CN104201362A - Preparing method of carbon-doped titanium oxide nanotube array lithium battery anode material - Google Patents
Preparing method of carbon-doped titanium oxide nanotube array lithium battery anode material Download PDFInfo
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- CN104201362A CN104201362A CN201410182014.XA CN201410182014A CN104201362A CN 104201362 A CN104201362 A CN 104201362A CN 201410182014 A CN201410182014 A CN 201410182014A CN 104201362 A CN104201362 A CN 104201362A
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- lithium cell
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000010405 anode material Substances 0.000 title abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000010936 titanium Substances 0.000 claims abstract description 31
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 22
- 238000000137 annealing Methods 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000003647 oxidation Effects 0.000 claims abstract description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000002071 nanotube Substances 0.000 claims description 35
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical class NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 239000002152 aqueous-organic solution Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 150000003457 sulfones Chemical class 0.000 claims description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000243 solution Substances 0.000 abstract description 4
- 125000004429 atom Chemical group 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 238000001149 thermolysis Methods 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- 238000009210 therapy by ultrasound Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 6
- 229960005196 titanium dioxide Drugs 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- -1 doping C Chemical compound 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a preparing method of a carbon-doped titanium oxide nanotube array lithium battery anode material and belongs to the technical field of lithium batteries. The method includes cleaning surfaces of a pure titanium sheet, connecting the pure titanium sheet to the cathode, connecting a platinum sheet to the anode, putting the pure titanium sheet into an aqueous solution or an organic solution of a dissoluble fluoride, performing anode oxidation, cleaning the pure titanium sheet, drying to obtain a titanium oxide nanotube array, subjecting the titanium oxide nanotube array to heating and ultrasonic treatment in an alcohol reagent, and annealing to obtain a carbon-doped titanium oxide nanotube array. The method utilizes thermolysis of the alcohol solution in a high-temperature annealing process, carbon atoms replace a part of Ti atoms in titanium oxide crystal lattices to form a Ti-O-C structure, thus achieving an objective of reducing the forbidden band width, and increasing electronic conductivity of the material. Operation is simple. Performance of a lithium battery is obviously improved.
Description
Technical field
The preparation method who the present invention relates to a kind of Carbou doped titanium-oxide nano-tube array Anode of lithium cell material, belongs to technical field of lithium batteries.
Background technology
Along with the exhaustion gradually of oil coal equal energy source, environment and energy problem are restricting the mankind's fast development.The demand of novel energy-storing system increases day by day.Compare traditional energy storage system, as lead-acid battery, nickel-cadmium cell and Ni-MH battery, lithium ion battery has high energy storage density, it is few to pollute, the remarkable advantages such as voltage is high, have extended cycle life, memory-less effect.
Many advanced persons' lithium ion battery negative material, silicon for example, having higher theoretical capacity value is 4200 mAh/g, but in the de-embedding process of lithium ion, easily causes that large change in volume causes active material to come off from electrode.In addition, widely used commercial materials graphite, because its operating voltage is too low, easily forms solid electrolyte interface, easily causes safety problem and capacity loss.And with titanium oxide as lithium cell cathode material, have price low, content is high, change in volume little (being less than 4%), high discharge voltage plateau, the advantages such as good cycle, have caused widely research.
Yet titanium oxide has wider energy gap (3.0～3.2ev), electron conduction is poor, is unfavorable for the de-embedding of Li ion, has restricted its practical application.Relevant report shows in recent years, utilize the methods such as electro-deposition, hydro thermal method, vapour deposition can loaded Ag, the metal such as Cu or or the forbidden band of the nonmetal attenuating titanium oxide nanotubes such as doping C, N wide, the charge/discharge capacity that has improved significantly lithium battery, has reduced the time of discharging and recharging.Above method, operation is many and complicated, and also high to experimental facilities requirement, production cost is expensive, is unfavorable for production application.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides a kind of preparation method of Carbou doped titanium-oxide nano-tube array Anode of lithium cell material, utilize alcoholic solution thermal decomposition in high-temperature annealing process, carbon atom replaces part Ti atom in titanium oxide lattice, form Ti-O-C structure, thereby reach the object that reduces energy gap, improve the electronic conductivity of material, simple to operate, lithium battery performance is obviously improved.
Technical scheme of the present invention possesses and comprises the following steps:
(1) titania nanotube array is prepared in anodic oxidation: pure titanium plate surface clean is clean, under the effect of constant voltage, pure titanium sheet connects positive pole, platinized platinum connects negative pole, then be placed in the aqueous solution or organic solution Anodic Oxidation containing solubilized villiaumite, finally pure titanium sheet is cleaned up to rear being dried, obtain titania nanotube array;
(2) electrolyte pyrolysis is prepared Carbou doped titanium-oxide nano-tube array: titania nanotube array is heated in organic solvent to ultrasonic processing, subsequently sample is annealed, after the ultrasonic processing of as above repeated multiple times heating and annealing in process, obtain the titania nanotube array of carbon doping.The ultrasonic processing of repeated multiple times heating and annealing in process are in order to increase the content of carbon in titanium oxide, and in titanium oxide, carbon content scope is 9.0%～27.5%.
Described pure titanium sheet is that titanium foil, titanium band, titanium plate all can.
Described pure titanium plate surface clean is to adopt successively chemical polishing after acetone, ethanol, deionized water ultrasonic cleaning.
The described aqueous solution containing solubilized villiaumite is for containing NaF, KF or NH
4the H of F
3pO
4, Na
2sO
4, (NH
4)
2sO
4or K
2sO
4the aqueous solution, wherein containing NaF, KF or NH in the aqueous solution of solubilized villiaumite
4the concentration of F is 0.2～0.5mol/L, H
3pO
4, Na
2sO
4, (NH
4)
2sO
4or K
2sO
4concentration be 0.1～1mol/L.
Described organic solution is alcohols, amine or sulfone class.
Described alcohols is for being preferably ethylene glycol, glycerol or diethylene glycol (DEG), and ammonium class is that formamide, sulfone class are dimethyl sulfoxide (DMSO).
Described anodic oxidation voltage is 20～60V, and oxidization time is 1～3 hour.
Described ultrasonic power is 20～60W, and ultrasonic time is 5 minutes～10 minutes, and heating-up temperature is 40～80 ℃.
Described annealing temperature is 200～600 ℃, and in annealing process, intensification per minute is 1～5 ℃, keeps 1～3 hour.
The present invention's raw material used be take pure Ti sheet as main (purity 99.99%), capital equipment is D.C. regulated power supply, the titania nanotube array of carbon doping prepared by the present invention has demonstrated good chemical property as Anode of lithium cell material: under identical current density, the charge/discharge capacity of the titania nanotube array lithium battery of carbon doping is significantly improved; Under identical test condition, the electrochemical impedance of the titania nanotube array lithium battery of carbon doping has had significantly and has reduced.
Advantage of the present invention and good effect: utilize anodic oxidation, thermolysis process to prepare Carbou doped titanium-oxide nano-tube array anode material, the method is low for equipment requirements, simple to operate, cost is low, in lithium rechargeable battery, show good chemical property, be conducive to the application of titanium black anode material suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the surface topography map of titania nanotube array of the present invention;
Fig. 2 is the XPS figure of the full spectrogram of Carbou doped titanium-oxide nanotube XPS of the present invention and C1s;
Fig. 3 is the XPS figure of Carbou doped titanium-oxide nanotube Ti2p of the present invention;
Fig. 4 is the XPS figure of titania nanotube array C1s of the present invention;
Fig. 5 is the charging and discharging curve of first three time of Carbou doped titanium-oxide nano-tube array of the present invention;
Fig. 6 is the charging and discharging curve of first three time of titania nanotube array of the present invention;
Fig. 7 is Carbou doped titanium-oxide nano-tube array of the present invention and the charging and discharging curve of titania nanotube array under different current densities;
Fig. 8 is the AC impedance figure of Carbou doped titanium-oxide nano-tube array of the present invention and titania nanotube array.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Execution mode one: as shown in Fig. 1 to 8, the preparation method of the Carbou doped titanium-oxide nano-tube array Anode of lithium cell material of present embodiment is:
(1) pure Ti sheet (thickness 0.2mm, diameter 14mm) is used successively to acetone, absolute ethyl alcohol, washed with de-ionized water 20 minutes, then at 5mlHF, 5mlHNO
3, 20mlH
2polishing in the mixed liquor of O, then cleaning-drying is standby.With Ti sheet, connect positive source, with Pt, connect negative pole, in containing 0.5wt%NH4F and the 0.2Mol H3PO4 aqueous solution, with 20V constant voltage anodic oxidation 2 hours, by the sample washed with de-ionized water making, dry adapted.Fig. 1 is the surface topography of titania nanotube array.It is in 99.5% ethylene glycol that dried sample is immersed in to concentration, 40W power, at 60 degree temperature ultrasonic 10 minutes.After repeatedly ultrasonic through 5 times, ethylene glycol is more retained in titania nanotube array.
(2) sample is placed in crucible, puts into tube furnace, with 5 degree per minute, rise to 450 degree, be incubated 1 hour, obtain the titania nanotube array of carbon doping.Fig. 2,3,4 is the C of titania nanotube array electrode and the XPS analysis of Ti of titania nanotube array electrode and carbon doping.Fig. 5,6, the 7th, the electrochemical properties of test sample, result shows that the capacity of the titania nanotube array of carbon doping is almost the twice of titania nanotube array capacity, and under different densities stable circulation.That Fig. 8 is the AC impedance figure of sample, and result shows, the conductivity of the titania nanotube array of carbon doping obviously strengthens.
Execution mode two: the preparation method of the Carbou doped titanium-oxide nano-tube array Anode of lithium cell material of present embodiment is:
(1) titania nanotube array is prepared in anodic oxidation: pure titanium plate surface clean is clean, adopt successively chemical polishing after acetone, ethanol, deionized water ultrasonic cleaning, under the effect of constant voltage, pure titanium sheet connects positive pole, platinized platinum connects negative pole, then be placed in the aqueous solution or organic solution Anodic Oxidation containing solubilized villiaumite, anodic oxidation voltage is 20V, and oxidization time is 1 hour, finally pure titanium sheet is cleaned up to rear being dried, obtain titania nanotube array; The aqueous solution containing solubilized villiaumite is the H containing NaF
3the aqueous solution of PO, wherein the concentration containing NaF in the aqueous solution of solubilized villiaumite is 0.2mol/L, H
3pO
4concentration be 0.1 mol/L;
(2) electrolyte pyrolysis is prepared Carbou doped titanium-oxide nano-tube array: titania nanotube array is heated in formamide to ultrasonic processing, ultrasonic power is 20W, ultrasonic time is 5 minutes, heating-up temperature is 40 ℃, subsequently sample is annealed, annealing temperature is 200 ℃, and in annealing process, intensification per minute is 1 ℃, keep 1 hour, after as above repeated multiple times immersion and annealing in process, obtain the titania nanotube array of carbon doping.
Execution mode three: the preparation method of the Carbou doped titanium-oxide nano-tube array Anode of lithium cell material of present embodiment is:
(1) titania nanotube array is prepared in anodic oxidation: pure titanium plate surface clean is clean, adopt successively chemical polishing after acetone, ethanol, deionized water ultrasonic cleaning, under the effect of constant voltage, pure titanium sheet connects positive pole, platinized platinum connects negative pole, then be placed in the aqueous solution or organic solution Anodic Oxidation containing solubilized villiaumite, anodic oxidation voltage is 60V, and oxidization time is 3 hours, finally pure titanium sheet is cleaned up to rear being dried, obtain titania nanotube array; The aqueous solution containing solubilized villiaumite is the Na containing KF
2sO
4the aqueous solution, wherein the concentration containing KF in the aqueous solution of solubilized villiaumite is 0.5mol/L, Na
2sO
4concentration be 1mol/L;
(2) electrolyte pyrolysis is prepared Carbou doped titanium-oxide nano-tube array: titania nanotube array is heated in dimethyl sulfoxide (DMSO) to ultrasonic processing, ultrasonic power is 60W, ultrasonic time is 10 minutes, heating-up temperature is 80 ℃, subsequently sample is annealed, annealing temperature is 600 ℃, and in annealing process, intensification per minute is 5 ℃, keep 3 hours, after as above repeated multiple times immersion and annealing in process, obtain the titania nanotube array of carbon doping.
Execution mode four: the preparation method of the Carbou doped titanium-oxide nano-tube array Anode of lithium cell material of present embodiment is:
(1) titania nanotube array is prepared in anodic oxidation: pure titanium plate surface clean is clean, adopt successively chemical polishing after acetone, ethanol, deionized water ultrasonic cleaning, under the effect of constant voltage, pure titanium sheet connects positive pole, platinized platinum connects negative pole, then be placed in the aqueous solution or organic solution Anodic Oxidation containing solubilized villiaumite, anodic oxidation voltage is 40V, and oxidization time is 2 hours, finally pure titanium sheet is cleaned up to rear being dried, obtain titania nanotube array; The aqueous solution containing solubilized villiaumite is containing NH
4(the NH of F
4)
2sO
4the aqueous solution, wherein containing NH in the aqueous solution of solubilized villiaumite
4the concentration of F is 0.3mol/L, (NH
4)
2sO
4concentration be 0.6mol/L;
(2) electrolyte pyrolysis is prepared Carbou doped titanium-oxide nano-tube array: titania nanotube array is heated in diethylene glycol (DEG) to ultrasonic processing, ultrasonic power is 20～60W, ultrasonic time is 9 minutes, heating-up temperature is 60 ℃, subsequently sample is annealed, annealing temperature is 300 ℃, and in annealing process, intensification per minute is 4 ℃, keep 2 hours, through as above repeatedly obtaining the titania nanotube array that carbon adulterates after the immersion of 6 times and annealing in process.
Below by reference to the accompanying drawings the specific embodiment of the present invention is explained in detail, but the present invention is not limited to above-mentioned execution mode, in the ken possessing those of ordinary skills, can also under the prerequisite that does not depart from aim of the present invention, make various variations.
Claims (8)
1. a preparation method for Carbou doped titanium-oxide nano-tube array Anode of lithium cell material, is characterized in that concrete steps comprise:
(1) pure titanium plate surface clean is clean, under the effect of constant voltage, pure titanium sheet connects positive pole, platinized platinum connects negative pole, is then placed in the aqueous solution or organic solution Anodic Oxidation containing solubilized villiaumite, finally pure titanium sheet is cleaned up to rear being dried, obtain titania nanotube array;
(2) titania nanotube array is heated in organic solvent to ultrasonic processing, subsequently sample is annealed, after the ultrasonic processing of as above repeated multiple times heating and annealing in process, obtain the titania nanotube array of carbon doping.
2. the preparation method of Carbou doped titanium-oxide nano-tube array Anode of lithium cell material according to claim 1, is characterized in that: described pure titanium plate surface clean is to adopt successively chemical polishing after acetone, ethanol, deionized water ultrasonic cleaning.
3. the preparation method of Carbou doped titanium-oxide nano-tube array Anode of lithium cell material according to claim 1, is characterized in that: the described aqueous solution containing solubilized villiaumite is for containing NaF, KF or NH
4the H of F
3pO
4, Na
2sO
4, (NH
4)
2sO
4or K
2sO
4the aqueous solution, wherein containing NaF, KF or NH in the aqueous solution of solubilized villiaumite
4the concentration of F is 0.2～0.5 wt%, H
3pO
4, Na
2sO
4, (NH
4)
2sO
4or K
2sO
4concentration be 0.1～1mol/L.
4. the preparation method of Carbou doped titanium-oxide nano-tube array Anode of lithium cell material according to claim 1, is characterized in that: described organic solvent is alcohols, amine or sulfone class.
5. the preparation method of Carbou doped titanium-oxide nano-tube array Anode of lithium cell material according to claim 1, is characterized in that: described anodic oxidation voltage is 20～60V, and oxidization time is 1～3 hour.
6. the preparation method of Carbou doped titanium-oxide nano-tube array Anode of lithium cell material according to claim 4, is characterized in that: described alcohols is ethylene glycol, glycerol or diethylene glycol (DEG), and ammonium class is that formamide, sulfone class are dimethyl sulfoxide (DMSO).
7. the preparation method of Carbou doped titanium-oxide nano-tube array Anode of lithium cell material according to claim 1, is characterized in that: described ultrasonic power is 20～60W, and ultrasonic time is 5 minutes～10 minutes, and heating-up temperature is 40～80 ℃.
8. the preparation method of Carbou doped titanium-oxide nano-tube array Anode of lithium cell material according to claim 1, is characterized in that: described annealing temperature is 200～600 ℃, and in annealing process, intensification per minute is 1～5 ℃, keeps 1～3 hour.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105390688A (en) * | 2015-03-23 | 2016-03-09 | 昆明理工大学 | Manufacturing method for copper oxide loaded titanium dioxide nano through tube array and application of copper oxide loaded titanium dioxide nano through tube array |
| CN107565114A (en) * | 2017-08-30 | 2018-01-09 | 北京理工大学 | A kind of binder free anode material of lithium-ion battery and preparation method thereof |
| CN114457367A (en) * | 2022-03-01 | 2022-05-10 | 厦门稀土材料研究所 | Preparation method and application of vacuum carbon-doped titanium dioxide nanotube array structure |
Citations (3)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105390688A (en) * | 2015-03-23 | 2016-03-09 | 昆明理工大学 | Manufacturing method for copper oxide loaded titanium dioxide nano through tube array and application of copper oxide loaded titanium dioxide nano through tube array |
| CN107565114A (en) * | 2017-08-30 | 2018-01-09 | 北京理工大学 | A kind of binder free anode material of lithium-ion battery and preparation method thereof |
| CN107565114B (en) * | 2017-08-30 | 2020-12-15 | 北京理工大学 | Binderless sodium ion battery negative electrode material and preparation method thereof |
| CN114457367A (en) * | 2022-03-01 | 2022-05-10 | 厦门稀土材料研究所 | Preparation method and application of vacuum carbon-doped titanium dioxide nanotube array structure |
| CN114457367B (en) * | 2022-03-01 | 2023-11-07 | 厦门稀土材料研究所 | Preparation method and application of vacuum carbon-doped titanium dioxide nanotube array structure |
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Application publication date: 20141210 |