CN111326779A - Method for improving transmission performance of eutectic solvent electrolyte flow battery and flow battery - Google Patents
Method for improving transmission performance of eutectic solvent electrolyte flow battery and flow battery Download PDFInfo
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
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Abstract
The invention provides a method for improving the transmission performance of a eutectic solvent electrolyte flow battery and the flow battery. The eutectic solvent electrolyte flow battery is placed in a magnetic field, so that the ionic conductivity of the electrolyte is improved. The chemical and physical properties of the eutectic solvent electrolyte are adjusted, the diffusion coefficient of ions in the electrolyte of the flow battery is increased, and the problem that the power density of the battery is low due to high viscosity of the conventional eutectic solvent electrolyte is effectively solved; thereby improving the energy efficiency and power density of the battery.
Description
Technical Field
The invention belongs to the technical field of flow batteries in electrochemical energy storage, and particularly relates to a method for improving the transmission performance of a eutectic solvent electrolyte flow battery and the flow battery.
Background
The concept of flow battery was first proposed by Thaller in 1974. The most reported in the current literature are water-based flow batteries, and the most studied are iron/chromium flow batteries, all-vanadium flow batteries, bromide/polysulfide flow batteries, and the like. In recent years, the flow battery technology has the advantages of safe and reliable operation, environmental friendliness, flexible design and arrangement, high energy efficiency, high starting speed and the like, so that the flow battery technology has a good prospect and is suitable for large-scale energy storage.
With the development of recent years, research on water-based flow batteries has made a great breakthrough, and a series of water-based flow batteries, such as all-vanadium flow batteries, have been commercially used, but due to the influence of electrochemical decomposition of water, the water-based flow batteries have problems of narrow electrochemical window (<2V), and the like, which limits further development thereof to some extent. In order to overcome the disadvantages of aqueous flow batteries, researchers have proposed the use of non-aqueous solvents; the non-aqueous solvents commonly used in the non-aqueous flow battery mainly comprise organic solvents and ionic liquids, which can provide a wide electrochemical window and high stability, but the problems of volatility, toxicity and flammability of the organic solvents, complex synthetic steps of the ionic liquids, high cost and the like limit the large-scale application of the organic solvents and the ionic liquids.
Therefore, we have used a low cost non-aqueous solvent, i.e., a eutectic solvent (DES), which is a two-component or three-component eutectic mixture of stoichiometric hydrogen bond acceptors, such as quaternary ammonium salts, and hydrogen bond donors, such as amides, carboxylic acids, and polyols, with a melting point significantly lower than the melting point of the pure materials of each component. The material has a series of advantages of wide electrochemical window, low volatility, high thermal stability, good conductivity, no toxicity, no flammability, convenient storage, environmental friendliness and the like, and is widely concerned by scholars in the electrochemical related field in recent years. However, due to the large viscosity of the eutectic solvent, the resistance to the movement of ions is too large, which is not favorable for the transmission of active ions therein, thereby limiting the application range thereof.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a flow battery taking a eutectic solvent as an electrolyte, which adjusts the chemical and physical properties of the eutectic solvent electrolyte through an external magnetic field, increases the diffusion coefficient of ions in the flow battery electrolyte and effectively solves the problem that the current eutectic solvent electrolyte has low power density due to high viscosity; thereby improving the energy efficiency and power density of the battery.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows:
the method for improving the transmission performance of the eutectic solvent electrolyte flow battery is characterized in that the eutectic solvent electrolyte flow battery is placed in a 165-605 mT magnetic field, so that under the action of Lorentz force, the ionic movement rate of charged particles in electrolyte is improved, and the conductivity of the flow battery is improved.
A flow battery using eutectic solvent as electrolyte comprises a positive liquid storage tank, a negative liquid storage tank, a first mechanical pump, a second mechanical pump, a magnetic field generator, an ion exchange membrane, a negative electrode, a positive electrode, a first current collecting plate, a second current collecting plate, a first end plate and a second end plate; the positive electrode liquid storage tank and the negative electrode liquid storage tank are respectively stored with positive electrolyte and negative electrolyte which take eutectic solvent as supporting electrolyte, and a first mechanical pump and a second mechanical pump are respectively arranged between the positive electrode liquid storage tank and the positive electrode and between the negative electrode liquid storage tank and the negative electrode; the ion exchange membrane is positioned between the cathode electrode and the anode electrode, a first current collecting plate and a second current collecting plate are respectively arranged on two sides of the cathode electrode and the anode electrode, and the first end plate and the second end plate are used for fixing on the outer sides of the first current collecting plate and the second current collecting plate; the flow battery is characterized in that the magnetic field generator is arranged on two sides of the negative electrode and the positive electrode and provides a magnetic field for the flow battery.
Further, the ion exchange membrane is a perfluorinated sulfonic acid ion exchange membrane.
Further, the negative electrode and the positive electrode are graphite felt, carbon cloth or foamed nickel.
Further, the eutectic solvent is prepared from choline chloride and ethylene glycol according to the ratio of 1:2 mol ratio, or 1:2 mol ratio of choline chloride and urea, or 1: 1mol ratio of choline chloride and malonic acid.
Further, the magnetic field intensity generated by the magnetic field generator is 165-605 mT.
Further, a positive active substance is added into the eutectic solvent in the positive liquid storage tank, and the positive active substance is one of divalent iron ions, tetravalent vanadium ions and divalent manganese ions.
Further, a negative electrode active substance is added into the eutectic solvent in the negative electrode liquid storage tank, and the negative electrode active substance is one of trivalent vanadium ions, trivalent chromium ions, divalent zinc ions and divalent copper ions.
Compared with the prior art, the invention has the following positive effects:
1. under the action of a magnetic field, charged particles in the electrolyte are acted by a Lorentz force, the resistance of ion movement is reduced, the ion movement rate is accelerated, so that the conductivity of the electrolyte is increased, the physical characteristics of the eutectic solvent electrolyte are adjusted, the internal loss of the flow battery is reduced, and the transmission performance of the flow battery is improved.
2. The magnetic field can improve the reaction kinetics of redox couples in the electrolyte, increase the diffusion capacity of ions in electrochemical reaction, further increase the collision among the ions, make the ions more easily overcome reaction activation energy and generate electrochemical reaction, and effectively improve the redox peak current of active substances; in addition, the introduction of the magnetic field can also reduce the ohmic resistance and the electrochemical reaction resistance of the electrolyte, so that the electrochemical performance of the electrolyte is obviously improved; at the same time, the method plays a positive role in the mass transfer process.
3. The eutectic solvent is used as the electrolyte of the flow battery, has simple preparation, low price, no toxicity, wider electrochemical window, good biocompatibility and degradability and can be used under the environmental condition.
Drawings
Fig. 1 is a schematic structural diagram of the flow battery using the eutectic solvent as the electrolyte.
Fig. 2 is a graph showing the variation of the conductivity of the negative electrolyte with different magnetic field strengths.
Fig. 3 is a cyclic voltammogram of the negative electrolyte with different magnetic field strengths added.
Fig. 4 is an electrochemical impedance spectrum of the negative electrode electrolyte with or without an added magnetic field.
FIG. 5 shows the addition ofThe flow battery with the same magnetic field intensity is 2mA/cm2Polarization curve at current density.
In the figure:
1-an anode liquid storage tank, 2-a cathode liquid storage tank, 3-a first mechanical pump, 4-a second mechanical pump, 5-a magnetic field generator, 6-an ion exchange membrane, 7-a cathode electrode, 8-an anode electrode, 9-a first current collecting plate, 10-a second current collecting plate, 11-a first end plate and 12-a second end plate.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings.
The method for improving the transmission performance of the eutectic solvent electrolyte flow battery is characterized in that the eutectic solvent electrolyte flow battery is placed in a 165-605 mT magnetic field, so that the ionic movement rate of charged particles in electrolyte is improved under the action of Lorentz force, and the conductivity of the flow battery is improved. Under the action of a magnetic field, charged particles in the electrolyte are acted by a Lorentz force, the resistance of ion movement is reduced, the ion movement rate is accelerated, so that the conductivity of the electrolyte is increased, the physical characteristics of the eutectic solvent electrolyte are adjusted, the internal loss of the flow battery is reduced, and the transmission performance of the flow battery is improved. The magnetic field can also improve the reaction kinetics of redox couples in the electrolyte, increase the diffusion capacity of ions in electrochemical reaction, further increase the collision among the ions, make the ions more easily overcome reaction activation energy and generate electrochemical reaction, and effectively improve the redox peak current of active substances; in addition, the introduction of the magnetic field can also reduce the ohmic resistance and the electrochemical reaction resistance of the electrolyte, so that the electrochemical performance of the electrolyte is obviously improved; at the same time, the method plays a positive role in the mass transfer process.
The flow battery using the eutectic solvent as the electrolyte based on the method is shown in fig. 1, and comprises an anode liquid storage tank 1, a cathode liquid storage tank 2, a first mechanical pump 3, a second mechanical pump 4, a magnetic field generator 5, an ion exchange membrane 6, a cathode electrode 7, an anode electrode 8, a first current collecting plate 9, a second current collecting plate 10, a first end plate 11 and a second end plate 12. The positive liquid storage tank 1 and the negative liquid storage tank 2 are respectively stored with positive electrolyte and negative electrolyte which take eutectic solvent as supporting electrolyte, and a first mechanical pump 3 and a second mechanical pump 4 are respectively arranged between the positive liquid storage tank 1 and the positive electrode 8 and between the negative liquid storage tank 2 and the negative electrode 7. The ion exchange membrane 6 is located between the negative electrode 7 and the positive electrode 8, a first current collecting plate 9 and a second current collecting plate 10 are respectively arranged on two sides of the negative electrode 7 and the positive electrode 8, and a first end plate 11 and a second end plate 12 are used for fixing on the outer sides of the first current collecting plate 9 and the second current collecting plate 10. The magnetic field generator 5 is arranged on two sides of the negative electrode 7 and the positive electrode 8 and provides a magnetic field for the flow battery.
The ion exchange membrane 6 is a perfluorinated sulfonic acid ion exchange membrane. The negative electrode 7 and the positive electrode 8 can be graphite felt, carbon cloth, foam nickel and the like. The eutectic solvent is prepared from choline chloride and ethylene glycol according to the weight ratio of 1:2 mol ratio, or 1:2 mol ratio of choline chloride and urea, or 1: 1mol ratio of choline chloride and malonic acid. And a positive active substance is added into the eutectic solvent in the positive liquid storage tank 1, and is one of divalent iron ions, tetravalent vanadium ions and divalent manganese ions. And adding a negative active substance into the eutectic solvent in the negative liquid storage tank 2, wherein the negative active substance is one of trivalent vanadium ions, trivalent chromium ions, divalent zinc ions and divalent copper ions.
Example 1
Preparing an ethylene glycol-based eutectic solvent solution, and mixing choline chloride and ethylene glycol according to a molar ratio of 1:2, mixing uniformly, continuously stirring at a heating temperature of 50 ℃ until a colorless and transparent eutectic solvent is formed, and cooling at room temperature of 25 ℃.
Positive and negative electrode active materials and negative electrode active material FeCl2And VCl3The electrolyte solutions were prepared by adding the solutions to 60mL of the eutectic solvent at a concentration of 0.1mol/L, respectively.
The prepared cathode electrolyte is placed in a magnetic field generator, and the magnetic field intensity is changed within the range of 0-605 mT.
And testing the conductivity change condition of the negative electrolyte added with different magnetic field strengths by using a conductivity meter. The test result is shown in fig. 2, when the magnetic field is not added, that is, when the magnetic field strength is 0, the conductivity of the negative electrode electrolyte is 7.01mS/cm, and the conductivity of the negative electrode electrolyte after the magnetic field is added can reach 7.54mS/cm at most.
And testing the peak current density and the peak potential of the negative electrolyte added with different magnetic field strengths by using a cyclic voltammetry method. Test data peak current densities at different scan rates were measured and the diffusion coefficient of V ions was calculated by Randles-Sevcik equation 12, as shown in fig. 3.
In the case of a reversible reaction, the reaction is,
ip=2.69×105An1.5cD0.5ν0.51
in the case of the irreversible reaction,
ip=2.99×105An1.5α0.5cD0.5ν0.52
wherein ipIs the peak current, n is the number of electrons involved in the electrode reaction, α is the charge transfer coefficient, a is the electrode area, c is the concentration of the active material, D is the diffusion coefficient, v is the scan rate.
The charge transfer coefficient α is obtained by the following equation:
wherein EpAnd Ep/2The potential of the peak current density and the potential of the half-peak current density are represented, respectively.
As is clear from Table 1, the diffusion coefficient of V ions without the addition of a magnetic field was 1.838 × 10-7~5.614×10- 7cm2·s-1In the range, the diffusion coefficient can reach 3.683 × 10 at most after the magnetic field is added-7~1.050×10-6cm2·s-1Within the interval.
Table 1 diffusion coefficient of 0.1M V ion with addition of different magnetic field strengths
And the electrochemical impedance test is utilized to research the ohmic resistance and the electrochemical reaction resistance of the electrolyte added under different magnetic field strengths. FIG. 4 shows that the ohmic resistance and electrochemical reaction resistance of the electrolyte without the addition of a magnetic field were 112.91 and 101.34ohm/cm, respectively2The minimum value can reach 67.13 and 57.48ohm/cm after the magnetic field is added2. Therefore, the addition of the magnetic field leads the charge transfer rate of the electrolyte to be increased, and the electrochemical reaction speed to be improved.
Example 2
Preparing positive electrolyte and negative electrolyte based on eutectic solvent, wherein the positive active substance is FeCl2VCl is used as the negative electrode active material3Assembling the flow battery by using a Nafion115 diaphragm as an ion exchange membrane and using a GFA series graphite felt electrode as an electrode; the assembled flow battery is shown in fig. 1.
Placing the assembled flow battery into a magnetic field generator, and performing constant current charge and discharge test on the flow battery under different magnetic field strengths, wherein the current is set to be 2mA/cm2. And setting a discharge program in the electrochemical test system under the same magnetic field environment condition: starting from the open-circuit voltage of 1.097V, the discharge current is gradually increased until the discharge voltage is reduced to zero, the discharge process is stopped, and the current measured at the moment is the limiting current.
The battery discharge polarization curve shown in fig. 5 is used for researching the influence of a magnetic field on the system performance of the eutectic solvent flow battery, and specific test data results are shown in table 2.
Table 2 relevant performance parameters of eutectic solvent batteries with different added magnetic field strengths
As can be seen from Table 2, the internal resistance of the battery can be reduced by adding the magnetic field, the energy efficiency is improved, the energy efficiency of the battery is improved from 53.20% to 66.64%, and the limiting current density and the power density of the battery are also obviousThe improvement is respectively from the original 8.49mA/cm2And 2.07mW/cm2Increased to 10.46mA/cm2And 3.43mW/cm2。
Finally, it should be noted that: the above examples are only for illustrating the technical solutions of the present invention, but not for limiting the same, i.e. it is not meant that the present invention must rely on the above detailed features and methods to be implemented. It will be apparent to those skilled in the art that any modifications, equivalent substitutions of materials and steps used in the present invention, as well as additions of auxiliary materials and steps, selection of specific means, etc., are within the scope and disclosure of the present invention.
Claims (8)
1. The method for improving the transmission performance of the eutectic solvent electrolyte flow battery is characterized in that the eutectic solvent electrolyte flow battery is placed in a 165-605 mT magnetic field, so that under the action of Lorentz force, the ionic movement rate of charged particles in electrolyte is improved, and the conductivity of the flow battery is improved.
2. A flow battery using eutectic solvent as electrolyte comprises a positive liquid storage tank (1), a negative liquid storage tank (2), a first mechanical pump (3), a second mechanical pump (4), a magnetic field generator (5), an ion exchange membrane (6), a negative electrode (7), a positive electrode (8), a first current collecting plate (9), a second current collecting plate (10), a first end plate (11) and a second end plate (12); the positive liquid storage tank (1) and the negative liquid storage tank (2) are respectively stored with positive electrolyte and negative electrolyte which take eutectic solvent as supporting electrolyte, and a first mechanical pump (3) and a second mechanical pump (4) are respectively arranged between the positive liquid storage tank (1) and the positive electrode (8) and between the negative liquid storage tank (2) and the negative electrode (7); the ion exchange membrane (6) is positioned between the negative electrode (7) and the positive electrode (8), a first current collecting plate (9) and a second current collecting plate (10) are respectively arranged on two sides of the negative electrode (7) and the positive electrode (8), and a first end plate (11) and a second end plate (12) are used for fixing on the outer sides of the first current collecting plate (9) and the second current collecting plate (10); the flow battery is characterized in that the magnetic field generator (5) is arranged on two sides of the negative electrode (7) and the positive electrode (8) and provides a magnetic field for the flow battery.
3. The flow battery using the eutectic solvent as the electrolyte according to claim 2, wherein the ion exchange membrane (6) is a perfluorinated sulfonic acid ion exchange membrane.
4. The flow battery using the eutectic solvent as the electrolyte according to claim 2, wherein the negative electrode (7) and the positive electrode (8) are graphite felt, carbon cloth or nickel foam.
5. The flow battery using the eutectic solvent as the electrolyte according to claim 2, wherein the eutectic solvent is prepared from choline chloride and ethylene glycol according to a ratio of 1:2 mol ratio, or 1:2 mol ratio of choline chloride and urea, or 1: 1mol ratio of choline chloride and malonic acid.
6. The flow battery taking the eutectic solvent as the electrolyte according to claim 2, wherein the magnetic field intensity generated by the magnetic field generator is 165-605 mT.
7. The flow battery using the eutectic solvent as the electrolyte according to claim 6, wherein a positive active material is added to the eutectic solvent in the positive liquid storage tank (1), and the positive active material is one of divalent iron ions, tetravalent vanadium ions and divalent manganese ions.
8. The flow battery using the eutectic solvent as the electrolyte according to claim 7, wherein a negative active material is added to the eutectic solvent in the negative liquid storage tank (2), and the negative active material is one of trivalent vanadium ions, trivalent chromium ions, divalent zinc ions and divalent copper ions.
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Cited By (5)
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CN112768733A (en) * | 2021-01-15 | 2021-05-07 | 江苏大学 | Method for improving transmission performance of flow battery and flow battery |
CN112928343A (en) * | 2021-04-15 | 2021-06-08 | 燕山大学 | Water system copper ion battery suitable for large-scale energy storage application |
CN113178607A (en) * | 2021-03-09 | 2021-07-27 | 江苏大学 | Method for improving transmission performance of flow battery under synergistic effect of magnetic field and temperature and flow battery |
CN113764713A (en) * | 2021-08-03 | 2021-12-07 | 江苏大学 | Flow battery based on ternary eutectic solvent |
CN114284530A (en) * | 2021-06-02 | 2022-04-05 | 北京化工大学 | Battery electrolyte self-driving system |
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Cited By (8)
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CN112768733A (en) * | 2021-01-15 | 2021-05-07 | 江苏大学 | Method for improving transmission performance of flow battery and flow battery |
CN113178607A (en) * | 2021-03-09 | 2021-07-27 | 江苏大学 | Method for improving transmission performance of flow battery under synergistic effect of magnetic field and temperature and flow battery |
CN113178607B (en) * | 2021-03-09 | 2023-10-13 | 江苏大学 | Method for improving transmission performance of flow battery through magnetic field and temperature synergistic effect and flow battery |
CN112928343A (en) * | 2021-04-15 | 2021-06-08 | 燕山大学 | Water system copper ion battery suitable for large-scale energy storage application |
CN112928343B (en) * | 2021-04-15 | 2022-04-29 | 燕山大学 | Water system copper ion battery suitable for large-scale energy storage application |
CN114284530A (en) * | 2021-06-02 | 2022-04-05 | 北京化工大学 | Battery electrolyte self-driving system |
CN113764713A (en) * | 2021-08-03 | 2021-12-07 | 江苏大学 | Flow battery based on ternary eutectic solvent |
CN113764713B (en) * | 2021-08-03 | 2023-10-13 | 江苏大学 | Flow battery based on ternary eutectic solvent |
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