CN105057679B - 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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- CN105057679B CN105057679B CN201510578890.9A CN201510578890A CN105057679B CN 105057679 B CN105057679 B CN 105057679B CN 201510578890 A CN201510578890 A CN 201510578890A CN 105057679 B CN105057679 B CN 105057679B
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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 fine aluminium or aluminium to close
Gold is as metal electrode negative pole.Either fine aluminium or aluminium alloy, is required for using highly purified aluminum metal.Industry aluminium processed is main
Using the method for electrolysis of aluminum oxide, it is electrolysed cost needed for one ton of aluminium more than 16000 yuan, high cost, this is to limit aluminium air electricity
The business-like one side in pond.
Fine aluminium contacts the oxide-film easily generating densification with oxygen, needs first to consume the oxidation on surface during as electrode
Film, reduces electrode activity, makes electrode passivation.Meanwhile, fine aluminium, easily from corroding in strong alkaline electrolytes, causes electrode polarization, fall
Low open-circuit voltage, and reduce the capacity of battery.For this reason, alloying element can be added in fine aluminium, anodizing film is made to form defect,
Accelerate electrode reaction, and improve electrode corrosion resistance.
What application was more at present has al and the binary alloy system such as zn, bi, te, in, ga, tl, al-ga-mg and al-in-mg
Deng the quaternary alloy such as ternary alloy system, al-ga-bi-pb, al-ga-sn-bi system and other five yuan, hexa-atomic alloy series.Close
Gold element is more, and the activity of electrode and corrosion resistance are stronger, but the element price such as bi, te, in, ga of comprising in multicomponent alloy system
Height, causes the high cost of multicomponent alloy anode.Even in binary alloy system, also the price of only zinc is relatively low.But bianry alloy
Effect is far below multicomponent alloy, and alloying element as such in zinc can only strengthen electrode activity, and antagonism is corrosive to improve simultaneously
Inconspicuous.
The current efficiency of aluminium-air cell is relevant with the ratio contact area between electrolyte and metal electrode board, increases metal
The ratio contact area of electrode and electrolyte can increase electrode discharge intensity.And existing aluminium-air cell anode, electrode surface light
Sliding, the ratio contact area between metal electrode and electrolyte is certain value, and strength of discharge cannot change.
Content of the invention
The present invention is high for aluminium-air cell metal electrode cost of manufacture, surface of metal electrode, electrolytic condenser contact surface
The problems such as long-pending not high, long preparation period, a kind of chip obtaining by the use of industrial aluminum processing is provided to connect as raw material with electrolytic condenser
Contacting surface amasss the preparation method of big aluminum alloy anode metallic plate.
A kind of preparation method of aluminium-air cell aluminum alloy anode metallic plate that the present invention provides, is processed using industrial aluminum and produces
Raw aluminium skimmings are raw material, mixs with zinc powder through draining oil removing, pulverizing, compaction moulding, heat treatment, obtain aluminium conjunction after thermal spraying
Gold anode metallic plate.
The preparation method of described aluminium-air cell aluminum alloy anode metallic plate, comprises the following steps:
(1) draining oil removing:
After the aluminium skimmings that industrial processes are produced reclaim, carry out oil removing, decontamination, drying；
(2) pulverize:
Aluminium skimmings after draining oil removing put into ball milling 2 ~ 3 hours in the ball mill of built-in diameter 20 ~ 30mm steel alloy steel ball,
Pulverized uniformly, obtained aluminium skimmings particle；Because aluminium skimmings surface has layer oxide film in itself, reduce electrode activity, if will
Aluminium skimmings are pulverized very thin, can increase oxidation membrane area further, therefore Ball-milling Time is unsuitable oversize, the aluminium skimmings particle diameter obtaining should
For 2 ~ 4mm；
(3) mix with zinc powder:
The zinc powder that particle diameter is 100 ~ 120 μm is added in aluminium skimmings particle, mixing and stirring, aluminium, zinc mixing
In grain, 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, suppresses under 170 ~ 200mpa
Shaping, make rectangular cross-section, thickness be 5 ~ 6mm, density be 2500 ~ 2600kg/m3Zinc-aluminium skimmings plate；
(5) it is heat-treated:
Zinc-aluminium skimmings plate carries out the annealing heat-treats of 5 hours at a temperature of 490 ~ 510 DEG C；
(6) thermal spraying:
Spray gun storage device is provided with aluminium, gallium, tin, bismuth mixed metal particles as thermal spraying spray gun material spray, by it
Equably in zinc-aluminium skimmings plate surface, carry out thermal spraying.
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 be material spray, average diameter of particles 1 ~ 1.2mm, from bore be
0.8 ~ 2.0mm spray gun, heating mixture particle sprays after so that it is melted to 1000 DEG C ~ 1200 DEG C, equably falls in zinc-aluminium skimmings plate
Large surface on, intactly on a surface cover a layer thickness be 0.01 ~ 0.03mm coating.
Battery pack for the corresponding air electrode of an anode is it is also possible to only spray wherein in two large surfaces
Individual, and when mounted by this surface just to air electrode, thus ensure as anode aluminium skimmings plate electrode reaction surface activity
High.
In spraying process, the quality of mixed metal particles material spray used is 50 ~ 60g.For batch production, described heat
In spraying process, added aluminium, gallium, tin, bismuth mixed metal particles material spray should fill it up with whole spray gun storage device as far as possible, with full
The continuous requirements of one's work of foot, are further continued for carrying out the spraying of next block positive plate after having sprayed one block of zinc-aluminium skimmings positive plate.
Extraction electrode, that is, obtaining can be used as the metal polar plate of aluminium-air cell anode.
The aluminum alloy anode metallic plate that said method is obtained also first can be scrubbed with dilute hydrochloric acid solution or soak 1 ~ 2 time, to subtract
The thickness of oxide-film in little aluminium skimmings, improves electrode discharge performance.
Beneficial effects of the present invention:
1. by the use of metal cutting process formed aluminium skimmings as raw material, solve the problems, such as waste aluminum recovery, eliminate aluminium
The technique considering Electrolyzed Processing again to be worth doing, reduces the cost of manufacture of metal electrode.
2. hole is had by the compressing aluminium skimmings plate surface of aluminium skimmings, big with the ratio contact area of electrolyte, enhance electricity
Pole exoelectrical reaction.
3. the alloying element zinc adding is cheap, and gallium, tin, bismuth only need to cover in electrode surface, and aequum is little, and energy
Effectively improve electrode activity.
4. due to aluminium skimmings low cost, therefore the impact to battery capacity for the negligible corrosion.
Specific embodiment
Below by way of specific embodiment, the present invention is described in further detail, but this should not be interpreted as the present invention's
Scope is only limitted to following examples.In the case of without departing from said method thought of the present invention, known according to ordinary skill
Know the various replacements made with customary means and change, should be included in 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) aluminium skimmings are put in the sodium bicarbonate solution of 20% mass fraction and soak 30 minutes, remove oil stain, then use water under high pressure
Rifle spraying-rinsing aluminium skimmings impurity, dries in drier.
2) aluminium skimmings are put into ball milling 2 hours in the ball mill of diameter 30mm steel alloy steel ball, obtaining average diameter is 4mm's
Uniformly aluminium skimmings particle.
3) 149.865g aluminium skimmings particle is mixed with 0.135g zinc powder, the mass fraction that zinc powder accounts for compound is 0.09%,
In mixer, mix and blend 15 minutes is so as to stir.
4) zinc-aluminium skimmings compound particles are put to the 100mm × 100mm of forcing press × 6mm square sectional die cavity,
170mpa depress to thickness be 6mm, density be 2500 ~ 2600kg/m3Zinc-aluminium skimmings plate.
5) zinc-aluminium skimmings plate is carried out 5 little enter annealing heat-treats, 490 DEG C of annealing temperature.
6) flame gun being 0.8mm with bore by average particulate diameter be 1mm, mass fraction be respectively 99.3%,
0.1%th, 0.1%, 0.5% aluminium, gallium, tin, the hybrid metal powder of bismuth is heated to 1000 DEG C makes it spray to zinc-aluminium skimmings after melting
On two of plate a size of one of face of 100mm × 100mm, cover completely, thickness is 0.01mm；Total matter of mixed powder
Measure as 50g.
This anode can be used for the battery pack of the corresponding air electrode of an anode, and needs through thermal spraying when mounted
Surface is right against air electrode.
Embodiment 2: the preparation method of aluminium-air cell aluminum alloy anode metallic plate
Possess and comprise the following steps:
1) dissolve and wash away brush aluminium skimmings 3 times with mass fraction for 30% sodium acid carbonate, remove oil stain, then use giant spraying-rinsing
Aluminium skimmings impurity, in the indoor standing 2 days being dried, dries.
2) aluminium skimmings are put into ball milling 2.5 hours in the ball mill of diameter 25mm steel alloy steel ball, obtaining average diameter is 3mm
Uniform aluminium skimmings particle.
3) 149.85g aluminium skimmings particle is mixed with 0.15g zinc powder, the mass fraction that zinc powder accounts for compound is 0.1%, is stirring
Mix in machine mix and blend 15 minutes so as to stir.
4) zinc-aluminium skimmings compound particles are put to the 100mm × 120mm of forcing press × 5.5mm square-section die cavity,
180mpa depress to thickness be 5.5mm, density be 2530 ~ 2600kg/m3Zinc-aluminium skimmings plate.
5) zinc-aluminium skimmings plate is carried out with the annealing heat-treats of 5 hours, 500 DEG C of annealing temperature.
6) scrub aluminium skimmings plate 1 time with the watery hydrochloric acid that concentration is 25%, reduce the surface oxidation film thickness of aluminium skimmings on aluminium skimmings plate.
7) plasma gun being 1.0mm with bore by average particulate diameter be 1.1mm, mass fraction be respectively 99.2%,
0.1%th, 0.1%, 0.6% aluminium, gallium, tin, the hybrid metal powder of bismuth is heated to 1100 DEG C makes it spray to zinc-aluminium skimmings after melting
On two of the plate a size of surface of 100mm × 120mm, cover completely, thickness is 0.02mm；The gross mass of mixed powder is
55g.
This anode corresponds to two air electrodes, and two large surfaces are respectively just to an air electrode；Can be used for a sun
Extremely correspond to the situation of an air electrode, now two large surfaces can arbitrarily 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) use mass fraction to be that 15% sodium acid carbonate is molten and soak aluminium skimmings 1 hour, remove oil stain, more clear with giant water spray
Wash aluminium skimmings impurity, in the indoor standing 2 days being dried, dry.
2) aluminium skimmings are put into ball milling 3 hours in the ball mill of steel alloy steel ball, obtain the more uniform aluminium that average diameter is 2mm
Bits particle.
3) scrub aluminium skimmings plate 1 time with the watery hydrochloric acid that concentration is 25%, reduce the surface oxidation film thickness of aluminium skimmings on aluminium skimmings plate.
4) 149.835g aluminium skimmings particle is mixed with 0.165g zinc powder, the mass fraction that zinc powder accounts for compound is 0.11%,
Stirring 15 minutes is mixed in mixer.
5) zinc-aluminium skimmings compound particles are put to the 100mm × 100mm of forcing press × 5mm square sectional die cavity,
200mpa depress to thickness be 5mm, density be 2580 ~ 2600kg/m3Zinc-aluminium skimmings plate.
6) zinc-aluminium skimmings plate is carried out with the annealing heat-treats of 5 hours, 510 DEG C of annealing temperature.
7) with the arc pistol of bore 1.5mm by average particulate diameter be 1.2mm, mass fraction be respectively 99.16%,
0.12%th, 0.12%, 0.6% aluminium, gallium, tin, the hybrid metal powder of bismuth is heated to 1200 DEG C makes it spray to zinc-aluminium after melting
On two of the bits plate a size of 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) use mass fraction to be that 20% sodium metasilicate is molten and soak aluminium skimmings half an hour, remove oil stain, then use giant spraying-rinsing
Aluminium skimmings impurity, dries in drier.
2) aluminium skimmings are placed with ball milling 3 hours in the ball mill of a diameter of 20mm steel alloy steel ball, obtaining average diameter is
The more uniform aluminium skimmings particle of 2mm.
3) 157.143g aluminium skimmings particle is mixed with 0.157g zinc powder, the mass fraction that zinc powder accounts for compound is 0.1%,
Stirring 15 minutes is mixed in mixer.
4) zinc-aluminium skimmings compound particles are put to the 110mm × 110mm of forcing press × 5mm square sectional die cavity,
190mpa depress to thickness be 5mm, density be 2570 ~ 2600kg/m3Zinc-aluminium skimmings plate.
5) zinc-aluminium skimmings plate is carried out with the annealing heat-treats of 5 hours, 505 DEG C of annealing temperature.
6) with the arc pistol of bore 2.0mm by average particulate diameter be 1mm, mass fraction be respectively 99.26%,
0.12%th, 0.12%, 0.5% aluminium, gallium, tin, the hybrid metal powder of bismuth is heated to 1150 DEG C makes it spray to zinc-aluminium after melting
On two of the bits plate a size of 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) add in the pond of 4m × 3m × 0.5m 1/3 volume mass fraction be 20% sodium bicarbonate solution.
2) 100kg aluminium skimmings are put into immersion half an hour in pond, then take out and rinsed with giant, then be placed in hothouse
Inside dry.
3) all aluminium skimmings are placed with ball milling 3 hours in the ball mill of a diameter of 20mm steel alloy steel ball, obtain averagely straight
Footpath is the more uniform aluminium skimmings particle of 2mm.
4) add 0.1kg zinc powder in 100kg aluminium skimmings, stirred 20 minutes with large-scale mixer.
5) take out the hybrid particles of 150g zinc and aluminium skimmings every time, put into the 100mm × 100mm × 5mm square of forcing press
In the die cavity of section, 200mpa depress to thickness be 5mm, density be 2500 ~ 2600kg/m3Zinc-aluminium skimmings plate.
6) average particulate diameter is 1.5mm, 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) start thermal spraying apparatus, mixed metal particles are heated to 1200 DEG C makes it melt, with bore be 0.8mm etc.
The hybrid metal of fusing is sprayed on one of 100mm × 100mm surface on zinc-aluminium skimmings plate ion spray gun, until this table
Face is completely covered by coating, closes spray gun；Coating layer thickness is 0.012mm.
8) overturn zinc-aluminium skimmings plate, open spray gun, continue to spray another 100mm × 100mm surface, until this surface quilt
Coating is completely covered.
9) continue the lower block zinc-aluminium skimmings plate of spraying, spraying method and 7), 8) identical.
10) when in thermal spraying storage device material spray be finished, change material spray, be further continued for spray.
Claims (6)
1. a kind of preparation method of aluminium-air cell aluminum alloy anode metallic plate it is characterised in that: using industrial aluminum process produce
Aluminium skimmings be raw material, mix with zinc powder through draining oil removing, pulverizing, compaction moulding, heat treatment, obtain aluminium alloy after thermal spraying
Anode metal plate；Specifically include following steps:
(1) draining oil removing:
The aluminium skimmings that industrial processes are produced carry out oil removing, decontamination, drying；
(2) pulverize:
Aluminium skimmings after draining oil removing are put in the ball mill of built-in steel alloy steel ball, are pulverized uniformly, obtain aluminium skimmings particle；
(3) mix with zinc powder:
Aluminium skimmings particle is mixed 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 skimmings plate；
(5) it is heat-treated:
Zinc-aluminium skimmings plate carries out the annealing heat-treats of 5 hours at a temperature of 490 ~ 510 DEG C；
(6) thermal spraying:
Spray gun storage device is provided with aluminium, gallium, tin, bismuth mixed metal particles be thermal spraying spray gun material spray, by it equably
Thermal spraying, prepared aluminum alloy anode metallic plate are carried out on zinc-aluminium skimmings plate surface.
2. aluminium-air cell aluminum alloy anode metallic plate according to claim 1 preparation method it is characterised in that: described
Crushing process is: is ground 2 ~ 3 hours with the ball mill of built-in steel alloy steel ball, is pulverized uniformly, obtaining particle diameter is 2 ~ 4mm
Aluminium skimmings particle.
3. aluminium-air cell aluminum alloy anode metallic plate according to claim 1 preparation method it is characterised in that: described
The particle diameter of zinc powder is 100 ~ 120 μm.
4. aluminium-air cell aluminum alloy anode metallic plate according to claim 1 preparation method it is characterised in that: described
The zinc that step (4) obtains-aluminium skimmings plate is rectangular structure, and thickness is 5 ~ 6mm, and density is 2500 ~ 2600kg/m3.
5. aluminium-air cell aluminum alloy anode metallic plate according to claim 1 preparation method it is characterised in that: described
In thermal spray process, with aluminium, gallium, tin, bismuth mixed metal particles as material spray, average diameter of particles 1 ~ 1.2mm, from bore be
0.8 ~ 2.0mm spray gun, heating mixture particle sprays after so that it is melted to 1000 DEG C ~ 1200 DEG C, equably falls in zinc-aluminium skimmings plate
Large surface on, intactly on a surface cover a layer thickness be 0.01 ~ 0.03mm coating.
6. aluminium-air cell aluminum alloy anode metallic plate according to claim 1 preparation method it is characterised in that: described
In thermal spray process, aluminium in spray gun storage device, gallium, tin, bismuth account for mixed metal powder mass fraction be respectively 99.16% ~
99.30%、0.1%~0.12%、0.1%~0.12%、0.5%~0.6%.
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| WO2023044264A1 (en) * | 2021-09-15 | 2023-03-23 | Novelis Inc. | Aluminum-based anode for lithium-ion batteries |
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| CN107419121B (en) * | 2017-04-05 | 2019-03-12 | 陕西科技大学 | A kind of sustainable stable preparation method for producing hydrogen aluminium anodes material |
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| CN108615960A (en) * | 2018-04-20 | 2018-10-02 | 东深金属燃料动力实验室有限责任公司 | The method that aluminium hydroxide is produced using discarded aluminium |
| CN109860956B (en) * | 2019-02-26 | 2021-11-23 | 中南大学 | Waste aluminum recovery system and method |
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| CN113097471B (en) * | 2021-03-16 | 2023-04-25 | 郑州大学 | Anode material for alkaline aluminum-air battery and preparation method thereof |
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| US6042781A (en) * | 1991-12-04 | 2000-03-28 | Materials Innovation, Inc. | Ambient temperature method for increasing the green strength of parts |
| CN1978099A (en) * | 2005-12-07 | 2007-06-13 | 中国电子科技集团公司第十八研究所 | PbTe powde material formation preparing method |
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