CN104103830B - Electrochemistry storage lithium combination electrode and the preparation method of a kind of high power capacity and stable circulation - Google Patents
Electrochemistry storage lithium combination electrode and the preparation method of a kind of high power capacity and stable circulation Download PDFInfo
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Abstract
The invention discloses electrochemistry storage lithium combination electrode of a kind of high power capacity and stable circulation and preparation method thereof, its electrochemistry storage lithium active material is MoS2-The composite nano materials of nanometer watt/Graphene, MoS in composite nano materials2The ratio of the amount of substance of nanometer watt and Graphene is 1:1-1:3, MoS2The nanometer watt layer structure for few number of plies, the average number of plies is 4 layers, the component of combination electrode and mass percentage content thereof are: MoS2Nanometer watt/Graphene composite nano materials is 80-85%, acetylene black 5-10%, Kynoar 5-10%. Preparation process comprises: first prepare MoS2Nanometer watt/Graphene composite nano materials, by prepared composite nano materials and acetylene black and Kynoar furnishing pastel, is coated onto dry on Copper Foil, roll extrusion and obtains electrode. Electrochemistry storage lithium combination electrode of the present invention has high electrochemistry storage lithium capacity, is with a wide range of applications.
Description
Technical field
The present invention relates to electrochemistry storage lithium electrode and preparation method thereof, relate in particular to and use MoS2Nanometer watt/Graphene is a kind of high power capacity of preparing of electroactive substance and combination electrode of stable circulation and preparation method thereof, belongs to new energy materials and applied technical field thereof.
Background technology
Lithium ion battery has the excellent properties such as high specific energy, memory-less effect, environmental friendliness, in the Portable movable such as mobile phone and notebook computer electrical equipment, is widely used. 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 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, the performance of lithium ion battery depends on the project of electrode material to a great extent, especially the performance of negative material, not only require negative material to there is high electrochemistry storage lithium specific capacity, and there is excellent stable circulation performance and high magnification characteristic.
Two-dimensional nano material has the characteristic of numerous excellences with its unique pattern, its research has caused people's very big interest. Graphene is most typical two-dimensional nano material, and its unique two-dimensional nano chip architecture makes the performances such as physics, chemistry and the mechanics of its numerous uniquenesses, has important scientific research meaning and technology application prospect widely. Graphene has high specific area, high conduction and heat conductivility, high charge mobility, excellent mechanical property, these excellent characteristics make Graphene be with a wide range of applications at aspects such as micro-nano electronic device, energy storage material and novel catalyst carriers, and Graphene and material thereof have obtained people's very big concern as the application of electrochemistry storage lithium recently.
MoS2Having and layer structure like graphite-like, is the S-Mo-S of very strong covalent bonds in its layer, is weak Van der Waals force between layers. MoS2Weak 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 MoS2Material can be used as the material of main part that inserts reaction. Therefore, MoS2Be a kind of rising electrochemical lithium storage and electrochemistry storage magnesium electrode material (G.X.Wang, S.Bewlay, J.Yao,etal., Electrochem.SolidState, 2004,7:A321; X.L.Li, Y.D.Li, J.Phys.Chem.B, 2004,108:13893.). Nineteen ninety-five Miki etc. has studied amorphous MoS2Electrochemical lithiation and de-lithium performance (Y.Miki, D.Nakazato, H.Ikuta, etal., J.PowerSources, 1995,54:508), found that the amorphous MoS of their synthesized2In powder, the reversible capacity of the electrochemistry doff lithium of the best sample of performance only has 200mAh/g, and after circulation 100 times, its reversible capacity drops to 100mAh/g, is the half of its initial capacity. Therefore, its reversible capacity and stable circulation performance also require further improvement. The electroactive material of synthesis of nano structure is an effective way improving its chemical property. Li etc. [J.AlloysCompounds, 2009,471 (1-2) 442-447] have synthesized the MoS of floriform appearance with the hydrothermal method that ionic liquid is assisted2, 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.
The immense success that the discovery of Graphene and research thereof obtain has excited the very big interest of people to other inorganic two-dimensional nano investigations of materials, as the transition metal dichalcogenide of individual layer or few number of plies etc. 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, in the time that its number of plies reduces (below 8 layers), especially while reducing to individual layer, its electronic property or band structure can produce obvious variation, thereby cause it to show the physics and chemistry characteristic different from corresponding body phase material. Except Graphene, research shows as body phase MoS2Reduce to few number of plies when individual layer (especially), shown and the visibly different physics of body phase material, chemistry and electronics property. Studies have reported that the MoS of individual layer or few number of plies2There is better electrochemistry storage lithium performance. But as the electrode material of electrochemistry storage lithium, MoS2Low electric conductivity between layers affected the performance of its application.
Due to MoS2Nanometer sheet and Graphene have similar two-dimensional nano sheet pattern, and both have good similitude on microscopic appearance and crystal structure. If by MoS2The composite of nanometer sheet and the compound preparation of Graphene, the high conduction performance of graphene nanometer sheet can further improve the electric conductivity of composite, strengthen the electronics transmission in electrochemistry storage lithium electrode course of reaction, can further improve the electrochemistry storage lithium performance of composite. With common MoS2Nanometer sheet comparison, the MoS of little nanometer watt shape pattern2Not only there is more edge, more short lithium ion diffusion admittance can be provided, and load on Graphene, there is more contact area with electrolyte. Therefore MoS2The composite nano materials of nanometer watt/Graphene can show the electrochemistry storage lithium performance of remarkable enhancing.
But, up to the present, use MoS2Nanometer watt/Graphene composite nano materials 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 sodium molybdate, and the hydrothermal method of assisting by Gemini surface active agent and heat treatment subsequently, prepared MoS2The composite nano materials of nanometer watt/Graphene, then uses MoS2The composite nano materials of nanometer watt/Graphene, as the active material of electrochemistry storage lithium, has been prepared the combination electrode of electrochemistry storage lithium. This preparation MoS2The method of nanometer watt/Graphene composite nano materials electrochemistry storage lithium combination electrode has simply, facilitates and be easy to expand industrial applications a little.
Summary of the invention
The object of the present invention is to provide electrochemistry storage lithium combination electrode of a kind of high power capacity and stable circulation and preparation method thereof, the electrochemistry storage lithium active material of this combination electrode is MoS2The composite nano materials of-nanometer watt/Graphene, MoS in composite nano materials2The ratio of the amount of substance of nanometer watt/Graphene is 1:2, MoS2The nanometer watt layer structure for few number of plies,, the component of combination electrode and mass percentage content thereof are: MoS2Nanometer watt/Graphene composite nano materials 80-85%, acetylene black 5-10%, Kynoar 10%.
In technique scheme, the layer structure of few number of plies refers to the layer structure of the number of plies below 6 layers or 6 layers.
As preferably, described MoS2The average number of plies of nanometer watt is 4 layers.
The preparation method of the electrochemistry storage lithium combination electrode of above-mentioned high power capacity and stable circulation carries out according to the following steps:
(1) be dispersed in deionized water ultrasonic graphene oxide, add the two ammonium bromides (its structure is shown in accompanying drawing 1) of Gemini surface active agent N-dodecyl trimethylene diamine, and fully stir, then add successively Cys and sodium molybdate, and constantly stir Cys and sodium molybdate are dissolved completely, the ratio of the amount of substance of Cys and sodium molybdate consumption is 5:1, and sodium molybdate is 1:2 with the ratio of the amount of substance of graphene oxide;
(2) mixed dispersion step (1) being obtained is transferred in hydrothermal reaction kettle, and add deionized water to adjust volume to 80% of hydrothermal reaction kettle nominal volume, the concentration of the two ammonium bromides of Gemini surface active agent N-dodecyl trimethylene diamine is 0.01 ~ 0.02mol/L, the content of graphene oxide is 30-70mmol/L, this reactor is put in constant temperature oven, at 230-250 DEG C after hydro-thermal reaction 24h, allow it naturally cool to room temperature, with centrifugation collection hydro-thermal reaction solid product, and fully wash by deionized water, vacuum drying at 100 DEG C, by the hydro-thermal reaction solid product obtaining in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C heat treatment 2h, in mist, hydrogen volume mark is 10%, finally prepare MoS2The composite nano materials of nanometer watt/Graphene;
(3) by the MoS of above-mentioned preparation2Nanometer watt/Graphene composite nano materials is as the electrochemistry storage lithium 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 fraction 5%, each constituent mass percentage is: MoS2Nanometer watt/Graphene composite nano materials 80-85%, acetylene black 5-10%, Kynoar 10%, is coated onto this pastel on the Copper Foil of collector equably, and dry, roll extrusion obtains combination electrode.
Above-mentioned graphene oxide adopts improved Hummers method preparation.
Hydrothermal method with the two ammonium bromides assistance of Gemini surface active agent N-dodecyl trimethylene diamine of the present invention is prepared MoS2The method of nanometer watt/Graphene composite nano materials has the following advantages: 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 MoO with negative electrical charge4 2-Ion is incompatible, and the present invention is first adsorbed onto graphene oxide surface by two Gemini surface active agent N-dodecyl trimethylene diamine ammonium bromides by electrostatic interaction, makes it with part positive charge, due to electrostatic interaction, and MoO4 2-Ion is just easy to interact and combine with the graphene oxide that has adsorbed Gemini surface active agent. The more important thing is, compared with common single cationic surfactant, in the two ammonium bromides of Gemini surface active agent N-dodecyl trimethylene diamine, there are 2 positively charged quaternary ammonium hydrophilic radicals, there is enough hydrophilies, and between electronegative graphene oxide, there is stronger mutual electrostatic interaction; The two ammonium bromides of N-dodecyl trimethylene diamine also have 2 hydrophobic long alkyl chain groups (its structure as shown in Figure 1), and its hydrophobicity is stronger. The two ammonium bromides of N-dodecyl trimethylene diamine are adsorbed on Graphene surface, there is (as shown in Figure 2) with irregular " brush head " form of bending in its hydrophobic grouping, this version has caused water-heat process and the heat treatment back loading MoS on Graphene surface2There is the pattern of nanometer watt. This undersized MoS2Nanometer watt has more edge, as electrochemistry Lithium storage materials, can provide more short lithium ion diffusion admittance, contributes to strengthen its electrochemistry storage lithium performance; In addition, MoS2Nanometer watt/graphene composite material can increase the contact area of itself and electrolyte, can further contribute to improve its chemical property. Therefore the present invention MoS2The electrochemistry storage lithium electrode that nanometer watt/graphene composite material is prepared as electroactive substance has high electrochemistry storage lithium capacity, excellent cycle performance and significantly strengthen large current density electrical characteristics.
Brief description of the drawings
The two ammonium bromide structural representations of Fig. 1 Gemini surface active agent N-dodecyl trimethylene diamine.
Fig. 2 Gemini surface active agent is adsorbed on the schematic diagram on graphene oxide surface.
The MoS that Fig. 3 embodiment 1 prepares2The XRD figure of nanometer watt/Graphene composite nano materials.
The MoS that Fig. 4 embodiment 1 prepares2SEM shape appearance figure and the transmission electron microscope photo of nanometer watt/Graphene composite nano materials.
MoS prepared by the comparative example of Fig. 5 embodiment 12The TEM of nanometer sheet and Graphene composite nano materials and HRTEM photo.
Detailed description of the invention
Further illustrate the present invention below in conjunction with embodiment.
Graphene oxide in following example adopts improved Hummers method preparation: 0oUnder C ice bath, 10.0mmol (0.12g) graphite powder dispersed with stirring, in the 50mL concentrated sulfuric acid, is slowly added to KMnO under constantly stirring4, institute adds KMnO4Quality be 4 times of graphite powder, stir 50 minutes, in the time of temperature rise to 35 DEG C, slowly add 50mL deionized water, then stir 30 minutes, add the H of 15mL mass fraction 30%2O2, stir 30 minutes, through centrifugation, after HCl solution, deionized water and the acetone cyclic washing with mass fraction 5%, obtain graphene oxide successively.
Embodiment 1
1) be dispersed in 60mL deionized water ultrasonic 2.5mmol graphene oxide, add again the two ammonium bromides of 0.8mmol Gemini surface active agent N-dodecyl trimethylene diamine, and fully stir, then add successively 0.76g (6.25mmol) Cys and 0.3g (1.25mmol) sodium molybdate (Na2MoO4·2H2O), and constantly stir Cys and sodium molybdate are dissolved completely, with extremely about 80mL of deionized water adjustment volume;
2) obtained mixed liquor is transferred in the hydrothermal reaction kettle of 100mL, this reactor is put in constant temperature oven, at 230 DEG C after hydro-thermal reaction 24h, allow it naturally cool to room temperature, collect solid product with centrifugation, and fully wash by deionized water, vacuum drying at 100 DEG C, by obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C heat treatment 2h, in mist, the volume fraction of hydrogen is 10%, prepares MoS2The composite nano materials of nanometer watt/Graphene, MoS in composite nano materials2With the ratio of Graphene amount of substance be 1:2, with XRD, SEM and TEM are to the prepared MoS that obtains2The composite nano materials of nanometer watt/Graphene characterizes, and XRD analysis result (seeing accompanying drawing 3) shows MoS in composite nano materials2For the layer structure of few number of plies, the average number of plies is 4 layers. SEM pattern and TEM photo (see accompanying drawing 4, wherein (a) is SEM shape appearance figure, be (b) and (c) transmission electron microscope photo, is (d) high-resolution-ration transmission electric-lens photo) have also shown the MoS loading on Graphene2Have little nanometer watt pattern, its number of plies is between 2-6, and most numbers of plies are 4 layers, consistent with XRD analysis;
3) by the MoS of above-mentioned preparation2Nanometer watt/Graphene composite nano materials is as the electrode active material of electrochemistry storage lithium, under agitation fully mix the uniform pastel of furnishing with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black and mass fraction 5%, this pastel is coated onto equably on the Copper Foil of collector, vacuum drying at 110 DEG C, then roll extrusion obtains MoS2Nanometer watt/Graphene electrochemistry storage lithium combination electrode, in combination electrode, each constituent mass percentage is: MoS2Nanometer watt/Graphene composite nano materials 80%, acetylene black 10%, Kynoar 10%.
Electrochemistry storage lithium performance test: as to electrode, electrolyte is 1.0MLiPF with lithium sheet6EC/DMC solution (1:1, volume ratio), barrier film is polypropylene screen (Celguard-2300), in the suitcase that is full of argon gas, be assembled into two electrode test batteries, 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 power charging-discharging characteristic.
Electrochemical results shows: MoS2The initial reversible capacity of electrochemistry storage lithium of nanometer watt/graphene combination electrode is 1253mAh/g, and after 50 and 100 circulations, reversible capacity is 1225 and 1135mAh/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 855mAh/g, is much higher than the theoretical capacity (372mA/g) of graphite material, has shown the high power charging-discharging characteristic of its enhancing.
Comparative example
Adopt DTAB cationic surfactant, prepared MoS by above-mentioned similar approach2Nanometer sheet/Graphene electrochemistry storage lithium combination electrode, concrete preparation process is as follows:
Be dispersed in 60mL deionized water ultrasonic 2.5mmol graphene oxide, add again 1.6mmol DTAB cationic surfactant, and fully stir, then add successively 0.76g (6.25mmol) Cys and 0.3g (1.25mmol) sodium molybdate (Na2MoO4·2H2O), and constantly stir Cys and sodium molybdate are dissolved completely, with extremely about 80mL of deionized water adjustment volume, obtained mixed liquor is transferred in the hydrothermal reaction kettle of 100mL, this reactor is put in constant temperature oven, at 230 DEG C after hydro-thermal reaction 24h, allow it naturally cool to room temperature, collect solid product with centrifugation, and fully wash by deionized water, vacuum drying at 100 DEG C, by obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C heat treatment 2h, in mist, the volume fraction of hydrogen is 10%, prepares MoS2The nano composite material of nanometer sheet/Graphene, MoS in composite nano materials2With the ratio of the amount of substance of Graphene be 1:2. With XRD, SEM and TEM are to finally preparing MoS2The nano composite material of nanometer sheet/Graphene characterizes, and XRD analysis result shows MoS in composite nano materials2For layer structure, its average number of plies is 7 layers, and TEM and HRTEM photo (see accompanying drawing 5, wherein figure (a) is transmission electron microscope photo, and figure (b) is high-resolution-ration transmission electric-lens photo) have shown the MoS loading on Graphene2For nanometer sheet pattern, its thickness and plane sizes are not so good as MoS above2Nanometer watt evenly, MoS2The number of plies of nanometer sheet is mainly at 4-9 layer, and the average number of plies is 7 layers, consistent with XRD analysis.
By above-mentioned steps 3) process prepare MoS2Nanometer sheet/Graphene electrochemistry storage lithium combination electrode. Electrochemical results shows: MoS2The initial reversible capacity of nanometer sheet/Graphene electrochemistry storage lithium combination electrode electrochemistry storage lithium is 915mAh/g, and after 50 and 100 circulations, reversible capacity is 910 and 885mAh/g; In the time of high current charge-discharge (charging and discharging currents is 1000mA/g), its capacity is 523mAh/g.
Claims (2)
1. the electrochemistry of a high power capacity and stable circulation storage lithium combination electrode, is characterized in that, the electrochemistry storage lithium of described combination electrodeActive material is MoS2The composite nano materials of nanometer watt/Graphene, MoS in composite nano materials2The thing of nanometer watt and GrapheneThe ratio of the amount of matter is 1:2, described MoS2The nanometer watt layer structure for few number of plies, the component of combination electrode and mass percent thereofContent is: MoS2Nanometer watt/Graphene composite nano materials 80-85%, acetylene black 5-10%, Kynoar 10%, described inThe layer structure of few number of plies refers to the layer structure of the number of plies below 6 layers or 6 layers;
The preparation method of described combination electrode carries out according to the following steps:
(1) be dispersed in deionized water ultrasonic graphene oxide, add Gemini surface active agent N-dodecyl trimethylene diamine twoAmmonium bromide, and fully stir, then add successively Cys and sodium molybdate, and constantly stir and make Cys and molybdic acidSodium dissolves completely, and the ratio of the amount of substance of Cys and sodium molybdate consumption is 5:1, the amount of sodium molybdate and graphene oxideRatio be 1:2;
(2) mixed dispersion step (1) being obtained is transferred in hydrothermal reaction kettle, and adds deionized water to adjust volume to water80% of thermal response still nominal volume, the concentration of the two ammonium bromides of Gemini surface active agent N-dodecyl trimethylene diamine is0.01～0.02mol/L, the content of graphene oxide is 30-70mmol/L, this reactor put in constant temperature oven,At 230-250 DEG C, after hydro-thermal reaction 24h, allow it naturally cool to room temperature, with centrifugation collection hydro-thermal reaction solid product, andFully wash by deionized water, vacuum drying at 100 DEG C, by the hydro-thermal reaction solid product obtaining at nitrogen/hydrogen mixed gasIn atmosphere at 800 DEG C heat treatment 2h, in mist, hydrogen volume mark is 10%, finally prepares MoS2Nanometer watt/stoneThe composite nano materials of China ink alkene;
(3) by the MoS of above-mentioned preparation2Nanometer watt/Graphene composite nano materials is as the electrochemistry storage lithium active material of electrode, with secondThe 1-METHYLPYRROLIDONE solution of the Kynoar of the black and mass fraction 5% of alkynes under agitation fully mixes the uniform pasty state of furnishingThing, is coated onto this pastel on the Copper Foil of collector equably, and dry, roll extrusion obtains combination electrode.
2. the electrochemistry of high power capacity according to claim 1 and stable circulation storage lithium combination electrode, is characterized in that described MoS2The average number of plies of nanometer watt is 4 layers.
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