CN106558706A - Carbon carries FeO/MnO2Spinelle bifunctional catalyst and its preparation method and application - Google Patents
Carbon carries FeO/MnO2Spinelle bifunctional catalyst and its preparation method and application Download PDFInfo
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- CN106558706A CN106558706A CN201611059011.2A CN201611059011A CN106558706A CN 106558706 A CN106558706 A CN 106558706A CN 201611059011 A CN201611059011 A CN 201611059011A CN 106558706 A CN106558706 A CN 106558706A
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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
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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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
- 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
Abstract
The invention discloses a kind of carbon carries FeO/MnO2Spinelle bifunctional catalyst and its preparation method and application.The catalyst includes CNT and FeO/MnO2Spinelle.Preparation method is：Potassium permanganate is incorporated in water, concentrated hydrochloric acid is added, is carried out hydro-thermal reaction 12h, obtain manganese dioxide presoma；Manganese dioxide presoma, ferric nitrate and CNT are dissolved in ammoniacal liquor, ultrasonic disperse, carry out hydro-thermal reaction, be cooled to room temperature, then cleaning, dry, calcining, obtain final product bifunctional catalyst.The present invention had both had efficient hydrogen reduction performance in atmosphere, while and there is efficiently analysis oxygen performance, particularly applied metal air cell not only there is excellent power generation performance to have excellent charging and discharging characteristic and cyclical stability simultaneously.
Description
Technical field
The invention belongs to dual-function catalyst technology field, and in particular to a kind of carbon carries FeO/MnO2Spinelle is difunctional to urge
Agent and its preparation method and application.
Background technology
In recent years, with fossil energy day and night consume and environmental pollution continuous aggravation, the scientific research machine of countries in the world
Structure and the continuable energy conversion device of the competing relative clean of business unit develop research, wherein using electrochemical reaction being
The energy stores of principle are greatly paid close attention to by people with converting apparatus, particularly the large power-consuming equipment such as new-energy automobile and
The fields such as fixed energy station [Chem.S DEG C of .Rev., 2014,43,5257-5259].Particularly secondary zinc-the air of rechargeable type
Battery is due to low cost, the safety theoretical specific energy that light, environmental friendliness is pollution-free, security performance is excellent and high and work(
Rate density etc. becomes the focus of world today's research.In addition；Either in terms of economic benefit and environmental protection, zinc-air electricity
Pond has been acknowledged as one of 21st century maximally efficient and reliable new energy technology [Nanoscale 2013,5,4657-
4661].In general, the theoretical energy density of zinc-air battery is 3-4 times of traditional lithium ion battery or so, therefore can
To meet demand for development [the Journal of Power of the high power electric vehicles such as wireless telecommunications system and electric automobile
Sources, 2014,249,13-20].But, as oxygen reduction reaction (ORR) and the slow dynamics of oxygen evolution reaction (OER) are entered
Journey limits the efficiency of metal-air battery, therefore bifunctional catalyst of the exploitation with high activity and stability is just particularly compeled
Cut.MnO2Although extensively applying in zinc-air battery, a zinc and air cell is still mainly used in, while its property
Also can be badly in need of improving [J.Am.Chem.S DEG C., 2010,132,13612-13614].In addition current cobalt type oxide quilt
It is widely studied, such as Co3O4[J.Mater.Chem.A 2014,2,3794-3800] and CoMn2O4[A.Chem.S DEG C of .2014,6,
16545-16555], the oxide and NiCo of cobalt acid nickel and nickel2O4The research such as/Graphene has been reported that, although its oxygen separates out anti-
Answer speed to increase, but its stability and self reason (such as Co toxicity and reserves etc.) limit its further
Exhibition, moreover catalyst directly applies to metallic zinc-sky battery also rare [J.Mater.Chem.2013, Isosorbide-5-Nitrae 754-
4762].Additionally, above-mentioned catalyst has preparation process complexity, it is unfavorable for prepared by industrially scalable.And environmental friendliness and reserves are rich
Bifunctional catalyst study hotspot of the rich iron rule into exploitation high activity and stability, at present, Dai etc. be prepared for cobalt oxide/
CNT and Ni-Fe-layered double-hydroxide elctro-catalyst are used for rechargeable type zinc-air battery negative electrode, but still
Under the conditions of resting on pure oxygen, and battery model making complexity [Nature Communications, 2013,249,1805-
1806].Bao etc. [Nano Energy, 2015,13,387-396] reports Fe/N-C catalyst and applies in zinc and air cell, iron
The activity of catalyst that improves of addition, but its efficiency for charge-discharge and stability are required for greatly raising.It is known that
CNT (CNT) is big with excellent electric conductivity and extra specific surface area, while with high electrochemical stability, often
It is combined with catalyst.But at present still nobody carries out relevant highly active iron, highly active manganese dioxide with
And three kinds of compounds of the CNT of high connductivity combine the exploration of aspect.Therefore by certain chemical method by this several element
Compound is prepared with extremely important realistic meaning.
The content of the invention
The technical problem to be solved is that existing catalyst preparation process is complicated, is not suitable for industrialized asking
Topic.
In order to solve the above problems, the invention provides a kind of carbon carries FeO/MnO2Spinelle bifunctional catalyst, which is special
Levy and be, including CNT and FeO/MnO2Spinelle.
Preferably, the FeO/MnO2Spinelle is the FeO nano particles of a diameter of 20-150nm, and its uniform load is in carbon
On nanotube and manganese dioxide.
Present invention also offers above-mentioned carbon carries FeO/MnO2The preparation method of spinelle bifunctional catalyst, its feature exist
In comprising the following steps：
Step 1)：1.4g potassium permanganate is incorporated in the water of 100g, 4mL concentrated hydrochloric acids after being completely dissolved, are rapidly added, is continued
Stir to being well mixed, then hydro-thermal reaction 12h under the conditions of 140-150 DEG C, be cooled to room temperature, clean, be dried, obtain dioxy
Change manganese presoma；
Step 2)：0.125g manganese dioxide presomas, 0.25g ferric nitrates and 0.05g CNTs are dissolved in into 15mL ammonia
In water, ultrasonic disperse, then hydro-thermal reaction 6h under the conditions of 160 DEG C, is cooled to room temperature, and then cleaning, dry, calcining, obtain final product
Bifunctional catalyst.
Preferably, the step 1) in liquor potassic permanganate potassium permanganate and the mass ratio of water be 1.4: 100.
Preferably, the step 1) in cleaning concretely comprise the following steps：5 times are cleaned with ethanol, deionized water successively；Dry
Concretely comprise the following steps：24h is dried at 70 DEG C.
Preferably, the step 2) in ammoniacal liquor concentration be 1-1.5mol/L.
Preferably, the step 2) in ultrasonic disperse time be 1h；That what is cleaned concretely comprises the following steps：Deionized water is cleaned
5 times；Baking temperature is 60 DEG C；Drying time is 10h；Calcining heat is 300 DEG C；Calcination time is 1-5h.
Present invention also offers above-mentioned carbon carries FeO/MnO2Spinelle bifunctional catalyst is preparing metal-air battery
Application in air electrode.
Preferably, concretely comprise the following steps：By bifunctional catalyst be dissolved in ethanol and 5% Nafion solution in, ultrasonic 20-
40min forms homogeneous catalyst slurry, then drop coating in glass carbon disk electrode or carbon paper, the catalyst in glass carbon disk electrode
Carrying capacity is 100g, and the catalyst loading on carbon paper is 1mg, is dried naturally；The wherein ratio of bifunctional catalyst, ethanol, Nafion
Example is 3-5mg: 1mL: 6-8 μ L.
Preferably, the metal-air battery is zinc-sky battery, aluminium-sky battery or magnesium-sky battery.
The catalyst that the present invention is provided especially shows good electrochemistry under 300 DEG C of calcinings preparation condition of 3 hours
Performance, the spike potential that rises of ORR is 0.92V, and it is 1.48V that OER plays spike potential, is 350mW/cm under power density normal temperature2, energy is close
Degree can reach 780Ah/g while having good stable charge/discharge；The method for preparing catalyst is simple, with low cost, is adapted to
In industrialized production.
Not only environmental friendliness, raw material are easy to get the present invention, low cost, and reaction condition is gentle, the reaction time is short, and only a step is
Can synthesize, have the advantages that process is simple, economical and practical, controllability are strong, it is easy to large-scale production, be can be used in zinc-sky,
The good air electrode catalyst in the metal-air battery such as aluminium-sky and magnesium-sky field.
The bifunctional catalyst with premium properties of the present invention is applied to prepare the air electrode of metal-air battery
On, can be using power supplys such as Medical Devices (such as audiphone), wireless telecommunications system, escape ways and as fixed energy station
Energy storage device.
Compared with prior art, the beneficial effects of the present invention is：
(1) bifunctional catalyst of the invention had both shown excellent chemical property, while with excellent discharge and recharge
Performance and stability, the catalyst for especially preparing at 300 DEG C, ORR's play spike potential in 0.92V, and OER plays spike potential and exists
1.48V；Under air conditionses, catalyst loading is 2mg/cm2Monocell by the way of gradual change current electric power generation power density
350mW/cm can be reached2；
(2) not only environmental friendliness, raw material are easy to get the present invention, low cost, and reaction condition is gentle, the reaction time is short, have
Process is simple, the advantages of economical and practical, controllability is strong, it is easy to large-scale production, be can be used in zinc-sky, aluminium-sky and
The good air electrode catalyst in the metal-air battery such as magnesium-sky field；
(3), after catalyst of the invention makes air electrode, can be enclosed with stable circulation 1390 in small current discharge and recharge,
Also there is excellent stability in high current charge-discharge, hence it is evident that better than Pt/C, can be directly used for metal-air battery, substantially reduce
The cost of manufacture of metal-air battery.
Description of the drawings
Fig. 1 is FeO/MnO2- CNTs, MnO2, ORR the and OER polarization curve comparison diagrams of CNTs and 20%Pt/C；
Fig. 2 is FeO/MnO2- CNTs, FeO/MnO2- CNTs-3 and FeO/MnO2The ORR and OER polarization of-CNTs-5 is bent
Line comparison diagram；
Fig. 3 is FeO/MnO2ORR and OER poles after 1000 circle of ORR and OER first times polarization curve and circulation of-CNTs-3
Change curve comparison figure；
Fig. 4 is 20%Pt/C, FeO/MnO2- CNTs, FeO/MnO2- CNTs-3 and FeO/MnO2Four kinds of catalysis of-CNTs-5
It is 2mg/cm that agent is prepared into air electrode respectively and constitutes carrying capacity after monocell with zine plate2Generating curve map；
Fig. 5 is 20%Pt/C, FeO/MnO2- CNTs, FeO/MnO2- CNTs-3 and FeO/MnO2Four kinds of catalysis of-CNTs-5
Agent is prepared into air electrode respectively and is constituted after monocell in 20mA/cm with zine plate2Under current density, electric discharge is schemed for a long time；
Fig. 6 is 20%Pt/C, FeO/MnO2- CNTs, FeO/MnO2- CNTs-3 and FeO/MnO2Four kinds of catalysis of-CNTs-5
Agent is prepared into air electrode respectively and is constituted after monocell in 20mA/cm with zine plate2Discharge under current density specific energy figure for a long time；
Fig. 7 is 20%Pt/C, FeO/MnO2- CNTs, FeO/MnO2- CNTs-3 and FeO/MnO2Four kinds of catalysis of-CNTs-5
Agent is prepared into air electrode respectively and is constituted after monocell in 0～65mA/cm with zine plate2Voltage change figure under current density；
Fig. 8 is FeO/MnO2- CNTs-3 catalyst preparations are constituted after monocell in 10mA/cm into air electrode with zine plate2Electricity
Charge and discharge electrograph under current density；
Fig. 9 is the transmission electron microscope picture of the bifunctional catalyst obtained by embodiment 1.
Specific embodiment
To become apparent the present invention, hereby with preferred embodiment, and accompanying drawing is coordinated to be described in detail below.
The CNT adopted by embodiment 1-6 is bought from Chengdu Ai Fa Nanosolutions GmbH；The length of CNT
Spend for 15nm, a diameter of 30-50nm；Using ferric nitrate buy from Chemical Reagent Co., Ltd., Sinopharm Group, analyze pure, molecule
Amount about 404.08g；Using potassium permanganate buy from Chemical Reagent Co., Ltd., Sinopharm Group, analyze it is pure, molecular weight is about
158.03g。
Embodiment 1
A kind of bifunctional catalyst, including CNT and FeO/MnO2FeO/MnO described in spinelle2Spinelle is diameter
In the FeO nano particles of 20-150nm, and uniform load is on CNT and manganese dioxide.
Preparation method is：
The first step：The mass ratio of configuration potassium permanganate and water is 1.4g: 100 liquor potassic permanganate, by Gao Meng under room temperature
In the liquor potassic permanganate of sour potassium solution and concentrated hydrochloric acid ratio for 101.4g: 4ml concentrated hydrochloric acid addition stirring, continue stirring until mixing
Close uniform, the mixed liquor of gained is transferred in autoclave hydro-thermal method at 140 DEG C and is reacted 12 hours, be cooled to room temperature, use respectively
Ethanol and deionized water clean 5 times, and then 70 DEG C of dryings 24 hours, obtain manganese dioxide presoma；
Second step：Quality is weighed respectively for the above-mentioned manganese dioxide presomas of 0.125g, 0.25g ferric nitrates and 0.05g carbon
Nanotube, is dissolved in 15mL concentrated ammonia liquors, ultrasonic disperse 1 hour, is then transferred in autoclave 160 DEG C and reacts 6 hours, cooling
To room temperature, after deionized water cleans 5 times；60 DEG C of dryings 10 hours；After drying, 3 hours are calcined in Muffle furnace at 300 DEG C i.e.
Obtain bifunctional catalyst.As shown in figure 9, FeO/MnO of the present invention2The size of-CNTs, FeO is left in 20-150nm nanometers
The right side, uniform load is on manganese dioxide and CNT.
By the catalyst fines of 5mg be dissolved in 1ml ethanol and 5% Nafion solution in, ultrasound is formed and homogeneous is urged for 30 minutes
Agent slurries, then in glass carbon disk electrode, catalyst loading is 100g to drop coating, is dried naturally.
The cyclic voltammetry curve of catalyst is determined with electrochemical workstation.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, satisfy calomel electrode and Pt electrodes be respectively reference electrode and
To electrode, sequentially determining FeO/MnO2- CNTs, MnO2, ORR the and OER polarization curves of CNTs and 20%Pt/C.
Experimental result is as shown in figure 1, FeO/MnO2Substantially, ORR's plays spike potential to the bifunctional performance of-CNTs catalyst
In 0.92V, OER plays spike potential in 1.48V.In 0.2V, FeO/MnO2- CNTs, MnO2, CNTs and 20%Pt/C electric currents are close
Degree is respectively 5mA/cm2, 3.1mA/cm2, 2.1mA/cm2And 3.2mA/cm2.The FeO/MnO on OER2- CNTs performances are substantially excellent
In 20%Pt/C catalyst and other catalyst.
Embodiment 2
A kind of bifunctional catalyst, including CNT and FeO/MnO2FeO/MnO described in spinelle2Spinelle is diameter
In the FeO nano particles of 20-150nm, and uniform load is on CNT and manganese dioxide.
The preparation of complexing agent is catalyzed under different calcination times：
The first step：The mass ratio of configuration potassium permanganate and water is 1.4g: 100 liquor potassic permanganate, by Gao Meng under room temperature
In the liquor potassic permanganate of sour potassium solution and concentrated hydrochloric acid ratio for 101.4g: 4ml concentrated hydrochloric acid addition stirring, continue stirring until mixing
Close uniform, the mixed liquor of gained is transferred in autoclave hydro-thermal method at 140 DEG C and is reacted 12 hours, be cooled to room temperature, use respectively
Ethanol and deionized water clean 5 times, and then 70 DEG C of dryings 24 hours, obtain manganese dioxide presoma；
Second step：Quality is weighed respectively for the above-mentioned manganese dioxide presomas of 0.125g, 0.25g ferric nitrates and 0.05g carbon
Nanotube, is dissolved in 15mL concentrated ammonia liquors, ultrasonic disperse 1 hour, is then transferred in autoclave 160 DEG C and reacts 6 hours, cooling
To room temperature, after deionized water cleans 5 times；60 DEG C of dryings 10 hours；
3rd step：After drying；To calcine 1,3 and 5 hours in above-mentioned product Muffle furnace respectively at 300 DEG C, with
After grind into powder when being cooled to less than 60 DEG C, obtain bifunctional catalyst, and be respectively designated as according to the time of heat treatment
FeO/MnO2- CNTs, FeO/MnO2- CNTs-3 and FeO/MnO2-CNTs-5。
Respectively by the FeO/MnO of 5mg2- CNTs, FeO/MnO2- CNTs-3 and FeO/MnO2- CNTs-5 catalyst fineses
Be dissolved in 1ml ethanol and 5% Nafion solution in, ultrasound form homogeneous catalyst slurry within 30 minutes, then drop coating is to disc electrode
On, catalyst loading is 100g, is dried naturally.The cyclic voltammetry curve of catalyst is determined with electrochemical workstation.In 0.1mol/
The potassium hydroxide solution of L is passed through oxygen 30 minutes, then the disc electrode for scribbling catalyst is made working electrode, and satisfy calomel electrode and Pt
Electrode is respectively reference electrode and to electrode, sequentially determining FeO/MnO2- CNTs, FeO/MnO2- CNTs-3 and FeO/MnO2-
ORR the and OER polarization curves of CNTs-5.In order to further characterize the stability of catalyst, drop there is into FeO/MnO2- CNTs-3 disks
Electrode is circulated voltammetry scanning 1000 under 0.2-1.7V voltages and encloses, and then retests ORR and OER polarization curves.
As a result experimental result as shown in Fig. 2 show catalyst under different calcining heats, the spike potential that rises of ORR is risen with OER
Spike potential occurs in that change, and wherein heat treatment time is that 3 hours catalyst effects are optimal.Moreover；Experimental result such as Fig. 3 institutes
Show that the stability of catalyst is very excellent, particularly OER reactions almost do not decay.
Embodiment 3
Respectively by the FeO/MnO of the embodiment 2 of 5mg2- CNTs, FeO/MnO2- CNTs-3 and FeO/MnO2- CNTs-5 is urged
Agent powder be dissolved in 1ml ethanol and 81 5% Nafion solution in, ultrasound form homogeneous catalyst slurry within 40 minutes, then
Be sprayed on the carbon paper of Jing hydrophobic treatments, catalyst loading is controlled for 2mg/cm2, 60 DEG C of dryings prepare air electricity for 40 minutes
Pole, while air electrode, zinc paper tinsel are put into the potassium hydroxide of 6mol/L using with carbon paper area identical zinc paper tinsel as negative electrode
In solution, reaction cell groove constitutes complete zinc and air cell, is tested using gradual change current-mode using activation of fuel cell system：
Normal temperature and pressure, tests generating curve and polarization curve is as shown in Figure 4, it can be seen that FeO/MnO2- CNTs-3 property
Can be the most excellent, its open-circuit voltage reaches 350mW/cm up to 1455mV, maximum power generation density2.When voltage is 1V, electricity
Current density is 275.1mA/cm2, corresponding generated output density reaches 275.1mW/cm2.These results can meet high-power electricity consumption
The requirement of equipment.The moreover FeO/MnO of poor-performing2- CNTs catalyst is also superior to Pt/C catalyst.
Embodiment 4
Respectively by the FeO/MnO of the embodiment 2 of 5mg2- CNTs, FeO/MnO2- CNTs-3 and FeO/MnO2- CNTs-5 is urged
Agent powder be dissolved in 1ml ethanol and 81 5% Nafion solution in, ultrasound form homogeneous catalyst slurry within 40 minutes, then
Be sprayed on the carbon paper of Jing hydrophobic treatments, catalyst loading is controlled for 2mg/cm2, 60 DEG C of dryings prepare air electricity for 40 minutes
Pole, at the same using with carbon paper area identical zinc paper tinsel as negative electrode, by the hydrogen of the 6mol/L of air electrode, zinc paper tinsel and 9mL
Potassium oxide solution is put in homemade zinc-air battery groove, after activation, and zinc-air battery is entered using blue electric system
Row test, test condition is 20mA/cm2Discharged under current density for a long time.
Test result is as shown in figure 5, with FeO/MnO2- CNTs-3 catalyst for air electrode zinc and air cell performance most
Good, its discharge voltage maintains 1.31V or so, and voltage can maintain 1V and be also within 34 hours.This just illustrates electricity
The charge-discharge performance in pond is sufficiently stable, with fine practical potential.When zine plate runs out of, the battery longevity can be improved by changing zine plate
Life.Through calculating, its actual energy density can reach 600mAh/g.With FeO/MnO2- CNTs and FeO/MnO2-CNTs-5
Catalyst then can be maintained 10 and 22 hours respectively for the zinc and air cell of air electrode.Simultaneously as shown in fig. 6, with FeO/MnO2-
CNTs-3 catalyst is up to 780Ah/g for the zinc and air cell specific energy density of air electrode.
Embodiment 5
Respectively by the FeO/MnO of the embodiment 2 of 5mg2- CNTs, FeO/MnO2- CNTs-3 and FeO/MnO2- CNTs-5 is urged
Agent powder be dissolved in 1ml ethanol and 5% Nafion solution in, ultrasound form homogeneous catalyst slurry within 30 minutes, then spray
On the carbon paper of Jing hydrophobic treatments, catalyst loading is controlled for 2mg/cm2, 60 DEG C of dryings prepare air electrode in 40 minutes,
Simultaneously using with carbon paper area identical zinc paper tinsel as negative electrode, respectively by the hydrogen of the 6mol/L of air electrode, zinc paper tinsel and 9mL
Potassium oxide solution is put in homemade zinc-air battery groove, after activation, and zinc-air battery is entered using blue electric system
Row test, test condition is 5～65mA/cm2Current density, charge and discharge cycles time carried out discharge and recharge for 10 minutes.
Test result is as shown in fig. 7, with FeO/MnO2- CNTs-3 catalyst is relative for the zinc and air cell performance of air electrode
For still preferably, within charging/discharging voltage difference maintains 1.3V, hence it is evident that better than Pt/C catalyst；Illustrate that catalyst has very
Excellent bi-functional.
Embodiment 6
By the FeO/MnO of the embodiment 2 of 5mg2- CNTs-3 catalyst fineses are dissolved in 1ml ethanol and 5% Nafion solution
In, ultrasound forms homogeneous catalyst slurry in 30 minutes, is then sprayed on the carbon paper of Jing hydrophobic treatments, and controlling catalyst loading is
2mg/cm2, 60 DEG C of dryings prepare air electrode in 40 minutes, at the same using with carbon paper area identical zinc paper tinsel as negative electricity
Pole, is put into the potassium hydroxide solution of the 6mol/L of air electrode, zinc paper tinsel and 9mL in homemade zinc-air battery groove respectively,
After activation, zinc and air cell is tested using blue electric system, test condition is 10mA/cm2Current density, fully electricity
Circulation time carried out discharge and recharge for 10 minutes.
Test result is as shown in figure 8, the charging voltage of zinc-sky battery is in 10mA/cm2Current density is discharged, discharge voltage
1.22V or so is maintained, in 2.23V or so, voltage difference has almost no change charging voltage Jing after 1390 charge and discharge cycles, says
The charge-discharge performance of bright battery is sufficiently stable, and future is can be applicable on the low-power equipments such as Medical Devices.
Claims (10)
1. a kind of carbon carries FeO/MnO2Spinelle bifunctional catalyst, it is characterised in that including CNT and FeO/MnO2It is sharp brilliant
Stone.
2. carbon as claimed in claim 1 carries FeO/MnO2Spinelle bifunctional catalyst, it is characterised in that the FeO/MnO2
Spinelle is the FeO nano particles of a diameter of 20-150nm, and its uniform load is on CNT and manganese dioxide.
3. the carbon described in a kind of claim 1 or 2 carries FeO/MnO2The preparation method of spinelle bifunctional catalyst, its feature exist
In comprising the following steps：
Step 1)：1.4g potassium permanganate is incorporated in the water of 100g, 4mL concentrated hydrochloric acids after being completely dissolved, are rapidly added, continues stirring
To being well mixed, then hydro-thermal reaction 12h under the conditions of 140-150 DEG C, is cooled to room temperature, cleans, is dried, obtains manganese dioxide
Presoma；
Step 2)：0.125g manganese dioxide presomas, 0.25g ferric nitrates and 0.05g CNTs are dissolved in 15mL ammoniacal liquor,
Ultrasonic disperse, then hydro-thermal reaction 6h under the conditions of 160 DEG C, is cooled to room temperature, and then cleaning, dry, calcining, obtain final product difunctional
Catalyst.
4. carbon as claimed in claim 3 carries FeO/MnO2The preparation method of spinelle bifunctional catalyst, it is characterised in that institute
State step 1) in liquor potassic permanganate potassium permanganate and the mass ratio of water be 1.4: 100.
5. carbon as claimed in claim 3 carries FeO/MnO2The preparation method of spinelle bifunctional catalyst, it is characterised in that institute
State step 1) in cleaning concretely comprise the following steps：5 times are cleaned with ethanol, deionized water successively；Dry concretely comprises the following steps：At 70 DEG C
It is dried 24h.
6. carbon as claimed in claim 3 carries FeO/MnO2The preparation method of spinelle bifunctional catalyst, it is characterised in that institute
State step 2) in ammoniacal liquor concentration be 1-1.5mol/L.
7. carbon as claimed in claim 3 carries FeO/MnO2The preparation method of spinelle bifunctional catalyst, it is characterised in that institute
State step 2) in ultrasonic disperse time be 1h；That what is cleaned concretely comprises the following steps：Deionized water is cleaned 5 times；Baking temperature is 60
℃；Drying time is 10h；Calcining heat is 300 DEG C；Calcination time is 1-5h.
8. the carbon described in a kind of claim 1 or 2 carries FeO/MnO2Spinelle bifunctional catalyst is preparing metal-air battery
Air electrode in application.
9. carbon as claimed in claim 8 carries FeO/MnO2The application of spinelle bifunctional catalyst, it is characterised in that concrete to walk
Suddenly it is：By bifunctional catalyst be dissolved in ethanol and 5% Nafion solution in, ultrasonic 20-40min forms homogeneous catalyst slurry
Liquid, then drop coating in glass carbon disk electrode or carbon paper, the catalyst loading in glass carbon disk electrode be 100g, urging on carbon paper
Agent carrying capacity is 1mg, is dried naturally；Wherein bifunctional catalyst, ethanol, the ratio of Nafion are 3-5mg：1mL：6-8μL.
10. carbon as claimed in claim 8 or 9 carries FeO/MnO2The application of spinelle bifunctional catalyst, it is characterised in that institute
Metal-air battery is stated for zinc-sky battery, aluminium-sky battery or magnesium-sky battery.
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| CN113066993A (en) * | 2021-03-16 | 2021-07-02 | 重庆大学 | From NH3·H2Preparation of carbon-supported nano MnO by O medium2Oxygen reduction cathode and MFC |
| CN113233511A (en) * | 2021-04-29 | 2021-08-10 | 西安交通大学 | FeMnO2Nanotube and preparation method and application thereof |
| CN113764678A (en) * | 2020-06-01 | 2021-12-07 | 南京航空航天大学 | Catalyst for flexible metal-air battery, preparation method of catalyst and metal-air battery |
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| CN113066993B (en) * | 2021-03-16 | 2022-10-11 | 重庆大学 | From NH 3 ·H 2 Preparation of carbon-supported nano MnO by O medium 2 Oxygen reduction cathode and MFC |
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| CN114759194A (en) * | 2022-03-16 | 2022-07-15 | 东华大学 | Manganese-based ternary integrated dual-functional oxygen electrode and preparation method and application thereof |
| CN114759194B (en) * | 2022-03-16 | 2024-01-30 | 东华大学 | Manganese-based ternary integrated difunctional oxygen electrode and preparation method and application thereof |
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