CN104103810B - Multiple edge WS2/ Graphene electrochemistry storage lithium combination electrode and preparation method - Google Patents
Multiple edge WS2/ Graphene electrochemistry storage lithium combination electrode and preparation method Download PDFInfo
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- 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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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of multiple edge WS2/ Graphene electrochemistry storage lithium combination electrode and preparation method thereof, its chemistry storage lithium active substance is the multiple edge WS of few number of plies2Nanometer sheet and the composite nano materials of Graphene, WS in composite nano materials2Being 1:2 with the ratio of the amount of the material of Graphene, the component of combination electrode and mass percentage content thereof be: multiple edge WS2Nanometer sheet/graphite composite nano materials is 80 85%, acetylene black 5 10%, Kynoar 5 10%.Preparation process: first prepare the multiple edge WS of few number of plies2Nanometer sheet/graphene composite nano material, by prepared multiple edge WS2Nanometer sheet/graphene composite nano material and acetylene black and the uniform slurry of Kynoar furnishing, prepare combination electrode after being coated onto on Copper Foil rolling.Multiple edge WS prepared by the present invention2/ Graphene electrochemistry storage lithium combination electrode has high electrochemistry storage lithium capacity.
Description
Technical field
The present invention relates to electrochemistry storage lithium electrode and preparation method thereof, particularly relate to a kind of multiple edge WS2/ Graphene electrochemistry storage lithium combination electrode and preparation method thereof, belongs to new energy materials, energy storage and switch technology field.
Background technology
Lithium ion battery has the excellent properties such as high specific energy, memory-less effect, environmental friendliness, is widely used in the Portable movable electrical equipment such as mobile phone and notebook computer.As electrokinetic cell, lithium ion battery is also with a wide range of applications at aspects such as electric bicycle, electric automobile and intelligent grids.The negative material of lithium ion battery mainly uses graphite material (such as: graphite microspheres, natural modified graphite and Delanium etc.) at present, these graphite materials have preferable stable circulation performance, but its capacity is relatively low, the theoretical capacity of graphite is 372 mAh/g.Capacity and the stable circulation performance of electrode material are had higher requirement by a new generation's lithium ion battery, the performance of lithium ion battery is heavily dependent on the project of electrode material, the especially performance of negative material, do not require nothing more than negative material and there is high electrochemistry storage lithium specific capacity, and there is stable circulation performance and the high-rate characteristics of excellence.
Two-dimension nano materials has the characteristic of numerous excellence with the pattern of its uniqueness, and its research causes the great interest of people.Graphene is most typical two-dimension nano materials, and the two-dimensional nano chip architecture of its uniqueness makes the performances such as the physics of its numerous uniquenesses, chemistry and mechanics, has important scientific research meaning and technology application prospect widely.Graphene has high specific surface area, high conduction and heat conductivility, high charge mobility, excellent mechanical property, the characteristic of these excellences makes Graphene be with a wide range of applications at aspects such as micro-nano electronic device, energy storage material and novel catalyst carriers, and the application that nearest Graphene and material thereof store lithium as electrochemistry has obtained greatly paying close attention to of people.
WS2Have with graphite-like as layer structure, be the S-W-S that combines of the strongest covalent bond in its layer, be the most then more weak Van der Waals force.WS2More weak interlaminar action power and bigger interlamellar spacing allow to introduce external atom or molecule by insertion reaction at its interlayer.Such characteristic makes WS2Material can be as the material of main part of insertion reaction.Therefore, WS2It it is a kind of rising electrochemical lithium storage electrode material.But general WS2The electrochemistry storage lithium capacity of nano material is relatively low, and especially charge and discharge cycles stability and high power charging-discharging characteristic is poor, needs to improve further and strengthen.
The immense success that the discovery of Graphene and research thereof obtain excites the great interest that other inorganic two-dimension nano materials are studied by people, such as monolayer or the transition metal dichalcogenide etc. of few number of plies.Recently, Graphene concept has expanded to the inorganic compound of other layer structures from material with carbon element, namely for the inorganic material of layer structure, when its number of plies reduces (less than about 6 layers), when being especially reduced to monolayer, its electronic property or band structure can produce significantly change, thus cause which show the physics different from corresponding body phase material and chemical characteristic.In addition to Graphene, research shows when body phase WS2It is reduced to few number of plies (especially during monolayer), it is shown that physics visibly different with body phase material, chemistry and electronics property.Studies have reported that monolayer or the WS of few number of plies2There is more preferable electrochemistry storage lithium performance.But as the electrode material of electrochemistry storage lithium, WS2The lowest electric conductivity have impact on its application performance.
Due to WS2Nanometer sheet has similar two-dimensional nano sheet pattern with Graphene, and both have good similarity on microscopic appearance and crystal structure.If by WS2Nanometer sheet and Graphene are combined the composite of preparation, the high conduction performance of graphene nanometer sheet can improve the electric conductivity of composite further, strengthen the electron transmission in electrochemistry storage lithium electrode course of reaction, the electrochemistry storage lithium performance of composite can be improved further.With common WS2Nanometer sheet compares, the multiple edge WS of few number of plies2Nanometer sheet can provide the shortest lithium ion diffusion admittance, has more contact area with electrolyte.Therefore, multiple edge WS2The composite nano materials of nanometer sheet/Graphene has more preferable electrochemistry storage lithium performance.
But, up to the present, use multiple edge WS2Nanometer sheet/graphene composite nano material have not been reported as electrochemistry storage lithium combination electrode and the preparation thereof of electroactive substance.First the present invention is raw material with graphene oxide and sulfur for ammonium tungstate, by with the addition of hydro-thermal reaction method and the heat treatment subsequently of ionic liquid, is prepared for few number of plies multiple edge WS2The composite nano materials of nanometer sheet/Graphene, then with this multiple edge WS2The composite nano materials of nanometer sheet/Graphene, as the active substance of electrochemistry storage lithium, is prepared for the combination electrode of electrochemistry storage lithium.This prepare multiple edge WS2The method of/graphene combination electrode has simple, convenient and is easily enlarged industrial applications a little.
Summary of the invention
It is an object of the invention to provide a kind of multiple edge WS2/ Graphene electrochemistry storage lithium combination electrode and preparation method thereof, the multiple edge WS that electrochemistry storage lithium active substance is few number of plies of this combination electrode2The composite nano materials of nanometer sheet/Graphene, multiple edge WS in composite nano materials2The ratio of the amount of the material of nanometer sheet and Graphene is 1:1-1:4, and the component of combination electrode and mass percentage content thereof be: multiple edge WS2Nanometer sheet/graphene composite nano material 80-85%, acetylene black 5-10%, Kynoar 5-10%.
In technique scheme, few number of plies refers to 6 layers or less than 6 layers.
As preferably, multiple edge WS2The number of plies of nanometer sheet is 2-5 layer, multiple edge WS2The ratio of the amount of the material of nanometer sheet and Graphene is 1:2.
The multiple edge WS of the present invention2The preparation method of/Graphene electrochemistry storage lithium combination electrode sequentially includes the following steps:
(1) by graphene oxide ultrasonic disperse in deionized water, ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIM] BF is added4), its structure is shown in the schematic diagram of Fig. 1, and be sufficiently stirred for, then Cys and sulfur are sequentially added for ammonium tungstate, and be stirred continuously and make Cys and sulfur be completely dissolved for ammonium tungstate, Cys and sulfur are 5:1 for the ratio of the amount of the material of ammonium tungstate consumption, sulfur for the ratio of ammonium tungstate and the amount of the material of graphene oxide at 1:2;
(2) mixed dispersion that step (1) obtains is transferred in hydrothermal reaction kettle, and add deionized water adjustment volume to the 80% of hydrothermal reaction kettle nominal volume, the content of ionic liquid is 6.25 mL/L, this reactor is put in constant temperature oven, at 240 DEG C after hydro-thermal reaction 24 h, it is allowed to naturally cool to room temperature, hydro-thermal solid product is collected with centrifugation, and fully wash with deionized water, it is vacuum dried at 100 DEG C, obtained by hydro-thermal solid product in nitrogen/hydrogen mixed gas atmosphere at 500 DEG C heat treatment 2 h, in mixed gas, the volume fraction of hydrogen is 10%, prepare multiple edge WS2The composite nano materials of nanometer sheet/Graphene;
(3) by the multiple edge WS of above-mentioned preparation2Nanometer sheet/graphene composite nano material stores lithium active substance as the electrochemistry of electrode, under agitation being sufficiently mixed the uniform slurry of furnishing with the N-Methyl pyrrolidone solution of acetylene black and the Kynoar of mass fraction 5%, each constituent mass percentage ratio is: multiple edge WS2Nanometer sheet/graphene composite nano material 80-85%, acetylene black 5-10%, Kynoar 5-10%, this slurry is coated onto equably on the Copper Foil of collector, is dried, after rolling, obtains multiple edge WS2/ Graphene electrochemistry storage lithium combination electrode.
Above-mentioned graphene oxide uses the Hummers method improved to prepare.
The multiple edge WS of the present invention2/ Graphene electrochemistry storage lithium combination electrode and preparation method thereof has the advantage that
Surface of graphene oxide and edge with a lot of oxygen-containing functional groups (such as hydroxyl, carbonyl, carboxyl), these oxygen-containing functional groups make graphene oxide more easily be dispersed in water or organic liquid, but these oxygen-containing functional groups make surface of graphene oxide with negative charge so that graphene oxide and the WS with negative charge4 2-Ion is incompatible, and the present invention is piled up by Π-Π and the positively charged ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate schematic diagram of Fig. 1 (its structure see) is first adsorbed onto surface of graphene oxide, WS by electrostatic interaction4 2-Ion is just easier to interact with the graphene oxide having adsorbed ionic liquid combine.Research shows WS2The surface energy of its basic side, therefore, WS prepared by general hydro-thermal reaction can be much higher than in the surface at nanometer sheet edge2Nanometer sheet edge is less.Prepare the WS of more multiple edge2Nanometer sheet will manage to reduce WS2The surface energy at nanometer sheet edge.In hydro-thermal reaction, add ionic liquid, WS can be reduced2The surface energy at nanometer sheet edge, the hydro-thermal reaction approach therefore assisted by ionic liquid can prepare the WS of more multiple edge2The composite nano materials of nanometer sheet/Graphene.Compared with common quaternary cationics, the positive charge of ionic liquid cationic be distributed across in nitrogen heterocyclic ring (such as: imidazole ring, see Fig. 1), this nitrogen heterocyclic ring containing positive charge can preferably interact with electronegative graphene oxide than general quaternary cationics.This is because positively charged quaternary ammonium N is sp in general quaternary cationics3Hydridization, in succession 3 methyl and a long alkyl chain, hamper the mutual electrostatic attraction effect of positively charged quaternary ammonium N and graphene oxide;And 2 N in heterocycle are the sp of planar structure in ionic liquid2Hydridization, is piled up by Π-Π and electrostatic attraction can preferably interact with graphene oxide.Composite prepared by the present invention has accurate three-dimensional loose structure, WS therein2It is the nanometer sheet of few number of plies multiple edge, it is provided that the shortest lithium ion diffusion admittance, increases the contact area with electrolyte, contribute to being obviously enhanced its electrochemistry storage lithium performance.Therefore, the multiple edge WS of the present invention2/ Graphene electrochemistry storage lithium combination electrode has the electrochemistry storage lithium performance being obviously enhanced.The preparation method of the present invention also has feature that is simple, convenient and that be easily enlarged industrial applications.
Accompanying drawing explanation
Fig. 1 ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIM] BF4) structural representation.
The multiple edge WS that Fig. 2 embodiment 1 prepares2The XRD figure of nanometer sheet/graphene composite nano material.
The multiple edge WS that Fig. 3 embodiment 1 prepares2The SEM shape appearance figure of nanometer sheet/graphene composite nano material and transmission electron microscope photo.
WS prepared by Fig. 4 comparative example2Nanometer sheet and the TEM/HRTEM photo of graphene composite nano material.
Detailed description of the invention
The present invention is further illustrated below in conjunction with embodiment.
Graphene oxide in following example uses the Hummers method improved to prepare: 0oUnder C ice bath, by 10.0 mmol (0.12 g) graphite powder dispersed with stirring to 50 mL concentrated sulphuric acids, it is stirred continuously down and is slowly added into KMnO4, added KMnO4Quality be 4 times of graphite powder, stir 50 minutes, when temperature rises to 35 DEG C, be slowly added into 50 mL deionized waters, be stirred for 30 minutes, add the H of 15 mL mass fractions 30%2O2, stir 30 minutes, through centrifugation, after the HCl solution of mass fraction 5%, deionized water and acetone cyclic washing, obtain graphene oxide successively.
Embodiment 1.
1) by 2.5 mmol graphene oxide ultrasonic disperse in 60 mL deionized waters, add the 0.5 mL ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate schematic diagram of Fig. 1 (its structure see), and be sufficiently stirred for, then 0.76 g (6.25 mmol) Cys and 1.25 mmol sulfur are sequentially added for ammonium tungstate, and be stirred continuously and make Cys and sulfur be completely dissolved for ammonium tungstate, adjust volume to about 80 mL with deionized water;
2) obtained mixed liquor is transferred in the hydrothermal reaction kettle of 100 mL, this reactor is put in constant temperature oven, at 240 DEG C after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, collect solid product with centrifugation, and fully wash with deionized water, it is vacuum dried at 100 DEG C, by obtained hydro-thermal solid product in nitrogen/hydrogen mixed gas atmosphere at 500 DEG C heat treatment 2h, in mixed gas, the volume fraction of hydrogen is 10%, prepares multiple edge WS2The composite nano materials of nanometer sheet/Graphene, multiple edge WS in composite nano materials2Nanometer sheet is 1:2 with the ratio of the amount of Graphene material, obtains multiple edge WS with XRD, SEM and TEM to prepared2The composite nano materials of nanometer sheet/Graphene characterizes, and characterization result display composite nano materials is accurate three-dimensional loose structure, WS therein2Being the nanometer sheet of few number of plies multiple edge, its number of plies is at 2-5 layer, and the average number of plies is 3 layers (see Fig. 2 and Fig. 3);
3) by the multiple edge WS of above-mentioned preparation2Nanometer sheet/graphene composite nano material is as the active substance of electrochemistry storage lithium, the uniform slurry of furnishing under agitation it is sufficiently mixed with the N-Methyl pyrrolidone solution of acetylene black and the Kynoar of mass fraction 5%, this uniform slurry is coated onto equably on the Copper Foil of collector, it is vacuum dried at 120 DEG C, after rolling, obtains multiple edge WS2/ Graphene electrochemistry storage lithium combination electrode, in combination electrode, each constituent mass percentage ratio is: multiple edge WS2Nanometer sheet/graphene composite nano material 80%, acetylene black 10%, Kynoar 10%.
Electrochemistry storage lithium performance test: with lithium sheet as to electrode, electrolyte is 1.0 M LiPF6EC/DMC solution (1:1 in volume), barrier film is polypropylene screen (Celguard-2400), two electrode test batteries it are assembled in the suitcase of full argon, the test of battery constant current charge-discharge is carried out on programme controlled auto charge and discharge instrument, charging and discharging currents density 100 mA/g, voltage range 0.005 ~ 3.00 V;The test of high-rate charge-discharge capability: test its electrochemistry storage lithium specific capacity when charging and discharging currents is 1000 mA/g, as measuring of its high power charging-discharging characteristic.
Electrochemical results shows: multiple edge WS2The electrochemistry storage initial reversible capacity of lithium of/graphene combination electrode is 1285 mAh/g, and after 50 and 100 circulations, reversible capacity is 1262 and 1251 mAh/g, it is shown that high specific capacity and excellent stable circulation performance;When high current charge-discharge (charging and discharging currents is 1000 mA/g), its capacity is 853 mAh/g, is much higher than the theoretical capacity (372 mA/g) of graphite material, it is shown that its high power charging-discharging characteristic strengthened.
Comparative example
Without ionic liquid, it is prepared for WS by above-mentioned similar approach2Nanometer sheet/Graphene electrochemistry storage lithium combination electrode, concrete preparation process is as follows:
nullBy 2.5 mmol graphene oxide ultrasonic disperse in 60 mL deionized waters,Then 0.76g (6.25 mmol) Cys and 1.25 mmol sulfur it are sequentially added into for ammonium tungstate,And be stirred continuously and make Cys and sulfur be completely dissolved for ammonium tungstate,With deionized water adjustment volume to about 80 mL,Obtained mixed liquor is transferred in the hydrothermal reaction kettle of 100 mL,This reactor is put in constant temperature oven,At 240 DEG C after hydro-thermal reaction 24 h,It is allowed to naturally cool to room temperature,Solid product is collected with centrifugation,And fully wash with deionized water,It is vacuum dried at 100 DEG C,By obtained hydro-thermal solid product in nitrogen/hydrogen mixed gas atmosphere at 500 DEG C heat treatment 2h,In mixed gas, the volume fraction of hydrogen is 10%,Prepare WS2The nano composite material of nanometer sheet/Graphene, WS in composite nano materials2It is 1:2 with the ratio of the amount of the material of Graphene.With XRD, SEM and TEM to preparing WS2The nano composite material of nanometer sheet/Graphene characterizes, characterization result display WS2Nanometer sheet (see Fig. 4) for layer structure.
By above-mentioned steps 3) process prepare WS2Nanometer sheet/Graphene electrochemistry storage lithium combination electrode, and test its electrochemistry storage lithium performance by above-mentioned identical method.Electrochemical results shows: WS2Nanometer sheet/Graphene electrochemistry storage lithium combination electrode electrochemistry storage initial reversible capacity of lithium is 923 mAh/g, and after 50 and 100 circulations, reversible capacity is 881 and 865 mAh/g;When high current charge-discharge (charging and discharging currents is 1000 mA/g), its capacity is 526 mAh/g.
Claims (2)
1. a multiple edge WS2/ Graphene electrochemistry storage lithium combination electrode, it is characterised in that multiple
The multiple edge WS that electrochemistry storage lithium active substance is few number of plies of composite electrode2Nanometer sheet/Graphene
Composite nano materials, described few number of plies is less than 6 layers, multiple edge in composite nano materials
WS2The ratio of the amount of the material of nanometer sheet and Graphene is 1:2, the component of combination electrode and matter thereof
Amount degree is: multiple edge WS2Nanometer sheet/graphene composite nano material 80-85%,
Acetylene black 5-10%, Kynoar 5-10%, the preparation method of described combination electrode by with
Lower step is carried out:
(1) by graphene oxide ultrasonic disperse in deionized water, ionic liquid 1-fourth is added
Base-3-methyl imidazolium tetrafluoroborate ([BMIM] BF4), and be sufficiently stirred for, add the most successively
Enter Cys and sulfur for ammonium tungstate, and be stirred continuously and make Cys and sulfur for wolframic acid
Ammonium is completely dissolved, and Cys and sulfur are 5:1 for the ratio of the amount of the material of ammonium tungstate consumption,
Sulfur is 1:2 for the ratio of ammonium tungstate with the amount of the material of graphene oxide;
(2) mixed dispersion that step (1) obtains is transferred in hydrothermal reaction kettle, and
Add deionized water and adjust volume to the 80% of hydrothermal reaction kettle nominal volume, containing of ionic liquid
Amount is 6.25mL/L, puts in constant temperature oven by this reactor, hydro-thermal reaction at 240 DEG C
After 24h, allow it naturally cool to room temperature, collect hydro-thermal solid product with centrifugation, and use
Deionized water fully washs, and is vacuum dried at 100 DEG C, and obtained hydro-thermal solid product exists
In nitrogen/hydrogen mixed gas atmosphere at 500 DEG C heat treatment 2h, the volume of hydrogen in mixed gas
Mark is 10%, prepares multiple edge WS2The composite nano materials of nanometer sheet/Graphene;
(3) by the multiple edge WS of above-mentioned preparation2Nanometer sheet/graphene composite nano material conduct
The electrochemistry storage lithium active substance of electrode, with acetylene black and the Kynoar of mass fraction 5%
N-Methyl pyrrolidone solution be under agitation sufficiently mixed the uniform slurry of furnishing, by this slurry
Material is coated onto equably as on the Copper Foil of collector, is dried, obtains multiple edge WS after rolling2/
Graphene electrochemistry storage lithium combination electrode.
Multiple edge WS the most according to claim 12/ Graphene electrochemistry storage lithium compound electric
Pole, it is characterised in that described multiple edge WS2The number of plies of nanometer sheet is 2~5 layers.
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CN102683648A (en) * | 2012-06-08 | 2012-09-19 | 浙江大学 | Preparation method of few-layer MoS2/graphene electrochemical storage lithium composite electrode |
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