1, 3-propane diamine intercalated potassium manganese oxide positive electrode material, preparation method thereof and application of 1, 3-propane diamine intercalated potassium manganese oxide positive electrode material in aqueous zinc ion battery

Abstract

The invention discloses a 1, 3-propane diamine intercalated potassium manganese oxide positive electrode material, a preparation method thereof and an application of the 1, 3-propane diamine intercalated potassium manganese oxide positive electrode material in an aqueous zinc ion battery, and belongs to the technical field of materials. The preparation method comprises the following steps: dissolving potassium permanganate and 1, 3-propane diamine in deionized water, stirring, adjusting the pH value of the solution, transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, carrying out a hydrothermal reaction, cooling to room temperature, carrying out centrifugal cleaning, and carrying out vacuum drying to obtain the positive electrode material DP-KMO. DP-KMO is prepared through a simple one-step hydrothermal method, DP is inserted into the electrode material through further reaction, the introduction of DP not only enlarges the interlayer spacing of KMO, but also participates in the storage of zinc ions, increases the active sites of the KMO, effectively promotes the diffusion of ions and charge transfer, improves the conductivity of the material, reduces the internal resistance of the material, and improves the electrochemical performance of the material. And the structural flexibility and stability of the material are maintained, so that the overall performance of the water-based zinc ion battery is improved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of materials, and particularly relates to a 1,3-propanediamine intercalated potassium manganese oxide positive electrode material, a preparation method thereof and application thereof in a water-based zinc ion battery. BACKGROUND

[0002] In the wave of global energy structure transformation, renewable energy represented by solar energy, biomass energy, water energy and wind energy is about to experience explosive growth. At the same time, the popularity of smart grids, the maturity of micro-grid technology and the construction of the energy internet all put forward higher requirements for new energy storage technologies. Among many energy storage technologies, electrochemical energy storage is highly valued due to its flexibility, high conversion efficiency and high power density. In recent years, in the field of electrochemical energy storage, although lithium ion batteries occupy a dominant position, their limitations are increasingly evident, such as lithium resource shortage, high cost, safety risks and other problems, which have prompted the scientific research and industrial communities to seek alternative solutions. Zinc ion batteries (ZIBs) have become a highly potential energy storage technology due to their unique advantages, including: 1) zinc is the 24th most abundant element in the earth's crust (about 75 ppm), with an annual global production of over 12 million tons, much higher than that of lithium (about 0.0017 ppm); 2) traditional lithium ion batteries use flammable organic electrolytes, which pose a risk of thermal runaway, while zinc ion batteries usually use water as electrolyte, fundamentally eliminating the risk of combustion and explosion, and are suitable for scenarios with high safety requirements (such as grid energy storage and wearable devices); 3) zinc is non-toxic and recyclable, which meets the trend of green energy development. Based on the three advantages of resource availability, safety and reliability and environmental friendliness, zinc ion batteries are gradually becoming an important development direction of the next generation of energy storage technology, and are expected to play a key role in the energy transformation process. Currently, many positive electrode materials have been applied to AZIBs, such as manganese oxides, vanadium oxides and Prussian blue analogues. However, the high charge-to-radius ratio and strong coulombic interaction of Zn 2+ result in slow diffusion in the lattice of these electrode materials, and the repeated intercalation of Zn 2+ may cause the collapse and dissolution of the positive electrode material, thereby reducing its electrochemical performance and making it difficult to meet the growing demand. SUMMARY

[0003] To solve the above-mentioned technical problems, the application provides a 1,3-propanediamine intercalated potassium manganese oxide positive electrode material, a preparation method thereof and application thereof in a water-based zinc ion battery.

[0004] The technical scheme adopted by the present application is: a 1,3-propanediamine intercalated potassium manganese oxide positive electrode material, and a preparation method thereof, which comprises the following steps: potassium permanganate and 1,3-propanediamine (DP) are dissolved in deionized water, after stirring at room temperature, the pH of the solution is adjusted, and the solution is fully mixed by continuing to stir, the fully mixed solution is transferred to a polytetrafluoroethylene lined stainless steel hydrothermal reaction kettle, hydrothermal reaction is carried out, and the solution is cooled to room temperature, centrifuged, washed and vacuum dried to obtain the 1,3-propanediamine intercalated potassium manganese oxide positive electrode material (DP-KMO).

[0005] Further, the molar ratio of potassium permanganate to 1,3-propanediamine is 4:(0.05-0.3).

[0006] Further, the pH of the solution is adjusted to 4.5-5.5.

[0007] Further, the hydrothermal reaction condition is 110-130 DEG C for 2-3 hours.

[0008] The present application provides a 1,3-propanediamine intercalated potassium manganese oxide positive electrode material in an aqueous zinc ion battery.

[0009] Further, the method comprises the following steps:

[0010] 1) Preparation of the positive electrode sheet: the 1,3-propanediamine intercalated potassium manganese oxide positive electrode material DP-KMO is uniformly mixed with a binder and a conductive material, a small amount of NMP is added as a solvent, and the mixture is uniformly mixed and directly coated on a substrate, vacuum dried, taken out, and a positive electrode sheet coated with DP-KMO is obtained;

[0011] 2) Preparation of the negative electrode sheet: a zinc sheet with a thickness of 0.1-0.2 mm is treated to form a negative electrode sheet;

[0012] 3) The aqueous zinc ion battery is assembled by taking the positive electrode sheet as the positive electrode, the negative electrode sheet as the negative electrode, and the electrolyte as a mixture of 2M zinc trifluoromethanesulfonate and 0.1M manganese sulfate.

[0013] Further, the binder is PVDF.

[0014] Further, the conductive material is Super-p.

[0015] The present application has the following advantages:

[0016] 1) The present application significantly improves the conductivity, ion diffusion rate and reduces the internal resistance of the material by introducing 1,3-propanediamine (DP) during the synthesis process.

[0017] 2) The introduction of DP enlarges the interlayer spacing of potassium manganese oxide (KMO), changes the charge distribution, and improves the Zn2+ The migration rate in hybrid materials improves the cycling stability of the material.

[0018] 3. In this invention, DP itself can store zinc, providing additional active sites for the material, thereby improving the specific capacity during the charge and discharge process.

[0019] 4. This invention has the characteristics of low cost, environmental friendliness, and high safety.

[0020] 5. This invention has advantages such as high energy density and power density.

[0021] 6. The present invention has simple synthesis and assembly processes, is easy to operate and control, and is suitable for continuous large-scale production.

[0022] 7. In this invention, after modification, the capacity of the electrode material is increased from 275mAh / g to 380mAh / g.

[0023] 8. The method of the present invention is applicable to other metal oxide cathode materials. Attached Figure Description

[0024] Figure 1 These are the XRD spectra of KMO and DP-KMO prepared in Example 1.

[0025] Figure 2 The figures show the cyclic voltammetry curves of KMO and DP-KMO prepared in Example 1.

[0026] Figure 3 These are SEM images of KMO and DP-KMO prepared in Example 1.

[0027] Figure 4 This is a specific capacity diagram of KMO and DP-KMO prepared in Example 1. Detailed Implementation

[0028] The technical solution of the present invention will be further described below, but it is not limited thereto. Any modifications or equivalent substitutions to the technical solution of the present invention that do not depart from the spirit and scope of the technical solution of the present invention should be covered within the protection scope of the present invention.

[0029] Example 1: 1,3-Propanediamine intercalated potassium manganese oxide cathode material (DP-KMO)

[0030] (a) The preparation method of DP-KMO is as follows:

[0031] Weigh out potassium permanganate (632 mg, 4 mmol) and 1,3-propanediamine (11.1 mg, 0.15 mmol), dissolve them in 30 mL of deionized water, stir at room temperature, add HCl to adjust the pH of the solution to 5, continue stirring to mix thoroughly, transfer the well mixed solution to a stainless steel hydrothermal reactor lined with polytetrafluoroethylene, react at 120 °C for 2 h, cool to room temperature, centrifuge to remove residual reactants, and vacuum dry to obtain DP-KMO electrode material.

[0032] (II) The preparation method of KMO is as follows:

[0033] Weigh out 632 mg, 4 mmol of potassium permanganate and dissolve it in 30 mL of deionized water. Stir at room temperature, add HCl to adjust the pH of the solution to 5, and continue stirring to mix thoroughly. Transfer the well mixed solution to a stainless steel hydrothermal reactor lined with polytetrafluoroethylene and react at 120 °C for 2 h. Cool to room temperature, centrifuge to remove residual reactants, and vacuum dry to obtain KMO electrode material.

[0034] (III) Testing

[0035] Figure 1 These are the XRD patterns of KMO and DP-KMO prepared in this embodiment. Figure 1 As can be seen, the diffraction peaks of all samples match well with MnO2. The diffraction peaks of DP-KMO at 37.2°, 42.6°, and 56.5° correspond to ε-MnO2, which is generated by the reduction of some MnO2 by DP under acidic conditions. Compared with KMO, the leftward shift of the DP-KMO peak at 24.8° indicates that the successful introduction of DP increased the interlayer spacing of the material.

[0036] Figure 2 These are the cyclic voltammetry curves for KMO and DP-KMO. Figure 2 It is evident that the area enclosed by DP-KMO is significantly larger than that of pure KMO, indicating that the capacity of DP-KMO is greater than that of pure KMO.

[0037] Figure 3 This is a SEM image of DP-KMO. (Source: [Insert source here]) Figure 3 It can be seen that the prepared DP-KMO has a typical nanoflower-like structure.

[0038] Figure 4 This is a specific capacity diagram of KMO and DP-KMO. (From...) Figure 4 It is evident that the specific capacity of DP-KMO is much higher than that of pure KMO.

[0039] Example 2: 1,3-Propanediamine intercalated potassium manganese oxide cathode material (DP-KMO)

[0040] The preparation method is as follows:

[0041] Potassium permanganate (632 mg, 4 mmol) and 1,3-propanediamine (5.55 mg, 0.075 mmol) were weighed and dissolved in 30 mL of deionized water, stirred at room temperature, and the pH of the solution was adjusted to 5 by adding HCl. The solution was fully mixed and transferred to a polytetrafluoroethylene-lined stainless steel hydrothermal reactor. The solution was reacted at 120°C for 2 h, cooled to room temperature, centrifuged to remove residual reactants, and vacuum dried to obtain the DP-KMO electrode material.

[0042] Example 3: Potassium manganese oxide positive electrode material intercalated with 1,3-propanediamine (DP-KMO)

[0043] The preparation method is as follows:

[0044] Potassium permanganate (632 mg, 4 mmol) and 1,3-propanediamine (22.2 mg, 0.3 mmol) were weighed and dissolved in 30 mL of deionized water, stirred at room temperature, and the pH of the solution was adjusted to 5 by adding HCl. The solution was fully mixed and transferred to a polytetrafluoroethylene-lined stainless steel hydrothermal reactor. The solution was reacted at 120°C for 2 h, cooled to room temperature, centrifuged to remove residual reactants, and vacuum dried to obtain the DP-KMO electrode material.

[0045] Example 4: Application of 1,3-propanediamine intercalated potassium manganese oxide positive electrode material in aqueous zinc ion battery (I) Preparation of aqueous zinc ion battery-1

[0046] 1) Preparation of positive electrode sheet:

[0047] The DP-KMO electrode material prepared in Example 1 was mixed with PVDF and Super-p in a mass ratio of 8:1:1, a small amount of NMP was added as a solvent, and the mixture was mixed uniformly. The mixture was then directly applied to a carbon paper substrate and dried in a vacuum drying oven. The resulting positive electrode sheet coated with the DP-KMO material was obtained.

[0048] 2) Preparation of negative electrode sheet:

[0049] A zinc sheet with a thickness of 0.1 mm and a purity of 99.99% was repeatedly polished with sandpaper to remove the surface oxide layer. The polished zinc sheet was then cut into a circular negative electrode sheet with a diameter of 12 mm for use.

[0050] 3) The aqueous zinc ion battery was assembled with the positive electrode sheet as the positive electrode, the negative electrode sheet as the negative electrode, and the electrolyte being a mixture of 2M zinc trifluoromethanesulfonate and 0.1M manganese sulfate.

[0051] (ii) Preparation of aqueous zinc ion battery-1

[0052] 1) Preparation of positive electrode sheet:

[0053] The DP-KMO electrode material prepared in Example 1 was mixed with PVDF and Super-p at a mass ratio of 8:1:1, and a small amount of NMP was added as a solvent. After mixing, the mixture was directly applied to a carbon paper substrate, and the coated carbon paper was dried in a vacuum drying oven. The positive electrode sheet coated with the DP-KMO material was obtained.

[0054] 2) Preparation of negative electrode sheet:

[0055] A zinc sheet with a thickness of 0.1 mm and a purity of 99.99% was repeatedly polished with sandpaper to remove the surface oxide layer. The polished zinc sheet was cut into a circular negative electrode sheet with a diameter of 12 mm for use.

[0056] 3) An aqueous zinc ion battery was assembled using the positive electrode sheet as the positive electrode, the negative electrode sheet as the negative electrode, and 2M zinc trifluoromethanesulfonate and 0.1M manganese sulfate as the electrolyte.

[0057] (iii) Preparation of aqueous zinc ion battery-2

[0058] 1) Preparation of positive electrode sheet:

[0059] The DP-KMO electrode material prepared in Example 2 was mixed with PVDF and Super-p at a mass ratio of 8:1:1, and a small amount of NMP was added as a solvent. After mixing, the mixture was directly applied to a carbon paper substrate, and the coated carbon paper was dried in a vacuum drying oven. The positive electrode sheet coated with the DP-KMO material was obtained.

[0060] 2) Preparation of negative electrode sheet:

[0061] A zinc sheet with a thickness of 0.1 mm and a purity of 99.99% was repeatedly polished with sandpaper to remove the surface oxide layer. The polished zinc sheet was cut into a circular negative electrode sheet with a diameter of 12 mm for use.

[0062] 3) An aqueous zinc ion battery was assembled using the positive electrode sheet as the positive electrode, the negative electrode sheet as the negative electrode, and 2M zinc trifluoromethanesulfonate and 0.1M manganese sulfate as the electrolyte.

[0063] (iv) Preparation of aqueous zinc ion battery-3

[0064] 1) Preparation of positive electrode sheet:

[0065] The DP-KMO electrode material prepared in Example 1 was mixed with PVDF and Super-p at a mass ratio of 8:1:1, a small amount of NMP was added as a solvent, and the mixture was uniformly mixed. Then, the mixture was directly applied to a carbon paper substrate, and the substrate was dried in a vacuum drying oven. The positive electrode sheet coated with the DP-KMO material was obtained.

[0066] 2) Preparation of a negative electrode sheet:

[0067] A zinc sheet with a thickness of 0.2 mm and a purity of 99.99% was repeatedly polished with sandpaper to remove the surface oxide layer. The polished zinc sheet was cut into a circular negative electrode sheet with a diameter of 12 mm for use.

[0068] 3) A water-based zinc ion battery was assembled using the positive electrode sheet as the positive electrode, the negative electrode sheet as the negative electrode, and a 2M zinc trifluoromethanesulfonate and 0.1M manganese sulfate mixture as the electrolyte.

[0069] (V) Preparation of water-based zinc ion battery-5

[0070] 1) Preparation of a positive electrode sheet:

[0071] The DP-KMO electrode material prepared in Example 2 was mixed with PVDF and Super-p at a mass ratio of 8:1:1, a small amount of NMP was added as a solvent, and the mixture was uniformly mixed. Then, the mixture was directly applied to a carbon paper substrate, and the substrate was dried in a vacuum drying oven. The positive electrode sheet coated with the DP-KMO material was obtained.

[0072] 2) Preparation of a negative electrode sheet:

[0073] A zinc sheet with a thickness of 0.2 mm and a purity of 99.99% was repeatedly polished with sandpaper to remove the surface oxide layer. The polished zinc sheet was cut into a circular negative electrode sheet with a diameter of 12 mm for use.

[0074] 3) A water-based zinc ion battery was assembled using the positive electrode sheet as the positive electrode, the negative electrode sheet as the negative electrode, and a 2M zinc trifluoromethanesulfonate and 0.1M manganese sulfate mixture as the electrolyte.

[0075] (VI) Preparation of water-based zinc ion battery-6

[0076] 1) Preparation of a positive electrode sheet:

[0077] The DP-KMO electrode material prepared in Example 3 was mixed with PVDF and Super-p at a mass ratio of 8:1:1, a small amount of NMP was added as a solvent, and the mixture was uniformly mixed. Then, the mixture was directly applied to a carbon paper substrate, and the substrate was dried in a vacuum drying oven. The positive electrode sheet coated with the DP-KMO material was obtained.

[0078] 2) Preparation of a negative electrode sheet:

[0079] The zinc sheet with a thickness of 0.2 mm and a purity of 99.99% was repeatedly sanded with sandpaper to remove the oxide layer on the surface. The sanded zinc sheet was then cut into a circular negative electrode sheet with a diameter of 12 mm for later use.

[0080] 3) Assemble an aqueous zinc-ion battery using a positive electrode as the positive electrode, a negative electrode as the negative electrode, and a 2M zinc trifluoromethanesulfonate and 0.1M manganese sulfate mixture as the electrolyte.

[0081] (vii) Performance Testing

[0082] Electrochemical tests were performed on the assembled aqueous zinc-ion batteries 1-6.

[0083] The aqueous zinc-ion battery-1 exhibits the best electrochemical performance, showing improved specific capacity at all current densities. For example... Figure 4 As shown, compared to pure KMO electrode material, the specific capacity of the DP-KMO electrode material prepared in Example 1 is significantly higher. After modification, the capacity of the electrode material increased from 275 mAh / g to 380 mAh / g. This is because the molar ratio of potassium permanganate to 1,3-propanediamine in the aqueous zinc-ion battery-1 is 4:0.15. The resulting DP-KMO, compared to pure KMO, expands the interlayer spacing, provides more active sites, and is more conducive to the insertion and extraction of zinc ions, thereby improving its electrochemical performance.

Claims

1. A 1,3-propanediamine-intercalated potassium manganese oxide cathode material, characterized in that, The preparation method includes the following steps: potassium permanganate and 1,3-propanediamine are dissolved in deionized water, stirred at room temperature, the pH of the solution is adjusted, and stirring is continued to ensure thorough mixing. The thoroughly mixed solution is transferred to a stainless steel hydrothermal reactor lined with polytetrafluoroethylene for hydrothermal reaction. After cooling to room temperature, the solution is centrifuged, washed, and vacuum dried to obtain DP-KMO, a potassium manganese oxide cathode material intercalated with 1,3-propanediamine.

2. The 1,3-propanediamine-intercalated potassium manganese oxide cathode material according to claim 1, characterized in that, The molar ratio is potassium permanganate:1,3-propanediamine = 4:(0.05-0.3).

3. The 1,3-propanediamine-intercalated potassium manganese oxide cathode material according to claim 1, characterized in that, Adjust the pH of the solution to 4.5-5.

5.

4. The 1,3-propanediamine-intercalated potassium manganese oxide cathode material according to claim 1, characterized in that, The hydrothermal reaction conditions are 110℃-130℃ for 2-3 hours.

5. The application of a 1,3-propanediamine-intercalated potassium manganese oxide cathode material according to any one of claims 1-4 in an aqueous zinc-ion battery.

6. The application according to claim 5, characterized in that, The method includes the following steps: 1) Preparation of positive electrode: After the 1,3-propanediamine-intercalated potassium manganese oxide positive electrode material DP-KMO is mixed evenly with binder and conductive material, a small amount of NMP is added as a solvent. After mixing evenly, it is directly coated on the substrate, vacuum dried, and taken out to obtain a positive electrode coated with DP-KMO. 2) Preparation of negative electrode sheet: A zinc sheet with a thickness of 0.1mm-0.2mm is processed to form a negative electrode sheet; 3) Assemble an aqueous zinc-ion battery using a positive electrode as the positive electrode, a negative electrode as the negative electrode, and a 2M zinc trifluoromethanesulfonate and 0.1M manganese sulfate mixture as the electrolyte.

7. The application according to claim 6, characterized in that, The adhesive is PVDF.

8. The application according to claim 6, characterized in that, The conductive material is Super-p.

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