CN118016944A - Water system iron-cerium flow battery - Google Patents
Water system iron-cerium flow battery Download PDFInfo
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- CN118016944A CN118016944A CN202410171545.2A CN202410171545A CN118016944A CN 118016944 A CN118016944 A CN 118016944A CN 202410171545 A CN202410171545 A CN 202410171545A CN 118016944 A CN118016944 A CN 118016944A
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- electrolyte
- cerium
- iron
- flow battery
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- ZGMCLEXFYGHRTK-UHFFFAOYSA-N [Fe].[Ce] Chemical compound [Fe].[Ce] ZGMCLEXFYGHRTK-UHFFFAOYSA-N 0.000 title claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 6
- 239000003792 electrolyte Substances 0.000 claims abstract description 70
- 239000000126 substance Substances 0.000 claims abstract description 31
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229960003330 pentetic acid Drugs 0.000 claims abstract description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002738 chelating agent Substances 0.000 claims abstract description 13
- 239000003115 supporting electrolyte Substances 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 235000002639 sodium chloride Nutrition 0.000 claims description 13
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 150000000703 Cerium Chemical class 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000013522 chelant Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000003411 electrode reaction Methods 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- FZQSLXQPHPOTHG-UHFFFAOYSA-N [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 Chemical compound [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 FZQSLXQPHPOTHG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 239000001103 potassium chloride Substances 0.000 claims description 6
- 235000011164 potassium chloride Nutrition 0.000 claims description 6
- 239000003014 ion exchange membrane Substances 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000007772 electrode material Substances 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 230000000087 stabilizing effect Effects 0.000 claims description 3
- AGMNQPKGRCRYQP-UHFFFAOYSA-N 2-[2-[2-[bis(carboxymethyl)amino]ethylamino]ethyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCNCCN(CC(O)=O)CC(O)=O AGMNQPKGRCRYQP-UHFFFAOYSA-N 0.000 claims description 2
- FPFSGDXIBUDDKZ-UHFFFAOYSA-N 3-decyl-2-hydroxycyclopent-2-en-1-one Chemical compound CCCCCCCCCCC1=C(O)C(=O)CC1 FPFSGDXIBUDDKZ-UHFFFAOYSA-N 0.000 claims description 2
- OZZDRAZPBLIJDX-UHFFFAOYSA-N C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.NCCNCCN.[Na].[Na] Chemical compound C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.NCCNCCN.[Na].[Na] OZZDRAZPBLIJDX-UHFFFAOYSA-N 0.000 claims description 2
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- BITPWMGGNIMTIN-UHFFFAOYSA-N [Na].[Na].[Na].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCN Chemical compound [Na].[Na].[Na].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCN BITPWMGGNIMTIN-UHFFFAOYSA-N 0.000 claims description 2
- WQCOKGWXGCPFBK-UHFFFAOYSA-N [Na].[Na].[Na].[Ca].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCN Chemical compound [Na].[Na].[Na].[Ca].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCN WQCOKGWXGCPFBK-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 229910021538 borax Inorganic materials 0.000 claims description 2
- 229960001759 cerium oxalate Drugs 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- 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 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- IZOOGPBRAOKZFK-UHFFFAOYSA-K gadopentetate Chemical compound [Gd+3].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O IZOOGPBRAOKZFK-UHFFFAOYSA-K 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 230000036647 reaction Effects 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- 239000004328 sodium tetraborate Substances 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 abstract description 10
- 239000012528 membrane Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000012864 cross contamination Methods 0.000 abstract 1
- 230000005518 electrochemistry Effects 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 10
- 239000013543 active substance Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000010248 power generation Methods 0.000 description 4
- 210000001787 dendrite Anatomy 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000032895 transmembrane transport Effects 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- Fuel Cell (AREA)
Abstract
A water system iron-cerium flow battery belongs to the field of electrochemistry, and has the characteristics of stable performance, low cost and environmental friendliness, and is suitable for the field of large-scale energy storage. The positive electrode electrolyte and the negative electrode electrolyte are prepared by adopting the same chelating agent coordination mode, so that the stability of the iron electrolyte and the cerium electrolyte is improved, and the cross-membrane cross-contamination is reduced. The chelating agent is mainly selected from one or more of diethylenetriamine pentaacetic acid (DTPA) and its derivative chemicals. Besides the chelating agent and the active component, the electrolyte also comprises a supporting electrolyte and an auxiliary electrolyte, so that the pH environment of the electrolyte is further stabilized and the conductivity is improved. The invention has the characteristics of easy scale, long cycle life, high energy density, high energy utilization efficiency and the like.
Description
Technical Field
The invention relates to the technical field of flow batteries, in particular to a novel iron-cerium flow battery which can be widely applied to large-scale energy storage of new energy sources such as wind energy, solar energy and the like and industries such as electric power, traffic and the like.
Background
In recent years, the wide application of renewable energy power generation technologies (such as solar power generation, wind power generation and the like) greatly increases the pressure bearing of power grid power facilities, and a large-scale energy storage technology is urgently needed to solve the problems of intermittence, periodicity and the like of renewable power. The existing electric power energy storage technology comprises pumping energy storage, compressed air energy storage, flywheel energy storage, battery energy storage and the like. The flow battery is a novel large-scale electrochemical energy storage device, and has the characteristics of long circulation, safety, reliability, low cost and the like, so that the flow battery is in global attention. Unlike conventional batteries, the active materials of flow batteries are stored in a storage tank, and electrolyte is circulated back and forth in the battery system by a pump. The electrode of the flow battery is made of electrochemical inert material, is a place where the active substance generates oxidation-reduction reaction, and does not participate in the electrode reaction. Therefore, the power and the capacity of the flow battery can be independently designed, the power depends on the type of active substances and the size of a galvanic pile, and the capacity mainly depends on the amount and the concentration of electrolyte.
However, current all-vanadium flow batteries with higher commercialization face the challenge of higher cost of vanadium raw materials, while other low-cost hybrid flow batteries present a risk of metal dendrites, largely impeding their widespread use. In this case, a new iron-cerium flow battery with low cost, full solubility is expected to be an attractive candidate in flow batteries. In the traditional iron-containing flow battery, the negative electrode reaction is deposition and stripping reaction of Fe on the electrode, and the coordination structure of Fe ions and water is easy to cause hydrogen evolution reaction, so that the failure and capacity loss of the battery are accelerated, and the service life of the flow battery is reduced. In addition, some ferrocyanide electrolytes on the positive electrode side have a problem in that ferric hydroxide precipitates. The invention prepares a novel iron-cerium flow battery which takes chelate formed by ferric salt chemicals, diethylenetriamine pentaacetic acid (DTPA) and derivative chemicals thereof as a negative electrode electrolyte and takes chelate formed by cerium salt chemicals, DTPA and derivative chemicals thereof as a positive electrode electrolyte by adopting a novel chelating agent coordination mode.
Disclosure of Invention
The invention aims to provide a novel iron-cerium flow battery with high stability and high energy density, which solves the problems of metal dendrite, hydrogen evolution reaction and high cost in the existing flow battery technology and expands the utilization range of cerium resources.
The novel iron-cerium flow battery is mainly improved on the basis of the existing flow battery. The structure of the flow battery comprises a negative electrode electrolyte storage tank, a negative electrode electrolyte delivery pump, a positive electrode electrolyte storage tank, a positive electrode electrolyte delivery pump, an ion exchange membrane, electrode materials, a pile with a plurality of single cells integrated, electrolyte and a control system. The key point of the invention is that the active component of the electrolyte, namely the negative electrode electrolyte, is chelate of ferric salt chemicals and DTPA and derivative chemicals thereof, and the active component of the positive electrode electrolyte is chelate of cerium salt chemicals and DTPA and derivative chemicals thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The novel iron-cerium flow battery comprises positive electrode electrolyte and negative electrode electrolyte, and is characterized in that: the active component of the negative electrode electrolyte is chelate of ferric salt chemicals and diethylenetriamine pentaacetic acid (DTPA) and derivative chemicals thereof, the active component of the positive electrode electrolyte is chelate of cerium salt chemicals and DTPA and derivative chemicals thereof, and the electrode reaction during charging is as follows:
Negative electrode reaction: fe (Fe) 3++e→Fe2+
Positive electrode reaction: ce (Ce) 3+-e→Ce4+
The total cell reaction is: fe (Fe) 3++Ce3+→Fe2++Ce4+
The discharge is the reverse reaction of the above reaction.
Inactive components in the positive and negative electrolytes include a supporting electrolyte and an auxiliary electrolyte for stabilizing the pH and improving the conductivity, preferably stabilizing the pH to alkaline.
The ferric salt chemical used by the negative electrode electrolyte is selected from one or more of ferric chloride, ferric ammonium sulfate, ferric nitrate and ferric acetate; the cerium salt chemical used by the anode is selected from one or more of cerium sulfate, cerium acetate, cerium nitrate, cerium trichloride and cerium oxalate; the concentration of the positive and negative active material ferric salt and cerium salt chemicals in the electrolyte is 0-2 mol/L and is not 0, and the preferable range is 0.5-1.2 mol/L;
The chelating agent is one or more of DTPA and its derivative chemicals, including one or more of disodium diethylenetriamine pentaacetic acid, trisodium diethylenetriamine pentaacetic acid, gadolinium diethylenetriamine pentaacetic acid, diethylenetriamine tetraacetic acid, trisodium calcium diethylenetriamine pentaacetic acid and its hydrate. The DTPA and the chelating agent of the derivative chemicals thereof for the anode and the cathode are 1 to 1.2 times, preferably 1 time, the mole number of the corresponding iron and cerium elements.
The supporting electrolyte in the solution is one or more selected from potassium carbonate, sodium carbonate, lithium carbonate, potassium tetraborate, sodium tetraborate, potassium hydroxide and sodium hydroxide; the auxiliary electrolyte is selected from one or more of potassium sulfate, sodium sulfate, ammonium sulfate, potassium chloride, ammonium chloride, sodium chloride, potassium nitrate and sodium nitrate. The concentration of the supporting electrolyte is 0 to 10mol/L, preferably 1 to 4mol/L; the concentration of the auxiliary electrolyte is 0-2 mol/L.
The structure of the battery comprises an anode liquid storage tank and a cathode liquid storage tank, an ion exchange membrane divides a battery cell into an anode chamber and a cathode chamber, the anode is arranged in the anode chamber, the cathode is arranged in the cathode chamber, the internally generated current is connected with an external load or a power supply through a current collecting plate, and the anode electrolyte and the cathode electrolyte are circulated in a loop formed by the respective liquid storage tanks and the anode chamber through a circulating pump for charge and discharge.
The anode and cathode electrode materials are selected from one of carbon felt, graphite plate, graphite paper, carbon paper and carbon cloth inert materials, one of Nafion117, nafion115, nafion212 and Nafion211 is a battery diaphragm, the operation temperature is 10-70 ℃, and the electrolyte is circulated by a pump.
Compared with the prior art, the invention has the following remarkable advantages and beneficial effects:
according to the novel iron-cerium flow battery, the anode electrolyte and the cathode electrolyte enable ferric salt, cerium salt and DTPA chelating agents to form ligand compounds in a chelating coordination mode, so that the problems of metal dendrite formation and hydrogen evolution reaction of iron in the traditional process are avoided, the service life of the flow battery is prolonged, the solubility and energy density of the electrolyte are greatly improved, and the running cost of a flow battery system is reduced. Meanwhile, the anode and the cathode adopt the same chelating agent ligand, so that capacity and energy loss caused by ligand transmembrane transport are eliminated, the stability of the battery is improved, and the loss of active substances caused by side reaction is reduced. The active substances, the chelating agent, the supporting electrolyte and the auxiliary electrolyte used in the invention are industrial chemicals which are widely applied, and the invention has the advantages of simple production process, low cost, easy scale and no environmental safety hidden trouble. In addition, the invention provides a new choice for the comprehensive, cyclic and green utilization of rare earth resources. The novel iron-cerium flow battery can be used as large-scale electric energy storage and high-efficiency conversion equipment in wind energy and solar power generation systems, and has wide application prospect and potential.
Drawings
Fig. 1 is a schematic diagram of the working principle and structure of an iron-cerium flow battery.
Fig. 2 is a graph showing the results of cycle test efficiency of the iron-cerium flow battery of the example.
Fig. 3 is a cycle test capacity result of the iron-cerium flow battery of the example.
Fig. 4 is a graph showing the results of the rate test of the iron-cerium flow battery of the example.
Fig. 5 is a graph showing the results of the rate test capacity of the iron-cerium flow battery of the example.
Detailed Description
The present invention will be described in detail by way of specific examples, but the purpose and purpose of these exemplary embodiments are merely to illustrate the present invention, and not to limit the actual scope of the present invention in any way.
Examples:
As shown in FIG. 1, the novel iron-cerium flow battery system comprises a single cell, an anode liquid storage tank, a cathode liquid storage tank, a peristaltic pump, an anti-corrosion circulating pipeline and a battery test system. Wherein the single cell assembly has: aluminum end plates, polytetrafluoroethylene gaskets, collector plates, graphite bipolar plates, fluororubber gaskets, proton exchange membranes and graphite felt electrodes. The internally generated current is connected with an external load or a power supply through a current collecting plate, and electrolyte is circularly charged and discharged in a loop formed by a liquid storage tank and a galvanic pile through a circulating pump. The active component of the negative electrode electrolyte is chelate of ferric salt chemicals, DTPA and derivative chemicals thereof, and the active component of the positive electrode electrolyte is chelate of cerium salt chemicals, DTPA and derivative chemicals thereof.
In the embodiment, ferric chloride is adopted as the negative electrode electrolyte ferric salt, DTPA is adopted as the chelating agent, potassium carbonate and potassium tetraborate are adopted as supporting electrolytes, potassium chloride is adopted as auxiliary electrolytes, and oxygen-free deionized water is adopted as a solvent. Wherein, the concentration of iron ions is 1mol/L, the concentration of DTPA is 1.05mol/L, the concentration of potassium chloride is 1mol/L, and the concentrations of potassium carbonate and potassium tetraborate regulate the final pH value of the solution to 8.
The positive electrolyte cerium salt adopts cerium sulfate, the chelating agent is DTPA, potassium carbonate and potassium tetraborate are used as supporting electrolytes, potassium chloride is used as auxiliary electrolyte, and the anaerobic deionized water is used as solvent. Wherein the concentration of cerium ions is 1mol/L, the concentration of DTPA is 1.05mol/L, the concentration of potassium chloride is 1mol/L, and the final pH value of the solution is adjusted to 8 by potassium carbonate and potassium tetraborate.
And taking a certain volume of the positive and negative electrolyte, and adding the positive and negative electrolyte into a liquid storage tank of the flow battery. Wherein the concentration and volume of the electrolyte determine the size of the battery capacity. The higher the electrolyte concentration, the higher the energy density of the cell and the smaller the electrolyte volume required. The electrode material is graphite felt electrode with 5mm thickness, and the compression ratio is 40%. The ion exchange membrane divides the battery cell into a positive electrode chamber and a negative electrode chamber, wherein the positive electrode is arranged in the positive electrode chamber, and the negative electrode is arranged in the negative electrode chamber. The ion exchange membrane is Nafion212. After the battery is assembled, inert gas is filled in the whole battery system pipeline, so that the deactivation of active substances and the deterioration of alkaline electrolyte are avoided. And (5) accessing a battery test system, and starting a peristaltic pump test.
170 Charge-discharge cycle tests were carried out on the iron-cerium flow battery, the charging current is 80mA/cm 2, the upper limit and the lower limit of charging are respectively 1.2V and 0.5V, and the efficiency results are shown in figure 2. Among them, coulombic Efficiency (CE) approaches 100% after the cell is stabilized, proving that the cell does not undergo side reactions such as hydrogen evolution reaction during charge and discharge or capacity loss due to trans-membrane transport. Energy Efficiency (EE) is mainly related to Voltage Efficiency (VE), demonstrating that the kinetics of redox reactions and internal cell resistance (performance of membrane materials, conductivity of electrolyte, etc.) are key factors limiting the performance of iron-cerium flow batteries. Fig. 3 shows the capacity fade over 170 cycles for a flow battery of an embodiment at 100% state of charge (SOC). After 170 charge-discharge cycles, the discharge capacity is 62% of the first discharge capacity, and the cycle stability is good.
Fig. 4 is a graph of the efficiency of the rate performance test of the iron-cerium flow battery, and the tested current densities are 60mA/cm2,80mA/cm2,100mA/cm2,120mA/cm2,140mA/cm2,160mA/cm2,180mA/cm2,60mA/cm2., which shows that the iron-cerium flow battery can still maintain the energy efficiency of more than 50% under the test of up to 180mA/cm 2, and the discharge capacity of the iron-cerium flow battery under different current densities in fig. 5 has no drastic change, so that the iron-cerium flow battery has excellent performance under high density and is very suitable for application scenarios of large-scale energy storage.
Claims (8)
1. The electrolyte of the iron-cerium flow battery is divided into positive electrolyte and negative electrolyte, and is characterized in that: the active component of the negative electrode electrolyte is chelate of ferric salt chemicals and diethylenetriamine pentaacetic acid (DTPA) and derivative chemicals thereof, the active component of the positive electrode electrolyte is chelate of cerium salt chemicals and DTPA and derivative chemicals thereof, and the electrode reaction during charging is as follows:
Negative electrode reaction: fe (Fe) 3++e→Fe2+
Positive electrode reaction: ce (Ce) 3+-e→Ce4+
The total cell reaction is: fe (Fe) 3++Ce3+→Fe2++Ce4+
The reverse reaction of the above reaction is performed during discharge;
inactive components in the positive and negative electrode electrolytes comprise a supporting electrolyte and an auxiliary electrolyte, and are used for stabilizing pH to be alkaline and improving conductivity.
2. The electrolyte of the iron-cerium flow battery according to claim 1, wherein: the ferric salt chemical used by the negative electrode electrolyte is selected from one or more of ferric chloride, ferric ammonium sulfate, ferric nitrate and ferric acetate; the cerium salt chemical used in the anode is one or more selected from cerium sulfate, cerium acetate, cerium nitrate, cerium trichloride and cerium oxalate.
3. The electrolyte of the iron-cerium flow battery according to claim 1, wherein: the chelating agent is one or more of DTPA and its derivative chemicals, including one or more of disodium diethylenetriamine pentaacetic acid, trisodium diethylenetriamine pentaacetic acid, gadolinium diethylenetriamine pentaacetic acid, diethylenetriamine tetraacetic acid, trisodium calcium diethylenetriamine pentaacetic acid and its hydrate.
4. The novel iron-cerium flow battery according to claim 1, wherein: the supporting electrolyte in the solution is one or more selected from potassium carbonate, sodium carbonate, lithium carbonate, potassium tetraborate, sodium tetraborate, potassium hydroxide and sodium hydroxide; the auxiliary electrolyte is selected from one or more of potassium sulfate, sodium sulfate, ammonium sulfate, potassium chloride, ammonium chloride, sodium chloride, potassium nitrate and sodium nitrate.
5. The electrolyte of the iron-cerium flow battery according to claim 1, wherein: the concentration of the positive and negative active material ferric salt and cerium salt chemicals in the electrolyte is 0-2 mol/L and is not 0, and the preferable range is 0.5-1.2 mol/L; the DTPA and the chelating agent of the derivative chemicals thereof for the anode and the cathode are 1 to 1.2 times, preferably 1 time, the mole number of the corresponding iron and cerium elements.
6. The electrolyte of the iron-cerium flow battery according to claim 1, wherein: the concentration of the supporting electrolyte is 0 to 10mol/L, preferably 1 to 4mol/L; the concentration of the auxiliary electrolyte is 0-2 mol/L.
7. An iron cerium flow battery, characterized in that: a flow battery comprising the iron-cerium flow battery electrolyte of any one of claims 1-7.
8. The iron-cerium flow battery of claim 7, wherein: the structure of the battery comprises an anode liquid storage tank and a cathode liquid storage tank, wherein an ion exchange membrane divides a battery cell into an anode chamber and a cathode chamber, the anode is arranged in the anode chamber, the cathode is arranged in the cathode chamber, the internally generated current is connected with an external load or a power supply through a current collecting plate, and the anode electrolyte and the cathode electrolyte are circulated in a loop formed by the respective liquid storage tanks and the anode chamber through a circulating pump for charge and discharge;
The anode and cathode electrode materials are selected from one of carbon felt, graphite plate, graphite paper, carbon paper and carbon cloth inert materials, one of Nafion117, nafion115, nafion212 and Nafion211 is a battery diaphragm, the operation temperature is 10-70 ℃, and the electrolyte is circulated by a pump.
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