Manganese-based ternary integrated difunctional oxygen electrode and preparation method and application thereof

A manganese-based ternary, bifunctional technology, applied in the field of electrocatalysis, can solve the problems of poor stability of cobalt-based transition metal oxides, low conductivity and poor stability of manganese oxides, and achieves improved catalyst performance, improved conductivity, The effect of improving oxygen evolution performance

Pending Publication Date: 2022-07-15
DONGHUA UNIV +1
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] The technical problem to be solved by the present invention is: how to overcome technical problems such as low electrical conductivity and poor stability of manganese oxide and poor stability and poor activity of cobalt-based transition metal oxides

Method used

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  • Manganese-based ternary integrated difunctional oxygen electrode and preparation method and application thereof
  • Manganese-based ternary integrated difunctional oxygen electrode and preparation method and application thereof
  • Manganese-based ternary integrated difunctional oxygen electrode and preparation method and application thereof

Examples

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Embodiment 1

[0033] This embodiment provides a manganese-based ternary integrated bifunctional oxygen electrode (NiCo 2 O 4 / MnO 2 / C@Ni-Foam) preparation method, the specific preparation steps are as follows:

[0034] Step 1: Put 0.79g KMnO 4 Add 50 mL of deionized water, stir until the crystals disappear, and continue to sonicate to ensure complete dissolution;

[0035] Step 2: 2ml (12mol / L) hydrochloric acid was added to the solution of step 1, transferred to the reaction kettle, and reacted at 140°C for 12 hours;

[0036] Step 3: Centrifuge step 2), wash with water and alcohol, dry the collected precipitate at 70°C, and obtain MnO after structural characterization 2Tubular crystals, i.e. MnO 2 nanotube;

[0037] Step 4: Put 0.249gCo(Ac) 2 ·4H 2 O and 0.248g Ni(Ac) 2 ·4H 2 O and 20mg carbon nanotubes (diameter 20~30nm, purity>98%wt, Zhongke Times Nano Center) add 30mL ammonia water, stir until the crystal disappears, continue to ultrasonically vibrate to ensure complete dissol...

Embodiment 2

[0067] 10 mg of the bifunctional oxygen electrodes prepared in Example 1 and Comparative Examples 1 to 3 were mixed with Pt / C-RuO 2 The powder was dissolved in ethanol and 5% Nafion solution, sonicated for 30 minutes to form a uniform catalyst slurry, and then spread on hydrophobic treated carbon paper (loading 2 mg / cm2). 2 ), and dried at 50°C for 40 minutes to prepare an air electrode. Using zinc foil as the negative electrode, the air electrode, zinc foil and 6 mol / L potassium hydroxide solution were put into the self-made zinc-air battery tank, and the blue electricity system was used for testing. . The test conditions are from 1 mA to 350 mA of gradual discharge with a rate of change of 1 mA / s.

[0068] Test results such as Figure 2a , 2b shown, Figure 2a NiCo prepared for Example 1 2 O 4 / MnO 2 / C@Ni-Foam catalyst and commercial Pt / C-RuO 2 The power comparison of the catalyst shows that (Ni,Co) / MnO 2 The peak power of 210mW / cm 2 Significantly better than Pt / C...

Embodiment 3

[0070] 10 mg of the bifunctional oxygen electrodes prepared in Example 1 and Comparative Examples 1 to 3 were mixed with Pt / C-RuO 2 The powder was dissolved in ethanol and 5% Nafion solution, sonicated for 30 minutes to form a uniform catalyst slurry, and then spread on hydrophobic treated carbon paper (loading 2 mg / cm2). 2 ), and dried at 50°C for 40 minutes to prepare an air electrode. Using zinc foil as the negative electrode, the air electrode, zinc foil and 6 mol / L potassium hydroxide solution were put into the self-made zinc-air battery tank, and the blue electricity system was used for testing. . Test condition 5mA / cm 2 Current density, 10 min full electrical cycle time.

[0071] Test results such as Figure 3a , 3b shown, it can be seen that at 5mA / cm 2 NiCo synthesized in Example 1 during constant current charge and discharge 2 O 4 / MnO 2 The / C@Ni-Foam catalyst has a larger open circuit voltage and discharge time (43h), the discharge voltage is maintained at ...

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Abstract

The invention discloses a manganese-based ternary integrated difunctional oxygen electrode as well as a preparation method and application thereof. The chemical composition of the bifunctional oxygen electrode is NiCo2O4 / MnO2 / C (at) Ni-Foam, and the bifunctional oxygen electrode is an integrated electrode which is of a kaleidoscope-shaped structure and is loaded with Co and Ni bimetal oxides and is formed by taking foamed nickel as a substrate, taking a MnO2 nanotube and a carbon nanotube as frameworks and taking cobalt salt and nickel salt as metal oxide sources through hydrothermal reaction self-assembly. Firstly, MnO2 tubular crystals are prepared through hydrothermal reaction, loading of an active carrier is facilitated, meanwhile, the difunctional oxygen electrode of a kaleidoscope-shaped structure is prepared by optimizing hydrothermal reaction conditions, the surface of the difunctional oxygen electrode is provided with a rich layered structure, a unique microstructure provides rich active sites, the difunctional oxygen electrode has good stability, and the difunctional oxygen electrode can be applied to the field of biochemistry. And when the composite material is used in the zinc-air battery, the composite material has good zinc-air battery charging and discharging performance.

Description

technical field [0001] The invention relates to a manganese-based ternary integrated bifunctional oxygen electrode, a preparation method and application thereof, and belongs to the technical field of electrocatalysis. Background technique [0002] The rechargeable zinc-air battery (RZAB) has a high theoretical energy density (1086Wh / Kg, which is 3-5 times that of the current lithium-ion battery, and the cost is only 1 / 40 of that of the lithium-ion battery), and its aqueous solution (KOH) electrolyte system is safe and reliable. control, has been favored by people in recent years. However, on the cathode side of Zn-air batteries, the oxygen reduction and oxygen evolution reaction (ORR / OER) at the three-phase interface seriously affects the energy efficiency and cycle life of the battery due to the slow kinetic reaction. Platinum-based catalysts are the most commonly used ORR active materials, while IrO 2 and RuO 2 All have high catalytic activity for OER. However, its lar...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/86H01M4/90C01B32/05C01G45/02C01G53/00
CPCH01M4/86H01M4/9075H01M4/9016H01M4/9083C01G53/00C01G45/02C01B32/05C01P2004/03C01P2006/40C01P2004/80C01P2004/61
Inventor 乔锦丽殷征宇徐能能薛怀斌和蕊叶笑笑刘嘉玺王越
Owner DONGHUA UNIV
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