JPS6319981B2 - - Google Patents
Info
- Publication number
- JPS6319981B2 JPS6319981B2 JP56197147A JP19714781A JPS6319981B2 JP S6319981 B2 JPS6319981 B2 JP S6319981B2 JP 56197147 A JP56197147 A JP 56197147A JP 19714781 A JP19714781 A JP 19714781A JP S6319981 B2 JPS6319981 B2 JP S6319981B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- air
- cyanocobalamin
- present
- iron phthalocyanine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- RMRCNWBMXRMIRW-BYFNXCQMSA-M cyanocobalamin Chemical compound N#C[Co+]N([C@]1([H])[C@H](CC(N)=O)[C@]\2(CCC(=O)NC[C@H](C)OP(O)(=O)OC3[C@H]([C@H](O[C@@H]3CO)N3C4=CC(C)=C(C)C=C4N=C3)O)C)C/2=C(C)\C([C@H](C/2(C)C)CCC(N)=O)=N\C\2=C\C([C@H]([C@@]/2(CC(N)=O)C)CCC(N)=O)=N\C\2=C(C)/C2=N[C@]1(C)[C@@](C)(CC(N)=O)[C@@H]2CCC(N)=O RMRCNWBMXRMIRW-BYFNXCQMSA-M 0.000 claims description 32
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 16
- 229960002104 cyanocobalamin Drugs 0.000 claims description 16
- 235000000639 cyanocobalamin Nutrition 0.000 claims description 16
- 239000011666 cyanocobalamin Substances 0.000 claims description 16
- 239000000446 fuel Substances 0.000 claims description 12
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000007772 electrode material Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000002940 repellent Effects 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 229910002515 CoAl Inorganic materials 0.000 description 1
- 229910003321 CoFe Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000645 Hg alloy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- -1 manganese and osmium Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9008—Organic or organo-metallic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inert Electrodes (AREA)
Description
【発明の詳細な説明】
本発明は、分極が小さく、大電流の取得を可能
にする燃料電池または空気電池用の電極、さらに
詳細には、燃料電池または空気電池の空気極また
は酸素極において、該電極が触媒として鉄フタロ
シアニンとシアノコバラミンの両遷移金属錯体を
含有する新規な上記電極に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention provides an electrode for a fuel cell or an air cell that has small polarization and can obtain a large current, and more specifically, an air electrode or an oxygen electrode for a fuel cell or an air cell. The present invention relates to the above novel electrode, wherein the electrode contains both transition metal complexes of iron phthalocyanine and cyanocobalamin as catalysts.
従来、燃料電池、空気電池用の空気極または酸
素極に用いる触媒については、種々の提案がなさ
れている。 Conventionally, various proposals have been made regarding catalysts used in air electrodes or oxygen electrodes for fuel cells and air cells.
すなわち、燃料電池用の空気極触媒又は酸素極
触媒としては、銅、銀、金、白金、パラジウム等
の金属類、タングステンブロンズ、鉄又は銅フタ
ロシニアン、活性炭及びリチウムをドープした酸
化ニツケル等が知られ、又、空気電池用の空気極
触としては、白金、パラジウム、ルチニウム及び
銀等の貴金属類、銀と水銀及びルチニウムと金等
の合金類、マンガン及びオスミウム等の遷移金属
の酸化物類及びNiFe2O4，CoFe2O4，NiCr2O4及
びCoAl2O4等のスピネル酸化物類が知られてい
る。 That is, as air electrode catalysts or oxygen electrode catalysts for fuel cells, metals such as copper, silver, gold, platinum, and palladium, tungsten bronze, iron or copper phthalocyanine, activated carbon, and nickel oxide doped with lithium are known. In addition, as air electrode catalysts for air batteries, noble metals such as platinum, palladium, rutinium and silver, alloys of silver and mercury and rutinium and gold, oxides of transition metals such as manganese and osmium, and NiFe Spinel oxides such as 2 O 4 , CoFe 2 O 4 , NiCr 2 O 4 and CoAl 2 O 4 are known.
しかしながら、従来技術におけるこれらの触媒
のうち、貴金属類は高価なため経済的でなく、そ
れ以外のもしは安価であるが、これを触媒として
用いた空気極又は酸化極はその分極が貴金属より
大きく、又、大電流密度領域におけるかなりの電
位低下が避けられない等、その電極特性が十分に
良好でなく、ひいては、このような電極を組み込
んだ燃料電池及び空気電池において、大電流が取
得できないという欠点があつた。 However, among these catalysts in the prior art, noble metals are expensive and are not economical, whereas other catalysts, which are inexpensive, such as air electrodes or oxidation electrodes, have a polarization greater than that of noble metals. In addition, the electrode characteristics are not good enough, such as a considerable potential drop in the high current density region, and as a result, large currents cannot be obtained in fuel cells and air cells incorporating such electrodes. There were flaws.
本発明はこのような現状に鑑みてなされたもの
であり、その目的は、分極が小さく、大電流密度
領域においても電位低下が殆んど起こらず大電流
の取得が可能である高エネルギー密度の燃料電
池、空気電池用電極を提供することである。 The present invention has been made in view of the current situation, and its purpose is to provide a high energy density device that has small polarization and can obtain a large current with almost no potential drop even in the large current density region. The purpose of the present invention is to provide electrodes for fuel cells and air cells.
本発明につき概説すれば、本発明の燃料電池及
び空気電池用電極は、正極が触媒として鉄フタロ
シアニン及びシアノコバラミン（ビタミン
B12）を含有することを特徴とするものである。 To summarize the present invention, the fuel cell and air cell electrodes of the present invention have positive electrodes containing iron phthalocyanine and cyanocobalamin (vitamin) as catalysts.
B 12 ).
これまで燃料電池及び空気電池用の空気極又は
酸素極に触媒として鉄フタロシアニン及びシアノ
コバラミンの両物質を共に用いた例はない。本発
明によれば、電極に鉄フタロシアニン及びシアノ
コバラミン両物質を含有させる新規な構成によ
り、後述するように各々単独に用いるよりも分極
を小さくし、かつ、大電流の取得を可能にすると
いう優れた複合効果が得られる。 Until now, there has been no example of using both iron phthalocyanine and cyanocobalamin as a catalyst in an air electrode or an oxygen electrode for a fuel cell or an air cell. According to the present invention, the novel structure in which the electrode contains both iron phthalocyanine and cyanocobalamin has the advantage of reducing polarization and making it possible to obtain a large current compared to when each is used alone, as described below. A combined effect can be obtained.
本発明を更に詳しく説明する。 The present invention will be explained in more detail.
燃料電池は、負極活物質として水素ガス等を使
用し、電解質としてKOH，NaOH等のアルカリ
電解質、NaCl、KCl等の中性電解質、リン酸等
の酸性電解質を使用して構成され、又、空気電池
は負極活物質として亜鉛、アルミニウム、マグネ
シウム、白金又はこれらの合金等使用し、電解質
として上記と同じものを使用して構成される。 A fuel cell is constructed using hydrogen gas as a negative electrode active material, alkaline electrolytes such as KOH and NaOH, neutral electrolytes such as NaCl and KCl, and acidic electrolytes such as phosphoric acid as electrolytes. The battery is constructed using zinc, aluminum, magnesium, platinum, or an alloy thereof as a negative electrode active material, and the same material as above as an electrolyte.
本発明にける電極は上述の燃料電池ないし空気
電池の正極として用いられるが、上記正極材料
は、炭素粉末、活性炭、グラフアイトまたはアセ
チレンブラツク等の炭素物質とテフロン等の撥水
剤等との混合粉体等であることができ、本発明に
よれば、これに鉄フタロシアニン及びシアノコバ
ラミンの混合物質を触媒として混合等の手段によ
り担持する。 The electrode of the present invention is used as a positive electrode of the above-mentioned fuel cell or air cell, and the above-mentioned positive electrode material is a mixture of a carbon material such as carbon powder, activated carbon, graphite, or acetylene black, and a water repellent such as Teflon. According to the present invention, a mixed substance of iron phthalocyanine and cyanocobalamin is supported on the powder by means of mixing or the like as a catalyst.
正極電極は、上記炭素物質、撥水剤及び鉄フタ
ロシアニン及びシアノコバラミンから成る混合粉
体をニツケル、銀等の金属網と共に成形圧着し、
これを加熱焼成して作成することができる。 The positive electrode is made by molding and press-bonding a mixed powder consisting of the carbon material, water repellent, iron phthalocyanine, and cyanocobalamin together with a metal mesh such as nickel or silver.
This can be created by heating and firing.
本発明における上記鉄フタロシアニン及びシア
ノコバラミン混合体が複合触媒として有効である
理由は、正極の電極反応のうち最も効率の良い４
電子反応（O2＋2H2O＋4e-→4OH-）を選択し得
る鉄フタロシアニンと、４電子反応の選択性が低
い場合（例えばO2＋H2O＋2e-→HO2 -＋OH-及
びHO2 -→1/2O2＋OH-のような２電子反応が起
る）においても生成する中間体（酸性電解質使用
の場合：H2O2，アルカリ電解質使用の場合：
HO2 -）の分解速度を大きくするシアノコバラミ
ンを共に担持することにより、どのような反応プ
ロセスをとろうとも電極反応を十分円滑に進める
に足る電子の供給が容易であるためと考えられ
る。特に測定の結果では、中間体の分解速度は、
白金黒より高く、鉄フタロシアニン単独の場合の
５倍に達している。 The reason why the above-mentioned iron phthalocyanine and cyanocobalamin mixture in the present invention is effective as a composite catalyst is that the most efficient of the positive electrode reactions is
Iron phthalocyanine that can select the electron reaction (O 2 + 2H 2 O + 4e - → 4OH - ) and when the selectivity of the 4-electron reaction is low (e.g. O 2 + H 2 O + 2e - → HO 2 - +OH - and HO 2 - → 1) /2O 2 + OH - (two-electron reactions such as
It is thought that this is because by supporting cyanocobalamin, which increases the decomposition rate of HO 2 - ), it is easy to supply enough electrons to make the electrode reaction proceed smoothly no matter what reaction process is used. In particular, the results of the measurements show that the decomposition rate of the intermediate is
It is higher than platinum black and five times higher than that of iron phthalocyanine alone.
次に、本発明における正極の構造を図面により
説明する。すなわち、第１図は本発明における正
極（空気極）の構造の一具体例を示した断面概略
図を示し、１は電極材料層、２はニツケル製網を
示す。 Next, the structure of the positive electrode in the present invention will be explained with reference to the drawings. That is, FIG. 1 shows a schematic cross-sectional view showing a specific example of the structure of the positive electrode (air electrode) according to the present invention, in which 1 shows an electrode material layer and 2 shows a nickel mesh.
この空気極を電池に組み込むに当つては、電極
材料層１が電解質に、ニツケル製網がガスに接す
るように向きを定める。この結果、電極材料層１
中に電解質、ガス及び電極粉体の三相界面が形成
される。なお、ニツケル製網２は、電極材料層１
の支持体及び集電体として設けられる。なお、こ
の際、電極の寿命を延ばすために、ガス側に接す
る金属網の外側に、第２の電極材料層をサンドイ
ツチ型に設けてもよく、この場合、第２の電極材
料層は、電解質側に設けた第１の電極材料層より
撥水剤の混合割合を多くして撥水性を高め、か
つ、多孔性を大にする。 When this air electrode is assembled into a battery, it is oriented so that the electrode material layer 1 is in contact with the electrolyte and the nickel mesh is in contact with the gas. As a result, electrode material layer 1
A three-phase interface of electrolyte, gas and electrode powder is formed therein. Note that the nickel net 2 has an electrode material layer 1
It is provided as a support and a current collector. In this case, in order to extend the life of the electrode, a second electrode material layer may be provided in a sanderch type on the outside of the metal mesh in contact with the gas side. In this case, the second electrode material layer The water repellent is mixed in a higher proportion than the first electrode material layer provided on the side to improve water repellency and increase porosity.
次に、本発明を実施例によつて説明するが、本
発明はこれにより何ら限定されるものではない。
なお、実施例における電極電位の電流依存性の測
定は20〜25℃の室温中で行なつた。 Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto in any way.
In addition, the measurement of the current dependence of the electrode potential in the Examples was carried out at room temperature of 20 to 25°C.
実施例 １
炭素粉末（200メツシユ通過）４ｇ、アセチレ
ンブラツク４ｇ、鉄フタロシアニンとシアノコバ
ラミンの触媒混合物0.2ｇとテフロンエマルジヨ
ン（テフロン60％含有）3.3ｇをよく混合し、ロ
ールでシート状にする。シートを30分間程度空気
中で乾燥させた後、片側にニツケル製網（50メツ
シユ）を置き、250℃の温度、100Kg／cm2の圧で30
分間ホツトプレスする。空気中で冷却し、直径30
mmの円形に切り出して空気極（正極）を作製し
た。Example 1 4 g of carbon powder (passed through 200 meshes), 4 g of acetylene black, 0.2 g of a catalyst mixture of iron phthalocyanine and cyanocobalamin, and 3.3 g of Teflon emulsion (containing 60% Teflon) were thoroughly mixed and formed into a sheet using a roll. After drying the sheet in the air for about 30 minutes, place a nickel mesh (50 mesh) on one side and dry it at a temperature of 250℃ and a pressure of 100Kg/ cm2 for 30 minutes.
Hot press for a minute. cooled in air, diameter 30
An air electrode (positive electrode) was prepared by cutting out a circular shape of mm.
電解質としてIN KOH を使用し、亜鉛を負
極として空気電池を構成し、空気中で空気極の電
極電位（Ｅ、対飽和カロメル電極）の電流密度依
存性を調べた。結果を第２図に示す。すなわち、
第２図は、本実施例における空気極の電流密度と
電極電圧との関係を示したグラフであり、Ａは本
実施例のうち、混合触媒重量の割合が鉄フタロシ
アニン１：１シアノコバラミンの場合、Ｂは本実
施例のうち混合触媒の重量割合が鉄フタロシアニ
ン４：１シアノコバラミシの場合、Ｃは本実施例
のうち割合が鉄フタロシアニン１：４シアノコバ
ラミンの場合Ｄ、Ｅは併せて行なつた従来既知の
触媒を用いた空気極の場合であり、Ｄは鉄フタロ
シアニン、Ｅは銀触媒を用いた場合である。 An air battery was constructed using IN KOH as the electrolyte and zinc as the negative electrode, and the dependence of the electrode potential of the air electrode (E, vs. saturated calomel electrode) on current density in air was investigated. The results are shown in Figure 2. That is,
FIG. 2 is a graph showing the relationship between the current density of the air electrode and the electrode voltage in this example. B is in this example when the weight ratio of the mixed catalyst is iron phthalocyanine 4:1 cyanocobalamin; C is in this example when the ratio is iron phthalocyanine 1:4 cyanocobalamin D is the case where an iron phthalocyanine is used, and E is the case where a silver catalyst is used.
第２図によると、鉄フタロシアニンとシアノコ
バラミンが１：１の重量比で混合担持された場
合、平衡電位が−0.033 Ｖ（対SCE≪飽和カロメ
ル電極≫）、100mA／cm2のとき−0.68V（対SCE）、
一方、鉄フタロシアニンとシアノコバラミンが
４：１の重量比で混合担持された場合には、平衡
電位が＋0.030V（対SCE）、100mA／cm2のとき−
0.60V（対SCE）となる。 According to Figure 2, when iron phthalocyanine and cyanocobalamin are mixed and supported at a weight ratio of 1:1, the equilibrium potential is -0.033 V (vs. SCE <<saturated calomel electrode>>), and -0.68 V at 100 mA/ cm2 ( vs. SCE),
On the other hand, when iron phthalocyanine and cyanocobalamin are mixed and supported at a weight ratio of 4:1, when the equilibrium potential is +0.030V (vs. SCE) and 100mA/ cm2 , -
0.60V (vs. SCE).
第２図から明らかなように、鉄フタロシアニン
や銀を用いた従来の場合に比し、鉄フタロシアニ
ンとシアノコバラミンを混合して用いた本発明の
場合には、平衡電位が高く、分極が小さく、かつ
大電流密度領域でも電位の大幅な低下が見られず
安定している。 As is clear from FIG. 2, compared to the conventional case using iron phthalocyanine and silver, the present invention using a mixture of iron phthalocyanine and cyanocobalamin has a higher equilibrium potential, smaller polarization, and Even in the high current density region, there is no significant drop in potential and it is stable.
以上説明したように、鉄フタロシアニンとシア
ノコバラミンの両物質を触媒として複合担持した
本発明における正極（空気極または酸素極）は、
分極が小さく、かつ、大電流密度領域においても
電位低下が殆んど起こらず、この点、従来のもの
に比し優れた効果を発揮するものである。したが
つて、この電極を正極として組み込んだ燃料電池
及び空気電池は、大電流の取得ができ、又、より
一層の高エネルギー密度化が可能であり、従来品
に比し極めて高い実用価値を期待することができ
る。 As explained above, the positive electrode (air electrode or oxygen electrode) of the present invention in which iron phthalocyanine and cyanocobalamin are compositely supported as catalysts,
The polarization is small, and there is almost no potential drop even in the high current density region, and in this respect, it exhibits superior effects compared to conventional ones. Therefore, fuel cells and air cells incorporating this electrode as a positive electrode can obtain large currents and have even higher energy density, and are expected to have extremely high practical value compared to conventional products. can do.
第１図は本発明における正極（空気極）の構造
の一具体例を示した断面概略図、第２図はそれぞ
れ本発明の実施例の空気極の電流密度と電極電位
の関係を示したグラフである。
１……電極材料層、２……ニツケル製網。
FIG. 1 is a cross-sectional schematic diagram showing a specific example of the structure of the positive electrode (air electrode) according to the present invention, and FIG. 2 is a graph showing the relationship between current density and electrode potential of the air electrode of the embodiment of the present invention. It is. 1... Electrode material layer, 2... Nickel net.
Claims (1)
移金属錯体を触媒として含有することを特徴とす
る燃料電池、空気電池用電極。1. An electrode for fuel cells and air cells, characterized by containing both transition metal complexes of iron phthalocyanine and cyanocobalamin as catalysts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56197147A JPS58100363A (en) | 1981-12-08 | 1981-12-08 | Electrode for fuel cell or air cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56197147A JPS58100363A (en) | 1981-12-08 | 1981-12-08 | Electrode for fuel cell or air cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58100363A JPS58100363A (en) | 1983-06-15 |
| JPS6319981B2 true JPS6319981B2 (en) | 1988-04-26 |
Family
ID=16369536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56197147A Granted JPS58100363A (en) | 1981-12-08 | 1981-12-08 | Electrode for fuel cell or air cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58100363A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4897278B2 (en) * | 2005-11-25 | 2012-03-14 | 株式会社リコー | Developing device, image forming cartridge, and image forming apparatus |
| JP2013016474A (en) * | 2011-06-06 | 2013-01-24 | Sumitomo Chemical Co Ltd | Positive electrode catalyst for air secondary battery and air secondary battery |
-
1981
- 1981-12-08 JP JP56197147A patent/JPS58100363A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58100363A (en) | 1983-06-15 |
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