CN114105893A - Electrolyte based on amino acid derivatives and application thereof in flow batteries - Google Patents

Electrolyte based on amino acid derivatives and application thereof in flow batteries Download PDF

Info

Publication number
CN114105893A
CN114105893A CN202110185442.8A CN202110185442A CN114105893A CN 114105893 A CN114105893 A CN 114105893A CN 202110185442 A CN202110185442 A CN 202110185442A CN 114105893 A CN114105893 A CN 114105893A
Authority
CN
China
Prior art keywords
compound
group
unsubstituted
substituted
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202110185442.8A
Other languages
Chinese (zh)
Inventor
王盼
季云龙
庞帅
王昕怡
徐建聪
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Westlake University
Original Assignee
Westlake University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Westlake University filed Critical Westlake University
Priority to PCT/CN2021/115459 priority Critical patent/WO2022042735A1/en
Publication of CN114105893A publication Critical patent/CN114105893A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C07D241/46—Phenazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
    • C07C229/18—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to carbon atoms of six-membered aromatic rings
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention provides an electrolyte based on an amino acid derivative and application thereof in a flow battery, and particularly provides a compound shown as the following formula (I), wherein the compound can be used for preparing a high-performance flow battery energy storage material.

Description

Electrolyte based on amino acid derivatives and application thereof in flow batteries
Technical Field
The invention belongs to the technical field of energy storage of flow batteries. In particular to a synthesis method of several phenothiazine, quinone, phenothiazine and kahiene electrolytes with amino acid derivatives with redox activity and application thereof in an aqueous phase flow battery energy storage system.
Background
The rapid consumption of traditional energy sources (such as petroleum and coal) and the serious environmental pollution caused by the traditional energy sources urgently require cleaner energy sources so as to reduce the environmental pollution. With the development of scientific technology, the cost of clean energy sources such as solar energy and wind energy is lower than that of the traditional energy sources, however, the two clean energy sources have strong fluctuation and intermittency and have high requirements on the surrounding environment. However, the demand of human daily production activities for electric energy is quite regular, so the intermittency and fluctuation of clean energy prevents the large-scale application of the clean energy in the power grid. The supply and demand contradiction requires that a large-scale energy storage technology is developed to adjust the peak and the valley of the power utilization, namely, the energy is stored in the valley of the power utilization and is output in the peak, and support and guarantee are provided for the stability of the power grid. By the regulation, the waste of resources is reduced, clean energy is properly stored and utilized, and the clean energy is converted into a high-value and reliable product from low-value and unplanned energy.
The existing large-scale energy storage technologies comprise pumped storage, compressed air energy storage, electrochemical energy storage (secondary battery), super capacitor energy storage, flywheel energy storage and the like. Of all the energy storage technologies mentioned above, the first three energy storage technologies have a sufficiently long discharge time and a sufficiently large capacity range for storing solar energy and wind energy. Pumped storage requires two huge reservoirs at different altitudes, is a large project limited by special geographical conditions, may be accompanied by ecological problems, and is difficult to popularize in many places. The compressed air energy storage is an energy storage mode that electric power is used for compressing air, compressed high-pressure air is sealed in an air storage facility, and the compressed air is released to generate electricity when needed. Therefore, special geographical conditions such as rock caverns, abandoned mines and the like are also required as large air storage chambers, and part of energy is converted into heat energy in the process of air compression and release, resulting in low technical efficiency. In contrast, electrochemical energy storage has attracted extensive attention due to its advantages of environmental friendliness, high energy efficiency, low maintenance cost, adjustable properties, no geographical limitations, and the like, and among them, the flow battery is one of the most promising energy storage modes in the flow battery due to its abundant electrolyte reserve selection.
Flow batteries are classified into aqueous flow batteries and nonaqueous (organic solvent) flow batteries according to the type of solvent used for the electrolyte. The organic solvent used by the nonaqueous flow battery has certain toxicity, the cost of the organic solvent is far higher than that of water, and the organic solvent may cause environmental pollution; potential safety hazards caused by the flammability and explosiveness of the organic solvent also make the nonaqueous flow battery unsuitable for a large-scale energy storage power station. Therefore, the water system flow battery has a greater application prospect and application potential worth being popularized on a large scale. Among them, the aqueous flow battery using organic material as energy storage material is a current research hotspot because the energy storage material has wide sources and can modify and functionalize organic molecules by chemical means.
In view of the above, there is an urgent need in the art to develop novel organic energy storage materials.
Disclosure of Invention
The invention aims to develop a novel organic energy storage material.
In a first aspect of the present invention, there is provided a compound represented by the following formula (I):
Figure BDA0002942879570000021
wherein Y and Z are each independently selected from the group consisting of: n, NH, C ═ O, or S;
the dotted line is a bond or absent;
m1 and m2 are selected from the group consisting of: 0.1, 2, 3 or 4;
p1 and p2 are selected from the group consisting of: 0.1, 2, 3 or 4;
each R is independently selected from the group consisting of: halogen, substituted or unsubstituted C1-C10 alkyl, cycloalkyl, heterocycloalkyl, substituted or unsubstituted C6-C10 aryl, hydroxy, thiol, amine, carboxyl, phosphate, sulfonate, or the following:
Figure BDA0002942879570000022
R0selected from the group consisting of: -COOX, -SO3X、-PO3H2、-NH2、-NHCH3、-N(CH3)2、-N+(CH3)3M-(ii) a Wherein X is selected from the group consisting of: h+、NH4 +、Li+、Na+、K+、Mg2+、Al3+、Ca2+(ii) a M is selected from the group consisting of: F. cl, Br or I; each Rg is independently a functional group; wherein the functional group is
Figure BDA0002942879570000023
Wherein:
ra and Rb are each independently selected from the group consisting of: H. substituted or unsubstituted C1-C10 alkyl, cycloalkyl, heterocycloalkyl, substituted or unsubstituted C6-C10 aryl, or Ra and Rb taken together form a substituted or unsubstituted 3-8 membered nitrogen-containing heterocycle or nitrogen-containing heteroaryl ring; and the Rg at least comprises one R0A substituent group;
unless otherwise specified, the substitution refers to the substitution of one or more hydrogen atoms on the group with a substituent selected from the group consisting of: halogen, C1-C10 alkyl, cycloalkyl, heterocycloalkyl, C6-C10 aryl, hydroxyl, thiol, amine, carboxyl, phosphate, sulfonate.
In another preferred embodiment, the compound has a structure represented by formula (Ia), formula (Ib), formula (Ic) or formula (Id):
Figure BDA0002942879570000024
wherein R is1、R2、R3、R4、R5、R6、R7、R8Each independently selected from the group consisting of: H. halogen, substituted or unsubstituted C1-C10 alkyl, cycloalkyl, heterocycloalkyl, substituted or unsubstituted C6-C10 aryl, hydroxy, thiol, amine, carboxyl, phosphate, sulfonate, or functional group;
with the proviso that R1、R2、R3、R4、R5、R6、R7、R8Comprises at least one functional group.
In another preferred embodiment, R1、R2、R3、R4、R5、R6、R7、R8Each independently selected from the group consisting of: H. a substituted or unsubstituted C1-C10 alkyl, cycloalkyl, heterocycloalkyl, or functional group; wherein the functional group is a group selected from the group consisting of:
Figure BDA0002942879570000031
wherein each X, X1And X2Each independently selected from the group consisting of: H. NH (NH)4 +、Li+、Na+、K+、Mg2+、Al3+、Ca2+；
R9、R10And R11Each independently selected from the group consisting of: H. substituted or unsubstituted C1-C10 alkyl, cycloalkyl, heterocycloalkyl, or substituted or unsubstituted C6-C10 aryl;
n is 1, 2, 3, 4, 5, 6, 7 or 8;
c1 is a substituted or unsubstituted 3-8 membered heterocyclic ring (including partially unsaturated or saturated rings), or a substituted or unsubstituted 5-8 membered heteroaromatic ring.
In another preferred embodiment, Ra and Rb are each independently selected from the group consisting of: H. substituted or unsubstituted C1-C10 alkyl, cycloalkyl, heterocycloalkyl, and at least one R is included on Rg0And (4) a substituent.
In another preferred embodiment, R is9、R10And R11Each independently selected from the group consisting of: H. substituted or unsubstituted C1-C10 alkyl, cycloalkyl, heterocycloalkyl.
In another preferred embodiment, the compound is selected from the group consisting of:
Figure BDA0002942879570000041
in a second aspect of the invention, there is provided a process for the preparation of a compound according to the first aspect of the invention, said process comprising the steps of:
Figure BDA0002942879570000051
(i) reacting RgH with a compound of formula (II) in an inert solvent to give a compound of formula (I);
or the method comprises the following steps:
Figure BDA0002942879570000052
(1) reacting a compound of formula (III) with CH in an inert solvent2(ii) reaction with CHCOOEt to give a compound of formula (IIIa);
Figure BDA0002942879570000053
(2) reducing the compound of the formula (IIIa) in a hydrogen atmosphere to obtain a compound of a formula (IIIb);
Figure BDA0002942879570000054
(3) carrying out hydrolysis deprotection on the compound of the formula (IIIb) to obtain a compound of a formula (I-1);
wherein M is F, Cl, Br or I.
In another preferred embodiment, in step (i), the process is carried out in the presence of a palladium catalyst, a ligand and a base; preferably, the palladium catalyst is Pd2(dba)3The base istBuOK or Cs2CO3And the ligand is selected from the group consisting of: brettphos, RuPhos, XPhos or Pd2(dba)3；
In another preferred embodiment, in the step (1), the reaction is carried out in the presence of a palladium catalyst, a ligand, a base and a catalyst; preferably, the palladium catalyst is PdCl2The alkali is potassium carbonate, and the ligand is P (o-Tol)3And the catalyst is Bu4NBr。
In another preferred embodiment, in the step (2), the reaction is performed in the presence of palladium/carbon.
In another preferred embodiment, in the step (3), the reaction is carried out in the presence of a base; preferably, the base is NaOH.
In another preferred embodiment, in the step (i), the inert solvent is selected from the group consisting of: t-butanol, n-butanol, toluene, or a combination thereof.
In another preferred embodiment, in the step (1), the inert solvent is selected from the group consisting of: DMF, water, or a combination thereof.
In another preferred embodiment, in the step (2), the inert solvent is selected from the group consisting of: and (3) ethyl acetate.
In another preferred embodiment, in the step (2), the inert solvent is selected from the group consisting of: methanol, water, or a combination thereof.
In another preferred example, the method further comprises: after the reaction is finished, filtering and collecting filter cakes, dissolving the filter cakes by deionized water and then filtering again to remove insoluble impurities in the water. And collecting the filtrate, acidifying the filtrate by using HCl until the pH value is 3-4, separating out a solid, and filtering.
In another preferred example, the method further comprises: after the reaction is finished, the product is purified by a reverse phase column.
In a third aspect of the present invention, there is provided a flow battery energy storage material, wherein the flow battery energy storage material is prepared by using the compound according to the first aspect as an active ingredient.
In a fourth aspect of the invention, there is provided a flow battery comprising a compound according to the first aspect of the invention as an energy storage material.
In another preferred embodiment, the compound according to the first aspect of the present invention is used as a negative electrode or a positive electrode solution in the flow battery.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Drawings
FIG. 1 is a drawing of Compound 31H NMR chart;
FIG. 2 is a drawing of Compound 313C NMR chart;
FIG. 3 is a drawing of Compound 51H NMR chart;
FIG. 4 is a drawing of Compound 513C NMR chart;
FIG. 5 is a drawing of Compound 71H NMR chart;
FIG. 6 is a drawing of Compound 713C NMR chart;
FIG. 7 is a drawing of Compound 91H NMR chart;
FIG. 8 is a drawing of Compound 913C NMR chart;
FIG. 9 is a drawing of Compound 111H NMR chart;
FIG. 10 is a drawing of Compound 1113C NMR chart;
FIG. 11 is a drawing of Compound 131H NMR chart;
FIG. 12 is a drawing of Compound 1313C NMR chart;
FIG. 13 is a drawing of Compound 141H NMR chart;
FIG. 14 is a drawing of Compound 1413C NMR chart;
FIG. 15 is a drawing of Compound 151H NMR chart;
FIG. 16 is a photograph of Compound 1513C NMR chart;
FIG. 17 is a drawing of Compound 161H NMR chart;
FIG. 18 is a drawing of Compound 1613C NMR chart;
FIG. 19 is a drawing of Compound 191H NMR chart;
FIG. 20 is a drawing of Compound 201H NMR chart;
FIG. 21 is a drawing of Compound 211H NMR chart;
FIG. 22 is of Compound 221H NMR chart;
FIG. 23 is a cyclic voltammogram of Compound 15 in 1M KCl solution;
FIG. 24 is a schematic diagram showing the main parameters of a flow cell device;
fig. 25 is a graph of cell capacity, current efficiency, and energy efficiency as a function of number of battery cycles for compound 15 as an energy storage material;
FIG. 26 is a graph showing the relationship between cell capacity and voltage change for different cycles of cell cycling in the case of compound 15 as an energy storage material;
FIG. 27 is a cyclic voltammogram of Compound 3 in 1M KCl solution;
FIG. 28 is a cyclic voltammogram of Compound 5 in 1M KCl solution;
FIG. 29 is a cyclic voltammogram of Compound 7 in 1M KCl solution;
FIG. 30 is a cyclic voltammogram of Compound 9 in 1M KCl solution;
FIG. 31 is a cyclic voltammogram of Compound 11 in 1M KCl solution;
FIG. 32 is a cyclic voltammogram of Compound 13 in 1M KCl solution;
FIG. 33 is a cyclic voltammogram of Compound 14 in 1M KCl solution;
FIG. 34 is a cyclic voltammogram of Compound 16 in 1M KCl solution;
FIG. 35 is of Compound 221H NMR chart;
FIG. 36 is a photograph of Compound 231H NMR chart;
FIG. 37 is a drawing of Compound 241H NMR chart;
FIG. 38 is of Compound 251H NMR chart
FIG. 39 is of Compound 261H NMR chart;
FIG. 40 is a cyclic voltammogram of Compound 21 in 1M KCl solution;
FIG. 41 is a cyclic voltammogram of Compound 22 in 1M KCl solution;
FIG. 42 is a cyclic voltammogram of Compound 23 in 1M KCl solution;
FIG. 43 is a cyclic voltammogram of Compound 24 in 1M KCl solution;
FIG. 44 is a cyclic voltammogram of Compound 25 in 1M KCl solution;
FIG. 45 is a cyclic voltammogram of Compound 26 in 1M KCl solution;
FIGS. 46 and 47 are the results of charge-discharge cycling tests of Compound 22 in 1M KCl solution;
FIGS. 48 and 49 are the results of charge-discharge cycling tests of Compound 24 in 1M KCl solution;
FIGS. 50 and 51 are the results of charge-discharge cycling tests of Compound 25 in 1M KCl solution;
FIGS. 52 and 53 are the results of charge-discharge cycling tests of Compound 26 in 1M KCl solution.
Detailed Description
The present inventors have conducted extensive and intensive studies for a long time to develop a compound that can be used as an energy storage material for an aqueous flow battery. The preparation method of the compound is simple, and the prepared battery energy storage material has good cycle stability and energy efficiency. Based on the above findings, the inventors have completed the present invention.
Term(s) for
In the present invention, the halogen is F, Cl, Br or I.
In the present invention, the term "C1-C10" means having 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms, "C3-C6" means having 3, 4, 5, or 6 carbon atoms, and so on.
In the present invention, the term "alkyl" denotes a saturated linear or branched hydrocarbon moiety, for example the term "C1-C10 alkyl" means a straight or branched chain alkyl group having 1 to 10 carbon atoms, including, but not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl and the like; ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl are preferred.
In the present invention, the term "aryl" or "aromatic ring" denotes a hydrocarbyl moiety comprising one or more aromatic rings. Examples of aryl groups include, but are not limited to, phenyl (Ph), naphthyl, pyrenyl, fluorenyl, anthracenyl, and phenanthrenyl.
In the present invention, the term "heteroaryl" denotes a moiety comprising one or more aromatic rings having at least one heteroatom (e.g. N, O or S). Examples of heteroaryl groups include furyl, pyrrolyl, thienyl, oxazolyl, imidazolyl, thiazolyl, pyridyl, pyrimidinyl, quinazolinyl, quinolinyl, isoquinolinyl, indolyl and the like.
Flow battery
In the flow battery, electrolytes of a positive pole and a negative pole are respectively stored in an external liquid storage tank and are conveyed into an electric pile through a peristaltic pump, and an active substance generates an oxidation-reduction reaction on the surface of an electrode to realize the storage and the release of energy. Compared with traditional chemical batteries such as lithium ion batteries and the like, the flow battery has the advantages that energy and power are independent, namely the energy depends on the concentration and volume of an energy storage material, and the power depends on the area of an electrode. The cost of this technology approaches the cost of energy storage materials as the energy storage scale is larger, so flow batteries are more suitable for large-scale energy storage power stations despite their higher energy density. Flow batteries are classified into aqueous flow batteries and nonaqueous (organic solvent) flow batteries according to the type of solvent used for the electrolyte.
The aqueous flow battery is classified into an aqueous inorganic flow battery and an aqueous organic flow battery, depending on whether the energy storage material used is an inorganic material or an organic material. At present, most studied and widely applied energy storage materials are inorganic materials, but the inorganic materials have high cost and limited resources, are easy to form dendrites in the using process, have slow electrochemical reaction rate and the like, and limit the large-scale application of inorganic flow batteries. The organic matter is used as an energy storage material, the source of the organic matter is wider than that of metal with limited storage in the earth crust, the use cost is lower, and the pollution of heavy metal to the environment can be reduced. Compared with inorganic materials, organic materials have the advantages of light weight, low price, ductility, plasticity and the like; the electrochemical reaction speed of the organic material is higher, which is 1-2 orders of magnitude higher than that of inorganic metal, and the membrane is not damaged by dendrite without using a catalyst; meanwhile, a synthetic chemist can modify, transform 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 mechanism of the organic energy storage material are researched, so that the performance, the energy density and the service life of the water system organic flow battery are improved, the cost is reduced, and the method has very important significance for promoting the application of the flow battery in the field of energy storage, reducing environmental pollution and energy waste and meeting the requirement of human production activities on electric energy.
Energy storage material of flow battery
In the invention, a compound capable of being used as an organic energy storage material of an aqueous flow battery is provided, and specifically, the compound has a structure shown in the following formula (I):
Figure BDA0002942879570000081
wherein Y and Z are each independently selected from the group consisting of: n, NH, C ═ O, or S;
the dotted line is a bond or absent;
m1 and m2 are selected from the group consisting of: 0.1, 2, 3 or 4;
p1 and p2 are selected from the group consisting of: 0.1, 2, 3 or 4;
each R is independently selected from the group consisting of: halogen, substituted or unsubstituted C1-C10 alkyl, cycloalkyl, heterocycloalkyl, substituted or unsubstituted C6-C10 aryl, hydroxy, thiol, amine, carboxyl, phosphate, sulfonate, or the following:
Figure BDA0002942879570000091
R0selected from the group consisting of: -COOX, -SO3X、-PO3H2、-NH2、-NHCH3、-N(CH3)2、-N+(CH3)3M-(ii) a Wherein X is selected from the group consisting of: h+、NH4 +、Li+、Na+、K+、Mg2+、Al3+、Ca2+(ii) a M is selected from the group consisting of: F. cl, Br or I; each Rg is independently a functional group; wherein the functional group is
Figure BDA0002942879570000092
Wherein:
ra and Rb are each independently selected from the group consisting of: H. substituted or unsubstituted C1-C10 alkyl, cycloalkyl, heterocycloalkyl, substituted or unsubstituted C6-C10 aryl, or Ra and Rb taken together form a substituted or unsubstituted 3-8 membered nitrogen-containing heterocycle or nitrogen-containing heteroaryl ring; and the Rg at least comprises one R0And (4) a substituent.
In a preferred embodiment, the compounds have the structure shown for each of the compounds prepared in the examples.
The compound is dissolved in a solvent to be used as a negative electrode or positive electrode solution for assembling a flow battery.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are by weight.
Examples 1-9 Synthesis of amino acid derivatives of the phenazine family
Figure BDA0002942879570000093
Under nitrogen atmosphere, 2, 7-dibromophenazine (3mmol,1.014g), glycine (7.2mmol,0.54g), Pd were weighed2(dba)3(5 mol%, 137.4mg), Brettphos (10 mol%, 161mg), potassium tert-butoxide (15mmol,1.68g), tert-butanol 30mL in a thick-walled pressure-resistant reaction tube. Fully stirring and heating to 100 ℃, reacting for 12h and then cooling to room temperature. Filtering and collecting filter cake, dissolving the filter cake with deionized water, and filtering again to remove insoluble impurities in water. And (3) collecting the filtrate, acidifying the filtrate by using HCl until the pH value is 3-4, precipitating a solid, filtering, collecting a filter cake, washing the filter cake by using deionized water (2X 5mL), and drying to obtain the target compound 3. Further, purification (MeOH: H) by reverse phase column (C18)2O15: 85), yield 92%.
By replacing the starting materials for the reaction using the general procedure 1 described above, the following compounds 5 to 16 are obtained:
Figure BDA0002942879570000101
the nuclear magnetic spectra (including hydrogen spectrum and carbon spectrum) of the above compounds are shown in FIGS. 1-18.
Example 10 Synthesis of Phenazine alanine derivatives
Figure BDA0002942879570000111
The synthesis steps are as follows:
under nitrogen atmosphere, 2, 7-dibromophenazine (3mmol,1.014g),3,3' -iminodipropionitrile (12mmol,1.48g), Pd were weighed2(dba)3(5 mol%, 137.4mg), Brettphos (10 mol%, 161mg), cesium carbonate (21mmol,6.842g), t-butanol 10mL, in a reaction tube. Fully stirring and heating to 100 ℃, reacting for 12h, and filtering while the solution is hot. Solid YiyiWashed with deionized water, EtOH next time and dried in a vacuum oven to afford compound 18. Weighing compound 18(1mmol,422mg), adding into a thick-wall pressure-resistant bottle, adding NaOH (4mmol,160mg) and 4mL of deionized water, stirring thoroughly, heating to 150 ℃, reacting for 12h, cooling, filtering, and collecting solid. Further, purification (MeOH: H) by reverse phase column (C18)2O ═ 5:95) to give compound 19. The yield was 90%.
Examples 11 to 13 Synthesis of amino acid derivatives of the anthraquinones
Figure BDA0002942879570000112
Under nitrogen atmosphere, 2, 6-diiodoanthraquinone (3mmol,1.38g), glycine (9mmol,0.68g), Pd were weighed2(dba)3(5 mol%, 137.4mg), Brettphos (10 mol%, 161mg), potassium tert-butoxide (15mmol,1.68g), tert-butanol 30mL in a thick-walled pressure-resistant reaction tube. Fully stirring and heating to 120 ℃, reacting for 12h and then cooling to room temperature. Filtering and collecting filter cake, dissolving the filter cake with deionized water, and filtering again to remove insoluble impurities in water. And (3) collecting the filtrate, acidifying the filtrate by using HCl until the pH value is 3-4, precipitating a solid, filtering, collecting a filter cake, washing the filter cake by using deionized water (2 x 5mL), and drying to obtain the target compound 21.
The nuclear magnetic spectrum of the compound 20-22 obtained by the method is shown in fig. 20-22.
Figure BDA0002942879570000113
Examples 14-17 Synthesis of phenazine derivatives
Figure BDA0002942879570000114
1, 8-dibromophenazine (10g,29.8mmol), ethyl acrylate (17.9g,178.8mmol), palladium chloride (106mg,0.596mmol), tris (o-methylphenyl) phosphorus (726mg,2.384mmol), tetrabutylammonium bromide (1.92g,5.96mmol), potassium carbonate (16.4g,119.2mmol), N, N-dimethylformamide (8mL), and water (80mL) were weighed in a thick-walled pressure-resistant reaction tube under nitrogen atmosphere, stirred thoroughly, and heated to 100 ℃ for 12 h. After the reaction is finished, the system is cooled to room temperature, deep color insoluble solid in the system is filtered under reduced pressure, and is dissolved in dichloromethane again after being washed by distilled water and petroleum ether, and is washed by adding distilled water and saturated salt solution. The organic phase of the system is then separated, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure and subjected to flash chromatography on silica gel (developing solvent: dichloromethane/ethyl acetate/triethylamine: 500/20/3) and a large amount of dark green solid is obtained. The dark green solid was washed with ethyl acetate and filtered to afford pure yellow-green product 27(11.9g) in 70.8% yield.
Yellow-green solid 27(4.6g,12.23mmol) and palladium on carbon (460mg) were weighed into a reaction flask, and the air in the reaction flask was replaced with nitrogen and further with hydrogen. Then 150mL of ethyl acetate was added to the system and the reaction was stirred at 85 ℃ under an atmosphere of hydrogen for 12 h. The system, which was completed and cooled to room temperature, was filtered through celite, concentrated under reduced pressure, and subjected to silica gel chromatography (developing solvent: petroleum ether/ethyl acetate/triethylamine ═ 400/100/3) to give pure target compound 28(4.4g) in 94.6% yield.
Finally, the pure compound 28(4.4g,11.6mmol) obtained in the previous step was dissolved in 25mL of methanol, and an aqueous solution of sodium hydroxide [ sodium hydroxide (9.28g,232mmol) in 25mL of water ] was added thereto, and the system was sufficiently stirred and warmed to 65 ℃ for reaction. After 12h of reaction, the reaction system is cooled to room temperature and acidified by hydrochloric acid until a large amount of yellow-green solid is precipitated. The filter cake was then collected by filtration and washed thoroughly with distilled water to obtain the objective compound 24(3.72g) after drying in a yield of 99%.
By replacing the starting materials in the reaction using the general procedure described above, the following compounds 25, 26 are obtained:
Figure BDA0002942879570000121
test examples
Test example 1 Cyclic voltammetry test (Compound 15)
Cyclic voltammetry tests used a three electrode system. Wherein 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 sweep range during test: -1.1V to-0.3V, and a scan rate of 20 mV/s.
The cyclic voltammogram of compound 15 in 1M KCl solution was tested as shown in FIG. 23. The results show that the compound can show better oxidation-reduction performance under neutral (KCl) conditions. And has a relatively high negative potential, E1/2＝-0.56V,ΔE＝341mV。
Test example 2 Current circulation test
The main parameters and schematic diagram of the flow cell device are shown in fig. 24. And (5) carrying out constant-current charge-discharge cycle test by using an electrochemical workstation. The cell was assembled with compound 15 using Nafion117 cation exchange membrane, SGL39AA carbon paper as electrode material. The charging and discharging current is 100mA, and the current density is 20mA/cm2。
In the circulating process of the battery, 6.9mL of 0.1M compound 15 is dissolved in 1M KCl solution as a negative electrode solution; the positive electrode solution is 40mL of 0.1M K4FeCN6And 0.02M K3FeCN6Dissolved in 1M KCl solution. The circulation process adopts constant current circulation, and the current density is 20mA/cm2。
The results of testing compound 15 in 1M KCl solution are shown in FIGS. 25 and 26. Test results show that the compound has excellent battery cycling stability, constant-current uninterrupted charge and discharge test is performed for 6d, a stable charge and discharge platform is kept in the process, the battery capacity is not attenuated, the actual capacity is 91% of theoretical capacity, and the energy efficiency is 73%. Research results fully show that the compounds are ideal energy storage materials for water-based flow batteries.
Test example 3 Cyclic voltammetry test (Compound 3)
The cyclic voltammogram of compound 3 in 1M KCl solution was tested as shown in FIG. 27. The results show that the compound can show better oxidation-reduction performance under neutral (KCl) conditions. And has a relatively high negative potential, E1/2＝-0.52V,ΔE＝95mV。
Test example 4 Cyclic voltammetry test (Compound 5)
The cyclic voltammogram of compound 5 in 1M KCl solution was tested as shown in FIG. 28. The results show that the compound can show better oxidation-reduction performance under neutral (KCl) conditions. And has a relatively high negative potential, E1/2＝-0.54V,ΔE＝276mV。
Test example 5 Cyclic voltammetry test (Compound 7)
The cyclic voltammogram of compound 7 in 1M KCl solution was tested as shown in FIG. 29. The results show that the compound can show better oxidation-reduction performance under neutral (KCl) conditions. And has a relatively high negative potential, E1/2＝-0.52V,ΔE＝115mV。
Test example 6 Cyclic voltammetry test (Compound 9)
The cyclic voltammogram of compound 9 in 1M KCl solution was tested as shown in FIG. 30. The results show that the compound can show better oxidation-reduction performance under neutral (KCl) conditions. And has a relatively high negative potential, E1/2＝-0.53V,ΔE＝95mV。
Test example 7 Cyclic voltammetry test (Compound 11)
The cyclic voltammogram of compound 11 in 1M KCl solution was tested as shown in FIG. 31. The results show that the compound can show better oxidation-reduction performance under neutral (KCl) conditions. And has a relatively high negative potential, E1/2＝-0.57V,ΔE＝205mV。
Test example 8 Cyclic voltammetry test (Compound 13)
The cyclic voltammogram of compound 13 in 1M KCl solution was tested as shown in FIG. 32. The results show that the compound can show better oxidation-reduction performance under neutral (KCl) conditions. And has a relatively high negative potential, E1/2＝-0.52V,ΔE＝376mV。
Test example 9 Cyclic voltammetry test (Compound 14)
The cyclic voltammogram of compound 14 in 1M KCl solution was tested as shown in FIG. 33. The results show that the compound can show better oxidation-reduction performance under neutral (KCl) conditions. And has a relatively high negative potential, E1/2＝-0.51V,ΔE＝425mV。
Test example 10 Cyclic voltammetry test (Compound 16)
The cyclic voltammogram of compound 16 in 1M KCl solution was tested as shown in FIG. 34. The results show that the compound can show better oxidation-reduction performance under neutral (KCl) conditions. And has a relatively high negative potential, E1/2＝-0.51V,ΔE＝425mV。
Test example 11 Cyclic voltammetry test (Compound 21)
The cyclic voltammogram of compound 21 in 1M KCl solution was tested as shown in FIG. 40. The results show that the compound can show better oxidation-reduction performance under neutral (KCl) conditions. And has a relatively high negative potential, E1/2＝-0.56V,ΔE＝44mV。
Test example 12 Cyclic voltammetry test (Compound 22)
Cyclic voltammograms of test compound 22 in 1M KCl solution are shown in figure 41. The results show that the compound can show better oxidation-reduction performance under neutral (KCl) conditions. And has a relatively high negative potential, E1/2＝-0.60V,ΔE＝59mV。
Test example 13 Cyclic voltammetry test (Compound 23)
The cyclic voltammogram of compound 23 in 1M KCl solution was tested as shown in FIG. 42. The results show that the compound can show better oxidation-reduction performance under neutral (KCl) conditions. And has a relatively high negative potential, E1/2＝-0.60V,ΔE＝48mV。
Test example 14 Cyclic voltammetry test (Compound 24)
The cyclic voltammogram of test compound 24 in 1M KOH solution is shown in FIG. 43. The results show that the compound can show better oxidation-reduction performance under alkaline (KOH) conditions. And has a relatively high negative potential, E1/2＝-0.59V,ΔE＝163mV。
Test example 15 Cyclic voltammetry test (Compound 25)
Cyclic voltammograms of test compound 25 in 1M KOH solution are shown in figure 44. The results show that the compound can show better oxidation-reduction performance under alkaline (KOH) conditions. And has a relatively high negative potential, E1/2＝-0.56V,ΔE＝195mV。
Test example 16 Cyclic voltammetry test (Compound 26)
The cyclic voltammogram of test compound 25 in 1M KOH solution is shown in FIG. 45. The results show that the compound can show better oxidation-reduction performance under alkaline (KOH) conditions. And has a relatively high negative potential, E1/2＝-0.61V,ΔE＝91mV。
Test example 17 Current cycling test (Compound 22)
Figure BDA0002942879570000141
The main parameters and schematic diagram of the flow cell device are shown in fig. 24. And (5) carrying out constant-current charge-discharge cycle test by using an electrochemical workstation. The cell was assembled with compound 22 using Nafion117 cation exchange membrane, SGL39AA carbon paper as electrode material. The charging and discharging current is 100mA, and the current density is 20mA/cm2。
During the cycling of the cell, the negative electrode solution was 7.0mL of 0.1M compound 22 dissolved in 1M KCl at pH 12; the positive electrode solution is 40mL of 0.1M K4FeCN6And 0.02M K3FeCN6Dissolved in 1M KCl solution at pH 12. The circulation process adopts constant current circulation, and the current density is 20mA/cm2。
The results of testing compound 22 in 1M KCl (pH 12) solution are shown in figures 46, 47. Test results show that the compound has excellent battery cycling stability, constant-current uninterrupted charge and discharge tests are carried out for 10 days in total, a stable charge and discharge platform is maintained in the process, the battery capacity is attenuated by 0.61%/day, the actual capacity is exerted to 88% of theoretical capacity, and the energy efficiency is 68%. Research results fully show that the compounds are ideal energy storage materials for water-based flow batteries.
Test example 18 Current cycling test (Compound 24)
Figure BDA0002942879570000151
Main parameters and display of flow battery deviceIntended as shown in fig. 24. And carrying out constant-current and constant-voltage charge-discharge cycle tests by using an electrochemical workstation. The cell was assembled with compound 24 using Nafion117 cation exchange membrane, SGL39AA carbon paper as electrode material. The charging and discharging current is 100mA, and the current density is 20mA/cm2。
During the cycling of the battery, the negative solution was 7.0mL of 0.1M compound 24 dissolved in 1M KCl at pH 12; the positive electrode solution is 40mL of 0.1M K4FeCN6And 0.02M K3FeCN6Dissolved in 1M KCl solution at pH 12. The circulation process adopts constant current and constant voltage circulation, and the current density is 20mA/cm2。
The results of testing compound 24 in 1M KCl (pH 12) solution are shown in figures 48, 49. Test results show that the compound has excellent battery cycling stability, constant-current and constant-voltage uninterrupted charge and discharge tests are carried out for 20 days in total, a stable charge and discharge platform is maintained in the process all the time, the battery capacity is attenuated by 0.0033%/day, the actual capacity is 96% of theoretical capacity, and the energy efficiency is 66%. Research results fully show that the compounds are ideal energy storage materials for water-based flow batteries.
Test example 19 Current cycling test (Compound 25)
Figure BDA0002942879570000152
The main parameters and schematic diagram of the flow cell device are shown in fig. 24. And carrying out constant-current and constant-voltage charge-discharge cycle tests by using an electrochemical workstation. The cell was assembled with compound 25 using Nafion117 cation exchange membrane, SGL39AA carbon paper as electrode material. The charging and discharging current is 100mA, and the current density is 20mA/cm2。
During the cycling of the battery, the negative electrode solution was 7.0mL of 0.1M compound 25 dissolved in 1M KCl at pH 12; the positive electrode solution is 40mL of 0.1M K4FeCN6And 0.02M K3FeCN6Dissolved in 1M KCl solution at pH 12. The circulation process adopts constant current and constant voltage circulation, and the current density is 20mA/cm2。
The results of testing compound 25 in 1M KCl (pH 12) solution are shown in figures 50, 51. Test results show that the compound has excellent battery cycling stability, constant-current and constant-voltage uninterrupted charge and discharge tests are carried out for 20d in total, a stable charge and discharge platform is maintained in the process all the time, the battery capacity is attenuated by 0.0044%/day, the actual capacity is 99% of theoretical capacity, and the energy efficiency is 65%. Research results fully show that the compounds are ideal energy storage materials for water-based flow batteries.
Test example 20 Current cycling test (Compound 26)
Figure BDA0002942879570000161
The main parameters and schematic diagram of the flow cell device are shown in fig. 24. And carrying out constant-current and constant-voltage charge-discharge cycle tests by using an electrochemical workstation. The cells were assembled with compound 26 using Nafion117 cation exchange membrane, SGL39AA carbon paper as electrode material. The charging and discharging current is 100mA, and the current density is 20mA/cm2。
During the cycling of the battery, the negative solution was 7.0mL of 0.1M compound 26 dissolved in 1M KCl at pH 12; the positive electrode solution is 40mL of 0.1M K4FeCN6And 0.02M K3FeCN6Dissolved in 1M KCl solution at pH 12. The circulation process adopts constant current and constant voltage circulation, and the current density is 20mA/cm2。
The results of testing compound 26 in 1M KCl (pH 12) solution are shown in figures 52, 53. Test results show that the compound has excellent battery cycling stability, constant-current and constant-voltage uninterrupted charge and discharge tests are 18d in total, a stable charge and discharge platform is maintained all the time in the process, the battery capacity is attenuated 0.1110%/day, the actual capacity is expressed by 96% of theoretical capacity, and the energy efficiency is 70%. Research results fully show that the compounds are ideal energy storage materials for water-based flow batteries.
The results of the above examples show that the compound of the present invention has a higher negative potential and better redox performance when used as an energy storage material of a flow battery, and therefore, the compound is an ideal energy storage material of an aqueous flow battery.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.

Claims (10)

1. A compound of the following formula (I):
Figure FDA0002942879560000011
wherein Y and Z are each independently selected from the group consisting of: n, NH, C ═ O, or S;
the dotted line is a bond or absent;
m1 and m2 are selected from the group consisting of: 0.1, 2, 3 or 4;
p1 and p2 are selected from the group consisting of: 0.1, 2, 3 or 4;
each R is independently selected from the group consisting of: halogen, substituted or unsubstituted C1-C10 alkyl, cycloalkyl, heterocycloalkyl, substituted or unsubstituted C6-C10 aryl, hydroxy, thiol, amine, carboxyl, phosphate, sulfonate, or the following:
Figure FDA0002942879560000012
R0selected from the group consisting of: -COOX, -SO3X、-PO3H2、-NH2、-NHCH3、-N(CH3)2、-N+(CH3)3M-(ii) a Wherein X is selected from the group consisting of: h+、NH4 +、Li+、Na+、K+、Mg2+、Al3+、Ca2+(ii) a M is selected from the group consisting of: F. cl, Br or I; each Rg is independentIs a functional group; wherein the functional group is
Figure FDA0002942879560000013
Wherein:
ra and Rb are each independently selected from the group consisting of: h, substituted or unsubstituted C1-C10 alkyl, cycloalkyl, heterocycloalkyl, substituted or unsubstituted C6-C10 aryl, or Ra and Rb taken together form a substituted or unsubstituted 3-8 membered nitrogen-containing heterocycle or nitrogen-containing heteroaryl ring; and the Rg at least comprises one R0A substituent group;
unless otherwise specified, the substitution refers to the substitution of one or more hydrogen atoms on the group with a substituent selected from the group consisting of: halogen, C1-C10 alkyl, cycloalkyl, heterocycloalkyl, C6-C10 aryl, hydroxyl, thiol, amine, carboxyl, phosphate, sulfonate.
2. The compound of claim 1, having a structure according to formula (Ia), formula (Ib), formula (Ic), or formula (Id):
Figure FDA0002942879560000014
wherein R is1、R2、R3、R4、R5、R6、R7、R8Each independently selected from the group consisting of: H. halogen, substituted or unsubstituted C1-C10 alkyl, cycloalkyl, heterocycloalkyl, substituted or unsubstituted C6-C10 aryl, hydroxy, thiol, amine, carboxyl, phosphate, sulfonate, or functional group;
with the proviso that R1、R2、R3、R4、R5、R6、R7、R8Comprises at least one functional group.
3. The compound of claim 1, wherein R is1、R2、R3、R4、R5、R6、R7、R8Each independently selected from the group consisting of: H. a substituted or unsubstituted C1-C10 alkyl, cycloalkyl, heterocycloalkyl, or functional group; wherein the functional group is a group selected from the group consisting of:
Figure FDA0002942879560000021
wherein each X, X1And X2Each independently selected from the group consisting of: H. NH (NH)4 +、Li+、Na+、K+、Mg2+、Al3+、Ca2+；
R9、R10And R11Each independently selected from the group consisting of: H. substituted or unsubstituted C1-C10 alkyl, cycloalkyl, heterocycloalkyl, or substituted or unsubstituted C6-C10 aryl;
n is 1, 2, 3, 4, 5, 6, 7 or 8;
c1 is a substituted or unsubstituted 3-8 membered heterocyclic ring (including partially unsaturated or saturated rings), or a substituted or unsubstituted 5-8 membered heteroaromatic ring.
4. The compound of claim 1, wherein said compound is selected from the group consisting of:
Figure FDA0002942879560000031
Figure FDA0002942879560000041
5. a process for the preparation of a compound according to claim 1, comprising the steps of:
Figure FDA0002942879560000042
(i) reacting RgH with a compound of formula (II) in an inert solvent to give a compound of formula (I);
or the method comprises the following steps:
Figure FDA0002942879560000043
(1) reacting a compound of formula (III) with CH in an inert solvent2(ii) reaction with CHCOOEt to give a compound of formula (IIIa);
Figure FDA0002942879560000044
(2) reducing the compound of the formula (IIIa) in a hydrogen atmosphere to obtain a compound of a formula (IIIb);
Figure FDA0002942879560000045
(3) carrying out hydrolysis deprotection on the compound of the formula (IIIb) to obtain a compound of a formula (I-1);
wherein M is F, Cl, Br or I.
6. The process of claim 5, wherein in step (i), the process is carried out in the presence of a palladium catalyst, a ligand and a base; preferably, the palladium catalyst is Pd2(dba)3The base istBuOK or Cs2CO3And the ligand is selected from the group consisting of: brettphos, RuPhos, XPhos or Pd2(dba)3；
In the step (1), the reaction is carried out in the presence of a palladium catalyst, a ligand, a base and a catalyst; preferably, the palladium catalyst is PdCl2The alkali is potassium carbonate, and the ligand is P (o-Tol)3And the catalyst is Bu4NBr；
In the step (2), the reaction is carried out in the presence of palladium/carbon;
in the step (3), the reaction is carried out in the presence of a base; preferably, the base is NaOH.
7. The process of claim 5, wherein in step (i), the inert solvent is selected from the group consisting of: t-butanol, n-butanol, toluene, or a combination thereof;
in the step (1), the inert solvent is selected from the group consisting of: DMF, water, or a combination thereof;
in the step (2), the inert solvent is selected from the group consisting of: ethyl acetate;
in the step (2), the inert solvent is selected from the group consisting of: methanol, water, or a combination thereof.
8. A flow battery energy storage material prepared using the compound according to any one of claims 1 to 5 as an active ingredient.
9. A flow battery comprising a compound of any one of claims 1-5 as an energy storage material.
10. The flow battery of claim 9, wherein the compound of any one of claims 1-5 is used as a negative or positive solution in the flow battery.
CN202110185442.8A 2020-08-28 2021-02-10 Electrolyte based on amino acid derivatives and application thereof in flow batteries Pending CN114105893A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2021/115459 WO2022042735A1 (en) 2020-08-28 2021-08-30 Phenazine derivative-based electrolyte and application thereof in flow battery

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202010892586 2020-08-28
CN2020108925862 2020-08-28

Publications (1)

Publication Number Publication Date
CN114105893A true CN114105893A (en) 2022-03-01

Family

ID=80359338

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110185442.8A Pending CN114105893A (en) 2020-08-28 2021-02-10 Electrolyte based on amino acid derivatives and application thereof in flow batteries

Country Status (1)

Country Link
CN (1) CN114105893A (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019157437A1 (en) * 2018-02-09 2019-08-15 President And Fellows Of Harvard College Quinones having high capacity retention for use as electrolytes in aqueous redox flow batteries
CN110526826A (en) * 2019-08-22 2019-12-03 中盐金坛盐化有限责任公司 Synthetic method, derivative and the battery system of anthraquinone derivative containing carboxyl
EP3605696A2 (en) * 2018-08-02 2020-02-05 United Technologies Corporation Redox flow battery with electrolyte balancing and compatibility enabling features

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019157437A1 (en) * 2018-02-09 2019-08-15 President And Fellows Of Harvard College Quinones having high capacity retention for use as electrolytes in aqueous redox flow batteries
EP3605696A2 (en) * 2018-08-02 2020-02-05 United Technologies Corporation Redox flow battery with electrolyte balancing and compatibility enabling features
CN110526826A (en) * 2019-08-22 2019-12-03 中盐金坛盐化有限责任公司 Synthetic method, derivative and the battery system of anthraquinone derivative containing carboxyl

Similar Documents

Publication Publication Date Title
EP3580302A1 (en) Redox flow battery electrolytes
CN112563521B (en) Alkaline water-system mixed liquid flow battery based on electroactive phenazine derivative negative electrode
CN116143618B (en) Metal organic frame material for water-based zinc ion battery, ligand and application
CN113512033B (en) Phenoxazine and phenothiazine covalent triazine framework material, and preparation method and application thereof
CN114105893A (en) Electrolyte based on amino acid derivatives and application thereof in flow batteries
WO2022042735A1 (en) Phenazine derivative-based electrolyte and application thereof in flow battery
CN104610775A (en) Phenanthro-carbazole dye and preparation method thereof, as well as dye-sensitized solar cell
CN113999217B (en) New compound, preparation method and application thereof as co-sensitizer
CN115440506B (en) Preparation method of annular quaternary ammonium salt with asymmetric structure, product and application thereof
CN109748918A (en) Double pyridine anchoring group dye sensitizing agents and preparation method and application
CN114497662A (en) Application of multi-electron hexaazanaphthalene compound in aqueous flow battery
JP5035502B2 (en) Quinizaline bridged metal complex
CN111171046B (en) Doping-free hole transport material based on tetrathienopyrrole and synthetic method and application thereof
CN108795090B (en) X-type double-anchoring dye sensitizer and preparation method and application thereof
CN109400622B (en) Asymmetric organic hole transport material with nitrogen pyrrole thiophene as mother nucleus and synthesis method and application thereof
CN114300723B (en) Aqueous organic flow battery based on mixed energy storage of insoluble phenazine-based negative electrode and soluble phenazine-based negative electrode electrolyte
CN114249746A (en) Spirofluorene xanthene triarylamine hole transport material and preparation method and application thereof
CN116706178A (en) Aqueous flow battery based on ferrocene derivative electrolyte
CN114824398B (en) Polyacrylic acid grafted polymer flow battery system
CN114315856B (en) Doping-free hole transport material containing phenazine dithiophene and preparation method and application thereof
CN115745972B (en) Nitrogen-containing organic positive electrode material, and preparation method and application thereof
CN115160323B (en) Conjugated macrocyclic dicarbazole derivative R- (BCz-Ph) m and synthetic method and application thereof
CN113690059B (en) FeCo 2 O 4 // AC water system asymmetric photo-assisted supercapacitor and preparation method thereof
CN117712439A (en) Oxidative reduction organic flow battery for energy storage and application thereof
CN116093391A (en) Electrolyte for positive electrode of organic flow battery and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination