CN104934568A - MoS2 hollow tube-transition metal oxide nano particle micro-nano structured lithium ion battery anode and preparation method thereof - Google Patents

MoS2 hollow tube-transition metal oxide nano particle micro-nano structured lithium ion battery anode and preparation method thereof Download PDF

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CN104934568A
CN104934568A CN201510237887.0A CN201510237887A CN104934568A CN 104934568 A CN104934568 A CN 104934568A CN 201510237887 A CN201510237887 A CN 201510237887A CN 104934568 A CN104934568 A CN 104934568A
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mos
metal oxide
transition metal
hollow tube
nano
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朱晓东
孙克宁
刘一涛
王可心
乐士儒
张乃庆
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Harbin Institute of Technology
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Harbin Institute of Technology
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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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a MoS2 hollow tube-transition metal oxide nano particle micro-nano structured lithium ion battery anode and a preparation method thereof. The micro-nano structured lithium ion battery anode takes MoS2 hollow tubes as a substrate, and transition metal oxide nano particles as a blocking agent, and the surfaces of the MoS2 hollow tubes are modified with the transition metal oxide nano particles. The transition metal oxide nano particles can be automatically assembled on the surfaces of the MoS2 hollow tubes by using a hydrothermal method or van der Waals interaction method. The MoS2 hollow tube-transition metal oxide nano particle micro-nano structure disclosed by the invention effectively combines the structural characteristics of the two high-specific capacity anode materials, the MoS2 hollow micro-nano tubes serving as the substrate can provide rich micropores and a large number of internal free hollow spaces, Li+ transmission and storage are promoted, and moreover, volume expansion caused by repeated intercalation and deintercalation of lithium ions are accommodated; and the granular transition metal oxide serving as the blocking agent can be used for suppressing the agglomeration of tubular MoS2, and the tube pitch for Li+ transmission is expanded.

Description

A kind of MoS 2hollow tube-transition metal oxide nano-particles micro-nano structure lithium cell negative pole and preparation method thereof
Technical field
The invention belongs to technical field of energy material, relate to a kind of MoS 2hollow tube-transition metal oxide nano-particles micro-nano structure lithium cell negative pole and preparation method thereof.
Background technology
Lithium ion battery because its operating voltage is high, energy density is large, have extended cycle life, memory-less effect and the advantage such as environmentally friendly and become the ideal source of portable type electronic product.In recent years along with the flourish and policy inclination of electric tool and new-energy automobile, the lithium ion battery of future generation that exploitation has more high-energy, a power density has become a kind of strategic choice of China's new forms of energy development.And the Design & preparation of novel high-capacity electrode material is the key obtaining high performance lithium ion battery.Current lithium ion battery commercialization negative material---graphite, not only specific capacity is low, and easily causes serious safety problem during repid discharge, can not meet the demand of high performance lithium ion battery of future generation far away.So the negative pole substitution material seeking to have more high electrochemical performance has attracted the extensive concern of whole world scientific research person.
MoS 2be a kind of typical transient metal sulfide, be mingled with one deck Mo atom by two-layer S atom and formed by van der Waals effect bonding.Such layer structure allows little ion, such as Li +, be reversibly embedded in inter-layer passages and can not produce large volumetric expansion.Yangization – according to its uniqueness reduces storage lithium mechanism and the transition metal of high-valence state can be reduced sufficiently, and lithium is then oxidized and be combined with sulphur and form Li 2s matrix, stores 4 lithium ions, has higher theoretical lithium storage content (670 mA h g – 1), the twice of commercial graphite material can be reached, become the Novel cathode material for lithium ion battery that a class specific capacity is high, fail safe good, low cost and other advantages is outstanding.
Unfortunately MoS 2nanometer sheet, in embedding repeatedly/deviate from process, be born huge change in volume, and can produce again stacking phenomenon, make cycle performance particularly rapid decay under high magnification condition.Solution utilizes different barriers, and such as graphene nano layer, carbon nano-tube, Nano carbon balls, noble metal nano particles and transition metal oxide nano-particles, stop MoS from physical space 2nanometer sheet stacking, the Yu Chen etc. of such as Singapore assembles Fe 3o 4nano particle/MoS 2nanosheet composite material; Another kind of strategy is by MoS 2nanometer sheet is assembled into more senior hollow structure, such as nanotube, nanometer box and nanosphere, the internal structure of this three-dimensional hollow can provide more free volume, thus the structural stress in charge and discharge process can be alleviated, and hold lithium ion and repeatedly embed the volumetric expansion caused with deintercalation, therefore cycle performance is more excellent.Such as Tsing-Hua University of China Wang Xun etc. are by MoS 2nanometer sheet has constructed MoS 2nanotube, improves 40% by reversible capacity.
But any one strategy above only can solve MoS 2a kind of defect of nanostructure, and another problem is not related to.Through finding prior art retrieval, there is not yet the open report simultaneously used by above two kinds of strategies at present both at home and abroad, therefore MoS 2the cycle performance of nanostructure particularly still can not be satisfactory under high magnification condition.
Summary of the invention
For nanometer MoS 2the defect of the volumetric expansion in cyclic process and stacking aspect, the present invention designs and has constructed a kind of MoS 2hollow tube-transition metal oxide nano-particles micro-nano structure lithium cell negative pole, utilizes its outstanding cooperative effect, has given play to excellent electrochemistry combination property.
MoS of the present invention 2hollow tube-transition metal oxide nano-particles micro-nano structure lithium cell negative pole, its architectural feature is with MoS 2hollow tube as matrix, transition metal oxide nano-particles as barrier, at MoS 2hollow tube surface uniform is also modified with transition metal oxide nano-particles densely; Composition characteristic is that three dimensional anodes is by MoS 2with transition metal oxide nano-particles be the heterostructure of the composition of proportions of 6:2 ~ 5 with weight ratio, two kinds of materials all belong to height ratio capacity lithium ion battery negative material.
MoS of the present invention 2hollow tube-transition metal oxide nano-particles micro-nano structure lithium cell negative pole has the feature that micron and nanostructure combine, that is: MoS 2hollow tube is macroscopically micron order or submicron order structure, microcosmic is by nanoscale MoS 2nanometer sheet assembling is formed, and the transition metal oxide nano-particles that area load is abundant.On the one hand, the MoS of tubulose 2abundant micropore and the internal structure of hollow can be provided as matrix, not only promote Li +transmission and storage, and the structural stress produced in self and transition metal oxide charge and discharge process can be alleviated, and hold lithium ion and repeatedly embed the volumetric expansion caused with deintercalation; On the other hand, granular transition metal oxide can suppress tubulose MoS as barrier 2reunion, be Li +transmission increase tube pitch.And compare other barrier, such as nano-sized carbon and noble metal, the huge advantage of transition metal oxide is its high theoretical capacity (750 ~ 1250 mA h g 1).This MoS 2hollow tube-transition metal oxide nano-particles micro-nano structure negative pole improves MoS significantly by the synergy between these two kinds of active materials 2reversible capacity and high rate performance.
In the present invention, the MoS of described hollow tubular 2refer to that outside dimension is at 200 ~ 600nm, length is at the both ends open formula MoS of 0.7 ~ 1.5 μm 2hollow tube.
In the present invention, the average grain diameter of described transition metal oxide nano-particles is between 4 ~ 12nm.
In the present invention, described transition metal oxide is Fe 2o 3, Fe 3o 4, SnO 2, Co 3o 4or MnO 2deng any one of height ratio capacity metal oxide.
In the present invention, described MoS 2with a kind of ratio that the weight ratio of transition metal oxide can be in 3:1,2:1,3:2,6:5, the actual electrical chemical property that this weight ratio reveals according to different composite material list is determined.
In the present invention, described MoS 2hollow tube-transition metal oxide nano-particles micro-nano structure negative pole can adopt hydro thermal method or the self assembly of van der Waals interaction method.The self-assembling method of micro-nano structure negative pole of the present invention is introduced below for van der Waals interaction method.
(1) with sulphur powder and ammonium molybdate for raw material, adopt hydro thermal method to prepare MoS 2hollow tube, and by this MoS 2pipe is transferred in its poor solvent oxolane (THF);
(2) hydro-thermal reaction, hydrolysis etc. is utilized to synthesize a kind of Fe 2o 3, Fe 3o 4, SnO 2, Co 3o 4or MnO 2nano particle, and transfer in its good solvent THF;
(3) above-mentioned two kinds of solution are mixed with certain proportion, under stirring or ultrasound condition, under the actuating force of free energy reducing system, be assembled into MoS 2hollow tube-transition metal oxide nano-particles micro-nano structure negative material.
In the present invention, the oxolane (THF) described in step (1) is MoS 2the poor solvent of pipe, MoS in THF 2have unmatched Hansen Solubility Parameter between pipe and THF, thus have strong again stacking tendency, thus THF can not reduce MoS 2the huge surface free energy that pipe has.
In the present invention, the THF described in step (2) is the good solvent of transition metal oxide nano-particles, these transition metal oxide nano-particles can in THF stable existence.
In the present invention, the stirring described in step (3) is magnetic agitation 6 ~ 12 hours, described ultrasonic be under 70 W intensity 8 ~ 24 hours.
In the present invention, the actuating force described in step (3) is reduce total free energy of solution system.MoS in THF 2pipe has huge surface free energy, once more stable transition metal oxide nano-particles is introduced in THF, will trend towards residing in MoS under van der Waals interacts 2on the exposed surface of pipe, to reduce the total surface free energy of solution system, make the MoS in THF 2pipe stabilisation, thus successfully assemble MoS 2hollow tube-transition metal oxide nano-particles micro-nano structure negative pole.
The present invention is by MoS 2pipe is transferred in its poor solvent-oxolane (THF), MoS in THF 2the again stacking tendency that pipe is strong because Hansen Solubility Parameter unmatched between solvent has, this step is very crucial to successfully carrying out self assembly later, because THF can not reduce the huge surface free energy that insoluble two-dimensional nano sheet has.Therefore more stable transition metal oxide nano-particles, once be introduced in THF, will trend towards residing in MoS because van der Waals interacts 2on the exposed surface of pipe, to reduce the total surface free energy of solution system, make the MoS in THF 2pipe stabilisation.This self-assembling method, because do not introduce external crosslinking agent, compares the method utilizing complexing to prepare composite material, has low cost and gentle advantage.
Accompanying drawing explanation
Fig. 1 is MoS in embodiment 1 2-Fe 3o 4the high-resolution Mo 3d XPS spectrum figure (Fe of hybrid material 3o 4/ MoS 2weight ratio is 1/2);
Fig. 2 is MoS in embodiment 1 2-Fe 3o 4the high-resolution S 2p XPS spectrum figure (Fe of hybrid material 3o 4/ MoS 2weight ratio is 1/2);
Fig. 3 is MoS in embodiment 1 2-Fe 3o 4the high-resolution Fe 2p XPS spectrum figure (Fe of hybrid material 3o 4/ MoS 2weight ratio is 1/2);
Fig. 4 is MoS in embodiment 1 2-Fe 3o 4the high-resolution O 1s XPS spectrum figure (Fe of hybrid material 3o 4/ MoS 2weight ratio is 1/2);
Fig. 5 is MoS in embodiment 1 2hollow tube-Fe 3o 4the transmission electron microscope picture of nano particle micro-nano structure negative material;
Fig. 6 is MoS in embodiment 1 2hollow tube-Fe 3o 4the high-resolution-ration transmission electric-lens figure of nano particle micro-nano structure negative material;
Fig. 7 is MoS in embodiment 1 2hollow tube-Fe 3o 4nano particle micro-nano structure negative pole is at 0.1A g 1cycle performance curve chart under current density;
Fig. 8 is MoS in embodiment 1 2hollow tube-Fe 3o 4the high rate performance curve of nano particle micro-nano structure negative pole.
Embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is further described; but be not limited thereto; everyly technical solution of the present invention modified or equivalent to replace, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
embodiment 1
For nanostructure MoS 2the defect of the volumetric expansion in cyclic process and stacking aspect, the present embodiment designs and has constructed a kind of high performance lithium ion battery MoS 2hollow tube-Fe 3o 4nano particle micro-nano structure negative pole, utilizes its outstanding cooperative effect, has given play to excellent electrochemistry combination property.
The MoS that the present embodiment provides 2hollow tube-Fe 3o 4nano particle micro-nano structure negative pole is by MoS 2hollow tube and Fe 3o 4nano particle is formed with the weight ratio of 2:1, and its preparation method is as follows:
(1) 2.4 mmol sulphur powder are dissolved in the mixed solution that 28 mL octylames and 24 mL ethanol form, then add 0.15 mmol ammonium molybdate.After stirring 30 min, transfer in polytetrafluoroethylene reactor and seal, at 200 DEG C, react 24 h.Naturally cool to room temperature, clean with ethanol and deionized water, and 60 DEG C of vacuumizes 12 hours, obtain black powder.
(2) by 9mmol Fe (acac) 3, 90mL oleyl amine and 90mL octadecylene mixing, and nitrogen atmosphere protection under be heated to 280 DEG C insulation 1 hour, then naturally cool to room temperature.Sedimentation afterproduct ethanol is washed 2 ~ 3 times, and 40 DEG C of vacuumizes 12 hours, obtains Fe 3o 4nano particle.
(3) above-mentioned two kinds of powder are dissolved in THF solution respectively, obtain 0.1 mg mL – 1tHF solution, then according to MoS 2/ Fe 3o 4the weight ratio mixing of=2:1, and under 70 W intensity ultrasonic 12 hours, under the actuating force of free energy reducing system, be assembled into MoS 2hollow tube-Fe 3o 4nano particle micro-nano structure negative pole.Then be isolated by magnet and clean, and at 60 DEG C, vacuum dry 12 hours.
The lithium ion battery MoS of the present embodiment 2hollow tube-Fe 3o 4nano particle micro-nano structure negative pole, its architectural feature is: Fe 3o 4nano particle uniform load is also combined closely at MoS 2the micro-nano structure that hollow tube is formed on the surface, wherein MoS 2hollow tube is micron scale construction in length, and Fe 3o 4for zero-dimension nano particle, the micro-nano structure that composite material possesses nanometer simultaneously, micron combines formed like this.This micro-nano structure negative pole can give full play to the architectural characteristic of each component, is embodied in:
(1) MoS 2hollow tube has huge free space, can alleviate self and Fe 3o 4the structural stress produced in charge and discharge process, and hold lithium ion and repeatedly embed the volumetric expansion caused with deintercalation;
(2) MoS 2hollow tube can provide abundant micropore and the internal structure of hollow as matrix, thus promotes Li +transmission and storage;
(3) MoS 2hollow tube can suppress Fe as matrix 3o 4the reunion of nano particle in cyclic process;
(4) Fe 3o 4nano particle can suppress tubulose MoS as barrier 2reunion, be Li +transmission increase tube pitch;
(5) other barrier is compared, such as nano-sized carbon and noble metal, Fe 3o 4huge advantage be its high theoretical capacity (927 mA h g 1).
This MoS 2hollow tube-Fe 3o 4nano particle micro-nano structure negative pole improves MoS significantly by the synergy between these two kinds of active materials 2reversible capacity and high rate performance.
Fig. 1-4 is MoS 2-Fe 3o 4the high-resolution Mo 3d of hybrid material, S 2p, Fe 2p and O 1s XPS spectrogram (Fe 3o 4/ MoS 2weight ratio is 1/2), result shows do not have Fe in this composite material 2o 3exist, prove that our assemble method is non-invasive, there is no the chemical nature of change two kinds of group element materials; Fig. 5 is MoS 2hollow tube-Fe 3o 4the transmission electron microscope picture of nano particle micro-nano structure negative material, can find out Fe 3o 4the even also load densely of nano particle is at MoS 2on hollow tube, wherein MoS 2the external diameter of hollow tube is about 500nm, and length is at about 1.3 μm, and Fe 3o 4the average grain diameter of nano particle is at about 6nm; Fig. 6 is MoS 2hollow tube-Fe 3o 4the high-resolution-ration transmission electric-lens figure of nano particle micro-nano structure negative material, the lattice fringe spacing recording 0.48nm and 0.6nm just and spinelle Fe 3o 4(111) crystal face and 2H – MoS 2(002) crystal face is corresponding, matches with document; Fig. 7 is MoS 2hollow tube-Fe 3o 4nano particle micro-nano structure negative pole is at 0.1A g 1cycle performance curve chart under current density, can find out that this electrode shows good cyclicity, and after 100 circulations, specific discharge capacity is 1113 mAh g 1, than pure MoS 2guan Yaogao 44%; Fig. 8 is MoS 2hollow tube-Fe 3o 4the high rate performance curve of nano particle micro-nano structure negative pole, at 0.1,0.2,0.5,1 and 2 A g 1under current density, specific discharge capacity can reach 1183,1110,1019,910 and 800 mA h g respectively – 1, be far superior to pure MoS 2the high rate performance of pipe.
embodiment 2
The present embodiment is step (3) as different from Example 1: be dissolved in respectively in THF solution by above-mentioned two kinds of solution, obtain 0.1 mg mL – 1tHF solution, then according to MoS 2/ Fe 3o 4the weight ratio mixing of=3:1, and stir 8 hours, under the actuating force of free energy reducing system, be assembled into MoS 2hollow tube-Fe 3o 4nano particle micro-nano structure negative pole.Then clean and centrifugation, and at 60 DEG C, vacuum dry 12 hours.
embodiment 3
For nanometer MoS 2the defect of the volumetric expansion in cyclic process and stacking aspect, the present embodiment designs and has constructed a kind of high performance lithium ion battery MoS 2hollow tube-SnO 2nano particle micro-nano structure negative pole, utilizes its outstanding cooperative effect, has given play to excellent electrochemistry combination property.
The MoS that the present embodiment provides 2hollow tube-SnO 2nano particle micro-nano structure negative pole, by MoS 2hollow tube and SnO 2nano particle is formed with the weight ratio of 2:1, and its preparation method is as follows:
(1) 2.4 mmol sulphur powder are dissolved in the mixed solution that 28 mL octylames and 24 mL ethanol form, then add 0.15 mmol ammonium molybdate.After stirring 30 min, transfer in polytetrafluoroethylene reactor and seal, at 200 DEG C, react 24 h.Naturally cool to room temperature, clean with ethanol and deionized water, and 60 DEG C of vacuumizes 12 hours, obtain black powder.
(2) 0.3g Sn (Cl) 45H 2o to be dissolved in 25mL deionized water and under the power of 240 W ultrasonic 10 minutes, is then transferred in reactor, 180 DEG C of reactions 8 hours, product ethanol is washed 3 times, naturally cools to room temperature, and 40 DEG C of vacuumizes 12 hours, obtain SnO 2nano particle.
(3) above-mentioned two kinds of powder are dissolved in THF solution respectively, obtain 0.1 mg mL – 1tHF solution, then according to MoS 2/ SnO 2the weight ratio mixing of=2:1, and under 70 W intensity ultrasonic 12 hours, under the actuating force of free energy reducing system, be assembled into MoS 2hollow tube-SnO 2nano particle micro-nano structure negative pole.Then clean and pass through centrifugal collection, and at 60 DEG C, vacuum dry 12 hours.
The lithium ion battery MoS of the present embodiment 2hollow tube-SnO 2nano particle micro-nano structure negative pole, its architectural feature is: SnO 2nano particle uniform load is also combined closely at MoS 2the micro-nano structure that hollow tube is formed on the surface, wherein MoS 2hollow tube is micron scale construction in length, and SnO 2for zero-dimension nano particle, the micro-nano structure that composite material possesses nanometer simultaneously, micron combines formed like this.This micro-nano structure anode can give full play to the architectural characteristic of each component, is embodied in:
(1) MoS 2hollow tube has huge free space, can alleviate self and SnO 2the structural stress produced in charge and discharge process, and hold lithium ion and repeatedly embed the volumetric expansion caused with deintercalation;
(2) MoS 2hollow tube can provide abundant micropore and the internal structure of hollow as matrix, thus promotes Li +transmission and storage;
(3) MoS 2hollow tube can suppress SnO as matrix 2the reunion of nano particle in cyclic process;
(4) SnO 2nano particle can suppress tubulose MoS as barrier 2reunion, be Li +transmission increase tube pitch;
(5) other barrier is compared, such as nano-sized carbon and noble metal, SnO 2huge advantage be its high theoretical capacity (782 mA h g 1).
This MoS 2hollow tube-SnO 2nano particle micro-nano structure negative pole improves MoS significantly by the synergy between these two kinds of active materials 2reversible capacity and high rate performance.
embodiment 4
The present embodiment is step (2) and (3) as different from Example 1: by above-mentioned MoS 2hollow tube and 0.7095 g FeCl 36H 2o, 0.6616 g NaHCO 3join in 30 mL deionized waters with 0.088 g L-AA, transfer to after stirring in the polytetrafluoroethylene reactor of 125 mL and seal, at 150 DEG C, react 6 h.Naturally cool to room temperature, clean with ethanol and deionized water, and vacuum freeze drying, obtain black MoS 2hollow tube-Fe 3o 4nanoparticle powder.
By the MoS described in above-described embodiment 2hollow tube-transition metal oxide nano-particles micro-nano structure negative material is assembled into button cell, in button cell, component ratio is composite material: acetylene black: PVDF=70:10:20, adopt Clgard2300 type barrier film, be that metal buries sheet to electrode, electrolyte is by LiPF 6, ethylene carbonate and carbonic acid diethyl ester composition (LiPF in electrolyte 6concentration is l mol/L, and the volume ratio of ethylene carbonate and carbonic acid diethyl ester is 1:1), in the glove box being full of hydrogen, be assembled into 2025 type button cells, charging/discharging voltage scope is 2.5 ~ 1.0V.
embodiment 5
The present embodiment is step (3) as different from Example 3: be dissolved in respectively in THF solution by above-mentioned two kinds of solution, obtain 0.1 mg mL – 1tHF solution, then according to MoS 2/ SnO 2the weight ratio mixing of=3:1, and stir 9 hours, under the actuating force of free energy reducing system, be assembled into MoS 2hollow tube-SnO 2nano particle micro-nano structure negative pole.Then clean and centrifugation, and at 60 DEG C, vacuum dry 12 hours.

Claims (10)

1. a MoS 2hollow tube-transition metal oxide nano-particles micro-nano structure lithium cell negative pole, is characterized in that described micro-nano structure lithium cell negative pole is with MoS 2hollow tube as matrix, transition metal oxide nano-particles as barrier, at MoS 2hollow tube finishing has transition metal oxide nano-particles, MoS 2be 6:2 ~ 5 with the weight ratio of transition metal oxide nano-particles.
2. MoS according to claim 1 2hollow tube-transition metal oxide nano-particles micro-nano structure lithium cell negative pole, is characterized in that described MoS 2hollow tube refers to that outside dimension is at 200 ~ 600nm, and length is at the both ends open formula MoS of 0.7 ~ 1.5 μm 2hollow tube.
3. MoS according to claim 1 and 2 2hollow tube-transition metal oxide nano-particles micro-nano structure lithium cell negative pole, is characterized in that the feature that described micro-nano structure lithium cell negative pole has micron and nanostructure and combines, MoS 2hollow tube is macroscopically micron order or submicron order structure, microcosmic is by nanoscale MoS 2nanometer sheet assembling is formed, and the transition metal oxide nano-particles that area load is abundant.
4. MoS according to claim 1 2hollow tube-transition metal oxide nano-particles micro-nano structure lithium cell negative pole, is characterized in that the average grain diameter of described transition metal oxide nano-particles is between 4 ~ 12nm.
5. MoS according to claim 1 2hollow tube-transition metal oxide nano-particles micro-nano structure lithium cell negative pole, is characterized in that described MoS 2be 3:1,2:1,3:2 or 6:5 with the weight ratio of transition metal oxide.
6. the MoS according to claim 1,3 or 4 2hollow tube-transition metal oxide nano-particles micro-nano structure lithium cell negative pole, is characterized in that described transition metal oxide is Fe 2o 3, Fe 3o 4, SnO 2, Co 3o 4or MnO 2.
7. MoS described in a claim 1 2the preparation method of hollow tube-transition metal oxide nano-particles micro-nano structure lithium cell negative pole, is characterized in that described micro-nano structure lithium cell negative pole adopts hydro thermal method or the self assembly of van der Waals interaction method.
8. MoS according to claim 7 2the preparation method of hollow tube-transition metal oxide nano-particles micro-nano structure lithium cell negative pole, is characterized in that described van der Waals interaction method concrete steps are as follows:
(1) with sulphur powder and ammonium molybdate for raw material, adopt hydro thermal method to prepare MoS 2hollow tube, and by this MoS 2pipe is transferred in its poor solvent oxolane;
(2) transition metal oxide nano-particles is transferred in its good solvent THF;
(3) above-mentioned two kinds of solution are mixed with certain proportion, under stirring or ultrasound condition, under the actuating force of free energy reducing system, be assembled into MoS 2hollow tube-transition metal oxide nano-particles micro-nano structure negative material.
9. MoS according to claim 8 2the preparation method of hollow tube-transition metal oxide nano-particles micro-nano structure lithium cell negative pole, is characterized in that the stirring described in step (3) is magnetic agitation 6 ~ 12 hours.
10. MoS according to claim 8 2the preparation method of hollow tube-transition metal oxide nano-particles micro-nano structure lithium cell negative pole, to it is characterized in that described in step (3) ultrasonic is under 70 W intensity 8 ~ 24 hours.
CN201510237887.0A 2015-05-12 2015-05-12 MoS2 hollow tube-transition metal oxide nano particle micro-nano structured lithium ion battery anode and preparation method thereof Pending CN104934568A (en)

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