CN-121698325-B - Preparation method of carbon composite material doped with multiple metal elements

CN121698325BCN 121698325 BCN121698325 BCN 121698325BCN-121698325-B

Abstract

The invention discloses a preparation method of a carbon composite material doped with multi-metal elements. The preparation method comprises the steps of S1, dispersing a porous carbon precursor, lithium organic fluoride, an organic rare earth compound and an organic catalyst in a solvent, carrying out hydrothermal reaction, and then drying to obtain a porous carbon precursor loaded with lithium/rare earth elements/catalysts, S2, uniformly mixing the obtained material with an activating agent and a doping agent, and activating at 900-1100 ℃ to obtain multi-metal element doped porous carbon, and S3, carrying out reduction treatment and surface passivation treatment on the multi-metal element doped porous carbon to obtain the multi-metal element porous carbon composite material. The obtained material utilizes lithium doped porous carbon and rare earth doped porous carbon to improve the electronic conductivity of the material and the interlayer spacing of the carbon material, and utilizes a catalyst to grow carbon nanotubes to improve the conductivity of the material and reduce expansion, and reduces the activity of the surface of the material and improves the first efficiency through reduction and passivation treatment.

Inventors

SONG FAN
GUO PANPAN
ZHAO DONG
CHEN FEI
GUO JINGQIANG
ZHAO HONGBO

Assignees

河北坤天新能源股份有限公司

Dates

Publication Date: 20260508
Application Date: 20251118

Claims (4)

1. The preparation method of the carbon composite material doped with the multi-metal elements is characterized by comprising the following steps of: step S1: Adding a porous carbon precursor, namely lithium organofluoro acid, an organic rare earth compound and an organic catalyst into a methanol solvent according to the mass ratio of = 100:1-5:1-5:1-5 to prepare a solution with the mass concentration of 5-30wt%, transferring the solution into a high-pressure reaction kettle, carrying out hydrothermal reaction for 1-6h under the conditions of the temperature of 100-200 ℃ and the pressure of 0.11-0.5MPa, filtering, and carrying out vacuum drying on the obtained filter residues for 24h at the temperature of 80 ℃ to obtain the porous carbon precursor loaded with lithium/rare earth elements/catalysts; step S2: Uniformly mixing a porous carbon precursor and an activating agent, wherein the activating agent and the doping agent are mixed uniformly according to the mass ratio of = 100:100-500:10-30, and activating for 1-6 hours at the temperature of 900-1100 ℃ to obtain the porous carbon doped with multi-metal elements; Step S3: Transferring the porous carbon doped with the multi-metal elements into a tube furnace, heating to 650-800 ℃, introducing carbon monoxide or hydrogen reducing gas for 100-600min according to the flow rate of 100-500ml/min, cooling the obtained material to 500-600 ℃, introducing fluorocarbon gas and carbon source mixed gas for 30-300min according to the flow rate of 100-500ml/min, and depositing to obtain the carbon composite material doped with the multi-metal elements.
2. The preparation method of the multi-metal element doped carbon composite material is characterized in that in the step S1, the porous carbon precursor is one of glucose, sucrose, maltose, lactose, fructose, cellulose and starch, the organic lithium fluoride is one of lithium tetrafluoroborate, lithium trifluoromethane sulfonate, lithium perfluorobutyl sulfonate, lithium difluoro oxalate borate, lithium difluoro acetate and lithium difluoro-dioxalate phosphate, the organic rare earth compound is one of lanthanum stearate, lanthanum acetate, cerium oxalate and neodymium oxalate, and the organic catalyst is one of ferrocene, cobalt acetylacetonate, stannous octoate, bismuth octoate, lithium isooctanoate and nickel isooctanoate.
3. The method for preparing the multi-metal element doped carbon composite material according to claim 1, wherein the activating agent in the step S2 is one of potassium hydroxide, sodium hydroxide, magnesium hydroxide, potassium carbonate, potassium bicarbonate and lithium hydroxide, and the doping agent is one of pyridine, 2-mercaptopyridine, 3-pyridine boric acid, pyridine boron and picoline phosphorus.
4. The method for preparing the multi-metal element doped carbon composite material according to claim 1, wherein in the step S3, the fluorocarbon gas is one of tetrafluoromethane, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene and perfluorocyclobutane, the carbon source gas is one of methane, ethane, ethylene, acetylene and propyne, and the volume ratio of the fluorocarbon gas to the carbon source gas is=1:0.5-2.

Description

Preparation method of carbon composite material doped with multiple metal elements Technical Field The invention belongs to the field of material preparation, and in particular relates to a preparation method of a carbon composite material doped with multi-metal elements. Background The porous carbon is used as one of raw materials for preparing the silicon-carbon material, has the characteristics of large specific surface area and rich pores, so that the porous carbon can contain more active substances, but the porous carbon has poor electronic conductivity and the pressure resistance is reduced due to the more pore structure, so that the porous carbon is required to be modified to improve the electronic or ionic conductivity of the material, the pressure resistance of the material is improved, and the stability of the material structure is maintained in the circulation process, so that the circulation performance is improved. The prior art mainly improves the electronic conductivity of the material by doping nonmetallic atoms or gold, but the ionic conductivity and the first effect of the material are not improved. Disclosure of Invention In order to improve the conductivity of the porous carbon, reduce the surface defects of the material and improve the first efficiency and the multiplying power performance thereof, the invention adopts multi-metal element doping and increases the interlayer spacing and orientation of the carbon material, thereby improving the electronic conductivity of the porous carbon, reducing the surface defects and improving the multiplying power performance and the first efficiency. The preparation method of the carbon composite material doped with the multi-metal elements is characterized by comprising the following steps of: step S1: Adding a porous carbon precursor, namely lithium organofluoro acid, an organic rare earth compound and an organic catalyst into a methanol solvent according to the mass ratio of = 100:1-5:1-5:1-5 to prepare a solution with the mass concentration of 5-30wt%, transferring the solution into a high-pressure reaction kettle, carrying out hydrothermal reaction for 1-6h at the temperature of 100-200 ℃ and the pressure of 0.11-0.5MPa, filtering, and carrying out vacuum drying on the obtained filter residues for 24h at the temperature of 80 ℃ to obtain the porous carbon precursor loaded with lithium/rare earth element/catalyst; step S2: Uniformly mixing a porous carbon precursor and an activating agent, wherein the activating agent and the doping agent are mixed uniformly according to the mass ratio of = 100:100-500:10-30, and activating for 1-6 hours at the temperature of 900-1100 ℃ to obtain the porous carbon doped with multi-metal elements; Step S3: Transferring the porous carbon doped with the multi-metal elements into a tube furnace, heating to 650-800 ℃, introducing carbon monoxide or hydrogen reducing gas for 60-600min according to the flow rate of 100-500ml/min, cooling the obtained material to 500-600 ℃, introducing fluorocarbon gas/carbon source mixed gas according to the flow rate of 100-500ml/min, and depositing for 30-300min to obtain the carbon composite material doped with the multi-metal elements. In the step S1, the porous carbon precursor is one of glucose, sucrose, maltose, lactose, fructose and cellulose, the organic lithium fluoride is one of lithium tetrafluoroborate, lithium trifluoromethane sulfonate, lithium perfluorohexane sulfonate, lithium perfluorobutyl sulfonate, lithium difluorooxalate borate, lithium difluoroacetate and lithium difluorodioxalate phosphate, the organic rare earth compound is one of lanthanum acetate, lanthanum stearate, lanthanum acetate, cerium oxalate, neodymium oxalate and neodymium oxalate, and the organic catalyst is one of ferrocene, cobalt acetylacetonate, stannous octoate, bismuth octoate, lithium isooctanoate and nickel isooctanoate. In the step S2, the activating agent is one of potassium hydroxide, sodium hydroxide, magnesium hydroxide, potassium carbonate, potassium bicarbonate and lithium hydroxide, and the doping agent is one of pyridine, 2-mercaptopyridine, 3-pyridine boric acid, pyridine boron and picoline phosphorus. In the step S3, the fluorocarbon gas is one of tetrafluoromethane, nitrogen trifluoride, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene and perfluorocyclobutane, the carbon source gas is one of methane, ethane, ethylene, acetylene and propyne, and the volume ratio of the fluorocarbon gas to the carbon source gas is 1:0.5-2. Advantageous effects 1. Adding organic lithium fluoride, an organic rare earth compound and an organic catalyst into a porous carbon precursor, and performing high-pressure reaction to realize doping of lithium and rare earth elements to the porous carbon precursor, wherein the doping of lithium reduces defects on the surface of a carbon material, the doping of rare earth promotes electronic conductivity, the rare earth elements can promote th