CN116470111A - Positive electrode electrolyte for alkaline all-iron flow battery and preparation method thereof - Google Patents
Positive electrode electrolyte for alkaline all-iron flow battery and preparation method thereof Download PDFInfo
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- flow battery
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 108
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000001301 oxygen Substances 0.000 claims abstract description 36
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003112 inhibitor Substances 0.000 claims abstract description 16
- 239000003381 stabilizer Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 8
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 239000000276 potassium ferrocyanide Substances 0.000 claims description 6
- 239000000264 sodium ferrocyanide Substances 0.000 claims description 6
- 235000012247 sodium ferrocyanide Nutrition 0.000 claims description 6
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 claims description 6
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 239000001103 potassium chloride Substances 0.000 claims description 5
- 235000011164 potassium chloride Nutrition 0.000 claims description 5
- MWCFXRVLEYZWBD-UHFFFAOYSA-N tetralithium;iron(2+);hexacyanide Chemical compound [Li+].[Li+].[Li+].[Li+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] MWCFXRVLEYZWBD-UHFFFAOYSA-N 0.000 claims description 5
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 4
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims description 4
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 4
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 claims description 4
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 4
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- 229940079864 sodium stannate Drugs 0.000 claims description 4
- 229910001631 strontium chloride Inorganic materials 0.000 claims description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 3
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 claims description 2
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 229960004887 ferric hydroxide Drugs 0.000 abstract description 7
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 abstract description 7
- 239000002244 precipitate Substances 0.000 abstract description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract 1
- 229910001447 ferric ion Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 25
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 16
- 239000013543 active substance Substances 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 238000007600 charging Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 4
- -1 potassium ferricyanide Chemical compound 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910000604 Ferrochrome Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229940006198 sodium phenylacetate Drugs 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000005406 washing Methods 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
-
- 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
Abstract
The invention discloses a positive electrode electrolyte for an alkaline all-iron flow battery and a preparation method thereof, wherein the positive electrode electrolyte is prepared from ferrocyanide, a stabilizer, an oxygen evolution inhibitor, an alkaline component, an auxiliary electrolyte and water at a certain temperature, and the positive electrode electrolyte comprises the following components: the total iron concentration is 0.1-2.0 mol/L, the mole ratio of stabilizer/Fe is 0.05-1.0, the concentration of oxygen evolution inhibitor is 0.5-10 mg/L, the alkaline component is 0.5-3.0 mol/L, and the auxiliary electrolyte is 0-1.0 mol/L. The positive electrode electrolyte for the alkaline all-iron flow battery can improve the oxygen evolution overpotential of the strong alkaline positive electrode electrolyte, reduce the oxygen evolution rate, improve the electrochemical activity of ferrocyanide, effectively prevent the generation of ferric hydroxide precipitate, improve the stability of ferric ions, greatly prolong the cycle life of the positive electrode electrolyte, and can be widely applied to water-based flow batteries.
Description
Technical Field
The invention relates to the field of flow batteries, in particular to positive electrode electrolyte for an alkaline all-iron flow battery and a preparation method thereof
Background
The flow battery is a liquid-phase electrochemical energy storage device, active substances of the flow battery are completely dissolved in electrolyte, and energy storage and release are realized through oxidation valence state change of active elements, so that the flow battery belongs to a redox battery. The vanadium redox flow battery is used as a novel energy storage technology, has the characteristics of good stability, quick response, high efficiency, long cycle life and the like, is a mature redox flow battery with commercial prospect at present, but the electrolyte cost of the vanadium redox flow battery is high, accounts for more than 40% of the total energy storage cost, and limits the application of the vanadium redox flow battery in the energy storage field to a certain extent.
Among positive electrode electrolyte active materials of all-iron flow batteries, ferrocyanide/ferricyanide has been a recent research hot spot due to its safety and stability and superior electrochemical reversibility. The Jian Luo et al research shows that under neutral or alkaline conditions, the electrochemical performance of the potassium ferrocyanide/potassium ferricyanide half-cell is very good, and the capacity attenuation rate of the half-cell is negligible; however, a significant decay in the capacity of the half-cell was observed under strongly alkaline conditions (ph=14) due to the cleavage of the fe—cn chemical bond in potassium ferricyanide, forming ferric hydroxide precipitates leading to a significant decay in capacity. (Luo, J., sam, A., hu, B., deBruler, C., wei, X., wang, W., and Liu, T.L. (2017) Unraveling pH Dependent cycling stability of ferricyanide/ferrocyanide in redox flow batteries. Nano Energy 42, 215-221)
Ferricyanide is slowly decomposed into ferric hydroxide precipitate in a strong alkaline environment (ph=14), so that the concentration of active substances in electrolyte is reduced, and ferric hydroxide generated by precipitation is attached to the surfaces of an electrode and a diaphragm, so that the internal resistance of a cell is increased, and the long-time cycling stability of a galvanic pile is affected. Meanwhile, in a strong alkaline environment (ph=14), the oxygen evolution potential of the positive electrode electrolyte is about 0.4V, which is close to the electrode potential of the active substance ferrocyanide, and the active substance (ferrocyanide) loses electrons and at the same time, OH - The ions can lose electrons and become oxygen, so that the charge and discharge capacity of positive and negative electrolyte active substances is unstable, the capacity retention rate of the alkaline all-iron flow battery is reduced, and the industrialization prospect of the flow battery of the system is limited.
CN113013461 a discloses a positive electrode electrolyte of an alkaline zinc-iron flow battery, sodium tetraborate is added to the strong alkaline positive electrode electrolyte as a buffer solution, the pH value of the positive electrode electrolyte is maintained between 8 and 11, and although the decomposition of ferricyanide as an active substance and the oxygen evolution rate are slowed down to a certain extent, the decomposition of ferricyanide as an active substance and the oxygen evolution rate still exist, and as the charge and discharge times of the alkaline zinc-iron flow battery are increased, the decomposition rate of ferricyanide and the oxygen evolution rate are gradually increased, so that the problems existing above cannot be effectively solved essentially; and the use environments of the alkaline all-iron flow battery and the alkaline zinc-iron flow battery positive electrolyte are strong alkaline, the pH value is more than 12, and the stability of the alkaline flow battery positive electrolyte cannot be regulated and controlled by controlling the pH value.
Disclosure of Invention
In order to solve the technical problems of short cycle life, low efficiency and the like of the alkaline all-iron flow battery, the invention provides the positive electrode electrolyte for the alkaline all-iron flow battery and the preparation method thereof, and the proper stabilizer and the oxygen evolution inhibitor are selected to solve the problems that the positive electrode electrolyte generates ferric hydroxide sediment and improves oxygen evolution overpotential under alkaline conditions, reduce oxygen evolution rate, improve the stability of iron ions, greatly improve the energy efficiency and the cycle life of the alkaline all-iron flow battery, and can be widely applied to water-based flow batteries.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the positive electrode electrolyte for the alkaline all-iron flow battery is characterized in that: the positive electrode electrolyte is prepared from ferrocyanide, a stabilizer, an oxygen evolution inhibitor, an alkaline component, an auxiliary electrolyte and water, wherein: the total iron concentration is 0.1-2.0 mol/L, the mole ratio of stabilizer/Fe is 0.05-1.0, the concentration of oxygen evolution inhibitor is 0.5-10 mg/L, the alkaline component is 0.5-3.0 mol/L, and the auxiliary electrolyte is 0-1.0 mol/L.
The invention has the better technical scheme that: the ferrocyanide in the positive electrode electrolyte is one or more of sodium ferrocyanide, potassium ferrocyanide and lithium ferrocyanide; the stabilizer in the positive electrode electrolyte is one or more of citric acid, hydroxyethylidene diphosphonic acid, ethylenediamine di-o-phenyl sodium acetate, amino trimethylene phosphonic acid, ethylenediamine tetramethylene sodium phosphate and sulfosalicylic acid; the oxygen evolution inhibitor in the positive electrode electrolyte is one or more of indium chloride or indium nitrate, strontium chloride or strontium nitrate, bismuth nitrate or bismuth chloride, stannic trichloride or sodium stannate, antimony trichloride and lead chloride; the alkaline component in the positive electrode electrolyte is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide; the auxiliary electrolyte in the positive electrode electrolyte is one or more of potassium chloride, sodium chloride and lithium chloride.
The preparation method of the invention comprises the following steps:
1) Adding ferrocyanide and deionized water into a reactor with a stirring jacket, and then continuously introducing high-purity nitrogen into the reactor as a protective gas, and heating to 30-60 ℃ while stirring;
2) Slowly adding a stabilizing agent into the solution in the step 1) until the stabilizing agent is completely dissolved, and continuously stirring and reacting for 1-2 hours;
3) Slowly adding an oxygen evolution inhibitor into the step 2) until the oxygen evolution inhibitor is completely dissolved, and continuously stirring and reacting for 1-2 hours;
4) Slowly dissolving the alkaline component in distilled water;
5) Slowly dripping the alkaline component water solution in the step 4) into the step 3), and continuously stirring for reacting for 1-2 hours after the alkaline component is completely dripped;
6) Slowly adding auxiliary electrolyte into the step 5), and continuously stirring at 30-60 ℃ for 8-24 hours after complete dissolution to obtain the positive electrode electrolyte.
Compared with the prior art, the invention has the following advantages:
(1) The stabilizer such as citric acid, ethylenediamine di-o-sodium phenylacetate (EDDHA) and sulfosalicylic acid is adopted, contains a plurality of hydrophilic groups such as hydrophilic-COOH, amide groups or sulfonic acid groups, can form a stable five-membered ring reticular three-dimensional structure with iron ions, has high stability constant, and is difficult to dissociate the iron ions even under the strong alkaline condition; the hydroxyl ethylidene diphosphonic acid (HEDP), amino trimethylene phosphonic Acid (ATMP), ethylenediamine tetramethylene sodium phosphate (EDTMPS) and the like contain a plurality of phosphate groups or N and other coordination heteroatoms, are easy to form coordination bonds with the outermost d orbit of the central ion iron to form a stable six-membered ring chelate, are stable at high temperature and high pH value, are not easy to hydrolyze, prevent ferricyanide from forming ferric hydroxide precipitation under the strong alkaline condition, and greatly improve the stability of the positive electrode electrolyte.
(2) The oxygen evolution inhibitor such as metal compound (ln, sr, bi, sn, sb and Pb) is added in the positive electrode electrolyte, which not only has higher electrocatalytic activity, but also greatly improves Fe 2+ /Fe 3+ The electrocatalytic activity and electrochemical reversibility of the oxidation-reduction reaction reduce the electron transfer resistance and improve the voltage efficiency and the energy efficiency of the all-iron flow battery; can also improve OH - The separation potential of the electrolyte of the positive electrode is reduced, so that the efficiency of the battery is improved, the performance attenuation is slowed down, and the long-term efficient and stable operation of the battery is ensured.
(3) The highest solubility of the lithium ferrocyanide can reach 2.0mol/L, the capacity is up to 53.6Ah/L, and the capacity is higher than the charge-discharge capacity of all-vanadium redox flow batteries, ferrochrome redox flow batteries and zinc-iron redox flow batteries; the energy density is very high, and the construction space of the energy storage power station is greatly reduced.
(4) The alkaline all-iron flow battery provided by the invention has the advantages of low cost, environmental protection, flame retardance, high safety and low cost, and can be stably circulated for a long time.
Drawings
FIG. 1 cyclic voltammograms (CV curves) of examples 1-5 and comparative example 1
FIG. 2 polarization curves (LSV curves) of examples 1-5 and comparative example 1
FIG. 3 discharge capacities of ferrocyanide/ferricyanide half-cells composed of examples 1 to 5 and comparative example 1
FIG. 4 capacity retention of alkaline all-iron flow batteries composed of examples 1-5 and comparative example 1
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, preferred embodiments of the present invention will be described below with reference to examples, but it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, and are not limiting the claims of the present invention.
1 preparation process of alkaline all-iron flow battery
1.1 preparation of positive electrolyte:
examples 1 to 5 and comparative example 1 were prepared as follows:
1) Adding ferrocyanide and deionized water into a reactor with a stirring jacket, and then continuously introducing high-purity nitrogen into the reactor as a protective gas, and heating to 30-60 ℃ while stirring;
2) Slowly adding a stabilizing agent into the solution in the step 1) until the stabilizing agent is completely dissolved, and continuously stirring and reacting for 1-2 hours;
3) Slowly adding an oxygen evolution inhibitor into the step 2) until the oxygen evolution inhibitor is completely dissolved, and continuously stirring and reacting for 1-2 hours;
4) Slowly dissolving the alkaline component in distilled water;
5) Slowly dripping the alkaline component water solution in the step 4) into the step 3), and continuously stirring for reacting for 1-2 hours after the alkaline component is completely dripped;
6) Slowly adding auxiliary electrolyte into the step 5), and continuously stirring at 30-60 ℃ for 8-24 hours after complete dissolution to obtain the positive electrode electrolyte.
1.2 preparation of negative electrode electrolyte:
the preparation process comprises the following steps: a negative electrode electrolyte containing Fe (0.1M) -TEA (0.4M) was prepared by metering 0.1mol of ferric chloride, 0.4mol of Triethanolamine (TEA), 2mol of NaOH,1mol of potassium chloride and a certain amount of distilled water with oxygen removal to 1L.
Example 1
A positive electrode electrolyte for an alkaline all-iron flow battery: 0.1mol of sodium ferrocyanide, 0.1mol of citric acid, 5mg of indium chloride, 5mg of indium nitrate, 3mol of potassium hydroxide, 1mol of sodium chloride and a certain amount of deoxidized distilled water are fixed to a volume of 1L, and a positive electrode electrolyte containing Fe (0.1M) -citric acid (0.1M) -indium chloride/indium nitrate (5 mg/L/5 mg/L) is prepared.
Example 2
A positive electrode electrolyte for an alkaline all-iron flow battery: 0.2mol of potassium ferrocyanide, 0.05mol of sulfosalicylic acid, 0.05mol of ethylenediamine di-o-phenyl sodium acetate (EDDHA), 5mg of strontium chloride, 5mg of strontium nitrate, 2mol of sodium hydroxide, 0.5mol of potassium chloride and a certain amount of deoxidized distilled water are fixed to a volume of 1L, and a positive electrode electrolyte containing Fe (0.2M) -sulfosalicylic acid/EDDHA (0.05M/0.05M) -strontium chloride/strontium nitrate (5 mg/L/5 mg/L) is prepared.
Example 3
A positive electrode electrolyte for an alkaline all-iron flow battery: 0.2mol of potassium ferrocyanide, 0.2mol of lithium ferrocyanide, 0.1mol of hydroxyethylidene diphosphonic acid (HEDP), 2mg of bismuth chloride, 2mg of bismuth nitrate, 1mol of lithium hydroxide, 0.5mol of lithium chloride and a certain amount of deoxidized distilled water are fixed to a volume of 1L, and a positive electrode electrolyte containing Fe (0.4M) -HEDP (0.1M) -bismuth chloride/bismuth nitrate (2 mg/L/2 mg/L) is prepared.
Example 4
A positive electrode electrolyte for an alkaline all-iron flow battery: 0.5mol of potassium ferrocyanide, 0.5mol of sodium ferrocyanide, 0.025mol of amino trimethylene phosphonic Acid (ATMP), 0.025mol of ethylenediamine tetramethylene sodium phosphate (EDTMPS), 1mg of stannic trichloride, 1mg of sodium stannate, 0.5mol of sodium hydroxide and a certain amount of deoxidized distilled water are fixed to a volume of 1L, and a positive electrode electrolyte containing Fe (1.0M) -ATMP/EDTMPS (0.025M/0.025M) -stannic trichloride/sodium stannate (1 mg/L/1 mg/L) is prepared.
Example 5
A positive electrode electrolyte for an alkaline all-iron flow battery: 2.0mol of lithium ferrocyanide, 0.1mol of citric acid, 0.5mg of indium chloride, 0.5mol of lithium hydroxide and a certain amount of deoxidized distilled water are fixed to a volume of 1L, and a positive electrode electrolyte containing Fe (2.0M) -citric acid (0.1M) -indium chloride (0.5 mg/L) is prepared.
Comparative example 1
The positive electrode electrolyte containing 0.1M sodium ferrocyanide was prepared by constant volume of 0.1mol sodium ferrocyanide, 1mol potassium hydroxide, 1mol potassium chloride and a certain amount of distilled water for oxygen removal to 1L.
2 electrochemical Performance test of alkaline all-iron flow Battery
2.1 cyclic voltammograms (CV curves) and polarization curves (LSV curves)
Experimental conditions: three electrode mode (electrochemical workstation: shanghai Chen Hua instruments Co., ltd., CHI 660E), working electrode: graphite felt electrode (commercial electrode), diameter 6mm, thickness 3mm, counter electrode: platinum sheet electrode (15×15×0.1 mm), reference electrode: ag/AgCl, voltage range: 0-1.0V; scanning voltage: the cyclic voltammograms of examples 1 to 5 and comparative example 1 are shown in FIG. 1, the peak current values (Ipa and Ipc), the peak current ratio (Ipa/Ipc), the peak potential difference (ΔEp) and the oxygen evolution potential are shown in Table 1.
TABLE 1 electrochemical parameters corresponding to cyclic voltammograms
Remarks: the total iron concentrations in examples 1 to 5 and comparative example 1 were diluted to 0.1mol/L with distilled water after oxygen removal.
As can be seen from the above table 1 and fig. 1, the peak current ratios of the positive electrode electrolytes of examples 1 to 5 are close to 1.0, the peak potential difference is less than 200mv, and the peak current ratio of the positive electrode electrolyte of comparative example 1 deviates from 1.0, the peak potential difference is higher than 200mv, and the peak current values of the positive electrode electrolytes of examples 1 to 5 are significantly higher than the peak current value of the positive electrode electrolyte of comparative example 1 by 20% to 80%. This indicates that the electrochemical activity of the positive electrode electrolytes of examples 1 to 5 is significantly higher than that of the positive electrode electrolyte of comparative example 1.
TABLE 2 oxygen evolution potential of the positive electrode electrolytes of examples 1 to 5 and comparative example 1
As is apparent from table 2 above and fig. 2 above, the positive electrode electrolytes of examples 1 to 5 have significantly higher oxygen evolution potential than comparative example 1, and the oxygen evolution rates of examples 1 to 5 are significantly lower than comparative example 1, which indicates that the positive electrode electrolytes of examples 1 to 5 have significantly higher oxygen evolution inhibition effect than the comparative examples.
2.2 alkaline all-iron flow Battery Performance test
(1) Assembly of alkaline all-iron flow battery
The single cells were assembled in the following order: an aluminum end plate for positive electrode, a copper plate plated with gold, a graphite current collector, a graphite felt (Liaoning Jingu carbon materials Co., ltd.) for positive electrode of 2cm x 3mm, an ion exchange membrane Nafion212 (which is prepared by repeatedly washing with distilled water for 1 day after immersing in the electrolyte for positive electrode before use), a graphite felt for negative electrode of 2cm x 3mm, a graphite current collector, a copper plate plated with gold and an aluminum end plate for negative electrode.
Flow battery: the battery is formed by connecting the positive electrode electrolyte, the negative electrode electrolyte, the positive electrode electrolyte tank, the negative electrode electrolyte tank, a circulating pump, a circulating pipeline and a single cell circuit in series.
(2) Ferrocyanide/ferricyanide half-cell charge-discharge performance
Charge and discharge tester: charging and discharging mode of the wuhan blue electric electronics company CT 3002A: in the constant-current charging mode, the volume of the positive and negative electrolyte is 15ml, the flow rate of the positive and negative electrolyte is 50ml/min, and the current density is: 100mA/cm2, temperature: 30 ℃, graphite felt: 2cm x 3mm, ion exchange membrane: nafion212 adopts argon as protective gas all the time in the charge and discharge process, and the charge and discharge cut-off voltage is as follows: -0.4V, charge-discharge times: 500 times. Positive electrode electrolyte: examples 1 to 5 and comparative example 1, negative electrode electrolytes: half cell experiments (total iron concentrations in examples 1 to 5 and comparative example 1 were diluted to 0.1mol/L with distilled water after oxygen removal) in which ferrocyanide in the positive electrode electrolyte was replaced with ferricyanide and ferrocyanide/ferricyanide was combined with the positive electrode electrolyte. Fig. 3 shows the discharge capacities of the ferrocyanide/ferricyanide half-cells having the compositions of examples 1 to 5 and comparative example 1.
As can be seen from the above fig. 3, the discharge capacity of the ferrocyanide/ferricyanide half-cell composed of examples 1 to 5 was maintained substantially unchanged after 500 charge and discharge cycles, and neither fine bubbles nor red flocculent precipitate were found in the positive and negative electrolyte tanks and the pipeline, but the discharge capacity of the ferrocyanide/ferricyanide half-cell composed of comparative example 1 was drastically reduced after 500 charge and discharge cycles, and fine bubbles and red flocculent precipitate were clearly observed in the positive and negative electrolyte tanks and the pipeline. It was found by examination that the concentration of ferricyanide in the negative electrode electrolyte of comparative example 1 was reduced by nearly 60% compared with the original concentration, because ferrocyanide in the positive electrode electrolyte lost electrons while OH - Partial electrons are lost to generate oxygen, so that the concentration of active substances in positive and negative electrolyte is unbalanced, the concentration of ferrocyanide in negative electrolyte is continuously accumulated, the charge and discharge capacity of the half cell is continuously reduced, and the capacity retention rate is also continuously reduced. This shows that the effect of the positive electrode electrolytes of examples 1 to 5 on preventing the formation of ferric hydroxide precipitate and on suppressing oxygen evolution are significantly higher than those of comparative example 1.
(3) Charging and discharging performance of alkaline all-iron flow battery
Charge and discharge tester: charging and discharging mode of the wuhan blue electric electronics company CT 3002A: in the constant-current charging mode, the volume of the electrolyte of the positive electrode and the negative electrode is 15ml, the flow rate of the electrolyte of the positive electrode and the negative electrode is 50ml/min, and the current density is 80mA/cm 2 Temperature: argon was used as a shielding gas during charging and discharging at 30℃and the charge and discharge cut-off voltages were 1.6V and 0.7V, respectively, and the number of times of charging and discharging was 500, and Table 3 shows the coulombic efficiencies and voltage efficiencies of examples 1 to 5 and comparative example 1The capacity retention rates of alkaline flow batteries having the compositions of examples 1 to 5 are shown in fig. 4.
Table 3 alkaline all-iron flow battery performance table
As is apparent from Table 3 above, examples 1 to 5 have coulombic efficiencies of 92 to 96%, voltage efficiencies of 90 to 94%, and energy efficiencies of 85 to 90%, which are significantly higher than comparative example 1.
As can be seen from fig. 4, the capacity retention rate after 500 charges and discharges in examples 1 to 5 is about 75 to 85%, and the capacity retention rate is relatively high, whereas the capacity retention rate after 500 charges and discharges in comparative example 1 is about 40%, and the capacity decay rate is relatively high. This demonstrates that the charge and discharge performance of alkaline all-iron flow batteries of examples 1-5 is significantly better than that of comparative example 1.
Claims (7)
1. The positive electrode electrolyte for the alkaline all-iron flow battery is characterized in that: the positive electrode electrolyte is prepared from ferrocyanide, a stabilizer, an oxygen evolution inhibitor, an alkaline component, an auxiliary electrolyte and water, wherein: the total iron concentration is 0.1-2.0 mol/L, the mole ratio of stabilizer/Fe is 0.05-1.0, the concentration of oxygen evolution inhibitor is 0.5-10 mg/L, the alkaline component is 0.5-3.0 mol/L, and the auxiliary electrolyte is 0-1.0 mol/L.
2. The positive electrode electrolyte for an alkaline all-iron flow battery according to claim 1, wherein the positive electrode electrolyte is characterized by: the ferrocyanide in the positive electrode electrolyte is one or more of sodium ferrocyanide, potassium ferrocyanide and lithium ferrocyanide.
3. The positive electrode electrolyte for an alkaline all-iron flow battery according to claim 1, wherein the positive electrode electrolyte is characterized by: the stabilizing agent in the positive electrode electrolyte is one or more of citric acid, hydroxyethylidene diphosphonic acid, ethylenediamine di-o-phenyl sodium acetate, amino trimethylene phosphonic acid, ethylenediamine tetramethylene sodium phosphate and sulfosalicylic acid.
4. The positive electrode electrolyte for an alkaline all-iron flow battery according to claim 3, wherein the positive electrode electrolyte is characterized by: the oxygen evolution inhibitor in the positive electrode electrolyte is one or more of indium chloride or indium nitrate, strontium chloride or strontium nitrate, bismuth nitrate or bismuth chloride, stannic trichloride or sodium stannate, antimony trichloride and lead chloride.
5. The negative electrode electrolyte for an alkaline all-iron flow battery of claim 1, wherein the negative electrode electrolyte comprises: the alkaline component in the positive electrode electrolyte is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
6. The positive electrode electrolyte for an alkaline all-iron flow battery according to claim 1, wherein the positive electrode electrolyte is characterized by: the auxiliary electrolyte in the positive electrode electrolyte is one or more of potassium chloride, sodium chloride and lithium chloride.
7. A negative electrode electrolyte for an alkaline all-iron flow battery is characterized in that: the preparation method of the negative electrode electrolyte comprises the following steps:
1) Adding ferrocyanide and deionized water into a reactor with a stirring jacket, and then continuously introducing high-purity nitrogen into the reactor as a protective gas, and heating to 30-60 ℃ while stirring;
2) Slowly adding a stabilizing agent into the solution in the step 1) until the stabilizing agent is completely dissolved, and continuously stirring and reacting for 1-2 hours;
3) Slowly adding an oxygen evolution inhibitor into the step 2) until the oxygen evolution inhibitor is completely dissolved, and continuously stirring and reacting for 1-2 hours;
4) Slowly dissolving the alkaline component in distilled water;
5) Slowly dripping the alkaline component water solution in the step 4) into the step 3), and continuously stirring for reacting for 1-2 hours after the alkaline component is completely dripped;
6) Slowly adding auxiliary electrolyte into the step 5), and continuously stirring at 30-60 ℃ for 8-24 hours after complete dissolution to obtain the positive electrode electrolyte.
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