CN115832328A - Porous carbon electrode, preparation method thereof and flow battery - Google Patents
Porous carbon electrode, preparation method thereof and flow battery Download PDFInfo
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Abstract
In order to overcome the problem of insufficient electrocatalytic activity of a carbon electrode of an existing flow battery, the invention provides a porous carbon electrode which comprises a porous carbon electrode body and antimony nanoparticles, wherein a plurality of nanopores are formed on the surface of the porous carbon electrode body, and the antimony nanoparticles are embedded into and at least partially coated in the nanopores. Meanwhile, the invention also discloses a preparation method of the porous carbon electrode and a flow battery comprising the porous carbon electrode. According to the invention, two steps of pore forming on the surface of the porous carbon electrode body and deposition of antimony nanoparticles are completed through one-time carbothermic reaction, and the formed catalyst antimony nanoparticles are coated in the nanopores, so that the storage stability is improved, the bonding strength with the porous carbon electrode body, the electrocatalytic activity and the electrochemical reversibility are improved, the charge transfer resistance is reduced, and the voltage efficiency and the energy efficiency of the flow battery are improved.
Description
Technical Field
The invention belongs to the technical field of new energy batteries, and particularly relates to a porous carbon electrode, a preparation method thereof and a flow battery.
Background
The use of a large amount of traditional fossil energy brings many problems such as climate warming and environmental pollution, and the vigorous development of renewable energy represented by wind energy and solar energy is an effective way to solve the problems. However, these renewable energy sources have the characteristics of instability, discontinuity and the like, and often cause great impact on the power grid, which becomes a bottleneck limiting the large-scale application of the power grid. The high-power, high-capacity and low-cost energy storage technology matched with the energy storage device is a key technology for promoting the structure adjustment of energy sources and popularizing the development of renewable energy sources.
As a novel electrochemical energy storage mode, the flow battery has the remarkable characteristics of intrinsic safety, long service life and the like, and the excellent comprehensive performance of the flow battery enables the flow battery to occupy an important position in the field of energy storage, so that the flow battery has a wide development prospect. The redox flow battery is used as a liquid-phase electrochemical energy storage device, active substances of the redox flow battery are completely dissolved in flowable electrolyte, energy storage and release are realized through valence state change of the active substances, particularly, vanadium ions with different valence states are used as the active substances of the battery in the all-vanadium redox flow battery, and V is adopted on the negative electrode side 2+ /V 3+ An electric pair, the positive side adopts V 4+ /V 5+ The vanadium ions with four valence states can stably exist in the acid electrolyte because only the vanadium ions are used as the electrolyteThe active material avoids the cross contamination problem caused by the diffusion of different ions across membranes, and is the flow battery system which is the most widely researched and most widely demonstrated in power stations.
However, as an active material of the all-vanadium redox flow battery, vanadium ions have a resource limitation problem, and the high price of vanadium ore is one of the main reasons of high cost of the existing all-vanadium redox flow battery. The total cost of the all-vanadium redox flow battery cannot be reduced from the cost of active materials, but the development of the redox flow battery is expected to be compatible with the cost problem, and actually, the cost of the galvanic pile is also one of the extremely high cost of the redox flow battery, and the proportion is more than 40%. Therefore, the overall cost of the flow battery can be preferentially considered from the cost of the galvanic pile, the most direct and effective way for reducing the cost of the galvanic pile of the flow battery is to increase the operating power density of the battery on the premise of not sacrificing energy efficiency, under the same power requirement, the increase of the operating power density can effectively reduce the active area of the battery, and the number of correspondingly required electrodes, bipolar plates and ion exchange membranes can be reduced, thereby improving the performance of the battery.
The improvement of the operating power density of the flow cell needs to reduce the activation polarization loss, the ohmic polarization loss and the concentration polarization loss in the cell operating process, and puts higher requirements on the electrode design, particularly needs to greatly increase the catalytic activity and the reaction sites of the electrode. The active specific surface area and electrochemical stability of the electrode material directly determine the power density, energy efficiency and service life of the vanadium battery. Among many carbonaceous and metallic materials, felt-based electrodes such as graphite felt are widely used as electrode materials for commercial vanadium batteries because of their advantages such as high corrosion resistance, good electrical conductivity, large specific surface area, high mechanical strength, and low cost. However, the untreated electrode generally has the defects of low electrocatalytic activity, poor wettability and the like, and has the problems of hydrogen evolution, oxygen evolution and the like in the electrochemical reaction process, so that the working current density and coulomb efficiency of the vanadium battery are limited to a great extent. Therefore, modification research based on the carbon felt has important significance for improving the comprehensive performance of the vanadium flow battery.
Disclosure of Invention
The invention provides a porous carbon electrode, a preparation method thereof and a flow battery, aiming at the problem of insufficient electrocatalytic activity of a carbon electrode of the existing flow battery.
The technical scheme adopted by the invention for solving the technical problems is as follows:
in one aspect, the invention provides a porous carbon electrode comprising a porous carbon electrode body having a surface formed with a plurality of nanopores and antimony nanoparticles embedded and at least partially coated in the nanopores.
Optionally, the porous carbon electrode body is one or more of carbon paper, carbon cloth, carbon felt, graphite felt and carbon mesh formed by overlapping, bonding or weaving carbon fibers.
Optionally, the diameter of the carbon fiber is 5-15 μm, and the thickness of the porous carbon electrode body is 0.5-2.5 mm.
Optionally, the pore diameter of the nanopore is 20-200nm, and the pore depth is 100-500nm.
Optionally, the particle size of the antimony nanoparticles is 5-150nm.
Optionally, the mass percentage of the antimony nanoparticles is 20-40% based on 100% of the total mass of the porous carbon electrode.
In a further aspect, the invention provides a method for preparing a porous carbon electrode as described above, comprising the following operative steps:
providing a porous carbon electrode precursor comprising a porous carbon electrode body and antimony salt nanoparticles attached to the surface of the porous carbon electrode body;
heating and decomposing: heating the porous carbon electrode precursor to decompose the antimony salt nanoparticles to antimony oxide;
c, carbothermal reaction: and further heating the porous carbon electrode precursor subjected to heating decomposition at 800-1000 ℃ to enable the antimony oxide and the porous carbon electrode body to perform carbothermic reaction, so that nanopores are formed on the surface of the porous carbon electrode body, and meanwhile, antimony nanoparticles generated by the antimony oxide are embedded in and at least partially coated in the nanopores.
Optionally, the porous carbon electrode precursor is prepared by the following method:
and (3) immersing the porous carbon electrode body into an antimonate solution, taking out and drying to attach the antimonate nanoparticles to the surface of the porous carbon electrode body.
Optionally, the solvent of the antimony salt solution is an organic solvent, the concentration of antimony salt in the antimony salt solution is 0.1M to 0.5M, and the organic solvent comprises one or more of ethanol, methanol, ethylene glycol and acetone; the solute of the antimony salt solution comprises one or more of antimony nitrate, antimony acetate and antimony chloride.
Optionally, the "thermal decomposition" operation includes:
heating the porous carbon electrode precursor to 100-300 ℃ per minute under a protective atmosphere at a rate of 2-5 ℃ and calcining for 40-60min.
Optionally, the antimony oxide is antimony trioxide.
Optionally, the operation of "carbothermal reaction" comprises:
heating the decomposed porous carbon electrode precursor to 800-1000 ℃ at the rate of 5-10 ℃ per minute in protective atmosphere, and calcining for 60-120min.
In still another aspect, the invention provides a flow battery, which comprises the porous carbon electrode as described above, or the porous carbon electrode prepared by the preparation method as described above.
Optionally, the flow battery is an all-vanadium flow battery, an iron-chromium flow battery, an iron-vanadium flow battery, a zinc-bromine flow battery, a vanadium-bromine flow battery or a vanadium-cerium flow battery.
According to the porous carbon electrode provided by the invention, the carbon thermal reaction is carried out on the carbon surface of the antimony oxide and the porous carbon electrode body, so that a structure that nano-pores cover nano-antimony is directly formed. The specific principle is that oxygen atoms in antimony oxide and carbon are subjected to a thermochemical reaction to generate carbon dioxide or carbon monoxide gas, so that a surface pore-forming step is completed, and the specific surface area of the electrode is greatly increased. The antimony oxide is reduced into conductive antimony nano particles coated in the nano holes, and the metallic antimony has extremely high hydrogen evolution overpotential and catalytic activityAnd (4) sex. The fact that the redox reaction in the flow cell can be promoted while suppressing the occurrence of the hydrogen evolution reaction means that the occurrence of the hydrogen evolution reaction can be suppressed. According to the invention, two steps of pore forming on the surface of the carbon fiber and high-performance catalyst deposition are completed through one carbothermic reaction, and the formed catalyst antimony nanoparticles are coated in the nanopores, so that on the one hand, the antimony nanoparticles have a good protection effect, the formed antimony nanoparticles are very stable, the antimony nanoparticles are suitable for being stored under the conventional air condition, and the storage difficulty of the treated electrode is reduced; in the second aspect, the bonding strength of the antimony nanoparticles and the porous carbon electrode body is also improved, the treated antimony nanoparticles are deposited inside the fabricated pores, and the problem that the antimony nanoparticles are directly washed away by flowing electrolyte when the antimony nanoparticles are applied to a flow battery is avoided, so that the battery performance is kept stable in a long-term cycle test; in the third aspect, the surface of the carbon material is coated with the antimony nanoparticle catalyst, so that the electrode material V is improved 3+ /V 2+ The electrocatalytic activity and the electrochemical reversibility of the redox reaction reduce the charge transfer resistance and improve the voltage efficiency and the energy efficiency of the all-vanadium redox flow battery. In the invention, all the steps are finished in one step in a high-temperature furnace, namely, pore forming, catalyst reduction and one-step carbothermal reaction of depositing the catalyst into pores are carried out. Therefore, the process is simple, secondary heating sintering is not needed, and the method is suitable for large-scale industrial production.
Drawings
FIG. 1 is a flow chart of the preparation of the porous carbon electrode provided by the present invention;
FIG. 2 is a graph of porous carbon electrodes treated with different concentrations of antimony salt according to example 1 of the present invention;
FIG. 3 is a schematic diagram of the morphology before and after the carbothermic reaction provided in example 1 of the present invention;
FIG. 4 is a topographical view of a porous carbon electrode provided in example 1 of the present invention;
FIG. 5 is an electron micrograph of a porous carbon electrode before and after treatment provided in example 2 of the present invention;
FIG. 6 is a battery performance test curve provided in example 3 of the present invention;
fig. 7 is a battery charge and discharge test curve provided in embodiment 3 of the present invention;
FIG. 8 is a graph of 200mA cm provided in example 4 of the present invention -2 Comparing the test curve of battery charge and discharge under the galvanic density.
Fig. 9 is an electron micrograph of a porous carbon electrode provided in comparative example 1 of the present invention.
Fig. 10 is an electron micrograph of a porous carbon electrode provided in example 5 of the present invention.
Fig. 11 is an electron micrograph of a porous carbon electrode provided in example 6 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
An embodiment of the present invention provides a porous carbon electrode, including a porous carbon electrode body and antimony nanoparticles, wherein a plurality of nanopores are formed on a surface of the porous carbon electrode body, and the antimony nanoparticles are embedded and at least partially coated in the nanopores.
A plurality of nano holes are formed on the surface of the porous carbon electrode body, so that the specific surface area of the electrode is greatly increased. The antimony nanoparticles coated in the nanopores have extremely high hydrogen evolution overpotential and catalytic activity, can inhibit the hydrogen evolution reaction and promote the redox reaction in the flow battery, which means that the antimony nanoparticles can inhibit the hydrogen evolution reaction, and greatly improve the power density, energy efficiency and cycle service life of the flow battery by increasing the specific surface area and utilizing the antimony catalytic activity. And the catalyst antimony nanoparticles are coated in the nanopores, so that on the first hand, the catalyst antimony nanoparticles have a good protection effect on the antimony nanoparticles, so that the formed antimony nanoparticles are very stable and are suitable for storage under the conventional air condition, and the storage difficulty is reduced; in the second aspect, the bonding strength of the antimony nanoparticles and the porous carbon electrode body is also improved, and the problem that the antimony nanoparticles are directly washed away by flowing electrolyte when the antimony nanoparticles are applied to a flow battery is avoided, so that the battery performance is kept stable in a long-term cycle test; in the third aspect, due toThe surface of the carbon material is coated with the antimony nanoparticle catalyst, so that the electrode material V is improved 3+ /V 2+ The electrocatalytic activity and the electrochemical reversibility of the redox reaction reduce the charge transfer resistance and improve the voltage efficiency and the energy efficiency of the all-vanadium redox flow battery.
Compared with the traditional carbon felt electrode, the porous carbon electrode has great advantages, and the power density, the energy efficiency and the cycle service life of the flow battery can be greatly improved by improving the structure of the electrode surface and the catalyst deposition, so that the efficiency of the battery is improved, and the performance of the battery is improved.
In some embodiments, the porous carbon electrode body is a carbon fiber lapped, bonded, or woven structure.
In some embodiments, the carbon fiber is a carbon fiber inorganic non-metallic material that is pressed and woven from graphite and contains carbon above 90%.
In other embodiments, the carbon fiber may also be obtained by carbonizing a polymer resin material, such as carbon fiber obtained by carbonizing an electrospun polymer resin fiber.
In some embodiments, the porous carbon electrode body comprises one or more of carbon paper, carbon cloth, carbon felt, graphite felt, and carbon mesh.
Specifically, the carbon paper, the carbon cloth, the carbon felt, the graphite felt and the carbon net are prepared from carbon fibers, have the characteristics of porosity and large specific surface area, and can meet the requirements of infiltration and flow of electrolyte in the flow battery.
In some embodiments, the diameter of the carbon fiber is 5-15 μm, and the thickness of the porous carbon electrode body is 0.5-2.5 mm.
In particular embodiments, the carbon fibers may have a diameter of 5 μm, 5.5 μm, 6 μm, 6.5 μm, 7 μm, 7.5 μm, 7.8 μm, 8 μm, 8.5 μm, 9 μm, 9.5 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, or 15 μm.
The porous carbon electrode body may have a thickness of 0.5mm, 0.8mm, 1mm, 1.2mm, 1.5mm, 1.8mm, 2mm, 2.2mm or 2.5mm.
In some embodiments, the nanopore has a pore size of 20-200nm and a pore depth of 100-500nm.
In particular embodiments, the nanopore can have an aperture of 20nm, 30nm, 40 nm, 50nm, 60 nm, 70 nm, 80nm, 90 nm, 100 nm, 110 nm, 120nm, 130nm, 140 nm, 150nm, 180nm, or 200nm.
In some embodiments, the antimony nanoparticles have a particle size of 5 to 150nm.
In some embodiments, the antimony nanoparticles are present in an amount of 20% to 40% by mass, based on 100% by mass of the porous carbon electrode.
Referring to fig. 1, another embodiment of the present invention provides a method for preparing a porous carbon electrode as described above, comprising the following operating steps:
providing a porous carbon electrode precursor comprising a porous carbon electrode body and antimony salt nanoparticles attached to the surface of the porous carbon electrode body;
heating and decomposing: heating the porous carbon electrode precursor to decompose the antimony salt nanoparticles to antimony oxide;
c, carbothermal reaction: and further heating the porous carbon electrode precursor subjected to heating decomposition at 800-1000 ℃ to enable the antimony oxide and the porous carbon electrode body to perform carbothermic reaction, so that nanopores are formed on the surface of the porous carbon electrode body, and meanwhile, antimony nanoparticles generated by the antimony oxide are embedded in and at least partially coated in the nanopores.
The preparation method breaks through the electrode preparation and modification process of the traditional flow battery, and directly forms the structure of the nano-pore coated antimony nano-particle catalyst by adopting the carbothermic reaction of antimony oxide and the carbon surface. The specific principle is as follows, wherein oxygen atoms and carbon are subjected to thermochemical reaction to generate carbon dioxide or carbon monoxide gas, the formation of surface nano-pores is completed, and the specific surface area of the electrode is greatly increased. And antimony oxide is reduced to conductive antimony nanoparticles that are encapsulated in the nanopores. The prepared porous carbon electrode has the characteristics of high specific surface area, high catalytic activity and high hydrophilicity. The preparation method provided by the invention is simple to operate, the used materials are cheap and easily-obtained carbon materials and antimony salt with low price and low dosage of antimony salt each time, so that the method is low in total cost and has commercial popularization and application values.
It should be noted that the heating temperature in the "carbothermic reaction" has a great influence on whether the carbothermic reaction can proceed, and then determines whether the nanopores on the surface of the porous carbon electrode body are formed, and whether the antimony nanoparticles can be coated by the nanopores of the porous carbon electrode body, especially, when the heating temperature is too low, the carbothermic reaction cannot be formed, and thus the nanopores and the coated antimony nanoparticles cannot be obtained.
In some embodiments, the porous carbon electrode precursor is prepared by:
and (3) immersing the porous carbon electrode body into an antimonate solution, taking out and drying to attach the antimonate nanoparticles to the surface of the porous carbon electrode body.
In some embodiments, the antimony salt solution is prepared by:
firstly, adding antimony salt into a solvent, and carrying out ultrasonic treatment for 20-60 min.
In some embodiments, when the porous carbon electrode body is immersed in the antimonate solution, ultrasonic treatment is performed simultaneously, so that the antimonate solution can fully enter pores of the porous carbon electrode body, and the porous carbon electrode body is ensured to be fully infiltrated.
In some embodiments, the solvent of the antimony salt solution is an organic solvent comprising one or more of ethanol, methanol, ethylene glycol, and acetone; the solute of the antimony salt solution comprises one or more of antimony nitrate, antimony acetate and antimony chloride.
In some embodiments, the concentration of antimony salt in the antimony salt solution is from 0.1m to 0.5m.
The size and depth of the nano-pores and the size of the formed catalyst particles can be effectively controlled by adjusting the concentration of the antimony salt solution.
In some embodiments, the "thermal decomposition" operation comprises:
heating the porous carbon electrode precursor to 100-300 ℃ per minute under a protective atmosphere at a rate of 2-5 ℃ and calcining for 40-60min.
In some embodiments, the antimony oxide is antimony trioxide.
In some embodiments, the "carbothermal reaction" operation comprises:
heating the decomposed porous carbon electrode precursor to 800-1000 ℃ at the rate of 5-10 ℃ per minute in protective atmosphere, and calcining for 60-120min.
The reaction equation is as follows:
Sb 2 O 3 +C→Sb+CO
Sb 2 O 3 +C→Sb+CO 2
another embodiment of the present invention provides a flow battery including the porous carbon electrode as described above, or including the porous carbon electrode prepared by the preparation method as described above.
The porous carbon electrode prepared by the invention not only can be used for an all-vanadium redox flow battery, but also can be used for an iron-chromium redox flow battery, an iron-vanadium redox flow battery, a zinc-bromine redox flow battery, a vanadium-cerium redox flow battery and a novel electric fuel energy storage system. When applied to an all-vanadium redox flow battery, the battery has a current density of 300mAcm -2 The energy efficiency is over 80 percent; at a current density of 400mAcm -2 The energy efficiency is over 75%. Compared with the situation that the traditional carbon electrode is applied to the all-vanadium redox flow battery, the current density is 100mAcm -2 The energy efficiency is improved from 75% to 90%; at a current density of 200mAcm -2 In the time, the traditional carbon electrode has the condition that the energy efficiency is sharply attenuated and effective data cannot be obtained, and the porous electrode prepared by the method is applied to the all-vanadium redox flow battery at the current density of 200mAcm -2 Can still maintain more than 85 percent of energy efficiency when in use, and the current density is 400mAcm -2 The energy efficiency still exceeds 75%, so that the porous carbon electrode prepared by the preparation method has great advantages compared with the traditional electrode, and the power density of the flow battery can be greatly improvedEnergy efficiency and cycle life, thereby having commercial popularization and application value.
The present invention will be further illustrated by the following examples.
Example 1:
dissolving antimony acetate with equal mass portions of 1, 2, 3, 4 and 5 into 50ml of absolute ethyl alcohol according to concentration ratio to form antimony acetate solutions with concentrations of about 0.1M,0.2M,0.3M,0.4M and 0.5M respectively, directly putting an original carbon felt into the solutions (shown in figure 2) and performing ultrasonic treatment, then putting a slightly dried porous carbon electrode into a vacuum oven for drying at 65 ℃, finally putting the obtained electrode into a tubular furnace for heating treatment under the atmosphere of argon, raising the temperature to 200 ℃ at the rate of 5 ℃ per minute for 60min, then raising the temperature to 800 ℃ at the rate of 10 ℃ per minute, and performing carbothermic reaction at the heat treatment temperature for 90min (the reaction principle is shown in figure 3), wherein the obtained porous carbon material is shown in figure 4.
Example 2:
the raw carbon felt and the porous carbon material prepared from the 0.5M antimony acetate solution in the example 1 are taken to be observed by an electron microscope, and the result is shown in fig. 5, the left side is the morphology of the raw carbon felt, and the right side is the surface morphology of the porous carbon material in the example 1, so that the carbon fiber surface of the raw carbon felt before treatment is smooth and flat, the surface of the treated carbon felt is densely distributed with nano holes and is coated with a catalyst particle structure, wherein the pore diameter of the nano holes is 10-100 nanometers, the pore depth is 100-200 nanometers, and the pore diameter of the nano particles is 10-100 nanometers.
Example 3:
the porous carbon material obtained in example 2, a heat-treated carbon felt electrode (only subjected to heat treatment at 350-550 ℃ and without an antimony catalyst), and an original carbon felt are respectively assembled into an all-vanadium redox flow battery for rate performance test, except for different electrodes, the other test conditions are kept consistent, the test comprises that an end plate adopted by the test is a copper plate, a flow field plate is a graphite bipolar plate, a diaphragm is 212 series of DuPont company, an electrolyte is a commercial 1.7M vanadium ion +3M sulfuric acid solution, and the energy efficiency under different current densities and the likeThe battery performance was examined in several respects and the test results are shown in fig. 6 and 7. It was found by testing that the best cell performance was maintained when the porous carbon electrode of example 2. Specifically, when the current density is 300mAcm -2 The energy efficiency is over 80 percent; when the current density is 400mAcm -2 The energy efficiency is over 75%.
Example 4:
the porous carbon material obtained in example 2 was subjected to a test after being exposed to air for one month, and the test results are shown in fig. 8, and it can be seen from the results of the charge and discharge test curve that the state was extremely stable and the whole exhibited the same performance as that immediately after the treatment. Unlike previous bismuth and other metal oxide porosities. The conventional metallic bismuth, tiC and other substances are unstable in air and are easily oxidized, so that the metallic bismuth, tiC and other substances are required to be stored in an air-isolated environment. The antimony nanoparticles in the porous carbon electrode have excellent stability, and the treated porous carbon electrode can be stored in the air for a long time, so that the porous carbon electrode is particularly suitable for factory-level large-scale production.
To investigate the effect of temperature on the overall experiment, we also performed several sets of comparative experiments with different temperatures, and representative four sets were selected for detailed description.
Example 5:
directly putting an original carbon felt into 0.5M antimonite solution, carrying out ultrasonic treatment, then putting a slightly dried porous carbon electrode into a 65 ℃ vacuum oven for drying, finally putting the obtained electrode into a tubular furnace for heating treatment, wherein the atmosphere is argon, the temperature is firstly increased to 200 ℃ at the rate of 5 ℃ per minute and is kept for 60min, then is increased to 900 ℃ at the rate of 10 ℃ per minute and is kept for 90min at the heat treatment temperature, and the nano holes are densely distributed on the surface of the electrode and are simultaneously coated with catalyst particles (as shown in figure 10).
Example 6:
directly putting an original carbon felt into 0.5M antimonite solution, carrying out ultrasonic treatment, then putting a slightly dried porous carbon electrode into a 65 ℃ vacuum oven for drying, finally putting the obtained electrode into a tubular furnace for heating treatment, wherein the atmosphere is argon, the temperature is firstly increased to 200 ℃ at the rate of 5 ℃ per minute and is kept for 60min, then is increased to 1000 ℃ at the rate of 10 ℃ per minute and is kept for 90min at the heat treatment temperature, and the fact that nano holes are densely distributed on the surface of the electrode and catalyst particles are coated in the nano holes is found (as shown in figure 11).
Comparative example 1:
the original carbon felt is directly put into 0.5M antimonite solution for ultrasonic treatment, then the slightly dried porous carbon electrode is put into a vacuum oven at 65 ℃ for drying, finally the obtained electrode is put into a tube furnace for heating treatment, the atmosphere is argon, the temperature is firstly increased to 200 ℃ at the rate of 5 ℃ per minute and is kept for 60min, then is increased to 700 ℃ at the rate of 10 ℃ per minute and is kept for 90min at the heat treatment temperature, and the surface of the electrode is found to have no uniform nano holes, the surface of the carbon fiber is totally in a more original state, and the holes are not uniformly and densely distributed (as shown in figure 9), so the temperature is not suitable for carrying out the experiment.
Comparative example 2:
directly putting an original carbon felt into 0.5M antimonite solution for ultrasonic treatment, then putting a slightly dried porous carbon electrode into a 65 ℃ vacuum oven for drying, finally putting the obtained electrode into a tubular furnace for heating treatment, wherein the atmosphere is argon, the temperature is firstly increased to 200 ℃ at the rate of 5 ℃ per minute and is kept for 60min, then is increased to 1100 ℃ at the rate of 10 ℃ per minute, and when the heat treatment temperature is kept for 90min for carbon thermal reaction, the surface of the carbon felt is damaged by naked eyes, so that the temperature is not suitable for the experiment.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A porous carbon electrode, which is characterized by comprising a porous carbon electrode body and antimony nanoparticles, wherein a plurality of nanopores are formed on the surface of the porous carbon electrode body, and the antimony nanoparticles are embedded in and at least partially coated in the nanopores.
2. The porous carbon electrode of claim 1, wherein the porous carbon electrode body is one or more of carbon paper, carbon cloth, carbon felt, graphite felt, and carbon mesh formed by overlapping, bonding, or weaving carbon fibers.
3. The porous carbon electrode according to claim 2, wherein the diameter of the carbon fiber is 5-15 μm, and the thickness of the porous carbon electrode body is 0.5 to 2.5mm.
4. The porous carbon electrode according to claim 1, wherein the diameter of the nanopore is 20-200nm, the depth of the nanopore is 100-500nm, and the diameter of the antimony nanoparticle is 5-150nm.
5. The porous carbon electrode according to claim 1, wherein the antimony nanoparticles are present in an amount of 20-40% by mass, based on 100% by mass of the porous carbon electrode.
6. The method of making a porous carbon electrode of any one of claims 1~5 comprising the steps of:
providing a porous carbon electrode precursor comprising a porous carbon electrode body and antimony salt nanoparticles attached to the surface of the porous carbon electrode body;
heating and decomposing: heating the porous carbon electrode precursor to decompose the antimony salt nanoparticles to antimony oxide;
c, carbon thermal reaction: and further heating the porous carbon electrode precursor subjected to heating decomposition at 800-1000 ℃ to enable the antimony oxide and the porous carbon electrode body to carry out carbothermic reaction, so that nano holes are formed on the surface of the porous carbon electrode body, and meanwhile, antimony nanoparticles generated by the antimony oxide are embedded in and at least partially coated in the nano holes.
7. The method for producing a porous carbon electrode according to claim 6, characterized in that the porous carbon electrode precursor is produced by:
immersing the porous carbon electrode body into an antimony salt solution, wherein the concentration of antimony salt in the antimony salt solution is 0.1M to 0.5M, taking out and drying to enable antimony salt nanoparticles to be attached to the surface of the porous carbon electrode body.
8. The method for preparing a porous carbon electrode according to claim 6, characterized in that said "thermal decomposition" operation comprises:
heating the porous carbon electrode precursor to 100-300 ℃ per minute under a protective atmosphere at a rate of 2-5 ℃ and calcining for 40-60min.
9. The method for preparing a porous carbon electrode according to claim 6, characterized in that the "carbothermic reaction" operation comprises:
heating the decomposed porous carbon electrode precursor to 800-1000 ℃ at the rate of 5-10 ℃ per minute in protective atmosphere, and calcining for 60-120min.
10. A flow battery comprising a porous carbon electrode according to any one of claims 1~5 or a porous carbon electrode prepared by the method of claim 6~9.
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