CN115275292A - Water-based organic flow battery based on vanadium-based organic cluster molecular aqueous solution - Google Patents
Water-based organic flow battery based on vanadium-based organic cluster molecular aqueous solution Download PDFInfo
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- CN115275292A CN115275292A CN202210766900.1A CN202210766900A CN115275292A CN 115275292 A CN115275292 A CN 115275292A CN 202210766900 A CN202210766900 A CN 202210766900A CN 115275292 A CN115275292 A CN 115275292A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
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- 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 discloses a water-based organic liquid flow battery based on a vanadium-based organic cluster molecular aqueous solution, which belongs to the field of organic liquid flow batteries, and is characterized in that vanadyl sulfate is used as a raw material to synthesize organic cluster molecules containing vanadium atoms through a hydrothermal reaction; the molecular weight of the vanadium-based organic cluster molecule is 2876, the potential is 1.0V, and the vanadium-based organic cluster molecule can be used as a positive electrode material of an aqueous flow battery; selecting phosphotungstic acid cluster molecules with the potential of 0.2V as a negative electrode material, wherein the molecular weight of the phosphotungstic acid cluster molecules is 2880; the two cluster molecules have high solubility in a sulfuric acid aqueous solution, can be respectively prepared into redox electrolytes of a positive electrode and a negative electrode, can be realized, effectively solves the problem of cross contamination of the positive electrode and the negative electrode by utilizing a size exclusion effect, and simultaneously greatly reduces the cost of the whole device of the flow battery.
Description
Technical Field
The invention relates to the field of organic flow batteries, in particular to a water-based organic flow battery based on a vanadium-based organic cluster molecular aqueous solution.
Background
At present, energy used globally mainly comes from nuclear power stations and thermal power stations, but the output power of the power stations still cannot meet the increasing energy demand. The large scale consumption of fossil energy makes the greenhouse effect a very serious environmental problem. Therefore, the development of clean energy such as solar energy, wind energy, geothermal energy and the like has great significance for the sustainable development of green environmental protection, and in order to utilize the sustainable energy, the sustainable energy needs to be properly stored and transported, the commercial all-vanadium redox flow battery can realize large-scale energy storage, and the energy storage scale reaches the MW level. The flow battery can improve the power of the flow battery by changing the number of the electric piles or the area of the electrodes, the total charge and discharge capacity of the flow battery can be realized by adjusting the volume and the concentration of the electrolyte, and the flow battery has high energy efficiency and high safety. However, some problems still exist at present and need to be solved, for example, the costs of the all-vanadium electrolyte and the ion exchange membrane are too high, the production technology is not complete, and particularly, the ion exchange membrane cannot effectively prevent the diffusion of vanadium ions, which may cause cross contamination of the positive and negative electrolytes, so that the specific capacity of the flow battery is reduced, and the cycle life of the flow battery is affected.
At present, in addition to all-vanadium flow batteries, aqueous flow batteries based on organic substances such as phenazine, anthraquinone, and ferrocene are also under development. Organic molecules have various structures, and the electrochemical performance can be adjusted by changing the functional groups of the organic molecules. However, conventional redox-active organic molecules are susceptible to degradation reactions in aqueous solutions, such as nucleophilic substitution or self-polymerization reactions, and have poor electrochemical stability and reversibility, short cycle life, and the cost of the ion-exchange membranes used remains high. Therefore, research and development of different redox active materials with high stability and reduction of the overall device cost of the flow battery are important for development and application of the aqueous flow battery.
In view of the above problems, we propose an aqueous organic flow battery based on an aqueous solution of vanadium-based organic cluster molecules.
Disclosure of Invention
1. Technical problem to be solved
Aiming at the problems in the prior art, the invention aims to provide a water system organic flow battery based on a vanadium-based organic cluster molecular aqueous solution, which can be realized, effectively solves the problem of cross contamination of positive and negative electrolytes by utilizing a size exclusion effect, and simultaneously greatly reduces the cost of the whole device of the flow battery.
2. Technical scheme
In order to solve the above problems, the present invention adopts the following technical solutions.
A water system organic liquid flow battery based on vanadium-based organic cluster molecule aqueous solution is characterized in that vanadyl sulfate is used as a raw material to synthesize organic cluster molecules containing vanadium atoms through a hydrothermal reaction;
the molecular weight of the vanadium-based organic cluster molecule is 2876, the potential is 1.0V, and the vanadium-based organic cluster molecule can be used as a positive electrode material of an aqueous flow battery;
selecting phosphotungstic acid cluster molecules with the potential of 0.2V as a negative electrode material, wherein the molecular weight of the phosphotungstic acid cluster molecules is 2880;
the two cluster molecules have high solubility in a sulfuric acid aqueous solution, and can be respectively prepared into redox electrolytes of a positive electrode and a negative electrode.
Further, the preparation method of the vanadium-based organic cluster molecule comprises the following steps:
mixing phenylphosphoric acid, vanadyl sulfate trihydrate and 1M of n-propyl ammonium hydroxide aqueous solution according to a certain proportion, placing the mixture in a hydrothermal kettle, reacting for 48 hours at 200 ℃, collecting obtained solids, washing with water, and drying washed vanadium-based organic cluster molecules.
Further, the preparation method of the anode and cathode redox electrolyte comprises the following steps:
dissolving a certain amount of vanadium-based organic cluster molecules in 1M sulfuric acid aqueous solution to be used as anode electrolyte;
excess phosphotungstic acid was dissolved in 1M sulfuric acid aqueous solution as a negative electrode electrolyte.
Further, assembling the water-based organic flow battery:
placing positive and negative redox electrolytes in a liquid storage tank, symmetrically placing a graphite felt, a graphite plate with a fluid channel and a copper plate on two sides of a dialysis membrane in sequence to assemble the water-based organic flow battery, communicating with the positive and negative redox electrolyte storage tanks, and allowing the electrolytes to flow through graphite felt electrodes under the driving of a peristaltic pump to generate electrochemical charge-discharge reaction.
Further, the preparation method of the vanadium-based organic cluster molecule comprises the following steps:
0.952g of phenylphosphoric acid, 0.434g of vanadyl sulfate trihydrate and 8g of 1M n-propyl ammonium hydroxide aqueous solution are mixed and then placed in a hydrothermal kettle to react for 48 hours at 200 ℃, the obtained solid is collected and washed for several times by water, and the washed vanadium-based organic cluster molecules are dried.
Further, the preparation of the positive and negative electrode redox electrolytes:
dissolving 576mg of vanadium-based organic cluster molecules in 1M sulfuric acid solution to prepare 5mL of positive electrolyte with the concentration of 40 mM;
9.22g of phosphotungstic acid was dissolved in 1M sulfuric acid solution to prepare 40mL of an anode electrolyte having a concentration of 80 mM.
Further, the assembly and the test of the water system organic flow battery are as follows:
placing the positive and negative redox electrolytes in a liquid storage tank, symmetrically placing a graphite felt, a graphite plate with a fluid channel and a copper plate on two sides of a dialysis membrane in sequence, packaging by using an acrylic plate, assembling into a water-based organic flow battery, and communicating with the liquid storage tank of the positive and negative redox electrolytes;
placing the battery in a glove box filled with nitrogen, and enabling the electrolyte to flow through a graphite felt electrode under the driving of a peristaltic pump, wherein the flow rate of the electrolyte is 60mL/min, and the charge-discharge current density is 20mA/cm & lt 2 & gt; electrochemical performance testing of the flow battery is completed in a blue battery testing system.
3. Advantageous effects
Compared with the prior art, the invention has the advantages that:
(1) The invention constructs an organic water system flow battery based on a vanadium-based organic cluster aqueous solution and a dialysis membrane diaphragm, wherein a redox active substance in positive electrolyte is vanadium-based organic cluster molecules, and a redox active substance in negative electrolyte is phosphotungstic acid. Experimental tests show that the diffusion coefficient of the vanadium-based organic cluster molecule in an aqueous solution is 3.07 x 10-6cm < 2 > s < -1 >, and the diffusion coefficient of phosphotungstic acid is 2.61 x 10-6cm < 2 > s < -1 >, and is equivalent to that of vanadium ions. Because the charge distribution on the vanadium-based organic cluster molecules is delocalized, the electron transmission speed is high, and the kinetic reaction is rapid. The molecular weights of the two are about 3000, the dialysis membrane with low price is used for replacing the traditional proton exchange membrane to be used as a diaphragm, the problem of cross contamination of positive and negative electrolytes is effectively solved by utilizing the size exclusion effect, and meanwhile, the cost of the whole device of the flow battery is greatly reduced.
(2) In addition, 12 vanadium atoms in the vanadium-based organic cluster molecules can participate in electrochemical reaction, the reaction utilization rate is high, the complete structure is still kept in an acidic solution, and the electrochemical stability is good. The assembled water system organic flow battery does not generate side reactions such as redox active substance decomposition, self-polymerization and the like in the circulating process, and the high stability and the long circulating life of the flow battery are ensured. After 300 cycles of charge and discharge of the aqueous organic flow battery based on the design, the capacity retention rate reaches 98.786%.
Drawings
FIG. 1 is (a) a ball-and-stick model of vanadium-based organic cluster molecules; (b) An actually measured XRD spectrogram and a simulated XRD spectrogram of the vanadium-based organic cluster molecule;
FIG. 2 is (a) a constant current charge and discharge curve of an aqueous organic flow battery at current densities of 15, 20, 30, 40 and 50mA/cm 2; (b) The coulomb efficiency, energy efficiency and specific capacity of the water system organic flow battery under different current densities; (c) Open-circuit voltage of the aqueous organic flow battery under different charge states; (d) Polarization and power density curves of the aqueous organic flow battery at 20%, 50% and 100% states of charge; (e) And the cycle performance of the water-based organic flow battery under the current density of 20mA/cm < 2 >.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention; it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and all other embodiments obtained by those skilled in the art without any inventive work are within the scope of the present invention.
Example 1:
a water system organic liquid flow battery based on vanadium-based organic cluster molecule aqueous solution is characterized in that vanadyl sulfate is used as a raw material to synthesize organic cluster molecules containing vanadium atoms through a hydrothermal reaction;
the molecular weight of the vanadium-based organic cluster molecule is 2876, the potential is 1.0V, and the vanadium-based organic cluster molecule can be used as a positive electrode material of an aqueous flow battery;
selecting phosphotungstic acid cluster molecules with the potential of 0.2V as a negative electrode material, wherein the molecular weight of the phosphotungstic acid cluster molecules is 2880;
the two cluster molecules have high solubility in a sulfuric acid aqueous solution, can be respectively prepared into redox electrolytes of a positive electrode and a negative electrode, and can effectively avoid the permeation of the electrolytes by adopting a low-cost dialysis membrane as a diaphragm due to the high molecular weight and large molecular size of the two redox active substances, so that the problem of cross contamination is solved.
The preparation method of the vanadium-based organic cluster molecule comprises the following steps:
mixing phenylphosphoric acid, vanadyl sulfate trihydrate and 1M of n-propyl ammonium hydroxide aqueous solution according to a certain proportion, placing the mixture in a hydrothermal kettle, reacting for 48 hours at 200 ℃, collecting obtained solids, washing the solids with water, and drying washed vanadium-based organic cluster molecules;
0.952g of phenylphosphoric acid, 0.434g of vanadyl sulfate trihydrate and 8g of 1M n-propyl ammonium hydroxide aqueous solution are mixed and then placed in a hydrothermal kettle to react for 48 hours at 200 ℃, the obtained solid is collected, washed with water for several times, and the washed vanadium-based organic cluster molecules are dried (as shown in figure 1).
The preparation method of the anode and cathode redox electrolytes comprises the following steps:
dissolving a certain amount of vanadium-based organic cluster molecules in 1M sulfuric acid aqueous solution to be used as anode electrolyte;
an excess amount of phosphotungstic acid was dissolved in a 1M aqueous sulfuric acid solution as a negative electrode electrolyte.
Assembling the aqueous organic flow battery:
placing positive and negative redox electrolytes in a liquid storage tank, symmetrically placing a graphite felt, a graphite plate with a fluid channel and a copper plate on two sides of a dialysis membrane in sequence to assemble the water-based organic flow battery, communicating with the positive and negative redox electrolyte storage tanks, and allowing the electrolytes to flow through graphite felt electrodes under the driving of a peristaltic pump to generate electrochemical charge-discharge reaction.
Example 2:
based on the embodiment 1, the preparation of the positive and negative electrode redox electrolytes further comprises the following steps:
dissolving 576mg of vanadium-based organic cluster molecules in 1M sulfuric acid solution to prepare 5mL of positive electrolyte with the concentration of 40 mM;
9.22g of phosphotungstic acid was dissolved in 1M sulfuric acid solution to prepare 40mL of negative electrode electrolyte having a concentration of 80 mM.
Example 3:
based on example 1, the assembly and testing of the water-based organic flow battery comprises the following steps:
and (3) placing the positive and negative redox electrolytes in a liquid storage tank, symmetrically placing a graphite felt, a graphite plate with a fluid channel and a copper plate on two sides of the dialysis membrane in sequence, packaging by using an acrylic plate, assembling into the aqueous organic flow battery, and communicating with the positive and negative redox electrolyte storage tank. The battery is placed in a glove box filled with nitrogen, and the electrolyte flows through a graphite felt electrode under the driving of a peristaltic pump, wherein the flow rate of the electrolyte is 60mL/min, and the charge-discharge current density is 20mA/cm < 2 >. Electrochemical performance testing of the flow battery is completed in a blue battery testing system.
Fig. 2a and 2b are rate performance of water-based organic flow batteries based on vanadium-based organic cluster molecules and dialysis membrane diaphragms at different current densities; the water system organic flow battery keeps stable voltage under different current densities, and when the current density is 20mA/cm < 2 >, the charging and discharging platforms are 0.87V and 0.79V respectively;
fig. 2c is the open circuit voltage of the water system organic flow battery in different charge states, the open circuit voltage in 50% charge state is 0.8V, and the open circuit voltage is consistent with the potential difference of the anode and cathode redox electrolytes;
FIG. 2d is a power density test of the water-based organic flow battery, wherein the power density is 126mW/cm2;
fig. 2e shows the long cycle performance of the aqueous organic flow battery based on the vanadium-based organic cluster molecular positive electrolyte with the concentration of 40mM and the volume of 5mL, the initial specific capacity of the aqueous organic flow battery is 6.26Ah/L, the coulombic efficiency is close to 100%, the energy efficiency reaches 90%, and after stable cycling for 300 cycles, the capacity retention rate reaches 98.786%.
The above are merely preferred embodiments of the present invention; the scope of the invention is not limited thereto. Any person skilled in the art should be able to cover the technical scope of the present invention by equivalent or modified solutions and modifications within the technical scope of the present invention.
Claims (7)
1. A water-based organic flow battery based on a vanadium-based organic cluster molecular aqueous solution is characterized in that vanadyl sulfate is used as a raw material to synthesize organic cluster molecules containing vanadium atoms through a hydrothermal reaction;
the molecular weight of the vanadium-based organic cluster molecule is 2876, the potential is 1.0V, and the vanadium-based organic cluster molecule is used for a positive electrode material of an aqueous flow battery;
phosphotungstic acid cluster molecules with the potential of 0.2V are selected as a negative electrode material, and the molecular weight of the phosphotungstic acid cluster molecules is 2880.
2. The aqueous organic flow battery based on the vanadium-based organic cluster molecule aqueous solution according to claim 1, characterized in that the preparation method of the vanadium-based organic cluster molecule comprises the following steps:
mixing phenyl phosphoric acid, vanadyl sulfate trihydrate and 1M of n-propyl ammonium hydroxide aqueous solution in proportion, placing the mixture in a hydrothermal kettle, reacting for 48 hours at 200 ℃, collecting obtained solid, washing with water, and drying washed vanadium-based organic cluster molecules.
3. The aqueous organic flow battery based on the vanadium-based organic cluster molecular aqueous solution is characterized in that the preparation method of the positive and negative electrode redox electrolytes comprises the following steps:
dissolving a certain amount of vanadium-based organic cluster molecules in 1M sulfuric acid aqueous solution to serve as anode electrolyte;
an excess amount of phosphotungstic acid was dissolved in a 1M aqueous sulfuric acid solution as a negative electrode electrolyte.
4. The aqueous organic flow battery based on the vanadium-based organic cluster molecular aqueous solution according to claim 1, characterized in that: assembling the aqueous organic flow battery:
placing positive and negative redox electrolytes in a liquid storage tank, symmetrically placing a graphite felt, a graphite plate with a fluid channel and a copper plate on two sides of a dialysis membrane in sequence to assemble the water-based organic flow battery, communicating with the positive and negative redox electrolyte storage tanks, and allowing the electrolytes to flow through graphite felt electrodes under the driving of a peristaltic pump to generate electrochemical charge-discharge reaction.
5. The aqueous organic flow battery based on the vanadium-based organic cluster molecule aqueous solution according to claim 1, wherein the preparation method of the vanadium-based organic cluster molecule comprises the following steps:
0.952g of phenylphosphoric acid, 0.434g of vanadyl sulfate trihydrate and 8g of 1M n-propyl ammonium hydroxide aqueous solution are mixed and then placed in a hydrothermal kettle to react for 48 hours at 200 ℃, the obtained solid is collected and washed for several times by water, and the washed vanadium-based organic cluster molecules are dried.
6. The aqueous organic flow battery based on the vanadium-based organic cluster molecular aqueous solution is characterized in that the preparation of the positive and negative electrode redox electrolytes comprises the following steps:
dissolving 576mg of vanadium-based organic cluster molecules in 1M sulfuric acid solution to prepare 5mL of positive electrolyte with the concentration of 40 mM;
9.22g of phosphotungstic acid was dissolved in 1M sulfuric acid solution to prepare 40mL of negative electrode electrolyte having a concentration of 80 mM.
7. The water-based organic flow battery based on the vanadium-based organic cluster molecular aqueous solution is characterized in that the assembly and test of the water-based organic flow battery are as follows:
placing the positive and negative redox electrolytes in a liquid storage tank, symmetrically placing a graphite felt, a graphite plate with a fluid channel and a copper plate on two sides of a dialysis membrane in sequence, packaging by using an acrylic plate, assembling into a water-based organic flow battery, and communicating with the liquid storage tank of the positive and negative redox electrolytes;
placing the battery in a glove box filled with nitrogen, and enabling the electrolyte to flow through a graphite felt electrode under the driving of a peristaltic pump, wherein the flow rate of the electrolyte is 60mL/min, and the charge-discharge current density is 20mA/cm & lt 2 & gt; electrochemical performance testing of the flow battery is completed in a blue battery testing system.
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