JP7347033B2 - electrode plate - Google Patents
electrode plate Download PDFInfo
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- JP7347033B2 JP7347033B2 JP2019162118A JP2019162118A JP7347033B2 JP 7347033 B2 JP7347033 B2 JP 7347033B2 JP 2019162118 A JP2019162118 A JP 2019162118A JP 2019162118 A JP2019162118 A JP 2019162118A JP 7347033 B2 JP7347033 B2 JP 7347033B2
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- coating film
- electrode plate
- corrosion resistance
- substrate
- phosphide
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- 239000011248 coating agent Substances 0.000 claims description 67
- 238000000576 coating method Methods 0.000 claims description 67
- 239000000758 substrate Substances 0.000 claims description 39
- 239000000446 fuel Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000005518 polymer electrolyte Substances 0.000 claims description 10
- 238000001228 spectrum Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 238000005868 electrolysis reaction Methods 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000010408 film Substances 0.000 description 68
- 238000005260 corrosion Methods 0.000 description 56
- 230000007797 corrosion Effects 0.000 description 56
- 238000010438 heat treatment Methods 0.000 description 26
- 239000010936 titanium Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 20
- 238000000034 method Methods 0.000 description 14
- 239000010409 thin film Substances 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000011651 chromium Substances 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 229910001069 Ti alloy Inorganic materials 0.000 description 7
- 238000004544 sputter deposition Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- -1 titanium alloys Chemical class 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Images
Classifications
-
- 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
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Fuel Cell (AREA)
Description
本発明は、電極板に関し、さらに詳しくは、固体高分子形燃料電池用セパレータ、固体高分子形（ＰＥＭ）水電解装置用バイポーラプレートなどに用いられる電極板に関する。 The present invention relates to an electrode plate, and more particularly to an electrode plate used in a separator for a polymer electrolyte fuel cell, a bipolar plate for a polymer electrolyte (PEM) water electrolyzer, and the like.
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（触媒層）が接合された膜電極接合体（Membrane Electrode Assembly，ＭＥＡ）を備えている。ＭＥＡの両面には、さらに、ガス拡散層を含むガス流路を備えた集電体（セパレータともいう）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。このような燃料電池のアノード及びカソードに、それぞれ、燃料ガス及び酸化剤ガスを供給すると、カソードにおいて水が生成すると同時に、電力を取り出すことができる。 A polymer electrolyte fuel cell includes a membrane electrode assembly (MEA) in which electrodes (catalyst layers) containing a catalyst are joined to both sides of an electrolyte membrane. Further, current collectors (also referred to as separators) each having a gas flow path including a gas diffusion layer are arranged on both sides of the MEA. A polymer electrolyte fuel cell usually has a structure (fuel cell stack) in which a plurality of single cells each made of such an MEA and a current collector are stacked. When fuel gas and oxidant gas are supplied to the anode and cathode of such a fuel cell, respectively, water is generated at the cathode and electric power can be extracted at the same time.
一方、ＰＥＭ水電解装置は、燃料電池とほぼ同様の構造を備えているが、燃料電池とは逆の反応を起こさせるものである。すなわち、酸素極に水を供給し、電極間に電力を供給すると、水の電気分解が進行し、水素及び酸素を取り出すことができる。 On the other hand, a PEM water electrolysis device has almost the same structure as a fuel cell, but causes a reaction opposite to that of a fuel cell. That is, when water is supplied to the oxygen electrode and electric power is supplied between the electrodes, electrolysis of the water proceeds and hydrogen and oxygen can be extracted.
なお、ＰＥＭ水電解装置において、ＭＥＡの両面に配置される部材は、一般に、バイポーラプレート（複極板）と呼ばれている。一方、上述したように、固体高分子形燃料電池において、ＭＥＡの両面に配置される部材は、一般に、集電体、あるいは、セパレータと呼ばれている。
本発明において「電極板」という時は、これらの総称、すなわち、ＭＥＡの用途を問わず、ＭＥＡの両面に配置される拡散層等を含む導電性部材の総称を表す。
Note that in the PEM water electrolysis device, the members arranged on both sides of the MEA are generally called bipolar plates. On the other hand, as described above, in a polymer electrolyte fuel cell, the members arranged on both sides of the MEA are generally called current collectors or separators.
In the present invention, the term "electrode plate" refers to these general terms, that is, a general term for conductive members including diffusion layers and the like disposed on both sides of the MEA, regardless of the purpose of the MEA.
固体高分子形燃料電池及びＰＥＭ水電解装置において、電解質膜には、通常、ポリパーフルオロカーボンスルホン酸膜が用いられている。そのため、電極板は、使用中に強酸性雰囲気に曝される。使用中に電極板の表面が酸化され、電極との接触面に高抵抗層が形成されると、電極反応又は電解反応が阻害される。 In polymer electrolyte fuel cells and PEM water electrolyzers, polyperfluorocarbon sulfonic acid membranes are usually used as electrolyte membranes. Therefore, the electrode plate is exposed to a strongly acidic atmosphere during use. When the surface of the electrode plate is oxidized during use and a high resistance layer is formed on the contact surface with the electrode, the electrode reaction or electrolytic reaction is inhibited.
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、チタン合金板とステンレス鋼板の積層板からなる複極板を備えた水電解槽が開示されている。
同文献には、
（ａ）複極板としてチタン合金を用いる場合、陰極側を白金メッキして水素脆化を防止する必要があるが、白金メッキを施しても水素脆化を完全に防止できない点、及び、
（ｂ）ステンレス鋼板が陰極側に来るように積層板を配置すると、チタン合金の水素脆化防止のために複極板の陰極側を白金メッキする必要がなくなる点、
が記載されている。
In order to solve this problem, various proposals have been made in the past.
For example,
In the same document,
(a) When using a titanium alloy as a bipolar plate, it is necessary to plate the cathode side with platinum to prevent hydrogen embrittlement, but even with platinum plating, hydrogen embrittlement cannot be completely prevented;
(b) If the laminated plate is arranged so that the stainless steel plate is on the cathode side, there is no need to plate the cathode side of the bipolar plate with platinum to prevent hydrogen embrittlement of the titanium alloy;
is listed.
従来、ＰＥＭ水電解装置用バイポーラプレートとして、白金メッキしたチタン合金、チタン合金とステンレス鋼板の積層板などが提案されている。しかし、白金及びチタン合金はいずれも高価であるため、使用量を極力少なくするのが好ましい。また、メッキプロセスも高コストプロセスであるため、被覆膜の成膜には低コストプロセスを用いるのが好ましい。しかし、高価な材料の使用量が少なく、かつ、高コストなプロセスを用いることなく製造が可能な、電極板が提案された例は、従来にはない。 Conventionally, platinum-plated titanium alloys, laminates of titanium alloys and stainless steel plates, and the like have been proposed as bipolar plates for PEM water electrolysis devices. However, since platinum and titanium alloys are both expensive, it is preferable to use as little amount as possible. Furthermore, since the plating process is also a high-cost process, it is preferable to use a low-cost process to form the coating film. However, there has never been an example in the past in which an electrode plate that can be manufactured using a small amount of expensive materials and without using expensive processes has been proposed.
本発明が解決しようとする課題は、耐食性及び導電性に優れ、しかも、低コストな電極板を提供することにある。 The problem to be solved by the present invention is to provide an electrode plate that is excellent in corrosion resistance and conductivity and is low in cost.
上記課題を解決するために本発明に係る電極板は、以下の構成を備えていることを要旨とする。
（１）前記電極板は、
基板と、
前記基板の表面の少なくとも一部に形成された被覆膜と
を備えている。
（２）前記被覆膜は、次の式（１）で表される組成を有するリン化物を含む。
Ｍ2-xＴｉxＰ …（１）
但し、
Ｍは、Ｎｉ、Ｃｏ、Ｆｅ、Ｍｎ、及びＣｒからなる群から選ばれるいずれか１以上の元素、
０．１≦ｘ≦１．９
（３）前記被覆膜は、ＸＲＤスペクトル測定を行った時に、前記リン化物の最強線ピークの半値全幅が０．６°以下であるものからなる。
In order to solve the above problems, the electrode plate according to the present invention has the following configuration.
(1) The electrode plate is
A substrate and
and a coating film formed on at least a portion of the surface of the substrate.
(2) The coating film contains a phosphide having a composition represented by the following formula (1).
M 2-x Ti x P…(1)
however,
M is any one or more elements selected from the group consisting of Ni, Co, Fe, Mn, and Cr;
0.1≦x≦1.9
(3) The coating film is such that the full width at half maximum of the strongest line peak of the phosphide is 0.6° or less when an XRD spectrum is measured.
ある種のリン化物は、耐食性及び導電性に優れている。また、リン化物は、貴金属を含まないため、低コストである。さらに、リン化物からなる薄膜は、比較的低コストなスパッタ法により成膜することができる。そのため、リン化物からなる薄膜を電極板の被覆膜に適用すれば、耐食性及び導電性に優れ、しかも低コストな電極板を得ることができる。
さらに、一般に、成膜直後のリン化物薄膜は、結晶性が低い。これに対し、種々の方法により成膜されたリン化物薄膜を適切な条件下で熱処理すると、リン化物薄膜の結晶性が向上する。その結果、熱処理前に比べて導電性がさらに向上する。
Certain phosphides have excellent corrosion resistance and electrical conductivity. In addition, phosphides do not contain noble metals, so they are low cost. Furthermore, a thin film made of phosphide can be formed by a relatively low-cost sputtering method. Therefore, if a thin film made of phosphide is applied to the coating film of an electrode plate, an electrode plate with excellent corrosion resistance and conductivity and low cost can be obtained.
Furthermore, a phosphide thin film that has just been formed generally has low crystallinity. On the other hand, when a phosphide thin film formed by various methods is heat-treated under appropriate conditions, the crystallinity of the phosphide thin film is improved. As a result, the conductivity is further improved compared to before the heat treatment.
以下、本発明の一実施の形態について詳細に説明する。
［１． 電極板］
本発明に係る電極板は、以下の構成を備えている。
（１）前記電極板は、
基板と、
前記基板の表面の少なくとも一部に形成された被覆膜と
を備えている。
（２）前記被覆膜は、次の式（１）で表される組成を有するリン化物を含む。
Ｍ2-xＴｉxＰ …（１）
但し、
Ｍは、Ｎｉ、Ｃｏ、Ｆｅ、Ｍｎ、及びＣｒからなる群から選ばれるいずれか１以上の元素、
０．１≦ｘ≦１．９
（３）前記被覆膜は、ＸＲＤスペクトル測定を行った時に、前記リン化物の最強線ピークの半値全幅が０．６°以下であるものからなる。
Hereinafter, one embodiment of the present invention will be described in detail.
[1. Electrode plate]
The electrode plate according to the present invention has the following configuration.
(1) The electrode plate is
A substrate and
and a coating film formed on at least a portion of the surface of the substrate.
(2) The coating film contains a phosphide having a composition represented by the following formula (1).
M 2-x Ti x P…(1)
however,
M is any one or more elements selected from the group consisting of Ni, Co, Fe, Mn, and Cr;
0.1≦x≦1.9
(3) The coating film is such that the full width at half maximum of the strongest line peak of the phosphide is 0.6° or less when an XRD spectrum is measured.
［１．１． 基板］
基板の形状は、特に限定されるものではなく、目的に応じて最適な形状を選択することができる。電極板には、通常、発電用燃料、酸化剤、電解用原料、あるいは反応生成物を流通させるためのガス流路が設けられている。
[1.1. substrate]
The shape of the substrate is not particularly limited, and an optimal shape can be selected depending on the purpose. The electrode plate is usually provided with a gas flow path for flowing fuel for power generation, an oxidizing agent, a raw material for electrolysis, or a reaction product.
電極板は、ＭＥＡの電極と、負荷（燃料電池の場合）又は電源（水電解装置の場合）との間で電子の授受を行う必要がある。そのため、電極板には、一般にＭＥＡの使用環境に耐える高い耐食性に加えて、高い導電性が求められる。
但し、本発明においては、被覆膜に高耐食性、かつ、高導電性のリン化物が用いられるため、基板は、少なくともＭＥＡの使用環境に耐える耐食性を持つものであれば良く、必ずしも導電性材料である必要はない。
基板の材料としては、例えば、
（ａ）チタン合金、ステンレス鋼、アルミニウム、銅、ニッケル、モリブデン、クロムなどの金属、
（ｂ）カーボン、
などがある。
The electrode plate needs to exchange electrons between the electrode of the MEA and a load (in the case of a fuel cell) or a power source (in the case of a water electrolysis device). Therefore, the electrode plate is generally required to have high electrical conductivity in addition to high corrosion resistance that can withstand the environment in which the MEA is used.
However, in the present invention, since a phosphide with high corrosion resistance and high conductivity is used for the coating film, the substrate may be made of a material having corrosion resistance that at least withstands the environment in which the MEA is used, and is not necessarily made of a conductive material. It doesn't have to be.
Examples of substrate materials include:
(a) Metals such as titanium alloys, stainless steel, aluminum, copper, nickel, molybdenum, chromium, etc.
(b) carbon,
and so on.
［１．２． 被覆膜］
［１．２．１． 材料］
被覆膜は、高耐食・高導電性のリン化物を含む。本発明において、「リン化物」とは、Ｔｉ、Ｐ、及び、Ｔｉ以外の金属元素Ｍを含む化合物であって、次の式（１）で表される組成を有するものをいう。
Ｍ2-xＴｉxＰ …（１）
但し、
Ｍは、Ｎｉ、Ｃｏ、Ｆｅ、Ｍｎ、及びＣｒからなる群から選ばれるいずれか１以上の元素、
０．１≦ｘ≦１．９
[1.2. Coating film]
[1.2.1. material]
The coating film contains a highly corrosion resistant and highly conductive phosphide. In the present invention, "phosphide" refers to a compound containing Ti, P, and a metal element M other than Ti, and has a composition represented by the following formula (1).
M 2-x Ti x P…(1)
however,
M is any one or more elements selected from the group consisting of Ni, Co, Fe, Mn, and Cr;
0.1≦x≦1.9
式（１）中、ｘは、金属元素の総原子数に対するＴｉの原子数の比を表す。ｘが小さすぎると、接触抵抗が増大する。従って、ｘは、０．１以上である必要がある。ｘは、好ましくは、０．２以上、さらに好ましくは、０．４以上である。
一方、ｘが大きくなりすぎると、かえって接触抵抗が増大する。従って、ｘは、１．９以下である必要がある。ｘは、好ましくは、１．８以下、さらに好ましくは、１．６以下である。
In formula (1), x represents the ratio of the number of Ti atoms to the total number of atoms of the metal elements. If x is too small, contact resistance will increase. Therefore, x needs to be 0.1 or more. x is preferably 0.2 or more, more preferably 0.4 or more.
On the other hand, if x becomes too large, the contact resistance will increase on the contrary. Therefore, x needs to be 1.9 or less. x is preferably 1.8 or less, more preferably 1.6 or less.
所定の組成を有するリン化物は、いずれも、燃料電池環境下又は水電解装置環境下における耐食性が高く、かつ、導電性も高いので、電極板の被覆膜として好適である。被覆膜は、これらのいずれか１種のリン化物を含むものでも良く、あるいは、２種以上を含むものでも良い。
被覆膜を構成するリン化物は、特に、金属元素Ｍとして、Ｎｉ、Ｆｅ、及びＭｎからなる群から選ばれるいずれか１以上の元素を含むものが好ましい。これらのリン化物は、いずれも高い耐久性と、高い導電性とを併せ持つ。
Any phosphide having a predetermined composition has high corrosion resistance in a fuel cell environment or a water electrolyzer environment and also has high conductivity, and therefore is suitable as a coating film for an electrode plate. The coating film may contain any one of these phosphides, or may contain two or more of these phosphides.
It is particularly preferable that the phosphide constituting the coating film contains one or more elements selected from the group consisting of Ni, Fe, and Mn as the metal element M. All of these phosphides have both high durability and high conductivity.
被覆膜は、実質的にリン化物のみからなるものが好ましいが、高耐食性及び高導電性を阻害しない限りにおいて、他の相が含まれていても良い。
他の相としては、例えば、
（ａ）不可避的不純物、
（ｂ）リン化物以外の高耐食性物質、
などがある。
It is preferable that the coating film consists essentially only of phosphide, but other phases may be included as long as they do not impede high corrosion resistance and high conductivity.
Other phases include, for example,
(a) unavoidable impurities;
(b) highly corrosion resistant substances other than phosphides;
and so on.
［１．２．２． 被覆膜の厚さ］
被覆膜の厚さは、特に限定されるものではなく、目的に応じて最適な厚さを選択することができる。一般に、被覆膜の厚さが薄くなりすぎると、十分な耐食性が得られない。従って、被覆膜の厚さは、０．０１μｍ以上が好ましい。被覆膜の厚さは、好ましくは、０．０５μｍ以上、さらに好ましくは、０．１μｍ以上である。
一方、被覆膜の厚さが厚くなりすぎると、基材との密着性が低下し、剥離や割れが生じるおそれがある。従って、被覆膜の厚さは、２００μｍ以下が好ましい。被覆膜の厚さは、好ましくは、１００μｍ以下、さらに好ましくは、８０μｍ以下である。
[1.2.2. Thickness of coating film]
The thickness of the coating film is not particularly limited, and an optimal thickness can be selected depending on the purpose. Generally, if the thickness of the coating film becomes too thin, sufficient corrosion resistance cannot be obtained. Therefore, the thickness of the coating film is preferably 0.01 μm or more. The thickness of the coating film is preferably 0.05 μm or more, more preferably 0.1 μm or more.
On the other hand, if the thickness of the coating film becomes too thick, the adhesion to the base material may decrease, and peeling or cracking may occur. Therefore, the thickness of the coating film is preferably 200 μm or less. The thickness of the coating film is preferably 100 μm or less, more preferably 80 μm or less.
［１．２．３． 被覆膜の形成位置］
基板が導電性材料からなる場合、被覆膜は、基板の全面に形成されていても良く、あるいは、電極との接触面にのみ形成されていても良い。基板には、通常、ガス流路を形成するための凹凸が形成されており、電極板は凸部を介して電極と接触する。このような場合、電極との非接触面に高抵抗層が形成されたとしても電子の授受に支障はないので、少なくとも電極との接触面（凸部の先端面）に被覆膜を形成すれば良い。
一方、基板が導電性材料でない場合、電子の授受は被覆膜を介して行われる。このような場合には、被覆膜は、電極との接触面だけでなく、電極と負荷又は電源との間で電子の授受が可能となる位置に形成する必要がある。
[1.2.3. Formation position of coating film]
When the substrate is made of a conductive material, the coating film may be formed on the entire surface of the substrate, or may be formed only on the surface in contact with the electrode. The substrate usually has projections and depressions formed thereon to form gas flow paths, and the electrode plate contacts the electrodes through the projections. In such a case, even if a high-resistance layer is formed on the surface that does not come into contact with the electrode, there will be no problem in transferring and receiving electrons, so it is necessary to form a coating film at least on the surface that comes into contact with the electrode (the tip surface of the convex part). Good.
On the other hand, when the substrate is not a conductive material, electrons are exchanged via the coating film. In such a case, the coating film needs to be formed not only on the contact surface with the electrode but also at a position where electrons can be exchanged between the electrode and the load or power source.
［１．２．４． 結晶性］
後述するように、本発明に係る電極板は、種々の方法を用いて基板表面に被覆膜を形成した後、熱処理することにより得られる。そのため、熱処理前に比べて結晶性が高い。
[1.2.4. crystalline]
As will be described later, the electrode plate according to the present invention can be obtained by forming a coating film on the surface of a substrate using various methods and then subjecting the film to heat treatment. Therefore, the crystallinity is higher than that before heat treatment.
結晶性の程度は、ＸＲＤスペクトル測定を行った時に、リン化物の最強線ピークの半値全幅により評価することができる。具体的には、ＣｕＫα1Ｘ線（波長＝１．５４０６Å）を用いてＸ線回折を行った場合、結晶性のリン化物のＸＲＤスペクトルには、その組成によらず、２θが４６°付近、５１°付近、及び６７°付近に、相対的に大きな回折ピークが現れる。これらの中の最強線ピークの半値全幅を測定することにより、結晶性の程度を知ることができる。製造条件を最適化すると、リン化物の最強線ピークの半値全幅は、０．６°以下、あるいは、０．４°以下となる。 The degree of crystallinity can be evaluated by the full width at half maximum of the strongest line peak of phosphide when performing XRD spectrum measurement. Specifically, when X-ray diffraction is performed using CuK α1 X-rays (wavelength = 1.5406 Å), the XRD spectrum of crystalline phosphide shows that 2θ is around 46°, regardless of its composition. Relatively large diffraction peaks appear near 51° and 67°. By measuring the full width at half maximum of the strongest line peak among these, the degree of crystallinity can be determined. When the manufacturing conditions are optimized, the full width at half maximum of the strongest line peak of phosphide becomes 0.6° or less, or 0.4° or less.
［１．２．５． 接触抵抗］
本発明に係る被覆膜は、結晶性が高い。そのため、低結晶性のリン化物からなる被覆膜に比べて接触抵抗が低い。製造条件を最適化すると、被覆膜の接触抵抗は、１０ｍΩｃｍ2以下となる。製造条件をさらに最適化すると、接触抵抗は、８ｍΩｃｍ2以下、あるいは、６ｍΩｃｍ2以下となる。
[1.2.5. Contact resistance]
The coating film according to the present invention has high crystallinity. Therefore, the contact resistance is lower than that of a coating film made of a low-crystalline phosphide. If the manufacturing conditions are optimized, the contact resistance of the coating film will be 10 mΩcm 2 or less. When the manufacturing conditions are further optimized, the contact resistance becomes 8 mΩcm 2 or less, or 6 mΩcm 2 or less.
［１．３． 用途］
本発明に係る電極板は、
（ａ）固体高分子形燃料電池用セパレータ、
（ｂ）ＰＥＭ水電解装置用バイポーラプレート、
などに用いることができる。
[1.3. Use]
The electrode plate according to the present invention is
(a) Separator for polymer electrolyte fuel cells,
(b) Bipolar plate for PEM water electrolysis device,
It can be used for etc.
［２． 電極板の製造方法］
電極板は、
（ａ）所定の形状を有する基板の表面に、所定のパターンで被覆膜を形成し、
（ｂ）被覆膜が形成された基板を熱処理する
ことにより製造することができる。
[2. Manufacturing method of electrode plate]
The electrode plate is
(a) forming a coating film in a predetermined pattern on the surface of a substrate having a predetermined shape;
(b) It can be manufactured by heat treating a substrate on which a coating film is formed.
［２．１． 被覆膜形成工程］
まず、所定の形状を有する基板の表面に、所定のパターンで被覆膜を形成する（被覆膜形成工程）。被覆膜の形成方法は、特に限定されるものではなく、目的に応じて最適な方法を選択することができる。
被覆膜の形成方法としては、例えば、スパッタリング法、蒸着法、めっき法、プラズマ法、ＣＶＤ法などがある。これらの中でも、スパッタリング法は、他の方法と比べて低コストであり、大面積の成膜も容易であるので、被覆膜の形成方法として好適である。
[2.1. Coating film formation process]
First, a coating film is formed in a predetermined pattern on the surface of a substrate having a predetermined shape (coating film forming step). The method of forming the coating film is not particularly limited, and an optimal method can be selected depending on the purpose.
Examples of methods for forming the coating film include sputtering, vapor deposition, plating, plasma, and CVD. Among these, the sputtering method is suitable as a method for forming a coating film because it is less expensive than other methods and can easily form a film over a large area.
［２．２． 熱処理工程］
次に、被覆膜が形成された基板を熱処理する（熱処理工程）。これにより、本発明に係る電極板が得られる。
[2.2. Heat treatment process]
Next, the substrate on which the coating film is formed is heat treated (heat treatment step). Thereby, an electrode plate according to the present invention is obtained.
熱処理温度は、目的に応じて最適な条件を選択するのが好ましい。一般に、熱処理温度が低すぎると、高い結晶性を有する被覆膜は得られない。従って、熱処理温度は、５００℃以上が好ましい。熱処理温度は、好ましくは、６００℃以上、さらに好ましくは、６５０℃以上である。
一方、熱処理温度が高すぎると、基板がダメージを受け、強度が低下する場合がある。従って、熱処理温度は、８００℃以下が好ましい。熱処理温度は、好ましくは、７８０℃以下、さらに好ましくは、７４０℃以下である。
As for the heat treatment temperature, it is preferable to select optimal conditions depending on the purpose. Generally, if the heat treatment temperature is too low, a coating film with high crystallinity cannot be obtained. Therefore, the heat treatment temperature is preferably 500°C or higher. The heat treatment temperature is preferably 600°C or higher, more preferably 650°C or higher.
On the other hand, if the heat treatment temperature is too high, the substrate may be damaged and its strength may decrease. Therefore, the heat treatment temperature is preferably 800°C or lower. The heat treatment temperature is preferably 780°C or lower, more preferably 740°C or lower.
熱処理は、被覆膜の酸化を防ぐために、不活性雰囲気下において行うのが好ましい。
熱処理時間は、熱処理温度に応じて最適な時間を選択する。一般に、熱処理温度が高くなるほど、短時間で結晶化を進行させることができる。好適な熱処理時間は、熱処理温度にもよるが、通常、２時間～１０時間程度である。
The heat treatment is preferably performed under an inert atmosphere in order to prevent oxidation of the coating film.
The optimum heat treatment time is selected depending on the heat treatment temperature. Generally, the higher the heat treatment temperature, the faster crystallization can proceed. The suitable heat treatment time is usually about 2 hours to 10 hours, although it depends on the heat treatment temperature.
［３． 作用］
ある種のリン化物は、耐食性及び導電性に優れている。また、リン化物は、貴金属を含まないため、低コストである。さらに、リン化物からなる薄膜は、比較的低コストなスパッタ法により成膜することができる。そのため、リン化物からなる薄膜を電極板の被覆膜に適用すれば、耐食性及び導電性に優れ、しかも低コストな電極板を得ることができる。
さらに、一般に、成膜直後のリン化物薄膜は、結晶性が低い。これに対し、種々の方法により成膜されたリン化物薄膜を適切な条件下で熱処理すると、リン化物薄膜の結晶性が向上する。その結果、熱処理前に比べて導電性がさらに向上する。
[3. Effect]
Certain phosphides have excellent corrosion resistance and electrical conductivity. In addition, phosphides do not contain noble metals, so they are low cost. Furthermore, a thin film made of phosphide can be formed by a relatively low-cost sputtering method. Therefore, if a thin film made of phosphide is applied to the coating film of an electrode plate, an electrode plate with excellent corrosion resistance and conductivity and low cost can be obtained.
Furthermore, a phosphide thin film that has just been formed generally has low crystallinity. On the other hand, when a phosphide thin film formed by various methods is heat-treated under appropriate conditions, the crystallinity of the phosphide thin film is improved. As a result, the conductivity is further improved compared to before the heat treatment.
（実施例１、比較例１）
［１． 試料の作製］
［１．１． 比較例１］
スパッタ法により、Ｔｉ基板（０．１×１００×５０ｍｍ、（株）ニラコ製）の表面にリン化物からなる被覆膜を成膜した。ターゲットには、ＮｉＴｉＰを用いた。スパッタ時の雰囲気は、Ａｒ雰囲気とした。
(Example 1, Comparative Example 1)
[1. Preparation of sample]
[1.1. Comparative example 1]
A coating film made of phosphide was formed on the surface of a Ti substrate (0.1×100×50 mm, manufactured by Nilaco Co., Ltd.) by sputtering. NiTiP was used as a target. The atmosphere during sputtering was an Ar atmosphere.
［１．２． 実施例１］
比較例１と同様にして、ＮｉＴｉＰ薄膜を成膜した。その後、Ａｒ雰囲気中で７００℃で５時間熱処理した。
[1.2. Example 1]
A NiTiP thin film was formed in the same manner as in Comparative Example 1. Thereafter, heat treatment was performed at 700° C. for 5 hours in an Ar atmosphere.
［２． 試験方法］
［２．１． 耐食試験］
［２．１．１． 電圧印加］
ＮｉＴｉＰ薄膜が形成されたＴｉ基板を切断し、１ｃｍ×４ｃｍの試料を得た。１Ｌのセパラブルフラスコに０．０１Ｎ硫酸を８００ｍＬ入れた。これをマントルヒーターにセットし、８０℃まで加熱した。８０℃に保たれた硫酸に試料を浸漬し、試料に２．０Ｖの電圧を６時間印加した。
[2. Test method]
[2.1. Corrosion resistance test]
[2.1.1. Voltage application]
The Ti substrate on which the NiTiP thin film was formed was cut to obtain a 1 cm x 4 cm sample. 800 mL of 0.01N sulfuric acid was placed in a 1 L separable flask. This was set on a mantle heater and heated to 80°C. The sample was immersed in sulfuric acid maintained at 80° C., and a voltage of 2.0 V was applied to the sample for 6 hours.
［２．１．２． 抵抗測定］
電圧印加前後の抵抗変化を測定するために、ロードセルで試料に１ＭＰａ加圧した。この状態で試料面に垂直方向に０～０．５Ａの電流を流し、その時の電圧値を測定した。さらに、電圧値から接触抵抗を算出した。
[2.1.2. Resistance measurement]
In order to measure the change in resistance before and after voltage application, a pressure of 1 MPa was applied to the sample using a load cell. In this state, a current of 0 to 0.5 A was applied in a direction perpendicular to the sample surface, and the voltage value at that time was measured. Furthermore, contact resistance was calculated from the voltage value.
［２．３． ＸＲＤスペクトルの測定］
ＮｉＴｉＰ薄膜が形成されたＴｉ基板について、ＸＲＤスペクトルを測定した。得られたＸＲＤスペクトルから、最強線ピークの半値全幅を求めた。
[2.3. Measurement of XRD spectrum]
The XRD spectrum was measured for the Ti substrate on which the NiTiP thin film was formed. From the obtained XRD spectrum, the full width at half maximum of the strongest line peak was determined.
［３． 結果］
［３．１． 耐食試験］
比較例１の場合、耐食試験前（電圧印加前）の接触抵抗は１５ｍΩｃｍ2であったのに対し、耐食試験後（電圧印加後）の接触抵抗は２８ｍΩｃｍ2であった。
一方、実施例１の場合、耐食試験前（電圧印加前）の接触抵抗、及び、耐食試験後（電圧印加後）の接触抵抗は、いずれも、５ｍΩｃｍ2であった。
[3. result]
[3.1. Corrosion resistance test]
In the case of Comparative Example 1, the contact resistance before the corrosion resistance test (before voltage application) was 15 mΩcm 2 , whereas the contact resistance after the corrosion resistance test (after voltage application) was 28 mΩcm 2 .
On the other hand, in the case of Example 1, the contact resistance before the corrosion resistance test (before voltage application) and the contact resistance after the corrosion resistance test (after voltage application) were both 5 mΩcm 2 .
［３．２． ＸＲＤスペクトル］
図１に、熱処理前（比較例１）及び熱処理後（実施例１）の被覆膜の耐食試験前及び耐食試験後のＸＲＤスペクトルを示す。比較例１の場合、ＮｉＴｉＰに由来する回折ピークが認められなかった。一方、実施例１の場合、２θが４６°付近、５１°付近、及び６７°付近に、明瞭な回折ピークが認められた。また、電圧印加前後でＸＲＤスペクトルの著しい変化はなく、ＮｉＴｉＰ薄膜が耐食性に優れていることが分かった。実施例１の場合、耐食試験前の最強線ピークの半値全幅は、０．３５°であった。
[3.2. XRD spectrum]
FIG. 1 shows XRD spectra before and after the corrosion resistance test of the coating film before heat treatment (Comparative Example 1) and after heat treatment (Example 1). In the case of Comparative Example 1, no diffraction peak derived from NiTiP was observed. On the other hand, in the case of Example 1, clear diffraction peaks were observed around 2θ of 46°, 51°, and 67°. Furthermore, there was no significant change in the XRD spectrum before and after voltage application, indicating that the NiTiP thin film has excellent corrosion resistance. In the case of Example 1, the full width at half maximum of the strongest line peak before the corrosion resistance test was 0.35°.
（実施例２～５）
［１． 試料の作製］
ターゲットとして、ＣｏＴｉＰ（実施例２）、ＦｅＴｉＰ（実施例３）、ＭｎＴｉＰ（実施例４）、又はＣｒＴｉＰ（実施例５）を用いた以外は、実施例１と同様にして、被覆膜の成膜及び熱処理を行った。
［２． 試験方法］
実施例１と同様にして耐食試験を行い、耐食試験後の接触抵抗、及び、耐食試験前の最強線ピークの半値全幅を測定した。
(Examples 2 to 5)
[1. Preparation of sample]
The coating film was formed in the same manner as in Example 1, except that CoTiP (Example 2), FeTiP (Example 3), MnTiP (Example 4), or CrTiP (Example 5) was used as the target. Film and heat treatment were performed.
[2. Test method]
A corrosion resistance test was conducted in the same manner as in Example 1, and the contact resistance after the corrosion resistance test and the full width at half maximum of the strongest line peak before the corrosion resistance test were measured.
［３． 結果］
図２に、耐食試験後の接触抵抗を示す。また、表１に、耐食試験後の接触抵抗、及び、最強線ピークの半値全幅を示す。なお、図１及び表１には、実施例１（ＮｉＴｉＰ）の結果も併せて示した。
[3. result]
FIG. 2 shows the contact resistance after the corrosion resistance test. Further, Table 1 shows the contact resistance after the corrosion resistance test and the full width at half maximum of the strongest line peak. Note that FIG. 1 and Table 1 also show the results of Example 1 (NiTiP).
ＣｏＴｉＰ（実施例２）、ＦｅＴｉＰ（実施例３）、ＭｎＴｉＰ（実施例４）、及び、ＣｒＴｉＰ（実施例５）の接触抵抗は、いずれも１０ｍΩｃｍ2以下であり、良好な導電性を示すことが分かった。
また、ＣｏＴｉＰ（実施例２）、ＦｅＴｉＰ（実施例３）、ＭｎＴｉＰ（実施例４）、及び、ＣｒＴｉＰ（実施例５）の耐食試験前の最強線ピークの半値全幅は、いずれも０．６０°以下であり、高い結晶性を示すことが分かった。
The contact resistances of CoTiP (Example 2), FeTiP (Example 3), MnTiP (Example 4), and CrTiP (Example 5) were all 10 mΩcm 2 or less, indicating good conductivity. Do you get it.
Furthermore, the full width at half maximum of the strongest line peak of CoTiP (Example 2), FeTiP (Example 3), MnTiP (Example 4), and CrTiP (Example 5) before the corrosion resistance test was all 0.60°. It was found that the crystallinity was as follows, indicating high crystallinity.
（実施例６～９）
［１． 試料の作製］
ターゲットとして、Ｎｉ0.5Ｃｏ0.5ＴｉＰ（実施例６）、Ｃｏ0.5Ｆｅ0.5ＴｉＰ（実施例７）、Ｆｅ0.5Ｍｎ0.5ＴｉＰ（実施例８）、又はＭｎ0.5Ｃｒ0.5ＴｉＰ（実施例９）を用いた以外は、実施例１と同様にして、被覆膜の成膜及び熱処理を行った。
［２． 試験方法］
実施例１と同様にして耐食試験を行い、耐食試験後の接触抵抗、及び、耐食試験前の最強線ピークの半値全幅を測定した。
(Examples 6 to 9)
[1. Preparation of sample]
As a target, Ni 0.5 Co 0.5 TiP (Example 6), Co 0.5 Fe 0.5 TiP (Example 7), Fe 0.5 Mn 0.5 TiP (Example 8), or Mn 0.5 Cr 0.5 TiP (Example 9) was used. Except for this, the coating film was formed and the heat treatment was performed in the same manner as in Example 1.
[2. Test method]
A corrosion resistance test was conducted in the same manner as in Example 1, and the contact resistance after the corrosion resistance test and the full width at half maximum of the strongest line peak before the corrosion resistance test were measured.
［３． 結果］
図３に、Ｔｉ基板の表面にＮｉ1-yＣｏyＴｉＰ（０≦ｙ≦１）からなる被覆膜が形成された試料の耐食試験後の接触抵抗を示す。図４に、Ｔｉ基板の表面にＣｏ1-yＦｅyＴｉＰ（０≦ｙ≦１）からなる被覆膜が形成された試料の耐食試験後の接触抵抗を示す。図５に、Ｔｉ基板の表面にＦｅ1-yＭｎyＴｉＰ（０≦ｙ≦１）からなる被覆膜が形成された試料の耐食試験後の接触抵抗を示す。図６に、Ｔｉ基板の表面にＭｎ1-yＣｒyＴｉＰ（０≦ｙ≦１）からなる被覆膜が形成された試料の耐食試験後の接触抵抗を示す。なお、図３～６には、端成分（実施例１～５）の結果も併せて示した。
また、表２に、耐食試験後の接触抵抗、及び、耐食試験前の最強線ピークの半値全幅を示す。
[3. result]
FIG. 3 shows the contact resistance after a corrosion resistance test of a sample in which a coating film made of Ni 1-y Co y TiP (0≦y≦1) was formed on the surface of a Ti substrate. FIG. 4 shows the contact resistance after a corrosion resistance test of a sample in which a coating film made of Co 1-y Fe y TiP (0≦y≦1) was formed on the surface of a Ti substrate. FIG. 5 shows the contact resistance after a corrosion resistance test of a sample in which a coating film made of Fe 1-y Mny TiP (0≦y≦1) was formed on the surface of a Ti substrate. FIG. 6 shows the contact resistance after a corrosion resistance test of a sample in which a coating film made of Mn 1-y Cr y TiP (0≦y≦1) was formed on the surface of a Ti substrate. Note that FIGS. 3 to 6 also show the results of end components (Examples 1 to 5).
Further, Table 2 shows the contact resistance after the corrosion resistance test and the full width at half maximum of the strongest line peak before the corrosion resistance test.
２種類の金属元素Ｍを含む被覆膜の接触抵抗は、いずれも、端成分のほぼ中間の値を示した。また、Ｎｉ0.5Ｃｏ0.5ＴｉＰ（実施例６）、Ｃｏ0.5Ｆｅ0.5ＴｉＰ（実施例７）、Ｆｅ0.5Ｍｎ0.5ＴｉＰ（実施例８）、及び、Ｍｎ0.5Ｃｒ0.5ＴｉＰ（実施例９）の接触抵抗は、いずれも１０ｍΩｃｍ2以下であり、良好な導電性を示すことが分かった。
また、Ｎｉ0.5Ｃｏ0.5ＴｉＰ（実施例６）、Ｃｏ0.5Ｆｅ0.5ＴｉＰ（実施例７）、Ｆｅ0.5Ｍｎ0.5ＴｉＰ（実施例８）、及び、Ｍｎ0.5Ｃｒ0.5ＴｉＰ（実施例９）の耐食試験前の最強線ピークの半値全幅は、いずれも０．６０°以下であり、高い結晶性を示すことが分かった。
The contact resistances of the coating films containing two types of metal elements M all showed values approximately intermediate between the end components. In addition, the contact resistance of Ni 0.5 Co 0.5 TiP (Example 6), Co 0.5 Fe 0.5 TiP (Example 7), Fe 0.5 Mn 0.5 TiP (Example 8), and Mn 0.5 Cr 0.5 TiP (Example 9) was 10 mΩcm 2 or less in all cases, indicating good conductivity.
In addition, corrosion resistance tests were conducted on Ni 0.5 Co 0.5 TiP (Example 6), Co 0.5 Fe 0.5 TiP (Example 7), Fe 0.5 Mn 0.5 TiP (Example 8), and Mn 0.5 Cr 0.5 TiP (Example 9). The full width at half maximum of the previous strongest line peak was all 0.60° or less, indicating high crystallinity.
（比較例１～６）
［１． 試料の作製］
ターゲットとして、ＮｉＰ（比較例１）、ＣｏＰ（比較例２）、ＦｅＰ（比較例３）、ＭｎＰ（比較例４）、ＣｒＰ（比較例５）、又はＴｉＰ（比較例６）を用いた以外は、実施例１と同様にして、被覆膜の成膜及び熱処理を行った。
［２． 試験方法］
実施例１と同様にして耐食試験を行い、耐食試験後の接触抵抗、及び、耐食試験前の最強線ピークの半値全幅を測定した。
(Comparative Examples 1 to 6)
[1. Preparation of sample]
Except that NiP (Comparative Example 1), CoP (Comparative Example 2), FeP (Comparative Example 3), MnP (Comparative Example 4), CrP (Comparative Example 5), or TiP (Comparative Example 6) was used as the target. The coating film was formed and heat treated in the same manner as in Example 1.
[2. Test method]
A corrosion resistance test was conducted in the same manner as in Example 1, and the contact resistance after the corrosion resistance test and the full width at half maximum of the strongest line peak before the corrosion resistance test were measured.
［３． 結果］
図７～図１１に、Ｔｉ基板の表面に、ＮｉＰ、ＣｏＰ、ＦｅＰ、ＭｎＰ、ＣｒＰ、又はＴｉＰからなる被膜が形成された試料の耐食試験後の接触抵抗を示す。図７～図１１には、ＮｉＴｉＰ、ＣｏＴｉＰ、ＦｅＴｉＰ、ＭｎＴｉＰ、及びＣｒＴｉＰの結果も併せて示した。また、表３に、耐食試験後の接触抵抗、及び、耐食試験前の最強線ピークの半値全幅を示す。
[3. result]
7 to 11 show the contact resistance after a corrosion resistance test of samples in which a film made of NiP, CoP, FeP, MnP, CrP, or TiP was formed on the surface of a Ti substrate. 7 to 11 also show the results for NiTiP, CoTiP, FeTiP, MnTiP, and CrTiP. Further, Table 3 shows the contact resistance after the corrosion resistance test and the full width at half maximum of the strongest line peak before the corrosion resistance test.
図７～図１１より、Ｔｉ及び金属元素Ｍを含むリン化物の接触抵抗は、１種類の金属元素を含むリン化物のそれより小さいことが分かる。
ＮｉＰ（比較例１）、ＣｏＰ（比較例２）、ＦｅＰ（比較例３）、ＭｎＰ（比較例４）、ＣｒＰ（比較例５）、及び、ＴｉＰ（比較例６）の耐食試験前の最強線ピークの半値全幅は、いずれも０．６°以下であった。しかしながら、これらの接触抵抗は、いずれも１０ｍΩｃｍ2を超えていた。
From FIGS. 7 to 11, it can be seen that the contact resistance of the phosphide containing Ti and the metal element M is smaller than that of the phosphide containing one type of metal element.
Strongest line before corrosion resistance test of NiP (Comparative Example 1), CoP (Comparative Example 2), FeP (Comparative Example 3), MnP (Comparative Example 4), CrP (Comparative Example 5), and TiP (Comparative Example 6) The full width at half maximum of each peak was 0.6° or less. However, all of these contact resistances exceeded 10 mΩcm 2 .
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.
本発明に係る電極板は、固体高分子形燃料電池用セパレータ、固体高分子形（ＰＥＭ）水電解装置用バイポーラプレートなどに使用することができる。 The electrode plate according to the present invention can be used as a separator for a polymer electrolyte fuel cell, a bipolar plate for a polymer electrolyte (PEM) water electrolyzer, and the like.
Claims (8)
（１）前記電極板は、
基板と、
前記基板の表面の少なくとも一部に形成された被覆膜と
を備えている。
（２）前記被覆膜は、次の式（１）で表される組成を有するリン化物を含む。
Ｍ2-xＴｉxＰ …（１）
但し、
Ｍは、Ｎｉ、Ｃｏ、Ｆｅ、Ｍｎ、及びＣｒからなる群から選ばれるいずれか１以上の元素、
０．１≦ｘ≦１．９
（３）前記被覆膜は、ＸＲＤスペクトル測定を行った時に、前記リン化物の最強線ピークの半値全幅が０．６°以下であるものからなる。 Electrode plate with the following configuration.
(1) The electrode plate is
A substrate and
and a coating film formed on at least a portion of the surface of the substrate.
(2) The coating film contains a phosphide having a composition represented by the following formula (1).
M 2-x Ti x P…(1)
however,
M is any one or more elements selected from the group consisting of Ni, Co, Fe, Mn, and Cr;
0.1≦x≦1.9
(3) The coating film is such that the full width at half maximum of the strongest line peak of the phosphide is 0.6° or less when an XRD spectrum is measured.
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|---|---|---|---|---|
| JP2011009124A (en) | 2009-06-26 | 2011-01-13 | Toyota Central R&D Labs Inc | Conductive film, conductive material and its manufacturing method, solid polymer fuel cell, its separator, conductive powder, and its manufacturing method |
| JP2014080668A (en) | 2012-10-18 | 2014-05-08 | Toyota Central R&D Labs Inc | Insoluble electrode material and insoluble electrode |
| JP2014082176A (en) | 2012-10-18 | 2014-05-08 | Toyota Central R&D Labs Inc | Corrosion resistant electroconductive material, corrosion resistant electroconductive film and corrosion resistant electroconductive member |
| JP2015132006A (en) | 2014-01-15 | 2015-07-23 | 株式会社豊田中央研究所 | crystalline electrode material and insoluble electrode |
| JP2019197667A (en) | 2018-05-10 | 2019-11-14 | 株式会社豊田中央研究所 | Bipolar plate |
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| JP2011009124A (en) | 2009-06-26 | 2011-01-13 | Toyota Central R&D Labs Inc | Conductive film, conductive material and its manufacturing method, solid polymer fuel cell, its separator, conductive powder, and its manufacturing method |
| JP2014080668A (en) | 2012-10-18 | 2014-05-08 | Toyota Central R&D Labs Inc | Insoluble electrode material and insoluble electrode |
| JP2014082176A (en) | 2012-10-18 | 2014-05-08 | Toyota Central R&D Labs Inc | Corrosion resistant electroconductive material, corrosion resistant electroconductive film and corrosion resistant electroconductive member |
| JP2015132006A (en) | 2014-01-15 | 2015-07-23 | 株式会社豊田中央研究所 | crystalline electrode material and insoluble electrode |
| JP2019197667A (en) | 2018-05-10 | 2019-11-14 | 株式会社豊田中央研究所 | Bipolar plate |
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