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Preparation method, product and application of a hollow carbon sphere composite with iron-cobalt-platinum-loaded three-dimensional mesh surface

A three-dimensional mesh, hollow carbon sphere technology, applied in structural parts, electrical components, battery electrodes, etc., can solve problems such as poisoning of non-platinum materials, no significant reduction in the actual use of platinum, and decreased catalyst activity.

Active Publication Date: 2021-09-28
HUNAN UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

For non-platinum ORR electrocatalysts, there has not been found that their ORR electroactivity in acidic media can reach or approach the level of metallic platinum; in addition, it has been found in practical applications that proton exchange membrane fuel cells use non-platinum materials as cathodes For electrocatalysts, during the operation of the battery, because the electrodes are in a static state, a small amount of hydrogen peroxide or peroxide ions generated by the cathode when catalyzing ORR continue to accumulate on the surface of the cathode, which has a poisoning effect on the activity of non-platinum materials. A significant decrease in catalyst activity
On the other hand, if platinum-based ORR electrocatalysts are used in proton exchange membrane fuel cells, although the effect of stable battery operation can be achieved, the actual use of platinum has not been significantly reduced, and there is also the problem of high cost.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021](1) The silica ball SiO wrapped in a carbon nitrogen complex was prepared according to the improved prior art (Kuang Sheng et al 2020 J. Electrochem. SOC.167: 070560) 2 @ @: First, silica nanospheres were prepared: 120 ml of water, 280 ml of ethanol and 14 ml of concentrated concentrated ammonia were mixed, and 18 ml of tetraethyl silicate was added dropwise under stirring. After the addition was completed, stirring was stirred for 3 hours, the resulting solid centrifugally, Wash each other three times with water and ethanol at 60 o The vacuum is dried under vacuum for 12 hours, the grinding is uniform, resulting in a silica ball having a particle diameter of about 250 nm; then the silica ball ultrasound is dispersed in ethanol, and the concentration is 30 mmol L is added to the continuous stirring. -1 The trihymethylmethylmethane buffer solution forms a uniform dispersion, and nitrogen gas is introduced into the dispersion, and the concentration is 40 mmol L. -1 Dopamine so...

Embodiment 2

[0029] Steps (1), (2), (3) are the same as steps (1), (2), (3) in Example 1;

[0030] (4) 25 mg of acetylacetonate and 5.5 mg of acetylacetonate iron C 15 Hide 21 Feo 6 Dissolve in ethanol, form a uniform solution; then add 3.7 g of the above SiO 2 @ 3D-C-N, the resulting mixture was stirred at room temperature for 30 min, continued to be heated to 70 under constant stirring o C and maintained 2 h; finally evaporated to ethanol, vacuum dry at room temperature, the resulting solid transferred to the tube furnace, in a nitrogen atmosphere o C MIN -1 Speed ​​heating to 900 o C and maintain 2 h at this temperature; cooled to room temperature to obtain a silicon dioxide ball wrapped in a black solid as iron-cobalt-nitrogen-doped three-dimensional mesh carbon layer wrapped in a silica ball SiO 2 @ 3D-C-N / FECO;

[0031] Step (5), (6) are the same as step (5) of Example 1; (6);

[0032] The test process of step (7) is the same as step (7) of Embodiment 1. The result is: oxygen reduction...

Embodiment 3

[0034] Steps (1), (2), (3) are the same as steps (1), (2), (3) in Example 1;

[0035] (4) 75 mg of porphyrin cobalt and 11 mg phthalocyanine sub-ferrous is dissolved in ethanol to form a uniform solution state; subsequent addition of 3.7 g of SiO 2 @ 3D-C-N, the resulting mixture was stirred at room temperature for 30 min, continued to be heated to 70 under constant stirring o C and maintained 2 h; finally evaporated to ethanol, vacuum dry at room temperature, the resulting solid transferred to the tube furnace, in a nitrogen atmosphere o C MIN -1 Speed ​​heating to 900 o C and maintain 2 h at this temperature; cooled to room temperature to obtain a silicon dioxide ball wrapped in a black solid as iron-cobalt-nitrogen-doped three-dimensional mesh carbon layer wrapped in a silica ball SiO 2 @ 3D-C-N / FECO;

[0036] Step (5), (6) are the same as step (5) of Example 1; (6);

[0037] The test process of step (7) is the same as step (7) of Embodiment 1. The result is: oxygen reduction...

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Abstract

A preparation method of hollow carbon sphere composites with iron-cobalt-platinum-supported three-dimensional network surface, firstly, nitrogen-doped carbon-wrapped silica nanospheres SiO 2 Zn-MOF particles are deposited on the surface of @C‑N; then it is mixed with melamine and pyrolyzed, and then pickled to remove the zinc oxide formed by pyrolysis, and a three-dimensional network nitrogen-doped porous carbon layer is obtained. Silicon oxide SiO 2 @porousC‑N; then the SiO 2 @porousC‑N and iron-cobalt salt were treated by solution impregnation and pyrolysis to obtain precursor-1 loaded with iron-cobalt nanoparticles; then the glycerol solution of precursor-1 and platinum salt was stirred under heating, and the obtained solid was the precursor ‑2; finally, the precursor ‑2 is pyrolyzed and the silica is removed to obtain a hollow carbon sphere composite catalyst with iron-cobalt-platinum-supported three-dimensional network surface. The present invention loads iron-cobalt-platinum nanoparticles in a three-dimensional network carbon-nitrogen layer, thereby forming a hollow carbon sphere composite catalyst with a three-dimensional network surface with high efficiency and stable electrical activity and low platinum loading, which has great potential in the field of fuel cells Wide range of applications.

Description

Technical field [0001] The present invention belongs to the field of electrochemical energy source novel materials, particularly to iron and cobalt Preparation and Application of a platinum loading surface of a three dimensional network of hollow carbon sphere composite. Background technique [0002] Oxygen reduction reaction (ORR) is a fuel cell, a metal - air cell the cathodic process is important. Since the ORR kinetics itself is a slow process, so to a large extent, ORR has become the key to whether or not such excellent battery performance constraints. To ensure ORR quickly and efficiently, must be selected if the problem of having excellent electrical ORR catalytic activity of the cathode catalyst. A lot of research and practical application indicates that platinum is all metals, the most effective ORR electrocatalysts currently found, but a large number of commercial use of platinum cause the battery to costly and platinum on the earth's resources are scarce, and the distr...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): H01M4/92H01M4/88
CPCH01M4/8878H01M4/921H01M4/926Y02E60/50
Inventor 易清风陈阿玲侯利锋
Owner HUNAN UNIV OF SCI & TECH