CN102383145B - Composite porous electrode for sulfuric acid system and preparation method thereof - Google Patents
Composite porous electrode for sulfuric acid system and preparation method thereof Download PDFInfo
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- CN102383145B CN102383145B CN2011103061569A CN201110306156A CN102383145B CN 102383145 B CN102383145 B CN 102383145B CN 2011103061569 A CN2011103061569 A CN 2011103061569A CN 201110306156 A CN201110306156 A CN 201110306156A CN 102383145 B CN102383145 B CN 102383145B
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Abstract
The invention provides a composite porous electrode for a sulfuric acid system and a preparation method thereof. The electrode comprises a reinforced metal substrate, a Pb or Pb-based alloy (Pb-Me') transition layer and a Pb or Pb-based alloy (Pb-Me'') porous layer from inside to outside in sequence. The preparation method is characterized in that the transition layer is obtained by chemical plating and metal melt dip plating in chloride molten salt or is obtained by directly adopting metal melt dip plating; and the porous layer is obtained by adopting an infiltration method or a counter-gravity infiltration method. By adopting the transition layer, the reinforced metal substrate and porous layer in the composite porous electrode are bonded more firmly and the electrolyte can not infiltrate via the porous layer and can not corrode the substrate, thus ensuring the electrode to have longer service life. The electrode has a simple process and a reasonable structure. The composite layers of the prepared composite porous electrode are bonded firmly. The electrode has high strength, strong corrosion resistance and long service life, thus solving the problems of short service life and low strength of the electrode existing in the sulfuric acid system for a long time. The electrode is suitable for industrial application.
Description
Technical field
The present invention relates to a kind of composite porous electrode for sulfuric acid system and preparation method thereof, particularly metal electro-deposition or plating synthesize with compound porous anode and Organic Electricity the preparation method who uses composite porous electrode.Belong to technical field of electrochemistry.
Background technology
Sulfuric acid is a kind of electrolytic solution that is widely used, but its strong corrosive nature make can be used for this electrolyte system anode seldom.Pb or Pb base alloy electrode can generate the anti-corrosion strong PbO of one deck when Sulfuric Acid Solution polarizes due to it
2Protective membrane and become a kind of electrode materials the most frequently used in the sulfur acid electrolyte system particularly is used for metal electrodeposition or plating and is used for Organic Electricity as solidity to corrosion negative electrode or anode synthetic as insoluble anode.
The current density that Organic Electricity synthesizes is generally less.When porous Pb or Pb base alloy electrode are used for this process, because it has larger specific surface area, can increase reaction area, improve the total reaction electric current, thereby improve production capacity.Patent ZL200710034340.6 shows, when Pb or Pb base alloy Multi-hole energy-saving anode are used for the non-ferrous metal galvanic deposit, can reduce anode real current density, reduces electrochemical polarization, reduces overpotential for oxygen evolution, and energy efficient improves current efficiency.When being used for the electrodeposition of Cu, Zn, Mn, Ni, Co, Cr etc., oxygen overpotential on anode can reduce by 50～180mV, and current efficiency improves 1～10%.Can reduce in addition creep and the distortion of anode, the oxide film that the surface is formed is more fine and close, reduces anodic corrosion speed, improves the quality of electrodeposition product.Therefore be subject to paying close attention to more and more widely.
But mechanical property and the conductivity of porous electrode are relatively poor, have affected its industrial applications, need to strengthen its performance.Patent 200810031807.6 adopts sandwich structure, tower structure and grid formula structure to promote mechanical property and the conductivity of porous electrode.The characteristics of these structure electrodes are that direct combination one material is the enhancing metal substrate of Pb, Al, Ti and alloy thereof in porous electrode, make the different component of electrode bring into play respectively different functions, wherein strengthen metal substrate carry load and conduction current, porous layer continues to bring into play the chemical property of porous material.Porous layer and enhancing metal substrate direct combination, the sulfuric acid electrolyte of severe corrosive can see through porous layer corrode substrate with strengthening metal substrate contact.Therefore, when requiring to strengthen metal substrate and must having outstanding physical strength and conductivity, also need the good corrosion resistance of its tool.But in patent 200810031807.6, the corrosion resistance of listed enhancing metal substrate in sulphuric acid soln is limited, greatly shortens the life-span of composite porous electrode, perhaps can form the passive film of high resistance on the surface, and bath voltage is sharply raise, and affects electric energy efficiency.Moreover when the material that strengthens metal substrate was non-Pb and Pb alloy, the direct combination of substrate and porous layer was more difficult, needed complicated casting device and casting technique.Therefore, need to improve this composite porous electrode and manufacture method thereof, to extend its work-ing life.
Summary of the invention
The object of the invention is to overcome the deficiency of prior art and provide between simple, rational in infrastructure, the prepared composite porous electrode composite bed of a kind of processing method in conjunction with firm, that intensity is high, erosion resistance is strong, the life-span is long composite porous electrode for sulfuric acid system and preparation method thereof.
A kind of composite porous electrode for sulfuric acid system of the present invention comprises three parts, is followed successively by from inside to outside metal substrate, Pb or Pb base alloy (Pb-Me ') transition layer, Pb or Pb base alloy (Pb-Me ") porous layer.
In a kind of composite porous electrode for sulfuric acid system of the present invention, described metal substrate is selected from a kind of in metal Pb or Pb base alloy (Pb-Me), metal A l or Al base alloy (Al-Me), metal Ti or Ti base alloy (Ti-Me), metal Fe or Fe base alloy (Fe-Me), metal Cu or Cu base alloy (Cu-Me); Wherein alloying element Me is selected from least a in Ag, Ca, Ba, Ce, Nd, Cr, Sn, Ni, Ti, Al, Zn, Fe, Si, Mg; The quality percentage composition of alloy constituent element Me is 0～50%; The structure of described enhancing metal substrate is a kind of in flat, radiation formula, sieve mesh type or grid formula; The thickness of described enhancing metal substrate is 0.5mm～8mm.
In a kind of composite porous electrode for sulfuric acid system of the present invention, described transition layer Pb or Pb base alloy (Pb-Me ') in, alloying element Me ' is selected from least a in Co, Ag, Nd, Al, Ce, Sn, alloying element content is 0wt.%～30wt.%, and the thickness of described transition layer is 0.05～1mm.
In a kind of composite porous electrode for sulfuric acid system of the present invention, in described porous layer Pb or Pb base alloy (Pb-Me "); alloying element Me " be at least a in Ag, Ca, Sn, Sr, Sb, Ti, Al, Zn, Ce, Ba, Tl, Si, Mn, Co, Fe, Bi, alloying element content is 0wt.%～49.9wt.%.
The preparation method of a kind of composite porous electrode for sulfuric acid system of the present invention comprises the steps:
The first step: strengthen the preparation of metal substrate
By enhancing metal substrate component and the structure of design, selective enhancement metal substrate material is made corresponding enhancing metal matrix slab A; Described enhancing metal substrate is selected from a kind of in metal Pb or Pb base alloy (Pb-Me), metal A l or Al base alloy (Al-Me), metal Ti or Ti base alloy (Ti-Me), metal Fe or Fe base alloy (Fe-Me), metal Cu or Cu base alloy (Cu-Me); Wherein alloying element Me is selected from least a in Ag, Ca, Ba, Ce, Nd, Cr, Sn, Ni, Ti, Al, Zn, Fe, Si, Mg; The quality percentage composition of alloy constituent element Me is 0～50%;
Second step: prepare transition layer on enhancing metal matrix slab
The metal Pb of the first step preparation or Pb base alloy (Pb-Me), metal Cu or Cu base alloy (Cu-Me) are strengthened metal matrix slab A, and to immerse temperature be 3～60s in the Pb of 320～550 ℃ or Pb base alloy (Pb-Me ') melt; Obtain the enhancing metal matrix slab B that the surface is coated with Pb or Pb base alloy (Pb-Me ') transition layer; Or
After the metal A l of the first step preparation or Al base alloy (Al-Me), metal Ti or Ti base alloy (Ti-Me), metal Fe or Fe base alloy (Fe-Me) are strengthened metal matrix slab A and are placed in the molten chloride that contains Pb and carry out electroless plating; Immerse temperature and be 3～60s in the Pb of 320～550 ℃ or Pb base alloy (Pb-Me ') melt; Obtain the enhancing metal matrix slab C that the surface is coated with Pb or Pb base alloy (Pb-Me ') transition layer; Described electroless plating temperature is 350～550 ℃, and the time is 30s～5min;
The 3rd step: THROUGH METHOD prepares porous layer
The second step gained is strengthened metal matrix slab B or strengthen metal matrix slab C being placed in center, seepage flow chamber, periphery is filled full filler grain, is heated to 180～310 ℃; Preferred 250～300 ℃; Then, with Pb or Pb base alloy (Pb-Me ") heat fused, inject seepage flow chamber, naturally cooling; Obtain strengthening metal matrix slab B or strengthening the electrode that metal matrix slab C surface coverage has Pb or Pb base alloy (Pb-Me ") porous layer; Be filled with a large amount of filler grains in described porous layer; Described Pb or Pb base alloy (Pb-Me ") temperature of fusion is 300～600 ℃, preferred 400～550 ℃,
The 4th step: the removal of filler grain
The 3rd step the electrode obtained is placed in solvent, applies ultra-sonic oscillation, remove filler grain, namely obtain composite porous electrode for sulfuric acid system.
In the preparation method of a kind of composite porous electrode for sulfuric acid system of the present invention, described THROUGH METHOD prepares porous layer and adopts Pb or Pb base alloy (Pb-Me ") heat fused; the seepage flow chamber is injected in the pressurization of alloy melt from bottom, seepage flow chamber along the antigravity direction; the alloy melt injection speed is 0.01～0.2m/s, preferred 0.05～0.1m/s.
In the preparation method of a kind of composite porous electrode for sulfuric acid system of the present invention, the structure of described enhancing metal substrate is a kind of in flat, radiation formula, sieve mesh type or grid formula; The thickness of described enhancing metal substrate is 0.5mm～8mm.
In the preparation method of a kind of composite porous electrode for sulfuric acid system of the present invention, described transition layer Pb or Pb base alloy (Pb-Me ') in, alloying element Me ' is selected from least a in Co, Ag, Nd, Al, Ce, Sn, alloying element content is 0wt.%～30wt.%, and the thickness of described transition layer is 0.05～1mm.
In the preparation method of a kind of composite porous electrode for sulfuric acid system of the present invention, in described porous layer Pb or Pb base alloy (Pb-Me "); alloying element Me " be at least a in Ag, Ca, Sn, Sr, Sb, Ti, Al, Zn, Ce, Ba, Tl, Si, Mn, Co, Fe, Bi, alloying element content is 0wt.%～49.9wt.%.
In the preparation method of a kind of composite porous electrode for sulfuric acid system of the present invention, described molten chloride comprises main salt PbCl
2-NaCl-CaCl
2And be selected from AgCl, RECl
2And SnCl
2In at least a auxiliary salt; Described main salt PbCl
2-NaCl-CaCl
2The quality percentage composition of each component is followed successively by 50%～90%, 5%～30%, 1%～20%; Preferred 75%～90%, 5%～15% and 8%～15%; Described auxiliary salt AgCl, RECl
2And SnCl
2The quality percentage composition of each component is followed successively by 0～5%, 0～5% and 0～10%; Preferred 0～1%, 0～5% and 0～1%.
In the preparation method of a kind of composite porous electrode for sulfuric acid system of the present invention, described filler grain is selected from CaSO
4, Na
2SO
4, K
2SO
4, MgSO
4, ZnSO
4, CaCl
2, at least a in NaCl and KCl, preferred CaSO
4, K
2SO
4Or ZnSO
4The particle diameter of filler grain is 0.01～5mm, preferred 0.5～2mm; Filler grain is shaped as spherical or cylindrical.
In the preparation method of a kind of composite porous electrode for sulfuric acid system of the present invention, described solvent is selected from Na
2CO
3Solution, NH
4HCO
3At least a in solution, clear water, pressure water, warm water.
The preparation method of a kind of composite porous electrode for sulfuric acid system of the present invention when the enhancing metal substrate is Pb or Pb base alloy, comprises the steps:
The first step: strengthen the preparation of metal substrate
By enhancing metal substrate component and the structure of design, select metal Pb or Pb base alloy (Pb-Me) as strengthening the metal substrate material; Wherein alloying element Me is selected from least a in Ag, Ca, Ba, Ce, Nd, Sn, Ti, Al; The quality percentage composition of alloy constituent element Me is 0～50%;
Second step: THROUGH METHOD prepares porous layer
The first step gained is strengthened the metal matrix slab be placed in center, seepage flow chamber, periphery is filled full filler grain, is heated to 180～310 ℃; Then, with Pb or Pb base alloy (Pb-Me ") heat fused, inject seepage flow chamber, naturally cooling; Obtain the electrode of Pb or Pb base alloy (Pb-Me ") porous layer being arranged strengthening metal matrix slab surface coverage; Be filled with a large amount of filler grains in described porous layer; Described Pb or Pb base alloy (Pb-Me ") temperature of fusion is 300～600 ℃;
The 3rd step: the removal of filler grain
The second step the electrode obtained is placed in solvent, applies ultra-sonic oscillation, remove filler grain, namely obtain composite porous electrode for sulfuric acid system.
The present invention strengthening the middle Pb base alloy transition layer that adds a sulfuric acid corrosion resistant of metal substrate and porous layer, can make the enhancing metal substrate directly not contact sulfuric acid electrolyte due to employing said structure and preparation method on the one hand, shields; Be conducive on the other hand Pb or Pb base alloy porous layer and the metallurgical binding that strengthens metal substrate; Compared with prior art, have the following advantages:
1, be coated with one deck Pb or Pb base alloy (Pb-Me ') transition layer strengthening metallic substrate surfaces; Transition layer guarantees that on the one hand substrate does not directly contact with electrolytic solution, and protective substrate is not corroded, and porous layer is combined firmly with the enhancing metal substrate.Therefore, transition layer must have good corrosion resistance, and with substrate can be in conjunction with firm.The fused salt chemistry plating is to utilize the redox principle.When strengthening metal substrate and immerse in the melting salt that contains Pb, Pb can be out replaced and be attached to fresh enhancing metallic substrate surfaces; Add auxiliary salt in the main salt of fused salt chemistry plating, can effectively improve the bonding strength of Pb or Pb base alloy layer and substrate.Plate gained Pb or Pb base alloy layer by fused salt chemistry and often have aperture, the surface also is difficult to smooth; Coating not exclusively, electrolytic solution is infiltrated and cause the corrosion of substrate.Therefore, after having plated in fused salt, to strengthen immediately in the Pb or Pb base alloy Pb-Me ' of metal substrate immersion melting, can repair coating on the one hand, can be covered with again on the other hand one deck Pb or Pb base alloy (Pb-Me ') on coating surface, coating is thickeied and controlled the coating surface composition.
2, in the antigravity flow event, the surface tension that metal melt overcomes between itself and filler grain is filled among the space of filler grain, and the size of filler grain is huge on the flow event impact.In general, the filler grain size is larger, and the space between particle is also larger, is conducive to seepage flow and the filling of melt, and filler grain is undersized, might make melt can't form effective seepage flow at all and obtain continuous porous material.Therefore, it is 0.01～5mm that the present invention selects the particle diameter of filler grain, can effectively guarantee to form effective seepage flow at Pb or Pb base alloy (Pb-Me ") metal melt between filler grain, obtains continuous porous material.
3, the temperature of controlling the seepage flow chamber remains on below the fusing point of Pb or Pb alloy (Pb-Me '), when Pb or Pb base alloy (Pb-Me ") when high-temperature metal melt enters the seepage flow chamber from the bottom; can partly or entirely melt Pb or Pb alloy (Pb-Me '); thus be frozen into as a whole together with strengthening metal substrate; be conducive to Pb or Pb base alloy porous layer and form metallurgical binding with strengthening metal substrate, effectively improve the structural strength of composite porous electrode of the present invention.
4, adopt the antigravity THROUGH METHOD to prepare porous vesicular surface, make Pb or Pb base alloy (Pb-Me ") high-temperature metal melt enter the seepage flow chamber from the bottom with certain speed.On the one hand, melt under the effect of self gravitation, guarantee melt retaining layer stream mode in mould filling process, fill type steadily, without volume gas be mingled with, thereby form to filler grain effectively, seepage flow continuously; On the other hand, be conducive to prepare the large size composite porous electrode.Utilize the antigravity THROUGH METHOD to prepare porous layer, can obtain zero defect, the large size composite porous electrode, and flow event is easy to control, and yield rate is high.
5, the structure of metal substrate adopts flat, grid formula, sieve mesh type or radiation formula, is guaranteeing that electrode has under the prerequisite of enough mechanical properties and conductivity, can utilize the production unit of existing electrode to produce, and lowers production cost.
In sum, between simple, rational in infrastructure, the prepared composite porous electrode composite bed of processing method of the present invention in conjunction with firmly, intensity is high, erosion resistance is strong, the life-span is long, solved for a long time in sulfuric acid system the problem that electrode life is short, intensity is low.Be suitable for industrial applications.
Description of drawings
Accompanying drawing 2 strengthens the metal substrate structure schematic diagram for grid formula of the present invention;
Accompanying drawing 3 strengthens the metal substrate structure schematic diagram for sieve mesh type of the present invention;
Accompanying drawing 4 strengthens the metal substrate structure schematic diagram for radiation formula of the present invention;
In figure: the 1-porous layer; The 2-transition layer; 3-strengthens metal substrate.
Embodiment
With the following Examples content of the present invention is elaborated.
Embodiment 1:
The Pb-Ca that 8mm is thick (0.09wt.%)-Sn (0.98wt.%)-Al (0.011wt.%) plate floods 5s in Pb-Ag (0.8wt.%) melt of 330 ℃, obtain the thick Pb-Ag transition layer of 0.05mm, the enhancing metal substrate and the particle diameter that then the surface are coated with the Pb-Ag transition layer are the K of 0.8mm-1.0mm
2SO
4Filler grain is made prefabricated section.With pack into seepage flow chamber of prefabricated section, and be heated to 250 ℃; Pb-Ag (0.8wt.%)-Bi (0.3wt.%) alloy is heated to 400 ℃ of fusings, apply mold filling pressure, drive melting Pb-Ag (0.8wt.%)-Bi (0.3wt.%) alloy and enter the seepage flow chamber with the speed of 0.05m/s, be full of rear naturally cooling, then with 50 ℃ of hot water wash, filler grain is removed, obtained Pb-Ca (0.09wt.%)-Sn (0.98wt.%)-Al (0.011wt.%)/Pb-Ag (0.8wt.%)/Pb-Ag (0.8wt.%)-Bi (0.3wt.%) composite porous electrode.
Embodiment 2:
304 stainless steel plates are placed in PbCl
2(70wt.%)-CaCl
2Be coated with Pb coating in (14wt.%)-NaCl (15wt.%) fused salt, described 304 stainless steel plate thickness are 0.5mm, and described temperature of molten salt is 480 ℃; Then flood 20s immediately in Pb-Nd (0.1wt.%) alloy melt of 400 ℃, obtaining thickness is the Pb-Nd transition layer of 0.1mm.Be the K of 4.0mm-5.0mm with particle diameter
2SO
4Pack into together with stainless steel plate that the surface is coated with Pb-Nd transition layer seepage flow chamber of filler grain, and be preheated to 200 ℃; Pb-Ag (0.8wt.%) alloy is heated to 400 ℃ of fusings.Apply mold filling pressure, drive melting Pb-Ag (0.8wt.%) alloy and enter the seepage flow chamber from bottom, seepage flow chamber along the antigravity direction with the speed of 0.2m/s, be full of rear naturally cooling, then with clear water, filler grain is removed, obtained Steel/Pb-Nd (0.1wt.%)/Pb-Ag (0.8wt.%) composite porous electrode.
Embodiment 3:
The Al-Si that 1mm is thick (1wt.%) alloy radiation formula framework is at the PbCl of 500 ℃
2(80wt.%)-CaCl
2(9wt.%)-NaCl (10wt.%)-SnCl
2(1wt.%) plating Pb-Sn alloy in the fused salt, and flood 5s in melting Pb-Sn (20wt.%) alloy of 400 ℃, obtain the thick Pb-Sn alloy transition layer of 0.15mm.Al-Si (1wt.%) the alloy radiation formula framework and the particle diameter that the surface are coated with Pb-Sn alloy transition layer are the CaSO of 1.6mm～2.0mm
4Filler grain is made prefabricated section, and prefabricated section is inserted the seepage flow chamber, and filler grain is together with strengthening basal plate preheating to 300 ℃; Pb-Ag (0.3wt.%)-Ca (0.03wt.%)-Sr (0.03wt.%) alloy is heated to 500 ℃ of fusings, apply mold filling pressure, drive melting Pb-Ag (0.3wt.%)-Ca (0.03wt.%)-Sr (0.03wt.%) alloy and enter the seepage flow chamber from bottom, seepage flow chamber along the antigravity direction with the speed of 0.1m/s, be full of rear coolingly, use NH
4HCO
3The aqueous solution is removed filler grain, obtains Al-Si (1wt.%)/Pb-Sn (20wt.%)/Pb-Ag (0.3wt.%)-Ca (0.03wt.%)-Sr (0.03wt.%) composite porous electrode.
Embodiment 4:
The Ti grid that 6mm is thick is at PbCl
2(70wt.%)-CaCl
2Be coated with pure Pb layer in (5wt.%)-NaCl (25wt.%) fused salt, and flood 15s in Pb-Ca (1.5wt.%) melt of 350 ℃, obtain the thick Pb-Ca alloy transition layer of 1mm.The Ti grid and the particle diameter that the surface are coated with the Pb-Ca transition layer are the K of 2.5mm～3mm
2SO
4Filler grain is made prefabricated section, and prefabricated section is inserted the seepage flow chamber, and filler grain is preheated to 270 ℃ together with strengthening metal substrate; Pb-Sb (1.3wt.%)-Sn (10.0wt.%)-Ag (0.8wt.%) alloy is heated to 600 ℃ of fusings, apply mold filling pressure, drive melting Pb-Sb (1.3wt.%)-Sn (10.0wt.%)-Ag (0.8wt.%) alloy and enter the seepage flow chamber from bottom, seepage flow chamber along the antigravity direction with the speed of 0.15m/s, be full of rear cooling, way with the ultrasound-enhanced washing is removed filler grain, obtain Ti/Pb-Ca (1.5wt%)/Pb-Sb (1.3wt.%)-Sn (10.0wt.%)-Ag (0.8wt.%) composite porous electrode.
Embodiment 5:
The Cu-Al that 3mm is thick (10wt.%)-Fe (4wt.%)-Ni (5wt.%) alloy sieve tray floods 60s in Pb-Co (0.1wt.%) melt of 400 ℃, obtain the thick Pb-Co alloy transition layer of 0.8mm and be coated with the Cu sieve tray of Pb-Co transition layer on seepage flow indoor location surface, particle diameter is the ZnSO of 0.01mm-0.05mm
4The filler grain pine is contained in the both sides that strengthen metal substrate, and filler grain is preheated to 250 ℃ together with strengthening metal substrate; Pb-Ag (0.6wt.%)-Ce (0.1wt.%) alloy is heated to 550 ℃ of fusings, apply mold filling pressure, drive melting Pb-Ag (0.6wt.%)-Ce (0.1wt.%) alloy and enter the seepage flow chamber from bottom, seepage flow chamber along the antigravity direction with the speed of 0.05m/s, be full of behind the seepage flow chamber cooling, adopt ultra-sonic oscillation, Na
2CO
3Solution washes away filler grain, namely obtains Cu-Al (10wt.%)-Fe (4wt.%)-Ni (5wt.%)/Pb-Co (0.1wt.%)/Pb-Ag (0.6wt.%)-Ce (0.1wt.%) composite porous electrode.
Embodiment 6
The Pb-Ag that 2mm is thick (0.8wt.%) strengthens metal substrate and is arranged on the seepage flow chamber, and both sides filling particle diameter is the Ca of 1.2-1.4mm
2SO
4Filler grain, and be heated to 310 ℃.Pb-Ag (0.8wt.%) alloy is heated to 500 ℃ of fusings, apply mold filling pressure, drive melting Pb-Ag (0.8wt.%) alloy and enter the seepage flow chamber with the speed of 0.03m/s, be full of rear naturally cooling, then with high pressure water, filler grain is rinsed well, obtained Pb-Ag (0.8wt.%)/Pb-Ag (0.8wt.%) composite porous electrode.
Claims (11)
1. a composite porous electrode for sulfuric acid system, comprise three parts, it is characterized in that: be followed successively by from inside to outside enhancing metal substrate, Pb or Pb base alloy Pb-Me ' transition layer, Pb or Pb base alloy Pb-Me ' ' porous layer; Described enhancing metal substrate is selected from a kind of in metal Pb or Pb base alloy Pb-Me, metal A l or Al base alloy A l-Me, metal Ti or Ti base alloy Ti-Me, metal Fe or Fe base alloy Fe-Me, metal Cu or Cu base alloy Cu-Me; Wherein alloying element Me is selected from least a in Ag, Ca, Ba, Ce, Nd, Cr, Sn, Ni, Ti, Al, Zn, Fe, Si, Mg; The quality percentage composition of alloy constituent element Me is 0～50%; The structure of described enhancing metal substrate is a kind of in flat, radiation formula, sieve mesh type or grid formula; The thickness of described enhancing metal substrate is 0.5mm～8mm.
2. a kind of composite porous electrode for sulfuric acid system according to claim 1, it is characterized in that: in described transition layer Pb or Pb base alloy Pb-Me ', alloying element Me ' is selected from least a in Co, Ag, Nd, Al, Ce, Sn, alloying element content is 0wt.%～30wt.%, and the thickness of described transition layer is 0.05～1mm.
3. a kind of composite porous electrode for sulfuric acid system according to claim 2, it is characterized in that: in described porous layer Pb or Pb base alloy Pb-Me ' ', alloying element Me ' ' is at least a in Ag, Ca, Sn, Sr, Sb, Ti, Al, Zn, Ce, Ba, Tl, Si, Mn, Co, Fe, Bi, and alloying element content is 0wt.%～49.9wt.%.
4. a method for preparing as composite porous electrode for sulfuric acid system as described in claim 1,2,3 any one, comprise the steps:
The first step: strengthen the preparation of metal substrate
By enhancing metal substrate component and the structure of design, selective enhancement metal substrate material is made corresponding enhancing metal matrix slab A; Described enhancing metal substrate is selected from a kind of in metal Pb or Pb base alloy Pb-Me, metal A l or Al base alloy A l-Me, metal Ti or Ti base alloy Ti-Me, metal Fe or Fe base alloy Fe-Me, metal Cu or Cu base alloy Cu-Me; Wherein alloying element Me is selected from least a in Ag, Ca, Ba, Ce, Nd, Cr, Sn, Ni, Ti, Al, Zn, Fe, Si, Mg; The quality percentage composition of alloy constituent element Me is 0～50%;
Second step: prepare transition layer on the metal matrix slab
The metal Pb of the first step preparation or Pb base alloy Pb-Me, metal Cu or Cu base alloy Cu-Me are strengthened metal matrix slab A, and to immerse temperature be 3～60s in the Pb of 320～550 ℃ or Pb base alloy Pb-Me ' melt; Obtain the enhancing metal matrix slab B that the surface is coated with Pb or Pb base alloy Pb-Me ' transition layer; Or
After the metal A l of the first step preparation or Al base alloy A l-Me, metal Ti or Ti base alloy Ti-Me, metal Fe or Fe base alloy Fe-Me are strengthened metal matrix slab A and are placed in the molten chloride that contains Pb and carry out electroless plating; Immerse temperature and be 3～60s in the Pb of 320～550 ℃ or Pb base alloy Pb-Me ' melt; Obtain the enhancing metal matrix slab C that the surface is coated with Pb or Pb base alloy Pb-Me ' transition layer; Described electroless plating temperature is 350～550 ℃, and the time is 30s～5min;
The 3rd step: THROUGH METHOD prepares porous layer
The second step gained is strengthened metal matrix slab B or strengthen metal matrix slab C being placed in center, seepage flow chamber, periphery is filled full filler grain, is heated to 180～310 ℃; Then, with Pb or Pb base alloy Pb-Me ' ' heat fused, inject seepage flow chamber, naturally cooling; Obtain strengthening metal matrix slab B or strengthening the electrode that metal matrix slab C surface coverage has Pb or Pb base alloy Pb-Me ' ' porous layer; Be filled with a large amount of filler grains in described porous layer; Described Pb or Pb base alloy Pb-Me ' ' temperature of fusion are 300～600 ℃;
The 4th step: the removal of filler grain
The 3rd step the electrode obtained is placed in solvent, applies ultra-sonic oscillation, remove filler grain, namely obtain composite porous electrode for sulfuric acid system.
5. the preparation method of a kind of composite porous electrode for sulfuric acid system according to claim 4, it is characterized in that: described THROUGH METHOD prepares porous layer and adopts Pb or Pb base alloy Pb-Me ' ' heat fused, the pressurization of alloy melt is from bottom, seepage flow chamber along antigravity direction injection seepage flow chamber, and the alloy melt injection speed is 0.01～0.2m/s.
6. the preparation method of a kind of composite porous electrode for sulfuric acid system according to claim 5 is characterized in that: the structure of described metal substrate is a kind of in flat, radiation formula, sieve mesh type or grid formula; The thickness of described enhancing metal substrate is 0.5mm～8mm.
7. the preparation method of a kind of composite porous electrode for sulfuric acid system according to claim 6, it is characterized in that: in described transition layer Pb or Pb base alloy Pb-Me ', alloying element Me ' is selected from least a in Co, Ag, Nd, Al, Ce, Sn, alloying element content is 0wt.%～30wt.%, and the thickness of described transition layer is 0.05～1mm.
8. the preparation method of a kind of composite porous electrode for sulfuric acid system according to claim 7, it is characterized in that: in described porous layer Pb or Pb base alloy Pb-Me ' ', alloying element Me ' ' is at least a in Ag, Ca, Sn, Sr, Sb, Ti, Al, Zn, Ce, Ba, Tl, Si, Mn, Co, Fe, Bi, and alloying element content is 0wt.%～49.9wt.%.
9. the preparation method of a kind of composite porous electrode for sulfuric acid system according to claim 8, it is characterized in that: described molten chloride comprises main salt PbCl
2-NaCl-CaCl
2And be selected from AgCl, ReCl
2And SnCl
2In at least a auxiliary salt; Described main salt PbCl
2-NaCl-CaCl
2The quality percentage composition of each component is followed successively by 50%～90%, 5%～30%, 1%～20%; Described auxiliary salt AgCl, ReCl
2And SnCl
2The quality percentage composition of each component is followed successively by 0～5%, 0～5% and 0～10%.
10. the preparation method of a kind of composite porous electrode for sulfuric acid system according to claim 9, it is characterized in that: described filler grain is selected from CaSO
4, Na
2SO
4, K
2SO
4, MgSO
4, ZnSO
4, CaCl
2, at least a in NaCl and KCl; The particle diameter of filler grain is 0.01～3mm; Filler grain is shaped as spherical or cylindrical.
11. the preparation method of a kind of composite porous electrode for sulfuric acid system according to claim 10 is characterized in that: described solvent is selected from Na
2CO
3Solution, NH
4HCO
3At least a in solution, clear water, 50 ℃ of hot water.
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| Publication number | Publication date |
|---|---|
| CN101949031A (en) | 2011-01-19 |
| ZA201302807B (en) | 2014-05-26 |
| WO2012051797A1 (en) | 2012-04-26 |
| CN102352498A (en) | 2012-02-15 |
| CN102383145A (en) | 2012-03-21 |
| CN102352498B (en) | 2013-01-02 |
| CN102315455A (en) | 2012-01-11 |
| CN102315455B (en) | 2013-08-14 |
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