JP2013117041A - Soluble electrode catalyst - Google Patents
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- JP2013117041A JP2013117041A JP2011264026A JP2011264026A JP2013117041A JP 2013117041 A JP2013117041 A JP 2013117041A JP 2011264026 A JP2011264026 A JP 2011264026A JP 2011264026 A JP2011264026 A JP 2011264026A JP 2013117041 A JP2013117041 A JP 2013117041A
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- 239000002184 metal Substances 0.000 claims abstract description 114
- 238000003411 electrode reaction Methods 0.000 claims abstract description 93
- 230000003197 catalytic effect Effects 0.000 claims abstract description 22
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- 239000001257 hydrogen Substances 0.000 claims description 21
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- 230000008859 change Effects 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
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- 239000007868 Raney catalyst Substances 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
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- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
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- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 239000003011 anion exchange membrane Substances 0.000 description 1
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- 229910001882 dioxygen Inorganic materials 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
本発明は、電解液中で行う電極反応用の電極に関し、特に触媒活性を長期間維持可能な活性電極に関する。 The present invention relates to an electrode for electrode reaction performed in an electrolytic solution, and more particularly to an active electrode capable of maintaining catalytic activity for a long period of time.
電気化学反応は、電気エネルギーと化学エネルギーとの相互変換である。電気分解は電気エネルギーを消費して化学変化を起こすプロセスであり、電池は化学変化から電気エネルギーを得る装置である。前者は従来から工業的規模での応用が極めて盛んであり、エネルギー原単位の低減を追求して精力的な研究が行われてきた。また後者についても近年のエネルギー効率向上への要求から、燃料電池を発電システムとして利用しようとする動きが盛んになりつつある。 An electrochemical reaction is an interconversion between electrical energy and chemical energy. Electrolysis is a process that consumes electrical energy to cause a chemical change, and a battery is a device that obtains electrical energy from a chemical change. The former has been very popular on an industrial scale and has been energetically studied in pursuit of reducing energy intensity. As for the latter, there is a growing trend to use fuel cells as a power generation system due to recent demands for improving energy efficiency.
電気分解、燃料電池のいずれについても、最大の関心事はエネルギー効率の向上と装置コストの低減である。例えば電気分解のエネルギー効率は電極反応の過電圧の値に大きく依存するため、電極反応の過電圧を下げるために反応に応じて種々の電極触媒及びその担持方法が研究されてきた。例えば食塩水の電気分解による水酸化ナトリウム製造プロセス等における陰極（カソード）での水素発生反応には、白金やパラジウム等が良好な触媒活性を示すことが旧来周知であるが、このような希少性の高い元素の使用は装置コストを大幅に押し上げる要因となる。そのため、より安価な触媒金属としてニッケルやコバルトが広く用いられている。例えば特許文献１には、耐食性の基材表面に、ニッケル、コバルト等から選ばれた触媒活性を有する金属からなる粉末を溶射被覆してなる水素発生用電極が開示されている。また、特許文献２には、ラネーニッケルの連続表面層で導電性基材が被覆されてなる多孔性の水素発生用電極が開示されている。 For both electrolysis and fuel cells, the biggest concerns are improving energy efficiency and reducing equipment costs. For example, since the energy efficiency of electrolysis greatly depends on the value of the overvoltage of the electrode reaction, various electrode catalysts and their loading methods have been studied in accordance with the reaction in order to reduce the overvoltage of the electrode reaction. For example, it has been well known that platinum, palladium, etc. show good catalytic activity in the hydrogen generation reaction at the cathode in the sodium hydroxide production process by electrolysis of saline solution. The use of a high element causes a significant increase in equipment cost. Therefore, nickel and cobalt are widely used as cheaper catalyst metals. For example, Patent Document 1 discloses a hydrogen generating electrode obtained by spray coating a powder made of a metal having catalytic activity selected from nickel, cobalt and the like on the surface of a corrosion-resistant substrate. Patent Document 2 discloses a porous electrode for hydrogen generation in which a conductive base material is coated with a continuous surface layer of Raney nickel.
しかしながら、触媒は一般に、使用に伴って触媒活性が低下する、ないしは失活するという問題を有している。特許文献２に記載のラネーニッケル等のラネー型の触媒は比較的耐蝕性を有する触媒金属と耐蝕性の低い他の金属との合金から当該他の金属を溶出させることにより製造され、表面積が大である結果として高い触媒活性（過電圧低減効果）を示すことで知られているが、このように形状を工夫してみても触媒活性は使用時間の累積に従って単調に低下することを免れない。触媒活性の低下した電極触媒は通常電極ごと交換されるため、電極触媒の長寿命化は省資源化及び装置コスト低減の観点から極めて重要である。 However, the catalyst generally has a problem that the catalyst activity decreases or deactivates with use. A Raney-type catalyst such as Raney nickel described in Patent Document 2 is manufactured by eluting the other metal from an alloy of a catalyst metal having relatively corrosion resistance and another metal having low corrosion resistance, and has a large surface area. As a result, it is known to show a high catalytic activity (overvoltage reduction effect). However, even if the shape is devised in this way, the catalytic activity is inevitably lowered monotonically as the usage time accumulates. Since the electrode catalyst with reduced catalytic activity is usually replaced with the electrode, extending the life of the electrode catalyst is extremely important from the viewpoints of resource saving and device cost reduction.
また、燃料電池として従来から盛んに研究されているものは、イオン交換膜としてカチオン交換膜を使用するカチオン交換型燃料電池である。カチオン交換型燃料電池においては系が強酸性条件下にあるため、電極触媒としては耐蝕性に優れる白金が専ら使用されてきた。しかし上述の通り白金は高価であり、燃料電池の普及を妨げる要因となっている。一方、イオン交換膜としてアニオン交換膜を用いるアニオン交換型燃料電池においては、系が塩基性条件下にあるため白金以外の安価な金属を触媒として使用することが可能である。最近になって、ニッケルやコバルト系の電極触媒を採用して従来のカチオン交換型水素燃料電池に匹敵する出力密度を発揮するアニオン交換型燃料電池が提案されており、アニオン交換型燃料電池に対する期待が高まっている。このような燃料電池においても、電極触媒の触媒活性を長期間にわたって高く維持することが上記同様に重要であることは言うまでもない。 Further, what has been actively studied as a fuel cell is a cation exchange type fuel cell that uses a cation exchange membrane as an ion exchange membrane. In the cation exchange fuel cell, since the system is under a strongly acidic condition, platinum having excellent corrosion resistance has been exclusively used as an electrode catalyst. However, as described above, platinum is expensive and is a factor that hinders the spread of fuel cells. On the other hand, in an anion exchange type fuel cell using an anion exchange membrane as an ion exchange membrane, since the system is under basic conditions, it is possible to use an inexpensive metal other than platinum as a catalyst. Recently, an anion exchange fuel cell has been proposed that employs nickel or cobalt based electrode catalysts and exhibits output density comparable to conventional cation exchange hydrogen fuel cells. Expectations for anion exchange fuel cells Is growing. In such a fuel cell, it goes without saying that maintaining the catalytic activity of the electrode catalyst high over a long period of time is as important as described above.
そこで本発明は、電極反応に対する触媒活性を長期間にわたって維持できる、電極反応用電極を提供することを課題とする。 Then, this invention makes it a subject to provide the electrode for electrode reactions which can maintain the catalyst activity with respect to an electrode reaction over a long period of time.
本発明は、電解液の存在下に行われる電極反応に用いる電極であって、該電極は、第１の金属群から選ばれる１種以上の金属元素と、第２の金属群から選ばれる１種以上の金属元素とを含み、第１の金属群は、上記電極反応に対する触媒活性を有し、かつ上記電極反応の条件下では電解液に溶解しない１種以上の金属元素からなる群であり、第２の金属群は、上記電極反応の条件下で上記電極反応の進行に伴って電解液に溶解する１種以上の金属元素からなる群であり、上記電極反応の進行に伴って比表面積が増大することを特徴とする電極反応用電極により、上記課題を解決する。 The present invention is an electrode used for an electrode reaction performed in the presence of an electrolytic solution, and the electrode is one or more metal elements selected from the first metal group and 1 selected from the second metal group. The first metal group is a group consisting of one or more metal elements that have catalytic activity for the electrode reaction and do not dissolve in the electrolyte under the conditions of the electrode reaction. The second metal group is a group consisting of one or more metal elements that dissolve in the electrolytic solution as the electrode reaction proceeds under the conditions of the electrode reaction, and has a specific surface area as the electrode reaction proceeds. The above-mentioned problem is solved by an electrode for electrode reaction characterized by an increase of
ここで本発明において「電解液」とは、溶媒と該溶媒に溶解した電解質とを含んでなり電気伝導性を有する液体を意味する。ただし溶媒は水に限られない。ある金属がある電極反応に対して「触媒活性を有する」とは、電気化学反応における電解液中の対象電解物質を電解した際の過電圧を少なくし、必要な電極電位を理論分解電圧（平衡電極電位）に近づける作用を有することを意味し、具体的には当該触媒金属を用いる条件下において、当該金属を当該電極反応の作用極として用いたときの過電圧が、同一条件下で一般構造用圧延鋼材（ＳＳ材）を当該電極反応の作用極として用いたときの過電圧よりも低いことを意味する。第１の金属群について、ある金属が「電極反応の条件下では電解液に溶解しない」とは、当該電極反応が電解反応である場合には当該電解反応、当該電極反応が電池反応である場合には当該電池反応の逆反応である電極反応において、当該金属を当該電極反応の作用極として用いた場合に少なくとも該作用極に印加する過電圧の絶対値が０Ｖ以上０．２Ｖ以下である範囲内では当該金属が酸化溶出しないことを意味する。ある金属が「電極反応の進行に伴って電解液に溶解する」とは、本発明の上記電極反応用電極の外表面に当該金属元素が存在しているときに、少なくとも当該電極反応が進行している限りは当該金属元素が当該電解液中に溶解する反応が進行することを意味する。また、「比表面積」とは、ＢＥＴ法で測定される比表面積を意味する。 Here, in the present invention, the “electrolytic solution” means a liquid having an electrical conductivity comprising a solvent and an electrolyte dissolved in the solvent. However, the solvent is not limited to water. “Metal having catalytic activity” for a certain electrode reaction means that the overvoltage when the target electrolyte in the electrolyte in the electrochemical reaction is electrolyzed is reduced, and the required electrode potential is the theoretical decomposition voltage (balanced electrode). In particular, under the conditions using the catalytic metal, the overvoltage when the metal is used as the working electrode for the electrode reaction is the same as that for the general structural rolling. It means that it is lower than the overvoltage when a steel material (SS material) is used as a working electrode for the electrode reaction. Regarding the first metal group, a certain metal “does not dissolve in the electrolyte under the conditions of electrode reaction” means that the electrode reaction is an electrolytic reaction, the electrolytic reaction, and the electrode reaction is a battery reaction. In the electrode reaction that is the reverse reaction of the battery reaction, when the metal is used as the working electrode of the electrode reaction, at least the absolute value of the overvoltage applied to the working electrode is in the range of 0 V or more and 0.2 V or less. Means that the metal does not oxidize and elute. A certain metal “dissolves in the electrolyte as the electrode reaction proceeds” means that at least the electrode reaction proceeds when the metal element is present on the outer surface of the electrode reaction electrode of the present invention. As long as it is, it means that the reaction in which the metal element is dissolved in the electrolytic solution proceeds. “Specific surface area” means a specific surface area measured by the BET method.
本発明の電極反応用電極は、導電性の芯部と該芯部を取り囲む外層部とから形成されており、外層部が、上記第１の金属群から選ばれる１種以上の金属元素と上記第２の金属群から選ばれる１種以上の金属元素とを含む合金相を有することが好ましい。かかる形態においては、外層部を構成する合金相の少なくとも一部が導電性の芯部の上に電析によって形成されたものであることがより好ましく、さらには当該電析が、導電性の芯部表面におけるメッキ液の電析浴線速度が０．００１ｃｍ／秒以上２０ｃｍ／秒以下となる条件にて行われたものであることが好ましい。 The electrode for electrode reaction of the present invention is formed of a conductive core part and an outer layer part surrounding the core part, and the outer layer part is one or more metal elements selected from the first metal group and the above. It is preferable to have an alloy phase containing one or more metal elements selected from the second metal group. In such a form, it is more preferable that at least a part of the alloy phase constituting the outer layer portion is formed on the conductive core portion by electrodeposition, and further, the electrodeposition is performed on the conductive core. The electrodeposition bath linear velocity of the plating solution on the surface of the part is preferably performed under the condition of 0.001 cm / second or more and 20 cm / second or less.
本発明の電極反応用電極において、電極反応が、水の電気分解により水素を発生させる還元反応である場合には、第１の金属群は、Ｎｉ、Ｃｏ、Ｆｅ、Ｃｕ、Ａｕ、Ａｇ、Ｒｈ、Ｉｒ、Ｒｅ、Ｒｕ、Ｐｔ、Ｐｄ、Ｍｏ、Ｗ、Ｔｉ、Ｚｎ及びＴａからなる群であり、第２の金属群は、第１の金属群と合金形成が可能な金属からなる群である。 In the electrode for electrode reaction of the present invention, when the electrode reaction is a reduction reaction that generates hydrogen by electrolysis of water, the first metal group includes Ni, Co, Fe, Cu, Au, Ag, Rh. , Ir, Re, Ru, Pt, Pd, Mo, W, Ti, Zn, and Ta, and the second metal group is a group made of metal capable of forming an alloy with the first metal group. .
本発明の電極反応用電極は、水の電気分解により水素を発生させるための水素発生用陰極であって、ＮｉとＳｎとからなる外層部を有し、該外層部は、ＮｉとＳｎとの組成比の異なる層が交互に積層された構造を有することを特徴とする、水素発生用陰極とすることができる。 The electrode for electrode reaction of the present invention is a hydrogen generating cathode for generating hydrogen by electrolysis of water, and has an outer layer portion made of Ni and Sn, and the outer layer portion is made of Ni and Sn. It can be set as the cathode for hydrogen generation characterized by having the structure where the layer from which a composition ratio differs was laminated | stacked alternately.
本発明の電極反応用電極によれば、第２の金属群に属する金属元素が電極反応の進行に伴って電解液中に溶出することにより、触媒活性な第１の金属群に属する金属元素の新たな活性面が随時電極表面に露出するので、電極全体としての触媒活性度を長期間にわたって維持することが可能な電極反応用電極を提供することができる。 According to the electrode for electrode reaction of the present invention, the metal element belonging to the second metal group elutes into the electrolytic solution as the electrode reaction proceeds, so that the metal element belonging to the first metal group that is catalytically active Since a new active surface is exposed to the electrode surface as needed, it is possible to provide an electrode for electrode reaction that can maintain the catalytic activity of the entire electrode over a long period of time.
本発明の上記した作用および利得は、以下に説明する発明を実施するための形態から明らかにされる。以下、本発明の実施の形態について説明する。ただし、本発明はこれらの形態に限定されるものではない。なお、以下においては、特に断らない限り、数値Ａ、Ｂについて「Ａ〜Ｂ」とはＡ以上Ｂ以下を意味する。 The above-mentioned operation and gain of the present invention will be clarified from embodiments for carrying out the invention described below. Embodiments of the present invention will be described below. However, the present invention is not limited to these forms. In the following, “A to B” for numerical values A and B means A or more and B or less unless otherwise specified.
＜電極反応用電極＞
本発明の電極反応用電極は、電解液の存在下に行う電極反応用の電極であり、該電極反応に対して触媒能を有する。
<Electrode for electrode reaction>
The electrode for electrode reaction of the present invention is an electrode for electrode reaction performed in the presence of an electrolytic solution, and has catalytic ability for the electrode reaction.
（電極反応）
上述のように電極反応は、電気エネルギーを化学エネルギーに変換する電解反応（例えば塩化ナトリウム水溶液の電気分解等。）と、化学エネルギーを電気エネルギーに変換する電池反応（例えば燃料電池等。）とに大別される。そのそれぞれについて、外部回路から電子が流入する電極（カソード）における反応と、外部回路へ電子が流出する電極（アノード）における反応とにさらに大別される。本発明の電極反応用電極は、電解反応及び電池反応のいずれにも適用可能であり、また、カソード反応及びアノード反応のいずれにも適用可能である。ただし、第１の金属群に属する金属及び第２の金属群に属する金属として安価な卑金属を用いることが容易である観点からは、カソードにおける電解反応が特に好ましい。
(Electrode reaction)
As described above, the electrode reaction includes an electrolytic reaction (for example, electrolysis of a sodium chloride aqueous solution) that converts electrical energy into chemical energy, and a cell reaction (for example, a fuel cell) that converts chemical energy into electrical energy. Broadly divided. Each of these is further broadly divided into a reaction at the electrode (cathode) into which electrons flow from the external circuit and a reaction at the electrode (anode) from which electrons flow out to the external circuit. The electrode for electrode reaction of the present invention can be applied to both electrolytic reaction and battery reaction, and can be applied to both cathode reaction and anode reaction. However, the electrolytic reaction at the cathode is particularly preferable from the viewpoint that it is easy to use an inexpensive base metal as the metal belonging to the first metal group and the metal belonging to the second metal group.
（電解液）
電解液としては、当該電解反応を進行させることが可能な電解液を適宜採用できる。電解液を構成する溶媒は特に制限されるものではなく、水やメタノール、エタノール、アセトニトリル、ベンゾニトリル、塩化メチレン、テトラヒドロフラン、エチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、ジメチルエーテル、プロピレンカーボネート、１，２−ジメトキシエタン、ジメチルスルホキシド、ジメチルホルムアミド等の有機溶媒単体あるいは支持電解質を加えたもの等といった極性溶媒にイオン性物質が溶解した電気伝導性を有する溶液が適宜採用可能である。またイオン液体も使用できる。ただし、当該電解反応が水を電気分解する反応である場合（例えば、塩化ナトリウム水溶液の電気分解におけるカソード反応である場合等。）には通常水を溶媒とする。電解液の液性は特に制限されるものではなく、酸性（ｐＨ＜７）、中性（ｐＨ＝７）、塩基性（ｐＨ＞７）のいずれの液性を有する電解液であってもよい。ただし、電極反応がカソードにおける電解反応である場合には、電極に負電位が印加されるために電極の金属元素は一般に酸化溶出しにくくなるので、第２の金属群に属する金属元素は少なくなる傾向にあるところ、電解液の液性が塩基性であれば第２の金属として両性金属を採用することが可能になる。よって電極反応がカソードにおける電解反応である場合には、塩基性の電解液を好ましく採用することができる。なお、例えば水の電気分解による水素発生反応のように電極反応の進行に伴って液性が塩基性に傾く電極反応の場合、電解液の初期の液性は例えば塩化ナトリウム水溶液のように中性であってもよい。
(Electrolyte)
As the electrolytic solution, an electrolytic solution capable of causing the electrolytic reaction to proceed can be appropriately employed. The solvent constituting the electrolytic solution is not particularly limited, and water, methanol, ethanol, acetonitrile, benzonitrile, methylene chloride, tetrahydrofuran, ethylene carbonate, dimethyl carbonate, diethyl carbonate, dimethyl ether, propylene carbonate, 1,2-dimethoxy A solution having an electrical conductivity in which an ionic substance is dissolved in a polar solvent such as an organic solvent alone such as ethane, dimethyl sulfoxide, dimethylformamide or a support electrolyte can be appropriately employed. An ionic liquid can also be used. However, when the electrolytic reaction is a reaction for electrolyzing water (for example, a cathode reaction in the electrolysis of an aqueous sodium chloride solution), water is usually used as a solvent. The liquid property of the electrolytic solution is not particularly limited, and may be any electrolytic solution having any of acidic (pH <7), neutral (pH = 7), and basic (pH> 7). . However, when the electrode reaction is an electrolytic reaction at the cathode, a negative potential is applied to the electrode, so that the metal element of the electrode is generally difficult to oxidize and elute, so the number of metal elements belonging to the second metal group is reduced. When it exists in the tendency, if the liquidity of electrolyte solution is basic, it becomes possible to employ | adopt an amphoteric metal as a 2nd metal. Therefore, when the electrode reaction is an electrolytic reaction at the cathode, a basic electrolytic solution can be preferably employed. In addition, in the case of an electrode reaction in which the liquidity becomes basic as the electrode reaction proceeds, for example, a hydrogen generation reaction by electrolysis of water, the initial liquidity of the electrolyte is neutral, for example, an aqueous sodium chloride solution It may be.
（電極）
本実施形態の電極反応用電極は、電解液の存在下に行う電極反応に用いる電極であって、第１の金属群から選ばれる１種以上の金属元素と、第２の金属群から選ばれる１種以上の金属元素とを含み、電解反応の進行に伴って比表面積が増大する。図１は、ワイヤ型の形状を有する電極反応用電極１０の断面を模式的に表した図である。電極反応用電極１０は、導電性の芯部１と、該芯部を取り囲む外層部２とを有し、外層部２が、上記第１の金属群から選ばれる１種以上の金属元素と、上記第２の金属群から選ばれる１種以上の金属元素とを含む合金相を有する。このように芯部１と外層部２とを有する構造とすることにより、長期間の使用後においても電極の機械的強度を所定の強度以上に維持することが容易になる。
(electrode)
The electrode for electrode reaction of the present embodiment is an electrode used for an electrode reaction performed in the presence of an electrolytic solution, and is selected from one or more metal elements selected from the first metal group and the second metal group. One or more metal elements are included, and the specific surface area increases as the electrolytic reaction proceeds. FIG. 1 is a diagram schematically showing a cross section of an electrode reaction electrode 10 having a wire shape. The electrode for electrode reaction 10 has a conductive core portion 1 and an outer layer portion 2 surrounding the core portion, and the outer layer portion 2 includes at least one metal element selected from the first metal group, It has an alloy phase containing one or more metal elements selected from the second metal group. By adopting a structure having the core portion 1 and the outer layer portion 2 in this way, it becomes easy to maintain the mechanical strength of the electrode at a predetermined strength or higher even after long-term use.
（導電性の芯部）
導電性の芯部１はワイヤ型の形状を有する。導電性の芯部１を構成する材料としては、導電性を有する公知の材料を特に制限なく使用可能であり、外層部を構成する材料の一部又は全部と重複していてもよい。例えばＣｕやＮｉ等を好適に用いることができる。
(Conductive core)
The conductive core portion 1 has a wire shape. As a material constituting the conductive core portion 1, a known material having conductivity can be used without particular limitation, and may overlap with part or all of the material constituting the outer layer portion. For example, Cu, Ni, etc. can be used suitably.
（外層部）
外層部２は、導電性の芯部１を取り囲むように形成されており、第１の金属群から選ばれる１種以上の金属元素と、第２の金属群から選ばれる１種以上の金属元素とを含む合金相を有する。外層部２がこのような合金相を有することにより、第２の金属群に属する金属の溶出が進行するにつれて当該外層部に多孔質構造を形成させることができるので、電極の活性を維持することが一層容易になる。
(Outer layer)
The outer layer part 2 is formed so as to surround the conductive core part 1, and one or more metal elements selected from the first metal group and one or more metal elements selected from the second metal group And an alloy phase containing Since the outer layer part 2 has such an alloy phase, a porous structure can be formed in the outer layer part as the elution of the metal belonging to the second metal group proceeds, so that the activity of the electrode is maintained. Becomes easier.
（第１の金属群）
第１の金属群は、電極反応に対する触媒活性を有し、かつ当該電極反応の条件下では電解液に溶解しない１種以上の金属元素からなる群である。例えば電極反応が中性ないし塩基性の電解質水溶液中における、
（酸化反応）：Ｈ２＋２ＯＨ−→２Ｈ２Ｏ＋２ｅ− （１）
又は
（還元反応）：２Ｈ２Ｏ＋２ｅ−→Ｈ２＋２ＯＨ− （２）
である場合に第１の金属群に属する金属元素としては、Ｎｉ、Ｃｏ、Ｆｅ、Ｃｕ、Ａｕ、Ａｇ、Ｒｈ、Ｉｒ、Ｒｅ、Ｒｕ、Ｐｔ、Ｐｄ、Ｍｏ、Ｗ、Ｔｉ、Ｚｎ及びＴａを好ましく例示することができる。これらの中では、触媒活性性能の観点からＮｉ、Ｐｔ、Ｒｕ、Ｃｏ、Ａｇがより好ましく、耐食性及び実用性、コスト面の観点からＮｉが特に好ましい。
(First metal group)
The first metal group is a group consisting of one or more metal elements that have catalytic activity for the electrode reaction and that do not dissolve in the electrolyte under the conditions of the electrode reaction. For example, in an aqueous electrolyte solution in which the electrode reaction is neutral or basic,
(Oxidation reaction): H 2 + 2OH − → 2H 2 O + 2e − (1)
Or (reduction reaction): 2H 2 O + 2e − → H 2 + 2OH − (2)
As the metal elements belonging to the first metal group, Ni, Co, Fe, Cu, Au, Ag, Rh, Ir, Re, Ru, Pt, Pd, Mo, W, Ti, Zn, and Ta are included. It can be illustrated preferably. Among these, Ni, Pt, Ru, Co, and Ag are more preferable from the viewpoint of catalytic activity performance, and Ni is particularly preferable from the viewpoint of corrosion resistance, practicality, and cost.
（第２の金属群）
第２の金属群は、電極反応の条件下で当該電極反応の進行に伴って電解液に溶解する１種以上の金属元素からなる群である。例えば電極反応が中性ないし塩基性の電解質水溶液中における、
（酸化反応）：Ｈ２＋２ＯＨ−→２Ｈ２Ｏ＋２ｅ− （１）
又は
（還元反応）：２Ｈ２Ｏ＋２ｅ−→Ｈ２＋２ＯＨ− （２）
である場合に第２の金属群に属する金属元素としては、第１の金属群に属する金属と合金形成が可能な金属を用いることができる。これら多くの金属の中で、両性金属であるＡｌ、Ｚｎ、Ｓｎ及びＰｂを好ましく例示することができる。これらの両性金属元素は、電極に負の電位を印加されていても、強い塩基性条件下（例えばｐＨが１４以上の水系電解液中。）では水酸化物イオンと錯イオンを形成して溶出できる。これらの両性金属の中では、毒性が比較的低い点でＡｌ、Ｚｎ、及びＳｎがより好ましく、塩基性条件下での溶出速度が遅いために長期にわたって電極の触媒活性を維持することが一層容易になる点でＳｎが特に好ましい。なお、電解液の溶媒が水以外の極性溶媒と水との混合溶媒である場合には、ＡｌやＺｎであっても塩基性条件下での溶出速度が遅くなるので、Ｓｎより安価なＡｌやＺｎが好ましく採用される場合もあり得る。
(Second metal group)
The second metal group is a group consisting of one or more metal elements that dissolve in the electrolytic solution as the electrode reaction proceeds under the conditions of the electrode reaction. For example, in an aqueous electrolyte solution in which the electrode reaction is neutral or basic,
(Oxidation reaction): H 2 + 2OH − → 2H 2 O + 2e − (1)
Or (reduction reaction): 2H 2 O + 2e − → H 2 + 2OH − (2)
In this case, as the metal element belonging to the second metal group, a metal capable of forming an alloy with the metal belonging to the first metal group can be used. Among these many metals, amphoteric metals such as Al, Zn, Sn and Pb can be preferably exemplified. These amphoteric metal elements elute by forming hydroxide ions and complex ions under strong basic conditions (for example, in an aqueous electrolyte having a pH of 14 or higher) even when a negative potential is applied to the electrodes. it can. Among these amphoteric metals, Al, Zn, and Sn are more preferred because of their relatively low toxicity, and it is easier to maintain the catalytic activity of the electrode over a long period due to the slow elution rate under basic conditions. In particular, Sn is particularly preferable. In addition, when the solvent of the electrolytic solution is a mixed solvent of a polar solvent other than water and water, the dissolution rate under basic conditions is slow even if Al or Zn is used. In some cases, Zn is preferably employed.
（合金相）
上記したように、外層部が有する合金相は、第１の金属群から選ばれる１種以上の金属元素と、第２の金属群から選ばれる１種以上の金属元素とを含む。このような合金相は、芯材を溶融金属に浸漬する方法や、無電解メッキ等の一般的な手法によっても形成することが可能ではあるが、電析により形成することが特に好ましい。なお、第１の金属群から選ばれる金属元素の水溶液中での還元電位と、第２の金属群から選ばれる金属元素の水溶液中での還元電位との差が比較的大きい場合（例えば、ＮｉとＳｎとの組み合わせの場合。）であっても、適切な錯化剤（例えば、ピロリン酸塩やアミノ酸等。）を加えることにより、錯形成が起きて還元電位の差が小さくなるので、両者を共電析させて合金相を形成することが可能になる。例えば、水の電気分解により水素を発生させるための水素発生用陰極の合金相として、第１の金属群に属する金属としてＮｉ、第２の金属群に属する金属としてＳｎを含む合金相を電析により形成する場合の好ましい条件としては、ＮｉＣｌ２０．００１ｍｏｌ／Ｌ〜０．５０ｍｏｌ／Ｌ、ＳｎＣｌ２０．００１ｍｏｌ／Ｌ〜０．５０ｍｏｌ／Ｌ、Ｋ４Ｐ２Ｏ７０．１０ｍｏｌ／Ｌ〜１．００ｍｏｌ／Ｌ、グリシン０．０５ｍｏｌ／Ｌ〜１．００ｍｏｌ／Ｌ、ｐＨ７．０〜１１．０の電析浴中、浴温度を２０℃〜９０℃、電流密度を０．１Ａ／ｄｍ２〜１００Ａ／ｄｍ２、導電性の芯部表面におけるメッキ液の電析浴線速度を０．００１ｃｍ／秒〜２０ｃｍ／秒に維持して０．０１〜１０．０時間電析させる条件を例示することができる。また、上記した電析条件は電析中に一定である必要はなく変動しても良い。また電流値を意図的に変動させる方法であるパルス法でも良い。
(Alloy phase)
As described above, the alloy phase of the outer layer portion includes one or more metal elements selected from the first metal group and one or more metal elements selected from the second metal group. Such an alloy phase can be formed by a general method such as a method of immersing the core material in a molten metal or electroless plating, but is particularly preferably formed by electrodeposition. In addition, when the difference between the reduction potential in the aqueous solution of the metal element selected from the first metal group and the reduction potential in the aqueous solution of the metal element selected from the second metal group is relatively large (for example, Ni In the case of a combination of Sn and Sn.), By adding an appropriate complexing agent (for example, pyrophosphate, amino acid, etc.), complex formation occurs and the reduction potential difference is reduced. Can be co-deposited to form an alloy phase. For example, as an alloy phase of a cathode for hydrogen generation for generating hydrogen by electrolysis of water, an alloy phase containing Ni as a metal belonging to the first metal group and Sn as a metal belonging to the second metal group is electrodeposited As preferable conditions in the case of forming by NiCl 2 0.001 mol / L to 0.50 mol / L, SnCl 2 0.001 mol / L to 0.50 mol / L, K 4 P 2 O 7 0.10 mol / L to In an electrodeposition bath of 1.00 mol / L, glycine 0.05 mol / L to 1.00 mol / L, pH 7.0 to 11.0, the bath temperature is 20 ° C. to 90 ° C., and the current density is 0.1 A / dm 2. -100 A / dm < 2 >, The conditions which make electrodeposition bath linear velocity of the plating solution in the surface of an electroconductive core part maintain at 0.001 cm / second-20 cm / second, and perform 0.01 to 10.0 hours of electrodeposition are illustrated. Can Kill. Further, the above-described electrodeposition conditions do not have to be constant during electrodeposition and may vary. Further, a pulse method that is a method of intentionally changing the current value may be used.
合金相を電析により形成することには、製造上の利点と性能上の利点とがある。製造上の利点は、電流密度や電析時間を調整することにより金属析出を容易に制御可能である点、並びに、厚い合金相を容易に形成可能な点である。性能上の利点は、電析中に生じる電極表面近傍における電析浴組成の微小な変動が合金相の組成及び／又は構造に反映されることにより、第２の金属群に属する金属元素が溶出しやすい部分と溶出しにくい部分とが混在する合金相を形成することが可能になるため、本発明の上記効果を奏することが一層容易になる点にある。本発明者らはその理由を次の機構によるものと推定している。すなわち：電解反応の進行に伴って第２の金属群に属する金属元素が合金相から溶出するところ、上記溶出しやすい部分から先に溶出して脆くなるので、当該脆くなった部分と比較的強度を維持している上記溶出しにくい部分とが混在することになる。電極反応用電極は使用中、電解液の流動等によって常に何らかの外力を受け、内部に応力を生じているのが通常であるところ、このように強度の異なる部分が混在することによって応力集中が起きて微小な欠損が起こり、細孔が成長する。このようにして細孔が成長することにより、第１の金属群に属する金属元素が存在する新たな触媒活性面が露出して電解液と直接接触を開始することが長期間にわたって継続して繰り返されるので、電極全体としての触媒活性が長期間にわたって維持されることになる。また、細孔が成長することにより電極表面は多孔質化し表面積が増大するので、反応サイトが増大する点でも有利である。このような性能上の利点を有する合金相を効率よく形成する観点からは、電析浴中の導電性の芯部表面におけるメッキ液の線速度を０．００１ｃｍ／秒〜２０ｃｍ／秒に維持することが好ましい。このような線速度の管理は、電析浴中のメッキ液を撹拌することでもよいが、ポンプ等を用いて一方向に循環させることにより好適に行うことができる。 Forming the alloy phase by electrodeposition has manufacturing advantages and performance advantages. The manufacturing advantage is that the metal deposition can be easily controlled by adjusting the current density and the electrodeposition time, and that a thick alloy phase can be easily formed. The performance advantage is that metal elements belonging to the second metal group are eluted by minute variations in the electrodeposition bath composition in the vicinity of the electrode surface occurring during electrodeposition being reflected in the composition and / or structure of the alloy phase. Since it is possible to form an alloy phase in which a portion that is easy to be dissolved and a portion that is difficult to elute are formed, the above-described effects of the present invention are further facilitated. The present inventors presume that the reason is due to the following mechanism. That is, as the metal element belonging to the second metal group elutes from the alloy phase with the progress of the electrolytic reaction, it elutes first from the part that tends to elute and becomes brittle. The above-described portion that is difficult to elute, which is maintained, is mixed. While the electrode for electrode reaction is usually subjected to some external force due to the flow of the electrolyte during use, stress is usually generated inside, and stress concentration occurs due to the mixture of parts with different strengths. Minute defects occur, and pores grow. As a result of the growth of the pores in this manner, a new catalytically active surface in which the metal element belonging to the first metal group is present is exposed and direct contact with the electrolyte solution is continuously repeated over a long period of time. Therefore, the catalytic activity of the entire electrode is maintained over a long period of time. Moreover, since the electrode surface becomes porous and the surface area is increased by the growth of the pores, it is advantageous in that the reaction sites are increased. From the viewpoint of efficiently forming an alloy phase having such performance advantages, the linear velocity of the plating solution on the surface of the conductive core in the electrodeposition bath is maintained at 0.001 cm / second to 20 cm / second. It is preferable. Such a linear velocity can be controlled by stirring the plating solution in the electrodeposition bath, but can be suitably performed by circulating it in one direction using a pump or the like.
上記のような、第２の金属群に属する金属元素が溶出しやすい部分と溶出しにくい部分とが混在する合金相の好ましい具体的態様としては、例えば第１の金属群に属する金属元素（例えばＮｉ等）と第２の金属群に属する金属元素（例えばＳｎ等）との組成比の異なる層が交互に積層された層状構造を挙げることができる。このような層状構造を形成する方法としては、上記のような電析が特に好適である。 As a preferable specific aspect of the alloy phase in which the portion where the metal element belonging to the second metal group easily elutes and the portion where it is difficult to elute is mixed as described above, for example, a metal element belonging to the first metal group (for example, Examples thereof include a layered structure in which layers having different composition ratios between Ni and the like and metal elements belonging to the second metal group (for example, Sn) are alternately stacked. Electrodeposition as described above is particularly suitable as a method for forming such a layered structure.
第１の金属群に属する金属元素の合金相における組成比率は、第１の金属群に属する全ての金属元素が当該合金相の全ての金属原子の中で占める割合として、５ａｔｏｍ％以上であることが好ましく、９５ａｔｏｍ％以下であることが好ましい。また、第２の金属群に属する金属元素の合金相における組成比率は、第２の金属群に属する全ての金属元素が当該合金相の全ての金属原子の中で占める割合として、５ａｔｏｍ％以上であることが好ましく、９５ａｔｏｍ％以下であることが好ましい。合金相中における第１の金属群に属する金属元素の組成比率及び第２の金属群に属する金属元素の組成比率を上記範囲内とすることにより、電極の触媒活性を長期間にわたって維持するという本発明の効果を奏することが容易になる。合金相を電析によって形成する場合には、例えば電析浴中の金属イオンの含有量比を適宜調整する等の手法により、所望の合金相組成を得ることが可能である。 The composition ratio of the metal element belonging to the first metal group in the alloy phase is 5 atom% or more as the ratio of all the metal elements belonging to the first metal group in all the metal atoms of the alloy phase. Is preferable, and it is preferable that it is 95 atom% or less. Further, the composition ratio of the metal element belonging to the second metal group in the alloy phase is 5 atom% or more as the ratio of all the metal elements belonging to the second metal group to all the metal atoms in the alloy phase. It is preferable that it is 95 atom% or less. The book of maintaining the catalytic activity of the electrode over a long period of time by setting the composition ratio of the metal element belonging to the first metal group and the composition ratio of the metal element belonging to the second metal group in the alloy phase within the above ranges. It becomes easy to produce the effects of the invention. When the alloy phase is formed by electrodeposition, a desired alloy phase composition can be obtained, for example, by appropriately adjusting the content ratio of metal ions in the electrodeposition bath.
本発明に関する上記説明では、ワイヤ型の形状を有する電極反応用電極１０を例示したが、本発明は当該形態に限定されない。電極反応用電極、及び、導電性の芯部の形状は特に制限されず、ワイヤ状、平板状等、電極反応用電極の形状として公知の形状を特に制限なく採用可能である。 In the above description regarding the present invention, the electrode reaction electrode 10 having a wire shape is illustrated, but the present invention is not limited to this form. The shape of the electrode reaction electrode and the conductive core is not particularly limited, and a known shape such as a wire shape or a flat plate shape can be employed without any particular limitation.
本発明に関する上記説明では、導電性の芯部と該芯部を取り囲む外層部とを有し、外層部が合金相を有する形態の電極反応用電極を例示したが、本発明は当該形態に限定されない。例えば、第１の金属群に属する金属元素と第２の金属群に属する金属元素とを含む合金粒子が導電性の芯部（例えば導電性のカーボン電極）表面に担持された形態とすることも可能である。 In the above description related to the present invention, the electrode for electrode reaction having a conductive core portion and an outer layer portion surrounding the core portion, and the outer layer portion having an alloy phase has been exemplified, but the present invention is limited to this mode. Not. For example, an alloy particle containing a metal element belonging to the first metal group and a metal element belonging to the second metal group may be supported on the surface of a conductive core (for example, a conductive carbon electrode). Is possible.
また、本発明に関する上記説明では、水の電気分解により水素を発生させるカソード電解反応用、又は、水素の酸化により電子を取り出すアノード電池反応用の電極を主に例示しつつ説明したが、本発明は当該形態に限定されない。例えば、酸素を還元して水酸化物イオンを発生させるカソード電池反応：
Ｏ２＋２Ｈ２Ｏ＋４ｅ−→４ＯＨ− （３）
用の電極である形態とすることも可能である。かかる電極反応用電極は、アニオン交換型燃料電池の酸素極用電極として好適に使用することができる。ただし、気液二相反応（例えば水素ガスや酸素ガスを用いる場合等。）の場合には、電極表面積が広い（例えば電極を多孔性とする等。）ことが好ましい。また、本発明の電極反応用電極が適用される電極反応は水素や酸素の酸化ないし還元を含む反応に限定されるものではなく、第１の金属群に属する金属元素が存在する種々の電極反応に対して適用可能である。
Further, in the above description of the present invention, the electrode for the cathode electrolysis reaction for generating hydrogen by electrolysis of water or the anode battery reaction for extracting electrons by oxidation of hydrogen has been mainly exemplified, but the present invention has been described. Is not limited to this form. For example, the cathode cell reaction that reduces oxygen to generate hydroxide ions:
O 2 + 2H 2 O + 4e − → 4OH − (3)
It is also possible to adopt a form that is an electrode for use. Such an electrode reaction electrode can be suitably used as an electrode for an oxygen electrode of an anion exchange type fuel cell. However, in the case of a gas-liquid two-phase reaction (for example, when hydrogen gas or oxygen gas is used), it is preferable that the electrode surface area is large (for example, the electrode is made porous, etc.). In addition, the electrode reaction to which the electrode reaction electrode of the present invention is applied is not limited to a reaction including oxidation or reduction of hydrogen or oxygen, but various electrode reactions in which a metal element belonging to the first metal group is present. Is applicable.
以下、実施例に基づき、本発明についてさらに詳述する。ただし本発明は下記実施例に限定されるものではない。 Hereinafter, based on an Example, this invention is further explained in full detail. However, the present invention is not limited to the following examples.
＜実施例＞
（水素発生用カソード電極の作製）
純ニッケル製金網（導電性芯材）を脱脂及びエッチング処理した後に、表１に示す電析浴および条件にて、当該ニッケル金網表面にＮｉとＳｎを定電流モードで共電析させることにより、食塩水の電解による水素発生用のカソード電極（陰極）を作製した。
<Example>
(Preparation of cathode electrode for hydrogen generation)
After degreasing and etching the pure nickel wire mesh (conductive core material), by co-depositing Ni and Sn in a constant current mode on the nickel wire mesh surface in the electrodeposition bath and conditions shown in Table 1, A cathode electrode (cathode) for generating hydrogen by electrolysis of saline was prepared.
（作製した電極の使用）
陽極としてチタン製の寸法安定電極（ＤＳＥ）、イオン交換膜としてナフィオンＮ２０１０（デュポン社製）を使用し、上記条件にて製作した水素発生用カソード電極を陰極として用い、これらを密着させたゼロギャップ方式の電解槽にて、平均濃度４．１ｍｏｌ／Ｌの塩化ナトリウム水溶液を平均電流密度４．３ｋＡ／ｍ２、平均温度８５℃の条件で約１０年間電解を行った。
(Use of prepared electrode)
Zero gap in which titanium dimensionally stable electrode (DSE) is used as the anode, Nafion N2010 (manufactured by DuPont) is used as the ion exchange membrane, and the cathode electrode for hydrogen generation produced under the above conditions is used as the cathode. In an electrolytic cell of the system, electrolysis was performed for about 10 years using a sodium chloride aqueous solution with an average concentration of 4.1 mol / L under the conditions of an average current density of 4.3 kA / m 2 and an average temperature of 85 ° C.
作製した使用前の電極、及び、使用した後の上記電極について、以下の評価を行った。 The following evaluation was performed about the produced electrode before use and the electrode after use.
（評価１：触媒活性維持能力）
同一の電解セル、陽極及びイオン交換膜を用いて同一量の電流を流すために必要なカソード電位を比較することにより、過電圧の変化を評価した。上記ゼロギャップ方式の電解槽にて温度８５．０℃の４．１０ｍｏｌ／Ｌ塩化ナトリウム水溶液に電流密度４．５ｋＡ／ｍ２で電流を流すのに必要なカソード電位は、使用前の電極では−１．２４０Ｖ、１０年間使用後の電極では−１．２５０Ｖであり、カソード過電圧はわずか１０ｍＶしか増大しなかった。この結果から、本発明の電極反応用電極によれば、長期間にわたる使用の後においても電極の触媒活性を維持できることが示された。
(Evaluation 1: Catalytic activity maintenance ability)
The change in overvoltage was evaluated by comparing the cathode potentials required to flow the same amount of current using the same electrolytic cell, anode and ion exchange membrane. The cathode potential required to flow a current at a current density of 4.5 kA / m 2 in a 4.10 mol / L sodium chloride aqueous solution at a temperature of 85.0 ° C. in the zero gap type electrolytic cell is − The electrode after 1.240 V, 10 years of use was -1.250 V, and the cathode overvoltage increased only 10 mV. This result shows that the electrode reaction electrode of the present invention can maintain the catalytic activity of the electrode even after long-term use.
（評価２：比表面積）
使用前及び使用後の電極について、ＢＥＴ法により比表面積を比較した。使用前の電極では０．０１ｍ２／ｇ未満であったが、使用後の電極では０．６７ｍ２／ｇまで増大しており、電極反応の進行に伴って比表面積が増大することが確かめられた。
(Evaluation 2: Specific surface area)
The specific surface areas of the electrodes before and after use were compared by the BET method. Although the prior use electrodes was less than 0.01 m 2 / g, the electrode after use has increased up to 0.67 m 2 / g, it is confirmed that the specific surface area with the progress of the electrode reaction is increased It was.
（評価３：細孔分布）
使用前及び使用後の電極について、ＢＪＨ法により窒素ガスの吸着側の吸着等温線から、細孔直径１０〜２０００Åの範囲に対応する累積細孔容積曲線を取得し、これを細孔直径で微分して細孔分布曲線を得た。なお、この細孔分布曲線は概ね、対応する細孔直径を有する細孔の表面積への寄与度を表すものと考えることができる。図２に両電極の累積細孔容積曲線を、図３に両電極の細孔分布曲線を示す。図２から、使用後の電極においては細孔容積が増大していることが判る。また図３から、使用前の電極には細孔はほとんど存在しないのに対して、使用後の電極では４０〜１００Å程度の径を有する細孔が成長して表面積の増大に寄与していることが読み取れる。
(Evaluation 3: Pore distribution)
For the electrode before and after use, a cumulative pore volume curve corresponding to a pore diameter range of 10 to 2000 mm is obtained from the adsorption isotherm on the nitrogen gas adsorption side by the BJH method, and this is differentiated by the pore diameter. Thus, a pore distribution curve was obtained. In addition, it can be considered that this pore distribution curve generally represents the degree of contribution to the surface area of pores having a corresponding pore diameter. FIG. 2 shows the cumulative pore volume curve of both electrodes, and FIG. 3 shows the pore distribution curve of both electrodes. From FIG. 2, it can be seen that the pore volume is increased in the electrode after use. From FIG. 3, the electrode before use has almost no pore, whereas the electrode after use has a growth of pores having a diameter of about 40 to 100 mm, contributing to an increase in surface area. Can be read.
（評価４：ＳＥＭ観察による断面形状）
使用前及び使用後の電極について、断面形状を走査電子顕微鏡（ＳＥＭ）による反射電子像で観察した。結果をそれぞれ図４（Ａ）及び図４（Ｂ）に示す。スケールバーは１０μｍを表す。いずれも中央の円形部分がＮｉ芯部であり、その周囲を取り囲む比較的白みの強い（明るい）部分がＮｉ／Ｓｎ合金相である。なお、図４（Ａ）及び（Ｂ）におけるＮｉ／Ｓｎ合金相のまわりの灰色の部分はＳＥＭ観察にあたって試料を保持するための樹脂の像であり、電極試料には何ら関係ない。図４（Ａ）と図４（Ｂ）との比較から、使用後の電極ではＳｎの溶出に伴うとみられる抜け落ちが起きていることがわかる。微小な欠損が多数起きることによりこのような抜け落ちに発展するものと推測される。
(Evaluation 4: Cross-sectional shape by SEM observation)
About the electrode before and after use, the cross-sectional shape was observed with the backscattered electron image by a scanning electron microscope (SEM). The results are shown in FIGS. 4 (A) and 4 (B), respectively. The scale bar represents 10 μm. In each case, the central circular portion is the Ni core portion, and the relatively white (bright) portion surrounding the periphery is the Ni / Sn alloy phase. 4A and 4B, the gray portion around the Ni / Sn alloy phase is an image of a resin for holding the sample in SEM observation, and has nothing to do with the electrode sample. From comparison between FIG. 4 (A) and FIG. 4 (B), it can be seen that in the electrode after use, a drop-off that seems to be accompanied by Sn elution occurs. It is presumed that such a dropout is caused by the occurrence of many minute defects.
（評価５：ＥＤＳ分析による断面細部の組成分布）
使用前及び使用後の電極について、断面の細部をＳＥＭにより反射電子検出モードで観察した。結果をそれぞれ図５（Ａ）及び（Ｂ）に示す。スケールバーは３μｍである。また、それぞれ画像中の６点について元素組成をエネルギー分散Ｘ線分光（ＥＤＳ）により分析した。反射電子検出モードで得られるＳＥＭ像においては、コントラストが高い（明るい）ほど、原子量の大きな（重い）元素が多い組成を有していることを意味する。すなわち２８Ｎｉ／５０Ｓｎ合金相においては、コントラストが高いほどＳｎの比が大きいことを意味している。図５（Ａ）から、使用前の電極の合金相は、Ｎｉ／Ｓｎの組成比の異なる層が交互に積層された構造を有していることが判る。図５（Ａ）中の「＋」字記号及びその下の００１〜００６の番号は、元素組成比の具体的な数値を測定した箇所を表す。測定箇所番号００２、００４、及び００６はコントラストが明るい部分であり、測定箇所番号００１、００２、及び００３はコントラストが比較的暗い部分である。それぞれの測定箇所について、番号と組成比の測定値を表２に示す。
(Evaluation 5: Composition distribution of cross-sectional details by EDS analysis)
About the electrode before use and after use, the detail of the cross section was observed by reflected electron detection mode by SEM. The results are shown in FIGS. 5 (A) and (B), respectively. The scale bar is 3 μm. In addition, the elemental composition of each of the six points in the image was analyzed by energy dispersive X-ray spectroscopy (EDS). In the SEM image obtained in the backscattered electron detection mode, the higher the contrast (brighter), the higher the atomic weight (heavy). That is, in the 28 Ni / 50 Sn alloy phase, the higher the contrast, the larger the Sn ratio. FIG. 5A shows that the alloy phase of the electrode before use has a structure in which layers having different Ni / Sn composition ratios are alternately stacked. The “+” character symbol in FIG. 5A and the numbers 001 to 006 below the symbol indicate the locations where specific numerical values of the elemental composition ratio were measured. Measurement location numbers 002, 004, and 006 are portions where the contrast is bright, and measurement location numbers 001, 002, and 003 are portions where the contrast is relatively dark. Table 2 shows the numbers and measured values of the composition ratio for each measurement location.
表２から、図５（Ａ）の合金相においては、層によって数ａｔｏｍ％程度の範囲でＮｉ／Ｓｎ組成比の変動がみられること、及び、Ｓｎの組成比率が比較的高い層と比較的低い層とが交互に積層された構造を有することが判る。 From Table 2, in the alloy phase of FIG. 5 (A), the Ni / Sn composition ratio fluctuates in the range of several atom% depending on the layer, and the layer having a relatively high Sn composition ratio It can be seen that it has a structure in which lower layers are alternately stacked.
図５（Ａ）と図５（Ｂ）との比較から、使用後の電極においてはＳＥＭ像中のコントラストが大幅に低下した（暗くなった）部分、すなわちＳｎの組成比率が大幅に低下した部分が存在することが判る。これは電極反応の進行に伴って、第２の金属群に属するＳｎが溶出したことを示すものである。さらに、図５（Ｂ）においては、コントラストが低下していないように見える部分が存在する。これはＳｎが溶出しやすい部分と溶出しにくい部分との両方が存在することを意味するものである。図５（Ｂ）中の「＋」字記号及びその下の００７〜０１２の番号は、元素組成比の具体的な数値を測定した箇所を表す。それぞれの測定箇所について、番号と組成比の測定値を表３に示す。測定箇所番号００８及び０１１はコントラストが明るい部分である。測定箇所番号００７及び０１０はコントラストが比較的暗い部分である。測定箇所番号００９及び０１２はコントラストが際立って暗い部分である。それぞれの測定箇所について、番号と組成比の測定値を表３に示す。 From the comparison between FIG. 5 (A) and FIG. 5 (B), in the electrode after use, the part in which the contrast in the SEM image was greatly reduced (darkened), that is, the part in which the composition ratio of Sn was greatly reduced. It can be seen that there exists. This indicates that Sn belonging to the second metal group was eluted with the progress of the electrode reaction. Further, in FIG. 5B, there is a portion where the contrast does not appear to decrease. This means that there are both a portion where Sn is easily eluted and a portion where it is difficult to elute. The “+” character symbol in FIG. 5B and the numbers 007 to 012 below the symbol indicate locations where specific numerical values of the elemental composition ratio were measured. Table 3 shows the numbers and the measured values of the composition ratio for each measurement location. Measurement location numbers 008 and 011 are bright contrast portions. Measurement location numbers 007 and 010 are portions where the contrast is relatively dark. Measurement location numbers 009 and 012 are dark portions where the contrast is conspicuous. Table 3 shows the numbers and the measured values of the composition ratio for each measurement location.
表３から、図５（Ｂ）でコントラストが際立って暗い箇所（測定箇所番号００９、００１２）では、使用前には４０％以上あったＳｎの組成比率が２０％程度にまで低下していることが判る。 From Table 3, the composition ratio of Sn, which was 40% or more before use, has been reduced to about 20% in a dark place (measurement place numbers 009, 0012) in FIG. I understand.
上記ＥＤＳ分析の結果から、上記電析条件によって形成されたＮｉ／Ｓｎ合金相は組成比の異なる層が交互に積層された構造を有すること、該合金相にはＳｎが溶出しやすい部分とＳｎが溶出しにくい部分とが存在することが示された。 From the result of the EDS analysis, the Ni / Sn alloy phase formed under the electrodeposition conditions has a structure in which layers having different composition ratios are alternately laminated, and the alloy phase has a portion where Sn is easily eluted and Sn. It was shown that there is a part that is difficult to elute.
（評価６：ＳＥＭ観察による断面組成像）
使用前の電極について、断面のさらなる細部をＳＥＭにより反射電子検出モードで観察して組成像を得た。結果を図６（Ａ）及び（Ｂ）に示す。図６（Ａ）のスケールバーは１０μｍであり、図６（Ｂ）のスケールバーは１μｍである。図６（Ａ）から、組成比の違いが層状に（電析の厚さ方向に）分布していることが判る。図６（Ｂ）からは、電析厚さ方向における合金相の組成分布の変動は、電析厚さにして１００ｎｍ以下のごく微小な範囲でも起きていることが推定される。
(Evaluation 6: Cross-sectional composition image by SEM observation)
About the electrode before use, the further detail of the cross section was observed by reflected electron detection mode by SEM, and the composition image was obtained. The results are shown in FIGS. 6 (A) and (B). The scale bar in FIG. 6 (A) is 10 μm, and the scale bar in FIG. 6 (B) is 1 μm. FIG. 6A shows that the difference in composition ratio is distributed in a layered manner (in the thickness direction of electrodeposition). From FIG. 6B, it is estimated that the variation in the composition distribution of the alloy phase in the electrodeposition thickness direction occurs even in a very small range of 100 nm or less in electrodeposition thickness.
本発明の電極反応用電極は、電解反応や燃料電池等の各種電極反応に好適に用いることができる。 The electrode for electrode reaction of the present invention can be suitably used for various electrode reactions such as electrolytic reactions and fuel cells.
１ 導電性の芯部
２ 外層部
１０ 電極反応用電極
DESCRIPTION OF SYMBOLS 1 Conductive core part 2 Outer layer part 10 Electrode for electrode reaction
Claims (6)
該電極は、第１の金属群から選ばれる１種以上の金属元素と、第２の金属群から選ばれる１種以上の金属元素とを含み、
前記第１の金属群は、前記電極反応に対する触媒活性を有し、かつ前記電極反応の条件下では前記電解液に溶解しない１種以上の金属元素からなる群であり、
前記第２の金属群は、前記電極反応の条件下で前記電極反応の進行に伴って前記電解液に溶解する１種以上の金属元素からなる群であり、
前記電極反応の進行に伴って比表面積が増大することを特徴とする、電極反応用電極。 An electrode used for an electrode reaction performed in the presence of an electrolyte solution,
The electrode includes one or more metal elements selected from the first metal group and one or more metal elements selected from the second metal group,
The first metal group is a group consisting of one or more metal elements that have catalytic activity for the electrode reaction and do not dissolve in the electrolyte under the conditions of the electrode reaction;
The second metal group is a group consisting of one or more metal elements that dissolve in the electrolytic solution as the electrode reaction proceeds under the conditions of the electrode reaction,
The electrode reaction electrode, wherein the specific surface area increases with the progress of the electrode reaction.
前記外層部が、前記第１の金属群から選ばれる１種以上の金属元素と、前記第２の金属群から選ばれる１種以上の金属元素とを含む合金相を有する、請求項１に記載の電極反応用電極。 Formed of a conductive core and an outer layer surrounding the core;
The said outer layer part has an alloy phase containing 1 or more types of metal elements chosen from the said 1st metal group, and 1 or more types of metal elements chosen from the said 2nd metal group. Electrode for electrode reaction.
前記第１の金属群が、Ｎｉ、Ｃｏ、Ｆｅ、Ｃｕ、Ａｕ、Ａｇ、Ｒｈ、Ｉｒ、Ｒｅ、Ｒｕ、Ｐｔ、Ｐｄ、Ｍｏ、Ｗ、Ｔｉ、Ｚｎ及びＴａからなる群であり、
前記第２の金属群は、第１の金属群と合金形成が可能な金属からなる群である、請求項１〜４のいずれか一項に記載の電極反応用電極。 The electrode reaction is a reduction reaction in which hydrogen is generated by electrolysis of water;
The first metal group is a group consisting of Ni, Co, Fe, Cu, Au, Ag, Rh, Ir, Re, Ru, Pt, Pd, Mo, W, Ti, Zn, and Ta;
The electrode for electrode reaction according to any one of claims 1 to 4, wherein the second metal group is a group made of a metal capable of forming an alloy with the first metal group.
ＮｉとＳｎとからなる外層部を有し、
該外層部は、ＮｉとＳｎとの組成比の異なる層が交互に積層された構造を有することを特徴とする、水素発生用陰極。 A hydrogen generating cathode for generating hydrogen by electrolysis of water,
Having an outer layer portion made of Ni and Sn;
The cathode for generating hydrogen, wherein the outer layer portion has a structure in which layers having different composition ratios of Ni and Sn are alternately stacked.
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| JPS57177984A (en) * | 1981-04-24 | 1982-11-01 | Toyo Soda Mfg Co Ltd | Cathode for electrolysis |
| JPS62253791A (en) * | 1986-04-25 | 1987-11-05 | Tokuyama Soda Co Ltd | Production of cathode for generating hydrogen |
| JPH071070U (en) * | 1993-02-16 | 1995-01-10 | 株式会社フジプレシャス | Laminated mesh electrode |
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| JPS57177984A (en) * | 1981-04-24 | 1982-11-01 | Toyo Soda Mfg Co Ltd | Cathode for electrolysis |
| JPS62253791A (en) * | 1986-04-25 | 1987-11-05 | Tokuyama Soda Co Ltd | Production of cathode for generating hydrogen |
| JPH071070U (en) * | 1993-02-16 | 1995-01-10 | 株式会社フジプレシャス | Laminated mesh electrode |
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| CN109750317A (en) * | 2018-12-26 | 2019-05-14 | 浙江工业大学 | A kind of preparation method of the compound hydrogen-precipitating electrode of porous Ni-base copper rhenium |
| CN109750317B (en) * | 2018-12-26 | 2020-06-30 | 浙江工业大学 | Preparation method of porous nickel-based copper-rhenium composite hydrogen evolution electrode |
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