CN111106325B - Nitrogen-doped molybdenum disulfide/C/graphene composite material - Google Patents

Nitrogen-doped molybdenum disulfide/C/graphene composite material Download PDF

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CN111106325B
CN111106325B CN201811262177.3A CN201811262177A CN111106325B CN 111106325 B CN111106325 B CN 111106325B CN 201811262177 A CN201811262177 A CN 201811262177A CN 111106325 B CN111106325 B CN 111106325B
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nitrogen
reaction
graphene
composite material
dispersion
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CN111106325A (en
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郭金
王少军
凌凤香
张会成
廖莎
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • 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
    • H01M4/362—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
    • 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
    • H01M4/58—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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • H01M4/58—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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

A nitrogen-doped molybdenum disulfide/C/graphene composite material is prepared by using formaldehyde as a bridge, enabling the formaldehyde to be appropriately crosslinked with melamine to form a nitrogen-doped precursor, carrying out hydrothermal reaction to enable the nitrogen-doped precursor, an active component precursor and graphene to be mutually and uniformly fused, and carrying out solvent-free microwave reaction to synthesize the high-nitrogen-content doped molybdenum disulfide/C/graphene composite material. The composite material avoids the loss caused by sublimation of the nitrogen-doped precursor in the heating process in the traditional nitrogen doping process, improves the nitrogen doping efficiency, and realizes the uniform fusion of the interaction of the nitrogen-doped precursor, the active component precursor and the graphene under mild to strong reaction conditions. The prepared nitrogen-doped molybdenum disulfide/C/graphene composite material has good stability, is not easy to denature in air, is easy to store, has a large specific surface area, is used as a lithium ion battery cathode material, provides a good channel for lithium ion transmission, and shows a large specific capacity and a good cycling stability performance.

Description

Nitrogen-doped molybdenum disulfide/C/graphene composite material
Technical Field
The invention relates to a nitrogen-doped molybdenum disulfide/C/graphene composite material, in particular to a high-nitrogen-content doped molybdenum disulfide/C/graphene lithium battery cathode material, and provides a preparation method thereof, belonging to the technical field of nano composite materials and application thereof.
Background
Graphene is a carbonaceous material having a two-dimensional honeycomb lattice structure formed by close packing of single-layer carbon atoms, and has received great attention in experimental science and theoretical science since the discovery of Andre K heim (Andre K. Geim) and the like at manchester university in 2004 england. Graphene, which is only one carbon atom thick, is the thinnest of known materials, but is very strong and hard, stronger than diamond, and 100 times stronger than the hardest steel in the world. Due to the special nano structure and excellent performance, the catalyst has the advantages of catalysis, lithium storage, composite materials, electrochemistry and the likeHas potential application prospect. However, since graphene has no band gap, its conductivity cannot be completely controlled like a semiconductor, and the surface of graphene is smooth and inert, which is not favorable for combination with other functional materials, and limits further applications of graphene. The nitrogen-doped graphene is prepared by carrying out nitrogen-doping modification on graphene, so that the defects of the graphene can be overcome, the energy band gap is opened, the conductivity type is adjusted, the electronic structure is changed, the free carrier density of the graphene is improved, and the conductivity and stability of the graphene are improved. The nitrogen-doped graphene has a key effect on promoting and expanding the application field of graphene, and at present, nitrogen-doped graphene materials with various advantages are combined with amorphous carbon-modified MoS with good stability and high specific capacity by few simple and practical methods2The material is compounded and applied to the lithium ion battery cathode material.
CN102887502B provides a chemical vapor deposition method for preparing nitrogen-doped graphene material, which firstly provides a clean and dry substrate; coating a solution containing a catalyst on the surface of the substrate, heating the substrate to 500-1300 ℃ under an oxygen-free condition, introducing a reducing gas and the reducing catalyst, and then introducing a gaseous organic carbon source compound and a gaseous nitrogen source compound for reaction to finally obtain the nitrogen-doped graphene. CN104393254B provides a solid-phase reaction method for preparing a nitrogen-doped molybdenum disulfide/graphene composite material, which comprises the steps of firstly mixing a graphene oxide solution, a nitrogen-containing precursor, a sulfur-containing precursor and a molybdenum-containing precursor in a solvent, then evaporating to obtain a precursor material, then removing the solvent and heteroatoms to obtain the precursor material, and then calcining at the temperature of 500-700 ℃ in an inert atmosphere to obtain the nitrogen-doped molybdenum disulfide/graphene composite material. However, these methods generally have the problems of multiple steps, long time (more than one week is needed in the whole composite material preparation process of CN 104393254B), difficulty in controlling the nitrogen doping content, and low nitrogen doping efficiency due to the large loss of the nitrogen doping precursor caused by the intensive sublimation of the nitrogen doping precursor during the heating process in the solid phase reaction. The preparation of high nitrogen content doped graphene and molybdenum disulfide/C/graphene composite materials is difficult, so that the wide application of the materials is limited.
Disclosure of Invention
The invention provides a method for efficiently, quickly and massively synthesizing a high-nitrogen-content doped molybdenum disulfide/C/graphene composite material, which has the advantages of high nitrogen content of the obtained material, obviously improved raw material utilization rate, no need of washing, separating, drying and other processes of the product, direct application to a lithium battery cathode material and good application performance.
In order to achieve the technical purpose, the invention provides a preparation method of a nitrogen-doped molybdenum disulfide/C/graphene composite material, which comprises the following steps:
(1) dispersing graphene oxide in a formaldehyde aqueous solution to obtain a dispersion liquid A;
(2) mixing molybdenum salt and ammonia water, heating to 40-70 ℃, adding ammonium sulfide, reacting for 0.5-2h, sequentially adding quaternary ammonium salt and melamine into reaction liquid, and enabling the reaction liquid to become turbid to form melamine/alkylated thiomolybdate suspension, namely dispersion liquid B;
(3) mixing the dispersion liquid A and the dispersion liquid B, heating to 50-80 ℃ for reaction for 10-60min, adjusting the pH of the reaction liquid to 7-9, heating in a sealed environment to 100-200 ℃ for hydrothermal reaction for 12-24 h, filtering, and drying to obtain black solid powder;
(4) and (4) placing the black solid powder obtained in the step (3) in a microwave reaction cavity, and heating for 1-60min at the microwave power of 300-1200W to obtain the nitrogen-doped molybdenum disulfide/C/graphene composite material.
In the above-mentioned production method, the concentration of the aqueous formaldehyde solution in the step (1) is not particularly limited, and in a preferred embodiment of the present invention, the concentration of formaldehyde is 37% to 40% by mass. And mixing the graphene oxide with the formaldehyde aqueous solution according to the solid-to-liquid ratio of 1g (10-100) mL. Preferably, the mixture is uniformly mixed and dispersed in an ultrasonic mode, and the ultrasonic time is 5-30 min.
In the preparation method, the molybdenum salt is ammonium paramolybdate and/or sodium molybdate.
In the above preparation method, the quaternary ammonium salt is an ammonium halide having 4 to 30 carbons, preferably an ammonium halide having 4 to 25 carbons, and more specifically, the quaternary ammonium salt is at least one selected from the group consisting of tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium chloride and octadecyltrimethylammonium bromide.
In the preparation method, the mixing mass ratio of the molybdenum salt, the ammonium sulfide, the quaternary ammonium salt and the melamine in the step (2) is 1:1-20:0.1-5: 0.5-5.
In the above production method, the dispersion liquid a and the dispersion liquid B are mixed in the step (3), and the dispersion liquid a is preferably poured into the dispersion liquid B. And mixing the dispersion liquid A and the dispersion liquid B according to the weight ratio of the graphene oxide in the dispersion liquid A to the melamine in the dispersion liquid B of 1: 5-10. After mixing, the mixture is preferably mixed and dispersed uniformly in an ultrasonic mode, and the ultrasonic time is 5-30 min.
In the above preparation method, the pH of the reaction solution in the step (3) may be adjusted by using an organic base or an inorganic base, and more specific embodiments are selected from one or more of triethanolamine, methylamine, ethylamine, ethylenediamine, propylamine, isopropylamine, aniline, cyclohexylamine, o-aminophenol, 2-chlorophenol, potassium carbonate, sodium bicarbonate, potassium hydroxide, and sodium hydroxide.
In the preparation method, the hydrothermal reaction temperature in the step (3) is preferably 120-160 ℃, and the time is preferably 12-18 h.
In the preparation method, the power of the microwave reaction in the step (4) is preferably 600-1000W, and the time is preferably 10-30 min.
In the preparation method, the microwave reaction cavity is purged by nitrogen or inert gas before and during the microwave reaction, and preferably, argon is used for purging.
In the above production method, the oxidationThe graphene is in particular selected from graphene oxides having the following properties: the area of the sheet layer is 100 mu m2The conductivity is 3500S/m or more.
In the above preparation method, the graphene oxide is obtained by oxidizing graphite, and the graphene oxide of the present invention is synthesized by Hummers method, and as a more specific embodiment, the present invention discloses a specific preparation method of the graphene oxide as follows: adding natural crystalline flake graphite into ice-bath concentrated sulfuric acid under stirring, cooling to 0-10 ℃, adding sodium nitrate and potassium permanganate, stirring for reaction, adding deionized water, heating to 50-100 ℃, reacting at constant temperature until the reaction solution turns to bright yellow, adding hydrogen peroxide, stirring for reaction, cooling, washing and drying to obtain graphene oxide.
The specification of the natural crystalline flake graphite is 100-500 meshes. After the reaction is finished, repeatedly settling with deionized water during post-treatment to remove unreacted graphite particles, centrifuging with hydrochloric acid, cleaning, removing Cl ions in the reaction solution, washing with deionized water until the pH value is close to neutral, drying, and grinding.
The stripping efficiency of the Hummers method is more than 93%, the yield is more than 90%, the structural integrity of the obtained graphene oxide sheet layer is high, and the crystal lattice is complete after thermal reduction.
The technical purpose of the second aspect of the invention is to provide the nitrogen-doped molybdenum disulfide/C/graphene composite material prepared by the method. In the preparation process of the method, formaldehyde and melamine are mixed firstly to generate moderate crosslinking reaction to form a water-soluble nitrogen-doped precursor, and then hydrothermal reaction is carried out to carry out graphene nitrogen doping, so that the nitrogen-doped precursor and graphene components are easy to interact, conditions are created for uniformly fusing composite materials, and the nitrogen-doped process and MoS are more favorably realized2Compounding with graphene; the subsequent microwave reaction has high heating speed and uniform heating, the graphene oxide is rapidly thermally reduced into the graphene, and the nitrogen-doped precursor and the active component single-source precursor are thermally decomposed simultaneouslyThe molybdenum disulfide/C/graphene composite material.
The technical purpose of the third aspect of the invention is to provide an application of the nitrogen-doped molybdenum disulfide/C/graphene composite material, and the material can be used as a lithium ion battery cathode material and shows good cycle stability and rate capability.
Compared with the prior art, the invention has the following advantages:
(1) according to the invention, formaldehyde is used as a bridge in the preparation process of the nitrogen-doped molybdenum disulfide/C/graphene composite material, so that the formaldehyde and melamine are appropriately crosslinked to form the nitrogen-doped precursor, and the problem of low nitrogen doping efficiency caused by large loss of the nitrogen-doped precursor due to strong sublimation of the nitrogen-doped precursor in the heating process in the traditional nitrogen fixation and fixation doping reaction is solved.
(2) In the preparation process, the formaldehyde and the melamine are subjected to a cross-linking reaction to form the water-soluble nitrogen-doped precursor, so that the nitrogen-doped precursor, the active component precursor and the graphene are interacted and fused uniformly in the subsequent hydrothermal reaction, and the preparation of the high-nitrogen-content doped material is realized.
(3) In the microwave reaction stage in the preparation process, the heating speed is high, the heating is uniform, on one hand, the loss caused by sublimation of the nitrogen-doped precursor due to slow temperature rise in the traditional reaction can be avoided, on the other hand, under the microwave condition, the graphene oxide is rapidly thermally reduced into the graphene, and due to the uniform fusion of the graphene, the nitrogen-doped precursor and the active component precursor in the hydrothermal reaction stage, the nitrogen doping of the graphene is more uniform, and the synthesis of the high-nitrogen-content doped graphene is more facilitated.
(4) Microwave reaction heating speed is high, and synthetic MoS2The combination of the nanosheets and the nitrogen-doped graphene is firm, the particles are not easy to accumulate, the time required by the synthetic material is greatly shortened, and the graphene and MoS are relieved2The problem of agglomeration under the condition of long-time heating is more favorable for synthesizing the high-performance nitrogen-doped molybdenum disulfide/C/graphene composite material.
(5) The microwave reaction in the preparation process adopts a solvent-free treatment mode, so that the post-treatment processes of washing, separating, drying and the like of the product are omitted, and the production process is simplified.
(6) The nitrogen-doped molybdenum disulfide/C/graphene composite material prepared by the method has good stability, is not easy to denature in air, is easy to store, has a large specific surface area, is used as a lithium ion battery cathode material, provides a good channel for lithium ion transmission, and shows a large specific capacity and a good cycling stability performance.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
Fig. 1 is an XRD pattern of graphene oxide prepared according to the present invention;
FIG. 2 is an SEM image of the nitrogen-doped molybdenum disulfide/C/graphene composite material prepared in example 8;
FIG. 3 is a graph of the current density of 100 mA-g for the nitrogen-doped molybdenum disulfide/C/graphene composite material in example 8-1Time charge and discharge cycle curve.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The graphene oxide used in the following examples was prepared by the following method:
100mL of 98% concentrated sulfuric acid was slowly added to a 500mL dry three-necked flask, and the three-necked flask was placed on a magnetic stirrer with ice-bath cooling. 2.0g of natural crystalline flake graphite (180 mesh) was added with rapid stirring, and when the temperature of the reaction solution was reduced to about 0 ℃, 4.0g of sodium nitrate was slowly added, and stirring was continued for 2 hours. Then slowly adding 10g of potassium permanganate in batches within 1h, continuously stirring for 2h, and controlling the reaction temperature below 10 ℃. The three-necked flask is transferred into a water bath at 40 ℃, and the reaction is continuously stirred for 2 hours. Subsequently, 200mL of warm deionized water was added slowly and the reaction solution was kept at a temperature within 100 ℃. The reaction was carried out at a constant temperature of 98 ℃ until the reaction solution became bright yellow. 20mL of 30% hydrogen peroxide was added to the reaction solution, and the mixture was stirred continuously to allow the mixture to react sufficiently. Cooling, replacing deionized water for repeatedly settling the obtained solution, removing unreacted graphite particles, and centrifuging with hydrochloric acidAnd (4) cleaning, removing Cl ions in the reaction solution, and then washing with deionized water until the pH value is close to neutral. And finally, vacuum drying for 12h at 80 ℃ to obtain graphene oxide, and grinding the graphene oxide into powder for later use. Its XRD pattern is shown in FIG. 1 and is located at 11oTo the left and right is the typical 001 diffraction peak of graphene oxide, which is mainly due to the intercalation of a large number of oxygen-containing functional groups between graphene sheets. The distance between graphite oxide sheets can be calculated to be 0.7 nm through the Sherle formula, and is obviously larger than the interlayer spacing 0.3254 nm of graphite. The increased interlayer spacing is primarily due to oxygen-containing functional groups intercalated between graphene sheets.
In examples 1 to 8, the nitrogen-doped molybdenum disulfide/C/graphene composite material of the present invention was prepared:
example 1
(1) 1.0g of graphene oxide was weighed and dispersed in 20mL of 37% aqueous formaldehyde solution, and the dispersion was uniformly dispersed in an ultrasonic instrument and recorded as dispersion A.
(2) 0.5g of ammonium paramolybdate and 20mL of concentrated ammonia (NH) were taken3·H2O), heating, adding 3.0g ammonium sulfide ((NH) when the temperature is raised to 60 DEG C4)2S), reacting for 0.5h under the magnetic stirring state, then respectively adding 0.1g of tetramethylammonium bromide and 0.6g of melamine into the solution, and uniformly mixing by ultrasonic waves to obtain a dispersion liquid B.
(3) Mixing the dispersion A and the dispersion B, heating in water bath to 60 ℃, and stirring for 10 min. And adding triethanolamine into the reaction solution, adjusting the pH value of a reaction solution system to 8.0, ultrasonically mixing uniformly, pouring the reaction solution into a high-pressure reaction kettle, and heating to 120 ℃ for reaction for 12 hours. And (4) carrying out suction filtration and vacuum drying to obtain black solid powder.
(4) And (4) placing the black solid powder obtained in the step (3) in a microwave reaction chamber, and purging for 1h by 100mL/min argon. Heating for 10min at 600W of microwave power to obtain the nitrogen-doped molybdenum disulfide/C/graphene composite material.
Example 2
(1) 1.0g of graphene oxide was weighed and dispersed in 20mL of 37% aqueous formaldehyde solution, and the dispersion was uniformly dispersed in an ultrasonic instrument and recorded as dispersion A.
(2) 0.5g of ammonium paramolybdate and 20mL of concentrated ammonia (NH) were taken3·H2O), heating, adding 9.0g ammonium sulfide ((NH) when the temperature is raised to 60 DEG C4)2S), reacting for 1h under the condition of magnetic stirring, then respectively adding 2.0g of tetramethylammonium bromide and 2.0g of melamine into the solution, and uniformly mixing by ultrasonic waves to obtain a dispersion liquid B.
(3) Mixing the dispersion A and the dispersion B, heating in water bath to 60 ℃, and stirring for 10 min. And adding triethanolamine into the reaction solution, adjusting the pH value of a reaction solution system to 8.0, ultrasonically mixing uniformly, pouring the reaction solution into a high-pressure reaction kettle, and heating to 120 ℃ for reaction for 12 hours. And (4) carrying out suction filtration and vacuum drying to obtain black solid powder.
(4) And (4) placing the black solid powder obtained in the step (3) in a microwave reaction chamber, and purging for 1h by 100mL/min argon. Heating for 10min at 600W of microwave power to obtain the nitrogen-doped molybdenum disulfide/C/graphene composite material.
Example 3
(1) 1.0g of graphene oxide was weighed and dispersed in 30mL of 37% aqueous formaldehyde solution, and the dispersion was uniformly dispersed in an ultrasonic instrument and recorded as dispersion A.
(2) 0.9g of ammonium paramolybdate and 20mL of concentrated ammonia (NH) were taken3·H2O), heating, adding 10.0g ammonium sulfide ((NH) when the temperature is raised to 60 DEG C4)2S), reacting for 1h under the magnetic stirring state, then respectively adding 2.5g of tetraethylammonium bromide and 2.0g of melamine into the solution, and uniformly mixing by ultrasonic waves to obtain a dispersion liquid B.
(3) Mixing the dispersion A and the dispersion B, heating in water bath to 70 ℃, and stirring for 10 min. And adding triethanolamine into the reaction solution, adjusting the pH value of a reaction solution system to 8.0, ultrasonically mixing uniformly, pouring the reaction solution into a high-pressure reaction kettle, and heating to 120 ℃ for reaction for 12 hours. And (4) carrying out suction filtration and vacuum drying to obtain black solid powder.
(4) And (4) placing the black solid powder obtained in the step (3) in a microwave reaction chamber, and purging for 1h by 100mL/min argon. And heating for 20min at 600W of microwave power to obtain the nitrogen-doped molybdenum disulfide/C/graphene composite material.
Example 4
(1) 1.0g of graphene oxide was weighed and dispersed in 30mL of 37% aqueous formaldehyde solution, and the dispersion was uniformly dispersed in an ultrasonic instrument and recorded as dispersion A.
(2) 1.0g of ammonium paramolybdate and 20mL of concentrated ammonia (NH)3·H2O), heating, adding 12.0g ammonium sulfide ((NH) when the temperature is raised to 60 DEG C4)2S), reacting for 2 hours under the magnetic stirring state, then respectively adding 1.5g of tetraethylammonium chloride and 2.5g of melamine into the solution, and uniformly mixing by ultrasonic waves to obtain a dispersion liquid B.
(3) Mixing the dispersion A and the dispersion B, heating in water bath to 70 ℃, and stirring for 20 min. And adding triethanolamine into the reaction solution, adjusting the pH value of a reaction solution system to 9.0, ultrasonically mixing uniformly, pouring the reaction solution into a high-pressure reaction kettle, and heating to 120 ℃ for reaction for 12 hours. And (4) carrying out suction filtration and vacuum drying to obtain black solid powder.
(4) And (4) placing the black solid powder obtained in the step (3) in a microwave reaction chamber, and purging for 1h by 100mL/min argon. Heating for 30min at 600W of microwave power to obtain the nitrogen-doped molybdenum disulfide/C/graphene composite material.
Example 5
(1) 1.0g of graphene oxide was weighed and dispersed in 20mL of 37% aqueous formaldehyde solution, and the dispersion was uniformly dispersed in an ultrasonic instrument and recorded as dispersion A.
(2) 1.5g of ammonium paramolybdate and 30mL of concentrated ammonia (NH)3·H2O), heating, adding 12.0g ammonium sulfide ((NH) when the temperature is raised to 60 DEG C4)2S), reacting for 2 hours under the magnetic stirring state, then respectively adding 1.5g of tetrabutylammonium bromide and 2.0g of melamine into the solution, and uniformly mixing by ultrasonic waves to obtain a dispersion liquid B.
(3) Mixing the dispersion A and the dispersion B, heating in water bath to 70 ℃, and stirring for 20 min. And then adding potassium hydroxide into the reaction liquid, adjusting the pH value of a reaction liquid system to 9.0, carrying out ultrasonic mixing uniformly, then pouring the reaction liquid into a high-pressure reaction kettle, and heating to 120 ℃ for reaction for 12 hours. And (4) carrying out suction filtration and vacuum drying to obtain black solid powder.
(4) And (4) placing the black solid powder obtained in the step (3) in a microwave reaction chamber, and purging for 1h by 100mL/min argon. Heating for 10min at the microwave power of 800W to obtain the nitrogen-doped molybdenum disulfide/C/graphene composite material.
Example 6
(1) 1.0g of graphene oxide was weighed and dispersed in 00mL of 37% aqueous formaldehyde solution, and the obtained dispersion was placed in an ultrasonic instrument and uniformly dispersed, and the obtained dispersion was recorded as dispersion A.
(2) 1.5g of ammonium paramolybdate and 30mL of concentrated ammonia (NH)3·H2O), heating, adding 12.0g ammonium sulfide ((NH) when the temperature is raised to 60 DEG C4)2S), reacting for 1h under the magnetic stirring state, then respectively adding 1.5g of hexadecyl trimethyl ammonium bromide and 2.5g of melamine into the solution, and uniformly mixing by ultrasonic waves to obtain a dispersion liquid B.
(3) Mixing the dispersion A and the dispersion B, heating in water bath to 80 ℃, and stirring for 30 min. And then adding potassium hydroxide into the reaction liquid, adjusting the pH value of a reaction liquid system to 9.0, carrying out ultrasonic mixing uniformly, then pouring the reaction liquid into a high-pressure reaction kettle, and heating to 140 ℃ for reaction for 15 hours. And (4) carrying out suction filtration and vacuum drying to obtain black solid powder.
(4) And (4) placing the black solid powder obtained in the step (3) in a microwave reaction chamber, and purging for 1h by 100mL/min argon. Heating for 10min at the microwave power of 800W to obtain the nitrogen-doped molybdenum disulfide/C/graphene composite material.
Example 7
(1) 1.0g of graphene oxide was weighed and dispersed in 20mL of 37% aqueous formaldehyde solution, and the dispersion was uniformly dispersed in an ultrasonic instrument and recorded as dispersion A.
(2) 0.5g of ammonium paramolybdate and 20mL of concentrated ammonia (NH) were taken3·H2O), heating, adding 10.0g ammonium sulfide ((NH) when the temperature is raised to 60 DEG C4)2S), reacting for 1 hour under the magnetic stirring state, then respectively adding 1.5g of hexadecyl trimethyl ammonium chloride and 2.5g of melamine into the solution, and uniformly mixing by ultrasonic waves to obtain a dispersion liquid B.
(3) Mixing the dispersion A and the dispersion B, heating in water bath to 80 ℃, and stirring for 30 min. And adding triethanolamine into the reaction solution, adjusting the pH value of a reaction solution system to 9.0, ultrasonically mixing uniformly, pouring the reaction solution into a high-pressure reaction kettle, and heating to 160 ℃ for reaction for 15 hours. And (4) carrying out suction filtration and vacuum drying to obtain black solid powder.
(4) And (4) placing the black solid powder obtained in the step (3) in a microwave reaction chamber, and purging for 1h by 100mL/min argon. Heating for 10min at the microwave power of 800W to obtain the nitrogen-doped molybdenum disulfide/C/graphene composite material.
Example 8
(1) 1.0g of graphene oxide was weighed and dispersed in 20mL of 37% aqueous formaldehyde solution, and the dispersion was uniformly dispersed in an ultrasonic instrument and recorded as dispersion A.
(2) 1.8g of ammonium paramolybdate and 20mL of concentrated ammonia (NH)3·H2O), heating, adding 18.0g ammonium sulfide ((NH) when the temperature is raised to 60 DEG C4)2S), reacting for 1h under the condition of magnetic stirring, then respectively adding 3.5g of tetramethylammonium bromide and 3.0g of melamine into the solution, and uniformly mixing by ultrasonic waves to obtain a dispersion liquid B.
(3) Mixing the dispersion A and the dispersion B, heating in water bath to 80 ℃, and stirring for 30 min. And adding triethanolamine into the reaction solution, adjusting the pH value of a reaction solution system to 9.0, ultrasonically mixing uniformly, pouring the reaction solution into a high-pressure reaction kettle, and heating to 160 ℃ for reacting for 18 hours. And (4) carrying out suction filtration and vacuum drying to obtain black solid powder.
(4) And (4) placing the black solid powder obtained in the step (3) in a microwave reaction chamber, and purging for 1h by 100mL/min argon. And heating for 30min at the microwave power of 1000W to obtain the nitrogen-doped molybdenum disulfide/C/graphene composite material.
An SEM image of the nitrogen-doped molybdenum disulfide/C/graphene composite material obtained in example 8 is shown in fig. 2, and MoS of a two-dimensional structure can be seen2The graphene is grown on the surface of graphene in a sheet shape, and shows a compact two-dimensional structure, which is beneficial to good conductivity of nitrogen-doped graphene and MoS2Active ingredient combinationThereby exerting more excellent electrochemical performance.
Comparative example 1
In the step (1), formaldehyde solution is not used, and deionized water is used:
(1) 1.0g of graphene oxide is weighed and dispersed in 20mL of deionized water, and the obtained product is placed in an ultrasonic instrument and is uniformly dispersed, and the obtained product is marked as a dispersion liquid A.
(2) 1.8g of ammonium paramolybdate and 20mL of concentrated ammonia (NH)3·H2O), heating, adding 18.0g ammonium sulfide ((NH) when the temperature is raised to 60 DEG C4)2S), reacting for 1h under the condition of magnetic stirring, then respectively adding 3.5g of tetramethylammonium bromide and 3.0g of melamine into the solution, and uniformly mixing by ultrasonic waves to obtain a dispersion liquid B.
(3) Mixing the dispersion A and the dispersion B, heating in water bath to 80 ℃, and stirring for 30 min. And adding triethanolamine into the reaction solution, adjusting the pH value of a reaction solution system to 9.0, ultrasonically mixing uniformly, pouring the reaction solution into a high-pressure reaction kettle, and heating to 160 ℃ for reacting for 18 hours. And (4) carrying out suction filtration and vacuum drying to obtain black solid powder.
(4) And (4) placing the black solid powder obtained in the step (3) in a microwave reaction chamber, and purging for 1h by 100mL/min argon. Heating the mixture for 30min at the microwave power of 1000W to obtain a comparative composite material.
Comparative example 2
Molybdenum salt, sulfur source and quaternary ammonium salt are not added in the step (2):
(1) 1.0g of graphene oxide was weighed and dispersed in 20mL of 37% aqueous formaldehyde solution, and the dispersion was uniformly dispersed in an ultrasonic instrument and recorded as dispersion A.
(2) 3.0g of melamine is weighed and added into 20mL of deionized water, and the mixture is placed in an ultrasonic instrument to be uniformly dispersed by ultrasonic, and the dispersion liquid B is marked.
(3) Mixing the dispersion A and the dispersion B, heating in water bath to 80 ℃, and stirring for 30 min. And adding triethanolamine into the reaction solution, adjusting the pH value of a reaction solution system to 9.0, ultrasonically mixing uniformly, pouring the reaction solution into a high-pressure reaction kettle, and heating to 160 ℃ for reacting for 18 hours. And (4) carrying out suction filtration and vacuum drying to obtain black solid powder.
(4) And (4) placing the black solid powder obtained in the step (3) in a microwave reaction chamber, and purging for 1h by 100mL/min argon. Heating for 30min with 1000W of microwave power to obtain the composite material.
Comparative example 3
And (3) adjusting the pH value of the reaction solution without adding alkali liquor, uniformly mixing the dispersion solution A and the dispersion solution B, and then directly carrying out hydrothermal reaction:
(1) 1.0g of graphene oxide was weighed and dispersed in 20mL of 37% aqueous formaldehyde solution, and the dispersion was uniformly dispersed in an ultrasonic instrument and recorded as dispersion A.
(2) 1.8g of ammonium paramolybdate and 20mL of concentrated ammonia (NH)3·H2O), heating, adding 18.0g ammonium sulfide ((NH) when the temperature is raised to 60 DEG C4)2S), reacting for 1h under the condition of magnetic stirring, then respectively adding 3.5g of tetramethylammonium bromide and 3.0g of melamine into the solution, and uniformly mixing by ultrasonic waves to obtain a dispersion liquid B.
(3) And mixing the dispersion liquid A and the dispersion liquid B, uniformly mixing by ultrasonic waves, pouring the reaction liquid into a high-pressure reaction kettle, and heating to 160 ℃ for reacting for 18 hours. And (4) carrying out suction filtration and vacuum drying to obtain black solid powder.
(4) And (4) placing the black solid powder obtained in the step (3) in a microwave reaction chamber, and purging for 1h by 100mL/min argon. Heating for 30min with 1000W of microwave power to obtain the composite material.
The materials of examples 1-8 and comparative examples 1-3 are used as the negative electrode material of the lithium ion battery. Taking the synthesized nitrogen-doped graphene as an active component, selecting a 2016 type battery shell, a metal lithium sheet (phi 16 mm multiplied by 1mm), and 1.0M LiPF6The mixed solution of Ethylene Carbonate (EC) and diethyl carbonate (DEC) (volume ratio of 1:1) is used as electrolyte, and Celgard2300 microporous polypropylene coal membrane is used as battery diaphragm. The materials are assembled into a button cell in a glove box filled with Ar gas, and the test is carried out after the working electrode is fully soaked by the electrolyte. The method comprises the following five steps:
(1) size mixing
The material has large specific surface area and can easily adsorb water in air, so that it can be used in air conditionerFirstly, the material for preparing the electrode is fully dried in a vacuum drying oven at 120 ℃ to remove the surface moisture. Then adding an active substance, a conductive additive (acetylene black) and a binder (PVDF) into the dispersant according to the mass percentage of 80:10:10N-methylpyrrolidone (NMP) mixed grinding, resulting in uniform mixing of the materials, making a viscous slurry.
(2) Coating film
The resulting viscous paste was uniformly coated on a copper foil (thickness of about 100 μm). The specific operation is as follows: 1) the copper foil of moderate size is cut and laid flat on a table top. 2) Removing stains on the surface of the copper foil. 3) The slurry was dispersed on a copper foil and uniformly spread on the copper foil using a die. 4) The copper foil coated with the slurry was dried in a vacuum drying oven at 120 ℃ for 12 hours.
(3) Roller compaction
After the completion of drying, the copper foil coated with the slurry was rolled with a small-sized rolling machine to prevent the electrode material from falling off from the surface of the copper foil.
(4) Tabletting
And cutting the rolled film into a plurality of circular electrode slices with the diameter of 12mm by using a manual slicer. In order to prevent the coating film from falling off during charge and discharge cycles, it was pressed into a sheet by an oil press. And taking out and weighing after drying, and waiting for battery loading.
(5) Assembled battery
The process of assembling the button cells was carried out in a glove box filled with Ar gas. The battery is assembled according to the sequence of negative battery shell/electrolyte/working electrode plate/electrolyte/diaphragm/lithium plate/positive battery shell. And standing for 24 hours, and carrying out electrochemical test after the electrolyte is fully soaked.
And carrying out charge and discharge tests on the assembled button type simulation battery. The material of example 8 was used at a voltage in the range of 0.01 to 3.0V and at a current of 100mA g-1The results of the cycle stability test at the current density of (a) are shown in fig. 3. The first charge and discharge capacities and the discharge capacities after 100 charge and discharge tests of examples 1 to 8 and comparative examples 1 to 3 are shown in table 1. Wherein the content of nitrogen element is determined by element analysis.
It can be seen from the test data that the present invention significantly improves the buckleThe first discharge specific capacity of the battery can reach 1377.4mAh g-1Compared with comparative example 1, the yield is improved by 12.2%, compared with comparative example 2, the yield is improved by 245.6%, and compared with comparative example 3, the yield is improved by 11.4%. And the high reversible capacity is still kept after the circulation for 100 times, the reversible capacity retention rate is close to 90.0 percent and reaches 91.4 percent at most, which shows that the invention has high reversible capacity and good circulation performance.
TABLE 1
Figure DEST_PATH_IMAGE001

Claims (16)

1. A preparation method of a nitrogen-doped molybdenum disulfide/C/graphene composite material comprises the following steps:
(1) dispersing graphene oxide in a formaldehyde solution to obtain a dispersion liquid A;
(2) mixing molybdenum salt and ammonia water, heating to 40-70 ℃, adding ammonium sulfide, reacting for 0.5-2h, sequentially adding quaternary ammonium salt and melamine into reaction liquid, and enabling the reaction liquid to become turbid to form melamine/alkylated thiomolybdate suspension, namely dispersion liquid B;
(3) mixing the dispersion liquid A and the dispersion liquid B, heating to 50-80 ℃ for reaction for 10-60min, adjusting the pH of the reaction liquid to 7-9, heating in a sealed environment to 100-200 ℃ for hydrothermal reaction for 12-24 h, filtering, and drying to obtain black solid powder;
(4) and (4) placing the black solid powder obtained in the step (3) in a microwave reaction cavity, and heating for 1-60min at the microwave power of 300-1200W to obtain the nitrogen-doped molybdenum disulfide/C/graphene composite material.
2. The preparation method according to claim 1, wherein in the step (1), the graphene oxide and the formaldehyde solution are mixed according to a solid-to-liquid ratio of 1g to 10-100 mL.
3. The method of claim 1, wherein the molybdenum salt is ammonium paramolybdate and/or sodium molybdate.
4. The method according to claim 1, wherein the quaternary ammonium salt is at least one selected from the group consisting of tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, octadecyltrimethylammonium chloride and octadecyltrimethylammonium bromide.
5. The production method according to claim 1, wherein the mixing mass ratio of the molybdenum salt, the ammonium sulfide, the quaternary ammonium salt and the melamine in the step (2) is 1:1-20:0.1-5: 0.5-5.
6. The method according to claim 1, wherein the dispersion A and the dispersion B are mixed in the step (3) by pouring the dispersion A into the dispersion B.
7. The method according to claim 1, wherein the dispersion liquid A and the dispersion liquid B are mixed in a ratio of 1:5 to 10 by weight of graphene oxide in the dispersion liquid A to melamine in the dispersion liquid B.
8. The method according to claim 1, wherein an organic base or an inorganic base is used for adjusting the pH of the reaction solution in the step (3).
9. The method according to claim 8, wherein the organic or inorganic base is selected from one or more of triethanolamine, methylamine, ethylamine, ethylenediamine, propylamine, isopropylamine, aniline, cyclohexylamine, o-aminophenol, 2-chlorophenol, potassium carbonate, sodium bicarbonate, potassium hydroxide, and sodium hydroxide.
10. The preparation method according to claim 1, wherein the hydrothermal reaction in the step (3) is carried out at a temperature of 120 to 160 ℃ for 12 to 18 hours.
11. The preparation method according to claim 1, wherein the microwave reaction in the step (4) has a power of 600-1000W and a time of 10-30 min.
12. The method according to claim 1, wherein the graphene oxide is selected from graphene oxides having the following properties: the area of the sheet layer is 100 mu m2The conductivity is 3500S/m or more.
13. The preparation method according to claim 12, wherein the graphene oxide is obtained by oxidizing graphite.
14. The preparation method according to claim 13, wherein the graphene oxide is synthesized by a Hummers method, and the preparation method comprises the following steps: adding natural crystalline flake graphite into ice-bath concentrated sulfuric acid under stirring, cooling to 0-10 ℃, adding sodium nitrate and potassium permanganate, stirring for reaction, adding deionized water, heating to 50-100 ℃, reacting at constant temperature until the reaction solution turns to bright yellow, adding hydrogen peroxide, stirring for reaction, cooling, washing and drying to obtain graphene oxide.
15. The nitrogen-doped molybdenum disulfide/C/graphene composite material prepared by the method of any one of claims 1 to 14.
16. The use of the nitrogen-doped molybdenum disulfide/C/graphene composite material of claim 15 as a negative electrode material for a lithium ion battery.
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