CN113698438A - Planar binuclear ferrocene derivative and synthetic method and application thereof - Google Patents
Planar binuclear ferrocene derivative and synthetic method and application thereof Download PDFInfo
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- CN113698438A CN113698438A CN202110930400.2A CN202110930400A CN113698438A CN 113698438 A CN113698438 A CN 113698438A CN 202110930400 A CN202110930400 A CN 202110930400A CN 113698438 A CN113698438 A CN 113698438A
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- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical class [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000010189 synthetic method Methods 0.000 title description 5
- 239000003792 electrolyte Substances 0.000 claims abstract description 32
- 150000003839 salts Chemical class 0.000 claims abstract description 29
- 239000007774 positive electrode material Substances 0.000 claims abstract description 17
- 239000013543 active substance Substances 0.000 claims abstract description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 38
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 34
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 28
- -1 hexafluorophosphate Chemical compound 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 19
- 239000007773 negative electrode material Substances 0.000 claims description 17
- 239000012265 solid product Substances 0.000 claims description 17
- 239000012044 organic layer Substances 0.000 claims description 16
- 239000012528 membrane Substances 0.000 claims description 15
- 239000012266 salt solution Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- 239000011780 sodium chloride Substances 0.000 claims description 14
- 239000003115 supporting electrolyte Substances 0.000 claims description 14
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 14
- 239000007832 Na2SO4 Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 12
- 230000007935 neutral effect Effects 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 9
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl chloride Substances ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 238000009987 spinning Methods 0.000 claims description 6
- 229910019213 POCl3 Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 150000001350 alkyl halides Chemical class 0.000 claims description 4
- CMHDNDSUFCCYNR-UHFFFAOYSA-N cyclopenta-1,3-diene 2-cyclopenta-2,4-dien-1-yl-1-(cyclopenta-2,4-dien-1-ylmethyl)benzimidazole iron(2+) Chemical compound [Fe++].[Fe++].c1cc[cH-]c1.c1cc[cH-]c1.C([c-]1cccc1)n1c(nc2ccccc12)-[c-]1cccc1 CMHDNDSUFCCYNR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 230000035515 penetration Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 3
- 239000003011 anion exchange membrane Substances 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- MBVFRSJFKMJRHA-UHFFFAOYSA-N 4-fluoro-1-benzofuran-7-carbaldehyde Chemical compound FC1=CC=C(C=O)C2=C1C=CO2 MBVFRSJFKMJRHA-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910001626 barium chloride Inorganic materials 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
- 150000001768 cations Chemical class 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 238000000502 dialysis Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000012535 impurity Substances 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
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 abstract description 6
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 14
- 238000001291 vacuum drying Methods 0.000 description 12
- 125000002346 iodo group Chemical group I* 0.000 description 8
- 238000007792 addition Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229960001156 mitoxantrone Drugs 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 1
- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000012546 transfer 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
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9008—Organic or organo-metallic compounds
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- 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
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- 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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Abstract
The invention discloses a planar binuclear ferrocene derivative and a synthesis method and application thereof. The planar type binuclear ferrocene derivative can be used as a positive active material of a flow battery. The structure of the synthesized planar dual-core ferrocene derivative active substance has two active centers, can provide double energy density under the condition of the same concentration, and has an ionic structure, the solubility of the active substance is further improved compared with ferrocene, the electrochemical performance of the ferrocene derivative is stable, and the battery efficiency and the battery capacity of the flow battery can still keep a higher level after the flow battery runs for a long time; the electrolyte storage tank adopts natural salt holes, has the advantages of large capacity, low cost, safety and environmental protection, and is suitable for being applied to large-scale energy storage power stations.
Description
Technical Field
The invention relates to the technical field of flow batteries, in particular to a planar dual-core ferrocene derivative and a synthetic method and application thereof.
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, intermittency and randomness, so that seamless connection of 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 water phase flow battery has a rich choice of electrolyte, and a neutral water phase electrolyte is environment-friendly, cheap and non-flammable, so that the organic water phase flow battery is considered to be one of the flow batteries with a relatively promising application prospect. Ferrocene is a low-toxicity organic metal compound, is low in price, but has low water solubility, so that the application of the ferrocene in an aqueous phase flow battery is limited. Aiming at the problem, the invention provides a planar dual-core ferrocene derivative, a synthetic method and application thereof in a water-based flow battery, so that the water solubility of ferrocene is improved, and double energy density can be provided under the condition of the same concentration.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the invention overcomes the defects of the prior art and provides a planar type binuclear ferrocene derivative and a synthesis method and application thereof, the planar type binuclear ferrocene derivative synthesized by the invention can reduce pi-pi accumulation caused by good planarity and increase the solubility of the derivative, and meanwhile, a flexible chain containing hydrophilic groups can be introduced into the N atom position, so that the solubility of the derivative is further improved; the single-molecule structure has two active centers, double energy density can be provided under the condition of the same concentration, the electrochemical performance is stable, and the service life of the flow battery is prolonged.
The technical scheme adopted by the invention for solving the technical problems is as follows: a planar type binuclear ferrocene derivative has the following chemical structural formula, and is used as a positive electrode active substance of a salt cavern flow battery;
wherein, X-Is Cl-、I-、Br-、PF6 -、BF4 -、TFSI-One of (1); r is linear chain, branched chain and cyclic structural unit containing C, N, O, S, H and halogen.
The ferrocene has better electrochemical activity, but is insoluble in water, the planar binuclear ferrocene derivative obtained by modification has good solubility and better electrochemical performance than the ferrocene, and meanwhile, the planar binuclear ferrocene derivative molecule has two active centers and can provide double energy density under the condition of the same concentration.
A synthetic method of a planar binuclear ferrocene derivative comprises the following steps:
S1、dissolving ferrocene and DMF (N, N-dimethylformamide) in chloroform in ice water bath, adding POCl3Heating for reaction reflux, after the reaction is finished, decompressing and spinning out chloroform, and then adding anhydrous Na in ice water bath2SO4Adjusting the pH value of the solution to be neutral, filtering the precipitated solid by suction, and drying the solid in vacuum at 45 ℃ to obtain a red solid product, wherein the reaction equation is as follows:
s2, under the protection of nitrogen, mixing and heating the ferrocenecarboxaldehyde synthesized in the step S1, o-phenylenediamine and chloroform, and adding p-toluenesulfonic acid for reaction; after the reaction was completed, it was cooled to room temperature, impurities were filtered off, the filtrate was washed with saturated sodium carbonate and sodium chloride aqueous solution 3 times, respectively, and the organic layer was washed with anhydrous Na2SO4The organic layer was dried and spun to give an orange solid product having the reaction equation:
s3, under the protection of nitrogen, mixing the 1-ferrocenylmethyl-2-ferrocenylbenzimidazole synthesized in the step S2 with halogenated alkane, heating and refluxing, after the reaction is finished, cooling to room temperature, and spin-drying an organic layer to obtain an orange solid product, wherein the reaction equation is as follows:
s4, dissolving the halogenated binuclear ferrocene synthesized in the step S3 in an organic solvent, adding an organic solution containing an anion displacer, and mixing and reacting to obtain the planar binuclear ferrocene derivative containing different anions.
Further, the reactant molar ratio in the step S1 is: ferrocene: DMF: POCl3: chloroform-1: (1-4): (1-4): (10 to 20) heating at a temperature ofThe reaction time is 8-48 h at 80-120 ℃. The heating temperature is adopted to facilitate the ferrocene, DMF and POCl3And chloroform.
Further, the reactant molar ratio in the step S2 is: ferrocene carboxaldehyde: o-phenylenediamine: chloroform: para-toluenesulfonic acid ═ 1: (0.3-0.8): (1-4): (0.01-0.1), the heating temperature is 80-120 ℃, and the reaction time is 4-24 h.
Further, the reactant molar ratio in the step S3 is: 1-ferrocenylmethyl-2-ferrocenylbenzimidazole: haloalkane ═ 1: (1-2), heating at 80-120 ℃, and reacting for 4-24 h; the halo group of the haloalkane is: -I, -Br, -Cl, the alkyl chain length being 1 to 4.
Further, in the step S4, the anion-exchange agent is hexafluorophosphate (abbreviated as PF)6 -) Tetrafluoroborate (BF for short)4 -) Bis (trifluoromethanesulfonyl) imide (TFSI for short)-) One kind of (1).
Further, the organic solvent in step S4 is one of methanol, DMF, and chloroform.
The application of the planar type binuclear ferrocene derivative is used for a positive active substance of a salt cavern flow battery;
the salt cavern flow battery comprises a positive electrode liquid storage, a negative electrode liquid storage and a plurality of flow battery stacks, wherein each flow battery stack is respectively communicated with the positive electrode liquid storage and the negative electrode liquid storage;
the flow cell stack includes:
the electrolyte tank is filled with electrolyte;
the positive plate and the negative plate are arranged in the electrolyte tank body and are opposite in position;
the battery diaphragm is arranged in the electrolyte tank body and divides the electrolyte tank body into a positive region and a negative region, the positive plate is positioned in the positive region, the negative plate is positioned in the negative region, the positive region is communicated with the positive liquid storage tank through a pipeline, and the negative region is communicated with the positive liquid storage tank through a pipeline; the positive electrolyte in the positive liquid storage bank consists of a positive active material and a supporting electrolyte, and the negative electrolyte in the negative liquid storage bank consists of a negative active material and a supporting electrolyte; the battery separator is capable of supporting electrolyte penetration and preventing penetration of positive and negative active materials.
The negative electrode active material is an organic active molecule, including but not limited to water-soluble organic substances having electrochemical activity, such as quinones and derivatives or polymers thereof, bipyridines and derivatives or polymers thereof, and the like.
Further, the molar concentration of the positive electrode active material is 0.01 to 4mol/L, and the molar concentration of the negative electrode active material is 0.01 to 4 mol/L. If the molar concentration of the positive electrode active material or the negative electrode active material is higher than the concentration range, the positive electrode active material or the negative electrode active material has a large viscosity, which is not favorable for the mass transfer process.
Further, the supporting electrolyte is a single-component neutral saline solution or a mixed neutral saline solution.
Further, the supporting electrolyte is NaCl salt solution, KCl salt solution and Na2SO4Salt solution, K2SO4Salt solution, MgCl2Salt solution, CaCl2Salt solution, BaCl2One or two or more of salt solutions.
Further, 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 molecular sieve membrane, a dialysis membrane or a porous membrane.
Further, the positive electrode liquid storage reservoir and the negative electrode liquid storage reservoir are respectively salt pits, the depth of each salt pit 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 salt cavern flow battery is applied to an energy storage power station, and is used for peak regulation and emergency power supply or for storing electric energy of intermittent renewable energy sources.
The invention has the beneficial effects that: the planar dual-core ferrocene derivative active substance has reasonable design, the solubility is improved compared with ferrocene, the planar dual-core ferrocene derivative active substance has two active centers in a single molecular structure, can provide double energy density under the condition of the same concentration, can be used as a positive electrode active substance in a flow battery, has low toxicity, can be suitable for a salt cavern battery, has stable electrochemical performance, and can still keep higher level of battery efficiency and battery capacity after the salt cavern battery is used for a long time; the electrolyte storage tank adopts natural salt holes, has the advantages of high capacity, low cost, safety and environmental protection, and is suitable for being applied to large-scale energy storage power stations.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a plot of cyclic voltammetry for iodo-dinuclear ferrocene of example 1;
FIG. 2 is a graph of cell efficiency versus cycle number for example 1;
FIG. 3 is a plot of cyclic voltammograms of hexafluorophosphates of binuclear ferrocene of example 2;
FIG. 4 is a graph of cell efficiency versus cycle number for example 2;
FIG. 5 is a plot of cyclic voltammograms of tetrafluoroborates of dinuclear ferrocene from example 3;
FIG. 6 is a graph of cell efficiency versus cycle number for example 3;
FIG. 7 is TFSI of binuclear ferrocene in example 4-Cyclic voltammogram of a salt;
fig. 8 is a graph of cell efficiency versus cycle number for example 4.
Detailed Description
The invention will now be further described with reference to examples and figures.
The structures of the salt-cavity flow batteries in the embodiments 1 to 4 all adopt the structure disclosed in the Chinese patent CN 201811250811.1.
Example 1
The synthesis method of iodo-binuclear ferrocene comprises the following steps:
0.05mol of ferrocene, 0.1mol of DMF are dissolved in 6 at 0 DEG C0mL of chloroform, stirred for 20 minutes, and then 0.1mol of POCl was added dropwise3After the dropwise addition is finished, heating and refluxing are carried out, and the reaction is carried out for 24 hours; after the reaction was completed, the reaction mixture was cooled to room temperature, chloroform was removed by spinning under reduced pressure, and the residue was poured into a large amount of ice water, followed by addition of anhydrous Na2SO4Adjusting the pH value of the powder to be neutral, standing, separating out solids, performing suction filtration, and drying the obtained solids in a vacuum drying oven at 45 ℃ for 24 hours to obtain a red solid product ferrocenecarboxaldehyde;
under the protection of nitrogen, 5mmol of ferrocenecarboxaldehyde, 2.5mmol of o-phenylenediamine and 50mL of chloroform are mixed in a 250mL flask, heated and refluxed for 10min, and added with 12.5mg of p-toluenesulfonic acid and reacted for 6 h. After the reaction was completed, it was cooled to room temperature, filtered, and the filtrate was washed with saturated sodium carbonate and sodium chloride aqueous solution 3 times, respectively, and the combined organic layers were washed with anhydrous Na2SO4Drying, namely drying the organic layer in a vacuum drying oven at 45 ℃ overnight to obtain an orange solid product 1-ferrocenyl methyl-2-ferrocenyl benzimidazole;
under the protection of nitrogen, 0.64mmol of iodomethane and 5ml of iodomethane are mixed, heated and refluxed for 12 hours, after the reaction is finished, the mixture is cooled to room temperature, an organic layer is dried in a vacuum drying oven at the temperature of 45 ℃ for one night, and a target product, namely the iodo binuclear ferrocene, is obtained, and the chemical structural formula of the iodo binuclear ferrocene is as follows:
performing electrochemical performance detection on the synthesized iodo-binuclear ferrocene: iodobinuclear ferrocene solution (5 mM in aqueous sodium chloride at pH 7) was studied by Cyclic Voltammetry (CV) at a scan rate of 100Mv/s and a scan number of 50, and the results are shown in FIG. 1. The CV curve for this compound in fig. 1 shows 2 pairs of characteristic redox peaks, the first pair of characteristic reduction peaks Epa ═ 0.48V, and the corresponding oxidation peak, Epc ═ 0.6V; the second pair of characteristic reduction peaks Epa at 0.78V and its corresponding oxidation peak Epa at 0.95V increased the ferrocene redox potential (0.4V). The 50-turn coincidence is good, which shows that the chemical property is stable.
And (3) carrying out battery performance test on the synthesized iodo-binuclear ferrocene:
the underground depth is 700m, and the physical volume is 9 ten thousand m3Two salt cavities with the height of 80m, the maximum diameter of 50m and the geothermal temperature of 40 ℃ are used as storage tanks of positive and negative electrolyte, the inner diameter of the sleeve is 20cm, and the outer diameter is 55 cm;
the positive electrode electrolyte used the material synthesized in example 1 as the positive electrode active material, the molar concentration of the positive electrode active material was 0.25mol/L, the negative electrode electrolyte used 4, 4' -bipyridine as the negative electrode active material, the molar concentration of the negative electrode active material was 0.25mol/L, and the supporting electrolyte used 1.5mol/L NaCl solution. The positive plate and the negative plate both adopt graphite felt electrode plates, and the battery diaphragm adopts an anion membrane. As can be seen from FIG. 2, at a current density of 20mA/cm2The coulombic efficiency is 99%, the voltage efficiency is 77%, and the energy efficiency is 76%.
Example 2
The method for synthesizing the hexafluorophosphate of the binuclear ferrocene comprises the following steps:
0.05mol of ferrocene, 0.2mol of DMF was dissolved in 80mL of chloroform at 0 ℃ and stirred for 20 minutes, after which 0.2mol of POCl was added dropwise3After the dropwise addition, heating and refluxing are carried out, and the reaction is carried out for 48 hours; after the reaction was completed, the reaction mixture was cooled to room temperature, chloroform was removed by spinning under reduced pressure, and the residue was poured into a large amount of ice water, followed by addition of anhydrous Na2SO4Adjusting the pH value of the powder to be neutral, standing, separating out solids, performing suction filtration, and drying the solids in a vacuum drying oven at 45 ℃ overnight to obtain a red solid product ferrocenecarboxaldehyde;
under the protection of nitrogen, mixing 20mmol of ferrocenecarboxaldehyde, 10mmol of o-phenylenediamine and 50mL of chloroform in a 250mL flask, heating and refluxing for 10min, adding 15.6mg of p-toluenesulfonic acid, and reacting for 12 h; after the reaction was completed, it was cooled to room temperature, filtered, and the filtrate was washed with saturated sodium carbonate and sodium chloride aqueous solution 3 times, respectively, and the combined organic layers were washed with anhydrous Na2SO4Drying, spin-drying the organic layer, and drying the obtained product in a vacuum drying oven at 45 ℃ for 18h to obtain an orange solid product;
under the protection of nitrogen, mixing 0.87mmol of the solid product with 9ml of ethyl iodide, heating and refluxing for 12h, after the reaction is finished, cooling to room temperature, drying an organic layer in a rotary manner, and drying the obtained product in a vacuum drying oven at 45 ℃ for 15h to obtain iodo binuclear ferrocene;
dissolving iodo binuclear ferrocene by using a small amount of methanol, dropwise adding a saturated methanol solution of ammonium hexafluorophosphate inwards to generate a large amount of precipitate, and stirring at room temperature for 2 hours; after the reaction is finished, centrifuging the reaction solution, washing the reaction solution for three times by using a small amount of methanol, and drying the solid to obtain the binuclear ferrocene hexafluorophosphate, wherein the chemical structural formula of the binuclear ferrocene hexafluorophosphate is as follows:
and (3) carrying out electrochemical performance test on the synthesized binuclear ferrocene hexafluorophosphate: the hexafluorophosphate solution of binuclear ferrocene (5 mM in aqueous sodium chloride solution at PH 7) was studied by Cyclic Voltammetry (CV) at a scan rate of 100Mv/s for 50 scans, and the results are shown in fig. 3. The CV curve of the compound in fig. 3 shows 2 pairs of characteristic redox peaks, which are characterized in that the characteristic reduction peaks Epa are 0.46V and 0.85V, and the corresponding oxidation peaks Epc are 0.61V and 0.95V, so that the electrochemical performance of ferrocene is improved, the coincidence of 50 circles is good, and the electrochemical performance of the hexafluorophosphate of the binuclear ferrocene is stable.
And (3) carrying out battery performance test on the synthesized binuclear ferrocene hexafluorophosphate:
adopts the underground depth of 800m and the physical volume of 20 ten thousand m3Two salt cavities with the height of 100m, the maximum diameter of 40m and the geothermal temperature of 40 ℃ are used as storage tanks of positive and negative electrolyte, and the inner diameter of the sleeve is 20cm and the outer diameter is 40 cm.
The electrolyte solution used the material synthesized in example 2 as a positive electrode active material, the molar concentration of the positive electrode active material was 0.25mol/L, the negative electrode electrolyte solution used 1, 8' -dihydroxyanthraquinone as a negative electrode active material, the concentration of the negative electrode active material was 0.25mol/L, the supporting electrolyte solution used 1.5mol/L NaCl solution, and the electrolyte viscosityAbout 4.7 mPas. The positive and negative plates are graphite felt electrode plates, and the battery diaphragm is an anion exchange membrane. As can be seen from FIG. 4, at a current density of 30mA/cm2The coulombic efficiency is 99%, the voltage efficiency is 72%, and the energy efficiency is 70%.
Example 3
The method for synthesizing the tetrafluoroborate of the binuclear ferrocene comprises the following steps:
0.05mol of ferrocene, 0.2mol of DMF was dissolved in 80mL of chloroform at 0 ℃ and stirred for 20 minutes, after which 0.2mol of POCl was added dropwise3After the dropwise addition, heating and refluxing are carried out, and the reaction is carried out for 48 hours; after the reaction was completed, the reaction mixture was cooled to room temperature, chloroform was removed by spinning under reduced pressure, and the residue was poured into a large amount of ice water, followed by addition of anhydrous Na2SO4Adjusting the pH value of the powder to be neutral, standing, separating out solids, performing suction filtration, and drying the solids in a vacuum drying oven at 45 ℃ overnight to obtain a red solid product ferrocenecarboxaldehyde;
under the protection of nitrogen, mixing 20mmol of ferrocenecarboxaldehyde, 10mmol of o-phenylenediamine and 50mL of chloroform in a 250mL flask, heating and refluxing for 10min, adding 15.6mg of p-toluenesulfonic acid, and reacting for 12 h; after the reaction was completed, it was cooled to room temperature, filtered, and the filtrate was washed with saturated sodium carbonate and sodium chloride aqueous solution 3 times, respectively, and the combined organic layers were washed with anhydrous Na2SO4Drying, spin-drying the organic layer, and drying the obtained product in a vacuum drying oven at 45 ℃ for 18h to obtain an orange solid product;
under the protection of nitrogen, mixing 0.87mmol of the solid product with 9ml of iodopropane, heating and refluxing for 12h, after the reaction is finished, cooling to room temperature, drying the solvent in a rotary manner, and drying the obtained solid in a vacuum drying oven at 45 ℃ for 15h to obtain iodo binuclear ferrocene;
dissolving iodo binuclear ferrocene by using a small amount of methanol, dropwise adding saturated DMF (dimethyl formamide) solution of tetrafluoroborate into the solution to generate a large amount of precipitate, and stirring the solution at room temperature for 2 hours; after the reaction is finished, centrifuging the reaction liquid, washing the reaction liquid for three times by using a small amount of methanol, and drying the solid to obtain the dinuclear ferrocene tetrafluoroborate, wherein the chemical structural formula of the dinuclear ferrocene tetrafluoroborate is as follows:
and (3) carrying out electrochemical performance test on the synthesized tetrafluoroborate of the binuclear ferrocene: a solution of binuclear ferrocene in tetrafluoroborate (5 mM in aqueous sodium chloride at PH 7) was studied by Cyclic Voltammetry (CV) at a scan rate of 100Mv/s for 50 scans, and the results are shown in fig. 5. The CV curve of the compound in fig. 5 shows 2 pairs of characteristic redox peaks, which are characterized in that the characteristic reduction peaks Epa are 0.42V and 0.8V, and the corresponding oxidation peaks Epc are 0.62V and 0.96V, so that the electrochemical performance of ferrocene is improved, the coincidence of 50 circles is good, and the electrochemical performance of the hexafluorophosphate of the binuclear ferrocene is stable.
And (3) carrying out battery performance test on the synthesized dicaryon ferrocene tetrafluoroborate:
adopts the underground depth of 650m and the physical volume of 15 ten thousand m3Two salt cavities with the height of 88m, the maximum diameter of 85m and the geothermal temperature of 35 ℃ are used as storage tanks of positive and negative electrolyte, the inner diameter of the sleeve is 20cm, and the outer diameter is 50 cm;
the positive electrode electrolyte used the dinuclear ferrocene tetrafluoroborate synthesized in example 3 as a positive electrode active material, the molar concentration of the positive electrode active material was 0.25mol/L, the negative electrode electrolyte used a quaternary ammonium salt of 1, 8' -dihydroxyanthraquinone as a negative electrode active material, the molar concentration of the negative electrode active material was 0.25mol/L, and the supporting electrolyte used a 1mol/L NaCl solution. The positive and negative plates are graphite felt electrode plates, and the battery diaphragm is a molecular sieve exchange membrane. As can be seen from FIG. 6, at a current density of 20mA/cm2When the flow battery is used, the coulombic efficiency is 99%, the voltage efficiency is 77%, the energy efficiency is 75%, and the capacitance and the stability of the coulombic efficiency of the flow battery are improved.
Example 4
TFSI of binuclear ferrocene-The salt synthesis method specifically comprises the following steps:
0.05mol of ferrocene, 0.06mol of DMF was dissolved in 80mL of chloroform at 0 ℃ and stirred for 20 minutes, after which 0.073mol of POCl was added dropwise3After the dripping is finished, addCarrying out thermal reflux and reacting for 11 h; after the reaction was completed, the reaction mixture was cooled to room temperature, chloroform was removed by spinning under reduced pressure, and the residue was poured into a large amount of ice water, followed by addition of anhydrous Na2SO4Adjusting the pH value of the powder to be neutral, standing, separating out solids, performing suction filtration, and drying the solids in a vacuum drying oven at 45 ℃ overnight to obtain a red solid product ferrocenecarboxaldehyde;
under the protection of nitrogen, mixing 20mmol of ferrocenecarboxaldehyde, 7mmol of o-phenylenediamine and 30mL of chloroform in a 250mL flask, heating and refluxing for 10min, adding 8.96mg of p-toluenesulfonic acid, and reacting for 12 h; after the reaction was completed, it was cooled to room temperature, filtered, and the filtrate was washed with saturated sodium carbonate and sodium chloride aqueous solution 3 times, respectively, and the combined organic layers were washed with anhydrous Na2SO4Drying, spin-drying the organic layer, and drying the obtained solid in a vacuum drying oven at 45 ℃ for 18h to obtain an orange solid product;
under the protection of nitrogen, mixing 0.87mmol of the solid product with 6ml of iodobutane, heating and refluxing for 12h at 80 ℃, cooling to room temperature after the reaction is finished, and spin-drying the solvent to obtain a solid, and drying the solid in a vacuum drying oven at 45 ℃ for 15h to obtain iodo binuclear ferrocene;
dissolving iodo binuclear ferrocene by using a small amount of DMF (dimethyl formamide), dropwise adding a saturated DMF solution of bis (trifluoromethanesulfonimide) into the solution to generate a large amount of precipitate, and stirring the solution at room temperature for 2 hours; after the reaction is finished, centrifuging the reaction solution, washing the reaction solution for three times by using a small amount of methanol, and drying the solid to obtain the TFSI of the binuclear ferrocene-A salt having the chemical formula;
TFSI of the binuclear ferrocene synthesized by the method-Salt electrochemical performance testing: TFSI study of binuclear ferrocene by Cyclic Voltammetry (CV)-The results of the test are shown in FIG. 7 for a salt solution (5 mM in aqueous sodium chloride at pH 7) with a scan rate of 100Mv/s and a number of scans of 50. The CV curve of the compound in fig. 7 shows 2 pairs of characteristic redox peaks, which are characteristic reduction peaks Epa ═ 0.48V and 0.75V, which areCorresponding oxidation peaks Epc are 0.6V and 0.92V, the electrochemical performance of the ferrocene is improved, the 50-turn coincidence is good, and the electrochemical performance of the binuclear ferrocene hexafluorophosphate is stable.
TFSI of the binuclear ferrocene synthesized by the method-Salt battery performance testing:
adopts the underground depth of 650m and the physical volume of 15 ten thousand m3Two salt cavities with the height of 88m, the maximum diameter of 85m and the geothermal temperature of 35 ℃ are used as storage tanks of positive and negative electrolyte, and the inner diameter of the sleeve is 20cm and the outer diameter is 50 cm.
The positive electrode active material synthesized in example 4 was used as the positive electrode electrolyte, the molar concentration of the positive electrode active material was 0.2mol/L, the viologen polymer (Mw 800 to 5000) was used as the negative electrode active material as the negative electrode electrolyte, and the NaCl solution at 1mol/L was used as the supporting electrolyte. The positive and negative plates are graphite felt electrode plates, and the battery diaphragm is a porous membrane. As can be seen from FIG. 8, at a current density of 30mA/cm2The coulombic efficiency is 99%, the voltage efficiency is 80%, the energy efficiency is 78%, and the capacitance and the stability of the coulombic efficiency of the flow battery are improved.
In summary, it can be seen from the CV curves of examples 1 to 4 that the active material has more symmetrical redox peaks when the anions are iodide and TFSI ions. Therefore, the two counter ions have higher redox reversibility.
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 planar type binuclear ferrocene derivative is characterized in that: the chemical structural formula of the planar type binuclear ferrocene derivative is as follows, and the planar type binuclear ferrocene derivative is used as a positive active substance of a salt cavity flow battery;
wherein, X-Is Cl-、I-、Br-、PF6 -、BF4 -、TFSI-One of (1); r is linear chain, branched chain and cyclic structural unit containing C, N, O, S, H and halogen.
2. A method for synthesizing the planar binuclear ferrocene derivative as claimed in claim 1, wherein: the method comprises the following steps:
s1, dissolving ferrocene and DMF in chloroform in ice water bath, and adding POCl3Heating for reaction reflux, after the reaction is finished, decompressing and spinning out chloroform, and then adding anhydrous Na in ice water bath2SO4Adjusting the pH value of the solution to be neutral, filtering the precipitated solid by suction, and drying the solid in vacuum at 45 ℃ to obtain a red solid product, wherein the reaction equation is as follows:
s2, under the protection of nitrogen, mixing and heating the ferrocenecarboxaldehyde synthesized in the step S1, o-phenylenediamine and chloroform, and adding p-toluenesulfonic acid for reaction; after the reaction was completed, it was cooled to room temperature, impurities were filtered off, the filtrate was washed with saturated sodium carbonate and sodium chloride aqueous solution 3 times, respectively, and the organic layer was washed with anhydrous Na2SO4The organic layer was dried and spun to give an orange solid product having the reaction equation:
s3, under the protection of nitrogen, mixing the 1-ferrocenylmethyl-2-ferrocenylbenzimidazole synthesized in the step S2 with halogenated alkane, heating and refluxing, after the reaction is finished, cooling to room temperature, and spin-drying an organic layer to obtain an orange solid product, wherein the reaction equation is as follows:
s4, dissolving the halogenated binuclear ferrocene synthesized in the step S3 in an organic solvent, adding an organic solution containing an anion displacer, and mixing and reacting to obtain the planar binuclear ferrocene derivative containing different anions.
3. The method for synthesizing a planar binuclear ferrocene derivative according to claim 2, wherein: the reactant molar ratio in the step S1 is: ferrocene: DMF: POCl3: chloroform-1: (1-4): (1-4): (10-20), the heating temperature is 80-120 ℃, and the reaction time is 8-48 h.
4. The method for synthesizing a planar binuclear ferrocene derivative according to claim 2, wherein: the reactant molar ratio in the step S2 is: ferrocene carboxaldehyde: o-phenylenediamine: chloroform: para-toluenesulfonic acid ═ 1: (0.3-0.8): (1-4): (0.01-0.1), the heating temperature is 80-120 ℃, and the reaction time is 4-24 h.
5. The method for synthesizing a planar binuclear ferrocene derivative according to claim 2, wherein: the reactant molar ratio in the step S3 is: 1-ferrocenylmethyl-2-ferrocenylbenzimidazole: haloalkane ═ 1: (1-2), heating at 80-120 ℃, and reacting for 4-24 h; the halo group of the haloalkane is: -I, -Br, -Cl, the alkyl chain length being 1 to 4.
6. The method for synthesizing a planar binuclear ferrocene derivative according to claim 2, wherein: and in the step S4, the anion displacer is one of hexafluorophosphate, tetrafluoroborate and bistrifluoromethanesulfonimide.
7. The method for synthesizing a planar binuclear ferrocene derivative according to claim 2, wherein: the organic solvent in step S4 is one of methanol, DMF, and chloroform.
8. The use of the planar binuclear ferrocene derivative as claimed in claim 1, wherein: the planar dual-core ferrocene derivative is used as a positive electrode active substance of a salt cavity flow battery;
the salt cavern flow battery comprises a positive electrode liquid storage, a negative electrode liquid storage and a plurality of flow battery stacks, wherein each flow battery stack is respectively communicated with the positive electrode liquid storage and the negative electrode liquid storage;
the flow cell stack includes:
the electrolyte tank is filled with electrolyte;
the positive plate and the negative plate are arranged in the electrolyte tank body and are opposite in position;
the battery diaphragm is arranged in the electrolyte tank body and divides the electrolyte tank body into a positive region and a negative region, the positive plate is positioned in the positive region, the negative plate is positioned in the negative region, the positive region is communicated with the positive liquid storage tank through a pipeline, and the negative region is communicated with the positive liquid storage tank through a pipeline; the positive electrolyte in the positive liquid storage bank consists of a positive active material and a supporting electrolyte, and the negative electrolyte in the negative liquid storage bank consists of a negative active material and a supporting electrolyte; the battery separator is capable of supporting electrolyte penetration and preventing penetration of positive and negative active materials.
9. The use of the planar binuclear ferrocene derivative according to claim 8, wherein: the negative active material is an organic active molecule.
10. The use of the planar binuclear ferrocene derivative according to claim 8, wherein: the molar concentration of the positive electrode active material is 0.01-4 mol/L, and the molar concentration of the negative electrode active material is 0.01-4 mol/L.
11. The use of the planar binuclear ferrocene derivative according to claim 8, wherein: the supporting electrolyte is a single-component neutral saline solution or a mixed neutral saline solution.
12. The use of the planar binuclear ferrocene derivative according to claim 11, wherein: the supporting electrolyte is NaCl salt solution, KCl salt solution and Na2SO4Salt solution, K2SO4Salt solution, MgCl2Salt solution, CaCl2Salt solution, BaCl2One or two or more of salt solutions.
13. The use of the planar binuclear ferrocene derivative according to claim 8, wherein: 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 molecular sieve membrane, a dialysis membrane or a porous membrane.
14. The use of the planar binuclear ferrocene derivative according to claim 8, wherein: the positive electrode liquid storage tank and the negative electrode liquid storage tank are respectively salt pits, the depth of each salt pit 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 cave is 40-120 m, and the height is 60-400 m.
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| 杨帆: "二茂铁系列衍生物的设计合成及其在有机液流电池中的应用" * |
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