CN113314751A - Aqueous organic flow battery - Google Patents

Aqueous organic flow battery Download PDF

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CN113314751A
CN113314751A CN202110575679.7A CN202110575679A CN113314751A CN 113314751 A CN113314751 A CN 113314751A CN 202110575679 A CN202110575679 A CN 202110575679A CN 113314751 A CN113314751 A CN 113314751A
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CN113314751B (en
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杨正金
徐铜文
陈倩如
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University of Science and Technology of China USTC
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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
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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Abstract

The invention discloses a water system organic flow battery, which comprises a positive electrode, a negative electrode and electrolyte, wherein the electrolyte comprises positive electrolyte and negative electrolyte; wherein the positive electrolyte comprises an aqueous solution containing a positive electroactive material; the positive electroactive material comprises a tetrathiafulvalene derivative containing at least one hydrophilic group; the negative electrode electrolyte includes an aqueous solution containing a negative electrode electroactive material.

Description

Aqueous organic flow battery
Technical Field
The invention belongs to the technical field of renewable energy storage, and particularly relates to a water system organic flow battery.
Background
The power generation of clean renewable energy sources such as wind, light and the like has fluctuation and discontinuity, the energy storage technology can solve the problems, and the supply and demand balance of a power system is adjusted, so that large-scale wind power photovoltaic facilities are smoothly merged into a power grid. The flow battery is used as a novel electrochemical energy storage facility with high capacity and low cost, and has the unique advantage that the energy and the power can be independently regulated and controlled. The traditional flow battery mainly uses transition metal as an electroactive material and has the defects of limited metal storage capacity, strong corrosion of electrolyte, serious transmembrane permeation, slow kinetics and the like.
The water-based organic flow battery adopts water-soluble organic electroactive molecules as electrolytes, has the advantages of rich raw material sources and highly adjustable performance, and has wider application prospect. However, most of the research on organic electrolytes is focused on negative electrode materials, the research and development of positive electrode materials are far behind, the developed types are limited to ferrocene, TEMPO and the like, and both electrolytes have the problem of easy degradation and cannot meet the requirements of practical application, so that the development of more potential molecules with high performance is urgently needed.
Disclosure of Invention
In view of the above, the present invention provides an aqueous organic flow battery, which is intended to at least partially solve the above technical problems.
The invention provides an aqueous organic flow battery, which comprises a positive electrode, a negative electrode and electrolyte, wherein the electrolyte comprises positive electrolyte and negative electrolyte; wherein the positive electrolyte comprises an aqueous solution containing a positive electroactive material; the positive electroactive material comprises a tetrathiafulvalene derivative containing at least one hydrophilic group; the negative electrode electrolyte includes an aqueous solution containing a negative electrode electroactive material.
According to an embodiment of the present invention, the tetrathiafulvalene derivative includes at least one of the compounds represented by structural formulas a to D:
structural formula a:
Figure BDA0003082485210000021
structural formula B:
Figure BDA0003082485210000022
structural formula C:
Figure BDA0003082485210000023
structural formula D:
Figure BDA0003082485210000024
wherein R is1、R2、R3、R4Is H, -COOH, -COOK, -NH2、-N(CH3)3 +、-CH2N(CH3)3 +、-OH、-SH、-OCH3、-N(CH3)2、-CH3、-CONH2、-PO3H2、-SO3H、-PO3K、-PO3Na、-PO3NH4、-SO3K、-SO3Na、SO3NH4-CONH(CH2)2NH2、-X、-(CH2OCH2)nCH2One or more of OH;
wherein n is a natural number of 1-9.
According to the embodiment of the invention, the positive electrode and the negative electrode both comprise electrodes, wherein the electrodes comprise one or more of carbon felt, carbon paper, carbon cloth, carbon black, activated carbon fibers, activated carbon particles, graphene, graphite felt and glassy carbon materials.
According to the embodiment of the invention, the molar concentration of the positive electrode electroactive material is 0.05-3 mol/L.
According to the embodiment of the invention, the positive electrode and the negative electrode both comprise current collecting plates, wherein the current collecting plates comprise one or more of conductive metal plates, graphite plates and carbon-plastic composite plates.
According to the embodiment of the invention, the negative electrode electroactive material comprises one or more of quinone derivatives, bipyridine derivatives, alloxazine derivatives, phenazine derivatives and vanadium salts.
According to an embodiment of the invention, the vanadium salt comprises one or more of a divalent vanadium salt, a trivalent vanadium salt.
According to the embodiment of the invention, the molar concentration of the negative electrode electroactive material is 0.05-3 mol/L.
According to an embodiment of the present invention, the electrolyte further comprises a supporting electrolyte, wherein the supporting electrolyte comprises one or more of sodium chloride, potassium phosphate, potassium nitrate, potassium sulfate, sodium nitrate, sodium sulfate, sodium phosphate, ammonium chloride, sulfuric acid, hydrochloric acid, potassium hydroxide, and sodium hydroxide.
According to the embodiment of the invention, the molar concentration of the supporting electrolyte comprises 0.5-5 mol/L.
The invention relates to an aqueous organic flow battery, wherein a positive electrode material of the aqueous organic flow battery adopts tetrathiafulvalene derivative with at least one hydrophilic group, as tetrathiafulvalene is a strong pi electron donor, reversible two-step one-electron redox reaction can be generated in an organic system, and the tetrathiafulvalene derivative with the hydrophilic group can be dissolved in aqueous electrolyte and keeps good redox reversibility and rapid reaction power.
Drawings
FIG. 1 schematically shows the preparation of TTF1, a tetrathiafulvalene derivative, prepared in example 11C NMR spectrum;
FIGS. 2 a-2 c schematically show cyclic voltammetry test profiles of tetrathiafulvalene derivative TTF1 in 1mol/L NaCl solution;
fig. 3 schematically shows an infrared spectrum of the tetrathiafulvalene derivative TTF2 prepared in example 2;
FIGS. 4 a-4 c schematically show the redox behavior of tetrathiafulvalene derivative TTF2 at different pH's in electrolytes of 1mol/L KOH solution, 1mol/L NaCl solution and 1mol/L H2SO4 solution, respectively;
FIGS. 5 a-5 c schematically show the tetrathiafulvalene derivative TTF2 at 2mol/L H2Cyclic voltammetry test plots in SO4 solution;
6 a-6 d schematically show graphs of the results of a rotating disk electrode test of tetrathiafulvalene derivative TTF 2;
7 a-7 b schematically show UV absorption curves and standard absorption curves at characteristic absorption peaks for the tetrathiafulvalene derivative TTF2 at different concentrations;
fig. 8 a-8 c schematically show test diagrams of an aqueous organic flow battery using tetrathiafulvalene derivative TTF2 as a positive electrode electroactive material.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
At present, research on electrolytes of water-based organic flow batteries mainly focuses on negative electrode materials, the development of positive electrode electrolytes lags behind, the existing molecular species are limited to ferrocene, TEMPO and the like, and the problems of easy degradation and the like exist, so that the water-based organic flow batteries are far away from practical application, and the development of more high-performance potential molecules is urgently needed. Tetrathiafulvalene is a strong pi electron donor, can undergo reversible two-step one-electron redox reactions in an organic system, and has been widely used as an organic dye sensitizer, a molecular probe and the like. However, tetrathiafulvalene has poor water solubility and cannot be directly used in an aqueous solution system. The tetrathiafulvalene derivative with good solubility is obtained by modifying tetrathiafulvalene with hydrophilic groups, and is used as an anode electroactive material to be applied to a water-based flow battery for the first time.
Therefore, the invention provides an aqueous organic flow battery, which comprises a positive electrode, a negative electrode and electrolyte, wherein the electrolyte comprises positive electrolyte and negative electrolyte; wherein the positive electrolyte comprises an aqueous solution containing a positive electroactive material; the positive electroactive material comprises a tetrathiafulvalene derivative containing at least one hydrophilic group; the negative electrode electrolyte includes an aqueous solution containing a negative electrode electroactive material.
In the embodiment of the invention, the positive electrode material adopts tetrathiafulvalene derivative with at least one hydrophilic group, and as tetrathiafulvalene is a strong pi electron donor, reversible two-step single electron redox reaction can occur in an organic system, and the tetrathiafulvalene derivative with the hydrophilic group can be dissolved in aqueous electrolyte and keep good redox reversibility and rapid reaction power.
In the embodiment of the invention, two one-electron redox reactions occur on a tetrathiafulvalene parent nucleus, and the reaction mechanism is as follows:
Figure BDA0003082485210000041
according to an embodiment of the present invention, the tetrathiafulvalene derivative includes at least one of the compounds represented by structural formulas a to D:
structural formula a:
Figure BDA0003082485210000042
structural formula B:
Figure BDA0003082485210000051
structural formula C:
Figure BDA0003082485210000052
structural formula D:
Figure BDA0003082485210000053
wherein R is1、R2、R3、R4Is H, -COOH, -COOK, -NH2、-N(CH3)3 +、-CH2N(CH3)3 +、-OH、-SH、-OCH3、-N(CH3)2、-CH3、-CONH2、-PO3H2、-SO3H、-PO3K、-PO3Na、-PO3NH4、-SO3K、-SO3Na、SO3NH4-CONH(CH2)2NH2、-X、-(CH2OCH2)nCH2One or more of OH; wherein n is a natural number of 1-9.
In the examples of the present invention, when R is1、R2、R3、R4When both are-COOK, the tetrathiafulvalene derivative TTF1 has the following structural formula (I):
Figure BDA0003082485210000054
in the examples of the present invention, when R is1、R2、R3、R4Are all-CONH (CH)2)2NH2The tetrathiafulvalene derivative TTF2 has the following structural formula (II):
Figure BDA0003082485210000055
according to the embodiment of the invention, the positive electrode and the negative electrode both comprise electrodes, wherein the electrodes comprise one or more of carbon felt, carbon paper, carbon cloth, carbon black, activated carbon fibers, activated carbon particles, graphene, graphite felt and glassy carbon materials.
According to the embodiment of the invention, the molar concentration of the positive electrode electroactive material is 0.05-3 mol/L. For example: 0.05mol/L, 1mol/L, 2mol/L and 3 mol/L.
According to the embodiment of the invention, the positive electrode and the negative electrode respectively comprise current collecting plates, wherein the current collecting plates comprise one or more of conductive metal plates, graphite plates and carbon-plastic composite plates.
According to the embodiment of the invention, the negative electrode electroactive material comprises one or more of quinone derivatives, bipyridine derivatives, alloxazine derivatives, phenazine derivatives and vanadium salts.
In the embodiment of the present invention, the quinone derivatives include, but are not limited to, 2, 7-anthraquinone disulfonic acid and 2, 6-dihydroxy anthraquinone. Bipyridine derivatives include, but are not limited to, methyl viologen, 1 '-bis [3- (trimethylammonium) propyl ] -4, 4' -bipyridine tetrachloride. Alloxazine derivatives include, but are not limited to, flavin mononucleotide, 7/8-alloxazine carboxylic acid. Phenazine derivatives include, but are not limited to, 7, 8-dihydroxyphenazine-2-sulfonic acid, 2-amino-3-hydroxyphenyloxazine.
According to an embodiment of the invention, the vanadium salt comprises one or more of a divalent vanadium salt, a trivalent vanadium salt.
In the embodiment of the invention, the divalent vanadium salt and the trivalent vanadium salt include, but are not limited to, by reducing VOSO4·3H2O, and the preparation method.
According to the embodiment of the invention, the molar concentration of the negative electrode electroactive material comprises 0.05-3 mol/L, such as: 0.05mol/L, 0.1mol/L, 0.5mol/L, 1mol/L, 3 mol/L.
According to an embodiment of the present invention, the electrolyte further comprises a supporting electrolyte, wherein the supporting electrolyte comprises one or more of sodium chloride, potassium phosphate, potassium nitrate, potassium sulfate, sodium nitrate, sodium sulfate, sodium phosphate, ammonium chloride, sulfuric acid, hydrochloric acid, potassium hydroxide, and sodium hydroxide.
According to the embodiment of the invention, the molar concentration of the supporting electrolyte comprises 0.5-5 mol/L. For example, 0.5mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5 mol/L.
The present invention will be described in detail below by taking tetrathiafulvalene derivative TTF1 and tetrathiafulvalene derivative TTF2 as examples.
Example 1
10.0g (0.04mol) of 1, 3-dithiole-2-thione-4, 5-dicarboxylic acid dimethyl ester and 10.0g (0.06mol) of triethyl phosphite are taken and added to 80mL of benzene and refluxed at 80 ℃ for 10 hours. And (5) waiting for the solution to be naturally cooled to room temperature, and removing benzene by rotary evaporation. 50mL of ethanol was added to the reaction flask and stirred, and the precipitate was filtered. Methanol is used as a solvent for recrystallization to obtain a purified product tetramethyl [2, 2' -bi (1, 3-dithio alkylidene)]-4, 4 ', 5, 5' -tetracarboxylic acid esters. 1mmol of the product was dissolved in 50mL of a mixed solution of methanol and tetrahydrofuran (volume ratio: 1), 6mL of a 2mol/L KOH solution was added, and the mixture was refluxed at 80 ℃ overnight. After the reaction was completed, water was added to the reaction solution until all the precipitate was dissolved, and the solution was acidified with 12mol/L HCl to pH 3, and a dark purple precipitate was observed. 4.5mmol of KOH was added to the reaction solution, and the reaction solution was left to stir at 75 ℃ for 12 hours. And filtering the reaction solution, washing a filter cake by using acetone, and drying in vacuum to obtain a product TTF1 of the tetrathiafulvalene derivative. Of the product1The C NMR spectrum is shown in figure 1,1c NMR spectra show that characteristic peaks on the C1, C2 and C3 in the structural formula of tetrathiafulvalene derivative TTF1 appear at 108.07ppm, 113.45ppm and 166.94ppm, and the molecular structure (III) of the compound is as follows:
Figure BDA0003082485210000071
the redox behavior of the tetrathiafulvalene derivative TTF1 was studied by cyclic voltammetry. The test instrument is a Zennium E workstation of Zahner, Germany, and the test adopts a three-electrode method, and comprises a glassy carbon electrode (working electrode), an Ag/AgCl electrode (reference electrode) and a platinum wire electrode (counter electrode). AlCl was prepared prior to testing3And polishing powder, which is prepared into slurry to polish and polish the glassy carbon electrode. Weighing tetrathiafulvalene derivative TTF1 and dissolving in 10mL of 1mol L-1In NaCl solution, the solution was shaken and stirred to prepare 10mmol L-1TTF1 solution of tetrathiafulvalene derivative.
S is 100mV in the interval of 0.2V to 1.0V (vs. SHE)-1Voltage change rate sweep. As a result, as shown in FIG. 2a, TTF1, a tetrathiafulvalene derivative, was able to undergo a two-step redox reaction, with a potential of 0.39V in the first step and 0.75V in the second step.
The first step electrochemical reaction was continuously scanned for 100 cycles in the range of 0.2V to 0.6V, and the result is shown in fig. 2b, in which the redox peak shape was significantly changed, and the turbidity of the test sample was observed, and the analysis was the change of the redox peak due to the precipitation.
After the test solution is diluted by 10 times, scanning is performed for 100 continuous cycles, and the result is shown in fig. 2c, the redox peak is not obviously changed before and after dilution, which indicates that the stability of the redox peak is obviously improved.
Example 2
10.0g (0.04mol) of 1, 3-dithiole-2-thione-4, 5-dicarboxylic acid dimethyl ester and 10.0g (0.06mol) of triethyl phosphite are taken and added to 80mL of benzene and refluxed at 80 ℃ for 10 hours. And (5) waiting for the solution to be naturally cooled to room temperature, and removing benzene by rotary evaporation. 50mL of ethanol was added to the reaction flask and stirred, and the precipitate was filtered. Methanol is used as a solvent for recrystallization to obtain a purified product tetramethyl [2, 2' -bi (1, 3-dithio alkylidene)]-4, 4 ', 5, 5' -tetracarboxylic acid esters. 0.60g (1.38mmol) of this product was taken up in 90mL of acetonitrile and the solution was stirred. Then slowly adding dropwise an excess8mL (50%, w/w) of an aqueous solution of ethylenediamine (Takeda). After all the drops were added, the reaction was left at room temperature and stirring was continued for 24 hours, whereupon a large amount of red solid appeared. And filtering the precipitate, washing the precipitate with acetonitrile, and drying the precipitate in vacuum to obtain the tetrathiafulvalene derivative TTF 2. Measuring its molecular weight by mass spectrometry 549.12, verifying its molecular structure by infrared spectrum, and showing C-H single bond (3200-3400 cm) in the infrared spectrum as shown in FIG. 3-1) C-O double bond (1600 cm)-1) C-C double bond (1700 cm)-1) N-H Single bond (1550 cm)-1) Thus demonstrating the molecular structure (tetra) of the tetrathiafulvalene derivative TTF2 as follows:
Figure BDA0003082485210000081
and (3) adopting cyclic voltammetry to examine the redox behavior of the tetrathiafulvalene derivative TTF2 molecule at different pH values. 10mmol L in 10mL three bottles-1TTF2 test samples were prepared using 1mol/L NaCl solution, 1mol L-1KOH solution and 1mol/L H2SO4The solution acts as a supporting electrolyte. The results for the three test samples are as follows:
as shown in FIG. 4a, the tetrathiafulvalene derivative TTF2 exhibits an irreversible redox peak in 1mol/L KOH solution. As shown in FIG. 4b, there was almost no redox peak in the 1mol/L NaCl solution. As shown in FIG. 4c, at 1mol/L H2SO4Two oxidation-reduction peaks with large potential difference can be shown in the solution.
The sulfuric acid concentration was adjusted to 2mol/L, as shown in FIG. 5a, at 2mol L-1H2SO4In solution, the tetrathiafulvalene derivative TTF2 is capable of undergoing a two-step one-electron redox reaction, wherein the electrode potential of the first step is 0.68V and the potential of the second step is 0.96V. The stability of the two-step redox reaction was tested using cyclic voltammetry, and as shown in fig. 5b, the redox peak shape changed significantly after 100 scans. If only the first step electrochemical reaction stability is tested, the redox peak shape is essentially unchanged after 1000 cycles of cyclic scanning, as shown in figure 5 c. Showing that the first step is electrochemical reactionIt should be very stable.
Example 3
The redox kinetic parameters of tetrathiafulvalene derivative TTF2 were determined by a rotating disk electrode method. The main instruments in this experiment were the CHI600E electrochemical workstation and the Pine E4TQ rotating disk electrode system. The test uses a three-electrode method (same cycle voltammetry test, in which the glassy carbon electrode is 50 mm). The concentration of the electrolyte in the test sample was 1mmol/L, and the concentration of the supporting electrolyte was 2mol/L H2SO4(ii) a Blank is 2mol/L H without adding electrolyte2SO4A solution; and subtracting the blank sample to obtain the output current of the electrolyte. Before testing, the working electrode is polished by alumina slurry, cleaned by deionized water and dried. During the test, N is continuously introduced2. The electrode voltage was scanned linearly at a rate of 5mV s-1The rotation speeds are sequentially set to be 100, 225, 400, 625, 900, 1225, 1600, 2025, 2500, 3025 and 3600rpm, the average value is obtained by scanning three times at each rotation speed, the scanning result is shown in FIG. 6a, and FIG. 6a schematically shows the response curve of current along with voltage change at different rotation speeds in the interval of 100-3600 rpm. For the square root omega of the measured limit diffusion current i and the rotating speed1/2The fitting is performed and the result is shown in fig. 6b, which fig. 6b schematically shows the limiting current i as a function of the square root of the rotational speed ω1/2The diffusion coefficient D is calculated by the Levich equation:
i＝0.620nFAcD2/3υ-1/6ω1/2
wherein i is the limiting diffusion current; n is a charge transfer number, and n is 1; f represents the Faraday constant of 96485C mol-1(ii) a A represents the area of the electrode, and is 0.196cm-2(ii) a c is electrolyte concentration and is 0.001mol L-1(ii) a Upsilon is 2mol L-1H2SO4Supporting the dynamic viscosity of the electrolyte; d represents the diffusion coefficient of the electrolyte molecules; ω is the set rotational speed of the electrode.
Under different overpotentials, the reciprocal 1/i of the current is converted into the reciprocal omega of the square root of the rotating speed-1/2The linear fit was performed and the results are shown in FIG. 6cFIG. 6c schematically shows the reciprocal 1/i of the current and the reciprocal ω of the square root of the rotation speed at different overpotentials-1/2Relation between (A) and (B)
Figure BDA0003082485210000091
Analysis) to obtain a kinetic control current ikFor the overpotential (. eta.) and the kinetic current (i)k) The linear fitting was performed, the fitting result is shown in FIG. 6d, FIG. 6d schematically shows a fitting curve of the Butler-Volmer equation, and the exchange current i was found by the intercept of the fitted straight line0And calculating an electron transfer rate constant k based on a Butler-Volmer equation0：
i0＝nFAck0
The results showed that the diffusion coefficient was 1.83X 10-6cm2 s-1The charge transfer rate constant was 0.018em s-1。
Example 4
The solubility of the tetrathiafulvalene derivative TTF2 was determined. The ultraviolet standard absorption curve of the tetrathiafulvalene derivative TTF2 was first plotted. Preparing a series of TTF2 standard samples of the tetrathiafulvalene derivative with different concentrations, performing spectral scanning at 0-900 nm by using an ultraviolet spectrophotometer to determine the position of a characteristic absorption peak, and performing linear fitting on the concentration by taking the absorption value at the characteristic peak to obtain a standard absorption curve of the tetrathiafulvalene derivative TTF 2. If the concentration of the unknown sample is within the concentration interval measured by the standard curve, the concentration of the unknown sample can be calculated through the fitted linear equation. Uv absorption curves of the tetrathiafulvalene derivative TTF2 at different concentrations (as shown in fig. 7 a) and standard absorption curves at characteristic absorption peaks (as shown in fig. 7 b). To 2mol L-1H2SO4Electrolyte is added to the solution continuously and dissolved by ultrasound, and the addition is stopped until the solution is saturated. And (3) diluting the saturated solution, measuring the ultraviolet absorption value of the diluted solution at the characteristic peak, calculating the electrolyte concentration of the diluted solution through a standard curve, and calculating the solubility of the electrolyte by combining the dilution times. The results show that the tetrathiafulvalene derivative TTF2 is 2mol L-1H2SO4The saturated solubility in (1) is 0.506mol L-1。
Example 5
Tetrathiafulvalene derivative TTF2 full flow battery performance was tested. Firstly, assembling the full flow battery, taking a middle diaphragm as a boundary, enabling components on the two sides of a positive electrode and a negative electrode to be consistent, and sequentially arranging a fixed plate frame, a conductive metal current collecting plate, a graphite plate containing a snakelike flow field, a polytetrafluoroethylene gasket and a carbon paper electrode (5 cm) from outside to inside2X 3) and Nafion 117 cation exchange membrane. The tetrathiafulvalene derivative TTF2 is used as a positive electrode electroactive material, and the concentration is 0.1mol L-1(ii) a Divalent vanadium salt and trivalent vanadium salt are used as negative electrode electroactive substances, and the concentration is 0.1mol L-1(ii) a The electrolyte on both sides takes water as a solvent and 2mol L-1H2SO4To support the electrolyte. The electrolyte is stored in a glass container, sealed with a rubber stopper, and connected to the battery assembly with a thin tube via a peristaltic pump. When the battery is in operation, the electrolyte is pumped by the pump to circulate in the battery stack and the external container.
The AC impedance spectrum (1 Hz-10 kHz) shows the results in FIG. 8a, the membrane resistance is 0.75 Ω cm2. When the battery is subjected to constant-current-constant-voltage cyclic charge and discharge tests, as shown in fig. 8b, a charging platform is obvious, the voltage is about 1.0V, a discharging platform is hardly visible, and the voltage quickly drops to the cut-off voltage of 0V. As shown in fig. 8C, the charge-discharge capacity decreased rapidly in the first 10 cycles and finally stabilized at about 5C.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. An aqueous organic flow battery comprises a positive electrode, a negative electrode and an electrolyte, wherein,
the electrolyte comprises a positive electrolyte and a negative electrolyte; wherein the content of the first and second substances,
the positive electrode electrolyte comprises an aqueous solution containing a positive electrode electroactive material;
the positive electroactive material comprises a tetrathiafulvalene derivative containing at least one hydrophilic group;
the negative electrolyte includes an aqueous solution containing a negative electroactive material.
2. The battery according to claim 1, wherein,
the tetrathiafulvalene derivative comprises at least one of compounds shown in structural formulas A-D:
structural formula a:
Figure FDA0003082485200000011
structural formula B:
Figure FDA0003082485200000012
structural formula C:
Figure FDA0003082485200000013
structural formula D:
Figure FDA0003082485200000014
wherein R is1、R2、R3、R4Is H, -COOH, -COOK, -NH2、-N(CH3)3 +、-CH2N(CH3)3 +、-OH、-SH、-OCH3、-N(CH3)2、-CH3、-CONH2、-PO3H2、-SO3H、-PO3K、-PO3Na、-PO3NH4、-SO3K、-SO3Na、-SO3NH4-CONH(CH2)2NH2、-X、-(CH2OCH2)nCH2One or more of OH;
wherein n is a natural number of 1-9.
3. The battery of claim 1, the positive electrode and the negative electrode each comprising an electrode, wherein the electrode comprises one or more of carbon felt, carbon paper, carbon cloth, carbon black, activated carbon fibers, activated carbon particles, graphene, graphite felt, glassy carbon material.
4. The battery according to claim 1, wherein the molar concentration of the positive electrode electroactive material is 0.05 to 3 mol/L.
5. The battery of claim 1, the positive electrode and the negative electrode each comprising a current collector, wherein the current collector comprises one or more of a conductive metal plate, a graphite plate, and a carbon-plastic composite plate.
6. The battery of claim 1, the negative electrode electroactive species comprising one or more of quinone derivatives, bipyridine derivatives, alloxazine derivatives, phenazine derivatives, vanadium salts.
7. The battery of claim 6, wherein the vanadium salt comprises one or more of a divalent vanadium salt, a trivalent vanadium salt.
8. The battery according to claim 6, wherein the molar concentration of the negative electrode electroactive material is 0.05 to 3 mol/L.
9. The battery of claim 1, the electrolyte further comprising a supporting electrolyte, wherein the supporting electrolyte comprises one or more of sodium chloride, potassium phosphate, potassium nitrate, potassium sulfate, sodium nitrate, sodium sulfate, sodium phosphate, ammonium chloride, sulfuric acid, hydrochloric acid, potassium hydroxide, and sodium hydroxide.
10. The battery of claim 9, wherein the molar concentration of the supporting electrolyte comprises 0.5-5 mol/L.
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