CN110357152A - A kind of preparation method of the anodic titanium nanotube of metallic element doping - Google Patents
A kind of preparation method of the anodic titanium nanotube of metallic element doping Download PDFInfo
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- CN110357152A CN110357152A CN201910681797.9A CN201910681797A CN110357152A CN 110357152 A CN110357152 A CN 110357152A CN 201910681797 A CN201910681797 A CN 201910681797A CN 110357152 A CN110357152 A CN 110357152A
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000010936 titanium Substances 0.000 title claims abstract description 31
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 26
- 239000002071 nanotube Substances 0.000 title claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000009835 boiling Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 24
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 42
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 39
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 15
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 claims description 4
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- 229910052742 iron Inorganic materials 0.000 claims 1
- 238000007743 anodising Methods 0.000 abstract description 7
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 23
- 239000012528 membrane Substances 0.000 description 18
- 229910052782 aluminium Inorganic materials 0.000 description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 16
- 239000004411 aluminium Substances 0.000 description 13
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 7
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 241001481828 Glyptocephalus cynoglossus Species 0.000 description 4
- -1 boiling point 181°C) Chemical compound 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 229910003091 WCl6 Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical group Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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Abstract
The invention discloses a kind of preparation methods of the anodic titanium nanotube of metallic element doping.Anodic titanium nanotube is prepared by conventional constant current or constant pressure anodizing, then in closed container, prepared anodic titanium nanotube and low boiling point (are lower than 400°C metallic compound (as metal-doped source)) is heated together, carries out the processing of certain time to anodic titanium nanotube using steam caused by metallic compound, metallic element may be implemented to the Effective Doping of titanium oxide nanotubes.It is easy to operate using the method for the invention, the performance of the supercapacitor being remarkably reinforced is shown by the anodic titanium nanotube that metallic element adulterates.
Description
Technical field
The invention belongs to electrochemical technology fields, are related to a kind of preparation of the anodic titanium nanotube of metallic element doping
Method.
Background technique
Titania nanotube array (the TiO that titanium is prepared by anodizing2NTAs, anodic titanium nanometer
Pipe) film, because of its many merits: such as high-specific surface area, vertically oriented nanostructure, chemical stability and simple preparation method
Deng getting more and more people's extensive concerning.Currently, the TiO of this special one-dimensional nano structure2NTAs film, in solar-electricity
Many fields such as pond, photocatalytic water, supercapacitor show the application prospect got a good chance of.When being applied to supercapacitor
When, the TiO of high-sequential2NTAs film can provide directapath, and TiO for electronics and ion transmission2Below NTAs film
Titanium substrate can be used as collector, and electrode of super capacitor is directly obtained without binder.However, because TiO2It is a kind of broadband
Gap semiconductor (anatase is 3.2 eV, and rutile is 3.0 eV), finite conductivity, electro-chemical activity is low, so causing it super
Grade capacitive property can not be with RuO2Performance etc. typical metal oxide materials compares.Therefore, try to explore to solve TiO2This
The method of a little limitations is very important.
According to the literature, by by metal (ZK Zheng, et al. Journal of Materials Chemistry
21 (2011) 9079) or nonmetallic inclusion (X Chen, et al. Chemical Reviews 107 (2007) 2891)
Introduce TiO2In the increase of its conductivity may be implemented because this can generate alms giver or acceptor state in band gap, to increase
TiO2In carrier concentration so that improve its conductivity.In order to improve TiO2The super capacitor performance of material, past 20
Various doping methods have been had investigated in year.These are to TiO2The method being doped is mainly included in vacuum, argon atmosphere
(example under (M. Salari, et al., Phys. Chem. Chem. Phys., 2012,14,4770.) or reducing condition
Such as H2、NH3Or acetylene) heat treatment (R. Hahn, et al., Angew. Chem. Int. Ed., 2009,48,
7236.), hydro-thermal process (R. Yuan, et al., J. Hazard. Mater., 2013,262,527.), hydrogen plasma
Body processing (H. Wu, et al., Nanotechnology, 2013,24,455401.), energetic ion inject (A.
Ghicov, et al., Nano Lett., 2006,6,1080.) and (CN103165283A such as reproducibility electrochemical doping；
W. Zhong, et al., J. Power Sources, 2015,294,216.).However, these reports and disclosed side
Method is primarily adapted for use in TiO2Auto-dope and nonmetal doping.Although hydro-thermal process and energetic ion injection are to realize metallic element
Adulterate TiO2Effective ways, but these methods there is limitations, such as: processing step is excessively complicated, may destroy sun
The harsh reaction condition of pole titanium oxide nanotubes, or need expensive equipment.In addition, the metastable state due to electrochemical doping is special
Property, so realizing the TiO of metallic element doping by electrochemistry2The cyclical stability of NTAs film there is a problem of very big.Cause
This, explores easy and economic method to realize that stable metallic element adulterates TiO2NTAs film is one in the urgent need to address
The problem of.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of the anodic titanium nanotube of metallic element doping.
The technical solution for realizing the aim of the invention is as follows: a kind of system of the anodic titanium nanotube of metallic element doping
Preparation Method, in closed container, by anodic titanium nanotube and low-boiling metallic compound at 220 ± 10 DEG C at heating
2 ~ 3h is managed, anodic titanium nanotube is handled using steam caused by metallic compound under heat treatment condition, is made
The anodic titanium nanotube of metallic element doping.
In above-mentioned steps, the boiling point of low-boiling metallic compound should be lower than the annealing temperature 400 of anatase-type titanium oxide°C, including aluminium chloride (AlCl3, boiling point 181°C), iron chloride (FeCl3, boiling point 315°C), copper citrate (C6H4Cu2O7, boiling point
It is 309.6 C) and tungsten chloride (WCl6, boiling point is 347 C) etc. in any one.
In above-mentioned steps, anodic titanium nanotube passes through conventional constant current or the preparation of constant pressure anodizing, wherein electricity
It solves liquid and uses the ethylene glycol solution containing 0.3 wt% ammonium fluoride and 2 vol% water, electrolyte temperature is controlled always 25°C hereinafter, with
Polishing titanium foil is anode, and graphite plate is cathode, with 10 mA cm of current density-225 min of constant current anodic oxidation, or with 60 V perseverance
Press 40 min of anodic oxidation.
Compared with prior art, the present invention its remarkable advantage are as follows:
(1) different from existing hydro-thermal process, energetic ion injection and hydrogen plasma process, the present invention is energy saving, easy to operate,
Expensive instrument and equipment is not needed, and can guarantee TiO2Integrality and and titanium of the NTAs film after doping treatment technique
The adhesiveness of substrate.
(2) different from the processing of existing electrochemical doping, the present invention can effectively realize stable metallic element doping
TiO2NTAs film, and its cyclical stability applied to supercapacitor when is significantly improved, it can meet well
The requirement of practical application.
(3) as long as boiling point of the invention is less than 400°The metallic compound of C may be used for steam treated and realize stable gold
Belong to element doping TiO2NTAs film, and make TiO2NTAs membrane electrode shows the performance of the supercapacitor being remarkably reinforced.
Detailed description of the invention
Fig. 1 is X-ray diffraction (X-ray diffraction, the XRD) figure and partial enlargement of comparative example 1 Yu embodiment 1
Figure.
Fig. 2 is x-ray photoelectron spectroscopy (the X-ray photoelectron of comparative example 1 Yu embodiment 1
Spectroscopy, XPS) figure and partial enlarged view.
Fig. 3 is Raman spectrum (Raman spectra, the Raman) figure and partial enlarged view of comparative example 1 Yu embodiment 1.
Fig. 4 is the cyclic voltammetry curve and constant current charge-discharge curve of comparative example 1 and embodiment 1.
Specific embodiment
Below with reference to embodiment and attached drawing, present invention is further described in detail.
The present invention prepares anodic titanium nanotube, that is, TiO in conventional constant current or constant pressure anodizing2NTAs film
After step, in closed container, by prepared TiO2NTAs film and low boiling point (are lower than 400°C metallic compound)
(as metal-doped source) is heated together, using steam caused by metallic compound to TiO2NTAs film carries out
The processing of certain time, so that it may realize metallic element to TiO2NTAs Effective Doping, the TiO adulterated by metallic element2
NTAs membrane electrode shows the performance of the supercapacitor being remarkably reinforced.
The principle of the present invention is as follows: in closed container, the TiO of anodic oxidation preparation2NTAs film and low boiling point are (low
In 400°C metallic compound (as metal-doped source)) is heated together, using caused by metallic compound
Steam is to TiO2The processing of NTAs film progress certain time.In treatment process, metal ion in metal compound vapor can be with
To replace Ti4+Form enter TiO2Lattice in, be inserted into TiO with the metal ion clearance-type realized by electrochemical doping2
The metastable state form of lattice is different, and the doping of substitution formula is a kind of stable dopant states, therefore, at metal compound vapor
Reason realizes the TiO of metallic element doping2NTAs membrane electrode shows good cyclical stability.Simultaneously because doping metals from
Sub- valence state is different from Ti4+, when it replaces Ti4+Into TiO2When lattice, in order to keep electroneutral necessarily lead to Lacking oxygen and (or)
Ti3+Gap, in TiO2Alms giver or acceptor state are generated in band gap, so that TiO2The conductivity of NTAs increases and electro-chemical activity increases
By force, the performance of the supercapacitor being remarkably reinforced finally is shown.
The present invention through the following steps that realize:
Step 1 prepares TiO by constant current or constant pressure anodizing2NTAs film.To contain 0.3 wt% ammonium fluoride and 2 vol%
The ethylene glycol solution of water is electrolyte, and to polish titanium foil as anode, graphite plate is cathode, and electrolyte temperature is controlled 25°C with
Under, with 10 mA cm of current density-225 min of constant current anodic oxidation, or TiO is obtained with 40 min of 60V constant pressure anodic oxidation2
NTAs film.
Step 2, in closed container, prepared TiO2NTAs film and low-boiling metallic compound one arise from 220
Heat 2 ~ 3h at ± 10 DEG C, using steam caused by metallic compound to TiO2NTAs film is handled, so that it may real
Existing metallic element is to TiO2The doping of NTAs.Wherein, the boiling point of metallic compound should be lower than the annealing temperature of anatase-type titanium oxide
Degree 400°C, such as aluminium chloride (AlCl3, boiling point 181°C), iron chloride (FeCl3, boiling point 315°C), copper citrate
(C6H4Cu2O7, 309.6 C of boiling point) and tungsten chloride (WCl6, boiling point is 347 C) etc..
Comparative example 1
First by purity 99.5%, 100 μm of thickness, the cm of 6 cm × 1 titanium foil item, immerse volume ratio 1:1:2 hydrofluoric acid, nitre
10 ~ 20 s are handled in the polishing fluid of acid and water composition, remove the oxidation film on titanium surface.Then it is rinsed well with deionized water.With
This titanium foil is as anode, and using the graphite flake of another same size as cathode, electrode spacing is 2 cm and keeping parallelism.Containing
In the ethylene glycol solution of 0.3 wt% ammonium fluoride and 2 vol% water, constant current anodic oxidation reactions, 10 mA cm of current density are carried out-2,
Anodizing time is 25 min；Or carry out constant pressure anodic oxidation reactions, 60 V of oxidation voltage, anodizing time 40
min.In anode oxidation process, the temperature of electrolyte is maintained at 20 by the sub-cooled circulatory system°C。TiO2The thickness of NTAs film
About 9.6 μm of degree.It is finally made annealing treatment, i.e., with 5 C min-1Heating rate, keep the temperature 2 h after being warming up to 150 C, with
Afterwards with 1 C min-1Heating rate continue to heat up, keep the temperature 3 h after rising to 450 C, then Temperature fall.Using three-electrode system
To TiO2NTAs membrane electrode carries out electrochemical property test, wherein TiO2NTAs membrane electrode is saturated calomel as working electrode
Electrode is as reference electrode, and platinized platinum is used as to electrode, and test area is 2 cm2.The sweep speed of cyclic voltammetry (CV) is
100 mV s–1, the current density of constant current charge-discharge test (GCD) is 0.5 mA cm-2, test electrolyte is 0.5 M H2SO4。
It is tested to obtain TiO by CV2The area specific capacitance of NTAs membrane electrode is 0.97 mF cm-2, see attached drawing 1 (a).It is tested by GCD
To TiO2The cyclical stability of NTAs membrane electrode is only to keep the 84% of initial capacitance after recycling 1000 times, sees attached drawing 1 (b).
Embodiment 1
Size, pretreatment and the anodic oxidation condition of titanium foil item are the same as comparative example 1.In the closed container of 50 mL, by anodic oxidation
The TiO of method preparation2NTAs film and 5 g aluminium chloride (AlCl3, boiling point 181°C) heated together, at 220 C, benefit
With chlorination aluminum vapor to TiO22 h of NTAs film process takes out after natural cooling.Then it carries out at the identical annealing of same comparative example 1
Reason.
To the TiO of aluminium doping2NTAs film show with the identical XRD of comparative example 1 test: obtained all TiO2
The peak of NTAs film is in addition to the TiO that the peak of Ti substrate (2 θ=40.20 °, 53.11 °, 70.72 °) is all Detitanium-ore-type2Peak,
Corresponding card number is JCPDF No. 44-1294 and JCPDF No. 21-1272 respectively, sees attached drawing 1 (a).Aluminium doping
TiO2(101) diffraction maximum of NTAs film deviates to low diffraction angular direction compared to comparative example 1, it was demonstrated that aluminium doping is shown in attached
Fig. 1 (b).
To the TiO of aluminium doping2NTAs film show with the identical XPS of comparative example 1 test: having obtained the TiO of aluminium doping2
The Photoelectron peak Al 2p (74.89 eV) of NTAs film, Ti 2p (457-464 eV), O 1s (527-534 eV), and C
1s (284.6 eV), is shown in attached drawing 2 (a).The TiO of aluminium doping2The XPS energy level spectrum of the Al 2p of NTAs film show one with
Clear peak centered on 74.89 eV, this is Al3+Peak, it was demonstrated that attached drawing 2 (b) is shown in aluminium doping.
To the TiO of aluminium doping2NTAs film show with the identical Raman of comparative example 1 test: the TiO of aluminium doping2
The Raman peaks of NTAs film broaden and mobile to long wave direction, blue shift occurs, it was demonstrated that the introducing i.e. aluminium doping of Lacking oxygen are shown in
Attached drawing 3 (a) and attached drawing 3 (b).
To the TiO of aluminium doping2NTAs membrane electrode tested with the identical electrochemical property test of comparative example 1 by CV
The TiO adulterated to aluminium2The area specific capacitance of NTAs membrane electrode is 2.46 mF cm-2, compared to comparative example 1, area specific capacitance increases
It is about 2.5 times big, see attached drawing 4 (a).It is tested to obtain the TiO of aluminium doping by GCD2The cyclical stability of NTAs membrane electrode, as a result
Show: still keeping the 100% of initial capacitance after circulation 8500 times, significantly improve, see attached compared to 1 cyclical stability of comparative example
Fig. 4 (b).
Embodiment 2
Size, pretreatment and the anodic oxidation condition of titanium foil item are the same as comparative example 1.In the closed container of 50 mL, by anodic oxidation
The TiO of method preparation2NTAs film and 5 g iron chloride (FeCl3, boiling point 315°C) heated together, at 450 C, benefit
With iron chloride steam to TiO23 h of NTAs film process takes out after natural cooling.Here heat-treatment process is doping and moves back
Fire one step of processing is completed, more convenient.XPS test shows to have obtained the TiO of Fe2O3 doping2NTAs.To the TiO of Fe2O3 doping2
NTAs membrane electrode carries out being tested to obtain the TiO of ferro element doping by CV with the identical electrochemical property test of comparative example 12 NTAs
The area specific capacitance of membrane electrode is 3.23 mF cm-2, compared to comparative example 1, area specific capacitance increases about 3.3 times.By GCD
Test obtains the TiO of Fe2O3 doping2The cyclical stability of NTAs membrane electrode, the results showed that still keep initial after circulation 10000 times
The 98.4% of capacitance is significantly improved compared to 1 cyclical stability of comparative example.
Embodiment 3
In addition to changing low-boiling metallic compound iron chloride into copper citrate (C6H4Cu2O7, 309.6 C of boiling point) outside, other
All techniques are the same as embodiment 2.XPS test shows to have obtained the TiO of Copper-cladding Aluminum Bar2NTAs.To the TiO of Copper-cladding Aluminum Bar2NTAs film electricity
Pole carries out being tested to obtain the TiO of Copper-cladding Aluminum Bar by CV with the identical electrochemical property test of comparative example 12The area of NTAs membrane electrode
Specific capacitance is 2.21 mF cm-2, compared to comparative example 1, area specific capacitance increases about 2.3 times.It tests to obtain copper by GCD and mix
Miscellaneous TiO2The cyclical stability of NTAs membrane electrode, the results showed that still keep initial capacitance after circulation 10000 times
97.8%, it is significantly improved compared to 1 cyclical stability of comparative example.
Embodiment 4
In addition to changing low-boiling metallic compound iron chloride into tungsten chloride (WCl6, 347 C of boiling point) outside, other all techniques
With embodiment 2.XPS test shows to have obtained the TiO of witch culture2NTAs.To the TiO of witch culture2NTAs membrane electrode carries out same
The identical electrochemical property test of comparative example 1, is tested to obtain the TiO of witch culture by CV2The area specific capacitance of NTAs membrane electrode is
3.28 mF cm-2, compared to comparative example 1, area specific capacitance increases about 3.4 times.It is tested to obtain the TiO of witch culture by GCD2
The cyclical stability of NTAs membrane electrode, the results showed that circulation 10000 times after still keep the 98.8% of initial capacitance, compared to than
It is significantly improved compared with 1 cyclical stability of example.
Claims (5)
1. a kind of preparation method of the anodic titanium nanotube of metallic element doping, which is characterized in that, will in closed container
Anodic titanium nanotube and low-boiling metallic compound heat 2 ~ 3h at 220 ± 10 DEG C, utilize heat treatment condition
Steam caused by the lower metallic compound handles anodic titanium nanotube, and the anodic oxygen of metallic element doping is made
Change titanium nanotube.
2. the method as described in claim 1, which is characterized in that the boiling point of low-boiling metallic compound is lower than Detitanium-ore-type
The annealing temperature of titanium oxide i.e. 400°C。
3. method according to claim 1 or 2, which is characterized in that low-boiling metallic compound includes aluminium chloride, chlorination
Any one in iron, copper citrate and tungsten chloride.
4. the method as described in claim 1, which is characterized in that anodic titanium nanotube passes through constant current anodic oxidation legal system
It is standby, wherein electrolyte uses the ethylene glycol solution containing 0.3 wt% ammonium fluoride and 2 vol% water, and electrolyte temperature is controlled 25°C
Hereinafter, to polish titanium foil as anode, graphite plate is cathode, with 10 mA cm of current density-225 min of constant current anodic oxidation.
5. the method as described in claim 1, which is characterized in that anodic titanium nanotube passes through constant pressure anodic oxidation legal system
It is standby, wherein electrolyte uses the ethylene glycol solution containing 0.3 wt% ammonium fluoride and 2 vol% water, and electrolyte temperature is controlled 25°C
Hereinafter, to polish titanium foil as anode, graphite plate is cathode, with 60 V constant pressure anodic oxidation, 40 min.
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