CN113909072B - Preparation method of metal doped porous carbon microsphere/CNTs composite material - Google Patents
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- CN113909072B CN113909072B CN202110995287.6A CN202110995287A CN113909072B CN 113909072 B CN113909072 B CN 113909072B CN 202110995287 A CN202110995287 A CN 202110995287A CN 113909072 B CN113909072 B CN 113909072B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
- B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0209—Multistage baking
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- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- B05D2506/00—Halogenated polymers
- B05D2506/10—Fluorinated polymers
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Abstract
The invention discloses a preparation method of a metal doped porous carbon microsphere/CNTs composite material, which is used for preparing the metal doped porous carbon microsphere/CNTs composite material by an electrostatic spraying method; dispersing CNTs into PVP solution, spraying the uniform mixed solution by an electrostatic spraying method, and finally pre-oxidizing and firing the product to obtain the metal doped porous carbon sphere/CNTs composite material; the metal doped porous carbon sphere/CNTs composite material prepared by the invention can be used as a host material of a sulfur anode of a lithium sulfur battery; the electrostatic spraying method is simple and easy to operate, and various Co (Fe, ni) salts can be added into the spinning solution to form Co (Fe, ni) doped porous carbon materials; the addition of CNTs can form a three-dimensional conductive network to improve the conductive performance of the porous carbon sphere, and can greatly improve the structural stability of the porous carbon sphere due to the excellent length-diameter ratio and mechanical toughness of the carbon nanotubes.
Description
Technical Field
The invention relates to the technical field of sulfur host materials, in particular to a preparation method of a metal doped porous carbon microsphere/CNTs composite material.
Background
Porous carbon is widely used in various fields such as electrode materials, storage and separation, gas adsorption, catalyst carriers, etc. because of its abundant pore volume, high specific surface area, and chemical stability. The template method is a method for efficiently preparing an ordered porous carbon material. The template method can be classified into a hard template method and a soft template method.
Although the ordered or disordered porous carbon material can be obtained by using the hard template method, and the pore size and the pore morphology are controllable, the operation process is complex, the time consumption is more, strong acid and strong alkali are needed to be used for removing the template after carbonization, and the problems of template residue and environmental pollution exist. The soft template mainly utilizes macromolecule self-assembly to form an ordered nano structure, and the ordered porous carbon material is obtained by a thermal polymerization method and a further carbonization method. Porous carbon spheres prepared by the templating & macromolecular polymer strategy typically suffer from poor electrical conductivity and structural stability.
Disclosure of Invention
The invention aims to provide a preparation method of a metal doped porous carbon microsphere/CNTs composite material, which aims to solve the problems of poor conductivity and structural stability of porous carbon spheres prepared by a template method and a macromolecular polymer strategy in the prior art.
The invention uses PVP of macromolecule as carbon source, polytetrafluoroethylene emulsion as template, adds conductive filler such as carbon nano tube and graphene, and adds metal salt and melamine, and forms porous carbon sphere with three-dimensional conductive network of metal-nitrogen-carbon single atom site through high temperature treatment, and is used as high performance sulfur host material.
In order to achieve the above purpose, the present invention provides the following technical solutions: a preparation method of a metal doped porous carbon microsphere/CNTs composite material comprises the following specific steps:
s1 CNTs dispersion: adding the CNTs containing the hydroxyl into deionized water, carrying out ultrasonic treatment, and carrying out ultrasonic dispersion to obtain CNTs dispersion liquid;
s2, preparing spraying liquid: adding nitrate and melamine into the CNTs dispersion liquid obtained in the step S1, and stirring; adding PVP solution, stirring for 4-5 h, fully dissolving, adding polytetrafluoroethylene emulsion, and stirring to obtain spraying liquid; the mass ratio of PVP to water in the PVP solution is 1:5 to 1:10;
s3, placing the solution in a 20mL syringe, fixing the syringe, connecting the syringe with a high-voltage power supply, connecting the aluminum foil paper covered with the syringe with a ground wire to serve as a receiving plate, applying 15-20kV high voltage to form an electrostatic field at the position right below the needle head, and performing electrostatic spraying at the glue pushing speed of 1 mL/h;
s4, preparing a metal doped porous carbon microsphere/CNTs composite material: the spray-coated product prepared in the step S3 is placed at 80-150 ℃ for stabilization, so that the solvent in the product is removed, the influence on the subsequent heat treatment is avoided, and after stabilization, the dried sample is placed in a tube furnace for pre-oxidation at 180-250 ℃ to form a stable carbon structure; heating to 700-900 ℃ in Ar atmosphere, carbonizing PVP, volatilizing polytetrafluoroethylene at high temperature, and forming stable chemical structure by metal atoms and nitrogen atoms at high temperature, thereby preparing the metal doped porous carbon microsphere/CNTs composite material.
Preferably, 15-20mg of hydrophilic CNTs are added into 5g of deionized water for ultrasonic treatment for 1h, and ultrasonic dispersion is carried out.
Preferably, in step S2, the nitrate is one or more of cobalt nitrate, nickel nitrate and ferric nitrate.
Preferably, in step S2, 50mg of cobalt nitrate and 200mg of melamine are added into the CNTs dispersion liquid and stirred; then adding 10g of PVP aqueous solution, stirring for 4-5 h, adding 10-12g of polytetrafluoroethylene emulsion after full dissolution, and stirring for 4h; finally, electrostatic spraying is carried out under the voltage of 15-20kV and the paste pushing speed of 1 ml/h.
Preferably, the prepared spray product is stable at 80-150 ℃ for 24 hours.
The invention prepares the metal doped porous carbon microsphere/CNTs composite material by an electrostatic spraying method; dispersing CNTs into PVP solution, and then spraying the uniform mixed solution by an electrostatic spraying method; pre-oxidizing the product after spraying, and then firing to obtain a metal doped porous carbon microsphere/CNTs composite material; the metal doped porous carbon microsphere/CNTs composite material prepared by the invention can be used as a host material of a sulfur anode of a lithium-sulfur battery.
The electrostatic spraying method is simple and easy to operate, and various Co (Fe, ni) salts can be added into the spraying liquid to form the Co (Fe, ni) -doped porous carbon material. The addition of CNTs can form a three-dimensional conductive network to improve the conductive performance of the porous carbon sphere, and can greatly improve the structural stability of the porous carbon sphere due to the excellent length-diameter ratio and mechanical toughness of the carbon nanotubes.
Compared with the prior art, the invention has the beneficial effects that:
(1) The process is controllable, the specific surface area and the pore diameter of the porous carbon sphere can be controlled by controlling the amount of the template added into the polytetrafluoroethylene emulsion, and the mass ratio of PVP to water in PVP solution is controlled to be 1:5 to 1:10, the invention adopts an electrostatic spraying method, applies high-voltage static electricity to charge sprayed PVP solution droplets with static electricity, forms a high-voltage electrostatic field among a spray head electrode, charged mist cloud and a receiver, the charged PVP solution droplets directionally move under the action of the electrostatic field force and are adsorbed on the receiver, and the water amount of PVP solution is regulated and controlled, so that the water amount is changed into the shape of droplets in the spraying process based on the existence of liquid surface tension, thereby preparing the metal doped porous carbon microsphere/CNTs composite material with a spherical structure; the porous carbon sphere prepared by the invention has a unique porous structure, larger specific surface area and rich pore structure, and can improve the loading capacity of S, and in addition, the larger specific surface area increases reactive sites and enhances the adsorption effect on polysulfide.
(2) The carbon material subjected to the PVP heat treatment is poor in conductivity, the carbon nano tube is added into the carbon sphere in the preparation process, the overall conductivity of the composite material can be improved, and the excellent length-diameter ratio and mechanical toughness of the carbon nano tube can greatly improve the structural stability of the porous carbon sphere.
(3) The various metal salts added in the invention can form metal doping, and can obviously improve the catalytic conversion effect of the lithium-sulfur battery. In addition, melamine is added into the spraying liquid to help form a metal-carbon-nitrogen structure, so that the number and stability of metal sites are improved.
Drawings
FIG. 1 is an SEM image of a Co-doped porous carbon sphere material;
FIG. 2 is an SEM image of Co-doped porous carbon spheres/CNTs composite;
FIG. 3 is an SEM image of a Co-doped porous carbon sphere/carbon black composite;
fig. 4 is an SEM image of a Co-doped porous carbon sphere/graphene composite.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below in connection with the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the specific techniques or conditions are not identified in the examples and are performed according to techniques or conditions described in the literature in this field or according to product specifications; the reagents and materials are all analytically pure reagents, which are commercially available unless otherwise specified.
Example 1
A preparation method of a Co-doped porous carbon microsphere/CNTs composite material comprises the following specific steps:
s1 carbon nanotube Dispersion
15-20mg of hydrophilic CNTs are added into 5g of deionized water for ultrasonic treatment for 1h, and ultrasonic dispersion is carried out.
S2, preparation of spraying liquid
50mg of cobalt nitrate and 200mg of melamine were added to the CNTs dispersion and stirred. Then adding 10g of PVP aqueous solution, stirring for 5h, adding 12g of polytetrafluoroethylene emulsion after full dissolution, and stirring for 4h; the mass ratio of PVP to water in the PVP solution is 1:8, 8;
s3, placing the solution in a 20mL syringe, fixing the syringe, connecting the syringe with a high-voltage power supply, connecting the aluminum foil paper covered with the syringe with a ground wire to serve as a receiving plate, applying 15-20kV high voltage to form an electrostatic field at the position right below the needle head, and performing electrostatic spraying at the glue pushing speed of 1 mL/h;
s4, preparing a metal doped porous carbon microsphere/CNTs composite material: the spray-coated product prepared in the step S3 is placed at 80-150 ℃ for stabilization, so that the solvent in the product is removed, the influence on the subsequent heat treatment is avoided, and after stabilization, the dried sample is placed in a tube furnace for pre-oxidation at 180-250 ℃ to form a stable carbon structure; heating to 700-900 ℃ in Ar atmosphere, carbonizing PVP, volatilizing polytetrafluoroethylene at high temperature, and forming stable chemical structure by metal atoms and nitrogen atoms at high temperature, thereby preparing the metal doped porous carbon microsphere/CNTs composite material.
As another example, CNTs can be exchanged for graphene, carbon black.
From fig. 1 to fig. 4, it can be seen that the porous carbon sphere structure with uniform distribution is prepared by the invention, and the highly conductive material, namely CNTs, graphene and carbon black, can be effectively limited in the porous carbon sphere by the electrostatic spraying technology, so that the conductivity and the structural stability of the material are improved.
In conclusion, the performance of the lithium-sulfur battery can be cooperatively improved through single-atom doping of a metal-nitrogen-carbon structure, a high-conductivity high-mechanical-performance network formed by the carbon nano tubes and the high specific surface area of the porous carbon spheres.
In this specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, so that the same or similar parts between the embodiments are referred to each other. The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (3)
1. The preparation method of the metal doped porous carbon microsphere/CNTs composite material is characterized by comprising the following specific steps:
s1 CNTs dispersion: adding the CNTs containing the hydroxyl into deionized water, carrying out ultrasonic treatment, and carrying out ultrasonic dispersion to obtain CNTs dispersion liquid;
s2, preparing spraying liquid: adding 50mg cobalt nitrate and 200mg melamine into the CNTs dispersion liquid and stirring; then adding 10g PVP solution, stirring for 4-5 h, adding 10-12g polytetrafluoroethylene emulsion after full dissolution, and stirring for 4h to prepare spraying liquid; the mass ratio of PVP to water in the PVP solution is 1: 5-1: 10;
s3, placing the solution in a 20mL injector, fixing the injector, connecting the injector with a high-voltage power supply, connecting the covered aluminum foil paper with a ground wire to serve as a receiving plate, applying 15-20kV high voltage to form an electrostatic field at the position right below a needle head, and performing electrostatic spraying at the glue pushing speed of 1 ml/h;
s4, preparing a metal doped porous carbon microsphere/CNTs composite material: the spray-coated product prepared in the step S3 is placed at 80-150 ℃ for stabilization, and then the dried sample is placed in a tube furnace for pre-oxidation at 180-250 ℃ to form a stable carbon structure; heating to 700-900 ℃ in Ar atmosphere, carbonizing PVP, volatilizing polytetrafluoroethylene at high temperature, and forming stable chemical structure by metal atoms and nitrogen atoms at high temperature, thereby preparing the metal doped porous carbon microsphere/CNTs composite material.
2. The method of claim 1, wherein in step S1, 15-20mg hydrophilic CNTs are added to 5g deionized water and sonicated for 1 hour to perform ultrasonic dispersion.
3. The method of claim 1, wherein the prepared spray product is stable at 80-150 ℃ for 24 hours.
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| US20190020037A1 (en) * | 2016-01-19 | 2019-01-17 | Institute Of Chemistry, Chinese Academy Of Sciences | Modified 3d current collector, its application in lithium metal batteries and method for preparing said composite material |
| CN110137466A (en) * | 2019-05-14 | 2019-08-16 | 北京科技大学 | Lithium ion battery silicon-carbon-carbon nanotube composite microsphere negative electrode material preparation method |
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| GB201416239D0 (en) * | 2014-09-15 | 2014-10-29 | Univ York And Consejo Superior De Investigaciones Cientificas | Mesoporous materials from nanoparticle enhanced polysaccharides |
| CN104966824A (en) * | 2015-06-25 | 2015-10-07 | 湖北工程学院 | Nitrogen-doped porous carbon sphere and cobaltous oxide nano-composite anode material based on chitosan and derivatives thereof and preparation method thereof |
| CN111039329A (en) * | 2019-01-16 | 2020-04-21 | 中国科学院过程工程研究所 | Hollow multi-shell metal oxide composite material and preparation method thereof |
| CN110911697B (en) * | 2019-11-22 | 2022-06-07 | 深圳大学 | Transition metal/nitrogen-doped porous carbon nanosphere electrocatalyst and preparation method thereof |
| CN112694080B (en) * | 2020-12-28 | 2022-08-19 | 北京化工大学 | Carbon microsphere with embedded conductive network structure, preparation method and energy storage application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20190020037A1 (en) * | 2016-01-19 | 2019-01-17 | Institute Of Chemistry, Chinese Academy Of Sciences | Modified 3d current collector, its application in lithium metal batteries and method for preparing said composite material |
| CN110137466A (en) * | 2019-05-14 | 2019-08-16 | 北京科技大学 | Lithium ion battery silicon-carbon-carbon nanotube composite microsphere negative electrode material preparation method |
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| Bin Yi et.al.High-performance carbon nanotube-implanted mesoporous carbon spheres for supercapacitors with low series resistance.Materials Research Bulletin.2011,(第undefined期),第2168-2172页. * |
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