CN105186007A - Nanostructure Ti/TiO2 composite electrode, preparation method and application thereof - Google Patents

Nanostructure Ti/TiO2 composite electrode, preparation method and application thereof Download PDF

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CN105186007A
CN105186007A CN201510373075.9A CN201510373075A CN105186007A CN 105186007 A CN105186007 A CN 105186007A CN 201510373075 A CN201510373075 A CN 201510373075A CN 105186007 A CN105186007 A CN 105186007A
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tio
combination electrode
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CN105186007B (en
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谢健
黄力梁
王国卿
赵新兵
曹高劭
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Zhejiang University ZJU
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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
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    • 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
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a preparation method of a nanostructure Ti/TiO2 composite electrode. The method includes: mixing a hydrogen peroxide solution, melamine and a nitric acid solution to obtain a mixed solution, dipping a metal Ti net subjected to multi-step washing in the mixed solution, carrying out hydrothermal reaction and aftertreatment to obtain an intermediate product, in the mixed solution, with the volume ratio of the nitric acid solution to the hydrogen peroxide solution being 1:10-50, and the mole ratio of melamine to nitric acid being 0.005-0.01; conducting heat treatment on the intermediate product at 400-550DEG C for 0.5-2h, and then performing cooling to obtain the Ti/TiO2 composite electrode. The Ti/TiO2 composite electrode prepared by the method provided by the invention has electrocatalysis and photocatalysis dual functions. During charging, the electrode has photosensitivity to ultraviolet, photo-induced electrons and holes can promote Li2O2 decomposition. Therefore, the nanostructure Ti/TiO2 composite electrode can be applied to a lithium-air battery air electrode to reduce the overpotential of the lithium-air battery.

Description

The Ti/TiO of nanostructure 2combination electrode and its preparation method and application
Technical field
The present invention relates to lithium-empty composite electrode for battery field, be specifically related to a kind of Ti/TiO of nanostructure 2combination electrode and its preparation method and application.
Background technology
Lithium-empty battery is a kind of is negative pole with lithium metal, and the battery that air (or oxygen) is positive pole, lithium ion conductor is electrolytical Novel energy storage apparatus.The theoretical energy density of lithium-empty battery (does not comprise O up to 11680Wh/kg 2if comprise O 2, be then 5200Wh/kg).Consider the weight of catalyst, electrolyte, battery packages etc., the reality of lithium-empty battery can obtain energy density and be about 1700Wh/kg, this value can be suitable with the energy density of gasoline, far above the energy density of nickel-hydrogen (50Wh/kg), lithium ion (160Wh/kg), lithium-sulphur (370Wh/kg), zinc-sky (350Wh/kg) battery.
Lithium-empty battery, due to its high energy density, has important application prospect in the field such as redundant electrical power of Vehicular dynamic battery and electrical network.Just because of lithium-empty battery has very important application prospect, some leading companys and scientific research institution start the research of the empty battery of lithium in the world.As American I BM company starts " Battery500Project " project, the final goal of this plan is that lithium-empty battery is used for automobile, and in this project, " 500 " represent each Rechargeable vehicle and travel 500 miles (800 kilometers).
The factor affecting lithium-empty battery performance is a lot, but the composition and structure of catalyst is key factor.Recently, various new catalyst is as noble metal M (M=Ru, Au, Pd, Pt), PtAu, MnO 2, MnO 2/ Ti, MnO 2/ Pd, MoN/ Graphene, MnCo 2o 4/ Graphenes etc. are developed.For catalyst component, relative to noble metal, metal oxide is (as Co 3o 4, MnO 2) price of catalyst is lower, preparation is comparatively simple, is the desirable catalyst of lithium-empty battery air pole.But in general, the catalytic activity of metal oxide is lower.
Therefore, develop the trend that high performance metal oxide catalyst is still catalyst development from now on, wherein designing catalyst that is dual or multi-functional is one of method.
Summary of the invention
The invention provides a kind of Ti/TiO of nanostructure 2the preparation method of combination electrode, technique is simple, and energy consumption is low, cost is low, is suitable for large-scale industrial production; The Ti/TiO prepared 2combination electrode has electro-catalysis and photocatalysis dual-use function, and this electrode, in charging process, has photosensitivity to ultraviolet light, and light induced electron and hole can promote Li 2o 2decomposition, be applied in lithium-empty battery air electrode, can be used to reduce the overpotential of lithium-empty battery.
A kind of Ti/TiO of nanostructure 2the preparation method of combination electrode, comprises the steps:
(1) hydrogen peroxide solution, melamine are mixed with salpeter solution, preparation mixed liquor, the metal Ti net after multistep cleaning is immersed in described mixed liquor, obtains intermediate product through hydro-thermal reaction and reprocessing;
In described mixed liquor, the volume ratio of salpeter solution and hydrogen peroxide solution is 1:10 ~ 50, and the mol ratio of melamine and nitric acid is 0.005 ~ 0.01;
(2) intermediate product that obtains of step (1) is after 400 ~ 550 DEG C of heat treatment 0.5 ~ 2h, and cooling obtains described Ti/TiO 2combination electrode.
TiO in the combination electrode of nanostructure prepared by the present invention 2for being directly grown on Ti net matrix, so-called direct growth refers under hydrothermal conditions, TiO 2nano wire is directly grown on the skeleton of Ti net; In contrast, non-immediate growth refers to the pre-synthesis TiO of hydro thermal method 2nano wire, then by TiO 2mix in organic solvent with binding agent, stir into slurry, then slurry is coated Ti online.
As preferably, in step (1), the concentration of described hydrogen peroxide solution is 10 ~ 40wt%, and the concentration of salpeter solution is 40 ~ 80wt%.
Further preferably, in mixed liquor, the concentration of hydrogen peroxide solution is 30wt%, and the concentration of salpeter solution is 63wt%; The volume ratio of salpeter solution and hydrogen peroxide solution is 1:50, and the mol ratio of melamine and nitric acid is 0.01.
What adopt in the present invention is 80 commercially available order metal Ti nets.As preferably, in step (1), the concrete steps that described metal Ti net cleans through multistep are:
Hydrofluoric acid aqueous solution, salpeter solution are mixed with water, preparation cleaning fluid, after metal Ti net being placed in described cleaning fluid cleaning 5 ~ 30s, then through ultrasonic cleaning 2 ~ 10min;
In described cleaning fluid, the volume ratio of hydrofluoric acid aqueous solution, salpeter solution and water is 1 ~ 2:2 ~ 4:5 ~ 7.
As preferably, in described cleaning fluid, the concentration of hydrofluoric acid aqueous solution is 35 ~ 65wt%, and the concentration of salpeter solution is 55 ~ 75wt%.Further preferably, the concentration of described hydrofluoric acid aqueous solution is 55wt%, and the concentration of salpeter solution is 63wt%, and in cleaning fluid, the volume ratio of hydrofluoric acid aqueous solution, salpeter solution and water is 1:3:6.
As preferably, in step (1), described hydro-thermal reaction carries out 12 ~ 72h at 60 ~ 100 DEG C.The temperature and time of hydro-thermal reaction can to the TiO of the online direct growth of Ti 2diameter and the length of nano wire impact.TiO 2the meticulous intensity of nanowire diameter is unfavorable for carrying Li 2o 2; Cross and be slightly unfavorable for forming space between nano wire, and then be unfavorable for diffusion and the Li of oxygen 2o 2deposition; Nano wire is long easily causes fracture to peel off from electrode; Too short deposition Li 2o 2the useful space just not enough.The Ti/TiO prepared under above-mentioned preferred hydrothermal reaction condition 2combination electrode is applied in lithium-empty battery, and performance is best.
The temperature of the cooling described in the present invention not strict restriction, based on adequate operation, generally can be cooled to the ambient temperature of 15 DEG C ~ 30 DEG C.
The invention also discloses the Ti/TiO of the nanostructure prepared according to above-mentioned method 2combination electrode, with Ti net for matrix, is direct oxidation into TiO by oxidizing process by the Ti of Ti net surface 2, described TiO 2present nano thread structure.
As preferably, TiO 2the diameter of nano wire is 30 ~ 100nm, and length is 1 ~ 2 μm.
The Ti/TiO of this nanostructure 2combination electrode has electro-catalysis and the two catalysis of photocatalysis, and mechanism is as follows: TiO 2self there is good hydrogen reduction electrocatalysis, namely can promote discharging product Li 2o 2in the formation on its surface; But it is more weak that its oxygen separates out electrocatalysis characteristic, the Li namely formed 2o 2not easily decompose during charging, cause charging overpotential higher.But TiO 2electrode pair ultraviolet light has sensitiveness, and during charging under the irradiation of ultraviolet light, light induced electron and hole can promote Li 2o 2decomposition, thus charging overpotential can be reduced.Therefore, can be applicable in lithium-empty battery, the air electrode as lithium-empty battery uses.
Compared with prior art, tool of the present invention has the following advantages:
1, the Ti/TiO of nanostructure for preparing of the present invention 2in combination electrode, TiO 2be directly grown on Ti net matrix, without other conductive agents and binding agent, have that technique is simple, cost is low, the cycle is short, energy consumption is low and the advantage such as applicable suitability for industrialized production.
2, the Ti/TiO of nanostructure for preparing of the present invention 2combination electrode has electro-catalysis and the two catalysis of photocatalysis simultaneously, and be conducive to the raising of catalytic performance, thus effectively reduce the overpotential of lithium-empty battery, particularly charge overpotential.
3, with traditional TiO prepared with anodic oxidation 2nanotube is compared, by hydrothermal oxidization legal system for TiO 2the method of nano wire is simpler, cost is lower.TiO prepared by what is more important 2nano wire has response to ultraviolet light, is more suitable for the efficient catalytic electrode making lithium-empty battery, and TiO 2nanotube, to ultraviolet light tool non-responsiveness, is not suitable for the catalysis electrode making lithium-empty battery.
4, compared with traditional electrode slurry coating process, catalyst direct growth method can keep Ti to net original mesh-like structure, and this structure is conducive to the transmission of oxygen, the deposition of the wetting and discharging product of electrode, thus improves the performance of lithium-empty battery.
Accompanying drawing explanation
The Ti/TiO of the nanostructure that Fig. 1 is embodiment 1, comparative example 1 and comparative example 2 are prepared respectively 2the X-ray diffractogram of combination electrode;
Fig. 2 is Ti/TiO prepared by embodiment 1 2the stereoscan photograph of combination electrode;
Fig. 3 is the Ti/TiO of the nanostructure prepared respectively with embodiment 1, comparative example 1 and comparative example 2 2combination electrode is as the first charge-discharge curve chart of the lithium-empty battery of positive pole;
Fig. 4 is Ti/TiO prepared by comparative example 3 2the stereoscan photograph of combination electrode;
Fig. 5 is the Ti/TiO prepared with comparative example 3 2combination electrode is the first charge-discharge curve chart of the lithium-empty battery of positive pole;
In figure, (a)-embodiment 1, (b)-comparative example 1, (c)-comparative example 2.
Embodiment
Embodiment 1
80 commercially available order metal Ti nets are placed in containing the 55wt%HF aqueous solution, in the cleaning fluid (volume ratio is 1:3:6) of 63wt% salpeter solution and deionized water, cleaned for 10 seconds, then clean 5 minutes in ultrasound bath; It is the H of 30wt% that clean Ti is netted immersion containing 50mL concentration 2o 2solution, 15 milligrams of melamine (C 3h 6n 6) and 1mL concentration be in the mixed liquor of the salpeter solution of 63wt%, be sealed in reactor, at 80 DEG C react 48 hours; Above-mentioned product after 1 hour through 450 DEG C of heat treatments, is cooled and obtains Ti/TiO 2combination electrode.
Ti/TiO prepared by the present embodiment 2the X ray diffracting spectrum of combination electrode and ESEM are shown in curve (a) and Fig. 2 in Fig. 1 respectively.A in (), the diffraction maximum of X ray all can be summed up as Ti net matrix and Anatase TiO 2.Stereoscan photograph display in Fig. 2, TiO 2present nano thread structure, nanowire diameter is 30 ~ 100nm, and length is 1 ~ 2 μm, and uniform load is on Ti net matrix.
The Ti/TiO of the nanostructure prepared with the present embodiment 2combination electrode, as positive pole, take lithium metal as negative pole, and polypropylene film (trade mark CelgardC380, Celgard company of the U.S.) is barrier film, LiClO 41,2-dimethoxy-ethane (DME) solution be electrolyte, in the glove box being full of argon gas, assemble battery.After passing into 1 atmospheric oxygen, carry out charge-discharge test, gained chemical property is as shown in curve (a) in Fig. 3.
(capacity limit is at 0.2mAh/cm for constant volume charge-discharge test 2, current density 0.04mA/cm 2, voltage range 2 ~ 4.5V, uses wavelength 365nm, intensity 2.8mW/cm 2uV-irradiation battery) show, the cut-ff voltage discharged first is 2.21V, and the cut-ff voltage 3.57V of initial charge, demonstrates lower polarization.
Comparative example 1
80 commercially available order metal Ti nets are placed in containing the 55wt%HF aqueous solution, in the cleaning fluid (volume ratio is 1:3:6) of 63wt% salpeter solution and deionized water, cleaned for 10 seconds, then clean 5 minutes in ultrasound bath; It is the H of 30wt% that clean Ti is netted immersion containing 50mL concentration 2o 2solution, 15 milligrams of C 3h 6n 6and 1mL concentration is in the mixed liquor of the salpeter solution of 63wt%, is sealed in reactor, react 48 hours at 80 DEG C; Above-mentioned product after 1 hour through 600 DEG C of heat treatments, is cooled and obtains Ti/TiO 2combination electrode.
Ti/TiO prepared by this comparative example 2the X ray diffracting spectrum of combination electrode is shown in curve (b) in Fig. 1.In figure, the diffraction maximum of X ray all can be summed up as Ti net matrix and anatase and rutile mixed phase TiO 2.Stereoscan photograph shows, TiO 2present nano thread structure, nanowire diameter is 30 ~ 100nm, and length is 1 ~ 2 μm, and uniform load is on Ti net matrix.
The Ti/TiO of the nanostructure prepared with this comparative example 2combination electrode, as positive pole, take lithium metal as negative pole, and polypropylene film (trade mark CelgardC380, Celgard company of the U.S.) is barrier film, LiClO 41,2-dimethoxy-ethane (DME) solution be electrolyte, in the glove box being full of argon gas, assemble battery.After passing into 1 atmospheric oxygen, carry out charge-discharge test, gained chemical property is as shown in curve (b) in Fig. 3.
(capacity limit is at 0.2mAh/cm for constant volume charge-discharge test 2, current density 0.04mA/cm 2, voltage range 2 ~ 4.5V, uses wavelength 365nm, intensity 2.8mW/cm 2uV-irradiation battery) show, the cut-ff voltage discharged first is 2.07V, and the cut-ff voltage 4.08V of initial charge, demonstrates higher polarization.
Comparative example 2
Be placed in containing the 55wt%HF aqueous solution by 80 commercially available order metal Ti nets, in the cleaning fluid (volume ratio is 1:3:6) of 63wt% salpeter solution and deionized water, cleaning is in 10 seconds, then cleans 5 minutes in ultrasound bath; It is the H of 30wt% that clean Ti is netted immersion containing 50mL concentration 2o 2solution, 15 milligrams of C 3h 6n 6and 1mL concentration is in the mixed liquor of the salpeter solution of 63wt%, is sealed in reactor, react 48 hours at 80 DEG C; Above-mentioned product after 1 hour through 800 DEG C of heat treatments, is cooled and obtains Ti/TiO 2combination electrode.
Ti/TiO prepared by this comparative example 2the X ray diffracting spectrum of combination electrode is shown in curve (c) in Fig. 1.In figure, the diffraction maximum of X ray all can be summed up as Ti net matrix and Rutile Type TiO 2.Stereoscan photograph shows, TiO 2present nano thread structure, nanowire diameter is 30 ~ 100nm, and length is 1 ~ 2 μm, and uniform load is on Ti net matrix.
The Ti/TiO of the nanostructure prepared with this comparative example 2combination electrode, as positive pole, take lithium metal as negative pole, and polypropylene film (trade mark CelgardC380, Celgard company of the U.S.) is barrier film, LiClO 41,2-dimethoxy-ethane (DME) solution be electrolyte, in the glove box being full of argon gas, assemble battery.After passing into 1 atmospheric oxygen, carry out charge-discharge test, gained chemical property is as shown in curve (c) in Fig. 3.
(capacity limit is at 0.2mAh/cm for constant volume charge-discharge test 2, current density 0.04mA/cm 2, voltage range 2 ~ 4.5V, uses wavelength 365nm, intensity 2.8mW/cm 2uV-irradiation battery) show, the cut-ff voltage discharged first is 2.00V, and the cut-ff voltage 4.32V of initial charge, demonstrates higher polarization.
Comparative example 3
Adopt anode oxidation method at Ti net surface direct growth TiO 2nanotube.80 commercially available order metal Ti nets are placed in containing the 55wt%HF aqueous solution, in the cleaning fluid (volume ratio is 1:3:6) of 63wt% salpeter solution and deionized water, cleaned for 10 seconds, then clean 5 minutes in ultrasound bath; Do anode, Pt electrode for negative electrode with the Ti net cleaned, two electrodes are entered into containing 160mL glycerine, 20mL deionized water, 20mLDMSO and 0.5wt%NH 4in the electrolytic cell of F, at 20V voltage anodic oxygen 3h; Above-mentioned product after 1 hour through 450 DEG C of heat treatments, is cooled and obtains Ti/TiO 2combination electrode.
Ti/TiO prepared by this comparative example 2combination electrode adopts X ray diffracting spectrum and ESEM to characterize.The diffraction maximum of X ray shows, gained TiO 2for Anatase TiO 2.Stereoscan photograph shows, TiO 2present nano tube structure (see Fig. 4), tube diameters is 50 ~ 100nm, and length is 1 ~ 2 μm, and uniform load is on Ti net matrix.
The Ti/TiO of the nanostructure prepared with this comparative example 2combination electrode, as positive pole, take lithium metal as negative pole, and polypropylene film (trade mark CelgardC380, Celgard company of the U.S.) is barrier film, LiClO 41,2-dimethoxy-ethane (DME) solution be electrolyte, in the glove box being full of argon gas, assemble battery.After passing into 1 atmospheric oxygen, carry out charge-discharge test.
(capacity limit is at 0.2mAh/cm for constant volume charge-discharge test 2, current density 0.04mA/cm 2, voltage range 2 ~ 4.5V, uses wavelength 365nm, intensity 2.8mW/cm 2uV-irradiation battery) show, the cut-ff voltage discharged first is 2.06V, the cut-ff voltage 4.16V of initial charge, demonstrates higher polarization (see Fig. 5).That is, the Anatase TiO of nano thread structure is different from 2, the Anatase TiO of nano tube structure 2response is not had to ultraviolet light.
Embodiment 2
80 commercially available order metal Ti nets are placed in containing the 55wt%HF aqueous solution, in the cleaning fluid (volume ratio is 1:3:6) of 63wt% salpeter solution and deionized water, cleaned for 10 seconds, then clean 5 minutes in ultrasound bath; It is the H of 30wt% that clean Ti is netted immersion containing 50mL concentration 2o 2solution, 15 milligrams of C 3h 6n 6and 1mL concentration is in the mixed liquor of the salpeter solution of 63wt%, is sealed in reactor, react 60 hours at 60 DEG C; Above-mentioned product after 2 hours through 400 DEG C of heat treatments, is cooled and obtains described Ti/TiO 2combination electrode.
Ti/TiO prepared by the present embodiment 2combination electrode adopts X ray diffracting spectrum and ESEM to characterize.The diffraction maximum of X ray shows, gained TiO 2for Anatase TiO 2.Stereoscan photograph shows, TiO 2present nano thread structure, nanowire diameter is 30 ~ 100nm, and length is 1 ~ 2 μm, and uniform load is on Ti net matrix.
The Ti/TiO of the nanostructure prepared with the present embodiment 2combination electrode, as positive pole, take lithium metal as negative pole, and polypropylene film (trade mark CelgardC380, Celgard company of the U.S.) is barrier film, LiClO 41,2-dimethoxy-ethane (DME) solution be electrolyte, in the glove box being full of argon gas, assemble battery.After passing into 1 atmospheric oxygen, carry out charge-discharge test.
(capacity limit is at 0.2mAh/cm for constant volume charge-discharge test 2, current density 0.04mA/cm 2, voltage range 2 ~ 4.5V, uses wavelength 365nm, intensity 2.8mW/cm 2uV-irradiation battery) show, the cut-ff voltage discharged first is 2.25V, and the cut-ff voltage 3.63V of initial charge, demonstrates lower polarization.
Embodiment 3
80 commercially available order metal Ti nets are placed in containing the 55wt%HF aqueous solution, in the cleaning fluid (volume ratio is 1:3:6) of 63wt% salpeter solution and deionized water, cleaned for 10 seconds, then clean 5 minutes in ultrasound bath; It is the H of 30wt% that clean Ti is netted immersion containing 50mL concentration 2o 2solution, 35 milligrams of C 3h 6n 6and 2mL concentration is in the mixed liquor of the salpeter solution of 63wt%, is sealed in reactor, react 36 hours at 100 DEG C; Above-mentioned product after 0.5 hour through 550 DEG C of heat treatments, is cooled and obtains described Ti/TiO 2combination electrode.
Ti/TiO prepared by the present embodiment 2combination electrode adopts X ray diffracting spectrum and ESEM to characterize.The diffraction maximum of X ray shows, gained TiO 2for Anatase TiO 2.Stereoscan photograph shows, TiO 2present nano thread structure, nanowire diameter is 30 ~ 100nm, and length is 1 ~ 2 μm, and uniform load is on Ti net matrix.
The Ti/TiO of the nanostructure prepared with the present embodiment 2combination electrode, as positive pole, take lithium metal as negative pole, and polypropylene film (trade mark CelgardC380, Celgard company of the U.S.) is barrier film, LiClO 41,2-dimethoxy-ethane (DME) solution be electrolyte, in the glove box being full of argon gas, assemble battery.After passing into 1 atmospheric oxygen, carry out charge-discharge test.
(capacity limit is at 0.2mAh/cm for constant volume charge-discharge test 2, current density 0.04mA/cm 2, voltage range 2 ~ 4.5V, uses wavelength 365nm, intensity 2.8mW/cm 2uV-irradiation battery) show, the cut-ff voltage discharged first is 2.27V, and the cut-ff voltage 3.67V of initial charge, demonstrates lower polarization.

Claims (8)

1. the Ti/TiO of a nanostructure 2the preparation method of combination electrode, is characterized in that, comprises the steps:
(1) hydrogen peroxide solution, melamine are mixed with salpeter solution, preparation mixed liquor, the metal Ti net after multistep cleaning is immersed in described mixed liquor, obtains intermediate product through hydro-thermal reaction and reprocessing;
In described mixed liquor, the volume ratio of salpeter solution and hydrogen peroxide solution is 1:10 ~ 50, and the mol ratio of melamine and nitric acid is 0.005 ~ 0.01;
(2) intermediate product that obtains of step (1) is after 400 ~ 550 DEG C of heat treatment 0.5 ~ 2h, and cooling obtains described Ti/TiO 2combination electrode.
2. the Ti/TiO of nanostructure according to claim 1 2the preparation method of combination electrode, is characterized in that, in step (1), the concentration of described hydrogen peroxide solution is 10 ~ 40wt%, and the concentration of salpeter solution is 40 ~ 80wt%.
3. the Ti/TiO of nanostructure according to claim 1 2the preparation method of combination electrode, is characterized in that, in step (1), the concrete steps that described metal Ti net cleans through multistep are:
Hydrofluoric acid aqueous solution, salpeter solution are mixed with water, preparation cleaning fluid, after metal Ti net being placed in described cleaning fluid cleaning 5 ~ 30s, then through ultrasonic cleaning 2 ~ 10min;
In described cleaning fluid, the volume ratio of hydrofluoric acid aqueous solution, salpeter solution and water is 1 ~ 2:2 ~ 4:5 ~ 7.
4. the Ti/TiO of nanostructure according to claim 3 2the preparation method of combination electrode, is characterized in that, in described cleaning fluid, the concentration of hydrofluoric acid aqueous solution is 35 ~ 65wt%, and the concentration of salpeter solution is 55 ~ 75wt%.
5. the Ti/TiO of nanostructure according to claim 1 2the preparation method of combination electrode, is characterized in that, in step (1), described hydro-thermal reaction carries out 12 ~ 72h at 60 ~ 100 DEG C.
6. the Ti/TiO of nanostructure prepared by the method according to the arbitrary claim of Claims 1 to 5 2combination electrode, is characterized in that, with Ti net for matrix, by oxidizing process, the Ti of Ti net surface is direct oxidation into TiO 2, described TiO 2present nano thread structure.
7. the Ti/TiO of nanostructure according to claim 6 2combination electrode, is characterized in that, TiO 2the diameter of nano wire is 30 ~ 100nm, and length is 1 ~ 2 μm.
8. the Ti/TiO of the nanostructure according to claim 6 or 7 2the application of combination electrode in the air electrode as lithium-empty battery.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108183242A (en) * 2017-11-20 2018-06-19 南京航空航天大学 A kind of preparation method of novel lithium-air battery and its anode
CN111370706A (en) * 2020-02-12 2020-07-03 童圣富 Positive electrode material of metal-air battery and preparation method thereof

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CN108183242B (en) * 2017-11-20 2021-01-08 南京航空航天大学 Lithium-air battery and preparation method of positive electrode thereof
CN111370706A (en) * 2020-02-12 2020-07-03 童圣富 Positive electrode material of metal-air battery and preparation method thereof
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