), polyaniline (PANi), polyacrylonitrile (PAN), polymethyl methacrylate Rate (PVIA), polyacrylic acid (PM), or polyvinylchloride (PVC).
- PVAc polyvinylacetate
- PW polyvinylpyridone
- PVA polyethylene oxide
- PANi polyaniline
- PAN polyacrylonitrile
- PVA polymethyl methacrylate Rate
- PM polyacrylic acid
- PVC polyvinylchloride
- the weight ratio of the metal precursor and the polymer may be characterized in that 5: 1 to 1: 5 to maintain the shape of the nanofiber, for example, to make a core-shell nanotube or composite double tube 3: You can make it from 1 to 1: 2.
- heterogeneous solvents having different boiling points may promote phase separation between the polymer and the metal oxide precursor during electrospinning.
- metal precursors are more easily soluble in other first solvents than solvents in which polymers are dissolved (second solvents), and these differences in solubility and boiling point This facilitates the synthesis of nano-sulfur with a core-shell structure of a polymer-metal precursor that has undergone phase separation.
- the first solvent rapidly evaporates during the electrospinning process.
- the metal precursor dissolved in the first solvent is moved to the surface of the nanofibers, and the polymer naturally gathers around the nanofibers to form the core-shell structured nanofibers of the polymer-metal precursor.
- the first or second solvent it should have sufficient solubility to dissolve the metal precursor and the polymer, dimethylformamide, phenol, acetone, toluene, tetrahydrofuran, distilled water or ethanol, methanol, propanol, butane, isopropanol, etc.
- Alcohol solvents may be used, and heterogeneous solvents having a difference in boiling point of 20 ° C or more may be selected from 10: 90 to 90: 10 by weight ratio of solvents of high boiling point and low boiling point.
- distilled water as the first solvent and dimethylformamide as the second solvent in a weight ratio of 1: 1
- the core-shell nanotubes and the composite heterotubes described above can be implemented.
- the electrospinning solution may be synthesized using the electrospinning method, polymer composite nanofibers containing a ruthenium precursor and a manganese precursor.
- Electrospinning solution is characterized in that it comprises the step of electrospinning using an electrospinning device consisting of a single nozzle to which a high voltage is applied, maintaining the ambient humidity less than 50% during the electrospinning, the scanning speed is 0.001 ⁇ Supplied at 1 ml / min, 10 to 24 kV This can be done by applying the above voltage.
- nanofibers may be obtained by using a drum type collector at a distance of 10 to 30 cm from a single nozzle tip.
- the polymer composite nanofibers may be heat-treated at a high temperature to form a ruthenium oxide-manganese oxide composite having a polycrystalline tube structure.
- Ruthenium oxide is characterized by having a phase of Ru0 2 , and may include, in addition to Ru0 2 , an iridium oxide (I r) or cobalt oxide (Co 3 0 4 ) having excellent 0ER catalytic activity, but is not limited thereto.
- I r iridium oxide
- Co 3 0 4 cobalt oxide
- the manganese oxide is characterized by having an image of Mn 2 0 3, Mn 2 0 3 other than ⁇ - ⁇ 0 2, ⁇ - ⁇ 0 2, ⁇ - ⁇ 0 2, ⁇ - ⁇ 0 2, and ⁇ - ⁇ ⁇ 0 2
- Other oxide catalysts superior to phase or 0RR catalytically active may be additionally included without limitation.
- Ruthenium oxide-manganese oxide having a core fiber-shell shell-shaped nanotube structure or a double-walled common double-tube structure obtained by heat-treating nanofibers containing polymer-metal precursors at different heating rates can be synthesized. have.
- At least one of a core fiber-shell 3 ⁇ 4 quality nanotube structure subjected to heat treatment at a low temperature increase rate and a double wall common double tube structure subjected to heat treatment at a high temperature increase rate is selected for high temperature heat treatment.
- a ruthenium oxide-manganese oxide composite having a polycrystalline tube structure is selected for high temperature heat treatment.
- Crystallization of ruthenium oxide and manganese oxide is achieved, and the polymer can be maintained for 5 minutes to 12 hours at a high temperature of 400 ⁇ 1000 ° C to burn. For example, It can be maintained for 1 to 3 hours at a temperature of 500-700 ° C to implement a ruthenium oxide-manganese oxide having a core fiber-shell shell-shaped nano-leave structure or a double wall-shaped common double tube structure.
- ruthenium oxide-manganese oxide having a core fiber-shell 3 ⁇ 4-shaped nanotube structure or a double-walled common double tube structure By varying the rate of temperature increase during the heat treatment process, it is possible to synthesize ruthenium oxide-manganese oxide having a core fiber-shell 3 ⁇ 4-shaped nanotube structure or a double-walled common double tube structure. For example, ruthenium oxide having a low crystallization temperature is first crystallized during a temperature raising process, and crystallization of manganese oxide may be sequentially performed.
- ruthenium oxide when maintaining a low temperature increase rate, first, ruthenium oxide may be provided with sufficient time for the first formed ruthenium oxide to converge in the middle of the Ostwar ld r ipening in the polymer matrix. Then, when the temperature rises, the crystallization of the remaining manganese oxide naturally left, the core fiber-shell shell-like nanotube structure in which the ruthenium oxide and manganese oxide completely phase separation can be made.
- the low temperature increase rate is in the range of 0.1 ⁇ 3 ° C / min
- the high temperature increase rate may mean in the range of 3 ⁇ 10 ° C / min, but is not limited thereto. It may vary depending on the type of metal precursor and the crystallization temperature of the metal oxide, the dielectric transition temperature according to the type of the polymer, the ratio of the metal oxide and the polymer.
- ruthenium oxide manganese oxide
- a temperature increase rate of 1 ° C./min was maintained, and to form a double-walled common double tube structure ruthenium oxide and manganese oxide.
- the temperature increase rate of 5 ° C / min can be maintained.
- a slurry may be formed using a ruthenium oxide-manganese oxide composite, and cast to form an air electrode, thereby forming a catalyst for a lithium-air battery.
- the process for forming a catalyst for lithium-air batteries is selected from at least one of a core fiber-shell shell-shaped nanotube structure and a double-walled common double-tube structure, such that a ruthenium oxide-manganese oxide composite is prepared by Ketjen-Block.
- Fins conductive materials containing at least one of carbon nanotubes and polyvinylidene fluoride (PVDF), Styrene—butadiene rubber (SBR) / car boxyme t hy 1 cel lulose (CMC), It may be mixed with an adhesive including at least one of polytetraflooroethylene (PTFE) and coated on a current collector to form an air electrode.
- PVDF polyvinylidene fluoride
- SBR Styrene—butadiene rubber
- CMC car boxyme t hy 1 cel lulose
- PTFE polytetraflooroethylene
- the lithium-air battery cathode may be formed by slurry casting on a slurry containing a lithium-air battery catalyst, a conductive material, and an adhesive to a well-flowing nickel mesh current collector.
- the cathode of a lithium-air battery may include a catalyst for lithium-air battery in an amount of 0 to 99% by weight, a conductive material in an amount of 1 to 99%, and an adhesive of 1 to 99% by weight.
- a catalyst for lithium-air battery in an amount of 0 to 99% by weight
- a conductive material in an amount of 1 to 99%
- an adhesive 1 to 99% by weight.
- 1 to 50% by weight of a catalyst for a lithium one air battery, 50 to 90% by weight of a conductive material, and 1 to 10% by weight of an adhesive may be included.
- a ruthenium oxide-manganese oxide catalyst having a core fiber-shell shell-shaped nanotube structure or a double-walled common double-tube structure was used to check the activity of the catalyst.
- an air electrode containing 60% by weight of Ketjen Black and 10% by weight of PVdF as an adhesive was used.
- an air electrode containing 90% by weight of Ketjen Black and 10 3/4> by weight of PVdF as an adhesive was used. Used.
- a catalyst for a lithium-ion air battery having a structure will be described in detail through one embodiment.
- a catalyst for a lithium-air battery having a one-dimensional polycrystalline tube structure composed of a complex of ruthenium oxide and manganese oxide includes a core fiber-shell 3 ⁇ 4-shaped nano-lube structure and a double-walled common double-tube structure. It may include a ruthenium oxide-manganese oxide composite having at least one polycrystalline tube structure, ruthenium oxide-manganese oxide composite may be used as a catalyst for the cathode.
- the ruthenium oxide in the ruthenium oxide-manganese oxide complex may be Ru0 2.
- the manganese oxide may be at least one or more of Mn 2 0 3 and Mn3 ⁇ 4.
- core is nanofiber structure
- ruthenium oxide is located
- shell is tube-shaped shell structure
- manganese oxide is located
- the nanotube structure may be separated from the shell.
- the pores between the core fibers and the shell shell may be unevenly distributed, so that the core fibers and the shell shell may be locally mixed.
- the core nanofibers have a diameter in the range of 10 to 500 ⁇ , and the nanotubes constituting the shell shell.
- the diameter of may have a diameter in the range of 15 ⁇ 1000 nm.
- phase separation does not occur, so it is not divided into core fibers and shell shells, and has a double-walled structure consisting of inner and outer tubes.
- the inner and outer tubes are ruthenium oxide and manganese. Oxides can be mixed with each other and evenly combined.
- the dual wall shaped double tube structure has pores between the inner wall and the outer wall so that each of the ribs can be separated into the pores at a distance of 5 to 500 nm from each other, and the inner wall and the outer wall are not locally separated.
- the double-walled common double-tube structure has a double-walled shape consisting of an inner tube and an outer tube, the inner tube having a diameter in the range of 10 to 500 ⁇ , and the outer tube having a diameter of 15 to 1000 ⁇ . It may include the diameter of the range.
- the thickness of the shell outer wall of the core fiber-shell shell-shaped nanotube structure and the thickness of the outer wall and inner wall of the double wall-shaped common double tube structure may include a range of 1 to 100 ⁇ ⁇ .
- a ruthenium oxide and a manganese oxide-based catalyst having a core tube-shell shell-shaped nanotube structure and to prepare a cathode for a lithium-air battery including the catalyst.
- An electrospinning solution containing ruthenium and manganese precursor may be prepared.
- PVP polyvinylpyridone
- DMF dimethylformamide
- DI—water distilled water
- the prepared electrospinning solution is injected at a rate of 10 ⁇ / min through the electrospinning technique, and the applied voltage is maintained at 17.5 kV and the distance between the single nozzle tip and the collector (current collector) is maintained at 15 cm. Can be.
- FIG. 2 is a view showing a nanofiber including a ruthenium precursor and a manganese precursor according to an embodiment of the present invention.
- the composite fiber obtained after the electrospinning before forming the core-shell nanotube or the heterogeneous composite tube provides an image of the nanofibers including the ruthenium precursor and the manganese precursor.
- the nanofibers containing the formed ruthenium precursor and the manganese precursor have a smooth surface and have a diameter of about 300 nm and can be randomly distributed through a scanning electron microscope.
- a ruthenium oxide-manganese oxide having a nanofiber structure of core fiber-shell 3 ⁇ 4 quality can be synthesized.
- the nanofibers were heat-treated at 600 ° C. for 1 hour at high temperature in air, and the heating rate was maintained at 1 ° C./min to prepare ruthenium oxide-cobalt oxide having a core fiber-shell 3 ⁇ 4 quality nanotube structure. can do.
- FIG. 3 is a view showing ruthenium oxide and manganese oxide having a core fiber-shell shell-shaped nanotube structure according to an embodiment of the present invention.
- FIG. 3 a scanning electron microscope image of a ruthenium oxide-cobalt oxide having a core fiber-shell 3 ⁇ 4-shaped nanotube structure, and the inside of a tube having a diameter of about 250 nm through synthesis. It can be seen that another nanofiber is formed separately.
- Core fiber-shell 3 ⁇ 4 quality nanotubes are formed by crystallization of ruthenium oxide first in the core site, and manganese oxide is later crystallized to form a shell.
- ruthenium oxide and manganese oxide may be used without limitation as long as it is a heterogeneous oxide having different crystallization temperatures, and may be used without limitation for heterogeneous metals made through reduction heat treatment after oxidation heat treatment.
- Core fiber-shell 3 ⁇ 4 quality nanotubes can be clearly distinguished by the presence of pores between the core ruthenium oxide and the manganese oxide of the shell, and the pores may vary depending on the diameter of the core fiber and the diameter of the outer wall.
- the core nanofibers of the core fiber-shell shell nanotubes have a diameter in the range of 10 to 500 nm, and the diameter of the nanotubes constituting the shell shell may include a diameter in the range of 15 to 1000 mm 3.
- the thickness of the shell outer wall of the core fiber-shell shell-shaped nanotube structure may include a range of 1 to 100 nm.
- the diameter of the nanotubes constituting the core nanofibers or shells of the core fiber-shell shell-shaped nanotubes, the thickness of the shell nanotube outer wall includes the amount of precursor, the ratio with the polymer, and the discharge rate of electrospinning. It can be freely adjusted according to the applied voltage, the distance between the single nozzle tip and the collecting part, the high temperature heat treatment temperature and the temperature increase rate.
- Figure 4 is a two-sided view showing a ruthenium oxide-cobalt oxide having a nano fiber structure of the core fiber-shell shell shape according to an embodiment of the present invention.
- ruthenium having a nanotube structure of the core fiber-shell 3 ⁇ 4 quality shape Transmission electron micrograph of fluorine-cobalt oxide, (a) is the magnification of transmission electron microscope, (bc) is the high magnification image, (cl) is the SAED pattern image, (e) is linear elemental analysis (f) Mapping elemental analysis represents an image.
- the shell portion coincides with the (222) plane of the manganese oxide (Mn 2 O 3 ).
- the core portion coincides with the (101) plane and (110) plane of the ruthenium oxide.
- FIG. 4D through SAED pattern analysis, the nanofibers can be seen that ruthenium oxide and manganese oxide exist while maintaining their respective phases, as shown in FIGS. 4E and 4F.
- Linear Elemental Analysis and Mapping Elemental analysis shows that the core and the shell have completely separate shapes of ruthenium oxide and manganese oxide, respectively.
- NMP N-Methyl-2-pyrrol idone
- the prepared slurry may be cast on a nickel mesh cut to a diameter of 11.8 pie through a brush to prepare a cathode.
- the fabricated cathode is assembled in a Swagelok cel l for lithium-air battery characterization in a glove box maintained in an Ar atmosphere. 2 sheets of lithium of 12 pi, 12.8 of Whatman's glass filter of 12.8 pi, and one sheet of 12 pi carbon paper as gas diffusion layer can be used.
- the lithium-air battery cell manufactured in this way may be connected to a frame manufactured to allow oxygen diffusion through the upper opening to evaluate the electrochemical characteristics.
- a cathode for a lithium-air battery including a ruthenium oxide-manganese oxide-based catalyst seto and a catalyst having a double-walled common double-tube structure was fabricated.
- An electrospinning solution containing ruthenium and manganese precursor may be prepared.
- 0.5 g of ruthenium chloride (RuCl 3 ) and 1.0 g of manganese acetate (Mn (CH 3 C00) 2 ⁇ 43 ⁇ 40) were added 0.5 g of polyvinylpyridone (PVP, Mw).
- PVP polyvinylpyridone
- -1, 300, 000 can be dissolved in a mixed solution of 4 g of dimethylformamide (DMF) and 1 g of distilled water (DI-water), followed by stirring at 50 ° C for 3 hours.
- DMF dimethylformamide
- DI-water distilled water
- Nanofibers containing ruthenium and manganese precursors may be synthesized through electrospinning.
- Example 1 and Example 2 is a form in which deformation occurs after heat treatment from nanofibers containing the same ruthenium precursor and manganese precursor Therefore, the same applies to FIG. 2, and as shown in FIG. 2, the nanofibers containing the formed ruthenium and manganese precursors have a smooth surface and are randomly distributed with a diameter of about 300 nm. You can check through
- Ruthenium oxide-manganese oxide having a double-walled common double tube structure can be synthesized.
- the nanofibers are heat-treated at 600 ° C. for 1 hour at high temperature in air, and the heating rate is maintained at 5 ° C./min to prepare ruthenium oxide-manganese oxide having a double-walled common double tube structure.
- FIG. 5 illustrates a ruthenium oxide-manganese oxide having a double wall-shaped common double tube structure according to an embodiment of the present invention.
- FIG. 5 a scanning electron micrograph of a ruthenium oxide-manganese oxide having a double-walled common double tube structure, (a) is a low magnification of the transmission electron microscope, (b) is a high magnification image, (c) The SAED pattern image, (d) shows a mapping elemental analysis image, and it can be seen that another rib is formed inside the tube having a diameter of about 250 nm through the synthesis process.
- ruthenium oxide and manganese oxide may be arbitrarily distributed without restriction on the positions of the outer tube and the inner tube, and may be formed at about the same time during the high temperature heat treatment process.
- double wall-shaped common double tube can be clearly divided into heterogeneous tube due to the presence of pores between the inner tube and the outer rib, the described pore diameter and thickness of the inner tube and outer rib It may vary.
- double wall The diameters of the inner and outer ribs and the outer wall thickness of the shaped common double-tube structure are determined by the amount of precursor contained, the ratio with the polymer, the discharge rate of the electrospinning, the strength of the applied voltage, and the distance between the single nozzle tip and the collecting part. , Can be freely adjusted according to the sintering temperature and the temperature increase rate.
- the diameter of the inner flow tube forming the composite double-walled tube structure includes a diameter in the range of 10 to 500 nm
- the diameter of the outer tube includes a diameter in the range of 15 to 1000 mm 3. can do.
- the thickness of the outer wall and the inner wall of the double-walled common double tube structure may include a range of 1 to 100 nm.
- FIG. 6 is a view showing a ruthenium oxide-manganese oxide having a double wall-shaped common double tube structure according to an embodiment of the present invention.
- a transmission electron micrograph of a ruthenium oxide-manganese oxide having a double-walled common double tube structure and as a result of checking the interplanar distance at an arbitrary point of FIG. 6A, showed manganese oxide (Mn 2 0 It can be seen that the (222) plane of 3 ) and the (110) plane of the ruthenium oxide coexist together.
- An air electrode containing a catalyst can be produced.
- a lute having a double wall shaped common double tube structure Slurry can be prepared with sufficient NMP solution containing 90 mg of nium oxide-manganese oxide catalyst, 180 mg of ketjen black as conductive material and 30 mg of PVdF as adhesive.
- the slurry thus produced may be cast on a nickel mesh cut to a diameter of 11.8 pie through a brush to produce a cathode.
- the fabricated cathode is assembled in Swagelok Cel l for lithium-air battery characterization in a glove box maintained in an Ar atmosphere, and 2 pieces of lithium of 12 pi for cathode and 12.8 pi of Whatman's Glass filter ter 1 for separator
- One sheet of 12 sheets of carbon paper may be used as the sheet or gas diffusion layer.
- the lithium-air battery cell manufactured as described above is connected to a frame made to diffuse oxygen through the upper opening, and the electrochemical characteristics can be evaluated.
- a cathode for a lithium-air battery without a catalyst can be produced.
- a cathode for an air cell using a ruthenium oxide-manganese oxide catalyst having a core fiber-shell shell-like nanotube structure or a double-walled common double-leube structure can be fabricated, and the electrochemical characteristics thereof can be evaluated.
- Example 1 The lithium-air battery produced through Example 1, Example 2, and Comparative Example 1 evaluated the electrochemical characteristics through the discharge and the whole layer process, and maintained the scanning speed at 400 mA / g.
- FIG. 7 is a graph showing initial charge and discharge curves according to an embodiment of the present invention.
- FIG. 7 a graph showing initial charge and discharge curves of a lithium-air battery cathode using the catalyst of Example 3 and a lithium-air battery cathode not including the catalyst of Comparative Example 1, wherein the initial charge and discharge curves are 5,.
- the comparison is made with a limit of 000 mAh / g, and the catalyst-free electrode (Fig. 7 (3)) has a discharge capacity of about 3,000 mAh / g and a layer capacity of about 500 mAh / g, and a very high 0RR. (Discharge process) and 0ER (layer discharge process) overvoltage, while the core fiber-shell shell-shaped nanotubes (FIG. 7 (1)) and the double-walled common double tube (FIG.
- FIG. 8 is a graph showing the life characteristics according to an embodiment of the present invention. Referring to FIG. 8, the life characteristics of the lithium-air battery cathode using the catalyst of Example 3 and the lithium-air battery cathode not including the catalyst of Comparative Example 1 may be shown.
- the life characteristics were evaluated by maintaining the capacity limit of 1,000 mAh / g.
- the electrode without a catalyst (Fig. 8 (3)) was confirmed that the capacity decrease occurs rapidly over 20 cycles, whereas the core fiber-shell shell-shaped nanotubes (Fig. 8) produced through Examples 1 and 2 (1)) and the double-walled common double tube (FIG. 8 (2)) showed significantly improved lifespan characteristics over 100 cycles.
- FIG. 9 is a graph showing the time-dependent voltage change of the lithium-air battery cathode according to an embodiment of the present invention.
- FIG. 9 a graph showing a time-varying voltage curve of a lithium-air battery cathode using the catalyst of Example 3 and a lithium-air battery cathode not including the catalyst of Comparative Example 1.
- the present invention provides a catalyst for a lithium-air battery comprising a ruthenium oxide-manganese oxide composite tube structure having a core fiber-shell shell-shaped nanotube structure or a double-walled common double tube structure. It is about.
- the method for preparing a ruthenium oxide-manganese oxide having a core fiber-shell shell-shaped nanotube structure or a double-walled common double tube structure is characterized in that ruthenium chloride and manganese acetate are combined with polyvinylpyridine (PVP).
- PVP polyvinylpyridine
- Dimethylformamide (DMF) and distilled water (DI-water) can be dissolved in a mixed solvent, electrospun through a single nozzle under high voltage to obtain nanofibers, and the composite nanofibers can be heat-treated at different temperatures. have.
- heterogeneous solvents induce phase separation between the polymer and the metal precursor by different boiling points, thereby promoting the leucine structure, and ruthenium oxide and manganese oxide have different crystallization at low temperature (1 ° C / min). Sufficient phase separation occurs depending on the temperature to form a core fiber-shell 3 ⁇ 4 quality nanotube structure in which the core fiber is ruthenium oxide and the shell shell is manganese oxide. On the other hand, at high temperature rates (5 ° C / min), ruthenium oxide and manganese oxide do not provide sufficient time for phase separation to occur, so ruthenium oxide and manganese oxide are uniformly distributed in the inner and outer tubes. To form a double walled common double tube structure. Core-shell-shaped nanotube structures or double-walled cores fabricated by the manufacturing method Excellent performance can be realized by using a ruthenium oxide-manganese oxide having a double tube structure as a cathode catalyst for lithium-air batteries.
Abstract
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JP2017507783A JP6421236B2 (ja) | 2015-07-06 | 2016-07-04 | ルテニウム酸化物とマンガン酸化物の複合体で構成された1次元の多結晶チューブ構造を有するリチウム−空気電池用触媒およびその製造方法 |
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