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Manganese ammonium fluoride/manganese dioxide composite material and preparation method thereof

A technology of manganese dioxide and ammonium manganese fluoride, which is applied in the manufacture of hybrid/electric double layer capacitors and electrodes of hybrid capacitors, can solve the problem of limiting specific capacitance, cycle stability of rate performance, and polluting fluorine-containing acetone waste Solve the problems such as poor cycle life of liquid and electrode materials, and achieve the effect of wide working voltage range, good application prospects, and high specific capacitance

Active Publication Date: 2019-04-16
SHANDONG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Manganese dioxide material has a large theoretical specific capacitance, but due to its poor conductivity, it is easy to form Mn(OH) with poor conductivity during the charge and discharge cycle. 2 Layer, which further limits its specific capacitance, rate performance, and cycle stability
However, the method he adopted has lengthy steps and high cost, and will produce polluting fluorine-containing acetone waste liquid
Zhang Lizhi et al. (CN102034965 A) used manganese nitrate, ammonium fluoride, and polyethylene glycol to prepare manganese difluoride cubic materials. Its size is uniform (2-4 μm), and its pore structure is rich, which is conducive to the improvement of the specific capacity of lithium-ion batteries. , but the cycle life of this electrode material is not good, and only 58.3% of the specific capacity remains after 30 cycles

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] (1) Disperse 1g of manganese silicate powder in 50mL of deionized water, ultrasonically homogenize, dissolve 20g of ammonium fluoride in 250mL of deionized water, transfer the two to the lining of a 500mL reactor, stir vigorously for 1 hour, and obtain a brown mixture;

[0019] (2) Introduce nitrogen gas into the brown mixture prepared in (1), and screw on the lid; put the reaction kettle into an oven, keep it warm at 180°C for 5 hours, and then take it out. First use deionized water twice, and finally use absolute ethanol as a cleaning agent to clean and centrifuge to separate the precipitate, dry at 105°C for 12 hours, and grind to obtain a brown powder ammonium manganese fluoride / manganese dioxide composite material.

[0020] The mass percent of each component in the prepared composite material is: 52.4% of ammonium manganese fluoride and 47.6% of manganese dioxide. The supercapacitor pole piece assembled with this electrode material has a maximum working voltage ran...

Embodiment 2

[0022] (1) Disperse 4g of manganese silicate powder in 50mL of ethanol, sonicate evenly, dissolve 20g of ammonium fluoride in 250mL of deionized water, transfer the two to the lining of a 500mL reactor, stir vigorously for 1 hour, and obtain a brown mixture;

[0023] (2) Introduce nitrogen gas into the brown mixture prepared in (1) for 1 min, and screw on the lid; put the reaction kettle in an oven, keep it warm at 180°C for 5 h, and then take it out. First use deionized water twice, and finally use absolute ethanol as a cleaning agent to clean and centrifuge to separate the precipitate, dry at 105°C for 12 hours, and grind to obtain a brown powder ammonium manganese fluoride / manganese dioxide composite material.

[0024] The mass percent of each component in the prepared composite material is: 47.4% of ammonium manganese fluoride and 52.6% of manganese dioxide. The supercapacitor pole piece assembled with this electrode material has a maximum working voltage range of 1V and a...

Embodiment 3

[0026] (1) Disperse 5g of manganese silicate powder in 50mL of deionized water, sonicate evenly, dissolve 20g of ammonium fluoride in 250mL of deionized water, transfer the two to the lining of a 500mL reactor, stir vigorously for 1 hour, and obtain a brown mixture;

[0027] (2) Put the reaction kettle in the step (1) into an oven, keep it warm at 150° C. for 10 hours, and then take it out. First use deionized water twice, and finally use absolute ethanol as a cleaning agent to clean and centrifuge to separate the precipitate, dry at 105°C for 12 hours, and grind to obtain a brown powder ammonium manganese fluoride / manganese dioxide composite material.

[0028] The mass percent of each component in the prepared composite material is: 44.4% of ammonium manganese fluoride and 55.6% of manganese dioxide. The supercapacitor pole piece assembled with this electrode material has a maximum working voltage range of 1V and a maximum specific capacitance of 160F g -1 .

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Abstract

The invention belongs to the field of new materials and relates to a manganese ammonium fluoride / manganese dioxide composite material mainly used in a supercapacitor and a preparation method thereof.The composite material of the invention comprises, by weight, 40% to 60% of manganese ammonium fluoride and 60% to 40% of manganese dioxide. The preparation method comprises the steps of firstly dissolving ammonium fluoride in deionized water, dispersing manganese silicate powders in a solvent, and achieving ultrasound uniformity; then transferring a mixture to a reaction vessel for hydrothermal reaction; collecting a solid reaction product, cleaning the solid reaction product with a cleaning agent, and separating the target ammonium manganese fluoride / manganese dioxide composite material. Themanganese ammonium fluoride / manganese dioxide composite material prepared by the method has high specific capacitance, a large working voltage range, good rate performance and cycle stability, and good application prospect. The preparation method is easy to operate, low in cost and convenient for mass production.

Description

technical field [0001] The invention belongs to the field of new materials, and relates to a manganese ammonium fluoride / manganese dioxide (NH 4 MnF 3 / MnO 2 ) Electrode composite material and its preparation method. Background technique [0002] With the continuous development of smart grid, electric vehicles, consumer electronics, aerospace and other fields, people have higher and higher requirements for energy storage and conversion devices. Supercapacitors have the advantages of long cycle life, good cycle stability, fast charge and discharge speed, strong anti-interference, and compact size. At present, supercapacitor electrode materials are mainly divided into three categories: one is electric double layer capacitor materials, the other is pseudocapacitive materials, and the third is battery capacitor materials. To research and develop supercapacitor devices with high energy density, high power density and good cycle stability, new energy storage electrode material...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01G11/30H01G11/46H01G11/86
CPCH01G11/30H01G11/46H01G11/86Y02E60/13
Inventor 张希华李斌
Owner SHANDONG UNIV