CN105514449B - A kind of metal air battery cathodes catalyst and preparation method thereof - Google Patents
A kind of metal air battery cathodes catalyst and preparation method thereof Download PDFInfo
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- CN105514449B CN105514449B CN201510764498.3A CN201510764498A CN105514449B CN 105514449 B CN105514449 B CN 105514449B CN 201510764498 A CN201510764498 A CN 201510764498A CN 105514449 B CN105514449 B CN 105514449B
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention provides a kind of metal air battery cathodes catalyst and preparation method thereof, catalyst provided by the invention by the manganese carbonate that silver powder coats by being sintered to obtain, wherein, in the manganese carbonate of the cladding silver powder, the mass ratio of the silver powder and the manganese carbonate is (0.5~10):1.In the present invention, by being sintered to the manganese carbonate for coating silver powder, so that silver powder is coated on the surface of Mn oxide in obtained catalyst, and it is not dispersed on Mn oxide matrix, and it is found surprisingly that by testing result, the silver powder that the present invention obtains is coated on the composite catalyst of Mn oxide compared with existing silver-colored Mn oxide composite catalyst, is significantly improved as catalyst applied to the output power of battery that air cell obtains.
Description
Technical field
The present invention relates to the catalyst field of air cell more particularly to a kind of metal air battery cathodes catalyst and
Preparation method.
Background technology
With increase severely consumption and the day of the fuel such as coal, oil and natural gas and the reserves of energy resources it is gradual withered
It exhausts, the energy technology for seeking environmental-friendly sustainable development is extremely urgent.Fuel cell is because it is with energy conversion efficiency height, nothing
The advantages that polluting, be noiseless, it has also become the hot spot of countries in the world research.
Fuel cell technology includes Proton Exchange Membrane Fuel Cells, solid oxide fuel cell, metal air fuel electricity
Pond and alkaline anion-exchange membrane fuel cell etc..Wherein, since metal-air battery fuel is in plentiful supply, storage life
Length, noise is low and oxygen electrode, that is, cathode can be used base metal reducing catalyst and be favored by research staff.Wherein, metal
The cathod catalyst of air cell has a great impact to the performance of battery, and at present, the cathode available for metal-air battery is urged
Agent is usually the compound etc. of Mn oxide, perovskite, noble metal, conductive Carbon Materials and above-mentioned material, wherein, Mn oxide
It is cheap, it is easy to get, but oxygen catalytic activity is relatively low in ORR reactions；Perovskite is not easy mass production；And noble metal and manganese oxygen
Although the compound better catalytic activity of compound, cost is higher, and silver-colored due to advantage of lower cost, so, about patina
The research for closing object and Mn oxide composite catalyst is relatively more, such as：Patent application No. is 201010563788.9 discloses one
Kind Ag/MnyOx/C catalyst and its preparation and application, the patent are reacted by using silver carbonate with potassium permanganate and graphite,
Precursor A gMnO4 crystal is obtained, then high temperature pyrolysis precursor A gMnO4 is obtained, and still, the catalyst which is prepared should
During for battery, the output power of battery is still relatively low.
Invention content
In view of this, the technical problems to be solved by the invention are to provide a kind of metal air battery cathodes catalyst
And preparation method thereof, the output power of the battery of catalyst preparation provided by the invention is high.
The present invention provides a kind of metal air battery cathodes catalyst, the manganese carbonate coated by silver powder is sintered to obtain,
Wherein, in the manganese carbonate of the silver powder cladding, the mass ratio of the silver powder and the manganese carbonate is (0.5~10):
1。
Preferably, the mass ratio of the silver powder and the manganese carbonate is (1~5):1.
Preferably, the grain size of the silver powder is 50~200nm.
The present invention also provides a kind of preparation method of catalyst of the present invention, including：
The manganese carbonate of silver powder cladding is sintered, obtains catalyst；
Wherein, in the manganese carbonate of the silver powder cladding, the mass ratio of the silver powder and the manganese carbonate is (0.5~10):
1。
Preferably, the manganese carbonate of the silver powder cladding is prepared in accordance with the following methods：
1-1) by manganese carbonate, surfactant and solvent mixing and ball milling, the slurry after ball milling is obtained；
Silver powder ball milling again 1-2) is added in into the slurry after ball milling, obtains the manganese carbonate of silver powder cladding.
Preferably, the step 1-1) ball milling in the grain size of ball milling pearl that adds in be 0.5~1.5mm.
Preferably, which is characterized in that the surfactant is dodecyl sodium sulfate, the poly- second two of polyvinylpyrrolidone
One or more of alcohol, polyoxyethylene ether, polyoxyethylene amine and alkylolamides.
Preferably, the solvent is one kind or several in terpinol, ethyl alcohol, isopropanol, ethylene glycol, n-butanol and n-hexyl alcohol
Kind.
Preferably, the temperature of the sintering is 350~550 DEG C.
Preferably, the step is further included mixes ball milling again with absolute ethyl alcohol by sintered catalyst, obtains catalyst.
Compared with prior art, the present invention provides a kind of metal sky cell cathode catalyst, by being coated by silver powder
Manganese carbonate be sintered to obtain, wherein, it is described cladding silver powder manganese carbonate in, the mass ratio of the silver powder and the manganese carbonate is
(0.5~10):1.In the present invention, by being sintered to the manganese carbonate for coating silver powder so that silver powder packet in obtained catalyst
The surface of Mn oxide (MnOx, 1≤x≤3) is overlayed on, and is not dispersed on Mn oxide matrix, and pass through testing result
Be found surprisingly that, the obtained silver powder of the present invention be coated on Mn oxide composite catalyst and existing silver-Mn oxide it is compound
Catalyst is compared, and is significantly improved as catalyst applied to the output power of battery that air cell obtains, experimental result table
Bright, the maximum power density that catalyst provided by the invention is applied to magnesium air battery may be up to 97.4mW/cm2。
Description of the drawings
Fig. 1 is the SEM figures of catalyst prepared by the embodiment of the present invention 1；
Fig. 2 is the partial enlarged view of the SEM figures of catalyst prepared by the embodiment of the present invention 1；
Fig. 3 is the X-ray power spectrum distribution diagram of element total figure of catalyst that the embodiment of the present invention 1 provides；
Fig. 4 is the X-ray power spectrum distribution diagram of element of the silver element in the catalyst that the embodiment of the present invention 1 provides；
Fig. 5 is the X-ray power spectrum distribution diagram of element of the manganese element in the catalyst that the embodiment of the present invention 1 provides；
Fig. 6 is the X-ray power spectrum distribution diagram of element of oxygen in the catalyst that the embodiment of the present invention 1 provides；
Fig. 7 is each element content distribution figure of catalyst that the embodiment of the present invention 1 provides；
Fig. 8 is the discharge performance test result of battery that the catalyst preparation provided using the embodiment of the present invention 1 is obtained；
Fig. 9 is the discharge performance test result of battery that the catalyst preparation provided using the embodiment of the present invention 2 is obtained；
Figure 10 is the discharge performance test result of battery that the catalyst preparation provided using the embodiment of the present invention 3 is obtained；
Figure 11 is the discharge performance of the battery that the catalyst preparation provided using the embodiment of the present invention 4 is obtained and uncoated
The discharge performance test result of battery that the catalyst preparation obtained after the manganese carbonate sintering of silver obtains；
The catalyst obtained after the manganese carbonate sintering of catalyst and uncoated silver that Figure 12 is obtained for the embodiment of the present invention 4
The performance test results；
Figure 13 is the SEM figures of catalyst prepared by comparative example 1 of the present invention；
Figure 14 is the discharge performance test result of battery obtained using the catalyst preparation that comparative example 1 of the present invention provides.
Specific embodiment
The present invention provides a kind of metal air battery cathodes catalyst, the manganese carbonate coated by silver powder is sintered to obtain,
Wherein, in the manganese carbonate of the silver powder cladding, the mass ratio of the silver powder and the manganese carbonate is (0.5~10):
1。
According to the present invention, in the manganese carbonate of the silver powder cladding, the mass ratio of the silver powder and the manganese carbonate is preferably
(1~5):1, more preferably (2~3):1；The grain size of manganese carbonate in the manganese carbonate of the silver powder cladding is preferably 0.1~20 micro-
Rice；More preferably 0.6~12 micron, most preferably 3~8 microns, the present invention is to the shape of manganese carbonate also without particular/special requirement, stick
Shape, it is spherical；The grain size of the silver powder is preferably 50~200 nanometers, more preferably 80~150 nanometers, most preferably 100~
120 nanometers；The grain size of the obtained catalyst is preferably 1~2 micron；
In the present invention, the present invention is not particularly limited the sintering, sintering processing well known in the art, the present invention
It is preferred that sintering temperature is 350~550 DEG C.
The present invention provides a kind of metal air battery cathodes catalyst, by being sintered by the manganese carbonate that silver powder coats
It arrives, wherein, in the manganese carbonate of the cladding silver powder, the mass ratio of the silver powder and the manganese carbonate is (0.5~10):1.This hair
In bright, by being sintered to the manganese carbonate for coating silver powder so that silver powder is coated on the table of Mn oxide in obtained catalyst
Face, i.e. silver powder are covered in Mn oxide surface, and are not dispersed on Mn oxide matrix with scatterplot, so that obtaining
Ag-MnOx(1≤x≤3) are significantly improved applied to the output power of air cell.
The present invention also provides a kind of preparation method of catalyst of the present invention, including：
The manganese carbonate of silver powder cladding is sintered, obtains catalyst；
Wherein, in the manganese carbonate of the cladding silver powder, the mass ratio of the silver powder and the manganese carbonate is (0.5~10):
1。
According to the present invention, the present invention is sintered by the manganese carbonate for coating silver powder, obtains catalyst；Wherein, the silver powder
In the manganese carbonate of cladding, the mass ratio of the silver powder and the manganese carbonate is preferably (1~5):1, more preferably (2~3):1；
The grain size of manganese carbonate in the manganese carbonate of the silver powder cladding is preferably 0.1~10 micron；More preferably 1~8 is micro-
Rice, most preferably 3~6 microns, the shape of the invention to manganese carbonate is rodlike also without particular/special requirement, spherical；The silver powder
Grain size be preferably 50~200 nanometers, more preferably 80~150 nanometers, most preferably 100~120 nanometers；The present invention is to sintering
Temperature be not particularly limited, well known to a person skilled in the art the temperature being sintered for manganese salt；The sintering temperature of the present invention
Preferably 350~550 DEG C, more preferably 400~500 DEG C of degree；The time of the sintering is preferably 1~5 hour, more preferably 2
~3 hours.
According to the present invention, the manganese carbonate of silver powder cladding of the present invention is preferably prepared in accordance with the following methods：
1-1) by manganese carbonate, surfactant and solvent mixing and ball milling, the slurry after ball milling is obtained；
Silver powder ball milling again 1-2) is added in into the slurry after ball milling, obtains the manganese carbonate of silver powder cladding.
In the present invention, manganese carbonate, surfactant and solvent mixing and ball milling are obtained the slurry after ball milling by the present invention；Its
In, the mass ratio of the manganese carbonate and the surfactant is preferably (0.5~5)：1, more preferably (1~4)：1, most preferably
For (2~3)：1；The amount ratio of the manganese carbonate and the solvent is 1g：(3~10) mL, more preferably 1g：(5~8) mL；This
Invention does not have particular/special requirement to the surfactant, and well known to a person skilled in the art the surfactant available for ball milling is equal
Can, surfactant of the present invention is preferably that the surfactant is dodecyl sodium sulfate, polyvinylpyrrolidone, gathers
One or more of ethylene glycol, polyoxyethylene ether, polyoxyethylene amine and alkylolamides；The present invention does not have the solvent yet
Special envoy requires, and solvent of the present invention is preferably one kind in terpinol, ethyl alcohol, isopropanol, ethylene glycol, n-butanol and n-hexyl alcohol
Or several, more preferably terpinol.
And in order to enable ball milling is abundant, the grain size of ball milling pearl added in ball milling of the present invention is preferably 0.5~
1.5mm, more preferably 0.8~1.3mm, most preferably 1.0~1.2mm；The mass ratio of the ball milling pearl and manganese carbonate is preferably
(2~5)：1, more preferably (3~4)：1；The present invention is not particularly limited the type of the ball milling pearl of ball milling, such as can be oxidation
Zirconium particle or alundum (Al2O3) particle.
Silver powder ball milling again is added in into the slurry after ball milling, obtains the manganese carbonate of silver powder cladding.The ball milling again
Time is preferably 4~6 hours；The present invention is to ball milling ball milling condition again also without particular/special requirement, ball milling side well known in the art
Formula, the present invention are ball milling under 300~500rpm preferably in rotating speed.
And in order to make the performance of catalyst that the present invention obtains more preferable, the present invention is preferably also by sintered catalyst and nothing
Water-ethanol mixes ball milling again, obtains catalyst.Wherein, the mass ratio of the sintered catalyst and absolute ethyl alcohol is preferably (3
~5)：1；The mass ratio of the ball milling pearl and the sintered catalyst is (3~5)：1；And the ball milling pearl used in ball milling
Grain size is preferably 1~5mm, more preferably 2~3mm.The present invention is not particularly limited the time of ball milling again, and preferably 1~5 is small
When, more preferably 2~3 hours.
The preparation method of metal sky cell cathode catalyst provided by the invention, by silver powder and carbon by way of ball milling
Sour manganese mixing, obtains the manganese carbonate of silver powder cladding, and then obtained presoma is sintered, then grind to obtain catalyst again so that
Silver is coated on the outside of Mn oxide in obtained silver/Mn oxide composite catalyst, so that the metal being prepared is empty
The cell output in pneumoelectric pond has significant raising.
It is clearly and completely described below in conjunction with the technical solution of the embodiment of the present invention, it is clear that described implementation
Example is only part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's all other embodiments obtained without making creative work belong to the model that the present invention protects
It encloses.
Embodiment 1
(1) it is 1 according to weight ratio with dodecyl sodium sulfate by manganese carbonate that grain size is 1~5 micron：1,2g is respectively taken, is added
Enter into 15ml terpinols, ball milling 5h, wherein ball milling bead diameter is 1.0mm, ball milling pearl 10g；Then slurry after milling
In addition grain size be 120 nanometers of 2g silver powder, continue ball milling 5h, obtain the manganese carbonate of silver powder cladding.
(2) manganese carbonate that silver powder coats is sintered 1.5h in air atmosphere, it is 400 DEG C to burn temperature, acquired powder
With absolute ethyl alcohol according to mass ratio be 3：1 mixed after ball milling, ball milling bead diameter is 2.0mm, ball milling pearl and forerunner's weight
Than being 3：1, ball milling 3h, gained slurry in air atmosphere at 50 DEG C dry 12h to get to catalyst fines.
Electron-microscope scanning, the result is shown in Figure 1~Fig. 2 are carried out to the powder that embodiment 1 is prepared, Fig. 1 is the embodiment of the present invention 1
The SEM figures of the catalyst of preparation；Fig. 2 is the partial enlarged view of the SEM figures of catalyst prepared by the embodiment of the present invention 1；
Obtained catalyst by energy spectrum analysis (EDS) is detected, as a result sees Fig. 3~Fig. 7, Fig. 3 is real for the present invention
The X-ray power spectrum distribution diagram of element total figure of the catalyst of the offer of example 1 is provided；Fig. 4 is in the catalyst that the embodiment of the present invention 1 provides
Silver element X-ray power spectrum distribution diagram of element；Fig. 5 is that the X- of the manganese element in the catalyst that the embodiment of the present invention 1 provides is penetrated
Line power spectrum distribution diagram of element；Fig. 6 is the X-ray power spectrum distribution diagram of element of oxygen in the catalyst that the embodiment of the present invention 1 provides；Fig. 7
Each element content distribution figure for the catalyst that the embodiment of the present invention 1 provides；Of the present invention urge is can be seen that from Fig. 3~Fig. 6
Ag elements are equally distributed with Mn elements in agent, and the distribution that non-exhibiting is dotted, illustrate that Ag is wrapped in the surface of MnOx, and
Non- simple spot distribution.From figure 7 it can be seen that in catalyst prepared by embodiment 1 of the present invention each element content
As shown in table 1, each element content in the catalyst that table 1 is prepared for the embodiment of the present invention 1.
Each element content in the catalyst that table 1 is prepared for the embodiment of the present invention 1
| Element | Wt% | Wt%Sigma |
| C | 16.78 | 0.47 |
| O | 24.88 | 0.51 |
| Mn | 29.91 | 0.41 |
| Ag | 24.49 | 0.40 |
| Au | 3.95 | 0.34 |
| Total amount: | 100.00 |
In addition, it is necessary to, it is noted that Au is test needs high electric conductivity and spray up, can be neglected.
(3) catalyst 0.5g, conductive Carbon Materials VX-721.0g, PTFE powder 0.3g, pine tar is prepared in Example 1
Ball milling 4h after alcohol 5.0g is mixed, ball milling bead diameter are 5mm, obtain cathode slurry；
After nickel foam is impregnated 30wt%PTFE lotions, 35min is sintered at 350 DEG C to get to nickel foam substrate.
Gained cathode slurry is coated to nickel foam substrate, 30min is sintered at 350 DEG C, you can obtains magnesium air electricity
Pool cathode.
(4) by magnesium air cell cathode and magnesium plate AZ61 assembled batteries in test device is made by oneself, electrolyte 10wt%
NaCl aqueous solutions carry out discharge performance test, and it is the catalyst preparation provided using the embodiment of the present invention 1 as a result to see Fig. 8, Fig. 8
The discharge performance test result of obtained battery, from figure 8, it is seen that using catalyst of the present invention assembling magnesium air electricity
Pond, test obtain maximum power density as 91.8mW/cm2, and corresponding voltage is 0.574V, current density 100mA/cm at this time.
Embodiment 2
(1) it is 2 according to weight ratio with dodecyl sodium sulfate by manganese carbonate that grain size is 0.3~10 micron：1, it takes respectively
2g and 1g is added in 10ml terpinols, ball milling 5h, and wherein ball milling bead diameter is 0.5mm, ball milling pearl 8g；Then ball milling it
The silver powder that 4g grain sizes are 60 nanometers is added in slurry afterwards, continues ball milling 6h, obtains the manganese carbonate of silver powder cladding.
(2) manganese carbonate that silver powder coats is sintered 2.0h in air atmosphere, it is 350 DEG C to burn temperature, acquired powder
With absolute ethyl alcohol according to mass ratio be 3：1 mixed after ball milling, ball milling bead diameter is 2.0mm, ball milling pearl and forerunner's weight
Than being 3：1, ball milling 4h, gained slurry in air atmosphere at 50 DEG C dry 10h to get to catalyst fines.
(3) catalyst 0.5g, conductive Carbon Materials VX-721.5g, PTFE powder 0.5g prepared by Example 2, terpinol
Ball milling 5h after 10.0g is mixed, ball milling bead diameter are 5mm, obtain cathode slurry；
After nickel foam is impregnated 40wt%PTFE lotions, it is sintered 30min at 300 DEG C, you can obtain nickel foam substrate.
Gained cathode slurry is coated to nickel foam substrate, 30min is sintered at 300 DEG C, you can obtains magnesium air electricity
Pool cathode.
(4) by magnesium air cell cathode and magnesium plate AZ61 assembled batteries in test device is made by oneself, electrolyte 10wt%
NaCl aqueous solutions carry out discharge performance test, and it is the catalyst preparation provided using the embodiment of the present invention 2 as a result to see Fig. 9, Fig. 9
The discharge performance test result of obtained battery, from fig. 9, it can be seen that using catalyst of the present invention assembling magnesium air electricity
Pond, test obtain maximum power density as 92.2mW/cm2, corresponding voltage is 0.594V, current density 155mA/cm at this time.
Embodiment 3
(1) it is 3 according to weight ratio with dodecyl sodium sulfate by manganese carbonate that grain size is 5~10 microns：1,3g is taken respectively
And 1g, it is added in 15ml terpinols, ball milling 6h, wherein ball milling bead diameter is 1.0mm, ball milling pearl 15g；Then after milling
Slurry in addition 6g grain sizes be 200 nanometers silver powder, continue ball milling 4h, obtain the manganese carbonate of silver powder cladding.
(2) manganese carbonate that silver powder coats is sintered 0.5h in air atmosphere, it is 500 DEG C to burn temperature, acquired powder
With absolute ethyl alcohol according to mass ratio be 4：1 mixed after ball milling, ball milling bead diameter is 3.0mm, ball milling pearl and forerunner's weight
Than being 4：1, ball milling 3h, gained slurry in air atmosphere at 60 DEG C dry 12h to get to catalyst fines.
(3) the catalyst fines 0.8g, conductive Carbon Materials VX-722.0g, PTFE powder 0.4g obtained, terpinol
Ball milling 4h after 12.0g is mixed, ball milling bead diameter are 10mm, must beat cathode slurry；
After nickel foam is impregnated 50wt%PTFE lotions, it is sintered 20min at 350 DEG C, you can obtain nickel foam substrate.
Gained cathode slurry is coated to nickel foam substrate, 20min is sintered at 330 DEG C, you can obtains magnesium air electricity
Pool cathode.
(4) by magnesium air cell cathode and magnesium plate AZ61 assembled batteries in test device is made by oneself, electrolyte 10wt%
NaCl aqueous solutions carry out discharge performance test, and the result is shown in Figure 10, Figure 10 is the catalyst system provided using the embodiment of the present invention 3
The standby obtained discharge performance test result of battery, from fig. 10 it can be seen that empty using catalyst of the present invention assembling magnesium
Pneumoelectric pond, test obtain maximum power density as 90.0mW/cm2, corresponding voltage is 0.630V, current density 143mA/ at this time
cm。
Embodiment 4
(1) it is 5 according to weight ratio with dodecyl sodium sulfate by manganese carbonate that grain size is 5~10 microns：1,5g is taken respectively
And 1g, it is added in 20ml terpinols, ball milling 5h, wherein ball milling bead diameter is 1.0mm, ball milling pearl 15g；Then after milling
Slurry in addition 5g grain sizes be 120 nanometers silver powder, continue ball milling 5h, obtain the manganese carbonate of silver powder cladding.
(2) manganese carbonate that silver powder coats is sintered 0.5h in air atmosphere, it is 450 DEG C to burn temperature, acquired powder
With absolute ethyl alcohol according to mass ratio be 4：1 mixed after ball milling, ball milling bead diameter is 3.0mm, ball milling pearl and forerunner's weight
Than being 4：1, ball milling 3h, gained slurry in air atmosphere at 60 DEG C dry 12h to get to catalyst fines.
(3) the catalyst fines 1.6g, conductive Carbon Materials VX-724.0g, PTFE powder 0.8g obtained, terpinol
Ball milling 5h after 24.0g is mixed, ball milling bead diameter are 10mm to get cathode slurry；
After nickel foam is impregnated 35wt%PTFE lotions, it is sintered 30min at 340 DEG C, you can obtain nickel foam substrate.
Gained cathode slurry is coated to nickel foam substrate, 20min is sintered at 330 DEG C, you can obtains magnesium air electricity
Pool cathode.
(4) by magnesium air cell cathode and magnesium plate AZ61 assembled batteries in test device is made by oneself, electrolyte 10wt%
NaCl aqueous solutions carry out discharge performance test, and the result is shown in Figure 11, Figure 11 is the catalyst system provided using the embodiment of the present invention 4
The battery that the catalyst preparation obtained after the manganese carbonate sintering of the discharge performance and uncoated silver of standby obtained battery obtains
Discharge performance test result, it can be seen from figure 11 that assembling magnesium air battery using catalyst of the present invention, test obtains
Maximum power density is 97.4mW/cm2, corresponding voltage is 0.649V, current density 150mA/cm at this time.And uncoated silver
The maximum power density of battery that the catalyst preparation obtained after manganese carbonate sintering obtains is 65.8mW/cm2, corresponding voltage at this time
For 0.548V, current density 120mA/cm2。
The catalyst and the manganese carbonate of uncoated silver obtained by linear sweep voltammetry (LSV) to the embodiment of the present invention
The catalyst obtained after sintering is tested for the property, the result is shown in Figure 12, Figure 12 be the obtained catalyst of the embodiment of the present invention 4 and
The performance test results of catalyst obtained after the manganese carbonate sintering of uncoated silver, it can be recognized from fig. 12 that provided by the invention
In catalyst, take-off potential is -0.005V, and limiting current density is -4.2mA/cm2, and half wave potential is -0.286V；It is uncoated
The take-off potential of catalyst obtained after the manganese carbonate sintering of silver is -0.028V, and limiting current density is -4.33mA/cm2, partly
Wave current potential is -0.321V；As it can be seen that the take-off potential and half wave potential numerical value of catalyst provided by the invention are than uncoated silver
The take-off potential and half wave potential numerical value of the catalyst obtained after manganese carbonate sintering are big, illustrate catalyst provided by the invention
Performance is high.
Comparative example 1
First manganese carbonate at a temperature of 350~550 DEG C is decomposed and obtains product, by the product and silver powder with certain proportion 1~
10：Ethyl alcohol is added after 1 mixing, the ball milling pearl that grain size is 0.5~1.5mm is chosen and ball milling 3 is carried out in the case where rotating speed is 300~500rpm
~5h, then 60 DEG C drying 12h stay overnight, obtain composite catalyst.
Electron-microscope scanning, the result is shown in Figure 13 are carried out to the powder that comparative example 1 is prepared, Figure 13 makes for comparative example 1 of the present invention
The SEM figures of standby catalyst；It can be seen from the figure that bright spot little particle is silver powder, products therefrom granular size differs, and silver powder
Only disperse wherein, not forming cladding.
Battery is prepared with above-mentioned product：The catalyst fines 1.6g obtained, conductive Carbon Materials VX-724.0g, PTFE powder
Last 0.8g, ball milling 5h after terpinol 24.0g is mixed, ball milling bead diameter are 10mm to get cathode slurry；Nickel foam is impregnated
After 35wt%PTFE lotions, it is sintered 30min at 340 DEG C, you can obtain nickel foam substrate.Gained cathode slurry is coated to bubble
On foam Ni substrate, 20min is sintered at 330 DEG C, you can obtain magnesium air cell cathode.
By magnesium air cell cathode and magnesium plate AZ61 assembled batteries in test device is made by oneself, electrolyte 10wt%NaCl
Aqueous solution, carries out discharge performance test, the result is shown in Figure 14, and Figure 14 is to be obtained using the catalyst preparation that comparative example 1 of the present invention provides
The discharge performance test result of the battery arrived, it is seen from figure 14 that using catalyst of the present invention assembling magnesium air electricity
Pond, test obtain maximum power density as 51mW/cm2, battery performance is very low, illustrates that the catalytic effect of catalyst is poor.
The explanation of above example is only intended to facilitate the understanding of the method and its core concept of the invention.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvement and modification are also fallen within the protection scope of the claims of the present invention.
Claims (10)
1. a kind of metal air battery cathodes catalyst, the manganese carbonate coated by silver powder is sintered to obtain catalyst,
Wherein, in the manganese carbonate of the silver powder cladding, the mass ratio of the silver powder and the manganese carbonate is (0.5~10):1；
Silver powder in the catalyst is coated on the surface of Mn oxide；
The structural formula of the Mn oxide be MnOx, 1≤x≤3.
2. catalyst according to claim 1, which is characterized in that the mass ratio of the silver powder and the manganese carbonate for (1~
5):1。
3. catalyst according to claim 1, which is characterized in that the grain size of the silver powder in the manganese carbonate of the silver powder cladding
For 50~200nm.
4. a kind of preparation method of the catalyst described in claims 1 to 3 any one, including：
The manganese carbonate of silver powder cladding is sintered, obtains catalyst；
Wherein, in the manganese carbonate of the silver powder cladding, the mass ratio of the silver powder and the manganese carbonate is (0.5~10):1.
5. preparation method according to claim 4, which is characterized in that the manganese carbonate of the silver powder cladding is in accordance with the following methods
It is prepared：
1-1) by manganese carbonate, surfactant and solvent mixing and ball milling, the slurry after ball milling is obtained；
Silver powder ball milling again 1-2) is added in into the slurry after ball milling, obtains the manganese carbonate of silver powder cladding.
6. preparation method according to claim 5, which is characterized in that the step 1-1) ball milling in the ball milling pearl that adds in
Grain size be 0.5~1.5mm.
7. preparation method according to claim 5, which is characterized in that the surfactant for dodecyl sodium sulfate,
One or more of polyvinylpyrrolidone, polyethylene glycol, polyoxyethylene ether, polyoxyethylene amine and alkylolamides.
8. preparation method according to claim 5, which is characterized in that the solvent is terpinol, ethyl alcohol, isopropanol, second
One or more of glycol, n-butanol and n-hexyl alcohol.
9. preparation method according to claim 4, which is characterized in that the temperature of the sintering is 350~550 DEG C.
10. preparation method according to claim 4, which is characterized in that further include sintered catalyst and anhydrous second
Alcohol mixes ball milling again, obtains catalyst.
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