CN101388457A - Aluminum alloy anode material for battery - Google Patents
Aluminum alloy anode material for battery Download PDFInfo
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- CN101388457A CN101388457A CNA2008101435240A CN200810143524A CN101388457A CN 101388457 A CN101388457 A CN 101388457A CN A2008101435240 A CNA2008101435240 A CN A2008101435240A CN 200810143524 A CN200810143524 A CN 200810143524A CN 101388457 A CN101388457 A CN 101388457A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses an aluminum alloy anode material of batteries, which uses aluminum whose purity is higher or equal to 99.99% as raw materials. Magnesium (Mg), stannum (Sn), gallium (Ga) and bismuth (Bi) are added, and the mass percentage of elements which are added is that Mg: 0.5-1.5%, Bi: 0.01-0.2%, Sn: 0.01-0.4%, Ga: 0.01-0.3%, and the mass content of impurities is equal to or less than 0.01%. The invention has the advantages of high operating factor of the cathode and the anode of a working potential, stable output of big power and even corrosion on the surface.
Description
Technical field
The present invention relates to a kind of long-time, high-power deposit chemical power source constituent material, refer in particular to aluminum alloy anode material for battery.
Background technology
Metallic aluminium is as anode material, and its electrode potential is negative, is-2.35V (vs SHE) in alkaline medium, specific energy height, cheap, good processability and aboundresources, and the aluminium anodes capacity is 2.98Ah/g, is only second to lithium; And its volume and capacity ratio is 8.05Ah/cm
3, be higher than other all metal materials, be desirable anode material.
The electrochemical power source that with aluminium is anode has advantages such as monomer voltage height, specific energy height, energy density be big than other battery.As aluminium/silver oxide cell, it is as the underwater propulsion system power source, specific energy can reach zinc-silver oxide cell and magnesium/chloride of silver cell 2～3 times under identical current density, and the metallic aluminium anodic current efficiency is greater than 90%, and electric propulsion system makes that the submarine system operation is more quiet.Aluminium/silver oxide cell is negative pole with the aluminum alloy anode, silver oxide is anodal, with the seawater that is dissolved with KOH or NaOH is electrolyte, adopted bipolarity plate electrode heap formula structure, theoretical specific energy is 1090Wh/kg, battery body actual specific energy can reach 260Wh/kg, and the monomer operating voltage is 1000mA/cm in current density
2In time, still can remain on about 1.6V, can work long hours during low discharging current simultaneously.The Al/AgO battery safety is good, and has anode material cheapness and nontoxic, preserves advantages such as Maintenance free easily, so become the first-selection of underwater operation and military battery.
Cathode material is all ripe or be tending towards ripe in the aluminum cell, and the critical material of decision aluminum cell performance is aluminum alloy anode material, all is in the state of maintaining complete secrecy for high-performance aluminium alloy anode material composition and manufacturing technology abroad at present.Because fine aluminium real work voltage in alkaline medium is lower, polarization and all very serious from corrosion, cause indexs such as its utilance, specific energy, specific power lower, and the hydrogen that produces of corrosion seriously influence the battery operate as normal certainly, can not use with metal anode as alkaline battery.For weakening or eliminating above-mentioned shortcoming, main solution route is for adding in pure aluminum substrate that suitable alloy element lowers its polarization and from corrosion rate, improve its anode utilance, increase its high-power output stability, long-time to be applicable to, high-power alkaline battery anode material.
In the known domestic and foreign literature, adding alloying element in the aluminum alloy anode mainly comprises as In, Bi, Mn, Mg, Zn, Ga, Sn, Sb, Pb, Cd, T1 and Hg etc., as the alloy of the BDW (Al-1Mg-0.1In-0.2Mn) of A.Maimoni in 1985 preparation, at 60 ℃ of 4mol/L NaOH+1mol/L Al (OH)
3In the solution, open circuit voltage is-1.78V (vs.Hg/HgO), at 600mA/cm
2Under the anode polarization current potential be-1.60V; The patent of the Al-0.45Mg-0.085Sn of application such as Hunter is in 80 ℃ of 25%KOH+3.5%NaCl solution, at 645mA/cm
2Under the anode polarization current potential be-1.52V (vs.Hg/HgO) its current efficiency 〉=99%.The Al-Ga-In-Zn-Mg-Mn series alloys anode of domestic southwestern Chinalco development is at 80 ℃ of 4mol/L NaOH+2.8mol/L NaAlO
2In+corrosion inhibiter the medium, current density is 620mA/cm
2Under the anode polarization current potential be-1.57V (vs.Hg/HgO).Yet related material high current density (〉=600mA/cm on the one hand in above-mentioned patent or the research
2) operating voltage is not high; On the other hand, aluminum alloy anode is in actual battery heap environment, and practical efficiency is not high.
Summary of the invention
Technical problem to be solved by this invention provides negative, the anode utilance height of a kind of operating potential, and high-power output is stable, the uniform aluminum alloy anode material for battery of surface corrosion.
In order to solve the problems of the technologies described above, aluminum alloy anode material for battery provided by the invention, aluminium with purity 〉=99.99% is raw material, adds element magnesium (Mg), tin (Sn), gallium (Ga) and bismuth (Bi), add element mass percent be: Mg:0.5～1.5%; Bi:0.01～0.2%; Sn:0.01～0.4%; Ga:0.01～0.3%; Impurity mass content≤0.01%.
Adopt the aluminum alloy anode material for battery of technique scheme; based on high-purity Al material, add Mg, Bi, Sn and the Ga element of trace, purpose is to destroy its fine and close alumina protective layer; improve its chemical property and surface dissolution uniformity, and reduce it from corrosion rate.Adopt common aluminum alloy anode manufacturing process to prepare five yuan of aluminum alloy anode materials of Al-Mg-Bi-Sn-Ga, smelting furnace is a resistance furnace, and melting kettle is a graphite crucible, and smelting temperature is 760 ℃, and solvent is the conventional aluminium solvent; After treating the complete fusion of aluminium ingot, add magnesium (Mg), tin (Sn), gallium (Ga) and bismuth (Bi) according to weight proportion, insulation is to melting fully, and graphite rod fully stirs, and casts from the water-cooled pig mold with leaving standstill, skim after the carbon trichloride degasification, watering.By strictness control alloy element magnesium, tin, gallium and the proportioning of bismuth and the content of impurity, can obtain that operating potential is negative, anode utilance height, and high-power output is stable, the uniform high-performance aluminium alloy anode material of surface corrosion.
The present invention adds an amount of alloying element Mg, Sn, Ga and Bi in the aluminium liquid after melting, founding becomes five yuan of aluminum alloy anodes of Al-Mg-Bi-Sn-Ga through being rolling to certain thickness sheet material, and it is at (80 ± 3) ℃ 4mol/LNaOH+10g/l Na
2SnO
3In the solution, Open Circuit Potential is defeated by-1.90V, current density 200mA/cm
2Under the anode polarization current potential be defeated by-1.80V (vs.Hg/HgO) electrode potential current density 800mA/cm
2Under the anode polarization current potential be defeated by-1.58V (vs.Hg/HgO) electrode potential, high-power output is stable, anode utilance 〉=96%.
Aluminum alloy anode material involved in the present invention is compared with prior art, has the following advantages: (1) chemical property is good, and Open Circuit Potential is negative, and output current is big, steady operation current potential height; (2) under the big current work condition, aluminum alloy anode utilance height.(3) can little electric current, long-time stable discharging.
Description of drawings
Fig. 1 is the surface topography of discharge back aluminum alloy anode sheet material.
Embodiment
The invention will be further described below in conjunction with drawings and Examples.
Embodiment 1:
Aluminium with purity 〉=99.99% is raw material, chooses each composition mass percent of aluminum alloy anode to be: Mg:1.5%, Bi:0.2%, Sn:0.4%, Ga:0.3% after preparing, adopts common aluminum alloy fusion casting and processing technology to prepare five yuan of aluminum alloy anode materials of Al-Mg-Bi-Sn-Ga.
Embodiment 2:
Aluminium with purity 〉=99.99% is raw material, chooses each composition mass percent of aluminum alloy anode to be: Mg:1.0%, Bi:0.01%, Sn:0.01%, Ga:0.01% after preparing, adopts common aluminum alloy fusion casting and processing technology to prepare five yuan of aluminum alloy anode materials of Al-Mg-Bi-Sn-Ga.
Embodiment 3:
Aluminium with purity 〉=99.99% is raw material, choosing each composition mass percent of aluminum alloy anode is: Mg:0.5%, Bi:0.025%, Sn:0.085%, Ga:0.035%, after preparing, adopt common aluminum alloy fusion casting and processing technology to prepare five yuan of aluminum alloy anode materials of Al-Mg-Bi-Sn-Ga.
Aluminum alloy anode chemical property detection method to preparation is:
(1) aluminum alloy anode sheet metal thickness after rolling is (0.5 ± 0.02) mm, and effectively work area is 1cm
2, reference electrode is mercury/mercury oxide (Hg/HgO) electrode, and auxiliary electrode is a graphite, and area is 4cm
2
(2) aluminum alloy anode sheet metal thickness after rolling is (0.5 ± 0.02) mm, and work area is 100cm
2, silver oxide (AgO) just very, area is 100cm
2
Test(ing) medium is (80 ± 3) ℃ 4mol/L NaOH+10g/lNa
2SnO
3Solution, discharging current are 200mA/cm
2And 800mA/cm
2, the testing time is 60min.Concrete chemical property sees Table 1.
Referring to Fig. 1, can find out that by above embodiment five yuan of aluminum alloy anode materials of Al-Mg-Bi-Sn-Ga of the present invention possess high chemical property and high-power output stability really, and uniform advantage such as surface dissolution.
Five yuan of aluminum alloy anode chemical properties of table 1 Al-Mg-Bi-Sn-Ga
| Anode material | Open Circuit Potential/V | 200mA/cm 2Operating potential/V | 800mA/cm 2Operating potential/V | 200mA/cm 2Battery operated voltage/the V of Al/AgO | 800mA/cm 2Battery operated voltage/the V of Al/AgO | The aluminum alloy anode utilance |
| Embodiment 1 | -1.901 | -1.785 | -1.601 | 1.89 | 1.68 | 96.2％ |
| Embodiment 2 | -1.862 | -1.736 | -1.585 | 1.84 | 1.65 | 95.1％ |
| Embodiment 3 | -1.879 | -1.761 | -1.590 | 1.86 | 1.66 | 96.6％ |
Claims (1)
1, a kind of aluminum alloy anode material for battery is characterized in that: the aluminium with purity 〉=99.99% is raw material, adds element magnesium (Mg), tin (Sn), gallium (Ga) and bismuth (Bi), add element mass percent be: Mg:0.5～1.5%; Bi:0.01～0.2%; Sn:0.01～0.4%; Ga:0.01～0.3%; Impurity mass content≤0.01%.
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|---|---|---|---|
| CNA2008101435240A CN101388457A (en) | 2008-11-07 | 2008-11-07 | Aluminum alloy anode material for battery |
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| CNA2008101435240A CN101388457A (en) | 2008-11-07 | 2008-11-07 | Aluminum alloy anode material for battery |
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| CN101388457A true CN101388457A (en) | 2009-03-18 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101901893A (en) * | 2010-08-06 | 2010-12-01 | 浙江巨科铝业有限公司 | Aluminum alloy anode material for battery and method for producing same |
| CN102820472A (en) * | 2012-08-07 | 2012-12-12 | 河南科技大学 | Manganese-aluminum containing anode material and preparation method thereof, as well as air cell prepared by using anode material |
| CN104018018A (en) * | 2014-06-04 | 2014-09-03 | 厦门火炬特种金属材料有限公司 | Processing method of novel Al-air fuel cell positive material Al-Sn-Bi-Mn |
| CN104451475A (en) * | 2014-12-15 | 2015-03-25 | 苏州宽温电子科技有限公司 | Aluminum alloy composite material and preparation method thereof |
| CN104561673A (en) * | 2014-12-30 | 2015-04-29 | 长安大学 | Rare-earth-modified aluminium alloy anode plate and preparation method thereof |
| CN105591089A (en) * | 2015-12-08 | 2016-05-18 | 黄静 | Magnesium battery |
| CN106917010A (en) * | 2017-04-25 | 2017-07-04 | 哈尔滨工业大学 | A kind of aluminum alloy anode material and its casting method and application |
| 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 |
| CN110484788A (en) * | 2019-09-06 | 2019-11-22 | 宁波烯铝新能源有限公司 | Aluminium-air cell anode material and preparation method thereof and aluminium-air cell |
| CN112599361A (en) * | 2020-12-14 | 2021-04-02 | 湖南大学 | Wide-temperature-range high-performance electrochemical energy storage device based on bismuth-based electrode |
-
2008
- 2008-11-07 CN CNA2008101435240A patent/CN101388457A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101901893A (en) * | 2010-08-06 | 2010-12-01 | 浙江巨科铝业有限公司 | Aluminum alloy anode material for battery and method for producing same |
| CN101901893B (en) * | 2010-08-06 | 2013-01-09 | 浙江巨科铝业有限公司 | Aluminum alloy anode material for battery and method for producing same |
| CN102820472A (en) * | 2012-08-07 | 2012-12-12 | 河南科技大学 | Manganese-aluminum containing anode material and preparation method thereof, as well as air cell prepared by using anode material |
| CN104018018B (en) * | 2014-06-04 | 2016-03-09 | 厦门火炬特种金属材料有限公司 | A kind of novel aluminum-air fuel cell anode material Al-Sn-Bi-Mn working method |
| CN104018018A (en) * | 2014-06-04 | 2014-09-03 | 厦门火炬特种金属材料有限公司 | Processing method of novel Al-air fuel cell positive material Al-Sn-Bi-Mn |
| CN104451475A (en) * | 2014-12-15 | 2015-03-25 | 苏州宽温电子科技有限公司 | Aluminum alloy composite material and preparation method thereof |
| CN104561673A (en) * | 2014-12-30 | 2015-04-29 | 长安大学 | Rare-earth-modified aluminium alloy anode plate and preparation method thereof |
| CN105591089A (en) * | 2015-12-08 | 2016-05-18 | 黄静 | Magnesium battery |
| CN106917010A (en) * | 2017-04-25 | 2017-07-04 | 哈尔滨工业大学 | A kind of aluminum alloy anode material and its casting method and application |
| CN106917010B (en) * | 2017-04-25 | 2018-11-13 | 哈尔滨工业大学 | A kind of aluminum alloy anode material and its casting method and application |
| 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 |
| CN110484788A (en) * | 2019-09-06 | 2019-11-22 | 宁波烯铝新能源有限公司 | Aluminium-air cell anode material and preparation method thereof and aluminium-air cell |
| CN112599361A (en) * | 2020-12-14 | 2021-04-02 | 湖南大学 | Wide-temperature-range high-performance electrochemical energy storage device based on bismuth-based electrode |
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Open date: 20090318 |