CN104103834A - WS2 perforated nanosheet/graphene electrochemical sodium storage composite electrode and preparation method - Google Patents
WS2 perforated nanosheet/graphene electrochemical sodium storage composite electrode and preparation method Download PDFInfo
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- CN104103834A CN104103834A CN201410339847.2A CN201410339847A CN104103834A CN 104103834 A CN104103834 A CN 104103834A CN 201410339847 A CN201410339847 A CN 201410339847A CN 104103834 A CN104103834 A CN 104103834A
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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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Abstract
The invention discloses a WS2 perforated nanosheet/graphene electrochemical sodium storage composite electrode and a preparation method thereof. An electrochemical sodium storage active substance of the WS2 perforated nanosheet/graphene electrochemical sodium storage composite electrode adopts a WS2 perforated nanosheet/graphene composite nanomaterial, a substance ratio of the WS2 perforated nanosheets to graphene is (1:1)-(1:3), a few layers of the WS2 perforated nanosheets are provided, and the composite electrode comprises components in percentage by mass as follows: 80% of the WS2 perforated nanosheet/graphene composite nanomaterial, 10% of acetylene black, 5% of carboxymethyl cellulose and 5% of polyvinylidene fluoride. The preparation method comprises the steps as follows: the WS2 perforated nanosheet/graphene composite nanomaterial is prepared firstly and is prepared into slurry with acetylene black, carboxymethyl cellulose and polyvinylidene fluoride, a current collector is coated with the slurry, and after the slurry is dried and rolled, the WS2 perforated nanosheet/graphene electrochemical sodium storage composite electrode is obtained. The electrochemical sodium storage composite electrode has high reversible sodium storage capacity, excellent cycle performance and enhanced magnification characteristic, thereby having wide application prospect in a novel sodium-ion battery.
Description
Technical field
The present invention relates to a kind of WS
2-nanometer sheet/Graphene electrochemistry storage sodium combination electrode with holes and preparation method thereof, relates in particular to and uses WS
2electrochemistry storage sodium combination electrode prepared by nanometer sheet/Graphene composite nano materials with holes and preparation method thereof, belongs to new energy materials, energy storage and switch technology field.
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 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 fail safe 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 sodium ion has less radius, can electrochemical intercalation and deintercalation in the compound of some layer of structure, as inorganic transition metal oxide, sulfide etc.Sodium also has aboundresources in addition, cheap, specific energy is high, nontoxic and process the advantages such as convenient.Therefore, chargeable sodium-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 sodium.
WS
2having 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.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 WS
2material can be used as the material of main part that inserts reaction.Therefore, WS
2it is a kind of electrode material of rising electrochemistry storage sodium.But general WS
2nano material electrochemistry storage sodium performance can't meet practical application, and its electrochemistry storage sodium 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 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 approximately 6 layers), especially reduce 4 layers and when following, 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 WS
2reduce to few number of plies when individual layer (particularly), shown and the visibly different physics of body phase material, chemical characteristic.Research shows the WS of individual layer or few number of plies
2nanometer sheet has better electrochemistry storage sodium performance.But as the electrode material of electrochemistry storage sodium, WS
2low electric conductivity between layers affected the performance of its application.
Due to 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 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 sodium electrode process, can further improve the electrochemistry storage sodium performance of composite material.With common WS
2nanometer sheet comparison, the WS of little nano-sheet pattern with holes
2not only there is more edge, more short sodium ion diffusion admittance can be provided, and load on Graphene, there is more contact area with electrolyte.Therefore WS
2the composite nano materials of nanometer sheet/Graphene with holes can show the electrochemistry storage sodium performance of remarkable enhancing.
But, up to the present, use WS
2nanometer sheet/Graphene composite nano materials with holes have not been reported as electrochemistry storage sodium 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 cationic post [5] arene-based supermolecule and heat treatment subsequently, prepared WS
2the composite nano materials of nanometer sheet/Graphene with holes, then uses WS
2the composite nano materials of nanometer sheet/Graphene with holes, as the active material of electrochemistry storage sodium, has been prepared the combination electrode of electrochemistry storage sodium.The present invention prepares WS
2the method of nanometer sheet/graphene nano material electrochemical storage sodium combination electrode with holes 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 WS
2-nanometer sheet/Graphene electrochemistry storage sodium combination electrode with holes and preparation method thereof, the electrochemistry storage sodium active material of described combination electrode is WS
2-the composite nano materials of nanometer sheet/Graphene with holes, WS in composite nano materials
2the ratio of the amount of substance of nanometer sheet with holes and Graphene is 1:1-1:3, described WS
2nanometer sheet with holes is the layer structure of few number of plies, and the component of described combination electrode and mass percentage content thereof are: WS
2nanometer sheet/Graphene composite nano materials 80% with holes, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%.
As preferably, described WS
2the number of plies of nanometer sheet with holes is 2 ~ 4 layers.
The layer structure of few number of plies refers to the layer structure of the number of plies below 6 layers or 6 layers.
WS of the present invention
2-the preparation method of nanometer sheet/Graphene electrochemistry with holes storage sodium combination electrode is according to the following steps:
(1) be dispersed in deionized water ultrasonic graphene oxide, add cationic post [5] arene-based supermolecule (its structure is shown in Fig. 1), 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 molar concentration of cationic post [5] arene-based supermolecule is 0.001 ~ 0.002 mol/L, the molar concentration of graphene oxide is 30-65 mmol/L, this reactor is put in constant temperature oven, at 230-250 DEG C after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, with centrifugation collection hydro-thermal reaction solid product, and fully wash with deionized water, vacuumize at 100 DEG C, by the hydro-thermal reaction solid product obtaining in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C heat treatment 2 h, in mist, hydrogen volume mark is 10%, finally prepare WS
2the composite nano materials of nanometer sheet/Graphene with holes,
(3) by the WS of above-mentioned preparation
2nanometer sheet/Graphene composite nano materials with holes is as the electrochemistry storage sodium active material of preparing combination 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: WS
2nanometer sheet/Graphene composite nano materials 80% with holes, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%, is then coated onto this slurry on the Copper Foil of collector equably, vacuumize at 110 DEG C, roll extrusion obtains WS
2nanometer sheet/Graphene electrochemistry storage sodium combination electrode with holes.
Above-mentioned graphene oxide adopts improved Hummers method preparation.
WS of the present invention
2nanometer sheet/Graphene electrochemistry storage sodium combination electrode with holes and preparation method thereof 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 charge
4 2-ion is incompatible, and the present invention is first adsorbed onto graphene oxide surface, WS by cationic post [5] arene-based supermolecule (its structure is shown in Fig. 1) by electrostatic interaction
4 2-ion is just easier to interact and combine with the graphene oxide that has adsorbed Gemini surface active agent.The more important thing is, compared with general quaternary cationics, respectively there is the quaternary ammonium hydrophilic radical of 5 positively chargeds at the two ends of cationic post [5] arene-based supermolecule that the present invention uses, and between electronegative graphene oxide, have stronger mutual electrostatic interaction; This cationic post [5] arene-based supermolecule can be vertically or the mode lying low be adsorbed on graphene oxide surface, and be entrained to together in hydrothermal product in hydrothermal treatment consists process, in heat treatment process, cationic post [5] arene-based supermolecule is carbonized, and finally can prepare with being permitted microporous WS
2the composite nano materials of nanometer sheet and Graphene.This WS
2nanometer sheet with holes has more edge, as electrochemistry storage sodium material, can provide more short sodium ion diffusion admittance, contributes to strengthen its electrochemistry storage sodium performance; In addition, WS
2nanometer sheet/graphene composite material with holes can increase the contact area of itself and electrolyte, can further contribute to improve its chemical property.Therefore, the present invention WS
2the electrochemistry storage sodium electrode that nanometer sheet/graphene composite material with holes is prepared as electroactive substance has high electrochemistry storage sodium capacity, excellent cycle performance and the remarkable large current density electrical characteristics that strengthen.
Brief description of the drawings
The structural representation of the cationic post of Fig. 1 [5] arene-based supermolecule.
The WS that Fig. 2 embodiment 1 prepares
2the XRD figure of nanometer sheet/Graphene composite nano materials with holes.
The WS that Fig. 3 embodiment 1 prepares
2the SEM shape appearance figure (a) of nanometer sheet/Graphene composite nano materials with holes and transmission electron microscope photo (b).
Embodiment
Further illustrate the present invention below in conjunction with embodiment.
Graphene oxide in following example adopts improved Hummers method preparation: 0
ounder C ice bath, by 10.0 mmol (0.12 g) graphite powder dispersed with stirring in the 50 mL concentrated sulfuric acids, under constantly stirring, slowly add KMnO
4, institute adds KMnO
4quality be 4 times of graphite powder, stir 50 minutes, in the time of temperature rise to 35 DEG C, 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 ultrasonic 2.5 mmol graphene oxides, add again the cationic post of 0.16 mmol [5] arene-based supermolecule, and fully stir, then add successively 0.76 g (6.25 mmol) Cys and 1.25 mmol sulfo-ammonium tungstates, and constantly stir Cys and sulfo-ammonium tungstate are dissolved completely, with extremely approximately 80 mL of deionized water adjustment volume;
2) obtained mixed liquor is transferred in the hydrothermal reaction kettle of 100 mL, this reactor is put in constant temperature oven, at 230 DEG C after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, collect solid product with centrifugation, and fully wash with deionized water, vacuumize 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 WS
2the composite nano materials of nanometer sheet/Graphene with holes, WS in composite nano materials
2with the ratio of Graphene amount of substance be 1:2, with XRD, SEM and TEM are to the prepared WS that obtains
2the composite nano materials of nanometer sheet/Graphene with holes characterizes (the results are shown in Figure 2 and Fig. 3), and characterization result shows in composite nano materials and loads on the WS on Graphene
2be the nanometer sheet with many holes, its number of plies is mainly at 2-5 layer, 4 layers of the average numbers of plies;
3) by the WS of above-mentioned preparation
2nanometer sheet/Graphene composite nano materials with holes is as the electrode active material of electrochemistry storage sodium, 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 Copper Foil of collector, vacuumize at 110 DEG C, then roll extrusion obtains WS
2nanometer sheet/Graphene electrochemistry storage sodium combination electrode with holes, in combination electrode, each constituent mass percentage is: WS
2nanometer sheet/Graphene composite nano materials 80% with holes, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%.
Electrochemistry storage sodium performance test: taking combination electrode as work electrode, as to electrode, electrolyte is 1.0 mol/L NaClO with sodium metal sheet
4perfluorocarbon acid vinyl acetate/propene carbonate (FEC/PC, volume ratio is 1:1) solution be electrolyte, porous polypropylene film (Celguard-2400) is barrier film, in the suitcase that is full of argon gas, is assembled into test battery.By the electrochemistry storage sodium 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: WS
2the initial reversible capacity of electrochemistry storage sodium of nanometer sheet/graphene combination electrode with holes is 425 mAh/g, and after 50 circulations, reversible capacity is 409 mAh/g, has shown high specific capacity and excellent stable circulation performance; In the time of high current charge-discharge (charging and discharging currents is 1000 mA/g), its capacity is 356 mAh/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 approach
2nanometer sheet/Graphene electrochemistry storage sodium nano material combination electrode, concrete preparation process is as follows:
Be dispersed in 60 mL deionized waters ultrasonic 2.5 mmol graphene oxides, add again 1.6 mmol DTAB cationic surfactants, and fully stir, then add successively 0.76g (6.25 mmol) Cys and 1.25 mmol sulfo-ammonium tungstates, and constantly stir Cys and sulfo-ammonium tungstate are dissolved completely, with extremely approximately 80 mL of deionized water adjustment volume, obtained mixed liquor is transferred in the hydrothermal reaction kettle of 100 mL, this reactor is put in constant temperature oven, at 230 DEG C after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, collect solid product with centrifugation, and fully wash with deionized water, vacuumize at 100 DEG C, by obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C heat treatment 2 h, in mist, the volume fraction of hydrogen is 10%, prepare WS
2the nano composite material of nanometer sheet/Graphene, WS in composite nano materials
2with the ratio of the amount of substance of Graphene be 1:2.With XRD, SEM and TEM are to finally preparing WS
2the nano composite material of nanometer sheet/Graphene characterizes, and XRD analysis result shows WS in composite nano materials
2for layer structure, its average number of plies is 7 layers, and TEM and HRTEM photo show the WS loading on Graphene
2for nanometer sheet pattern, its thickness and plane sizes are not so good as WS above
2nanometer sheet with holes evenly, WS
2the 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 WS
2nanometer sheet/Graphene composite nano materials is electrochemistry storage sodium active material, by above-mentioned steps 3) process prepare WS
2nanometer sheet/Graphene electrochemistry storage sodium combination electrode, and test its electrochemistry storage sodium performance by aforementioned identical electrochemistry storage sodium method of testing.Result shows: WS
2the initial reversible capacity of nanometer sheet/Graphene electrochemistry storage sodium combination electrode is that 206 mAh/g(charging and discharging currents are 50 mA/g), after 50 circulations, reversible capacity is 191 mAh/g; In the time of high current charge-discharge (charging and discharging currents is 1000 mA/g), its capacity is 112 mAh/g.
Claims (3)
1. a WS
2-nanometer sheet/Graphene electrochemistry storage sodium combination electrode with holes, is characterized in that, the electrochemistry storage sodium active material of described combination electrode is WS
2-the composite nano materials of nanometer sheet/Graphene with holes, WS in composite nano materials
2the ratio of the amount of substance of nanometer sheet with holes and Graphene is 1:1-1:3, described WS
2nanometer sheet with holes is the layer structure of few number of plies, and the component of described combination electrode and mass percentage content thereof are: WS
2nanometer sheet/Graphene composite nano materials 80% with holes, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%.
2. WS according to claim 1
2-nanometer sheet/Graphene electrochemistry storage sodium combination electrode with holes, is characterized in that described WS
2the number of plies of nanometer sheet with holes is 2 ~ 5 layers.
3. WS described in a claim 1 or 2
2-the preparation method of nanometer sheet/Graphene electrochemistry storage sodium combination electrode with holes, is characterized in that, preparation method carries out according to the following steps:
(1) be dispersed in deionized water ultrasonic graphene oxide, add cationic post [5] arene-based supermolecule, 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, sulfo-ammonium tungstate with the ratio of the amount of substance of graphene oxide at 1:1-1:3;
(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 molar concentration of cationic post [5] arene-based supermolecule is 0.001 ~ 0.002 mol/L, the molar concentration of graphene oxide is 30-65 mmol/L, this reactor is put in constant temperature oven, at 230-250 DEG C after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, with centrifugation collection hydro-thermal reaction solid product, and fully wash with deionized water, vacuumize at 100 DEG C, by the hydro-thermal reaction solid product obtaining in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C heat treatment 2 h, in mist, hydrogen volume mark is 10%, finally prepare WS
2the composite nano materials of nanometer sheet/Graphene with holes,
(3) by the WS of above-mentioned preparation
2nanometer sheet/Graphene composite nano materials with holes is as the electrochemistry storage sodium active material of preparing combination 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%, this slurry is coated onto equably on the Copper Foil of collector, vacuumize at 110 DEG C, roll extrusion obtains WS
2nanometer sheet/Graphene electrochemistry storage sodium combination electrode with holes.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109103279A (en) * | 2018-07-16 | 2018-12-28 | 深圳大学 | Optical detector and preparation method thereof based on nanometer SnS material |
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