CN104091923A - 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 PDFInfo
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- CN104091923A CN104091923A CN201410339880.5A CN201410339880A CN104091923A CN 104091923 A CN104091923 A CN 104091923A CN 201410339880 A CN201410339880 A CN 201410339880A CN 104091923 A CN104091923 A CN 104091923A
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- 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
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- 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
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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
- H01M4/58—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
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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
- H01M4/62—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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- 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
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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 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 20-24h, 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
Technical field
The present invention relates to composite nano materials and preparation method thereof, relate in particular to WS
2nanometer sheet/Graphene composite nano materials with holes and hydrothermal preparing process thereof, belong to inorganic composite nano material technology field.
Background technology
Two dimension ultrathin nanometer sheet 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 sheet material, and its unique two-dimensional nano chip architecture makes the performances such as physics, chemistry and mechanics of its numerous uniquenesses, has important scientific research meaning and technology application prospect widely.Graphene has high specific area, high conduction and heat conductivility, high charge mobility, excellent mechanical property, these excellent characteristics make Graphene be with a wide range of applications at micro-nano electronic device, energy storage material and the novel aspects such as catalyst carrier.
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 sheet material researchs, as the transition metal dichalcogenide of individual layer or few number of plies etc.As a kind of typical case and important transition metal dichalcogenide, WS
2having and layer structure like graphite-like, is the S-W-S unit of covalent bonds in its layer, and combination is between layers weak Van der Waals force.This typical layered structure and weak Van der Waals force, make WS
2as kollag, having lower friction factor, particularly under the conditions such as high temperature, high vacuum, still have lower coefficient of friction, is a kind of good kollag.In addition, layer structure WS
2can allow the embedding of external atom or ion, so WS
2lamellar compound is also 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, namely for the inorganic material of layer structure, when 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, research recently shows as body phase WS
2reduce to few number of plies when individual layer (particularly), shown and the visibly different physics of body phase material, chemistry and electronics property.Studies have reported that the WS of individual layer or few number of plies
2there is better electrochemistry storage lithium performance and high electrocatalytic hydrogen evolution reactivity.But as storage lithium electrode material and the electrocatalysis material of electrochemical reaction, 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 lithium and electrocatalytic reaction process, can further improve electrochemistry storage lithium performance and the electrocatalysis characteristic of composite material.WS
2the catalytic activity of the electrocatalytic hydrogen evolution reaction of nanometer sheet is mainly derived from its active sites edge, increases WS
2the edge of nanometer sheet is an approach of the electrocatalysis characteristic of enhancing.As electrochemistry storage lithium electrode material, the more WS of multiple edge
2nanometer sheet can provide more and relatively short lithium ion diffusion admittance, contributes to booster electrochemistry storage lithium performance.With common WS
2nanometer sheet comparison, nanometer sheet WS with holes
2there is more edge, there is more contact area with electrolyte, can strengthen its chemical property.Therefore, this WS
2the chemical property that the composite nano materials of nanometer sheet/Graphene with holes has a wide range of applications and strengthens as electrochemistry storage lithium electrode material and evolving hydrogen reaction eelctro-catalyst.
But, up to the present, WS
2nanometer sheet/Graphene composite nano materials with holes and preparation thereof have not been reported.It is raw material that graphene oxide and sulfo-ammonium tungstate are take in the present invention, 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.This preparation WS
2the method of the composite nano materials of nanometer sheet/Graphene 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
2nanometer sheet/Graphene composite nano materials with holes and preparation method thereof, this composite nano materials is by WS
2the compound formation of nanometer sheet with holes and Graphene, described WS
2nanometer sheet with holes is the layer structure of individual layer or few number of plies, described WS
2the ratio of the amount of substance between nanometer sheet with holes and Graphene is 1:1-1:3.
The layer structure of few number of plies refers to that the number of plies is in the layer structure below 6 layers or 6 layers.
WS of the present invention
2the preparation method's of nanometer sheet/Graphene composite nano materials with holes step is as follows:
(1) be dispersed in deionized water graphene oxide is ultrasonic, then add cationic post [5] arene-based supermolecule (its structure is shown in Fig. 1), and fully stir;
(2) Cys and sulfo-ammonium tungstate are added in the mixed system of step (1) successively, 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;
(3) mixed dispersion step (2) 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 ℃ after hydro-thermal reaction 20-24 h, allow it naturally cool to room temperature, with centrifugation, collect solid product, and with deionized water, fully wash vacuumize at 100 ℃; By above-mentioned resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2 h, in mist, the volume fraction of hydrogen is 10%, prepares WS
2the composite nano materials of nanometer sheet/Graphene with holes.
Above-mentioned graphene oxide adopts improved Hummers method preparation.
WS of the present invention
2nanometer sheet/Graphene composite nano materials 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 with the WS of 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, compare 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 adsorbed on graphene oxide surface in mode vertical or that lie low, 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 not only has more active sites edge, can strengthen its electrocatalysis characteristic to evolving hydrogen reaction, and more short lithium ion diffusion admittance can be provided, and has assistant to strengthen its electrochemistry storage lithium performance.WS
2nanometer sheet/graphene composite material with holes can increase the contact area of itself and electrolyte, further contributes to improve its chemical property.Preparation method of the present invention has simply, facilitates and be easy to expand the feature of industrial applications.
Accompanying drawing explanation
The cationic post of Fig. 1 [5] arene-based supermolecule structural representation.
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).
WS prepared by Fig. 4 comparative example
2the SEM shape appearance figure (a) of nanometer sheet/Graphene composite nano materials, TEM photo (b) and HRTEM photo (c).
Embodiment
Below in conjunction with embodiment, further illustrate the present invention.
Graphene oxide in following example adopts improved Hummers method preparation: 0
ounder C ice bath, 10.0 mmol (0.12 g) graphite powder dispersed with stirring, in the 50 mL concentrated sulfuric acids, is slowly added to KMnO under constantly stirring
4, institute adds KMnO
4quality be 4 times of graphite powder, stir 50 minutes, when temperature rises to 35 ℃, slowly add 50 mL deionized waters, then stir 30 minutes, add the H of 15 mL mass fractions 30%
2o
2, stir 30 minutes, through centrifugation, after HCl solution, deionized water and the acetone cyclic washing with mass fraction 5%, obtain graphene oxide successively.
Embodiment 1.
1) be dispersed in 60 mL deionized waters 2.5 mmol graphene oxides are ultrasonic, then add the cationic post of 0.16 mmol [5] arene-based supermolecule, and fully stir;
2) 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 deionized water, adjust volume to approximately 80 mL;
3) resulting mixed liquor is transferred in the hydrothermal reaction kettle of 100 mL, this reactor is put in constant temperature oven, at 230 ℃ after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, with centrifugation, collect solid product, and fully wash with deionized water, vacuumize at 100 ℃, by resulting hydro-thermal solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2h, prepare WS
2the composite nano materials of nanometer sheet/Graphene with holes, in mist, the volume fraction of hydrogen is 10%.
With XRD, SEM and TEM are to the prepared WS that obtains
2the composite nano materials of nanometer sheet/Graphene with holes characterizes.XRD analysis result shows WS in composite nano materials
2the average number of plies be 2 layers of (see figure 2), SEM pattern and transmission electron microscope photo (seeing Fig. 3) have also clearly illustrated respectively WS in composite material
2be the nanometer sheet with micropore, its number of plies is at 1-3 layer, WS
2wS in nanometer sheet/Graphene composite nano materials with holes
2with the ratio of Graphene amount of substance be 1:2.
Comparative example
Adopt DTAB cationic surfactant, by above-mentioned similar approach, prepared WS
2the composite nano materials of nanometer sheet and Graphene, concrete preparation process is as follows:
Be dispersed in 60 mL deionized waters 2.5 mmol graphene oxides are ultrasonic, add again 1.6 mmol DTAB cationic surfactants, and fully stir, then add successively 0.76 g (6.25 mmol) Cys and 1.25 mmol sulfo-ammonium tungstates, and constantly stir Cys and sulfo-ammonium tungstate are dissolved completely, with deionized water, adjust volume to approximately 80 mL, resulting mixed liquor is transferred in the hydrothermal reaction kettle of 100 mL, this reactor is put in constant temperature oven, at 230 ℃ after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, with centrifugation, collect solid product, and fully wash with deionized water, vacuumize at 100 ℃, by resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2 h, in mist, the volume fraction of hydrogen is 10%, prepare WS
2the nano composite material of nanometer sheet/Graphene.
With XRD, SEM and TEM are to finally preparing WS
2the nano composite material of nanometer sheet and Graphene characterizes, and XRD analysis result shows WS in composite nano materials
2for layer structure, the average number of plies is 7 layers.SEM shape appearance figure, TEM photo and HRTEM photo (seeing Fig. 4) have shown the WS loading on Graphene
2for the pattern of nanometer sheet not with holes, the main number of plies is 7 layers
The test of electrocatalytic reaction Hydrogen Evolution Performance is compared: by the WS of the above-mentioned preparation of 4 .0 mg
2nanometer sheet/Graphene composite nano materials with holes (or WS of preparing of comparative example
2nanometer sheet/Graphene composite nano materials) in deionized water-alcohol mixeding liquid body of 1.0 mL (volume ratio 1:1), the Nafion solution (5 wt%) that adds again 30 uL, ultrasonic processing 2 h, make it fully mix and be uniformly dispersed, obtain uniform slurry, the mixed slurry of getting 5 uL with liquid-transfering gun drips on the glassy carbon electrode of diameter 5 mm, after drying at 80 ℃, obtains test job electrode.Electrolyte is the aqueous sulfuric acid of 0.5 M, and reference electrode is saturated calomel electrode, and platinized platinum, as to electrode, is tested the electrocatalysis characteristic of evolving hydrogen reaction with linear potential sweep test material on CHI660B electrochemical workstation, and sweep speed is 5 mV/s.Test result is presented under identical cathodic polarization overpotential, WS
2nanometer sheet/Graphene composite nano materials electrode with holes compares WS
2nanometer sheet/Graphene composite nano materials electrode has higher evolving hydrogen reaction electric current, as: under 0.20 V vs. RHE current potential, at WS
2electrochemical catalysis evolving hydrogen reaction electric current position 16.5 mA on nanometer sheet/Graphene composite nano materials electrode with holes, at WS
2on nanometer sheet/Graphene composite nano materials electrode, evolving hydrogen reaction electric current is 6.5 mA.To the enhancing of evolving hydrogen reaction electrocatalysis characteristic, be due to WS
2wS in nanometer sheet/Graphene composite nano materials with holes
2nanometer sheet with holes compares WS
2wS in nanometer sheet/Graphene composite nano materials
2nanometer sheet has more active sites edge.In addition, WS
2nanometer sheet/Graphene composite nano materials with holes compares WS
2nanometer sheet/Graphene composite nano materials has the area more contacting with electrolyte.
Claims (2)
1. a WS
2the composite nano materials of nanometer sheet/Graphene with holes, is characterized in that, this composite nano materials is by WS
2the compound formation of nanometer sheet with holes and Graphene, described WS
2nanometer sheet with holes is the layer structure of individual layer or few number of plies, described WS
2the ratio of the amount of substance between nanometer sheet with holes and Graphene is 1:1-1:3.
2. WS described in a claim 1
2the preparation method of the composite nano materials of nanometer sheet/Graphene with holes, is characterized in that, described preparation method carries out according to the following steps:
(1) be dispersed in deionized water graphene oxide is ultrasonic, then add cationic post [5] arene-based supermolecule, and fully stir;
(2) then Cys and sulfo-ammonium tungstate are joined successively in the mixed system that step (1) obtains, 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;
(3) mixed dispersion step (2) being obtained is transferred in hydrothermal reaction kettle, and add deionized water to adjust volume to 80% of hydrothermal reaction kettle nominal volume, cationic post [5] arene-based supermolecule molar concentration 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 ℃ after hydro-thermal reaction 20-24 h, allow it naturally cool to room temperature, with centrifugation, collect hydro-thermal reaction solid product, and fully wash with deionized water, vacuumize at 100 ℃, by the hydro-thermal reaction solid product obtaining in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2 h, in mist, the volume fraction of hydrogen is 10%, finally prepare WS
2the composite nano materials of nanometer sheet/Graphene with holes.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104091932A (en) * | 2014-07-17 | 2014-10-08 | 浙江大学 | Porous WS2 nanosheet and graphene composite nanomaterial and preparation method thereof |
| CN104801319A (en) * | 2015-03-21 | 2015-07-29 | 复旦大学 | Hydrogen evolution reaction catalyst nanosheet layer-graphene three-dimensional composite material and preparation method thereof |
| CN110371964A (en) * | 2019-07-17 | 2019-10-25 | 中国科学院金属研究所 | A kind of preparation method of the graphene oxide composite material of nanoscale piece diameter size |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104091932A (en) * | 2014-07-17 | 2014-10-08 | 浙江大学 | Porous WS2 nanosheet and graphene composite nanomaterial and preparation method thereof |
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| CN110371964A (en) * | 2019-07-17 | 2019-10-25 | 中国科学院金属研究所 | A kind of preparation method of the graphene oxide composite material of nanoscale piece diameter size |
| CN110371964B (en) * | 2019-07-17 | 2022-10-11 | 中国科学院金属研究所 | Preparation method of graphene oxide material with nanoscale sheet diameter size |
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