Preparation method and application of different ion doped manganese-based material

Abstract

The application discloses an electrode material with phase transition caused by different ion doping, and is implemented according to the following steps: (NH4)2SO4, (NH4)2S2O8, MnSO4 and Al 3+ Compound or Ce 3+ Compound or Ag + Compound or Co 2+ Compound; the weighed (NH4)2SO4, (NH4)2S2O8 and MnSO4 are dissolved in deionized water and uniformly stirred to obtain a mixed solution A; the weighed Al 3+ Compound or Ce 3+ Compound or Ag + Compound or Co 2+ Compound is added into the mixed solution A and uniformly stirred to obtain a mixed solution B; the mixed solution B is transferred into a stainless steel autoclave with a polytetrafluoroethylene liner, and is reacted at 140 DEG C to 200 DEG C for 8h to 12h; the stainless steel autoclave is naturally cooled to room temperature, the precipitate is washed with deionized water for multiple times, and then is centrifuged and dried to obtain a manganese-based material with different ion doping.

Description

Technical Field

[0001] This invention belongs to the field of electrode material preparation and energy storage technology, specifically relating to the preparation and application of manganese-based materials doped with different ions. Background Technology

[0002] To achieve the national strategic goal of "peak carbon and carbon neutrality," the search for and development of sustainable clean energy sources has become an urgent priority. Rechargeable batteries, with their high energy density, low production cost, and clean and environmentally friendly characteristics, have attracted significant attention from researchers for large-scale energy storage applications.

[0003] Currently, lithium-ion batteries have become one of the most widely used energy storage devices due to their high energy density, long service life, and high energy efficiency. However, the flammable and explosive organic electrolytes, as well as the limited lithium reserves and high prices, have seriously hindered the further development and application of lithium-ion batteries in the field of large-scale energy storage. Therefore, aqueous batteries with high safety and low cost have gradually gained favor among researchers. Among the aqueous batteries reported so far, zinc-ion batteries have shown strong competitiveness, with the following main advantages: (1) Zinc metal has abundant resources, high chemical stability, suitable redox potential (-0.763V vs. SHE), and high theoretical capacity (820mAh g). -1 5855mAh cm -3 (2) Neutral zinc salt aqueous solution is an electrolyte with the characteristics of low cost, safety, high ionic conductivity and environmental friendliness.

[0004] However, due to the small ionic radius of zinc ions... With a large charge (+2 valence), zinc readily forms hydrated cations with large radii, leading to strong electrostatic interactions with the crystal structure during embedding into the cathode material. Therefore, finding suitable cathode materials for zinc storage is crucial for the development of aqueous zinc-ion batteries. Manganese-based materials, with their abundant resources, non-toxicity, environmental friendliness, low production cost, diverse ionic valence states, suitable redox potential, and high specific capacity, have long been considered the most promising cathode materials for aqueous zinc-ion batteries. However, the instability of their structure is a key factor restricting their commercialization. Summary of the Invention

[0005] The purpose of this invention is to provide a method for preparing manganese-based materials with different ion doping. Ion doping can improve the structural stability of manganese-based materials, thereby improving their cycle stability and rate performance in aqueous zinc-ion batteries.

[0006] To achieve the above objectives, the technical solution adopted by this invention is: a method for preparing manganese-based materials doped with different ions, specifically implemented according to the following steps:

[0007] Step 1: Weigh (NH4)2SO4, (NH4)2S2O8, MnSO4 and Al according to the molar ratio of 2:1:1:0.1-0.3. 3+ Compound or Ce 3+ Compound or Ag + Compound or Co 2+ Compounds;

[0008] Step 2: Dissolve the weighed (NH4)2SO4, (NH4)2S2O8 and MnSO4 in deionized water and stir until homogeneous to obtain mixed solution A;

[0009] Step 3, weigh out the Al 3+ Compound or Ce 3+ Compound or Ag + Compound or Co 2+ The compound is added to mixed solution A and stirred until homogeneous to obtain mixed solution B;

[0010] Step 4: Transfer the mixed solution B to a stainless steel autoclave lined with polytetrafluoroethylene and react at 140℃-200℃ for 8-12 hours. After the stainless steel autoclave cools naturally to room temperature, wash the precipitate multiple times with deionized water, then centrifuge and dry to obtain manganese-based materials doped with different ions.

[0011] The technical solution of the present invention also has the following characteristics:

[0012] As a further improvement to the technical solution of the present invention, in step 1, (NH4)2SO4, (NH4)2S2O8, MnSO4 and Al are weighed out. 3+ Compound or Ce 3+ Compound or Ag + Compound or Co 2+ The compounds were 2 mmol, 1 mmol, 1 mmol, and 0.1 mmol-0.3 mmol, respectively.

[0013] As a further improvement to the technical solution of the present invention, in step 2, the amount of deionized water is 10mL-30mL.

[0014] As a further improvement to the technical solution of the present invention, in step 2, the stirring time is 5 min-10 min.

[0015] As a further improvement to the technical solution of the present invention, in step 3, the stirring time is 10 min-15 min.

[0016] As a further improvement to the technical solution of the present invention, the Al 3+ The compound is AlCl3.

[0017] As a further improvement to the technical solution of the present invention, the Ce 3+ The compound is Ce(NO3)3·6H2O.

[0018] As a further improvement to the technical solution of the present invention, the Ag + The compound is AgNO3.

[0019] As a further improvement to the technical solution of the present invention, the Co 2+ The compound is Co(NO3)2·6H2O.

[0020] As a further improvement to the technical solution of this invention, it is applied to electrode materials.

[0021] The beneficial effects of this invention are as follows: The method for preparing manganese-based materials with different ion doping is based on a one-step hydrothermal method to synthesize manganese-based materials with different ion doping. A series of characterization methods have proven that the materials have been successfully prepared. Electrochemical tests have demonstrated that when applied to secondary batteries, they exhibit excellent cycle stability and rate performance. At the same time, this also broadens the scope of ion doping in the preparation and application of electrode materials for secondary batteries. Attached Figure Description

[0022] Figure 1 The images show the XRD patterns of Al doping MnO2 electrode materials obtained by the preparation method of this invention under different Al content conditions.

[0023] Figure 2 These are SEM (a) and TEM (b) images of the Al doping MnO2 electrode material obtained by the preparation method of this invention.

[0024] Figure 3 The Al doping MnO2 electrode material obtained by the preparation method of this invention is in 0.5A g -1 The following is a graph showing the cyclic performance.

[0025] Figure 4 This is a rate performance diagram of the Al doping MnO2 electrode material obtained by the preparation method of this invention under different current densities.

[0026] Figure 5 These are the XRD patterns of Ce-doping MnO2 electrode materials obtained by the preparation method of this invention under different Ce content conditions.

[0027] Figure 6 This is a TEM image of the Ce doping MnO2 electrode material obtained by the preparation method of this invention. Figure 7These are the cyclic voltammetry curves, charge-discharge curves, cycle performance diagrams, and rate performance diagrams of the Ce doping MnO2 electrode material obtained by the preparation method of this invention.

[0028] Figure 8 These are the XRD patterns of Ag doping MnO2 electrode materials obtained by the preparation method of this invention under different Ag content conditions.

[0029] Figure 9 At a current density of 0.5 A g -1 Cyclic performance graphs for undoped and doped states.

[0030] Figure 10 The images show the XRD patterns of Co-doping MnO2 electrode materials obtained by the preparation method of this invention under different Co content conditions.

[0031] Figure 11 At a current density of 0.5 A g -1 Cyclic performance graphs for undoped and doped states. Detailed Implementation

[0032] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments. A method for preparing a manganese-based material doped with different ions according to the present invention is implemented according to the following steps: Step 1, weigh 2 mmol (NH4)2SO4, 1 mmol (NH4)2S2O8, 1 mmol MnSO4 and 0.1 mmol-0.3 mmol AlCl3 respectively;

[0033] Step 2: Dissolve the weighed (NH4)2SO4, (NH4)2S2O8 and MnSO4 in 10mL-30mL of deionized water and stir for 5min-10min to obtain mixed solution A;

[0034] Step 3: Add the weighed AlCl3 to mixed solution A and stir for 10-15 minutes to obtain mixed solution B;

[0035] Step 4: Transfer mixed solution B to a stainless steel autoclave lined with polytetrafluoroethylene (PTFE), and react at 140℃-200℃ for 8-12 hours. After the autoclave cools naturally to room temperature, wash the precipitate multiple times with deionized water, then centrifuge and dry to obtain Al. 3+ Manganese-based doped materials.

[0036] Example 1

[0037] The present invention provides a method for preparing manganese-based materials doped with different ions, which is specifically implemented according to the following steps: Step 1, weigh 2 mmol (NH4)2SO4, 1 mmol (NH4)2S2O8, 1 mmol MnSO4 and 0.1 mmol AlCl3 respectively;

[0038] Step 2: Dissolve the weighed (NH4)2SO4, (NH4)2S2O8 and MnSO4 in 10 mL of deionized water and stir for 5 min to obtain mixed solution A;

[0039] Step 3: Add the weighed AlCl3 to mixed solution A and stir for 10 minutes to obtain mixed solution B;

[0040] Step 4: Transfer mixed solution B to a polytetrafluoroethylene-lined stainless steel autoclave and react at 140°C for 12 hours. After the autoclave cools naturally to room temperature, wash the precipitate multiple times with deionized water, then centrifuge and dry to obtain Al. 3+ Manganese-based doped materials.

[0041] Example 2

[0042] The present invention provides a method for preparing manganese-based materials doped with different ions, which is specifically implemented according to the following steps: Step 1, weigh 2 mmol (NH4)2SO4, 1 mmol (NH4)2S2O8, 1 mmol MnSO4 and 0.2 mmol AlCl3 respectively;

[0043] Step 2: Dissolve the weighed (NH4)2SO4, (NH4)2S2O8 and MnSO4 in 20 mL of deionized water and stir for 8 min to obtain mixed solution A;

[0044] Step 3: Add the weighed AlCl3 to mixed solution A and stir for 12 minutes to obtain mixed solution B;

[0045] Step 4: Transfer mixed solution B to a polytetrafluoroethylene-lined stainless steel autoclave and react at 170°C for 10 hours. After the autoclave cools naturally to room temperature, wash the precipitate multiple times with deionized water, then centrifuge and dry to obtain Al. 3+ Manganese-based doped materials.

[0046] Example 3

[0047] Step 1: Weigh out 2 mmol (NH4)2SO4, 1 mmol (NH4)2S2O8, 1 mmol MnSO4 and 0.3 mmol AlCl3 respectively;

[0048] Step 2: Dissolve the weighed (NH4)2SO4, (NH4)2S2O8 and MnSO4 in 30 mL of deionized water and stir for 10 min to obtain mixed solution A;

[0049] Step 3: Add the weighed AlCl3 to mixed solution A and stir for 15 minutes to obtain mixed solution B;

[0050] Step 4: Transfer mixed solution B to a polytetrafluoroethylene-lined stainless steel autoclave and react at 200°C for 8 hours. After the autoclave cools naturally to room temperature, wash the precipitate multiple times with deionized water, then centrifuge and dry to obtain Al. 3+ Manganese-based doped materials.

[0051] Figure 1 XRD patterns of doped and undoped metal ion sources were characterized. In the undoped state, the diffraction peaks point to the characteristic diffraction peaks of β-MnO2. In contrast, after adding an AlCl3 metal ion doping source, the peak intensity corresponds well to the characteristic diffraction peaks of α-MnO2. These results further confirm that a simple one-step hydrothermal method can successfully achieve the phase transition of MnO2 from the β phase to the α phase.

[0052] Figure 2 The image includes a SEM image (a) and a TEM image (b) showing the doped nanorods. Image (a) shows that the synthesized nanorods have a uniform morphology, and image (b) further verifies the synthesis of uniform nanorods under high magnification transmission.

[0053] Figure 3 At a current density of 0.5Ag -1 The cycling performance graphs show the undoped and doped states. In the undoped state, the specific capacity gradually decreases with cycling. After doping with a metal ion source, the cycling stability is significantly improved, with almost no capacity decay after 200 cycles. This indicates that doping helps improve the cycling stability of aqueous zinc-ion batteries.

[0054] Figure 4 This is a rate performance diagram of doped and undoped electrode materials at different current densities. At various tested current densities, the doped electrode materials all exhibited higher specific capacity than the undoped ones. The present invention provides a method for preparing manganese-based materials doped with different ions, specifically implemented according to the following steps: Step 1, weigh out 2 mmol (NH4)2SO4, 1 mmol (NH4)2S2O8, 1 mmol MnSO4, and 0.1 mmol-0.3 mmol Ce(NO3)3·6H2O, respectively;

[0055] Step 2: Dissolve the weighed (NH4)2SO4, (NH4)2S2O8 and MnSO4 in 10mL-30mL of deionized water and stir for 5min-10min to obtain mixed solution A;

[0056] Step 3: Add the weighed Ce(NO3)3·6H2O to mixed solution A and stir for 10-15 minutes to obtain mixed solution B;

[0057] Step 4: Transfer mixed solution B to a stainless steel autoclave lined with polytetrafluoroethylene (PTFE), and react at 140℃-200℃ for 8-12 hours. After the autoclave cools naturally to room temperature, wash the precipitate multiple times with deionized water, then centrifuge and dry to obtain Ce. 3+ Manganese-based doped materials.

[0058] Example 4

[0059] The present invention provides a method for preparing manganese-based materials doped with different ions, which is specifically implemented according to the following steps: Step 1, weigh out 2 mmol (NH4)2SO4, 1 mmol (NH4)2S2O8, 1 mmol MnSO4 and 0.1 mmol Ce(NO3)3·6H2O respectively;

[0060] Step 2: Dissolve the weighed (NH4)2SO4, (NH4)2S2O8 and MnSO4 in 10 mL of deionized water and stir for 5 min to obtain mixed solution A;

[0061] Step 3: Add the weighed Ce(NO3)3·6H2O to mixed solution A and stir for 10 min to obtain mixed solution B;

[0062] Step 4: Transfer mixed solution B to a polytetrafluoroethylene-lined stainless steel autoclave and react at 140°C for 12 hours. After the stainless steel autoclave cools naturally to room temperature, wash the precipitate multiple times with deionized water, then centrifuge and dry to obtain Ce. 3+ Manganese-based doped materials.

[0063] Example 5

[0064] The present invention provides a method for preparing manganese-based materials doped with different ions, which is specifically implemented according to the following steps: Step 1, weigh 2 mmol (NH4)2SO4, 1 mmol (NH4)2S2O8, 1 mmol MnSO4 and 0.2 mmol Ce(NO3)3·6H2O respectively;

[0065] Step 2: Dissolve the weighed (NH4)2SO4, (NH4)2S2O8 and MnSO4 in 20 mL of deionized water and stir for 8 min to obtain mixed solution A;

[0066] Step 3: Add the weighed Ce(NO3)3·6H2O to mixed solution A and stir for 12 minutes to obtain mixed solution B;

[0067] Step 4: Transfer mixed solution B to a polytetrafluoroethylene-lined stainless steel autoclave and react at 170°C for 10 hours. After the autoclave cools naturally to room temperature, wash the precipitate multiple times with deionized water, then centrifuge and dry to obtain Ce. 3+ Manganese-based doped materials.

[0068] Example 6

[0069] Step 1: Weigh out 2 mmol (NH4)2SO4, 1 mmol (NH4)2S2O8, 1 mmol MnSO4 and 0.3 mmol Ce(NO3)3·6H2O respectively;

[0070] Step 2: Dissolve the weighed (NH4)2SO4, (NH4)2S2O8 and MnSO4 in 30 mL of deionized water and stir for 10 min to obtain mixed solution A;

[0071] Step 3: Add the weighed Ce(NO3)3·6H2O to mixed solution A and stir for 15 min to obtain mixed solution B;

[0072] Step 4: Transfer mixed solution B to a polytetrafluoroethylene-lined stainless steel autoclave and react at 200°C for 8 hours. After the autoclave cools naturally to room temperature, wash the precipitate multiple times with deionized water, then centrifuge and dry to obtain Ce. 3+ Manganese-based doped materials.

[0073] Figure 5 The XRD patterns of doped and undoped metal ion sources were characterized. In the undoped state, the diffraction peaks pointed to the characteristic diffraction peaks of β-MnO2. After adding the Ce(NO3)3·6H2O metal ion doping source, its peak intensity corresponded well to the characteristic diffraction peaks of α-MnO2. Figure 6 The images include TEM images (a), high-resolution TEM images (b) and (c), and elemental mappings (d) and (e). Image (a) shows that the synthesized nanorods have a uniform morphology. Images (b) and (c) show that the characterized lattice spacing values ​​match well with the (110) and (200) crystal planes of α-MnO2. Images (d) and (e) show that Mn, O, and Ce elements are uniformly distributed on the nanorods.

[0074] Figure 7The figures include the CV (a), GCD (b), cycle performance (c), and rate performance (d) after doping. Figures (a) and (b) show the reduction in polarization of the electrode material after doping. Figure (c) shows the cycle performance at a current density of 5C for both the undoped and doped states. The cycle stability is significantly improved after doping with a metal ion source, indicating that doping contributes to improving the cycle stability of aqueous zinc-ion batteries. Figure (d) shows the rate performance of the doped and undoped electrode materials at different current densities. At all tested current densities, the doped electrode material exhibits a higher specific capacity than the undoped form.

[0075] The present invention provides a method for preparing manganese-based materials doped with different ions, which is specifically implemented according to the following steps: Step 1, weigh 2 mmol (NH4)2SO4, 1 mmol (NH4)2S2O8, 1 mmol MnSO4 and 0.1 mmol-0.3 mmol AgNO3 respectively;

[0076] Step 2: Dissolve the weighed (NH4)2SO4, (NH4)2S2O8 and MnSO4 in 10mL-30mL of deionized water and stir for 5min-10min to obtain mixed solution A;

[0077] Step 3: Add the weighed AgNO3 to mixed solution A and stir for 10-15 minutes to obtain mixed solution B;

[0078] Step 4: Transfer mixed solution B to a polytetrafluoroethylene-lined stainless steel autoclave and react at 140℃-200℃ for 8-12 hours. After the stainless steel autoclave cools naturally to room temperature, wash the precipitate multiple times with deionized water, then centrifuge and dry to obtain Ag. + Manganese-based doped materials.

[0079] Example 7

[0080] The present invention provides a method for preparing manganese-based materials doped with different ions, which is specifically implemented according to the following steps: Step 1, weigh 2 mmol (NH4)2SO4, 1 mmol (NH4)2S2O8, 1 mmol MnSO4 and 0.1 mmol AgNO3 respectively;

[0081] Step 2: Dissolve the weighed (NH4)2SO4, (NH4)2S2O8 and MnSO4 in 10 mL of deionized water and stir for 5 min to obtain mixed solution A;

[0082] Step 3: Add the weighed AgNO3 to mixed solution A and stir for 10 minutes to obtain mixed solution B;

[0083] Step 4: Transfer mixed solution B to a polytetrafluoroethylene-lined stainless steel autoclave and react at 140°C for 12 hours. After the stainless steel autoclave cools naturally to room temperature, wash the precipitate multiple times with deionized water, then centrifuge and dry to obtain Ag. + Manganese-based doped materials.

[0084] Example 8

[0085] The present invention provides a method for preparing manganese-based materials doped with different ions, which is specifically implemented according to the following steps: Step 1, weigh 2 mmol (NH4)2SO4, 1 mmol (NH4)2S2O8, 1 mmol MnSO4 and 0.2 mmol AgNO3 respectively;

[0086] Step 2: Dissolve the weighed (NH4)2SO4, (NH4)2S2O8 and MnSO4 in 20 mL of deionized water and stir for 8 min to obtain mixed solution A;

[0087] Step 3: Add the weighed AgNO3 to mixed solution A and stir for 12 minutes to obtain mixed solution B;

[0088] Step 4: Transfer mixed solution B to a polytetrafluoroethylene-lined stainless steel autoclave and react at 170°C for 10 hours. After the stainless steel autoclave cools naturally to room temperature, wash the precipitate multiple times with deionized water, then centrifuge and dry to obtain Ag. + Manganese-based doped materials.

[0089] Example 9

[0090] Step 1: Weigh out 2 mmol (NH4)2SO4, 1 mmol (NH4)2S2O8, 1 mmol MnSO4 and 0.3 mmol AgNO3 respectively;

[0091] Step 2: Dissolve the weighed (NH4)2SO4, (NH4)2S2O8 and MnSO4 in 30 mL of deionized water and stir for 10 min to obtain mixed solution A;

[0092] Step 3: Add the weighed AgNO3 to mixed solution A and stir for 15 minutes to obtain mixed solution B;

[0093] Step 4: Transfer mixed solution B to a polytetrafluoroethylene-lined stainless steel autoclave and react at 200°C for 8 hours. After the stainless steel autoclave cools naturally to room temperature, wash the precipitate multiple times with deionized water, then centrifuge and dry to obtain Ag. + Manganese-based doped materials.

[0094] Figure 8XRD patterns of doped and undoped metal ion sources are shown in Figure (a). Figure (a) shows that, in the undoped state, the diffraction peaks point to the characteristic diffraction peaks of β-MnO2. In contrast, the phase state of MnO2 changes after the addition of AgNO3 metal ion doping source. Figure 9 At a current density of 0.5 A g -1 The graphs show the cycling performance in both undoped and doped states. The cycling stability is significantly improved after doping with a metal ion source. This indicates that doping helps improve the cycling stability of aqueous zinc-ion batteries.

[0095] The present invention provides a method for preparing manganese-based materials doped with different ions, which is specifically implemented according to the following steps: Step 1, weigh out 2 mmol (NH4)2SO4, 1 mmol (NH4)2S2O8, 1 mmol MnSO4 and 0.1 mmol-0.3 mmol Co(NO3)2·6H2O respectively;

[0096] Step 2: Dissolve the weighed (NH4)2SO4, (NH4)2S2O8 and MnSO4 in 10mL-30mL of deionized water and stir for 5min-10min to obtain mixed solution A;

[0097] Step 3: Add the weighed Co(NO3)2·6H2O to mixed solution A and stir for 10-15 minutes to obtain mixed solution B;

[0098] Step 4: Transfer mixed solution B to a stainless steel autoclave lined with polytetrafluoroethylene (PTFE), and react at 140℃-200℃ for 8-12 hours. After the autoclave cools naturally to room temperature, wash the precipitate multiple times with deionized water, then centrifuge and dry to obtain Co. 2+ Manganese-based doped materials.

[0099] Example 10

[0100] The present invention provides a method for preparing manganese-based materials doped with different ions, which is specifically implemented according to the following steps: Step 1, weigh 2 mmol (NH4)2SO4, 1 mmol (NH4)2S2O8, 1 mmol MnSO4 and 0.1 mmol Co(NO3)2·6H2O respectively;

[0101] Step 2: Dissolve the weighed (NH4)2SO4, (NH4)2S2O8 and MnSO4 in 10 mL of deionized water and stir for 5 min to obtain mixed solution A;

[0102] Step 3: Add the weighed Co(NO3)2·6H2O to mixed solution A and stir for 10 min to obtain mixed solution B;

[0103] Step 4: Transfer mixed solution B to a polytetrafluoroethylene-lined stainless steel autoclave and react at 140°C for 12 hours. After the autoclave cools naturally to room temperature, wash the precipitate multiple times with deionized water, then centrifuge and dry to obtain Co. 2+ Manganese-based doped materials.

[0104] Example 11

[0105] The present invention discloses a method for preparing manganese-based materials doped with different ions, which is specifically implemented according to the following steps:

[0106] Step 1: Weigh out 2 mmol (NH4)2SO4, 1 mmol (NH4)2S2O8, 1 mmol MnSO4 and 0.2 mmol Co(NO3)2·6H2O respectively;

[0107] Step 2: Dissolve the weighed (NH4)2SO4, (NH4)2S2O8 and MnSO4 in 20 mL of deionized water and stir for 8 min to obtain mixed solution A;

[0108] Step 3: Add the weighed Co(NO3)2·6H2O to mixed solution A and stir for 12 minutes to obtain mixed solution B;

[0109] Step 4: Transfer mixed solution B to a polytetrafluoroethylene-lined stainless steel autoclave and react at 170°C for 10 hours. After the autoclave cools naturally to room temperature, wash the precipitate multiple times with deionized water, then centrifuge and dry to obtain Co. 2+ Manganese-based doped materials.

[0110] Example 12

[0111] Step 1: Weigh out 2 mmol (NH4)2SO4, 1 mmol (NH4)2S2O8, 1 mmol MnSO4 and 0.3 mmol Co(NO3)2·6H2O respectively;

[0112] Step 2: Dissolve the weighed (NH4)2SO4, (NH4)2S2O8 and MnSO4 in 30 mL of deionized water and stir for 10 min to obtain mixed solution A;

[0113] Step 3: Add the weighed Co(NO3)2·6H2O to mixed solution A and stir for 15 min to obtain mixed solution B;

[0114] Step 4: Transfer mixed solution B to a polytetrafluoroethylene-lined stainless steel autoclave and react at 200°C for 8 hours. After the autoclave cools naturally to room temperature, wash the precipitate multiple times with deionized water, then centrifuge and dry to obtain Co. 2+Manganese-based doped materials.

[0115] Figure 10 XRD patterns of doped and undoped metal ion sources are shown in Figure (a). Figure (a) shows that when undoped, the diffraction peaks point to the characteristic diffraction peaks of β-MnO2. In contrast, when a certain concentration of Co(NO3)2·6H2O metal ion dopant source is added, the phase state of MnO2 changes.

[0116] Figure 11 At a current density of 0.5 A g -1 The graphs show the cycling performance in both undoped and doped states. The cycling stability is significantly improved after doping with a metal ion source. This indicates that doping helps improve the cycling stability of aqueous zinc-ion batteries.

Claims

1. A method for preparing manganese-based materials doped with different ions, characterized in that, The specific steps are as follows: Step 1: Weigh (NH4)2SO4, (NH4)2S2O8, MnSO4 and Al according to the molar ratio of 2:1:1:0.1-0.

3. 3+ Compound or Ce 3+ Compound or Ag + Compound or Co 2+ Compound; the Al 3+ The compound is AlCl3, and the Ce 3+ The compound is Ce(NO3)3·6H2O, and the Ag... + The compound is AgNO3, and the Co 2+ The compound is Co(NO3)2·6H2O; Step 2: Dissolve the weighed (NH4)2SO4, (NH4)2S2O8 and MnSO4 in deionized water and stir until homogeneous to obtain mixed solution A; Step 3, weigh out the Al 3+ Compound or Ce 3+ Compound or Ag + Compound or Co 2+ The compound is added to mixed solution A and stirred until homogeneous to obtain mixed solution B; Step 4: Transfer the mixed solution B to a stainless steel autoclave lined with polytetrafluoroethylene and react at 140℃-200℃ for 8-12 hours. After the stainless steel autoclave cools naturally to room temperature, wash the precipitate multiple times with deionized water, then centrifuge and dry to obtain manganese-based materials doped with different ions.

2. The method for preparing manganese-based materials with different ion doping according to claim 1, characterized in that, In step 1, the following substances were weighed: (NH4)2SO4, (NH4)2S2O8, MnSO4, and Al. 3+ Compound or Ce 3+ Compound or Ag + Compound or Co 2+ The compounds were 2 mmol, 1 mmol, 1 mmol, and 0.1 mmol-0.3 mmol, respectively.

3. The method for preparing manganese-based materials with different ion doping according to claim 2, characterized in that, In step 2, the amount of deionized water is 10 mL to 30 mL.

4. The method for preparing manganese-based materials with different ion doping according to claim 3, characterized in that, In step 2, the stirring time is 5-10 minutes.

5. The method for preparing manganese-based materials with different ion doping according to claim 4, characterized in that, In step 3, the stirring time is 10-15 minutes.

6. The manganese-based material obtained by the preparation method of manganese-based materials with different ion doping according to any one of claims 1-5, characterized in that, Applications in electrode materials.

Images