CA1044754A - Process for making titanium supported lead electrode - Google Patents
Process for making titanium supported lead electrodeInfo
- Publication number
- CA1044754A CA1044754A CA235,633A CA235633A CA1044754A CA 1044754 A CA1044754 A CA 1044754A CA 235633 A CA235633 A CA 235633A CA 1044754 A CA1044754 A CA 1044754A
- Authority
- CA
- Canada
- Prior art keywords
- titanium
- solution
- electrolyte
- lead
- treatment bath
- 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
Links
- 239000010936 titanium Substances 0.000 title claims abstract description 35
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims description 19
- 239000000243 solution Substances 0.000 claims abstract description 22
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 238000005554 pickling Methods 0.000 claims abstract description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 150000002500 ions Chemical class 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 238000009835 boiling Methods 0.000 claims abstract description 6
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000003368 amide group Chemical group 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 3
- 150000003608 titanium Chemical class 0.000 claims abstract 2
- 229910000464 lead oxide Inorganic materials 0.000 claims description 8
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims description 2
- 239000002738 chelating agent Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 3
- 230000001706 oxygenating effect Effects 0.000 claims 3
- 150000007513 acids Chemical class 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 235000011007 phosphoric acid Nutrition 0.000 claims 1
- 150000003016 phosphoric acids Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 abstract description 3
- 229910019142 PO4 Inorganic materials 0.000 abstract description 2
- 238000007743 anodising Methods 0.000 abstract description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-M fluorosulfonate Chemical compound [O-]S(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-M 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 2
- 239000010452 phosphate Substances 0.000 abstract description 2
- 150000004767 nitrides Chemical class 0.000 abstract 1
- 230000008021 deposition Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000274 adsorptive effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000002048 anodisation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BBJSDUUHGVDNKL-UHFFFAOYSA-J oxalate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BBJSDUUHGVDNKL-UHFFFAOYSA-J 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- 208000031872 Body Remains Diseases 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- -1 amido sulfate Chemical compound 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000001609 comparable effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
Classifications
-
- 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
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
-
- 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
-
- 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
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Chemical Treatment Of Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
In making a lead electrode for a lead-acid accumulator or the like, a supporting body of titanium is pickled in a boiling solution of oxalic acid and then adsorptively coated with a titanium (IV) layer in a treatment bath. This treatment is followed by the anodic coating of the titanium body with PbO2 in an electrolyte containing the lens of lead (II), in the presence of a lead (II) nitrate or a lead (II) salt of an amido. imido, nitride or fluoro sulfate or phosphate. The treatment bath may be an aqueous solution of an organic titanium salt, the pickling solution, or the electrolyte. If the pickling solution is used for this purpose, the titanium body is anodically connected or the solution is oxygenated. If the electrolyte is utilized, Ti(IV) ions are introduced into that liquid in which the titanium body is immersed for an extended period before closure of the anodizing circuit.
In making a lead electrode for a lead-acid accumulator or the like, a supporting body of titanium is pickled in a boiling solution of oxalic acid and then adsorptively coated with a titanium (IV) layer in a treatment bath. This treatment is followed by the anodic coating of the titanium body with PbO2 in an electrolyte containing the lens of lead (II), in the presence of a lead (II) nitrate or a lead (II) salt of an amido. imido, nitride or fluoro sulfate or phosphate. The treatment bath may be an aqueous solution of an organic titanium salt, the pickling solution, or the electrolyte. If the pickling solution is used for this purpose, the titanium body is anodically connected or the solution is oxygenated. If the electrolyte is utilized, Ti(IV) ions are introduced into that liquid in which the titanium body is immersed for an extended period before closure of the anodizing circuit.
Description
~V~7S~
SPECIFIC~TION
Field of the Invention Our present invention relates to the manufacture of an electrode which contains lead oxide as an active material, as used in lead-acid accumulators or for electrolytic purposes.
Background of the Invention Solid electrodes of leaa oxide are mechanically weak and are thus of limited practical utility. Use is therefore frequently made of an inert metallic support, such as a plate or a grid, which is coated with lead oxide lQ PbOn~ preferably by electrolytic deposition. Such a support advantageously consists of titanium; however, firmly adhering coatings of lead oxide have heretofore been achieved on titanium bodies only by relatively complicated and costly processes.
In commonly owned U.S. patent application Ser. No. ~68,80~ filed 10 May 1974, now patent No. 3,935,082, there has been disclosed a process for manufacturing electrodes of this nature. ~ccording to that prior appli~
cation, a titanium body is cleansed in a hot mordanting or pickling solution of aqueous oxallc acid, this operation being followed by prolonged immersion in the same bath in which a titanium-oxalate complex has been dissolved.
Thereafter, the titanium body is anodically connected against a suitable conterelectrode in an electrolytecontaining the ions of lead ~II) in the presence of a Pb~II) salt of an amido, imido, nitrido or fluoro sulfate nr phosphate. A f1nal treatment state may comprise prolonged immersion in a weakly alkaline medium.
Thoagh the process described in the prior U.S. patent has been practiced successfully, and is also fuIly reproducible, there has as yet not been establlshed a compreh:nsive theory which would allow the develop-ment of a variety of techniques for the formation of different types of PbO2 deposits firmly adhering to the supporting titanium body.
Object of _he Invention ` :' ""':
.~,'.'" '" ,"
The object of our present invention, therefore, is to provide a process for effectively obviating the formation of poor]y conductive or practically nonconductive oxide layers on a titanium substrate to be laden -~-with lead oxide.
We have found, in accord~nce with the present invention, that such oxide formation can be effectively inhibited by the adsorptive coating of the titanium substrate with a titanium (IV) layer prior to the deposition o~ PbO2 thereon from a suitable electrolyte, such as those described in U.S. patent 3,935,082.
Such an adsorptive Ti(IV) layer, whose thickness is not critical, may be formed in a variety of treatment baths, specifically in the pickling solution used in the initial cleansing step or in the electrolyte serving for the anodic deposition of PbO2. In the first instance, the titanium body may be anodically connected in the pickling or mordanting solution (which is not necessarily limited to oxalic acid but may be any liquid capable of : .
~ dissolving titanium) and/or that solution may be oxygenated by the intro-., , ' '. : .
duction of air, oxygen or some other oxidizing agent into same. In the second instance, the titanium body may be exposed for an extended period to ~ the electrolyte before the anodic circuit is closed, the electrolyte being f enriched in this case with Ti(IV) ions by the prior dissolution of a suit-20 able titanium c~mpound therein.
There exists also the possibility of immersing the titanium body, after pickling and before anodization, in a preferably boiling aqueous solution of a Ti(IV) salt of an organic acid, advantageously a chelating agent such as ethylene-diaminetetracidlc acid ~EDTA). -We have found, that the presence of an adsorptive Ti~IV) coating ~:
in a titanium substrate establishes an electrochemical surface potential substantially different from that of a body covered with Ti(III). As a ~ result of this differqnce in potential, the flow of anodizing current in the ;' electro:Lyte does not cause an initial surface oxidation of the subs-trate 30 but brings about an immediate deposition of lead oxide thereon, possibly ,, , . . . ~, :~ , accompanied by a lead titanate.
Sui-table electrolytes include not only the aEorementioned solutions of lead(II) salt of an amido, imido, nitrido or fluoro derivative of sulfuric or phosphoric acid, as noted in the prior application and patent, but also the lead(II) salt of nitric acid.
EXAMPLE I
A titanium body in the form of an expanded-metal sheet or a solid plate is subjected to the following steps:
(aj Pickling for one hour in aqueous o~alic acid at 15%i concentra-tion and at 100 C.
(b) Immersion for two hours in a boiling EDT~/Ti(IV~ solution.
~ c) Anodic coating with lead oxide from a Pb(II) electrolyte as described above, e.g. a solution of Pb(II) amido sulfate ranging in conductivity between 10 and 10 mho-cm . The electroiyte may be maintained at 65 C and the current flow, e.g. of 20 mA/cm , may be periodically interrupted as described in the commonly owned application and patent ~;
identified above.
(d) Rinsing of the fully coated electrode in ~ater, (e) Treatment for two hours in a boiling aqueous solution of NaOH with pH ~g 8.
Tha result is a dense, firmly adhering layer of lead oxide com-parable to that obtained by the process of the copending application and patent. -EXAMPLE II :
(a) Same as in Example I.
.
(b) The titanium body remains immersed in the pickling solution of step (a) for at least half an hour and is anodically biased, with a ~;
current flow of about 10 to 20 mA/cm .
(c) - (e) Same as in Example I, with similar result.
EXAMPLE III
. .... ..
- 3 - ~
,:
5~ :
(a) Same as in Example I.
(b) The titanium body is left immersed in the pickling solution o~
step (a), reduced to a temperature of 50 C, with bubling of air or oxygen through the solution until the color of the body has changed from dark brown to light yellow. This is followed by boiling in the solution for one hour.
(c) - (e) Same as in Example I, with similar result.
EXAMPLE IV ~
(a) Same as in Example I. ~ ~;
(b) The pickling solution used in step (a) is admixed with 30% ' hydrogen peroxide in a proportion of about 5~ by volume. The titanium body is boiled for two hours in this mixture.
(c) - (e) Same as in Example I. The result is a highly fine-grained, 1rmly adhering PbO2 layer.
EX~MPLE V
(a) Same as Example I.
tb) Immerslon for at least 30 m mutes in an electrolyte of Pb~II) nitrate in which a small quantity of titanium nitrate has been dissolved to supply Ti~IV) ions to the bath.
(c) Anodization, as in Example ~, in the bath of step (b), followed by steps (d) and (e) of Example I. The result is a glossy, deep-black, smooth coating of lèad oxide.
Step (e) may be omitted in some instances. The pickling or mordanting bath of step (a) and the electrolyte of step (c) may be modified, as discussed above, and an additional treatment with a titanium-oxalate complex as described in the prior applicàtion and patent may be inser~ed between steps (b) and (c), if desired, especially in Examples I - IV. -Between steps (c) and (d) a second eletrodeposition may be carried out, as also described in the prior application and patent, with an electrolyte I
containing only lead nitrate; this is particularly advantageous in the case of Example V to enhance the gloss and the smoothness of the coating.
, .
SPECIFIC~TION
Field of the Invention Our present invention relates to the manufacture of an electrode which contains lead oxide as an active material, as used in lead-acid accumulators or for electrolytic purposes.
Background of the Invention Solid electrodes of leaa oxide are mechanically weak and are thus of limited practical utility. Use is therefore frequently made of an inert metallic support, such as a plate or a grid, which is coated with lead oxide lQ PbOn~ preferably by electrolytic deposition. Such a support advantageously consists of titanium; however, firmly adhering coatings of lead oxide have heretofore been achieved on titanium bodies only by relatively complicated and costly processes.
In commonly owned U.S. patent application Ser. No. ~68,80~ filed 10 May 1974, now patent No. 3,935,082, there has been disclosed a process for manufacturing electrodes of this nature. ~ccording to that prior appli~
cation, a titanium body is cleansed in a hot mordanting or pickling solution of aqueous oxallc acid, this operation being followed by prolonged immersion in the same bath in which a titanium-oxalate complex has been dissolved.
Thereafter, the titanium body is anodically connected against a suitable conterelectrode in an electrolytecontaining the ions of lead ~II) in the presence of a Pb~II) salt of an amido, imido, nitrido or fluoro sulfate nr phosphate. A f1nal treatment state may comprise prolonged immersion in a weakly alkaline medium.
Thoagh the process described in the prior U.S. patent has been practiced successfully, and is also fuIly reproducible, there has as yet not been establlshed a compreh:nsive theory which would allow the develop-ment of a variety of techniques for the formation of different types of PbO2 deposits firmly adhering to the supporting titanium body.
Object of _he Invention ` :' ""':
.~,'.'" '" ,"
The object of our present invention, therefore, is to provide a process for effectively obviating the formation of poor]y conductive or practically nonconductive oxide layers on a titanium substrate to be laden -~-with lead oxide.
We have found, in accord~nce with the present invention, that such oxide formation can be effectively inhibited by the adsorptive coating of the titanium substrate with a titanium (IV) layer prior to the deposition o~ PbO2 thereon from a suitable electrolyte, such as those described in U.S. patent 3,935,082.
Such an adsorptive Ti(IV) layer, whose thickness is not critical, may be formed in a variety of treatment baths, specifically in the pickling solution used in the initial cleansing step or in the electrolyte serving for the anodic deposition of PbO2. In the first instance, the titanium body may be anodically connected in the pickling or mordanting solution (which is not necessarily limited to oxalic acid but may be any liquid capable of : .
~ dissolving titanium) and/or that solution may be oxygenated by the intro-., , ' '. : .
duction of air, oxygen or some other oxidizing agent into same. In the second instance, the titanium body may be exposed for an extended period to ~ the electrolyte before the anodic circuit is closed, the electrolyte being f enriched in this case with Ti(IV) ions by the prior dissolution of a suit-20 able titanium c~mpound therein.
There exists also the possibility of immersing the titanium body, after pickling and before anodization, in a preferably boiling aqueous solution of a Ti(IV) salt of an organic acid, advantageously a chelating agent such as ethylene-diaminetetracidlc acid ~EDTA). -We have found, that the presence of an adsorptive Ti~IV) coating ~:
in a titanium substrate establishes an electrochemical surface potential substantially different from that of a body covered with Ti(III). As a ~ result of this differqnce in potential, the flow of anodizing current in the ;' electro:Lyte does not cause an initial surface oxidation of the subs-trate 30 but brings about an immediate deposition of lead oxide thereon, possibly ,, , . . . ~, :~ , accompanied by a lead titanate.
Sui-table electrolytes include not only the aEorementioned solutions of lead(II) salt of an amido, imido, nitrido or fluoro derivative of sulfuric or phosphoric acid, as noted in the prior application and patent, but also the lead(II) salt of nitric acid.
EXAMPLE I
A titanium body in the form of an expanded-metal sheet or a solid plate is subjected to the following steps:
(aj Pickling for one hour in aqueous o~alic acid at 15%i concentra-tion and at 100 C.
(b) Immersion for two hours in a boiling EDT~/Ti(IV~ solution.
~ c) Anodic coating with lead oxide from a Pb(II) electrolyte as described above, e.g. a solution of Pb(II) amido sulfate ranging in conductivity between 10 and 10 mho-cm . The electroiyte may be maintained at 65 C and the current flow, e.g. of 20 mA/cm , may be periodically interrupted as described in the commonly owned application and patent ~;
identified above.
(d) Rinsing of the fully coated electrode in ~ater, (e) Treatment for two hours in a boiling aqueous solution of NaOH with pH ~g 8.
Tha result is a dense, firmly adhering layer of lead oxide com-parable to that obtained by the process of the copending application and patent. -EXAMPLE II :
(a) Same as in Example I.
.
(b) The titanium body remains immersed in the pickling solution of step (a) for at least half an hour and is anodically biased, with a ~;
current flow of about 10 to 20 mA/cm .
(c) - (e) Same as in Example I, with similar result.
EXAMPLE III
. .... ..
- 3 - ~
,:
5~ :
(a) Same as in Example I.
(b) The titanium body is left immersed in the pickling solution o~
step (a), reduced to a temperature of 50 C, with bubling of air or oxygen through the solution until the color of the body has changed from dark brown to light yellow. This is followed by boiling in the solution for one hour.
(c) - (e) Same as in Example I, with similar result.
EXAMPLE IV ~
(a) Same as in Example I. ~ ~;
(b) The pickling solution used in step (a) is admixed with 30% ' hydrogen peroxide in a proportion of about 5~ by volume. The titanium body is boiled for two hours in this mixture.
(c) - (e) Same as in Example I. The result is a highly fine-grained, 1rmly adhering PbO2 layer.
EX~MPLE V
(a) Same as Example I.
tb) Immerslon for at least 30 m mutes in an electrolyte of Pb~II) nitrate in which a small quantity of titanium nitrate has been dissolved to supply Ti~IV) ions to the bath.
(c) Anodization, as in Example ~, in the bath of step (b), followed by steps (d) and (e) of Example I. The result is a glossy, deep-black, smooth coating of lèad oxide.
Step (e) may be omitted in some instances. The pickling or mordanting bath of step (a) and the electrolyte of step (c) may be modified, as discussed above, and an additional treatment with a titanium-oxalate complex as described in the prior applicàtion and patent may be inser~ed between steps (b) and (c), if desired, especially in Examples I - IV. -Between steps (c) and (d) a second eletrodeposition may be carried out, as also described in the prior application and patent, with an electrolyte I
containing only lead nitrate; this is particularly advantageous in the case of Example V to enhance the gloss and the smoothness of the coating.
, .
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for making an electrode containing lead oxide as an active material, comprising the steps of:
(a) immersing a body of titanium in a hot pickling solution for cleansing said body;
(b) adsorptively coating the cleansed titanium body with a layer of titanium (IV) in a treatment bath; and (c) anodically coating the titanium body, treated in step (b), with PbO2 in an electrolyte containing Pb(II) ions.
(a) immersing a body of titanium in a hot pickling solution for cleansing said body;
(b) adsorptively coating the cleansed titanium body with a layer of titanium (IV) in a treatment bath; and (c) anodically coating the titanium body, treated in step (b), with PbO2 in an electrolyte containing Pb(II) ions.
2. A process as defined in claim 1 wherein said treatment bath is a boiling solution of a titanium salt of an organic acid.
3. A process as defined in claim 2 wherein said organic acid is a chelating agent.
4. A process as defined in claim 2 wherein said organic acid is ethylenediaminetetraacetic acid.
5. A process as defined in claim 1 wherein said treatment bath is said pickling solution.
6. A process as defined in claim 5 wherein said titanium body is anodically biased in step (b).
7. A process as defined in claim 5 wherein an oxygenating agent is introduced into said pickling solution in step (b).
8. A process as defined in claim 7 wherein said oxygenating agent is a flow of oxygen-rich gas bubbled through said solution.
9. A process as defined in claim 7 wherein said oxygenating agent is an admixture of hydrogen peroxide.
10. A process as defined in claim 1 wherein said treatment bath is said electrolyte enriched with Ti(IV) ions.
11. A process as defined in claim 1 wherein said pickling solution is a hot aqueous solution of oxalic acid.
12. A process as defined in claim 1 wherein said electrolyte contains Pb(II) ions from a substance selected from, Pb(II) salts of nitric acid, amido-, imido-, nitro- or fluoro-derivatives of sulphuric, or phosphoric acids; and soluble Pb(II) salts with one of said acids.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19742444691 DE2444691A1 (en) | 1974-09-18 | 1974-09-18 | PROCESS FOR THE PRODUCTION OF ELECTRODES BUILT UP FROM TITANIUM CARRIER AND LEAD DIOXIDE PAD FOR ELECTROLYTIC PURPOSES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1044754A true CA1044754A (en) | 1978-12-19 |
Family
ID=5926140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA235,633A Expired CA1044754A (en) | 1974-09-18 | 1975-09-17 | Process for making titanium supported lead electrode |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US4019970A (en) |
| JP (1) | JPS5172975A (en) |
| AT (1) | AT351627B (en) |
| BE (1) | BE833544A (en) |
| CA (1) | CA1044754A (en) |
| CH (1) | CH597370A5 (en) |
| DD (1) | DD120597A5 (en) |
| DE (1) | DE2444691A1 (en) |
| FR (1) | FR2285726A1 (en) |
| GB (1) | GB1472028A (en) |
| IT (1) | IT7527381A1 (en) |
| NL (1) | NL7510848A (en) |
| NO (1) | NO145768C (en) |
| SE (1) | SE7510411L (en) |
| YU (1) | YU234775A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113970211A (en) * | 2021-10-12 | 2022-01-25 | 海信（山东）冰箱有限公司 | A kind of refrigerator |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2722840A1 (en) * | 1977-05-20 | 1978-11-23 | Rheinische Westfaelisches Elek | METHOD OF MANUFACTURING ELECTRODES FOR ELECTROLYTIC PURPOSES |
| JPS5927215B2 (en) | 1978-12-27 | 1984-07-04 | 日産自動車株式会社 | Functional materials subjected to surface activation treatment and their manufacturing method |
| DE3003781C2 (en) * | 1980-02-02 | 1982-08-26 | Rheinisch-Westfälisches Elektrizitätswerk AG, 4300 Essen | Use of an electrode with a lead dioxide coating as a working electrode in the production of ozone |
| US4595044A (en) * | 1984-04-10 | 1986-06-17 | Vsi Corporation | Die casting apparatus |
| US4593741A (en) * | 1984-04-10 | 1986-06-10 | Caugherty William C | Die casting apparatus |
| DE3432684A1 (en) * | 1984-09-05 | 1986-03-13 | Michael Dipl.-Chem. 8068 Pfaffenhofen Gnann | Process and apparatus for generating ozone in high concentrations |
| JPH0690934B2 (en) * | 1987-08-07 | 1994-11-14 | 日本電信電話株式会社 | Secondary battery and manufacturing method thereof |
| US7314685B2 (en) * | 2001-07-30 | 2008-01-01 | Greatbatch Ltd. | Oxidized titanium as a cathodic current collector |
| CN101985202B (en) * | 2010-11-01 | 2012-02-15 | 安徽华东光电技术研究所 | Manufacturing process of multi-beam traveling wave tube grid |
| CN102881949B (en) * | 2012-10-25 | 2014-07-16 | 北斗航天新能源科技开发（北京）有限公司 | Electrolyte used for ion state mixed crystal salt storage battery |
| CN111855754B (en) * | 2019-04-29 | 2021-12-03 | 深圳安吉尔饮水产业集团有限公司 | Water hardness detection probe, sensor, detection method and water softener |
| CN118600423A (en) * | 2024-05-31 | 2024-09-06 | 东北大学 | A method for preparing a lead dioxide-titanium coating composite anode |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3463707A (en) * | 1965-06-16 | 1969-08-26 | Pacific Eng & Production Co | Electrodeposition of lead dioxide |
| GB1105388A (en) * | 1965-07-01 | 1968-03-06 | Imp Metal Ind Kynoch Ltd | Surface treatment of titanium |
| GB1327760A (en) * | 1969-12-22 | 1973-08-22 | Imp Metal Ind Kynoch Ltd | Electrodes |
| US3935082A (en) * | 1973-02-13 | 1976-01-27 | Rheinisch-Westfalisches Elektrizitatswerk Ag | Process for making lead electrode |
-
1974
- 1974-09-18 DE DE19742444691 patent/DE2444691A1/en not_active Ceased
-
1975
- 1975-09-15 NL NL7510848A patent/NL7510848A/en not_active Application Discontinuation
- 1975-09-16 DD DD188369A patent/DD120597A5/xx unknown
- 1975-09-16 US US05/613,797 patent/US4019970A/en not_active Expired - Lifetime
- 1975-09-16 JP JP50111005A patent/JPS5172975A/en active Granted
- 1975-09-16 NO NO753152A patent/NO145768C/en unknown
- 1975-09-17 SE SE7510411A patent/SE7510411L/en not_active Application Discontinuation
- 1975-09-17 CA CA235,633A patent/CA1044754A/en not_active Expired
- 1975-09-17 AT AT713875A patent/AT351627B/en not_active IP Right Cessation
- 1975-09-17 FR FR7528488A patent/FR2285726A1/en active Granted
- 1975-09-17 YU YU02347/75A patent/YU234775A/en unknown
- 1975-09-18 IT ITMI1975A27381A patent/IT7527381A1/en unknown
- 1975-09-18 GB GB3833474A patent/GB1472028A/en not_active Expired
- 1975-09-18 BE BE833544A patent/BE833544A/en unknown
- 1975-09-18 CH CH1212675A patent/CH597370A5/xx not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113970211A (en) * | 2021-10-12 | 2022-01-25 | 海信（山东）冰箱有限公司 | A kind of refrigerator |
Also Published As
| Publication number | Publication date |
|---|---|
| SE7510411L (en) | 1976-03-19 |
| FR2285726B1 (en) | 1979-08-03 |
| NL7510848A (en) | 1976-03-22 |
| NO145768C (en) | 1982-05-26 |
| GB1472028A (en) | 1977-04-27 |
| FR2285726A1 (en) | 1976-04-16 |
| DD120597A5 (en) | 1976-06-20 |
| YU234775A (en) | 1982-06-30 |
| IT7527381A1 (en) | 1977-03-18 |
| AT351627B (en) | 1979-08-10 |
| DE2444691A1 (en) | 1976-04-01 |
| NO753152L (en) | 1976-03-19 |
| ATA713875A (en) | 1979-01-15 |
| BE833544A (en) | 1976-01-16 |
| US4019970A (en) | 1977-04-26 |
| CH597370A5 (en) | 1978-03-31 |
| NO145768B (en) | 1982-02-15 |
| JPS5172975A (en) | 1976-06-24 |
| JPS5345191B2 (en) | 1978-12-05 |
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