CN105289617A - Nickel cobalt oxide/carbon nanotube composite catalyst, preparation and application thereof - Google Patents
Nickel cobalt oxide/carbon nanotube composite catalyst, preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a nickel cobalt oxide/carbon nanotube composite catalyst, a preparation and an application thereof. The bi-functional catalyst comprises carbon nanotube and nickel cobalt oxide NiCo2O4 spinel; according to the preparation, nickel acetate, cobalt nitrate and carbon nanotube are respectively weighed, and then dissolved in ammoniacal liquor and the obtained material is performed with ultrasonic dispersion, then is subjected to a hydrothermal reaction at temperature of 140-160 DEG C for 3-6 hours, the obtained product is cooled to room temperature, cleaned and dried, calcined and ground to obtain the bi-functional catalyst. The invention also provides an application of the bifunctional catalyst in preparation of an air electrode of a metal air battery. The bi-functional catalyst has efficient oxygen reduction performance and efficient oxygen evolution performance in air.
Description
Technical field
The invention belongs to catalyst and Synthesis and applications field thereof, particularly a kind of cobalt acid nickel/carbon nano tube composite catalyst and Synthesis and applications thereof.
Background technology
In recent years, along with the consumption of fossil energy, the continuous increase of energy demand and environmental friendliness consciousness are constantly ripe, research developed by the countries in the world continuable energy conversion device of competing relative clean, wherein utilize the stored energy of electrochemical reaction and converting apparatus to be subject to people and greatly pay close attention to [NanoLett.2012,12,1946-1952].Secondary metal-air batteries have that preparation is simple, security performance is excellent and advantages of environment protection.In economic benefit and environmental protection, zinc-air battery has been acknowledged as one of 21 century the most effective and reliable new energy technology [Nanoscale2013,5,4657-4661].Particularly the theoretical energy density of zinc-air battery is much higher than traditional lithium ion battery, can be applied to the powerful devices such as electric automobile [ChemSocRev2014,43,5143-5402].But, owing to still lacking suitable air diffusion electrode eelctro-catalyst so far, make the discharge current density of air cell less than normal, shorter with the life-span under efficiency, thus greatly limit application and the industrialization paces of zinc-air battery.At present, the noble metal catalyst such as platinum carbon is still counted as ORR the highest active eelctro-catalyst.But the noble metal catalyst preparation costs such as platinum are quite high, earth reserves are rare simultaneously, cannot produce in a large number and generally use.In addition, although such catalyst shows good activity to ORR, and perform poor on OER [NanoLett.2011,11,5362-5366].Thus be extremely restricted in the large-scale application of reversible air electrode catalyst.Therefore develop cheap, corrosion-resistant and the bifunctional catalyst simultaneously with oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) seems particularly urgent.According to bibliographical information, cobaltosic oxide nano line be grown directly upon stainless steel mesh collector plate have excellent rechargeable performance and and stability, but zinc-air battery utilizes the not high [AdvancedEnergyMaterials of natural air generated energy in practice, 2014,6,1301389 – 1301395].The chemical property of the oxide of nickel and nickel is widely studied, but is mainly limited to oxygen evolution reaction (OER) [NatureCommunications, 2013,249,1805-1812 ,].NiCo
2o
4/ Graphene also has studied for ORR and OER, but directly applies to actual zinc and air cell and but have no report [J.Mater.Chem.2013, Isosorbide-5-Nitrae 754 – 4762].CNT (CNT) has excellent electric conductivity and extra specific surface area is large, has high electrochemical stability simultaneously, by carrying out composite modified with catalyst, and can the performance of significant increase catalyst.In the present invention, we have prepared cobalt acid nickel/carbon nano tube composite nano material as high activity and stable bifunctional electrocatalyst raw material, not only cheaply be easy to get, preparation method is simple, and it is environmentally friendly, being easy to suitability for industrialized production, is to be used in the good air electrode catalyst in the metal-air battery fields such as zinc-sky, aluminium-sky and magnesium-sky.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of cobalt acid nickel/carbon nano tube composite catalyst and Synthesis and applications thereof, cobalt acid nickel/carbon nano tube composite catalyst of the present invention had both shown excellent chemical property, had excellent charge-discharge performance and stability simultaneously; The present invention's not only environmental protection, raw material are easy to get, cost is low, and reaction condition is gentle, the reaction time is short, have the simple only step of technique can, practical, can the handling advantage such as by force, be easy to large-scale production.To be used in the good air electrode catalyst in the metal-air battery fields such as zinc-sky, aluminium-sky and magnesium-sky.
A kind of cobalt acid nickel/carbon nano tube composite catalyst of the present invention, is characterized in that: described cobalt acid nickel/carbon nano tube composite catalyst comprises CNT, cobalt acid nickel Co
2o
4spinelle.
Described cobalt acid nickel Co
2o
4spinelle is that nanosphere diameter is at 20-150nm.
Described cobalt acid nickel/carbon nano tube composite catalyst is nanotube, cobalt acid nickel Co
2o
4the compound of spinelle.
The preparation method of a kind of cobalt acid nickel/carbon nano tube composite catalyst of the present invention, comprising:
Take nickel acetate, cobalt nitrate and CNT respectively, be dissolved in ammoniacal liquor, ultrasonic disperse, then at 140-160 DEG C of hydro-thermal reaction 3-6h, be cooled to room temperature, cleaning, drying, calcining, grinding, obtain cobalt acid nickel/carbon nano tube composite catalyst; Wherein the mass volume ratio of nickel acetate, cobalt nitrate, CNT, ammoniacal liquor is 0.5-2g:0.5-2g:0.2-0.5g:10-25ml, preferred 1g:1g:0.25g:25ml.
The concentration of described ammoniacal liquor is 1-1.5mol/L.
The described ultrasonic disperse time is 0.5-2h;
Cleaning is washed with de-ionized water 3-5 time; Drying is 50-70 DEG C of dry 6-10h; 1-5 hour is calcined in Muffle furnace at calcining is 200-500 DEG C; Be ground to and be cooled to less than 60 DEG C grindings.
Preferably, the calcining heat in described Muffle furnace is 200-400 DEG C, and the time is 1h-4h.
More preferably, the calcining heat in described Muffle furnace is 400 DEG C, and the time is 3 hours.
Preferably, the described ultrasonic disperse time is 1.5 hours.
Preferably, the mass ratio of described nickel nitrate, cobalt nitrate and CNT is 1:1:0.25.
The application of a kind of cobalt acid nickel/carbon nano tube composite catalyst of the present invention, the application of described cobalt acid nickel/carbon nano tube composite catalyst in the air electrode preparing metal-air battery: be specially: catalyst fines is dissolved in the Nafion solution of ethanol and 5% (mass percentage concentration), ultrasonic, form homogeneous catalyst slurry, then spread upon on the carbon paper of hydrophobic treatment, carrying capacity is 0.5-5mg/cm
2, dry, prepare air electrode; Wherein the ratio of catalyst, ethanol, Nafion solution is 3-5 μ g:0.5-1ml:5-8 μ L.
Described ultrasonic time is 30min; Drying is 50 DEG C of dry 20-40min.
Described metal-air battery is zinc-empty battery, aluminium-empty battery or magnesium-empty battery.
Catalyst prepared by the present invention especially at 400 DEG C preparation table reveal good chemical property, ORR rise a spike potential play spike potential at 1.43V at 1.09V, OER, power density can reach 300mW/cm
-2, energy density can reach 850mAh/g, has good stable charge/discharge simultaneously.
Catalyst of the present invention can be the cobalt acid nickel (NiCo of nanosphere
2o
4) spinelle grows on the carbon nanotubes, or CNT passes the cobalt acid nickel (NiCo of nanosphere simultaneously
2o
4) spinelle, i.e. cobalt acid nickel (NiCo
2o
4) spinelle and the intact compound of CNT and be mixed into one.The bifunctional catalyst with premium properties of the present invention is applied to be prepared on the air electrode of metal-air battery, can apply power supply and the energy storage devices as fixed energy station such as electric automobile, Medical Devices (as audiphone) and escape way.
" difunctional " of the present invention, for both to have had hydrogen reduction (ORR) performance in atmosphere, has again oxygen simultaneously and separates out (OER) performance.
beneficial effect
(1) cobalt acid nickel/carbon nano tube composite catalyst catalyst of the present invention is that bifunctional catalyst had both shown excellent chemical property, there is excellent charge-discharge performance and stability simultaneously, the spike potential that rises of the special catalyst ORR that preparation table reveals at 400 DEG C plays spike potential at 1.43V at 1.09V, OER.Under air conditions, catalyst loading is 2mg/cm
2monocell adopt the mode power density of gradual change current electric power generation to reach 300mW/cm
2;
(2) the present invention's not only environmental protection, raw material are easy to get, cost is low, and reaction condition is gentle, the reaction time is short, have the simple only step of technique can, practical, can the handling advantage such as by force, be easy to large-scale production.To be used in the good air electrode catalyst in the metal-air battery fields such as zinc-sky, aluminium-sky and magnesium-sky;
(3) after air electrode made by catalyst of the present invention, 100 hours can be stabilized in small area analysis discharge and recharge, in high current charge-discharge, also there is excellent stability, can metal-air battery be directly used in, significantly reduce the cost of manufacture of metal-air battery;
(4) use this catalyst preparing gas-diffusion electrode (GDL) and zine plate to be assembled into zinc-air battery, can obtain excellent chemical property and charge-discharge performance in 6MKOH solution, its generated output reaches 300mW/cm in atmosphere
2, 100 hours can be stabilized in discharge and recharge, show superior chemical property and secondary cell can charge and discharge performance.
Accompanying drawing explanation
Fig. 1 is the Electronic Speculum figure of the bifunctional catalyst of embodiment 1 gained; A is the overall transmission electron microscope picture of catalyst; B is figure a partial enlargement transmission electron microscope picture.
Fig. 2 is CNTs, NiCo
2o
4, NiCo
2o
4oRR and the OER polarization curve comparison diagram of/CNTs and 20%Pt/C;
Fig. 3 is the polarization curve of catalyst at different heat treatment temperature;
Fig. 4 is that after catalyst preparing becomes air electrode and zine plate to form monocell, carrying capacity is 2mg/cm
2generating curve map;
Fig. 5 is that catalyst preparing becomes air electrode and zine plate to form after monocell at 10mAcm
-2discharge under current density figure for a long time;
Fig. 6 is that catalyst preparing becomes air electrode and zine plate to form after monocell at 10mAcm
-2discharge under current density and cyclic electrolysis matter figure for a long time;
Fig. 7 is that catalyst preparing becomes air electrode and zine plate to form after monocell at 10mAcm
-2whether under current density and discharge under cyclic electrolysis matter comparison diagram for a long time;
Fig. 8 is that zinc and air cell is at 0 ~ 65mAcm
-2voltage change figure under current density;
Fig. 9 is that zinc and air cell is at 10mAcm
-2the charge and discharge electrograph that current density once circulates for lower 10 minutes;
Figure 10 is that zinc and air cell is at 50mAcm
-2the charge and discharge electrograph that current density once circulates for lower 8 hours.
Detailed description of the invention
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
CNT described in various embodiments of the present invention is bought from Chengdu Ai Fa Nanosolutions GmbH, and its length is 15nm, and diameter is 30-50nm.Described nickel acetate is bought from Chemical Reagent Co., Ltd., Sinopharm Group, and pure for analyzing, molecular weight is about 176.68g.Described cobalt nitrate is bought from Chemical Reagent Co., Ltd., Sinopharm Group, and pure for analyzing, molecular weight is about 291.03g.
Embodiment 1
Catalyst: comprise CNT, cobalt acid nickel (NiCo
2o
4) spinelle; Wherein cobalt acid nickel (NiCo
2o
4) spinelle is nanosphere, diameter is at 20-150nm; Cobalt acid nickel (NiCo
2o
4) spinelle and CNT be combined with each other.
Preparation method:
Take 1g nickel acetate, 1g cobalt nitrate and 0.25g CNT respectively, be dissolved in the ammoniacal liquor of the 1-1.5mol/L of 25mL, ultrasonic disperse 1 hour, then 140 DEG C of reactions 5 hours are transferred in autoclave, be cooled to room temperature, forward 70 DEG C of drying box inner dryings 10 hours to neutrality 5 times by washed with de-ionized water.After drying, calcine 1 ~ 5 hour in Muffle furnace at 400 DEG C, cool to less than 60 DEG C thereupon and pulverize, obtain bifunctional catalyst.As shown in Figure 1, cobalt acid nickel (NiCo of the present invention
2o
4) spinelle is nanosphere, diameter is at 20-150nm; Cobalt acid nickel (NiCo
2o
4) spinelle and CNT be combined with each other.
Be dissolved in by the catalyst fines of 5mg in the nafion solution of 5% of 1ml ethanol and 8 μ l, within ultrasonic 30 minutes, form homogeneous catalyst slurry, then drip to be coated onto on disc electrode and then naturally dry, catalyst loading is 100 μ g.
The cyclic voltammetry curve of catalyst is measured with electrochemical workstation.Pass into oxygen 30 minutes at the potassium hydroxide solution of 0.1mol/L, then the disc electrode scribbling catalyst is made working electrode, full calomel electrode and Pt electrode is respectively reference electrode and to electrode, sequentially determining CNTs, NiCo
2o
4, NiCo
2o
4oRR and the OER polarization curve of/CNTs and 20%Pt/C.
As shown in Figure 2, result shows that the difunctional performance of catalyst is obvious to experimental result, and the spike potential that rises of ORR plays spike potential at 1.43V at 0.935V, OER.When 0.2V, CNTs, NiCo
2o
4, NiCo
2o
4/ CNTs and 20%Pt/C current density are respectively 1.8mA/cm
-2, 1.7mA/cm
-2, 6.1mA/cm
-2and 3.6mA/cm
-2.NiCo on OER
2o
4/ CNTs then shows very excellent chemical property, is much better than 20%Pt/C catalyst.
Embodiment 2
Bifunctional catalyst: comprise CNT, cobalt acid nickel (NiCo
2o
4) spinelle, wherein cobalt acid nickel (NiCo
2o
4) spinelle is nanosphere, diameter is at 20-150nm; Cobalt acid nickel (NiCo
2o
4) spinelle and CNT be combined with each other.
Preparation method is:
Take 1g nickel acetate, 1g cobalt nitrate and 0.25g CNT respectively, be dissolved in the ammoniacal liquor of the 1-1.5mol/L of 25mL, ultrasonic disperse 1 hour, then 150 DEG C of reactions 5 hours are transferred in autoclave, be cooled to room temperature, forward 70 DEG C of drying box inner dryings 10 hours to neutrality 3-5 time by washed with de-ionized water; After drying, at 200 DEG C, 300 DEG C, 400 DEG C, calcine 1 hour in Muffle furnace at 500 DEG C, pulverize when dropping to below 60 DEG C, obtain bifunctional catalyst.
Be dissolved in by the catalyst fines of 5mg in the nafion solution of 5% of 1ml ethanol and 8 μ l, within ultrasonic 30 minutes, form homogeneous catalyst slurry, then drip and be coated onto on disc electrode, catalyst loading is 100 μ g, then naturally dries.
The cyclic voltammetry curve of catalyst is measured with electrochemical workstation.Pass into oxygen 30 minutes at the potassium hydroxide solution of 0.1mol/L, then the disc electrode scribbling catalyst is made working electrode, full calomel electrode and Pt electrode is respectively reference electrode and to electrode, sequentially determining is at 200 DEG C, 300 DEG C, 400 DEG C, NiCo under 500 DEG C of calcining heats
2o
4oRR and the OER polarization curve of/CNTs.
Experimental result as shown in Figure 3, when 0.2V, 200 DEG C, 300 DEG C, 400 DEG C, NiCo under 500 DEG C of calcining heats
2o
4/ CNTs current density is respectively 1.8mA/cm
-2, 5.8mA/cm
-2, 6.1mA/cm
-2and 9mA/cm
-2.When calcining heat is 400 DEG C, catalyst effect is best, and meanwhile, the spike potential that rises of ORR reaches 0.935V, and OER plays spike potential and reaches 1.43V.
Embodiment 3
The catalyst fines of the embodiment 1 of 5mg is dissolved in the Nafion solution of 5% of 1ml ethanol and 8 μ l, within ultrasonic 30 minutes, forms homogeneous catalyst slurry, be then coated on the carbon paper of hydrophobic treatment that (carrying capacity is 2mg/cm
2), 50 DEG C of dryings prepare air electrode in 30 minutes, simultaneously using the zinc paper tinsel identical with carbon paper area as negative electrode, air electrode, zinc paper tinsel are put into reaction cell groove and the potassium hydroxide solution 9mL adding 6mol/L forms complete zinc and air cell, utilize activation of fuel cell system to utilize gradual change current-mode to test:
Under normal temperature and pressure, as shown in Figure 4, can find out that monocell open-circuit voltage reaches 1395mV, maximum generation power density reaches 321mW/cm for test generating curve and polarization curve
2.When voltage is 1V, electric current reaches 213.9/cm
2, generated output density then reaches 215.1mW/cm
2.
Embodiment 4
The catalyst fines of the embodiment 1 of 5mg is dissolved in the Nafion solution of 5% of 1ml ethanol and 8 μ l, within ultrasonic 30 minutes, forms homogeneous catalyst slurry, then spread upon on the carbon paper of hydrophobic treatment that (carrying capacity is 0.5mg/cm
2), 50 DEG C of dryings prepare air electrode in 30 minutes, simultaneously using the zinc paper tinsel identical with carbon paper area as negative electrode, the potassium hydroxide solution of air electrode, zinc paper tinsel and 9mL6mol/L is put into homemade zinc and air cell groove, after overactivation, utilized by zinc and air cell blue electric system to test, test condition is 10mAcm
-2discharge for a long time under current density.
As shown in Figure 5, the charging voltage of zinc and air cell is at 10mA/cm for test result
2electric current discharge for a long time, discharge voltage maintains about 1.25V, and almost no change in 60 hours.Illustrate that the charge-discharge performance of battery is very stable, there is fine practical potential.When zine plate runs out of, improve battery life by changing zine plate.As shown in Figure 7, through calculating, its actual energy density can reach 670mAh/g.
Embodiment 5
The catalyst fines of the embodiment 1 of 5mg is dissolved in the Nafion solution of 5% of 1ml ethanol and 8 μ l, within ultrasonic 30 minutes, forms homogeneous catalyst slurry, then spread upon on the carbon paper of hydrophobic treatment that (carrying capacity is 0.5mg/cm
2), 50 DEG C of dryings prepare air electrode in 40 minutes, simultaneously using the zinc paper tinsel identical with carbon paper area as negative electrode, air electrode, zinc paper tinsel are put into homemade zinc and air cell groove, constantly supplement the potassium hydroxide solution of 6mol/L simultaneously, after overactivation, utilized by zinc and air cell blue electric system to test, test condition is 10mA/cm
2discharge for a long time under current density.
As shown in Figure 6, the charging voltage of zinc and air cell is at 10mA/cm for test result
2electric current discharge for a long time, discharge voltage maintains about 1.25V, and voltage almost no change in 100 hours.Illustrate that the charge-discharge performance of battery is very stable.Known compared with case study on implementation 5, under sufficient electrolyte conditions, battery life is improved significantly.As shown in Figure 7, through calculating, its actual energy density can reach 870mAh/g.
Embodiment 6
The catalyst fines of the embodiment 1 of 5mg is dissolved in the Nafion solution of 5% of 1ml ethanol and 8 μ l, within ultrasonic 30 minutes, forms homogeneous catalyst slurry, then spread upon on the carbon paper of hydrophobic treatment that (carrying capacity is 0.5mg/cm
2), 50 DEG C of dryings prepare air electrode in 40 minutes, simultaneously using the zinc paper tinsel identical with carbon paper area as negative electrode, respectively the potassium hydroxide solution of the 6mol/L of air electrode, zinc paper tinsel and 9mL is put into homemade zinc and air cell groove, after overactivation, blue electric system is utilized by zinc and air cell to test.As shown in Figure 8, zinc-air battery is at 5 ~ 65mA/cm for test result
2current density, charge and discharge cycles time are carry out discharge and recharge under condition in 10 minutes.At 5 ~ 65mA/cm
2current density range, within discharge voltage difference maintains 1V.Illustrate that catalyst has very excellent chemical property.
Embodiment 7
The catalyst fines of the embodiment 1 of 5mg is dissolved in the Nafion solution of 5% of 1ml ethanol and 8 μ l, within ultrasonic 30 minutes, forms homogeneous catalyst slurry, then spread upon on the carbon paper of hydrophobic treatment that (carrying capacity is 0.5mg/cm
2), 50 DEG C of dryings prepare air electrode in 40 minutes, simultaneously using the zinc paper tinsel identical with carbon paper area as negative electrode, respectively the potassium hydroxide solution of the 6mol/L of air electrode, zinc paper tinsel and 9mL is put into homemade zinc and air cell groove, after overactivation, utilized by zinc and air cell blue electric system to test, test condition is 10mA/cm
2current density, fully electric circulation timei are carry out discharge and recharge in 10 minutes.
As shown in Figure 9, zinc and air cell is at 10mA/cm for test result
2the close long-time electric discharge of electric current, discharge voltage maintains about 1.25V, and charging voltage is at about 2.1V, and voltage difference is 0.95V.After 240 charge and discharge cycles, voltage difference has almost no change, and illustrates that the charge-discharge performance of battery is very stable, can be applicable to the low-power equipments such as Medical Devices.
Embodiment 8
The catalyst fines of the embodiment 1 of 5mg is dissolved in the Nafion solution of 5% of 1ml ethanol and 8 μ l, within ultrasonic 30 minutes, forms homogeneous catalyst slurry, be then coated on the carbon paper of hydrophobic treatment that (carrying capacity is 0.5mg/cm
2), 50 DEG C of dryings prepare air electrode in 40 minutes, simultaneously using the zinc paper tinsel identical with carbon paper area as negative electrode, respectively the potassium hydroxide solution of the 6mol/L of air electrode, zinc paper tinsel and 9mL is put into homemade zinc and air cell groove, after overactivation, utilized by zinc and air cell blue electric system to test, test condition is 50mA/cm
2current density, fully electric circulation timei are carry out discharge and recharge in 10 minutes.
Test result as shown in Figure 10, zinc and air cell discharge voltage maintains about 1.22V, charging voltage at about 2.2V, and in 20 hours after multiple circulation voltage difference unchanged, illustrate that the high rate during charging-discharging of battery is very stable, potentially can be applied to the powerful devices such as electric automobile.
Claims (10)
1. cobalt acid nickel/carbon nano tube composite catalyst, is characterized in that: described cobalt acid nickel/carbon nano tube composite catalyst comprises CNT, cobalt acid nickel Co
2o
4spinelle.
2. a kind of cobalt acid nickel/carbon nano tube composite catalyst according to claim 1, is characterized in that: described cobalt acid nickel Co
2o
4spinelle is that nanosphere diameter is at 20-150nm.
3. a kind of cobalt acid nickel/carbon nano tube composite catalyst according to claim 1, is characterized in that: described cobalt acid nickel/carbon nano tube composite catalyst is nanotube, cobalt acid nickel Co
2o
4the compound of spinelle.
4. a preparation method for the cobalt acid nickel/carbon nano tube composite catalyst as described in as arbitrary in claim 1-3, comprising:
Take nickel acetate, cobalt nitrate and CNT respectively, be dissolved in ammoniacal liquor, ultrasonic disperse, then at 140-160 DEG C of hydro-thermal reaction 3-6h, be cooled to room temperature, cleaning, drying, calcining, grinding, obtain cobalt acid nickel/carbon nano tube composite catalyst; Wherein the mass volume ratio of nickel acetate, cobalt nitrate, CNT, ammoniacal liquor is 0.5-2g:0.5-2g:0.2-0.5g:10-25ml.
5. the preparation method of a kind of cobalt acid nickel/carbon nano tube composite catalyst according to claim 4, is characterized in that: the concentration of described ammoniacal liquor is 1-1.5mol/L.
6. the preparation method of a kind of cobalt acid nickel/carbon nano tube composite catalyst according to claim 4, is characterized in that: the described ultrasonic disperse time is 1h; Cleaning is washed with de-ionized water 3-5 time; Drying is 70 DEG C of dry 10h; 1-5 hour is calcined in Muffle furnace at calcining is 200-500 DEG C; Be ground to and be cooled to less than 60 DEG C grindings.
7. the preparation method of a kind of cobalt acid nickel/carbon nano tube composite catalyst according to claim 6, is characterized in that: the described ultrasonic disperse time is 0.5-2h; Calcining heat is 400 DEG C, and the time is 3h.
8. the application of cobalt acid nickel/carbon nano tube composite catalyst as claimed in claim 1, it is characterized in that: the application of described cobalt acid nickel/carbon nano tube composite catalyst in the air electrode preparing metal-air battery, be specially: catalyst fines is dissolved in ethanol and 5% Nafion solution in, ultrasonic, form homogeneous catalyst slurry, then be coated on the carbon paper of hydrophobic treatment, carrying capacity is 0.5-5mg/cm
2, dry, prepare air electrode.
9. the application of a kind of cobalt acid nickel/carbon nano tube composite catalyst according to claim 8, is characterized in that: the ratio of described catalyst, ethanol, Nafion solution is 3-5 μ g:0.5-1ml:5-8 μ L; Metal-air battery is zinc-empty battery, aluminium-empty battery or magnesium-empty battery.
10. the application of a kind of cobalt acid nickel/carbon nano tube composite catalyst according to claim 8, is characterized in that: described ultrasonic time is 20-30min; Drying is 45-50 DEG C of dry 30-40min.
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