CN112786865A - MoS2Preparation method and application of quasi-quantum dot/nitrogen-sulfur co-doped biomass carbon composite nano material - Google Patents

MoS2Preparation method and application of quasi-quantum dot/nitrogen-sulfur co-doped biomass carbon composite nano material Download PDF

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CN112786865A
CN112786865A CN202110128044.2A CN202110128044A CN112786865A CN 112786865 A CN112786865 A CN 112786865A CN 202110128044 A CN202110128044 A CN 202110128044A CN 112786865 A CN112786865 A CN 112786865A
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nitrogen
doped
nano material
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sulfur
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杜祝祝
艾伟
黄维
杜洪方
王天
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Ningbo Research Institute of Northwestern Polytechnical University
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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
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
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    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
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    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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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    • H01M4/36—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
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    • H—ELECTRICITY
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    • H01M4/00—Electrodes
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a MoS2The quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon nano material and the preparation method and application thereof are characterized in that nitrogen-doped biomass carbon obtained by carbonizing lobster shells is used as a substrate material; subsequent in situ synthesis of MoS by solid phase method2Quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material; the morphology analysis of the obtained product shows that MoS2Quasi-quantum dot densificationIs wrapped on the surface of a three-dimensional nitrogen and sulfur co-doped biomass carbon substrate material, thereby effectively relieving sheet MoS2Structure collapse, electrode pulverization and MoS of nano structure in sodium ion extraction process2The invention has the advantages of simple preparation method, controllable reaction temperature, short period and simple process equipment, and is suitable for large-scale production. Meanwhile, the prepared carbon nano material is used for the cathode of the sodium ion battery, and the current density is 100mA g‑1After circulating for 100 circles under the condition of (1), the product still has 340mAh g‑1The capacity of (2) shows excellent electrochemical performance.

Description

MoS2Preparation method and application of quasi-quantum dot/nitrogen-sulfur co-doped biomass carbon composite nano material
Technical Field
The invention belongs to the technical field of preparation of electrode materials of sodium-ion batteries, and particularly relates to MoS2A preparation method and application of a quasi-quantum dot/nitrogen-sulfur co-doped biomass carbon composite nano material.
Background
Lithium ion batteries are used as energy storage systems and are increasingly widely applied in the fields of portable electronic equipment, electric automobiles and unmanned aerial vehicles. In addition, the new energy electric automobile industry develops rapidly, and the development of the lithium ion battery towards higher energy density and long service life is greatly promoted. However, lithium resources are scarce and are unevenly distributed, so that the price is increased rapidly, and the large-scale development of the lithium ion battery is severely limited.
Sodium belongs to the same main group as lithium and has similar chemical properties. Because of abundant sodium resources and low cost, the sodium ion battery is expected to replace a lithium ion battery in the field of energy storage. Meanwhile, the manufacturing of the sodium ion battery can also refer to the process flow of the lithium ion battery. Related research has shown that replacing commercial lithium ion batteries with sodium ion batteries will reduce costs by about 30%, which also makes sodium ion batteries have a greater advantage over lithium ion batteries. Cong, H.M.Xie, J.H.Li, et al.Hierarchical structures based on two-dimensional nanomaterials for rechargeable lithium batteries, 2017,7,1601906]. However, when a graphite negative electrode of a commercial lithium ion battery is selected as a negative electrode of a sodium ion battery, the capacity thereof is only 35mAh g-1. This is because the radius (r ═ 0.112 nm) of sodium ions is larger than that of lithium ions (r ═ 0.076nm), so that the intercalation/deintercalation process of sodium ions in the electrode material exhibits slow kinetics; at the same time, the insertion/extraction process easily causes the collapse of the crystal lattice structure of the host material, resulting inThe cycling performance of the electrode is poor. Therefore, finding a suitable sodium host material has certain difficulties. [ Y.Wen, K.He, Y.J.Zhu, et al, Expanded graphite as super anode for sodium-ion batteries. Nature Communications,2014,5, 4033.Z.Hu, L.X.Wang, K.Zhang, et al.MoS2 nanoflowers with expanded interlayers as high-performance anodes for sodium-ion batteries.Angewandte Chemie International Edition, 2014,53,12794]。MoS2As the transition metal sulfide, there is an S-Mo-S sandwich layered structure similar to graphite, in which S atoms and Mo atoms are bonded by covalent bonds and the layers are connected by weak van der waals force. It exhibits a high specific capacity (670mAh g) as an electrode material-1) And has wide research value. However, MoS2As a sodium ion battery electrode, it is difficult to maintain its structural stability during ion extraction/insertion, sheet structure collapse is likely to occur, ion conduction between S — Mo — S sheets is affected, and thus poor electrochemical performance is exhibited.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a MoS2A preparation method of a quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material (representing a composite material, the same below) aims at solving the problem of the conventional MoS2The problem of poor electrochemical performance and stability when used as the electrode material of the sodium ion battery; the preparation method has the advantages of simple operation, controllable reaction temperature, short reaction period and low requirement on equipment, and is suitable for large-scale production.
In order to solve the problems, the technical scheme adopted by the invention is as follows: provides a MoS2The preparation method of the quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material comprises the following steps:
(1) preparing a nitrogen-doped carbon nano material: carbonizing the cleaned biomass, mixing with acid, stirring, and drying to obtain nitrogen-doped carbon nanomaterial;
(2)MoO3preparation of nitrogen-doped carbon precursor: mixing the nitrogen-doped carbon nano material prepared in the step (1) with MoO3Mixing the liquid phases, and adding N-methyl pyrrole under stirringKeton, heat evaporating to dryness to obtain MoO3A nitrogen-doped carbon precursor;
(3)MoS2preparing a quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material: MoO prepared in the step (2)3Mixing the nitrogen-doped carbon precursor and thiourea, and then placing the mixture in a protective atmosphere for two-stage heating calcination to obtain MoS2Quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material.
Preferably, the biomass used in step (1) is lobster shells.
Preferably, the carbonization treatment comprises the following specific steps: putting the lobster shells into a tube furnace, and performing argon treatment at 5-10 ℃ for min-1The temperature rising rate is increased from room temperature to 550-750 ℃ for carbonization, and the carbonization furnace is cooled to room temperature after heat preservation for 1-3 h.
Preferably, the specific operation after the carbonization treatment is as follows: the biomass was treated with dilute hydrochloric acid under magnetic stirring until no bubbles were produced and the pH was adjusted to 7.0. Cleaning and filtering the product, and freeze-drying the product to obtain the nitrogen-doped carbon nano material; and the concentration of the dilute hydrochloric acid is 0.2-1.0mol L-1(ii) a In the step 1), the product after hydrochloric acid treatment is washed by deionized water and ethanol for several times, and then is freeze-dried for 8-12 h at the temperature of-10 to-50 ℃.
Preferably, in the step (2), the nitrogen-doped carbon nanomaterial and the MoO are mixed3The mass ratio of (1.0-5.0) to (0.4).
Preferably, in the step (3), the specific conditions of the two-stage temperature-rising calcination are as follows: and introducing inert gas, heating from room temperature to 110-150 ℃ under inert atmosphere, carrying out heat preservation reaction for 0.5-2 h, then continuously heating to 600-800 ℃, and carrying out heat preservation reaction for 0.5-2 h. And cooling to room temperature along with the furnace after the reaction is finished.
Preferably, in the step (3), the inert gas is stopped from being introduced when the temperature of the tubular furnace is increased from room temperature to 100 ℃, and the rate of temperature increase is 2 ℃ for min-1。
Preferably, the step (3) further comprises a treatment of washing and drying the reaction product after the two-stage temperature-raising calcination, and the specific treatment method is as follows: and washing the calcined product with deionized water and ethanol, and freeze-drying for 8-12 h.
The invention also discloses the MoS prepared by the preparation method2The quasi-quantum dot/nitrogen-sulfur co-doped biomass carbon composite nano material.
The invention also discloses the MoS adopting the above2The application of the quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material in the preparation of a sodium ion battery cathode material.
Compared with the prior art, the invention has the following beneficial technical effects:
according to the invention, firstly, nitrogen-doped biomass carbon obtained by carbonizing lobster shells is used as a substrate material. Subsequent in situ synthesis of MoS by solid phase method2Quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material. MoS can be seen through morphology analysis2The quasi-quantum dots are wrapped on the surface of the biomass carbon substrate with a three-dimensional structure, and the strategy can effectively relieve MoS2Structural collapse, electrode pulverization and MoS of nanosheet in sodium ion deintercalation process2The problem of quasi-quantum dot agglomeration, and finally prepared MoS with high sodium storage performance2Quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material. The preparation method is simple, the reaction temperature is controllable, the reaction period is short, the process equipment is simple, and the method is suitable for large-scale production.
MoS prepared by the invention2The quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material has uniform chemical composition, higher purity and uniform appearance, and the MoS prepared by the method2Quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite powder, wherein the morphology of the quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite powder is MoS with the dimension of about 10nm2The quasi-quantum dots are anchored on nitrogen and sulfur co-doped biomass carbon and can be used as a negative electrode material of a sodium ion secondary battery. MoS prepared by the invention2The quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material is used as a cathode of a sodium ion battery, and is compared with MoS2For the nano-sheet, the nano-sheet has smaller particle size and higher specific surface area, so that the material has better wettability with electrolyte, and the migration distance of sodium ions can also be changedShort. Meanwhile, the structure effectively improves the rapid storage of sodium ions on the surface of the electrode material, thereby improving the electrochemical performance of the material; MoS prepared by the method of the invention2The quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nanomaterial has excellent conductivity, cycling stability and high sodium storage specific capacity, and therefore can be widely used as a sodium ion battery cathode material.
Drawings
In FIG. 1, (a), (b), and (c) are MoS prepared according to example 3, respectively2SEM and TEM images of quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material;
FIG. 2 is a MoS prepared according to the present invention2An XRD (X-ray diffraction) pattern of the quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material; in FIG. 2, the curve with the larger ordinate is MoS2The curve of the quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon nanomaterial is the curve of the nitrogen-doped biomass carbon nanomaterial with the smaller ordinate;
FIG. 3 is a MoS prepared according to example 3 of the present invention2And the quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nanomaterial is used as a cycle performance and coulombic efficiency diagram of the negative electrode of the sodium-ion battery.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The electrochemical performance of the sample can be influenced to a certain extent due to the composition, morphology, size and the like of the material. The two-dimensional, three-dimensional and multi-dimensional mixed or porous structure is beneficial to the desorption of sodium ions, so that the capacity of the material is increased. The smaller the particle, the larger the specific surface area, the material and electrolyteThe better the contact, the migration distance of sodium ions will also shorten, more is favorable to the promotion of sodium ion battery material multiplying power performance. In addition, due to MoS2The lattice parameter is changed during the process of sodium ion deintercalation, so that MoS with high surface energy is obtained2Collapse, agglomeration and the like of the lamellar structure.
Therefore, the invention aims to prepare uniform and superfine molybdenum disulfide nano particles by a liquid-solid reinforcement method to be dotted on a three-dimensional structure functionalized carbon substrate, so that the problems of structure collapse prevention, lattice parameter change in the sodium ion extraction process and the like are effectively relieved.
The method comprises the following specific operation steps and embodiments:
example 1
MoS2The preparation method of the quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material comprises the following steps:
step 1: preparation of nitrogen-doped carbon nano material
1) Placing 20g of cleaned lobster shells in a tube furnace, and heating at 5 deg.C for min under the condition of argon gas-1The temperature rising rate is increased from room temperature to 550 ℃ for carbonization, and the carbonized product is cooled to room temperature along with the furnace after heat preservation for 1 h;
2) dispersing carbonized lobster shells in 100mL of deionized water, and stirring with magnetic force with a concentration of 0.2mol L-1Hydrochloric acid was treated until no bubbles were generated and adjusted to PH 7.0. Cleaning the filtered product, and freeze-drying to obtain the nitrogen-doped carbon nano material;
step 2: MoO3Preparation of nitrogen-doped carbon precursor
Doping nitrogen with carbon and MoO3Dispersing the mixture into deionized water according to the mass ratio of 0.4:1.0, dropwise adding 2mL of azomethylpyrrolidone into the mixed solution under the condition of magnetic stirring, and preparing MoO by adopting a mode of stirring and evaporating to dryness3A nitrogen-doped carbon precursor;
and step 3: MoS2Preparation of quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon nano material
1) Adding MoO3Nitrogen-doped carbon precursor and thiourea in a ratio of 0.5:2.0Mixing the raw materials according to the quantity ratio, grinding the mixture evenly and then placing the mixture in a tubular furnace;
2) ar gas is introduced at the beginning of the reaction at a flow rate of 100sccm to ensure that the reaction is carried out under inert conditions. At 2 ℃ for min-1The temperature rising rate is increased from room temperature to 100 ℃, the gas flow rate of argon is controlled to be 100sccm, the temperature is continuously increased to 110 ℃, and the heat preservation reaction is carried out for 0.5 h;
3) then continuing to control the temperature for 2 ℃ min-1The temperature is raised to 600 ℃ at the temperature raising rate, and the reaction is carried out for 0.5h under the condition of heat preservation. During this process, the argon supply was stopped to maintain a high concentration of H2S gas and MoO3Fully reacting with nitrogen-doped carbon;
4) cooling to room temperature along with the furnace after the reaction is finished, cleaning and drying the reaction product, and finally obtaining the MoS2Quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon nano material.
Example 2
MoS2The preparation method of the quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material comprises the following steps:
step 1: preparation of nitrogen-doped carbon nano material
1) Placing 25g of cleaned lobster shells in a tube furnace, and heating at 6 deg.C for min under the condition of argon gas-1The temperature rising rate is increased from room temperature to 600 ℃ for carbonization, and the carbonized product is cooled to room temperature along with the furnace after heat preservation for 1.5 h;
2) dispersing carbonized lobster shells in 120mL of deionized water, and stirring with magnetic force with a concentration of 0.4mol L-1Hydrochloric acid was treated until no bubbles were generated and adjusted to PH 7.0. Cleaning the filtered product, and freeze-drying to obtain the nitrogen-doped carbon nano material;
step 2: MoO3Preparation of nitrogen-doped carbon precursor
Doping nitrogen with carbon and MoO3Dispersing the mixture into deionized water according to the mass ratio of 0.4:2.0, dropwise adding 3mL of azomethylpyrrolidone into the mixed solution under the condition of magnetic stirring, and preparing MoO by adopting a mode of stirring and evaporating to dryness3A nitrogen-doped carbon precursor;
and step 3: MoS2Quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon nanoPreparation of rice material
1) Adding MoO3Mixing the nitrogen-doped carbon precursor and thiourea according to the mass ratio of 0.5:3.0, uniformly grinding, and placing in a tubular furnace;
2) ar is introduced at the beginning of the reaction at a gas flow rate of 100sccm to ensure that the reaction is carried out under inert conditions. At 2 ℃ for min-1The temperature rising rate is increased from room temperature to 100 ℃, the gas flow rate of argon is controlled to be 100sccm, the temperature is continuously increased to 120 ℃, and the heat preservation reaction is carried out for 0.8 h;
3) then continuing to control the temperature for 2 ℃ min-1The temperature is raised to 650 ℃ at the temperature raising rate, and the reaction is carried out for 0.8h under the condition of heat preservation. During this process, the argon supply was stopped to maintain a high concentration of H2S gas and MoO3Fully reacting with nitrogen-doped carbon;
4) cooling to room temperature along with the furnace after the reaction is finished, cleaning and drying the reaction product, and finally obtaining the MoS2Quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon nano material.
Example 3
MoS2The preparation method of the quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material comprises the following steps:
step 1: preparation of nitrogen-doped carbon nano material
1) 30g of cleaned lobster shells are placed in a tube furnace and are put at 7 ℃ for min under the condition of argon gas-1The temperature rising rate is increased from room temperature to 650 ℃ for carbonization, and the carbonized product is cooled to room temperature along with the furnace after heat preservation for 2.0 h;
2) dispersing carbonized lobster shells in 150mL of deionized water, and stirring with magnetic force with a concentration of 0.6mol L-1Hydrochloric acid was treated until no bubbles were generated and adjusted to PH 7.0. Cleaning the filtered product, and freeze-drying to obtain the nitrogen-doped carbon nano material;
step 2: MoO3Preparation of nitrogen-doped carbon precursor
Doping nitrogen with carbon and MoO3Dispersing the mixture into deionized water according to the mass ratio of 0.4:3.0, dropwise adding 4mL of azomethylpyrrolidone into the mixed solution under the condition of magnetic stirring, and preparing MoO by adopting a mode of stirring and evaporating to dryness3Nitrogen dopingA carbon precursor;
and step 3: MoS2Preparation of quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon nano material
1) Adding MoO3Mixing the nitrogen-doped carbon precursor and thiourea according to the mass ratio of 0.5:4.0, uniformly grinding, and placing in a tubular furnace;
2) ar gas is introduced at the beginning of the reaction at a flow rate of 100sccm to ensure that the reaction is carried out under inert conditions. At 2 ℃ for min-1The temperature rising rate is increased from room temperature to 100 ℃, the gas flow rate of argon is controlled to be 100sccm, the temperature is continuously increased to 130 ℃, and the heat preservation reaction is carried out for 1.0 h;
3) then continuing to control the temperature for 2 ℃ min-1The temperature is raised to 700 ℃ at the temperature raising rate, and the reaction is carried out for 1.0 hour under the condition of heat preservation. During this process, the argon supply was stopped to maintain a high concentration of H2S gas and MoO3Fully reacting with nitrogen-doped carbon;
4) cooling to room temperature along with the furnace after the reaction is finished, cleaning and drying the reaction product, and finally obtaining the MoS2Quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon nano material.
Example 4
MoS2The preparation method of the quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material comprises the following steps:
step 1: preparation of nitrogen-doped carbon nano material
1) Putting 35g of cleaned lobster shells into a tube furnace, and performing argon gas treatment at 8 ℃ for min-1The temperature rising rate is increased from room temperature to 700 ℃ for carbonization, and the carbonized product is cooled to room temperature along with the furnace after heat preservation for 2.5 hours;
2) dispersing carbonized lobster shells in 180mL of deionized water, and stirring with magnetic force with the concentration of 0.8mol L-1Hydrochloric acid was treated until no bubbles were generated and adjusted to PH 7.0. Cleaning the filtered product, and freeze-drying to obtain the nitrogen-doped carbon nano material;
step 2: MoO3Preparation of nitrogen-doped carbon precursor
Doping nitrogen with carbon and MoO3Dispersing in deionized water at a mass ratio of 0.4:4.0, and magnetically treating the mixed solution5mL of nitrogen methyl pyrrolidone is added dropwise under the stirring condition, and the MoO is prepared by adopting a mode of stirring and evaporating to dryness3A nitrogen-doped carbon precursor;
and step 3: MoS2Preparation of quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon nano material
1) Adding MoO3Mixing the nitrogen-doped carbon precursor and thiourea according to the mass ratio of 0.5:5.0, uniformly grinding, and placing in a tubular furnace;
2) ar gas is introduced at the beginning of the reaction at a flow rate of 100sccm to ensure that the reaction is carried out under inert conditions. At 2 ℃ for min-1The temperature rising rate is increased from room temperature to 100 ℃, the gas flow rate of argon is controlled to be 100sccm, the temperature is continuously increased to 140 ℃, and the reaction is carried out for 1.2 hours in a heat preservation way;
3) then continuing to control the temperature for 2 ℃ min-1The temperature rises to 750 ℃ at the temperature rising rate, and the reaction is carried out for 1.2h under the condition of heat preservation. During this process, the argon supply was stopped to maintain a high concentration of H2S gas and MoO3Fully reacting with nitrogen-doped carbon;
4) cooling to room temperature along with the furnace after the reaction is finished, cleaning and drying the reaction product, and finally obtaining the MoS2Quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon nano material.
Example 5
MoS2The preparation method of the quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material comprises the following steps:
step 1: preparation of nitrogen-doped carbon nano material
1) Putting 40g of cleaned lobster shells into a tube furnace, and heating at 10 ℃ for min under the condition of argon gas-1The temperature rising rate is increased from room temperature to 750 ℃ for carbonization, and the carbonized product is cooled to room temperature along with the furnace after heat preservation for 3 hours;
2) the carbonized lobster shells were dispersed in 180mL of deionized water, treated with 0.8mol L-1 hydrochloric acid under magnetic stirring until no bubbles were generated, and adjusted to PH 7.0. Cleaning the filtered product, and freeze-drying to obtain the nitrogen-doped carbon nano material;
step 2: MoO3Preparation of nitrogen-doped carbon precursor
Doping nitrogen with carbon and MoO3Dispersing the mixture into deionized water according to the mass ratio of 0.4:5.0, dropwise adding 6mL of azomethylpyrrolidone into the mixed solution under the condition of magnetic stirring, and preparing MoO by adopting a mode of stirring and evaporating to dryness3A nitrogen-doped carbon precursor;
and step 3: MoS2Preparation of quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon nano material
1) Adding MoO3Mixing the nitrogen-doped carbon precursor and thiourea according to the mass ratio of 0.5:6.0, grinding uniformly, and placing in a tubular furnace;
2) ar gas is introduced at the beginning of the reaction at a flow rate of 100sccm to ensure that the reaction is carried out under inert conditions. At 2 ℃ for min-1The temperature rising rate is increased from room temperature to 100 ℃, the gas flow rate of argon is controlled to be 100sccm, the temperature is continuously increased to 150 ℃, and the reaction is carried out for 1.5 hours in a heat preservation way;
3) then continuing to control the temperature for 2 ℃ min-1The temperature is raised to 800 ℃ at the temperature raising rate, and the reaction is carried out for 1.5h under the condition of heat preservation. During this process, the argon supply was stopped to maintain a high concentration of H2S gas and MoO3Fully reacting with nitrogen-doped carbon;
4) cooling to room temperature along with the furnace after the reaction is finished, cleaning and drying the reaction product, and finally obtaining the MoS2Quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon nano material.
Referring to FIG. 1, it can be seen from FIG. 1 that the product prepared exhibits a three-dimensional structure, MoS of about 10nm in size2The quasi-quantum dots are densely wrapped on the surface of the three-dimensional carbon substrate material.
Referring to FIG. 2, MoS can be prepared by in situ synthesis2Quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon nano material (curve with larger ordinate in figure 2), each diffraction peak in XRD diffraction pattern can be matched with MoS2The diffraction peaks of the standard card corresponded, indicating better crystallinity and higher purity. Meanwhile, the standard diffraction peak of the carbon material also appears in the nitrogen-doped biomass carbon nano material (a curve with a smaller ordinate in fig. 2).
Further, the MoS obtained above was used2Quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon nano materialThe material is used in a negative electrode material of a sodium-ion battery and is tested to have the following performance:
see FIG. 3, for MoS2And the electrical property display diagram of the quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon nano material as the cathode of the sodium ion battery. As can be seen, MoS2The quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon nano material as the cathode of the sodium ion battery has excellent cycling stability and higher specific capacity, and the specific capacity is 100mAg-1The capacity can still be kept at 340mAh g after 100 cycles under the current density of (1)-1The above. This indicates that MoS2The quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon nano material has better electrochemical performance when being applied to a cathode of a sodium ion battery.
In conclusion, the invention synthesizes MoS in situ by a solid phase method2Quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon nano material. The method has the characteristics of simple and easily-controlled preparation process, short reaction period, low energy consumption, high repeatability, high yield and the like. Meanwhile, the method also solves the problems of preparation of N, S co-doped biomass carbon and MoS in the prior art2The growth on the surface of the silicon dioxide needs to be carried out in two steps. MoS prepared by the method2The quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon nano material as the negative electrode of the sodium ion battery has the characteristics of high specific capacity, good cycling stability and the like.
The foregoing has described preferred embodiments of the present invention and is not to be construed as limiting the claims. The present invention is not limited to the above embodiments, and the specific structure thereof is allowed to vary, and various changes made within the scope of the independent claims of the present invention are within the scope of the present invention.

Claims (10)

1. MoS2The preparation method of the quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material is characterized by comprising the following steps of:
(1) preparing a nitrogen-doped carbon nano material: carbonizing the cleaned biomass, mixing with acid, stirring, and drying to obtain nitrogen-doped carbon nanomaterial;
(2)MoO3preparation of nitrogen-doped carbon precursor: mixing the nitrogen-doped carbon nano material prepared in the step (1) with MoO3Liquid phase mixing is carried out, N-methyl pyrrolidone is added under the stirring condition, and MoO is obtained after thermal evaporation to dryness3A nitrogen-doped carbon precursor;
(3)MoS2preparing a quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material: MoO prepared in the step (2)3Mixing the nitrogen-doped carbon precursor and thiourea, and then placing the mixture in a protective atmosphere for two-stage heating calcination to obtain MoS2Quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material.
2. A MoS according to claim 12The preparation method of the quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material is characterized by comprising the following steps of: the biomass adopted in the step (1) is lobster shells.
3. A MoS according to claim 22The preparation method of the quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material is characterized by comprising the following steps of: the carbonization treatment comprises the following specific steps: putting the lobster shells into a tube furnace, and performing argon treatment at 5-10 ℃ for min-1The temperature rising rate is increased from room temperature to 550-750 ℃ for carbonization, and the carbonization furnace is cooled to room temperature after heat preservation for 1-3 h.
4. A MoS according to claim 12The preparation method of the quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material is characterized by comprising the following steps of: in the step (1), the concrete operations after the carbonization treatment are as follows: treating with dilute hydrochloric acid under magnetic stirring until no bubbles are generated, and adjusting pH to 7.0; freeze-drying the product after cleaning and filtering to obtain the nitrogen-doped carbon nano material; and the concentration of the dilute hydrochloric acid is 0.2-1.0mol L-1(ii) a In the step 1), the product after hydrochloric acid treatment is washed by deionized water and ethanol for several times, and then is freeze-dried for 8-12 h at the temperature of-10 to-50 ℃.
5. A MoS according to claim 12The preparation method of the quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material is characterized by comprising the following steps of: in the step (2), nitrogen is doped with the carbon nano material and MoO3The mass ratio of (1.0-5.0) to (0.4); MoO in the step (3)3The mass ratio of the nitrogen-doped carbon precursor to the thiourea is 0.5: (2.0-6.0).
6. A MoS according to claim 12The preparation method of the quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material is characterized by comprising the following steps of: in the step (3), the specific conditions of the two-stage temperature-raising calcination are as follows: and introducing inert gas, heating to 110-150 ℃ from room temperature under inert atmosphere, carrying out heat preservation reaction for 0.5-2 h, then continuously heating to 600-800 ℃, carrying out heat preservation reaction for 0.5-2 h, and cooling to room temperature along with the furnace after the reaction is finished.
7. A MoS according to claim 62The preparation method of the quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material is characterized by comprising the following steps of: in the step (3), the inert gas is stopped to be introduced when the temperature of the tubular furnace is increased from room temperature to 100 ℃, and the rate of temperature increase is 2 ℃ for min-1。
8. A MoS according to claim 12The preparation method of the quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material is characterized by comprising the following steps of: in the step (3), the two-stage heating calcination further comprises the treatment of cleaning and drying the reaction product, and the specific treatment mode is as follows: and washing the calcined product with deionized water and ethanol, and freeze-drying for 8-12 h.
9. MoS produced by the method according to any of claims 1 to 82Quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material.
10. The MoS of claim 92The quasi-quantum dot/nitrogen and sulfur co-doped biomass carbon composite nano material is applied as a negative electrode material of a sodium ion battery.
CN202110128044.2A 2021-01-29 2021-01-29 MoS2Preparation method and application of quasi-quantum dot/nitrogen-sulfur co-doped biomass carbon composite nano material Pending CN112786865A (en)

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Application publication date: 20210511