CN109244442A - A kind of porous anodized aluminum and aluminium-air cell - Google Patents
A kind of porous anodized aluminum and aluminium-air cell Download PDFInfo
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- CN109244442A CN109244442A CN201810897780.2A CN201810897780A CN109244442A CN 109244442 A CN109244442 A CN 109244442A CN 201810897780 A CN201810897780 A CN 201810897780A CN 109244442 A CN109244442 A CN 109244442A
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- aluminium
- anodized aluminum
- porous anodized
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/463—Aluminium based
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of porous anodized aluminum and aluminium-air cell, the structure of the aluminium anodes is three-dimensional porous structure, and the specific surface area of the three-dimensional porous structure is 10~45cm2/cm3.The structure of the aluminium anodes is obturator-type, through-hole type or micro through hole type foam constructed of aluminium.The aperture of the closed pore foam aluminium is 2~25mm, and porosity is 65~98%；The aperture of the through-hole type foamed aluminium is 0.01mm~5mm, and porosity is 84~95%；The aperture of the micro through hole type foamed aluminium is 0.001mm~0.01mm, and porosity is 85~95%.Compared with prior art, the anode density of the porous anodized aluminum of the present invention program significantly reduces, and the utilization rate of aluminium and quality specific power are substantially improved.
Description
Technical field
The present invention relates to field of new energy technologies, and in particular to a kind of porous anodized aluminum and aluminium-air cell.
Background technique
It is cathode that aluminium-air cell, which is with raffinal (Al), oxygen is anode, with potassium hydroxide (KOH) or sodium hydroxide
(NaOH) aqueous solution is a kind of battery of electrolyte, since it is with theoretical specific capacity height (2.98Ahg-1), specific energy it is big
(8100Wh·kg-1), resourceful, lower production costs, it is environmentally protective the advantages that, have become at present alternative energy source storage equipment
Hot spot.However, due to aluminium anodes in aqueous electrolyte (aqueous solution of NaOH, KOH, NaCl etc.) there are passivation phenomenon and
Liberation of hydrogen self-corrosion is serious, so that the discharge rate of aluminium anodes is compared with slow, utilization rate is low, aluminium-air cell is difficult in higher current density
Lower electric discharge, the power density of battery are low, it is difficult to meet the needs of high power discharge.
The power density of metal-air battery and the contact area of metal electrode and electrolyte solution are closely related, improve gold
The power density of battery discharge can be improved in the specific surface area for belonging to electrode.Existing aluminium-air cell anode is dense form flat aluminum,
Electrode surface is smooth, smooth, and the contact area of electrode and electrolyte is essentially fixed value, in the electric discharge rate of dissolution one of aluminium alloy
Periodically, the power density of aluminium-air cell can not change.Chinese invention patent CN105057679B discloses a kind of aluminium air electricity
The preparation method of pond aluminum alloy anode metal plate, this method are made using aluminium skimmings as raw material through compaction moulding, heat treatment, thermal spraying
Aluminum alloy anode metal plate, gained aluminium skimmings version surface has gap, big with the contact area of electrolyte, and it is anti-to enhance electrode discharge
It answers.Institutes Of Technology Of Taiyuan Yang Wen logical Master's thesis " alkaline aluminium-air cell electrode research " once inquired into aluminium anodes foamed to it
The influence of performance, but the closed pore foam aluminium more because of, impurities lower using purity, so can not be by foam electrode
It is compared with fine aluminium electrode.Existing research shows that metal electrode foamed is conducive to improve battery for metal-air battery
Electric current or power, while reduce anode self-corrosion, improve anode utilization rate.However, but there has been no can be real in the prior art
Now reduce anode self-corrosion, improve anode utilization rate foam aluminium anodes specific structure relevant report.
Summary of the invention
The technical problems to be solved by the present invention are: providing one kind is capable of increasing anode material and electrolyte solution contacts face
Long-pending approach, the power for being capable of increasing anode reaction electric current and battery by promoting galvanic anode active area, is conducive to simultaneously
Self-corrosion behavior, activity of conversion substance and the utilization rate and battery specific capacity that improve anode for inhibiting aluminium anodes, solve existing
The problem of aluminium-air cell anode specific surface area is not high in technology, cell power density is low, aluminium anodes utilization rate.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention are as follows: a kind of porous anodized aluminum, the aluminium anodes
Structure be three-dimensional porous structure, the specific surface area of the three-dimensional porous structure is 10~45cm2/cm3。
Further, the structure of the aluminium anodes is obturator-type, through-hole type and/or micro through hole type foam constructed of aluminium.
Further, the aperture of the closed pore foam aluminium is 2~25mm, and porosity is 65~98%；The through-hole type
The aperture of foamed aluminium is 0.01mm~5mm, and porosity is 84~95%；The aperture of the micro through hole type foamed aluminium is 0.001mm
~0.01mm, porosity are 85~95%.
Further, the aluminium anodes contains the Al that mass percent is 80.0%~99.95%, also containing Zn, Sn and
At least one of Ga.
Further, if so, the content of the Zn is 0.01%~5.0%；If so, the content of Sn is 0.01~3.0%；
If so, the content of Ga is 0.0001%~0.5%.
Further, the aluminium anodes also contains one or both of Mg and In, and the content of the Mg is 0.01%~
The content of 5.0%, the In are 0.01%~0.5%.
Further, the aluminium anodes further includes the component of following mass percent: Ti 0.0001%~3.0%, Ca
0.01%~2%, Mn 0.001~0.05%, Pb 0.0001~0.1%.
Further, impurity is also contained in the aluminium anodes, the impurity includes one in Cu, Fe, Cr, Ni, Si, V, P
Kind is a variety of, and the mass percentage of the impurity is 0.0016%~0.45%.
Further, if so, the mass percentage of the Cu is 0.001~0.05%；If so, the quality hundred of the Fe
Dividing content is 0.0001~0.05wt%；If so, the mass percentage of the Cr is 0.0001~0.05wt%；If so, institute
The mass percentage for stating Ni is 0.0001~0.05wt%；If so, the mass percentage of the Si be 0.0001~
0.05wt%；If so, the mass percentage of the V is 0.0001~0.05wt%；If so, the mass percentage of the P
For 0.0001~0.05wt%.
Further, the foam constructed of aluminium of the porous anodized aluminum uses foam melt method, infiltration casting or powder smelting
Golden method is prepared.
The beneficial effects of the present invention are: porous anodized aluminum of the invention uses three-dimensional porous structure, has big ratio table
Area substantially increases the contact area of anode and electrolyte solution, to increase the area specific power of aluminium-air cell；
Specific surface area is 10~45cm2/cm3Three-dimensional porous structure aluminium anodes while increasing with the contact area of electrolyte, also drop
The low density of aluminium anodes (can make anode density be reduced to 0.1~1.0g/cm3), to increase the quality of aluminium-air cell
Specific power, compared with prior art, the aluminium-air cell short-circuit current density that the porous anodized aluminum of structure of the invention is prepared
It is higher.
The invention also includes more than one to state the aluminium-air cell that porous anodized aluminum is anode.
The beneficial effects of the present invention are: the aluminium-air cell prepared using the aluminium anodes of the present invention program, short circuit current
Density and quality specific power are substantially improved.
Detailed description of the invention
Fig. 1 is the aluminium-air cell in the comparative example and Examples 1 to 2 of the embodiment of the present invention under different operating voltage
Polarization curve and power density-current density plot；
Fig. 2 is voltage-specific capacity of the aluminium-air cell in constant-current discharge in comparative example of the present invention and Examples 1 to 2
Curve.
Specific embodiment
To explain the technical content, the achieved purpose and the effect of the present invention in detail, below in conjunction with embodiment and cooperate attached
Figure is explained.
A kind of porous anodized aluminum, the structure of the aluminium anodes are three-dimensional porous structure, the ratio table of the three-dimensional porous structure
Area is 10~45cm2/cm3。
The beneficial effects of the present invention are: porous anodized aluminum of the invention uses three-dimensional porous structure, has big ratio table
Area substantially increases the contact area of anode and electrolyte solution, to increase the area specific power of aluminium-air cell；
Specific surface area is 10~45cm2/cm3Three-dimensional porous structure aluminium anodes while increasing with the contact area of electrolyte, also drop
The low density of aluminium anodes (can make anode density be reduced to 0.1~1.0g/cm3), to increase the quality of aluminium-air cell
Specific power, compared with prior art, the aluminium-air cell short-circuit current density that the porous anodized aluminum of structure of the invention is prepared
It is higher.
Further, the structure of the aluminium anodes is obturator-type, through-hole type and/or micro through hole type foam constructed of aluminium.
Further, the aperture of the closed pore foam aluminium is 2~25mm, and porosity is 65~98%；The through-hole type
The aperture of foamed aluminium is 0.01mm~5mm, and porosity is 84~95%；The aperture of the micro through hole type foamed aluminium is 0.001mm
~0.01mm, porosity are 85~95%.
Further, the aluminium anodes contains the Al that mass percent is 80.0%~99.95%, also containing Zn, Sn and
At least one of Ga.
Further, if so, the content of the Zn is 0.01%~5.0%；If so, the content of Sn is 0.01~3.0%；
If so, the content of Ga is 0.0001%~0.5%.
Further, the aluminium anodes also contains one or both of Mg and In, if so, the content of the Mg is
0.01%~5.0%；If so, the content of the In is 0.01%~0.5%.
As can be seen from the above description, the beneficial effects of the present invention are: the Zn element liberation of hydrogen with higher of the present invention program
Overpotential can reduce the liberation of hydrogen side reaction of aluminium anodes, improve the utilization rate of aluminium anodes.But Zn element will increase the anode of aluminium anodes
Polarization, reduces the power output of aluminium-air cell.Mg element advantageously reduces the anode polarization of aluminium anodes dissolution, improves aluminium anodes
Current density, but Mg easily reacted with Al generate have cathode characteristic intermediate product Mg5Al18, lead to intercrystalline corrosion, reduce
The utilization rate of aluminium anodes.Sn element can make aluminium surface passivating film generate hole, destroy passivating film, reduce the resistance of aluminium anodes dissolution
Power, while overpotential of hydrogen evolution with higher, can effectively inhibit gas-evolving electrodes.Ga element can prevent aluminium surface from generating passivation
Film changes aluminium grain anisotropy present in course of dissolution, to make aluminium anodes corrosion uniformly, chemical property is also obtained
Improve.The addition of In element is also easy to produce segregation phase, forms activation site, promotes the aluminum substrate of surrounding to dissolve, dissolve simultaneously
In in the solution3+Being deposited on aluminum substrate surface makes aluminum substrate and oxidation UF membrane, is conducive to anode activation, but easily causes aluminium positive
The utilization rate of pole reduces.Therefore, one of Mg, Zn, Sn, Ga and In or a variety of are added in foamed aluminium, using between element
Mutual containing enables aluminium anodes to effectively inhibit liberation of hydrogen self-corrosion, and is conducive to active material conversion, also improves simultaneously
The utilization rate of aluminium anodes and the specific discharge capacity of battery.
Further, the aluminium anodes further includes the component of following mass percent: Ti 0.0001%~3.0%, Ca
0.01%~2%, Mn 0.001~0.05%, Pb 0.0001~0.1%.
Further, impurity is also contained in the aluminium anodes, the impurity includes one in Cu, Fe, Cr, Ni, Si, V, P
Kind is a variety of, and the mass percentage of the impurity is 0.0016%~0.45%.
Further, if so, the mass percentage of the Cu is 0.001~0.05%；If so, the quality hundred of the Fe
Dividing content is 0.0001~0.05wt%；If so, the mass percentage of the Cr is 0.0001~0.05wt%；If so, institute
The mass percentage for stating Ni is 0.0001~0.05wt%；If so, the mass percentage of the Si be 0.0001~
0.05wt%；If so, the mass percentage of the V is 0.0001~0.05wt%；If so, the mass percentage of the P
For 0.0001~0.05wt%.
Further, the foam constructed of aluminium of the porous anodized aluminum uses foam melt method, infiltration casting or powder smelting
Golden method is prepared.
As can be seen from the above description, the beneficial effects of the present invention are: the production technology of foamed aluminium is increasingly mature, and the present invention adopts
Foamed aluminium only need to be during preparing melt or preparing powder according to component requirements, the powder of metallic addition needed for being added
Last (Zn, Mg, Sn, Ga, In etc.).
The invention also includes more than one to state the aluminium-air cell that porous anodized aluminum is anode.
As can be seen from the above description, the beneficial effects of the present invention are: the aluminium prepared using the aluminium anodes of the present invention program is empty
Pneumoelectric pond, short-circuit current density and quality specific power are substantially improved.
The embodiment of the present invention one are as follows: (chemical component is Al 95.16%, Ti with closed-cell aluminum foam made from foam melt method
0.85%, Ca 1.78%, Mg 1.72%, Zn 0.14%, Ga 0.015%, In 0.037%, Fe 0.018%, Si
0.05%, Mn 0.042%, Pb 0.096%, Cu 0.037%, Ni0.0033%, Cr 0.0014%, V 0.0083wt%, P
0.042%, aperture is 3~8mm, porosity 82.4%, density 0.44g/cm3) it is anode, commerical grade α-MnO2For cathode
Catalyst, 4mol/L NaOH solution are electrolyte solution, are assembled into aluminium-air cell.
The embodiment of the present invention two are as follows: with through-hole type foamed aluminium made from powder metallurgic method (chemical component be Al 91.23%,
Ti 0.0001%, Ca 0.015%, Mg 3.72%, Zn 4.61%, Ga 0.34%, In 0.045%, Fe 0.0018%,
Si 0.0051%, Mn 0.0063%, Pb 0.0056%, Cu 0.0068%, Ni0.0035%, Cr 0.0019%, P
0.0045%, V 0.0044%, aperture are 0.1~1mm, porosity 79.2%, density 0.52g/cm3) it is anode, commodity
Grade α-MnO2For cathod catalyst, 4mol/L NaOH solution is electrolyte solution, is assembled into aluminium-air cell.
Reference examples are as follows: with purity be that (chemical component is Al 99.9% to 99.9% flat aluminum, Ti 0.015%, Ca
0.0036%, Mg 0.0007%, Zn 0.0096%, Ga 0.017%, Fe 0.021%, Si 0.03%, Cu
0.0007%, Cr 0.0009%, Ni 0.0015%) it is anode, with commerical grade α-MnO2For cathod catalyst, 4mol/L
NaOH solution is electrolyte solution, is assembled into aluminium-air cell.
Aluminium-air cell made from Examples 1 to 2 and comparative example is subjected to electric performance test, specific as follows:
1, each aluminium-air cell is measured in 200mA/cm2Operating voltage and discharge capacity under operating current, obtain battery
Discharge voltage-specific capacity curve is as shown in Figure 1；
2, current density of each aluminium-air cell under different operating voltages is measured, the polarization curve and power of battery are obtained
Density-current density plot is as shown in Figure 2.
As can be seen that the anode of comparative example is fine and close flat aluminum from Fig. 1 and Fig. 2, the short-circuit current density of battery is
360.7mA/cm2, specific discharge capacity 1810mAh/g, maximum area specific power is 136.2mW/cm2, quality specific power is
100.8mW/g (by the Mass Calculation of aluminium anodes)；The anode of embodiment 1 is closed-cell aluminum foam, the short-circuit current density of battery
For 492mA/cm2, specific discharge capacity 2556mAh/g, maximum area specific power is 169.8mW/cm2, quality specific power is
771.8mW/g (by the Mass Calculation of aluminium anodes)；The anode of embodiment 2 is fine-crystal spume aluminium alloy, the short-circuit current density of battery
For 803.5mA/cm2, specific discharge capacity 2375mAh/g, maximum area specific power is 296.8mW/cm2, quality specific power is
1141.5mW/g (by the Mass Calculation of aluminium anodes).
The short-circuit current density of closed pore foam aluminium anode is increased compared to conventional fine and close flat aluminum in embodiment 1
36% or more, and through-hole type foamed aluminium then increases 122% in embodiment 2；The quality of closed pore foam aluminium anode in embodiment 1
Specific power increases 6.65 times compared to conventional fine and close flat aluminum, and through-hole type foamed aluminium then increases 11.3 in embodiment 2
Times；The electrochemical equivalent of metallic aluminium is 2980mAh/g, and the utilization rate of aluminium is only 60.7% in comparative example, and closed pore in embodiment 1
The utilization rate of type foamed aluminium is up to being 85.7%, and the through-hole type foamed aluminium in embodiment 2 is up to 79.7%.
When foam melt method and powder metallurgic method prepare foamed aluminium in the embodiment of the present invention, operating procedure is routinely operated
It is designed with conventional parameter, unknown act in text.
In conclusion a kind of porous anodized aluminum provided by the invention and aluminium-air cell, compared with prior art, the present invention
The anode density of the porous anodized aluminum of scheme significantly reduces, and the utilization rate of aluminium and quality specific power are substantially improved.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalents made by bright specification and accompanying drawing content are applied directly or indirectly in relevant technical field, similarly include
In scope of patent protection of the invention.
Claims (10)
1. a kind of porous anodized aluminum, it is characterised in that: the structure of the aluminium anodes is three-dimensional porous structure, the three-dimensional porous knot
The specific surface area of structure is 10~45cm2/cm3。
2. porous anodized aluminum according to claim 1, it is characterised in that: the structure of the aluminium anodes is obturator-type, through-hole
Type and/or micro through hole type foam constructed of aluminium.
3. porous anodized aluminum according to claim 2, it is characterised in that: the aperture of the closed pore foam aluminium be 2~
25mm, porosity are 65~98%；The aperture of the through-hole type foamed aluminium is 0.01mm~5mm, and porosity is 84~95%；Institute
The aperture for stating micro through hole type foamed aluminium is 0.001mm~0.01mm, and porosity is 85~95%.
4. porous anodized aluminum according to claim 1, it is characterised in that: the aluminium anodes contains mass percent and is
80.0%~99.95% Al, also containing at least one of Zn, Sn and Ga.
5. porous anodized aluminum according to claim 4, it is characterised in that: the aluminium anodes also contains one of Mg and In
Or two kinds, if so, the content of the Mg is 0.01%~5.0%；If so, the content of the In is 0.01%~0.5%.
6. porous anodized aluminum according to claim 4, it is characterised in that: the aluminium anodes further includes following mass percent
Component: Ti 0.0001%~3.0%, Ca 0.01%~2%, Mn 0.001~0.05%, Pb 0.0001~0.1%.
7. porous anodized aluminum according to claim 4, it is characterised in that: the aluminium anodes further includes following mass percent
Component: also contain impurity in the aluminium anodes, the impurity includes at least one of Cu, Fe, Cr, Ni, Si, V, P, described
The mass percentage of impurity is 0.0016%~0.45%.
8. porous anodized aluminum according to claim 7, it is characterised in that: if so, the mass percentage of the Cu is
0.001~0.05%；If so, the mass percentage of the Fe is 0.0001~0.05wt%；If so, the quality hundred of the Cr
Dividing content is 0.0001~0.05wt%；If so, the mass percentage of the Ni is 0.0001~0.05wt%；If so, institute
The mass percentage for stating Si is 0.0001~0.05wt%；If so, the mass percentage of the V be 0.0001~
0.05wt%；If so, the mass percentage of the P is 0.0001~0.05wt%.
9. porous anodized aluminum according to claim 2, it is characterised in that: the foam constructed of aluminium of the porous anodized aluminum uses
Foam melt method, infiltration casting or powder metallurgic method are prepared.
10. a kind of using such as described in any item porous anodized aluminums of claim 1-9 as the aluminium-air cell of anode.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110551911A (en) * | 2019-09-27 | 2019-12-10 | 中南大学 | micron-pore capillary structure foamed aluminum block with high water absorption |
| CN114086205A (en) * | 2021-11-17 | 2022-02-25 | 中南大学 | Preparation method of foam metal-based modified material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110551911A (en) * | 2019-09-27 | 2019-12-10 | 中南大学 | micron-pore capillary structure foamed aluminum block with high water absorption |
| CN114086205A (en) * | 2021-11-17 | 2022-02-25 | 中南大学 | Preparation method of foam metal-based modified material |
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