Hollow LDH/MnO2 nanocage composite material as well as preparation method and application thereof

A composite material, nano-cage technology, applied in nanotechnology, nanotechnology, nanotechnology for materials and surface science, etc., can solve the problems of low discharge capacity, inability to achieve high capacity of lithium-air batteries, easy stacking, etc. The effect of accelerating mass transfer process, excellent catalytic activity, and improving kinetics

Active Publication Date: 2020-12-08
SHANDONG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the above-mentioned layered double metal hydroxides are OER catalysts, and the catalyst for ORR is weak, which will lead to low discharge capacity and cannot achieve high capacity of lithium-air batteries.
[0005] Therefore, it is of great significance to develop a LDHs material with a simple preparation process, which can effectively avoid the shortcoming of easy stacking of two-dimensional materials and has excellent ORR / OER catalytic activity, for improving the performance of lithium-air batteries.

Method used

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  • Hollow LDH/MnO2 nanocage composite material as well as preparation method and application thereof
  • Hollow LDH/MnO2 nanocage composite material as well as preparation method and application thereof
  • Hollow LDH/MnO2 nanocage composite material as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0052] A Hollow NiCo LDH / MnO 2 The preparation method of nano cage composite material, comprises steps as follows:

[0053] (1) Add 0.728g of cobalt nitrate hexahydrate and 0.821g of 2-methylimidazole into 20mL of methanol respectively, and ultrasonically vibrate for 5 minutes to obtain a methanol solution of cobalt nitrate and a methanol solution of 2-methylimidazole, and 2-methylimidazole The methanol solution of cobalt nitrate was added to the methanol solution of cobalt nitrate and mixed evenly. The resulting mixed solution was aged at room temperature for 24 hours, and the precipitate was collected by centrifugation. The obtained precipitate was washed with methanol three times, and dried at 60°C for 12 hours to obtain ZIF-67.

[0054] (2) 0.1g ZIF-67 and 0.5g nickel nitrate are added in 20mL ethanol respectively, ultrasonic vibration 10min, obtain ZIF-67 dispersion liquid and nickel nitrate dispersion liquid, nickel nitrate dispersion liquid is added in ZIF-67 dispersion...

Embodiment 2

[0067] A Hollow CoCo LDH / MnO 2 The preparation method of nano cage composite material, comprises steps as follows:

[0068] (1) Described with embodiment 1 step (1).

[0069] (2) 0.1g ZIF-67 and 0.5g cobalt nitrate are added in 20mL methanol respectively, ultrasonic vibration 10min, obtain ZIF-67 dispersion liquid and cobalt nitrate dispersion liquid, cobalt nitrate dispersion liquid is added in ZIF-67 dispersion liquid, in The reaction was continuously stirred in a water bath at 60° C. for 1 h, and the precipitate was collected by centrifugation. The obtained precipitate was washed with ethanol three times, and dried at 60° C. for 12 h to obtain a CoCo LDH material.

[0070] (3) Add 70mg CoCo LDH material to 20mL 0.03mol / L KMnO 4 solution, stirred and mixed for 1 h, transferred the resulting mixture to a 50 mL polytetrafluoroethylene-lined stainless steel autoclave, and reacted hydrothermally at 160°C for 3 h; after the reaction was completed, centrifuged, and the centrifug...

Embodiment 3

[0074] A Hollow CuCo LDH / MnO 2 The preparation method of nano cage composite material, comprises steps as follows:

[0075] (1) Described with embodiment 1 step (1).

[0076] (2) Add 0.1g ZIF-67 and 0.5g cupric chloride into 20mL ethanol respectively, and oscillate ultrasonically for 10min to obtain ZIF-67 dispersion and cupric chloride dispersion, and add cupric chloride dispersion to ZIF-67 dispersion In 60 °C water bath, the reaction was continuously stirred for 1 h, the precipitate was collected by centrifugation, the obtained precipitate was washed with ethanol three times, and dried at 60 °C for 12 h to obtain the CuCo LDH material.

[0077] (3) Add 70mg CuCo LDH material to 20mL 0.03mol / L KMnO 4 solution, stirred and mixed for 1 h, transferred the resulting mixture to a 50 mL polytetrafluoroethylene-lined stainless steel autoclave, and reacted hydrothermally at 160°C for 3 h; after the reaction was completed, centrifuged, and the centrifuged precipitate was washed 3 t...

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Abstract

The invention provides a hollow LDH/MnO2 nanocage composite material as well as a preparation method and application thereof, and the preparation method comprises the following steps: by taking ZIF-67as a self-template, forming a hollow LDH nanocage in situ by adopting simple etching and hydrothermal reaction, and growing ultrathin MnO2 nanosheets on the hollow LDH nanocage to obtain the LDH/MnO2nanocage composite material with a hollow dodecahedron structure. The preparation method disclosed by the invention is simple and easy to control in preparation process, environment-friendly and suitable for large-scale industrial production. The hollow structure and synergistic effect of the composite material can fully expose active sites and accelerate the mass transfer process, and when the composite material is used as a positive electrode material for a lithium-air battery, the reaction kinetics can be accelerated, the charging overpotential can be reduced, and the cycling stability ofthe battery can be improved.

Description

technical field [0001] The invention relates to a hollow LDH / MnO 2 The nano cage composite material and its preparation method and application belong to the technical field of lithium-air batteries. Background technique [0002] As a new generation of batteries, lithium-air batteries (Li-O 2 ) has the advantages of low cost and environmental friendliness, and has the highest theoretical energy density (theoretical value is 3505Wh kg -1 ), three to four times that of state-of-the-art lithium-ion batteries, meeting the needs of large-scale energy storage. [0003] The lithium-air battery reaction is divided into two processes: oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). During the ORR process, a large amount of Li 2 o 2 Formed and deposited on the surface of the electrode, it hinders the transport of ions and gases, increases the interfacial impedance, and leads to a decrease in battery capacity and charge transport capability. In the OER process...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/86H01M4/88H01M4/90H01M12/08B82Y30/00B82Y40/00
CPCH01M4/8647H01M4/8825H01M4/9016H01M4/9075H01M12/08B82Y30/00B82Y40/00H01M2004/8689Y02E60/10
Inventor 尹龙卫丁明洁王朋张志薇赵瑞正
Owner SHANDONG UNIV
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