CN104091923B - Porous WS2 nanosheet and graphene electrochemical lithium storage composite electrode and preparation method thereof - Google Patents

Porous WS2 nanosheet and graphene electrochemical lithium storage composite electrode and preparation method thereof Download PDF

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Publication number
CN104091923B
CN104091923B CN201410339880.5A CN201410339880A CN104091923B CN 104091923 B CN104091923 B CN 104091923B CN 201410339880 A CN201410339880 A CN 201410339880A CN 104091923 B CN104091923 B CN 104091923B
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graphene
nanometer sheet
holes
nanosheet
porous
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CN104091923A (en
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陈卫祥
叶剑波
马琳
王臻
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • 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 porous WS2 nanosheet and graphene composite nanomaterial and a preparation method thereof. The porous WS2 nanosheet and graphene composite nanomaterial is formed by compounding a porous WS2 nanosheet and graphene, wherein the porous WS2 nanosheet has a single layer or few layers, and the mass ratio of WS2 to graphene ranges from 1 to 1-1 to 3. The preparation method comprises the following steps of firstly, ultrasonically dispersing graphene oxide into deionized water; then, adding cationic column[5]arene supramolecules, and sufficiently stirring; next, sequentially adding L-cysteine and ammonium thiotungstate, and sufficiently stirring to dissolve L-cysteine and ammonium thiotungstate; and transferring the mixed dispersion system into a hydrothermal reaction kettle to carry out hydrothermal reaction at the temperature of 230-250 DEG C for 20-24 h, then, naturally cooling to the room temperature, centrifuging to collect a solid product, washing, drying and carrying out heat treatment to obtain the porous WS2 nanosheet and graphene composite nanomaterial. The method disclosed by the invention has the characteristics of simplicity and convenience; in addition, no organic solvent is needed to be consumed.

Description

WS2Nanometer sheet with holes/Graphene electrochemistry storage lithium combination electrode and preparation method
Technical field
The present invention relates to composite nano materials and preparation method thereof, more particularly to WS2Nanometer sheet/Graphene with holes is compound to be received Rice material and its hydrothermal preparing process, belong to inorganic composite nano field of material technology.
Background technology
Two-dimensional ultrathin nanometer sheet material has numerous excellent characteristics with its unique pattern, and its research causes people's Great interest.Graphene is most typical two-dimensional nano sheet material, and its unique two-dimensional nano chip architecture makes its numerous uniqueness The performances such as physics, chemistry and mechanics, with important scientific research meaning and extensive technology application prospect.Graphene has pole High specific surface area, high conductive and heat conductivility, high charge mobility, excellent mechanical property, these excellent characteristics So that Graphene is before the aspects such as micro-nano electronic device, energy storage material and new catalyst carrier have a wide range of applications Scape.
The immense success that the discovery of Graphene and its research are obtained excites people to other inorganic two-dimensional nano sheet materials The great interest of research, the such as transition metal dichalcogenide of monolayer or few number of plies.As a kind of typical and important transition gold Category disulphide, WS2With with layer structure as graphite-like, be the S-W-S units of Covalent bonding together in its layer, layer and layer it Between combination be weaker Van der Waals force.This typical layered structure and weak Van der Waals force, make WS2As kollag tool There is relatively low friction factor, still there is relatively low coefficient of friction particularly under the conditions of high temperature, fine vacuum etc., be a kind of excellent Kollag.In addition, layer structure WS2The embedded of external atom or ion, therefore WS can be allowed2Lamellar compound It is a kind of rising electrochemical lithium storage and storage Development of Magnesium Electrode Materials.
Recently, Graphene concept has expanded to the inorganic compound of other layer structures from material with carbon element, that is, for The inorganic material of layer structure, when its number of plies is reduced (less than about 6 layers), especially 4 layers of reduction and its it is following when, its is electro Matter or band structure can produce significantly change, special so as to cause to which show the physics different from corresponding body phase material and chemistry Property.In addition to Graphene, recent research indicate that when body phase WS2It is reduced to few number of plies when monolayer (particularly), it is shown that with body phase The visibly different physics of material, chemistry and electronics property.Studies have reported that the WS of monolayer or few number of plies2With more preferable electrification Learn storage lithium performance and high electrocatalytic hydrogen evolution reactivity.But the storage lithium electrode material and electro-catalysis as electrochemical reaction Material, WS2Electric conductivity low between layers have impact on its application performance.
Due to WS2Nanometer sheet has similar two-dimensional nano piece pattern with Graphene, and both tie in microscopic appearance and crystal There is good similarity on structure.If by WS2Nanometer sheet is combined with Graphene and prepares both composites, graphene nano The high conduction performance of piece can further improve the electric conductivity of composite, strengthen electrochemistry storage lithium and electrocatalytic reaction process In electron transmission, can further improve the electrochemistry storage lithium performance and electrocatalysis characteristic of composite.WS2The electricity of nanometer sheet The catalysis activity of catalytic hydrogen evolution reaction is mainly derived from its active sites edge, increases WS2The edge of nanometer sheet is that enhanced electricity is urged Change an approach of performance.Lithium electrode material, the WS of more multiple edge are store as electrochemistry2Nanometer sheet can provide more and phase To shorter lithium ion diffusion admittance, contribute to booster electrochemistry storage lithium performance.With common WS2Nanometer sheet compares, with holes Nanometer sheet WS2With more edge, there are more contacts area with electrolyte, its chemical property can be strengthened.Cause This, this WS2The composite nano materials of nanometer sheet/Graphene with holes store lithium electrode material as electrochemistry and evolving hydrogen reaction electricity is urged Agent has a wide range of applications and enhanced chemical property.
But, up to the present, WS2Nanometer sheet/graphene composite nano material with holes and its preparation have not been reported.This Invention with graphene oxide and thio ammonium tungstate as raw material, by cationic post [5] arene-based supermolecule assist hydrothermal method With subsequent heat treatment, WS is prepared for2The composite nano materials of nanometer sheet/Graphene with holes.This preparation WS2Nanometer sheet with holes/ The method of the composite nano materials of Graphene has simple, convenient and is easily enlarged industrial applications a little.
The content of the invention
It is an object of the invention to provide a kind of WS2Nanometer sheet/graphene composite nano material with holes and preparation method thereof, The composite nano materials are by WS2Nanometer sheet with holes is compound with Graphene to be constituted, the WS2Nanometer sheet with holes is monolayer or few layer Several layer structures, the WS2The ratio of the amount of the material between nanometer sheet with holes and Graphene is 1:1-1:3.
The layer structure of few number of plies refers to the number of plies in 6 layers or less than 6 layers of layer structure.
WS of the present invention2The step of preparation method of nanometer sheet/graphene composite nano material with holes, is as follows：
(1) by graphene oxide ultrasonic disperse in deionized water, it is subsequently adding cationic post [5] arene-based supermolecule (its structure is shown in Fig. 1), and be sufficiently stirred for；
(2) L-Cysteine and thio ammonium tungstate are sequentially added in the mixed system of step (1), and is stirred continuously and makes L- Cysteine and thio ammonium tungstate are completely dissolved, and the ratio of the amount of the material of L-Cysteine and thio ammonium tungstate consumption is 5:1, sulfur For ammonium tungstate and the amount of the material of graphene oxide ratio 1:1-1:3；
(3) mixed dispersion that step (2) is obtained is transferred in hydrothermal reaction kettle, and adds deionized water adjusting body Product to the 80% of hydrothermal reaction kettle nominal volume, the molar concentration of cationic post [5] arene-based supermolecule is 0.001～ 0.002mol/L, the molar concentration of graphene oxide is 30-65mmol/L, the reactor is put in constant temperature oven, 230-250 At DEG C after hydro-thermal reaction 20-24h, allow it to naturally cool to room temperature, with centrifugation solid product is collected, and deionized water is filled Divide washing, be vacuum dried at 100 DEG C；By above-mentioned resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C Heat treatment 2h, the volume fraction of hydrogen is 10% in mixed gas, prepares WS2The compound of nanometer sheet/Graphene with holes is received Rice material.
Above-mentioned graphene oxide is prepared using improved Hummers methods.
The WS of the present invention2Nanometer sheet/graphene composite nano material with holes and preparation method thereof has advantages below：
Surface of graphene oxide and edge carry many oxygen-containing functional groups (such as hydroxyl, carbonyl, carboxyl), these oxygen-containing senses Group makes graphene oxide more easily be dispersed in water or organic liquid, but these oxygen-containing functional groups make surface of graphene oxide With negative charge so that graphene oxide and the WS with negative charge4 2-Ion is incompatible, and the present invention first will by electrostatic interaction Cationic post [5] arene-based supermolecule (its structure is shown in Fig. 1) is adsorbed onto surface of graphene oxide, WS4 2-Ion is just easier to and suction The graphene oxide of attached Gemini surface active agent interacts and is combined together.Importantly, positive with general quaternary ammonium salt Ionic surface active agent is compared, and respectively there is the quaternary ammonium of 5 positively chargeds at the two ends of cationic post [5] arene-based supermolecule that the present invention is used There is higher mutual electrostatic interaction between hydrophilic group, with electronegative graphene oxide；Cationic post [5] aromatic hydrocarbons surpasses Molecule vertically or in the way of lying low to adsorb in surface of graphene oxide, and can together be entrained in hydrothermal treatment process In hydrothermal product, in heat treatment process, cationic post [5] arene-based supermolecule is carbonized, and can finally prepare and carry Perhaps microporous WS2The composite nano materials of nanometer sheet and Graphene.This WS2Nanometer sheet with holes not only has more activity Position edge, can strengthen its electrocatalysis characteristic to evolving hydrogen reaction, and can provide more short lithium ion diffusion admittances, There is assistant to strengthen its electrochemistry storage lithium performance.WS2Nanometer sheet/graphene composite material with holes can increase it with electrolyte Contact area, further helping in improves its chemical property.The preparation method of the present invention has simple, convenient and is easily enlarged The characteristics of industrial applications.
Description of the drawings
Fig. 1 cationic post [5] arene-based supermolecule structural representations.
The WS that Fig. 2 embodiments 1 are prepared2The XRD figure of nanometer sheet/graphene composite nano material with holes.
The WS that Fig. 3 embodiments 1 are prepared2SEM shape appearance figures (a) of nanometer sheet/graphene composite nano material with holes and Transmission electron microscope photo (b).
WS prepared by Fig. 4 comparative examples2SEM shape appearance figures (a) of nanometer sheet/graphene composite nano material, TEM photos (b) With HRTEM photos (c).
Specific embodiment
The present invention is further illustrated with reference to embodiments.
Graphene oxide in following examples is prepared using improved Hummers methods：Under 0 DEG C of ice bath, will 10.0mmol (0.12g) graphite powder dispersed with stirring is stirred continuously down and is slowly added into KMnO in 50mL concentrated sulphuric acids4, added KMnO4 Quality be 4 times of graphite powder, stir 50 minutes, when temperature rises to 35 DEG C, be slowly added into 50mL deionized waters, be stirred for 30 minutes, add the H of 15mL mass fractions 30%2O2, stir 30 minutes, through centrifugation, successively with mass fraction 5% Graphene oxide is obtained after HCl solution, deionized water and acetone cyclic washing.
Embodiment 1.
1) by 2.5mmol graphene oxides ultrasonic disperse in 60mL deionized waters, 0.16mmol cationics are added Post [5] arene-based supermolecule, and be sufficiently stirred for；
2) 0.76g (6.25mmol) L-Cysteine and the thio ammonium tungstates of 1.25mmol are then sequentially added, and is constantly stirred Mixing is completely dissolved L-Cysteine and thio ammonium tungstate, and deionized water adjusts volume to about 80mL；
3) resulting mixed liquor is transferred in the hydrothermal reaction kettle of 100mL, the reactor is put in constant temperature oven, At 230 DEG C after hydro-thermal reaction 24h, allow it to naturally cool to room temperature, with centrifugation solid product is collected, and deionized water is filled Point washing, at 100 DEG C be vacuum dried, by resulting hydro-thermal solid product in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C Heat treatment 2h, prepares WS2The composite nano materials of nanometer sheet/Graphene with holes, the volume fraction of hydrogen in mixed gas For 10%.
WS is obtained with XRD, SEM and TEM to prepared2The composite nano materials of nanometer sheet/Graphene with holes are characterized. XRD analysis result shows WS in composite nano materials2The average number of plies be 2 layers (see Fig. 2), SEM patterns and transmission electron microscope photo (see Fig. 3) also clearly demonstrates respectively WS in composite2It is the nanometer sheet with micropore, its number of plies is in 1-3 layers, WS2It is with holes to receive WS in rice piece/graphene composite nano material2It is 1 with the ratio of the amount of graphite olefinic substance:2.
Comparative example
Using Dodecyl trimethyl ammonium chloride cationic surfactant, by above-mentioned similar approach WS is prepared for2Nanometer The composite nano materials of piece and Graphene, concrete preparation process is as follows：
By 2.5mmol graphene oxides ultrasonic disperse in 60mL deionized waters, 1.6mmol dodecyl front threes are added Bromide ammonium cationic surfactant, and being sufficiently stirred for, then sequentially add 0.76g (6.25mmol) L-Cysteine and The thio ammonium tungstates of 1.25mmol, and being stirred continuously is completely dissolved L-Cysteine and thio ammonium tungstate, deionized water adjustment Volume is transferred to resulting mixed liquor in the hydrothermal reaction kettle of 100mL to about 80mL, and the reactor is put into into constant temperature oven In, at 230 DEG C after hydro-thermal reaction 24h, allow it to naturally cool to room temperature, solid product is collected with centrifugation, and use deionization Water is fully washed, at 100 DEG C be vacuum dried, by resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C Heat treatment 2h, the volume fraction of hydrogen is 10% in mixed gas, prepares WS2The nano combined material of nanometer sheet/Graphene Material.
With XRD, SEM and TEM to finally preparing WS2Nanometer sheet is characterized with the nano composite material of Graphene, XRD analysis result shows WS in composite nano materials2For layer structure, the average number of plies is 7 layers.SEM shape appearance figures, TEM photos and HRTEM photos (see Fig. 4) show the WS being supported on Graphene2For the pattern of nanometer sheet not with holes, the main number of plies is 7 layers
Electrocatalytic reaction Hydrogen Evolution Performance test and comparison：By the WS of the above-mentioned preparations of 4.0mg2Nanometer sheet/Graphene with holes is combined Nano material (or WS prepared by comparative example2Nanometer sheet/graphene composite nano material) 1.0mL deionization water-ethanol mixing (volume ratio 1 in liquid:1) Nafion solution (5wt%) of 30uL, supersound process 2h so as to be sufficiently mixed dispersion, are added Uniformly, uniform slurry is obtained, the mixed slurry for taking 5uL with liquid-transfering gun is dripped on the glassy carbon electrode of diameter 5mm, at 80 DEG C Test job electrode is obtained after drying.Electrolyte is the aqueous sulfuric acid of 0.5M, and reference electrode is saturated calomel electrode, and platinized platinum is made It is, to electrode, electrocatalysis characteristic of the linear sweep voltametry test material to evolving hydrogen reaction to be used on CHI660B electrochemical workstations Tested, scanning speed is 5mV/s.Test result is displayed under identical cathodic polarization overpotential, WS2Nanometer sheet with holes/ Graphene composite nano material electrode compares WS2Nanometer sheet/graphene composite nano material electrode has higher evolving hydrogen reaction electricity Stream, such as：Under 0.20V vs.RHE current potentials, in WS2Electrochemical catalysis on nanometer sheet with holes/graphene composite nano material electrode Evolving hydrogen reaction electric current position 16.5mA, in WS2Evolving hydrogen reaction electric current is 6.5mA on nanometer sheet/graphene composite nano material electrode. Enhancing to evolving hydrogen reaction electrocatalysis characteristic is due to WS2WS in nanometer sheet/graphene composite nano material with holes2Nanometer with holes Piece compares WS2WS in nanometer sheet/graphene composite nano material2Nanometer sheet has more active sites edges.In addition, WS2It is with holes to receive Rice piece/graphene composite nano material compares WS2Nanometer sheet/graphene composite nano material have more with electrolyte contacts Area.

Claims (1)

1. a kind of WS2The composite nano materials of nanometer sheet/Graphene with holes, it is characterised in that the composite nano materials are by WS2 Nanometer sheet with holes is compound with Graphene to be constituted, the WS2Nanometer sheet with holes is tied for the stratiform of few number of plies that the number of plies is less than 6 layers Structure, the WS2The ratio of the amount of the material between nanometer sheet with holes and Graphene is 1:1-1:3, the system of the composite nano materials Preparation Method is carried out according to the following steps：
(1) by graphene oxide ultrasonic disperse in deionized water, cationic post [5] arene-based supermolecule is subsequently adding, and is filled Divide stirring, the preparation method of the graphene oxide is as follows：Under 0 DEG C of ice bath, 10.0mmol graphite powder dispersed with stirring is arrived In 50mL concentrated sulphuric acids, it is stirred continuously down and is slowly added into KMnO4, added KMnO4Quality be 4 times of graphite powder, stir 50 minutes, When temperature rises to 35 DEG C, 50mL deionized waters are slowly added into, are stirred for 30 minutes, add 15mL mass fractions 30% H2O2, stir 30 minutes, through centrifugation, successively with the HCl solution of mass fraction 5%, deionized water and acetone cyclic washing After obtain graphene oxide；
(2) and then by L-Cysteine and thio ammonium tungstate it is added sequentially in the mixed system that step (1) is obtained, and constantly stirs Mixing is completely dissolved L-Cysteine and thio ammonium tungstate, and the ratio of the amount of the material of L-Cysteine and thio ammonium tungstate consumption is 5:1, thio ammonium tungstate is 1 with the ratio of the amount of the material of graphene oxide:1-1:3；
(3) mixed dispersion that step (2) is obtained is transferred in hydrothermal reaction kettle, and adds deionized water adjustment volume extremely The 80% of hydrothermal reaction kettle nominal volume, cationic post [5] arene-based supermolecule molar concentration is 0.001～0.002mol/L, The molar concentration of graphene oxide is 30-65mmol/L, the reactor is put in constant temperature oven, the hydro-thermal at 230-250 DEG C After reaction 20-24h, allow it to naturally cool to room temperature, with centrifugation hydro-thermal reaction solid product is collected, and deionized water is filled Point washing, at 100 DEG C be vacuum dried, by the hydro-thermal reaction solid product for obtaining in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C Lower heat treatment 2h, the volume fraction of hydrogen is 10% in mixed gas, finally prepares WS2Nanometer sheet/Graphene with holes Composite nano materials, the structural formula of cationic post [5] aromatic hydrocarbons is as follows：
CN201410339880.5A 2014-07-17 2014-07-17 Porous WS2 nanosheet and graphene electrochemical lithium storage composite electrode and preparation method thereof Expired - Fee Related CN104091923B (en)

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