CN104466105A - Molybdenum disulfide/polyaniline composite material, preparation method thereof and lithium ion battery - Google Patents
Molybdenum disulfide/polyaniline composite material, preparation method thereof and lithium ion battery Download PDFInfo
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- CN104466105A CN104466105A CN201410638073.3A CN201410638073A CN104466105A CN 104466105 A CN104466105 A CN 104466105A CN 201410638073 A CN201410638073 A CN 201410638073A CN 104466105 A CN104466105 A CN 104466105A
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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
- 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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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/137—Electrodes based on electro-active polymers
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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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
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- 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 provides a molybdenum disulfide/polyaniline composite material, a preparation method thereof, a lithium ion battery cathode and a lithium ion battery. The preparation method of the molybdenum disulfide/polyaniline composite material comprises the steps of preparing polyaniline dispersed with molybdate, performing ahydrothermal reaction on polyaniline dispersed with molybdate and a sulphur source, and the like. The molybdenum disulfide/polyaniline composite material prepared by the preparation method of the molybdenum disulfide/polyaniline composite material is steady in structure and good in conductivity, when the molybdenum disulfide/polyaniline composite material taken as a lithium ion battery negative electrode material is applied to the lithium ion battery, a device is endowed with excellent rate capability and circulatory stability capability, and the lithium storage capacity is high.
Description
Technical field
The invention belongs to technical field of lithium batteries, be specifically related to a kind of molybdenum bisuphide/polyaniline composite material and preparation method thereof, lithium ion battery negative, lithium ion battery.
Background technology
Energy density is high, output voltage is high owing to having for lithium ion battery, memory-less effect and the advantage such as environmental pollution is little, obtain applying more and more widely, not only can as the main power source of various mobile electronic device, and having very large application prospect in fields such as the energy storage devices as new forms of energy such as electric powered motor power supplys, the life for people provides countless facility.And along with growth in the living standard, people pay close attention to resource, environment, security problems more, therefore, lithium ion battery more and more can come into one's own and have more wide application.
Lithium ion battery mainly comprises important several parts such as positive pole, negative pole and electrolyte.Wherein, the electrode material of lithium ion battery is for improving the chemical property of battery and the aspect such as to reduce costs most important.Wherein, for lithium ion battery negative, negative material commercial is at present mainly graphite type material, and it has the advantages such as embedding lithium plateau potential is low, structural stability good, electrochemical cycle stability is good.But the theoretical capacity of graphite itself is lower, only has 372mAh/g, therefore, prepare high performance negative material and become the focus of Study on Li-ion batteries in recent years.
Molybdenum bisuphide, as the typical two-dimensional layer transient metal sulfide of one, has the structure similar with Graphene, the compound with sandwich structure that it is made up of S-Mo-S.Wherein intermediate layer is Mo atomic layer, is two-layerly up and down S atomic layer, and is combined by strong covalent bond in layer, interlayer is then combined by Van der Waals force.This layer structure is conducive to Lithium-ion embeding and deviates from, and its reversible specific capacity reaches ~ 900mAh/g.Although molybdenum bisuphide has good lithium ion battery applications prospect, the electrons/ions conductivity of itself is lower, and it serious volumetric expansion occurs in removal lithium embedded process makes its cyclical stability poor, limits its application.
Polyaniline, as the typical conducting polymer of one, because it has the redox performance of good reversible electrochemical, the reversible character of doping/dedoping and conductivity higher at ambient temperature, has good chemical property.In the application of lithium ion battery, polyaniline not only can play and improve the effect of conductivity, and can the stability of enhanced activity material.Therefore, if molybdenum bisuphide is combined formation composite material with polyaniline, will obtain higher capacity and good circulation stability, this is also for the development of new type lithium ion battery electrode material provides Research foundation.
Therefore, people is had to prepare the defect of molybdenum bisuphide and the compound of polyaniline for by the defect of molybdenum bisuphide and the advantage of polyaniline at present.
Particularly, as current disclosed a kind of polyaniline and molybdenum disulfide hybrid composite material, its with molybdenum bisuphide powder for raw material, adopt chemical graft process to prepare the suspension of class Graphene molybdenum bisuphide, add aniline monomer wherein, oxidant, organic acid dopant adopt the method for in-situ emulsion polymerization to prepare polyaniline/molybdenum disulfide hybrid composite material.But find in actual production process, there is the shortcomings such as molybdenum bisuphide lamella size, the thickness prepared is uncontrollable in the preparation method of this polyaniline and molybdenum disulfide hybrid composite material, as being applied in lithium ion battery, then still effectively can not improve the electro-chemical activity of molybdenum bisuphide.
Current disclosed another kind has the molybdenum bisuphide/polyaniline nano-line of hierarchy, and the preparation method of this material is: first prepare Mo
3o
10(C
6h
5nH
3)
2h
2o nano wire, then grow polyaniline by the method for chemical polymerization, finally at 200 DEG C, hydro-thermal reaction 48h obtains end product.This composite material improves electronics and the ionic conductivity of molybdenum bisuphide, and lithium ion battery chemical property increases.But find that the method preparation technology of the molybdenum bisuphide/polyaniline nano-line of this hierarchy is loaded down with trivial details, product molybdenum bisuphide/polyaniline nano-line high rate performance and cyclical stability still undesirable, still need to be improved further.
Current disclosed another kind has the molybdenum bisuphide/polyaniline composite material of three-dimensional flower-shaped hierarchy, the preparation method of this material is as follows: first with aniline, perchloric acid and ammonium persulfate for raw material generates polyaniline by chemical oxidising polymerisation, then polyaniline, molybdenum trioxide, potassium rhodanate three are mixed in water, at 210 DEG C, hydro-thermal reaction 24h obtains end product.This material has higher specific capacity and good cyclical stability as lithium ion battery negative material.But the method adopts synthesis material potassium rhodanate, this material is met acid and is discharged high toxicity gas, and like this to workman Yi Zaocheng actual bodily harm, to environment, the cost being difficult to suitability for industrialized production or suitability for industrialized production is too high.
Summary of the invention
The object of the invention is to the above-mentioned deficiency overcoming prior art, a kind of molybdenum bisuphide/polyaniline composite material and preparation method thereof is provided, be intended to solve existing molybdenum bisuphide/polyaniline material high rate performance and the undesirable technical problem of cyclical stability.
Another object of the present invention is to provide a kind of Stability Analysis of Structures, the lithium ion battery negative of high rate performance and cyclical stability excellence and lithium ion battery.
In order to realize foregoing invention object, the technical scheme of the embodiment of the present invention is as follows:
A preparation method for molybdenum bisuphide/polyaniline composite material, comprises the steps:
At 0 ~ 50 DEG C, carrying out chemical oxidising polymerisation reaction containing adding after molybdate carries out mixing treatment in aniline reaction thing mixed system to what prepare polyaniline, obtaining the polyaniline being dispersed with molybdate; Again
In the reacted reaction system of described chemical oxidising polymerisation, add sulphur source, and at 180 ~ 240 DEG C, carry out hydro-thermal reaction after carrying out mixing treatment obtain molybdenum bisuphide/polyaniline black product; By filtration, washing, dry process.
And a kind of molybdenum bisuphide/polyaniline composite material, described molybdenum bisuphide/polyaniline composite material is prepared by above-mentioned molybdenum bisuphide/polyaniline composite material preparation method.
And, a kind of lithium ion battery negative, comprise collector and be combined in the active layer containing negative material on described collector, described negative material is molybdenum bisuphide/polyaniline composite material that above-mentioned molybdenum bisuphide/polyaniline composite material preparation method prepares.
And a kind of lithium ion battery, described lithium ion battery comprises above-mentioned lithium ion battery negative.
Compared with prior art, molybdate is first dissolved in the reactant system of polyaniline by the preparation method of above-mentioned molybdenum bisuphide/polyaniline composite material, makes in polymerization process, and molybdate is dispersed in along with the generation of polyaniline in polyaniline molecule structure.In hydrothermal reaction process, sulphur source and the molybdate be dispersed in polyaniline molecule structure react, thus make the molybdenum bisuphide generated be dispersed in polyaniline, form molybdenum bisuphide/polyaniline composite material.
Therefore, the molybdenum bisuphide/polyaniline composite material Stability Analysis of Structures obtained by the preparation method of above-mentioned molybdenum bisuphide/polyaniline composite material, has good electrons/ions conductivity.
Above-mentioned lithium ion battery negative and the lithium ion battery containing this negative pole are due to containing above-mentioned molybdenum bisuphide/polyaniline composite material, therefore, in the course of the work, this lithium ion battery negative and lithium ion battery lithium ion battery high rate performance and cyclical stability excellent, and lithium storage content is high.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is embodiment of the present invention molybdenum bisuphide/polyaniline composite material preparation method flow chart;
The scanning electron microscope (SEM) photograph of molybdenum bisuphide/polyaniline composite material that Fig. 2 provides for the embodiment of the present invention 1;
The X-ray diffraction spectrogram of molybdenum bisuphide/polyaniline composite material that Fig. 3 provides for the embodiment of the present invention 1;
The lithium ion battery high rate performance resolution chart of molybdenum bisuphide/polyaniline composite material that Fig. 4 provides for the employing embodiment of the present invention 1;
The cycle performance of lithium ion battery resolution chart of molybdenum bisuphide/polyaniline composite material that Fig. 5 provides for the employing embodiment of the present invention 1.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Example of the present invention provides a kind of Environmental Safety, and can prepare conduct electricity very well, the molybdenum bisuphide/polyaniline composite material preparation method of high rate performance and cyclical stability excellence.This molybdenum bisuphide/polyaniline composite material preparation method technological process refers to Fig. 1, and it comprises the steps:
Step S01. preparation is dispersed with the polyaniline of molybdate:
At 0 ~ 50 DEG C, carrying out chemical oxidising polymerisation reaction containing adding after molybdate dissolves in aniline reaction thing mixed system to what prepare polyaniline, obtaining the polyaniline being dispersed with molybdate.
The polyaniline and sulphur source that are dispersed with molybdate are carried out hydro-thermal reaction by step S02.:
In the reacted reaction system of described chemical oxidising polymerisation, add sulphur source, and at 180 ~ 240 DEG C, carry out hydro-thermal reaction after carrying out mixing treatment obtain molybdenum bisuphide/polyaniline black product; By filtration, washing, dry process.
Particularly, in above-mentioned steps S01, at 0 ~ 50 DEG C, carry out chemical oxidising polymerisation course of reaction containing aniline reaction thing mixed system, this reactant aniline monomer meeting polymerization reaction take place, thus generate polyaniline.And molybdate is dissolved in advance this containing in aniline reaction thing mixed system, making this molybdate can be dispersed in this should containing in aniline reaction thing mixed system, like this, when in chemical oxidising polymerisation course of reaction, this molybdenum acid ion can be dispersed on polyaniline and form intermediate product.
In one embodiment, this molybdate amount joined containing aniline reaction thing mixed system controls in the mol ratio of described molybdate and described aniline is (1 ~ 3): 1.By the control to molybdate addition, realize molybdenum acid ion amount in oxidative polymerization product polyaniline, and the final ratio controlling molybdenum bisuphide.In certain embodiments, the mol ratio of this molybdate and described aniline can be 1:1,1.5:1,2:1,2.5:1,3:1 etc.
In another embodiment, this molybdate selects at least one in the molybdate of sodium molybdate, ammonium molybdate, potassium molybdate, calcium molybdate, magnesium molybdate and First Series transition metal wherein, and First Series transition metal is selected as Cr, Mn, Fe, Co, Ni, Cu and Zn.This molybdate selected can keep the stability of molybdenum acid ion in chemical oxidising polymerisation course of reaction, simultaneously the generation of p-poly-phenyl amine can not cause adverse effect.
On the basis of the various embodiments described above, what this prepared polyaniline can be the popular response thing mixed system preparing polyaniline containing aniline reaction thing mixed system.In order to ensure the stability of molybdenum acid ion, in one embodiment, this prepares the comprising watery hydrochloric acid, ammonium persulfate and aniline answer thing containing aniline reaction thing mixed system of polyaniline, and described reactant is soluble in water.In a further embodiment, the mol ratio of this aniline and ammonium persulfate is 1:(0.8 ~ 1.2).In certain embodiments, the mol ratio of this aniline and ammonium persulfate is 1:0.8,1:0.9,1:1,1:1.1,1:1.2 etc.
In other words, in this step S01, the solvent of chemical oxidising polymerisation reaction preferably uses water.In one embodiment, should be containing aniline reaction thing mixed system concentration: aniline is 0.01 ~ 1mol/L in the concentration containing aniline reaction thing mixed system.
In above-mentioned steps S02, sulphur source adds directly in the reacted mixed liquor of chemical oxidising polymerisation in step S01.In one embodiment, the mol ratio that the amount that this sulphur source adds controls the molybdate added in described sulphur source and step S01 is 1:0.5 ~ 3.In certain embodiments, the mol ratio of this sulphur source and molybdate is 1:0.5,1:0.8,1:1,1:1.2,1:1.5,1:1.8,1:2,1:2.2,1:2.5,1:2.8,1:3 etc.The addition controlling this sulphur source makes the molybdate that contains in the polyaniline generated in step 1 and sulphur source fully react thus generate molybdenum bisuphide.
In one embodiment, this sulphur source selects described sulphur source to select at least one in thiocarbamide, cysteine, thioacetamide, mercaptan, thioether, thiophenol.This sulphur source in hydrothermal reaction process can effectively and molybdate react and generate molybdenum bisuphide, can not toxic gas be broken down into simultaneously, make preparation method's safety and environmental protection of above-mentioned molybdenum bisuphide/polyaniline composite material.
On the embodiment basis of above-mentioned each hydro-thermal reaction, the reaction temperature of this hydro-thermal reaction controls at 180 ~ 240 DEG C, and the reaction time controls at 12 ~ 48h.By hydrothermal temperature and the control of time, make the molybdenum bisuphide/polyaniline composite material generated on the basis with superior electrical conductivity energy and reversible specific capacity, structure is more stable, thus gives high rate performance and the stable circulation performance of its excellence.
Conventional mode can be adopted to carry out, as directly adopted filtration or centrifugal treating etc. until carrying out Separation of Solid and Liquid process to the mixture after hydro-thermal reaction after hydro-thermal reaction.Filter residue is collected after this Separation of Solid and Liquid process.To remove reactant remaining in filter residue or other accessory substances to residue washing process.As can the mode carrying out washing treatment such as washing be adopted.
To remove cleaning solvent to the object of drying process of the filter residue after washing, therefore, in one embodiment, its can at 0 ~ 80 DEG C vacuum drying treatment.
From the above, molybdate is first dissolved in the reactant system of polyaniline by the preparation method of above-mentioned molybdenum bisuphide/polyaniline composite negative pole material, and make in polymerization process, molybdate is dispersed in polyaniline structure along with the generation of polyaniline.In hydrothermal reaction process, sulphur source and the molybdate be dispersed in polyaniline structure react, thus make the molybdenum bisuphide generated be dispersed in polyaniline, form Stability Analysis of Structures, good conductivity, there is the molybdenum bisuphide/polyaniline composite material of the chemical properties such as excellent high rate performance and cyclical stability.In the method, effectively can pass through Controlling Technology parameter, the amount added as molybdate, sulphur source and hydrothermal reaction condition etc., effective realization control effectively to the content of molybdenum bisuphide in embodiment of the present invention molybdenum bisuphide/polyaniline composite material and crystal structure, thus effectively improves the Stability Analysis of Structures performance of molybdenum bisuphide/polyaniline composite material and electric conductivity and high rate performance, cyclical stability.
In addition, above-mentioned molybdenum bisuphide/polyaniline composite material preparation method is by selecting sulphur source and molybdate, realize the control to fail safe in molybdenum bisuphide/polyaniline composite material stability preparation method process, make above-mentioned molybdenum bisuphide/polyaniline composite material preparation method safety and environmental protection, and it is economical, be suitable for industrial production, effectively reduce production cost.
Correspondingly, on the basis of above-mentioned molybdenum bisuphide/polyaniline composite material preparation method, the embodiment of the present invention additionally provides a kind of molybdenum bisuphide/polyaniline composite material.This molybdenum bisuphide/polyaniline composite material asks that from above described molybdenum bisuphide/polyaniline composite material preparation method prepares.
In order to the stability of the electric conductivity and structure that improve molybdenum bisuphide/polyaniline composite material further, it is made to have superior electrical conductivity energy, high rate performance and cyclical stability, in one embodiment, the pattern of this molybdenum bisuphide/polyaniline composite material is controlled as three-dimensional loose flowers shape laminated structure by said method.Molybdenum disulfide content in molybdenum bisuphide/polyaniline composite material is 1 ~ 50%.
Therefore, above-mentioned molybdenum bisuphide/polyaniline composite material has excellent electric conductivity, high rate performance and cyclical stability.By its preparation method, the pattern of molybdenum bisuphide/polyaniline composite material and molybdenum disulfide content are controlled, to realize optimizing the electric conductivity of molybdenum bisuphide/polyaniline composite material, high rate performance and cyclical stability.
Correspondingly, on the basis of molybdenum bisuphide/polyaniline composite material described above and preparation method thereof, the embodiment of the present invention further provides a kind of lithium ion battery negative.Lithium ion battery negative comprises collector and is combined in the active layer containing negative material on this collector, and wherein, this negative material is molybdenum bisuphide/polyaniline composite material mentioned above; The collector that collector can select this area conventional, as Copper Foil etc.Like this, this lithium ion battery negative is due to containing above-mentioned molybdenum bisuphide/polyaniline composite material, again because this molybdenum bisuphide/polyaniline composite material has excellent electric conductivity, structural stability as above, therefore, in the course of the work, this lithium ion battery negative good cycle, lithium storage content is high.
Correspondingly, at molybdenum bisuphide/polyaniline composite material described above and preparation method thereof with on the basis of lithium ion battery negative, the embodiment of the present invention further provides a kind of lithium ion battery, and this lithium ion battery comprises lithium ion battery negative mentioned above.It is axiomatic that this lithium ion battery also comprises the necessary miscellaneous part of lithium ion battery, because this miscellaneous part is conventional, therefore, miscellaneous part is not repeated at this.
Like this, this lithium ion battery is due to containing above-mentioned lithium ion battery negative, then this lithium ion battery is in discharge and recharge with recycle for a long time in process and have good cycle performance and high rate performance.Therefore, this lithium ion battery can be applied in such as communication equipment, electric automobile, but is not limited only to communication equipment, electric automobile, can also with in other field.
The aspects such as above-mentioned molybdenum bisuphide/polyaniline composite material and preparation method thereof, lithium ion battery negative and lithium ion battery are illustrated below by way of multiple embodiment.
Embodiment 1
A kind of above-mentioned molybdenum bisuphide/polyaniline composite material and preparation method thereof.This molybdenum bisuphide/polyaniline composite material is prepared by following method:
S11. get sodium molybdate 0.121g, aniline 0.2mL joins in 50mL deionized water, add 1M watery hydrochloric acid and adjust about pH to 2, continue in reactant liquor, add ammonium persulfate 0.6g, at 50 DEG C, carry out chemical oxidising polymerisation reaction, reaction time is 6h, obtains blackish green intermediate product;
S12. in the reactant liquor in step S11, add thiocarbamide 0.38g, after mixing, put into hydrothermal reaction kettle, at 200 DEG C, carry out hydro-thermal reaction 24h, obtain molybdenum bisuphide/polyaniline black combination product;
S13. vacuum drying chamber is put into, vacuumize 12h at 60 DEG C by after molybdenum bisuphide described in step S12/polyaniline combination product filtration, washing.
Embodiment 2
A kind of above-mentioned molybdenum bisuphide/polyaniline composite material and preparation method thereof.This molybdenum bisuphide/polyaniline composite material is prepared by following method:
S21. get sodium molybdate 0.121g, aniline 0.4mL joins in 50mL deionized water, add 1M watery hydrochloric acid and adjust about pH to 2, continue in reactant liquor, add ammonium persulfate 1.2g, at 50 DEG C, carry out chemical oxidising polymerisation reaction, reaction time is 6h, obtains blackish green intermediate product;
S22. in the reactant liquor in step S21, add thiocarbamide 0.38g, after mixing, put into hydrothermal reaction kettle, at 200 DEG C, carry out hydro-thermal reaction 12h, obtain molybdenum bisuphide/polyaniline black combination product;
S23. freeze drier is put into, freeze drying 12h by after molybdenum bisuphide described in step S22/polyaniline combination product filtration, washing.
Embodiment 3
A kind of above-mentioned molybdenum bisuphide/polyaniline composite material and preparation method thereof.This molybdenum bisuphide/polyaniline composite material is prepared by following method:
S31. get sodium molybdate 0.121g, aniline 0.2mL joins in 50mL deionized water, add 1M watery hydrochloric acid and adjust about pH to 2, continue in reactant liquor, add ammonium persulfate 0.6g, at 0 DEG C, carry out chemical oxidising polymerisation reaction, reaction time is 6h, obtains blackish green intermediate product;
S32. in the reactant liquor in step S31, add thiocarbamide 0.38g, after mixing, put into hydrothermal reaction kettle, at 200 DEG C, carry out hydro-thermal reaction 12h, obtain molybdenum bisuphide/polyaniline black combination product;
S33. vacuum drying chamber is put into, vacuumize 12h at 60 DEG C by after molybdenum bisuphide described in step S32/polyaniline combination product filtration, washing.
Embodiment 4
A kind of above-mentioned molybdenum bisuphide/polyaniline composite material and preparation method thereof.This molybdenum bisuphide/polyaniline composite material is prepared by following method:
S41. get sodium molybdate 0.121g, aniline 0.2mL joins in 50mL deionized water, add 1M watery hydrochloric acid and adjust about pH to 2, continue in reactant liquor, add ammonium persulfate 0.6g, at 0 DEG C, carry out chemical oxidising polymerisation reaction, reaction time is 6h, obtains blackish green intermediate product;
S42. in the reactant liquor in step S41, add thiocarbamide 0.38g, after mixing, put into hydrothermal reaction kettle, at 180 DEG C, carry out hydro-thermal reaction 12h, obtain molybdenum bisuphide/polyaniline black combination product;
S43. vacuum drying chamber is put into, vacuumize 12h at 80 DEG C by after molybdenum bisuphide described in step S42/polyaniline combination product filtration, washing.
Embodiment 5
A kind of above-mentioned molybdenum bisuphide/polyaniline composite material and preparation method thereof.This molybdenum bisuphide/polyaniline composite material is prepared by following method:
S51. get sodium molybdate 0.121g, aniline 0.2mL joins in 50mL deionized water, add 1M watery hydrochloric acid and adjust about pH to 2, continue in reactant liquor, add ammonium persulfate 0.6g, at 0 DEG C, carry out chemical oxidising polymerisation reaction, reaction time is 6h, obtains blackish green intermediate product;
S52. in the reactant liquor in step S51, add thiocarbamide 0.38g, after mixing, put into hydrothermal reaction kettle, at 220 DEG C, carry out hydro-thermal reaction 12h, obtain molybdenum bisuphide/polyaniline black combination product;
S53. vacuum drying chamber is put into, vacuumize 12h at 80 DEG C by after molybdenum bisuphide described in step S52/polyaniline combination product filtration, washing.
Embodiment 6
A kind of above-mentioned molybdenum bisuphide/polyaniline composite material and preparation method thereof.This molybdenum bisuphide/polyaniline composite material is prepared by following method:
S61. get ammonium molybdate 0.618g, aniline 0.2mL joins in 50mL deionized water, add 1M watery hydrochloric acid and adjust about pH to 2, continue in reactant liquor, add ammonium persulfate 0.6g, at 0 DEG C, carry out chemical oxidising polymerisation reaction, reaction time is 6h, obtains blackish green intermediate product;
S62. in the reactant liquor in step S61, add thiocarbamide 0.38g, after mixing, put into hydrothermal reaction kettle, at 200 DEG C, carry out hydro-thermal reaction 12h, obtain molybdenum bisuphide/polyaniline black combination product;
S63. vacuum drying chamber is put into, vacuumize 12h at 80 DEG C by after molybdenum bisuphide described in step S62/polyaniline combination product filtration, washing.
Embodiment 7
A kind of above-mentioned molybdenum bisuphide/polyaniline composite material and preparation method thereof.This molybdenum bisuphide/polyaniline composite material is prepared by following method:
S71. get ammonium molybdate 0.618g, aniline 0.2mL joins in 50mL deionized water, add 1M watery hydrochloric acid and adjust about pH to 2, continue in reactant liquor, add ammonium persulfate 0.6g, at 0 DEG C, carry out chemical oxidising polymerisation reaction, reaction time is 6h, obtains blackish green intermediate product;
S72. in the reactant liquor in step S71, add cysteine 0.605g, after mixing, put into hydrothermal reaction kettle, at 200 DEG C, carry out hydro-thermal reaction 48h, obtain molybdenum bisuphide/polyaniline black combination product;
S73. vacuum drying chamber is put into, vacuumize 12h at 80 DEG C by after molybdenum bisuphide described in step S72/polyaniline combination product filtration, washing.
Embodiment 8
A kind of above-mentioned molybdenum bisuphide/polyaniline composite material and preparation method thereof.This molybdenum bisuphide/polyaniline composite material is prepared by following method:
S81. get potassium molybdate 0.119g, aniline 0.2mL joins in 50mL deionized water, add 1M watery hydrochloric acid and adjust about pH to 2, continue in reactant liquor, add ammonium persulfate 0.6g, at 0 DEG C, carry out chemical oxidising polymerisation reaction, reaction time is 6h, obtains blackish green intermediate product;
S82. in the reactant liquor in step S81, add thiocarbamide 0.38g, after mixing, put into hydrothermal reaction kettle, at 200 DEG C, carry out hydro-thermal reaction 12h, obtain molybdenum bisuphide/polyaniline black combination product;
S83. vacuum drying chamber is put into, vacuumize 12h at 80 DEG C by after molybdenum bisuphide described in step S82/polyaniline combination product filtration, washing.
Embodiment 9
A kind of above-mentioned molybdenum bisuphide/polyaniline composite material and preparation method thereof.This molybdenum bisuphide/polyaniline composite material is prepared by following method:
S91. get sodium molybdate 0.119g, aniline 0.2mL joins in 50mL deionized water, add 1M watery hydrochloric acid and adjust about pH to 2, continue in reactant liquor, add ammonium persulfate 0.6g, at 0 DEG C, carry out chemical oxidising polymerisation reaction, reaction time is 6h, obtains blackish green intermediate product;
S92. in the reactant liquor in step S91, add thiocarbamide 0.38g, after mixing, put into hydrothermal reaction kettle, at 200 DEG C, carry out hydro-thermal reaction 48h, obtain molybdenum bisuphide/polyaniline black combination product;
S93. vacuum drying chamber is put into, vacuumize 12h at 80 DEG C by after molybdenum bisuphide described in step S92/polyaniline combination product filtration, washing.
Lithium ion battery embodiment
Molybdenum bisuphide/the polyaniline composite material provided in the various embodiments described above lithium ion battery negative preparation method is conveniently prepared into lithium ion battery negative respectively.
According to lithium ion battery customary preparation methods, the lithium ion battery negative utilizing the molybdenum bisuphide/polyaniline composite material provided in the various embodiments described above to prepare is assembled into lithium ion battery respectively.
Performance test:
1. molybdenum bisuphide/polyaniline composite material that prepared by pair above-described embodiment 1 ~ 9 carries out micro-analysis:
Molybdenum bisuphide/polyaniline composite material prepared by above-described embodiment 1 ~ 9 is carried out ESEM and X-ray diffraction analysis.
Wherein, the scanning electron microscope analysis of the molybdenum bisuphide/polyaniline composite material of embodiment 1 preparation as shown in Figure 2.From the picture of Fig. 2, this molybdenum bisuphide/polyaniline composite material presents three-dimensional flowers laminated structure, and structure is more loose.This structure is conducive to the turnover of lithium ion in charge and discharge process, improves its ionic conductivity, thus improves the high rate performance of battery.
The X-ray diffraction result of molybdenum bisuphide/polyaniline composite material prepared by embodiment 1 as shown in Figure 3.As can be seen from this X-ray diffractogram, compared to pure molybdenum bisuphide material, the molybdenum bisuphide characteristic diffraction peak broadening of this molybdenum bisuphide/polyaniline composite material, illustrates that polyaniline is evenly dispersed in composite material, makes material transfer the open structure of amorphous phase to by crystalline phase.This structure is conducive to the turnover of lithium ion in charge and discharge process, improves its ionic conductivity, thus improves the high rate performance of battery.
Molybdenum bisuphide/polyaniline composite negative pole material in molybdenum bisuphide/polyaniline composite negative pole material ESEM prepared by embodiment 2 ~ 9 and X-ray diffraction analysis result and embodiment 1 is similar.
2. be carry out cycle performance and high rate performance test for the various embodiments described above lithium ion battery below, this cycle performance and high rate performance method of testing are conventionally carried out, and record result as follows:
As shown in Figure 4, high rate performance test result as shown in Figure 5 for embodiment 1 cycle performance of lithium ion battery test result.From Fig. 4,5, in embodiment 1 cyclicity of lithium ion battery and high rate performance excellent.
By test, the cycle performance of the lithium ion battery in embodiment 2 ~ 3 is similar to embodiment 1 with high rate performance, all has excellent cyclicity and high rate performance.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a preparation method for molybdenum bisuphide/polyaniline composite material, comprises the steps:
At 0 ~ 50 DEG C, carrying out chemical oxidising polymerisation reaction containing adding after molybdate dissolves in aniline reaction thing mixed system to what prepare polyaniline, obtaining the polyaniline being dispersed with molybdate; In the reacted reaction system of described chemical oxidising polymerisation, add sulphur source again, and at 180 ~ 240 DEG C, carry out hydro-thermal reaction after carrying out mixing treatment obtain molybdenum bisuphide/polyaniline product; By Separation of Solid and Liquid, washing, dry process.
2. the preparation method of molybdenum bisuphide/polyaniline composite material according to claim 1, is characterized in that: it is (1 ~ 3) that the amount that described molybdate adds controls in the mol ratio of described molybdate and described aniline: 1.
3. the preparation method of molybdenum bisuphide/polyaniline composite material according to claim 1, is characterized in that: it is 1:0.5 ~ 3 that the amount that described sulphur source adds controls in the mol ratio of described sulphur source and molybdate.
4., according to the preparation method of the arbitrary described molybdenum bisuphide/polyaniline composite material of claims 1 to 3, it is characterized in that: described molybdate selects at least one in the molybdate of sodium molybdate, ammonium molybdate, potassium molybdate, calcium molybdate, magnesium molybdate, First Series transition metal.
5., according to the preparation method of the arbitrary described molybdenum bisuphide/polyaniline composite material of claims 1 to 3, it is characterized in that: at least one in thiocarbamide, cysteine, thioacetamide, mercaptan, thioether, thiophenol is selected in described sulphur source.
6., according to the preparation method of the arbitrary described molybdenum bisuphide/polyaniline composite material of claims 1 to 3, it is characterized in that: when described hydrothermal temperature is 180 ~ 240 DEG C, the described hydro-thermal reaction time is 12 ~ 48h.
7. the preparation method of the molybdenum bisuphide/polyaniline composite material described in arbitrary according to claims 1 to 3, it is characterized in that: the described aniline reaction thing mixed system that contains preparing polyaniline comprises watery hydrochloric acid, ammonium persulfate and aniline, and described reactant is soluble in water.
8. molybdenum bisuphide/polyaniline composite material, is characterized in that: described molybdenum bisuphide/polyaniline composite material is prepared by the molybdenum bisuphide/polyaniline composite material preparation method as described in as arbitrary in claim 1 ~ 7.
9. a lithium ion battery negative, comprise collector and be combined on described collector containing the active layer of negative material, it is characterized in that: described negative material be as arbitrary in claim 1 ~ 7 as described in molybdenum bisuphide/polyaniline composite material of preparing of molybdenum bisuphide/polyaniline composite material preparation method.
10. a lithium ion battery, is characterized in that, described lithium ion battery comprises lithium ion battery negative according to claim 9.
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