CN102723463B - Preparation method of single-layer MoS2/grapheme combined electrode of lithium ion battery - Google Patents
Preparation method of single-layer MoS2/grapheme combined electrode of lithium ion battery Download PDFInfo
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Abstract
The invention relates to a preparation method of a single-layer MoS2/grapheme combined electrode of lithium ion battery. The prepared method comprises the following steps of: ultrasonically dispersing graphene oxide in deionized water, sequentially adding cationic surfactant and sulfo-ammonium molybdate while stirring, slowly dripping hydrazine hydrate, reacting under 95-DEG C circulation reflux, respectively reducing the sulfo-ammonium molybdate and the graphene oxide into MoS2 and grapheme, centrifuging and collecting a solid product, washing, drying, carrying out heat treatment in a nitrogen/hydrogen mixing gas, and obtaining composite nanometer material of single-layer MoS2 and the grapheme; and mixing the composite nanometer material of single-layer MoS2 and the grapheme, acetylene black and polyvinylidene fluoride into mash, coating the mash on a copper foil, thus obtaining an electrode by rolling the mash. According to the preparation method disclosed by the invention, the technology is simple, the organic solvent is not needed to be consumed, and the combined electrode of the lithium ion battery has the advantages that the electrochemical lithium storage specific capacity is high, the circulation performance is stable, and the high-rate charge-discharge performance is good.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery combination electrode, especially lithium ion battery individual layer MoS
2the preparation method of/graphene combination electrode.
Background technology
Lithium ion battery has the excellent properties such as specific energy is high, memory-less effect, environmental friendliness, has been widely used in the Portable movable such as mobile phone and notebook computer electrical equipment.As electrokinetic cell, lithium ion battery is also with a wide range of applications on electric bicycle and electric automobile.The negative material of lithium ion battery mainly adopts graphite material (as: graphite microspheres, natural modified graphite and Delanium etc.) at present, these graphite materials have good stable circulation performance, but its capacity is lower, the theoretical capacity of graphite is 372mAh/g.Capacity and the stable circulation performance of a new generation's lithium ion battery to electrode material had higher requirement, and not only requires negative material to have high electrochemistry storage lithium capacity, and requires it to have good stable circulation performance and high power charging-discharging characteristic.
MoS
2and WS
2have the typical layered structure of similar graphite, in its layer, S-Mo-S is with covalent bonds, and interlayer, with weak Van der Waals force combination, is easily peeled off between layers.MoS
2weak interlaminar action power and larger interlamellar spacing allow to be reacted at its interlayer and introduced external atom or molecule by insertion.Such characteristic makes MoS
2material can be used as the material of main part that inserts reaction.Therefore, MoS
2electrode material (G.X.Wang, S.Bewlay, J.Yao, et al., Electrochem.Solid State, 2004, the 7:A321 of a kind of rising electrochemical lithium storage and electrochemistry storage magnesium; X.L.Li, Y.D.Li, J.Phys.Chem.B, 2004,108:13893).Li etc. [J.Alloys Compounds, 2009,471 (1-2) 442-447] have synthesized the MoS of floriform appearance with the hydrothermal method that ionic liquid is assisted
2, its electrochemistry storage lithium reversible capacity reaches 850mAh/g, but its charge and discharge cycles stability and high power charging-discharging characteristic are still not good enough, remain to be further improved and strengthen.
Recently, the research of individual layer two-dimensional nano material has caused people's very big interest.Graphene is current maximum individual layer two-dimensional nano materials of research, and Graphene has the performances such as physics, chemistry and the mechanics of numerous uniquenesses with its unique two-dimensional nano chip architecture, has important scientific research meaning and application prospect widely.Graphene has high specific area, high conduction and heat conductivility, high charge mobility, excellent mechanical property.Graphene is with a wide range of applications as the electrode material of micro-nano electronic device, new forms of energy battery, kollag and novel catalyst carrier.Graphene and composite material thereof have obtained broad research as the application of lithium ion battery negative material.Lithium can be store in the both sides of the bright graphene nanometer sheet of theoretical computational chart, and its theoretical capacity is 744mAh/g, is the twice of graphite theoretical capacity (372mAh/g).Yoo etc. [Nano Letters, 2008,8 (8): 2277-2282] studies show that Graphene has higher electrochemical reversible storage lithium capacity (540mAh/g), Graphene and carbon nano-tube or C
60the electrochemistry storage lithium capacity of compound composite material is respectively 730 and 784mAh/g.But the cycle performance that also has some bibliographical information Graphenes and composite electrode thereof need to improve.
The discovery of Graphene and research thereof have also evoked the research interest of people to other inorganic individual layer two-dimensional nano materials, and the inorganic two-dimensional nano material of the non-carbon of these individual layers has and the similar two-dimensional nano chip architecture of Graphene, as: the transition metal dichalcogenide MoS of individual layer
2and WS
2.Studies have shown that the inorganic compound of layer structure, its Electronic Performance and its number of plies have substantial connection.Recent studies have shown that compared with body phase material individual layer MoS
2and WS
2there are some new physical chemistry and photoelectric properties.Individual layer MoS
2also show good performance as lithium ion battery negative material, there is higher electrochemistry storage lithium capacity [Xiao Jie, Choi Daiwon, Cosimbescu Lelia, et al., Chemistry of Materials, 2010,22 (16): 4522-4524].But due to MoS
2be semi-conducting material in essence, its electronic conductivity is not high enough, need to strengthen its electric conductivity as the application of electrode material.
Individual layer MoS
2on microscopic appearance and crystal structure, there is good similitude, individual layer MoS with Graphene
2can store the application of lithium electrode material as electrochemistry with Graphene.If by individual layer MoS
2with the composite material of the compound preparation of Graphene, the high conductivity of graphene nanometer sheet can further improve the electric conductivity of composite material, strengthens the electronics transmission in electrochemical electrode reaction, the further chemical property of reinforced composite.Individual layer MoS in addition
2compound with graphene nanometer sheet, the large Π key of graphene nanometer sheet can with MoS
2the interaction of Electronic Structure, further strengthens the ability of electronics transmission and charge migration.Therefore, this individual layer MoS
2more excellent chemical property will be there is with the composite nano materials of graphene nanometer sheet as electrode material.
But, up to the present, individual layer MoS
2preparation be mainly the insertion based on lithium ion and the method peeled off, there is following shortcoming in this method: to the environment high such as air, moisture sensitivity, need to consume a large amount of organic solvents, time that need to be longer.Consider research and development one lithium ion battery individual layer MoS simply and easily from large-scale application
2the preparation method of/graphene combination electrode is still challenging and an innovate job.
Summary of the invention
The object of the present invention is to provide a kind of lithium ion battery individual layer MoS
2the preparation method of/graphene combination electrode.
Lithium ion battery individual layer MoS of the present invention
2the preparation method of/graphene combination electrode, the electrochemistry storage lithium active material of this combination electrode is individual layer MoS
2with Graphene composite nano materials, the component of combination electrode and mass percentage content thereof are: individual layer MoS
2/ Graphene composite nano materials 80-85%, acetylene black 5-10%, Kynoar 10%, wherein individual layer MoS
2individual layer MoS in/Graphene composite nano materials active material
2with the ratio of the amount of Graphene be 1:1-1:4; Preparation process is as follows: (1) is dispersed in deionized water ultrasonic graphene oxide, then adds cationic surfactant, and fully stirs, and cationic surfactant concentration is 0.01-0.05M, and the content of graphene oxide is 26.9-60.5mmol/L; (2) ammonium thiomolybdate is joined in the mixed system of step (1), ammonium thiomolybdate with the ratio of the amount of graphene oxide at 1:1-1:4, fully stir, under agitation slowly drip wherein mass percent concentration and be 85% hydrazine hydrate, dripping hydrazine hydrate volume is X, X/mL=YZ/mmol, Y=1.239-3.717, Z represents ammonium thiomolybdate amount of substance and graphene oxide amount of substance sum, continuous stirring is also heated to 95 ℃, constantly reacting 5-9h under stirring and counterflow condition, make ammonium thiomolybdate and graphene oxide be reduced into respectively MoS simultaneously
2and Graphene, collect solid product by centrifugation, and fully wash with deionization, then 100 ℃ of vacuumizes; (3) by obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2h, in mist, the volume ratio of hydrogen is 10%, obtains individual layer MoS
2composite nano materials with Graphene; (4) by the individual layer MoS of above-mentioned preparation
2/ Graphene composite nano materials is as the active material of electrode, under agitation fully mixes the uniform pastel of furnishing with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black and mass concentration 5%, and each constituent mass percentage is: individual layer MoS
2/ Graphene composite nano materials 80-85%, acetylene black 5-10%, Kynoar 10%, is coated onto this pastel on the Copper Foil of collector equably, vacuumize, roll extrusion obtains electrode.
In the present invention, described cationic surfactant is softex kw, DTAB, eight alkyl trimethyl ammonium bromides or tetra-n-butyl ammonium bromide.
Above-mentioned graphene oxide can adopt improved Hummers method preparation.
Method of the present invention has advantages of following outstanding compared with the prior art: graphene oxide surface and edge with a lot of oxygen-containing functional groups (as hydroxyl, carbonyl, carboxyl), these oxygen-containing functional groups are more easily dispersed in water or organic liquid graphene oxide, but these oxygen-containing functional groups make graphene oxide surface with negative electrical charge, make graphene oxide and the MoS with negative electrical charge
4 2-ion is incompatible, and the present invention is first adsorbed onto cationic surfactant graphene oxide surface by electrostatic interaction, and make it with part positive charge, and then mix with ammonium thiomolybdate, due to electrostatic interaction, MoS
4 2-ion just easily interacts and combines with the graphene oxide that has adsorbed cationic surfactant, more just prepares individual layer MoS by simple reduction and heat treatment
2with Graphene composite nano materials.Method of the present invention has technique feature simply and easily, does not consume organic solvent.Adopt individual layer MoS
2/ graphene composite material, as the electrochemistry storage lithium active material of lithium ion battery combination electrode, can make lithium ion battery have high electrochemistry storage lithium specific capacity, the high power charging-discharging characteristic that excellent cycle performance is become reconciled.
Accompanying drawing explanation
Fig. 1 is individual layer MoS
2with the XRD diffraction pattern of Graphene composite nano materials, in figure, * is individual layer MoS
2with individual layer MoS
2between interlamellar spacing, # is individual layer MoS
2and the interlamellar spacing between Graphene; The individual layer MoS that curve (a) is prepared for embodiment 1
2with Graphene composite nano materials; The individual layer MoS that curve (b) is prepared for embodiment 2
2with Graphene composite nano materials; The individual layer MoS that curve (c) is prepared for embodiment 6
2with Graphene composite nano materials; The simple MoS that curve (d) is prepared for comparative example
2material XRD figure.
Fig. 2 is individual layer MoS
2with the XRD diffraction pattern of Graphene composite nano materials, wherein: the individual layer MoS that curve (a) is prepared for embodiment 3
2with Graphene composite nano materials; The individual layer MoS that curve (b) is prepared for embodiment 4
2with Graphene composite nano materials.
Fig. 3 is individual layer MoS prepared by embodiment 2
2sEM pattern with Graphene composite nano materials.
Fig. 4 is individual layer MoS prepared by embodiment 2
2hRTEM figure with Graphene composite nano materials.
Embodiment
Further illustrate the present invention below in conjunction with embodiment.
Graphene oxide in following example adopts improved Hummers method preparation: under 0 ° of C ice bath, 5.38-12.10mmol (0.065-0.145g) graphite powder dispersed with stirring, in the 30mL concentrated sulfuric acid, is slowly added to KMnO under constantly stirring
4, institute adds KMnO
4quality be 4 times of graphite powder, stir 50 minutes, in the time of temperature rise to 35 ℃, slowly add 50ml deionized water, then stir 30 minutes, add the H of 15ml mass concentration 30%
2o
2, stir 30 minutes, through centrifugation, successively with obtaining graphene oxide after mass concentration 5%HCl solution, deionized water and acetone cyclic washing.
The hydrazine hydrate mass percent concentration dripping in following examples is 85%.
Embodiment 1 1) by the ultrasonic 10.76mmol graphene oxide deionized water that is dispersed in 200mL, add 0.01mol softex kw cationic surfactant (concentration 0.05M), and fully stir; 2) then 1.4g (5.38mmol) ammonium thiomolybdate is joined wherein, fully stir, under agitation slowly drip wherein hydrazine hydrate 20mL, continuous stirring is also heated to 95 ℃, constantly reacting 5h under stirring and counterflow condition, make ammonium thiomolybdate and graphene oxide be reduced into respectively MoS simultaneously
2and Graphene, collect solid product by centrifugation, and fully wash with deionization, then 100 ℃ of vacuumizes; 3) by obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2h, in mist, the volume ratio of hydrogen is 10%, prepares individual layer MoS after heat treatment
2composite nano materials with Graphene.With XRD, SEM and HRTEM to heat treatment after the end product that obtains characterize, characterization result shows that the product obtaining is individual layer MoS
2the composite material of/Graphene, wherein MoS
2with the ratio=1:2 of Graphene amount, XRD diffraction pattern is shown in Fig. 1 curve (a).
4) by the individual layer MoS of above-mentioned preparation
2/ Graphene composite nano materials is as the active material of electrode, under agitation fully mix the uniform pastel of furnishing with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black and mass concentration 5%, this pastel is coated onto equably on the Copper Foil of collector, vacuumize at 120 ℃, roll extrusion obtains lithium ion battery class Graphene/graphene combination electrode again, and in combination electrode, each constituent mass percentage is: individual layer MoS
2/ Graphene composite nano materials 80%, acetylene black 10%, Kynoar 10%.
Electrochemistry storage lithium performance test: as to electrode, electrolyte is 1.0M LiPF with lithium paper tinsel
6eC/DMC solution (1:1in volume), barrier film is polypropylene film (Celguard-2300), in the suitcase that is full of argon gas, be assembled into test battery, the test of battery constant current charge-discharge is carried out on programme controlled auto charge and discharge instrument, charging and discharging currents density 100mA/g, voltage range 0.005 ~ 3.00V; The test of high-rate charge-discharge capability: test its electrochemistry storage lithium specific capacity in the time that charging and discharging currents is 1000mA/g, as measuring of its high-rate charge-discharge capability.
Electro-chemical test shows: individual layer MoS
2the electrochemistry storage lithium reversible capacity of/graphene combination electrode is 810mAh/g, and after 50 circulations, capacity is 750mAh/g, has shown high specific capacity and excellent stable circulation performance.
In the time of high current charge-discharge (charging and discharging currents is 1000mA/g), individual layer MoS
2the capacity of/graphene combination electrode is 512mAh/g, is much higher than the theoretical capacity (372mA/g) of graphite material, has shown good high-rate charge-discharge capability.
Comparative example, does not add cationic surfactant and graphene oxide in preparation process, prepared simple MoS by above-mentioned similar approach
2with the simple MoS of lithium ion battery
2electrode, concrete preparation process is as follows: 1.4g (5.38mmol) ammonium thiomolybdate is joined in 200mL deionized water, fully stir and make its dissolving, under agitation slowly drip wherein hydrazine hydrate 20mL, continuous stirring is also heated to 95 ℃, constantly reacting 5h under stirring and counterflow condition, make ammonium thiomolybdate be reduced into MoS
2, collect solid product by centrifugation, and fully wash with deionization, then 100 ℃ of vacuumizes, by the solid product obtaining in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2h, in mist, the volume ratio of hydrogen is 10%, prepares simple MoS after heat treatment
2, its XRD diffraction pattern is shown in Fig. 1 curve (d), XRD characterizes and shows prepared simple MoS
2there is very strong (002) face XRD diffraction maximum, the simple MoS that surface is prepared
2for sandwich construction, its average number of plies is 18 layers, by above-mentioned 4) process prepares the simple MoS of lithium ion battery
2electrode, and test in the same way simple MoS
2the electrochemistry storage lithium performance of electrode.
Electro-chemical test shows: simple MoS
2the electrochemistry storage lithium reversible capacity of electrode is 820mAh/g, and after 50 circulations, capacity is 420mAh/g.In the time of high current charge-discharge (charging and discharging currents is 1000mA/g), individual layer MoS
2the capacity of/graphene combination electrode is 350mAh/g.
Test the chemistry storage lithium performance of prepared combination electrode by the method for embodiment 1.
Electro-chemical test shows: the lithium ion battery individual layer MoS of preparation
2the electrochemistry storage lithium reversible capacity of/graphene combination electrode is 903mAh/g, and after 60 circulations, capacity is 805mAh/g, has shown high specific capacity and excellent stable circulation performance.
In the time of high current charge-discharge (charging and discharging currents is 1000mA/g), its capacity is 621mAh/g, is much higher than the theoretical capacity (372mA/g) of graphite material, has shown good high-rate charge-discharge capability.
Embodiment 3 1) by the ultrasonic 10.76mmol graphene oxide deionized water that is dispersed in 200mL, add 0.004mol DTAB cationic surfactant (concentration 0.02M), and fully stir; 2) then 1.4g (5.38mmol) ammonium thiomolybdate is joined wherein, fully stir, under agitation slowly drip wherein hydrazine hydrate 20mL, continuous stirring is also heated to 95 ℃, constantly reacting 8h under stirring and counterflow condition, make ammonium thiomolybdate and graphene oxide be reduced into respectively MoS simultaneously
2and Graphene, collect solid product by centrifugation, and fully wash with deionization, then 100 ℃ of vacuumizes; 3) by obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2h, in mist, the volume ratio of hydrogen is 10%, prepares individual layer MoS after heat treatment
2composite nano materials with Graphene.With XRD, SEM and HRTEM to heat treatment after the end product that obtains characterize, characterization result shows that the product obtaining is individual layer MoS
2the composite material of/Graphene, wherein MoS
2with the ratio=1:2 of Graphene amount, XRD figure is shown in Fig. 2 curve (a); 4) by the individual layer MoS of above-mentioned preparation
2/ Graphene composite nano materials is as the active material of electrode, under agitation fully mix the uniform pastel of furnishing with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black and mass concentration 5%, this pastel is coated onto equably on the Copper Foil of collector, vacuumize at 120 ℃, then roll extrusion obtains lithium ion battery individual layer MoS
2/ graphene combination electrode, in combination electrode, each constituent mass percentage is: individual layer MoS
2/ Graphene composite nano materials 80%, acetylene black 10%, Kynoar 10%.
Test the chemistry storage lithium performance of prepared combination electrode by the method for embodiment 1.
Electro-chemical test shows: the lithium ion battery individual layer MoS of preparation
2the electrochemistry storage lithium reversible capacity of/graphene combination electrode is 906mAh/g, and after 70 circulations, capacity is 860mAh/g, has shown high specific capacity and excellent stable circulation performance.
In the time of high current charge-discharge (charging and discharging currents is 1000mA/g), its capacity is 650mAh/g, is much higher than the theoretical capacity (372mA/g) of graphite material, has shown good high-rate charge-discharge capability.
Embodiment 4 1) by the ultrasonic 10.76mmol graphene oxide deionized water that is dispersed in 200mL, add 0.01mol eight alkyl trimethyl ammonium bromide cationic surfactants (concentration 0.05M), and fully stir; 2) then 1.4g (5.38mmol) ammonium thiomolybdate is joined wherein, fully stir, under agitation slowly drip wherein hydrazine hydrate 20mL, continuous stirring is also heated to 95 ℃, constantly reacting 7h under stirring and counterflow condition, make ammonium thiomolybdate and graphene oxide be reduced into respectively MoS simultaneously
2and Graphene, collect solid product by centrifugation, and fully wash with deionization, then 100 ℃ of vacuumizes; 3) by obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2h, in mist, the volume ratio of hydrogen is 10%, prepares individual layer MoS after heat treatment
2composite nano materials with Graphene.With XRD, SEM and HRTEM to heat treatment after the end product that obtains characterize, characterization result shows that the product obtaining is individual layer MoS
2the composite material of/Graphene, wherein MoS
2with the ratio=1:2 of Graphene amount, XRD figure is shown in Fig. 2 curve (b).
4) by the individual layer MoS of above-mentioned preparation
2/ Graphene composite nano materials is as the active material of electrode, under agitation fully mix the uniform pastel of furnishing with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black and mass concentration 5%, this pastel is coated onto equably on the Copper Foil of collector, vacuumize at 120 ℃, then roll extrusion obtains lithium ion battery individual layer MoS
2/ graphene combination electrode, in combination electrode, each constituent mass percentage is: individual layer MoS
2/ Graphene composite nano materials 80%, acetylene black 10%, Kynoar 10%.
Test the chemistry storage lithium performance of prepared combination electrode by the method for embodiment 1.
Electro-chemical test shows: the lithium ion battery individual layer MoS of preparation
2the electrochemistry storage lithium reversible capacity of/graphene combination electrode is 880mAh/g, and after 60 circulations, capacity is 945mAh/g, has shown high specific capacity and excellent stable circulation performance.
In the time of high current charge-discharge (charging and discharging currents is 1000mA/g), its capacity is 680mAh/g, is much higher than the theoretical capacity (372mA/g) of graphite material, has shown good high-rate charge-discharge capability.
Embodiment 5 1) by the ultrasonic 5.38mmol graphene oxide deionized water that is dispersed in 200mL, add 0.01mol softex kw cationic surfactant (concentration 0.05M), and fully stir; 2) then 1.4g (5.38mmol) ammonium thiomolybdate is joined wherein, fully stir, under agitation slowly drip wherein hydrazine hydrate 20mL, continuous stirring is also heated to 95 ℃, constantly reacting 7h under stirring and counterflow condition, make ammonium thiomolybdate and graphene oxide be reduced into respectively MoS simultaneously
2and Graphene, collect solid product by centrifugation, and fully wash with deionization, then 100 ℃ of vacuumizes; 3) by obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2h, in mist, the volume ratio of hydrogen is 10%, prepares individual layer MoS after heat treatment
2with the composite nano materials of Graphene, with XRD, SEM and HRTEM to heat treatment after the end product that obtains characterize, characterization result shows that the product obtaining is individual layer MoS
2the composite material of/Graphene, wherein MoS
2ratio=1:1 with Graphene amount.
4) by the individual layer MoS of above-mentioned preparation
2/ Graphene composite nano materials is as the active material of electrode, under agitation fully mix the uniform pastel of furnishing with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black and mass concentration 5%, this pastel is coated onto equably on the Copper Foil of collector, vacuumize at 120 ℃, then roll extrusion obtains lithium ion battery individual layer MoS
2/ graphene combination electrode, in combination electrode, each constituent mass percentage is: individual layer MoS
2/ Graphene composite nano materials 80%, acetylene black 10%, Kynoar 10%.
Test the chemistry storage lithium performance of prepared combination electrode by the method for embodiment 1.
Electro-chemical test shows: the lithium ion battery individual layer MoS of preparation
2the electrochemistry storage lithium reversible capacity of/graphene combination electrode is 810mAh/g, and after 60 circulations, capacity is 820mAh/g, has shown high specific capacity and excellent stable circulation performance.
In the time of high current charge-discharge (charging and discharging currents is 1000mA/g), its capacity is 610mAh/g, is much higher than the theoretical capacity (372mA/g) of graphite material, has shown good high-rate charge-discharge capability.
Embodiment 6 1) by the ultrasonic 12.10mmol graphene oxide deionized water that is dispersed in 200mL, add 0.008mol softex kw cationic surfactant (concentration 0.03M), and fully stir; 2) then 1.05g (4.03mmol) ammonium thiomolybdate is joined wherein, fully stir, under agitation slowly drip wherein hydrazine hydrate 30mL, continuous stirring is also heated to 95 ℃, constantly reacting 9h under stirring and counterflow condition, make ammonium thiomolybdate and graphene oxide be reduced into respectively MoS simultaneously
2and Graphene, collect solid product by centrifugation, and fully wash with deionization, then 100 ℃ of vacuumizes; 3) by obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2h, in mist, the volume ratio of hydrogen is 10%, prepares individual layer MoS after heat treatment
2composite nano materials with Graphene.With XRD, SEM and HRTEM to heat treatment after the end product that obtains characterize, characterization result shows that the product obtaining is individual layer MoS
2the composite material of/Graphene, wherein MoS
2ratio=1:3 with Graphene amount; 4) by the individual layer MoS of above-mentioned preparation
2/ Graphene composite nano materials is as the active material of electrode, under agitation fully mix the uniform pastel of furnishing with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black and mass concentration 5%, this pastel is coated onto equably on the Copper Foil of collector, vacuumize at 120 ℃, then roll extrusion obtains lithium ion battery individual layer MoS
2/ graphene combination electrode, in combination electrode, each constituent mass percentage is: individual layer MoS
2/ Graphene composite nano materials 83%, acetylene black 7%, Kynoar 10%.
Test the chemistry storage lithium performance of prepared combination electrode by the method for embodiment 1.
Electro-chemical test shows: the lithium ion battery individual layer MoS of preparation
2the electrochemistry storage lithium reversible capacity of/graphene combination electrode is 853mAh/g, and after 60 circulations, capacity is 842mAh/g, has shown high specific capacity and excellent stable circulation performance.
In the time of high current charge-discharge (charging and discharging currents is 1000mA/g), its capacity is 605mAh/g, is much higher than the theoretical capacity (372mA/g) of graphite material, has shown good high-rate charge-discharge capability.
Embodiment 7 fully stirs; 2) then 0.7g (2.69mmol) ammonium thiomolybdate is joined wherein, fully stir, under agitation slowly drip wherein hydrazine hydrate 50mL, continuous stirring is also heated to 95 ℃, constantly reacting 6h under stirring and counterflow condition, make ammonium thiomolybdate and graphene oxide be reduced into respectively MoS simultaneously
2and Graphene, collect solid product by centrifugation, and fully wash with deionization, then 100 ℃ of vacuumizes; 3) by obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2h, in mist, the volume ratio of hydrogen is 10%, prepares individual layer MoS after heat treatment
2composite nano materials with Graphene.With XRD, SEM and HRTEM to heat treatment after the end product that obtains characterize, characterization result shows that the product obtaining is individual layer MoS
2the composite material of/Graphene, wherein MoS
2ratio=1:4 with Graphene amount.
4) by the individual layer MoS of above-mentioned preparation
2/ Graphene composite nano materials is as the active material of electrode, under agitation fully mix the uniform pastel of furnishing with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black and mass concentration 5%, this pastel is coated onto equably on the Copper Foil of collector, vacuumize at 120 ℃, then roll extrusion obtains lithium ion battery individual layer MoS
2/ graphene combination electrode, in combination electrode, each constituent mass percentage is: individual layer MoS
2/ Graphene composite nano materials 85%, acetylene black 5%, Kynoar 10%.
Test the chemistry storage lithium performance of prepared combination electrode by the method for embodiment 1.
Electro-chemical test shows: the lithium ion battery individual layer MoS of preparation
2the electrochemistry storage lithium reversible capacity of/graphene combination electrode is 920mAh/g, and after 60 circulations, capacity is 930mAh/g, has shown high specific capacity and excellent stable circulation performance.
In the time of high current charge-discharge (charging and discharging currents is 1000mA/g), its capacity is 635mAh/g, is much higher than the theoretical capacity (372mA/g) of graphite material, has shown good high-rate charge-discharge capability.
Embodiment 8 1) by the ultrasonic 10.76mmol graphene oxide deionized water that is dispersed in 200mL, add 0.004mol TBAB cationic surfactant (concentration 0.02M), and fully stir; 2) then 1.4g (5.38mmol) ammonium thiomolybdate is joined wherein, fully stir, under agitation slowly drip wherein hydrazine hydrate 30mL, continuous stirring is also heated to 95 ℃, constantly reacting 7h under stirring and counterflow condition, make ammonium thiomolybdate and graphene oxide be reduced into respectively MoS simultaneously
2and Graphene, collect solid product by centrifugation, and fully wash with deionization, then 100 ℃ of vacuumizes; 3) by obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2h, in mist, the volume ratio of hydrogen is 10%, prepares individual layer MoS after heat treatment
2composite nano materials with Graphene.With XRD, SEM and HRTEM to heat treatment after the end product that obtains characterize, characterization result shows that the product obtaining is individual layer MoS
2the composite material of/Graphene, wherein MoS
2ratio=1:2 with Graphene amount; 4) by the individual layer MoS of above-mentioned preparation
2/ Graphene composite nano materials is as the active material of electrode, under agitation fully mix the uniform pastel of furnishing with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black and mass concentration 5%, this pastel is coated onto equably on the Copper Foil of collector, vacuumize at 120 ℃, then roll extrusion obtains lithium ion battery individual layer MoS
2/ graphene combination electrode, in combination electrode, each constituent mass percentage is: individual layer MoS
2/ Graphene composite nano materials 80%, acetylene black 10%, Kynoar 10%.
Test the chemistry storage lithium performance of prepared combination electrode by the method for embodiment 1.
Electro-chemical test shows: the lithium ion battery individual layer MoS of preparation
2the electrochemistry storage lithium reversible capacity of/graphene combination electrode is 915mAh/g, and after 60 circulations, capacity is 870mAh/g, has shown high specific capacity and excellent stable circulation performance.
In the time of high current charge-discharge (charging and discharging currents is 1000mA/g), its capacity is 612mAh/g, is much higher than the theoretical capacity (372mA/g) of graphite material, has shown good high-rate charge-discharge capability.
Claims (1)
1. a lithium ion battery individual layer MoS
2the preparation method of/graphene combination electrode, is characterized in that the electrochemistry storage lithium active material of this combination electrode is individual layer MoS
2with Graphene composite nano materials, the component of combination electrode and mass percentage content thereof are: individual layer MoS
2/ Graphene composite nano materials 80-85%, acetylene black 5-10%, Kynoar 10%, wherein individual layer MoS
2individual layer MoS in/Graphene composite nano materials active material
2with the ratio of the amount of substance of Graphene be 1:1-1:4; Preparation process is as follows:
(1) be dispersed in deionized water ultrasonic graphene oxide, then add cationic surfactant, and fully stir, cationic surfactant concentration is 0.01-0.05 M, the content of graphene oxide is 26.9-60.5 mmol/L, described cationic surfactant is softex kw, DTAB, eight alkyl trimethyl ammonium bromides or tetra-n-butyl ammonium bromide;
(2) ammonium thiomolybdate is joined in the mixed system of step (1), ammonium thiomolybdate with the ratio of the amount of substance of graphene oxide at 1:1-1:4, fully stir, under agitation slowly drip wherein mass percent concentration and be 85% hydrazine hydrate, dripping hydrazine hydrate volume is X, X/mL=YZ/mmol, Y=1.239-3.717, Z represents ammonium thiomolybdate amount of substance and graphene oxide amount of substance sum, continuous stirring is also heated to 95 ℃, constantly under stirring and counterflow condition, reacting 5-9 h, make ammonium thiomolybdate and graphene oxide be reduced into respectively MoS simultaneously
2and Graphene, collect solid product by centrifugation, and fully wash with deionized water, then 100 ℃ of vacuumizes,
(3) by obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2h, in mist, the volume ratio of hydrogen is 10%, obtains individual layer MoS
2composite nano materials with Graphene;
(4) by the individual layer MoS of above-mentioned preparation
2/ Graphene composite nano materials is as the active material of electrode, under agitation fully mixes the uniform pastel of furnishing with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black and mass concentration 5%, and each constituent mass percentage is: individual layer MoS
2/ Graphene composite nano materials 80-85%, acetylene black 5-10%, Kynoar 10%, is coated onto this pastel on the Copper Foil of collector equably, vacuumize, roll extrusion obtains electrode.
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| CN104415771A (en) * | 2013-08-20 | 2015-03-18 | 中国科学院大连化学物理研究所 | Method for simply and massively preparing graphene dispersed molybdenum base sulfide catalyst |
| CN104124435B (en) * | 2014-07-17 | 2016-08-10 | 浙江大学 | Multiple edge MoS2nanometer sheet/Graphene electrochemistry storage sodium combination electrode and preparation method |
| CN104134783B (en) * | 2014-07-31 | 2017-03-15 | 北京科技大学 | Nano nickel sulphide/grapheme composite positive electrode material and preparation method thereof |
| CN105633344A (en) * | 2015-12-29 | 2016-06-01 | 上海大学 | Molybdenum disulfide nanosheet/nanocellulose/carbon nanotube/graphene composite lithium battery thin film negative electrode material and preparation method therefor |
| CN106298259B (en) * | 2016-08-22 | 2018-03-06 | 河南师范大学 | A kind of preparation method of 2H phases individual layer molybdenum disulfide nano sheet |
| CN106987857B (en) * | 2017-03-09 | 2018-12-25 | 陕西科技大学 | Single-layer metal structure molybdenum disulfide/redox graphene complex and preparation method thereof |
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| CN112875754B (en) * | 2021-01-19 | 2021-12-03 | 北京科技大学 | Preparation and application method of graphene intercalation molybdenum disulfide composite material |
| CN113140803A (en) * | 2021-04-29 | 2021-07-20 | 天能帅福得能源股份有限公司 | Based on lamella MoS2Preparation method of high-rate lithium ion battery as anode |
| CN113652292A (en) * | 2021-08-13 | 2021-11-16 | 四川欧力泰尔新材料有限公司 | Preparation method of microemulsion cutting fluid for machining aluminum alloy of aircraft engine |
| CN114203983B (en) * | 2021-11-04 | 2022-11-18 | 江苏大学 | Preparation method of porous zinc molybdate/zinc oxide/graphene composite material and application of porous zinc molybdate/zinc oxide/graphene composite material to negative electrode of lithium ion battery |
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