Application of tris (4-nitrophenyl) amine in zinc organic battery

Abstract

The invention discloses application of tris (4-nitrophenyl) amine in a zinc organic battery, and belongs to the technical field of electrochemical energy storage. According to the application of the tris (4-nitrophenyl) amine in the zinc organic battery, the tris (4-nitrophenyl) amine is used as an organic positive electrode material for preparing the zinc organic battery. The tris (4-nitrophenyl) amine is used for preparing the zinc organic battery, n-type (-NO2 group) and p-type (-N group, derived from triphenylamine) active sites are simultaneously introduced into a molecular structure of the tris (4-nitrophenyl) amine, a co-storage mechanism of zinc ions and anions is realized by TNPA, and the energy density and the power density of the battery are remarkably improved; the n-type active sites provide abundant zinc ion adsorption sites, and the p-type active sites promote rapid reaction kinetics and anion storage. The invention provides a new design thought for research and development of an organic positive electrode material of a high-performance aqueous zinc ion battery.

Description

Technical Field

[0001] This invention relates to the field of electrochemical energy storage technology, specifically to the application of tris(4-nitrophenyl)amine in zinc organic batteries. Background Technology

[0002] With the rapid development of energy storage technology, zinc-organic batteries, as a promising new battery system, are attracting widespread attention from the scientific community. Leveraging its advantages such as abundant zinc resources, low cost, high safety, and environmental friendliness, it is expected to play a crucial role in future large-scale energy storage, wearable devices, and other fields. As the core component of zinc-organic batteries, the performance of the cathode material directly determines the overall performance of the battery.

[0003] Organic cathode materials have become a research hotspot in the field of zinc-organic batteries due to their significant advantages such as wide availability of resources, flexible controllable molecular structure, and environmental friendliness. However, most organic cathode materials currently suffer from key problems such as poor conductivity and single active sites, which prevent them from fully realizing their electrochemical performance and make it difficult to meet the urgent demand for high-performance cathode materials in zinc-organic batteries.

[0004] Molecular design, as a cutting-edge and highly innovative strategy, has opened up new pathways for optimizing the performance of organic cathode materials. By precisely controlling the molecular structure and introducing dual active sites, materials can be endowed with unique electron transport and ion storage properties. Nitro groups, due to their high redox activity and flexible controllable electron cloud density, have become an ideal choice for constructing active sites. Developing dual-active-site nitro organic cathode materials suitable for zinc-organic batteries based on molecular design holds promise for breaking through the performance bottlenecks of traditional cathode materials and achieving excellent performance such as high specific capacity, long cycle life, and fast charge-discharge. However, this field still faces many challenges in molecular structure design and precise performance characterization, requiring further exploration and innovation. Summary of the Invention

[0005] The purpose of this invention is to provide an application of tris(4-nitrophenyl)amine in zinc organic batteries, which solves the technical problem that organic cathode materials for zinc organic batteries are difficult to meet the high performance requirements of zinc organic batteries in the prior art.

[0006] To achieve the above objectives, one embodiment of the present invention provides an application of tris(4-nitrophenyl)amine in a zinc organic battery, wherein tris(4-nitrophenyl)amine is used as an organic cathode material to prepare a zinc organic battery.

[0007] In one preferred embodiment of the present invention, tris(4-nitrophenyl)amine is used as an organic cathode material to prepare electrode sheets for zinc organic batteries.

[0008] In one preferred embodiment of the present invention, the mass loading of the electrode sheet is 1 mg / cm². 2 -10mg / cm 2 .

[0009] One preferred embodiment of the present invention uses tris(4-nitrophenyl)amine as an organic cathode material to prepare an electrode sheet for a zinc organic battery, comprising: mixing tris(4-nitrophenyl)amine, a binder and a conductive material to prepare the electrode sheet.

[0010] In one preferred embodiment of the present invention, the mass ratio of tris(4-nitrophenyl)amine, binder and conductive material is 3-6:3-6:1.

[0011] One preferred embodiment of the present invention involves mixing tris(4-nitrophenyl)amine, a binder, and a conductive material to prepare an electrode sheet, comprising:

[0012] Tris(4-nitrophenyl)amine, binder, and conductive material are mixed in a solvent to obtain a slurry;

[0013] The slurry is dried and pressed to obtain electrode sheets.

[0014] In one preferred embodiment of the present invention, the adhesive is a polytetrafluoroethylene emulsion.

[0015] In one preferred embodiment of the present invention, the concentration of the polytetrafluoroethylene emulsion is 55%-65%.

[0016] In one preferred embodiment of the present invention, the conductive material includes either super P or graphite.

[0017] In one preferred embodiment of the present invention, the solvent is any one of ethanol, N,N-dimethylformamide and N-methylpyrrolidone.

[0018] One preferred embodiment of the present invention uses tris(4-nitrophenyl)amine as an organic positive electrode material to prepare a zinc organic battery, comprising: a positive electrode containing tris(4-nitrophenyl)amine, a zinc sheet as a negative electrode, a glass fiber separator, and a 2.5 mol / L-3.5 mol / L Zn(CF3SO3)2 solution as an electrolyte, and assembling the zinc organic battery.

[0019] One preferred embodiment of the present invention uses tris(4-nitrophenyl)amine as an organic positive electrode material to prepare a zinc organic battery, comprising: a positive electrode containing tris(4-nitrophenyl)amine, a negative electrode made of zinc foil, a glass fiber separator, and 2.5 mol / L-3.5 mol / L aqueous zinc trifluoromethanesulfonate as an electrolyte, and assembling the zinc organic battery.

[0020] In summary, the beneficial effects of the present invention are as follows:

[0021] 1. This invention utilizes tris(4-nitrophenyl)amine in zinc-organic batteries, significantly improving their electrochemical performance. The tris(4-nitrophenyl)amine (TNPA) molecule integrates both n-type and p-type active sites. The -NO2 group, as an n-type active site, provides abundant zinc ion binding sites, while the -N- group (derived from triphenylamine) serves as a p-type active site, promoting rapid reaction kinetics and enabling efficient anion storage. This unique molecular structure allows the Zn / TNPA battery to achieve an electron transfer mechanism during a single charge-discharge cycle, thereby significantly improving the battery's energy density and capacity.

[0022] 2. In this invention, tris(4-nitrophenyl)amine is used in the preparation of zinc organic batteries. Tris(4-nitrophenyl)amine is based on an organic molecule containing a conjugated structure as its backbone. The conjugated structure can enhance the intramolecular electron transport capability, providing a fundamental guarantee for the electrochemical performance of zinc organic batteries.

[0023] 3. This invention uses tris(4-nitrophenyl)amine in the preparation of zinc organic batteries. The raw materials used in the preparation are widely available, inexpensive and environmentally friendly. Furthermore, the preparation process is simple and easy to operate, and does not involve toxic or harmful reagents or high-pressure and high-temperature reaction conditions.

[0024] Other features and advantages of the invention will be set forth in the description which follows, and will be apparent in part from the description, or may be learned by practicing the invention. The objects and other advantages of the invention will be apparent from the effects described in the description and the accompanying drawings. Attached Figure Description

[0025] Figure 1 This is a scanning electron microscope image of tris(4-nitrophenyl)amine in Example 1 of the present invention;

[0026] Figure 2 This is the band gap diagram of tris(4-nitrophenyl)amine in Example 1 of the present invention;

[0027] Figure 3 The infrared spectrum of tris(4-nitrophenyl)amine in Example 1 of this invention;

[0028] Figure 4 This is a cyclic voltammetry curve of the aqueous zinc organic battery electrode in Example 2 of the present invention;

[0029] Figure 5 This is a constant current charge-discharge curve of the aqueous zinc organic battery electrode in Embodiment 2 of the present invention;

[0030] Figure 6 This is a cycle life curve of the aqueous zinc organic battery electrode in Example 2 of the present invention. Detailed Implementation

[0031] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0032] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this invention.

[0033] This invention provides an application of tris(4-nitrophenyl)amine in zinc organic batteries, using tris(4-nitrophenyl)amine as an organic cathode material in the preparation of zinc organic batteries. The chemical structural formula of tris(4-nitrophenyl)amine is shown below:

[0034]

[0035] Specifically, tris(4-nitrophenyl)amine is used as an organic cathode material to prepare electrode sheets for zinc organic batteries, wherein the mass loading of the electrode sheets is 1 mg / cm³. 2 -10mg / cm 2 .

[0036] Furthermore, tris(4-nitrophenyl)amine is used as an organic cathode material to prepare electrode sheets for zinc organic batteries, including: mixing tris(4-nitrophenyl)amine, a binder, and a conductive material to prepare the electrode sheet; specifically, it includes:

[0037] Step (1): Tris(4-nitrophenyl)amine, binder and conductive material are mixed evenly in a solvent to obtain a slurry; wherein the solvent is any one of ethanol, N,N-dimethylformamide and N-methylpyrrolidone;

[0038] Step (2): The slurry is dried and pressed to obtain an electrode sheet; specifically, the slurry is placed in an oven to dry, the dried sample is pressed onto a stainless steel mesh, and vacuum dried at 100℃ for 24 hours to obtain a positive electrode sheet.

[0039] The mass ratio of tris(4-nitrophenyl)amine, binder, and conductive material is 3-6:3-6:1. The binder is polytetrafluoroethylene emulsion with a concentration of 55%-65%, preferably 60%. The conductive material includes either super P or graphite.

[0040] Tris(4-nitrophenyl)amine was used as an organic positive electrode material to prepare a zinc organic battery. The process included: using a button cell, a positive electrode containing tris(4-nitrophenyl)amine, a zinc sheet as the negative electrode, a glass fiber separator, and a 3 mol / L Zn(CF3SO3)2 solution as the electrolyte, and assembling the zinc organic battery.

[0041] Preferably, tris(4-nitrophenyl)amine is used as an organic positive electrode material to prepare a zinc organic battery, comprising: a positive electrode containing tris(4-nitrophenyl)amine, a negative electrode containing zinc foil, a glass fiber separator, and 2.5 mol / L-3.5 mol / L aqueous zinc trifluoromethanesulfonate as an electrolyte, and assembling the zinc organic battery.

[0042] Example 1

[0043] Performance testing of tris(4-nitrophenyl)amine: Scanning electron microscopy, band gap, and infrared spectroscopy were performed on tris(4-nitrophenyl)amine. The scanning electron microscope image of tris(4-nitrophenyl)amine is shown below. Figure 1 As shown, the band gap diagram of tris(4-nitrophenyl)amine is as follows. Figure 2 As shown, the infrared spectrum of tris(4-nitrophenyl)amine is as follows: Figure 3 As shown.

[0044] from Figures 1-3 As can be seen from the scanning electron microscope, tris(4-nitrophenyl)amine exhibits a stacked structure with uniformly distributed dual active sites; the band gap diagram shows that tris(4-nitrophenyl)amine can achieve a rapid ion response; and the presence of dual active sites in tris(4-nitrophenyl)amine can be detected by infrared spectroscopy.

[0045] Example 2

[0046] An application of tris(4-nitrophenyl)amine in zinc organic batteries, using tris(4-nitrophenyl)amine as an organic cathode material in the preparation of zinc organic batteries, includes the following steps:

[0047] Tris(4-nitrophenyl)amine, 60 wt% polytetrafluoroethylene emulsion (purchased from Shanghai Sanai Fu New Material Co., Ltd.), and Super P were mixed evenly in N-methylpyrrolidone (the mass ratio of tris(4-nitrophenyl)amine, 60 wt% polytetrafluoroethylene emulsion, and Super P was 6:3:1). The mixture was then dried in an oven. The dried sample was pressed onto a stainless steel mesh (purchased from Jiangsu Ningcong Wire Mesh) under a pressure of 20 MPa and vacuum dried at 100℃ for 24 h to obtain a mass loading of 2 mg / cm³. 2 Positive electrode plate.

[0048] A zinc-organic battery was assembled using a CR2032 button cell casing, an electrode sheet containing tris(4-nitrophenyl)amine as the positive electrode, a zinc sheet (purity ≥99.99%) as the negative electrode, a GE-Whatman glass fiber separator, and a 3 mol / L Zn(CF3SO3)2 solution as the electrolyte.

[0049] The electrochemical performance of the device was tested using a CHI760E electrochemical workstation. The electrochemical performance of the aqueous zinc organic battery electrode prepared based on tris(4-nitrophenyl)amine is as follows: Figure 4-6 As shown.

[0050] from Figure 4 As can be seen from the cyclic voltammetry curves of tris(4-nitrophenyl)amine, this cathode material involves the storage of two ions; from... Figure 5 As can be seen from the data, the capacity output of the electrode in the aqueous zinc organic battery prepared based on tris(4-nitrophenyl)amine can reach 300 mAh g. -1 The above; from Figure 6 As can be seen, the aqueous zinc organic battery prepared based on tris(4-nitrophenyl)amine retains more than 80% of its capacity after 10,000 charge-discharge cycles, demonstrating excellent capacity output and outstanding cycle life.

[0051] As demonstrated in Example 1, from a molecular design perspective, the examples are a crucial step in verifying the feasibility of the design concept. After proposing the molecular design idea of ​​dual-active-site nitro organic cathode materials, the examples, through specific material synthesis and characterization practices, transform the abstract design into an observable and quantifiable entity. This provides experimental evidence for molecular design, allowing us to clearly determine whether the designed molecular structure can truly achieve the expected dual-active-site function, and whether these active sites can synergistically function in actual materials.

[0052] Examples 1 and 2 demonstrate the significant effects of the embodiments. On one hand, the application of tris(4-nitrophenyl)amine to zinc-organic batteries significantly improves their performance. The synergistic effect of the dual active sites increases the number of redox reaction sites, leading to increased ion insertion and extraction; the rational molecular structure design enhances the material's structural stability and reduces performance degradation caused by structural changes during charging and discharging. On the other hand, Example 2 provides direction for molecular design optimization. By analyzing relevant data, structural problems can be identified, allowing for design adjustments to continuously improve material performance.

[0053] In summary, this invention utilizes tris(4-nitrophenyl)amine in the preparation of zinc organic batteries. By simultaneously introducing n-type (-NO2 group) and p-type (-N- group, derived from triphenylamine) active sites into its molecular structure, tris(4-nitrophenyl)amine achieves a co-storage mechanism of zinc ions and anions through TNPA, significantly improving the energy density and power density of the battery. The n-type active sites provide abundant zinc ion adsorption sites, while the p-type active sites promote rapid reaction kinetics and anion storage. This invention provides a new design approach for the development of organic cathode materials for high-performance aqueous zinc-ion batteries.

[0054] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made to the technical solutions of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. Use of tris(4-nitrophenyl)amine in a zinc organic battery, characterized in that: Tris(4-nitrophenyl)amine was used as an organic cathode material to prepare zinc organic batteries.

2. Use of tris(4-nitrophenyl)amine in zinc organic batteries according to claim 1, characterized in that: Tris(4-nitrophenyl)amine was used as an organic cathode material to prepare electrode sheets for zinc organic batteries.

3. Use of tris(4-nitrophenyl)amine in zinc organic batteries according to claim 2, characterized in that: The mass loading of the electrode sheet is 1 mg / cm 2 - 10 mg / cm 2 .

4. Use of tris(4-nitrophenyl)amine according to claim 2 in a zinc organic battery, characterized in that: The method of using tris(4-nitrophenyl)amine as an organic cathode material to prepare an electrode sheet for a zinc organic battery includes: mixing tris(4-nitrophenyl)amine, a binder, and a conductive material to prepare the electrode sheet.

5. Use of tris(4-nitrophenyl)amine in zinc organic batteries according to claim 4, characterized in that: The mass ratio of the tris(4-nitrophenyl)amine, binder, and conductive material is 3-6:3-6:

1.

6. Use of tris(4-nitrophenyl)amine in zinc organic batteries according to claim 4, characterized in that: The method of mixing tris(4-nitrophenyl)amine, binder, and conductive material to prepare an electrode sheet includes: Tris(4-nitrophenyl)amine, binder, and conductive material are mixed in a solvent to obtain a slurry; The slurry is dried and pressed to obtain electrode sheets.

7. Use of tris(4-nitrophenyl)amine in zinc organic batteries according to claim 4, characterized in that: The adhesive is a polytetrafluoroethylene emulsion.

8. Use of tris(4-nitrophenyl)amine in zinc organic batteries according to claim 4, characterized in that: The concentration of the polytetrafluoroethylene emulsion is 55%-65%.

9. Use of tris(4-nitrophenyl)amine in zinc organic batteries according to claim 4, characterized in that: The conductive material includes either super P or graphite.

10. Use of tris(4-nitrophenyl)amine in zinc organic batteries according to claim 6, characterized by the fact that: The solvent is any one of ethanol, N,N-dimethylformamide, and N-methylpyrrolidone.

11. Use of tris(4-nitrophenyl)amine in zinc organic batteries according to claim 1, characterized in that: The method of using tris(4-nitrophenyl)amine as an organic positive electrode material to prepare a zinc organic battery includes: a positive electrode containing tris(4-nitrophenyl)amine, a zinc sheet as a negative electrode, a glass fiber membrane, and a 2.5 mol / L-3.5 mol / L Zn(CF3SO3)2 solution as an electrolyte, and assembling the zinc organic battery.

12. Use of tris(4-nitrophenyl)amine in zinc organic batteries according to claim 1, characterized in that: The method of using tri(4-nitrophenyl)amine as an organic positive electrode material to prepare a zinc organic battery includes: a positive electrode containing tri(4-nitrophenyl)amine, a negative electrode made of zinc foil, a glass fiber separator, and 2.5 mol / L-3.5 mol / L aqueous zinc trifluoromethanesulfonate as an electrolyte, and assembling the zinc organic battery.

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