CN1051204A - hydrogen release cathode - Google Patents
hydrogen release cathode Download PDFInfo
- Publication number
- CN1051204A CN1051204A CN90108623A CN90108623A CN1051204A CN 1051204 A CN1051204 A CN 1051204A CN 90108623 A CN90108623 A CN 90108623A CN 90108623 A CN90108623 A CN 90108623A CN 1051204 A CN1051204 A CN 1051204A
- Authority
- CN
- China
- Prior art keywords
- coating
- chromium
- nitrate
- matrix
- cathode
- 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
Images
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)
- Automation & Control Theory (AREA)
- Inorganic Chemistry (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
一种释氢阴极，该阴极含有一层在电极基体上 的，由Co3O4和一种不同于Co3O4的化合物所共同 组成的涂层，根据X-射线衍射图形，该化合物被认 为是Co2CrO4，该化合物包含存在于涂层中的铬，所 述的铬的含量以涂层中铬的原子数目对铬与钴的原 子数目总和之比值来表示，所述铬的含量低于能引起 Co3O4从涂层中消失时所相应的铬含量。本发明还 包括所述阴极的制备方法和该阴极在电解中的用 途。A hydrogen-releasing cathode comprising a coating on an electrode substrate consisting of Co 3 O 4 and a compound other than Co 3 O 4 which, according to the X-ray diffraction pattern, is Considered to be Co 2 CrO 4 , this compound contains chromium present in the coating, said chromium content being expressed as the ratio of the number of chromium atoms in the coating to the sum of the atomic numbers of chromium and cobalt, said chromium content Below the corresponding chromium content that would cause Co 3 O 4 to disappear from the coating. The invention also includes the preparation method of the cathode and the use of the cathode in electrolysis.
Description
本发明涉及一种释氢阴极、它的制造方法及它在电解工艺中的应用。The invention relates to a hydrogen releasing cathode, its manufacturing method and its application in electrolysis process.
本发明所提供的这种阴极包含一个导电基体（在下文中将其简称为基体），在此基体上涂覆有一层其本身是导电的，由钴和铬两种金属的氧化物共同组成的涂层（在下文中将其简称为涂层）。按照本发明，以简单而价廉的方法制成的这种涂层能牢固地粘结在基体上并且具有低的释氢超电压，而且该阴极在电解时具有良好的操作稳定性。The cathode provided by the present invention comprises a conductive substrate (hereinafter referred to as the substrate for short), which is coated with a coating which is conductive in itself and composed of two metal oxides of cobalt and chromium. layer (hereinafter referred to simply as coating). According to the invention, the coating is produced in a simple and inexpensive manner, which adheres firmly to the substrate and has a low hydrogen evolution overvoltage, and the cathode has good operational stability during electrolysis.
欧洲专利申请公开EP-A-0，126，189指出，由于能源价格的不断上涨，从工业利益考虑，希望获得一种可将超额能耗减少到最低程度的阴极，而这种超额能耗与释氢的超电压直接有关。European Patent Application Publication EP-A-0, 126, 189 pointed out that due to the continuous rise of energy prices, it is desirable to obtain a cathode that can minimize excess energy consumption from the perspective of industrial interests, and this excess energy consumption is related to It is directly related to the overvoltage of hydrogen release.
该文件也指出，这个问题已在许多出版物中提出过。The paper also states that this issue has been raised in a number of publications.
本发明的主题是一种释氢阴极，在该阴极上的涂层含有一种铬化合物和一种选自镍和钴中至少一种金属的氧化物。按照从下列三种方法中选择的一种方法将所述涂层涂布在所述基体上，所述的三种方法是：将粉末状前体混合物于熔融状态下喷射;将溶解状态的前体混合物在一种氧化性的气氛中烧结;先进行电镀或化学镀，然后再在氧化性气氛中进行氧化煅烧。在将铬与另一种金属配合使用时，对这两种金属的配比所作的选择应使得铬与所述另一种金属产生特定比例的结合，并且，这种特定比例的结合形式与存在另一种金属时的结合形式没有什么不同。The subject of the invention is a hydrogen-releasing cathode on which the coating contains a chromium compound and an oxide of at least one metal selected from nickel and cobalt. The coating is applied to the substrate by one of the following three methods: spraying the powdered precursor mixture in a molten state; spraying the precursor mixture in a dissolved state; The body mixture is sintered in an oxidizing atmosphere; electroplating or electroless plating is performed first, and then oxidized and calcined in an oxidizing atmosphere. When chromium is used in combination with another metal, the ratio of the two metals should be selected such that chromium is combined with the other metal in a specific ratio, and the specific ratio of the combined form and the presence of The binding form is no different when another metal is used.
本发明的释氢阴极的特征在于，钴在涂层中的存在形式，既有氧化物Co3O4，又有一种不同于Co3O4的，按X-射线衍射图可认为是Co2CrO4的化合物，这种化合物包含了存在于涂层中的铬，涂层中的铬含量以铬原子数目对铬与钴原子数目的总和之比值来表示，在所述涂层中的铬含量低于可引起Co3O4在涂层中消失时所相应的铬含量。The hydrogen release cathode of the present invention is characterized in that the existing form of cobalt in the coating includes oxide Co 3 O 4 , and another type different from Co 3 O 4 , which can be considered as Co 2 according to the X-ray diffraction pattern. The compound of CrO4 , which contains chromium present in the coating, the chromium content in the coating is expressed as the ratio of the number of chromium atoms to the sum of the number of chromium and cobalt atoms, the chromium content in the coating Below the corresponding chromium content that would cause Co 3 O 4 to disappear in the coating.
这样限定的阴极的制造方法的特征在于，阴极上的涂层是对处于阴极基体上由硝酸钴和硝酸铬所组成的混合物进行热分解而制得的，所说热分解在惰性气氛（例如氮或氩）中进行，热分解温度在250℃至700℃之间，在多数情况下高于约300℃，而较佳的温度在约350℃至500℃之间，所述处于基体上的混合物的制备方法是首先选择一种能同时溶解硝酸钴和硝酸铬的溶剂，将这两种硝酸盐溶解，将所获溶液涂覆到所述基体上，然后将所述溶剂除去。The manufacturing method of the cathode thus defined is characterized in that the coating on the cathode is obtained by thermally decomposing a mixture of cobalt nitrate and chromium nitrate on the cathode substrate, said thermal decomposition being carried out in an inert atmosphere (such as nitrogen or argon), the thermal decomposition temperature is between 250°C and 700°C, in most cases above about 300°C, and the preferred temperature is between about 350°C and 500°C, the mixture on the substrate The preparation method is to firstly select a solvent capable of simultaneously dissolving cobalt nitrate and chromium nitrate, dissolve the two nitrates, apply the obtained solution on the substrate, and then remove the solvent.
本发明的阴极可用于在含水介质中的电解（电解所用条件除另有说明外皆是众所周知的），例如用于碱金属氯化物水溶液的电解以制备所述金属的氯酸盐，例如由氯化钠制备氯酸钠，或者用于碱金属氯酸盐水溶液的电解以制备所述金属的高氯酸盐，例如由氯酸钠制备高氯酸钠。本发明的阴极在由所述氯化物、氯酸盐或高氯酸盐所组成的电解液中进行电解时，可以使用酸性的、中性的或者碱性的介质，但介质的较佳pH值在大约5至12之间。The cathode according to the invention can be used for electrolysis in an aqueous medium (under which conditions are well known unless otherwise stated), for example for the electrolysis of an aqueous solution of an alkali metal chloride to prepare the chlorate of said metal, for example from chlorine Sodium chloride is used to prepare sodium chlorate, or is used in the electrolysis of alkali metal chlorate aqueous solution to prepare the perchlorate of said metal, such as preparing sodium perchlorate from sodium chlorate. When the cathode of the present invention is electrolyzed in an electrolyte composed of said chloride, chlorate or perchlorate, acidic, neutral or alkaline media can be used, but the preferred pH value of the media Between about 5 and 12.
除另有说明或其他显而易见的情况以外，上述的本发明的三个目的和/或在下文中所述的内容可以概括如下：Except for otherwise stated or other obvious situations, the above-mentioned three purposes of the present invention and/or the content described hereinafter can be summarized as follows:
-铬原子数目对钴和铬原子数目总和的比值以百分数表示，下文把该比值称为铬含量，- the ratio of the number of chromium atoms to the sum of the number of cobalt and chromium atoms, hereinafter referred to as the chromium content, expressed as a percentage,
-该化合物可认为是Co2CrO4，这句话的含义是指在用X-射线衍射法或用电子显微镜法对基体上的涂层进行鉴定时，发现该化合物不同于Co3O4，- the compound may be considered to be Co 2 CrO 4 , which means that the compound is found to be different from Co 3 O 4 when the coating on the substrate is identified by X-ray diffraction or by electron microscopy,
-Co3O4已经消失，这句话的含义是指在用X-射线衍射法对基体上的涂层进行鉴定时不能再检出Co3O4，-Co 3 O 4 has disappeared, the meaning of this sentence is that Co 3 O 4 can no longer be detected when the coating on the substrate is identified by X-ray diffraction method,
-所用的硝酸铬和硝酸钴通常是水合结晶盐的形式，例如Co（NO3）2·6H2O和Cr（NO3）3·9H2O的形式，首先用它们制成同时含有这两种盐的溶液，然后将此溶液涂覆到基体上。这两种硝酸盐用量的相对比例应保证所获的溶液能使最后涂层中的铬浓度符合于所要求的数值，- The chromium nitrate and cobalt nitrate used are generally in the form of hydrated crystalline salts, such as Co(NO 3 ) 2 6H 2 O and Cr(NO 3 ) 3 9H 2 O, which are first prepared containing both A solution of the salt is then applied to the substrate. The relative proportions of these two nitrates should ensure that the solution obtained can make the chromium concentration in the final coating comply with the required value,
-为了制成同时含有这两种硝酸盐的溶液，对所选择的溶剂的性质要求并不严格，其条件是，该溶剂对这两种硝酸盐只起一种溶剂的作用，该溶剂对这两种硝酸盐都必须是中性的，而且，在将所获溶液涂覆到基体上以后，溶液中的溶剂可以通过蒸发等方法除去而不会导致硝酸盐的热分解（部分的结晶水挥发除外），也就是说不会导致硝酸盐的分解;所说的溶剂可以是，例如水或醇类，如乙醇，或者是一种醇-水溶液，例如95°的乙醇，- In order to prepare a solution containing both nitrates, the nature of the solvent chosen is not critical, provided that the solvent acts only as a solvent for the two nitrates, the solvent acts as a solvent for the two nitrates Both nitrates must be neutral, and after the obtained solution is applied to the substrate, the solvent in the solution can be removed by evaporation and other methods without causing thermal decomposition of the nitrate (part of the crystal water volatilization Except), that is to say, it will not lead to the decomposition of nitrates; said solvent can be, for example, water or alcohols, such as ethanol, or an alcohol-water solution, such as 95° ethanol,
-在基体上涂覆溶液的操作可在所说基体的两个表面或一个表面上的全部表面或一部分表面上进行，例如可用刷子涂抹的方法，也可用喷射或浸涂的方法，- the operation of applying the solution on the substrate can be carried out on both surfaces of said substrate or on all or part of one surface, for example by brushing, by spraying or dipping,
-为了获得符合于本发明的涂层，对所述两种硝酸盐进行热分解处理的时间主要取决于热处理所选的温度;热分解所需时间通常在约5分钟至2小时之间，大多数情况下在约0.5小时至1小时之间，- In order to obtain a coating according to the invention, the time for the thermal decomposition treatment of the two nitrates depends mainly on the temperature selected for the thermal treatment; the time required for thermal decomposition is usually between about 5 minutes and 2 hours, approximately Between about 0.5 hour and 1 hour in most cases,
-在基体上的涂层的最终厚度可以在较宽范围内变化，例如可在约1μm至300μm之间变化;在实际操作中可在基体上连续多次涂覆所述硝酸盐溶液来达到所需最终厚度，涂覆的次数特别地要随所述溶液中的硝酸盐浓度而定，每一次后续的涂覆操作都必须在除去溶剂之后并在进行热处理之后进行，或者仅仅在除去溶剂之后进行，合乎要求的热处理只是在最后才进行。- the final thickness of the coating on the substrate can vary in a wide range, for example between about 1 μm and 300 μm; The final thickness is required, the number of coatings depends especially on the nitrate concentration in the solution, each subsequent coating operation must be carried out after the solvent has been removed and after the heat treatment, or only after the solvent has been removed , the required heat treatment is only carried out at the end.
用于本发明阴极的基体是通常用于释氢阴极的基体;例如，该基体可以是铁，或者较佳是低碳钢或不锈钢，镍或钛;上面提到的欧洲专利申请Ep-A-0，126，189叙述了对原始状态的基体应进行的一些预处理，对本发明同样适用。The substrate used for the cathode of the present invention is a substrate conventionally used for hydrogen-releasing cathodes; for example, the substrate may be iron, or preferably mild steel or stainless steel, nickel or titanium; the above-mentioned European patent application Ep-A- 0, 126, 189 describe some pretreatments that should be carried out to the substrate in the original state, which is also applicable to the present invention.
除了用X-射线衍射分析外，还用电子能谱化学分析法（ESCA）和电子显微镜法进行鉴定，以判别究竟什么特征属于本发明的基体的涂层所显示的特征，或者什么特征不属于本发明的这种特征。In addition to X-ray diffraction analysis, electron spectrochemical analysis (ESCA) and electron microscopy are also used to identify which features are exhibited by the coating of the substrate of the present invention, or which features are not. This feature of the present invention.
对所述的涂层，已经有可能作出如下的判断：For the coatings described, it has been possible to make the following judgments:
-既不存在可测出的金属铬，也不存在可测出的氧化铬Cr2O3，- neither detectable metallic chromium nor detectable chromium oxide Cr 2 O 3 is present,
-一种具有Co2CrO4的外观，并且是包含了涂层中所有的铬在内的化合物，其本身很可能就是Co2CrO4，- a compound that has the appearance of Co 2 CrO 4 and contains all the chromium in the coating, which itself is probably Co 2 CrO 4 ,
-涂层的组织特殊，并且与按本发明的方法但单独用硝酸钴作为起始原料时所制得的涂层有显著不同;根据本发明的涂层所具有的表面显示出好得多的均质性和连续性。- the structure of the coating is special and significantly different from the coating produced by the method of the invention but using cobalt nitrate alone as a starting material; the coating according to the invention has a surface that shows much better homogeneity and continuity.
-铬的浓度需控制在不会导致Co3O4从涂层中消失所相应的铬浓度以下，该浓度通常约为30%。- The concentration of chromium needs to be controlled below the corresponding chromium concentration which does not cause the disappearance of Co 3 O 4 from the coating, which is usually about 30%.
在图1、2和3中所复制的电子显微镜照片分别示出了上面刚谈到的有关涂层的表面状态。The electron micrographs reproduced in Figures 1, 2 and 3 respectively show the surface state of the coating concerned immediately above.
图1是对处于本发明的阴极基体上，铬浓度等于0.5%的涂层表面放大2000倍的电子显微照片，该涂层是按本发明的方法来制备的，即以Co（NO3）2·6H2O或Cr（NO3）3·9H2O为起始原料，用95°的乙醇作为溶剂，在400℃下和在氮气流中将基体上的硝酸盐热分解0.5小时，这样反复地进行把硝酸盐溶液涂覆到所述基体上，使溶液蒸发和使涂层热分解这几个步骤，直到获得所需的涂层厚度为止。Fig. 1 is to be on the cathode base body of the present invention, the electron micrograph that chromium concentration is equal to 0.5% coating surface magnifies 2000 times, and this coating is prepared by the method of the present invention, namely with Co (NO 3 ) 2 · 6H 2 O or Cr (NO 3 ) 3 · 9H 2 O as the starting material, using 95 ° ethanol as the solvent, thermally decompose the nitrate on the substrate at 400 ° C and in nitrogen flow for 0.5 hours, so that The steps of applying the nitrate solution to the substrate, evaporating the solution and thermally decomposing the coating are repeated until the desired coating thickness is obtained.
图2是对基体上铬浓度等于19.5%的涂层表面放大2000倍的电子显微照片，有关涂层的其他条件与对图1的解释中所述的条件相同。Figure 2 is an electron micrograph at 2000X magnification of the surface of a coating with a chromium concentration equal to 19.5% on a substrate, the other conditions concerning the coating being the same as those described in the explanation of Figure 1.
图3作为对比用，它示出了对铬浓度等于零的涂层表面放大2000倍的电子显微照片，在制备此涂层时仅仅使用了Co（NO3）2·6H2O作为硝酸盐，除此以外，对图1和图2的涂层制备过程中的条件也适用于图3中的涂层。Figure 3, for comparison, shows an electron micrograph at 2000X magnification of the surface of a coating with a chromium concentration equal to zero, in the preparation of which only Co(NO 3 ) 2 ·6H 2 O was used as nitrate, In addition, the conditions in the coating preparation process of Fig. 1 and Fig. 2 are also applicable to the coating in Fig. 3.
在上述的所有三种情况中，所用的基体皆为实心的低碳钢钢板，首先对其进行除油和刚玉抛光处理，然后再在此基体上进行涂覆操作，每种情况下所制的涂层皆取相同的厚度。In all three cases above, the substrate used was a solid mild steel plate, which was first degreased and corundum polished before the coating operation was carried out on this substrate, and in each case the produced The coatings are all of the same thickness.
所有阴极（不管它是否属于本发明的阴极）的特征，也就是指在它表面上的涂层的电化学特征皆以释氢的电活性来表示，而释氢电活性是以相对于饱和甘汞电极（以SCE表示）的极化电位（20A/dm2）来量度，在所用的电解液中，除水以外，还含有NaCl 120g/升，NaClO3580g/升和Na2Cr2O76g/升，电解液的pH值为6.5，温度为65℃，在测量极化电位时使用一根鲁金毛细管，众所周知，该毛细管的作用是避免在测量时发生欧姆值的下降。The characteristics of all cathodes (whether or not they belong to the cathode of the present invention), that is to say, the electrochemical characteristics of the coating on its surface, are expressed in terms of the electrical activity of hydrogen release, which is expressed relative to saturated gamma Measured by the polarization potential (20A/dm 2 ) of a mercury electrode (expressed as SCE), in the electrolyte used, in addition to water, it also contains NaCl 120g/liter, NaClO 3 580g/liter and Na 2 Cr 2 O 7 6g/liter, the pH value of the electrolyte is 6.5, and the temperature is 65°C. A Lukin capillary is used when measuring the polarization potential. As we all know, the function of this capillary is to avoid the decrease of the ohm value during the measurement.
将所获的测量结果以表示但非限定的方式列于下面的表1中，这些结果说明了本发明的优点。在阴极3的情况，为了对比起见，使铬浓度等于0%，因为在制备该阴极的涂层时只用了硝酸钴作为硝酸盐，这一点已在图3的文字解释中作了说明。在阴极4的情况，也是作为一种对比的方法，没有示出铬的浓度，因为所述的基体是以其原始的状态作为阴极使用。对于阴极7的情况，按照本发明的方法在阴极上连续涂覆了很多次，但为了对比起见，使铬的浓度高于可使Co3O4在涂层中消失所相应的铬浓度。电极1、2、5和6则是完全按照本发明的方法制备的。在所有的情况，对于涂覆到基体上的涂层来说，每次所获的涂层厚度皆相同。The results of the measurements obtained, which illustrate the advantages of the present invention, are presented in Table 1 below in an indicative but not limiting manner. In the case of cathode 3, the chromium concentration was made equal to 0% for comparison, since only cobalt nitrate was used as nitrate in the preparation of the coating of this cathode, as explained in the textual explanation of FIG. 3 . In the case of cathode 4 , also as a way of comparison, the chromium concentration is not shown, since the substrate is used in its original state as cathode. In the case of cathode 7, the cathode was coated several times in succession according to the method of the invention, but for comparison, the chromium concentration was higher than that corresponding to the disappearance of Co3O4 in the coating. Electrodes 1, 2, 5 and 6 were prepared completely according to the method of the present invention. In all cases, the same coating thickness was obtained each time for the coating applied to the substrate.
表1释氢阴极的电化学特征 Table 1 Electrochemical characteristics of hydrogen releasing cathode
Claims (12)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8914334A FR2653786B1 (en) | 1989-10-26 | 1989-10-26 | HYDROGEN RELEASE CATHODE. |
| FR8914334 | 1989-10-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1051204A true CN1051204A (en) | 1991-05-08 |
Family
ID=9386998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90108623A Pending CN1051204A (en) | 1989-10-26 | 1990-10-26 | hydrogen release 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) | FI905274A7 (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 |
| JP2013512349A (en) * | 2009-12-01 | 2013-04-11 | ウイスコンシン アラムナイ リサーチ ファウンデーシヨン | Buffered cobalt oxide catalyst |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2460343A1 (en) * | 1979-06-29 | 1981-01-23 | Solvay | CATHODE FOR THE ELECTROLYTIC PRODUCTION OF HYDROGEN |
| JPS6286187A (en) * | 1985-10-09 | 1987-04-20 | Asahi Chem Ind Co Ltd | Electrode for hydrogen generation |
| 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/FI905274A7/en not_active IP Right Cessation
- 1990-10-25 NO NO90904628A patent/NO904628L/en unknown
- 1990-10-25 PT PT95694A patent/PT95694A/en not_active Application Discontinuation
- 1990-10-25 CA CA002028595A patent/CA2028595A1/en not_active Abandoned
- 1990-10-26 CN CN90108623A patent/CN1051204A/en active Pending
- 1990-10-26 ZA ZA908611A patent/ZA908611B/en unknown
- 1990-10-26 KR KR1019900017253A patent/KR930001973B1/en not_active Expired - Fee Related
- 1990-10-26 NZ NZ235855A patent/NZ235855A/en unknown
- 1990-10-26 AU AU65568/90A patent/AU6556890A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| NZ235855A (en) | 1992-01-29 |
| FR2653786B1 (en) | 1992-01-17 |
| FI905274A7 (en) | 1991-04-27 |
| NO904628D0 (en) | 1990-10-25 |
| KR930001973B1 (en) | 1993-03-20 |
| EP0425395A1 (en) | 1991-05-02 |
| AU6556890A (en) | 1991-05-02 |
| IL95944A0 (en) | 1991-07-18 |
| FR2653786A1 (en) | 1991-05-03 |
| BR9005388A (en) | 1991-09-17 |
| KR910008171A (en) | 1991-05-30 |
| CA2028595A1 (en) | 1991-04-27 |
| FI905274A0 (en) | 1990-10-25 |
| NO904628L (en) | 1991-04-29 |
| ZA908611B (en) | 1991-07-31 |
| PT95694A (en) | 1991-09-13 |
| JPH03240986A (en) | 1991-10-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wen et al. | Hydrogen and Oxygen Evolutions on Ru‐Ir Binary Oxides | |
| JP3188361B2 (en) | Chrome plating method | |
| TWI224632B (en) | Method of producing copper foil | |
| Gamboa et al. | Evaluation of the corrosion resistance of Ni–Co–B coatings in simulated PEMFC environment | |
| MXPA01003960A (en) | Cathode for electrolysing aqueous solutions. | |
| Danilov et al. | Electrodeposition of Ni–Fe alloy from a choline chloride-containing ionic liquid | |
| JP2574699B2 (en) | Oxygen generating anode and its manufacturing method | |
| CA1256057A (en) | Process for electrolytic treatment of metal by liquid power feeding | |
| CA2043423A1 (en) | Electrocatalytic cathodes and methods of preparation | |
| CN1051204A (en) | hydrogen release cathode | |
| JPS6017086A (en) | Cathode for aqueous solution electrolysis | |
| US5948223A (en) | Low hydrogen overvoltage cathode and process for the production thereof | |
| JPH0499294A (en) | Oxygen generating anode and its production | |
| JPH0774470B2 (en) | Manufacturing method of anode for oxygen generation | |
| JP3676554B2 (en) | Activated cathode | |
| JPS58500617A (en) | Cathode and bipolar electrodes | |
| JP3358465B2 (en) | Low hydrogen overvoltage cathode and method of manufacturing the same | |
| EP0328128B1 (en) | Process concerning the adhesion between metallic materials and galvanic aluminium layers and the non-aqueous electrolyte used therein | |
| JP2722263B2 (en) | Electrode for electrolysis and method for producing the same | |
| JP3463966B2 (en) | Manufacturing method of electrode for electrolysis | |
| JP3941898B2 (en) | Activated cathode and method for producing the same | |
| JP3723898B2 (en) | Low hydrogen overvoltage cathode | |
| KR100635300B1 (en) | Manufacturing Method of Crystalline Molybdenum-Cobalt Alloy Thin Film by Electrodeposition | |
| JP3658823B2 (en) | Electrode for electrolysis and method for producing the same | |
| JPH0631455B2 (en) | Oxygen generating anode and its manufacturing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |