CN106531989A - Ferroferric oxide@titanium dioxide nanorod array electrode on titanium substrate and preparation method of ferroferric oxide@titanium dioxide nanorod array electrode - Google Patents
Ferroferric oxide@titanium dioxide nanorod array electrode on titanium substrate and preparation method of ferroferric oxide@titanium dioxide nanorod array electrode Download PDFInfo
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- CN106531989A CN106531989A CN201610935364.8A CN201610935364A CN106531989A CN 106531989 A CN106531989 A CN 106531989A CN 201610935364 A CN201610935364 A CN 201610935364A CN 106531989 A CN106531989 A CN 106531989A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 86
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 84
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000010936 titanium Substances 0.000 title claims abstract description 79
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 79
- 239000000758 substrate Substances 0.000 title claims abstract description 54
- 239000002073 nanorod Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000003990 capacitor Substances 0.000 claims abstract description 6
- 238000012983 electrochemical energy storage Methods 0.000 claims abstract description 4
- 229940056319 ferrosoferric oxide Drugs 0.000 claims description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 230000008859 change Effects 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 12
- 230000008021 deposition Effects 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 238000000231 atomic layer deposition Methods 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000004087 circulation Effects 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 238000003491 array Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229940126062 Compound A Drugs 0.000 claims 1
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 238000005868 electrolysis reaction Methods 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 2
- 239000007773 negative electrode material Substances 0.000 abstract 1
- 229960005196 titanium dioxide Drugs 0.000 description 42
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 22
- 238000002484 cyclic voltammetry Methods 0.000 description 11
- 238000010586 diagram Methods 0.000 description 8
- 230000005611 electricity Effects 0.000 description 7
- 238000005253 cladding Methods 0.000 description 6
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 241000549556 Nanos Species 0.000 description 3
- 229910003087 TiOx Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229940075397 calomel Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 241000292525 Titanio Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229950000845 politef Drugs 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
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- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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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- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
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- H01G11/46—Metal oxides
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- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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Abstract
The invention relates to a ferroferric oxide@titanium dioxide nanorod array electrode on a titanium substrate and a preparation method of the ferroferric oxide@titanium dioxide nanorod array electrode. The ferroferric oxide@titanium dioxide nanorod array electrode on the titanium substrate is characterized by comprising a titanium metal substrate and a ferroferric oxide@titanium dioxide composite nanorod array growing on the titanium metal substrate; the diameter of a single composite nanorod is 85-115nm and the composite nanorods are vertically, uniformly and densely distributed on the surface of the titanium metal substrate and are in an array form; and titanium dioxide coats the outer surface of ferroferric oxide. According to a titanium dioxide protection layer of the ferroferric oxide@titanium dioxide nanorod array electrode on the titanium substrate, the cycle performance of the electrode can be greatly improved, the side reaction of water electrolysis in an electrolyte is effectively suppressed, the capacity of the electrode is improved, the electrochemical properties are greatly improved, and particularly, the cycle performance is outstanding; and the ferroferric oxide@titanium dioxide nanorod array electrode can be used as a negative electrode material for a water-based hybrid super-capacitor (or other hybrid electrochemical energy storage devices).
Description
Technical field
The invention belongs to field of inorganic material preparing technology, and in particular in a kind of titanium substrate, ferroso-ferric oxide@titanium dioxide is received
Rice bar array electrode and preparation method thereof, belongs to the fields such as electrochemistry, materialogy, the energy.
Background technology
Aquo-lithium ion battery has with low cost relative to organic electrolyte lithium ion battery, and safe, power is close
The advantages of spending big.Used as typical energy storage material, transition metal oxide theoretical specific capacity is very high.Ferroso-ferric oxide is used as one kind
Common oxide, with low cost, good conductivity and advantages of environment protection.Research finds that ferroso-ferric oxide can be with
High specific capacity is obtained by the complete oxidation reduction reaction of ferrum valence state, it is such as excellent further combined with the kinetics of array structure electrode
Gesture (particularly active material forms robust bond with collector, it is ensured that effective electrical contact), it is expected to obtain high area
Specific capacity, has important practical value in film type energy storage field.But the continuous phase transistion in oxidoreduction thermal energy storage process can cause
Structural damage is so as to causing its cyclical stability extreme difference in aqueous electrolyte.Prior art is mainly for ferroso-ferric oxide powder
Powder material, be related to it is compound with Graphene wait strategy to improve cyclical stability, these strategies effect but have not been suitable for array
Pattern.And the measure such as carbon coating suitable for array pattern for proposing can not significantly improve cycle performance.
The content of the invention
The goal of the invention of the present invention is for the deficiencies in the prior art, there is provided ferroso-ferric oxide@dioxies in a kind of titanium substrate
Change titanium nano-bar array electrode and preparation method thereof.
For achieving the above object, the technical solution used in the present invention is：
Ferroso-ferric oxide@titanic oxide nanorod array electrodes in a kind of titanium substrate, the electrode by titanium metal substrate and
The ferroso-ferric oxide@titanium dioxide composite nanorods array grown in titanium metal substrate is constituted, wherein single composite nanorod
A diameter of 85～115 nanometers, titanium metal substrate surface vertically, uniformly, is densely distributed in, array format, titanium dioxide is presented
It is coated on the outer surface of ferroso-ferric oxide.
By such scheme, the thickness of titanium dioxide is 5-14nm.
By such scheme, described titanium dioxide is deposited in titanium dioxide substrate using technique for atomic layer deposition, is sunk
Product condition be：Using titanium tetrachloride and water as titanium source, oxygen source, first make titanium source enter cavity, will be many after reaching saturation absorption
Remaining titanium source is taken away, is purged with nitrogen, then makes oxygen source enter cavity, takes unnecessary oxygen source away, use nitrogen after reaching saturation absorption
Rinse, this is a deposition cycle, titanium source and oxygen source successively pulse are alternately passed through into reactor cavity according to this, control deposition is followed
Ring number of times.Deposition obtains the titanium dioxide shell after difference.
It is 0.2s by the time that is passed through of such scheme, titanium source and oxygen source, nitrogen flushing times are 20s.
By such scheme, the pressure of described reaction cavity is maintained at 14hPa, and ald temperature is 75 DEG C.
By such scheme, described number of deposition cycles is 50-125 time.
In a kind of titanium substrate, the preparation method of ferroso-ferric oxide@titanic oxide nanorod array electrodes, comprises the steps：
(1) mixed solution is obtained after being sufficiently mixed iron chloride, sodium sulfate and deionized water uniformly；；By titanium sheet and above-mentioned
Solution is placed in hydrothermal reaction kettle carries out hydro-thermal reaction, obtains growing the titanium sheet for having a hydrated ferric oxide nanometer stick array, by which
Take out, after washing and drying, be placed in quartz tube furnace and 600-650 DEG C be heated under argon atmosphere, and kept for one section in this temperature
Time is annealed, and obtains ferriferrous oxide nano rod array in titanium sheet substrate；
(2) sample after annealing is deposited using titanium tetrachloride and water as titanium source, oxygen source with technique for atomic layer deposition
Titanium dioxide；Then sample is placed in quartz tube furnace and 350-450 DEG C is heated under argon atmosphere, and keep one in this temperature
The section time is annealed, and obtains ferroso-ferric oxide@titanic oxide nanorod array electrodes in titanium substrate.
By such scheme, the retention time in step (1) is 2h.
By such scheme, the retention time in step (2) is 30min.
By such scheme, the hydrothermal temperature of the step (1) is 120-160 DEG C, the hydro-thermal reaction time 6 hours.Water
Autoclave of the thermal response kettle for polytetrafluoroethylliner liner substrate.
By such scheme, in the hydro-thermal reaction of the step (1), iron chloride, the concentration of sodium sulfate are 0.05mol/L.
Ferroso-ferric oxide@titanic oxide nanorod array electrodes in above-mentioned titanium substrate, with hybrid energy-storing characteristic, can make
To apply in water system hybrid super capacitor or other electrochemical energy storing device negative materials.
Beneficial effects of the present invention：
(1), in the titanium substrate that the present invention is provided, the titanium dioxide of ferroso-ferric oxide@titanic oxide nanorod array electrodes is protected
Sheath can greatly improve the cycle performance of electrode, effectively suppress the side reaction of water electrolysis in electrolyte, improve electrode capacity, make electricity
Chemical property is greatly improved, particularly outstanding cycle performance；Can be used as water system hybrid super capacitor (or other mixing electricity
Chemical energy storage device) negative material.
(2) in the titanium substrate that the present invention is provided, ferroso-ferric oxide@titanic oxide nanorod arrays electrode is in array pattern, can
So that electrolyte is fully contacted with active material, increase the penetrating power of electrolyte, reduce interface resistance；And the nanometer of nanometer rods
The diameter of yardstick make ion it is embedded/the evolving path shortens, nanometer rods one-dimentional structure provides direct electron propagation ducts；Nanometer rods
It is grown directly upon on titanium substrate collector, increased mechanical stability, and be conducive to electric transmission.
(3), unmodified ferroso-ferric oxide array electrode as aquo-lithium ion battery negative pole, show a pair it is obvious
Redox peaks, with good electrochemical characteristic.
(4) the heavy of titanium dioxide is carried out by technique for atomic layer deposition (a kind of surface vapor deposition technique) in the present invention,
Product cladding is capable of achieving titanium dioxide shell thickness controllable precise, large area, uniform, fine and close cladding, to meet different applications
Need.
Description of the drawings
Fig. 1 is electrode (ferriferrous oxide nano rod array in titanium substrate) scanning electron microscope diagram prepared by embodiment 1,
X-ray diffractogram, wherein a, scanning electron microscope diagrams of the b for different amplification, X-ray diffractograms of the c for electrode.
Fig. 2 is electrode (ferriferrous oxide nano rod array in titanium substrate) three-electrode electro Chemical performance prepared by embodiment 1
Figure, wherein a are cyclic voltammogram, and b is constant current charge-discharge diagram.
Fig. 3 is the scanning electron of electrode (ferroso-ferric oxide@TiOx nanos rod array in titanium substrate) prepared by embodiment 2
Microscope figure, wherein a, composite array scanning electron microscope diagrams of the b for titanium oxide shell ald thickness 5.4nm, c, d
For the composite array scanning electron microscope diagram that titanium oxide shell thickness is 10nm, e, f are titanium oxide shell thickness 13.6nm's
Composite array scanning electron microscope diagram.
Fig. 4 is the transmitted electron of electrode (ferroso-ferric oxide@TiOx nanos rod array in titanium substrate) prepared by embodiment 2
Microscope figure, the composite array transmission electron microscope figure of X-ray diffractogram, wherein a for titanium oxide shell thickness 5.4nm, b is
The composite array transmission electron microscope figure of titanium oxide shell thickness 10nm, compound matrices of the c for titanium oxide shell thickness 13.6nm
Row transmission electron microscope figure, X-ray diffractograms of the d for composite array.
Fig. 5 is electrode (ferroso-ferric oxide@TiOx nanos rod array in titanium substrate) three electrode electrochemicals prepared by embodiment 2
Performance map is learned, combination electrode cyclic voltammograms of the wherein a for titanium oxide shell thickness 5.4nm, b are titanium oxide shell thickness 10nm
Combination electrode cyclic voltammogram, combination electrode cyclic voltammograms of the c for titanium oxide shell thickness 13.6nm, d, e are different oxygen
Change constant current charge-discharge diagram, the cycle performance figure of titanium shell thickness electrode.
Fig. 6 is the comparison diagram of different number of turns cyclic voltammetry curves during electrode cycle prepared by embodiment 2, and a, b distinguish
For different titanium oxide shell thickness electrodes first and the 20000th cyclic voltammogram, c is for titanium oxide shell thickness 10nm electrodes
The cyclic voltammogram of the different number of turns.
Specific embodiment
For a better understanding of the present invention, present disclosure is further elucidated with reference to embodiment, but the present invention
Content is not limited solely to the following examples.
Embodiment 1
Ferriferrous oxide nano bar array electrode in a kind of titanium substrate, its preparation method include：By 0.946 gram of iron chloride
(FeCl3·6H2O) and 0.497 gram of sodium sulfate (Na2SO4) be dissolved in 70 ml deionized waters, with magnetic stirrer so as to
Fully dissolve, mix homogeneously obtains mixed solution；Titanium sheet and the mixed solution for having prepared are placed in into politef together
In the autoclave of inner bag substrate, and 160 DEG C of hydro-thermal reactions in baking oven are proceeded to, kept for 6 hours；Length there are into nanometer rods after natural cooling
The titanium sheet of array takes out, is washed with deionized drying；600 DEG C annealing 2 are heated in argon atmosphere quartz tube furnace subsequently
Hour, take out after cooling, obtain ferriferrous oxide nano rod array sample in titanium substrate.Sample is done into scanning electron microscope sight
Examine, X-ray diffraction, as a result see Fig. 1, Fig. 1 results show, its single ferriferrous oxide nano rod diameter is about 80～100 to receive
Rice, vertically, uniformly, is densely distributed in titanio basal surface, array format is presented.Main peak position and four oxygen after annealing in XRD figure
Change three-iron identical.This shows to have successfully been obtained ferriferrous oxide nano rod array material in titanium substrate.
Using ferriferrous oxide nano bar array electrode in the titanium substrate that embodiment is prepared as working electrode, platinum electrode
As to electrode, calomel electrode (SCE) as reference electrode, in 1mol/L lithium sulfate (Li2SO4) three electrode waters are carried out in solution
Series lithium ion battery performance test, is as a result shown in that Fig. 2, wherein a are that sweep speed distinguishes 5mV/s, 20mV/s, 50mV/s and 100mV/
The cyclic voltammetry curve figure of s, as can be seen from Figure：Obvious oxygen is shown in the interval neutrality lithium salt solution of -1.25 0V potentials
Change reaction peak, illustrate that the material has energy storage and the feature for releasing energy, can be used as a kind of aquo-lithium ion battery negative material.
B is constant current discharge curve chart of the electrode under different electric current densities, is 0.27mA/cm in electric current density2Under the conditions of constant current
During electric discharge, discharge electricity amount is 26.3mC/cm2, after electric current density increases to a certain extent, electrode capacity change is little.With electricity
Current density is 0.27mA/cm2When electricity compare, electric current density increase 12.3 times, capacity residue 23.2%.The above results are said
Bright, the ferriferrous oxide nano bar array electrode that the present embodiment is prepared has good electricity as water system lithium cell negative pole material
Chemical feature and performance.
Embodiment 2
Ferroso-ferric oxide titanium dioxide composite Nano bar array electrode in a kind of titanium substrate, its preparation method include：Will be real
The sample in example 1 is applied using titanium tetrachloride and water as titanium source and oxygen source, by technique for atomic layer deposition deposition of titania：With
Titanium tetrachloride and water are first made titanium source enter cavity, are passed through time 0.2s respectively as titanium source, oxygen source, after reaching saturation absorption, will
Unnecessary titanium source is taken away, after being purged with nitrogen 20 seconds, then makes oxygen source enter cavity, is passed through time 0.2s, after reaching saturation absorption
Unnecessary oxygen source is taken away, after being purged with nitrogen 20 seconds, this is a deposition cycle, is replaced titanium source and oxygen source successively pulse by this
Be passed through reactor cavity, be a deposition cycle, control number of deposition cycles deposition and obtain the titanium dioxide shell after difference.
In deposition process, the pressure of reaction cavity is maintained at 14hPa.
Deposit the titanium oxide shell that 50,100 and 125 circulations obtain 5.4,10 and 13.6 nanometers at 75 DEG C respectively.With
400 DEG C are heated in argon atmosphere quartz tube furnace afterwards to anneal 30 minutes, are taken out after cooling, obtain four oxidation three in titanium substrate
Ferrum@titanium dioxide array samples, are designated as Fe3O4@5TiO2, Fe3O4@10TiO2, Fe3O4@13TiO2.Sample is done scanning electron to show
Micro mirror is observed, and as a result sees Fig. 3.Fig. 3 results show that the titanium dioxide of different-thickness is uniformly coated on nanometer stick array, its
The single composite nanorod of the titanium dioxide shell sample of middle 10nm is a diameter of 80～115 nanometers, vertically, uniformly, densely divides
Cloth is presented array format in surface of metal titanium.The sample of different titanium dioxide shell thicknesses is done into transmission electron microscope observation,
X-ray diffraction, is as a result shown in Fig. 4, as a result shows：The titanium dioxide ald thickness of different condition is respectively 5.4,10 Hes
13.6nm.In XRD figure, after ald, peak position is also shown titanium dioxide and is spread out except being coincide with ferroso-ferric oxide, titanium
Penetrate peak position.
Using composite ferroferric oxide@titanic oxide nanorod array electrodes in the titanium substrate that embodiment is prepared as work
Make electrode, used as to electrode, calomel electrode (SCE) is reference electrode to platinum electrode, in 1mol/L lithium sulfate (Li2SO4) enter in solution
Row three-electrode electro Chemical performance test, all tests are measured after being 40 circle of activation, as a result see Fig. 5.Wherein a, b, c are respectively not
The combination electrode cyclic voltammogram of stack pile titanium dioxide shell.Found out by figure, different from embodiment 1, cyclic voltammetry curve is near
Like rectangle, and as the significantly change of sweep speed, the shape of curve do not have significant change, after illustrating to be combined, electrode material
In the case of fast charging and discharging, can also keep good capacitive characteristics, the cladding of simultaneous oxidation titanium shell to inhibit the electricity of water
Solution, can be used as the negative material of water system hybrid super capacitor (or other hybrid electrochemical energy storage devices).D is different thick
The electrode of degree is in 0.4mA/cm2Constant current charge-discharge curve chart under electric current density, image approximate isosceles triangle, charging and discharging curve
Symmetrically.The combination electrode of cladding 10nm titanium oxide shells is respectively 0.1,0.2,0.4,0.8,2.8 and 7mA/cm in electric current density2
Under the conditions of constant current charge-discharge when, its capacity is respectively 83.5,44.9,21.5,14.6,8.7 and 6.4mF/cm2.In 0.1mA/
cm2Under the conditions of constant current charge-discharge when, 5.4, the electrode capacity of the titanium oxide shell of 13.6nm be respectively 67.5,41.0mF/cm2；
In 7mA/cm2Under the conditions of constant current charge-discharge when, 5.4, the electrode capacity of the titanium oxide shell of 13.6nm be respectively 7.2,
10.1mF/cm2.The different shell thickness electrode capacities of contrast, the combination electrode of 10nm titanium oxide shells show maximum capacity, are
Optimum thickness.
Meanwhile, we experiments verify that, after cladding titanium dioxide shell, in constant current charge-discharge reaction, electric current density
Test scope is bigger, can particularly adopt less electric current density to test, this further demonstrates, and titanium dioxide shell can be played
Suppress the effect of water electrolysis.E is the cycle performance figure of different-thickness electrode (including pure ferroso-ferric oxide array in embodiment 1).
Test is circulated under conditions of 50mV/s, after as a result showing the modification of ald titanium-oxide-coated, the circulation of electrode
Performance is increased substantially.Unmodified front ferroso-ferric oxide electrode declines to a great extent in front 400 circle capacity, after circulating 10000 times, capacity
34.7%, and after being modified is remained only, the electrode of the different-thickness capacity in cyclic process obtains the lifting of different levels,
After circulation 10000 times, titanium oxide shell thickness is respectively initial capacity for the electrode capacity of 5.4nm, 10nm and 13.6nm
123.6%, 469.2% and 217.3%；After 20000 times, capacity still maintains 117.0%, 464.7% and 228.2% respectively.
Shown by loop test, the titanium oxide protective layer of 10nm thickness is optimum thickness, is still had after circulating 30000 times
305.6% growth.Fig. 6 presents the circulation volt of the different number of turns in the combination electrode cyclic process of different titanium oxide shell thicknesses
Antu is compared, and by figure explanation, the electrode after modification keeps preferable electrochemical behavior, and capacity significantly to increase in cyclic process
Long, particularly the combination electrode of 10nm titanium oxides shell cladding the 20000th time and the 30000th cyclic voltammetry curve difference are little, table
Reveal the cycle performance of brilliance.The above results illustrate that ferroso-ferric oxide@titanium oxides are multiple in the titanium substrate that the present embodiment is prepared
Close nano-bar array electrode to have as the negative pole of water system hybrid super capacitor (or other hybrid electrochemical energy storage devices)
Good chemical property, particularly superior cycle performance.
Obviously, above-described embodiment is only intended to clearly illustrate made example, and the not restriction to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description other multi-forms change or
Change.There is no need to be exhaustive to all of embodiment.And therefore the obvious change amplified or change
Move within still in the protection domain of the invention.
Claims (10)
1. ferroso-ferric oxide@titanic oxide nanorod array electrodes in a kind of titanium substrate, it is characterised in that：The electrode is by titanium
The ferroso-ferric oxide@titanium dioxide composite nanorods array grown in category substrate and titanium metal substrate is constituted, wherein single compound
A diameter of 85～115 nanometers of nanometer rods, vertically, uniformly, are densely distributed in titanium metal substrate surface, array format are presented,
Outer surface of the coated by titanium dioxide in ferroso-ferric oxide.
2. ferroso-ferric oxide@titanic oxide nanorod array electrodes in titanium substrate according to claim 1, its feature exist
In：The thickness of titanium dioxide is 5-14nm.
3. ferroso-ferric oxide@titanic oxide nanorod array electrodes in titanium substrate according to claim 1, its feature exist
In：Described titanium dioxide is deposited in titanium dioxide substrate using technique for atomic layer deposition, and sedimentary condition is：With four chlorinations
Titanium and water first make titanium source enter cavity respectively as titanium source, oxygen source, after reaching saturation absorption, unnecessary titanium source is taken away, nitrogen is used
Gas flushing, then make oxygen source enter cavity, unnecessary oxygen source to be taken away after reaching saturation absorption, be purged with nitrogen, this is deposited for one
Titanium source and oxygen source successively pulse are alternately passed through reactor cavity by circulation according to this, control number of deposition cycles.Deposition is obtained not
Titanium dioxide shell with after.
4. ferroso-ferric oxide@titanic oxide nanorod array electrodes in titanium substrate according to claim 1, its feature exist
In：The time that is passed through of titanium source and oxygen source is 0.2s, and nitrogen flushing times are 20s.
5. ferroso-ferric oxide@titanic oxide nanorod array electrodes in titanium substrate according to claim 1, its feature exist
In：The pressure of described reaction cavity is maintained at 14hPa, and ald temperature is 75 DEG C.
6. ferroso-ferric oxide@titanic oxide nanorod array electrodes in titanium substrate according to claim 1, its feature exist
In：Described number of deposition cycles is 50-125 time.
7. in the titanium substrate described in claim 1 ferroso-ferric oxide@titanic oxide nanorod array electrodes preparation method, which is special
Levy and be：Comprise the steps：
(1) mixed solution is obtained after being sufficiently mixed iron chloride, sodium sulfate and deionized water uniformly；；By titanium sheet and above-mentioned solution
Being placed in hydrothermal reaction kettle carries out hydro-thermal reaction, obtains growing the titanium sheet for having a hydrated ferric oxide nanometer stick array, is drawn off,
After washing and drying, be placed in quartz tube furnace and 600-650 DEG C be heated under argon atmosphere, and kept for a period of time enter in this temperature
Row annealing, obtains ferriferrous oxide nano rod array in titanium sheet substrate；
(2) sample after annealing deposits dioxy with technique for atomic layer deposition using titanium tetrachloride and water as titanium source, oxygen source
Change titanium；Then sample is placed in quartz tube furnace 350-450 DEG C is heated under argon atmosphere, and when this temperature is kept for one section
Between annealed, obtain ferroso-ferric oxide@titanic oxide nanorod array electrodes in titanium substrate.
8. in titanium substrate according to claim 1 ferroso-ferric oxide@titanic oxide nanorod array electrodes preparation method,
It is characterized in that：Retention time in step (1) is 2h；Retention time in step (2) is 30min.
9. in titanium substrate according to claim 1 ferroso-ferric oxide@titanic oxide nanorod array electrodes preparation method,
It is characterized in that：The hydrothermal temperature of the step (1) is 120-160 DEG C, the hydro-thermal reaction time 6 hours.Hydrothermal reaction kettle
For the autoclave of polytetrafluoroethylliner liner substrate.
10. in the titanium substrate described in claim 1 ferroso-ferric oxide@titanic oxide nanorod arrays electrode in water system lithium salt solution
The middle negative material application as water system hybrid super capacitor or other hybrid electrochemical energy storage devices.
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