CN114008247A - 电解用电极 - Google Patents
电解用电极 Download PDFInfo
- Publication number
- CN114008247A CN114008247A CN202080045589.0A CN202080045589A CN114008247A CN 114008247 A CN114008247 A CN 114008247A CN 202080045589 A CN202080045589 A CN 202080045589A CN 114008247 A CN114008247 A CN 114008247A
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- Prior art keywords
- electrode
- electrolysis
- mesh
- coating
- ruthenium
- Prior art date
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- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 65
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- 239000011247 coating layer Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000010410 layer Substances 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 34
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 31
- 238000000576 coating method Methods 0.000 claims description 31
- 229910052707 ruthenium Inorganic materials 0.000 claims description 31
- 239000000758 substrate Substances 0.000 claims description 31
- 239000011248 coating agent Substances 0.000 claims description 29
- 239000008199 coating composition Substances 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 239000000654 additive Substances 0.000 claims description 16
- 230000000996 additive effect Effects 0.000 claims description 16
- 229910052697 platinum Inorganic materials 0.000 claims description 16
- 150000001412 amines Chemical class 0.000 claims description 15
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 15
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 14
- 229910052684 Cerium Inorganic materials 0.000 claims description 10
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 claims description 8
- 229910003446 platinum oxide Inorganic materials 0.000 claims description 8
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000012695 Ce precursor Substances 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 claims description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 46
- 229910052759 nickel Inorganic materials 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000012267 brine Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- IBMCQJYLPXUOKM-UHFFFAOYSA-N 1,2,2,6,6-pentamethyl-3h-pyridine Chemical compound CN1C(C)(C)CC=CC1(C)C IBMCQJYLPXUOKM-UHFFFAOYSA-N 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000001994 activation Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 239000003014 ion exchange membrane Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- LJZVDOUZSMHXJH-UHFFFAOYSA-K ruthenium(3+);triiodide Chemical compound [Ru+3].[I-].[I-].[I-] LJZVDOUZSMHXJH-UHFFFAOYSA-K 0.000 description 2
- 238000005488 sandblasting Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910009112 xH2O Inorganic materials 0.000 description 2
- 229920003934 Aciplex® Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910019029 PtCl4 Inorganic materials 0.000 description 1
- 229910021603 Ruthenium iodide Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- DOSXDVYWNFUSBU-UHFFFAOYSA-N [O-][N+](=O)[Pt][N+]([O-])=O Chemical compound [O-][N+](=O)[Pt][N+]([O-])=O DOSXDVYWNFUSBU-UHFFFAOYSA-N 0.000 description 1
- ROZSPJBPUVWBHW-UHFFFAOYSA-N [Ru]=O Chemical group [Ru]=O ROZSPJBPUVWBHW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- MEXSQFDSPVYJOM-UHFFFAOYSA-J cerium(4+);disulfate;tetrahydrate Chemical compound O.O.O.O.[Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MEXSQFDSPVYJOM-UHFFFAOYSA-J 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000003843 chloralkali process Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- NHWBVRAPBLSUQQ-UHFFFAOYSA-H ruthenium hexafluoride Chemical compound F[Ru](F)(F)(F)(F)F NHWBVRAPBLSUQQ-UHFFFAOYSA-H 0.000 description 1
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 1
- WYRXRHOISWEUST-UHFFFAOYSA-K ruthenium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Ru+3] WYRXRHOISWEUST-UHFFFAOYSA-K 0.000 description 1
- PMMMCGISKBNZES-UHFFFAOYSA-K ruthenium(3+);tribromide;hydrate Chemical compound O.Br[Ru](Br)Br PMMMCGISKBNZES-UHFFFAOYSA-K 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- KPZSTOVTJYRDIO-UHFFFAOYSA-K trichlorocerium;heptahydrate Chemical compound O.O.O.O.O.O.O.Cl[Ce](Cl)Cl KPZSTOVTJYRDIO-UHFFFAOYSA-K 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C25B11/02—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
- C25B11/031—Porous electrodes
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- 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
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- 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
- C23C18/12—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 inorganic material other than metallic material
- C23C18/1204—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 inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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- 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
- C23C18/12—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 inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1241—Metallic substrates
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- 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
- C23C18/12—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 inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
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- 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
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- 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
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
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- 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
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- 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
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- 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
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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
- C25B11/02—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
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Abstract
本发明涉及一种其中金属基底层的结构得到优化的电解用电极及其制备方法,其中,本发明的电解用电极与常规电极相比表现出改善的过电压,同时由于涂层损失小而具有优异的耐久性。
Description
技术领域
相关申请的交叉引用
本申请要求于2019年12月19日提交的韩国专利申请No.10-2019-0170677的优先权,该专利申请的公开内容通过引用并入本说明书中。
技术领域
本发明涉及一种可以改善过电压的电解用电极和制备该电解用电极的方法。
背景技术
通过低成本的盐水如海水的电解制备氢氧化物、氢气和氯气的技术是公知的。这种电解工艺也被称为氯碱工艺,并且可以被认为是经过数十年已经在商业操作中证明其性能和技术可靠性的方法。
对于盐水的电解,目前最广泛使用的方法是离子交换膜法,其中,将离子交换膜安装在电解槽中以将电解槽分为阳离子室和阴离子室,并且使用盐水作为电解质以在阳极得到氯气并在阴极得到氢气和苛性钠。
盐水的电解通过如下面电化学反应式中所示的反应进行。
阳极反应:2Cl-→Cl2+2e-(E0=+1.36V)
阴极反应:2H2O+2e-→2OH-+H2(E0=-0.83V)
总反应:2Cl-+2H2O-→2OH-+Cl2+H2(E0=-2.19V)
在盐水的电解中,除了盐水电解所需要的理论电压之外,电解电压还必须考虑阳极的过电压、阴极的过电压、由于离子交换膜的电阻引起的电压和由于阳极与阴极之间的距离引起的电压,并且在这些电压中由电极引起的过电压是重要的变量。
因此,已经研究能够降低电极的过电压的方法,其中,例如,已经开发一种被称为DSA(尺寸稳定阳极)的贵金属类电极并且用作阳极,并且需要开发一种具有耐久性和低的过电压的优异材料用于阴极。
已经主要使用不锈钢或镍作为阴极,并且,特别地,由于电解反应中的过电位(η)与活性表面积(A)成反比,因此,已经主要使用编织网或扩张网形式的镍,其可以具有大的活性比表面积。
然而,在增加镍网的孔径以增加活性比表面积的情况下,在电极制备过程中在基底的预处理过程中难以确保平坦性,会存在的问题是,即使在形成涂层的过程中网孔也会被堵塞,即使当制备的电极用于电解反应时,也会影响电解液的物质转移和氢气的解吸,因此,需要开发一种满足适当条件的镍网。
现有技术文献
(专利文献1)JP2003-277967A
发明内容
技术问题
本发明的一个方面提供一种电解用电极和制备该电解用电极的方法,在所述电解用电极中,通过优化在电解用电极中使用的金属基底的线厚度和网目尺寸,与常规电极相比,过电压得到改善。
技术方案
根据本发明的一个方面,提供一种电解用电极,包括:金属基底层;和包含钌氧化物和氮的涂层,其中,所述金属基底层具有网目尺寸为45目至60目的网状结构,所述网状结构的单线厚度在100μm至160μm的范围内,并且基于所述钌氧化物,所述涂层中的氮含量在20摩尔%至60摩尔%的范围内。
有益效果
本发明的电解用电极由于在电解过程中涂层的损失小而表现出优异的耐久性,同时由于大的活性比表面积而表现出低的过电压以及更少的由涂层引起的孔堵塞。
具体实施方式
下文中,将更详细地描述本发明。
应当理解的是,本说明书和权利要求书中使用的词语或术语不应理解为在常用字典中定义的含义。还应当理解的是,词语或术语应当基于发明人可以适当地定义词语或术语的含义以便以最好地说明发明的原则,理解为具有与它们在相关技术的背景中和在本发明的技术构思中的含义一致的含义。
本发明中描述的作为网目尺寸单位的表述“目”被定义为在1英寸之内包括的网眼的数目,并且,例如,40目是指网状结构在1英寸以内具有40个网眼的尺寸。
电解用电极
本发明提供一种电解用电极,包括:金属基底层;和包含钌氧化物和氮的涂层,其中,所述金属基底层具有网目尺寸为45目至60目的网状结构,所述网状结构的单线厚度在100μm至160μm的范围内,并且基于所述钌氧化物,所述涂层中的氮含量在20摩尔%至60摩尔%的范围内。
对于常规的电解用电极,主要使用网目尺寸为40目的金属基底,但是,在使用40目的网状结构作为电解用电极的金属基底的情况下,由于不能提供足够量的活性比表面积,因此,存在出现相对高的过电压的问题。因此,本发明的发明人发明了一种电解用电极,该电解用电极由于在电解过程中涂层较少脱离而具有优异的耐久性,同时能够通过优化在电解用电极中使用的金属基底的结构来改善过电压。
具体地,本发明中提供的电解用电极的金属基底具有网目尺寸为45目至60目的网状结构,并且构成该网状结构的单线的厚度在100μm至160μm的范围内。更具体地,网目尺寸在50目至60目的范围内,并且单线的厚度在120μm至150μm的范围内。在金属基底的网目尺寸和单线的厚度分别在上述范围内的情况下,涂层组分的脱离少,同时过电压得到改善。特别地,在线厚度小于本发明的范围的情况下,在电极制备过程中的预处理过程中不能保持平坦度,并且由于物理耐久性差,即使在小冲击下也会出现划痕。此外,由于随着线厚度减小,有效面积也减小,因此,与常规电极相比,会出现过电压增加的问题。此外,在线厚度大于本发明的范围的情况下,由于单线厚,因此不能均匀地形成涂层,涂层组分的脱离会更容易发生,并且由于在线与膜之间产生死体积,因此会发生气阱现象。
所述金属基底可以是镍、钛、钽、铝、铪、锆、钼、钨、不锈钢或它们的合金,并且,在这些金属中,所述金属基底可以优选是镍。在本发明的电解用电极中,在使用上述类型的金属基底的情况下,可以为电极提供更好的耐久性和机械强度。
在本发明的电解用电极中,所述涂层包含钌氧化物。钌氧化物作为活性材料起到向涂层提供钌元素的作用,其中,在电解用电极的涂层中使用钌氧化物的情况下,电极性能随时间的变化小,同时过电压现象得到改善,并且,随后,可以使单独的活化过程最小化。钌氧化物包括所有类型的钌元素与氧原子键合的氧化物,并且具体地,可以是二氧化物或四氧化物。
在本发明的电解用电极中,所述涂层包含氮。氮是由于在涂层的制备过程中在涂料组合物中包含的胺类添加剂,其中,在将胺类添加剂加入到涂料组合物中的情况下,所述胺类添加剂可以改善涂层中包含的钌元素之间的键合力以及当包含另一金属元素时钌元素与另一金属元素之间的键合力,并且可以控制包含钌元素的粒子的氧化态,从而制备更适于反应的形式的电极。
基于钌氧化物,涂层中的氮含量可以在30摩尔%至70摩尔%,例如,在40摩尔%至60摩尔%的范围内,并且,在氮含量在上述范围内的情况下,可以使钌元素之间的键合力的改善最大化。此外,当氮含量小于上述范围时,由氮产生的作用不显著,并且,当氮含量大于上述范围时,会出现氮反而在涂层中充当杂质的问题。
在本发明的电解用电极中,所述涂层还可以包含铈氧化物,铈氧化物起到向所述电解用电极的催化剂层提供铈元素的作用。在活化或电解过程中,通过提高电解用电极的耐久性,由铈氧化物提供的铈元素可以使作为电解用电极的催化剂层中的活性材料的钌元素的损失最小化。
具体地,在电解用电极的活化或电解的过程中,催化剂层中的包含铈元素的粒子成为不改变其结构的金属元素,或者部分地水合并且被还原为活性物质。此外,由于催化剂层中的包含铈元素的粒子将其结构改变为针状,因此,粒子充当保护材料,防止催化剂层中的包含钌元素的粒子物理脱离,并且,由此,可以改善电解用电极的耐久性以防止催化剂层中的钌元素的损失。铈氧化物包括所有类型的铈元素与氧原子键合的氧化物,并且具体地,可以是(II)、(III)或(IV)的氧化物。
涂层中包含的钌元素与铈元素之间的摩尔比可以在100:5至100:30,例如,在100:10至100:20的范围内。在涂层中包含的钌元素与铈元素的摩尔比在上述范围内的情况下,电解用电极的耐久性与导电性之间的平衡可以优异。
在本发明的电解用电极中,所述涂层还可以包含铂氧化物。由铂氧化物提供的铂元素可以像钌元素一样充当活性材料,并且,在涂层中一起包含铂氧化物和钌氧化物的情况下,在电极的耐久性和过电压方面可以表现出更好的效果。铂氧化物包括所有类型的铂元素与氧原子键合的氧化物,并且具体地,可以是二氧化物或四氧化物。
涂层中包含的钌元素与铂元素之间的摩尔比可以在100:2至100:20,例如,在100:5至100:15的范围内。在涂层中包含的钌元素与铂元素之间的摩尔比在上述范围内的情况下,在改善耐久性和过电压方面是理想的,其中,在铂元素的含量低于上述范围的情况下,耐久性和过电压会降低,并且,在铂元素的含量高于上述范围的情况下,在经济效率方面不利。
制备电解用电极的方法
本发明提供一种制备电解用电极的方法,该方法包括以下步骤:在金属基底的至少一个表面上涂布涂料组合物,所述金属基底具有网状结构,其中网目尺寸在45目至60目的范围内,并且所述网状结构的单线厚度在100μm至160μm的范围内;和通过干燥和热处理涂布有所述涂料组合物的金属基底而涂层化,其中,所述涂料组合物包含摩尔比为100:5至100:20的钌前体和胺类添加剂。
在本发明的制备电解用电极的方法中,所述金属基底可以与先前描述的电解用电极的金属基底相同。
在本发明的制备电解用电极的方法中,所述涂料组合物可以包含钌前体和胺类添加剂。在涂布之后,钌前体通过在热处理步骤中被氧化而转化为氧化物。
对钌前体的使用没有特别地限制,只要它是能够形成钌氧化物的化合物即可,可以是,例如,钌的水合物、氢氧化物、卤化物或氧化物,并且可以具体是选自六氟化钌(RuF6)、氯化钌(III)(RuCl3)、氯化钌(III)水合物(RuCl3·xH2O)、溴化钌(III)(RuBr3)、溴化钌(III)水合物(RuBr3·xH2O)、碘化钌(RuI3)和乙酸钌中的至少一种。当使用上面列出的钌前体时,钌氧化物的形成可以容易。
在本发明的制备电解用电极的方法中,所述涂料组合物还可以包含胺类添加剂,以在涂层与金属基底之间提供强粘合力。具体地,胺类添加剂可以改善涂层中包含的钌元素之间的键合力,并且可以控制包含钌元素的粒子的氧化态以制备更适合于反应的形式的电极。
本发明中使用的胺类添加剂由于在具有胺基的同时在水中的溶解性高,因此特别适合用于形成涂层。本发明中可以使用的胺类添加剂包括三聚氰胺、氨、尿素、1-丙胺、1-丁胺、1-戊胺、1-庚胺、1-辛胺、1-壬胺或1-十二烷胺,并且可以使用选自它们中的至少一种。
在本发明的电解用电极中,涂层的钌元素和胺类添加剂可以以100:20至100:40,例如,以100:25至100:35的摩尔比被包含。在胺类添加剂以小于上述摩尔比的范围被包含的情况下,通过添加剂改善键合力的效果不显著,并且,在胺类添加剂以大于上述摩尔比的范围被包含的情况下,由于在涂布液中会容易产生沉淀物,因此,不仅涂层的均匀性会降低,而且还会抑制钌氧化物的功能。
所述涂料组合物还可以包含用于在涂料层中形成铈氧化物的铈前体。对铈前体的使用没有特别地限制,只要它是能够形成铈氧化物的化合物即可,可以是,例如,铈元素的水合物、氢氧化物、卤化物或氧化物,并且可以具体是选自硝酸铈(III)六水合物(Ce(NO3)3·6H2O)、硫酸铈(IV)四水合物(Ce(SO4)2·4H2O)和氯化铈(III)七水合物(CeCl3·7H2O)中的至少一种铈前体。当使用上面列出的铈前体时,铈氧化物的形成可以容易。
所述涂料组合物还可以包含用于在涂层中形成铂氧化物的铂前体。对铂前体的使用没有特别地限制,只要它是能够形成铂氧化物的化合物即可,并且,例如,可以使用选自氯铂酸六水合物(H2PtCl6·6H2O)、二胺二硝基铂(Pt(NH3)2(NO)2)、氯化铂(IV)(PtCl4)、氯化铂(II)(PtCl2)、四氯铂酸钾(K2PtCl4)和六氯铂酸钾(K2PtCl6)中的至少一种铂前体。当使用上面列出的铂前体时,铂氧化物的形成可以容易。
在本发明的制备电解用电极的方法中,可以使用醇类溶剂作为涂料组合物的溶剂。在使用醇类溶剂的情况下,上述组分容易溶解,并且即使在涂布涂料组合物之后在形成涂层的步骤中,也可以保持各个组分的粘合力。优选地,可以使用异丙醇和丁氧基乙醇中的至少一种作为溶剂,并且,更优选地,可以使用异丙醇与丁氧基乙醇的混合物。与单独使用异丙醇和丁氧基乙醇的情况相比,在将异丙醇与丁氧基乙醇混合并且使用的情况下,可以进行均匀涂布。
在本发明的制备方法中,所述制备方法可以包括在进行涂布之前对金属基底进行预处理的步骤。
所述预处理可以包括通过化学蚀刻、喷砂或热喷涂在金属基底的表面上形成不规则体。
所述预处理可以通过对金属基底的表面喷砂以形成细小的不规则体并进行盐或酸处理来进行。例如,所述预处理可以以如下方式进行:用氧化铝对金属基底的表面进行喷砂以形成不规则体,浸渍在硫酸水溶液中,洗涤,并且干燥,以在金属基底的表面上形成细小的不规则体。
对涂布没有特别地限制,只要可以将催化剂组合物均匀地涂布在金属基底上并且可以通过本领域中已知的方法进行即可。
涂布可以通过选自刮刀刮涂、压铸、逗号涂布、丝网印刷、喷涂、静电纺丝、辊涂和刷涂中的任意一种方法进行。
干燥可以在50℃至300℃下进行5分钟至60分钟,并且可以优选在50℃至200℃下进行5分钟至20分钟。
当满足上述条件时,可以使能量消耗最小化,同时可以充分除去溶剂。
热处理可以在400℃至600℃下进行1小时以下,并且可以优选在450℃至550℃下进行5分钟至30分钟。
当满足上述条件时,它不会影响金属基底的强度,同时容易除去催化剂层中的杂质。
涂层化可以通过顺序地重复涂布、干燥和热处理来进行,使得每单位面积(m2)的金属基底的钌氧化物的量为10g以上。即,将催化剂组合物涂布在金属基底的至少一个表面上,干燥,并且热处理之后,可以通过重复地涂布、干燥和热处理已经涂布有第一涂料组合物的金属基底的一个表面来进行根据本发明的另一实施方案的制备方法。
下文中,将根据实施例和实验例更详细地描述本发明,但是本发明不限于这些实施例和实验例。然而,本发明可以以许多不同的形式来实施,并且不应理解为局限于本文中阐述的实施例。而是,提供这些示例性实施例使得本说明书将是透彻和完整的,并且将向本领域技术人员充分传达本发明的范围。
材料
在实施例中,使用氯化钌(III)水合物(RuCl3·nH2O)作为钌前体,使用氯化铂(IV)作为铂前体,并且使用硝酸铈(III)六水合物(Ce(NO3)3·6H2O)作为铈前体。此外,使用尿素作为胺类添加剂,并且使用2.375ml的异丙醇与2.375ml的2-丁氧基乙醇的混合物作为涂料组合物的溶剂。
制备涂料组合物
将2.41mmol的氯化钌(III)水合物、0.842mmol的硝酸铈(III)六水合物(Ce(NO3)3·6H2O)和0.1928mmol的氯化铂(IV)经1小时充分溶解在上述材料的混合溶剂中,并且加入0.045g的尿素并混合以制备涂料组合物。
金属基底的预处理
在金属基底上形成涂层之前,在0.4MPa的压力下用氧化铝(白色氧化铝,F120)喷砂将在各个实施例和比较例中使用的金属基底的表面之后,将基底放入到被加热至80℃的5M的H2SO4水溶液中,处理3分钟,然后用蒸馏水洗涤以完成预处理。
实施例1
通过前面描述的预处理方法在线厚度为120μm且网目尺寸为60目的镍网(纯度为99%以上)上进行预处理之后,使用刷子将预先制备的涂料组合物涂布在预处理过的镍网上。之后,将涂布后的镍网在180℃的对流干燥箱中干燥10分钟,并在500℃的电加热炉中进一步热处理10分钟。将上述涂布、干燥和热处理工艺进一步进行9次之后,通过在500℃的电加热炉中进行热处理1小时来最终制备电解用电极。
实施例2
除了在实施例1中使用线厚度为150μm且网目尺寸为60目的镍网(纯度为99%以上)作为镍网之外,以相同的方式制备电解用电极。
实施例3
除了在实施例1中使用线厚度为150μm且网目尺寸为50目的镍网(纯度为99%以上)作为镍网之外,以相同的方式制备电解用电极。
比较例1
除了在实施例1中使用线厚度为150μm且网目尺寸为40目的镍网(纯度为99%以上)作为镍网之外,以相同的方式制备电解用电极。
比较例2
除了在实施例1中使用线厚度为150μm且网目尺寸为30目的镍网(纯度为99%以上)作为镍网之外,以相同的方式制备电解用电极。
比较例3
除了在实施例1中使用线厚度为150μm且网目尺寸为80目的镍网(纯度为99%以上)作为镍网之外,以相同的方式制备电解用电极。
比较例4
除了在实施例1中使用线厚度为180μm且网目尺寸为60目的镍网(纯度为99%以上)作为镍网之外,以相同的方式制备电解用电极。
比较例5
除了在实施例1中使用线厚度小于80μm且网目尺寸为60目的镍网(纯度为99%以上)作为镍网之外,以相同的方式制备电解用电极。
比较例6
除了在实施例1中的涂料组合物中不包含铂前体和尿素之外,以相同的方式制备电解用电极。
通过能量色散X射线光谱法(EDX)分析来确认在实施例和比较例中制备的电极的涂层中的金属基底结构以及钌和氮含量,并且总结在下面表1中。使用BrukerD4 Endeavor作为用于EDX分析的仪器。
[表1]
比较例1至比较例3是在本发明的网目尺寸之外的范围的情况,比较例4和比较例5是在本发明的单线厚度之外的情况,比较例6是不包含本发明的部分涂层组分的情况。对于实施例,由于涂布顺利进行,因此,氮与钌的比例高于比较例,并且,具体地,对于涂料组合物中不包含尿素的比较例6,氮含量显著低于实施例和其它比较例。
实验例1.制备的电解用电极的性能检查
为了确认在实施例和比较例中制备的电极的性能,进行在氯碱电解中的性能试验。使用实验室规模的零间隙单电池试验设备作为性能试验设备,并且电池尺寸为50mm×50mm,其中,使用Aciplex F6808膜。使用制备的电解用电极作为阴极,并且使用由AKC制造的市售电极作为阳极。试验条件包括:电流密度为6.2kA/m2,浓度为305g/L的氯化钠溶液作为阳极电解液,30.6%的NaOH水溶液作为阴极电解液,反应温度为90℃,并且在上面试验条件下测量电压。测量的电压值示于下面表2中。
[表2]
根据上面结果,对于网目尺寸在本发明的范围之外的比较例1至比较例3,可以确认,电极性能比本发明的实施例差。此外,可以确认,不包含本发明的涂料组分中的氮的比较例6的电极性能也比本发明的实施例差。此外,对于网状结构的线厚度小于本发明的范围的比较例5,可以确认,电极性能也比实施例差。对于线厚度大于实施例的比较例4,表现出与本发明的实施例相似的电极性能。
实验例2.检查在加速试验之前和加速试验之后涂层损失的存在
检查在实施例和比较例中制备的电极的加速试验之前和加速试验之后涂层损失的存在。使用制备的电极作为半电池进行加速试验,并且在通过恒定电流方法在恒定电流密度(60kA/m2)下进行电解反应1小时之后,通过X射线荧光(XRF)分析仪确认加速试验之前和加速试验之后涂层的金属含量。使用32%的氢氧化钠水溶液作为电解液,使用铂(Pt)线作为对电极,使用Hg/HgO电极作为参比电极。加速试验之前和加速试验之后涂层的钌、铈和铂组分的组成比示于下面表3中。
[表3]
根据上面结果,在本发明的实施例中几乎不发生涂层的脱离,但是,对于表现出与本发明相似的过电压的比较例4,可以发现,发生约25%的钌损失。涂层的脱离成为妨碍电解反应均匀进行的因素。比较例1至比较例3中Ru的变化为100%以上被确认为由于测量误差。
Claims (10)
1.一种电解用电极,该电解用电极包括:
金属基底层;和
包含钌氧化物和氮的涂层,
其中,所述金属基底层具有网目尺寸为45目至60目的网状结构,
所述网状结构的单线厚度在100μm至160μm的范围内,并且
基于所述钌氧化物,所述涂层中的氮含量在30摩尔%至70摩尔%的范围内。
2.根据权利要求1所述的电解用电极,其中,所述金属基底层的网目尺寸在50目至60目的范围内。
3.根据权利要求1所述的电解用电极,其中,所述网状结构的单线厚度在120μm至150μm的范围内。
4.根据权利要求1所述的电解用电极,其中,所述涂层还包含铈氧化物。
5.根据权利要求4所述的电解用电极,其中,所述涂层中的钌元素与铈元素的摩尔比在100:5至100:30的范围内。
6.根据权利要求1所述的电解用电极,其中,所述涂层还包含铂氧化物。
7.根据权利要求6所述的电解用电极,其中,所述涂层中的钌元素与铂元素的摩尔比在100:2至100:20的范围内。
8.一种制备电解用电极的方法,该方法包括:
在金属基底的至少一个表面上涂布涂料组合物,所述金属基底具有网状结构,其中网目尺寸在45目至60目的范围内,并且该网状结构的单线厚度在100μm至160μm的范围内;和
通过干燥和热处理涂布有所述涂料组合物的金属基底而涂层化,
其中,所述涂料组合物包含摩尔比为100:20至100:40的钌前体和胺类添加剂。
9.根据权利要求8所述的方法,其中,所述胺类添加剂是选自三聚氰胺、氨、尿素、1-丙胺、1-丁胺、1-戊胺、1-庚胺、1-辛胺、1-壬胺和1-十二烷胺中的至少一种。
10.根据权利要求8所述的方法,其中,所述涂料组合物还包含铈前体和铂前体。
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