CN110048106B - Cobalt sulfide and multilevel carbon nanostructure composite material and preparation method and application thereof - Google Patents

Cobalt sulfide and multilevel carbon nanostructure composite material and preparation method and application thereof Download PDF

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CN110048106B
CN110048106B CN201910317689.3A CN201910317689A CN110048106B CN 110048106 B CN110048106 B CN 110048106B CN 201910317689 A CN201910317689 A CN 201910317689A CN 110048106 B CN110048106 B CN 110048106B
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黄剑锋
席乔
李嘉胤
曹丽云
党欢
王璐
郭鹏辉
王海
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Shaanxi University of Science and Technology
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Abstract

The invention discloses a cobalt sulfide and multilevel carbon nanostructure composite material and a preparation method and application thereof. The coating structure is skillfully designed to solve the problem of capacity attenuation of the transition metal sulfide as the cathode material of the sodium-ion battery, effectively inhibit the agglomeration effect of transition metal sulfide particles, and the carbon nanotube coating structure is beneficial to relieving the pulverization effect of the transition metal sulfide particles, and the preparation process is safe and easy to operate; the prepared cobalt sulfide and multilevel carbon nanostructure composite material can be applied to electrode materials of lithium ion batteries and sodium ion batteries.

Description

Cobalt sulfide and multilevel carbon nanostructure composite material and preparation method and application thereof
Technical Field
The invention belongs to the field of nano energy materials, and relates to a cobalt sulfide and multilevel carbon nano structure composite material, and a preparation method and application thereof.
Background
Transition Metal Sulfides (MSs) are considered as one of the most potential candidates as anode materials for Sodium Ion Batteries (SIBs) due to their high theoretical capacity, low cost and good electronic conductivity. However, the pulverization effect of the MSs due to volume expansion during repeated sodium insertion and sodium removal and dissolution of sulfide in the electrolyte during the reaction lead to a drastic decrease in the cycle capacity of the MSs. Therefore, studies for improving the cycle stability of MSs in lithium ion batteries and sodium ion batteries have been the subject of attention.
The compounding of MSs with carbon materials is considered to be the most effective way to overcome the above problems. On one hand, the high-conductivity carbon material can be used as a matrix of the MSs to achieve the effect of effectively dispersing the MSs nanoparticles; on the other hand, in the carbon material-coated MSs electrode, the carbon material acts as a barrier to prevent the electrolyte from directly contacting the MSs, thereby inhibiting the sulfide in the reaction intermediate from dissolving in the electrolyte to improve the utilization rate of the electrode material, and further reacting at a relatively stable cycle capacity. More importantly, carbon materials doped with hetero atoms (e.g., N, S, B, etc.) can provide higher sodium storage performance because the introduction of the doping atoms can create localized highly reactive regions and improve conductivity. Establishing a three-dimensional (3D) structure of carbon materials is also a good choice, which can better accommodate the volume expansion of MSs. However, it remains a great challenge to develop a simple and mild method for preparing transition metal sulfides that can be used to build three-dimensional structures in situ and disperse transition metal sulfides efficiently.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a cobalt sulfide and multilevel carbon nanostructure composite material, a preparation method and application thereof, and the method adopts a method of coating transition metal sulfide in a carbon nanotube grown in situ to solve the problem of capacity attenuation of the transition metal sulfide as a sodium ion battery cathode material.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a cobalt sulfide and multilevel carbon nanostructure composite material comprises the following steps:
1) dispersing graphene oxide, melamine, trithiocyanuric acid and cobalt salt in a proper amount of deionized water, stirring for reacting fully, and then freeze-drying a sample;
the concentration of the graphene oxide dispersed in the deionized water is 0.5-4 mg/ml; the mass ratio of the graphene oxide to the melamine to the trithiocyanuric acid to the cobalt salt is 1: (1.2-25) in (1.7-9): (1-22);
2) heat treatment of the samples: placing the dried sample in a tubular furnace protected by inert gas for calcining;
in the heat treatment process, the temperature is raised to 600-1000 ℃ at the temperature rise rate of 2-20 ℃/min, and the temperature is kept for 1-5 h;
3) and (3) vulcanization treatment, namely mixing the substances subjected to heat treatment in the step 2) with sulfur powder according to the mass ratio of 1: (1-5) mixing, and then carrying out vulcanization treatment in a tube furnace protected by inert gas; heating to 500-800 ℃ at a speed of 5-30 ℃/min in the vulcanization process, and preserving heat for 1-3 h; and after the vulcanization treatment is finished, taking out the sample after the sample is naturally cooled in the inert gas protective atmosphere to obtain the cobalt sulfide and multilevel carbon nanostructure composite material.
Further, the cobalt salt in the step 1) is one of cobalt acetate, cobalt nitrate, cobalt sulfate and cobalt chloride.
Further, the stirring temperature in the step 1) is 60-120 ℃, and the stirring time is 1-10 h.
Further, the flow rate of the protective gas in the heat treatment process in the step 2) is 0-300 sccm.
Further, the flow rate of the protective gas during the vulcanization treatment in the step 3) is 0-200 sccm.
An application of a cobalt sulfide and multilevel carbon nanostructure composite material as a lithium battery negative active material or a sodium battery negative active material.
The beneficial effects of the invention are as follows:
according to the preparation method of the cobalt sulfide and multilevel carbon nanostructure composite material, nitrogen and sulfur co-doped graphene is used as a matrix, a carbon nanotube is grown in situ on the graphene by a method of generating the carbon nanotube by metal catalysis, cobalt particles are wrapped in the carbon nanotube, and then the cobalt particles are subjected to vulcanization treatment to generate the cobalt sulfide and multilevel carbon nanostructure composite material. The coating structure is skillfully designed to solve the problem of capacity attenuation of the transition metal sulfide as the cathode material of the sodium-ion battery, effectively inhibit the agglomeration effect of transition metal sulfide particles, and the carbon nanotube coating structure is beneficial to relieving the pulverization effect of the transition metal sulfide particles, and the preparation process is safe and easy to operate; the prepared cobalt sulfide and multilevel carbon nanostructure composite material can be applied to electrode materials of lithium ion batteries and sodium ion batteries.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of the cobalt sulfide and multi-stage carbon nanostructure composite prepared in example 2
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the following examples.
Example 1
(1) Dispersing 0.05g of graphene oxide into 50ml of deionized water, carrying out ultrasonic stripping, then adding 0.252g of melamine and 0.177g of trithiocyanuric acid, and stirring for 30min at 60 ℃. 0.05g of cobalt acetate was added. Stirring was continued at 60 ℃ for 1 h. The product was then freeze dried.
(2) And (3) placing the precursor in a tube furnace, introducing argon for protection, heating to 600 ℃ at the heating rate of 2 ℃/min, and preserving heat for 2h, wherein the flow rate of argon gas is 0 sccm.
(3) Then mixing the product with sulfur powder in a mass ratio of 1:1, heating to 500 ℃ at a heating rate of 5 ℃/min under the protection of argon gas, and preserving heat for 1h, wherein the flow rate of argon gas is 50 sccm; and after the vulcanization treatment is finished, taking out the sample after the sample is naturally cooled in the inert gas protective atmosphere to obtain the cobalt sulfide and multilevel carbon nanostructure composite material.
Example 2
(1) 0.05g of graphene oxide is dispersed in 25ml of deionized water, ultrasonic stripping is carried out, then 0.504g of melamine and 0.304g of trithiocyanuric acid are added, and stirring is carried out for 30min at 80 ℃. 0.5g of cobalt acetate was added. Stirring was continued at 80 ℃ for 4 h. The product was then freeze dried.
(2) And (3) placing the precursor in a tube furnace, introducing argon for protection, heating to 700 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 2 hours, wherein the flow rate of argon gas is 50 sccm.
(3) Then mixing the product with sulfur powder in a mass ratio of 1:2, heating to 600 ℃ at a heating rate of 5 ℃/min under the protection of argon gas, and preserving heat for 1.5h, wherein the flow rate of argon gas is 150 sccm; and after the vulcanization treatment is finished, taking out the sample after the sample is naturally cooled in the inert gas protective atmosphere to obtain the cobalt sulfide and multilevel carbon nanostructure composite material.
Referring to fig. 1, fig. 1 is an SEM photograph of a sample prepared in this example. The morphology observation is carried out by an S-4800 type Scanning Electron Microscope (SEM) of Japan Electron company, three-dimensional graphene assembled by graphene with the thickness of nanometer level can be obviously seen, and a carbon nanotube structure grows on the graphene. The two are jointly constructed into a three-dimensional multilevel carbon nano structure.
Example 3
(1) 0.1g of graphene oxide is dispersed in 40ml of deionized water, ultrasonic stripping is carried out, then 1.26g of melamine and 0.708g of trithiocyanuric acid are added, and stirring is carried out for 1h at 70 ℃. 0.8g of cobalt chloride was added. Stirring was continued at 70 ℃ for 1 h. The product was then freeze dried.
(2) And (3) placing the precursor in a tube furnace, introducing argon for protection, heating to 800 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 2 hours, wherein the flow rate of argon gas is 100 sccm.
(3) Then mixing the product with sulfur powder in a mass ratio of 1:2.5, heating to 700 ℃ at a heating rate of 5 ℃/min under the protection of argon gas, and preserving heat for 2 hours, wherein the flow rate of the argon gas is 200 sccm; and after the vulcanization treatment is finished, taking out the sample after the sample is naturally cooled in the inert gas protective atmosphere to obtain the cobalt sulfide and multilevel carbon nanostructure composite material.
Example 4
(1) Dispersing 0.1g of graphene oxide into 100ml of deionized water, carrying out ultrasonic stripping, then adding 2.5g of melamine and 0.354g of trithiocyanuric acid, and stirring for 2h at 80 ℃. 0.4g of cobalt acetate was added. Stirring was continued at 80 ℃ for 2 h. The product was then freeze dried.
(2) And (3) placing the precursor in a tube furnace, introducing argon for protection, heating to 900 ℃ at the heating rate of 4 ℃/min, and keeping the temperature for 2 hours, wherein the flow rate of argon gas is 150 sccm. .
(3) Then mixing the product with sulfur powder in a mass ratio of 1:3, heating to 800 ℃ at a heating rate of 20 ℃/min under the protection of argon gas, and preserving heat for 2 hours, wherein the flow rate of the argon gas is 100 sccm; and after the vulcanization treatment is finished, taking out the sample after the sample is naturally cooled in the inert gas protective atmosphere to obtain the cobalt sulfide and multilevel carbon nanostructure composite material.
Example 5
(1) 50mg of graphene oxide is dispersed in 50ml of deionized water, ultrasonic stripping is carried out, then 0.126g of melamine and 0.177g of trithiocyanuric acid are added, and stirring is carried out for 1h at 60 ℃. 0.6g of cobalt sulfate was added. Stirring was continued at 60 ℃ for 10 h. The product was then freeze dried.
(2) And (3) placing the precursor in a tube furnace, introducing argon for protection, heating to 1000 ℃ at the heating rate of 20 ℃/min, and preserving heat for 2h, wherein the flow rate of argon gas is 200 sccm. .
(3) Then mixing the product with sulfur powder in a mass ratio of 1:4, heating to 600 ℃ at a heating rate of 10 ℃/min under the protection of argon gas, and preserving heat for 3 hours, wherein the flow rate of argon gas is 50 sccm; and after the vulcanization treatment is finished, taking out the sample after the sample is naturally cooled in the inert gas protective atmosphere to obtain the cobalt sulfide and multilevel carbon nanostructure composite material.
Example 6
(1) 0.1g of graphene oxide is dispersed in 25ml of deionized water, ultrasonic stripping is carried out, then 0.756g of melamine and 0.9g of trithiocyanuric acid are added, and stirring is carried out for 1h at 120 ℃.1g of cobalt nitrate was added. Stirring was continued at 120 ℃ for 3 h. The product was then freeze dried.
(2) And (3) placing the precursor in a tube furnace, introducing argon for protection, heating to 700 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 1h, wherein the flow rate of argon gas is 300 sccm.
(3) Then mixing the product with sulfur powder in a mass ratio of 1:5, heating to 700 ℃ at a heating rate of 5 ℃/min under the protection of argon gas, and preserving heat for 2 hours, wherein the flow rate of the argon gas is 0 sccm; and after the vulcanization treatment is finished, taking out the sample after the sample is naturally cooled in the inert gas protective atmosphere to obtain the cobalt sulfide and multilevel carbon nanostructure composite material.
Example 7
(1) Dispersing 0.1g of graphene oxide into 200ml of deionized water, carrying out ultrasonic stripping, then adding 0.12g of melamine and 0.17g of trithiocyanuric acid, and stirring for 1h at 120 ℃. 2.2g of cobalt nitrate were added. Stirring was continued at 120 ℃ for 3 h. The product was then freeze dried.
(2) And (3) placing the precursor in a tube furnace, introducing argon for protection, heating to 600 ℃ at the heating rate of 10 ℃/min, and preserving heat for 5 hours, wherein the flow rate of argon gas is 200 sccm.
(3) Then mixing the product with sulfur powder in a mass ratio of 1:3, heating to 700 ℃ at a heating rate of 30 ℃/min under the protection of argon gas, and preserving heat for 2 hours, wherein the flow rate of the argon gas is 0 sccm; and after the vulcanization treatment is finished, taking out the sample after the sample is naturally cooled in the inert gas protective atmosphere to obtain the cobalt sulfide and multilevel carbon nanostructure composite material.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.

Claims (5)

1. A preparation method of a cobalt sulfide and multilevel carbon nano-structure composite material is characterized by comprising the following steps:
1) dispersing graphene oxide, melamine, trithiocyanuric acid and cobalt salt in a proper amount of deionized water, stirring at 60-120 ℃ for 1-10 h for full reaction, and then freeze-drying the sample;
the concentration of the graphene oxide dispersed in the deionized water is 0.5-4 mg/ml; the mass ratio of the graphene oxide to the melamine to the trithiocyanuric acid to the cobalt salt is 1: (1.2-25) in (1.7-9): (1-22); the cobalt salt in the step 1) is one of cobalt acetate, cobalt nitrate, cobalt sulfate and cobalt chloride;
2) heat treatment of the samples: placing the dried sample in a tubular furnace protected by inert gas for calcining;
in the heat treatment process, the temperature is raised to 600-1000 ℃ at the temperature rise rate of 2-20 ℃/min, and the temperature is kept for 1-5 h;
3) and (3) vulcanization treatment, namely mixing the substances subjected to heat treatment in the step 2) with sulfur powder according to the mass ratio of 1: (1-5) mixing, and then carrying out vulcanization treatment in a tube furnace protected by inert gas; heating to 500-800 ℃ at a speed of 5-30 ℃/min in the vulcanization process, and preserving heat for 1-3 h; and after the vulcanization treatment is finished, taking out the sample after the sample is naturally cooled in the inert gas protective atmosphere to obtain the cobalt sulfide and multilevel carbon nanostructure composite material.
2. The method of claim 1, wherein the cobalt sulfide and multilevel carbon nanostructure composite is prepared by: the flow rate of the protective gas in the heat treatment process in the step 2) is 0-300 sccm.
3. The method of claim 1, wherein the cobalt sulfide and multilevel carbon nanostructure composite is prepared by: the flow rate of the protective gas in the vulcanization treatment in the step 3) is 0-200 sccm.
4. A cobalt sulphide and multilevel carbon nanostructured composite material prepared according to the method of any one of claims 1 to 3.
5. Use of the cobalt sulfide and multilevel carbon nanostructure composite of claim 4 as a negative active material for a lithium battery or a negative active material for a sodium battery.
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CN112010353A (en) * 2020-09-04 2020-12-01 吉林大学 Metal sulfide nano material and preparation method and application thereof
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