CN112993355B

CN112993355B - Organic flow battery

Info

Publication number: CN112993355B
Application number: CN201911275513.2A
Authority: CN
Inventors: 李先锋; 刘婉秋; 张华民
Original assignee: Dalian Institute of Chemical Physics of CAS
Current assignee: Dalian Institute of Chemical Physics of CAS
Priority date: 2019-12-12
Filing date: 2019-12-12
Publication date: 2022-05-31
Anticipated expiration: 2039-12-12
Also published as: CN112993355A

Abstract

An organic flow battery comprises a single cell or a cell stack consisting of more than 2 single cells. The monocell comprises a positive electrode, a diaphragm and a negative electrode, wherein the electrolyte of the positive electrode is introduced between the positive electrode and the diaphragm, and the electrolyte of the negative electrode is introduced between the negative electrode and the diaphragm. The positive electrode electrolyte in the positive electrode electrolyte is a dihydroxybiphenyl compound.

Description

Organic flow battery

Technical Field

The invention belongs to the field of flow batteries, and particularly relates to an organic flow battery.

Background

Due to the resource problem of fossil energy and the environmental pollution problem, renewable energy accounts for increasing proportion of energy consumption. However, renewable energy sources such as wind energy and solar energy have the defects of discontinuity, instability and uncontrollable, which causes great economic loss and resource waste. Therefore, an efficient, reliable and safe energy storage technology is required to improve the quality and utilization rate of renewable energy. The flow battery has the advantages of being safe and reliable, and the like, and is the most promising large-scale energy storage technology at present because the power and the energy can be separately regulated and controlled, and are not limited by regional environment.

The current developed and mature flow batteries comprise all-vanadium flow batteries and the like, but all-vanadium flow batteries need to use high-concentration sulfuric acid, cause corrosion to pipelines, are limited in metal resources such as vanadium and the like, and belong to non-renewable energy sources. The organic flow battery has the advantages of wide variety, convenient regulation and control, low cost, sustainability and the like, and is widely concerned.

Disclosure of Invention

In order to achieve the purpose, the specific technical scheme of the invention is as follows:

the invention provides an organic flow battery, which comprises single cells or an electric pile consisting of more than 2 single cells; the single cell comprises a positive electrode, a diaphragm and a negative electrode, wherein the electrolyte of the positive electrode is introduced between the positive electrode and the diaphragm, and the electrolyte of the negative electrode is introduced between the negative electrode and the diaphragm; the method is characterized in that: the positive electrode electrolyte in the positive electrode electrolyte is a dihydroxybiphenyl compound.

The flow battery is characterized in that the dihydroxybiphenyl compound is an organic compound represented by the following general formula (1),

Y1-Y8 in the formula (1) independently represent a hydroxyl group, hydrogen, fluorine, chlorine, bromine, a cyano group, a nitro group, a C1-C20 chain saturated hydrocarbon group, a C2-C20 chain unsaturated hydrocarbon group, a C3-C20 Cyclic saturated hydrocarbyl, C3-C20 Cyclic unsaturated hydrocarbyl, -COR1 or-N (R2)₂One of (1);

r1 and R2 are each independently one member selected from the group consisting of hydrogen, a C1-C20 chain saturated hydrocarbon group, a C2-C20 chain unsaturated hydrocarbon group, a C2-C20 cyclic saturated hydrocarbon group, a C3-C20 cyclic unsaturated hydrocarbon group, a cyano group and a nitro group, -N (R2)₂Two of R2 may be the same or different;

the chain saturated hydrocarbon group, the chain unsaturated hydrocarbon group, the cyclic saturated hydrocarbon group or the cyclic unsaturated hydrocarbon group described in the optional substituents for Y1 to Y8 and R1 and R2 does not contain or contains at least 1 selected from an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom.

The flow battery is characterized in that the concentration of the dihydroxybiphenyl compound in the positive electrode electrolyte is 0.05mol/L to the saturated concentration of the dihydroxybiphenyl compound.

The organic flow battery is characterized in that the anode or the cathode is respectively a carbon felt, a carbon cloth, a carbon paper or a graphite plate. The flow battery is characterized in that the negative electrolyte in the negative electrolyte solution of the flow battery contains one or more than two of the following substances: silicotungstic acid, 2, 7-anthraquinone-disodium disulfonate, stannic chloride, lead sulfate, cadmium chloride and vanadium trichloride. The flow battery is characterized in that hydroxyl in a dihydroxy biphenyl compound in a positive electrolyte in the positive electrolyte undergoes an oxidation-reduction reaction of electron transfer; the negative electrode electrolyte in the negative electrode electrolyte solution undergoes an oxidation-reduction reaction of electron transfer.

The flow battery is characterized in that the total concentration of the negative electrolyte in the negative electrolyte solution is 0.05mol/L to the saturated concentration of the negative electrolyte solution.

The flow battery is characterized in that the diaphragm is an ion exchange membrane or a porous membrane.

The flow battery is characterized in that the positive electrode electrolyte and/or the negative electrode electrolyte further comprise a supporting electrolyte, the supporting electrolyte contains one or more of hydrochloric acid, sulfuric acid, perchloric acid, acetic acid, methanesulfonic acid, sulfamic acid, trifluoromethanesulfonic acid and phosphoric acid, and the concentration of the supporting electrolyte in the electrolyte is 0.05 mol/L-6.0 mol/L.

Advantageous effects

According to the organic flow battery provided by the invention, the dihydroxybiphenyl compound is used as the positive electrode electrolyte of the flow battery, and the dihydroxybiphenyl compound can perform reversible redox reaction and has good reversibility and excellent dynamic performance. In particular, under acidic supporting electrolyte conditions, the dihydroxybiphenyl compounds can exhibit a relatively positive potential, and matching with a suitable negative electrolyte can match an organic flow battery with excellent performance. In addition, the main constituent elements of the dihydroxybiphenyl compound are carbon, hydrogen and oxygen, and the element sources are cheap and rich, so that the cost of the dihydroxybiphenyl compound organic flow battery after large-scale production and manufacturing is greatly reduced compared with the existing heavy metal ion flow battery such as vanadium, the cost is favorable for sustainable development, and the dihydroxybiphenyl compound organic flow battery is suitable for a large-scale energy storage technology.

Drawings

FIG. 1 shows the results of cyclic voltammetry tests of a solution of 1,1'- (4,4' -dihydroxy- [1,1 '-biphenyl ] -3,3', 5,5 '-tetrayl) tetrakis (N, N-dimethylmethylammonium) (hereinafter referred to as 4,4' -BPTDAM) prepared in example 1 of the present invention, with saturated calomel as a reference electrode, at sweep rates of 10mV/s,30mV/s,50mV/s,70mV/s,90mV/s, and 200 mV/s.

FIG. 2 shows the results of the cyclic voltammetry test of the 4,4' -BPTTAE solution prepared in example 1.

FIG. 3 shows the results of cyclic voltammetry tests of a solution of 1,1' - (4,4' -dihydroxy- [1,1' -biphenyl ] -3,3' -diyl) bis (N, N-dimethylmethylammonium) (hereinafter referred to as 4,4' -BPDDAM) prepared in example 2 of the present invention, using saturated calomel as a reference electrode, at sweep rates of 10mV/s,30mV/s,50mV/s,70mV/s,90mV/s, and 200 mV/s.

Fig. 4 is a graph of the efficiency of the assembled battery of example 3 of the present invention at different current charging and discharging conditions.

Fig. 5 is a voltage-capacity diagram for different current charging and discharging situations of the assembled battery in example 3 of the present invention.

Fig. 6 is a graph showing the cycle performance of the assembled battery of example 3 of the present invention at a current of 270 mA.

Fig. 7 is a graph showing the cycle performance of the assembled battery of comparative example 1 of the present invention at a current of 50 mA.

Detailed Description

Example 1

Weighing 4,4 '-BPTDAM and 30 ml of 2mol/L hydrochloric acid solution, oscillating and stirring to form a uniform solution, and then obtaining 0.001 mol/L4, 4' -BPTDAM solution. And (3) carrying out cyclic voltammetry test on the prepared electrolyte by using a three-electrode system, wherein saturated calomel is used as a reference electrode, a graphite electrode is used as a counter electrode, and a carbon felt electrode is used as a working electrode. The sweep rate was 10mV/s,30mV/s,50mV/s,70mV/s,90mV/s,200 mV/s.

From the cyclic voltammetry data in fig. 1, under the condition, a pair of obviously reversible redox peaks exist, the electrochemical reversibility is good, and when saturated calomel is taken as a reference electrode, the average potential of 4,4' -BPTDAM is more than 0.5V.

From the cyclic voltammetry data of fig. 2 at different cycle times, the cyclic voltammetry curves of 5 th, 50 th and 100 th times are basically overlapped, which shows that the stability is good.

Example 2

Weighing 4,4 '-BPTDDM and 30 ml of 2mol/L hydrochloric acid solution, oscillating and stirring to form a uniform solution, and then obtaining 0.001 mol/L4, 4' -BPTDDM solution. And (3) carrying out cyclic voltammetry test on the prepared electrolyte by using a three-electrode system, wherein saturated calomel is used as a reference electrode, a graphite electrode is used as a counter electrode, and a carbon felt electrode is used as a working electrode. The sweep rates were 10mV/s,30mV/s,50mV/s,70mV/s,90mV/s,200 mV/s.

Example 3

Weighing 4,4 '-BPTDAM and dissolving in 8 ml of 2mol/L hydrochloric acid solution, oscillating and stirring, and forming 0.1 mol/L4, 4' -BPTDAM solution as the anode electrolyte after the solution is formed into a uniform solution. Weighing 2, 7-disulfonic acid-anthraquinone-disodium, dissolving the 2, 7-disulfonic acid-anthraquinone-disodium in 8 ml of 2mol/L hydrochloric acid solution, oscillating and stirring the solution to form a uniform solution, and preparing 0.1 mol/L2, 7-disulfonic acid-anthraquinone-disodium solution as a negative electrode electrolyte. And (3) introducing the electrolyte into the flow battery device to serve as positive and negative electrolyte. The battery is assembled by the sequence and the positions of the graphite current collector, the graphite felt electrode, the ion exchange membrane, the graphite felt electrode and the graphite current collector, and the liquid is driven by a peristaltic pump to be charged and discharged.

As shown in FIG. 4, when the flow battery is charged and discharged under the currents of 9mA,18mA,27mA,36mA and 45mA, the coulomb efficiency, the voltage efficiency and the energy efficiency of the flow battery are all kept at a high level. As shown in fig. 5, the flow battery maintains a high capacity at different currents. As shown in FIG. 6, the flow battery is subjected to charge-discharge circulation under the current of 270mA, and the efficiency and the capacity are not greatly attenuated.

Comparative example 1

Weighing 2, 5-dihydroxy benzene disulfonate disodium salt, dissolving the 2, 5-dihydroxy benzene disulfonate disodium salt in 8 ml of 2mol/L hydrochloric acid solution, oscillating and stirring the solution until the solution forms a uniform solution, and then obtaining 0.1 mol/L2, 5-dihydroxy benzene disulfonate disodium salt solution as the anode electrolyte. Weighing 2, 7-disulfonic acid-anthraquinone-disodium, dissolving the 2, 7-disulfonic acid-anthraquinone-disodium in 8 ml of 2mol/L hydrochloric acid solution, oscillating and stirring the solution to form a uniform solution, and preparing a 0.1 mol/L2, 7-disulfonic acid-anthraquinone-disodium solution as a negative electrode electrolyte. And (3) introducing the electrolyte into the flow battery device to serve as positive and negative electrolyte. The battery is assembled by the sequence and the positions of a graphite current collector, carbon paper/graphite felt electrode, an ion exchange membrane, carbon paper/graphite felt electrode and a graphite current collector, and liquid is driven by a peristaltic pump to be charged and discharged.

As shown in fig. 7, the flow battery of comparative example 1 was cycled charge and discharge at a lower current (50mA) with both efficiency and capacity degradation.

Claims

1. An organic flow battery comprises a single cell or a galvanic pile consisting of more than 2 single cells; the single cell comprises a positive electrode, a diaphragm and a negative electrode, wherein the electrolyte of the positive electrode is introduced between the positive electrode and the diaphragm, and the electrolyte of the negative electrode is introduced between the negative electrode and the diaphragm; the method is characterized in that: the positive electrolyte in the positive electrolyte is a dihydroxybiphenyl compound; the positive electrode electrolyte and the negative electrode electrolyte also comprise supporting electrolyte, and the supporting electrolyte contains one or more of hydrochloric acid, sulfuric acid, perchloric acid, acetic acid, methanesulfonic acid, sulfamic acid, trifluoromethanesulfonic acid and phosphoric acid;

the dihydroxybiphenyl compound is an organic compound represented by the following general formula (1),

（1）

y1 to Y8 in the formula (1) independently represent hydrogen, fluorine, chlorine, bromine, hydroxyl, cyano, nitro, sulfonic acid group, C1 to C20 chain saturated alkyl, C2 to C20 chain unsaturated alkyl, C3 to C20 cyclic saturated alkyl, C3 to C20 cyclic unsaturated alkyl, -COR1 or-N (R2)₂One of (1);

the chain saturated hydrocarbon group, the chain unsaturated hydrocarbon group, the cyclic saturated hydrocarbon group or the cyclic unsaturated hydrocarbon group described in the optional substituents for Y1 to Y8 and R1 and R2 does not contain or contains at least 1 or two or more selected from an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom.

2. The flow battery as recited in claim 1, wherein the concentration of the dihydroxybiphenyl compound in the positive electrolyte is from 0.05mol/L to its saturated concentration in solution.

3. The organic flow battery as recited in claim 1, wherein the positive or negative electrode is a carbon felt, a carbon cloth, a carbon paper, or a graphite sheet, respectively.

4. The flow battery of claim 1, wherein the negative electrolyte in the negative electrolyte solution of the flow battery comprises one or more of: silicotungstic acid, 2, 7-anthraquinone-disodium disulfonate, stannic chloride, lead sulfate, cadmium chloride and vanadium trichloride.

5. The flow battery of claim 1, 2, or 4, wherein hydroxyl groups in a dihydroxybiphenyl compound of the positive electrolyte in the positive electrolyte undergo an electron transfer redox reaction;

the negative electrode electrolyte in the negative electrode electrolyte solution undergoes an oxidation-reduction reaction of electron transfer.

6. The flow battery as recited in claim 5, wherein the total concentration of negative electrolyte in the negative electrolyte solution is from 0.05mol/L to its saturated concentration.

7. The flow battery of claim 1, wherein the separator is an ion exchange membrane or a porous membrane.

8. The flow battery as recited in claim 1, wherein the supporting electrolyte is present in the electrolyte at a concentration of 0.05mol/L to 6.0 mol/L.