CN102938461A - Nano sheet self-assembled MoS2 nano hollow material and preparation and application of MoS2 nano hollow material serving as lithium storage electrode material - Google Patents
Nano sheet self-assembled MoS2 nano hollow material and preparation and application of MoS2 nano hollow material serving as lithium storage electrode material Download PDFInfo
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Abstract
The invention discloses a nano sheet self-assembled MoS2 nano hollow material and preparation and application of the MoS2 nano hollow material serving as a lithium storage electrode material. The nano sheet self-assembled MoS2 nano hollow material is obtained by mixing raw materials including molybdenum oxide, sodium fluoride and potassium thiocyanate according to the mass ratio of 0.8-0.9:0.5-0.6:1.5-2.9; adding into water-ethanol mixed solvent; placing into a reaction kettle to be sealed; reacting at 140-220 DEG C for 12-30h; and performing washing, separating and drying to obtain products. The method is simple and easy in required condition, cheap and facile in raw materials and controllable in shape and height and easily achieves industrial production. Lithium storage electrodes prepared by adopting the prepared nano sheet self-assembled MoS2 nano hollow material not only have high electro-chemical lithium storage reversible capacity and excellent cycling performance, but also have good rate capability.
Description
Technical field
The invention belongs to electrochemical nano material preparation technology and new energy materials field, be specifically related to a kind of MoS of nanometer sheet self assembly
2The application of nano-hollow material and preparation thereof and conduct storage lithium electrode material.
Background technology
Secondary cell has represented the main direction of studying of energy storage technology.Existing secondary cell is because the factors such as life-span, power, capacity, cost can't satisfy the demand of Future Mobile Communication and electric automobile.Preparations of nanomaterials is just becoming the crucial science and technology that promotes conventional batteries performance, development of new battery, reduces cost with research, be the inevitable choice of the existing secondary cell combination property of General Promotion and development of new battery, represented main flow and the leading edge developments direction of current battery material and technical research.
Along with the development of lithium battery in the electric automobile field, people propose higher requirement to present business-like storage lithium electrode material, not only wish further to improve its energy density and power density, and also having great expectations of to have better cycle performance and security performance.Present business-like storage lithium stratified material mainly is graphite material, but its theoretical specific capacity only has 372mAh/g.In addition because its fail safe, cycle life and to negative issues such as limiting temperature tolerances have restricted its widely used bottleneck in extensive energy storage and electric automobile.Therefore, seek a kind of specific capacity height, the lithium storage materials of cycle performance and high rate performance excellence has important practical significance for the storage lithium performance that improves serondary lithium battery.
The MoS of class graphite
2Have typical sandwich layered structure, clip a metal M o layer between two S atomic layers, at MoS
2Be the S-Mo-S strong covalent bond between the S-Mo atom in the crystal structure, adjacent two layers links up by the Van der Waals force between the S layer.Therefore interlaminar action power relatively a little less than, the distance between the molecular layer is 0.62nm, this feature makes it be conducive to reversible doff lithium ion.The molybdenum in China source is abundant, and under the condition of deep discharge, in theory MoS
2Can in conjunction with 4 Li(~ 672mAh/g) relatively graphite have very high specific capacity, be a kind of very potential can business-like lithium storage materials.Change in volume causes greatly structural instability and the low shortcoming of conductance in the cyclic process yet it still exists, and the method for modifying of at present people's employing mainly is two kinds: one, the nanometer of material is simultaneously with MoS
2Interlamellar spacing enlarges, and not only shortens the lithium ion migrating channels and can also improve Li
+Embedded space; Two, by being combined to improve multiplying power and the cycle performance that conductance is improved material with conduction out-phase matrix, suppress simultaneously the bulk effect of active electrode material.Du, G.D. is with business-like MoS
2By peeling off-the synthetic MoS that has than large interlamellar spacing of the method for re-assemble
2(Chem.Commun., 2010,46,1106.); Xiao, J. etc. are with ethylene oxide monomer and the MoS that peels off
2The hydrolysis oxidation polymerization changes into (PEO) MoS
2(Chem.Mater., 2010,22,4522.); Chang, K. is inserted into MoS by hydro thermal method with a-C
2In the molecular layer, further high-temperature calcination obtains the combination electrode material (J.Mater.Chem., 2011,21,6251.) of carbon dope again; Liu, H. first synthetic phosphorus are impregnated into a period of time in this system with molecular sieve (SBA-15), at H for ammonium molybdate
2Calcining obtains three-dimensional mesoporous MoS in the S atmosphere
2(Adv.Energy Mater., 2012,2,970.); And Hwang, H. decomposes Mo (CO) in the paraxylene organic solvent
6With the S powder, make (0.69nm) the unordered MoS than large interlamellar spacing of having about 30 ~ 50nm
2Nanometer sheet (Nano Lett., 2011,11,4826.).Above-mentioned these nano materials show excellent cycle performance and the performance of high current charge-discharge, possess certain chemical property advantage.But often there are the problems such as harsh, the higher cost of technique or environmental pollution be more serious.
CN 102142538A (CN201110046460.4) discloses a kind of Graphene/MoS
2With lithium ion cell electrode and the preparation method of amorphous carbon, active material wherein is graphene nanometer sheet, MoS
2With the composite material of amorphous carbon, mainly improve reversible capacity and cycle performance.Technical scheme of the present invention is: component and weight percent content are as follows: graphene nanometer sheet: 4.2 ~ 15%, MoS
2: 44 ~ 65%, all the other are amorphous carbon.This invention mainly comprises: first with chemical oxidization method prepare the graphite oxide nanometer sheet take graphite as raw material, again by the synthetic graphene nanometer sheet/MoS that obtains of hydro-thermal approach
2The composite nano materials of class graphene nanometer sheet and amorphous carbon prepares electrode take this composite material as electroactive substance at last.Have high electrochemical lithium storage reversible capacity and excellent stable circulation performance.
CN102142541A (CN201110046491.X) provides the preparation of the lithium ion battery electrode material of a kind of high power capacity and stable cycle performance, and wherein active material is graphene nanometer sheet/MoS
2The ratio of the two amount of composite nano materials is: the electrode preparation method that 1:1 ~ 4:1. should invent comprises: prepare the graphite oxide nanometer sheet take graphite as raw material with chemical oxidization method, the more synthetic graphene nanometer sheet/MoS that obtains of further hydro-thermal local reduction way
2Composite nano materials. prepare electrode take this composite nano materials as active material at last.
At present also not about independent MoS
2Nano material is as the report of storage lithium electrode active material and preparation method thereof.
Summary of the invention
In order to overcome the MoS of existing report
2Deficiency as storage lithium electrode material the invention provides a kind of easy storage lithium MoS that is easy to get
2Electrode material of nano hollow structure and preparation method thereof.
The present invention also provides this MoS
2Nano-hollow material is as the application of storage lithium electrode material, MoS of the present invention
2Nano-hollow material (nanometer sheet self assembly) and solid nano-electrode material phase specific energy improve performance and the cyclical stability of high current charge-discharge effectively.
Technical scheme of the present invention is as follows:
A kind of MoS
2Nano-hollow material makes by the following method:
Raw material molybdenum oxide, sodium fluoride, potassium rhodanide are mixed 0.8 ~ 0.9:0.5 ~ 0.6:1.5 ~ 2.0 in mass ratio, join in the water-ethanol mixed solvent, the mass volume ratio of raw material and mixed solvent is (5.6 ~ 7)/100, and unit is g/mL; Place reactor to seal, in 140 ~ 220 ℃ of reaction 12 ~ 30h, products therefrom is through washing, separate, being drying to obtain.
Preferred according to the present invention, described mixed solvent is water: ethanol volume ratio (3 ~ 1): (1 ~ 3), further preferred water: the mixed solvent of ethanol volume ratio 3:1.
According to the present invention, a kind of MoS
2The preparation method of nano-hollow material, step is as follows:
Raw material molybdenum oxide, sodium fluoride, potassium rhodanide are mixed 0.8 ~ 0.9:0.5 ~ 0.6:1.5 ~ 2.0 in mass ratio, join in the water-ethanol mixed solvent, the mass volume ratio of raw material and mixed solvent is (5.6 ~ 7)/100, and unit is g/mL; Stir 0.5 ~ 1h, place the polytetrafluoroethylene reactor to seal, in 140 ~ 220 ℃ of reaction 12 ~ 30h, the reaction products therefrom is through deionized water and absolute ethanol washing, centrifugation and under 60 ℃ of conditions of vacuum dry 6 ~ 8h, obtain the MoS of nanometer sheet self assembly
2Nano-hollow material.
According to the present invention, preferred a kind of MoS
2The preparation method of nano-hollow material, step is as follows:
Molybdenum oxide 0.865g, sodium fluoride 0.515g, potassium rhodanide 1.930g are mixed, join the water-ethanol (3 ~ 1) of 50mL: in the mixed solvent reaction system of (1 ~ 3) volume ratio, uniform stirring 0.5h changes in the 60mL polytetrafluoroethylene reactor, sealing, in 180 ~ 220 ℃ of reaction 16 ~ 20h, the reaction products therefrom is through deionized water and absolute ethanol washing, centrifugation and under 60 ℃ of conditions of vacuum dry 6 ~ 7h, obtain MoS
2Nano-hollow material.
Further preferred, MoS
2The preparation method of nano-hollow material is, molybdenum oxide 0.865g, sodium fluoride 0.515g, potassium rhodanide 1.930g are mixed, join in the mixed solvent reaction system of water-ethanol 3:1 volume ratio of 50mL, uniform stirring 0.5h changes in the 60mL polytetrafluoroethylene reactor, sealing, in 180 ~ 220 ℃ of reaction 16h, the reaction products therefrom is through deionized water and absolute ethanol washing, centrifugation and under 60 ℃ of conditions of vacuum dry 6h, obtain the MoS of nanometer sheet self assembly
2Nano-hollow material.
Most preferred, MoS
2The preparation method of nano-hollow material is, molybdenum oxide 0.865g, sodium fluoride 0.515g, potassium rhodanide 1.930g are mixed, join in the mixed solvent reaction system of water-ethanol 3:1 volume ratio of 48mL, uniform stirring 0.5h changes in the 60mL polytetrafluoroethylene reactor and seals, under 200 ℃ of conditions, react 16h, product is through deionized water and absolute ethanol washing, and centrifugation and at 60 ℃ of lower vacuumize 6h obtains MoS
2Nano-hollow material.
Gained MoS of the present invention
2Nano-hollow material is the powder-product of black.Compared with prior art, the invention provides a kind of MoS of preparation
2The new method of nano-hollow material, reaction temperature is lower, easy control simple to operate, the products therefrom pattern is better.Described MoS
2Nanometer hollow granule is to form MoS by the regular self assembly of the nanometer sheet of two dimension
2The size of nanometer hollow granule is at 300～800nm(such as Fig. 2).In addition, by transmission electron microscope and XRD characterized by techniques combine the required expansion of electrode material molecular layer spacing, three-dimensional self assembly and hollow-core construction, have larger specific area, be conducive to improve the storage lithium performance of material.The inventive method is easy to realize suitability for industrialized production simultaneously.
The MoS of nanometer sheet self assembly of the present invention
2Nano-hollow material is as the application of storage lithium electrode material activity material.Can prepare by the following method electrode:
With conductive agent: binding agent: active material (MoS
2) with the quality of 20:10:70 than mixed slurry, conductive agent adopts acetylene black, binding agent adopts the PVDF Kynoar, active material adopts the MoS of nanometer sheet self assembly
2Nano-hollow material; Mixed slurry is coated on the Copper Foil collector.Be cut into electrode slice, 80 ℃ were dried by the fire 12 hours in vacuum, formed button cell by prior art, and the lithium sheet is to electrode, and battery operated interval is 0.01V-3.0V.
MoS with nanometer sheet self assembly of the present invention
2The battery that nano-hollow material forms carries out the electrochemical property test of electrode, and test result shows: be used as electroactive substance MoS
2The reversible capacity that nano-hollow material prepares the initial electrochemistry embedding of electrode/take off Li ion reaches 907mAh/g, circulates after 80 times, and its reversible capacity can also be at 902mAh/g.
The present invention is to stratiform molybdenum bisuphide MoS
2Probe into except the effective way in conjunction with the raising material electrochemical performance of interlamellar spacing, high-specific surface area, three-dimensional self assembly and the hollow-core construction equivalence of its increase, preparation technology of reaction raw materials, simple possible is significant too to possible commercial applications cheaply for it.
The inventor is conducting extensive research the inorganic layered compounds field, adopts the method for mixed solvent heat to synthesize the MoS of nanometer sheet self assembly
2Nano-hollow material is studied discovery MoS to its chemical property
2Demonstrate the multiplying power and the cycle performance that obviously strengthen with respect to solid nanosphere, for the study on the modification of sulfide provides a kind of effective way, use for its possible high current charge-discharge and lay a good foundation.MoS by the nanometer sheet self assembly of the inventive method preparation
2Nano-hollow material effectively improved high current charge-discharge multiplying power and cycle performance as lithium storage materials, may further be the large electric current on the electric automobile and discharging and recharging for a long time provides application product.The inventive method is workable, favorable reproducibility, and products obtained therefrom steady quality.
Description of drawings
Fig. 1 is the MoS of embodiment of the invention preparation
2The XRD spectra of nano-hollow material.
Fig. 2 is the embodiment of the invention 1 gained MoS
2Nano-hollow material transmission electron microscope and stereoscan photograph.
Fig. 3 embodiment of the invention 1 gained MoS
2Nanometer solid material transmission electron microscope and stereoscan photograph.
Fig. 4 is the embodiment of the invention 1 gained MoS
2The chemical property high rate performance contrast of nano-hollow material and nanometer solid material.
Fig. 5 is the embodiment of the invention 1 gained MoS
2The performance comparison that nano-hollow material and nanometer solid material circulate under the current density of 100mA/g first.
Embodiment
Below in conjunction with drawings and Examples the present invention is more at large illustrated.
Embodiment 1:MoS
2The preparation of nano-hollow material
With molybdenum oxide, sodium fluoride, potassium rhodanide get successively 0.865g, 0.515g, 1.930g place water-ethanol (36mL water/12mL ethanol, V/V=3:1) in the mixed solvent, uniform stirring 0.5h.Be transferred in the 60mL polytetrafluoroethylene reactor and seal reaction 16h under 200 ℃.The reaction products therefrom through deionized water and absolute ethanol washing, centrifugation and under 60 ℃ of conditions of vacuum dry 6h, obtain MoS
2Nano-hollow material.
Gained MoS
2The XRD spectra of nano-hollow material product as shown in Figure 1; Gained MoS
2Nano-hollow material transmission electron microscope and stereoscan photograph are as shown in Figure 2.
Control sample: MoS
2The preparation of nanometer solid material
With molybdenum oxide, sodium fluoride, potassium rhodanide (0.865g, 0.515g, 1.930g) in 50mL water-glycerine (36/12mL, V/V=3:1) mixed solvent, uniform stirring 0.5h.Place 60mL polytetrafluoroethylene reactor, 210 ℃ of lower reactions 16 hours.
Gained MoS
2The transmission electron microscope of nanometer solid material and stereoscan photograph are as shown in Figure 3.
The below is MoS
2The chemical property of nano-hollow material and MoS
2The contrast test of nanometer solid material
Respectively with in above-described embodiment 1 preparation MoS
2Nano-hollow material and comparative sample MoS
2The nanometer solid material is the active material in the electrode material, characterizes chemical property.
Electrode preparation method is as follows: with conductive agent: binding agent: active material (MoS
2Nano-hollow or nanometer solid material) with the ratio mixed slurry of 10:20:70, conductive agent adopts acetylene black, and binding agent adopts Kynoar (PVDF), controls being coated on the Copper Foil collector of certain even thickness.The electrode slice of the suitable size of cutting, 80 ℃ were dried by the fire 12 hours in vacuum, in glove box, form button cell, the lithium sheet is to electrode, 1M LiPF6-EC/DMC/DMC (V/V/V=1:1:1) is electrolyte, barrier film is Celgard2400 (PP monofilm), forms button cell (CR2032).Battery operated interval is 0.01V ~ 3.0V.
Fig. 4 is MoS
2Hollow nano-material and MoS
2Nanometer solid material high rate performance figure, under the 1000mA/g current density, MoS
2The hollow nano-material specific capacity reaches 780mAh/g, when returning low current density, still can obtain higher specific capacity, compares solid nano material and is greatly improved.Fig. 5 is gained MoS
2Hollow nano-material and MoS
2The performance comparison that the nanometer solid material circulates under the 100mA/g current density, MoS
2Hollow nano-material can also keep the specific capacity of 902mAh/g after 80 circles, demonstrate the electrochemical stability of obvious enhancing.
Embodiment 2:
Molybdenum oxide, sodium fluoride, potassium rhodanide (0.865g, 0.515g, 1.930g) are mixed to join in the 50mL water-ethanol mixed solvent reaction system, and the mixed solvent volume ratio is pressed respectively water/ethanol=3/1 or 1/1.Uniform stirring 0.5h changes in the 60mL polytetrafluoroethylene reactor, the sealing, in 140 ~ 220 ℃ the reaction 17h, the reaction products therefrom through deionized water and absolute ethanol washing, centrifugation and under 60 ℃ of conditions of vacuum dry 8h, obtain MoS
2Nano-hollow material.
Embodiment 3:MoS
2The preparation of nano-hollow material
Molybdenum oxide 0.865g, sodium fluoride 0.515g, potassium rhodanide 1.930g are mixed, join (water/ethanol volume ratio is 1/2) in the 50mL water-ethanol mixed solvent reaction system, be sealed in the polytetrafluoroethylene reactor, under 200 ℃ of conditions, react 18h, product is through deionized water and absolute ethanol washing, centrifugation and 60 ℃ of lower vacuumizes 6 hours obtains the powder-product of black, i.e. MoS at last
2Nano-hollow material.
Embodiment 4: nanometer sheet is self-assembled into MoS
2The preparation of nano-hollow material
0.865g molybdenum oxide, 0.515g sodium fluoride, 1.930g potassium rhodanide are mixed, be sealed in the polytetrafluoroethylene reactor, join by (water/ethanol=2/1 volume ratio) in the 50mL water-ethanol mixed solvent reaction system, under 180 ~ 220 ℃ of conditions, react 16h, product is through deionized water and absolute ethanol washing, centrifugation and 60 ℃ of lower vacuumizes 6 hours obtains the powder-product of black, i.e. MoS at last
2Nano-hollow material.
Claims (7)
1. MoS
2Nano-hollow material makes by the following method:
Raw material molybdenum oxide, sodium fluoride, potassium rhodanide are mixed 0.8 ~ 0.9:0.5 ~ 0.6:1.5 ~ 2.0 in mass ratio, join in the water-ethanol mixed solvent, the mass volume ratio of raw material and mixed solvent is (5.6 ~ 7)/100, and unit is g/mL; Place reactor to seal, in 140 ~ 220 ℃ of reaction 12 ~ 30h, products therefrom is through washing, separate, being drying to obtain.
2. MoS as claimed in claim 1
2Nano-hollow material is characterized in that described mixed solvent is water: ethanol volume ratio (3 ~ 1): (1 ~ 3).
3. MoS
2The preparation method of nano-hollow material, step is as follows:
Raw material molybdenum oxide, sodium fluoride, potassium rhodanide are mixed 0.8 ~ 0.9:0.5 ~ 0.6:1.5 ~ 2.0 in mass ratio, join in the water-ethanol mixed solvent, the mass volume ratio of raw material and mixed solvent is (5.6 ~ 7)/100, and unit is g/mL; Stir 0.5 ~ 1h, place the polytetrafluoroethylene reactor to seal, in 140 ~ 220 ℃ of reaction 12 ~ 30h, the reaction products therefrom is through deionized water and absolute ethanol washing, centrifugation and under 60 ℃ of conditions of vacuum dry 6 ~ 8h, obtain the MoS of nanometer sheet self assembly
2Nano-hollow material.
4. MoS as claimed in claim 3
2The preparation method of nano-hollow material, it is characterized in that step is as follows: the water-ethanol (3 ~ 1) that molybdenum oxide 0.865g, sodium fluoride 0.515g, potassium rhodanide 1.930g is mixed to join 50mL: in the mixed solvent reaction system of (1 ~ 3) volume ratio, uniform stirring 0.5h changes in the 60mL polytetrafluoroethylene reactor, sealing, in 180 ~ 220 ℃ of reaction 16 ~ 20h, the reaction products therefrom is through deionized water and absolute ethanol washing, centrifugation and under 60 ℃ of conditions of vacuum dry 6 ~ 7h, and get final product.
5. MoS as claimed in claim 3
2The preparation method of nano-hollow material, it is characterized in that step is as follows: molybdenum oxide 0.865g, sodium fluoride 0.515g, potassium rhodanide 1.930g are mixed to join in the mixed solvent reaction system of water-ethanol 3:1 volume ratio of 48mL, uniform stirring 0.5h changes in the 60mL polytetrafluoroethylene reactor and seals, under 200 ℃ of conditions, react 16h, product is through deionized water and absolute ethanol washing, centrifugation and at 60 ℃ of lower vacuumize 6h obtains MoS
2Nano-hollow material.
6. claim 1 or 2 described MoS
2Nano-hollow material is as the application of storage lithium electrode material activity material.
7. claim 1 or 2 described MoS
2Nano-hollow material is used for preparing by the following method electrode:
With conductive agent: binding agent: than mixed slurry, conductive agent adopts acetylene black to active material with the quality of 20:10:70, and binding agent adopts Kynoar (PVDF), and active material adopts the MoS of described nanometer sheet self assembly
2Nano-hollow material; Mixed slurry is coated on the Copper Foil collector, is cut into electrode slice, 80 ℃ were dried by the fire 12 hours in vacuum; Form button cell by prior art, the lithium sheet is to electrode, and battery operated interval is 0.01V-3.0V.
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| CN104140124A (en) * | 2014-07-31 | 2014-11-12 | 中国科学技术大学 | Preparation method of TiO2 nanowire and preparation method of TiO2/MoS2 compound |
| CN104148099A (en) * | 2014-07-21 | 2014-11-19 | 河南师范大学 | Preparation method for MoS2-BiPO4 composite photocatalyst |
| CN106532040A (en) * | 2016-11-23 | 2017-03-22 | 广东轻工职业技术学院 | H-MoS2/NG nanocomposite material and preparation method and application thereof |
| CN106876731A (en) * | 2017-01-23 | 2017-06-20 | 吉林大学 | A kind of molybdenum disulfide nano superstructure material and its application |
| CN113697856A (en) * | 2021-08-30 | 2021-11-26 | 齐齐哈尔大学 | NbS2Solvothermal preparation method of nanosheet self-assembled hollow microsphere |
| CN114520327A (en) * | 2020-11-20 | 2022-05-20 | 中国科学院大连化学物理研究所 | Preparation method and application of mesoporous molybdenum disulfide/carbon composite material |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104148099A (en) * | 2014-07-21 | 2014-11-19 | 河南师范大学 | Preparation method for MoS2-BiPO4 composite photocatalyst |
| CN104148099B (en) * | 2014-07-21 | 2016-06-08 | 河南师范大学 | A kind of MoS2-BiPO4The preparation method of composite photo-catalyst |
| CN104140124A (en) * | 2014-07-31 | 2014-11-12 | 中国科学技术大学 | Preparation method of TiO2 nanowire and preparation method of TiO2/MoS2 compound |
| CN104140124B (en) * | 2014-07-31 | 2016-07-06 | 中国科学技术大学 | One-dimensional TiO2The preparation method of nano wire and TiO2/MoS2The preparation method of complex |
| CN106532040A (en) * | 2016-11-23 | 2017-03-22 | 广东轻工职业技术学院 | H-MoS2/NG nanocomposite material and preparation method and application thereof |
| CN106532040B (en) * | 2016-11-23 | 2019-05-07 | 广东轻工职业技术学院 | A kind of H-MoS2/ NG nanocomposite and preparation method and application |
| CN106876731A (en) * | 2017-01-23 | 2017-06-20 | 吉林大学 | A kind of molybdenum disulfide nano superstructure material and its application |
| CN114520327A (en) * | 2020-11-20 | 2022-05-20 | 中国科学院大连化学物理研究所 | Preparation method and application of mesoporous molybdenum disulfide/carbon composite material |
| CN114520327B (en) * | 2020-11-20 | 2023-11-07 | 中国科学院大连化学物理研究所 | Preparation method and application of mesoporous molybdenum disulfide/carbon composite material |
| CN113697856A (en) * | 2021-08-30 | 2021-11-26 | 齐齐哈尔大学 | NbS2Solvothermal preparation method of nanosheet self-assembled hollow microsphere |
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