CN104681815B - Spherical molybdenum disulfide composite material and preparation method and application thereof - Google Patents
Spherical molybdenum disulfide composite material and preparation method and application thereof Download PDFInfo
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- CN104681815B CN104681815B CN201510072736.4A CN201510072736A CN104681815B CN 104681815 B CN104681815 B CN 104681815B CN 201510072736 A CN201510072736 A CN 201510072736A CN 104681815 B CN104681815 B CN 104681815B
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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
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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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- 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
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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 spherical molybdenum disulfide composite material and a preparation method and an application thereof. The preparation method disclosed by the invention comprises the following steps: (1) respectively adding sodium molybdate and L-cysteine in deionized water, mixing uniformly, heating for 8-16 hours, naturally cooling, and alternatively washing with water and ethanol to obtain spherical molybdenum disulfide nano spheres; (2) soaking molybdenum disulfide in oleic acid for 24-72 hours, and centrifuging to remove excessive oleic acid; and (3) heating the soaked molybdenum disulfide in nitrogen or argon for 2-6 hours at 400-1100 DEG C to obtain a spherical molybdenum disulfide composite material coated with amorphous carbon. In the preparation method disclosed by the invention, the oleic acid is used for adsorbing crystal face and annealing to form the amorphous carbon, so that molybdenum disulfide is coated by an amorphous carbon layer, and the preparation method is simple and easy to operate; the prepared molybdenum disulfide composite material has uniform particle size distribution and good conductivity, and has the advantages of high capacity, good cycle stability and high rate capacity and the like, when being used as battery anode.
Description
Technical field
The application is related to lithium ion battery negative material field, more particularly to a kind of spherical molybdenum bisuphide composite and
Its preparation method and application.
Background technology
With becoming increasingly conspicuous for energy and environment problem, electric automobile, hybrid vehicle obtain fast-developing.For this purpose,
Lithium ion battery to providing the energy proposes harsher requirement.Negative material be lithium ion battery critical material it
One.The negative material of current research mainly includes tinbase, silicon substrate and material with carbon element etc..At present, business-like carbon negative pole material has
The low advantage of charging/discharging voltage platform, but while there is also the low defect such as have an effect with electrolyte of tap density.Tinbase, silicon substrate
Although negative material capacity is high, volumetric expansion and shrinkage ratio are larger in its charge and discharge process, cause cycle performance serious deterioration.
Therefore, the more excellent negative material of high power capacity, stable circulation performance is found imperative.
Molybdenum bisuphide is that the lamellar compound with class graphene-structured is conducive to the embedded of lithium ion, with higher ratio
Capacity (1334mAh/g), during as high capacity lithium ion cells cathode, the characteristics of its sufficiency of natural resources has low cost.This
Outward, the molybdenum bisuphide material of chondritic has compared with high-tap density, can improve electrode material volume energy density, and electrode is tied
Structure good stability.But spherical molybdenum bisuphide material conductivity is poor, this significantly limit its charge/discharge capacity and high rate performance.
Ding Guqiao et al., in order to improve the chemical property of molybdenum bisuphide, is prepared for Graphene/bis- in patent 201210326035.5
Molybdenum sulfide combination electrode material, the anti-of molybdenum bisuphide is evenly spread in the patent by previously prepared graphene oxide liquid mixture
In answering solution, molybdate is adsorbed in the surface of graphite oxide nanometer sheet, in-situ preparation using the functional group on graphite oxide surface
Molybdenum bisuphide, so as to obtain the Graphene/molybdenum disulfide composite electrode material of high uniformity.In the patent, Graphene and two sulfur
Change the compound of molybdenum, although the comprehensive electrochemical of negative material is increased, but, also simply Graphene and molybdenum bisuphide
Trading off for both advantage performances, it is limited to the improvement of molybdenum bisuphide material conductivity.
The content of the invention
The purpose of the application be to provide improved spherical molybdenum bisuphide composite of a kind of micro structure and preparation method thereof and
Using.
To achieve these goals, the application employs technical scheme below：
The one side of the application discloses a kind of preparation method of spherical molybdenum bisuphide composite, comprises the following steps,
(1) sodium molybdate and L-Cysteine are separately added in deionized water, are mixed, reacting by heating 8-16 hour, natural cooling, then
Alternately washed with water and ethanol, obtain the molybdenum disulfide nano ball constructed by nanometer sheet；(2) by spherical two obtained by step (1)
Molybdenum sulfide is immersed in Oleic acid, and after immersion 24-72 hours, centrifugation removes unnecessary Oleic acid；(3) oil by the absorption of step (2)
The molybdenum bisuphide of acid molecule heats 2-6 hours at 400-1100 DEG C, in nitrogen or argon gas atmosphere, obtains agraphitic carbon cladding
Spherical molybdenum bisuphide composite.
Wherein, the spherical molybdenum disulfide nano ball that nanometer sheet is constructed, the nanosphere for referring to the application is by small nanometer
Piece composition, i.e., the molybdenum disulfide nano ball constructed by small nanometer sheet.Centrifugation removes unnecessary Oleic acid, specifically,
Precipitate of molysulfides is made by centrifugation, it is unnecessary Oleic acid to remove supernatant.
It should be noted that it is critical only that for the application anneals the hydro-thermal method for preparing spherical molybdenum bisuphide with Oleic acid to be formed
Amorphous carbon combines, the creative Surface coating at least one of which amorphous carbon in spherical molybdenum disulfide nano ball, and independent
Molybdenum bisuphide compare, the composite of the application not only further increases specific capacity, and with good electric conductivity.
Also, it should be noted that the concrete operations mode that water and ethanol are alternately washed is with reference to conventional molybdenum bisuphide production stream
Mode of washing in journey, here is not specifically limited；Centrifugation removes the purpose of unnecessary Oleic acid, is ensureing molybdenum bisuphide
Oleic acid is fully adsorbed on surface, in order to form amorphous carbon coating layer in the case of, it is to avoid unnecessary amorphous carbon is generated, and
And, the Oleic acid of recovery can continue to use；Additionally, the key of the application is the spherical molybdenum bisuphide to form agraphitic carbon cladding
Composite, in follow-up application, for example prepare negative material when, its following process is according to specific working condition or life
Depending on producing purpose, here is not specifically limited.
Preferably, sodium molybdate and the mol ratio of L-Cysteine are 1 in step (1):4-1:16.It should be noted that molybdenum
Sour sodium and the amount ratio of L-Cysteine, are defined by generating molybdenum bisuphide to greatest extent, that is to say, that with its participation reaction
Chemical dosage ratio is defined, and with reference to the concrete working condition and purpose of the application, the application is preferred, using sodium molybdate and the Guangs of L- half
The mol ratio of propylhomoserin is 1:4-1:16 amount is reacted.
Preferably, the concentration of sodium molybdate is 0.02mol/L-0.1mol/L in step (1).It should be noted that sodium molybdate
The restriction of the restriction of concentration, actually reaction solution concentration, it will be understood that sodium molybdate is needed two when reacting with L-Cysteine
Person fully mixes, and concentration is too low, and yield is also low, affects production efficiency, and concentration is too high, is unfavorable for that reaction is carried out；Therefore, originally
Application preferably adopts the concentration of sodium molybdate to be reacted for 0.02mol/L-0.1mol/L.
Preferably, reaction temperature is 180-240 DEG C in step (1).It should be noted that reaction temperature refer to sodium molybdate with
The temperature of L-Cysteine hydro-thermal reaction, the application preferably adopts 180-240 DEG C, that is to say, that react at 180-240 DEG C
12 hours.
Preferably, molybdenum bisuphide and the weight ratio of Oleic acid are 1 in step (2):20-1:100.It should be noted that Oleic acid
Effect be to be sufficiently soaked molybdenum bisuphide, then, molybdenum bisuphide surface formed amorphous carbon；It is appreciated that Oleic acid
As long as consumption can be by molybdenum bisuphide immersion cmpletely；The application is preferably using molybdenum bisuphide and the weight of Oleic acid
Than for 1:20 to 1:100.
The another side of the application also discloses spherical molybdenum bisuphide composite prepared by the preparation method of the application, and this is answered
In condensation material, molybdenum bisuphide is in spherical, and its Surface coating has amorphous carbon.
It should be noted that the spherical molybdenum bisuphide composite of the application is compound with existing molybdenum bisuphide/Graphene
Material is compared, and there is essential distinction in microstructure, therefore, both when using as cell negative electrode material, either lithium
Ion embedded mode, or electric conductivity, tap density etc. are all different.
Preferably, amorphous carbon accounts for the 6%-14% of gross weight.It should be noted that the Main Function of amorphous carbon is to send out
Electric conductivity is waved, to make up the defect of molybdenum bisuphide poorly conductive, therefore, as long as can be complete wrap up molybdenum bisuphide is wherein
Can；In the application, it is contemplated that the composite factor such as specific capacity and electric conductivity, it is preferred that the amorphous carbon for making cladding molybdenum bisuphide is accounted for
The 6%-14% of gross weight.Additionally, the content of amorphous carbon can be adjusted by carburizing temperature, Oleic acid is in hot conditionss
Under, can be carbonized to form amorphous carbon, but temperature is too high, and the content of carbon can be than relatively low, the contrary feelings required in satisfaction carbonization
Under condition, the comparision contents of carbon are high at relatively low temperature, and this is gas generated with carbonisation under different temperatures relation.
Additionally, the application is used Shortcomings as lithium ion battery negative material and enters for existing molybdenum bisuphide
Row research, therefore, the application further provides the spherical molybdenum bisuphide composite of the application and is preparing lithium ion battery
Application in negative material.It should be noted that in a kind of implementation of the application, spherical curing prepared by the application
Molybdenum composite material is prepared into negative material for lithium ion battery together with conventional conductive agent and binding agent.Wherein, conductive agent
Preferably acetylene black, the preferred PVdF of binding agent.
Therefore, the application simultaneously discloses again a kind of negative material for lithium ion battery, contains in the negative material
There is the spherical molybdenum bisuphide composite of the application.
Further, in a kind of implementation of the application, by the spherical molybdenum bisuphide composite containing the application
Negative material makes lithium ion battery；Therefore, the application simultaneously discloses again a kind of spherical molybdenum bisuphide containing the application
Lithium ion battery made by the negative material of composite.
Due to being using the beneficial effect of above technical scheme, the application：
The preparation method of the application anneals to form agraphitic carbon using Oleic acid absorption crystal face, spherical two prepared in hydro-thermal method
Molybdenum sulfide nanosphere Surface coating amorphous carbon layer, preparation method is simple, easy to operate.Also, the preparation method of the application is made
The spherical molybdenum bisuphide composite of standby agraphitic carbon cladding, uses with capacity height, cyclical stability as battery cathode
Well, the features such as rate capability is high.
Description of the drawings
Fig. 1 is the scanning electron microscope of the spherical molybdenum disulfide nano ball composite of agraphitic carbon cladding in the embodiment of the present application
Figure；
Fig. 2 is the high power transmission of the spherical molybdenum disulfide nano ball composite of agraphitic carbon cladding in the embodiment of the present application
Electron microscope；
Fig. 3 is the spherical molybdenum bisuphide composite that the application is adopted in the embodiment of the present application as the button of negative material
The charging and discharging curve of battery；
Fig. 4 is the spherical molybdenum bisuphide composite that the application is adopted in the embodiment of the present application as the button of negative material
The cycle characteristics curve chart of battery.
Specific embodiment
, used as a kind of special defect grapheme material, in being rarely used in composite, the application is creative for amorphous carbon
Utilization Oleic acid anneal the characteristics of forming amorphous carbon, in advance Oleic acid is uniformly adhered to into molybdenum bisuphide surface, then moved back
Fire, forms the spherical molybdenum disulfide nano ball composite of amorphous carbon cladding.Composite prepared by the application, not only has
Good specific capacity, and electric conductivity is good；Lithium ion battery negative material is made into, with capacity height, cyclical stability
Well, the features such as rate capability is high.
It should be noted that spherical molybdenum disulfide nano ball prepared by the application, its surface is in flower-like structure；Such as Fig. 1 institutes
Show, whole molybdenum bisuphide is in spherical, and the surface of spherical molybdenum disulfide is flower-like structure；This has benefited from the molybdic acid that the application is adopted
The method that sodium and L-Cysteine hydro-thermal prepare molybdenum bisuphide.The molybdenum disulfide nano ball of flower-shaped surface texture is absorption Oleic acid,
Form amorphous carbon coating layer to provide convenience.
The application is described in further detail below by specific embodiments and the drawings.Following examples are only to the application
It is further described, should not be construed as the restriction to the application.
Embodiment one
This example prepares molybdenum bisuphide, spherical two sulfur of this example with sodium molybdate and L-Cysteine as raw material using hydro-thermal method
The preparation method for changing molybdenum composite material is as follows：
(1) respectively by the L-Cysteine mixing of the sodium molybdate aqueous solution of 20ml 0.04mol/L and 20ml 0.16mol/L
Together, in being transferred to 50 milliliters of polytetrafluoro container, and it is fixed in stainless reactor, is then directly existed with baking oven
220 DEG C, heat 12 hours, when the temperature of question response kettle is reduced to 25 DEG C naturally, by resulting reactant respectively with water and ethanol
Wash 3 times successively, the sample after washing is dried 5 hours in 70 DEG C of baking ovens, obtain spherical molybdenum disulfide nano ball；
(2) the spherical molybdenum disulfide nano ball for preparing step (1) compares 1 with Oleic acid according to weight：20 mixing, ultrasound is mixed
2 hours, unnecessary Oleic acid was removed in centrifugation, obtained adsorbing the molybdenum bisuphide of oleic acid molecular；
(3) by step (2) obtain abundant absorption oleic acid molecular molybdenum bisuphide in argon 400 DEG C heat 2 hours, i.e.,
Obtain the spherical molybdenum bisuphide composite of the agraphitic carbon cladding of this example.
Jing is measured, and in the composite of this example, agraphitic carbon content accounts for agraphitic carbon and coats spherical molybdenum bisuphide composite wood
The 13.9% of material gross weight.
Composite prepared by this example is observed using scanning electron microscope, as a result as depicted in figs. 1 and 2, Fig. 1 is this example
The agraphitic carbon of preparation coats the scanning electron microscope (SEM) photograph of spherical molybdenum bisuphide, and Fig. 2 is high power transmission electron microscope picture.As shown in Figure 1, this example
Agraphitic carbon coat a diameter of 500 ran of molybdenum disulfide nano ball, even particle size distribution, its nanometer sheet thickness is about
5-8 nanometers；As shown in Figure 2, agraphitic carbon is about 1-2 layers.
Agraphitic carbon prepared by this example coats spherical molybdenum bisuphide composite and makes lithium ion battery negative material, and
Its chemical property is tested using button cell.In the lithium ion battery negative material of this example, conductive agent adopts acetylene black, bonding
Agent adopts PVdF, molybdenum bisuphide composite：Acetylene black：PVdF is according to weight than 90wt.%: 5wt.%: 5wt.% ratio
Mix homogeneously, coats on Copper Foil.In button cell, electrolyte adopts LiPF6/EC-DEC-DMC (1: 1: 1, the w/ of 1mol/L
w).Respectively charged/discharged is carried out with 100mA/g, potential range is 0~3.0V.Jing is tested, when the electric current with 100mA/g charges
During electric discharge, the 1st week charge specific capacity can reach 1289mAh/g, and discharge capacity is 842mAh/g after 100 circulations.Fig. 3, Fig. 4 point
Not Wei agraphitic carbon coat spherical molybdenum bisuphide different circulations charging and discharging curve, cycle characteristics curves.
Embodiment two
This example is blended in the L-Cysteine of the sodium molybdate aqueous solution of the 0.2mol/L of 20ml and the 0.32mol/L of 20ml
Molybdenum bisuphide is prepared together, and remaining step and condition are identical with embodiment one.
Composite prepared by this example is observed using scanning electron microscope, is as a result shown, the agraphitic carbon cladding of this example
A diameter of 350 ran of molybdenum disulfide nano ball, even particle size distribution, its nanometer sheet thickness is about 5-8 nanometers.Jing is surveyed
Amount, in the composite of this example, agraphitic carbon content accounts for agraphitic carbon and coats spherical molybdenum bisuphide composite gross weight
13.6%.
This example prepares negative material using the identical method of embodiment one, equally tests its electrochemistry using button cell
Can, the preparation method and method of testing of button cell is identical with embodiment one.Test result shows, when with the electricity of 100mA/g
When current charge discharges, the 1st week charge specific capacity can reach 1156mAh/g, and discharge capacity is 870mAh/g after 100 circulations..
Embodiment three
This example is blended in the L-Cysteine of the sodium molybdate aqueous solution of the 0.1mol/L of 20ml and the 0.16mol/L of 20ml
Molybdenum bisuphide, and baking oven are prepared together directly at 240 DEG C, are heated 12 hours, that is to say, that hydrothermal temperature is 240 DEG C,
Remaining step and condition are identical with embodiment one.
Composite prepared by this example is observed using scanning electron microscope, is as a result shown, the agraphitic carbon cladding of this example
A diameter of 400 ran of molybdenum disulfide nano ball, even particle size distribution, its nanometer sheet thickness is about 5-8 nanometers.Jing is surveyed
Amount, in the composite of this example, agraphitic carbon content accounts for agraphitic carbon and coats spherical molybdenum bisuphide composite gross weight
13.7%.
This example prepares negative material using the identical method of embodiment one, equally tests its electrochemistry using button cell
Can, the preparation method and method of testing of button cell is identical with embodiment one.Test result shows, when with the electricity of 100mA/g
When current charge discharges, the 1st week charge specific capacity can reach 1085mAh/g, and discharge capacity is 857mAh/g after 100 circulations.
Example IV
This example is mixed with the L-Cysteine of the sodium molybdate aqueous solution of the 0.04mol/L of 20ml and the 0.16mol/L of 20ml
Molybdenum bisuphide, and baking oven are prepared together directly at 180 DEG C, are heated 12 hours, that is to say, that hydrothermal temperature is 180
DEG C, remaining step and condition it is identical with embodiment one.
Composite prepared by this example is observed using scanning electron microscope, is as a result shown, the agraphitic carbon cladding of this example
A diameter of 350 ran of molybdenum disulfide nano ball, even particle size distribution, its nanometer sheet thickness is about 5-8 nanometers.Jing is surveyed
Amount, in the composite of this example, agraphitic carbon content accounts for agraphitic carbon and coats spherical molybdenum bisuphide composite gross weight
13.5%.
This example prepares negative material using the identical method of embodiment one, except that, molybdenum bisuphide composite：Second
Acetylene black：PVdF is according to weight than 80wt.%: 10wt.%: 10wt.% ratio mix homogeneously, coats on Copper Foil, remaining with
Embodiment one is identical.Equally its chemical property is tested using button cell, the preparation method and method of testing of button cell is equal
It is identical with embodiment one.Test result shows, when the electric current charging and discharging with 100mA/g, charge specific capacity can reach within the 1st week
1205mAh/g, discharge capacity is 827mAh/g after 100 circulations.
Embodiment five
This example is blended in the L-Cysteine of the sodium molybdate aqueous solution of the 0.1mol/L of 20ml and the 0.8mol/L of 20ml
Molybdenum bisuphide, and baking oven are prepared together directly at 180 DEG C, are heated 12 hours, that is to say, that hydrothermal temperature is 180 DEG C,
In step (3), molybdenum bisuphide is heated 2 hours for 600 DEG C in argon, and remaining step and condition are identical with embodiment one.
Composite prepared by this example is observed using scanning electron microscope, is as a result shown, the agraphitic carbon cladding of this example
A diameter of 350 ran of molybdenum disulfide nano ball, even particle size distribution, its nanometer sheet thickness is about 5-8 nanometers.Jing is surveyed
Amount, in the composite of this example, agraphitic carbon content accounts for agraphitic carbon and coats spherical molybdenum bisuphide composite gross weight
9%.
This example prepares negative material using the identical method of embodiment one, except that, molybdenum bisuphide composite：Second
Acetylene black：PVdF is according to weight than 80wt.%: 10wt.%: 10wt.% ratio mix homogeneously, coats on Copper Foil, remaining with
Embodiment one is identical.Equally its chemical property is tested using button cell, the preparation method and method of testing of button cell is equal
It is identical with embodiment one.Test result shows, when the electric current charging and discharging with 100mA/g, charge specific capacity can reach within the 1st week
1090mAh/g, discharge capacity is 831mAh/g after 100 circulations.
Embodiment six
This example is mixed with the L-Cysteine of the sodium molybdate aqueous solution of the 0.04mol/L of 20ml and the 0.16mol/L of 20ml
In preparing molybdenum bisuphide, and step (3) together, molybdenum bisuphide is heated 2 hours for 1100 DEG C in argon, remaining step and bar
Part is identical with embodiment one.
Composite prepared by this example is observed using scanning electron microscope, is as a result shown, the agraphitic carbon cladding of this example
A diameter of 450 ran of molybdenum disulfide nano ball, even particle size distribution, its nanometer sheet thickness is about 5-8 nanometers.Jing is surveyed
Amount, in the composite of this example, agraphitic carbon content accounts for agraphitic carbon and coats spherical molybdenum bisuphide composite gross weight
6.1%.
This example prepares negative material using the identical method of embodiment one, except that, molybdenum bisuphide composite：Second
Acetylene black：PVdF is according to weight than 80wt.%: 10wt.%: 10wt.% ratio mix homogeneously, coats on Copper Foil, remaining with
Embodiment one is identical.Equally its chemical property is tested using button cell, the preparation method and method of testing of button cell is equal
It is identical with embodiment one.Test result shows, when the electric current charging and discharging with 100mA/g, charge specific capacity can reach within the 1st week
1093mAh/g, discharge capacity is 862mAh/g after 100 circulations.
Embodiment seven
This example is mixed with the L-Cysteine of the sodium molybdate aqueous solution of the 0.04mol/L of 20ml and the 0.16mol/L of 20ml
In preparing molybdenum bisuphide, and step (3) together, molybdenum bisuphide is heated 2 hours for 800 DEG C in argon, remaining step and bar
Part is identical with embodiment one.
Composite prepared by this example is observed using scanning electron microscope, is as a result shown, the agraphitic carbon cladding of this example
A diameter of 350 ran of molybdenum disulfide nano ball, even particle size distribution, its nanometer sheet thickness is about 5-8 nanometers.Jing is surveyed
Amount, in the composite of this example, agraphitic carbon content accounts for agraphitic carbon and coats spherical molybdenum bisuphide composite gross weight
8.9%.
This example prepares negative material using the identical method of embodiment one, except that, molybdenum bisuphide composite：Second
Acetylene black：PVdF is according to weight than 80wt.%: 10wt.%: 10wt.% ratio mix homogeneously, coats on Copper Foil, remaining with
Embodiment one is identical.Equally its chemical property is tested using button cell, the preparation method and method of testing of button cell is equal
It is identical with embodiment one.Test result shows, when the electric current charging and discharging with 100mA/g, charge specific capacity can reach within the 1st week
1151mAh/g, discharge capacity is 878mAh/g after 100 circulations.
Visible according to above example, the agraphitic carbon of the application coats spherical molybdenum bisuphide composite as lithium ion
Cell negative electrode material is used, the features such as with capacity height, good cycling stability, high rate capability.On the basis of above example
On, the application is also tested the atmosphere of Oleic acid annealing, is as a result found, process can be other lazy using beyond argon
Property gas, such as nitrogen can be used for the application.
Above content is to combine the further description that specific embodiment is made to the application, it is impossible to assert this Shen
Being embodied as please is confined to these explanations.For the application person of an ordinary skill in the technical field, do not taking off
On the premise of conceiving from the application, some simple deduction or replace can also be made, should all be considered as belonging to the protection of the application
Scope.
Claims (10)
1. a kind of preparation method of spherical molybdenum bisuphide composite, it is characterised in that：The preparation method is comprised the following steps,
(1) sodium molybdate and L-Cysteine are separately added in deionized water, are mixed, reacting by heating 8-16 hour, natural cooling,
Then alternately washed with water and ethanol, obtain the molybdenum disulfide nano ball constructed by nanometer sheet；
(2) the spherical molybdenum bisuphide obtained by step (1) is immersed in Oleic acid, after immersion 24-72 hours, it is unnecessary that centrifugation is removed
Oleic acid；
(3) by the molybdenum bisuphide for having adsorbed oleic acid molecular of step (2) at 400-1100 DEG C, heat in nitrogen or argon gas atmosphere
2-6 hours, obtain the spherical molybdenum bisuphide composite of agraphitic carbon cladding.
2. preparation method according to claim 1, it is characterised in that：Sodium molybdate and L-Cysteine in the step (1)
Mol ratio be 1:4-1:16.
3. preparation method according to claim 1, it is characterised in that：The concentration of sodium molybdate is in the step (1)
0.02mol/L-0.1mol/L。
4. preparation method according to claim 1, it is characterised in that：Reaction temperature is 180-240 in the step (1)
℃。
5. preparation method according to claim 1, it is characterised in that：The weight of molybdenum bisuphide and Oleic acid in the step (2)
Amount is than being 1:20-1:100.
6. the spherical molybdenum bisuphide composite that prepared by the preparation method according to any one of claim 1-5, its feature exists
In：Molybdenum bisuphide is in spherical, and its Surface coating has amorphous carbon.
7. spherical molybdenum bisuphide composite according to claim 6, it is characterised in that：The amorphous carbon accounts for gross weight
6%-14%.
8. the spherical molybdenum bisuphide composite according to claim 6 or 7 is in lithium ion battery negative material is prepared
Using.
9. a kind of negative material for lithium ion battery, it is characterised in that：Contain claim 6 or 7 in the negative material
Described spherical molybdenum bisuphide composite.
10. the lithium ion battery of the negative material described in a kind of employing claim 9.
Priority Applications (1)
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| CN105098151B (en) * | 2015-06-19 | 2017-05-24 | 上海交通大学 | Molybdenum disulfide-carbon hollow ball hybrid material and preparation method thereof |
| CN105126876B (en) * | 2015-09-07 | 2017-06-06 | 复旦大学 | A kind of flower-shaped carbon load MoS2Composite of nano particle and preparation method thereof |
| CN105161692A (en) * | 2015-10-23 | 2015-12-16 | 西南大学 | Preparation method for C-MoS2 composite material and products and electrochemical application thereof |
| CN105609769A (en) * | 2016-03-04 | 2016-05-25 | 河源广工大协同创新研究院 | Preparation method for multi-level structured molybdenum disulfide microsphere negative electrode material of lithium battery |
| CN105883921A (en) * | 2016-04-14 | 2016-08-24 | 北京航空航天大学 | Preparation of 3D molybdenum disulfide nano-microparticles with high broadband wave absorption capability |
| CN106362775B (en) * | 2016-08-10 | 2018-10-19 | 西北工业大学 | A kind of high efficiency photocatalysis based on molybdenum sulfide prepares the nano material and preparation method of hydrogen |
| CN106564951A (en) * | 2016-11-08 | 2017-04-19 | 中国检验检疫科学研究院 | Synthesis method of MoS2 nano-structure material |
| CN106876702B (en) * | 2017-02-08 | 2019-10-22 | 大连理工大学 | A kind of preparation method and application of sodium-ion battery cathode |
| CN107248573A (en) * | 2017-06-26 | 2017-10-13 | 浙江工业大学 | Polyphosphazene is combined the preparation method of carbon composite electrode material for the molybdenum disulfide of carbon source |
| CN110311122A (en) * | 2019-07-12 | 2019-10-08 | 青岛大学 | Carbon coating molybdenum disulfide/graphene nanocomposite material preparation method and application |
| CN110498447A (en) * | 2019-08-05 | 2019-11-26 | 河南师范大学 | A kind of synthetic method of tennis shape molybdenum disulfide micro Nano material and its preparing the application in photo-thermal anticancer drug |
| CN111204808B (en) * | 2020-01-10 | 2022-04-12 | 安徽师范大学 | Preparation method of molybdenum disulfide microcapsule, magnesium ion battery positive electrode and magnesium ion battery |
| CN111900408B (en) * | 2020-08-04 | 2022-03-01 | 四川轻化工大学 | MoS for lithium ion battery2@ C composite negative electrode material and preparation method thereof |
| CN113277562A (en) * | 2021-05-18 | 2021-08-20 | 信阳师范学院 | Flower-shaped MoS2Preparation method and application thereof |
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