US20120267242A1 - Spherical electrode and electrolysis cell including same - Google Patents
Spherical electrode and electrolysis cell including same Download PDFInfo
- Publication number
- US20120267242A1 US20120267242A1 US13/504,235 US200913504235A US2012267242A1 US 20120267242 A1 US20120267242 A1 US 20120267242A1 US 200913504235 A US200913504235 A US 200913504235A US 2012267242 A1 US2012267242 A1 US 2012267242A1
- Authority
- US
- United States
- Prior art keywords
- electrode
- electrode layer
- divinylbenzene
- ion
- resins
- 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.)
- Abandoned
Links
- 238000005868 electrolysis reaction Methods 0.000 title abstract description 43
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 27
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims description 36
- 229920005989 resin Polymers 0.000 claims description 36
- 239000011159 matrix material Substances 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 claims description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 125000000129 anionic group Chemical group 0.000 claims description 16
- 125000002091 cationic group Chemical group 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 15
- 230000002378 acidificating effect Effects 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 239000011135 tin Substances 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 239000011133 lead Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 239000011324 bead Substances 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 229910010272 inorganic material Inorganic materials 0.000 claims description 4
- 239000011147 inorganic material Substances 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052762 osmium Inorganic materials 0.000 claims description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- -1 platinum group metals Chemical class 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 abstract description 22
- 238000000034 method Methods 0.000 abstract description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 10
- 239000001257 hydrogen Substances 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000446 fuel Substances 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000011780 sodium chloride Substances 0.000 abstract description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 3
- 230000005611 electricity Effects 0.000 abstract description 3
- 229960002218 sodium chlorite Drugs 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 48
- 239000010410 layer Substances 0.000 description 39
- 238000006243 chemical reaction Methods 0.000 description 27
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 238000003487 electrochemical reaction Methods 0.000 description 11
- 230000009467 reduction Effects 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 239000012279 sodium borohydride Substances 0.000 description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000004155 Chlorine dioxide Substances 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 7
- 229910001415 sodium ion Inorganic materials 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 239000003014 ion exchange membrane Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000019398 chlorine dioxide Nutrition 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000008364 bulk solution Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229940005989 chlorate ion Drugs 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910021650 platinized titanium dioxide Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000012691 Cu precursor Substances 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 229910021639 Iridium tetrachloride Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000012696 Pd precursors Substances 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000010457 zeolite Substances 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
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to a spherical cell suitable for electrolysis of water or an aqueous solution of electrolyte (e.g. sodium chloride or sodium chlorite) or the like, and to an electrolysis cell including the same.
- electrolyte e.g. sodium chloride or sodium chlorite
- An electrochemical cell is a kind of energy conversion system.
- electrochemical cells may be classified into electrolysis cells producing oxygen or hydrogen gas by using reactants, such as water, or decomposing a solution containing sodium chloride or sodium chlorite electrolyte, and fuel cells generating electricity by using oxygen and hydrogen fuel.
- FIG. 1 shows a typical electrolysis cell, including an anode chamber 20 having an anode 10 , a cathode chamber 40 having a cathode 30 , and an ion-exchange membrane 50 serving as an electrolyte transfer medium between the anode and the cathode.
- the operation mechanism of such an electrolysis cell will be described by taking, as an example, an electrolysis cell in which NaClO 2 is supplied to the anode chamber as an electrolyte to produce chlorine dioxide.
- the electrolyte, NaClO 2 is supplied to the anode in the anode chamber, and then is decomposed into chlorine dioxide (ClO 2 ) gas, electron (e ⁇ ) and sodium ion (Na + ), while a non-reacted portion is discharged out of the anode chamber of the electrolysis cell together with chlorine dioxide (ClO 2 ) gas.
- sodium ion (Na + ) passes through the ion-exchange membrane 50 and moves toward the cathode 30 (hydrogen electrode), while electron moves along an outer path 60 by which the anode 10 and the cathode 30 are connected with each other.
- Pure water is supplied to the cathode chamber 40 , and then decomposed at the cathode 30 by the electron (e′′) transferred from the anode 10 (reduction).
- pure water is decomposed into hydrogen (H 2 ) gas and hydroxide ion.
- Hydroxide ion reacts with sodium ion transferred from the anode chamber 20 through the ion-exchange membrane 50 , thereby forming NaOH.
- the electrochemical reactions occurring at the anode 10 and the cathode 30 separately may be represented by the following Reaction Formulae 1 to 4.
- the system of FIG. 1 may be applied to electrochemical decomposition of water to produce hydrogen gas and oxygen gas.
- water (H 2 O) is supplied to the anode catalyst, and then decomposed into oxygen gas (O 2 ), electron (e ⁇ ) and proton (H + ) by an electrochemical reaction.
- O 2 oxygen gas
- e ⁇ electron
- H + proton
- a portion of water is discharged out through the product outlet of the electrolysis cell together with oxygen (O 2 ) gas.
- decomposed proton (H + ) passes through the ion-exchange membrane and moves toward the cathode catalyst (hydrogen electrode), so that it may react with the electron (e) transferred along an external path (not shown) connected between the anode catalyst and the cathode catalyst to produce hydrogen (H 2 ) gas.
- the electrochemical reactions occurring at the anode catalyst and the cathode catalyst separately are represented by the following Reaction Formulae 5 and 6.
- reaction Formulae 2 & 3 Reaction Formulae 5 & 6, and Reaction Formulae 7 & 8
- reactions occur at the interface of an electrode.
- a solid-liquid-gas three-phase reaction is involved.
- Particular phenomena involved herein include provision of an electron transfer path in a solid portion, transfer of ions to an electrode in a liquid as an electrolyte, transfer of a product (in the case of a liquid) to a bulk solution, and transfer of a gas product to a bulk solution in a gaseous portion.
- FIG. 2 shows another embodiment of a typical electrolysis cell.
- a spherical electrode 26 is disposed between an anode 22 and a membrane 28 , and between a membrane 28 and a cathode 24 .
- the area of an electrode in the electrolysis cell is maximized as compared to the electrolysis cell shown in FIG. 1 .
- patents related to a spherical electrode is U.S. Pat. No. 6,024,850 (Title: Modified Ion Exchange Materials, Applicant: Assignee: Halox technologies Corporation).
- the spherical electrode disclosed therein is characterized in that an ion-exchange resin is used as a matrix and an electrode catalyst is present in the ion-exchange resin.
- an electrolyte is transferred into an ion-exchange membrane to cause an electrochemical reaction, thereby causing degradation of reaction efficiency (this is because diffusion resistance is too high to transfer ions into the ion-exchange resin, and it is more difficult to transfer thus generated gas to the exterior of the ion-exchange resin).
- an electrode catalyst may be discharged, resulting in rapid degradation of durability.
- the electrode of the related art includes a structure having an electrode catalyst containing a counterion at the active site in the ion-exchange resin.
- a high-concentration electrolyte such as saturated brine
- the catalyst ion may be discharged easily. This may be predicted easily from a regeneration process using brine in a general ion-exchange resin.
- the present invention is directed to providing a spherical electrode structure capable of being filled in an electrolysis cell and applicable to various conditions including electrolytes or concentration.
- the present invention provides an electrode for an electrochemical cell including an ion-exchange resin matrix and a first electrode layer coated on a surface of the ion-exchange resin matrix, characterized in that the electrode has a shape selected from the group consisting of spheres, granules, beads, grains and fibers.
- the first electrode layer may be coated on 1-100% of the total surface area of the electrode for an electrochemical cell. Particularly, a coating ratio of at least 70% is preferable in view of overall electrochemical performance or efficiency.
- the electrode for an electrochemical cell further includes a second electrode layer, wherein the second electrode layer is coated on a surface of the ion-exchange resin matrix, and may be provided as a multilayer type electrode in which the first electrode layer is coated on a surface of the second electrode layer.
- the electrode for an electrochemical cell may further include a third electrode layer coated on a surface of the first electrode layer.
- Such a multilayer type electrode may exhibit electrode quality equal to or better than an electrode using a noble metal catalyst, while reducing the amount of an expensive noble metal catalyst significantly.
- the present invention provides an electrochemical cell including an ion-exchange resin matrix, a first electrode layer coated on a surface of the ion-exchange resin matrix, and a second electrode layer coated on the surface of the ion-exchange resin matrix, characterized in that the electrode has a shape selected from the group consisting of spheres, granules, beads, grains and fibers, and the first electrode layer and the second electrode layer correspond to an anode and a cathode, respectively, or to a cathode and an anode, respectively.
- the first electrode layer and the second electrode layer have a combined surface area corresponding to 1-99%, particularly 30-90% of the total surface area of the electrode chemical cell.
- each of the first electrode layer and the second electrode layer may be coated on 0.5-60% of the total surface area of the electrochemical cell.
- the resultant electrochemical cell is capable of normal operation even without a short-preventing medium, such as a non-woven web, between the anode and the cathode.
- Controlling the surface coating degree of the electrode may be performed easily by those skilled in the art as long as it is based on the present disclosure.
- the matrix may be selected from the group consisting of: strongly acidic crosslinked polystyrene-divinylbenzene cationic resins; weakly acidic crosslinked polystyrene-divinylbenzene cationic resins; iminodiacetic acid-chelated crosslinked polystyrene-divinylbenzene cationic resins; strongly basic polystyrene-divinylbenzene anionic resins; weakly basic polystyrene-divinylbenzene anionic resins; strongly basic/weakly basic polystyrene-divinylbenzene anionic resins; strongly basic/weakly basic acrylic anionic resins; strongly acidic perfluorosulfonated cationic resins; strongly basic perfluroroaminated anionic resins; natural anion exchangers; natural cation exchangers; porous inorganic materials; and combinations thereof.
- the first electrode layer may be selected from the group consisting of platinum group metals (platinum, ruthenium, rhodium, palladium, osmium, iridium), as well as gold, silver, chrome, iron, lead, titanium, manganese, cobalt, nickel, molybdenum, tungsten, aluminum, silicon, zinc, tin and alloys or combinations thereof.
- the second electrode layer may be selected from the group consisting of titanium, silver, copper, tin and alloys or combinations thereof.
- the first electrode layer may have a thickness of 0.1-5 ⁇ m.
- the present invention provides a hollow sphere electrode capable of being filled between an anode and a cathode, between an anode and a membrane, between a cathode and a membrane, between a membrane and a membrane, or the like, in an electrolysis cell for an aqueous solution containing an electrolyte, characterized in that the electrode is filled in such a manner that the electrode has an area of 1,000-1,000,000 cm 2 per m 3 of volume of the electrolysis cell.
- the hollow sphere electrode has a structure in which a metal is precipitated as an electrochemical catalyst on a surface of a medium capable of ion exchange in an amount of 1-100%.
- the electrolysis cell includes a medium capable of ion exchange, and at least one metal precipitated as an electrochemical catalyst on a surface of the medium at a ratio of 1-99%.
- the electrode according to an embodiment has an electrode surface area up to 100 m 2 per m 3 of an electrolysis cell, and thus maximizes the performance of an electrolysis system, makes an electrolysis system compact, and reduces manufacturing cost.
- FIG. 1 is a schematic view of a typical electrolysis cell
- FIG. 2 is a schematic view showing another typical electrolysis cell (U.S. Pat. No. 6,024,850 (Title: Modified Ion Exchange Materials, Applicant: Assignee: Halox Technologies Corporation);
- FIG. 3 is a schematic view illustrating a problem of the electrolysis cell as shown in FIG. 2 ;
- FIG. 4 is a schematic view showing a spherical electrode 400 according to an embodiment of the present invention.
- FIG. 5 is a schematic view showing a spherical electrode 500 having a multilayer type metal layer according to another embodiment of the present invention.
- FIG. 6 is a schematic view showing a spherical electrode according to still another embodiment of the present invention.
- FIG. 7 shows a spherical electrochemical cell 700 according to an embodiment of the present invention.
- FIG. 8 is a scanning electron microscope (SEM) image of a first Ti coating layer obtained from Example 9;
- FIG. 9 is an SEM image of a second Pt coating layer obtained from Example 9;
- FIG. 10 is an X-ray diffraction (XRD) image of the sample obtained from Example 9;
- FIG. 11 is a schematic view showing the electrolysis cell according to an embodiment of the present invention.
- FIG. 12 is a graph showing the results of comparison of the electrode of the present invention with the electrode according to a comparative example in terms of electrolysis voltage
- FIG. 13 is a graph showing the results of comparison of the electrode of the present invention with the electrode according to a comparative example in terms of chlorine concentration
- FIG. 14 is a graph showing the results of comparison of the electrode of the present invention with the electrode according to a comparative example in terms of current efficiency
- FIG. 15 is a photo showing the spherical electrolysis cell of FIG. 7 ;
- FIG. 16 is a photo showing a magnified view of the interface of the spherical electrolysis cell of FIG. 10 .
- FIG. 4 is a schematic view showing a spherical electrode 400 according to an embodiment.
- the spherical electrode 400 uses an ion exchanger as a matrix 410 and includes an electrode catalyst 420 on the surface of the matrix.
- the shape of the matrix is not limited to a particular shape, such as a spherical shape.
- the matrix 410 may be any medium capable of ion exchange.
- the matrix material include: strongly acidic crosslinked polystyrene-divinylbenzene cationic resins; weakly acidic crosslinked polystyrene-divinylbenzene cationic resins; iminodiacetic acid-chelated crosslinked polystyrene-divinylbenzene cationic resins; strongly basic polystyrene-divinylbenzene anionic resins; weakly basic polystyrene-divinylbenzene anionic resins; strongly basic/weakly basic polystyrene-divinylbenzene anionic resins; strongly basic/weakly basic acrylic anionic resins; strongly acidic perfluorosulfonated cationic resins; strongly basic perfluroroaminated anionic resins; natural anion exchangers, such as clay; natural cation exchangers, such as manganese greensand; porous inorganic materials, such
- the catalyst 420 coated on the matrix may be selected from the group consisting of platinum group metals (platinum, ruthenium, rhodium, palladium, osmium, iridium), as well as gold, silver, chrome, iron, lead, titanium, manganese, cobalt, nickel, molybdenum, tungsten, aluminum, silicon, zinc, tin and alloys or oxides thereof.
- platinum group metals platinum group metals
- the electrode catalyst layer 420 may have a thickness of 0.1-5 ⁇ m, more particularly 0.1-2 ⁇ m. In the case of a thickness greater than 2 ⁇ m, a non-active reaction layer that does not participate in a reaction becomes too thick, thereby causing catalyst loss and poor cost efficiency.
- the electrode catalyst layer 420 may have a surface area covering 1-100% of the surface of the matrix depending on the particular purpose of electrochemical reaction.
- Methods for forming the electrode catalyst layer on the ion exchange resin body include chemical methods, such as adsorption-reduction and electroplating, physical methods, such as vacuum deposition, etc. However, considering coating on a large amount of spherical ion exchanger particles, chemical adsorption-reduction methods may be used. Chemical adsorption-reduction methods are carried out by allowing an electrode catalyst material to be adsorbed on an ion exchange resin and reducing the electrode catalyst material on the surface of the ion exchange resin. Such methods may be applied and performed easily by those skilled in the art.
- FIG. 5 shows a spherical electrode 500 having a multilayer type metal layer according to another embodiment of the present invention.
- the same or different metal catalyst layer 530 is further formed on the first metal layer to provide an electrode having a bilayer structure.
- the first layer 520 may include a metal, such as titanium, silver, copper or tin, having excellent electron conductivity.
- the second layer 530 may include the electrode catalyst layer as mentioned with reference to FIG. 4 .
- FIG. 6 is a schematic view showing a spherical electrode according to still another embodiment.
- the spherical electrode is a hollow spherical electrode structure obtained by firing the spherical electrode as shown in FIG. 4 or FIG. 5 at about 800° C. so that the inner ion exchange layer is pyrolyzed.
- FIG. 7 shows a spherical electrochemical cell 700 according to an embodiment.
- the sphere functions as a unit electrolysis cell 700 .
- the spherical electrochemical cell 700 includes fundamental elements of an electrochemical cell, such as an anode, cathode, electrolyte, or the like.
- the spherical electrochemical cell includes an ion conductor matrix 710 as an electrolyte, a metal 720 having an anodic function (oxidation) as an anode catalyst, and a metal 730 having a cathodic function (reduction) as a cathode catalyst.
- Particular types of the anode catalyst 720 or cathode catalyst 730 coated on the matrix are the same as described with reference to FIG. 4 .
- the metal forming the anode catalyst 720 may be different from the metal forming the cathode catalyst 730 .
- the electrode catalyst layer may have a thickness of 1-5 ⁇ m. In the case of a thickness greater than 5 ⁇ m, a non-active reaction layer that does not participate in a reaction becomes too thick, thereby causing catalyst loss.
- the surface area may be within a range of 1-99% depending on the particular purpose of electrochemical reaction. More particularly, the surface area (combined surface area of the anode catalyst surface with the cathode catalyst surface) may be within a range of 30-90%.
- the surface area that equals to 100% means a contact between the anode and the cathode, suggesting a short between the anode and the cathode as a physical meaning. Thus, in this case, no electrochemical reaction occurs.
- Methods for forming the anode catalyst metal 720 and the cathode catalyst metal 730 are the same as described above with reference to FIG. 4 .
- a metal catalyst as the anode catalyst metal 720 is formed first partially on the total surface by an adsorption-reduction method, and then the cathode catalyst metal 730 is further formed partially on the total surface by an adsorption-reduction method. Since an adsorption-reduction method is used, it is possible to form the anode catalyst metal 720 and the cathode catalyst metal 730 at different positions.
- FIG. 15 is a photo showing the spherical electrolysis cell of FIG. 7 , wherein Pt is used as an anode catalyst metal and Sn is used as a cathode catalyst metal.
- FIG. 16 is a photo showing a magnified view of the interface of the spherical electrolysis cell of FIG. 10 .
- FIG. 8 is an SEM image showing the first Ti coating layer obtained from Example 9. It is shown that Ti is developed well with a uniform shape.
- FIG. 9 is an SEM image showing the second Pt coating layer obtained from Example 9. It is shown that Pt is not concentrated locally but is dispersed uniformly.
- FIG. 10 is an image of the sample obtained from Example 9 taken by XRD analysis. It is shown that Pt, TiO 2 and the like are formed desirably. It is thought that Ti present in the form of TiO 2 results from oxide formation with oxygen in water.
- F is the Faraday constant (96500 (C)
- ⁇ is an actual residual chlorine concentration (ppm, mg/L)
- V is a volume (L) of water supplied to an electrolysis cell
- I is an applied current (A)
- t is a time (s) of electrolysis.
- the electrode according to the present invention has the same electrolysis voltage as the electrode according to Comparative Example.
- the electrode according to the present invention has a chlorine concentration two times higher than a chlorine concentration of the electrode according to Comparative Example. It is thought that such a higher current density is derived from a larger electrode area in the same space and a lower current density at a filled electrode.
- FIG. 13 illustrates comparison of the current efficiencies between the electrode according to the present invention and the electrode according to Comparative Example. The current density values are obtained from the results of FIG. 10 and FIG. 11 and the formula of current density as mentioned in Comparative Example 1.
Abstract
Description
- The present invention relates to a spherical cell suitable for electrolysis of water or an aqueous solution of electrolyte (e.g. sodium chloride or sodium chlorite) or the like, and to an electrolysis cell including the same.
- An electrochemical cell is a kind of energy conversion system. For example, such electrochemical cells may be classified into electrolysis cells producing oxygen or hydrogen gas by using reactants, such as water, or decomposing a solution containing sodium chloride or sodium chlorite electrolyte, and fuel cells generating electricity by using oxygen and hydrogen fuel.
- Fundamental constitutional unit elements of an electrochemical cell include an anode, a cathode and an electrolyte.
FIG. 1 shows a typical electrolysis cell, including ananode chamber 20 having ananode 10, acathode chamber 40 having acathode 30, and an ion-exchange membrane 50 serving as an electrolyte transfer medium between the anode and the cathode. The operation mechanism of such an electrolysis cell will be described by taking, as an example, an electrolysis cell in which NaClO2 is supplied to the anode chamber as an electrolyte to produce chlorine dioxide. The electrolyte, NaClO2, is supplied to the anode in the anode chamber, and then is decomposed into chlorine dioxide (ClO2) gas, electron (e−) and sodium ion (Na+), while a non-reacted portion is discharged out of the anode chamber of the electrolysis cell together with chlorine dioxide (ClO2) gas. After the decomposition, sodium ion (Na+) passes through the ion-exchange membrane 50 and moves toward the cathode 30 (hydrogen electrode), while electron moves along anouter path 60 by which theanode 10 and thecathode 30 are connected with each other. Pure water is supplied to thecathode chamber 40, and then decomposed at thecathode 30 by the electron (e″) transferred from the anode 10 (reduction). As a result, pure water is decomposed into hydrogen (H2) gas and hydroxide ion. Hydroxide ion reacts with sodium ion transferred from theanode chamber 20 through the ion-exchange membrane 50, thereby forming NaOH. Herein, the electrochemical reactions occurring at theanode 10 and thecathode 30 separately may be represented by the followingReaction Formulae 1 to 4. -
NaClO2→Na++ClO2 − (dissociation of electrolyte at anode) [Reaction Formula 1] -
ClO2 −→ClO2 (gas)+e − (oxidation at anode) [Reaction Formula 2] -
H2O+e −→1/2H2+OH− (reduction at cathode) [Reaction Formula 3] -
Na++OH−→NaOH (production of sodium hydroxide at cathode) [Reaction Formula 4] - In addition, the system of
FIG. 1 may be applied to electrochemical decomposition of water to produce hydrogen gas and oxygen gas. In the system ofFIG. 1 , water (H2O) is supplied to the anode catalyst, and then decomposed into oxygen gas (O2), electron (e−) and proton (H+) by an electrochemical reaction. Herein, a portion of water is discharged out through the product outlet of the electrolysis cell together with oxygen (O2) gas. Then, thus decomposed proton (H+) passes through the ion-exchange membrane and moves toward the cathode catalyst (hydrogen electrode), so that it may react with the electron (e) transferred along an external path (not shown) connected between the anode catalyst and the cathode catalyst to produce hydrogen (H2) gas. Herein, the electrochemical reactions occurring at the anode catalyst and the cathode catalyst separately are represented by the followingReaction Formulae 5 and 6. -
2H2O→4H++4e −+O2 (oxidation at anode) [Reaction Formula 5] -
4H++4e −→2H2 (reduction at cathode) [Reaction Formula 6] - Meanwhile, in a fuel cell, reactions occur through a mechanism opposite to the reaction mechanism of the above-described electrolysis of water. In other words, in a fuel cell, hydrogen, methanol or other hydrogen fuel sources react with oxygen to generate electricity. Herein, general reactions occurring in a fuel cell are represented by the following Reaction Formulae 7 and 8
-
2H2→4H++4e − (oxidation at anode) [Reaction Formula 7] -
4H++4e −+O2→2H2O (reduction at cathode) [Reaction Formula 8] - In the above-mentioned electrochemical reactions (
Reaction Formulae 2 & 3,Reaction Formulae 5 & 6, and Reaction Formulae 7 & 8), reactions occur at the interface of an electrode. At the interface of an electrode, a solid-liquid-gas three-phase reaction is involved. Particular phenomena involved herein include provision of an electron transfer path in a solid portion, transfer of ions to an electrode in a liquid as an electrolyte, transfer of a product (in the case of a liquid) to a bulk solution, and transfer of a gas product to a bulk solution in a gaseous portion. Therefore, to maximize the efficiency of an electrochemical reaction, it is required to maximize electrolyte transferability (conductivity), to maximize an electron transfer path (electrode area), and to maximize gas product transfer (electrode shape). As a result, a general electrochemical reactor, in which an electrode having a predetermined space takes a structure of a plate-like electrode or a mesh-like electrode, requires stacking of a plurality of electrodes, thereby limiting significant improvement in its performance. -
FIG. 2 shows another embodiment of a typical electrolysis cell. InFIG. 2 , aspherical electrode 26 is disposed between ananode 22 and amembrane 28, and between amembrane 28 and acathode 24. Thus, the area of an electrode in the electrolysis cell is maximized as compared to the electrolysis cell shown inFIG. 1 . - A particular example of patents related to a spherical electrode is U.S. Pat. No. 6,024,850 (Title: Modified Ion Exchange Materials, Applicant: Assignee: Halox technologies Corporation). The spherical electrode disclosed therein is characterized in that an ion-exchange resin is used as a matrix and an electrode catalyst is present in the ion-exchange resin.
- However, such a spherical electrode having an electrode catalyst in an ion-exchange resin is functionally problematic, as described hereinafter with reference to
FIG. 3 on the basis of the above-described reaction phenomena occurring at an electrode surface. - First, an electrolyte is transferred into an ion-exchange membrane to cause an electrochemical reaction, thereby causing degradation of reaction efficiency (this is because diffusion resistance is too high to transfer ions into the ion-exchange resin, and it is more difficult to transfer thus generated gas to the exterior of the ion-exchange resin).
- Second, there is no electron transfer path (specifically, metal) for the electron formed by the electrochemical reaction in the ion-exchange resin, thereby increasing electron resistance and reducing reaction efficiency.
- Moreover, in the case of an electrochemical reaction dealing with a high-concentration electrolyte, an electrode catalyst may be discharged, resulting in rapid degradation of durability. The electrode of the related art includes a structure having an electrode catalyst containing a counterion at the active site in the ion-exchange resin. Thus, when electrolyzing a high-concentration electrolyte, such as saturated brine, the catalyst ion may be discharged easily. This may be predicted easily from a regeneration process using brine in a general ion-exchange resin.
- The present invention is directed to providing a spherical electrode structure capable of being filled in an electrolysis cell and applicable to various conditions including electrolytes or concentration.
- In one general aspect, the present invention provides an electrode for an electrochemical cell including an ion-exchange resin matrix and a first electrode layer coated on a surface of the ion-exchange resin matrix, characterized in that the electrode has a shape selected from the group consisting of spheres, granules, beads, grains and fibers.
- According to an embodiment, the first electrode layer may be coated on 1-100% of the total surface area of the electrode for an electrochemical cell. Particularly, a coating ratio of at least 70% is preferable in view of overall electrochemical performance or efficiency.
- According to another embodiment, the electrode for an electrochemical cell further includes a second electrode layer, wherein the second electrode layer is coated on a surface of the ion-exchange resin matrix, and may be provided as a multilayer type electrode in which the first electrode layer is coated on a surface of the second electrode layer. In addition, the electrode for an electrochemical cell may further include a third electrode layer coated on a surface of the first electrode layer. Such a multilayer type electrode may exhibit electrode quality equal to or better than an electrode using a noble metal catalyst, while reducing the amount of an expensive noble metal catalyst significantly.
- In another general aspect, the present invention provides an electrochemical cell including an ion-exchange resin matrix, a first electrode layer coated on a surface of the ion-exchange resin matrix, and a second electrode layer coated on the surface of the ion-exchange resin matrix, characterized in that the electrode has a shape selected from the group consisting of spheres, granules, beads, grains and fibers, and the first electrode layer and the second electrode layer correspond to an anode and a cathode, respectively, or to a cathode and an anode, respectively.
- According to an embodiment, the first electrode layer and the second electrode layer have a combined surface area corresponding to 1-99%, particularly 30-90% of the total surface area of the electrode chemical cell. According to another embodiment, to provide the above-defined range of combined surface area, each of the first electrode layer and the second electrode layer may be coated on 0.5-60% of the total surface area of the electrochemical cell.
- Particularly, when the first electrode layer and the second electrode layer have a combined surface area corresponding to 50-70% of the total surface area of the electrochemical cell, and each of the anode and the cathode is coated in such a manner that each surface area is 30-35% of the total surface area of the electrochemical cell, the resultant electrochemical cell is capable of normal operation even without a short-preventing medium, such as a non-woven web, between the anode and the cathode.
- Controlling the surface coating degree of the electrode may be performed easily by those skilled in the art as long as it is based on the present disclosure.
- The matrix may be selected from the group consisting of: strongly acidic crosslinked polystyrene-divinylbenzene cationic resins; weakly acidic crosslinked polystyrene-divinylbenzene cationic resins; iminodiacetic acid-chelated crosslinked polystyrene-divinylbenzene cationic resins; strongly basic polystyrene-divinylbenzene anionic resins; weakly basic polystyrene-divinylbenzene anionic resins; strongly basic/weakly basic polystyrene-divinylbenzene anionic resins; strongly basic/weakly basic acrylic anionic resins; strongly acidic perfluorosulfonated cationic resins; strongly basic perfluroroaminated anionic resins; natural anion exchangers; natural cation exchangers; porous inorganic materials; and combinations thereof.
- The first electrode layer may be selected from the group consisting of platinum group metals (platinum, ruthenium, rhodium, palladium, osmium, iridium), as well as gold, silver, chrome, iron, lead, titanium, manganese, cobalt, nickel, molybdenum, tungsten, aluminum, silicon, zinc, tin and alloys or combinations thereof. The second electrode layer may be selected from the group consisting of titanium, silver, copper, tin and alloys or combinations thereof. In addition, the first electrode layer may have a thickness of 0.1-5 μm.
- In still another general aspect, the present invention provides a hollow sphere electrode capable of being filled between an anode and a cathode, between an anode and a membrane, between a cathode and a membrane, between a membrane and a membrane, or the like, in an electrolysis cell for an aqueous solution containing an electrolyte, characterized in that the electrode is filled in such a manner that the electrode has an area of 1,000-1,000,000 cm2 per m3 of volume of the electrolysis cell.
- According to an embodiment, the hollow sphere electrode has a structure in which a metal is precipitated as an electrochemical catalyst on a surface of a medium capable of ion exchange in an amount of 1-100%.
- The electrolysis cell includes a medium capable of ion exchange, and at least one metal precipitated as an electrochemical catalyst on a surface of the medium at a ratio of 1-99%.
- The electrode according to an embodiment has an electrode surface area up to 100 m2 per m3 of an electrolysis cell, and thus maximizes the performance of an electrolysis system, makes an electrolysis system compact, and reduces manufacturing cost.
-
FIG. 1 is a schematic view of a typical electrolysis cell; -
FIG. 2 is a schematic view showing another typical electrolysis cell (U.S. Pat. No. 6,024,850 (Title: Modified Ion Exchange Materials, Applicant: Assignee: Halox Technologies Corporation); -
FIG. 3 is a schematic view illustrating a problem of the electrolysis cell as shown inFIG. 2 ; -
FIG. 4 is a schematic view showing aspherical electrode 400 according to an embodiment of the present invention; -
FIG. 5 is a schematic view showing aspherical electrode 500 having a multilayer type metal layer according to another embodiment of the present invention; -
FIG. 6 is a schematic view showing a spherical electrode according to still another embodiment of the present invention; -
FIG. 7 shows a sphericalelectrochemical cell 700 according to an embodiment of the present invention; -
FIG. 8 is a scanning electron microscope (SEM) image of a first Ti coating layer obtained from Example 9; -
FIG. 9 is an SEM image of a second Pt coating layer obtained from Example 9; -
FIG. 10 is an X-ray diffraction (XRD) image of the sample obtained from Example 9; -
FIG. 11 is a schematic view showing the electrolysis cell according to an embodiment of the present invention; -
FIG. 12 is a graph showing the results of comparison of the electrode of the present invention with the electrode according to a comparative example in terms of electrolysis voltage; -
FIG. 13 is a graph showing the results of comparison of the electrode of the present invention with the electrode according to a comparative example in terms of chlorine concentration; -
FIG. 14 is a graph showing the results of comparison of the electrode of the present invention with the electrode according to a comparative example in terms of current efficiency; -
FIG. 15 is a photo showing the spherical electrolysis cell ofFIG. 7 ; and -
FIG. 16 is a photo showing a magnified view of the interface of the spherical electrolysis cell ofFIG. 10 . - Hereinafter, the embodiments of the present disclosure will be described in detail with reference to accompanying drawings.
-
FIG. 4 is a schematic view showing aspherical electrode 400 according to an embodiment. As shown inFIG. 4 , thespherical electrode 400 uses an ion exchanger as amatrix 410 and includes anelectrode catalyst 420 on the surface of the matrix. However, the shape of the matrix is not limited to a particular shape, such as a spherical shape. - The
matrix 410 may be any medium capable of ion exchange. Particular examples of the matrix material include: strongly acidic crosslinked polystyrene-divinylbenzene cationic resins; weakly acidic crosslinked polystyrene-divinylbenzene cationic resins; iminodiacetic acid-chelated crosslinked polystyrene-divinylbenzene cationic resins; strongly basic polystyrene-divinylbenzene anionic resins; weakly basic polystyrene-divinylbenzene anionic resins; strongly basic/weakly basic polystyrene-divinylbenzene anionic resins; strongly basic/weakly basic acrylic anionic resins; strongly acidic perfluorosulfonated cationic resins; strongly basic perfluroroaminated anionic resins; natural anion exchangers, such as clay; natural cation exchangers, such as manganese greensand; porous inorganic materials, such as zeolite, capable of absorbing ions; and combinations thereof. Such matrix materials are commercially available. - The
catalyst 420 coated on the matrix may be selected from the group consisting of platinum group metals (platinum, ruthenium, rhodium, palladium, osmium, iridium), as well as gold, silver, chrome, iron, lead, titanium, manganese, cobalt, nickel, molybdenum, tungsten, aluminum, silicon, zinc, tin and alloys or oxides thereof. - Although there is no limitation in thickness of the
electrode catalyst layer 420, the electrode catalyst layer may have a thickness of 0.1-5 μm, more particularly 0.1-2 μm. In the case of a thickness greater than 2 μm, a non-active reaction layer that does not participate in a reaction becomes too thick, thereby causing catalyst loss and poor cost efficiency. - The
electrode catalyst layer 420 may have a surface area covering 1-100% of the surface of the matrix depending on the particular purpose of electrochemical reaction. - Methods for forming the electrode catalyst layer on the ion exchange resin body include chemical methods, such as adsorption-reduction and electroplating, physical methods, such as vacuum deposition, etc. However, considering coating on a large amount of spherical ion exchanger particles, chemical adsorption-reduction methods may be used. Chemical adsorption-reduction methods are carried out by allowing an electrode catalyst material to be adsorbed on an ion exchange resin and reducing the electrode catalyst material on the surface of the ion exchange resin. Such methods may be applied and performed easily by those skilled in the art.
-
FIG. 5 shows aspherical electrode 500 having a multilayer type metal layer according to another embodiment of the present invention. After forming afirst metal layer 520 on the ionexchange resin matrix 510 as shown inFIG. 4 by an adsorption-reduction method, or the like, the same or differentmetal catalyst layer 530 is further formed on the first metal layer to provide an electrode having a bilayer structure. Thefirst layer 520 may include a metal, such as titanium, silver, copper or tin, having excellent electron conductivity. Thesecond layer 530 may include the electrode catalyst layer as mentioned with reference toFIG. 4 . -
FIG. 6 is a schematic view showing a spherical electrode according to still another embodiment. The spherical electrode is a hollow spherical electrode structure obtained by firing the spherical electrode as shown inFIG. 4 orFIG. 5 at about 800° C. so that the inner ion exchange layer is pyrolyzed. -
FIG. 7 shows a sphericalelectrochemical cell 700 according to an embodiment. As shown inFIG. 7 , the sphere functions as aunit electrolysis cell 700. The sphericalelectrochemical cell 700 includes fundamental elements of an electrochemical cell, such as an anode, cathode, electrolyte, or the like. The spherical electrochemical cell includes anion conductor matrix 710 as an electrolyte, ametal 720 having an anodic function (oxidation) as an anode catalyst, and ametal 730 having a cathodic function (reduction) as a cathode catalyst. Particular types of theanode catalyst 720 orcathode catalyst 730 coated on the matrix are the same as described with reference toFIG. 4 . In practice, the metal forming theanode catalyst 720 may be different from the metal forming thecathode catalyst 730. - In the spherical electrochemical cell, the electrode catalyst layer may have a thickness of 1-5 μm. In the case of a thickness greater than 5 μm, a non-active reaction layer that does not participate in a reaction becomes too thick, thereby causing catalyst loss.
- The surface area (combined surface area of the anode layer surface with the cathode layer surface) may be within a range of 1-99% depending on the particular purpose of electrochemical reaction. More particularly, the surface area (combined surface area of the anode catalyst surface with the cathode catalyst surface) may be within a range of 30-90%. The surface area that equals to 100% means a contact between the anode and the cathode, suggesting a short between the anode and the cathode as a physical meaning. Thus, in this case, no electrochemical reaction occurs.
- Methods for forming the
anode catalyst metal 720 and thecathode catalyst metal 730 are the same as described above with reference toFIG. 4 . For example, a metal catalyst as theanode catalyst metal 720 is formed first partially on the total surface by an adsorption-reduction method, and then thecathode catalyst metal 730 is further formed partially on the total surface by an adsorption-reduction method. Since an adsorption-reduction method is used, it is possible to form theanode catalyst metal 720 and thecathode catalyst metal 730 at different positions. -
FIG. 15 is a photo showing the spherical electrolysis cell ofFIG. 7 , wherein Pt is used as an anode catalyst metal and Sn is used as a cathode catalyst metal.FIG. 16 is a photo showing a magnified view of the interface of the spherical electrolysis cell ofFIG. 10 . - The examples and experiments will now be described. The following examples and experiments are for illustrative purposes only and not intended to limit the scope of the present disclosure.
-
-
TABLE 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Catalyst type Pt Ru Ni Pd Precursor type Pt(NH3)6]Cl4 RuCl4 NiCl2 PdCl2 Precursor 1 mM 1 mM 1 mM 1 mM concentration Adsorption time 1 hr 1 hr 1 hr 1 hr Reducing agent NaBH4 NaBH4 NaBH4 NaBH4 type Reducing agent 5% 5% 5% 5% concentration Reduction time 1 hr 1 hr 1 hr 1 hr Reduction pH 8 8 8 8 Determination of SEM SEM SEM SEM precipitation Result Surface Surface Surface Surface coating coating coating coating -
TABLE 2 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Catalyst type Ir Pb Sn Cu Precursor type IrCl4 Pb(SO4) SnCl4 CuSO4 Precursor 1 mM 1 mM 1 mM 1 mM concentration Adsorption time 1 hr 1 hr 1 hr 1 hr Reducing agent NaBH4 NaBH4 NaBH4 NaBH4 type Reducing agent 5% 5% 5% 5% concentration Reduction time 1 hr 1 hr 1 hr 1 hr Reduction pH 8 8 8 8 Determination of SEM SEM SEM SEM precipitation Result Surface Surface Surface coating Surface coating coating coating -
TABLE 3 Ex. 9 Ex. 10 Catalyst type Pt/TiO2 Pt (Anode), Ni (Cathode) Precursor type TiCl4(1st) Pt(NH3)6]Cl4NiCl2 H2PtCl6(2nd) Precursor 1 mM 1 mM/1 mM concentration Adsorption time 1 hr 1 hr Reducing agent NaBH4 NaBH4 type Reducing agent 5% 5% concentration Reduction time 1 hr 1 hr Reduction pH 8 8 Determination of SEM SEM precipitation Result Surface coating Surface coating -
FIG. 8 is an SEM image showing the first Ti coating layer obtained from Example 9. It is shown that Ti is developed well with a uniform shape. -
FIG. 9 is an SEM image showing the second Pt coating layer obtained from Example 9. It is shown that Pt is not concentrated locally but is dispersed uniformly. -
FIG. 10 is an image of the sample obtained from Example 9 taken by XRD analysis. It is shown that Pt, TiO2 and the like are formed desirably. It is thought that Ti present in the form of TiO2 results from oxide formation with oxygen in water. - 1. Manufacture of Spherical Electrode (see Example 9)
- 2. Structure of Electrolysis Cell
- (1) Schematic View of Electrolysis Cell:
FIG. 11 - (2) Structural Parameters of Electrolysis Cell
-
TABLE 4 Parameter Value Presence of diaphragm No Distance between anode and 4 mm cathode Type and size of anode IrO2—RuO2 pyrolyzed electrode current collector on Ti, 4 cm × 4 cm Type and size of cathode Pt electroplated electrode on current collector Ti, 4 cm × 4 cm Short-preventing member on Nylon polymer-based nonwoven web with cathode current collector a porosity of 80% Position of filled electrode Filled in a 4 mm space between an anode and a cathode - 3. Operation Condition of Electrolysis Cell
-
TABLE 5 Parameter Value Current density 0.1 A/cm2 Electrolyte 3% aqueous NaCl solution Electrolyte retention time (min) 10 - 4. Analysis of Performance
- (1) Method of Calculating Current Efficiency
- Current efficiency is obtained by dividing a measured value of hypochlorous acid generated under an applied current (I) by a theoretical value according to the following formula:
-
Current efficiency (%)={(F×ρ×V)/(35500 (mg)×l×t)}×100, - wherein F is the Faraday constant (96500 (C)), ρ is an actual residual chlorine concentration (ppm, mg/L), V is a volume (L) of water supplied to an electrolysis cell, I is an applied current (A), and t is a time (s) of electrolysis.
- (2) Performance parameters and Determination Methods
-
TABLE 6 Analysis Parameter Analysis method interval (hr) Results Voltage Determined by a 1 hr Expressed as Ex. multimeter 11 in FIG. 11 Chlorine Iodometry 1 hr Expressed as Ex. concentration 11 in FIG. 12 Current efficiency Calculated 1 hr Expressed as Ex. according to 11 in FIG. 13 Formula 1 - 1. Structure of Electrolysis Cell
-
TABLE 7 Parameter Value Presence of diaphragm No Distance between anode and 4 mm cathode Type and size of anode current IrO2—RuO2 pyrolyzed electrode on Ti, collector 4 cm × 4 cm Type and size of cathode current Pt electroplated electrode on Ti, collector 4 cm × 4 cm Short-preventing member on None cathode current collector Position of filled electrode None - 2. Operation Condition of Electrolysis Cell
-
TABLE 8 Parameter Value Current density 0.1 A/cm2 Electrolyte 3% aqueous NaCl solution Electrolyte retention time (min) 10 - 3. Performance Analysis
-
TABLE 9 Analysis Parameter Analysis method interval (hr) Results Voltage Determined by 1 hr Expressed as multimeter Comp. Ex. 1 in FIG. 11 Chlorine Iodometry 1 hr Expressed as concentration Comp. Ex. 1 in FIG. 12 Current efficiency Calculated 1 hr Expressed as according to Comp. Ex. 1 in FIG. Formula 113 - As shown in
FIG. 11 , the electrode according to the present invention has the same electrolysis voltage as the electrode according to Comparative Example. Referring toFIG. 12 , the electrode according to the present invention has a chlorine concentration two times higher than a chlorine concentration of the electrode according to Comparative Example. It is thought that such a higher current density is derived from a larger electrode area in the same space and a lower current density at a filled electrode.FIG. 13 illustrates comparison of the current efficiencies between the electrode according to the present invention and the electrode according to Comparative Example. The current density values are obtained from the results ofFIG. 10 andFIG. 11 and the formula of current density as mentioned in Comparative Example 1.
Claims (8)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2009-0104524 | 2009-10-30 | ||
KR20090104524 | 2009-10-30 | ||
PCT/KR2009/007012 WO2011052842A1 (en) | 2009-10-30 | 2009-11-26 | Spherical electrode and electrolysis cell including same |
Publications (1)
Publication Number | Publication Date |
---|---|
US20120267242A1 true US20120267242A1 (en) | 2012-10-25 |
Family
ID=43922259
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/504,235 Abandoned US20120267242A1 (en) | 2009-10-30 | 2009-11-26 | Spherical electrode and electrolysis cell including same |
Country Status (2)
Country | Link |
---|---|
US (1) | US20120267242A1 (en) |
WO (1) | WO2011052842A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140158526A1 (en) * | 2012-12-06 | 2014-06-12 | Hon Hai Precision Industry Co., Ltd. | Cathode catalyst, cathode material using the same, and reactor using the same |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5268082A (en) * | 1991-02-28 | 1993-12-07 | Agency Of Industrial Science And Technology | Actuator element |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5652059A (en) * | 1991-11-20 | 1997-07-29 | Bar Ilan University | Method for attaching microspheres to a substrate |
KR101161884B1 (en) * | 2003-10-20 | 2012-07-03 | 지이 이오닉스 인코포레이티드 | Spiral electrodeionization device and components thereof |
-
2009
- 2009-11-26 US US13/504,235 patent/US20120267242A1/en not_active Abandoned
- 2009-11-26 WO PCT/KR2009/007012 patent/WO2011052842A1/en active Application Filing
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5268082A (en) * | 1991-02-28 | 1993-12-07 | Agency Of Industrial Science And Technology | Actuator element |
Non-Patent Citations (3)
Title |
---|
Chen et al. (International Journal of Hydrogen Energy, 34, 2009, pages 2164-2173, as cited by application in IDS). * |
Dioos et al. (Advanced Synthesis & Catalysis, 348, 2006, 1413-1446) * |
Gonzalez-Huerta et al. (Journal of Power Sources, 153, 2006, 11-17) * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140158526A1 (en) * | 2012-12-06 | 2014-06-12 | Hon Hai Precision Industry Co., Ltd. | Cathode catalyst, cathode material using the same, and reactor using the same |
US10400340B2 (en) * | 2012-12-06 | 2019-09-03 | Tsinghua University | Cathode catalyst, cathode material using the same, and reactor using the same |
Also Published As
Publication number | Publication date |
---|---|
WO2011052842A1 (en) | 2011-05-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Liu et al. | Recent advances in electrocatalysts for seawater splitting | |
Chen et al. | Stability challenges of electrocatalytic oxygen evolution reaction: From mechanistic understanding to reactor design | |
AU2016289094B2 (en) | Redox flow battery with carbon dioxide based redox couple | |
Asghari et al. | Advances, opportunities, and challenges of hydrogen and oxygen production from seawater electrolysis: An electrocatalysis perspective | |
Bolar et al. | Progress in theoretical and experimental investigation on seawater electrolysis: opportunities and challenges | |
CN105821436B (en) | A kind of double electrolytic cell two-step method chloric alkali electrolysis method and devices based on three-electrode system | |
KR102200474B1 (en) | Bifunctional electrocatalyst for water electrolysis with high oxygen vacancy and nanoporous structure, a manufacturing method thereof, and battery for water electrolysis including the electrocatalyst | |
AU2020313943A1 (en) | A method for eficient electrocatalytic synthesis of pure liquid procuct solutions including H2O2, oxygenates, ammonia, and so on | |
US20100252422A1 (en) | Carbon fiber-electrocatalysts for the oxidation of ammonia and ethanol in alkaline media and their application to hydrogen production, fuel cells, and purification processes | |
KR101399172B1 (en) | Oxygen gas diffusion cathode, electrolytic cell employing same, method of producing chlorine gas and method of producing sodium hydroxide | |
CN110199055B (en) | Anode, anode for water electrolysis, electrolysis cell, and method for producing hydrogen | |
JP2000104189A (en) | Production of hydrogen peroxide and electrolytic cell for production | |
KR102237529B1 (en) | Bifunctional electrocatalyst for water electrolysis with high oxygen vacancy and nanoporous structure, a manufacturing method thereof, and battery for water electrolysis including the electrocatalyst | |
KR20130024109A (en) | Electrolytically ionized water generator | |
JPWO2019117199A1 (en) | Manganese oxide for water splitting catalyst, manganese oxide-carbon mixture, manganese oxide composite electrode material and method for producing them | |
Wang et al. | Inverse doping IrOx/Ti with weakened Ir-O interaction toward stable and efficient acidic oxygen evolution | |
KR20090091503A (en) | The oxygen generator | |
Yoon et al. | Perspectives on the development of highly active, stable, and cost‐effective OER electrocatalysts in acid | |
CA3177207A1 (en) | An anion exchange membrane electrolyzer having a platinum-group-metal free self-supported oxygen evolution electrode | |
Chang et al. | Advancements in Seawater Electrolysis: Progressing from Fundamental Research to Applied Electrolyzer Application | |
US20120267242A1 (en) | Spherical electrode and electrolysis cell including same | |
Park et al. | Heterostructured nanocatalysts to boost the hydrogen evolution reaction in neutral electrolyte | |
KR100704440B1 (en) | Method for manufacturing membrane electrode assemblies with porous electro catalytic layer | |
WO2021193467A1 (en) | Manganese-iridium complex oxide for water decomposition catalyst, manganese-iridium complex oxide electrode material, and production methods therefor | |
JP2019525995A (en) | Method and system for producing chlorine and caustic using an oxygen depolarized cathode |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: ELCHEM TECH CO., LTD., KOREA, REPUBLIC OF Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MOON, SANG BONG;LEE, TAI-LIM;KIM, EUN-SOO;AND OTHERS;REEL/FRAME:028547/0902 Effective date: 20120618 Owner name: MOON, SANG BONG, KOREA, REPUBLIC OF Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:LEE, TAI-LIM;KIM, EUN-SOO;CHOI, YUN-KI;REEL/FRAME:028547/0976 Effective date: 20120618 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |