CN104505509A - Carbon-coated porous vanadium nitride nanowire film and preparation method thereof - Google Patents
Carbon-coated porous vanadium nitride nanowire film and preparation method thereof Download PDFInfo
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Abstract
The invention specifically relates to a carbon-coated porous vanadium nitride nanowire film and a preparation method thereof. The preparation method comprises the following steps: 1) preparing vanadium pentoxide nanowires, and diluting the vanadium pentoxide nanowires by water to obtain a dispersion liquid with a concentration of 0.3mg/mL; 2) taking 100mL of the dispersion and uniformly stirring, adding trishydroxymethyl aminomethane buffering liquid and then stirring, then adding 10-200mg of dopamine hydrochloride, stirring for 0.5-4h until the solution is dark green, cleaning the polymerized sample by deionized water, and drying in a drying box to obtain a polydopamine-coated vanadium pentoxide nanowire film; 3) placing the dried-formed sample film in a tubular furnace and carrying out a heat treatment, insulating for 3h at 300-1000 DEG C under an NH3 condition, and naturally cooling to a room temperature with the furnace, so as to obtain the carbon-coated porous vanadium nitride nanowire film. The method disclosed by the invention is reliable in preparation process, low in energy consumption and high in yield; the prepared carbon-coated porous vanadium nitride nanowires are uniform in distribution, obvious in pore 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 porous vanadium nitride nano wire film of a kind of carbon and preparation method thereof.
Background technology
In recent years, because nano material has huge application prospect, be 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.VN is a kind of transition metal nitride, has feature [Xihong Lu, the Minghao Yu such as larger theoretical capacity, higher electron conductivity, wider potential windows scope due to it, Teng Zhai, Gongming Wang, Shilei Xie, Tianyu Liu, Chaolun Liang, Yexiang Tong, and Yat Li, Nano Lett.2013,13,2628-2633], be widely used in the field such as ultracapacitor, lithium ion battery material.And in the field such as lithium ion battery and ultracapacitor, because VN is very easily oxidized to VO as surface during electrode material
x, and this barium oxide very easily dissolves in aqueous electrolyte, causes the poor [Glushenkov of its electrochemical cycle stability, A.M., Hulicova-Jurcakova, D.L., lewellyn, D., Lu G.Q., Chen Y, Chem.Mater.2010,22 (3), 914-921], therefore have researcher to alleviate VN problem of oxidation by preparing nitride porous vanadium nano wire, its electrochemical cycle stability is improved, but still cannot overcome the problem of oxidation of VN superficial layer completely.
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 vanadium nitride is that fragility is larger, pure vanadium nitride can not form flexible electrode film.
Summary of the invention
The present invention is intended to overcome existing technological deficiency and achievement restriction, object is to provide coated porous vanadium nitride nano wire film of carbon of the simple and process of a kind of method and preparation method thereof, the coated vanadium nitride nano wire film of the carbon prepared by the method is without template, and size uniform, porous, 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 porous vanadium nitride nano wire film of carbon, comprises the following steps:
1) prepare vanadium pentoxide nanowires, and vanadium pentoxide nanowires dilute with water is obtained the dispersion liquid that concentration is 0.3mg/mL;
2) get above-mentioned dispersion liquid 100mL to stir, stir after adding trishydroxymethylaminomethane, add Dopamine hydrochloride 10 ~ 200mg again, stirring 0.5 ~ 4h is blackish green to solution, with sample after washed with de-ionized water polymerization, be placed in drying box drying and obtain the poly-coated vanadium pentoxide nanowires film of dopamine;
3) sample film of drying and moulding is placed in tube furnace heat treatment, NH
3under condition, 300 ~ 1000 DEG C of insulation 3h, naturally cool to room temperature with stove, obtain the coated porous vanadium nitride nano wire film of carbon.
In such scheme, described step 1) in the preparation method of vanadium pentoxide nanowires be specially: 2.73g vanadic oxide is dissolved in 25ml hydrogen peroxide, add distilled water to 300mL, mixing time is 0.5h, form transparent salmon solution, pour transparency liquid into water heating kettle, 180 DEG C of hot 96h of Water Under in drying box, finally, the vanadium pentoxide nanowires obtained is cleaned out.
In such scheme, the quality adding described trishydroxymethylaminomethane is 1mmol.
In such scheme, described step 2) in baking temperature be 60 DEG C, drying time is more than 12h.
The coated porous vanadium nitride nano wire film of the preparation-obtained carbon of preparation method of described carbon coated porous vanadium nitride nano wire film.
In such scheme, internal layer vanadium nitride nanowire width is 200-400nm, and length is more than 50 μm, and there is the consistent mesoporous hole that is evenly distributed; Outer carbon-coating is 5-7 nanometer.
The application of the coated porous vanadium nitride nano wire film of described carbon in lithium ion battery and ultracapacitor.
Adopt technique scheme, the present invention proposes the method for the coated vanadium nitride nano wire film of a kind of reliable carbon, adopt simple hydrothermal method, thus decrease much numerous and diverse operation, because vanadium in predecessor vanadic oxide is highest price state, under hydrogen peroxide effect, generate pervanadic acid, first vanadic oxide is under hydrone special adsorption, form flake, water-heat process releases energy, and makes thin slice cracking, thin slice after last cracking is curling due to tension force effect, thus forms the nano thread structure of size uniform.By the concentration of modulation dopamine (DA), can the thickness of the coated poly-dopamine (PDA) of modulation polymerization vanadium pentoxide nanowires, by the vanadium pentoxide nano wire film after PDA is coated, be placed in tube furnace, obtain the coated porous vanadium nitride nano wire film of carbon by ammonia annealing.
The present invention compared with prior art, has following beneficial effect:
1, the coated porous vanadium nitride nano wire of carbon prepared of the present invention, its even size distribution, there is a large amount of pore space structures, be conducive to the specific area improving material, and the problem that the cyclical stability that the oxidation of the effectively VN of preventing causes is poor, for the flowing of electrolyte and Ion transfer provide passage, shortens the transmission path of ion, effective alleviation Lithium-ion embeding and deviate from caused electrode material volume and change, has excellent chemical property.
2, the present invention's vanadium pentoxide nanowires of utilizing hydro thermal method to obtain, course of reaction, without additionally adding template, also without the need to adding additional surfactants, obtains the vanadium pentoxide nanowires of size uniform, and largely saved cost, and energy consumption is low, productive rate is high.
3, the present invention can control the thickness of the coated PDA of vanadic oxide by modulation condition DA concentration, finally reach the thickness of control surface carbon-coating, make it improve cycle performance, do not affect vanadium nitride electro-chemical activity again, make the chemical property optimization of material.
4, the present invention by annealing in ammonia, vanadic oxide nitrogenize coated for PDA is obtained the vanadium nitride of loose structure, by the pore space structure of size uniformity can be obtained after nitrogenize, be conducive to electrode material and fully contact with electrolyte and the assembling of electrochemical device.
5, the vanadium pentoxide nano wire prepared by hydro thermal method of the present invention, follow-up through the coated porous vanadium nitride nano wire film of a series of process flexible 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 hydrogen peroxide by the present invention, follow-up through a series of process, achieves the preparation obtaining the coated porous vanadium nitride nano wire film of carbon, reliable preparation process, energy consumption is lower, and productive rate is high, the carbon prepared by the method coated porous vanadium nitride flexible nano line film, size uniform, hole distribution is even, 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 porous vanadium nitride nano wire film of described carbon
Fig. 2 is the X ray diffracting spectrum of the coated porous vanadium nitride nano wire film of described carbon.
Fig. 3 is the transmission electron microscope high power front picture of the coated porous vanadium nitride nano wire film of described carbon;
Fig. 4 is the EDS power spectrum picture of the coated porous vanadium nitride nano wire film of described carbon.
Fig. 5 is the bending photo of described carbon coated porous vanadium nitride nano wire film.
Fig. 6 is after the coated porous vanadium nitride nano wire film of described carbon is prepared into electrode material, the multiplying power figure tested in 6M KOH electrolyte.
Fig. 7 is after the coated porous vanadium nitride nano wire film of described carbon is prepared into electrode material, the cycle graph tested in 6M KOH electrolyte.
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 carbon coated porous vanadium nitride nano wire fexible film of process, vanadic oxide is utilized to form orange-red solution as vanadium source as being dissolved in hydrogen peroxide, the more uniform vanadium pentoxide nanowires of size can be obtained through hydro-thermal, greatly reduce cost, then stir at certain density DA solution, at vanadic oxide surface aggregate one deck PDA film, form the coated vanadium pentoxide nanowires membrane structure of PDA, the process of follow-up process in ammonia, the nitride porous vanadium nano wire film that carbon is coated can be obtained, the loose structure of its size uniform, be more conducive to the embedding of lithium ion and deviate from, 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
The preparation method of the coated porous vanadium nitride nano wire film of a kind of carbon.First 2.73g vanadic oxide is dissolved in 25ml hydrogen peroxide, adding distilled water to liquor capacity is again 300ml, mixing time is 0.5h, form transparent salmon solution, pour transparency liquid into water heating kettle, in drying box, 180 DEG C of hot 96h of Water Under, finally, clean out the vanadium pentoxide nanowires obtained; Sample deionized water after cleaning is diluted to certain concentration, get dispersion liquid 100mL to stir, add Tris (trishydroxymethylaminomethane) and stir 2min afterwards, add Dopamine hydrochloride 10 ~ 30mg again, mixing time 0.5 ~ 1h is blackish green to solution, with sample after washed with de-ionized water polymerization, is placed in drying box, 60 degree of dry 12h, obtain the coated vanadium pentoxide nanowires film of PDA; The sample film of drying and moulding is placed in tube furnace heat treatment, NH
3under condition, 300 ~ 400 DEG C of insulation 3h, naturally cool to room temperature with stove and prepare the coated porous vanadium nitride nano wire film of carbon.
In the present embodiment: Dopamine hydrochloride 10 ~ 30mg, mixing time 0.5 ~ 1h, NH
3300 ~ 400 DEG C of insulation 3h under condition.
Can clearly be found out, in 2 θ=24 by the X ray diffracting spectrum of the coated porous vanadium nitride nano wire film of Fig. 2 carbon
°near there is diffraction maximum, the signal of corresponding carbon, because carbon is that non-type carbon causes its signal relatively mixed and disorderly, known by comparison card, the signal corresponding to other peak positions and JCPDS 73-2038 card completely, are the characteristic signal of VN.
Fig. 1 and Fig. 3 is respectively scanning electron microscopic picture and transmission electron microscope picture, can clearly find out, its carbon coated porous vanadium nitride film dimensions is longer, and be evenly distributed, and its carbon layers having thicknesses is thinner, general is 5-7 ran, very little to extending influence of ion, there are some holes between nano wire, illustrate that in nitridation process, vanadium pentoxide nanowires forms consistent meso-hole structure, not only construct larger specific area, and shorten the transmission path of ion, add the avtive spot of material, be conducive to electrolyte to contact more fully with electrode material, 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.
Fig. 5 further confirms that the material prepared by us has excellent flexible.Fig. 4 is the EDS power spectrum of the coated porous vanadium nitride material of carbon, by showing by spectrogram, we can clearly find out wherein there is the elements such as C, V, N, and completely the same with element contained by VN@C sample prepared by us, Cu element is element contained by conductive substrates copper sheet then.
Result proves by experiment, form the coated porous vanadium nitride nano wire film of carbon, effectively can improve chemical property, when Fig. 6 is shown as carbon coated porous pipe vanadium nitride nano wire film as electrode material, the high rate performance figure surveyed in 6MKOH electrolyte, from figure, we can clearly find out, under higher sweep speed 500mV/s, its specific capacity still can keep about 80% compared to the specific capacity under 100mV/s sweep speed, there is good high rate performance, when Fig. 7 is shown as the coated porous vanadium nitride nano wire film of carbon as electrode material, cyclical stability in 6MKOH electrolyte, known by curve chart, the 2000 recycle ratio capacity that its cyclical stability is mentioned compared to patent (201010548528.4) keep 88.4%, after 12000 circulations, specific capacity still can keep 92.4%, there is more excellent cyclical stability, there is huge application prospect.
Embodiment 2
The preparation method of the coated porous vanadium nitride nano wire film of a kind of carbon.First 2.73g vanadic oxide is dissolved in 25ml hydrogen peroxide, adding distilled water to liquor capacity is again 300ml, mixing time is 0.5h, form transparent salmon solution, pour transparency liquid into water heating kettle, in drying box, 180 DEG C of hot 96h of Water Under, finally, clean out the vanadium pentoxide nanowires obtained; Sample deionized water after cleaning is diluted to certain concentration, get dispersion liquid 100mL to stir, add Tris (trishydroxymethylaminomethane) to stir 2min afterwards and add Dopamine hydrochloride 10 ~ 30mg again, mixing time 1 ~ 2h is blackish green to solution, with sample after washed with de-ionized water polymerization, be placed in drying box, 60 degree of dry 12h, obtain the coated vanadium pentoxide nanowires film of PDA; The sample film of drying and moulding is placed in tube furnace heat treatment, NH
3under condition, 400 ~ 500 DEG C of insulation 3h, naturally cool to room temperature with stove and prepare the coated porous vanadium nitride nano wire film of carbon.
In the present embodiment: Dopamine hydrochloride 10 ~ 30mg, mixing time 1 ~ 2h, NH
3400 ~ 500 DEG C of insulation 3h under condition.
Embodiment 3
The preparation method of the coated porous vanadium nitride nano wire film of a kind of carbon.First 2.73g vanadic oxide is dissolved in 25ml hydrogen peroxide, adding distilled water to liquor capacity is again 300ml, mixing time is 0.5h, form transparent salmon solution, pour transparency liquid into water heating kettle, in drying box, 180 DEG C of hot 96h of Water Under, finally, clean out the vanadium pentoxide nanowires obtained; Sample deionized water after cleaning is diluted to certain concentration, get dispersion liquid 100mL to stir, add Tris (trishydroxymethylaminomethane) to stir 2min afterwards and add Dopamine hydrochloride 30 ~ 50mg again, mixing time 2 ~ 4h is blackish green to solution, with sample after washed with de-ionized water polymerization, be placed in drying box, 60 degree of dry 12h, obtain the coated vanadium pentoxide nanowires film of PDA; The sample film of drying and moulding is placed in tube furnace heat treatment, NH
3under condition, 300 ~ 400 DEG C of insulation 3h, naturally cool to room temperature with stove and prepare the coated porous vanadium nitride nano wire film of carbon.
In the present embodiment: Dopamine hydrochloride 30 ~ 50mg, mixing time 2 ~ 4h, NH
3300 ~ 400 DEG C of insulation 3h under condition.
Embodiment 4
The preparation method of the coated porous vanadium nitride nano wire film of a kind of carbon.First 2.73g vanadic oxide is dissolved in 25ml hydrogen peroxide, adding distilled water to liquor capacity is again 300ml, mixing time is 0.5h, form transparent salmon solution, pour transparency liquid into water heating kettle, in drying box, 180 DEG C of hot 96h of Water Under, finally, clean out the vanadium pentoxide nanowires obtained; Sample deionized water after cleaning is diluted to certain concentration, get dispersion liquid 100mL to stir, add Tris (trishydroxymethylaminomethane) to stir 2min afterwards and add Dopamine hydrochloride 30 ~ 50mg again, mixing time 1 ~ 2h is blackish green to solution, with sample after washed with de-ionized water polymerization, be placed in drying box, 60 degree of dry 12h, obtain the coated vanadium pentoxide nanowires film of PDA; The sample film of drying and moulding is placed in tube furnace heat treatment, NH
3under condition, 400 ~ 500 DEG C of insulation 3h, naturally cool to room temperature with stove and prepare the coated porous vanadium nitride nano wire film of carbon.
In the present embodiment: Dopamine hydrochloride 30 ~ 50mg, mixing time 1 ~ 2h, NH
3400 ~ 500 DEG C of insulation 3h under condition.
Embodiment 5
The preparation method of the coated porous vanadium nitride nano wire film of a kind of carbon.First 2.73g vanadic oxide is dissolved in 25ml hydrogen peroxide, adding distilled water to liquor capacity is again 300ml, mixing time is 0.5h, form transparent salmon solution, pour transparency liquid into water heating kettle, in drying box, 180 DEG C of hot 96h of Water Under, finally, clean out the vanadium pentoxide nanowires obtained; Sample deionized water after cleaning is diluted to certain concentration, get dispersion liquid 100mL to stir, add Tris (trishydroxymethylaminomethane) to stir 2min afterwards and add Dopamine hydrochloride 30 ~ 50mg again, mixing time 1 ~ 2h is blackish green to solution, with sample after washed with de-ionized water polymerization, be placed in drying box, 60 degree of dry 12h, obtain the coated vanadium pentoxide nanowires film of PDA; The sample film of drying and moulding is placed in tube furnace heat treatment, NH
3under condition, 500 ~ 600 DEG C of insulation 3h, naturally cool to room temperature with stove and prepare the coated porous vanadium nitride nano wire film of carbon.
In the present embodiment: Dopamine hydrochloride 30 ~ 50mg, mixing time 1 ~ 2h, NH
3500 ~ 600 DEG C of insulation 3h under condition.
Embodiment 6
The preparation method of the coated porous vanadium nitride nano wire film of a kind of carbon.First 2.73g vanadic oxide is dissolved in 25ml hydrogen peroxide, adding distilled water to liquor capacity is again 300ml, mixing time is 0.5h, form transparent salmon solution, pour transparency liquid into water heating kettle, in drying box, 180 DEG C of hot 96h of Water Under, finally, clean out the vanadium pentoxide nanowires obtained; Sample deionized water after cleaning is diluted to certain concentration, get dispersion liquid 100mL to stir, add Tris (trishydroxymethylaminomethane) to stir 2min afterwards and add Dopamine hydrochloride 50 ~ 70mg again, mixing time 0.5 ~ 1h is blackish green to solution, with sample after washed with de-ionized water polymerization, be placed in drying box, 60 degree of dry 12h, obtain the coated vanadium pentoxide nanowires film of PDA; The sample film of drying and moulding is placed in tube furnace heat treatment, NH
3under condition, 600 ~ 700 DEG C of insulation 3h, naturally cool to room temperature with stove and prepare the coated porous vanadium nitride nano wire film of carbon.
In the present embodiment: Dopamine hydrochloride 50 ~ 70mg, mixing time 0.5 ~ 1h, NH
3600 ~ 700 DEG C of insulation 3h under condition.
Embodiment 7
The preparation method of the coated porous vanadium nitride nano wire film of a kind of carbon.First 2.73g vanadic oxide is dissolved in 25ml hydrogen peroxide, adding distilled water to liquor capacity is again 300ml, mixing time is 0.5h, form transparent salmon solution, pour transparency liquid into water heating kettle, in drying box, 180 DEG C of hot 96h of Water Under, finally, clean out the vanadium pentoxide nanowires obtained; Sample deionized water after cleaning is diluted to certain concentration, get dispersion liquid 100mL to stir, add Tris (trishydroxymethylaminomethane) to stir 2min afterwards and add Dopamine hydrochloride 50 ~ 70mg again, mixing time 0.5 ~ 1h is blackish green to solution, with sample after washed with de-ionized water polymerization, be placed in drying box, 60 degree of dry 12h, obtain the coated vanadium pentoxide nanowires film of PDA; The sample film of drying and moulding is placed in tube furnace heat treatment, NH
3under condition, 700 ~ 800 DEG C of insulation 3h, naturally cool to room temperature with stove and prepare the coated porous vanadium nitride nano wire film of carbon.
In the present embodiment: Dopamine hydrochloride 50 ~ 70mg, mixing time 0.5 ~ 1h, NH
3700 ~ 800 DEG C of insulation 3h under condition.
Embodiment 8
The preparation method of the coated porous vanadium nitride nano wire film of a kind of carbon.First 2.73g vanadic oxide is dissolved in 25ml hydrogen peroxide, adding distilled water to liquor capacity is again 300ml, mixing time is 0.5h, form transparent salmon solution, pour transparency liquid into water heating kettle, in drying box, 180 DEG C of hot 96h of Water Under, finally, clean out the vanadium pentoxide nanowires obtained; Sample deionized water after cleaning is diluted to certain concentration, get dispersion liquid 100mL to stir, add Tris (trishydroxymethylaminomethane) to stir 2min afterwards and add Dopamine hydrochloride 50 ~ 70mg again, mixing time 1 ~ 2h is blackish green to solution, with sample after washed with de-ionized water polymerization, be placed in drying box, 60 degree of dry 12h, obtain the coated vanadium pentoxide nanowires film of PDA; The sample film of drying and moulding is placed in tube furnace heat treatment, NH
3under condition, 800 ~ 900 DEG C of insulation 3h, naturally cool to room temperature with stove and prepare the coated porous vanadium nitride nano wire film of carbon.
In the present embodiment: Dopamine hydrochloride 50 ~ 70mg, mixing time 1 ~ 2h, NH
3800 ~ 900 DEG C of insulation 3h under condition.
Embodiment 9
The preparation method of the coated porous vanadium nitride nano wire film of a kind of carbon.First 2.73g vanadic oxide is dissolved in 25ml hydrogen peroxide, adding distilled water to liquor capacity is again 300ml, mixing time is 0.5h, form transparent salmon solution, pour transparency liquid into water heating kettle, in drying box, 180 DEG C of hot 96h of Water Under, finally, clean out the vanadium pentoxide nanowires obtained; Sample deionized water after cleaning is diluted to certain concentration, get dispersion liquid 100mL to stir, add Tris (trishydroxymethylaminomethane) to stir 2min afterwards and add Dopamine hydrochloride 70 ~ 100mg again, mixing time 0.5 ~ 1h is blackish green to solution, with sample after washed with de-ionized water polymerization, be placed in drying box, 60 degree of dry 12h, obtain the coated vanadium pentoxide nanowires film of PDA; The sample film of drying and moulding is placed in tube furnace heat treatment, NH
3under condition, 500 ~ 600 DEG C of insulation 3h, naturally cool to room temperature with stove and prepare the coated porous vanadium nitride nano wire film of carbon.
In the present embodiment: Dopamine hydrochloride 70 ~ 100mg, mixing time 0.5 ~ 1h, NH
3500 ~ 600 DEG C of insulation 3h under condition.
Embodiment 10
The preparation method of the coated porous vanadium nitride nano wire film of a kind of carbon.First 2.73g vanadic oxide is dissolved in 25ml hydrogen peroxide, adding distilled water to liquor capacity is again 300ml, mixing time is 0.5h, form transparent salmon solution, pour transparency liquid into water heating kettle, in drying box, 180 DEG C of hot 96h of Water Under, finally, clean out the vanadium pentoxide nanowires obtained; Sample deionized water after cleaning is diluted to certain concentration, get dispersion liquid 100mL to stir, add Tris (trishydroxymethylaminomethane) to stir 2min afterwards and add Dopamine hydrochloride 100 ~ 200mg again, mixing time 0.5 ~ 1h is blackish green to solution, with sample after washed with de-ionized water polymerization, be placed in drying box, 60 degree of dry 12h, obtain the coated vanadium pentoxide nanowires film of PDA; The sample film of drying and moulding is placed in tube furnace heat treatment, NH
3under condition, 900 ~ 1000 DEG C of insulation 3h, naturally cool to room temperature with stove and prepare the coated porous vanadium nitride nano wire film of carbon.
In the present embodiment: Dopamine hydrochloride 100 ~ 200mg, mixing time 0.5 ~ 1hNH
3900 ~ 1000 DEG C of insulation 3h under condition.
The present invention compared with prior art, has following good effect:
1, the coated porous vanadium nitride nano wire of carbon prepared of the present invention, its even size distribution, there is a large amount of pore space structures, be conducive to the specific area improving material, and provide one dimension passage for the flowing of electrolyte and Ion transfer, shorten the transmission path of ion, effectively alleviate Lithium-ion embeding and deviate from caused electrode material volume and become, there is the chemical property of excellence.
2, the present invention's vanadium pentoxide nanowires of utilizing hydro thermal method to obtain, course of reaction, without additionally adding template, does not add additional surfactants yet, obtain the vanadium pentoxide nanowires of size uniform, and largely saved cost, and energy consumption is low, productive rate is high.
3, the present invention can control the thickness of the coated PDA of vanadic oxide by modulation condition DA concentration, thus can obtain the better electrode material of electrochemistry combination property better as required.
4, the present invention by annealing in ammonia, vanadic oxide nitrogenize coated for PDA is obtained the vanadium nitride of loose structure, by the pore space structure of size uniformity can be obtained after nitrogenize, be conducive to electrode material and fully contact with electrolyte and the assembling of electrochemical device.
5, the vanadium pentoxide nano wire prepared by hydro thermal method of the present invention, follow-uply obtains the coated porous vanadium nitride nano wire film of carbon through a series of process, and treatment process is reliable, can large-scale production, has good industrialization prospect.
Therefore, vanadic oxide is dissolved in hydrogen peroxide by the present invention, follow-up through a series of process, achieves the preparation obtaining the coated porous vanadium nitride nano wire film of carbon, reliable preparation process, energy consumption is lower, and productive rate is high, the coated porous vanadium nitride nano wire film of the carbon prepared by the method, size uniform, hole distribution is even, and output is high, is applicable to electrochemical field.
Claims (7)
1. a preparation method for the coated porous vanadium nitride nano wire film of carbon, is characterized in that, comprise the following steps:
1) prepare vanadium pentoxide nanowires, and vanadium pentoxide nanowires dilute with water is obtained the dispersion liquid that concentration is 0.3mg/mL;
2) get above-mentioned dispersion liquid 100mL to stir, stir after adding trishydroxymethylaminomethane, add Dopamine hydrochloride 10 ~ 200mg again, stirring 0.5 ~ 4h is blackish green to solution, with sample after washed with de-ionized water polymerization, be placed in drying box drying and obtain the poly-coated vanadium pentoxide nanowires film of dopamine;
3) sample film of drying and moulding is placed in tube furnace heat treatment, NH
3under condition, 300 ~ 1000 DEG C of insulation 3h, naturally cool to room temperature with stove, obtain the coated porous vanadium nitride nano wire film of carbon.
2. the preparation method of the coated porous vanadium nitride nano wire film of carbon according to claim 1, it is characterized in that, described step 1) in the preparation method of vanadium pentoxide nanowires be specially: 2.73g vanadic oxide is dissolved in 25ml hydrogen peroxide, add distilled water to 300mL, mixing time is 0.5h, forms transparent salmon solution, pour transparency liquid into water heating kettle, in drying box, 180 DEG C of hot 96h of Water Under, finally, clean out the vanadium pentoxide nanowires obtained.
3. the preparation method of the coated porous vanadium nitride nano wire film of carbon according to claim 1, is characterized in that, the quality adding described trishydroxymethylaminomethane is 1mmol.
4. the preparation method of the coated porous vanadium nitride nano wire film of carbon according to claim 1, is characterized in that, described step 2) in baking temperature be 60 DEG C, drying time is more than 12h.
5. the coated porous vanadium nitride nano wire film of the preparation-obtained carbon of preparation method of the coated porous vanadium nitride of the carbon according to any one of Claims 1 to 4 nano wire film.
6. the coated porous vanadium nitride nano wire film of carbon according to claim 5, is characterized in that, internal layer vanadium nitride nanowire width is 200-400nm, and length is more than 50 μm, and there is the consistent mesoporous hole that is evenly distributed; The thickness of outer carbon-coating is 5-7 nanometer.
7. the application of the coated porous vanadium nitride nano wire film of carbon according to claim 1 in lithium ion battery and ultracapacitor.
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