JPH03240986A - Hydrogen producing cathode - Google Patents
Hydrogen producing cathodeInfo
- Publication number
- JPH03240986A JPH03240986A JP2286918A JP28691890A JPH03240986A JP H03240986 A JPH03240986 A JP H03240986A JP 2286918 A JP2286918 A JP 2286918A JP 28691890 A JP28691890 A JP 28691890A JP H03240986 A JPH03240986 A JP H03240986A
- Authority
- JP
- Japan
- Prior art keywords
- support
- chromium
- film
- nitrate
- nitrates
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000001257 hydrogen Substances 0.000 title claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 14
- 239000011651 chromium Substances 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 14
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims abstract description 12
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims description 35
- 239000011248 coating agent Substances 0.000 claims description 31
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 27
- 229910052804 chromium Inorganic materials 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 150000002823 nitrates Chemical class 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- -1 alkali metal chlorate Chemical class 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001209 Low-carbon steel Inorganic materials 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims 1
- 229910001485 alkali metal perchlorate Inorganic materials 0.000 claims 1
- 239000012300 argon atmosphere Substances 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 abstract description 4
- 125000004429 atom Chemical group 0.000 abstract 3
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 238000000386 microscopy Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000001941 electron spectroscopy Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Automation & Control Theory (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Chemically Coating (AREA)
- Conductive Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inert Electrodes (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は水素発生カソード、該カソードの製造方法及び
該カソードの電解への適用に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a hydrogen generating cathode, a method of manufacturing the cathode, and an application of the cathode to electrolysis.
本発明により得られるようなカソードは電気伝導性のあ
る支持体（以後単に支持体と称する）を備え、該支持体
上にはコバルトのまたクロムの酸化化合物からなる伝導
性のある被膜く以後単に被膜と称する〉が塗布されてい
る。本発明に従って簡単に且つ安価に製造される被膜は
支持体に堅固に密着し、それにより水素発生の過電圧は
低くなり、また電解でのカソードの作動安定性が良好と
なり得る。The cathode as obtained according to the invention comprises an electrically conductive support (hereinafter simply referred to as support), on which a conductive coating consisting of a cobalt or chromium oxide compound is coated. A coating (referred to as a coating) is applied. The coating produced simply and inexpensively according to the invention adheres firmly to the support, so that the overpotential for hydrogen evolution can be low and the operational stability of the cathode in electrolysis can be good.
ヨーロッパ特許公開第０．１２６，１８９号は、水素発
生の過電圧の大きさと関連する過剰なエネルギー消費を
最小限にするカソードを利用することが、エネルギーコ
ストの増大に鑑み、産業界の利点となると説明している
。European Patent Publication No. 0.126,189 states that, in view of increasing energy costs, it would be advantageous for industry to utilize cathodes that minimize the excessive energy consumption associated with the magnitude of overvoltages in hydrogen generation. Explaining.
該特許公開公報は更に、この問題が多くの論文が公報で
提起されていることを示している。The patent publication further indicates that this issue has been raised in many articles in the publication.
該特許公開公報は、クロム化合物と、ニッケル及びコバ
ルトの中から選択される少なくとも１種の金属の酸化物
とを被膜が含んでいる水素発生カソードの提示を目的と
している。この被膜は専ら３つの方法（粉末状前駆体混
合物の溶融状態での噴霧、酸化雰囲気下での可溶化状態
の前駆体混合物の焼結、及び電気化学的又は化学的めっ
き後の酸化雰囲気下での酸化■焼）の中から選択された
技術により支持体に塗布される。金属元素の比率の選択
と関連するこの方法選択により、クロムからまた他の金
属から誘導される特別の会合物が生じる。該会合物の形
態はこの他の金属の存在形態とは異なっていない。The patent publication aims to present a hydrogen-generating cathode whose coating contains a chromium compound and an oxide of at least one metal selected from among nickel and cobalt. This coating can be produced by three methods exclusively: spraying of the powdered precursor mixture in the molten state, sintering of the precursor mixture in the solubilized state under an oxidizing atmosphere, and electrochemical or chemical plating followed by an oxidizing atmosphere. The coating is applied to the support by a technique selected from the following: This method selection in conjunction with the selection of the proportions of the metal elements results in special associations derived from chromium and also from other metals. The form of this association is not different from the forms of other metals.
しかしながら本発明の水素発生カソードは、その被膜に
存在するコバルトが酸化物Ｃｏ３Ｏ４の形態であると同
時に、Ｘ線回折ではＣｏ２ＣｒＯ４として示されるＣｏ
、Ｏ，以外の化合物の形態であり、また被膜に存在する
クロム及びコバルトの原子の累積数（総数）に対するク
ロム原子数の比の値がＣＯコ０４の消失する場合の値よ
り低いままであるような量だけ、被膜に存在するクロム
を前記化合物が含んでいることを特徴とする。However, in the hydrogen generating cathode of the present invention, the cobalt present in the coating is in the form of oxide Co3O4, and at the same time Co
, O, and the ratio of the number of chromium atoms to the cumulative number (total number) of chromium and cobalt atoms present in the coating remains lower than the value when CO04 disappears. The compound is characterized in that said compound contains chromium present in the coating in an amount such that:
このように定義されるカソードの製造方法は、最初に支
持体上に塗布された溶液形態の硝酸コバルトと硝酸クロ
ムとを溶解するために選択された溶媒を除去して支持体
上に得られる前記２つの硝酸塩の混合物を、例えば窒素
又はアルゴンのような不活性雰囲気下において、２５０
℃〜７００℃、大抵の場合は約３００℃より高い温度で
、好ましくは約３５０℃〜５００℃の温度で支持体上に
て熱分解することにより被膜を得ることを特徴とする。The method for producing a cathode defined in this way is to first remove the solvent selected for dissolving cobalt nitrate and chromium nitrate in the form of a solution coated on the support to obtain the above-mentioned material on the support. A mixture of two nitrates is heated under an inert atmosphere such as nitrogen or argon for 250 min.
The coating is characterized in that it is obtained by pyrolysis on the support at temperatures between 700°C and 700°C, often above about 300°C, preferably between about 350°C and 500°C.
本発明に基づくカソードを使用するのは例えば、他のカ
ソードでよく知られた条件下において、アルカリ金属の
塩化物から該金属の塩素酸塩へのく例えば塩化ナトリウ
ムから塩素酸ナトリウムへの）、又はアルカリ金属の塩
素酸塩から該金属の過塩素酸塩への（例えば塩素酸ナト
リウムから過塩素酸ナトリウムへの）水性媒体での電解
である。本発明のカソードは塩化物、塩素酸塩及び過塩
素酸塩からなる電解質中において酸性、中性又はアルカ
リ性の媒体、好ましくはｐＨが約５〜１２の媒体で使用
され得る。The cathode according to the invention can be used, for example, to convert the chloride of an alkali metal to the chlorate of said metal (e.g. from sodium chloride to sodium chlorate) under conditions well known for other cathodes. or electrolysis of an alkali metal chlorate to a perchlorate of the metal (eg, sodium chlorate to sodium perchlorate) in an aqueous medium. The cathodes of the invention can be used in acidic, neutral or alkaline media, preferably with a pH of about 5 to 12, in electrolytes consisting of chlorides, chlorates and perchlorates.
本発明の３つの要旨（独立発明）について前述した定義
及び／′又はそれに伴う全ての説明においては、他に明
記しない限りまた自明でない限り次の事項が適用される
。In the foregoing definitions and/or all accompanying explanations of the three aspects of the invention (independent inventions), the following applies, unless otherwise specified or obvious:
一部をパーセントで表すコバルト原子とクロム原子との
累積（総）数に対するクロム原子数の比率を、クロム含
量として示す。The ratio of the number of chromium atoms to the cumulative (total) number of cobalt atoms and chromium atoms, expressed as a percentage, is shown as the chromium content.
支持体上の被膜をＸ線回折及び／又は電子検鏡法により
検査するときにＣｏ２ＣｒＯ４がＣｏ、０．と異なって
いる点で、Ｃｏ２Ｃｒ０＜とじて示される化合物はＣｏ
）０４以外の化合物であると考えられる。When the coating on the support is examined by X-ray diffraction and/or electronic microscopy, Co2CrO4 is Co, 0. The difference is that the compound represented by Co2Cr0< is Co
)04.
−Ｃｏ、０４が支持体上の被膜のＸ線検査によりもはや
検出できないときにＣｏ＝０．は消失したと考える。-Co=0.0 when Co,04 can no longer be detected by X-ray examination of the coating on the support. I think it has disappeared.
−硝酸クロムと硝酸コバルトとを含んでいて最初に支持
体上に塗布される溶液を生成するために使用される硝酸
クロム及び硝酸コバルトは通常水和結晶塩、例えばＣｏ
（ＮＯｌ）２．６Ｈ２０又はＣｒ（ＮＯｓ）ｉ−９Ｈ２
０である。溶液中では２つの硝酸塩は被膜で規定された
クロム濃度に適合するような相対的な量で使用される。- The chromium nitrate and cobalt nitrate used to produce the solution containing chromium nitrate and cobalt nitrate which is first applied onto the support are usually hydrated crystalline salts, e.g.
(NOl)2.6H20 or Cr(NOs)i-9H2
It is 0. In solution, the two nitrates are used in relative amounts to match the chromium concentration specified in the coating.
溶媒の作用が２つの硝酸塩に対して影響せず、該硝酸塩
の担持の作用に限定されるならば、また硝酸塩の熱分解
が結晶水の一部の離脱を越えて拡がることなく、即ち硝
酸塩自体が分解されることなく、−旦支持体上に塗布さ
れたｆＪ液がらの溶媒の除去が通常蒸発により実施され
得るならば、２つの硝酸塩の共存溶液を生成するために
選択される溶媒の性質は重要ではない。それで、溶媒は
例えば水、エタノールのようなアルコール又は９５゜エ
タノールのようなヒドロアルコール溶液であり得る。If the action of the solvent has no effect on the two nitrates and is limited to the action of supporting the nitrates, then the thermal decomposition of the nitrates does not extend beyond the withdrawal of some of the water of crystallization, i.e. the nitrates themselves The nature of the solvent chosen to produce a coexisting solution of the two nitrates, provided that the removal of the solvent from the fJ solution once coated on the support can be carried out, usually by evaporation, without decomposition of the is not important. Thus, the solvent may be, for example, water, an alcohol such as ethanol or a hydroalcoholic solution such as 95° ethanol.
溶液の支持体上への塗布は、例えばブラシによる塗装、
噴霧又は浸漬により、該支持体の一面又は両面の全体又
は一部で実施する。Application of the solution onto the support can be carried out, for example, by painting with a brush,
This is carried out on all or part of one or both sides of the support by spraying or dipping.
本発明の被膜を得るために実施する２つの硝酸塩の熱分
解の処理時間は本質的に、該処理のために選択した温度
に依存する。処理時間は一般に約５分〜２時間であり、
大抵の場合は約０．５時間〜１時間である。The treatment time for the pyrolysis of the two nitrates carried out to obtain the coatings of the invention essentially depends on the temperature chosen for the treatment. Processing time is generally about 5 minutes to 2 hours;
In most cases it will be about 0.5 to 1 hour.
支持体上の被膜の最終厚さは広範囲内で、例えば約１μ
ＩＩ〜３００μ輪の間で変動し得る。実際にはこの厚さ
は支持体上に硝酸塩溶液を連続的に塗布することにより
得られる。塗布回数は特に該溶液の硝酸塩濃度に応じて
変動する。溶媒除去と熱分解処理を実施するか、又は単
に溶媒を除去する工程を各塗布後実施する。そのとき、
適切な熱処理を最後にのみ実施する。The final thickness of the coating on the support can vary within a wide range, for example about 1μ.
It can vary between II and 300μ rings. In practice, this thickness is obtained by continuous application of the nitrate solution onto the support. The number of applications varies depending, among other things, on the nitrate concentration of the solution. A solvent removal and pyrolysis treatment or simply a solvent removal step is performed after each application. then,
Appropriate heat treatment is carried out only at the end.
本発明のカソード内の支持体は、通常水素発生カソード
の場合に使用される支持体である。該支持体は例えば鉄
、好ましくは軟鋼若しくはステンレス鋼、ニッケル又は
チタンからなる。既に引用したヨーロッパ特許公開第０
．１２６，１８９号は、支持体の初期状態に関して講ず
べき措置を説明している。これらの措置は本発明にも当
てはまり得る。The support in the cathode of the present invention is a support normally used in the case of hydrogen generating cathodes. The support may be made of iron, preferably mild or stainless steel, nickel or titanium. Already cited European patent publication no.
．． No. 126,189 describes the measures to be taken regarding the initial condition of the support. These measures may also apply to the present invention.
Ｘ線回折測定の外に、電子分光測定（ＥＳＣ＾）及び電
子検鏡法を使用する化学分析が、本発明の支持体上の被
膜の性質及び外観がいかなるものがを決定するために使
用される方法であった。Besides X-ray diffraction measurements, chemical analysis using electron spectroscopy (ESC^) and electronic microscopy can be used to determine what the nature and appearance of the coatings on the supports of the present invention are. It was a method of
従って、当該被膜の場合、
クロム金属も酸化クロムＣｒ２Ｏ，も検出できないこと
、
Ｃｏ２Ｃｒ０＜の外観を有すると考えられる、被膜に存
在する総てのクロムを含んでいる化合物が恐ら（Ｃｏ２
ＣｒＯ４自体であること、
一形態が特殊であり、硝酸コバルトのみを出発材料とす
る以外は本発明の方法に従って形成される被膜の形態等
とは異なっており、また本発明の被膜の表面の外観が遥
かに均質、均−及び連続的であること、
ＣｏＪ４が被膜から消失するときのクロム濃度が参考ま
でに通常的３０％であること
を証明することができた。Therefore, in the case of this film, neither chromium metal nor chromium oxide Cr2O can be detected, and all the chromium-containing compounds present in the film, which are thought to have an appearance of <Co2Cr0, are probably (Co2
It is different from the form of the film formed according to the method of the present invention except that it is CrO4 itself, has a special form, and uses only cobalt nitrate as a starting material, and the appearance of the surface of the film of the present invention. It was possible to prove that the chromium concentration is much more homogeneous, uniform and continuous, and that the chromium concentration when the CoJ4 disappears from the coating is typically 30% for reference.
第１図、第２図及び第３図に再現した電子検鏡法による
像はそれぞれ、被膜面の状態に関して令達べてきたこと
を例示している。The electronic microscopic images reproduced in FIGS. 1, 2, and 3 each illustrate what has been achieved regarding the condition of the coating surface.
第１図はクロム濃度値が０．５％に等しい場合ての、本
発明のカソード中の支持体の被膜面を電子検鏡法により
２０００倍に拡大した像を再現したものである。その被
膜面は本発明方法に従ってＣ０（ＮＯ：＋）２．６）１
２０又はＣｒ（ＮＯ３）、、９Ｈ２０から次のように製
造した。溶媒としては９５°アルコールを使用し、窒素
流下で支持体上の硝酸塩を４００℃で０，５時間熱分解
した。硝酸塩溶液の支持体上への被覆、溶媒の蒸発及び
熱分解処理という以後の作業を、所望の被膜厚さが得ら
れるまで繰り返し行った。FIG. 1 is a reproduction of an image magnified 2000 times by electronic microscopy of the coated surface of the support in the cathode of the present invention when the chromium concentration value is equal to 0.5%. The coating surface is C0(NO:+)2.6)1 according to the method of the present invention.
20 or Cr(NO3), 9H20 as follows. The nitrates on the support were pyrolyzed at 400° C. for 0.5 h under nitrogen flow using 95° alcohol as a solvent. The subsequent operations of coating the nitrate solution onto the support, evaporation of the solvent and pyrolysis treatment were repeated until the desired coating thickness was obtained.
第２図はクロム濃度値が１９５％に等しい場合での被膜
面を電子検鏡法により２０００倍に拡大した像を再現し
たものである。なお、この被覆には第１図の場合で説明
した方法を適用した。FIG. 2 is a reproduction of an image magnified 2000 times by electronic microscopy of the coating surface when the chromium concentration value is equal to 195%. Note that the method explained in the case of FIG. 1 was applied to this coating.
第３図はクロム濃度値がゼロに等しい場合での被膜面を
比較用として電子検鏡方法により２０００倍に拡大した
像を再現したものである。導入した硝酸塩は単に硝酸塩
Ｃｏ（ＮＯ３）２．６Ｈ２０であり、第１図及び第２図
の被膜の製造の場合で説明した方法をこの場合にも適用
した。FIG. 3 is a reproduction of a 2000 times magnified image using an electronic microscopy method for comparison of the coating surface when the chromium concentration value is equal to zero. The nitrate introduced was simply the nitrate Co(NO3)2.6H20, and the method described in the case of the production of the coatings of FIGS. 1 and 2 was also applied in this case.
前記３つの場合の各々においては、支持体は頑丈な軟鋼
板である。この鋼板は各々同一厚さの被膜の塗布前ｌ脱
脂して、コランダムで研磨されたものである。In each of the three cases, the support is a solid mild steel plate. The steel plates were each degreased and polished with corundum before being coated with a coating of the same thickness.
本発明に適合するカソード及び本発明に適合しないカソ
ードの電気化学的特性、従って被膜の電気化学的特性を
水素発生についての電気活動度により示した。この電気
活動度を決定するには、水、１２０ｇ／Ｉ！のＮａＣＩ
、５８０ｇ／ＩのＮａＣｌＯｓ及び６ｇ／ｌのＮａ２Ｃ
ｒ２Ｏ７からなる、ｐＮが６゜５に等しく、温度が６５
℃に等しい電解質中で、測定中の抵抗性降下（オーミッ
クドロップ）防止を周知機能とするＬｕｇｇｉｎキャピ
ラリーによって、２０＾／ｄＩ１１２の分極下でＳＣＥ
と称する飽和カロメル電極に相対するカソード電位を測
定することによる。The electrochemical properties of the cathodes compatible with the invention and of the cathodes not compatible with the invention, and thus of the coatings, were illustrated by electrical activity for hydrogen evolution. To determine this electrical activity, water, 120 g/I! of NaCI
, 580 g/I NaClOs and 6 g/l Na2C
consisting of r2O7, pN equal to 6°5 and temperature 65
SCE under polarization of 20^/dI 112 in an electrolyte equal to
By measuring the cathode potential relative to a saturated calomel electrode called .
本発明の利点を示す測定結果を参考までに以下の表１（
非制限的例）に示す。比較用に評価したカソード３の場
合、クロム濃度値は０％に等しい。For reference, the measurement results showing the advantages of the present invention are shown in Table 1 below (
Non-limiting example). In the case of cathode 3 evaluated for comparison, the chromium concentration value is equal to 0%.
何故ならば、第３図の対象であるカソードの場合と同様
に、この被膜は単に硝酸コバルトから得られるからであ
る。比較用に評価したカソード４の場合、クロム濃度は
示されていない。何故ならば支持体は本来の形態（それ
自身のみ）で使用されるからである。本発明方法と同様
に一連の段階が適用されたカソード７を比較用に評価す
る。そのクロム濃度値は被膜のＣｏ３０．消失に対応す
るクロム濃度値より高い。電極１，２，５．６は本発明
に基づいている。支持体の被膜がある総ての場合におい
て、被膜厚さはいずれも同一である。This is because, as in the case of the cathode, the subject of FIG. 3, this coating is obtained solely from cobalt nitrate. In the case of Cathode 4, which was evaluated for comparison, the chromium concentration is not shown. This is because the support is used in its original form (only on its own). A cathode 7, to which a series of steps similar to the method of the invention were applied, is evaluated for comparison. The chromium concentration value is Co30. higher than the chromium concentration value corresponding to disappearance. Electrodes 1, 2, 5.6 are based on the invention. In all cases where there is a coating of the support, the coating thickness is the same in both cases.
艮１ 水素発生カソード议1 hydrogen generating cathode
第１図はクロム濃度値が０５％に等しい場合での支持体
の被膜面を電子検鏡法により２０００倍に拡大した像を
再現した図、第２図はクロム濃度値が１９．５％に等し
い場合での被膜面を電子検鏡法により２０００倍に拡大
した像を再現した図、第３図はクロム濃度値かゼロの場
合での被膜面を電子検鏡法により２０００倍に拡大した
像を再現した図である。Figure 1 is a reproduction of an image magnified 2000 times by electronic microscopy of the coated surface of the support when the chromium concentration value is equal to 0.5%, and Figure 2 is a reproduction of the image when the chromium concentration value is 19.5%. Figure 3 is a reproduction of an image of the coating surface magnified 2000 times using electronic microscopy in the same case. Figure 3 is an image of the coating surface magnified 2000 times using electronic microscopy when the chromium concentration value is zero. This is a diagram that reproduces.
Claims (12)
バルトのまたクロムの酸化化合物からなる被膜が同時に
形成されている水素発生カソードであって、被膜に存在
するコバルトが酸化物Ｃｏ＿３Ｏ＿４の形態であると同
時に、Ｘ線回折ではＣｏ＿２ＣｒＯ＿４として示される
Ｃｏ＿３Ｏ＿４以外の化合物の形態であり、被膜に存在
するクロム原子及びコバルト原子の総数に対するクロム
原子数の比の値がＣｏ＿３Ｏ＿４の消失する場合の値よ
り低いままであるような量だけ、被膜に存在するクロム
を前記化合物が含んでいることを特徴とする水素発生カ
ソード。(1) A hydrogen-generating cathode comprising an electrically conductive support, on which a film consisting of an oxide compound of cobalt or chromium is simultaneously formed, and the cobalt present in the film is an oxide Co_3O_4. At the same time, it is in the form of a compound other than Co_3O_4, which is shown as Co_2CrO_4 in X-ray diffraction, and the value of the ratio of the number of chromium atoms to the total number of chromium atoms and cobalt atoms present in the film is the same as when Co_3O_4 disappears. A hydrogen generating cathode, characterized in that said compound contains chromium present in the coating in such an amount that the value remains below the value.
ンの中から選択された物質からなることを特徴とする請
求項１に記載の水素発生カソード。(2) The hydrogen generating cathode according to claim 1, wherein the support is made of a material selected from mild steel, stainless steel, nickel and titanium.
方法であって、最初に支持体上に塗布された溶液形態の
硝酸コバルトと硝酸クロムとを共に溶解するために選択
された溶媒を除去して支持体上に得られる前記２つの硝
酸塩の混合物を、不活性雰囲気下において、２５０℃〜
７００℃の温度にて支持体上で熱分解することにより、
被膜を得ることを特徴とする方法。(3) A method for producing a hydrogen generating cathode according to claim 1 or 2, wherein a solvent selected for dissolving together cobalt nitrate and chromium nitrate in solution form coated on a support is provided. The mixture of the two nitrates obtained on the support by removal is heated at 250° C. to 250° C. under an inert atmosphere.
By pyrolysis on the support at a temperature of 700°C,
A method characterized by obtaining a film.
膜で規定されたクロム濃度が該溶液中で認められるよう
な量となる各硝酸塩を含んでいることを特徴とする請求
項４に記載の方法。(4) The solution of the two nitrates applied to the support contains an amount of each nitrate such that a chromium concentration defined in the coating is observed in the solution. The method described in.
に塗布される当該両硝酸塩の溶液から溶媒が除去される
ことを特徴とする請求項３又は４に記載の方法。(5) The method according to claim 3 or 4, characterized in that the solvent is removed from the solution of both nitrates applied to the support without thermally decomposing the nitrates themselves.
求項３から５のいずれか一項に記載の方法。(6) A method according to any one of claims 3 to 5, characterized in that the solvent is removed by evaporation.
の混合物の中から選択されることを特徴とする請求項３
から６のいずれか一項に記載の方法。(7) Claim 3, characterized in that the solvent is selected from water, ethanol, and a mixture of water and ethanol.
6. The method according to any one of 6.
の熱分解が、窒素又はアルゴン雰囲気下で実施されるこ
とを特徴とする請求項３から７のいずれか一項に記載の
方法。(8) Process according to any one of claims 3 to 7, characterized in that the pyrolysis of the mixture of cobalt nitrate and chromium nitrate on the support is carried out under a nitrogen or argon atmosphere.
０℃より高い温度で実施されることを特徴とする請求項
３から８のいずれか一項に記載の方法。(9) Thermal decomposition of a mixture of two nitrates on a support is 30
9. Process according to any one of claims 3 to 8, characterized in that it is carried out at a temperature above 0<0>C.
する請求項９に記載の方法。(10) The method according to claim 9, wherein the temperature is 350°C to 500°C.
から該アルカリ金属の塩素酸塩への、又は塩素酸ナトリ
ウムのようなアルカリ金属の塩素酸塩から該アルカリ金
属の過塩素酸塩への水性媒体中での電解に対する、請求
項１又は２に記載の水素発生カソードの適用。(11) From an alkali metal chloride, such as sodium chloride, to an alkali metal chlorate, or from an alkali metal chlorate, such as sodium chlorate, to an alkali metal perchlorate in an aqueous medium. 3. Application of the hydrogen generating cathode according to claim 1 or 2 to electrolysis in.
ことを特徴とする請求項１１に記載の適用。(12) Application according to claim 11, characterized in that the electrolysis is carried out in an aqueous medium with a pH of 5 to 12.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8914334 | 1989-10-26 | ||
| FR8914334A FR2653786B1 (en) | 1989-10-26 | 1989-10-26 | HYDROGEN RELEASE CATHODE. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03240986A true JPH03240986A (en) | 1991-10-28 |
Family
ID=9386998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2286918A Pending JPH03240986A (en) | 1989-10-26 | 1990-10-24 | Hydrogen producing cathode |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0425395A1 (en) |
| JP (1) | JPH03240986A (en) |
| KR (1) | KR930001973B1 (en) |
| CN (1) | CN1051204A (en) |
| AU (1) | AU6556890A (en) |
| BR (1) | BR9005388A (en) |
| CA (1) | CA2028595A1 (en) |
| FI (1) | FI905274A0 (en) |
| FR (1) | FR2653786B1 (en) |
| IL (1) | IL95944A0 (en) |
| NO (1) | NO904628L (en) |
| NZ (1) | NZ235855A (en) |
| PT (1) | PT95694A (en) |
| ZA (1) | ZA908611B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100460102B1 (en) * | 2002-07-15 | 2004-12-03 | 한화석유화학 주식회사 | Method for preparing fine metal oxide particles |
| WO2011068743A2 (en) * | 2009-12-01 | 2011-06-09 | Wisconsin Alumni Research Foundation | Buffered cobalt oxide catalysts |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5620181A (en) * | 1979-06-29 | 1981-02-25 | Solvay | Cathode for hydrogen electrolytic manufacture |
| JPS6286187A (en) * | 1985-10-09 | 1987-04-20 | Asahi Chem Ind Co Ltd | Electrode for generating hydrogen |
| JPS62161975A (en) * | 1986-10-01 | 1987-07-17 | ペルメレック電極株式会社 | Electrode used in electrolytic cell and its production |
-
1989
- 1989-10-26 FR FR8914334A patent/FR2653786B1/en not_active Expired - Lifetime
-
1990
- 1990-10-10 IL IL95944A patent/IL95944A0/en unknown
- 1990-10-24 EP EP19900420459 patent/EP0425395A1/en not_active Ceased
- 1990-10-24 JP JP2286918A patent/JPH03240986A/en active Pending
- 1990-10-24 BR BR909005388A patent/BR9005388A/en unknown
- 1990-10-25 FI FI905274A patent/FI905274A0/en not_active IP Right Cessation
- 1990-10-25 NO NO90904628A patent/NO904628L/en unknown
- 1990-10-25 CA CA002028595A patent/CA2028595A1/en not_active Abandoned
- 1990-10-25 PT PT95694A patent/PT95694A/en not_active Application Discontinuation
- 1990-10-26 NZ NZ235855A patent/NZ235855A/en unknown
- 1990-10-26 AU AU65568/90A patent/AU6556890A/en not_active Abandoned
- 1990-10-26 KR KR1019900017253A patent/KR930001973B1/en not_active IP Right Cessation
- 1990-10-26 CN CN90108623A patent/CN1051204A/en active Pending
- 1990-10-26 ZA ZA908611A patent/ZA908611B/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5620181A (en) * | 1979-06-29 | 1981-02-25 | Solvay | Cathode for hydrogen electrolytic manufacture |
| JPS6286187A (en) * | 1985-10-09 | 1987-04-20 | Asahi Chem Ind Co Ltd | Electrode for generating hydrogen |
| JPS62161975A (en) * | 1986-10-01 | 1987-07-17 | ペルメレック電極株式会社 | Electrode used in electrolytic cell and its production |
Also Published As
| Publication number | Publication date |
|---|---|
| KR930001973B1 (en) | 1993-03-20 |
| CA2028595A1 (en) | 1991-04-27 |
| KR910008171A (en) | 1991-05-30 |
| NO904628D0 (en) | 1990-10-25 |
| EP0425395A1 (en) | 1991-05-02 |
| FR2653786A1 (en) | 1991-05-03 |
| PT95694A (en) | 1991-09-13 |
| CN1051204A (en) | 1991-05-08 |
| NZ235855A (en) | 1992-01-29 |
| FI905274A0 (en) | 1990-10-25 |
| NO904628L (en) | 1991-04-29 |
| IL95944A0 (en) | 1991-07-18 |
| BR9005388A (en) | 1991-09-17 |
| FR2653786B1 (en) | 1992-01-17 |
| AU6556890A (en) | 1991-05-02 |
| ZA908611B (en) | 1991-07-31 |
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