CN105261743B - A kind of beanpod structure carbon coating vanadium trioxide nano wire film and preparation method thereof - Google Patents
A kind of beanpod structure carbon coating vanadium trioxide nano wire film and preparation method thereof Download PDFInfo
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- CN105261743B CN105261743B CN201510562574.2A CN201510562574A CN105261743B CN 105261743 B CN105261743 B CN 105261743B CN 201510562574 A CN201510562574 A CN 201510562574A CN 105261743 B CN105261743 B CN 105261743B
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- 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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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
Present invention relates particularly to a kind of beanpod structure carbon coating vanadium trioxide nano wire films and preparation method thereof.This method includes the following steps：1) seven three vanadium nano wires of oxidation are prepared；2) above-mentioned 40 ml of uniform dispersion is taken, then 50~500mg glucose is added in, stir 10 min, it is uniformly mixed, finally uniformly mixed above-mentioned solution is poured into water heating kettle, oven temperature is risen to 180 DEG C, water heating kettle is put into baking oven and keeps the temperature 0.5~5h, sample after water cleaning hydro-thermal, vacuum filtration film forming are placed in drying box and are dried to obtain the three vanadium nano wire films of oxidation of carbon coating seven；3) sample film of drying and moulding is placed in tube furnace heat treatment, 3h is kept the temperature for 400~1000 DEG C under the conditions of argon gas, with stove cooled to room temperature, obtain beanpod structure carbon coating vanadium trioxide nano wire film.The reliable preparation process of the present invention, low energy consumption, and yield is high, and prepared carbon coating vanadium trioxide nano wire is evenly distributed, and beanpod structure is apparent, and length is controllable, suitable for electrochemical field.
Description
Technical field
The invention belongs to nano composite structure technical fields.It is received more particularly to a kind of beanpod structure carbon coating vanadium trioxide
Rice noodles film and preparation method thereof.
Background technology
In recent years, consuming excessively for fossil feedstock brings unprecedented energy crisis and environmental problem.Because of this person
It is positive make great efforts to develop various new energy and energy storage device, wherein nano material shows huge application prospect, by wide
Big researcher's extensive concern.Theoretical and experimental studies results show that for common powder body material nano material is shown
More excellent performance.Particularly monodimension nanometer material (such as nano wire, nanotube, nanobelt) has one-dimensional electron-transport
Channel for compared to common powder body material, shows more excellent photoelectrochemical behaviour.V2O3It is higher due to having
Specific capacity, the advantages that resourceful and preparation method is simple and easy to get, be widely used in ultracapacitor, lithium-ion electric
The fields such as pond material.And in the fields such as lithium ion battery and ultracapacitor, due to V2O3Electric conductivity is bad, and in charge and discharge
Generated in electric process larger volume expansion be easy to cause its structure destruction so that capacity sharp-decay, so as to limit its into
One step application.
In addition, the rise of flexible electronic devices, causes interest of the people to flexible energy storage device, flexible electrode is flexible
The key factor of energy storage device.Since pure vanadium trioxide hardly results in long nano wire, it is difficult to form flexible electrode film.
Invention content
The present invention is directed to existing technological deficiency and achievement is overcome to limit, it is therefore an objective to provide a kind of method simply and technique can
The beanpod structure carbon coating vanadium trioxide nano wire that leans on is thin and preparation method thereof, the beanpod structure carbon coating prepared with this method
The advantages that vanadium trioxide nano wire film is without template, and size uniform, and beanpod structure is apparent, and yield is high.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of preparation method of beanpod structure carbon coating vanadium trioxide nano wire film, includes the following steps：
1) seven three vanadium nano wires of oxidation are prepared, 50mg samples is taken to add in water, stirring obtains seven oxidations, three vanadium overlong nanowire
Dispersion liquid；2) above-mentioned uniform dispersion 40ml is taken, then adds in 50~500mg glucose, is stirred, is uniformly mixed, it finally will be mixed
It closing uniform above-mentioned solution to pour into water heating kettle, oven temperature is risen to 180 DEG C, water heating kettle is put into baking oven keeps the temperature 0.5~5h,
Sample after water cleaning hydro-thermal, vacuum filtration film forming are placed in drying box and are dried to obtain the three vanadium nano wire films of oxidation of carbon coating seven；
3) sample film of drying and moulding is placed in tube furnace heat treatment, 3h is kept the temperature for 400~1000 DEG C under the conditions of argon gas, with stove natural cooling
To room temperature, beanpod structure carbon coating vanadium trioxide nano wire film is obtained.
In said program, the preparation method of seven three vanadium nano wires of oxidation is specially in the step 1)：Take vanadic anhydride
Yellow powder 0.524g adds in water, and ultrasound is sufficiently mixed and is formed uniformly yellow solution, then adds in bis- oxalic acid hydrates of 0.1443g
After stirring, solution is poured into water heating kettle for white powder, in an oven 210 DEG C of condition hydro-thermal 72h, is finally cleaned and dry
The seven three vanadium nano wires of oxidation obtained.
In said program, the rotating speed of blender is 600r/min, mixing time 1h in the step 1).
In said program, the drying temperature that the step 2) is placed in drying box is 60 DEG C, and drying time is more than 12h.
The preparation-obtained beanpod knot of preparation method of the beanpod structure carbon coating vanadium trioxide nano wire film
Structure carbon coating vanadium trioxide nano wire film.
In said program, which be interwoven by a large amount of nano wire in the longitudinal direction, the nano wire be by
The compound long nano wire that the vanadium trioxide stick or particle that carbon pipe package multistage extends along nanowire length direction are formed, it is described
Gap is respectively provided between multistage vanadium trioxide stick or adjacent two sections of particle so as to show apparent cowpea pod structure, every section
The length of vanadium trioxide stick or particle is 200-500nm；The thickness of outer layer carbon-coating is about 10-100nm.
The beanpod structure carbon coating vanadium trioxide nano wire film is in lithium ion battery and ultracapacitor
Using.
Using above-mentioned technical proposal, the present invention proposes that a kind of reliable beanpod structure carbon coating vanadium trioxide nano wire is thin
The preparation method of film, using simple hydrothermal method, so as to reduce many numerous and diverse processes, due to predecessor vanadic anhydride
Middle vanadium is highest valence state, and by being gradually transformed into seven three vanadium of oxidation of both sexes after oxalic acid reduction reaction, first seven three vanadium of oxidation exist
Under hydrone special adsorption, form flake, water-heat process releases energy, and cracks thin slice, the thin slice after finally cracking by
It is crimped in tension force effect, so as to form overlong nanowire structure.It, can be with modulation by the content of modulation glucose and hydro-thermal time
Carbon coating seven aoxidizes the thickness that three vanadium nano wires coat glucose polymer, passes through seven after glucose polymer is coated
Three vanadium nano wire films are aoxidized, are placed in tube furnace, beanpod structure carbon coating vanadium trioxide nanometer is obtained by argon annealed
Line film.
Compared with prior art, the present invention it has the advantages that：
1st, beanpod structure carbon coating vanadium trioxide nano wire prepared by the present invention, even size distribution pass through carbon packet
There is apparent beanpod structure after covering annealing, the material of beanpod structure can preferably promote due to having big specific surface area
The insertion and abjection of lithium ion in lithium-ion battery electrolytes.The conductive layer of outer layer can provide effective electron-transport path simultaneously
And the dissolving and precipitation of limitation internal layer substance in the electrolytic solution.The spatial joint clearance of internal layer can effectively buffer kernel electrode material and exist
The volume expansion generated during embedding lithium/de- lithium, so as to preferably improve the charge-discharge performance of lithium ion battery, is greatly promoted
Its specific capacity and electrochemical cycle stability.
2nd, the seven three vanadium nano wires of oxidation that the present invention is obtained using hydro-thermal method, reaction process without additional addition template, also without
Additional surfactants need to be added, seven three vanadium nano wires of oxidation of size uniform is obtained, has largely saved cost, and energy
Consume low, yield height.
3rd, the Portugal of the invention that seven oxidations, three vanadium can be controlled to be coated by modulation condition concentration of glucose and hydro-thermal time
The thickness of grape glycopolymers finally reaches the thickness of control surface carbon-coating, makes it that can improve cycle performance and influences three oxygen
Change two vanadium electro-chemical activities so that the chemical property of material optimizes.
4th, seven oxidation three vanadium carbonizations of glucose polymer cladding are obtained beanpod knot by the present invention by annealing in argon gas
Structure carbon coating vanadium trioxide by that can obtain the cowpea pod structure of size uniformity after carbonization, is conducive to electrode material and electricity
Solution liquid comes into full contact with and the assembling of electrochemical device.
5th, the seven three vanadium nano wires of oxidation that the present invention is prepared by hydro-thermal method, subsequently obtain flexible beans by a series of processing
Pod structure carbon coating vanadium trioxide nano wire film, for Powder electrode material, without adding additional conductive agent
And collector, chemical property can be effectively improved, and treatment process is reliable, can mass produced, there is production well
Industry prospect.
Therefore, vanadic anhydride is dissolved in distilled water and adds in oxalic acid reduction by the present invention, real subsequently by a series of processing
The preparation for obtaining beanpod structure carbon coating vanadium trioxide nano wire film is showed, reliable preparation process, energy consumption is relatively low, yield
Height, the beanpod structure carbon coating vanadium trioxide nano wire film prepared with this method, size uniform, beanpod structure is apparent, production
Amount is high, suitable for electrochemical field.
Description of the drawings
Fig. 1 is the scanning electron microscope high power and low power front elevation of the beanpod structure carbon coating vanadium trioxide nano wire film
Piece.
Fig. 2 is the X ray diffracting spectrum of the beanpod structure carbon coating vanadium trioxide nano wire film.
Fig. 3 is the transmission electron microscope front picture of the beanpod structure carbon coating vanadium trioxide nano wire film.
After Fig. 4 is prepared into electrode material for the beanpod structure carbon coating vanadium trioxide nano wire film, it is packaged into knob
The multiplying power figure tested after button battery.
After Fig. 5 is prepared into electrode material for the beanpod structure carbon coating vanadium trioxide nano wire film, it is packaged into knob
The cycle figure tested after button battery.
Specific embodiment
The present invention will be further described with reference to the accompanying drawings and detailed description, does not form to its protection domain
Limitation.
Present embodiment propose a kind of process to prepare beanpod structure carbon coating vanadium trioxide nano wire soft
Property film method, by the use of oxalic acid reduction vanadic anhydride as vanadium source, can obtain size more uniform seven by hydro-thermal and aoxidize
Three vanadium nano wires, greatly reduce cost, then add in glucose solution stirring and the hydro-thermal of certain mass, three are aoxidized seven
One layer of glucose polymer film of vanadium surface aggregate forms seven three vanadium nano wire film structures of oxidation of glucose polymer cladding,
Subsequently by being handled in argon gas, beanpod structure carbon coating vanadium trioxide nano wire film, the beans of size uniform can be obtained
The insertion and abjection of pod structure structure, more conducively lithium ion, and volume cushion space is provided, in lithium ion battery and super capacitor
Device etc. has huge application value, and its nano thread structure provides the one-dimensional electron propagation ducts of an overlength.
Embodiment 1
A kind of beanpod structure carbon coating vanadium trioxide nano wire film and preparation method thereof.The preparation method includes following
Step：First, vanadic anhydride yellow powder 0.524g is taken to add in 40ml distilled water, ultrasonic 30min or so, is sufficiently mixed uniformly
Yellow solution is formed, then adds in bis- oxalic acid hydrate white powders of 0.1443g, after stirring 10min, by solution water heating kettle,
210 DEG C of condition hydro-thermal 72h in an oven, finally cleaning and dry seven obtained three vanadium nano wires of oxidation；50mg samples is taken to add
Enter 40ml distilled water, be placed under the blender that rotating speed is 600r/min, stir 1h, obtain three vanadium overlength of dark green seven oxidation and receive
Rice noodles dispersion liquid；Then, above-mentioned uniform dispersion 40ml is taken, then adds in 50~200mg glucose, stirs 10min, mixing is equal
It is even, finally uniformly mixed above-mentioned solution is poured into 60ml water heating kettles, oven temperature is risen to 180 DEG C, water heating kettle is put into
Baking oven keeps the temperature 0.5~1h, and water cleans sample after hydro-thermal, and vacuum filtration film forming is placed in drying box, and drying temperature is 60 DEG C, is done
The dry time is 12h, obtains carbon coating seven and aoxidizes three vanadium nano wire films；The sample film of drying and moulding is placed in tubular type furnace treatment
It manages, 400~500 DEG C of heat preservation 3h under the conditions of Ar with stove cooled to room temperature, obtain beanpod structure carbon coating vanadium trioxide and receive
Rice noodles film.
In the present embodiment：50~200mg of glucose, hydro-thermal keep the temperature 0.5~1h, and 3h are kept the temperature for 400~500 DEG C under the conditions of Ar.
Comparing collection of illustrative plates by the X-ray diffraction of Fig. 2 beanpod structure carbon coating vanadium trioxide nano wire films can be very bright
Aobvious to find out, in 2 θ=24 °, nearby there are diffraction maximum, the signals of corresponding carbon, since carbon is that non-type carbon causes its signal more miscellaneous
Disorderly, by comparing card it is found that signal and JCPDS 34-0187 cards corresponding to other peak positions are complete, for vanadium trioxide
Characteristic signal.
Fig. 1 and Fig. 3 is respectively scanning electron microscopic picture and transmission electron microscope picture, can be with it is clear to see that its beanpod structural carbon
It is longer to coat vanadium trioxide nanowire size, since inner core materials are partly evaporated at high temperature, and external carbon-coating has maintained
Whole nanometer linear structure, so as to obtain beanpod structure, this structure is conducive to improve the specific surface area of material, is the stream of electrolyte
Dynamic and Ion transfer provides channel, shortens the transmission path of ion, while space interval is capable of providing V2O3In removal lithium embedded mistake
The space of volume expansion release occurs in journey, is conducive to improve the cyclical stability of material, and its carbon layers having thicknesses is relatively thin, about
For 10 rans, to the very little that extends influence of ion, and conductive network can be provided.In addition outer layer carbon-coating is to keeping complete knot
Structure plays an important roll, if uncoated carbon, the nano wire of beanpod structure cannot be obtained after annealing.Simultaneously because its nano wire
Structure can filter into flexible film, can be made into flexible electrode material, for the powder body material studied extensively before,
When it is as electrode material, without adding conductive agent, without external current collector is introduced, directly as electrode material, no
The contact resistance between electrode and electrolyte is only reduced, and its cost and experimental technique also obtain the improvement of high degree.
By the results show, beanpod structure carbon coating vanadium trioxide nano wire film is formed, can be effectively improved
Chemical property, when Fig. 4 is shown as beanpod structure carbon coating vanadium trioxide nano wire film as electrode material, when electric current is close
When spending for 0.1A/g, beanpod structure V2O3The specific capacity of@C overlong nanowire electrodes is 187mAh/g, when current density is by 0.1A/g
When increasing to 1A/g, V2O3The specific capacity of@C still has 145.2mAh/g, and capacity maintains 77.65%；And when current density weight
When newly returning to 0.1A/g, the V of beanpod structure2O3@C specific capacities are returned to 185mAh/g again, have no apparent attenuation.Fig. 5 is shown
During for beanpod structure carbon coating vanadium trioxide nano wire film as electrode material, the charge and discharge under the current density of 100mA/g
After electricity cycle 125 times, specific capacity remains to keep original more than 96.4%, and coulombic efficiency after third time charge and discharge
Up to 99.5%.
Embodiment 2
A kind of beanpod structure carbon coating vanadium trioxide nano wire film and preparation method thereof.The preparation method includes following
Step：First, vanadic anhydride yellow powder 0.524g is taken to add in 40ml distilled water, ultrasonic 30min or so, is sufficiently mixed uniformly
Yellow solution is formed, then adds in bis- oxalic acid hydrate white powders of 0.1443g, after stirring 10min, by solution water heating kettle,
210 DEG C of condition hydro-thermal 72h in an oven, finally cleaning and dry seven obtained three vanadium nano wires of oxidation；50mg samples is taken to add
Enter 40ml distilled water, be placed under the blender that rotating speed is 600r/min, stir 1h, obtain three vanadium overlength of dark green seven oxidation and receive
Rice noodles dispersion liquid；Then, above-mentioned uniform dispersion 40ml is taken, then adds in 50~200mg glucose, stirs 10min, mixing is equal
It is even, finally uniformly mixed above-mentioned solution is poured into 60ml water heating kettles, oven temperature is risen to 180 DEG C, water heating kettle is put into
Baking oven keeps the temperature 1~2.5h, and water cleans sample after hydro-thermal, and vacuum filtration film forming is placed in drying box, and drying temperature is 60 DEG C, is done
The dry time is 12h, obtains carbon coating seven and aoxidizes three vanadium nano wire films；The sample film of drying and moulding is placed in tubular type furnace treatment
It manages, 400~500 DEG C of heat preservation 3h under the conditions of Ar with stove cooled to room temperature, obtain beanpod structure carbon coating vanadium trioxide and receive
Rice noodles film.
In the present embodiment：50~200mg of glucose, hydro-thermal keep the temperature 1~2.5h, and 3h are kept the temperature for 400~500 DEG C under the conditions of Ar.
Pass through the results show, when current density is 0.1A/g, beanpod structure V2O3The ratio of@C overlong nanowire electrodes
Capacity is 191mAh/g, when current density increases to 1A/g by 0.1A/g, V2O3The specific capacity of@C still has 143.6mAh/g,
Capacity maintains 72.18%；And when current density comes back to 0.1A/g, the V of beanpod structure2O3@C specific capacities are again
189mAh/g is returned to, has no apparent attenuation.When beanpod structure carbon coating vanadium trioxide nano wire film is as electrode material,
Under the current density of 100mA/g after charge and discharge cycles 125 times, specific capacity remains to keep original more than 97.1%, and
And after third time charge and discharge coulombic efficiency up to 99.8%.
Embodiment 3
A kind of beanpod structure carbon coating vanadium trioxide nano wire film and preparation method thereof.The preparation method includes following
Step：First, vanadic anhydride yellow powder 0.524g is taken to add in 40ml distilled water, ultrasonic 30min or so, is sufficiently mixed uniformly
Yellow solution is formed, then adds in bis- oxalic acid hydrate white powders of 0.1443g, after stirring 10min, by solution water heating kettle,
210 DEG C of condition hydro-thermal 72h in an oven, finally cleaning and dry seven obtained three vanadium nano wires of oxidation；50mg samples is taken to add
Enter 40ml distilled water, be placed under the blender that rotating speed is 600r/min, stir 1h, obtain three vanadium overlength of dark green seven oxidation and receive
Rice noodles dispersion liquid；Then, above-mentioned uniform dispersion 40ml is taken, then adds in 50~200mg glucose, stirs 10min, mixing is equal
It is even, finally uniformly mixed above-mentioned solution is poured into 60ml water heating kettles, oven temperature is risen to 180 DEG C, water heating kettle is put into
Baking oven keeps the temperature 1~2.5h, and water cleans sample after hydro-thermal, and vacuum filtration film forming is placed in drying box, and drying temperature is 60 DEG C, is done
The dry time is 12h, obtains carbon coating seven and aoxidizes three vanadium nano wire films；The sample film of drying and moulding is placed in tubular type furnace treatment
It manages, 500~700 DEG C of heat preservation 3h under the conditions of Ar with stove cooled to room temperature, obtain beanpod structure carbon coating vanadium trioxide and receive
Rice noodles film.
In the present embodiment：50~200mg of glucose, hydro-thermal keep the temperature 1~2.5h, and 3h are kept the temperature for 500~700 DEG C under the conditions of Ar.
Pass through the results show, when current density is 0.1A/g, beanpod structure V2O3The ratio of@C overlong nanowire electrodes
Capacity is 190mAh/g, when current density increases to 1A/g by 0.1A/g, V2O3The specific capacity of@C still has 143.8mAh/g,
Capacity maintains 75.68%；And when current density comes back to 0.1A/g, the V of beanpod structure2O3@C specific capacities are again
188mAh/g is returned to, has no apparent attenuation.When beanpod structure carbon coating vanadium trioxide nano wire film is as electrode material,
Under the current density of 100mA/g after charge and discharge cycles 125 times, specific capacity remains to keep original more than 98.2%, and
And after third time charge and discharge coulombic efficiency up to 99.8%.
Embodiment 4
A kind of beanpod structure carbon coating vanadium trioxide nano wire film and preparation method thereof.The preparation method includes following
Step：First, vanadic anhydride yellow powder 0.524g is taken to add in 40ml distilled water, ultrasonic 30min or so, is sufficiently mixed uniformly
Yellow solution is formed, then adds in bis- oxalic acid hydrate white powders of 0.1443g, after stirring 10min, by solution water heating kettle,
210 DEG C of condition hydro-thermal 72h in an oven, finally cleaning and dry seven obtained three vanadium nano wires of oxidation；50mg samples is taken to add
Enter 40ml distilled water, be placed under the blender that rotating speed is 600r/min, stir 1h, obtain three vanadium overlength of dark green seven oxidation and receive
Rice noodles dispersion liquid；Then, above-mentioned uniform dispersion 40ml is taken, then adds in 200~350mg glucose, stirs 10min, mixing
Uniformly, finally uniformly mixed above-mentioned solution is poured into 60ml water heating kettles, oven temperature is risen to 180 DEG C, water heating kettle is put
Entering baking oven and keep the temperature 1~2.5h, water cleans sample after hydro-thermal, and vacuum filtration film forming is placed in drying box, and drying temperature is 60 DEG C,
Drying time is 12h, obtains carbon coating seven and aoxidizes three vanadium nano wire films；The sample film of drying and moulding is placed in tubular type furnace treatment
It manages, 500~700 DEG C of heat preservation 3h under the conditions of Ar with stove cooled to room temperature, obtain beanpod structure carbon coating vanadium trioxide and receive
Rice noodles film.
In the present embodiment：200~350mg of glucose, hydro-thermal keep the temperature 1~2.5h, and 3h are kept the temperature for 500~700 DEG C under the conditions of Ar.
Pass through the results show, when current density is 0.1A/g, beanpod structure V2O3The ratio of@C overlong nanowire electrodes
Capacity is 194mAh/g, when current density increases to 1A/g by 0.1A/g, V2O3The specific capacity of@C still has 143.4mAh/g,
Capacity maintains 73.92%；And when current density comes back to 0.1A/g, the V of beanpod structure2O3@C specific capacities are again
194mAh/g is returned to, has no apparent attenuation.When beanpod structure carbon coating vanadium trioxide nano wire film is as electrode material,
Under the current density of 100mA/g after charge and discharge cycles 125 times, specific capacity remains to keep original more than 97.8%, and
And after third time charge and discharge coulombic efficiency up to 99.8%.
Embodiment 5
A kind of beanpod structure carbon coating vanadium trioxide nano wire film and preparation method thereof.The preparation method includes following
Step：First, vanadic anhydride yellow powder 0.524g is taken to add in 40ml distilled water, ultrasonic 30min or so, is sufficiently mixed uniformly
Yellow solution is formed, then adds in bis- oxalic acid hydrate white powders of 0.1443g, after stirring 10min, by solution water heating kettle,
210 DEG C of condition hydro-thermal 72h in an oven, finally cleaning and dry seven obtained three vanadium nano wires of oxidation；50mg samples is taken to add
Enter 40ml distilled water, be placed under the blender that rotating speed is 600r/min, stir 1h, obtain three vanadium overlength of dark green seven oxidation and receive
Rice noodles dispersion liquid；Then, above-mentioned uniform dispersion 40ml is taken, then adds in 350~500mg glucose, stirs 10min, mixing
Uniformly, finally uniformly mixed above-mentioned solution is poured into 60ml water heating kettles, oven temperature is risen to 180 DEG C, water heating kettle is put
Entering baking oven and keep the temperature 1~2.5h, water cleans sample after hydro-thermal, and vacuum filtration film forming is placed in drying box, and drying temperature is 60 DEG C,
Drying time is 12h, obtains carbon coating seven and aoxidizes three vanadium nano wire films；The sample film of drying and moulding is placed in tubular type furnace treatment
It manages, 500~700 DEG C of heat preservation 3h under the conditions of Ar with stove cooled to room temperature, obtain beanpod structure carbon coating vanadium trioxide and receive
Rice noodles film.
In the present embodiment：350~500mg of glucose, hydro-thermal keep the temperature 1~2.5h, and 3h are kept the temperature for 500~700 DEG C under the conditions of Ar.
Pass through the results show, when current density is 0.1A/g, beanpod structure V2O3The ratio of@C overlong nanowire electrodes
Capacity is 191mAh/g, when current density increases to 1A/g by 0.1A/g, V2O3The specific capacity of@C still has 150.2mAh/g,
Capacity maintains 78.64%；And when current density comes back to 0.1A/g, the V of beanpod structure2O3@C specific capacities are again
189mAh/g is returned to, has no apparent attenuation.Fig. 5 is shown as beanpod structure carbon coating vanadium trioxide nano wire film as electricity
During the material of pole, under the current density of 100mA/g after charge and discharge cycles 125 times, specific capacity remains to keep original
More than 96.8%, and after third time charge and discharge coulombic efficiency up to 99.1%.
Embodiment 6
A kind of beanpod structure carbon coating vanadium trioxide nano wire film and preparation method thereof.The preparation method includes following
Step：First, vanadic anhydride yellow powder 0.524g is taken to add in 40ml distilled water, ultrasonic 30min or so, is sufficiently mixed uniformly
Yellow solution is formed, then adds in bis- oxalic acid hydrate white powders of 0.1443g, after stirring 10min, by solution water heating kettle,
210 DEG C of condition hydro-thermal 72h in an oven, finally cleaning and dry seven obtained three vanadium nano wires of oxidation；50mg samples is taken to add
Enter 40ml distilled water, be placed under the blender that rotating speed is 600r/min, stir 1h, obtain three vanadium overlength of dark green seven oxidation and receive
Rice noodles dispersion liquid；Then, above-mentioned uniform dispersion 40ml is taken, then adds in 350~500mg glucose, stirs 10min, mixing
Uniformly, finally uniformly mixed above-mentioned solution is poured into 60ml water heating kettles, oven temperature is risen to 180 DEG C, water heating kettle is put
Entering baking oven and keep the temperature 1~2.5h, water cleans sample after hydro-thermal, and vacuum filtration film forming is placed in drying box, and drying temperature is 60 DEG C,
Drying time is 12h, obtains carbon coating seven and aoxidizes three vanadium nano wire films；The sample film of drying and moulding is placed in tubular type furnace treatment
It manages, 700~1000 DEG C of heat preservation 3h under the conditions of Ar with stove cooled to room temperature, obtain beanpod structure carbon coating vanadium trioxide
Nano wire film.
In the present embodiment：350~500mg of glucose, hydro-thermal keep the temperature 1~2.5h, are kept the temperature for 700~1000 DEG C under the conditions of Ar
3h。
Pass through the results show, when current density is 0.1A/g, beanpod structure V2O3The ratio of@C overlong nanowire electrodes
Capacity is 188mAh/g, when current density increases to 1A/g by 0.1A/g, V2O3The specific capacity of@C still has 146.1mAh/g,
Capacity maintains 77.71%；And when current density comes back to 0.1A/g, the V of beanpod structure2O3@C specific capacities are again
184mAh/g is returned to, has no apparent attenuation.When beanpod structure carbon coating vanadium trioxide nano wire film is as electrode material,
Under the current density of 100mA/g after charge and discharge cycles 125 times, specific capacity remains to keep original more than 98.7%, and
And after third time charge and discharge coulombic efficiency up to 99.2%.
Compared with prior art, the present invention it has the advantages that：
1st, beanpod structure carbon coating vanadium trioxide nano wire prepared by the present invention, even size distribution pass through carbon packet
There is apparent beanpod structure after covering annealing, be conducive to improve the specific surface area of material, be flowing and the Ion transfer of electrolyte
Channel is provided, shortens the transmission path of ion, while space interval is capable of providing V2O3Volume occurs during removal lithium embedded
The space of release is expanded, is conducive to improve the cyclical stability of material, there is excellent chemical property.
2nd, the seven three vanadium nano wires of oxidation that the present invention is obtained using hydro-thermal method, reaction process without additional addition template, also without
Additional surfactants need to be added, seven three vanadium nano wires of oxidation of size uniform is obtained, has largely saved cost, and energy
Consume low, yield height.
3rd, the Portugal of the invention that seven oxidations, three vanadium can be controlled to be coated by modulation condition concentration of glucose and hydro-thermal time
The thickness of grape glycopolymers finally reaches the thickness of control surface carbon-coating, in the case where keeping complete nano wire section postcondition, has made it both
Cycle performance can be improved, and do not influence vanadium trioxide electro-chemical activity so that the chemical property of material optimizes.
4th, seven oxidation three vanadium carbonizations of glucose polymer cladding are obtained beanpod knot by the present invention by annealing in argon gas
Structure carbon coating vanadium trioxide by that can obtain the beanpod structure of size uniform after carbonization, is conducive to electrode material and electrolysis
Liquid comes into full contact with and the assembling of electrochemical device.
5th, the seven three vanadium nano wires of oxidation that the present invention is prepared by hydro-thermal method, subsequently obtain flexible beans by a series of processing
Pod structure carbon coating vanadium trioxide nano wire film, for Powder electrode material, without adding additional conductive agent
And collector, chemical property can be effectively improved, and treatment process is reliable, can mass produced, there is production well
Industry prospect.
Therefore, vanadic anhydride is dissolved in distilled water and adds in oxalic acid reduction by the present invention, real subsequently by a series of processing
The preparation for obtaining beanpod structure carbon coating vanadium trioxide nano wire film is showed, reliable preparation process, energy consumption is relatively low, yield
Height, the beanpod structure carbon coating vanadium trioxide nano wire film prepared with this method, size uniform, beanpod structure is apparent, production
Amount is high, suitable for electrochemical field.
Claims (6)
1. a kind of preparation method of beanpod structure carbon coating vanadium trioxide nano wire film, which is characterized in that including following step
Suddenly：1) seven three vanadium nano wires of oxidation are prepared, 50 mg samples is taken to add in water, stirring obtains seven oxidations, three vanadium overlong nanowire point
Dispersion liquid；2) above-mentioned 40 ml of uniform dispersion is taken, then adds in 50~500 mg glucose, is stirred, is uniformly mixed, finally will
Uniformly mixed above-mentioned solution is poured into water heating kettle, and oven temperature is risen to 180 DEG C, and water heating kettle is put into baking oven heat preservation 0.5
~5 h, water clean sample after hydro-thermal, and vacuum filtration film forming is placed in drying box and is dried to obtain the three vanadium nanometers of oxidation of carbon coating seven
Line film；3) sample film of drying and moulding is placed in tube furnace heat treatment, 400~1000 DEG C of heat preservation 3h of argon gas, with stove nature
It is cooled to room temperature, obtains beanpod structure carbon coating vanadium trioxide nano wire film；Seven three vanadium nanometers of oxidation in the step 1)
The preparation method of line is specially：0.524 g of vanadic anhydride yellow powder is taken to add in water, ultrasound is sufficiently mixed and is formed uniformly Huang
Then color solution adds in 0.1443 g, bis- oxalic acid hydrate white powders, after stirring, solution is poured into water heating kettle, in baking oven
In 210 DEG C of 72 h of condition hydro-thermal, finally clean simultaneously dry seven obtained three vanadium nano wires of oxidation.
2. the preparation method of the beanpod structure carbon coating vanadium trioxide nano wire film according to claim 1, feature
It is, the rotating speed stirred in the step 1) is 600 r/min, mixing time 1h.
3. the preparation method of the beanpod structure carbon coating vanadium trioxide nano wire film according to claim 1, feature
It is, the drying temperature that the step 2) is placed in drying box is 60 DEG C, and drying time is more than 12h.
4. the system of the beanpod structure carbon coating vanadium trioxide nano wire film according to any one of claim 1~3
The preparation-obtained beanpod structure carbon coating vanadium trioxide nano wire film of Preparation Method.
5. the beanpod structure carbon coating vanadium trioxide nano wire film according to claim 4, which is characterized in that this is thin
Film is interwoven by a large amount of nano wire in the longitudinal direction, and the nano wire is to wrap up multistage along nanowire length by carbon pipe
The compound long nano wire that the vanadium trioxide stick or particle of direction extension are formed, the multistage vanadium trioxide stick or particle
Gap is respectively provided between adjacent two sections so as to show the length of apparent cowpea pod structure, every section of vanadium trioxide stick or particle
For 200-500 nm；The thickness of outer layer carbon-coating is 10nm.
6. the beanpod structure carbon coating vanadium trioxide nano wire film according to claim 4 in lithium ion battery and surpasses
Application in grade capacitor.
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| Beltlike V2O3@C Core–Shell-Structured Composite: Design, Preparation,Characterization, Phase Transition, and Improvement of Electrochemical Properties of V2O3;Yifu Zhang等;《Eur. J. Inorg. Chem.》;20120214;第2012卷(第10期);第1650–1659页 * |
| Single-crystal H2V3O8 nanowires: a competitive anode with large capacity for aqueous lithium-ion batteries;Huiqiao Li等;《J. Mater. Chem.》;20111126;第21卷;第1780–1787页 * |
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