CN112410849B - Preparation method and application of defect black phosphorus alkene carbon nanotube composite material - Google Patents

Preparation method and application of defect black phosphorus alkene carbon nanotube composite material Download PDF

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CN112410849B
CN112410849B CN202011287764.5A CN202011287764A CN112410849B CN 112410849 B CN112410849 B CN 112410849B CN 202011287764 A CN202011287764 A CN 202011287764A CN 112410849 B CN112410849 B CN 112410849B
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black phosphorus
carbon nanotube
phosphorus alkene
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CN112410849A (en
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王新
许元妹
张永光
水玲玲
张文娜
马恒
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Zhaoqing South China Normal University Optoelectronics Industry Research Institute
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Abstract

The invention belongs to the technical field of nano material preparation, and discloses a preparation method and application of a defect black phosphorus alkene carbon nano tube composite material. The constructed defective black phosphorus alkene is embedded into the carbon nano tube to form a three-dimensional conductive network, and can be used as a high-performance sulfur fixing agent and a polysulfide conversion catalytic promoter of the lithium-sulfur battery, so that the conductivity of the battery electrode is better, the shuttle effect is lower, and the performance of the lithium-sulfur battery is remarkably improved; the preparation method provided by the invention has the advantages of low cost, easiness in operation, good efficiency improvement effect and larger application prospect.

Description

Preparation method and application of defect black phosphorus alkene carbon nanotube composite material
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a preparation method and application of a defect black phosphorus alkene carbon nano tube composite material.
Background
In the past decades, the development of traditional fossil energy has greatly promoted the development of human society and economy, but at the same time, with the continuous consumption of non-renewable petroleum energy and the strong demand of advanced energy for new generations, people are continuously promoted to explore new chargeable energy storage equipment. Due to abundant reserves, low cost, environmental friendliness and its high theoretical capacity, lithium sulfur batteries are considered to be an excellent next-generation energy source of choice. However, the performance of the catalyst is affected by the low conductivity of sulfur and the shuttling effect of polysulfide, and thus the catalyst is difficult to satisfy the actual wide application. Therefore, a material is needed to improve the conductivity and inhibit the polysulfide shuttling effect, which is of great significance to improve the performance of the lithium-sulfur battery.
The black phosphorus alkene two-dimensional material is a novel non-noble metal electrode material with a very promising prospect. High black phosphorus charge mobility (1000 cm)2V.S), has large specific surface area, has lone pair electrons, and has adjustable band gap (can realize the adjustment of 2.0eV to 0.3 eV). Since 2014, the subject group of professor of the tensor wave of the university of compound denier successfully applies the novel two-dimensional crystal material black phosphorus to the field effect transistor, and finds that the transistor based on the black phosphorus has higher on-off ratio and excellent carrier mobility, and once the transistor based on the black phosphorus is a van der waals layered crystal material, the black phosphorus material generates new light again and becomes a new research hotspot quickly. Black phosphorus has good stability in polar solvents such as N, N-Dimethylformamide (DMF), and dimethyl pyrrolidone (NMP). By depositing Al on the black phosphorus surface2O3、SiO2Or a passivation layer such as boron nitride may also serve to increase the stability of the black phosphorus. The black phosphorus also shows great potential in the lithium-sulfur field, and is expected to bring a new opportunity for breakthrough of the lithium-sulfur battery technology. However, the existing preparation method of the thin-layer black phosphorus alkene/carbon nanotube composite structure mainly adopts a two-step method, firstly adopts a physical high-intensity ultrasonic method to strip black phosphorus, and then adopts hydrothermal method and other methods to compound other functional materials, so that the steps are multiple, the time consumption is long, and therefore, the search for a preparation method of the black phosphorus alkene/carbon nanotube composite structure which is simple and rapid is still a great challenge.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a preparation method of a defective black phosphorus alkene carbon nanotube composite material.
The second purpose of the invention is to provide the defect black phosphorus alkene carbon nanotube composite material obtained by the method.
It is a third object of the present invention to provide a lithium sulfur battery containing the defective black phosphorus alkene carbon nanotube composite material.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a defect black phosphorus alkene carbon nano tube composite material adopts an H-shaped double electrochemical cell reactor, takes a mixture of a carbon nano tube, an adsorption auxiliary agent, a dispersing agent and organic amine as an electrolyte, takes a black phosphorus crystal as a cathode, takes platinum as an anode, separates a cathode chamber and an anode chamber by a proton exchange membrane, and obtains the defect black phosphorus alkene carbon nano tube composite material after electrolysis through electrification and ultrasonic and centrifugal separation.
Preferably, the organic amine is one or two of urea, polyethyleneimine and melamine.
Preferably, the carbon nanotubes may be single-walled carbon nanotubes, double-walled carbon nanotubes, and multi-walled carbon nanotubes.
Preferably, the size of the black phosphorus crystal is 0.3-2 cm; the black phosphorus crystal is blocky and is generally obtained by a chemical vapor deposition method, and the carbon nano tube is embedded into the surface of the black phosphorus alkene after electrolysis to form a three-dimensional conductive network, so that the conductivity of the material is increased, the specific surface area of the material is greatly increased, and adsorption sites are increased.
Preferably, the dosage ratio of the carbon nano tube to the dispersant is as follows: 1-20 mg/ml.
More preferably, the ratio of the carbon nanotubes to the dispersant is: 5-15 mg/ml.
Most preferably, the amount ratio of the carbon nanotubes to the dispersant is: 8-10 mg/ml.
Preferably, the dosage ratio of the organic amine to the dispersant is as follows: 1-10 mg/ml.
Preferably, the voltage of electrolysis is 5-30V, and the time is 1-20 min; the black phosphorus alkene defect is constructed by the applied electric field, the electric charge is generated on the black phosphorus surface, and the adsorption capacity of the black phosphorus alkene defect on the carbon nano tube is improved.
Preferably, the voltage of electrolysis is 15V, and the time is 5-15 min.
Preferably, the dispersant is one or two of N, N-dimethylformamide, N-methylpyrrolidone and N, N-dimethylacetamide; besides the dispersing function of the dispersing agent on the carbon nano tube, a solvent layer can be formed on the surface of the black phosphorus, and the effect of protecting the black phosphorus from oxidation is achieved.
Preferably, the adsorption aid is selected from tetramethylphosphonium chloride, tetrabutylphosphonium bromide, tetramethylphosphonium chloride, ethoxycarbonylethylidene triphenylphosphine and 2-carboxyethyltriphenylphosphonium bromide.
Preferably, the single-chamber volume of the H-shaped double electrochemical cell reactor is 10-200 ml; the platinum electrode comprises a platinum sheet electrode, a platinum mesh electrode, a platinum rod electrode, a platinum strip electrode or a platinum wire electrode.
Preferably, the specific operations of ultrasound, separation are: taking out the black phosphorus alkene/carbon nano tube composite structure, performing ultrasonic treatment for 1 to 5 minutes, centrifuging the mixture at 3000 rpm for 5 minutes to obtain an upper-layer solution of the black phosphorus alkene/carbon nano tube composite structure, centrifuging the mixture at 10000 rpm for 30 minutes to obtain a lower-layer black phosphorus alkene/carbon nano tube composite structure, and drying the lower-layer black phosphorus alkene/carbon nano tube composite structure.
As a preferred embodiment, the preparation method of the defect black phosphorus alkene carbon nanotube composite material comprises the following steps:
s1: preparing an electrolyte: carbon nanotubes (only required when the electrolyte of the cathode chamber is provided), organic amine and an adsorption aid are stirred and dispersed in a dispersant such as N, N-dimethylformamide, N-methylpyrrolidone, N-dimethylacetamide;
s2: an H-shaped double electrochemical pool reactor is adopted, and a proton exchange membrane is used for separating a cathode chamber and an anode chamber; adding electrolyte into the cathode chamber and the anode chamber respectively; fixing the black phosphorus crystal on an electrode as a cathode and placing the cathode in a cathode chamber, and assembling a platinum electrode as an anode into an electrolytic cell;
s3: electrifying and electrolyzing for 1-20 minutes under the voltage of 5-30V, and taking out the obtained product after electrolysis, and performing slight ultrasonic and centrifugal separation to obtain the defect black phosphorus alkene/carbon nano tube composite structure.
The invention also provides a defective black phosphorus alkene carbon nanotube composite material obtained by the method.
The invention also provides application of the defective black phosphorus alkene carbon nanotube composite material as an electrode material in preparation of a lithium-sulfur battery.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts an electrochemical method to prepare the carbon nano tube loaded black phosphorus alkene composite material. The constructed defective black phosphorus alkene is embedded into the carbon nano tube to form a three-dimensional conductive network, and can be used as a high-performance sulfur fixing agent and a polysulfide conversion catalytic promoter of the lithium-sulfur battery, so that the conductivity of the battery electrode is better, the shuttle effect is lower, and the performance of the lithium-sulfur battery is remarkably improved; the preparation method provided by the invention has the advantages of low cost, easiness in operation, good efficiency improvement effect and larger application prospect.
Drawings
FIG. 1 is a schematic diagram of the preparation of a defective black phosphorus alkene/carbon nanotube composite structure;
FIG. 2 is an EPR diagram of defective black phosphenes and bulk black phosphorus;
FIG. 3 is a graph comparing the performance (specific discharge capacity) of a defective black phosphene/carbon nanotube composite structure prepared and a black phosphene prepared in comparative example 1;
FIG. 4 is a graph comparing the performance (specific capacity at high density) of a defective black phosphene/carbon nanotube composite structure prepared and a black phosphene prepared in comparative example 1;
fig. 5 is a graph comparing the performance (cycle stability) of the prepared defective black phosphene/carbon nanotube composite structure and the black phosphene prepared in comparative example 1.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The test methods used in the following examples and experimental examples are conventional methods unless otherwise specified; the materials, reagents and the like used, unless otherwise specified, are commercially available reagents and materials; the equipment used, unless otherwise specified, is conventional laboratory equipment.
Example 1
The embodiment provides a preparation method of a defect black phosphorus alkene/carbon nanotube composite structure, which comprises the following steps:
(1) preparing an electrolyte: stirring and dispersing carbon nano tubes (which are only needed when cathode chamber electrolyte is prepared), 5mg of urea and 15mg of adsorption aid tetramethyl phosphorus chloride in dispersing agent N, N-dimethylformamide, wherein the dosage ratio of the carbon nano tubes to the dispersing agent is 1 mg/ml;
(2) an H-shaped double electrochemical pool reactor is adopted, and a proton exchange membrane is used for separating a cathode chamber and an anode chamber; adding electrolyte into the cathode chamber and the anode chamber respectively; fixing the black phosphorus crystal on an electrode as a cathode and placing the cathode in a cathode chamber, and assembling a platinum sheet electrode as an anode into an electrolytic cell;
(3) electrifying and electrolyzing for 15 minutes under the voltage of 10V, taking out the obtained product after electrolysis, and performing ultrasonic and centrifugal separation to obtain the black phosphorus alkene/carbon nano tube composite structure.
Example 2
The embodiment provides a preparation method of a black phosphorus alkene/carbon nanotube composite structure, which comprises the following steps:
(1) preparing an electrolyte: stirring and dispersing carbon nano tubes (which are only needed when cathode chamber electrolyte is prepared), 1mg of urea and 15mg of adsorption aid tetramethyl phosphorus chloride in dispersing agent N, N-dimethylformamide; the dosage ratio of the carbon nano tube to the dispersant is 5 mg/ml;
(2) an H-shaped double electrochemical pool reactor is adopted, and a proton exchange membrane is used for separating a cathode chamber and an anode chamber; adding electrolyte into the cathode chamber and the anode chamber respectively; fixing the black phosphorus crystal on an electrode as a cathode and placing the cathode in a cathode chamber, and assembling a platinum sheet electrode as an anode into an electrolytic cell;
(3) electrifying and electrolyzing for 15 minutes under the voltage of 10V, taking out the obtained product after electrolysis, and performing ultrasonic and centrifugal separation to obtain the black phosphorus alkene/carbon nano tube composite structure.
Example 3
The embodiment provides a preparation method of a black phosphorus alkene/carbon nanotube composite structure, which comprises the following steps:
(1) preparing an electrolyte: stirring and dispersing carbon nano tubes (which are only needed when cathode chamber electrolyte is prepared), 5mg of urea and 15mg of adsorption aid tetramethyl phosphorus chloride in dispersing agent N, N-dimethylformamide; the dosage ratio of the carbon nano tube to the dispersant is 10 mg/ml;
(2) an H-shaped double electrochemical pool reactor is adopted, and a proton exchange membrane is used for separating a cathode chamber and an anode chamber; adding electrolyte into the cathode chamber and the anode chamber respectively; fixing the black phosphorus crystal on an electrode as a cathode and placing the cathode in a cathode chamber, and assembling a platinum sheet electrode as an anode into an electrolytic cell;
(3) electrifying and electrolyzing for 15 minutes under the voltage of 10V, taking out the obtained product after electrolysis, and performing ultrasonic and centrifugal separation to obtain the black phosphorus alkene/carbon nano tube composite structure.
Example 4
The embodiment provides a preparation method of a black phosphorus alkene/carbon nanotube composite structure, which comprises the following steps:
(1) preparing an electrolyte: stirring and dispersing carbon nano tubes (which are only needed when cathode chamber electrolyte is prepared), 3mg of urea and 15mg of adsorption aid tetramethyl phosphorus chloride in dispersing agent N, N-dimethylformamide; the dosage ratio of the carbon nano tube to the dispersant is 20 mg/ml;
(2) an H-shaped double electrochemical pool reactor is adopted, and a proton exchange membrane is used for separating a cathode chamber and an anode chamber; adding electrolyte into the cathode chamber and the anode chamber respectively; fixing the black phosphorus crystal on an electrode as a cathode and placing the cathode in a cathode chamber, and assembling a platinum sheet electrode as an anode into an electrolytic cell;
(3) electrifying and electrolyzing for 15 minutes under the voltage of 10V, taking out the obtained product after electrolysis, and performing ultrasonic and centrifugal separation to obtain the black phosphorus alkene/carbon nano tube composite structure.
Example 5
The embodiment provides a preparation method of a black phosphorus alkene/carbon nanotube composite structure, which comprises the following steps:
(1) preparing an electrolyte: stirring and dispersing carbon nano tubes (which are only needed when cathode chamber electrolyte is prepared), 7mg of urea and 15mg of adsorption aid tetramethyl phosphorus chloride in dispersing agent N, N-dimethylformamide; the dosage ratio of the carbon nano tube to the dispersant is 10 mg/ml;
(2) an H-shaped double electrochemical pool reactor is adopted, and a proton exchange membrane is used for separating a cathode chamber and an anode chamber; adding electrolyte into the cathode chamber and the anode chamber respectively; fixing the black phosphorus crystal on an electrode as a cathode and placing the cathode in a cathode chamber, and assembling a platinum sheet electrode as an anode into an electrolytic cell;
(3) electrifying and electrolyzing for 15 minutes under the voltage of 5V, taking out the obtained product after electrolysis, and performing ultrasonic and centrifugal separation to obtain the black phosphorus alkene/carbon nano tube composite structure.
Example 6
The embodiment provides a preparation method of a black phosphorus alkene/carbon nanotube composite structure, which comprises the following steps:
(1) preparing an electrolyte: stirring and dispersing carbon nano tubes (which are only needed when cathode chamber electrolyte is prepared), 9mg of urea and 15mg of adsorption aid tetramethyl phosphorus chloride in dispersing agent N, N-dimethylformamide; the dosage ratio of the carbon nano tube to the dispersant is 10 mg/ml;
(2) an H-shaped double electrochemical pool reactor is adopted, and a proton exchange membrane is used for separating a cathode chamber and an anode chamber; adding electrolyte into the cathode chamber and the anode chamber respectively; fixing the black phosphorus crystal on an electrode as a cathode and placing the cathode in a cathode chamber, and assembling a platinum sheet electrode as an anode into an electrolytic cell;
(3) electrifying and electrolyzing for 15 minutes under the voltage of 20V, taking out the obtained product after electrolysis, and performing ultrasonic and centrifugal separation to obtain the black phosphorus alkene/carbon nano tube composite structure.
Example 7
The embodiment provides a preparation method of a black phosphorus alkene/carbon nanotube composite structure, which comprises the following steps:
(1) preparing an electrolyte: stirring and dispersing carbon nano tubes (which are only needed when cathode chamber electrolyte is prepared), 10mg of urea and 15mg of adsorption aid tetramethyl phosphorus chloride in dispersing agent N, N-dimethylformamide; the dosage ratio of the carbon nano tube to the dispersant is 10 mg/ml;
(2) an H-shaped double electrochemical pool reactor is adopted, and a proton exchange membrane is used for separating a cathode chamber and an anode chamber; adding electrolyte into the cathode chamber and the anode chamber respectively; fixing the black phosphorus crystal on an electrode as a cathode and placing the cathode in a cathode chamber, and assembling a platinum sheet electrode as an anode into an electrolytic cell;
(3) electrifying and electrolyzing for 15 minutes under the voltage of 30V, taking out the obtained product after electrolysis, and performing ultrasonic and centrifugal separation to obtain the black phosphorus alkene/carbon nano tube composite structure.
Comparative example 1
The comparative example provides a preparation method of black phosphorus alkene, which comprises the following steps:
(1) preparing an electrolyte: stirring and dispersing the adsorption aid in dispersing agent N, N-dimethylformamide;
(2) an H-shaped double electrochemical pool reactor is adopted, and a proton exchange membrane is used for separating a cathode chamber and an anode chamber; adding electrolyte into the cathode chamber and the anode chamber respectively; fixing the black phosphorus crystal on an electrode as a cathode and placing the cathode in a cathode chamber, and assembling a platinum sheet electrode as an anode into an electrolytic cell;
(3) electrifying and electrolyzing for 15 minutes under the voltage of 10V, taking out the black phosphorus alkene after electrolysis, and carrying out ultrasonic and centrifugal separation to obtain the black phosphorus alkene.
The black phosphene and defective black phosphene/carbon nanotube composite structures obtained in comparative example 1 and examples 1 to 7 were applied to a lithium-sulfur battery for performance testing.
As shown in FIG. 3, the initial specific discharge capacity (about 1120mAh/g) of the defective black phosphorus alkene/carbon nanotube composite (example 3) is significantly higher than that of the comparative example (about 850 mAh/g). After 100 cycles of circulation, the specific capacity of the defective black phosphorus alkene/carbon nanotube composite material is maintained to be about 750mAh/g, and the specific capacity of the comparative example is about 500 mAh/g.
As shown in fig. 4, at high current density (4C), the specific capacity of the defective black phospholene/carbon nanotube composite material was still maintained at about 680 mAh/g.
As shown in fig. 5, a cycle stability test of 500 cycles indicates that the defective black phosphorus alkene/carbon nanotube composite material electrode has better stability, and the reduction rate is 0.05% per cycle.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.

Claims (6)

1. A preparation method of a defect black phosphorus alkene carbon nanotube composite material is characterized in that an H-shaped double electrochemical cell reactor is adopted, a mixture of a carbon nanotube, an adsorption auxiliary agent, a dispersing agent and organic amine is used as an electrolyte, a black phosphorus crystal is used as a cathode, platinum is used as an anode, a cathode chamber and an anode chamber are separated by a proton exchange membrane, and the defect black phosphorus alkene carbon nanotube composite material is obtained by ultrasonic and centrifugal separation after electrification and electrolysis; the size of the black phosphorus crystal is 0.3-2 cm; the dosage ratio of the carbon nano tube to the dispersant is as follows: 1-20 mg/ml; the dosage ratio of the organic amine to the dispersant is as follows: 1-10 mg/ml; the voltage of electrolysis is 5-30V, and the time is 1-20 min.
2. The method for preparing the defective black phosphorus alkene carbon nanotube composite material of claim 1, wherein the organic amine is one or two of urea, polyethyleneimine and melamine.
3. The method for preparing the defective black phosphorus alkene carbon nanotube composite material of claim 1, wherein the dispersant is one or two of N, N-dimethylformamide, N-methylpyrrolidone and N, N-dimethylacetamide.
4. The method for preparing a defective black phosphorus alkene carbon nanotube composite material according to claim 1, wherein the adsorption aid is selected from tetramethylphosphonium chloride, tetrabutylphosphonium bromide, tetramethylolphosphonium chloride, ethoxycarbonylethylidene triphenylphosphine, 2-carboxyethyltriphenylphosphonium bromide.
5. The defective black phosphorus alkene carbon nanotube composite material obtained by the method of any one of claims 1 to 4.
6. The use of the defective black phosphorus alkene carbon nanotube composite of claim 5 as an electrode material in the preparation of a lithium sulfur battery.
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Synthesis of high-quality black phosphorus sponges for all-solid-state supercapacitors;MinWen;《Mater.Horiz.》;20181024;实验部分 *

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