A method for preparing a manganese dioxide / quinoiide polymer composite and its zinc ion storage application

Abstract

The present invention provides a manganese dioxide / quinone polymer composite material, its preparation method, and application. The preparation method mainly comprises: using an interfacial oxidative polymerization method, potassium permanganate as an oxidant, and a quinone monomer as a reducing agent, to prepare the manganese dioxide / quinone polymer composite material in one step, and then washing and drying the composite material. The present invention significantly enhances the reversible dissolution and deposition of the manganese dioxide material during the charge and discharge process through the auxiliary effect of the quinone polymer, so that the prepared manganese dioxide / quinone polymer composite material has a capacity of 417 mAh g as the positive electrode of an aqueous zinc ion secondary battery. ‑1 The specific capacity is about 200 nm, which has great value for the development and application of positive electrode materials for aqueous zinc-ion batteries.

Description

TECHNICAL FIELD

[0001] The application relates to a preparation method of a composite material and application thereof, in particular to a preparation method of a "manganese dioxide / quinone polymer" composite material and zinc ion storage application thereof. BACKGROUND

[0002] In order to alleviate the huge impact of fossil fuels on climate change, environmental pollution and life quality, the industry urgently needs new sustainable energy. At the same time, the intermittent characteristics of renewable energy such as solar energy and wind energy require the development of low-cost and scalable energy storage technology. Secondary batteries are considered to be the most efficient energy storage technology and have been widely used in portable electronic products, electric vehicles and grid energy storage. Although lithium ion batteries currently dominate the market of electric vehicles and portable electronic devices, their application in grid energy storage has just begun due to high cost, limited service life and safety hazards. Other existing secondary batteries such as sodium-sulfur, lead-acid batteries and redox flow batteries are also gradually applied to grid storage, but they also have insurmountable obstacles. In contrast, aqueous ion batteries, as a new grid storage technology, have attracted the interest of a large number of researchers and industrial personnel due to their advantages of easy manufacturing, high capacity and good safety, and the advantages of abundant zinc metal negative electrode reserves, high theoretical specific capacity and good stability in aqueous system, and environmentally friendly electrolyte system.

[0003] The current aqueous zinc ion secondary battery is still in the early stage of development, and one of the important reasons limiting its practical application is the lack of positive electrode materials with high specific capacity and high energy density. Based on previous research, the commonly used manganese dioxide material for the positive electrode of the aqueous zinc ion secondary battery generally has the problems of low specific capacity and poor electrochemical stability, which affects the realization of high energy density of the electrode. SUMMARY

[0004] The application aims to provide a preparation method of a manganese dioxide / quinone polymer composite material with high specific capacity and high energy density; another purpose of the application is to provide the application of the manganese dioxide / quinone polymer composite material as a positive electrode material of an aqueous zinc ion secondary battery.

[0005] Technical scheme: The preparation method of the manganese dioxide / quinone polymer composite material provided by the application comprises the following steps:

[0006] (1) Dissolve an oxidizing manganese source and a quinone monomer in deionized water and an organic solvent respectively, and add the aqueous solution of the oxidizing manganese source drop by drop into the quinone organic solution in a dropwise manner, and the organic solution is kept at a uniform speed stirring; the molar ratio of the oxidizing manganese source to the quinone monomer is 1:(1-10);

[0007] (2) After the end of the dropwise addition process, continue stirring, and then, the product is washed and dried to obtain a manganese dioxide / quinoxaline polymer composite material.

[0008] Further, in step (1), the oxidizing manganese source is one of potassium permanganate, potassium manganate or sodium permanganate; the quinone monomer is one of 1,5-diaminoanthraquinone, 1-aminoanthraquinone or 1,4-diaminoanthraquinone; the organic solvent is one of N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone; the concentration of the aqueous oxidizing manganese source is (0.003-0.3) mol / L; the dropwise addition time is 2-10 h; and the stirring rate is 200-500 rpm.

[0009] Further, in step (2), the stirring time is 12-48 h; the drying temperature is 60-80℃, and the drying time is 12-24 h.

[0010] The method for assembling a zinc ion secondary battery using the manganese dioxide / quinoxaline polymer composite material prepared by the preparation method comprises the following steps: mixing the obtained manganese dioxide / quinoxaline polymer composite material with a conductive agent and a binder to obtain an electrode slurry by solvent dispersion stirring, coating the electrode slurry on a stainless steel foil, drying, punching, and obtaining a battery positive electrode; and assembling a button cell using the battery positive electrode, a zinc metal negative electrode, a zinc sulfate / manganese sulfate mixed solution and a separator to perform electrochemical testing.

[0011] Further, the binder is polyvinylidene fluoride; the conductive agent is Ketjen black; the solvent is N-methylpyrrolidone; the concentration of zinc sulfate in the zinc sulfate / manganese sulfate mixed solution is 2 mol / L, and the concentration of manganese sulfate is 0.1-1 mol / L; and the separator is a glass fiber separator.

[0012] Further, the drying temperature of the coated stainless steel foil is 60-120℃, and the drying time is 12-24 h.

[0013] The manganese dioxide / quinoxaline polymer composite material prepared by the preparation method can be used as a water-based zinc ion secondary battery positive electrode material.

[0014] Advantages: Compared with the prior art, the present application has the following advantages: in the present application, the reversible dissolution and deposition of the manganese dioxide material in the charging and discharging process is significantly enhanced by the auxiliary effect of the quinoxaline polymer, and the manganese dioxide / quinoxaline polymer composite material prepared as a water-based zinc ion secondary battery positive electrode has a higher specific capacity (the specific capacity is 417 mAh g-1 at 0.2 C, which is 1.5 times that of the manganese dioxide material without the quinoxaline polymer). -1The manganese dioxide / quinoiide polymer composite material has high energy density, high capacity, high voltage plateau, high power density and high energy density, and has great value in the development and application of the positive electrode material of the aqueous zinc ion battery. BRIEF DESCRIPTION OF DRAWINGS

[0015] Figure 1 An infrared diffraction pattern of the manganese dioxide / quinoiide polymer composite material provided in Embodiment 1 of the present application;

[0016] Figure 2 An electron energy spectrum of the manganese dioxide / quinoiide polymer composite material provided in Embodiment 1 of the present application;

[0017] Figure 3 A transmission electron microscope image and a corresponding selected area electron diffraction pattern of the manganese dioxide / quinoiide polymer composite material provided in Embodiment 1 of the present application;

[0018] Figure 4 A charge-discharge curve diagram of the manganese dioxide / quinoiide polymer composite material provided in Embodiment 1 of the present application as a positive electrode of an aqueous zinc ion secondary battery;

[0019] Figure 5 A comparison diagram of the voltage plateau / capacity, energy density and power density of the manganese dioxide / quinoiide polymer composite material provided in Embodiment 1 of the present application as a positive electrode of an aqueous zinc ion secondary battery and the previously reported positive electrode materials. DETAILED DESCRIPTION

[0020] The technical solutions of the present application will be further described below in combination with the drawings.

[0021] Embodiment 1

[0022] 0.3g of potassium permanganate powder was weighed and dissolved in 100mL of deionized water, and then transferred to a 250mL separation funnel which had been pre-cleaned and dried; at the same time, 2g of 1,5-diaminoanthraquinone powder was weighed and dissolved in a beaker containing 100mL of N,N-dimethylformamide; while stirring the organic solution, the potassium permanganate aqueous solution was slowly added dropwise, and the process lasted for 4h, followed by continuous stirring for 24h. After the reaction was completed, the brown-red precipitate product in the beaker was transferred to a suction filtration and washing device, and the product was subjected to repeated three times of suction filtration and washing operation using an organic solvent, and the fully washed product was transferred to a forced air drying oven for drying at 80℃ for 15h to obtain a manganese dioxide / quinoiide polymer composite material. The obtained manganese dioxide / quinoiide polymer composite material, Ketjen black and polyvinylidene fluoride were mixed in N-methyl pyrrolidone solvent in a mass ratio of 7:2:1 to obtain an electrode slurry by dispersion and stirring, and then coated on a stainless steel foil and dried at 60℃ for 12h, and then punched to obtain a battery positive electrode; a button cell was assembled using the battery positive electrode, a zinc metal negative electrode, a 2mol / L zinc sulfate / manganese sulfate mixed solution and a glass fiber separator for electrochemical test.

[0023] Example 2

[0024] 0.4 g of potassium manganate powder was weighed and dissolved in 100 mL of deionized water, and transferred to a 250 mL separation funnel which was pre-cleaned and dried; at the same time, 2.2 g of 1,4-diaminoanthraquinone powder was weighed and dissolved in a beaker containing 100 mL of N,N-dimethylacetamide; while stirring the organic solution, the aqueous solution of potassium manganate was slowly added dropwise, the process lasted for 8 h, and then the stirring was continued for 36 h. After the reaction was completed, the brown-red precipitate product in the beaker was transferred to a suction filtration and washing device, the product was subjected to repeated three times of suction filtration and washing operation using organic solvent, and the fully washed product was transferred to a forced air drying oven for drying at 80°C for 15 h, to obtain a manganese dioxide / quinone polymer composite material. The obtained manganese dioxide / quinone polymer composite material was mixed with Ketjen black and polyvinylidene fluoride in a mass ratio of 7:2:1 in N-methylpyrrolidone solvent to disperse and stir to obtain an electrode slurry, which was coated on a stainless steel foil and dried at 60°C for 12 h, and after punching, a battery positive electrode was obtained; a button cell was assembled using the battery positive electrode, a zinc metal negative electrode, a mixed solution of 2 mol / L zinc sulfate / 0.2 mol / L manganese sulfate, and a glass fiber separator, and electrochemical test was performed.

[0025] Example 3

[0026] 0.5 g of sodium permanganate powder was weighed and dissolved in 100 mL of deionized water, and transferred to a 250 mL separation funnel which was pre-cleaned and dried; at the same time, 3 g of 1-aminoanthraquinone powder was weighed and dissolved in a beaker containing 100 mL of N-methylpyrrolidone; while stirring the organic solution, the aqueous solution of sodium permanganate was slowly added dropwise, the process lasted for 6 h, and then the stirring was continued for 48 h. After the reaction was completed, the brown-red precipitate product in the beaker was transferred to a suction filtration and washing device, the product was subjected to repeated three times of suction filtration and washing operation using organic solvent, and the fully washed product was transferred to a forced air drying oven for drying at 80°C for 15 h, to obtain a manganese dioxide / quinone polymer composite material. The obtained manganese dioxide / quinone polymer composite material was mixed with Ketjen black and polyvinylidene fluoride in a mass ratio of 7:2:1 in N-methylpyrrolidone solvent to disperse and stir to obtain an electrode slurry, which was coated on a stainless steel foil and dried at 60°C for 12 h, and after punching, a battery positive electrode was obtained; a button cell was assembled using the battery positive electrode, a zinc metal negative electrode, a mixed solution of 2 mol / L zinc sulfate / 0.2 mol / L manganese sulfate, and a glass fiber separator, and electrochemical test was performed.

[0027] In order to verify the structure of the manganese dioxide / quinone polymer composite material prepared in the application, infrared spectroscopy diffraction technology was used to characterize the manganese dioxide / quinone polymer composite material prepared in Example 1 of the application, as shown in FIG. 1, which shows the infrared characteristic peaks of manganese dioxide and quinone polymer, respectively. Figure 1 ​

[0028] The manganese dioxide / quion polymer composite prepared in Example 1 of the present application was characterized by X-ray photoelectron spectroscopy, as shown in Figure 1, the valence state of manganese in the material is +4, indicating the successful preparation of the manganese dioxide / quion polymer composite. Figure 2

[0029] From the transmission electron microscope observation of the sample, it can be seen that the micro-morphology of the sample can be expressed as a reticular morphology of quinone polymer and manganese dioxide in the form of nanoparticles with a size of 4-6 nm, and the bright and regular ring diffraction pattern indicates that the manganese dioxide is a polycrystalline structure. Figure 3

[0030] In order to verify the electrochemical performance of the manganese dioxide / quinone polymer composite prepared by the present application, the electrochemical performance test of the manganese dioxide / quinone polymer composite prepared by the present application was carried out: from Figure 4 It can be seen that when the manganese dioxide / quinone polymer composite prepared in Example 1 of the present application is used as the positive electrode material of the aqueous zinc ion secondary battery, the positive electrode material has a voltage platform of 1.3 V, a specific capacity of 417 mAh g -1 , and an energy density of up to 542.1 Wh·kg -1 at a power density of 208 W·kg -1 . From Figure 5 it can be seen that the comprehensive electrochemical performance (including energy density and power density) of the manganese dioxide / quinone polymer composite prepared by the present application exceeds that of most conventional positive electrode materials, including manganese-based, vanadium-based compounds, phosphate, sulfide, organic materials and prussian blue analogues.​​

Claims

1. A method for assembling a zinc ion secondary battery as a positive electrode material using a manganese dioxide / quinone polymer composite material, characterized in that the steps include: The obtained manganese dioxide / quinone polymer composite material is mixed with a conductive agent and a binder, dispersed and stirred with a solvent to obtain an electrode slurry, and then coated on a stainless steel foil, dried, and punched to obtain a battery positive electrode. A button cell is assembled using the battery positive electrode, a zinc metal negative electrode, a zinc sulfate / manganese sulfate mixed solution, and a separator for electrochemical testing. The mass ratio of the manganese dioxide / quinone polymer composite material to the conductive agent and the binder is (7-8): (1-2): (0.5-1). The method for preparing the manganese dioxide / quinone polymer composite material comprises the following steps: (1) dissolving an oxidizing manganese source and a quinone monomer in deionized water and an organic solvent, respectively, and adding the aqueous solution of the oxidizing manganese source dropwise to the quinone organic solution while stirring at a constant speed; the molar ratio of the oxidizing manganese source to the quinone monomer is 1:(1-10); (2) After the addition process is completed, stirring is continued, and then the product is washed and dried to obtain a manganese dioxide / quinone polymer composite material.

2. A method for assembling a zinc ion secondary battery using the manganese dioxide / quinone polymer composite material as a positive electrode material according to claim 1, characterized in that: In the step (1), the oxidizing manganese source is one of potassium permanganate, potassium manganate or sodium permanganate; and the quinone monomer is one of 1,5-diaminoanthraquinone, 1-aminoanthraquinone or 1,4-diaminoanthraquinone.

3. A method for assembling a zinc ion secondary battery using the manganese dioxide / quinone polymer composite material as a positive electrode material according to claim 1, characterized in that: In the step (1), the organic solvent is one of N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone.

4. A method for assembling a zinc ion secondary battery using the manganese dioxide / quinone polymer composite material as a positive electrode material according to claim 1, characterized in that: In the step (1), the concentration of the oxidizing manganese source aqueous solution is 0.003-0.3 mol / L.

5. A method for assembling a zinc ion secondary battery using the manganese dioxide / quinone polymer composite material as a positive electrode material according to claim 1, characterized in that: In the step (1), the dropwise addition time is 2-10 h; and the stirring rate is 200-500 rpm.

6. A method for assembling a zinc ion secondary battery using the manganese dioxide / quinone polymer composite material as a positive electrode material according to claim 1, characterized in that: In the step (2), the stirring time is 12-48 h; the drying temperature is 60-80 °C, and the drying time is 12-24 h.

7. A method for assembling a zinc ion secondary battery using the manganese dioxide / quinone polymer composite material as a positive electrode material according to claim 1, characterized in that: The binder is polyvinylidene fluoride; the conductive agent is Ketjen black; the solvent is N-methylpyrrolidone; the zinc sulfate concentration in the zinc sulfate / manganese sulfate mixed solution is 2 mol / L, and the manganese sulfate concentration is 0.1-1 mol / L; and the diaphragm is a glass fiber diaphragm.

8. A method for assembling a zinc ion secondary battery using the manganese dioxide / quinone polymer composite material as a positive electrode material according to claim 1, characterized in that: The coated stainless steel foil is dried at a temperature of 60-120°C and a drying time of 12-24 hours.

9. Application of a manganese dioxide / quinone polymer composite material as a positive electrode material for an aqueous zinc ion secondary battery, characterized in that: The method for preparing the manganese dioxide / quinone polymer composite material comprises the following steps: (1) dissolving an oxidizing manganese source and a quinone monomer in deionized water and an organic solvent, respectively, and adding the aqueous solution of the oxidizing manganese source dropwise to the quinone organic solution while stirring at a constant speed; the molar ratio of the oxidizing manganese source to the quinone monomer is 1:(1-10); (2) After the addition process is completed, stirring is continued, and then the product is washed and dried to obtain a manganese dioxide / quinone polymer composite material.

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