WO2015115592A1 - 金属空気二次電池用空気極用触媒及び空気極 - Google Patents
金属空気二次電池用空気極用触媒及び空気極 Download PDFInfo
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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
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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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
- 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
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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
- 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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- 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
- H01M4/42—Alloys based on zinc
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
- the present invention relates to a catalyst for an air electrode for a metal-air secondary battery and an air electrode.
- the present invention further relates to a metal-air secondary battery using the air electrode.
- metal-air secondary batteries are expected as a new high-capacity storage battery to replace the currently mainstream lithium ion secondary batteries, and research and development are being promoted with the aim of spreading around 2030.
- OER highly active oxygen generation reaction
- Perovskite-type transition metal oxide ABO 3 has been reported as a non-noble metal OER catalyst containing no precious metal.
- Perovskite oxides have a transition metal at the B site and consist of an octahedral structure combined with six oxygen atoms.
- e g electron number of the B site transition metal is associated with its OER activity, e g the number of electrons 1 near La 0.5 Ca 0.5 CoO 3- ⁇ such a high activity (1.5 mA / cm 2 @ 1.6 V vs RHE, in 0.1 mol dm -3 NaOH aqueous solution) [Non-Patent Document 2].
- Non-Patent Document 1 Y. Lee, et al., J. Phys. Chem. Lett. 2012, 3, 399.
- Non-Patent Document 2 Suntivich, et al., Science 2011, 334, 1383. The entire description of Non-Patent Documents 1 and 2 is hereby specifically incorporated by reference.
- an object of the present invention is to develop a new transition metal oxide catalyst comparable to a noble metal catalyst, and to provide an air electrode and an air secondary battery using the catalyst.
- the non-noble metal OER catalyst is expected as a new energy material in the future, but the perovskite type oxides reported at present are still not sufficient in OER activity.
- the present invention by using a brown mirror light type transition metal oxide A 2 B 2 O 5 that has not been attracting attention as an oxygen generation catalyst until now, it exhibits an activity comparable to that of a Pt catalyst for the OER reaction.
- the present invention was completed by finding out that it exhibits an activity superior to that of a noble metal catalyst by using one containing a transition metal.
- a catalyst for an air electrode containing a brown mirror light type transition metal oxide [2] The catalyst for an air electrode according to [1], wherein the brown mirror light type transition metal oxide is represented by the following general formula (1).
- A represents Ca, Sr, Ba or rare earth element (RE)
- B 1 is a metal atom that takes a tetrahedral structure with an oxygen atom.
- B 2 is a metal atom having an octahedral structure with an oxygen atom.
- B 1 represents a 3d transition element, Al, Ga or In
- B 2 represents a 3d transition element
- the 3d transition element of B 1 is at least one metal atom selected from the group consisting of Fe, Co, Ni, and Zn
- the brown mirror light type transition metal oxide is Ca 2 Fe 2 O 5 , Ca 2 FeCoO 5 , Ca 2 FeMnO 5 , Ca 2 AlFeO 5 , Sr 2 Fe 2 O 5 , Sr 2 Co 2 O 5 or Ba 2 In.
- the catalyst for an air electrode according to [1] or [2], which is 2-x Mn x O 5 + x (x 0 to 0.7).
- An air electrode for a metal-air secondary battery comprising the catalyst according to any one of [1] to [6].
- a metal-air secondary battery comprising the air electrode according to [8] or [9], a negative electrode containing a negative electrode active material, and an electrolyte interposed between the air electrode and the negative electrode.
- the metal-air secondary battery according to [10] further including an oxygen reduction air electrode including an oxygen reduction catalyst.
- an air electrode for a metal-air secondary battery using the air electrode catalyst and a metal-air secondary battery using the air electrode can also be provided.
- the electrochemical measurement results (electrolytic solution: 0.1 mol / dm -3 KOH aq.) Are shown.
- the electrochemical measurement results (electrolyte: 4.0 mol / dm -3 KOH aq.) Are shown.
- the structural example of the metal air secondary battery of this invention is shown.
- Example 1 The sample obtained by the solid phase reaction method (Example 1) and the liquid phase reaction method (Example 2) and the X-ray diffraction pattern of Ca 2 FeCoO 5 obtained by simulation are shown.
- Solid phase reaction method (Example 1) shows a scanning electron micrograph of the Ca 2 FeCoO 5 obtained by the liquid-phase reaction method (Example 2).
- Solid phase reaction method (Example 1) shows the results of electrochemical measurements when using Ca 2 FeCoO 5 obtained by a liquid-phase reaction method (Example 2).
- the present invention relates to an air electrode catalyst containing a brown mirror light type transition metal oxide.
- the brown mirror light type transition metal oxide A 2 B 2 O 5 has a transition metal at the B site, and an octahedral structure bonded to 6 oxygen atoms and a tetrahedral structure bonded to 4 oxygen atoms as shown below. Consists of.
- the brown mirror light type transition metal oxide can be represented by the following general formula (1).
- A represents Ca, Sr, Ba or a rare earth element (RE).
- Rare earth element (RE) is Sc and Y 2 elements and lanthanoid 15 elements, lanthanoid is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.
- the rare earth element (RE) is preferably exemplified by La, Pr, Nd, Sm, Eu, Gd and the like having a relatively large ionic radius.
- B 1 is a metal atom having a tetrahedral structure with an oxygen atom, and more specifically, B 1 represents a 3d transition element, Al, Ga, or In.
- the 3d transition element represented by B 1 is, for example, at least one metal atom selected from the group consisting of Fe, Co, Ni, and Zn.
- B 2 is a metal atom having an octahedral structure with an oxygen atom, and more specifically, B 2 represents a 3d transition element.
- the transition metal represented by B 2 is, for example, at least one metal atom selected from the group consisting of Fe, Co, Mn, Cr, Ni, Ti, and Cu.
- B 1 and B 2 may be atoms of the same element, but may also be composed of atoms of different elements, and depending on the combination of different elements, there may be a case where a better catalytic activity for the air electrode is exhibited.
- the brown mirror light type transition metal oxide can be synthesized by using a liquid phase reaction method in addition to a solid phase reaction method.
- a salt of each metal for example, nitrate, acetate, citrate, or the like is used as a raw material for each metal oxide.
- Ca salt for example, Ca (NO 3 ) 2
- Fe salt for example, Fe (NO 3 ) 3
- Co salt for example, Co (NO 3 )
- a gelling agent for example, water (distilled water or ion-exchanged water) or the like
- citric acid for example, water (distilled water or ion-exchanged water) or the like
- the ratio of each metal salt is appropriately determined in consideration of the composition of the target metal oxide.
- the amount of citric acid used as the gelling agent can be, for example, in the range of 10 to 1000 parts by mass with respect to 100 parts by mass of the metal salt.
- EDTA ethylenediaminetetraacetic acid
- glycine glycine
- the mixture is gelled by heating the mixture to, for example, 50 to 90 ° C. to remove the solvent.
- This gelled product is calcined, for example, in air at 300 to 500 ° C. (eg, 450 ° C.) for 10 minutes to 6 hours (eg, 1 hour) to synthesize a precursor.
- the precursor is calcined at 600 to 800 ° C. for 1 to 24 hours, for example, in the atmosphere, thereby synthesizing a target brown mirror light type Ca 2 FeCoO 5 .
- the firing conditions for example, after firing at 600 ° C. for a predetermined time (1 to 12 hours), the temperature is raised and, for example, firing can be performed at 800 ° C. for a predetermined time (6 to 12 hours).
- the liquid phase reaction method can synthesize the target brown mirror light transition metal oxide at a lower temperature than the solid phase reaction method, and the resulting oxide has a smaller particle size due to the lower firing temperature. Obtained as particles. Since the small particle size has a large surface area, it can be expected to have a high activity per unit mass when used as a catalyst.
- the air electrode catalyst containing the brown mirror light type transition metal oxide of the present invention can have a surface area in the range of, for example, 0.1 to 100 m 2 / g, and preferably in the range of 1 to 100 m 2 / g. . However, it is not intended to be limited to this range.
- the air electrode catalyst containing the brown mirror light type transition metal oxide of the present invention has a particle size of, for example, 100 ⁇ m or less, and the catalyst obtained by the solid phase reaction method has a particle size of, for example, 1 to 50 ⁇ m,
- the particle diameter of the catalyst obtained by the liquid phase reaction method is, for example, 10 to 1000 nm, preferably 20 to 500 nm. However, these particle diameters are merely examples.
- the brown mirror light type transition metal oxide of the present invention is extremely useful for an air electrode, hydrogen production by photohydrolysis, and air of a metal-air secondary battery that is expected as a next-generation high-capacity secondary battery. Very promising as a pole. It should be noted that the OER activity is remarkably improved by using Ca 2 FeCoO 5 containing Fe and Co as compared with Ca 2 Fe 2 O 5 containing only Fe as the B site metal. From this, it is highly possible that the excellent OER catalytic properties of Ca 2 FeCoO 5 are expressed by the synergistic effect of two kinds of transition metals (Co, Fe), and B 1 and B 2 in formula (1) are A combination of different elements is preferable because it may show more excellent catalytic activity for the air electrode.
- the air electrode usually has a porous structure and contains a conductive material in addition to the oxygen reaction catalyst.
- the air electrode may contain an oxygen reduction (ORR) catalyst, a binder, and the like as necessary.
- ORR oxygen reduction
- the air electrode in the secondary battery must have OER catalytic activity as a function during charging and ORR catalytic activity as a function during discharging. Since the catalyst of the present invention is an OER catalyst, the air electrode may contain an ORR catalyst in addition to this catalyst.
- ORR oxygen reduction
- the content of the catalyst of the present invention (OER catalyst) in the air electrode is not particularly limited, but is preferably 1 to 90% by mass, particularly 10 to 60% by mass from the viewpoint of improving the oxygen reaction performance of the air electrode. %, And more preferably 30 to 50% by mass.
- ORR catalyst examples include, but are not particularly limited to, for example, Pt or Pt-based materials (for example, PtCo, PtCoCr, Pt-W 2 C, Pt-RuOx, etc.), Pd-based materials (for example, PdTi, PdCr, PdCo) , PdCoAu, etc.), metal oxides (e.g., ZrO 2-x , TiO x , TaN x O y , IrMO x, etc.), complex systems (Co-porphyrin complexes), others (PtMoRuSeO x , RuSe etc.) it can. Furthermore, LaNiO 3 (Nat. Chem.
- a plurality of catalysts may be used in combination in consideration of the performance and properties of each catalyst.
- a cocatalyst for example, TiO x , RuO 2 , SnO 2, etc.
- the content when the ORR catalyst is used in combination can be appropriately determined in consideration of the type of the ORR catalyst, the catalytic activity, and the like, and can be, for example, 1 to 90% by mass. However, it is not intended to be limited to this numerical range.
- the conductive material is not particularly limited as long as it is generally usable as a conductive auxiliary agent.
- Preferred examples include conductive carbon.
- Specific examples include mesoporous carbon, graphite, acetylene black, carbon nanotube, and carbon fiber.
- Conductive carbon having a large specific surface area is preferable because it provides many reaction fields at the air electrode.
- conductive carbon having a specific surface area of 1 to 3000 m 2 / g, particularly 500 to 1500 m 2 / g is preferable.
- the catalyst for the air electrode may be supported on a conductive material.
- the content of the conductive material in the air electrode is not particularly limited, but is preferably, for example, 10 to 99% by mass, particularly preferably 20 to 80% by mass, from the viewpoint of increasing the discharge capacity. More preferably, it is 50 mass%.
- the binder is not particularly limited, and examples thereof include polyvinylidene fluoride (PVDF) and a copolymer thereof, polytetrafluoroethylene (PTFE) and a copolymer thereof, and styrene butadiene rubber (SBR).
- PVDF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- SBR styrene butadiene rubber
- the binder content in the air electrode is not particularly limited, but is preferably 1 to 40% by mass, particularly 5 to 35% by mass from the viewpoint of the binding force between carbon (conductive material) and the catalyst. It is preferably 10 to 35% by mass.
- the air electrode can be formed, for example, by applying and drying a slurry prepared by dispersing the above-described air electrode constituent material in a suitable solvent on a substrate.
- the solvent is not particularly limited, and examples thereof include acetone, N, N-dimethylformamide, N-methyl-2-pyrrolidone (NMP) and the like. Mixing of the air electrode constituent material and the solvent is usually performed for 3 hours or longer, preferably 4 hours.
- the mixing method is not particularly limited, and a general method can be adopted.
- the substrate on which the slurry is applied is not particularly limited, and examples thereof include a glass plate and a Teflon (registered trademark) plate. These substrates are peeled from the obtained air electrode after the slurry is dried. Alternatively, the current collector of the air electrode and the solid electrolyte layer can be handled as the base material. In this case, the substrate is used as it is as a constituent member of the metal-air secondary battery without peeling off.
- the slurry application method and the drying method are not particularly limited, and general methods can be employed.
- a coating method such as a spray method, a doctor blade method, or a gravure printing method, or a drying method such as heat drying or reduced pressure drying can be employed.
- the thickness of the air electrode is not particularly limited and may be appropriately set according to the use of the metal-air secondary battery, etc., but is usually preferably 5 to 100 ⁇ m, 10 to 60 ⁇ m, and particularly preferably 20 to 50 ⁇ m.
- the air electrode is normally connected to an air electrode current collector that collects the air electrode.
- the material and shape of the air electrode current collector are not particularly limited. Examples of the material for the air electrode current collector include stainless steel, aluminum, iron, nickel, titanium, and carbon (carbon). Examples of the shape of the air electrode current collector include a foil shape, a plate shape, a mesh (grid shape), and a fiber shape. Among them, a porous shape such as a mesh shape is preferable. This is because the porous current collector is excellent in the efficiency of supplying oxygen to the air electrode.
- the metal-air secondary battery of the present invention includes an air electrode containing a catalyst containing the above-described brown mirror light type transition metal oxide, a negative electrode containing a negative electrode active material, and an electrolyte interposed between the air electrode and the negative electrode. And having.
- the air electrode of the metal-air secondary battery of the present invention contains a catalyst containing a brown mirror light type transition metal oxide, and this catalyst exhibits excellent OER catalytic properties. Therefore, by using the air electrode using this catalyst, the metal-air secondary battery of the present invention is excellent in charging speed and charging voltage.
- the air electrode can coexist with a catalyst having ORR catalytic activity as described above.
- an oxygen reduction (ORR) air electrode containing a catalyst having ORR catalytic activity may be provided separately from an oxygen generation (OER) air electrode containing a catalyst containing a brown mirror light type transition metal oxide.
- OER oxygen generation
- the metal-air secondary battery has an oxygen electrode for oxygen reduction and an air electrode for oxygen generation (three-electrode system).
- An air electrode for oxygen reduction is used during discharging, and an air electrode for generating oxygen is used during charging.
- the catalyst having the ORR catalytic activity is as described above, and an air electrode for oxygen generation can be obtained by using this catalyst and the conductive material and binder described in the description of the air electrode.
- FIG. 7 is a cross-sectional view showing an embodiment of the metal-air secondary battery of the present invention.
- a metal-air secondary battery 1 includes an air electrode 2 that uses oxygen as an active material, a negative electrode 3 that contains a negative electrode active material, an electrolyte 4 that conducts ion conduction between the air electrode 2 and the negative electrode 3, and current collection of the air electrode 2.
- An air electrode current collector 5 to be performed and a negative electrode current collector 6 to collect current of the negative electrode 3 are accommodated in a battery case (not shown).
- the air electrode 2 is electrically connected to an air electrode current collector 5 that collects the air electrode 2, and the air electrode current collector 5 has a porous structure capable of supplying oxygen to the air electrode 2.
- the negative electrode 3 is electrically connected to a negative electrode current collector 6 that collects current from the negative electrode 3, and one of the end portions of the air electrode current collector 5 and the negative electrode current collector 6 protrudes from the battery case. Yes.
- the negative electrode contains a negative electrode active material.
- a negative electrode active material the negative electrode active material of a general air battery can be used, and it is not specifically limited.
- the negative electrode active material is usually capable of occluding and releasing metal ions.
- Specific examples of the negative electrode active material include metals such as Li, Na, K, Mg, Ca, Zn, Al, and Fe, alloys of these metals, oxides and nitrides, and carbon materials.
- zinc-air secondary batteries are excellent in safety and are expected as next-generation secondary batteries. From the viewpoint of high voltage and high output, lithium-air secondary batteries and magnesium air secondary batteries are promising. An example of a zinc-air secondary battery will be described below.
- the reaction formula is as follows.
- a material capable of inserting and extracting zinc ions is used as the negative electrode.
- a zinc alloy can also be used in addition to zinc metal.
- the zinc alloy include a zinc alloy containing one or more elements selected from aluminum, indium, magnesium, tin, titanium, and copper.
- Examples of the negative electrode active material of the lithium-air secondary battery include metal lithium; lithium alloys such as lithium aluminum alloy, lithium tin alloy, lithium lead alloy, and lithium silicon alloy; tin oxide, silicon oxide, lithium titanium oxide, Metal oxides such as niobium oxide and tungsten oxide; metal sulfides such as tin sulfide and titanium sulfide; metal nitrides such as lithium cobalt nitride, lithium iron nitride and lithium manganese nitride; and graphite A carbon material etc. can be mentioned, Among these, metallic lithium is preferable.
- a material capable of occluding and releasing magnesium ions is used as the negative electrode active material of the magnesium-air secondary battery.
- a negative electrode in addition to metallic magnesium, magnesium alloys such as magnesium aluminum, magnesium silicon, and magnesium gallium can be used.
- the foil-like or plate-like negative electrode active material can be used as the negative electrode itself.
- the negative electrode only needs to contain at least the negative electrode active material, but may contain a binder for immobilizing the negative electrode active material, if necessary.
- a binder for immobilizing the negative electrode active material, if necessary.
- the negative electrode is usually connected to a negative electrode current collector that collects the negative electrode current.
- the material and shape of the negative electrode current collector are not particularly limited. Examples of the material for the negative electrode current collector include stainless steel, copper, and nickel. Examples of the shape of the negative electrode current collector include a foil shape, a plate shape, and a mesh (grid shape).
- the electrolyte is disposed between the air electrode and the negative electrode. Metal ion conduction is performed between the negative electrode and the air electrode through the electrolyte.
- the form of the electrolyte is not particularly limited, and examples thereof include a liquid electrolyte, a gel electrolyte, and a solid electrolyte.
- the electrolyte may be an alkaline aqueous solution such as a potassium hydroxide aqueous solution or a sodium hydroxide aqueous solution containing zinc oxide, or zinc chloride or zinc perchlorate may be used.
- a nonaqueous solvent containing zinc perchlorate or a nonaqueous solvent containing zinc bis (trifluoromethylsulfonyl) imide may be used.
- the negative electrode is made of magnesium or an alloy thereof, a non-aqueous solvent containing magnesium perchlorate or magnesium bis (trifluoromethylsulfonyl) imide may be used.
- non-aqueous solvent examples include conventional secondary batteries such as ethylene carbonate (EC), propylene carbonate (PC), ⁇ -butyrolactone ( ⁇ -BL), diethyl carbonate (DEC), and dimethyl carbonate (DMC).
- EC ethylene carbonate
- PC propylene carbonate
- ⁇ -BL ⁇ -butyrolactone
- DEC diethyl carbonate
- DMC dimethyl carbonate
- organic solvents used in capacitors may be used alone or in combination.
- an ionic liquid such as N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethylsulfonyl) imide (am) can be used.
- the electrolytic solution preferably contains a dendrite formation inhibitor.
- the dendrite formation inhibitor is considered to suppress the generation of dendrite by adsorbing to the negative electrode surface during charging to reduce the energy difference between crystal faces and preventing preferential orientation.
- the dendrite formation inhibitor is not particularly limited, and can be, for example, at least one selected from the group consisting of polyalkylenimines, polyallylamines and asymmetric dialkyl sulfones (for example, JP 2009 -93983).
- generation inhibitor is although it does not specifically limit, For example, you may use only the quantity saturated to electrolyte solution at normal temperature normal pressure, and may use it as a solvent.
- the liquid electrolyte having lithium ion conductivity is usually a non-aqueous electrolyte containing a lithium salt and a non-aqueous solvent.
- the lithium salt include inorganic lithium salts such as LiPF 6 , LiBF 4 , LiClO 4, and LiAsF 6 ; and LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , An organic lithium salt such as LiC (CF 3 SO 2 ) 3 can be used.
- non-aqueous solvent examples include ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), butylene carbonate, ⁇ -butyrolactone, sulfolane, acetonitrile, Examples thereof include 1,2-dimethoxymethane, 1,3-dimethoxypropane, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and mixtures thereof.
- An ionic liquid can also be used as the nonaqueous solvent.
- the concentration of the lithium salt in the nonaqueous electrolytic solution is not particularly limited, but is preferably in the range of 0.1 mol / L to 3 mol / L, for example, and preferably 1 mol / L.
- a low-volatile liquid such as an ionic liquid may be used as the nonaqueous electrolytic solution.
- the gel electrolyte having lithium ion conductivity can be obtained, for example, by adding a polymer to the non-aqueous electrolyte and gelling.
- a polymer such as polyethylene oxide (PEO), polyvinylidene fluoride (PVDF, trade name Kynar manufactured by Arkema), polyacrylonitrile (PAN), or polymethyl methacrylate (PMMA) is added to the non-aqueous electrolyte.
- PEO polyethylene oxide
- PVDF polyvinylidene fluoride
- PAN polyacrylonitrile
- PMMA polymethyl methacrylate
- Solid electrolyte which has lithium ion conductivity It does not specifically limit as a solid electrolyte which has lithium ion conductivity,
- the general solid electrolyte which can be used with a lithium metal air secondary battery can be used.
- Li 2 S-P 2 S 5 compound, Li 2 S-SiS 2 compound, Li 2 S-GeS 2 compounds sulfide solid electrolyte can be mentioned.
- the thickness of the electrolyte varies greatly depending on the configuration of the battery, but is preferably in the range of 10 ⁇ m to 5000 ⁇ m, for example.
- a separator is preferably disposed between the air electrode and the negative electrode in order to ensure electrical insulation between these electrodes.
- the separator is not particularly limited as long as electrical insulation between the air electrode and the negative electrode can be ensured and an electrolyte can be interposed between the air electrode and the negative electrode.
- the separator examples include porous films such as polyethylene, polypropylene, cellulose, polyvinylidene fluoride, and glass ceramics; and nonwoven fabrics such as a resin nonwoven fabric and a glass fiber nonwoven fabric. Among them, a glass ceramic separator is preferable.
- a general metal-air secondary battery case can be used as a battery case for storing the metal-air secondary battery.
- the shape of the battery case is not particularly limited as long as it can hold the above-described air electrode, negative electrode, and electrolyte, and specifically includes a coin type, a flat plate type, a cylindrical type, a laminate type, and the like. Can do.
- the metal-air secondary battery of the present invention can be discharged by supplying oxygen as an active material to the air electrode.
- oxygen supply source include air, oxygen gas, and the like, preferably oxygen gas.
- the pressure of the supplied air or oxygen gas is not particularly limited and may be set as appropriate.
- the air electrode catalyst containing the brown mirror light type transition metal oxide of the present invention is useful not only for a metal-air secondary battery but also in a field where other OER electrode catalysts are used.
- OER electrocatalysts have long been studied or used as counter reactions of various electrochemical reactions, and can be diverted to electrolytic techniques such as alkali metal plating and electrolytic degreasing, and to anticorrosion techniques.
- electrolytic techniques such as alkali metal plating and electrolytic degreasing, and to anticorrosion techniques.
- Example 1 Brown mirror light type transition metal oxides Ca 2 Fe 2 O 5 , Ca 2 FeCoO 5 , Ca 2 FeMnO 5 are mixed using CaCO 3 , Fe 2 O 3 , Co 3 O 4 , Mn 2 O 3 as raw materials.
- Ca 2 Fe 2 O 5 and Ca 2 FeCoO 5 were synthesized by firing at 1100 ° C in air for 12 hours, 1200 ° C for 12 hours, and Ca 2 FeMnO 5 by firing at 1100 ° C in an argon stream for 12 hours (solid-phase reaction method).
- phase identification X-ray diffraction, Rigaku Ultima IV Equipped with a high-speed one-dimensional semiconductor detector
- the obtained sample was subjected to phase identification and structural analysis by X-ray diffraction (FIGS. 1 to 3). From the X-ray diffraction pattern obtained by simulation and the previous report [Non-Patent Document 3-6], a single phase of Ca 2 Fe 2 O 5 , Ca 2 FeCoO 5 , and Ca 2 FeMnO 5 has been synthesized by the solid-phase reaction method. (Ca 2 FeMnO 5 was mixed with a small amount of impurities).
- Non-Patent Document 5 F. Ramezanipour et al., J. Solid State Chem. 2009, 182, 153.
- Non-Patent Document 6 F. Ramezanipour et al., J. Am. Chem. Soc. 2012, 134, 3215.
- ketjen black (KB) and dinitrodiamineplatinum (II) nitric acid solution were mixed, reacted for 4 hours at 100 ° C in an oil bath, washed and dried to synthesize a 30 wt% Pt / KB precious metal catalyst. This was also applied to the GC electrode in the same manner as described above.
- Electrochemical measurement> A three-electrode Teflon (registered trademark) electrochemical cell was used for the electrochemical measurement, a platinum plate was used as the counter electrode, and Hg / HgO / 0.1 mol dm -3 KOH aq. was used as the reference electrode. Sweep was performed in a predetermined potential range at a sweep rate of 1 mV / s, and 0.1 mol dm -3 and 4.0 mol dm -3 aqueous KOH solutions were used as the electrolyte.
- Electrochemical measurement was performed by the conventional method under the following conditions.
- WE Ca 2 Fe 2 O 5 or Ca 2 FeCoO 5 or Ca 2 FeMnO 5 / GC CE: Pt RE: Hg / HgO / 0.1 mol dm -3 KOH aq.
- Electrolyte 0.1 or 4.0 mol / dm -3 KOH aq.
- Sweep speed 1 mV / sec
- Example 2 The liquid phase synthesis method of Ca 2 FeCoO 5 , which is a brown mirror light type transition metal oxide, is shown below.
- Ca (NO 3 ) 2 ⁇ 4H 2 O, Fe (NO 3 ) 3 ⁇ 9H 2 O, Co (NO 3 ) 2 ⁇ 6H 2 O, and citric acid (CA) as raw materials
- the obtained aqueous solution was heated to about 70 ° C., the solvent was removed, and gelation was performed. This was calcined in air at 450 ° C. for 1 hour to synthesize a precursor. Next, this precursor was calcined in the atmosphere at 600 ° C. for 6 hours. Further, a sample fired at 800 ° C. for 12 hours was also produced.
- Ca 2 FeCoO 5 obtained in Example Brown mirror light type transition metal oxide Ca 2 FeCoO 5 obtained by a liquid-phase reaction method described above 1 (solid phase reaction method), were soaked overnight at 80oC in nitric acid After washing and drying, acetylene black and Nafion (registered trademark) neutralized with NaOH were mixed at a weight ratio of 5: 1: 1, and an appropriate amount of ethanol was added to prepare a catalyst suspension. This was dropped onto a glassy carbon (GC) electrode so that the brown mirror light type transition metal oxide catalyst was in a ratio of 1.0 mg / cm 2 and dried at room temperature to obtain an OER catalyst.
- GC glassy carbon
- an electrode using commercially available IrO 2 (0.89 m 2 / g) and RuO 2 (8.38 m 2 / g) instead of Ca 2 FeCoO 5 was also evaluated.
- a three-electrode Teflon (registered trademark) electrochemical cell was used for electrochemical measurement, a platinum plate was used as the counter electrode, and Hg / HgO / KOH was used as the reference electrode. Sweep in a specified potential range at a sweep rate of 1 mV / s, and a 4.0 mol dm -3 KOH aqueous solution, which is a high-concentration alkaline electrolyte, is assumed for the electrolyte as an air electrode for metal-air secondary batteries. Using.
- FIG. 8 shows an X-ray diffraction pattern of the solid phase reaction method, a sample obtained by the phase reaction method, and Ca 2 FeCoO 5 obtained by simulation. Even in the sample synthesized by this example (liquid phase reaction method), a peak attributed to Ca 2 FeCoO 5 was confirmed, indicating that the compound was synthesized in a single phase.
- FIG. 9 shows a scanning electron microscope image of Ca 2 FeCoO 5 obtained by the solid phase reaction method and the liquid phase reaction method.
- the particle size obtained by the solid phase reaction method (Example 1) is 10 to 5 ⁇ m, whereas the particle size obtained by the liquid phase reaction method (Example 2) is 200 to 400 at 800 ° C.
- the particle size was about 50 to 20 nm at 600 ° C.
- the one synthesized by the solid phase reaction method is 0.13 m 2 / g
- the one synthesized by the liquid phase reaction method is 800 ° C. at 3.85 m 2 / g and 600 ° C. 18.9 m 2 / g and high surface area more than 100 times.
- FIG. 10 shows the results of electrochemical measurement using Ca 2 FeCoO 5 obtained by the solid phase reaction method and the liquid phase reaction method.
- the measurement results of IrO 2 and RuO 2 which are currently said to have the highest OER activity in the most precious metal oxide catalysts, are also shown.
- the current derived from OER was observed from around 1.48 V vs RHE, which is about 6 mA / cm 2 at 1.6 V vs RHE. .
- the liquid phase reaction method Example 2
- a current derived from OER was observed from around 1.42 V vs RHE at 800 ° C. and 600 ° C., and 800 ° C. at 1.6 V vs RHE.
- the current was about 100 mA / cm 2 at about 140 mA / cm 2 at 600 ° C., which was 20 times higher than that of the Ca 2 FeCoO 5 obtained by the solid phase reaction method. It can be seen that the activation is increased by increasing the surface area.
- the present invention is useful in the field of secondary batteries, metal-air secondary batteries that are expected as next-generation high-capacity secondary batteries, and hydrogen production by light water splitting.
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Abstract
Description
[関連出願の相互参照]
本出願は、2014年1月31日出願の日本特願2014-17891号の優先権を主張し、その全記載は、ここに特に開示として援用される。
非特許文献2: Suntivich, et al., Science 2011, 334, 1383.
非特許文献1及び2の全記載は、ここに特に開示として援用される。
[1]
ブラウンミラーライト型遷移金属酸化物を含む空気極用触媒。
[2]
前記ブラウンミラーライト型遷移金属酸化物が下記一般式(1)で示される[1]に記載の空気極用触媒。
A2B1B2O5 (1)
式中、Aは、Ca、Sr、Ba又は希土類元素(RE)を表し、
B1は、酸素原子と四面体構造を取る金属原子であり
B2は、酸素原子と八面体構造を取る金属原子である。
[3]
B1は、3d遷移元素、Al、Ga又はInを表し、
B2は、3d遷移元素を表し、
B1及びB2は異なる元素からなる[2]に記載の空気極用触媒。
[4]
B1の3d遷移元素は、Fe、Co、Ni及びZnから成る群から選ばれる少なくとも1種の金属原子であり、
B2の遷移金属は、Fe、Co、Mn、Cr、Ni、Ti及びCuから成る群から選ばれる少なくとも1種の金属原子である[3]に記載の空気極用触媒。
[5]
前記ブラウンミラーライト型遷移金属酸化物が、Ca2Fe2O5、Ca2FeCoO5、Ca2FeMnO5、Ca2AlFeO5、Sr2Fe2O5、Sr2Co2O5又はBa2In2-xMnxO5+x(x=0~0.7)である[1]又は[2]に記載の空気極用触媒。
[6]
表面積が0.1~100m2/gの範囲である[1]~[5]のいずれかに記載の空気極用触媒。
[7]
[1]~[6]のいずれかに記載のブラウンミラーライト型遷移金属酸化物の空気極用触媒としての使用。
[8]
[1]~[6]のいずれかに記載の触媒を含む金属空気二次電池用空気極。
[9]
前記ブラウンミラーライト型遷移金属酸化物は酸素発生用触媒として含有され、酸素還元用触媒をさらに含む[8]に記載の空気極。
[10][8]又は[9]に記載の空気極と、負極活物質を含有する負極と、前記空気極と前記負極との間に介在する電解質と、を有する金属空気二次電池。
[11]
酸素還元用触媒を含む酸素還元用空気極をさらに含む[10]に記載の金属空気二次電池。
本発明は、ブラウンミラーライト型遷移金属酸化物を含む空気極用触媒に関する。
A2B1B2O5 (1)
Ca2AlFeO5、Sr2Fe2O5、Sr2Co2O5及びBa2In2-xMnxO5+x(x=0~0.7)についての合成方法は、以下の文献を参照できる。
Ca2AlFeO5: M. Zoetzl et al.,J. Am. Ceram. Soc.89, 3491 (2006).
Sr2Fe2O5: A. Nemudry et al.,Chem. Mater.10, 2403 (1998).
Sr2Co2O5: A. Nemudry et al.,Chem. Mater.8, 2232 (1996).
Ba2In2-xMnxO5+x: P. Jiang et al., Inorg. Chem.52, 1349 (2013).
空気極は、通常、多孔質構造を有し、酸素反応触媒の他、導電性材料を含む。また、空気極は、必要に応じて、酸素還元(ORR)触媒、バインダー等を含んでいてもよい。二次電池における空気極には、充電時の機能としてOER触媒活性と、放電時の機能としてORR触媒活性を有することを要する。本発明の触媒はOER触媒であるので、空気極には、この触媒に加えて、ORR触媒を含有させることもできる。空気極における充電及び放電時の化学式を以下に示す。
池のサイクル特性を向上させることができる。バインダーとしては特に限定されず、例えば、ポリフッ化ビニリデン(PVDF)及びその共重合体、ポリテトラフルオロエチレン(PTFE)及びその共重合体、スチレンブタジエンゴム(SBR)等が挙げられる。空気極におけるバインダーの含有量は、特に限定されないが、カーボン(導電性材料)と触媒との結着力の観点から、例えば、1~40質量%であることが好ましく、特に5~35質量%であることが好ましく、10~35質量%であることがより好ましい。
本発明の金属空気二次電池は、上記したブラウンミラーライト型遷移金属酸化物を含む触媒を含有する空気極と、負極活物質を含有する負極と、空気極と負極との間に介在する電解質と、を有する。本発明の金属空気二次電池の空気極には、ブラウンミラーライト型遷移金属酸化物を含む触媒が含有され、この触媒は優れたOER触媒特性を示す。従って、この触媒を用いた空気極を用いることで、本発明の金属空気二次電池は、充電速度及び充電電圧に優れたものとなる。
負極は、負極活物質を含有する。負極活物質としては、一般的な空気電池の負極活物質を用いることができ、特に限定されるものではない。負極活物質は、通常、金属イオンを吸蔵・放出することができるものである。具体的な負極活物質としては、例えば、Li、Na、K、Mg、Ca、Zn、Al、及びFe等の金属、これら金属の合金、酸化物及び窒化物、並びに炭素材料等が挙げられる。
亜鉛-空気二次電池の例を以下に説明すると、反応式は以下の通りである。
電解質は、空気極と負極との間に配置される。電解質を介して、負極と空気極との間の金属イオン伝導が行われる。電解質の形態は、特に限定されるものではなく、液体電解質、ゲル電解質、固体電解質等を挙げることができる。
本発明の金属空気二次電池において、空気極と負極との間には、これら電極間の電気的絶縁を確実に行うために、セパレータが配置されることが好ましい。セパレータは、空気極と負極との間の電気的絶縁が確保可能であると共に、空気極と負極との間に電解質が介在することが可能な構造を有していれば特に限定されない。
<合成方法>
ブラウンミラーライト型遷移金属酸化物Ca2Fe2O5、Ca2FeCoO5、Ca2FeMnO5は、原料としてCaCO3、Fe2O3、Co3O4、Mn2O3を用いて混合し、Ca2Fe2O5、Ca2FeCoO5は空気中1100oCで12時間、1200oCで12時間、Ca2FeMnO5はアルゴン気流中1100oCで12時間焼成することにより合成した(固相反応法)。
相同定:
X 線回折, Rigaku Ultima IV
高速1次元半導体検出器を装備
Pcmn
a = 0.5595 nm
b = 1.4827 nm
c = 0.5407 nm
[非特許文献3] P. Berastegui et al., Mater. Res. Bull. 1999, 34, 303.
Pbcm
a = 0.5365 nm
b = 1.1100 nm
c = 1.4798 nm
[非特許文献4] F. Ramezanipour et al., Chem. Mater. 2010, 22, 6008.
Pnma
x = 0.96:
a = 0.53055 nm
b = 1.5322 nm
c = 0.54587 nm
x = 0.67:
a = 0.53385 nm
b = 1.5154 nm
c = 0.55009 nm
[非特許文献5] F. Ramezanipour et al., J. Solid State Chem. 2009, 182, 153.
[非特許文献6] F. Ramezanipour et al., J. Am. Chem. Soc. 2012, 134, 3215.
得られたCa2Fe2O5、Ca2FeCoO5、又はCa2FeMnO5 50 mgと、硝酸に80℃で一晩浸漬した後に洗浄乾燥したアセチレンブラック、及びNaOHで中和したNafion(R)を重量比5:1:1で混合し、適量のエタノールを加えて触媒懸濁液を調製した。これをブラウンミラーライト型遷移金属酸化物触媒が1.0 mg/cm2の割合になるようにグラッシーカーボン(GC)電極(直径5mm)上に4回に分けて滴下し、室温乾燥することでOER触媒とした(図4参照)。また比較用としてケッチェンブラック(KB)とジニトロジアミン白金(II)硝酸溶液を混合し、オイルバス100℃で4時間反応後、洗浄乾燥することで30 wt% Pt/KB貴金属触媒を合成した。これも上記と同様の方法でGC電極に塗布した。
電気化学測定には三電極式のテフロン(登録商標)製電気化学セルを用い、対極には白金板、参照極にはHg/HgO/0.1 mol dm-3 KOH aq.を用いた。掃引速度1 mV/sで所定の電位範囲で掃引し、電解液には0.1 mol dm-3およびの4.0 mol dm-3のKOH水溶液を用いた。
WE : Ca2Fe2O5 又は Ca2FeCoO5又は Ca2FeMnO5/GC
CE : Pt
RE : Hg/HgO/0.1 mol dm-3 KOH aq.
電解液 : 0.1 又は 4.0 mol/dm-3 KOH aq.
掃引範囲: -0.8 ~ 0.66 V vs. Hg/HgO/0.1 mol dm-3 KOH aq.
掃引速度: 1 mV / sec
ブラウンミラーライト型遷移金属酸化物であるCa2FeCoO5の液相合成法を以下に示す。原料として、Ca(NO3)2・4H2O、Fe(NO3)3・9H2O、Co(NO3)2・6H2O、クエン酸 (CA)を用いてCa:Fe:Co:CA=2:1:1:4の比率で混合し、得られた混合物16gと100gの水とを混合して水溶液を得た。得られた水溶液を約70℃に加熱、溶媒の除去、及びゲル化を行った。これを空気中、450℃で1時間仮焼成し、前駆体を合成した。次にこの前駆体を大気中、600℃で6時間焼成した。また、さらに800℃で12時間焼成した試料も作製した。
Claims (11)
- ブラウンミラーライト型遷移金属酸化物を含む空気極用触媒。
- 前記ブラウンミラーライト型遷移金属酸化物が下記一般式(1)で示される請求項1に記載の空気極用触媒。
A2B1B2O5 (1)
式中、Aは、Ca、Sr、Ba又は希土類元素(RE)を表し、
B1は、酸素原子と四面体構造を取る金属原子であり
B2は、酸素原子と八面体構造を取る金属原子である。 - B1は、3d遷移元素、Al、Ga又はInを表し、
B2は、3d遷移元素を表し、
B1及びB2は異なる元素からなる請求項2に記載の空気極用触媒。 - B1の3d遷移元素は、Fe、Co、Ni及びZnから成る群から選ばれる少なくとも1種の金属原子であり、
B2の遷移金属は、Fe、Co、Mn、Cr、Ni、Ti及びCuから成る群から選ばれる少なくとも1種の金属原子である請求項3に記載の空気極用触媒。 - 前記ブラウンミラーライト型遷移金属酸化物が、Ca2Fe2O5、Ca2FeCoO5、Ca2FeMnO5、Ca2AlFeO5、Sr2Fe2O5、Sr2Co2O5又はBa2In2-xMnxO5+x(x=0~0.7)である請求項1又は2に記載の空気極用触媒。
- 表面積が0.1~100m2/gの範囲である請求項1~5のいずれかに記載の空気極用触媒。
- 請求項1~6のいずれかに記載のブラウンミラーライト型遷移金属酸化物の空気極用触媒としての使用。
- 請求項1~6のいずれかに記載の触媒を含む金属空気二次電池用空気極。
- 前記ブラウンミラーライト型遷移金属酸化物は酸素発生用触媒として含有され、酸素還元用触媒をさらに含む請求項8に記載の空気極。
- 請求項8又は9に記載の空気極と、負極活物質を含有する負極と、前記空気極と前記負極との間に介在する電解質と、を有する金属空気二次電池。
- 酸素還元用触媒を含む酸素還元用空気極をさらに含む請求項10に記載の金属空気二次電池。
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WO2019093441A1 (ja) * | 2017-11-10 | 2019-05-16 | 国立大学法人北海道大学 | 非晶質遷移金属酸化物及びその利用 |
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JP2018070396A (ja) * | 2016-10-26 | 2018-05-10 | Jfeスチール株式会社 | ブラウンミラーライト型酸化物の製造方法 |
WO2019093441A1 (ja) * | 2017-11-10 | 2019-05-16 | 国立大学法人北海道大学 | 非晶質遷移金属酸化物及びその利用 |
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US20160344037A1 (en) | 2016-11-24 |
EP3101718A1 (en) | 2016-12-07 |
US10693145B2 (en) | 2020-06-23 |
EP3101718A4 (en) | 2017-07-26 |
JP6436444B2 (ja) | 2018-12-12 |
JPWO2015115592A1 (ja) | 2017-03-23 |
EP3101718B1 (en) | 2018-11-28 |
ES2710074T3 (es) | 2019-04-22 |
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