CN104681815A - 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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- 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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- 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 relates to lithium ion battery negative material field, particularly relates to a kind of spherical molybdenum bisuphide composite material and its preparation method and application.
Background technology
Along with becoming increasingly conspicuous of energy and environment problem, electric automobile, hybrid vehicle obtain fast-developing.For this reason, to providing the lithium ion battery of the energy to propose harsher requirement.Negative material is one of critical material of lithium ion battery.The negative material of current research mainly comprises tinbase, silica-based and material with carbon element etc.At present, business-like carbon negative pole material has the advantages such as charging/discharging voltage platform is low, but also there is the low defect such as to have an effect with electrolyte of tap density simultaneously.Although tinbase, silicon based anode material capacity are high, in its charge and discharge process, volumetric expansion and shrinkage ratio are comparatively large, cause cycle performance serious deterioration.Therefore, find high power capacity, negative material that stable circulation performance is more excellent is imperative.
Molybdenum bisuphide is the embedding that the lamellar compound with class graphene-structured is conducive to lithium ion, and have higher specific capacity (1334mAh/g), during as high capacity lithium ion cells cathode, its sufficiency of natural resources has the low feature of cost.In addition, the molybdenum bisuphide material of chondritic has comparatively high-tap density, can improve electrode material volume energy density, and electrode structure good stability.But spherical molybdenum bisuphide material conductivity is poor, this significantly limit its charge/discharge capacity and high rate performance.The people such as fourth Gu Qiao in patent 201210326035.5 in order to improve the chemical property of molybdenum bisuphide, prepare Graphene/molybdenum disulfide composite electrode material, in this patent, previously prepared graphene oxide liquid mixture is evenly spread in the reaction solution of molybdenum bisuphide, the functional group on graphite oxide surface is utilized molybdate to be adsorbed on the surface of graphite oxide nanometer sheet, in-situ preparation molybdenum bisuphide, thus the Graphene/molybdenum disulfide composite electrode material obtaining high uniformity.In this patent, the compound of Graphene and molybdenum bisuphide, although the comprehensive electrochemical of anticathode material increases, also just Graphene and molybdenum bisuphide advantage performance is compromise, to the improvement limited efficiency of molybdenum bisuphide material conductivity.
Summary of the invention
The object of the application is to provide spherical molybdenum bisuphide composite material of a kind of micro-structural improvement and its preparation method and application.
To achieve these goals, the application have employed following technical scheme:
The one side of the application discloses a kind of preparation method of spherical molybdenum bisuphide composite material, comprise the following steps, (1) sodium molybdate and Cys are added in deionized water respectively, mix, add thermal response 8-16 hour, naturally cool, then with water and ethanol alternately washing, the molybdenum disulfide nano ball constructed by nanometer sheet is obtained; (2) the spherical molybdenum bisuphide of step (1) gained is immersed in oleic acid, soaks after 24-72 hour, the oleic acid that centrifugal segregation is unnecessary; (3) by the molybdenum bisuphide having adsorbed oleic acid molecular of step (2) at 400-1100 DEG C, heat 2-6 hour in nitrogen or argon gas atmosphere, obtain the spherical molybdenum bisuphide composite material that agraphitic carbon is coated.
Wherein, the spherical molybdenum disulfide nano ball that nanometer sheet is constructed, refers to what the nanosphere of the application was made up of small nanometer sheet, the molybdenum disulfide nano ball namely constructed by small nanometer sheet.The oleic acid that centrifugal segregation is unnecessary, concrete, namely make precipitate of molysulfides by centrifugal, remove supernatant and unnecessary oleic acid.
It should be noted that, the key of the application is the hydro thermal method of the spherical molybdenum bisuphide of preparation and oleic acid to anneal and forms amorphous carbon and combine, the creationary Surface coating at spherical molybdenum disulfide nano ball at least one deck amorphous carbon, compared with independent molybdenum bisuphide, the composite material of the application, not only further increase specific capacity, and there is good conductivity.
Also it should be noted that, the concrete operations mode that water and ethanol alternately wash, with reference to the mode of washing in conventional molybdenum bisuphide production procedure, is not specifically limited at this; The object of the oleic acid that centrifugal segregation is unnecessary is, fully adsorbs oleic acid on guarantee molybdenum bisuphide surface, so that when forming amorphous carbon coating layer, avoids unnecessary amorphous carbon to generate, and the oleic acid of recovery also can continue to use; In addition, the key of the application forms the coated spherical molybdenum bisuphide composite material of agraphitic carbon, in follow-up application, such as prepare negative material time, its following process is determined according to concrete working condition or production object, is not specifically limited at this.
Preferably, in step (1), the mol ratio of sodium molybdate and Cys is 1:4-1:16.It should be noted that, the amount ratio of sodium molybdate and Cys, be as the criterion to generate molybdenum bisuphide to greatest extent, that is, be as the criterion with the chemical dosage ratio that it participates in reaction, in conjunction with concrete working condition and the object of the application, the application is preferred, adopts the mol ratio of sodium molybdate and Cys to be that the amount of 1:4-1:16 is reacted.
Preferably, in step (1), the concentration of sodium molybdate is 0.02mol/L-0.1mol/L.It should be noted that the restriction of sodium molybdate concentration is actually the restriction of reaction solution concentration, be appreciated that sodium molybdate and Cys need both fully to mix when reacting, concentration is too low, output is also low, affects production efficiency, and concentration is too high, is unfavorable for that reaction is carried out; Therefore, the application preferably adopts the concentration of sodium molybdate to be that 0.02mol/L-0.1mol/L reacts.
Preferably, in step (1), reaction temperature is 180-240 DEG C.It should be noted that, reaction temperature refers to the temperature of sodium molybdate and Cys hydro-thermal reaction, and the application preferably adopts 180-240 DEG C, that is, reacts 12 hours at 180-240 DEG C.
Preferably, in step (2), the weight ratio of molybdenum bisuphide and oleic acid is 1:20-1:100.It should be noted that, the effect of oleic acid is that molybdenum bisuphide is sufficiently soaked, and then, forms amorphous carbon on molybdenum bisuphide surface; As long as be appreciated that the consumption of oleic acid can by molybdenum bisuphide immersion cmpletely; The application preferably adopts the weight ratio of molybdenum bisuphide and oleic acid to be 1:20 to 1:100.
Spherical molybdenum bisuphide composite material prepared by the preparation method that the another side of the application also discloses the application, in this composite material, molybdenum bisuphide is spherical, and its Surface coating has amorphous carbon.
It should be noted that, the spherical molybdenum bisuphide composite material of the application is compared with existing molybdenum bisuphide/graphene composite material, there is essential distinction in microstructure, therefore, both are when using as cell negative electrode material, no matter be Lithium-ion embeding mode, or conductivity, tap density etc. are all different.
Preferably, amorphous carbon accounts for the 6%-14% of total weight.It should be noted that, the Main Function of amorphous carbon plays conductivity, to make up the defect of molybdenum bisuphide poorly conductive, therefore, as long as can be complete by molybdenum bisuphide parcel wherein; In the application, consider the composite factor such as specific capacity and conductivity, preferably, make the amorphous carbon of coated molybdenum bisuphide account for the 6%-14% of total weight.In addition, the content of amorphous carbon can be regulated by carburizing temperature, oleic acid under the high temperature conditions, carbonization can form amorphous carbon, but temperature is too high, the content of carbon can be lower, contrary to meeting carbonization and requiring, at lower temperature, the comparision contents of carbon is high, and gas generated in carbonisation under this and different temperatures have relation.
In addition, the application uses Shortcomings for existing molybdenum bisuphide as lithium ion battery negative material and studies, therefore, the application in lithium ion battery negative material prepared by the spherical molybdenum bisuphide composite material that the application further provides the application.It should be noted that, in a kind of implementation of the application, spherical molybdenum bisuphide composite material the application prepared and conventional conductive agent, together with binding agent, are prepared into negative material for lithium ion battery.Wherein, conductive agent is preferably acetylene black, the preferred PVdF of binding agent.
Therefore, the one side again of the application discloses a kind of negative material for lithium ion battery, the spherical molybdenum bisuphide composite material containing the application in this negative material.
Further, in a kind of implementation of the application, the negative material of the spherical molybdenum bisuphide composite material containing the application is made lithium ion battery; Therefore, the one side again of the application discloses a kind of lithium ion battery made by negative material of the spherical molybdenum bisuphide composite material containing the application.
Owing to adopting above technical scheme, the beneficial effect of the application is:
The preparation method of the application utilizes oleic acid to adsorb crystal face annealing and forms agraphitic carbon, and at spherical molybdenum disulfide nano ball Surface coating amorphous carbon layer prepared by hydro thermal method, preparation method is simple, easy to operate.Further, the spherical molybdenum bisuphide composite material that the agraphitic carbon prepared by the preparation method of the application is coated, uses as battery cathode and has that capacity is high, good cycling stability, rate capability high.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the spherical molybdenum disulfide nano ball composite material that in the embodiment of the present application, agraphitic carbon is coated;
Fig. 2 is the high power transmission electron microscope picture of the spherical molybdenum disulfide nano ball composite material that in the embodiment of the present application, agraphitic carbon is coated;
Fig. 3 adopts the spherical molybdenum bisuphide composite material of the application as the charging and discharging curve of the button cell of negative material in the embodiment of the present application;
Fig. 4 adopts the spherical molybdenum bisuphide composite material of the application as the cycle characteristics curve chart of the button cell of negative material in the embodiment of the present application.
Embodiment
Amorphous carbon is as a kind of special defect grapheme material, be rarely used in composite material, the creationary feature utilizing oleic acid annealing to form amorphous carbon of the application, in advance oleic acid is attached to molybdenum bisuphide surface uniformly, anneal again, form the spherical molybdenum disulfide nano ball composite material that amorphous carbon is coated.Composite material prepared by the application, not only have good specific capacity, and conductivity is good; Be made into lithium ion battery negative material, have that capacity is high, good cycling stability, rate capability high.
It should be noted that, spherical molybdenum disulfide nano ball prepared by the application, its surface is in flower-like structure; As shown in Figure 1, whole molybdenum bisuphide is spherical, and the surface of spherical molybdenum disulfide is flower-like structure; This has benefited from the method that sodium molybdate that the application adopts and Cys hydro-thermal prepare molybdenum bisuphide.The molybdenum disulfide nano ball of flower-shaped surface texture is absorption oleic acid, forms amorphous carbon coating layer and provides convenience.
Below by specific embodiments and the drawings, the application is described in further detail.Following examples are only further described the application, should not be construed as the restriction to the application.
Embodiment one
This example is with sodium molybdate and Cys for raw material, and adopt hydro thermal method to prepare molybdenum bisuphide, the preparation method of the spherical molybdenum bisuphide composite material of this example is as follows:
(1) respectively the Cys of the sodium molybdate aqueous solution of 20ml 0.04mol/L and 20ml 0.16mol/L is mixed, be transferred in the polytetrafluoro container of 50 milliliters, and be fixed in stainless reactor, then with baking oven directly at 220 DEG C, heat 12 hours, when the temperature of question response still is reduced to 25 DEG C naturally, obtained reactant is washed 3 times successively with water and ethanol respectively, by the sample after washing in 70 DEG C of baking ovens dry 5 hours, obtain spherical molybdenum disulfide nano ball;
(2) spherical molybdenum disulfide nano ball prepared by step (1) is mixed according to weight ratio 1:20 with oleic acid, ultrasonic mixing 2 hours, centrifugally remove unnecessary oleic acid, obtain the molybdenum bisuphide of adsorbed oil acid molecule;
(3) the 400 DEG C of heating 2 hours in argon gas of the molybdenum bisuphide of abundant adsorbed oil acid molecule step (2) obtained, namely obtain the spherical molybdenum bisuphide composite material that the agraphitic carbon of this example is coated.
Through measuring, in the composite material of this example, agraphitic carbon content accounts for 13.9% of the coated spherical molybdenum bisuphide composite material total weight of agraphitic carbon.
Adopt ESEM to observe composite material prepared by this example, as depicted in figs. 1 and 2, Fig. 1 is the scanning electron microscope (SEM) photograph of the coated spherical molybdenum bisuphide of agraphitic carbon of this example preparation to result, and Fig. 2 is high power transmission electron microscope picture.As shown in Figure 1, the diameter of the coated molybdenum disulfide nano ball of agraphitic carbon of this example is 500 ran, even particle size distribution, and its nanometer sheet thickness is about 5-8 nanometer; As shown in Figure 2, agraphitic carbon is about 1-2 layer.
The coated spherical molybdenum bisuphide composite material of agraphitic carbon prepared by this example is made lithium ion battery negative material, and adopts button cell to test its chemical property.In the lithium ion battery negative material of this example, conductive agent adopts acetylene black, and binding agent adopts PVdF, and molybdenum bisuphide composite material: acetylene black: PVdF mixes according to the ratio of weight ratio 90wt.%: 5wt.%: 5wt.%, coats on Copper Foil.In button cell, electrolyte adopts the LiPF6/EC-DEC-DMC (1: 1: 1, w/w) of 1mol/L.Carry out charged/discharged with 100mA/g respectively, potential range is 0 ~ 3.0V.After tested, when discharging with the current charges of 100mA/g, within the 1st week, charge specific capacity can reach 1289mAh/g, and after 100 circulations, discharge capacity is 842mAh/g.Fig. 3, Fig. 4 are respectively charging and discharging curve, the cycle characteristics curve of the difference circulation of the coated spherical molybdenum bisuphide of agraphitic carbon.
Embodiment two
This example mixes with the Cys of the 0.32mol/L of the sodium molybdate aqueous solution of the 0.2mol/L of 20ml and 20ml prepares molybdenum bisuphide, and all the other steps and condition are all identical with embodiment one.
Adopt ESEM to observe composite material prepared by this example, result shows, and the diameter of the coated molybdenum disulfide nano ball of agraphitic carbon of this example is 350 ran, and even particle size distribution, its nanometer sheet thickness is about 5-8 nanometer.Through measuring, in the composite material of this example, agraphitic carbon content accounts for 13.6% of the coated spherical molybdenum bisuphide composite material total weight of agraphitic carbon.
This example adopts the identical method of embodiment one to prepare negative material, and its chemical property tested by the same button cell that adopts, and the preparation method of button cell is all identical with embodiment one with method of testing.Test result shows, and when discharging with the current charges of 100mA/g, within the 1st week, charge specific capacity can reach 1156mAh/g, and after 100 circulations, discharge capacity is 870mAh/g.。
Embodiment three
This example mixes with the Cys of the 0.16mol/L of the sodium molybdate aqueous solution of the 0.1mol/L of 20ml and 20ml prepares molybdenum bisuphide, and baking oven is directly at 240 DEG C, heat 12 hours, that is, hydrothermal temperature is 240 DEG C, and all the other steps and condition are all identical with embodiment one.
Adopt ESEM to observe composite material prepared by this example, result shows, and the diameter of the coated molybdenum disulfide nano ball of agraphitic carbon of this example is 400 ran, and even particle size distribution, its nanometer sheet thickness is about 5-8 nanometer.Through measuring, in the composite material of this example, agraphitic carbon content accounts for 13.7% of the coated spherical molybdenum bisuphide composite material total weight of agraphitic carbon.
This example adopts the identical method of embodiment one to prepare negative material, and its chemical property tested by the same button cell that adopts, and the preparation method of button cell is all identical with embodiment one with method of testing.Test result shows, and when discharging with the current charges of 100mA/g, within the 1st week, charge specific capacity can reach 1085mAh/g, and after 100 circulations, discharge capacity is 857mAh/g.
Embodiment four
This example mixes with the Cys of the 0.16mol/L of the sodium molybdate aqueous solution of the 0.04mol/L of 20ml and 20ml prepares molybdenum bisuphide, and baking oven is directly at 180 DEG C, heat 12 hours, that is, hydrothermal temperature is 180 DEG C, and all the other steps and condition are all identical with embodiment one.
Adopt ESEM to observe composite material prepared by this example, result shows, and the diameter of the coated molybdenum disulfide nano ball of agraphitic carbon of this example is 350 ran, and even particle size distribution, its nanometer sheet thickness is about 5-8 nanometer.Through measuring, in the composite material of this example, agraphitic carbon content accounts for 13.5% of the coated spherical molybdenum bisuphide composite material total weight of agraphitic carbon.
This example adopts the identical method of embodiment one to prepare negative material, difference is, molybdenum bisuphide composite material: acetylene black: PVdF mixes according to the ratio of weight ratio 80wt.%: 10wt.%: 10wt.%, coats on Copper Foil, and all the other are identical with embodiment one.Its chemical property tested by same employing button cell, and the preparation method of button cell is all identical with embodiment one with method of testing.Test result shows, and when discharging with the current charges of 100mA/g, within the 1st week, charge specific capacity can reach 1205mAh/g, and after 100 circulations, discharge capacity is 827mAh/g.
Embodiment five
This example mixes with the Cys of the 0.8mol/L of the sodium molybdate aqueous solution of the 0.1mol/L of 20ml and 20ml prepares molybdenum bisuphide, and baking oven is directly at 180 DEG C, heat 12 hours, that is, hydrothermal temperature is 180 DEG C, in step (3), molybdenum bisuphide in argon gas 600 DEG C heating 2 hours, all the other steps and condition are all identical with embodiment one.
Adopt ESEM to observe composite material prepared by this example, result shows, and the diameter of the coated molybdenum disulfide nano ball of agraphitic carbon of this example is 350 ran, and even particle size distribution, its nanometer sheet thickness is about 5-8 nanometer.Through measuring, in the composite material of this example, agraphitic carbon content accounts for 9% of the coated spherical molybdenum bisuphide composite material total weight of agraphitic carbon.
This example adopts the identical method of embodiment one to prepare negative material, difference is, molybdenum bisuphide composite material: acetylene black: PVdF mixes according to the ratio of weight ratio 80wt.%: 10wt.%: 10wt.%, coats on Copper Foil, and all the other are identical with embodiment one.Its chemical property tested by same employing button cell, and the preparation method of button cell is all identical with embodiment one with method of testing.Test result shows, and when discharging with the current charges of 100mA/g, within the 1st week, charge specific capacity can reach 1090mAh/g, and after 100 circulations, discharge capacity is 831mAh/g.
Embodiment six
This example mixes with the Cys of the 0.16mol/L of the sodium molybdate aqueous solution of the 0.04mol/L of 20ml and 20ml prepares molybdenum bisuphide, and in step (3), molybdenum bisuphide in argon gas 1100 DEG C heating 2 hours, all the other steps and condition are all identical with embodiment one.
Adopt ESEM to observe composite material prepared by this example, result shows, and the diameter of the coated molybdenum disulfide nano ball of agraphitic carbon of this example is 450 ran, and even particle size distribution, its nanometer sheet thickness is about 5-8 nanometer.Through measuring, in the composite material of this example, agraphitic carbon content accounts for 6.1% of the coated spherical molybdenum bisuphide composite material total weight of agraphitic carbon.
This example adopts the identical method of embodiment one to prepare negative material, difference is, molybdenum bisuphide composite material: acetylene black: PVdF mixes according to the ratio of weight ratio 80wt.%: 10wt.%: 10wt.%, coats on Copper Foil, and all the other are identical with embodiment one.Its chemical property tested by same employing button cell, and the preparation method of button cell is all identical with embodiment one with method of testing.Test result shows, and when discharging with the current charges of 100mA/g, within the 1st week, charge specific capacity can reach 1093mAh/g, and after 100 circulations, discharge capacity is 862mAh/g.
Embodiment seven
This example mixes with the Cys of the 0.16mol/L of the sodium molybdate aqueous solution of the 0.04mol/L of 20ml and 20ml prepares molybdenum bisuphide, and in step (3), molybdenum bisuphide in argon gas 800 DEG C heating 2 hours, all the other steps and condition are all identical with embodiment one.
Adopt ESEM to observe composite material prepared by this example, result shows, and the diameter of the coated molybdenum disulfide nano ball of agraphitic carbon of this example is 350 ran, and even particle size distribution, its nanometer sheet thickness is about 5-8 nanometer.Through measuring, in the composite material of this example, agraphitic carbon content accounts for 8.9% of the coated spherical molybdenum bisuphide composite material total weight of agraphitic carbon.
This example adopts the identical method of embodiment one to prepare negative material, difference is, molybdenum bisuphide composite material: acetylene black: PVdF mixes according to the ratio of weight ratio 80wt.%: 10wt.%: 10wt.%, coats on Copper Foil, and all the other are identical with embodiment one.Its chemical property tested by same employing button cell, and the preparation method of button cell is all identical with embodiment one with method of testing.Test result shows, and when discharging with the current charges of 100mA/g, within the 1st week, charge specific capacity can reach 1151mAh/g, and after 100 circulations, discharge capacity is 878mAh/g.
Visible according to above embodiment, the coated spherical molybdenum bisuphide composite material of agraphitic carbon of the application uses as lithium ion battery negative material, has that capacity is high, good cycling stability, rate capability high.On the basis of above embodiment, the application also tests the atmosphere of oleic acid annealing, and found that, process can adopt beyond argon gas, and other inert gas, such as nitrogen also may be used for the application.
Above content is the further description done the application in conjunction with concrete execution mode, can not assert that the concrete enforcement of the application is confined to these explanations.For the application person of an ordinary skill in the technical field, under the prerequisite not departing from the application's design, some simple deduction or replace can also be made, all should be considered as the protection range belonging to the application.
Claims (10)
1. a preparation method for spherical molybdenum bisuphide composite material, is characterized in that: described preparation method comprises the following steps,
(1) sodium molybdate and Cys are added in deionized water respectively, mix, add thermal response 8-16 hour, naturally cool, then with water and ethanol alternately washing, obtain the molybdenum disulfide nano ball constructed by nanometer sheet;
(2) the spherical molybdenum bisuphide of step (1) gained is immersed in oleic acid, soaks after 24-72 hour, the oleic acid that centrifugal segregation is unnecessary;
(3) by the molybdenum bisuphide having adsorbed oleic acid molecular of step (2) at 400-1100 DEG C, heat 2-6 hour in nitrogen or argon gas atmosphere, obtain the spherical molybdenum bisuphide composite material that agraphitic carbon is coated.
2. preparation method according to claim 1, is characterized in that: in described step (1), the mol ratio of sodium molybdate and Cys is 1:4-1:16.
3. preparation method according to claim 1, is characterized in that: in described step (1), the concentration of sodium molybdate is 0.02mol/L-0.1mol/L.
4. preparation method according to claim 1, is characterized in that: in described step (1), reaction temperature is 180-240 DEG C.
5. preparation method according to claim 1, is characterized in that: in described step (2), the weight ratio of molybdenum bisuphide and oleic acid is 1:20-1:100.
6. spherical molybdenum bisuphide composite material prepared by the preparation method according to any one of claim 1-5, it is characterized in that: molybdenum bisuphide is spherical, and its Surface coating has amorphous carbon.
7. spherical molybdenum bisuphide composite material according to claim 6, is characterized in that: described amorphous carbon accounts for the 6%-14% of total weight.
8. the application in lithium ion battery negative material prepared by the spherical molybdenum bisuphide composite material according to claim 6 or 7.
9. for a negative material for lithium ion battery, it is characterized in that: containing the spherical molybdenum bisuphide composite material described in claim 6 or 7 in described negative material.
10. one kind adopts the lithium ion battery of negative material according to claim 9.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105098151A (en) * | 2015-06-19 | 2015-11-25 | 上海交通大学 | Molybdenum disulfide-carbon hollow ball hybrid material and preparation method thereof |
| CN105126876A (en) * | 2015-09-07 | 2015-12-09 | 复旦大学 | Flowerlike carbon-loaded MoS<2> nano-particle composite 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 |
| CN106362775A (en) * | 2016-08-10 | 2017-02-01 | 西北工业大学 | Molybdenum sulfide-based nano-material for high-efficiency photocatalytic preparation of hydrogen and preparation method thereof |
| 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 |
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| CN111204808A (en) * | 2020-01-10 | 2020-05-29 | 安徽师范大学 | Preparation method of molybdenum disulfide microcapsule, magnesium ion battery positive electrode and magnesium ion battery |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105098151A (en) * | 2015-06-19 | 2015-11-25 | 上海交通大学 | Molybdenum disulfide-carbon hollow ball hybrid material and preparation method thereof |
| CN105126876A (en) * | 2015-09-07 | 2015-12-09 | 复旦大学 | Flowerlike carbon-loaded MoS<2> nano-particle composite 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 |
| CN106362775A (en) * | 2016-08-10 | 2017-02-01 | 西北工业大学 | Molybdenum sulfide-based nano-material for high-efficiency photocatalytic preparation of hydrogen and preparation method thereof |
| 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 |
| CN106876702A (en) * | 2017-02-08 | 2017-06-20 | 大连理工大学 | A kind of sodium-ion battery negative pole coal tar pitch resin base amorphous carbon coats the preparation method and application of few layer molybdenum disulfide nano box |
| 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 |
| CN111204808A (en) * | 2020-01-10 | 2020-05-29 | 安徽师范大学 | Preparation method of molybdenum disulfide microcapsule, magnesium ion battery positive electrode and magnesium ion battery |
| 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 |
| CN111900408A (en) * | 2020-08-04 | 2020-11-06 | 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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