CN104616910B - Carbon coating titanium-based nano array material and its preparation method and application - Google Patents
Carbon coating titanium-based nano array material and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of carbon coating titanium-based nano array material, it is characterised in that：Including conductive substrates (1), titanium-based nano array (2) and amorphous carbon layer (3)；The titanium-based nano array (2) is arranged vertically on conductive substrates (1) surface, is interconnected with one another to form integral structure；The amorphous carbon layer (3) is completely evenly coated at titanium-based nano array (2) surface.Electrochemical energy storage application present invention also offers the preparation method of the nano-array material and its in ultracapacitor.Carbon coating titanium-based nano array material provided by the invention has " shell core " nano structure of ordered arrangement, may be directly applied to the electrode material of ultracapacitor, has the electrochemistry storing up electricity performance of fast charging and discharging and high-capacitance.
Description
Technical field
The invention belongs to electrode material for super capacitor preparation field, more particularly to a kind of carbon bag for ultracapacitor
Cover the preparation method of titanium-based nano array material.
Background technology
Currently, efficient, stable and environment-friendly energy storage device is accelerated development for rationally effectively using for the energy
It is very necessary.It is desirable to new energy storage device occur, the characteristic of high-energy-density and high power density is had concurrently, can be with
Meet the requirement that following electronic equipment, vehicle and industrial equipment export to hybrid power.Ultracapacitor is with its quick charge and discharge
The advantages such as electric speed, high power density and long life, greatly attract the interest of researcher, and are expected in the near future
Industrialized production is realized, providing the energy for the colourful life of the mankind supports.However, one that current ultracapacitor faces
Huge challenge is how while electrode material power density is ensured, to increase its energy density and stability.
Titanium base material includes titanium nitride, titanium oxide and N doping titanium oxide, wherein, titanium oxide and N doping titanium oxide have
Good optical electro-chemistry activity, is widely used in photosensitized solar cell.Titanium nitride has good electric conductivity and mechanically stable
Property, it is a kind of new very promising electrode material, titanium nitride has been widely used in photosensitized solar cell, fuel
Among battery and ultracapacitor.And the titanium nitride of ordered porous structural has the logical of high specific surface area and the diffusion of suitable ion
Road, high conductivity titanium nitride are often used as electrode base materials, however, titanium nitride can be because irreversible in aqueous phase electrolyte
Electrochemical oxidation reactions cause it is unstable, therefore, improve titanium nitride material energy density and cyclical stability to really real
Its existing application in energy storage field is also significant.
Carbon coating is considered as to strengthen a kind of simple and effective method of electrode material electrical conductance and stability.Largely
Carbon encapsulated material, such as LiFePO4/ C, NiO/C and TiO2/ C etc., it is developed and studies and be used for electrochemical energy storage field.Cause
This, rationally prepares nano-array material, the stability that can solve titanium nitride material is asked using the means of carbon-coating cladding to design
Topic, while realize electrode material high power density and energy density.
The content of the invention
Goal of the invention：The present invention provides a kind of carbon coating titanium-based nano array material and preparation method thereof, described nanometer
Array material is applied to the electrochemical energy storage of electrode of super capacitor.
Technical scheme：A kind of carbon coating titanium-based nano array material provided by the invention, including conductive substrates (1), titanium-based
Nano-array (2) and amorphous carbon layer (3)；The titanium-based nano array (2) vertical arrangement is on conductive substrates (1) surface, each other
It is interconnected to form integral structure；The amorphous carbon layer (3) is completely evenly coated at titanium-based nano array (2) surface.
As an improvement, the carbon coating titanium-based nano array material has " shell-core " of ordered arrangement in conductive substrates (1)
Nanostructured, described core are titanium-based nano line, nano-pillar or nano-tube array, and described shell is amorphous carbon layer.
Improved as another kind, the conductive substrates (1) include titanium sheet, electro-conductive glass, carbon cloth, carbon paper, graphene film, carbon
Nanotube films and porous carbon film.
Improved as another kind, the titanium-based includes titanium nitride, titanium oxide and N doping titanium oxide；The titanium-based nano battle array
Arrange single nano-wire, cluster nano line, nano-pillar or the nanotube that (2) are one group of ordered arrangement；Wherein, single nano-wire diameter
For 10~30nm；Cluster nano linear diameter is 20~200nm, and length is 1~1.5 μm；A diameter of 100~the 300nm of nano-pillar, it is long
Spend for 1~1.5 μm；Tube diameters are 50~100nm, and wall thickness is 10~30nm, and length is 3~5 μm.
Improved as another kind, the thickness of the amorphous carbon layer (3) is 3~10nm.
Present invention also offers a kind of preparation method of above-mentioned carbon coating titanium-based nano array material, comprise the following steps：
(1) titanium oxide nano wire or nano-pillar battle array are prepared using seed auxiliary hydro-thermal reaction method and high-temperature calcination processing method
Row：In conductive substrates material surface physical absorption titaniferous seed liquor, it is placed in after drying in sealing hydrothermal reaction kettle, addition hydrochloric acid,
The mixed reaction solution of water and titanium-based presoma, carry out hydro-thermal reaction；Reaction product carries out high-temperature calcination under inert gas shielding
Processing, produces crystal phase titanium oxide nano wire or nano column array；
Titania nanotube array is prepared using constant voltage anodizing and high-temperature calcination processing：In two electrode electro Chemicals
In reaction system, using titanium sheet as anode, platinized platinum as negative electrode, be electrolysed using the mixed liquor of ethylene glycol, water, ammonium fluoride as reaction
Liquid, carry out constant voltage anodic oxidation reactionses；Reaction product high-temperature calcination under inert gas shielding is handled, and produces crystal phase oxidation
Titanium nano-tube array；
(2) N doping titanium oxide or titanium nitride nano battle array are prepared using the processing of controlled N doping or nitridation treatment method completely
Row：Titanium oxide nano wire, nano-pillar or nano-tube array made from crystal phase step (1) are placed in tube-type atmosphere furnace, in ammonia
High temperature nitridation completely or the processing of part N doping are carried out under gas atmosphere, produces titanium nitride or N doping TiOx nano array；
(3) carbon coating titanium-based nano array material is prepared using hydro-thermal reaction method and high-temperature calcination processing method：Will nitridation
Titanium, titanium oxide and N doping TiOx nano array material are placed in sealing hydrothermal reaction kettle, are added hydro-thermal reaction liquid and are entered water-filling
Thermal response；Reaction product carries out high-temperature calcination processing under nitrogen protection, produces carbon coating titanium-based nano array material.
In step (1), the seed auxiliary hydro-thermal reaction law part is：Titaniferous seed liquor is 0.3~0.9mol/L titanium-baseds
Precursor ethanol solution, the volume ratio of hydrochloric acid, water and titanium-based presoma in hydro-thermal reaction liquid is 1:(1~1.1):(0.02~
0.04), hydrochloric acid is 37% hydrochloric acid solution, and the hydro-thermal reaction time is 7~20h, and hydrothermal temperature is 150~200 DEG C, titanium-based
Presoma is titanium tetrachloride, butyl titanate or tetraisopropyl titanate；The constant voltage anodizing condition is：Anodic oxidation
Voltage is 30~60V, and the reaction time is 1~3h, and reaction temperature is 23~27 DEG C, is reacted in electrolyte, the volume integral of ethylene glycol
Number is 97~99%, and the volume fraction of distilled water is 1~3%, and the mass fraction of ammonium fluoride is 0.2~0.3%；At high-temperature calcination
Manage bar part is：Nitrogen gas concn is more than 99.7%, and nitrogen flow is 45~55mL/min；Heating rate is：Room temperature is to 450 DEG C
2h is incubated at 2 DEG C/min, 450 DEG C.
In step (2), described complete nitrogen treatment condition is：Nitridation reaction, ammonia concentration are carried out in ammonia atmosphere
For 99.6~99.9%, ammonia flow is 30~60mL/min, and heating rate is 5 DEG C/min from room temperature to 300 DEG C, from 300 to
550 DEG C are 3 DEG C/min, DEG C are 1 DEG C/min, 900 DEG C of isothermal reaction 1h from 550 to 900；Described controlled N doping treatment conditions
For：N doping reaction is carried out in ammonia atmosphere, ammonia concentration is 99.6~99.9%, and ammonia flow is 30~60mL/min,
Heating rate is 5 DEG C/min from room temperature to 300 DEG C, DEG C is 2 DEG C/min, 600 DEG C of isothermal reaction 3h from 300 to 600.
In step (3), the hydro-thermal reaction method condition is：Hydro-thermal reaction liquid is 0.05~0.2mol/L carbon-source cpd water
Solution, the hydro-thermal reaction time are 1~5h, and hydrothermal temperature is 160~180 DEG C, and carbon-source cpd is glucose, sucrose or shallow lake
Powder；The high-temperature calcination treatment conditions are：Nitrogen gas concn is more than 99.9%, and nitrogen flow is 30~50mL/min；Heating rate
For room temperature to 550 DEG C be 3 DEG C/min, 550 DEG C to 800 DEG C be 2 DEG C/min, be incubated 1h at 800 DEG C.
Present invention also offers a kind of application of above-mentioned carbon coating titanium-based nano array material in ultracapacitor.
Beneficial effect：Carbon coating titanium-based nano array material provided by the invention has " shell-core " nanometer of ordered arrangement
Architectural feature, the electrode material of ultracapacitor is may be directly applied to, there is the storage of the electrochemistry of fast charging and discharging and high-capacitance
Electrical property.
Specifically, the carbon coating titanium-based nano array material be completely evenly coated at by amorphous carbon layer titanium oxide or
N doping titanium oxide or titanium nitride nano array surface, " shell-core " nanostructured is formed, titanium oxide can be effectively lifted or nitrogen is mixed
Titanium oxide doped or nitridation titanium substrate electrical conductance and electrochemical cycle stability, while realize quick charge transport ability；Cause
This, the characteristics of obtained carbon coating titanium-based nano array material has high-specific-power, high-energy-density and high stability concurrently, can answer very well
Also there is actual application value for electrode material for super capacitor, and in related electrochemical field.Through electrochemical property test, institute
The area specific capacitance for the nano-array material stated is up to 94F/cm2, specific volume after 2000 circulations of charge and discharge cycles stability test
Amount is still maintained at more than 99%.
The preparation of the carbon coating titanium-based nano array material is using seed auxiliary hydro-thermal reaction method and high-temperature calcination processing
Method prepares titanium oxide nano wire or nano column array, and oxygen is prepared using constant voltage anodizing and high-temperature calcination processing method
Change titanium nano-tube array, then N doping titanium oxide or titanium nitride are prepared using the processing of controlled N doping or nitridation treatment method completely
Nano wire, nano-pillar or nano-tube array, carbon coating titanium-based is finally prepared using hydro-thermal reaction method and high-temperature calcination processing method
The pattern rule of nano-array material is controllable, and reliable preparation process.
Brief description of the drawings
Fig. 1 is the structural representation of carbon coating titanium-based nano array material.
Fig. 2 is the preparation technology flow chart of carbon coating titanium-based nano array material.
Fig. 3 A are the scanning electron microscope (SEM) photograph of titanium nitride nano linear array；3B is the scanning electricity of carbon coating titanium nitride nano linear array
Mirror figure；3C is the scanning electron microscope (SEM) photograph of titanium nitride nano post array；3D is the scanning electron microscope (SEM) photograph of carbon coating titanium nitride nano post array；
3E is the scanning electron microscope (SEM) photograph of titanium nitride nano pipe array；3F is the scanning electron microscope (SEM) photograph of carbon coating titanium nitride nano pipe array.
Fig. 4 is the X-ray diffractogram of titanium nitride nano linear array and carbon coating titanium nitride nano linear array.
Fig. 5 A are the transmission electron microscope picture of carbon coating titanium nitride nano line, and Fig. 5 B are carbon coating N doping titanium oxide nano wire
Transmission electron microscope picture.
Fig. 6 A are the scanning electron microscope (SEM) photograph of N doping TiOx nano linear array；6B is carbon coating N doping titanium oxide nano wire
The scanning electron microscope (SEM) photograph of array.
Fig. 7 A are the cyclic voltammetry figure of carbon coating titanium nitride nano post array；7B is carbon coating titanium nitride nano post battle array
The constant current charge-discharge test chart of row；7C is that the cycle charge-discharge capacitance conservation rate of carbon coating titanium nitride nano post array is tested
Figure.
Embodiment
The present invention is described in further detail with embodiment below in conjunction with accompanying drawing, it should be pointed out that reality as described below
Example is applied to be intended to be easy to the understanding of the present invention.
Embodiment 1
The preparation of carbon coating titanium-based nano array material, is shown in Fig. 2, comprises the following steps：
Hydro-thermal reaction method and the reaction of controlled N doping or completely nitridation reaction process (A) are aided in based on seed, prepared
Titanium oxide or N doping titanium oxide or titanium nitride nano line, the nano column array (A1) of conductive substrates surface ordered arrangement：It will lead
Electric substrate is immersed in dipping seed liquor, Seed Layer is formed in substrate material surface by physical absorption, after high-temperature calcination processing
It is put into sealing hydrothermal reaction kettle, carries out hydro-thermal reaction by reaction solution of the mixed liquor of hydrochloric acid, water and titanium-based presoma, react institute
Obtain material and controlled N doping reaction or complete nitridation reaction are carried out under ammonia atmosphere, obtain conductive substrates surface ordered arrangement
Titanium oxide, the nano wire or nano column array (A1) of titanium nitride or N doping titanium oxide.
Based on constant voltage anodizing and the reaction of controlled N doping or complete nitridation reaction process (B), prepare and lead
Titanium oxide or the N doping oxidation of electric substrate surface ordered arrangement or titanium nitride nano pipe array (B1)：It is anti-in two electrode electro Chemicals
Answer in system, using titanium sheet as anode, platinized platinum as negative electrode, using ethylene glycol, water, ammonium fluoride mixed liquor as reaction electrolyte,
Constant voltage anodic oxidation reactionses are carried out, reaction resulting materials carry out controlled N doping reaction or completely nitridation under ammonia atmosphere
Reaction, obtain the titanium oxide or N doping oxidation or titanium nitride nano pipe array (B1) of conductive substrates surface ordered arrangement.
Based on hydrothermal reaction process (C), the amorphous carbon layer for preparing conductive substrates surface ordered arrangement coats titanium oxide
Or N doping oxidation or titanium nitride nano array (C1)：In hydrothermal reaction kettle is sealed, conductive substrates surface ordered arrangement is put into
Titanium oxide or N doping oxidation or titanium nitride nano line, nano-pillar, nano-tube array, add the mixing of carbon-source cpd and water
Reaction solution carries out hydro-thermal reaction, and high-temperature calcination is handled reaction resulting materials under nitrogen protection, is aoxidized in titanium oxide or N doping
Or titanium nitride nano line, nano-pillar, nano-tube array surface formation amorphous carbon coating layer, conductive substrates surface is made and arranges in order
The carbon coating titanium-based nano array material (C1) of row.
Embodiment 2
The preparation method of carbon coating titanium nitride nano linear array material, is comprised the following steps that：
(1) TiOx nano linear array is prepared using seed auxiliary hydro-thermal reaction method and high-temperature calcination processing method：By carbon
Cloth substrate is cleaned up with acetone, ethanol and deionized water successively.Dried carbon cloth is put into titanium tetrachloride containing 0.5mol/L
Ethanol solution in, stir lower fully immersion, be put into after taking out drying in tube furnace, 400 DEG C of high-temperature calcinations in a nitrogen atmosphere
Handle 10min；Then post-calcination sample is put into 100mL hydrothermal reaction kettle, adds the concentrated hydrochloric acid containing 30mL 37%, 30mL
The mixed reaction solution of water and 0.6mL butyl titanates, the hydro-thermal reaction time is 7h at 180 DEG C, and reaction takes out product after terminating
It is placed in tube furnace, in a nitrogen atmosphere 450 DEG C of high-temperature calcination 2h, nitrogen gas concn 99.7%, nitrogen flow 45mL/min,
Heating rate is：Room temperature is 2 DEG C/min to 450 DEG C, and crystal phase TiOx nano linear array is made.
(2) titanium nitride nano linear array is prepared using high-temperature ammonolysis reaction method：By crystal phase TiOx nano linear array
It is placed in tube-type atmosphere furnace, under ammonia atmosphere, ammonia concentration 99.7%, ammonia flow 48mL/min, heating rate
It is 5 DEG C/min from room temperature to 300 DEG C, DEG C is 3 DEG C/min from 300 to 550, DEG C is 1 DEG C/min from 550 to 900,900 DEG C of constant temperature
React 1h, you can titanium nitride nano linear array is made.The scanning electron microscope (SEM) photograph of titanium nitride nano linear array is shown in Fig. 3 A, titanium nitride nano
The spaced separation of line, length be 1~1.5 μm, a diameter of 10~30nm of single nano-wire, cluster nano linear diameter be 20~
200nm.The X-ray diffractogram of titanium nitride nano linear array is shown in Fig. 4, and titanium nitride nano linear array shows good Emission in Cubic and received
Rice crystal structure.
(3) carbon coating titanium nitride nano linear array material is prepared using hydro-thermal reaction method and high-temperature calcination processing method：Will
Conductive substrates surface ordered arrangement titanium nitride nano linear array material is placed in sealing hydrothermal reaction kettle, adds 0.05mol/L Portugals
Grape sugar aqueous solution reaction solution, the hydro-thermal reaction time is 4h at 170 DEG C, and reaction is taken out product after terminating and is placed in tube furnace,
Progress high-temperature calcination processing, nitrogen gas concn 99.9%, nitrogen flow 30mL/min, heating rate are under nitrogen atmosphere：Room
Temperature is 3 DEG C/min to 550 DEG C, is 2 DEG C/min from 550 DEG C to 800 DEG C, 1h is incubated at last 800 DEG C, and carbon coating titanium nitride is made
Nano wire nano-array material.The scanning electron microscope (SEM) photograph of carbon coating titanium nitride nano line nano-array material is shown in Fig. 3 B, carbon coating nitrogen
The aobvious mirror figure of transmitted electron for changing titanium nano wire nano-array material is shown in Fig. 5 A, the thickness about 6nm of carbon-coating.Titanium nitride nano linear array
See Fig. 4, titanium nitride and the X of carbon coating titanium nitride nano linear array with the X-ray diffractogram of carbon coating titanium nitride nano linear array
X ray diffration pattern x is basically identical, and the carbon-coating for illustrating surface parcel is amorphous state.
Structural characterization result shows that carbon coating titanium nitride nano linear array material is " shell-core " nano junction of ordered arrangement
Structure, the described spaced separation of titanium nitride nano linear array, length are 1~1.5 μm, single nano-wire a diameter of 10~
30nm, cluster nano linear diameter are 20~200nm, and the carbon-coating is coated on titanium nitride nano linear array surface, amorphous carbon layer
Thickness is 3~10nm.
Embodiment 3
The preparation method of carbon coating titanium nitride nano post array material, is comprised the following steps that：
(1) TiOx nano post array is prepared using seed auxiliary hydro-thermal reaction method and high-temperature calcination processing：By graphite flake
Clean and dry, be then placed in the ethanol solution of tetraisopropyl titanate containing 0.8mol/L, be put into after taking out drying after immersion 10min
In tube furnace, 400 DEG C of high-temperature calcinations in a nitrogen atmosphere handle 10min.Then sample obtained by calcining is put into 100mL hydro-thermal
In reactor, the mixed reaction solution for containing the concentrated hydrochloric acids of 30mL 37%, 30mL water and 1.0mL butyl titanates is added, at 150 DEG C
Lower the hydro-thermal reaction time is 20h, and reaction is taken out product after terminating and is placed in tube furnace, 450 DEG C of high-temperature calcinations in a nitrogen atmosphere
Processing 2h, nitrogen gas concn 99.7%, nitrogen flow 55mL/min, heating rate are：Room temperature is 2 DEG C/min to 450 DEG C, system
Obtain the TiOx nano post array of anatase-phase nano crystal structure.
(2) titanium nitride nano post array is prepared using complete nitridation reaction method：By crystal phase TiOx nano post array
It is placed in tube-type atmosphere furnace, under ammonia atmosphere, ammonia concentration 99.7%, ammonia flow 45mL/min, heating rate
It is 5 DEG C/min from room temperature to 300 DEG C, DEG C is 3 DEG C/min from 300 to 550, DEG C is 1 DEG C/min from 550 to 900,900 DEG C of constant temperature
React 1h, you can titanium nitride nano post array is made, the aobvious figure of scanning electricity of titanium nitride nano post array is shown in Fig. 3 C, described nitridation
A diameter of 100~300nm of titanium nano column array, length are 1~1.5 μm.
(3) carbon coating titanium nitride nano post array material is prepared using hydro-thermal reaction method and high-temperature calcination processing method：Will
Carbon-based basal surface ordered arrangement titanium nitride nano post array material is placed in sealing hydrothermal reaction kettle, adds 0.15mol/L grapes
Sugar aqueous solution reaction solution, the hydro-thermal reaction time is 2h at 180 DEG C, and reaction is taken out product after terminating and is placed in tube furnace, in nitrogen
Progress high-temperature calcination processing, nitrogen gas concn 99.9%, nitrogen flow 45mL/min, heating rate are under gas atmosphere：Room temperature
It is 3 DEG C/min to 550 DEG C, is 2 DEG C/min from 550 DEG C to 800 DEG C, 1h is incubated at last 800 DEG C, carbon coating titanium nitride is made and receives
Rice post nano-array material.The scanning electron microscope (SEM) photograph of carbon coating titanium nitride nano post array material is shown in Fig. 3 D, and characterization result shows carbon
Layer is completely evenly coated at titanium nitride nano post surface, and carbon coating layer thickness is about 8nm.
Embodiment 4
The preparation method of carbon coating titanium nitride nano pipe array material, is comprised the following steps that：
(1) using constant voltage anodizing synthesis titania nanotube array：In two electrode electro Chemical reaction systems,
Using titanium sheet as anode, platinized platinum as negative electrode, using ethylene glycol, water, ammonium fluoride mixed liquor as reaction electrolyte, carry out anodic oxygen
Change reaction and titania nanotube array is made；The constant voltage anodizing condition is：Anodic oxidation voltage is 60V, reaction
Time is 1h, and reaction temperature is 23 DEG C, is reacted in electrolyte, and the volume fraction of ethylene glycol is 97%, and the volume fraction of water is
3%, the mass fraction of ammonium fluoride is 0.30%.Reaction is placed in Muffle furnace after terminating, 450 DEG C of high-temperature calcinations in a nitrogen atmosphere
Processing 2h, nitrogen gas concn 99.7%, nitrogen flow 55mL/min, heating rate are：Room temperature is 2 DEG C/min to 450 DEG C, system
Obtain the titania nanotube array of anatase-phase nano crystal structure.
(2) titanium nitride nano pipe array is prepared using complete nitridation reaction method：By the oxygen of anatase-phase nano crystal structure
Change titanium nano-tube array to be placed in tube-type atmosphere furnace, ammonia concentration 99.6%, ammonia flow 60mL/min, heating rate
It is 5 DEG C/min from room temperature to 300 DEG C, DEG C is 3 DEG C/min from 300 to 550, DEG C is 1 DEG C/min from 550 to 900,900 DEG C of constant temperature
React 1h, you can titanium nitride nano pipe array is made, the scanning electron microscope (SEM) photograph of titanium nitride nano pipe array is shown in Fig. 3 E, described nitridation
The bore dia of titanium nanotube is 50~100nm, and wall thickness is 10~30nm, and length is 3~5 μm.
(3) carbon coating titanium nitride nano pipe nano-array material is prepared using hydrothermal synthesis method：Titanium plate surface is arranged in order
Row titanium nitride nano pipe array material is placed in sealing hydrothermal reaction kettle, adds 0.1mol/L D/W reaction solutions,
The hydro-thermal reaction time is 5h at 160 DEG C, and reaction is taken out product after terminating and is placed in tube furnace, carries out high temperature in a nitrogen atmosphere and forges
Burning processing, nitrogen gas concn 99.9%, nitrogen flow 35mL/min, heating rate are：Room temperature is 3 DEG C/min to 550 DEG C, from
550 DEG C to 800 DEG C are 2 DEG C/min, and 1h is incubated at last 800 DEG C, and carbon coating titanium nitride nano pipe nano-array material, carbon is made
The scanning electron of cladding titanium nitride nano pipe array material shows mirror figure and refers to Fig. 3 F, and characterization result shows that carbon-coating completely uniformly coats
On titanium nitride nano tube wall face, carbon coating layer thickness is about 4nm.
Embodiment 5
The preparation method of carbon coating N doping titanium oxide nano wire array material, is comprised the following steps that：
(1) TiOx nano linear array is prepared using seed auxiliary hydro-thermal reaction method and high-temperature calcination processing method：By carbon
Paper substrates are put into titanium tetrachloride solution containing 0.9mol/L, stir 20min, are put into after taking out drying in tube furnace in air atmosphere
10min is calcined at 400 DEG C.Then post-calcination sample is put into 50mL hydrothermal reaction kettle, addition contains 37% dense salt of 15mL
The mixed reaction solution of acid, 16mL water and 0.4mL butyl titanates, the hydro-thermal reaction time is 8h at 170 DEG C, and reaction takes after terminating
Go out product to be placed in tube furnace, 450 DEG C of high-temperature calcination 2h, the titanium dioxide nano thread battle array of anatase-phase nano crystal structure is made
Row.
(2) N doping TiOx nano linear array is prepared using the controlled N doping processing method of high temperature：By Anatase
The titanium dioxide nanowire array of nanocrystalline structure is placed in tube-type atmosphere furnace, and under ammonia atmosphere, ammonia concentration is
99.6%, ammonia flow 60mL/min, heating rate are 5 DEG C/min from room temperature to 300 DEG C, from 300 to 600 DEG C for 2 DEG C/
Min, 600 DEG C of isothermal reaction 3h, N doping TiOx nano linear array is made.The scanning electricity of N doping TiOx nano linear array
Mirror figure refers to Fig. 6 A, the spaced separation of N doping titanium oxide nano wire, and cluster nano linear diameter is 20~200nm, length 1
~1.5 μm.
(3) carbon coating N doping titanium oxide nano wire array material is prepared using hydrothermal synthesis method：Carbon paper surface is orderly
Arrangement N doping titanium oxide nano wire array material is placed in sealing hydrothermal reaction kettle, adds the reaction of 0.1mol/L aqueous sucrose solutions
Liquid, the hydro-thermal reaction time is 4h at 170 DEG C, and reaction is taken out product after terminating and is placed in tube furnace, carries out in a nitrogen atmosphere
High-temperature calcination is handled, nitrogen gas concn 99.9%, nitrogen flow 40mL/min, and heating rate is：Room temperature to 550 DEG C be 3 DEG C/
Min, it is 2 DEG C/min from 550 DEG C to 800 DEG C, 1h is incubated at last 800 DEG C, carbon coating N doping TiOx nano linear array is made
Row material.The transmitted electron of carbon coating N doping titanium oxide nano wire array material shows mirror figure and refers to Fig. 5 B, carbon coating N doping
The scanning electron microscope diagram of TiOx nano linear array refers to Fig. 6 B.Characterization result shows that carbon-coating is completely uniformly wrapped on nitrogen and mixed
Titanium oxide doped nanowire surface, carbon coating layer thickness are about 6nm.
Embodiment 6
The preparation method of carbon coating titanium nitride nano pipe array material, is comprised the following steps that：
(1) using constant voltage anodizing synthesis titania nanotube array：In two electrode electro Chemical reaction systems,
Using titanium sheet as anode, platinized platinum as negative electrode, using ethylene glycol, water, ammonium fluoride mixed liquor as reaction electrolyte, carry out anodic oxygen
Change reaction and titania nanotube array is made；The constant voltage anodizing condition is：Anodic oxidation voltage is 30V, reaction
Time is 3h, and reaction temperature is 27 DEG C, is reacted in electrolyte, and the volume fraction of ethylene glycol is 99%, and the volume fraction of water is
1%, the mass fraction of ammonium fluoride is 0.20%.Reaction is placed in Muffle furnace after terminating, 450 DEG C of high-temperature calcinations in a nitrogen atmosphere
Processing 2h, nitrogen gas concn 99.7%, nitrogen flow 45mL/min, heating rate are：Room temperature is 2 DEG C/min to 450 DEG C, system
Obtain the titania nanotube array of anatase-phase nano crystal structure.
(2) titanium nitride nano pipe array is prepared using complete nitridation reaction method：By the oxygen of anatase-phase nano crystal structure
Change titanium nano-tube array to be placed in tube-type atmosphere furnace, ammonia concentration 99.9%, ammonia flow 30mL/min, heating rate
It is 5 DEG C/min from room temperature to 300 DEG C, DEG C is 3 DEG C/min from 300 to 550, DEG C is 1 DEG C/min from 550 to 900,900 DEG C of constant temperature
React 1h, you can titanium nitride nano pipe array is made.
(3) carbon coating titanium nitride nano pipe nano-array material is prepared using hydrothermal synthesis method：Titanium plate surface is arranged in order
Row titanium nitride nano pipe array material is placed in sealing hydrothermal reaction kettle, 0.2mol/L aqueous sucrose solution reaction solutions is added, 180
The hydro-thermal reaction time is 1h at DEG C, and reaction is taken out product after terminating and is placed in tube furnace, carries out high-temperature calcination in a nitrogen atmosphere
Processing, nitrogen gas concn 99.9%, nitrogen flow 50mL/min, heating rate are：Room temperature is 3 DEG C/min to 550 DEG C, from
550 DEG C to 800 DEG C are 2 DEG C/min, and 1h is incubated at last 800 DEG C, and carbon coating titanium nitride nano pipe nano-array material is made.
Embodiment 8
The preparation method of carbon coating N doping titanium oxide nano wire array material, is comprised the following steps that：
(1) TiOx nano linear array is prepared using seed auxiliary hydro-thermal reaction method and high-temperature calcination processing method：It will lead
Electric substrate of glass is put into titanium tetrachloride solution containing 0.3mol/L, stirs 20min, and air atmosphere in tube furnace is put into after taking out drying
In calcine 10min at 400 DEG C.Then post-calcination sample is put into 50mL hydrothermal reaction kettle, added dense containing 10mL 37%
The mixed reaction solution of hydrochloric acid, 11mL water and 0.4mL butyl titanates, the hydro-thermal reaction time is 8h at 170 DEG C, after reaction terminates
Take out product to be placed in tube furnace, 450 DEG C of high-temperature calcination 2h, the titanium dioxide nano thread battle array of anatase-phase nano crystal structure is made
Row.
(2) N doping TiOx nano linear array is prepared using the controlled N doping processing method of high temperature：By Anatase
The titanium dioxide nanowire array of nanocrystalline structure is placed in tube-type atmosphere furnace, and under ammonia atmosphere, ammonia concentration is
99.9%, ammonia flow 30mL/min, heating rate are 5 DEG C/min from room temperature to 300 DEG C, from 300 to 600 DEG C for 2 DEG C/
Min, 600 DEG C of isothermal reaction 3h, N doping TiOx nano linear array is made.
(3) carbon coating N doping titanium oxide nano wire array material is prepared using hydrothermal synthesis method：Carbon paper surface is orderly
Arrangement N doping titanium oxide nano wire array material is placed in sealing hydrothermal reaction kettle, adds the reaction of 0.1mol/L amidins
Liquid, the hydro-thermal reaction time is 4h at 170 DEG C, and reaction is taken out product after terminating and is placed in tube furnace, carries out in a nitrogen atmosphere
High-temperature calcination is handled, nitrogen gas concn 99.9%, nitrogen flow 40mL/min, and heating rate is：Room temperature to 550 DEG C be 3 DEG C/
Min, it is 2 DEG C/min from 550 DEG C to 800 DEG C, 1h is incubated at last 800 DEG C, carbon coating N doping TiOx nano linear array is made
Row material.
Embodiment 9
The preparation method of carbon coating titanium nitride nano linear array material, is comprised the following steps that：
(1) TiOx nano linear array is prepared using seed auxiliary hydro-thermal reaction method and high-temperature calcination processing method：By carbon
Cloth substrate is cleaned up with acetone, ethanol and deionized water successively.Dried carbon cloth is put into titanium tetrachloride containing 0.5mol/L
Ethanol solution in, stir lower fully immersion, be put into after taking out drying in tube furnace, 400 DEG C of high-temperature calcinations in a nitrogen atmosphere
Handle 10min；Then post-calcination sample is put into 100mL hydrothermal reaction kettle, adds the concentrated hydrochloric acid containing 30mL 37%, 30mL
The mixed reaction solution of water and 0.9mL butyl titanates, the hydro-thermal reaction time is 7h at 200 DEG C, and reaction takes out product after terminating
It is placed in tube furnace, in a nitrogen atmosphere 450 DEG C of high-temperature calcination 2h, nitrogen gas concn 99.7%, nitrogen flow 45mL/min,
Heating rate is：Room temperature is 2 DEG C/min to 450 DEG C, and crystal phase TiOx nano linear array is made.
(2) titanium nitride nano linear array is prepared using high-temperature ammonolysis reaction method：By crystal phase TiOx nano linear array
It is placed in tube-type atmosphere furnace, under ammonia atmosphere, ammonia concentration 99.7%, ammonia flow 48mL/min, heating rate
It is 5 DEG C/min from room temperature to 300 DEG C, DEG C is 3 DEG C/min from 300 to 550, DEG C is 1 DEG C/min from 550 to 900,900 DEG C of constant temperature
React 1h, you can titanium nitride nano linear array is made.
(3) carbon coating titanium nitride nano linear array material is prepared using hydro-thermal reaction method and high-temperature calcination processing method：Will
Conductive substrates surface ordered arrangement titanium nitride nano linear array material is placed in sealing hydrothermal reaction kettle, adds 0.05mol/L Portugals
Grape sugar aqueous solution reaction solution, the hydro-thermal reaction time is 4h at 170 DEG C, and reaction is taken out product after terminating and is placed in tube furnace,
Progress high-temperature calcination processing, nitrogen gas concn 99.9%, nitrogen flow 30mL/min, heating rate are under nitrogen atmosphere：Room
Temperature is 3 DEG C/min to 550 DEG C, is 2 DEG C/min from 550 DEG C to 800 DEG C, 1h is incubated at last 800 DEG C, and carbon coating titanium nitride is made
Nano wire nano-array material.
The structure of carbon coating titanium-based nano array material of the present invention as seen from the above embodiment：Including conductive substrates 1, titanium-based
Nano-array 2 and amorphous carbon layer 3；Titanium-based nano array 2 is arranged vertically on the surface of conductive substrates 1, is interconnected with one another to be formed
Integral structure；Amorphous carbon layer 3 is completely evenly coated at the surface of titanium-based nano array 2.Carbon coating titanium-based nano array material
" shell-core " nanostructured with ordered arrangement in conductive substrates 1, core are titanium-based nano line, nano-pillar or nano-tube array, shell
It is amorphous carbon layer.Titanium-based includes titanium nitride, titanium oxide and N doping titanium oxide；Titanium-based nano array 2 is one group of ordered arrangement
Single nano-wire, cluster nano line, nano-pillar or nanotube；Wherein, a diameter of 10~30nm of single nano-wire；Cluster nano
Linear diameter is 20~200nm, and length is 1~1.5 μm；A diameter of 100~the 300nm of nano-pillar, length are 1~1.5 μm；Nanotube
A diameter of 50~100nm, wall thickness are 10~30nm, and length is 3~5 μm.The thickness of amorphous carbon layer 3 is 3~10nm.
Embodiment 10
Carbon coating titanium nitride nano post array material produced by the present invention is applied to the electricity of electrode material for super capacitor
Chemical energy storage.
Electrochemical test method is as follows：In three-electrode system, using 1.0mol/L sulfuric acid solution as Working electrolyte, carbon
It is working electrode to coat titanium nitride nano post array material, and platinized platinum is auxiliary electrode, and saturated calomel electrode is reference electrode, is used
Electrochemical workstation carries out cyclic voltammetry, sets initial potential 0V, high potential 0.6V, low potential 0V, sweep speed difference
For 10,20,40,60mV/s.The cyclic voltammetry figure of carbon coating titanium nitride nano post array refers to Fig. 7 A, cyclic voltammetry curve
The similar rectangular characteristic of display, the electric double layer capacitance characteristic done well.
Constant current charge and discharge test is carried out using electrochemical workstation, sets high potential 0.6V, low potential 0V, current density is
0.5~2.0mA/cm2, 1 circulation of scan period.The constant current charge-discharge test chart of carbon coating titanium nitride nano post array refers to
Fig. 7 B, constant current charge-discharge curve show symmetrical triangle feature, show good electrochemical reversible characteristic, result of calculation shows
Show the quality specific capacitance of carbon coating titanium nitride nano post array up to 94F/cm2。
Constant current test is carried out using electrochemical workstation, sets high potential 0.6V, low potential 0V, current density 2.0mA/
cm2, 2000 circulations of scan period.The cycle charge-discharge capacitance conservation rate test chart of carbon coating titanium nitride nano post array is detailed
See Fig. 7 C, after being carried out continuously 2000 cycle charge discharge electrical testings, specific capacity conservation rate is still maintained at more than 99%, shows very well
Cyclical stability.
Claims (9)
- A kind of 1. carbon coating titanium-based nano array material, it is characterised in that：Including conductive substrates (1), titanium-based nano array (2) and Amorphous carbon layer (3)；The titanium-based nano array (2) is arranged vertically on conductive substrates (1) surface, is interconnected with one another to form one Body formula structure；The amorphous carbon layer (3) is completely evenly coated at titanium-based nano array (2) surface；On the conductive substrates (1) " shell-core " nanostructured of ordered arrangement, described core is titanium-based nano line, nano-pillar or nano-tube array, and described shell is Amorphous carbon layer；The titanium-based includes titanium oxide or N doping titanium oxide；The titanium-based nano array (2) is one group of ordered arrangement Single nano-wire, cluster nano line, nano-pillar or nanotube.
- A kind of 2. carbon coating titanium-based nano array material according to claim 1, it is characterised in that：The conductive substrates (1) titanium sheet, electro-conductive glass, carbon cloth, carbon paper, graphene film, carbon nano-tube film or porous carbon film are included.
- A kind of 3. carbon coating titanium-based nano array material according to claim 1, it is characterised in that：The single nano-wire A diameter of 10~30nm；Cluster nano linear diameter is 20~200nm, and length is 1~1.5 μm；Nano-pillar a diameter of 100~ 300nm, length are 1~1.5 μm；Tube diameters are 50~100nm, and wall thickness is 10~30nm, and length is 3~5 μm.
- A kind of 4. carbon coating titanium-based nano array material according to claim 1, it is characterised in that：The amorphous carbon layer (3) thickness is 3~10nm.
- 5. a kind of preparation method of carbon coating titanium-based nano array material described in any one of Claims 1-4, its feature exist In：Comprise the following steps：(1) using seed auxiliary hydro-thermal reaction method and high-temperature calcination processing method prepare titanium oxide nano wire or Nano column array：In conductive substrates material surface physical absorption titaniferous seed liquor, it is placed in sealing hydrothermal reaction kettle, adds after drying Enter the mixed reaction solution of hydrochloric acid, water and titanium-based presoma, carry out hydro-thermal reaction；Reaction product carries out height under inert gas shielding Warm calcination processing, produce crystal phase titanium oxide nano wire or nano column array；Using constant voltage anodizing and high-temperature calcination Processing prepares titania nanotube array：In two electrode electro Chemical reaction systems, using titanium sheet as anode, platinized platinum be used as it is cloudy Pole, using ethylene glycol, water, ammonium fluoride mixed liquor as reaction electrolyte, carry out constant voltage anodic oxidation reactionses；Reaction product is lazy Property gas shield under high-temperature calcination handle, produce crystal phase titania nanotube array；(2) N doping TiOx nano array is prepared using controlled N doping processing method：By oxygen made from crystal phase step (1) Change titanium nano wire, nano-pillar or nano-tube array to be placed in tube-type atmosphere furnace, part N doping processing carried out under ammonia atmosphere, Produce N doping TiOx nano array；(3) carbon coating titanium-based nano array material is prepared using hydro-thermal reaction method and high-temperature calcination processing method：By titanium oxide and N doping TiOx nano array material is placed in sealing hydrothermal reaction kettle, is added hydro-thermal reaction liquid and is carried out hydro-thermal reaction；Reaction Product carries out high-temperature calcination processing under nitrogen protection, produces carbon coating titanium-based nano array material.
- A kind of 6. preparation method of carbon coating titanium-based nano array material according to claim 5, it is characterised in that：Step (1) in, the seed auxiliary hydro-thermal reaction law part is：Titaniferous seed liquor is that 0.3~0.9mol/L titanium-based precursor ethanols are molten Liquid, the volume ratio of hydrochloric acid, water and titanium-based presoma in hydro-thermal reaction liquid is 1:(1~1.1):(0.02~0.04), hydrochloric acid are 37% hydrochloric acid solution, the hydro-thermal reaction time are 7~20h, and hydrothermal temperature is 150~200 DEG C, and titanium-based presoma is tetrachloro Change titanium, butyl titanate or tetraisopropyl titanate；The constant voltage anodizing condition is：Anodic oxidation voltage be 30~ 60V, reaction time are 1~3h, and reaction temperature is 23~27 DEG C, is reacted in electrolyte, the volume fraction of ethylene glycol for 97~ 99%, the volume fraction of distilled water is 1~3%, and the mass fraction of ammonium fluoride is 0.2~0.3%；High-temperature calcination treatment conditions are equal For：Nitrogen gas concn is more than 99.7%, and nitrogen flow is 45~55mL/min；Heating rate is：Room temperature is 2 DEG C/min to 450 DEG C, 2h is incubated at 450 DEG C.
- A kind of 7. preparation method of carbon coating titanium-based nano array material according to claim 5, it is characterised in that：Step (2) in, described controlled N doping treatment conditions are：In ammonia atmosphere carry out N doping reaction, ammonia concentration be 99.6~ 99.9%, ammonia flow is 30~60mL/min, and heating rate is 5 DEG C/min from room temperature to 300 DEG C, is from 300 DEG C to 600 DEG C 2 DEG C/min, 600 DEG C of isothermal reaction 3h.
- A kind of 8. preparation method of carbon coating titanium-based nano array material according to claim 5, it is characterised in that：Step (3) in, the hydro-thermal reaction method condition is：Hydro-thermal reaction liquid is 0.05~0.2mol/L carbon-source cpd aqueous solution, and hydro-thermal is anti- It is 1~5h between seasonable, hydrothermal temperature is 160~180 DEG C, and carbon-source cpd is glucose, sucrose or starch；The high temperature Calcination processing condition is：Nitrogen gas concn is more than 99.9%, and nitrogen flow is 30~50mL/min；Heating rate is room temperature to 550 DEG C be 3 DEG C/min, 550 DEG C to 800 DEG C be 2 DEG C/min, be incubated 1h at 800 DEG C.
- 9. application of the carbon coating titanium-based nano array material in ultracapacitor described in any one of Claims 1-4.
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| CN112563509A (en) * | 2020-12-08 | 2021-03-26 | 昆山宝创新能源科技有限公司 | Titanium dioxide nanotube-loaded carbon-coated nano-silicon composite material and preparation method and application thereof |
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