CN106611837A - Cobalt-intercalated molybdenum sulfide secondary battery material and preparation method and application thereof - Google Patents
Cobalt-intercalated molybdenum sulfide secondary battery material and preparation method and application thereof Download PDFInfo
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- 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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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- 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
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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
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to a cobalt-intercalated molybdenum sulfide secondary battery material and a preparation method and an application thereof. A three-dimensional cobalt-intercalated molybdenum sulfide multi-level structure is prepared by adopting a chemical solution method; firstly, a cobalt salt, a molybdenum salt and a sulfur source are dispersed into a solvent to prepare a reaction liquid; and then the prepared reaction liquid is subjected to solvent thermal treatment to obtain the three-dimensional cobalt-uniformly-intercalated molybdenum sulfide multi-level structure which is self-assembled by graphene-like ultra-thin nanosheets, wherein the size of the multi-level structure is about 100nm. The invention also discloses a preparation method for the multi-level structure. The secondary battery material prepared by the method is stable in nanomaterial performance, and long in cycle life when the secondary battery material is used as a negative electrode material of a lithium ion battery and an electrode material of a supercapacitor.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, more particularly, to a kind of cobalt intercalation molybdenum sulfide secondary cell
Material and its preparation method and application.
Background technology
Lithium ion battery (LIBs) and ultracapacitor as advanced energy storage technology representative, either now or
In the future, in portable electric appts power supply, mixed power electric car and aeronautical technology play vital effect.
In view of lithium ion battery possesses, energy density is high, and specific capacity is big, and service life cycle is long, advantages of environment protection,
It is current to be widely used in mobile phone, notebook computer, digital camera and digital video camera products.
And grapheme material, used as most widely used lithium ion battery negative material, its theoretical maximum capacity is 372mAh
g-1, on the electronic device that high power capacity and energy density are required, the current progress of grapheme material is slow.Cause
This, develops high performance lithium ion battery active material, and the development and application to lithium ion battery is most important.
Stratiform transition metal dichalcogenide (M=Mo, Ti, V, and W, X=S or Se), current most study is
The molybdenum bisuphide of class graphene-structured, theoretical capacity (the 670mAh g due to being twice in Graphene-1), and layer
Between weaker Van der Waals force do not produce obvious volumetric expansion beneficial to the diffusion of lithium ion, it is negative in lithium ion battery
Cause highest attention in the investigation of materials of pole.But the molybdenum bisuphide of layer structure causes the heap of lamella during storage lithium
Folded deformation makes electrode material that efflorescence inactivation to occur, and the cyclical stability for ultimately resulting in material is deteriorated.And two sulfur being layered
Change molybdenum can be introduced by strong covalent bond or Intercalation reaction is external metal or alkali metal atom, while pure molybdenum bisuphide
The effect of the weak van der Waals of interlayer, the structure of " sandwich " type for formation being capable of effectively padded coaming
The volume deformation caused during storage lithium and raising battery capacity.Therefore, stratiform transition metal molybdenum bisuphide conduct
Negative material obtains the concern of people.Such as molybdenum bisuphide, (Graphene, 3D Graphene networks, carbon is received with other materials
Mitron, Fe3O4Nano-particle, TiO2Nanotube, carbon fiber etc.) it is compound.
In recent years, in design synthesis height ratio capacity, high magnification row, the new MoS of stability2The nanometer of/C bases is answered
Condensation material obtains major progress.For example, Weixiang Chen et al. reports is steady with height ratio capacity and good circulation
Fixed MoS2/ amorphous carbon complex, it is in 100mA g-1When capacitance reach 962mA h g-1,
And capacity remains at 912mA h g after 100 circle circulations-1.Capacitance and cyclical stability are in MoS2
All improved well after compound.Chunzhong Li et al. reports design recently has been synthesized and has been synthesized by three steps
Its interlamellar spacing has 0.98nm, a 2D MoS of new " sanwich " structure2/ mesoporous carbon complex,
Outstanding forthright again and cyclical stability (500cycles) is shown.And at present transition metal (manganese, ferrum, nickel,
Cobalt etc.) doping molybdenum bisuphide material be mainly used in catalytic field, the especially hydrodesulfurization in petroleum refining industry
(HDS), hydrodenitrogeneration (HDN) and the field such as the catalysis oxidation to sulphion in waste water and electro-catalysis hydrogen manufacturing.
Applications of such as Dungey K.E. to the edge of molybdenum bisuphide composite, heat stability and as catalyst is entered
Go a series of researchs, find Co2+、Co3+Or Fe3+Addition molybdenum bisuphide can be made to expect hydrodesulfurization for thiophene
The reactivity of catalyst is greatly improved.Cui etc. is designed on the basis of calculating simulation and is used chemical gaseous phase
The MoS of different transition metal atoms (Fe, Co, Ni, the Cu) doping that sedimentation is obtained2Add with preferable electro-catalysis
Hydrogen performance, the MoS of its vertical basal plane2Sulfur side metal atom doped rear exchange current density improve twice with
On, electrocatalytic hydrogenation performance is significantly improved.But transient metal doped material molybdenum sulfide is all displacement replaces sulfuration
Molybdenum on molybdenum layer, and it prepares transient metal doped MoS2Method more use physical vapor synthetic method
And chemical gas phase synthetic method, these methods often require that higher system temperature, loaded down with trivial details preparation process, accurate
Instrument, and product morphology is difficult to control to, and yield is few, limits it and applies in energy storage as electrode material.Cause
This, unique " sandwich " structure of design synthesis and with the class Material cladding of Graphene one, and on this basis can
It is extended to the nano material compound with transition metal and is applied to the energy storage devices such as lithium ion battery and ultracapacitor
On urgently can not treat.
The content of the invention
The purpose of the present invention is exactly the defect in order to overcome above-mentioned prior art to exist and provides a kind of long-life and height
Cobalt intercalation molybdenum sulfide secondary battery material of high rate performance and its preparation method and application.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of cobalt intercalation molybdenum sulfide secondary battery material, is three-dimensional multistage structure that nanometer sheet is assembled into, in two-layer two
The sulfide atomic layer of cobalt is inserted between molybdenum sulfide atomic layer substrate, the interlamellar spacing of two-layer molybdenum bisuphide atomic layer is
0.67-1.5nm, preferably 1.07nm, more than molybdenum bisuphide interlamellar spacing 0.615nm of standard, cobalt and molybdenum mole
Than less than 1.
The material of atomic layer substrate can also adopt tungsten disulfide, stannic disulfide, two selenizing molybdenums, two tungsten selenides or two
One or two in Tin diselenide.,
Metallic cobalt can also adopt one or more in manganese, nickel, ferrum or copper.
The preparation method of cobalt intercalation molybdenum sulfide secondary battery material, using following steps：
1) cobalt salt, molybdenum salt, sulphur source are added in alcoholic solvent, are configured to reactant liquor；The concentration of wherein cobalt salt is
0.0025～0.025moll-1, cobalt salt and molybdenum salt mol ratio be 4～16 less than the mol ratio of 1, sulphur source and molybdenum salt；
2) reactant liquor is moved into into the autoclave with polytetrafluoroethylliner liner, at 160-250 DEG C of solvent thermal
After 24～72h of reason, during the course of the reaction using the pre- intercalation and complexing of solvent so that metal ion is easy to embedding
Enter and be stable in the presence of MoS2Between, product is separated after natural cooling, respectively with dehydrated alcohol and water washing number
It is secondary, obtain cobalt intercalation material molybdenum sulfide after being dried.
Preferably, step 1) in cobalt salt concentration be 0.01～0.02moll-1, cobalt salt is with the mol ratio of molybdenum salt
0.1～0.8, sulphur source is 4～12 with the mol ratio of molybdenum salt；Step 2) in solvent heat treatment temperature be 180～220 DEG C,
Time is 24～48h.
It is further preferred that step 1) in cobalt salt concentration be 0.0125moll-1, cobalt salt is with the mol ratio of molybdenum salt
0.5, sulphur source is 4 with the mol ratio of molybdenum salt；Step 2) in solvent heat treatment temperature be 200 DEG C, the time is 24h.
Preferably, cobalt salt is in cobaltous acetate, cobaltous chloride, cobaltous sulfate, cobalt nitrate, cobalt carbonate or acetylacetone cobalt
It is at least one；Molybdenum salt is sodium molybdate, ammonium molybdate, acetyl acetone, potassium molybdate, magnesium molybdate, lithium molybdate or seven molybdenums
At least one in sour ammonium；Sulphur source is Sublimed Sulfur, cysteine, Carbon bisulfide, thioacetamide or dithioglycol
In at least one；Alcoholic solvent is ethylene glycol, diethylene glycol, methanol, ethanol, isopropanol, glycerol or different
At least one in butanol.
Preferably, step 1) in also add dressing agent, dressing agent is 0～12 with the mol ratio of cobalt salt, preferably
0.001～1, more preferably 0.001～0.5.The dressing agent for adopting is surfactant or the activity of increase conductivity
Agent.
It is further preferred that dressing agent selected from ethylenediaminetetraacetic acid and its salt, citric acid and its salt, tartaric acid and its salt,
Malic acid and its salt, sulfosalicylic acid and its salt, polyvinylpyrrolidone, Polyethylene Glycol, P123, F127,
Cetyl trimethylammonium bromide, dodecylbenzene sodium sulfonate, dodecyl sodium sulfate, sodium lauryl sulphate,
At least one in enuatrol, oleyl amine, cetylamine or poly- (3,4- Ethylenedioxy Thiophenes)-poly- (styrene sulfonic acid).
The material is in lithium ion battery and lithium ion super capacitor or sodium-ion battery and sodium ion ultracapacitor
It is middle as negative pole lithium storage materials application, it can in addition contain in aqueouss capacitor as electrode material application.
Compared with prior art, the present invention can occur for stratiform transition metal molybdenum bisuphide in charge and discharge process
Fold or stacking cause the shortcoming that cycle performance is deteriorated, and we introduce new " sandwich " structure, make transition
Metallic cobalt inserts the interlayer of layer structure, produces " support " and two kinds of action effects of bimetallic " collaboration " reach resistance
Only in charge and discharge process the stacking of structure and improve specific capacity purpose.Pre- intercalation and complexation of the present invention using solvent
Effect so that metal ion is easy to embedded and is stable in the presence of MoS2Between, by the simple solvent heat seal of a step
Synthesize the MoS of the cobalt intercalation of the thin slice assembling of three-dimensional into process2Multilevel hierarchy, cobalt intercalation improves in the material
The electric conductivity of material, the size of multilevel hierarchy is solved in 100nm or so, bigger serface and meso-hole structure fills
Volumetric expansion before and after electric discharge, and three dimensional structure shorten lithium ion the evolving path and store electrolyte beneficial to lithium from
Son diffusion, therefore synthesized material has good cyclical stability and high rate performance.While the method process is simple,
Processing cost is low, is adapted to industrialized production, with advantages below：
(1) as a result of the environmental friendliness system of surfactant-free, due to the intercalation of cobalt element so that three
The molybdenum sulfide multilevel hierarchy of the cobalt intercalation of dimension forms " sanwich " structure during growth, to by ultrathin nanometer
The multilevel hierarchy of piece assembling serves preferable supporting role, it is therefore prevented that the reunion of nanometer sheet and stacking, is allowed to have
The three-dimensional stability structure of two dimension assembling.
(2) due to present invention employs chemical solution method reaction, raw material is cheap, simple to operate, low cost, effect
Rate is high, it is easy to further commercial production.The molybdenum sulfide multilevel hierarchy of the cobalt intercalation of preparation is three-dimensional flower-shaped, its chi
Very little size is about 100 nanometers, and multilevel hierarchy is the three-dimensional flower-shaped stable knot being self-assembly of by ultrathin nanometer piece
Structure.
Description of the drawings
Fig. 1 is the thing phase composition collection of illustrative plates of the molybdenum sulfide of the multilevel hierarchy cobalt intercalation of the gained of embodiment 1.
Fig. 2 is the stereoscan photograph of the molybdenum sulfide of the multilevel hierarchy cobalt intercalation of the gained of embodiment 1.
Fig. 3 shines for the transmission electron microscope of the different amplification of the molybdenum sulfide of the gained multilevel hierarchy cobalt intercalation of embodiment 1
Piece.
Fig. 4 is the high-resolution-ration transmission electric-lens photo of the molybdenum sulfide of the gained multilevel hierarchy cobalt intercalation of embodiment 1.
Fig. 5 is the x-ray photoelectron energy spectrum diagram of the molybdenum sulfide of the gained multilevel hierarchy cobalt intercalation of embodiment 1, wherein
A () is the full spectrogram of material, (b) be the High Resolution Spectrum of molybdenum, (c) be S High Resolution Spectrum.
Fig. 6 is the high-resolution-ration transmission electric-lens Surface scan photo of the molybdenum sulfide of the gained multilevel hierarchy cobalt intercalation of embodiment 1.
Fig. 7 is the electricity of the molybdenum sulfide as lithium ion battery negative material of the gained multilevel hierarchy cobalt intercalation of embodiment 1
Chemical property figure, (a) cyclic voltammetry, (b) constant current charge-discharge test, (c) 200mA h g-1Follow
Ring test, (d) 500mA h g-1Long-life loop test
Fig. 8 is the electricity of the molybdenum sulfide as electrode material for super capacitor of the gained multilevel hierarchy cobalt intercalation of embodiment 1
Chemical property figure, (a) constant current charge-discharge test, (b) the long-life loop test of 10A/g.
Fig. 9 is the stereoscan photograph of the molybdenum sulfide of the gained of embodiment 2.
Figure 10 is the stereoscan photograph of the molybdenum sulfide of the gained of embodiment 3.
Figure 11 is the stereoscan photograph of the molybdenum sulfide of the gained of embodiment 4.
Figure 12 is the stereoscan photograph of the molybdenum sulfide of the gained of embodiment 5.
Specific embodiment
Embodiment of the present invention is further described below in conjunction with accompanying drawing：Following examples are with technical solution of the present invention
Premised under implemented, give detailed embodiment and specific operation process, but protection scope of the present invention
It is not limited to the above embodiments.
Battery is assembled：Using the electrochemical lithium storage performance of CR2016 type button cell test materials.In mass ratio
Weigh 75% electrode active material, 15% acetylene black and 15% polyacrylic acid (PAA) binding agent (0.05g
mL-1Aqueous solution), it is placed in small beaker and mixes 8h, obtain the electrode slurry of mix homogeneously.Slurry is equal
It is even to coat on Copper Foil, and dry in 60-80 DEG C of hollow baking oven, dried pole piece Jing tablettings, punching,
The disk of a diameter of 12mm is made, by electrode slice 80℃Precision balance is adopted after lower vacuum drying 6h
(0.01mg) weigh.The blank Copper Foil of same area is beaten after piece and is weighed, the 70% of difference is each electrode
Active substance quality on piece.Electrode slice after drying is weighed is immediately transferred to the glove full of argon atmosphere
Case (that (China) company limited of Super 1220/750, meter Kai Luo, oxygen<5ppm, water<Assembling in 1ppm)
Battery, metal lithium sheet is used as to electrode, 1M LiPF4EC:DMC(1:1) and the FEC of mass fraction 10% is added
Used as electrolyte, Celgard2300 is barrier film, and foaming nickel sheet makes CR2016 types button electricity as implant
Pond.
Charge-discharge test：Charge-discharge test is carried out on LAND battery test systems (CT2001A), is arranged
For the form of constant current charge-discharge, for setting value, charging/discharging voltage scope is set to 0.001-3.0 to the electric current density for adopting
V。
Embodiment 1
(1) in the flask of a 100ml, by the cobaltous acetate of 0.5mmol, the sodium molybdate of 1.0mmol, 4
The Sublimed Sulfur of mmol is added in the ethylene glycol of 40ml, strong agitation and is kept for 1 hour under room temperature, it is prepared into
The reactant liquor of multilevel hierarchy.
(2) high pressure that the reactant liquor that will be prepared according to step (1) is moved into 50ml polytetrafluoroethylliner liners is anti-
In answering kettle, after reacting 24 hours at 200 DEG C, reactor naturally cools to 20 DEG C, after centrifugation, is used with this
Dehydrated alcohol and water washing for several times, lyophilization, you can obtain the molybdenum sulfide multilevel hierarchy of three-dimensional cobalt intercalation.
X-ray diffractogram such as Fig. 1 of the molybdenum sulfide multilevel hierarchy of resulting three-dimensional cobalt intercalation.Institute as seen from the figure
The material of preparation is the MoS of hexagonal structure2.Fig. 2 is the molybdenum sulfide multilevel hierarchy scanning of the cobalt intercalation for obtaining three-dimensional
Electron microscopic picture, as seen from the figure prepared material is multilevel hierarchy nanosphere.Fig. 3 is the cobalt of the difference three-dimensional of gained
The transmission electron microscope picture of the different amplification of the molybdenum sulfide of intercalation.From Fig. 3 a, the three-dimensional cobalt intercalation
Molybdenum sulfide multilevel hierarchy size is about 100nm, it is possible to interior on a large scale to find out that nanosphere has ultrathin nanometer piece from group
Dress forms three-dimensional multilevel hierarchy, illustrate the method can synthesize on a large scale three-dimensional cobalt intercalation molybdenum sulfide it is multistage
Structure.The molybdenum sulfide of the three-dimensional cobalt intercalation of gained is can be seen that from transmission electron microscope photo Fig. 4 of bigger amplification
Multilevel hierarchy is the nanometer sheet being made up of less than 10 layers of molybdenum sulfide layer structure, and especially its interlamellar spacing size is
0.68nm and 1.08nm, is distributed with the layer structure that interlamellar spacing expands, and itself and XRD test results one
Cause.Fig. 5 is x-ray photoelectron power spectrum, and a is the full spectrogram of material, demonstrates prepared material by figure and mainly contains
There are cobalt, molybdenum and sulfur.Fig. 5 b and c are the material molybdenum sulfides for contrasting the molybdenum sulfide and commodity synthesized on similarity condition
Molybdenum 3d peaks and sulfur 2p peaks, the material molybdenum sulfide of cobalt doped offsets to low electronic energy, and this mixes with cobalt of Cui's report
The peak phenomenon of miscellaneous molybdenum sulfide (cobalt is substituted in the layer top edge of molybdenum sulfide) is different, is eliminated on the layer of cobalt
Position, while XPS test results show that cobalt is present with the sulphided form of Co, also turned out cobalt be with
The weak bonding form of Co-S is inserted into the interlayer of molybdenum sulfide.Fig. 6 is the mapping figures of TEM-EDS, it is seen that
Element contained by prepared material is cobalt, molybdenum and sulfur, and cobalt atom is uniformly dispersed in material, illustrates that cobalt is equal
Even intercalation is wherein.Obtain made by ICP-AES (ICP) test result
The atom content ratio of standby material cobalt, molybdenum and sulfur three is 0.415:0.719：2, meet MoS2Stoichiometric proportion.
The chemical property of the sample of embodiment 1 is presented in Fig. 7.Cyclic voltammetry curve from a can be seen that embodiment
The electrochemical behavior of 1 sample is typical molybdenum sulfide electrochemical lithium storage mechanism.B can be obvious for charging and discharging curve figure
Ground observe charging and discharging curve be with the cyclic voltammogram of a it is corresponding, the initial discharge capacity of the sample of embodiment 1 with
Charging capacity is respectively 1246 and 928mAh g-1, first coulombic efficiency is 74% or so.The cycle performance figure of c
In can see that the stability of the sample of embodiment 1 very well, after 200 circle discharge and recharges, still maintains 99%
Possible capacity (discharging relative to second), and the sample of embodiment 2 and embodiment 3 is decayed to soon
Less than 50%.D is the cycle performance figure under high magnification 500mA/g, and the stability of the sample of embodiment 1 is substantially fine,
After 1000 circle circulations, there is no apparent change in charge/discharge capacity, and as electrode material
Apply on ultracapacitor, as shown in a of Fig. 8, in 0.5A/g constant current charge-discharges, specific capacity is up to
453.5F/g, and under the electric current density of 10A/g, charge and discharge cycles 25000 are enclosed, and capacity is not decayed substantially
(b of Fig. 8), illustrates that the sample of embodiment 2 is with long-life good nano material.Additionally as sodium from
During sub- cell negative electrode material, voltage range is 0.4V-3V, and under 500mA/g, after the circle of circulation 65, capacity does not have substantially
Change, remain at the specific capacity of 200mAh/g.
Embodiment 2
(1) in the flask of a 100ml, the Sublimed Sulfur of the sodium molybdate of 1.5mmol, 4mmol is added
To in the ethylene glycol of 40ml, strong agitation and kept for 1 hour under room temperature, it is prepared into the reactant liquor of multilevel hierarchy.
(2) high pressure that the reactant liquor that will be prepared according to step (1) is moved into 50ml polytetrafluoroethylliner liners is anti-
In answering kettle, after reacting 24 hours at 200 DEG C, reactor naturally cools to 20 DEG C, after centrifugation, is used with this
Dehydrated alcohol and water washing for several times, lyophilization, you can obtain molybdenum sulfide nanoparticles.Fig. 9 is the sulfuration of gained
The stereoscan photograph of molybdenum.
Embodiment 3
(1) in the flask of a 100ml, the Sublimed Sulfur of the cobaltous acetate of 1.5mmol, 4mmol is added
Enter in the ethylene glycol of 40ml, strong agitation and kept for 1 hour under room temperature, it is prepared into the anti-of multilevel hierarchy
Answer liquid.
(2) reactant liquor that will be prepared according to step (1) moves into the high pressure with 50ml polytetrafluoroethylliner liners
In reactor, after reacting 24 hours at 200 DEG C, reactor naturally cools to 20 DEG C, after centrifugation, with
This uses dehydrated alcohol and water washing for several times, lyophilization, you can obtain the molybdenum sulfide similar to three-dimensional cobalt intercalation
Multilevel hierarchy.Figure 10 is resulting CoS2The stereoscan photograph of nano material.
Embodiment 4
(1) in the flask of a 100ml, by the cobaltous acetate of 0.5mmol, the sodium molybdate of 1.0mmol,
The Sublimed Sulfur of 4mmol is added in the ethylene glycol of 40ml, strong agitation and is kept for 1 hour under room temperature, is prepared
Into the reactant liquor of material.
(2) reactant liquor that will be prepared according to step (1) moves into the high pressure with 50ml polytetrafluoroethylliner liners
In reactor, after reacting 36 hours at 200 DEG C, reactor naturally cools to 20 DEG C, after centrifugation, with
This uses dehydrated alcohol and water washing for several times, lyophilization, you can obtain product.Figure 11 is prepared material
Stereoscan photograph.
Embodiment 5
(1) in the flask of a 100ml, by the cobaltous acetate of 0.5mmol, the sodium molybdate of 1.0mmol, 4
The Sublimed Sulfur of mmol is added in the ethylene glycol of 40ml, strong agitation and is kept for 1 hour under room temperature, is prepared into
The reactant liquor of material.
(2) high pressure that the reactant liquor that will be prepared according to step (1) is moved into 50ml polytetrafluoroethylliner liners is anti-
In answering kettle, after reacting 48 hours at 200 DEG C, reactor naturally cools to 20 DEG C, after centrifugation, is used with this
Dehydrated alcohol and water washing for several times, lyophilization, you can obtain product.Figure 12 is the scanning electricity of prepared material
Mirror photo.
Embodiment 6
(1) in the flask of a 100ml, by the cobaltous acetate of 0.5mmol, the sodium molybdate of 1.0mmol, 4
The Sublimed Sulfur of mmol is added in the ethylene glycol of 40ml, strong agitation and is kept for 1 hour under room temperature, is prepared into
The reactant liquor of material.
(2) high pressure that the reactant liquor that will be prepared according to step (1) is moved into 50ml polytetrafluoroethylliner liners is anti-
In answering kettle, after reacting 72 hours at 200 DEG C, reactor naturally cools to 20 DEG C, after centrifugation, is used with this
Dehydrated alcohol and water washing for several times, lyophilization, you can obtain product.
Embodiment 7
A kind of cobalt intercalation molybdenum sulfide secondary battery material, is three-dimensional multistage structure that nanometer sheet is assembled into, in two-layer two
The sulfide atomic layer of cobalt is inserted between molybdenum sulfide atomic layer substrate, the interlamellar spacing of two-layer molybdenum bisuphide atomic layer is
0.67nm, more than molybdenum bisuphide interlamellar spacing 0.615nm of standard, cobalt is less than 1 with the mol ratio of molybdenum.
The preparation method of cobalt intercalation molybdenum sulfide secondary battery material, using following steps：
1) cobalt salt, molybdenum salt, sulphur source are added in alcoholic solvent, are configured to reactant liquor；The concentration of wherein cobalt salt is
0.0025mol·l-1, cobalt salt and molybdenum salt mol ratio be the mol ratio of 0.95, sulphur source and molybdenum salt be 4, the cobalt for using
Salt is cobaltous acetate, and molybdenum salt is sodium molybdate, and sulphur source is Sublimed Sulfur, and alcoholic solvent is ethylene glycol；
2) reactant liquor is moved into into the autoclave with polytetrafluoroethylliner liner, in 160 DEG C of solvent heat treatments 72h
Afterwards, during the course of the reaction using the pre- intercalation and complexing of solvent so that metal ion is easy to embedded and stably deposits
It is MoS2Between, product is separated after natural cooling, respectively with dehydrated alcohol and water washing for several times, after being dried
Obtain cobalt intercalation material molybdenum sulfide.
Prepare can with material lithium ion battery and lithium ion super capacitor or sodium-ion battery and sodium from
As negative pole lithium storage materials application in sub- ultracapacitor, it can in addition contain in aqueouss capacitor as electrode material
Using.
Embodiment 8
A kind of cobalt intercalation molybdenum sulfide secondary battery material, is three-dimensional multistage structure that nanometer sheet is assembled into, in two-layer two
The sulfide atomic layer of cobalt is inserted between molybdenum sulfide atomic layer substrate, the interlamellar spacing of two-layer molybdenum bisuphide atomic layer is
1.07nm, more than molybdenum bisuphide interlamellar spacing 0.615nm of standard, cobalt is less than 1 with the mol ratio of molybdenum.
The preparation method of cobalt intercalation molybdenum sulfide secondary battery material, using following steps：
1) cobalt salt, molybdenum salt, sulphur source are added in alcoholic solvent, are configured to reactant liquor；The concentration of wherein cobalt salt is
0.0125mol·l-1, cobalt salt and molybdenum salt mol ratio be the mol ratio of 0.1, sulphur source and molybdenum salt be 6, the cobalt salt for using
For cobaltous acetate, molybdenum salt is ammonium molybdate, and sulphur source is Sublimed Sulfur, and alcoholic solvent is diethylene glycol, in addition, is also added
Plus dressing agent ethylenediaminetetraacetic acid, dressing agent is 0.001 with the mol ratio of cobalt salt；
2) reactant liquor is moved into into the autoclave with polytetrafluoroethylliner liner, in 180 DEG C of solvent heat treatments 48h
Afterwards, during the course of the reaction using the pre- intercalation and complexing of solvent so that metal ion is easy to embedded and stably deposits
It is MoS2Between, product is separated after natural cooling, respectively with dehydrated alcohol and water washing for several times, after being dried
Obtain cobalt intercalation material molybdenum sulfide.
The material for preparing can lithium ion battery and lithium ion super capacitor or sodium-ion battery and sodium from
As negative pole lithium storage materials application in sub- ultracapacitor, it can in addition contain in aqueouss capacitor as electrode material
Using.
Embodiment 9
A kind of cobalt intercalation molybdenum sulfide secondary battery material, is three-dimensional multistage structure that nanometer sheet is assembled into, in two-layer two
The sulfide atomic layer of cobalt is inserted between molybdenum sulfide atomic layer substrate, the interlamellar spacing of two-layer molybdenum bisuphide atomic layer is
1.07nm, more than molybdenum bisuphide interlamellar spacing 0.615nm of standard, cobalt is less than 1 with the mol ratio of molybdenum.
The preparation method of cobalt intercalation molybdenum sulfide secondary battery material, using following steps：
1) cobalt salt, molybdenum salt, sulphur source are added in alcoholic solvent, are configured to reactant liquor；The concentration of wherein cobalt salt is
0.02mol·l-1, cobalt salt and molybdenum salt mol ratio be the mol ratio of 0.8, sulphur source and molybdenum salt be 12, the cobalt salt for using
For cobaltous sulfate and the mixture of cobalt carbonate, molybdenum salt is the mixture of potassium molybdate and lithium molybdate, and sulphur source is dithioglycol,
Alcoholic solvent is methanol, the mixture of ethanol, and dodecylbenzene sodium sulfonate is also added in addition as dressing agent, modification
Agent is 0.5 with the mol ratio of cobalt salt；
2) reactant liquor is moved into into the autoclave with polytetrafluoroethylliner liner, in 200 DEG C of solvent heat treatments 24h
Afterwards, during the course of the reaction using the pre- intercalation and complexing of solvent so that metal ion is easy to embedded and stably deposits
It is MoS2Between, product is separated after natural cooling, respectively with dehydrated alcohol and water washing for several times, after being dried
Obtain cobalt intercalation material molybdenum sulfide.
The material for preparing can lithium ion battery and lithium ion super capacitor or sodium-ion battery and sodium from
As negative pole lithium storage materials application in sub- ultracapacitor, it can in addition contain in aqueouss capacitor as electrode material
Using.
Embodiment 10
A kind of cobalt intercalation molybdenum sulfide secondary battery material, is three-dimensional multistage structure that nanometer sheet is assembled into, in two-layer two
The sulfide atomic layer of cobalt is inserted between molybdenum sulfide atomic layer substrate, the interlamellar spacing of two-layer molybdenum bisuphide atomic layer is
1.5nm, more than molybdenum bisuphide interlamellar spacing 0.615nm of standard, cobalt is less than 1 with the mol ratio of molybdenum.
The preparation method of cobalt intercalation molybdenum sulfide secondary battery material, using following steps：
1) cobalt salt, molybdenum salt, sulphur source are added in alcoholic solvent, are configured to reactant liquor；The concentration of wherein cobalt salt is
0.025mol·l-1, cobalt salt and molybdenum salt mol ratio be the mol ratio of 0.5, sulphur source and molybdenum salt be 16, cobalt salt is nitric acid
Cobalt, molybdenum salt is ammonium heptamolybdate, and sulphur source is dithioglycol, and alcoholic solvent is isobutanol, in addition, being also added into cetylamine
Used as dressing agent, dressing agent is 12 with the mol ratio of cobalt salt；
2) reactant liquor is moved into into the autoclave with polytetrafluoroethylliner liner, in 250 DEG C of solvent heat treatments 24h
Afterwards, during the course of the reaction using the pre- intercalation and complexing of solvent so that metal ion is easy to embedded and stably deposits
It is MoS2Between, product is separated after natural cooling, respectively with dehydrated alcohol and water washing for several times, after being dried
Obtain cobalt intercalation material molybdenum sulfide.
The material for preparing can lithium ion battery and lithium ion super capacitor or sodium-ion battery and sodium from
As negative pole lithium storage materials application in sub- ultracapacitor, it can in addition contain in aqueouss capacitor as electrode material
Using.
Claims (10)
1. a kind of cobalt intercalation molybdenum sulfide secondary battery material, it is characterised in that what the material was assembled into for nanometer sheet
Three-dimensional multistage structure, inserts the sulfide atomic layer of cobalt, the sulfur of two-layer two between two-layer molybdenum bisuphide atomic layer substrate
The interlamellar spacing for changing molybdenum atom layer is 0.62-1.50nm, and cobalt is less than 1 with the mol ratio of molybdenum.
2. a kind of cobalt intercalation molybdenum sulfide secondary battery material according to claim 1, it is characterised in that
The interlamellar spacing of two-layer molybdenum bisuphide atomic layer is 1.07nm,
The material of atomic layer substrate can also adopt tungsten disulfide, stannic disulfide, two selenizing molybdenums, two tungsten selenides or two
One or two in Tin diselenide.,
Metallic cobalt can also adopt one or more in manganese, nickel, ferrum or copper.
3. the preparation method of cobalt intercalation molybdenum sulfide secondary battery material as claimed in claim 1, it is characterised in that
The method adopts following steps：
1) cobalt salt, molybdenum salt, sulphur source are added in alcoholic solvent, are configured to reactant liquor；The concentration of wherein cobalt salt is
0.0025～0.025moll-1, cobalt salt and molybdenum salt mol ratio be 4～16 less than the mol ratio of 1, sulphur source and molybdenum salt；
2) reactant liquor is moved into into the autoclave with polytetrafluoroethylliner liner, at 160-250 DEG C of solvent thermal
After 24～72h of reason, product is separated after natural cooling, respectively with dehydrated alcohol and water washing for several times, after being dried i.e.
Obtain cobalt intercalation material molybdenum sulfide.
4. the preparation method of a kind of cobalt intercalation molybdenum sulfide secondary battery material according to claim 3, it is special
Levy and be,
Step 1) in cobalt salt concentration be 0.01～0.02moll-1, be preferably 0.0125moll-1, cobalt salt and molybdenum salt
Mol ratio is 0.1～0.8, is preferably 0.5, the mol ratio of sulphur source and molybdenum salt is 4～12, is preferably 4；
Step 2) in solvent heat treatment temperature be 180～220 DEG C, be preferably 200 DEG C, the time be 24～48h,
Preferably 24h.
5. the preparation method of a kind of cobalt intercalation molybdenum sulfide secondary battery material according to claim 3, it is special
Levy and be,
Described cobalt salt be cobaltous acetate, cobaltous chloride, cobaltous sulfate, cobalt nitrate, cobalt carbonate or acetylacetone cobalt in extremely
Few one kind；
Described molybdenum salt is sodium molybdate, ammonium molybdate, acetyl acetone, potassium molybdate, magnesium molybdate, lithium molybdate or seven molybdenums
At least one in sour ammonium；
Described sulphur source is Sublimed Sulfur, in cysteine, Carbon bisulfide, thioacetamide or dithioglycol at least
It is a kind of；
Described alcoholic solvent is ethylene glycol, diethylene glycol, methanol, ethanol, isopropanol, glycerol or isobutanol
In at least one, preferred ethylene glycol.
6. the preparation method of a kind of cobalt intercalation molybdenum sulfide secondary battery material according to claim 3, it is special
Levy and be, step 1) in also add dressing agent, dressing agent is 0～12 with the mol ratio of cobalt salt.
7. the preparation method of a kind of cobalt intercalation molybdenum sulfide secondary battery material according to claim 6, it is special
Levy and be, the activating agent that described dressing agent is surfactant or increases conductivity.
8. the preparation method of a kind of cobalt intercalation molybdenum sulfide secondary battery material according to claim 6 or 7,
Characterized in that, described dressing agent selected from ethylenediaminetetraacetic acid and its salt, citric acid and its salt, tartaric acid and its
Salt, malic acid and its salt, sulfosalicylic acid and its salt, polyvinylpyrrolidone, Polyethylene Glycol, P123, F127,
Cetyl trimethylammonium bromide, dodecylbenzene sodium sulfonate, dodecyl sodium sulfate, sodium lauryl sulphate,
At least one in enuatrol, oleyl amine, cetylamine or poly- (3,4- Ethylenedioxy Thiophenes)-poly- (styrene sulfonic acid).
9. the application of cobalt intercalation molybdenum sulfide secondary battery material as claimed in claim 1, it is characterised in that should
Material conduct in lithium ion battery and lithium ion super capacitor or sodium-ion battery and sodium ion ultracapacitor
Negative pole lithium storage materials application.
10. the application of cobalt intercalation molybdenum sulfide secondary battery material as claimed in claim 1, it is characterised in that should
Material is in aqueouss capacitor as electrode material application.
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