Preparation method of yttrium-doped manganese oxide battery positive electrode material and application of yttrium-doped manganese oxide battery positive electrode material in aqueous zinc ion battery
By introducing yttrium ions during the synthesis process, the positive electrode material of yttrium doped manganese oxide battery was prepared, which solved the problems of conductivity and ion transport kinetics of manganese-based materials, and significantly improved the performance of aqueous zinc ion batteries.
Patent Information
- Application Number
- CN202510119813.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-25
- Publication Date
- 2025-05-02
AI Technical Summary
The inherent poor conductivity of manganese-based materials, manganese dissolution and slow ion transport kinetics limit the development of aqueous zinc ion batteries.
Yttrium ions are introduced during the synthesis process, and the positive electrode material of yttrium doped manganese oxide battery is prepared through hydrothermal reaction, adjust its electronic structure, and improve the electron transport rate and material conductivity.
It significantly improves the conductivity and ion transport rate of the material, improves the specific capacity and cycling performance during the charging and discharging process, and improves the overall performance of the aqueous zinc ion battery.
Smart Images
Figure CN119911971A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of materials, and specifically relates to a method for preparing a positive electrode material of an yttrium-doped manganese oxide battery and an application of the material in an aqueous zinc ion battery. Background Art
[0002] The modern economy and society have an increasing demand for electrical energy, and the global demand for renewable energy and environmental protection technologies is growing. Energy storage technology, especially efficient and environmentally friendly battery technology, has become a research hotspot. As a common energy form for modern electronic devices, lithium-ion batteries have been widely used in portable electronics, electric vehicles, and energy storage systems. However, like all technological products, lithium-ion batteries also have problems such as limited lifespan, poor environmental protection, low energy density, and in some cases, overheating, combustion, and even explosion, which limit their further development. In the context of resource constraints and environmental pressures faced by traditional battery technologies such as lithium-ion batteries, aqueous zinc-ion batteries stand out with their unique advantages.
[0003] The main advantage of aqueous zinc-ion batteries is that they use water as an electrolyte, which is safer and more environmentally friendly than traditional organic electrolytes. In addition, zinc, as an abundant element in the earth's crust, has sufficient resources and is relatively cheap, which is conducive to large-scale production and application. At the same time, aqueous zinc-ion batteries also have high energy density and long cycle life, which can meet a variety of application requirements. The electrochemical performance of zinc-ion batteries is highly dependent on their positive electrode materials. In recent years, the development of positive electrode materials has mainly focused on manganese-based materials, vanadium-based materials, Prussian blue and its analogs. Among them, manganese-based materials are considered to be the most promising positive electrode materials due to their different crystal structures and three-dimensional spatial frameworks. However, the inherent poor conductivity of manganese-based materials, the dissolution of manganese and the slow ion transport kinetics also limit their development. The present invention reduces the charge transfer resistance, promotes mass transfer kinetics, significantly improves the material conductivity and ion transport rate, and makes it have high electrochemical reversibility, thereby greatly improving the overall performance of aqueous zinc-ion batteries. Summary of the invention
[0004] To solve the above problems, the present invention provides a method for preparing a positive electrode material for a yttrium-doped manganese oxide battery and its application in an aqueous zinc ion battery.
[0005] The technical solution adopted by the present invention is:
[0006] A method for preparing a positive electrode material for a yttrium-doped manganese oxide battery comprises the following steps:
[0007] At room temperature, potassium permanganate and manganese sulfate monohydrate are dissolved in deionized water, stirred evenly, yttrium nitrate hexahydrate is added, and stirred again to fully mix, the fully mixed solution is subjected to hydrothermal reaction, cooled to room temperature, centrifuged and washed, and vacuum dried to obtain Y-MnO2 electrode material.
[0008] Furthermore, in the above-mentioned method for preparing the positive electrode material of yttrium-doped manganese oxide battery, the molar ratio of potassium permanganate: manganese sulfate monohydrate: yttrium nitrate hexahydrate is 6:1:0.1-0.4.
[0009] Furthermore, in the above-mentioned method for preparing a positive electrode material for a yttrium-doped manganese oxide battery, the hydrothermal reaction is to transfer the fully mixed solution to a stainless steel hydrothermal reactor lined with polytetrafluoroethylene and react at 160° C. for 12 hours.
[0010] Application of a yttrium-doped manganese oxide battery positive electrode material as described in any one of the above items in an aqueous zinc ion battery.
[0011] Furthermore, the above application method comprises the following steps:
[0012] 1) Preparation of positive electrode: After the Y-MnO2 electrode material is evenly mixed with the binder and the conductive material, a small amount of NMP is added as a solvent, and after being evenly mixed, it is directly applied on the substrate carbon paper, dried in a vacuum drying oven, and taken out to obtain a positive electrode sheet coated with the Y-MnO2 electrode material;
[0013] 2) Preparation of negative electrode: Grind the zinc sheet with sandpaper to remove the oxide layer on the surface, and cut the polished zinc sheet into small discs with a diameter of 12 mm;
[0014] 3) Using the positive electrode sheet coated with Y-MnO2 electrode material prepared in step 1) as the positive electrode, the zinc sheet prepared in step 2) as the negative electrode, and 1M Zn(CF3SO3)2+0.1M MnSO4 as the electrolyte, an aqueous zinc ion battery is obtained.
[0015] Furthermore, in the above application method, in step 1), the binder is PVDF.
[0016] Furthermore, in the above application method, in step 1), the conductive material is Super-p.
[0017] Furthermore, in the above application method, in step 2), the zinc sheet has a thickness of 0.1 mm to 0.3 mm and a purity of 99.99%.
[0018] The present invention has the following advantages:
[0019] 1. The present invention introduces yttrium ions during the synthesis process to finely adjust its electronic structure, thereby significantly improving the electron transport rate and material conductivity and reducing its internal resistance.
[0020] 2. The introduction of yttrium ions expands the interlayer spacing of the material, thereby improving the specific capacity and cycle performance during the charge and discharge process.
[0021] 3. The electrode material of the present invention has the characteristics of low cost, environmental friendliness and high safety.
[0022] 4. The electrode material of the present invention has the advantages of higher energy density and power density.
[0023] 5. The synthesis process and assembly process of the present invention are simple, easy to operate and control, and suitable for continuous large-scale production.
[0024] 6. The method of the present invention is also applicable to other metal oxide positive electrode materials and has good versatility. BRIEF DESCRIPTION OF THE DRAWINGS
[0025] Figure 1 It is the XRD diagram of MnO2 and Y-MnO2 prepared in Example 1.
[0026] Figure 2 It is a comparison chart of the rates of MnO2 and Y-MnO2 prepared in Example 1.
[0027] Figure 3 It is a comparison chart of the cycle curves and coulombic efficiencies of MnO2 and Y-MnO2 prepared in Example 1.
[0028] Figure 4 It is a CV comparison chart of MnO2 and Y-MnO2 prepared in Example 1. DETAILED DESCRIPTION
[0029] The technical solution of the present invention is further described below, but is not limited thereto. Any modification or equivalent replacement of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention should be included in the protection scope of the present invention.
[0030] Example 1
[0031] (I) The preparation method of Y-MnO2 electrode material is as follows:
[0032] At room temperature, 1.896g potassium permanganate and 0.312g manganese sulfate monohydrate were weighed and dissolved in 50mL deionized water, and 0.144g yttrium nitrate hexahydrate was added after stirring evenly, and then stirred for 2h to make it fully mixed. The fully mixed solution was transferred to a stainless steel hydrothermal reactor lined with polytetrafluoroethylene, and the hydrothermal reaction was carried out at 160°C for 12h. When the reactor was completely cooled to room temperature, the product was taken out, centrifuged and washed three times with deionized water and anhydrous ethanol respectively, and vacuum dried to obtain Y-MnO2 electrode material.
[0033] (II) Comparative Example: The preparation method of manganese dioxide is as follows:
[0034] At room temperature, 1.896 g potassium permanganate and 0.312 g manganese sulfate monohydrate were weighed and dissolved in 50 mL deionized water. After stirring evenly, the well-mixed solution was transferred to a stainless steel hydrothermal reactor lined with polytetrafluoroethylene, and the hydrothermal reaction was carried out at 160 ° C for 12 hours. When the reactor was completely cooled to room temperature, the product was taken out, centrifuged and washed three times with deionized water and anhydrous ethanol respectively, and vacuum dried to obtain MnO2 electrode material.
[0035] (III) Detection
[0036] Figure 1 is the XRD comparison diagram of MnO2 and Y-MnO2 prepared in this embodiment. Figure 1 It can be seen that pure MnO2 can match the standard card, and no new peaks appear in the sample doped with yttrium, indicating that both materials have been successfully synthesized. Figure 2 This is a comparison chart of the rates of MnO2 and Y-MnO2. Figure 2 It is clearly visible that the specific capacity of Y-MnO2 at different current densities is much greater than that of pure MnO2. Figure 3 MnO2 and Y-MnO2 at 0.8A g -1 Comparison of cycle stability and Coulomb efficiency at . Figure 3 It can be seen that the Y-MnO2 sample has a -1 The energy storage capacity is increased by 20%, the cycle performance is more stable, and the Coulomb efficiency is also enhanced compared to the pure sample. Figure 4 MnO2 and Y-MnO2 at 0.1mV s -1 The CV comparison chart below. Figure 4 It can be seen that Y-MnO2 has a more obvious redox peak, and its integrated area is larger than that of MnO2, indicating that the Y-MnO2 electrode material has a higher specific capacity.
[0037] Example 2 Preparation of Y-MnO2 electrode material
[0038] At room temperature, 1.896g potassium permanganate and 0.312g manganese sulfate monohydrate were weighed and dissolved in 50mL deionized water, and 0.072g yttrium nitrate hexahydrate was added after stirring evenly, and then stirred for 2h to fully mix, and the fully mixed solution was transferred to a stainless steel hydrothermal reactor lined with polytetrafluoroethylene, and the hydrothermal reaction was carried out at 160°C for 12h. When the reactor was completely cooled to room temperature, the product was taken out, centrifuged and washed three times with deionized water and anhydrous ethanol respectively, and vacuum dried to obtain Y-MnO2 electrode material.
[0039] Example 3 Preparation of Y-MnO2 electrode material
[0040] At room temperature, 1.896g potassium permanganate and 0.312g manganese sulfate monohydrate were weighed and dissolved in 50mL deionized water, and 0.288g yttrium nitrate hexahydrate was added after stirring evenly, and then stirred for 2h to make it fully mixed. The fully mixed solution was transferred to a stainless steel hydrothermal reactor lined with polytetrafluoroethylene, and the hydrothermal reaction was carried out at 160°C for 12h. When the reactor was completely cooled to room temperature, the product was taken out, centrifuged and washed three times with deionized water and anhydrous ethanol respectively, and vacuum dried to obtain Y-MnO2 electrode material.
[0041] Example 4 Preparation of negative electrode material
[0042] A zinc sheet with a thickness of 0.1 mm and a purity of 99.99% is repeatedly polished with sandpaper to remove the oxide layer on the surface, and the polished zinc sheet is cut into small discs with a diameter of 12 mm for later use.
[0043] Example 5 Preparation of negative electrode material
[0044] A zinc sheet with a thickness of 0.2 mm and a purity of 99.99% was repeatedly polished with sandpaper to remove the oxide layer on the surface, and the polished zinc sheet was cut into small discs with a diameter of 12 mm for later use.
[0045] Example 6 Preparation of negative electrode material
[0046] A zinc sheet with a thickness of 0.3 mm and a purity of 99.99% was repeatedly polished with sandpaper to remove the oxide layer on the surface, and the polished zinc sheet was cut into small discs with a diameter of 12 mm for later use.
[0047] Example 7 Preparation of Aqueous Zinc Ion Battery
[0048] 1) Preparation of positive electrode: After the Y-MnO2 electrode material prepared in Example 1 is uniformly mixed with PVDF and Super-p, a small amount of NMP is added as a solvent, and after uniform mixing, it is directly applied on the substrate carbon paper, dried in a vacuum drying oven, and taken out to obtain a positive electrode sheet coated with the Y-MnO2 electrode material;
[0049] 2) The positive electrode sheet prepared in step 1) was used as the positive electrode, the negative electrode material prepared in Example 4 was used as the negative electrode, and 1MZn(CF3SO3)2+0.1M MnSO4 was selected as the electrolyte to obtain an aqueous zinc ion battery and perform electrochemical testing.
[0050] Example 8 Preparation of Aqueous Zinc Ion Battery
[0051] 1) Preparation of positive electrode: After the Y-MnO2 electrode material prepared in Example 2 is uniformly mixed with PVDF and Super-p, a small amount of NMP is added as a solvent, and after uniform mixing, it is directly applied on the substrate carbon paper, dried in a vacuum drying oven, and taken out to obtain a positive electrode sheet coated with the Y-MnO2 electrode material;
[0052] 2) The positive electrode sheet prepared in step 1) was used as the positive electrode, the negative electrode material prepared in Example 4 was used as the negative electrode, and 1MZn(CF3SO3)2+0.1M MnSO4 was selected as the electrolyte to obtain an aqueous zinc ion battery and perform electrochemical testing.
[0053] Example 9 Preparation of Aqueous Zinc Ion Battery
[0054] 1) Preparation of positive electrode: After the Y-MnO2 electrode material prepared in Example 3 is uniformly mixed with PVDF and Super-p, a small amount of NMP is added as a solvent, and after uniform mixing, it is directly applied on the substrate carbon paper, dried in a vacuum drying oven, and taken out to obtain a positive electrode sheet coated with the Y-MnO2 electrode material;
[0055] 2) The positive electrode sheet prepared in step 1) was used as the positive electrode, the negative electrode material prepared in Example 4 was used as the negative electrode, and 1MZn(CF3SO3)2+0.1M MnSO4 was selected as the electrolyte to obtain an aqueous zinc ion battery and perform electrochemical testing.
[0056] Example 10 Preparation of aqueous zinc ion battery
[0057] 1) Preparation of positive electrode: After the Y-MnO2 electrode material prepared in Example 1 is uniformly mixed with PVDF and Super-p, a small amount of NMP is added as a solvent, and after uniform mixing, it is directly applied on the substrate carbon paper, dried in a vacuum drying oven, and taken out to obtain a positive electrode sheet coated with the Y-MnO2 electrode material;
[0058] 2) The positive electrode sheet prepared in step 1) was used as the positive electrode, the negative electrode material prepared in Example 5 was used as the negative electrode, and 1MZn(CF3SO3)2+0.1M MnSO4 was selected as the electrolyte to obtain an aqueous zinc ion battery and perform electrochemical testing.
[0059] Example 11 Preparation of aqueous zinc ion battery
[0060] 1) Preparation of positive electrode: After the Y-MnO2 electrode material prepared in Example 2 is uniformly mixed with PVDF and Super-p, a small amount of NMP is added as a solvent, and after uniform mixing, it is directly applied on the substrate carbon paper, dried in a vacuum drying oven, and taken out to obtain a positive electrode sheet coated with the Y-MnO2 electrode material;
[0061] 2) The positive electrode sheet prepared in step 1) was used as the positive electrode, the negative electrode material prepared in Example 5 was used as the negative electrode, and 1MZn(CF3SO3)2+0.1M MnSO4 was selected as the electrolyte to obtain an aqueous zinc ion battery and perform electrochemical testing.
[0062] Example 12 Preparation of aqueous zinc ion battery
[0063] 1) Preparation of positive electrode: After the Y-MnO2 electrode material prepared in Example 3 is uniformly mixed with PVDF and Super-p, a small amount of NMP is added as a solvent, and after uniform mixing, it is directly applied on the substrate carbon paper, dried in a vacuum drying oven, and taken out to obtain a positive electrode sheet coated with the Y-MnO2 electrode material;
[0064] 2) The positive electrode sheet prepared in step 1) was used as the positive electrode, the negative electrode material prepared in Example 5 was used as the negative electrode, and 1MZn(CF3SO3)2+0.1M MnSO4 was selected as the electrolyte to obtain an aqueous zinc ion battery and perform electrochemical testing.
[0065] Example 13 Preparation of aqueous zinc ion battery
[0066] 1) Preparation of positive electrode: After the Y-MnO2 electrode material prepared in Example 1 is uniformly mixed with PVDF and Super-p, a small amount of NMP is added as a solvent, and after uniform mixing, it is directly applied on the substrate carbon paper, dried in a vacuum drying oven, and taken out to obtain a positive electrode sheet coated with the Y-MnO2 electrode material;
[0067] 2) The positive electrode sheet prepared in step 1) was used as the positive electrode, the negative electrode material prepared in Example 6 was used as the negative electrode, and 1MZn(CF3SO3)2+0.1M MnSO4 was selected as the electrolyte to obtain an aqueous zinc ion battery and perform electrochemical testing.
[0068] Example 14 Preparation of aqueous zinc ion battery
[0069] 1) Preparation of positive electrode: After the Y-MnO2 electrode material prepared in Example 2 is uniformly mixed with PVDF and Super-p, a small amount of NMP is added as a solvent, and after uniform mixing, it is directly applied on the substrate carbon paper, dried in a vacuum drying oven, and taken out to obtain a positive electrode sheet coated with the Y-MnO2 electrode material;
[0070] 2) The positive electrode sheet prepared in step 1) was used as the positive electrode, the negative electrode material prepared in Example 6 was used as the negative electrode, and 1MZn(CF3SO3)2+0.1M MnSO4 was selected as the electrolyte to obtain an aqueous zinc ion battery and perform electrochemical testing.
[0071] Example 15 Preparation of aqueous zinc ion battery
[0072] 1) Preparation of positive electrode: After the Y-MnO2 electrode material prepared in Example 3 is uniformly mixed with PVDF and Super-p, a small amount of NMP is added as a solvent, and after uniform mixing, it is directly applied on the substrate carbon paper, dried in a vacuum drying oven, and taken out to obtain a positive electrode sheet coated with the Y-MnO2 electrode material;
[0073] 2) The positive electrode sheet prepared in step 1) was used as the positive electrode, the negative electrode material prepared in Example 6 was used as the negative electrode, and 1MZn(CF3SO3)2+0.1M MnSO4 was selected as the electrolyte to obtain an aqueous zinc ion battery and perform electrochemical testing.
[0074] According to the nine aqueous zinc ion batteries assembled in Examples 7 to 15, we found that Example 7 had the best electrochemical performance. -1 The cycle life can reach 700 cycles, and the capacity retention rate is 81.6% (such as Figure 3 As shown). Since the positive electrode material in Example 1 is used in Example 7, 0.144g of yttrium nitrate hexahydrate is added, which shows that the ratio is the most suitable at this time, and the generated Y-MnO2 is more orderly, the charge transfer resistance is lower, and the conductivity and ion diffusion rate of the material are significantly improved; Example 7 uses the negative electrode material in Example 4, which has a suitable thickness and is more conducive to the release of zinc ions, thereby improving its electrochemical performance.
Claims
1. A positive electrode material for a yttrium-doped manganese oxide battery, characterized in that: The preparation method thereof comprises the following steps: At room temperature, potassium permanganate and manganese sulfate monohydrate are dissolved in deionized water, stirred evenly, yttrium nitrate hexahydrate is added, and stirred again to fully mix, the fully mixed solution is subjected to hydrothermal reaction, cooled to room temperature, centrifuged and washed, and vacuum dried to obtain Y-MnO2 electrode material.
2. The yttrium-doped manganese oxide battery positive electrode material according to claim 1, characterized in that: In molar ratio, potassium permanganate: manganese sulfate monohydrate: yttrium nitrate hexahydrate = 6:1:0.1~0.
4.
3. The yttrium-doped manganese oxide battery positive electrode material according to claim 1, characterized in that: The hydrothermal reaction is to transfer the fully mixed solution into a stainless steel hydrothermal reactor lined with polytetrafluoroethylene and react at 160° C. for 12 hours.
4. Use of the yttrium-doped manganese oxide battery positive electrode material according to claim 1, 2 or 3 in aqueous zinc ion batteries.
5. The use according to claim 4, characterized in that: The method comprises the following steps: 1) Preparation of positive electrode: After the Y-MnO2 electrode material is evenly mixed with the binder and the conductive material, a small amount of NMP is added as a solvent, and after being evenly mixed, it is directly applied on the substrate carbon paper, dried in a vacuum drying oven, and taken out to obtain a positive electrode sheet coated with the Y-MnO2 electrode material; 2) Preparation of negative electrode: Grind the zinc sheet with sandpaper to remove the oxide layer on the surface, and cut the polished zinc sheet into small discs with a diameter of 12 mm; 3) Using the positive electrode sheet coated with Y-MnO2 electrode material prepared in step 1) as the positive electrode, the zinc sheet prepared in step 2) as the negative electrode, and 1M Zn(CF3SO3)2+0.1M MnSO4 as the electrolyte, an aqueous zinc ion battery is obtained.
6. The use according to claim 5, characterized in that: In step 1), the binder is PVDF.
7. The use according to claim 5, characterized in that: In step 1), the conductive material is Super-p.
8. The use according to claim 5, characterized in that: In step 2), the zinc sheet has a thickness of 0.1 mm to 0.3 mm and a purity of 99.99%.