CN115172774B - Cyano group modified Zr-Fe MOF, preparation method thereof and zinc-based flow battery zinc anode material - Google Patents
Cyano group modified Zr-Fe MOF, preparation method thereof and zinc-based flow battery zinc anode material Download PDFInfo
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Abstract
The invention discloses a cyano group modified Zr-Fe MOF protective layer for a zinc anode of a zinc-based flow battery and a preparation method thereof, and belongs to the technical field of preparation of battery electrode materials. According to the preparation method, a cyano group modifier is introduced in the preparation process of the Zr-Fe MOF nanosheets, so that the high-quality cyano group modified Zr-Fe MOF nanosheets are obtained. The cyano group modified Zr-Fe MOF nanosheets are coated on the surface of a zinc bromine flow zinc cathode to construct a protective layer, so that the problems of dendrite and side reaction existing in zinc electrodeposition in the circulation of the zinc-based flow battery are effectively solved, a feasible strategy is provided for stabilizing future development of the zinc-based flow battery, and opportunities are further provided for the zinc-based flow battery with controllable zinc electrodeposition for large-scale energy storage application.
Description
Technical Field
The invention belongs to the technical field of preparation of battery electrode materials, and relates to a cyano group modified Zr-Fe MOF protective layer for a zinc anode of a zinc-based flow battery and a preparation method thereof. The Zr-Fe MOF nanosheets modified by cyano groups/coated on the surface of the zinc anode of the zinc-based flow battery can solve the problem of short circuit of the battery caused by continuous growth of sharp zinc dendrites penetrating through a diaphragm, and dead Zn can be formed by preventing deposited zinc from peeling off from the surface of the anode, so that the problem of capacity reduction of the battery caused by active material loss is solved, and meanwhile, the problems of side reaction between the surface of the zinc anode and electrolyte are inhibited, so that the practical application of the zinc-based flow battery is further promoted.
Background
As the worldwide demand for clean and renewable energy is becoming more stringent, the use of alternative and sustainable energy types is critical in this situation. The high volatility of the clean energy makes the use of the clean energy worse. In this regard, the development of energy storage systems is critical to provide a more versatile and stable energy supply for industrial applications. In all current energy storage systems, the battery plays an important role.
The zinc-based flow battery is a new generation of low-cost and safe energy storage system device, and the negative electrode of the zinc-based flow battery can be directly composed of a zinc metal negative electrode, which is beneficial to obtaining high capacity. In addition, the compatibility of metallic zinc and aqueous electrolyte is good, and compared with the organic electrolyte which is low in ionic conductivity and highly inflammable in lithium ion battery, the zinc-based flow battery has higher safety and ionic conductivity. However, zinc inhomogeneities during electrodeposition tend to induce zinc dendrite growth, and as the reaction proceeds, further deposition of zinc dendrites will puncture the separator, causing shorting of the cell. The pierced brittle zinc dendrites can form dead crystals in the electrolyte, leading to capacity degradation and even cell failure. In addition, the bare zinc cathode in the battery is directly contacted with the aqueous electrolyte, which can lead to the problem that the zinc cathode is corroded by hydrogen evolution for a long time, and further aggravates the problems of capacity loss, passivation and the like of the zinc cathode. Therefore, the zinc anode interface of the zinc-based flow battery is modified by the composite material, the uniform galvanization of the surface of the zinc anode is controlled deeply, the hydrogen evolution overpotential of the surface of the zinc anode is improved to inhibit side reaction, and the zinc-based flow battery has important significance in promoting the practical application of the zinc-based flow battery.
At present, no research work exists on the aspect of cyano group modified Zr-Fe MOF in the aspect of zinc cathode of zinc-based flow battery. According to our study, zr and Fe metal nodes in the Zr-Fe MOF structure can homogenize the surface electric field of zinc, reduce the fluctuation of the surface electric field of the zinc cathode in the charging process, homogenize the zinc cathodeIs a surface current density of (a). Importantly, a large number of cyano groups on the surface of the Zr-Fe MOF can deeply adsorb the diffused Zn through the modification of cyano groups 2+ While reducing Zn 2+ The desolvation barrier of (2) can be used as Zn by combining with the rich pore canal structure in Zr-Fe MOF 2+ The channel with rapid transmission has the structural advantage that the cyano group modified Zr-Fe MOF can improve Zn affinity of a matrix, reduce energy barrier of Zn nucleation, be beneficial to uniform deposition of Zn, inhibit growth of zinc dendrites and prolong cycle life of a zinc-based flow battery. Meanwhile, the protective layer prevents the zinc cathode from being in direct contact with the aqueous electrolyte, weakens corrosion reaction related to the electrolyte, and further improves the stability of the zinc cathode of the zinc-based flow battery.
Based on the research background, the cyano group modified Zr-Fe MOF nanosheets for the zinc-based flow battery zinc cathode protective layer are efficiently prepared, and the synthesis method is simple, low in cost and easy for large-scale production. The method opens up a new strategy for manufacturing the high-efficiency protective layer for the zinc cathode of the zinc-based flow battery, effectively solves the problems of dendrite growth and hydrogen evolution corrosion of the zinc cathode, and provides valuable guidance for the design and development of the zinc-based flow battery with commercial application value.
Disclosure of Invention
The invention aims to provide a cyano group modified Zr-Fe MOF protective layer for a zinc anode of a zinc-based flow battery and a preparation method thereof in the technical field of preparation of battery electrode materials. The synthesized cyano group modified Zr-Fe MOF nano material has high yield and low cost, and the zinc negative electrode protective layer developed based on the cyano group modified Zr-Fe MOF nano sheet effectively inhibits the zinc dendrite growth and hydrogen evolution corrosion side reaction in the zinc-based flow battery, thereby providing a feasible strategy for stabilizing the future development of the zinc-based flow battery and further providing opportunities for the zinc-based flow battery with controllable zinc electrodeposition for large-scale energy storage application.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a cyano group modified Zr-Fe MOF nano-sheet is prepared by introducing cyano group modifier such as terephthalonitrile and terephthalonitrile into the preparation process of Zr-Fe MOF nano-sheet to pre-cyanate the Zr-Fe MOF nano-sheet, and then continuously using cyano group modifier such as terephthalonitrile and terephthalonitrile to perform stable cyano group modification treatment on the pre-cyanated Zr-Fe MOF nano-sheet to obtain the cyano group modified Zr-Fe MOF nano-sheet. A cyano group modified Zr-Fe MOF nano-sheet is coated on the surface of a zinc bromine flow zinc cathode to construct a protective layer, so that the problems of dendrite and side reaction existing in zinc electrodeposition in the circulation of a zinc-based flow battery can be effectively solved.
Specifically, the cyano group modified Zr-Fe MOF nano-sheet comprises the following steps:
(1) Adding a cyano group modifier in the preparation process of the Zr-Fe MOF nanosheets, fully mixing raw materials required by the preparation of the Zr-Fe MOF nanosheets and the cyano group modifier, carrying out hydrothermal reaction on the mixed solution under the high-temperature oil bath condition, and maintaining the reaction solution at a constant temperature and a high temperature in the reaction process;
(2) Centrifugally collecting the reaction solution obtained in the step (1) to obtain a pre-cyanated Zr-Fe MOF nano-sheet, ultrasonically mixing the pre-cyanated Zr-Fe MOF nano-sheet with a strong alkali solution of a cyano group modifier according to a certain proportion, performing hydrothermal reaction on the mixed solution again under the condition of high-temperature oil bath, and maintaining the reaction solution at high temperature and constant temperature in the reaction process;
(3) And (3) centrifugally collecting the reaction solution obtained in the step (2), washing the precipitate with deionized water for a plurality of times, centrifugally collecting the precipitate again, and drying the precipitate to obtain the cyano group modified Zr-Fe MOF nano-sheet.
In the above technical scheme, further, the raw materials required for preparing the Zr-Fe MOF nanosheets in the step (1) are mixed solution of anhydrous zirconium chloride, ferrocene dicarboxylic acid and acetic acid, the solvent is DMF, the molar ratio of the anhydrous zirconium chloride, ferrocene dicarboxylic acid and acetic acid is 1:1:50, and the concentration of the anhydrous zirconium chloride is 0.03mol L -1 ；
Further, the cyano group modifier in the step (1) is at least one of terephthalonitrile and terephthalonitrile.
In the step (1), the molar ratio of the cyano group modifier to the ferrocene dicarboxylic acid is 0.1:1-0.3:1;
the reaction solution temperature is always maintained at a high temperature of 100-130 ℃ in the reaction process in the step (1);
the strong alkali solution in the step (2) is at least one of sodium hydroxide aqueous solution and potassium hydroxide aqueous solution, and the concentration of the strong alkali is 1-2M;
the concentration of the cyano group modifier in the strong alkali solution of the cyano group modifier in the step (2) is in the range of 0.1-0.3M;
the mass ratio of the pre-cyanated Zr-Fe MOF nano-sheet to the cyano group modifier in the step (2) is 1:1-1:3;
the temperature of the reaction solution is always maintained at a high temperature of 140-160 ℃ in the reaction process in the step (2);
the drying mode of the precipitate in the step (3) is at least one of vacuum drying, forced air drying and freeze drying;
a zinc-based flow battery zinc cathode material is prepared by mixing cyano group modified Zr-Fe MOF nano-sheets prepared in the step (3) with one or more of binders PAN and PVDF solution according to a certain proportion to obtain slurry; and coating the mixed slurry on the surface of zinc, and drying to obtain the zinc anode with the Zr-Fe MOF coating protective layer, which is used for the zinc-based flow battery anode.
In the scheme, the mass ratio of the cyano group modified Zr-Fe MOF nano-sheet to the binder is 1:1-8:1.
The concentration of the binder solution was 10mg ml -1 ～60mg ml -1 ；
The solvent of the binder solution is at least one of DMF and NMP;
according to the preparation method, a cyano group modifier is introduced in the preparation process of the Zr-Fe MOF nanosheets to pre-cyanate the Zr-Fe MOF nanosheets, and then the cyano group modifier is continuously used for carrying out stable cyano group modification treatment on the pre-cyanated Zr-Fe MOF nanosheets on the basis of the pre-cyanated Zr-Fe MOF nanosheets to obtain the controllable-preparation high-quality cyano group modified Zr-Fe MOF nanosheets. Coating a cyano group modified Zr-Fe MOF nano sheet on the surface of a zinc-bromine liquid flow zinc anode to construct a protective layer, and constructing a Zr-Fe MOF structureThe Zr and Fe metal nodes in the zinc anode can homogenize the surface electric field of the zinc, reduce the fluctuation of the surface electric field of the zinc anode in the charging process and homogenize the surface current density of the zinc anode. Importantly, a large number of cyano groups on the surface of the Zr-Fe MOF can deeply adsorb the diffused Zn through the modification of cyano groups 2+ While reducing Zn 2+ The desolvation barrier of (2) can be used as Zn by combining with the rich pore canal structure in Zr-Fe MOF 2+ The channel with rapid transmission has the structural advantage that the cyano group modified Zr-Fe MOF can improve Zn affinity of a matrix, reduce energy barrier of Zn nucleation, be beneficial to uniform deposition of Zn, inhibit growth of zinc dendrites and prolong cycle life of a zinc-based flow battery. Meanwhile, the protective layer prevents the zinc cathode from being in direct contact with the aqueous electrolyte, weakens corrosion reaction related to the electrolyte, and further improves the stability of the zinc cathode of the zinc-based flow battery.
The method has the advantages that:
the growth preparation operation is simple and quick, the cost is low, and expensive material growth equipment is not needed; the Zr-Fe MOF modified by the cyano group prepared by the method has stable morphology and high crystal quality. The cyano group modified Zr-Fe MOF nanosheets are coated on the surface of a zinc bromine flow zinc cathode to construct a protective layer, so that the problems of dendrite and side reactions existing in zinc electrodeposition in the circulation of the zinc-based flow battery can be effectively solved, a feasible strategy is provided for stabilizing future development of the zinc-based flow battery, and important guiding significance is further provided for the zinc-based flow battery with controllable zinc electrodeposition for large-scale energy storage application.
Drawings
FIG. 1 is a projection electron microscope (TEM) image of the cyano group modified Zr-Fe MOF nanoplatelets prepared in example 1;
FIG. 2 is a projection electron microscope (TEM) image of the cyano group modified Zr-Fe MOF nanoplatelets prepared in example 2;
FIG. 3 is an EDS spectrum of the cyano group modified Zr-Fe MOF nanoplatelets prepared in example 1;
FIG. 4 is a coulombic efficiency performance test of the Zn negative electrode of the cyano group-modified Zr-Fe MOF protective layer prepared in example 1;
FIG. 5 is a long-cycle performance test of the cyano group-modified Zr-Fe MOF protective layer prepared in example 1;
FIG. 6 is a cycle performance test of zinc anodes coated with a non-cyanated Zr-Fe MOF protective layer;
FIG. 7 is a cycle performance test of bare Zn negative electrode without any protective layer;
FIG. 8 is a long-cycle performance test of the Zn electrode of the cyano group-modified Zr-Fe MOF protective layer in example 1 under the condition of high current density.
FIG. 9 is a long cycle performance test of Zn negative electrode coated with non-cyanated Zr-Fe MOF protective layer under high current density condition;
FIG. 10 is a long cycle performance test of a bare Zn anode without any protective layer under high current density conditions;
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Example 1:
(1) 3mmol of anhydrous zirconium chloride, 3mmol of ferrocene dicarboxylic acid, and 0.15mol of acetic acid were taken and dissolved in 100mL of DMF.
(2) And (3) putting 0.3mmol of terephthalonitrile into the mixed solution in the step (1), and performing ultrasonic dissolution, wherein the ultrasonic power is 100W, and the time is 1h.
(3) And (3) carrying out hydrothermal reaction on the mixed solution in the step (2) at a constant temperature under the high condition of 120 ℃ oil bath for 12 hours.
(4) Centrifuging the solution after the reaction in the step (3), and collecting precipitate to obtain the pre-cyanated Zr-Fe MOF nano-sheet.
(5) An aqueous sodium hydroxide solution having a concentration of 1M was prepared.
(6) 30ml of the aqueous sodium hydroxide solution (5) was added to terephthalonitrile to prepare a 0.1M terephthalonitrile solution.
(7) Adding all the pre-cyanated Zr-Fe MOF nano-sheets collected in the step (4) into the terephthalonitrile solution in the step (6), and performing ultrasonic assisted dispersion, wherein the ultrasonic power is 200W, and the ultrasonic time is 30min.
(8) And (3) carrying out reaction on the mixed solution obtained in the step (7) under the oil bath condition of 140 ℃ for 2 hours.
(9) Centrifuging the solution reacted in the step (8) to collect precipitate, repeatedly washing the precipitate with deionized water for 3 times, centrifuging again to collect precipitate, and vacuum drying the precipitate at 60 ℃ for 12 hours to obtain the cyano group modified Zr-Fe MOF nanosheets.
(10) Weighing 60mg of cyano group modified Zr-Fe MOF nanosheets in (9), adding 1ml of 10mg ml -1 And (3) mixing the NMP solution of PAN under the magnetic stirring condition, wherein the magnetic stirring rotating speed is 1000rpm, and the stirring time is 24 hours, so as to obtain PAN slurry of the cyano group modified Zr-Fe MOF nano-sheet.
(11) PAN slurry of the cyano group modified Zr-Fe MOF nano sheet in the step (10) is coated on the surface of a zinc anode with the thickness of 15 mu m and the coating speed of 5cmmin by a vacuum flat coater -1 。
(12) And (3) drying the zinc cathode coated with the slurry in the step (11) in a blast drying oven at a drying temperature of 60 ℃ for 12 hours to obtain the zinc cathode with the cyano group modified Zr-Fe MOF nanosheet protective layer, which is used for the zinc-based flow battery cathode.
Example 2:
the same procedure as in example 1 was followed to prepare a cyano group-modified zr—fe MOF nanoplatelet, except that: the terephthalonitrile cyano group modifier in the step of example 1 was changed to terephthalonitrile cyano, and the other reaction conditions were not changed.
TEM characterization shows that the morphology of the cyano group modified Zr-Fe MOF nano-sheet is slightly larger than that of the cyano group modified Zr-Fe MOF nano-sheet (shown in figure 1) prepared in the example 1, and no other substantial difference exists, which indicates that both cyano group modifying agents can obtain the cyano group modified Zr-Fe MOF nano-sheet with uniform morphology.
Example 3:
the same procedure as in example 1 was followed to prepare a cyano group-modified zr—fe MOF nanoplatelet, except that: the 0.1M concentration of terephthalonitrile solution in step (6) of example 1 was changed to 0.3M concentration of terephthalonitrile solution, and the other reaction conditions were not changed.
Characterization and analysis of energy Spectrometry (EDS)
EDS was used to determine if the cyano group was successfully modified in the Zr-Fe MOF nanoplatelet structure. FIG. 3 is an EDS image of the sample of example 1, revealing that the characteristic atom signal nitrogen (N) atom of cyano group is present in the entire cyano group modified Zr-Fe MOF nanoplatelet structure, demonstrating the successful preparation of cyano group modified Zr-Fe MOF nanoplatelets.
Example 4:
a zinc anode coated with a cyano group-modified zr—fe MOF nanoplatelet was prepared by the same procedure as in example 1, except that: 10mg ml in step (10) of example 1 -1 The NMP solution of PAN was changed to 10mg ml -1 The NMP solution of PVDF was unchanged in other reaction conditions.
Coulombic efficiency performance test of cyano group modified Zr-Fe MOF nanosheets coated zinc anode for zinc-based flow battery
FIG. 4 is a battery coulombic efficiency performance test of a zinc anode coated with a cyano group modified Zr-Fe MOF nanoplate of example 1, test current conditions of 5mA cm -2 The galvanization capacity is 1mAh cm -2 The average coulomb efficiency of the zinc anode coated by the cyano group modified Zr-Fe MOF nano-sheet reaches more than 99.68 percent, and the short circuit phenomenon does not occur in 1000 circles of circulation. The cyano group modified Zr-Fe MOF nanosheet protective layer on the surface of the zinc negative electrode effectively inhibits the growth of zinc dendrites in the circulating process of the zinc negative electrode, improves the zinc plating/stripping stability in the long-period circulating process, inhibits side reactions, and greatly improves the effective utilization rate of active zinc.
And (3) testing the cycle performance of the symmetrical battery of the zinc-based flow battery with the cyano group modified Zr-Fe MOF nanosheets coated with the zinc anode.
FIG. 5 is a cyano group of example 1And testing the cycle performance of the electric symmetric battery of the zinc cathode coated by the modified Zr-Fe MOF nano-sheet, wherein the test current condition is 5mA cm -2 The galvanization capacity is 1mAh cm -2 The cycle time of the zinc anode coated by the cyano group modified Zr-Fe MOF nano-sheet reaches 1100 hours, and the short circuit phenomenon does not occur.
In addition, the symmetrical cell cycle performance was also tested under the same conditions using the same method as in example 1 (but without the addition of cyano group modifier for cyanation, i.e., the method was substantially the same as in example 1 but without steps (2) - (8)) for non-cyanated zr—fe MOF nanoplatelet coated zinc anode and bare zinc anode. As shown in fig. 6, which shows the cycling performance of the Zr-Fe MOF nanoplatelets coated with zinc negative electrode without cyano group modification, we found that the battery was short circuited at 550h because zinc dendrite growth penetrated the separator. Fig. 7 shows the cycle performance of a symmetric battery with a bare zinc anode, and the polarization voltage of the battery increases substantially near 50 hours, because the bare zinc anode lacks protection, severe corrosion occurs on the surface, resulting in increased internal resistance, poor cycle stability, and increased voltage polarization. It can be seen that the cycle performance of the zinc negative electrode and the electric symmetric battery coated by adopting the cyano group modified Zr-Fe MOF nanosheets is greatly improved.
To further verify the cycling stability of the cyano group modified Zr-Fe MOF nanoplatelets coated zinc anode, we tested cycling under high current conditions. FIG. 8 shows that cyano group modified Zr-Fe MOF nanoplatelets coated zinc anode at 10mA cm -2 The galvanization capacity is 1mAh cm -2 And (5) testing the cycle performance of the symmetrical battery under the condition. When the current density was increased to 10mA cm -2 When the cyano group modified Zr-Fe MOF nano-sheet coated zinc anode is used, stable circulation can still be realized for 900 hours without dendrite, and the charge-discharge overpotential is maintained at a very low level (100 mV vs. Zn) 2+ /Zn)。
FIG. 9 shows the cycle performance of a zinc negative electrode coated with non-cyanated Zr-Fe MOF nanoplatelets under the same conditions, wherein the voltage fluctuation occurs at 100h and the short circuit condition occurs at about 170 h. Fig. 10 shows the cycling performance of a bare zinc anode under the same conditions at a high current density, and as such, the polarization voltage of the cell increases substantially as the cell cycles for approximately 50 hours. The method shows that the cyanated Zr-Fe MOF protective layer on the surface of the zinc anode plays a prominent role in promoting uniform deposition of Zn, improving Zn affinity of a matrix and reducing energy barrier of Zn nucleation. Meanwhile, the protective layer prevents the zinc cathode from being in direct contact with the aqueous electrolyte, weakens corrosion reaction related to the electrolyte, and further improves the stability of the zinc cathode of the zinc-based flow battery.
In conclusion, the cyano group modified Zr-Fe MOF protective layer for the zinc negative electrode of the zinc-based flow battery and the preparation method thereof provided by the invention effectively inhibit the growth of zinc dendrite and the occurrence of hydrogen evolution side reaction, and the prepared zinc negative electrode shows long-period circulation stability.
Claims (8)
1. A preparation method of cyano group modified Zr-Fe MOF is characterized by comprising the following steps:
(1) Fully mixing raw materials required by preparing Zr-Fe MOF nanosheets and cyano group modifier, carrying out hydrothermal reaction on the mixed solution under the condition of high-temperature oil bath, and maintaining the reaction solution at a constant temperature and a high temperature in the reaction process; the Zr-Fe MOF nanosheets are prepared from mixed solution of anhydrous zirconium chloride, ferrocene dicarboxylic acid and acetic acid, wherein the solvent is DMF, the molar ratio of the anhydrous zirconium chloride, the ferrocene dicarboxylic acid and the acetic acid is 1:1:50, and the concentration of the anhydrous zirconium chloride is 0.03mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the The cyano group modifier is at least one of terephthalonitrile and terephthalonitrile, and the molar ratio of the cyano group modifier to ferrocene dicarboxylic acid is 0.1:1-0.3:1;
(2) Centrifugally collecting the reaction solution obtained in the step (1) to obtain a pre-cyanated Zr-Fe MOF nano-sheet, ultrasonically mixing the pre-cyanated Zr-Fe MOF nano-sheet with a strong alkali solution of a cyano group modifier according to a certain proportion, performing hydrothermal reaction on the mixed solution again under the condition of high-temperature oil bath, and maintaining the reaction solution at high temperature and constant temperature in the reaction process;
(3) And (3) centrifugally collecting the reaction solution obtained in the step (2), washing the precipitate with deionized water for a plurality of times, centrifugally collecting the precipitate again, and drying the precipitate to obtain the cyano group modified Zr-Fe MOF nano-sheet.
2. The method for preparing a cyano group modified Zr-Fe MOF according to claim 1, wherein the reaction solution temperature is maintained at a high temperature of 100-130 ℃ all the time in the reaction process in the step (1).
3. The method for preparing a cyano group modified Zr-Fe MOF according to claim 1, wherein the strong alkali solution in step (2) is at least one of aqueous sodium hydroxide solution and aqueous potassium hydroxide solution, and the concentration of strong alkali is 1-2M; the concentration of the cyano group modifier in the strong base solution of the cyano group modifier ranges from 1 to 3M.
4. The method for preparing cyano-group modified Zr-Fe MOF according to claim 1, wherein the molar ratio of the pre-cyanated Zr-Fe MOF nanosheets to the cyano-group modifier in the step (2) is 1:1-1:3.
5. The method for preparing a cyano group modified Zr-Fe MOF according to claim 1, wherein the reaction solution temperature is maintained at a high temperature of 140-160 ℃ all the time in the reaction process in the step (2).
6. A zinc-based flow battery zinc cathode material, which is characterized in that cyano group modified Zr-Fe MOF nano-sheets prepared by the method of any one of claims 1-5 are mixed with one or more of binder PAN and PVDF solution according to a certain proportion to obtain slurry; and coating the mixed slurry on the surface of zinc, and drying to obtain the zinc anode with the Zr-Fe MOF coating protective layer, which is used for the zinc-based flow battery anode.
7. The zinc-based flow battery zinc anode material according to claim 6, wherein the mass ratio of the cyano group modified Zr-Fe MOF nanosheets to the binder is 1:1-8:1.
8. A zinc-based flow battery comprising the zinc anode material of claim 6.
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| CN202210671797.2A CN115172774B (en) | 2022-06-14 | 2022-06-14 | Cyano group modified Zr-Fe MOF, preparation method thereof and zinc-based flow battery zinc anode material |
| PCT/CN2022/128493 WO2023240891A1 (en) | 2022-06-14 | 2022-10-31 | Cyano group-modified zr-fe mof, preparation method therefor, and zinc-based flow battery zinc negative electrode material |
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| CN115172774B (en) * | 2022-06-14 | 2023-08-11 | 浙江大学 | Cyano group modified Zr-Fe MOF, preparation method thereof and zinc-based flow battery zinc anode material |
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| CN112707413A (en) * | 2020-12-29 | 2021-04-27 | 佛山仙湖实验室 | Preparation method and application of high-crystallinity Prussian blue micro-flower electrode material |
| CN113121836A (en) * | 2021-03-04 | 2021-07-16 | 华南师范大学 | Nano-framework-shaped super-structure Fe-Co-Ni metal organic framework and preparation method and application thereof |
| CN113856635A (en) * | 2021-10-25 | 2021-12-31 | 中国科学院长春应用化学研究所 | Macro-size continuous MOF (metal organic framework) membrane material as well as preparation method and application thereof |
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