CN105057679A - Method for manufacturing aluminum alloy anode metal plate of aluminum-air battery - Google Patents
Method for manufacturing aluminum alloy anode metal plate of aluminum-air battery Download PDFInfo
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- CN105057679A CN105057679A CN201510578890.9A CN201510578890A CN105057679A CN 105057679 A CN105057679 A CN 105057679A CN 201510578890 A CN201510578890 A CN 201510578890A CN 105057679 A CN105057679 A CN 105057679A
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Abstract
The invention discloses a method for manufacturing an aluminum alloy anode metal plate of an aluminum-air battery, and belongs to the field of aluminum-air battery electrodes. Aluminum skimmings produced due to industrial aluminum machining are adopted to serve as raw materials, and the aluminum alloy anode metal plate is obtained in the steps that water drainage and oil removal are carried out, the skimmings are smashed, mixed with zinc powder, compacted and formed, and thermal treatment and thermal spraying are carried out. The aluminum skimmings produced due to metal cutting serve as the raw materials, so that the problem of waste aluminum recycle is solved, the process that the aluminum skimmings are electrolyzed again is omitted, and manufacturing cost of metal electrodes is reduced. The surface of an aluminum skimmings plate formed by pressing the aluminum skimmings is provide with holes, the specific contact area of electrolyte is large, and electrode discharge reaction is enhanced. Gallium, tin and bismuth are added and little in required amount, and electrode activity can be effectively improved.
Description
Technical field
The present invention relates to a kind of preparation method of aluminium-air cell aluminum alloy anode metallic plate, belong to aluminium-air cell electrode field.
Background technology
Aluminum metal electrode is the important component part of aluminium-air cell.Existing aluminium-air cell mainly adopts pure aluminum or aluminum alloy as metal electrode negative pole.No matter be fine aluminium or aluminium alloy, all need to use highly purified aluminum metal.Industry aluminium processed mainly adopts the method for electrolysis of aluminum oxide, and needed for electrolysis one ton of aluminium, cost is more than 16000 yuan, and cost is high, and this is the restriction business-like aspect of aluminium-air cell.
Fine aluminium contacts with oxygen and very easily generates fine and close oxide-film, as needing the oxide-film first consuming surface during electrode, reducing electrode activity, making electrode passivation.Meanwhile, fine aluminium easily from corrosion, causes electrode polarization in strong alkaline electrolytes, reduces open-circuit voltage, and reduces the capacity of battery.For this reason, alloying element can be added in fine aluminium, make anodizing film form defect, accelerate electrode reaction, and improve electrode corrosion resistance.
What current application was more has the quaternary alloy such as ternary alloy system, Al-Ga-Bi-Pb, Al-Ga-Sn-Bi system and other five yuan, the hexa-atomic alloy series such as the binary alloy system such as Al and Zn, Bi, Te, In, Ga, Tl, Al-Ga-Mg and Al-In-Mg.Alloying element is more, and activity and the corrosion resistance of electrode are stronger, but the element prices such as Bi, Te, In, Ga of comprising in multicomponent alloy system are high, cause the cost of multicomponent alloy anode high.Even in binary alloy system, also only have the price of zinc lower.But bianry alloy effect is far below multicomponent alloy, and alloying element as zinc can only intensifier electrode active, resist corrosive raising and not obvious.
The current efficiency of aluminium-air cell is relevant with the ratio contact area between electrolyte and metal electrode board, increases metal electrode and can increase electrode discharge intensity with electrolytical than contact area.And existing aluminium-air cell anode, electrode surface is smooth, and the ratio contact area between metal electrode and electrolyte is certain value, and strength of discharge cannot change.
Summary of the invention
The present invention is directed to aluminium-air cell metal electrode cost of manufacture high, the problems such as surface of metal electrode, electrolytic condenser contact area are not high, manufacturing cycle is long, provide a kind of chip utilizing industrial aluminum process to obtain as raw material, and the preparation method of the large aluminum alloy anode metallic plate of electrolytic condenser contact area.
The preparation method of a kind of aluminium-air cell aluminum alloy anode metallic plate provided by the invention, the aluminium bits adopting industrial aluminum processing to produce for raw material, through draining oil removing, pulverizing, mix with zinc powder, compaction moulding, heat treatment, obtain aluminum alloy anode metallic plate after thermal spraying.
The preparation method of described aluminium-air cell aluminum alloy anode metallic plate, comprises the following steps:
(1) draining oil removing:
After aluminium bits industrial processes produced reclaim, carry out oil removing, decontamination, drying;
(2) pulverize:
Aluminium bits after draining oil removing put into the ball mill ball milling 2 ~ 3 hours of built-in diameter 20 ~ 30mm steel alloy steel ball, are pulverized evenly, obtain aluminium and consider particle to be worth doing; Because aluminium bits surface itself has layer oxide film, reduce electrode activity, if pulverize very thin by aluminium bits, can increase oxide-film area further, therefore Ball-milling Time is unsuitable oversize, the aluminium bits particle diameter obtained should be 2 ~ 4mm;
(3) mix with zinc powder:
Be that the zinc powder of 100 ~ 120 μm joins in aluminium bits particle by particle diameter, mixing and stirring, in aluminium, zinc hybrid particles, the mass fraction of zinc powder is 0.09% ~ 0.11%;
(4) compaction moulding:
The hybrid particles raw material of step (3) gained is placed in the rectangle die cavity of forcing press, compressing under 170 ~ 200MPa, make that cross section is rectangle, thickness is 5 ~ 6mm, density is 2500 ~ 2600kg/m
3zinc-aluminium bits plate;
(5) heat treatment:
Zinc-aluminium bits plate carries out the annealing heat treatment of 5 hours at the temperature of 490 ~ 510 DEG C;
(6) thermal spraying:
In spray gun storage device, be provided with aluminium, gallium, tin, bismuth mixed metal particles as the material spray of thermal spraying spray gun, it is carried out thermal spraying on the surface at zinc-aluminium bits plate equably.
In described thermal spray process, with aluminium (99.16wt% ~ 99.30wt%), gallium (0.1wt% ~ 0.12wt%), tin (0.1wt% ~ 0.12wt%), bismuth (0.5wt% ~ 0.6wt%) mixed metal particles for material spray, average diameter of particles 1 ~ 1.2mm, bore is selected to be 0.8 ~ 2.0mm spray gun, spray after heating compound particles to 1000 DEG C ~ 1200 DEG C makes its melting, drop on equably on the large surface of zinc-aluminium bits plate, intactly covering a layer thickness is on a surface the coating of 0.01 ~ 0.03mm.
For the battery pack of the corresponding air electrode of anode, also can one of them only on spraying two large surfaces, and when mounted by this surface just to air electrode, thus ensure that the aluminium bits plate electrode reaction surface activity as anode is the highest.
In a spraying process, the quality of mixed metal particles material spray used is 50 ~ 60g.For batch production, aluminium added in described thermal spray process, gallium, tin, bismuth mixed metal particles material spray should fill it up with whole spray gun storage device as far as possible, to meet the needs of continuous operation, after having sprayed one block of zinc-aluminium bits positive plate, proceed the spraying of next block positive plate again.
Extraction electrode, namely obtains the metal polar plate that can be used as aluminium-air cell anode.
The aluminum alloy anode metallic plate that said method obtains also can first be scrubbed with dilute hydrochloric acid solution or soak 1 ~ 2 time, to reduce the thickness of the upper oxide-film of aluminium bits, improves electrode discharge performance.
Of the present invention
beneficial effect:
1. the aluminium bits utilizing metal cutting process to be formed, as raw material, solve the problem of waste aluminum recovery, eliminate the technique that aluminium considers again Electrolyzed Processing to be worth doing, reduce the cost of manufacture of metal electrode.
2. consider compressing aluminium bits plate surface to be worth doing by aluminium and there is hole, with electrolytical larger than contact area, enhance electrode discharge reaction.
3. the alloying element zinc added is cheap, and gallium, tin, bismuth only need cover electrode surface, and aequum is little, and effectively can improve electrode activity.
4. because aluminium bits cost is low, therefore the impact of corrosion on battery capacity can be ignored.
Detailed description of the invention
Below by way of specific embodiment, the present invention is described in further detail, but this should be interpreted as scope of the present invention is only limitted to following examples.When not departing from said method thought of the present invention, the various replacement made according to ordinary skill knowledge and customary means and change, all should be within the scope of the present invention.
Embodiment 1: the preparation method of aluminium-air cell aluminum alloy anode metallic plate
Possess and comprise the following steps:
1) sodium bicarbonate solution aluminium bits being put into 20% mass fraction soaks 30 minutes, removing oil stain, then with giant spraying-rinsing aluminium bits impurity, dries in drier.
2) aluminium bits are put into the ball mill ball milling 2 hours of diameter 30mm steel alloy steel ball, obtain the even aluminium bits particle that average diameter is 4mm.
3) mixed with 0.135g zinc powder by 149.865g aluminium bits particle, the mass fraction that zinc powder accounts for compound is 0.09%, and in mixer, mix and blend 15 minutes, makes it stir.
4) zinc-aluminium bits compound particles is put in the 100mm × 100mm × 6mm square sectional die cavity of forcing press, depress at 170MPa that thickness is 6mm, density is 2500 ~ 2600kg/m
3zinc-aluminium bits plate.
5) to zinc-aluminium bits plate carry out 5 little enter annealing heat treatment, annealing temperature 490 DEG C.
6) be the flame gun of 0.8mm with bore be 1mm by average particulate diameter, mass fraction be respectively 99.3%, 0.1%, 0.1%, 0.5% aluminium, gallium, tin, bismuth hybrid metal powder be heated to 1000 DEG C make it melt after spray to two of zinc-aluminium bits plate and be of a size of on one of them face of 100mm × 100mm, cover completely, thickness is 0.01mm; The gross mass of mixed powder is 50g.
This anode can be used for the battery pack of the corresponding air electrode of an anode, and needs the surface through thermal spraying to be right against air electrode when mounted.
Embodiment 2: the preparation method of aluminium-air cell aluminum alloy anode metallic plate
Possess and comprise the following steps:
1) be that 30% sodium acid carbonate dissolves and washes away brush aluminium and considers 3 times to be worth doing with mass fraction, remove oil stain, then with giant spraying-rinsing aluminium bits impurity, in the indoor of drying standing 2 days, dry.
2) aluminium bits are put into the ball mill ball milling 2.5 hours of diameter 25mm steel alloy steel ball, obtain the even aluminium bits particle that average diameter is 3mm.
3) mixed with 0.15g zinc powder by 149.85g aluminium bits particle, the mass fraction that zinc powder accounts for compound is 0.1%, and in mixer, mix and blend 15 minutes, makes it stir.
4) zinc-aluminium bits compound particles is put in the 100mm × 120mm × 5.5mm square-section die cavity of forcing press, depress at 180MPa that thickness is 5.5mm, density is 2530 ~ 2600kg/m
3zinc-aluminium bits plate.
5) zinc-aluminium bits plate is carried out to the annealing heat treatment of 5 hours, annealing temperature 500 DEG C.
6) scrub aluminium bits plate 1 time with the watery hydrochloric acid that concentration is 25%, reduce the surface oxidation film thickness of aluminium bits on aluminium bits plate.
7) be the plasma gun of 1.0mm with bore be 1.1mm by average particulate diameter, mass fraction be respectively 99.2%, 0.1%, 0.1%, 0.6% aluminium, gallium, tin, bismuth hybrid metal powder be heated to 1100 DEG C make it melt after spray to two of zinc-aluminium bits plate and be of a size of on the surface of 100mm × 120mm, cover completely, thickness is 0.02mm; The gross mass of mixed powder is 55g.
Corresponding two air electrodes of this anode, two large surfaces are respectively just to an air electrode; Also can be used for the situation of the corresponding air electrode of anode, now two large surfaces arbitrarily can select one for just to air electrode.
Embodiment 3: the preparation method of aluminium-air cell aluminum alloy anode metallic plate
Possess and comprise the following steps:
1) be that the molten immersion aluminium of 15% sodium acid carbonate considers 1 hour to be worth doing with mass fraction, remove oil stain, then with giant spraying-rinsing aluminium bits impurity, in the indoor of drying standing 2 days, dry.
2) aluminium bits are put into the ball mill ball milling 3 hours of steel alloy steel ball, obtain the more even aluminium bits particle that average diameter is 2mm.
3) scrub aluminium bits plate 1 time with the watery hydrochloric acid that concentration is 25%, reduce the surface oxidation film thickness of aluminium bits on aluminium bits plate.
4) mixed with 0.165g zinc powder by 149.835g aluminium bits particle, the mass fraction that zinc powder accounts for compound is 0.11%, mixes stirring 15 minutes in mixer.
5) zinc-aluminium bits compound particles is put in the 100mm × 100mm × 5mm square sectional die cavity of forcing press, depress at 200MPa that thickness is 5mm, density is 2580 ~ 2600kg/m
3zinc-aluminium bits plate.
6) zinc-aluminium bits plate is carried out to the annealing heat treatment of 5 hours, annealing temperature 510 DEG C.
7) be 1.2mm with the arc pistol of bore 1.5mm by average particulate diameter, mass fraction be respectively 99.16%, 0.12%, 0.12%, 0.6% aluminium, gallium, tin, bismuth hybrid metal powder be heated to 1200 DEG C make it melt after spray to two of zinc-aluminium bits plate and be of a size of on the surface of 100mm × 100mm, cover completely, thickness is 0.01mm; The gross mass of mixed powder is 58g.
Embodiment 4: the preparation method of aluminium-air cell aluminum alloy anode metallic plate
Possess and comprise the following steps:
1) be 20% sodium metasilicate molten immersion aluminium bits half an hour with mass fraction, remove oil stain, then consider impurity to be worth doing with giant spraying-rinsing aluminium, dry in drier.
2) aluminium bits to be placed with in ball mill that diameter is 20mm steel alloy steel ball ball milling 3 hours, to obtain the more even aluminium bits particle that average diameter is 2mm.
3) mixed with 0.157g zinc powder by 157.143g aluminium bits particle, the mass fraction that zinc powder accounts for compound is 0.1%, mixes stirring 15 minutes in mixer.
4) zinc-aluminium bits compound particles is put in the 110mm × 110mm × 5mm square sectional die cavity of forcing press, depress at 190MPa that thickness is 5mm, density is 2570 ~ 2600kg/m
3zinc-aluminium bits plate.
5) zinc-aluminium bits plate is carried out to the annealing heat treatment of 5 hours, annealing temperature 505 DEG C.
6) be 1mm with the arc pistol of bore 2.0mm by average particulate diameter, mass fraction be respectively 99.26%, 0.12%, 0.12%, 0.5% aluminium, gallium, tin, bismuth hybrid metal powder be heated to 1150 DEG C make it melt after spray to two of zinc-aluminium bits plate and be of a size of on the surface of 110mm × 110mm, cover completely, thickness is 0.03mm; The gross mass of mixed powder is 60g.
Embodiment 5: the batch preparation of aluminium-air cell aluminum alloy anode metallic plate
1) mass fraction adding 1/3 volume in the pond of 4m × 3m × 0.5m is the sodium bicarbonate solution of 20%.
2) 100kg aluminium bits are put into pond and soaked half an hour, then taking-up giant rinses, then is placed in hothouse and dries.
3) all aluminium bits to be placed with in the ball mill that diameter is 20mm steel alloy steel ball ball milling 3 hours, to obtain the more even aluminium bits particle that average diameter is 2mm.
4) in 100kg aluminium bits, add 0.1kg zinc powder, stir 20 minutes with large-scale mixer.
5) each hybrid particles taking out 150g zinc and aluminium and consider to be worth doing, puts into the 100mm × 100mm × 5mm square sectional die cavity of forcing press, depresses to that thickness is 5mm, density is 2500 ~ 2600kg/m at 200MPa
3zinc-aluminium bits plate.
6) be 1.5mm by average particulate diameter, gross mass is the aluminium (99.26wt%) of 10kg, gallium (0.12wt%), tin (0.12wt%), bismuth (0.5wt%) mixed metal particles add in thermal spraying storage device.
7) thermal spraying apparatus is started, mixed metal particles being heated to 1200 DEG C makes it melt, be that the hybrid metal of fusing is sprayed on one of them 100mm × 100mm on zinc-aluminium bits plate and on the surface, until this surface is covered completely by coating, closes spray gun by the plasma gun of 0.8mm with bore; Coating layer thickness is 0.012mm.
8) overturn zinc-aluminium bits plate, open spray gun, continue another 100mm × 100mm surface of spraying, until this surface is covered completely by coating.
9) continue the lower block zinc of spraying-aluminium bits plate, spraying method and 7), 8) identical.
10) when material spray in thermal spraying storage device is finished, change material spray, then continue spraying.
Claims (8)
1. the preparation method of an aluminium-air cell aluminum alloy anode metallic plate, it is characterized in that: the aluminium bits adopting industrial aluminum processing to produce for raw material, through draining oil removing, pulverizing, mix with zinc powder, compaction moulding, heat treatment, obtain aluminum alloy anode metallic plate after thermal spraying.
2. the preparation method of aluminium-air cell aluminum alloy anode metallic plate according to claim 1, is characterized in that: comprise the following steps:
(1) draining oil removing:
Aluminium bits industrial processes produced carry out oil removing, decontamination, drying;
(2) pulverize:
Aluminium bits after draining oil removing put into the ball mill of built-in steel alloy steel ball, are pulverized evenly, obtain aluminium bits particle;
(3) mix with zinc powder:
Consider aluminium to be worth doing particle to mix with zinc powder, in aluminium, zinc hybrid particles, the mass fraction of zinc powder is 0.09% ~ 0.11%;
(4) compaction moulding:
The hybrid particles raw material of step (3) gained is placed in the rectangle die cavity of forcing press, compressing under 170 ~ 200MPa, obtain zinc-aluminium bits plate;
(5) heat treatment:
Zinc-aluminium bits plate carries out the annealing heat treatment of 5 hours at the temperature of 490 ~ 510 DEG C;
(6) thermal spraying:
In spray gun storage device, be provided with aluminium, material spray that gallium, tin, bismuth mixed metal particles are thermal spraying spray gun, it is carried out thermal spraying, obtained aluminum alloy anode metallic plate on the surface at zinc-aluminium bits plate equably.
3. the preparation method of aluminium-air cell aluminum alloy anode metallic plate according to claim 2, it is characterized in that: described crushing process is: with the grinding of ball grinder 2 ~ 3 hours of built-in steel alloy steel ball, pulverized evenly, obtained the aluminium bits particle that particle diameter is 2 ~ 4mm.
4. the preparation method of aluminium-air cell aluminum alloy anode metallic plate according to claim 2, is characterized in that: the particle diameter of described zinc powder is 100 ~ 120 μm.
5. the preparation method of aluminium-air cell aluminum alloy anode metallic plate according to claim 2, is characterized in that: the zinc that described step (4) obtains-aluminium bits plate is rectangular structure, and thickness is 5 ~ 6mm, and density is 2500 ~ 2600kg/m
3.
6. the preparation method of aluminium-air cell aluminum alloy anode metallic plate according to claim 2, it is characterized in that: in described thermal spray process, with aluminium, gallium, tin, bismuth mixed metal particles for material spray, average diameter of particles 1 ~ 1.2mm, bore is selected to be 0.8 ~ 2.0mm spray gun, spray after heating compound particles to 1000 DEG C ~ 1200 DEG C makes its melting, drop on equably on the large surface of zinc-aluminium bits plate, intactly covering a layer thickness is on a surface the coating of 0.01 ~ 0.03mm.
7. the preparation method of aluminium-air cell aluminum alloy anode metallic plate according to claim 2, it is characterized in that: in described thermal spray process, in spray gun storage device, the mass fraction of aluminium, gallium, tin, bismuth mixed metal powder is respectively 99.16% ~ 99.30%, 0.1% ~ 0.12%, 0.1% ~ 0.12%, 0.5% ~ 0.6%.
8. the preparation method of aluminium-air cell aluminum alloy anode metallic plate according to claim 1 and 2, it is characterized in that: described aluminum alloy anode metallic plate dilute hydrochloric acid solution is scrubbed or soaks 1 ~ 2 time, to reduce the thickness of the upper oxide-film of aluminium bits, improve electrode discharge performance.
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| CN107419121A (en) * | 2017-04-05 | 2017-12-01 | 陕西科技大学 | A kind of preparation method of sustainable stable production hydrogen aluminium anodes material |
| CN107658423A (en) * | 2017-08-07 | 2018-02-02 | 云南靖创液态金属热控技术研发有限公司 | Liquid metal alloy pole piece and preparation method, lithium ion battery and preparation method |
| CN109860956A (en) * | 2019-02-26 | 2019-06-07 | 中南大学 | A kind of waste aluminum recovery system and method |
| WO2019201070A1 (en) * | 2018-04-20 | 2019-10-24 | 东深金属燃料动力实验室有限责任公司 | Method for producing aluminum hydroxide from aluminum waste material |
| CN110819844A (en) * | 2019-11-19 | 2020-02-21 | 刘海涛 | Aluminum alloy door frame manufacturing device based on electrode reaction principle |
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| CN113097471A (en) * | 2021-03-16 | 2021-07-09 | 郑州大学 | Anode material for alkaline aluminum-air battery and preparation method thereof |
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