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Preparation method of cluster MnO2, secondary zinc-manganese battery positive electrode material and secondary zinc-manganese battery

A zinc-manganese battery and cluster technology, applied in secondary batteries, battery electrodes, manganese oxide/manganese hydroxide, etc., can solve the problem of reducing the utilization rate of active materials and the electrochemical activity of electrodes, limiting large-scale market applications, and recycling Poor stability and other issues, to achieve the effect of improving conductivity and electrochemical activity, enhancing electrode reversibility, and easy handling

Active Publication Date: 2022-06-03
NANJING UNIV OF INFORMATION SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, at present, secondary aqueous zinc-manganese batteries still generally suffer from poor cycle stability and serious capacity fading, which limits their large-scale market application.
Studies have shown that one of the reasons for its capacity fading may be that inert substances are generated and attached to the surface of the positive electrode material during the charge-discharge cycle of the battery, reducing the utilization rate of the active material and the electrochemical activity of the electrode.

Method used

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  • Preparation method of cluster MnO2, secondary zinc-manganese battery positive electrode material and secondary zinc-manganese battery
  • Preparation method of cluster MnO2, secondary zinc-manganese battery positive electrode material and secondary zinc-manganese battery
  • Preparation method of cluster MnO2, secondary zinc-manganese battery positive electrode material and secondary zinc-manganese battery

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] (1) Weigh MnSO in a molar ratio of 1:1 4 ·H 2 O and (NH 4 ) 2 S 2 O 8 Dissolved in deionized water, adding phenylphosphonic acid as an additive to make it compatible with MnSO 4 ·H 2 The O molar ratio was 0.04. Dilute to 250mL to make MnSO 4 ·H 2 O and (NH 4 ) 2 S 2 O 8 The concentration is 0.05mol / L, and the concentration of phenylphosphonic acid is 0.002mol / L; a homogeneous solution is obtained;

[0033] (2) transfer the obtained homogeneous solution into a hydrothermal kettle, put it into a muffle furnace to carry out a hydrothermal process, and the reaction conditions are 110° C. for 16 h to obtain a gray-black suspension;

[0034] (3) The gray-black suspension was filtered by suction, washed with deionized water, and then the precipitate was vacuum-dried at 60 °C for 24 h to obtain the micro-nano-clustered manganese dioxide material.

[0035] like figure 1 As shown, the material obtained by XRD characterization is β-type manganese dioxide, and its di...

Embodiment 2

[0037] (1) Weigh MnSO in a molar ratio of 1:1 4 ·H 2 O and (NH 4 ) 2 S 2 O 8 Dissolved in deionized water, disodium phenylphosphonate dihydrate was added as an additive to make it compatible with MnSO 4 ·H 2 The O molar ratio was 0.12. Dilute to 250mL to make MnSO 4 ·H 2 O and (NH 4 )2 S 2 O 8 The concentrations are all 0.1 mol / L, and the concentration of disodium phenylphosphonate is 0.012 mol / L; a homogeneous solution is obtained;

[0038] (2) transfer the obtained homogeneous solution to a hydrothermal kettle, put it into a muffle furnace to carry out a hydrothermal process, and the reaction conditions are 130° C. for 6 h to obtain a gray-black suspension;

[0039] (3) The gray-black suspension was filtered by suction, washed with deionized water, and then the precipitate was vacuum-dried at 90° C. for 12 h to obtain the micro-nano-clustered manganese dioxide material.

[0040] like image 3 As shown, the SEM characterization shows that the material is organic...

Embodiment 3

[0042] (1) Weigh MnSO in a molar ratio of 1:1 4 ·H 2 O and (NH 4 ) 2 S 2 O 8 Dissolved in deionized water, disodium phenylphosphonate dihydrate was added as an additive to make it compatible with MnSO 4 ·H 2 The O molar ratio is 0.1. Dilute to 250mL to make MnSO 4 ·H 2 O and (NH 4 ) 2 S 2 O 8 The concentrations are all 0.07mol / L, and the concentration of disodium phenylphosphonate is 0.007mol / L; a homogeneous solution is obtained;

[0043] (2) transfer the obtained homogeneous solution into a hydrothermal kettle, put it into a muffle furnace to carry out a hydrothermal process, and the reaction conditions are 120° C. for 12 h to obtain a gray-black suspension;

[0044] (3) The gray-black suspension was filtered by suction, washed with deionized water, and then the precipitate was vacuum-dried at 90° C. for 12 h to obtain the micro-nano-clustered manganese dioxide material.

[0045] The micro-nano-clustered manganese dioxide material was used as the positive elect...

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Abstract

The invention discloses a preparation method of cluster MnO2, a secondary zinc-manganese battery positive electrode material and a secondary zinc-manganese battery, the preparation method comprises the following steps: dissolving manganese salt and peroxydisulfate in water, and adding phenyl phosphonic acid or phenyl phosphonate to obtain a mixed solution; carrying out hydrothermal reaction on the mixed solution to obtain turbid liquid containing manganese dioxide precipitate; and carrying out suction filtration, washing and drying on the turbid liquid to obtain the micro-nano cluster spherical manganese dioxide. The cluster MnO2 prepared by the method disclosed by the invention is of a micro-nano cluster structure, specifically, nano wires are organically polymerized into micron-sized cluster particles, and the cluster MnO2 has the characteristic of high specific surface area of a nano material and can be in full contact with electrolyte, so that the reaction sites of active substances are increased, and the conductivity and electrochemical activity of an electrode are improved; the electrode reversibility of the secondary aqueous zinc-manganese battery positive electrode material is effectively enhanced, and the cycling stability is improved; and the capacity retention ratio reaches up to 94.2% after 500 cycles at the current density of 500mA / g.

Description

technical field [0001] The invention relates to a preparation method of a manganese oxide material, a secondary battery positive electrode material and a secondary battery, in particular to a cluster MnO 2 Preparation method, cathode material of secondary zinc-manganese battery and secondary zinc-manganese battery. Background technique [0002] Compared with the lithium-ion batteries that are generally studied at present, the secondary aqueous zinc-manganese batteries have received more and more attention due to their outstanding advantages such as high energy density, cheap and environmentally friendly materials, high safety, and more convenient battery assembly. Research. The research on secondary water-based zinc-manganese batteries mainly focuses on positive electrode materials, electrolytes, negative electrodes, etc., among which the research on positive electrode materials is the most extensive. 2 , MnO, Mn 3 O 4 , ZnMn 2 O 4 etc.), especially MnO 2 Because of i...

Claims

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Application Information

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IPC IPC(8): C01G45/02B82Y40/00H01M4/50H01M10/36
CPCC01G45/02B82Y40/00H01M4/50H01M10/36C01P2004/32C01P2004/45C01P2004/16C01P2006/40Y02E60/10
Inventor 李龙燕涂天成代启航胡冰洁贾益阳
Owner NANJING UNIV OF INFORMATION SCI & TECH
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