JPWO2016132932A1 - Catalyst for oxygen reduction reaction and air electrode for metal-air secondary battery - Google Patents
Catalyst for oxygen reduction reaction and air electrode for metal-air secondary battery Download PDFInfo
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- JPWO2016132932A1 JPWO2016132932A1 JP2017500604A JP2017500604A JPWO2016132932A1 JP WO2016132932 A1 JPWO2016132932 A1 JP WO2016132932A1 JP 2017500604 A JP2017500604 A JP 2017500604A JP 2017500604 A JP2017500604 A JP 2017500604A JP WO2016132932 A1 JPWO2016132932 A1 JP WO2016132932A1
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- catalyst
- oxygen
- transition metal
- reduction reaction
- metal oxide
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- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- DMFBPGIDUUNBRU-UHFFFAOYSA-N magnesium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Mg+2].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F DMFBPGIDUUNBRU-UHFFFAOYSA-N 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000002429 nitrogen sorption measurement Methods 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 description 1
- 239000002203 sulfidic glass Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000005469 synchrotron radiation Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- QEORIOGPVTWFMH-UHFFFAOYSA-N zinc;bis(trifluoromethylsulfonyl)azanide Chemical compound [Zn+2].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QEORIOGPVTWFMH-UHFFFAOYSA-N 0.000 description 1
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
Abstract
本発明は、高活性な貴金属を含まない酸素還元反応(ORR)触媒を提供する。このORR触媒を用いた空気極及び空気二次電池を提供する。本発明は、ダブルペロブスカイト型遷移金属酸化物及び酸素欠損ペロブスカイト型遷移金属酸化物から成る群から選ばれる少なくとも1種の化合物を含む酸素還元反応用触媒、この触媒を含む金属空気二次電池用空気極、この空気極と、負極活物質を含有する負極と、空気極と負極との間に介在する電解質と、を有する金属空気二次電池に関する。The present invention provides an oxygen reduction reaction (ORR) catalyst free of highly active noble metals. An air electrode and an air secondary battery using the ORR catalyst are provided. The present invention relates to an oxygen reduction reaction catalyst comprising at least one compound selected from the group consisting of a double perovskite type transition metal oxide and an oxygen deficient perovskite type transition metal oxide, and an air for a metal-air secondary battery containing this catalyst. The present invention relates to a metal-air secondary battery having an electrode, the air electrode, a negative electrode containing a negative electrode active material, and an electrolyte interposed between the air electrode and the negative electrode.
Description
本発明は、高活性の酸素還元反応用触媒及び金属空気二次電池用空気極に関する。
関連出願の相互参照
本出願は、２０１５年２月１８日出願の日本特願２０１５−０２９８５６号および２０１５年９月４日出願の日本特願２０１５−１７４８４１号の優先権を主張し、それらの全記載は、ここに特に開示として援用される。The present invention relates to a highly active catalyst for oxygen reduction reaction and an air electrode for a metal-air secondary battery.
This application claims the priority of Japanese Patent Application No. 2015-029856 filed on Feb. 18, 2015 and Japanese Patent Application No. 2015-174841 filed on Sep. 4, 2015. The description is hereby specifically incorporated by reference.
リチウムイオン二次電池は様々なところで利用されており、最近では化石燃料を使わないクリーンな電気自動車への搭載も進められている。しかしながらその容量は十分とは言えず、ガソリン車並みの走行距離を実現するには更なる高容量化が必須であり、リチウムイオン二次電池に代わる革新的蓄電池の開発が盛んに行われている。中でも金属空気二次電池は正極反応の燃料として外気から取り入れた空気を用いるため、電池本体の大部分に負極燃料を充填することができる。そのため、例えば安全性に優れている亜鉛空気二次電池においても、理論的には現状のリチウムイオン二次電池の5〜10倍もの高容量化が可能である。 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. . In particular, since 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. Therefore, for example, even in a zinc-air secondary battery that is excellent in safety, it is theoretically possible to increase the capacity 5 to 10 times that of the current lithium ion secondary battery.
しかしながら現状では様々な課題が残されており、その1つとして挙げられるのが、正極に用いられる高活性酸素還元反応（Oxygen Reduction Reaction (ORR)）触媒の開発である。一般にORRには大きな過電圧が生じることが知られており、このために十分な出力での放電ができていないのが現状である。またこのことは同じく正極反応がORRであり、既に実用化されているアルカリ形燃料電池においても言えることである。そのため、放電時の電圧を大きく左右する高活性ORR触媒の開発が急務となっている。 However, various problems remain, and one of them is the development of a highly active oxygen reduction reaction (ORR) catalyst used for the positive electrode. In general, it is known that a large overvoltage occurs in the ORR, and for this reason, the discharge is not performed with a sufficient output. This is also true for alkaline fuel cells that have already been put to practical use because the positive electrode reaction is ORR. Therefore, there is an urgent need to develop a highly active ORR catalyst that greatly affects the voltage during discharge.
一般的にORRに対して高活性な触媒として、PtやPdなどの貴金属触媒が知られているが、これら貴金属はコストが高く埋蔵量も少ないため、広く普及させるためには貴金属を含まないORR触媒の開発が必要である。 In general, noble metal catalysts such as Pt and Pd are known as highly active catalysts for ORR. However, these noble metals are expensive and have a small reserve, so they are free of ORR for widespread use. Catalyst development is required.
最近では貴金属を含まない非貴金属ORR触媒として、ペロブスカイト型遷移金属酸化物ABO3が報告されている。ペロブスカイト型酸化物はBサイトに遷移金属を有し、酸素6つと結合した八面体構造から成る。最近ではこのBサイト遷移金属のeg電子数がそのORR活性と関連していることが報告されており、eg電子数が1付近のLaNiO3などが高活性 [非特許文献1,2]であることが報告されている。Recently, a 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. Recently, it has been reported that 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.
非特許文献１：J. Suntivich, H. A. Gasteiger, N. Yabuuchi, H. Nakanishi, J. B. Goodenough and Y. S.-Horn, Nature Chem. 2012, 3, 546-550.
非特許文献２：J. Suntivich, H. A. Gasteiger, N. Yabuuchi and Y. S.-Horn, J. Electrochem. Soc. 2010, 157, B1263-B1268.
非特許文献３：F. Millange et al., Mater. Res. Bull. 1999, 34, 1.
非特許文献４：C. Perca et al., Chem. Mater. 2005, 17, 1835.
非特許文献５：A. J. Williams et al., Phys. Rev. B 2005, 72, 024436.
非特許文献６：V. Vashook et al., Solid State Ionics 2008, 179, 135.Non-Patent Document 1: J. Suntivich, HA Gasteiger, N. Yabuuchi, H. Nakanishi, JB Goodenough and YS-Horn, Nature Chem. 2012, 3, 546-550.
Non-Patent Document 2: J. Suntivich, HA Gasteiger, N. Yabuuchi and YS-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: AJ Williams et al., Phys. Rev. B 2005, 72, 024436.
Non-Patent Document 6: V. Vashook et al., Solid State Ionics 2008, 179, 135.
しかし、非特許文献1及び2に記載の遷移金属酸化物触媒においてもその触媒活性は十分とは言えず、更なる高活性遷移金属酸化物群の開発が必要である。 However, even the transition metal oxide catalysts described in 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.
そこで本発明の目的は、非特許文献1及び2に記載の遷移金属酸化物より、さらに高活性な貴金属を含まないORR触媒を提供することにある。さらに本発明は、この触媒を用いた空気極及び空気二次電池を提供することも発明の目的とする。 Accordingly, an object of the present invention is to provide an ORR catalyst that does not contain a noble metal having higher activity 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.
本発明者らは、上記課題を解決すべく、種々の検討を行った結果、ダブルペロブスカイト型遷移金属酸化物及び酸素欠損ペロブスカイト型遷移金属酸化物が優れたORR触媒を有することを見出して本発明を完成させた。 As a result of various studies to solve the above problems, the present inventors have found that double perovskite type transition metal oxides and oxygen-deficient perovskite type transition metal oxides have excellent ORR catalysts. Was completed.
本発明は以下のとおりである。
［１］
ダブルペロブスカイト型遷移金属酸化物及び酸素欠損ペロブスカイト型遷移金属酸化物から成る群から選ばれる少なくとも1種の化合物を含む酸素還元反応用触媒。
［２］
前記ダブルペロブスカイト型遷移金属酸化物が、一般式BaLnMn2O5+δ（式中、LnはY，Er，Ho，Dy，Tb，Gd，Eu，Sm，Nd，Pr，及びLaから成る群から選ばれる少なくとも1種の遷移金属であり、δは0〜1の数値である）で表される［１］に記載の酸素還元反応用触媒。
［３］
前記一般式BaLnMn2O5+δは、AサイトにBaとLn、Bサイトにマンガンを有するペロブスカイト関連化合物であり、酸素6つと結合した八面体構造、あるいは酸素5つと結合したピラミッド構造から成る［２］に記載の酸素還元反応用触媒。
［４］
前記酸素欠損ペロブスカイト型遷移金属酸化物が、A1-xA’xB1-yB’yO3-δ（A: +3価のカチオン、A’: +2価のカチオン、B、B’: 独立に遷移金属イオン、0≦x≦0.5、0≦y≦0.5、δ>0）で表される［１］に記載の酸素還元反応用触媒。
［５］
前記一般式A1-xA’xB1-yB’yO3-δは、一般式A1-xA’xMn1-yNiyO3-δで表される酸素欠損ペロブスカイト型遷移金属酸化物である［４］に記載の酸素還元反応用触媒。
［６］
前記一般式A1-xA’xMn1-yNiyO3-δにおいて、AはLa、Pr、Nd、Sm、Eu、及びGdから成る群から選ばれる少なくとも1種の希土類であり、A’はCa及び／又はSrである［５］に記載の酸素還元反応用触媒。
［７］
前記酸素還元反応が水溶液中での酸素分子の還元反応である［１］〜［６］のいずれかに記載の酸素還元反応用触媒。
［８］
表面積が0.1〜100m2/gの範囲である［１］〜［７］のいずれかに記載の酸素還元反応用触媒。
［９］
空気電極用である［１］〜［８］のいずれかに記載の酸素還元反応用触媒。
［１０］
［１］〜［８］のいずれかに記載のダブルペロブスカイト型遷移金属酸化物及び酸素欠損ペロブスカイト型遷移金属酸化物から成る群から選ばれる少なくとも1種の化合物の酸素還元反応用触媒又は空気電極用触媒としての使用。
［１１］
［１］〜［８］のいずれかに記載の触媒を含む金属空気二次電池用空気極。
［１２］
前記ダブルペロブスカイト型遷移金属酸化物及び酸素欠損ペロブスカイト型遷移金属酸化物から成る群から選ばれる少なくとも1種の化合物は酸素還元反応用触媒として含有され、酸素発生用触媒をさらに含む［１１］に記載の空気極。
［１３］
多孔質構造を有し、かつ導電性材料をさらに含む［１１］又は［１２］に記載の空気極。
［１４］
［１１］〜［１３］のいずれかに記載の空気極と、負極活物質を含有する負極と、前記空気極と前記負極との間に介在する電解質と、を有する金属空気二次電池。
［１５］
酸素還元用触媒を含む酸素還元用空気極をさらに含む［１４］に記載の金属空気二次電池。The present invention is as follows.
[1]
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.
[2]
The double perovskite transition metal oxide has a general formula BaLnMn 2 O 5 + δ (where Ln is a group consisting of Y, Er, Ho, Dy, Tb, Gd, Eu, Sm, Nd, Pr, and La). The oxygen reduction reaction catalyst according to [1], which is at least one selected transition metal, and δ is a numerical value of 0 to 1.
[3]
The general formula BaLnMn 2 O 5 + δ 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].
[4]
The oxygen-deficient perovskite transition metal oxide is A 1-x A ′ x B 1-y B ′ y O 3-δ (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, δ> 0).
[5]
The general formula A 1-x A ′ x B 1-y B ′ y O 3-δ is an oxygen deficient perovskite type represented by the general formula A 1-x A ′ x Mn 1-y Ni y O 3-δ The catalyst for oxygen reduction reaction according to [4], which is a transition metal oxide.
[6]
In the general formula A 1-x A ′ x Mn 1-y Ni y O 3-δ , A is at least one rare earth selected from the group consisting of La, Pr, Nd, Sm, Eu, and Gd, The catalyst for oxygen reduction reaction according to [5], wherein A ′ is Ca and / or Sr.
[7]
The catalyst for oxygen reduction reaction according to any one of [1] to [6], wherein the oxygen reduction reaction is a reduction reaction of oxygen molecules in an aqueous solution.
[8]
The catalyst for oxygen reduction reaction according to any one of [1] to [7], wherein the surface area is in the range of 0.1 to 100 m 2 / g.
[9]
The catalyst for oxygen reduction reaction according to any one of [1] to [8], which is for an air electrode.
[10]
For oxygen reduction reaction catalyst or air electrode of at least one compound selected from the group consisting of double perovskite type transition metal oxide and oxygen deficient perovskite type transition metal oxide according to any one of [1] to [8] Use as a catalyst.
[11]
The air electrode for metal air secondary batteries containing the catalyst in any one of [1]-[8].
[12]
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.
[13]
The air electrode according to [11] or [12], which has a porous structure and further includes a conductive material.
[14]
[11] A metal-air secondary battery comprising the air electrode according to any one of [13] to [13], a negative electrode containing a negative electrode active material, and an electrolyte interposed between the air electrode and the negative electrode.
[15]
[14] The metal-air secondary battery according to [14], further including an oxygen reduction air electrode including an oxygen reduction catalyst.
本発明によれば、ダブルペロブスカイト型遷移金属酸化物及び酸素欠損ペロブスカイト型遷移金属酸化物から成る群から選ばれる少なくとも1種の化合物を用いることで、LaNiO3よりさらに高活性のORR触媒を提供することができる。さらに、本発明によれば上記ORR触媒を用いた金属空気二次電池用空気極、及びこの空気極を用いた金属空気二次電池も提供できる。According to the present invention, by using at least one compound selected from the group consisting of a double perovskite type transition metal oxide and an oxygen deficient perovskite type transition metal oxide, an ORR catalyst having higher activity than LaNiO 3 is provided. be able to. Furthermore, according to the present invention, 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.
＜酸素還元反応用触媒＞
本発明は、ダブルペロブスカイト型遷移金属酸化物(Double perovskite-type transition metal oxides)及び酸素欠損ペロブスカイト型遷移金属酸化物(Oxygen-deficient perovskite-type transition metal oxides)から成る群から選ばれる少なくとも1種の化合物を含む酸素還元反応用触媒(Catalysts for oxygen reduction reaction)に関する。<Catalyst for oxygen reduction reaction>
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.
ペロブスカイト、及びダブルペロブスカイト（酸素欠損なし）について
a. 一般にペロブスカイトは、一般式「ABO3（A: 希土類など、B: 遷移金属など）」であらわされる化合物で、A:B:O=1:1:3を満たす。具体例としては、LaMnO3、LaCoO3、LaNiO3などが該当する。About perovskite and double perovskite (no oxygen deficiency)
In general, perovskite is a compound represented by the general formula “ABO 3 (A: rare earth, B: transition metal, etc.)” and satisfies A: B: O = 1: 1: 3. Specific examples include LaMnO 3 , LaCoO 3 , and LaNiO 3 .
b. 次に、Aサイト、及びBサイトに複数の元素を有しているペロブスカイトは、例えば、AサイトにA、A’、BサイトにB、B’とそれぞれ2種類の元素を含んでいる場合には、A1-xA’xB1-yB’yO3（0≦x≦1、0≦y≦1） で表され、[(1-x)A+xA’]: [(1-y)B+yB’]:O=1:1:3を満たす。具体例としては、Ba0.8Sr0.2Co0.5Fe0.5O3などが該当する。b. Next, 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.
c. 上記bにおいて、AとA’、あるいはBとB’が規則的に配列しているペロブスカイトを特別に、ダブルペロブスカイトと呼ぶ（ダブルペロブスカイトの構造は、後述する）。この際、化学式でペロブスカイトと区別できるように、ダブルペロブスカイトは、bのそれぞれの原子数を2倍して、A2(1-x)A’2xB2(1-y)B’2yO6（0≦x≦1、0≦y≦1）と表記する。例えば、Ba0.5La0.5MnO3とBaLaMn2O6とを比較すると（ここではB=B’=Mn）、前者がAサイトにBaとLaが1:1でランダムに混ざっているペロブスカイトであるのに対し、後者はAサイトにBaとLaが交互に積層しているペロブスカイト、つまりダブルペロブスカイトを表す。c. In the above b, 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). In this case, 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). For example, when comparing Ba 0.5 La 0.5 MnO 3 and BaLaMn 2 O 6 (here B = B '= Mn), the former is a perovskite with a 1: 1 mixture of Ba and La at the A site. On the other hand, the latter represents a perovskite in which Ba and La are alternately laminated on the A site, that is, a double perovskite.
＜ダブルペロブスカイト型遷移金属酸化物＞
本発明のダブルペロブスカイト型遷移金属酸化物は、例えば、一般式BaLnMn2O5+δで表される遷移金属酸化物であることができ、式中のLnはY，Er，Ho，Dy，Tb，Gd，Eu，Sm，Nd，Pr，及びLaからなる少なくとも１種の遷移金属酸化物であることができる。<Double perovskite type transition metal oxide>
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 + δ , where Ln is Y, Er, Ho, Dy, Tb. , Gd, Eu, Sm, Nd, Pr, and La can be at least one transition metal oxide.
ダブルペロブスカイトは、前述のように一般には、一般式A2(1-x)A’2xB2(1-y)B’2yO6（0≦x≦1、0≦y≦1）と表記される化合物であり、6個の酸素原子を含む。一方、本発明における上記一般式BaLnMn2O5+δで表されるダブルペロブスカイト型遷移金属酸化物は、δが0〜1の範囲の数値である。δ=1の場合は、上記A2(1-x)A’2xB2(1-y)B’2yO6（0≦x≦1、0≦y≦1）と表記される化合物に相当する。δが0以上、1未満の範囲の数値の場合には、上記化学式における酸素原子の個数は6個未満であり、酸素欠損状態である。一般式A2(1-x)A’2xB2(1-y)B’2yO6（0≦x≦1、0≦y≦1）と表記されるダブルペロブスカイトが酸素欠損状態となるのは、化合物の電荷は0(ゼロ)であるから、A、A’、B、及びB’の少なくとも1つの原子が+3価未満の価数を有する原子である場合である。また、A、A’、B、及びB’の少なくとも1つの原子が、+3価未満の価数を有する原子であるダブルペロブスカイトが酸素欠損のない状態(δ=1に相当する)となる場合もあり、具体的には、+3価未満の価数を有する原子以外の少なくとも1つの原子が+3価を超える価数を有する場合である。As described above, 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. On the other hand, the double perovskite type transition metal oxide represented by the general formula BaLnMn 2 O 5 + δ in the present invention has a value in the range of δ from 0 to 1. In the case of δ = 1, it corresponds to the compound expressed as A 2 (1-x) A ′ 2x B 2 (1-y) B ′ 2y O 6 (0 ≦ x ≦ 1, 0 ≦ y ≦ 1) To do. When δ is a numerical value in the range of 0 or more and less than 1, the number of oxygen atoms in the above chemical formula is less than 6, which is an oxygen deficient state. 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). In addition, when at least one atom of A, A ′, B, and B ′ is an atom having a valence less than +3, the double perovskite is in a state without oxygen deficiency (corresponding to δ = 1) Specifically, this is the case where at least one atom other than an atom having a valence less than +3 has a valence greater than +3.
本発明の上記一般式BaLnMn2O5+δで表されるダブルペロブスカイト型遷移金属酸化物の場合、Baが+2価の原子であるので、Ln及びMnが+3価の場合、δ=0.5である。それに対して、δ=0の場合には、Mnの少なくとも一部が+3価未満の価数であり、δ=0.5の場合と同様に、化合物は酸素欠損状態である。一方、δ=1の場合には、Mnの少なくとも一部が+3価を超える価数であり、酸素欠損のない状態である。In the case of the double perovskite type transition metal oxide represented by the general formula BaLnMn 2 O 5 + δ of the present invention, since Ba is a +2 valent atom, when Ln and Mn are +3 valent, δ = 0.5 It is. On the other hand, when δ = 0, at least a part of Mn has a valence less than +3, and the compound is in an oxygen deficient state as in the case of δ = 0.5. On the other hand, when δ = 1, at least a part of Mn has a valence exceeding +3 valence, and there is no oxygen deficiency.
一般式BaLnMn2O5+δで表されるダブルペロブスカイト型遷移金属酸化物の酸素還元反応用触媒の性能は、Lnの種類によって変化する。酸素還元反応用触媒の活性が高いという観点から、LnはNdまたはLaであることが好ましく、Laであることが特に好ましい。δは0〜1の範囲の数値であり、主に0、0.5または1を取るが、実際の化合物では、それぞれの場合において、多少の酸素欠陥や酸素過剰（見かけ上、δが1を超える）の状態もあり得る。δ=0は酸素放出状態の化合物であり、δ=0.5は酸素部分吸収状態の化合物であり、δ=1は酸素吸収状態の化合物である。The performance of an oxygen reduction reaction catalyst of a double perovskite transition metal oxide represented by the general formula BaLnMn 2 O 5 + δ varies depending on the type of Ln. From the viewpoint of high activity of the oxygen reduction reaction catalyst, Ln is preferably Nd or La, and particularly preferably La. δ is a numerical value in the range of 0 to 1 and mainly takes 0, 0.5, or 1. In actual compounds, in each case, some oxygen defects or excess oxygen (apparently δ exceeds 1) There may also be a situation. δ = 0 is a compound in an oxygen releasing state, δ = 0.5 is a compound in an oxygen partial absorption state, and δ = 1 is a compound in an oxygen absorption state.
一般式BaLnMn2O5+δで表される遷移金属酸化物であるダブルペロブスカイト型遷移金属酸化物は、AサイトにBaとLnを有し、Bサイトにマンガンを有するペロブスカイト関連化合物(perovskite-related compounds)であり、酸素6つと結合した八面体構造(octahedrally-coordinated structures)、あるいは酸素5つと結合したピラミッド構造(pyramidally-coordinated structures)から成る。結晶構造の模式図を以下に示す。酸素6つと結合した八面体構造はδ=0.5とδ=1の化合物において現れ、酸素5つと結合したピラミッド構造はδ=0とδ=0.5の化合物に現れる。δ=0.5の場合は、八面体構造とピラミッド構造が共存する。A double perovskite type transition metal oxide, which is a transition metal oxide represented by the general formula BaLnMn 2 O 5 + δ , 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. A schematic diagram of the crystal structure is shown below. An octahedral structure bonded to 6 oxygens appears in a compound of δ = 0.5 and δ = 1, and a pyramid structure bonded to 5 oxygens appears in a compound of δ = 0 and δ = 0.5. In the case of δ = 0.5, the octahedral structure and the pyramid structure coexist.
一般式BaLnMn2O5+δで表されるダブルペロブスカイト型遷移金属酸化物は、例えば、非特許文献３〜５において報告されており、物質としては知られている。一般式BaLnMn2O5で表されるダブルペロブスカイト型遷移金属酸化物(δ=0)の製法は、例えば、金属硝酸塩等の塩を出発原料とし、クエン酸法(citrate routes)により作製した前駆体を用いて、真空封管法(vacuum encapsulation method)により合成することができる。あるいは、金属酢酸酸塩等の塩を出発原料とし不活性雰囲気下で焼成する方法（不活性雰囲気下焼成法(firing under inert atmospheres））によっても合成することはできる。Double perovskite type transition metal oxides represented by the general formula BaLnMn 2 O 5 + δ are reported, for example, in Non-Patent Documents 3 to 5, and are known as substances. The method for producing a double perovskite type transition metal oxide (δ = 0) represented by the general formula BaLnMn 2 O 5 is, for example, a precursor prepared by a citric acid method (citrate routes) using a salt such as a metal nitrate as a starting material. Can be synthesized by a vacuum encapsulation method. Alternatively, 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).
また、δ=0.5とδ=1の化合物は、一般式BaLnMn2O5で表されるダブルペロブスカイト型遷移金属酸化物(δ=0)を含酸素雰囲気中でのポストアニール(post-annealing)（後熱処理(post-heat treatment)）すること、あるいは電解酸化すること(electrochemical oxidation)で得られる。ポストアニールによるδ=0.5の化合物及びδ=1の化合物の調製は、Lnの種類及びδに応じて、含酸素雰囲気中の酸素濃度及び温度条件をコントロールすることで実施できる。δ=0.5の化合物は、δ=0の化合物を酸化する以外にδ=1の化合物を還元雰囲気下で部分還元することでも調製できる。δ=1の化合物は、例えば、酸素または空気あるいはその他の含酸素雰囲気中で、２００〜６００℃、０.５〜１２時間の条件で調製することができる。δ=0.5の化合物は、δ=1まで酸化が進まず、δ=0.5で止めるために、δ=1の化合物の調製の場合に比べてLnの種類に応じて酸化条件を厳密に制御する必要がある。LnがYの場合、δ=0の化合物を、例えば、０.１ｖｏｌ％以下の酸素濃度の含酸素雰囲気中で７００〜７５０℃、３〜１２時間加熱することで、δ=0.5の化合物が得られる。あるいは、δ=1の化合物(相)を調製し、これを窒素中で７５０℃、３〜１２時間加熱することでもδ=0.5の化合物が得られる。LnがLa, Nd, Gdの場合、δ=0の化合物を、例えば、０.１ｖｏｌ％以下の酸素濃度、２００〜３５０℃で加熱しながらＴＧで重量の経時変化を測定し、δ=0.5に相当する重量増加の所で試料を急冷することでδ=0.5の化合物が得られる。Further, a compound of δ = 0.5 and δ = 1 is obtained by subjecting a double perovskite transition metal oxide (δ = 0) represented by the general formula BaLnMn 2 O 5 to post-annealing in an oxygen-containing atmosphere (post-annealing ( It can be obtained by post-heat treatment) or by electrochemical oxidation. Preparation of a compound of δ = 0.5 and a compound of δ = 1 by post-annealing can be performed by controlling the oxygen concentration and temperature conditions in the oxygen-containing atmosphere according to the type of Ln and δ. A compound with δ = 0.5 can also be prepared by partially reducing the compound with δ = 1 in a reducing atmosphere in addition to oxidizing the compound with δ = 0. The compound of δ = 1 can be prepared, for example, under conditions of 200 to 600 ° C. and 0.5 to 12 hours in oxygen, air or other oxygen-containing atmosphere. The compound of δ = 0.5 does not proceed to oxidation until δ = 1 and stops at δ = 0.5. Therefore, it is necessary to strictly control the oxidation conditions according to the type of Ln compared to the preparation of the compound of δ = 1. There is. When Ln is Y, a compound of δ = 0 is obtained by heating a compound of δ = 0, for example, at 700 to 750 ° C. for 3 to 12 hours in an oxygen-containing atmosphere having an oxygen concentration of 0.1 vol% or less. It is done. Alternatively, a compound (phase) with δ = 1 is prepared and heated in nitrogen at 750 ° C. for 3 to 12 hours to obtain a compound with δ = 0.5. When Ln is La, Nd, or Gd, the compound with δ = 0 is measured for change in weight over time with TG while heating at an oxygen concentration of 0.1 vol% or less at 200 to 350 ° C., and δ = 0.5. By quenching the sample at a corresponding weight increase, a compound with δ = 0.5 is obtained.
さらに、一般式BaLnMn2O5+δで表されるダブルペロブスカイト型遷移金属酸化物のδ=0、δ=0.5及びδ=1の各化合物は、X線回折実験(X-ray diffraction analyses) により判別できる。Furthermore, each compound of δ = 0, δ = 0.5 and δ = 1 of the double perovskite type transition metal oxide represented by the general formula BaLnMn 2 O 5 + δ is determined by X-ray diffraction experiments. Can be determined.
真空封管法では、硝酸バリウム、遷移金属酸化物(transition metal oxides)及び希土類硝酸塩(rare earth element nitrates)を所定の比率でクエン酸と混合してゲル化した後、ゲル化した混合物を空気中で３５０〜６００℃で０．１〜６時間、次いで窒素雰囲気下で９００〜１０００℃で１〜７２時間加熱して酸化物前駆体を形成する。次いで酸化物前駆体を酸素ゲッター（例えば、一酸化鉄ＦｅＯ）の存在下に真空封管し、１０００〜１２００℃で１〜７２時間加熱し、加熱終了後に急冷することで、ダブルペロブスカイト型遷移金属酸化物が得られる。 In the vacuum sealed tube method, barium nitrate, transition metal oxides, and rare earth element nitrates are mixed with citric acid at a predetermined ratio to gel, and then the gelled mixture is put into air. To 350 to 600 ° C. for 0.1 to 6 hours, and then in a nitrogen atmosphere at 900 to 1000 ° C. for 1 to 72 hours to form an oxide precursor. Next, 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 completion of heating, whereby a double perovskite transition metal An oxide is obtained.
不活性雰囲気下焼成法では、酢酸バリウム、遷移金属酢酸塩及び希土類酢酸塩を所定の比率で混合し、酢酸水溶液とした後、得られた酢酸水溶液を６０〜７０℃で加熱して水を除去し、次いで空気中で３５０〜６００℃で０．１〜６時間加熱して前駆体を形成する。次いで前駆体を窒素雰囲気下（好ましくは窒素気流中）、９００〜１１００℃で１〜７２時間加熱することで、ダブルペロブスカイト型遷移金属酸化物が得られる。 In the firing method under an inert atmosphere, 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. The precursor is then 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 transition metal oxide.
真空封管法の方が、結晶性が良好なダブルペロブスカイト型遷移金属酸化物が得られる傾向があり、不活性雰囲気下焼成法では、ダブルペロブスカイト型遷移金属酸化物の結晶性がやや劣ることがある。一方、ダブルペロブスカイト型遷移金属酸化物の表面積は、不活性雰囲気下焼成法で得られた試料の方が大きい傾向がある。但し、結晶性及び表面積については、不活性雰囲気下焼成法の条件を最適化することで、より良好な結晶性を有し、かつ触媒として有利なより大きな表面積を有するダブルペロブスカイト型遷移金属酸化物を得ることができる。また、不活性雰囲気下焼成法の方が、ダブルペロブスカイト型遷移金属酸化物の量産には向いている。 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. On the other hand, 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. However, with regard to 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. Further, the firing method in an inert atmosphere is more suitable for mass production of a double perovskite type transition metal oxide.
ダブルペロブスカイト型遷移金属酸化物の同定は、Ｘ線回折実験（例えば、Ｒｉｇａｋｕ Ｕｌｔｉｍａ ＩＶ利用）により行うことができ、酸素量の分析は、例えば、ヨウ素滴定(iodometric titration)により行うことができる。ダブルペロブスカイト型遷移金属酸化物の表面積は、例えば、0.1〜100m2/gの範囲であることができ、好ましくは、0.2〜100m2/gの範囲であることができ、より好ましくは、0.3〜100m2/gの範囲であることができる。本発明で用いるダブルペロブスカイト型遷移金属酸化物の粒径については特に制限はないが、平均粒径は例えば、10nm〜10μm、好ましくは100nm〜5μm、より好ましくは200nm〜2μm程度である。但しこれらは単なる例示であり、これらの範囲に限定される意図ではない。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, for example, can be in the range of 0.1 to 100 m 2 / g, preferably, be in the range of 0.2~100m 2 / g, more preferably, 0.3 Can be in the range of 100m 2 / g. The particle size of the double perovskite 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 μm, preferably 100 nm to 5 μm, more preferably about 200 nm to 2 μm. However, these are merely examples and are not intended to be limited to these ranges.
ダブルペロブスカイト型遷移金属酸化物が触媒する酸素還元反応は、例えば、水溶液中での酸素分子の還元反応である。 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.
実施例において具体的に示すが、いずれの試料も高いORR活性を示すことが判明したが、中でもLnにLaやNdを用いたBaLaMn2O5、BaNdMn2O5が特に優れていた。さらに微粒子化したBaLaMn2O5では、4 mol dm-3 KOH水溶液中で約0.925 V vs RHE@50μA/cm2というORRに対する小さな過電圧(overvoltage)、及び、約-0.73 mA/cm2@0.8 V vs RHEという大きな還元電流を観測した。これは同条件で測定した従来材料であるLaNiO3の0.910 V vs RHE@50μA/cm2よりも過電圧が小さく、-0.36 mA/cm2 @0.8 V vs RHEの電流値の約2倍もの値であった。As specifically shown in the Examples, it was found that all the samples showed high ORR activity, but BaLaMn 2 O 5 and BaNdMn 2 O 5 using La or Nd as Ln were particularly excellent. In addition, BaLaMn 2 O 5 that is micronized has a small overvoltage for ORR of about 0.925 V vs RHE @ 50 μA / 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. This is because the overvoltage is smaller than 0.910 V vs RHE @ 50μA / cm 2 of the conventional material LaNiO 3 measured under the same conditions, and it is about twice the current value of -0.36 mA / cm 2 @ 0.8 V vs RHE. there were.
本発明のダブルペロブスカイト型遷移金属酸化物BaLnMn2O5では、Lnサイトの元素を変えることによりMnの形式価数が同一であるにもかかわらず、ORR活性を変化させることができ、特にLaやNdを用いることで高活性ORR触媒として働く。さらに不活性雰囲気下焼成法によりグラムオーダーで作製したBaLaMn2O5微粒子試料では、遷移金属高活性触媒としてこれまで報告されているLaNiO3の2倍ものORR活性を達成した。In the double perovskite type transition metal oxide BaLnMn 2 O 5 of the present invention, the ORR activity can be changed by changing the element at the Ln site, although the formal valence of Mn is the same. By using Nd, it works as a highly active ORR catalyst. In addition, 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.
これは、次世代型高容量二次電池(New generation high capacity secondary (rechargeable) batteries)として期待されている金属空気二次電池(metal-air secondary batteries)やアルカリ形燃料電池(alkaline fuel cells)の空気極(air electrodes)として極めて有望である。 This is because metal-air secondary batteries and alkaline fuel cells, which are expected as new generation high capacity secondary (rechargeable) batteries, are used. Very promising as air electrodes.
＜酸素欠損ペロブスカイト型遷移金属酸化物＞
酸素欠損ペロブスカイト型遷移金属酸化物は酸素欠損を有することを特徴とし、ダブルペロブスカイト型遷移金属酸化物と同様に、ORR反応において優れた触媒活性を有する。ペロブスカイト型遷移金属酸化物触媒に酸素欠損を意図的に導入することで、酸素欠損ペロブスカイト型遷移金属酸化物触媒を得ることができる。
本発明で触媒として用いる酸素欠損ペロブスカイト型遷移金属酸化物は、例えば、一般式Ln1-xA”xMn1-yB”yO3-δで示すことができる。Lnは、La、Pr、Nd、Sm、Eu、及びGdからなる少なくとも1種の遷移金属であることができる。A”は、価数が+3価未満の原子であり、例えば、アルカリ土類金属（例えば、Ca、Sr）原子であることができる。B”は、価数が+3価未満の原子であり、例えば、+3価未満の価数を示す遷移金属原子であることができる。式中のx及びyは、例えば、0≦x≦0.5、0≦y≦0.5であることができる。また、δは、化合物を構成する原子の種類と量により適宜変化するが、例えば、0<δ<(x+y)/2を満たす範囲である。但し、この範囲に限定される意図ではない。<Oxygen-deficient perovskite transition metal oxide>
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−δ . 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. For example, it can be a transition metal atom exhibiting a valence of less than +3. For example, x and y in the formula can satisfy 0 ≦ x ≦ 0.5 and 0 ≦ y ≦ 0.5. Further, δ varies as appropriate depending on the kind and amount of atoms constituting the compound, but for example, is a range satisfying 0 <δ <(x + y) / 2. However, it is not intended to be limited to this range.
前述のように一般にペロブスカイトは一般式ABO3で示され、AやBサイトに+3価のカチオンを有しており、化合物全体として価数が0になっている。そこで、AやBサイトの一部を+2価のカチオンで一部置換することで、化合物全体のカチオンを減らし、これに伴い酸素アニオンを減少させることで酸素欠損が導入される。
一例として、一般式Ln1-xA”xMn1-yB”yO3-δにおけるA”がCaであり、B”がNiである化合物は、一般式La1-xCaxMn1-yNiyO3-δで示され、酸素欠損を有するペロブスカイト型遷移金属酸化物である。以下、La1-xCaxMn1-yNiyO3-δ（0≦x≦0.5、0≦y≦0.5、δ>0）を例に、ペロブスカイト型遷移金属酸化物について説明する。As described above, 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.
As an example, a compound in which A ″ in the general formula Ln 1-x A ″ x Mn 1-y B ″ y O 3-δ is Ca and B ″ is Ni is represented by the general formula La 1-x Ca x Mn 1 This is a perovskite type transition metal oxide represented by -y Ni y O 3-δ and having oxygen deficiency. Hereinafter, the perovskite type transition metal oxide will be described with reference to La 1-x Ca x Mn 1-y Ni y O 3−δ (0 ≦ x ≦ 0.5, 0 ≦ y ≦ 0.5, Δ> 0).
La1-xCaxMn1-yNiyO3-δ（0≦x≦0.5、0≦y≦0.5、δ>0）で表される遷移金属酸化物である酸素欠損を有するペロブスカイト型遷移金属酸化物は、Aサイトに例えば、LaとCaを有し、BサイトにMnとNiを有するペロブスカイト関連化合物であり、酸素6つと結合した八面体構造、酸素5つと結合したピラミッド構造、あるいは酸素4つと結合した平面四角形構造(square-coordinated structures)などから成る。結晶構造の模式図を以下に示す。酸素5つと結合したピラミッド構造は、酸素欠損と隣接するMn、あるいはNiサイトに存在する。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-δ (0 ≦ x ≦ 0.5, 0 ≦ y ≦ 0.5, δ> 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.
La1-xCaxMn1-yNiyO3-δ（0≦x≦0.5、0≦y≦0.5）で表される遷移金属酸化物である酸素欠損を有するペロブスカイト型遷移金属酸化物は、例えば、非特許文献６において報告されており、物質としては知られている。La1-xCaxMn1-yNiyO3-δ（0≦x≦0.5、0≦y≦0.5）で表される遷移金属酸化物である酸素欠損を有するペロブスカイト型遷移金属酸化物の製法は、例えば、金属硝酸塩等の塩を出発原料とし、クエン酸法により作製した前駆体を用いて、クエン酸ゲル化法(citrate polymerization methods)により合成することができる。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-δ (0 ≦ x ≦ 0.5, 0 ≦ y ≦ 0.5) For example, it is reported in Non-Patent Document 6 and is known as a substance. La 1-x Ca x Mn 1-y Ni y O 3-δ (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.
また、La1-xCaxMn1-yNiyO3-δ（0≦x≦0.5、0≦y≦0.5、δ>0）で表される遷移金属酸化物である酸素欠損を有するペロブスカイト型遷移金属酸化物は、X線回折実験により判別できる。In addition, 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-δ (0 ≦ x ≦ 0.5, 0 ≦ y ≦ 0.5, δ> 0) Type transition metal oxides can be identified by X-ray diffraction experiments.
クエン酸ゲル化法では、硝酸ランタン、硝酸カルシウム、及び遷移金属酸化物を所定の比率でクエン酸と混合してゲル化した後、ゲル化した混合物を空気中で３５０〜４５０℃で０．１〜６時間加熱して酸化物前駆体を形成する。次いで、６００〜１０００℃で３〜１２時間加熱することで、酸素欠損を有するペロブスカイト型遷移金属酸化物が得られる。 In the citric acid gelation method, lanthanum nitrate, calcium nitrate, and a transition metal oxide are mixed with citric acid at a predetermined ratio to be gelled, 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. Subsequently, the perovskite type | mold transition metal oxide which has oxygen deficiency is obtained by heating at 600-1000 degreeC for 3 to 12 hours.
酸素欠損を有するペロブスカイト型遷移金属酸化物の同定は、Ｘ線回折実験（例えば、Ｒｉｇａｋｕ Ｕｌｔｉｍａ ＩＶ利用）により行うことができ、酸素量の分析は、例えば、ヨウ素滴定または水素還元分解時の熱重量分析により行うことができる。ダブルペロブスカイト型遷移金属酸化物の表面積は、例えば、0.1〜100 m2/gの範囲であることができ、好ましくは、0.2〜100m2/gの範囲であることができ、より好ましくは、0.3〜100m2/gの範囲であることができる。本発明で用いる酸素欠損を有するペロブスカイト型遷移金属酸化物の粒径については特に制限はないが、平均粒径は例えば、10nm〜10μm、好ましくは100nm〜5μm、より好ましくは200nm〜2μm程度である。但しこれらは単なる例示であり、これらの範囲に限定される意図ではない。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 reduction decomposition It can be done by analysis. The surface area of the double perovskite type transition metal oxide, for example, be in the range of 0.1 to 100 m 2 / g, preferably, be in the range of 0.2~100m 2 / g, more preferably, 0.3 it can range ~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 μm, preferably 100 nm to 5 μm, more preferably about 200 nm to 2 μm. . However, these are merely examples and are not intended to be limited to these ranges.
酸素欠損を有するペロブスカイト型遷移金属酸化物が触媒する酸素還元反応は、例えば、水溶液中での酸素分子の還元反応である。 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.
実施例において具体的に示すが、例えばLa1-xCaxMn0.5Ni0.5O3-δ（0≦x≦0.5、δ>0）において、x=0.1〜0.3の試料が高いORR活性を示すことが判明したが、中でもx=0.1を用いたLa0.9Ca0.1Mn0.5Ni0.5O3-δが特に優れていた。さらにNi/Mn比を調整することで、x=0.4、y=0.1のLa0.6Ca0.4Mn0.9Ni0.1O3-δにおいて、4 mol dm-3KOH水溶液中で約0.940 V vs RHE@50μA/cm2というORRに対する小さな過電圧、及び、約-0.55 mA/cm2@0.9 V vs RHEという大きな還元電流を観測した。これは同条件で測定した従来材料であるLaNiO3の0.910 V vs RHE@50μA/cm2よりも過電圧が小さく、-0.09 mA/cm2 @0.9 V vs RHEの電流値の約6倍もの値であった。As specifically shown in the Examples, for example, in La 1-x Ca x Mn 0.5 Ni 0.5 O 3-δ (0 ≦ x ≦ 0.5, δ> 0), a sample with x = 0.1 to 0.3 exhibits high ORR activity. However, La 0.9 Ca 0.1 Mn 0.5 Ni 0.5 O 3-δ using x = 0.1 was particularly excellent. Furthermore, by adjusting the Ni / Mn ratio, in La 0.6 Ca 0.4 Mn 0.9 Ni 0.1 O 3-δ with x = 0.4 and y = 0.1, about 0.940 V vs RHE @ 50μA / in 4 mol dm -3 KOH aqueous solution A small overvoltage for ORR of cm 2 and a large reduction current of about -0.55 mA / cm 2 @ 0.9 V vs RHE were observed. This is because the overvoltage is smaller than 0.910 V vs RHE @ 50μA / cm 2 of the conventional material LaNiO 3 measured under the same conditions, and it is about 6 times the current value of -0.09 mA / cm 2 @ 0.9 V vs RHE. there were.
本発明のLa1-xCaxMn1-yNiyO3-δ（0≦x≦0.5、0≦y≦0.5）では、AサイトのCa置換量、及びBサイトのNi置換量を変えることにより酸素欠損を導入し、ORR活性を変化させることができ、特に10%程度のCa置換を行うことで高活性ORR触媒として働く。さらにCa置換量、及びNi置換量を最適化したLa0.9Ca0.1Mn0.5Ni0.5O3-δでは、遷移金属高活性触媒としてこれまで報告されているLaNiO3の6倍ものORR活性を達成した。In La 1-x Ca x Mn 1-y Ni y O 3-δ (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. Thus, oxygen deficiency can be introduced and ORR activity can be changed. In particular, by performing about 10% Ca substitution, it works as a highly active ORR catalyst. Furthermore, La 0.9 Ca 0.1 Mn 0.5 Ni 0.5 O 3-δ with optimized Ca substitution and Ni substitution achieved 6 times higher ORR activity than LaNiO 3 reported so far as a transition metal high activity catalyst.
これは、次世代型高容量二次電池として期待されている金属空気二次電池やアルカリ形燃料電池の空気極として極めて有望である。 This is extremely promising as an air electrode for metal-air secondary batteries and alkaline fuel cells, which are expected as next-generation high-capacity secondary batteries.
＜空気極＞
空気極は、通常、多孔質構造(porous structures)を有し、酸素還元反応触媒の他、導電性材料(electro-conductive material)を含む。また、空気極は、必要に応じて、酸素発生反応（Oxygen Evolution Reaction (OER)）触媒、バインダー等を含んでいてもよい。二次電池における空気極には、充電(charging)時の機能としてOER触媒活性と、放電(discharging)時の機能としてORR触媒活性を有することを要する。本発明の触媒はORR触媒であるので、空気極には、この触媒に加えて、OER触媒を含有させることもできる。空気極における充電及び放電時の化学式を以下に示す。<Air electrode>
The air electrode usually has a porous structure and includes an electro-conductive material in addition to an oxygen reduction reaction catalyst. In addition, the air electrode may contain an oxygen generation reaction (OER) catalyst, a binder, and the like as necessary. 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.
空気極における本発明の触媒(ORR触媒)の含有量は、特に限定されないが、空気極の酸素還元反応性能を高める観点から、例えば、１〜９０質量％であることが好ましく、特に１０〜６０質量％であることが好ましく、３０〜５０質量％であることがより好ましい。 The content of the catalyst of the present invention (ORR catalyst) in the air electrode is not particularly limited, but is preferably 1 to 90% by mass, particularly 10 to 60%, from the viewpoint of improving the oxygen reduction reaction performance of the air electrode. It is preferable that it is mass%, and it is more preferable that it is 30-50 mass%.
OER触媒の例としては、特に制限はないが、例えば、貴金属酸化物(例えば、IrO2、RuO2など)、NiまたはNi系材料(例えば、NiOなど)、Co系材料（例えば、Co3O4、）、ペロブスカイト酸化物（例えば、BaxSr1-xCoxFe1-xO3、SrCoO3、LaNiO3、La1-xCaxCoO3、LaFe1-xNixO3、LaMnO3など）、スピネル酸化物（例えば、CoFe2O4、NiCo2O4、MnxCu1-xCo2O4、など）、金属有機構造体（例えば、CoやFeを含むMOFなど）、錯体系(例えば、Co-ポルフィリン錯体、など)、グラフェン複合系（例えば、CoO/グラフェン、Co-Fe/グラフェン、など）、その他(例えば、NiCo2S4、Mn2O3、など)を挙げることができる。Examples of the OER catalyst are not particularly limited. For example, 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.), and others (eg, NiCo 2 S 4 , Mn 2 O 3 , etc.) be able to.
但し、これらに限定される意図ではない。また、各触媒の性能や性質を考慮して複数の触媒を組み合わせて用いることもできる。さらに上記触媒には、助触媒(例えば、TiOx、RuO2、SnO2など)を組み合わせて用いることもできる。OER触媒を併用する場合の含有量は、OER触媒の種類や触媒活性等を考慮して適宜決定することができ、例えば、１〜９０質量％であることができる。但し、この数値範囲に限定される意図ではない。However, it is not the intention limited to these. A plurality of catalysts may be used in combination in consideration of the performance and properties of each catalyst. Furthermore, a cocatalyst (for example, TiO x , RuO 2 , SnO 2, etc.) can be used in combination with the above catalyst. 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.
導電性材料としては、特に限定されず、導電助剤として一般的に使用可能なものであればよいが、好適なものとして導電性カーボンが挙げられる。具体的には、メソポーラスカーボン、グラファイト、アセチレンブラック、カーボンナノチューブ、カーボンファイバー等が挙げられる。空気極において多くの反応場を提供することから、比表面積が大きい導電性カーボンが好ましい。具体的には、比表面積が１〜３０００ｍ2／ｇ、特に５００〜１５００ｍ2／ｇである導電性カーボンが好ましい。空気極の触媒は、導電性材料に担持させてもよい。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. Specifically, the specific surface area of 1~3000m 2 / g, which conductive carbon is particularly preferably 500 to 1500 2 / g. The catalyst for the air electrode may be supported on a conductive material.
空気極における導電性材料の含有量は、特に限定されないが、放電容量を高める観点から、例えば、１０〜９９質量％であることが好ましく、特に２０〜８０質量％であることが好ましく、２０〜５０質量％であることがより好ましい。 Although content of the electroconductive material in an air electrode is not specifically limited, From a viewpoint of raising discharge capacity, it is preferable that it is 10-99 mass%, for example, and it is especially preferable that it is 20-80 mass%, and 20-20. More preferably, it is 50 mass%.
空気極にバインダーを含有させることで、触媒や導電性材料を固定化し、電池のサイクル特性を向上させることができる。バインダーとしては特に限定されず、例えば、ポリフッ化ビニリデン（ＰＶＤＦ）及びその共重合体、ポリテトラフルオロエチレン（ＰＴＦＥ）及びその共重合体、スチレンブタジエンゴム（ＳＢＲ）等が挙げられる。空気極におけるバインダーの含有量は、特に限定されないが、カーボン（導電性材料）と触媒との結着力の観点から、例えば、１〜４０質量％であることが好ましく、特に５〜３５質量％であることが好ましく、１０〜３５質量％であることがより好ましい。 By including a binder in the air electrode, the catalyst and the conductive material can be fixed and the cycle characteristics of the battery can be improved. 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). Although 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 force between carbon (conductive material) and the catalyst. It is preferably 10 to 35% by mass.
空気極は、例えば、上記した空気極構成材料を適当な溶媒に分散させて調製したスラリーを基材上に塗布、乾燥することで形成することができる。溶媒としては、特に限定されず、例えば、アセトン、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチル−２−ピロリドン（ＮＭＰ）等が挙げられる。空気極構成材料と溶媒との混合は、通常、３時間以上、好ましくは４時間行うことが好ましい。混合方法は特に限定されず、一般的な方法を採用することができる。 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.
スラリーを塗布する基材は、特に限定されず、ガラス板、テフロン(登録商標)板等が挙げられる。これら基材は、スラリーの乾燥後、得られた空気極から剥離される。或いは、空気極の集電体や、固体電解質層を、上記基材として扱うこともできる。この場合、基材は剥離せずに、金属空気二次電池の構成部材としてそのまま利用する。 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.
スラリーの塗布方法、乾燥方法は、特に限定されず、一般的な方法を採用することができる。例えば、スプレー法、ドクターブレード法、グラビア印刷法等の塗布方法、加熱乾燥、減圧乾燥等の乾燥方法を採用することができる。 A method for applying the slurry and a method for drying the slurry are not particularly limited, and general methods can be employed. For example, 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.
空気極の厚さは、特に限定されず、金属空気二次電池の用途等に応じて適宜設定すればよいが、通常、５〜１００μｍ、１０〜６０μｍ、特に２０〜５０μｍであることが好ましい。 The thickness of the air electrode is not particularly limited, and may be set as appropriate according to the use of the metal-air secondary battery, but is usually 5 to 100 μm, 10 to 60 μm, and particularly preferably 20 to 50 μm.
空気極には、通常、空気極の集電を行う空気極集電体が接続される。空気極集電体の材料、形状は特に限定されない。空気極集電体の材料としては、例えば、ステンレス、アルミニウム、鉄、ニッケル、チタン、炭素（カーボン）等が挙げられる。また、空気極集電体の形状としては、箔状、板状、メッシュ（グリッド状）、繊維状等が挙げられ、中でもメッシュ状等の多孔質形状であることが好ましい。多孔質形状の集電体は、空気極への酸素供給効率に優れているからである。 An air electrode current collector that normally collects the air electrode is connected to 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.
＜金属空気二次電池＞
本発明の金属空気二次電池は、上記したダブルペロブスカイト型遷移金属酸化物を含む触媒を含有する空気極と、負極活物質を含有する負極と、空気極と負極との間に介在する電解質と、を有する。本発明の金属空気二次電池の空気極には、ダブルペロブスカイト型遷移金属酸化物を含む触媒が含有され、この触媒は優れたORR触媒特性を示す。従って、この触媒を用いた空気極を用いることで、本発明の金属空気二次電池は、充電速度及び充電電圧に優れたものとなる。<Metal-air secondary battery>
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. Have. 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.
また、空気極は前記のようにOER触媒活性を有する触媒を共存させることもできる。あるいは、ダブルペロブスカイト型遷移金属酸化物を含む触媒を含有する酸素発生(ORR)用の空気極とは別に、OER触媒活性を有する触媒を含む酸素反応(OER)用の空気極を設けることもできる。この場合、金属空気二次電池は、酸素還元用の空気極と酸素発生用の空気極とを有することになる(3電極方式)。放電時には酸素還元用の空気極が用いられ、充電時には酸素発生用の空気極が用いられる。OER触媒活性を有する触媒は前述の通りであり、この触媒と上記空気極の説明で記載した導電性材料及びバインダー等を用いて酸素発生用の空気極を得ることができる。 The air electrode can also coexist with a catalyst having OER catalytic activity as described above. Alternatively, 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. . In this case, 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.
以下、本発明の金属空気二次電池の一構成例について説明する。尚、本発明の金属空気二次電池は、以下の構成に限定されるものではない。図８は、本発明の金属空気二次電池の一形態例を示す断面図である。金属空気二次電池１は、酸素を活物質とする空気極２、負極活物質を含有する負極３、空気極２及び負極３の間でイオン伝導を担う電解質４、空気極２の集電を行う空気極集電体５、及び負極３の集電を行う負極集電体６からなり、これらが図示しない電池ケースに収容されている。空気極２には、該空気極２の集電を行う空気極集電体５が電気的に接続され、空気極集電体５は、空気極２への酸素供給が可能な多孔質構造を有している。負極３には、該負極３の集電を行う負極集電体６が電気的に接続され、空気極集電体５及び負極集電体６の端部のうち一方は、電池ケースから突出している。それぞれ、正極端子（図示せず）、負極端子（図示せず）として機能する。 Hereinafter, a configuration example of the metal-air secondary battery of the present invention will be described. In addition, the metal air secondary battery of this invention is not limited to the following structures. 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. Have. 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. Each functions as a positive terminal (not shown) and a negative terminal (not shown).
（負極）
負極は、負極活物質を含有する。負極活物質としては、一般的な空気電池の負極活物質を用いることができ、特に限定されるものではない。負極活物質は、通常、金属イオンを吸蔵・放出することができるものである。具体的な負極活物質としては、例えば、Ｌｉ、Ｎａ、Ｋ、Ｍｇ、Ｃａ、Ｚｎ、Ａｌ、及びＦｅ等の金属、これら金属の合金、酸化物及び窒化物、並びに炭素材料等が挙げられる。(Negative electrode)
The negative electrode contains a negative electrode active material. As 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.
中でも、亜鉛−空気二次電池(Zinc-air secondary batteries)は安全面において優れており、次世代の二次電池として期待されている。尚、高電圧高出力という観点からはリチウム−空気二次電池及びマグネシウム空気二次電池が有望である。
亜鉛−空気二次電池の例を以下に説明すると、反応式は以下の通りである。Among these, 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 the zinc-air secondary battery will be described below. The reaction formula is as follows.
本発明の亜鉛−空気二次電池において、負極としては、亜鉛イオンを吸蔵・放出可能な材料を用いる。このような負極としては、金属亜鉛のほかに、亜鉛合金を用いることもできる。亜鉛合金としては、例えば、アルミニウム、インジウム、マグネシウム、スズ、チタン、銅、から選択される一種または二種以上の元素を含有する亜鉛合金を挙げることができる。 In the zinc-air secondary battery of the present invention, as the negative electrode, a material capable of occluding and releasing zinc ions is used. As such a negative electrode, a zinc alloy can also be used in addition to zinc metal. Examples of the zinc alloy include a zinc alloy containing one or more elements selected from aluminum, indium, magnesium, tin, titanium, and copper.
リチウム−空気二次電池の負極活物質としては、例えば金属リチウム；リチウムアルミニウム合金、リチウムスズ合金、リチウム鉛合金、リチウムケイ素合金等のリチウム合金；スズ酸化物、ケイ素酸化物、リチウムチタン酸化物、ニオブ酸化物、タングステン酸化物等の金属酸化物；スズ硫化物、チタン硫化物等の金属硫化物；リチウムコバルト窒化物、リチウム鉄窒化物、リチウムマンガン窒化物等の金属窒化物；並びにグラファイト等の炭素材料等を挙げることができ、中でも金属リチウムが好ましい。 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.
さらに、マグネシウム−空気二次電池の負極活物質としては、マグネシウムイオンを吸蔵・放出可能な材料を用いる。このような負極としては、金属マグネシウムのほかに、マグネシウムアルミニウム、マグネシウムシリコン、マグネシウムガリウムなどのマグネシウム合金などを用いることができる。 Furthermore, as the negative electrode active material of the magnesium-air secondary battery, a material capable of occluding and releasing magnesium ions is used. As such a negative electrode, in addition to metallic magnesium, magnesium alloys such as magnesium aluminum, magnesium silicon, and magnesium gallium can be used.
箔状や板状の金属や合金等を負極活物質として用いる場合には、該箔状や板状の負極活物質を負極そのものとして使用することができる。 When a foil-like or plate-like metal or alloy is used as the negative electrode active material, the foil-like or plate-like negative electrode active material can be used as the negative electrode itself.
負極は、少なくとも負極活物質を含有してればよいが、必要に応じて、負極活物質を固定化する結着材を含有していてもよい。結着材の種類、使用量等については、上述した空気極と同様であるため、ここでの説明は省略する。 The negative electrode only needs to contain at least a negative electrode active material, but may contain a binder for immobilizing the negative electrode active material, if necessary. About the kind of binder, usage-amount, etc., since it is the same as that of the air electrode mentioned above, description here is abbreviate | omitted.
負極には、通常、負極の集電を行う負極集電体が接続される。負極集電体の材料、形状は特に限定されない。負極集電体の材料としては、例えば、ステンレス、銅、ニッケル等が挙げられる。また、負極集電体の形状としては、箔状、板状、メッシュ（グリッド状）等が挙げられる。 A negative electrode current collector that normally collects current from the negative electrode is connected to the negative electrode. 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).
（電解質）
電解質は、空気極と負極との間に配置される。電解質を介して、負極と空気極との間の金属イオン伝導が行われる。電解質の形態は、特に限定されるものではなく、液体電解質、ゲル電解質、固体電解質等を挙げることができる。(Electrolytes)
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.
電解液は、負極が亜鉛又はその合金の場合を例に挙げれば、酸化亜鉛を含む水酸化カリウム水溶液や水酸化ナトリウム水溶液などのアルカリ水溶液を用いてもよいし、塩化亜鉛や過塩素酸亜鉛を含む水溶液を用いてもよいし、過塩素酸亜鉛を含む非水系溶媒や亜鉛ビス（トリフルオロメチルスルフォニル）イミドを含む非水系溶媒を用いてもよい。また、負極がマグネシウム又はその合金の場合を例に挙げれば、過塩素酸マグネシウムやマグネシウムビス（トリフルオロメチルスルフォニル）イミドを含む非水系溶媒を用いてもよい。ここで、非水系溶媒としては、例えば、エチレンカーボネート（ＥＣ）、プロピレンカーボネート（ＰＣ）、γ−ブチロラクトン（γ−ＢＬ）、ジエチルカーボネート（ＤＥＣ）、ジメチルカーボネート（ＤＭＣ）など従来の二次電池やキャパシタに使われる有機溶媒が挙げられる。これらは単独で用いてもよいし、複数を混合して用いてもよい。あるいは、Ｎ，Ｎ−ジエチル−Ｎ−メチル−Ｎ−（２−メトキシエチル）アンモニウムビス（トリフルオロメチルスルホニル）イミド（ａｍ）などのイオン性液体を用いることもできる。 If the negative electrode is zinc or an alloy thereof as an example, 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. Further, if 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. Here, as the non-aqueous solvent, for example, conventional secondary batteries such as ethylene carbonate (EC), propylene carbonate (PC), γ-butyrolactone (γ-BL), diethyl carbonate (DEC), dimethyl carbonate (DMC), Examples include organic solvents used in capacitors. These may be used alone or in combination. Alternatively, an ionic liquid such as N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethylsulfonyl) imide (am) can be used.
本発明の二次電池において、電解液は、デンドライト生成防止剤を含むことが好ましい。デンドライト生成防止剤は、充電時に負極表面に吸着して結晶面間のエネルギー差を小さくし、優先配向を防ぐことによりデンドライトの発生を抑制すると考えられる。デンドライト生成防止剤については特に限定はないが、例えば、ポリアルキレンイミン類、ポリアリルアミン類及び非対称ジアルキルスルフォン類からなる群より選ばれた少なくとも１種のものであることができる(例えば、日本特開2009-93983号公報参照)。また、デンドライト生成防止剤の使用量は、特に限定されるものではないが、例えば常温常圧で電解液に飽和する量だけ用いてもよいし、溶媒として用いてもよい。 In the secondary battery of the present invention, 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). Moreover, the usage-amount of a dendrite production | 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.
リチウムイオン伝導性を有する液体電解質は、通常、リチウム塩及び非水溶媒を含有する非水電解液である。上記リチウム塩としては、例えばＬｉＰＦ6、ＬｉＢＦ4、ＬｉＣｌＯ4及びＬｉＡｓＦ6等の無機リチウム塩；並びにＬｉＣＦ3ＳＯ3、ＬｉＮ（ＣＦ3ＳＯ2）2、ＬｉＮ（Ｃ2Ｆ5ＳＯ2）2、ＬｉＣ（ＣＦ3ＳＯ2）3等の有機リチウム塩等を挙げることができる。The liquid electrolyte having lithium ion conductivity is usually a non-aqueous electrolyte containing a lithium salt and a non-aqueous solvent. Examples of 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.
上記非水溶媒としては、例えばエチレンカーボネート（ＥＣ）、プロピレンカーボネート（ＰＣ）、ジメチルカーボネート（ＤＭＣ）、ジエチルカーボネート（ＤＥＣ）、エチルメチルカーボネート（ＥＭＣ）、ブチレンカーボネート、γ−ブチロラクトン、スルホラン、アセトニトリル、１，２−ジメトキシメタン、１，３−ジメトキシプロパン、ジエチルエーテル、テトラヒドロフラン、２−メチルテトラヒドロフラン及びこれらの混合物等を挙げることができる。非水溶媒としては、イオン液体を用いることもできる。 Examples of the non-aqueous solvent include ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), butylene carbonate, γ-butyrolactone, sulfolane, acetonitrile, Examples 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.
非水電解液におけるリチウム塩の濃度は、特に限定されないが、例えば０．１ｍｏｌ／Ｌ〜３ｍｏｌ／Ｌの範囲内であることが好ましく、好ましくは１ｍｏｌ／Ｌである。尚、本発明においては、非水電解液として、例えばイオン性液体等の低揮発性液体を用いてもよい。 The concentration of the lithium salt in the nonaqueous 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. In the present invention, a low-volatile liquid such as an ionic liquid may be used as the nonaqueous electrolytic solution.
リチウムイオン伝導性を有するゲル電解質は、例えば、上記非水電解液にポリマーを添加してゲル化することで得ることができる。具体的には、上記非水電解液に、ポリエチレンオキシド（ＰＥＯ）、ポリビニリデンフルオライド（ＰＶＤＦ、Ａｒｋｅｍａ社製商品名Ｋｙｎａｒ（登録商標）など）ポリアクリロニトリル（ＰＡＮ）またはポリメチルメタクリレート（ＰＭＭＡ）等のポリマーを添加することにより、ゲル化を行うことができる。 The gel electrolyte having lithium ion conductivity can be obtained, for example, by adding a polymer to the non-aqueous electrolyte and gelling. 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.
リチウムイオン伝導性を有する固体電解質としては、特に限定されず、リチウム金属空気二次電池で使用可能な一般的な固体電解質を用いることができる。例えば、Ｌｉ1.5Ａｌ0.5Ｇｅ1.5（ＰＯ4）3等の酸化物固体電解質；Ｌｉ2Ｓ−Ｐ2Ｓ5化合物、Ｌｉ2Ｓ−ＳｉＳ2化合物、Ｌｉ2Ｓ−ＧｅＳ2化合物等硫化物固体電解質；を挙げることができる。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. For example, oxide solid electrolyte such as Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 ; sulfide solid electrolyte such as Li 2 S—P 2 S 5 compound, Li 2 S—SiS 2 compound, Li 2 S—GeS 2 compound Can be mentioned.
電解質の厚さは、電池の構成によって大きく異なるものであるが、例えば１０μｍ〜５０００μｍの範囲内であることが好ましい。 The thickness of the electrolyte varies greatly depending on the configuration of the battery, but is preferably in the range of 10 μm to 5000 μm, for example.
（付属構成）
本発明の金属空気二次電池において、空気極と負極との間には、これら電極間の電気的絶縁を確実に行うために、セパレータが配置されることが好ましい。セパレータは、空気極と負極との間の電気的絶縁が確保可能であると共に、空気極と負極との間に電解質が介在することが可能な構造を有していれば特に限定されない。(Accessory configuration)
In the metal-air secondary battery of the present invention, 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.
セパレータとしては、例えば、ポリエチレン、ポリプロピレン、セルロース、ポリフッ化ビニリデン、ガラスセラミックス等の多孔膜；及び樹脂不織布、ガラス繊維不織布等の不織布等を挙げることができる。中でも、ガラスセラミックス製のセパレータが好ましい。 Examples of the separator 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 glass ceramic separator is preferable.
また、金属空気二次電池を収納する電池ケースとしては、一般的な金属空気二次電池の電池ケースを用いることができる。電池ケースの形状としては、上述した空気極、負極、及び電解質を保持することができれば特に限定されるものではないが、具体的にはコイン型、平板型、円筒型、ラミネート型等を挙げることができる。 Moreover, as a battery case which accommodates a metal air secondary battery, the 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, and specifically includes a coin type, a flat plate type, a cylindrical type, a laminate type, and the like. Can do.
本発明の金属空気二次電池は、空気極に活物質である酸素が供給されることにより、放電が可能となる。酸素供給源としては、空気の他、酸素ガス等が挙げられ、好ましくは酸素ガスである。供給する空気又は酸素ガスの圧力は特に限定されず、適宜設定すればよい。 The metal-air secondary battery of the present invention can be discharged by supplying oxygen as an active material to the air electrode. Examples of the 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.
以下、本発明を実施例に基づいて更に詳細に説明する。但し、実施例は本発明の例示であって、本発明は実施例に限定される意図ではない。 Hereinafter, the present invention will be described in more detail based on examples. However, the examples are illustrative of the present invention, and the present invention is not intended to be limited to the examples.
実施例１
＜ダブルペロブスカイト型遷移金属酸化物＞
合成例
ダブルペロブスカイト型遷移金属酸化物BaLnMn2O5（Ln: Y, Gd, Nd,又はLa）は、真空封管法及び不活性雰囲気下焼成法により合成した。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.
真空封管法
真空封管法では原料としてBa(NO3)2、Ln2O3、Mn(NO3)2を用いて硝酸塩水溶液を調製し、この水溶液を加熱攪拌してゲル化後、空気中450℃で1時間、1000℃で24時間仮焼することで前駆体を合成した。これを酸素ゲッターであるFeOと共に石英管に真空封入し、1100℃で24時間焼成後、氷水中で急冷することで合成した。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.
不活性雰囲気下焼成法
BaLaMn2O5の不活性雰囲気下焼成法では、原料としてBa(CH3COO)2、La(CH3COO)3・1.5H2O、Mn(CH3COO)2・4H2Oを用いて酢酸塩水溶液を調製し、この水溶液を加熱攪拌してゲル化後、空気中350℃で1時間仮焼することで前駆体を合成した。これを窒素気流中、1000℃で12時間焼成することで合成した。Baking method under inert atmosphere
In BaLaMn 2 O Under an inert atmosphere firing method 5, using Ba (CH 3 COO) 2, La (CH 3 COO) 3 · 1.5H 2 O, Mn (CH 3 COO) 2 · 4H 2 O as raw materials An aqueous acetate solution was prepared, this aqueous solution was heated and stirred to gel, and then calcined in air at 350 ° C. for 1 hour to synthesize a precursor. This was synthesized by firing at 1000 ° C. for 12 hours in a nitrogen stream.
得られた試料に対してX線回折により相同定および構造解析を行った。シミュレーションにより求めたX線回折パターンおよび既報[1〜4]より、真空封管法によりBaLnMn2O5（Ln: Y, Gd, Nd, La）の単一相が合成できていることを確認した（図1）。また不活性雰囲気下焼成法においても、X線回折より、やや結晶性は低いものBaLaMn2O5が合成できていることを確認した（不純物として若干のMnOあり）（図2）。なお、δ=0.5、あるいはδ=1の場合は、δ=0の場合に比べ、各ピーク位置が0.2°程度高角側にシフトするため、本試料は高角のシフトがないので、δ=0の酸素欠損を有していることも確認できた。
[1] F. Millange, E. Suard, V. Caignaert and B. Raveau, Mater. Res. Bull. 1999, 34, 1-9. (非特許文献3)
[2] M. Karppinen, H. Okamoto, H. Fjellag, T. Motohashi and H. Yamauchi, J. Solid State Chem. 2004, 177, 2122-2128.
[3] F. Millange, V. Caignaert, B. Domenges and B. Raveau, Chem. Mater. 1998, 10, 1974-1983.
[4] S. V. Trukhanov, I. O. Troyanchuk, M. Hervieu, H. Szymczak and K. Baerner, Phys. Rev. B 2002, 66, 184424/1-84424/10.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). When δ = 0.5 or δ = 1, each peak position is shifted to the high angle side by about 0.2 ° compared to δ = 0, so this sample has no high angle shift. It was also confirmed that it had oxygen deficiency.
[1] F. Millange, E. Suard, V. Caignaert and B. Raveau, Mater. Res. Bull. 1999, 34, 1-9.
[2] M. Karppinen, H. Okamoto, H. Fjellag, T. Motohashi and H. Yamauchi, J. Solid State Chem. 2004, 177, 2122-2128.
[3] F. Millange, V. Caignaert, B. Domenges and B. Raveau, Chem. Mater. 1998, 10, 1974-1983.
[4] SV Trukhanov, IO Troyanchuk, M. Hervieu, H. Szymczak and K. Baerner, Phys. Rev. B 2002, 66, 184424 / 1-84424 / 10.
これらについて、走査型電子顕微鏡（SEM）において、その粒径、及び表面積を評価した。真空封管により合成した試料は、どの試料についても平均粒径が1〜2μm程度であり、表面積も0.25〜0.75 m2 g-1程度と同程度であることを確認した（図3）。About these, the particle size and surface area were evaluated in the scanning electron microscope (SEM). The samples synthesized by the vacuum sealed tube were confirmed to have an average particle size of about 1 to 2 μm and a surface area of about 0.25 to 0.75 m 2 g −1 for any sample (FIG. 3).
また不活性雰囲気下焼成法により合成したBaLaMn2O5では、数百nm程度と微粒子化されており、窒素吸着法により評価した表面積は3.93 m2 g-1と真空封管法により合成したものの約10倍であることが分かった（図4）。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).
電極作製 (図5参照)
得られたBaLnMn2O5（Ln: Y, Gd, Nd, La）と、硝酸に80℃で一晩浸漬した後に洗浄乾燥したアセチレンブラック、及びNaOHで中和したNafion(R)を重量比5:1:1で混合し、適量のエタノールを加えて触媒懸濁液を調製した。これをダブルペロブスカイト型遷移金属酸化物触媒が1.0 mg/cm2の割合になるようにグラッシーカーボン（GC）電極上に滴下し、室温乾燥することでORR触媒とした。また比較用として、金属硝酸塩を出発原料とし、クエン酸法により作製した前駆体を酸素気流中850℃で焼成して得たLaNiO3遷移金属触媒（表面積3.07 m2 g-1）についても同様の方法でGC電極に塗布した。Electrode fabrication (see Fig. 5)
The obtained BaLnMn 2 O 5 (Ln: Y, Gd, Nd, La), acetylene black that was immersed in nitric acid at 80 ° C. overnight, washed and dried, and Nafion (R) neutralized with NaOH at a weight ratio of 5 The mixture was mixed 1: 1 and an appropriate amount of ethanol was added to prepare a catalyst suspension. This was dropped on a glassy carbon (GC) electrode so that the double perovskite type transition metal oxide catalyst was in a ratio of 1.0 mg / cm 2 and dried at room temperature to obtain an ORR catalyst. For comparison, the same applies to a LaNiO 3 transition metal catalyst (surface area 3.07 m 2 g -1 ) obtained by calcining a precursor prepared by the citric acid method using metal nitrate as a starting material in an oxygen stream at 850 ° C. It applied to the GC electrode by the method.
電気化学測定(図5参照)
電気化学測定(electrochemical measurements)には三電極式(Three-electrode system)のテフロン(登録商標)製電気化学セル(electrochemical cells)を用い、対極には白金板、参照極(reference electrode)にはHg/HgO/KOHを用いた。掃引速度(sweep rate)1 mV/sで-0.324〜0.076 V vs Hg/HgO/KOH（1.00〜0.60 V vs RHE）の電位範囲で掃引し、電解液にはAr飽和4.0 mol dm-3のKOH水溶液で測定した後、O2飽和溶液にて同じ電位範囲で測定し、これらの電流値の差よりORR活性を評価した。Electrochemical measurement (see Fig. 5)
For electrochemical measurements, 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, and the electrolyte is KOH with Ar saturation 4.0 mol dm -3 After measurement with an aqueous solution, 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.
真空封管法により合成したBaLnMn2O5（Ln: Y, Gd, Nd, La）について電気化学測定を行った結果、BaYMn2O5、BaGdMn2O5、BaNdMn2O5、BaLaMn2O5の全ての試料において、0.9〜0. 85 V vs RHE付近からORRに由来する電流が観測された。またそれぞれにおいて、-50μA cm-2における電位に注目すると、Lnのイオン半径が大きくなるにしたがって、電位が大きくなりORRに対する過電圧が小さくなっていることが分かった。中でもLa、及びNdを用いた際には高いORR活性を示すことを見出した（図6）。As a result of electrochemical measurement of BaLnMn 2 O 5 (Ln: Y, Gd, Nd, La) synthesized by vacuum sealed tube method, BaYMn 2 O 5 , BaGdMn 2 O 5 , BaNdMn 2 O 5 , BaLaMn 2 O 5 In all the samples, currents derived from ORR were observed from around 0.9 to 0.85 V vs RHE. In each case, focusing on the potential at −50 μA cm −2, it was found that as the ionic radius of Ln increased, the potential increased and the overvoltage against ORR decreased. In particular, it was found that high ORR activity was exhibited when La and Nd were used (FIG. 6).
真空封管法はミリグラムオーダーでの合成に適しているが、次世代高容量二次電池として期待されている金属空気二次電池の空気極として応用する際には、グラムオーダーでの合成方法が必要である。 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.
そこで、上述の方法にて最も高活性であったBaLaMn2O5を不活性雰囲気下焼成法により合成した試料について、同様にしてORR活性を評価した。その結果、-50μA cm-2における電位は0.925 V vs RHEであり、真空封管法により合成したものに比べ、0.05 V以上の過電圧の低減に成功した。これは現在、ORRに対して最も高活性が遷移金属酸化物の1つであるLaNiO3（0.910 V vs RHE@50μA/cm2）よりも過電圧が小さい。また電流値についても、0.8 V vs RHEにおいてLaNiO3が-0.36 mA/cm2であるのに対し、不活性雰囲気下焼成法により合成したBaLaMn2O5は-0.73 mA/cm2と2倍以上の還元電流を得ることができており、ORRに対して極めて高活性な遷移金属酸化物触媒の合成に成功した（図7）。Therefore, 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. As a result, the potential at -50μA 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 μA / cm 2 ), which is currently one of the transition metal oxides with the highest activity for ORR. Also, the current value of LaNiO 3 is -0.36 mA / cm 2 at 0.8 V vs RHE, whereas BaLaMn 2 O 5 synthesized by the firing method in an inert atmosphere is -0.73 mA / cm 2 and more than doubled. As a result, we succeeded in synthesizing a transition metal oxide catalyst with extremely high activity against ORR (Fig. 7).
実施例２
＜酸素欠損ペロブスカイト型＞
合成例
酸素欠損ペロブスカイト型遷移金属酸化物La1-xCaxMn1-yNiyO3-δは、硝酸塩を用いたクエン酸ゲル化法により合成した。原料としてLa(NO3)3・6H2O、Ca(NO3)2・4H2O、Ni(NO3)2・6H2O、Mn(NO3)2・6H2O、クエン酸を用いて混合し、ゲル化後空気中350℃で1時間仮焼することで前駆体を合成した。これをさらに、600℃で12時間焼成することで合成した。
得られた試料に対してX線回折により、相同定および構造解析を行った結果を図９に示す。シミュレーションにより求めたX線回折パターンより、Ca置換量とNi置換量の合計が50%以上の場合に、600℃といった低温でアモルファス相を含まない結晶微粒子の合成が確認された。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-δ 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. 9 shows the results of phase identification and structural analysis performed on the obtained sample by X-ray diffraction. From the X-ray diffraction pattern obtained by simulation, it was confirmed that fine crystalline particles containing no amorphous phase were synthesized at a low temperature of 600 ° C. when the total amount of Ca substitution and Ni substitution was 50% or more.
図１０に600℃焼成により得られたLa1-xCaxMn0.5Ni0.5O3-δ（0≦x≦0.5）のXRDパターンを示す。La1-xCaxMn0.5Ni0.5O3-δ（0≦x≦0.2）において、単一相が合成できていることを確認した。一方、x > 0.3では、NiOの不純物相の形成を確認した。また、Ca置換量の増加に伴い、XRDピークの高角側へのシフトが確認され、MnやNiの価数の連続的な上昇が示唆された。FIG. 10 shows an XRD pattern of La 1-x Ca x Mn 0.5 Ni 0.5 O 3-δ (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-δ (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.
図１１に各試料のSEM像を示す。どの試料についても平均粒径が30〜40 nm程度であり、また窒素吸着測定により表面積を求めると、表面積も20〜30 m2 g-1程度と同程度であり、高表面積であることを確認した。FIG. 11 shows an SEM image of each sample. For any sample, the average particle size is about 30 to 40 nm, and when the surface area is determined by nitrogen adsorption measurement, the surface area is about the same as about 20 to 30 m 2 g -1 and it is confirmed that the surface area is high. did.
電極作製
得られたLa1-xCaxMn1-yNiyO3-δ（0≦x≦0.5、0≦y≦0.5、δ>0）と、硝酸に80℃で一晩浸漬した後に洗浄乾燥したアセチレンブラック、及びNaOHで中和したNafion(R)を重量比5:1:1で混合し、適量のエタノールを加えて触媒懸濁液を調製した。これをペロブスカイト型遷移金属酸化物触媒が1.0 mg/cm2の割合になるようにグラッシーカーボン（GC）電極上に滴下し、室温乾燥することでORR触媒とした。また比較用として、金属硝酸塩を出発原料とし、クエン酸法により作製した前駆体を酸素気流中850℃で焼成して得たLaNiO3遷移金属触媒（表面積3.07 m2 g-1）についても同様の方法でGC電極に塗布した。電気化学測定には三電極式のテフロン(登録商標)製電気化学セルを用い、対極には白金板、参照極にはHg/HgO/KOHを用いた。掃引速度1 mV/sで所定の電位範囲で掃引し、電解液にはAr飽和4.0 mol dm-3のKOH水溶液で測定した後、O2飽和溶液にて同じ電位範囲で測定し、これらの電流値の差よりORR活性を評価した。Electrode fabrication
La 1-x Ca x Mn 1-y Ni y O 3-δ (0 ≤ x ≤ 0.5, 0 ≤ y ≤ 0.5, δ> 0) and soaked in nitric acid at 80 ° C overnight, washed and dried the acetylene black, and Nafion was neutralized with NaOH (R) in a weight ratio of 5: 1: 1 mixture, to prepare a catalyst suspension was added an appropriate amount of ethanol. This was dripped onto a glassy carbon (GC) electrode so that the perovskite type transition metal oxide catalyst had a ratio of 1.0 mg / cm 2 and dried at room temperature to obtain an ORR catalyst. For comparison, the same applies to a LaNiO 3 transition metal catalyst (surface area 3.07 m 2 g -1 ) obtained by calcining a precursor prepared by the citric acid method using metal nitrate as a starting material in an oxygen stream at 850 ° C. It applied to the GC electrode by the method. 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. After sweeping in the specified potential range at a sweep rate of 1 mV / s, 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.
クエン酸ゲル化法により合成したLa1-xCaxMn0.5Ni0.5O3-δ（0≦x≦0.5）について電気化学測定を行った結果を図１２に示す。全ての試料において、0.93〜0.90 V vs RHE付近からORRに由来する電流が観測された。またそれぞれにおいて50 μA cm-2における電位に注目すると、10%Ca部分置換を行うことで、ORRに対する過電圧がLaNiO3よりも小さいことが分かった。これらのORR活性をCa置換量に対してプロットした結果、ORR活性について、10%置換で活性が大きく向上し、その後一定となり、NiO不純物が生成する30%以上から活性が低下することが分かった。即ち、この系では、xは0.1〜0.3の範囲が好ましい。FIG. 12 shows the results of electrochemical measurements of La 1-x Ca x Mn 0.5 Ni 0.5 O 3-δ (0 ≦ x ≦ 0.5) synthesized by the citric acid gelation method. In all samples, a current derived from ORR was observed from around 0.93 to 0.90 V vs RHE. Further, focusing on the potential at 50 μA cm −2 in each case, it was found that the overvoltage with respect to ORR was smaller than LaNiO 3 by performing 10% Ca partial substitution. As a result of plotting these ORR activities against the amount of Ca substitution, it was found that the ORR activity was greatly improved with 10% substitution, then became constant, and the activity decreased from 30% or more when NiO impurities were generated. . That is, in this system, x is preferably in the range of 0.1 to 0.3.
これらの活性向上の原因を調べるために、各試料の放射光によるXAFS測定を行った。その結果を図１３に示す。得られた動径分布関数から、ORR活性の向上が見られるCa10%置換において、Mn、Ni原子からもっとも近い酸素に由来するピーク強度が減少しており、また活性がほぼ同じである10%置換と20%置換ではピーク強度がほぼ一定であることが分かった。これらのことは、10%Ca置換の際に、ORR活性サイトであるMnやNiの周りに酸素欠損が生成していることを示唆しており、酸素欠損による活性向上が確認された。一方、Ca置換によりMn、Niの価数の向上も確認されているが、これはCa置換量に対して単調に増加しており、ORR活性変化と一致していない。 In order to investigate the cause of these activity improvements, XAFS measurement was performed on each sample using synchrotron radiation. The result is shown in FIG. From the obtained radial distribution function, in the Ca 10% substitution in which the ORR activity is improved, the peak intensity derived from the oxygen closest to the Mn and Ni atoms decreases, and the 10% substitution where the activity is almost the same With 20% substitution, the peak intensity was found to be almost constant. These facts suggested that oxygen deficiency was generated around Mn and Ni, which are ORR active sites, when 10% Ca substitution was performed, and the activity improvement due to oxygen deficiency was confirmed. On the other hand, improvement of the valences of Mn and Ni was also confirmed by Ca substitution, but this monotonically increased with respect to the amount of Ca substitution and does not coincide with the change in ORR activity.
また、さらに酸素欠損量をより明確に評価するために、Ca置換量0〜20%の試料について熱重量（TG）分析を行った結果を図14に示す。各試料に対して、酸素中400℃で前処理を行うことで吸着している詩文の除去を行った後、5%水素、95%アルゴン混合雰囲気下において、1℃/minの昇温速度で分析を行った。その結果、Ca置換なしでは酸素量が3.02であるのに対し、Ca10%置換では2.96と酸素量が減少しており、酸素欠損が生じていることが明らかとなった。またCa20％置換においては酸素量が2.97とCa10%置換とほとんど変化しておらず（図14左図）、これらの酸素量の変化とORR過電圧の変化（図14右図）からも、酸素欠損が生じることによりORR活性が向上していることが示唆された。 Furthermore, in order to more clearly evaluate the oxygen deficiency, FIG. 14 shows the result of thermogravimetric (TG) analysis performed on a sample with a Ca substitution amount of 0 to 20%. After removing the poetry adsorbed by pre-treating each sample at 400 ° C in oxygen, it was heated at a rate of 1 ° C / min in a mixed atmosphere of 5% hydrogen and 95% argon. Analysis was carried out. As a result, the oxygen content was 3.02 without Ca substitution, whereas the oxygen content decreased to 2.96 with Ca 10% substitution, indicating that oxygen deficiency occurred. In addition, the oxygen content in Ca20% substitution is almost the same as that in Ca10% substitution with 2.97 (Fig. 14 left figure). From these oxygen quantity changes and ORR overvoltage changes (right figure in Fig. 14), oxygen deficiency This suggests that ORR activity is improved.
さらにNi置換量を最適化した際のORR活性を図15に示す。Ni置換量を0.5から0.1に減少させることにより、ORR活性が極めて大きく向上することが分かった。ただし、600℃での低温焼成を行うために、Ni置換量の減少に伴うCa置換量の最適化を行った。その結果、La1-xCaxMn1-yNiyO3-δ（0≦x≦0.5、0≦y≦0.5）において、x=0.4、y=0.1にすることで、50 μA cm-2における電位は約0.940 V vs RHEというこれまでにない小さな過電圧を達成した。これは現在、ORRに対して最も高活性な遷移金属酸化物の1つであるLaNiO3（0.910 V vs RHE@50 μA/cm2）よりも過電圧が0.03 Vほど小さい。また電流値についても、0.9 V vs RHEにおいてLaNiO3が-0.09 mA/cm2であるのに対し、約-0.55 mA/cm2@0.9 V vs RHEという、LaNiO3の6倍もの大きな還元電流を得ることができており、これまで報告してきた酸素欠損を有するダブルペロブスカイト型BaLaMn2O5+δをもしのぐ、ORRに対して極めて高活性な遷移金属酸化物触媒の合成に成功した。Further, FIG. 15 shows the ORR activity when the Ni substitution amount is optimized. It was found that ORR activity was greatly improved by reducing the Ni substitution amount from 0.5 to 0.1. However, in order to perform low-temperature firing at 600 ° C., the amount of Ca substitution was optimized as the amount of Ni substitution decreased. As a result, in La 1-x Ca x Mn 1-y Ni y O 3-δ (0 ≦ x ≦ 0.5, 0 ≦ y ≦ 0.5), x = 0.4, y = 0.1, 50 μA cm − The potential at 2 achieved an unprecedented small overvoltage of about 0.940 V vs RHE. This has an overvoltage of 0.03 V smaller than LaNiO 3 (0.910 V vs RHE @ 50 μA / cm 2 ), which is currently one of the most active transition metal oxides for ORR. As for the current value, 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. We have succeeded in synthesizing a transition metal oxide catalyst with extremely high activity against ORR, which surpasses the double perovskite BaLaMn 2 O 5 + δ with oxygen deficiency reported so far.
次に最もORR活性に優れていたx=0.4、y=0.1（La0.6Ca0.4Mn0.9Ni0.1O3-d）の試料について、ORR条件下での安定性を評価した。評価条件を以下に示し、結果を図16、17に示す。Next, the stability under ORR conditions was evaluated for samples with x = 0.4 and y = 0.1 (La 0.6 Ca 0.4 Mn 0.9 Ni 0.1 O 3-d ), which had the highest ORR activity. The evaluation conditions are shown below, and the results are shown in FIGS.
安定性は、酸素飽和4 mol dm-3 KOH水溶液中においてORRが起こる0.6 V vs RHEで24 h定電位保持し、その前後でのXRD測定、及びORR活性評価を行うことで評価した。定電位保持前後でのXRD測定の結果（図16）より、定電位保持後もLa0.6Ca0.4Mn0.9Ni0.1O3-dのパターンが確認されており、導電性補助剤として加えているアセチレンブラック（AB）以外のピークも現れていないことから、定電位保持後も不純物が生成しておらず、安定であることが分かった。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.
また0.6 V vs RHE定電位保持中の電流値変化（図17左図）より、電位保持中に大きな電流変化が起こっていないことが分かった。さらに定電位保持前後でのORR活性比較（図17右図）より、電流電位曲線に大きな変化は見られず、このことからもLa0.6Ca0.4Mn0.9Ni0.1O3-dがORRに対して安定であることが示唆された。In addition, it was found from the change in the current value while holding the constant potential at 0.6 V vs RHE (the left figure in FIG. 17) that no large current change occurred during the holding of the potential. Furthermore, from the comparison of ORR activity before and after holding the constant potential (Fig. 17 right), there was no significant change in the current-potential curve, indicating that La 0.6 Ca 0.4 Mn 0.9 Ni 0.1 O 3-d It was suggested to be stable.
本発明は、二次電池、次世代型高容量二次電池として期待されている金属空気二次電池や、光水分解による水素製造の分野において有用である。 INDUSTRIAL APPLICABILITY 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.
Claims (15)
The metal-air secondary battery according to claim 14, further comprising an oxygen reduction air electrode including an oxygen reduction catalyst.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08504998A (en) * | 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 | Bifunctional air electrode |
| WO2010100752A1 (en) * | 2009-03-06 | 2010-09-10 | トヨタ自動車株式会社 | Air electrode and non-aqueous air battery |
| JP2011016684A (en) * | 2009-07-08 | 2011-01-27 | Hokkaido Univ | Oxygen deficit perovskite-type metal oxide excellent in oxygen storage capability, exhaust gas purifying catalyst and functional ceramic containing the metal oxide, and method and apparatus using the metal oxide |
| JP2013218986A (en) * | 2012-04-12 | 2013-10-24 | Nippon Telegr & Teleph Corp <Ntt> | Lithium air secondary battery |
| JP2013255911A (en) * | 2012-06-14 | 2013-12-26 | Mitsubishi Chemicals Corp | Catalyst for producing synthesis gas and production method of synthesis gas |
-
2016
- 2016-02-05 JP JP2017500604A patent/JP6731199B2/en not_active Expired - Fee Related
- 2016-02-05 WO PCT/JP2016/053451 patent/WO2016132932A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08504998A (en) * | 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 | Bifunctional air electrode |
| WO2010100752A1 (en) * | 2009-03-06 | 2010-09-10 | トヨタ自動車株式会社 | Air electrode and non-aqueous air battery |
| JP2011016684A (en) * | 2009-07-08 | 2011-01-27 | Hokkaido Univ | Oxygen deficit perovskite-type metal oxide excellent in oxygen storage capability, exhaust gas purifying catalyst and functional ceramic containing the metal oxide, and method and apparatus using the metal oxide |
| JP2013218986A (en) * | 2012-04-12 | 2013-10-24 | Nippon Telegr & Teleph Corp <Ntt> | Lithium air secondary battery |
| JP2013255911A (en) * | 2012-06-14 | 2013-12-26 | Mitsubishi Chemicals Corp | Catalyst for producing synthesis gas and production method of synthesis gas |
Non-Patent Citations (7)
| Title |
|---|
| FEIFEI DONG ET AL.: "Structural and oxygen-transport studies of double perovskites PrBa1-xCo2O5+δ (x = 0.00, 0.05, and 0", JOURNAL OF MATERIALS CHEMISTRY A, vol. Volume 2, Issue48, JPN6016009944, 2014, pages 20520 - 20529, ISSN: 0004222112 * |
| JING DU ET AL.: "Nonstoichiometric Perovskite CaMnO3-δ for Oxygen Electrocatalysis with High Activity", INORGANIC CHEMISTRY, vol. Volume 53, Issue 17, JPN6016009919, 2014, pages 9106 - 9114, ISSN: 0004222115 * |
| MABROUK CHERITI ET AL.: "Double perovskite oxides Sr2MMoO6 (M = Fe and Co) as cathode materials for oxygen reduction in alkal", MATERIALS RESEARCH BULLETIN, vol. Volume 47, Issue 1, JPN6016009922, 2012, pages 135 - 141, ISSN: 0004222110 * |
| SEONYOUNG YOO ET AL.: "Development of Double-Perovskite Compounds as Cathode Materials for Low-Temperature Solid Oxide Fuel", ANGEWANDTE CHEMIE INTERNATIONAL EDITION, vol. 53, JPN6016009923, 2014, pages 13064 - 13067, ISSN: 0004222113 * |
| YAN LI ET AL.: "Oxygen-Deficient Perovskite Sr0.7Y0.3CoO2.65-δ as a Cathode for Intermediate-Temperature Solid Oxid", CHEMISTRY OF MATERIALS, vol. Volume 23, Issue 22, JPN6016009921, 2011, pages 5037 - 5044, ISSN: 0004222114 * |
| ZHONG MA ET AL.: "The double perovskite oxide Sr2CrMoO6-δ as an efficient electrocatalyst for rechargeable lithium ai", CHEMICAL COMMUNICATIONS, vol. Volume 50, Issue 94, JPN6016009942, 2014, pages 14855 - 14858, ISSN: 0004222111 * |
| 野田裕之: "酸素不定性比を有する金属酸化物の酸素還元／酸素発生電極触媒活性", 化学系学協会北海道支部冬季研究発表会講演要旨集, JPN6016009946, 28 January 2014 (2014-01-28), pages 1 - 07, ISSN: 0004222109 * |
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