CN105261743A - Carbon-coated vanadium trioxide nanowire thin film with pod structure and preparation method of carbon-coated vanadium trioxide nanowire thin film with pod structure - Google Patents
Carbon-coated vanadium trioxide nanowire thin film with pod structure and preparation method of carbon-coated vanadium trioxide nanowire thin film with pod structure Download PDFInfo
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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
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- 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
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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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- 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
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- Y02E60/10—Energy storage using batteries
Abstract
The invention particularly relates to a carbon-coated vanadium trioxide nanowire thin film with a pod structure and a preparation method of the carbon-coated vanadium trioxide nanowire thin film with the pod structure. The method comprises the following steps: (1) preparing a V<3>O<7> nanowire; (2) taking 40ml of homogeneous dispersion liquid, adding 50-500mg of glucose, stirring the dispersion liquid for 10 minutes, mixing the dispersion liquid evenly, finally pouring the evenly mixed solution into a hydrothermal kettle, heating an oven to 180 DEG C, putting the hydrothermal kettle into the oven for heat preservation for 0.5-5 hours, cleaning the sample after a hydrothermal reaction, carrying out vacuum filtration to form a film, and drying the film in a drying oven to obtain the carbon-coated V<3>O<7> nanowire thin film; and (3) putting the dried and formed sample film into a tube furnace for heat treatment, carrying out the heat preservation in an argon condition at 400-1,000 DEG C for 3 hours, naturally cooling the film to a room temperature along with the furnace and obtaining the carbon-coated vanadium trioxide nanowire thin film with the pod structure. The preparation method is reliable in preparation technology, low in energy consumption and high in yield; and the prepared carbon-coated vanadium trioxide nanowire thin film is even in distribution, obvious in pod structure, controllable in length and suitable for the field of electrochemistry.
Description
Technical field
The invention belongs to nano composite structure technical field.Be specifically related to coated vanadium trioxide nano wire film of a kind of beanpod structural carbon and preparation method thereof.
Background technology
In recent years, consuming excessively of fossil feedstock brings unprecedented energy crisis and environmental problem.Therefore people are just making great efforts to develop various new forms of energy and energy storage device, and wherein nano material shows huge application prospect, are subject to numerous researchers' extensive concern.Theoretical and experimental studies results shows, relative to common powder body material, nano material shows more excellent performance.Particularly monodimension nanometer material (as nano wire, nanotube, nanobelt etc.) has the electron propagation ducts of one dimension, thus compared to common powder body material, shows more excellent photoelectrochemical behaviour.V
2o
3owing to possessing the advantages such as higher specific capacity, aboundresources and preparation method be simple and easy to get, be widely used in the field such as ultracapacitor, lithium ion battery material.And in the field such as lithium ion battery and ultracapacitor, due to V
2o
3conductivity is bad, and in charge and discharge process, produces larger volumetric expansion easily cause its structural deterioration, makes capacity sharp-decay, thus limits it and apply further.
In addition, the rise of flexible electronic devices, causes the interest of people to flexible energy storage device, and flexible electrode is the key factor of flexible energy storage device.Because pure vanadium trioxide is difficult to obtain long nano wire, be difficult to form flexible electrode film.
Summary of the invention
The present invention is intended to overcome existing technological deficiency and achievement restriction, it is thin and preparation method thereof that object is to provide a kind of method beanpod structural carbon coated vanadium trioxide nano wire that is simple and process, the coated vanadium trioxide nano wire film of the beanpod structural carbon prepared by the method is without template, and size uniform, beanpod structure is obvious, productive rate advantages of higher.
For achieving the above object, the technical solution used in the present invention is:
A preparation method for the coated vanadium trioxide nano wire film of beanpod structural carbon, comprises the following steps:
1) prepare seven oxidation three vanadium nano wires, get 50mg sample and add water, stir, obtain seven oxidation three vanadium overlong nanowire dispersion liquids; 2) above-mentioned uniform dispersion 40ml is got, then 50 ~ 500mg glucose is added, stir, mix, finally the above-mentioned solution mixed is poured in water heating kettle, oven temperature is risen to 180 DEG C, water heating kettle is put into baking oven insulation 0.5 ~ 5h, sample after water cleaning hydro-thermal, vacuum filtration film forming, is placed in drying box drying and obtains the coated seven oxidation three vanadium nano wire films of carbon; 3) sample film of drying and moulding is placed in tube furnace heat treatment, under argon gas condition, 400 ~ 1000 DEG C of insulation 3h, naturally cool to room temperature with stove, obtain the coated vanadium trioxide nano wire film of beanpod structural carbon.
In such scheme, described step 1) in seven oxidation three vanadium nano wires preparation methods be specially: get vanadic oxide yellow powder 0.524g and add water, ultrasonic, fully mix formation yellow solution, then add 0.1443g bis-oxalic acid hydrate white powder, after stirring, solution is poured in water heating kettle, 210 DEG C of condition hydro-thermal 72h in an oven, finally cleaning is the dry seven oxidation three vanadium nano wires obtained also.
In such scheme, described step 1) in the rotating speed of blender be 600r/min, mixing time is 1h.
In such scheme, described step 2) baking temperature that is placed in drying box is 60 DEG C, drying time is more than 12h.
The coated vanadium trioxide nano wire film of preparation method's preparation-obtained beanpod structural carbon of described beanpod structural carbon coated vanadium trioxide nano wire film.
In such scheme, this film is be interwoven by a large amount of nano wires in the longitudinal direction, described nano wire wraps up by carbon pipe the long nano wire of compound that the excellent or particle of the vanadium trioxide that extends along nanowire length direction of multistage formed, all have gap between described multistage vanadium trioxide rod or particle adjacent two sections thus present obvious cowpea pod structure, the length of every section of vanadium trioxide rod or particle is 200-500nm; The thickness of outer carbon-coating is about 10-100nm.
The application of the coated vanadium trioxide nano wire film of described beanpod structural carbon in lithium ion battery and ultracapacitor.
Adopt technique scheme, the present invention proposes the preparation method of the coated vanadium trioxide nano wire film of a kind of reliable beanpod structural carbon, adopt simple hydrothermal method, thus decrease much numerous and diverse operation, because vanadium in predecessor vanadic oxide is highest price state, by being gradually transformed into seven oxidation three vanadium of both sexes after oxalic acid reduction reaction, first seven oxidation three vanadium are under hydrone special adsorption, form flake, water-heat process releases energy, make thin slice cracking, the thin slice after last cracking is curling due to tension force effect, thus forms overlong nanowire structure.By content and the hydro-thermal time of modulation glucose, can the coated seven oxidation three vanadium nano wires of modulation carbon the thickness of coated glucose polymer, by seven oxidation three vanadium nano wire films after glucose polymer is coated, be placed in tube furnace, obtain the coated vanadium trioxide nano wire film of beanpod structural carbon by argon annealed.
The present invention compared with prior art, has following beneficial effect:
1, the coated vanadium trioxide nano wire of beanpod structural carbon prepared of the present invention, its even size distribution, by there is obvious beanpod structure after the coated annealing of carbon, the material of beanpod structure, owing to having large specific area, can better promote the embedding of lithium ion in lithium-ion battery electrolytes and deviate from.Outer field conductive layer can provide effective electric transmission path and limit the dissolving in the electrolytic solution of internal layer material and precipitation.The spatial joint clearance of internal layer effectively can cushion the volumetric expansion that kernel electrode material produces in embedding lithium/de-lithium process, thus better improves the charge-discharge performance of lithium ion battery, improves its specific capacity and electrochemical cycle stability greatly.
2, the present invention's seven oxidation three vanadium nano wires of utilizing hydro thermal method to obtain, course of reaction is without additionally adding template, and also without the need to adding additional surfactants, obtain seven oxidation three vanadium nano wires of size uniform, largely saved cost, and energy consumption is low, productive rate is high.
3, the present invention can control the thickness of the coated glucose polymer of seven oxidation three vanadium by modulation condition concentration of glucose and hydro-thermal time, finally reach the thickness of control surface carbon-coating, it is made to improve cycle performance, do not affect vanadium trioxide electro-chemical activity again, make the chemical property optimization of material.
4, the present invention by annealing in argon gas, coated for glucose polymer seven oxidation three vanadium carbonizations are obtained the coated vanadium trioxide of beanpod structural carbon, by the cowpea pod structure of size uniformity can be obtained after carbonization, be conducive to electrode material and fully contact with electrolyte and the assembling of electrochemical device.
5, the present invention by hydro thermal method prepare seven oxidation three vanadium nano wires, follow-up through the coated vanadium trioxide nano wire film of a series of process flexible beanpod structural carbon of acquisition, relative to Powder electrode material, without the need to adding extra conductive agent and collector, effectively can improve chemical property, and treatment process is reliable, can large-scale production, there is good industrialization prospect.
Therefore, vanadic oxide is dissolved in distilled water and adds oxalic acid reduction by the present invention, follow-up through a series of process, achieves the preparation obtaining the coated vanadium trioxide nano wire film of beanpod structural carbon, reliable preparation process, energy consumption is lower, and productive rate is high, the coated vanadium trioxide nano wire film of the beanpod structural carbon prepared by the method, size uniform, beanpod structure is obvious, and output is high, is applicable to electrochemical field.
Accompanying drawing explanation
Fig. 1 is ESEM high power and the low power front picture of the coated vanadium trioxide nano wire film of described beanpod structural carbon.
Fig. 2 is the X ray diffracting spectrum of the coated vanadium trioxide nano wire film of described beanpod structural carbon.
Fig. 3 is the transmission electron microscope front picture of the coated vanadium trioxide nano wire film of described beanpod structural carbon.
Fig. 4 is after the coated vanadium trioxide nano wire film of described beanpod structural carbon is prepared into electrode material, the multiplying power figure tested after being packaged into button cell.
Fig. 5 is after the coated vanadium trioxide nano wire film of described beanpod structural carbon is prepared into electrode material, the cycle graph tested after being packaged into button cell.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention will be further described, do not form the restriction to its protection range.
This embodiment proposes a kind of method preparing beanpod structural carbon coated vanadium trioxide nano wire fexible film of process, oxalic acid is utilized to reduce vanadic oxide as vanadium source, the more uniform seven oxidation three vanadium nano wires of size can be obtained through hydro-thermal, greatly reduce cost, then the glucose solution adding certain mass stirs and hydro-thermal, at seven oxidation three vanadium surface aggregate one deck glucose polymer films, form the coated seven oxidation three vanadium nano wire film structures of glucose polymer, follow-up process processes in argon gas, the coated vanadium trioxide nano wire film of beanpod structural carbon can be obtained, the beanpod structure structure of its size uniform, be more conducive to the embedding of lithium ion and deviate from, and volume cushion space is provided, there is huge using value in lithium ion battery and ultracapacitor etc., and its nano thread structure provides the one dimension electron propagation ducts of an overlength.
Embodiment 1
Coated vanadium trioxide nano wire film of a kind of beanpod structural carbon and preparation method thereof.This preparation method comprises the following steps: first, get vanadic oxide yellow powder 0.524g and add 40ml distilled water, ultrasonic about 30min, fully mix formation yellow solution, then 0.1443g bis-oxalic acid hydrate white powder is added, after stirring 10min, by solution water heating kettle, 210 DEG C of condition hydro-thermal 72h in an oven, finally cleaning is the dry seven oxidation three vanadium nano wires obtained also; Get 50mg sample and add 40ml distilled water, being placed in rotating speed is under the blender of 600r/min, stirs 1h, obtains dark green seven oxidation three vanadium overlong nanowire dispersion liquids; Then, get above-mentioned uniform dispersion 40ml, then add 50 ~ 200mg glucose, stir 10min, mix, finally the above-mentioned solution mixed is poured in 60ml water heating kettle, oven temperature is risen to 180 DEG C, water heating kettle is put into baking oven insulation 0.5 ~ 1h, sample after water cleaning hydro-thermal, vacuum filtration film forming, be placed in drying box, baking temperature is 60 DEG C, and drying time is 12h, obtains the coated seven oxidation three vanadium nano wire films of carbon; The sample film of drying and moulding is placed in tube furnace heat treatment, and under Ar condition, 400 ~ 500 DEG C of insulation 3h, naturally cool to room temperature with stove, obtain the coated vanadium trioxide nano wire film of beanpod structural carbon.
In the present embodiment: glucose 50 ~ 200mg, 400 ~ 500 DEG C of insulation 3h under hydro-thermal insulation 0.5 ~ 1h, Ar condition.
Can clearly be found out by the X-ray diffraction contrast collection of illustrative plates of the coated vanadium trioxide nano wire film of Fig. 2 beanpod structural carbon, diffraction maximum is there is near 2 θ=24 °, the signal of corresponding carbon, because carbon is that non-type carbon causes its signal more mixed and disorderly, known by comparison card, signal corresponding to other peak positions and JCPDS34-0187 card completely, are the characteristic signal of vanadium trioxide.
Fig. 1 and Fig. 3 is respectively scanning electron microscopic picture and transmission electron microscope picture, can clearly find out, its beanpod structural carbon coated vanadium trioxide nanowire size is longer, due to inner core materials at high temperature part evaporation, and outside carbon-coating maintains complete nanometer linear structure, thus obtains beanpod structure, this structure is conducive to the specific area improving material, for the flowing of electrolyte and Ion transfer provide passage, shorten the transmission path of ion, space interval can provide V simultaneously
2o
3in removal lithium embedded process, there is the space of volumetric expansion release, be conducive to the cyclical stability improving material, and its carbon layers having thicknesses is thinner, is approximately 10 ran, very little to extending influence of ion, and can conductive network be provided.In addition outer carbon-coating has important function to maintenance complete structure, if non-carbon coated, then can not obtain the nano wire of beanpod structure after annealing.Simultaneously due to its nano thread structure, flexible film can be become by suction filtration, can be made into flexible electrode material, compared to the powder body material of extensively research before, when it is as electrode material, without the need to adding conductive agent, also without the need to introducing external current collector, directly it can be used as electrode material, not only reduce the contact resistance between electrode and electrolyte, and its cost and experimental technique also obtain the improvement of high degree.
Result proves by experiment, form the coated vanadium trioxide nano wire film of beanpod structural carbon, effectively can improve chemical property, when Fig. 4 is shown as the coated vanadium trioxide nano wire film of beanpod structural carbon as electrode material, when current density is 0.1A/g, beanpod structure V
2o
3the specific capacity of C overlong nanowire electrode is 187mAh/g, when current density is increased to 1A/g by 0.1A/g, and V
2o
3the specific capacity of C still has 145.2mAh/g, and capacity maintains 77.65%; And when current density comes back to 0.1A/g, the V of beanpod structure
2o
3c specific capacity is returned to 185mAh/g again, there is no obvious decay.When Fig. 5 is shown as the coated vanadium trioxide nano wire film of beanpod structural carbon as electrode material, under the current density of 100mA/g after charge and discharge cycles 125 times, its specific capacity still can keep original more than 96.4%, and after third time discharge and recharge, coulombic efficiency can reach 99.5%.
Embodiment 2
Coated vanadium trioxide nano wire film of a kind of beanpod structural carbon and preparation method thereof.This preparation method comprises the following steps: first, get vanadic oxide yellow powder 0.524g and add 40ml distilled water, ultrasonic about 30min, fully mix formation yellow solution, then 0.1443g bis-oxalic acid hydrate white powder is added, after stirring 10min, by solution water heating kettle, 210 DEG C of condition hydro-thermal 72h in an oven, finally cleaning is the dry seven oxidation three vanadium nano wires obtained also; Get 50mg sample and add 40ml distilled water, being placed in rotating speed is under the blender of 600r/min, stirs 1h, obtains dark green seven oxidation three vanadium overlong nanowire dispersion liquids; Then, get above-mentioned uniform dispersion 40ml, then add 50 ~ 200mg glucose, stir 10min, mix, finally the above-mentioned solution mixed is poured in 60ml water heating kettle, oven temperature is risen to 180 DEG C, water heating kettle is put into baking oven insulation 1 ~ 2.5h, sample after water cleaning hydro-thermal, vacuum filtration film forming, be placed in drying box, baking temperature is 60 DEG C, and drying time is 12h, obtains the coated seven oxidation three vanadium nano wire films of carbon; The sample film of drying and moulding is placed in tube furnace heat treatment, and under Ar condition, 400 ~ 500 DEG C of insulation 3h, naturally cool to room temperature with stove, obtain the coated vanadium trioxide nano wire film of beanpod structural carbon.
In the present embodiment: glucose 50 ~ 200mg, 400 ~ 500 DEG C of insulation 3h under hydro-thermal insulation 1 ~ 2.5h, Ar condition.
Result proves by experiment, when current density is 0.1A/g, and beanpod structure V
2o
3the specific capacity of C overlong nanowire electrode is 191mAh/g, when current density is increased to 1A/g by 0.1A/g, and V
2o
3the specific capacity of C still has 143.6mAh/g, and capacity maintains 72.18%; And when current density comes back to 0.1A/g, the V of beanpod structure
2o
3c specific capacity is returned to 189mAh/g again, there is no obvious decay.When the coated vanadium trioxide nano wire film of beanpod structural carbon is as electrode material, under the current density of 100mA/g after charge and discharge cycles 125 times, its specific capacity still can keep original more than 97.1%, and after third time discharge and recharge, coulombic efficiency can reach 99.8%.
Embodiment 3
Coated vanadium trioxide nano wire film of a kind of beanpod structural carbon and preparation method thereof.This preparation method comprises the following steps: first, get vanadic oxide yellow powder 0.524g and add 40ml distilled water, ultrasonic about 30min, fully mix formation yellow solution, then 0.1443g bis-oxalic acid hydrate white powder is added, after stirring 10min, by solution water heating kettle, 210 DEG C of condition hydro-thermal 72h in an oven, finally cleaning is the dry seven oxidation three vanadium nano wires obtained also; Get 50mg sample and add 40ml distilled water, being placed in rotating speed is under the blender of 600r/min, stirs 1h, obtains dark green seven oxidation three vanadium overlong nanowire dispersion liquids; Then, get above-mentioned uniform dispersion 40ml, then add 50 ~ 200mg glucose, stir 10min, mix, finally the above-mentioned solution mixed is poured in 60ml water heating kettle, oven temperature is risen to 180 DEG C, water heating kettle is put into baking oven insulation 1 ~ 2.5h, sample after water cleaning hydro-thermal, vacuum filtration film forming, be placed in drying box, baking temperature is 60 DEG C, and drying time is 12h, obtains the coated seven oxidation three vanadium nano wire films of carbon; The sample film of drying and moulding is placed in tube furnace heat treatment, and under Ar condition, 500 ~ 700 DEG C of insulation 3h, naturally cool to room temperature with stove, obtain the coated vanadium trioxide nano wire film of beanpod structural carbon.
In the present embodiment: glucose 50 ~ 200mg, 500 ~ 700 DEG C of insulation 3h under hydro-thermal insulation 1 ~ 2.5h, Ar condition.
Result proves by experiment, when current density is 0.1A/g, and beanpod structure V
2o
3the specific capacity of C overlong nanowire electrode is 190mAh/g, when current density is increased to 1A/g by 0.1A/g, and V
2o
3the specific capacity of C still has 143.8mAh/g, and capacity maintains 75.68%; And when current density comes back to 0.1A/g, the V of beanpod structure
2o
3c specific capacity is returned to 188mAh/g again, there is no obvious decay.When the coated vanadium trioxide nano wire film of beanpod structural carbon is as electrode material, under the current density of 100mA/g after charge and discharge cycles 125 times, its specific capacity still can keep original more than 98.2%, and after third time discharge and recharge, coulombic efficiency can reach 99.8%.
Embodiment 4
Coated vanadium trioxide nano wire film of a kind of beanpod structural carbon and preparation method thereof.This preparation method comprises the following steps: first, get vanadic oxide yellow powder 0.524g and add 40ml distilled water, ultrasonic about 30min, fully mix formation yellow solution, then 0.1443g bis-oxalic acid hydrate white powder is added, after stirring 10min, by solution water heating kettle, 210 DEG C of condition hydro-thermal 72h in an oven, finally cleaning is the dry seven oxidation three vanadium nano wires obtained also; Get 50mg sample and add 40ml distilled water, being placed in rotating speed is under the blender of 600r/min, stirs 1h, obtains dark green seven oxidation three vanadium overlong nanowire dispersion liquids; Then, get above-mentioned uniform dispersion 40ml, then add 200 ~ 350mg glucose, stir 10min, mix, finally the above-mentioned solution mixed is poured in 60ml water heating kettle, oven temperature is risen to 180 DEG C, water heating kettle is put into baking oven insulation 1 ~ 2.5h, sample after water cleaning hydro-thermal, vacuum filtration film forming, be placed in drying box, baking temperature is 60 DEG C, and drying time is 12h, obtains the coated seven oxidation three vanadium nano wire films of carbon; The sample film of drying and moulding is placed in tube furnace heat treatment, and under Ar condition, 500 ~ 700 DEG C of insulation 3h, naturally cool to room temperature with stove, obtain the coated vanadium trioxide nano wire film of beanpod structural carbon.
In the present embodiment: glucose 200 ~ 350mg, 500 ~ 700 DEG C of insulation 3h under hydro-thermal insulation 1 ~ 2.5h, Ar condition.
Result proves by experiment, when current density is 0.1A/g, and beanpod structure V
2o
3the specific capacity of C overlong nanowire electrode is 194mAh/g, when current density is increased to 1A/g by 0.1A/g, and V
2o
3the specific capacity of C still has 143.4mAh/g, and capacity maintains 73.92%; And when current density comes back to 0.1A/g, the V of beanpod structure
2o
3c specific capacity is returned to 194mAh/g again, there is no obvious decay.When the coated vanadium trioxide nano wire film of beanpod structural carbon is as electrode material, under the current density of 100mA/g after charge and discharge cycles 125 times, its specific capacity still can keep original more than 97.8%, and after third time discharge and recharge, coulombic efficiency can reach 99.8%.
Embodiment 5
Coated vanadium trioxide nano wire film of a kind of beanpod structural carbon and preparation method thereof.This preparation method comprises the following steps: first, get vanadic oxide yellow powder 0.524g and add 40ml distilled water, ultrasonic about 30min, fully mix formation yellow solution, then 0.1443g bis-oxalic acid hydrate white powder is added, after stirring 10min, by solution water heating kettle, 210 DEG C of condition hydro-thermal 72h in an oven, finally cleaning is the dry seven oxidation three vanadium nano wires obtained also; Get 50mg sample and add 40ml distilled water, being placed in rotating speed is under the blender of 600r/min, stirs 1h, obtains dark green seven oxidation three vanadium overlong nanowire dispersion liquids; Then, get above-mentioned uniform dispersion 40ml, then add 350 ~ 500mg glucose, stir 10min, mix, finally the above-mentioned solution mixed is poured in 60ml water heating kettle, oven temperature is risen to 180 DEG C, water heating kettle is put into baking oven insulation 1 ~ 2.5h, sample after water cleaning hydro-thermal, vacuum filtration film forming, be placed in drying box, baking temperature is 60 DEG C, and drying time is 12h, obtains the coated seven oxidation three vanadium nano wire films of carbon; The sample film of drying and moulding is placed in tube furnace heat treatment, and under Ar condition, 500 ~ 700 DEG C of insulation 3h, naturally cool to room temperature with stove, obtain the coated vanadium trioxide nano wire film of beanpod structural carbon.
In the present embodiment: glucose 350 ~ 500mg, 500 ~ 700 DEG C of insulation 3h under hydro-thermal insulation 1 ~ 2.5h, Ar condition.
Result proves by experiment, when current density is 0.1A/g, and beanpod structure V
2o
3the specific capacity of C overlong nanowire electrode is 191mAh/g, when current density is increased to 1A/g by 0.1A/g, and V
2o
3the specific capacity of C still has 150.2mAh/g, and capacity maintains 78.64%; And when current density comes back to 0.1A/g, the V of beanpod structure
2o
3c specific capacity is returned to 189mAh/g again, there is no obvious decay.When Fig. 5 is shown as the coated vanadium trioxide nano wire film of beanpod structural carbon as electrode material, under the current density of 100mA/g after charge and discharge cycles 125 times, its specific capacity still can keep original more than 96.8%, and after third time discharge and recharge, coulombic efficiency can reach 99.1%.
Embodiment 6
Coated vanadium trioxide nano wire film of a kind of beanpod structural carbon and preparation method thereof.This preparation method comprises the following steps: first, get vanadic oxide yellow powder 0.524g and add 40ml distilled water, ultrasonic about 30min, fully mix formation yellow solution, then 0.1443g bis-oxalic acid hydrate white powder is added, after stirring 10min, by solution water heating kettle, 210 DEG C of condition hydro-thermal 72h in an oven, finally cleaning is the dry seven oxidation three vanadium nano wires obtained also; Get 50mg sample and add 40ml distilled water, being placed in rotating speed is under the blender of 600r/min, stirs 1h, obtains dark green seven oxidation three vanadium overlong nanowire dispersion liquids; Then, get above-mentioned uniform dispersion 40ml, then add 350 ~ 500mg glucose, stir 10min, mix, finally the above-mentioned solution mixed is poured in 60ml water heating kettle, oven temperature is risen to 180 DEG C, water heating kettle is put into baking oven insulation 1 ~ 2.5h, sample after water cleaning hydro-thermal, vacuum filtration film forming, be placed in drying box, baking temperature is 60 DEG C, and drying time is 12h, obtains the coated seven oxidation three vanadium nano wire films of carbon; The sample film of drying and moulding is placed in tube furnace heat treatment, and under Ar condition, 700 ~ 1000 DEG C of insulation 3h, naturally cool to room temperature with stove, obtain the coated vanadium trioxide nano wire film of beanpod structural carbon.
In the present embodiment: glucose 350 ~ 500mg, 700 ~ 1000 DEG C of insulation 3h under hydro-thermal insulation 1 ~ 2.5h, Ar condition.
Result proves by experiment, when current density is 0.1A/g, and beanpod structure V
2o
3the specific capacity of C overlong nanowire electrode is 188mAh/g, when current density is increased to 1A/g by 0.1A/g, and V
2o
3the specific capacity of C still has 146.1mAh/g, and capacity maintains 77.71%; And when current density comes back to 0.1A/g, the V of beanpod structure
2o
3c specific capacity is returned to 184mAh/g again, there is no obvious decay.When the coated vanadium trioxide nano wire film of beanpod structural carbon is as electrode material, under the current density of 100mA/g after charge and discharge cycles 125 times, its specific capacity still can keep original more than 98.7%, and after third time discharge and recharge, coulombic efficiency can reach 99.2%.
The present invention compared with prior art, has following beneficial effect:
1, the coated vanadium trioxide nano wire of beanpod structural carbon prepared of the present invention, its even size distribution, by there is obvious beanpod structure after the coated annealing of carbon, be conducive to the specific area improving material, for the flowing of electrolyte and Ion transfer provide passage, shorten the transmission path of ion, space interval can provide V simultaneously
2o
3in removal lithium embedded process, there is the space of volumetric expansion release, be conducive to the cyclical stability improving material, there is excellent chemical property.
2, the present invention's seven oxidation three vanadium nano wires of utilizing hydro thermal method to obtain, course of reaction is without additionally adding template, and also without the need to adding additional surfactants, obtain seven oxidation three vanadium nano wires of size uniform, largely saved cost, and energy consumption is low, productive rate is high.
3, the present invention can control the thickness of the coated glucose polymer of seven oxidation three vanadium by modulation condition concentration of glucose and hydro-thermal time, finally reach the thickness of control surface carbon-coating, under maintenance complete nano wire joint postcondition, it is made to improve cycle performance, do not affect vanadium trioxide electro-chemical activity again, make the chemical property optimization of material.
4, the present invention by annealing in argon gas, coated for glucose polymer seven oxidation three vanadium carbonizations are obtained the coated vanadium trioxide of beanpod structural carbon, by the beanpod structure of size uniform can be obtained after carbonization, be conducive to electrode material and fully contact with electrolyte and the assembling of electrochemical device.
5, the present invention by hydro thermal method prepare seven oxidation three vanadium nano wires, follow-up through the coated vanadium trioxide nano wire film of a series of process flexible beanpod structural carbon of acquisition, relative to Powder electrode material, without the need to adding extra conductive agent and collector, effectively can improve chemical property, and treatment process is reliable, can large-scale production, there is good industrialization prospect.
Therefore, vanadic oxide is dissolved in distilled water and adds oxalic acid reduction by the present invention, follow-up through a series of process, achieves the preparation obtaining the coated vanadium trioxide nano wire film of beanpod structural carbon, reliable preparation process, energy consumption is lower, and productive rate is high, the coated vanadium trioxide nano wire film of the beanpod structural carbon prepared by the method, size uniform, beanpod structure is obvious, and output is high, is applicable to electrochemical field.
Claims (7)
1. a preparation method for the coated vanadium trioxide nano wire film of beanpod structural carbon, is characterized in that, comprise the following steps: 1) prepare seven oxidation three vanadium nano wires, get 50mg sample and add water, stirs, obtains seven oxidation three vanadium overlong nanowire dispersion liquids; 2) above-mentioned uniform dispersion 40ml is got, then 50 ~ 500mg glucose is added, stir, mix, finally the above-mentioned solution mixed is poured in water heating kettle, oven temperature is risen to 180 DEG C, water heating kettle is put into baking oven insulation 0.5 ~ 5h, sample after water cleaning hydro-thermal, vacuum filtration film forming, is placed in drying box drying and obtains the coated seven oxidation three vanadium nano wire films of carbon; 3) sample film of drying and moulding is placed in tube furnace heat treatment, argon gas 400 ~ 1000 DEG C insulation 3h, naturally cools to room temperature with stove, obtains the coated vanadium trioxide nano wire film of beanpod structural carbon.
2. the preparation method of the coated vanadium trioxide nano wire film of beanpod structural carbon according to claim 1, it is characterized in that, described step 1) in seven oxidation three vanadium nano wires preparation methods be specially: get vanadic oxide yellow powder 0.524g and add water, ultrasonic, fully mix formation yellow solution, then 0.1443g bis-oxalic acid hydrate white powder is added, after stirring, solution is poured in water heating kettle, 210 DEG C of condition hydro-thermal 72h in an oven, finally cleaning is the dry seven oxidation three vanadium nano wires obtained also.
3. the preparation method of the coated vanadium trioxide nano wire film of beanpod structural carbon according to claim 1, is characterized in that, described step 1) in the rotating speed of blender be 600r/min, mixing time is 1h.
4. the preparation method of the coated vanadium trioxide nano wire film of beanpod structural carbon according to claim 1, is characterized in that, described step 2) baking temperature that is placed in drying box is 60 DEG C, drying time is more than 12h.
5. the coated vanadium trioxide nano wire film of preparation method's preparation-obtained beanpod structural carbon of the beanpod structural carbon coated vanadium trioxide nano wire film according to any one of Claims 1 to 4.
6. the coated vanadium trioxide nano wire film of beanpod structural carbon according to claim 5, it is characterized in that, this film is be interwoven by a large amount of nano wires in the longitudinal direction, described nano wire wraps up by carbon pipe the long nano wire of compound that the excellent or particle of the vanadium trioxide that extends along nanowire length direction of multistage formed, all have gap between described multistage vanadium trioxide rod or particle adjacent two sections thus present obvious cowpea pod structure, the length of every section of vanadium trioxide rod or particle is 200-500nm; The thickness of outer carbon-coating is about 10-100nm.
7. the application of the coated vanadium trioxide nano wire film of beanpod structural carbon according to claim 5 in lithium ion battery and ultracapacitor.
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| CN106684365A (en) * | 2017-01-23 | 2017-05-17 | 陕西科技大学 | Preparation of C-coated LiMn2O4 nanowire with high-temperature solid-state method |
| CN109650441A (en) * | 2018-12-19 | 2019-04-19 | 广东工业大学 | One kind seven aoxidizes three vanadium Zinc ion battery positive electrodes and preparation method thereof |
| CN110707301A (en) * | 2019-09-05 | 2020-01-17 | 珠海恒力源机电有限公司 | Vanadium trioxide/carbon composite material with nanosphere structure and preparation method and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106684365A (en) * | 2017-01-23 | 2017-05-17 | 陕西科技大学 | Preparation of C-coated LiMn2O4 nanowire with high-temperature solid-state method |
| CN109650441A (en) * | 2018-12-19 | 2019-04-19 | 广东工业大学 | One kind seven aoxidizes three vanadium Zinc ion battery positive electrodes and preparation method thereof |
| CN110707301A (en) * | 2019-09-05 | 2020-01-17 | 珠海恒力源机电有限公司 | Vanadium trioxide/carbon composite material with nanosphere structure and preparation method and application thereof |
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