EP0707095B1 - Electrode pour procédé électrochimique et utilisation de ladite électrode - Google Patents

Electrode pour procédé électrochimique et utilisation de ladite électrode Download PDF

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Publication number
EP0707095B1
EP0707095B1 EP95202666A EP95202666A EP0707095B1 EP 0707095 B1 EP0707095 B1 EP 0707095B1 EP 95202666 A EP95202666 A EP 95202666A EP 95202666 A EP95202666 A EP 95202666A EP 0707095 B1 EP0707095 B1 EP 0707095B1
Authority
EP
European Patent Office
Prior art keywords
coating
platinum
electrode
iridium
oxide
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.)
Expired - Lifetime
Application number
EP95202666A
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German (de)
English (en)
French (fr)
Other versions
EP0707095A1 (fr
Inventor
Alessandra Pastacaldi
Francesco Posar
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.)
Solvay SA
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Solvay SA
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Filing date
Publication date
Application filed by Solvay SA filed Critical Solvay SA
Publication of EP0707095A1 publication Critical patent/EP0707095A1/fr
Application granted granted Critical
Publication of EP0707095B1 publication Critical patent/EP0707095B1/fr
Anticipated expiration legal-status Critical
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    • 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

Definitions

  • the invention relates to electrochemical processes, in particular to electrolysis processes.
  • It relates more particularly to an electrode usable in such processes.
  • Important parameters of industrial electrolysis processes are, on the one hand, the potentials of electrochemical reactions at the electrodes and, on the other hand, the current efficiency at the electrodes.
  • the difficulty in achieving acceptable current yields is particularly present in the electrolysis processes of the salts of alkali metals in aqueous solution, the reaction at the anode being accompanied usually of parasitic oxygen formation.
  • This difficulty is particularly present in chlorine manufacturing processes by electrolysis of aqueous solutions of alkali metal chloride (in particular sodium).
  • anodes comprising, on an electroconductive substrate, a coating of oxide of ruthenium and tin oxide, combined with platinum, platinum oxide or iridium oxide.
  • anode whose coating consists of a mixture of 14 mol% platinum, 6 mol% iridium and 80 mol% tin.
  • iridium and tin are in the form of oxides.
  • the invention therefore relates to an electrode for an electrochemical process, comprising, on an electroconductive substrate, a coating including from 12 to 17% by weight of platinum, from 30 to 40% by weight of iridium oxide and from 43 to 58% by weight of tin oxide.
  • the substrate must be made of a material electroconductive, inert under the electrolysis conditions at which the electrode is intended. Notwithstanding this condition, the electrode substrate according to the invention is not critical and its constitution does not constitute the object of the invention.
  • the substrate can advantageously be in a metal selected from titanium, tantalum, zirconium, vanadium, niobium and tungsten or an alloy of these metals.
  • the substrate profile is not critical and does not constitute the object of the invention, the most suitable profile depending on the destination of the electrode and must therefore be determined in each particular case.
  • the substrate of the electrode according to the invention may be a plate solid or openwork, rigid or flexible, a wire, a lattice of intertwined wires or a stack of beads.
  • the coating must be present on the substrate in an amount sufficient to cover a substantial part of the substrate and to catalyze the electrochemical reaction for which the electrode is intended.
  • the optimum amount of coating will therefore depend on the electrochemical reaction for which the electrode is intended and it can be determined in each particular case by routine laboratory work.
  • it is desirable that the coating is present on the substrate in an amount at least equal to 1 g (preferably 5 g) per m 2 of the surface of the substrate to which it is applied.
  • 1 g preferably 5 g
  • thickness of the coating on the substrate there is, in principle, no upper limit to the thickness of the coating on the substrate, in practice there is no point in it exceeding 20 g per m 2 of the aforementioned surface of the substrate, thicknesses of 8 to 12 g / m 2 being specially recommended.
  • platinum, iridium oxide and the tin oxide are preferably distributed homogeneously in the coating.
  • this expression is meant that the relative concentrations of platinum, iridium oxide and tin oxide are substantially identical in all coating points or that they do not diverge more 5% (preferably 1%) between any two points of the coating.
  • any suitable means may be used to apply the coating on the substrate.
  • One recommended way is to apply on the substrate a coating of thermally decomposable platinum compounds, iridium and tin and then subject the coating to treatment thermal in an oxidizing atmosphere, so as to decompose the compounds thermally decomposable and to form the coating.
  • Heat-decomposable compounds can be any compound which, heated in an atmosphere oxidizing, release platinum or platinum oxide, iridium dioxide and tin dioxide. They can for example be selected from the nitrates, sulfates, phosphates, halides and acid salts carboxylic.
  • heat-decomposable compounds above can be used in the solid state, for example in the state a powder, or in a liquid state, for example in the form of molten salts, suspensions or solutions.
  • the heat treatment consists, by definition, by heating the coating to a sufficient temperature in controlled oxidizing atmosphere to decompose thermally decomposable compounds and coprecipitate platinum or platinum oxide, iridium oxide and tin oxide.
  • the oxidizing atmosphere can consist of atmospheric air, enriched air or pure oxygen. We prefer to use atmospheric air.
  • the choice of thermally decomposable compounds and the temperature of the heat treatment are interdependent.
  • the choice of thermally decomposable compounds is notably influenced by the permissible temperature for heat treatment, so as to prevent it from damaging the substrate.
  • the thermally decomposable compounds are selected from the halides and these are used at the state dissolved in an organic solvent.
  • Chlorides are preferred, in particular especially iridium tetrachloride, tin tetrachloride and acid hexachloroplatinic
  • the organic solvent is advantageously selected from alcohols, preferably aliphatic alcohols such as methanol, ethanol and isopropanol, for example.
  • temperatures from 100 to 1000 ° C are suitable in the majority of cases, those of 200 to 750 ° C being specially recommended.
  • an iridium oxide content greater than 8% (preferably at least equal to 25%) of the weight of the coating allows to substantially increase the overvoltage of discharge of oxygen anions, when the electrode is used as an anode in an electrolysis process of an aqueous solution an alkali metal salt, in particular sodium chloride.
  • the platinum content of the coating is at least 10% (from preferably at least 12%) by weight.
  • This embodiment of the electrode has the additional advantage of having lower overvoltage at electrochemical discharge of chloride anions and it is therefore specially adapted to serve as an anode in processes electrolytic production of chlorine.
  • the electrode coating can consist exclusively of platinum, iridium oxide and tin oxide, or it may include a or several additional compounds, different from platinum, oxide iridium and tin oxide. In general it is preferred that the coating of the electrode according to the invention consists essentially of platinum, iridium oxide and tin oxide.
  • the coating of the electrode essentially consists of 12 to 17% by weight of platinum, from 30 to 40% by weight of iridium oxide and from 43 to 58% by weight of oxide of tin.
  • the electrode according to this embodiment of the invention especially suitable as an anode for the production of chlorine by electrolysis of aqueous solutions of alkali metal chloride.
  • the invention therefore also relates to the use of the electrode according to the invention as an anode in the electrolysis processes of the salts of alkali metals in aqueous solution, especially for the production of chlorine by electrolysis of aqueous metal chloride solutions alkaline. It especially concerns the use of the electrode according to the invention as an anode for the production of chlorine by electrolysis of a aqueous sodium chloride solution.
  • electrodes were prepared comprising a titanium substrate and a coating of platinum, iridium oxide and tin oxide on the substrate.
  • the substrate consisted of a lattice in the form of a disc of approximately 100 cm 2 in area and the coating was applied to the entire area of the disc.
  • three separate organic solutions were first prepared, namely a solution of hexachloroplatinic acid in isopropanol (30 g of hexachloroplatinic acid per liter of solution), a solution of iridium tetrachloride in isopropanol (20 g iridium tetrachloride per liter of solution) and a solution of tin tetrachloride in isopropanol (23 g tin tetrachloride per liter of solution).
  • the three solutions were then mixed in adequate proportions to form the coating and it was then applied to the disc in ten successive layers. After each layer of plaster, the disc and the plaster were heated in atmospheric air, at a temperature of 450 ° C for one hour.
  • the electrodes obtained as described above were used as anodes in a laboratory electrolysis cell, the cathode of which consisted of a 100 cm 2 nickel disc, separated from the anode by a membrane of the NAFION brand. ® (DU PONT), selectively permeable to cations.
  • the distance between the anode and the cathode was set at 1 mm.
  • an appreciably saturated aqueous solution of sodium chloride was electrolysed at 85 ° C., under an anodic current density of 3.5 kA / m 2 .
  • the anode chamber of the cell was continuously supplied with the sodium chloride solution, so as to produce, in the cathode chamber, an aqueous solution of approximately 32% by weight of hydroxide. sodium.
  • chlorine was produced at the anode and hydrogen was produced at the cathode.
  • the oxygen content in the gas collected at the anode was measured. The results of the measurements were plotted on the diagram of the appended drawing. On this diagram, the abscissa scale represents time, expressed in days, and the ordinate scale represents the oxygen content in the gas produced at the anode (expressed in% by weight of gas).

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)
  • Battery Electrode And Active Subsutance (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Primary Cells (AREA)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
  • Inert Electrodes (AREA)
  • Chemically Coating (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Secondary Cells (AREA)
EP95202666A 1994-10-11 1995-10-04 Electrode pour procédé électrochimique et utilisation de ladite électrode Expired - Lifetime EP0707095B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI942070A IT1270649B (it) 1994-10-11 1994-10-11 Elettrodo per un procedimento elettrochimico e impiego di detto elettrodo
ITMI942070 1994-10-11

Publications (2)

Publication Number Publication Date
EP0707095A1 EP0707095A1 (fr) 1996-04-17
EP0707095B1 true EP0707095B1 (fr) 1999-03-31

Family

ID=11369689

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95202666A Expired - Lifetime EP0707095B1 (fr) 1994-10-11 1995-10-04 Electrode pour procédé électrochimique et utilisation de ladite électrode

Country Status (11)

Country Link
US (1) US5679225A (it)
EP (1) EP0707095B1 (it)
JP (1) JP3943151B2 (it)
AT (1) ATE178367T1 (it)
BR (1) BR9504362A (it)
CA (1) CA2160221C (it)
DE (1) DE69508689T2 (it)
DK (1) DK0707095T3 (it)
ES (1) ES2131758T3 (it)
IT (1) IT1270649B (it)
PL (1) PL178811B1 (it)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2716207B1 (fr) * 1994-02-15 1996-05-31 Rhone Poulenc Chimie Matériau électroactive, sa préparation et son utilisation pour l'obtention d'éléments cathodiques.
US5989396A (en) * 1997-04-02 1999-11-23 Eltech Systems Corporation Electrode and electrolytic cell containing same
US6271131B1 (en) * 1998-08-26 2001-08-07 Micron Technology, Inc. Methods for forming rhodium-containing layers such as platinum-rhodium barrier layers
US6323081B1 (en) 1998-09-03 2001-11-27 Micron Technology, Inc. Diffusion barrier layers and methods of forming same
US6284655B1 (en) 1998-09-03 2001-09-04 Micron Technology, Inc. Method for producing low carbon/oxygen conductive layers
US6239028B1 (en) * 1998-09-03 2001-05-29 Micron Technology, Inc. Methods for forming iridium-containing films on substrates
US6329286B1 (en) 1999-04-27 2001-12-11 Micron Technology, Inc. Methods for forming conformal iridium layers on substrates
US6660631B1 (en) * 2000-08-31 2003-12-09 Micron Technology, Inc. Devices containing platinum-iridium films and methods of preparing such films and devices
JP4476759B2 (ja) * 2004-09-17 2010-06-09 多摩化学工業株式会社 電解用電極の製造方法、及びこの電解用電極を用いた水酸化第四アンモニウム水溶液の製造方法
KR20190022333A (ko) * 2017-08-23 2019-03-06 주식회사 엘지화학 전기분해용 양극 및 이의 제조방법
CN112041482B (zh) 2018-07-06 2023-06-16 株式会社Lg化学 用于电解的还原电极的活性层组合物以及由其得到的还原电极
WO2022103102A1 (ko) 2020-11-12 2022-05-19 주식회사 엘지화학 전기분해용 전극

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3460087D1 (en) * 1983-03-11 1986-05-22 Bbc Brown Boveri & Cie Catalyst for the coating of anodes, and its manufacturing process
JPS60162787A (ja) * 1984-01-31 1985-08-24 Tdk Corp 電解用電極
JPH0633489B2 (ja) * 1984-08-17 1994-05-02 ティーディーケイ株式会社 希薄塩水電解用電極
JPS62243790A (ja) * 1986-04-15 1987-10-24 Osaka Soda Co Ltd 塩化アルカリ電解用陽極
JP2885913B2 (ja) * 1990-09-04 1999-04-26 ペルメレック電極株式会社 クロムめっき用陽極およびその製造方法

Also Published As

Publication number Publication date
EP0707095A1 (fr) 1996-04-17
ITMI942070A1 (it) 1996-04-11
ATE178367T1 (de) 1999-04-15
ITMI942070A0 (it) 1994-10-11
JP3943151B2 (ja) 2007-07-11
DK0707095T3 (da) 1999-10-18
PL178811B1 (pl) 2000-06-30
DE69508689T2 (de) 1999-09-30
PL310881A1 (en) 1996-04-15
CA2160221A1 (fr) 1996-04-12
ES2131758T3 (es) 1999-08-01
BR9504362A (pt) 1997-09-02
US5679225A (en) 1997-10-21
JPH08176876A (ja) 1996-07-09
CA2160221C (fr) 2007-02-20
IT1270649B (it) 1997-05-07
DE69508689D1 (de) 1999-05-06

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