CN104993159B - A kind of bifunctional catalyst and its preparation and the application in metal-air battery - Google Patents
A kind of bifunctional catalyst and its preparation and the application in metal-air battery Download PDFInfo
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- CN104993159B CN104993159B CN201510313325.XA CN201510313325A CN104993159B CN 104993159 B CN104993159 B CN 104993159B CN 201510313325 A CN201510313325 A CN 201510313325A CN 104993159 B CN104993159 B CN 104993159B
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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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
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Abstract
A kind of application the present invention provides bifunctional catalyst and its preparation and in metal-air battery.The preparation method of the bifunctional catalyst, it is characterised in that including：The first step：Prepare manganese dioxide presoma；Second step：Manganese dioxide presoma, cobalt nitrate and the carbon nanotubes that mass ratio is 0.5 1: 1: 0.25 0.5 are weighed respectively, it is dissolved in the ammonium hydroxide of 1 1.5mol/L, when ultrasonic disperse 0.5 1.5 is small, be then transferred in autoclave 140 160 DEG C of reactions 3~6 it is small when, it is cooled to room temperature, when 50 70 DEG C of dryings 6 10 are small after cleaning 35 times with deionized water；After drying, when calcining 0.5 1.5 is small in Muffle furnace at 350 450 DEG C, pulverize when dropping to less than 60 DEG C, up to bifunctional catalyst.The present invention not only has efficient hydrogen reduction performance in atmosphere, but also with efficiently analysis oxygen performance.
Description
Technical field
The invention belongs to the preparation of new energy battery and application field, more particularly to a kind of system of efficient bifunctional catalyst
The standby and its application in metal-air.
Background technology
In recent years, since the waste of fossil fuel, the global demand to the energy are continuously increased and environmentally friendly consciousness
Constantly ripe, the sustainable energy conversion device of the competing relative clean in countries in the world carries out developmental research, wherein anti-using electrochemistry
The high efficiency energy storage answered and converting apparatus are subject to people greatly to pay close attention to [NanoLett.2012,12,1946-1952].Particularly
The metal-air battery of rechargeable type is simple, safe and environmental-friendly due to being prepared with uniqueness, and compares energy with high theory
The advantage such as amount and energy density has caused the extensive concern of people.Wherein particularly in terms of economic benefit and environmental protection,
Zinc-air battery be acknowledged as one of 21 century maximally efficient and reliable new energy technology [Nanoscale 2013,
5,4657-4661].In addition, metal-air battery theoretical energy density is much higher than traditional lithium ion battery.And it is used as raw material
Selection, zinc is the 4th most abundant metal in the earth's crust, can bear larger battery production to meet ever-increasing need
Ask, while oxygen is widely existed in air again.However, electrocatalytic oxidation reduction reaction (ORR) and oxygen evolution reaction (OER) are in the moon
Extremely upper slow dynamics process, limits the efficiency of metal-air battery.At present, the noble metal catalyst such as platinum carbon still by
Regard the highest elctro-catalyst of ORR activity as.However, the noble metal catalyst manufacturing cost such as platinum is quite high, while earth reserves are dilute
Lack.Although in addition, such catalyst shows ORR good activity, and [the Nano that performs poor on OER
Lett.2011,11,5362-5366].Thus it is extremely restricted in the large-scale application of reversible air electrode.Therefore develop
The air electrode that cheap, corrosion-resistant and with high activity bifunctional catalyst is used as just seems particularly urgent.According to report
Road, cobaltosic oxide nano line, which is grown directly upon stainless steel mesh collector plate, to be had excellent rechargeable performance and and stablizes
Property, however in practice zinc-air battery using natural air generated energy it is not high [Advanced Energy Materials,
Vol4.A6, pp.1301389-1301395, APR 2014].Dai etc. is prepared for cobalt oxide/carbon nanotubes and Ni-Fe-stratiform
Double-hydroxide elctro-catalyst is used for rechargeable type zinc-air battery cathode, and generated output reaches 265mW, but still stops
Under the conditions of pure oxygen, and battery model complex [Nature Communications, vol249.A, pp.1805-
1812, APR 2013].Since carbon nanotubes (CNT) has, excellent electric conductivity and extra specific surface area are big, while have height
Electrochemical stability.In addition, other cobalt spinel-like oxides electro catalytic activity and oxide stability such as：Co3O4
[J.Mater.Chem.A 2014,2,3794-3800], Co3O4/MnCo2O4[Nanoscale 2013,5,5312-5315] and
MnCo2O4/CoMn2O4[Sci.Rep.2012,2 (986), 1-8] also has been reported that.Particularly MnCo2O4 has been widely used for alkalescence
Fuel cell, but above catalyst is cumbersome there are preparation process, whether in chemical property or charge-discharge performance and
Cycle life etc. all need to be improved.In order to overcome the above insufficient, we are prepared for manganese dioxide/tetra- and aoxidize three in the present invention
Bifunctional electrocatalyst raw material of the cobalt/carbon nano tube composite nano material as high activity and stabilization, not only cheap and easily-available, preparation
Method is simple, and environmentally friendly, is easy to industrialized production, is that can be used in the metals such as zinc-sky, aluminium-sky and magnesium-sky sky
The good air electrode catalyst of gas field of batteries.
The content of the invention
Technical problems to be solved needed for the present invention are to provide a kind of preparation of the bifunctional catalyst with excellent performance
Method and its application in metal-air, the catalyst prepare especially at 400 DEG C and show preferable chemical property,
ORR's plays spike potential in 1.04V, and OER plays spike potential in 1.45V, while has good stable charge/discharge, preparation method letter
Single, cost is low, is suitable for industrialized production.
In order to solve the above technical problem, the present invention provides a kind of bifunctional catalyst, it is characterised in that is received including carbon
Mitron, cobalt oxide and manganese dioxide.
Preferably, the manganese dioxide is tubulose, and length is at 1-3 μm, and internal diameter is in 7-10nm；Cobalt oxide is diameter 10-
The nano particle of 20nm；The length of carbon nanotubes is 3-10 μm, and carbon nanotubes, cobalt oxide and manganese dioxide are combined with each other.
Present invention also offers the preparation method of above-mentioned bifunctional catalyst, it is characterised in that including：
The first step：The mass ratio of configuration potassium permanganate and water is 1~2: 100 liquor potassic permanganate, at room temperature by Gao Meng
The concentrated hydrochloric acid that sour potassium solution and concentrated hydrochloric acid ratio is 101~102g: 4ml is added in the liquor potassic permanganate of stirring, and it is straight to continue stirring
To being uniformly mixed, by the mixed liquor of gained be transferred in autoclave at 135-145 DEG C hydro-thermal method reaction 10-14 it is small when, be cooled to
Room temperature, is cleaned 3-5 times with ethanol and deionized water respectively, when then 60-80 DEG C of dry 12-24 is small, obtains manganese dioxide forerunner
Body；
Second step：Manganese dioxide presoma, cobalt nitrate and the carbon that mass ratio is 0.5-1: 1: 0.25-0.5 are weighed respectively
Nanotube, is dissolved in the ammonium hydroxide of 1-1.5mol/L, when ultrasonic disperse 0.5-1.5 is small, is then transferred to 140-160 in autoclave
When DEG C reaction 3~6 is small, it is cooled to room temperature, when clean 3-5 times with deionized water 50-70 DEG C of dry 6-10 is small afterwards；After drying,
When calcining 0.5-1.5 is small in Muffle furnace at 350-450 DEG C, pulverize when dropping to less than 60 DEG C, up to bifunctional catalyst.
Preferably, the calcining heat in the Muffle furnace be 200-400 DEG C, the time for 0.5 it is small when -4 it is small when.
It is highly preferred that the calcining heat in the Muffle furnace is 400 DEG C, when the time is 3 small.
Preferably, the mass ratio of the manganese dioxide presoma in the second step, cobalt nitrate and carbon nanotubes is
0.5∶1∶0.25。
Preferably, when the ultrasonic disperse time is 1.5 small.
Preferably, the mass ratio of the manganese dioxide presoma, cobalt nitrate and carbon nanotubes is 0.5: 1: 0.25.
Present invention also offers application of the above-mentioned bifunctional catalyst in the air electrode of metal-air battery is prepared.
Preferably, the metal-air battery is zinc-sky battery, aluminium-sky battery or magnesium-sky battery.
The catalyst of the present invention can be that particulate oxidation cobalt is grown in manganese dioxide and carbon nanotubes, or load at the same time
The manganese dioxide of cobalt oxide and carbon nanotubes are compound and mix.The double-function catalyzing with excellent performance of the present invention
Agent be applied to prepare on the air electrode of metal-air battery, can apply electric automobile, Medical Devices (such as hearing aid) and
The power supplys such as escape way.
It is of the present invention " difunctional " not only to have hydrogen reduction (ORR) performance in atmosphere, but also separated out with oxygen
(OER) performance.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) bifunctional catalyst of the invention had both shown excellent chemical property, while had excellent discharge and recharge
Performance and stability, the spike potential that rises that the catalyst ORR shown is especially prepared at 400 DEG C play spike potential in 1.04V, OER
In 1.45V, it is 3.3mg/cm to be assembled into monocell rear catalyst carrying capacity2When, generated energy can reach 315mW/ under natural air
cm2。
(2) present invention is not only environmentally protective, raw material is easy to get, cost is low, and reaction condition is gentle, the reaction time is short, has
The advantages that technique is simple, practical, and controllability is strong, is easy to large-scale production.Be can be used in zinc-sky, aluminium-sky and magnesium-
The good air electrode catalyst in the metal-air battery such as sky field.
(3) after air electrode is made in catalyst of the invention, can stablize in low current discharge and recharge left when 200 is small
The right side, also has excellent stability in high current charge-discharge, can be directly used for metal-air battery, significantly reduce metal-air
The cost of manufacture of battery.
(4) use the catalyst preparation gas-diffusion electrode (GDL) and be assembled into zinc-air battery, in 6MKOH solution
Excellent chemical property and charge-discharge performance can be obtained, its generated output can reach 313mW/cm2, discharge and recharge in atmosphere
In can stablize when 200 is small or so, show superior chemical property and repeatability.
Brief description of the drawings
Fig. 1 is CNTs, Co3O4/MnO2/CNTs、Co3O4The cyclic voltammetry curve figure of/MnO2
Fig. 2 is CNTs, Co3O4/MnO2ORR the and OER polarization curve comparison diagrams of/CNTs and 20%Pt/C；
Fig. 3 is polarization curve of the catalyst under different carrying capacity；
Fig. 4 is the polarization curve of different manganese dioxide, cobalt nitrate and carbon nanotube mass than preparing three-way catalyst；
Fig. 5 is the polarization curve of catalyst different heat treatment time at 400 DEG C；
Fig. 6 is polarization curve of the catalyst at a temperature of different heat treatment；
Fig. 7 be catalyst preparation into air electrode carrying capacity be 3.213mg/cm2Power generation curve map；
Fig. 8 is the zinc and air cell charge and discharge electrograph under electric current 5mA and 50mA respectively；
Fig. 9 is zinc and air cell respectively in 5mA/cm2Under charge and discharge electrograph；
Figure 10 is the electron microscope of the bifunctional catalyst of the gained of embodiment 1.
Embodiment
With reference to specific embodiment, the present invention is further explained.It will be appreciated that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.It should also be understood that be, after reading the content taught by the present invention, this area skill
Art personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims institute
The scope of restriction.
Carbon nanotubes described in various embodiments of the present invention is bought from Chengdu Ai Fa Nanosolutions GmbH, its Length is
15nm, OD 30-50nm.The potassium permanganate is bought from Sinopharm Chemical Reagent Co., Ltd., to analyze pure, molecular weight
About 158.03g.The cobalt nitrate is bought from Sinopharm Chemical Reagent Co., Ltd., and pure to analyze, molecular weight is about
291.03g。
Embodiment 1
A kind of bifunctional catalyst, including carbon nanotubes, cobalt oxide and manganese dioxide.The manganese dioxide is tubulose,
Length is at 1-3 μm, and internal diameter is in 7-10nm；Cobalt oxide is the nano particle of diameter 10-20nm；Carbon nanotubes, cobalt oxide and dioxy
Change manganese to be combined with each other.
The preparation method of bifunctional catalyst of the present invention is：
(1) mass ratio of configuration potassium permanganate and water is 1.2: 100 homogeneous mixed aqueous solution, at room temperature by potassium permanganate
The ratio of solution and concentrated hydrochloric acid (concentration 37.5%, similarly hereinafter) is that 101.2g: 4ml concentrated hydrochloric acid is slowly added to the potassium permanganate of stirring
In solution, stirring is until be uniformly mixed, when homogeneous solution poured into autoclave hydro-thermal method reaction 12 is small at 140 DEG C, cooling
To room temperature, respectively with respectively cleaning 3 times of ethanol and deionized water, when then 70 DEG C of dryings 24 are small, manganese dioxide presoma is obtained；
(2) the above-mentioned manganese dioxide precursors of 0.125g, 0.2g cobalt nitrates and 0.075g carbon nanotubes are weighed respectively, are dissolved
In the 1.3mol/L ammonium hydroxide of 15ml, when ultrasonic disperse 1 is small, then transfer put 150 DEG C of autoclave reaction 3 it is small when, be cooled to room
Temperature, when 60 DEG C of dryings 8 are small after cleaning 3 times with deionized water；
(3) when by above-mentioned product, calcining 1 is small in Muffle furnace at 400 DEG C, then grind into powder when dropping to less than 60 DEG C,
Up to bifunctional catalyst, as shown in Figure 10, particulate oxidation cobalt of the present invention is grown in manganese dioxide and carbon nanometer
Guan Shang.
The catalyst fines of 5mg is dissolved in 1ml ethanol and the 5% nafion solution of 8 μ l, ultrasound forms equal for 30 minutes
One catalyst slurry, then in drop coating to disc electrode, catalyst loading is 50 μ g, then naturally dry.
With the cyclic voltammetry curve of electrochemical workstation measure catalyst.Oxygen is passed through in the potassium hydroxide solution of 0.1mol/L
Gas 30 minutes, then the disc electrode for scribbling catalyst is made into working electrode, full calomel electrode and Pt electrodes be respectively reference electrode and
To electrode, sequentially determining
The cyclic voltammetry curve of CNTs, Co3O4/MnO2/CNTs, Co3O4/MnO2.
Experimental result is as shown in Figure 1, the results showed that catalyst has obvious reduction peak and an oxidation peak, and reduction peak with
Oxidation peak is more symmetrical.
Embodiment 2
Catalyst fines prepared by the embodiment 1 of 5mg is dissolved in 1ml ethanol and the 5% nafion solution of 8 μ l, is surpassed
Sound forms homogeneous catalyst slurry in 30 minutes, and catalyst loading of then attaining the Way in drop coating to disc electrode is 50 μ g, is then dried in the air naturally
It is dry.With the polarization curve of electrochemical workstation measure catalyst.Oxygen 30 is passed through in the potassium hydroxide solution of 0.1mol/L to divide
Clock, then will scribble the disc electrode of catalyst as working electrode, full calomel electrode and Pt electrodes are respectively reference electrode and to electricity
Pole, the polarization curve of sequentially determining CNTs, Co3O4/MnO2/CNTs, Co3O4/MnO2.
Experimental result is as shown in Figure 2, the results showed that the difunctional performance of catalyst is obvious, and the spike potential that rises of ORR exists
1.04V, OER play spike potential in 1.45V.In 0.2V, Co3O4/MnO2/CNTs, 20%Pt/C, CNTs；Current density is distinguished
For 3.6mA*cm-2, 3.8mA*cm-2And 2.2mA*cm-2, Co3O4/MnO2/CNTs then shows very excellent electricity on OER
Chemical property, is much better than 20%Pt/C catalyst.
Embodiment 3
Catalyst fines prepared by the embodiment 1 of 5mg is dissolved in 1ml ethanol and the 5% nafion solution of 8 μ l, is surpassed
Sound forms homogeneous catalyst slurry in 30 minutes, then make catalyst loading for 50 in drop coating to disc electrode respectively, 100,150,
200th, 250 μ g, then naturally dry.With the polarization curve of electrochemical workstation measure catalyst.In the hydrogen-oxygen of 0.1mol/L
Change potassium solution and be passed through oxygen 30 minutes, then the disc electrode of catalyst will be scribbled as working electrode, full calomel electrode and Pt electrodes
Respectively reference electrode and to electrode, the polarization curve of three-way catalyst under sequentially determining difference carrying capacity.
Experimental result is as shown in Figure 3, the results showed that the difunctional performance of catalyst is obvious, the ORR under different carrying capacity
Spike potential is played almost in 1.04V, and OER plays spike potential in 1.45V, while is can be found that with the increase dissufion current of carrying capacity
It is remarkably reinforced.
Embodiment 4
A kind of bifunctional catalyst, including carbon nanotubes, cobalt oxide and manganese dioxide.The manganese dioxide is tubulose,
Length is at 1-3 μm, and internal diameter is in 7-10nm；Cobalt oxide is the nano particle of diameter 10-20nm；Carbon nanotubes, cobalt oxide and dioxy
Change manganese to be combined with each other.
The different quality of bifunctional catalyst raw material than preparation method：
(1) mass ratio of configuration potassium permanganate and water is 1.2: 100 homogeneous mixed aqueous solution, at room temperature by potassium permanganate
The concentrated hydrochloric acid that the ratio of solution and concentrated hydrochloric acid is 101.2g: 4ml is slowly added in the liquor potassic permanganate of stirring, and stirring is until mixing
Uniformly, by homogeneous solution pour into autoclave 140 DEG C of hydro-thermal methods reactions 12 it is small when, be cooled to room temperature, with ethanol and go respectively
Ionized water respectively cleaning 3 times, when then 70 DEG C of dryings 24 are small, obtain manganese dioxide presoma；
(2) mass ratio weighed is respectively the above-mentioned manganese dioxide precursor in 1: 1: 0.5,0.5: 1: 0.5 and 0.5: 1: 0.25,
It is ultrasonic disperse 1 in 0.2g: 15ml 1.3mol/L ammonium hydroxide that cobalt nitrate and carbon nanotubes, which are dissolved in cobalt oxide and the ratio of ammonium hydroxide,
Hour, when being transferred to that 150 DEG C of hydro-thermal reactions 5 are small in autoclave, it is cooled to room temperature, is cleaned 5 times with deionized water, then 60 DEG C of dryings
8 it is small when；
(3) by when calcining 1 is small in Muffle furnace at 400 DEG C above-mentioned of product.Then grind into powder when dropping to less than 60 DEG C,
Up to bifunctional catalyst.
The catalyst fines for weighing 5mg respectively is dissolved in 1ml ethanol and the 5% nafion solution of 8 μ l, ultrasound 30 minutes
Homogeneous catalyst slurry is formed, it is 100 μ g then to make catalyst loading in drop coating to disc electrode respectively, then naturally dry.
With the polarization curve of electrochemical workstation measure catalyst.Oxygen is passed through in the potassium hydroxide solution of 0.1mol/L 30 minutes,
The disc electrode of catalyst will be scribbled again as working electrode, full calomel electrode and Pt electrodes are respectively reference electrode and to electrode,
The different quality of sequentially determining three-way catalyst is than polarization curve prepared by raw material.
Experimental result is as shown in Figure 4, the results showed that different manganese dioxide, cobalt nitrate and carbon nanotube mass compare catalyst
Difunctional performance it is obvious, particularly in manganese dioxide, cobalt nitrate and carbon nanotube mass ratio are 0.5: 1: 0.25 performance
Performance substantially increases compared with other two kinds of ratios, and ORR dissufion currents can reach 5.7mA/cm-2, OER dissufion currents then exist
1.7V has reached 17mA/cm-2。
Embodiment 5
A kind of bifunctional catalyst, including carbon nanotubes, cobalt oxide and manganese dioxide.The manganese dioxide is tubulose,
Length is at 1-3 μm, and internal diameter is in 7-10nm；Cobalt oxide is the nano particle of diameter 10-20nm；The length of carbon nanotubes is 3-10m,
Carbon nanotubes, cobalt oxide and manganese dioxide are combined with each other.
The preparation of ternary bifunctional catalyst under different calcination times：
(1) it is 1.2: 100 homogeneous mixed aqueous solutions to configure potassium permanganate and the mass ratio of water, at room temperature by potassium permanganate
The concentrated hydrochloric acid that the ratio of solution and concentrated hydrochloric acid is 101.2g: 4ml is slowly added in the liquor potassic permanganate of stirring, and stirring is until mixing
Uniformly, when homogeneous solution being poured into 140 DEG C 12 small in autoclave, it is cooled to room temperature, it is each clear with ethanol and deionized water respectively
Wash 3 times, when then 70 DEG C of dryings 24 are small, obtain manganese dioxide precursor；
(2) mass ratio weighed is respectively 1: 1: 0.5 above-mentioned manganese dioxide precursor, cobalt nitrate and carbon nanotubes dissolving
In the 1.3mol/L ammonium hydroxide that the ratio of cobalt oxide and ammonium hydroxide is 0.2g: 15ml, when ultrasonic disperse 1 is small, 150 DEG C are transferred in autoclave
When hydro-thermal reaction 5 is small, it is cooled to room temperature, is cleaned 5 times with deionized water, when then 60 DEG C of dryings 8 are small；
(3) by when calcining 1,2,3,4 is small in above-mentioned the product respectively Muffle furnace at 400 DEG C.When dropping to less than 60 DEG C
Then grind into powder, obtains bifunctional catalyst.
The catalyst fines for weighing 5mg difference calcination times respectively is dissolved in 1ml ethanol and the 5% nafion solution of 8 μ l
In, ultrasound forms homogeneous catalyst slurry in 30 minutes, and it is 100 μ then to make catalyst loading in drop coating to disc electrode respectively
G, then naturally dry.With the polarization curve of electrochemical workstation measure catalyst.In the potassium hydroxide solution of 0.1mol/L
It is passed through oxygen 30 minutes, then the disc electrode for scribbling catalyst is respectively joined as working electrode, full calomel electrode and Pt electrodes
The polarization curve prepared than electrode and to electrode, sequentially determining three-way catalyst under different calcining heats.
Experimental result is as shown in Figure 5, the results showed that for catalyst under 400 DEG C of different calcination times, ORR's plays spike potential
Play spike potentials with OER and significant changes occur, the effect of catalyst is worst when calcination time is 2 hours, and upon calcination between be 3
Hour catalyst effect reaches maximum.
Embodiment 6
A kind of bifunctional catalyst, including carbon nanotubes, cobalt oxide and manganese dioxide.The manganese dioxide is tubulose,
Length is at 1-3 μm, and internal diameter is in 7-10nm；Cobalt oxide is the nano particle of diameter 10-20nm；The length of carbon nanotubes is 3-10m,
Carbon nanotubes, cobalt oxide and manganese dioxide are combined with each other.
The preparation of three-way catalyst under different calcining heats：
(1) it is 1.2: 100 homogeneous mixed aqueous solutions to configure potassium permanganate and the mass ratio of water, at room temperature by potassium permanganate
The concentrated hydrochloric acid that the ratio of solution and concentrated hydrochloric acid is 101.2g: 4ml is slowly added in the liquor potassic permanganate of stirring, and stirring is until mixing
Uniformly, when homogeneous solution being poured into 140 DEG C 12 small in autoclave, it is cooled to room temperature, it is each clear with ethanol and deionized water respectively
Wash 3 times, when then 70 DEG C of dryings 24 are small, obtain manganese dioxide precursor；
(2) mass ratio weighed is respectively 1: 1: 0.5 above-mentioned manganese dioxide precursor, cobalt nitrate and carbon nanotubes dissolving
In the 1.3mol/L ammonium hydroxide that the ratio of cobalt oxide and ammonium hydroxide is 0.2g: 15ml, when ultrasonic disperse 1 is small, 150 DEG C are transferred in autoclave
When hydro-thermal reaction 5 is small, it is cooled to room temperature, is cleaned 5 times with deionized water, when then 60 DEG C of dryings 8 are small；
(3) by when calcining 1 is small in above-mentioned the product respectively Muffle furnace at 200,300,400,500 DEG C.Drop to 60 DEG C
Then grind into powder when following, obtains bifunctional catalyst.
The catalyst fines under 5mg different temperatures is weighed respectively to be dissolved in 1ml ethanol and the 5% nafion solution of 8 μ l,
Ultrasound forms homogeneous catalyst slurry in 30 minutes, and it is 100 μ g then to make catalyst loading in drop coating to disc electrode respectively, so
Naturally dry afterwards.With the polarization curve of electrochemical workstation measure catalyst.It is passed through in the potassium hydroxide solution of 0.1mol/L
Oxygen 30 minutes, then will scribble the disc electrode of catalyst as working electrode, full calomel electrode and Pt electrodes is respectively reference electricity
Pole and the polarization curve prepared to electrode, sequentially determining three-way catalyst under different calcining heats.
Experimental result is as shown in Figure 6, the results showed that under different calcining heats, the spike potential that rises of ORR rises catalyst with OER
There is change in spike potential, and at 200-400 DEG C, the spike potential that rises of ORR reaches 1.04V, and OER plays spike potential and reaches 1.45V, and
The effect of catalyst then significantly declines at 500 DEG C.
Embodiment 7
The catalyst fines of the embodiment 1 of 5mg is dissolved in 1ml ethanol and 5% Nafion solution of 8 μ l, ultrasound 30
Minute forms homogeneous catalyst slurry, is then applied to (carrying capacity 3.3mg/cm on the carbon paper of hydrophobic treatment2), 60 DEG C are dry
Air electrode is prepared within dry 30 minutes, while using the zinc paper tinsel identical with carbon paper area as negative electrode, by air electrode, zinc
Paper tinsel is put into reaction cell groove in the potassium hydroxide solution of 6mol/L and forms complete zinc and air cell, utilizes activation of fuel cell system
Tested using gradual change current-mode：
Normal temperature and pressure, test power generation curve and polarization curve are as shown in Figure 7, it can be seen that monocell open-circuit voltage is reachable
1399mV, maximum power generation density reach 313.2mWcm-2.When voltage is 1V, electric current reaches 223.9mA, generated output
Density then reaches 223.1mWcm-2
Embodiment 8
The catalyst fines of the embodiment 1 of 5mg is dissolved in 1ml ethanol and 5% Nafion solution of 8 μ l, ultrasound 30
Minute forms homogeneous catalyst slurry, is then applied to (carrying capacity 0.5mg/cm on the carbon paper of hydrophobic treatment2), 60 DEG C are dry
Air electrode is prepared within dry 30 minutes, while using the zinc paper tinsel identical with carbon paper area as negative electrode, by air electrode, zinc
Paper tinsel is put into reaction cell groove in the potassium hydroxide solution of 6mol/L and is assembled into complete zinc and air cell, after overactivation, by zinc
Empty battery is tested using blue electric system, and test condition is the current charging and discharging of 5mA each 4 minutes, after 55 circles, by charge and discharge
The electric current of electricity is changed to 50mA, and the time was circulated for 10 minutes one.
Test result is as shown in figure 8, condition of the charging voltage in each 15 minutes of the current charging and discharging of 5mA of zinc and air cell
Lower charging voltage maintains 2.05V or so, and discharge voltage maintains 1.25V or so, and does not change within 55 circles；Change big
Charging voltage is still maintained at 2.1V or so after current charging and discharging, and discharge voltage maintains 1.05V or so, and multiple follow of charging
Have almost no change after ring, illustrate that the charge-discharge performance of battery is sufficiently stable, there is practical potential very well.
Embodiment 9
The catalyst fines of the embodiment 1 of 5mg is dissolved in 1ml ethanol and 5% Nafion solution of 8 μ l, ultrasound 30
Minute forms homogeneous catalyst slurry, is then applied to (carrying capacity 0.5mg/cm on the carbon paper of hydrophobic treatment2), 60 DEG C are dry
Air electrode is prepared within dry 30 minutes, while using the zinc paper tinsel identical with carbon paper area as negative electrode, by air electrode, zinc
Paper tinsel is put into reaction cell groove in the potassium hydroxide solution of 6mol/L and is assembled into complete zinc and air cell, after overactivation, by zinc
Empty battery is tested using blue electric system, and test condition is 20mA/cm2Each 10 minutes of current charging and discharging.
Test result as shown in figure 9, the charging voltage of zinc and air cell in 20mA/cm2Current charging and discharging in each 10 minutes
Under conditions of charging voltage in 2.52V or so, discharge voltage in 1.01V or so, and circulate 200 it is small when after it is still very steady
It is fixed.
Embodiment 10
The catalyst fines of the embodiment 1 of 5mg is dissolved in 1ml ethanol and 5% Nafion solution of 8 μ l, ultrasound 30
Minute forms homogeneous catalyst slurry, is then applied to (carrying capacity 0.5mg/cm on the carbon paper of hydrophobic treatment2), 60 DEG C are dry
Air electrode is prepared within dry 30 minutes, while using the zinc paper tinsel identical with carbon paper area as negative electrode, by air electrode, zinc
Paper tinsel is put into reaction cell groove in the potassium hydroxide solution of 6mol/L and forms complete zinc and air cell, utilizes activation of fuel cell system
System, after a gradual change current electric power generation, can make generation model (small fan) continuous work up to 90 it is small when more than.Together
When, by three cells in series get up to be formed battery pack can make operating voltage 3V small racing car contact work 8 it is small when more than.
Claims (6)
1. a kind of preparation method of bifunctional catalyst, it is characterised in that the bifunctional catalyst includes carbon nanotubes, oxygen
Change cobalt and manganese dioxide；Its preparation method includes：The first step：The mass ratio for configuring potassium permanganate and water is 1 ~ 2:100 Gao Meng
Sour potassium solution, is at room temperature 101 ~ 102g by liquor potassic permanganate and concentrated hydrochloric acid ratio:The concentrated hydrochloric acid of 4ml adds the permanganic acid of stirring
In potassium solution, continue stirring until being uniformly mixed, the mixed liquor of gained is transferred to 135-145 in autoclaveoHydro-thermal method is anti-under C
When answering 10-14 small, it is cooled to room temperature, is cleaned 3-5 times with ethanol and deionized water respectively, then 60-80oC dryings 12-24 is small
When, obtain manganese dioxide presoma；Second step：It is 0.5-1 to weigh mass ratio respectively:1:The manganese dioxide forerunner of 0.25-0.5
Body, cobalt nitrate and carbon nanotubes, are dissolved in the ammonium hydroxide of 1-1.5mol/L, when ultrasonic disperse 0.5-1.5 is small, are then transferred to
140-160 in autoclaveoWhen C reactions 3~6 are small, it is cooled to room temperature, 50-70 after being cleaned 3-5 times with deionized wateroC dries 6-10
Hour；After drying, in 350-450oWhen calcining 0.5-1.5 is small in Muffle furnace under C, 60 are dropped tooPulverize during below C, up to double
Function catalyst.
2. the preparation method of bifunctional catalyst as claimed in claim 1, it is characterised in that the manganese dioxide is pipe
Shape, length is at 1-3 μm, and internal diameter is in 7-10nm；Cobalt oxide is the nano particle of diameter 10-20nm；Carbon nanotubes, cobalt oxide and two
Manganese oxide is combined with each other.
3. the preparation method of bifunctional catalyst as claimed in claim 1, it is characterised in that the dioxy in the second step
The mass ratio for changing manganese presoma, cobalt nitrate and carbon nanotubes is 0.5:1:0.25.
4. the preparation method of bifunctional catalyst as claimed in claim 1, it is characterised in that the ultrasonic disperse time is
1.5 it is small when.
5. the bifunctional catalyst prepared by the preparation method of the bifunctional catalyst any one of claim 1-4 is being made
Application in the air electrode of standby metal-air battery.
6. application as claimed in claim 5, it is characterised in that the metal-air battery is zinc-sky battery, aluminium-sky electricity
Pond or magnesium-sky battery.
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| CN105289643B (en) * | 2015-11-11 | 2018-01-02 | 东华大学 | A kind of mangaic acid nickel carbon nano-tube composite catalyst and its preparation and application |
| CN105289617A (en) * | 2015-11-11 | 2016-02-03 | 东华大学 | Nickel cobalt oxide/carbon nanotube composite catalyst, preparation and application thereof |
| CN105609792A (en) * | 2015-12-18 | 2016-05-25 | 东华大学 | La-Ca-Mn/carbon nanotube dual-functional composite catalyst and preparation and application thereof |
| CN105609791A (en) * | 2015-12-18 | 2016-05-25 | 东华大学 | La-Co-Mn and carbon nanotube dual-functional composite catalyst and preparation and application thereof |
| CN106602087A (en) * | 2016-11-25 | 2017-04-26 | 东华大学 | Nickel-cobalt-manganese-carbon nanotube difunctional composite catalyst and preparation method and application thereof |
| CN106558706A (en) * | 2016-11-25 | 2017-04-05 | 东华大学 | Carbon carries FeO/MnO2Spinelle bifunctional catalyst and its preparation method and application |
| CN106910903B (en) * | 2017-02-23 | 2019-08-02 | 新乡医学院 | A kind of preparation method of nickel cobalt carbon nanotube aerogel zinc and air cell catalyst |
| CN108470919A (en) * | 2018-03-28 | 2018-08-31 | 合肥国轩高科动力能源有限公司 | Composite metal oxide catalyst for aluminum-air battery and preparation method and application thereof |
| CN110219011A (en) * | 2019-07-09 | 2019-09-10 | 广州市健崎电子科技有限公司 | A kind of oxygen conduction liquid processed |
| CN110947407A (en) * | 2019-11-20 | 2020-04-03 | 东莞理工学院 | Iron nitride carbon nanotube composite material and preparation method and application thereof |
| CN111082077B (en) * | 2019-12-30 | 2021-03-30 | 华南理工大学 | High-dispersion heterogeneous interface composite nanowire and preparation method and application thereof |
| CN112382769B (en) * | 2020-11-04 | 2021-10-15 | 江苏科技大学 | High-performance metal-air battery anode catalyst and preparation method thereof |
| CN114068963B (en) * | 2021-11-10 | 2022-07-22 | 西安航空职业技术学院 | Preparation method and application of transition metal and compound thereof anchored nitrogen-doped carbon catalyst |
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