CN104466105B - molybdenum disulfide/polyaniline composite material, preparation method and lithium ion battery - Google Patents
molybdenum disulfide/polyaniline composite material, preparation method and lithium ion battery Download PDFInfo
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- CN104466105B CN104466105B CN201410638073.3A CN201410638073A CN104466105B CN 104466105 B CN104466105 B CN 104466105B CN 201410638073 A CN201410638073 A CN 201410638073A CN 104466105 B CN104466105 B CN 104466105B
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- 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
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Abstract
The present invention provides a kind of molybdenum disulfide/polyaniline composite material and preparation method thereof, negative electrode of lithium ion battery and lithium ion battery.The molybdenum disulfide/polyaniline composite material preparation method includes preparing the polyaniline for being dispersed with molybdate, will be dispersed with the polyaniline of molybdate with sulphur source progress hydro-thermal reaction.Molybdenum disulfide/polyaniline composite material stable structure prepared by the preparation method of molybdenum disulfide/polyaniline composite material of the present invention, conduct electricity very well, when it is applied to lithium ion battery as lithium ion battery negative material, the excellent high rate performance of device and stable circulation performance are assigned, and lithium storage content is high.
Description
Technical field
The invention belongs to technical field of lithium batteries, and in particular to a kind of molybdenum disulfide/polyaniline composite material and its preparation
Method, negative electrode of lithium ion battery, lithium ion battery.
Background technology
Lithium ion battery is small due to having the advantages that high energy density, output voltage height, memory-less effect and environmental pollution,
Have been more and more widely used, act not only as the main power source of various mobile electronic devices, and as electronic vapour
There is very big application prospect in the fields such as the energy storage device of the new energy such as car electrical source of power, for people life provide it is countless just
Profit.And with the improvement of living standards, people focus more on resource, environment, security problems, therefore, lithium ion battery meeting
Increasingly it is taken seriously and has a broader practice.
Lithium ion battery is mainly comprising important several parts such as cathode, anode and electrolyte.Wherein, lithium ion battery
Electrode material is for improving the chemical property of battery and to reduce cost etc. most important.Wherein, for lithium ion battery
For anode, negative material commercial at present is mainly graphite type material, it has, and embedding lithium plateau potential is low, structural stability
Well, the advantages that electrochemical cycle stability is good.But the theoretical capacity of graphite in itself is relatively low, only 372mAh/g, therefore, prepares
Hot spot of the high performance negative material into Study on Li-ion batteries in recent years.
Molybdenum disulfide has the structure similar with graphene as a kind of typical two-dimensional layer transient metal sulfide,
The compound with sandwich structure that it is made of S-Mo-S.Wherein intermediate layer is Mo atomic layers, and upper and lower two layers equal
For S atom layer, layer is interior to be combined by strong covalent bond, and interlayer is then combined by Van der Waals force.This layer structure be conducive to lithium from
Son is embedded and abjection, its reversible specific capacity reach~900mAh/g.Although molybdenum disulfide has good lithium ion battery applications
Prospect, still, the electrons/ions electrical conductivity of itself are relatively low, and serious volumetric expansion occurs in it during removal lithium embedded
So that its cyclical stability is poor, its application is limited.
Polyaniline is as a kind of typical conducting polymer, since it is with the good redox property of reversible electrochemical
Energy, the reversible nature of doping/dedoping and electrical conductivity higher at ambient temperature, have good chemical property.
In the application of lithium ion battery, polyaniline can not only play the role of improving electric conductivity, but also can strengthen active material
Stability.Therefore, if molybdenum disulfide is combined to form composite material with polyaniline, it will obtain higher capacity and good
Cyclical stability, this development also for new type lithium ion battery electrode material provide Research foundation.
Therefore, someone is directed to the defects of molybdenum disulfide and the defects of the advantage of polyaniline has prepared molybdenum disulfide at present
With the compound of polyaniline.
Specifically, such as a kind of presently disclosed polyaniline and molybdenum disulfide hybrid composite material, it is with molybdenum disulfide powder
For raw material, the suspension of class graphene molybdenum disulfide is prepared using chemical graft process, add wherein aniline monomer, oxidant,
Organic acid dopant prepares polyaniline/molybdenum disulfide hybrid composite material using the method for in-situ emulsion polymerization.But
Found in actual production process, the preparation method of the polyaniline and molybdenum disulfide hybrid composite material has the curing prepared
Molybdenum sheet layer size, the shortcomings of thickness is uncontrollable, as being applied in lithium ion battery, then still cannot effectively improve molybdenum disulfide
Electro-chemical activity.
The presently disclosed another molybdenum disulfide/polyaniline nano-line with hierarchy, the preparation method of the material
It is：Mo is prepared first3O10(C6H5NH3)2·H2O nano wires, then polyaniline is grown by the method for chemical polymerization, finally exist
Hydro-thermal reaction 48h obtains final product at 200 DEG C.The composite material improves the electronics and ionic conductivity of molybdenum disulfide, lithium
Ion battery chemical property increases.However, it was found that the method system of molybdenum disulfide/polyaniline nano-line of the hierarchy
Standby technique is cumbersome, and product molybdenum disulfide/polyaniline nano-line high rate performance and cyclical stability are still undesirable, still need into one
Step improves.
The presently disclosed another molybdenum disulfide/polyaniline composite material with three-dimensional flower-shaped hierarchy, the material
Preparation method it is as follows：Polyaniline is generated by chemical oxidising polymerisation using aniline, perchloric acid and ammonium persulfate as raw material first, is connect
And be uniformly mixed polyaniline, molybdenum trioxide, potassium rhodanate three in water, hydro-thermal reaction 24h is finally produced at 210 DEG C
Thing.The material has higher specific capacity and good cyclical stability as lithium ion battery negative material.But the party
Method uses synthesis material potassium rhodanate, which meets acid and discharge high toxicity gas, and actual bodily harm is so easily caused to worker, right
Environment pollutes, it is difficult to which the cost of industrialized production or industrialized production is too high.
The content of the invention
It is an object of the invention to overcome the above-mentioned deficiency of the prior art, there is provided a kind of molybdenum disulfide/polyaniline composite wood
Material and preparation method thereof, it is intended to solve existing molybdenum disulfide/polyaniline material high rate performance and the undesirable skill of cyclical stability
Art problem.
Another object of the present invention is to provide a kind of stable structure, high rate performance and the excellent lithium ion of cyclical stability
Battery cathode and lithium ion battery.
In order to realize foregoing invention purpose, the technical solution of the embodiment of the present invention is as follows：
A kind of preparation method of molybdenum disulfide/polyaniline composite material, includes the following steps：
Molybdate is added into the mixed system of thing containing aniline reaction for prepare polyaniline and carries out mixing treatment after 0~50 DEG C
Lower progress chemical oxidising polymerisation reaction, obtains being dispersed with the polyaniline of molybdate；Again
Add sulphur source in reaction system after being reacted to the chemical oxidising polymerisation, and carry out mixing treatment after 180~
Hydro-thermal reaction is carried out at 240 DEG C and obtains molybdenum disulfide/polyaniline black product；By filtering, washing, drying process.
And a kind of molybdenum disulfide/polyaniline composite material, the molybdenum disulfide/polyaniline composite material is by above-mentioned
Molybdenum disulfide/polyaniline composite material preparation method prepares.
And a kind of negative electrode of lithium ion battery, including collector and be incorporated on the collector and contain negative material
Active layer, the negative material is the curing for preparing of above-mentioned molybdenum disulfide/polyaniline composite material preparation method
Molybdenum/polyaniline composite material.
And a kind of lithium ion battery, the lithium ion battery include above-mentioned negative electrode of lithium ion battery.
Compared with prior art, molybdate is first dissolved in by the preparation method of above-mentioned molybdenum disulfide/polyaniline composite material
In the reactant system of polyaniline so that in polymerization process, molybdate is dispersed in polyphenyl with the generation of polyaniline
In amine molecule structure.In hydrothermal reaction process, sulphur source reacts with the molybdate being dispersed in polyaniline molecule structure, from
And make it that the molybdenum disulfide of generation is dispersed in polyaniline, form molybdenum disulfide/polyaniline composite material.
Therefore, the molybdenum disulfide/polyaniline obtained by the preparation method of above-mentioned molybdenum disulfide/polyaniline composite material is compound
Material structure is stablized, and has good electrons/ions electrical conductivity.
Above-mentioned negative electrode of lithium ion battery and lithium ion battery containing the anode are due to containing above-mentioned molybdenum disulfide/polyaniline
Composite material, therefore, during the work time, the negative electrode of lithium ion battery and lithium ion battery lithium ion battery high rate performance and is followed
Ring excellent in stability, and lithium storage content is high.
Brief description of the drawings
Below in conjunction with accompanying drawings and embodiments, the invention will be further described, in attached drawing：
Fig. 1 is molybdenum disulfide of the embodiment of the present invention/polyaniline composite material preparation method flow chart；
Fig. 2 is the scanning electron microscope (SEM) photograph for molybdenum disulfide/polyaniline composite material that the embodiment of the present invention 1 provides；
Fig. 3 is the X-ray diffraction spectrogram for molybdenum disulfide/polyaniline composite material that the embodiment of the present invention 1 provides；
Fig. 4 is that the lithium ion battery of the molybdenum disulfide/polyaniline composite material provided using the embodiment of the present invention 1 is forthright again
Can test chart；
Fig. 5 is the lithium ion battery cyclicity of the molybdenum disulfide/polyaniline composite material provided using the embodiment of the present invention 1
Can test chart.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, it is right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
Present example provides a kind of Environmental Safety, and can prepare and conduct electricity very well, high rate performance and stable circulation
Excellent molybdenum disulfide/polyaniline composite material the preparation method of property.The molybdenum disulfide/polyaniline composite material preparation method technique
Flow refers to Fig. 1, it includes the following steps：
Step S01. prepares the polyaniline for being dispersed with molybdate：
Into the mixed system of thing containing aniline reaction for prepare polyaniline add molybdate dissolved after at 0~50 DEG C into
Row chemical oxidising polymerisation reacts, and obtains being dispersed with the polyaniline of molybdate.
The polyaniline for being dispersed with molybdate is carried out hydro-thermal reaction by step S02. with sulphur source：
Add sulphur source in reaction system after being reacted to the chemical oxidising polymerisation, and carry out mixing treatment after 180~
Hydro-thermal reaction is carried out at 240 DEG C and obtains molybdenum disulfide/polyaniline black product；By filtering, washing, drying process.
Specifically, in above-mentioned steps S01, the mixed system of thing containing aniline reaction carries out chemical oxidising polymerisation at 0~50 DEG C
Reaction process, which can occur polymerisation, so as to generate polyaniline.And molybdate is dissolved in this in advance
In the mixed system of thing containing aniline reaction so that the molybdate can be dispersed in this, and this contains in aniline reaction thing mixed system,
In this way, when in chemical oxidising polymerisation reaction process, which can be dispersed on polyaniline and form intermediate product.
In one embodiment, the molybdate be added to the mixed system of thing containing aniline reaction amount control the molybdate with
The molar ratio of the aniline is (1~3)：1.By the control to molybdate addition, realize and oxidative polymerization product is gathered
Molybdenum acid ion amount in aniline, and finally control the ratio of molybdenum disulfide.In certain embodiments, the molybdate with it is described
The molar ratio of aniline can be 1：1、1.5：1、2：1、2.5：1、3：1 etc..
In another embodiment, which selects sodium molybdate, ammonium molybdate, potassium molybdate, calcium molybdate, magnesium molybdate and the first system
At least one of molybdate of row transition metal wherein, First Series transition metal select as Cr, Mn, Fe, Co, Ni, Cu and
Zn.The molybdate of the selection can keep the stability of molybdenum acid ion in chemical oxidising polymerisation reaction process, while will not be right
The generation of polyaniline adversely affects.
On the basis of the various embodiments described above, the mixed system of thing containing aniline reaction for preparing polyaniline can be prepare it is poly-
The popular response thing mixed system of aniline.In order to ensure the stability of molybdenum acid ion, in one embodiment, this prepares polyaniline
The mixed system of thing containing aniline reaction answer thing including dilute hydrochloric acid, ammonium persulfate and aniline, and the reactant is soluble in water.Into
In one step embodiment, the molar ratio of the aniline and ammonium persulfate is 1:(0.8~1.2).In certain embodiments, the aniline
Molar ratio with ammonium persulfate is 1:0.8、1:0.9、1:1、1:1.1、1:1.2 wait.
In other words, the solvent that chemical oxidising polymerisation reacts in step S01 preferably uses water.In one embodiment, this contains
Aniline reaction thing mixed system concentration is：Aniline is 0.01~1mol/L in the concentration of the mixed system of thing containing aniline reaction.
In above-mentioned steps S02, sulphur source is added in the mixed liquor directly into step S01 after chemical oxidising polymerisation reaction.
In one embodiment, it is 1 that the amount which adds, which controls the molar ratio of the molybdate added in the sulphur source and step S01,:
0.5~3.In certain embodiments, the sulphur source and the molar ratio of molybdate are 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 of the sulphur source is controlled so that the polyphenyl generated in step 1
The molybdate contained in amine is fully reacted with sulphur source so as to generate molybdenum disulfide.
In one embodiment, which selects the sulphur source to select thiocarbamide, cysteine, thioacetamide, mercaptan, sulphur
At least one of ether, thiophenol.The sulphur source can effectively react generation molybdenum disulfide in hydrothermal reaction process with molybdate, at the same time
Toxic gas will not be broken down into so that the preparation method safety and environmental protection of above-mentioned molybdenum disulfide/polyaniline composite material.
On the basis of the embodiment of above-mentioned each hydro-thermal reaction, the reaction temperature of the hydro-thermal reaction is controlled at 180~240 DEG C,
Reaction time is controlled in 12~48h.Pass through the control of hydrothermal temperature and time so that molybdenum disulfide/polyaniline of generation
Composite material is on the basis of with superior electrical conductivity energy and reversible specific capacity, and structure is more stablized, so that it is excellent to assign its
High rate performance and stable circulation performance.
Conventional side can be used after carrying out solid-liquid separation treatment after hydro-thermal reaction to the mixture after hydro-thermal reaction
Formula carries out, such as directly using filtering or centrifugal treating.Filter residue is collected after the solid-liquid separation treatment.To residue washing processing be for
Remove reactant or other accessory substances remaining in filter residue.Washing mode carrying out washing treatment can such as be used.
The purpose of drying process to the filter residue after washing be in order to remove cleaning solvent, therefore, in one embodiment, its
Can at 0~80 DEG C vacuum drying treatment.
It can be seen from the above, molybdate is first dissolved in by the preparation method of above-mentioned molybdenum disulfide/polyaniline composite negative pole material
In the reactant system of polyaniline so that in polymerization process, molybdate is dispersed in polyphenyl with the generation of polyaniline
In amine structure.In hydrothermal reaction process, sulphur source reacts with the molybdate being dispersed in polyaniline structure, so that raw
Into molybdenum disulfide be dispersed in polyaniline, form stable structure, good conductivity, have excellent high rate performance and the circulation steady
Qualitative molybdenum disulfide/the polyaniline composite material for waiting chemical property.In the method, can effectively by controlling technological parameter,
The amount and hydrothermal reaction condition that such as molybdate, sulphur source add, are effectively realized multiple to molybdenum disulfide of the embodiment of the present invention/polyaniline
The content of molybdenum disulfide and crystal structure control effectively in condensation material, so that it is multiple to effectively improve molybdenum disulfide/polyaniline
The structural stability can and electric conductivity and high rate performance of condensation material, cyclical stability.
In addition, above-mentioned molybdenum disulfide/polyaniline composite material preparation method is realized by the selection to sulphur source and molybdate
Control to security during molybdenum disulfide/polyaniline composite material stability preparation method so that above-mentioned molybdenum disulfide/
Polyaniline composite material preparation method safety and environmental protection, and it is economical, suitable for industrial production, effectively reduce production cost.
Correspondingly, on the basis of above-mentioned molybdenum disulfide/polyaniline composite material preparation method, the embodiment of the present invention also carries
A kind of molybdenum disulfide/polyaniline composite material is supplied.Molybdenum disulfide/the polyaniline composite material asks the curing from above
Molybdenum/polyaniline composite material preparation method prepares.
In order to further improve the stability of the electric conductivity of molybdenum disulfide/polyaniline composite material and structure so that
It is with superior electrical conductivity energy, high rate performance and cyclical stability, in one embodiment, the molybdenum disulfide/polyaniline composite wood
The pattern of material is three-dimensional loose flowers shape laminated structure by above method control.In molybdenum disulfide/polyaniline composite material
Molybdenum disulfide content is 1~50%.
Therefore, above-mentioned molybdenum disulfide/polyaniline composite material has excellent electric conductivity, high rate performance and stable circulation
Property.The pattern and molybdenum disulfide content of molybdenum disulfide/polyaniline composite material are controlled by its preparation method, to realize
Optimize electric conductivity, high rate performance and the cyclical stability of molybdenum disulfide/polyaniline composite material.
Correspondingly, on the basis of molybdenum disulfide/polyaniline composite material described above and preparation method thereof, the present invention
Embodiment further provides a kind of negative electrode of lithium ion battery.Negative electrode of lithium ion battery includes collector and is incorporated in the afflux
The active layer containing negative material on body, wherein, which is molybdenum disulfide described above/polyaniline composite wood
Material；Collector can select collector commonly used in the art, such as copper foil.In this way, the negative electrode of lithium ion battery is due to containing upper
Molybdenum disulfide/polyaniline composite material is stated, and since the molybdenum disulfide/polyaniline composite material is as described above with excellent
Electric conductivity, structural stability, therefore, during the work time, the negative electrode of lithium ion battery good cycle, lithium storage content height.
Correspondingly, born in molybdenum disulfide/polyaniline composite material described above and preparation method thereof and lithium ion battery
On the basis of pole, the embodiment of the present invention further provides a kind of lithium ion battery, which includes described above
Negative electrode of lithium ion battery.It is axiomatic that the lithium ion battery further includes the necessary miscellaneous part of lithium ion battery, due to
The miscellaneous part is conventional, therefore, miscellaneous part is not repeated herein.
In this way, the lithium ion battery is due to containing above-mentioned negative electrode of lithium ion battery, then the lithium ion battery in discharge and recharge and
There is good cycle performance and high rate performance during recycling for a long time.Therefore, which can be such as logical
Applied in letter equipment, electric automobile, but be not limited only to communication equipment, electric automobile, can also used in other field.
Illustrated below by way of multiple embodiments above-mentioned molybdenum disulfide/polyaniline composite material and preparation method thereof,
Negative electrode of lithium ion battery and lithium ion battery etc..
Embodiment 1
A kind of above-mentioned molybdenum disulfide/polyaniline composite material and preparation method thereof.Molybdenum disulfide/the polyaniline composite material
Prepared by following methods：
S11. take sodium molybdate 0.121g, aniline 0.2mL to be added in 50mL deionized waters, add 1M dilute hydrochloric acid tune pH to 2
Left and right, continues to add ammonium persulfate 0.6g into reaction solution, chemical oxidising polymerisation reaction is carried out at 50 DEG C, the reaction time is
6h, obtains blackish green intermediate product；
S12. thiocarbamide 0.38g is added in the reaction solution into step S11, is put into after mixing in hydrothermal reaction kettle,
Hydro-thermal reaction 24h is carried out at 200 DEG C, obtains molybdenum disulfide/polyaniline black combination product；
S13. will be put into after molybdenum disulfide described in step S12/polyaniline combination product filtering, washing in vacuum drying chamber,
12h is dried in vacuo at 60 DEG C.
Embodiment 2
A kind of above-mentioned molybdenum disulfide/polyaniline composite material and preparation method thereof.Molybdenum disulfide/the polyaniline composite material
Prepared by following methods：
S21. take sodium molybdate 0.121g, aniline 0.4mL to be added in 50mL deionized waters, add 1M dilute hydrochloric acid tune pH to 2
Left and right, continues to add ammonium persulfate 1.2g into reaction solution, chemical oxidising polymerisation reaction is carried out at 50 DEG C, the reaction time is
6h, obtains blackish green intermediate product；
S22. thiocarbamide 0.38g is added in the reaction solution into step S21, is put into after mixing in hydrothermal reaction kettle,
Hydro-thermal reaction 12h is carried out at 200 DEG C, obtains molybdenum disulfide/polyaniline black combination product；
S23. will be put into after molybdenum disulfide described in step S22/polyaniline combination product filtering, washing in freeze drier,
It is freeze-dried 12h.
Embodiment 3
A kind of above-mentioned molybdenum disulfide/polyaniline composite material and preparation method thereof.Molybdenum disulfide/the polyaniline composite material
Prepared by following methods：
S31. take sodium molybdate 0.121g, aniline 0.2mL to be added in 50mL deionized waters, add 1M dilute hydrochloric acid tune pH to 2
Left and right, continues to add ammonium persulfate 0.6g into reaction solution, the progress chemical oxidising polymerisation reaction at 0 DEG C, reaction time 6h,
Obtain blackish green intermediate product；
S32. thiocarbamide 0.38g is added in the reaction solution into step S31, is put into after mixing in hydrothermal reaction kettle,
Hydro-thermal reaction 12h is carried out at 200 DEG C, obtains molybdenum disulfide/polyaniline black combination product；
S33. will be put into after molybdenum disulfide described in step S32/polyaniline combination product filtering, washing in vacuum drying chamber,
12h is dried in vacuo at 60 DEG C.
Embodiment 4
A kind of above-mentioned molybdenum disulfide/polyaniline composite material and preparation method thereof.Molybdenum disulfide/the polyaniline composite material
Prepared by following methods：
S41. take sodium molybdate 0.121g, aniline 0.2mL to be added in 50mL deionized waters, add 1M dilute hydrochloric acid tune pH to 2
Left and right, continues to add ammonium persulfate 0.6g into reaction solution, the progress chemical oxidising polymerisation reaction at 0 DEG C, reaction time 6h,
Obtain blackish green intermediate product；
S42. thiocarbamide 0.38g is added in the reaction solution into step S41, is put into after mixing in hydrothermal reaction kettle,
Hydro-thermal reaction 12h is carried out at 180 DEG C, obtains molybdenum disulfide/polyaniline black combination product；
S43. will be put into after molybdenum disulfide described in step S42/polyaniline combination product filtering, washing in vacuum drying chamber,
12h is dried in vacuo at 80 DEG C.
Embodiment 5
A kind of above-mentioned molybdenum disulfide/polyaniline composite material and preparation method thereof.Molybdenum disulfide/the polyaniline composite material
Prepared by following methods：
S51. take sodium molybdate 0.121g, aniline 0.2mL to be added in 50mL deionized waters, add 1M dilute hydrochloric acid tune pH to 2
Left and right, continues to add ammonium persulfate 0.6g into reaction solution, the progress chemical oxidising polymerisation reaction at 0 DEG C, reaction time 6h,
Obtain blackish green intermediate product；
S52. thiocarbamide 0.38g is added in the reaction solution into step S51, is put into after mixing in hydrothermal reaction kettle,
Hydro-thermal reaction 12h is carried out at 220 DEG C, obtains molybdenum disulfide/polyaniline black combination product；
S53. will be put into after molybdenum disulfide described in step S52/polyaniline combination product filtering, washing in vacuum drying chamber,
12h is dried in vacuo at 80 DEG C.
Embodiment 6
A kind of above-mentioned molybdenum disulfide/polyaniline composite material and preparation method thereof.Molybdenum disulfide/the polyaniline composite material
Prepared by following methods：
S61. take ammonium molybdate 0.618g, aniline 0.2mL to be added in 50mL deionized waters, add 1M dilute hydrochloric acid tune pH to 2
Left and right, continues to add ammonium persulfate 0.6g into reaction solution, the progress chemical oxidising polymerisation reaction at 0 DEG C, reaction time 6h,
Obtain blackish green intermediate product；
S62. thiocarbamide 0.38g is added in the reaction solution into step S61, is put into after mixing in hydrothermal reaction kettle,
Hydro-thermal reaction 12h is carried out at 200 DEG C, obtains molybdenum disulfide/polyaniline black combination product；
S63. will be put into after molybdenum disulfide described in step S62/polyaniline combination product filtering, washing in vacuum drying chamber,
12h is dried in vacuo at 80 DEG C.
Embodiment 7
A kind of above-mentioned molybdenum disulfide/polyaniline composite material and preparation method thereof.Molybdenum disulfide/the polyaniline composite material
Prepared by following methods：
S71. take ammonium molybdate 0.618g, aniline 0.2mL to be added in 50mL deionized waters, add 1M dilute hydrochloric acid tune pH to 2
Left and right, continues to add ammonium persulfate 0.6g into reaction solution, the progress chemical oxidising polymerisation reaction at 0 DEG C, reaction time 6h,
Obtain blackish green intermediate product；
S72. cysteine 0.605g is added in the reaction solution into step S71, is put into hydrothermal reaction kettle after mixing
In, hydro-thermal reaction 48h is carried out at 200 DEG C, obtains molybdenum disulfide/polyaniline black combination product；
S73. will be put into after molybdenum disulfide described in step S72/polyaniline combination product filtering, washing in vacuum drying chamber,
12h is dried in vacuo at 80 DEG C.
Embodiment 8
A kind of above-mentioned molybdenum disulfide/polyaniline composite material and preparation method thereof.Molybdenum disulfide/the polyaniline composite material
Prepared by following methods：
S81. take potassium molybdate 0.119g, aniline 0.2mL to be added in 50mL deionized waters, add 1M dilute hydrochloric acid tune pH to 2
Left and right, continues to add ammonium persulfate 0.6g into reaction solution, the progress chemical oxidising polymerisation reaction at 0 DEG C, reaction time 6h,
Obtain blackish green intermediate product；
S82. thiocarbamide 0.38g is added in the reaction solution into step S81, is put into after mixing in hydrothermal reaction kettle,
Hydro-thermal reaction 12h is carried out at 200 DEG C, obtains molybdenum disulfide/polyaniline black combination product；
S83. will be put into after molybdenum disulfide described in step S82/polyaniline combination product filtering, washing in vacuum drying chamber,
12h is dried in vacuo at 80 DEG C.
Embodiment 9
A kind of above-mentioned molybdenum disulfide/polyaniline composite material and preparation method thereof.Molybdenum disulfide/the polyaniline composite material
Prepared by following methods：
S91. take sodium molybdate 0.119g, aniline 0.2mL to be added in 50mL deionized waters, add 1M dilute hydrochloric acid tune pH to 2
Left and right, continues to add ammonium persulfate 0.6g into reaction solution, the progress chemical oxidising polymerisation reaction at 0 DEG C, reaction time 6h,
Obtain blackish green intermediate product；
S92. thiocarbamide 0.38g is added in the reaction solution into step S91, is put into after mixing in hydrothermal reaction kettle,
Hydro-thermal reaction 48h is carried out at 200 DEG C, obtains molybdenum disulfide/polyaniline black combination product；
S93. will be put into after molybdenum disulfide described in step S92/polyaniline combination product filtering, washing in vacuum drying chamber,
12h is dried in vacuo at 80 DEG C.
Lithium ion battery embodiment
By the molybdenum disulfide/polyaniline composite material provided in the various embodiments described above according to conventional negative electrode of lithium ion battery
Preparation method is prepared into negative electrode of lithium ion battery respectively.
According to lithium ion battery customary preparation methods, the molybdenum disulfide/polyaniline provided in the various embodiments described above will be utilized
Negative electrode of lithium ion battery prepared by composite material is assembled into lithium ion battery respectively.
Performance test：
1. molybdenum disulfide prepared by pair above-described embodiment 1~9/polyaniline composite material carries out micro-analysis：
Molybdenum disulfide/polyaniline composite material prepared by above-described embodiment 1~9 is scanned Electronic Speculum and X-ray diffraction
Analysis.
Wherein, the scanning electron microscope analysis of molybdenum disulfide/polyaniline composite material prepared by embodiment 1 is as shown in Figure 2.By scheming
2 picture understands that the molybdenum disulfide/polyaniline composite material shows three-dimensional flowers laminated structure, and structure is more loose.This
Kind structure is conducive to the disengaging of lithium ion in charge and discharge process, its ionic conductivity is improved, so as to improve the high rate performance of battery.
The results are shown in Figure 3 for the X-ray diffraction of molybdenum disulfide/polyaniline composite material prepared by embodiment 1.Penetrated from the X
Ray diffraction diagram can be seen that special compared to pure molybdenum disulfide material, the molybdenum disulfide of the molybdenum disulfide/polyaniline composite material
Diffraction peaks broadening is levied, illustrates that polyaniline is evenly dispersed in composite material so that material switchs to the loose of amorphous phase by crystalline phase
Structure.This structure is conducive to the disengaging of lithium ion in charge and discharge process, improves its ionic conductivity, so as to improve times of battery
Rate performance.
Molybdenum disulfide/polyaniline composite negative pole material scanning electron microscope and X-ray diffraction analysis knot prepared by embodiment 2~9
Fruit is similar with the molybdenum disulfide in embodiment 1/polyaniline composite negative pole material.
2. it is to carry out cycle performance and high rate performance test, the cyclicity for the various embodiments described above lithium ion battery below
It can conventionally be carried out with high rate performance test method, it is as follows to measure result：
1 cycle performance of lithium ion battery test result of embodiment is as shown in figure 4, high rate performance test result is as shown in Figure 5.
From Fig. 4,5, the cyclicity of lithium ion battery and high rate performance are excellent in embodiment 1.
By test, the cycle performance and high rate performance of the lithium ion battery in embodiment 2~3 are similar to Example 1,
With excellent cyclicity and high rate performance.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should all be included within protection scope of the present invention.
Claims (3)
1. a kind of preparation method of molybdenum disulfide/polyaniline composite material, includes the following steps：
Molybdate is added into the mixed system of thing containing aniline reaction for prepare polyaniline and is dissolved and is changed after at 0~50 DEG C
Oxidative polymerization is learned, obtains being dispersed with the polyaniline of molybdate；Reaction system after being reacted again to the chemical oxidising polymerisation
Middle addition sulphur source, and carry out mixing treatment and obtain molybdenum disulfide/polyphenyl after progress 12~48h of hydro-thermal reaction at 180~240 DEG C
Amine product；By separation of solid and liquid, washing, drying process；The molybdenum disulfide/polyaniline product is the open structure of amorphous phase；
The mixed system of thing containing aniline reaction for preparing polyaniline includes dilute hydrochloric acid, ammonium persulfate and aniline, and the reaction
Thing is soluble in water, and it is 2 that the dilute hydrochloric acid, which adjusts pH value,；The aniline the concentration of the mixed system of thing containing aniline reaction be 0.01~
1mol/L, it is (1~3) that the amount that the molybdate adds, which control the molar ratio in the molybdate and the aniline,：1；
It is 1 that the amount that the sulphur source adds, which is controlled in the sulphur source and the molar ratio of molybdate,:0.5~3, the molybdate selects molybdenum
Sour ammonium, potassium molybdate, calcium molybdate, magnesium molybdate, at least one of the molybdate of First Series transition metal, the sulphur source select sulphur
At least one of urea, thioacetamide, mercaptan, thioether, thiophenol.
2. a kind of negative electrode of lithium ion battery, including collector and the activity containing negative material that is incorporated on the collector
Layer, it is characterised in that：The negative material is the preparation side of molybdenum disulfide/polyaniline composite material as claimed in claim 1
Molybdenum disulfide/polyaniline composite material that method prepares.
3. a kind of lithium ion battery, it is characterised in that the lithium ion battery that the lithium ion battery includes described in claim 2 is born
Pole.
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| CN105924665B (en) * | 2016-04-26 | 2018-10-30 | 上海应用技术学院 | A kind of preparation method and applications of superhigh cross-linking layering microporous polymer |
| CN105845910B (en) * | 2016-05-01 | 2019-10-11 | 上海大学 | Flower-shaped MoS2@graphene nanocomposite material and preparation method thereof |
| CN107364890B (en) * | 2016-05-11 | 2020-01-03 | 中国科学院宁波材料技术与工程研究所 | Liquid phase stripping method of two-dimensional molybdenum disulfide nano material, molybdenum disulfide dispersing method and application |
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| CN107219283B (en) * | 2017-06-14 | 2019-05-28 | 青岛科技大学 | A kind of method of photic electrochemical gaging glutathione |
| CN108987699B (en) * | 2018-07-13 | 2021-09-14 | 广州明美新能源股份有限公司 | High-stability high-capacity lithium ion battery cathode active material and preparation method thereof |
| CN110690419B (en) * | 2019-09-10 | 2021-06-08 | 深圳先进技术研究院 | Transition metal chalcogenide composite material and preparation method and application thereof |
| CN113436892B (en) * | 2021-06-08 | 2022-10-25 | 湖南艾华集团股份有限公司 | Based on MoS 2 -PANI solid aluminum electrolytic capacitor and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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Non-Patent Citations (1)
| Title |
|---|
| "Fabrication of 3D Hierarchical MoS2/Polyaniline and MoS2/C Architectures for Lithium-Ion Battery Applications";Lianren Hu et al;《ACS Applied Materials & Interfaces》;20140806;第6 卷;第14644–14652页 * |
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