WO2016132932A1 - Catalyseur pour réaction de réduction de l'oxygène et électrode à air pour accumulateurs métal-air - Google Patents

Catalyseur pour réaction de réduction de l'oxygène et électrode à air pour accumulateurs métal-air Download PDF

Info

Publication number
WO2016132932A1
WO2016132932A1 PCT/JP2016/053451 JP2016053451W WO2016132932A1 WO 2016132932 A1 WO2016132932 A1 WO 2016132932A1 JP 2016053451 W JP2016053451 W JP 2016053451W WO 2016132932 A1 WO2016132932 A1 WO 2016132932A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
oxygen
transition metal
reduction reaction
air
Prior art date
Application number
PCT/JP2016/053451
Other languages
English (en)
Japanese (ja)
Inventor
悦司 辻
本橋　輝樹
裕之 野田
浩樹 幅▲ざき▼
佳士 井上
Original Assignee
国立大学法人北海道大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 国立大学法人北海道大学 filed Critical 国立大学法人北海道大学
Priority to JP2017500604A priority Critical patent/JP6731199B2/ja
Publication of WO2016132932A1 publication Critical patent/WO2016132932A1/fr

Links

Images

Classifications

    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J35/60—
    • 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

Definitions

  • the present invention relates to a highly active catalyst for oxygen reduction reaction and an air electrode for a metal-air secondary battery.
  • Lithium ion secondary batteries are used in various places, and recently, they are also being installed in clean electric vehicles that do not use fossil fuels. However, the capacity is not sufficient, and in order to realize a mileage similar to that of a gasoline vehicle, further increase in capacity is essential, and development of innovative storage batteries to replace lithium ion secondary batteries is actively underway. .
  • the metal-air secondary battery uses air taken from the outside air as the fuel for the positive electrode reaction, the negative electrode fuel can be filled in most of the battery body. For this reason, for example, a zinc-air secondary battery that is excellent in safety can theoretically be increased in capacity by 5 to 10 times that of the current lithium ion secondary battery.
  • ORR oxygen Reduction Reaction
  • noble metal catalysts such as Pt and Pd are known as highly active catalysts for ORR.
  • these noble metals are expensive and have a small reserve, so they are free of ORR for widespread use. Catalyst development is required.
  • Perovskite-type transition metal oxide ABO3 has been reported as a non-noble metal ORR 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.
  • the number of eg electrons of this B-site transition metal is related to its ORR activity, and LaNiO 3 and the like having an eg electron number of 1 are highly active [Non-patent Documents 1 and 2]. It has been reported.
  • Non-Patent Document 1 J. Suntivich, H. A. Gasteiger, N. Yabuuchi, H. Nakanishi, J. B. Goodenough and Y. S.-Horn, Nature Chem. 2012, 3, 546-550.
  • Non-Patent Document 2 J. Suntivich, H. A. Gasteiger, N. Yabuuchi and Y. S.-Horn, J. Electrochem. Soc. 2010, 157, B1263-B1268.
  • Non-Patent Document 3 F. Millange et al., Mater. Res. Bull. 1999, 34, 1.
  • Non-Patent Document 4 C. Perca et al., Chem. Mater. 2005, 17, 1835.
  • Non-Patent Document 5 A. J. Williams et al., Phys. Rev. B 2005, 72, 024436.
  • Non-Patent Document 6 V. Vashook et al., Solid State Ionics 2008, 179, 135.
  • Non-Patent Documents 1 and 2 cannot be said to have sufficient catalytic activity, and further development of a highly active transition metal oxide group is necessary.
  • an object of the present invention is to provide an ORR catalyst that does not contain a highly active noble metal than the transition metal oxides described in Non-Patent Documents 1 and 2. It is another object of the present invention to provide an air electrode and an air secondary battery using the catalyst.
  • a catalyst for oxygen reduction reaction comprising at least one compound selected from the group consisting of a double perovskite transition metal oxide and an oxygen-deficient perovskite transition metal oxide.
  • the double perovskite transition metal oxide has a general formula BaLnMn 2 O 5 + ⁇ (where Ln is a group consisting of Y, Er, Ho, Dy, Tb, Gd, Eu, Sm, Nd, Pr, and La).
  • Ln is a group consisting of Y, Er, Ho, Dy, Tb, Gd, Eu, Sm, Nd, Pr, and La).
  • the catalyst for oxygen reduction reaction according to [1] which is at least one selected transition metal, and ⁇ is a numerical value of 0 to 1.
  • the general formula BaLnMn 2 O 5 + ⁇ is a perovskite-related compound having Ba and Ln at the A site and manganese at the B site, and consists of an octahedral structure bonded to six oxygen atoms or a pyramid structure bonded to five oxygen atoms [ The catalyst for oxygen reduction reaction according to 2].
  • the oxygen-deficient perovskite transition metal oxide is A 1-x A ′ x B 1-y B ′ y O 3- ⁇ (A: +3 valent cation, A ′: +2 valent cation, B, B ': The oxygen reduction reaction catalyst according to [1], independently represented by a transition metal ion, 0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.5, ⁇ > 0).
  • the general formula A 1-x A ′ x B 1-y B ′ y O 3- ⁇ is an oxygen deficient perovskite type represented by the general formula A 1-x A ′ x Mn 1-y Ni y O 3- ⁇
  • A is at least one rare earth selected from the group consisting of La, Pr, Nd, Sm, Eu, and Gd
  • For oxygen reduction reaction catalyst or air electrode of at least one compound selected from the group consisting of double perovskite type transition metal oxides and oxygen deficient perovskite type transition metal oxides according to any one of [1] to [8] Use as a catalyst.
  • [11] [1] An air electrode for a metal-air secondary battery comprising the catalyst according to any one of [8].
  • the at least one compound selected from the group consisting of the double perovskite transition metal oxide and the oxygen-deficient perovskite transition metal oxide is contained as an oxygen reduction reaction catalyst, and further includes an oxygen generation catalyst [11]. Air pole.
  • an ORR catalyst having higher activity than LaNiO 3 is provided. be able to.
  • an air electrode for a metal-air secondary battery using the ORR catalyst and a metal-air secondary battery using the air electrode can also be provided.
  • the surface area evaluated by the nitrogen adsorption method is 3.93 m 2 g -1 and vacuum It was found to be about 10 times that synthesized by the sealed tube method.
  • Electrode preparation conditions and electrochemical measurement conditions are shown.
  • the electrochemical measurement results are shown for BaLnMn 2 O 5 (Ln: Y, Gd, Nd, La) synthesized by the vacuum sealed tube method.
  • For BaLaMn 2 O 5 prepared in an inert atmosphere firing method shows the electrochemical measurements.
  • the structural example of the metal air secondary battery of this invention is shown.
  • the present invention provides at least one member selected from the group consisting of double perovskite-type transition metal oxides and oxygen-deficient perovskite-type transition metal oxides.
  • the present invention relates to a catalyst for oxygen reduction reaction containing a compound.
  • Specific examples include LaMnO 3 , LaCoO 3 , and LaNiO 3 .
  • a perovskite having a plurality of elements at the A site and the B site contains, for example, A, A ′ at the A site, and B, B ′ at the B site, respectively.
  • Is represented by A 1-x A ' x B 1-y B' y O 3 (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1), and [(1-x) A + xA ']: [ (1-y) B + yB ']: O 1: 1: 3 is satisfied.
  • Specific examples include Ba 0.8 Sr 0.2 Co 0.5 Fe 0.5 O 3 and the like.
  • the perovskite in which A and A ′ or B and B ′ are regularly arranged is specifically called a double perovskite (the structure of the double perovskite will be described later).
  • double perovskite doubles the number of each atom of b so that it can be distinguished from perovskite by chemical formula, and A 2 (1-x) A ' 2x B 2 (1-y) B' 2y O 6 (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1).
  • the former is a perovskite with a 1: 1 mixture of Ba and La at the A site.
  • the latter represents a perovskite in which Ba and La are alternately laminated on the A site, that is, a double perovskite.
  • the double perovskite type transition metal oxide of the present invention can be, for example, a transition metal oxide represented by the general formula BaLnMn 2 O 5 + ⁇ , where Ln is Y, Er, Ho, Dy, Tb. , Gd, Eu, Sm, Nd, Pr, and La can be at least one transition metal oxide.
  • the double perovskite is generally represented by the general formula A 2 (1-x) A ′ 2x B 2 (1-y) B ′ 2y O 6 (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1) Compound containing 6 oxygen atoms.
  • the double perovskite represented by the general formula A 2 (1-x) A ′ 2x B 2 (1-y) B ′ 2y O 6 (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1) Is the case where at least one atom of A, A ′, B, and B ′ is an atom having a valence less than +3 since the charge of the compound is 0 (zero).
  • an oxygen reduction reaction catalyst of a double perovskite transition metal oxide represented by the general formula BaLnMn 2 O 5 + ⁇ varies depending on the type of Ln.
  • Ln is preferably Nd or La, and particularly preferably La.
  • ⁇ is a numerical value in the range of 0 to 1, and mainly takes 0, 0.5, or 1, but in actual compounds, in each case, some oxygen defects or excess oxygen (apparently ⁇ exceeds 1) There may also be a situation.
  • a double perovskite type transition metal oxide which is a transition metal oxide represented by the general formula BaLnMn 2 O 5 + ⁇ , is a perovskite-related compound having Ba and Ln at the A site and manganese at the B site. compounds), consisting of octahedrally-coordinated structures combined with six oxygens, or pyramidally-coordinated structures combined with five oxygens.
  • Double perovskite type transition metal oxides represented by the general formula BaLnMn 2 O 5 + ⁇ have been reported, for example, in Non-Patent Documents 3 to 5, and are known as substances.
  • it can also be synthesized by a method of firing in an inert atmosphere using a salt such as metal acetate as a starting material (firing under inert atmospheres).
  • Ln is Y
  • Ln La, Nd, or Gd
  • barium nitrate, transition metal oxides, and rare earth nitrates are mixed with citric acid at a predetermined ratio to form a gel.
  • the oxide precursor is formed by heating at 350 to 600 ° C. for 0.1 to 6 hours and then at 900 to 1000 ° C. for 1 to 72 hours in a nitrogen atmosphere.
  • the oxide precursor is vacuum sealed in the presence of an oxygen getter (for example, iron monoxide FeO), heated at 1000 to 1200 ° C. for 1 to 72 hours, and rapidly cooled after the heating is completed, whereby a double perovskite transition metal An oxide is obtained.
  • an oxygen getter for example, iron monoxide FeO
  • barium acetate, transition metal acetate and rare earth acetate are mixed at a predetermined ratio to obtain an acetic acid aqueous solution, and then the obtained acetic acid aqueous solution is heated at 60 to 70 ° C. to remove water. And then heated in air at 350-600 ° C. for 0.1-6 hours to form the precursor. Next, the precursor is heated at 900 to 1100 ° C. for 1 to 72 hours in a nitrogen atmosphere (preferably in a nitrogen stream) to obtain a double perovskite type transition metal oxide.
  • the vacuum-sealed tube method tends to obtain a double perovskite type transition metal oxide with good crystallinity, and the crystallinity of the double perovskite type transition metal oxide may be slightly inferior in the firing method under an inert atmosphere. is there.
  • the surface area of the double perovskite type transition metal oxide tends to be larger in the sample obtained by the firing method in an inert atmosphere.
  • crystallinity and surface area a double perovskite type transition metal oxide having better crystallinity and having a larger surface area advantageous as a catalyst by optimizing the conditions of the firing method in an inert atmosphere Can be obtained.
  • the firing method in an inert atmosphere is more suitable for mass production of a double perovskite type transition metal oxide.
  • the identification of the double perovskite type transition metal oxide can be performed by an X-ray diffraction experiment (for example, using Rigaku Ultima IV), and the analysis of the oxygen amount can be performed by, for example, iodometric titration.
  • the surface area of the double perovskite type transition metal oxide can be, for example, in the range of 0.1 to 100 m 2 / g, preferably in the range of 0.2 to 100 m 2 / g, more preferably 0.3 to Can be in the range of 100m 2 / g.
  • the particle size of the double perovskite type transition metal oxide used in the present invention is not particularly limited, but the average particle size is, for example, about 10 nm to 10 ⁇ m, preferably about 100 nm to 5 ⁇ m, more preferably about 200 nm to 2 ⁇ m. However, these are merely examples and are not intended to be limited to these ranges.
  • the oxygen reduction reaction catalyzed by the double perovskite transition metal oxide is, for example, a reduction reaction of oxygen molecules in an aqueous solution.
  • BaLaMn 2 O 5 and BaNdMn 2 O 5 using La or Nd as Ln were particularly excellent.
  • BaLaMn 2 O 5 that is micronized has a small overvoltage for ORR of about 0.925 V vs RHE @ 50 ⁇ A / cm 2 in 4 mol dm -3 KOH aqueous solution, and about -0.73 mA / cm 2 @ 0.8 V. A large reduction current of vs RHE was observed.
  • the ORR activity can be changed by changing the element at the Ln site, although the formal valence of Mn is the same.
  • Nd By using Nd, it works as a highly active ORR catalyst.
  • BaLaMn 2 O 5 fine particle samples prepared in a gram order by an inert atmosphere firing method achieved twice the ORR activity of LaNiO 3 reported so far as a transition metal highly active catalyst.
  • alkaline fuel cells metal-air secondary batteries and alkaline fuel cells (alkaline fuel cells), which are expected as next generation high-capacity secondary batteries (New generation high capacity secondary batteries (rechargeable batteries)) and alkaline fuel cells (alkaline fuel cells). It is extremely promising as an air electrode.
  • the oxygen-deficient perovskite type transition metal oxide is characterized by having an oxygen deficiency, and has an excellent catalytic activity in the ORR reaction like the double perovskite type transition metal oxide.
  • An oxygen-deficient perovskite-type transition metal oxide catalyst can be obtained by intentionally introducing oxygen-deficiency into the perovskite-type transition metal oxide catalyst.
  • the oxygen-deficient perovskite transition metal oxide used as a catalyst in the present invention can be represented by, for example, the general formula Ln 1-x A ′′ x Mn 1-y B ′′ y O 3 ⁇ .
  • Ln can be at least one transition metal composed of La, Pr, Nd, Sm, Eu, and Gd.
  • a ′′ is an atom having a valence of less than +3, for example, an alkaline earth metal (eg, Ca, Sr) atom.
  • B ′′ is an atom having a valence of less than +3.
  • it can be a transition metal atom exhibiting a valence of less than +3.
  • x and y in the formula can satisfy 0 ⁇ x ⁇ 0.5 and 0 ⁇ y ⁇ 0.5.
  • ⁇ varies as appropriate depending on the kind and amount of atoms constituting the compound, but for example, is a range satisfying 0 ⁇ ⁇ (x + y) / 2. However, it is not intended to be limited to this range.
  • perovskite is generally represented by the general formula ABO 3 and has a + 3-valent cation at the A and B sites, and the valence of the compound as a whole is zero. Therefore, by substituting part of the A and B sites with +2 valent cations, the number of cations in the entire compound is reduced, and oxygen anions are reduced accordingly, thereby introducing oxygen deficiency.
  • a compound in which A ′′ in the general formula Ln 1-x A ′′ x Mn 1-y B ′′ y O 3- ⁇ is Ca and B ′′ is Ni is represented by the general formula La 1-x Ca x Mn 1
  • the perovskite type transition metal oxide will be described with reference to La 1-x Ca x Mn 1-y Ni y O 3 ⁇ (0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.5, ⁇ > 0).
  • Perovskite-type transition with oxygen deficiency which is a transition metal oxide expressed by La 1-x Ca x Mn 1-y Ni y O 3- ⁇ (0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.5, ⁇ > 0)
  • a metal oxide is a perovskite-related compound having, for example, La and Ca at the A site and Mn and Ni at the B site.
  • the octahedral structure is bonded to 6 oxygen atoms
  • the pyramid structure is bonded to 5 oxygen atoms, or oxygen. It consists of square-coordinated structures connected to four.
  • a schematic diagram of the crystal structure is shown below. The pyramid structure combined with five oxygen atoms is present at the Mn or Ni site adjacent to the oxygen deficiency.
  • Perovskite type transition metal oxide having oxygen deficiency which is a transition metal oxide represented by La 1-x Ca x Mn 1-y Ni y O 3- ⁇ (0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.5)
  • La 1-x Ca x Mn 1-y Ni y O 3- ⁇ (0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.5)
  • the production method can be synthesized by a citrate polymerization method using a precursor such as a metal nitrate as a starting material and a precursor prepared by the citric acid method.
  • a perovskite having an oxygen deficiency which is a transition metal oxide represented by La 1-x Ca x Mn 1-y Ni y O 3- ⁇ (0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.5, ⁇ > 0)
  • Type transition metal oxides can be identified by X-ray diffraction experiments.
  • lanthanum nitrate, calcium nitrate, and a transition metal oxide are mixed with citric acid at a predetermined ratio for gelation, and then the gelled mixture is 0.1 to 350 ° C. in air at 350 to 450 ° C. Heat for ⁇ 6 hours to form oxide precursor. Next, by heating at 600 to 1000 ° C. for 3 to 12 hours, a perovskite type transition metal oxide having oxygen vacancies can be obtained.
  • Identification of a perovskite type transition metal oxide having an oxygen deficiency can be performed by an X-ray diffraction experiment (for example, using Rigaku Ultima IV).
  • the analysis of the amount of oxygen can be performed, for example, by thermogravimetry during iodine titration or hydrogen reductive decomposition. It can be done by analysis.
  • the surface area of the double perovskite type transition metal oxide can be, for example, in the range of 0.1 to 100 m 2 / g, preferably in the range of 0.2 to 100 m 2 / g, more preferably 0.3. It can be in the range of ⁇ 100m 2 / g.
  • the particle size of the perovskite type transition metal oxide having oxygen deficiency used in the present invention is not particularly limited, but the average particle size is, for example, about 10 nm to 10 ⁇ m, preferably 100 nm to 5 ⁇ m, more preferably about 200 nm to 2 ⁇ m. . However, these are merely examples and are not intended to be limited to these ranges.
  • the oxygen reduction reaction catalyzed by the perovskite transition metal oxide having oxygen deficiency is, for example, a reduction reaction of oxygen molecules in an aqueous solution.
  • La 1-x Ca x Mn 1-y Ni y O 3- ⁇ (0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.5) of the present invention, the amount of Ca substitution at the A site and the amount of Ni substitution at the B site are changed.
  • oxygen deficiency can be introduced and ORR activity can be changed.
  • ORR activity can be changed.
  • it works as a highly active ORR catalyst.
  • the air electrode usually has a porous structure and includes an electro-conductive material in addition to an oxygen reduction reaction catalyst.
  • the air electrode may contain an oxygen generation reaction (OER) catalyst, a binder, and the like as necessary.
  • OER oxygen generation reaction
  • the air electrode in the secondary battery needs to have an OER catalytic activity as a function during charging and an ORR catalytic activity as a function during discharging. Since the catalyst of the present invention is an ORR catalyst, the air electrode can contain an OER catalyst in addition to this catalyst.
  • the chemical formulas at the time of charging and discharging at the air electrode are shown below.
  • the content of the catalyst of the present invention (ORR catalyst) in the air electrode is not particularly limited, but is preferably, for example, 1 to 90% by mass, particularly 10 to 60% from the viewpoint of improving the oxygen reduction reaction performance of the air electrode.
  • the content is preferably mass%, more preferably 30 to 50 mass%.
  • OER catalyst examples are not particularly limited.
  • noble metal oxides for example, IrO 2 , RuO 2, etc.
  • Ni or Ni-based materials for example, NiO
  • Co-based materials for example, Co 3 O) 4
  • perovskite oxides eg Ba x Sr 1-x Co x Fe 1-x O 3 , SrCoO 3 , LaNiO 3 , La 1-x Ca x CoO 3 , LaFe 1-x Ni x O 3 , LaMnO 3
  • spinel oxides eg, CoFe 2 O 4 , NiCo 2 O 4 , Mn x Cu 1-x Co 2 O 4 , etc.
  • metal organic structures eg, MOF containing Co or Fe
  • Complex systems eg, Co-porphyrin complexes, etc.
  • graphene composite systems eg, CoO / graphene, Co-Fe / graphene, etc.
  • others eg, NiCo 2 S 4 , Mn 2 O 3
  • 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 OER catalyst is used in combination can be appropriately determined in consideration of the type of OER 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 double perovskite 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.
  • the air electrode of the metal-air secondary battery of the present invention contains a catalyst containing a double perovskite type transition metal oxide, and this catalyst exhibits excellent ORR catalyst characteristics. 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 OER catalytic activity as described above.
  • an oxygen reaction (OER) air electrode containing a catalyst having OER catalytic activity can be provided separately from an oxygen generation (ORR) air electrode containing a catalyst containing a double perovskite type transition metal oxide.
  • 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 OER catalytic activity is as described above, and an air electrode for oxygen generation can be obtained using the catalyst and the conductive material and binder described in the description of the air electrode.
  • FIG. 8 is a cross-sectional view showing one 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, Japanese Patent Application (See 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 Specifically, polyethylene oxide (PEO), polyvinylidene fluoride (PVDF, trade name Kynar (registered trademark), etc., manufactured by Arkema), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), etc.
  • the gelation can be performed by adding the polymer.
  • 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.
  • Example 1 ⁇ Double perovskite type transition metal oxide> Synthesis Example Double perovskite type transition metal oxide BaLnMn 2 O 5 (Ln: Y, Gd, Nd, or La) was synthesized by a vacuum sealed tube method and a firing method in an inert atmosphere.
  • Vacuum sealed tube method In the vacuum sealed tube method, an aqueous nitrate solution is prepared using Ba (NO 3 ) 2 , Ln 2 O 3 , and Mn (NO 3 ) 2 as raw materials. Precursors were synthesized by calcining at 450 ° C for 1 hour and 1000 ° C for 24 hours. This was vacuum sealed in a quartz tube with FeO as an oxygen getter, synthesized at 1100 ° C for 24 hours, and then rapidly cooled in ice water.
  • Baking method under inert atmosphere In BaLaMn 2 O 5 baking method under inert atmosphere, Ba (CH 3 COO) 2 , La (CH 3 COO) 3 ⁇ 1.5H 2 O, Mn (CH 3 COO) 2 ⁇ An aqueous acetate solution was prepared using 4H 2 O, the aqueous solution was gelled by heating and stirring, and then calcined at 350 ° C. for 1 hour in air to synthesize a precursor. This was synthesized by firing at 1000 ° C. for 12 hours in a nitrogen stream.
  • the obtained sample was subjected to phase identification and structural analysis by X-ray diffraction. From the X-ray diffraction pattern obtained by simulation and the previous reports [1-4], it was confirmed that a single phase of BaLnMn 2 O 5 (Ln: Y, Gd, Nd, La) was synthesized by the vacuum sealed tube method. ( Figure 1). In addition, it was confirmed from the X-ray diffraction that BaLaMn 2 O 5 was synthesized with a slightly lower crystallinity in the inert atmosphere firing method (with some MnO as an impurity) (FIG. 2).
  • the particle size and surface area were evaluated in the scanning electron microscope (SEM). It was confirmed that the samples synthesized by the vacuum sealed tube had an average particle size of about 1 to 2 ⁇ m and a surface area of about 0.25 to 0.75 m 2 g -1 for all samples (Fig. 3).
  • BaLaMn 2 O 5 synthesized by firing in an inert atmosphere has a particle size of about several hundred nanometers.
  • the surface area evaluated by the nitrogen adsorption method is 3.93 m 2 g -1, which is synthesized by the vacuum sealed tube method. It was found to be about 10 times ( Figure 4).
  • LaNiO 3 transition metal catalyst surface area 3.07 m 2 g -1
  • Electrochemical measurement (see Fig. 5)
  • three-electrode system Teflon (registered trademark) electrochemical cells are used, the counter electrode is a platinum plate, and the reference electrode is Hg. / HgO / KOH was used.
  • Sweep rate is -0.324 to 0.076 V vs Hg / HgO / KOH (1.00 to 0.60 V vs RHE) at 1 mV / s
  • the electrolyte is KOH with Ar saturation 4.0 mol dm -3
  • measurement was performed with an O 2 saturated solution in the same potential range, and ORR activity was evaluated from the difference between these current values.
  • the vacuum sealed tube method is suitable for synthesis on the order of milligrams, but when applied as the air electrode of a metal-air secondary battery, which is expected as a next-generation high-capacity secondary battery, the synthesis method on the order of grams is is necessary.
  • the ORR activity was evaluated in the same manner for a sample obtained by synthesizing BaLaMn 2 O 5 , which had the highest activity by the above-described method, by a firing method in an inert atmosphere.
  • the potential at -50 ⁇ A cm -2 was 0.925 V vs RHE, and succeeded in reducing the overvoltage by 0.05 V or more compared to the one synthesized by the vacuum sealed tube method.
  • This has a lower overvoltage than LaNiO 3 (0.910 V vs RHE @ 50 ⁇ A / cm 2 ), which is currently one of the transition metal oxides with the highest activity for ORR.
  • Example 2 ⁇ Oxygen deficient perovskite type> Synthesis Example The oxygen-deficient perovskite transition metal oxide La 1-x Ca x Mn 1-y Ni y O 3- ⁇ was synthesized by a citric acid gelation method using nitrate. La (NO 3 ) 3 ⁇ 6H 2 O, Ca (NO 3 ) 2 ⁇ 4H 2 O, Ni (NO 3 ) 2 ⁇ 6H 2 O, Mn (NO 3 ) 2 ⁇ 6H 2 O, citric acid The precursor was synthesized by gelling and calcining in air at 350 ° C. for 1 hour. This was further synthesized by baking at 600 ° C. for 12 hours. FIG.
  • FIG. 10 shows an XRD pattern of La 1-x Ca x Mn 0.5 Ni 0.5 O 3- ⁇ (0 ⁇ x ⁇ 0.5) obtained by firing at 600 ° C. It was confirmed that a single phase was synthesized in La 1-x Ca x Mn 0.5 Ni 0.5 O 3- ⁇ (0 ⁇ x ⁇ 0.2). On the other hand, when x> 0.3, formation of a NiO impurity phase was confirmed. As the amount of Ca substitution increased, the XRD peak shifted to the high angle side, suggesting a continuous increase in the valence of Mn and Ni.
  • FIG. 11 shows an SEM image of each sample.
  • the average particle size is about 30-40 nm, and when the surface area is determined by nitrogen adsorption measurement, the surface area is also about 20-30 m 2 g -1 , confirming that the surface area is high. did.
  • GC glassy carbon
  • LaNiO 3 transition metal catalyst surface area 3.07 m 2 g -1
  • a three-electrode Teflon (registered trademark) electrochemical cell was used for electrochemical measurement, a platinum plate was used for the counter electrode, and Hg / HgO / KOH was used for the reference electrode.
  • the electrolyte was measured with KOH aqueous solution of Ar saturated 4.0 mol dm -3 and then measured in the same potential range with O 2 saturated solution.
  • the ORR activity was evaluated from the difference in values.
  • FIG. 12 shows the results of electrochemical measurements of La 1-x Ca x Mn 0.5 Ni 0.5 O 3- ⁇ (0 ⁇ x ⁇ 0.5) synthesized by the citric acid gelation method.
  • currents derived from ORR were observed from around 0.93 to 0.90 V vs RHE.
  • the overvoltage with respect to ORR was smaller than LaNiO 3 by performing 10% Ca partial substitution.
  • x is preferably in the range of 0.1 to 0.3.
  • FIG. 14 shows the results of thermogravimetric (TG) analysis on a sample with a Ca substitution amount of 0 to 20%.
  • TG thermogravimetric
  • LaNiO 3 is -0.09 mA / cm 2 at 0.9 V vs RHE, while it is about -0.55 mA / cm 2 @ 0.9 V vs RHE, a reduction current 6 times larger than LaNiO 3.
  • Stability was evaluated by maintaining a constant potential for 24 h at 0.6 V vs RHE in which ORR occurs in an oxygen-saturated 4 mol dm -3 KOH aqueous solution, and performing XRD measurement and ORR activity evaluation before and after that. From the XRD measurement results before and after holding the constant potential (Fig. 16), the pattern of La 0.6 Ca 0.4 Mn 0.9 Ni 0.1 O 3-d was confirmed even after holding the constant potential, and acetylene added as a conductive auxiliary agent. Since no peaks other than black (AB) appeared, it was found that no impurities were generated even after holding at a constant potential, and that it was stable.
  • 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.

Abstract

La présente invention concerne un catalyseur pour la réaction de réduction de l'oxygène (ORR), qui ne contient pas de métal noble hautement actif. La présente invention concerne également : une électrode à air qui utilise ce catalyseur ORR ; et un accumulateur à air. La présente invention concerne : un catalyseur pour la réaction de réduction de l'oxygène, qui contient au moins un composé choisi dans le groupe constitué par des oxydes de métal de transition pérovskite doubles et des oxydes de métal de transition pérovskite pauvres en oxygène ; une électrode à air pour accumulateurs métal-air, qui contient ce catalyseur ; et un accumulateur métal-air qui comprend cette électrode à air, une électrode négative qui contient un matériau actif d'électrode négative, et un électrolyte qui est interposé entre l'électrode à air et l'électrode négative.
PCT/JP2016/053451 2015-02-18 2016-02-05 Catalyseur pour réaction de réduction de l'oxygène et électrode à air pour accumulateurs métal-air WO2016132932A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2017500604A JP6731199B2 (ja) 2015-02-18 2016-02-05 酸素還元反応用触媒及び金属空気二次電池用空気極

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2015029856 2015-02-18
JP2015-029856 2015-02-18
JP2015174841 2015-09-04
JP2015-174841 2015-09-04

Publications (1)

Publication Number Publication Date
WO2016132932A1 true WO2016132932A1 (fr) 2016-08-25

Family

ID=56688888

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/053451 WO2016132932A1 (fr) 2015-02-18 2016-02-05 Catalyseur pour réaction de réduction de l'oxygène et électrode à air pour accumulateurs métal-air

Country Status (2)

Country Link
JP (1) JP6731199B2 (fr)
WO (1) WO2016132932A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107293718A (zh) * 2017-06-26 2017-10-24 合肥国轩高科动力能源有限公司 R2‑xMxEMnO6改性镍锰酸锂材料及制备、应用
US20200119391A1 (en) * 2018-10-11 2020-04-16 Samsung Electronics Co., Ltd. Cathode and lithium-air battery including the cathode
CN111653789A (zh) * 2020-06-17 2020-09-11 泰州市海创新能源研究院有限公司 一种锌-空气电池催化剂及其制备方法
CN111668503A (zh) * 2020-07-20 2020-09-15 山东大学 一种双金属硫化物锂空气电池正极材料及其制备方法与应用
CN112226780A (zh) * 2020-10-17 2021-01-15 石河子大学 用于全解水的NiCo2S4/氮、硫共掺杂还原氧化石墨烯双功能电催化剂的制备方法
CN112946030A (zh) * 2021-02-03 2021-06-11 吉林大学 基于La2NiFeO6敏感电极的CeO2基三乙胺传感器、制备方法及其应用
CN113231108A (zh) * 2021-05-11 2021-08-10 江南大学 一种可低温催化氧化甲醛的纳米纤维膜材料及其制备方法与应用
CN116060076A (zh) * 2022-12-22 2023-05-05 厦门大学 氮磷掺杂石墨烯钙钛矿LaNiO3催化制氢催化剂及制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08504998A (ja) * 1992-10-30 1996-05-28 エア エナジー リソースィズ インコーポレイテッド 二官能性の空気電極
WO2010100752A1 (fr) * 2009-03-06 2010-09-10 トヨタ自動車株式会社 Electrode à air et batterie à air non aqueuse
JP2011016684A (ja) * 2009-07-08 2011-01-27 Hokkaido Univ 酸素貯蔵能に優れた酸素欠損ペロブスカイト型金属酸化物、該金属酸化物を含む排ガス浄化触媒及び機能セラミックス、及び、該金属酸化物を用いる方法及び装置
JP2013218986A (ja) * 2012-04-12 2013-10-24 Nippon Telegr & Teleph Corp <Ntt> リチウム空気二次電池
JP2013255911A (ja) * 2012-06-14 2013-12-26 Mitsubishi Chemicals Corp 合成ガス製造用触媒および合成ガスの製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08504998A (ja) * 1992-10-30 1996-05-28 エア エナジー リソースィズ インコーポレイテッド 二官能性の空気電極
WO2010100752A1 (fr) * 2009-03-06 2010-09-10 トヨタ自動車株式会社 Electrode à air et batterie à air non aqueuse
JP2011016684A (ja) * 2009-07-08 2011-01-27 Hokkaido Univ 酸素貯蔵能に優れた酸素欠損ペロブスカイト型金属酸化物、該金属酸化物を含む排ガス浄化触媒及び機能セラミックス、及び、該金属酸化物を用いる方法及び装置
JP2013218986A (ja) * 2012-04-12 2013-10-24 Nippon Telegr & Teleph Corp <Ntt> リチウム空気二次電池
JP2013255911A (ja) * 2012-06-14 2013-12-26 Mitsubishi Chemicals Corp 合成ガス製造用触媒および合成ガスの製造方法

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
FEIFEI DONG ET AL.: "Structural and oxygen- transport studies of double perovskites PrBa1-x Co2O5+delta (x = 0.00, 0.05, and 0.10) toward their application as superior oxygen reduction electrodes", JOURNAL OF MATERIALS CHEMISTRY A, vol. 2, no. 48, 2014, pages 20520 - 20529 *
HIROYUKI NODA: "Sanso Futeiseihi o Yusuru Kinzoku Sankabutsu no Sanso Kangen/Sanso Hassei Denkyoku Shokubai Kassei", KAGAKUKEI GAKUKYOKAI HOKKAIDO SHIBU TOKI KENKYU HAPPYOKAI KOEN YOSHISHU, vol. 1C07, 28 January 2014 (2014-01-28) *
JING DU ET AL.: "Nonstoichiometric Perovskite CaMnO3-delta for Oxygen Electrocatalysis with High Activity", INORGANIC CHEMISTRY, vol. 53, no. 17, 2014, pages 9106 - 9114 *
MABROUK CHERITI ET AL.: "Double perovskite oxides Sr2MMoO6 (M = Fe and Co) as cathode materials for oxygen reduction in alkaline medium", MATERIALS RESEARCH BULLETIN, vol. 47, no. 1, 2012, pages 135 - 141 *
SEONYOUNG YOO ET AL.: "Development of Double- Perovskite Compounds as Cathode Materials for Low-Temperature Solid Oxide Fuel Cells", ANGEWANDTE CHEMIE INTERNATIONAL EDITION, vol. 53, 2014, pages 13064 - 13067 *
YAN LI ET AL.: "Oxygen-Deficient Perovskite Sr0.7Y0.3CoO2.65-delta as a Cathode for Intermediate-Temperature Solid Oxide Fuel Cells", CHEMISTRY OF MATERIALS, vol. 23, no. 22, 2011, pages 5037 - 5044 *
ZHONG MA ET AL.: "The double perovskite oxide Sr2CrMoO6-delta as an efficient electrocatalyst for rechargeable lithium air batteries", CHEMICAL COMMUNICATIONS, vol. 50, no. 94, 2014, pages 14855 - 14858 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107293718B (zh) * 2017-06-26 2020-05-26 合肥国轩高科动力能源有限公司 R2-xMxEMnO6改性镍锰酸锂材料及制备、应用
CN107293718A (zh) * 2017-06-26 2017-10-24 合肥国轩高科动力能源有限公司 R2‑xMxEMnO6改性镍锰酸锂材料及制备、应用
US20200119391A1 (en) * 2018-10-11 2020-04-16 Samsung Electronics Co., Ltd. Cathode and lithium-air battery including the cathode
US11848411B2 (en) * 2018-10-11 2023-12-19 Samsung Electronics Co., Ltd. Cathode and lithium-air battery including the cathode
CN111653789A (zh) * 2020-06-17 2020-09-11 泰州市海创新能源研究院有限公司 一种锌-空气电池催化剂及其制备方法
CN111668503A (zh) * 2020-07-20 2020-09-15 山东大学 一种双金属硫化物锂空气电池正极材料及其制备方法与应用
CN112226780B (zh) * 2020-10-17 2023-09-29 石河子大学 用于全解水的NiCo2S4/氮、硫共掺杂还原氧化石墨烯双功能电催化剂的制备方法
CN112226780A (zh) * 2020-10-17 2021-01-15 石河子大学 用于全解水的NiCo2S4/氮、硫共掺杂还原氧化石墨烯双功能电催化剂的制备方法
CN112946030A (zh) * 2021-02-03 2021-06-11 吉林大学 基于La2NiFeO6敏感电极的CeO2基三乙胺传感器、制备方法及其应用
CN112946030B (zh) * 2021-02-03 2022-02-08 吉林大学 基于La2NiFeO6敏感电极的CeO2基三乙胺传感器、制备方法及其应用
CN113231108B (zh) * 2021-05-11 2022-06-21 江南大学 一种可低温催化氧化甲醛的纳米纤维膜材料及其制备方法与应用
CN113231108A (zh) * 2021-05-11 2021-08-10 江南大学 一种可低温催化氧化甲醛的纳米纤维膜材料及其制备方法与应用
CN116060076A (zh) * 2022-12-22 2023-05-05 厦门大学 氮磷掺杂石墨烯钙钛矿LaNiO3催化制氢催化剂及制备方法

Also Published As

Publication number Publication date
JP6731199B2 (ja) 2020-07-29
JPWO2016132932A1 (ja) 2017-11-30

Similar Documents

Publication Publication Date Title
JP6731199B2 (ja) 酸素還元反応用触媒及び金属空気二次電池用空気極
Liu et al. General synthesis of x Li 2 MnO 3·(1− x) LiMn 1/3 Ni 1/3 Co 1/3 O 2 nanomaterials by a molten-salt method: towards a high capacity and high power cathode for rechargeable lithium batteries
KR101257852B1 (ko) 리튬 공기 전지용 양극, 그 제조방법 및 이를 채용한 리튬 공기 전지
JP6257066B2 (ja) リチウムイオン２次電池用リチウムマンガン酸化物正極活物質およびそれを含むリチウムイオン２次電池
EP2985260A1 (fr) Composite pour batterie lithium-air, procédé de préparation du matériau composite et batterie lithium-air utilisant une électrode positive comprenant le composite
JP5733912B2 (ja) リチウム空気二次電池用の正極とその製造方法ならびにリチウム空気二次電池
JP6436444B2 (ja) 亜鉛−空気二次電池の空気極用触媒、ブラウンミラーライト型遷移金属酸化物の亜鉛−空気二次電池の空気極用触媒としての使用、亜鉛−空気二次電池用空気極、亜鉛−空気二次電池、電解用の電極触媒、電解用電極及び電解方法
US20130316253A1 (en) Method for producing cathode material for rechargeable lithium-air batteries, cathode material for rechargeable lithium-air batteries and rechargeable lithium-air battery
JP5580931B2 (ja) 金属−空気二次電池用正極触媒及び金属−空気二次電池
WO2020096022A1 (fr) Matériau pour catalyseur d&#39;électrode de dégagement d&#39;oxygène (oer) et son utilisation
KR101550956B1 (ko) 금속 도핑된 양극 활물질
CN113611856B (zh) 正极材料及其制备方法、锂离子电池
JP5594241B2 (ja) 電解液及びリチウムイオン二次電池
WO2019093441A1 (fr) Oxyde de métal de transition amorphe et son utilisation
JP2016071970A (ja) 酸化物複合体及び非水系リチウムイオン二次電池
JP5032038B2 (ja) 非水電解質電池用電極材料、非水電解質電池および電池パック
JP5562204B2 (ja) リチウム空気二次電池用正極とその製造方法ならびにリチウム空気二次電池
JP2015187929A (ja) 非水電解質二次電池
JP2015069960A (ja) リチウム空気二次電池
JP6059632B2 (ja) リチウム空気二次電池
JP5643182B2 (ja) リチウム空気二次電池及びその空気極作製方法
KR20210123900A (ko) 내염기성이 우수한 양극, 이의 제조방법, 및 이를 포함하는 금속공기전지 및 전기화학소자
US20220199992A1 (en) Cathode material, cathode including the same, and lithium-air battery including the cathode
JP6995346B2 (ja) リチウム二次電池用の正極材料およびその製造方法
KR20110021384A (ko) 신규한 리튬 이차전지용 양극 활물질 및 이를 이용한 리튬 이차전지용 양극 박막의 제조방법

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16752319

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017500604

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16752319

Country of ref document: EP

Kind code of ref document: A1