CN103618093A - Heat treatment method for aluminum alloy anodic material of aluminum battery - Google Patents

Heat treatment method for aluminum alloy anodic material of aluminum battery Download PDF

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CN103618093A
CN103618093A CN201310532523.6A CN201310532523A CN103618093A CN 103618093 A CN103618093 A CN 103618093A CN 201310532523 A CN201310532523 A CN 201310532523A CN 103618093 A CN103618093 A CN 103618093A
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aluminum alloy
heat treatment
treatment method
alloy anode
aluminum
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马正青
曾波伟
滕昭阳
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Central South University
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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
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • 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

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Abstract

The invention discloses a heat treatment method for an aluminum alloy anodic material of an aluminum battery. The method comprises the following steps: putting a plastically-deformed aluminum alloy into an electric resistance furnace with a temperature of 230 to 260 DEG C, maintaining the temperature for 3 to 6 hours, taking out the aluminum alloy, and cooling to the room temperature in the air. The heat treatment method has the advantages of simple technology method and convenient operation. Through controlling the annealing temperature and annealing time of the aluminum alloy and modulating the organization form and secondary phase distribution, the method can obtain an aluminum alloy material with excellent electrochemical comprehensive properties of stable negative working potential, low hydrogen releasing speed, and uniform corrosion. The heat treatment method is suitable for being applied in industry.

Description

A kind of aluminum cell aluminum alloy anode material heat treatment method
Technical field
The present invention relates to a kind of anode material heat treatment method of long-time, high-power deposit chemical power source: refering in particular to is a kind of aluminum cell aluminum alloy anode material heat treatment method, and the aluminum alloy anode material of preparation can be applicable to aluminium-silver oxide cell, aluminium-air cell as anode material.
Technical background
Metallic aluminium is as anode material, and its electrode potential is negative, is-2.35V(vs SHE in alkaline medium), specific energy is high, cheap, good processability and aboundresources, and aluminium anodes weight ratio capacity is 2.98Ah/g, is only second to lithium; And volume and capacity ratio is 8.05Ah/cm 3, higher than other all metal materials, be desirable anode material, can be widely used in aluminium-air cell, aluminium-silver oxide cell.
Aluminium is that the electrochemical power source of anode has compared with other batteries that monomer voltage is high, specific energy is high, energy density is large, can banish greatly the advantages such as electricity, fail safe height.As take aluminium alloy as anode, and silver oxide is anodal aluminium-silver oxide cell, and theoretical specific energy reaches 1090Wh/kg, and actual specific energy can reach 300～400Wh/kg, and this numerical value is far above the specific energy of current various batteries.Although Li/SOCl 2the specific energy of battery is suitable therewith, but its fail safe is bad, and this makes it cannot be for electrokinetic cell.Specific power is high, and actual specific power reaches 50～200W/kg, higher than the specific power of hydrogen oxygen fuel cell, and this characteristic is obviously to be determined by aluminium electrode.Metallic aluminium anodic current efficiency is greater than 96%, and monomer operating voltage is 1000mA/cm in current density 2time still can remain on about 1.6V, can work long hours during low discharging current simultaneously.Al/AgO battery safety is good, has anode material cheap and nontoxic, easily preserves the advantages such as Maintenance free.
Aluminium alloy is a kind of novel high specific energy battery as the Al-air cell of anode, has the actual specific energy up to 300～400Wh/kg, and far above other metal-airs, aluminium, with its unique advantage, will become the preferred material of metal-air battery anode.The features such as aluminium-air cell has high specific energy, long service life, safety non-pollution, aboundresources, cost is low, activationary time is short, as electrical source of power, field power supply, undersea ship, monitor, UUV and the driving power of diving facility and the driving powers of electric automobile such as communication network station in developed countries such as America and Europes, have been used for.
In known foreign literature, mainly studied and in aluminum alloy anode, added alloying element and mainly comprise as In, Bi, Mn, Mg, Zn, Ga, Sn, Sb, Pb, Cd, Tl and Hg etc., the BDW(Al-1Mg-0.1In-0.2Mn preparing as A.Maimoni in 1985) alloy, at 60 ℃ of 4mol/L NaOH+1mol/L Al(OH) 3in solution, Open Circuit Potential is-1.78V(vs. Gong ∕ mercuric oxide electrode, Hg/HgO), and at 600mA/cm 2under anode polarization current potential be-1.56V, current efficiency≤98%; The patent of the Al-0.45Mn-0.085Sn of the application such as Hunter, in 80 ℃ of 25%KOH+3.5NaCl solution, at 645mA/cm 2under anode polarization current potential be-1.52V(vs.Hg/HgO), the Al-Ga-In-Zn-Mg-Mn series alloys anode of the domestic southwestern Chinalco in its current efficiency>=98%. development, at 80%4mol/LNaOH+2.8mol/NaAlO 2in+corrosion inhibiter medium, current density is 620mA/cm 2under anode polarization current potential be-1.55V(vs.Hg/HgO), current efficiency>=96%.Yet the aluminum alloy anode material relating in above-mentioned patent or research is high current density (>=600mA/cm on the one hand 2) operating voltage is not high, on the other hand, aluminum alloy anode is in actual battery environment, and liberation of hydrogen corrosion rate is large, and practical efficiency is not high; Aluminum alloy anode only carries out stress relief annealing processing by the sheet material after its rolling before reality is used, and heat treatment method does not have relevant report to the research of aluminum alloy anode material for battery performance.
Summary of the invention
The object of the invention is to overcome the deficiency of prior art and provide a kind of process simple, easy to operate, by controlling aluminium alloy annealing temperature, annealing time, regulate the tissue morphology of aluminum alloy plate materials and the distribution of second-phase, obtain the aluminum cell aluminum alloy anode material heat treatment method that steady operation current potential is negative, liberation of hydrogen speed is low, corrode the aluminum alloy anode material of uniform electrochemistry high comprehensive performance.
A kind of aluminum cell of the present invention aluminum alloy anode material heat treatment method, is by the 230-260 ℃ of insulation 3-6 hour in resistance furnace of the aluminium alloy after plastic deformation, takes out air cooling to room temperature.
A kind of aluminum cell of the present invention aluminum alloy anode material heat treatment method, described Al-Mg-Pb-Sn-Ga aluminium alloy, by mass percentage, comprises that following component forms:
Figure BDA0000406140940000031
A kind of aluminum cell of the present invention aluminum alloy anode material heat treatment method, plastic deformation adopts hot rolling technology, hot rolling total deformation >=95%.
Mechanism of the present invention sketch under: cast metals is through plastic deformation, and under the acting in conjunction of tension stress and compression, along with the variation of metallic profiles, corresponding variation has occurred its inner grain shape, and as-cast structure is transformed into the micro-shape tissue of fibre of processing state; External force is to metal institute work, approximately have≤10% merit is converted into internal stress residue in metal, making can increase in metal, work hardening, residual stress increase, thereby cause its burn into chemical property to change, liberation of hydrogen corrosion rate and the electrode potential of aluminum alloy anode material change.The present invention is by holding temperature and the time of strict controlled rolling state aluminium alloy, the fine micro-tissue of rolling state aluminum alloy anode material lath-shaped is disappeared, form " primary crystal " that low-angle sub boundary and disperse distribute, change the distribution of its interior tissue and second-phase, residualinternal stress is eliminated substantially, finally obtains that a kind of operating potential is negative, liberation of hydrogen corrosion rate is low, the aluminum alloy anode material of the uniform high comprehensive performance of surface corrosion.
Aluminum alloy heat treatment technology involved in the present invention compared with prior art has the following advantages: process is simple, easy to operate, by controlling aluminium alloy annealing temperature, annealing time, regulate the tissue morphology of aluminum alloy plate materials and the distribution of second-phase, obtain the aluminum alloy anode material that steady operation current potential is negative, liberation of hydrogen speed is low, corrode uniform electrochemistry high comprehensive performance.
Accompanying drawing explanation
Accompanying drawing 1 is that comparative example is without the microscopic structure of five yuan of aluminum alloy anode sheet materials of heat treated Al-Mg-Pb-Sn-Ga.
Accompanying drawing 2 is that comparative example is without the erosion profile of five yuan of aluminum alloy anode sheet materials of heat treated Al-Mg-Pb-Sn-Ga.
Accompanying drawing 3 is the microscopic structure of five yuan of aluminum alloy anode sheet materials of Al-Mg-Pb-Sn-Ga of embodiment 1.
Accompanying drawing 4 is the erosion profile of five yuan of aluminum alloy anode sheet materials of Al-Mg-Pb-Sn-Ga of embodiment 1.
Accompanying drawing 5 is the microscopic structure of five yuan of aluminum alloy anode sheet materials of Al-Mg-Pb-Sn-Ga of embodiment 2.
Accompanying drawing 6 is the erosion profile of five yuan of aluminum alloy anode sheet materials of Al-Mg-Pb-Sn-Ga of embodiment 2.
Accompanying drawing 7 is the microscopic structure of five yuan of aluminum alloy anode sheet materials of Al-Mg-Pb-Sn-Ga of embodiment 3.
Accompanying drawing 8 is the erosion profile of five yuan of aluminum alloy anode sheet materials of Al-Mg-Pb-Sn-Ga of embodiment 3.
Accompanying drawing 9 is the microscopic structure of five yuan of aluminum alloy anode sheet materials of Al-Mg-Pb-Sn-Ga of embodiment 4.
Accompanying drawing 10 is the erosion profile of five yuan of aluminum alloy anode sheet materials of Al-Mg-Pb-Sn-Ga of embodiment 4.
Accompanying drawing 11 is the microscopic structure of five yuan of aluminum alloy anode sheet materials of Al-Mg-Pb-Sn-Ga of embodiment 5.
Accompanying drawing 12 is the erosion profile of five yuan of aluminum alloy anode sheet materials of Al-Mg-Pb-Sn-Ga of embodiment 5.
From Fig. 1,2, can find out, the microscopic structure that five yuan of aluminum alloy anode materials are rolled state is fibrous, has higher processing internal stress, and the liberation of hydrogen speed of alloy is large, corrode inhomogeneous, stable potential calibration;
From Fig. 3,4, can find out, 230 ℃-3h annealed alloy fibr tissue border in slow disappearance, occur to distribute, tiny unstable state subgrain tissue, residualinternal stress reduces, liberation of hydrogen speed diminishes, corrosion all with, stable potential is born and is moved;
From Fig. 5,6, can find out, 230 ℃-6h annealed alloy fibr tissue substantially disappear, there is disperse and be uniformly distributed, tiny unstable state subgrain tissue, residualinternal stress is eliminated substantially, liberation of hydrogen speed is less, evenly, stable potential is negative moves in corrosion;
From Fig. 7,8, can find out, 260 ℃-3h annealed alloy tissue and 230 ℃-6h annealing is resulting, and to organize similar be that fibr tissue disappears, and subgrain is grown up, the crystal grain that forming section is tiny, residualinternal stress is eliminated substantially, liberation of hydrogen rate reduction, evenly, stable potential is negative moves in corrosion;
From Fig. 9,10, can find out, 260 ℃-6h annealed alloy tissue and 230 ℃-3h annealing is resulting, and to organize similar be that fibr tissue disappears, and subgrain is grown up, the crystal grain that forming section is tiny, residualinternal stress is eliminated substantially, liberation of hydrogen rate reduction, evenly, stable potential is negative moves in corrosion;
From Figure 11,12, can find out, 300 ℃ and above annealing, crystal grain becomes greatly gradually, generates thick uniform crystal grain, and second-phase is separated out at crystal boundary, corrodes inhomogeneously, and the liberation of hydrogen speed of five aluminum alloy anode materials increases, and the negative degree of moving of stable potential reduces.
From Fig. 3-12, alloy material is at 230 ℃～260 ℃, and the liberation of hydrogen speed of the five yuan of aluminum alloy anode materials of Al-Mg-Pb-Sn-Ga that obtain under the final annealing technique of insulation 3h～6h is minimum, operating potential negative, combination property is best.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further described.
In the embodiment of the present invention, the component proportion of aluminium alloy is: Mg0.5%, and Pb0.1%, Sn0.1%, Ga0.05%, surplus is Al.
Comparative example
Five yuan of aluminum alloy anode materials of Al-Mg-Pb-Sn-Ga that the rolling reduction of take is 95% are raw material, without any heat treatment, directly carry out electrochemistry experiment.
Embodiment 1
Five yuan of aluminum alloy anode materials of Al-Mg-Pb-Sn-Ga that the rolling reduction of take is 95% are raw material, and 230 ℃ of insulation 3h in air resistance furnace, obtain the final aluminum alloy anode material that obtains.
Embodiment 2
Five yuan of aluminum alloy anode materials of Al-Mg-Pb-Sn-Ga that the rolling reduction of take is 95% are raw material, and 230 ℃ of insulation 6h in air resistance furnace, obtain the final aluminum alloy anode material that obtains.
Embodiment 3
Five yuan of aluminum alloy anode materials of Al-Mg-Pb-Sn-Ga that the rolling reduction of take is 95% are raw material, and 260 ℃ of insulation 3h in air resistance furnace, obtain the final aluminum alloy anode material that obtains.
Embodiment 4
Five yuan of aluminum alloy anode materials of Al-Mg-Pb-Sn-Ga that the rolling reduction of take is 95% are raw material, and 260 ℃ of insulation 6h in air resistance furnace, obtain the final aluminum alloy anode material that obtains.
Embodiment 5
Five yuan of aluminum alloy anode materials of Al-Mg-Pb-Sn-Ga that the rolling reduction of take is 95% are raw material, and 300 ℃ of insulation 6h in air resistance furnace, obtain the final aluminum alloy anode material that obtains.
Liberation of hydrogen rate test method: collect sample at 4mol/LNaOH+10g/LNa with drainage 2snO 3the hydrogen-separating quantity of unit are, unit interval inside in medium, calculates liberation of hydrogen speed.
The volume ÷ time ÷ specimen surface of liberation of hydrogen speed=gas is long-pending;
The method of testing of chemical property:
1, method of testing: galvanostatic polarization; Five yuan of aluminum alloy plate materials of anode: Al-Mg-Pb-Sn-Ga, work area: 4.0cm 2; Reference electrode: Hg/HgO; Auxiliary electrode: platinum, area is 10.0cm 2.
2, experimental condition:
(1) (80 ± 3) ℃ 4mol/LNaOH+10g/LNa 2snO 3, discharge current density: 800mA/cm 2, the testing time: 30min;
(2) (25 ± 3) ℃ 4mol/L NaOH+10g/L Na 2snO 3, discharge current density: 200mA/cm 2, the testing time: 60min.
The chemical property parameter of the embodiment of the present invention and comparative example is in Table 1
The chemical property of five yuan of aluminum alloy anode materials of table 1Al-Mg-Pb-Sn-Ga
Figure BDA0000406140940000081
From above parameter, the liberation of hydrogen speed of five yuan of aluminum alloy materials of Al-Mg-Pb-Sn-Ga that alloy material obtains under the final thermal anneal process method of 230-260 ℃-3h～6h is minimum, operating potential negative, combination property is best.

Claims (3)

1. an aluminum cell aluminum alloy anode material heat treatment method, is that the air cooling of coming out of the stove is to room temperature by the 230-260 ℃ of insulation 3-6 hour in resistance furnace of the aluminum alloy anode sheet material after plastic deformation.
2. a kind of aluminum cell aluminum alloy anode material heat treatment method according to claim 1, is characterized in that: described aluminum alloy anode material, and batching by mass percentage, comprises that following component forms:
Figure FDA0000406140930000011
3. a kind of aluminum cell aluminum alloy anode material heat treatment method according to claim 1, is characterized in that: plastic deformation adopts hot rolling, hot rolling total deformation >=95%.
CN201310532523.6A 2013-10-31 2013-10-31 Heat treatment method for aluminum alloy anodic material of aluminum battery Pending CN103618093A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106756665A (en) * 2016-11-28 2017-05-31 云南冶金集团创能铝空气电池股份有限公司 Aluminium alloy, preparation method and purposes
CN108666561A (en) * 2018-05-16 2018-10-16 湖南源达新材料有限公司 A kind of air cell electrode material and preparation method thereof
CN116043077A (en) * 2023-01-16 2023-05-02 中南大学 High-cube-texture-content high-electrochemical-activity aluminum alloy negative electrode material and heat treatment method thereof

Citations (2)

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CN1108007A (en) * 1994-03-03 1995-09-06 胜利石油管理局钻井工艺研究院 Sea water or salt solution, aluminium-air battery and its producing method
US20120068107A1 (en) * 2010-09-20 2012-03-22 Korea Institute Of Science And Technology Recovery and synthesis method for metaloxidic cathodic active material for lithium ion secondary battery

Patent Citations (2)

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CN1108007A (en) * 1994-03-03 1995-09-06 胜利石油管理局钻井工艺研究院 Sea water or salt solution, aluminium-air battery and its producing method
US20120068107A1 (en) * 2010-09-20 2012-03-22 Korea Institute Of Science And Technology Recovery and synthesis method for metaloxidic cathodic active material for lithium ion secondary battery

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106756665A (en) * 2016-11-28 2017-05-31 云南冶金集团创能铝空气电池股份有限公司 Aluminium alloy, preparation method and purposes
CN108666561A (en) * 2018-05-16 2018-10-16 湖南源达新材料有限公司 A kind of air cell electrode material and preparation method thereof
CN116043077A (en) * 2023-01-16 2023-05-02 中南大学 High-cube-texture-content high-electrochemical-activity aluminum alloy negative electrode material and heat treatment method thereof
CN116043077B (en) * 2023-01-16 2023-08-15 中南大学 High-cube-texture-content high-electrochemical-activity aluminum alloy negative electrode material and heat treatment method thereof

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Application publication date: 20140305