CN104091924B - Mo0.5W0.5S2Nanometer watt/Graphene electrochemistry storage magnesium combination electrode and preparation method - Google Patents
Mo0.5W0.5S2Nanometer watt/Graphene electrochemistry storage magnesium combination electrode and preparation method Download PDFInfo
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Abstract
The invention discloses a kind of Mo0.5W0.5S2-Nanometer watt/Graphene electrochemistry storage magnesium combination electrode and preparation method thereof, its electrochemistry storage magnesium active material is Mo0.5W0.5S2-The composite nano materials of nanometer watt/Graphene, Mo in composite nano materials0.5W0.5S2With the ratio of the amount of substance of Graphene be 1:2, Mo0.5W0.5S2The nanometer watt layer structure for few number of plies, the average number of plies is 3-5 layer, the component of combination electrode and mass percentage content thereof are: Mo0.5W0.5S2Nanometer watt/Graphene composite nano materials is 80%, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%. Preparation process: first prepare Mo0.5W0.5S2Nanometer watt/Graphene composite nano materials, then with acetylene black and Kynoar furnishing slurry, is coated onto roll extrusion on foam copper and obtains. Combination electrode of the present invention has high electrochemistry storage magnesium capacity.
Description
Technical field
The present invention relates to electrochemistry storage magnesium electrode and preparation method thereof, relate in particular to and use Mo0.5W0.5S2Nanometer watt/GrapheneComposite 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 electrochmical power source is in modern societyIn played more and more important effect. 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, is movingIn the Portable movable such as mobile phone and notebook computer electrical equipment, be widely used. As electrokinetic cell, lithium ion batteryAlso be with a wide range of applications at aspects such as electric bicycle, electric automobile and intelligent grids. But due to lithium ion batteryNever solution carefully and lithium resource limited of security, lithium ion battery is wide as electrokinetic cell and storage batteryGeneral application is still subject to certain restrictions. Along with the development of new-energy automobile and the large-scale application of storage battery are in the urgent need to seekingLook for a kind of energy to substitute the secondary cell of a kind of cheapness, environmental friendliness and the height ratio capacity of existing secondary cell system. Due to divalenceMagnesium ion has less radius, can electrochemical intercalation and deintercalation in the compound of some layer of structure, as transition metal sulfurationThing MoS2And WS2Deng. 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 high propertyThe electrode material of the electrochemistry storage magnesium of energy or little.
MoS2And WS2Having and layer structure like graphite-like, is the S-M-S (M=of very strong covalent bonds in its layerMo, W), be weak Van der Waals force between layers. MoS2And WS2Weak interlaminar action power and larger interlamellar spacing permitPerhaps react at its interlayer and introduce external atom or molecule by insertion. Such characteristic makes MoS2And WS2Material can be used asInsert the material of main part of reaction. Therefore, MoS2And WS2A kind of electrode material (X.L. of rising electrochemistry storage magnesiumLi, Y.D.Li, J.Phys.Chem.B, 2004,108:13893), but general MoS2And WS2Its electricity of materialChemistry storage magnesium poor-performing, its electrochemistry storage magnesium capacity is lower, only has 50-100mAh/g.
Two-dimensional nano material has the characteristic of numerous excellences with its unique pattern, its research has caused that people's is greatly emergingInterest. Graphene is most typical two-dimensional nano material, and its unique two-dimensional nano chip architecture makes physics, the chemistry of its numerous uniquenessesWith performances such as mechanics, there is important scientific research meaning and technology application prospect widely. Graphene has high ratio tableArea, high conduction and heat conductivility, high charge mobility, excellent mechanical property, these excellent characteristics make graphiteAlkene is before nano electron device, the novel field such as catalyst material and electrochemistry energy storage and energy conversion have a wide range of applicationsScape.
The immense success that the discovery of Graphene and research thereof obtain has excited people to grind other inorganic two-dimensional nano materialsThe very big interest of studying carefully, if the transition metal dichalcogenide of individual layer or few number of plies etc. is (as MoS2And WS2). Recently, Graphene conceptExpand to the inorganic compound of other layer structures from material with carbon element, namely for the inorganic material of layer structure, when itWhen the number of plies reduces (8 layers are following), 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 MoS2WithWS2Reduce to few number of plies when individual layer (especially), shown and the visibly different physics of body phase material, chemical characteristic. Research tableThe MoS of bright individual layer or few number of plies2And WS2Nanometer sheet has better electrochemistry storage magnesium performance. But as electrochemistry storage magnesiumElectrode material, MoS2And WS2Low electric conductivity between layers affected the performance of its application.
Due to MoS2And WS2Nanometer sheet and Graphene have similar two-dimensional nano sheet pattern, both at microscopic appearance andOn crystal structure, there is good similitude. If by MoS2And WS2The composite wood of nanometer sheet and the compound preparation of GrapheneMaterial, the high conduction performance of graphene nanometer sheet can further improve the electric conductivity of composite, strengthens electrochemistry storage magnesium electricityElectronics transmission in utmost point course of reaction, can further improve the electrochemistry of composite and store magnesium performance. With common MoS2And WS2Nanometer sheet comparison, the MoS of little nanometer watt shape pattern2And WS2Not only there is more edge, more short magnesium can be providedIon diffusion admittance, and load on Graphene, more contact area there is with electrolyte. Therefore MoS2And WS2NanometerWatt/composite nano materials of Graphene can show the electrochemistry storage magnesium performance of enhancing.
In addition, research also finds that MoS2 nano material has than WS2 nano material as electrochemistry storage Development of Magnesium Electrode MaterialsHigh electrochemistry storage magnesium reversible capacity, and WS2 nano material has good high rate during charging-discharging than MoS2 nano material,What therefore, the compound heterogeneous stratified material of MoS2 and WS2 bi-material should have as electrochemistry storage magnesium material is comprehensiveEnergy. The composite nano materials of therefore, Mo0.5W0.5S2 nanometer watt/Graphene has extensively as electrochemistry storage Development of Magnesium Electrode MaterialsApplication and the chemical property of enhancing.
But, up to the present, use Mo0.5W0.5S2Nanometer watt/Graphene composite nano materials is as electro-chemical activity thingElectrochemistry storage magnesium combination electrode and the preparation thereof of matter have not been reported. The present invention first use graphene oxide, ammonium thiomolybdate andSulfo-ammonium tungstate etc. is raw material, and the hydrothermal method of assisting by Gemini surface active agent and heat treatment subsequently, preparedMo0.5W0.5S2The composite nano materials of nanometer watt/Graphene, then uses Mo0.5W0.5S2The composite Nano material of nanometer watt/GrapheneMaterial, as the active material of electrochemistry storage magnesium, has been prepared the combination electrode of electrochemistry storage magnesium. This preparation Mo0.5W0.5S2NanometerWatt/method of Graphene composite nano materials electrochemistry storage magnesium combination electrode has simply, facilitates and is easy to expand industrialization shouldWith a little.
Summary of the invention
The object of the present invention is to provide a kind of Mo0.5W0.5S2Nanometer watt/Graphene electrochemistry storage magnesium combination electrode andPreparation method, the electrochemistry storage magnesium active material of combination electrode is Mo0.5W0.5S2-The composite nano materials of nanometer watt/Graphene,Mo in composite nano materials0.5W0.5S2Nanometer watt is 1:2 with the ratio of the amount of substance of Graphene, described Mo0.5W0.5S2Nanometer watt isThe layer structure of few number of plies, the component of combination electrode and mass percentage content thereof are: Mo0.5W0.5S2Nanometer watt/Graphene is multipleClose nano material 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 inMo0.5W0.5S2The average number of plies of nanometer watt is 3 layers.
Above-mentioned Mo0.5W0.5S2The preparation method of nanometer watt/Graphene electrochemistry storage magnesium 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 Asia thirdThe two ammonium bromides (seeing accompanying drawing 1) of base diamines, and fully stir, then add successively Cys, ammonium thiomolybdate and sulfo-tungstenAcid ammonium, and constantly stir Cys, ammonium thiomolybdate and sulfo-ammonium tungstate are dissolved completely, Cys, molybdenum dithiophosphateThe ratio of the amount of substance of acid ammonium and sulfo-ammonium tungstate consumption is 5:0.5:0.5, ammonium thiomolybdate, sulfo-ammonium tungstate and graphite oxideThe ratio of the amount of substance of alkene is 0.5:0.5:2;
(2) mixed dispersion step (1) being obtained is transferred in hydrothermal reaction kettle, and adds deionized water to adjust bodyAmass to 80% of hydrothermal reaction kettle nominal volume the concentration of the two ammonium bromides of Gemini surface active agent N-dodecyl trimethylene diamineBe 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, mixes the hydro-thermal reaction solid product obtaining at nitrogen/hydrogenClose in atmosphere heat treatment 2h at 800 DEG C, in mist, hydrogen volume mark is 10%, finally prepares Mo0.5W0.5S2The composite nano materials of nanometer watt/Graphene;
(3) by the Mo of above-mentioned preparation0.5W0.5S2Nanometer watt/Graphene composite nano materials is as the electrochemistry storage magnesium of electrodeActive material, with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5%Under agitation fully mix the uniform slurry of furnishing, each constituent mass percentage is: Mo0.5W0.5S2Nanometer watt/Graphene is compoundNano material 80%, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%, is coated onto this slurry equably as collectionOn the foam copper of fluid, dry, roll extrusion obtains electrode.
Above-mentioned graphene oxide adopts improved Hummers method preparation.
Hydrothermal method system of assisting with the two ammonium bromides of Gemini surface active agent N-dodecyl trimethylene diamine of the present inventionStandby Mo0.5W0.5S2The method of nanometer watt/Graphene composite nano materials has the following advantages: graphene oxide surface and marginal beltHave a lot of oxygen-containing functional groups (as hydroxyl, carbonyl, carboxyl), these oxygen-containing functional groups make graphene oxide more easily be dispersed in waterOr in organic liquid, but these oxygen-containing functional groups make graphene oxide surface with negative electrical charge, make graphene oxide and bandThere is the MoS of negative electrical charge4 2-And WS4 2-Ion is incompatible, and the present invention passes through electrostatic interaction first by Gemini surface active agent N-dodecaneThe two ammonium bromides of base trimethylene diamine are adsorbed onto graphene oxide surface, make it with part positive charge, due to electrostatic interaction,MoS4 2-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, Gemini surface active agent N-dodecyl trimethylene diamineIn two ammonium bromides, have 2 positively charged quaternary ammonium hydrophilic radicals, there is enough hydrophilies, with electronegative graphene oxide itBetween there is stronger mutual electrostatic interaction; The two ammonium bromides of N-dodecyl trimethylene diamine also have 2 hydrophobic long alkyl chain basesGroup's (seeing accompanying drawing 1), its hydrophobicity is stronger. The two ammonium bromides of N-dodecyl trimethylene diamine are adsorbed on Graphene surface, and it is hydrophobicThere is (seeing accompanying drawing 2) with irregular " brush head " form of bending in group, this version has caused water-heat process and heatProcess the Mo of back loading on Graphene surface0.5W0.5S2There is the pattern of nanometer watt. This undersized Mo0.5W0.5S2Nanometer wattThere is more edge, as electrochemistry storage magnesium material, can provide more short lithium ion diffusion admittance, contribute to strengthenIts electrochemistry storage magnesium performance; Mo0.5W0.5S2Nanometer watt/graphene composite material can increase the contact area of itself and electrolyte,Can further contribute to improve its chemical property; Mo0.5W0.5S2A nanometer watt heterogeneous stratified material also makes Mo0.5W0.5S2ReceiveRice watt/graphene composite material has comprehensively good electrochemistry storage magnesium performance. Therefore, the present invention Mo0.5W0.5S2Nanometer watt/stoneThe electrochemistry storage magnesium electrode that China ink alkene composite is prepared as electroactive substance has high electrochemistry storage magnesium capacity, excellenceCycle 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 Mo that Fig. 3 embodiment 1 prepares0.5W0.5S2The 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 10.5W0.5S2The TEM of nanometer sheet and Graphene composite nano materials andHRTEM 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, by 10.0Mmol (0.12g) graphite powder dispersed with stirring, in the 50mL concentrated sulfuric acid, slowly adds KMnO under constantly stirring4, institute adds KMnO4'sQuality is 4 times of graphite powder, stirs 50 minutes, in the time of temperature rise to 35 DEG C, slowly adds 50mL deionized water, then stirs30 minutes, add the H of 15mL mass fraction 30%2O2, stir 30 minutes, through centrifugation, use successively mass fraction 5%HCl solution, deionized water and acetone cyclic washing after obtain graphene oxide.
Embodiment 1.
1) be dispersed in 60mL deionized water ultrasonic 2.5mmol graphene oxide, then add 0.8mmol Shuangzi tableThe two ammonium bromides of surface-active agent N-dodecyl trimethylene diamine, and fully stir, then add successively 0.76g (6.25mmol)Cys, 0.625mmol ammonium thiomolybdate and 0.625mmol sulfo-ammonium tungstate, and constantly stir and make L-half Guang ammoniaAcid, ammonium thiomolybdate and sulfo-ammonium tungstate dissolve 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 into constant temperature ovenIn, after hydro-thermal reaction 24h, allow it naturally cool to room temperature at 230 DEG C, collect solid product with centrifugation, and use deionizationWater fully washs, vacuum drying at 100 DEG C, by obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 DEG CHeat treatment 2h, in mist, the volume fraction of hydrogen is 10%, prepares Mo0.5W0.5S2Nanometer watt/Graphene compoundNano material, Mo in composite nano materials0.5W0.5S2With the ratio of Graphene amount of substance be 1:2, with XRD, SEM and TEM are to institutePrepare Mo0.5W0.5S2The composite nano materials of nanometer watt/Graphene characterizes, XRD analysis result (seeing accompanying drawing 3(a))Show Mo in composite nano materials0.5W0.5S2For the layer structure of few number of plies, the average number of plies is 3 layers. SEM pattern (is shown in accompanying drawing 3(b)) and TEM photo (seeing accompanying drawing 3(c, d)) also shown the Mo loading on Graphene0.5W0.5S2There is little nanometer watt shapeLooks, 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 preparation0.5W0.5S2Nanometer watt/Graphene composite nano materials is as the electrode of electrochemistry storage magnesiumActive material, with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5%Under agitation fully mix the uniform slurry of furnishing, this slurry is coated onto to (foam copper on the foam copper of collector equablyPorosity is greater than 90%), vacuum drying at 110 DEG C, then roll extrusion obtains Mo0.5W0.5S2Nanometer watt/Graphene electrochemistry storage magnesium is compoundElectrode, in combination electrode, each constituent mass percentage is: Mo0.5W0.5S2Nanometer watt/Graphene composite nano materials 80%, acetyleneBlack 10%, carboxymethyl cellulose 5%, Kynoar 5%.
Electrochemistry storage magnesium performance test: taking combination electrode as working electrode, as to electrode, electrolyte is with metal magnesium sheetThe Mg[AlCl of 0.25mol/L2(C4H9)(C2H5)]2Tetrahydrofuran solution be electrolyte, porous polypropylene film(Celguard-2300) be barrier film, in the suitcase that is full of argon gas, be assembled into test battery. Multiple with constant current charge-discharge testThe electrochemistry storage magnesium performance of composite electrode, charge and discharge cycles is carried out on programme controlled auto charge and discharge instrument, charging and discharging currentsDensity 50mA/g, voltage range 0.3 ~ 3.0V. Electrochemical results shows: Mo0.5W0.5S2Nanometer watt/Graphene compound electricThe initial reversible capacity of electrochemistry storage magnesium of the utmost point is 283mAh/g, and after 50 circulations, reversible capacity is 275mAh/g, has shown heightSpecific capacity and excellent stable circulation performance; In the time of high current charge-discharge (charging and discharging currents is 800mA/g), its capacity is232mAh/g, has shown its high power charging-discharging characteristic (with comparative example comparison below) significantly strengthening.
Comparative example
Adopt DTAB cationic surfactant, prepared by above-mentioned similar approachMo0.5W0.5S2Nanometer sheet/Graphene electrochemistry storage magnesium combination electrode, concrete preparation process is as follows:
Be dispersed in 60mL deionized water ultrasonic 2.5mmol graphene oxide, then add 1.6mmol dodecylTrimethylammonium bromide cationic surfactant, and fully stir, then add successively 0.76g (6.25mmol) L-half GuangPropylhomoserin, 0.625mmol ammonium thiomolybdate and 0.625mmol sulfo-ammonium tungstate, and constantly stir and make Cys and sulfo-Ammonium molybdate and sulfo-ammonium tungstate dissolve completely, adjust volume to about 80mL by deionized water, and obtained mixed liquor is shiftedIn the hydrothermal reaction kettle of 100mL, this reactor is put in constant temperature oven, at 230 DEG C after hydro-thermal reaction 24h, allow its fromSo be cooled to room temperature, collect solid product with centrifugation, and fully wash by deionized water, vacuum drying at 100 DEG C, willThe solid product obtaining in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C heat treatment 2h, the volume integral of hydrogen in mistNumber is 10%, prepares Mo0.5W0.5S2The nano composite material of nanometer sheet/Graphene, Mo in composite nano materials0.5W0.5S2With the ratio of the amount of substance of Graphene be 1:2. With XRD, SEM and TEM are to finally preparing Mo0.5W0.5S2Nanometer sheet/graphiteThe nano composite material of alkene characterizes, and XRD analysis result shows Mo in composite nano materials0.5W0.5S2For layer structure, itsThe average number of plies is 7 layers, and TEM and HRTEM photo (seeing accompanying drawing 4) have shown the Mo loading on Graphene0.5W0.5S2For nanometer sheetPattern, its thickness and size are not so good as Mo above0.5W0.5S2Nanometer watt evenly, Mo0.5W0.5S2The average number of plies of nanometer sheet is 6-7 layers, consistent with XRD analysis;
By above-mentioned steps 3) process prepare Mo0.5W0.5S2Nanometer sheet/Graphene electrochemistry storage magnesium combination electrode, and by upperState the electrochemistry storage magnesium performance of identical method test compound electrode. Electrochemical results shows: Mo0.5W0.5S2Nanometer sheet/The initial reversible capacity of Graphene electrochemistry storage magnesium combination electrode electrochemistry storage magnesium is that 183mAh/g(charging and discharging currents is 50mA/G), after 50 circulations, reversible capacity is 171mAh/g; In the time of high current charge-discharge (charging and discharging currents is 800mA/g), its appearanceAmount is 96mAh/g.
Claims (2)
1. a Mo0.5W0.5S2Nanometer watt/Graphene electrochemistry storage magnesium combination electrode, is characterized in that the electrochemistry of combination electrodeStorage magnesium active material is Mo0.5W0.5S2The composite nano materials of nanometer watt/Graphene, Mo in composite nano materials0.5W0.5S2NanometerWatt and the ratio of the amount of substance of Graphene be 1:2, described Mo0.5W0.5S2The nanometer watt layer structure for few number of plies, combination electrodeComponent and mass percentage content thereof be: Mo0.5W0.5S2Nanometer 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 propylidene twoThe two ammonium bromides of amine, and fully stir, then add successively Cys, ammonium thiomolybdate and sulfo-ammonium tungstate, and constantly stirMix Cys, ammonium thiomolybdate and sulfo-ammonium tungstate are dissolved completely, Cys, ammonium thiomolybdate and sulfo-wolframic acidThe ratio of the amount of substance of ammonium consumption is 5:0.5:0.5, the amount of substance of ammonium thiomolybdate, sulfo-ammonium tungstate and graphene oxide itThan being 0.5:0.5:2;
(2) mixed dispersion step (1) being obtained is transferred in hydrothermal reaction kettle, and adds deionized water to adjust volume extremely80% of hydrothermal reaction kettle 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 is put in constant temperature oven, at 230-At 250 DEG C, after hydro-thermal reaction 24h, allow it naturally cool to room temperature, with centrifugation collection hydro-thermal reaction solid product, and spendIonized water fully washs, vacuum drying at 100 DEG C, by the hydro-thermal reaction solid product obtaining at nitrogen/hydrogen mixed gas atmosphereIn at 800 DEG C heat treatment 2h, in mist, hydrogen volume mark is 10%, finally prepares Mo0.5W0.5S2Nanometer watt/The composite nano materials of Graphene;
(3) by the Mo of above-mentioned preparation0.5W0.5S2Nanometer watt/Graphene composite nano materials is as electrochemistry storage magnesium active material, withThe 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5% under agitation fillsDivide and mix the uniform slurry of furnishing, this slurry is coated onto equably on the foam copper of collector, dry rear roll extrusion obtains multipleComposite electrode.
2. Mo according to claim 10.5W0.5S2Nanometer watt/Graphene electrochemistry storage magnesium combination electrode, is characterized in that,Described Mo0.5W0.5S2The average number of plies of nanometer watt is 3 layers.
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| CN102142537A (en) * | 2011-02-25 | 2011-08-03 | 浙江大学 | Graphene/MoS2 compound nano material lithium ion battery electrode and preparation method thereof |
| CN102683648A (en) * | 2012-06-08 | 2012-09-19 | 浙江大学 | Preparation method of few-layer MoS2/graphene electrochemical storage lithium composite electrode |
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