CN107170974A - A kind of carbon coating MoSe2/ graphene electro spinning nano fiber and preparation method thereof - Google Patents
A kind of carbon coating MoSe2/ graphene electro spinning nano fiber and preparation method thereof Download PDFInfo
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- CN107170974A CN107170974A CN201710386691.7A CN201710386691A CN107170974A CN 107170974 A CN107170974 A CN 107170974A CN 201710386691 A CN201710386691 A CN 201710386691A CN 107170974 A CN107170974 A CN 107170974A
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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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- 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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
Carbon coating MoSe is prepared the present invention relates to a kind of electrostatic spinning2/ graphene nano fiber and preparation method thereof.The nanofiber is by carbon coated, MoSe2, graphene composition.Its preparation method is：Water-soluble molybdenum salt and high polymer are dissolved in deionized water and ethylene glycol mixed solution, graphene is added molybdenum salting liquid formation electrospun solution by heating until forming stable transparent colloidal sol；Electrostatic spinning is carried out to gained electrospun solution, hybridized fiber is obtained；Then at 500 800 DEG C, hybridized fiber obtained by step 2 and zeroth order selenium powder is subjected to vacuum-sintering in tube furnace, carbon coating MoSe is obtained2/ graphene nano fiber material.Fiber morphology and length are uniform, MoSe2Crystal is evenly distributed in fiber, is coated by agraphitic carbon；Graphene is uniformly distributed in fiber as conductive network.Raw material of the present invention is easy to get, and preparation technology is simple, controllable reaction mild condition, and gained finished product has higher specific surface area, and excellent electric conductivity and structural stability can be used as a kind of preferable lithium/anode material of lithium-ion battery and high-performance electric catalysis material.
Description
Technical field
The present invention relates to field of nanometer material technology, and in particular to a kind of electrostatic spinning prepares carbon coating MoSe2/ graphene nano
Fiber and preparation method thereof.
Background technology
The current whole world is faced with from global warming, and the serious pressure that energy crisis is brought, rechargeable battery is used as fossil
The alternative energy source storage device of fuel has attracted huge notice, such as lithium ion battery and sodium-ion battery.Although lithium ion
Battery has been achieved for commercial success, but the scarcity of elemental lithium and its high cost are difficult to the demand that meets future development.
Because the content of sodium in the earth's crust is high, the low and similar working mechanism of cost is considered as follow-on rechargeable battery.However, more
Big sodium ion radius Na+With Li+(0.102vs 0.076nm) may result in big Volumetric expansion and poor power
Performance is learned, causes the stable circulation and high rate performance of sode cell undesirable.
The Transition-metal dichalcogenide of stratiform is due to its unique physicochemical properties and novel structure, by people
Extensive concern and further investigation.Wherein MoSe2Material is a kind of typical transition metal selenides, and class graphene-structured has
Very big interlamellar spacing, can promote Na+Quick insertion and deintercalation, obtain storing up sodium performance well.It is right both at home and abroad at present
MoSe2There is a little research as sode cell negative material.HeFei University of Technology college of materials science and engineering Yang
Jiang seminars draw MoSe by theoretical calculation2The theoretical discharge specific capacity of material is 422.28mAh g-1, have in theory
Sodium performance is stored up well.MoSe is prepared by thermal decomposition process2Nanometer sheet, voltage range 0.1C of the electrode material in 0.1-3V
Current density under initial discharge specific capacity reach 513mAh g-1, but have poor cyclical stability.Korea University of South Korea
College of materials science and engineering Yun Chan Kang et al. are to MoO3The MoSe of core shell structure is prepared in the direct selenizing of microballoon2It is micro-
Ball, by many thin layer MoSe2Nanometer sheet aggregation is formed, with abundant space and specific surface area.Electrode material is in 0.001-3V
Voltage range 0.2A g-1Current density under initial discharge specific capacity reach 527mAh g-1, maintained after 50 circle circulations
433mAh g-1Capacity (capability retention is only 82.163%).Central South University's metallurgy and Environmental Studies Institute Zhian Zhang team
MoSe is prepared for using hydro-thermal method2/ rGO composites, MoSe2Growth is fixed on redox graphene (rGO) lamella.West
Pacify university of communications material behavior National Key Laboratory Yaping Du team by solvent structure MoSe2Length exists
Composite on carbon cloth.MoSe2Nanometer sheet thickness 20nm, is uniformly grown in carbon cloth surfaces.In 0.2A g-1Current density
Under, maintain 452.6mAh g after 100 circle circulations-1Capacity, capability retention is 85.5%.Dalian University of Technology's chemical engineering science
Zongbin Zhao seminars of institute pass through the acid-functionalized MoSe of the first artificial oil of solvent-thermal method2Material, adds dopamine, at it
Carbon intercalation MoSe can be can be obtained by by amidation and elaidin reaction after calcining in polymerization process2Nanometer sheet.The material
In 5A g-1High current density under still have 367mAh g-1Capacity, 1A g-1Under still maintain 445mAh g-1Capacity circulating 100
Circle.
Existing MoSe2Material preparation method is generally hydro-thermal method, and pattern is mostly microballoon or three-dimensional structure, specific surface area mistake
Conference causes the formation of excessive SEI films, causes the loss of capacity.The structure of one-dimensional material has more preferable uniformity, correspondence
Power change has extremely strong resistivity, and the electrons/ions transmission channel of orientation can efficiently transmit sodium ion and electronics.This
The research of aspect is fewer.Although some seminars improve the electric conductivity of material by doped graphene, their stone
Black alkene simply simply adulterates, and does not spread out well, the reunion of graphene is caused, so as to influence chemical property.
At present on MoSe2Nanofiber prepares rare report, therefore, develops a kind of MoSe2Nanofiber and its simple and effective system
Preparation Method is just particularly important.
The content of the invention
It is an object of the invention to provide a kind of carbon coating MoSe2/ graphene electro spinning nano fiber and preparation method thereof.
A kind of carbon coating MoSe of the present invention2/ graphene electro spinning nano fiber；The carbon coating MoSe2/ graphene electrospinning is received
Rice fiber is by carbon coated, MoSe2, graphene composition, wherein carbon coated and MoSe2Mass ratio be 15-40:85-60；By every
100g carbon coatings MoSe2/ graphene electro spinning nano fiber meter, in 100g carbon coatings MoSe2In/graphene electro spinning nano fiber, stone
The content of black alkene is 0.2-1g；The MoSe2It is uniformly distributed with lenticular in fiber, and is wrapped by carbon coating；The graphene
Run through or be embedded in carbon coated as conductive network.The carbon coating MoSe2The diameter 200 of/graphene electro spinning nano fiber
To 300nm, draw ratio is more than 10000.
Preferably, nano fiber coated carbon and MoSe are defined2Gross mass be 100 parts, then carbon coated quality be
15-40 parts, MoSe2Quality be 85-60 parts.
Carbon coating MoSe designed by the present invention2In/graphene electro spinning nano fiber, selenizing molybdenum crystal is uniformly dispersed in
Inside carbon fiber, the agraphitic carbon generated after being carbonized by high polymer is wrapped in, so as to effectively inhibit selenium in charge and discharge process
Change the volumetric expansion of molybdenum；Graphene is not reunited blocking, well with carbon fiber main body agraphitic carbon mixed distribution, is formed conductive
Network.
Carbon coating MoSe designed by the present invention2In/graphene electro spinning nano fiber, fibrous material diameter 200 is arrived
300nm, pattern is uniform；Draw ratio is more than 10000.In theory, in the technique designed by the present invention, the length of products obtained therefrom
Degree can be prepared and adjusted according to the actual requirements.
A kind of carbon coating MoSe of the present invention2/ graphene electro spinning nano fiber；The carbon coated is the nothing after high polymer is carbonized
Sizing carbon.
A kind of carbon coating MoSe of the present invention2The preparation method of/graphene electro spinning nano fiber, comprises the steps：
Step one
Water-soluble molybdenum salt and high polymer are dissolved in solvent, heating will be dispersed through uniform until forming stable transparent colloidal sol
Graphene solution add molybdenum salting liquid formation electrospun solution；The solvent is made up of ethylene glycol and deionized water；The electrospinning
In solution, the volume ratio of ethylene glycol and deionized water is 0.5-2:5；
Step 2
To step one gained electrospun solution, electrostatic spinning is carried out, hybridized fiber is obtained；
Step 3
At 500-800 DEG C, hybridized fiber obtained by step 2 and zeroth order selenium are heated, carbon coating MoSe is obtained2/ graphite
Alkene nano-fiber material.
A kind of carbon coating MoSe of the present invention2In the preparation method of/graphene electro spinning nano fiber, the electrospun solution, stone
The concentration range of black alkene is 0.001-2mg/mL, preferably 0.5-1mg/mL；The volume ratio of ethylene glycol and deionized water is 0.5-
2:5, preferably 1-1.5:5th, it is more preferably 1:5；Mo concentration is 0-1mol/L, is preferably 0.1- in the electrospun solution
0.6mol/L, more preferably 0.3-0.5mol/L.
A kind of carbon coating MoSe of the present invention2The preparation method of/graphene electro spinning nano fiber, the water-soluble molybdenum salt is selected from
At least one of ammonium molybdate, sodium molybdate.
A kind of carbon coating MoSe of the present invention2The preparation method of/graphene electro spinning nano fiber, the high polymer is selected from poly- second
At least one of alkene pyrrolidone (PVP), polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA).
Preferably, a kind of carbon coating MoSe of the invention2The preparation method of/graphene electro spinning nano fiber, Gao Ju
Thing is dissolved in deionized water, obtains the liquid that mass percentage concentration is 8-12%.The high polymer is preferably polyvinylpyrrolidine
Ketone (PVP).
Preferably, a kind of carbon coating MoSe of the invention2The preparation method of/graphene electro spinning nano fiber, step
In graphene solution described in one, the concentration of graphene is 0.5-1mg/mL.
Using when, water-soluble molybdenum salt and high polymer are dissolved in deionization and ethylene glycol mixed solution, and 60 DEG C of heating water baths are straight
To stable transparent colloidal sol is formed, molybdenum salting liquid formation electrospun solution will be added by graphene solution scattered at a high speed, while excellent
In selected control electrospun solution, the volume ratio of deionized water and ethylene glycol is 5:1.
Preferably, a kind of carbon coating MoSe of the invention2The preparation method of/graphene electro spinning nano fiber, step
In two, electrospun solution is inserted into syringe, then hybridized fiber is prepared with method of electrostatic spinning；During electrostatic spinning, voltage is 25-
30KV, syringe needle is away from collecting board apart from 10-30cm, and fltting speed is 0.1-0.5mL/h.
Preferably, a kind of carbon coating MoSe of the invention2The preparation method of/graphene electro spinning nano fiber, step
In three, be placed in after processing is dried to hybridized fiber obtained by step 2 together with selenium powder in vacuum-sintering, in 500-800 DEG C,
Preferably 600-700 DEG C, more preferably 640-660 DEG C sintering 0.5-6h, preferably 1.5-3h, more preferably 2.-
2.5h obtains carbon coating MoSe2/ graphene nano fiber material.
Preferably, a kind of carbon coating MoSe of the invention2The preparation method of/graphene electro spinning nano fiber, step
In three, during drying process, it is 50-100 DEG C to control temperature, and the time is 5-24h.
Preferably, a kind of carbon coating MoSe of the invention2The preparation method of/graphene electro spinning nano fiber, with 1-
10 DEG C/min heating rates are warming up to 500-800 DEG C and are sintered.
Carbon coating MoSe that is of the invention designed and preparing2/ graphene electro spinning nano fiber；When it is used for sode cell,
Current density is 0.2Ag-1, after 200 circle circulations, capability retention is more than or equal to 86%.
Carbon coating MoSe that is of the invention designed and preparing2/ graphene electro spinning nano fiber；It can be also used for lithium-ion electric
The fields such as pond, solar cell, photocatalysis and electro-catalysis.
Principle and advantage
This experimental method first passage electrospinning combines carbonization and prepares carbon coating MoSe with the step of selenization technology one2/ graphene is received
Rice fibrous material.Repeatedly grope to probe into excessively more than this seminar, have been surprisingly found that a certain amount of ethylene glycol is added in solvent to be had
Effect realizes the high-quality electrospinning of molybdenum salt.Specific vacuum carburization selenization technology is combined after electrospinning, the one of superior performance has been prepared
Tie up carbon coating MoSe2/ graphene nano fiber material.The raw material of the inventive method is easy to get, and preparation is simple, reacts bar
Part is gentle, and excellent storage sodium performance is shown as anode material of lithium-ion battery, close in electric current when being used for sode cell such as it
Spend for 0.2Ag-1, after 200 circle circulations, capability retention is more than or equal to 86%.
Brief description of the drawings：
Fig. 1 is the carbon coating MoSe that the present invention is obtained in embodiment 12The X-ray diffraction of/graphene nano fiber material
Collection of illustrative plates；
Fig. 2 is the carbon coating MoSe that the present invention is obtained in embodiment 12The SEM figures of/graphene nano fiber material；
Fig. 3 is the carbon coating MoSe that the present invention is obtained in embodiment 12The TEM figures of/graphene nano fiber material；
Fig. 4 is the carbon coating MoSe that the present invention is obtained in embodiment 12The cycle performance of/graphene nano fiber material
Figure；
Fig. 5 is the carbon coating MoSe that the present invention is obtained in embodiment 12The high rate performance of/graphene nano fiber material
Figure；
Fig. 6 is the cycle performance figure of products obtained therefrom in comparative example 1 of the present invention；
Fig. 7 is the high rate performance figure of products obtained therefrom in comparative example 1 of the present invention.
Fig. 8 is the cycle performance figure of products obtained therefrom in comparative example 2 of the present invention；
Fig. 9 is the high rate performance figure of products obtained therefrom in comparative example 2 of the present invention.
As can be seen from Figure 1 the material prepared is well and MoSe2Diffraction peak match, determines that final product is
MoSe2。
Fiber morphology is uniform as can be seen from Figure 2, reunites without big bulk, illustrates electrospinning effect very well, graphene does not have
There is reunion
Fibre diameter is in 200nm or so as can be seen from Figure 3, and graphene is shown as polycrystalline, and it is fine to be dispersed in carbon
Dimension is internal.
It is as can be seen from Figure 4 0.2A g in current density-1, material can be enclosed with stable circulation 200, and the 200th circle is still put
366.9mAh g are gone out-1Capacity, the 200th circle capability retention is still up to 86%.
As can be seen from Figure 5 when current density is set to 0.2,0.5,1.0,1.5 and 2.0Ag-1, the reversible capacity of products obtained therefrom
Respectively 402.4,380.8,353,334.2 and 320mAhg-1.Current density is reduced to 0.2Ag again after 50 enclose-1, electric discharge ratio
Capacity still maintains 384mAhg-1, with very excellent high rate performance.
It is as can be seen from Figure 6 0.2A g in current density-1, material can be enclosed with stable circulation 120, and capacity is maintained at
350mAhg-1, subsequent capacity starts significantly to fail, and cycle performance is poor.
As can be seen from Figure 7 when current density is set to 0.2,0.5,1.0,1.5 and 2.0Ag-1, the reversible capacity of products obtained therefrom
Respectively 397.4,342,287,235.1 and 176.4mAhg-1Current density is reduced to 0.2A g again after 50 enclose-1, electric discharge ratio
Capacity begins to return to 352.9mAhg-1, subsequent fast decay to 290.5mAhg-1, conductive network, carbon bag are used as without graphene
Cover MoSe2/ nano-fiber material has slightly worse high rate performance.
It is as can be seen from Figure 8 0.2A g in current density-1, after 100 circle circulations, specific discharge capacity has been decayed to
100mAhg-1Hereinafter, circulate particularly poor.
High rate performance lands vertically trend as can be seen from Figure 9, illustrates that material has excessively poor high rate performance.
Embodiment：
Using the nano-fiber material prepared by the present invention as active material, in mass ratio, active material：Bond agent carboxymethyl
Sodium cellulosate (CMC)：Conductive agent acetylene black=8:1:1, it is made into uniform sizing material, solvent is absolute ethyl alcohol and deionized water, and nothing
The volume ratio of water-ethanol and deionized water is 2:3.It is applied on copper foil, is cut out after 60 DEG C of vacuum drying 12h after stirring 12 hours
Into electrode slice.It is CR2025 button cells from battery case, barrier film model Whatman GF/D, the sodium piece that rolling is cut out is made
For negative pole, from electrolyte, battery is assembled in glove box, battery performance is tested on blue electrical measurement test system；It is described
Electrolyte is by NaClO4Sodium salt, ethylene carbonate (EC), diethyl carbonate (DEC), fluorinated ethylene carbonate (FEC) solvent group
Into；NaClO in the electrolyte4Concentration be 1mol/L；EC and DEC volume ratio 1:1, FEC concentration is 5wt%.
Embodiment 1：
Weigh 0.5297gH24Mo7N6O24·4H2O is dissolved in 1mL deionized water solution and 1mL ethylene glycol mixed solution
In, stir and wait to take, weigh 0.6114g PVP powder and be dissolved in 2mL deionized water solution and stirring half in 60 DEG C of water-baths
Hour forms vitreosol, and molybdenum salting liquid is added thereto, and the graphene for weighing 5mg is placed in 2mL deionized waters, high-speed stirred
Added after 5min in sol solution, 6h is stirred at room temperature and is made into electrospun solution, 10mL syringes are inserted, prepared and received using method of electrostatic spinning
Rice fiber, electrospinning parameters：Voltage is 30KV, and syringe needle is away from collecting board apart from 20cm, and fltting speed is 0.3mL/h.Obtained spinning
Fiber 60 DEG C of dry 12h in vacuum drying oven, after the vacuum-sintering together with 2g selenium powders, sintering temperature be 650 DEG C, the time is 2h,
Heating rate is 10 DEG C/min, obtains a diameter of 200 and arrives 300nm carbon coatings MoSe2/ graphene nano fiber material；Gained is produced
The draw ratio of product is more than 10000.By preceding method, using gained nano-fiber material as active material, battery, detection electricity are prepared into
The electric property in pond；Circulation and high rate performance are tested on blue electrical measurement test system, and test condition is 0.01-3V, and 30 DEG C of constant temperature are surveyed
Examination.Products obtained therefrom better performances, are 0.2A g in current density-1, after 200 circle circulations, the 200th circle is still released
366.9mAh g-1Capacity, the 200th circle capability retention is still up to 86%.
When current density is set to 0.2,0.5,1.0,1.5 and 2.0Ag-1, the reversible capacity of products obtained therefrom is respectively 402.4,
And 320mAhg 380.8,353,334.2-1.Current density is reduced to 0.2A g again after 50 enclose-1, specific discharge capacity still maintains
384mAhg-1, with very excellent high rate performance.
Embodiment 2：
Weigh 0.5297gH24Mo7N6O24·4H2O is dissolved in 1mL deionized water solution and 1mL ethylene glycol mixed solution
In, stir and wait to take, weigh 0.6114g PVP powder and be dissolved in 2mL deionized water solution and stirring half in 60 DEG C of water-baths
Hour forms vitreosol, and molybdenum salting liquid is added thereto, and the graphene for weighing 5mg is placed in 2mL deionized waters, high-speed stirred
Added after 5min in sol solution, 6h is stirred at room temperature and is made into electrospun solution, 10mL syringes are inserted, prepared and received using method of electrostatic spinning
Rice fiber, electrospinning parameters：Voltage is 25KV, and syringe needle is away from collecting board apart from 20cm, and fltting speed is 0.3mL/h.Obtained spinning
Fiber 60 DEG C of dry 12h in vacuum drying oven, after the vacuum-sintering together with 2g selenium powders, sintering temperature be 650 DEG C, the time is 2h,
Heating rate is 10 DEG C/min, obtains a diameter of 200 and arrives 350nm carbon coatings MoSe2/ graphene nano fiber material products obtained therefrom
Draw ratio be more than 10000.By preceding method, using gained nano-fiber material as active material, battery is prepared into.
Embodiment 3：
Weigh 0.5297gH24Mo7N6O24·4H2O is dissolved in 1mL deionized water solution and 1mL ethylene glycol mixed solution
In, stir and wait to take, weigh 0.6114g PVP powder and be dissolved in 2mL deionized water solution and stirring half in 60 DEG C of water-baths
Hour forms vitreosol, and molybdenum salting liquid is added thereto, and the graphene for weighing 1mg is placed in 2mL deionized waters, high-speed stirred
Added after 5min in sol solution, 6h is stirred at room temperature and is made into electrospun solution, 10mL syringes are inserted, prepared and received using method of electrostatic spinning
Rice fiber, electrospinning parameters：Voltage is 30KV, and syringe needle is away from collecting board apart from 20cm, and fltting speed is 0.3mL/h.Obtained spinning
Fiber 60 DEG C of dry 12h in vacuum drying oven, after the vacuum-sintering together with 2g selenium powders, sintering temperature be 650 DEG C, the time is 2h,
Heating rate is 10 DEG C/min, obtains a diameter of 200 and arrives 300nm carbon coatings MoSe2/ graphene nano fiber material；Gained is produced
The draw ratio of product is more than 10000；By preceding method, using gained nano-fiber material as active material, battery is prepared into.
Comparative example 1：
Weigh 0.5297gH24Mo7N6O24·4H2O is dissolved in 1mL deionized water solution and 1mL ethylene glycol mixed solution
In, stir and wait to take, weigh 0.6114g PVP powder and be dissolved in 4mL deionized water solution and stirring half in 60 DEG C of water-baths
Hour forms vitreosol, and molybdenum salting liquid is added thereto, 6h is stirred at room temperature and is made into electrospun solution, 10mL syringes are inserted, and uses
Method of electrostatic spinning prepares nanofiber, electrospinning parameters：Voltage is 30KV, and syringe needle is away from collecting board apart from 20cm, and fltting speed is
0.3mL/h.Obtained spinning fibre 60 DEG C of dry 12h in vacuum drying oven, after the vacuum-sintering together with 2g selenium powders, sintering temperature
For 650 DEG C, the time is 2h, and heating rate is 10 DEG C/min, obtains 150 and arrives 300nm carbon coatings MoSe2Nano-fiber material.Press
Preceding method, using gained nano-fiber material as active material, is prepared into battery, detects the electric property of battery；Circulation and times
Rate performance is tested on blue electrical measurement test system, and test condition is 0.01-3V, 30 DEG C of constant temperature tests.It is 0.2A g in current density-1, after 200 circle circulations, the 200th circle has still released 245mAh g-1Capacity, the 200th circle capability retention be 70%.
When current density is set to 0.2,0.5,1.0,1.5 and 2.0Ag-1, the reversible capacity of products obtained therefrom is respectively 397.4,
342,287,235.1 and 176.4mAhg-1Current density is reduced to 0.2A g again after 50 enclose-1, specific discharge capacity begins to return to
352.9mAhg-1, subsequent fast decay to 290.5mAhg-1, conductive network, carbon coating MoSe are used as without graphene2/ Nanowire
Dimension material has slightly worse high rate performance.
Comparative example 2：
Weigh 0.5297gH24Mo7N6O24·4H2O is dissolved in 1mL deionized water solution and 1mL ethylene glycol mixed solution
In, weigh 0.6114g PVP powder be dissolved in 2mL deionized water solution and in 60 DEG C of water-baths stir half an hour form transparent
Colloidal sol, molybdenum salting liquid is added thereto, and the graphene for weighing 1mg is placed in 2mL deionized waters, is added after high-speed stirred 5min molten
In sol solution, 6h is stirred at room temperature and is made into electrospun solution, insert 10mL syringes, nanofiber, electrospinning are prepared using method of electrostatic spinning
Parameter：Voltage is 30KV, and syringe needle is away from collecting board apart from 20cm, and fltting speed is 0.3mL/h.Obtained spinning fibre dries in vacuum
60 DEG C of dry 12h in case, after the vacuum-sintering together with 2g selenium powders, sintering temperature be 300 DEG C, the time is 2h, and heating rate is 10
DEG C/min, obtain carbon coating MoSe2/ graphene nano fiber material, by preceding method, using gained nano-fiber material as activity
Material, is prepared into battery, detects the electric property of battery；Circulation and high rate performance are tested on blue electrical measurement test system, test-strips
Part is 0.01-3V, 30 DEG C of constant temperature tests.It is 0.2Ag in current density-1, after 100 circle circulations, specific discharge capacity has been decayed
To 100mAhg-1Hereinafter, high rate performance is also the trend of landing vertically.
Comparative example and comparative example 2 can be seen that：Sintering temperature is less than 500 DEG C, and high polymer is not carbonized completely, property
Can be poor.
Comparative example 3：
Weigh 0.5297gH24Mo7N6O24·4H2O is dissolved in 3mL deionized water solution, is stirred and is waited to take, weighs
0.6114g PVP powder is dissolved in 3mL deionized water solution, and stirring half an hour forms transparent molten in 60 DEG C of water-baths
Glue, molybdenum salting liquid is added thereto, and 6h is stirred at room temperature and is made into electrospun solution, is inserted 10mL syringes, is prepared using method of electrostatic spinning
Nanofiber, discovery is not added with conditions of ethylene glycol, it is impossible to normal spinning.
Comparative example 4：
Weigh 0.5297gH24Mo7N6O24·4H2O is dissolved in 3mL ethylene glycol solution, is stirred and is waited to take, weighs
0.6114g PVP powder is dissolved in 1mL deionized water solution and 1mL ethylene glycol mixed solution, and in 60 DEG C of water-baths
Half an hour formation vitreosol is stirred, molybdenum salting liquid is added thereto, the graphene for weighing 1mg is placed in 1mL deionized waters, it is high
Added after speed stirring 5min in sol solution, 6h is stirred at room temperature and is made into electrospun solution, 10mL syringes are inserted, using method of electrostatic spinning
Nanofiber is prepared, it is found that the consumption of ethylene glycol is added and excessively causes solution viscosity excessive, it is impossible to normal spinning.
Comparative example 5
Weigh 0.5297g H24Mo7N6O24·4H2The ethylene glycol mixing that O is dissolved in 2mL deionized water solution and 0.4mL is molten
In liquid, stir and wait to take, weigh 0.6114g PVP powder and be dissolved in 2mL deionized water solution and stirred in 60 DEG C of water-baths
Half an hour forms vitreosol, and molybdenum salting liquid is added thereto, and the graphene for weighing 5mg is placed in 2mL deionized waters, high-speed stirring
Mix and added after 5min in sol solution, 6h is stirred at room temperature and is made into electrospun solution, inserts 10mL syringes, is prepared using method of electrostatic spinning
Nanofiber, electrospinning parameters：Voltage is 30KV, and syringe needle is away from collecting board apart from 20cm, and fltting speed is 0.3mL/h.In spinning
, there is fracture of wire phenomenon in Cheng Zhong.Obtained spinning fibre 60 DEG C of dry 12h in vacuum drying oven, after together with 2g selenium powders vacuum burn
Knot, sintering temperature is 650 DEG C, and the time is 2h, and heating rate is 10 DEG C/min, obtains a diameter of 200 and arrives 300nm carbon coatings
MoSe2/ graphene nano fiber material.In products obtained therefrom, draw ratio maximum is only 1250.
Claims (10)
1. a kind of carbon coating MoSe2/ graphene electro spinning nano fiber；It is characterized in that：The carbon coating MoSe2/ graphene electrospinning
Nanofiber is by carbon coated, MoSe2, graphene composition, wherein carbon coated and MoSe2Mass ratio be 15-40:85-60；By every
100g carbon coatings MoSe2/ graphene electro spinning nano fiber meter, in 100g carbon coatings MoSe2In/graphene electro spinning nano fiber, stone
The content of black alkene is 0.2-1g；The MoSe2It is uniformly distributed with lenticular in fiber, and is wrapped by carbon coating；The graphene
Run through or be embedded in carbon coated as conductive network；The carbon coating MoSe2The diameter 200 of/graphene electro spinning nano fiber
To 300nm, draw ratio is more than 10000.
2. one kind prepares carbon coating MoSe as claimed in claim 12The method of/graphene electro spinning nano fiber, its feature exists
In；Comprise the steps：
Step one
Water-soluble molybdenum salt and high polymer are dissolved in solvent, heating will be dispersed through uniform stone until forming stable transparent colloidal sol
Black alkene solution adds molybdenum salting liquid formation electrospun solution；The solvent is made up of ethylene glycol and deionized water；The electrospun solution
In, the volume ratio of ethylene glycol and deionized water is 0.5-2:5；
Step 2
To step one gained electrospun solution, electrostatic spinning is carried out, hybridized fiber is obtained；
Step 3
At 500-800 DEG C, hybridized fiber obtained by step 2 and zeroth order selenium are subjected to vacuum-sintering in tube furnace, carbon coating is obtained
MoSe2/ graphene nano fiber material.
3. a kind of carbon coating MoSe according to claim 22The preparation method of/graphene electro spinning nano fiber, its feature exists
In：In the electrospun solution, the concentration range of graphene is 0.01-2mg/mL；The volume ratio of ethylene glycol and deionized water is
0.5-2:5；Mo concentration is 0-1mol/L in the electrospun solution.
4. a kind of carbon coating MoSe according to claim 22The preparation method of/graphene electro spinning nano fiber, its feature exists
In：The water-soluble molybdenum salt is selected from least one of ammonium molybdate, sodium molybdate.
5. a kind of carbon coating MoSe according to claim 22The preparation method of/graphene electro spinning nano fiber, its feature exists
In：The high polymer is selected from least one of polyvinylpyrrolidone, polyvinyl alcohol, polymethyl methacrylate.
6. a kind of carbon coating MoSe according to claim 22The preparation method of/graphene electro spinning nano fiber, its feature exists
In：High polymer is dissolved in deionized water, obtains the colloidal sol that mass percentage concentration is 5-20%.
7. a kind of carbon coating MoSe according to claim 22The preparation method of/graphene electro spinning nano fiber, its feature exists
In：In graphene solution described in step one, the concentration of graphene is 0.5-1mg/mL.
8. a kind of carbon coating MoSe according to claim 22The preparation method of/graphene electro spinning nano fiber, its feature exists
In：In step 2, electrospun solution is inserted into syringe, then hybridized fiber is prepared with method of electrostatic spinning；During electrostatic spinning, voltage
For 20-30KV, syringe needle is away from collecting board apart from 10-30cm, and fltting speed is 0.1-1mL/h.
9. a kind of carbon coating MoSe according to claim 22The preparation method of/graphene electro spinning nano fiber, its feature exists
In：In step 3, it is placed in after processing is dried to hybridized fiber obtained by step 2 together with selenium powder in vacuum-sintering, in 500-
800 DEG C of sintering 0.5-6h obtain carbon coating MoSe2/ graphene nano fiber material.
10. a kind of carbon coating MoSe according to claim 92The preparation method of/graphene electro spinning nano fiber, its feature
It is：In step 3, during drying process, it is 50-100 DEG C to control temperature, and the time is 5-24h；After drying process, with 1-10 DEG C/
Min heating rates are warming up to 500-800 DEG C and are sintered.
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