CN121237900A - Preparation method of modified zinc-bromine flow battery carbon felt anode and the carbon felt anode prepared by the method - Google Patents
Preparation method of modified zinc-bromine flow battery carbon felt anode and the carbon felt anode prepared by the methodInfo
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- CN121237900A CN121237900A CN202511811556.3A CN202511811556A CN121237900A CN 121237900 A CN121237900 A CN 121237900A CN 202511811556 A CN202511811556 A CN 202511811556A CN 121237900 A CN121237900 A CN 121237900A
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Abstract
The invention discloses a preparation method of a modified zinc-bromine flow battery carbon felt anode and the carbon felt anode prepared by the method, and belongs to the field of zinc-bromine flow batteries. According to the invention, after the carbon felt is soaked in a mixed solution of cuprous sulfate in water and acetonitrile, acetonitrile is gradually evaporated from the solution by heating, the cuprous sulfate gradually undergoes disproportionation reaction, and a copper simple substance generated by the disproportionation reaction of the cuprous sulfate is deposited on the surface of the carbon felt, so that the purpose of carrying the modified carbon felt by the copper simple substance is realized. The simple substance copper has relatively stable chemical property and good zinc affinity, and the zinc nucleation overpotential can be reduced by loading the simple substance copper on the surface of the carbon felt, so that the reactive sites on the surface of the carbon felt are increased. In addition, the copper and the zinc have stronger action force, which is beneficial to the uniform deposition/stripping of zinc in the charge and discharge process, thereby forming a more uniform zinc deposition layer on the surface of the carbon felt, reducing the formation of zinc dendrites and improving the electrochemical performance of the zinc-bromine flow battery.
Description
Technical Field
The invention belongs to the field of zinc-bromine flow batteries, and particularly relates to a preparation method of a modified zinc-bromine flow battery carbon felt negative electrode and a carbon felt negative electrode prepared by the method.
Background
In order to meet the continuously increasing energy demands of economic and social development, renewable energy sources such as wind energy, solar energy, tidal energy and the like must be greatly developed. However, these renewable energy sources are susceptible to geographical environmental changes, with intermittent and fluctuating problems. This makes direct grid connection of renewable energy power generation possible to impair the power system stability. Thus, the development of renewable energy sources has greatly driven the need for high-safety, low-cost, long-life and environmentally friendly electrochemical energy storage technologies.
Among the numerous electrochemical energy storage technologies, zinc-bromine flow batteries are considered as the most promising large-scale long-term energy storage technology in the future due to the characteristics of low cost, high energy density, high safety, long service life and the like. However, zinc dendrites are easily formed at the negative electrode of the zinc-bromine flow battery during charge and discharge. Along with the continuous growth of zinc dendrites, the diaphragm can be pierced to cause mixed flow of positive and negative electrolyte, so that the serious self-discharge of the zinc-bromine flow battery is caused. The electrode material is used as a main place of the electrochemical reaction of the zinc-bromine flow battery, and plays an important role in the aspect of loading and depositing zinc although not directly participating in the oxidation-reduction reaction, and the physicochemical properties of the surface of the electrode material greatly influence the zinc deposition process. The carbon felt is the first electrode material of the zinc-bromine flow battery because of the advantages of low price, large porosity, good chemical stability and the like, but the electrochemical activity of the carbon felt can not completely meet the requirements of the zinc-bromine flow battery, so the modification of the surface of the carbon felt is particularly important.
A layer of metal simple substance or oxide is loaded on the surface of the carbon felt, and the active site of zinc deposition is increased, so that the local zinc deposition speed is reduced, a more uniform and compact zinc deposition structure is formed, and finally, the aim of inhibiting the formation of zinc dendrites of the negative electrode can be achieved. The Chinese patent document with publication number CN117832517A discloses a method for loading nickel, tin, cobalt and other metal oxides on the surface of a carbon felt by utilizing a high-temperature sintering process, and after modification, the surface active sites of the carbon felt are increased, so that the performance of a battery is improved. However, this type of method requires high temperature sintering to decompose the metal salt into the corresponding metal oxide, which causes the carbon felt to be excessively oxidized, and excessive oxygen-containing functional groups are formed on the surface of the carbon felt, thereby reducing the conductivity and strength of the carbon felt. In addition, the metal oxide has lower conductivity and is used as an electrochemical reaction active site, which is not beneficial to the rapid transfer of electrons between the carbon felt and the zinc deposition layer, is not beneficial to the transfer of electrons in the zinc deposition/stripping process, and increases the interfacial charge transfer resistance. The Chinese patent document with publication number CN117039019A discloses a method for depositing metallic tin on the surface of a carbon felt by adopting an electrodeposition process, more zinc deposition anchoring sites are added after tin deposition, and the electrochemical performance of a battery is improved. However, the tin deposited by the process has strong chemical reactivity, and is easy to react with acidic substances in electrolyte during the charge and discharge processes of the battery, so that the active sites are invalid.
Disclosure of Invention
The invention aims to provide a preparation method of a modified zinc-bromine flow battery carbon felt anode, which can solve the problems of excessive oxidation of a carbon felt and influence of low oxide conductivity on electron transfer in a zinc deposition/stripping process caused by adopting an oxide loaded on the surface of the carbon felt in the prior art, and solve the problem of failure of a tin active site of zinc deposition caused by reaction of a loaded metal active site with an acidic substance in electrolyte. The method is a liquid phase deposition process which is simple in process and suitable for large-scale production.
In order to solve the technical problems, the invention provides a preparation method of a modified zinc-bromine flow battery carbon felt negative electrode, which comprises the following steps:
(1) Vacuum drying is carried out on the cleaned carbon felt to obtain a carbon felt A;
(2) Adding cuprous sulfate into a mixed solution of organic nitrile and water and stirring to obtain a cuprous sulfate solution, soaking a carbon felt A in the cuprous sulfate solution, and heating for reaction to obtain a carbon felt B, wherein the mass ratio of the cuprous sulfate to the carbon felt A is 1-10:1;
(3) And washing the carbon felt B, and drying in vacuum to obtain the modified zinc-bromine flow battery carbon felt anode.
Preferably, in the step (1), the temperature of vacuum drying is 80-200 ℃ and the time is 5-20 hours.
Preferably, in the step (2), the organic nitrile is one of acetonitrile, propionitrile and butyronitrile, the molar ratio of the organic nitrile to water is 2-10:10, the stirring time is 0.5-3 h, the molar ratio of cuprous sulfate in the cuprous sulfate solution to the organic nitrile is 1:5-9, and the heating reaction temperature is 70-110 ℃ for 4-10 h. .
Preferably, in the step (3), the temperature of vacuum drying is 100-180 ℃ and the time is 10-24 hours.
The invention also provides a modified zinc-bromine flow battery carbon felt anode which is prepared by the preparation method, and comprises a carbon felt substrate and copper simple substance particles loaded on the carbon felt.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides a preparation method of a modified zinc-bromine flow battery carbon felt anode, which comprises the steps of regulating and controlling a cuprous sulfate disproportionation reaction, and loading elemental copper particles on the surface of the carbon felt anode. Because cuprous sulfate is unstable, disproportionation reaction occurs when dissolved in water, and copper sulfate are formed. When the aqueous solution contains organic nitrile, the disproportionation reaction is inhibited and cuprous sulfate is stably present. After the carbon felt is soaked in the mixed solution of the cuprous sulfate and the organic nitrile, the cuprous sulfate gradually starts to perform disproportionation reaction by heating the organic nitrile to evaporate from the solution. The elemental copper generated by the disproportionation reaction of the cuprous sulfate can be deposited on the surface of the carbon felt, so that the aim of loading the elemental copper on the modified carbon felt is fulfilled. The method has simple process steps and low equipment requirement, does not need high-temperature heating in the implementation process, and can avoid the increase of oxygen-containing functional groups on the surface of the carbon felt caused by excessive oxidation of the carbon felt, thereby maintaining the inherent conductivity and mechanical strength of the carbon felt to the greatest extent.
(2) According to the technical scheme provided by the invention, the copper simple substance loaded on the surface of the carbon felt has stable chemical property, is difficult to chemically react with substances such as zinc bromide solute, complexing agent and acid in electrolyte, effectively avoids the problem that zinc deposition active sites fail due to reaction in the charge and discharge process, and provides a basis for long-service life operation of the battery. Meanwhile, the copper simple substance has excellent conductivity. In the charge-discharge process, the elemental copper particles loaded on the carbon felt can serve as active sites for zinc deposition, can rapidly transfer electrons between the carbon felt and a zinc deposition layer, promote rapid transfer of electrons in the zinc deposition/stripping process, remarkably reduce interface charge transfer resistance, reduce polarization phenomenon, and further promote efficient electrochemical reaction.
(3) According to the technical scheme provided by the invention, the elemental copper loaded on the surface of the carbon felt can be used as an efficient electrochemical reaction active site in the charging process, and the key effect is that the activation energy barrier required by zinc ion reduction nucleation can be remarkably reduced, and the active site of electrochemical reaction is formed on the surface of the carbon felt. The zinc atoms have good zinc-philic characteristics, and zinc can be led to be deposited on active sites formed by copper rather than deposited zinc sites preferentially, so that the further development of zinc deposition non-uniformity phenomenon in the charging process is effectively inhibited, the inhibition of zinc dendrite growth is realized, and the uniform deposition of zinc is effectively promoted and led. Further, the strong interaction between copper and zinc is not limited to the deposition phase, but throughout the charge-discharge cycle, and can bi-directionally promote the uniform deposition and stripping process of zinc. The synergistic effect of the zinc-philic characteristic of copper and the reduction of the zinc nucleation barrier directly results in the microstructure of the zinc deposition layer on the surface of the carbon felt being significantly optimized and becoming more uniform and compact. The optimized deposition layer structure can obviously inhibit the growth and the spread of zinc dendrites. The zinc dendrite is effectively inhibited, so that the risk of short circuit of the battery caused by the zinc dendrite penetrating through the diaphragm is eliminated, and more importantly, the shuttle effect of bromine simple substance in the positive electrode area to the negative electrode through a dendrite channel is blocked. Through the positive influence of the series of linkage, the overall electrochemical performance of the zinc-bromine flow battery, including the circulation stability, the coulombic efficiency, the safety and the like, is greatly improved.
(4) According to the technical scheme, the performance of the zinc-bromine flow battery is improved obviously by optimizing the process parameters. For example, the mass ratio of cuprous sulfate to carbon felt a, the molar ratio of organic nitrile to water, etc. The mass ratio of the cuprous sulfate to the carbon felt A plays a decisive role in the quantity of the elemental copper loaded by the carbon felt. The inventor finds that when the mass ratio of the cuprous sulfate to the carbon felt A is smaller, the elemental copper particles loaded on the carbon felt are fewer, and the active sites for zinc deposition cannot be effectively increased, and when the mass ratio is larger, the elemental copper particles loaded on the carbon felt are more, so that the pore structure of the carbon felt can be blocked, the transmission of electrolyte in the carbon felt is influenced, and the available space positions for zinc deposition are reduced. And the proper mass ratio of the cuprous sulfate to the carbon felt A can introduce enough copper simple substance zinc deposition active sites on the carbon felt, and meanwhile, the phenomenon that the copper simple substance blocks the pore structure of the carbon felt is avoided. The inventors have also found that the molar ratio of organic nitrile to water has an effect on the process of the disproportionation reaction of cuprous sulfate. When the molar ratio of the organic nitrile to the water is too high, a large amount of water is taken away in the evaporation process of the organic nitrile, so that the disproportionation reaction of the cuprous sulfate is obviously inhibited, the copper simple substance is not supported on the carbon felt, when the molar ratio of the organic nitrile to the water is too low, the organic nitrile is quickly evaporated, the effect of inhibiting the disproportionation reaction of the cuprous sulfate cannot be achieved, the disproportionation reaction can quickly occur, and a large amount of formed copper simple substance is not supported on the carbon felt. The proper molar ratio of the organic nitrile to the water is favorable for the controllable execution of the disproportionation reaction of the cuprous sulfate, and simultaneously ensures that the elemental copper particles are loaded on the carbon felt.
(5) According to the invention, through regulating and controlling the disproportionation reaction of the cuprous sulfate, the elemental copper particles are loaded on the carbon felt, so that the comprehensive electrochemical performance of the zinc-bromine flow battery is remarkably improved. Specifically, when the specific capacity of the charging area of the battery is set to 40mAh/cm < 2> under the current density of 60mA/cm < 2>, the zinc-bromine flow battery taking the copper simple substance modified carbon felt prepared by the technical scheme as the negative electrode shows excellent performance indexes that the coulomb efficiency can reach 94.1% -96.2%, the voltage efficiency reaches 83.2% -86.7%, and the energy efficiency is 78.3% -83.4%. Of particular interest, zinc-bromine flow batteries assembled with the elemental copper modified carbon felt anode prepared in example 1, after charge and discharge cycle testing for up to 1500 weeks, have energy efficiency and coulombic efficiency retention rates of up to 96.2% and 97.2%, respectively, strongly demonstrate that the modified anode material imparts excellent long-term cycling stability to the battery. Therefore, the copper simple substance modified carbon felt anode prepared by the method has excellent chemical stability and electrochemical stability, remarkably improves the efficiency index and the cycle life of the zinc-bromine flow battery, lays a solid foundation for popularization of the zinc-bromine flow battery in the practical application fields of large-scale energy storage and the like, and has wide commercial application prospect. The technological breakthrough makes the zinc-bromine flow battery possess excellent electrochemical performance and long service life.
Drawings
FIG. 1 is a constant current charge-discharge graph of electrochemical performance test using the elemental copper modified carbon felt prepared in example 1 of the present invention and the carbon felt of comparative example 1 as the negative electrode of a zinc-bromine flow battery, respectively;
FIG. 2 is a cycle chart of electrochemical performance test using the elemental copper modified carbon felt prepared in example 1 of the present invention as the negative electrode of a zinc-bromine flow battery;
FIG. 3 is a cycle graph of electrochemical performance testing using the carbon felt of comparative example 1 as the negative electrode of a zinc bromine flow battery;
FIG. 4 is an X-ray diffraction (XRD) pattern of elemental copper modified and unmodified carbon mats prepared in example 1 of the invention;
FIG. 5 is a Scanning Electron Microscope (SEM) image of the elemental copper modified carbon mat prepared in example 1 of the present invention;
FIG. 6 is a Scanning Electron Microscope (SEM) image of a comparative example 1 carbon felt of the present invention;
FIG. 7 is an electronic graph collected during energy dispersive X-ray spectrometry of the elemental copper modified carbon mat prepared in example 1 of the present invention;
FIG. 8 is an energy dispersive X-ray spectrometry (EDS) plot of the selected region of FIG. 7.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below by way of examples with reference to the accompanying drawings, but are not intended to limit the scope of the present invention.
The cuprous sulfate used in the embodiment of the invention is purchased from the Gede chemical industry network, and other medicines and reagents are purchased from the Allatin network or the national medicine reagent network.
Example 1
And cleaning the carbon felt to remove impurities on the surface of the carbon felt, and placing the cleaned carbon felt in a vacuum oven for drying at 130 ℃ for 13 hours to obtain a carbon felt A. And (3) controlling the mass ratio of the cuprous sulfate to the carbon felt A obtained after drying to be 5:1, wherein the molar ratio of the cuprous sulfate to the acetonitrile to be 1:7, adding the cuprous sulfate into the mixed solution with the acetonitrile to water molar ratio of 6:10, and stirring for 1.75 hours to obtain the cuprous sulfate solution. Carbon felt a was immersed in a cuprous sulfate solution and heated at 90 ℃ for 7h, followed by removal to give carbon felt B. And washing the obtained carbon felt B with water and ethanol, and vacuum drying the washed carbon felt B at 140 ℃ for 17 hours to obtain the modified zinc-bromine flow battery carbon felt anode.
Example 2
And cleaning the carbon felt to remove impurities on the surface of the carbon felt, and placing the cleaned carbon felt in a vacuum oven for drying at 125 ℃ for 14 hours to obtain a carbon felt A. And (3) controlling the mass ratio of the cuprous sulfate to the carbon felt A obtained after drying to be 4:1, wherein the molar ratio of the cuprous sulfate to the acetonitrile to be 1:6, adding the cuprous sulfate into the mixed solution with the acetonitrile to water molar ratio of 7:10, and stirring for 2 hours to obtain the cuprous sulfate solution. Carbon felt a was immersed in a cuprous sulfate solution and heated at 85 ℃ for 8h, followed by removal to give carbon felt B. And washing the obtained carbon felt B with deionized water and ethanol, and vacuum drying the washed carbon felt B at 135 ℃ for 18 hours to obtain the modified zinc-bromine flow battery carbon felt anode.
Example 3
And cleaning the carbon felt to remove impurities on the surface of the carbon felt, and placing the cleaned carbon felt in a vacuum oven for drying at 135 ℃ for 12 hours to obtain a carbon felt A. And (3) controlling the mass ratio of the cuprous sulfate to the carbon felt A obtained after drying to be 6:1, wherein the molar ratio of the cuprous sulfate to the acetonitrile to be 1:8, adding the cuprous sulfate into the mixed solution with the acetonitrile to water molar ratio of 6:10, and stirring for 1.5h to obtain a cuprous sulfate solution. Carbon felt a was immersed in a cuprous sulfate solution and heated at 95 ℃ for 6 hours, followed by removal to give carbon felt B. And washing the obtained carbon felt B with deionized water and ethanol, and vacuum drying the washed carbon felt B for 16 hours at 145 ℃ to obtain the modified zinc-bromine flow battery carbon felt anode.
Example 4
And cleaning the carbon felt to remove impurities on the surface of the carbon felt, and placing the cleaned carbon felt in a vacuum oven for drying at 100 ℃ for 17 hours to obtain a carbon felt A. And (3) controlling the mass ratio of the cuprous sulfate to the carbon felt A obtained after drying to be 2:1, wherein the molar ratio of the cuprous sulfate to the propionitrile to be 1:5, adding the cuprous sulfate into the mixed solution with the propionitrile to water molar ratio of 4:10, and stirring for 1h to obtain a cuprous sulfate solution. Carbon felt a was immersed in a cuprous sulfate solution and heated at 100 ℃ for 5 hours, followed by removal to give carbon felt B. And washing the obtained carbon felt B with deionized water and ethanol, and vacuum drying the washed carbon felt B at 120 ℃ for 21 hours to obtain the modified zinc-bromine flow battery carbon felt anode.
Example 5
And cleaning the carbon felt to remove impurities on the surface of the carbon felt, and placing the cleaned carbon felt in a vacuum oven for drying at 160 ℃ for 9 hours to obtain a carbon felt A. And (3) controlling the mass ratio of the cuprous sulfate to the carbon felt A obtained after drying to be 8:1, wherein the molar ratio of the cuprous sulfate to the acetonitrile to be 1:9, adding the cuprous sulfate into the mixed solution with the acetonitrile to water molar ratio of 8:10, and stirring for 2.5h to obtain a cuprous sulfate solution. Carbon felt a was immersed in a cuprous sulfate solution and heated at 80 ℃ for 9h, followed by removal to give carbon felt B. And washing the obtained carbon felt B with deionized water and ethanol, and vacuum drying the washed carbon felt B at 160 ℃ for 13 hours to obtain the modified zinc-bromine flow battery carbon felt anode.
Example 6
And cleaning the carbon felt to remove impurities on the surface of the carbon felt, and placing the cleaned carbon felt in a vacuum oven for drying at 200 ℃ for 5 hours to obtain a carbon felt A. And (3) controlling the mass ratio of the cuprous sulfate to the carbon felt A obtained after drying to be 10:1, wherein the molar ratio of the cuprous sulfate to the butyronitrile to be 1:6, adding the cuprous sulfate into the mixed solution with the butyronitrile to water molar ratio of 2:10, and stirring for 3 hours to obtain a cuprous sulfate solution. Carbon felt a was immersed in a cuprous sulfate solution and heated at 110 ℃ for 4 hours, followed by removal to give carbon felt B. And washing the obtained carbon felt B with deionized water and ethanol, and vacuum drying the washed carbon felt B for 10 hours at 180 ℃ to obtain the modified zinc-bromine flow battery carbon felt anode.
Example 7
And cleaning the carbon felt to remove impurities on the surface of the carbon felt, and placing the cleaned carbon felt in a vacuum oven to be dried for 20 hours at 80 ℃ to obtain a carbon felt A. And (3) controlling the mass ratio of the cuprous sulfate to the carbon felt A obtained after drying to be 1:1, wherein the molar ratio of the cuprous sulfate to the acetonitrile to be 1:7, adding the cuprous sulfate into the mixed solution with the acetonitrile to water molar ratio of 10:10, and stirring for 0.5h to obtain a cuprous sulfate solution. Carbon felt a was immersed in a cuprous sulfate solution and heated at 70 ℃ for 10 hours, followed by removal to give carbon felt B. And washing the obtained carbon felt B with deionized water and ethanol, and vacuum drying the washed carbon felt B at 100 ℃ for 24 hours to obtain the modified zinc-bromine flow battery carbon felt anode.
The cuprous sulfate is unstable and undergoes disproportionation when dissolved in water to form copper and copper sulfate. 1mol of cuprous ions can be complexed by 2-4 mol of acetonitrile. When the aqueous solution contains enough organic nitriles such as acetonitrile, cuprous ions formed by ionization of cuprous sulfate are completely complexed by the organic nitriles such as acetonitrile, disproportionation reaction is inhibited, and the cuprous sulfate can stably exist in the mixed solution. Soaking the carbon felt in a mixed solution of cuprous sulfate in water and acetonitrile, heating, evaporating acetonitrile in the mixed solution from the solution, gradually reducing the amount of acetonitrile in the solution, and keeping the amount of cuprous ions unchanged. When the amount of acetonitrile is reduced to a value that the mole number of cuprous ions in the solution is more than half of that of acetonitrile, the complexed cuprous ions start to dissociate, the cuprous sulfate gradually starts to perform disproportionation reaction, and the elementary substance of copper generated by the disproportionation reaction is deposited on the surface of the carbon felt, so that the aim of loading the modified carbon felt with the elementary substance of copper is fulfilled.
The method has simple technical process and required equipment, does not need high-temperature heating in the implementation process, can avoid excessive oxidation of the carbon felt, increases oxygen-containing functional groups on the surface of the carbon felt, and reduces the conductivity and strength of the carbon felt. Copper has good zinc affinity, and the carrier on the surface of the carbon felt can reduce the over-potential of zinc nucleation and increase the reactive sites on the surface of the carbon felt. In the charging process, due to the good zinc-philic characteristic of copper atoms, zinc can be led to be deposited on active sites formed by copper preferentially instead of deposited zinc sites, so that the further development of zinc deposition non-uniformity phenomenon in the charging process is effectively inhibited, the inhibition of zinc dendrite growth is realized, and the uniform deposition of zinc is effectively promoted and led. The chemical property of the copper simple substance is relatively stable, and the copper simple substance is not easy to react with acid. The method can avoid the failure of the active site caused by the reaction of copper loaded on the surface of the carbon felt and acidic substances in the electrolyte in the charge and discharge process of the zinc-bromine flow battery. The conductivity of copper is extremely high, and the copper is used as an electrochemical reaction active site, can rapidly transfer electrons between a carbon felt and a zinc deposition layer, is favorable for rapid transfer of electrons in a zinc deposition/stripping process, reduces interface charge transfer resistance, reduces polarization, and is favorable for accelerating electrochemical reaction. In addition, stronger force is applied between copper and zinc, so that uniform deposition/stripping of zinc in the charge and discharge process is facilitated, a more uniform zinc deposition layer is formed on the surface of the carbon felt, zinc dendrite formation is reduced, membrane back puncture is avoided, shuttling of an anode bromine simple substance is avoided, and the cycle life of the zinc-bromine flow battery is prolonged.
Comparative example 1
And cleaning the carbon felt to remove impurities on the surface of the carbon felt, and placing the cleaned carbon felt in a vacuum oven for drying at 130 ℃ for 13 hours to obtain a carbon felt A. Carbon felt A was immersed in a mixed solution of acetonitrile and water in a molar ratio of 6:10 and heated at 90℃for 7h, followed by removal to give carbon felt B. And washing the obtained carbon felt B with water and ethanol, and vacuum drying the washed carbon felt B at 140 ℃ for 17 hours to obtain the modified zinc-bromine flow battery carbon felt anode.
The difference from example 1 is that comparative example 1 simply soaked a carbon felt in a mixed solution of acetonitrile and water and vacuum-dried, and no elemental copper was supported on the carbon felt.
Comparative example 2
And cleaning the carbon felt to remove impurities on the surface of the carbon felt, and placing the cleaned carbon felt in a vacuum oven for drying at 130 ℃ for 13 hours to obtain a carbon felt A. And (3) controlling the mass ratio of the cuprous sulfate to the carbon felt A obtained after drying to be 20:1, wherein the molar ratio of the cuprous sulfate to the acetonitrile to be 1:7, adding the cuprous sulfate into the mixed solution with the acetonitrile to water molar ratio of 6:10, and stirring for 1.75 hours to obtain the cuprous sulfate solution. Carbon felt a was immersed in a cuprous sulfate solution and heated at 90 ℃ for 7h, followed by removal to give carbon felt B. And washing the obtained carbon felt B with water and ethanol, and vacuum drying the washed carbon felt B at 140 ℃ for 17 hours to obtain the modified zinc-bromine flow battery carbon felt anode.
The difference from example 1 is that the ratio of the copper sulphate of comparative example 2 to the mass of carbon felt a obtained after drying is 20:1, which is higher than the value of the process parameter in all examples.
Comparative example 3
And cleaning the carbon felt to remove impurities on the surface of the carbon felt, and placing the cleaned carbon felt in a vacuum oven for drying at 130 ℃ for 13 hours to obtain a carbon felt A. And (3) controlling the mass ratio of the cuprous sulfate to the carbon felt A obtained after drying to be 0.1:1, wherein the molar ratio of the cuprous sulfate to the acetonitrile to be 1:7, adding the cuprous sulfate into the mixed solution with the acetonitrile to water molar ratio of 6:10, and stirring for 1.75 hours to obtain the cuprous sulfate solution. Carbon felt a was immersed in a cuprous sulfate solution and heated at 90 ℃ for 7h, followed by removal to give carbon felt B. And washing the obtained carbon felt B with water and ethanol, and vacuum drying the washed carbon felt B at 140 ℃ for 17 hours to obtain the modified zinc-bromine flow battery carbon felt anode.
The difference from example 1 is that the ratio of the mass of the cuprous sulfate of comparative example 3 to the mass of the carbon felt a obtained after drying is 0.1:1, which is lower than the process parameter value in all examples.
Comparative example 4
And cleaning the carbon felt to remove impurities on the surface of the carbon felt, and placing the cleaned carbon felt in a vacuum oven for drying at 130 ℃ for 13 hours to obtain a carbon felt A. And (3) controlling the mass ratio of the cuprous sulfate to the carbon felt A obtained after drying to be 5:1, wherein the molar ratio of the cuprous sulfate to the acetonitrile to be 1:7, adding the cuprous sulfate into the mixed solution with the acetonitrile to water molar ratio of 25:10, and stirring for 1.75 hours to obtain the cuprous sulfate solution. Carbon felt a was immersed in a cuprous sulfate solution and heated at 90 ℃ for 7h, followed by removal to give carbon felt B. And washing the obtained carbon felt B with water and ethanol, and vacuum drying the washed carbon felt B at 140 ℃ for 17 hours to obtain the modified zinc-bromine flow battery carbon felt anode.
The difference from example 1 is that the molar ratio of acetonitrile to water of comparative example 4 is 25:10, which is higher than the process parameter value in all examples.
Comparative example 5
And cleaning the carbon felt to remove impurities on the surface of the carbon felt, and placing the cleaned carbon felt in a vacuum oven for drying at 130 ℃ for 13 hours to obtain a carbon felt A. And (3) controlling the mass ratio of the cuprous sulfate to the carbon felt A obtained after drying to be 5:1, wherein the molar ratio of the cuprous sulfate to the acetonitrile to be 1:7, adding the cuprous sulfate into the mixed solution with the acetonitrile to water molar ratio of 1:10, and stirring for 1.75 hours to obtain a cuprous sulfate solution. Carbon felt a was immersed in a cuprous sulfate solution and heated at 90 ℃ for 7h, followed by removal to give carbon felt B. And washing the obtained carbon felt B with water and ethanol, and vacuum drying the washed carbon felt B at 140 ℃ for 17 hours to obtain the modified zinc-bromine flow battery carbon felt anode.
The difference from example 1 is that the molar ratio of acetonitrile to water of comparative example 5 is 1:10, which is below the value of the process parameter in all examples.
Comparative example 6
And cleaning the carbon felt to remove impurities on the surface of the carbon felt, and placing the cleaned carbon felt in a vacuum oven for drying at 130 ℃ for 13 hours to obtain a carbon felt A. And (3) controlling the mass ratio of the cuprous sulfate to the carbon felt A obtained after drying to be 5:1, wherein the molar ratio of the cuprous sulfate to the acetonitrile to be 1:7, adding the cuprous sulfate into the mixed solution with the acetonitrile to water molar ratio of 6:10, and stirring for 1.75 hours to obtain the cuprous sulfate solution. Carbon felt a was immersed in a cuprous sulfate solution and heated at 90 ℃ for 7h, followed by removal to give carbon felt B. And washing the obtained carbon felt B with water and ethanol, and vacuum-drying the washed carbon felt B for 17 hours at 140 ℃ to obtain a carbon felt C. And (3) placing the carbon felt C in a muffle furnace, heating to 650 ℃ at 3 ℃ per min under the air atmosphere, preserving heat for 0.5h, and naturally cooling the muffle furnace to room temperature after the heat preservation is finished to obtain the modified zinc-bromine flow battery carbon felt anode.
The difference from example 1 is that comparative example 6 was carried out by holding the copper-loaded carbon felt in a muffle furnace at 650 ℃ for 0.5h, and oxidizing part of the copper loaded on the carbon felt to copper oxide.
Comparative example 7
And cleaning the carbon felt to remove impurities on the surface of the carbon felt, and placing the cleaned carbon felt in a vacuum oven for drying at 130 ℃ for 13 hours to obtain a carbon felt A. And (3) controlling the mass ratio of the cuprous sulfate to the carbon felt A obtained after drying to be 5:1, wherein the molar ratio of the cuprous sulfate to the acetonitrile to be 1:7, adding the cuprous sulfate into the mixed solution with the acetonitrile to water molar ratio of 6:10, and stirring for 1.75 hours to obtain the cuprous sulfate solution. Carbon felt a was immersed in a cuprous sulfate solution and heated at 90 ℃ for 7h, followed by removal to give carbon felt B. And washing the obtained carbon felt B with water and ethanol, and vacuum-drying the washed carbon felt B for 17 hours at 140 ℃ to obtain a carbon felt C. And (3) placing the carbon felt C in a muffle furnace, heating to 650 ℃ at 3 ℃ per min under the air atmosphere, preserving heat for 10 hours, and naturally cooling the muffle furnace to room temperature after the heat preservation is finished to obtain the modified zinc-bromine flow battery carbon felt anode.
The difference from example 1 is that the carbon felt after copper loading was kept at 650 ℃ for 10 hours in a muffle furnace in comparative example 7, and copper loaded on the carbon felt was oxidized to copper oxide.
Comparative example 8
And cleaning the carbon felt to remove impurities on the surface of the carbon felt, and placing the cleaned carbon felt in a vacuum oven for drying at 130 ℃ for 13 hours to obtain a carbon felt A. The platinum-plated titanium mesh is used as an anode material, the carbon felt A is used as a cathode, 100ml of a mixed aqueous solution of 20mM InCl 3 and 3M KBr is used as an electroplating solution, and the carbon felt A is electroplated for 10min under the current density of 30mA/cm 2. And washing the carbon felt B obtained by electroplating with water and ethanol, and vacuum drying the washed carbon felt at 140 ℃ for 17 hours to obtain the modified zinc-bromine flow battery carbon felt anode.
The difference from example 1 is that comparative example 8 uses an electroplating process to load elemental indium on the carbon mat.
And assembling the zinc-bromine flow battery for electrochemical performance test. The zinc-bromine flow battery is prepared by the example and the comparative example, wherein the carbon felt is used as a negative electrode, the unmodified carbon felt is used as a positive electrode, a microporous filter membrane is used as a diaphragm, and electrolytes of the positive electrode and the negative electrode consist of 2mol/L zinc bromide, 3mol/L potassium chloride, 0.2M tetramethyl ammonium bromide and 0.2M tetrabutyl ammonium bromide. The effective area of the anode and cathode carbon felt electrodes is 3 cm multiplied by 3 cm.
And testing the electrochemical performance of the zinc-bromine flow battery by adopting a constant-current charge-discharge mode. In the test process, the electrolyte flows at 35 mL/min, is charged at 40 min (the specific capacity of the charging area is 40mAh/cm <2 >) with a constant current of 60mA/cm 2, and is discharged to a voltage of 0.6V with the same constant current. And according to the battery charge-discharge curve, electrochemical performance indexes such as Coulomb Efficiency (CE), voltage Efficiency (VE) and Energy Efficiency (EE) of the battery are calculated.
The electrochemical performance results of the first-turn charge and discharge tests of the materials are shown in Table 1.
As can be seen from table 1, the coulombic efficiency, the voltage efficiency and the energy efficiency of the zinc-bromine flow battery using the carbon felts obtained in examples 1 to 7 as the negative electrode are all superior to those of the zinc-bromine flow battery using the carbon felts obtained in comparative examples 1 to 8 as the negative electrode, which indicates that the electrochemical performance of the carbon felts can be significantly improved after modification by loading the elemental copper on the surface of the carbon felts. In all examples, example 1, which was carried out with the optimal process parameters, exhibited the most excellent overall performance, with all three efficiency parameters reaching the highest level. As the process parameter range adopted becomes larger gradually, three key indexes of coulomb efficiency, voltage efficiency and energy efficiency of examples 2 to 7 have a tendency to decrease. The coulombic, voltage and energy efficiencies of example 1 were 96.2%, 86.7% and 83.4%, respectively, while the coulombic, voltage and energy efficiencies of example 7 were 94.1%, 83.2% and 78.3%, respectively. The method can show that the effect of the modified carbon felt loaded by the copper simple substance can be better realized by optimally combining various technological parameters such as the mass ratio of the cuprous sulfate to the carbon felt A in the modification process, the mole ratio of the organic nitrile to water, the mole ratio of the cuprous sulfate to the organic nitrile, the heating temperature and time and the like, so that the electrochemical performance of the zinc-bromine flow battery is obviously improved.
With the same charge capacity, a greater coulombic efficiency indicates more discharge capacity. The coulombic efficiency of examples 1-7 is greater than 94%, while the coulombic efficiency of comparative examples 1-8 is no more than 88%. This shows that the carbon felt modified by the copper simple substance load can reversibly release more charges, because the copper loaded on the surface of the carbon felt has good zinc affinity, and the loading on the surface of the carbon felt can reduce the overpotential of zinc nucleation and increase the reactive sites on the surface of the carbon felt. In addition, stronger force is exerted between copper and zinc, which is beneficial to uniform deposition/stripping of zinc in the charge-discharge process, so that a more uniform zinc deposition layer is formed on the surface of the carbon felt, and zinc dendrite formation is reduced. The voltage efficiency is the ratio of the average discharge voltage to the average charge voltage, and is related to the polarization phenomenon during the charge and discharge of the battery. The voltage efficiency of examples 1-7 was greater than 83%, while the voltage efficiency of comparative examples 1-8 was no more than 80%. This shows that the zinc-bromine flow battery using the carbon felt obtained in examples 1-7 as the negative electrode has lower polarization and lower voltage loss. This is because the copper supported on the carbon felt surface has extremely high conductivity, which acts as an electrochemically reactive site, facilitating electron transfer during zinc deposition/stripping. The energy efficiency is an evaluation index of the electric energy conversion efficiency of the battery in the charging and discharging processes, and the value of the energy efficiency is the comprehensive effect of coulomb efficiency and voltage efficiency. The energy efficiency of examples 1 to 7 was more than 78%, while the energy efficiency of comparative examples 1 to 8 was not more than 71%. The copper loaded on the surface of the carbon felt has the comprehensive beneficial effects of reducing the overpotential of zinc nucleation, increasing the reactive sites on the surface of the carbon felt, reducing polarization and the like, so that the energy efficiency of the zinc-bromine flow battery is improved after copper loading modification.
As can be seen from comparative example 1 and comparative example 1, the performance index of example 1 is far superior to that of comparative example 1. It can be stated that the carbon felt is simply soaked in the mixed solution of organic nitrile and water and dried in vacuum, and the simple substance of copper is not loaded on the carbon felt, so that the aim of improving the electrochemical performance of the carbon felt cannot be achieved.
As can be seen from comparative examples 1 and 2 and comparative example 3, the mass ratio of cuprous sulfate to carbon felt a plays a decisive role in the amount of elemental copper supported by the carbon felt. When the mass ratio of the cuprous sulfate to the carbon felt A is smaller, the elemental copper particles loaded on the carbon felt are fewer, and the active sites for zinc deposition cannot be effectively increased, and when the mass ratio is larger, the elemental copper particles loaded on the carbon felt are more, so that the pore structure of the carbon felt can be blocked, the transmission of electrolyte in the carbon felt is influenced, and the available space positions for zinc deposition are reduced. And the proper mass ratio of the cuprous sulfate to the carbon felt A can introduce enough copper simple substance zinc deposition active sites on the carbon felt, and meanwhile, the phenomenon that the copper simple substance blocks the pore structure of the carbon felt is avoided.
As can be seen from comparative example 1 and comparative examples 4 and 5, the molar ratio of organic nitrile to water has an effect on the process of the disproportionation reaction of cuprous sulfate. When the molar ratio of the organic nitrile to the water is too high, a large amount of water is taken away in the process of evaporation of the organic nitrile, so that the disproportionation reaction of the cuprous sulfate is obviously inhibited, the copper simple substance is not supported on the carbon felt, when the molar ratio of the organic nitrile to the water is too low, the disproportionation reaction of the cuprous sulfate cannot be inhibited, the disproportionation reaction can occur rapidly, and a large amount of formed copper simple substance is not supported on the carbon felt. The proper molar ratio of the organic nitrile to the water is favorable for the disproportionation reaction of the cuprous sulfate, and simultaneously ensures that the elemental copper particles are loaded on the carbon felt.
Comparative example 6 when incubated at 650 ℃ for 0.5h in an air atmosphere, a portion of elemental copper supported on the carbon felt was oxidized to copper oxide, and the support was a composite of copper and copper oxide. Comparative example 7 elemental copper supported on a carbon mat was oxidized to copper oxide with the support being a composite of copper oxide when incubated at 650 ℃ for 10 hours in an air atmosphere. As can be seen from comparative example 1, comparative example 6 and comparative example 7, the substances loaded on the carbon felt in the technical scheme of the invention are only copper simple substance particles, and the performance indexes of the substances are far better than those of the substances loaded with copper and copper oxide compound in comparative example 6 and copper oxide compound in comparative example 7. Compared with copper, copper oxide compound and copper oxide, the conductivity of the copper simple substance loaded on the carbon felt is higher, electrons can be rapidly transmitted between the carbon felt and the zinc deposition layer, the rapid charge transfer in the zinc deposition/stripping process is facilitated, the interface charge transfer resistance can be effectively reduced, and the polarization is reduced. In addition, the long-time heat treatment of comparative example 7 under the air atmosphere condition causes the carbon felt to be excessively oxidized, and excessive oxygen-containing functional groups are formed on the surface of the carbon felt, which decreases the conductivity and strength of the carbon felt. This also results in comparative example 7 having much lower performance than example 1.
As can be seen from comparative examples 1 and 8, the performance index of example 1 is far superior to that of comparative example 8. In addition, comparative example 8 was subjected to a long cycle test, and after only 500 weeks, its coulombic efficiency, voltage efficiency and energy efficiency were reduced to 67.3%, 69.2% and 46.6%, respectively. This is because the elemental indium loaded on the carbon felt is relatively active in chemical nature and is susceptible to chemical reaction with acidic substances in the electrolyte, resulting in failure of the zinc deposited indium active sites on the carbon felt.
Fig. 1 is a constant current charge-discharge graph of electrochemical performance test using the elemental copper modified carbon felt prepared in example 1 of the present invention and the carbon felt of comparative example 1 as the negative electrode of a zinc-bromine flow battery, respectively. Comparative example 1 differs from example 1 in that comparative example 1 simply soaked a carbon felt in a mixed solution of acetonitrile and water and dried under vacuum, and no elemental copper was supported on the carbon felt. In the electrochemical performance test process, the electrolyte flows at 35mL/min, is charged for 40min at a constant current of 60mA/cm 2 (the specific capacity of the charging area is 40mAh/cm <2 >), and is discharged to a voltage of 0.6V at the same constant current. As can be seen from the graph, the elemental copper modified carbon felt anode obtained in example 1 was about 4mAh/cm 2 higher than that of comparative example 1 on the discharge area specific capacity index, which resulted in the carbon felt obtained in example 1 having a coulombic efficiency about 10% higher than that of comparative example 1. The charging plateau between the two was not very different, but the elemental copper modified carbon felt anode discharge voltage was about 160mV higher than comparative example 1, which resulted in a carbon felt with voltage efficiency of about 7.9% higher for example 1 than comparative example 1. The combined effect of coulombic and voltage efficiencies is such that the energy efficiency of the carbon felt obtained in example 1 is 16% higher than that of comparative example 1. According to the comparison, the copper loaded on the surface of the carbon felt has beneficial effects in the aspects of reducing the overpotential of zinc nucleation, increasing the reactive sites on the surface of the carbon felt, reducing polarization and the like, so that the coulomb efficiency, the voltage efficiency and the energy efficiency of the zinc-bromine flow battery are improved after copper loading modification.
Fig. 2 and 3 are cycle graphs of electrochemical performance tests using the elemental copper modified carbon felt prepared in example 1 of the present invention and the carbon felt of comparative example 1 as the negative electrode of a zinc-bromine flow battery, respectively. It can be seen that the elemental copper modified carbon felt anode obtained in example 1 has little decay in coulombic efficiency and energy efficiency after 1500 weeks of cycle, and the retention rates of the energy efficiency and the coulombic efficiency are as high as 96.2% and 97.2%, respectively. The carbon felt anode of comparative example 1 had a relatively large fluctuation during the cycle, and the coulombic efficiency and the energy efficiency were attenuated by approximately 30% and 20%, respectively, after only 140 weeks of cycle. The formation of zinc dendrites is closely related to the coulombic efficiency, energy efficiency and cycle retention rate of a zinc bromine flow battery, and the continuous growth of zinc dendrites can penetrate through a diaphragm, cause a short circuit phenomenon, and lead to the generation of "dead" zinc, thereby significantly reducing the coulombic efficiency, energy efficiency and adversely affecting the stability and life of the system. Therefore, comparison shows that the copper simple substance modified carbon felt prepared by the technical scheme of the invention has good effect in inhibiting zinc dendrites.
FIG. 4 is an X-ray diffraction (XRD) pattern of elemental copper modified and unmodified carbon mats prepared in example 1 of the invention. The (111), (200) and (220) diffraction peaks of copper are clearly observed at 43.2 °, 50.7 ° and 74.4 ° for the modified carbon felt obtained in example 1, which indicates that example 1 successfully loads elemental copper on the carbon felt. Further comparing the XRD patterns of the modified carbon felt and the unmodified carbon felt prepared in example 1, it can be seen that the diffraction peaks of the two are substantially identical except for the diffraction peak of the elemental copper. The results show that the modification process in the embodiment 1 only carries simple substances of copper on the surface of the carbon felt, does not generate compounds such as cuprous oxide, cupric oxide and the like, does not damage the crystal structure of the carbon felt, and completely maintains the original crystal phase characteristics of the carbon felt while realizing the loading of copper particles.
Fig. 5 and 6 are Scanning Electron Microscope (SEM) images of the elemental copper modified carbon felt prepared in example 1 and the carbon felt of comparative example 1, respectively. As is apparent from fig. 5, the carbon fiber of the elemental copper modified carbon mat prepared in example 1 has a plurality of nanoparticles thereon. In fig. 6, the carbon fibers of the carbon felt of comparative example 1 were smoother, and no significant amount of particles were seen.
Fig. 7 is an electron spectrum collected during energy dispersive X-ray spectroscopy analysis of the elemental copper modified carbon mat prepared in example 1 of the present invention, and fig. 8 is an energy dispersive X-ray spectrum (EDS) of the selected area of fig. 7, showing significant copper signals in addition to carbon and oxygen signals. By combining the X-ray diffraction (XRD) patterns of the elemental copper modified carbon mat prepared in example 1 of fig. 7,8 and 4, it can be confirmed that the nanoparticles on the carbon fiber of fig. 5 are elemental copper. It can be further explained that elemental copper is supported on the carbon felt by the technical scheme of example 1.
The invention has been described in further detail in the foregoing description of the embodiments, but such description is not to be construed as limiting the invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. The preparation method of the modified zinc-bromine flow battery carbon felt anode is characterized by comprising the following steps of:
(1) Vacuum drying is carried out on the cleaned carbon felt to obtain a carbon felt A;
(2) Adding cuprous sulfate into a mixed solution of organic nitrile and water and stirring to obtain a cuprous sulfate solution, soaking a carbon felt A in the cuprous sulfate solution, and heating for reaction to obtain a carbon felt B, wherein the mass ratio of the cuprous sulfate to the carbon felt A is 1-10:1;
(3) Washing the carbon felt B and drying in vacuum to obtain a modified zinc-bromine flow battery carbon felt anode;
In the step (2), the organic nitrile is one of acetonitrile, propionitrile and butyronitrile, the molar ratio of the organic nitrile to water is 2-10:10, the stirring time is 0.5-3 h, the molar ratio of cuprous sulfate in the cuprous sulfate solution to the organic nitrile is 1:5-9, and the heating reaction temperature is 70-110 ℃ for 4-10 h.
2. The method for preparing the modified zinc-bromine flow battery carbon felt anode according to claim 1, wherein in the step (1), the vacuum drying temperature is 80-200 ℃ and the time is 5-20 hours.
3. The method for preparing the modified zinc-bromine flow battery carbon felt negative electrode according to claim 1, wherein in the step (3), the vacuum drying temperature is 100-180 ℃ and the time is 10-24 hours.
4. The modified zinc-bromine flow battery carbon felt anode is characterized by being prepared by the preparation method of any one of claims 1-3, and comprises a carbon felt substrate and elemental copper particles loaded on the carbon felt.
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