JP7279458B2 - Method for producing manganese oxide/conductive carrier composite - Google Patents
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims description 141
- 239000002131 composite material Substances 0.000 title claims description 40
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000002245 particle Substances 0.000 claims description 19
- 150000002696 manganese Chemical class 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000005868 electrolysis reaction Methods 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 11
- 150000001340 alkali metals Chemical class 0.000 claims description 11
- 239000012266 salt solution Substances 0.000 claims description 6
- 229910003174 MnOOH Inorganic materials 0.000 claims description 4
- 229910016978 MnOx Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 11
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 10
- 239000011572 manganese Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003273 ketjen black Substances 0.000 description 5
- 229940099596 manganese sulfate Drugs 0.000 description 5
- 235000007079 manganese sulphate Nutrition 0.000 description 5
- 239000011702 manganese sulphate Substances 0.000 description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- -1 manganese alkali salt Chemical class 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- KVGMATYUUPJFQL-UHFFFAOYSA-N manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++] KVGMATYUUPJFQL-UHFFFAOYSA-N 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
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Description
本発明は、マンガン酸化物／導電性担体複合体の製造方法に関するものであり、より詳しくは、電池、例えば空気電池において、酸素還元／酸素発生触媒として使用されるマンガン酸化物／導電性担体複合体の製造方法に関する。 TECHNICAL FIELD The present invention relates to a method for producing a manganese oxide/conductive support composite, and more particularly to a manganese oxide/conductive support composite used as an oxygen reduction/oxygen evolution catalyst in a battery, such as an air battery. It relates to the manufacturing method of the body.
マンガン酸化物／導電性担体は、高価な貴金属元素や貴金属元素／カーボン担体等の酸素還元／酸素発生触媒の安価な代替品として種々検討行われていることが知られている。例えば非特許文献１では各種マンガン酸化物の酸素還元／酸素発生触媒能を評価しており、特許文献１では高純度ラムズデライト型二酸化マンガンをカーボンに担持し空気極触媒に用いた空気電池が検討されており、特許文献２では平均粒子径１００ｎｍ以下のＭｎＯｘ（ｘ＝４／３～８／５）を触媒として用いた空気電池用触媒が検討されている。 It is known that manganese oxides/conductive supports have been variously studied as inexpensive substitutes for oxygen reduction/oxygen evolution catalysts such as expensive noble metal elements and noble metal elements/carbon supports. For example, Non-Patent Document 1 evaluates the oxygen reduction/oxygen generation catalytic ability of various manganese oxides, and Patent Document 1 examines an air battery in which high-purity ramsdellite-type manganese dioxide is supported on carbon and used as an air electrode catalyst. In Patent Document 2, an air battery catalyst using MnOx (x=4/3 to 8/5) having an average particle size of 100 nm or less is studied.
一方、高効率なマンガン酸化物の製造方法として非特許文献２では、電極上にマンガン酸化物を電着させずに電解を実施する方法が提案されている。 On the other hand, as a highly efficient method for producing manganese oxide, Non-Patent Document 2 proposes a method of performing electrolysis without electrodepositing manganese oxide on an electrode.
非特許文献１の材料は、合成方法の煩雑さや導電性担体であるカーボンとの混合を、後工程で実施している点から導電性担体上にマンガン酸化物が高分散しにくいことに加え、工程数が多くなり工業的には効率が低いことが予想される。また、マンガンアルカリ塩を用いた合成かつ、アルカリを構造中に取り込んでしまう結晶構造であるため、触媒反応上不要なアルカリ金属を材料中に余分に含有してしまう問題点を有している。特許文献１は、触媒電極として使用する際のマンガン酸化物の分散性や二次粒子の状態については言及されておらず、有効に三相界面を形成できていないことが予想される。また、工程数も多くなる。特許文献２は、記載の平均粒子径は導電性担体に担持する前の一次粒子径であり、後工程で導電性担体と混合した際に、粒子が凝集していることが予想される。 In the material of Non-Patent Document 1, manganese oxide is difficult to disperse highly on the conductive support because the synthesis method is complicated and the mixing with carbon, which is the conductive support, is performed in a post-process. It is expected that the number of steps will increase and the efficiency will be low industrially. In addition, since it is synthesized using a manganese alkali salt and has a crystal structure that incorporates alkali into the structure, there is a problem that the material contains excess alkali metal unnecessary for the catalytic reaction. Patent document 1 does not refer to the dispersibility of manganese oxide or the state of secondary particles when used as a catalytic electrode, and it is expected that a three-phase interface cannot be effectively formed. Moreover, the number of steps is also increased. In Patent Document 2, the average particle size described is the primary particle size before being supported on the conductive carrier, and it is expected that the particles are aggregated when mixed with the conductive carrier in the subsequent step.
一方、非特許文献２では、アルカリ電池の材料として求められる粒子密度を高めることができず、工業化には至っていない。また、アルカリ電池向け材料として検討されていることから、導電性担体との複合化、酸素還元、発生触媒としての検討等は行われていない。 On the other hand, in Non-Patent Document 2, the particle density required as a material for alkaline batteries cannot be increased, and industrialization has not yet been achieved. In addition, since it is being studied as a material for alkaline batteries, it has not been studied as a composite with a conductive carrier, oxygen reduction, or as a generation catalyst.
本発明の目的は、電解により導電性担体の表面に、マンガン酸化物を担持させることで、簡便なマンガン酸化物／導電性担体複合体の製造方法を提供することである。 An object of the present invention is to provide a simple method for producing a manganese oxide/conductive carrier composite by supporting manganese oxide on the surface of a conductive carrier by electrolysis.
本発明者は、特に酸素還元・酸素発生用触媒として使用されるマンガン酸化物／導電性担体複合体の製造方法について鋭意検討を重ねた結果、マンガン塩水溶液中の電解により導電性担体表面に、マンガン酸化物を担持させることで、微細なマンガン酸化物粒子が導電性担体に高分散したマンガン酸化物／導電性担体複合体を効率よく製造できることを見出し、本発明を完成するに至った。すなわち、本発明は、マンガン塩水溶液に導電性担体を懸濁させて得られた導電性担体懸濁マンガン塩水溶液を用いて電解を行い、導電性担体表面に、マンガン酸化物を担持させる、ＭｎＯｘ（ｘ＝１．３～２．０５）又はＭｎＯＯＨで表される粒子径０．０１μｍ以上５０μｍ以下のマンガン酸化物が導電性担体の表面に担持しており、アルカリ金属元素の含有量が１．０ｗｔ％未満であるマンガン酸化物／導電性担体複合体の製造方法である。 As a result of intensive studies on a method for producing a manganese oxide/conductive support composite, which is used as a catalyst for oxygen reduction/oxygen generation, the present inventors found that electrolysis in an aqueous manganese salt solution produces the following: The inventors have found that by supporting manganese oxide, a manganese oxide/conductive carrier composite in which fine manganese oxide particles are highly dispersed in a conductive carrier can be efficiently produced, leading to the completion of the present invention. That is, in the present invention, electrolysis is performed using a conductive carrier-suspended manganese salt aqueous solution obtained by suspending a conductive carrier in a manganese salt aqueous solution, and manganese oxide is supported on the surface of the conductive carrier, MnOx (x=1.3 to 2.05) or manganese oxide having a particle size of 0.01 μm or more and 50 μm or less represented by MnOOH is supported on the surface of the conductive carrier, and the content of the alkali metal element is 1.0 μm. A method for producing a manganese oxide/conductive support composite that is less than 0 wt%.
以下、本発明について詳細に説明する。 The present invention will be described in detail below.
本発明のマンガン酸化物／導電性担体複合体の製造方法は、マンガン塩水溶液に導電性担体を懸濁させて得られた導電性担体懸濁マンガン塩水溶液を用いて電解を行い、導電性担体の表面に、マンガン酸化物を担持させるものである。 In the method for producing a manganese oxide/conductive carrier composite of the present invention, electrolysis is performed using a conductive carrier-suspended manganese salt aqueous solution obtained by suspending a conductive carrier in an aqueous manganese salt solution, Manganese oxide is supported on the surface of .
マンガン塩水溶液は電解槽内の電解液として用いるものである。マンガン塩に特に制限はないが、例えば、硝酸マンガン、塩化マンガン、硫酸マンガン等が例示できる。 The manganese salt aqueous solution is used as the electrolyte in the electrolytic cell. Manganese salts are not particularly limited, but examples include manganese nitrate, manganese chloride, and manganese sulfate.
導電性担体懸濁マンガン塩水溶液中の導電性担体の濃度は特に限定するものではないが、０．２ｇ／Ｌ以上１５．０ｇ／Ｌ以下が好ましく、０．５ｇ／Ｌ以上５．０ｇ／Ｌ以下がさらに好ましい。 The concentration of the conductive carrier in the conductive carrier-suspended manganese salt aqueous solution is not particularly limited, but is preferably 0.2 g/L or more and 15.0 g/L or less, and 0.5 g/L or more and 5.0 g/L. More preferred are:
本発明のマンガン酸化物／導電性担体複合体の製造方法では、電解を行う前又は電解を行っている間に、導電性担体懸濁マンガン塩水溶液に酸を添加してもよい。酸としては、例えば、硝酸、塩酸、硫酸等が例示できる。添加する量は特に限定するものではないが、０．１ｇ／Ｌ以上６０ｇ／Ｌ以下が好ましく、０．２ｇ／Ｌ以上５０ｇ／Ｌ以下がより好ましい。 In the method for producing a manganese oxide/conductive carrier composite of the present invention, an acid may be added to the conductive carrier-suspended aqueous manganese salt solution before or during electrolysis. Examples of acids include nitric acid, hydrochloric acid, sulfuric acid, and the like. Although the amount to be added is not particularly limited, it is preferably 0.1 g/L or more and 60 g/L or less, more preferably 0.2 g/L or more and 50 g/L or less.
本発明のマンガン酸化物／導電性担体複合体の製造方法では、電解を行う前又は電解を行っている間に、導電性担体懸濁マンガン塩水溶液に、さらにマンガン塩水溶液を添加してもよい。添加する量は特に限定するものではないが、３ｇ／Ｌ以上１４０ｇ／Ｌ以下が好ましく、５ｇ／Ｌ以上１３０ｇ／Ｌ以下がより好ましい。 In the method for producing a manganese oxide/conductive carrier composite of the present invention, an aqueous manganese salt solution may be added to the aqueous manganese salt solution suspended in the conductive carrier before or during electrolysis. . Although the amount to be added is not particularly limited, it is preferably 3 g/L or more and 140 g/L or less, more preferably 5 g/L or more and 130 g/L or less.
本発明のマンガン酸化物／導電性担体複合体の製造方法は、電析時の温度に特に制限はないが、マンガン塩水溶液の凝固・蒸発を抑える観点から１℃以上９９℃以下が好ましく、さらに、マンガン酸化物生成の副反応を抑制する観点から１℃以上８０℃以下がより好ましく、１℃以上６０℃以下がさらに好ましい。 In the method for producing a manganese oxide/conductive carrier composite of the present invention, the temperature during electrodeposition is not particularly limited. From the viewpoint of suppressing the side reaction of manganese oxide formation, the temperature is more preferably 1° C. or higher and 80° C. or lower, and further preferably 1° C. or higher and 60° C. or lower.
本発明のマンガン酸化物／導電性担体複合体の製造方法では、電解の期間に特に制限はなく、任意の量、任意のマンガン酸化物／導電性担体複合体の割合の複合体が得られる時間（例えば、３０分以上５日以下）でよい。 In the method for producing a manganese oxide/conductive support composite of the present invention, the period of electrolysis is not particularly limited, and the amount of time required to obtain a composite of any manganese oxide/conductive support composite ratio is obtained. (for example, 30 minutes or more and 5 days or less).
本発明のマンガン酸化物／導電性担体複合体の製造方法では、電流密度に特に制限はないが、電極一枚当たりのマンガン酸化物／導電性担体複合体の生産量を維持して、生産性を維持し、さらに、電極電位を低くして、電流効率を向上して、生産性を維持するため、０．５Ａ／ｄｍ２以上６０Ａ／ｄｍ２以下が好ましく、０．８Ａ／ｄｍ２以上５０Ａ／ｄｍ２以下がより好ましく、１．０Ａ／ｄｍ２以上４０Ａ／ｄｍ２以下がさらに好ましい。 In the method for producing a manganese oxide/conductive carrier composite of the present invention, the current density is not particularly limited. Furthermore, in order to lower the electrode potential, improve current efficiency, and maintain productivity, 0.5 A / dm 2 or more and 60 A / dm 2 or less is preferable, 0.8 A / dm 2 or more and 50 A /dm 2 or less is more preferable, and 1.0 A/dm 2 or more and 40 A/dm 2 or less is even more preferable.
導電性担体懸濁マンガン塩水溶液に対する電流量は特に限定するものではないが、０．０５Ａ／Ｌ以上８．０Ａ／Ｌ以下が好ましく、０．１Ａ／Ｌ以上６．５Ａ／Ｌ以下がより好ましく、０．１２Ａ／Ｌ以上５．０Ａ／Ｌ以下がさらに好ましい。 The amount of electric current for the manganese salt aqueous solution suspended in the conductive carrier is not particularly limited, but is preferably 0.05 A/L or more and 8.0 A/L or less, more preferably 0.1 A/L or more and 6.5 A/L or less. , more preferably 0.12 A/L or more and 5.0 A/L or less.
本発明のマンガン酸化物／導電性担体複合体の製造方法で得られるマンガン酸化物／導電性担体複合体は、導電性担体の表面に特定のマンガン酸化物が担持しているものである。 The manganese oxide/conductive support composite obtained by the method for producing a manganese oxide/conductive support composite of the present invention has a specific manganese oxide supported on the surface of the conductive support.
導電性担体の表面に担持しているマンガン酸化物は、ＭｎＯｘ（式中、ｘ＝１．３以上２．０５以下である）又はＭｎＯＯＨで表されるもので、一方又は両方を含有する。マンガン酸化物がこれらの一般式に該当しないと、酸素還元、発生触媒としての活性は低く、大気中での構造安定性も低くなる。 The manganese oxide supported on the surface of the conductive carrier is represented by MnOx (where x is 1.3 or more and 2.05 or less) or MnOOH, and contains one or both of them. If the manganese oxide does not meet these general formulas, its activity as a catalyst for oxygen reduction and generation will be low, and its structural stability in the atmosphere will also be low.
導電性担体の表面に担持しているマンガン酸化物の粒子径は、０．０１μｍ以上５０μｍ以下である。マンガン酸化物の粒子径が５０μｍより大きいと、触媒表面が少なくなり、触媒活性が低くなる。マンガン酸化物の粒子径が０．０１μｍより小さいと、マンガン酸化物の凝集により、触媒表面が少なくなり、触媒活性が低くなる。触媒表面をより確保するため、０．０２μｍ以上４０μｍ以下が好ましく、０．０３μｍ以上３０μｍ以下がさらに好ましい。 The particle size of the manganese oxide supported on the surface of the conductive carrier is 0.01 μm or more and 50 μm or less. If the particle size of the manganese oxide is larger than 50 μm, the surface area of the catalyst becomes small, resulting in low catalytic activity. If the particle size of the manganese oxide is less than 0.01 μm, the manganese oxide aggregates to reduce the surface area of the catalyst and lower the catalytic activity. In order to secure the catalyst surface more, it is preferably 0.02 μm or more and 40 μm or less, more preferably 0.03 μm or more and 30 μm or less.
マンガン酸化物／導電性担体複合体は、アルカリ金属元素の含有量が１．０ｗｔ％未満である。アルカリ金属元素の含有量が１．０ｗｔ％以上であると、アルカリ金属がマンガン酸化物の触媒活性を阻害し、触媒活性が低くなる。触媒活性をより維持するため、０．７ｗｔ％以下が好ましく、０．５ｗｔ％以下がさらに好ましい。ここに、アルカリ金属とは、例えば、Ｌｉ、Ｎａ、Ｋ等が例示され、Ｎａが好ましい。また、アルカリ金属の含有量の測定は、ＩＣＰ法により行われる。 The manganese oxide/conductive support composite has an alkali metal element content of less than 1.0 wt %. If the content of the alkali metal element is 1.0 wt % or more, the alkali metal inhibits the catalytic activity of the manganese oxide, resulting in low catalytic activity. 0.7 wt % or less is preferable, and 0.5 wt % or less is more preferable in order to maintain the catalytic activity. Alkali metals are exemplified by Li, Na, K and the like, with Na being preferred. Moreover, the measurement of content of an alkali metal is performed by ICP method.
マンガン酸化物／導電性担体複合体に含まれる導電性担体は、例えば、炭素材料、微細な金属粉、導電性金属酸化物等が例示される。炭素材料としては、炭素を含有し、マンガン酸化物を十分担持する表面があれば特に限定はないが、例えば、アセチレンブラック、カーボンブラック、グラファイト、ケッチェンブラック、活性炭素、カーボンナノチューブ、グラフェンシート等が例示され、カーボンブラック、ケッチェンブラックが好ましい。 Examples of the conductive carrier contained in the manganese oxide/conductive carrier composite include carbon materials, fine metal powders, and conductive metal oxides. The carbon material is not particularly limited as long as it contains carbon and has a surface that sufficiently supports manganese oxide. Examples include acetylene black, carbon black, graphite, ketjen black, activated carbon, carbon nanotubes, and graphene sheets. are exemplified, and carbon black and ketjen black are preferred.
マンガン酸化物／導電性担体複合体は、高いマンガン酸化物の分散性と触媒面積から、高性能な酸素還元・酸素発生用電極として、電池、特に空気電池の作用極として好適に使用することができる。 The manganese oxide/conductive carrier composite can be suitably used as a high-performance electrode for oxygen reduction/oxygen generation and as a working electrode for batteries, particularly air batteries, due to the high dispersibility and catalytic area of manganese oxide. can.
電池用の作用極として使用する方法として特に限定はなく、例えば、特許第５２１１８５８号公報等に記載される既知の方法で添加物と混合して作用極合剤として用いることができる。例えば、マンガン酸化物／導電性担体複合体に導電性を付与するためのカーボン、結着剤を加えた混合粉末を調製し、金属メッシュに圧着して作用極とすることができる。 There is no particular limitation on the method of using the working electrode for a battery, and for example, it can be used as a working electrode mixture by mixing with an additive by a known method described in Japanese Patent No. 5211858 or the like. For example, a mixed powder may be prepared by adding carbon and a binder for imparting conductivity to the manganese oxide/conductive support composite, and pressing it against a metal mesh to form a working electrode.
使用する作用極に特に限定はなく、例えば、Ｔｉ、グラファイト、ＰｂＯ２、ダイヤモンド電極、Ｐｔ、金、鉛、銅等が例示できる。 The working electrode to be used is not particularly limited, and examples thereof include Ti, graphite, PbO 2 , diamond electrode, Pt, gold, lead, copper and the like.
また、対極に関しても特に限定はなく、例えば、グラファイト、Ｐｔ、金、鉛、銅等が例示できる。 Also, the counter electrode is not particularly limited, and examples thereof include graphite, Pt, gold, lead, and copper.
マンガン酸化物／導電性担体複合体は、高いマンガン酸化物の分散性と触媒面積を有するため、出力特性に優れた電池として使用することができる。電池とは、空気電池、特に亜鉛－空気電池、リチウム－空気電池等が例示できる。 Since the manganese oxide/conductive carrier composite has high dispersibility of manganese oxide and high catalyst area, it can be used as a battery with excellent output characteristics. Examples of batteries include air batteries, particularly zinc-air batteries, lithium-air batteries, and the like.
本発明のマンガン酸化物／導電性担体複合体の製造方法は触媒活性の高いマンガン酸化物／導電性担体複合体を効率よく生産できる。 The method for producing a manganese oxide/conductive support composite of the present invention can efficiently produce a manganese oxide/conductive support composite with high catalytic activity.
以下、本発明を実施例及び比較例により詳細に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
＜粒子径の測定＞
粒子径の測定は「ＪＩＳ Ｈ ７８０４：２００５ 電子顕微鏡による金属触媒の粒子径測定方法」に準拠した。すなわち、ＳＥＭ－ＥＤＳ（走査型電子顕微鏡）にて倍率５，０００倍で観察した際のＭｎ粒子の長径Ｌｌと短径Ｌｓを求め、以下の式により粒子径ｄを算出した。
<Measurement of particle size>
The particle size was measured according to "JIS H 7804:2005 Method for measuring particle size of metal catalyst by electron microscope". That is, the major axis L l and the minor axis L s of the Mn particles observed at a magnification of 5,000 with a SEM-EDS (scanning electron microscope) were determined, and the particle diameter d was calculated by the following formula.
ｄ＝（Ｌｌ＋Ｌｓ）／２
実施例１
２．０ｍｏｌ／Ｌの硫酸マンガン水溶液中に、１．０ｇのケッチェンブラックを懸濁させて得たケッチェンブラック懸濁硫酸マンガン水溶液（硫酸マンガン水溶液中のケッチェンブラック濃度：１．２５ｇ／Ｌ）を用いて、ホウ素ドープダイヤモンド電極（１０ｃｍ２）を作用極、対極をＰｔ板とし、電流密度を２０Ａ／ｄｍ２、ケッチェンブラック懸濁硫酸マンガン水溶液に対する電流量を２．５Ａ／Ｌ、電解温度を１０℃として、１時間半電解し、マンガン酸化物／導電性担体複合体を得た。電解後のマンガン酸化物／導電性担体複合体は、洗浄後、６０℃で一晩乾燥させた。
d=(L l +L s )/2
Example 1
Ketjenblack-suspended manganese sulfate aqueous solution obtained by suspending 1.0 g of Ketjenblack in a 2.0 mol/L manganese sulfate aqueous solution (Ketjenblack concentration in manganese sulfate aqueous solution: 1.25 g/L ), a boron-doped diamond electrode (10 cm 2 ) was used as the working electrode and a Pt plate as the counter electrode, the current density was 20 A/dm 2 , the current amount for Ketjenblack-suspended manganese sulfate aqueous solution was 2.5 A/L, and electrolysis was performed. Electrolysis was carried out at a temperature of 10° C. for 1 hour and a half to obtain a manganese oxide/conductive carrier composite. The manganese oxide/conductive carrier composite after electrolysis was dried overnight at 60° C. after washing.
実施例１のマンガン酸化物／導電性担体複合体のＳＥＭ画像（×５，０００）およびＭｎ元素マッピング（５，０００倍）を図１に示す。 An SEM image (×5,000) and Mn elemental mapping (×5,000) of the manganese oxide/conductive support composite of Example 1 are shown in FIG.
Ｍｎ元素マッピングは、エネルギー分散型Ｘ線分析（ＥＤＳ）により、ＳＥＭ画像上の特性Ｘ線の強度を調べることで含有元素の濃度を調べることで行った。 Mn element mapping was performed by examining the concentration of contained elements by examining the intensity of characteristic X-rays on the SEM image by energy dispersive X-ray spectroscopy (EDS).
得られたＳＥＭ画像から、担体上に１μｍから５μｍ程度の粒子径のマンガン酸化物が分散していることが確認できた（マンガン酸化物の一般式：ＭｎＯＯＨ、マンガン酸化物の粒子径：１～５μｍ、マンガン酸化物／導電性担体複合体中のアルカリ金属元素の含有量：０．１ｗｔ％）。 From the obtained SEM image, it was confirmed that manganese oxide with a particle size of about 1 μm to 5 μm was dispersed on the carrier (general formula of manganese oxide: MnOOH, particle size of manganese oxide: 1 to 5 μm, content of alkali metal element in manganese oxide/conductive support composite: 0.1 wt %).
得られたサンプルをエタノールに分散させ、ＲＲＤＥ評価装置（商品名：ＲＲＤＥ－３、ＢＡＳ社製）用ディスク電極上に塗布し、走査速度５ｍＶ／ｓｅｃ、電極回転数１６００ｒｐｍでリニアスイープボルタンメトリー測定を実施し、参照極には飽和カロメル電極を使用し、－０．３Ｖでの電流値を測定した。還元電流値は４００μＡであった。 The resulting sample is dispersed in ethanol, applied to a disk electrode for an RRDE evaluation device (trade name: RRDE-3, manufactured by BAS), and subjected to linear sweep voltammetry measurement at a scanning speed of 5 mV/sec and an electrode rotation speed of 1600 rpm. A saturated calomel electrode was used as a reference electrode, and the current value at -0.3 V was measured. The reduction current value was 400 μA.
比較例１
ケッチェンブラック１ｇ、電解二酸化マンガンを２ｇ、エタノール１５０ｍｌを、ボールミルで４時間混合し、１５分間超音波処理した後、乾燥して、マンガン酸化物／導電性担体複合体を得た（マンガン酸化物の一般式：ＭｎＯ２、マンガン酸化物の粒子径：１８μｍ、マンガン酸化物／導電性担体複合体中のアルカリ金属元素の含有量：０．１ｗｔ％）。実施例１と同様の方法でリニアスイープボルタンメトリー測定を実施し、－０．３Ｖでの電流値を測定した。還元電流値は２８０μＡであった。
Comparative example 1
1 g of Ketjenblack, 2 g of electrolytic manganese dioxide, and 150 ml of ethanol were mixed in a ball mill for 4 hours, ultrasonically treated for 15 minutes, and dried to obtain a manganese oxide/conductive carrier composite (manganese oxide general formula: MnO 2 , particle size of manganese oxide: 18 μm, content of alkali metal element in manganese oxide/conductive support composite: 0.1 wt %). A linear sweep voltammetry measurement was performed in the same manner as in Example 1 to measure the current value at -0.3V. The reduction current value was 280 μA.
比較例２
電解二酸化マンガンを四三酸化マンガン（Ｍｎ３Ｏ４）に変更した以外は、比較例１と同様の方法により、マンガン酸化物／導電性担体複合体を得た（マンガン酸化物の一般式：Ｍｎ３Ｏ４、マンガン酸化物の粒子径：２５μｍ、マンガン酸化物／導電性担体複合体中のアルカリ金属元素の含有量：０．１ｗｔ％）。実施例１と同様の方法でリニアスイープボルタンメトリー測定を実施し、－０．３Ｖでの電流値を測定した。還元電流値は４０μＡであった。
Comparative example 2
A manganese oxide/conductive carrier composite was obtained in the same manner as in Comparative Example 1, except that the electrolytic manganese dioxide was changed to trimanganese tetraoxide (Mn 3 O 4 ) (general formula of manganese oxide: Mn 3 O 4 , particle size of manganese oxide: 25 μm, content of alkali metal element in manganese oxide/conductive support composite: 0.1 wt %). A linear sweep voltammetry measurement was performed in the same manner as in Example 1 to measure the current value at -0.3V. The reduction current value was 40 μA.
リニアスイープボルタンメトリーの結果に示されるように、実施例１で得られたマンガン酸化物／導電性担体複合体は比較例１、比較例２で得られた複合体と比較すると高い電流値を示した。これは、実施例１で得られたマンガン酸化物／導電性担体複合体において、マンガン酸化物が高分散しており、電解液、導電性担体、触媒の三相界面を形成しやすく、触媒活性が、比較例１、比較例２の粉砕混合品と比較し、高かったためであると考えられる。このことから、電池用の酸素還元・酸素発生用電極として考えた際に、優れた特性を示すことが分かった。 As shown in the results of linear sweep voltammetry, the manganese oxide/conductive carrier composite obtained in Example 1 showed a higher current value than the composites obtained in Comparative Examples 1 and 2. . This is because in the manganese oxide/conductive support composite obtained in Example 1, the manganese oxide is highly dispersed, and the three-phase interface of the electrolytic solution, the conductive support, and the catalyst is easily formed, and the catalytic activity was higher than the pulverized mixed products of Comparative Examples 1 and 2. From this, it was found that when considered as an electrode for oxygen reduction/oxygen generation for a battery, it exhibits excellent characteristics.
本発明のマンガン酸化物／導電性担体複合体の製造方法は、高い触媒活性を示すことが期待される電池用、酸素還元・酸素発生用電極に用いるマンガン酸化物／導電性担体複合体を簡便に製造することができる。 The method for producing a manganese oxide/conductive support composite of the present invention is a simple method for manufacturing a manganese oxide/conductive support composite for use in electrodes for oxygen reduction/oxygen generation, which is expected to exhibit high catalytic activity. can be manufactured to
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