CN114351178A - Electrode for electrolysis, electrolysis cell, electrolytic cell, electrode laminate, and method for renewing electrode - Google Patents
Electrode for electrolysis, electrolysis cell, electrolytic cell, electrode laminate, and method for renewing electrode Download PDFInfo
- Publication number
- CN114351178A CN114351178A CN202210045889.XA CN202210045889A CN114351178A CN 114351178 A CN114351178 A CN 114351178A CN 202210045889 A CN202210045889 A CN 202210045889A CN 114351178 A CN114351178 A CN 114351178A
- Authority
- CN
- China
- Prior art keywords
- electrode
- electrolysis
- mesh
- opening
- openings
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 275
- 238000000034 method Methods 0.000 title claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 claims abstract description 85
- 239000002184 metal Substances 0.000 claims abstract description 78
- 239000003054 catalyst Substances 0.000 claims abstract description 60
- 239000000463 material Substances 0.000 claims abstract description 56
- 239000003014 ion exchange membrane Substances 0.000 claims description 41
- 239000000758 substrate Substances 0.000 claims description 37
- 239000000126 substance Substances 0.000 claims description 10
- 238000003466 welding Methods 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 59
- 239000002585 base Substances 0.000 description 56
- 238000000576 coating method Methods 0.000 description 40
- 239000011248 coating agent Substances 0.000 description 38
- 230000002093 peripheral effect Effects 0.000 description 36
- 239000007788 liquid Substances 0.000 description 33
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 30
- 229910052719 titanium Inorganic materials 0.000 description 25
- 239000010936 titanium Substances 0.000 description 24
- 150000003839 salts Chemical class 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 21
- 238000010304 firing Methods 0.000 description 20
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 15
- 229910052707 ruthenium Inorganic materials 0.000 description 15
- 239000008151 electrolyte solution Substances 0.000 description 13
- 229910052741 iridium Inorganic materials 0.000 description 13
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 239000006104 solid solution Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000002411 adverse Effects 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 230000007420 reactivation Effects 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 7
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 6
- 238000010191 image analysis Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000012267 brine Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 229910000457 iridium oxide Inorganic materials 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- -1 platinum group metal oxide Chemical class 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003892 spreading Methods 0.000 description 4
- 230000007480 spreading Effects 0.000 description 4
- 229910052715 tantalum Inorganic materials 0.000 description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- 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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 150000003304 ruthenium compounds Chemical class 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 3
- 229920003934 Aciplex® Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000007610 electrostatic coating method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002504 iridium compounds Chemical class 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000008569 process Effects 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
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 2
- 238000005488 sandblasting Methods 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- ZQVHTTABFLHMPA-UHFFFAOYSA-N 2-(4-chlorophenoxy)-5-nitropyridine Chemical compound N1=CC([N+](=O)[O-])=CC=C1OC1=CC=C(Cl)C=C1 ZQVHTTABFLHMPA-UHFFFAOYSA-N 0.000 description 1
- 241000723353 Chrysanthemum Species 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000002146 bilateral effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- GSNZLGXNWYUHMI-UHFFFAOYSA-N iridium(3+);trinitrate Chemical compound [Ir+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GSNZLGXNWYUHMI-UHFFFAOYSA-N 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C25B11/02—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
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The present invention relates to an electrode for electrolysis, an electrolysis cell, an electrolytic cell, an electrode laminate, and a method for renewing an electrode. An electrode for electrolysis, comprising: the electrolytic electrode comprises a conductive base material comprising a metal plate having holes, and at least one catalyst layer formed on the surface of the conductive base material, wherein the shape of the opening of the electrolytic electrode is bilaterally symmetric with respect to a 1 st imaginary center line extending in the short lattice direction of the mesh, and vertically asymmetric with respect to a 2 nd imaginary center line extending in the long lattice direction of the mesh, and the thickness of the electrolytic electrode is more than 0.5mm and 1.2mm or less.
Description
The invention relates to a divisional application, which is originally applied with the international application number of PCT/JP2017/047365, the international application date of 12 and 28 in 2017, the national application number of 201780073743.3 in China, and the date of entering China of 5 and 29 in 2019, and is named as an electrode for electrolysis, an electrolytic cell, an electrode laminate and a method for updating the electrode.
Technical Field
The invention relates to an electrode for electrolysis, an electrolytic cell, an electrode laminate, and a method for renewing an electrode.
Background
The ion exchange membrane method of salt electrolysis is a method of producing sodium hydroxide, chlorine, and hydrogen by electrically decomposing (electrolyzing) brine using an electrode for electrolysis. In the process of salt electrolysis by an ion exchange membrane method, a technique capable of maintaining a low electrolysis voltage for a long period of time is required in order to reduce the power consumption from the viewpoint of the load on the environment and the problem of energy.
As is apparent from a detailed analysis of the electrolysis voltage, the electrolysis voltage includes, in addition to the theoretically required electrolysis voltage, a voltage due to the resistance of the ion exchange membrane and the structural resistance of the electrolytic cell, an overvoltage between the anode and the cathode as the electrodes for electrolysis, a voltage due to the distance between the anode and the cathode, and the like. Further, when electrolysis is continued for a long period of time, a voltage rise or the like due to various causes such as impurities in the brine is also generated.
Among the above-mentioned electrolytic voltages, various studies have been made for the purpose of reducing the overvoltage of the anode for chlorine generation. For example, patent document 1 discloses a technique of an insoluble anode in which a titanium substrate is coated with an oxide of a platinum group metal such as ruthenium. This Anode is called DSA (registered trademark, Dimension Stable Anode). Non-patent document 1 describes transition of sodium electrolysis technology using DSA.
With respect to the DSA, various improvements have been achieved so far, and studies for improving the performance have been made.
For example, patent document 2 proposes an electrolysis method in which electrolysis is performed as close as possible to the anode surface of a cation exchange membrane for an anode using a metallic porous plate having a predetermined thickness, pore diameter, and porosity or a metal expanded metal having a predetermined thickness, major diameter, minor diameter, and aperture ratio. Patent document 3 proposes an anode made of a substantially diamond-shaped metal mesh, in which the ratio of wires to openings of the mesh, and the longitudinal and width distances LWD and SWD of the openings are predetermined values. Patent document 3 discloses that a platinum group metal oxide, magnetite, ferrite, cobalt spinel, or a mixed metal oxide can be used as a coating layer on the surface of the metal mesh having such a shape.
Patent document 4 proposes a technique of using a titanium expanded metal or titanium expanded metal as an anode base material, and setting the aperture ratio and the thickness of the anode base material to predetermined ranges, and setting the maximum value of the difference in level between the irregularities on the anode surface after the catalyst is coated on the anode base material to a predetermined range, thereby improving the electrolytic performance.
Patent document 5 describes that the electrolytic cell voltage at the time of electrolysis can be reduced by adjusting the thickness of the anode to about half or less of the conventional thickness and the ratio of the longitudinal and transverse openings of the openings, and that an attempt is made to reduce the amount of impurity gas (i.e., oxygen gas) generated by the reaction of hydroxide ions diffusing from the cathode chamber through the ion exchange membrane by using the electrode.
As described above, conventionally, the voltage at the time of electrolysis is reduced in a direction of reducing the thickness of the anode and increasing the aperture ratio of the anode base material.
Documents of the prior art
Patent document
Patent document 1: japanese examined patent publication No. 46-021884
Patent document 2: japanese laid-open patent publication No. 58-130286
Patent document 3: japanese Kohyo publication No. 62-502820
Patent document 4: japanese patent No. 4453973 Specification
Patent document 5: international publication No. 2015/108115
Non-patent document
Non-patent document 1: the book of the Ministry of the Japan, the 8 th set of the systematic survey report of the technology of the national science museum, issued by the independent administrative Law of the national science museum, 3.30.3.2007, p32
Disclosure of Invention
Problems to be solved by the invention
However, in the conventional anode such as DSA described in patent document 1, the overvoltage immediately after the start of electrolysis is high, and a certain period of time is required until the overvoltage becomes low by activation of the catalyst, and therefore, there is a problem that power consumption loss occurs at the time of electrolysis.
In addition, in patent documents 2 to 4, although studies have been made on the aperture ratio of the expanded metal, the intervals in the longitudinal direction and the width direction of the mesh, and the like, the relationship between the shape of the anode and the electrolytic voltage has not been sufficiently studied, and further reduction in the electrolytic voltage is required. In particular, in an anode having a thin anode mesh and a high aperture ratio, there is a problem that the practical strength is insufficient.
Patent document 5 adopts a method of reducing the voltage of the anode and reducing the amount of oxygen generated by making the thickness of the anode about half or less of the conventional method, but in industrial-grade ion exchange membrane electrolytic cells, since the cathode chamber is pressurized and operated, strength cannot be secured if the thickness of the anode mesh is too thin, and it is necessary to use 2 metal mesh sheets in an overlapping manner, and further improvement is required to meet the reduction in the strength of the anode and the reduction in the electrolytic voltage.
The present invention has been made to solve the above problems. Accordingly, an object of the present invention is to provide an electrolysis electrode and an electrolytic cell provided with the same, which can suppress the voltage and the power consumption at the time of electrolysis to low levels and have practical strength.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems. As a result, the present inventors have found that an electrolysis electrode capable of suppressing the voltage and the electric energy consumption at the time of electrolysis at low levels and having practical strength can be provided by setting the thickness of the electrolysis electrode in a specific range and setting the value obtained by dividing the total of the peripheral lengths of the openings of the electrolysis electrode by the aperture ratio of the electrolysis electrode in a specific range, and have completed the present invention. The present inventors have also found that the above problems can be solved by making the opening of the electrolysis electrode a specific shape, and have achieved the present invention.
Namely, the present invention is as follows.
[1]
An electrode for electrolysis, comprising:
conductive base material comprising perforated metal plate, and
at least one catalyst layer formed on the surface of the conductive substrate,
wherein the content of the first and second substances,
the thickness of the electrode for electrolysis is more than 0.5mm and less than 1.2mm,
a value C obtained by dividing the total length B of the periphery of the opening of the electrolysis electrode by the opening ratio A of the electrolysis electrode is greater than 2 and not more than 5.
[2]
The electrolysis electrode according to [1], wherein the aperture ratio A is 5% or more and less than 25%.
[3]
The electrolysis electrode according to [1] or [2], wherein the center-to-center distance SW in the short cell direction of the mesh of the opening is 1.5 or more and 3 or less, and the center-to-center distance LW in the long cell direction of the mesh is 2.5 or more and 5 or less.
[4]
The electrolysis electrode according to any one of [1] to [3], wherein the thickness of the electrolysis electrode is more than 0.5mm and 0.9mm or less.
[5]
The electrolysis electrode according to any one of [1] to [4], wherein the value E represented by the following formula (1) is 0.5 or more.
E＝B/(A×(SW2+LW2)1/2) (1)
[6]
An electrolytic cell comprising:
an anode chamber comprising the electrode for electrolysis of any one of [1] to [5] as an anode,
A cathode chamber comprising a cathode, and
and an ion exchange membrane for separating the anode chamber from the cathode chamber.
[7]
The electrolytic cell as recited in [6], wherein the ion-exchange membrane has a protrusion on the anode-side surface thereof, the protrusion containing a polymer constituting the ion-exchange membrane.
[8]
An electrode laminate comprising:
[1] the electrode for electrolysis as described in any one of [1] to [3], and
a base electrode different from the electrolysis electrode.
[9]
The electrode laminate as set forth in [8], wherein the thickness of the electrode for electrolysis is more than 0.5mm and 0.65mm or less.
[10]
A method for replacing an electrode, comprising a step of welding the electrode for electrolysis according to any one of [1] to [3] to an existing electrode in an electrolytic cell.
[11]
An electrode for electrolysis, comprising:
conductive base material comprising perforated metal plate, and
at least one catalyst layer formed on the surface of the conductive substrate,
wherein the content of the first and second substances,
the shape of the opening of the electrolysis electrode is bilaterally symmetrical with respect to a 1 st imaginary center line extending in the short lattice direction of the mesh and vertically asymmetrical with respect to a 2 nd imaginary center line extending in the long lattice direction of the mesh,
the thickness of the electrode for electrolysis is more than 0.5mm and less than 1.2 mm.
[12]
The electrolysis electrode according to [11], wherein when the opening is divided into a portion a and another portion b by the 2 nd virtual center line, a value obtained by dividing an area Sa of the portion a by an area Sb of the portion b is 1.15 to 2.0.
[13]
The electrolysis electrode according to [11] or [12], wherein a value obtained by dividing a difference St obtained by subtracting a maximum mesh width in the short mesh direction of the meshes of the openings from an inter-center distance SW in the short mesh direction of the meshes of the openings by the SW is 0.4 or more.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide an electrode for electrolysis which can suppress the voltage and the power consumption at the time of electrolysis to low levels and has both practical strength.
Drawings
FIG. 1 is a schematic view for explaining the relationship between the total length of the periphery of the opening and the aperture ratio of the electrolysis electrode, assuming that the electrolysis electrode and the opening are square.
Fig. 2 is a schematic view of a typical example of a projection surface obtained by observing the electrolysis electrode according to one embodiment of the present embodiment with a microscope.
Fig. 3 is an explanatory diagram showing the relationship between the short cell direction center-to-center distance SW of the mesh of the opening portion and the long cell direction center-to-center distances LW and d of the mesh in the present embodiment, based on the schematic diagram of fig. 2.
Fig. 4 (a) is an explanatory view schematically showing a typical example of the shape of the opening of the electrolysis electrode in another embodiment of the present embodiment. Fig. 4 (B) is an explanatory diagram showing a part a and a part B in fig. 4 (a). Fig. 4 (C) is an explanatory view schematically showing a typical example of the shape of the opening of the conventional electrolysis electrode.
Fig. 5 is an explanatory view schematically showing an example of the positional relationship between adjacent openings in an electrolysis electrode according to another embodiment of the present embodiment.
FIG. 6 is a schematic diagram showing an example of a cross section of the electrolytic cell of the present embodiment.
Detailed Description
The following describes embodiments of the present invention (hereinafter, simply referred to as "the present embodiment") in detail. The following embodiments are examples for illustrating the present invention, and the present invention is not intended to be limited to the following. The present invention can be suitably modified and implemented within the scope of the gist thereof.
An electrolysis electrode according to claim 1 of the present embodiment (hereinafter also simply referred to as "1 st electrolysis electrode") is an electrolysis electrode comprising a conductive base material including a perforated metal plate and at least one catalyst layer formed on a surface of the conductive base material, wherein the thickness of the electrolysis electrode is greater than 0.5mm and 1.2mm or less, and a value C obtained by dividing the total B of the peripheral length of an opening of the electrolysis electrode by the aperture ratio a of the electrolysis electrode is greater than 2 and 5 or less. With this configuration, the 1 st electrolysis electrode can suppress the voltage and the electric power consumption at the time of electrolysis to low levels and has practical strength. The 1 st electrolysis electrode is particularly useful as an electrode for chlorine generation suitable for salt electrolysis by an ion exchange membrane method.
An electrolysis electrode according to claim 2 of the present embodiment (hereinafter also simply referred to as "2 nd electrolysis electrode") is an electrolysis electrode comprising a conductive base material including a perforated metal plate and at least one catalyst layer formed on a surface of the conductive base material, wherein the shape of an opening of the electrolysis electrode is bilaterally symmetric with respect to a 1 st virtual center line extending in a short lattice direction of a mesh, and vertically asymmetric with respect to a 2 nd virtual center line extending in a long lattice direction of the mesh, and the thickness of the electrolysis electrode is greater than 0.5mm and 1.2mm or less. With such a configuration, the 2 nd electrolysis electrode can also suppress the voltage and the electric power consumption at the time of electrolysis to low levels and has practical strength. The 2 nd electrolysis electrode is also particularly useful as an electrode for chlorine generation suitable for salt electrolysis by an ion exchange membrane method.
Hereinafter, the term "electrolysis electrode according to the present embodiment" includes the 1 st electrolysis electrode and the 2 nd electrolysis electrode.
(conductive substrate)
In the electrode for electrolysis of the present embodiment, the conductive base material comprises a porous metal plate, and is used in a chlorine generating atmosphere in a high concentration brine that is nearly saturated. Therefore, as a material of the conductive base material, a valve metal having corrosion resistance is preferable. Examples of the valve metal include, but are not limited to, titanium, tantalum, niobium, and zirconium. Among these valve metals, titanium is preferable from the viewpoint of economy and affinity with the catalyst layer.
The shape of the conductive base material is not particularly limited as long as it is made of metal and has a flat shape with holes, and examples thereof include shapes such as a metal lath, a perforated plate, and a wire mesh. Expanded metal is typically a substrate obtained as follows: a metal plate or a metal foil is formed into a mesh by drawing slits into the metal plate or the metal foil with an upper blade and a lower blade while spreading the slits, and flattened to a desired thickness by rolling or the like. Since continuous winding processing can be performed, the production efficiency is high, waste loss of the original plate is not caused, and the economy is excellent, and since the structure is integrated, complete conductivity is ensured unlike a wire mesh, and loosening is not caused.
The electrolysis electrode of the present embodiment is formed by forming at least one catalyst layer on the surface of the conductive base material. The thickness of the electrode for electrolysis of the present embodiment is more than 0.5mm and 1.2mm or less. When the electrode for electrolysis is a thin substrate having a thickness of 0.5mm or less, the pressure of the anode chamber and the cathode chamber generated during electrolysis and the pressing pressure of the cathode cause the anode to sink due to the pressing force of the ion exchange membrane against the anode, and the distance between the electrodes increases, thereby increasing the electrolysis voltage. In addition, if the thickness of the electrolysis electrode is more than 1.2mm, it is not possible to form the expanded metal having an appropriate aperture ratio and SW (short cell direction center distance of the meshes of the opening) and LW (long cell direction center distance of the meshes of the opening) of the opening in the present embodiment. From the same aspect as above, the thickness of the electrolysis electrode is preferably more than 0.5mm and 1.0mm or less, more preferably more than 0.5mm and 0.9mm or less, and still more preferably 0.7mm or more and 0.9mm or less.
In the 1 st electrolysis electrode, a value C (═ B/a) obtained by dividing the total length B of the periphery of the opening of the electrolysis electrode by the opening ratio a of the electrolysis electrode is greater than 2 and 5 or less, preferably 2.5 to 4.5 or less, and more preferably 3 to 4 or less.
The term "aperture ratio" A "as used herein means the projected area S of any one surface of the electrode for electrolysisATotal area S of the opening partBRatio (S)B/SA). Total area S of the openingBThe total projected area of the region of the electrolysis electrode, which is not cut by the conductive base material (porous metal plate), such as cations or an electrolytic solution, may be referred to.
The total B of the peripheral lengths of the openings referred to herein is a value obtained by measuring the peripheral length Li of the opening per unit area of the electrolysis electrode and integrating the peripheral length by the number n per unit area (Σ Li, i is 1 to n).
The relationship between the total length of the periphery of the opening and the opening ratio will be described with reference to fig. 1. In fig. 1, the opening is assumed to be square for simplicity of explanation, but the shape is different from the shape of the opening formed in the electrode for electrolysis of the present embodiment. As shown in FIG. 1(a), when 1 square (2 mm. times.2 mm) opening 2 is formed in a square (4 mm. times.4 mm) electrode 1, the opening area is 4mm2The aperture ratio was 25%, and the total of the peripheral lengths of the openings was 8 mm. On the other hand, as shown in FIG. 1(b), when 4 square (1 mm. times.1 mm) openings 3 are formed in the same-shaped electrode 1, the opening area is 4mm2The aperture ratio was 25% as in FIG. 1(a), but the total of the peripheral lengths of the openings was 16mm, which is larger than that in FIG. 1 (a). In this way, when compared at the same aperture ratio, the number of openings increases as the total of the peripheral lengths of the openings increases. That is, the sum of the peripheral length of the opening is divided by the aperture ratioThe larger the value, the larger the number of openings. The larger the number of openings, the more the gas flow paths are dispersed, so that the number of trapped bubbles is reduced, contributing to suppression of voltage rise.
Examples of a method for measuring the sum of the aperture ratio and the peripheral length of the opening include, but are not limited to: (I) a method of cutting an electrode for electrolysis into a square having a length of 10cm and a width of 10cm, cutting an opening portion from a sheet obtained by copying with a copying machine, and measuring the weight and the peripheral length of the cut portion as the opening portion; (II) a method of observing any one surface of the electrode for electrolysis by an image observation device such as a microscope, and measuring by analyzing image data obtained by imaging the projection plane; and so on. Fig. 2 gives a diagram schematically showing a typical example of the image data. As shown in FIG. 2, it is understood that a plurality of openings 20 are formed in the electrolysis electrode 10.
Regarding the above (I), the opening ratio (%) can be calculated from the weight w1 of the paper before the opening portion is cut out and the weight w2 of the paper after the opening portion is completely cut out by 100 × (w1-w2)/w 1. Further, the sum of the peripheral lengths of the portions cut out as the opening portions may be obtained as the total of the peripheral lengths.
As the method of analyzing the image data in the above (II), for example, "ImageJ" developed and shared by National Institute of Health (NIH) is used for image processing.
When the value C (B/a) obtained by dividing the total length B of the periphery of the opening of the electrolysis electrode by the opening ratio a of the electrolysis electrode is 2 or less, the opening ratio is increased or the electrolysis electrode having a small number of large openings is formed, and the specific surface area of the electrolysis electrode is reduced, whereby the apparent current density is increased and the electrolysis voltage is increased. When the value of C is greater than 5, a conductive base material having a decreased aperture ratio or a large number of small openings is formed, and the circulation of the electrolytic solution or the removability of the gas generated in the electrode may be adversely affected, thereby increasing the electrolytic voltage.
In the prior art, various techniques for reducing the electrolytic voltage by making the thickness of the electrode 0.5mm or less have been disclosed, but in the 1 st electrode for electrolysis, by making the thickness of the electrode for electrolysis greater than 0.5mm and 1.2mm or less and making the value C (═ B/a) obtained by dividing the total B of the peripheral length of the opening of the electrode for electrolysis by the opening ratio a greater than 2 and 5 or less, it is possible to produce an electrode for electrolysis which is capable of suppressing the voltage and the electric energy consumption at the time of electrolysis to low levels and has practical strength.
In the electrode for electrolysis of the present embodiment, the opening ratio of the electrode for electrolysis is preferably 5% or more and less than 25%, more preferably 7% or more and 20% or less, and particularly preferably 10% or more and 18% or less. When the opening ratio of the electrolysis electrode is 5% or more, adverse effects such as gas retention generated by the electrode during electrolysis can be effectively eliminated without adversely affecting the liquid circulation of the electrolytic solution, and the electrolysis voltage tends to be reduced. When the aperture ratio of the electrolysis electrode is less than 25%, the specific surface area of the electrolysis electrode, that is, the substantial electrode surface facing the ion exchange membrane tends to be sufficiently ensured, and as a result, the apparent current density and the electrolysis voltage tend to be reduced.
In the electrolysis electrode of the present embodiment, the length of the periphery of one opening of the electrolysis electrode is preferably 1mm or more, and more preferably 2.5mm or more. When the length of the periphery of one opening of the electrolysis electrode is 1mm or more, the pressure loss of the flow of the electrolytic solution at the opening is suppressed, and the electrolysis voltage tends to be reduced. From the viewpoint of sufficiently securing the specific surface area of the electrolysis electrode, the length of the periphery of one opening of the electrolysis electrode is preferably 4.8mm or less, and more preferably 4.55mm or less. The peripheral length of one opening of the electrolysis electrode can be measured by image analysis, which is a method of: the measurement is performed by observing one of the surfaces of the electrolysis electrode with an image observation device such as a microscope, and analyzing image data obtained by imaging the projection surface.
In the electrolysis electrode of the present embodiment, the short diameter SW of the distance between the centers in the short cell direction of the openings of the electrolysis electrode as the mesh is preferably 1.5mm or more and 3mm or less, and the long diameter LW of the distance between the centers in the long cell direction of the mesh is preferably 2.5mm or more and 5mm or less, and more preferably, the short diameter SW is 1.5mm or more and 2.5mm or less, and the long diameter LW is 3mm or more and 4.5mm or less.
The SW and LW described above may be defined as shown in fig. 3. That is, SW can be defined as a distance connecting centers of 2 openings adjacent in the short lattice direction of the mesh. LW may be defined as a distance connecting centers of 2 openings adjacent to each other in the longitudinal direction of the mesh.
When SW is 1.5mm or more and LW is 2.5mm or more, it is easy to ensure a thickness and an aperture ratio suitable for the present embodiment. In addition, when SW is 3mm or less and LW is 5mm or less, it is easy to secure an appropriate aperture ratio range, that is, to secure a specific surface area of the electrolysis electrode in the present embodiment.
Further, as shown in fig. 3, it is preferable to further adjust the distance d between the openings. The distance d is calculated by the square root of the value obtained by adding the square of LW and the square of SW, and the smaller the value, the more likely the movement of the gas or the like is promoted. From this viewpoint, the value of d is preferably 2.9 to 5.8mm, more preferably 3.4 to 5.1 mm.
In the electrolysis electrode of the present embodiment, the value E represented by the following formula (1), which is obtained from the sum B of the peripheral lengths of the openings, the opening ratio a of the openings, the short diameter SW of the openings, and the long diameter LW of the openings, is preferably 0.5 or more, more preferably 0.69 or more, and still more preferably 0.69 or more and 1.5 or less.
E＝B/(A×(SW2+LW2)1/2) (1)
In the formula (1), (SW)2+LW2)1/2Corresponding to d above. By adjusting the relationship between A, B and d to an appropriate range in this way, the degree of spatial dispersion of the openings is appropriate, and the electrolytic voltage tends to be reduced. That is, when the value of E in the electrolysis electrode is 0.5 to 1.5, the degree of spatial dispersion of the opening of the electrolysis electrode is suitable for the liquid circulation of the electrolytic solution, and the electrolysis voltage tends to be reduced.
Next, the 2 nd electrolysis electrode will be described in detail. The 2 nd electrolysis electrode comprises a conductive base material comprising a perforated metal plate and at least one catalyst layer formed on the surface of the conductive base material, wherein the shape of the opening of the electrolysis electrode is bilaterally symmetric with respect to a 1 st virtual center line extending in the short lattice direction of the mesh, and vertically asymmetric with respect to a 2 nd virtual center line extending in the long lattice direction of the mesh, and the thickness of the electrolysis electrode is more than 0.5mm and 1.2mm or less.
A typical example of the shape of the opening in the No. 2 electrolysis electrode is shown in FIG. 4 (A). The openings 100 in fig. 4 (a) are bilaterally symmetric with respect to a 1 st virtual center line 101 extending in the mesh opening direction α. The left-right symmetry is that, when the opening portion is divided into a right portion and a left portion with reference to the 1 st virtual center line, the shape of the right portion coincides with the shape of the left portion, that is, the right portion and the left portion are line-symmetric with reference to the 1 st virtual center line. The bilateral symmetry can be confirmed by the image analysis described above.
The openings 100 are vertically asymmetrical with respect to a 2 nd virtual center line 102 extending in the lattice direction β of the mesh. The vertically asymmetric shape means that when the opening portion is divided into the upper portion and the lower portion with reference to the 2 nd imaginary center line, the shape of the upper portion does not coincide with the shape of the lower portion, that is, the upper portion and the lower portion are not line-symmetric with reference to the 2 nd imaginary center line. The upper and lower symmetry can be confirmed by the image analysis described above. For example, in the example shown in fig. 4 (B), the opening 100 may be divided into an upper portion a and a lower portion B with reference to the 2 nd virtual center line 102 extending in the mesh length direction β, and the shape of the portions a and B may be easily confirmed by comparing the shapes.
The reason why the 2 nd electrolysis electrode can suppress the voltage and the electric energy consumption at the time of electrolysis to low levels is not clear, and the present inventors speculate that the reason is as follows. However, the present invention is not limited to this, and the electrolysis electrode having the above-described configuration is included in the 2 nd electrolysis electrode.
Typical shapes of the openings in the conventional electrolysis electrode include a shape that is symmetrical to the left and right with respect to the 1 st virtual center line and symmetrical to the top and bottom with respect to the 2 nd virtual center line. For example, in the example shown in fig. 4 (C), the opening portions 100' are bilaterally symmetrical with respect to the 1 st virtual center line 101 extending in the mesh opening short direction α. When the 2 nd virtual center line 102 extending in the mesh length direction β is defined as a reference, the opening 100' is formed such that the upper portion a and the lower portion b are line-symmetrical with respect to the virtual center line 102. In such a shape, the opening is typically diamond-shaped, and the 4 sides constituting the opening are located at substantially equal distances from the center point of the opening. It is presumed that, in such a conventional electrode for electrolysis, when the generated gas (typically, spherical) passes through the opening, the gas comes into contact with 4 sides (i.e., 4 points) constituting the opening, and thus the passing resistance tends to increase. That is, during electrolysis, gas generated from the electrode tends to contact the opening and easily accumulate therein, which adversely affects the liquid circulation of the electrolytic solution and causes a problem of an increase in electrolytic voltage.
On the other hand, by making the 2 nd electrolysis electrode bilaterally symmetrical with respect to the 1 st virtual center line and vertically asymmetrical with respect to the 2 nd virtual center line, it is estimated that the passing resistance tends to decrease when the gas (typically, spherical) generated from the electrode passes through the opening. That is, since the contact points between the gas generated from the electrode and each side constituting the opening portion tend to decrease during electrolysis, the gas tends to be effectively released, and the electrolysis voltage can be reduced without adversely affecting the liquid circulation of the electrolytic solution.
The 2 nd electrode for electrolysis had a projected area of 1cm on any one surface2The area of the opening (2) is not particularly limited, but is preferably 0.05cm from the viewpoint of further reducing the voltage and the power consumption during electrolysis2The above. In addition, the projection area is 1cm2The number of the openings (2) is not particularly limited, and is preferably 15 or more in terms of further reducing the voltage and the power consumption during electrolysis. The values of the area of the opening and the number of openings can be measured by the image analysis.
In the 2 nd electrolysis electrode, when the opening is divided into a part a and another part b by the 2 nd virtual center line, a value (Sa/Sb) obtained by dividing an area Sa of the part a by an area Sb of the part b is preferably 1.15 to 2.0. In this case, the vertical asymmetry of the processed portion tends to become more significant. That is, the Sa/Sb value also suggests that the shape of the opening of the electrolysis electrode is vertically asymmetrical with respect to the 2 nd virtual center line extending in the lattice direction of the mesh. When the value of Sa/Sb is 1.15 to 2.0, gas generated at the electrode during electrolysis tends to be efficiently desorbed without adversely affecting the liquid circulation of the electrolytic solution, and the electrolytic voltage tends to be reduced. Sa and Sb correspond to the area of the portion a and the area of the portion B in the example of fig. 4 (B), respectively, and Sa > Sb. The values of Sa and Sb can be measured by the above-described image analysis.
In the 2 nd electrolysis electrode, a value (St/SW) obtained by dividing a difference St obtained by subtracting a maximum mesh width in the short lattice direction of the meshes of the openings from a center-to-center distance SW in the short lattice direction of the meshes of the openings by the SW is preferably 0.4 or more, more preferably more than 0.67 and less than 1.0. In the example shown in FIG. 5, a plurality of openings are formed in the electrolysis electrode 300, and SW is defined by the distance 310 between the centers in the short lattice direction of the meshes of the openings in the adjacent 2 openings. The term "adjacent 2 openings" as used herein means an opening which is first contacted by the 1 st virtual center line when the 1 st virtual center line extends from a certain opening. In addition, LW is defined by the inter-center distance 320 in the lattice direction of the meshes of the openings in the adjacent 2 openings. The term "adjacent 2 openings" as used herein means an opening which is first contacted by the 2 nd virtual center line when the 2 nd virtual center line extends from a certain opening. In fig. 5, in the electrolysis electrode 300, the 2 nd virtual center line 330 divides the opening into a part a and a part b, and it is shown that the part a (340) and the part b (350) are vertically asymmetrical with respect to the virtual center line 330. In fig. 5, the distance 360 between 2 openings adjacent to each other in the short lattice direction of the meshes of the openings corresponds to the difference St obtained by subtracting the maximum mesh width in the short lattice direction of the meshes of the openings from the distance SW between the centers in the short lattice direction of the meshes of the openings. In the example shown in fig. 4 (a), the maximum mesh width in the short-lattice direction of the meshes of the opening corresponds to the length of the 1 st virtual center line 101. When St/SW is 0.4 or more, the specific surface area of the electrolysis electrode can be sufficiently secured, and the electrolysis voltage can be reduced without adversely affecting the liquid circulation of the electrolytic solution. The values of St and SW can be determined by image analysis as described above.
The electrode for electrolysis of the present embodiment is formed by forming at least one catalyst layer on the surface of the conductive base material, and in order to improve the adhesion to the catalyst layer, the surface of the conductive base material in contact with the catalyst layer is preferably subjected to a treatment for increasing the surface area of the conductive base material. Examples of the treatment method for increasing the surface area include, but are not limited to: sand blasting using steel wire particles, steel grit, alumina grit, or the like; acid treatment using sulfuric acid or hydrochloric acid, and the like. Among these treatments, a method of forming irregularities on the surface of the conductive base material by sandblasting and then further performing acid treatment is preferable.
(catalyst layer)
In order to reduce the electrolytic voltage, the catalyst layer formed on the surface of the conductive base material in the electrode for electrolysis of the present embodiment (preferably on the surface of the conductive base material subjected to the above treatment) preferably contains an electrode catalyst substance such as a platinum group metal oxide, magnetite, ferrite, cobalt spinel, or a mixed metal oxide. In the electrode catalyst material, it is more preferable that the ruthenium element, the iridium element, and the titanium element are in the form of oxides, respectively, from the viewpoint of suppressing the voltage at the time of electrolysis to be lower.
Examples of the ruthenium oxide include, but are not limited to, RuO2And the like.
Examples of iridium oxide include, but are not limited to, IrO2And the like.
Examples of the titanium oxide include, but are not limited to, TiO2And the like.
In the catalyst layer of the electrolysis electrode of the present embodiment, the ruthenium oxide, iridium oxide, and titanium oxide preferably form a solid solution. Ruthenium oxide, iridium oxide, and titanium oxide form a solid solution, and the durability of ruthenium oxide is further improved, and the electrolytic voltage tends to be kept low for a long period of time.
A solid solution generally refers to a substance in which two or more substances are fused with each other and the whole substance becomes a uniform solid phase. Examples of the substance forming a solid solution include a simple metal, a metal oxide, and the like. In particular, in the case of a solid solution suitable for the metal oxide of the present embodiment, two or more kinds of metal atoms are irregularly arranged on equivalent lattice nodes in a unit cell in the oxide crystal structure. Specifically, a substitution type solid solution in which ruthenium oxide, iridium oxide, and titanium oxide are mixed with each other and ruthenium atom is substituted with iridium atom or titanium atom or both of them as viewed from the ruthenium oxide side is preferable. The solid solution state is not particularly limited, and a region in which a solid solution is partially formed may exist.
By solid solution, the unit cell size in the crystal structure will vary slightly. The degree of the change can be confirmed by, for example, no change in the diffraction pattern due to the crystal structure or a change in the peak position due to the unit cell size in the measurement of powder X-ray diffraction.
In the catalyst layer of the electrolysis electrode of the present embodiment, the content ratio of the ruthenium element, the iridium element, and the titanium element is preferably 0.2 to 3 mol of the iridium element and 0.2 to 8 mol of the titanium element with respect to 1 mol of the ruthenium element; more preferably, the amount of iridium is 0.3 to 2 mol and the amount of titanium is 0.2 to 6 mol based on 1 mol of ruthenium; particularly preferably, the amount of iridium is 0.5 to 1.5 mol and the amount of titanium is 0.2 to 3 mol based on 1 mol of ruthenium. When the content ratio of the 3 elements is in the above range, the long-term durability of the electrode for electrolysis tends to be further improved. The iridium, ruthenium, and titanium may be contained in the catalyst layer in a form other than an oxide, for example, in the form of a simple metal.
The catalyst layer in the electrolysis electrode according to the present embodiment may contain, as constituent elements, only the ruthenium element, iridium element, and titanium element described above, or may contain other metal elements in addition to these. Specific examples of the other metal element include, but are not limited to, elements selected from tantalum, niobium, tin, platinum, vanadium, and the like. Examples of the form in which these other metal elements are present include the form in which the metal elements are contained in an oxide.
When the catalyst layer in the present embodiment contains another metal element, the content ratio of the other metal element is preferably 20 mol% or less, and more preferably 10 mol% or less, in terms of a molar ratio to the total metal elements contained in the catalyst layer.
The thickness of the catalyst layer in the present embodiment is preferably 0.1 to 5 μm, and more preferably 0.5 to 3 μm. When the thickness of the catalyst layer is not less than the lower limit value, the initial electrolysis performance tends to be sufficiently maintained. Further, when the thickness of the catalyst layer is not more than the above upper limit, an electrolytic electrode having excellent economical efficiency tends to be obtained. As for the thickness of the catalyst layer, a substrate section may be cut out and measured using an optical microscope or an electron microscope.
The catalyst layer may be composed of only one layer, or may be two or more layers.
When the catalyst layer is two or more layers, at least one of the layers may be the catalyst layer in the present embodiment. When the catalyst layer is two or more layers, at least the innermost layer is preferably the catalyst layer in the present embodiment. When at least the innermost layer is a solid solution formed of ruthenium oxide, iridium oxide, and titanium oxide, the durability of the catalyst layer tends to be further improved. It is also preferable to have two or more catalyst layers in the present embodiment in the same composition or different compositions.
When the catalyst layer is two or more layers, as described above, the thickness of the catalyst layer in the present embodiment is preferably 0.1 to 5 μm, and more preferably 0.5 to 3 μm.
(method of manufacturing electrode for electrolysis)
Next, the method for producing the electrolysis electrode according to the present embodiment will be described in detail by taking a case where a metal lath is used as the conductive base material as an example.
The electrode for electrolysis of the present embodiment can be produced as follows: the electrolytic electrode is produced by forming a mesh by drawing slits into an upper blade and a lower blade for a valve metal flat plate and simultaneously pushing and spreading the slits apart, rolling the mesh by a rolling roll or the like to a desired thickness to obtain a metal lath, using the metal lath as an electrically conductive base material, subjecting the electrically conductive base material to the above treatment for increasing the surface area, and then forming a catalyst layer containing ruthenium element, iridium element, and titanium element on the electrically conductive base material.
In the method of manufacturing a metal lath according to the present embodiment, when an electrolytic electrode having at least one catalyst layer formed on the surface of a conductive base material is manufactured by performing a step of forming a mesh by scoring a slit into an upper blade and a lower blade for a valve metal flat plate while pushing and spreading the slit, and then performing a step of flattening the mesh by rolling or the like, a metal lath having a thickness of more than 0.5mm and 1.2mm or less and a value C (═ B/a) obtained by dividing the total B of the peripheral lengths of openings by the aperture ratio a of the electrolytic electrode is more than 2 and 5 or less is manufactured.
The thickness of the electrode for electrolysis can be adjusted to a range suitable for the present embodiment by adjusting the thickness of the valve metal flat plate used as the material of the conductive base material and the rolling strength at the time of flattening by rolling or the like.
In a series of steps of forming meshes by cutting slits into the upper blade and the lower blade for the valve metal flat plate and simultaneously pushing and spreading the slits, the cutting width of the forward feed is continuously adjusted by the feed roller in conjunction with the vertical movement of the upper blade, whereby the aperture ratio of the electrolysis electrode and the minor axis SW of the distance between the centers in the direction of the mesh, which is the minor axis of the openings, can be adjusted to be suitable for the scope of the present embodiment. That is, from the viewpoint of adjusting the degree of dispersion of the openings in the present embodiment, it is preferable to adjust the notch width when the slits are notched with the upper blade and the lower blade for the valve metal flat plate to 0.8mm or less. In addition, from the viewpoint of maintaining the shape of the opening in the present embodiment, it is preferable to adjust the thickness to 0.5mm or more.
Further, by appropriately selecting the types of the upper blade and the lower blade for forming the slits in the valve metal flat plate, the major axis LW of the distance between the centers in the longitudinal direction of the mesh of the opening can be adjusted to be suitable for the range of the present embodiment.
Further, since the total of the peripheral length of the opening of the electrolysis electrode is increased or decreased depending on the increase or decrease of the number of openings, the total length can be adjusted by the number of upper and lower blades engraved in the slit, or the like.
On the other hand, when a porous plate such as a perforated metal plate is used as the conductive base material, the porous plate can be obtained by punching a flat metal plate with a die of a punch press, and in this case, the aperture ratio, the sum of the peripheral lengths of the openings, and SW and LW can be adjusted to appropriate ranges in accordance with the embodiment by appropriately selecting the shape and arrangement of the die, for example.
In the case of using a wire mesh as the conductive base material, the conductive base material can be obtained by knitting a plurality of wires for wire mesh production obtained by various known methods, and in this case, the aperture ratio, the sum of the peripheral lengths of the openings, and SW and LW can be adjusted to appropriate ranges in accordance with the embodiment by appropriately selecting, for example, the weight per unit length (denier, thickness corresponding to the wires) of the wire for wire mesh production, and the number of wires (mesh number) knitted into the wire mesh per unit area. In addition, the shape of the 2 nd electrolysis electrode tends to be easily obtained by the same control as described above.
The catalyst layer is preferably formed on the conductive substrate by a thermal decomposition method.
In the production method by the thermal decomposition method, a coating liquid containing a mixture of compounds (precursors) containing the above-mentioned elements is applied to a conductive substrate, and then firing is performed in an oxygen-containing atmosphere to thermally decompose components in the coating liquid, thereby forming a catalyst layer. By this method, the electrode for electrolysis can be produced with a higher productivity in a smaller number of steps than in the conventional production method.
The thermal decomposition here means that a metal salt or the like as a precursor is fired in an oxygen-containing atmosphere and decomposed into a metal oxide, a metal and a gaseous substance. The obtained decomposition product can be controlled by the kind of metal contained in the precursor mixed as a raw material in the coating liquid, the kind of metal salt, the atmosphere in which thermal decomposition is performed, and the like. In general, many metals tend to form oxides easily under an oxidizing atmosphere. In the industrial production process of an electrode for electrolysis, thermal decomposition is generally carried out in air. In the present embodiment, the oxygen concentration range during firing is not particularly limited, and it is sufficient to carry out the firing in air. However, air or oxygen may be circulated in the firing furnace as necessary.
Of the compounds contained in the coating liquid, the ruthenium compound, the iridium compound, and the titanium compound may be, but need not be, oxides. For example, a metal salt or the like can be used. Examples of the metal salt include, but are not limited to, any 1 selected from the group consisting of chloride salts, nitrates, sulfates, and metal alkoxides.
Examples of the metal salt of the ruthenium compound include, but are not limited to, ruthenium chloride, ruthenium nitrate, and the like.
Examples of the metal salt of the iridium compound include, but are not limited to, iridium chloride and iridium nitrate.
Examples of the metal salt of the titanium compound include, but are not limited to, titanium tetrachloride and the like.
The above-mentioned compound is appropriately selected and used in accordance with the desired ratio of the metal element in the catalyst layer.
The coating liquid may further contain other compounds than the compounds contained in the above-mentioned compounds. Examples of the other compounds include, but are not limited to, metal compounds containing metal elements such as tantalum, niobium, tin, platinum, rhodium, and vanadium; and organic compounds containing metal elements such as tantalum, niobium, tin, platinum, rhodium, and vanadium.
The coating liquid is preferably a liquid composition obtained by dissolving or dispersing the above-mentioned compound group in an appropriate solvent. The solvent of the coating liquid used here may be selected according to the kind of the above-mentioned compound. For example, water may be used; alcohols such as butanol. The total compound concentration in the coating liquid is not particularly limited, and is preferably 10 to 150g/L from the viewpoint of appropriately controlling the thickness of the catalyst layer.
As a method of applying the coating liquid to the surface on the conductive substrate, for example, but not limited to: an immersion method in which the conductive base material is immersed in the coating liquid; a method of applying a coating liquid to the surface of a conductive substrate with bristles; a roller method in which a conductive base material is passed through a sponge-like roller impregnated with a coating liquid; an electrostatic coating method in which the conductive base material and the coating liquid are charged oppositely and are atomized by spraying; and so on. Among these coating methods, a roll method and an electrostatic coating method are preferable in terms of excellent industrial productivity. By these coating methods, a coating film of the coating liquid can be formed on at least one surface of the conductive substrate.
After the coating liquid is applied to the conductive base material, a step of drying the coating film is preferably performed as necessary. By this drying step, a coating film can be formed more firmly on the surface of the conductive substrate. The drying conditions may be appropriately selected depending on the composition of the coating liquid, the kind of the solvent, and the like. The drying step is preferably carried out at a temperature of 10 to 90 ℃ for 1 to 20 minutes.
After a coating film of the coating liquid is formed on the surface of the conductive base material, firing is performed in an oxygen-containing atmosphere. The firing temperature may be appropriately selected depending on the composition of the coating liquid and the kind of the solvent. The firing temperature is preferably 300 to 650 ℃. When the firing temperature is less than 300 ℃, the decomposition of the precursor such as a ruthenium compound is insufficient, and a catalyst layer containing ruthenium oxide or the like may not be obtained. When the firing temperature is more than 650 ℃, the conductive substrate may be oxidized, and thus the adhesion at the interface between the catalyst layer and the substrate may be reduced. In particular, when a titanium substrate is used as the conductive substrate, such a tendency should be emphasized.
The firing time is preferably long. On the other hand, from the viewpoint of electrode productivity, it is preferable to adjust the firing time so as not to become excessively long. In consideration of these circumstances, the primary firing time is preferably 5 to 60 minutes.
The catalyst layer can be formed to a desired thickness by repeating the steps of coating, drying, and firing the catalyst layer 2 or more times as necessary. After the catalyst layer is formed, the catalyst layer may be fired for a longer time as necessary, thereby further improving the stability of the catalyst layer which is extremely stable in terms of chemistry, physics and heat. The firing conditions for a long time are preferably about 30 minutes to 4 hours at 400 to 650 ℃.
The electrolysis electrode of the present embodiment is also low in overvoltage at the initial stage of electrolysis, and can perform electrolysis at a low voltage and low power consumption for a long period of time. And thus can be used for various kinds of electrolysis. In particular, the use as an anode for chlorine generation is preferable, and the use as an anode for salt electrolysis by an ion exchange membrane method is more preferable.
(electrolytic bath)
The electrolytic cell of the present embodiment includes the electrode for electrolysis of the present embodiment. That is, the electrolytic cell of the present embodiment includes an anode chamber including the electrode for electrolysis of the present embodiment as an anode, a cathode chamber including a cathode, and an ion exchange membrane separating the anode chamber and the cathode chamber. The electrolytic cell can reduce the initial voltage during electrolysis. FIG. 6 schematically shows an example of a cross section of the electrolytic cell of the present embodiment.
The electrolytic cell 200 includes an electrolytic solution 210, a container 220 for containing the electrolytic solution 210, an anode 230 and a cathode 240 immersed in the electrolytic solution 210, an ion exchange membrane 250, and a wire 260 for connecting the anode 230 and the cathode 240 to a power supply. In the electrolytic cell 200, the space on the anode side partitioned by the ion exchange membrane 250 is referred to as an anode chamber, and the space on the cathode side is referred to as a cathode chamber. The electrolytic cell of the present embodiment can be used for various types of electrolysis. Hereinafter, a case of using the electrolytic solution for the alkali metal chloride aqueous solution will be described as a representative example thereof.
As the electrolyte 210 to be supplied to the electrolytic cell of the present embodiment, for example, an alkali metal chloride aqueous solution such as a sodium chloride aqueous solution (saline solution) or a potassium chloride aqueous solution of 2.5 to 5.5 equivalents (N) may be used in the anode chamber, and an alkali metal hydroxide aqueous solution (for example, a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution) or water may be used in the cathode chamber after dilution.
As the anode 230, the electrolysis electrode of the present embodiment is used.
As the ion exchange membrane 250, for example, a fluororesin membrane having an ion exchange group or the like can be used. Of the ion exchange membranes, an ion exchange membrane in which a protrusion (fine protrusion: triangular shape) containing a polymer constituting the ion exchange membrane is formed on the anode side surface of the ion exchange membrane is preferably used as the electrolytic cell in combination with the electrode for electrolysis of the present embodiment. Specific examples thereof include "Aciplex" (registered trademark) F6801 (manufactured by asahi chemicals co., ltd.).
By using the ion exchange membrane having a triangular shape, the supply of brine between the ion exchange membrane and the anode can be promoted, and damage to the ion exchange membrane and an increase in the salt concentration in sodium hydroxide tend to be suppressed. By combining the ion exchange membrane having a triangular shape with the electrode for electrolysis of the present embodiment, the electrolysis performance can be stably maintained. The method for forming the protruding portion is not particularly limited, and may be formed by, for example, the methods described in japanese patent No. 4573715 and japanese patent No. 4708133.
As the cathode 240, an electrode formed by coating a catalyst on a conductive substrate, which is a cathode for hydrogen generation, or the like is used. As the cathode, a known cathode can be used, and specific examples thereof include: a cathode coated with nickel, nickel oxide, an alloy of nickel and tin, a combination of activated carbon and an oxide, ruthenium oxide, platinum, or the like on a nickel base material; a cathode coated with ruthenium oxide is formed on a nickel wire mesh substrate; and so on.
The structure of the electrolytic cell of the present embodiment is not particularly limited, and may be a monopolar type or a bipolar type. The material constituting the electrolytic cell is not particularly limited, and for example, as the material of the anode chamber, titanium or the like having resistance to alkali metal chloride and chlorine is preferable; as a material of the cathode chamber, nickel or the like having resistance to alkali metal hydroxide and hydrogen is preferable.
The electrolysis electrode (anode 230) of the present embodiment may be disposed with an appropriate space between it and the ion exchange membrane 250, or may be disposed in contact with the ion exchange membrane 250, and may be used without any problem. The cathode 240 may be disposed at an appropriate interval from the ion exchange membrane 250, or may be a contact type electrolytic cell (zero-pitch electrolytic cell) having no interval between the cathode and the ion exchange membrane 250.
The electrolysis conditions of the electrolytic cell of the present embodiment are not particularly limited, and the electrolytic cell can be operated under known conditions. For example, it is preferable to adjust the electrolysis temperature to 50 to 120 ℃ and the current density to 0.5 to 10kA/m2To carry out electrolysis.
(reactivation of electrode for Electrolysis)
The electrode for electrolysis of the present embodiment can be suitably used for the purpose of renewing the electrode when the activity of the catalyst-coated electrode existing in the electrolytic cell is lowered. That is, the method for replacing an electrode in the present embodiment includes a step of welding the electrode for electrolysis in the present embodiment to an existing electrode in an electrolytic cell. In this way, by simply welding the electrode for electrolysis of the present embodiment to the existing electrode newly, the electrolytic performance of the existing electrode with reduced activity can be restored to the level before deterioration, or further improved, that is, reactivation can be easily performed. Therefore, the burden of the conventional electrode renewal due to the two steps of peeling the conventional electrode from the electrolytic bath and welding a new electrode when renewing the conventional electrode with reduced activity can be reduced.
As described above, the electrode for electrolysis of the present embodiment and the existing electrode in the electrolytic cell to be welded can be regarded as a laminate. That is, the electrode laminate of the present embodiment includes the electrode for electrolysis of the present embodiment and a base electrode different from the electrode for electrolysis. The base electrode as used herein is not particularly limited, and typical examples thereof include conventional electrodes in the electrolytic cell described above, i.e., electrodes having reduced activity.
The electrolysis electrode of the present embodiment suitable for reactivation of the electrolysis electrode preferably has a thickness of more than 0.5mm and 0.65mm or less, and a value C (═ B/a) obtained by dividing the total sum B of the peripheral lengths of the openings by the opening ratio a is more than 2 and 5 or less. When the thickness is within the above range, welding is easily performed when welding is performed newly on the conventional electrode, and the electrolytic performance can be restored to a level before deterioration or further improved, that is, reactivation can be performed without particularly changing the internal structure, the used members, and the like of the conventional electrolytic cell. That is, in the electrode laminate of the present embodiment, the thickness of the electrode for electrolysis is preferably more than 0.5mm and 0.65mm or less.
The electrolysis electrode of the present embodiment can reduce the electrolysis voltage in salt electrolysis compared to conventional electrodes. Therefore, the electrolytic cell of the present embodiment provided with the electrode for electrolysis can reduce the electric energy consumption required for salt electrolysis.
Further, the electrode for electrolysis of the present embodiment has a catalyst layer that is extremely stable chemically, physically, and thermally, and thus has excellent long-term durability. Therefore, the electrolytic cell of the present embodiment including the electrode for electrolysis can stably produce high-purity chlorine while maintaining high catalytic activity of the electrode for a long period of time.
Examples
The present embodiment will be described in more detail below based on examples. The present embodiment is not limited to these examples.
First, the evaluation methods in examples and comparative examples are shown below.
(salt electrolysis test by ion exchange Membrane method)
As the electrolysis unit, an electrolysis unit including an anode unit having an anode chamber and a cathode unit having a cathode chamber was prepared.
The electrodes for electrolysis prepared in each of examples and comparative examples were cut into a predetermined size (95X 110 mm: 0.01045 m)2) The test electrode was attached to a rib of the anode chamber of the anode unit by welding and used as an anode.
As the cathode, a member coated with a ruthenium oxide catalyst on a nickel wire mesh substrate was used. First, a metal nickel expanded metal substrate as a current collector was cut into the same size as the anode and welded to the ribs of the cathode chamber of the cathode unit, and then a buffer pad made of nickel wires was placed thereon, and the cathode was disposed thereon.
As the gasket, a rubber gasket made of EPDM (ethylene propylene diene) was used, and an ion exchange membrane was interposed between the anode cell and the cathode cell. As the ion exchange membrane, a cation exchange membrane "Aciplex" (registered trademark) F6801 (manufactured by asahi chemicals co., ltd.) for salt electrolysis was used.
The measurement of the electrolytic voltage was carried out by measuring the potential difference between the cathode and the anode. In order to measure the initial electrolytic performance of the anode, the electrolytic voltage was measured after 5 days from the start of electrolysis. As for the electrolysis conditions, at a current density of 6kA/m2The brine concentration in the anode cell was 205g/L, the NaOH concentration in the cathode cell was 32 mass%, and the temperature was 90 ℃. As a rectifier for electrolysis, "PAD 36-100 LA" (manufactured by Chrysanthemum electronics industries, Ltd.) was used.
[ example 1]
As the conductive substrate, a titanium metal lath having a mesh opening with a center-to-center distance in the short lattice direction (SW) of 2.1mm, a mesh opening with a center-to-center distance in the long lattice direction (LW) of 3mm, and a plate thickness of 0.81mm was used. The thickness of the plate was measured by a thickness meter. The values of SW, LW, St, the aperture ratio, and the total of the peripheral length of the opening are determined as follows: the predetermined range of the surface of the conductive base material is observed by an image observation device such as a microscope, and the image data obtained by imaging the projection surface is analyzed. As an analysis method of image data, "ImageJ" developed and shared by National Institute of Health (NIH) is used for image processing. The image size used in the image processing was in the range of 8.0 × 5.3mm of the conductive substrate. That is, for the openings existing in this range, the center-to-center distances in the short cell direction, the center-to-center distances in the long cell direction, and the maximum cell width in the short cell direction of the openings defined for each adjacent opening are measured, and the average values thereof are calculated as SW, LW, and St, respectively. Hereinafter, SW, LW, St, aperture ratio a, and opening were also determined for the conductive base material and the electrode for electrolysis in each of examples and comparative examples in the same manner as described aboveThe total peripheral length of the openings B, the peripheral length of 1 opening E (B/(a × (SW))2+LW2)1/2) And the value of thickness. This metal lath was fired at 540 ℃ for 4 hours in the air to form an oxide film on the surface, and then acid-treated in 25 mass% sulfuric acid at 85 ℃ for 4 hours to perform pretreatment for forming fine irregularities on the surface of the conductive substrate.
Then, the ratio of the elements ruthenium, iridium and titanium (molar ratio) was 25: 25: 50, while cooling an aqueous ruthenium chloride solution (100 g/L ruthenium concentration, manufactured by Takara Shuzo Co., Ltd.) to 5 ℃ or lower with dry ice and stirring, titanium tetrachloride (manufactured by Kishida Chemical Co., Ltd.) was added little by little, and thereafter an aqueous iridium chloride solution (100 g/L iridium concentration, manufactured by Takara Shuzo Co., Ltd.) was added little by little to obtain a coating solution CL1 which is an aqueous solution having a total metal concentration of 100 g/L. On the other hand, the ratio of the elements ruthenium and titanium (molar ratio) was 35: 65, the aqueous solution of ruthenium chloride and titanium tetrachloride were mixed in the same manner as described above to obtain a coating solution CL2 which was an aqueous solution having a total metal concentration of 100 g/L.
The coating liquid CL1 was poured into a liquid receiving tray of the coater, and the EPDM sponge roller was rotated to suck the impregnation coating liquid CL1, and the PVC roller was disposed so as to contact the upper part of the sponge roller. After that, the pretreated conductive substrate was passed between the EPDM sponge roll and the PVC roll to be coated. Immediately after the application, the conductive substrate after the application was passed between 2 sponge rolls made of EPDM around which cloth was wound, and excess coating liquid was wiped off. Thereafter, the mixture was dried at 50 ℃ for 10 minutes and then fired at 475 ℃ for 10 minutes in the air.
The cycle consisting of roll coating, drying and firing described above was repeated 7 times in total, and then firing was further performed at 520 ℃ for 1 hour, thereby forming a blackish brown first catalyst layer on the conductive base material. The substrate on which the first catalyst layer was formed was roll-coated in the same manner as in the case of coating with coating liquid CL1, except that the coating liquid was replaced with CL2, and then dried and baked at 440 ℃ for 10 minutes in the air. Finally, firing was carried out at 440 ℃ for 60 minutes in the atmosphere to produce an electrode for electrolysis.
The obtained electrode for electrolysis had a thickness of 0.81mm and an aperture ratio of 7.4%, and the number of openings per unit projected area of the electrode was more than 20/cm2The value obtained by dividing the total of the peripheral lengths of the openings by the aperture ratio was 4.54. In addition, regarding the shape of the openings, the same shape as that of fig. 4 (a) is observed, and the openings 100 are bilaterally symmetric with respect to a 1 st virtual center line 101 extending in the short lattice direction α of the mesh. The openings 100 are vertically asymmetrical with respect to a 2 nd virtual center line 102 extending in the lattice direction β of the mesh. Further, the value obtained by dividing the area Sa of the portion a by the area Sb of the portion b was 1.28, and the value obtained by dividing St by SW was 0.76.
Comparative example 1
An electrode for electrolysis was produced in the same manner as in example 1, except for using a titanium expanded metal having a mesh opening as the conductive base material in example 1, wherein the center-to-center distance in the short cell direction (SW) was 3mm, the center-to-center distance in the long cell direction (LW) was 6mm, and the thickness was 1.0 mm.
The obtained electrode for electrolysis had a thickness of 1.0mm, an aperture ratio of 37.8%, and the number of openings per projected area of the electrode was 13/cm2The value obtained by dividing the total of the peripheral lengths of the openings by the aperture ratio was 1.06. In addition, regarding the shape of the openings, the same shape as that of fig. 4 (C) is observed, and the openings 100' are bilaterally symmetric with respect to the 1 st virtual center line 101 extending in the mesh cell direction α. The openings 100' are vertically symmetrical with respect to a 2 nd virtual center line 102 extending in the lattice direction β of the mesh. Further, the value obtained by dividing the area Sa of the portion a by the area Sb of the portion b was 1.03, and the value obtained by dividing St by SW was 0.667.
[ example 2]
An electrode for electrolysis was produced in the same manner as in example 1, except that the conductive base material in example 1 was a titanium expanded metal having a mesh opening center-to-center distance in the short cell direction (SW) of 2.2mm, a mesh opening center-to-center distance in the long cell direction (LW) of 4.2mm, and a plate thickness of 0.8 mm.
The resulting electrolysisThe thickness of the electrode was 0.80mm, the aperture ratio was 10.9%, and the number of openings per unit projected area of the electrode was 20/cm2The value obtained by dividing the total of the peripheral lengths of the openings by the aperture ratio was 3.26. In addition, regarding the shape of the openings, the same shape as that of fig. 4 (a) is observed, and the openings 100 are bilaterally symmetric with respect to a 1 st virtual center line 101 extending in the short lattice direction α of the mesh. The openings 100 are vertically asymmetrical with respect to a 2 nd virtual center line 102 extending in the lattice direction β of the mesh. Further, the value obtained by dividing the area Sa of the portion a by the area Sb of the portion b was 1.64, and the value obtained by dividing St by SW was 0.73.
[ example 3]
An electrode for electrolysis was produced in the same manner as in example 1, except that the conductive base material in example 1 was a titanium expanded metal having a mesh center-to-center distance in the short cell direction (SW) of 2.3mm, a mesh center-to-center distance in the long cell direction (LW) of 3.3mm, and a plate thickness of 0.83 mm.
The obtained electrode for electrolysis had a thickness of 0.83mm, an aperture ratio of 9.25%, and the number of openings per unit projected area of the electrode was more than 20/cm2The value obtained by dividing the total of the peripheral lengths of the openings by the aperture ratio was 3.65. In addition, regarding the shape of the openings, the same shape as that of fig. 4 (a) is observed, and the openings 100 are bilaterally symmetric with respect to a 1 st virtual center line 101 extending in the short lattice direction α of the mesh. The openings 100 are vertically asymmetrical with respect to a 2 nd virtual center line 102 extending in the lattice direction β of the mesh. Further, the value obtained by dividing the area Sa of the portion a by the area Sb of the portion b was 1.27, and the value obtained by dividing St by SW was 0.70.
[ example 4]
An electrode for electrolysis was produced in the same manner as in example 1, except that the conductive substrate in example 1 was a titanium expanded metal having a mesh center-to-center distance in the short cell direction (SW) of 2.3mm, a mesh center-to-center distance in the long cell direction (LW) of 3.3mm, and a plate thickness of 0.81 mm.
The obtained electrode for electrolysis had a thickness of 0.81mm and an aperture ratio of 22.1%, and the number of openings per unit projected area of the electrode was more than 20/cm2The value obtained by dividing the total of the peripheral lengths of the openings by the aperture ratio was 2.05. In addition, regarding the shape of the openings, the same shape as that of fig. 4 (a) is observed, and the openings 100 are bilaterally symmetric with respect to a 1 st virtual center line 101 extending in the short lattice direction α of the mesh. The openings 100 are vertically asymmetrical with respect to a 2 nd virtual center line 102 extending in the lattice direction β of the mesh. Further, the value obtained by dividing the area Sa of the portion a by the area Sb of the portion b was 1.28, and the value obtained by dividing St by SW was 0.43.
[ example 5]
An electrode for electrolysis was produced in the same manner as in example 1, except that the conductive substrate in example 1 was a titanium expanded metal having a mesh opening center-to-center distance in the short cell direction (SW) of 1.6mm, a mesh opening center-to-center distance in the long cell direction (LW) of 3.0mm, and a plate thickness of 0.56 mm.
The obtained electrode for electrolysis had a thickness of 0.56mm, an aperture ratio of 17.5%, and the number of openings per projected area of the electrode was 43 pieces/cm2The value obtained by dividing the total of the peripheral lengths of the openings by the aperture ratio was 3.30. In addition, regarding the shape of the openings, the same shape as that of fig. 4 (a) is observed, and the openings 100 are bilaterally symmetric with respect to a 1 st virtual center line 101 extending in the short lattice direction α of the mesh. The openings 100 are vertically asymmetrical with respect to a 2 nd virtual center line 102 extending in the lattice direction β of the mesh. Further, the value obtained by dividing the area Sa of the portion a by the area Sb of the portion b was 1.88, and the value obtained by dividing St by SW was 0.65.
[ example 6]
An electrode for electrolysis was produced in the same manner as in example 1, except that the conductive substrate in example 1 was a titanium expanded metal having a mesh center-to-center distance in the short cell direction (SW) of 2.1mm, a mesh center-to-center distance in the long cell direction (LW) of 3.1mm, and a plate thickness of 0.81 mm.
The obtained electrode for electrolysis had a thickness of 0.81mm and an aperture ratio of 15.5%, and the number of openings per unit projected area of the electrode was more than 20/cm2The value obtained by dividing the total of the peripheral lengths of the openings by the aperture ratio was 2.72. In addition, regarding the opening partThe shape is the same as that of fig. 4 (a), and the openings 100 are bilaterally symmetric with respect to a 1 st virtual center line 101 extending in the mesh opening direction α. The openings 100 are vertically asymmetrical with respect to a 2 nd virtual center line 102 extending in the lattice direction β of the mesh. Further, the value obtained by dividing the area Sa of the portion a by the area Sb of the portion b was 1.42, and the value obtained by dividing St by SW was 0.67.
[ example 7]
The coating solution CL1 in example 1 was applied to the titanium expanded metal sheet (SW: 2.2mm, LW: 3.2mm, sheet thickness 0.82mm) prepared in the same manner as in example 6 by the same method as in example 1, and a first catalyst layer was formed on the conductive substrate.
Then, the ratio of the elements ruthenium, iridium, titanium and vanadium (molar ratio) was 21.25: 21.25: 42.5: in the embodiment of 15, while cooling an aqueous ruthenium nitrate solution (manufactured by Furuya Metal Co., Ltd., ruthenium concentration 100g/L) to 5 ℃ or lower with dry ice and stirring, titanium tetrachloride (manufactured by Wako pure Chemical industries, Ltd.) was added little by little, and thereafter, an aqueous iridium chloride solution (manufactured by Takara noble metals Co., Ltd., iridium concentration 100g/L) and vanadium (III) chloride (manufactured by Kishida Chemical Co., Ltd.) were added little by little to obtain a coating solution CL3 which was an aqueous solution having a total Metal concentration of 100 g/L. The substrate on which the first catalyst layer was formed was subjected to a cycle consisting of roll coating, drying and firing using coating liquid CL3 in the same manner as in example 1, wherein the firing temperature in the 1 st stage was set to 400 ℃, the temperature was then raised to 450 ℃ and the process was repeated 3 times, and finally firing was carried out at 520 ℃ for 1 hour, thereby producing an electrode for electrolysis.
The obtained electrode for electrolysis had a thickness of 0.82mm, an aperture ratio of 16.1%, and the number of openings per unit projected area of the electrode was more than 20/cm2The value obtained by dividing the total of the peripheral lengths of the openings by the aperture ratio was 2.73. In addition, regarding the shape of the openings, the same shape as that of fig. 4 (a) is observed, and the openings 100 are bilaterally symmetric with respect to a 1 st virtual center line 101 extending in the short lattice direction α of the mesh. The openings 100 are vertically asymmetrical with respect to a 2 nd virtual center line 102 extending in the lattice direction β of the mesh.Further, the value obtained by dividing the area Sa of the portion a by the area Sb of the portion b is 1.38, and the value obtained by dividing St by SW is 0.63.
Comparative example 2
An electrode for electrolysis was produced in the same manner as in example 1, except that the conductive base material in example 1 was a titanium expanded metal sheet having a mesh opening center-to-center distance in the short cell direction (SW) of 2.3mm, a mesh opening center-to-center distance in the long cell direction (LW) of 3.0mm, and a sheet thickness of 0.6mm, and which was not flattened by a reduction roll.
The thickness of the obtained electrode for electrolysis was 0.6mm, the aperture ratio was 43.3%, and the value obtained by dividing the total of the peripheral length of the opening by the aperture ratio was 1.07. In addition, regarding the shape of the openings, the same shape as that of fig. 4 (C) is observed, and the openings 100' are bilaterally symmetric with respect to the 1 st virtual center line 101 extending in the mesh cell direction α. The openings 100' are vertically symmetrical with respect to a 2 nd virtual center line 102 extending in the lattice direction β of the mesh. Further, the value obtained by dividing the area Sa of the portion a by the area Sb of the portion b is 0.90, and the value obtained by dividing St by SW is 0.45.
Comparative example 3
An electrode for electrolysis was produced in the same manner as in example 1, except that the conductive base material in example 1 was a titanium expanded metal having a mesh opening center-to-center distance in the short cell direction (SW) of 2.1mm, a mesh opening center-to-center distance in the long cell direction (LW) of 4.0mm, and a plate thickness of 0.5 mm.
The thickness of the obtained electrode for electrolysis was 0.5mm, the aperture ratio was 35.7%, and the value obtained by dividing the total of the peripheral length of the opening by the aperture ratio was 1.78. In addition, regarding the shape of the openings, the same shape as that of fig. 4 (C) is observed, and the openings 100' are bilaterally symmetric with respect to the 1 st virtual center line 101 extending in the mesh cell direction α. The openings 100' are vertically symmetrical with respect to a 2 nd virtual center line 102 extending in the lattice direction β of the mesh. Further, the value obtained by dividing the area Sa of the portion a by the area Sb of the portion b was 1.10, and the value obtained by dividing St by SW was 0.48.
[ ion exchange Membrane method salt Electrolysis test ]
Salt electrolysis test by ion exchange membrane method was carried out using the electrodes for electrolysis prepared in examples 1 to 6 and comparative examples 1 to 3, respectively. The results are shown in table 1.
In table 1, the case where the metal lath used as the conductive substrate was flattened by the reduction rolls is referred to as "FR formation o", and the case where it was not flattened is referred to as "FR formation x". The reduction in electrolytic voltage based on comparative example 1 is in the following manner: Δ V "is represented as a positive value.
With respect to 6kA/m2The amount of reduction in electrolytic voltage based on comparative example 1 was 35mV in example 1, 43mV in example 2, 41mV in example 3, 8mV in example 4, 42mV in example 5, and 19mV in example 6 at the current density of (1), and it was found that the electrolytic voltage could be reduced compared to comparative example 1.
On the other hand, in comparative examples 2 and 3, the electrolytic voltage was increased by 23mV and 19mV, respectively, compared with that in comparative example 1.
An ion exchange membrane salt electrolysis test was performed using the electrolysis electrodes prepared in examples 6 to 7 and comparative example 1. The results are shown in table 2 together with the kind of the coating liquid for the catalyst layer.
With respect to 6kA/m2The reduction in electrolytic voltage based on comparative example 1, 19mV in example 6 and 39mV in example 7, at the current density of (1) was observed, indicating that the electrolytic voltage could be reduced compared to comparative example 1. In particular, as is clear from comparison between example 6 and example 7, when the electrolysis electrode of the present embodiment has a catalyst layer containing vanadium, the effect of reducing the electrolysis voltage is further increased.
[ example 8]
The electrode for electrolysis of example 5 was usedThe reduced reactivation of the electrode occurs. As an electrode whose activity was decreased, an electrode for electrolysis produced in the same manner as in comparative example 1, which was electrified for 6.9 years in an electrolytic cell of a semi-commercial factory, was cut into a predetermined size (95 × 110 mm: 0.01045 m)2) As the base electrode, the base electrode is attached to a rib of the anode chamber of the anode unit by welding. The substrate electrode was at 6kA/m2The electrolytic voltage at the current density of (2) was increased by 32mV based on comparative example 1. The electrode for electrolysis of example 5 was welded to the base electrode as a replacement electrode to prepare an electrolytic cell comprising an electrode laminate.
[ example 9]
An electrode for electrolysis was produced in the same manner as in example 1, except that the conductive substrate in example 1 was a titanium expanded metal having a mesh opening center-to-center distance in the short cell direction (SW) of 2.2mm, a mesh opening center-to-center distance in the long cell direction (LW) of 3.0mm, and a plate thickness of 0.52 mm.
The thickness of the obtained electrode for electrolysis was 0.52mm, the aperture ratio was 23.3%, and the value obtained by dividing the total of the peripheral length of the opening by the aperture ratio was 2.36.
The electrolysis electrode is used for reactivation of the electrode whose activity is reduced. As an electrode whose activity was decreased, an electrode for electrolysis produced in the same manner as in comparative example 1, which was electrified for 7.1 years in an electrolytic cell in a manufacturing plant, was cut into a predetermined size (95 × 110 mm: 0.01045 m)2) As the base electrode, the base electrode is attached to a rib of the anode chamber of the anode unit by welding. The substrate electrode was at 6kA/m2The electrolytic voltage at the current density of (2) was increased by 35mV based on comparative example 1. The electrolysis electrode is welded to the base electrode as a renewal electrode to produce an electrolytic cell comprising an electrode laminate.
Salt electrolysis test was performed by ion exchange membrane method using the electrolytic cells prepared in examples 8 to 9, respectively. The results are shown in table 3.
[ Table 3]
| FR conversion | Thickness [ mm ]] | SW[mm] | LW[mm] | A: opening ratio [% ]] | B, peripheral length [ mm ]] | B/A | The effect is as follows: delta V | |
| Example 8 | ○ | 0.56 | 1.6 | 3.0 | 17.5 | 57.7 | 3.30 | 33 |
| Example 9 | ○ | 0.52 | 2.2 | 3.0 | 23.3 | 55.0 | 2.36 | 24 |
With respect to 6kA/m2The reduction in electrolytic voltage based on comparative example 1 at the current density of (1) was 33mV in example 8 and 24mV in example 9, but the electrolytic voltage was reduced compared to comparative example 1, and it was found that when the conventional electrode having a reduced activity was renewed, the electrolytic performance was restored to the level before the deterioration or further improved, that is, reactivation could be performed.
Industrial applicability
The electrolysis electrode of the present invention can suppress the voltage and the power consumption at the time of electrolysis to a low level and has practical strength, and therefore, can be suitably used in the field of salt electrolysis. In particular, the method is useful as an anode for salt electrolysis by an ion exchange membrane method, and can produce a high-purity chlorine gas having a low oxygen concentration at a low voltage and a low power consumption for a long period of time.
Description of the symbols
1 electrode
2,3 opening part
10 electrode for electrolysis
20 opening part
100 opening part
100' opening part
101 th 1 st imaginary central line
102 nd 2 imaginary center line
Part a
b part b
Electrolytic bath for 200 electrolysis
210 electrolyte
220 container
230 anode (electrode for electrolysis)
240 cathode
250 ion exchange membrane
260 wiring
300 electrode for electrolysis
310 mesh of opening part short grid direction center distance (short diameter SW)
Distance between centers in longitudinal direction of meshes at opening 320 (major diameter LW)
330 th 2 imaginary central line
340 part a
350 part b
360 openings of the mesh in the short lattice direction and the distance between the openings
Claims (10)
1. An electrode for electrolysis, comprising:
conductive base material comprising perforated metal plate, and
at least one catalyst layer formed on the surface of the conductive substrate,
wherein the content of the first and second substances,
in a use state, the shape of the opening of the electrolysis electrode is bilaterally symmetrical with respect to a 1 st imaginary center line extending in the short lattice direction of the mesh and vertically asymmetrical with respect to a 2 nd imaginary center line extending in the long lattice direction of the mesh,
the thickness of the electrode for electrolysis is more than 0.5mm and less than 1.2 mm.
2. The electrolysis electrode according to claim 1, wherein when the opening is divided into a portion a and another portion b by the 2 nd virtual center line, a value obtained by dividing an area Sa of the portion a by an area Sb of the portion b is 1.15 or more and 2.0 or less.
3. The electrolysis electrode according to claim 2, wherein the upper portion of the 2 nd imaginary center line is the portion a, and the lower portion thereof is the portion b.
4. The electrolysis electrode according to any one of claims 1 to 3, wherein a value obtained by dividing a difference St obtained by subtracting a maximum mesh width in the short cell direction of the mesh of the opening from a center-to-center distance in the short cell direction of the mesh of the opening by the SW is 0.4 or more.
5. An electrolysis cell equipped with the electrode for electrolysis according to any one of claims 1 to 4.
6. An electrolytic cell comprising:
an anode chamber comprising the electrode for electrolysis according to any one of claims 1 to 4 as an anode,
A cathode chamber comprising a cathode, and
an ion exchange membrane separating the anode compartment from the cathode compartment.
7. The electrolytic cell according to claim 6, wherein a projection is provided on an anode side surface of the ion exchange membrane, the projection containing a polymer constituting the ion exchange membrane.
8. An electrode laminate comprising:
the electrode for electrolysis as claimed in any one of claims 1 to 4, and
a base electrode different from the electrolysis electrode.
9. The electrode laminate according to claim 8, wherein the thickness of the electrolysis electrode is more than 0.5mm and 0.65mm or less.
10. A method for replacing an electrode, comprising a step of welding the electrode for electrolysis according to any one of claims 1 to 4 to an existing electrode in an electrolytic cell.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017004383 | 2017-01-13 | ||
| JP2017-004383 | 2017-01-13 | ||
| CN201780073743.3A CN110023541B (en) | 2017-01-13 | 2017-12-28 | Electrode for electrolysis, electrolytic cell, electrode laminate, and method for renewing electrode |
| PCT/JP2017/047365 WO2018131519A1 (en) | 2017-01-13 | 2017-12-28 | Electrode for electrolysis, electrolytic cell, electrode laminate and method for renewing electrode |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780073743.3A Division CN110023541B (en) | 2017-01-13 | 2017-12-28 | Electrode for electrolysis, electrolytic cell, electrode laminate, and method for renewing electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114351178A true CN114351178A (en) | 2022-04-15 |
Family
ID=62839803
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210045889.XA Pending CN114351178A (en) | 2017-01-13 | 2017-12-28 | Electrode for electrolysis, electrolysis cell, electrolytic cell, electrode laminate, and method for renewing electrode |
| CN201780073743.3A Active CN110023541B (en) | 2017-01-13 | 2017-12-28 | Electrode for electrolysis, electrolytic cell, electrode laminate, and method for renewing electrode |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780073743.3A Active CN110023541B (en) | 2017-01-13 | 2017-12-28 | Electrode for electrolysis, electrolytic cell, electrode laminate, and method for renewing electrode |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20190360112A1 (en) |
| EP (1) | EP3569740A4 (en) |
| JP (2) | JP6778459B2 (en) |
| KR (2) | KR102349667B1 (en) |
| CN (2) | CN114351178A (en) |
| BR (1) | BR112019013822A2 (en) |
| TW (1) | TWI666343B (en) |
| WO (1) | WO2018131519A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102503553B1 (en) * | 2019-02-22 | 2023-02-27 | 주식회사 엘지화학 | Electrode for Electrolysis |
| JP7236568B2 (en) * | 2019-06-18 | 2023-03-09 | ティッセンクルップ・ウーデ・クロリンエンジニアズ ゲー エム ベー ハー | Electrodes for electrolysis and electrolysis equipment |
| JP7464313B1 (en) | 2023-01-20 | 2024-04-09 | ウェスコ エレクトロード シーオーエルティーディー | Electrode for chlor-alkali electrolysis using ion exchange membrane method, its manufacturing method and zero gap type ion exchange membrane electrolytic cell using same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3930981A (en) * | 1973-06-25 | 1976-01-06 | Oronzio De Nora Impianti Elettrochimici S.P.A. | Bipolar electrolysis cells with perforate metal anodes and baffles to deflect anodic gases away from the interelectrodic gap |
| EP0039171A2 (en) * | 1980-04-15 | 1981-11-04 | Asahi Kasei Kogyo Kabushiki Kaisha | A method for the electrolysis of an aqueous solution of an alkali metal chloride and an electrolytic cell therefor |
| US4708888A (en) * | 1985-05-07 | 1987-11-24 | Eltech Systems Corporation | Coating metal mesh |
| JPH0456791A (en) * | 1990-06-22 | 1992-02-24 | Permelec Electrode Ltd | Reactivating method for insoluble metallic electrode |
| CN1717507A (en) * | 2002-11-27 | 2006-01-04 | 旭化成化学株式会社 | Bipolar zero-gap electrolytic cell |
| CN101263245A (en) * | 2005-09-14 | 2008-09-10 | 旭化成化学株式会社 | Cation-exchange fluorinated membrane for electrolysis and process for producing the same |
Family Cites Families (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4621884Y1 (en) | 1966-07-13 | 1971-07-28 | ||
| JPS5842778B2 (en) * | 1979-05-28 | 1983-09-21 | 新日本製鐵株式会社 | Continuous casting method for slabs for cold-rolled steel sheets |
| JPS5842778Y2 (en) * | 1979-07-06 | 1983-09-28 | 株式会社東芝 | Drain recovery processing equipment |
| JPS5689520A (en) * | 1979-12-21 | 1981-07-20 | Unitika Ltd | Bonding method of metal plate |
| JPS6244589Y2 (en) * | 1979-12-26 | 1987-11-26 | ||
| JPS5842778A (en) * | 1981-09-09 | 1983-03-12 | Toyo Soda Mfg Co Ltd | Electrolytic method |
| JPS5842778U (en) * | 1981-09-18 | 1983-03-22 | シチズン時計株式会社 | Structure to prevent rotation of register ring in diver watch |
| JPS5883466U (en) * | 1981-11-27 | 1983-06-06 | ペルメレツク電極株式会社 | Electrolyte using ion exchange membrane |
| JPS58130286A (en) | 1982-01-26 | 1983-08-03 | Toyo Soda Mfg Co Ltd | Electrolytic method |
| WO1986006758A1 (en) * | 1985-05-07 | 1986-11-20 | Eltech Systems Corporation | Expanded metal mesh and coated anode structure |
| JPS6244589A (en) * | 1985-08-23 | 1987-02-26 | Permelec Electrode Ltd | Electrode for electrolysis |
| JPS6227584A (en) * | 1985-07-29 | 1987-02-05 | Permelec Electrode Ltd | Electrode for electrolysis |
| JPS6244589U (en) * | 1985-09-05 | 1987-03-18 | ||
| JPS6321251A (en) * | 1986-07-16 | 1988-01-28 | 新日本製鐵株式会社 | Silicon carbide base ceramic sintered body |
| JP2594245B2 (en) * | 1988-11-23 | 1997-03-26 | ペルメレック電極株式会社 | Reactivation method of insoluble metal electrode |
| JPH02141593U (en) * | 1989-04-26 | 1990-11-28 | ||
| JP3002232B2 (en) * | 1990-05-29 | 2000-01-24 | ペルメレック電極株式会社 | Reactivation method of electrode for electrolysis |
| JPH0456791U (en) * | 1990-09-20 | 1992-05-15 | ||
| JP3075580B2 (en) * | 1991-04-05 | 2000-08-14 | 旭硝子株式会社 | Fluorine-containing cation exchange membrane for electrolysis |
| JP2003041388A (en) * | 2001-07-31 | 2003-02-13 | Association For The Progress Of New Chemistry | Electrolysis cell with ion exchange membrane and electrolysis method |
| KR100603536B1 (en) * | 2003-11-19 | 2006-07-26 | 박상길 | Electrolysis having a mesh type electrode |
| JP4573715B2 (en) | 2004-07-09 | 2010-11-04 | 旭化成ケミカルズ株式会社 | Fluorine cation exchange membrane for electrolysis |
| JP2007023374A (en) * | 2005-07-12 | 2007-02-01 | Ask:Kk | Electrolytic electrode structure |
| JP5437651B2 (en) * | 2009-01-30 | 2014-03-12 | 東ソー株式会社 | Ion exchange membrane electrolytic cell and method for producing the same |
| CN101656320B (en) * | 2009-09-04 | 2012-01-18 | 新奥科技发展有限公司 | Flow-field plate for electrochemical cell |
| EP2653589B1 (en) * | 2010-12-15 | 2016-11-16 | Asahi Kasei Kabushiki Kaisha | Electrode for electrolysis, electrolytic cell and production method for electrode for electrolysis |
| CN201990733U (en) * | 2011-01-10 | 2011-09-28 | 华南理工大学 | Hydrogen production unit based on solid electrolyte electrolyzers |
| KR101533205B1 (en) * | 2011-12-26 | 2015-07-01 | 도레이 카부시키가이샤 | Gas diffusion electrode substrate for fuel cell, membrane electrode assembly, and fuel cell |
| HUE031699T2 (en) * | 2012-03-19 | 2017-07-28 | Asahi Chemical Ind | Electrolysis cell and electrolysis tank |
| JP5548296B1 (en) * | 2013-09-06 | 2014-07-16 | ペルメレック電極株式会社 | Method for producing electrode for electrolysis |
| CN105917027A (en) * | 2014-01-15 | 2016-08-31 | 蒂森克虏伯伍德氯工程公司 | Anode for ion exchange membrane electrolysis vessel, and ion exchange membrane electrolysis vessel using same |
| WO2016042801A1 (en) * | 2014-09-19 | 2016-03-24 | 株式会社 東芝 | Electrode unit, electrolytic bath provided with electrode unit, electrolysis device, and method of manufacturing electrode of electrode unit |
| US20160191181A1 (en) * | 2014-12-31 | 2016-06-30 | Qualcomm Technologies International, Ltd. | Audio broadcast retransmissions |
| WO2016125333A1 (en) * | 2015-02-02 | 2016-08-11 | 株式会社 東芝 | Electrode unit and electrolysis device using same |
| JP2016196674A (en) * | 2015-04-02 | 2016-11-24 | 株式会社東芝 | Electrochemical cell, electrochemical device using the electrochemical cell and storage using the electrochemical device |
| JP6938261B2 (en) | 2017-07-21 | 2021-09-22 | 株式会社ディスコ | Wafer processing method and cutting equipment |
-
2017
- 2017-12-28 EP EP17891083.2A patent/EP3569740A4/en active Pending
- 2017-12-28 CN CN202210045889.XA patent/CN114351178A/en active Pending
- 2017-12-28 CN CN201780073743.3A patent/CN110023541B/en active Active
- 2017-12-28 US US16/477,343 patent/US20190360112A1/en active Pending
- 2017-12-28 KR KR1020197019742A patent/KR102349667B1/en active IP Right Grant
- 2017-12-28 BR BR112019013822A patent/BR112019013822A2/en not_active Application Discontinuation
- 2017-12-28 KR KR1020217011243A patent/KR102422917B1/en active IP Right Grant
- 2017-12-28 WO PCT/JP2017/047365 patent/WO2018131519A1/en unknown
- 2017-12-28 JP JP2018561333A patent/JP6778459B2/en active Active
-
2018
- 2018-01-12 TW TW107101251A patent/TWI666343B/en active
-
2020
- 2020-10-08 JP JP2020170207A patent/JP6956842B2/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3930981A (en) * | 1973-06-25 | 1976-01-06 | Oronzio De Nora Impianti Elettrochimici S.P.A. | Bipolar electrolysis cells with perforate metal anodes and baffles to deflect anodic gases away from the interelectrodic gap |
| EP0039171A2 (en) * | 1980-04-15 | 1981-11-04 | Asahi Kasei Kogyo Kabushiki Kaisha | A method for the electrolysis of an aqueous solution of an alkali metal chloride and an electrolytic cell therefor |
| US4354905A (en) * | 1980-04-15 | 1982-10-19 | Asahi Kasei Kogyo Kabushiki Kaisha | Method for the electrolysis of an aqueous solution of an alkali metal chloride and an anode therefor |
| US4708888A (en) * | 1985-05-07 | 1987-11-24 | Eltech Systems Corporation | Coating metal mesh |
| JPH0456791A (en) * | 1990-06-22 | 1992-02-24 | Permelec Electrode Ltd | Reactivating method for insoluble metallic electrode |
| CN1717507A (en) * | 2002-11-27 | 2006-01-04 | 旭化成化学株式会社 | Bipolar zero-gap electrolytic cell |
| CN101263245A (en) * | 2005-09-14 | 2008-09-10 | 旭化成化学株式会社 | Cation-exchange fluorinated membrane for electrolysis and process for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3569740A4 (en) | 2020-04-08 |
| JP6778459B2 (en) | 2020-11-04 |
| CN110023541A (en) | 2019-07-16 |
| KR102349667B1 (en) | 2022-01-12 |
| KR20210044912A (en) | 2021-04-23 |
| TW201829847A (en) | 2018-08-16 |
| KR20190088067A (en) | 2019-07-25 |
| KR102422917B1 (en) | 2022-07-21 |
| JPWO2018131519A1 (en) | 2019-11-07 |
| US20190360112A1 (en) | 2019-11-28 |
| BR112019013822A2 (en) | 2020-01-21 |
| CN110023541B (en) | 2022-02-08 |
| JP6956842B2 (en) | 2021-11-02 |
| WO2018131519A1 (en) | 2018-07-19 |
| TWI666343B (en) | 2019-07-21 |
| EP3569740A1 (en) | 2019-11-20 |
| JP2021008672A (en) | 2021-01-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6956842B2 (en) | Electrode for electrolysis, electrolytic cell, electrode laminate and electrode renewal method | |
| JP5705879B2 (en) | Electrode for electrolysis, electrolytic cell and method for producing electrode for electrolysis | |
| JP2013166994A (en) | Electrolysis electrode, electrolysis tank, and method for manufacturing electrolysis electrode | |
| JP5681343B2 (en) | Electrode for electrolysis | |
| JP6506983B2 (en) | Negative electrode for hydrogen generation and method for producing the same | |
| KR20230038437A (en) | Anode for electrolysis and preparation method thereof | |
| JP4578348B2 (en) | Electrode for hydrogen generation | |
| US20130078536A1 (en) | Gas diffusion electrodes and process for production thereof | |
| JP6216806B2 (en) | Ion exchange membrane electrolytic cell | |
| JP5932791B2 (en) | Oxygen consuming electrode and method for producing the same | |
| US20220018032A1 (en) | Electrode For Electrolysis | |
| JP2016204732A (en) | Electrode for electrolysis | |
| JP5462460B2 (en) | Electrode for electrolysis | |
| JP7236568B2 (en) | Electrodes for electrolysis and electrolysis equipment | |
| JP2006265649A (en) | Method for producing electrode for generating hydrogen | |
| JP2012077381A (en) | Method for manufacturing transport- and storage-stable oxygen-consuming electrode | |
| KR102347982B1 (en) | Anode for electrolysis and preparation method thereof | |
| KR102358447B1 (en) | Coating composition for electrolysis anode | |
| CN113994029B (en) | Electrolytic electrode and electrolytic cell | |
| JPH06173060A (en) | Gas electrode structure and electrolytic method using said structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |