CN119252838B - Fluorine-substituted graphylene-protected zinc-ion secondary battery zinc anode, its preparation method and application - Google Patents
Fluorine-substituted graphylene-protected zinc-ion secondary battery zinc anode, its preparation method and applicationInfo
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Abstract
本发明提供了一种氟取代石墨炔保护的锌离子二次电池锌负极及其制备方法和应用。制备方法包括：(1)配制反应液，其中，反应液包括1,3,5‑三氟‑2,4,6‑三炔基苯，碘化亚铜，吡啶，四氢呋喃和N,N,N’,N’‑四甲基乙二胺；(2)以锌箔为基底，在反应液中1,3,5‑三氟‑2,4,6‑三炔基苯发生交叉偶联反应，在锌箔表面原位制备出所述氟取代石墨炔保护的锌离子二次电池锌负极。本发明所提出的制备方法，通过原位制备方法在锌箔表面可控生长氟取代石墨炔，该制备方法条件温和、操作简单且适于大规模制备。并且，制备出的氟取代石墨炔保护的锌离子二次电池锌负极，可作为锌离子二次电池的一种新负极材料使用，抑制锌枝晶生长，缓解析氢反应，从而显著提高锌离子二次电池的循环寿命。
This invention provides a zinc anode for a zinc-ion secondary battery protected by fluorine-substituted graphyne, its preparation method, and its application. The preparation method includes: (1) preparing a reaction solution, wherein the reaction solution includes 1,3,5-trifluoro-2,4,6-triynylbenzene, cuprous iodide, pyridine, tetrahydrofuran, and N,N,N',N'-tetramethylethylenediamine; (2) using zinc foil as a substrate, 1,3,5-trifluoro-2,4,6-triynylbenzene undergoes a cross-coupling reaction in the reaction solution, thereby preparing the fluorine-substituted graphyne-protected zinc anode for a zinc-ion secondary battery in situ on the zinc foil surface. The preparation method proposed in this invention allows for the controlled growth of fluorine-substituted graphyne on the zinc foil surface through an in-situ preparation method. This preparation method is mild, simple to operate, and suitable for large-scale preparation. Furthermore, the prepared fluorine-substituted graphyne-protected zinc anode for a zinc-ion secondary battery can be used as a new anode material for zinc-ion secondary batteries, inhibiting zinc dendrite growth and slowing down hydrogen release reactions, thereby significantly improving the cycle life of zinc-ion secondary batteries.
Description
Technical Field
The invention belongs to the technical field of nano materials and preparation, and particularly relates to a fluorine substituted graphite alkyne-protected zinc anode of a zinc ion secondary battery, and a preparation method and application thereof. More particularly, the invention relates to a zinc anode of a fluorine-substituted graphite alkyne-protected zinc ion secondary battery, a preparation method thereof and a zinc ion secondary battery using the same.
Background
At present, development of a novel secondary battery has become an important solution for human coping with energy and environmental problems. Among a plurality of novel secondary battery systems, the zinc ion secondary battery is widely focused on due to the advantages of abundant reserve, low price, high specific capacity, environmental friendliness, safety, stability and the like, and brings brand-new opportunities and challenges for the development of the novel secondary battery.
The negative electrode material of the zinc ion secondary battery generally uses zinc metal, and can be directly used for the negative electrode assembly of the zinc ion secondary battery due to convenient processing, low cost, good conductivity, safety and environmental protection. In recent years, a series of studies on negative electrode materials for zinc ion secondary batteries have been reported （Zheng, J.;Zhao, Q.;Tang, T.;Yin, J.;Quilty, C. D.;Renderos, G. D.;Liu, X.;Deng, Y.;Wang, L.;Bock, D. C.;Jaye, C.;Zhang, D.;Takeuchi, E. S.;Takeuchi, K. J.;Marschilok, A. C.;Archer, L. A., Reversible epitaxial electrodeposition of metals in battery anodes. Science 2019, 366(6465), 645-648; Zhao, Z.;Zhao, J.;Hu, Z.;Li, J.;Li, J.;Zhang, Y.;Wang, C.;Cui, G., Long-life and deeply rechargeable aqueous Zn anodes enabled by a multifunctional brightener-inspired interphase. Energy Environ. Sci. 2019, 12(6), 1938-1949; Zeng, Y.;Zhang, X.;Qin, R.;Liu, X.;Fang, P.;Zheng, D.;Tong, Y.;Lu, X., Dendrite-Free Zinc Deposition Induced by Multifunctional CNT Frameworks for Stable Flexible Zn-Ion Batteries. Adv. Mater. 2019, 31(36), 1903675; Yu, M.;Chandrasekhar, N.;Raghupathy, R. K. M.;Ly, K. H.;Zhang, H.;Dmitrieva, E.;Liang, C.;Lu, X.;Kühne, T. D.;Mirhosseini, H.;Weidinger, I. M.;Feng, X., A High-Rate Two-Dimensional Polyarylimide Covalent Organic Framework Anode for Aqueous Zn-Ion Energy Storage Devices. J. Am. Chem. Soc. 2020, 142(46), 19570-19578; Wang, C.;Wang, D.;Lv, D.;Peng, H.;Song, X.;Yang, J.;Qian, Y., Interface Engineering by Hydrophilic and Zincophilic Aluminum Hydroxide Fluoride for Anode-Free Zinc Metal Batteries at Low Temperature. Adv. Energy Mater. 2023, 13(20), 2204388; Luo, J.;Xu, L.;Zhou, Y.;Yan, T.;Shao, Y.;Yang, D.;Zhang, L.;Xia, Z.;Wang, T.;Zhang, L.;Cheng, T.;Shao, Y., Regulating the Inner Helmholtz Plane with a High Donor Additive for Efficient Anode Reversibility in Aqueous Zn-Ion Batteries. Angew. Chem. Int. Ed. 2023, 62(21), e202302302.）, these studies providing a great deal of experience for the development of negative electrodes for zinc ion secondary batteries.
However, the zinc metal cathode still has the problems that zinc dendrites are easy to pierce through a diaphragm to cause short circuit of the battery, and hydrogen evolution side reaction is easy to occur to cause electrolyte loss and the like in the battery cycle process. These problems seriously affect the cycle life of the zinc ion secondary battery.
Accordingly, there is still a need for improvement in the negative electrode material of the zinc ion secondary battery at this stage.
Disclosure of Invention
Aiming at the problems of dendrite, side reaction and the like of the zinc ion battery cathode material at the present stage, the inventor discovers that fluorine substituted graphite alkyne is formed into a conjugated structure by connecting a diacetylenic bond with fluorine substituted benzene ring in the research process, and has zinc-philic fluorine atoms and uniformly distributed macropores. Based on the method, the fluorine-substituted graphite alkyne-protected zinc ion secondary battery zinc anode obtained by the in-situ preparation method is used as a zinc ion battery anode material, and can inhibit zinc dendrite growth and hydrogen evolution side reaction at the same time, so that the cycle life of the zinc ion secondary battery is obviously prolonged.
In view of the above, an object of the present invention is to provide a simple and easy method for mass-producing a zinc anode for a fluorine-substituted graphite alkyne-protected zinc ion secondary battery.
The method for preparing the zinc anode of the fluorine substituted graphite alkyne-protected zinc ion secondary battery provided by the invention comprises the following steps:
(1) Preparing a reaction solution, wherein the reaction solution comprises 1,3, 5-trifluoro-2, 4, 6-trialkynylbenzene, cuprous iodide, pyridine, tetrahydrofuran and N, N, N ', N' -tetramethyl ethylenediamine;
(2) Taking zinc foil as a substrate, cuprous iodide as a catalyst, tetrahydrofuran as a solvent, N, N, N ', N' -tetramethyl ethylenediamine as a solvent and alkali simultaneously, and pyridine as alkali, wherein 1,3, 5-trifluoro-2, 4, 6-trialkynyl benzene in the reaction liquid undergoes cross coupling reaction, and the zinc anode of the zinc ion secondary battery protected by fluorine substituted graphite alkyne is prepared in situ on the surface of the zinc foil.
The inventor finds that the fluorine is controllably grown on the surface of the zinc foil to replace graphite alkyne through an in-situ preparation method, and the preparation method has mild conditions and simple operation and is suitable for large-scale preparation. And the prepared zinc anode of the zinc ion secondary battery protected by fluorine substituted graphite alkyne can be used as a novel anode material of the zinc ion secondary battery, inhibit zinc dendrite growth and relieve hydrogen evolution reaction, thereby remarkably prolonging the cycle life of the zinc ion secondary battery.
In the step (1) of the method, the weight ratio of the 1,3, 5-trifluoro-2, 4, 6-trialkynylbenzene, cuprous iodide, pyridine, tetrahydrofuran and N, N, N ', N' -tetramethyl ethylenediamine in the reaction liquid can be 10 (1-2): (197-393): (8900-17800): (7750-15500) in sequence.
In one embodiment of the invention, the weight ratio of 1,3, 5-trifluoro-2, 4, 6-trialkynylbenzene, cuprous iodide, pyridine, tetrahydrofuran and N, N, N ', N' -tetramethyl ethylenediamine in the reaction solution is 10:1:197:13350:11625 in sequence;
in one embodiment of the invention, the weight ratio of 1,3, 5-trifluoro-2, 4, 6-trialkynylbenzene, cuprous iodide, pyridine, tetrahydrofuran and N, N, N ', N' -tetramethyl ethylenediamine in the reaction solution is 10:1:197:8900:7750 in sequence;
in one embodiment of the invention, the weight ratio of 1,3, 5-trifluoro-2, 4, 6-trialkynylbenzene, cuprous iodide, pyridine, tetrahydrofuran and N, N, N ', N' -tetramethyl ethylenediamine in the reaction solution is 10:2:393:13350:11625 in sequence.
In the step (2), the reaction temperature of the in-situ preparation is 50+/-10 ℃;
in one embodiment of the invention, the reaction temperature of the in situ preparation is 50 degrees celsius;
The reaction time of the in-situ preparation is 36-60 hours;
in one embodiment of the invention, the reaction time for the in situ preparation is 48 hours;
In one embodiment of the invention, the reaction time for the in situ preparation is 36 hours;
In one embodiment of the invention, the reaction time for the in situ preparation is 60 hours.
Another object of the invention is to provide a zinc anode of a zinc ion secondary battery protected by fluorine substituted graphite alkyne.
The zinc cathode of the fluorine substituted graphite alkyne-protected zinc ion secondary battery is prepared by the method.
The inventor finds that the fluorine substituted graphite alkyne protected zinc ion secondary battery zinc cathode prepared by the invention can be used as a novel cathode material of the zinc ion secondary battery, inhibit zinc dendrite growth, and relieve hydrogen evolution reaction, thereby remarkably prolonging the cycle life of the zinc ion secondary battery.
Those skilled in the art will appreciate that the features and advantages described above for the method of preparing a zinc anode for a fluorine substituted graphite alkyne protected zinc ion secondary battery are applicable to the zinc anode for a fluorine substituted graphite alkyne protected zinc ion secondary battery, and will not be described in detail herein.
The invention also provides a zinc ion secondary battery.
The zinc ion secondary battery comprises a negative electrode, and the negative electrode is the zinc negative electrode of the zinc ion secondary battery protected by the fluorine substituted graphite alkyne.
The inventor finds that the negative electrode of the zinc ion secondary battery is formed by the zinc negative electrode of the zinc ion secondary battery protected by fluorine substituted graphite alkyne through research, and can inhibit zinc dendrite growth and relieve hydrogen evolution reaction, so that the cycle life of the zinc ion secondary battery is obviously prolonged.
Drawings
FIG. 1 is a flow chart of a method for preparing a zinc anode of a fluorine substituted graphite alkyne-protected zinc ion secondary battery in accordance with an embodiment of the present invention;
FIG. 2 is a schematic illustration of a chemical reaction according to an embodiment of the present invention;
FIG. 3 is a photograph of a zinc anode of a fluorine substituted graphite alkyne-protected zinc ion secondary battery prepared in accordance with an embodiment of the present invention;
FIG. 4 is an SEM photograph of a zinc anode of a fluorine substituted graphite alkyne-protected zinc ion secondary battery prepared in the example of the present invention;
FIG. 5 is a Raman spectrum of a zinc anode of a fluorine substituted graphite alkyne-protected zinc ion secondary battery prepared by an embodiment of the invention;
FIG. 6 is a photoelectron spectroscopy analysis chart of a zinc anode of a zinc ion secondary battery protected by fluorine substituted graphite alkyne prepared by the embodiment of the invention;
FIG. 7 is a graph showing a comparison of the battery cycle performance test of the comparative example of the present invention and the example;
FIG. 8 is a SEM photograph of a comparative example of the present invention compared with an example after battery cycling;
fig. 9 is a graph of a comparison of linear sweep voltammetry tests for comparative and example examples of the present invention.
Detailed Description
The following detailed description of the invention is provided in connection with the accompanying drawings that are presented to illustrate the invention and not to limit the scope thereof. The examples provided below are intended as guidelines for further modifications by one of ordinary skill in the art and are not to be construed as limiting the invention in any way.
The experimental methods in the following examples, unless otherwise specified, are conventional methods, and are carried out according to techniques or conditions described in the literature in the field or according to the product specifications. Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
In one aspect, the invention provides a method for preparing a zinc anode of a fluorine substituted graphite alkyne-protected zinc ion secondary battery. The preparation method of the present invention will be described in detail with reference to fig. 1.
According to an embodiment of the present invention, referring to fig. 1, the preparation method includes:
S100, preparing a reaction solution.
In the step, a reaction solution is prepared, wherein the weight ratio of 1,3, 5-trifluoro-2, 4, 6-trialkynylbenzene, cuprous iodide, pyridine, tetrahydrofuran and N, N, N ', N' -tetramethyl ethylenediamine is 10 (1-2): (197-393): (8900-17800): (7750-15500). Thus, the reaction liquid formed by adopting the proportion can obtain the zinc cathode of the zinc ion secondary battery protected by the fluorine substituted graphite alkyne through in-situ reaction. According to the embodiment of the present invention, the specific method for forming the reaction solution is not particularly limited, and specifically, for example, cuprous iodide may be dispersed in a mixed solution of tetrahydrofuran and N, N' -tetramethyl ethylenediamine, and 1,3, 5-trifluoro-2, 4, 6-trialkynylbenzene and pyridine may be added after ultrasonic dissolution. The degree of dispersion of the reaction solution can be adjusted by those skilled in the art accordingly.
In some embodiments of the invention, the weight ratio of1, 3, 5-trifluoro-2, 4, 6-trialkynylbenzene, cuprous iodide, pyridine, tetrahydrofuran and N, N, N ', N' -tetramethyl ethylenediamine is 10 (1-2): (197-393): (8900-17800): (7750-15500), so that the zinc anode of the zinc ion secondary battery protected by fluorine substituted graphite alkyne can be successfully prepared. In addition, the inventor also found through long-term researches that if the content of cuprous iodide and pyridine is lower than the above ratio, or the content of tetrahydrofuran and N, N, N ', N' -tetramethyl ethylenediamine is higher than the above ratio, the reaction degree of1, 3, 5-trifluoro-2, 4, 6-trialkynylbenzene is low, a compact fluorine substituted graphite alkyne protective layer is difficult to form, and if the content of cuprous iodide and pyridine is higher than the above ratio, or the content of tetrahydrofuran and N, N, N ', N' -tetramethyl ethylenediamine is lower than the above ratio, the 1,3, 5-trifluoro-2, 4, 6-trialkynylbenzene is preferentially reacted in the solution, and the compact fluorine substituted graphite alkyne protective layer is also difficult to form, and the waste of reactants is caused. In some specific examples, the weight ratio of1, 3, 5-trifluoro-2, 4, 6-trialkynylbenzene, cuprous iodide, pyridine, tetrahydrofuran and N, N, N ', N' -tetramethyl ethylenediamine is 10:1:197:13350:11625, so that the zinc anode of the zinc ion secondary battery protected by the fluorine substituted graphite alkyne with higher quality can be obtained efficiently.
And S200, preparing the zinc anode of the zinc ion secondary battery protected by the fluorine substituted graphite alkyne in situ in the reaction solution by taking the zinc foil as a substrate.
In the step, zinc foil is used as a substrate, and a zinc anode of the zinc ion secondary battery protected by fluorine substituted graphite alkyne is prepared in situ in the reaction liquid prepared in the step S100.
According to the embodiment of the invention, the specific size of the zinc foil and the specific conditions for in-situ preparation are not particularly limited, and the person skilled in the art can correspondingly adjust according to the specific electrical performance result of the prepared zinc anode of the zinc ion secondary battery protected by fluorine substituted graphite alkyne. In some embodiments of the invention, the zinc foil may be square with a thickness of 0.1 mm and a side length of 23 mm, and the in situ preparation may be performed at 50±10 degrees celsius. Therefore, the condition of preparing the zinc anode of the zinc ion secondary battery protected by the fluorine substituted graphite alkyne in situ at the temperature of 50+/-10 ℃ is milder, the energy consumption is lower, and the quality of the fluorine substituted graphite alkyne protective layer of the zinc anode of the zinc ion secondary battery protected by the fluorine substituted graphite alkyne prepared under the size is better.
In some embodiments of the invention, the in-situ preparation time can be 36-60 hours, so that the zinc anode of the zinc ion secondary battery protected by the fluorine-substituted graphite alkyne prepared in-situ by adopting the time range has better electrochemical performance. In addition, the inventor discovers through long-term research that if the in-situ preparation time is less than 36 hours, the reaction degree of 1,3, 5-trifluoro-2, 4, 6-trialkynyl benzene is low, fluorine substituted graphite alkyne can only form a loose structure, and if the in-situ preparation time is more than 60 hours, the fluorine substituted graphite alkyne layer obtained by the reaction is too thick, and the electrochemical performance of the zinc anode of the zinc ion secondary battery protected by the fluorine substituted graphite alkyne is reduced. In some specific examples, the in-situ preparation time can be 48 hours, so that the zinc anode of the fluorine-substituted graphite alkyne-protected zinc ion secondary battery with excellent electrochemical performance can be prepared in-situ more efficiently.
In summary, according to the embodiment of the invention, the preparation method is provided, and the fluorine substituted graphite alkyne protective layer can be grown on the surface of the zinc foil in situ by the in-situ preparation method. And the prepared zinc anode of the zinc ion secondary battery protected by fluorine substituted graphite alkyne can be used as a novel anode material of the zinc ion secondary battery, inhibit zinc dendrite growth and relieve hydrogen evolution reaction, thereby remarkably prolonging the cycle life of the zinc ion secondary battery.
In another aspect of the invention, the invention provides a zinc anode of a fluorine substituted graphite alkyne-protected zinc ion secondary battery.
According to an embodiment of the present invention, the fluorine substituted graphite alkyne-protected zinc anode of the zinc ion secondary battery is prepared by the above-described method.
In summary, according to the embodiment of the invention, the zinc anode of the zinc ion secondary battery protected by fluorine substituted graphite alkyne is provided and used as a negative electrode material of the zinc ion secondary battery, and can inhibit zinc dendrite growth and relieve hydrogen evolution reaction, so that the cycle life of the zinc ion secondary battery is obviously prolonged. Those skilled in the art will appreciate that the features and advantages described above for the method of preparing a zinc anode for a fluorine substituted graphite alkyne protected zinc ion secondary battery are applicable to the zinc anode for a fluorine substituted graphite alkyne protected zinc ion secondary battery, and will not be described in detail herein.
In another aspect of the present invention, a zinc ion secondary battery is provided.
According to an embodiment of the present invention, the zinc ion secondary battery includes a negative electrode, and the negative electrode is formed of the zinc ion secondary battery zinc negative electrode protected by the above-described fluorine substituted graphite alkyne.
In summary, according to the embodiments of the present invention, the present invention provides a zinc ion secondary battery, in which the negative electrode is formed by a zinc ion secondary battery zinc negative electrode protected by fluorine substituted graphite alkyne, and can inhibit zinc dendrite growth, alleviate hydrogen evolution reaction, and thereby significantly improve the cycle life of the zinc ion secondary battery. Those skilled in the art will appreciate that the features and advantages described above for the fluorine substituted graphite alkyne protected zinc ion secondary battery zinc anode are applicable to the zinc ion secondary battery and will not be described in detail herein.
The 1,3, 5-trifluoro-2, 4, 6-trialkynylbenzene used in the examples described below can be synthesized by reference to the following documents ：Wang, Y.; Wei, S.; Qi, Z.-H.; Chen, S.; Zhu, K.; Ding, H.; Cao, Y.; Zhou, Q.; Wang, C.; Zhang, P.; Guo, X.; Yang, X.; Wu, X.; Song, L., Intercalant-induced Vt2gorbital occupation in vanadium oxide cathode toward fast-charging aqueous zinc-ion batteries. PNAS 2023, 120(13), e2217208120..
The ammonium-doped vanadium pentoxide used in the examples below can be synthesized by reference to the following documents ：Xing, C.; Xue, Y.; Huang, B.; Yu, H.; Hui, L.; Fang, Y.; Liu, Y.; Zhao, Y.; Li, Z.; Li, Y., Fluorographdiyne: A Metal-Free Catalyst for Applications in Water Reduction and Oxidation. Angew. Chem. Int. Ed. 2019, 58(39), 13897-13903..
Example 1
In this example, a zinc anode of a fluorine substituted graphite alkyne-protected zinc ion secondary battery was prepared.
The specific method is that 1.0 mg cuprous iodide is ultrasonically dissolved in a mixed solvent of 15mL tetrahydrofuran and 15mL of N, N, N ', N' -tetramethyl ethylenediamine, and then 0.25 mL pyridine and 10 mg of 1,3, 5-trifluoro-2, 4, 6-tri-alkynyl benzene, namely 1,3, 5-trifluoro-2, 4, 6-tri-alkynyl benzene, are added, and the weight ratio of the cuprous iodide to the pyridine to the tetrahydrofuran to the N, N, N ', N' -tetramethyl ethylenediamine is 10:1:197:13350:11625. And after uniformly mixing, placing square zinc foil with the thickness of 0.1 mm and the side length of 23: 23 mm into the reaction liquid, and reacting for 48 hours at 50 ℃ to obtain the zinc anode of the zinc ion secondary battery protected by fluorine substituted graphite alkyne.
The chemical reaction schematic diagram involved in the example is shown in fig. 2, and the photograph of the obtained zinc negative electrode of the fluorine substituted graphite alkyne protected zinc ion secondary battery is shown in fig. 3.
Then, scanning Electron Microscope (SEM), raman spectroscopy, and photoelectron spectroscopy analysis were performed on the zinc anode of the fluorine-substituted graphite alkyne-protected zinc ion secondary battery of the example. The SEM photograph, the Raman spectrum and the energy spectrum analysis chart of the embodiment are respectively shown in figures 4-6, which shows that the preparation method successfully prepares the zinc cathode of the zinc ion secondary battery protected by fluorine substituted graphite alkyne. FIGS. 4-6 demonstrate successful synthesis of fluorine substituted graphite alkyne materials.
Example 2
In this example, 1.0 mg cuprous iodide was sonicated in a mixed solvent of 10 mL tetrahydrofuran and 10 mL of N, N, N ', N' -tetramethyl ethylenediamine, and then 0.25 mL pyridine and 10 mg of 1,3, 5-trifluoro-2, 4, 6-trialkynylbenzene, i.e., 1,3, 5-trifluoro-2, 4, 6-trialkynylbenzene, cuprous iodide, pyridine, tetrahydrofuran and N, N, N ', N' -tetramethyl ethylenediamine were added in a weight ratio of 10:7751:197:8900:0, in substantially the same manner and under the same conditions as in example 1. And after uniformly mixing, placing the zinc foil into a reaction solution, and reacting for 48 hours at 50 ℃ to obtain the zinc anode of the zinc ion secondary battery protected by fluorine substituted graphite alkyne.
Example 3
In this example, 2.0 mg of cuprous iodide was ultrasonically dissolved in a mixed solvent of 15 mL tetrahydrofuran and 15 mL of N, N, N ', N' -tetramethyl ethylenediamine, and then 0.50 of mL pyridine and 10 mg of 1,3, 5-trifluoro-2, 4, 6-trialkynylbenzene, i.e., 1,3, 5-trifluoro-2, 4, 6-trialkynylbenzene, cuprous iodide, pyridine, tetrahydrofuran and N, N, N ', N' -tetramethyl ethylenediamine were added at a weight ratio of 10:2:393:13350:11625, according to substantially the same method and conditions as in example 1. And after uniformly mixing, placing the zinc foil into a reaction solution, and reacting for 48 hours at 50 ℃ to obtain the zinc anode of the zinc ion secondary battery protected by fluorine substituted graphite alkyne.
Example 4
In this example, 1.0 mg of cuprous iodide was ultrasonically dissolved in a mixed solvent of 15mL of tetrahydrofuran and 15mL of N, N, N ', N' -tetramethyl ethylenediamine, and then 0.25 of mL pyridine and 10 mg of 1,3, 5-trifluoro-2, 4, 6-trialkynylbenzene, i.e., 1,3, 5-trifluoro-2, 4, 6-trialkynylbenzene, cuprous iodide, pyridine, tetrahydrofuran and N, N, N ', N' -tetramethyl ethylenediamine were added at a weight ratio of 10:1:197:13350:11625, according to substantially the same method and conditions as in example 1. And (3) after uniformly mixing, placing the zinc foil into a reaction solution, and reacting for 36 hours at 50 ℃ to obtain the zinc anode of the zinc ion secondary battery protected by fluorine substituted graphite alkyne.
Example 5
In this example, 1.0 mg of cuprous iodide was ultrasonically dissolved in a mixed solvent of 15mL of tetrahydrofuran and 15mLN, N, N ', N' -tetramethyl ethylenediamine, and then 0.25 of mL pyridine and 10 mg of 1,3, 5-trifluoro-2, 4, 6-trialkynylbenzene, i.e., 1,3, 5-trifluoro-2, 4, 6-trialkynylbenzene, cuprous iodide, pyridine, tetrahydrofuran and N, N, N ', N' -tetramethyl ethylenediamine were added in a weight ratio of 10:1:197:13350:11625, according to substantially the same method and conditions as in example 1. And (3) after uniformly mixing, placing the zinc foil into a reaction solution, and reacting for 60 hours at 50 ℃ to obtain the zinc anode of the zinc ion secondary battery protected by fluorine substituted graphite alkyne.
Example 6
In this example, the fluorine substituted graphite alkyne protected zinc ion secondary battery zinc anode prepared in example 1 was pressed into a round negative electrode sheet having a diameter of 10 mm. Ammonium doped vanadium pentoxide is used as an anode, qualitative filter paper is used as a diaphragm, and 3M zinc trifluoromethane sulfonate aqueous solution is used as electrolyte to assemble the 2032 button cell.
Comparative example 1
In this comparative example, a 2032-type button cell was assembled with zinc foil as the negative electrode, ammonium-doped vanadium pentoxide as the positive electrode, qualitative filter paper as the separator, and 3M zinc trifluoromethane sulfonate aqueous solution as the electrolyte.
Example 7
In this example, the zinc anode of the zinc ion secondary battery protected by fluorine-substituted graphite alkyne prepared in example 1 was cut into square electrode pieces with a side length of 10 mm as working electrodes. The three-electrode system is assembled by using a silver/silver chloride electrode as a reference electrode, a carbon rod as a counter electrode and a 1M zinc sulfate aqueous solution as an electrolyte.
Comparative example 2
In this comparative example, a three-electrode system was assembled using zinc foil as the working electrode, a silver/silver chloride electrode as the reference electrode, a carbon rod as the counter electrode, and 1M aqueous zinc sulfate as the electrolyte.
Example 8
In this example, electrochemical performance tests were performed on the button cell of example 6 and the button cell of comparative example 1, and the three-electrode system of example 7 and the three-electrode system of comparative example 2, respectively. Specifically, the coin cell of example 6 and the coin cell of comparative example 1 were tested for cycle performance at a current density of 1A g -1, and the three electrode system of example 7 and the three electrode system of comparative example 2 were tested for linear sweep voltammetry at a sweep rate of 10 mV s -1. The test results show that:
Referring to fig. 7, the button cell of comparative example 1 had a maximum cell specific capacity of 205.2 mA h g -1, a cycle life of 475 times, and a capacity retention of 43.1% at a current density of 1A g -1. The button cell of example 6 had a maximum cell specific capacity of 214.3 mA h g -1, a cycle life of 2000 times, and a capacity retention of 67.3% at a current density of 1A g -1. The cycle performance test demonstrates that the cell of example 6 has a significantly improved cycle life compared to the cell of comparative example 1.
Referring to fig. 8, the negative electrode of comparative example 1 grew a large amount of zinc dendrites after battery cycling, and the negative electrode of example 6 was flat in morphology after battery cycling. SEM photographs showed that the negative electrode of example 6 was effective in inhibiting zinc dendrite growth.
Referring to fig. 9, the corresponding potential is-1.356, V when the current density of comparative example 2 reaches-50, mA cm -2 at a sweep rate of 10 mV s -1, and-1.395, V when the current density of example 7 reaches-50, mA cm -2. The results of the linear sweep voltammetric test demonstrate that the working electrode of example 7 has a greater hydrogen evolution potential than the working electrode of comparative example 2, and that the working electrode of example 7 has a greater ability to inhibit hydrogen evolution reactions than the working electrode of comparative example 2.
The preparation method provided by the invention can be used for controllably growing fluorine to replace graphite alkyne on the surface of zinc foil by an in-situ preparation method, and has the advantages of mild condition, simple operation and suitability for large-scale preparation. The prepared zinc anode of the zinc ion secondary battery protected by the fluorine substituted graphite alkyne can be used as a novel anode material of the zinc ion secondary battery, and can prolong the cycle life of the zinc ion secondary battery, inhibit zinc dendrite growth and relieve hydrogen evolution reaction.
The present application is described in detail above. It will be apparent to those skilled in the art that the present application can be practiced in a wide range of equivalent parameters, concentrations, and conditions without departing from the spirit and scope of the application and without undue experimentation. While the application has been described with respect to specific embodiments, it will be appreciated that the application may be further modified. In general, this application is intended to cover any variations, uses, or adaptations of the application following, in general, the principles of the application and including such departures from the present disclosure as come within known or customary practice within the art to which the application pertains.
Claims (6)
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