CN114759236A - Assembling and testing method of polysulfide flow battery based on membrane electrode - Google Patents
Assembling and testing method of polysulfide flow battery based on membrane electrode Download PDFInfo
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
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- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
Abstract
The invention provides a method for assembling and testing a polysulfide flow battery based on a membrane electrode. The battery has high coulombic efficiency and good cyclicity.
Description
Technical Field
The invention relates to a polysulfide flow battery based on a membrane electrode and a preparation method thereof, belonging to the technical field of flow batteries.
Background
The flow battery is characterized in that the electrolyte solution of the positive electrode and/or the negative electrode is stored in a storage tank outside the battery and is conveyed to the inside of the battery through a pump and a pipeline to carry out reaction. Inside the battery, the positive and negative electrolytes are separated by ion exchange membrane (or ion diaphragm), and the positive and negative electrolytes are separated and respectively circulated. Different from the common secondary battery, the energy storage active substance of the flow battery is completely separated from the electrode, the power and the capacity are designed independently, and the module combination and the battery structure are easy to place; the electrode only provides a place for electrochemical reaction, and oxidation-reduction reaction does not occur per se; active substances are dissolved in electrolyte, and the danger that the dendritic crystal of the electrode grows to pierce the diaphragm is greatly reduced in the flow battery; meanwhile, the flowing electrolyte can take away heat generated in the charging/discharging process of the battery, and the damage and even combustion of the battery structure caused by the heat generated by the battery are avoided. The flow battery has the characteristics of high capacity, wide application field (environment) and long cycle service life, and has wide application prospect.
Polysulfide is the most potential negative active material for constructing high energy density flow batteries because of its advantages of multiple electrons, high solubility, and low cost. However, the output of the cell is low due to the retarded redox kinetics of polysulfides; the coulombic efficiency and cycle performance of the battery are poor due to the fact that the film penetration of polysulfide generates non-conductive elemental sulfur to deposit on the film and the positive current collector (film penetration effect). Due to the above disadvantages, large-scale industrial application of current polysulfide flow batteries is not possible.
Disclosure of Invention
The invention provides a method for assembling and testing a polysulfide flow battery based on a membrane electrode, which can effectively solve the problems.
The invention is realized in the following way:
a polysulfide redox flow battery based on a membrane electrode is characterized in that a first catalyst layer is coated on a negative electrode of the battery in a scraping manner, and a second catalyst layer is sprayed on one side surface, close to the negative electrode, of a cation exchange membrane of the battery.
As a further improvement, the catalyst material of the first catalyst layer and the second catalyst layer is a graphene-supported transition metal sulfide or a transition metal-nitrogen-carbon material.
As a further improvement, the graphene-supported transition metal sulfide is selected from CoSx@rGO、CuSx@rGO、Ni3S4@rGO、Ni1-xCoxS2@rGO、Ni3-xCoxS4@ rGOOne or more of them.
As a further improvement, the transition metal-nitrogen-carbon material is selected from one or more of Fe-N-C, Co-N-C, Ni-N-C.
As a further improvement, the loading of the catalyst of the first catalyst layer is 2-30mg/cm2The catalyst loading of the second catalyst layer is 1-20mg/cm2。
The method for assembling the polysulfide flow battery based on the membrane electrode comprises the following steps:
s1, preparing a catalyst material into blade coating slurry, and blade-coating the slurry on the surface of the negative electrode;
s2, preparing the catalyst material into spraying slurry, and spraying the spraying slurry on the surface of the cation exchange membrane;
and S3, assembling the polysulfide flow battery, and ensuring that the side, sprayed with the catalyst, of the cation exchange membrane faces to the negative electrode.
As a further improvement, the preparation of the catalyst material into a blade coating slurry or a spray coating slurry is as follows: uniformly dispersing the catalyst material in the organic solvent A, simultaneously dissolving the binder in the organic solvent B, mixing the two solutions, and performing ultrasonic dispersion to obtain blade coating slurry or spraying slurry.
As a further improvement, the organic solvent A is selected from one or more of ethanol, isopropanol or n-propanol; the organic solvent B is selected from one or more of N, N-dimethylformamide or N-methylpyrrolidone; the binder is selected from one or more of PVDF, PTFE and Nafion.
As a further improvement, the mass ratio of the catalyst material to the binder is 20: 1-2: 1.
as a further improvement, the sprayed cation exchange membrane is hot-pressed for 1-20min at 80-200 ℃ and 0.1-10 MPa.
The invention has the beneficial effects that:
the catalyst layer is sprayed on one side surface of the cation exchange membrane close to the negative electrode to form a membrane electrode, the distribution area of the catalyst layer is large, the catalytic efficiency is high, meanwhile, the catalyst layer can also inhibit the serious membrane penetrating effect of polysulfide, and the polysulfide redox kinetics and the power density of the battery are improved.
The catalyst provided by the invention adopts the graphene-loaded transition metal sulfide, and the graphene two-dimensional material is used as a carrier, so that the exposure condition of active sites in the transition metal sulfide is improved, the utilization rate of the catalyst is increased, and the polysulfide redox kinetics and the power density of a battery are further improved. Meanwhile, due to the large specific surface and electronegativity of the graphene, the graphene-loaded transition metal sulfide nano material sprayed on the cation exchange membrane can block and repel negative polysulfide to inhibit the serious membrane penetrating effect of the polysulfide, so that the coulomb efficiency and the cyclicity of the battery are obviously improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a schematic diagram of a membrane electrode-based polysulfide flow cell provided by an embodiment of the present invention.
Fig. 2 is a graph of the power density of a membrane electrode-based polysulfide flow cell provided in examples and comparative examples of the present invention.
FIG. 3 shows a 20mA/cm membrane electrode based polysulfide flow cell provided by examples and comparative examples of the present invention2100-turn long cycle coulombic efficiency plots at current density.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
In the description of the present invention, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or to imply that the number of technical features indicated is significant. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The embodiment of the invention provides a polysulfide flow battery based on a membrane electrode. The catalyst layer is sprayed on the cation exchange membrane to form a membrane electrode, so that the distribution area of the catalyst can be increased, the catalytic efficiency of the catalyst can be increased, and meanwhile, the catalyst layer can also prevent polysulfide from penetrating through the membrane, and further polysulfide redox dynamics and the power density of a battery can be increased.
As a further modification, the catalyst material of the first catalyst layer and the second catalyst layer is a graphene-supported transition metal sulfide or a transition metal-nitrogen-carbon material, but is not limited thereto. Preferably, the graphene-supported transition metal sulfide is selected from CoSx@rGO、CuSx@rGO、Ni3S4@rGO、Ni1-xCoxS2@rGO、Ni3-xCoxS4@ rGO. The transition metal-nitrogen-carbon material is selected from one or more of Fe-N-C, Co-N-C, Ni-N-C. Further preferably, theThe catalyst material of the first catalyst layer and the second catalyst layer is selected from the transition metal sulfide loaded on the graphene. According to the embodiment of the invention, the graphene loaded transition metal sulfide is adopted, so that on one hand, the graphene loaded transition metal sulfide is used as a two-dimensional carrier of the transition metal sulfide, the exposure condition of active sites in the transition metal sulfide is improved, the utilization rate of a catalyst is increased, and the oxidation-reduction kinetics of polysulfide and the power density of a battery are further improved; on the other hand, due to the large specific surface and electronegativity of the graphene, the graphene-loaded transition metal sulfide nanometer material sprayed on the cation exchange membrane can have blocking and repelling effects on polysulfide with negative charge, so that the serious membrane penetrating effect of the polysulfide is inhibited, and the coulomb efficiency and the cyclicity of the battery are remarkably improved.
As a further improvement, the preparation method of the graphene-supported transition metal sulfide comprises the following steps: and (2) ultrasonically dispersing and dissolving graphene oxide in a solvent, adding a sulfur source and transition metal nitrate, uniformly stirring, heating for 8-24 hours at the temperature of 120-200 ℃ in a hydrothermal reaction kettle, cooling, and washing for several times to obtain a product, namely the graphene-loaded transition metal sulfide. The sulfur source is selected from one of thiourea, thioacetamide and sodium thiosulfate; the transition metal nitrate is selected from one of nickel nitrate, cobalt nitrate and copper nitrate. Wherein the concentration of the graphene oxide solution is 1mg/ml, and the mass ratio of the graphene oxide to the transition metal nitrate is 1: 5-1: 20; the mass ratio of the transition metal nitrate to the sulfur source is 1: 5-1: 20.
as a further improvement, the solvent used for dissolving the graphene oxide is one of water, ethylene glycol, glycerol and other solvents.
As a further improvement, the loading of the catalyst of the first catalyst layer is 2-30mg/cm2Preferably 5mg/cm2、10mg/cm2、15mg/cm2、18mg/cm2. The catalyst loading of the second catalyst layer is 1-20mg/cm2Preferably 2mg/cm2、5mg/cm2、9mg/cm2、12mg/cm2、15mg/cm2、18mg/cm2。
As a further improvement, the positive and negative electrodes are made of one of carbon felt or carbon paper.
As a further improvement, the cation exchange membrane is one of Nafion N212, N115 or N117. The cation exchange membrane has stronger cation conductivity than the traditional ceramic diaphragm and small internal resistance of the battery, so that the power density and the energy efficiency are high.
As a further improvement, the negative active material is Na2S2Or Na2S4Of (2) at a concentration of 0.1 to 7 mol/L.
As a further improvement, the positive active substance is I-Na4[Fe(CN)6]、Mn2+TEMPO, ferrocene, Pb2+、Ce3+Etc. and one of their derivatives in a concentration of 0.5-8 mol/L.
The embodiment of the invention also provides an assembly method of the polysulfide flow battery based on the membrane electrode, which comprises the following steps:
s1, preparing a catalyst material into blade coating slurry, and blade-coating the slurry on the surface of the negative electrode;
s2, preparing the catalyst material into spraying slurry, and spraying the spraying slurry on the surface of the cation exchange membrane;
and S3, assembling the polysulfide flow battery according to a conventional method, and ensuring that the surface of the cation exchange membrane sprayed with the catalyst faces to the negative electrode.
As a further improvement, the preparation of the catalyst material into a blade coating slurry or a spray coating slurry is as follows: uniformly dispersing the catalyst material in the organic solvent A, simultaneously dissolving the binder in the organic solvent B, mixing the two solutions, and performing ultrasonic dispersion to obtain blade coating slurry or spraying slurry. Preferably, the organic solvent A is one or a mixed solvent of ethanol, isopropanol or n-propanol. Preferably, the organic solvent B is one or a mixture of N, N-dimethylformamide, N-methylpyrrolidone, and the like. Preferably, the binder is one or more of PVDF, PTFE, Nafion and other organic polymers. The solvent and the binder can form blade coating slurry or spraying slurry with good performance, the blade coating slurry has good adhesiveness, uniform blade coating is convenient to form, and the spraying slurry does not block a spraying machine.
As a further improvement, the mass ratio of the catalyst material to the binder is 20: 1-2: 1, preferably 20:1, 18:1, 15:1, 10:1, 5: 1. The volume ratio of the organic solvent A to the organic solvent B in the blade coating slurry to the spraying slurry is 50: 1-10: 1, preferably 50:1, 40:1, 30:1, 20: 1.
As a further improvement, the sprayed cation exchange membrane is hot-pressed for 1-20min at 80-200 ℃ and 0.1-10MPa, so that the catalyst layer is more firmly attached to the cation exchange membrane, and the stability of the flow battery is improved.
As a further improvement, the blade coating or spray coating process is accompanied by a drying process at 45-120 ℃ to accelerate the volatilization of the solvent.
Example 1
Referring to fig. 1, a polysulfide redox flow battery based on a membrane electrode comprises a battery main body, a positive liquid storage tank and a negative liquid storage tank.
The battery main body includes a cation exchange membrane, a negative electrode, and a positive electrode, which divide the battery main body into left and right chambers. Wherein, the surface of the cation exchange membrane close to one side of the cathode electrode is sprayed with a catalyst layer. The negative electrode also supports a catalyst layer.
The negative electrode chamber of the negative electrode storage tank battery main body is communicated with a pipeline through a pump and is used for storing polysulfide negative electrode solution.
The positive storage tank is communicated with the positive chamber of the battery main body through a pump and a pipeline and is used for storing a positive solution.
Ni loaded with graphene2CoS4(Ni2CoS4@ rGO) as catalyst, 4cm2The carbon felt is used as a positive electrode, and 4cm coated with a catalyst is scraped2The carbon felt is used as a negative electrode, and the N115 membrane with one side sprayed with the catalyst is used as a cation exchange membrane. The loading amount of the catalyst on the negative carbon felt is 18mg/cm2The loading capacity of the catalyst on the surface of the sprayed cation exchange membrane is 9mg/cm2. The positive electrode active material was 10mL of 0.5M Na4[Fe(CN)6]Solutions of. The negative electrode active material was 6mL of 1M Na2S2And (3) solution. And the surface of the N115 film sprayed with the catalyst layer faces to a negative electrode, and the flow battery is assembled by a conventional method.
Ni2CoS4The preparation method of @ rGO comprises the following steps: and (3) ultrasonically dispersing and dissolving the graphene oxide in a solvent, adding thiourea and cobalt nitrate, and uniformly stirring. Heating the mixture in a hydrothermal reaction kettle at 180 ℃ for 20 hours, cooling and washing the mixture for a plurality of times to obtain the product. The concentration of the graphene oxide solution is 1mg/ml, and the mass ratio of the graphene oxide to the cobalt nitrate is 1: 10, the mass ratio of the cobalt nitrate to the sulfur source is 1: 15. The solvent used to dissolve the graphene oxide is ethylene glycol.
The preparation method of the scraping coating slurry and the spraying slurry comprises the following steps: uniformly dispersing the catalyst material in the organic solvent A, simultaneously dissolving the binder in the organic solvent B, mixing the two solutions, and performing ultrasonic dispersion to obtain blade coating slurry or spraying slurry. The organic solvent A is ethanol. The organic solvent B is N, N-dimethylformamide. The binder is PVDF. The mass ratio of the catalyst material to the binder is 10: 1. the volume ratio of the organic solvent A to the organic solvent B in the blade coating slurry to the spraying slurry is 30: 1.
the sprayed ion exchange membrane is hot pressed for 10min at 150 ℃ and 8 MPa.
The blade coating or spraying process is accompanied with a drying process at 90 ℃ so as to accelerate the volatilization of the solvent.
And respectively pumping positive and negative active substances into the positive and negative electrodes, and carrying out constant-current charging and discharging on the battery under different current densities. Finally selecting the current density at 20mA/cm2And (5) carrying out 100-turn long cycle performance test, and obtaining the coulombic efficiency under long cycle according to the charge-discharge capacity ratio.
Example 2
The same procedure as in example 1 was repeated, except that a transition metal-nitrogen-carbon material Fe-N-C was used as a catalyst.
Comparative example 1
By using Ni2CoS4The catalyst was the same as in example 1 except that no graphene was supported.
Comparative example 2
The cation exchange membrane N115 was not sprayed with catalyst (blank without membrane electrode) and the procedure was otherwise the same as in example 1.
Comparative example 3
The procedure is as in example 1 except that no catalyst is used (blank control).
The power density test data for the flow batteries of examples 1-2 and comparative examples 1, 3 are shown in fig. 2.
As can be seen from fig. 2, the power density of the flow batteries of examples 1 and 2 is significantly higher than that of comparative examples 1 and 3, illustrating that Ni supported by graphene is used2CoS4The catalyst can be used as a catalyst, so that the catalytic efficiency of the catalyst can be remarkably improved, and the power density of the flow battery can be further improved. The analysis reason suggests that the graphene can improve the exposure condition of active sites in the transition metal sulfide, so that the utilization rate of the catalyst is increased. The power density of the flow battery in example 2 is significantly higher than that of comparative examples 1 and 3, which shows that the power density of the flow battery can be significantly improved by coating Fe-N-C as a catalyst on the negative electrode side of the cation exchange membrane. The analysis reason is that Fe-N-C is used as a catalyst and coated on one side of the negative electrode of the cation exchange membrane, the distribution area of the catalyst layer is large, the catalytic efficiency is high, meanwhile, the catalyst layer can also inhibit the serious membrane penetrating effect of polysulfide, and the polysulfide redox dynamics and the power density of the battery are improved.
The coulombic efficiencies of the flow batteries of example 1 and comparative example 2 are shown in fig. 3.
As can be seen from fig. 3, the coulombic efficiency and the number of cycles of the flow cell of example 1 are significantly higher than those of comparative example 2, which shows that the coulombic efficiency and the number of cycles of the flow cell can be significantly improved by spraying the catalyst layer on one side of the cation exchange membrane close to the negative electrode. The analysis reason is that the catalyst layer is sprayed on one side surface of the cation exchange membrane close to the negative electrode, the catalyst distribution area is large, the catalytic efficiency is improved, and meanwhile, the catalyst layer can also prevent the membrane penetrating effect of polysulfide.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes may be made to the present invention by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A polysulfide flow battery based on a membrane electrode is characterized in that a first catalyst layer is coated on a negative electrode of the battery in a scraping mode, and a second catalyst layer is sprayed on one side face, close to the negative electrode, of a cation exchange membrane of the battery.
2. The membrane electrode-based polysulfide flow battery of claim 1 wherein the catalyst material of the first and second catalyst layers is graphene-supported transition metal sulfide or transition metal-nitrogen-carbon material.
3. The membrane electrode-based polysulfide flow battery of claim 2 wherein the graphene-supported transition metal sulfide is selected from CoSx@rGO、CuSx@rGO、Ni3S4@rGO、Ni1-xCoxS2@rGO、Ni3-xCoxS4@ rGO.
4. The membrane electrode-based polysulfide flow battery of claim 2 wherein the transition metal-nitrogen-carbon material is selected from one or more of Fe-N-C, Co-N-C, Ni-N-C.
5. The membrane electrode-based polysulfide flow battery of claim 1 wherein the catalyst loading of the first catalyst layer is 2-30mg/cm2The catalyst loading of the second catalyst layer is 1-20mg/cm2。
6. A method of assembling a membrane electrode-based polysulfide flow cell of any one of claims 1 to 5, comprising the steps of:
s1, preparing a catalyst material into blade coating slurry, and blade-coating the slurry on the surface of the negative electrode;
s2, preparing the catalyst material into spraying slurry, and spraying the spraying slurry on the surface of the cation exchange membrane;
and S3, assembling the polysulfide flow battery, and ensuring that the side, sprayed with the catalyst, of the cation exchange membrane faces to the negative electrode.
7. The method of claim 6, wherein the preparing the catalyst material as a draw down slurry or a spray coating slurry is: uniformly dispersing the catalyst material in the organic solvent A, simultaneously dissolving the binder in the organic solvent B, mixing the two solutions, and performing ultrasonic dispersion to obtain blade coating slurry or spraying slurry.
8. The method according to claim 7, wherein the organic solvent A is selected from one or more of ethanol, isopropanol or n-propanol; the organic solvent B is selected from one or more of N, N-dimethylformamide or N-methylpyrrolidone; the binder is selected from one or more of PVDF, PTFE and Nafion.
9. The method of claim 7, wherein the catalyst material and binder are present in a mass ratio of 20: 1-2: 1.
10. the method of claim 6, wherein the sprayed cation exchange membrane is hot pressed at 80 ℃ to 200 ℃ and 0.1 to 10MPa for 1 to 20 min.
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