CN104091924A - Mo(0.5)W(0.5)S2 nano tile/graphene electrochemical magnesium storage composite electrode and preparation method thereof - Google Patents

Mo(0.5)W(0.5)S2 nano tile/graphene electrochemical magnesium storage composite electrode and preparation method thereof Download PDF

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CN104091924A
CN104091924A CN201410339888.1A CN201410339888A CN104091924A CN 104091924 A CN104091924 A CN 104091924A CN 201410339888 A CN201410339888 A CN 201410339888A CN 104091924 A CN104091924 A CN 104091924A
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graphene
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ammonium
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CN104091924B (en
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陈卫祥
马琳
黄国创
王臻
叶剑波
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Zhejiang University ZJU
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
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    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a Mo(0.5)W(0.5)S2 nano tile/graphene electrochemical magnesium storage composite electrode and a preparation method thereof. The electrochemical magnesium storage active substance is a Mo(0.5)W(0.5)S2 nano tile/graphene composite nano material; the substance amount ratio of the Mo(0.5)W(0.5)S2 to graphene in the composite nano material is 1 to 2; the Mo(0.5)W(0.5)S2 nano tile is of a few-layer layered structure, and the average layer number is 3-5; the composite electrode comprises the following components by weight percent: 80% of Mo(0.5)W(0.5)S2 nano tile/graphene composite nano material, 10% of acetylene black, 5% of carboxymethyl cellulose and 5% of polyvinylidene fluoride. The preparation method comprises the following steps: preparing a Mo(0.5)W(0.5)S2 nano tile/graphene composite nano material, and blending the Mo(0.5)W(0.5)S2 nano tile/graphene composite nano material with acetylene black and polyvinylidene fluoride to obtain slurry; and smearing the slurry on foamy copper, and rolling to obtain the Mo(0.5)W(0.5)S2 nano tile/graphene electrochemical magnesium storage composite electrode. The composite electrode disclosed by the invention has high electrochemical magnesium storage capacity.

Description

Mo 0.5w 0.5s 2nanometer watt/Graphene electrochemistry storage magnesium combination electrode and preparation method
Technical field
The present invention relates to electrochemistry storage magnesium electrode and preparation method thereof, relate in particular to and use Mo 0.5w 0.5s 2nanometer watt/Graphene composite nano materials is prepared the preparation method of electrochemistry storage magnesium combination electrode, belongs to technical field of new energies.
Background technology
Along with the development of modern mobile communication, new-energy automobile and intelligent grid, novel chemical power source has played more and more important effect in modern society.Traditional secondary cell, if lead acid accumulator is because it is containing harmful metallic element Pb, its application is restricted.Lithium ion battery has the excellent properties such as high specific energy, memory-less effect, environmental friendliness, in the Portable movable electrical equipment such as mobile phone and notebook computer, 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.But due to the fail safe of lithium ion battery solution carefully and lithium resource limited never, lithium ion battery is still subject to certain restrictions as the extensive use of electrokinetic cell and storage battery.Along with the development of new-energy automobile and the large-scale application of storage battery substitute the secondary cell of a kind of cheapness, environmental friendliness and the height ratio capacity of existing secondary cell system in the urgent need to finding a kind of energy.Because divalence magnesium ion has less radius, can electrochemical intercalation and the de-compound that is embedded in some layer of structure, as: transient metal sulfide MoS 2and WS 2deng.Magnesium also has aboundresources in addition, cheap, specific energy is high, nontoxic and process the advantages such as convenient.Therefore, rechargeable magnesium ion battery also becomes the research system of a new secondary cell in recent years.But up to the present as the electrode material of high performance electrochemistry storage magnesium still seldom.
MoS 2and WS 2having and layer structure like graphite-like, is the S-M-S (M=Mo, W) of very strong covalent bonds in its layer, is weak Van der Waals force between layers.MoS 2and WS 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 2and WS 2material can be used as the material of main part that inserts reaction.Therefore, MoS 2and WS 2be a kind of rising electrochemistry storage magnesium electrode material (X. L. Li, Y. D. Li, J. Phys. Chem. B, 2004,108:13893), but general MoS 2and WS 2its electrochemistry storage magnesium poor-performing of material, its electrochemistry storage magnesium capacity is lower, only has 50-100 mAh/g.
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 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 in fields such as nano electron device, novel catalyst material and electrochemistry energy storage and energy conversion.
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, if the transition metal dichalcogenide of individual layer or few number of plies etc. is (as MoS 2and WS 2).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 (below 8 layers), while especially 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, as body phase MoS 2and WS 2reduce to few number of plies when individual layer (especially), shown and the visibly different physics of body phase material, chemical characteristic.Research shows the MoS of individual layer or few number of plies 2and WS 2nanometer sheet has better electrochemistry storage magnesium performance.But as the electrode material of electrochemistry storage magnesium, MoS 2and WS 2low electric conductivity between layers affected the performance of its application.
Due to MoS 2and WS 2nanometer sheet and Graphene have similar two-dimensional nano sheet pattern, and both have good similitude on microscopic appearance and crystal structure.If by MoS 2and WS 2the composite material 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 material, strengthen the electronics transmission in electrochemistry storage magnesium electrode course of reaction, can further improve the electrochemistry storage magnesium performance of composite material.With common MoS 2and WS 2nanometer sheet comparison, the MoS of little nanometer watt shape pattern 2and WS 2not only there is more edge, more short magnesium ion diffusion admittance can be provided, and load on Graphene, there is more contact area with electrolyte.So MoS 2and WS 2the composite nano materials of nanometer watt/Graphene can show the electrochemistry storage magnesium performance of enhancing.
In addition, research is also found as electrochemistry storage Development of Magnesium Electrode Materials, MoS2 nano material has higher electrochemistry storage magnesium reversible capacity than WS2 nano material, and WS2 nano material has good high rate during charging-discharging than MoS2 nano material, therefore the combination property that, the compound heterogeneous stratified material of MoS2 and WS2 bi-material should have as electrochemistry storage magnesium material.Therefore the chemical property that, the composite nano materials of Mo0.5W0.5S2 nanometer watt/Graphene has a wide range of applications and strengthens as electrochemistry storage Development of Magnesium Electrode Materials.
But, up to the present, use Mo 0.5w 0.5s 2nanometer watt/Graphene composite nano materials have not been reported as electrochemistry storage magnesium combination electrode and the preparation thereof of electroactive substance.First the present invention is raw material with graphene oxide, ammonium thiomolybdate and sulfo-ammonium tungstate etc., and the hydrothermal method of assisting by Gemini surface active agent and heat treatment subsequently, prepared Mo 0.5w 0.5s 2the composite nano materials of nanometer watt/Graphene, then uses Mo 0.5w 0.5s 2the composite nano materials of nanometer watt/Graphene, as the active material of electrochemistry storage magnesium, has been prepared the combination electrode of electrochemistry storage magnesium.This preparation Mo 0.5w 0.5s 2the method of nanometer watt/Graphene composite nano materials electrochemistry storage magnesium 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 a kind of Mo 0.5w 0.5s 2nanometer watt/Graphene electrochemistry storage magnesium combination electrode and preparation method thereof, the electrochemistry storage magnesium active material of combination electrode is Mo 0.5w 0.5s 2-the composite nano materials of nanometer watt/Graphene, Mo in composite nano materials 0.5w 0.5s 2nanometer watt is 1:2 with the ratio of the amount of substance of Graphene, described Mo 0.5w 0.5s 2the nanometer watt layer structure for few number of plies, the component of combination electrode and mass percentage content thereof are: Mo 0.5w 0.5s 2nanometer watt/Graphene composite nano materials 80%, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%.
In technique scheme, the layer structure of few number of plies refers to that the number of plies is in the layer structure below 6 layers or 6 layers, described Mo 0.5w 0.5s 2the average number of plies of nanometer watt is 3 layers.
Above-mentioned Mo 0.5w 0.5s 2the preparation method of nanometer watt/Graphene electrochemistry storage magnesium combination electrode carries out according to the following steps:
(1) be dispersed in deionized water graphene oxide is ultrasonic, add the two ammonium bromides (seeing accompanying drawing 1) of Gemini surface active agent N-dodecyl trimethylene diamine, and fully stir, then add successively Cys, ammonium thiomolybdate and sulfo-ammonium tungstate, and constantly stir Cys, ammonium thiomolybdate and sulfo-ammonium tungstate are dissolved completely, the ratio of the amount of substance of Cys, ammonium thiomolybdate and sulfo-ammonium tungstate consumption is 5:0.5:0.5, and ammonium thiomolybdate, sulfo-ammonium tungstate are 0.5:0.5:2 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 ~ 0.02 mol/L, the content of graphene oxide is 30-65 mmol/L, this reactor is put in constant temperature oven, at 230-250 ℃ after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, with centrifugation, collect hydro-thermal reaction solid product, and fully wash with deionized water, vacuumize at 100 ℃, by the hydro-thermal reaction solid product obtaining in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2 h, in mist, hydrogen volume mark is 10%, finally prepare Mo 0.5w 0.5s 2the composite nano materials of nanometer watt/Graphene,
(3) by the Mo of above-mentioned preparation 0.5w 0.5s 2nanometer watt/Graphene composite nano materials is as the electrochemistry storage magnesium active material of electrode, under agitation fully mix the uniform slurry of furnishing with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5%, each constituent mass percentage is: Mo 0.5w 0.5s 2nanometer watt/Graphene composite nano materials 80%, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%, is coated onto this slurry on the foam copper of collector equably, and dry, roll extrusion obtains 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 Mo 0.5w 0.5s 2the 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 with the MoS of negative electrical charge 4 2-and WS 4 2-ion is incompatible, and the present invention is first adsorbed onto graphene oxide surface by the two ammonium bromides of Gemini surface active agent N-dodecyl trimethylene diamine by electrostatic interaction, makes it with part positive charge, due to electrostatic interaction, and MoS 4 2-and WS 4 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, compare 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 (seeing accompanying drawing 1), and its hydrophobicity is stronger.The two ammonium bromides of N-dodecyl trimethylene diamine are adsorbed on Graphene surface, and its hydrophobic grouping exists (seeing accompanying drawing 2) with irregular " brush head " form of bending, and this version has caused water-heat process and heat treatment back loading at the Mo on Graphene surface 0.5w 0.5s 2the pattern with nanometer watt.This undersized Mo 0.5w 0.5s 2nanometer watt has more edge, as electrochemistry storage magnesium material, can provide more short lithium ion diffusion admittance, contributes to strengthen its electrochemistry storage magnesium performance; Mo 0.5w 0.5s 2nanometer watt/graphene composite material can increase the contact area of itself and electrolyte, can further contribute to improve its chemical property; Mo 0.5w 0.5s 2a nanometer watt heterogeneous stratified material also makes Mo 0.5w 0.5s 2nanometer watt/graphene composite material has comprehensively good electrochemistry storage magnesium performance.Therefore, the present invention Mo 0.5w 0.5s 2the electrochemistry storage magnesium electrode that nanometer watt/graphene composite material is prepared as electroactive substance has high electrochemistry storage magnesium capacity, excellent cycle performance and significantly strengthen large current density electrical characteristics.
Accompanying drawing explanation
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 Mo that Fig. 3 embodiment 1 prepares 0.5w 0.5s 2the XRD figure (a) of nanometer watt/Graphene composite nano materials, SEM shape appearance figure (b) and transmission electron microscope photo (c, d).
Mo prepared by the comparative example of Fig. 4 embodiment 1 0.5w 0.5s 2the TEM of nanometer sheet and Graphene composite nano materials and HRTEM photo.
Embodiment
Below in conjunction with embodiment, further illustrate the present invention.
Graphene oxide in following example adopts improved Hummers method preparation: 0 ounder C ice bath, 10.0 mmol (0.12 g) graphite powder dispersed with stirring, in the 50 mL concentrated sulfuric acids, is slowly added to KMnO under constantly stirring 4, institute adds KMnO 4quality be 4 times of graphite powder, stir 50 minutes, when temperature rises to 35 ℃, slowly add 50 mL deionized waters, then stir 30 minutes, add the H of 15 mL mass fractions 30% 2o 2, 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 60 mL deionized waters 2.5 mmol graphene oxides are ultrasonic, add again the two ammonium bromides of 0.8 mmol Gemini surface active agent N-dodecyl trimethylene diamine, and fully stir, then add successively 0.76g (6.25 mmol) Cys, 0.625 mmol ammonium thiomolybdate and 0.625 mmol sulfo-ammonium tungstate, and constantly stir Cys, ammonium thiomolybdate and sulfo-ammonium tungstate are dissolved completely, with deionized water, adjust volume to approximately 80 mL;
2) resulting mixed liquor is transferred in the hydrothermal reaction kettle of 100 mL, this reactor is put in constant temperature oven, at 230 ℃ after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, with centrifugation, collect solid product, and fully wash with deionized water, vacuumize at 100 ℃, by resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2h, in mist, the volume fraction of hydrogen is 10%, prepares Mo 0.5w 0.5s 2the composite nano materials of nanometer watt/Graphene, Mo in composite nano materials 0.5w 0.5s 2with the ratio of Graphene amount of substance be 1:2, with XRD, SEM and TEM are to the prepared Mo that obtains 0.5w 0.5s 2the composite nano materials of nanometer watt/Graphene characterizes, XRD analysis result (seeing accompanying drawing 3(a)) show Mo in composite nano materials 0.5w 0.5s 2for the layer structure of few number of plies, the average number of plies is 3 layers.SEM pattern (seeing accompanying drawing 3(b)) and TEM photo (seeing accompanying drawing 3(c, d)) also shown the Mo loading on Graphene 0.5w 0.5s 2have little nanometer watt pattern, its number of plies is at layer 2-4, and majority is 3 layers, consistent with XRD analysis;
3) by the Mo of above-mentioned preparation 0.5w 0.5s 2nanometer watt/Graphene composite nano materials is as the electrode active material of electrochemistry storage magnesium, under agitation fully mix the uniform slurry of furnishing with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5%, this slurry is coated onto on the foam copper of collector (foam copper porosity is greater than 90%) equably, vacuumize at 110 ℃, then roll extrusion obtains Mo 0.5w 0.5s 2nanometer watt/Graphene electrochemistry storage magnesium combination electrode, in combination electrode, each constituent mass percentage is: Mo 0.5w 0.5s 2nanometer watt/Graphene composite nano materials 80%, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%.
?electrochemistry storage magnesium performance test: take combination electrode as work electrode, as to electrode, electrolyte is the Mg[AlCl of 0.25 mol/L with metal magnesium sheet 2(C 4h 9) (C 2h 5)] 2tetrahydrofuran solution be electrolyte, porous polypropylene film (Celguard-2300) is barrier film, in being full of the suitcase of argon gas, is assembled into test battery.By the electrochemistry storage magnesium performance of constant current charge-discharge test compound electrode, charge and discharge cycles is carried out on programme controlled auto charge and discharge instrument, charging and discharging currents density 50 mA/g, voltage range 0.3 ~ 3.0 V.Electrochemical results shows: Mo 0.5w 0.5s 2the initial reversible capacity of electrochemistry storage magnesium of nanometer watt/graphene combination electrode is 283 mAh/g, and after 50 circulations, reversible capacity is 275 mAh/g, has shown high specific capacity and excellent stable circulation performance; When high current charge-discharge (charging and discharging currents is 800 mA/g), its capacity is 232 mAh/g, has shown its high power charging-discharging characteristic (with comparative example comparison below) significantly strengthening.
Comparative example
Adopt DTAB cationic surfactant, by above-mentioned similar approach, prepared Mo 0.5w 0.5s 2nanometer sheet/Graphene electrochemistry storage magnesium combination electrode, concrete preparation process is as follows:
Be dispersed in 60 mL deionized waters 2.5 mmol graphene oxides are ultrasonic, add again 1.6 mmol DTAB cationic surfactants, and fully stir, then add successively 0.76 g (6.25 mmol) Cys, 0.625 mmol ammonium thiomolybdate and 0.625 mmol sulfo-ammonium tungstate, and constantly stir Cys and ammonium thiomolybdate and sulfo-ammonium tungstate are dissolved completely, with deionized water, adjust volume to approximately 80 mL, resulting mixed liquor is transferred in the hydrothermal reaction kettle of 100 mL, this reactor is put in constant temperature oven, at 230 ℃ after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, with centrifugation, collect solid product, and fully wash with deionized water, vacuumize at 100 ℃, by resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2h, in mist, the volume fraction of hydrogen is 10%, prepare Mo 0.5w 0.5s 2the nano composite material of nanometer sheet/Graphene, Mo in composite nano materials 0.5w 0.5s 2with the ratio of the amount of substance of Graphene be 1:2.With XRD, SEM and TEM are to finally preparing Mo 0.5w 0.5s 2the nano composite material of nanometer sheet/Graphene characterizes, and XRD analysis result shows Mo in composite nano materials 0.5w 0.5s 2for layer structure, its average number of plies is 7 layers, and TEM and HRTEM photo (seeing accompanying drawing 4) have shown the Mo loading on Graphene 0.5w 0.5s 2for nanometer sheet pattern, its thickness and size are not so good as Mo above 0.5w 0.5s 2nanometer watt evenly, Mo 0.5w 0.5s 2the average number of plies of nanometer sheet is 6-7 layer, consistent with XRD analysis;
By above-mentioned steps 3) process prepare Mo 0.5w 0.5s 2nanometer sheet/Graphene electrochemistry storage magnesium combination electrode, and by the electrochemistry storage magnesium performance of above-mentioned identical method test compound electrode.Electrochemical results shows: Mo 0.5w 0.5s 2the initial reversible capacity of nanometer sheet/Graphene electrochemistry storage magnesium combination electrode electrochemistry storage magnesium is that 183 mAh/g(charging and discharging currents are 50 mA/g), after 50 circulations, reversible capacity is 171 mAh/g; When high current charge-discharge (charging and discharging currents is 800 mA/g), its capacity is 96 mAh/g.

Claims (3)

1. a Mo 0.5w 0.5s 2nanometer watt/Graphene electrochemistry storage magnesium combination electrode, is characterized in that, the electrochemistry storage magnesium active material of combination electrode is Mo 0.5w 0.5s 2-the composite nano materials of nanometer watt/Graphene, Mo in composite nano materials 0.5w 0.5s 2the ratio of the amount of substance of nanometer watt and Graphene is 1:2, described Mo 0.5w 0.5s 2the nanometer watt layer structure for few number of plies, the component of combination electrode and mass percentage content thereof are: Mo 0.5w 0.5s 2nanometer watt/Graphene composite nano materials 80%, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%.
2. Mo according to claim 1 0.5w 0.5s 2nanometer watt/Graphene electrochemistry storage magnesium combination electrode, is characterized in that described Mo 0.5w 0.5s 2the average number of plies of nanometer watt is 3 layers.
3. Mo described in a claim 1 or 2 0.5w 0.5s 2the preparation method of nanometer watt/Graphene electrochemistry storage magnesium combination electrode, is characterized in that, its preparation method carries out according to the following steps:
(1) be dispersed in deionized water graphene oxide is ultrasonic, add the two ammonium bromides of Gemini surface active agent N-dodecyl trimethylene diamine, and fully stir, then add successively Cys, ammonium thiomolybdate and sulfo-ammonium tungstate, and constantly stir Cys, ammonium thiomolybdate and sulfo-ammonium tungstate are dissolved completely, the ratio of the amount of substance of Cys, ammonium thiomolybdate and sulfo-ammonium tungstate consumption is 5:0.5:0.5, and ammonium thiomolybdate, sulfo-ammonium tungstate are 0.5:0.5:2 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 ~ 0.02 mol/L, the content of graphene oxide is 30-65 mmol/L, this reactor is put in constant temperature oven, at 230-250 ℃ after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, with centrifugation, collect hydro-thermal reaction solid product, and fully wash with deionized water, vacuumize at 100 ℃, by the hydro-thermal reaction solid product obtaining in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2 h, in mist, hydrogen volume mark is 10%, finally prepare Mo 0.5w 0.5s 2the composite nano materials of nanometer watt/Graphene,
(3) by the Mo of above-mentioned preparation 0.5w 0.5s 2nanometer watt/Graphene composite nano materials is as electrochemistry storage magnesium active material, under agitation fully mix the uniform slurry of furnishing with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5%, this slurry is coated onto equably on the foam copper of collector, and dry rear roll extrusion obtains combination electrode.
CN201410339888.1A 2014-07-17 2014-07-17 Mo0.5W0.5S2Nanometer watt/Graphene electrochemistry storage magnesium combination electrode and preparation method Expired - Fee Related CN104091924B (en)

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