CN104762639B - Hydrometallurgy electro-deposition operation porous aluminum based composite anode and preparation method - Google Patents
Hydrometallurgy electro-deposition operation porous aluminum based composite anode and preparation method Download PDFInfo
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Abstract
The invention discloses a kind of hydrometallurgy electro-deposition operation porous aluminum based composite anode and preparation method.The anode substrate is the aluminium alloy with " three-dimensional through hole structure ", on the hole wall of " the three-dimensional through hole structure " of alloy matrix aluminum and aluminium alloy matrix surface is provided with clad, the clad is made up of the metal outer layer of pb-ag alloy internal layer and hydrometallurgy electrodeposition operation maturation lead anode；Its preparation method includes：The pretreatment of porous aluminum substrate, pb-ag alloy bottom on porous aluminum substrate be accompanied by and three big step of post processing.By porous aluminum based composite anode prepared by the inventive method, with low overpotential for oxygen evolution, good electric conductivity and creep resistance, high using the produced cathode product quality of the anode, anode manufactures the low cost of adopted raw material；In addition, the manufacturing process route of anode is simple, large-scale industrial production anode is can be used to.
Description
Technical field
The present invention relates to a kind of porous metal composite material preparation method, more particularly to a kind of hydrometallurgy electro-deposition operation
With porous aluminum based composite anode and preparation method, belong to metal material and prepare and technical field of wet metallurgy.
Background technology
As hydrometallurgy has comprehensive resource utilization rate high, process environmental protection and excellent to low-grade ore strong adaptability etc.
The non-ferrous metals such as point, Cu, Zn, Ni, Co, Cd, Mn are carried out extracting the share for accounting for by wet method and gradually being increased.Electro-deposition is wet method smelting
An important procedure in non-ferrous metal technical process is extracted in refining, industrial at present mostly using insoluble Pb alloys as sun
Pole, but as lead density is big, electrical conductivity is not high and tensile strength is little, compacted so as to cause anode easily to occur in use
Become, anode drop is big and the appearance of the low defect of current efficiency；In addition, in some anodes, also contain the silver of many contents,
Result in anode material high cost.Therefore mitigate anode weight, improve anode conductivity and tensile strength, your gold in anode reduced
Category content is significant to the lifting of existing hydrometallurgical technology.
Lead and aluminum are combined with each other to prepare aluminium base lead composite anode be an effective means improving anode performance, front
People also does a lot in this respect.Patent 200710065927.3 employs similar method with patent 01135605.7,
The mode of dipping or chemical plating is first passed through in one layer of transition metal layer of aluminum surface layer preplating, is then poured on pre-plating layer again
Casting metal, as the oxide layer of aluminium surface is readily formed, this kind of method certainly will be difficult to ensure that card pre-plating layer is long-acting with aluminum substrate
In conjunction with.Patent 200910094290.X disclose a class directly on aluminum substrate lead plating alloy-layer method, the method remove work
Skill is complicated outer, and the combination between the control of thickness of coating and coating and aluminum substrate is still its subject matter.
For the developed aluminium base lead composite anode of prior art exist aluminum substrate and metal top layer be difficult to long-acting combination with
And the aspect problem such as complex process, the present inventor invented a kind of hydrometallurgy electro-deposition operation porous aluminum through studying repeatedly
The compound lead anode preparation method of base.
Content of the invention
It is an object of the invention to overcoming the deficiency of prior art, there is provided a kind of rational in infrastructure, aluminum/lead interface cohesion is tight
Close, electric conductivity is good with creep-resistant property, hydrometallurgy electro-deposition operation porous aluminum based composite anode and system of long service life
Preparation Method.
A kind of hydrometallurgy electro-deposition operation porous aluminum based composite anode of the present invention, the composite anode matrix be with
The aluminium alloy of " three-dimensional through hole structure ", on the hole wall of " the three-dimensional through hole structure " of alloy matrix aluminum and aluminium alloy matrix surface
Clad is provided with, outside metal of the clad by pb-ag alloy internal layer with hydrometallurgy electrodeposition operation maturation lead anode
Layer composition；
A kind of hydrometallurgy electro-deposition operation porous aluminum based composite anode of the present invention, " three-dimensional through hole in alloy matrix aluminum
The clear size of opening of structure " is 4-8mm, and the porosity of alloy matrix aluminum is 60-80%；
A kind of hydrometallurgy electro-deposition operation porous aluminum based composite anode of the present invention, internal layer pb-ag alloy in clad
Thickness is 0.2-0.5mm, and the thickness of outer layer metal is 0.8-2.5mm；In pb-ag alloy, the weight/mass percentage composition of silver is 0.2-
0.6wt%.
A kind of hydrometallurgy electro-deposition operation porous aluminum based composite anode of the present invention, the matter of each element in alloy matrix aluminum
Measuring percentage composition is：
0.5-1.5wt%Mg, 3-5wt%Si, 0.5-1.5wt%Cu, aluminum surplus.
A kind of hydrometallurgy electro-deposition operation porous aluminum based composite anode of the present invention, the size of anode hole is 1-2mm,
The porosity of anode is 55-65%.
A kind of preparation method of the hydrometallurgy electro-deposition operation of the present invention with porous aluminum based composite anode, including following steps
Suddenly：
The first step：Alloy matrix aluminum pretreatment
Be interconnected from hole, bore hole size be 4-8mm, porosity for 60-80% alloy matrix aluminum,
By alloy matrix aluminum, it is placed in the nitric acid vapor that temperature is 60-100 DEG C and aoxidizes, after surface produces micropore, washing；
Then, by oxidation after alloy matrix aluminum be placed in sodium hydroxide lye soak, make nitric acid oxidation formed micropore expand, most
Afterwards, deionized water rinsed clean, drying；
Second step：Aluminium alloy matrix surface coats pb-ag alloy
By packaged to first step gained alloy matrix aluminum and pb-ag alloy ingot one enter hermetic container, hermetic container is evacuated down to
0.01-10Pa, then, maintains vacuum, and hermetic container is warmed up to after 350-520 DEG C of insulation 10-30min, to hermetic container
In be passed through noble gases, make the pressure of hermetic container reach 15-120Mpa, after pressurize 30-60mi；320-330 is cooled to stove
DEG C, release at this temperature, alloy matrix aluminum is taken out from lead melt, air-cooled, obtains surface and is combined with pb-ag alloy layer
Porous anode crude green body；
3rd step：To second step gained porous anode, just base carries out post processing
After to second step gained anode crude green body surface chemistry terne coating, in the hydrometallurgy that temperature is 350-450 DEG C
Electrodeposition operation with ripe lead anode with metal melt in carry out at least 3 times recycle metals baths, obtain hydrometallurgy electro-deposition
Operation porous aluminum based composite anode.
A kind of preparation method of the hydrometallurgy electro-deposition operation of the present invention with porous aluminum based composite anode, alloy matrix aluminum exist
Aoxidize in nitric acid vapor, be by the salpeter solution liquid level hanging in closed reactor of alloy matrix aluminum, heat salpeter solution
Alloy matrix aluminum is aoxidized；The mass percentage concentration of described salpeter solution is 65-68%, and its volume accounts for closed reactor
The 5-30% of volume, oxidization time 5-30min；
In sodium hydroxide lye, sodium hydrate content is 40-60g/l, and the temperature of sodium hydroxide lye is 40-55 DEG C, immersion
Time 5-10min.
A kind of preparation method of the hydrometallurgy electro-deposition operation of the present invention with porous aluminum based composite anode, when lowering the temperature with stove,
, in 15-120Mpa, rate of temperature fall is 1-5 DEG C/min to keep pressure in hermetic container.
A kind of preparation method of the hydrometallurgy electro-deposition operation of the present invention with porous aluminum based composite anode, surface chemistry lead plating
Tin alloy, is that just base is placed in chemical plating fluid by porous anode, reacts 20-60min at a temperature of 75-100 DEG C (preferably 90 DEG C)
(preferably 30min), in chemical plating fluid, the content of each component is：
Pyrovinic acid 150-350ml/l (preferably 200ml/l),
Tin methane sulfonate 200-400ml/l (preferably 320ml/l),
Pyrovinic acid lead 100-300ml/l (preferably 160ml/l),
Thiourea 50-100g/l (preferably 80g/l),
Sodium hypophosphite 5-15g/l (preferably 10g/l),
EDTA1-3g/l (preferably 2g/l),
Ascorbic acid 1-3g/l (preferably 2g/l).
The method of the invention achieves " long-acting seamless " combination between aluminum substrate and metal, is based on following original
Cause：When 1. carrying out pretreatment to porous aluminum substrate, acid gas atmosphere and dilute alkaline soln dual corrosion, this not only can remove porous aluminium surface
Oxide skin, especially by nitric acid vapor to core surfaces corrosion treatmentCorrosion Science, etch pit can be produced；During follow-up alkali process,
Due to Al2O3Can react with alkali with Al, further expand aluminium surface pore size, be conducive to pb-ag alloy melt to soak
Enter in the micropore of aluminium alloy matrix surface；Subsequently, using the infiltration for applying certain pressure in hermetic container, using external pressurized
Power, overcomes that aluminum, lead interface wettability are poor, and lead melt is difficult the obstacle combined with aluminum alloy surface, makes the pb-ag alloy melt can be with
Immersion aluminium alloy matrix surface micropore in, then, near metal melting temperature (320-330 DEG C) by alloy matrix aluminum from
Take out in pb-ag alloy melt, air-cooled, the pb-ag alloy quick solidification for sticking to aluminium alloy matrix surface is made, aluminium alloy table is immersed
Pb-ag alloy in the micropore of face and for forming mechanical snap between micropore, realizes that pb-ag alloy and the physics of alloy matrix aluminum are tied
Close；2., in the aluminium alloy that alloy matrix aluminum of the present invention is selected, master alloying element is Mg, at 350-520 DEG C or so, pressurization, guarantor
Wen Shi, the lead of molten state form Mg-Pb or Al-Mg-Pb alloys with magnesium, realize " the metallurgical junction at aluminium alloy core matrix/lead interface
Close ".The present invention has the alloy matrix aluminum of three-dimensional through hole by arranging, and selects master alloying element for the aluminium alloy of magnesium, adopts
The combination of air-cooled technique rapidly after pressure infiltration, makes to be formed that " physics is tied between composite anode top layer metal and core aluminium alloy
Close " and " metallurgical binding ", it is ensured that " long-acting seamless " combination between aluminum substrate and metal.Overcome prepared by prior art
There is the defect that aluminum substrate and metal top layer are difficult to long-acting combination and complex process in aluminium base lead composite anode.
Subsequently, terne coating and recycle metal bath are learned on pb-ag alloy surface, on pb-ag alloy surface, parcel is applied to
The ripe lead anode metal outer layer of hydrometallurgy electrodeposition operation, prepares porous porous aluminum-base composite anode.
The electric conductivity of anode prepared by the inventive method is good with mechanical strength, mainly due to adopted foamed aluminium radical
The composition of the standby aluminium alloy of system similar to ZL101A, there are some researches show (see " Special Processes of Metal Castings and non-ferrous alloy, 2010,30
[12]:1162-1165 "), electrical conductivity of such alloy at 20 DEG C is 23.20-23.78MS m-1, anti-after T6 process
Tensile strength up to 285MPa, the i.e. electrical conductivity from aluminium alloy be close to 5 times of lead, tensile strength be close to the 15 of high-strength metal
Times；In addition, anode adopts loose structure, by controlling its porosity, on the premise of anode strength character is ensured, anode weight is made
Amount is considerably reduced, and the anode of preparation has outstanding creep-resistant property and lightweight.
The developed anode of the present invention has the positive effect of low overpotential for oxygen evolution, long life and high-quality cathode product
Really, this is because：1. the conductive surface area that " the three-dimensional through hole structure " of anode makes which actual is a lot of compared with the increase of classic flat-plate anode
Times, so that the actual current density of anode is greatly lowered, according to Tafel equation η=a+blogi, reduce electric current density
The reduction of achievable oxygen overpotential on anode；2. under low current density, the formed oxide-film in electrodeposition process Anodic surface
Densification, can effectively improve the acid corrosion-resistant performance of anode, this not only reduces anode lead be etched into electrolyte speed,
The lead content in cathode product is reduced, but also effectively extends anode life.
The cost of raw material (particularly bullion content) of anode prepared by the inventive method is more industrial to be made
Anode is greatly reduced, caused by this unique loose structure and high porosity mainly due to anode.
Therefore, composite anode of the present invention is compared with the announced anode of known technology, have following major advantage with positive
Effect：
(1) compared with known technology, porous aluminum pretreatment of the present invention simultaneously combines vacuum pressure infiltration, can achieve
Aluminum/lead interface is " long-acting seamless " to be combined, it is to avoid the method such as traditional plating may cause the presence of the defects such as plating dead angle, trachoma
Appearance；
(2) anode prepared by the technology of the present invention has good electric conductivity and creep resistance, and this is beneficial to tank voltage
Reduce and reduce anode in short circuit number of times, so as to can achieve the saving of electrodeposition process energy consumption；
(3) loose structure of anode so that the actual current density for flowing through anode is greatly lowered, this are anodic overpotential
It is greatly reduced, saves electro-deposition power consumption and further lay a good foundation；Low current density can be such that the passivating film of anode surface more causes
Close, this is very beneficial for extending anode life and improves cathode product quality；
(4) loose structure of anode not only makes quality of anode significantly mitigate, the metal raw material of anode manufacture significantly subtracts
Few, and labor intensity when being effectively reduced workman's change poles plate.
Description of the drawings
The shaping schematic view of 1 porous al base sacrificial anode of the present invention of accompanying drawing；
Accompanying drawing 2 is I enlarged drawing in accompanying drawing 1；
Accompanying drawing 3 is II enlarged drawing in accompanying drawing 1；
Accompanying drawing 4 is III enlarged drawing in accompanying drawing 1；
In figure：Alloy matrix aluminum --- 100, porous anode crude green body --- 200, porous aluminum based composite anode --- 300, aluminum is closed
The through hole of " three-dimensional through hole structure " in auri body --- 101, the micropore of aluminium alloy matrix surface --- 102, pb-ag alloy internal layer ---
201, metal outer layer --- 301.
Specific embodiment
The invention will be further described below in conjunction with the accompanying drawings, but the present invention is not limited thereto.
Referring to accompanying drawing 1,2,3,4.
Preparation of 1 Zinc electrolysis of embodiment with porous al base sacrificial anode
A kind of hydrometallurgy electro-deposition operation porous aluminum based composite anode, the composite anode matrix are with " three-dimensional
The aluminium alloy of through-hole structure ", on the hole wall of " the three-dimensional through hole structure " of alloy matrix aluminum (100) and aluminium alloy matrix surface
It is provided with clad, lead of the clad by the ripe lead anode of pb-ag alloy internal layer (201) and hydrometallurgy electrodeposition operation
Alloy outer (301) is constituted；In alloy matrix aluminum through hole (101) size of " three-dimensional through hole structure " be 4-6mm, alloy matrix aluminum
Porosity be 60%；In clad, the thickness of internal layer pb-ag alloy is 0.3mm, and the thickness of outer layer metal is 1mm；Lead silver is closed
The weight/mass percentage composition of Jin Zhongyin is that the weight/mass percentage composition of each element in 0.2-0.6wt% alloy matrix aluminums is：
0.5wt%Mg, 3wt%Si and 0.5wt%Cu, aluminum surplus.
The size of anode hole is 1-2mm, and the porosity of anode is 55-65%.
Its preparation method, comprises the steps：
The first step：Alloy matrix aluminum pretreatment
Be interconnected from hole, bore hole size be 4-8mm, porosity for 60-80% alloy matrix aluminum,
By alloy matrix aluminum, vacantly on the salpeter solution liquid level in closed reactor, salpeter solution is heated to 100 DEG C,
Produce nitric acid vapor to aoxidize alloy matrix aluminum, oxidization time 5min, after surface produces micropore (102), washing；Then,
Alloy matrix aluminum after by oxidation is placed in the sodium hydroxide lye that sodium hydrate content is 60g/l and soaks 5min, sodium hydroxide
The temperature of alkali liquor is 55 DEG C, and the micropore for being formed nitric acid oxidation expands, finally, deionized water rinsed clean, drying；
The mass percentage concentration of described salpeter solution is 66%, and its volume accounts for the 5% of closed reactor volume；
Second step：Aluminium alloy matrix surface coats pb-ag alloy
By packaged for the pb-ag alloy ingot one of first step gained alloy matrix aluminum and silver content 0.2wt% enter hermetic container, will
Hermetic container is evacuated down to 0.01Pa, then, maintains vacuum, hermetic container is warmed up to after 520 DEG C of insulation 40min, Xiang Mi
Close, the pressure of hermetic container is made up to 60Mpa, after pressurize 60mi；Keep hermetic container in pressure not
Become, rate of temperature fall is 2 DEG C/min, cools to 320 DEG C with stove, and release, at this temperature, slowly by alloy matrix aluminum from lead melt
Middle taking-up, air-cooled, obtain the porous anode crude green body (200) that surface is combined with pb-ag alloy layer；
3rd step：To second step gained porous anode, just base carries out post processing
Second step gained anode crude green body is placed in chemical plating fluid, after 25min being reacted at a temperature of 80 DEG C, in temperature is
350 DEG C of hydrometallurgy electrodeposition operation with ripe lead anode with metal melt in carry out the bath circulation of 3 minor metals, obtain wet method
Metallurgical electro-deposition operation is with porous aluminum based composite anode (300)；
In chemical plating fluid, the content of each component is：
Pyrovinic acid 200ml/l,
Tin methane sulfonate 320ml/l,
Pyrovinic acid lead 150ml/l,
Thiourea 80g/l,
Sodium hypophosphite 10g/l,
EDTA 2g/l,
Ascorbic acid 2g/l.
Quantitative measurement result shows：In anode prepared by the present embodiment, silver content is 0.13%, only current wet method
Zinc metallurgy with Pb-Ag (0.8wt%) anode industrial 16%；Electrical conductivity 5.85MS m-1, it is higher by flat board Pb-Ag (0.8wt%)
Anode 20%；Tensile strength 42.5MPa, equivalent to 2 times of flat board alloy lead anode.By contrasting porous base described in the present embodiment
Electrodeposition behavior of the anode with flat board Pb-Ag (0.8wt%) anode under the conditions of the industrial electrolysis of Zinc electrolysis finds：Porous aluminium base sun
The overpotential for oxygen evolution of pole reduces 148mV compared with flat board Pb-Ag (0.8wt%) anode；Rate of corrosion in electrolyte system is only flat
The 20% of plate anode；Lead content in cathode product zinc is 0.00079%, only flat board anode gained cathode product 51%.This
A little test results show that the combination property of anode of the present invention is far superior to traditional flat board lead anode.
Preparation of the 2 bronze medal electrodeposition of embodiment with porous al base sacrificial anode
A kind of hydrometallurgy electro-deposition operation porous aluminum based composite anode, the composite anode matrix are with " three-dimensional
The aluminium alloy of through-hole structure ", on the hole wall of " the three-dimensional through hole structure " of alloy matrix aluminum (100) and aluminium alloy matrix surface
It is provided with clad, lead of the clad by the ripe lead anode of pb-ag alloy internal layer (201) and hydrometallurgy electrodeposition operation
Alloy outer (301) is constituted；In alloy matrix aluminum through hole (101) size of " three-dimensional through hole structure " be 5-8mm, alloy matrix aluminum
Porosity be 70%；In clad, the thickness of internal layer pb-ag alloy is 0.3mm, and the thickness of outer layer metal is 1.2mm；Lead silver
In alloy, the weight/mass percentage composition of silver is that the weight/mass percentage composition of each element in 0.2-0.6wt% alloy matrix aluminums is：
0.9wt%Mg, 4wt%Si and 1wt%Cu, aluminum surplus.
The size of anode hole is 1-2mm, and the porosity of anode is 55-65%.
Its preparation method, comprises the steps：
The first step：Alloy matrix aluminum pretreatment
Be interconnected from hole, bore hole size be 4-8mm, porosity for 60-80% alloy matrix aluminum,
By alloy matrix aluminum, vacantly on the salpeter solution liquid level in closed reactor, heating salpeter solution is produced to 60 DEG C
Caliche acid vapor is aoxidized to alloy matrix aluminum, oxidization time 8min, after surface produces micropore (102), washing；Then, will
Alloy matrix aluminum after oxidation is placed in the sodium hydroxide lye that sodium hydrate content is 40g/l and soaks 10min, sodium hydroxide alkali
The temperature of liquid is 45 DEG C, and the micropore for being formed nitric acid oxidation expands, finally, deionized water rinsed clean, drying；
The mass percentage concentration of described salpeter solution is 66%, and its volume accounts for the 30% of closed reactor volume；
Second step：Aluminium alloy matrix surface coats pb-ag alloy
By packaged for the pb-ag alloy ingot one of first step gained alloy matrix aluminum and silver content 0.6wt% enter hermetic container, will
Hermetic container is evacuated down to 1Pa, then, maintains vacuum, and hermetic container is warmed up to after 520 DEG C of insulation 30min, to closed appearance
Noble gases are passed through in device, make the pressure of hermetic container up to 90Mpa, after pressurize 45mi；Keep pressure in hermetic container constant, drop
Warm speed is 5 DEG C/min, cools to 330 DEG C with stove, and alloy matrix aluminum at this temperature, is slowly taken from lead melt by release
Go out, air-cooled, obtain the porous anode crude green body (200) that surface is combined with pb-ag alloy layer；
3rd step：To second step gained porous anode, just base carries out post processing
Second step gained anode crude green body is placed in chemical plating fluid, after 30min being reacted at a temperature of 90 DEG C, in temperature is
350 DEG C of hydrometallurgy electrodeposition operation with ripe lead anode with metal melt in carry out the bath circulation of 6 minor metals, obtain wet method
Metallurgical electro-deposition operation is with porous aluminum based composite anode (300)；
In chemical plating fluid, the content of each component is：
Pyrovinic acid 200ml/l,
Tin methane sulfonate 320ml/l,
Pyrovinic acid lead 150ml/l,
Thiourea 80g/l,
Sodium hypophosphite 10g/l,
EDTA 2g/l,
Ascorbic acid 2g/l.
Quantitative measurement result shows：In anode prepared by the present embodiment, silver content is 0.04%, electrical conductivity
5.46MS·m-1, it is higher by flat board Pb-Ag (0.8wt%) anode 12%；Tensile strength 34.5MPa, equivalent to flat board metal sun
1.5 times of pole.By porous base anode described in relative analyses the present embodiment and classic flat-plate Pb-Ca-Sn anode in copper electrodeposition
Behavior finds that the overpotential for oxygen evolution of porous al base sacrificial anode reduces 128mV compared with flat board anode；Rate of corrosion in electrolyte system is only
For flat board anode 25%；Lead content in cathode product copper is only flat board anode gained cathode product 51%.These test knots
Fruit shows that the combination property of anode of the present invention is far superior to traditional flat board lead anode.
Claims (9)
1. hydrometallurgy electro-deposition operation porous aluminum based composite anode, it is characterised in that：The composite anode matrix be with
The aluminium alloy of " three-dimensional through hole structure ", on the hole wall of " the three-dimensional through hole structure " of alloy matrix aluminum and aluminium alloy matrix surface
Clad is provided with, outside metal of the clad by pb-ag alloy internal layer with hydrometallurgy electrodeposition operation maturation lead anode
Layer composition；
The preparation method of described composite anode, comprises the steps：
The first step：Alloy matrix aluminum pretreatment
Be interconnected from hole, bore hole size be 4-8mm, porosity for 60-80% alloy matrix aluminum,
By alloy matrix aluminum, it is placed in the nitric acid vapor that temperature is 60-100 DEG C and aoxidizes, after surface produces micropore, washing；Then,
Alloy matrix aluminum after by oxidation is placed in sodium hydroxide lye and soaks, and the micropore for being formed nitric acid oxidation expands, and finally, spends
Ionized water rinsed clean, drying；
Second step：Aluminium alloy matrix surface coats pb-ag alloy
By packaged to first step gained alloy matrix aluminum and pb-ag alloy ingot one enter hermetic container, hermetic container is evacuated down to
0.01-10Pa, then, maintains vacuum, and hermetic container is warmed up to after 350-520 DEG C of insulation at least 10min, to hermetic container
In be passed through noble gases, make the pressure of hermetic container reach 15-120Mpa, after pressurize at least 30 min, cool to 320- with stove
330 DEG C, release at this temperature, alloy matrix aluminum is taken out from lead melt, air-cooled, obtains surface and is combined with pb-ag alloy
The porous anode crude green body of layer；
3rd step：To second step gained porous anode, just base carries out post processing
After to second step gained anode crude green body surface chemistry terne coating, in the hydrometallurgy electrodeposition that temperature is 350-450 DEG C
Operation with ripe lead anode with metal melt in carry out at least 3 times recycle metals baths, obtain hydrometallurgy electro-deposition operation
Use porous aluminum based composite anode.
2. composite anode according to claim 1, it is characterised in that：The through hole of " three-dimensional through hole structure " in alloy matrix aluminum
Size is 4-8mm, and the porosity of alloy matrix aluminum is 60-80%.
3. composite anode according to claim 1, it is characterised in that：In clad, the thickness of internal layer pb-ag alloy is 0.2-
0.5mm, the thickness of outer layer metal is 0.8-2.5mm.
4. composite anode according to claim 3, it is characterised in that：In pb-ag alloy, the weight/mass percentage composition of silver is 0.2-
0.6wt%.
5. composite anode according to claim 1, it is characterised in that：The weight/mass percentage composition of each element in alloy matrix aluminum
For：0.5-1.5wt%Mg, 3-5wt%Si, 0.5-1.5wt%Cu, aluminum surplus.
6. composite anode according to claim 1-5 any one, it is characterised in that：The size of anode hole is 1-2mm, positive
The porosity of pole is 55-65%.
7. composite anode according to claim 6, it is characterised in that：Alloy matrix aluminum is aoxidized in nitric acid vapor, be by
On alloy matrix aluminum salpeter solution liquid level vacantly in closed reactor, heating salpeter solution carries out oxygen to alloy matrix aluminum
Change；The mass percentage concentration of described salpeter solution is 65-68%, and its volume accounts for the 5-30% of closed reactor volume, during oxidation
Between 5-30min；
In sodium hydroxide lye, sodium hydrate content is 40-60g/l, and the temperature of sodium hydroxide lye is 40-55 DEG C, soak time
5-10min.
8. composite anode according to claim 6, it is characterised in that：When lowering the temperature with stove, pressure in hermetic container is kept to exist
15-120Mpa, rate of temperature fall are 1-5 DEG C/min.
9. composite anode according to claim 6, it is characterised in that：Surface chemistry terne coating, is by porous anode
Just base is placed in chemical plating fluid, at a temperature of 75-100 DEG C reacts 20-60min, and in chemical plating fluid, the content of each component is：
Pyrovinic acid 150-350ml/l,
Tin methane sulfonate 200-400 ml/l,
Pyrovinic acid lead 100-300 ml/l,
Thiourea 50-100g/l,
Sodium hypophosphite 5-15g/l,
EDTA1-3 g/l,
Ascorbic acid 1-3 g/l.
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| CN115101722B (en) * | 2022-06-28 | 2023-06-23 | 晖阳(贵州)新能源材料有限公司 | Preparation method of porous silver-coated hard carbon composite material by magnetron sputtering method |
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| CN101333668A (en) * | 2008-07-18 | 2008-12-31 | 中南大学 | Method for preparing Pb-based porous energy-conserving anode for non-ferrous metal deposition |
| CN104313652A (en) * | 2014-09-25 | 2015-01-28 | 昆明理工大学 | Preparation method of aluminum-based multiphase inert composite anode material |
| CN204570063U (en) * | 2015-03-09 | 2015-08-19 | 中南大学 | Hydrometallurgy galvanic deposit operation porous aluminum based composite anode |
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| CN101333668A (en) * | 2008-07-18 | 2008-12-31 | 中南大学 | Method for preparing Pb-based porous energy-conserving anode for non-ferrous metal deposition |
| CN104313652A (en) * | 2014-09-25 | 2015-01-28 | 昆明理工大学 | Preparation method of aluminum-based multiphase inert composite anode material |
| CN204570063U (en) * | 2015-03-09 | 2015-08-19 | 中南大学 | Hydrometallurgy galvanic deposit operation porous aluminum based composite anode |
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| 锌电积用新型铝基铅银合金复合阳极材料的制备及性能研究;杨海涛;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20120515;第27页，41页第1段，第42页第3段 * |
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