CN105186007B - The Ti/TiO of nanostructured2Combination electrode and its preparation method and application - Google Patents

The Ti/TiO of nanostructured2Combination electrode and its preparation method and application Download PDF

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CN105186007B
CN105186007B CN201510373075.9A CN201510373075A CN105186007B CN 105186007 B CN105186007 B CN 105186007B CN 201510373075 A CN201510373075 A CN 201510373075A CN 105186007 B CN105186007 B CN 105186007B
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tio
solution
combination electrode
lithium
electrode
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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
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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
    • H01M4/86—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
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Abstract

The invention discloses a kind of Ti/TiO of nanostructured2The preparation method of combination electrode mixes hydrogen peroxide solution, melamine with salpeter solution, prepares mixed liquor, and the metal Ti nets after multistep is cleaned are immersed in the mixed liquor, intermediate product is obtained through hydro-thermal reaction and post processing；In mixed liquor, the volume ratio of salpeter solution and hydrogen peroxide solution is 1:10~50, the molar ratio of melamine and nitric acid is 0.005~0.01；For intermediate product after 400~550 DEG C are heat-treated 0.5~2h, cooling obtains the Ti/TiO2Combination electrode.The Ti/TiO that the present invention is prepared2Combination electrode has electro-catalysis and photocatalysis dual function, which has photosensitivity in charging process, to ultraviolet light, and light induced electron and hole can promote Li2O2Decomposition, be applied in lithium sky battery air electrode, can be used to reduce the overpotential of lithium sky battery.

Description

The Ti/TiO of nanostructured2Combination electrode and its preparation method and application
Technical field
The present invention relates to lithium-sky composite electrode for battery fields, and in particular to a kind of Ti/TiO of nanostructured2It is compound Electrode and its preparation method and application.
Background technology
Lithium-sky battery is a kind of using lithium metal as cathode, and air (or oxygen) is the battery of anode, and lithium ion conductor is electricity Solve the novel energy storage apparatus of matter.The theoretical energy density of lithium-sky battery is up to 11680Wh/kg (not including O2If including O2, then For 5200Wh/kg).In view of the weight of catalyst, electrolyte, battery packages etc., the reality of lithium-sky battery can obtain energy density About 1700 Wh/kg, the value can be suitable with the energy density of gasoline, far above nickel-hydrogen (50Wh/kg), lithium ion (160Wh/ Kg), lithium-sulphur (370Wh/kg), the energy density of zinc-sky (350Wh/kg) battery.
Lithium-sky battery has due to its high energy density in fields such as the redundant electrical powers of Vehicular dynamic battery and power grid There is important application prospect.Just because of lithium-sky battery has very important application prospect, in the world some leading companies and section Grind the research that mechanism starts lithium sky battery.If IBM companies of the U.S. start " Battery 500Project " project, The final goal of the plan is that lithium-sky battery is used for automobile, and " 500 " represent each Rechargeable vehicle traveling in the project 500 miles (800 kilometers).
It is many to influence the factor of lithium-sky battery performance, but the ingredient of catalyst and structure are key factors.Recently, it is various New catalyst such as noble metal M (M=Ru, Au, Pd, Pt), PtAu, MnO2、 MnO2/Ti、MnO2/ Pd, MoN/ graphenes, MnCo2O4/ graphene etc. is developed.For catalyst component, compared with noble metal, metal oxide (such as Co3O4、MnO2) catalysis The price of agent is relatively low, and preparation is simpler, is the preferable catalyst of lithium-sky battery air pole.But in general, metal oxide Catalytic activity it is relatively low.
Therefore, the trend that high performance metal oxide catalyst is still catalyst development from now on is developed, wherein design is double The catalyst of weight or multi-functional is one of method.
The content of the invention
The present invention provides a kind of Ti/TiO of nanostructured2The preparation method of combination electrode, it is simple for process, low energy consumption, It is at low cost, it is suitable for large-scale industrial production；The Ti/TiO being prepared2Combination electrode is dual with electro-catalysis and photocatalysis Function, the electrode have photosensitivity in charging process, to ultraviolet light, and light induced electron and hole can promote Li2O2Decomposition, It is applied in lithium-sky battery air electrode, can be used to reduce the overpotential of lithium-sky battery.
A kind of Ti/TiO of nanostructured2The preparation method of combination electrode, includes the following steps：
(1) hydrogen peroxide solution, melamine with salpeter solution are mixed, mixed liquor is prepared, by the gold after multistep is cleaned Belong to Ti nets to immerse in the mixed liquor, intermediate product is obtained through hydro-thermal reaction and post processing；
In the mixed liquor, the volume ratio of salpeter solution and hydrogen peroxide solution is 1:10~50, melamine and nitric acid Molar ratio is 0.005~0.01；
(2) for the intermediate product that step (1) obtains after 400~550 DEG C are heat-treated 0.5~2h, cooling obtains the Ti/ TiO2Combination electrode.
TiO in the combination electrode of nanostructured prepared by the present invention2It is so-called direct to be directly grown on Ti net matrixes It grows and refers under hydrothermal conditions, TiO2Nano wire is directly grown on the skeleton of Ti nets；In contrast, indirect growth refers to With the pre-synthesis TiO of hydro-thermal method2Nano wire, then by TiO2It is uniformly mixed in organic solvent with binding agent, stirs into slurry, so It is online that slurry is coated on Ti afterwards.
Preferably, in step (1), the concentration of the hydrogen peroxide solution is 10~40wt%, and the concentration of salpeter solution is 40~80wt%.
Further preferably, the concentration of hydrogen peroxide solution is 30wt% in mixed liquor, and the concentration of salpeter solution is 63wt%；Nitre The volume ratio of acid solution and hydrogen peroxide solution is 1:50, the molar ratio of melamine and nitric acid is 0.01.
It is commercially available 80 mesh metal Ti nets to be used in the present invention.Preferably, in step (1), the metal Ti nets warp Multistep cleaning concretely comprises the following steps：
Hydrofluoric acid aqueous solution, salpeter solution with water are mixed, cleaning solution is prepared, metal Ti nets is placed in the cleaning solution After cleaning 5~30s, then through being cleaned by ultrasonic 2~10min；
The volume ratio of hydrofluoric acid aqueous solution, salpeter solution and water is 1~2 in the cleaning solution:2~4:5~7.
Preferably, in the cleaning solution, the concentration of hydrofluoric acid aqueous solution is 35~65wt%, and the concentration of salpeter solution is 55~75wt%.Further preferably, the concentration of the hydrofluoric acid aqueous solution is 55wt%, and the concentration of salpeter solution is 63wt%, The volume ratio of hydrofluoric acid aqueous solution, salpeter solution and water is 1 in cleaning solution:3:6.
Preferably, in step (1), the hydro-thermal reaction carries out 12~72h at 60~100 DEG C.The temperature of hydro-thermal reaction Degree and time can be to the TiO of the online direct growths of Ti2The diameter and length of nano wire impact.TiO2Nanowire diameter is meticulous Intensity is unfavorable for carrying Li2O2；It crosses and is slightly unfavorable for forming gap between nano wire, and then be unfavorable for diffusion and the Li of oxygen2O2 Deposition；Nano wire is long to be easily caused fracture and is peeled off from electrode；Too short deposition Li2O2The useful space just deficiency.It is above-mentioned preferred Hydrothermal reaction condition under the Ti/TiO for preparing2Combination electrode is applied in lithium-sky battery, and performance is optimal.
The temperature of heretofore described cooling based on adequate operation, can be generally cooled to there is no stringent restriction 15 DEG C~30 DEG C of environment temperature.
The invention also discloses the Ti/TiO of the nanostructured according to above-mentioned method preparation2Combination electrode, using Ti nets as The Ti of Ti net surfaces is direct oxidation into TiO by matrix by oxidizing process2, the TiO2Nano thread structure is presented.
Preferably, TiO2A diameter of 30~100nm of nano wire, length are 1~2 μm.
The Ti/TiO of the nanostructured2Combination electrode has electro-catalysis and the double catalysis of photocatalysis, and mechanism is as follows：TiO2 Itself has preferable hydrogen reduction electrocatalysis, you can to promote discharging product Li2O2Formation on its surface；But its oxygen is analysed Go out the Li that electrocatalysis characteristic is weaker, that is, is formed2O2It is not easily decomposed during charging, causes charging overpotential higher.But TiO2Electrode pair Ultraviolet light has sensibility, and during charging under the irradiation of ultraviolet light, light induced electron and hole can promote Li2O2Decomposition, so as to Charging overpotential can be reduced.Therefore, can be applied in lithium-sky battery, the air electrode as lithium-sky battery uses.
Compared with prior art, the invention has the advantages that：
1st, the Ti/TiO of nanostructured prepared by the present invention2In combination electrode, TiO2It is directly grown on Ti net matrixes, no With other conductive agents and binding agent, have many advantages, such as that simple for process, at low cost, the cycle is short, low energy consumption and suitable industrialized production.
2nd, the Ti/TiO of nanostructured prepared by the present invention2Combination electrode has electro-catalysis and the double catalysis work(of photocatalysis simultaneously Can, be conducive to the raising of catalytic performance, so as to effectively reduce the overpotential of lithium-sky battery, particularly charge overpotential.
3rd, with it is traditional with anodic oxidation prepare TiO2Nanotube is compared, and TiO is prepared with hydrothermal oxidization method2Nano wire Method is simpler, cost is lower.TiO prepared by what is more important2Nano wire has response to ultraviolet light, is more suitable for doing The efficient catalytic electrode of lithium-sky battery, and TiO2Nanotube has non-responsiveness to ultraviolet light, is not suitable for doing urging for lithium-sky battery Polarizing electrode.
4th, compared with traditional electrode slurry coating process, catalyst direct growth method can keep Ti to net original mesh Structure, the structure are conducive to the transmission of oxygen, the wetting of electrode and the deposition of discharging product, so as to improve the property of lithium-sky battery Energy.
Description of the drawings
Fig. 1 is the Ti/TiO for the nanostructured that embodiment 1, comparative example 1 and comparative example 2 are prepared respectively2The X of combination electrode is penetrated Ray diffraction diagram；
Fig. 2 is Ti/TiO prepared by embodiment 12The stereoscan photograph of combination electrode；
Fig. 3 is the Ti/TiO of the nanostructured prepared respectively with embodiment 1, comparative example 1 and comparative example 22Combination electrode is made For the first charge-discharge graph of lithium-sky battery of anode；
Fig. 4 is Ti/TiO prepared by comparative example 32The stereoscan photograph of combination electrode；
Fig. 5 is the Ti/TiO prepared with comparative example 32Combination electrode is the first charge-discharge curve of lithium-sky battery of anode Figure；
In figure, (a)-embodiment 1, (b)-comparative example 1, (c)-comparative example 2.
Specific embodiment
Embodiment 1
Commercially available 80 mesh metal Ti nets are placed in aqueous solution containing 55wt%HF, 63wt% salpeter solutions and deionized water it is clear Washing lotion (volume ratio 1:3:6) cleaning 10 seconds in, then cleaned 5 minutes in ultrasound bath；Clean Ti nets are immersed and are contained There is the H that 50mL concentration is 30wt%2O2Solution, 15 milligrams of melamine (C3H6N6) and 1mL concentration be 63wt% salpeter solution Mixed liquor in, be sealed in reaction kettle, at 80 DEG C react 48 it is small when；By above-mentioned product through 450 DEG C heat treatment 1 it is small when after, Cooling obtains Ti/TiO2Combination electrode.
Ti/TiO manufactured in the present embodiment2The X ray diffracting spectrum and scanning electron microscope of combination electrode are shown in curve in Fig. 1 respectively (a) and Fig. 2.(a) diffraction maximum of X-ray can be attributed to Ti nets matrix and Anatase TiO in2.Scanning electron microscope in Fig. 2 is shone Piece shows, TiO2Nano thread structure is presented, nanowire diameter is 30~100nm, and length is 1~2 μm, and uniform load is in Ti nets On matrix.
With the Ti/TiO of nanostructured manufactured in the present embodiment2Combination electrode is as anode, using lithium metal as cathode, poly- third Alkene film (trade mark Celgard C380, Celgard companies of the U.S.) be membrane, LiClO41,2- dimethoxy-ethanes (DME) Solution is electrolyte, and battery is assembled in the glove box full of argon gas.After being passed through the oxygen of 1 atmospheric pressure, charge and discharge electrical measurement is carried out In examination, gained chemical property such as Fig. 3 shown in curve (a).
(capacity limit is in 0.2mAh/cm for constant volume charge-discharge test2, current density 0.04mA/cm2, voltage range 2~ 4.5V, with wavelength 365nm, intensity 2.8mW/cm2Ultraviolet light battery) blanking voltage that shows to discharge for the first time is 2.21V, the blanking voltage 3.57V of initial charge, shows relatively low polarization.
Comparative example 1
Commercially available 80 mesh metal Ti nets are placed in aqueous solution containing 55wt%HF, 63wt% salpeter solutions and deionized water it is clear Washing lotion (volume ratio 1:3:6) cleaning 10 seconds in, then cleaned 5 minutes in ultrasound bath；Clean Ti nets are immersed and are contained There is the H that 50mL concentration is 30wt%2O2Solution, 15 milligrams of C3H6N6And in the mixed liquor for the salpeter solution that 1mL concentration is 63wt%, It is sealed in reaction kettle, when reaction 48 is small at 80 DEG C；By above-mentioned product through 600 DEG C heat treatment 1 it is small when after, cooling obtain Ti/ TiO2Combination electrode.
Ti/TiO prepared by this comparative example2The X ray diffracting spectrum of combination electrode is shown in curve (b) in Fig. 1.X-ray in figure Diffraction maximum can be attributed to Ti nets matrix and anatase and rutile mixed phase TiO2.Stereoscan photograph shows, TiO2It presents Nano thread structure, nanowire diameter are 30~100 nm, and length is 1~2 μm, and uniform load is on Ti net matrixes.
With the Ti/TiO of nanostructured prepared by this comparative example2Combination electrode is as anode, using lithium metal as cathode, poly- third Alkene film (trade mark Celgard C380, Celgard companies of the U.S.) be membrane, LiClO41,2- dimethoxy-ethanes (DME) Solution is electrolyte, and battery is assembled in the glove box full of argon gas.After being passed through the oxygen of 1 atmospheric pressure, charge and discharge electrical measurement is carried out In examination, gained chemical property such as Fig. 3 shown in curve (b).
(capacity limit is in 0.2mAh/cm for constant volume charge-discharge test2, current density 0.04mA/cm2, voltage range 2~ 4.5V, with wavelength 365nm, intensity 2.8mW/cm2Ultraviolet light battery) blanking voltage that shows to discharge for the first time is 2.07V, the blanking voltage 4.08V of initial charge, shows higher polarization.
Comparative example 2
Commercially available 80 mesh metal Ti nets are placed in aqueous solution containing 55wt%HF, 63wt% salpeter solutions and deionized water it is clear Washing lotion (volume ratio 1:3:6) in being cleaned 10 seconds in, then cleaned 5 minutes in ultrasound bath；Clean Ti nets are immersed and are contained There is the H that 50mL concentration is 30wt%2O2Solution, 15 milligrams of C3H6N6And in the mixed liquor for the salpeter solution that 1mL concentration is 63wt%, It is sealed in reaction kettle, when reaction 48 is small at 80 DEG C；By above-mentioned product through 800 DEG C heat treatment 1 it is small when after, cooling obtain Ti/ TiO2Combination electrode.
Ti/TiO prepared by this comparative example2The X ray diffracting spectrum of combination electrode is shown in curve (c) in Fig. 1.X-ray in figure Diffraction maximum can be attributed to Ti nets matrix and Rutile Type TiO2.Stereoscan photograph shows, TiO2Nano thread structure is presented, Nanowire diameter is 30~100nm, and length is 1~2 μm, and uniform load is on Ti net matrixes.
With the Ti/TiO of nanostructured prepared by this comparative example2Combination electrode is as anode, using lithium metal as cathode, poly- third Alkene film (trade mark Celgard C380, Celgard companies of the U.S.) be membrane, LiClO41,2- dimethoxy-ethanes (DME) Solution is electrolyte, and battery is assembled in the glove box full of argon gas.After being passed through the oxygen of 1 atmospheric pressure, charge and discharge electrical measurement is carried out In examination, gained chemical property such as Fig. 3 shown in curve (c).
(capacity limit is in 0.2mAh/cm for constant volume charge-discharge test2, current density 0.04mA/cm2, voltage range 2~ 4.5V, with wavelength 365nm, intensity 2.8mW/cm2Ultraviolet light battery) blanking voltage that shows to discharge for the first time is 2.00V, the blanking voltage 4.32V of initial charge, shows higher polarization.
Comparative example 3
Using anodizing in Ti net surface direct growths TiO2Nanotube.Commercially available 80 mesh metal Ti nets are placed in and are contained Cleaning solution (the volume ratio 1 of 55wt%HF aqueous solutions, 63wt% salpeter solutions and deionized water:3:6) cleaning 10 seconds in, then It is cleaned 5 minutes in ultrasound bath；Anode, Pt electrodes are done as cathode using clean Ti nets, by two electrodes enter containing 160mL glycerine, 20mL deionized waters, 20mL DMSO and 0.5wt%NH4In the electrolytic cell of F, in 20V voltage anodic oxygens 3h；By above-mentioned product through 450 DEG C heat treatment 1 it is small when after, cooling obtain Ti/TiO2Combination electrode.
Ti/TiO prepared by this comparative example2Combination electrode is characterized using X ray diffracting spectrum and scanning electron microscope.X is penetrated The diffraction maximum of line shows gained TiO2For Anatase TiO2.Stereoscan photograph shows TiO2Nano tube structure is presented (see figure 4), tube diameters are 50~100nm, and length is 1~2 μm, and uniform load is on Ti net matrixes.
With the Ti/TiO of nanostructured prepared by this comparative example2Combination electrode is as anode, using lithium metal as cathode, poly- third Alkene film (trade mark Celgard C380, Celgard companies of the U.S.) be membrane, LiClO41,2- dimethoxy-ethanes (DME) Solution is electrolyte, and battery is assembled in the glove box full of argon gas.After being passed through the oxygen of 1 atmospheric pressure, charge and discharge electrical measurement is carried out Examination.
(capacity limit is in 0.2mAh/cm for constant volume charge-discharge test2, current density 0.04mA/cm2, voltage range 2~ 4.5V, with wavelength 365nm, intensity 2.8mW/cm2Ultraviolet light battery) blanking voltage that shows to discharge for the first time is 2.06V, the blanking voltage 4.16V of initial charge show higher polarization (see Fig. 5).That is, different from the sharp of nano thread structure Titanium ore phase TiO2, the Anatase TiO of nano tube structure2To not responding to property of ultraviolet light.
Embodiment 2
Commercially available 80 mesh metal Ti nets are placed in aqueous solution containing 55wt%HF, 63wt% salpeter solutions and deionized water it is clear Washing lotion (volume ratio 1:3:6) cleaning 10 seconds in, then cleaned 5 minutes in ultrasound bath；Clean Ti nets are immersed and are contained There is the H that 50mL concentration is 30wt%2O2Solution, 15 milligrams of C3H6N6And in the mixed liquor for the salpeter solution that 1mL concentration is 63wt%, It is sealed in reaction kettle, when reaction 60 is small at 60 DEG C；By above-mentioned product when 400 DEG C of heat treatments 2 are small after, cooling obtains described Ti/TiO2Combination electrode.
Ti/TiO manufactured in the present embodiment2Combination electrode is characterized using X ray diffracting spectrum and scanning electron microscope.X is penetrated The diffraction maximum of line shows gained TiO2For Anatase TiO2.Stereoscan photograph shows TiO2Nano thread structure, nanometer is presented Linear diameter is 30~100nm, and length is 1~2 μm, and uniform load is on Ti net matrixes.
With the Ti/TiO of nanostructured manufactured in the present embodiment2Combination electrode is as anode, using lithium metal as cathode, poly- third Alkene film (trade mark Celgard C380, Celgard companies of the U.S.) be membrane, LiClO41,2- dimethoxy-ethanes (DME) Solution is electrolyte, and battery is assembled in the glove box full of argon gas.After being passed through the oxygen of 1 atmospheric pressure, charge and discharge electrical measurement is carried out Examination.
(capacity limit is in 0.2mAh/cm for constant volume charge-discharge test2, current density 0.04mA/cm2, voltage range 2~ 4.5V, with wavelength 365nm, intensity 2.8mW/cm2Ultraviolet light battery) blanking voltage that shows to discharge for the first time is 2.25V, the blanking voltage 3.63V of initial charge, shows relatively low polarization.
Embodiment 3
Commercially available 80 mesh metal Ti nets are placed in aqueous solution containing 55wt%HF, 63wt% salpeter solutions and deionized water it is clear Washing lotion (volume ratio 1:3:6) cleaning 10 seconds in, then cleaned 5 minutes in ultrasound bath；Clean Ti nets are immersed and are contained There is the H that 50mL concentration is 30wt%2O2Solution, 35 milligrams of C3H6N6And in the mixed liquor for the salpeter solution that 2mL concentration is 63wt%, It is sealed in reaction kettle, when reaction 36 is small at 100 DEG C；By above-mentioned product through 550 DEG C heat treatment 0.5 it is small when after, cooling obtains The Ti/TiO2Combination electrode.
Ti/TiO manufactured in the present embodiment2Combination electrode is characterized using X ray diffracting spectrum and scanning electron microscope.X is penetrated The diffraction maximum of line shows gained TiO2For Anatase TiO2.Stereoscan photograph shows TiO2Nano thread structure, nanometer is presented Linear diameter is 30~100nm, and length is 1~2 μm, and uniform load is on Ti net matrixes.
With the Ti/TiO of nanostructured manufactured in the present embodiment2Combination electrode is as anode, using lithium metal as cathode, poly- third Alkene film (trade mark Celgard C380, Celgard companies of the U.S.) be membrane, LiClO41,2- dimethoxy-ethanes (DME) Solution is electrolyte, and battery is assembled in the glove box full of argon gas.After being passed through the oxygen of 1 atmospheric pressure, charge and discharge electrical measurement is carried out Examination.
(capacity limit is in 0.2mAh/cm for constant volume charge-discharge test2, current density 0.04mA/cm2, voltage range 2~ 4.5V, with wavelength 365nm, intensity 2.8mW/cm2Ultraviolet light battery) blanking voltage that shows to discharge for the first time is 2.27V, the blanking voltage 3.67V of initial charge, shows relatively low polarization.

Claims (3)

1. a kind of Ti/ of nanostructured with electro-catalysis and photocatalysis dual function applied to lithium-sky battery air electrode TiO2Combination electrode, which is characterized in that the Ti/TiO2Combination electrode is using Ti nets as matrix, by oxidizing process by Ti net surfaces Ti be direct oxidation into TiO2, the TiO2Nano thread structure is presented, is Anatase TiO2；
The lithium-sky battery is using lithium metal as cathode, and polypropylene film is membrane, LiClO41,2- dimethoxyethane solutions For electrolyte；
The Ti/TiO2The preparation method of combination electrode, includes the following steps：
(1) hydrogen peroxide solution, melamine with salpeter solution are mixed, mixed liquor is prepared, by the metal Ti after multistep is cleaned Net is immersed in the mixed liquor, and intermediate product is obtained through hydro-thermal reaction and post processing；
In the mixed liquor, the concentration of hydrogen peroxide solution is 30wt% in mixed liquor, and the concentration of salpeter solution is 63wt%；Nitric acid The volume ratio of solution and hydrogen peroxide solution is 1:50, the molar ratio of melamine and nitric acid is 0.01；
The metal Ti nets are concretely comprised the following steps through what multistep was cleaned：
Hydrofluoric acid aqueous solution, salpeter solution with water are mixed, cleaning solution is prepared, metal Ti nets is placed in the cleaning solution and are cleaned After 5~30s, then through being cleaned by ultrasonic 2~10min；
The concentration of the hydrofluoric acid aqueous solution is 55wt%, and the concentration of salpeter solution is 63wt%, and hydrofluoric acid is water-soluble in cleaning solution The volume ratio of liquid, salpeter solution and water is 1:3:6；
(2) for the intermediate product that step (1) obtains after 400~550 DEG C are heat-treated 0.5~2h, cooling obtains the Ti/TiO2 Combination electrode.
2. according to claim 1 have electro-catalysis and photocatalysis dual function applied to lithium-sky battery air electrode Nanostructured Ti/TiO2Combination electrode, which is characterized in that in step (1), the hydro-thermal reaction at 60~100 DEG C into 12~72h of row.
3. according to claim 1 have electro-catalysis and photocatalysis dual function applied to lithium-sky battery air electrode Nanostructured Ti/TiO2Combination electrode, which is characterized in that TiO2A diameter of 30~100nm of nano wire, length are 1~2 μ m。
CN201510373075.9A 2015-06-26 2015-06-26 The Ti/TiO of nanostructured2Combination electrode and its preparation method and application Expired - Fee Related CN105186007B (en)

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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
CN111370706B (en) * 2020-02-12 2022-01-25 金华高等研究院 Positive electrode material of metal-air battery and preparation method thereof

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