CN109273749B - Preparation method of special colloidal electrolyte for flow battery - Google Patents
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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
- H01M2300/0085—Immobilising or gelification of electrolyte
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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
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- 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 preparation method of a special colloidal electrolyte for a flow battery, and belongs to the technical field of battery materials. Firstly, stirring and dissolving aniline and water, adding hydrogen peroxide and biological enzyme, stirring for reaction more stably, filtering, washing and drying to obtain low molecular weight polyaniline; dispersing graphene oxide in a solvent, slowly adding low-molecular-weight polyaniline under a constant-temperature stirring state, carrying out constant-temperature closed stirring reaction, filtering, washing and drying to obtain intercalation modified graphene oxide; mixing and dispersing the intercalated modified graphene oxide and absolute ethyl alcohol, adding silicate ester and stearic acid, heating, stirring, reacting, and concentrating under reduced pressure to obtain a concentrated solution; the solution was finally concentrated. And mixing the copper sulfate solution and the sulfuric acid solution in proportion to obtain the special colloidal electrolyte for the flow battery. The special colloidal electrolyte for the flow battery prepared by the technical scheme of the invention has the characteristics of excellent high-current discharge performance and initial capacity.
Description
Technical Field
The invention discloses a preparation method of a special colloidal electrolyte for a flow battery, and belongs to the technical field of battery materials.
Background
At present, the problems of environmental pollution and energy shortage are serious, new energy can be used as supplement of non-renewable energy and can effectively reduce environmental pollution, development and utilization of the new energy are concerned more and more, and support is placed on new energy industries in main fields such as coal-based clean fuel, wind energy, solar energy, smart power grids and the like, but power generation systems of the renewable energy such as the wind energy, the solar energy and the like are unstable and discontinuous and cannot be stably supplied with power, so that in the process of developing and utilizing the renewable energy, a very important core link is to develop a large-scale power energy storage system to realize peak load regulation of the power grids and alleviate contradictions between power supply and demand. The existing energy storage technology mainly has physical energy storage, electromagnetic energy storage and chemical energy storage, and due to the defects of low conversion rate of physical energy storage energy efficiency, expensive electromagnetic energy storage technology and the like, the chemical energy storage has a current application prospect, and the chemical energy storage systems which are researched more currently have the following characteristics: cadmium suppression batteries, lead-acid batteries, lithium ion batteries, flow batteries and the like. However, the ideal device suitable for large-scale fixed energy storage is a flow battery, and compared with other energy storage technologies, the flow battery has the following advantages: first, the scale is large. The large-scale energy storage requirement in the solar and wind power generation process can be met by changing the amount of the electrolyte in the storage tank; the rated discharge power is met by adjusting the logarithm and the electrode area of the positive half cell and the negative half cell in the cell stack. Therefore, the electric pile can be designed according to different practical situations; and secondly, the service life is long. Because the active substance exists in the electrolyte, the problems of appearance change of a battery material and capacity loss caused by falling of the active substance cannot occur in the charging and discharging process, and theoretically, the charging and discharging cycle of any degree can be carried out infinitely, so that the service life of the battery is prolonged. Thirdly, the cost is low. Most of the key components of the flow battery are cheap materials, and the flow battery has strong market competitiveness. By combining various chemical energy storage batteries, the flow battery becomes the best energy storage device for large-scale electricity storage due to the obvious advantages of the flow battery.
When the conventional gel electrolyte used in the flow battery is prepared, the internal resistance of the gel battery is relatively large due to the direct addition of fumed silica, which causes the disadvantages of large-current discharge performance and initial capacity reduction of the battery product, so how to exert better performance of the gel electrolyte special for the flow battery becomes one of the technical problems to be solved urgently in the technical field.
Disclosure of Invention
The invention mainly solves the technical problems that: the preparation method of the special colloidal electrolyte for the flow battery is provided for overcoming the defects that the internal resistance of the colloidal battery is relatively large due to the direct addition of the fumed silica during the preparation of the colloidal electrolyte adopted by the traditional flow battery, and the large-current discharge performance and the initial capacity of the battery product are reduced.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a special colloidal electrolyte for a flow battery comprises the following specific preparation steps:
(1) sequentially taking 8-10 parts of aniline, 30-40 parts of hydrogen peroxide, 200-300 parts of water and 0.06-0.08 part of biological enzyme according to parts by weight, heating, stirring and dissolving aniline and water, cooling to 35-40 ℃, adding hydrogen peroxide and biological enzyme, stirring and reacting at constant temperature, filtering, washing and drying to obtain low molecular weight polyaniline;
(2) according to the mass ratio of 1: 10-1: 20, dispersing graphene oxide in a solvent, slowly adding low molecular weight polyaniline with the mass of 0.1-0.2 times that of the graphene oxide under the constant-temperature stirring state, after the adding is finished, carrying out constant-temperature closed stirring reaction for 8-12 h, filtering, washing and drying to obtain the intercalation modified graphene oxide;
(3) sequentially taking 20-30 parts by weight of intercalated modified graphene oxide, 60-80 parts by weight of silicate ester, 8-10 parts by weight of stearic acid and 200-300 parts by weight of absolute ethyl alcohol, mixing and dispersing the intercalated modified graphene oxide and the absolute ethyl alcohol, then adding the silicate ester and the stearic acid, heating, stirring, reacting, and concentrating under reduced pressure to obtain a concentrated solution;
(4) and sequentially taking 40-60 parts by weight of copper sulfate solution, 40-60 parts by weight of sulfuric acid solution and 8-10 parts by weight of concentrated solution, shearing at a high speed, and defoaming in vacuum to obtain the special colloidal electrolyte for the flow battery.
The biological enzyme in the step (1) is horseradish peroxidase and laccase in a mass ratio of 3: 1-5: 1 is prepared by compounding.
The hydrogen peroxide solution in the step (1) is 15-25% by mass.
And (3) slowly adding the mixture at the rate of 3-8 g/min.
The solvent in the step (2) is any one of N-methyl pyrrolidone or N, N-dimethylformamide.
The silicate in the step (3) is any one of methyl orthosilicate, ethyl orthosilicate and propyl orthosilicate.
The copper sulfate solution in the step (4) is a copper sulfate solution with the concentration of 0.7-0.8 mol/L.
The sulfuric acid solution in the step (4) is a sulfuric acid solution with the concentration of 1.6-1.8 mol/L.
The invention has the beneficial effects that:
(1) according to the technical scheme, firstly, in an aqueous system, biological enzyme is used as a catalyst to catalyze hydrogen peroxide to polymerize aniline, and because the system is an aqueous system and polyaniline has poor water solubility, low molecular weight polyaniline with relatively low polymerization degree can be continuously precipitated in the preparation process, and the self-made low molecular weight polyaniline is used as one of effective components because: on one hand, the molecular weight of the graphene oxide is much smaller than that of common polyaniline, so that the graphene oxide is easier to be successfully embedded into an interlayer structure of graphene oxide in the reaction process; on the other hand, residual amino groups in the low-molecular polyaniline can react with epoxy groups in an oxidized region of graphene oxide, so that new chemical bonding is formed between the polyaniline and the graphene oxide, a benzene ring structure in a polyaniline molecular structure is adsorbed by a pi-pi interaction force and a non-oxidized region of the graphene oxide, and compared with fumed silica, the polyaniline has better conductivity;
(2) the technical proposal of the invention abandons the conventional technical means of adding gas phase silicon dioxide, but takes organic silicate ester as a silicon source, in the heating process, the stearic acid and the water generated by esterification and dehydration of absolute ethyl alcohol are contacted with silicate ester, so that the stearic acid and the silicate ester are subjected to hydrolysis reaction to slowly and uniformly generate nano-silica crystal nuclei, and because the polyaniline is successfully introduced into the interlayer structure, the interlayer structure of the graphene oxide is effectively widened, the adsorption and the embedding of nano silicon dioxide crystal nucleus are facilitated, compared with the traditional method of directly adding the precipitating agent, the process has the advantages that the size of the produced nano silicon dioxide crystal is more uniform, the monodispersity is better, therefore, in the process of forming colloid due to the interaction force of hydrogen bonds in the system, a better gas and electron diffusion channel can be obtained between particles, and the high-current discharge performance and the initial capacity of the product are further improved.
Detailed Description
According to the weight parts, sequentially taking 8-10 parts of aniline, 30-40 parts of hydrogen peroxide, 200-300 parts of water and 0.06-0.08 part of biological enzyme, firstly mixing aniline and water, pouring into a No. 1 beaker, moving the No. 1 beaker into a water bath kettle, stirring and dissolving for 1-2 hours at a constant temperature of 55-65 ℃ and at a stirring speed of 300-500 r/min, taking out the No. 1 beaker, naturally cooling to 35-40 ℃, then sequentially adding hydrogen peroxide and the biological enzyme into the No. 1 beaker, moving the No. 1 beaker to a digital display speed measurement constant temperature magnetic stirrer, stirring and reacting for 4-6 hours at a constant temperature of 35-40 ℃ and at a rotation speed of 300-500 r/min, filtering to obtain filter residue, washing the filter residue for 4-6 times by deionized water, then transferring the washed filter residue into a vacuum drying oven, and controlling the temperature to 85-90 ℃ and the pressure to be 80-120 Pa, vacuum drying to constant weight to obtain low molecular weight polyaniline; according to the mass ratio of 1: 10-1: 20, mixing graphene oxide and a solvent, pouring the mixture into a three-neck flask, performing ultrasonic dispersion for 45-60 min under the condition that the ultrasonic frequency is 55-60 kHz, moving the three-neck flask to a digital display speed measurement constant temperature magnetic stirrer, slowly adding low molecular weight polyaniline with the mass of 0.1-0.2 times that of the graphene oxide into the three-neck flask at the speed of 3-8 g/min while stirring at the constant temperature of 80-85 ℃ and the stirring speed of 400-600 r/min, after the low molecular weight polyaniline is completely added, sealing the three-neck flask, continuously stirring and reacting for 8-12 h at constant temperature in a sealed way, filtering to obtain a filter cake, washing the filter cake with N-methyl pyrrolidone for 3-5 times, transferring the washed filter cake into a vacuum drying oven, drying the graphene oxide to constant weight under the conditions that the temperature is 105-110 ℃ and the pressure is 80-100 Pa to obtain the intercalation modified graphene oxide; taking 20-30 parts by weight of intercalated modified graphene oxide, 60-80 parts by weight of silicate ester, 8-10 parts by weight of stearic acid and 200-300 parts by weight of absolute ethyl alcohol in sequence, firstly mixing the intercalated modified graphene oxide and the absolute ethyl alcohol, pouring the mixture into a reaction kettle, carrying out ultrasonic dispersion for 1-2 hours under the ultrasonic frequency of 55-65 kHz, then sequentially adding the silicate ester and the stearic acid into the reaction kettle, then carrying out heating stirring reaction for 4-6 hours under the conditions of 85-90 ℃ and 600-800 r/min of rotation speed, transferring the materials in the reaction kettle into a rotary evaporator, carrying out reduced pressure concentration for 30-40 minutes under the conditions of 75-85 ℃ and 400-450 mmHg of temperature, and obtaining a concentrated solution; and sequentially taking 40-60 parts by weight of copper sulfate solution, 40-60 parts by weight of sulfuric acid solution and 8-10 parts by weight of concentrated solution, mixing, shearing at a high speed of 8000-12000 r/min for 20-30 min, standing, and defoaming in vacuum to obtain the special colloidal electrolyte for the flow battery. The biological enzyme is horseradish peroxidase and laccase in a mass ratio of 3: 1-5: 1 is prepared by compounding. The hydrogen peroxide is a hydrogen peroxide solution with the mass fraction of 15-25%. The solvent is any one of N-methyl pyrrolidone or N, N-dimethylformamide. The silicate is any one of methyl orthosilicate, ethyl orthosilicate and propyl orthosilicate. The copper sulfate solution is a copper sulfate solution with the concentration of 0.7-0.8 mol/L. The sulfuric acid solution is 1.6-1.8 mol/L.
Example 1
Sequentially taking 10 parts of aniline, 40 parts of hydrogen peroxide, 300 parts of water and 0.08 part of biological enzyme according to parts by weight, firstly mixing aniline and water, pouring the mixture into a No. 1 beaker, moving the No. 1 beaker into a water bath kettle, stirring and dissolving the mixture for 2 hours at a constant temperature under the conditions that the temperature is 65 ℃ and the stirring speed is 500r/min, taking out the No. 1 beaker, naturally cooling the mixture to 40 ℃, then sequentially adding hydrogen peroxide and the biological enzyme into the No. 1 beaker, moving the No. 1 beaker to a digital display speed measurement constant temperature magnetic stirrer, stirring and reacting for 6 hours at a constant temperature under the conditions that the temperature is 40 ℃ and the rotating speed is 500r/min, filtering to obtain filter residue, washing the filter residue for 6 times by deionized water, then transferring the washed filter residue into a vacuum drying oven, and drying the filter residue in vacuum at a temperature of 90 ℃ and a pressure of 120Pa to a constant weight to obtain low molecular weight polyaniline; according to the mass ratio of 1: 20, mixing graphene oxide and a solvent, pouring the mixture into a three-neck flask, carrying out ultrasonic dispersion for 60min under the condition that the ultrasonic frequency is 60kHz, moving the three-neck flask to a digital display speed measurement constant-temperature magnetic stirrer, slowly adding low-molecular-weight polyaniline with the mass of 0.2 times that of the graphene oxide into the three-neck flask at the constant-temperature stirring speed of 600r/min while carrying out constant-temperature stirring, sealing the three-neck flask after the low-molecular-weight polyaniline is added, continuously carrying out constant-temperature sealed stirring reaction for 12h, filtering to obtain a filter cake, washing the filter cake for 5 times by using N-methyl pyrrolidone, transferring the washed filter cake into a vacuum drying oven, and drying to constant weight under the conditions that the temperature is 110 ℃ and the pressure is 100Pa to obtain the intercalation modified graphene oxide; taking 30 parts of intercalation modified graphene oxide, 80 parts of silicate ester, 10 parts of stearic acid and 300 parts of absolute ethyl alcohol in sequence, mixing the intercalation modified graphene oxide and the absolute ethyl alcohol, pouring the mixture into a reaction kettle, carrying out ultrasonic dispersion for 2 hours under the ultrasonic frequency of 65kHz, then sequentially adding the silicate ester and the stearic acid into the reaction kettle, heating and stirring the mixture for reaction for 6 hours under the conditions of the temperature of 90 ℃ and the rotating speed of 800r/min, transferring the material in the reaction kettle into a rotary evaporator, and carrying out reduced pressure concentration for 40 minutes under the conditions of the temperature of 85 ℃ and the pressure of 450mmHg to obtain a concentrated solution; and sequentially taking 60 parts of copper sulfate solution, 60 parts of sulfuric acid solution and 10 parts of concentrated solution according to parts by weight, mixing, shearing at a high speed for 30min at a rotating speed of 12000r/min, standing, and defoaming in vacuum to obtain the special colloidal electrolyte for the flow battery. The biological enzyme is horseradish peroxidase and laccase in a mass ratio of 5: 1 is prepared by compounding. The hydrogen peroxide solution is 25% by mass of hydrogen peroxide solution. The solvent is N-methyl pyrrolidone. The silicate is methyl orthosilicate. The copper sulfate solution is 0.8mol/L copper sulfate solution. The sulfuric acid solution is 1.8mol/L sulfuric acid solution.
Example 2
According to the mass ratio of 1: 20, mixing graphene oxide and a solvent, pouring the mixture into a three-neck flask, carrying out ultrasonic dispersion for 60min under the condition that the ultrasonic frequency is 60kHz, moving the three-neck flask to a digital display speed measurement constant-temperature magnetic stirrer, slowly adding polyaniline with the mass of 0.2 time of that of the graphene oxide into the three-neck flask at the constant-temperature stirring speed of 600r/min while carrying out constant-temperature stirring, sealing the three-neck flask after the polyaniline is completely added, continuously carrying out constant-temperature sealed stirring reaction for 12h, filtering to obtain a filter cake, washing the filter cake for 5 times by using N-methyl pyrrolidone, transferring the washed filter cake into a vacuum drying oven, and drying to constant weight under the conditions that the temperature is 110 ℃ and the pressure is 100Pa to obtain the intercalation modified graphene oxide; taking 30 parts of intercalation modified graphene oxide, 80 parts of silicate ester, 10 parts of stearic acid and 300 parts of absolute ethyl alcohol in sequence, mixing the intercalation modified graphene oxide and the absolute ethyl alcohol, pouring the mixture into a reaction kettle, carrying out ultrasonic dispersion for 2 hours under the ultrasonic frequency of 65kHz, then sequentially adding the silicate ester and the stearic acid into the reaction kettle, heating and stirring the mixture for reaction for 6 hours under the conditions of the temperature of 90 ℃ and the rotating speed of 800r/min, transferring the material in the reaction kettle into a rotary evaporator, and carrying out reduced pressure concentration for 40 minutes under the conditions of the temperature of 85 ℃ and the pressure of 450mmHg to obtain a concentrated solution; and sequentially taking 60 parts of copper sulfate solution, 60 parts of sulfuric acid solution and 10 parts of concentrated solution according to parts by weight, mixing, shearing at a high speed for 30min at a rotating speed of 12000r/min, standing, and defoaming in vacuum to obtain the special colloidal electrolyte for the flow battery. The biological enzyme is horseradish peroxidase and laccase in a mass ratio of 5: 1 is prepared by compounding. The hydrogen peroxide solution is 25% by mass of hydrogen peroxide solution. The solvent is N-methyl pyrrolidone. The silicate is methyl orthosilicate. The copper sulfate solution is 0.8mol/L copper sulfate solution. The sulfuric acid solution is 1.8mol/L sulfuric acid solution.
Example 3
Sequentially taking 10 parts of aniline, 40 parts of hydrogen peroxide, 300 parts of water and 0.08 part of biological enzyme according to parts by weight, firstly mixing aniline and water, pouring the mixture into a No. 1 beaker, moving the No. 1 beaker into a water bath kettle, stirring and dissolving the mixture for 2 hours at a constant temperature under the conditions that the temperature is 65 ℃ and the stirring speed is 500r/min, taking out the No. 1 beaker, naturally cooling the mixture to 40 ℃, then sequentially adding hydrogen peroxide and the biological enzyme into the No. 1 beaker, moving the No. 1 beaker to a digital display speed measurement constant temperature magnetic stirrer, stirring and reacting for 6 hours at a constant temperature under the conditions that the temperature is 40 ℃ and the rotating speed is 500r/min, filtering to obtain filter residue, washing the filter residue for 6 times by deionized water, then transferring the washed filter residue into a vacuum drying oven, and drying the filter residue in vacuum at a temperature of 90 ℃ and a pressure of 120Pa to a constant weight to obtain low molecular weight polyaniline; according to the mass ratio of 1: 20, mixing graphene oxide and a solvent, pouring the mixture into a three-neck flask, carrying out ultrasonic dispersion for 60min under the condition that the ultrasonic frequency is 60kHz, moving the three-neck flask to a digital display speed measurement constant-temperature magnetic stirrer, slowly adding low-molecular-weight polyaniline with the mass of 0.2 times that of the graphene oxide into the three-neck flask at the constant-temperature stirring speed of 600r/min while carrying out constant-temperature stirring, sealing the three-neck flask after the low-molecular-weight polyaniline is added, continuously carrying out constant-temperature sealed stirring reaction for 12h, filtering to obtain a filter cake, washing the filter cake for 5 times by using N-methyl pyrrolidone, transferring the washed filter cake into a vacuum drying oven, and drying to constant weight under the conditions that the temperature is 110 ℃ and the pressure is 100Pa to obtain the intercalation modified graphene oxide; taking 30 parts of intercalated modified graphene oxide, 80 parts of silicate ester, 10 parts of ionized water and 300 parts of absolute ethyl alcohol in sequence, mixing the intercalated modified graphene oxide and the absolute ethyl alcohol, pouring the mixture into a reaction kettle, carrying out ultrasonic dispersion for 2 hours under the ultrasonic frequency of 65kHz, then sequentially adding the silicate ester and the ionized water into the reaction kettle, heating and stirring the mixture for reaction for 6 hours under the conditions of the temperature of 90 ℃ and the rotating speed of 800r/min, transferring the materials in the reaction kettle into a rotary evaporator, and carrying out reduced pressure concentration for 40 minutes under the conditions of the temperature of 85 ℃ and the pressure of 450mmHg to obtain a concentrated solution; and sequentially taking 60 parts of copper sulfate solution, 60 parts of sulfuric acid solution and 10 parts of concentrated solution according to parts by weight, mixing, shearing at a high speed for 30min at a rotating speed of 12000r/min, standing, and defoaming in vacuum to obtain the special colloidal electrolyte for the flow battery. The biological enzyme is horseradish peroxidase and laccase in a mass ratio of 5: 1 is prepared by compounding. The hydrogen peroxide solution is 25% by mass of hydrogen peroxide solution. The solvent is N-methyl pyrrolidone. The silicate is methyl orthosilicate. The copper sulfate solution is 0.8mol/L copper sulfate solution. The sulfuric acid solution is 1.8mol/L sulfuric acid solution.
Example 4
Sequentially taking 10 parts of aniline, 40 parts of hydrogen peroxide, 300 parts of water and 0.08 part of biological enzyme according to parts by weight, firstly mixing aniline and water, pouring the mixture into a No. 1 beaker, moving the No. 1 beaker into a water bath kettle, stirring and dissolving the mixture for 2 hours at a constant temperature under the conditions that the temperature is 65 ℃ and the stirring speed is 500r/min, taking out the No. 1 beaker, naturally cooling the mixture to 40 ℃, then sequentially adding hydrogen peroxide and the biological enzyme into the No. 1 beaker, moving the No. 1 beaker to a digital display speed measurement constant temperature magnetic stirrer, stirring and reacting for 6 hours at a constant temperature under the conditions that the temperature is 40 ℃ and the rotating speed is 500r/min, filtering to obtain filter residue, washing the filter residue for 6 times by deionized water, then transferring the washed filter residue into a vacuum drying oven, and drying the filter residue in vacuum at a temperature of 90 ℃ and a pressure of 120Pa to a constant weight to obtain low molecular weight polyaniline; according to the mass ratio of 1: 20, mixing graphene oxide and a solvent, pouring the mixture into a three-neck flask, carrying out ultrasonic dispersion for 60min under the condition that the ultrasonic frequency is 60kHz, moving the three-neck flask to a digital display speed measurement constant-temperature magnetic stirrer, slowly adding low-molecular-weight polyaniline with the mass of 0.2 times that of the graphene oxide into the three-neck flask at the constant-temperature stirring speed of 600r/min while carrying out constant-temperature stirring, sealing the three-neck flask after the low-molecular-weight polyaniline is added, continuously carrying out constant-temperature sealed stirring reaction for 12h, filtering to obtain a filter cake, washing the filter cake for 5 times by using N-methyl pyrrolidone, transferring the washed filter cake into a vacuum drying oven, and drying to constant weight under the conditions that the temperature is 110 ℃ and the pressure is 100Pa to obtain the intercalation modified graphene oxide; taking 30 parts of intercalation modified graphene oxide, 80 parts of fumed silica, 10 parts of stearic acid and 300 parts of absolute ethyl alcohol in sequence according to parts by weight, firstly mixing the intercalation modified graphene oxide and the absolute ethyl alcohol, pouring the mixture into a reaction kettle, carrying out ultrasonic dispersion for 2 hours under the ultrasonic frequency of 65kHz, then sequentially adding the fumed silica and the stearic acid into the reaction kettle, then carrying out heating stirring reaction for 6 hours under the conditions of the temperature of 90 ℃ and the rotating speed of 800r/min, transferring the materials in the reaction kettle into a rotary evaporator, and carrying out reduced pressure concentration for 40 minutes under the conditions of the temperature of 85 ℃ and the pressure of 450mmHg to obtain a concentrated solution; and sequentially taking 60 parts of copper sulfate solution, 60 parts of sulfuric acid solution and 10 parts of concentrated solution according to parts by weight, mixing, shearing at a high speed for 30min at a rotating speed of 12000r/min, standing, and defoaming in vacuum to obtain the special colloidal electrolyte for the flow battery. The biological enzyme is horseradish peroxidase and laccase in a mass ratio of 5: 1 is prepared by compounding. The hydrogen peroxide solution is 25% by mass of hydrogen peroxide solution. The solvent is N-methyl pyrrolidone. The copper sulfate solution is 0.8mol/L copper sulfate solution. The sulfuric acid solution is 1.8mol/L sulfuric acid solution.
Comparative example: the colloidal electrolyte specially used for the flow battery and produced by the new material company Limited is tin-free.
The performance of the special colloid electrolyte for the flow battery and the comparative product obtained in the examples 1 to 4 is tested, and the specific testing method is as follows:
a CT2001C-10V/2A type battery tester (Wuhan dynasty) is adopted to carry out charge and discharge tests, and the coulomb efficiency is calculated.
Specific detection results are shown in table 1:
table 1 specific detection results of colloidal electrolyte for flow battery
| Detecting items | Coulomb efficiency/%) | First discharge capacity/mAh/g |
| Example 1 | 99.8 | 1300 |
| Example 2 | 96.2 | 1100 |
| Example 3 | 90.7 | 930 |
| Example 4 | 87.6 | 700 |
| Comparative example | 83.4 | 600 |
The detection results in table 1 show that the colloidal electrolyte special for the flow battery prepared by the technical scheme of the invention has the characteristics of excellent high-current discharge performance and initial capacity, and has a wide prospect in the development of the battery material technology industry.
Claims (8)
1. A preparation method of a special colloidal electrolyte for a flow battery is characterized by comprising the following specific preparation steps:
(1) sequentially taking 8-10 parts of aniline, 30-40 parts of hydrogen peroxide, 200-300 parts of water and 0.06-0.08 part of biological enzyme according to parts by weight, heating, stirring and dissolving aniline and water, cooling to 35-40 ℃, adding hydrogen peroxide and biological enzyme, stirring and reacting at constant temperature, filtering, washing and drying to obtain low molecular weight polyaniline;
(2) according to the mass ratio of 1: 10-1: 20, dispersing graphene oxide in a solvent, slowly adding low molecular weight polyaniline with the mass of 0.1-0.2 times that of the graphene oxide under the constant-temperature stirring state, after the adding is finished, carrying out constant-temperature closed stirring reaction for 8-12 h, filtering, washing and drying to obtain the intercalation modified graphene oxide;
(3) sequentially taking 20-30 parts by weight of intercalated modified graphene oxide, 60-80 parts by weight of silicate ester, 8-10 parts by weight of stearic acid and 200-300 parts by weight of absolute ethyl alcohol, mixing and dispersing the intercalated modified graphene oxide and the absolute ethyl alcohol, then adding the silicate ester and the stearic acid, heating, stirring, reacting, and concentrating under reduced pressure to obtain a concentrated solution;
(4) and sequentially taking 40-60 parts by weight of copper sulfate solution, 40-60 parts by weight of sulfuric acid solution and 8-10 parts by weight of concentrated solution, shearing at a high speed, and defoaming in vacuum to obtain the special colloidal electrolyte for the flow battery.
2. The preparation method of the colloidal electrolyte special for flow batteries according to claim 1, wherein the biological enzyme in step (1) is horseradish peroxidase and laccase in a mass ratio of 3: 1-5: 1 is prepared by compounding.
3. The preparation method of the colloidal electrolyte special for the flow battery according to claim 1, wherein the hydrogen peroxide in the step (1) is a hydrogen peroxide solution with a mass fraction of 15-25%.
4. The method for preparing the colloidal electrolyte special for the flow battery according to claim 1, wherein the slow addition in the step (2) is performed at a rate of 3-8 g/min.
5. The method for preparing the colloidal electrolyte special for flow batteries according to claim 1, wherein the solvent in step (2) is any one of N-methylpyrrolidone or N, N-dimethylformamide.
6. The preparation method of the colloidal electrolyte special for flow batteries according to claim 1, wherein the silicate in step (3) is any one of methyl orthosilicate, ethyl orthosilicate and propyl orthosilicate.
7. The method for preparing the colloidal electrolyte special for the flow battery as claimed in claim 1, wherein the copper sulfate solution in the step (4) is a copper sulfate solution with a concentration of 0.7-0.8 mol/L.
8. The preparation method of the colloidal electrolyte special for flow batteries according to claim 1, wherein the sulfuric acid solution in step (4) is a sulfuric acid solution with a concentration of 1.6-1.8 mol/L.
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