CN106299282B - Nitrogen-doped carbon nanotube sulfur composite material and preparation method thereof - Google Patents

Nitrogen-doped carbon nanotube sulfur composite material and preparation method thereof Download PDF

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CN106299282B
CN106299282B CN201610798267.9A CN201610798267A CN106299282B CN 106299282 B CN106299282 B CN 106299282B CN 201610798267 A CN201610798267 A CN 201610798267A CN 106299282 B CN106299282 B CN 106299282B
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nitrogen
carbon nanotube
doped carbon
composite material
sulfur
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CN106299282A (en
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曹勇
许家齐
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Hefei Gotion High Tech Power Energy Co Ltd
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Hefei Guoxuan High Tech Power Energy Co Ltd
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a nitrogen-doped carbon nanotube sulfur composite material and a preparation method thereof. The method comprises the steps of acidizing the carbon nano tube, and carrying out polymerization reaction with amines to obtain a dark green precursor; placing the precursor in a tube furnace, and treating the precursor in a nitrogen atmosphere to obtain a nitrogen-doped carbon nanotube; and carrying out ball milling and mixing treatment on the nitrogen-doped carbon nanotube and sulfur according to the mass ratio of 1: 10-3: 7 to obtain the nitrogen-doped carbon nanotube-sulfur composite material. The nitrogen-doped carbon nanotube sulfur composite material prepared by the method of the invention shows better performance when being used in a lithium sulfur battery: the nitrogen doping can play a certain role in catalyzing and adsorbing the fracture and generation of S-S bonds in the charging and discharging processes, and reduces the dissolution of intermediate products in electrolyte, so that the electrolyte has better multiplying power and cycle performance.

Description

Nitrogen-doped carbon nanotube sulfur composite material and preparation method thereof
Technical Field
The invention belongs to the field of lithium battery anode materials, and particularly relates to a nitrogen-doped carbon nanotube sulfur composite material and a preparation method thereof.
Background
With the rapid development of economy and the continuous improvement of human living standard, people pay more and more attention to energy problems and environmental problems, and the development of renewable resources and green energy becomes a problem to be solved urgently. Secondary batteries play an indispensable role in the development and utilization of new energy. And with the rapid development of various portable electronic devices, new requirements for energy density of batteries have been made by humans. Therefore, the development of various novel high specific energy batteries is urgent.
Currently, the cathode material is the most competitive and largest market capacity domain in the lithium ion battery market. The anode material is expensive, which is a direct reason for limiting the application range of lithium ion batteries. Currently, lithium ion anode materials are mainly divided into layered LiMO2(M ═ Co, Ni, Mn), lithium manganate (LiMn) of spinel structure2O4) And ternary metal composite oxide positive electrode materials (such as lithium iron phosphate and manganese-based lithium-rich materials). Current LiCoO2The positive electrode material is commercialized, but the defects of poor thermal stability, poor overcharge resistance and the like exist, the element Co belongs to a rare element and is high in price, and the metal Co can cause environmental pollution and has certain influence on a human body; and LiNiO of the layered material2The disadvantage of harsh preparation exists; in contrast, the lithium manganate with spinel structure has the advantages of good safety, high voltage, low cost, environmental protection and the like, but has poor high-temperature performance, and is not suitable for being used in the field of lithium ion batteriesStorage and the like. For example, the application of lithium iron phosphate in power batteries is seriously influenced because the electronic conductivity and the ionic conductivity of the lithium iron phosphate are both low. In a novel electrochemical energy storage system, elemental sulfur is used as a positive electrode material of a lithium-sulfur battery, metal lithium is used as a negative electrode, the theoretical specific energy is as high as 2600Wh/kg, and the lithium-sulfur battery is a battery system which is generally accepted to have the highest energy density except for a lithium-air battery. The working voltage of the lithium-sulfur battery is 2.1V, which is suitable for the voltage range of various market demands at present, and is one of the most promising secondary battery systems recognized at present.
The direct use of elemental sulfur as a positive electrode material has many problems: the electronic and ionic conductance of elemental sulfur is very low; the volume change of reactants and products is large before and after charging and discharging, so that the anode material is pulverized and the active substance falls off in the charging and discharging process; the "shuttling effect" caused by soluble polysulfides generated during charging and discharging.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a nitrogen-doped carbon nanotube sulfur composite material and a preparation method thereof. The method effectively dopes 1-4% of nitrogen element in the carbon nano tube, improves the reaction active site on the surface of the carbon nano tube, and obviously improves the cycle and rate capability of the carbon nano tube sulfur composite material.
The purpose of the invention can be realized by the following technical scheme:
the nitrogen-doped carbon nanotube sulfur composite material is characterized by comprising a nitrogen-doped carbon nanotube framework and sulfur attached to the surface or inside of the nitrogen-doped carbon nanotube, wherein the mass percent of nitrogen element is 1-4%; the mass percent of the sulfur is 60-92%.
Another object of the present invention is to provide a method for preparing a nitrogen-doped carbon nanotube sulfur composite material, comprising the following steps:
(1) mixing a carbon nano tube and concentrated hydrochloric acid according to the mass ratio of 1: 20-100, placing the mixture on a magnetic stirrer for stirring treatment for 1-6 hours, and placing the mixture in an oven at the temperature of 45-90 ℃ for treatment for 18-24 hours to obtain a functionalized carbon nano tube;
(2) adding a functionalized carbon nano tube, amines and a catalyst ammonium persulfate according to the mass ratio of 1:1-7, uniformly stirring, placing in a constant-temperature water bath, and reacting at 40-80 ℃ until the color of the solution is changed into dark green; after the reaction is finished, filtering, washing, drying and grinding to obtain a dark green precursor;
(3) placing the dark green precursor in a tube furnace, and treating for 2-4 h at 700-900 ℃ in a nitrogen atmosphere to obtain a nitrogen-doped carbon nanotube;
(4) and ball-milling and mixing the nitrogen-doped carbon nanotube and sulfur according to the proportion of 1: 10-3: 7, and treating for 4-8 hours at the temperature of 150-160 ℃ to obtain the nitrogen-doped carbon nanotube-sulfur composite material.
Preferably, the diameter of the raw material carbon nanotube used in the step (1) is 5-100 nm, and the specific surface area is 50-300 m2/g。
Preferably, the amine substance in the step (2) is at least one of aniline and m-diphenylamine.
Preferably, the nitrogen-doped carbon nanotube in the step (3) has a tube diameter of 5-100 nm and a specific surface area of 100-400 m2/g。
Preferably, the adding amount of the catalyst ammonium persulfate in the step (2) is 7-14 times of the weight of the carbon nano tube.
Preferably, the sulfur in the step (4) is sublimed sulfur with the purity of more than 99.5 percent.
Preferably, the adding amount of the catalyst ammonium persulfate in the step (2) is 7-14 times of the weight of the carbon nano tube.
The invention has the beneficial effects that: the nitrogen-doped carbon nanotube sulfur composite material obtained by the invention has higher specific capacity and cycle performance. The method effectively dopes 1-4% of nitrogen atoms in the carbon nano tube, improves the reactive sites on the surface of the carbon nano tube, and obviously improves the cycle and rate performance.
Drawings
Fig. 1 is an SEM of the nitrogen-doped carbon nanotube prepared in example 1 of the present invention.
Fig. 2 is a TEM of the nitrogen-doped carbon nanotube prepared in example 1 of the present invention.
Fig. 3 is a graph of rate capability of the nitrogen-doped carbon nanotube sulfur composite material prepared in example 1 of the present invention.
Fig. 4 is a cycle performance diagram of the nitrogen-doped carbon nanotube sulfur composite material prepared in example 1 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the figures and specific embodiments.
Example 1
Mixing the carbon nano tube and concentrated hydrochloric acid according to the mass ratio of 1:20, placing the mixture on a magnetic stirrer, stirring the mixture for 2 hours, and placing the mixture in an oven at the temperature of 80 ℃ for 24 hours to obtain a functionalized carbon nano tube;
adding a functionalized carbon nano tube, m-diphenylamine and a catalyst ammonium persulfate according to the mass ratio of 1:7, wherein the addition amount of the ammonium persulfate is 7 times of the weight of the carbon nano tube, uniformly stirring, placing in a constant-temperature water bath, and reacting at 60 ℃ until the color of the solution is changed into dark green; after the reaction is finished, filtering, washing, drying and grinding to obtain a dark green precursor;
placing the dark green precursor in a tube furnace, and treating for 2h at 900 ℃ in a nitrogen atmosphere to obtain a nitrogen-doped carbon nanotube;
and carrying out ball milling and mixing on the nitrogen-doped carbon nanotube and sulfur according to the mass ratio of 3:7, and treating at 155 ℃ for 5 hours to obtain the nitrogen-doped carbon nanotube-sulfur composite material (NCNT-S).
Comparative example 1
And (2) ball-milling and mixing the carbon nano tube and sulfur according to the mass ratio of 3:7, and treating at 155 ℃ for 5 hours to obtain the carbon nano tube sulfur composite material (CNT-S).
The nitrogen-doped carbon nanotube sulfur composite prepared in example 1 was characterized and assembled into a 2016 type button cell for electrochemical testing, and fig. 1 is an SEM image of the nitrogen-doped nanotubes. Fig. 2 is a TEM of a nitrogen doped carbon nanotube sulfur composite. It can be seen from a that a layer of coating layer with relatively dark color is left on the surface of the carbon tube after polyaniline carbonization, and it can be seen from b that the thickness of the carbon layer left after polyaniline carbonization on the surface of the carbon tube is about 10 nm. FIG. 3 shows the rate capability of the nitrogen-doped carbon nanotube-sulfur composite material, after the nitrogen-doped carbon nanotube is compounded with sulfur, the first discharge capacity reaches 1100mAh/g, and the discharge capacity is 567mAh/g at a current density of 2A/g; more importantly, the capacity of the battery still has 518mAh/g and 425mAh/g under the current density of 5A/g and 10A/g, which is the result that the carbon nano tube before doping can not achieve. FIG. 4 shows the cycle performance of the composite material before and after doping in comparative example and example 1, wherein the capacities of the composite material after the activation of the first five cycles are 797mAh/g and 835mAh/g respectively at a current density of 1A/g, the capacities of the composite material after the circulation of 200 cycles are 471mAh/g and 608mAh/g respectively, and the capacity retention rates of the composite material are 60.5% and 78.7% respectively; after 400 cycles, the capacity retention rates are 427mAh/g and 607mAh/g, and the capacity retention rates are 53.6 percent and 78.7 percent; after 500 cycles, the capacities are respectively 401mAh/g and 599mAh/g, the capacity retention rates are respectively 41.1% and 66.4%, and the cycle performance is greatly improved after nitrogen doping.
Example 2
Mixing the carbon nano tube and concentrated hydrochloric acid in a ratio of 1:50, placing the mixture on a magnetic stirrer, stirring for 6 hours, and placing the mixture in a baking oven at the temperature of 45 ℃ for 20 hours to obtain a functionalized carbon nano tube;
adding a functionalized carbon nano tube, aniline and catalyst ammonium persulfate according to the proportion of 1:1, wherein the addition amount of the ammonium persulfate is 7 times of the weight of the carbon nano tube, uniformly stirring, placing in a constant-temperature water bath kettle, and reacting at 40 ℃ until the color of the solution is changed into dark green; after the reaction is finished, filtering, washing, drying and grinding to obtain a dark green precursor;
placing the dark green precursor in a tube furnace, and treating for 4 hours at 700 ℃ in a nitrogen atmosphere to obtain a nitrogen-doped carbon nanotube;
and carrying out ball milling and mixing on the nitrogen-doped carbon nanotube and sulfur according to the mass ratio of 3:7, and treating for 4h at 150 ℃ to obtain the nitrogen-doped carbon nanotube-sulfur composite material.
Example 3
Mixing the carbon nano tube and concentrated hydrochloric acid in a ratio of 1:100, placing the mixture on a magnetic stirrer, stirring the mixture for 1 hour, and placing the mixture in a drying oven at the temperature of 90 ℃ for 18 hours to obtain a functionalized carbon nano tube;
adding a functionalized carbon nano tube, aniline and catalyst ammonium persulfate according to the proportion of 1:3, wherein the adding amount of the ammonium persulfate is 10 times of the weight of the carbon nano tube, uniformly stirring, placing in a constant-temperature water bath kettle, and reacting at 80 ℃ until the color of the solution is changed into dark green; after the reaction is finished, filtering, washing, drying and grinding to obtain a dark green precursor;
placing the dark green precursor in a tube furnace, and treating for 3h at 800 ℃ in a nitrogen atmosphere to obtain a nitrogen-doped carbon nanotube;
and carrying out ball milling and mixing on the nitrogen-doped carbon nanotube and sulfur according to the mass ratio of 1:10, and treating for 8 hours at 160 ℃ to obtain the nitrogen-doped carbon nanotube-sulfur composite material.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the spirit of the invention or exceeding the scope defined by the claims.

Claims (5)

1. The preparation method of the nitrogen-doped carbon nanotube sulfur composite material is characterized by comprising the following steps of:
(1) mixing a carbon nano tube and concentrated hydrochloric acid according to the mass ratio of 1: 20-100, placing the mixture on a magnetic stirrer for stirring treatment for 1-6 hours, and placing the mixture in an oven at the temperature of 45-90 ℃ for treatment for 18-24 hours to obtain a functionalized carbon nano tube;
(2) adding a functionalized carbon nano tube, aniline or m-diphenylamine and catalyst ammonium persulfate according to the mass ratio of 1:1-7, uniformly stirring, placing in a constant-temperature water bath, and reacting at 40-80 ℃ until the color of the solution is changed into dark green; after the reaction is finished, filtering, washing, drying and grinding to obtain a dark green precursor;
(3) placing the dark green precursor in a tube furnace, and treating for 2-4 h at 700-900 ℃ in a nitrogen atmosphere to obtain a nitrogen-doped carbon nanotube;
(4) and ball-milling and mixing the nitrogen-doped carbon nanotube and sulfur according to the proportion of 1: 10-3: 7, and treating for 4-8 hours at the temperature of 150-160 ℃ to obtain the nitrogen-doped carbon nanotube-sulfur composite material.
2. The method for preparing the nitrogen-doped carbon nanotube sulfur composite material as claimed in claim 1, wherein the diameter of the raw material carbon nanotube used in the step (1) is 5 to 100nm, and the specific surface area is 50 to 300m2/g。
3. The method for preparing the N-doped carbon nanotube-sulfur composite material according to claim 1, wherein the diameter of the N-doped carbon nanotube in the step (3) is 5 to 100nm, and the specific surface area is 100 to 400m2/g。
4. The method for preparing the nitrogen-doped carbon nanotube sulfur composite material according to claim 1, wherein the addition amount of the catalyst ammonium persulfate in the step (2) is 7-14 times of the weight of the carbon nanotube.
5. The method for preparing the nitrogen-doped carbon nanotube sulfur composite material as claimed in claim 1, wherein the sulfur of the step (4) is sublimed sulfur with a purity of more than 99.5%.
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CN106876673B (en) * 2017-03-10 2019-06-11 哈尔滨工业大学 The method that one-step method prepares the core-shell structure lithium sulfur battery anode material that titanium dioxide and graphene bilayer coat altogether
CN109921041B (en) * 2017-12-12 2021-10-08 中国科学院大连化学物理研究所 Preparation and application of non-noble metal nitrogen-doped hollow carbon nanotube electrocatalyst
CN110729436B (en) * 2018-07-17 2022-10-28 南京理工大学 Heteroatom-doped carbon nanotube modified carbon fiber paper and preparation method and application thereof
CN110858651B (en) * 2018-08-24 2021-04-02 清华大学 Carbon nanotube composite structure and preparation method thereof
CN110858644B (en) * 2018-08-24 2021-04-02 清华大学 Positive electrode, method for producing same, and battery using same
CN111362254B (en) * 2020-03-17 2022-07-05 广西师范大学 Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material
CN111675208B (en) * 2020-06-08 2023-02-03 齐鲁工业大学 Sulfur-nitrogen doped hollow carbon nanotube composite material and preparation method and application thereof
CN113675387A (en) * 2021-07-15 2021-11-19 南京信息工程大学 Sulfur-carbon composite material, preparation method and application thereof

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