CN112500438A - Ferrocene-viologen bipolar active substance and preparation method and application thereof - Google Patents
Ferrocene-viologen bipolar active substance and preparation method and application thereof Download PDFInfo
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- CN112500438A CN112500438A CN202011310192.8A CN202011310192A CN112500438A CN 112500438 A CN112500438 A CN 112500438A CN 202011310192 A CN202011310192 A CN 202011310192A CN 112500438 A CN112500438 A CN 112500438A
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- 239000013543 active substance Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title description 3
- 239000003792 electrolyte Substances 0.000 claims description 83
- 150000003839 salts Chemical class 0.000 claims description 40
- 239000007788 liquid Substances 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 22
- 239000012266 salt solution Substances 0.000 claims description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011149 active material Substances 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- 150000001450 anions Chemical class 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 239000003115 supporting electrolyte Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000003011 anion exchange membrane Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000011550 stock solution Substances 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 239000007832 Na2SO4 Substances 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052925 anhydrite Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910001626 barium chloride Inorganic materials 0.000 claims description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000005341 cation exchange Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 238000000502 dialysis Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims 1
- 239000007774 positive electrode material Substances 0.000 claims 1
- 238000003756 stirring Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
The invention belongs to the technical field of flow batteries, and particularly relates to a ferrocene-viologen bipolar active substance and an application thereof in an organic water-phase salt-cavern battery.
Description
Technical Field
The invention belongs to the technical field of flow batteries, and particularly relates to a ferrocene-viologen bipolar active substance and application thereof in an organic water phase salt cavern battery.
Background
The ever-increasing energy demand necessitates a wide range of more efficient use of some renewable energy sources such as wind, solar and tidal energy. But renewable energy power generation has volatility, intermittence and randomness, so that seamless connection between the renewable energy power generation and a power grid is a problem, and energy storage is a necessary means for realizing high-proportion access of renewable energy to the power grid. Among various energy storage technologies, the flow battery technology is a battery with a good application prospect, and has the advantages of large capacity, high safety, long service life, high efficiency and the like, so that the flow battery technology is the first choice of a large-scale energy storage technology.
The salt cavity is an underground cavity of an underground salt layer after water-soluble salt mine exploitation, has the advantages of large capacity, good sealing performance, small permeability coefficient and the like, and is commonly used for storing petroleum, natural gas and the like. The flow battery needs a larger storage tank to store the battery electrolyte, the floor area is large, the underground salt cavern is used as the storage tank to store the flow battery electrolyte, the problem is solved, and the comprehensive utilization of salt cavern resources is realized. Currently, the developed flow batteries mainly adopt inorganic electrolytes, such as vanadium flow batteries and zinc-bromine flow batteries, but face the problems of strong acid systems or high toxicity of active substances, and the like, and have great influence on the ecological environment. In recent years, an organic aqueous phase flow battery has been considered as one of the promising applications in flow batteries, because the electrolyte has rich choices, and the neutral aqueous phase electrolyte is environmentally friendly and cheap. However, both inorganic flow batteries and organic flow batteries have the problem that electrolytes on both sides cross and penetrate during the long-time operation of the batteries, so that the efficiency of the batteries is influenced.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the invention provides a cation and anion type bipolar active material which can be used as an anode active material and a cathode active material of a flow battery simultaneously and improves the battery efficiency, aiming at the technical problem that the battery efficiency is influenced by the fact that electrolytes on two sides are crossed and permeated in the long-time running process of the battery.
The technical scheme adopted by the invention for solving the technical problems is as follows: a ferrocene-viologen bipolar active substance is prepared by introducing anions to ferrocene or its derivatives through functional modification to form a novel organic metal salt with viologen organic matter in an ionic form. The reaction equation is as follows:
wherein R is1、R2、R3Represents a group containing carbon, hydrogen, nitrogen, oxygen, fluorine or sulfur elements.
The preparation method of the ferrocene-viologen bipolar active substance comprises the following steps:
s1: introducing an anion on the ferrocene or the derivative thereof;
s2: respectively dissolving the modified ferrocene derivatives with negative charges and the viologen organic matters in an organic solvent;
s3: and (4) reacting the two solutions in the step S2 according to the charge molar ratio, filtering the precipitated solid, and spin-drying the solvent to obtain the solid of the ferrocene-viologen bipolar active substance.
In the step S1, the anion includes-COO-、-SO3 -Or PO3 2-。
The organic solvent in the step S2 is acetonitrile, DMF, methanol or DMSO.
The application of the ferrocene-viologen bipolar active substance can be used as a positive electrode active substance and a negative electrode active substance of a flow battery at the same time.
The application of the ferrocene-viologen bipolar active substance in an organic water phase salt cavern battery comprises the following steps:
the electrolyte tank is filled with electrolyte;
the two polar plates are respectively arranged in the electrolyte tank body and are opposite in position;
the battery diaphragm, the battery diaphragm is located in the electrolyte tank body and will the electrolyte tank body divide for one the positive pole district of electrolyte stock solution storehouse intercommunication and with another the negative pole district of electrolyte stock solution storehouse intercommunication, one the polar plate is located the positive pole district, another the polar plate is located the negative pole district, all have the electrolyte including ferrocene-viologen bipolar active material in the positive pole district and the negative pole district, the battery diaphragm can allow the effective of supporting the electrolyte to pass through.
The concentration of the ferrocene-viologen bipolar active substance is 0.01-4 mol/L.
The supporting electrolyte is a single-component neutral saline solution or a mixed neutral saline solution.
The supporting electrolyte is NaCl salt solution, KCl salt solution, Na2SO4Salt solution, K2SO4Salt solution, MgCl2Salt solution, MgSO4Salt solution, CaCl2Salt solution, CaSO4Salt solution, BaCl2Salt solution, BaSO4At least one salt solution.
The battery diaphragm is one of an anion exchange membrane, a cation exchange membrane, a selective permeable membrane, an anion and cation composite exchange membrane, a dialysis membrane or a porous membrane.
The application of the ferrocene-viologen bipolar active substance in the organic water phase salt cavern battery also comprises the following steps:
the two electrolyte liquid storage banks are respectively filled with electrolyte;
the circulating pipeline inputs or outputs the electrolyte in one electrolyte storage reservoir to or from the anode region, and the circulating pipeline inputs or outputs the electrolyte in the other electrolyte storage reservoir to or from the cathode region;
and the circulating pump is arranged on the circulating pipeline and enables the electrolyte to circularly flow and be supplied through the circulating pump.
The depth of the salt cavern is 100-2000 m underground, and the physical volume is 5 ten thousand m3About 50 km3The geothermal temperature is 25-70 ℃, the diameter of the dissolving cavity of the salt cavern is 40-120 m, and the height is 60-400 m.
The application of the ferrocene-viologen bipolar active substance in the organic water phase salt cavern battery also comprises the following steps:
the electrolyte liquid outlet pipe is arranged at the opening of the salt cavity, the lower end of the electrolyte liquid outlet pipe extends below the liquid level of the electrolyte in the salt cavity, and the upper end of the electrolyte liquid outlet pipe is connected with the circulating pipeline so as to output the electrolyte in the salt cavity through the electrolyte liquid outlet pipe;
the electrolyte liquid inlet pipe is arranged at the opening of the salt cavern and sleeved in the electrolyte liquid outlet pipe, the lower end of the electrolyte liquid inlet pipe faces the direction of the electrolyte in the salt cavern, and the upper end of the electrolyte liquid inlet pipe is connected with the circulating pipeline so as to input the electrolyte in the electrolyte liquid storage to the salt cavern.
The inner diameters of the electrolyte outlet pipe and the electrolyte inlet pipe are 10 cm-60 cm, and the outer diameters of the electrolyte outlet pipe and the electrolyte inlet pipe are 20 cm-80 cm.
The ferrocene-viologen bipolar active substance has the beneficial effects that the ferrocene-viologen bipolar active substance has bipolar property, can be used as a positive electrode active substance and a negative electrode active substance of a flow battery at the same time, avoids the problem of cross permeation pollution in the operation of the flow battery, improves the service life and the efficiency of the flow battery, has better water solubility and stability, does not need to be charged and discharged under the protection of inert gas, and can be applied to a salt cavity organic flow battery.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is a 200-cycle voltammogram according to example 1 of the present invention;
FIG. 2 is a rotating disk electrode test and active species diffusion coefficient calculation according to example 1 of the present invention;
FIG. 3 is a graph of cell efficiency versus cycle number according to example 1 of the present invention;
FIG. 4 is a graph of charge and discharge capacity versus cycle number according to example 1 of the present invention;
FIG. 5 is a graph of potential versus charge-discharge capacity for different numbers of charge and discharge cycles according to example 1 of the present invention;
Detailed Description
The present invention will now be described in further detail with reference to the accompanying drawings. These drawings are simplified schematic views illustrating only the basic structure of the present invention in a schematic manner, and thus show only the constitution related to the present invention.
Example 1
Respectively dissolving the solid (A) and the solid (B) in acetonitrile of 10mL according to the molar ratio of 2:1, mixing and stirring the solution in which the solid (A) and the solid (B) are dissolved after all the raw materials are dissolved to generate a white solid, continuously stirring for 2 hours, carrying out suction filtration on the white solid, and carrying out spin drying on the solvent to obtain the target product.
FIGS. 1 to 5 show the electrochemical properties of the prepared active material, and the diffusion coefficient of the positive part of the prepared anion-cation bipolar active material is 1.061 × 10-5cm2(s) the diffusion coefficient of the negative electrode portion was 5.288X 10-6cm2/s。
And (3) testing the battery performance:
the underground depth of 600m and the physical volume of 10 ten thousand m are adopted3Two salt cavities with height of 80m, maximum diameter of 60m and geothermal temperature of 30 ℃ are used as storage tanks of the negative and positive electrolytes, and the inner diameter of the sleeve is 20cm and the outer diameter is 50 cm.
The positive and negative electrode electrolytes used the electrolyte synthesized in example 1, and had a concentration of 0.2mol/L, and the supporting electrolyte used a 1.5mol/L NaCl solution, and had a volume of 8.0 mL. The electrolyte viscosity was about 10 mPas. The positive and negative electrodes are graphite felt electrodes, and the battery diaphragm is anion exchangeAnd (5) replacing the film. Single cell stack at a current density of 10mA/cm2The coulombic efficiency is 99%, the voltage efficiency is 88% and the energy efficiency is 88%.
Example 2
Respectively dissolving the solid (A) and the solid (B) in 12mL of DMF according to the molar ratio of 2:1, mixing and stirring the solution in which the solid (A) and the solid (B) are dissolved after all the raw materials are dissolved to generate a white solid, continuously stirring for 4 hours, carrying out suction filtration on the white solid, and spin-drying the solvent to obtain the target product.
And (3) testing the battery performance:
adopts the underground depth of 800m and the physical volume of 12 ten thousand m3Two salt cavities with the height of 83m, the maximum diameter of 605m and the geothermal temperature of 40 ℃ are used as storage tanks of the negative and positive electrolytes, the inner diameter of the sleeve is 20cm, and the outer diameter is 53 cm.
The positive and negative electrode electrolytes used the electrolyte synthesized in example 1, and had a concentration of 0.25mol/L, and the supporting electrolyte used a 1.2mol/L NaCl solution, and a volume of 10 mL. The electrolyte viscosity was about 12 mPas. The positive and negative electrodes are graphite felt electrodes, and the battery diaphragm is an anion exchange membrane. Single cell stack at a current density of 15mA/cm2The coulombic efficiency is 99%, the voltage efficiency is 80%, and the energy efficiency is 82%.
Example 3
Respectively dissolving the solid (A) and the solid (B) in 15mL of DMSO according to a molar ratio of 2:1, mixing and stirring the solution in which the solid (A) and the solid (B) are dissolved after all the raw materials are dissolved, generating a white solid, continuously stirring for 3h, carrying out suction filtration on the white solid, and spin-drying the solvent to obtain the target product.
And (3) testing the battery performance:
the underground depth is 1000m, and the physical volume is 20 ten thousandm3Two salt cavities with the height of 100m, the maximum diameter of 80m and the geothermal temperature of 45 ℃ are used as storage tanks of the negative and positive electrolytes, and the inner diameter of the sleeve is 20cm and the outer diameter is 60 cm.
The positive and negative electrode electrolytes used the electrolyte synthesized in example 1, and had a concentration of 0.5mol/L, and the supporting electrolyte used a 2mol/L NaCl solution, and a volume of 10 mL. The electrolyte viscosity was about 10 mPas. The positive and negative electrodes are graphite felt electrodes, and the battery diaphragm is an anion exchange membrane. Single cell stack at a current density of 20mA/cm2The coulombic efficiency is 99%, the voltage efficiency is 80%, and the energy efficiency is 82%.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (14)
1. A ferrocene-viologen bipolar active substance is characterized in that: anion is introduced to ferrocene or its derivative through functional modification, so that it and viologen organic matter form new organic metal salt in ionic form. The reaction equation is as follows:
wherein R is1、R2、R3Represents a group containing carbon, hydrogen, nitrogen, oxygen, fluorine or sulfur elements.
2. A method for preparing a ferrocene-viologen bipolar active material as defined in claim 1, wherein: the method comprises the following steps:
s1: introducing an anion on the ferrocene or the derivative thereof;
s2: respectively dissolving the modified ferrocene derivatives with negative charges and the viologen organic matters in an organic solvent;
s3: and (4) reacting the two solutions in the step S2 according to the charge molar ratio, filtering the precipitated solid, and spin-drying the solvent to obtain the solid of the ferrocene-viologen bipolar active substance.
3. The method for preparing a ferrocene-viologen bipolar active material as claimed in claim 2, wherein: in the step S1, the anion includes-COO-、-SO3 -Or PO3 2-。
4. The method for preparing a ferrocene-viologen bipolar active material as claimed in claim 2, wherein the organic solvent in the step S2 is acetonitrile, DMF, methanol or DMSO.
5. The application of the ferrocene-viologen bipolar active material as claimed in claim 1, wherein the ferrocene-viologen bipolar active material can be used as a positive electrode active material and a negative electrode active material of a flow battery at the same time.
6. The application of the ferrocene-viologen bipolar active substance in an organic water phase salt cavern battery as defined in claim 1, which comprises the following components in percentage by weight:
the electrolyte tank is filled with electrolyte;
the two polar plates are respectively arranged in the electrolyte tank body and are opposite in position;
the battery diaphragm, the battery diaphragm is located in the electrolyte tank body and will the electrolyte tank body divide for one the positive pole district of electrolyte stock solution storehouse intercommunication and with another the negative pole district of electrolyte stock solution storehouse intercommunication, one the polar plate is located the positive pole district, another the polar plate is located the negative pole district, all have the electrolyte including ferrocene-viologen bipolar active material in the positive pole district and the negative pole district, the battery diaphragm can allow the effective of supporting the electrolyte to pass through.
7. The application of the ferrocene-viologen bipolar active substance in the organic water phase salt cavern battery as recited in claim 6, wherein the concentration of the ferrocene-viologen bipolar active substance is 0.01mol/L to 4 mol/L.
8. The application of the ferrocene-viologen bipolar active substance in an organic water phase salt cavern battery as claimed in claim 6, wherein the supporting electrolyte is a single-component neutral saline solution or a mixed neutral saline solution.
9. The application of the ferrocene-viologen bipolar active substance in the organic-aqueous salt cavern battery as claimed in claim 6, wherein the supporting electrolyte is NaCl salt solution, KCl salt solution, Na2SO4Salt solution, K2SO4Salt solution, MgCl2Salt solution, MgSO4Salt solution, CaCl2Salt solution, CaSO4Salt solution, BaCl2Salt solution, BaSO4At least one salt solution.
10. The application of the ferrocene-viologen bipolar active substance in an organic water-phase salt cavern battery as recited in claim 6, wherein the battery diaphragm is one of an anion exchange membrane, a cation exchange membrane, a selective permeable membrane, an anion-cation composite exchange membrane, a dialysis membrane or a porous membrane.
11. The application of the ferrocene-viologen bipolar active substance in an organic water phase salt cavern battery as recited in claim 6, further comprising:
the two electrolyte liquid storage banks are respectively filled with electrolyte;
the circulating pipeline inputs or outputs the electrolyte in one electrolyte storage reservoir to or from the anode region, and the circulating pipeline inputs or outputs the electrolyte in the other electrolyte storage reservoir to or from the cathode region;
and the circulating pump is arranged on the circulating pipeline and enables the electrolyte to circularly flow and be supplied through the circulating pump.
12. The application of the ferrocene-viologen bipolar active substance in an organic water phase salt cavern battery as claimed in claim 11, wherein the depth of the salt cavern is 100m to 2000m underground, and the physical volume is 5 ten thousand m3About 50 km3The geothermal temperature is 25-70 ℃, the diameter of the dissolving cavity of the salt cavern is 40-120 m, and the height is 60-400 m.
13. The use of a ferrocene-viologen bipolar active material in an organic water phase salt cavern cell as recited in claim 11, further comprising:
the electrolyte liquid outlet pipe is arranged at the opening of the salt cavity, the lower end of the electrolyte liquid outlet pipe extends below the liquid level of the electrolyte in the salt cavity, and the upper end of the electrolyte liquid outlet pipe is connected with the circulating pipeline so as to output the electrolyte in the salt cavity through the electrolyte liquid outlet pipe;
the electrolyte liquid inlet pipe is arranged at the opening of the salt cavern and sleeved in the electrolyte liquid outlet pipe, the lower end of the electrolyte liquid inlet pipe faces the direction of the electrolyte in the salt cavern, and the upper end of the electrolyte liquid inlet pipe is connected with the circulating pipeline so as to input the electrolyte in the electrolyte liquid storage to the salt cavern.
14. The application of the ferrocene-viologen bipolar active substance in an organic water phase salt cavern battery as recited in claim 11, wherein the inner diameters of the electrolyte liquid outlet pipe and the electrolyte liquid inlet pipe are 10cm to 60cm, and the outer diameters are 20cm to 80 cm.
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Cited By (1)
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| WO2023087993A1 (en) * | 2021-11-16 | 2023-05-25 | 西湖大学 | Ion exchange liquid film flow battery |
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