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A carbon-supported spinel material and its preparation method and application

A spinel, carbon-supported technology, applied in nanotechnology for materials and surface science, chemical instruments and methods, nanocarbon, etc. Effective control of element distribution and surface properties, inability to effectively control element distribution, etc., to achieve the effect of compounding

Active Publication Date: 2021-06-25
惠州市亿纬新能源研究院
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] CN102082270A discloses a preparation method of a class of manganese spinel nanomaterials, including Co x mn 3-x o 4 , MgMn 2 o 4 , Mn 3 o 4 Nanoparticles, ZnMn 2 o 4 Hollow nanospheres, hollow microspheres or nanosheets, which are prepared by reducing MnO 2 prepared by reduction; although this scheme can prepare spinel and control the microscopic morphology of the product, it cannot effectively control the element distribution on the surface of the prepared spinel nanoparticles
[0004] CN104810518A discloses a cobalt-manganese series spinel nanomaterial and a preparation method thereof, the chemical general formula of the cobalt-manganese series spinel nanomaterial is Co 3-x mn x o 4 , where 1≤x≤2, including cubic phase nanoparticles and tetragonal phase nanoparticles, the particle size of the nanoparticles is 5-15nm, and the molar ratio of Co to Mn is 0.4-2.2:1; the preparation method is: Under normal pressure air atmosphere, the two-step method of oxidation precipitation and embedded crystallization is used to control the crystal phase and composition, so as to obtain cobalt-manganese spinel nanomaterials. Although this method can prepare cobalt-manganese spinel nanomaterials, However, the element distribution and chemical properties of the surface of the prepared cobalt-manganese spinel nanomaterials cannot be effectively controlled.
[0005] CN108636422A discloses a manganese-cobalt spinel catalyst and a preparation method thereof, the method comprising the following steps: (1) mixing a manganese salt and a cobalt salt and performing the first grinding treatment to obtain mixed salt powder; (2) mixing The mixed salt powder is mixed with microporous ceramics, diluent and water for a second grinding treatment and aging to obtain a compound intermediate; (3) drying the compound intermediate to obtain a precursor; ( 4) Roasting the precursor to obtain the manganese-cobalt spinel catalyst; the method described in this scheme cannot effectively regulate the distribution of elements on the surface of the manganese-cobalt spinel, and the manganese-cobalt spinel prepared by it Insufficient catalyst activity for catalyzing oxygen reduction
[0006] Although the above-mentioned documents disclose some preparation methods of spinel, none of them can realize the effective control of the distribution of elements on the surface of spinel and the surface properties.

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  • A carbon-supported spinel material and its preparation method and application
  • A carbon-supported spinel material and its preparation method and application
  • A carbon-supported spinel material and its preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0074] (1) Ultrasonically disperse 60mg of carbon carrier (solid carbon spheres with a particle size of 30nm) in 15mL of cobalt acetate aqueous solution with a concentration of 17.04mmol / L, then add 0.5mL of ammonia water with a concentration of 14mol / L dropwise, and stir in an air atmosphere 10min, obtain solution A;

[0075] (2) adding dropwise 15mL concentration in the solution A that step (1) obtains is 17.04mmol / L manganese acetate aqueous solution, obtains solution B;

[0076] (3) Aging solution B at 60°C for 120min, then adding it into a 35mL closed reaction kettle, and performing solvothermal reaction at 150°C for 3h;

[0077] (4) The product of step (3) is naturally cooled to room temperature, centrifuged, washed and dried to obtain the carbon-loaded spinel material, which is recorded as the surface manganese and cobalt elements evenly distributed Mn 1.5 co 1.5 o 4 / C.

[0078] In the carbon-supported spinel material prepared in this example, the mass ratio of car...

Embodiment 2

[0080] In this example, the aging temperature of step (3) in Example 1 is replaced by 40°C, and the other conditions are exactly the same as those in Example 1, and a carbon-supported spinel material is prepared, which is recorded as the surface manganese enriched Mn 1.5 co 1.5 o 4 / C.

[0081] In the carbon-supported spinel material prepared in this example, the mass ratio of carbon carrier to spinel is 0.67:1, and the spinel is Mn 1.5 co 1.5 o 4 The nanoparticle has an average particle diameter of 20nm; the surface of the spinel nanoparticle is rich in manganese, and the molar ratio of manganese to cobalt on the surface is 1.35:1.

Embodiment 3

[0083]In this example, the aging temperature of step (3) in Example 1 is replaced by 80°C, and the other conditions are exactly the same as those in Example 1, and a carbon-supported spinel material is prepared, which is recorded as surface cobalt enriched with Mn 1.5 co 1.5 o 4 / C.

[0084] In the carbon-supported spinel material prepared in this example, the mass ratio of carbon carrier to spinel is 0.67:1, and the spinel is Mn 1.5 co 1.5 o 4 The nanoparticles have an average particle size of 20nm; the surface of the spinel nanoparticles is enriched in cobalt, and the molar ratio of manganese to cobalt on the surface is 0.5:1.

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Abstract

The invention relates to a carbon-supported spinel material and its preparation method and use. The preparation method comprises the following steps: (1) mixing the carbon support with a cobalt-containing salt solution, and then adding ammonia water to obtain a solution A; (2) Add a manganese salt solution to the solution A obtained in step (1) to obtain a solution B; (3) heat and age the solution B, and then perform a solvothermal reaction to obtain a carbon-supported spinel material containing manganese and cobalt elements The method of the present invention can be used to realize the effective compounding of carbon carrier and spinel, and effectively regulate and control the surface element distribution and chemical properties of the spinel nanoparticles in the obtained carbon-loaded spinel material, prepared by the above method The oxygen reduction half-wave potential of the carbon-supported spinel material with uniform distribution of manganese and cobalt elements on the surface can reach up to 0.872V.

Description

technical field [0001] The invention relates to the field of new energy materials, in particular to a carbon-supported spinel material and its preparation method and application. Background technique [0002] Spinel materials containing manganese and cobalt have a wide range of sources, and can be obtained using a variety of synthetic methods at temperatures below 200 °C (F.Cheng, et al.Nat.Chem., 2011,3,79 ; C.Li, etal.Nat.Commun., 2015, 6, 7345), and its raw material cost and manufacturing cost are relatively cheap. [0003] CN102082270A discloses a preparation method of a class of manganese spinel nanomaterials, including Co x mn 3-x o 4 , MgMn 2 o 4 , Mn 3 o 4 Nanoparticles, ZnMn 2 o 4 Hollow nanospheres, hollow microspheres or nanosheets, which are prepared by reducing MnO 2 It is prepared by reduction; although this scheme can prepare spinel and control the microscopic morphology of the product, it cannot effectively control the element distribution on the na...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C01G51/00C01B32/15B82Y30/00B01J23/889C25B11/077
Inventor 汪瀛庄林袁中直刘金成
Owner 惠州市亿纬新能源研究院
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