EP1235658A1 - Catalytic powder and electrode made therewith - Google Patents
Catalytic powder and electrode made therewithInfo
- Publication number
- EP1235658A1 EP1235658A1 EP00973563A EP00973563A EP1235658A1 EP 1235658 A1 EP1235658 A1 EP 1235658A1 EP 00973563 A EP00973563 A EP 00973563A EP 00973563 A EP00973563 A EP 00973563A EP 1235658 A1 EP1235658 A1 EP 1235658A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oxide
- metal
- porous coating
- electrode
- mixture
- 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.)
- Granted
Links
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
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/148—Agglomerating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/1103—Making porous workpieces or articles with particular physical characteristics
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/002—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of porous nature
- B22F7/004—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of porous nature comprising at least one non-porous part
-
- 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
- C25B11/095—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 of the compounds being organic
Definitions
- the present invention is directed to electrocatalytic electrodes. More particularly, the present invention is directed to cathodes useful in electrolysis cells such as a chlor-alkali cell.
- Chlorine and caustic soda are typically produced by electrolysis of aqueous solutions of sodium chloride, a process commonly referred to as a chlor-alkali process.
- chlor-alkali processes employ either diaphragm or membrane type cells.
- a diaphragm cell an alkali metal halide brine solution is fed into an anolyte compartment where halide ions are oxidized to produce halogen gas.
- Alkali metal ions migrate into a catholyte compartment through a hydraulically-permeable microporous diaphragm disposed between the anolyte compartment and the catholyte compartment.
- Hydrogen gas and aqueous alkali metal hydroxide solutions are produced at the cathode. Due to the hydraulically-permeable diaphragm, brine may flow into the catholyte compartment and mix with the alkali metal hydroxide solution.
- a membrane cell functions similarly to a diaphragm cell, except that the diaphragm is replaced by an hydraulically-impermeable, cation-selective membrane which selectively permits passage of hydrated alkali metal ions to the catholyte compartment.
- a membrane cell produces aqueous alkali metal hydroxide solution essentially uncontaminated with brine.
- Electrodes are usually prepared by providing an electrocatalytic coating on a conducting substrate.
- Useful catalytic coatings include, for example, the platinum group metals, such as ruthenium, rhodium, osmium, iridium, palladium and platinum.
- Useful conducting substrates include, for example, nickel, iron, and steel.
- overvoltage is used herein to refer to the excess voltage required for an electrolytic cell
- overpotential is used herein to refer to the excess voltage required for an individual electrode within the electrolytic cell.
- the overpotential for an electrode is a function of its chemical characteristics and current density.
- Current density is defined as the current applied per unit of actual surface area on an electrode. Techniques which increase the actual surface area of an electrode, such as acid etching or sandblasting the surface of the electrode, result in a corresponding decrease of the current density for a given amount of applied current and also decrease overpotential requirements.
- Efforts to reduce overpotential requirements include, for example, those described in U.S. Patent No. 4,66,8370 and U.S. Patent No. 4,798,662, which disclose electrodes useful as cathodes in an electrolytic cell. These are prepared by coating an electrically conducting substrate such as nickel with a catalytic coating comprising one or more platinum group metals from a solution comprising a platinum group metal salt. Both of these Patents disclose electrodes designed to reduce the operating voltage of an electrolytic cell by reducing the overpotential requirements of the electrodes.
- U.S. Patent. No. 5,035,789, U.S. Patent. No. 5,227,030, and U.S. Patent. No. 5,066,380 disclose cathode coatings which exhibit low hydrogen ove ⁇ otentials.
- a desirable characteristic of a cathode coating is high porosity with large internal surface areas. Large internal surface areas result in lower effective current density and, accordingly, lower ove ⁇ otentials.
- Another result of a porous electrode is higher resistance to impurity poisoning. Rough outer surfaces of a typical porous electrode render difficult the electrodeposition of metal ions as impurities and the large internal electroactive surface areas are not easily accessible to the impurity ions present in the electrolyte because of long
- Figure 2 is a magnified representation of a cross section of a portion of an electrode of the present invention.
- the present invention is a catalytic powder comprising a plurality of support metal particles comprising a transition metal or an alloy thereof; and a coating surrounding the support metal particles, the coating either comprising an electrocatalytic metal coating or comprising a coating with a metal continuous phase in admixture with a particulate material.
- the present invention is an electrode comprising a conductive metal substrate; and a first layer comprising a matrix with a catalytic powder dispersed therethrough, the matrix comprising a platinum group metal oxide or a mixture of a platinum group metal oxide and a valve metal oxide, the catalytic powder comprising support metal particles covered either with an electrocatalytic metal coating, or with a coating comprising an electrocatalytic metal in admixture with a particulate material.
- the present invention is advantageous because a porous coating mixture is first applied to a powder rather than being applied directly to a metal substrate, thereby creating a larger internal surface area relative to the prior art. Large internal surface areas result in lower effective current density and, accordingly, lower ove ⁇ otentials. Therefore, because the surface area is enhanced using the present invention, the ove ⁇ otential required for electrodes made according to the present invention is also reduced relative to electrodes of the prior art cited above.
- FIG. 1 illustrates a magnified view of a catalytic powder particle 10 of the present invention.
- the catalytic powder particle 10 comprises a support metal particle 1 1 surrounded by a porous coating comprising a continuous phase 12 with a particulate material 13 dispersed therethrough.
- the support metal particle 1 1 is a transition metal or alloy thereof.
- Preferred transition metals include nickel, cobalt, iron, steel, stainless steel or copper.
- Preferred transition metal alloys include nickel, cobalt, or copper, alloyed with phosphorous, boron or sulfur.
- the support metal particles before the porous coating is applied thereto, have an average diameter of at least 0.2 microns, more preferably at least about 1 micron, even more preferably at least 2 microns, and yet even more preferably at least 3 microns.
- the metal particles have an average diameter of up to 20.0 microns, more preferably up to 10.0 microns and even more preferably up to 6.0 microns.
- the electrocatalytic metal continuous phase 12 is ruthenium, iridium, osmium, platinum, palladium, rhodium, rhenium, or an alloy of any one or more of these.
- the continuous phase 12 has a particulate material 13 dispersed therethrough.
- particulate material 13 comprises the metal oxides of ruthenium, iridium, osmium, platinum, palladium, rhodium, rhenium, technetium, molybdenum, chromium, niobium, tungsten, tantalum, manganese or lead, with the oxides of ruthenium, iridium osmium, platinum, palladium and rhodium being more preferred.
- the palladium metal ion concentration suitably can be 0.001 percent to 5 percent; preferably from 0.005 percent to 2 percent and, most preferably, from 0.01 percent to 0.05 percent, by weight of the coating solution.
- a weight percent of less 5 than 0.001 percent is generally insufficient to promote deposition of the electrocatalytic metal.
- a weight percentage greater than percent 5 results in the deposition of an excessive amount of electrocatalytic metal primary phase of the coating on the substrate.
- the pH of the deposition solution may be adjusted by inclusion of organic acids or inorganic acids therein.
- suitable inorganic acids are hydrobromic acid, o hydrochloric acid, sulfuric acid, perchloric acid, and phosphoric acid.
- organic acids are acetic acid, oxalic acid, and formic acid. Hydrobromic acid and hydrochloric acid are preferred.
- the pH range for the deposition solution is, generally, 0 pH to 2.8 pH. Precipitation of hydrous platinum group metal oxide results at higher pHs. A low pH can encourage competing side reactions such as the dissolution of the substrate.
- At least one electrocatalytic metal compound soluble in water or an aqueous acid is added to the deposition solution.
- a suitable electrocatalytic metal is, generally, one that is more noble than the metal employed for the metal particles, that is, the electrocatalytic metal precursor compound has a Gibbs free energy greater than the Gibbs free energy of the metal compound from dissolution of the metal particles, such that non-electrolytic reductive o deposition occurs on the metal particles.
- such electrocatalytic metal is a platinum group metal. More details non-electrolytic reductive deposition can be found in U.S. Patent 5,645,930.
- the optional particulate material is suspended in the deposition solution at a concentration of from 0.002 to 2 percent, preferably, 0.005 to 0.5 percent, and most preferably, 0.01 to 0.2 percent.
- the deposition solution comprising the palladium promoter, the acid, and the 5 optional particulate material is prepared, it is held at an elevated temperature and stirred at a high speed, while a powder comprising support metal particles is added thereto. After a period of time, the electrocatalytic metal precursor compound is added, and the electrocatalytic metal is formed and deposited on the support metal particles with simultaneous partial dissolution of the support metal particles.
- the rate at which the electrocatalytic metal deposits to form the porous coating on the metal particles is a function of the solution temperature.
- the temperature generally, ranges from 25°C to 90°C. Low temperatures are not practical, since uneconomically long times are required to deposit an effective amount of electrocatalytic metal on the metal particles. Temperatures higher than 90°C are operable, but generally result in an excessive amount of 5 metal deposition and side reactions. A temperature ranging from between 40°C to 80°C is preferred, with 45°C to 65°C being most preferred.
- the conductive metal substrate 21 is nickel, iron, steel, stainless steel, cobalt, copper or silver.
- the shape of the substrate is not critical and can be, for example, a flat sheet, a curved surface, a punched plate, a woven wire screen, or a mesh sheet.
- the matrix 22 of the first layer comprises either a platinum group metal oxide or a mixture of a platinum group metal oxide and a valve metal oxide.
- Platinum group metal oxides include oxides of ruthenium, iridium, rhodium, osmium, platinum, palladium or a mixture of any one or more of these.
- Valve metal oxides include oxides of titanium, zirconium, tantalum, tungsten, niobium, bismuth, or a mixture of any one or more of these.
- the above described catalytic powder is mixed with a dispensing medium to form a mixture which is applied to the conductive metal substrate to form a covered substrate.
- the covered substrate is then baked in the presence of oxygen.
- the dispensing medium forms the matrix of the electrode and comprises either a platinum group metal oxide precursor or a mixture of a platinum group metal oxide precursor and a valve metal oxide precursor.
- Platinum group metal oxide precursors are those materials that form platinum group metal oxides upon baking in the presence of oxygen.
- Preferred platinum group metal oxide precursors include platinum group metal halides, sulfates, nitrates, nitrites, and phosphates. More preferred are platinum group metal halides, nitrates and phosphates, with platinum group metal chlorides being the most preferred.
- Valve metal oxide precursors are those materials that form valve metal oxides upon baking in the presence of oxygen.
- the valve metal oxide precursor is titanium alkoxide, tantalum alkoxide, zirconium acetylacetonate, or niobium alkoxide.
- the dispensing medium further comprises a solvent.
- Suitable solvents include methanol, ethanol, 1 -propanol, 2-propanol, butanol, or a mixture of any of these.
- the dispensing medium further includes a compound soluble in alkaline solutions.
- soluble compounds include aluminum chloride and zinc chloride.
- alkaline soluble compounds are useful in generating pores in the coating after they are dissolved in an alkaline solution.
- Any appropriate method may be used for dispersing the catalytic powder in the dispensing medium. Examples include mechanical stirring, sonicating, or combinations thereof.
- Loadings greater than 2000 ug/cm 2 do not significantly reduce the applied overvoltage when compared to lesser loadings within the preferred range. It should be understood that the effective amount of deposition specified above refers only to loading of the platinum group electrocatalytic metal and metal oxides in the electrode and does not include the amount of the palladium metal promoter which can be used to provide increased loading or any optional secondary electrocatalytic metal or the metal particles.
- the substrate is protected before the mixture is applied thereto, by, for example, electroless nickel plating.
- a baking step is used to convert the platinum group metal oxide precursor and valve metal oxide precursor to an oxide form.
- the coated substrate is baked in the presence of oxygen at a temperature of preferably at least 350°C more preferably at least 420°C and even more preferably at least 450°C.
- the coated substrate is baked at a temperature of not more than 550°C more preferably not more than 500°C even more preferably not more than 480°C
- the baking step occurs for anywhere from 30 to 90 minutes.
- the coated substrate be baked in the presence of oxygen, be it air or some other oxygen-containing substance, so that the platinum group metal oxide precursor and the valve metal oxide precursor convert to platinum group metal oxide and valve metal oxide.
- oxygen be it air or some other oxygen-containing substance
- the electrode of the present invention further comprises a reinforcement layer 23.
- a reinforcement layer 23 preferably comprises a transition metal or alloy thereof. More preferably, the reinforcement layer is nickel, cobalt, copper, or alloys thereof with boron, phosphorous or sulfur.
- a second electroless plating step which consists of plating the coated substrate with a transition metal or a transition metal alloy.
- a reinforcement layer helps hold the catalyst powder and matrix together and also helps ensure that the first layer adheres to the substrate. More details forming the reinforcement layer can be found in U.S. Patent No. 5,645,930.
- a porous coating solution was prepared, with PdCl 2 as palladium promoter and 0.5 N HC1 as acid. The solution was heated to a reaction temperature and continuously stirred. RuCl xH 2 O was added as the electrocatalytic platinum group metal compound. The resulting solution was held at the reaction temperature and stirred using a COWLES high-speed disperser, while 3-micron nickel powder (Aldrich) was added. After stirring the mixture at the elevated temperature for a desired contact time, the resulting Ru-coated nickel powder was collected on a filter paper, dried for several hours at 90 °C and weighed. The amount of Ru in the powder was determined using X-ray fluorescence. Table I lists the variables and the results.
- a porous coating solution was prepared, with PdCl as palladium promoter and 0.5 N HCl as acid. The solution was heated to a reaction temperature and continuously stirred. RuO 2 was added as the platinum group metal oxide. The resulting solution was held at the reaction temperature and stirred using a COWLES high-speed disperser operated at 3000 ⁇ m, while 3-micron nickel powder (Aldrich) was added. RuCl 3 xH 2 O was then added as the electrocatalytic platinum group metal compound. After stirring the mixture at the elevated temperature for a desired contact time, the resulting Ru-coated nickel powder was dried and weighed. The amount of Ru in the powder was determined using X-ray fluorescence. Table II lists the variables and the results.
- the sprayed sample was allowed to dry at 90°C for 20 minutes and baked at 490°C for 60 min. X-ray fluorescence of the sample was used to determine loading of the metal on the substrate. Table III lists the parameters and results.
- a 5inch by 6 inch plate was electroless nickel-plated according to procedures described in U.S. Patent 4,061 ,802.
- the powder weight percent in the spraying mixture is around 10 percent.
- the dispensing medium comprises 2.37 weight percent RuCl 3 xH 2 O as the platinum group metal oxide precursor, 2.87 weight percent titanium isopropoxide as the valve metal oxide precursor, 8.86 weight percent methanol and 83.80 weight percent 2-propanol as the solvent, and 2.10 weight percent AlCl x6H 2 O as the compound soluble in an alkaline solution.
- the sprayed sample was allowed to dry at 90°C for 20 minutes and baked at 490°C for 60 min. X-ray fluorescence of the sample was used to determine loading of the metal on the substrate. Table IV lists the parameters and results.
- the plates were dipped in the following mixture of solutions for a period of five minutes at ambient temperature: 25cc 0.01 M (NH 4 )2PdCl in methanol, 50cc 0.1 M poly(4- vinylpyridine) in methanol, and 425cc methanol.
- the coated plates were then dried in a horizontal position at 90°C. The dipping and drying steps were repeated. Thereafter, the coated plates were placed in a plastic horizontal container with the thread of the plate fitted in a fitting in the bottom of the container.
- the solution was then poured out and 500ml of an electroless nickel-plating solution was then added to the container and electroless plating was conducted for 20 min.
- the composition of the electroless plating solution is:
- Example 4 Weight gains for Example 4 (Example 7), Example 5 (Example 8) and Example 6 (Example 9) were 2.63 mg/cm", 3.26 mg/cm " , and 2.69 mg/cm", respectively.
- the plates were connected to a nickel rod and placed in a caustic bath at an elevated temperature. A platinum plate welded to a nickel rod was used as the anode. Current densities of 0.46 amps per square inch (ASI), 1.0 ASI, and/or 1.09 ASI were applied to the cathode sample and the anode from a rectifier. The potential of the cathode was measured with the aid of a LUGGIN probe with a Hg/HgO reference electrode. The parameters and results were listed in Table V.
- Example 10 Weight gains for Example 10 (Example 17), Example 11 (Example 18), Example 12 (Example 19) and Example 13 (Example 20) are 0.550g, 0.578g., 0.683g, and 0.489g, respectively.
- Example 17 Example 20
- Example 18 Example 21
- Example 19 Example 22
- Example 20 Example 23
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Composite Materials (AREA)
- Catalysts (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Powder Metallurgy (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US16054599P | 1999-10-20 | 1999-10-20 | |
US160545P | 1999-10-20 | ||
PCT/US2000/028563 WO2001028714A1 (en) | 1999-10-20 | 2000-10-13 | Catalytic powder and electrode made therewith |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1235658A1 true EP1235658A1 (en) | 2002-09-04 |
EP1235658B1 EP1235658B1 (en) | 2004-07-21 |
Family
ID=22577327
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00973563A Expired - Lifetime EP1235658B1 (en) | 1999-10-20 | 2000-10-13 | Electrode made with catalytic powder |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP1235658B1 (en) |
JP (1) | JP2003512520A (en) |
CN (1) | CN1379703A (en) |
AU (1) | AU1206301A (en) |
BR (1) | BR0015062A (en) |
CA (1) | CA2387563A1 (en) |
DE (1) | DE60012363T2 (en) |
WO (1) | WO2001028714A1 (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW200304503A (en) | 2002-03-20 | 2003-10-01 | Asahi Chemical Ind | Electrode for generation of hydrogen |
EP1859850A1 (en) * | 2006-05-24 | 2007-11-28 | Globe Union Industrial Corp. | Metal-supported photocatalyst and method for preparing the same |
CN101077478B (en) * | 2006-05-24 | 2010-06-30 | 深圳成霖洁具股份有限公司 | Photocatalyst compound structures body and preparation method thereof |
KR100839372B1 (en) * | 2006-11-01 | 2008-06-19 | 삼성에스디아이 주식회사 | Method of preparing catalyst for fuel cell |
CN101335166B (en) * | 2007-06-27 | 2010-06-30 | 中国科学院电子学研究所 | Cathode three-element alloy film and method for preparing film covered dipping diffusion cathode |
JP4857255B2 (en) * | 2007-12-17 | 2012-01-18 | 株式会社日立製作所 | Electrolysis electrode, method for producing the same, and hydrogen production apparatus |
ITMI20090880A1 (en) * | 2009-05-19 | 2010-11-20 | Industrie De Nora Spa | CATHODE FOR ELECTROLYTIC PROCESSES |
JP2013014813A (en) * | 2011-07-06 | 2013-01-24 | Murata Mfg Co Ltd | Porous metal particle, and manufacturing method thereof |
CN103145222B (en) * | 2012-12-29 | 2014-07-23 | 胜宏科技(惠州)股份有限公司 | Electro-catalysis method for disposing waste brown liquid |
JP2016204732A (en) * | 2015-04-28 | 2016-12-08 | 旭化成株式会社 | Electrode for electrolysis |
JP6733904B2 (en) * | 2016-06-20 | 2020-08-05 | 仲山貴金属鍍金株式会社 | Sintered body and manufacturing method thereof |
EP3676896A4 (en) * | 2017-08-31 | 2021-11-03 | A123 Systems LLC | Process for metallization of electrochemically active powders |
TW202146707A (en) | 2020-01-24 | 2021-12-16 | 英商億諾斯技術有限公司 | Electrode assembly and electrolyser |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3486928A (en) * | 1965-10-21 | 1969-12-30 | Int Nickel Co | Bath and process for platinum and platinum alloys |
EP0174413A1 (en) * | 1984-09-17 | 1986-03-19 | Eltech Systems Corporation | Composite catalytic material particularly for electrolysis electrodes and method of manufacture |
IN164233B (en) * | 1984-12-14 | 1989-02-04 | Oronzio De Nora Impianti | |
US5645930A (en) * | 1995-08-11 | 1997-07-08 | The Dow Chemical Company | Durable electrode coatings |
-
2000
- 2000-10-13 DE DE60012363T patent/DE60012363T2/en not_active Expired - Fee Related
- 2000-10-13 JP JP2001531535A patent/JP2003512520A/en active Pending
- 2000-10-13 CA CA002387563A patent/CA2387563A1/en not_active Abandoned
- 2000-10-13 AU AU12063/01A patent/AU1206301A/en not_active Abandoned
- 2000-10-13 WO PCT/US2000/028563 patent/WO2001028714A1/en active IP Right Grant
- 2000-10-13 EP EP00973563A patent/EP1235658B1/en not_active Expired - Lifetime
- 2000-10-13 BR BR0015062-2A patent/BR0015062A/en active Search and Examination
- 2000-10-13 CN CN00814520A patent/CN1379703A/en active Pending
Non-Patent Citations (1)
Title |
---|
See references of WO0128714A1 * |
Also Published As
Publication number | Publication date |
---|---|
EP1235658B1 (en) | 2004-07-21 |
DE60012363T2 (en) | 2004-12-09 |
CN1379703A (en) | 2002-11-13 |
BR0015062A (en) | 2002-07-16 |
WO2001028714A1 (en) | 2001-04-26 |
JP2003512520A (en) | 2003-04-02 |
CA2387563A1 (en) | 2001-04-26 |
AU1206301A (en) | 2001-04-30 |
DE60012363D1 (en) | 2004-08-26 |
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