JP5255989B2 - Electrocatalyst for polymer electrolyte fuel cell - Google Patents
Electrocatalyst for polymer electrolyte fuel cell Download PDFInfo
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- JP5255989B2 JP5255989B2 JP2008272640A JP2008272640A JP5255989B2 JP 5255989 B2 JP5255989 B2 JP 5255989B2 JP 2008272640 A JP2008272640 A JP 2008272640A JP 2008272640 A JP2008272640 A JP 2008272640A JP 5255989 B2 JP5255989 B2 JP 5255989B2
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- 239000000446 fuel Substances 0.000 title claims description 22
- 239000005518 polymer electrolyte Substances 0.000 title claims description 16
- 239000010411 electrocatalyst Substances 0.000 title claims 2
- 239000003054 catalyst Substances 0.000 claims description 70
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 61
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 47
- 229910052799 carbon Inorganic materials 0.000 claims description 43
- 239000010931 gold Substances 0.000 claims description 37
- 229910052697 platinum Inorganic materials 0.000 claims description 23
- 239000005871 repellent Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 230000002940 repellent Effects 0.000 claims description 13
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- 239000010419 fine particle Substances 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 239000010948 rhodium Substances 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 description 27
- 239000006229 carbon black Substances 0.000 description 24
- 230000000704 physical effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 238000010248 power generation Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910002837 PtCo Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229910001260 Pt alloy Inorganic materials 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005087 graphitization Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910002058 ternary alloy Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- UYXRCZUOJAYSQR-UHFFFAOYSA-N nitric acid;platinum Chemical compound [Pt].O[N+]([O-])=O UYXRCZUOJAYSQR-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- ZWZLRIBPAZENFK-UHFFFAOYSA-J sodium;gold(3+);disulfite Chemical compound [Na+].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O ZWZLRIBPAZENFK-UHFFFAOYSA-J 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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Classifications
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- 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
Description
本発明は高発電性能であり耐久後の電圧特性に優れた固体高分子型燃料電池用電極触媒に関する。 The present invention relates to an electrode catalyst for a polymer electrolyte fuel cell having high power generation performance and excellent voltage characteristics after durability.
従来、固体高分子電解質型燃料電池の電極触媒のカソード触媒及びアノード触媒としては、白金又は白金合金等の貴金属をカーボン担体に担持した触媒が用いられてきた。白金担持カーボン担体は、塩化白金酸水溶液に、亜硫酸水素ナトリウムを加えた後、過酸化水素水と反応させ、生じた白金コロイドをカーボン担体に担持させ、洗浄後、必要に応じて熱処理することにより調製するのが一般的である。固体高分子電解質型燃料電池の電極は、白金担持カーボン担体を高分子電解質溶液に分散させてインクを調製し、そのインクをカーボンペーパーなどのガス拡散基材に塗布し、乾燥することにより作製される。この２枚の電極で高分子電解質膜を挟み、ホットプレスをすることにより電解質膜−電極接合体（ＭＥＡ）が組立られる。 Conventionally, as a cathode catalyst and an anode catalyst of an electrode catalyst of a solid polymer electrolyte fuel cell, a catalyst in which a noble metal such as platinum or a platinum alloy is supported on a carbon carrier has been used. The platinum-supported carbon support is obtained by adding sodium hydrogen sulfite to a chloroplatinic acid aqueous solution, then reacting with hydrogen peroxide solution, supporting the resulting platinum colloid on the carbon support, washing, and then heat-treating as necessary. It is common to prepare. An electrode of a solid polymer electrolyte fuel cell is prepared by dispersing a platinum-supported carbon carrier in a polymer electrolyte solution, preparing an ink, applying the ink to a gas diffusion substrate such as carbon paper, and drying. The An electrolyte membrane-electrode assembly (MEA) is assembled by sandwiching a polymer electrolyte membrane between these two electrodes and performing hot pressing.
触媒金属である白金は高価な貴金属であり、少ない担持量で十分な性能を発揮させることが望まれている。そのため、より少量の白金で触媒活性を高める検討がなされている。 Platinum, which is a catalyst metal, is an expensive noble metal, and it is desired to exhibit sufficient performance with a small amount of support. Therefore, studies have been made to increase the catalytic activity with a smaller amount of platinum.
下記特許文献１には、炭素粉末担体上に白金とコバルトを合金化してなる触媒粒子が担持された高分子固体電解質形燃料電池の空気極用の触媒が開示されている。具体的には、白金とコバルトとの配合比は６：１〜３：１（モル比）とし、比表面積６００〜１２００ｍ２／ｇの炭素粉末からなる担体に、触媒粒子を担持密度４０〜６５％で担持することが開示されている。
又、下記特許文献２には、白金又は白金合金触媒がカーボン担体に担持された燃料電池用電極触媒の製造方法が開示されている。ここで、白金合金触媒として、白金と、ニッケル、コバルト、クロム、マンガン及び鉄より選ばれる１種又は２種以上からなる合金触媒が開示されている。
上記特許文献１及び２に開示された触媒は、初期性能の面では優れているものの、カーボン酸化耐久性の面では未だ改良の余地が残されていた。
Although the catalysts disclosed in
固体高分子型燃料電池用電極触媒においては、燃料電池の起動時、停止時及び運転中に、電位が上昇することで、次式に示すように、電極触媒のカーボン担体の酸化反応が促進され、カーボンが腐食することで、触媒が劣化し、燃料電池の発電性能が低下する。
Ｃ＋２Ｈ２Ｏ→ＣＯ２＋２Ｈ２ （１）
In an electrode catalyst for a polymer electrolyte fuel cell, an oxidation reaction of a carbon support of the electrode catalyst is promoted as shown in the following equation by increasing the potential at the start, stop and operation of the fuel cell. As the carbon corrodes, the catalyst deteriorates, and the power generation performance of the fuel cell decreases.
C + 2H 2 O → CO 2 + 2H 2 (1)
このような現象は、燃料電池の起動時のみならず、停止時にも同様に生じ、さらに燃料電池の起動・停止の操作を繰り返すと、この現象がさらに加速する傾向にあり、セル電圧の低下に伴い、発電性能が低下する可能性があった。 This phenomenon occurs not only when the fuel cell is started but also when it is stopped, and when the fuel cell is started / stopped repeatedly, this phenomenon tends to accelerate further, leading to a decrease in cell voltage. Along with this, the power generation performance may be reduced.
このため、初期発電性能とカーボン酸化耐久性の両面で優れた電極触媒が望まれていた。 For this reason, an electrode catalyst excellent in both initial power generation performance and carbon oxidation durability has been desired.
本発明は、発電の初期性能を長く維持することのできる耐久後の電圧特性に優れた固体高分子型燃料電池用電極触媒を提供することを目的とする。 An object of the present invention is to provide an electrode catalyst for a polymer electrolyte fuel cell, which can maintain the initial performance of power generation for a long time and has excellent voltage characteristics after durability.
本発明者は、特定の合金触媒系において、カーボン担体の結晶性に着目し、カーボン結晶性と耐久性（発電性能維持率）との間に強い相関関係があることを見出し、本発明に到達した。 The present inventor has focused on the crystallinity of the carbon support in a specific alloy catalyst system, found that there is a strong correlation between the carbon crystallinity and durability (power generation performance maintenance ratio), and reached the present invention. did.
即ち、ＰｔＣｏ系触媒について鋭意検討を行った結果ＰｔＣｏにＡｕなどの撥水性元素をある限られた範囲内で配合し合金化したものと、Ｌａをある限られた範囲内に限定した高結晶化カーボンブラックを担体として組み合わせることで、前述の課題を解決することができた。ＰｔＣｏに担持する物質はＡｕの他にＲｈ、Ｐｄなどがあげられる。 That is, as a result of diligent study on PtCo-based catalysts, PtCo was mixed with a water repellent element such as Au within a limited range and alloyed, and high crystallization with La limited to a limited range. By combining carbon black as a carrier, the above-mentioned problems could be solved. Examples of the substance supported on PtCo include Au, Rh, Pd and the like.
Ａｕなどの撥水性元素の添加によるカーボン酸化耐性向上のメカニズムについては、Ａｕなどの撥水性元素の撥水作用がカーボン酸化反応
Ｃ＋２Ｈ２Ｏ→ＣＯ２＋２Ｈ２ （１）
を抑制する効果があると考えられ、従来より酸化耐性をもつ高結晶化カーボンの酸化を飛躍的に抑制すると推定される。
Regarding the mechanism of improving carbon oxidation resistance by adding a water repellent element such as Au, the water repellent action of a water repellent element such as Au is the carbon oxidation reaction C + 2H 2 O → CO 2 + 2H 2 (1)
Therefore, it is estimated that the oxidation of highly crystallized carbon having oxidation resistance is greatly suppressed.
本発明は、高結晶性カーボン担体上に白金（Ｐｔ）、コバルト（Ｃｏ）、及び撥水性元素から選択される１種以上からなる触媒微粒子が担持された固体高分子型燃料電池用電極触媒の発明であって、高結晶性カーボンの結晶子の六員環面方向の長さＬａが４．５ｎｍ以上であり、触媒微粒子が白金（Ｐｔ）：コバルト（Ｃｏ）：撥水性元素＝１：０．０１〜０．１：０．０３〜０．１、好ましくは白金（Ｐｔ）：コバルト（Ｃｏ）：撥水性元素＝１：０．０２〜０．０６：０．０３〜０．０７であることを特徴とする。 The present invention relates to an electrode catalyst for a polymer electrolyte fuel cell in which catalyst fine particles comprising at least one selected from platinum (Pt), cobalt (Co), and a water repellent element are supported on a highly crystalline carbon support. In the invention, the length La in the six-membered ring plane direction of the crystallite of the highly crystalline carbon is 4.5 nm or more, and the catalyst fine particles are platinum (Pt): cobalt (Co): water repellent element = 1: 0. 0.01-0.1: 0.03-0.1, preferably platinum (Pt): cobalt (Co): water repellent element = 1: 0.02-0.06: 0.03-0.07 It is characterized by that.
本発明の燃料電池用電極触媒により、カーボン結晶化度が所定値より大であることにより、Ｐｔ−Ｃｏ−撥水性元素からなる３元系電極触媒の耐久性（発電性能維持率）を向上できた。ここで、結晶子の六員環面方向の長さＬａとは、カーボン担体を構成する炭素の黒鉛構造に基づく六員環面のＡ、Ｂ軸方向の長さを示し、カーボン担体のＸ線回折パターンから算出される値である。 With the fuel cell electrode catalyst of the present invention, the durability (power generation performance maintenance rate) of the ternary electrode catalyst composed of Pt—Co—water-repellent element can be improved when the carbon crystallinity is larger than a predetermined value. It was. Here, the length La in the six-membered ring plane direction of the crystallite indicates the length in the A and B axis directions of the six-membered ring plane based on the graphite structure of carbon constituting the carbon support. It is a value calculated from the diffraction pattern.
本発明の電極触媒では、撥水性元素として、金（Ａｕ）、ロジウム（Ｒｈ）、パラジウム（Ｐｄ）から選択される１種以上が好ましく例示される。これらの撥水性元素は、白金、コバルトと３元系合金からなる触媒微粒子を形成する。
本発明の電極触媒では、触媒微粒子の平均粒径が３〜１０ｎｍであることが好ましい。
In the electrode catalyst of the present invention, one or more types selected from gold (Au), rhodium (Rh), and palladium (Pd) are preferably exemplified as the water repellent element. These water repellent elements form catalyst fine particles composed of platinum, cobalt and a ternary alloy.
In the electrode catalyst of the present invention, the average particle diameter of the catalyst fine particles is preferably 3 to 10 nm.
本発明は、高結晶性カーボン担体上にＰｔ−Ｃｏ−撥水性元素からなる３元系合金媒微粒子を担持させて燃料電池用電極触媒とすることにより、高い初期発電性能を長期間維持することができる。具体的には、本発明の燃料電池用電極触媒によれば、炭素担体の耐腐食性を高めると共に、触媒活性の低下を防ぎ、長期に亘って、安定した発電性能が得られる。 The present invention maintains high initial power generation performance for a long period of time by using a ternary alloy medium fine particle composed of Pt—Co—water-repellent element on a highly crystalline carbon support to form a fuel cell electrode catalyst. Can do. Specifically, according to the electrode catalyst for a fuel cell of the present invention, the corrosion resistance of the carbon support is enhanced and the catalytic activity is prevented from being lowered, and stable power generation performance can be obtained over a long period of time.
カーボン担体の結晶化度は、カーボン担体のグラファイト化により容易に調整することができる。カーボン担体のグラファイト化は、熱処理など、従来一般的に用いられているものであれば特に限定されない。前記熱処理は、窒素、アルゴン、ヘリウムなどの不活性ガス雰囲気下で行うのが好ましい。また、熱処理温度、熱処理時間は、用いるカーボン担体の材質によって異なるが、１，０００〜２，０００℃で、５〜２０時間程度行えばよい。このように、グラファイト化などによりカーボン担体の結晶化度が向上する。 The crystallinity of the carbon support can be easily adjusted by graphitization of the carbon support. The graphitization of the carbon support is not particularly limited as long as it is conventionally used, such as heat treatment. The heat treatment is preferably performed in an inert gas atmosphere such as nitrogen, argon, or helium. Moreover, although heat processing temperature and heat processing time change with materials of the carbon support | carrier to be used, what is necessary is just to carry out at 1,000-2,000 degreeC for about 5 to 20 hours. Thus, the crystallinity of the carbon support is improved by graphitization or the like.
以下、本発明の実施例と比較例を示す。
［実施例１］
比表面積が７６０ｍ２／ｇのカーボンブラックをアルゴンガス雰囲気中、昇温速度２０℃／ｍｉｎで１３００℃まで昇温し、６時間熱処理を行い黒鉛化カーボンを得た。ＸＲＤで４２°近辺にあるピークの位置（角度）と半価幅からＬａ、２６°近辺にあるピークの位置（角度）と半価幅からＬｃを出した結果、Ｌａ＝７．３ｎｍ、Ｌｃ＝３．４ｎｍであった。
Examples of the present invention and comparative examples are shown below.
[Example 1]
Carbon black having a specific surface area of 760 m 2 / g was heated to 1300 ° C. at a heating rate of 20 ° C./min in an argon gas atmosphere, and heat-treated for 6 hours to obtain graphitized carbon. As a result of calculating La from the position (angle) and half-value width of a peak near 42 ° in XRD, and Lc from the position (angle) and half-value width of a peak near 26 °, La = 7.3 nm, Lc = It was 3.4 nm.
この熱処理で得られた黒鉛化カーボン粉末６．０３ｇに純水０．５Ｌを加え、分散させた。この分散液に、Ｐｔ５．１２ｇを含むヘキサヒドロキソ白金硝酸溶液、Ａｕ０．２ｇを含む亜硫酸金ナトリウム、Ｃｏ１．０２ｇを含む硝酸コバルト水溶液の順にそれぞれ滴下し、十分にカーボンとなじませた。これに０．０１Ｎアンモニア約５ｍＬを添加してＰＨを約９とし、それぞれ水酸化物を形成させ、カーボン上に析出させた。この分散液をろ過排液の導電率が５０μＳ／ｃｍ以下になるまで繰返しろ過洗浄して得られた粉末を１００℃で１０時間真空乾燥させた。 To 6.03 g of the graphitized carbon powder obtained by this heat treatment, 0.5 L of pure water was added and dispersed. To this dispersion, a hexahydroxo platinum nitric acid solution containing 5.12 g of Pt, a sodium gold sulfite containing 0.2 g of Au, and an aqueous cobalt nitrate solution containing 1.02 g of Co were added dropwise in this order, and were sufficiently blended with carbon. About 5 mL of 0.01N ammonia was added thereto to adjust the pH to about 9, and hydroxides were formed and precipitated on carbon. The powder obtained by repeatedly filtering and washing this dispersion liquid until the electric conductivity of the filtrate drainage solution was 50 μS / cm or less was vacuum-dried at 100 ° C. for 10 hours.
次に水素ガス中で５００℃、２時間保持して還元処理した後、窒素ガス中で９００℃、２時間保持して合金化した。さらにこの触媒粉末を１Ｎ塩酸０．５Ｌ中で攪拌して未合金コバルト約４０ｗｔ％を酸洗浄除去した後、ろ過排液の導電率が５０μＳ／ｃｍ以下になるまで純水で繰返し洗浄した。 Next, after reducing in hydrogen gas at 500 ° C. for 2 hours, it was alloyed by holding in nitrogen gas at 900 ° C. for 2 hours. Further, this catalyst powder was stirred in 0.5 L of 1N hydrochloric acid to remove about 40 wt% of unalloyed cobalt with acid, and then repeatedly washed with pure water until the conductivity of the filtered effluent became 50 μS / cm or less.
得られたＰｔ合金担持カーボン触媒粉末のＰｔ担持密度は４１．９ｗｔ％、Ａｕ担持密度は１．６０ｗｔ％で、Ｃｏ担持密度は６．９０ｗｔ％であった。Ｐｔ合金担持カーボン触媒粉末の各元素の原子比率はＰｔ：Ｃｏ：Ａｕ＝１：０．０５：０．０４であった。さらにＸＲＤを測定したところ、Ｐｔのピークのみ観察され、３９°付近のＰｔ（１１１）面のピークシフトから不規則配列合金の形成を確認した。さらにＰｔ（１１１）面のピーク位置と半価幅から平均粒径を算出したところ４．２ｎｍであった。
得られた触媒粉末の物性を表１に示す。
The obtained Pt alloy-supported carbon catalyst powder had a Pt support density of 41.9 wt%, an Au support density of 1.60 wt%, and a Co support density of 6.90 wt%. The atomic ratio of each element of the Pt alloy-supported carbon catalyst powder was Pt: Co: Au = 1: 0.05: 0.04. Furthermore, when XRD was measured, only the peak of Pt was observed, and formation of a disordered alloy was confirmed from the peak shift of the Pt (111) plane near 39 °. Furthermore, it was 4.2 nm when the average particle diameter was computed from the peak position and half value width of Pt (111) plane.
Table 1 shows the physical properties of the obtained catalyst powder.
［実施例２］
カーボンの熱処理温度を１７００℃、６時間とすることで結晶化度の異なる（ＬａとＬｃの異なる）カーボンブラックを得た。このカーボンブラックに実施例１と同様の手法でＰｔＣｏＡｕを担持した。
得られた触媒粉末の物性を表１に示す。
[Example 2]
Carbon black having different crystallinity (different in La and Lc) was obtained by setting the heat treatment temperature of carbon to 1700 ° C. for 6 hours. This carbon black was loaded with PtCoAu in the same manner as in Example 1.
Table 1 shows the physical properties of the obtained catalyst powder.
［実施例３］
カーボンの熱処理温度を２０００℃、８時間とすることで結晶化度の異なる（ＬａとＬｃの異なる）カーボンブラックを得た。このカーボンブラックに実施例１と同様の手法でＰｔＣｏＡｕを担持した。
得られた触媒粉末の物性を表１に示す。
[Example 3]
Carbon black having different crystallinity (different in La and Lc) was obtained by setting the heat treatment temperature of carbon to 2000 ° C. for 8 hours. This carbon black was loaded with PtCoAu in the same manner as in Example 1.
Table 1 shows the physical properties of the obtained catalyst powder.
［比較例１］
カーボンの熱処理なしとすることで結晶化度の異なる（ＬａとＬｃの異なる）カーボンブラックを得た。このカーボンブラックに実施例１と同様の手法でＰｔＣｏＡｕを担持した。
得られた触媒粉末の物性を表１に示す。
[Comparative Example 1]
Carbon black with different crystallinity (different in La and Lc) was obtained by eliminating the heat treatment of carbon. This carbon black was loaded with PtCoAu in the same manner as in Example 1.
Table 1 shows the physical properties of the obtained catalyst powder.
［実施例４］
実施例１のカーボンブラックに、Ｃｏの比率の異なるＰｔＣｏＡｕを担持した。Ｃｏの比率はカーボンブラックに対するＰｔ及びＡｕ重量比率を一定として変化させた。Ｃｏの比率をＰｔ：Ｃｏ：Ａｕ＝１：０．０１：０．０４にした以外は、実施例１と同様にして触媒粉末を調製した。得られた触媒粉末の物性を表１に示す。
[Example 4]
The carbon black of Example 1 was loaded with PtCoAu having a different Co ratio. The ratio of Co was changed with the weight ratio of Pt and Au to carbon black being constant. A catalyst powder was prepared in the same manner as in Example 1 except that the ratio of Co was changed to Pt: Co: Au = 1: 0.01: 0.04. Table 1 shows the physical properties of the obtained catalyst powder.
［実施例５］
実施例１のカーボンブラックに、Ｃｏの比率の異なるＰｔＣｏＡｕを担持した。Ｃｏの比率はカーボンブラックに対するＰｔ及びＡｕ重量比率を一定として変化させた。Ｃｏの比率をＰｔ：Ｃｏ：Ａｕ＝１：０．１：０．０４にした以外は、実施例１と同様にして触媒粉末を調製した。得られた触媒粉末の物性を表１に示す。
[Example 5]
The carbon black of Example 1 was loaded with PtCoAu having a different Co ratio. The ratio of Co was changed with the weight ratio of Pt and Au to carbon black being constant. A catalyst powder was prepared in the same manner as in Example 1 except that the ratio of Co was changed to Pt: Co: Au = 1: 0.1: 0.04. Table 1 shows the physical properties of the obtained catalyst powder.
［比較例２］
実施例１のカーボンブラックに、Ｃｏの比率の異なるＰｔＣｏＡｕを担持した。Ｃｏの比率はカーボンブラックに対するＰｔ及びＡｕ重量比率を一定として変化させた。Ｃｏの比率をＰｔ：Ｃｏ：Ａｕ＝１：０．００４：０．０４にした以外は、実施例１と同様にして触媒粉末を調製した。得られた触媒粉末の物性を表１に示す。
[Comparative Example 2]
The carbon black of Example 1 was loaded with PtCoAu having a different Co ratio. The ratio of Co was changed with the weight ratio of Pt and Au to carbon black being constant. A catalyst powder was prepared in the same manner as in Example 1 except that the ratio of Co was changed to Pt: Co: Au = 1: 0.004: 0.04. Table 1 shows the physical properties of the obtained catalyst powder.
［比較例３］
実施例１のカーボンブラックに、Ｃｏの比率の異なるＰｔＣｏＡｕを担持した。Ｃｏの比率はカーボンブラックに対するＰｔ及びＡｕ重量比率を一定として変化させた。Ｃｏの比率をＰｔ：Ｃｏ：Ａｕ＝１：０．３：０．０４にした以外は、実施例１と同様にして触媒粉末を調製した。得られた触媒粉末の物性を表１に示す。
[Comparative Example 3]
The carbon black of Example 1 was loaded with PtCoAu having a different Co ratio. The ratio of Co was changed with the weight ratio of Pt and Au to carbon black being constant. A catalyst powder was prepared in the same manner as in Example 1 except that the ratio of Co was changed to Pt: Co: Au = 1: 0.3: 0.04. Table 1 shows the physical properties of the obtained catalyst powder.
［実施例６］
実施例１のカーボンブラックに、Ａｕの比率の異なるＰｔＣｏＡｕを担持した。Ａｕの比率はカーボンブラックに対するＰｔ及びＣｏ重量比率を一定として変化させた。Ａｕの比率をＰｔ：Ｃｏ：Ａｕ＝１：０．０５：０．０３にした以外は、実施例１と同様にして触媒粉末を調製した。得られた触媒粉末の物性を表１に示す。
[Example 6]
The carbon black of Example 1 was loaded with PtCoAu having a different Au ratio. The Au ratio was varied with the weight ratio of Pt and Co to carbon black being constant. A catalyst powder was prepared in the same manner as in Example 1 except that the Au ratio was changed to Pt: Co: Au = 1: 0.05: 0.03. Table 1 shows the physical properties of the obtained catalyst powder.
［実施例７］
実施例１のカーボンブラックに、Ａｕの比率の異なるＰｔＣｏＡｕを担持した。Ａｕの比率はカーボンブラックに対するＰｔ及びＣｏ重量比率を一定として変化させた。Ａｕの比率をＰｔ：Ｃｏ：Ａｕ＝１：０．０５：０．１にした以外は、実施例１と同様にして触媒粉末を調製した。得られた触媒粉末の物性を表１に示す。
[Example 7]
The carbon black of Example 1 was loaded with PtCoAu having a different Au ratio. The Au ratio was varied with the weight ratio of Pt and Co to carbon black being constant. A catalyst powder was prepared in the same manner as in Example 1 except that the Au ratio was changed to Pt: Co: Au = 1: 0.05: 0.1. Table 1 shows the physical properties of the obtained catalyst powder.
［比較例４］
実施例１のカーボンブラックに、Ａｕの比率の異なるＰｔＣｏＡｕを担持した。Ａｕの比率はカーボンブラックに対するＰｔ及びＣｏ重量比率を一定として変化させた。Ａｕの比率をＰｔ：Ｃｏ：Ａｕ＝１：０．０５：０．０１３にした以外は、実施例１と同様にして触媒粉末を調製した。得られた触媒粉末の物性を表１に示す。
[Comparative Example 4]
The carbon black of Example 1 was loaded with PtCoAu having a different Au ratio. The Au ratio was varied with the weight ratio of Pt and Co to carbon black being constant. A catalyst powder was prepared in the same manner as in Example 1 except that the Au ratio was changed to Pt: Co: Au = 1: 0.05: 0.013. Table 1 shows the physical properties of the obtained catalyst powder.
［比較例５］
実施例１のカーボンブラックに、Ａｕの比率の異なるＰｔＣｏＡｕを担持した。Ａｕの比率はカーボンブラックに対するＰｔ及びＣｏ重量比率を一定として変化させた。Ａｕの比率をＰｔ：Ｃｏ：Ａｕ＝１：０．０５：０．１３にした以外は、実施例１と同様にして触媒粉末を調製した。
[Comparative Example 5]
The carbon black of Example 1 was loaded with PtCoAu having a different Au ratio. The Au ratio was varied with the weight ratio of Pt and Co to carbon black being constant. A catalyst powder was prepared in the same manner as in Example 1 except that the Au ratio was changed to Pt: Co: Au = 1: 0.05: 0.13.
［単セルの作製］
実施例１〜７および比較例１〜５の触媒粉末を用い、次に示す手法で単セルを作製した。
触媒粉末を水、アルコール系溶媒、及びナフィオン（登録商標）溶液の混合液に分散させ、この分散液をテフロン（登録商標）シートへ塗布して触媒層を形成した。電極面積１ｃｍ２あたりのＰｔ触媒の量は０．４ｍｇとした。これらの触媒粉末から形成した電極をそれぞれ高分子電解質膜を介してホットプレスにより貼り合わせその両側に拡散層を設置して単セル電極を形成した。
[Production of single cell]
Using the catalyst powders of Examples 1 to 7 and Comparative Examples 1 to 5, single cells were produced by the following method.
The catalyst powder was dispersed in a mixed solution of water, an alcohol solvent, and a Nafion (registered trademark) solution, and this dispersion was applied to a Teflon (registered trademark) sheet to form a catalyst layer. The amount of Pt catalyst per 1 cm 2 of electrode area was 0.4 mg. The electrodes formed from these catalyst powders were bonded by hot pressing through polymer electrolyte membranes, respectively, and diffusion layers were installed on both sides thereof to form single cell electrodes.
［カーボン酸化劣化耐久評試験］
実施例１〜７および比較例１〜５の触媒粉末で作製した単セルについてカーボン酸化劣化耐久試験を行った。試験は１Ｖ、３０ｍｉｎの定電圧連続運転により行い試験後の０．９Ａ／ｃｍ２の電圧値で比較した。
以上、実施例１〜７および比較例１〜５の触媒物性を表１に示す。
[Carbon oxidation deterioration durability evaluation test]
The carbon oxidation deterioration durability test was done about the single cell produced with the catalyst powder of Examples 1-7 and Comparative Examples 1-5. The test was carried out by constant voltage continuous operation at 1 V for 30 min, and comparison was made with a voltage value of 0.9 A / cm 2 after the test.
The catalyst physical properties of Examples 1 to 7 and Comparative Examples 1 to 5 are shown in Table 1.
又、図１に、Ａｕ原子比率と耐久試験後の電圧の関係を示す。図２に、高結晶性カーボンの結晶子の六員環面方向の長さＬａと耐久試験後の電圧の関係を示す。図３に、Ｃｏ原子比率と耐久試験後の電圧の関係を示す。 FIG. 1 shows the relationship between the Au atomic ratio and the voltage after the durability test. FIG. 2 shows the relationship between the length La of the crystallites of highly crystalline carbon in the six-membered ring plane direction and the voltage after the durability test. FIG. 3 shows the relationship between the Co atomic ratio and the voltage after the durability test.
表１の結果より、高結晶性カーボンの結晶子の六員環面方向の長さＬａが４．５ｎｍ以上であり、触媒微粒子が白金（Ｐｔ）：コバルト（Ｃｏ）：撥水性元素＝１：０．０１〜０．１：０．０３〜０．１である場合に耐久試験後も高活性が維持されることが分かる。 From the results of Table 1, the length La of the crystallites of highly crystalline carbon is 4.5 nm or more, and the catalyst fine particles are platinum (Pt): cobalt (Co): water repellent element = 1: It can be seen that high activity is maintained even after the durability test when 0.01 to 0.1: 0.03 to 0.1.
本発明の固体高分子型燃料電池用電極触媒は、従来のＰｔＣｏ／Ｃ触媒に更にＡｕなどの撥水性元素を担持し、加えて高結晶性カーボンを担体として用いることで、優れた初期発電性能を長期間維持するという耐久性を飛躍的に向上できる。これにより、燃料電池の普及に貢献する。 The electrode catalyst for a polymer electrolyte fuel cell of the present invention has excellent initial power generation performance by further supporting a water-repellent element such as Au on a conventional PtCo / C catalyst, and additionally using highly crystalline carbon as a carrier. Durability of maintaining for a long time can be dramatically improved. This contributes to the spread of fuel cells.
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