CN118970130B - A flow battery cycle recovery system and recovery method - Google Patents
A flow battery cycle recovery system and recovery method Download PDFInfo
- Publication number
- CN118970130B CN118970130B CN202411438680.5A CN202411438680A CN118970130B CN 118970130 B CN118970130 B CN 118970130B CN 202411438680 A CN202411438680 A CN 202411438680A CN 118970130 B CN118970130 B CN 118970130B
- Authority
- CN
- China
- Prior art keywords
- gas
- positive electrode
- catalyst
- storage tank
- electrolyte
- 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
- 238000011084 recovery Methods 0.000 title claims abstract description 124
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000003792 electrolyte Substances 0.000 claims abstract description 140
- 239000007788 liquid Substances 0.000 claims abstract description 119
- 239000003054 catalyst Substances 0.000 claims abstract description 113
- 150000002500 ions Chemical class 0.000 claims abstract description 113
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 95
- 230000001590 oxidative effect Effects 0.000 claims abstract description 89
- 238000007086 side reaction Methods 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims description 234
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 239000003115 supporting electrolyte Substances 0.000 claims description 20
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 238000006479 redox reaction Methods 0.000 claims description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- -1 iron ions Chemical class 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910001437 manganese ion Inorganic materials 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000006722 reduction reaction Methods 0.000 description 18
- 238000007254 oxidation reaction Methods 0.000 description 15
- 230000008569 process Effects 0.000 description 13
- 230000009467 reduction Effects 0.000 description 13
- 230000003647 oxidation Effects 0.000 description 11
- 229910052720 vanadium Inorganic materials 0.000 description 11
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 10
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- 230000002238 attenuated effect Effects 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229940006460 bromide ion Drugs 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 229910001451 bismuth ion Inorganic materials 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- TXKAQZRUJUNDHI-UHFFFAOYSA-K bismuth tribromide Chemical compound Br[Bi](Br)Br TXKAQZRUJUNDHI-UHFFFAOYSA-K 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04276—Arrangements for managing the electrolyte stream, e.g. heat exchange
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
Abstract
The application discloses a flow battery circulation recovery system and a recovery method, and belongs to the technical field of flow batteries. The recovery system comprises an anode liquid storage tank, a cathode electrolyte, a catalytic reaction device, a cathode liquid storage tank and a catalytic reaction device, wherein the anode liquid storage tank is filled with anode electrolyte, the anode electrolyte contains reducing ions and active ions, the reducing ions can react with the active ions to reduce the valence state of the active ions and generate first oxidizing gas, the catalytic reaction device is filled with a catalyst and can receive the first oxidizing gas to oxidize and fix the catalyst, the cathode liquid storage tank is filled with cathode electrolyte, the cathode electrolyte generates side reaction to generate first reducing gas, the catalytic reaction device receives the first reducing gas, the first reducing gas is used for reducing the oxidized catalyst, and the generated acid gas can return to the cathode liquid storage tank. According to the application, the valence balance of the positive and negative electrode solutions can be maintained without adding a restorative agent into the positive electrode solution, so that the electrolyte is prevented from being polluted, and the long-life stable operation of the flow battery is realized.
Description
Technical Field
The application belongs to the technical field of flow batteries, and particularly relates to a flow battery circulation recovery system and a recovery method.
Background
In the long-time charge and discharge process of the flow battery, the average valence state of the positive and negative electrode solutions is gradually increased due to hydrogen evolution side reaction of the negative electrode, so that the capacity of the flow battery is reduced, in order to restore the capacity of the flow battery, a reducing substance is added into the positive electrode solution under the condition of a high state of charge (SOC), and high valence active ions with high oxidability can be subjected to oxidation-reduction reaction with the reducing substance to generate low valence active ions, so that the average valence state of the positive and negative electrode electrolyte active ions is reduced, and the oxidation-reduction reaction residues of a reducing agent are continuously introduced.
The fuel cell can also be constructed by reducing gas and positive electrode solution, such as hydrogen, and the noble metal catalyst is used for catalyzing and reducing the positive electrode active material to reduce the valence state, but the noble metal catalyst is easy to fall into the electrolyte, so that the negative electrode hydrogen evolution of the flow battery is aggravated and the capacity of the battery is rapidly attenuated.
Both of the above methods are not optimal for flow battery recovery methods.
Disclosure of Invention
The application provides a circulation recovery system and a recovery method of a flow battery, which realize capacity recovery of the flow battery on the premise of not introducing chemical substances to pollute electrolyte.
The technical scheme is that the flow battery cycle recovery system comprises:
The positive electrode liquid storage tank is internally provided with positive electrode electrolyte, the positive electrode electrolyte contains reducing ions and active ions, and the reducing ions can react with the active ions so as to reduce the valence state of the active ions and generate first oxidizing gas;
The catalytic reaction device is internally provided with a catalyst, is connected with the anode liquid storage tank, can receive the first oxidizing gas and is used for oxidizing and fixing the catalyst;
the negative electrode liquid storage tank is internally provided with a negative electrode electrolyte, the negative electrode electrolyte contains a supporting electrolyte, side reactions are easy to occur in the battery charging process or in the charging state of the supporting electrolyte to generate first reducing gas, the negative electrode liquid storage tank is connected with the catalytic reaction device, the catalytic reaction device can also receive the first reducing gas, the first reducing gas is used for reducing the oxidized catalyst, and the generated acid gas can return to the negative electrode liquid storage tank and is absorbed by the negative electrode electrolyte.
In some embodiments, the positive electrode liquid storage tank comprises a first air outlet end and a first air inlet end, the catalytic reaction device comprises a second air inlet end and a second air outlet end, and the recovery system further comprises:
the first pipeline is connected with the first air outlet end and the second air inlet end respectively and is used for conveying the first oxidizing gas from the positive electrode liquid storage tank to the catalytic reaction device;
and the second pipeline is respectively connected with the second air outlet end and the first air inlet end and is used for conveying the rest first oxidizing gas back to the positive electrode liquid storage tank through the catalytic reaction device after the catalyst is oxidized.
In some embodiments, the recovery system further comprises:
the first one-way conduction valve is arranged on the first pipeline.
In some embodiments, further comprising:
the positive electrode recovery device is connected with the positive electrode liquid storage tank, and can receive the positive electrode electrolyte and promote the positive electrode electrolyte to react to generate second oxidizing gas;
the positive electrode recovery device is also connected with the catalytic reaction device, the catalytic reaction device can receive the second oxidizing gas, and the second oxidizing gas is used for oxidizing and fixing the catalyst.
In some embodiments, the positive electrode reservoir includes a first liquid outlet end and a first liquid inlet end, the positive electrode recovery device includes a second liquid inlet end and a second liquid outlet end, and the recovery system further includes:
the third pipeline is respectively connected with the first liquid outlet end and the second liquid inlet end and is used for conveying the positive electrode electrolyte from the positive electrode liquid storage tank to the positive electrode recovery device;
and the fourth pipeline is respectively connected with the second liquid outlet end and the first liquid inlet end and is used for conveying the reacted positive electrolyte back to the positive liquid storage tank.
In some embodiments, the positive electrode restoration device further comprises a third air outlet end and a third air inlet end, and the restoration system further comprises:
the fifth pipeline is respectively connected with the third air outlet end and the second air inlet end and is used for conveying the second oxidizing gas from the positive electrode recovery device to the catalytic reaction device;
and the sixth pipeline is respectively connected with the second air outlet end and the third air inlet end and is used for conveying the rest second oxidizing gas from the catalytic reaction device back to the positive electrode recovery device after the catalyst is oxidized.
In some embodiments, the recovery system further comprises:
The second one-way conduction valve is arranged on the fifth pipeline.
In some embodiments, the negative electrode liquid storage tank comprises a fourth air outlet end and a fourth air inlet end, and the recovery system further comprises a seventh pipeline, a second pipeline and a third pipeline, wherein the seventh pipeline is respectively connected with the fourth air outlet end and the second air inlet end and is used for conveying the first reducing gas from the negative electrode liquid storage tank to the catalytic reaction device;
and the eighth pipeline is respectively connected with the second air outlet end and the fourth air inlet end and is used for conveying the gas generated after the oxidation of the catalyst in the catalytic reaction device back to the negative electrode liquid storage tank.
In some embodiments, the recovery system further comprises:
And the third one-way conduction valve is arranged on the seventh pipeline.
In some embodiments, further comprising:
The reduction gas source is connected with the catalytic reaction device and is used for introducing a second reduction gas into the catalytic reaction device; the catalytic reaction device receives the second reducing gas, and the second reducing gas is used for reducing the catalyst which has been oxidized;
and the tail gas treatment device is connected with the negative electrode liquid storage tank and is used for treating gas exhausted by the negative electrode liquid storage tank.
In some embodiments, the catalyst is selected from at least one of a copper-based catalyst, a nickel-based catalyst, a bismuth-based catalyst, or
The reducing ion is at least one selected from chloride ion and bromide ion, or
The active ion is selected from at least one of vanadium ion, manganese ion, bromine ion, iron ion, and lead ion, or
The supporting electrolyte is selected from at least one of sulfuric acid, hydrochloric acid and phosphoric acid;
the first oxidizing gas is selected from at least one of chlorine and bromine;
The first reducing gas is hydrogen.
In some embodiments, the second oxidizing gas is selected from at least one of chlorine, bromine, or
The second reducing gas is selected from at least one of hydrogen, carbon monoxide, methane and propane.
In some embodiments, the SOC of the positive electrode electrolyte before the reaction is 60% -100%, and the SOC of the positive electrode electrolyte after the reaction is 50% -100%.
In some embodiments, the present application further provides a flow battery cycle recovery method, including the steps of:
The method comprises the steps that positive electrolyte is filled in a positive liquid storage tank, wherein the positive electrolyte contains reducing ions and active ions, and the reducing ions react with the active ions to reduce the valence state of the active ions and generate first oxidizing gas;
Introducing the first oxidizing gas into a catalytic reaction device, wherein a catalyst is filled in the catalytic reaction device, and the first oxidizing gas reacts with the catalyst to oxidize and fix the catalyst;
The negative electrode liquid storage tank is filled with a negative electrode electrolyte, the negative electrode electrolyte contains a supporting electrolyte, and the supporting electrolyte is easy to generate side reaction to generate first reducing gas in the charging process or in the charging state of the battery;
And introducing the first reducing gas into a catalytic reaction device, wherein the first reducing gas and the oxidized catalyst undergo oxidation-reduction reaction, the catalyst is reduced and releases acid gas, and the generated acid gas can return to the negative electrode liquid storage tank and be absorbed by the negative electrode electrolyte.
In some embodiments, the molar ratio of the reducing ion to the active ion is (1-10): 0.1-5;
wherein the concentration of the reducing ions in the positive electrode electrolyte is 0.5-10 mol/L;
The concentration of the active ions in the positive electrode electrolyte is 0.1-5 mol/L.
The concentration of the supporting electrolyte in the negative electrode electrolyte is 0.5-10 mol/L.
In some embodiments, the reaction temperature of the reducing ion and the active ion is 20-100℃, or
The temperature of the reaction of the first oxidizing gas and the catalyst is 20-400 ℃, or
The reaction temperature of the first reducing gas with the catalyst that has been oxidized is 100-550 ℃, or in some embodiments, before the step of reacting the reducing ions with the active ions, further comprises:
introducing the positive electrode electrolyte into a positive electrode recovery device, reacting the positive electrode electrolyte to generate second oxidizing gas by adjusting the temperature, and reducing the valence state of the active ions;
And introducing a second oxidizing gas into the catalytic reaction device, wherein the second oxidizing gas reacts with the catalyst to oxidize the catalyst.
In some embodiments, in the positive electrode recovery device, the temperature is adjusted to a range of 20-100 ℃.
In some embodiments, before the step of reacting the first oxidizing gas with the catalyst and/or after the step of reacting the first reducing gas with the catalyst that has been oxidized,
Introducing a second reducing gas provided by a reducing gas source into a catalytic reaction device, and reacting the first reducing gas with the catalyst which is at least partially oxidized to completely reduce the catalyst;
and introducing the reacted gas into a negative electrode liquid storage tank, and then treating and discharging the gas through a tail gas treatment device.
Compared with the prior art, the circulation recovery system of the flow battery has the beneficial effects that the circulation recovery system comprises an anode liquid storage tank, an anode electrolyte is arranged in the anode liquid storage tank, the anode electrolyte contains reducing ions and active ions, the reducing ions can react with the active ions to reduce the valence state of the active ions and generate first oxidation gas, a catalytic reaction device is arranged in the catalytic reaction device and is connected with the anode liquid storage tank, the catalytic reaction device can receive the first oxidation gas and is used for oxidizing the catalyst, a cathode electrolyte is arranged in the cathode liquid storage tank, the cathode electrolyte contains supporting electrolyte, side reactions are easy to generate in the battery charging process or state, the supporting electrolyte is connected with the catalytic reaction device, the catalytic reaction device can also receive the first reduction gas, and the first reduction gas is used for reducing the oxidized catalyst. According to the circulating recovery system of the flow battery, provided by the application, the valence balance of the positive and negative solutions can be maintained without adding a recovery agent into the positive solution, so that the electrolyte is prevented from being polluted, and the application of the flow battery with long service life and no attenuation is realized. The application relates to a circulating recovery system of a flow battery, which is also introduced with an auxiliary reducing gas source to realize sufficient reduction of a catalyst and realize circulating application of the catalyst.
The flow battery cycle recovery system also comprises a positive electrode recovery device, wherein the positive electrode recovery device is connected with the positive electrode liquid storage tank, the positive electrode recovery device can receive positive electrode electrolyte and promote the reaction of the positive electrode electrolyte to generate second oxidizing gas, the positive electrode recovery device is also connected with a catalytic reaction device, the catalytic reaction device can receive the second oxidizing gas, and the second oxidizing gas is used for oxidizing the catalyst. The positive electrode recovery device can promote the reaction of the positive electrode electrolyte and generate second oxidizing gas, and the generated second oxidizing gas can react with the catalyst, so that the valence state of active ions in the positive electrode electrolyte is reduced, and the purpose of recovering the battery capacity is achieved.
The application discloses a circulation recovery method of a flow battery, which comprises the following steps that positive electrolyte is filled in a positive liquid storage tank, the positive electrolyte contains reducing ions and active ions, the reducing ions react with the active ions to reduce the valence state of the active ions and generate first oxidizing gas, the first oxidizing gas is introduced into a catalytic reaction device, a catalyst is filled in the catalytic reaction device, the first oxidizing gas reacts with the catalyst to oxidize the catalyst, negative electrolyte is filled in a negative liquid storage tank, the negative electrolyte contains supporting electrolyte, side reactions are easy to occur in the battery charging process or in the battery charging state to generate first reducing gas, the first reducing gas is introduced into the catalytic reaction device, the first reducing gas reacts with the oxidized catalyst in an oxidation-reduction reaction mode, the catalyst is reduced and releases acid gas, and the generated acid gas can return to the negative liquid storage tank and be absorbed by the negative electrolyte. The method of the application links the recovery process with the attenuation quantity and the SOC of the capacity of the flow battery, realizes the automatic operation of the recovery of the flow battery, can also prepare an optional recovery system externally connected with a reduction gas source, and can carry out external intervention adjustment of electrolyte according to the actual running condition.
Drawings
The technical solution and other advantageous effects of the present application will be made apparent by the following detailed description of the specific embodiments of the present application with reference to the accompanying drawings.
FIG. 1 is a schematic connection diagram of a flow battery cycle recovery system according to an embodiment of the present application;
FIG. 2 is a schematic connection diagram of an anode recovery device according to an embodiment of the present application;
FIG. 3 is a schematic diagram illustrating the connection of a reducing gas source according to an embodiment of the present application;
FIG. 4 is a schematic diagram of a flow battery configuration;
FIG. 5 is a flowchart of a flow battery cycle recovery method according to an embodiment of the present application;
FIG. 6 is a graph showing the comparison of the catalyst provided in the example of the present application before and after oxidation of chlorine and before and after reduction of hydrogen;
Reference numerals, 10-positive electrode liquid storage tank, 101-first air outlet end, 102-first air inlet end, 103-first liquid outlet end, 104-first liquid inlet end, 20-catalytic reaction device, 201-second air inlet end, 202-second air outlet end, 30-negative electrode liquid storage tank, 301-fourth air outlet end, 302-fourth air inlet end, 40-first pipeline, 401-first one-way conduction valve, 50-second pipeline, 60-positive electrode recovery device, 601-second liquid inlet end, 602-second liquid outlet end, 603-third air outlet end, 604-third air inlet end, 70-third pipeline, 80-fourth pipeline, 90-fifth pipeline, 901-second one-way conduction valve, 100-sixth pipeline, 200-seventh pipeline, 2001-third one-way conduction valve, 300-eighth pipeline, 400-reduction air source and 500-tail gas treatment device.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application. It will be apparent that the described embodiments are only some, but not all, embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to fall within the scope of the application.
In the description of the present application, unless explicitly stated or limited otherwise, the terms "connected" and "connected" should be interpreted broadly, for example, as being fixedly connected, detachably connected, or integrally connected, as being mechanically connected, electrically connected, or communicable with each other, as being directly connected, or indirectly connected through an intermediary, as being an internal connection between two elements, or as being an interaction relationship between two elements. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art according to the specific circumstances. In the description of the present application, the meaning of "a plurality" is two or more, unless explicitly defined otherwise. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more features.
In this example, the reagents or apparatus used were conventional products commercially available without the manufacturer's knowledge.
The following disclosure provides many different embodiments, or examples, for implementing different features of the application. In order to simplify the present disclosure, components and arrangements of specific examples are described below. They are, of course, merely examples and are not intended to limit the application.
Applicants have found that flow batteries are a new battery, which is an electrochemical energy storage technology proposed by thaeller. The flow battery consists of a pile unit, electrolyte, an electrolyte storage and supply unit, a management control unit and the like, is a high-performance storage battery which is separated by utilizing positive and negative electrolytes and circulates respectively, and has the characteristics of high capacity, wide use field (environment) and long circulating service life. The flow battery technology is used as a novel large-scale efficient electrochemical energy storage (electricity) technology, and the mutual conversion and energy storage of electric energy and chemical energy are realized through the valence state change of reactive substances. The schematic structural diagram of the flow battery is shown in fig. 4, the positive electrolyte and the negative electrolyte of the battery are respectively arranged in two storage tanks, and the electrolyte is circulated in the battery system by using a liquid feeding pump. The positive electrolyte and the negative electrolyte are separated by an ion exchange membrane (or ion diaphragm) in the electric pile, the battery is externally connected with a load and a power supply, the positive electrolyte and the negative electrolyte realize the oxidation-reduction reaction of corresponding pairs on the electrodes in the electric pile in the charge-discharge process, and the charge-discharge capacity of the flow battery can be inevitably attenuated to different degrees along with the continuous charge-discharge circulation operation.
Taking a vanadium-containing flow battery as an example, the average valence rise of vanadium ions in the positive and negative electrolyte caused by the hydrogen evolution reaction of the negative electrode is one of the important reasons for capacity fading of the flow battery. Positive electrodeNegative electrodeThe positive and negative active materials in the initial stage are equal in quantity, and in the circulating process, the negative electrolyte continuously generates hydrogen evolution reaction:
;
the valence state of vanadium ions is continuously increased, which is shown by gradually increasing the concentration of pentavalent vanadium in the positive electrode solution at the end of the discharging step, and the gradual attenuation of the battery capacity is directly caused.
In order to restore the capacity of the battery, usually, under the high SOC condition, a reducing substance is added into the positive electrode solution, and high valence active ions with stronger oxidizing property can undergo oxidation-reduction reaction with the reducing substance to generate low valence active ions, so that the average valence of the active ions of the positive and negative electrode electrolyte is reduced. The process continues with the introduction of redox reaction residues of the reducing agent. On the other hand, the method of fuel cells is one of the current research and application directions, a cell is constructed by using a reducing gas and a positive electrode solution, and a noble metal catalyst is used for catalyzing and reducing a positive electrode active material to reduce the valence state, but the noble metal catalyst is easy to fall off into an electrolyte, so that the hydrogen evolution of a negative electrode is increased, and the capacity of the cell is rapidly attenuated.
Therefore, a recovery method of a flow battery is needed to realize capacity recovery of the battery without introducing chemical substances to pollute electrolyte.
In view of the above problems, referring to fig. 1, an embodiment of the present application provides a circulation recovery system for a flow battery, including a positive electrode reservoir 10, a catalytic reaction device 20, and a negative electrode reservoir 30, wherein the positive electrode reservoir 10 is filled with a positive electrode electrolyte containing a reducing ion and an active ion, the reducing ion is capable of reacting with the active ion to reduce the valence state of the active ion and generate a first oxidizing gas, the catalytic reaction device 20 is filled with a catalyst, the catalytic reaction device 20 is connected with the positive electrode reservoir 10, the catalytic reaction device 20 is capable of receiving the first oxidizing gas and the first oxidizing gas is used for oxidizing the catalyst, the negative electrode reservoir 30 is filled with a negative electrode electrolyte containing a supporting electrolyte, a side reaction is liable to occur during or in a state of battery charging to generate a first reducing gas, the negative electrode reservoir 30 is connected with the catalytic reaction device 20, and the first reducing gas is also capable of receiving the first reducing gas and is used for reducing the catalyst that has been oxidized, so that the generated acidic gas is capable of returning to the negative electrode reservoir 30 and being absorbed by the negative electrode electrolyte.
The all-vanadium redox flow battery consists of a positive reaction pair and a negative reaction pair, wherein in the charging process, the positive electrode performs oxidation reaction, and the negative electrode performs reduction reaction:
VO 2++H2O=e-+VO2 ++2H+ (1V)
Negative electrode reaction V 3++ e-=V2+; (0.225V)
During the discharge process, the positive electrode undergoes a reduction reaction, and the negative electrode undergoes an oxidation reaction, contrary to the above reaction.
The positive electrode and the negative electrode of the battery are provided with active ions with the same mass, so that the battery can realize charge and discharge capacity theoretically, namely, when the mass of tetravalent vanadium ions in the positive electrode electrolyte is the same as that of trivalent vanadium ions in the negative electrode electrolyte in the initial state of charge, the number of electrons which can be charged in the positive electrode and the negative electrode is the same, or when the mass of pentavalent vanadium ions in the positive electrode is the same as that of divalent vanadium ions in the negative electrode in the initial state of discharge, the number of electrons which can be discharged in the electrochemical reaction of the positive electrode and the negative electrode is the same. The capacity of the battery depends on the minimum value of the two, namely, the lowest value of tetravalent vanadium ions in the positive electrode electrolyte and trivalent vanadium ions in the negative electrode electrolyte determines chargeable quantity in the initial state of charge, and the lowest value of pentavalent vanadium ions in the positive electrode and divalent vanadium ions in the negative electrode determines dischargeable quantity in the initial state of discharge.
At the battery negative electrode, a reduction reaction of hydrogen easily occurs:
2H++2e-=H2;(0V)
the potential of the anode II and the trivalent vanadium is lower than the standard potential of Hydrogen Evolution Reaction (HER), but the carbon felt is adopted as an electrode in the battery, so that the hydrogen evolution overpotential is higher, and the occurrence of the hydrogen evolution reaction can be greatly inhibited. However, the hydrogen evolution reaction cannot be completely inhibited and is irreversible. When the hydrogen evolution reaction occurs, the corresponding reaction of the positive electrode is oxidation of vanadium, the hydrogen evolution quantity is gradually accumulated along with the cyclic progress of the charging and discharging process of the battery, the total quantity of tetravalent vanadium contained in the positive electrode electrolyte is lower and lower, and the chargeable quantity of the battery is gradually reduced.
It can be understood that, in order to restore the capacity of the battery, in the system of this embodiment, the valence state of the active ions is reduced and the first oxidizing gas is generated by the reaction of the positive electrode electrolyte in the positive electrode liquid storage tank 10, specifically, the pentavalent vanadium is reduced to tetravalent, so that the total amount of tetravalent vanadium in the positive electrode is increased, and the total amount of tetravalent vanadium in the positive electrode is close to the trivalent vanadium in the negative electrode in the initial stage of charging, thereby realizing the restoration of the capacity of the battery. Referring to fig. 1, in some embodiments, the recovery system of the present application is a self-circulating closed system, and no additional device or gas source is introduced in the whole process, and no external recovery agent is needed, so that the recovery of the battery capacity can be ensured, and the electrolyte is prevented from being polluted.
In some embodiments, further referring to FIG. 1, positive electrode liquid reservoir 10 comprises a first gas outlet end 101 and a first gas inlet end 102, catalytic reaction device 20 comprises a second gas inlet end 201 and a second gas outlet end 202, the recovery system further comprises a first pipeline 40 and a second pipeline 50, the first pipeline 40 is respectively connected with the first gas outlet end 101 and the second gas inlet end 201 for conveying a first oxidizing gas from positive electrode liquid reservoir 10 to catalytic reaction device 20, and the second pipeline 50 is respectively connected with the second gas outlet end 202 and the first gas inlet end 102 for conveying remaining first oxidizing gas from catalytic reaction device 20 back to positive electrode liquid reservoir 10 after oxidation of the catalyst. It will be appreciated that the arrangement of the first and second lines 40, 50 enables the cyclic delivery of the first oxidizing gas from the positive electrode liquid reservoir 10 through the first line 40 to the catalytic reactor 20 and then back to the positive electrode liquid reservoir 10 through the second line 50, which ensures full use of the gas. The balance of active ions and reducing ions in the positive electrode electrolyte and the negative electrode electrolyte can be kept, so that the problem that the average valence state of the positive electrode electrolyte and the negative electrode electrolyte is higher due to side reactions such as hydrogen evolution in the traditional flow battery can be avoided, and the influence of capacity attenuation of the battery is reduced.
In some embodiments, with further reference to fig. 1, the recovery system further comprises a first one-way conduction valve 401, the first one-way conduction valve 401 being disposed on the first conduit 40. The first one-way conduction valve 401 allows the first oxidizing gas to flow out of the positive electrode tank 10 only, but not back into the positive electrode tank 10.
In some embodiments, referring further to fig. 2, the recovery system further comprises a positive electrode recovery device 60, the positive electrode recovery device 60 being connected to the positive electrode reservoir 10, the positive electrode recovery device 60 being capable of receiving a positive electrode electrolyte and promoting a reaction of the positive electrode electrolyte to produce a second oxidizing gas, the positive electrode recovery device 60 being further connected to the catalytic reaction device 20, the catalytic reaction device 20 being capable of receiving the second oxidizing gas, and the second oxidizing gas being used to oxidize the catalyst.
The positive electrode recovery device 60 is a device that promotes the reaction of the positive electrode electrolyte, reduces the active material in the positive electrode electrolyte, and generates a second oxidizing gas, which may be either chlorine or bromine. When the reaction speed of the reducing ions in the positive electrolyte and the high-valence active ions is too slow or the valence state of the active ions in the electrolyte needs to be greatly reduced, the positive electrode recovery device 60 needs to be connected, the high-SOC positive electrode electrolyte is pumped into the positive electrode recovery device, the temperature is regulated to realize the oxidation-reduction reaction of the reducing ions and the high-valence active ions, and a second oxidizing gas is generated, so that the valence state of the active ions in the positive electrode electrolyte is reduced, and the purpose of recovering the battery capacity is achieved.
In some embodiments, further referring to FIG. 2, positive electrode reservoir 10 includes a first liquid outlet end 103 and a first liquid inlet end 104, positive electrode restoration device 60 includes a second liquid inlet end 601 and a second liquid outlet end 602, and the restoration system further includes a third conduit 70 and a fourth conduit 80, wherein third conduit 70 is respectively connected to first liquid outlet end 103 and second liquid inlet end 601 for delivering positive electrode electrolyte from positive electrode reservoir 10 to positive electrode restoration device 60, and fourth conduit 80 is respectively connected to second liquid outlet end 602 and first liquid inlet end 104 for delivering reacted positive electrode electrolyte back to positive electrode reservoir 10. It will be appreciated that the third and fourth lines 70 and 80 are used to pump out the high SOC positive electrolyte from the positive electrode reservoir 10 and introduce it into the positive electrode restoration device 60 for reaction restoration and then return to the positive electrode reservoir 10.
In some embodiments, referring further to FIG. 2, positive electrode restoration device 60 further includes a third outlet port 603 and a third inlet port 604, the restoration system further includes a fifth conduit 90 and a sixth conduit 100, the fifth conduit 90 being respectively connected to the third outlet port 603 and the second inlet port 201 for delivering the second oxidizing gas from positive electrode restoration device 60 to catalytic reaction device 20, and the sixth conduit 100 being respectively connected to the second outlet port 202 and the third inlet port 604 for delivering the remaining second oxidizing gas from catalytic reaction device 20 back to positive electrode restoration device 60 after oxidation of the catalyst. The arrangement of the fifth pipeline 90 and the sixth pipeline 100 can keep the balance of active ions and reducing ions in the positive electrode electrolyte and the negative electrode electrolyte, which is helpful to avoid the problem of higher average valence state of the positive electrode electrolyte and the negative electrode electrolyte caused by side reactions such as hydrogen evolution in the traditional flow battery, thereby reducing the influence of capacity attenuation of the battery.
In some embodiments, referring to FIG. 2, the recovery system further comprises a second one-way conduction valve 901, the second one-way conduction valve 901 being disposed on the fifth conduit 90. The second one-way conduction valve 901 allows the first oxidizing gas to flow out from the positive electrode restoration device 60, preventing the first reducing gas from flowing into the positive electrode restoration device 60.
In some embodiments, referring further to FIG. 1, the negative electrode liquid reservoir 30 includes a fourth outlet port 301 and a fourth inlet port 302, and the recovery system further includes a seventh conduit 200 and an eighth conduit 300, the seventh conduit 200 being connected to the fourth outlet port 301 and the second inlet port 201, respectively, for delivering the first reducing gas from the negative electrode liquid reservoir 30 to the catalytic reaction device 20, and the eighth conduit 300 being connected to the second outlet port 202 and the fourth inlet port 302, respectively, for delivering the gas generated after oxidation of the catalyst in the catalytic reaction device 20 back to the negative electrode liquid reservoir 30. The seventh and eighth lines 200 and 300 circulate the first reducing gas and the gas generated after the oxidation by the catalyst in the catalytic reactor 20.
In some embodiments, the recovery system further comprises a third one-way conduction valve 2001, the third one-way conduction valve 2001 being provided on the seventh conduit 200. The third one-way conduction valve 2001 allows the first reducing gas to flow out of the anode reservoir 30, preventing the first oxidizing gas and the second oxidizing gas from flowing into the anode reservoir 30.
In some embodiments, referring to FIG. 3, the abatement system further includes a reducing gas source 400 and an exhaust gas treatment device 500, the reducing gas source 400 being coupled to the catalytic reaction device 20 for introducing a second reducing gas to the catalytic reaction device 20, the catalytic reaction device 20 receiving the second reducing gas and the second reducing gas for reducing the catalyst that has been oxidized, the exhaust gas treatment device 500 being coupled to the negative electrode liquid reservoir 30 for treating the gas exhausted by the negative electrode liquid reservoir 30. It will be appreciated that the arrangement of the reducing gas source 400 may further provide the second reducing gas to the catalytic reaction device 20, so as to ensure that the catalyst in the catalytic reaction device 20 is completely reduced, and maximize the reaction amount of the catalyst with the first oxidizing gas and the second oxidizing gas. The tail gas treatment device 500 can ensure that the gas discharged from the negative electrode liquid storage tank 30 is discharged after being catalyzed and oxidized to produce water or carbon dioxide, thereby avoiding environmental pollution.
In some embodiments, the catalyst is selected from at least one of copper-based catalysts, nickel-based catalysts, bismuth-based catalysts. Copper-based catalysts include, but are not limited to, copper oxide, copper chloride, cuprous chloride, cupric bromide, cupric iodide, copper-containing alloys, nickel-based catalysts include, but are not limited to, nickel oxide, nickel chloride, nickel bromide, nickel-containing alloys, and bismuth-based catalysts include, but are not limited to, bismuth oxide, bismuth chloride, bismuth bromide, bismuth-containing alloys.
In some embodiments, the catalyst reduction state may be judged by a color appearance, such as metallic luster, or the like. Referring to fig. 6, the pre-oxidation catalyst is in a light state, the post-oxidation catalyst is in a dark state, and the post-reduction catalyst returns to a light state.
In some embodiments, the reducing ion is selected from at least one of chloride and bromide.
In some embodiments, the reducing ion is provided by a component that releases chloride or bromide, such as one or more of perchloric acid, hypochlorous acid, chloric acid, hydrochloric acid, liquid bromine, hypobromous acid, hydrobromic acid, and hydrobromic acid.
In some embodiments, the active ion is selected from at least one of vanadium ion, manganese ion, bromide ion, iron ion, lead ion.
In some embodiments, the negative electrode electrolyte contains one or a mixture of several of vanadium ions, chromium ions, manganese ions, titanium ions, iron ions, zinc ions, tin ions, bismuth ions and mercury ions.
In some embodiments, the supporting electrolyte is selected from at least one of sulfuric acid, hydrochloric acid, phosphoric acid.
In some embodiments, the first oxidizing gas is selected from at least one of chlorine and bromine.
In some embodiments, the first reducing gas is hydrogen.
In some embodiments, the second oxidizing gas is selected from at least one of chlorine and bromine.
In some embodiments, the second reducing gas is selected from at least one of hydrogen, carbon monoxide, methane, propane.
In some embodiments, the SOC of the positive electrode electrolyte before the reaction is 60% -100%, and the SOC of the positive electrode electrolyte after the reaction is 50% -100%. Preferably, the SOC of the positive electrode electrolyte before the reaction is 75% -90%, and the SOC of the positive electrode electrolyte after the reaction is 60% -70%. Wherein SOC (State of Charge) represents the state of charge of the battery, which represents the ratio between the amount of charge currently stored by the battery and its maximum charge capacity.
In some embodiments, referring to fig. 5, there is also provided a flow battery cycle recovery method, comprising the steps of:
Introducing positive electrolyte into the positive liquid storage tank 10, wherein the positive electrolyte contains reducing ions and active ions, and the reducing ions react with the active ions to reduce the valence state of the active ions and generate first oxidizing gas;
Introducing a first oxidizing gas into the catalytic reaction device 20, wherein a catalyst is arranged in the catalytic reaction device 20, and the first oxidizing gas reacts with the catalyst to oxidize the catalyst;
Introducing a negative electrode electrolyte into the negative electrode liquid storage tank 30, wherein the negative electrode electrolyte contains a supporting electrolyte, and the supporting electrolyte is easy to generate side reaction to generate first reducing gas in the battery charging process or state;
The first reducing gas is introduced into the catalytic reaction device 20, and undergoes an oxidation-reduction reaction with the oxidized catalyst, the catalyst is reduced and acid gas is released, and the generated acid gas can be returned to the anode liquid storage tank 30 and absorbed by the anode electrolyte.
It can be understood that the method of the application links the recovery process with the attenuation amount and the SOC of the battery capacity, realizes the automatic operation of battery recovery, and solves the problem of battery capacity attenuation caused by higher average valence state of the positive and negative electrolyte due to side reactions such as hydrogen evolution of the flow battery.
In some embodiments, the molar ratio of reducing ion to active ion is (1-10): 0.1-5. Further preferably, the molar ratio of reducing ions to active ions may be any one or in a range between any two of 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1.
In some embodiments, the concentration of the reducing ion in the positive electrode electrolyte is 0.5-10 mol/L, and for example, the concentration can be any value or a range between any two values in 0.5 mol/L、0.6 mol/L、0.7 mol/L、0.8 mol/L、0.9 mol/L、1 mol/L、2 mol/L、3 mol/L、4 mol/L、5 mol/L、6 mol/L、7 mol/L、8 mol/L、9 mol/L、10 mol/L.
In some embodiments, the concentration of the active ions in the positive electrode electrolyte is 0.1-5 mol/L. For example, any one or a range between any two of 0.1 mol/L、0.2 mol/L、0.3 mol/L、0.4 mol/L、0.5 mol/L、0.6 mol/L、0.7 mol/L、0.8 mol/L、0.9 mol/L、1 mol/L、2 mol/L、3 mol/L、4 mol/L、5 mol/L.
In some embodiments, the concentration of the supporting electrolyte in the negative electrode electrolyte is 0.5-10 mol/L. For example, any one or a range between any two of 0.5 mol/L、0.6 mol/L、0.7 mol/L、0.8 mol/L、0.9 mol/L、1 mol/L、2 mol/L、3 mol/L、4 mol/L、5 mol/L、6 mol/L、7 mol/L、8 mol/L、9 mol/L、10 mol/L.
In some embodiments, the temperature at which the reducing ions react with the active ions is 20-100 ℃. For example, it may be any one value or a range between any two values of 20 ℃,30 ℃,40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃.
In some embodiments, the first oxidizing gas reacts with the catalyst at a temperature of 20-400 ℃, e.g., may be any one or a range between any two of 20 ℃, 50 ℃, 100 ℃, 120 ℃, 150 ℃, 180 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃.
In some embodiments, the reaction temperature of the first reducing gas and the catalyst that has been oxidized is 100-550 ℃, e.g., may be any one or a range between any two of 100 ℃, 150 ℃,200 ℃, 250 ℃,300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃.
In some embodiments, prior to the step of reacting the reducing ion with the active ion, further comprising:
Introducing the positive electrode electrolyte into a positive electrode recovery device 60, reacting the positive electrode electrolyte to generate a second oxidizing gas by adjusting the temperature, and reducing the valence state of the active ions;
The second oxidizing gas is introduced into the catalytic reaction device 20, and reacts with the catalyst to oxidize the catalyst.
It will be appreciated that the positive electrode restoring device 60 may further enhance the reaction between the reducing ions and the active ions in the positive electrode electrolyte to ensure the generation of the second oxidizing gas, thereby reducing the valence state of the active ions in the positive electrode electrolyte and achieving the purpose of restoring the battery capacity. The second oxidizing gas and the first oxidizing gas are the same gas and can be used for the reaction and oxidation reaction with the catalyst.
In some embodiments, in the positive electrode restoration device 60, the temperature is adjusted to be 20-100 ℃. For example, the adjusted temperature may be any one or a range between any two of 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃,50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃.
In some embodiments, the step of reacting the first oxidizing gas with the catalyst is preceded and/or followed by the step of reacting the first reducing gas with the catalyst that has been oxidized. When the amount of the first reducing gas is insufficient, the catalyst cannot be completely reduced.
Introducing a second reducing gas provided by a reducing gas source 400 into the catalytic reaction device 20 to completely reduce the catalyst;
The reacted gas is introduced into the anode liquid storage tank 30, and then treated and discharged through the exhaust gas treatment device 500.
It can be appreciated that, in addition to the flow battery cycle recovery system, an optional recovery system with an external reducing gas source 400 is configured, and external intervention adjustment of the electrolyte can be performed according to actual operation conditions.
By using the flow battery circulation recovery method, the charge-discharge circulation capacity of the battery is almost not attenuated, and the characteristics of the long-life non-attenuation flow battery are truly realized.
Specifically, a method for recovering a flow battery is provided, which comprises the following steps:
Step 1, loading a catalyst into a catalytic reaction device 20, circularly connecting the catalytic reaction device 20 into a reduction gas source 400, and introducing a second reduction gas into the catalyst placed in the catalytic reaction device 20 for pre-reduction, wherein the following reactions occur by taking nickel oxide as an example:
NiO(s)+CO(g)=Ni(s)+CO2(g);
The gas generated after the reaction is led into a negative electrode liquid storage tank through an external circulation pipeline and then is discharged after passing through a tail gas treatment device 500, and the step 2 is carried out after the reaction is finished;
Step 2, under high SOC, the reducing ions in the positive electrode liquid storage tank 10 react with the high valence active ions to generate a first oxidizing gas, and the reaction is as follows:
;
Step 3, switching an internal circulation pipeline, pumping a first oxidizing gas into the catalytic reaction device 20 through a first pipeline 40, taking a nickel catalyst as an example, and generating nickel chloride by the catalytic reaction device 20 through an absorption reaction;
Step 4, switching the circulation pipeline, pumping the first reducing gas generated in the negative electrode liquid storage tank 30 into the catalytic reaction device 20 through the seventh pipeline 200 to reduce the catalyst, wherein the reaction is as follows, taking nickel chloride as an example:
NiCl2(s)+H2(g) = Ni (s)+2HCl(g);
The gas (hydrogen chloride) generated in the catalytic reaction device 20 is introduced into the negative electrode liquid storage tank 30 through the eighth pipeline 300, the catalyst in a certain circulation volume is reduced to a target state, the step 2 is returned to, the internal circulation is realized, and otherwise, the step 5 is entered;
step 5, switching a circulating pipeline, and introducing external reducing gas (H 2) to reduce the catalyst, wherein the reaction is the same as the step 4;
Step 6, when the reaction speed of the reducing ions of the positive electrolyte and the high-valence active ions is too slow or the valence state of the active ions in the positive electrolyte needs to be greatly reduced, connecting the positive electrode recovery device 60, pumping the high-SOC positive electrolyte into the positive electrode recovery device 60 through a third pipeline 70, regulating the temperature to realize the oxidation-reduction reaction of the reducing ions and the active high-valence ions, generating halogen gas (such as chlorine), reducing the valence state of the active ions in the positive electrolyte, achieving the purpose of recovering the battery capacity, and conveying the reacted positive electrolyte back to the positive electrode liquid storage tank 10 through a fourth pipeline 80;
step 7, pumping the gas (containing the halogen gas) in the positive electrode recovery device 60 into the catalytic reaction device 20 through a fifth pipeline 90 for reaction in step 3, pumping the residual gas into the positive electrode recovery device 60 through a sixth pipeline 100 for realizing cyclic absorption, and then entering step 4 or step 5 again.
In the recovery method, the liquid circulation mode of the positive electrode electrolyte recovery is that a positive electrode liquid storage tank, a positive electrode recovery device and a positive electrode liquid storage tank.
In the recovery method, the circulation mode of the gas oxidation catalyst comprises 1) a positive electrode liquid storage tank, a catalytic reaction device and a positive electrode liquid storage tank, 2) a positive electrode recovery device, a catalytic reaction device and a positive electrode recovery device;
In the recovery method, the circulation mode of the gas reduction catalyst comprises 1) a negative electrode liquid storage tank, a gas device, a negative electrode liquid storage tank, and 2) a reduction gas source, a catalytic reaction device, a negative electrode liquid storage tank and a tail gas treatment device.
Specific application
Referring to Table 1, the initial average valence state of vanadium ions of the positive and negative electrolytes of the flow battery is 3.503, the single-side capacities of the positive and negative electrolytes are respectively positive 15894.83 Ah and negative 15964.52 Ah, the theoretical maximum capacity of the battery is 15894.83 Ah, and the initial concentration of positive pentavalent vanadium is 0.069 mol/L. After 100 charge-discharge cycles, the average valence state of the vanadium ions of the positive electrode and the negative electrode is increased from original 3.503 to 3.601, and the single-side capacity of the positive electrode electrolyte and the negative electrode electrolyte is respectively that the positive electrode 14054.07 Ah and the negative electrode 16800.69 Ah, and the theoretical maximum capacity of the battery is reduced to 14054.07 Ah. Charging the flow battery after 100 circles of circulation to a high SOC state, adjusting the valence state by adopting the flow battery circulation recovery system provided by the embodiment of the application, adjusting the temperature of a catalytic reaction device to 100 ℃, circulating chlorine gas introduced into a positive electrode liquid storage tank until the surface of a catalyst becomes black gray, adjusting the catalytic reaction device to 450 ℃, circulating hydrogen gas generated by hydrogen evolution reaction introduced into a negative electrode liquid storage tank for 60min, and switching to an external reducing gas until the color of the catalyst becomes silver gray.
TABLE 1
The sectional sampling detection results are shown in Table 1. After the first recovery cycle procedure, the positive electrode SOC is reduced from 88.81% to 73.17%, the average valence state of vanadium ions is recovered to 3.495, and the theoretical maximum capacity is recovered to 16119.37 Ah. The recovery cycle of the charge and discharge test is continuously completed for three periods, and the result shows that the theoretical maximum capacity is recovered to 15964.52 Ah, so that the recovery system can well maintain the battery capacity.
The above describes in detail a circulation recovery system and recovery method for a flow battery provided by the embodiments of the present application, and specific examples are applied to describe the principles and implementation manners of the present application, and the description of the above embodiments is only for helping to understand the technical solutions and core ideas of the present application, and those skilled in the art should understand that they can still modify the technical solutions described in the foregoing embodiments or substitute some technical features thereof, and these modifications or substitutions do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.
Claims (18)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411438680.5A CN118970130B (en) | 2024-10-15 | 2024-10-15 | A flow battery cycle recovery system and recovery method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411438680.5A CN118970130B (en) | 2024-10-15 | 2024-10-15 | A flow battery cycle recovery system and recovery method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN118970130A CN118970130A (en) | 2024-11-15 |
| CN118970130B true CN118970130B (en) | 2025-01-24 |
Family
ID=93387652
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202411438680.5A Active CN118970130B (en) | 2024-10-15 | 2024-10-15 | A flow battery cycle recovery system and recovery method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118970130B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111200154A (en) * | 2020-01-10 | 2020-05-26 | 西南交通大学 | Polyhalide-chromium flow battery |
| CN116711110A (en) * | 2020-12-31 | 2023-09-05 | 环球油品有限责任公司 | Redox flow battery with balancing cells |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003303611A (en) * | 2002-04-10 | 2003-10-24 | Sumitomo Electric Ind Ltd | How to operate a redox flow battery |
| CN113067025B (en) * | 2020-01-02 | 2022-04-29 | 中国科学院大连化学物理研究所 | Online recovery method for electrolyte of alkaline zinc-iron flow battery |
| CN114094148B (en) * | 2022-01-19 | 2022-04-19 | 杭州德海艾科能源科技有限公司 | Online capacity recovery method for all-vanadium redox flow battery |
-
2024
- 2024-10-15 CN CN202411438680.5A patent/CN118970130B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111200154A (en) * | 2020-01-10 | 2020-05-26 | 西南交通大学 | Polyhalide-chromium flow battery |
| CN116711110A (en) * | 2020-12-31 | 2023-09-05 | 环球油品有限责任公司 | Redox flow battery with balancing cells |
Also Published As
| Publication number | Publication date |
|---|---|
| CN118970130A (en) | 2024-11-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5318865A (en) | Redox battery | |
| US11233263B2 (en) | Redox flow battery systems and methods of manufacture and operation and reduction of metallic impurities | |
| ES2905553T3 (en) | Redox flow battery with a carbon dioxide-based redox couple | |
| Pan et al. | Preliminary study of alkaline single flowing Zn–O2 battery | |
| EP3641041B1 (en) | Carbon electrode for dichromate redox flow batteries | |
| CN108461758B (en) | A kind of negative electrode for all-vanadium redox flow battery and preparation method thereof, and all-vanadium redox flow battery | |
| JP3163370B2 (en) | Redox battery | |
| JP2018516428A (en) | Treatment method for liquid electrolyte | |
| JP2020087712A (en) | Method for manufacturing catalyst-supporting negative electrode for redox flow battery | |
| JP2994337B1 (en) | Method for regenerating electrolyte solution for all vanadium redox flow batteries | |
| CN118970130B (en) | A flow battery cycle recovery system and recovery method | |
| CN115020756B (en) | Zinc-bromine/iodine double flow battery | |
| CN113036195B (en) | Electrolyte of biomass flow fuel cell, preparation method of electrolyte and biomass flow fuel cell | |
| CN118743072A (en) | Increasing reactant utilization in FE/V flow batteries | |
| KR102063753B1 (en) | Energy storage system via iodine compound redox couples | |
| CN110071317A (en) | A kind of tin bromine flow battery | |
| JPH0628167B2 (en) | Secondary battery rebalancing method | |
| CN113871668A (en) | A reversible battery system and method based on electrochemical cycling of hydrogen peroxide | |
| CN112599829A (en) | Electrolyte for flow battery and polyhalide-chromium flow battery | |
| JPH07101615B2 (en) | Redox type secondary battery | |
| RU2803292C1 (en) | Method for producing an electrolyte for a vanadium flow redox battery | |
| CN119833690A (en) | Flow battery system and balancing method | |
| CN118431532B (en) | Electrolyte of iron-vanadium redox flow battery, preparation method and redox flow battery | |
| Jameson et al. | High Activity Carbonaceous Electrodes for Zinc-Iodine Flow Batteries | |
| KR20240144513A (en) | Apparatus for green hydrogen generation using redox active material and method for generating green hydrogen using the same |
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 |