JP4085772B2 - Alloy electrode for hydrogen generation and method for producing the same - Google Patents
Alloy electrode for hydrogen generation and method for producing the same Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は、水素発生用合金電極とその製造方法に関する。本発明の電極は、高温の、中性ないし強アルカリ性の液中における電解に使用したとき、水素を高い速度で発生させることができ、電解時および電解停止時における耐久性にすぐれている。
【０００２】
【従来の技術】
発明者らは、高温の海水の電解あるいはソーダ工業における食塩水の電解において、水素を発生する電極、すなわち陰極として高性能な電極を求めて研究し、その成果として、高活性で耐久性にすぐれたＮｉ−Ｍｏ−Ｃ合金電極を見出してすでに開示した（特願２００１−２９７９９２）。この合金電極は、５〜２０原子％のＭｏ、２〜１５原子％のＣおよび残部を占めるＮｉからなる。
【０００３】
発明者らは、長年にわたって、電解により水素を発生するための電極の材料とする合金の性質を研究し、合金を構成する元素の電気化学的な役割を明らかにしてきた。その過程で、コバルトがニッケルとともに、白金族元素についで電解による水素発生に対し高活性な元素であることと、コバルトにモリブデンを合金化することによって、白金族元素をしのぐ高活性を示すことを見出した。
【０００４】
Ｃｏ−Ｍｏ合金電極は、基材金属上に電気メッキを行なうという、きわめて単純な方法によって製造することができ、高温の中性ないしアルカリ性の溶液を電解する場合に使用できる点で、すぐれたものである。しかし、電解を停止したときに、モリブデンがモリブデン酸イオンとなって溶液中に溶解するため、耐久性において劣る。この電極の実用化には、こうした耐久性の向上がキーポイントであった。
【０００５】
そこでさらに研究を進めた結果、ニッケルと並んで水素発生に対して高い活性を発揮することが期待されるコバルトをベースとし、これにモリブデンと炭素とを添加してＣｏ−Ｍｏ−Ｃ合金電極とすることによって、Ｍｏ−Ｃｏ合金電極の弱点であった、電解停止時のモリブデンの溶解が防止できること、しかも、Ｃｏ−Ｍｏ−Ｃ合金電極は、前記したニッケルベースの合金電極に匹敵する性能をもつ電極であることを見出した。また、コバルトでニッケルを置換しても、さほど性能に変りはないことを見出した。炭素の添加は、合金中の金属と炭素が結合することによって、金属元素の溶解を防止するものと考えられる。
【０００６】
【発明が解決しようとする課題】
本発明の目的は、上述した発明者らの知見を活用し、水素発生に対する活性が高く、しかも電解時および電解停止時を通じて耐久性が高い水素発生用合金電極を提供することにある。そのような合金電極を製造する有利な方法を提供することもまた、本発明の目的に包含される。
【０００７】
【課題を解決するための手段】
上記の目的を達成する本発明の水素発生用合金電極の基本的な態様は、モリブデン：５〜４０原子％および炭素：２〜１５原子％を含有し、残部がコバルトおよび不可避な不純物からなる組成の合金を材料とする電極である。
【０００８】
本発明の水素発生用合金電極の変更態様は、モリブデン：５〜４０原子％および炭素：２〜１５原子％を含有し、残部が０．１原子％以上のコバルトとその残りのニッケル、および不可避な不純物からなる組成の合金を材料とする電極である。
【０００９】
【発明の実施形態】
上記した基本的な態様の水素発生用合金電極を製造する本発明の方法は、モリブデンの可溶性塩、コバルトの可溶性塩、オキシカルボン酸およびアミノカルボン酸を含有し、アルカリを加えてｐＨ５以上としたメッキ液を使用して電解を行ない、陰極基材上にＭｏ−Ｃｏ−Ｃ合金を析出させることからなる。
【００１０】
変更態様の水素発生用合金電極を製造する本発明の方法は、モリブデンの可溶性塩、コバルトの可溶性塩、ニッケルの可溶性塩、オキシカルボン酸およびアミノカルボン酸を含有し、アルカリを加えてｐＨ５以上としたメッキ液を使用して電解を行ない、陰極基材上にＭｏ−Ｃｏ−Ｎｉ−Ｃ合金を析出させることからなる。
【００１１】
上記の製造方法において使用するオキシカルボン酸およびアミノカルボン酸については、前掲の特願２００１−２９７９９２の明細書に記述したが、好適な具体例を挙げれば、クエン酸：ＨＯＯＣＣＨ2Ｃ(ＯＨ)(ＣＯＯＨ)ＣＨ2ＣＯＯＨ・Ｈ2Ｏおよびリシン：Ｈ2Ｎ(ＣＨ2)4ＣＨ(ＮＨ2)ＣＯＯＨ・ＨＣｌである。以下に、本発明の電極を構成する合金の成分組成を上記のように限定した理由を説明する。
【００１２】
モリブデン：５〜４０原子％
モリブデンは、コバルトやニッケルが電気メッキされる際に共同析出し、コバルトおよびニッケル上での水素の放電を加速する作用をもつ元素であって、炭素と共存して水素発生に高活性を付与する。この効果を得るためには、電極とする合金中に、モリブデンが５原子％以上存在する必要がある。しかし、４０原子％を超えてモリブデンを存在させても、水素発生の活性を高める効果が飽和する。モリブデンの過剰な存在はまた、電解停止時の高温濃厚アルカリ液中におけるモリブデンの溶解をひき起こし、電極の耐久性を損なう危険がある。
【００１３】
炭素：２〜１５原子％
炭素は、Ｃｏ-Ｍｏ合金およびＣｏ-Ｎｉ-Ｍｏ合金中で金属元素と結合し、電荷移動によって水素の放電を加速して、水素発生に対する活性を向上させる。それとともに、電解停止時の金属元素の溶解を防止する作用を有する。合金中の含有量が２原子％以上であるとき、この効果が確保される。一方、多量に炭素を存在させることは、水素発生を担う金属元素の濃度を低下させる結果となり、好ましくない。そこで、１５原子％という上限を設けた。
【００１４】
コバルト：残部
コバルトは本発明の合金電極の中心的な成分であって、水素発生の活性を主として担う元素である。したがって、モリブデンおよび炭素を除いた部分を、コバルトが占めるようにする。ニッケルを共存させる場合は、この部分のうち０．１原子％に相当する量のコバルトが存在すれば、その残りはニッケルとすることができる。
【００１５】
ニッケル：残部のうちコバルトが占める０．１原子％を除く部分
コバルトに対して適量のニッケルを共存させると、水素発生過電圧がいっそう低下した、高活性の電極を得ることができる。
【００１６】
本発明の電極を構成する合金において、イオウやリンのような不純物が少量含まれていても、水素発生に対する活性と耐久性には、実質的な影響は認められない。
【００１７】
【実施例１】
下記の成分を溶解した水溶液を用意し、
１）硫酸コバルトＣｏＳＯ4・７Ｈ2Ｏ ６２g/L
２）クエン酸ＨＯＯＣＣＨ2Ｃ(ＯＨ)(ＣＯＯＨ)ＣＨ2ＣＯＯＨ・Ｈ2Ｏ 66g/L
３）サッカリン １g/L
４）ラウリル硫酸ナトリウム ０．０８g/L
５）モリブデン酸ナトリウムＮａ2ＭｏＯ4・２Ｈ2Ｏ ５g/L
６）リシンＨ2Ｎ(ＣＨ2)4ＣＨ(ＮＨ2)ＣＯＯＨ・ＨＣｌ 1.8265g/L
これに４Ｍ−ＮａＯＨを滴下して、ｐＨを５とした。２５℃において、電流密度５０Ａ／ｍ2でメッキを行なって、
Ｃｏ−２６．４原子％Ｍｏ−１０．１原子％Ｃ
の組成のメッキ合金を得た。
【００１８】
この合金を陰極として使用し、９０℃の８Ｍ−ＮａＯＨの電解を行なったところ、１２５Ａ／ｍ2という電流密度においても、水素発生過電圧がわずかに４３ｍＶと、高い活性を示した。この電極は、８Ｍ−ＮａＯＨ中に浸漬し、９０℃に保って５０日間経過した後も、水素発生過電圧はまったく上昇することなく、カソード分極曲線は浸漬前と同じであって、耐久性が高い電極であることが確認された。
【００１９】
【実施例２】
実施例１で使用したものと同じ成分からなる溶液において、モリブデン酸ナトリウムおよびクエン酸の濃度を表１に示すように変化させた、ｐＨが５〜６の溶液を使用して、やはり表２に示す組成をもつ合金を製造した。これらの合金を、９０℃の８Ｍ−ＮａＯＨの電解に陰極として使用し、１２５Ａ／ｍ2の電流密度における水素発生過電圧を測定した。その結果を、表１にあわせて掲げる。表１のデータは、各電極が高活性であることを示している。これらの電極を９０℃の８Ｍ−ＮａＯＨ中に１５〜２０日間浸漬した後も、水素発生過電圧には変化がないことが確認された。
【００２０】
表１
【実施例３】
実施例1で使用したメッキ液の硫酸コバルト６２ｇ／Ｌの一部を硫酸ニッケルＮｉＳＯ4・６Ｈ2Ｏで置き換え、さらにホウ酸Ｈ3ＢＯ3を６ｇ／Ｌ添加した溶液において、モリブデン酸ナトリウムおよびクエン酸の濃度を表２に示すように種々変化させたｐＨ５〜６の溶液を使用し、表２に示す合金組成のメッキ金属を得た。それらを陰極として９０℃の８Ｍ−ＮａＯＨを電気分解し、１２５Ａ／ｍ2の電流密度における水素発生過電圧を測定した。その結果を、表２にあわせて掲げる。これらの合金の電極もまた、水素発生過電圧が低い高活性な電極であることが確認され、９０℃の８Ｍ−ＮａＯＨ中に１５〜２０日間浸漬した後も、水素発生過電圧にまったく変化がないことが確認された。
【００２２】
表２
【発明の効果】
本発明のＣｏ−Ｍｏ−Ｃ合金またはＣｏ−Ｎｉ−Ｍｏ−Ｃ合金を材料とする水素発生用電極は、高温の中性ないし強アルカリ性の水溶液中における電解に使用したとき、水素発生に対して高活性であって、高い電流密度においても、水素過電圧は低い。またこれらの電極は、高温の濃厚なアルカリ液中に浸漬したまま放置しても安定であって、成分金属が溶出することなく、高い耐久性を示す。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an alloy electrode for hydrogen generation and a method for producing the same. The electrode of the present invention can generate hydrogen at a high rate when it is used for electrolysis in a high-temperature neutral or strong alkaline solution, and has excellent durability during electrolysis and when electrolysis is stopped.
[0002]
[Prior art]
The inventors have studied for an electrode that generates hydrogen, that is, a high-performance electrode as a cathode in electrolysis of high-temperature seawater or salt water in the soda industry. As a result, the inventors have achieved high activity and excellent durability. A Ni-Mo-C alloy electrode was found and already disclosed (Japanese Patent Application No. 2001-279992). This alloy electrode consists of 5-20 atomic% Mo, 2-15 atomic% C and the balance Ni.
[0003]
For many years, the inventors have studied the properties of an alloy used as an electrode material for generating hydrogen by electrolysis, and have clarified the electrochemical role of the elements constituting the alloy. In the process, cobalt, together with nickel, is a highly active element for hydrogen generation by electrolysis following the platinum group element, and shows high activity that surpasses the platinum group element by alloying molybdenum with cobalt. I found it.
[0004]
Co-Mo alloy electrodes are excellent in that they can be manufactured by a very simple method of electroplating on a base metal and can be used when electrolyzing neutral or alkaline solutions at high temperatures. It is. However, when electrolysis is stopped, molybdenum becomes molybdate ions and dissolves in the solution, so that the durability is inferior. Such improvement in durability was a key point for practical use of this electrode.
[0005]
Therefore, as a result of further research, it was based on cobalt, which is expected to exhibit high activity against hydrogen generation along with nickel, and by adding molybdenum and carbon to this, a Co—Mo—C alloy electrode and By doing so, it is possible to prevent the melting of molybdenum when the electrolysis is stopped, which was a weak point of the Mo—Co alloy electrode, and the Co—Mo—C alloy electrode has a performance comparable to the nickel-based alloy electrode described above. It was found to be an electrode. Moreover, even if nickel was substituted by cobalt, it discovered that a performance did not change so much. The addition of carbon is considered to prevent dissolution of the metal element by bonding the metal and carbon in the alloy.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to provide an alloy electrode for hydrogen generation having high activity for hydrogen generation and high durability during electrolysis and when electrolysis is stopped, utilizing the knowledge of the inventors described above. It is also within the scope of the present invention to provide an advantageous method of manufacturing such an alloy electrode.
[0007]
[Means for Solving the Problems]
The basic aspect of the alloy electrode for hydrogen generation of the present invention that achieves the above object is a composition containing molybdenum: 5 to 40 atomic% and carbon: 2 to 15 atomic%, with the balance being cobalt and inevitable impurities. This is an electrode made of the above alloy.
[0008]
The modification of the alloy electrode for hydrogen generation of the present invention includes molybdenum: 5 to 40 atomic% and carbon: 2 to 15 atomic%, with the balance being 0.1 atomic% or more of cobalt and the remaining nickel , and unavoidable It is an electrode made of an alloy having a composition composed of various impurities .
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The method of the present invention for producing the alloy electrode for hydrogen generation of the basic aspect described above contains a soluble salt of molybdenum, a soluble salt of cobalt, an oxycarboxylic acid and an aminocarboxylic acid, and an alkali is added so as to have a pH of 5 or more. Electrolysis is performed using a plating solution to deposit a Mo—Co—C alloy on the cathode substrate.
[0010]
The method of the present invention for producing an alloy electrode for hydrogen generation according to a modified embodiment contains a soluble salt of molybdenum, a soluble salt of cobalt, a soluble salt of nickel, an oxycarboxylic acid and an aminocarboxylic acid, and an alkali is added to adjust the pH to 5 or more. Electrolysis is performed using the plated plating solution, and a Mo—Co—Ni—C alloy is deposited on the cathode substrate.
[0011]
The oxycarboxylic acid and aminocarboxylic acid used in the above production method are described in the specification of the above-mentioned Japanese Patent Application No. 2001-297990. However, citric acid: HOOCCH 2 C (OH) ( COOH) CH 2 COOH · H 2 O and lysine: H 2 N (CH 2) a 4 CH (NH 2) COOH · HCl. The reason why the component composition of the alloy constituting the electrode of the present invention is limited as described above will be described below.
[0012]
Molybdenum: 5 to 40 atomic%
Molybdenum co-precipitates when cobalt or nickel is electroplated, and has the effect of accelerating the discharge of hydrogen on cobalt and nickel. It coexists with carbon and imparts high activity to hydrogen generation. . In order to obtain this effect, it is necessary that 5 atomic% or more of molybdenum be present in the alloy used as the electrode. However, even if molybdenum exceeds 40 atomic%, the effect of increasing the activity of hydrogen generation is saturated. The excessive presence of molybdenum also causes the dissolution of molybdenum in the hot concentrated alkaline solution when the electrolysis is stopped, and there is a risk of impairing the durability of the electrode.
[0013]
Carbon: 2-15 atomic%
Carbon binds to a metal element in the Co—Mo alloy and the Co—Ni—Mo alloy, accelerates the discharge of hydrogen by charge transfer, and improves the activity against hydrogen generation. At the same time, it has an effect of preventing dissolution of the metal element when the electrolysis is stopped. This effect is ensured when the content in the alloy is 2 atomic% or more. On the other hand, the presence of a large amount of carbon is not preferable because it results in a decrease in the concentration of the metal element responsible for hydrogen generation. Therefore, an upper limit of 15 atomic% was set.
[0014]
Cobalt: The remaining cobalt is a central component of the alloy electrode of the present invention, and is an element mainly responsible for the activity of hydrogen generation. Accordingly, cobalt is occupied in the portion excluding molybdenum and carbon. In the case where nickel is present, if the amount of cobalt corresponding to 0.1 atomic% is present in this portion, the remainder can be nickel.
[0015]
Nickel: When an appropriate amount of nickel is allowed to coexist with partial cobalt other than 0.1 atomic% occupied by cobalt in the balance, a highly active electrode with a further reduced hydrogen generation overvoltage can be obtained.
[0016]
Even if the alloy constituting the electrode of the present invention contains a small amount of impurities such as sulfur and phosphorus, there is no substantial effect on the activity and durability against hydrogen generation.
[0017]
[Example 1]
Prepare an aqueous solution in which the following ingredients are dissolved:
1) Cobalt sulfate CoSO 4 · 7H 2 O 62g / L
2) Citric acid HOOCCH 2 C (OH) (COOH) CH 2 COOH · H 2 O 66 g / L
3) Saccharin 1g / L
4) Sodium lauryl sulfate 0.08g / L
5) Sodium molybdate Na 2 MoO 4 · 2H 2 O 5g / L
6) Lysine H 2 N (CH 2 ) 4 CH (NH 2 ) COOH · HCl 1.8265 g / L
4M NaOH was added dropwise thereto to adjust the pH to 5. Plating at a current density of 50 A / m 2 at 25 ° C.
Co-26.4 atomic% Mo-10. 1 atomic% C
A plating alloy having the following composition was obtained.
[0018]
When this alloy was used as a cathode and electrolysis of 8 M NaOH at 90 ° C. was performed, even at a current density of 125 A / m 2 , the hydrogen generation overvoltage was as high as 43 mV, indicating a high activity. This electrode is immersed in 8M-NaOH, and after 50 days at 90 ° C., the hydrogen generation overvoltage does not increase at all, and the cathodic polarization curve is the same as before the immersion, and the durability is high. It was confirmed to be an electrode.
[0019]
[Example 2]
In a solution composed of the same components as those used in Example 1, the concentration of sodium molybdate and citric acid was changed as shown in Table 1, and a solution having a pH of 5 to 6 was used. An alloy having the composition shown was produced. These alloys were used as cathodes for electrolysis of 8M NaOH at 90 ° C., and the hydrogen generation overvoltage at a current density of 125 A / m 2 was measured. The results are listed in Table 1. The data in Table 1 indicates that each electrode is highly active. It was confirmed that the hydrogen generation overvoltage did not change even after these electrodes were immersed in 8 M NaOH at 90 ° C. for 15 to 20 days.
[0020]
Table 1
[Example 3]
In a solution in which a part of cobalt sulfate 62 g / L of the plating solution used in Example 1 was replaced with nickel sulfate NiSO 4 .6H 2 O and boric acid H 3 BO 3 was added 6 g / L, sodium molybdate and citric acid were added. Using solutions having a pH of 5 to 6 in which the acid concentration was variously changed as shown in Table 2, plated metals having an alloy composition shown in Table 2 were obtained. Using them as cathodes, 8 M NaOH at 90 ° C. was electrolyzed, and the hydrogen generation overvoltage at a current density of 125 A / m 2 was measured. The results are listed in Table 2. The electrodes of these alloys were also confirmed to be highly active electrodes with low hydrogen generation overvoltage, and there was no change in the hydrogen generation overvoltage even after immersion in 8M NaOH at 90 ° C. for 15 to 20 days. Was confirmed.
[0022]
Table 2
【The invention's effect】
The electrode for hydrogen generation using the Co—Mo—C alloy or Co—Ni—Mo—C alloy of the present invention as a material against hydrogen generation when used for electrolysis in a high temperature neutral or strong alkaline aqueous solution. The hydrogen overvoltage is low even at high activity and high current density. In addition, these electrodes are stable even when left immersed in a hot concentrated alkaline solution, and show high durability without elution of component metals.
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| KR20200096178A (en) | 2018-07-09 | 2020-08-11 | 충남대학교산학협력단 | Porous Ni-Al-Mo Cathode for Alkaline Water Electrolysis |
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| CN110433835A (en) * | 2019-07-02 | 2019-11-12 | 常州大学 | A kind of efficient liberation of hydrogen catalyst and preparation method thereof |
| CN114959786B (en) * | 2022-05-24 | 2023-02-17 | 哈尔滨工业大学 | Cobalt-aluminum-doped 1T-phase molybdenum disulfide powder and preparation method and application thereof |
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| KR20200005828A (en) | 2018-07-09 | 2020-01-17 | 충남대학교산학협력단 | Porous Ni-Al-Mo Cathod for Alkaline Water Electrolysis, Preparation Method thereof and Ni-Al-Mo Coating Material for Thermal Spray |
| KR20200096178A (en) | 2018-07-09 | 2020-08-11 | 충남대학교산학협력단 | Porous Ni-Al-Mo Cathode for Alkaline Water Electrolysis |
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