CN116706178A - Aqueous flow battery based on ferrocene derivative electrolyte - Google Patents
Aqueous flow battery based on ferrocene derivative electrolyte Download PDFInfo
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- CN116706178A CN116706178A CN202210178382.1A CN202210178382A CN116706178A CN 116706178 A CN116706178 A CN 116706178A CN 202210178382 A CN202210178382 A CN 202210178382A CN 116706178 A CN116706178 A CN 116706178A
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- unsubstituted
- substituted
- alkyl
- flow battery
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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 33
- 239000003792 electrolyte Substances 0.000 title claims abstract description 29
- 239000007774 positive electrode material Substances 0.000 claims abstract description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 77
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 17
- 238000006467 substitution reaction Methods 0.000 claims description 16
- 125000000623 heterocyclic group Chemical group 0.000 claims description 15
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 14
- 125000001072 heteroaryl group Chemical group 0.000 claims description 14
- -1 hydroxy, mercapto Chemical class 0.000 claims description 14
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000003115 supporting electrolyte Substances 0.000 claims description 9
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 8
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 claims description 4
- 125000006714 (C3-C10) heterocyclyl group Chemical group 0.000 claims description 4
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 125000006584 (C3-C10) heterocycloalkyl group Chemical group 0.000 claims 1
- 239000010405 anode material Substances 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 67
- 239000000243 solution Substances 0.000 description 58
- 239000011780 sodium chloride Substances 0.000 description 37
- 150000001875 compounds Chemical class 0.000 description 30
- 238000002484 cyclic voltammetry Methods 0.000 description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 238000004146 energy storage Methods 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 229940125904 compound 1 Drugs 0.000 description 15
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
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- 230000033116 oxidation-reduction process Effects 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
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- AAAXMNYUNVCMCJ-UHFFFAOYSA-N 1,3-diiodopropane Chemical compound ICCCI AAAXMNYUNVCMCJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
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- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 1
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- 150000003573 thiols Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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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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- 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 System
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
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Abstract
The application provides an aqueous flow battery based on ferrocene derivative electrolyte, which comprises: the electrolyte comprises a positive electrode material, wherein the positive electrode material is a water-soluble ferrocene derivative. The ferrocene derivative electrolyte flow battery provided by the application has high voltage and high energy density.
Description
Technical Field
The application belongs to the technical field of energy storage of flow batteries. In particular, the application relates to an aqueous flow battery based on ferrocene derivative electrolyte and application thereof.
Background
The increase in energy demand and the increasing increase in environmental problems have made efficient use of renewable energy sources such as solar energy, wind energy, and the like a more realistic countermeasure. However, the inherent intermittence and volatility of these clean energy sources prevents their direct large-scale integration into the power grid. Therefore, by utilizing a proper intermediate energy storage system, solar energy, wind energy and the like are stored in an electric energy form, the electric energy is stored in a low electricity consumption valley, and the electric energy is released in a high electricity consumption peak, so that the method becomes an effective method for realizing stable power transmission of renewable energy sources.
Flow batteries are considered to be viable technologies for achieving large-scale energy storage. Compared with a static rechargeable battery (such as a lead-acid battery and a lithium ion battery), the flow battery can be well applied to integration of renewable energy sources and power grid balance due to the advantages of high power input and output, energy and power decoupling, safety, scalability (up to megawatts/megawatt hour) and the like. Conventional inorganic flow batteries, including vanadium and zinc bromine flow batteries, have evolved into relatively sophisticated technologies. However, their use in large-scale energy storage has several major technical and economic drawbacks, including the expensive and limited resources of the active material (vanadium), corrosive and toxic electrolyte, unstable active material, easy dendrite precipitation, expensive ion exchange membrane, and cross-contamination of the positive and negative electrolytes. Therefore, there is an urgent need to develop low-cost, safe, environmentally friendly flow battery technology to meet the increasing energy demands.
Aqueous organic flow batteries are distinguished in large-scale energy storage, and in particular have the following several outstanding advantages: (1) The organic redox active material composed of elements rich in the earth is a sustainable strategy, the organic energy storage molecular structure is adjustable, and the oxidizable/reducible potential is adjustable and the solubility is high, so that the energy density is high; (2) The safety of the energy storage link is ensured by using water as a medium; (3) The electrolyte composed of water and simple inorganic supporting electrolyte such as sodium chloride, potassium hydroxide and the like is low in cost; (4) The high-conductivity water electrolyte and the proper selective ion exchange membrane can simultaneously realize high-energy efficiency and high-power operation in the charge and discharge process.
Ferrocene is a typical sandwich metallocene comprising two cyclopentadienyl ligands and an iron centre, undergoing an electron transfer (relative to SHE) at around 0.4V. Organometallic complexes such as ferrocene and its derivatives have been discovered since the 50 th century of 20 due to reversible Fe 3+/2 +redox properties and good thermal stability, with a high degree of reversibilityElectrochemical reactions, which are often used as internal references for organic solvents, find widespread use in materials science. However, ferrocene compounds are almost insoluble in water, so it is a promising task to design water-soluble ferrocene derivatives for water-based organic flow batteries to store energy. In addition, the ferrocene derivative is synthesized by taking elements rich in the earth such as carbon, hydrogen, nitrogen, iron and the like as raw materials, so that the synthesis cost is low, and the ferrocene derivative is hopefully applied to large-scale low-cost energy storage.
The ferrocene compound is used as a core skeleton, a series of organic electrolyte which can be used for a neutral water system organic flow battery is designed, and the non-corrosive and nonflammable neutral water electrolyte and low-cost inorganic salt are used as supporting electrolyte, so that the ferrocene compound has the advantages of high safety, low corrosiveness, low cost, environmental friendliness and the like.
Disclosure of Invention
The application aims to provide an aqueous flow battery based on ferrocene derivative electrolyte and application thereof.
In a first aspect of the application, there is provided an aqueous flow battery based on a ferrocene derivative electrolyte, comprising:
the electrolyte comprises a positive electrode material, wherein the positive electrode material is a water-soluble ferrocene derivative;
and the ferrocene derivative has a structure selected from the group consisting of:
wherein,,
m and n are each independently 0, 1,2, 3, 4 or 5;
p, q, x are each independently 1,2, 3, 4, 5, 6, 7 or 8;
R、R 1 、R 2 or R 3 Each independently selected from the group consisting of: H. halogen, hydroxy, mercapto, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted 3-10 membered heterocyclyl, substituted or unsubstituted C6-C10Aryl, substituted or unsubstituted 4-10 membered heteroaryl, amino, carboxyl, -PO 3 X、-SO 3 X, or a group selected from the group consisting of:
R 0 selected from the group consisting of: -COOX, -SO 3 X、-PO 3 X、-NH 2 、-NHCH 3 、-N(CH 3 ) 2 、-N + (CH 3 ) 3 M - ;
Wherein X is selected from the group consisting of: h + 、NH 4 + 、Li + 、Na + 、K + 、Mg 2+ 、Al 3+ 、Ca 2+ The method comprises the steps of carrying out a first treatment on the surface of the Or X is a negative charge;
M - selected from the group consisting of: f (F) - 、Cl - 、Br - 、I - 、OH - 、OAc - 、OTf - 、OTs - 、SO 4 2- 、SO 3 2- 、PO 4 3- 、HPO 4 2- 、H 2 PO 4 - 、NO 2 - 、NO 3 - 、CO 3 2- 、HCO 3 - 、ClO 4 - 、ClO 3 - 、ClO 2 - 、ClO - Or CN - ;
R 4 、R 5 Each independently selected from the group consisting of: H. a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted 3-10 membered heterocyclic group, or a substituted or unsubstituted C6-C10 aryl group, or a substituted or unsubstituted 4-10 membered heteroaryl group; or R is 4 And R is 5 Together with the carbon atoms to which they are attached form a 3-to 6-membered cycloalkyl or heterocyclyl group;
unless otherwise indicated, the substitution means substitution with a group selected from the group consisting of: C1-C10 alkyl, -COOX, -SO 3 X、-PO 3 X。
In another preferred embodiment, R is selected from the group consisting of: H. substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted 3-6 membered heterocyclyl;
R 1 、R 2 or R is 3 Each independently selected from the group consisting of: H. halogen, hydroxy, mercapto, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted 3-6 membered heterocyclyl, or a group selected from the group consisting of:
R 0 selected from the group consisting of: -COOX, -SO 3 X、-PO 3 X、-NH 2 、-NHCH 3 、-N(CH 3 ) 2 、-N + (CH 3 ) 3 M - ;
Wherein X is selected from the group consisting of: h + 、NH 4 + 、Li + 、Na + 、K + 、Mg 2+ 、Al 3+ 、Ca 2+ The method comprises the steps of carrying out a first treatment on the surface of the Or X is a negative charge;
M - selected from the group consisting of: f (F) - 、Cl - 、Br - Or I - ;
R 4 、R 5 Each independently selected from the group consisting of: H. substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl; or R is 4 And R is 5 Together with the carbon atoms to which they are attached form a 3-to 6-membered cycloalkyl or heterocyclyl group;
unless otherwise indicated, the substitution means substitution with a group selected from the group consisting of: C1-C10 alkyl, -COOX, -SO 3 X、-PO 3 X。
In another preferred embodiment, the ferrocene derivative has a structure selected from the group consisting of:
in another preferred embodiment, R is selected from the group consisting of: H. a substituted or unsubstituted C1-C4 alkyl group;
R 1 、R 2 or R is 3 Each independently of the otherIs selected from the group consisting of: H. a substituted or unsubstituted C1-C4 alkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted 3-6 membered heterocyclic group, or a group selected from the group consisting of:
R 0 selected from the group consisting of: -COOX, -SO 3 X、-PO 3 X、-NH 2 、-NHCH 3 、-N(CH 3 ) 2 、-N + (CH 3 ) 3 M - ;
Wherein X is selected from the group consisting of: h + 、NH 4 + 、Li + 、Na + 、K + 、Mg 2+ 、Al 3+ 、Ca 2+ ;
M - Selected from the group consisting of: f (F) - 、Cl - 、Br - Or I - ;
R 4 、R 5 Each independently selected from the group consisting of: H. substituted or unsubstituted C1-C4 alkyl;
unless otherwise indicated, the substitution means substitution with a group selected from the group consisting of: C1-C10 alkyl, -COOX, -SO 3 X、-PO 3 X。
In another preferred embodiment, R 1 Selected from the group consisting of: a substituted or unsubstituted C1-C4 alkyl group, or a group selected from the group consisting of:
wherein p is 1,2, 3 or 4, R 0 Selected from the group consisting of: -SO 3 X、-N + (CH 3 ) 3 M - ;
R 2 And R is 3 Each independently is methyl.
In another preferred embodiment, M - Is Cl - 。
In another preferred embodiment, R is H; p, q, x are each independently 1,2, 3 or 4; m and n are each independently 0, 1 or 2.
In another preferred embodiment, the ferrocene derivative is selected from the group consisting of:
in another preferred embodiment, the concentration of the water-soluble ferrocene derivative is 0.05-0.2M.
In another preferred example, the negative electrode material is BTMAP-VI and has the following structure:
in another preferred embodiment, the supporting electrolyte is an inorganic supporting electrolyte and is selected from the group consisting of: sodium chloride salt solution, potassium hydroxide salt solution, or a combination thereof.
In another preferred embodiment, the concentration of the inorganic supporting electrolyte is 0.8 to 1.5M.
In another preferred embodiment, the aqueous flow battery further comprises flow battery reactors (membranes), and the flow battery reactors are respectively communicated with the two storage tanks.
In another preferred embodiment, the flow battery reactor comprises:
the electrolytic cell body is filled with the electrolyte;
the two polar plates are oppositely arranged;
battery separator: the battery diaphragm is positioned in the electrolytic tank body, the battery diaphragm divides the electrolytic tank body into an anode area communicated with one electrolyte storage tank and a cathode area communicated with the other electrolyte storage tank, one polar plate is arranged in the anode area, the other polar plate is arranged in the cathode area, positive electrolyte containing the positive active substance is arranged in the anode area, negative electrolyte containing the negative active substance is arranged in the cathode area, and the battery diaphragm can be penetrated by the supporting electrolyte to prevent the positive active substance and the negative active substance from penetrating;
the circulating pipeline is used for inputting or outputting the electrolyte in one electrolyte storage tank into or from the anode region, and inputting or outputting the electrolyte in the other electrolyte storage tank into or from the cathode region;
and the pump is arranged on the circulating pipeline, and electrolyte is circularly supplied by the pump.
In another preferred example, the polar plate is an SGL39AA carbon paper electrode or a carbon cloth electrode.
In another preferred example, the battery separator is a semion AMV anion exchange membrane.
In a second aspect of the present application there is provided a ferrocene derivative having a structure selected from the group consisting of:
wherein,,
m and n are each independently 0, 1,2, 3, 4 or 5;
p, q, x are each independently 1,2, 3, 4, 5, 6, 7 or 8;
R、R 1 、R 2 or R 3 Each independently selected from the group consisting of: H. halogen, hydroxy, mercapto, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted 3-10 membered heterocyclyl, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted 4-10 membered heteroaryl, amino, carboxy, -PO 3 H. A sulfonic acid group, or a group selected from the group consisting of:
R 0 selected from the group consisting of: -COOX, -SO 3 X、-PO 3 X、-NH 2 、-NHCH 3 、-N(CH 3 ) 2 、-N + (CH 3 ) 3 M - ;
Wherein X is selected from the group consisting of: h + 、NH 4 + 、Li + 、Na + 、K + 、Mg 2+ 、Al 3+ 、Ca 2+ The method comprises the steps of carrying out a first treatment on the surface of the Or X is a negative charge;
M - selected from the group consisting of: f (F) - 、Cl - 、Br - 、I - 、OH - 、OAc - 、OTf - 、OTs - 、SO 4 2- 、SO 3 2- 、PO 4 3- 、HPO 4 2- 、H 2 PO 4 - 、NO 2 - 、NO 3 - 、CO 3 2- 、HCO 3 - 、ClO 4 - 、ClO 3 - 、ClO 2 - 、ClO - Or CN - ;
R 4 、R 5 Each independently selected from the group consisting of: H. a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C3-C10 heterocycloalkyl group, or a substituted or unsubstituted C6-C10 aryl group, or a substituted or unsubstituted 4-10 membered heteroaryl group; or R is 4 And R is 5 Together form a 3-6 membered cycloalkyl or heterocyclyl group;
unless otherwise indicated, the substitution means substitution with a group selected from the group consisting of: C1-C10 alkyl, -COOX, -SO 3 X、-PO 3 X。
In another preferred embodiment, R 1 Is methyl.
In another preferred embodiment, M - Is Cl - 。
In a third aspect of the application, there is provided the use of a ferrocene derivative according to the second aspect of the application for the preparation of a flow battery positive electrode material.
It is understood that within the scope of the present application, the above-described technical features of the present application and technical features specifically described below (e.g., in the examples) may be combined with each other to constitute new or preferred technical solutions. And are limited to a space, and are not described in detail herein.
Detailed Description
The inventor has studied extensively and intensively and provided a novel aqueous flow battery based on ferrocene derivative electrolyte for the first time. The water-based flow battery has the advantages of high safety, low corrosiveness, low cost, environmental friendliness and the like. On this basis, the present application has been completed.
Terminology
In the present application, unless otherwise indicated, terms used have the ordinary meanings known to those skilled in the art.
The term "C1-C10 alkyl" refers to a straight or branched chain alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, or the like.
The term "C3-C10 cycloalkyl" refers to a cyclic alkyl group having 3 to 10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or the like.
The term "3-10 membered heterocyclic group" means that at least one of the atoms forming the heterocyclic skeleton is not carbon, and is nitrogen, oxygen or sulfur. Typically, the heterocycle contains no more than 4 nitrogens, no more than 2 oxygens, and/or no more than 2 thiols. Unless otherwise indicated, a heterocycle may be a saturated, partially unsaturated, or fully unsaturated ring.
The term "C6-C10 aryl" refers to an aromatic cyclic group having 6 to 10 carbon atoms, such as phenyl, naphthyl, and the like, which does not contain heteroatoms in the ring.
The term "heteroaryl" refers to a heteroaromatic system containing 1 to 4 heteroatoms including nitrogen, oxygen and S (O) r (where r is an integer of 0, 1, 2), e.g., 4-10 membered heteroaryl refers to a heteroaromatic system containing 4-10 ring atoms, 4-8 membered heteroaryl refers to a heteroaromatic system containing 4-8 ring atoms, including but not limited to pyrrolyl, furanyl, thienyl, pyrazolyl, thiazolyl, imidazolyl, oxazolyl, isoxazolyl, pyridinyl, pyranyl, pyridazinyl, pyrimidinyl, pyrazinyl, benzimidazolyl, triazolyl, and the like.
Flow battery
The working principle of the flow battery is shown in fig. 19, and the liquid electrolyte stored in the external storage tank is conveyed to the electrode surface in the reactor through the circulating pump to perform reversible oxidation-reduction reaction, so that energy storage and release of electric energy are realized. Compared with traditional chemical batteries such as lithium ion batteries, the flow battery has the advantage that energy and power are independent, namely the energy depends on the concentration and the volume of an energy storage material, and the power depends on the electrode area. The cost of this technology approaches the cost of the energy storage material as the energy storage scale is larger, so although lithium ion batteries have higher energy densities, flow batteries are more suitable for large scale energy storage power stations. Flow batteries are classified into aqueous flow batteries and non-aqueous (organic solvent) flow batteries according to the type of solvent used for the electrolyte.
Aqueous flow batteries are classified into aqueous inorganic flow batteries and aqueous organic flow batteries according to the energy storage materials used. The inorganic material has high cost and limited resources, dendrites are easy to form in the using process, and the defects of low electrochemical reaction rate and the like limit the large-scale application of the inorganic flow battery. The organic matter is used as an energy storage material, the source of the energy storage material is wider than that of limited metals stored in the crust, the use cost is lower, and the pollution of heavy metals to the environment can be reduced. Compared with inorganic materials, the organic materials have the advantages of light weight, low cost, ductility, plasticity and the like; the electrochemical reaction speed of the organic material is higher, usually 1 to 2 orders of magnitude higher than that of inorganic metal, no catalyst is needed, dendrites are not formed, and the diaphragm is damaged; meanwhile, a synthetic chemist can modify and functionalize the organic material from the molecular level, and the solubility and the oxidation-reduction potential of the organic material are optimized by introducing functional groups, so that the energy density and the open-circuit voltage of the battery are adjusted. Therefore, the structural characteristics, the electrochemical characteristics and the possible degradation mechanisms of the organic energy storage material are researched, so that the performance, the energy density and the service life of the water-based organic flow battery are improved, the cost of the water-based organic flow battery is reduced, and the water-based organic flow battery has very important significance for promoting the application of the flow battery in the energy storage field, reducing the environmental pollution and the energy waste and meeting the electric energy requirement of human production activities.
Compared with the prior art, the application has the main advantages that:
(1) The ferrocene derivative is synthesized by taking relatively abundant elements on earth such as carbon, hydrogen, nitrogen, iron and the like as raw materials, and has lower synthesis cost.
(2) The non-corrosive and nonflammable neutral water electrolyte and the cheap inorganic salt are used as the supporting electrolyte, so that the safety is high, the corrosiveness is low, the cost is low and the environment is friendly.
(3) And the energy storage scale is large.
Drawings
FIG. 1 is a cyclic voltammogram of Compound 1 in 1M NaCl solution;
FIG. 2 is a cyclic voltammogram of compound 2 in 1M NaCl solution;
FIG. 3 is a cyclic voltammogram of compound 3 in 1M NaCl solution;
FIG. 4 is a cyclic voltammogram of compound 4 in 1M NaCl solution;
FIG. 5 is a cyclic voltammogram of compound 5 in 1M NaCl solution;
FIG. 6 is a cyclic voltammogram of compound 6 in 1M NaCl solution;
FIGS. 7 and 8 are the results of charge-discharge cycle test of Compound 1 in 1M NaCl solution;
FIGS. 9 and 10 are the results of charge-discharge cycle test of Compound 2 in 1M NaCl solution;
FIGS. 11 and 12 are the results of charge-discharge cycle test of Compound 3 in 1M NaCl solution;
FIGS. 13 and 14 are charge-discharge cycle test results of Compound 4 in 1M NaCl solution;
FIGS. 15 and 16 are the results of charge-discharge cycle test of Compound 5 in 1M NaCl solution;
FIGS. 17 and 18 are the results of charge-discharge cycle test of Compound 6 in 1M NaCl solution;
fig. 19 is a schematic diagram and main parameters of a flow battery device.
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. Percentages and parts are by weight unless otherwise indicated.
Examples
Example 1 (Compound 1)
Step 1
Ferrocene 7 (50 mmol,9.32 g) was weighed into a 500mL Schlenk flask under nitrogen, and tetramethyl ethylenediamine (2.2 eq,16.5 mL) was added, followed by 100mL of ultra-dry diethyl ether. After cooling to-78 ℃, 69mL (2.2 eq,110 mmol) of n-butyllithium solution (1.6M in hexane) was added dropwise, and the mixture was stirred at room temperature overnight. Cooled again to-78 ℃, 15.4mL DMF (4 eq,110 mmol) was added dropwise, stirred at-78 ℃ for 0.5h, moved to room temperature and stirred further for 12h, quenched with water, then extracted with dichloromethane, washed with saturated sodium chloride solution, the combined organic phases dried over anhydrous magnesium sulfate and the solvent removed in vacuo. Column chromatography gave compound 8 (9.62 g, 83% yield) as a bright red solid.
Step 2
Compound 8 (10.46 g,43.2 mmol) was weighed into a 500mL Schlenk flask, 250mL of ultra-dry methylene chloride was added under nitrogen, followed by 54mL (2.5 eq,108 mmol) of dimethylamine solution (2M in THF), stirred at room temperature for 12h, sodium triacetoxyborohydride (27.5 g,3eq,130 mmol) was added, and the reaction was continued at room temperature for 12h. After the reaction, 1M NaOH (250 mL) was added to the reaction mixture to hydrolyze, the organic phase was separated, and the aqueous phase was extracted with methylene chloride several times. The combined organic phases were dried over anhydrous magnesium sulfate and the solvent was removed in vacuo. Petroleum ether dissolves crude product, filters, discards filter residue, spin-dries filtrate to obtain compound 9 as black red liquid (11.7 g,39 mmol) with a yield of 90%.
Step 3
Compound 9 (3.0 g,10 mmol) was weighed into a 350mL tube sealer, 20mL tetrahydrofuran was added, 60mL (6 eq) of methyl chloride (1M in THF) was added, the stopper was sealed and reacted overnight at 80 ℃ to precipitate a large amount of yellow solid in the reaction solution, which was filtered, washed with ethyl acetate, dried in a vacuum oven and purified by a C18 reverse phase silica gel column to give compound 1 as a bright yellow solid (3.7 g,9.3 mmol) in 93% yield.
1 H NMR(500MHz,D 2 O)δ4.64(s,2H),4.55(t,J=1.9Hz,2H),4.45(s,2H),3.02(s,9H). 13 C NMR(126MHz,D 2 O)δ73.65,73.24,71.88,66.23,66.22,66.20,51.98,51.95,51.92.
Example 2 (Synthesis of Compound 2)
Step 1
Compound 8 (2.42 g,10 mmol) was weighed into a 500mL Schlenk flask under nitrogen, 150mL of ultra-dry methylene chloride was added, followed by 1.22g (1.1 eq,11 mmol) of methylamine solution (27% -32% ethanol solution) and stirred overnight at room temperature, and 6.4g of sodium triacetoxyborohydride (3 eq,30 mmol) was added in two portions over 24 h. After the reaction is completed, saturated NaHCO is used 3 The aqueous solution was quenched and the organic phase separated and the aqueous phase extracted multiple times with dichloromethane. The combined organic phases were dried over anhydrous magnesium sulfate and the resulting solution was directly passed through a short silica gel column eluting with ethyl acetate, the solvent was removed from the collected solution and dried to give compound 10 as a yellow solid (1.08 g,4.5 mmol) in 45% yield.
Step 2
Compound 10 (1.34 g,5.56 mmol) was weighed into a 100mL Schlenk flask, 20mL of tetrahydrofuran, 3.9g (5 eq) of methyl iodide were added under nitrogen atmosphere, reacted overnight at room temperature, filtered, the filter cake was washed with ethyl acetate, compound 11 obtained after drying was orange yellow solid, and compound 2 (1.5 g,5.2 mmol) was obtained as yellow solid after ion exchange in 94% yield.
1 H NMR(500MHz,D 2 O)δ4.47(s,4H),4.40(s,4H),3.91(s,4H),3.40(s,6H). 13 CNMR(126MHz,D 2 O)δ73.74,72.21,71.80,59.68,52.74.
Example 3 (Synthesis of Compound 3)
Step 1
Compound 10 (2 g,8.3 mmol) was weighed into a 100mL Schlenk flask, acetonitrile 16mL,1, 3-diiodopropane 9.8g (4 eq) was added under nitrogen atmosphere, reacted for 20 hours at 50 ℃, the system precipitated a large amount of yellow solid, filtered, the filter cake was washed with ethyl acetate, and dried to give compound 12 as yellow solid 3.7g, which was used in the next step without further purification.
Step 2
Compound 12 (3.2 g,5.98 mmol) was weighed into a pressure-resistant bottle, 30mL of N, N-dimethylformamide, 11mL (6 eq,36 mmol) of trimethylamine (3.2M in ethanol) solution were sequentially added, and after sealing, the reaction was carried out at 50 ℃ for 24 hours to obtain compound 13 as an orange-yellow solid, which was purified by ion exchange followed by reverse phase column purification to obtain compound 3 as a yellow solid (1.7 g,4.2 mmol) in 70% yield.
1 H NMR(500MHz,D 2 O)δ4.50(s,4H),4.42(s,2H),4.38(s,2H),4.01(d,J=4.5Hz,4H),3.77(t,J=8.3Hz,2H),3.63–3.54(m,2H),3.45(s,3H),3.26(s,9H),2.58(t,J=8.0Hz,2H). 13 C NMR(126MHz,D 2 O)δ72.69,72.23,71.94,62.55,58.59,53.27,53.24,53.21,17.47.
Example 4 (Synthesis of Compound 4)
Compound 9 (1.35 g,4.5mmol,1 eq) was weighed into a pressure-resistant bottle, 20ml of tetrahydrofuran, 1, 3-diiodopropane 1.33g (4.5 mmol,1 eq) were added sequentially, the reaction was carried out for 3 hours at 80 ℃, a large amount of orange-yellow solid was precipitated from the system, filtered, the filter cake was washed with ethyl acetate to obtain compound 14 as a yellow solid 2.62g, yield 96%, and finally compound 4 was obtained by ion exchange.
1 H NMR(500MHz,D 2 O)δ4.66–4.62(m,4H),4.58–4.51(m,8H),3.25(t,J=8.2Hz,4H),3.02(s,12H),2.31(s,2H).
Example 5 (Synthesis of Compound 5)
Compound 9 (0.15 g,0.5mmol,1 eq) and ethylene glycol bistrifluoromethane sulfonate 0.163g (1 eq,0.5 mmol) were weighed and dissolved in 5ml of 1, 2-dichloroethane, reacted at 50 ℃ for 3h under nitrogen protection, a large amount of orange-yellow solid was precipitated from the system, filtered, the filter cake was washed with ethyl acetate to give compound 15, after ion exchange compound 5 was 1.4g as orange-yellow solid, yield 70%.
1 H NMR(500MHz,DMSO-d6)δ4.67(s,2H),4.48(s,4H),3.73(d,J=8.1Hz,2H),3.37(s,8H),2.95(s,6H).
Example 6 (Synthesis of Compound 6)
Compound 10 (0.483 g,2mmol,1 eq) and 0.488mg (4 mmol,2 eq) of 1, 3-propane sultone are weighed out and dissolved in 8mL of acetone, reacted for 10h at 60℃under nitrogen protection, filtered and the filter cake is washed with ethyl acetate to give compound 21 as an orange yellow solid, 0.6g, 83% yield.
1 H NMR(600MHz,D 2 O)δ4.51(td,J=2.6,1.3Hz,2H),4.49(td,J=2.6,1.3Hz,2H),4.44(ddt,J=7.5,2.7,1.4Hz,4H),4.08(d,J=14.2Hz,2H),3.91–3.83(m,4H),3.43(s,3H),3.14(t,J=6.9Hz,2H),2.49–2.40(m,2H).
Testing
Test example 1 cyclic voltammetry test (Compound 1)
The cyclic voltammetry test uses a three-electrode system. The working electrode is a 5mm glassy carbon electrode, the reference electrode is aqueous phase Ag/AgCl, and the counter electrode is a platinum wire electrode. Voltage scan range at test: the scanning rate is 20mV/s and is 0.2V-0.9V.
Cyclic voltammograms of test compound 1 in 1M NaCl solution are shown in fig. 1. The results show that the compound can show better oxidation under neutral conditionReduction performance. And has a high positive potential, E 1/2 =0.85V(vs SHE),ΔE=65mV。
Test example 2 cyclic voltammetry test (Compound 2)
The cyclic voltammetry test uses a three-electrode system. The working electrode is a 5mm glassy carbon electrode, the reference electrode is aqueous phase Ag/AgCl, and the counter electrode is a platinum wire electrode. Voltage scan range at test: the scanning rate is 20mV/s and is 0.2V-0.9V.
Cyclic voltammograms of test compound 2 in 1M NaCl solution are shown in fig. 2. The results show that the compound can show better oxidation-reduction performance under neutral conditions. And has a high positive potential, E 1/2 =0.76V(vs SHE),ΔE=64mV。
Test example 3 cyclic voltammetry test (Compound 3)
The cyclic voltammetry test uses a three-electrode system. The working electrode is a 5mm glassy carbon electrode, the reference electrode is aqueous phase Ag/AgCl, and the counter electrode is a platinum wire electrode. Voltage scan range at test: the scanning rate is 20mV/s and is 0.2V-0.9V.
Cyclic voltammograms of test compound 3 in 1M NaCl solution are shown in fig. 3. The results show that the compound can show better oxidation-reduction performance under neutral conditions. And has a high positive potential, E 1/2 =0.78V(vs SHE),ΔE=60mV。
Test example 4 cyclic voltammetry test (Compound 4)
The cyclic voltammetry test uses a three-electrode system. The working electrode is a 5mm glassy carbon electrode, the reference electrode is aqueous phase Ag/AgCl, and the counter electrode is a platinum wire electrode. Voltage scan range at test: the scanning rate is 20mV/s and is 0.3V-1.0V.
Cyclic voltammograms of test compound 4 in 1M NaCl solution are shown in fig. 4. The results show that the compound can show better oxidation-reduction performance under neutral conditions. And has a high positive potential, E 1/2 =0.87V(vs SHE),ΔE=75mV。
Test example 5 cyclic voltammetry test (Compound 5)
The cyclic voltammetry test uses a three-electrode system. The working electrode is a 5mm glassy carbon electrode, the reference electrode is aqueous phase Ag/AgCl, and the counter electrode is a platinum wire electrode. Voltage scan range at test: the scanning rate is 20mV/s and is 0.5V-0.9V.
Cyclic voltammograms of test compound 5 in 1M NaCl solution are shown in fig. 5. The results show that the compound can show better oxidation-reduction performance under neutral conditions. And has a high positive potential, E 1/2 =0.90V(vs SHE),ΔE=86mV。
Test example 6 cyclic voltammetry test (Compound 6)
The cyclic voltammetry test uses a three-electrode system. The working electrode is a 5mm glassy carbon electrode, the reference electrode is aqueous phase Ag/AgCl, and the counter electrode is a platinum wire electrode. Voltage scan range at test: the scanning speed is 20mV/s and is 0V-1.0V.
Cyclic voltammograms of test compound 6 in 1M NaCl solution are shown in fig. 6. The results show that the compound can show better oxidation-reduction performance under neutral conditions. And has a high positive potential, E 1/2 =0.77V(vs SHE),ΔE=80mV。
Test example 7 current cycle test (Compound 1)
The main parameters and schematic diagrams of the flow battery device are shown in fig. 19. And (3) performing constant-current constant-voltage charge-discharge cycle test by using an electrochemical workstation. The cell was assembled with compound 1 using a semion AMV anion exchange membrane, SGL39AA carbon paper as the electrode material. The charge and discharge current in the constant current stage is 100mA, and the current density is 20mA/cm 2 The voltage range in the constant voltage stage is 1.35V-0.4V, and the cut-off current is 20mA.
During the cycling of the cell, 7.0ml of 0.1M compound 1 as positive electrode solution was dissolved in 1M NaCl solution; the negative electrode solution was 30mL of 0.1M BTMAP-VI dissolved in 1M NaCl solution.
The results of compound 1 testing in 1M NaCl solution are shown in FIGS. 7 and 8. The constant-current constant-voltage charge and discharge test is performed for 300 circles, a stable charge and discharge platform can be maintained in the later stage of charge and discharge, the battery capacity is attenuated by 0.015%/circle (70 circles-300 circles), the actual capacity plays a role of 93% of theoretical capacity, and the coulomb efficiency in the stable stage can be more than 99%.
Test example 8 Current cycle test (Compound 2)
The main parameters and schematic diagrams of the flow battery device are shown in fig. 19. And (3) performing constant-current constant-voltage charge-discharge cycle test by using an electrochemical workstation. The cell was assembled with compound 2 using a semion AMV anion exchange membrane, SGL39AA carbon paper as the electrode material. The charge and discharge current in the constant current stage is 100mA, and the current density is 20mA/cm 2 The voltage range in the constant voltage stage is 1.35V-0.4V, and the cut-off current is 20mA.
During the cycling of the cell, 7.0ml of 0.1M compound 1 as positive electrode solution was dissolved in 1M NaCl solution; the negative electrode solution was 30mL of 0.1M BTMAP-VI dissolved in 1M NaCl solution.
The results of the test of compound 2 in 1M NaCl solution are shown in fig. 9 and 10. The constant-current constant-voltage charge and discharge test is carried out for 220 circles, a stable charge and discharge platform can be maintained in the later stage of charge and discharge, the battery capacity is kept stable, no attenuation is observed, the actual capacity plays a role of 99% of theoretical capacity, and the coulomb efficiency in the stable stage can reach more than 99%.
Test example 9 Current cycle test (Compound 3)
The main parameters and schematic diagrams of the flow battery device are shown in fig. 19. And (3) performing constant-current constant-voltage charge-discharge cycle test by using an electrochemical workstation. The cell was assembled with compound 3 using a semion AMV anion exchange membrane, SGL39AA carbon paper as the electrode material. The charge and discharge current in the constant current stage is 100mA, and the current density is 20mA/cm 2 The voltage range in the constant voltage stage is 1.35V-0.4V, and the cut-off current is 20mA.
During the cycling of the cell, 7.0ml of 0.1M compound 1 as positive electrode solution was dissolved in 1M NaCl solution; the negative electrode solution was 30mL of 0.1M BTMAP-VI dissolved in 1M NaCl solution.
The results of the test of compound 3 in 1M NaCl solution are shown in FIGS. 11 and 12. The constant-current constant-voltage charge and discharge test is carried out for 400 circles, a stable charge and discharge platform can be maintained in the later stage of charge and discharge, the battery capacity is kept stable, no attenuation is observed, the actual capacity plays a role of 99% of theoretical capacity, and the coulomb efficiency in the stable stage can reach more than 99%.
Test example 10 current cycle test (Compound 4)
The main parameters and schematic diagrams of the flow battery device are shown in fig. 19. And (3) performing constant-current constant-voltage charge-discharge cycle test by using an electrochemical workstation. The cell was assembled with compound 4 using a semion AMV anion exchange membrane, SGL39AA carbon paper as the electrode material. The charge and discharge current in the constant current stage is 100mA, and the current density is 20mA/cm 2 The voltage range in the constant voltage stage is 1.35V-0.4V, and the cut-off current is 20mA.
During the cycling of the cell, 7.0ml of 0.1M compound 1 as positive electrode solution was dissolved in 1M NaCl solution; the negative electrode solution was 20mL of 0.1M BTMAP-VI dissolved in 1M NaCl solution.
The results of compound 4 testing in 1M NaCl solution are shown in FIGS. 13 and 14. The constant-current constant-voltage charge and discharge test is carried out for 400 circles, the battery capacity is attenuated by 0.06 percent per circle (40 circles-400 circles), the actual capacity plays a role in occupying 69 percent of theoretical capacity, and the coulomb efficiency in the stationary phase can reach more than 99 percent.
Test example 11 current cycle test (Compound 5)
The main parameters and schematic diagrams of the flow battery device are shown in fig. 19. And (5) performing constant-current charge-discharge cycle test by using an electrochemical workstation. Assembled cell with Compound 5 Using SeThe lemion AMV anion exchange membrane is characterized in that carbon cloth is used as an electrode material. The constant current charge and discharge current is 100mA, and the current density is 20mA/cm 2 。
During the cycling of the cell, 7.0ml of 0.1M compound 1 as positive electrode solution was dissolved in 1M NaCl solution; the negative electrode solution was 20mL of 0.1M BTMAP-VI dissolved in 1M NaCl solution.
The results of the test of compound 5 in 1M NaCl solution are shown in fig. 15 and 16. The constant current charge and discharge test is carried out for 300 circles, the battery capacity is attenuated by 0.09 percent/circle (36-300 circles), the actual capacity plays the highest theoretical capacity of 67 percent, and the coulomb efficiency in the stationary phase can reach more than 99 percent.
Test example 12 current cycle test (Compound 6)
The main parameters and schematic diagrams of the flow battery device are shown in fig. 19. And (3) performing constant-current constant-voltage charge-discharge cycle test by using an electrochemical workstation. The cell was assembled with compound 6 using a semion AMV anion exchange membrane, SGL39AA carbon paper as the electrode material. The charge and discharge current in the constant current stage is 100mA, and the current density is 20mA/cm 2 The voltage range in the constant voltage stage is 1.35V-0.4V, and the cut-off current is 20mA.
During the cycling of the cell, 7.0ml of 0.1M compound 1 as positive electrode solution was dissolved in 1M NaCl solution; the negative electrode solution was 30mL of 0.1M BTMAP-VI dissolved in 1M NaCl solution.
The results of the test of compound 6 in 1M NaCl solution are shown in FIGS. 17 and 18. The constant-current constant-voltage charge and discharge test is carried out for 200 circles, the battery capacity is attenuated by 0.003 percent/circle (122 circles-200 circles), the actual capacity plays a role in occupying 99 percent of theoretical capacity, and the coulomb efficiency in the stationary phase can reach more than 99 percent.
In conclusion, compared with the prior art, the ferrocene derivative flow battery has the advantages of high voltage, high energy density, high charge and discharge efficiency, low battery capacity attenuation and high battery capacity.
All documents mentioned in this disclosure are incorporated by reference in this disclosure as if each were individually incorporated by reference. Further, it will be appreciated that various changes and modifications may be made by those skilled in the art after reading the above teachings, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Claims (11)
1. An aqueous flow battery based on ferrocene derivative electrolyte, comprising:
the electrolyte comprises a positive electrode material, wherein the positive electrode material is a water-soluble ferrocene derivative;
and the ferrocene derivative has a structure selected from the group consisting of:
wherein,,
m and n are each independently 0, 1,2, 3, 4 or 5;
p, q, x are each independently 1,2, 3, 4, 5, 6, 7 or 8;
R、R 1 、R 2 or R 3 Each independently selected from the group consisting of: H. halogen, hydroxy, mercapto, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted 3-10 membered heterocyclyl, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted 4-10 membered heteroaryl, amino, carboxy, -PO 3 X、-SO 3 X, or a group selected from the group consisting of:
R 0 selected from the group consisting of: -COOX, -SO 3 X、-PO 3 X、-NH 2 、-NHCH 3 、-N(CH 3 ) 2 、-N + (CH 3 ) 3 M - ;
Wherein X is selected from the group consisting of: h + 、NH 4 + 、Li + 、Na + 、K + 、Mg 2+ 、Al 3+ 、Ca 2+ The method comprises the steps of carrying out a first treatment on the surface of the Or X is a negative charge;
M - selected from the group consisting of: f (F) - 、Cl - 、Br - 、I - 、OH - 、OAc - 、OTf - 、OTs - 、SO 4 2- 、SO 3 2- 、PO 4 3- 、HPO 4 2- 、H 2 PO 4 - 、NO 2 - 、NO 3 - 、CO 3 2- 、HCO 3 - 、ClO 4 - 、ClO 3 - 、ClO 2 - 、ClO - Or CN - ;
R 4 、R 5 Each independently selected from the group consisting of: H. a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted 3-10 membered heterocycloalkyl group, or a substituted or unsubstituted C6-C10 aryl group, or a substituted or unsubstituted 4-10 membered heteroaryl group; or R is 4 And R is 5 Together with the carbon atoms to which they are attached form a 3-to 6-membered cycloalkyl or heterocyclyl group;
unless otherwise indicated, the substitution means substitution with a group selected from the group consisting of: C1-C10 alkyl, -COOX, -SO 3 X、-PO 3 X。
2. The flow battery of claim 1, wherein R is selected from the group consisting of: H. substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted 3-6 membered heterocyclyl;
R 1 、R 2 or R is 3 Each independently selected from the group consisting of: H. halogen, hydroxy, mercapto, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted 3-6 membered heterocyclyl, or a group selected from the group consisting of:
R 0 selected from the group consisting of: -COOX, -SO 3 X、-PO 3 X、-NH 2 、-NHCH 3 、-N(CH 3 ) 2 、-N + (CH 3 ) 3 M - ;
Wherein X is selected from the group consisting of: h + 、NH 4 + 、Li + 、Na + 、K + 、Mg 2+ 、Al 3+ 、Ca 2+ The method comprises the steps of carrying out a first treatment on the surface of the Or X is a negative charge;
M - selected from the group consisting of: f (F) - 、Cl - 、Br - Or I - ;
R 4 、R 5 Each independently selected from the group consisting of: H. substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl; or R is 4 And R is 5 Together with the carbon atoms to which they are attached form a 3-to 6-membered cycloalkyl or heterocyclyl group;
unless otherwise indicated, the substitution means substitution with a group selected from the group consisting of: C1-C10 alkyl, -COOX, -SO 3 X、-PO 3 X。
3. The flow battery of claim 1, wherein the ferrocene derivative has a structure selected from the group consisting of:
4. the flow battery of claim 1, wherein R is selected from the group consisting of: H. a substituted or unsubstituted C1-C4 alkyl group;
R 1 、R 2 or R is 3 Each independently selected from the group consisting of: H. a substituted or unsubstituted C1-C4 alkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted 3-6 membered heterocyclic group, or a group selected from the group consisting of:
R 0 selected from the group consisting of: -COOX、-SO 3 X、-PO 3 X、-NH 2 、-NHCH 3 、-N(CH 3 ) 2 、-N + (CH 3 ) 3 M - ;
Wherein X is selected from the group consisting of: h + 、NH 4 + 、Li + 、Na + 、K + 、Mg 2+ 、Al 3+ 、Ca 2+ ;
M - Selected from the group consisting of: f (F) - 、Cl - 、Br - Or I - ;
R 4 、R 5 Each independently selected from the group consisting of: H. substituted or unsubstituted C1-C4 alkyl;
unless otherwise indicated, the substitution means substitution with a group selected from the group consisting of: C1-C10 alkyl, -COOX, -SO 3 X、-PO 3 X。
5. The flow battery of claim 1, wherein R 1 Selected from the group consisting of: a substituted or unsubstituted C1-C4 alkyl group, or a group selected from the group consisting of:
wherein p is 1,2, 3 or 4, R 0 Selected from the group consisting of: -SO 3 X、-N + (CH 3 ) 3 M - ;
R 2 And R is 3 Each independently is methyl.
6. The flow battery of claim 2, wherein R is H; p, q, x are each independently 1,2, 3 or 4; m and n are each independently 0, 1 or 2.
7. The flow battery of claim 1, wherein the ferrocene derivative is selected from the group consisting of:
8. the flow battery of claim 1, wherein the negative electrode material is BTMAP-VI and has the following structure:
9. the flow battery of claim 1, wherein the supporting electrolyte is an inorganic supporting electrolyte and is selected from the group consisting of: sodium chloride salt solution, potassium hydroxide salt solution, or a combination thereof.
10. A ferrocene derivative, wherein said ferrocene derivative has a structure selected from the group consisting of:
wherein,,
m and n are each independently 0, 1,2, 3, 4 or 5;
p, q, x are each independently 1,2, 3, 4, 5, 6, 7 or 8;
R、R 1 、R 2 or R 3 Each independently selected from the group consisting of: H. halogen, hydroxy, mercapto, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted 3-10 membered heterocyclyl, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted 4-10 membered heteroaryl, amino, carboxy, -PO 3 H. A sulfonic acid group, or a group selected from the group consisting of:
R 0 selected from the group consisting of: -COOX, -SO 3 X、-PO 3 X、-NH 2 、-NHCH 3 、-N(CH 3 ) 2 、-N + (CH 3 ) 3 M - ;
Wherein X is selected from the group consisting of: h + 、NH 4 + 、Li + 、Na + 、K + 、Mg 2+ 、Al 3+ 、Ca 2+ The method comprises the steps of carrying out a first treatment on the surface of the Or X is a negative charge;
M - selected from the group consisting of: f (F) - 、Cl - 、Br - 、I - 、OH - 、OAc - 、OTf - 、OTs - 、SO 4 2- 、SO 3 2- 、PO 4 3- 、HPO 4 2- 、H 2 PO 4 - 、NO 2 - 、NO 3 - 、CO 3 2- 、HCO 3 - 、ClO 4 - 、ClO 3 - 、ClO 2 - 、ClO - Or CN - ;
R 4 、R 5 Each independently selected from the group consisting of: H. a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C3-C10 heterocycloalkyl group, or a substituted or unsubstituted C6-C10 aryl group, or a substituted or unsubstituted 4-10 membered heteroaryl group; or R is 4 And R is 5 Together form a 3-6 membered cycloalkyl or heterocyclyl group;
unless otherwise indicated, the substitution means substitution with a group selected from the group consisting of: C1-C10 alkyl, -COOX, -SO 3 X、-PO 3 X。
11. Use of a ferrocene derivative according to claim 10 for the preparation of a flow battery anode material.
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