US20230151503A1 - Method for the treatment of a metal substrate for the preparation of electrodes - Google Patents
Method for the treatment of a metal substrate for the preparation of electrodes Download PDFInfo
- Publication number
- US20230151503A1 US20230151503A1 US17/906,429 US202117906429A US2023151503A1 US 20230151503 A1 US20230151503 A1 US 20230151503A1 US 202117906429 A US202117906429 A US 202117906429A US 2023151503 A1 US2023151503 A1 US 2023151503A1
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- Prior art keywords
- metal substrate
- nickel
- electrode
- oxides
- current density
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- Pending
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 124
- 239000002184 metal Substances 0.000 title claims abstract description 124
- 239000000758 substrate Substances 0.000 title claims abstract description 113
- 238000000034 method Methods 0.000 title claims abstract description 71
- 238000011282 treatment Methods 0.000 title description 25
- 238000002360 preparation method Methods 0.000 title description 3
- 230000008569 process Effects 0.000 claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000004381 surface treatment Methods 0.000 claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004327 boric acid Substances 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 70
- 238000000576 coating method Methods 0.000 claims description 37
- 239000011248 coating agent Substances 0.000 claims description 36
- 229910052759 nickel Inorganic materials 0.000 claims description 35
- 230000003197 catalytic effect Effects 0.000 claims description 34
- 150000002739 metals Chemical class 0.000 claims description 13
- 229910000510 noble metal Inorganic materials 0.000 claims description 9
- 150000002910 rare earth metals Chemical group 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000004070 electrodeposition Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 229910002065 alloy metal Inorganic materials 0.000 claims description 3
- 239000003014 ion exchange membrane Substances 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 2
- 238000007654 immersion Methods 0.000 abstract description 8
- 239000000243 solution Substances 0.000 description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 14
- 238000007788 roughening Methods 0.000 description 13
- 230000004580 weight loss Effects 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 238000005530 etching Methods 0.000 description 11
- 229910052777 Praseodymium Inorganic materials 0.000 description 10
- 229910052763 palladium Inorganic materials 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 10
- 238000005488 sandblasting Methods 0.000 description 10
- 239000004576 sand Substances 0.000 description 9
- 238000010561 standard procedure Methods 0.000 description 8
- 230000010287 polarization Effects 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000010431 corundum Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 238000003486 chemical etching Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000001033 granulometry Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
- C25F3/06—Etching of iron or steel
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
- C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
-
- 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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
-
- 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
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
- C25D17/12—Shape or form
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
Definitions
- the present invention relates to a method for preparing a metal substrate suitable for use as electrode support in industrial electrochemical applications, and to an electrode prepared using the metal substrate thus obtained. Said method allows to obtain a metal substrate characterized by a surface with controlled roughness.
- One procedure for example, consists in dry sandblasting in which the surface of the metal substrate is abraded by a high pressure air impacting jet with sand or grit, or alternatively in wet sandblasting, in which the surface of the metal substrate is abraded by a high pressure water jet with sand or grit.
- a further drawback of these methods of the prior art is represented by the poor homogeneity of the roughness profile obtained, due to the complexity in controlling it as it depends on a combination of several treatment parameters such as sand or grit granulometry, the air or water pressure, the size of the nozzles and the angle of the jet with respect to the surface. Furthermore, once this type of surface treatment has been completed, the metal substrate may be polluted by residues of grit or sand which negatively affect the adhesion of the catalytic coating.
- this method has the disadvantage due to the need to frequently change the sand or grit used since the particle size varies and decreases during the treatment, with a consequent reduction in the abrasion efficiency.
- the disposal of sand, or grit, polluted by the particles abraded by the treated metal substrates, is complex and expensive.
- Chinese patent application CN 110760862 A describes a surface treatment of very thin copper foils used in high-density PCB circuit boards where, within a complex multi-step procedure, an electrochemical treatment with low-concentration sulfuric acid at high current densities is employed.
- Chinese patent application CN 106521587 A relates to surface preparation of stainless steel strips used as structural components in nuclear plants for holding the fuel rods which employs an electrochemical treatment using concentrated sulfuric acid.
- the substrates used in these Chinese patent applications are not suitable as substrates for electrodes in industrial electrochemical applications.
- the reduction of said current voltage can be achieved by using anodes and cathodes with catalytic coatings suitable to facilitate the required electrochemical processes, such as for example the evolution of hydrogen, chlorine or oxygen.
- the present invention is therefore directed, among other things, to a method for the treatment of metal meshes or sheets used as metal substrates of electrodes to be installed as anodes or cathodes in electrochemical cells where the minimization of electrical energy consumption is of utmost importance.
- the metal substrate can be any metal suitable to be used as electrodic support for electrochemical processes.
- metal substrate for a cathode to be used in chlor-alkali electrolysis and water electrolysis processes can be chosen from nickel, nickel alloys, copper and steel.
- a catalytic coating is typically applied onto the metal substrate.
- the catalytic coating of the metal substrate has the purpose of being electrochemically active for the reactions of interest and, by way of example, can comprise noble metals, their alloys or their oxides.
- the most commonly used noble metals can be chosen from ruthenium, platinum, palladium, rhodium or their alloys.
- the catalytic coating may comprise metals belonging to the rare earth group, or their oxides, without departing from the scope of the invention.
- the most frequently used metals belonging to the rare earth group can be chosen from praseodymium, cerium and lanthanum.
- Said catalytic coating can be applied to the metal substrate by methods known in the art, which include, among others, galvanic methods or thermal decomposition methods, comprising several steps, of solutions containing suitable precursors of said metals conducted at temperatures ranging from 300° C. at 600° C.
- the heat treatment has a typical duration ranging from a few minutes to a few tens, with an optional final heat treatment.
- the performance of these types of electrodes depends, among other features, on the adhesion of the catalytic coating to the metal substrate, which is a function of a series of surface properties of said metal substrate and in particular of the cleanliness and degree of surface roughness.
- the cleaning of said metal substrates can be obtained with any treatment known in the art to obtain clean metal substrates, including, among others, the use of particular solvents or mechanical cleaning treatments.
- the degree of roughness, dependent on the roughness profile of the surface is one of the parameters that affects the adhesion of the catalytic coating to the metal substrate. It is expressed through a numerical parameter Ra which is defined as the average value (in ⁇ m) of the absolute deviations of the roughness profile with respect to its average line.
- the invention is directed to a method for surface treatment of at least one face of a metal substrate of an electrode for electrochemical applications, comprising acid etching in the presence of electrical polarization at controlled current density.
- Current density is the amount of current applied to a surface, expressed in A/dm 2 .
- Such as manufacturing process can have the advantage of being easily applicable to substrates of several geometries such as solid, perforated, stretched or woven sheets and/or meshes, possibly of very reduced thickness, without causing substantial changes to the surface treatment process according to the various geometries and dimensions, as would happen in the case of sandblasting treatments.
- the surface treatment comprises a method for surface roughening of a metal substrate having a thickness below 1.2 mm.
- Said method comprises a step (a) of immersion of said metal substrate, of which it has to be provided the surface roughening, in an acid solution in the proximity of at least one further conductive element as counter-electrode.
- Said acid solution acts as the electrolyte in the electrochemical system thus formed.
- an electric potential difference is applied between the metal substrate and at least one counter-electrode such that an anodic current density is applied to the metal substrate to obtain the desired roughness on the surface of said metal substrate.
- Said metal substrate can comprise nickel, copper, nickel metal alloys.
- the metal substrate can be in any form able to accomplish its purpose and can be in the form of a mesh, for instance an expanded mesh or a woven mesh, or a sheet, for instance a punched or expanded sheet, with thicknesses below 1.2 mm.
- the metal substrate has a thickness of 0.5 mm or less.
- the metal substrate has a thickness in the range between 0.01 to 1.2 mm, preferably in the range from 0.02 to 1 mm and. In certain embodiment, the metal substrate has a thickness in the range from 0.05 to 0.5 mm.
- said acid solution acting as electrolyte in which the metal substrate is immersed is selected from the group of mineral acids comprising hydrochloric acid, nitric acid, sulfuric acid and boric acid at a concentration by weight of between 10-40%, preferably between 15-30%.
- the electrolyte comprises hydrochloric acid at a concentration by weight of between 10-40%, preferably between 15-30%.
- the method according to the present invention for surface treatment of a metal substrate suitable for use as electrode support in electrochemical processes comprising the following steps:
- steps (a) and (b) are only applied once with no intervening steps such as curing steps.
- the electrolyte does not comprise any additional metals or metal salts, such as copper ions or chopper chloride, except for typical residual amounts in water, and in any case only in concentrations by weight of below 1%.
- said at least one counter-electrode can be in any form suitable for achieving its purpose; the choice, number, distance and dimensioning of said at least one counter-electrode depends on various factors, such as for example the degree of roughening to be provided to said metal substrate or the dimensions and thickness of said metal substrate.
- Said at least one counter-electrode can be advantageously sized and positioned in such a way as to be able to obtain different degrees of roughening on the same surface of said metal substrate.
- Said at least one counter-electrode can be advantageously sized and positioned in such a way as to be able to provide a different degree of roughening on the two faces of said metal substrate.
- Said at least one counter-electrode can be advantageously sized and positioned in such a way as to be able to provide a degree of roughening to a single face of said metal substrate.
- the metal substrate and at least one counter-electrode are coupled to a power source.
- Said power source is configured to apply an anodic current density of between 0.1 and 30 A/dm 2 to said metal substrate to roughen its surface.
- the anodic current density is in the range between 5 and 10 A/dm 2 .
- the current density, its application time and the temperature of the electrolyte are parameters that can be varied to obtain the desired roughening degree.
- said anodic current density can be applied for a time equal to or less than 120 minutes allowing to obtain a typical weight loss, less than 10%, corresponding to the roughening of the surface of a metal mesh with thickness equal or less than 1.2 mm.
- the application time of said anodic current density is equal to or less than 60 minutes, preferably equal to or less than 30 minutes.
- the application time of said anodic current density is between 2 and 10 minutes, for instance, an anodic current density in the range between 5 and 10 A/dm 2 can be applied of a time between 2 and 10 minutes.
- the metal substrate to be roughened is a thin metal surface, for example with a thickness of 0.5 mm or less.
- this type of metal substrate cannot be subjected to the surface treatment, necessary to ensure the best adhesion of the catalytic layer, by sandblasting, as the energy of the pressurized sand jet could cause severe deformation of said metal substrate which would also increase in the event of a heat treatment associated with the application of the catalytic coating.
- the current flows between the metal substrate and at least one counter-electrode through the electrolyte.
- the positive and negative ions of the electrolyte are separated and are attracted to the metal substrate and by at least one counter-electrode having the opposite polarity to the ions.
- Positive ions are attracted to at least one counter-electrode which acts as a cathode and negative ions are attracted to the metal substrate which acts as an anode in the electrochemical system here described, oxidizing with consequent corrosion of its surface.
- a homogeneous roughness layer is formed on the surface of the metal substrate.
- the process requires a few minutes to have a weight loss corresponding to the roughening of the surface.
- the weight loss expressed as a percentage with respect to the initial weight value, is usually used as an index of surface roughening due to the surface removal of material from the metal substrate.
- the applied anodic current density is between 5 and 10 A/dm 2 ; an anodic current density between these values has the advantage of allowing to obtain in a limited time of a few minutes, and in any case less than 10 minutes, a typical weight loss, between 3 and 6%, corresponding to the roughening of the surface of a metal mesh with a thickness of less than 1 mm. Thanks to the high speed of similar surface treatments, fast and continuous processes can be developed that can lead to greater efficiency of the production process.
- the invention is directed to an electrode for industrial electrochemical applications comprising a metal substrate and a catalytic coating, said metal substrate being a mesh or sheet having a controlled roughness profile provided by an acid etching treatment in the presence of polarization according to the method described above and having a catalytic coating comprising one or more noble metals, their alloy or their oxides and/or one or more metals belonging to the rare earth group or their oxides.
- the temperature of the electrolyte can be varied between 15 and 40° C.
- the present invention is directed to a method for manufacturing an electrode for gas evolution in electrochemical processes, comprising the steps of treating a metal substrate with the method described above and applying a catalytic coating comprising one or more noble or alloy metals or their oxides and/or one or more metals belonging to the rare earth group or their oxides, to said treated metal substrate.
- the invention is directed to an electrode for industrial electrochemical applications comprising a metal substrate and a catalytic coating, said metal substrate being a mesh or sheet having a controlled roughness profile provided by an acid etching treatment in the presence of polarization according to the method described above and having a catalytic coating comprising one or more noble metals selected from ruthenium, platinum, palladium, rhodium or their alloys or their oxides and/or one or more metals belonging to the selected rare earth group between praseodymium, cerium, lanthanum or their oxides.
- the method for treating the metal substrate according to the present invention results in the metal substrate having roughened surface with a high degree of homogeneity in the roughness profile.
- a degree of homogeneity of the roughness profile expressed as the mean square deviation of the Ra values of less than 25% ( ⁇ 25%), preferably less than 20% is achieved.
- the surface treatment typically results in the substrate experiencing a weight loss between 3 and 6% (calculated as the weight difference of the substrate before and after treatment divided by the weight of the substrate before treatment times 100%).
- the invention is directed to an electrode for industrial electrochemical applications comprising a metal substrate and a catalytic coating, said metal substrate being a mesh or sheet provided with a controlled roughness profile, different in the two faces of said substrate, provided by an acid etching treatment in the presence of polarization according to the method described above.
- the invention is directed to an electrode for industrial electrochemical applications comprising a metal substrate and a catalytic coating, said metal substrate being a mesh or sheet with a thickness equal to or less than 1.2 mm and provided with degrees of roughening different on the same surface of said substrate, provided by an acid etching treatment in the presence of polarization according to the method described above.
- the invention is directed to an electrode for industrial electrochemical applications comprising a metal substrate and a catalytic coating, said metal substrate being a mesh or sheet with a thickness equal to or less than 0.1 mm and provided with a profile of controlled roughness provided by an acid etching treatment in the presence of polarization according to the method described above and having a catalytic coating comprising one or more noble metals or their alloy or their oxides and/or one or more metals belonging to the rare earth group or their oxides.
- the method of preparation of said metal substrate can comprise a further step (c), subsequent to step (b), represented by the electrodeposition of nickel directly on the metal substrate through cathodic polarization.
- Said embodiment comprises the addition to said electrolyte of a nickel salt in a weight concentration of between 100 and 300 g/l and subsequent application of a cathodic current density to said metal substrate of between 0.1 and 3 A/dm 2 for a time between 0.5 and 120 minutes at a temperature between 15 and 70° C.
- Said further step (c) can contribute to increasing the surface area of said metal substrate through nickel electrodeposition which can serve to provide specific properties, for example, to further improve the conductivity and/or the catalytic activity of the coating, to inhibit undesirable side reactions or to improve the physical or chemical stability of the coating.
- the invention relates to a cell for water electrolysis or for the electrolysis of alkaline chloride solutions comprising an anodic compartment and a cathodic compartment, separated by an ion exchange membrane or a diaphragm where the cathodic compartment is equipped with a cathode for hydrogen evolution having a metal substrate obtained with the method of the invention.
- the invention relates to an electrolyser for the production of chlorine and alkali starting from alkaline brine, comprising a modular arrangement of electrolytic cells with the anodic and cathodic compartments separated by ion exchange membranes or diaphragms, wherein the cathodic compartment comprises a cathode having a metal substrate obtained with the method of the invention.
- the invention relates to an electrolyzer for the production of hydrogen by electrolysis of water comprising an anodic compartment and a cathodic compartment separated by a diaphragm where the cathodic compartment is equipped with a cathode for the evolution of hydrogen having a metal substrate obtained with the method of the invention.
- a nickel mesh with dimensions 100 mm ⁇ 100 mm ⁇ 0.89 mm was washed and degreased with acetone according to standard procedure, then subjected to a surface treatment by immersion in a 20% HCl solution at room temperature close to a nickel counter-electrode. An anodic current density equivalent to 10 A/m 2 was applied to the nickel mesh for 1.7 minutes.
- a nickel mesh with dimensions 100 mm ⁇ 100 mm ⁇ 0.89 mm was washed and degreased with acetone according to standard procedure, then subjected to a surface treatment by immersion in a 20% HCl solution at room temperature close to a nickel counter-electrode. An anodic current density equivalent to 5 A/m 2 was applied to the nickel mesh for 3.3 minutes.
- a nickel mesh of dimensions 100 mm ⁇ 100 mm ⁇ 0.89 mm was washed and degreased with acetone according to the standard procedure, then subjected to a surface treatment by immersion in a 10% HCl solution at room temperature close to a nickel counter-electrode. An anodic current density equivalent to 12 A/m 2 was applied to the nickel mesh for 1.6 minutes.
- a nickel mesh with dimensions 100 mm ⁇ 100 mm ⁇ 0.89 mm was washed and degreased with acetone according to standard procedure, then subjected to a surface treatment by immersion in a 20% HCl solution at room temperature close to a nickel counter-electrode. An anodic current density equivalent to 1.5 A/m 2 was applied to the nickel mesh for 6 minutes.
- a nickel mesh with dimensions 100 mm ⁇ 100 mm ⁇ 0.89 mm was washed and degreased with acetone according to standard procedure, then subjected to a surface treatment by immersion in a 20% HCl solution at room temperature close to a nickel counter-electrode. An anodic current density equivalent to 1.5 A/m 2 was applied to the nickel mesh for 3 minutes.
- the nickel mesh was subsequently subjected to a nickel electro-deposition treatment after the addition of NiCl 2 , at a concentration of 190 g/l, to the HCl solution 20%.
- a cathodic current density equivalent to 1.5 A/m 2 was applied to the nickel mesh for 13 minutes.
- the nickel mesh thus obtained was coated with 5 coats of an aqueous solution containing Pt, Pr and Pd with a heat treatment of 15 minutes at 450° C. after each coat until obtaining a coating of 1.90 g/m 2 of Pt, 1.24 g/m 2 of Pd and 3.17 g/m 2 of Pr.
- a nickel mesh with dimensions 100 mm ⁇ 100 mm ⁇ 0.89 mm was washed and degreased with acetone according to a standard procedure, then subjected to a process of sandblasting with corundum and etching in 20% HCl at room temperature for a time of 1100 minutes.
- a nickel mesh with dimensions 100 mm ⁇ 100 mm ⁇ 0.89 mm was washed and degreased with acetone according to standard procedure, then subjected to a process of sandblasting with corundum and etching in 20% HCl at a temperature of 60° C. for a period of 40 minutes.
- a nickel mesh with dimensions 100 mm ⁇ 100 mm ⁇ 0.89 mm was washed and degreased with acetone according to standard procedure, then subjected to a process of sandblasting with corundum and etching in HNO 3 21% at room temperature for a time of 15 minutes.
- a nickel mesh with dimensions 100 mm ⁇ 100 mm ⁇ 0.89 mm was subjected to an etching process in 20% HCl at a temperature of 60° C. for 5 minutes.
- the mesh was then coated with 5 coats of an aqueous solution containing Pt, Pr and Pd with a 15-minute heat treatment at 450° C. after each coat until obtaining a coating of 1.90 g/m 2 of Pt, 1.24 g/m 2 of Pd and 3.17 g/m 2 of Pr.
- the electrode thus obtained was identified as sample CE4.
- a nickel mesh with dimensions of 100 mm ⁇ 100 mm ⁇ 0.89 mm was subjected to a process of sandblasting with corundum, etching in 20% HCl at room temperature and stress relieving through heat treatment according to the procedure known in the art.
- the mesh was then coated with 5 coats of an aqueous solution containing Pt, Pr and Pd with a 15-minute heat treatment at 450° C. after each coat until obtaining a coating of 1.90 g/m 2 of Pt, 1.24 g/m 2 of Pd and 3.17 g/m 2 of Pr.
- the electrode thus obtained was identified as sample CE5.
- Table 1 reports the results of the tests carried out to evaluate the time necessary to achieve a weight loss of between 3 and 6% of a metal substrate; the degree of homogeneity of the roughness profile was also measured, expressed as the mean square deviation in % (% a) of the Ra values measured in different points of the nickel mesh.
- example E5 and counterexample CE5 described above were subjected to performance tests, under hydrogen evolution, in a laboratory cell fed with 32% NaOH at a temperature of 90° C., furthermore they were subsequently subjected to cyclic voltammetry tests in the voltage range from ⁇ 1 to +0.5 V/NHE with a scan rate of 10 mV/s.
- Table 2 reports the initial cathodic voltage and the one after 25 cycles of cyclic voltammetry (25 CV), index of resistance to inversions and therefore of robustness, measured at a current density of 3 kA/m 2 .
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Abstract
A method for surface treatment of a metal substrate, suitable for use as electrode support in electrochemical processes by: (a) immersion of the metal substrate and of at least one counter electrode in an electrolyte selected from hydrochloric acid, nitric acid, boric acid or sulfuric acid at a weight concentration of between 10-40%; (b) application of an anodic current density to the metal substrate of between 0.1 and 30 A/dm2 for a time of between 0.5 and 120 minutes. An electrode for gas evolution in electrochemical processes obtained from a correspondingly treated substrate.
Description
- The present invention relates to a method for preparing a metal substrate suitable for use as electrode support in industrial electrochemical applications, and to an electrode prepared using the metal substrate thus obtained. Said method allows to obtain a metal substrate characterized by a surface with controlled roughness.
- Generally electrochemical processes involve the evolution of different gases which subject the catalytic coating, which is generally deposited on a metal substrate, to a continuous chemical-physical stress; the adhesion of this coating to the metal substrate therefore plays a fundamental role in obtaining an electrode with an industrially acceptable service life.
- It is known to those skilled in the art that the adhesion of the catalytic layer to the metal substrate is closely related to the surface roughness profile of the metal substrate itself, a roughness that guarantees a suitable anchoring base for the catalytic coating.
- In literature several types of surface treatment suitable for imparting roughness to metal substrates are described. One procedure, for example, consists in dry sandblasting in which the surface of the metal substrate is abraded by a high pressure air impacting jet with sand or grit, or alternatively in wet sandblasting, in which the surface of the metal substrate is abraded by a high pressure water jet with sand or grit.
- However, these treatments produce on the metal structure a considerable amount of residual compressive stress. When thin meshes or sheets are used, for example with a thickness of less than 1 mm, it is possible that the aforementioned residual stresses produce deformations on the metal substrate with consequent loss of planarity. For this reason, dry or wet blasting can only be applied to relatively thick metal substrates.
- In addition, these mechanical impact treatments show disadvantages even when applied to thick metal substrates. The action of sandblasting, in fact, can cause a substantial increase in the hardness of the metal substrate which will result in cracks during the application of the catalytic coating and subsequent heat treatment.
- A further drawback of these methods of the prior art is represented by the poor homogeneity of the roughness profile obtained, due to the complexity in controlling it as it depends on a combination of several treatment parameters such as sand or grit granulometry, the air or water pressure, the size of the nozzles and the angle of the jet with respect to the surface. Furthermore, once this type of surface treatment has been completed, the metal substrate may be polluted by residues of grit or sand which negatively affect the adhesion of the catalytic coating.
- In addition, this method has the disadvantage due to the need to frequently change the sand or grit used since the particle size varies and decreases during the treatment, with a consequent reduction in the abrasion efficiency. Finally, the disposal of sand, or grit, polluted by the particles abraded by the treated metal substrates, is complex and expensive.
- Other surface treatments known in the art include coupling sandblasting, with sand or grit, with a chemical etching in acid solutions, or with heat treatment followed by chemical etching in acid solutions and spraying by melting metals or ceramic oxides, thus favoring the growth of a rough layer. Each of these techniques, however, has drawbacks mainly related to the difficulty in imparting a homogeneous roughness profile to the entire treated surface.
- From other fields of endeavor, surface treatment methods using electrochemical processes are known. For instance, Chinese patent application CN 110760862 A describes a surface treatment of very thin copper foils used in high-density PCB circuit boards where, within a complex multi-step procedure, an electrochemical treatment with low-concentration sulfuric acid at high current densities is employed. Chinese patent application CN 106521587 A relates to surface preparation of stainless steel strips used as structural components in nuclear plants for holding the fuel rods which employs an electrochemical treatment using concentrated sulfuric acid. The substrates used in these Chinese patent applications are not suitable as substrates for electrodes in industrial electrochemical applications.
- Therefore, it would be desirable to provide a method of treating metal substrates suitable for electrodes in industrial electrochemical applications that overcomes both the drawbacks due to insufficient cleaning of the treated surface, which can negatively affect the adhesion of the catalytic coating, and the difficulty of obtaining homogeneous, reproducible roughness profile of the entire surface of a single metal substrate and on the different samples of a batch of an industrial production, as well as the costs of disposal of the spent sand or grit.
- In the electrochemical process industry, competitiveness is linked to various factors, the main one being the reduction of energy consumption, directly linked to the current voltage of the global process.
- The reduction of said current voltage can be achieved by using anodes and cathodes with catalytic coatings suitable to facilitate the required electrochemical processes, such as for example the evolution of hydrogen, chlorine or oxygen. The present invention is therefore directed, among other things, to a method for the treatment of metal meshes or sheets used as metal substrates of electrodes to be installed as anodes or cathodes in electrochemical cells where the minimization of electrical energy consumption is of utmost importance.
- In the method according to the invention, the metal substrate can be any metal suitable to be used as electrodic support for electrochemical processes. In particular, as metal substrate for a cathode to be used in chlor-alkali electrolysis and water electrolysis processes. In this case, the most commonly used metal substrates can be chosen from nickel, nickel alloys, copper and steel.
- When used as an electrode, a catalytic coating is typically applied onto the metal substrate. The catalytic coating of the metal substrate has the purpose of being electrochemically active for the reactions of interest and, by way of example, can comprise noble metals, their alloys or their oxides. The most commonly used noble metals can be chosen from ruthenium, platinum, palladium, rhodium or their alloys.
- In addition to the claimed noble metals, the catalytic coating may comprise metals belonging to the rare earth group, or their oxides, without departing from the scope of the invention. The most frequently used metals belonging to the rare earth group can be chosen from praseodymium, cerium and lanthanum.
- Said catalytic coating can be applied to the metal substrate by methods known in the art, which include, among others, galvanic methods or thermal decomposition methods, comprising several steps, of solutions containing suitable precursors of said metals conducted at temperatures ranging from 300° C. at 600° C. For each step of the catalytic layer deposition, the heat treatment has a typical duration ranging from a few minutes to a few tens, with an optional final heat treatment.
- The performance of these types of electrodes depends, among other features, on the adhesion of the catalytic coating to the metal substrate, which is a function of a series of surface properties of said metal substrate and in particular of the cleanliness and degree of surface roughness.
- The cleaning of said metal substrates can be obtained with any treatment known in the art to obtain clean metal substrates, including, among others, the use of particular solvents or mechanical cleaning treatments.
- The degree of roughness, dependent on the roughness profile of the surface, is one of the parameters that affects the adhesion of the catalytic coating to the metal substrate. It is expressed through a numerical parameter Ra which is defined as the average value (in μm) of the absolute deviations of the roughness profile with respect to its average line.
- In one embodiment, the invention is directed to a method for surface treatment of at least one face of a metal substrate of an electrode for electrochemical applications, comprising acid etching in the presence of electrical polarization at controlled current density. Current density is the amount of current applied to a surface, expressed in A/dm2.
- Such as manufacturing process can have the advantage of being easily applicable to substrates of several geometries such as solid, perforated, stretched or woven sheets and/or meshes, possibly of very reduced thickness, without causing substantial changes to the surface treatment process according to the various geometries and dimensions, as would happen in the case of sandblasting treatments.
- According to an embodiment, the surface treatment comprises a method for surface roughening of a metal substrate having a thickness below 1.2 mm. Said method comprises a step (a) of immersion of said metal substrate, of which it has to be provided the surface roughening, in an acid solution in the proximity of at least one further conductive element as counter-electrode. Said acid solution acts as the electrolyte in the electrochemical system thus formed. In the next step (b) of the present method, an electric potential difference is applied between the metal substrate and at least one counter-electrode such that an anodic current density is applied to the metal substrate to obtain the desired roughness on the surface of said metal substrate. Said metal substrate can comprise nickel, copper, nickel metal alloys. Under various embodiments, the metal substrate can be in any form able to accomplish its purpose and can be in the form of a mesh, for instance an expanded mesh or a woven mesh, or a sheet, for instance a punched or expanded sheet, with thicknesses below 1.2 mm.
- In one embodiment, the metal substrate has a thickness of 0.5 mm or less.
- In certain embodiments, the metal substrate has a thickness in the range between 0.01 to 1.2 mm, preferably in the range from 0.02 to 1 mm and. In certain embodiment, the metal substrate has a thickness in the range from 0.05 to 0.5 mm.
- In one embodiment said acid solution acting as electrolyte in which the metal substrate is immersed is selected from the group of mineral acids comprising hydrochloric acid, nitric acid, sulfuric acid and boric acid at a concentration by weight of between 10-40%, preferably between 15-30%. In certain embodiments, the electrolyte comprises hydrochloric acid at a concentration by weight of between 10-40%, preferably between 15-30%.
- Accordingly, the method according to the present invention for surface treatment of a metal substrate suitable for use as electrode support in electrochemical processes comprising the following steps:
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- (a) immersion of said metal substrate and of at least one counter electrode in an electrolyte selected from hydrochloric acid, nitric acid, boric acid or sulfuric acid at a weight concentration of between 10-40%;
- (b) application of an anodic current density to said metal substrate of between 0.1 and 30 A/dm2 for a time of between 0.5 and 120 minutes.
- Preferably steps (a) and (b) are only applied once with no intervening steps such as curing steps.
- In certain embodiments, the electrolyte does not comprise any additional metals or metal salts, such as copper ions or chopper chloride, except for typical residual amounts in water, and in any case only in concentrations by weight of below 1%.
- In an embodiment, said at least one counter-electrode can be in any form suitable for achieving its purpose; the choice, number, distance and dimensioning of said at least one counter-electrode depends on various factors, such as for example the degree of roughening to be provided to said metal substrate or the dimensions and thickness of said metal substrate.
- The person skilled in the art will be able to determine the features of said at least one counter-electrode and the optimal distance of said at least one counter-electrode to said metal substrate according to the degree of roughening to be imparted to said metal substrate.
- Said at least one counter-electrode can be advantageously sized and positioned in such a way as to be able to obtain different degrees of roughening on the same surface of said metal substrate.
- Said at least one counter-electrode can be advantageously sized and positioned in such a way as to be able to provide a different degree of roughening on the two faces of said metal substrate.
- Said at least one counter-electrode can be advantageously sized and positioned in such a way as to be able to provide a degree of roughening to a single face of said metal substrate.
- It has been surprisingly observed that the appropriate regulation of said current density allows to operate making the most of the advantages of the invention such as in situations wherein said metal substrate has a thickness equal to or less than 0.1 mm, producing a homogeneous roughness profile sufficient to ensure optimal anchoring of the catalytic coating.
- In the illustrated embodiment, the metal substrate and at least one counter-electrode are coupled to a power source. Said power source is configured to apply an anodic current density of between 0.1 and 30 A/dm2 to said metal substrate to roughen its surface. In one embodiment, the anodic current density is in the range between 5 and 10 A/dm2.
- The current density, its application time and the temperature of the electrolyte are parameters that can be varied to obtain the desired roughening degree.
- The inventors have surprisingly observed that said anodic current density can be applied for a time equal to or less than 120 minutes allowing to obtain a typical weight loss, less than 10%, corresponding to the roughening of the surface of a metal mesh with thickness equal or less than 1.2 mm. In one embodiment, the application time of said anodic current density is equal to or less than 60 minutes, preferably equal to or less than 30 minutes. In one embodiment, the application time of said anodic current density is between 2 and 10 minutes, for instance, an anodic current density in the range between 5 and 10 A/dm2 can be applied of a time between 2 and 10 minutes.
- This result is particularly important when the metal substrate to be roughened is a thin metal surface, for example with a thickness of 0.5 mm or less. As is known to those skilled in the art, this type of metal substrate cannot be subjected to the surface treatment, necessary to ensure the best adhesion of the catalytic layer, by sandblasting, as the energy of the pressurized sand jet could cause severe deformation of said metal substrate which would also increase in the event of a heat treatment associated with the application of the catalytic coating.
- When a voltage is applied between the metal substrate and at least one counter-electrode, the current flows between the metal substrate and at least one counter-electrode through the electrolyte. The positive and negative ions of the electrolyte are separated and are attracted to the metal substrate and by at least one counter-electrode having the opposite polarity to the ions. Positive ions are attracted to at least one counter-electrode which acts as a cathode and negative ions are attracted to the metal substrate which acts as an anode in the electrochemical system here described, oxidizing with consequent corrosion of its surface. As a result, a homogeneous roughness layer is formed on the surface of the metal substrate. The process requires a few minutes to have a weight loss corresponding to the roughening of the surface. The weight loss, expressed as a percentage with respect to the initial weight value, is usually used as an index of surface roughening due to the surface removal of material from the metal substrate.
- In one embodiment the applied anodic current density is between 5 and 10 A/dm2; an anodic current density between these values has the advantage of allowing to obtain in a limited time of a few minutes, and in any case less than 10 minutes, a typical weight loss, between 3 and 6%, corresponding to the roughening of the surface of a metal mesh with a thickness of less than 1 mm. Thanks to the high speed of similar surface treatments, fast and continuous processes can be developed that can lead to greater efficiency of the production process.
- In another embodiment, the invention is directed to an electrode for industrial electrochemical applications comprising a metal substrate and a catalytic coating, said metal substrate being a mesh or sheet having a controlled roughness profile provided by an acid etching treatment in the presence of polarization according to the method described above and having a catalytic coating comprising one or more noble metals, their alloy or their oxides and/or one or more metals belonging to the rare earth group or their oxides.
- In some embodiments, the temperature of the electrolyte can be varied between 15 and 40° C.
- In a further embodiment, the present invention is directed to a method for manufacturing an electrode for gas evolution in electrochemical processes, comprising the steps of treating a metal substrate with the method described above and applying a catalytic coating comprising one or more noble or alloy metals or their oxides and/or one or more metals belonging to the rare earth group or their oxides, to said treated metal substrate.
- In a further embodiment, the invention is directed to an electrode for industrial electrochemical applications comprising a metal substrate and a catalytic coating, said metal substrate being a mesh or sheet having a controlled roughness profile provided by an acid etching treatment in the presence of polarization according to the method described above and having a catalytic coating comprising one or more noble metals selected from ruthenium, platinum, palladium, rhodium or their alloys or their oxides and/or one or more metals belonging to the selected rare earth group between praseodymium, cerium, lanthanum or their oxides. The method for treating the metal substrate according to the present invention results in the metal substrate having roughened surface with a high degree of homogeneity in the roughness profile. Typically, a degree of homogeneity of the roughness profile expressed as the mean square deviation of the Ra values of less than 25% (σ<25%), preferably less than 20% is achieved. The surface treatment typically results in the substrate experiencing a weight loss between 3 and 6% (calculated as the weight difference of the substrate before and after treatment divided by the weight of the substrate before treatment times 100%).
- Under a further aspect, the invention is directed to an electrode for industrial electrochemical applications comprising a metal substrate and a catalytic coating, said metal substrate being a mesh or sheet provided with a controlled roughness profile, different in the two faces of said substrate, provided by an acid etching treatment in the presence of polarization according to the method described above.
- Under a further aspect, the invention is directed to an electrode for industrial electrochemical applications comprising a metal substrate and a catalytic coating, said metal substrate being a mesh or sheet with a thickness equal to or less than 1.2 mm and provided with degrees of roughening different on the same surface of said substrate, provided by an acid etching treatment in the presence of polarization according to the method described above.
- Under a further aspect, the invention is directed to an electrode for industrial electrochemical applications comprising a metal substrate and a catalytic coating, said metal substrate being a mesh or sheet with a thickness equal to or less than 0.1 mm and provided with a profile of controlled roughness provided by an acid etching treatment in the presence of polarization according to the method described above and having a catalytic coating comprising one or more noble metals or their alloy or their oxides and/or one or more metals belonging to the rare earth group or their oxides.
- According to an embodiment, the method of preparation of said metal substrate can comprise a further step (c), subsequent to step (b), represented by the electrodeposition of nickel directly on the metal substrate through cathodic polarization. Said embodiment comprises the addition to said electrolyte of a nickel salt in a weight concentration of between 100 and 300 g/l and subsequent application of a cathodic current density to said metal substrate of between 0.1 and 3 A/dm2 for a time between 0.5 and 120 minutes at a temperature between 15 and 70° C.
- Said further step (c) can contribute to increasing the surface area of said metal substrate through nickel electrodeposition which can serve to provide specific properties, for example, to further improve the conductivity and/or the catalytic activity of the coating, to inhibit undesirable side reactions or to improve the physical or chemical stability of the coating.
- Under a further aspect, the invention relates to a cell for water electrolysis or for the electrolysis of alkaline chloride solutions comprising an anodic compartment and a cathodic compartment, separated by an ion exchange membrane or a diaphragm where the cathodic compartment is equipped with a cathode for hydrogen evolution having a metal substrate obtained with the method of the invention.
- Under a further aspect, the invention relates to an electrolyser for the production of chlorine and alkali starting from alkaline brine, comprising a modular arrangement of electrolytic cells with the anodic and cathodic compartments separated by ion exchange membranes or diaphragms, wherein the cathodic compartment comprises a cathode having a metal substrate obtained with the method of the invention.
- Under a further aspect, the invention relates to an electrolyzer for the production of hydrogen by electrolysis of water comprising an anodic compartment and a cathodic compartment separated by a diaphragm where the cathodic compartment is equipped with a cathode for the evolution of hydrogen having a metal substrate obtained with the method of the invention.
- The following examples are included to demonstrate particular embodiments of the invention, the practicability of which has been extensively verified in the range of values claimed. It will remain clear to those skilled in the art that the compositions and techniques described in the following examples represent compositions and techniques of which the inventors have found a good functioning in the practice of the invention; however, the person skilled in the art will also appreciate that in light of the present description, various changes can be made to the various embodiments described, still giving rise to identical or similar results without departing from the scope of the invention.
- A nickel mesh with dimensions 100 mm×100 mm×0.89 mm was washed and degreased with acetone according to standard procedure, then subjected to a surface treatment by immersion in a 20% HCl solution at room temperature close to a nickel counter-electrode. An anodic current density equivalent to 10 A/m2 was applied to the nickel mesh for 1.7 minutes.
- At the end of the treatment, the weight loss was verified and the degree of roughness was measured in different points of the mesh
- The mesh thus obtained was identified as sample E1
- A nickel mesh with dimensions 100 mm×100 mm×0.89 mm was washed and degreased with acetone according to standard procedure, then subjected to a surface treatment by immersion in a 20% HCl solution at room temperature close to a nickel counter-electrode. An anodic current density equivalent to 5 A/m2 was applied to the nickel mesh for 3.3 minutes.
- At the end of the treatment, the weight loss was verified and the degree of roughness was measured in different points of the mesh.
- The mesh thus obtained was identified as sample E2.
- A nickel mesh of dimensions 100 mm×100 mm×0.89 mm was washed and degreased with acetone according to the standard procedure, then subjected to a surface treatment by immersion in a 10% HCl solution at room temperature close to a nickel counter-electrode. An anodic current density equivalent to 12 A/m2 was applied to the nickel mesh for 1.6 minutes.
- At the end of the treatment, the weight loss was verified and the degree of roughness was measured in different points of the mesh.
- The mesh thus obtained was identified as sample E3.
- A nickel mesh with dimensions 100 mm×100 mm×0.89 mm was washed and degreased with acetone according to standard procedure, then subjected to a surface treatment by immersion in a 20% HCl solution at room temperature close to a nickel counter-electrode. An anodic current density equivalent to 1.5 A/m2 was applied to the nickel mesh for 6 minutes.
- It was then coated with 5 coats of an aqueous solution containing Pt, Pr and Pd with a 15-minute heat treatment at 450° C. after each coat until obtaining a coating of 1.90 g/m2 of Pt, 1.24 g/m2 of Pd and 3.17 g/m2 of Pr.
- On the catalytic layer thus obtained 4 coats of a second solution containing Pt, Pr and Pd were applied in a different ratio compared to the first solution with a heat treatment of 15 minutes at 450° C. after each coat until obtaining a coating of 1.77 g/m2 of Pt, 1.18 g/m2 of Pd and 1.59 g/m2 of Pr.
- The electrode thus obtained was identified as sample E4.
- A nickel mesh with dimensions 100 mm×100 mm×0.89 mm was washed and degreased with acetone according to standard procedure, then subjected to a surface treatment by immersion in a 20% HCl solution at room temperature close to a nickel counter-electrode. An anodic current density equivalent to 1.5 A/m2 was applied to the nickel mesh for 3 minutes.
- The nickel mesh was subsequently subjected to a nickel electro-deposition treatment after the addition of NiCl2, at a concentration of 190 g/l, to the HCl solution 20%. A cathodic current density equivalent to 1.5 A/m2 was applied to the nickel mesh for 13 minutes.
- The nickel mesh thus obtained was coated with 5 coats of an aqueous solution containing Pt, Pr and Pd with a heat treatment of 15 minutes at 450° C. after each coat until obtaining a coating of 1.90 g/m2 of Pt, 1.24 g/m2 of Pd and 3.17 g/m2 of Pr.
- On the catalytic layer thus obtained 4 coats of a second solution containing Pt, Pr and Pd were applied in a different ratio compared to the first solution with a heat treatment of 15 minutes at 450° C. after each coat until obtaining a coating of 1.77 g/m2 of Pt, 1.18 g/m2 of Pd and 1.59 g/m2 of Pr.
- The electrode thus obtained was identified as sample E5.
- A nickel mesh with dimensions 100 mm×100 mm×0.89 mm was washed and degreased with acetone according to a standard procedure, then subjected to a process of sandblasting with corundum and etching in 20% HCl at room temperature for a time of 1100 minutes.
- At the end of the treatment, the weight loss was verified and the degree of roughness was measured in different points of the mesh.
- The mesh thus obtained was identified as sample CE1 sample.
- A nickel mesh with dimensions 100 mm×100 mm×0.89 mm was washed and degreased with acetone according to standard procedure, then subjected to a process of sandblasting with corundum and etching in 20% HCl at a temperature of 60° C. for a period of 40 minutes.
- At the end of the treatment, the weight loss was verified and the degree of roughness was measured in different points of the mesh.
- The mesh thus obtained was identified as sample CE2.
- A nickel mesh with dimensions 100 mm×100 mm×0.89 mm was washed and degreased with acetone according to standard procedure, then subjected to a process of sandblasting with corundum and etching in HNO3 21% at room temperature for a time of 15 minutes.
- At the end of the treatment, the weight loss was verified and the degree of roughness was measured in different points of the mesh.
- The mesh thus obtained was identified as sample CE3.
- A nickel mesh with dimensions 100 mm×100 mm×0.89 mm was subjected to an etching process in 20% HCl at a temperature of 60° C. for 5 minutes.
- The mesh was then coated with 5 coats of an aqueous solution containing Pt, Pr and Pd with a 15-minute heat treatment at 450° C. after each coat until obtaining a coating of 1.90 g/m2 of Pt, 1.24 g/m2 of Pd and 3.17 g/m2 of Pr.
- On the catalytic layer thus obtained 4 coats of a second solution containing Pt, Pr and Pd were applied in a different ratio compared to the first solution with a heat treatment of 15 minutes at 450° C. after each coat until obtaining a coating of 1.77 g/m2 of Pt, 1.18 g/m2 of Pd and 1.59 g/m2 of Pr.
- The electrode thus obtained was identified as sample CE4.
- A nickel mesh with dimensions of 100 mm×100 mm×0.89 mm was subjected to a process of sandblasting with corundum, etching in 20% HCl at room temperature and stress relieving through heat treatment according to the procedure known in the art. The mesh was then coated with 5 coats of an aqueous solution containing Pt, Pr and Pd with a 15-minute heat treatment at 450° C. after each coat until obtaining a coating of 1.90 g/m2 of Pt, 1.24 g/m2 of Pd and 3.17 g/m2 of Pr.
- On the catalytic layer thus obtained 4 coats of a second solution containing Pt, Pr and Pd were applied in a different ratio compared to the first solution with a heat treatment of 15 minutes at 450° C. after each coat until obtaining a coating of 1.77 g/m2 of Pt, 1.18 g/m2 of Pd and 1.59 g/m2 of Pr.
- The electrode thus obtained was identified as sample CE5.
- Table 1 reports the results of the tests carried out to evaluate the time necessary to achieve a weight loss of between 3 and 6% of a metal substrate; the degree of homogeneity of the roughness profile was also measured, expressed as the mean square deviation in % (% a) of the Ra values measured in different points of the nickel mesh.
-
TABLE 1 % Weight loss Minutes % σ E1 4.46% 1.7 <25% E2 4.46% 3.3 <25% E3 4.46% 1.6 <25% CE1 4.46% 1100 >30% CE2 4.46% 40 >40% CE3 4.46% 15 >30% - The samples of example E5 and counterexample CE5 described above were subjected to performance tests, under hydrogen evolution, in a laboratory cell fed with 32% NaOH at a temperature of 90° C., furthermore they were subsequently subjected to cyclic voltammetry tests in the voltage range from −1 to +0.5 V/NHE with a scan rate of 10 mV/s.
- Table 2 reports the initial cathodic voltage and the one after 25 cycles of cyclic voltammetry (25 CV), index of resistance to inversions and therefore of robustness, measured at a current density of 3 kA/m2.
-
TABLE 2 mV vs NHE mV vs NHE (25 CV) E5 916 934 CE5 922 971 - The previous description does not intend to limit the invention, which can be used according to different embodiments without thereby deviating from the purposes and whose scope is uniquely defined by the attached claims.
- In the description and claims of the present application, the term “comprises” and “contains” and their variants such as “comprising” and “containing” are not intended to exclude the presence of other elements, components or additional process steps.
- Discussion of documents, records, materials, apparatuses, articles and the like is included in the text for the sole purpose of providing context to the present invention; However, it is not to be understood that this matter or part of it constituted general knowledge in the field relating to the invention before the priority date of each of the claims attached to this application.
Claims (14)
1. A method for surface treatment of a metal substrate selected from nickel or nickel alloy, suitable for use as electrode support in electrochemical processes, comprising the following steps:
(a) immersing said metal substrate and at least one counter electrode in an electrolyte selected from hydrochloric acid, nitric acid, boric acid or sulfuric acid at a weight concentration of between 10-40%;
(b) applying an anodic current density to said metal substrate between 0.1 and 30 A/dm2 for a time between 0.5 and 120 minutes.
2. The method according claim 1 wherein said metal substrate is a mesh or a punched or expanded sheet.
3. The method according to claim 1 wherein said metal substrate has a thickness below 1.2 mm.
4. The method according to claim 3 wherein said metal substrate has a thickness equal to or less than 0.5 mm.
5. (canceled)
6. The method according to claim 1 wherein the applied anodic current density is between 5 and 10 A/dm2.
7. The method according to claim 6 wherein the application time of the anodic current density is between 2 and 10 minutes.
8. The method according to claim 1 wherein the weight concentration of said electrolyte is between 15-30%.
9. The method according to claim 1 wherein the metal substrate is nickel or nickel alloy comprising a further step (c) subsequent to step (b) of nickel electrodeposition comprising the addition to said electrolyte of a nickel salt in a concentration by weight between 150 and 300 g/l and subsequent application of a cathodic current density to said metal substrate between 0.1 and 3 A/dm2 for a time between 0.5 and 120 minutes at a temperature between 15 and 70° C.
10. A method for manufacturing an electrode for gas evolution in electrochemical processes, comprising the following steps:
treating a metal substrate with the method of claim 1 , and
applying a catalytic coating comprising one or more noble or alloy metals or their oxides and/or one or more metals belonging to the rare earth group or their oxides, to said treated metal substrate.
11. An electrode for gas evolution in electrochemical processes comprising a metal substrate, selected from nickel or nickel alloy, prepared according to the method described in claim 1 , said metal substrate having a degree of homogeneity of the roughness profile, expressed as the mean square deviation Ra values, of less than 25%, and a catalytic coating comprising one or more noble or alloy metals or their oxides and/or one or more metals belonging to the rare earth group or their oxides.
12. (canceled)
13. An electrode for gas evolution in electrochemical processes comprising a metal substrate, selected from nickel or nickel alloy, prepared according to the method described in claim 9 , comprising a layer of nickel electrodeposited directly on the metal substrate and a catalytic coating comprising one or more metals or alloys or their oxides and/or one or more metals belonging to the group of rare earths or their oxides.
14. A cell for the electrolysis of water or for the electrolysis of alkali chloride solutions comprising an anodic compartment and a cathodic compartment separated by an ion-exchange membrane or by a diaphragm, wherein the cathodic compartment is equipped with an electrode according to claim 11 .
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GB526854A (en) * | 1939-03-27 | 1940-09-26 | Battelle Memorial Institute | Improvements in or relating to the electrolytic polishing of metal surfaces and an electrolyte therefor |
IT1317969B1 (en) * | 2000-06-09 | 2003-07-21 | Nora Elettrodi De | ELECTRODE CHARACTERIZED BY A HIGH ADHESION OF A SURFACE CATALYTIC LAYER. |
CN101660194A (en) * | 2009-09-18 | 2010-03-03 | 西北有色金属研究院 | Electrochemical polishing method of nickel-tungsten alloy base-band for coated conductor |
JP5042389B2 (en) * | 2010-02-10 | 2012-10-03 | ペルメレック電極株式会社 | Active cathode for hydrogen generation |
US9404191B2 (en) * | 2012-10-31 | 2016-08-02 | Osaka Soda Co., Ltd. | Anode for use in zero-gap brine electrolyzer, brine electrolyzer and method for zero-gap brine electrolysis employing same |
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