CN114395773B - Carbon dioxide electrolytic cell and carbon dioxide electrolysis pile device - Google Patents
Carbon dioxide electrolytic cell and carbon dioxide electrolysis pile device Download PDFInfo
- Publication number
- CN114395773B CN114395773B CN202111631131.6A CN202111631131A CN114395773B CN 114395773 B CN114395773 B CN 114395773B CN 202111631131 A CN202111631131 A CN 202111631131A CN 114395773 B CN114395773 B CN 114395773B
- Authority
- CN
- China
- Prior art keywords
- carbon dioxide
- flow
- plate
- gas
- electrode
- 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.)
- Active
Links
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 224
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 112
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 112
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 50
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 239000011148 porous material Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 25
- 239000012528 membrane Substances 0.000 claims description 18
- 238000009792 diffusion process Methods 0.000 claims description 17
- 238000009826 distribution Methods 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000012530 fluid Substances 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 238000005363 electrowinning Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 238000005341 cation exchange Methods 0.000 claims description 6
- 239000003011 anion exchange membrane Substances 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004020 conductor Substances 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000012263 liquid product Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 description 62
- 239000000243 solution Substances 0.000 description 25
- 239000003792 electrolyte Substances 0.000 description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 description 10
- -1 hydrogen ions Chemical class 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000003014 ion exchange membrane Substances 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910020647 Co-O Inorganic materials 0.000 description 3
- 229910020704 Co—O Inorganic materials 0.000 description 3
- 229910017135 Fe—O Inorganic materials 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 239000004801 Chlorinated PVC Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229940063013 borate ion Drugs 0.000 description 2
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 229910000457 iridium oxide Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229940085991 phosphate ion Drugs 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920003935 Flemion® Polymers 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 229910020923 Sn-O Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 239000002608 ionic liquid Substances 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
- 238000010030 laminating Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/02—Diaphragms; Spacing elements characterised by shape or form
-
- 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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
-
- 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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
- C25B3/26—Reduction of carbon dioxide
-
- 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
- C25B9/70—Assemblies comprising two or more cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention relates to the technical field of carbon dioxide electrolysis, in particular to a carbon dioxide electrolytic cell and a carbon dioxide electrolysis galvanic pile device. The carbon dioxide electrolytic cell comprises: a first plate; the cathode electrode is arranged on one side of the first polar plate, and the cathode electrode and the first polar plate form a carbon dioxide gas chamber; the liquid flow plate is arranged on one side of the cathode electrode, which is far away from the first polar plate, and is provided with a pore canal for the passage of the catholyte; a diaphragm arranged on one side of the liquid flow plate, which is far away from the cathode electrode, and a catholyte chamber is formed between the diaphragm and the cathode electrode; an anode electrode arranged on one side of the diaphragm, which is away from the flow plate; and the second polar plate is arranged on one side of the anode electrode, which is far away from the diaphragm, and an anolyte chamber is formed between the second polar plate and the diaphragm.
Description
Technical Field
The invention relates to the technical field of carbon dioxide electrolysis, in particular to a carbon dioxide electrolytic cell and a carbon dioxide electrolysis galvanic pile device.
Background
Along with the development of efficient carbon dioxide emission reduction technology in China, among a plurality of technologies, carbon dioxide electrolysis is widely considered to have broad prospects, and carbon dioxide can be efficiently converted into high-added-value chemicals such as formic acid, ethanol and the like by using low-cost renewable power. However, most of carbon dioxide electrolysis researches are still in a laboratory research stage at present, the total reaction current is lower than 0.1A, and the total electrolysis power is lower than 0.5W; the only few carbon dioxide electrowinning devices are based on single cell studies, with overall power still limited (< 20W), and most employ two-chamber membrane electrode configurations based on anionic membranes. The two-chamber electrolytic cell configuration only comprises a cathode gas chamber and an anode electrolyte chamber, the anionic membrane is in direct contact with a cathode electrode, the running stability of the device is mainly dependent on the service life of the anionic membrane under the strong alkaline condition and is limited by the low performance of the current anionic membrane, and the running time of the carbon dioxide electrolytic cell with the configuration is generally less than 50 hours. Therefore, a carbon dioxide electrolytic cell and a carbon dioxide electrolysis pile device which can keep the operation time for more than 200 hours and the electrolysis power for more than 1kW are still lacking, and the industrial application of the carbon dioxide electrolysis is severely limited.
Disclosure of Invention
Based on the above, the invention provides the carbon dioxide electrolytic cell and the carbon dioxide electrolysis pile device which can stably operate for a long time, have low energy consumption and higher electrolysis efficiency.
In one aspect of the present invention, there is provided a carbon dioxide cell comprising:
a first plate;
the cathode electrode is arranged on one side of the first polar plate, and the cathode electrode and the first polar plate form a carbon dioxide gas chamber;
the liquid flow plate is arranged on one side of the cathode electrode, which is far away from the first polar plate, and is provided with a pore canal for the passage of the catholyte;
a diaphragm arranged on one side of the liquid flow plate, which is far away from the cathode electrode, and a catholyte chamber is formed between the diaphragm and the cathode electrode;
an anode electrode arranged on one side of the diaphragm, which is away from the flow plate; and
The second polar plate is arranged on one side of the anode electrode, which is far away from the diaphragm, and an anolyte chamber is formed between the second polar plate and the diaphragm;
the first electrode plate is provided with a first groove towards one surface of the cathode electrode, the second electrode plate is provided with a second groove towards one surface of the anode electrode, the first grooves and/or the second grooves extend to form a runner, and the runner is a multi-channel runner.
In one embodiment, the flow channel is a multi-channel serpentine flow channel, the number of the channels is 3-8, the width of a single channel is 0.5-5 mm, and the depth is 0.1-3 mm.
In one embodiment, the anode electrode is a porous material formed by an anode catalyst or a catalyst layer formed by a porous substrate and an anode catalyst disposed on the surface of the porous substrate.
In one embodiment, the cathode electrode is a porous gas diffusion electrode comprising a stack of gas diffusion layers disposed toward the first plate side and cathode catalyst layers disposed toward the flow plate side.
In one embodiment, the gas diffusion layer comprises at least one gas diffusion sublayer and the cathode catalyst layer comprises at least one cathode catalyst sublayer.
In one embodiment, the membrane is an anion exchange membrane or a cation exchange membrane.
In one embodiment, the first electrode plate and the second electrode plate are made of conductive materials, and are respectively and independently selected from one or more of aluminum, titanium, stainless steel and graphite, and/or the material of the liquid flow plate is insulating resin.
In one embodiment, the carbon dioxide electrolytic cell further comprises a flow limiting channel, wherein the flow limiting channel comprises a pipeline for conveying the anolyte from outside to the second polar plate, a pipeline for conveying the gas from outside to the first polar plate and a pipeline for conveying the catholyte from outside to the liquid flow plate, and the length of each pipeline is 5 cm-50 cm. .
In still another aspect of the present invention, there is provided a carbon dioxide electrolysis cell stack apparatus comprising a plurality of carbon dioxide electrolysis cells, a plurality of said carbon dioxide electrolysis cells being stacked in series, wherein at least one of the carbon dioxide electrolysis cells is said carbon dioxide electrolysis cell.
In one embodiment, each of the carbon dioxide cells is a carbon dioxide cell as claimed in any one of claims 1 to 7.
In one embodiment, at least two adjacent carbon dioxide electrolytic cells are provided, wherein a first polar plate of one carbon dioxide electrolytic cell and a second polar plate of the other carbon dioxide electrolytic cell are shared, one surface of the shared polar plate is provided with the first groove, and the other surface is provided with the second groove.
Compared with the prior art, the invention at least comprises the following beneficial effects:
according to the carbon dioxide electrolytic cell provided by the invention, on one hand, the cathode electrolyte chamber is introduced at one side of the cathode on the basis of a two-chamber configuration, so that the carbon dioxide electrolytic cell forms a three-chamber structure of the carbon dioxide gas chamber, the cathode electrolyte chamber and the anode electrolyte chamber, the cathode electrolyte is positioned between the diaphragm and the cathode electrode as a buffer layer, and direct contact between the diaphragm and the cathode electrode is avoided, so that the diaphragm can adopt an anion exchange membrane and a cation exchange membrane, and compared with the anion exchange membrane, the cation exchange membrane can ensure long-term stable operation of the electrolytic cell, and the service life of the electrolytic cell is remarkably prolonged; on the other hand, grooves are formed on the first polar plate, the second polar plate and the liquid flow plate to form a multichannel runner, and the flow resistance pressure drop in the runner and the resistance pressure drop in the flow limiting channel are regulated and controlled through the multichannel runner, so that the mass transfer rate is improved, the energy consumption is reduced, the reaction performance is not damaged in the process of amplifying the area of the reaction electrode, and the electrolytic efficiency of the electrolytic cell is further improved.
The carbon dioxide electrolytic cell provided by the invention can also realize that a plurality of electrolytic cells are connected in series to form a carbon dioxide electrolysis galvanic pile device, effectively enlarge the area of a reaction electrode, and even enlarge the total electrode area to 0.3m 2 And above, the electrolysis power can reach more than 1kW, and the reaction scale and the stable operation time close to the industrial grade are realized.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a carbon dioxide cell according to one embodiment;
FIG. 2 is a schematic structural diagram of a first plate according to an embodiment;
FIG. 3 is a schematic view of a cathode electrode according to an embodiment;
FIG. 4a is a schematic plan view of a flow plate according to an embodiment;
FIG. 4b is a schematic cross-sectional view of a flow plate according to an embodiment;
FIG. 5 is a schematic structural diagram of a second plate according to an embodiment;
FIG. 6 is a schematic diagram of a carbon dioxide electrolysis cell stack device according to an embodiment;
FIG. 7 is a schematic view showing a carbon dioxide electrolysis cell stack device according to another embodiment
Reference numerals illustrate:
100. a carbon dioxide electrolysis cell;
110. a first plate; 120. a cathode electrode; 121. a gas diffusion layer; 122. a cathode catalyst layer; 130. A flow plate; 140. a diaphragm; 150. an anode electrode; 160. a second polar plate;
200. a fixing plate;
300. screwing a fastener;
l1, an anolyte distributing pipe;
m1, an anolyte converging tube;
l2, catholyte distribution tube;
m2, an anolyte converging tube;
l3, a gas distribution pipe;
m3, a gas converging pipe.
Detailed Description
Reference now will be made in detail to embodiments of the invention, one or more examples of which are described below. Each example is provided by way of explanation, not limitation, of the invention. Indeed, it will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the scope or spirit of the invention. For example, features illustrated or described as part of one embodiment can be used on another embodiment to yield still a further embodiment.
Accordingly, it is intended that the present invention cover such modifications and variations as fall within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention will be disclosed in or be apparent from the following detailed description. It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention.
Except where shown or otherwise indicated in the operating examples, all numbers expressing quantities of ingredients, physical and chemical properties, and so forth, used in the specification and claims are to be understood as being modified in all instances by the term "about". For example, therefore, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be varied appropriately by those skilled in the art utilizing the teachings disclosed herein seeking to obtain the desired properties. The use of numerical ranges by endpoints includes all numbers subsumed within that range and any range within that range, e.g., 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, 5, and the like.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Referring to fig. 1, an embodiment of the present invention provides a carbon dioxide electrolytic cell 100, which includes a first electrode plate 110, a cathode electrode 120, a liquid flow plate 130, a diaphragm 140, an anode electrode 150, and a second electrode plate 160.
A surface of the first electrode plate 110 facing the cathode electrode 120 is provided with a first groove a. Referring to fig. 2, the first trench a extends to form a flow channel having a plurality of channels. The flow channels may be serpentine, parallel or interdigitated flow channels, in the particular example shown in fig. 2.
In some preferred embodiments, the flow channels are multichannel serpentine flow channels, the number of channels is 3-8, the width of a single channel is 0.5-5 mm, and the depth is 0.1-3 mm. The channel design can control the ratio of the fluid resistance pressure drop in the flow channel to the resistance pressure drop in the flow limiting channel to be between 10 and 100, can control the operation pressure of the fluid to be in a better range, further improves the mass transfer rate, reduces the energy consumption and improves the electrolysis efficiency of the Gao Dianjie pool.
The material of the first electrode plate 110 may be independently selected from a chemically stable conductive material (such as aluminum, titanium, stainless steel, or graphite), so that the first electrode plate 110 may serve as a current collector. In some embodiments, a current collector is also provided on the first plate 110, and communicates with an external circuit through the current collector.
The cathode electrode 120 is disposed at one side of the first electrode plate 110, and the cathode electrode 120 and the first electrode plate 110 form a carbon dioxide gas chamber through which carbon dioxide gas can flow. A gas inlet (not shown) and a gas outlet (not shown) are connected to the first electrode plate 110, and carbon dioxide gas or a gas containing carbon dioxide is introduced and discharged through the gas inlet and the gas outlet by a flow controller (not shown). The carbon dioxide gas or the carbon dioxide-containing gas flows through the carbon dioxide gas chamber so as to contact the cathode electrode 120.
What happens at the cathode electrode 120 is carbon dioxide (CO 2 ) To form formic acid (HCOOH), carbon monoxide (CO) and methane (CH) 4 ) Acetic acid (CH) 3 COOH), ethylene (C 2 H 4 ) Methanol (CH) 3 OH), ethanol (C) 2 H 5 OH), n-propanol (C) 3 H 7 OH), and the like.
Referring to fig. 3, in some embodiments, a cathode electrode 120 has a gas diffusion layer 121 and a cathode catalyst layer 122 disposed on the gas diffusion layer 121. As shown in fig. 3, the gas diffusion layer 121 is disposed on the carbon dioxide gas flow path side, and is provided in the carbon dioxide cell, that is, on the side facing the first electrode plate 110. The cathode catalyst layer 122 is disposed on the cathode solution flow path side, and is provided on the carbon dioxide cell, i.e., toward the liquid flow plate 130 side. The cathode catalyst layer 122 preferably has catalyst nanoparticles and catalyst nanostructures. The gas diffusion layer 111 is made of a porous carbon substrate such as carbon paper or carbon cloth, a metal mesh, a foam metal, a porous film, or the like.
In the cathode catalyst layer 122, catholyte, ions are supplied and discharged from the catholyte chamber, and in the gas diffusion layer 121, CO 2 The gas is supplied from a carbon dioxide gas chamber. The gas diffusion layer 121 has a porous structure with water repellency and gas permeability, thereby ensuring CO 2 The gas may reach the cathode catalyst layer 122 through the gas diffusion layer 121. CO 2 The reduction reaction of (a) occurs near the boundary between the gas diffusion layer 121 and the cathode catalyst layer 122, the gas phase product is mainly discharged from the carbon dioxide gas chamber, and the liquid phase product is mainly discharged from the catholyte chamber.
The cathode catalyst layer 122 is preferably made of a catalytic material (cathode catalytic material) that is capable of reducing carbon dioxide to produce specific carbon-containing compounds, and has a low overpotential and high selectivity. As such a material, one or more of a carbon material, a transition metal material, a composite material of carbon and a transition metal oxide, an alloy of a noble metal and a transition metal, and a composite material of a noble metal and a transition metal oxide can be cited, wherein the transition metal can be selected from one or more of copper, tin, bismuth, lead, indium, cadmium, zinc, and nickel, and the noble metal can be selected from one or more of gold, silver, and a platinum group metal. The preparation mode of the composite material can be one or more selected from electrodeposition, physical mixing, hydrothermal method, pyrolysis method, ball milling method and vapor deposition method. In the composite material, the mass percentage of the transition metal or the transition metal oxide can be 30-100%, and the mass percentage of the noble metal or the carbon is not more than 70%. The cathode catalyst layer 122 may be formed in various shapes such as a plate, a mesh, a wire, a particle, a porous, a film, and an island.
The flow plate 130 is disposed on a side of the cathode electrode 120 facing away from the first plate 110. Referring to fig. 4a and 4b, the flow plate 130 is provided with hollow channels c for passing the catholyte. The plurality of channels c extend to form channels, and the channels can also be serpentine channels, parallel channels or crossed comb-shaped channels, preferably multichannel serpentine channels, the number of the channels is 3-8, the width of a single channel is 0.5-5 mm, and the depth is 0.1-10 mm. By arranging the multichannel serpentine flow channel on the liquid flow plate, the operating pressure of the fluid can be further reduced, the mass transfer rate is improved, the energy consumption is reduced, and the electrolytic efficiency of the Gao Dianjie cell is improved. The width of the channel c is the width of a single channel, and the depth of the channel c is the depth of a single channel. In some embodiments, a plurality of connection ribs d are further provided in the channel c of the flow plate 130, and the connection ribs d are disposed between two panels constituting the channel c to reinforce the mechanical strength of the flow channel, and the connection ribs d have a thickness of 0.1 to mm mm to 8mm.
The material of the liquid flow plate 130 may be independently selected from chemically stable insulating materials, preferably insulating resin materials with high chemical stability and high mechanical strength, such as Polyetheretherketone (PEEK), chlorinated polyvinyl chloride, ABS plastic, and the like. .
The membrane 140 is disposed on a side of the flow plate 130 facing away from the cathode electrode 120. A catholyte chamber through which catholyte can flow is formed between separator 140 and cathode electrode 120. The catholyte chamber is disposed between the cathode electrode 120 and the membrane 140 such that the catholyte is in contact with the cathode electrode 120 and the membrane 140. A catholyte inlet (not shown) and a catholyte outlet (not shown) are connected to the flow plate 130, and a catholyte is introduced and discharged by a pump (not shown) through the catholyte inlet and the catholyte outlet. The catholyte flows through the catholyte flow path (catholyte chamber) so as to contact the cathode electrode 120 and the separator 140.
The separator 140 is composed of an ion exchange membrane or the like that can move ions between the anode electrode 150 and the cathode electrode 120 and can separate the anode and the cathode of the electrolytic cell. As the ion exchange membrane, for example, a cation exchange membrane such as Nafion, flemion or an anion exchange membrane such as Neosepta, selemion can be used. Preferably, the membrane 140 is composed of a cation exchange membrane. However, in addition to the ion exchange membrane, a glass filter, a porous polymer membrane, a porous insulating material, or the like may be applied to the separator 140 as long as it is a material capable of moving ions between the anode electrode 150 and the cathode electrode 120.
Anode electrode 150 is disposed on a side of diaphragm 140 facing away from flow plate 130. The anode electrode 150 is capable of supplying water (H 2 O) is oxidized to form oxygen, hydrogen ions or hydroxyl ions (OH) - ) The catalyst material (anode catalyst material) is preferably mainly composed of a catalyst material (anode catalyst material) capable of reducing the overvoltage of such a reaction. Examples of such catalytic materials include metals such as platinum (Pt), palladium (Pd), and nickel (Ni), alloys containing these metals, intermetallic compounds, manganese oxide (Mn-O), iridium oxide (Ir-O), nickel oxide (Ni-O), cobalt oxide (Co-O), iron oxide (Fe-O), tin oxide (Sn-O), indium oxide (In-O), ruthenium oxide (Ru-O), binary metal oxides such as lithium oxide (Li-O), and lanthanum oxide (La-O), ternary metal oxides such as Ni-Co-O, ni-Fe-O, la-Co-O, ni-La-O, sr-Fe-O, quaternary metal oxides such as Pb-Ru-Ir-O, la-Sr-Co-O, ru complexes, and Fe complexes.
The anode 150 has a structure capable of moving an anolyte or ions between the separator and the anolyte chamber, and includes a porous substrate such as a mesh material, a punched material, a porous body, or a metal fiber sintered body. The substrate may be made of a metal material such as titanium (Ti), nickel (Ni), iron (Fe), or an alloy (e.g., stainless steel) containing at least 1 of these metals, or may be made of the anode catalytic material described above. In the case of using an oxide as the anode catalytic material, the catalyst layer is preferably formed by attaching or laminating the anode catalytic material to the surface of the base material formed of the above-described metal material. In terms of enhancing the oxidation reaction, the anode catalytic material preferably has nanoparticles, nanostructures, nanowires, or the like. The nanostructure is a structure in which nano-scale irregularities are formed on the surface of a catalytic material.
The second electrode plate 160 is disposed on a side of the anode electrode 150 facing away from the separator 140. An anolyte chamber through which anolyte can flow is formed between the second plate 160 and the membrane 140. The anolyte chamber is used to supply anolyte to the anode electrode 150, and the second plate is provided with an anolyte inlet (not shown) and an anolyte outlet (not shown) through which anolyte is introduced and discharged by a pump (not shown). Anolyte circulates within the anolyte chamber in contact with second plate 160.
Referring to fig. 5, a surface of the second electrode plate 160 facing the anode electrode 150 is provided with a second groove b. The second grooves b extend to form a flow channel having a plurality of channels, and the flow channel formed by the second grooves b may be a serpentine flow channel, a parallel flow channel or an interdigitated flow channel, and fig. 5 shows a serpentine flow channel.
The material of the second electrode plate 160 may be independently selected from a chemically stable conductive material (such as aluminum, titanium, stainless steel, or graphite), so as to ensure that the second electrode plate 160 may serve as a current collector. In some embodiments, a header is also provided on the second plate 160, through which it communicates with external circuitry.
The anolyte and catholyte of the carbon dioxide cell of the present invention preferably contain at least water (H 2 O) solution. Carbon dioxide (CO) 2 ) Is CO from 2 The gas chamber is supplied so that the catholyte may contain carbon dioxide (CO 2 ) May not be contained. The anolyte and catholyte may be applied in the same solution or in different solutions. H-containing compounds as anolyte and catholyte 2 The solution of O may be, for example, an aqueous solution containing an arbitrary electrolyte. Examples of the aqueous solution containing an electrolyte include solutions containing a compound selected from the group consisting of hydroxide ions (OH) - ) Hydrogen ions (H) + ) Potassium ion (K) + ) Sodium ion (Na) + ) Lithium ion (Li) + ) Cesium ions (Cs) + ) Chloride ion (Cl) - ) Bromide ion (Br) - ) Iodide ion (I) - ) Nitrate ions (NO) 3 - ) Sulfate ion (SO) 4 2- ) Formate ion (HCOO) - ) Phosphate ion (PO) 4 3- ) Borate ion (BO) 3 3- ) Bicarbonate ion (HCO) 3 - ) An aqueous solution of at least 1 ion of (a) a group of ions. In order to reduce the resistance of the solution, it is preferable to use a solution in which an electrolyte such as potassium hydroxide, sodium hydroxide, potassium bicarbonate or the like is dissolved at a high concentration as the anolyte and the catholyte.
The catholyte can also be prepared from cations such as imidazolium ions and pyridinium ions and BF 4 - 、PF 6 - The salt of the plasma may be an ionic liquid or an aqueous solution thereof in a liquid state over a wide temperature range. Examples of the other catholyte include amine solutions such as ethanolamine, imidazole, and pyridine, and aqueous solutions thereof. The amine may be any of primary amine, secondary amine, and tertiary amine.
In some embodiments, the carbon dioxide cell further comprises a restricted flow channel (not shown). The flow-limiting channels include a pipe for transferring the anolyte from the outside to the second plate 160, a pipe for transferring the gas from the outside to the first plate 120, and a pipe for transferring the catholyte from the outside to the flow plate 130, each section of pipe having a length of 5cm to 50cm.
Further, the invention also provides a carbon dioxide electrolysis cell stack device, which comprises a plurality of carbon dioxide electrolysis cells, wherein a plurality of carbon dioxide electrolysis cells are stacked in a serial manner, and at least one carbon dioxide electrolysis cell is the carbon dioxide electrolysis cell 100 in any embodiment.
Referring to fig. 6, in some embodiments, each carbon dioxide cell in the carbon dioxide electrolysis cell stack device is the carbon dioxide cell 100 described above. Two adjacent carbon dioxide electrolytic cells 100, wherein a first electrode plate 110 of one carbon dioxide electrolytic cell 100 and a second electrode plate 160 of the other carbon dioxide electrolytic cell 100 are shared, one surface of the shared electrode plate is provided with a first groove a, and the other surface is provided with the second groove b.
In order to ensure good sealing performance of the carbon dioxide electrolysis cell stack device, in some embodiments, positioning holes are provided on each of the first electrode plate 110, the liquid flow plate 130 and the second electrode plate 160. Preferably, the number of the fixing holes on each plate is 4, and more preferably, the fixing holes are uniformly distributed around the plate. The positioning holes on the first polar plate 110, the liquid flow plate 130 and the second polar plate 160 are respectively in one-to-one correspondence.
Further, in some embodiments, the carbon dioxide electrowinning cell stack apparatus is also provided with a securing assembly comprising two securing plates 200 and a plurality of threaded fasteners 300. Regarding the plurality of carbon dioxide cells stacked in a serial manner as a whole, as a device to be fixed, two fixing plates are respectively arranged at opposite sides of the device to be fixed, and fixing holes are formed in the fixing plates 200. Preferably, the number of the fixing holes on the fixing plate is 8, and more preferably, the fixing holes are uniformly distributed around the fixing plate. The fixing holes on the two fixing plates are respectively in one-to-one correspondence.
In some preferred embodiments, the threaded fastener 300 is a spring screw fastener, including a threaded rod, a nut, and a coil spring. The spring screw fastener is adopted to realize the sealing of the carbon dioxide electrolysis cell pile, so that the problem that the carbon dioxide electrolysis cell pile expands with heat and contracts with cold when running at different temperatures can be solved, the device is prevented from being damaged, and the running stability and the service life of the device are improved.
To further ensure sealing performance of the carbon dioxide electrolysis cell stack, in some embodiments, a sealing assembly is also provided between the first plate 110 and the flow plate 130, and/or between the second plate 160 and the flow plate 130, and/or between the flow plate 130 and the diaphragm 140.
In some embodiments, the seal assembly includes a seal ring disposed about the periphery of the desired seal member and a gasket disposed between the seal ring and the desired seal member.
Further, referring to fig. 7, the carbon dioxide electrolysis cell stack device of the present invention further includes:
a power source (not shown in the drawings) that causes an electric current to flow between an anode portion and a cathode portion of each cell of the carbon dioxide electrolysis cell stack;
a solution system for controlling the flow of solution in the device; and
and the gas system is used for controlling the circulation of the gas in the device.
The power supply is not limited to a general commercial power supply, a battery, or the like, and may be a power supply that supplies electric power generated by using renewable energy sources such as a solar battery and wind power generation.
The solution system comprises a 1 st solution system which is connected with the anolyte chamber and provided with a pressure control part, an anolyte distributing pipe L1, a flow control part (pump) and an anolyte converging pipe M1; and
and a 2 nd solution system connected to the catholyte chamber and having a pressure control part, a catholyte distribution pipe L2, a flow control part (pump), and an anolyte collecting pipe M2.
The gas system includes a pressure control unit, a temperature control unit, a gas distribution pipe L3, a flow control unit (flow controller), and a gas converging pipe M3 connected to the carbon dioxide gas chamber.
The solution flow rate and pressure of the anolyte and catholyte are controlled by a solution system. The solution flow rates of the anolyte and the catholyte were controlled at about 100mL/min and the pressures were controlled at 1bar to 5bar. The carbon dioxide electrolysis galvanic pile device provided by the invention controls the ratio of the fluid resistance pressure drop in the flow channel to the resistance pressure drop in the flow limiting channel to be between 10 and 100, wherein the ratio of the fluid resistance pressure drop to the resistance pressure drop in the flow limiting channel is higher than 10, so that the uniform distribution of fluid in each electrolysis cell can be ensured, and the power consumption of the pump can be reduced when the ratio of the fluid resistance pressure drop to the resistance pressure drop in the flow limiting channel is lower than 100, and the energy efficiency can be improved.
In the carbon dioxide electrolysis cell stack device, the flow-restricting passage includes a pipe from the anolyte distribution pipe L1 to the second electrode plate 160, a pipe from the gas distribution pipe L31 to the first electrode plate 110, and a pipe from the catholyte distribution pipe L2 to the liquid flow plate 130.
The flow rate, pressure and temperature of the gas are controlled by the gas system. The gas flow rate is controlled to be 100-500 sccm (single electrolytic cell). If the concentration is less than 100sccm, sufficient CO cannot be supplied 2 Participating in the reaction; if the amount is more than 500sccm, the energy efficiency of the reaction is significantly lowered. Gas pressureControlled to be slightly higher than normal pressure. The gas temperature is controlled between 0 ℃ and 100 ℃.
The following are specific examples. The present invention is further described in detail to assist those skilled in the art and researchers in further understanding the present invention, and the technical conditions and the like are not to be construed as limiting the present invention in any way. Any modification made within the scope of the claims of the present invention is within the scope of the claims of the present invention.
Example 1
The carbon dioxide electrolytic cell shown in fig. 7 was connected to a solution system and a gas system to form an electrolytic cell stack device, and the carbon dioxide electrolysis performance was measured. The carbon dioxide electrolysis cell stack comprises 30 electrolytic cells, wherein a gas diffusion electrode (Sieglini Sigracet 39 BC) loaded with tin dioxide is used as a cathode electrode, foam titanium (0.8 mm thick and with a pore diameter of 50 microns) loaded with iridium is used as an anode electrode, nafion 211 of DuPont is used as an ion exchange membrane, and potassium bicarbonate solution (the concentration is 1 mol/L) is used as electrolyte. The polar plate material adopts titanium, the liquid flow plate material adopts chlorinated polyvinyl chloride resin, and the flow channel formed by the polar plate and the groove on the liquid flow plate is a snake-shaped flow channel (as shown in the figure).
In this electrolytic device, a 1 st solution system having a pressure control unit (not shown), an anolyte distribution pipe L1, a flow control unit (pump), and an anolyte collecting pipe M1 is connected to the anolyte flow path.
A 2 nd solution system having a pressure control part (not shown), a catholyte distribution pipe L2, a flow control part (not shown), and an anolyte collecting pipe M2 is connected to the catholyte flow path.
The carbon dioxide gas flow path is connected to a pressure control unit (not shown), a temperature control unit (not shown), a gas distribution pipe L3, a flow control unit (not shown), and a gas collection pipe M3.
After passing through the gas distribution pipe L3, the humidified carbon dioxide raw material gas is divided into 30 airflows with the same flow velocity, and flows into the serpentine flow channels on the cathode side of the bipolar plates of the 30 single electrolytic cells respectively, then reaches the surface of a cathode catalyst through a gas diffusion electrode, is reduced into formate after fast electron transfer, and unreacted carbon dioxide flows out of the bipolar plates. The formate enters the flow plate, flows out along with the electrolyte through the flow channel, and flows out of the galvanic pile after being converged in the electrolyte converging tube, so that the subsequent product separation process can be performed. The gas flow rate in the cathode plate is controlled to be 500sccm (single electrolytic cell) through a flow controller, the gas pressure is controlled to be slightly higher than normal pressure through a back pressure controller, and the gas temperature is controlled to be 0-100 ℃.
The anolyte flows through the anolyte distributing pipe L1, is equally divided into 30 branches with the same flow rate, flows into serpentine flow passages on the anode side of the bipolar plate of the 30 single electrolytic cells respectively, and then reaches the surface of the anode catalyst through pore passages of a foam electrode (anode electrode). The electrolyte is oxidized on the surface of the catalyst to generate oxygen, generated bubbles flow out of the polar plate along with flowing electrolyte, flow out of the galvanic pile after being converged in the liquid converging pipe, and the generated oxygen can flow into the electrolysis device to participate in the reaction after being discharged. The anolyte was delivered using peristaltic pumps and the single cell flow rate was controlled at about 100mL/min, with the liquid pressure being controlled at 1bar to 5bar by a backpressure controller.
In the above-described electrolyzer, the ratio of the fluid resistance pressure drop in the serpentine flow path to the resistance pressure drop in the restrictor passage is controlled to be about 100.
The carbon dioxide electrolysis cell stack device showed a total current of 10A (current density of 100mA/cm 2 ) The total voltage of the electrolytic stack was 102.7V. The total power is 1027W, the energy efficiency is 53% in the running time of 300 hours and is always kept between 1020W and 1030W, and excellent performance is shown.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples merely represent a few embodiments of the present invention, which facilitate a specific and detailed understanding of the technical solutions of the present invention, but are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. It should be understood that, based on the technical solutions provided by the present invention, those skilled in the art may obtain technical solutions through logical analysis, reasoning or limited experiments, which are all within the scope of protection of the appended claims. The scope of the patent is therefore intended to be covered by the appended claims, and the description and drawings may be interpreted as illustrative of the contents of the claims.
Claims (7)
1. A carbon dioxide electrolysis cell stack device, characterized in that at least two adjacent carbon dioxide electrolysis cells are arranged in series in a stacked manner for converting carbon dioxide into a liquid product;
the carbon dioxide electrolytic cell includes:
a first plate;
the cathode electrode is arranged on one side of the first polar plate, and the cathode electrode and the first polar plate form a carbon dioxide gas chamber;
the liquid flow plate is arranged on one side of the cathode electrode, which is far away from the first polar plate, and is provided with a pore canal for the passage of the catholyte;
a diaphragm arranged on one side of the liquid flow plate, which is far away from the cathode electrode, and a catholyte chamber is formed between the diaphragm and the cathode electrode;
an anode electrode arranged on one side of the diaphragm, which is away from the flow plate; and
The second polar plate is arranged on one side of the anode electrode, which is far away from the diaphragm, and an anolyte chamber is formed between the second polar plate and the diaphragm;
the first electrode plate is provided with a first groove towards one surface of the cathode electrode, the second electrode plate is provided with a second groove towards one surface of the anode electrode, the first groove and/or the second groove extend to form a flow channel, the flow channel is a multichannel snake-shaped flow channel, the number of the channels is 3-8, the width of a single channel is 0.5 mm-5 mm, and the depth is 0.1 mm-3 mm; the first polar plate and the second polar plate are made of conductive materials;
wherein a first polar plate of one carbon dioxide electrolytic cell and a second polar plate of the other carbon dioxide electrolytic cell are shared, one surface of the shared polar plate is provided with the first groove, and the other surface is provided with the second groove;
the carbon dioxide electrolysis cell stack device further comprises:
a power supply that causes an electric current to flow between an anode portion and a cathode portion of each of the carbon dioxide cells of the carbon dioxide electrolysis cell stack device;
a solution system for controlling the flow of solution in the device;
a gas system for controlling the flow of gas in the apparatus; and
a flow restricting passage;
the solution system comprises a 1 st solution system which is connected with the anolyte chamber and provided with a pressure control part, an anolyte distributing pipe L1, a flow control part and an anolyte converging pipe M1; and
a 2 nd solution system which is connected with the catholyte chamber and provided with a pressure control part, a catholyte distributing pipe L2, a flow control part and a catholyte converging pipe M2;
the gas system comprises a pressure control part, a temperature adjusting part, a gas distribution pipe L3, a flow control part and a gas converging pipe M3 which are connected with the carbon dioxide gas chamber;
the flow limiting channel comprises a pipeline from the anolyte distributing pipe L1 to the second polar plate, a pipeline from the gas distributing pipe L3 to the first polar plate and a pipeline from the catholyte distributing pipe L2 to the liquid flow plate, and the length of each pipeline is 5 cm-50 cm;
controlling the solution flow rate and the solution pressure of the anolyte and the catholyte through the solution system, wherein the ratio of the fluid resistance pressure drop in the flow channel to the resistance pressure drop in the flow-limiting channel is controlled between 10 and 100 by the carbon dioxide electrolysis galvanic pile device;
and controlling the flow rate, pressure and temperature of the gas through the gas system, wherein the flow rate of the gas of each carbon dioxide electrolytic cell is controlled to be 100-500 sccm.
2. The carbon dioxide electrowinning cell device in accordance with claim 1, wherein said anode electrode is a porous material formed with an anode catalyst.
3. The carbon dioxide electrowinning cell device as recited in claim 1, wherein the anode electrode is formed from a porous substrate and an anode catalyst layer disposed on a surface of the porous substrate.
4. The carbon dioxide electrowinning cell device in accordance with claim 1, wherein the cathode electrode comprises a gas diffusion layer and a cathode catalyst layer stacked, the gas diffusion layer being disposed toward the first plate side, the cathode catalyst layer being disposed toward the flow plate side.
5. The carbon dioxide electrolysis cell stack device according to claim 1, wherein the membrane is an anion exchange membrane or a cation exchange membrane.
6. The carbon dioxide electrowinning cell device as recited in any one of claims 1-5, wherein the first and second electrode plates are each independently selected from one or more of aluminum, titanium, stainless steel and graphite.
7. The carbon dioxide electrowinning cell device as claimed in any one of claims 1 to 5, wherein the material of the flow plate is insulating resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111631131.6A CN114395773B (en) | 2021-12-28 | 2021-12-28 | Carbon dioxide electrolytic cell and carbon dioxide electrolysis pile device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111631131.6A CN114395773B (en) | 2021-12-28 | 2021-12-28 | Carbon dioxide electrolytic cell and carbon dioxide electrolysis pile device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114395773A CN114395773A (en) | 2022-04-26 |
| CN114395773B true CN114395773B (en) | 2023-07-25 |
Family
ID=81228301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111631131.6A Active CN114395773B (en) | 2021-12-28 | 2021-12-28 | Carbon dioxide electrolytic cell and carbon dioxide electrolysis pile device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114395773B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116288441A (en) * | 2022-12-01 | 2023-06-23 | 清华大学 | Carbon dioxide electrolysis device and carbon dioxide electrolysis method |
| EP4382637A1 (en) | 2022-12-05 | 2024-06-12 | Technische Universität Berlin | Gas diffusion electrode based on porous hydrophobic substrates with a current collector and production thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6672193B2 (en) * | 2017-02-02 | 2020-03-25 | 株式会社東芝 | Carbon dioxide electrolysis cell and electrolyzer |
| JP6813525B2 (en) * | 2018-03-16 | 2021-01-13 | 株式会社東芝 | Carbon dioxide electrolyzer and electrolyzer |
| SG11202113062TA (en) * | 2019-05-25 | 2021-12-30 | Univ Szegedi | Modular electrolyzer cell and process to convert carbon dioxide to gaseous products at elevated pressure and with high conversion rate |
| JP7204619B2 (en) * | 2019-09-17 | 2023-01-16 | 株式会社東芝 | Carbon dioxide electrolysis device and carbon dioxide electrolysis method |
-
2021
- 2021-12-28 CN CN202111631131.6A patent/CN114395773B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114395773A (en) | 2022-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI414636B (en) | Membrane reactor | |
| US20240011172A1 (en) | Electrochemical reaction device | |
| TWI448325B (en) | Method for electrochemically transforming carbon dioxide | |
| US20180138517A1 (en) | Modular electrochemical cells | |
| CN114196975B (en) | Carbon dioxide electrolysis device and carbon dioxide electrolysis method | |
| CN114395773B (en) | Carbon dioxide electrolytic cell and carbon dioxide electrolysis pile device | |
| US10494725B2 (en) | Electrochemical reaction device | |
| KR102254704B1 (en) | Organic hydride manufacturing apparatus and organic hydride manufacturing method | |
| EP3366813B1 (en) | Hydrogen system and method of operation | |
| TWI448327B (en) | Membrane reactor | |
| AU2022201214B2 (en) | Carbon dioxide electrolysis device | |
| EP4060086B1 (en) | Carbon dioxide electrolytic device | |
| WO2018037774A1 (en) | Cathode, electrolysis cell for producing organic hydride, and organic hydride production method | |
| WO2018139597A1 (en) | Electrolytic cell, electrolysis device, and electrolysis method | |
| EP4060087B1 (en) | Carbon dioxide electrolysis device | |
| CN113265670A (en) | Electrolytic cell and electrochemical system containing a support membrane | |
| CN109234768A (en) | A kind of electrochemical appliance preparing nano-Ag particles and method | |
| CN219547111U (en) | Hydrogen peroxide generating device with modified cation exchange membrane | |
| EP4431641A1 (en) | Electrode, membrane electrode assembly, electrochemical cell, stack, and electrolyzer | |
| EP4249639A1 (en) | Carbon dioxide electrolytic device | |
| EP4455371A2 (en) | Electrolysis cell and electrolysis device | |
| CN116949467A (en) | Photovoltaic cell and electrocatalyst integrated photolytic device and module system | |
| CN116732549A (en) | Electrolytic tank system and production method of hydrogen and oxygen | |
| AU2022221423A1 (en) | Electrolytic device and method of driving electrolytic device | |
| CN118173835A (en) | Direct formate fuel cell capable of continuously producing alkali |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |