CN111276679A - Double-carbon composite molybdenum sulfide composite material for sodium ion battery cathode material and preparation method thereof - Google Patents

Double-carbon composite molybdenum sulfide composite material for sodium ion battery cathode material and preparation method thereof Download PDF

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CN111276679A
CN111276679A CN202010075907.XA CN202010075907A CN111276679A CN 111276679 A CN111276679 A CN 111276679A CN 202010075907 A CN202010075907 A CN 202010075907A CN 111276679 A CN111276679 A CN 111276679A
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walled carbon
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molybdenum sulfide
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孙晓红
郭金泽
安世乾
罗俊鹏
蔡顺汀
郑春明
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Tianjin University
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    • H—ELECTRICITY
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    • H—ELECTRICITY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a double-carbon composite molybdenum sulfide composite material for a sodium ion battery cathode material and a preparation method thereof. The multi-walled carbon nanotubes in the material are inserted among the nitrogen-doped carbon composite molybdenum sulfide particles to form a three-dimensional conductive network structure, wherein the nano diameter of the nitrogen-doped carbon composite molybdenum sulfide particles is 50-100 nm. Firstly, adding a multi-walled carbon nanotube into deionized water, and performing ultrasonic treatment to obtain a multi-walled carbon nanotube mixed solution; adding polyvinylpyrrolidone, sodium molybdate, thiourea and urea into the solution, fully stirring, and transferring to a hydrothermal reaction kettle for hydrothermal reaction;then separating, washing, drying and carbonizing the obtained product to obtain the MoS with double carbon composition2. The carbon nano tube in the composite material can control the volume expansion of molybdenum sulfide in the conductive process, the conductivity of the material can be improved by the three-dimensional conductive structure, and the stability of the structure of the molybdenum sulfide material is effectively improved, so that the capacity is kept not to be attenuated.

Description

Double-carbon composite molybdenum sulfide composite material for sodium ion battery cathode material and preparation method thereof
Technical Field
The invention belongs to the field of inorganic nano material synthesis. In particular, it relates to the preparation of dual carbon composite MoS by hydrothermal and carbonization processes2A method of forming a composite material of (1). In particular to a double-carbon composite molybdenum sulfide composite material for a sodium ion battery cathode material and a preparation method thereof.
Background
As a large number of mobile devices enter people's lives, more demands are placed on energy storage devices. The lithium ion energy storage device has the advantages of small volume, high energy density and recycling, and is widely used. However, the lithium resource reserves of the earth are limited and distributed unevenly, and the requirements of people on production and life are difficult to meet, so that the development of a material suitable for large-scale use is urgent. The sodium in the same main group with lithium has similar physical and chemical properties with lithium, and the sodium resource has abundant reserves on the earth and low cost, so the sodium ion energy storage device is expected to become the next generation of energy storage equipment for large-scale application. However, sodium ions have a larger ion radius (Na) than lithium ions+Radius of
Figure BDA0002378483590000012
Li+Radius of
Figure BDA0002378483590000011
) And the structure of the material is greatly damaged in the energy storage process, so that the anode material which is used for storing more mature lithium ions cannot be directly used as a sodium ion anode material. Therefore, the research and development of the cathode material with stable structural cycle for sodium ion energy storage becomes a key technical problem to be solved.
Recently, MoS with graphene-like two-dimensional layered structure2The material has attracted wide attention as a sodium ion energy storage material, the interlayer spacing of the material is 0.615nm, and the wider interlayer spacing provides theoretical possibility for the sodium ion energy storage material to have good rate capability. However, good layer structure also has some disadvantages, including inevitable contribution of MoS during intercalation/deintercalation of sodium ions2The volume changes, thereby causing the damage of the material structure, and the poor conductivity prevents the transmission of electrons in the energy storage process, and the two defects jointly cause the rapid capacity attenuation of sodium ions in the energy storage process.
In response to such problems, researchers have synthesized MoS2Improvement of MoS by using/carbon composite material2The base active material has poor ion transport kinetics and solves the problem of volume expansion during energy storage, and the form of carbon mainly comprises amorphous carbon, graphene and carbon nanotubes. Ren group by mixing graphene, carbon nanotubes and MoS2The composite structure establishes a three-dimensional structure, the carbon nano tube wrapped by the graphene provides a good substrate condition for the transmission of electrons, and the MoS is compensated2The conductivity of the material is poor. Carbon nanotubes as an excellent conductive agent can establish a three-dimensional conductive network, and Sun groups utilize multi-walled carbon tubes to establish a three-dimensional neural network, FeS2Distributed therein. While in-situ amorphous carbon and MoS are used2The compounding can not only improve the conductivity of the material, but also inhibit MoS2Change in volume of (a). The Tang group synthesizes hollow tubular MoS by adopting a microwave solvothermal method2the/C composite material shows good cycling stability when used for a sodium ion battery. Guan is combined into a core-shell structure, and amorphous carbon pair SnS is utilized2Carry out coating to limit SnS2In Na+The volume change in the energy storage process stabilizes the structure, thereby having excellent electrochemical performance at 100mA g-1Under the condition of current density, the specific capacity of 100 cycles of circulation is kept at 690mA h g-1. And by the defect-rich carbon and MoS2The compounding can also obviously shorten the diffusion distance of sodium ions and improve the rate capability of the material. Most preferablyTypically, carbon defects are constructed by doping nitrogen elements, Sun groups synthesize nitrogen-rich doped porous carbon for a sodium ion battery cathode material by a spray drying method, the nitrogen content reaches 17.72%, and rich nitrogen doping provides more active sites for sodium ions and improves the electron transmission rate. Nitrogen-doped carbon and MoS synthesized by Liang group through hydrothermal method2The composite material is used for sodium ion battery cathode, and half battery performance test is carried out at 2A g-1Under the condition of current density of (1), the capacity of 5000 circles of circulation is kept at 128mA h g-1Good cycling stability fully reflects the stable MoS of nitrogen-doped carbon2The structure of (1). But currently for MoS2The modification (2) still has the defect that the capacity is greatly attenuated during charge-discharge cycles. This is because the structurally stable carbon does not adequately protect the MoS2The function of the structure. Thus, a scientific design of a dual-carbon composite MoS2Is to improve MoS2The material is one of effective measures for the cycling stability of the cathode material of the sodium-ion battery.
Disclosure of Invention
The invention aims to provide a dual-carbon composite MoS for a sodium ion battery cathode material by adopting a hydrothermal and carbonization method2The composite material and the preparation method. The double carbon in the material refers to a multi-walled carbon nanotube and nitrogen-doped carbon, the multi-walled carbon nanotube is inserted between the nitrogen-doped carbon composite molybdenum disulfide particles to form a three-dimensional conductive network structure, wherein the nano diameter of the nitrogen-doped carbon composite molybdenum disulfide is 50-100 nm.
The composite material is used as a sodium electric anode material, the multiwalled carbon nanotube with the three-dimensional conductive network structure can provide excellent conductivity for the material, and the nitrogen-doped carbon is wrapped in the MoS2The structure plays a stable role, prevents the structure in the circulation process from being crushed, and simultaneously plays a role in promoting the transmission of electrons and shortening the diffusion distance of sodium ions. Therefore, the material with the structure has good rate capability and cycling stability.
The technical scheme of the invention is as follows:
dual-carbon composite MoS for sodium ion battery cathode material2Preparation of the composite MaterialThe preparation method is characterized by comprising the following steps:
1) adding the multi-walled carbon nano-tube into deionized water, carrying out ultrasonic treatment for 1-3h, and stirring at the rotating speed of 200-400r/min for 3-6h to prepare a mixed solution in which the multi-walled carbon nano-tube is uniformly dispersed;
2) adding polyvinylpyrrolidone, sodium molybdate, thiourea and urea into the mixed solution with uniformly dispersed multi-walled carbon nanotubes prepared in the step 1), and stirring at the rotating speed of 200-400r/min for 3-6h to prepare the mixed solution containing polyvinylpyrrolidone, multi-walled carbon nanotubes, sodium molybdate, thiourea and urea;
3) transferring the mixed solution prepared in the step 2) into a lining of a polytetrafluoroethylene hydrothermal reaction kettle, sealing the lining by using a stainless steel reaction kettle, and carrying out hydrothermal reaction; after the reaction is finished, cooling along with the furnace, taking out the reactant, respectively washing with absolute ethyl alcohol and deionized water, and drying in vacuum to obtain the reactant;
4) placing the reactant obtained in the step 3) in a quartz boat, and then placing the quartz boat in a tube furnace filled with Ar gas for carbonization treatment to obtain the three-dimensional conductive carbon nano tube and nitrogen-doped carbon composite MoS with good crystallinity2The composite material of (1).
The mass ratio of the sodium molybdate to the polyvinylpyrrolidone and the thiourea is 1:1-7:1-5, and the mass ratio of the thiourea to the urea and the multi-walled carbon nano tube is 10-70:1: 1-5.
The concentration of the multi-wall carbon nano-tube in the step 1) is 0.5-4.0 g/L.
The hydrothermal conditions in the step 3): 180 ℃ and 220 ℃, and the heat preservation time is 12-36 h.
The washing times of the step 4) by using deionized water and absolute ethyl alcohol are 3-8 times
The drying conditions in the step 4) are as follows: vacuum drying at 60-80 deg.C for 10-12 h.
The carbonization conditions in the step 5) are as follows: the heating rate is 2-5 ℃/min, and the temperature is kept at 500-800 ℃ for 2-5 h.
Used in sodium ion battery, at 100mA g-1The performance of the alloy is tested under the current density, and after the alloy is cycled for 100 times, the specific capacity of the alloy reaches 430mA h g-1The above. At 1A g-1Current density cycle of 1000 timesThen the specific capacity can reach 230mA h g-1The above. The excellent electrochemical performance shows that the material has good conductivity and structural stability, and can be used as a negative electrode material of a sodium-ion battery.
The invention has the effect of preparing the three-dimensional conductive carbon nano tube and nitrogen-doped carbon composite MoS for the cathode of the sodium ion battery2The composite material of (1). The material is nitrogen-doped carbon-coated MoS2And multi-walled carbon nanotubes interpenetrated within nitrogen-doped carbon-wrapped MoS2In which a three-dimensional network structure is formed, nitrogen-doped carbon-coated MoS2The diameter is 50-100nm, the formed three-dimensional conductive network structure can provide excellent conductivity for the material, and the nitrogen-doped carbon wraps the MoS2The structure plays a stable role, prevents the structure in the circulation process from being crushed, and simultaneously plays a role in promoting the transmission of electrons and shortening the diffusion distance of sodium ions.
Drawings
FIG. 1 is an X-ray diffraction chart of example 1, in which peaks of (002), (100), (103) and (110) planes at 14.36 °, 32.7 °, 39.5 ° and 58.3 ° correspond to those of a standard card accurately, and the peaks are in good shapes, which shows that MoS with good crystallinity is prepared2And a wider steamed bun peak exists at about 19.8 degrees, and can be classified into a multi-wall carbon nano tube and carbon. The composite material prepared was made of MoS2Carbon and multi-walled carbon nanotubes.
Fig. 2 is a scanning electron microscope image of example 2, and it can be seen from the image that the product is composed of multi-walled carbon nanotubes and carbon-compounded molybdenum sulfide nanoparticles, and the multi-walled carbon nanotubes are inserted into the molybdenum sulfide nanoparticles to form a three-dimensional conductive network structure.
FIG. 3 is a transmission electron micrograph of example 3, from which it can be seen that the molybdenum sulfide nanoparticles have a size distribution between 50 and 100 nm.
Detailed Description
The examples were carried out in the following proportions:
Figure BDA0002378483590000041
Figure BDA0002378483590000042
example 1:
1) adding 0.035g of multi-walled carbon nano-tube into 70ml of deionized water, carrying out ultrasonic treatment for 1h, and stirring at the rotating speed of 200r/min for 3h to obtain a mixed solution in which the multi-walled carbon nano-tube is uniformly dispersed, wherein the concentration of the multi-walled carbon nano-tube in the mixed solution is 0.5 g/L;
2) adding 0.350g of polyvinylpyrrolidone, 0.350g of sodium molybdate, 0.350g of thiourea and 0.035g of urea into the uniformly dispersed mixed solution of the multi-walled carbon nano-tubes prepared in the step 1), and stirring at the rotating speed of 200r/min for 3 hours to prepare a mixed solution of the polyvinylpyrrolidone, the multi-walled carbon nano-tubes, the sodium molybdate, the thiourea and the urea;
3) transferring the mixed solution prepared in the step 2) into a lining of a polytetrafluoroethylene hydrothermal reaction kettle, sealing the lining by using a stainless steel reaction kettle, and carrying out hydrothermal reaction for 12 hours at 180 ℃;
4) repeatedly washing the hydrothermal product by using deionized water and absolute ethyl alcohol for 3 times respectively to remove impurities, and carrying out vacuum drying at 60 ℃ for 10 hours to obtain a reactant;
5) placing the reactant obtained in the step 4) in a quartz boat, then placing the quartz boat in a tube furnace filled with Ar gas, heating to 500 ℃ at the speed of 2 ℃/min, preserving heat for 2h for carbonization, and cooling to room temperature along with the furnace to obtain the three-dimensional conductive carbon nanotube and nitrogen-doped carbon composite MoS with good crystallinity2The composite material of (1).
As shown in FIG. 1, the product produced is illustrated as being made from MoS2Carbon and multi-walled carbon nanotubes. Used in sodium ion battery, at 100mA g-1The performance of the alloy is tested under the current density of (1), and after the alloy is cycled for 100 times, the specific capacity of the alloy is 380mA h g-1The above. At 1A g-1The performance of the alloy is tested under the current density of (1), and after the alloy is cycled for 500 times, the specific capacity of the alloy is 180mA h g-1The above.
Example 2:
1) adding 0.158g of multi-walled carbon nano-tube into 70ml of deionized water, carrying out ultrasonic treatment for 2h, and stirring at the rotating speed of 300r/min for 4h to obtain a mixed solution in which the multi-walled carbon nano-tube is uniformly dispersed, wherein the concentration of the multi-walled carbon nano-tube in the mixed solution is 2.0 g/L;
2) adding 2.809g of polyvinylpyrrolidone, 0.702g of sodium molybdate, 2.107g of thiourea and 0.053g of urea into the uniformly dispersed mixed solution of the multi-walled carbon nano-tubes prepared in the step 1), and stirring at the rotating speed of 300r/min for 3 hours to prepare a mixed solution of the polyvinylpyrrolidone, the multi-walled carbon nano-tubes, the sodium molybdate, the thiourea and the urea;
3) transferring the mixed solution prepared in the step 2) into a lining of a polytetrafluoroethylene hydrothermal reaction kettle, sealing the lining by using a stainless steel reaction kettle, and carrying out hydrothermal treatment for 18h at the temperature of 200 ℃;
4) repeatedly washing the hydrothermal product with deionized water and absolute ethyl alcohol for 5 times respectively to remove impurities, and carrying out vacuum drying at 70 ℃ for 11 hours to obtain a reactant;
5) placing the reactant obtained in the step 4) in a quartz boat, then placing the quartz boat in a tube furnace filled with Ar gas, heating to 700 ℃ at the speed of 3 ℃/min, preserving heat for 3h for carbonization, and cooling to room temperature along with the furnace to obtain the three-dimensional conductive carbon nanotube and nitrogen-doped carbon composite MoS with good crystallinity2The composite material of (1).
As shown in FIG. 2, the prepared product is a composite MoS of three-dimensional conductive carbon nano-tube and nitrogen-doped carbon2The composite material of (1). Used in sodium ion battery, at 100mA g-1The performance of the alloy is tested under the current density of (1), and after the alloy is cycled for 100 times, the specific capacity of the alloy is 430mA h g-1The above. At 1A g-1The performance of the alloy is tested under the current density of (1), and after the alloy is cycled for 1000 times, the specific capacity of the alloy is 230mAh g-1The above.
Example 3:
1) adding 0.28g of multi-walled carbon nano-tube into 70ml of deionized water, carrying out ultrasonic treatment for 3h, and stirring at the rotating speed of 400r/min for 6h to obtain a mixed solution in which the multi-walled carbon nano-tube is uniformly dispersed, wherein the concentration of the multi-walled carbon nano-tube in the mixed solution is 4.0 g/L;
2) adding 5.488g of polyvinylpyrrolidone, 0.784g of sodium molybdate, 3.92g of thiourea and 0.056g of urea into the uniformly dispersed mixed solution of the multi-walled carbon nano-tubes prepared in the step 1), and stirring at the rotating speed of 400r/min for 6 hours to prepare a mixed solution of the polyvinylpyrrolidone, the multi-walled carbon nano-tubes, the sodium molybdate, the thiourea and the urea;
3) transferring the mixed solution prepared in the step 2) into a lining of a polytetrafluoroethylene hydrothermal reaction kettle, sealing the lining by using a stainless steel reaction kettle, and carrying out hydrothermal reaction for 24 hours at the temperature of 220 ℃;
4) repeatedly washing the hydrothermal product with deionized water and absolute ethyl alcohol for 8 times respectively to remove impurities, and carrying out vacuum drying at 80 ℃ for 12 hours to obtain a reactant;
5) placing the reactant obtained in the step 4) in a quartz boat, then placing the quartz boat in a tube furnace filled with Ar gas, heating to 800 ℃ at the speed of 5 ℃/min, preserving heat for 5h for carbonization, and cooling to room temperature along with the furnace to obtain the three-dimensional conductive carbon nanotube and nitrogen-doped carbon composite MoS with good crystallinity2The composite material of (1).
As shown in fig. 3, the prepared product is illustrated to have a size distribution of molybdenum disulfide nanoparticles between 50-100 nm. Used in sodium ion battery, at 100mA g-1The performance of the test piece is tested under the current density of (1), and after the test piece is cycled for 100 times, the specific capacity of the test piece is 412mA hg-1The above. At 1A g-1The performance of the alloy is tested under the current density of (1), and after the alloy is cycled for 800 times, the specific capacity of the alloy is 200mA h g-1The above.
While the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and/or modifications of the methods and techniques described herein may be made without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.

Claims (8)

1. Dual-carbon composite MoS for sodium ion battery cathode material2A composite material; it is characterized by multi-wall carbon nano-tubeAnd the nano-diameter of the nitrogen-doped carbon composite molybdenum disulfide is 50-100 nm.
2. Dual-carbon composite MoS for sodium ion battery cathode material2The preparation method of the composite material is characterized by comprising the following steps:
1) adding the multi-walled carbon nano-tube into deionized water, carrying out ultrasonic treatment for 1-3h, and stirring at the rotating speed of 200-400r/min for 3-6h to prepare a mixed solution in which the multi-walled carbon nano-tube is uniformly dispersed;
2) adding polyvinylpyrrolidone, sodium molybdate, thiourea and urea into the mixed solution with uniformly dispersed multi-walled carbon nanotubes prepared in the step 1), and stirring at the rotating speed of 200-400r/min for 3-6h to prepare the mixed solution containing polyvinylpyrrolidone, multi-walled carbon nanotubes, sodium molybdate, thiourea and urea;
3) transferring the mixed solution prepared in the step 2) into a lining of a polytetrafluoroethylene hydrothermal reaction kettle, sealing the lining by using a stainless steel reaction kettle, and carrying out hydrothermal reaction; after the reaction is finished, cooling along with the furnace, taking out the reactant, respectively washing with absolute ethyl alcohol and deionized water, and drying in vacuum to obtain the reactant;
4) placing the reactant obtained in the step 3) in a quartz boat, and then placing the quartz boat in a tube furnace filled with Ar gas for carbonization treatment to obtain the three-dimensional conductive carbon nanotube and nitrogen-doped dual-carbon composite MoS with good crystallinity2A composite material.
3. The method as set forth in claim 2, wherein the concentration of the multi-walled carbon nanotubes in the step 1) is 0.5 to 4.0 g/L.
4. The method as set forth in claim 2, characterized in that the mass ratio of the sodium molybdate to the polyvinylpyrrolidone and the thiourea is 1:1-7: 1-5; the mass ratio of the thiourea to the urea to the multi-walled carbon nano-tubes is 10-70:1: 1-5.
5. The method as set forth in claim 2, characterized in that the hydrothermal conditions in said step 3): 180 ℃ and 220 ℃, and the heat preservation time is 12-36 h.
6. The method as set forth in claim 2, characterized in that in the step 4), washing is performed 3 to 8 times with deionized water and absolute ethyl alcohol.
7. The method as set forth in claim 2, wherein the drying conditions in the step 4) are: vacuum drying at 60-80 deg.C for 10-12 h.
8. The method according to claim 2, characterized in that the carbonization conditions in step 5) are: the heating rate is 2-5 ℃/min, and the temperature is kept at 500-800 ℃ for 2-5 h.
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CN113622055A (en) * 2021-08-17 2021-11-09 四川轻化工大学 Sodium-ion battery negative electrode material and preparation method thereof
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