Fluorine-substituted graphdiyne-protected zinc-ion secondary battery zinc anode and preparation method and application thereof

Abstract

The application provides a fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc negative electrode and a preparation method and application thereof. The preparation method comprises the following steps: (1) preparing a reaction solution, wherein the reaction solution comprises 1,3,5-trifluoro-2,4,6-tri-alkynyl benzene, cuprous iodide, pyridine, tetrahydrofuran and N,N,N',N'-tetramethyl ethylenediamine; and (2) taking a zinc foil as a substrate, and preparing the fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc negative electrode in situ on the surface of the zinc foil through a cross-coupling reaction of 1,3,5-trifluoro-2,4,6-tri-alkynyl benzene in the reaction solution. According to the preparation method, the fluorine-substituted graphdiyne can be controllably grown on the surface of the zinc foil through an in-situ preparation method, the preparation method has the advantages of mild conditions, simple operation and suitability for large-scale preparation. Moreover, the prepared fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc negative electrode can be used as a new negative electrode material of the zinc ion secondary battery, can inhibit zinc dendrite growth and relieve hydrogen evolution, and can significantly improve the cycle life of the zinc ion secondary battery.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of nanomaterials and preparation, and particularly relates to a fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc negative electrode and a preparation method and application thereof. BACKGROUND

[0002] At present, developing new secondary batteries has become an important solution for human beings to cope with energy and environmental problems. Among many new secondary battery systems, zinc ion secondary batteries have attracted widespread attention due to their abundant reserves, low price, high specific capacity, environmental friendliness, safety and stability, and have brought new opportunities and challenges for the development of new secondary batteries.

[0003] The negative electrode material of zinc ion secondary battery generally uses zinc metal, because it is convenient to process, low cost, good electrical conductivity and safe and environmentally friendly, can be directly used for the negative electrode assembly of zinc ion secondary battery. In recent years, a series of researches on the negative electrode material of zinc ion secondary battery 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.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.), which provide a lot of experience for the development of zinc-ion secondary battery anodes.

[0004] However, the zinc metal anode still has problems such as easy generation of zinc dendrites to pierce the separator and cause short circuit of the battery, and easy occurrence of hydrogen evolution side reaction to cause loss of electrolyte during battery cycling. These problems seriously affect the cycle life of the zinc-ion secondary battery.

[0005] Therefore, the anode material of the zinc-ion secondary battery at the present stage still needs to be improved. SUMMARY

[0006] In view of the problems of dendrite and side reaction of the negative electrode material of the zinc ion battery at present, the inventors have found, in the research process, that fluorine-substituted graphdiyne has a conjugated structure formed by the connection of diacetylenic bond and fluorine-substituted benzene ring, has zincophilic fluorine atoms and uniformly distributed macropores. Based on this, the fluorine-substituted graphdiyne protected zinc ion secondary battery zinc negative electrode obtained by the in-situ preparation method can be used as the negative electrode material of the zinc ion battery, can simultaneously inhibit zinc dendrite growth and hydrogen evolution side reaction, and thus significantly improves the cycle life of the zinc ion secondary battery.

[0007] Therefore, one object of the present application is to provide a method for preparing fluorine-substituted graphdiyne protected zinc ion secondary battery zinc negative electrode simply and easily in large scale.

[0008] The method for preparing fluorine-substituted graphdiyne protected zinc ion secondary battery zinc negative electrode provided by the present application comprises the following steps:

[0009] (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'-tetramethylethylenediamine;

[0010] (2) in the reaction solution, 1,3,5-trifluoro-2,4,6-trialkynylbenzene undergoes cross-coupling reaction with zinc foil as a substrate, cuprous iodide as a catalyst, tetrahydrofuran as a solvent, N,N,N',N'-tetramethylethylenediamine as a solvent and a base, and pyridine as a base, to in-situ prepare the fluorine-substituted graphdiyne protected zinc ion secondary battery zinc negative electrode on the surface of the zinc foil.

[0011] The inventors have found, through research, that fluorine-substituted graphdiyne can be controllably grown on the surface of zinc foil by the in-situ preparation method, and the preparation method has mild conditions, simple operation and is suitable for large-scale preparation. Moreover, the prepared fluorine-substituted graphdiyne protected zinc ion secondary battery zinc negative electrode can be used as a new negative electrode material of zinc ion secondary battery, can inhibit zinc dendrite growth and relieve hydrogen evolution reaction, and thus significantly improves the cycle life of the zinc ion secondary battery.

[0012] In the above method step (1), in the reaction solution, the weight ratio of 1,3,5-trifluoro-2,4,6-trialkynylbenzene, cuprous iodide, pyridine, tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine can be 10:(1~2):(197~393):(8900~17800):(7750~15500) in turn.

[0013] In one embodiment of the present application, in the reaction solution, the weight ratio of 1,3,5-trifluoro-2,4,6-trialkynylbenzene, cuprous iodide, pyridine, tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine can be 10:1:197:13350:11625 in turn.

[0014] In one embodiment of the present application, the weight ratio of 1,3,5-trifluoro-2,4,6-tri-alkynylbenzene, cuprous iodide, pyridine, tetrahydrofuran and N,N,N',N'-tetramethyl ethylenediamine in the reaction solution is 10:1:197:8900:7750, respectively.

[0015] In one embodiment of the present application, the weight ratio of 1,3,5-trifluoro-2,4,6-tri-alkynylbenzene, cuprous iodide, pyridine, tetrahydrofuran and N,N,N',N'-tetramethyl ethylenediamine in the reaction solution is 10:2:393:13350:11625, respectively.

[0016] In step (2), the reaction temperature of the in-situ preparation is 50±10 degrees Celsius.

[0017] In one embodiment of the present application, the reaction temperature of the in-situ preparation is 50 degrees Celsius.

[0018] The reaction time of the in-situ preparation is 36-60 hours.

[0019] In one embodiment of the present application, the reaction time of the in-situ preparation is 48 hours.

[0020] In one embodiment of the present application, the reaction time of the in-situ preparation is 36 hours.

[0021] In one embodiment of the present application, the reaction time of the in-situ preparation is 60 hours.

[0022] Another object of the present application is to provide a fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc anode.

[0023] The fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc anode is prepared by the method described above.

[0024] The inventor has found through research that the fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc anode prepared by the present application can be used as a new anode material for zinc ion secondary batteries, inhibits zinc dendrite growth, and alleviates hydrogen evolution, thereby significantly improving the cycle life of zinc ion secondary batteries.

[0025] Those skilled in the art can understand that the features and advantages described above for the method of preparing the fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc anode also apply to the fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc anode, which will not be described here.

[0026] The present application also provides a zinc ion secondary battery.

[0027] The zinc ion secondary battery comprises a negative electrode, and the negative electrode is the above-mentioned fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc negative electrode.

[0028] The inventor has found through research that the zinc ion secondary battery of the embodiment of the present application, whose negative electrode is formed by the fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc negative electrode, can inhibit zinc dendrite growth and relieve hydrogen evolution reaction, thereby significantly improving the cycle life of the zinc ion secondary battery. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 is a method flow chart for preparing the fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc negative electrode of the embodiment of the present application;

[0030] Figure 2 is a chemical reaction schematic diagram related to the embodiment of the present application;

[0031] Figure 3 is a photo of the fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc negative electrode prepared by the embodiment of the present application;

[0032] Figure 4 is an SEM photo of the fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc negative electrode prepared by the embodiment of the present application;

[0033] Figure 5 is a Raman spectrum of the fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc negative electrode prepared by the embodiment of the present application;

[0034] Figure 6 is a photoelectron spectroscopy analysis diagram of the fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc negative electrode prepared by the embodiment of the present application;

[0035] Figure 7 is a battery cycle performance test comparison diagram of the comparative example and the embodiment of the present application;

[0036] Figure 8 is a comparison of SEM photos of the comparative example and the embodiment of the present application after battery cycling;

[0037] Figure 9 is a linear sweep voltammetry test comparison diagram of the comparative example and the embodiment of the present application. DETAILED DESCRIPTION

[0038] The present application will be further described in detail below in conjunction with specific embodiments, and the embodiments given are only for illustrating the present application, rather than limiting the scope of the present application. The embodiments provided below can serve as a guide for further improvement by those of ordinary skill in the art, and do not in any way constitute a limitation on the present application.

[0039] The experimental methods in the following examples are all conventional methods, and are performed according to the techniques or conditions described in the literature in the field or according to the product instructions, unless otherwise specified. The materials, reagents, etc. used in the following examples can be obtained commercially, unless otherwise specified.

[0040] In one aspect of the present application, the present application provides a method for preparing a fluorine-substituted graphdiyne-protected zinc-ion secondary battery zinc anode. Referring to Figure 1 The method for preparing the present application is described in detail.

[0041] According to an embodiment of the present application, referring to Figure 1 The method for preparing the present application is described in detail.

[0042] S100: Preparing a reaction solution.

[0043] In this step, a reaction solution is prepared, wherein the weight ratio of 1,3,5-trifluoro-2,4,6-triethynylbenzene, cuprous iodide, pyridine, tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine is 10:(1~2):(197~393):(8900~17800):(7750~15500). In this way, the reaction solution formed by the above-mentioned ratio can obtain a fluorine-substituted graphdiyne-protected zinc-ion secondary battery zinc anode through in-situ reaction. According to an embodiment of the present application, the specific method for preparing the reaction solution is not particularly limited, and for example, cuprous iodide can be dispersed in a mixture of tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine first, and then 1,3,5-trifluoro-2,4,6-triethynylbenzene and pyridine can be added after ultrasonic dissolution. Those skilled in the art can adjust accordingly according to the dispersion degree of the reaction solution.

[0044] In some embodiments of the present application, the weight ratio of 1,3,5-trifluoro-2,4,6-triylbenzene, cuprous iodide, pyridine, tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine is 10:(1~2):(197~393):(8900~17800):(7750~15500), so that the fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc negative electrode can be successfully prepared. In addition, the inventors have found through long-term research 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'-tetramethylethylenediamine is higher than the above ratio, the reaction degree of 1,3,5-trifluoro-2,4,6-triylbenzene is low, and it is difficult to form a dense fluorine-substituted graphdiyne protective layer; if the content of cuprous iodide and pyridine is higher than the above ratio, or the content of tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine is lower than the above ratio, 1,3,5-trifluoro-2,4,6-triylbenzene will preferentially react in the solution, and it is also difficult to form a dense fluorine-substituted graphdiyne protective layer, and it will cause waste of reactants. In some specific examples, the weight ratio of 1,3,5-trifluoro-2,4,6-triylbenzene, cuprous iodide, pyridine, tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine is 10:1:197:13350:11625, so that a zinc ion secondary battery zinc negative electrode with a fluorine-substituted graphdiyne protective layer of higher quality can be efficiently obtained.

[0045] S200: In-situ preparation of a fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc negative electrode in the reaction solution with zinc foil as the substrate.

[0046] In this step, a fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc negative electrode is prepared in-situ in the reaction solution prepared in step S100 with zinc foil as the substrate.

[0047] According to the embodiments of the present application, the specific size of the zinc foil and the specific conditions for in-situ preparation are not particularly limited, and those skilled in the art can adjust them according to the specific electrical performance of the fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc negative electrode. In some embodiments of the present application, the zinc foil can be a square with a thickness of 0.1 mm and a side length of 23 mm, and the in-situ preparation can be carried out at 50±10 degrees Celsius. In this way, the conditions for in-situ preparation of a fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc negative electrode at a temperature of 50±10 degrees Celsius are more moderate and have lower energy consumption, and the fluorine-substituted graphdiyne protective layer of the fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc negative electrode prepared under this size has better quality.

[0048] In some embodiments of the present application, the in-situ preparation time can be 36-60 hours, so that the zinc ion secondary battery zinc negative electrode protected by fluorine-substituted graphdiyne prepared in-situ in the above time range has better electrochemical performance. In addition, the inventors have found 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-triazylbenzene is low, and the fluorine-substituted graphdiyne can only form a loose structure; if the in-situ preparation time is greater than 60 hours, the fluorine-substituted graphdiyne layer obtained by the reaction is too thick, and the electrochemical performance of the zinc ion secondary battery zinc negative electrode protected by fluorine-substituted graphdiyne decreases. In some specific examples, the in-situ preparation time can be 48 hours, so that the zinc ion secondary battery zinc negative electrode protected by fluorine-substituted graphdiyne with excellent electrochemical performance can be more efficiently prepared in-situ.

[0049] In summary, according to the embodiments of the present application, the present application proposes a preparation method, through which a fluorine-substituted graphdiyne protective layer can be grown in-situ on the surface of a zinc foil, and the preparation method has mild conditions, simple operation and is suitable for large-scale preparation. Moreover, the zinc ion secondary battery zinc negative electrode protected by fluorine-substituted graphdiyne prepared by the preparation method can be used as a new negative electrode material of a zinc ion secondary battery, inhibits zinc dendrite growth, alleviates hydrogen evolution reaction, and thus significantly improves the cycle life of the zinc ion secondary battery.

[0050] In another aspect of the present application, the present application proposes a zinc ion secondary battery zinc negative electrode protected by fluorine-substituted graphdiyne.

[0051] According to the embodiments of the present application, the zinc ion secondary battery zinc negative electrode protected by fluorine-substituted graphdiyne is prepared by the above method.

[0052] In summary, according to the embodiments of the present application, the present application proposes a zinc ion secondary battery zinc negative electrode protected by fluorine-substituted graphdiyne, which can be used as a negative electrode material of a zinc ion secondary battery, inhibits zinc dendrite growth, alleviates hydrogen evolution reaction, and thus significantly improves the cycle life of the zinc ion secondary battery. It can be understood by those skilled in the art that the features and advantages described above for the method of preparing the zinc ion secondary battery zinc negative electrode protected by fluorine-substituted graphdiyne are still applicable to the zinc ion secondary battery zinc negative electrode protected by fluorine-substituted graphdiyne, and will not be described here.

[0053] In another aspect of the present application, the present application proposes a zinc ion secondary battery.

[0054] According to the embodiments of the present application, the zinc ion secondary battery comprises a negative electrode, and the negative electrode is formed by the above-mentioned zinc ion secondary battery zinc negative electrode protected by fluorine-substituted graphdiyne.

[0055] In summary, according to the embodiments of the present application, the present application proposes a zinc-ion secondary battery, the negative electrode of which is formed by a fluorine-substituted graphdiyne-protected zinc-ion secondary battery zinc negative electrode, which can inhibit zinc dendrite growth and relieve hydrogen evolution reaction, thereby significantly improving the cycle life of the zinc-ion secondary battery. Those skilled in the art can understand that the features and advantages described above for the fluorine-substituted graphdiyne-protected zinc-ion secondary battery zinc negative electrode are still applicable to the zinc-ion secondary battery, and will not be repeated here.

[0056] The 1,3,5-trifluoro-2,4,6-triethynylbenzene used in the following examples can be synthesized with reference to the following literature: 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 V t 2g orbital occupation in vanadium oxide cathode toward fast-charging aqueouszinc-ion batteries. PNAS 2023, 120(13), e2217208120.。

[0057] The ammonium-doped vanadium pentoxide used in the following examples can be synthesized with reference to the following literature: 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.

[0058] Example 1

[0059] In this example, a fluorine-substituted graphdiyne-protected zinc-ion secondary battery zinc negative electrode was prepared.

[0060] Specifically, 1.0 mg of cuprous iodide was ultrasonically dissolved in a mixed solvent of 15 mL of tetrahydrofuran and 15 mL of N,N,N',N'-tetramethylethylenediamine, and then 0.25 mL of pyridine and 10 mg of 1,3,5-trifluoro-2,4,6-triethynylbenzene were added, i.e., the weight ratio of 1,3,5-trifluoro-2,4,6-triethynylbenzene, cuprous iodide, pyridine, tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine was 10:1:197:13350:11625. After mixing, a square zinc foil with a thickness of 0.1 mm and a side length of 23 mm was placed in the reaction solution, and the reaction was carried out at 50 degrees Celsius for 48 hours to obtain a fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc negative electrode.

[0061] The chemical reaction schematic involved in this example is shown in Figure 2 The photo of the fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc negative electrode obtained is shown in Figure 3 .

[0062] Then, the fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc negative electrode of the example was subjected to scanning electron microscope (SEM), Raman spectrum and photoelectron spectroscopy analysis. The SEM photo, Raman spectrum and energy spectrum analysis chart of this example are shown in Figures 4 to 6 , respectively, indicating that the fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc negative electrode was successfully prepared by the preparation method. Figures 4 to 6 to prove the successful synthesis of fluorine-substituted graphdiyne material.

[0063] Example 2

[0064] In this example, according to the basically same method and conditions as in Example 1, 1.0 mg of cuprous iodide was ultrasonically dissolved in a mixed solvent of 10 mL of tetrahydrofuran and 10 mL of N,N,N',N'-tetramethylethylenediamine, and then 0.25 mL of pyridine and 10 mg of 1,3,5-trifluoro-2,4,6-triethynylbenzene were added, i.e., the weight ratio of 1,3,5-trifluoro-2,4,6-triethynylbenzene, cuprous iodide, pyridine, tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine was 10:1:197:8900:7750. After mixing, the zinc foil was placed in the reaction solution, and the reaction was carried out at 50 degrees Celsius for 48 hours to obtain a fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc negative electrode.

[0065] Example 3

[0066] In this embodiment, 2.0 mg of cuprous iodide was ultrasonically dissolved in a mixed solvent of 15 mL of tetrahydrofuran and 15 mL of N,N,N',N'-tetramethylethylenediamine, and then 0.50 mL of pyridine and 10 mg of 1,3,5-trifluoro-2,4,6-triethynylbenzene were added, i.e., the weight ratio of 1,3,5-trifluoro-2,4,6-triethynylbenzene, cuprous iodide, pyridine, tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine was 10:2:393:13350:11625. After mixing evenly, zinc foil was put into the reaction solution, and reacted at 50 degrees Celsius for 48 hours to obtain a fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc negative electrode.

[0067] Example 4

[0068] In this embodiment, 1.0 mg of cuprous iodide was ultrasonically dissolved in a mixed solvent of 15 mL of tetrahydrofuran and 15 mL of N,N,N',N'-tetramethylethylenediamine, and then 0.25 mL of pyridine and 10 mg of 1,3,5-trifluoro-2,4,6-triethynylbenzene were added, i.e., the weight ratio of 1,3,5-trifluoro-2,4,6-triethynylbenzene, cuprous iodide, pyridine, tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine was 10:1:197:13350:11625. After mixing evenly, zinc foil was put into the reaction solution, and reacted at 50 degrees Celsius for 36 hours to obtain a fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc negative electrode.

[0069] Example 5

[0070] In this embodiment, 1.0 mg of cuprous iodide was ultrasonically dissolved in a mixed solvent of 15 mL of tetrahydrofuran and 15 mL of N,N,N',N'-tetramethylethylenediamine, and then 0.25 mL of pyridine and 10 mg of 1,3,5-trifluoro-2,4,6-triethynylbenzene were added, i.e., the weight ratio of 1,3,5-trifluoro-2,4,6-triethynylbenzene, cuprous iodide, pyridine, tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine was 10:1:197:13350:11625. After mixing evenly, zinc foil was put into the reaction solution, and reacted at 50 degrees Celsius for 60 hours to obtain a fluorine-substituted graphdiyne-protected zinc ion secondary battery zinc negative electrode.

[0071] Example 6

[0072] In this example, the zinc anode of the zinc ion secondary battery protected by fluorine-substituted graphdiyne prepared in Example 1 was pressed into a circular negative electrode sheet with a diameter of 10 mm. A 2032 type button cell was assembled with ammonium-doped vanadium pentoxide as the positive electrode, qualitative filter paper as the separator, and 3 M zinc trifluoromethanesulfonate aqueous solution as the electrolyte.

[0073] Comparative Example 1

[0074] 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 3 M zinc trifluoromethanesulfonate aqueous solution as the electrolyte.

[0075] Example 7

[0076] In this example, the zinc anode of the zinc ion secondary battery protected by fluorine-substituted graphdiyne prepared in Example 1 was cut into a square electrode sheet with a side length of 10 mm as the working electrode. A three-electrode system was assembled with a silver / silver chloride electrode as the reference electrode, a carbon rod as the counter electrode, and 1 M zinc sulfate aqueous solution as the electrolyte.

[0077] Comparative Example 2

[0078] In this comparative example, a three-electrode system was assembled with zinc foil as the working electrode, a silver / silver chloride electrode as the reference electrode, and a carbon rod as the counter electrode, and 1 M zinc sulfate aqueous solution as the electrolyte.

[0079] Example 8

[0080] In this example, the button cells of Example 6 and Comparative Example 1, and the three-electrode systems of Example 7 and Comparative Example 2 were respectively subjected to electrochemical performance tests. Specifically, the cycle performance test was performed on the button cells of Example 6 and Comparative Example 1 at a current density of 1 A g -1 -1, and the linear sweep voltammetry test was performed on the three-electrode systems of Example 7 and Comparative Example 2 at a scan rate of 10 mV s -1 -1. The test results showed that:

[0081] Reference Figure 7 The maximum specific capacity of the button cell of Comparative Example 1 was 205.2 mAh g -1 -1 at a current density of 1 A g -1 , the cycle life was 475 times, and the capacity retention rate was 43.1%. The maximum specific capacity of the button cell of Example 6 was 214.3 mA h g -1 -1 at a current density of 1 A g -1, the cycle life is 2000 times, and the capacity retention rate is 67.3%. The cycle performance test shows that the coin cell of Example 6 has a significantly improved cycle life compared with the coin cell of Comparative Example 1.

[0082] Reference is made to Figure 8 The negative electrode of Comparative Example 1 grows a large number of zinc dendrites after battery cycling; the negative electrode of Example 6 still has a smooth morphology after battery cycling. The SEM photos show that the negative electrode of Example 6 can effectively inhibit the growth of zinc dendrites.

[0083] Reference is made to Figure 9 At a scan rate of 10 mV s -1 , the current density of Comparative Example 2 reaches -50 mA cm -2 , and the corresponding potential is -1.356 V; the current density of Example 7 reaches -50 mA cm -2 , and the corresponding potential is -1.395 V. The linear sweep voltammetry test results show that the working electrode of Example 7 has a larger hydrogen evolution potential than the working electrode of Comparative Example 2, and the working electrode of Example 7 has a stronger ability to inhibit the hydrogen evolution reaction than the working electrode of Comparative Example 2.

[0084] In summary, Examples 1-8 and Comparative Examples 1-2 show that the preparation method proposed in the present application can controllably grow fluorine-substituted graphdiyne on the surface of zinc foil by in-situ preparation method, and the preparation method has mild conditions, simple operation and is suitable for large-scale preparation. Moreover, the zinc ion secondary battery zinc negative electrode prepared by the fluorine-substituted graphdiyne can be used as a new negative electrode material for zinc ion secondary batteries, which can improve the cycle life of zinc ion secondary batteries, inhibit the growth of zinc dendrites, and alleviate the hydrogen evolution reaction.

[0085] The present application has been described in detail. For those skilled in the art, without departing from the spirit and scope of the present application, and without unnecessary experiments, the present application can be implemented in a wider range with equivalent parameters, concentrations and conditions. Although the present application gives a special example, it should be understood that further improvements can be made to the present application. In summary, according to the principle of the present application, this application intends to include any changes, uses or improvements of the present application, including changes made by conventional techniques known in the art, which are outside the scope disclosed in the present application.

Claims

1. A method for preparing a fluorine-substituted graphdiyne-protected zinc-ion secondary battery zinc anode, comprising the following steps: (1) preparing a reaction solution, wherein, a reaction solution comprising 1, 3, 5-trifluoro-2, 4, 6-triethynylbenzene, cuprous iodide, pyridine, tetrahydrofuran and N, N, N', N'-tetramethylethylenediamine; (2) cross-coupling reaction of 1, 3, 5-trifluoro-2, 4, 6-triethynylbenzene in the reaction solution to prepare the fluorine-substituted graphdiyne-protected zinc-ion secondary battery zinc anode in situ on the surface of a zinc foil.

2. The method of claim 1, wherein, In step (1), in the reaction solution, the weight ratio of 1, 3, 5-trifluoro-2, 4, 6-triethynylbenzene, cuprous iodide, pyridine, tetrahydrofuran and N, N, N', N'-tetramethylethylenediamine is 10: (1-2) : (197-393) : (8900-17800) : (7750-15500) in turn.

3. The method of claim 1, wherein, In step (2), the reaction temperature for the in situ preparation is 50±10℃, and the reaction time for the in situ preparation is 36-60 hours. 4.The fluorine-substituted graphdiyne-protected zinc-ion secondary battery zinc anode prepared by the method of any one of claims 1-3. 5.Use of the fluorine-substituted graphdiyne-protected zinc-ion secondary battery zinc anode of claim 4 as a zinc-ion secondary battery anode. 6.A zinc-ion secondary battery, wherein the anode of the zinc-ion secondary battery is the fluorine-substituted graphdiyne-protected zinc-ion secondary battery zinc anode of claim 4.

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