US20130153411A1 - Electrode base, negative electrode for aqueous solution electrolysis using same, method for producing the electrode base, and method for producing the negative electrode for aqueous solution electrolysis - Google Patents

Electrode base, negative electrode for aqueous solution electrolysis using same, method for producing the electrode base, and method for producing the negative electrode for aqueous solution electrolysis Download PDF

Info

Publication number
US20130153411A1
US20130153411A1 US13/579,092 US201113579092A US2013153411A1 US 20130153411 A1 US20130153411 A1 US 20130153411A1 US 201113579092 A US201113579092 A US 201113579092A US 2013153411 A1 US2013153411 A1 US 2013153411A1
Authority
US
United States
Prior art keywords
nickel
electrode
catalyst layer
negative electrode
aqueous solution
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.)
Abandoned
Application number
US13/579,092
Other languages
English (en)
Inventor
Sanae Ishimaru
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
De Nora Permelec Ltd
Original Assignee
Chlorine Engineers Corp Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Chlorine Engineers Corp Ltd filed Critical Chlorine Engineers Corp Ltd
Assigned to CHLORINE ENGINEERS CORP., LTD. reassignment CHLORINE ENGINEERS CORP., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ISHIMARU, SANAE
Publication of US20130153411A1 publication Critical patent/US20130153411A1/en
Assigned to PERMELEC ELECTRODE LTD. reassignment PERMELEC ELECTRODE LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHLORINE ENGINEERS CORP., LTD.
Abandoned legal-status Critical Current

Links

Images

Classifications

    • C25B11/0478—
    • 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

Definitions

  • the present invention relates to an electrode base used in an electrode for aqueous solution electrolysis.
  • the present invention relates to a negative electrode for aqueous solution electrolysis in which an electrode catalyst layer is formed on the electrode base and which is preferably used as a negative electrode for electrolysis of an aqueous solution of an alkali metal halide, and a production method thereof.
  • Negative electrodes for aqueous solution electrolysis having a low hydrogen overvoltage and a long operating life have been proposed as a negative electrode for aqueous solution electrolysis used in an aqueous solution electrolysis, which are obtained by forming, on a base made of nickel, an electrode catalyst layer including a platinum group metal or metal oxide, or an electrode catalyst layer including a rare earth metal such as a lanthanum or its compound and a platinum group metal.
  • These negative electrodes for aqueous solution electrolysis have a low hydrogen overvoltage, and a feature in which they have smoother surfaces of the electrode catalyst layer than that of conventional electrodes having particulate substances deposited on the surface, and thus damage caused by repetitive contact with an ion-exchange membrane can be prevented even if the electrolysis is performed with the ion-exchange membrane being in close contact with the electrode.
  • the metal nickel which is used as the base of the negative electrode for aqueous solution electrolysis, is brought into contact with the electrode catalyst layer showing a more noble potential than the nickel, the nickel base is easily corroded due to galvanic corrosion during a downtime of electrolysis or exposure to the atmosphere.
  • a electrolytic cell is assembled from negative electrodes, positive electrodes and ion-exchange membranes and then the cell is stored in a state in which an electrolytic solution is not filled in the electrolytic cell, nickel ions generated by corrosion of the nickel base, which is caused by contact of the negative electrode with the ion-exchange membrane, permeate into the ion-exchange membrane to cause a phenomenon that the ions are deposited in the ion-exchange membrane as a nickel compound, which leads to deterioration of properties of the ion-exchange membrane and thus sometimes to a rise of an electrolysis voltage and a decrease in current efficiency.
  • a method for producing a negative electrode in which a nickel substrate surface is heated and baked at a temperature of 350 to 550° C. for 5 to 60 minutes to form an intermediate layer including a nickel oxide as a main component on the conductive base surface (see, for example, Patent Document 1).
  • the document describes that according to this method, the adhesion is strong because the intermediate layer and the base are formed from an originally integral material, and therefore peeling-off or lacking of the intermediate layer is not caused.
  • Patent Document 1 The negative electrode described in Patent Document 1 seems that elution of the nickel component from the electrode base can be prevented. However, the document also describes that the cell voltage is risen after the electrolysis is started and then the electrolytic cell operation is shutdown.
  • the electrode described in Patent Document 2 has superior electrolysis properties to those of similar kinds of conventional electrodes, but resistance to reverse current is required to be more sufficient at emergency shutdown of the electrolytic cell operation, and the like.
  • the present invention aims to provide an negative electrode for aqueous solution electrolysis whose electrode base is a conductive substrate having nickel on its surface, which prevents elusion of nickel from the electrode base, prevents elusion of nickel from the negative electrode base during storage of an electrolytic cell integrally assembled from three components of a positive electrode, an ion-exchange membrane and the negative electrode in the atmosphere or suspension of the electrolytic cell operation, and is little affected by a reverse current generated at the time of emergency shutdown of the electrolytic cell operation.
  • the present invention also aims to provide a negative electrode for aqueous solution electrolysis, having a low electrolytic cell voltage at the start of initial operation as well as at re-start of operation after shutdown of the electrolytic cell.
  • the present invention has the following constitution features [1] to [15].
  • An electrode base including a mixture layer including metal nickel, a nickel oxide and carbon atoms, formed on a surface of a conductive substrate having a nickel surface.
  • a negative electrode for aqueous solution electrolysis including:
  • a conductive substrate having a nickel surface; a mixture layer including metal nickel, a nickel oxide and carbon atoms, formed on the surface of the conductive substrate; and an electrode catalyst layer including a platinum group metal or a platinum group metal compound, formed on a surface of the mixture layer.
  • the negative electrode for aqueous solution electrolysis according to the item 5 above, wherein the electrode catalyst layer is formed by thermally decomposing an electrode catalyst layer-forming solution including a ruthenium nitrate and a lanthanum acetate at 400° C. to 600° C. in an atmosphere containing oxygen.
  • a method for producing an electrode base including the steps of:
  • a nickel compound including a nickel atom, a carbon atom, an oxygen atom and a hydrogen atom to a surface of a conductive substrate having a nickel surface; and performing thermal decomposition at 250° C. to 600° C. in an atmosphere containing oxygen, thereby forming a mixture layer including metal nickel, a nickel oxide and carbon atoms.
  • a method for producing a negative electrode for aqueous solution electrolysis including the steps of:
  • an electrode base by applying a nickel compound including a nickel atom, a carbon atom, an oxygen atom and a hydrogen atom to a surface of a conductive substrate having a nickel surface, and performing thermal decomposition at 250° C. to 600° C. in an atmosphere containing oxygen, thereby forming a mixture layer including metal nickel, a nickel oxide and carbon atoms; and forming an electrode catalyst layer by applying an electrode catalyst layer-forming solution including a platinum group metal compound to a surface of the mixture layer of the electrode base, and performing thermal decomposition in an atmosphere containing oxygen.
  • the electrode base of the present invention is one in which a mixture layer including metal nickel, a nickel oxide and carbon is formed on a conductive substrate having nickel on its surface by thermal decomposition of a nickel compound composed of nickel atoms, carbon atoms, oxygen atoms and hydrogen atoms such as a nickel carboxylate at a low temperature. Due to the presence of the mixture layer, even if a reverse current flows to a negative electrode in a case of, for example, emergency shutdown of electrolytic cell operation, nickel does not elute from the nickel substrate to deposit in an ion-exchange membrane. In addition, due to the presence of the mixture layer, corrosion resistance of the conductive substrate is enhanced and also adhesion between the conductive substrate and the electrode catalyst layer is increased.
  • an initial potential stability is high when electrolysis is started, the electrolysis can be stably operated right from the beginning, and a negative electrode for aqueous solution electrolysis having a small hydrogen overvoltage can be provided.
  • the effects described above is more extensive when the mixture layer is formed by thermal decomposition of a nickel carboxylate as typified by nickel formate or nickel acetate at a low temperature.
  • FIG. 1 is a diagram showing results of anodic polarization tests of a negative electrode of the present invention.
  • FIG. 2 is a diagram showing change in a negative electrode potential in one Example of the present invention.
  • FIG. 3 is a diagram showing change in a negative electrode potential in another Example of the present invention.
  • FIG. 4 is a diagram showing change in a negative electrode potential in still another Example of the present invention.
  • FIG. 5 is a diagram showing change in a negative electrode potential in still another Example of the present invention.
  • the electrode base of the present invention is one in which a mixture layer including metal nickel, a nickel oxide and carbon atoms is provided on a surface of a conductive substrate having a nickel surface.
  • the electrode base of the present invention has the mixture layer including the metal nickel, nickel oxide and carbon atoms on the conductive substrate having the nickel surface, and therefore the electrode base has an advantage in which it is not broken even at the time of occurrence of anodic polarization, which is caused by reverse current occurring when electrolytic power is urgently stopped during electrolytic cell operation to shut down the operation, and after the electricity is turned on again, the operation can be performed just as the operation was performed before it was shutdown.
  • the conductive substrate having a nickel surface refers to nickel, or one in which a nickel layer is formed on a surface of a conductive material such as stainless steel, iron or copper by plating or cladding.
  • the mixture layer is a layer in which the metal nickel, the nickel oxide and the carbon atoms exist in a mixed state, from its analysis results. Though the reason why excellent properties can be obtained by providing such a mixture layer is not clear, it can be considered that the mixture layer has a good adhesion with the nickel surface of the conductive base, it has corrosion resistance even if it is subjected to an anodic polarization, and it suppresses a corrosion reaction with the conductive substrate surface.
  • the electrode base of the present invention may be produced by, for example, a method shown below.
  • the nickel compound composed of nickel atoms, carbon atoms, oxygen atoms and hydrogen atoms is applied to the surface of the conductive substrate having the nickel surface, and the resulting substrate is baked in an atmosphere containing oxygen, for example, in the atmosphere.
  • the mixture layer including the metal nickel, the nickel oxide and the carbon atoms can be formed.
  • the nickel compound can be applied to the conductive substrate surface by, for example, coating the surface with a coating solution including the nickel compound.
  • Organic acid salts of nickel can also be used as the nickel compound, and nickel carboxylates as typified by nickel formate and nickel acetate are particularly preferably used.
  • the mixture layer is preferably baked at a temperature of 250° C. to 600° C., and more preferably 250° C. to 500° C.
  • the baking time is preferably from 5 minutes to 60 minutes, and more preferably from 5 minutes to 30 minutes.
  • the thermal decomposition reaction of the nickel carboxylates such as nickel formate and nickel acetate can proceed at a lower temperature compared with the reaction of inorganic salts such as nickel nitrate and nickel sulfate, and the nickel surface of the base is not seemingly affected, because acidic gases capable of causing metal corrosion such as nitrogen oxides and sulfur oxides are not generated upon the baking.
  • the method has features that a special removing facility is not necessary for gases exhausted from a furnace and a working environment is good.
  • the thickness of the mixture layer is, accordingly, preferably from 0.001 ⁇ m to 1 ⁇ m.
  • the negative electrode for aqueous solution electrolysis of the present invention is one in which an electrode catalyst layer is formed on the mixture layer surface of the electrode base.
  • the electrode catalyst layer is formed of a layer including a platinum group metal or platinum group metal compound, and preferably a layer including the platinum group metal or platinum group metal compound, and a lanthanoid compound.
  • the components forming the electrode catalyst layer i.e., the platinum group component including the platinum group metal or platinum group metal compound, and the lanthanoid component including the lanthanoid compound, have a low hydrogen overvoltage and a high resistance as a negative electrode used in an ion-exchange membrane electrolysis of a brine.
  • the negative electrode for aqueous solution electrolysis of the present invention owing to the mixture layer of the electrode base, the elution of the nickel from the nickel substrate can be prevented, the potential stability can be improved upon the start-up of the passage of electric current through the electrolytic cell, and the deterioration of the electrode caused by a reverse current can be effectively prevented when the electrolytic cell operation is suddenly shutdown.
  • the deterioration of the electrolytic cell can be effectively prevented during storage thereof before an electric current is passed through the electrolytic cell.
  • the negative electrode for aqueous solution electrolysis in which the electrode catalyst layer including the platinum group metal or platinum group metal compound, and the lanthanoid compound is formed furthermore shows the properties.
  • the negative electrode for aqueous solution electrolysis of the present invention can be produced by, for example, a method described below.
  • the electrode base was produced in the same manner as described above. Then, the electrode catalyst layer is formed on the mixture layer surface of the electrode base.
  • the electrode catalyst layer can be formed by application of an electrode catalyst-forming solution in which the platinum group metal or platinum group metal compound, and optionally the lanthanoid compound are dissolved or dispersed, and then thermal decomposition in an atmosphere containing oxygen.
  • the elements of the platinum group may include platinum, palladium, ruthenium, iridium, and the like.
  • platinum it is preferable to dissolve it in the electrode catalyst layer-forming solution as a dinitrodiammine platinum salt
  • the ruthenium it is preferable to dissolved it in the electrode catalyst layer-forming solution as a ruthenium nitrate.
  • the use of a compound including no chlorine enables prevention of a negative influence on the mixture layer and the conductive substrate upon the formation of the electrode catalyst layer.
  • the lanthanoid elements may include lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium having an atomic number of 57 to 71, and the like.
  • the lanthanum and cerium are preferably used.
  • calboxylic acid salts thereof such as lanthanum acetate are preferably used, and when the cerium is used, cerium nitrate is preferably used.
  • the atomic ratio of the platinum group atoms to the lanthanoid atoms is preferably from 30/70 to 90/10 in the electrode catalyst layer-forming solution.
  • the electrode catalyst layer is formed by applying the electrode catalyst layer-forming solution to the mixture layer surface of the electrode base, and drying and baking (thermal decomposition) it.
  • the thickness may be controlled by repeating the procedure of applying, drying and baking several times.
  • the electrode catalyst layer-forming solution applied is dried at 60 to 80° C. for 10 to 20 minutes, and it is baked at a temperature of 400 to 600° C. for 10 to 20 minutes in an atmosphere containing oxygen.
  • the thickness of the electrode catalyst layer formed is preferably from 3 to 6 ⁇ m.
  • the thus formed electrode catalyst layer has a high catalytic activity in a hydrogen generation reaction as a negative electrode for aqueous solution electrolysis, and can maintain a hydrogen overvoltage low for a long time when electrolysis is performed at not only a low current density but also a high current density.
  • the negative electrode surface has a good current uniformity, and the ion-exchange membrane can be prevented from the contamination with the heavy metals, even if the electrolysis is performed with the ion-exchange membrane being in contact with the negative electrode.
  • the electrode catalyst layer can be prevented from the deterioration due to oxidation and the like, even if the negative electrode is exposed to the atmosphere.
  • the electrode catalyst layer formed by applying the electrode catalyst layer-forming solution to the electrode base, and then performing the thermal decomposition in the atmosphere containing oxygen does not include chlorine compounds as a component other than the metals forming the metal compound which forms the electrode catalyst layer, and therefore, it can be thought that any negative influence is not exerted on the conductive base, the mixture layer and the electrode catalyst layer.
  • the electrode catalyst layer formed has a chlorine compound. It is preferable to use salts from which chlorine compounds are not generated such as ruthenium nitrate as in the present invention.
  • the lanthanoid carboxylate when used together with the ruthenium component, it is preferable to use at least one lanthanum carboxylate selected from the group consisting of, for example, lanthanum acetate, lanthanum formate and lanthanum oxalate, and more preferably lanthanum acetate having a high solubility.
  • an oxycarbonate or carbonate may be generated from the lanthanum carboxylate in the thermal decomposition step forming the electrode catalyst layer in an atmosphere containing oxygen having a temperature of 400 to 600° C.
  • the electrode properties of the negative electrode for aqueous solution electrolysis of the present invention are not deteriorated even if the electrolytic cell operation is shutdown, the electrode is taken out from the electrolytic cell, exposed to the atmosphere, and put in the electrolytic cell again, and then the operation is resumed.
  • This may show that the properties of the electrode catalyst layer formed from the ruthenium nitrate and the lanthanum carboxylate are not changed in the atmosphere, and the conductive substrate of the electrode is covered with the dense mixture layer and electrode catalyst layer.
  • the electrode catalyst layer-forming solution which is used for forming the electrode catalyst layer, may be added a component including a platinum compound having no chlorine atom in addition to the ruthenium compound and the lanthanum carboxylate, whereby the platinum may be contained in the electrode catalyst layer.
  • the atomic ratio of Pt/La in the electrode catalyst layer-forming solution is preferably 0.005 or more. When the ratio is less than 0.005, sufficient effects cannot be obtained.
  • the platinum compound having no chlorine atom at least one of dinitrodiammine platinum and hexahydroxoplatinum acid may be used.
  • a sufficient catalytic activity can be maintained in a hydrogen generation reaction for a long term, even if the thickness of the electrode catalyst layer is 5 ⁇ m or less, because the abrasion of the electrode catalyst layer can be more effectively inhibited due to the presence of the platinum.
  • the electrode catalyst layer is formed by heat-treatment in the atmosphere containing oxygen at a temperature of preferably 400° C. to 600° C., and more preferably 460° C. to 540° C.
  • a temperature preferably 400° C. to 600° C., and more preferably 460° C. to 540° C.
  • the atmosphere containing oxygen may include the air, an atmosphere containing 100% by volume of oxygen, and the like.
  • the corrosion of the nickel base may be easily caused due to galvanic corrosion, because the platinum have a more noble oxidation-reduction potential.
  • the corrosion reaction of the electrode base can be inhibited, because it has the mixture layer including the metal nickel, nickel oxide and carbon atoms on the conductive substrate surface, and therefore it is also possible to inhibit the corrosion of nickel in the electrode base in the case where the electrode base includes the electrode catalyst layer including the platinum.
  • the nickel surface of the base is likely to give rise to the corrosion reaction after the electrolysis, though the nickel surface of the base is covered with the stable oxide layer before the electrolysis operation.
  • Examples and Comparative Examples described below show comparisons of a nickel contamination into an ion-exchange membrane when a negative electrode for aqueous solution electrolysis was brought into contact with an ion-exchange membrane after the start of the passage of electric current.
  • the elusion of nickel was not observed from the unelectrolyzed sample in the mixture layer formed from the nickel carboxylate; whereas the elusion of nickel was observed in a case where nickel sulfate was used as a coating material for forming the mixture layer, despite the sample was not subjected to the electrolysis.
  • the component analysis of this mixture layer shows that the nickel sulfate is not thermally decomposed and remains in a salt form, and therefore it can be understood that the stable mixture layer is not formed.
  • the nickel oxide is more easily formed when baking at a high temperature, but the initial potential stability at the start of electrolysis can be more improved when the mixture layer is formed at a lower temperature.
  • the mixture layer including the metal nickel, the nickel oxide and the carbon atoms is characterized by a higher corrosion resistance than the nickel oxide layer formed by baking the nickel base in the atmosphere when anodic polarization occurs, and characterized that the destruction of the mixture layer is not advanced even when the anodic polarization occurs.
  • the nickel carboxylate which can be formed at a low temperature, is preferably used for the mixture layer formed on the surface of the electrode base, in the negative electrode for aqueous solution electrolysis having the electrode catalyst layer including the platinum group metal or the compound thereof.
  • the mixture layer formed by the thermal decomposition of nickel carboxylate is preferable, in a case where the mixture layer is formed in low-temperature baking conditions for improving the potential stability after the start of the passage of electric current through the electrolytic cell.
  • a surface of a nickel expanded metal having a thickness of 0.9 mm, a length of 20 mm and a width of 20 mm was sand-blasted with alumina particles having a particle size of 50 ⁇ m to roughen the surface, thereby obtaining a conductive substrate for a sample.
  • the conductive substrate was immersed in 30% by mass sulfuric acid having a temperature of 60° C. for 10 minutes to perform etching, thereby removing the surface oxide coating film and the remaining alumina particles.
  • an aqueous solution including 0.1 mol/L nickel formate (II) dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared to be used as a coating solution for a mixture layer.
  • the coating solution for a mixture layer was applied to the nickel expanded metal which had been surface-treated, and the resulting metal was dried at 60° C. for 3 minutes and baked in a muffle furnace (KDF-P80G manufactured by Denken Co., Ltd.) at 300° C. for 10 minutes to give a sample 1 (electrode base) for an anodic polarization test.
  • a first pre-electrolysis was performed at a current density of 10 kA/m 2 for one hour using an aqueous 32% by mass sodium hydroxide solution having a temperature of 90° C. as an electrolytic solution.
  • a first anodic polarization test was performed in which the direction of the passage of electric current was immediately reversed, the anodic polarization test sample 1 was subjected to anodic polarization at a current density of 10 A/m 2 , a change in the electrode potential of the anodic polarization test sample 1 to a mercury/mercury oxide reference electrode in an electric quantity was determined until the electrode potential was suddenly increased from the oxidation-reduction potential of the nickel to a noble potential, and the passage of electric current was intercepted. The results are shown in FIG. 1 as Test 1 .
  • Example 1 a comparative anodic polarization test sample 1 was made by baking a conductive substrate at 500° C. for 10 minutes to form a nickel oxide coating film.
  • a first comparative anodic polarization test, a second comparative anodic polarization test and a third comparative anodic polarization test were performed in the same manner as in Example 10.
  • Comparative anodic polarization test 1 Comparative anodic polarization test 1
  • Comparative anodic polarization test 2 Comparative anodic polarization test 3 .
  • the electrode base of the present invention has a higher resistance to an electric current generated by the anodic polarization and oxidizing the negative electrode than that of the oxide coating film formed by the oxidation of the substrate nickel formed in the atmosphere.
  • Example 1 The aqueous nickel formate solution prepared in Example 1 was applied to a nickel plate and a procedure of baking at 300° C. in the atmosphere was repeated ten times to produce a sample 1 for confirmation of thermal decomposition products.
  • the abundance ratio of nickel, oxygen and carbon was 45.5:39.8:14.7 by atom on an average of the ten portions.
  • a comparative sample 1 for confirmation of thermal decomposition products was produced by repeating the procedure of baking at 300° C. in the atmosphere ten times in the same manner as in Example 2, except that the aqueous nickel formate solution was not applied to the nickel plate. The products on the surface were measured in the same manner as in Example 2. The abundance ratio of nickel, oxygen and carbon was 91.1:8.9:0 by atom.
  • a comparative sample 2 for confirmation of thermal decomposition products was produced in the same manner as above except that the baking temperature was changed to 500° C., and the same measurement as above was performed.
  • the abundance ratio of nickel, oxygen and carbon was 80.9:19.1:0 by atom on an average of ten portions.
  • Example 1 The nickel formate powder used in Example 1 was heated at 300° C. and 500° C. in the atmosphere to perform thermal decomposition. The resulting sample was measured for an X-ray absorption fine structure (XAFS) using beam line BL-12C in Radiation Science Research Facility (Photon Factory) of High Energy Acceleration Research Organization.
  • XAFS X-ray absorption fine structure
  • Spectrometer an Si (111) two crystal spectrometer.
  • Mirror a focusing mirror.
  • Absorption edge a transmission method.
  • Detector used Ionization chamber. The abundance ratio was obtained using XANES spectra.
  • the measured results were obtained according to a general analysis method of XANES spectra in which a computation process was performed so that a difference between a synthesized peak which was synthesized from the standard peaks of the metal nickel and the nickel oxide which could be thought as the components based on the measured peak, and a measured peak becomes the minimum in a least squares method.
  • the percentage was shown as the abundance ratio of each component.
  • the nickel formate which had been thermally decomposed at 300° C. had 31.6% of metal nickel and 68.4% of nickel oxide.
  • the nickel formate which had been thermally decomposed at 500° C. had 18.6% of metal nickel and 81.4% of nickel oxide.
  • a surface of a nickel expanded metal having a thickness of 0.9 mm, a length of 20 mm and a width of 20 mm was sand-blasted with alumina particles having a particle size of 50 ⁇ m to roughen the surface, thereby obtaining a conductive substrate for a sample.
  • the conductive substrate was immersed in 30% by mass sulfuric acid having a temperature of 60° C. for 10 minutes to perform etching, thereby removing the surface oxide coating film and the remaining alumina particles.
  • an aqueous solution including 0.1 mol/L nickel acetate (II) tetrahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared to be used as a coating solution for a mixture layer.
  • the coating solution for a mixture layer was applied to the nickel expanded metal which had been surface-treated, and the resulting metal was dried at 60° C. for 3 minutes and baked in a muffle furnace (KDF-P80G manufactured by Denken Co., Ltd.) at 300° C. for 10 minutes to give a sample 1-1 (electrode base) on which the mixture layer was formed, or baked at 500° C. for 10 minutes to give a sample 1-2 (electrode base) on which the mixture layer was formed.
  • KDF-P80G manufactured by Denken Co., Ltd.
  • the electrode catalyst layer-forming solution 1 was coated to the mixture layer-formed sample 1-1 or 1-2 previously produced and was dried, and a procedure of baking at 500° C. for 10 minutes was repeated five times to produce test negative electrodes 1 - 1 and 1 - 2 .
  • Electrolysis was performed in an aqueous solution including 30% by mass of sodium hydroxide at 90° C. at a current density of 10 kA/m 2 for one hour using the test negative electrode 1 - 1 or 1 - 2 produced and the same nickel expanded metal as that used in the base of the test negative electrode 1 - 1 as a positive electrode, and electrolysis was continued at a current density of 20 kA/m 2 for further one hour.
  • test negative electrodes 1 - 1 and 1 - 2 were observed after the electrolysis by using a scanning electron microscope (JSM-6490 manufactured by JEOL Ltd.) about peeling-off of the coating film, and the like. The results are shown in Table 2.
  • test negative electrode 1 - 1 or 1 - 2 after the electrolysis was brought into close contact with a positive ion-exchange membrane (N-2030 manufactured by Du Pont), which had been immersed in an aqueous sodium hydroxide solution having a pH of 11, and a pressure of 981 Pa was applied thereto, which was sealed in a polyethylene bag and allowed to stand for 24 hours.
  • a positive ion-exchange membrane N-2030 manufactured by Du Pont
  • nickel in the positive ion-exchange membrane taken out was detected using an ICP emission spectrophotometric analyzer (ICPS-8100 manufactured by Shimadzu Corporation). The results are shown in Table 2 as a nickel deposition amount per 4 cm 2 area.
  • test negative electrode 2 - 1 whose mixture layer was formed at 300° C. and a test negative electrode 2 - 2 whose mixture layer was formed at 500° C. were produced in the same manner as in Example 6, except that nickel formate was used as the mixture layer-forming material instead of the nickel acetate, and the evaluation test was performed in the same manner as in Example 6. The results are shown in Table 2.
  • a mixture layer-formed sample 3-1 whose mixture layer was formed at 300° C. and a mixture layer-formed sample 3-2 whose mixture layer was formed at 500° C. were produced in the same manner as in Example 6.
  • cerium nitrate and a dinitrodiammine platinum salt were dissolved in 8% by mass nitric acid so that the atomic ratio of Pt:Ce was 1:1 to prepare an electrode catalyst layer-forming solution 2 having a total concentration of cerium and platinum of 5% by mass.
  • the electrode catalyst layer-forming solution 2 was applied and dried, and a procedure of baking at 500° C. for 10 minutes was repeated five times to produce test negative electrodes 3 - 1 and 3 - 2 .
  • the evaluation test was performed in the same manner as in Example 6. The results are shown in Table 2.
  • a mixture layer-formed sample 4-1 whose mixture layer was formed at 300° C. and a mixture layer-formed sample 4-2 whose mixture layer was formed at 500° C. were produced in the same manner as in Example 7.
  • Example 8 the electrode catalyst layer-forming solution 2 was applied to the sample and dried, and a procedure of baking at 500° C. for 10 minutes was repeated five times in the same manner as in Example 8 to produce test negative electrodes 4 - 1 and 4 - 2 .
  • the evaluation test was performed in the same manner as in Example 6. The results are shown in Table 2.
  • a comparative negative electrode 2 - 1 whose mixture layer was formed at 300° C. and a comparative negative electrode 2 - 2 whose mixture layer was formed at 500° C. were produced in the same manner as in Example 6, except that nickel sulfate was used for the mixture layer instead of nickel acetate.
  • the evaluation test was performed in the same manner as in Example 6. The results are shown in Table 2.
  • a comparative negative electrode 2 - 1 whose mixture layer was formed at 300° C. and a comparative negative electrode 2 - 2 whose mixture layer was formed at 500° C. were produced in the same manner as in Example 6, except that nickel nitrate was used for the mixture layer instead of the nickel acetate.
  • the evaluation test was performed in the same manner as in Example 6. The results are shown in Table 2.
  • a comparative negative electrode 3 was produced in the same manner as in Example 6, except that the mixture layer was not formed.
  • the evaluation test was performed in the same manner as in Example 6. The results are shown in Table 2.
  • a comparative negative electrode 4 was produced in the same manner as in Example 6, except that a mixture layer was formed by baking the conductive substrate at 500° C. in the atmosphere without applying a nickel salt such as nickel acetate.
  • the evaluation test was performed in the same manner as in Example 6. The results are shown in Table 2.
  • a comparative negative electrode 5 - 1 whose mixture layer was formed at 300° C. and a comparative negative electrode 5 - 2 whose mixture layer was formed at 500° C. were produced in the same manner as in Example 8, except that nickel sulfate was used for the mixture layer instead of the nickel acetate.
  • the evaluation test was performed in the same manner as in Example 6. The results are shown in Table 2.
  • a comparative negative electrode 6 - 1 whose mixture layer was formed at 300° C. and a comparative negative electrode 6 - 2 whose mixture layer was formed at 500° C. were produced in the same manner as in Example 8, except that nickel nitrate was used for the mixture layer instead of the nickel acetate.
  • the evaluation test was performed in the same manner as in Example 6. The results are shown in Table 2.
  • a comparative negative electrode 7 was produced in the same manner as in Example 8, except that the mixture layer was not formed.
  • the evaluation test was performed in the same manner as in Example 6. The results are shown in Table 2.
  • a comparative negative electrode 8 was produced in the same manner as in Example 8, except that a mixture layer was formed by baking the conductive substrate at 500° C. in the atmosphere without applying a nickel salt such as nickel acetate.
  • the evaluation test was performed in the same manner as in Example 6. The results are shown in Table 2.
  • a mixture layer was formed at 300° C. in the same manner as in Example 6 except that a nickel expanded metal having a thickness of 0.15 mm was used as the conductive substrate.
  • the same electrode catalyst layer-forming solution 1 as in Example 6 was applied thereto, and a test negative electrode 5 was produced in the same manner as in Example 6.
  • test electrolytic cell On a test electrolytic cell were mounted the test negative electrode 5 produced above as the negative electrode and an electrode for generating chlorine whose base was a titanium expanded metal (DSE JP-202 manufactured by Permelec Electrode Ltd.) as a positive electrode, and a negative electrode room and a positive electrode room were divided with a positive ion-exchange membrane (N-2030 manufactured by Du Pont) treated with an aqueous solution of 2% by mass sodium hydroxide. A zero-gap ion-exchange membrane in which the negative electrode, the ion-exchange membrane and the positive electrode were integrally touched was assembled. The electrolytic cell was stored for 15 hours after the assembly without filling an electrolytic solution therein.
  • DSE JP-202 manufactured by Permelec Electrode Ltd.
  • electrolysis was performed at an operation temperature of 90° C. at a current density of 6 kA/m 2 .
  • electrolysis was stopped for two days of the 51st day and 52nd day, and the electrolytic cell was disassembled and stored under exposure to the atmosphere. After the storage, the electrolysis was performed, but the increase of the electrolytic cell voltage was not observed and the current efficiency was kept at 97%.
  • the electrolytic cell was disassembled, and the ion-exchange membrane was observed. The deposition of nickel was not found.
  • the electrolytic cell voltage was increased by 0.004 V and the hydrogen overvoltage was increased by 0.7 mV.
  • the electrolytic cell voltage was increased by 0.004 V and the hydrogen overvoltage was increased by 2.4 mV. That is to say, the increase of the electrolytic cell voltage was only 0.008 V and the increase of the hydrogen overvoltage was only 3.1 mV after the second short-circuit test, compared to those before the first short-circuit test.
  • a comparative test negative electrode 9 was produced in the same manner as in Example 10, except that a mixture layer was formed by baking a conductive substrate at 500° C. for 10 minutes instead of formation of a mixture layer by the application of the nickel salt and the thermal decomposition, and the electrolysis was performed in the same manner as in Example 10.
  • the initial electrolytic cell voltage showed a voltage 0.010 V higher than that in Example 10.
  • electrolysis was stopped for two days of the 51st day and 52nd day, and the electrolytic cell was disassembled and stored under exposure to the atmosphere, in the same manner as in Example 10.
  • the increase of the electrolytic cell voltage was not observed in the subsequent electrolysis, and the current efficiency was kept at 97%.
  • the electrolytic cell voltage was increased by 0.010 V.
  • the nickel deposition to the ion-exchange membrane was not confirmed after the electrolytic cell was disassembled.
  • the electrolytic cell voltage was increased by 0.007 V, and the hydrogen overvoltage was increased by 7.0 mV.
  • the electrolytic cell voltage was increased by 0.018 V, and the hydrogen overvoltage was increased by 6.2 mV. That is to say, the electrolytic cell voltage was increased by 0.025 V and the hydrogen overvoltage was increased by 13.2 mV after the second short-circuit test, compared to those before the first short-circuit test.
  • the negative electrode for aqueous solution electrolysis of the present invention has a low hydrogen overvoltage; nickel on the conductive substrate surface does not elute even when the passage of electric current is stopped; only a small amount of nickel is deposited in the ion-exchange membrane when it is used as a negative electrode in the ion-exchange membrane electrolytic cell; the operation can be stably performed for a long term; the electrolysis voltage is kept stable from the beginning of the electrolysis even when the platinum electrode catalyst layer is formed; and it is possible to stably operate the electrolytic cell.
  • the negative electrode for aqueous solution electrolysis of the invention having the effects described above is preferably used for the electrolysis of an aqueous solution of an alkali metal halide, and the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Chemically Coating (AREA)
US13/579,092 2010-02-17 2011-02-17 Electrode base, negative electrode for aqueous solution electrolysis using same, method for producing the electrode base, and method for producing the negative electrode for aqueous solution electrolysis Abandoned US20130153411A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2010032578 2010-02-17
JP2010-32578 2010-02-17
PCT/JP2011/053418 WO2011102431A1 (ja) 2010-02-17 2011-02-17 電極基体およびそれを用いた水溶液電気分解用陰極、およびそれらの製造方法

Publications (1)

Publication Number Publication Date
US20130153411A1 true US20130153411A1 (en) 2013-06-20

Family

ID=44483017

Family Applications (1)

Application Number Title Priority Date Filing Date
US13/579,092 Abandoned US20130153411A1 (en) 2010-02-17 2011-02-17 Electrode base, negative electrode for aqueous solution electrolysis using same, method for producing the electrode base, and method for producing the negative electrode for aqueous solution electrolysis

Country Status (5)

Country Link
US (1) US20130153411A1 (enrdf_load_stackoverflow)
EP (1) EP2537961A4 (enrdf_load_stackoverflow)
JP (1) JP5006456B2 (enrdf_load_stackoverflow)
CN (1) CN102770587B (enrdf_load_stackoverflow)
WO (1) WO2011102431A1 (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10472723B2 (en) 2015-01-06 2019-11-12 Thyssenkrupp Uhde Chlorine Engineers (Japan) Ltd. Method of preventing reverse current flow through an ion exchange membrane electrolyzer
CN110791769A (zh) * 2019-11-06 2020-02-14 南通大学 一种基于卤盐盐蚀的电极及其制备方法
US12146232B2 (en) 2018-07-06 2024-11-19 Lg Chem, Ltd. Active layer composition of reduction electrode for electrolysis and reduction electrode derived therefrom

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101726575B1 (ko) 2015-08-21 2017-04-14 한국과학기술연구원 극소량의 백금이 도포된 니켈 전극촉매, 이의 제조방법 및 이를 이용한 음이온 교환막 물 전기분해 장치
JP7720136B2 (ja) * 2019-08-09 2025-08-07 株式会社大阪ソーダ 電解用電極の製造方法
IT202100020735A1 (it) 2021-08-02 2023-02-02 Industrie De Nora Spa Elettrodo per evoluzione elettrolitica di idrogeno
IL292647B2 (en) * 2022-05-01 2024-03-01 Electriq Global Energy Solutions Ltd A catalyst for generating hydrogen and a method for its preparation
TW202507073A (zh) * 2023-08-07 2025-02-16 翔名科技股份有限公司 抗腐蝕鎳基合金的表面處理方法及其結構

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4394231A (en) * 1979-06-29 1983-07-19 Solvay & Cie Cathode for the electrolytic production of hydrogen
US6312571B1 (en) * 1999-02-24 2001-11-06 Permelec Electrode Ltd. Activated cathode and process for preparation thereof

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6047352B2 (ja) * 1977-06-27 1985-10-21 株式会社トクヤマ 陰極の製造法
JPS59162288A (ja) * 1983-03-08 1984-09-13 Asahi Chem Ind Co Ltd 水素発生用電極
JPH0633483B2 (ja) * 1983-07-22 1994-05-02 旭化成工業株式会社 水素発生用電極
JPH022A (ja) 1984-06-20 1990-01-05 Tomio Konno 真空フアイバー電子通信の方法とその装置
JPH0633487B2 (ja) * 1985-03-22 1994-05-02 徳山曹達株式会社 陰極の製造方法
JPS6286187A (ja) * 1985-10-09 1987-04-20 Asahi Chem Ind Co Ltd 水素発生用の電極
JPH0344154A (ja) * 1989-07-11 1991-02-26 Nec Eng Ltd 指定時刻呼出し方式
DE4342859A1 (de) * 1993-12-10 1995-06-14 Winsel August Kathode für Wasserstoffentwicklungszellen
JP4341838B2 (ja) * 2004-10-01 2009-10-14 ペルメレック電極株式会社 電解用陰極
JP4274489B2 (ja) 2006-10-25 2009-06-10 クロリンエンジニアズ株式会社 水素発生用電極およびその製造方法
JP2010032578A (ja) 2008-07-25 2010-02-12 Tmc Co Ltd 情報処理装置および方法、並びにプログラム

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4394231A (en) * 1979-06-29 1983-07-19 Solvay & Cie Cathode for the electrolytic production of hydrogen
US6312571B1 (en) * 1999-02-24 2001-11-06 Permelec Electrode Ltd. Activated cathode and process for preparation thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Jesus et al. (Journal of Molecular Catalysis A: Chemical, Volume 228, Issue 1-2, 2005, Pages 283-291) *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10472723B2 (en) 2015-01-06 2019-11-12 Thyssenkrupp Uhde Chlorine Engineers (Japan) Ltd. Method of preventing reverse current flow through an ion exchange membrane electrolyzer
US12146232B2 (en) 2018-07-06 2024-11-19 Lg Chem, Ltd. Active layer composition of reduction electrode for electrolysis and reduction electrode derived therefrom
CN110791769A (zh) * 2019-11-06 2020-02-14 南通大学 一种基于卤盐盐蚀的电极及其制备方法

Also Published As

Publication number Publication date
EP2537961A4 (en) 2016-09-07
CN102770587B (zh) 2015-07-15
JP2011190534A (ja) 2011-09-29
WO2011102431A1 (ja) 2011-08-25
JP5006456B2 (ja) 2012-08-22
CN102770587A (zh) 2012-11-07
EP2537961A1 (en) 2012-12-26

Similar Documents

Publication Publication Date Title
US20130153411A1 (en) Electrode base, negative electrode for aqueous solution electrolysis using same, method for producing the electrode base, and method for producing the negative electrode for aqueous solution electrolysis
EP2518185B1 (en) Cathode, electrolytic cell for electrolysis of alkali metal chloride, and method for producing the cathode
JP5307270B2 (ja) 食塩電解に使用する水素発生用陰極
US8425740B2 (en) Cathode for hydrogen generation and method for producing the same
EP2653589B1 (en) Electrode for electrolysis, electrolytic cell and production method for electrode for electrolysis
IL170874A (en) Process for the production of an electrolytic electrode with a platinum group metal oxide coating and electrodes made therefrom
US8034221B2 (en) Electrode for hydrogen generation and process for preparation thereof
CA2501229A1 (en) Coatings for the inhibition of undesirable oxidation in an electrochemical cell
JP2006104502A (ja) 電解用陰極
Komiya et al. Dynamic stabilization of nickel-based oxygen evolution electrocatalysts in the presence of chloride ions using a phosphate additive
EP3819402B1 (en) Reduction electrode for electrolysis and manufacturing method therefor
JP6753195B2 (ja) 水素発生用電極の製造方法及び水素発生用電極を用いた電気分解方法
JP2010209420A (ja) 低水素過電圧陰極の製法
CN112342566B (zh) 电解用电极的制造方法
KR20190037520A (ko) 전기분해 음극용 코팅액 조성물
TW202407156A (zh) 氫產生電極及其製造方法
e Azevedo Influence of the Atmospheric Plasma Spray Coating in Electrodes Properties to Use in Alkaline Electrolysis
KR20200142463A (ko) 전기분해용 전극
KR20210004560A (ko) 전기분해용 환원 전극

Legal Events

Date Code Title Description
AS Assignment

Owner name: CHLORINE ENGINEERS CORP., LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ISHIMARU, SANAE;REEL/FRAME:029041/0436

Effective date: 20120911

AS Assignment

Owner name: PERMELEC ELECTRODE LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:CHLORINE ENGINEERS CORP., LTD.;REEL/FRAME:033564/0224

Effective date: 20140806

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION