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WO2019093441A1 - Oxyde de métal de transition amorphe et son utilisation - Google Patents

Oxyde de métal de transition amorphe et son utilisation Download PDF

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WO2019093441A1
WO2019093441A1 PCT/JP2018/041555 JP2018041555W WO2019093441A1 WO 2019093441 A1 WO2019093441 A1 WO 2019093441A1 JP 2018041555 W JP2018041555 W JP 2018041555W WO 2019093441 A1 WO2019093441 A1 WO 2019093441A1
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metal oxide
transition metal
catalyst
range
oxygen
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PCT/JP2018/041555
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English (en)
Japanese (ja)
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芳尚 青木
浩樹 幅▲ざき▼
ダミアン コヴァルスキー
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国立大学法人北海道大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • 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
    • 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
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates to amorphous transition metal oxides and their use. Further, the present invention relates to a catalyst for an air electrode using an amorphous transition metal oxide and a catalyst for a water electrolysis anode. In addition, the present invention relates to a metal air secondary battery using the catalyst for the air electrode.
  • a perovskite type transition metal oxide ABO 3 has been reported as a non-precious metal OER catalyst containing no precious metal.
  • the perovskite oxide has a transition metal at the B site and is composed of an octahedral structure bonded to six oxygens.
  • 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 as a high activity (1.5 It is reported that mA / cm 2 @ 1.6 V vs RHE, 0.1 mol dm ⁇ 3 in a NaOH aqueous solution) [Non-patent document 2].
  • the material which has a CoOOH nanosheet structure is reported as an example of the OER catalyst which has a novel structure (nonpatent literature 3).
  • This material was prepared by layer peeling by sonicating an ⁇ -Co (OH) 2 sheet in the presence of Cl anion and water, followed by oxidation using NaClO, as shown in FIG.
  • the TEM image of and the AFFM image of 1c it has a particle size of 200-300 nm.
  • the result of XRD in FIG. 1 d it has crystallinity.
  • Patent Document 1 WO 2015/115592
  • Non-Patent Document 1 Y. Lee, et al., J. Phys. Chem. Lett. 2012, 3, 399.
  • Non-patent document 2 Suntivich Science 2011, 334, 1383.
  • Non-Patent Document 3 J. Huang, et al., Angewandte_Chemie_International_Edition 2015, 54, 8722-8727 The entire descriptions of Patent Document 1 and Non-Patent Documents 1 to 3 are specifically incorporated herein by reference.
  • the brown mirror light type transition metal oxide A 2 B 2 O 5 containing two types of transition metals described in Patent Document 1 exhibits OER activity superior to that of a noble metal catalyst.
  • the materials described in Non-Patent Document 3 have a complicated manufacturing method and there is room for further improvement because the OER activity is not high.
  • an object of the present invention is to develop a new transition metal oxide catalyst having higher OER activity, and further provide an air electrode catalyst, a water electrolytic anode catalyst, an air electrode and an air secondary battery using this catalyst. It is.
  • the present invention is as follows.
  • Amorphous, non-oxygen-deficient or oxygen-deficient transition metal oxide containing one or more elements selected from the following group A, one or more elements selected from group B, and cobalt Yes However, A group consists of Ca, Sr, Ba and rare earth elements (RE), Group B consists of 3d transition elements other than Co, And an oxide in which a cluster structure having a particle size in the range of 0.1 to 10 nm is observed in high resolution transmission electron microscopy, wherein the cluster structure portion has an element arrangement structure of ⁇ -CoOOH type or an element arrangement structure similar thereto. Having transition metal oxide.
  • An element arrangement structure of ⁇ -CoOOH type or an element arrangement structure similar to this is formed for charge compensation in a [CoO x ] planar monolayer formed by two-dimensionally connecting CoO 6 octahedra by sharing a ring.
  • protons coordinated [CoO x H y] plane monolayer can be n layer laminated to a [CoO x H y] n molecules layer, [CoO x H y] one side of the planar monolayer 10nm or less X is in the range of 1.5 to 2.0, y is in the range of 0.01 to 1, and n is the number of laminations in the direction (c-axis direction) perpendicular to the molecular layer plane of the planar monolayer, In the range of ⁇ 25, a part of Co in the [CoO x H y ] planar monolayer may be substituted with Fe, or a part of oxygen of the CoO 6 octahedron may be deficient Transition metal oxides described in [1].
  • Amorphous, non-oxygen-depleted type having an element arrangement structure of ⁇ -CoOOH type or an element arrangement structure similar thereto and having a cluster structure with a particle size in the range of 0.1 to 10 nm in high resolution transmission electron microscopy Or a method of producing an oxygen deficient transition metal oxide.
  • a x B 1 2-y B 2 y O 5 (1)
  • A represents Ca, Sr, Ba or a rare earth element (RE)
  • B 1 represents Co
  • B 2 represents a 3d transition element other than Co
  • x is a numerical value in the range of 1.5 to 2.0
  • y is a numerical value in the range of 0 to 1.0.
  • the metal air secondary battery which has an air electrode as described in [11] or [12], the negative electrode containing a negative electrode active material, and the electrolyte interposed between the said air electrode and the said negative electrode.
  • the metal-air secondary battery according to [13] further including an oxygen reduction air electrode containing a catalyst for oxygen reduction.
  • a novel oxide which is an amorphous transition metal oxide and in which a cluster structure having a particle size in the range of 0.1 to 10 nm can be found in a matrix structure. Since the ORR activity is higher than light type transition metal oxide A 2 B 2 O 5 , an excellent catalyst for air electrode and a catalyst for water electrolytic anode can be provided. Further, according to the present invention, it is possible to provide an air electrode for a metal air secondary battery using the catalyst for the air electrode and a metal air secondary battery using the air electrode.
  • FIG. 1 is a current-time curve when a Ca 2 FeCoO 5 carbon sheet electrode sample is subjected to constant-potential polarization at 1.7 V vs RHE for 20 h and oxygen generation reaction (OER).
  • (a) shows the current-voltage curve when the potential scan from 1.2 V vs RHE to 1.7 V vs RHE and OER is performed for the sample before and after the 20 h constant potential OER in FIG.
  • (b) shows a current-voltage curve when a potential scan from 1.0 V vs RHE to 0.6 V vs RHE is performed and oxygen reduction reaction (ORR) is performed for the sample before and after the 20 h constant potential OER in FIG.
  • ORR oxygen reduction reaction
  • FIG 1 shows a 20 h polarization before and after Ca 2 FeCoO 5 electrode sample XRD pattern.
  • TEM transmission electron microscope
  • TEM High resolution transmission electron microscope
  • TEM High resolution transmission electron microscope
  • the present invention is an amorphous non-oxygen-deficient or oxygen-deficient transition including one or more elements selected from the following group A, one or more elements selected from group B, and cobalt.
  • the cluster structure portion is a transition metal oxide having an element arrangement structure of ⁇ -CoOOH type or an element arrangement structure similar thereto.
  • the amorphous transition metal oxide of the present invention has a structure in which a cluster structure portion is dispersed in a matrix portion which is a portion other than the cluster structure portion. This structure can be observed and confirmed by high resolution transmission electron microscopy. Furthermore, the cluster structure portion had a particle size in the range of 0.1 to 10 nm, and the cluster structure shown in the example had a particle size in the range of approximately 0.5 to 5 nm.
  • the amorphous transition metal oxide of the present invention is an amorphous oxide because no diffraction pattern is observed in the limited field electron diffraction pattern and the halo pattern is exhibited.
  • the amorphous transition metal oxide of this invention is an amorphous oxide also in this point.
  • the matrix portion is amorphous, it does not matter whether the cluster structure portion is amorphous or not.
  • Amorphous in the oxide of the present invention means that a diffraction pattern can not be seen in a limited field electron diffraction image and a halo pattern is shown.
  • the amorphous transition metal oxide of the present invention is a material which is clearly different from the material described in Non-patent Document 3 because at least the particle diameter and diffraction peaks due to crystals are not observed by XRD.
  • the cluster structure part of the transition metal oxide of the present invention has an atomic arrangement structure that is the same as or similar to the atomic arrangement structure of ⁇ -CoOOH type.
  • the atomic arrangement structure of the ⁇ -CoOOH type is an atomic arrangement structure possessed by the crystal structure model of ⁇ -CoOOH (hexagonal), and FIG. 8 shows a crystal structure model of ⁇ -CoOOH (hexagonal). Red spheres (small), blue spheres (large) and white spheres (small, isolated between layers) in the figure indicate oxygen atom, cobalt atom and hydrogen atom, respectively.
  • the ⁇ -CoOOH has a layered structure in which a [CoO 2 ] planar molecular layer formed by the sharing of CoO 6 octahedra is stacked on the c-axis by hydrogen bonding via protons.
  • the transition metal oxide of the present invention has an atomic arrangement structure identical or similar to the crystal structure model of ⁇ -CoOOH (hexagonal crystal) shown in FIG. Such an atomic structure will be described later in the manufacturing method, but OER polarization causes rearrangement of the atoms to form a Co-rich oxide portion in the oxide matrix, which is similar to ⁇ -CoOOH. It is guessed that it formed.
  • the cluster structure in the oxide of the present invention observed by high resolution TEM is shown in FIG. 4b.
  • This cluster structure is a cluster structure having an atomic arrangement structure identical or similar to that of the ⁇ -CoOOH type atomic arrangement structure. is there.
  • the cluster structure part of the present invention may have oxygen vacancies, the part having oxygen vacancies is not identical to the atomic arrangement structure of ⁇ -CoOOH type, and an atom similar to the atomic arrangement structure of ⁇ -CoOOH type It is defined as having an array structure.
  • protons for charge compensation are arranged in a [CoO x ] planar monolayer formed by two-dimensionally connecting CoO 6 octahedra by ring sharing. It is a transition metal oxide containing a cluster structure portion of a [CoO x H y ] n molecular layer sheet-like substance formed by n-layer lamination of layered [CoO x H y ] planar monolayers, and [CoO x H]
  • One side of the [1] planar monolayer is 10 nm or less, x is in the range of 1.5 to 2.0, y is in the range of 0.01 to 1, and n is the direction perpendicular to the molecular layer plane of the planar monolayer (c Number of layers in the axial direction, in the range of 1 to 25, and a part of Co in the [CoO x H y ] planar monolayer may be substituted with Fe, and the CoO 6 octahedron It is an
  • Cluster structure of transition metal oxides of the present invention is a [CoO x] protons for charge compensation in the plane monolayer coordinated [CoO x H y] cluster structure of the n molecules layer sheet material .
  • the oxygen coordination number around Co was 5.1 for 1 hour polarization (Table 2).
  • the Co coordination number in the [CoO 2 ] n plane molecular layer sheet having no oxygen deficiency is six. Therefore, the cluster structure portion of the transition metal oxide of the present invention shown in the experimental example is considered to be a material having, as a basic skeleton, a [CoO x ] n molecular layer sheet having oxygen deficiency.
  • the atomic arrangement structure of such [CoO x H y ] n molecular sheet material is not identical to the atomic arrangement structure of the ⁇ -CoOOH type, but has an atomic arrangement structure similar to that of the ⁇ -CoOOH type It can be said that.
  • x is in the range of 1.5 to 2.0, preferably in the range of 1.6 to 1.9
  • y is in the range of 0.01 to 1, preferably in the range of 0.05 to 0.5
  • n is 1 It is in the range of ⁇ 25.
  • the maximum outer diameter of the cluster structure portion observed in the TEM image is in the range of 0.3 to 10 nm, preferably in the range of 0.6 to 7 nm, more preferably 0.9 to 5 nm.
  • the diameter of the CoO 6 octahedron is about 0.29 nm (approximately 0.3 nm), and the interlayer distance of the [CoO x H y ] monolayer is about 0.4 nm.
  • the number of CoO X H y octahedral molecules in the [CoO X H y ] monolayer is 10 / 0.29 x in order to form a cluster structure of this particle diameter.
  • the cluster structure portion of the oxide of the present invention is a [CoO X H y ] n molecular layer sheet-like material in which a stack in the plane vertical direction exists but is not developed, and n is a plane monolayer Is the number of layers stacked in the direction (c-axis direction) perpendicular to the molecular layer plane.
  • n is 1 to 10 / 0.4 (about 25). Therefore, the above n is in the range of 1 to 25.
  • n is 2 to 7 / 0.4 (about 18) in the range of 0.6 to 7 nm in diameter
  • n is 2 or 3 to 5 / 0.4 (about 12) in the range of 0.9 to 5 nm in diameter.
  • Group A consists of Ca, Sr, Ba and rare earth elements (RE), Group B consists of 3d transition elements other than Co.
  • the A group element consists of Ca, Sr, Ba and a rare earth element (RE).
  • the rare earth elements (RE) are two elements of Sc and Y and 15 elements of lanthanoid, and the lanthanoid is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.
  • the rare earth element (RE) is preferably, for example, La, Pr, Nd, Sm, Eu, Gd, etc., which have a relatively large ion radius.
  • Group B elements are 3d transition elements other than Co.
  • the 3d transition element represented by B is, for example, at least one metal element selected from the group consisting of Fe, Mn, Cr, Ni, Ti, Cu, and Zn.
  • the group B element is preferably iron from the viewpoint of providing a new transition metal oxide catalyst with higher OER activity.
  • the molar ratio of the group A element, the group B element and cobalt in the cluster structure part is in the range of 0 to 1.99: 0.01 to 1.0: 1.0. And preferably in the range of 0.01 to 1.0: 0.1 to 1.0: 1.0.
  • the molar ratio of the group A element, the group B element and cobalt in the matrix part which is the part other than the cluster structure part is 0.01 or more, 2.0 or less: 0.5 or more: 1.0, preferably 0.01 or more, 2.0 or less: 1 or more: 1.0, more preferably 0.5 to 1.9: 0.5 to 2.0: 1.0.
  • the molar ratio of the elements can be determined by electron energy loss spectroscopy.
  • the amorphous transition metal oxide of the present invention is non-oxygen deficient or oxygen deficient.
  • the ratio of oxygen to other elements is a stoichiometric ratio, while in the oxygen-deficient oxide, oxygen is more chemically related to the amount of other elements. Less than stoichiometric ratio.
  • the degree of oxygen deficiency is not particularly limited, but for example, it is more than 0 and 25% or less of the total valence of elements other than oxygen it can. However, there may be more oxygen deficiency than this.
  • the transition metal oxide of the present invention can be produced by amorphizing a brown mirror light type transition metal oxide.
  • a x B 1 2-y B 2 y O 5 (1)
  • A represents Ca, Sr, Ba or a rare earth element (RE)
  • B 1 represents Co
  • B 2 represents a 3d transition element other than Co
  • B 1 and B 2 consist of different elements
  • x is a numerical value in the range of 1.5 to 2.0
  • y is a numerical value in the range of 0 to 1.0.
  • Amorphization can be carried out, for example, by immersing a brown mirrorlite type transition metal oxide in an aqueous alkaline solution or polarization treatment in an aqueous alkaline solution.
  • the alkaline aqueous solution immersion can be carried out, for example, by immersion in an aqueous solution of an alkali metal hydroxide and an alkaline earth metal hydroxide at a temperature range of 0 to 80 ° C., for example.
  • concentration of the aqueous alkaline solution is not particularly limited, but should be, for example, in the range of 0.1 M to 10 M in consideration of the type of transition metal oxide of brown mirror light type, the immersion temperature, the time required for amorphization, etc. Can.
  • the immersion time can be appropriately determined in consideration of the type of brown mirror light type transition metal oxide, the immersion temperature, the concentration of the aqueous alkali solution, and the like.
  • the polarization treatment in the alkaline aqueous solution can be carried out by applying an electric potential of, for example, 1.0 to 2.0 V based on RHE, using the same alkaline aqueous solution as that shown in the alkaline aqueous solution immersion as an electrolytic solution.
  • the temperature of the electrolytic solution and the electrolysis time can be appropriately determined in consideration of the type of the brown mirror light type transition metal oxide and the progress of the amorphization. If the polarization process in the alkaline aqueous solution is the same as in alkaline aqueous solution immersion, the treatment in a short time may be possible if the concentration of the alkaline aqueous solution is the same.
  • the brown mirror light type transition metal oxide to be subjected to amorphization can be, for example, a crystalline transition metal oxide represented by the following general formula (1).
  • a x B 1 2-y B 2 y O 5 (1)
  • A represents Ca, Sr, Ba or a rare earth element (RE)
  • B 1 represents Co
  • B 2 represents a 3d transition element other than Co
  • B 1 and B 2 consist of different elements
  • x is a numerical value in the range of 1.5 to 2.0
  • y is a numerical value in the range of 0 to 1.0.
  • the brown mirror light type transition metal oxide can be synthesized by a solid phase reaction method using each metal oxide as a raw material with reference to the method described in Patent Document 1 and the method described in the following document.
  • the following Non-patent documents 4 to 7 can be referred to for a synthesis method for Ca 2 FeCoO 5 .
  • Non-patent document 4 P. Berastegui et al., Mater. Res. Bull. 1999, 34, 303.
  • the brown mirror light type transition metal oxide can also be synthesized using a liquid phase reaction method.
  • the liquid phase reaction method salts of the respective metals, for example, nitrates, acetates, citrates and the like are used as raw materials of the respective metal oxides.
  • a Ca salt eg, Ca (NO 3 ) 2
  • an Fe salt eg, Fe (NO 3 ) 3 .9H 2 O
  • a Co salt eg, Co (NO) 3 ) 2
  • a mixture to which citric acid is added as a gelling agent are mixed as a solvent, for example, using 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 a 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 heated, for example, to 50 to 90 ° C. to remove the solvent to gelate the mixture.
  • the gelled product is, for example, calcined in air at 300 to 500 ° C. (eg, 450 ° C.) for 10 minutes to 6 hours (eg, 1 hour) to synthesize a precursor.
  • this precursor can be baked, for example, in the air at 600 to 800 ° C. for 1 to 24 hours to synthesize brown mirror light type Ca 2 FeCoO 5 .
  • the firing conditions may be, for example, firing at 600 ° C. for a predetermined time (1 to 12 hours), and then raising the temperature, for example, firing at 800 ° C. for a predetermined time (6 to 12 hours).
  • the amorphous transition metal oxide of the present invention when used as a catalyst, the Braun Millerite type transition metal oxide having the same or similar composition and the OER activity are equivalent and higher ORR activity Indicates
  • Brown mirror light type Ca 2 FeCoO 5 as a raw material which was amorphous Ca
  • amorphous oxides containing Fe and Co as compared to brown mirror light type Ca 2 FeCoO 5 as a raw material It shows high ORR activity.
  • OER activity is equivalent.
  • the present invention includes a catalyst for an air electrode comprising the amorphous transition metal oxide of the present invention. Furthermore, the present invention includes a catalyst for a water electrolysis anode comprising the amorphous transition metal oxide of the present invention.
  • the catalyst for air electrode of the present invention and the catalyst for water electrolysis anode contain brown mirror light type transition metal oxide represented by the above general formula (1) in addition to the amorphous transition metal oxide of the present invention. You can also.
  • Amorphous transition metal oxide cathode catalyst and water electrolysis anode catalyst including the present invention can range from 1 ⁇ 100m 2 / g, preferably, 10 ⁇ 100 m 2 / It is in the range of g. However, it is not the intention limited to this range.
  • the amorphous transition metal oxide of the present invention is extremely useful as an air electrode, and is an air electrode of a metal-air secondary battery expected as hydrogen production by light water decomposition and as a next-generation high-capacity secondary battery. It is very promising as
  • the reaction at the anode of water electrolysis is represented by the following reaction formula.
  • Both reactions are oxygen evolution reactions (OER).
  • the amorphous transition metal oxide of the present invention is one having excellent OER activity, and is extremely useful as a catalyst for water electrolysis anode.
  • the cathode usually has a porous structure and contains a conductive material in addition to an 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 needs to have OER catalyst activity as a function at the time of charge and ORR catalyst activity as a function at the time of discharge. Since the catalyst of the present invention is an OER catalyst, the air electrode can also contain an ORR catalyst in addition to the catalyst.
  • ORR oxygen reduction
  • the content of the catalyst (OER catalyst) of the present invention in the air electrode is not particularly limited, but it is preferably, for example, 1 to 90% by mass, particularly 10 to 60 mass, from the viewpoint of enhancing the oxygen reaction performance of the air electrode. % Is preferable, and 30 to 50% by mass is more preferable.
  • ORR catalysts include, but are not limited to, Pt or Pt-based materials (eg, PtCo, PtCoCr, Pt-W 2 C, Pt-RuOx, etc.), Pd-based materials (eg, PdTi, PdCr, PdCo) , etc.), metal oxides PdCoAu (e.g., ZrO 2-x, TiO x , TaN x O y, etc. Irmo x), complex type (Co- porphyrin complexes), and the like other (PtMoRuSeO x, etc. RuSe) it can. Furthermore, LaNiO 3 (Nat. Chem.
  • the conductive material is not particularly limited as long as it can be generally used as a conductive aid, and conductive carbon is preferably mentioned. Specifically, mesoporous carbon, graphite, acetylene black, carbon nanotubes, carbon fibers and the like can be mentioned. Conductive carbon having a large specific surface area is preferred because it provides many reaction sites at the air electrode. Specifically, 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 of the cathode may be supported on a conductive material.
  • the content of the conductive material in the air electrode is not particularly limited, but is preferably 10 to 99% by mass, particularly preferably 20 to 80% by mass, from the viewpoint of enhancing the discharge capacity. More preferably, it is 50% by mass.
  • the binder is not particularly limited, and examples thereof include polyvinylidene fluoride (PVDF) and copolymers thereof, polytetrafluoroethylene (PTFE) and copolymers thereof, and styrene butadiene rubber (SBR).
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • SBR styrene butadiene rubber
  • the content of the binder in the air electrode is not particularly limited, it is preferably, for example, 1 to 40% by mass, particularly 5 to 35% by mass from the viewpoint of the binding ability between carbon (conductive material) and the catalyst. 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.
  • the mixing of the cathode constituent material and the solvent is preferably carried out usually for 3 hours or more, preferably 4 hours.
  • the mixing method is not particularly limited, and a general method can be adopted.
  • the substrate to which the slurry is applied is not particularly limited, and examples thereof include a glass plate, a Teflon (registered trademark) plate, and the like. These substrates are peeled off from the obtained air electrode after drying of the slurry.
  • the current collector of the air electrode or the solid electrolyte layer can be treated as the above-mentioned base material.
  • the base material is used as it is as a constituent member of the metal-air secondary battery without peeling off.
  • the coating method and the drying method of the slurry are not particularly limited, and a general method can be adopted.
  • 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 usually 5 to 100 ⁇ m, 10 to 60 ⁇ m, particularly preferably 20 to 50 ⁇ m.
  • An air electrode current collector for collecting current from the air electrode is usually connected to the air electrode.
  • the material and shape of the air electrode current collector are not particularly limited. Examples of the material of the air electrode current collector include stainless steel, aluminum, iron, nickel, titanium, carbon (carbon) and the like. Further, the shape of the air electrode current collector may be a foil shape, a plate shape, a mesh (grid shape), a fiber shape or the like, and among them, a porous shape such as a mesh shape is preferable. The porous current collector is excellent in the efficiency of oxygen supply to the air electrode.
  • the metal-air secondary battery of the present invention comprises an air electrode containing a catalyst containing the above amorphous transition metal oxide, a negative electrode containing a negative electrode active material, and an electrolyte interposed between the air electrode and the negative electrode.
  • the air electrode of the metal-air secondary battery of the present invention contains a catalyst containing an amorphous transition metal oxide transition metal oxide, which exhibits excellent OER catalytic properties. Therefore, by using an air electrode using this catalyst, the metal-air secondary battery of the present invention becomes excellent in charge rate and charge voltage.
  • the air electrode can also coexist a catalyst having ORR catalytic activity as described above.
  • an air electrode for oxygen reduction (ORR) containing a catalyst having ORR catalytic activity can be provided separately from an air electrode for oxygen generation (OER) containing a catalyst containing amorphous transition metal oxide.
  • the metal-air secondary battery has an air electrode for oxygen reduction and an air electrode for oxygen generation (three-electrode system). At the time of discharge, an air electrode for oxygen reduction is used, and at the time of charge, an air electrode for oxygen generation is used.
  • the catalyst having ORR catalytic activity is as described above, and an air electrode for oxygen generation can be obtained using this catalyst and the conductive material and the binder described in the explanation of the air electrode.
  • FIG. 10 is a cross-sectional view showing an embodiment of the metal-air secondary battery of the present invention.
  • the metal-air secondary battery 1 includes an air electrode 2 using oxygen as an active material, a negative electrode 3 containing a negative electrode active material, an electrolyte 4 responsible for ion conduction between the air electrode 2 and the negative electrode 3, and a current collector of the air electrode 2.
  • An air electrode current collector 5 to be performed and a negative electrode current collector 6 to collect current from the negative electrode 3 are accommodated in a battery case (not shown).
  • An air electrode current collector 5 for collecting current of the air electrode 2 is electrically connected to 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 current collector 6 for collecting current of the negative electrode 3 is electrically connected to 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 There is. It functions as a positive electrode terminal (not shown) and a negative electrode terminal (not shown), respectively.
  • the negative electrode contains a negative electrode active material.
  • a negative electrode active material the negative electrode active material of a common air battery can be used, It does not specifically limit.
  • the negative electrode active material is usually capable of inserting and extracting 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 terms of safety, and are expected as next-generation secondary batteries.
  • Lithium-air secondary batteries and magnesium-air secondary batteries are promising from the viewpoint of high voltage and high output.
  • An example of the zinc-air secondary battery will be described below, and 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 as such a negative electrode.
  • the zinc alloy include zinc alloys containing one or more elements selected from aluminum, indium, magnesium, tin, titanium, and copper.
  • metal lithium As a negative electrode active material of a lithium-air secondary battery, for example, metal lithium; lithium alloy such as lithium aluminum alloy, lithium tin alloy, lithium lead alloy, lithium silicon alloy, etc .; 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 and metal lithium is preferable among them.
  • metal lithium is preferable among them.
  • the negative electrode active material of the magnesium-air secondary battery a material capable of inserting and extracting magnesium ions is used.
  • a negative electrode magnesium aluminum, magnesium silicon, magnesium alloys such as magnesium gallium and the like can be used besides metal magnesium.
  • the foil-like or plate-like negative electrode active material can be used as the negative electrode itself.
  • the negative electrode may contain at least a negative electrode active material, but may contain a binder for immobilizing the negative electrode active material, if necessary.
  • the type of binder, the amount used, and the like are the same as those of the above-described air electrode, and thus the description thereof is omitted here.
  • the negative electrode is usually connected to a negative electrode current collector for collecting current from the negative electrode.
  • the material and shape of the negative electrode current collector are not particularly limited. Examples of the material of the negative electrode current collector include stainless steel, copper, nickel and the like. Moreover, as a shape of a negative electrode collector, foil shape, plate shape, mesh (grid shape) etc. are mentioned.
  • An electrolyte is disposed between the air electrode and the negative electrode. Metal ion conduction between the negative electrode and the air electrode takes place via the electrolyte.
  • the form of the electrolyte is not particularly limited, and examples thereof include a liquid electrolyte, a gel electrolyte, a solid electrolyte and the like.
  • the electrolytic solution may be an alkaline aqueous solution such as an aqueous solution of potassium hydroxide containing zinc oxide or an aqueous solution of sodium hydroxide, for example, when the negative electrode is zinc or an alloy thereof, or zinc chloride or zinc perchlorate.
  • An aqueous solution may be used, or a non-aqueous solvent containing zinc perchlorate or a non-aqueous solvent containing zinc bis (trifluoromethylsulfonyl) imide may be used.
  • a negative electrode is magnesium or its alloy is mentioned as an example, you may use the non-aqueous solvent containing magnesium perchlorate and magnesium bis (trifluoromethyl sulfonyl) imide.
  • non-aqueous solvent for example, conventional secondary batteries such as ethylene carbonate (EC), propylene carbonate (PC), ⁇ -butyrolactone ( ⁇ -BL), diethyl carbonate (DEC), dimethyl carbonate (DMC) or the like
  • EC ethylene carbonate
  • PC propylene carbonate
  • ⁇ -BL ⁇ -butyrolactone
  • DEC diethyl carbonate
  • DMC dimethyl carbonate
  • ionic liquids such as N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethylsulfonyl) imide (am) can also be used.
  • the electrolyte preferably contains a dendrite formation inhibitor. It is believed that the dendrite formation inhibitor suppresses the generation of dendrite by adsorbing to the negative electrode surface at the time of charge to reduce the energy difference between crystal planes and preventing preferential orientation.
  • the dendrite formation inhibitor is not particularly limited, and may be, for example, at least one selected from the group consisting of polyalkyleneimines, polyallylamines and asymmetric dialkyl sulfones (for example, JP-A-2009 -93983)).
  • the amount of the dendrite formation inhibitor used is not particularly limited, but may be used, for example, as an amount that saturates the electrolyte at normal temperature and pressure, or 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 , Organic lithium salts such as LiC (CF 3 SO 2 ) 3 and the like can be mentioned.
  • 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, 1,2-dimethoxymethane, 1,3-dimethoxypropane, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran and mixtures thereof can be mentioned.
  • An ionic liquid can also be used as a non-aqueous solvent.
  • the concentration of the lithium salt in the non-aqueous electrolytic solution is not particularly limited, but is preferably in the range of, for example, 0.1 mol / L to 3 mol / L, and preferably 1 mol / L.
  • a low volatility liquid such as an ionic liquid may be used as the non-aqueous electrolyte.
  • the gel electrolyte having lithium ion conductivity can be obtained, for example, by adding a polymer to the above-mentioned non-aqueous electrolyte and gelling it.
  • a polymer such as polyethylene oxide (PEO), polyvinylidene fluoride (PVDF, trade name Kynar manufactured by Arkema, etc.) polyacrylonitrile (PAN) or polymethyl methacrylate (PMMA) is added to the non-aqueous electrolyte. Gelation can be performed by carrying out.
  • the solid electrolyte having lithium ion conductivity is not particularly limited, and a general solid electrolyte usable in a lithium metal air secondary battery can be used.
  • oxide solid electrolytes such as Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 ; Li 2 S—P 2 S 5 compounds, Li 2 S—SiS 2 compounds, Li 2 S—GeS 2 And compounds such as sulfide solid electrolytes.
  • the thickness of the electrolyte varies depending on the configuration of the battery, but is preferably in the range of, for example, 10 ⁇ m to 5000 ⁇ m.
  • a separator is preferably disposed between the air electrode and the negative electrode in order to ensure electrical insulation between the electrodes.
  • the separator is not particularly limited as long as it has a structure in which electrical insulation between the air electrode and the negative electrode can be secured and an electrolyte can be interposed between the air electrode and the negative electrode.
  • separator examples include porous films such as polyethylene, polypropylene, cellulose, polyvinylidene fluoride, and glass ceramics; and nonwoven fabrics such as resin nonwoven fabrics and glass fiber nonwoven fabrics. Among them, a separator made of glass ceramic is preferable.
  • a battery case for housing the metal air secondary battery a battery case of a general metal air secondary battery can be used.
  • 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, but specific examples include coin type, flat type, cylindrical type, laminate type, etc. Can.
  • the metal-air secondary battery of the present invention can be discharged by supplying oxygen, which is an active material, to the air electrode.
  • oxygen supply source in addition to air, oxygen gas etc. may be mentioned, preferably oxygen gas.
  • oxygen gas preferably oxygen gas.
  • the pressure of the supplied air or oxygen gas is not particularly limited, and may be set as appropriate.
  • the catalyst for air electrode containing the amorphous transition metal oxide of the present invention is useful not only in the metal air secondary battery but also in the field where other OER electrode catalysts are used.
  • OER electrode catalysts have long been studied or used as counter electrodes for various electrochemical reactions, and can be used for alkali metal plating, electrolytic degreasing, and cathodic protection technology.
  • it is expected to be applied to highly efficient and clean hydrogen production technology by combining with solar cells and photocatalysts.
  • x 1.0
  • catalyst ink Ca 2 Fe 2-x Co x O 5 catalyst and amorphous Ca 1 Fe m Co n O k catalyst, carbon powder and Nafion binder in a weight ratio of 5: 1: 1 respectively It was added to 5 ml of ethanol and well dispersed by an ultrasonic mixer. From the above, a catalyst ink having a catalyst concentration of 5 mg cm -3 was prepared.
  • the catalyst ink was collected by a pipette and applied onto a glassy carbon disk or a carbon sheet so as to be 1 mg cm ⁇ 2 to prepare an electrode sample.
  • a 4 M KOH solution was used as an electrolyte, and the above-mentioned electrode sample was used as a working electrode.
  • RHE is a relative standard electrode potential.
  • FIG. 1 is a current-time curve when Ca 2 FeCoO 5 carbon sheet electrode sample is subjected to constant-potential polarization at 1.7 V vs RHE for 20 h and oxygen evolution reaction (OER).
  • the current value decreased with the passage of time, and the current after 20 h decreased by about 40% compared to the initial current. This is because at 1.7 V, carbon which plays a role of current collection is oxidized and consumed.
  • FIG. 2 (a) shows a current-voltage curve when a potential scan from 1.2 V vs RHE to 1.7 V vs RHE and OER is performed for the sample before and after the 20 h constant potential OER in FIG.
  • the potential at which the OER current starts to rise is approximately equal around 1.48 V vs RHE, and that the OER catalytic activity has not changed.
  • FIG. 2 (b) shows a current-voltage curve when the potential reduction scan (ORR) is performed from 1.0 V vs RHE to 0.6 V vs RHE for the sample before and after the 20 h constant potential OER in FIG. There is.
  • ORR potential reduction scan
  • FIG. 3 shows the XRD pattern of the Ca 2 FeCoO 5 electrode sample before and after 20 h polarization at 1.7 V vs RHE in FIG. It can be seen that the brown mirror light type structure collapses and an amorphous phase is formed.
  • FIG. 4 shows high resolution TEM photographs before and after 1 h OER polarization at 1.7 V vs RHE.
  • a clean checkerboard derived from the brown mirror light type crystal structure is observed.
  • the limited field electron diffraction pattern also showed a diffraction pattern showing a brown mirror light structure.
  • the lattice disappears and an amorphous phase is formed, and the electron diffraction pattern also shows only the halo pattern.
  • dark clusters of about 0.5-1 nm in size were observed, and it was found that they had a nonuniform structure.
  • Table 1 shows the results of metal composition analysis of this dark cluster and the other light colored portions by EELS.
  • the dark portion has a relatively higher Co concentration than the composition of the base material, and lower Ca and Fe instead.
  • Ca was slightly lower than the composition of the base material, but the ratio of Fe / Co remained almost 1/1.
  • FIG. 5 (a) shows that OER was subjected to potential scanning from 1.2 V vs RHE to 1.7 V vs RHE for the amorphization sample by KOH aqueous solution immersion (80 ° C. 24 h) Current-voltage curve.
  • the potential at which the OER current starts to rise is approximately equal around 1.48 V vs RHE, which indicates that the OER catalytic activity has not changed.
  • Fig. 5 (b) shows the current-voltage curve when the potential reduction scan from 1.0 V vs RHE to 0.6 V vs RHE and the oxygen reduction reaction (ORR) were performed on the amorphized sample by KOH aqueous solution immersion (80 ° C 24 h). Is shown. In the sample before the KOH aqueous solution immersion, the onset potential of the negative ORR current is 0.78 V vs RHE, but after the KOH aqueous solution immersion, the current rises from 0.82 V vs RHE, and thus the KOH aqueous solution immersion sample has a higher potential. It was shown that more ORR reaction occurred, that is, ORR high activity.
  • FIG. 6 shows the XRD pattern of the amorphized sample by KOH aqueous solution immersion (80 ° C. 24 h). It can be seen that the brown mirror light type structure collapses and an amorphous phase is formed.
  • EXAFS oscillations of the sample after polarization can be well fitted by the crystal model of ⁇ -CoOOH.
  • the fitting results are shown in FIG. 7 (d) and Table 2.
  • the ⁇ -CoOOH has a layered structure in which a [CoO 2 ] n plane molecular layer sheet formed by the sharing of CoO 6 octahedra is laminated on the c-axis by hydrogen bonding via protons (FIG. 8).
  • the oxide of the present invention undergoes atomic rearrangement by OER to form a Co-rich oxide portion in the oxide matrix, which forms an ordered structure similar to ⁇ -CoOOH. Indicated. That is, the nanoclusters observed by the high resolution TEM in FIG. 4 were determined to be nanoclusters having this ⁇ -CoOOH type array structure or an array structure similar thereto.
  • the oxygen coordination number around Co is 5.1 for 1 hour polarization (Table 2).
  • the coordination number of Co in the [CoO 2 ] planar monolayer having no oxygen deficiency is six. Therefore, the nanoclusters formed in the oxide of the present invention are considered to be materials having a [CoO 1.8 ] planar monolayer sheet having oxygen deficiency as a basic skeleton.
  • the stacking in the c-axis direction of this nanocluster is to some extent inferred from the particle diameter observed in the TEM image.
  • the cluster structure in the oxide of the present invention has some stacking in the direction perpendicular to the plane, this stacking is not so developed, [CoO 1.8 ] planar monolayer and charge compensation For [CoO 1.8 H y ] n molecular sheet with coordinated protons.
  • the present invention is useful in the fields of secondary batteries, metal-air secondary batteries expected as next-generation high-capacity secondary batteries, and hydrogen production by water electrolysis and light water decomposition.

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Abstract

La présente invention concerne un oxyde de métal de transition amorphe qui comprend un élément du groupe A (Ca, Sr, Ba, et des éléments de terres rares (RE)), du cobalt et un élément du groupe B (élément de transition 3d autre que Co). L'observation avec un microscope électronique à transmission à haute résolution révèle que cet oxyde de métal de transition amorphe a une structure en grappe ayant un diamètre de particule tombant dans une plage allant de 0,1-10 nm. La partie de structure en grappe a une structure de réseau d'éléments de type γ-CoOOH ou une structure de réseau d'éléments similaire à celle-ci. Dans la partie de structure en grappe, le rapport molaire de l'élément du groupe-A, du cobalt et de l'élément du groupe B se situe dans la plage de 0 à 1,99 : 0,01 à 1,0 : 1,0. Dans une partie matrice, le rapport molaire de l'élément du groupe-A, du cobalt, et de l'élément du groupe B se situe dans la plage allant de moins de 1,0 mais inférieure à 2,0 : pas moins de 1 : 1,0. La présente invention concerne également un catalyseur d'électrode positive d'électrolyse de l'eau et un catalyseur d'électrode à air comprenant ledit oxyde de métal de transition amorphe. L'invention concerne : une électrode à air pour une batterie secondaire métal-air comprenant le catalyseur mentionné ci-dessus ; et une batterie secondaire métal-air qui a une électrode à air comprenant le catalyseur mentionné ci-dessus, une électrode négative comprenant un matériau actif d'électrode négative, et un électrolyte intercalé entre l'électrode à air et l'électrode négative.
PCT/JP2018/041555 2017-11-10 2018-11-08 Oxyde de métal de transition amorphe et son utilisation WO2019093441A1 (fr)

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