EP3268511A1 - Alkalische photoelektrochemische zelle - Google Patents
Alkalische photoelektrochemische zelleInfo
- Publication number
- EP3268511A1 EP3268511A1 EP16708672.7A EP16708672A EP3268511A1 EP 3268511 A1 EP3268511 A1 EP 3268511A1 EP 16708672 A EP16708672 A EP 16708672A EP 3268511 A1 EP3268511 A1 EP 3268511A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- solar cell
- layer
- nickel
- transparent
- separator
- 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.)
- Withdrawn
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 104
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 50
- 239000012736 aqueous medium Substances 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 28
- 239000000956 alloy Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 150000002739 metals Chemical class 0.000 claims abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001301 oxygen Substances 0.000 claims abstract description 25
- 238000005260 corrosion Methods 0.000 claims abstract description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004332 silver Substances 0.000 claims abstract description 14
- 229910052709 silver Inorganic materials 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 9
- 239000011651 chromium Substances 0.000 claims abstract description 9
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 9
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 9
- 239000010937 tungsten Substances 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 229910001868 water Inorganic materials 0.000 claims description 51
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 44
- 229910052710 silicon Inorganic materials 0.000 claims description 44
- 239000010703 silicon Substances 0.000 claims description 44
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000013543 active substance Substances 0.000 claims description 16
- 230000007797 corrosion Effects 0.000 claims description 16
- 230000008878 coupling Effects 0.000 claims description 15
- 238000010168 coupling process Methods 0.000 claims description 15
- 238000005859 coupling reaction Methods 0.000 claims description 15
- 229920000554 ionomer Polymers 0.000 claims description 12
- 239000002609 medium Substances 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000010409 thin film Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 6
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 6
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- -1 sulfate Compound Chemical class 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 4
- 229920001400 block copolymer Polymers 0.000 claims description 4
- 239000004020 conductor Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 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 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 238000003776 cleavage reaction Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000005518 polymer electrolyte Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 230000007017 scission Effects 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 13
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
- 239000010410 layer Substances 0.000 description 150
- 239000007789 gas Substances 0.000 description 22
- 239000003792 electrolyte Substances 0.000 description 13
- 239000011148 porous material Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000002346 layers by function Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 150000003376 silicon Chemical class 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015556 catabolic process Effects 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
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000003071 parasitic effect Effects 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- 229910001339 C alloy Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229920005372 Plexiglas® Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910000971 Silver steel Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000012994 industrial processing Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 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 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 239000006163 transport media Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
-
- 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
- C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2045—Light-sensitive devices comprising a semiconductor electrode comprising elements of the fourth group of the Periodic System (C, Si, Ge, Sn, Pb) with or without impurities, e.g. doping materials
-
- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/548—Amorphous silicon PV cells
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Definitions
- the invention relates to a photoelectrochemical cell for the light-driven production of
- Hydrogen and oxygen from an aqueous medium in a basic medium deals with the preparation of the photoelectrochemical cell photoelectrode and with a process for the light-driven production of hydrogen and oxygen using
- a photo-electrochemical cell (engl .: photo electro chemical cell, short: PEC) is a device that allows, of water (H 2 0) to gain and molecular oxygen (0 2) molecular hydrogen (H 2), wherein the energy required for this from light, more precisely from sunlight.
- H 2 0 water
- H 2 0 molecular oxygen
- H 2 molecular hydrogen
- the high-quality hydrogen can be sustainably made available from water, which in turn can be burned or released without C0 2 emissions, but can also be further refined chemically into secondary products.
- the availability of efficient, low-cost photoelectrochemical cells is thus an essential prerequisite for a sustainable, hydrogen-based energy industry.
- a PEC essentially comprises two functional units, namely a photovoltaic element and an electrolyzer.
- the photovoltaic element converts light into electrical energy. With the help of electrical energy, the electrolyzer is operated, which splits water electrochemically into hydrogen and oxygen and separates the two gases. The splitting of the water is therefore not directly with light energy, but via the electrical detour. So that the electrical voltage generated by the solar cell can be transferred to the electrolyzer, photovoltaic element and electrolyzer are electrically interconnected.
- photovoltaic element and electrolyzer can be provided as separate components and electrically connected. Both solar cells and electrolyzers are industrially available as separate components. In order to adapt the photovoltaic voltage tapped at the solar cell to the electrochemical voltage required for the water splitting in the electrolyzer, it is generally necessary to connect power electronics therebetween. This one described separate structure has the disadvantage that it is comparatively expansive and that occur through the current transport and power electronics losses.
- photoelectrochemical cells which integrate the two functional units - photovoltaic element and electrolyzer - in one component.
- the individual functional units are realized in layers and interconnected electrically.
- the photovoltaic element and an electrode of the electrolyzer are combined in a so-called photoelectrode.
- a power electronics is not provided, but rather a solar cell is used, which is suitable for water splitting
- Photovoltage supplies The obvious advantage of an integrated PEC is that its space is smaller and that it can be produced cheaper in mass production.
- a further advantage of such a layered, integrated PEC can be seen in the fact that the surface area of the electrodes of the electrolyzer substantially corresponds to the surface area of the solar cell, precisely because the solar cell and an electrode of the electrolyzer are combined in the photoelectrode. Due to the large electrode area, the current density in the electrolyzer decreases, which increases its efficiency.
- an electrochemical cell is always to be understood below as an integrated device in which the two main functional elements (photovoltaic element and electrolyzer) are built up in layers .
- Such PEC always have a photoelectrode, ie the assembly which on the one hand comprises the complete photovoltaic element and on the other hand serves as an electrode of the electrolyzer, as a rule as a cathode.
- PEC include a counter electrode and a separator. The separator electrically isolates the two electrodes from each other, but at the same time allows an ion exchange and causes the separation of the gases obtained. Inside the electrolyzer there is a reaction space separated by the separator into two parts.
- the water molecules are split into oxygen and hydrogen atoms, which in turn combine to form molecular hydrogen and oxygen. That's why the
- Reaction space of the electrolyzer are filled with the water to be split.
- water to be split not only water can be used, since pure water has insufficient ionic conductivity for (H + or OH " ) .
- an aqueous medium which is acidic or basic is filled into the reaction space
- Acid or a base which acts as an electrolyte on the one hand due to their acidic or alkaline character and on the other hand also provides the to be split H 2 0 molecules due to their water content.
- the acidic or basic character of the aqueous medium introduced into the reaction space of the electrolyzer first of all has an influence on the catalysts used in the electrolyzer.
- correspondingly catalytically active substances are provided in the electrolyzer. These may be noble metals such as platinum, ruthenium or iridium, but also base metals such as molybdenum, manganese, iron, nickel or cobalt, which act catalytically active in their oxidic or partially oxidic form. If an acid is used as an aqueous medium, a noble metal catalyst must be used, since only the precious metals of the acid lastingly withstand.
- alkaline media prove to be problematic because they attack the semiconductor material contained in the solar cells.
- the contact with alkaline media should be avoided as much as possible because significant damage is to be feared - after all, it is not without reason that the semiconductor industry uses potassium hydroxide as an etchant for silicon components by default.
- Durability of an integrated PEC In particular, if cost reasons do not apply to noble metal catalysts and inexpensive potassium hydroxide solution is to be used as an aqueous medium, precautions must be taken to protect the silicon-based solar cell or the entire photoelectrode from attacks from the alkali.
- a use of a semiconductor material other than silicon does not lead further here: Although semiconductor materials for solar cells are known, which could be more resistant to alkalis than silicon. This may be the case with gallium arsenide solar cells. However, such solar cells are significantly more expensive than silicon-based solar cells because gallium is not as abundant on earth as silicon and little technology is available for its industrial processing. For cost and sustainability reasons, therefore, the use of solar cells, which do not consist of conventional silicon or its alloys excluded.
- WO2013 / 143885A1 discloses a PEC which operates either in acidic or alkaline conditions. To protect the silicon-based solar cell from the electrolyte is the
- Photo electrode provided on its side facing the reaction space with a corrosion-inhibiting coupling layer based on graphite, silver or stainless steel or other electrolyte-resistant metals.
- the corrosion-inhibiting coupling layer is considered a conductive
- the invention is based on the object to further optimize an integrated, working with the alkaline electrolyte PEC: It has namely shown that silver, which has the best reflector properties and thus increases the yield of solar cells, itself rapidly dissociates from the solar cell in the presence of alkaline media; probably because the alkali creeps behind the silver due to the poor bonding of silver to the silicon and etches the underlying silicon of the solar cell.
- the basis is a transparent substrate, which is the simplest case of inorganic glass.
- the transparent substrate is disposed on the light side of the PEC and is reflected by the incident light.
- a transparent, electrically conductive layer is applied on the side facing away from the incident light of the transparent substrate.
- This may consist of doped ZnO, In 2 O 3 or SnO 2 , which can be deposited by sputter deposition, chemical vapor deposition (CVD) or liquid phase deposition (eg, spray pyrolysis), typically 50 nm in thickness has up to 3 ⁇ .
- the transparent, conductive layer makes the transparent substrate electrically conductive in order to serve as a current collector, because inorganic glass is known to be electrically insulating.
- the transparent, electrically conductive layer can be provided with a texture or be applied in textured form. More on that later.
- At least one partially transparent solar cell based on silicon is applied to the transparent, electrically conductive layer.
- a solar cell which is known per se, again comprises a plurality of functionalized layers of silicon which are characterized by a different doping (n- and p-type), intrinsic conductor behavior, crystallinity and alloying elements such as oxygen, Hydrogen, carbon or germanium can differ.
- n- and p-type doping
- Such a Si-based solar cell comprises three layers, namely an n-doped, a p-doped and in between an intrinsic layer. These three functional layers together form a so-called pin or nip junction.
- the functional layers of the solar cell do not have to by order
- a solar cell which is based on inexpensive silicon and which is partially transparent. Such a solar cell is preferably deposited by way of thin-film technology from the gas phase, it is thus a so-called thin-film solar cell.
- further transparent solar cells may in turn be applied comprising a plurality of differently functionalized silicon layers in order to increase the luminous efficacy and to achieve a sufficiently high photovoltage (> 1.5 V) for direct water splitting.
- a single solar cell will usually not be able to deliver the necessary photovoltage.
- the applied solar cells can have different band gaps to the
- solar cells which adsorb in the UV or IR range. It is recommended to provide two or three solar cells (i.e., two or three pin junctions) on top of each other, that is, a tandem or triple solar cell. It is also possible to stack more than three solar cells one above the other. According to the invention, at least one solar cell, that is to say a pin junction, is necessary.
- the solar cells are to be designed as thin-film solar cells, so a piece of transparent, so that the unadsorbed light on the back of the solar cell exits again.
- the transparency of the thin-film solar cells is due to the low layer thicknesses of the silicon layers.
- the solar cell is not completely transparent, since it has to absorb light. That's why the term partial-transparent is used here. Since the solar cells used are hydrogenated silicon or an alloy of hydrogenated silicon with germanium,
- the solar cell may also have other functional layers, such as ZnO: Al or ⁇ ⁇ ⁇ : ⁇ . These materials can be applied in particular to the boundary layers of the solar cells in order to reduce plasmotic effects. Such layers based on ZnO or SiO are considered here as part of the solar cell.
- a transparent adhesion-promoting layer is applied directly to the last applied solar cell, namely from one of the following metals: nickel, chromium, tungsten or hafnium.
- the primer layer may also consist of an alloy of one or more of these metals.
- Mirror layer is applied, which consists of silver, copper, aluminum or an alloy of one or more of these metals.
- the mirror layer serves to reflect the light fallen through the solar cells in the direction of the transparent substrate, so that the hitherto unadsorbed light hits the solar cells again. This increases the luminous efficacy. It is crucial that between the solar cell and mirror layer, the adhesion-promoting layer is provided, which ensures that the mirror layer does not peel off. It has been found that the highly reflective metals silver, copper or aluminum with a thin layer of nickel, chromium, tungsten or hafnium can bind to the silicon of the solar cell and this compound is stable even in an alkaline medium. This makes it possible to use an inexpensive silicon solar cell in an alkaline PEC. Incidentally, a layer of nickel, chromium, tungsten or hafnium can be applied so thinly to the last solar cell that the adhesion-promoting layer is transparent and thus does not shade the mirror.
- Another essential feature of the invention is that directly adjacent to the rear side of the mirror layer, ie toward the reaction space, one still adjacent to the reaction space
- Corrosion protection layer of nickel or a nickel-containing alloy is applied.
- This anticorrosive layer need not be transparent, unlike the primer layer, since it is arranged on the shadow side of the mirror. However, it is directly exposed to the alkaline medium in the reaction space and must therefore be corrosion resistant.
- a comparatively thick layer of nickel has proven itself, since it is stable in the alkaline medium and does not detach from the silver.
- the nickel layer acts catalytically in the water splitting, which is why it achieves a bonus effect over other anticorrosion layers of photoelectrodes.
- a photoelectrode layered in this manner can be combined with a per se known separator and a counterelectrode to form a PEC, which achieves the stated objects.
- the invention therefore relates to a photoelectrochemical cell for the light-driven production of hydrogen and oxygen from an aqueous medium in a basic medium, with a photoelectrode arranged on the light side, with a shadow side arranged
- the photoelectrode comprising a transparent substrate arranged on the light side, which is coated in the direction of the separator with the following
- Layer order a) a transparent, electrically conductive layer
- transparent primer layer which consists of one of the following metals or of an alloy of one or more of these metals: nickel, chromium, tungsten, hafnium; e) with a mirror layer applied directly to the primer layer and consisting of one of the following metals or of an alloy of one or more of these metals: silver, copper, aluminum;
- An essential aspect of the invention is that the layer sequence described here and the mentioned coating materials are precisely adhered to, since the layers only fulfill their respective function and give a total of a photoelectrode, which achieves a good luminous efficacy, which is durable under alkaline conditions, therefore allows the use of an alkaline electrolyte and therefore does not necessarily rely on noble metal catalysts.
- the photoelectrochemical cell operates in a basic medium.
- the electrolyzer to set alkaline conditions, namely via the aqueous medium and / or via the separator.
- the basicity is adjusted via the aqueous medium.
- a basic aqueous medium whose pH is greater than 7 is used.
- the aqueous medium must contain on the one hand the water to be split, and on the other hand at least one hydroxide or carbonate or phosphate or hydrogen carbonate or hydrogen phosphate or nitrate or sulphate compound of any of the following: lithium, sodium, potassium, magnesium, calcium,
- the aqueous medium is preferably potassium hydroxide solution or sodium hydroxide solution, ie a mixture of water and potassium hydroxide or sodium hydroxide. Potassium hydroxide and caustic soda are cheap mass chemicals. Of course, several alkaline compounds can be used mixed.
- the separator should be made of a material which does not conduct any electrons. Nevertheless, the separator must allow hydroxide ions to pass, so that a charge balance can take place and the hydroxide ions released by the electrolysis can diffuse through the separator from the cathode to the anode in order to be oxidized to oxygen there.
- Gas-impermeable must be the separator, so that the gas molecules collected on both sides of the separator do not mix again, otherwise it can lead to a back reaction to water up to a blast gas explosion.
- Gas impermeable means impermeable to 0 2 and H 2 . Any permeability to other gases is not relevant.
- Suitable materials for the separator are anion-conducting ceramics, polymers functionalized with ion-conducting groups, such as polyolefins, polyethers, polyimides, polyamides and
- Polysulfones wherein said polymers are used in pure form, as a mixture or as co-polymers or as block polymers or as block copolymers. Especially preferred
- Membrane material is a cross-linked, hydrocarbon-only polyolefin with quaternary ammonium groups.
- a separator made of such basic materials is a solid state electrolyte.
- the separator is a solid electrolyte
- the aqueous medium itself need not have electrolytic properties. It is then possible to use pure water with neutral pH 7.
- the basicity of the system then comes out of the separator. Pure water within the meaning of this invention is water having an electrical conductivity of less than 1 * 10 "4 S / m. If the ionic conductivity of the separator is not sufficient (worse solid electrolyte), it may be useful, if necessary, still additionally a basic Liquid electrolyte (water or alkali with pH> 7) to use.
- Solid-state electrolyte is therefore characterized in that the aqueous medium is water having an electrical conductivity of less than 1 ⁇ 10 -4 S / m, and that the separator is a gas-impermeable, anion-conducting and electronically insulating
- Polymer electrolyte membrane wherein the separation-active material of the membrane is preferably selected from the following materials: ceramics, polyolefins, polyethers, polyimides, Polyamides, polysulfones, wherein said polymers are used in pure form, as a mixture or as copolymers or as block polymers or as block copolymers.
- the photoelectrochemical cell has a reaction space which extends on both sides of the separator and in which the electrochemical water splitting takes place.
- the reaction space is not empty but at least filled with the aqueous medium.
- the reaction space at the corrosion protection layer ends, since it is not overcome by the aqueous medium.
- Anticorrosion layer and the separator should therefore be as small as possible but as large as necessary.
- a porous structure made of an electrically conductive material between the anticorrosion layer and the separator, which is electrically contacted at least with the anticorrosion layer.
- This arrangement causes the reaction space to extend at least partially in the pores of the porous structure.
- the pores are therefore to be sized so that they can absorb the aqueous medium and release the resulting gases.
- the porous structure is electrically conductive and is electrically contacted with the anticorrosion layer, it becomes electrochemically a part of the electrode. As a result, the photoelectrode moves closer to the separator and thereby lowers the resistance contributions without consuming the reaction space.
- the porous, electrically conductive structure is applied to the separator.
- the porous structure consists of a catalytically active in the water splitting material and / or is provided therewith. Since the water splitting in the Pores of the porous material, it is promoted by the presence of the catalytically active material.
- the porous structure may be foamed nickel or a textile fabric made of nickel fibers or stainless steel fibers.
- the porous structure may be impregnated with catalytically active substances, such as nickel oxide and / or cobalt oxide.
- the catalyst is preferably located at the interface between electrode and separator, and as close as possible to the separator. If the porous structure is impregnated with nickel oxide and / or cobalt oxide, the porous material itself need not be catalytically active, it is sufficient electrical conductivity.
- the porous material may be a fabric of carbon fibers impregnated with nickel oxide and / or cobalt oxide.
- the textile structure can also be integrated into the photoelectrode
- Corrosion protection layer of nickel applied very thick and porous to the separator out. It is also possible to provide the nickel layer with corresponding grooves and depressions to make room for the reaction space. Likewise, the separator can be geometrically patterned to create reaction space in the separator.
- a porous nickel structure can be provided on both sides of the separator. It is possible to provide different catalysts on both sides, each for the desired reaction, i. Water oxidation at the anode and water reduction at the cathode, are optimized.
- the entire counterelectrode can be made porous, for example from a solid nickel foam.
- the catalytically active substances can also be applied to the separator in the form of an ionomer-containing paste: Under a lonomer-containing paste is a mixture of water and an organic solvent, a hydroxyl ion-conducting polymer as needed an electrically conductive additive and a in the Water splitting catalytically active substance to understand. Catalytically active substances are enriched in this paste in the water splitting, so that when the aqueous medium is filled in, it saturates the ionomer-containing paste. The reaction space then extends at least partially within the ionomer-containing paste.
- the paste may also be used in combination with a porous nickel-containing structure.
- the water splitting catalytically active substances is preferably nickel oxide and / or cobalt oxide.
- nickel oxide and / or cobalt oxide Alternatively, palladium or platinum could be used, but these metals are significantly more expensive than nickel and cobalt. Since in the PEC invention, no acidic, but basic conditions prevail, no expensive precious metal catalyst needs to be used.
- the solar cell can be designed as a tandem or triple solar cell:
- the photoelectrode has two solar cells applied in layers, each of which in turn comprises several layers of differently doped silicon or its alloys, wherein the first solar cell is applied directly to the transparent, electrically conductive layer, wherein the second solar cell directly the first solar cell is applied, and wherein the coupling layer is applied directly to the second solar cell.
- the photoelectrode has three solar cells applied in layers, each of which in turn comprises several layers of differently doped silicon or different crystallinity or its alloys, wherein the first solar cell is applied directly to the transparent, electrically conductive layer, wherein the second solar cell is applied directly to the first solar cell, wherein the third solar cell is applied directly to the second solar cell and wherein the coupling layer is applied directly to the third solar cell.
- solar cells with the same or different band gap can be stacked. With different band gaps, the adsorption spectrum can be extended, so that the efficiency increases.
- the crystallinity and the degree of hydrogenation can be used to vary the band gap of the silicon, whereby tandem or triple cells can be produced purely from silicon whose sub-cells absorb in different spectral ranges.
- Solar cell (s) to so-called thin-film sola cell (s) acts.
- the layers of a thin-film solar cell are not cut out of a wafer, but separated from the gas phase. They are therefore significantly thinner than the layers of a wafer-based solar cell and are therefore partially transparent.
- a wafer solar cell is not transparent.
- the thickness of the thin-film solar cell depends on the layer thickness of the individual layers.
- the intrinsic silicon layers i-layer of the pin or nip structure
- the intrinsic silicon layers may well be more than 1 ⁇ m thick, in particular the ⁇ -5 ⁇ : ⁇ -5 ⁇ .
- Amorphous intrinsic layers within the solar cell are typically 50-500 nm thick, microcrystalline intrinsic layers: 0.1-10 ⁇ .
- the doped layers on the backside (n-doped) can also be significantly thicker than 20 nm, since parasitic absorption plays no role there.
- the solar cell can also comprise further functional layers, such as those based on SiO or ZnO, in order to reduce plasmotic effects.
- the transparent substrate is an organic or inorganic glass.
- An inorganic glass is usually made of Si0 2 .
- Organic glasses consist of one
- the substrate is preferably provided on its coated side facing the coupling layer with a texture which allows incident light to pass in the direction of the coupling layer, but scatters incident light back from the direction of the coupling layer in the direction of the coupling layer.
- the texture scatters the light into larger angles, thus leading to a
- the texture thus increases the light output.
- the texture is a surface modification of the glass, which is etched wet-chemically.
- the texture can also be applied to the transparent, electrically conductive layer. This is done subtractively by etching the transparent, electrically conductive layer or additively by textured application of the transparent, electrically conductive layer.
- the invention relates essentially to the layer structure of the photoelectrode, a method for producing this photoelectrode is likewise provided by the invention.
- the preparation is carried out by coating the transparent substrate successively as follows: a) with a transparent, electrically conductive layer;
- a directly applied to the last applied solar cell, transparent, primer layer which consists of one of the following metals or of an alloy of one or more of these metals: nickel, chromium, tungsten, hafnium;
- a mirror layer applied directly to the primer layer, which layer consists of one of the following metals or of an alloy of one or more of these metals: silver, copper, aluminum;
- bordering corrosion protection layer of nickel or of a nickel-containing alloy is bordering corrosion protection layer of nickel or of a nickel-containing alloy.
- PVD physical vapor deposition
- the PEC according to the invention serves to produce molecular hydrogen and molecular oxygen from the aqueous medium introduced into the reaction space, the electrical energy necessary for the electrolytic water splitting being obtained from the visible and / or invisible sunlight with which the photoelectrode is illuminated ,
- the invention therefore also provides a process for the light-driven production of hydrogen and oxygen from an aqueous medium, using a
- the photoelectrochemical cell according to the invention in which the aqueous medium is introduced into the reaction space of the photoelectrochemical cell and light is applied to the transparent substrate of the photoelectrode, so that incident and reflected light is adsorbed in the solar cell, resulting in electric current between the photoelectrode and the photoelectrochemical cell
- Counter electrode is converted, which causes a cleavage of the water in the aqueous medium contained in oxygen and hydrogen and a separation of oxygen and hydrogen on both sides of the separator in the reaction space.
- Figure 2 as Figure 1, but in an exploded view
- FIG. 3 Second embodiment II of a PEC with neutral aqueous medium
- the first embodiment I of a photoelectrochemical cell according to the invention is shown in FIG.
- the three basic components of the PEC are a photoelectrode 1, a separator 2 and a counterelectrode 3.
- the photoelectrode here forms the cathode of the PEC, the counterelectrode forms the anode. But it is also the other way around.
- the photoelectrode faces the sun 0.
- the sun 0 is not part of the invention.
- the counter electrode 3 is located on the side of the shadow facing away from the sun 0.
- the separator 2 is arranged between the photoelectrode 1 and the counterelectrode 3.
- the photoelectrode 1 and counterelectrode 3 are not directly adjacent to the separator 2, but are spaced therefrom.
- reaction space 4 is formed between the two electrodes 1, 3, which is divided symmetrically into two parts by the separator 2.
- the reaction space 4 is not empty, but filled with a, not shown in the drawing, aqueous medium having a pH greater than 7, such as potassium hydroxide, on the other hand, on both sides of the separator 2 each have a porous, nickel-containing structure 5K , 5A inserted. It is a nickel sponge, which is impregnated with catalytically active substances 6K, 6A.
- the porous, nickel-containing structure 5K on the side of the cathode is directly on the photoelectrode 1, so that there is an electrical contact with it.
- the cathode-side, porous, nickel-containing structure 5K abuts the separator 2.
- another catalytically active substance 6A is introduced as the catalytically active substance 6K on the cathode side of the separator. Since the aqueous medium is in the pores of the nickel sponges 5K, 5A, it comes in contact with the respective catalytically active substance 6K, 6A everywhere.
- the separator 2 is gas-impermeable and ionically conductive. He isolated photoelectrode 1 and
- the separator 2 therefore consists of a non-electrically conductive ceramic or of an organic polymer which has hydroxide ion-conducting groups.
- the counter electrode 3 consists of an alkaline
- Solution stable metal such as nickel or titanium or of a conductive material which is provided with a protective layer of nickel or titanium or its alloys.
- the counterelectrode can also be porous itself. Decisive is the layer structure of the photoelectrode 1. This is based on a glassy substrate 7, on the side facing the separator 2 a texture 8 is introduced. On the textured side of the substrate 7, a transparent, electrically conductive layer 9 is applied, for example, doped ZnO, ln 2 0 3 or Sn0 second As an alternative to the texture on the glassy substrate 7, the electrically conductive layer 9 can also be textured.
- a first solar cell 10 is applied and on this in turn a second solar cell 11.
- the two solar cells 10, 11 thus form a tandem Solar cell.
- Each of the two solar cells 10, 11 each again consists of three silicon-based layers, namely a p-doped silicon layer, an n-doped silicon layer and an intrinsically doped silicon layer therebetween.
- the three silicon layers form a pin junction and thus a solar cell.
- the layer sequence pin can also be reversed in nip, whereby the polarity of the solar cell changes and the photoelectrode becomes the anode.
- On the second solar cell 11 may still be a third solar cell to obtain a triple solar cell.
- the solar cell can contain several functional intermediate layers, for example of ZnO: Al or SiO x : H, in order to minimize plasmotic effects.
- a coupling layer 12 is applied directly, which in turn is designed in multiple layers. It comprises an adhesion-promoting layer 13, a mirror layer 14 and a corrosion-protection layer 15.
- the adhesion-promoting layer consists of nickel and is very thin, it preferably consists of a few atomic monolayers of nickel. This corresponds to a layer thickness between 0.5 nm and 5 nm. Due to its low layer thickness, the adhesion-promoting layer is transparent.
- the primer layer may consist of chromium, tungsten or hafnium.
- the mirror layer 14 is made of silver and therefore reflects light well. Alternatively, aluminum can be used, which is less reflective but less expensive than silver. Their layer thickness is between 10 nm and 500 nm.
- the corrosion protection layer 15 is made of nickel, but is thicker than the
- the adhesion-promoting layer 13 directly connects the last solar cell 11 with the mirror layer 14.
- the adhesion-promoting layer can be applied directly to an Si-based layer or to any functional ZnO or SiO-based functional layer.
- the corrosion protection layer 15 is applied directly to the mirror layer 14 and, with its other end of the layer, directly adjoins the reaction space 4. It therefore comes into contact with the alkaline aqueous medium contained therein.
- the nickel of the anticorrosive layer 15, however, is stable in an alkaline medium and protects the entire photoelectrode from attack by the base.
- the Primer layer is durable, so that the mirror layer is not peeled off by the solar cell if the caustic should creep behind the mirror.
- the PEC is completed by an electrically conductive connection 16 between front contact (on the light side) of the photoelectrode 1 and counterelectrode 2. On the side of the photoelectrode, this is connected to the transparent, electrically conductive layer 9. In the case of the counter electrode, the place of connection is not so important because the counter electrode is completely metallic and therefore conducts the electric current everywhere.
- the electrically conductive connection 16 is led around the outside of the PEC. It does not have to
- the electrically conductive connection 16 is, in the simplest case, a cable.
- the transparent substrate 7 is directed to the sun 0 or other light source.
- the light 17 enters the PEC through the transparent substrate 7.
- the light 17 may include several wavelengths 171, 172 also in the invisible area.
- the texture 8 and the transparent, electrically conductive layer 9 the light 17 strikes the first solar cell 10. In this case, the light with the band gap corresponding wavelength 171 and below is adsorbed as much as possible.
- Longer-wavelength light 172 passes through the first solar cell 10 and is largely adsorbed in the second solar cell 11 in accordance with a smaller band gap to be sensibly selected.
- the light 17 also includes even longer wavelength components that are not adsorbed, but the tandem solar cell 10, 11 is for the adsorption of two
- Light 173 which was not adsorbed by the two solar cells in the first pass, falls through the transparent adhesion-promoting layer 13 on the mirror layer 14 and is reflected there. It passes through the two solar cells again (this time in the opposite direction) and is further adsorbed.
- Light 174 which was still not adsorbed in the second pass, is reflected at the texture 8 of the substrate 7 and thereby prevented from leaving the photoelectrode.
- the incident light 17 is therefore repeatedly thrown back and forth between the mirror layer 17 and the texture 8, passing through both solar cells 10, 11 several times. This increases the luminous efficacy.
- Corrosion protection layer 15 and counter electrode 3. This means that due to the structure of the photoelectrode 1, the electrically conductive corrosion protection 15 act as a cathode and the counter electrode 3 as an anode. This causes within the reaction space 4, the electrolysis of the water contained in the aqueous medium.
- the hydrogen H 2 formed accumulates on the cathode side of the separator 2, during which the oxygen 0 2 formed is accumulated on the anode side of the separator. 2
- Hydrogen H 2 and oxygen 0 2 are drawn off separately on both sides of the separator. 2 Due to its gas impermeability, the separator prevents backmixing of hydrogen H 2 and oxygen 0 2 and thus a blast gas explosion (2 H 2 +0 2 -> 2 H 2 0).
- the aqueous medium During operation, the aqueous medium must be continuously pumped through the reaction space in the circulation process in order to ensure effective removal of the electrochemically formed gases (H 2 and O 2 ).
- the aqueous medium thus also assumes the function of a transport medium for O 2 and H 2 .
- the water splitting concentrates the basic
- Component e.g., potassium hydroxide or sodium hydroxide
- the concentrated medium must always be rediluted with fresh water before it re-enters the PEC.
- sodium hydroxide itself is not consumed and therefore does not have to be topped up.
- the PEC absorbs light and water and releases hydrogen and oxygen.
- the layer structure of the first embodiment I is more apparent from the exploded view in Figure 2.
- FIG. 3 shows a second embodiment II of the invention. This is particularly compact since photoelectrode 2 and counterelectrode 3 rest directly on the separator 2.
- the reaction space 4 is therefore minimal.
- the separator 2 is made of a material having anion conductive properties. Therefore, it can be called a solid electrolyte.
- ionomer paste 19A, 19K which is applied on both sides to the separator 2, on the anode and cathode side with the corresponding catalyst
- ionomer paste 19a has a different composition than the cathode-side ionomer paste 19k
- a 800 nm thick, transparent, conductive aluminum-doped ZnO layer is applied to a transparent glass substrate by means of cathode ray evaporation (magnetron sputtering @ 13.56 MHz) of a ceramic ZnO: Al 2 O 3 target (1 at.%) At a temperature of 300 ° C, a power density of 2 W / cm 2 and an argon pressure of 0.1 Pa deposited. The sample is heated for one hour prior to deposition and the base pressure in the chamber prior to deposition is 8x10 "5 Pa. The surface of the ZnO: Al layer is then wet-chemically roughened in dilute HCl (1%) to produce crater-like surface structures scattering visible light (texture).
- a-Si: H amorphous hydrogenated silicon
- PECVD plasma assisted vapor deposition
- the intrinsic layer of the bottom cell becomes at a substrate temperature of 130 ° C at a Silane concentration in the gas phase of 10% for 120 minutes deposited so that it has a thickness of 400 nm.
- the p-doped layers are deposited at a temperature of 180 ° C with the addition of trimethylborane to the gas phase as a doping source for 90 seconds so that they have a thickness of about 15 nanometers. The same applies to the n-doped layers, but with the addition of phosphine to the gas phase.
- a 0.6 nm nickel layer is thick, optically almost completely transparent applied to the surface of the second n-doped silicon layer. This provides for improved adhesion of the subsequently also by means of electron applied 200 nm
- the layer stack is closed by a 100 nm thick, electron beam evaporated closed nickel layer, which protects the underlying layers from the electrolyte and is suitable as a catalyst for the hydrogen evolution in alkaline solution.
- a photoelectrochemical cell for light-driven water splitting can be built up as follows:
- the photoelectrode is inserted with its glass side to the outside in a holding frame / tray, whereby these z. B. can be sealed using a flat gasket to the frame.
- a catalytically active formulation was applied by means of spray coating and thermally cured / activated.
- An anion-directing membrane is placed on the catalytically active side of the sponge electrode (eg Fumatech FAA-3).
- Another sponge electrode is placed with its functionalized side on the membrane. This sponge electrode is fired by means of a cable to the front contact located at the edge of the solar cell.
- Electron spaces can come on the two sides of the membrane. • The two sponge electrodes are perfused with IM KOH. The electrolyte flow simultaneously removes the gas produced during the splitting of water (H2 and 02).
- Hydrogen of> 8%. This means that 8% of the radiant energy introduced by the light is converted into chemical energy of hydrogen.
- H 2 is hydrogen
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Abstract
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AU2018408211B9 (en) * | 2018-02-12 | 2020-10-22 | Khaled A.H. ABO-HASHEMA | Method and device for the preparation of alcohols from hydrocarbons |
DE102018206452A1 (de) * | 2018-04-26 | 2019-10-31 | Evonik Degussa Gmbh | Siliciumbasierte Schutzschichten für Bauteile photoelektrochemischer Zellen |
DE102020003913B3 (de) * | 2020-06-22 | 2021-06-24 | Edmund Philipp | Verfahren zur Anwendung von 3-D-Funktionstextilstrukturen mit aktivierbaren und ansteuerbaren Hardware- und Softwarekomponenten. |
CN114086195A (zh) * | 2020-08-06 | 2022-02-25 | 四川大学 | 一种太阳电池电解水制氢的系统 |
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DE102012205258A1 (de) | 2012-03-30 | 2013-10-02 | Evonik Industries Ag | Photoelektrochemische Zelle, System und Verfahren zur lichtgetriebenen Erzeugung von Wasserstoff und Sauerstoff mit einer photoelektrochemischen Zelle und Verfahren zur Herstellung der photoelektrochemischen Zelle |
KR102014990B1 (ko) * | 2013-01-29 | 2019-08-27 | 삼성전자주식회사 | 광전극 구조체용 복합 보호층, 이를 포함하는 광전극 구조체 및 이를 포함하는 광전기화학 전지 |
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WO2016142382A1 (de) | 2016-09-15 |
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