JP2021072268A - Catalyst layer and solid polymer fuel cell - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 221
- 239000000446 fuel Substances 0.000 title claims abstract description 36
- 229920000642 polymer Polymers 0.000 title abstract 3
- 239000007787 solid Substances 0.000 title abstract 3
- 230000004913 activation Effects 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 229920000554 ionomer Polymers 0.000 claims abstract description 14
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 42
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 42
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 28
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 230000007812 deficiency Effects 0.000 claims description 16
- 239000005518 polymer electrolyte Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 229910019897 RuOx Inorganic materials 0.000 claims description 4
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 17
- 230000003647 oxidation Effects 0.000 abstract description 15
- 230000000694 effects Effects 0.000 description 47
- 239000002245 particle Substances 0.000 description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 230000002950 deficient Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910001260 Pt alloy Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000003411 electrode reaction Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- -1 atomic arrangement Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 229920003934 Aciplex® Polymers 0.000 description 1
- 229920003937 Aquivion® Polymers 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229920003935 Flemion® Polymers 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910002835 Pt–Ir Inorganic materials 0.000 description 1
- 229910002845 Pt–Ni Inorganic materials 0.000 description 1
- 229910002848 Pt–Ru Inorganic materials 0.000 description 1
- 229910018879 Pt—Pd Inorganic materials 0.000 description 1
- 229910000929 Ru alloy Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910000756 V alloy Inorganic materials 0.000 description 1
- ZSBZBFTZJNOILL-UHFFFAOYSA-N [Ir]=O.[Ru]=O Chemical compound [Ir]=O.[Ru]=O ZSBZBFTZJNOILL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 229910000487 osmium oxide Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- JIWAALDUIFCBLV-UHFFFAOYSA-N oxoosmium Chemical compound [Os]=O JIWAALDUIFCBLV-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Images
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
Abstract
Description
本発明は、触媒層及び固体高分子形燃料電池に関し、さらに詳しくは、カーボン材料の酸化に対する耐性が高い触媒層、及び、これをアノード側触媒層に用いた固体高分子形燃料電池に関する。 The present invention relates to a catalyst layer and a polymer electrolyte fuel cell, and more particularly to a catalyst layer having high resistance to oxidation of a carbon material and a polymer electrolyte fuel cell using the catalyst layer as an anode side catalyst layer.
固体高分子形燃料電池は、電解質膜の両面に触媒を含む電極が接合された膜電極接合体（Membrane Electrode Assembly，ＭＥＡ）を備えている。電極は、通常、触媒層とガス拡散層の２層構造を取る。ＭＥＡの両面には、さらに、ガス流路を備えた集電体（セパレータ）が配置される。固体高分子形燃料電池は、通常、このようなＭＥＡと集電体からなる単セルが複数個積層された構造（燃料電池スタック）を備えている。 The polymer electrolyte fuel cell includes a membrane electrode assembly (MEA) in which electrodes containing a catalyst are bonded to both sides of an electrolyte membrane. The electrode usually has a two-layer structure of a catalyst layer and a gas diffusion layer. Further, current collectors (separators) provided with gas flow paths are arranged on both sides of the MEA. The polymer electrolyte fuel cell usually has a structure (fuel cell stack) in which a plurality of single cells composed of such an MEA and a current collector are stacked.
燃料電池スタック内の各単セルは、電気的に直列に接続されている。このような燃料電池スタックを用いて発電する場合において、一部の単セルのみが、燃料供給が途絶えた状態（燃料欠状態）になることがある。例えば、低温始動時において燃料ガス流路の一部が凍結により閉塞していると、一部の単セルのみが燃料欠状態となる。以下、燃料欠状態にある単セルを「燃料欠セル」ともいう。この状態で発電を続けると、残りの単セルが電源となる形で燃料欠セルにも電流が流れる。その結果、燃料欠セルのアノード電位が上昇し、燃料以外のアノードの成分（例えば、触媒を担持するための担体カーボン、単セル内に保持されている水など）の酸化反応が進行する。燃料欠セルにおいて担体カーボンの酸化が起こると、触媒層構造が破壊され、セル性能が著しく低下する。 Each single cell in the fuel cell stack is electrically connected in series. When power is generated using such a fuel cell stack, only a part of the single cells may be in a state where the fuel supply is cut off (fuel shortage state). For example, if a part of the fuel gas flow path is blocked by freezing at the time of low temperature start, only a part of the single cells will be in a fuel shortage state. Hereinafter, a single cell in a fuel shortage state is also referred to as a "fuel shortage cell". If power generation is continued in this state, current will flow to the fuel-deficient cell with the remaining single cell as the power source. As a result, the anode potential of the fuel-deficient cell rises, and the oxidation reaction of the anode components other than the fuel (for example, carrier carbon for supporting the catalyst, water held in the single cell, etc.) proceeds. When the carrier carbon is oxidized in the fuel-deficient cell, the catalyst layer structure is destroyed and the cell performance is significantly deteriorated.
そこでこの問題を解決するために、従来から種々の提案がなされている。
例えば、特許文献１には、燃料を電気化学的に酸化させるための第１の触媒組成物と、水から酸素を発生させるための第２の触媒組成物（いわゆる、水電解触媒）とを備えたアノードが開示されている。
同文献には、
（Ａ）アノードに水電解触媒を添加すると、水の電気分解が促進され、アノード成分の劣化が抑制される点、及び、
（Ｂ）酸化ルテニウムと酸化イリジウムの固溶体からなる触媒は、Ｐｔ／Ｒｕ合金からなる触媒よりも酸素発生機能が良好である点、
が記載されている。
Therefore, in order to solve this problem, various proposals have been made conventionally.
For example, Patent Document 1 includes a first catalyst composition for electrochemically oxidizing a fuel and a second catalyst composition for generating oxygen from water (so-called water electrolysis catalyst). The anode is disclosed.
In the same document,
(A) When a water electrolysis catalyst is added to the anode, electrolysis of water is promoted and deterioration of the anode component is suppressed, and
(B) A catalyst composed of a solid solution of ruthenium oxide and iridium oxide has a better oxygen evolution function than a catalyst composed of a Pt / Ru alloy.
Is described.
特許文献１に記載されているように、酸素生成反応（ＯＥＲ）を促進する触媒（以下、「ＯＥＲ触媒」ともいう）をアノードに添加すると、水素欠時でもカーボン酸化の代わりに水の酸化が優先的に起こり、アノードの劣化をある程度抑制することができる。
しかし、酸化イリジウムは、高温での活性が酸化ルテニウムより低い。他方、酸化ルテニウムは低温での活性が低いため、単独で使用すると氷点下時の水素欠に対応できない。酸化ルテニウムと酸化イリジウムの固溶体については、温度のロバスト性にどのような問題があるかは、組成や構造によって活性の絶対値や温度依存性が異なるので、一概には言えない。さらに、固溶体は、触媒合成のプロセスコストが高くなる可能性がある。
As described in Patent Document 1, when a catalyst that promotes an oxygen production reaction (OER) (hereinafter, also referred to as “OER catalyst”) is added to the anode, water is oxidized instead of carbon oxidation even when hydrogen is deficient. It occurs preferentially, and deterioration of the anode can be suppressed to some extent.
However, iridium oxide is less active at high temperatures than ruthenium oxide. On the other hand, ruthenium oxide has low activity at low temperatures, so when used alone, it cannot cope with hydrogen deficiency at sub-zero temperatures. Regarding the solid solution of ruthenium oxide and iridium oxide, the problem of temperature robustness cannot be unequivocally determined because the absolute value of activity and temperature dependence differ depending on the composition and structure. In addition, solid solutions can increase the process cost of catalyst synthesis.
本発明が解決しようとする課題は、高温運転時及び低温運転時のいずれの条件下においても、燃料欠によるアノード成分の酸化を抑制することが可能な触媒層を提供することにある。
また、本発明が解決しようとする他の課題は、このような触媒層を備えた固体高分子形燃料電池を提供することにある。
An object to be solved by the present invention is to provide a catalyst layer capable of suppressing oxidation of an anode component due to lack of fuel under both high temperature operation and low temperature operation conditions.
Another problem to be solved by the present invention is to provide a polymer electrolyte fuel cell provided with such a catalyst layer.
上記課題を解決するために本発明に係る触媒層は、以下の構成を備えている。
（１）前記触媒層は、
電極触媒と、
アイオノマと、
第１〜第ｎ酸素生成（ＯＥＲ）触媒（ｎ≧２）と
を備えている。
（２）第ｉＯＥＲ触媒（１≦ｉ≦ｎ）のＯＥＲ反応の活性化エネルギーＥiは、第ｊＯＥＲ触媒（１≦ｊ≦ｎ、ｉ≠ｊ）のＯＥＲ反応の活性化エネルギーＥjより大きい。
（３）前記第ｉＯＥＲ触媒及び前記第ｊＯＥＲ触媒は、後述する式（３）の関係を満たす。
In order to solve the above problems, the catalyst layer according to the present invention has the following constitution.
(1) The catalyst layer is
With the electrode catalyst
With ionomer
It is provided with a first to nth oxygen production (OER) catalyst (n ≧ 2).
(2) The activation energy E i of the OER reaction of the third iOER catalyst (1 ≦ i ≦ n) is larger than the activation energy E j of the OER reaction of the jOER catalyst (1 ≦ j ≦ n, i ≠ j).
(3) The iOER catalyst and the jOER catalyst satisfy the relationship of the formula (3) described later.
本発明に係る固体高分子形燃料電池は、本発明に係る触媒層をアノード側触媒層として用いたことを要旨とする。 The gist of the polymer electrolyte fuel cell according to the present invention is that the catalyst layer according to the present invention is used as the anode side catalyst layer.
ＯＥＲ反応の活性化エネルギーが大きい第ｉＯＥＲ触媒は、活性の温度依存性が大きい。そのため、第ｉＯＥＲ触媒は、低温では活性が低いが、高温では高い活性を示す。
一方、ＯＥＲ反応の活性化エネルギーが小さい第ｊＯＥＲ触媒は、活性の温度依存性が小さい。そのため、第ｊＯＥＲ触媒は、高温では活性が低いが、低温では比較的高い活性を示す。
The iOER catalyst having a large activation energy of the OER reaction has a large temperature dependence of activity. Therefore, the iOER catalyst has low activity at low temperature, but shows high activity at high temperature.
On the other hand, the jOER catalyst having a small activation energy of the OER reaction has a small temperature dependence of activity. Therefore, the jOER catalyst has low activity at high temperature, but relatively high activity at low temperature.
このような活性の温度依存性が異なる少なくとも２種類のＯＥＲ触媒を触媒層に添加すると、高温運転時には主として第ｉＯＥＲ触媒がアノード成分の酸化を抑制し、低温運転時には主として第ｊＯＥＲ触媒がアノード成分の酸化を抑制する。その結果、高温運転時及び低温運転時のいずれの条件下においても、アノード成分の酸化を抑制することができる。特に、各ＯＥＲ触媒の性状（すなわち、活性化エネルギー、総表面積、及び頻度因子）を最適化すると、各ＯＥＲ触媒を単独で用いた場合に比べて、高い活性を示す。 When at least two types of OER catalysts having different activity depending on the temperature are added to the catalyst layer, the iOER catalyst mainly suppresses the oxidation of the anode component during high temperature operation, and the jOER catalyst mainly suppresses the oxidation of the anode component during low temperature operation. Suppresses oxidation. As a result, oxidation of the anode component can be suppressed under both high temperature operation and low temperature operation conditions. In particular, when the properties of each OER catalyst (that is, activation energy, total surface area, and frequency factor) are optimized, higher activity is exhibited as compared with the case where each OER catalyst is used alone.
以下、本発明の一実施の形態について詳細に説明する。
［１． 触媒層］
本発明に係る触媒層は、
電極触媒と、
アイオノマと、
第１〜第ｎ酸素生成（ＯＥＲ）触媒（ｎ≧２）と
を備えている。
Hereinafter, an embodiment of the present invention will be described in detail.
[1. Catalyst layer]
The catalyst layer according to the present invention is
With the electrode catalyst
With ionomer
It is provided with a first to nth oxygen production (OER) catalyst (n ≧ 2).
［１．１． 電極触媒］
「電極触媒」とは、電極反応を生じさせるための触媒をいう。本発明に係る触媒層はアノードに用いられるので、電極反応とは、具体的には、水素酸化反応（ＨＯＲ）（Ｈ2→２Ｈ+＋２ｅ-）をいう。
電極触媒は、このような電極反応を生じさせる触媒粒子のみからなるものでも良く、あるいは、このような触媒粒子が担体表面に担持されているものでも良い。
[1.1. Electrode catalyst]
"Electrode catalyst" refers to a catalyst for causing an electrode reaction. Since the catalyst layer according to the present invention is used for the anode, the electrode reaction, specifically, hydrogen oxidation reaction (HOR) - refers to the (H 2 → 2H + + 2e ).
The electrode catalyst may be composed of only catalyst particles that cause such an electrode reaction, or may be those in which such catalyst particles are supported on the surface of a carrier.
［１．１．１． 触媒粒子］
［Ａ． 触媒粒子の組成］
本発明において、触媒粒子の材料は、特に限定されない。触媒粒子の材料としては、
（ａ）貴金属（Ｐｔ、Ａｕ、Ａｇ、Ｐｄ、Ｒｈ、Ｉｒ、Ｒｕ、Ｏｓ）、
（ｂ）２種以上の貴金属元素を含む合金、
（ｃ）１種又は２種以上の貴金属元素と、１種又は２種以上の卑金属元素（例えば、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｒ、Ｖ、Ｔｉなど）とを含む合金、
などがある。
[1.1.1. Catalyst particles]
[A. Composition of catalyst particles]
In the present invention, the material of the catalyst particles is not particularly limited. As a material for catalyst particles,
(A) Precious metals (Pt, Au, Ag, Pd, Rh, Ir, Ru, Os),
(B) Alloys containing two or more precious metal elements,
(C) An alloy containing one or more noble metal elements and one or more base metal elements (for example, Fe, Co, Ni, Cr, V, Ti, etc.).
and so on.
これらの中でも、触媒粒子は、Ｐｔ又はＰｔ合金が好ましい。これは、燃料電池の電極反応に対して高い活性を有するためである。
Ｐｔ合金としては、例えば、Ｐｔ−Ｆｅ合金、Ｐｔ−Ｃｏ合金、Ｐｔ−Ｎｉ合金、Ｐｔ−Ｐｄ合金、Ｐｔ−Ｃｒ合金、Ｐｔ−Ｖ合金、Ｐｔ−Ｔｉ合金、Ｐｔ−Ｒｕ合金、Ｐｔ−Ｉｒ合金などがある。
Among these, the catalyst particles are preferably Pt or Pt alloy. This is because it has high activity for the electrode reaction of the fuel cell.
Examples of Pt alloys include Pt-Fe alloys, Pt-Co alloys, Pt-Ni alloys, Pt-Pd alloys, Pt-Cr alloys, Pt-V alloys, Pt-Ti alloys, Pt-Ru alloys, and Pt-Ir. There are alloys and so on.
［Ｂ． 触媒粒子の粒径］
触媒粒子の粒径は、特に限定されるものではなく、目的に応じて最適な粒径を選択することができる。一般に、触媒粒子の粒径が小さすぎると、触媒粒子が溶解しやすくなる。従って、触媒粒子の粒径は、１ｎｍ以上が好ましい。
一方、触媒粒子の粒径が大きくなりすぎると、質量活性が低下する。従って、触媒粒子の粒径は、２０ｎｍ以下が好ましい。触媒粒子の粒径は、好ましくは、１０ｎｍ以下、さらに好ましくは、５ｎｍ以下である。
[B. Particle size of catalyst particles]
The particle size of the catalyst particles is not particularly limited, and the optimum particle size can be selected according to the intended purpose. In general, if the particle size of the catalyst particles is too small, the catalyst particles are likely to dissolve. Therefore, the particle size of the catalyst particles is preferably 1 nm or more.
On the other hand, if the particle size of the catalyst particles becomes too large, the mass activity decreases. Therefore, the particle size of the catalyst particles is preferably 20 nm or less. The particle size of the catalyst particles is preferably 10 nm or less, more preferably 5 nm or less.
［１．１．２． 担体］
［Ａ． 材料］
触媒粒子は、そのままの状態で各種用途に用いても良く、あるいは、担体表面に担持された状態で用いても良い。触媒粒子を担体表面に担持させると、微細な触媒粒子を安定して分散させることができるので、触媒使用量を低減することができる。
担体としては、例えば、カーボンブラック、カーボンナノチューブ、カーボンナノホーン、活性炭、天然黒鉛、メソカーボンマイクロビーズ、ガラス状炭素粉末などがある。
[1.1.2. Carrier]
[A. material]
The catalyst particles may be used as they are for various purposes, or may be used while being supported on the surface of a carrier. When the catalyst particles are supported on the surface of the carrier, the fine catalyst particles can be stably dispersed, so that the amount of catalyst used can be reduced.
Examples of the carrier include carbon black, carbon nanotubes, carbon nanohorns, activated carbon, natural graphite, mesocarbon microbeads, and glassy carbon powder.
［Ｂ． 触媒担持量］
触媒粒子が担体表面に担持されている場合、触媒担持量は、特に限定されるものではなく、目的に応じて最適な担持量を選択することができる。一般に、触媒担持量が少なすぎると、十分な活性が得られない。一方、触媒担持量を必要以上に多くしても、効果に差がなく、実益がない。
例えば、カーボン担体表面にＰｔ又はＰｔ合金からなる触媒粒子を担持させる場合、触媒担持量は、５ｍａｓｓ％〜７０ｍａｓｓ％が好ましい。
[B. Catalyst support amount]
When the catalyst particles are supported on the surface of the carrier, the amount of the catalyst supported is not particularly limited, and the optimum amount of the catalyst can be selected depending on the intended purpose. Generally, if the amount of catalyst supported is too small, sufficient activity cannot be obtained. On the other hand, even if the amount of catalyst supported is increased more than necessary, there is no difference in the effect and there is no actual benefit.
For example, when catalyst particles made of Pt or a Pt alloy are supported on the surface of a carbon carrier, the amount of catalyst supported is preferably 5 mass% to 70 mass%.
［１．２． アイオノマ］
［１．２．１． 組成］
アイオノマは、触媒粒子とプロトンの授受を行うためのものである。本発明において、アイオノマの種類は、特に限定されない。
[1.2. Ionomer]
[1.2.1. composition]
Ionomers are for exchanging protons with catalytic particles. In the present invention, the type of ionomer is not particularly limited.
アイオノマとしては、例えば、
（ａ）分子内に脂肪族環構造と、酸基とを備えた含フッ素イオン交換樹脂（以下、これを「高酸素透過アイオノマ」ともいう）、
（ｂ）ナフィオン（登録商標）、フレミオン（登録商標）、アクイヴィオン（登録商標）、アシプレックス（登録商標）などの、フッ化スルホニルビニルエーテルモノマに基づく繰り返し単位を含む含フッ素イオン交換樹脂（以下、これらを総称して、「低酸素透過アイオノマ」ともいう）
などがある。
アイオノマには、これらのいずれか１種を用いても良く、あるいは、２種以上を組み合わせて用いても良い。
As an ionomer, for example
(A) Fluorine-containing ion exchange resin having an aliphatic ring structure and an acid group in the molecule (hereinafter, this is also referred to as "high oxygen permeation ionoma"),
(B) Fluorine-containing ion exchange resins containing repeating units based on fluoride sulfonyl vinyl ether monomas, such as Nafion (registered trademark), Flemion (registered trademark), Aquivion (registered trademark), and Aciplex (registered trademark). Collectively, it is also called "low oxygen permeation ionoma")
and so on.
Any one of these may be used for the ionomer, or two or more of them may be used in combination.
アイオノマは、特に、高酸素透過アイオノマが好ましい。高酸素透過アイオノマを含む触媒インクを用いて作製される触媒層は、高い酸素透過性を示す。そのため、これを空気極側の触媒層として用いると、高い発電性能が得られる。 As the ionomer, a highly oxygen-permeable ionomer is particularly preferable. A catalyst layer made using a catalyst ink containing a highly oxygen permeable ionomer exhibits high oxygen permeability. Therefore, when this is used as a catalyst layer on the air electrode side, high power generation performance can be obtained.
［１．２．２． 含有量］
触媒層に含まれるアイオノマの量は、触媒層の性能に影響を与える。例えば、電極触媒がカーボン担体表面に触媒粒子が担持されているものである場合、触媒層に含まれるカーボン担体の質量に対するアイオノマの質量の比（Ｉ／Ｃ）は、触媒層の性能に影響を与える。そのため、電極触媒がカーボン担体を含む場合、触媒インク中のアイオノマの含有量は、Ｉ／Ｃが所定の値となるように設定するのが好ましい。
[1.2.2. Content]
The amount of ionomer contained in the catalyst layer affects the performance of the catalyst layer. For example, when the electrode catalyst has catalyst particles supported on the surface of the carbon carrier, the ratio of the mass of ionoma to the mass of the carbon carrier contained in the catalyst layer (I / C) affects the performance of the catalyst layer. give away. Therefore, when the electrode catalyst contains a carbon carrier, the content of ionomer in the catalyst ink is preferably set so that the I / C becomes a predetermined value.
一般に、Ｉ／Ｃ比が小さくなりすぎると、プロトン伝導度が低下し、触媒層の性能が低下する。従って、Ｉ／Ｃ比は、０．２以上が好ましい。Ｉ／Ｃ比は、好ましくは、０．４以上である。
一方、Ｉ／Ｃ比が過剰になると、電極中の細孔容積の減少が大きくなり、触媒層の性能が低下する。従って、Ｉ／Ｃ比は、１．５以下が好ましい。Ｉ／Ｃ比は、好ましくは、１．４以下である。
In general, if the I / C ratio becomes too small, the proton conductivity decreases and the performance of the catalyst layer deteriorates. Therefore, the I / C ratio is preferably 0.2 or more. The I / C ratio is preferably 0.4 or more.
On the other hand, when the I / C ratio becomes excessive, the decrease in the pore volume in the electrode becomes large, and the performance of the catalyst layer deteriorates. Therefore, the I / C ratio is preferably 1.5 or less. The I / C ratio is preferably 1.4 or less.
［１．３． 酸素生成（ＯＥＲ）触媒］
［１．３．１． 組成］
「酸素生成（ＯＥＲ）触媒」とは、燃料電池のアノードにおいて、酸素生成反応（２Ｈ2Ｏ→Ｏ2＋４Ｈ+＋４ｅ-）を生じさせることが可能な触媒をいう。
本発明において、触媒層には、２種以上のＯＥＲ触媒、すなわち、第１〜第ｎ酸素生成（ＯＥＲ）触媒（ｎ≧２）が添加される。これらの内、少なくとも２種類のＯＥＲ触媒（すなわち、第ｉＯＥＲ触媒及び第ｊＯＥＲ触媒、ｉ≠ｊ）は、後述する条件を満たしている必要がある。これら以外のＯＥＲ触媒は、後述する条件をさらに満たしていても良く、あるいは、満たしていなくても良い。
[1.3. Oxygen production (OER) catalyst]
[13.1. composition]
The "oxygen production (OER) catalyst", at the anode of the fuel cell, the oxygen generation reaction (2H 2 O → O 2 + 4H + + 4e -) refers to a catalyst capable of yielding.
In the present invention, two or more kinds of OER catalysts, that is, first to nth oxygen production (OER) catalysts (n ≧ 2) are added to the catalyst layer. Of these, at least two types of OER catalysts (that is, the iOER catalyst and the jOER catalyst, i ≠ j) need to satisfy the conditions described later. The OER catalyst other than these may or may not further satisfy the conditions described later.
後述する条件を満たす限りにおいて、各ＯＥＲ触媒の組成は、特に限定されない。ＯＥＲ触媒としては、例えば、酸化ルテニウム、酸化イリジウム、酸化オスミウムなどがある。 The composition of each OER catalyst is not particularly limited as long as the conditions described later are satisfied. Examples of the OER catalyst include ruthenium oxide, iridium oxide, and osmium oxide.
［１．３．２． 平均粒径］
「平均粒径」とは、レーザー回折散乱法により測定される粒径のメディアン値（ｄ50）をいう。
一般に、ＯＥＲ触媒の平均粒径が小さくなるほど、少量の添加で高い効果が得られる。従って、ＯＥＲ触媒の平均粒径は、１μｍ以下が好ましい。平均粒径は、好ましくは、０．５μｍ以下、さらに好ましくは、０．２μｍ以下である。
一方、ＯＥＲ触媒の平均粒径が小さくなりすぎると、耐久性が低下する。従って、ＯＥＲ触媒の平均粒径は、１ｎｍ以上が好ましい。
[1.3.2. Average particle size]
The "average particle size" refers to the median value (d 50 ) of the particle size measured by the laser diffraction / scattering method.
Generally, the smaller the average particle size of the OER catalyst, the higher the effect can be obtained by adding a small amount. Therefore, the average particle size of the OER catalyst is preferably 1 μm or less. The average particle size is preferably 0.5 μm or less, more preferably 0.2 μm or less.
On the other hand, if the average particle size of the OER catalyst becomes too small, the durability will decrease. Therefore, the average particle size of the OER catalyst is preferably 1 nm or more.
［１．３．３． 活性化エネルギー］
燃料欠は、燃料電池の温度が高温である場合及び低温である場合のいずれの環境下でも起こりうる。高温運転時及び低温運転時のいずれの運転条件下においても、アノード成分の酸化を抑制するためには、少なくとも、第ｉＯＥＲ触媒（１≦ｉ≦ｎ）のＯＥＲ反応の活性化エネルギーＥiは、第ｊＯＥＲ触媒（１≦ｊ≦ｎ、ｉ≠ｊ）のＯＥＲ反応の活性化エネルギーＥjより大きいことが必要である。
[1.3.3. Activation energy]
Fuel shortage can occur in any environment where the temperature of the fuel cell is high or low. In order to suppress the oxidation of the anode component under both high temperature operation and low temperature operation, at least the activation energy E i of the OER reaction of the iOER catalyst (1 ≦ i ≦ n) is set. It is necessary that the activation energy E j of the OER reaction of the first jOER catalyst (1 ≦ j ≦ n, i ≠ j) is larger.
より大きな活性化エネルギーＥiを持つ第ｉＯＥＲ触媒は、活性の温度依存性が高く、高温において活性が高くなる。一方、より小さな活性化エネルギーＥjを持つ第ｊＯＥＲ触媒は、活性の温度依存性が低く、低温でも比較的高い活性を持つ。そのため、少なくともこれらの２種類のＯＥＲ触媒を触媒層に添加すると、高温運転時及び低温運転時のいずれの条件下においても、燃料欠によるアノード成分の酸化を抑制することができる。
なお、３種類以上のＯＥＲ触媒を用いる場合において、第ｉＯＥＲ触媒及び第ｊＯＥＲ触媒以外のＯＥＲ触媒の活性化エネルギーは、特に限定されるものではなく、目的に応じて最適な値を選択することができる。
The iOER catalyst having a larger activation energy E i has a high temperature dependence of activity, and the activity becomes high at a high temperature. On the other hand, the jOER catalyst having a smaller activation energy E j has a low temperature dependence of activity and has a relatively high activity even at a low temperature. Therefore, when at least these two types of OER catalysts are added to the catalyst layer, oxidation of the anode component due to fuel shortage can be suppressed under both high temperature operation and low temperature operation conditions.
When three or more types of OER catalysts are used, the activation energy of the OER catalysts other than the iOER catalyst and the jOER catalyst is not particularly limited, and the optimum value may be selected according to the purpose. it can.
［１．３．４． 活性化エネルギーの差］
アノード成分の酸化を効率良く抑制するためには、第ｉＯＥＲ触媒と第ｊＯＥＲ触媒の活性化エネルギーの差（＝Ｅi−Ｅj）は、後述する条件を満たしているのが好ましい。以下に、高い活性を得るための活性化エネルギーの差の条件、並びに、これを満たすためのＯＥＲ触媒の総面積及び頻度因子の条件の導出過程を示す。
[13.4. Difference in activation energy]
In order to efficiently suppress the oxidation of the anode component, it is preferable that the difference in activation energy (= E i −E j ) between the iOER catalyst and the jOER catalyst satisfies the conditions described later. The process of deriving the condition of the difference in activation energy for obtaining high activity and the condition of the total area of the OER catalyst and the condition of the frequency factor for satisfying the condition are shown below.
触媒層の温度をＴ、水素欠が起こりうる最低温度をＴL、水素欠が起こりうる最高温度をＴHとする。
また、触媒層に含まれる第ｉＯＥＲ触媒の活性化エネルギーをＥi、総表面積をＷi、ＯＥＲ反応の触媒表面積当たりの頻度因子をＡiとする。
さらに、触媒層に含まれる第ｊＯＥＲ触媒の活性化エネルギーをＥj（＜Ｅi）、総表面積をＷj、ＯＥＲ反応の触媒表面積当たりの頻度因子をＡjとする。
Let T be the temperature of the catalyst layer, T L be the minimum temperature at which hydrogen deficiency can occur, and TH be the maximum temperature at which hydrogen deficiency can occur.
Further, the activation energy of the iOER catalyst contained in the catalyst layer is E i , the total surface area is W i , and the frequency factor per catalyst surface area of the OER reaction is A i .
Further, let E j (<E i ) be the activation energy of the jOER catalyst contained in the catalyst layer, W j be the total surface area, and A j be the frequency factor per catalyst surface area of the OER reaction.
ここで、
（ａ）活性化エネルギーの異なる２種類の触媒を同時に用いた場合（ケース１）、
（ｂ）第ｉＯＥＲ触媒を添加せずに第ｊＯＥＲ触媒の量を多くし、第ｊＯＥＲ触媒のみで総表面積がＷi＋Ｗjとなるようにした場合（ケース２）、及び、
（ｃ）第ｊＯＥＲ触媒を添加せずに第ｉＯＥＲ触媒の量を多くし、第ｉＯＥＲ触媒のみで総表面積がＷi＋Ｗjとなるようにした場合（ケース３）
について、温度ＴH及びＴLのいずれの条件下においてもケース１の活性が最低とならない条件を導く。
here,
(A) When two types of catalysts with different activation energies are used at the same time (Case 1)
(B) increasing the amount of the jOER catalyst without adding a second iOER catalyst, when the total surface area only in the first jOER catalyst is set to be W i + W j (case 2), and,
(C) increasing the amount of the iOER catalyst without adding a second jOER catalyst, when the total surface area only in the first iOER catalyst is set to be W i + W j (Case 3)
From the above, the condition that the activity of Case 1 is not the minimum is derived under both the temperature TH and T L conditions.
まず、温度ＴHにおいて、ケース１がケース２より活性が高くなる十分条件は、式（１）で表される。ここで、Ｒは気体定数であり、式（１）においては、ケース１に含まれる第ｉＯＥＲ触媒のみでケース２より活性が高くなるとしている。さらに、式（１）を変形すると、式（１）’が得られる。 First, the temperature T H, sufficient condition for case 1 activity is higher than the case 2 is represented by the formula (1). Here, R is a gas constant, and in the formula (1), it is said that only the iOER catalyst contained in the case 1 has higher activity than the case 2. Further, by modifying the equation (1), the equation (1)'is obtained.
次に、温度ＴLにおいて、ケース１がケース３より活性が高くなる十分条件は、式（２）で表される。ここで、式（２）においては、ケース１に含まれる第ｊＯＥＲ触媒のみでケース３より活性が高くなるとしている。さらに、式（２）を変形すると、式（２）’が得られる。 Next, the sufficient condition that the activity of Case 1 is higher than that of Case 3 at the temperature TL is represented by the formula (2). Here, in the formula (2), it is said that the activity is higher than that of the case 3 only by the jOER catalyst contained in the case 1. Further, by modifying the equation (2), the equation (2)'is obtained.
式（１）’及び式（２）’より、式（３）が得られる。
但し、
ＴLは、水素欠状態が起こりうる最低温度、
ＴHは、水素欠状態が起こりうる最高温度、
Ｗiは、前記触媒層に含まれる前記第ｉＯＥＲ触媒の総表面積、
Ａiは、前記第ｉＯＥＲ触媒の前記ＯＥＲ反応の触媒表面積当たりの頻度因子、
Ｗjは、前記触媒層に含まれる前記第ｊＯＥＲ触媒の総表面積、
Ａjは、前記第ｊＯＥＲ触媒の前記ＯＥＲ反応の触媒表面積当たりの頻度因子、
Ｒは、気体定数。
However,
TL is the lowest temperature at which hydrogen deficiency can occur.
TH is the maximum temperature at which hydrogen deficiency can occur.
W i is the total surface area of the first iOER catalyst contained in the catalyst layer,
A i is a pre-exponential factor per catalyst surface area of the OER reaction of the iOER catalyst.
W j is the total surface area of the jOER catalyst contained in the catalyst layer.
A j is a pre-exponential factor per catalyst surface area of the OER reaction of the jOER catalyst.
R is the gas constant.
ＴH及びＴLは、燃料電池の使用環境が決まると、一義的に定まる。ＯＥＲ触媒の活性化エネルギーＥは、ＯＥＲ触媒の組成、原子配列、粒子形態などが決まると、一義的に定まる。ＯＥＲ触媒の総表面積Ｗは、ＯＥＲ触媒の比表面積及び添加量が決まると、一義的に定まる。 TH and T L are uniquely determined when the usage environment of the fuel cell is determined. The activation energy E of the OER catalyst is uniquely determined when the composition, atomic arrangement, particle morphology, etc. of the OER catalyst are determined. The total surface area W of the OER catalyst is uniquely determined when the specific surface area and the amount of addition of the OER catalyst are determined.
ＯＥＲ触媒の頻度因子Ａは、単位面積当たりの活性サイトの数、反応中間体の占有数、ＯＥＲ触媒の粒径、組成、原子配列、粒子形態などに依存する。一般に、粒径が大きいほど、頻度因子Ａが大きくなる傾向がある。頻度因子Ａは、例えば、回転ディスク電極法を用いて、材料間で電位を揃えて活性を測定することにより知ることができる。 The frequency factor A of the OER catalyst depends on the number of active sites per unit area, the number of occupied reaction intermediates, the particle size, composition, atomic arrangement, particle morphology, etc. of the OER catalyst. In general, the larger the particle size, the larger the frequency factor A tends to be. The pre-exponential factor A can be known by, for example, using a rotating disc electrode method and measuring the activity by aligning the potentials between the materials.
［１．３．５． ＯＥＲ触媒の組み合わせの具体例］
［Ａ． 活性化エネルギーＥ］
例えば、過電圧０．５ＶでのＯＥＲの活性化エネルギーＥは、酸化ルテニウムが６６ｋＪ／ｍｏｌ（参考文献１）、酸化イリジウムが２６ｋＪ／ｍｏｌ（参考文献２）と報告されている。従って、第ｉＯＥＲ触媒として酸化ルテニウムを用い、第ｊＯＥＲ触媒として、酸化イリジウムを用いることができる。
［参考文献１］J. Phys. Chem., 97(1989)7381
［参考文献２］Electrochimica acta 281(2018)466
[1.3.5. Specific examples of OER catalyst combinations]
[A. Activation energy E]
For example, the activation energy E of OER at an overvoltage of 0.5 V is reported to be 66 kJ / mol for ruthenium oxide (Reference 1) and 26 kJ / mol for iridium oxide (Reference 2). Therefore, ruthenium oxide can be used as the iOER catalyst, and iridium oxide can be used as the jOER catalyst.
[Reference 1] J. Phys. Chem., 97 (1989) 7381
[Reference 2] Electrochimica acta 281 (2018) 466
［Ｂ． 総表面積Ｗ］
上述したように、総表面積Ｗは、ＯＥＲ触媒の比表面積と添加量で決まる。また、ＯＥＲ触媒の添加量は、ＯＥＲ触媒の比表面積、失活のしやすさ、コスト等を考慮して決定する。一般に、失活しやすいＯＥＲ触媒の場合、その添加量は、「失活しないための下限値」以上とするのが好ましい。一方、失活しにくいＯＥＲ触媒の場合、必要以上に添加しても効果に差が無く、実益がない。従って、そのようなＯＥＲ触媒の添加量は、「その効果が飽和する上限値」以下、又は、その上限値に安全係数をかけた値以下が好ましい。
[B. Total surface area W]
As described above, the total surface area W is determined by the specific surface area of the OER catalyst and the amount added. The amount of the OER catalyst added is determined in consideration of the specific surface area of the OER catalyst, the ease of deactivation, the cost, and the like. In general, in the case of an OER catalyst that is easily deactivated, the amount of the OER catalyst added is preferably at least the “lower limit value for not deactivating”. On the other hand, in the case of an OER catalyst that is hard to be deactivated, there is no difference in effect even if it is added more than necessary, and there is no actual benefit. Therefore, the amount of such an OER catalyst added is preferably not more than or equal to the "upper limit value at which the effect is saturated" or less than or equal to the value obtained by multiplying the upper limit value by a safety factor.
例えば、酸化ルテニウムは、失活しやすいことが知られている。本願発明者らによる研究より、酸化ルテニウムが失活しないための、触媒層の幾何学的面積（geometric area）当たりの酸化ルテニウムの添加量の下限値は、０．０２ｍｇ／ｃｍ2 GEOと判明している。一方、市販の酸化ルテニウム粉末のＢＥＴ比表面積は、約５０ｍ2／ｇである。
従って、酸化ルテニウムを第ｉＯＥＲ触媒として用いる場合において、酸化ルテニウムの総表面積Ｗiの下限値は、５０×１０4ｃｍ2 RuOx／ｇ×０．０２×１０-3ｇ／ｃｍ2 GEO＝１０ｃｍ2 RuOx／ｃｍ2 GEOと見積もられる。すなわち、酸化ルテニウムを第ｉＯＥＲ触媒として用いる場合において、酸化ルテニウムの失活を抑制するためには、Ｗiは、１０ｃｍ2 RuOｘ／ｃｍ2 GEO以上が好ましい。
For example, ruthenium oxide is known to be easily deactivated. From the research by the inventors of the present application, it was found that the lower limit of the amount of ruthenium oxide added per geometric area of the catalyst layer for not inactivating ruthenium oxide is 0.02 mg / cm 2 GEO. ing. On the other hand, the BET specific surface area of the commercially available ruthenium oxide powder is about 50 m 2 / g.
Accordingly, in the case of using ruthenium oxide as the iOER catalyst, the lower limit of the total surface area W i of ruthenium oxide, 50 × 10 4 cm 2 RuOx /g×0.02×10 -3 g / cm 2 GEO = 10cm 2 Estimated to be RuOx / cm 2 GEO . That is, when ruthenium oxide is used as the iOER catalyst, Wi i is preferably 10 cm 2 RuOx / cm 2 GEO or more in order to suppress the inactivation of ruthenium oxide.
一方、酸化イリジウムは、失活しにくいことが知られている。本願発明者らによる研究により、触媒層の幾何学的面積当たりの酸化イリジウムの添加量は、０．０１ｍｇ／ｃｍ2 GEO程度で十分であることが分かっている。そこで、酸化イリジウムの上限を、上記の値より若干大きい０．０１５ｍｇ／ｃｍ2 GEOとする。一方、市販の酸化イリジウム粉末のＢＥＴ比表面積は、約２５ｍ2／ｇである。
従って、酸化イリジウムを第ｊＯＥＲ触媒として用いる場合において、酸化イリジウムの総表面積Ｗjの上限値は、２５×１０4ｃｍ2 IrOx／ｇ×０．０１５×１０-3ｇ／ｃｍ2 GEO＝３．７５ｃｍ2 IrOx／ｃｍ2 GEOと見積もられる。すなわち、酸化ルテニウムを第ｊＯＥＲ触媒として用いる場合において、不必要なコスト増を抑制するためには、Ｗjは、３．７５ｃｍ2 IrOx／ｃｍ2 GEO以下が好ましい。
On the other hand, iridium oxide is known to be difficult to inactivate. Studies by the inventors of the present application have shown that the amount of iridium oxide added per geometric area of the catalyst layer is about 0.01 mg / cm 2 GEO. Therefore, the upper limit of iridium oxide is set to 0.015 mg / cm 2 GEO, which is slightly larger than the above value. On the other hand, the BET specific surface area of the commercially available iridium oxide powder is about 25 m 2 / g.
Therefore, when iridium oxide is used as the jOER catalyst, the upper limit of the total surface area W j of iridium oxide is 25 × 10 4 cm 2 IrOx / g × 0.015 × 10 -3 g / cm 2 GEO = 3. Estimated to be 75 cm 2 IrOx / cm 2 GEO. That is, in the case of using ruthenium oxide as the jOER catalyst, in order to suppress the increase in unnecessary cost, W j is preferably less 3.75cm 2 IrOx / cm 2 GEO.
［Ｃ． 頻度因子］
例えば、Ｗi＝６Ｗj、Ａi＝４×１０7×Ａj、ＴH＝３３３Ｋ（６０℃）、ＴL＝２４３Ｋ（−３０℃）である場合、式（３）より、次の式（４）が導かれる。
３９．３ｋＪ／ｍｏｌ＜Ｅi−Ｅj＜４８．０ｋＪ／ｍｏｌ …（４）
式（４）は、
（ａ）第ｉＯＥＲ触媒として酸化ルテニウムを用い、第ｊＯＥＲ触媒として酸化イリジウムを用いることが可能であること、及び、
（ｂ）この場合において、Ｗi＝６Ｗj、及び、Ａi＝４×１０7×Ａjとなるように、各ＯＥＲ触媒の添加量及び性状を最適化すると、酸化ルテニウム単独又は酸化イリジウム単独で用いた場合よりも、ＯＥＲ反応の活性が高くなること、
を表す。
[C. Frequency factor]
For example, W i = 6W j, A i = 4 × 10 7 × A j, T H = 333K (60 ℃), when it is T L = 243K (-30 ℃) , the equation (3), the following equation (4) is derived.
39.3kJ / mol <E i −E j <48.0kJ / mol… (4)
Equation (4) is
(A) It is possible to use ruthenium oxide as the iOER catalyst and iridium oxide as the jOER catalyst, and
(B) In this case, if the addition amount and properties of each OER catalyst are optimized so that W i = 6 W j and A i = 4 × 10 7 × A j, ruthenium oxide alone or iridium oxide alone The activity of the OER reaction is higher than that used in
Represents.
これらの内、Ｗi＝６Ｗjの条件は、各ＯＥＲ触媒の比表面積及び添加量を制御することにより、容易に満たすことができる。
一方、Ａi＝４×１０7×Ａjの条件は、例えば、
（ａ）各ＯＥＲ触媒の粒径を制御する方法、
（ｂ）各ＯＥＲ触媒の酸素親和性を制御する方法、
などにより満たすことができる。
Of these, the conditions of W i = 6W j, by controlling the specific surface area and the amount of each OER catalyst, can easily be met.
On the other hand, the condition of A i = 4 × 10 7 × A j is, for example,
(A) A method for controlling the particle size of each OER catalyst,
(B) A method for controlling the oxygen affinity of each OER catalyst,
It can be satisfied by.
［２． 固体高分子形燃料電池］
本発明に係る固体高分子形燃料電池は、本発明に係る触媒層をアノード側触媒層として用いたことを特徴とする。
本発明に係る触媒層の詳細については、上述した通りであるので、説明を省略する。
また、固体高分子形燃料電池のその他の構成要素（電解質膜、カソード側触媒層、ガス拡散層、セパレータ等）の材料、構造等については、特に限定されるものではなく、目的に応じて最適なものを選択することができる。
[2. Polymer electrolyte fuel cell]
The polymer electrolyte fuel cell according to the present invention is characterized in that the catalyst layer according to the present invention is used as the anode side catalyst layer.
The details of the catalyst layer according to the present invention are as described above, and thus the description thereof will be omitted.
The materials, structures, etc. of other components (electrolyte membrane, cathode side catalyst layer, gas diffusion layer, separator, etc.) of the polymer electrolyte fuel cell are not particularly limited and are optimal according to the purpose. You can choose the one you like.
［３． 作用］
ＯＥＲ反応の活性化エネルギーが大きい第ｉＯＥＲ触媒は、活性の温度依存性が大きい。そのため、第ｉＯＥＲ触媒は、低温では活性が低いが、高温では高い活性を示す。
一方、ＯＥＲ反応の活性化エネルギーが小さい第ｊＯＥＲ触媒は、活性の温度依存性が小さい。そのため、第ｊＯＥＲ触媒は、高温では活性が低いが、低温では比較的高い活性を示す。
[3. Action]
The iOER catalyst having a large activation energy of the OER reaction has a large temperature dependence of activity. Therefore, the iOER catalyst has low activity at low temperature, but shows high activity at high temperature.
On the other hand, the jOER catalyst having a small activation energy of the OER reaction has a small temperature dependence of activity. Therefore, the jOER catalyst has low activity at high temperature, but relatively high activity at low temperature.
このような活性の温度依存性が異なる少なくとも２種類のＯＥＲ触媒を触媒層に添加すると、高温運転時には主として第ｉＯＥＲ触媒がアノード成分の酸化を抑制し、低温運転時には主として第ｊＯＥＲ触媒がアノード成分の酸化を抑制する。その結果、高温運転時及び低温運転時のいずれの条件下においても、アノード成分の酸化を抑制することができる。特に、各ＯＥＲ触媒の性状（すなわち、活性化エネルギー、総表面積、及び頻度因子）を最適化すると、各ＯＥＲ触媒を単独で用いた場合に比べて、高い活性を示す。 When at least two types of OER catalysts having different activity depending on the temperature are added to the catalyst layer, the iOER catalyst mainly suppresses the oxidation of the anode component during high temperature operation, and the jOER catalyst mainly suppresses the oxidation of the anode component during low temperature operation. Suppresses oxidation. As a result, oxidation of the anode component can be suppressed under both high temperature operation and low temperature operation conditions. In particular, when the properties of each OER catalyst (that is, activation energy, total surface area, and frequency factor) are optimized, higher activity is exhibited as compared with the case where each OER catalyst is used alone.
例えば、高温（〜６０℃）では、酸化ルテニウムは酸化イリジウムよりＯＥＲ活性が高いため、通常運転時の急な水素欠に対する耐性を向上させる上で有力な添加剤である。しかし、低温（３０℃以下）では、酸化ルテニウムは活性が著しく低いため、これを単独で用いると、氷点下始動時の水素欠に対する耐性がほとんど無くなってしまう。
これに対し、酸化ルテニウムと酸化イリジウムとを共存させると、高温と低温の両方での水素欠耐性が高い燃料電池にすることが可能となる。
For example, at high temperatures (~ 60 ° C.), ruthenium oxide has higher OER activity than iridium oxide, and is therefore a powerful additive for improving resistance to sudden hydrogen deficiency during normal operation. However, at low temperatures (30 ° C. or lower), ruthenium oxide has extremely low activity, and when used alone, the resistance to hydrogen deficiency at sub-zero starting is almost lost.
On the other hand, when ruthenium oxide and iridium oxide coexist, it becomes possible to obtain a fuel cell having high resistance to hydrogen deficiency at both high and low temperatures.
［１． 試験方法］
アノードに酸化イリジウムを添加した場合、及び、酸化ルテニウムを添加した場合の耐水素欠運転の特性を調べるため、以下の実験を行った。
サンプルとして、アノオードに、
（ａ）酸化イリジウムを０．０１ｍｇ／ｃｍ2添加したＭＥＡ（試料Ｎｏ．１）、
（ｂ）酸化ルテニウムを０．０１ｍｇ／ｃｍ2添加したＭＥＡ（試料Ｎｏ．２）、及び、
（ｃ）酸化ルテニウムを０．０３ｍｇ／ｃｍ2添加したＭＥＡ（試料Ｎｏ．３）
の３種類を準備した。
[1. Test method]
The following experiments were conducted to investigate the characteristics of hydrogen-deficient operation when iridium oxide was added to the anode and when ruthenium oxide was added.
As a sample, to Anoode,
(A) MEA (Sample No. 1) to which 0.01 mg / cm 2 of iridium oxide was added,
(B) MEA (Sample No. 2) to which 0.01 mg / cm 2 of ruthenium oxide was added, and
(C) MEA to which 0.03 mg / cm 2 of ruthenium oxide was added (Sample No. 3)
We prepared three types.
これらを用い、水素欠運転模擬耐久試験を行った。すなわち、アノードに窒素、カソードに空気を供給した状態で、３０℃又は６０℃にセル温度を設定した。この状態で電流を１．０Ａ／ｃｍ2に保持し、セル電圧及び運転継続時間を調べた。 Using these, a hydrogen-deficient operation simulated durability test was conducted. That is, the cell temperature was set to 30 ° C. or 60 ° C. with nitrogen supplied to the anode and air supplied to the cathode. In this state, the current was maintained at 1.0 A / cm 2 , and the cell voltage and operation duration were examined.
［２． 結果］
図１に、酸化イリジウム又は酸化ルテニウムを添加したＭＥＡの３０℃での水素欠運転耐性を示す。図２に、酸化イリジウム又は酸化ルテニウムを添加したＭＥＡの６０℃での水素欠運転耐性を示す。図１及び図２において、横軸は電流保持時間、縦軸はセル電圧（＝カソード電位−アノード電位）である。
[2. result]
FIG. 1 shows the resistance to hydrogen deficiency operation of MEA supplemented with iridium oxide or ruthenium oxide at 30 ° C. FIG. 2 shows the resistance to hydrogen deficiency operation of MEA supplemented with iridium oxide or ruthenium oxide at 60 ° C. In FIGS. 1 and 2, the horizontal axis represents the current holding time, and the vertical axis represents the cell voltage (= cathode potential-anode potential).
［２．１． ６０℃での水素欠運転］
まず、酸化ルテニウムを０．０１ｍｇ／ｃｍ2添加した場合、いずれの温度においても、試験開始直後に運転が継続できなくなっていることが分かる。これは、酸化ルテニウムは高電流域でＯＥＲ活性が失活するためである。
これに対しては、酸化ルテニウムの添加量を単純に増やす（すなわち、総表面積を増やす）ことが有効である。図２から分かるように、酸化ルテニウムを０．０３ｍｇ／ｃｍ2添加した場合、６０℃、１．０Ａ／ｃｍ2の条件では酸化イリジウム添加品よりセル電圧が高く、アノード電位上昇の抑制効果が高い。
[2.1. Hydrogen shortage operation at 60 ° C]
First, when 0.01 mg / cm 2 of ruthenium oxide was added, it was found that the operation could not be continued immediately after the start of the test at any temperature. This is because ruthenium oxide inactivates OER activity in the high current range.
To this end, it is effective to simply increase the amount of ruthenium oxide added (that is, increase the total surface area). As can be seen from FIG. 2, when 0.03 mg / cm 2 of ruthenium oxide is added, the cell voltage is higher than that of the iridium oxide-added product under the conditions of 60 ° C. and 1.0 A / cm 2, and the effect of suppressing the increase in anode potential is high. ..
なお、酸化ルテニウム０．０３ｍｇ／ｃｍ2添加品の運転継続時間は酸化イリジウム添加品のそれより短いが、２００秒程度はある。実際に起こりうる水素欠運転状態の継続時間は数十秒程度であるため、２００秒程度の運転継続時間があれば十分といえる。
以上から、酸化ルテニウム０．０３ｍｇ／ｃｍ2添加品（試料Ｎｏ．３）は、酸化イリジウム０．０１ｍｇ／ｃｍ2添加品（試料Ｎｏ．１）より、６０℃での水素欠運転時のカーボン劣化抑制効果が高いと言える。
The operation duration of the ruthenium oxide 0.03 mg / cm 2 additive is shorter than that of the iridium oxide additive, but it is about 200 seconds. Since the duration of the hydrogen-deficient operation state that can actually occur is about several tens of seconds, it can be said that an operation duration of about 200 seconds is sufficient.
From the above, the ruthenium oxide 0.03 mg / cm 2 additive (Sample No. 3) is more carbon-deteriorated during hydrogen-deficient operation at 60 ° C. than the iridium oxide 0.01 mg / cm 2 additive (Sample No. 1). It can be said that the inhibitory effect is high.
［２．２． ３０℃での水素欠運転］
図１に示すように、酸化ルテニウム０．０３ｍｇ／ｃｍ2添加品は、３０℃、１．０Ａ／ｃｍ2の条件下では水素欠耐性が低い。そのため、酸化ルテニウムを単独で使用した場合において、このような条件で水素欠運転状態に陥った時には、セルが致命的なダメージを受ける可能性がある。
他方、酸化イリジウム添加品は、この条件でも長い時間運転を継続できていることから、比較的高いＯＥＲ活性を発揮できていることが分かる。このことから、酸化ルテニウム添加品に酸化イリジウムを追加で添加すると、酸化ルテニウムの高温での高ＯＥＲ活性を活用しつつ、低温域での水素欠運転にも耐性が高いセルになると考えられる。
[2.2. Hydrogen shortage operation at 30 ° C]
As shown in FIG. 1, the ruthenium oxide 0.03 mg / cm 2 additive has low hydrogen deficiency resistance under the conditions of 30 ° C. and 1.0 A / cm 2. Therefore, when ruthenium oxide is used alone, the cell may be fatally damaged when it falls into a hydrogen-deficient operation state under such conditions.
On the other hand, since the iridium oxide-added product can continue to operate for a long time even under these conditions, it can be seen that it can exhibit relatively high OER activity. From this, it is considered that when iridium oxide is additionally added to the ruthenium oxide additive, the cell becomes highly resistant to hydrogen deficiency operation in a low temperature range while utilizing the high OER activity of ruthenium oxide at high temperature.
ここで、酸化イリジウムと酸化ルテニウムとでＯＥＲ活性が高い温度域が異なる理由は、これらの活性化エネルギーが異なるためである。従って、酸化イリジウムと酸化ルテニウムとの組み合わせに限らず、活性化エネルギーが異なる触媒の組み合わせであれば、酸化イリジウム−酸化ルテニウム系と同様の効果（すなわち、作動温度に応じて、異なる触媒が高ＯＥＲ活性を示すという効果）が得られると考えられる。 Here, the reason why the temperature range in which the OER activity is high differs between iridium oxide and ruthenium oxide is that their activation energies are different. Therefore, not only the combination of iridium oxide and ruthenium oxide, but also the combination of catalysts having different activation energies has the same effect as the iridium oxide-ruthenium oxide system (that is, different catalysts have a high OER depending on the operating temperature. It is considered that the effect of showing activity) can be obtained.
以上、本発明の実施の形態について詳細に説明したが、本発明は上記実施の形態に何ら限定されるものではなく、本発明の要旨を逸脱しない範囲内で種々の改変が可能である。 Although the embodiments of the present invention have been described in detail above, the present invention is not limited to the above embodiments, and various modifications can be made without departing from the gist of the present invention.
本発明に係る触媒層は、固体高分子形燃料電池のアノード側触媒層に用いることができる。 The catalyst layer according to the present invention can be used for the anode side catalyst layer of the polymer electrolyte fuel cell.
Claims (4)
（１）前記触媒層は、
電極触媒と、
アイオノマと、
第１〜第ｎ酸素生成（ＯＥＲ）触媒（ｎ≧２）と
を備えている。
（２）第ｉＯＥＲ触媒（１≦ｉ≦ｎ）のＯＥＲ反応の活性化エネルギーＥiは、第ｊＯＥＲ触媒（１≦ｊ≦ｎ、ｉ≠ｊ）のＯＥＲ反応の活性化エネルギーＥjより大きい。
（３）前記第ｉＯＥＲ触媒及び前記第ｊＯＥＲ触媒は、次の式（３）の関係を満たす。
ＴLは、水素欠状態が起こりうる最低温度、
ＴHは、水素欠状態が起こりうる最高温度、
Ｗiは、前記触媒層に含まれる前記第ｉＯＥＲ触媒の総表面積、
Ａiは、前記第ｉＯＥＲ触媒の前記ＯＥＲ反応の触媒表面積当たりの頻度因子、
Ｗjは、前記触媒層に含まれる前記第ｊＯＥＲ触媒の総表面積、
Ａjは、前記第ｊＯＥＲ触媒の前記ＯＥＲ反応の触媒表面積当たりの頻度因子、
Ｒは、気体定数。 A catalyst layer having the following configuration.
(1) The catalyst layer is
With the electrode catalyst
With ionomer
It is provided with a first to nth oxygen production (OER) catalyst (n ≧ 2).
(2) The activation energy E i of the OER reaction of the third iOER catalyst (1 ≦ i ≦ n) is larger than the activation energy E j of the OER reaction of the jOER catalyst (1 ≦ j ≦ n, i ≠ j).
(3) The iOER catalyst and the jOER catalyst satisfy the relationship of the following formula (3).
TL is the lowest temperature at which hydrogen deficiency can occur.
TH is the maximum temperature at which hydrogen deficiency can occur.
W i is the total surface area of the first iOER catalyst contained in the catalyst layer,
A i is a pre-exponential factor per catalyst surface area of the OER reaction of the iOER catalyst.
W j is the total surface area of the jOER catalyst contained in the catalyst layer.
A j is a pre-exponential factor per catalyst surface area of the OER reaction of the jOER catalyst.
R is the gas constant.
前記第ｊＯＥＲ触媒は、酸化イリジウムからなる
請求項１に記載の触媒層。 The iOER catalyst is composed of ruthenium oxide and is composed of ruthenium oxide.
The catalyst layer according to claim 1, wherein the jOER catalyst is made of iridium oxide.
前記Ｗjは、３．７５ｃｍ2 IrOx／ｃｍ2 GEO以下である
請求項２に記載の触媒層。 The W i is a 10cm 2 RuOx / cm 2 GEO or more,
The catalyst layer according to claim 2 , wherein W j is 3.75 cm 2 IrOx / cm 2 GEO or less.
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