CN105977503A - Lanthanum-modified manganese dioxide and carbon composite catalyst for metal-air battery and preparation method of catalyst - Google Patents
Lanthanum-modified manganese dioxide and carbon composite catalyst for metal-air battery and preparation method of catalyst Download PDFInfo
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- CN105977503A CN105977503A CN201610590992.7A CN201610590992A CN105977503A CN 105977503 A CN105977503 A CN 105977503A CN 201610590992 A CN201610590992 A CN 201610590992A CN 105977503 A CN105977503 A CN 105977503A
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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
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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
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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
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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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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Abstract
The invention provides a lanthanum-modified manganese dioxide and carbon composite catalyst for a metal-air battery. The catalyst comprises a lanthanum-doped manganese dioxide nanosheet layer and carbon material particles, the lanthanum-doped manganese dioxide nanosheet layer and the carbon material particles are evenly mixed, and a composite sphere with the corrugated surface is formed. The invention further provides a preparation method of the lanthanum-modified manganese dioxide and carbon composite catalyst for the metal-air battery. The composite sphere prepared from the raw materials through the technological steps is large in specific surface area and rich in defect, has more active centers and is high in catalytic activity. It is shown through experimental results that the metal-air battery prepared from the lanthanum-modified manganese dioxide and carbon composite catalyst is high in power density which is not lower than 220 mW/cm<2>.
Description
Technical field
The invention belongs to field of batteries, particularly relate to a kind of lanthanum modification titanium dioxide for metal-air battery
Manganese/carbon composite catalytic agent and preparation method thereof.
Background technology
Metal-air battery is the fuel cell that a class is special, is also the representative of new generation of green secondary cell
One of, there is low cost, nontoxic, pollution-free, specific power is high, specific energy advantages of higher, existing abundant
Resource, moreover it is possible to regeneration, and ratio hydrogen fuel cell simple in construction, be have very much development and application before
The new forms of energy of scape.
Metal-air battery is made up of positive pole, negative pole and electrolyte.Wherein, positive pole i.e. air cathode, by
Catalyst, hydrophobic layer and metal conducting layer composition.Air cathode with the oxygen in air as active substance,
In discharge process, oxygen is reduced to hydroxide ion by catalysis on three phase boundary, is shown below:
O2+2H2O+4e-→4OH-
Negative pole i.e. metal anode, is made up of metal, usually the metal or alloy such as magnesium metal, aluminum and zinc,
As a example by zinc, during electric discharge, zinc reacts generation zinc hydroxide in alkaline solution, and discharges electronics,
It is shown below:
2Zn+4OH-→2Zn(OH)2+4e-
Electrolyte generally selects KOH solution, NaOH solution, NaCl aqueous solution or sea water etc..
In the these three ingredient of metal-air battery, air cathode is the core of metal-air battery
Parts, have a direct impact the battery performance of metal-air battery, and air cathode redox reaction is used
Catalyst be typically metal-air battery can one of business-like key factor.
And catalyst that air cathode can use is varied, be typically used for have noble metal and alloy thereof,
Metal-oxide, mixed-metal oxides, transition metal nitride, transition metal macrocycle and novel
Carbon Materials etc., in these catalyst, metal-oxide is cheap with it, catalysis activity is moderate by extensively
General application.Wherein, manganese dioxide because of aboundresources, cheap, synthesis easily, relative nontoxic and electricity
The chemistry features such as window is wider, chemical property is good, and become and use most metal-oxides.But,
Owing to manganese dioxide electrical conductivity is relatively low, redox reaction generally happens is that 2 electron transfers, as catalysis
During agent, catalysis activity is relatively low so that the chemical property of battery is restricted, and and hence, limit it at sky
Pneumoelectric pond is applied.
In order to solve the problems referred to above, prior art occurring in that, rare-earth metal doped compound is to manganese dioxide
Modify, prepare combination electrode, although improve the electrification of metal-air battery to a certain extent
Learn performance, but the power density of the metal-air battery finally given or relatively low, discharge performance is also paid no attention to
Think.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of for metal-air battery
Lanthanum modified manganese dioxide/carbon composite catalytic agent and preparation method thereof, the lanthanum modified manganese dioxide of the employing present invention/
The power density of the metal-air battery that carbon composite catalytic agent prepares is higher.
The invention provides a kind of lanthanum modified manganese dioxide/carbon composite catalytic agent for metal-air battery,
Including manganese dioxide nano-plates layer and the carbon material particles of La doped, the manganese dioxide nano of described La doped
Lamella uniformly mixes with described carbon material particles, forms the composite balls of surface folding.
Preferably, the specific surface area of described composite balls is 100m2/ g～150m2/g。
The invention provides a kind of lanthanum modified manganese dioxide/carbon composite catalytic agent for metal-air battery
Preparation method, comprises the following steps:
A) material is mixed, after reaction, obtain target product precursor；Described material includes potassium permanganate water
Solution, the aminoacid of sulfur-bearing, lanthanum salt and material with carbon element；
B) described target product precursor is carried out roasting, obtain lanthanum modified manganese dioxide/carbon composite catalytic
Agent.
Preferably, the concentration of described potassium permanganate solution is 0.005mol/L～0.5mol/L.
Preferably, the aminoacid of described sulfur-bearing is cysteine or methionine.
Preferably, one or more in Lanthanum (III) nitrate, lanthanum acetate and lanthanum chloride of described lanthanum salt.
Preferably, the potassium permanganate in described potassium permanganate solution, the aminoacid of sulfur-bearing, lanthanum salt and carbon
The mass ratio of material is (5～50): (0.1～1): (1～10): (1～10).
Preferably, step A) in material also include alkaline solution.
Preferably, the temperature of described reaction is 50 DEG C～100 DEG C, and the time of described reaction is 0.5h～10h.
Preferably, the temperature of described roasting is 300 DEG C～500 DEG C, and the time of described roasting is 1h～8h
The invention provides a kind of lanthanum modified manganese dioxide/carbon composite catalytic agent for metal-air battery,
Including manganese dioxide nano-plates layer and the carbon material particles of La doped, the manganese dioxide nano of described La doped
Lamella uniformly mixes with described carbon material particles, forms the composite balls of surface folding.This composite balls compares table
Area is big and defect is enriched, and active center is more, and catalysis activity is higher.By this lanthanum modified manganese dioxide/
The power density of the metal-air battery that carbon composite catalytic agent prepares is higher.
Present invention also offers a kind of lanthanum modified manganese dioxide/carbon composite catalytic agent for metal-air battery
Preparation method, comprise the following steps: A) by material mix, obtain target product precursor after reaction；
Described material includes potassium permanganate solution, the aminoacid of sulfur-bearing, lanthanum salt and material with carbon element；B) by described mesh
Mark product presoma carries out roasting, obtains lanthanum modified manganese dioxide/carbon composite catalytic agent.The present invention is by Gao Meng
Acid aqueous solutions of potassium, the aminoacid of sulfur-bearing, lanthanum salt and material with carbon element mixing, in material mixed process, sulfur-bearing
Aminoacid be attached to around high manganese ion and lanthanum ion, add after material with carbon element, the aminoacid of sulfur-bearing
Generating manganese dioxide with MnO4 generation redox reaction, manganese dioxide adheres to material with carbon element for matrix
On it, the aminoacid of lanthanum ion and sulfur-bearing is attached to around manganese dioxide granule simultaneously, and is formed spherical
Target product precursor.Described target product precursor when carrying out roasting, having in the aminoacid of sulfur-bearing
Machine thing acutely decomposes, and causes target product precursor surface to form fold, ultimately generates target product lanthanum and change
Property manganese dioxide/carbon composite catalyst.Use the surface that raw material disclosed by the invention and processing step prepare
The composite balls of fold, specific surface area is big and defect is enriched, and active center is more, and catalysis activity is higher.Real
Test result to show, this lanthanum modified manganese dioxide/carbon composite catalytic agent the merit of the metal-air battery prepared
Rate density is higher, is all not less than 220mW/cm2。
Accompanying drawing explanation
Fig. 1 is the SEM figure of the target product precursor of the embodiment of the present invention 1 preparation；
Fig. 2 is the SEM figure of the lanthanum modified manganese dioxide/carbon composite catalytic agent of the embodiment of the present invention 1 preparation；
Fig. 3 is the TEM figure of the lanthanum modified manganese dioxide/carbon composite catalytic agent of the embodiment of the present invention 1 preparation；
Fig. 4 is the XRD figure of the lanthanum modified manganese dioxide/carbon composite catalytic agent of the embodiment of the present invention 1 preparation；
Fig. 5 is that the BET of the lanthanum modified manganese dioxide/carbon composite catalytic agent of the embodiment of the present invention 1 preparation compares table
The graph of a relation of the ability of area and Catalyst Adsorption oxygen；
Fig. 6 is the linear scanning of the lanthanum modified manganese dioxide/carbon composite catalytic agent of the embodiment of the present invention 1 preparation
Volt-ampere curve figure；
Fig. 7 is that the lanthanum modified manganese dioxide/carbon composite catalytic agent of the embodiment of the present invention 1 preparation is at different rotating speeds
Under linear sweep voltammetry curve chart；
Fig. 8 is that the lanthanum modified manganese dioxide/carbon composite catalytic agent of the embodiment of the present invention 1 preparation is in oxidoreduction
Electron transfer number in course of reaction；
Fig. 9 is the discharge performance of the lanthanum modified manganese dioxide/carbon composite catalytic agent of the embodiment of the present invention 1 preparation
Test result.
Detailed description of the invention
Below in conjunction with the embodiment of the present invention, technical scheme is clearly and completely described,
Obviously, described embodiment is only a part of embodiment of the present invention rather than whole embodiments.
Based on the embodiment in the present invention, those of ordinary skill in the art are not under making creative work premise
The every other embodiment obtained, broadly falls into the scope of protection of the invention.
The invention provides a kind of lanthanum modified manganese dioxide/carbon composite catalytic agent for metal-air battery,
Including manganese dioxide nano-plates layer and the carbon material particles of La doped, the manganese dioxide nano of described La doped
Lamella uniformly mixes with described carbon material particles, forms the composite balls of surface folding.
The micro-sphere structure that composite balls is non-nucleocapsid structure formed, specific surface area is big and defect is enriched, activity
Center is more, and catalysis activity is higher.The metal prepared by this lanthanum modified manganese dioxide/carbon composite catalytic agent
The power density of air cell is higher.
Described carbon material particles is preferably carbon black granules, and the carbon black in described carbon black granules is preferably KB
One or more in EC-300J, Vxc-72, PT XE2-B and Super P.Specific in the present invention,
The Vxc-72 of KB EC-300J, Shanghai Cabot cabot production, win wound moral for Japan's lion king production are solid
One or several in the Super P that the PT XE2-B and the high TIMCAL of Switzerland's spy's rice of match company production produces
Kind.
The specific surface area of described composite balls is 100m2/ g～150m2/ g, preferably 115m2/ g～130m2/g。
Present invention also offers a kind of lanthanum modified manganese dioxide/carbon composite catalytic agent for metal-air battery
Preparation method, comprise the following steps:
A) material is mixed, after reaction, obtain target product precursor；Described material includes potassium permanganate water
Solution, the aminoacid of sulfur-bearing, lanthanum salt and material with carbon element；
B) described target product precursor is carried out roasting, obtain lanthanum modified manganese dioxide/carbon composite catalytic
Agent.
Material is mixed by the present invention, and described material includes potassium permanganate solution, the aminoacid of sulfur-bearing, lanthanum
Salt and material with carbon element, obtain mixed solution；It is preferably and the aminoacid of sulfur-bearing, lanthanum salt and material with carbon element are added height
In potassium manganate aqueous solution, obtain mixed solution.
The present invention there is no special restriction to the preparation of described potassium permanganate solution, uses art technology
Compound method known to personnel.Potassium permanganate solid is preferably dissolved in deionized water by the present invention,
Prepare potassium permanganate solution.In the present invention, the concentration of described potassium permanganate solution is preferably
0.005mol/L～0.5mol/L.The present invention there is no special restriction to the lanthanum salt used, and uses this area
Lanthanum salt known to technical staff, the present invention is preferably the one in Lanthanum (III) nitrate, lanthanum acetate and lanthanum chloride
Or it is several.The aminoacid of described sulfur-bearing is preferably cysteine and/or methionine.Described material with carbon element is preferred
For carbon black, the one or several in more preferably KB EC-300J, Vxc-72, PT XE2-B and Super P
Kind.Specific in the present invention, the KB EC-300J, the Shanghai Cabot cabot that produce for Japan lion king are raw
The Vxc-72, the PT XE2-B and the high TIMCAL of Switzerland's spy's rice of Evonik Degussa Corp.'s production that produce produce
Super P in one or more.
Potassium permanganate, the aminoacid of sulfur-bearing, lanthanum salt and the matter of material with carbon element in described potassium permanganate solution
Amount ratio preferably 5～50:0.1～1:1～10:1～10, more preferably 10～30:0.2～0.5:2～8:3～8.
In above-mentioned material disclosed by the invention, also include alkaline solution.Concrete, by the aminoacid of sulfur-bearing,
Lanthanum salt and material with carbon element add in potassium permanganate solution, are then added thereto to alkaline solution and are mixed
Solution.The present invention there is no special restriction to described alkaline solution, uses well known to those skilled in the art
Alkaline solution.Present invention preferably employs sodium hydroxide solution and/or potassium hydroxide solution.Described alkalescence
The concentration of solution is preferably 0.1mol/L～1mol/L.The solvent of described alkaline solution is preferably water.Described alkali
Property solution solute and described potassium permanganate solution in the mass ratio of potassium permanganate be preferably 0.01～0.1:1,
More preferably 0.01～0.05:1.
After obtaining mixed solution, described mixed solution is reacted obtains target product precursor.Described reaction
Temperature be preferably 50 DEG C～100 DEG C, more preferably 60 DEG C～80 DEG C；The time of described reaction is 0.5h～10h,
More preferably 1h～3h.
After obtaining target product precursor, described target product precursor is carried out roasting by the present invention, obtains
Lanthanum modified manganese dioxide/carbon composite catalytic agent.Described target product precursor when carrying out roasting, sulfur-bearing
Organic substance in aminoacid acutely decomposes, and causes target product precursor surface to form fold, the mesh of generation
The specific surface area of mark product lanthanum modified manganese dioxide/carbon composite catalytic agent is big and defect is enriched, and active center is relatively
Many, catalysis activity is higher.The temperature of described roasting is preferably 300 DEG C～500 DEG C, more preferably
300 DEG C～400 DEG C；The time of described roasting is preferably 1h～8h, more preferably 3h～5h.
After described roasting, the product after roasting is preferably carried out and is dried by the present invention, obtains lanthanum modified
Manganese dioxide/carbon composite catalyst.The present invention there is no special restriction to the mode of described cleaning, uses this
Cleaning way known to skilled person, the present invention is preferably clear with deionized water and ethanol successively
Washing the product after roasting, number of times >=4 time of described cleaning, the volume fraction of described ethanol is preferably
10%～50%, more preferably 30%.The present invention also without special restriction, uses ability to dry mode
Drying mode known to field technique personnel, present invention preferably employs vacuum drying.Described dry temperature
Degree is preferably 80 DEG C～100 DEG C, more preferably 90～100 DEG C, and the described dry time is preferably 6～24h, more
It is preferably 8～12h.
The present invention there is no particular determination to the source of above-mentioned used raw material components, can be the most commercially available.
Above-mentioned lanthanum modified manganese dioxide/carbon composite catalytic agent is made the positive pole of metal-air battery by the present invention.
The present invention there is no special restriction to the preparation method of described metal-air battery positive pole, uses this area skill
The preparation method of the metal-air battery positive pole known to art personnel.The present invention is preferably modified by described lanthanum
Manganese dioxide/carbon composite catalyst, conduction Carbon Materials (activated carbon VX-72), politef (PTFE)
Powder and terpineol are that 1:2:2:5 mixes according to weight ratio, and ball milling prepares anode sizing agent；Then,
Nickel foam be impregnated in 30wt%PTFE emulsion, high temperature sintering (sinters at 250～400 DEG C
10～120min), nickel foam substrate is obtained；Again described anode sizing agent is coated to described nickel foam substrate,
High temperature sintering (sinters 10～120min) at 250～400 DEG C, obtain the positive pole of metal-air battery.
Described positive pole and negative pole, electrolyte are assembled into metal-air battery by the present invention.The present invention is to described
The kind of negative pole and electrolyte does not has special restriction, described negative pole can use metal, such as: magnesium, aluminum,
Zinc or alloy；Described electrolyte can use potassium hydroxide solution, sodium hydroxide solution, sodium chloride water-soluble
Liquid or sea water etc..Concrete, the present invention uses fine aluminium as negative pole, and potassium hydroxide solution is as electrolysis
Liquid is assembled into simulated battery, at room temperature carries out discharge performance test.
Test result indicate that, use lanthanum modified manganese dioxide/carbon composite catalytic agent that the present invention provides, oxidation
Happens is that 4 electron transfers during reduction reaction, use lanthanum modified manganese dioxide/carbon that the present invention provides
The metal-air battery that composite catalyst prepares, test obtains the maximum power density of battery and is all not less than
220mW/cm2。
The invention provides a kind of lanthanum modified manganese dioxide/carbon composite catalytic agent for metal-air battery,
Including manganese dioxide nano-plates layer and the carbon material particles of La doped, the manganese dioxide nano of described La doped
Lamella uniformly mixes with described carbon material particles, forms the composite balls of surface folding.This composite balls compares table
Area is big and defect is enriched, and active center is more, and catalysis activity is higher.By this lanthanum modified manganese dioxide/
The power density of the metal-air battery that carbon composite catalytic agent prepares is higher.
Present invention also offers a kind of lanthanum modified manganese dioxide/carbon composite catalytic agent for metal-air battery
Preparation method, comprise the following steps: A) by material mix, obtain target product precursor after reaction；
Described material includes potassium permanganate solution, the aminoacid of sulfur-bearing, lanthanum salt and material with carbon element；B) by described mesh
Mark product presoma carries out roasting, obtains lanthanum modified manganese dioxide/carbon composite catalytic agent.The present invention is by Gao Meng
Acid aqueous solutions of potassium, the aminoacid of sulfur-bearing, lanthanum salt and material with carbon element mixing, in mixed process, the ammonia of sulfur-bearing
Base acid is attached to around high manganese ion and lanthanum ion, and after adding material with carbon element, the aminoacid of sulfur-bearing is with high
Mangaic acid root generation redox reaction generates manganese dioxide, and manganese dioxide adheres on it with material with carbon element for matrix,
The aminoacid of lanthanum ion and sulfur-bearing is attached to around manganese dioxide granule simultaneously, and forms spherical target product
Thing presoma.Described target product precursor is when carrying out roasting, and the Organic substance in the aminoacid of sulfur-bearing is acute
Strong decomposition, causes target product precursor surface to form fold, ultimately generates target product lanthanum modification dioxy
Change manganese/carbon composite catalytic agent.Use the composite balls that raw material disclosed by the invention and processing step prepare, than
Surface area is big and defect is enriched, and active center is more, and catalysis activity is higher.Test result indicate that, use
Lanthanum modified manganese dioxide/carbon composite catalytic agent prepared by the present invention, happens is that during redox reaction
4 electron transfers, the metal that the lanthanum modified manganese dioxide/carbon composite catalytic agent using the present invention to prepare prepares is empty
Pneumoelectric pond, test obtains the maximum power density of battery and is all not less than 220mW/cm2。
In order to further illustrate the present invention, the one provided the present invention below in conjunction with embodiment is used for metal
Lanthanum modified manganese dioxide/carbon composite catalytic agent of air cell and preparation method thereof is described in detail, but not
Limiting the scope of the present invention can be understood as.
Embodiment 1
Take the potassium permanganate solution 200ml of 0.25mol/L, then by cysteine, Lanthanum (III) nitrate and Vxc-72
(Shanghai Cabot cabot) adds described potassium permanganate solution, reacts 2h under the conditions of 70 DEG C,
To target product precursor；Potassium permanganate in described potassium permanganate solution, cysteine, Lanthanum (III) nitrate
It is 30:0.5:5:5 with the mass ratio of Vxc-72 (Shanghai Cabot cabot).
By described target product precursor successively with deionized water and ethanol purge, number of times >=4 of described cleaning
Secondary, the volume fraction of described ethanol is 30%, is then vacuum dried 10h at 100 DEG C, obtains target product
Presoma；By target product precursor at 400 DEG C of roasting 5h, obtain that lanthanum modified manganese dioxide/carbon is compound urges
Agent.
The target product precursor that embodiment 1 is prepared by the present invention is scanned electronic microscope photos, result such as Fig. 1
Shown in, Fig. 1 is the SEM figure of the target product precursor of the embodiment of the present invention 1 preparation.Permissible from Fig. 1
Finding out, target product precursor is spheroidal particle.
The present invention is scanned Electronic Speculum to lanthanum modified manganese dioxide/carbon composite catalytic agent that embodiment 1 prepares and divides
Analysis, result is as in figure 2 it is shown, lanthanum modified manganese dioxide/carbon that Fig. 2 is the embodiment of the present invention 1 preparation is combined
The SEM figure of catalyst.Figure it is seen that described lanthanum modified manganese dioxide/carbon composite catalytic agent surface
Having fold to be formed, the lanthanum modified manganese dioxide/carbon composite catalytic agent prepared is the spheroidal particle of surface folding.
Lanthanum modified manganese dioxide/carbon composite catalytic the agent obtained is carried out transmission electron microscope analysis, result by the present invention
As it is shown on figure 3, lanthanum modified manganese dioxide/carbon composite catalytic agent that Fig. 3 is the embodiment of the present invention 1 preparation
TEM schemes, and the 0.71nm shown in Fig. 3 is the interlamellar spacing in catalyst, and 0.35nm is the crystalline substance in catalyst
Compartment away from, it is all corresponding with the structure of the manganese dioxide of water sodium manganese type.
Utilize X-ray diffractometer that the lanthanum modified manganese dioxide/carbon composite catalytic agent obtained is analyzed,
The XRD figure of lanthanum modified manganese dioxide/carbon composite catalytic agent in the embodiment of the present invention 1, as shown in Figure 4.
As seen from Figure 4, the embodiment of the present invention 1 preparation lanthanum modified manganese dioxide/carbon composite catalytic agent 12 °,
24 °, 37 ° and 66 ° have obvious characteristic peak, and this shows described lanthanum modified manganese dioxide/carbon composite catalytic agent master
Body is the manganese dioxide structure of water sodium manganese type.
The present invention have studied the relation of the BET specific surface area of catalyst and the ability of Catalyst Adsorption oxygen, as
Shown in Fig. 5.Fig. 5 is the BET of the lanthanum modified manganese dioxide/carbon composite catalytic agent of the embodiment of the present invention 1 preparation
The graph of a relation of the ability of specific surface area and Catalyst Adsorption oxygen, meanwhile, the present invention has also measured prepared
The specific surface area of lanthanum modified manganese dioxide/carbon composite catalytic agent is 118.29m3/g.From fig. 5, it can be seen that
Relatively big through the BET specific surface area of the manganese dioxide/carbon composite catalyst of lanthanum modification, Catalyst Adsorption oxygen
Ability is higher.
The present invention have studied the linear scanning of the lanthanum modified manganese dioxide/carbon composite catalytic agent of embodiment 1 preparation
Volt-ampere curve (LSV curve), as shown in Figure 6.From fig. 6, it can be seen that the lanthanum of embodiment 1 preparation changes
In the linear sweep voltammetry curve of property manganese dioxide/carbon composite catalyst, take-off potential and half wave potential are the most relatively
Height, shows that the activity of lanthanum modified manganese dioxide/carbon composite catalytic agent is higher.
The present invention is investigated catalyst LSV curve under different rotating speeds, as shown in Figure 7.Fig. 7 is
Lanthanum modified manganese dioxide/carbon composite catalytic the agent of embodiment 1 preparation LSV curve under different rotating speeds.Logical
Cross this curve, turn according to calculating the catalyst that can draw correspondence electronics during redox reaction
Move number, the most as shown in Figure 8.From figure 8, it is seen that the lanthanum modification titanium dioxide of embodiment 1 preparation
Manganese/carbon composite catalytic agent electron transfer number during redox reaction is 4 electronics, i.e. its oxidation
The path of reduction is four electron reaction path completely.
By described lanthanum modified manganese dioxide/carbon composite catalytic agent, activated carbon VX-72, politef
(PTFE) powder and terpineol are that 1:2:2:5 mixes according to weight ratio, and ball milling prepares positive pole slurry
Material；Then, nickel foam be impregnated in 30wt%PTFE emulsion, high temperature sintering (sinters at 350 DEG C
30min), nickel foam substrate is obtained；Again by described anode sizing agent coating to described nickel foam substrate, high
Temperature sintering (sinters 120min) at 330 DEG C, obtain the positive pole of metal-air battery.By described positive pole with negative
Pole (metal Al, purity 99.99%), electrolyte (4mol/L potassium hydroxide) are assembled into simulated battery,
At room temperature carry out discharge performance test, as shown in Figure 9.Fig. 9 provides for using the embodiment of the present invention 1
The discharge performance test result of battery for preparing of lanthanum modified manganese dioxide/carbon composite catalytic agent, wherein,
Medicine ball curve and closed square curve corresponding voltage side, hollow ball curve is corresponding with hollow square curve
Power density side.From fig. 9, it can be seen that the lanthanum modified manganese dioxide/carbon using embodiment 1 to provide is multiple
Closing the metal-air battery that catalyst prepares, test obtains the maximum power density of battery and can reach
235mW/cm2, now corresponding voltage is 1.0V, and electric current density is 235mA/cm2。
Embodiment 2
Take the potassium permanganate solution 200ml of 0.005mol/L, then by cysteine, Lanthanum (III) nitrate and KB
EC-300J (Japan lion king) adds described potassium permanganate solution, reacts 0.5h under the conditions of 50 DEG C,
To target product precursor；Potassium permanganate in described potassium permanganate solution, cysteine, Lanthanum (III) nitrate
It is 30:0.5:5:5 with the mass ratio of KB EC-300J (Japan lion king).
By described target product precursor successively with deionized water and ethanol purge, number of times >=4 of described cleaning
Secondary, the volume fraction of described ethanol is 30%, is then vacuum dried 16h at 80 DEG C, before obtaining target product
Drive body；By target product precursor at 300 DEG C of roasting 3h, obtain lanthanum modified manganese dioxide/carbon composite catalytic
Agent.
By described lanthanum modified manganese dioxide/carbon composite catalytic agent, activated carbon VX-72, politef
(PTFE) powder and terpineol are that 1:2:2:5 mixes according to weight ratio, and ball milling prepares positive pole slurry
Material；Then, nickel foam be impregnated in 30wt%PTFE emulsion, high temperature sintering (sinters at 350 DEG C
30min), nickel foam substrate is obtained；Again by described anode sizing agent coating to described nickel foam substrate, high
Temperature sintering (sinters 120min) at 330 DEG C, obtain the negative electrode of metal-air battery.By described negative electrode and sun
Pole (metal Al, purity 99.99%), electrolyte (4mol/L potassium hydroxide) are assembled into simulated battery,
At room temperature carry out discharge performance test.Test result indicate that, use the lanthanum modification two that embodiment 2 provides
The metal-air battery that manganese oxide/carbon composite catalytic agent prepares, test obtains the maximum power density of battery can
Reach 222mW/cm2, now corresponding voltage is 1.0V, and electric current density is 222mA/cm2。
Embodiment 3
Take the potassium permanganate solution 200ml of 0.005mol/L, then by cysteine, lanthanum acetate and PT
XE2-B (Evonik Degussa Corp.) adds described potassium permanganate solution, reacts 10h under the conditions of 100 DEG C,
Obtain target product precursor；Potassium permanganate in described potassium permanganate solution, cysteine, acetic acid
The mass ratio of lanthanum and PT XE2-B (Evonik Degussa Corp.) is 30:0.5:5:5.
By described target product precursor successively with deionized water and ethanol purge, number of times >=4 of described cleaning
Secondary, the volume fraction of described ethanol is 30%, is then vacuum dried 8h at 100 DEG C, before obtaining target product
Drive body；By target product precursor at 400 DEG C of roasting 5h, obtain lanthanum modified manganese dioxide/carbon composite catalytic
Agent.
By described target product precursor successively with deionized water and ethanol purge, number of times >=4 of described cleaning
Secondary, the volume fraction of described ethanol is 30%, then at 80 DEG C of vacuum dryings, obtains target product forerunner
Body；By target product precursor at 500 DEG C of roasting 8h, obtain lanthanum modified manganese dioxide/carbon composite catalytic agent.
By described lanthanum modified manganese dioxide/carbon composite catalytic agent, activated carbon VX-72, politef
(PTFE) powder and terpineol are that 1:2:2:5 mixes according to weight ratio, and ball milling prepares positive pole slurry
Material；Then, nickel foam be impregnated in 30wt%PTFE emulsion, high temperature sintering (sinters at 350 DEG C
30min), nickel foam substrate is obtained；Again by described anode sizing agent coating to described nickel foam substrate, high
Temperature sintering (sinters 120min) at 330 DEG C, obtain the negative electrode of metal-air battery.By described negative electrode and sun
Pole (metal Al, purity 99.99%), electrolyte (4mol/L potassium hydroxide) are assembled into simulated battery,
At room temperature carry out discharge performance test.Test result indicate that, use the lanthanum modification two that embodiment 3 provides
The metal-air battery that manganese oxide/carbon composite catalytic agent prepares, test obtains the maximum power density of battery can
Reach 225mW/cm2, now corresponding voltage is 1.0V, and electric current density is 220mA/cm2。
Embodiment 4
Take the potassium permanganate solution 200ml of 0.25mol/L, then by potassium permanganate, cysteine, chlorine
Change lanthanum and Super P (the high TIMCAL of Switzerland's spy's rice) adds described potassium permanganate solution, at 100 DEG C
Under the conditions of react 10h, obtain target product precursor；Potassium permanganate in described potassium permanganate solution,
The mass ratio of cysteine, lanthanum chloride and Super P (the high TIMCAL of Switzerland's spy's rice) is 5:0.1:2:
2。
By described target product precursor successively with deionized water and ethanol purge, number of times >=4 of described cleaning
Secondary, the volume fraction of described ethanol is 30%, is then vacuum dried 18h at 80 DEG C, before obtaining target product
Drive body；By target product precursor at 500 DEG C of roasting 8h, obtain lanthanum modified manganese dioxide/carbon composite catalytic
Agent.
By described lanthanum modified manganese dioxide/carbon composite catalytic agent, activated carbon VX-72, politef
(PTFE) powder and terpineol are that 1:2:2:5 mixes according to weight ratio, and ball milling prepares positive pole slurry
Material；Then, nickel foam be impregnated in 30wt%PTFE emulsion, high temperature sintering (sinters at 350 DEG C
30min), nickel foam substrate is obtained；Again by described anode sizing agent coating to described nickel foam substrate, high
Temperature sintering (sinters 120min) at 330 DEG C, obtain the negative electrode of metal-air battery.By described negative electrode and sun
Pole (metal Al, purity 99.99%), electrolyte (4mol/L potassium hydroxide) are assembled into simulated battery,
At room temperature carry out discharge performance test.Test result indicate that, use the lanthanum modification two that embodiment 4 provides
The metal-air battery that manganese oxide/carbon composite catalytic agent prepares, test obtains the maximum power density of battery can
Reach 220mW/cm2, now corresponding voltage is 1.0V, and electric current density is 225mA/cm2。
Embodiment 5
Take the potassium permanganate solution 200ml of 0.25mol/L, by cysteine, Lanthanum (III) nitrate and Vxc-72
(Shanghai Cabot cabot) adds in described potassium permanganate solution, is subsequently adding the water-soluble of sodium hydroxide
Liquid, reacts 2h under the conditions of 70 DEG C, obtains target product precursor；In described potassium permanganate solution
The mass ratio of potassium permanganate, cysteine, Lanthanum (III) nitrate and Vxc-72 (Shanghai Cabot cabot) is 30:
0.5:5:5；The concentration of the aqueous solution of described sodium hydroxide is 0.2mol/L, and described sodium hydroxide is with described
The mass ratio of potassium permanganate is 0.03:1.
By described target product precursor successively with deionized water and ethanol purge, number of times >=4 of described cleaning
Secondary, the volume fraction of described ethanol is 30%, is then vacuum dried 6h at 100 DEG C, before obtaining target product
Drive body；By target product precursor at 400 DEG C of roasting 5h, obtain lanthanum modified manganese dioxide/carbon composite catalytic
Agent.
By described lanthanum modified manganese dioxide/carbon composite catalytic agent, activated carbon VX-72, politef
(PTFE) powder and terpineol are that 1:2:2:5 mixes according to weight ratio, and ball milling prepares positive pole slurry
Material；Then, nickel foam be impregnated in 30wt%PTFE emulsion, high temperature sintering (sinters at 350 DEG C
30min), nickel foam substrate is obtained；Again by described anode sizing agent coating to described nickel foam substrate, high
Temperature sintering (sinters 120min) at 330 DEG C, obtain the negative electrode of metal-air battery.By described negative electrode and sun
Pole (metal Al, purity 99.99%), electrolyte (4mol/L potassium hydroxide) are assembled into simulated battery,
At room temperature carry out discharge performance test.Test result indicate that, use the lanthanum modification two that embodiment 5 provides
The metal-air battery that manganese oxide/carbon composite catalytic agent prepares, test obtains the maximum power density of battery can
Reach 232mW/cm2, now corresponding voltage is 1.0V, and electric current density is 232mA/cm2。
Embodiment 6
Take the potassium permanganate solution 200ml of 0.25mol/L, by cysteine, Lanthanum (III) nitrate and PT XE2-B
(Evonik Degussa Corp.) adds in described potassium permanganate solution, is subsequently adding the water-soluble of potassium hydroxide
Liquid, reacts 2h under the conditions of 70 DEG C, obtains target product precursor；In described potassium permanganate solution
The mass ratio of potassium permanganate, cysteine, lanthanum chloride and PT XE2-B (Evonik Degussa Corp.) is 35:
0.7:1:2；The concentration of the aqueous solution of described potassium hydroxide is 0.5mol/L, and described potassium hydroxide is with described
The mass ratio of potassium permanganate is 0.08:1.
By described target product precursor successively with deionized water and ethanol purge, number of times >=4 of described cleaning
Secondary, the volume fraction of described ethanol is 30%, is then vacuum dried 10h at 100 DEG C, obtains target product
Presoma；By target product precursor at 500 DEG C of roasting 2h, obtain that lanthanum modified manganese dioxide/carbon is compound urges
Agent.
By described lanthanum modified manganese dioxide/carbon composite catalytic agent, activated carbon VX-72, politef
(PTFE) powder and terpineol are that 1:2:2:5 mixes according to weight ratio, and ball milling prepares positive pole slurry
Material；Then, nickel foam be impregnated in 30wt%PTFE emulsion, high temperature sintering (sinters at 350 DEG C
30min), nickel foam substrate is obtained；Again by described anode sizing agent coating to described nickel foam substrate, high
Temperature sintering (sinters 120min) at 330 DEG C, obtain the negative electrode of metal-air battery.By described negative electrode and sun
Pole (metal Al, purity 99.99%), electrolyte (4mol/L potassium hydroxide) are assembled into simulated battery,
At room temperature carry out discharge performance test.Test result indicate that, use the lanthanum modification two that embodiment 6 provides
The metal-air battery that manganese oxide/carbon composite catalytic agent prepares, test obtains the maximum power density of battery can
Reach 225mW/cm2, now corresponding voltage is 1.0V, and electric current density is 225mA/cm2。
Described above to the disclosed embodiments, makes professional and technical personnel in the field be capable of or uses
The present invention.Multiple amendment to these embodiments will be aobvious and easy for those skilled in the art
See, generic principles defined herein can without departing from the spirit or scope of the present invention,
Realize in other embodiments.Therefore, the present invention is not intended to be limited to the embodiments shown herein,
And it is to fit to the widest scope consistent with principles disclosed herein and features of novelty.
Claims (10)
1. the lanthanum modified manganese dioxide/carbon composite catalytic agent for metal-air battery, it is characterised in that
Including manganese dioxide nano-plates layer and the carbon material particles of La doped, the manganese dioxide nano of described La doped
Lamella uniformly mixes with described carbon material particles, forms the composite balls of surface folding.
Lanthanum modified manganese dioxide/carbon composite catalytic agent the most according to claim 1, it is characterised in that
The specific surface area of described composite balls is 100m2/ g～150m2/g。
3. it is used for a preparation method for the lanthanum modified manganese dioxide/carbon composite catalytic agent of metal-air battery,
It is characterized in that, comprise the following steps:
A) material is mixed, after reaction, obtain target product precursor；Described material includes potassium permanganate water
Solution, the aminoacid of sulfur-bearing, lanthanum salt and material with carbon element；
B) described target product precursor is carried out roasting, obtain lanthanum modified manganese dioxide/carbon composite catalytic
Agent.
The preparation method of lanthanum modified manganese dioxide/carbon composite catalytic agent the most according to claim 3, its
Being characterised by, the concentration of described potassium permanganate solution is 0.005mol/L～0.5mol/L.
The preparation method of lanthanum modified manganese dioxide/carbon composite catalytic agent the most according to claim 3, its
Being characterised by, the aminoacid of described sulfur-bearing is cysteine or methionine.
The preparation method of lanthanum modified manganese dioxide/carbon composite catalytic agent the most according to claim 3, its
It is characterised by, one or more in Lanthanum (III) nitrate, lanthanum acetate and lanthanum chloride of described lanthanum salt.
The preparation method of lanthanum modified manganese dioxide/carbon composite catalytic agent the most according to claim 3, its
It is characterised by, potassium permanganate, the aminoacid of sulfur-bearing, lanthanum salt and the carbon material in described potassium permanganate solution
The mass ratio of material is 5～50:0.1～1:1～10:1～10.
The preparation method of lanthanum modified manganese dioxide/carbon composite catalytic agent the most according to claim 3, its
Be characterised by, step A) in material also include alkaline solution.
The preparation method of lanthanum modified manganese dioxide/carbon composite catalytic agent the most according to claim 3, its
Being characterised by, the temperature of described reaction is 50 DEG C～100 DEG C, and the time of described reaction is 0.5h～10h.
The preparation method of lanthanum modified manganese dioxide/carbon composite catalytic agent the most according to claim 3,
It is characterized in that, the temperature of described roasting is 300 DEG C～500 DEG C, and the time of described roasting is 1h～8h.
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