Application of conjugated microporous polymer material in preparation of photoresponse zinc ion battery

Abstract

The invention belongs to the technical field of high polymer materials, and discloses an application of a conjugated microporous polymer material in preparation of a photoresponse zinc ion battery. The conjugated microporous polymer material has a narrow forbidden band, high carrier mobility and a small electron transfer barrier, is beneficial to improving the light capture capability, accelerating charge separation and transportation and effectively improving the photocatalytic activity, can also be directly used as a photo-anode in a photo-assisted rechargeable zinc ion battery, and can be applied to the field of photo-assisted rechargeable zinc ion batteries. According to the present invention, the zinc ion battery prepared by the method can absorb photons, produce photo-induced electrons and holes, promote the charge-discharge reaction of the battery, has the energy saving effect when applied to construction of the zinc ion battery, and can achieve the efficient synergistic conversion of solar energy and electric energy, and the photo-assisted rechargeable zinc ion battery prepared by using the zinc ion battery has significant photo-response voltage under illumination, the method has a wide application scene in the field of photoresponse cells.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and particularly relates to application of a conjugated microporous polymer material in preparing a light-responsive zinc ion battery. Background Art

[0002] The growing demand for energy and environmental issues have accelerated the transition from traditional fossil fuels to clean, renewable energy, especially solar energy. As a renewable energy source, although solar energy has the advantages of being clean and environmentally friendly, its energy acquisition has obvious intermittent characteristics. The efficiency of solar energy collection is significantly affected by geographical location, seasonal changes, and climatic conditions. In order to overcome this limitation, it is usually necessary to combine solar panels with rechargeable batteries, electrochemical capacitors, or other types of energy storage systems to achieve efficient storage and stable supply of energy.

[0003] Innovation in the field of materials science is particularly critical in the process of energy storage. Although inorganic materials have a long history of application in photoresponsive cathode materials, their technical complexity and high cost in battery recycling and reuse have gradually become bottlenecks restricting their further application. It is in this context that an emerging photoresponsive material, conjugated microporous polymers (CMPs), is gradually becoming the focus of research. This type of material is composed of lightweight elements and is interconnected through its inherent π-conjugated structure and strong covalent bonds, showing great application potential.

[0004] CMPs not only have advantages in structure, but also are regarded as important candidate materials in future energy storage and conversion technologies due to their unique optoelectronic properties and environmental friendliness. Due to their adjustable and flexible structure, CMPs have a wide range of potential applications, including gas adsorption, catalysis, sensors and energy storage. Moreover, compared with other microporous organic polymers (such as COFs and MOFs), they have the advantages of high physical and chemical stability, easy synthesis, adjustable structure, high surface area and high microporosity. Summary of the invention

[0005] In order to overcome the shortcomings and deficiencies in the above-mentioned prior art, the purpose of the present invention is to provide an application of a conjugated microporous polymer material in the preparation of a light-responsive zinc ion battery.

[0006] The purpose of the present invention is achieved through the following technical solutions:

[0007] The invention discloses an application of a conjugated microporous polymer material in preparing a light-responsive zinc ion battery. The conjugated microporous polymer material is prepared according to the following steps: 1,2,4,5-benzenetetramine hydrochloride and hexaketone cyclohexane are subjected to a solvothermal reaction in a reaction solvent under the action of an acid, and the conjugated microporous polymer material is obtained after washing and drying.

[0008] The molar ratio of the 1,2,4,5-benzenetetraamine hydrochloride to hexaketone cyclohexane is 1:1.5.

[0009] The reaction solvent is one or more of 1,4-dioxane, mesitylene, N-methylpyrrolidone, toluene, methanol, and N,N-dimethylformamide.

[0010] The reaction solvent is a mixed solvent of 1,4-dioxane and mesitylene in a volume ratio of 3:1.

[0011] The acid is 1-4 mol / L acetic acid.

[0012] The volume ratio of the reaction solvent to the acid is 12:1.

[0013] The solvent thermal reaction is carried out at 110-170° C. for 3-7 days.

[0014] The solvothermal reaction was carried out at 125° C. for 5 days.

[0015] The washing is performed with ethanol, dichloromethane and tetrahydrofuran in sequence.

[0016] The solvent thermal reaction is carried out under sealed and degassed conditions; the drying is carried out under vacuum at 80-140° C. for 1-7 days.

[0017] The conjugated microporous polymer material has the following structural units and structures:

[0018]

[0019] Compared with the prior art, the present invention has the following advantages and effects:

[0020] (1) Conjugated microporous polymer materials have narrow bandgap, high carrier mobility and small electron transfer barrier, which are beneficial to improving light capture ability, accelerating charge separation and transport, and effectively improving photocatalytic activity. The material of this invention is used in the photocatalytic positive electrode of the battery, and by absorbing light energy to excite carriers, it effectively promotes the charging and discharging process of the battery, while reducing energy loss and making full use of solar energy, a clean energy, showing its potential in improving energy efficiency and promoting sustainable development.

[0021] (2) The present invention realizes the continuous conversion of light energy to electrical energy and then to chemical energy through conjugated microporous polymer materials, optimizes the charging process of zinc ion batteries, reduces the charging voltage and power consumption under light, improves the charging efficiency, and demonstrates the efficient application of solar energy in battery technology.

[0022] (3) The present invention simplifies the structure of the device by integrating solar cells with rechargeable batteries, making the collection and use of solar energy more direct and convenient. This integrated design not only reduces the complexity of the system, but also improves the efficiency of energy conversion, making the use of solar energy more efficient.

[0023] (4) When the battery assembled by the present invention is exposed to light, the photocatalytic positive electrode can efficiently absorb photons, trigger the generation of photogenerated electrons and holes, and further participate in electrochemical reactions, thereby promoting the charging process of the zinc ion battery. This design strategy not only achieves a voltage drop of more than 200mV, but also significantly reduces the voltage required for charging and reduces energy consumption. The material and battery show great application potential in the field of solar cells. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 The schematic diagram of the synthesis route and chemical structure of C5N2 is shown;

[0025] Figure 2 The infrared spectra of BTA, HKH and C5N2 are shown;

[0026] Figure 3 The XRD pattern of C5N2 is shown;

[0027] Figure 4 An SEM image of C5N2 at a magnification of 20,000 times is shown;

[0028] Figure 5 The in situ UV spectrum of C5N2 is shown;

[0029] Figure 6 shows the UV photoelectron spectrum of C5N2;

[0030] Figure 7 A schematic diagram of the energy band structure of C5N2 is shown;

[0031] Figure 8 A schematic diagram of assembling a photoresponsive zinc-ion battery based on C5N2 is shown;

[0032] Fig. 9 It shows the battery under light conditions and 1mA·cm -2 The charging voltage drop diagram at the current density of , the sampling interval is 30 minutes. DETAILED DESCRIPTION

[0033] The present invention is further described below with reference to specific embodiments, but they should not be construed as limiting the present invention.

[0034] The present invention is further described below with reference to specific examples, but the examples do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0035] Example 1: Preparation method of conjugated microporous polymer material

[0036] 1,2,4,5-benzenetetramine hydrochloride (BTA, 17.4 mg, 0.1 mmol) and hexaketone cyclohexane (HKH, 25.2 mg, 0.15 mmol), dioxane (3 mL), and mesitylene (1 mL) were added to a 35 mL thick-walled pressure-resistant glass tube in sequence, ultrasonically treated for 10 minutes, and then 0.5 mL of 1 M acetic acid was added; thereafter, the thick-walled pressure-resistant glass tube was sealed, cooled in a liquid nitrogen bath, degassed through three freeze-pump-thaw cycles, and then heated in a metal bath at a constant temperature of 125°C for 3 days; after the reaction was completed, the reaction tube was cooled to room temperature, washed and filtered three times with ethanol, tetrahydrofuran, and dichloromethane in sequence; the filtered precipitate was vacuum dried in a vacuum drying oven at 120°C for 12 h, and finally a black powder product conjugated microporous polymer material was obtained, named C5N2( Figure 1 shows the synthetic route of C5N2).

[0037] C5N2 was characterized by infrared spectroscopy. Figure 2 The infrared spectra of BTA, HKH and C5N2 are shown in Figure 2. By comparing the infrared spectra of monomers BTA and HKH with the conjugated microporous polymer C5N2, it was found that C5N2 formed a phenazine bond, and its characteristic band was located at 1400 cm -1 (-C=N-), the -NH2 group of BTA (3380cm -1 ) and the -C=O unit of HKH (1638 cm -1 The above results show that the phenazine-like material condensed by amino and keto groups, namely the conjugated microporous polymer material C5N2, was successfully synthesized.

[0038] The crystallinity of the conjugated microporous polymer material C5N2 was characterized by X-ray powder diffraction (PXRD). Figure 3 The PXRD spectrum of C5N2 shows a diffraction peak at 25° (2θ), which corresponds to the characteristic peak of the conjugated microporous polymer and also proves that it has a π-conjugated structure, indicating that the conjugated microporous polymer material C5N2 is successfully synthesized by the method of the present invention.

[0039] The scanning electron microscope (SEM) image of C5N2 is shown in Figure 2. Figure 4 As shown, the π-conjugated microporous polymer of the C5N2 material has a layer-layer stacked structure.

[0040] Combined with the above characterization, it can be concluded that the C5N2 material was successfully synthesized, and its structure is shown below.

[0041]

[0042] The photoelectric properties of C5N2 were studied by in situ UV-visible absorption spectroscopy and UV photoelectron spectroscopy (UPS). Figure 5 , Figure 6 They are the in-situ UV-visible absorption spectrum and UV photoelectron spectrum of C5N2. Further, after processing the in-situ UV-visible absorption spectrum and UV photoelectron spectrum, the energy band structure diagram of C5N2 can be obtained (such as Figure 7 ). Thus, it can be concluded that C5N2 can effectively absorb light in the ultraviolet and visible light regions, and has a wide light absorption band and a narrow band gap.

[0043] Example 2: Application of conjugated microporous polymer materials

[0044] Preparation of button battery: From bottom to top, the negative electrode shell, spring, gasket, zinc negative electrode (zinc foil), electrolyte (100 μL 2M zinc trifluoromethanesulfonate solution), diaphragm (glass fiber), photoanode (conjugated microporous polymer material obtained in Example 1), high light transmittance PVC film and positive electrode shell with a light-transmitting window are assembled in sequence, wherein the zinc negative electrode and the photoanode are immersed in the electrolyte, and then the assembled battery is placed on a battery sealing machine to apply pressure to seal the battery, so as to obtain a light-responsive zinc ion battery, as shown in the schematic diagram. Figure 8 .

[0045] The light source used in the lighting condition test was a 300W xenon lamp. The xenon lamp was vertically irradiated on the side with a light-transmitting glass window, and the light intensity was controlled at 100mW·cm -2 .

[0046] The battery was tested under alternating light and dark conditions to verify the photoresponse performance of the photoanode under charging conditions, with a current density of 1 mA cm -2 The illumination time was 30 minutes. Fig. 9 As shown, the photoresponse voltage of the battery is 210mV. After the light-dark alternating test, its photoresponse performance remains good, indicating that the photoanode has excellent photoresponse performance and light stability in lithium-ion batteries.

[0047] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. Application of a conjugated microporous polymer material in the preparation of a light-responsive zinc ion battery, characterized in that: The conjugated microporous polymer material is prepared according to the following steps: 1,2,4,5-benzenetetraamine hydrochloride and hexaketone cyclohexane are subjected to a solvothermal reaction in a reaction solvent under the action of an acid, and the conjugated microporous polymer material is obtained after washing and drying.

2. The use according to claim 1, characterized in that: The molar ratio of the 1,2,4,5-benzenetetraamine hydrochloride to hexaketone cyclohexane is 1:1.

5.

3. The use according to claim 1, characterized in that: The reaction solvent is one or more of 1,4-dioxane, mesitylene, N-methylpyrrolidone, toluene, methanol, and N,N-dimethylformamide.

4. The use according to claim 3, characterized in that: The reaction solvent is a mixed solvent of 1,4-dioxane and mesitylene in a volume ratio of 3:

1.

5. The use according to claim 1, characterized in that: The acid is 1-4 mol / L acetic acid.

6. The use according to claim 1, characterized in that: The volume ratio of the reaction solvent to the acid is 12:

1.

7. The use according to claim 1, characterized in that: The solvent thermal reaction is carried out at 110-170° C. for 3-7 days.

8. The use according to claim 1, characterized in that: The solvothermal reaction was carried out at 125° C. for 5 days.

9. The use according to claim 1, characterized in that: The washing is performed with ethanol, dichloromethane and tetrahydrofuran in sequence.

10. The use according to claim 1, characterized in that: The solvent thermal reaction is carried out under sealed and degassed conditions; the drying is carried out under vacuum at 80-140° C. for 1-7 days.

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