CN102534630B - Porous titanium nitride nanotube array film and preparation method thereof - Google Patents
Porous titanium nitride nanotube array film and preparation method thereof Download PDFInfo
- Publication number
- CN102534630B CN102534630B CN201210027249.2A CN201210027249A CN102534630B CN 102534630 B CN102534630 B CN 102534630B CN 201210027249 A CN201210027249 A CN 201210027249A CN 102534630 B CN102534630 B CN 102534630B
- Authority
- CN
- China
- Prior art keywords
- metal plate
- titanium nitride
- array film
- titanium metal
- nanotube array
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The invention particularly relates to a porous titanium nitride nanotube array film and a preparation method thereof. The technical scheme of the method is that: first, a polished and buffed titaniferous metal sheet is used as an anode to be put into electrolyte for carrying out anodic oxidation, the voltage of anodic oxidation is 10-60 V, and the time of anodic oxidation is 0.5-5 hours; then the titaniferous metal sheet after anodic oxidation is washed and dried, and the dried titaniferous metal sheet is subjected to annealing treatment at the temperature of 300 to 600 DEG C in the air; finally the titaniferous metal sheet after the annealing treatment is subjected to annealing at the temperature of 300 to 600 DEG C in the atmosphere that the volume of a nitrogenous precursor is 10-100 percent at a speed of 1-20 DEG C/min, and is cooled along a furnace; and the titanium nitride nanotube array film is obtained on the surface of the titaniferous metal sheet. The preparation method disclosed by the invention is simple, and the process is reliable. The prepared porous titanium nitride nanotube array film is uniformly distributed with nanometer-size holes from a tube mouth to a tube bottom, and the size of the holes can be adjusted. The porous titanium nitride nanotube array film is suitable for the field of electrochemistry.
Description
Technical field
The invention belongs to the nano composite structure technical field.Be specifically related to a kind of porous titanium nitride nanotube array film and preparation method thereof.
Technical background
In recent years, nano material, due to its great scientific value and potential using value, has caused people's extensive concern.Theoretical and experimental study shows, with respect to block materials, nanostructure shows more superior performance.Particularly monodimension nanometer material (as nano wire and nanotube) has the electronic conduction passage of one dimension, thereby shows excellent photoelectrochemical behaviour.TiN is a kind of good metalloid material, due to its good conductivity and wear resisting property, stable Physicochemical performance, low-cost and nontoxic characteristics, and the precious metal such as TiN and Pt has similar electron structure [E. Furimsky, Appl. Catal. A 2003, 240, 1.[20] Q.W. Jiang, G. R. Li, X. P. Gao, Chem. Commun. 2009, 6720.], and there is good corrosion resistance [Q.W. Jiang in the electrolytic solution such as KOH, G.R. Li, X.P. Gao, Chem. Commun. (2009) 6720.] be widely used in solar cell, superconducting material and energy and material Material Field.And all wish that TiN has larger specific surface area, the performance of favourable absorption electrolytic solution in the fields such as solar cell and lithium ion battery and ultracapacitor.Porous material due to its large specific surface area and easily the material transfer passage be widely used in solar cell, the electrical condenser ecosphere is with a wide range of applications.Porous material is because it has huge specific surface area and three-dimensional passage, thereby is conducive to flowing and the migration of ion of electrolytic solution, becomes one of solar cell, lithium ion battery and the optimal material of ultracapacitor.
The patent of relevant preparation TiN powder has much at present, the method related to has gas assisted evaporative method, fused salt electrolysis process, the plasma chemical gas-phase reaction method, as " preparation method of TiN nano-powder " (200810062468.8) technology, the metallic titanium powder direct oxidation method, and mechanical alloying method etc.By fused salt electrolysis process or in nitrogen containing atmosphere ball milling metal titanium powder production unit require highly, cost is higher, and the high-energy ball milling method impurity in products is many.The TiN film is due to higher in the visible region transmissivity and higher at the near-infrared region reflectivity, thereby is widely used in the low emissivity glass field.The method of relevant synthetic TiN film, the general magnetron sputtering chemical gas-phase method that adopts deposits the even compact film on metal base or semiconductor base, as " a kind of method of utilizing magnetically controlled DC sputtering to prepare colored TiN film " (201110102624.0) patented technology.The method of same poromerics also much comprises the employing polymkeric substance, and silicon oxide and other organism are template, but nitride carbide porous material is but studied less.Jin Ho Bang etc. adopt Zn
2tiO
4for precursor, in the high temperature annealing ammonification, Zn is evaporated simultaneously, obtain porous TiN microballoon [Adv. Mater. 2009,21,3186 – 3190].But also there is no relevant patent and the synthesizing porous TiN nano-pipe array thin film of report.
Summary of the invention
Purport of the present invention overcomes existing technological deficiency, purpose is to provide a kind of method simply and the preparation method of the porous titanium nitride nanotube array film of process, and the porous titanium nitride nanotube array film prepared by the method is distributed with the hole of nano-scale from the mouth of pipe to the pipe bottom even.
For achieving the above object, the technical solution used in the present invention is: first, using containing titanium metal plate, as anode, inserting in electrolytic solution and carrying out anodic oxidation after grinding and buffing, anodised voltage is 10 ~ 60V, and the anodised time is 0.5 ~ 5 hour; Again by being cleaned containing titanium metal plate after anodic oxidation, dry, then carry out anneal containing titanium metal plate by dried under 300 ~ 600 ℃ of conditions in air, finally by after anneal containing titanium metal plate under 300 ~ 800 ℃ of conditions, in the atmosphere that the volume content of nitrogen-containing precursor is 10～100%, with the speed of 1～20 ℃/min, annealed, furnace cooling, obtaining titanium nitride nano pipe array film containing the titanium metal plate surface.
The described titanium content containing titanium metal plate is 50 ~ 99.99wt%.
Described polishing is that the titanium metal plate that contains after first polishing successively carries out ultrasonic cleaning with ethanol, acetone and distilled water respectively, then at HF ︰ HNO
3︰ H
2the volume ratio of O is that (carry out chemical rightenning in the solution of 2 ~ 5) ︰ (4 ~ 7), the time of chemical rightenning is 3～10min to 1 ︰; Then clean with distilled water, dry up with nitrogen.
The Na that described electrolytic solution is 1 ~ 20wt%
2sO
4, the citric acid of 0 ~ 2wt%, the fluoride ion of 0.05 ~ 5wt% and the H of 75 ~ 98wt%
2the mixing solutions of O, or be the fluoride ion of 0.05 ~ 5wt%, the H of 0.5 ~ 35wt%
2the mixing solutions of the ethylene glycol of O and 60 ~ 99wt%, or be the fluoride ion of 0.05 ~ 5wt%, the H of 0.5 ~ 35wt%
2the mixing solutions of the glycerol of O and 60 ~ 99wt%.
Described cleaning is by containing titanium metal plate, from electrolytic solution, taking out and being placed in baking oven after anodic oxidation, be incubated 0.5 ~ 3 hour under 100 ~ 600 ℃ of conditions in air, cooling rear taking-up, in the mixing solutions of methyl alcohol and water or ultrasonic cleaning in the mixing solutions of ethanol and water.
Described nitrogen-containing precursor is more than one in ammonia, pyridine and acetonitrile.
Described fluoride ion is KF, NaF, NH
4more than one in F and HF.
Owing to adopting technique scheme, the present invention proposes a kind of simple and reliable method for preparing porous titanium nitride nanotube array film, utilizes nitrogen-containing precursor as nitrogenous source, adopts simple annealing method, thereby has reduced a lot of numerous and diverse operations.Due to precursor TiO
2be Detitanium-ore-type, and be gradually transformed into a cube TiN after nitrogen-containing precursor is reacted, the lattice parameter of nano-pipe array thin film is changed, thereby form vesicular structure.By controlling nitriding temperature, thereby control the size in nanotube tube wall aperture.Because TiN has good electroconductibility, the tube wall vesicular structure has large specific surface area, and infiltration and the mobile unlimited system that a three-dimensional is provided for electrolytic solution, being conducive to the electrolytic solution intermediate ion passes in and out in electrode interior, can regulate according to the kind of electrolytic solution the size of hole, thereby be conducive to the coupling of electrolytic solution and electrode materials.The results show, form the porous titanium nitride nano-tube array and can effectively improve chemical property.
The present invention adopts simple annealing method, by after anodic oxidation containing titanium metal plate high-temperature ammonolysis under nitrogen-containing precursor atmosphere, change the titanium nitride nano pipe of porous into, and regulate and control the aperture of nanotube tube wall by nitriding temperature and heat-up rate, realized the controlled preparation of porous titanium nitride nanotube array film.
The present invention compared with prior art, has following positively effect:
1, the porous titanium nitride nano-tube array that prepared by the present invention, its tube wall hole from the top to the bottom is evenly distributed, be conducive to improve the nanotube specific surface area, and flowing that its tube wall vesicular structure is electrolytic solution provides three-dimensional channel with ion migration, titanium nitride has high electronic migration ability and anti-electrolytic solution corrosive power, thereby has good chemical property and recycle performance.
2, the present invention utilizes nitriding temperature and heat-up rate to control the nitridation of titanium oxide nanotubes, further to control the size in titanium nitride nano tube wall aperture, thereby can select as required better the kind of electrolytic solution, the matching degree of effectively regulating electrode materials and electrolytic solution.
3, the present invention passes through brief heat treating by the titanium metal plate that contains after anodic oxidation, and the original position on titanium metal plate that contains after anodic oxidation generates porous titanium nitride nanotube array film, and treatment process is simple, and cost is lower.
4, the present invention is containing preparing porous titanium nitride nanotube array film on titanium metal plate, can scale operation, there is good industrialization prospect.
Therefore, the present invention passes through brief heat treating by the titanium metal plate that contains after anodic oxidation, realized the preparation of porous titanium nitride nanotube array film, simple and the process of preparation method, the porous titanium nitride nanotube array film prepared by the method is distributed with the hole of nano-scale from the mouth of pipe to the pipe bottom even, hole size is adjustable, is applicable to electrochemical field.
The accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum of a kind of porous titanium nitride nanotube array film of preparing of the present invention.
Fig. 2 is the scanning electron microscope full face of the described porous titanium nitride nanotube array film of Fig. 1;
Fig. 3 is the scanning electron microscope cross-section photograph of the described porous titanium nitride nanotube array film of Fig. 1.
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 domain.
For avoiding repetition, first the technique unification of the polishing of this embodiment and cleaning is described below, in embodiment, repeat no more:
Polishing is that the titanium metal plate that contains after first polishing successively carries out ultrasonic cleaning with ethanol, acetone and distilled water respectively, then at HF ︰ HNO
3︰ H
2the volume ratio of O is that (carry out chemical rightenning in the solution of 2 ~ 5) ︰ (4 ~ 7), the time of chemical rightenning is 3～10min to 1 ︰; Then clean with distilled water, dry up with nitrogen.
Cleaning is by containing titanium metal plate, from electrolytic solution, taking out and being placed in baking oven after anodic oxidation, be incubated 0.5 ~ 3 hour under 100 ~ 600 ℃ of conditions in air, cooling rear taking-up, in the mixing solutions of methyl alcohol and water or ultrasonic cleaning in the mixing solutions of ethanol and water.
embodiment 1
A kind of porous titanium nitride nanotube array film and preparation method thereof.First, using containing titanium metal plate, as anode, inserting in electrolytic solution and carrying out anodic oxidation after grinding and buffing, anodised voltage is 40 ~ 60V, and the anodised time is 0.5 ~ 2.0 hour; Again by being cleaned containing titanium metal plate after anodic oxidation, dry, then carry out anneal containing titanium metal plate by dried under 300 ~ 400 ℃ of conditions in air, finally by after anneal containing titanium metal plate under 300 ~ 450 ℃ of conditions, in the atmosphere that the volume content of nitrogen-containing precursor is 10～40%, with the speed of 12～20 ℃/min, annealed, furnace cooling, obtaining titanium nitride nano pipe array film containing the titanium metal plate surface.
In the present embodiment: the titanium content containing titanium metal plate is 50 ~ 70 wt%; The H of the fluoride ion that electrolytic solution is 0.05 ~ 0.5 wt%, 0.5 ~ 5 wt%
2the mixing solutions of the ethylene glycol of O and 95 ~ 99 wt%, fluoride ion wherein is NH
4f; The mixed gas that nitrogen-containing precursor is ammonia and acetonitrile.
embodiment 2
A kind of porous titanium nitride nanotube array film and preparation method thereof.First, using containing titanium metal plate, as anode, inserting in electrolytic solution and carrying out anodic oxidation after grinding and buffing, anodised voltage is 40 ~ 60V, and the anodised time is 0.5 ~ 2.0 hour; Again by being cleaned containing titanium metal plate after anodic oxidation, dry, then carry out anneal containing titanium metal plate by dried under 350 ~ 450 ℃ of conditions in air, finally by after anneal containing titanium metal plate under 400 ~ 600 ℃ of conditions, in the atmosphere that the volume content of nitrogen-containing precursor is 20～60%, with the speed of 3～10 ℃/min, annealed, furnace cooling, obtaining titanium nitride nano pipe array film containing the titanium metal plate surface.
In the present embodiment: the titanium content containing titanium metal plate is 60 ~ 80 wt%; The H of the fluoride ion that electrolytic solution is 0.3 ~ 0.8 wt%, 2 ~ 15 wt%
2the mixing solutions of the ethylene glycol of O and 85 ~ 95 wt%, fluoride ion wherein is NH
4the mixture of F and NaF; The mixed gas that nitrogen-containing precursor is ammonia and pyridine.
A kind of porous titanium nitride nanotube array film and preparation method thereof.First, using containing titanium metal plate, as anode, inserting in electrolytic solution and carrying out anodic oxidation after grinding and buffing, anodised voltage is 40 ~ 60V, and the anodised time is 0.5 ~ 2.0 hour; Again by being cleaned containing titanium metal plate after anodic oxidation, dry, then carry out anneal containing titanium metal plate by dried under 500 ~ 600 ℃ of conditions in air, finally by after anneal containing titanium metal plate under 550 ~ 700 ℃ of conditions, in the atmosphere that the volume content of nitrogen-containing precursor is 50～90%, with the speed of 9～15 ℃/min, annealed, furnace cooling, obtaining titanium nitride nano pipe array film containing the titanium metal plate surface.
In the present embodiment: the titanium content containing titanium metal plate is 80 ~ 95 wt%; The H of the fluoride ion that electrolytic solution is 0.8 ~ 3.0 wt%, 5 ~ 20 wt%
2the mixing solutions of the ethylene glycol of O and 80 ~ 85 wt%, fluoride ion wherein is NH
4the mixture of F and KF; The mixed gas that nitrogen-containing precursor is ammonia, acetonitrile and pyridine.
embodiment 4
A kind of porous titanium nitride nanotube array film and preparation method thereof.First, using containing titanium metal plate, as anode, inserting in electrolytic solution and carrying out anodic oxidation after grinding and buffing, anodised voltage is 40 ~ 60V, and the anodised time is 0.5 ~ 2.0 hour; Again by being cleaned containing titanium metal plate after anodic oxidation, dry, then carry out anneal containing titanium metal plate by dried under 450 ~ 550 ℃ of conditions in air, finally by after anneal containing titanium metal plate under 650 ~ 800 ℃ of conditions, in the atmosphere that the volume content of nitrogen-containing precursor is 80～100%, with the speed of 1～6 ℃/min, annealed, furnace cooling, obtaining titanium nitride nano pipe array film containing the titanium metal plate surface.
In the present embodiment: the titanium content containing titanium metal plate is 95 ~ 99.99 wt%; The H of the fluoride ion that electrolytic solution is 1.5 ~ 5.0 wt%, 15 ~ 35 wt%
2the mixing solutions of the ethylene glycol of O and 60 ~ 80 wt%, fluoride ion wherein is NH
4the mixture of F and HF; Nitrogen-containing precursor is ammonia.
embodiment 5
A kind of porous titanium nitride nanotube array film and preparation method thereof.First, using containing titanium metal plate, as anode, inserting in electrolytic solution and carrying out anodic oxidation after grinding and buffing, anodised voltage is 30 ~ 50V, and the anodised time is 4.0 ~ 5.0 hours; Again by being cleaned containing titanium metal plate after anodic oxidation, dry, then carry out anneal containing titanium metal plate by dried under 300 ~ 400 ℃ of conditions in air, finally by after anneal containing titanium metal plate under 300 ~ 450 ℃ of conditions, in the atmosphere that the volume content of nitrogen-containing precursor is 10～40%, with the speed of 12～20 ℃/min, annealed, furnace cooling, obtaining titanium nitride nano pipe array film containing the titanium metal plate surface.
In the present embodiment: the titanium content containing titanium metal plate is 50 ~ 70 wt%; The H of the fluoride ion that electrolytic solution is 0.05 ~ 0.5 wt%, 0.5 ~ 5 wt%
2the mixing solutions of the ethylene glycol of O and 95 ~ 99 wt%, fluoride ion wherein is HF; State the mixed gas that nitrogen-containing precursor is acetonitrile and pyridine.
embodiment 6
A kind of porous titanium nitride nanotube array film and preparation method thereof.First, using containing titanium metal plate, as anode, inserting in electrolytic solution and carrying out anodic oxidation after grinding and buffing, anodised voltage is 30 ~ 50V, and the anodised time is 4.0 ~ 5.0 hours; Again by being cleaned containing titanium metal plate after anodic oxidation, dry, then carry out anneal containing titanium metal plate by dried under 350 ~ 450 ℃ of conditions in air, finally by after anneal containing titanium metal plate under 400 ~ 600 ℃ of conditions, in the atmosphere that the volume content of nitrogen-containing precursor is 20～60%, with the speed of 3～10 ℃/min, annealed, furnace cooling, obtaining titanium nitride nano pipe array film containing the titanium metal plate surface.
In the present embodiment: the titanium content containing titanium metal plate is 60 ~ 80wt%; The H of the fluoride ion that electrolytic solution is 0.3 ~ 0.8 wt%, 2 ~ 15 wt%
2the mixing solutions of the ethylene glycol of O and 85 ~ 95 wt%, the mixture that fluoride ion wherein is HF and NaF; The mixed gas that nitrogen-containing precursor is ammonia, acetonitrile and pyridine.
embodiment 7
A kind of porous titanium nitride nanotube array film and preparation method thereof.First, using containing titanium metal plate, as anode, inserting in electrolytic solution and carrying out anodic oxidation after grinding and buffing, anodised voltage is 30 ~ 50V, and the anodised time is 4.0 ~ 5.0 hours; Again by being cleaned containing titanium metal plate after anodic oxidation, dry, then carry out anneal containing titanium metal plate by dried under 500 ~ 600 ℃ of conditions in air, finally by after anneal containing titanium metal plate under 550 ~ 700 ℃ of conditions, in the atmosphere that the volume content of nitrogen-containing precursor is 50～90%, with the speed of 9～15 ℃/min, annealed, furnace cooling, obtaining titanium nitride nano pipe array film containing the titanium metal plate surface.
In the present embodiment: the titanium content containing titanium metal plate is 80 ~ 95 wt%; The H of the fluoride ion that electrolytic solution is 0.05 ~ 0.5 wt%, 0.5 ~ 5 wt%
2the mixing solutions of the ethylene glycol of O and 95 ~ 99 wt%, fluoride ion wherein is NH
4the mixture of F, KF and NaF; The mixed gas that nitrogen-containing precursor is ammonia and acetonitrile.
embodiment 8
A kind of porous titanium nitride nanotube array film and preparation method thereof.First, using containing titanium metal plate, as anode, inserting in electrolytic solution and carrying out anodic oxidation after grinding and buffing, anodised voltage is 30 ~ 50V, and the anodised time is 4.0 ~ 5.0 hours; Again by being cleaned containing titanium metal plate after anodic oxidation, dry, then carry out anneal containing titanium metal plate by dried under 450 ~ 550 ℃ of conditions in air, finally by after anneal containing titanium metal plate under 650 ~ 800 ℃ of conditions, in the atmosphere that the volume content of nitrogen-containing precursor is 80～100%, with the speed of 1～6 ℃/min, annealed, furnace cooling, obtaining titanium nitride nano pipe array film containing the titanium metal plate surface.
In the present embodiment: the titanium content containing titanium metal plate is 95 ~ 99.99 wt%; The H of the fluoride ion that electrolytic solution is 1.5 ~ 5.0 wt%, 15 ~ 35 wt%
2the mixing solutions of the ethylene glycol of O and 60 ~ 80 wt%, the mixture that fluoride ion wherein is KF and HF; Nitrogen-containing precursor is acetonitrile.
embodiment 9
A kind of porous titanium nitride nanotube array film and preparation method thereof.First, using containing titanium metal plate, as anode, inserting in electrolytic solution and carrying out anodic oxidation after grinding and buffing, anodised voltage is 20 ~ 40V, and the anodised time is 2.0 ~ 3.5 hours; Again by being cleaned containing titanium metal plate after anodic oxidation, dry, then carry out anneal containing titanium metal plate by dried under 300 ~ 400 ℃ of conditions in air, finally by after anneal containing titanium metal plate under 300 ~ 450 ℃ of conditions, in the atmosphere that the volume content of nitrogen-containing precursor is 10～40%, with the speed of 12～20 ℃/min, annealed, furnace cooling, obtaining titanium nitride nano pipe array film containing the titanium metal plate surface.
In the present embodiment: the titanium content containing titanium metal plate is 50 ~ 70 wt%; The Na that electrolytic solution is 1.0 ~ 10 wt%
2sO
4, the citric acid of 0.1 ~ 0.8 wt%, the fluoride ion of 0.05 ~ 0.5 wt% and the H of 90 ~ 98 wt%
2the mixing solutions of O, fluoride ion wherein is NaF; Nitrogen-containing precursor is pyridine.
embodiment 10
A kind of porous titanium nitride nanotube array film and preparation method thereof.First, using containing titanium metal plate, as anode, inserting in electrolytic solution and carrying out anodic oxidation after grinding and buffing, anodised voltage is 20 ~ 40V, and the anodised time is 2.0 ~ 3.5 hours; Again by being cleaned containing titanium metal plate after anodic oxidation, dry, then carry out anneal containing titanium metal plate by dried under 350 ~ 450 ℃ of conditions in air, finally by after anneal containing titanium metal plate under 400 ~ 600 ℃ of conditions, in the atmosphere that the volume content of nitrogen-containing precursor is 20～60%, with the speed of 3～10 ℃/min, annealed, furnace cooling, obtaining titanium nitride nano pipe array film containing the titanium metal plate surface.
In the present embodiment: the titanium content containing titanium metal plate is 60 ~ 80 wt%; The Na that electrolytic solution is 8.0 ~ 15 wt%
2sO
4, the fluoride ion of 0.3 ~ 0.8 wt% and the H of 85 ~ 95 wt%
2the mixing solutions of O, fluoride ion wherein is NaF; The mixed gas that nitrogen-containing precursor is acetonitrile and pyridine.
embodiment 11
A kind of porous titanium nitride nanotube array film and preparation method thereof.First, using containing titanium metal plate, as anode, inserting in electrolytic solution and carrying out anodic oxidation after grinding and buffing, anodised voltage is 20 ~ 40V, and the anodised time is 2.0 ~ 3.5 hours; Again by being cleaned containing titanium metal plate after anodic oxidation, dry, then carry out anneal containing titanium metal plate by dried under 500 ~ 600 ℃ of conditions in air, finally by after anneal containing titanium metal plate under 550 ~ 700 ℃ of conditions, in the atmosphere that the volume content of nitrogen-containing precursor is 50～90%, with the speed of 9～15 ℃/min, annealed, furnace cooling, obtaining titanium nitride nano pipe array film containing the titanium metal plate surface.
In the present embodiment: the titanium content containing titanium metal plate is 80 ~ 95 wt%; The Na that electrolytic solution is 12 ~ 20 wt%
2sO
4, the citric acid of 1.3 ~ 2.0 wt%, the fluoride ion of 1.5 ~ 5.0 wt% and the H of 75 ~ 85 wt%
2the mixing solutions of O, fluoride ion wherein is NaF; The mixed gas that nitrogen-containing precursor is ammonia and acetonitrile.
embodiment 12
A kind of porous titanium nitride nanotube array film and preparation method thereof.First, using containing titanium metal plate, as anode, inserting in electrolytic solution and carrying out anodic oxidation after grinding and buffing, anodised voltage is 20 ~ 40V, and the anodised time is 2.0 ~ 3.5 hours; Again by being cleaned containing titanium metal plate after anodic oxidation, dry, then carry out anneal containing titanium metal plate by dried under 450 ~ 550 ℃ of conditions in air, finally by after anneal containing titanium metal plate under 650 ~ 800 ℃ of conditions, in the atmosphere that the volume content of nitrogen-containing precursor is 80～100%, with the speed of 1～6 ℃/min, annealed, furnace cooling, obtaining titanium nitride nano pipe array film containing the titanium metal plate surface.
In the present embodiment: the titanium content containing titanium metal plate is 95 ~ 99.99 wt%; The Na that electrolytic solution is 5.0 ~ 12 wt%
2sO
4, the citric acid of 0.8 ~ 1.4 wt%, the fluoride ion of 0.8 ~ 1.5 wt% and the H of 85 ~ 90 wt%
2the mixing solutions of O, the mixture that fluoride ion wherein is NaF and KF; Nitrogen-containing precursor is pyridine.
embodiment 13
A kind of porous titanium nitride nanotube array film and preparation method thereof.First, using containing titanium metal plate, as anode, inserting in electrolytic solution and carrying out anodic oxidation after grinding and buffing, anodised voltage is 10 ~ 20V, and the anodised time is 3.0 ~ 4.5 hours; Again by being cleaned containing titanium metal plate after anodic oxidation, dry, then carry out anneal containing titanium metal plate by dried under 300 ~ 400 ℃ of conditions in air, finally by after anneal containing titanium metal plate under 300 ~ 450 ℃ of conditions, in the atmosphere that the volume content of nitrogen-containing precursor is 10～40%, with the speed of 12～20 ℃/min, annealed, furnace cooling, obtaining titanium nitride nano pipe array film containing the titanium metal plate surface.
In the present embodiment: the titanium content containing titanium metal plate is 50 ~ 70 wt%; The H of the fluoride ion that electrolytic solution is 0.05 ~ 0.5 wt%, 0.5 ~ 5.0 wt%
2the mixing solutions of the glycerol of O and 95 ~ 99 wt%, fluoride ion wherein is KF; Nitrogen-containing precursor is acetonitrile.
embodiment 14
A kind of porous titanium nitride nanotube array film and preparation method thereof.First, using containing titanium metal plate, as anode, inserting in electrolytic solution and carrying out anodic oxidation after grinding and buffing, anodised voltage is 10 ~ 20V, and the anodised time is 3.0 ~ 4.5 hours; Again by being cleaned containing titanium metal plate after anodic oxidation, dry, then carry out anneal containing titanium metal plate by dried under 350 ~ 450 ℃ of conditions in air, finally by after anneal containing titanium metal plate under 400 ~ 650 ℃ of conditions, in the atmosphere that the volume content of nitrogen-containing precursor is 20～60%, with the speed of 3～10 ℃/min, annealed, furnace cooling, obtaining titanium nitride nano pipe array film containing the titanium metal plate surface.
In the present embodiment: the titanium content containing titanium metal plate is 60 ~ 80 wt%; The H of the fluoride ion that electrolytic solution is 0.3 ~ 0.8 wt%, 2.0 ~ 5.0 wt%
2the mixing solutions of the glycerol of O and 85 ~ 95 wt%, fluoride ion wherein is NH
4the mixture of F, KF, NaF and HF; The mixed gas that nitrogen-containing precursor is ammonia and pyridine.
embodiment 15
A kind of porous titanium nitride nanotube array film and preparation method thereof.First, using containing titanium metal plate, as anode, inserting in electrolytic solution and carrying out anodic oxidation after grinding and buffing, anodised voltage is 10 ~ 20V, and the anodised time is 3.0 ~ 4.5 hours; Again by being cleaned containing titanium metal plate after anodic oxidation, dry, then carry out anneal containing titanium metal plate by dried under 500 ~ 600 ℃ of conditions in air, finally by after anneal containing titanium metal plate under 550 ~ 700 ℃ of conditions, in the atmosphere that the volume content of nitrogen-containing precursor is 50～90%, with the speed of 9～15 ℃/min, annealed, furnace cooling, obtaining titanium nitride nano pipe array film containing the titanium metal plate surface.
In the present embodiment: the titanium content containing titanium metal plate is 80 ~ 95 wt%; The H of the fluoride ion that electrolytic solution is 0.8 ~ 3.0 wt%, 5.0 ~ 20 wt%
2the mixing solutions of the glycerol of O and 77 ~ 85 wt%, the mixture that fluoride ion wherein is KF, NaF and HF; The mixed gas that nitrogen-containing precursor is ammonia, acetonitrile and pyridine.
embodiment 16
A kind of porous titanium nitride nanotube array film and preparation method thereof.First, using containing titanium metal plate, as anode, inserting in electrolytic solution and carrying out anodic oxidation after grinding and buffing, anodised voltage is 10 ~ 20V, and the anodised time is 3.0 ~ 4.5 hours; Again by being cleaned containing titanium metal plate after anodic oxidation, dry, then carry out anneal containing titanium metal plate by dried under 450 ~ 550 ℃ of conditions in air, finally by after anneal containing titanium metal plate under 650 ~ 800 ℃ of conditions, in the atmosphere that the volume content of nitrogen-containing precursor is 80～100%, with the speed of 1～6 ℃/min, annealed, furnace cooling, obtaining titanium nitride nano pipe array film containing the titanium metal plate surface.
In the present embodiment: the titanium content containing titanium metal plate is 95 ~ 99.99 wt%; The H of the fluoride ion that electrolytic solution is 1.5 ~ 5.0 wt%, 15 ~ 35 wt%
2the mixing solutions of the glycerol of O and 60 ~ 80 wt%, fluoride ion wherein is NH
4the mixture of F, NaF and HF; Nitrogen-containing precursor is ammonia.
This embodiment proposes a kind of simple and reliable method for preparing porous titanium nitride nanotube array film, utilizes nitrogen-containing precursor as nitrogenous source, adopts simple annealing method, thereby has reduced a lot of numerous and diverse operations.Due to precursor TiO
2be Detitanium-ore-type, and be gradually transformed into a cube TiN after nitrogen-containing precursor is reacted, as shown in Figure 1, illustrate that the film that titanium plate surface generates is the TiN structure.In turning brilliant process, the lattice parameter of nano-pipe array thin film changes, thereby form vesicular structure as shown in Figure 2, can find out at titanium plate surface and form the TiN nano-tube array, nanotube diameter 80nm, and the tube wall of TiN nanotube is vesicular structure, by controlling nitriding temperature, thereby control the size in nanotube tube wall aperture.And the porous TiN nanotube prepared by the method is distributed with the hole of nano-scale from the mouth of pipe to the pipe bottom even, as shown in Figure 3.Because TiN has good electroconductibility, the tube wall vesicular structure has large specific surface area, and infiltration and the mobile unlimited system that a three-dimensional is provided for electrolytic solution, being conducive to the electrolytic solution intermediate ion passes in and out in electrode interior, can regulate according to the kind of electrolytic solution the size of hole, thereby be conducive to the coupling of electrolytic solution and electrode materials.The results show, form the porous titanium nitride nano-tube array and can effectively improve chemical property.
This embodiment adopts simple annealing method, by after anodic oxidation containing titanium metal plate high-temperature ammonolysis under nitrogen-containing precursor atmosphere, change the titanium nitride nano pipe of porous into, and regulate and control the aperture of nanotube tube wall by nitriding temperature and heat-up rate, realized the controlled preparation of porous titanium nitride nanotube array film.
This embodiment compared with prior art, has following positively effect:
1, the porous titanium nitride nano-tube array that prepared by this embodiment, its tube wall hole from the top to the bottom is evenly distributed, be conducive to improve the nanotube specific surface area, and flowing that its tube wall vesicular structure is electrolytic solution provides three-dimensional channel with ion migration, titanium nitride has high electronic migration ability and anti-electrolytic solution corrosive power, thereby has good chemical property and recycle performance.
2, this embodiment utilizes nitriding temperature and heat-up rate to control the nitridation of titanium oxide nanotubes, further to control the size in titanium nitride nano tube wall aperture, thereby can select as required better the kind of electrolytic solution, the matching degree of effectively regulating electrode materials and electrolytic solution.
3, this embodiment is passed through brief heat treating by the titanium metal plate that contains after anodic oxidation, and the original position on titanium metal plate that contains after anodic oxidation generates porous titanium nitride nanotube array film, and treatment process is simple, and cost is lower.
4, this embodiment is containing preparing porous titanium nitride nanotube array film on titanium metal plate, can scale operation, there is good industrialization prospect.
Therefore, this embodiment is passed through brief heat treating by the titanium metal plate that contains after anodic oxidation, realized the preparation of porous titanium nitride nanotube array film, simple and the process of preparation method, the porous titanium nitride nanotube array film prepared by the method is distributed with the hole of nano-scale from the mouth of pipe to the pipe bottom even, hole size is adjustable, is applicable to electrochemical field.
Claims (8)
1. the preparation method of a porous titanium nitride nanotube array film, it is characterized in that first using containing titanium metal plate, as anode, inserting in electrolytic solution and carrying out anodic oxidation after grinding and buffing, anodised voltage is 10 ~ 60V, and the anodised time is 0.5 ~ 5 hour; Again by being cleaned containing titanium metal plate after anodic oxidation, dry, then carry out anneal containing titanium metal plate by dried under 300 ~ 600 ℃ of conditions in air, finally by after anneal containing titanium metal plate under 300 ~ 800 ℃ of conditions, in the atmosphere that the volume content of nitrogen-containing precursor is 10～100%, with the speed of 1～20 ℃/min, annealed, furnace cooling, obtaining titanium nitride nano pipe array film containing the titanium metal plate surface; The tube wall of described titanium nitride nano pipe is distributed with the hole of nano-scale to the pipe bottom even from the mouth of pipe.
2. the preparation method of porous titanium nitride nanotube array film according to claim 1, is characterized in that the described titanium content containing titanium metal plate is 50 ~ 99.99wt%.
3. the preparation method of porous titanium nitride nanotube array film according to claim 1, is characterized in that described polishing is successively to carry out ultrasonic cleaning with ethanol, acetone and distilled water respectively containing titanium metal plate after first polishing, then at HF ︰ HNO
3︰ H
2the volume ratio of O is that (carry out chemical rightenning in the solution of 2 ~ 5) ︰ (4 ~ 7), the time of chemical rightenning is 3～10min to 1 ︰; Then clean with distilled water, dry up with nitrogen.
4. the preparation method of porous titanium nitride nanotube array film according to claim 1, is characterized in that the Na that described electrolytic solution is 1 ~ 20wt%
2sO
4, the citric acid of 0 ~ 2wt%, the fluoride ion of 0.05 ~ 5wt% and the H of 75 ~ 98wt%
2the mixing solutions of O, or be the fluoride ion of 0.05 ~ 5wt%, the H of 0.5 ~ 35wt%
2the mixing solutions of the ethylene glycol of O and 60 ~ 99wt%, or be the fluoride ion of 0.05 ~ 5wt%, the H of 0.5 ~ 35wt%
2the mixing solutions of the glycerol of O and 60 ~ 99wt%.
5. the preparation method of porous titanium nitride nanotube array film according to claim 1, it is characterized in that described cleaning is by containing titanium metal plate, from electrolytic solution, taking out and being placed in baking oven after anodic oxidation, be incubated 0.5 ~ 3 hour under 100 ~ 600 ℃ of conditions in air, cooling rear taking-up, in the mixing solutions of methyl alcohol and water or ultrasonic cleaning in the mixing solutions of ethanol and water.
6. the preparation method of porous titanium nitride nanotube array film according to claim 1, is characterized in that described nitrogen-containing precursor is more than one in ammonia, pyridine and acetonitrile.
7. the preparation method of porous titanium nitride nanotube array film according to claim 4, is characterized in that described fluoride ion is KF, NaF, NH
4more than one in F and HF.
8. according to the prepared porous titanium nitride nanotube array film of preparation method of the described porous titanium nitride nanotube array film of any one in claim 1 ~ 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210027249.2A CN102534630B (en) | 2012-02-08 | 2012-02-08 | Porous titanium nitride nanotube array film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210027249.2A CN102534630B (en) | 2012-02-08 | 2012-02-08 | Porous titanium nitride nanotube array film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102534630A CN102534630A (en) | 2012-07-04 |
| CN102534630B true CN102534630B (en) | 2014-01-01 |
Family
ID=46342618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210027249.2A Expired - Fee Related CN102534630B (en) | 2012-02-08 | 2012-02-08 | Porous titanium nitride nanotube array film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102534630B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103952763B (en) * | 2014-05-15 | 2016-05-04 | 东南大学 | A kind of gold microsphere-titanium nitride nano pipe array composite material and its preparation method and application |
| CN104240967B (en) * | 2014-09-26 | 2017-02-22 | 东南大学 | Polyaniline-manganese dioxide-titanium nitride nanowire array composite material and preparation method and application thereof |
| CN106319616A (en) * | 2015-06-24 | 2017-01-11 | 中国科学院金属研究所 | Method for in-situ growth of metal oxide/nitride monocrystal array film on metal matrix |
| CN105543935A (en) * | 2016-02-01 | 2016-05-04 | 同济大学 | Surface-strengthened Raman scattering substrate, and production method and application thereof |
| CN106683881B (en) * | 2016-08-05 | 2018-06-12 | 南京理工大学 | A kind of nanostructured dielectric capacitor and preparation method thereof |
| CN106498478B (en) * | 2016-11-22 | 2019-05-14 | 华南理工大学 | A kind of preparation method of transparent independent titanium dioxide nano-pipe array thin film |
| CN106938192A (en) * | 2017-02-13 | 2017-07-11 | 武汉科技大学 | A kind of porous carbon nano pipe array material and preparation method and its method for carried metal nano particle |
| CN109811389B (en) * | 2018-12-27 | 2020-11-24 | 浙江工业大学 | Preparation method of titanium niobium nitride nanotube array and nitriding layer composite structure |
| CN109609993B (en) * | 2018-12-27 | 2020-11-24 | 浙江工业大学 | Preparation method of titanium niobium nitride nanotube array |
| US11319640B2 (en) * | 2019-05-03 | 2022-05-03 | Purdue Research Foundation | Solar thermoplasmonic nanofurnaces and method for making and using same |
| CN111926345B (en) * | 2020-09-08 | 2023-05-16 | 华北水利水电大学 | IrO2-Ta2O5 anode with TiN nanotube interlayer |
| CN112198203A (en) * | 2020-09-16 | 2021-01-08 | 北京科技大学 | Preparation method of titanium nitride nanowire/nanotube array integrated electrode for simultaneously detecting dopamine, uric acid and ascorbic acid |
| CN112342478B (en) * | 2020-11-06 | 2022-02-08 | 西北有色金属研究院 | Preparation method of nano-porous titanium alloy film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101191248A (en) * | 2006-12-01 | 2008-06-04 | 西南交通大学 | Method for preparing titanium dioxide nano tube array on titanium-substrate material surface |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102034985B (en) * | 2010-11-15 | 2013-06-19 | 中国科学院青岛生物能源与过程研究所 | Oxygen electrode of lithium air battery as well as preparation method and application thereof |
| CN102251265B (en) * | 2011-07-08 | 2013-09-11 | 武汉科技大学 | Titanium dioxide nanometer composite structure film and preparation method thereof |
-
2012
- 2012-02-08 CN CN201210027249.2A patent/CN102534630B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101191248A (en) * | 2006-12-01 | 2008-06-04 | 西南交通大学 | Method for preparing titanium dioxide nano tube array on titanium-substrate material surface |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102534630A (en) | 2012-07-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102534630B (en) | Porous titanium nitride nanotube array film and preparation method thereof | |
| Chen et al. | Microwave–hydrothermal crystallization of polymorphic MnO2 for electrochemical energy storage | |
| CN104538597B (en) | Preparation method of snowflake titanium dioxide/two-dimensional nanometre titanium carbide composite material | |
| CN102556941B (en) | A kind of cobaltosic oxide nano linear array, its preparation method and the purposes as lithium ion battery negative | |
| CN108597892B (en) | Nano-porous copper-loaded copper-based oxide composite material with controllable morphology as well as preparation method and application thereof | |
| JP2016538709A (en) | Titanium oxide-based supercapacitor electrode material and manufacturing method thereof | |
| CN106229485A (en) | A kind of method being prepared transition metal oxide/carbon composite in situ by two-dimensional layer transition metal carbide MXene | |
| CN104711528A (en) | Sheet-like tungsten trioxide photoelectrode and preparation method thereof | |
| CN102280570B (en) | Trace Cu-doped Bi2S3-based thermoelectric material | |
| CN105498773A (en) | Preparation method for doped iron oxide nanorod catalyst | |
| CN102820459A (en) | Preparation method for lithium titanate material with high specific energy from mesoporous titanium dioxide | |
| CN101498051B (en) | Preparation of zinc oxide nano-wire array | |
| CN109167054B (en) | Phosphorus-doped sodium titanate nanowire and preparation method and application thereof | |
| Xu et al. | SnO2/CNT nanocomposite supercapacitors fabricated using scanning atmospheric-pressure plasma jets | |
| CN107055490B (en) | A kind of preparation method of porous nano vanadium nitride crystallite | |
| CN106058189A (en) | Method for synthesizing high-capacity anode material of lithium ion battery | |
| CN106115785A (en) | A kind of pure phase MoO2anode material of lithium-ion battery and preparation method thereof | |
| CN105826547A (en) | Method for preparing graphene-doped/carbon-clad lithium titanate composite negative electrode material through three-step method | |
| CN108910933A (en) | A kind of cuprous nano material preparation method and its Hydrogen Evolution Performance | |
| CN106299301B (en) | A kind of Li with excellent storage lithium performance3VO4The pattern of nano wire mutually regulates and controls method with object | |
| CN102263244B (en) | Method for preparing carbon confined-clad Sn/MgO nanowire array for lithium ion battery | |
| CN112331845A (en) | Preparation method of cobaltosic oxide nanowire array negative electrode material | |
| CN101250705B (en) | Method for manufacturing nickel-cuprum metallic baseband layer of highly oriented double-shaft texture | |
| CN108483459B (en) | Two-dimensional CrB nano ceramic material and preparation method thereof | |
| CN101320796A (en) | Preparation method of NiO nano-crystalline anode film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140101 Termination date: 20150208 |
|
| EXPY | Termination of patent right or utility model |