CN106549162B - Composite electrode material, preparation method thereof and application of composite electrode material in all-vanadium redox flow battery - Google Patents

Composite electrode material, preparation method thereof and application of composite electrode material in all-vanadium redox flow battery Download PDF

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CN106549162B
CN106549162B CN201510607684.6A CN201510607684A CN106549162B CN 106549162 B CN106549162 B CN 106549162B CN 201510607684 A CN201510607684 A CN 201510607684A CN 106549162 B CN106549162 B CN 106549162B
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electrode material
acid
composite electrode
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carbonate
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CN106549162A (en
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姚川
付华峰
李�浩
孟晶晶
孙红
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Xuchang University
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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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • H—ELECTRICITY
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    • 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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Abstract

The invention discloses a composite electrode material, a preparation method thereof and application thereof in an all-vanadium redox flow battery. The preparation method comprises the following steps: dissolving an organic carbon source precursor in water or an organic solvent or a mixture thereof; adding a certain amount of micro-nano spherical particle materials as a hard template; and (2) fully soaking the three-dimensional carbon substrate material in the suspension, then carbonizing the three-dimensional carbon substrate material in a tube furnace, finally, pickling the material to remove particles serving as hard templates, and repeatedly washing and drying. The surface of the composite electrode material is in a uniform porous shape, the pore channels are communicated, the pore size is in a micro-nano level, the specific surface area and the porosity are high, and meanwhile, the surface contains a certain number of oxygen-containing functional groups such as hydroxyl, carboxyl, lactone group and the like. The composite electrode material can be simultaneously used as an electrode material of an all-vanadium redox flow battery, has stronger electrocatalytic activity, and obviously reduces VO2+/VO2 +The charge transfer impedance of the redox electrode reaction and the resulting polarization overpotential.

Description

Composite electrode material, preparation method thereof and application of composite electrode material in all-vanadium redox flow battery
Technical Field
The invention relates to the technical field of large-scale energy storage batteries, in particular to a composite electrode material, a preparation method thereof and application thereof in an all-vanadium redox flow battery.
Background
With the excessive consumption of fossil fuels and the increasing increase of environmental pollution, governments of various countries are continuously increasing the research and development efforts on the investment of renewable energy sources such as wind energy and solar energy, and striving to find an effective substitute before the exhaustion of fossil energy sources. The U.S. energy information agency speculates that by 2030 about 40% of the us electricity supply will come from renewable energy generation (qianbei, us renewable energy utilization status and forecast, world wide energy network, www]. In 2009, the government of China promises the world in the 'Chinese new energy industry happy planning', and the renewable energy consumption accounts for 15% of the total energy consumption by 2020 [ the national energy agency bulletin, www.nea.gov.cn/2012-02/10/c _131402482.htm, 2013-03-22%]. At the moment, the installed wind power capacity is increased from 30GW in 2010 to 150GW, and the installed photovoltaic power generation capacity is also increased from 1GW in 2010 to 20 GW. However, due to the influence of random variables such as seasons, climate, day and night temperature difference, the power generation of renewable energy sources such as wind energy and solar energy generates random fluctuation and has the characteristics of discontinuity and instability. If the low-grade electric energy is directly connected to the grid, impact hazard and harmonic pollution are brought to the power grid, and great obstacles are brought to large-scale application of the power grid, so that the phenomena of large-area waste of resources such as 'electricity abandonment', 'waste electricity', and the like are caused. According to incomplete statistical data, in 2012, wind power resources wasted by China exceed 20TWhhttp://finance.sina.com.cn/roll/20141119/ 205420864737.shtml]. This, in the present day when the power supply is increasingly tense, causes wind power generation andunreasonable "relative overage" of photovoltaic power generation electrodes and operational stagnation and large-area loss of related enterprises.
An effective solution to this problem is to introduce an energy storage technology with a regular and smooth function between "renewable energy power generation" and "power grid" as an intermediary, so as to change the traditional "instant power and instant use" power supply mode. The low-grade electric energy is stored firstly, and is integrated and then is output in a smooth and stable mode. Among many energy storage technologies, the all Vanadium Flow Battery (VFB) has the following advantages: 1) high energy efficiency, safe and stable operation and long cycle life (the charge-discharge cycle reaches more than 13000 times, and the service life exceeds 20 years); 2) the site selection is free, the power and the capacity are mutually independent, and the system design is flexible; 3) the method is the most promising technology for solving the problems of randomness and intermittent unsteadiness of a renewable energy power generation system such as solar energy and wind energy, and has important requirements in the construction of renewable energy power generation and a smart grid [ Journal of the electrochemical Society,2011,158, R55, and the like]. In addition, the technology has important potential application value in the fields of 'peak clipping and valley filling' of a power grid, uninterrupted emergency power supplies, electric vehicle charging stations, communication base stations and military affairs. In the energy storage technology development program made in 2012 of the united states, the name of the all-vanadium redox flow energy storage battery is the first priority of the development technology. This technology was first introduced in 1985 by professor Marria Kacos and co-workers at university of New south Wales, Australia, who employed vanadium ions VO of different valency2+/VO2 +，V2+/V3+The active materials are respectively used as positive and negative electrode active materials, so that the cross contamination of positive and negative electrode electrolyte solutions is avoided to a great extent. The standard electromotive force of the battery is 1.26V, and the working principle is as follows:
and (3) positive electrode:
Figure BDA0000808773950000021
negative electrode:
Figure BDA0000808773950000022
several demonstration projects are currently in operation in different regions, with the core technology being dominated by developed countries such as japan, the usa, australia, canada and europe. In the coming home of China, various technical issues and issues are carried out and demonstration operation is actively carried out since the nineties of the last century, and main research units comprise research institutes such as the institute of chemical and physical in the university of Chinese academy, the university of Qinghua, the university of China and the like, and enterprises such as the energy storage in the department of great junctional science and the Beijing general energy. Recently, the applied demonstration engineering with the scale of 5MW/10MWh developed by the institute of chemical and physical research of the Chinese academy of sciences is accepted by the Liaoning electric power survey design institute, and becomes the largest-scale all-vanadium flow energy storage battery system in the world to date. However, in order to realize commercial popularization and application, a series of problems still exist in the all-vanadium redox flow energy storage technology battery and need to be solved urgently. The important research direction in the field in recent years is to improve the charge-discharge current density of the all-vanadium liquid flow current, reduce the size of the battery module and further reduce the production and manufacturing cost. At present, the charge-discharge current density of an all-vanadium redox flow battery system is reported to be about 80-120 mA/cm under the condition that the energy conversion efficiency is kept higher than 80%2. If the value can be increased to 160-200 mA/cm2Without reducing the energy conversion efficiency, the power density of the battery module can be improved by nearly one time, which inevitably promotes the commercialization process of the all-vanadium redox flow energy storage battery.
The electrode material is one of the key materials in the flow energy storage battery and is also an important factor for determining the power density of the battery. The main electrode material for VFB at present is carbon fiber felt or graphite felt. The electrode material is mainly characterized by high porosity and relatively large active area, but the electrode material is used for VO2+/VO2 +The poor electrode reaction activity and reversibility of redox couple become one of the main factors limiting the increase of power density of batteries [ Carbon,2012,50,2347-]. In order to improve the performance of carbon fiber materials, surface treatment or modification is usually performed, and the common methods mainly include surface oxidation and metal coating [ Electrochimica Acta,1992,37, 1253-1269-]. The oxidation treatment easily reduces the carbon fiberThe mechanical property and the conductivity of the electrode are maintained, and the reduction of oxygen evolution overpotential of the electrode material in the charging process is easily caused; the stability problem of the surface-coated metal material in the long-term operation of a strong-acid and strong-oxidizing electrolyte system is difficult to solve, most of the used metals are noble metals or alloys thereof such as Ir, Pt and Ru, and the high cost is also an obstacle to the large-scale application of the metal material. In recent years, several novel Carbon materials such as Carbon nanotubes [ Carbon,2014,9,3463-]Graphene [ Carbon,2014,9,693-]Nitrogen-doped mesoporous carbon [ Journal of Power Sources,2010,195,4375-]Carbon nanowall [ Nano Energy,2012,1,833-]Also reported for use as VFB positive electrode materials. However, these materials are complicated to prepare, are in powder form, and are difficult to use directly (or use a large amount of binder to support on a carbon fiber felt substrate to reduce the electronic conductivity). Therefore, development of an electrode material having a large specific surface area, high catalytic activity, stable cycle performance, and low cost is still an important research topic in this field.
Disclosure of Invention
The invention aims to provide a composite electrode material with large specific surface area, high catalytic activity, stable cycle performance and low price, a preparation method and application thereof, so as to improve the energy conversion efficiency and power density of an all-vanadium redox flow battery, thereby solving the problem that carbon fiber fabrics (such as carbon felt, carbon paper, carbon cloth and the like) have VO (vacuum organic vapor) effect2+/VO2 +The electrocatalytic activity of the redox couple is low; and other modified electrode materials are difficult to apply on a large scale.
In order to achieve the above object, in one aspect, the invention adopts the technical scheme that: a method of preparing a composite electrode material for an all-vanadium flow battery, the method comprising the steps of:
1) dissolving an organic carbon source precursor in water, or an organic solvent, or a mixture of water and the organic solvent;
2) adding a micro-nano granular inorganic material into the solution to serve as a hard template, and then placing the hard template and the micro-nano granular inorganic material into an ultrasonic washing tank for oscillation until uniformly dispersed suspension is formed;
3) placing the three-dimensional carbon substrate material into the suspension for full impregnation so as to uniformly coat the inner surface of the three-dimensional carbon substrate material, taking out the coated three-dimensional carbon substrate material, and drying the coated three-dimensional carbon substrate material in a vacuum drying oven at room temperature;
4) placing the fully dried material in a temperature programmed tube furnace, introducing inert gas into the furnace, raising the temperature of the furnace to a target temperature so as to carbonize the organic carbon source precursor, and naturally cooling the furnace to room temperature;
5) acid washing the carbonized material by using an acid solution to remove the micro-nano granular material serving as the hard template;
6) the acid-washed material was repeatedly washed with deionized water and then dried in a vacuum oven at room temperature for use in assembling a battery.
Further, the organic carbon source precursor in the step 1) is at least one of cellulose, starch, fructose, maltose, hemicellulose, arabic gum, carrageenan, arabinose, glucose, sucrose, polyvinyl alcohol, polyethylene glycol and polypropylene alcohol.
Further, the organic solvent in step 1) is at least one of methanol, ethanol, n-propanol, isopropanol, acetone, ethylene glycol and dimethyl sulfoxide.
Further, the hard template material in the step 2) is at least one of calcium carbonate, zinc oxide, sodium carbonate, potassium carbonate, iron carbonate, barium carbonate, strontium carbonate, zinc carbonate, magnesium carbonate, lithium carbonate, magnesium hydroxide, zinc hydroxide and iron oxide
Further, the three-dimensional carbon substrate material is at least one of carbon fiber felt, graphite fiber felt, carbon fiber paper, graphite fiber paper, foam carbon and carbon cloth.
Further, the inert gas in the step 4) is at least one of nitrogen, argon and helium.
Further, the temperature rise rate of the carbonization process in the step 4) is 1-20 ℃/min; the target temperature is 600-1500 ℃; and the carbonization time is 0.5-20 h.
Further, the acid solution in step 5) is a solution obtained by dissolving at least one of hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, hydrochloric acid, acetic acid, and benzenesulfonic acid in water.
Furthermore, the molar concentration of the acid solution is 0.1-3.0 mol/L.
In another aspect, the present invention provides a composite electrode material prepared by the method described above.
In another aspect, the invention provides a use of the composite electrode material prepared by the above-described method in an electrode material of an all-vanadium flow battery.
In a further aspect, the invention provides a composite electrode material prepared by the method, or a material taking the composite electrode material as a carrier and further carrying other catalysts, for use in an electrode material of an all-vanadium flow battery.
The composite electrode material prepared by the method has the following beneficial effects:
(1) the surface of the composite electrode material is in a uniform porous shape, the pore channels are communicated, the pore size is in a micro-nano level, the specific surface area and the porosity are high, and meanwhile, the surface contains a certain number of oxygen-containing functional groups such as hydroxyl, carboxyl, lactone group and the like.
(2) The composite electrode material can be used as an electrode material of an all-vanadium redox flow battery, has stronger electrocatalytic activity, and obviously reduces VO2+/VO2 +The charge transfer impedance of the redox couple electrode reaction and the polarization overpotential generated by the charge transfer impedance significantly improve the reversibility of the electrode reaction.
(3) In the process of preparing the composite electrode by using the composite electrode material, an adhesive is not needed, and the prepared composite electrode has good conductivity; the preparation process is simple and easy to implement, the cost is low, and the industrial production is easy to realize.
(4) The composite electrode prepared by using the composite electrode material can be used for an all-vanadium redox flow battery, the energy conversion efficiency and the charge-discharge current density of the battery are greatly improved, the power density of the battery is further improved, and the volume and the production and manufacturing cost of a battery module can be reduced while the same energy storage task is completed. The commercialization of the all-vanadium flow battery is promoted.
Drawings
Fig. 1(a) and (b) are the micro-morphologies of the novel composite electrode material prepared in example 1 of the present invention.
FIG. 2 shows the VO of 0.05mol/L of the novel composite electrode material prepared in example 1 of the present invention2++0.05mol/L VO2 ++3mol/L H2SO4Cyclic voltammogram in an electrolyte solution.
FIG. 3 shows an all vanadium flow battery assembled at 80mA/cm using the novel composite electrode material prepared in example 1 of the present invention2、100mA/cm2、120mA/cm2、140mA/cm2And 160mA/cm2Current density of (a).
FIG. 4 shows an all vanadium flow battery assembled at 40mA/cm using the novel composite electrode material prepared in example 2 of the present invention2、60mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2Current density of (a).
Detailed Description
In order to make the objects and advantages of the present invention clearer, the technical solutions claimed in the present invention will now be described in further detail with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting.
In one embodiment of the invention, the invention provides a method for preparing a composite electrode material for an all-vanadium flow battery, comprising the steps of:
1) dissolving an organic carbon source precursor in water, or an organic solvent, or a mixture of water and the organic solvent;
2) adding micro-nano granular materials serving as hard templates into the solution, and placing the micro-nano granular materials into an ultrasonic washing tank for oscillation until uniformly dispersed suspension is formed;
3) placing the three-dimensional carbon substrate material into the suspension for full impregnation, uniformly coating the inner surface of the three-dimensional carbon substrate material, taking out the coated three-dimensional carbon substrate material, and drying the coated three-dimensional carbon substrate material in a vacuum drying oven at room temperature;
4) placing the fully dried material in a temperature programmed tube furnace, introducing inert gas into the furnace, raising the temperature of the furnace to a target temperature to carbonize the organic carbon source precursor, and naturally cooling the furnace to room temperature;
5) acid washing the carbonized material by using an acid solution to remove the micro-nano granular material serving as the hard template;
6) the acid-washed material was repeatedly washed with deionized water and then dried in a vacuum oven at room temperature for use.
Preferably, the organic carbon source precursor in step 1) is at least one of cellulose, starch, fructose, maltose, hemicellulose, acacia, carrageenan, arabinose, glucose, sucrose, polyvinyl alcohol, polyethylene glycol and polypropylene alcohol.
Preferably, the organic solvent in step 1) is at least one of methanol, ethanol, n-propanol, isopropanol, acetone, ethylene glycol and dimethylsulfoxide.
Preferably, the hard template material in step 2) is at least one of calcium carbonate, zinc oxide, sodium carbonate, potassium carbonate, iron carbonate, barium carbonate, strontium carbonate, zinc carbonate, magnesium carbonate, lithium carbonate, magnesium hydroxide, zinc hydroxide, and iron oxide. The hard template material accounts for 5-40% of the total mass fraction of the suspension.
Preferably, in the method for preparing the composite electrode material for the all-vanadium flow battery, the three-dimensional carbon substrate material is at least one of carbon fiber felt, graphite fiber felt, carbon fiber paper, graphite fiber paper, carbon foam and carbon cloth.
Preferably, in the method for preparing the composite electrode material for the all-vanadium flow battery, the inert gas in the step 4) is at least one of nitrogen, argon and helium.
Preferably, in the method for preparing the composite electrode material for the all-vanadium redox flow battery, the temperature rise rate of the carbonization process in the step 4) is 1-20 ℃/min; the target temperature is 600-1500 ℃; and the carbonization time is 0.5-20 h.
Preferably, the acid solution in step 5) is a solution obtained by dissolving at least one of hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, hydrochloric acid, acetic acid, and benzenesulfonic acid in water.
Preferably, in the method for preparing the composite electrode material for the all-vanadium flow battery, the mass concentration of the acid solution is 0.1-3.0 mol/L.
In another aspect, the present invention provides a composite electrode material prepared by the method described above.
In another aspect, the invention provides a use of the composite electrode material prepared by the above-described method in an electrode material of an all-vanadium flow battery.
In a further aspect, the invention provides a composite electrode material prepared by the method, or a material taking the composite electrode material as a carrier and further carrying other catalysts, for use in an electrode material of an all-vanadium flow battery.
Example 1
In this example, in preparing the composite electrode material for the all-vanadium flow battery, the following steps are adopted:
1) 10g of maltose as an organic carbon source precursor was dissolved in 100mL of total water and ethanol at a water to ethanol volume ratio of 1: 1.
2) Adding 20g of micro-nano granular zinc carbonate as a hard template into the solution, wherein the particle size of the zinc carbonate is about 50-100 nm, and then placing the zinc carbonate into an ultrasonic washing tank for oscillation until uniformly dispersed suspension is formed.
3) Cutting the carbon fiber felt into the size of 30mm multiplied by 5mm, then putting the carbon fiber felt into the suspension liquid for full dipping so as to ensure that the inner surface of the carbon fiber felt is uniformly coated, then taking out the coated carbon fiber felt, and putting the coated carbon fiber felt into a vacuum drying oven for drying at room temperature.
4) Placing the fully dried material in a temperature programmed tube furnace, introducing nitrogen gas into the furnace as protective gas, purging the tube furnace to replace air in the tube before temperature rise, raising the temperature of the furnace to 1000 ℃ at a temperature rise rate of 5 ℃/min, preserving heat for 3h to carbonize the material, and naturally cooling the furnace to room temperature.
5) And preparing a hydrochloric acid solution with the mass concentration of 1mol/L for pickling the carbonized material so as to remove the micro-nano particle zinc carbonate serving as the hard template.
6) The acid-washed material was repeatedly washed with deionized water and then dried in a vacuum oven at room temperature for use.
Carrying out appearance characterization on the prepared novel composite electrode material: the microscopic morphology was observed using a field emission scanning electron microscope and the results are shown in FIGS. 1(a) and (b). As shown in FIG. 1, the surface of the electrode material is a uniform porous structure, the pore size is about 50-100 nm, the pore wall is only a few nanometers, and the pore channels are through. This structure will make the electrode material have high specific surface area and porosity, thus facilitating the transfer and adsorption of the electrode active substance.
Performing electrochemical performance characterization on the prepared novel composite electrode material: firstly, constructing a three-electrode system electrolytic cell which consists of a prepared novel composite electrode material as a working electrode, a large-area graphite plate as a counter electrode and a saturated calomel electrode as a reference electrode; then preparing an electrolyte solution: 0.05mol/L VO2++0.05mol/L VO2 ++3mol/LH2SO4Performing cyclic voltammetry scanning to obtain the prepared novel composite electrode material for VO2+/VO2 +The cyclic voltammogram of the redox couple is shown in figure 2. Through the magnitude and the ratio of the peak current values in the oxidation and reduction processes, the potential difference of the oxidation and reduction peaks and the change relation of the oxidation and reduction peak currents along with the scanning speed, the novel composite electrode material can be seen to VO2+/VO2 +The redox couples all have good electrocatalytic activity. VO at a scanning speed of 10mV/s2+/VO2 +The difference in the potential of the oxidation and reduction peaks of the redox couple was only about 100mV, and as the scan rate increased, the position of the oxidation and reduction peaks was essentially unchanged, indicating good reversibility of the electrode process.
In addition, in the present example, the novel composite electrode material was applied to the assembly of an all vanadium flow battery. The cell was assembled in a filter press in the order of end plate-collector plate-electrode-separator-electrode-collector plate-end plate. Wherein, the diaphragm adopts a perfluorosulfonic acid membrane. The battery was subjected to charge and discharge tests at different current densities, and the results are shown in fig. 3. The results show that the cell is at 80mA/cm2、100mA/cm2、120mA/cm2、140mA/cm2And 160mA/cm2Can be normally charged and discharged at a current density of (2), and has a smooth curve. At 80mA/cm2The energy conversion efficiency of the battery reaches up to 86.5 percent under the current density of the battery; and even at 160mA/cm2Under the high-rate condition, the energy conversion efficiency of the battery is still close to 80%.
Comparative example 1
In contrast to example 1, an all vanadium flow battery was assembled using untreated carbon fiber felt of the same size as the electrode material, which is currently in common use. The cell was assembled in the same manner as in example 1 except that the working electrode was made of the same material at 80mA/cm2、100mA/cm2、120mA/cm2、140mA/cm2And 160mA/cm2The battery was subjected to a charge and discharge test at the current density of (1). The results showed that at 80mA/cm2The energy conversion efficiency of the battery is 82.2% at the current density of (3); and at 160mA/cm2The energy conversion efficiency of the battery is only 73.5 percent under the high-rate condition.
Example 2
In this example, in preparing the composite electrode material for the all-vanadium flow battery, the following steps are adopted:
1) 5g of fructose as an organic carbon source precursor is dissolved in 100mL of total water and dimethyl sulfoxide, wherein the volume ratio of the water to the dimethyl sulfoxide is 5: 1.
2) Adding 15g of micro-nano granular magnesium carbonate into the solution to serve as a hard template, wherein the particle size of the magnesium carbonate is about 100-300 nm. They were then placed in an ultrasonic wash tank and shaken until a uniformly dispersed suspension was formed.
3) The carbon fiber paper was cut into a size of 30mm × 30mm, and the thickness thereof was about 200 μm. And then placing the carbon fiber paper into the suspension to be fully soaked so as to enable the inner surface of the carbon fiber paper to be uniformly coated, taking out the coated carbon fiber paper, and placing the coated carbon fiber paper into a vacuum drying oven to be dried at room temperature.
4) Placing the fully dried material in a temperature programmed tube furnace, introducing nitrogen gas into the furnace as protective gas, purging the tube furnace to replace air in the tube before temperature rising, raising the temperature of the furnace to 700 ℃ at a temperature rising rate of 10 ℃/min, preserving heat for 4h, carbonizing the material, and naturally cooling the furnace to room temperature.
5) And preparing a nitric acid solution with the mass concentration of 0.5mol/L for pickling the carbonized material to remove the micro-nano granular magnesium carbonate serving as the hard template.
6) The acid-washed material was repeatedly washed with deionized water and then dried in a vacuum oven at room temperature for use.
In this example, the novel composite electrode material was applied to the assembly of an all vanadium flow battery. The cell was assembled in a filter press in the order of end plate-collector plate-electrode-separator-electrode-collector plate-end plate. Wherein, the diaphragm adopts a perfluorosulfonic acid membrane. The results of the charge and discharge tests performed on the batteries at different current densities are shown in fig. 4. The results show that the cell is at 40mA/cm2、60mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2Can be normally charged and discharged at a current density of (2), and has a smooth curve. At 40mA/cm2The energy conversion efficiency of the battery reaches up to 81.4 percent under the current density of the battery; and even at 120mA/cm2The energy conversion efficiency of the battery can still reach 70.9 percent under the high-rate condition.
Comparative example 2
In contrast to example 2, an all vanadium flow battery was assembled using untreated carbon fiber paper of the same size as the electrode material, which is currently commonly used. The cell was assembled in the same manner as in example 1 except that the working electrode was made of the same material at 40mA/cm2、60mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2The charge and discharge test was performed at the current density of (1). The results showed that at 40mA/cm2The energy conversion efficiency of the battery was 67.0% at the current density of (d); and at 120mA/cm2Under the high rate condition of (2), the battery can not complete normal charging and discharging.
Example 3
In this example, in preparing the composite electrode material for the all-vanadium flow battery, the following steps are adopted:
1) 12g of sucrose as an organic carbon source precursor was dissolved in a total volume of 100mL of water and acetone. The volume ratio of water to acetone was 4: 1.
2) And adding 25g of micro-nano granular calcium carbonate into the solution to serve as a hard template, wherein the particle size of the calcium carbonate is about 50-200 nm. They were then placed in an ultrasonic wash tank and shaken until a uniformly dispersed suspension was formed.
3) The graphite fiber paper was cut into a size of 30mm × 30mm and a thickness of about 250 μm. And then the graphite fiber paper is fully soaked in the suspension liquid so that the inner surface of the graphite fiber paper is uniformly coated, and then the coated graphite fiber paper is taken out and is placed in a vacuum drying oven to be dried at room temperature.
4) Placing the fully dried material in a temperature programmed tube furnace, introducing argon gas into the furnace as protective gas, purging the tube furnace to replace air in the tube before temperature rising, raising the temperature of the furnace to 900 ℃ at a temperature rising rate of 15 ℃/min, preserving heat for 5h, carbonizing the material, and naturally cooling the furnace to room temperature.
5) And the hydrochloric acid solution with the quantity concentration of the prepared substance being 1.5mol/L is used for carrying out acid washing on the carbonized material so as to remove the micro-nano granular calcium carbonate serving as the hard template.
6) The acid-washed material was repeatedly washed with deionized water and then dried in a vacuum oven at room temperature for use.
In this example, the novel composite electrode material was applied to the assembly of an all vanadium flow battery. The cell was assembled in a filter press in the order of end plate-collector plate-electrode-separator-electrode-collector plate-end plate. Wherein, the diaphragm adopts a perfluorosulfonic acid membrane. The battery was subjected to charge and discharge tests at different current densities. The results show that the cell is at 40mA/cm2、60mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2Can be normally charged and discharged at a current density of (2), and has a smooth curve. At 40mA/cm2Under the current density, the energy conversion efficiency of the battery reaches up to 83.1 percent; and at 120mA/cm2Under the condition of high rate, the energy conversion efficiency of the battery can still reach 72.4 percent.
Comparative example 3
In contrast to example 3, an all vanadium flow battery was assembled using untreated graphite fiber paper of the same size as the electrode material, which is currently in common use. The assembly of the cell and the materials other than the working electrode were the same as in example 1, and the current was also 40mA/cm2、60mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2The charge and discharge test was performed at the current density of (1). The results showed that at 40mA/cm2The energy conversion efficiency of the battery is 65.0% at the current density of (3); and at 120mA/cm2The battery cannot be normally charged and discharged even under high rate conditions.
Example 4
In this example, in preparing the composite electrode material for the all-vanadium flow battery, the following steps are adopted:
1) 5g of cellulose acetate as an organic carbon source precursor was dissolved in 100mL of total volume of water and ethylene glycol. The volume ratio of water to ethylene glycol was 4: 1.
2) And 5g of micro-nano granular inorganic material lithium carbonate is added into the solution to serve as a hard template, and the particle size of the lithium carbonate is about 300-500 nm. They were then placed in an ultrasonic wash tank and shaken until a uniformly dispersed suspension was formed.
3) Cutting the carbon foam into the size of 30mm multiplied by 5mm, wherein the size of the inner aperture is about 100-200 mu m, then fully soaking the carbon foam in the suspension to ensure that the inner surface of the carbon foam is uniformly coated, then taking out the carbon foam, and putting the carbon foam into a vacuum drying oven to dry at room temperature.
4) Placing the fully dried material in a temperature programmed tube furnace, introducing nitrogen gas into the furnace as protective gas, purging the tube furnace to replace air in the tube before temperature rising, raising the temperature of the furnace to 1100 ℃ at a temperature rising rate of 10 ℃/min, preserving the temperature for 2h, carbonizing the material, and naturally cooling the furnace to room temperature.
5) And preparing a sulfuric acid solution with the mass concentration of 2mol/L for acid washing of the carbonized material to remove the micro-nano particle lithium carbonate serving as the hard template.
6) The acid-washed material was repeatedly washed with deionized water and then dried in a vacuum oven at room temperature for use.
In this example, the novel composite electrode material was applied to the assembly of an all vanadium flow battery. The cell was assembled in a filter press in the order of end plate-collector plate-electrode-separator-electrode-collector plate-end plate. Wherein, the diaphragm adopts a perfluorosulfonic acid membrane. The battery was subjected to charge and discharge tests at different current densities. The results show that the cell is at 40mA/cm2、60mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2Can be normally charged and discharged at a current density of (2), and has a smooth curve. At 40mA/cm2The energy conversion efficiency of the battery reaches 85.7 percent under the current density of the battery; and at 120mA/cm2Under the condition of high rate, the energy conversion efficiency of the battery can still reach 78.2 percent.
Comparative example 4
In contrast to example 4, an all vanadium flow battery was assembled using the same size carbon foam that is currently used untreated as the electrode material. The assembly of the batteryThe procedure and the materials other than the working electrode were the same as in example 1, and were also at 40mA/cm2、60mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2The charge and discharge test was performed at the current density of (1). The results showed that at 40mA/cm2The energy conversion efficiency of the battery is 70.3% at the current density of (3); and at 120mA/cm2The energy conversion efficiency of the battery is only 60.1% under the high rate condition.
Example 5
In this example, in preparing the composite electrode material for the all-vanadium flow battery, the following steps are adopted:
1) 5g of starch as an organic carbon source precursor was dispersed in a total volume of 100mL of water and n-propanol. The volume ratio of water to n-propanol was 5: 1.
2) Adding 20g of micro-nano granular inorganic material zinc oxide into the solution to serve as a hard template, wherein the particle size of the zinc oxide is about 500 nm-1 mu m. They were then placed in an ultrasonic wash tank and shaken until a uniformly dispersed suspension was formed.
3) Cutting the graphite fiber felt into the size of 30mm multiplied by 5mm, then putting the graphite fiber felt into the suspension liquid to be fully soaked so as to ensure that the inner surface of the graphite fiber felt is uniformly coated, then taking out the coated graphite fiber felt, and putting the coated graphite fiber felt into a vacuum drying oven to be dried at room temperature.
4) Placing the fully dried material in a temperature programmed tube furnace, introducing helium gas into the furnace as protective gas, purging the tube furnace to replace air in the tube before temperature rising, raising the temperature of the furnace to 1200 ℃ at a temperature rising rate of 2 ℃/min, preserving the temperature for 1h, carbonizing the material, and naturally cooling to room temperature.
5) And (3) pickling the carbonized material by using a phosphoric acid solution with the quantity concentration of the prepared substance being 1.2mol/L to remove the micro-nano granular zinc oxide serving as the hard template.
6) And repeatedly washing the acid-washed material by using deionized water, and then drying the material in a vacuum drying oven at room temperature for later use.
In this embodimentThe novel composite electrode material is applied to the assembly of the all-vanadium redox flow battery. The cell was assembled in a filter press in the order of end plate-collector plate-electrode-separator-electrode-collector plate-end plate. Wherein, the diaphragm adopts a perfluorosulfonic acid membrane. The battery was subjected to charge and discharge tests at different current densities. The results show that the cell is at 40mA/cm2，60mA/cm2，80mA/cm2，100mA/cm2And 120mA/cm2Can be normally charged and discharged at a current density of (2), and has a smooth curve. At 40mA/cm2The energy conversion efficiency of the battery reaches 89.6 percent under the current density of the battery; and at 120mA/cm2Under the condition of high rate, the energy conversion efficiency of the battery can still reach 82.6 percent.
Comparative example 5
In contrast to example 5, an all vanadium flow battery was assembled using the same size graphite fiber felt as the electrode material, which is currently commonly used, untreated. The manner of assembling the battery and the materials other than the electrode were the same as those of example 1, and the current was also 40mA/cm2、60mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2The charge and discharge test was performed at the current density of (1). The results showed that at 40mA/cm2The energy conversion efficiency of the battery is 81.2% under the current density; and at 120mA/cm2The energy conversion efficiency of the battery is only 75.0% under the high rate condition.
Example 6
In this example, in preparing the composite electrode material for the all-vanadium flow battery, the following steps are adopted:
1) 8g of acacia gum as an organic carbon source precursor was dissolved in 100mL of total volume of water and acetone. The volume ratio of water to acetone was 4: 1.
2) And adding 15g of micro-nano granular inorganic materials magnesium hydroxide and 10g of potassium carbonate into the solution to serve as hard templates, wherein the particle sizes of the magnesium hydroxide and the potassium carbonate are both 100-200 nm. They were then placed in an ultrasonic wash tank and shaken until a uniformly dispersed suspension was formed.
3) The carbon cloth was cut into a size of 30mm × 30mm and a thickness of about 250 μm. And then placing the carbon cloth into the suspension to be fully soaked so as to enable the inner surface of the carbon cloth to be uniformly coated, taking out the coated carbon cloth, and placing the coated carbon cloth into a vacuum drying oven to be dried at room temperature.
4) Placing the fully dried material in a temperature programmed tube furnace, introducing helium gas into the furnace as protective gas, purging the tube furnace to replace air in the tube before temperature rising, raising the temperature of the furnace to 650 ℃ at a temperature rising rate of 1 ℃/min, preserving heat for 1.5h, carbonizing the material, and naturally cooling the furnace to room temperature.
5) And preparing a formic acid solution with the mass concentration of 0.5mol/L for pickling the carbonized material to remove the micro-nano granular magnesium hydroxide serving as the hard template.
6) And repeatedly washing the acid-washed material by using deionized water, and then drying the acid-washed material in a vacuum drying oven at room temperature for later use.
In this example, the novel composite electrode material was applied to the assembly of an all vanadium flow battery. The cell was assembled in a filter press in the order of end plate-collector plate-electrode-separator-electrode-collector plate-end plate. Wherein, the diaphragm adopts a perfluorosulfonic acid membrane. The cell was subjected to charge and discharge tests at different current densities. The results show that the cell is at 40mA/cm2、60mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2Can be normally charged and discharged at a current density of (2), and has a smooth curve. At 40mA/cm2The energy conversion efficiency of the battery reaches 75.6 percent under the current density of the battery; and at 120mA/cm2The energy conversion efficiency of the battery is 65.8% under the high rate condition.
Comparative example 6
In contrast to example 6, an all vanadium flow battery was assembled using untreated carbon cloth of the same size as the electrode material, which is currently commonly used. The assembly of the cell and the materials other than the working electrode were the same as in example 1, and the current was also 40mA/cm2、60mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2Is charged at a current density ofAnd (5) discharging and testing. The results showed that at 40mA/cm2The energy conversion efficiency of the battery is 66.3% at the current density of (3); and at 120mA/cm2Under the high rate condition of (2), the battery cannot be normally charged and discharged.
Example 7
In this example, in preparing the composite electrode material for the all-vanadium flow battery, the following steps are adopted:
1) 5g of arabinose serving as an organic carbon source precursor is dissolved in water and butanone with the total volume of 100 mL. The volume ratio of water to ethanol was 3: 1.
2) And 8g of micro-nano granular zinc hydroxide is added into the solution to serve as a hard template, and the size of zinc hydroxide particles is about 10-50 nm. They were then placed in an ultrasonic wash tank and shaken until a uniformly dispersed suspension was formed.
3) Cutting the carbon fiber felt into the size of 30mm multiplied by 5mm, then putting the carbon fiber felt into the suspension liquid to be fully soaked so as to ensure that the inner surface of the carbon fiber felt is uniformly coated, then taking out the coated carbon fiber felt, and putting the coated carbon fiber felt into a vacuum drying oven to be dried at room temperature.
4) Placing the fully dried material in a temperature programmed tube furnace, introducing nitrogen gas into the furnace as protective gas, purging the tube furnace to replace air in the tube before temperature rising, raising the temperature of the furnace to 1500 ℃ at a temperature rising rate of 20 ℃/min, preserving heat for 1h, carbonizing the material, and naturally cooling the furnace to room temperature.
5) And (3) pickling the carbonized material by using an acetic acid solution with the quantity concentration of the prepared substance being 1.5mol/L to remove the micro-nano particle zinc hydroxide serving as the hard template.
6) The acid-washed material was repeatedly washed with deionized water and then dried in a vacuum oven at room temperature for use.
In this example, the novel composite electrode material was applied to the assembly of an all vanadium flow battery. The cell was assembled in a filter press in the order of end plate-collector plate-electrode-separator-electrode-collector plate-end plate. Wherein, the diaphragm adopts a perfluorosulfonic acid membrane. At different electricityThe cell was subjected to a charge and discharge test at current density. The results show that the cell is at 40mA/cm2、60mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2Can be normally charged and discharged at a current density of (2), and has a smooth curve. At 40mA/cm2The energy conversion efficiency of the battery reaches 88.3 percent under the current density of the battery; and at 120mA/cm2Under the condition of high rate, the energy conversion efficiency of the battery can still reach 83.5 percent.
Comparative example 7
In contrast to example 7, an all vanadium flow battery was assembled using untreated carbon fiber felt of the same size as the electrode material, which is currently in common use. The assembly of the cell and the materials other than the working electrode were the same as in example 1, and the current was also 40mA/cm2、60mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2The charge and discharge test was performed at the current density of (1). The results showed that at 40mA/cm2The energy conversion efficiency of the battery is 84.4% at the current density of (a); and at 120mA/cm2The energy conversion efficiency of the battery is only 78.2% under the high rate condition.
Example 8
In this example, in preparing the composite electrode material for the all-vanadium flow battery, the following steps are adopted:
1) 15g of glucose as an organic carbon source precursor was dissolved in a total volume of 100mL of water and methanol. The volume ratio of water to methanol was 3: 1.
2) And adding 38g of micro-nano granular inorganic material iron oxide serving as a hard template into the solution, wherein the size of iron oxide particles is about 30-80 nm. They were then placed in an ultrasonic wash tank and shaken until a uniformly dispersed suspension was formed.
3) The carbon cloth was cut into a size of 30mm × 30mm and a thickness of about 250 μm. And then the carbon cloth is put into the suspension liquid to be fully soaked, so that the inner surface of the carbon cloth is uniformly coated, and then the coated carbon cloth is taken out and is put into a vacuum drying oven to be dried at room temperature.
4) Placing the fully dried material in a temperature programmed tube furnace, introducing helium gas into the furnace as protective gas, purging the tube furnace to replace air in the tube before temperature rising, then raising the temperature to 700 ℃ at a temperature rise rate of 12 ℃/min and preserving heat for 4h, thereby carbonizing the material, and then naturally cooling the furnace to room temperature.
5) And (3) pickling the carbonized material by using a benzenesulfonic acid solution with the quantity concentration of the prepared substance of 2.5mol/L to remove the micro-nano granular iron oxide serving as the hard template.
6) The acid-washed material was repeatedly washed with deionized water and then dried in a vacuum oven at room temperature for use.
In this example, the novel composite electrode material was applied to the assembly of an all vanadium flow battery. The cell was assembled in a filter press in the order of end plate-collector plate-electrode-separator-electrode-collector plate-end plate. Wherein, the diaphragm adopts a perfluorosulfonic acid membrane. The cell was subjected to charge and discharge tests at different current densities. The results show that the cell is at 40mA/cm2、60mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2Can be normally charged and discharged at a current density of (2), and has a smooth curve. At 40mA/cm2The energy conversion efficiency of the battery reaches 79.5 percent under the current density of the battery; and at 120mA/cm2The energy conversion efficiency of the battery is up to 67.6%.
Comparative example 8
In contrast to example 8, an all vanadium flow battery was assembled using untreated carbon cloth of the same size as the electrode material, which is currently commonly used. The manner of assembling the battery and the materials other than the electrode were the same as those of example 1, and the current was also 40mA/cm2、60mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2The charge and discharge test was performed at the current density of (1). The results showed that at 40mA/cm2The energy conversion efficiency of the battery is 66.0% at the current density of (3); and at 120mA/cm2Under the high rate condition of (2), the battery cannot be normally charged and discharged.
Example 9
In this example, in preparing the composite electrode material for the all-vanadium flow battery, the following steps are adopted:
1) 4g of polyvinyl alcohol as an organic carbon source precursor was dissolved in 100mL of total volume of water and ethanol. The volume ratio of water to ethanol was 3: 1.
2) And adding 10g of micro-nano granular barium carbonate into the solution to serve as a hard template, wherein the particle size of the barium carbonate is about 7-10 mu m. They were then placed in an ultrasonic wash tank and shaken until a uniformly dispersed suspension was formed.
3) The carbon fiber paper was cut into a size of 30mm × 30mm, and the thickness thereof was about 200 μm. And then placing the carbon fiber paper into the suspension to be fully soaked so as to enable the inner surface of the carbon fiber paper to be uniformly coated, taking out the coated carbon fiber paper, and placing the coated carbon fiber paper into a vacuum drying oven to be dried at room temperature.
4) Placing the fully dried material in a temperature programmed tube furnace, introducing nitrogen gas into the furnace as protective gas, purging the tube furnace to replace air in the tube before temperature rising, raising the temperature of the furnace to 800 ℃ at a temperature rising rate of 10 ℃/min, preserving heat for 3h, carbonizing the material, and naturally cooling to room temperature.
5) And (3) pickling the carbonized material by using a hydrofluoric acid solution with the quantity concentration of the prepared substance being 1.5mol/L to remove the micro-nano barium carbonate particles serving as the hard template.
6) The acid-washed material was repeatedly washed with deionized water and then dried in a vacuum oven at room temperature for use.
In this example, the novel composite electrode material was applied to the assembly of an all vanadium flow battery. The cell was assembled in a filter press in the order of end plate-collector plate-electrode-separator-electrode-collector plate-end plate. Wherein, the diaphragm adopts a perfluorosulfonic acid membrane. The cell was subjected to charge and discharge tests at different current densities. The results show that the cell is at 40mA/cm2、60mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2Can be normally charged and discharged at a current density of (2), and has a smooth curve. At 40mA/cm2The energy conversion efficiency of the battery reaches 85.2 percent under the current density of the battery; and at 120mA/cm2Under the condition of high rate, the energy conversion efficiency of the battery can still reach 77.8 percent.
Comparative example 9
In contrast to example 9, an all vanadium flow battery was assembled using untreated carbon fiber paper of the same size as the electrode material, which is currently in common use. The assembly of the cell and the materials other than the working electrode were the same as in example 1, and the current was also 40mA/cm2、60mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2The charge and discharge test was performed at the current density of (1). The results showed that at 40mA/cm2The energy conversion efficiency of the battery was 67.0% at the current density of (d); at 120mA/cm2Under the high rate condition of (2), the battery cannot be normally charged and discharged.
Example 10
In this example, in preparing the composite electrode material for the all-vanadium flow battery, the following steps are adopted:
1) 7g of polyethylene glycol as an organic carbon source precursor was dispersed in 100mL of total volume of water and toluene. The volume ratio of water to ethanol was 3: 1.
2) And adding 15g of micro-nano granular strontium carbonate serving as a hard template into the solution, wherein the size of strontium carbonate particles is about 1-5 mu m. They were then placed in an ultrasonic wash tank and shaken until a uniformly dispersed suspension was formed.
3) The carbon cloth was cut into a size of 30mm × 30mm and a thickness of about 250 μm. And then putting the carbon cloth into the suspension for full immersion so as to uniformly coat the inner surface of the carbon cloth, taking out the coated carbon cloth, and putting the coated carbon cloth into a vacuum drying oven for drying at room temperature.
4) Placing the fully dried material in a temperature programmed tube furnace, introducing helium gas into the furnace as protective gas, purging the tube furnace to replace air in the tube before temperature rising, raising the temperature of the furnace to 1400 ℃ at a temperature rising rate of 12 ℃/min, preserving heat for 3h, carbonizing the material, and naturally cooling the furnace to room temperature.
5) And (3) pickling the carbonized material by using a hydrochloric acid solution with the quantity concentration of the prepared substance being 0.8mol/L to remove the micro-nano granular strontium carbonate serving as the hard template.
6) The acid-washed material was repeatedly washed with deionized water and then dried in a vacuum oven at room temperature for use.
In this example, the novel composite electrode material was applied to the assembly of an all vanadium flow battery. The cell was assembled in a filter press in the order of end plate-collector plate-electrode-separator-electrode-collector plate-end plate. Wherein, the diaphragm adopts a perfluorosulfonic acid membrane. The cell was subjected to charge and discharge tests at different current densities. The results show that the cell is at 40mA/cm2、60mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2Can be normally charged and discharged at a current density of (2), and has a smooth curve. At 40mA/cm2The energy conversion efficiency of the battery reaches 80.1 percent under the current density of the battery; and at 120mA/cm2The energy conversion efficiency of the battery is 70.3% under the high rate condition.
Comparative example 10
In contrast to example 10, an all vanadium flow battery was assembled using untreated carbon cloth of the same size as the electrode material, which is currently commonly used. The assembly of the cell and the materials other than the working electrode were the same as in example 1, and the current was also 40mA/cm2、60mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2The charge and discharge test was performed at the current density of (1). The results showed that at 40mA/cm2The energy conversion efficiency of the battery is 67.4% at the current density of (3); and at 120mA/cm2Under the high rate condition of (2), the battery cannot be normally charged and discharged.
The above examples are only some preferred embodiments of the present invention, but the scope of the present invention is not limited thereto. It will be understood by those skilled in the art that all modifications and substitutions without departing from the spirit and scope of the present invention are within the scope of the present invention.

Claims (11)

1. A method of preparing a composite electrode material for an all-vanadium flow battery, the method comprising the steps of:
1) dissolving an organic carbon source precursor in water, or an organic solvent, or a mixture of water and the organic solvent;
2) adding a micro-nano granular material into the solution formed in the step 1) to serve as a hard template, and then placing the micro-nano granular material into an ultrasonic washing tank to vibrate until uniformly dispersed suspension is formed;
3) placing the three-dimensional carbon substrate material into the suspension for full impregnation so as to uniformly coat the inner surface of the three-dimensional carbon substrate material, taking out the coated three-dimensional carbon substrate material, and drying the coated three-dimensional carbon substrate material in a vacuum drying oven at room temperature;
4) placing the dried material in a temperature programmed tube furnace, introducing inert gas into the furnace, raising the temperature of the furnace to a target temperature to carbonize the organic carbon source precursor, and naturally cooling the furnace to room temperature;
5) acid washing the carbonized material with an acid solution to remove the micro-nano granular material as a hard template;
6) and repeatedly washing the acid-washed material by using deionized water to remove residual acid and salt impurities on the surface of the material, and then drying the material in a vacuum drying oven at room temperature for later use.
2. The method according to claim 1, wherein the organic carbon source precursor in step 1) is at least one of cellulose, starch, fructose, maltose, hemicellulose, gum arabic, carrageenan, arabinose, glucose, sucrose, polyvinyl alcohol, polyethylene glycol and polypropylene glycol.
3. The method according to claim 1, wherein the organic solvent in step 1) is at least one of methanol, ethanol, n-propanol, isopropanol, acetone, ethylene glycol, and dimethylsulfoxide.
4. The method according to claim 1, wherein the micro-nano granular material in step 2) is at least one of calcium carbonate, zinc oxide, sodium carbonate, potassium carbonate, iron carbonate, barium carbonate, strontium carbonate, zinc carbonate, magnesium carbonate, lithium carbonate, magnesium hydroxide, zinc hydroxide and iron oxide.
5. The method according to claim 4, wherein the micro-nano granular material has a size of 10nm to 10 μm, and is used in an amount of 5% to 40% of the total mass fraction of the suspension.
6. The method of claim 1, wherein the three-dimensional carbon substrate material in step 3) is at least one of carbon fiber felt, graphite fiber felt, carbon fiber paper, graphite fiber paper, carbon foam, and carbon cloth.
7. The method according to claim 1, wherein the temperature rise rate of the carbonization process in the step 4) is 1-20 ℃/min, the target temperature is 600-1500 ℃, and the carbonization time is 0.5-20 h.
8. The method according to claim 1, wherein the acid solution in step 5) is a solution obtained by dissolving at least one of hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, hydrochloric acid, acetic acid, and benzenesulfonic acid in water.
9. A composite electrode material prepared by the method according to any one of claims 1-8.
10. Use of a composite electrode material prepared by the method according to any one of claims 1-8 in an electrode material of an all-vanadium flow battery.
11. Use of a material further loaded with other catalysts on a support of a composite electrode material prepared by a process according to any one of claims 1 to 8 in an electrode material for an all vanadium flow battery.
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