CN113506867A - MoS for lithium ion battery2N/N doped composite material and preparation method thereof - Google Patents
MoS for lithium ion battery2N/N doped composite material and preparation method thereof Download PDFInfo
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- CN113506867A CN113506867A CN202110772285.0A CN202110772285A CN113506867A CN 113506867 A CN113506867 A CN 113506867A CN 202110772285 A CN202110772285 A CN 202110772285A CN 113506867 A CN113506867 A CN 113506867A
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- 239000002131 composite material Substances 0.000 title claims abstract description 77
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 44
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims description 16
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 32
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 28
- 239000002135 nanosheet Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000011229 interlayer Substances 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 43
- 229920000877 Melamine resin Polymers 0.000 claims description 25
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000007773 negative electrode material Substances 0.000 claims description 7
- 235000015393 sodium molybdate Nutrition 0.000 claims description 7
- 239000011684 sodium molybdate Substances 0.000 claims description 7
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
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- 238000002791 soaking Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims 2
- 239000007772 electrode material Substances 0.000 abstract description 12
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- 238000007599 discharging Methods 0.000 abstract description 7
- 239000010410 layer Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
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- 239000000463 material Substances 0.000 description 5
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229910016043 LixMoS2 Inorganic materials 0.000 description 4
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- 239000002210 silicon-based material Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910001216 Li2S Inorganic materials 0.000 description 3
- -1 Transition metal sulfides Chemical class 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
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- 238000002441 X-ray diffraction Methods 0.000 description 2
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- QTTMOCOWZLSYSV-QWAPEVOJSA-M equilin sodium sulfate Chemical compound [Na+].[O-]S(=O)(=O)OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4C3=CCC2=C1 QTTMOCOWZLSYSV-QWAPEVOJSA-M 0.000 description 2
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- IQMAMZYAQFTIAU-UHFFFAOYSA-N lithium;sulfanylidenemolybdenum Chemical compound [Li].[Mo]=S IQMAMZYAQFTIAU-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
- H01M4/58—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
The invention discloses a MoS for a lithium ion battery2The composite material is a flower-shaped structure formed by mutually stacking staggered and connected nanosheets, wherein the nanosheets are transparent and curled, and the interlayer spacing is slightly larger than MoS2The transverse size of petals in the flower is 1-2 mu m, and the structure can effectively limit MoS2Flake growth of electrolyteThe lithium ion battery electrode material is soaked in the electrode material, so that the diffusion path of lithium ions is shortened, and the volume expansion of the composite material in the circulation process can be limited, so that the lithium ion battery electrode material has good conductivity, structural stability, electrochemical stability and the like. MoS of the invention2The/nitrogen-doped composite material has higher specific capacitance which can reach about 862.6mAh/g, has good retentivity under multiple cycles, shows good and stable electrochemical performance, solves the problems of low capacity and capacity attenuation during charging and discharging of the existing lithium ion battery, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a MoS for a lithium ion battery2A nitrogen-doped composite material and a preparation method thereof.
Background
Although the lithium ion battery has been commercialized for many years, and with the progress of various technologies, it is widely used in various fields of human production and life. However, with the improvement of life and the increasing demand of people, we have higher requirements on the size and quality of various electronic devices, which means that the energy density of the battery must be further improved.
The electrode materials used by the existing batteries are many, for example, the invention patent CN201610750365.5 discloses a silicon-carbon composite material for a lithium ion battery and a preparation method thereof, wherein the silicon-carbon composite material is a secondary particle structure formed by uniformly dispersing and embedding silicon materials on the surface of a graphite material and among the graphite materials; through the steric hindrance and the adhesive effect of the high molecular polymer, the floating and agglomeration of the silicon material and the layering of the silicon material and the graphite are effectively inhibited, the silicon material is uniformly dispersed in the graphite flake and effectively compounded with the graphite, and the advantages of high efficiency, small expansion and good circulation are realized. In patent CN201811023519.6, graphite nanoplatelets are used as the nano core material, and the surface of the graphite nanoplatelets is modified by ionic liquid, so that the positive charge of the surface of the graphite nanoplatelets can be realized; meanwhile, the coating material is prepared by a sol-gel method, on one hand, the double electric layer structure of the metal oxide in the gel is broken by using the inorganic salt modifier, so that the surface of the nano metal oxide is charged with negative charges, and on the other hand, the inorganic salt modifier can be doped in the coating material to improve the discharge performance of the cathode material. Although the above method can improve the capacity of the battery by compounding with some common carbon materials, the stability of the material needs to be further improved.
Transition metal sulfides are concerned by a plurality of scientific researchers due to the graphite-like structure and higher theoretical specific capacity of the transition metal sulfides. Molybdenum disulfide as a typical representative of transition metal sulfides is concerned about due to unique physicochemical properties, and has a wide application prospect in the fields of lithium ion batteries and the like. However, molybdenum disulfide has very low intrinsic conductivity, and changes in volume during charging and discharging processes, which leads to capacity fading and affects the electrochemical performance of the electrode material. Currently, most of the problems are modified by preparing a single layer or few layers of molybdenum disulfide by a physical or chemical method, compounding the molybdenum disulfide with some materials with good conductivity such as carbon nanotubes or graphene, and stabilizing metals by an ion doping method. The properties of nanocomposites of different morphologies are also different. Synthesis of MoS by salt template-assisted solid phase method, e.g., Zhou2The nano material has a three-dimensional honeycomb structure, has close interface bonding capacity between adjacent nano sheet walls, and is used as a lithium battery cathode material with the concentration of 100 mA.g-1The first charge-discharge specific capacity under the current density is 877 mA.h.g-1And 938mA · h · g-1The first effect is close to 93.5%, and the specific discharge capacity is increased to 1025 mA.h.g after 50 times of charging and discharging-1At 2 A.g-1Under a large current, 463mA · h · g-1The specific capacity of the resin shows excellent cycling and rate performance. Tian et al synthesized layered MoS by one-step hydrothermal method2And interconnected Graphene Nanoribbons (GNRs), found by cycling tests at 200mA · g-1The specific discharge capacity after 80 cycles under the current density is 1009.4mA · h · g-1At 3 A.g-1The specific capacity of the alloy still remains 606.8 mA.h.g under the current density-1From structural, morphological and chemical analyses, it is shown that the composite material of 3D structure is due to large surface area and abundant mesopores, so thatThe contact area between the electrode and the electrolyte is larger; furthermore, 2D MoS2The synergistic effect between the layer and the GNRs within the 3D structure allows for fast lithium ion and electron transport while suppressing MoS2And the nano sheets are agglomerated, so that stable cycle performance and high rate performance are obtained. However, the lithium ion intercalation and deintercalation process induces MoS2The problem of volume change causes the practical electrochemical performance of the product to be unstable, and the MoS is seriously influenced2The electrochemical performance of the composite material is exerted, particularly the high rate performance is influenced, and the MoS is limited to a great extent2The composite material is applied to the electrode material of the lithium ion battery.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention is directed to providing a MoS for a lithium ion battery2The nitrogen doped composite material and the preparation method solve the problem of MoS2The lithium ion battery electrode material has the problems of low capacity, serious capacity attenuation caused by serious volume expansion in the charging and discharging processes and the like, and meanwhile, the infiltration of electrolyte in the electrode material is accelerated, and the diffusion path of lithium ions is shortened.
In order to achieve the purpose, the invention adopts the following technical scheme: MoS for lithium ion battery2The composite material is nitrogen-doped by taking melamine as a template and is mixed with MoS2Prepared by compounding, the MoS2Form Mo-N bond with nitrogen element, the composite material is in a flower-shaped structure formed by mutually stacking staggered connected nano-sheet layers, the nano-sheet layers are transparent and curled, and the interlayer spacing is slightly larger than MoS2The transverse dimension of petals in the flower is 1-2 mu m. In this way, although the nanosheets are stacked layer by layer, the phenomenon of transparency still occurs, which indicates that the nanosheets are very thin, the obtained structure is very thin and curled, and the infiltration of the electrolyte in the electrode material can be accelerated, and the diffusion path of lithium ions can be shortened.
The invention also provides the MoS for the lithium ion battery2The preparation method of the/nitrogen-doped composite material comprises the following steps:
1) adding melamine into a dilute hydrochloric acid solution, soaking, cleaning for several times until the solution is neutral, collecting a sample, then carrying out vacuum drying, activating in a tube furnace under an air atmosphere, then adding water, and uniformly stirring to obtain a melamine template solution;
2) weighing sodium molybdate and thiourea, dissolving in the melamine template solution obtained in the step 1), and continuously stirring uniformly to obtain a mixed solution;
3) transferring the mixed solution obtained in the step 2) into a reaction kettle for hydrothermal reaction, after the reaction is finished, centrifuging and collecting precipitates, then alternately cleaning the precipitates with deionized water and absolute ethyl alcohol, drying the precipitates in vacuum, and annealing the products in an inert atmosphere to obtain the MoS2A/nitrogen doped composite material.
Preferably, the concentration of the melamine template solution is 0.2 mol/L.
Preferably, the molar ratio of the sodium molybdate to the thiourea is 7: 30.
preferably, the activation is carried out for 1-2 h at 350-450 ℃.
Preferably, the hydrothermal reaction temperature is 150-300 ℃, and the reaction time is 15-20 h.
Preferably, the inert atmosphere is nitrogen or argon.
Preferably, the drying temperature is 70-90 ℃, and the time is 10-12 h.
Preferably, the annealing temperature is 600-800 ℃, and the annealing time is 1-3 h.
The invention also provides the application of the composite material or the composite material prepared by the method in a negative electrode material of a lithium battery.
Compared with the prior art, the invention has the following beneficial effects:
1. the MoS for the lithium ion battery provided by the invention2The composite material is in a flower-shaped structure formed by mutually stacking staggered and connected nanosheets, the number of the nanosheets is small, the nanosheets are thin and curled, and the interlayer spacing is slightly larger than MoS2Spacing of crystal planes of, said "petals"The transverse dimension of the structure is 1-2 mu m, and the structure can effectively limit MoS2The flaky growth can also accelerate the infiltration of electrolyte in the electrode material, shorten the diffusion path of lithium ions, and limit the volume expansion of the composite material in the circulation process, so that the composite material has good conductivity, structural stability, electrochemical stability and the like. MoS of the invention2The/nitrogen-doped composite material has higher specific capacitance which can reach about 862.6mAh/g, has good retentivity under multiple cycles, shows good and stable electrochemical performance, solves the problems of low capacity and capacity attenuation during charging and discharging of the existing lithium ion battery, and has good application prospect.
2. The composite material prepared by the invention is nitrogen-doped by taking melamine as a template and is mixed with MoS2The melamine is rich in nitrogen elements, nitrogen can be doped in the carbonization process, but when the concentration of the melamine is too high or too low, the stacking condition and the thickness of the nanosheets can be influenced, so that the specific capacity can be reduced, and because lithium ions and nitrogen can generate irreversible reaction in the discharge process, the lithium ions capable of being combined with the base material are reduced, the capacity is reduced, and the nitrogen doping amount needs to be proper. In addition, MoS2The structure can form Mo-N bonds with nitrogen elements, provide more paths for electron transmission and ion diffusion and improve MoS2Structural stability of the nanosheets. The invention takes the melamine as the raw material, has low cost, easy acquisition and simple and easy operation of the preparation method, and has good application prospect.
Drawings
FIG. 1 is a MoS made according to the present invention2XRD pattern of the/nitrogen doped composite material.
FIG. 2 is a MoS made according to the present invention2SEM image of/nitrogen doped composite;
a. b is example 1, c, d are example 2, e, f are example 3.
FIG. 3 is the MoS obtained in example 22Elemental surface scan of the/nitrogen doped composite.
FIG. 4 shows the present inventionMing-made MoS2TEM image of/nitrogen-doped composite;
a. b is example 1, c, d are example 2, e, f are example 3.
Fig. 5 is a schematic view of the assembly process of the button cell.
FIG. 6 shows MoS prepared according to the present invention2Electrochemical performance of the nitrogen-doped composite material;
a is the cyclic voltammogram of example 1, b is the charge-discharge curve of example 1; c is the cyclic voltammogram of example 2, d is the charge-discharge curve of example 2; e is the cyclic voltammogram of example 3, and f is the charge and discharge curve of example 3.
FIG. 7 shows MoS prepared by the present invention2The cycle performance (a) and the rate performance curve (b) of the/nitrogen-doped composite material.
FIG. 8 shows MoS prepared according to the present invention2Electrochemical impedance diagram of the/nitrogen-doped composite material.
Detailed Description
The present invention will be described in further detail with reference to the following specific embodiments and the accompanying drawings. The experimental procedures are not specifically described in the following examples, and are carried out in a conventional manner using reagents which are generally commercially available.
MoS for lithium ion battery2Preparation method of/nitrogen-doped composite material
Example 1
1) Adding a certain amount of melamine into 100mL of 0.1mol/L diluted hydrochloric acid solution, soaking for 12h, cleaning for several times until the solution is neutral, collecting a sample, then placing the sample in a tube furnace for vacuum drying at 80 ℃ for 6h, then placing the sample in the tube furnace for activation at 400 ℃ for 1h in an air atmosphere, and then adding water for full dissolution to obtain a melamine template solution.
2) 0.726g of sodium molybdate and 1.14g of thiourea are weighed and dissolved in 30mL of melamine template solution with the concentration of 0.1mol/L, and stirring is continued for 1h to obtain a mixed solution.
3) Transferring the mixed solution obtained in the step 2) into a stainless steel reaction kettle, carrying out hydrothermal reaction at 200 ℃ for 18h, centrifuging, collecting precipitate, then alternately cleaning the precipitate for 3 times by using deionized water and absolute ethyl alcohol, carrying out vacuum drying at 80 ℃ for 12h,then in N2Annealing at 700 ℃ for 2h in a/Ar atmosphere to obtain the MoS2A/nitrogen doped composite material.
Example 2
1) Adding a certain amount of melamine into 100mL of 0.1mol/L diluted hydrochloric acid solution, soaking for 12h, cleaning for several times until the solution is neutral, collecting a sample, then placing the sample in a tube furnace for vacuum drying at 80 ℃ for 6h, and then placing the sample in the tube furnace for activation at 400 ℃ for 1h under the air atmosphere to obtain a melamine template.
2) 0.726g of sodium molybdate and 1.14g of thiourea are weighed and dissolved in 30mL of melamine template solution with the concentration of 0.2mol/L, and stirring is continued for 1h to obtain a mixed solution.
3) Transferring the mixed solution obtained in the step 2) into a stainless steel reaction kettle, carrying out hydrothermal reaction at 200 ℃ for 18h, centrifuging, collecting precipitate, alternately cleaning the precipitate for 3 times by using deionized water and absolute ethyl alcohol, drying the precipitate in vacuum at 80 ℃ for 12h, and then carrying out N-ion exchange2Annealing at 700 ℃ for 2h in a/Ar atmosphere to obtain the MoS2A/nitrogen doped composite material.
Example 3
1) Adding a certain amount of melamine into 100mL of 0.1mol/L diluted hydrochloric acid solution, soaking for 12h, cleaning for several times until the solution is neutral, collecting a sample, then placing the sample in a tube furnace for vacuum drying at 80 ℃ for 6h, and then placing the sample in the tube furnace for activation at 400 ℃ for 1h under the air atmosphere to obtain a melamine template.
2) 0.726g of sodium molybdate and 1.14g of thiourea are weighed and dissolved in 30mL of melamine template solution with the concentration of 0.3mol/L, and stirring is continued for 1h to obtain a mixed solution.
3) Transferring the mixed solution obtained in the step 2) into a stainless steel reaction kettle, carrying out hydrothermal reaction at 200 ℃ for 18h, centrifuging, collecting precipitate, alternately cleaning the precipitate for 3 times by using deionized water and absolute ethyl alcohol, drying the precipitate in vacuum at 80 ℃ for 12h, and then carrying out N-ion exchange2Annealing at 700 ℃ for 2h in a/Ar atmosphere to obtain the MoS2A/nitrogen doped composite material.
Two, MoS2Characterization of the/Nitrogen-doped composites
1. MoS obtained in examples 1 to 32The/nitrogen-doped composite material is characterized by X-ray diffraction (XRD),as shown in fig. 1.
As can be seen from the figure, the composite material of the present invention has distinct diffraction peaks at 14.2, 33.4, 39.6, 49.3 and 58.6 degrees, corresponding to MoS, respectively2The (002), (100), (103), (105) and (110) planes of (a) and (b), which are substantially identical to the hexagonal structure of the 2H phase. In addition, no diffraction peak of impurities appears in the figure, which shows that the composite material synthesized by the template method has higher purity.
2. MoS prepared in examples 1-3 was observed by scanning electron microscopy2The results of the nitrogen-doped composite material are shown in FIGS. 2(a) to (f).
As can be seen from the figure, the micro-morphologies of the composite material prepared by the invention are all in a staggered and connected nano petal-shaped lamellar structure, and a sphere-like structure formed by winding nano sheets can be observed from fig. 2(a), fig. 2(b), fig. 2(e) and fig. 2(f), and the diameter of each microsphere is about 2 μm; there is also an irregular bulk, sheet-like structure in fig. 2(e) and 2(f), probably due to the inhibition of the nanoplate growth by too high a concentration of template. In FIG. 2(c) and FIG. 2(d), the sheet structure is transparent, the nano sheets are thinner and more curled, and are stacked into a flower-like structure, and the transverse dimension of the petals is about 1-2 μm. The nano-sheet layer in the composite material shows different structures along with the change of the template concentration in the synthesis process.
3. To further observe MoS2Composition of nitrogen doped composite the composite prepared in example 2 was subjected to surface scanning elemental analysis and the results are shown in figure 3.
As can be seen from the figure, the composite material is composed of four elements of Mo, S, C and N, and the distribution of the elements is relatively uniform.
4. MoS prepared in examples 1-32The transmission electron microscopic analysis of the/nitrogen-doped composite material was carried out, and the results are shown in FIG. 4.
As can be seen from fig. 4(a) and 4(e), the stacking of the nanosheets is relatively loose, which increases the ion diffusion path, resulting in poor battery rate performance. It can be seen from fig. 4(b) and 4(f) that the thickness of the nanosheets is 10 layers or more, which also affects the cyclicity of the electrode materialThe number of layers of the nanosheet in FIG. 4(d) is relatively small (less than 8 layers), with the interlayer spacing being about 0.7nm, slightly larger than MoS2Possibly due to some carbon material intercalation.
Electrochemical test
MoS prepared in examples 1-32The/nitrogen-doped composite material is a negative electrode material, and is prepared from the following components in percentage by weight: conductive agent: binder 7: 2: 1 MoS is weighed according to the mass ratio2The nitrogen-doped composite material, Super P and CMC solution are used for standby; grinding and mixing the CMC solution and the Super P in a mortar uniformly, adding the active substance, continuously grinding and mixing uniformly to obtain pasty slurry; spreading the cut Cu foil on a coating machine, cleaning with absolute ethyl alcohol to remove dirt and dust, and then adjusting the thickness of a scraper to 100 mu m; transferring the ground slurry to a Cu foil for coating and drying, and then performing rolling treatment by using a roller press; and transferring the Cu foil coated with the slurry to a vacuum drying oven at 80 ℃ for drying for 12 h. And finally, assembling by using a CR2032 button cell, wherein the CR2032 button cell mainly comprises a positive electrode, a negative electrode, a diaphragm, electrolyte, a cell shell and the like, a metal lithium sheet is used as a counter electrode, and a Celgard2400 type commercial microporous membrane is used as the diaphragm. The specific process is shown in fig. 5 (from bottom to top): positive electrode shell-electrode slice-diaphragm-metal lithium slice-gasket-spring slice-negative electrode shell. The resulting button cells were then subjected to electrochemical performance testing.
1. The electrochemical performance of the assembled CR2032 button cell is tested under the condition of 0.01-3V, and the result is shown in figure 6.
As shown in FIG. 6(a), during the first negative scan, a weak reduction peak at 1.40V was observed, which may be the occurrence of MoS2+xLi++xe-→LixMoS2Conversion reaction, expressed as Li+Insertion into MoS2Lithium molybdenum sulfur cluster is formed between the layers, and in addition, a remarkable reduction peak is positioned at 0.38V, which is mainly LixMoS2Is reduced into metallic Mo nano-particles and Li2And S. During the second and third negative electrode scanning, two new reduction peaks at 1.77V and 1.31V, and 1.77VIs mainly due to the reduction of S to Li2And the reduction reaction at 1.31V is the same as that at 0.44V at the first negative scan. During the first positive scan, two distinct oxidation peaks can be observed at 1.61 and 2.28V, corresponding to re-oxidation of metallic Mo particles to MoS, respectively2And Li2S undergoes oxidation to form S, but then the position of the oxidation peak shifts, which may be that some irreversible reaction occurs. The reduction peaks at 0.31V and 0.36V during the first negative scan in fig. 6(c), 6(e) are mainly due to the occurrence of LixMoS2+(4-x)Li++(4-x)e-→Mo+2Li2In the transformation process such as S, the reactions occurring in the subsequent reduction peaks are the same as those in (a), and the oxidation reaction occurring in the positive electrode scanning process is the same as that in fig. 6(a), except that the peaks around 1.60V are not shifted, indicating that the latter two kinds of composite materials have fewer side reactions.
In fig. 6(b), 6(d) and 6(f), it can be observed that the position of the discharge plateau in the first discharge curve is around 0.5V, which is mainly LixMoS2Reduction reaction is carried out to generate Mo nano particles and Li2S and electrolyte are decomposed to form a gel polymer layer, and S is generated on the discharge platforms of about 1.75V and 1.4V in the second and third discharge processes8To Li2S conversion and Li+And Mo. In addition, we can see that the first discharge specific capacities of the three composite materials are 731 mA.h.g respectively-1、884mA·h·g-1And 700 mA. h.g-1The composite material prepared in example 2 has the lowest first coulombic efficiency and high capacity retention, which is probably because the composite material has a larger contact surface with the electrolyte and consumes more lithium ions when generating the SEI film. In addition, it can be seen from the curves of fig. 6(d) and 6(f) that there is a large capacity loss during the first charge and discharge, which may be an irreversible reaction.
2. The assembled CR2032 button cell was subjected to cycling performance tests at a current density of 200mA/g and at 50, 100, 200, 500, 1000 and 2000mA g-1Different charging and discharging current carrying multiplying power performanceThe results of the tests are shown in FIG. 7.
As shown in FIG. 7(a), the current density was 200mA · g-1Under the conditions of (1) three MoS2The first charge-discharge specific capacity of the/nitrogen-doped composite material is 671.5 mA.h.g-1、746mA·h·g-1，607.4mA·h·g-1、862.6mA·h·g-1And 526.5mA · h · g-1、701.1mA·h·g-1The composite material prepared in example 2 had the lowest initial coulombic efficiency and high capacity retention rate, which also met the results obtained in the above charge-discharge curves. After 100 times of charging and discharging, the specific discharge capacity of the three composite electrodes is 459.2 mA.h.g-1、554.6mA·h·g-1And 448.3mA · h · g-1In contrast, the capacity retention rate of the composite material prepared in example 2 is up to 90.9%, and the capacity fading of the composite material prepared in example 1 is relatively serious, and the capacity retention rate of the composite material prepared in example 3 is also 87.8%, but the specific discharge capacity is relatively low. It is evident from FIG. 7(b) that the composite material prepared in example 2 has better rate capability, and the specific discharge capacity is 617mA · h · g under different current densities-1、588mA·h·g-1、543mA·h·g-1、458mA·h·g-1、380mA·h·g-1And 338 mA. h. g-1When the current density returns to 50mA · g-1When the discharge capacity is recovered to 615 mA.h.g-1. This shows that proper amount of nitrogen doping can improve the stability and rate performance of the composite material, but when the concentration is too high, nitrogen and lithium can generate too much irreversible reaction, which causes Li+The active sites are reduced, resulting in a decrease in capacity.
FIG. 8 shows MoS prepared in examples 1 to 32Electrochemical Impedance (EIS) plot of/nitrogen-doped composites. The fitted Nyquist plot is composed of a semicircle whose diameter represents the charge transfer resistance (Rct) inside the electrode and an inclined straight line whose slope represents the diffusion resistance Warburg resistance of lithium ions in the electrode material, and whose intercept with the abscissa represents the ohmic resistance (Re) of the battery. According to the fitting result, three MoS can be obtained2N-doped composite materialThe charge transfer resistances of 177.4 omega, 108.7 omega and 270.9 omega respectively show that the impedance of the composite material is minimum when the template concentration is 0.2mol/L, and the slope of the straight line is maximum as shown in the figure, which shows that Li is in the composite material+The rate of migration in the electrode material is also relatively fast.
Through analysis and comparison, the electrochemical performance of the composite material after nitrogen doping is improved to a certain extent, and MoS is obtained when the concentration of melamine is 0.2mol/L2The nitrogen-doped composite material is at 200 mA.g-1The specific capacity of the first discharge at the current density of (A) is 862.6mA · h · g-1After 100 times of charging and discharging, the reversible capacity is still 550mA · h · g-1(ii) a When the current density is from 2 A.g-1Reduced to 50mA g-1The discharge specific capacity can still be reduced to 615 mA.h.g-1. However, when the melamine concentration is too high or too low, the specific capacity is rather lowered because the lithium ions and nitrogen react irreversibly during discharge, and the lithium ions capable of binding to the matrix material are reduced, thereby resulting in a decrease in capacity, so that the nitrogen doping cannot be excessive.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (10)
1. MoS for lithium ion battery2The nitrogen-doped composite material is characterized in that the composite material is nitrogen-doped by taking melamine as a template and is mixed with MoS2The composite material is prepared by mutually stacking staggered and connected nanosheets into a flower-shaped structure, wherein the nanosheets are transparent and curled, and the interlayer spacing is slightly larger than MoS2The transverse dimension of petals in the flower is 1-2 mu m.
2. A method as claimed in1 said MoS for lithium ion battery2The preparation method of the/nitrogen-doped composite material is characterized by comprising the following steps of:
1) adding melamine into a dilute hydrochloric acid solution, soaking, cleaning for several times until the solution is neutral, collecting a sample, then carrying out vacuum drying, activating in a tube furnace under an air atmosphere, then adding water, and uniformly stirring to obtain a melamine template solution;
2) weighing sodium molybdate and thiourea, dissolving in the melamine template solution obtained in the step 1), and continuously stirring uniformly to obtain a mixed solution;
3) transferring the mixed solution obtained in the step 2) into a reaction kettle for hydrothermal reaction, after the reaction is finished, centrifuging and collecting precipitates, then alternately cleaning the precipitates with deionized water and absolute ethyl alcohol, drying the precipitates in vacuum, and annealing the products in an inert atmosphere to obtain the MoS2A/nitrogen doped composite material.
3. MoS for lithium ion battery according to claim 12The preparation method of the/nitrogen-doped composite material is characterized in that the concentration of the melamine template solution is 0.2 mol/L.
4. MoS for lithium ion battery according to claim 12The preparation method of the @ C composite negative electrode material is characterized in that the molar ratio of sodium molybdate to thiourea is 7: 30.
5. MoS for lithium ion battery according to claim 12The preparation method of the @ C composite negative electrode material is characterized in that the activation is carried out for 1-2 hours at the temperature of 350-450 ℃.
6. MoS for lithium ion battery according to claim 12The preparation method of the @ C composite anode material is characterized in that the hydrothermal reaction temperature is 150-300 ℃, and the reaction time is 15-20 hours.
7. MoS for lithium ion battery according to claim 12The preparation method of the @ C composite anode material is characterized in that the inert atmosphere is nitrogen or argon.
8. MoS for lithium ion battery according to claim 12The preparation method of the @ C composite negative electrode material is characterized in that the drying temperature is 70-90 ℃ and the drying time is 10-12 h.
9. MoS for lithium ion battery according to claim 12The preparation method of the @ C composite negative electrode material is characterized in that the annealing temperature is 600-800 ℃, and the annealing time is 1-3 hours.
10. Use of the composite material according to claim 1 or the composite material prepared by the method according to any one of claims 2 to 9 in a negative electrode material for a lithium battery.
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