CN104091929B - WS2Nanometer watt/Graphene electrochemistry storage magnesium combination electrode and preparation method - Google Patents
WS2Nanometer watt/Graphene electrochemistry storage magnesium combination electrode and preparation method Download PDFInfo
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- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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 kind of WS2-nanometer watt/Graphene electrochemistry storage magnesium combination electrode and preparation method thereof, its electrochemistry storage magnesium active material is WS2-The composite nano materials of nanometer watt/Graphene, WS in composite2The ratio of the amount of substance of nanometer watt and Graphene is 1:1-1:3, WS2Nanometer watt is few number of plies, approximately 4 layers of the average numbers of plies, and the component of combination electrode and mass percentage content thereof are: WS2Nanometer watt/Graphene composite nano materials is 80%, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%. Preparation process: first prepare WS2Nanometer watt/Graphene composite nano materials, then, with acetylene black and Kynoar furnishing pastel, is coated onto this pastel on the foam copper of collector equably, and after vacuum drying, roll extrusion obtains combination electrode. Combination electrode prepared by the present invention has high reversible storage magnesium capacity, excellent cycle performance and the multiplying power property of enhancing, and application prospect is extensive.
Description
Technical field
The present invention relates to electrochemistry storage magnesium combination electrode and preparation method thereof, relate in particular to WS2Nanometer watt/Graphene electrochemistry storage magnesium nano material combination electrode and preparation method thereof, belongs to technical field of new energy application.
Background technology
Along with the development of modern mobile communication, new-energy automobile and intelligent grid, novel electrochmical 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 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. But due to never solution carefully and lithium resource limited of the security of lithium ion battery, lithium ion battery still also exists a lot of work to do 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 deintercalation in the compound of some layer of structure, as inorganic transition metal oxide, sulfide etc. 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 still little as the electrode material of high performance electrochemistry storage magnesium.
WS2Having and layer structure like graphite-like, is the S-W-S of covalent bonds in its layer, is weak Van der Waals force between layers. WS2Weak 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 WS2Material can be used as the material of main part that inserts reaction. Therefore, WS2It is a kind of electrode material of rising electrochemistry storage magnesium. But general WS2Nano material electrochemistry storage magnesium performance can't meet practical application, and its electrochemistry storage magnesium capacity is lower, only has 50-60mAh/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 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 in nano electron device, the novel field such as 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, 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, as body phase WS2Reduce to few number of plies when individual layer (especially), shown and the visibly different physics of body phase material, chemical characteristic. Research shows the WS of individual layer or few number of plies2Nanometer sheet has better electrochemistry storage magnesium performance. But as the electrode material of electrochemistry storage magnesium, WS2Low electric conductivity between layers affected the performance of its application.
Due to WS2Nanometer sheet and Graphene have similar two-dimensional nano sheet pattern, and both have good similitude on microscopic appearance and crystal structure. If by WS2The 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 magnesium electrode course of reaction, can further improve the electrochemistry storage magnesium performance of composite. With common WS2Nanometer sheet comparison, the WS of little nanometer watt shape pattern2Not 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. Therefore WS2The composite nano materials of nanometer watt/Graphene can show the electrochemistry storage magnesium performance of remarkable enhancing.
But, up to the present, use WS2Nanometer 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 and sulfo-ammonium tungstate, and the hydrothermal method of assisting by Gemini surface active agent and heat treatment subsequently, prepared WS2The composite nano materials of nanometer watt/Graphene, then uses WS2The 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. The present invention prepares WS2The method of nanometer watt/graphene nano material electrochemical storage magnesium combination electrode has simply, facilitates and be easy to expand industrial applications a little.
Summary of the invention
The invention provides a kind of WS2-Nanometer watt/Graphene electrochemistry storage magnesium combination electrode and preparation method thereof, the electrochemistry storage magnesium active material of combination electrode is WS2-The composite nano materials of nanometer watt/Graphene, WS in composite nano materials2The ratio of the amount of substance of nanometer watt and Graphene is 1:1-1:3, described WS2The nanometer watt layer structure for few number of plies, the component of combination electrode and mass percentage content thereof are: WS2Nanometer 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 the layer structure of the number of plies below 6 layers or 6 layers, described WS2The average number of plies of nanometer watt is 4 layers.
Above-mentioned WS2-The preparation method of nanometer watt/Graphene electrochemistry storage magnesium combination electrode comprises the following steps:
(1) be dispersed in deionized water ultrasonic graphene oxide, 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 and sulfo-ammonium tungstate, and constantly stir Cys and sulfo-ammonium tungstate are dissolved completely, the ratio of the amount of substance of Cys and sulfo-ammonium tungstate consumption is 5:1, and sulfo-ammonium tungstate is 1:1-1:3 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 30-65mmol/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 WS2The composite nano materials of nanometer watt/Graphene;
(3) by the WS of above-mentioned preparation2Nanometer watt/Graphene composite nano materials is as the electrochemistry storage magnesium active material of preparing combination electrode, under agitation fully mix the uniform pastel of furnishing with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5%, each constituent mass percentage is: WS2Nanometer watt/Graphene composite nano materials 80%, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%, is coated onto this pastel on the foam copper of collector equably, vacuum drying at 110 DEG C, roll extrusion obtains WS2Nanometer watt/Graphene electrochemistry storage magnesium 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 WS2The 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 WS 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 WS4 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 (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 the heat treatment back loading WS on Graphene surface2There is the pattern of nanometer watt. This undersized WS2Nanometer watt has more edge, as electrochemistry storage magnesium material, can provide more short magnesium ion diffusion admittance, contributes to strengthen its electrochemistry storage magnesium performance; In addition, WS2Nanometer 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 WS2The electrochemistry storage magnesium combination 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.
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 WS that Fig. 3 embodiment 1 prepares2The XRD figure (a) of nanometer watt/Graphene composite nano materials, SEM shape appearance figure (b) and transmission electron microscope photo (c, d).
WS prepared by the comparative example of Fig. 4 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 1.25mmol sulfo-ammonium tungstate, and constantly stir Cys and sulfo-ammonium tungstate 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 WS2The composite nano materials of nanometer watt/Graphene, WS in composite nano materials2With the ratio of Graphene amount of substance be 1:2, with XRD, SEM and TEM are to the prepared WS that obtains2The composite nano materials of nanometer watt/Graphene characterizes, XRD analysis result (seeing accompanying drawing 3(a)) show WS in composite nano materials2The nanometer watt layer structure for few number of plies, the average number of plies is 4 layers; SEM pattern (seeing accompanying drawing 3(b)) and transmission electron microscope photo (seeing accompanying drawing 3(c), (d)) also show the WS loading on Graphene2Have little nanometer watt pattern, its number of plies is at 3-6 layer, and most numbers of plies are 4 layers, consistent with XRD analysis;
3) by the WS of above-mentioned preparation2Nanometer watt/Graphene composite nano materials is as the electrode active material of electrochemistry storage magnesium, under agitation fully mix the uniform pastel of furnishing with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5%, this pastel is coated onto equably on the foam copper of collector, vacuum drying at 110 DEG C, then roll extrusion obtains WS2Nanometer watt/Graphene electrochemistry storage magnesium combination electrode, in combination electrode, each constituent mass percentage is: WS2Nanometer watt/Graphene composite nano materials 80%, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%.
The performance test of electrochemistry storage magnesium: taking combination electrode as working electrode, with metal magnesium sheet as to electrode, the Mg[AlCl that electrolyte is 0.25mol/L2(C4H9)(C2H5)]2Tetrahydrofuran solution be electrolyte, porous polypropylene film (Celguard-2300) is barrier film, in the suitcase that is full 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 50mA/g, voltage range 0.3 ~ 3.0V. Electrochemical results shows: WS2The initial reversible capacity of electrochemistry storage magnesium of nanometer watt/graphene combination electrode is 278mAh/g, and after 50 circulations, reversible capacity is 262mAh/g, has shown high specific capacity and excellent stable circulation performance; In the time of high current charge-discharge (charging and discharging currents is 800mA/g), its capacity is 225mAh/g, has shown its high power charging-discharging characteristic (with comparative example comparison below) significantly strengthening.
Comparative example
Adopt DTAB cationic surfactant, prepared WS by above-mentioned similar approach2Nanometer sheet/Graphene electrochemistry storage magnesium nano material 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 1.25mmol sulfo-ammonium tungstate, and constantly stir Cys and sulfo-ammonium tungstate 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%, prepare WS2The nano composite material of nanometer sheet/Graphene, WS 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 WS2The nano composite material of nanometer sheet/Graphene characterizes, and XRD analysis result shows WS in composite nano materials2For layer structure, its average number of plies is 7 layers, and TEM and HRTEM photo (seeing accompanying drawing 4, is (a) TEM photo, is (b) HRTEM photo) have shown the WS loading on Graphene2For nanometer sheet pattern, its thickness and plane sizes are not so good as WS above2Nanometer watt evenly, WS2The number of plies of nanometer sheet is mainly at 6-9 layer, and the average number of plies is 7 layers, consistent with XRD analysis.
With prepared WS2 nanometer sheet/Graphene composite nano materials be electrochemistry storage magnesium active material, by above-mentioned steps 3) process prepare WS2Nanometer sheet/Graphene electrochemistry storage magnesium combination electrode, and test its electrochemistry storage magnesium performance by aforementioned identical electrochemistry storage magnesium method of testing. Result shows: WS2The initial reversible capacity of nanometer sheet/Graphene electrochemistry storage magnesium combination electrode electrochemistry storage magnesium is that 173mAh/g(charging and discharging currents is 50mA/g), after 50 circulations, reversible capacity is 155mAh/g; In the time of high current charge-discharge (charging and discharging currents is 800mA/g), its capacity is 103mAh/g.
Claims (2)
1. a WS2Nanometer watt/Graphene electrochemistry storage magnesium combination electrode, is characterized in that, the electrochemistry storage magnesium active matter of combination electrodeMatter is WS2The composite nano materials of nanometer watt/Graphene, WS in composite nano materials2The amount of substance of nanometer watt and GrapheneRatio be 1:1-1:3, WS2The nanometer watt layer structure for few number of plies, the component of combination electrode and mass percentage content thereof are:WS2Nanometer watt/Graphene composite nano materials 80%, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%,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 stirring, then adds Cys and sulfo-ammonium tungstate successively, and constantly stir make Cys andSulfo-ammonium tungstate dissolves completely, and the ratio of the amount of substance of Cys and sulfo-ammonium tungstate consumption is 5:1, sulfo-ammonium tungstate and oxygenThe ratio of the amount of substance of functionalized graphene is 1:1-1:3;
(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 30-65mmol/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 solid product, and useDeionized water is fully washed, vacuum drying at 100 DEG C, by the hydro-thermal solid product obtaining in nitrogen/hydrogen mixed gas atmosphereHeat treatment 2h at 800 DEG C, in mist, hydrogen volume mark is 10%, finally prepares WS2Answering of nanometer watt/GrapheneClose nano material;
(3) by the WS of above-mentioned preparation2Nanometer watt/Graphene composite nano materials is as the electrochemistry storage magnesium active matter of preparing combination electrodeMatter, with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5% under agitationFully mix the uniform pastel of furnishing, this pastel is coated onto equably on the foam copper of collector, true at 110 DEG CEmpty dry, roll extrusion obtains WS2Nanometer watt/Graphene electrochemistry storage magnesium combination electrode.
2. WS according to claim 12Nanometer watt/Graphene electrochemistry storage magnesium combination electrode, is characterized in that described WS2ReceiveRice watt the average number of plies be 4 layers.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102142550A (en) * | 2011-02-25 | 2011-08-03 | 浙江大学 | Compound nano material of graphene nano slice and WS2 and preparation method thereof |
| CN102214816A (en) * | 2011-02-25 | 2011-10-12 | 浙江振龙电源股份有限公司 | Grapheme/WS2 nanocomposite electrode of lithium ion battery and manufacturing method thereof |
| CN102694172A (en) * | 2012-06-08 | 2012-09-26 | 浙江大学 | Preparation method of composite nano material of single-layer WS2 and graphene |
| CN102694171A (en) * | 2012-06-08 | 2012-09-26 | 浙江大学 | Hydrothermal preparation method for composite material of single-layer WS2 and graphene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102142550A (en) * | 2011-02-25 | 2011-08-03 | 浙江大学 | Compound nano material of graphene nano slice and WS2 and preparation method thereof |
| CN102214816A (en) * | 2011-02-25 | 2011-10-12 | 浙江振龙电源股份有限公司 | Grapheme/WS2 nanocomposite electrode of lithium ion battery and manufacturing method thereof |
| CN102694172A (en) * | 2012-06-08 | 2012-09-26 | 浙江大学 | Preparation method of composite nano material of single-layer WS2 and graphene |
| CN102694171A (en) * | 2012-06-08 | 2012-09-26 | 浙江大学 | Hydrothermal preparation method for composite material of single-layer WS2 and graphene |
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