US3880728A - Manufacture of lead dioxide/titanium composite electrodes - Google Patents

Manufacture of lead dioxide/titanium composite electrodes Download PDF

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Publication number
US3880728A
US3880728A US502666A US50266674A US3880728A US 3880728 A US3880728 A US 3880728A US 502666 A US502666 A US 502666A US 50266674 A US50266674 A US 50266674A US 3880728 A US3880728 A US 3880728A
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United States
Prior art keywords
titanium
lead dioxide
disilicide
silicide
carbide
Prior art date
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Expired - Lifetime
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US502666A
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English (en)
Inventor
Wolfgang Habermann
Heinz Nohe
Peter Jaeger
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BASF SE
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BASF SE
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Filing date
Publication date
Priority claimed from DE19732344645 external-priority patent/DE2344645C3/de
Priority claimed from DE2436394A external-priority patent/DE2436394A1/de
Application filed by BASF SE filed Critical BASF SE
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Publication of US3880728A publication Critical patent/US3880728A/en
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Expired - Lifetime legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • Composite electrodes of a base consisting of titanium to which lead dioxide coatings have been applied are known. Such electrodes are manufactured by conventional methods, through anodic deposition of the oxide from lead-ll salt solution onto the titanium substrate. Because titanium blocks the passage of current if it is wired as the anode in an electrolysis system, it is hovw ever not possible anodically to deposit an even and well-adhering lead dioxide coating on a titanium surface. It is known to avoid this blockage by adding fluorides to the lead salt bath or by mechanically roughening. and degreasing. the titanium surface.
  • lead dioxide/titanium composite electrodes by applying seeds of finely divided platinum. palladium. gold, magnetite. graphite and/or lead dioxide to the titanium surface before the anodic deposition of lead dioxide.
  • the electrodes produced in accordance with the processes which have been disclosed are not equally suitable for all applications. Thus. for example. they suffer from the disadvantage that if they are employed as anodes in electrolysis cells of high current throughput the lead dioxide layers flake off. especially after prolonged anodic polarization. and this results in the gradual formation of a blocking layer of titanium dioxide between the titanium and the lead dioxide. If the process carried out uses noble metals, such electrodes can, for example when employed as anodes in electrolysis cells with cathodes of high hydrogen overvoltage, inactivate the cathodes. Furthermore. some of the conventional processes are costly and time-consuming.
  • this object is achieved by a process for the production of lead dioxide/titanium composite electrodes by anodic deposition of lead dioxide on titanium surfaces wherein an intermediate layer of a carbide or boride of an element of sub-group 4 or 5 and/or a silicide of an element of sub-group 4. 5 or 6 of the periodic table of the elements and/or silicon carbide, is applied to the titanium surface before depositing the lead dioxide.
  • Particularly suitable carbides and borides are those of titanium and tantalum. and titanium carbide. tantalum carbide and tantalum boride should be singled out specifically.
  • Preferred silicides for use in the intermediate layers are titanium disilicide. zirconium disilicide. tantalum disilicide. chromium disilicide and niobium disilicide. amongst which chromium disilicide. titanium disilicide and zirconium disilicide give particularly dense intermediate layers because of their low melting points. which are from l.500 to l.700C. Silicon carbide is also preferred.
  • the intermediate layers can also consist of a mixture of these compounds.
  • the base is first cleaned. preferably mechanically, for example by sandblasting or corundum blasting. Thereafter, the carbides and borides of the elements of sub-groups 4 and 5 of the periodic system (Ti, Zr. Hf. V. Nb and Ta) and the silicides of the elements of sub-groups 4 to 6 of the periodic system (Ti, Zr. Hf. V, Nb. Ta. Cr. Mo and W) and/or silicon carbide are applied.
  • the plasma spraying process can be used and is advantageously carried out under a protective atmosphere of argon gas; in this process. the powders of the compounds mentioned. of particle sizes preferably from 15 to 90 ,u.
  • the thickness of the intermediate layers produced in preferably from about to 200 ,u.. but where the layers contain more than 20 percent by weight of the silicides mentioned. and/or of silicon carbide, a thickness down to 20 ,u. suffices.
  • the silicides or the silicon carbide can also be modified with metals or halides of the iron group. especially with iron itself.
  • the proportion of metals or halides of the iron group is so chosen that the content. based on pure metal. in the silicide does not exceed 5 percent by weight.
  • carbides or silicides and the silicon carbide are the flame spraying process and high vacuum vapor-coating. In these processes, as in the plasma spraying process. it is important that the electrically conducting base should be freed from oxides on the surface which is to be coated.
  • a particularly suitable process for applying intermediate layers of silicon or silicon carbide to electrically conducting shapes has proved to be vapor phase deposition by a chemical reaction with application of radiant energy or heat energy.
  • halides of elements of sub-groups 4 to 6 can be reacted with silanes or silicon halides and hydrogen or base metals to give silicides which deposit as dense coatings on the surface of the electrically conducting bases.
  • the titanium bodies pretreated in this way are then provided with a PbO coating by conventional anodic methods.
  • lead(ll) nitrate or lead(ll) perchlorate solutions which can advantageously contain up to 0.5 percentof copper( ll) nitrate and up to 0.2 percent of a wetting agent. for example based on ethoxylated alcohols.
  • the current density is advantageously from 1 to A/dm and the temperature is advantageously from 40 to 80C.
  • Copper is a suitable cathode material. Good convection is advantageously ensured by stirring or circulation.
  • the pH value of the solution, which decreases during the electrolysis. is preferably maintained within the range 1 pH s 5 by adding basic lead carbonate.
  • EXAMPLE 1 An expanded metal mesh of titanium, of dimensions 100 X 40 mm. was corundum-blasted and coated with fine-grained titanium carbide. particle size from 40 to 90 ,u, to a thickness of about 0. mm by means of a plasma torch, under a blanket or argon gas. In carrying out the coating. the plasma torch was operated with argon containing less than 0.5 percent of nitrogen. The expanded titanium metal was at a temperature of s 60C during coating.
  • the expanded titanium metal mesh pretreated in this way was dipped to a depth of 5 cm, along its longitudinal axis, into a solution which was prepared by dissolving 300 g of Pb(NO;,)- 3 g of Cu(NO,,) 3 H 0 and l g of a wetting agent based on ethoxylated alcohols in water to make a total of 1 liter. and was coated at a temperature of from 60 to 70C for 3 hours, using a current of 0.8 A i 0.1 A 4 i 0.5 A/dm A copper sheet was used as the cathode.
  • This treatment resulted I in the deposition of 10.96 g of PbO
  • the lead dioxide/titanium composite electrode thus produced was subjected. in approx.
  • the mesh was then immersed, as the anode. into a lead-ll salt bath under the same conditions as in Example l, causing the deposition of 10.68 g of PbO- EXAMPLE 3
  • the mesh was first coated with tantalum boride of particle size from 40 to 90 y. and then with lead dioxide. using the methods described in Example 1. A total of 10.20 g of PbO were deposited.
  • EXAMPLE 4 An expanded titanium metal mesh of dimensions 100 X 40 mm was corundum-blasted and coated with finegrained titanium disilicide, particle size from 20 to 40 u. to a thickness of about 100 ,u by means of a plasma torch. under a blanket of argon gas. In carrying out the coating. the plasma torch was operated with argon containing less than 0.5 percent of nitrogen. The expanded titanium metal was at a temperature of s 60C during coating.
  • the expanded titanium metal mesh pretreated in this way was dipped to a depth of 5 cm. along its longitudinal axis. into a solution which was prepared by dissolving 300 g of Pb(NO 3 g of Cu(NO 3 H 0 and l g ofa wetting agent based on ethoxylated alcohols in water to make a total of 1 liter. and was coated at a temperature of from 60 to C for 3 hours. using a current of 0.8 A i 0.1 A 4 i 0.5 A/dm A copper sheet was used as the cathode. This treatment resulted in the deposition of 8.36 g of PbO- the geometrical surface area was 0.2 dm
  • the lead dioxide/titanium composite electrode thus produced was subjected to a current of 20 A 100 A/dm in approx. 20 percent strength sulfuric acid at from 30 to 35C for 100 hours.
  • the weight loss of the anode at this current density was approx. 0.7 mg/ampere hour.
  • EXAMPLE 5 An expanded titanium metal mesh was coated with tantalum disilicide of particle size from 20 to 40 ,U. by the method described in Example 4.
  • the mesh was then immersed, as the anode, into a lead-ll salt bath under the same conditions as in Example 4, causing the deposition of 9.84 g of PbO
  • the weight loss of the lead dioxide/titanium composite electrode thus produced was approx. 0.9 mg/ampere hour under the conditions specified in Example 1.
  • EXAMPLE 6 Using the method described in Example 4. the mesh was first coated with chromium disilicide of particle size from 20 to 40 ,u and then with lead dioxide. 1 L g of PbOg deposited and the weight loss under the conditions specified in Example I was approx. 0.6 mg/ampere hour.
  • EXAMPLE 7 Using the method described in Example 4. the mesh was first coated with silicon carbide of particle size from 20 to 40 ,u. and then with lead dioxide. 9.41 g of Pb0 deposited and the weight loss under the conditions specified in Example 1 was approx. 0.5 mg/ampere hour.
  • a process for the manufacture of a lead dioxide/- titanium composite electrode by anodic deposition of lead dioxide on a titanium surface wherein an intermediate layer of a carbide or boride of an element of subgroup 4 or 5 and/or a silicide of an element of subgroup 4, 5 or 6 of the periodic table of the elements and/or silicon carbide, is applied to the titanium surface before depositing the lead dioxide.
  • a process as claimed in claim 1 wherein the intermediate layer applied is from 60 to 200 p. thick if it contains less than 20 percent by weight of silicide and- /or silicon carbide.
  • intermediate layer applied is from 20 to 200 p. thick if it contains more than 20 percent by weight of silicide and/or silicon carbide.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Coating By Spraying Or Casting (AREA)
US502666A 1973-09-05 1974-09-03 Manufacture of lead dioxide/titanium composite electrodes Expired - Lifetime US3880728A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19732344645 DE2344645C3 (de) 1973-09-05 Verfahren zur Herstellung von Bleidioxid-Titanverbundelektroden
DE2436394A DE2436394A1 (de) 1974-07-29 1974-07-29 Verfahren zur herstellung von bleidioxid-titanverbundelektroden

Publications (1)

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US3880728A true US3880728A (en) 1975-04-29

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US (1) US3880728A (enrdf_load_stackoverflow)
JP (1) JPS5072878A (enrdf_load_stackoverflow)
CA (1) CA1030482A (enrdf_load_stackoverflow)
CH (1) CH592162A5 (enrdf_load_stackoverflow)
FR (1) FR2242783B1 (enrdf_load_stackoverflow)
GB (1) GB1476487A (enrdf_load_stackoverflow)
IT (1) IT1019188B (enrdf_load_stackoverflow)
SE (1) SE392622B (enrdf_load_stackoverflow)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4038170A (en) * 1976-03-01 1977-07-26 Rhees Raymond C Anode containing lead dioxide deposit and process of production
US4039403A (en) * 1975-03-05 1977-08-02 Imperial Metal Industries (Kynoch) Limited Electrowinning metals
US4051000A (en) * 1974-11-04 1977-09-27 The International Nickel Company, Inc. Non-contaminating anode suitable for electrowinning applications
US4057679A (en) * 1974-09-06 1977-11-08 P. R. Mallory & Co. Inc. Organic electrolyte batteries
US4236978A (en) * 1980-02-08 1980-12-02 Rsr Corporation Stable lead dioxide anode and method for production
ES2037614A1 (es) * 1991-12-26 1993-06-16 Tudor Acumulador Procedimiento para la preparacion de placas o electrodos bipolares plomo-bioxido de plomo para acumuladores electricos.
US5407556A (en) * 1992-11-11 1995-04-18 Permelec Electrode Ltd. Process of producing metallic foil by electrolysis
US20030136669A1 (en) * 2002-01-03 2003-07-24 Fritz Gestermann Electrode for electrolysis in acidic media
US20090269666A1 (en) * 2008-04-28 2009-10-29 Edgar Lara-Curzio Lightweight, Durable Lead-Acid Batteries
WO2013106419A1 (en) * 2012-01-13 2013-07-18 Energy Power Systems Llc. Improved substrate for electrode of electrochemical cell
US8808914B2 (en) 2012-01-13 2014-08-19 Energy Power Systems, LLC Lead-acid battery design having versatile form factor
CN104562094A (zh) * 2015-01-20 2015-04-29 昆明理工恒达科技股份有限公司 一种有色金属电积用梯度复合阳极的制备方法
US9263721B2 (en) 2012-01-13 2016-02-16 Energy Power Systems LLC Lead-acid battery design having versatile form factor
US9595360B2 (en) 2012-01-13 2017-03-14 Energy Power Systems LLC Metallic alloys having amorphous, nano-crystalline, or microcrystalline structure

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4040939A (en) * 1975-12-29 1977-08-09 Diamond Shamrock Corporation Lead dioxide electrode
JPS5923890A (ja) * 1982-07-29 1984-02-07 Plasma Giken Kogyo Kk 不溶性電極
CH665429A5 (en) * 1985-04-04 1988-05-13 Bbc Brown Boveri & Cie Electrochemical cell anode - with titanium carbide layer between titanium support and lead di:oxide layer

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2636856A (en) * 1948-06-29 1953-04-28 Mallory & Co Inc P R Electrode for electrochemical oxidation
US3486940A (en) * 1968-07-30 1969-12-30 Samuel Ruben Storage battery having a positive electrode comprising a supporting base of titanium nitride having a surface film of non-polarizing material
US3499795A (en) * 1968-04-08 1970-03-10 Samuel Ruben Storage battery having electrodes comprising a supporting base of titanium nitride
US3649485A (en) * 1968-10-02 1972-03-14 Ppg Industries Inc Electrolysis of brine using coated carbon anodes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2636856A (en) * 1948-06-29 1953-04-28 Mallory & Co Inc P R Electrode for electrochemical oxidation
US3499795A (en) * 1968-04-08 1970-03-10 Samuel Ruben Storage battery having electrodes comprising a supporting base of titanium nitride
US3486940A (en) * 1968-07-30 1969-12-30 Samuel Ruben Storage battery having a positive electrode comprising a supporting base of titanium nitride having a surface film of non-polarizing material
US3649485A (en) * 1968-10-02 1972-03-14 Ppg Industries Inc Electrolysis of brine using coated carbon anodes
US3770613A (en) * 1968-10-02 1973-11-06 Nora Int Co Novel electrode

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4057679A (en) * 1974-09-06 1977-11-08 P. R. Mallory & Co. Inc. Organic electrolyte batteries
US4051000A (en) * 1974-11-04 1977-09-27 The International Nickel Company, Inc. Non-contaminating anode suitable for electrowinning applications
US4039403A (en) * 1975-03-05 1977-08-02 Imperial Metal Industries (Kynoch) Limited Electrowinning metals
US4038170A (en) * 1976-03-01 1977-07-26 Rhees Raymond C Anode containing lead dioxide deposit and process of production
US4236978A (en) * 1980-02-08 1980-12-02 Rsr Corporation Stable lead dioxide anode and method for production
ES2037614A1 (es) * 1991-12-26 1993-06-16 Tudor Acumulador Procedimiento para la preparacion de placas o electrodos bipolares plomo-bioxido de plomo para acumuladores electricos.
US5407556A (en) * 1992-11-11 1995-04-18 Permelec Electrode Ltd. Process of producing metallic foil by electrolysis
US7211177B2 (en) * 2002-01-03 2007-05-01 Bayer Aktiengesellschaft Electrode for electrolysis in acidic media
US20030136669A1 (en) * 2002-01-03 2003-07-24 Fritz Gestermann Electrode for electrolysis in acidic media
CN100415937C (zh) * 2002-01-03 2008-09-03 拜尔材料科学股份公司 用于在酸性介质中进行电解的电极
US20090269666A1 (en) * 2008-04-28 2009-10-29 Edgar Lara-Curzio Lightweight, Durable Lead-Acid Batteries
US8017273B2 (en) * 2008-04-28 2011-09-13 Ut-Battelle Llc Lightweight, durable lead-acid batteries
US8445138B2 (en) 2008-04-28 2013-05-21 Ut-Battelle Llc Lightweight, durable lead-acid batteries
WO2013106419A1 (en) * 2012-01-13 2013-07-18 Energy Power Systems Llc. Improved substrate for electrode of electrochemical cell
US8808914B2 (en) 2012-01-13 2014-08-19 Energy Power Systems, LLC Lead-acid battery design having versatile form factor
US9263721B2 (en) 2012-01-13 2016-02-16 Energy Power Systems LLC Lead-acid battery design having versatile form factor
US9595360B2 (en) 2012-01-13 2017-03-14 Energy Power Systems LLC Metallic alloys having amorphous, nano-crystalline, or microcrystalline structure
CN104562094A (zh) * 2015-01-20 2015-04-29 昆明理工恒达科技股份有限公司 一种有色金属电积用梯度复合阳极的制备方法
CN104562094B (zh) * 2015-01-20 2016-11-16 昆明理工恒达科技股份有限公司 一种有色金属电积用梯度复合阳极的制备方法

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Publication number Publication date
GB1476487A (en) 1977-06-16
CA1030482A (en) 1978-05-02
IT1019188B (it) 1977-11-10
SE392622B (sv) 1977-04-04
JPS5072878A (enrdf_load_stackoverflow) 1975-06-16
FR2242783B1 (enrdf_load_stackoverflow) 1981-04-17
FR2242783A1 (enrdf_load_stackoverflow) 1975-03-28
SE7411031L (enrdf_load_stackoverflow) 1975-03-06
CH592162A5 (enrdf_load_stackoverflow) 1977-10-14

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