CN102383145A - 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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- CN102383145A CN102383145A CN2011103061569A CN201110306156A CN102383145A CN 102383145 A CN102383145 A CN 102383145A CN 2011103061569 A CN2011103061569 A CN 2011103061569A CN 201110306156 A CN201110306156 A CN 201110306156A CN 102383145 A CN102383145 A CN 102383145A
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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 sulfuric acid system with compound porous electrode and preparation method thereof, particularly metal electrodeposition or electroplate with compound porous anode and organic electrosynthesis preparation method with compound 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 is because it can generate the anti-corrosion strong PbO of one deck during anodic polarization in sulphuric acid soln
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 electrosynthesis as solidity to corrosion negative electrode or anode as insoluble anode.
The current density of organic electrosynthesis is generally less.When porous Pb or Pb base alloy electrode are used for this process,, can increase reaction area, improve the total reaction electric current, thereby improve production capacity because it has bigger specific surface area.Patent ZL200710034340.6 shows, when Pb or Pb base alloy porous energy-conserving 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., the anode overpotential for oxygen evolution can reduce by 50～180mV, and current efficiency improves 1～10%.Can reduce anodic creep and distortion in addition, the sull that the surface is formed is more fine and close, reduces anodic corrosion speed, improves the quality of electrodeposition product.Therefore received concern more and more widely.
But the mechanical property and the conductivity of porous electrode are relatively poor, have influenced its industrial applications, need strengthen its performance.Patent 200810031807.6 adopts sandwich structure, tower structure and grid formula structure to promote the mechanical property and the conductivity of porous electrode.The characteristics of these structure electrodes are enhancing metal substrates that a direct compound material is Pb, Al, Ti and alloy thereof in porous electrode; Make the different component of electrode bring into play different functions respectively; Wherein strengthen metal substrate carry load and conduction current, porous layer then continues to bring into play the chemical property of porous material.Porous layer is directly compound with the enhancing metal substrate, and the sulfuric acid electrolyte of severe corrosive can see through porous layer corrode substrate with strengthening metal substrate to 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 the corrosion resistance of listed enhancing metal substrate in sulphuric acid soln is limited in the patent 200810031807.6, shortens the life-span of compound porous electrode greatly, perhaps can form the passive film of high resistance on the surface, and bath voltage is sharply raise, and influences electric energy efficiency.Moreover when the material that strengthens metal substrate was non-Pb and Pb alloy, the direct compound relatively difficulty of substrate and porous layer needed complicated casting device and casting technique.Therefore, need improve this compound porous electrode and method of manufacture thereof, to prolong its work-ing life.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art and provide that a kind of process method is simple, rational in infrastructure, combine firmly between the prepared composite porous electrode composite bed, intensity is high, erosion resistance is strong, the life-span is long sulfuric acid system is with compound porous electrode and preparation method thereof.
A kind of sulfuric acid system of the present invention is used compound porous electrode, comprises three parts, is followed successively by metal substrate, Pb or Pb base alloy (Pb-Me ') transition layer, Pb or Pb base alloy (Pb-Me ") porous layer from inside to outside.
A kind of sulfuric acid system of the present invention is with in the compound porous electrode, and said 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 the Cu base alloy (Cu-Me); Wherein alloying element Me is selected from least a among Ag, Ca, Ba, Ce, Nd, Cr, Sn, Ni, Ti, Al, Zn, Fe, Si, the Mg; The quality percentage composition of alloy constituent element Me is 0～50%; The structure of said enhancing metal substrate is a kind of in flat, radiation formula, sieve aperture formula or the grid formula; The thickness of said enhancing metal substrate is 0.5mm～8mm.
A kind of sulfuric acid system of the present invention is with in the compound porous electrode; Said transition layer Pb or Pb base alloy (Pb-Me ') in; Alloying element Me ' is selected from least a among Co, Ag, Nd, Al, Ce, the Sn, and alloying element content is 0wt.%～30wt.%, and the thickness of said transition layer is 0.05～1mm.
A kind of sulfuric acid system of the present invention is with in the compound porous electrode; In said porous layer Pb or the Pb base alloy (Pb-Me "); alloying element Me " be at least a among Ag, Ca, Sn, Sr, Sb, Ti, Al, Zn, Ce, Ba, Tl, Si, Mn, Co, Fe, the Bi, alloying element content is 0wt.%～49.9wt.%.
A kind of sulfuric acid system of the present invention comprises the steps: with the preparation method of compound porous electrode
The first step: strengthen the preparation of metal substrate
By the enhancing metal substrate component and the structure of design, select to strengthen the metal substrate material and process corresponding enhancing metal-based slab A; Said 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 the Cu base alloy (Cu-Me); Wherein alloying element Me is selected from least a among Ag, Ca, Ba, Ce, Nd, Cr, Sn, Ni, Ti, Al, Zn, Fe, Si, the Mg; The quality percentage composition of alloy constituent element Me is 0～50%;
Second step: on enhancing metal-based slab, prepare transition layer
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-based slab A, and to immerse temperature be 3～60s in 320～550 ℃ Pb or Pb base alloy (the Pb-Me ') melt; Obtain the enhancing metal-based 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) strengthened metal-based slab A and place the molten chloride that contains Pb to carry out electroless plating; Immerse temperature and be 3～60s in 320～550 ℃ Pb or Pb base alloy (the Pb-Me ') melt; Obtain the enhancing metal-based slab C that the surface is coated with Pb or Pb base alloy (Pb-Me ') transition layer; Said electroless plating temperature is 350～550 ℃, and the time is 30s～5min;
The 3rd step: THROUGH METHOD prepares porous layer
The second step gained enhancing metal-based slab B or enhancing metal-based slab C are placed center, seepage flow chamber, and 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 the seepage flow chamber, naturally cooling; Obtain strengthening metal-based slab B or strengthening the electrode that metal-based slab C surface coverage has Pb or Pb base alloy (Pb-Me ") porous layer; Be filled with a large amount of filler grains in the said porous layer; Said 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 gained electrode is placed solvent, apply ultra-sonic oscillation, remove filler grain, promptly obtain sulfuric acid system and use compound porous electrode.
Among the preparation method of a kind of sulfuric acid system of the present invention with compound porous electrode; Said THROUGH METHOD prepares porous layer and adopts Pb or Pb base alloy (Pb-Me ") heat fused; the alloy melt pressurization is injected the seepage flow chamber 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.
Among the preparation method of a kind of sulfuric acid system of the present invention with compound porous electrode, the structure of said enhancing metal substrate is a kind of in flat, radiation formula, sieve aperture formula or the grid formula; The thickness of said enhancing metal substrate is 0.5mm～8mm.
Among the preparation method of a kind of sulfuric acid system of the present invention with compound porous electrode; Said transition layer Pb or Pb base alloy (Pb-Me ') in; Alloying element Me ' is selected from least a among Co, Ag, Nd, Al, Ce, the Sn; Alloying element content is 0wt.%～30wt.%, and the thickness of said transition layer is 0.05～1mm.
Among the preparation method of a kind of sulfuric acid system of the present invention with compound porous electrode; In said porous layer Pb or the Pb base alloy (Pb-Me "); alloying element Me " be at least a among Ag, Ca, Sn, Sr, Sb, Ti, Al, Zn, Ce, Ba, Tl, Si, Mn, Co, Fe, the Bi, alloying element content is 0wt.%～49.9wt.%.
Among the preparation method of a kind of sulfuric acid system of the present invention with compound porous electrode, said molten chloride comprises main salt PbCl
2-NaCl-CaCl
2And be selected from AgCl, RECl
2And SnCl
2In at least a auxilliary salt; Said 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%; Said auxilliary 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%.
Among the preparation method of a kind of sulfuric acid system of the present invention with compound porous electrode, said filler grain is selected from CaSO
4, Na
2SO
4, K
2SO
4, MgSO
4, ZnSO
4, CaCl
2, at least a among NaCl and the 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.
Among the preparation method of a kind of sulfuric acid system of the present invention with compound porous electrode, said solvent is selected from Na
2CO
3Solution, NH
4HCO
3At least a in solution, clear water, pressure water, the warm water.
A kind of sulfuric acid system of the present invention, comprises the steps: when the enhancing metal substrate is Pb or Pb base alloy with the preparation method of compound porous electrode
The first step: strengthen the preparation of metal substrate
By the 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 among Ag, Ca, Ba, Ce, Nd, Sn, Ti, the 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-based slab place 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 the seepage flow chamber, naturally cooling; Obtain the electrode of Pb or Pb base alloy (Pb-Me ") porous layer being arranged strengthening metal-based slab surface coverage; Be filled with a large amount of filler grains in the said porous layer; Said Pb or Pb base alloy (Pb-Me ") temperature of fusion is 300～600 ℃;
The 3rd step: the removal of filler grain
The second step gained electrode is placed solvent, apply ultra-sonic oscillation, remove filler grain, promptly obtain sulfuric acid system and use compound porous electrode.
The present invention adds the Pb base alloy transition layer of a sulfuric acid corrosion resistant owing to adopt said structure and preparation method in the middle of enhancing metal substrate and porous layer, can make the enhancing metal substrate directly not contact sulfuric acid electrolyte on the one hand, shields; Help Pb or Pb base alloy porous layer and the metallurgical binding that strengthens metal substrate on the other hand; Compared with prior art, have the following advantages:
1, is 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 can combine firmly with substrate.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 cemented out and attached to fresh enhancing metallic substrate surfaces; In the main salt of fused salt chemistry plating, add auxilliary salt, can effectively improve the bonding strength of Pb or Pb base alloy layer and substrate.Often have aperture through fused salt chemistry plating gained Pb or Pb base alloy layer, the surface also is difficult to smooth; Coating not exclusively, electrolytic solution is infiltrated and cause the corrosion of substrate.Therefore; After in fused salt, having plated, will strengthen metal substrate immediately and immerse among fused Pb or the Pb base alloy Pb-Me ', can repair coating on the one hand; One deck Pb or Pb base alloy (Pb-Me ') be can on coating surface, be covered with on the other hand again, coating thickening and control coating surface composition made.
2, in the antigravity flow event, the surface tension that metal melt overcomes between itself and the filler grain is filled among the space of filler grain, and the size of filler grain is huge to the flow event influence.Generally speaking, the filler grain size is big more, and the space between the particle is also big more, helps the seepage flow and the filling of melt, and filler grain is undersized, might make melt can't form effective seepage flow and acquisition successive porous material at all.Therefore, it is 0.01～5mm that the present invention selects the particle diameter of filler grain, can effectively guarantee between filler grain, to form effective seepage flow, acquisition successive porous material at Pb or Pb base alloy (Pb-Me ") metal melt.
3, the temperature of control 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 gets into the seepage flow chamber from the bottom; can partly or entirely melt Pb or Pb alloy (Pb-Me '); thus be frozen into as a wholely with strengthening metal substrate, help Pb or Pb base alloy porous layer and form metallurgical binding with strengthening metal substrate, effectively improve the structural strength of the compound 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 get into the seepage flow chamber from the bottom with certain speed.On the one hand, melt under the effect of self gravitation, guarantee that melt keeps laminar flow regime in the mould filling process, fill type steadily, do not have volume gas and be mingled with, thereby form to filler grain effectively, seepage flow continuously; On the other hand, help preparing the compound porous electrode of large size.Utilize the antigravity THROUGH METHOD to prepare porous layer, can obtain zero defect, the compound porous electrode of large size, and flow event is easy to control, the yield rate height.
5, the structure of metal substrate adopts flat, grid formula, sieve aperture formula 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, the attenuating production cost.
In sum; Process method of the present invention is simple, rational in infrastructure, combine between the prepared composite porous electrode composite bed firmly, intensity is high, erosion resistance is strong, the life-span is long; Solved for a long time in the sulfuric acid system problem that electrode life is short, intensity is low.Be suitable for industrial applications.
Description of drawings
Accompanying drawing 2 strengthens the metal substrate structural representation for grid formula of the present invention;
Accompanying drawing 3 strengthens the metal substrate structural representation for sieve aperture formula of the present invention;
Accompanying drawing 4 strengthens the metal substrate structural representation for radiation formula of the present invention;
Among the figure: the 1-porous layer; The 2-transition layer; 3-strengthens metal substrate.
Embodiment
In conjunction with 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 330 ℃ Pb-Ag (0.8wt.%) melt; 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 processed prefabricated section.With the prefabricated section seepage flow chamber of packing into, and be heated to 250 ℃; Pb-Ag (0.8wt.%)-Bi (0.3wt.%) alloy is heated to 400 ℃ of fusings; Apply mold filling pressure; Drive the speed entering seepage flow chamber of fusion Pb-Ag (0.8wt.%)-Bi (0.3wt.%) alloy with 0.05m/s; Be full of the back naturally cooling, with 50 ℃ of hot water wash filler grain removed then, obtain Pb-Ca (0.09wt.%)-Sn (0.98wt.%)-Al (0.011wt.%)/Pb-Ag (0.8wt.%)/Pb-Ag (0.8wt.%)-compound porous electrode of Bi (0.3wt.%).
Embodiment 2:
304 stainless steel plates are placed PbCl
2(70wt.%)-CaCl
2(14wt.%)-and being coated with Pb coating in NaCl (15wt.%) fused salt, said 304 stainless steel plate thickness are 0.5mm, said temperature of molten salt is 480 ℃; In 400 ℃ Pb-Nd (0.1wt.%) alloy melt, flood 20s immediately then, obtaining thickness is the Pb-Nd transition layer of 0.1mm.With particle diameter is the K of 4.0mm-5.0mm
2SO
4The stainless steel plate that filler grain is coated with the Pb-Nd transition layer with the surface seepage flow chamber of packing into, and be preheated to 200 ℃; Pb-Ag (0.8wt.%) alloy is heated to 400 ℃ of fusings.Apply mold filling pressure; Driving fusion Pb-Ag (0.8wt.%) alloy gets into seepage flow chamber from bottom, seepage flow chamber along the antigravity direction with the speed of 0.2m/s; Be full of the back naturally cooling; With clear water filler grain is removed then, obtained Steel/Pb-Nd (0.1wt.%)/compound porous electrode of Pb-Ag (0.8wt.%).
Embodiment 3:
The Al-Si that 1mm is thick (1wt.%) alloy radiation formula framework is at 500 ℃ PbCl
2(80wt.%)-CaCl
2(9wt.%)-NaCl (10wt.%)-SnCl
2(1wt.%) plating Pb-Sn alloy in the fused salt, and in 400 ℃ fusion Pb-Sn (20wt.%) alloy, flood 5s, 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 processed 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; Driving fusion Pb-Ag (0.3wt.%)-Ca (0.03wt.%)-Sr (0.03wt.%) alloy gets into seepage flow chamber from bottom, seepage flow chamber along the antigravity direction with the speed of 0.1m/s; Be full of postcooling, use NH
4HCO
3The aqueous solution is removed filler grain, obtains Al-Si (1wt.%)/Pb-Sn (20wt.%)/Pb-Ag (0.3wt.%)-Ca (0.03wt.%)-compound porous electrode of Sr (0.03wt.%).
Embodiment 4:
The Ti grid that 6mm is thick is at PbCl
2(70wt.%)-CaCl
2(5wt.%)-be coated with pure Pb layer in NaCl (25wt.%) fused salt, and in 350 ℃ Pb-Ca (1.5wt.%) melt, flood 15s, 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 processed 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; Driving fusion Pb-Sb (1.3wt.%)-Sn (10.0wt.%)-Ag (0.8wt.%) alloy gets into seepage flow chamber from bottom, seepage flow chamber along the antigravity direction with the speed of 0.15m/s; Be full of postcooling; The way that strengthens washing with UW is removed filler grain, obtains Ti/Pb-Ca (1.5wt%)/Pb-Sb (1.3wt.%)-Sn (10.0wt.%)-compound porous electrode of Ag (0.8wt.%).
Embodiment 5:
The Cu-Al that 3mm is thick (10wt.%)-Fe (4wt.%)-Ni (5wt.%) alloy sieve tray floods 60s in 400 ℃ Pb-Co (0.1wt.%) melt; Obtain the thick Pb-Co alloy transition layer of 0.8mm and be coated with the Cu sieve tray of Pb-Co transition layer in the indoor installation surface of seepage flow, 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; Driving fusion Pb-Ag (0.6wt.%)-Ce (0.1wt.%) alloy gets into seepage flow chamber from bottom, seepage flow chamber along the antigravity direction with the speed of 0.05m/s; Be full of seepage flow chamber postcooling, adopt ultra-sonic oscillation, Na
2CO
3Solution flush away filler grain promptly obtains Cu-Al (10wt.%)-Fe (4wt.%)-Ni (5wt.%)/Pb-Co (0.1wt.%)/Pb-Ag (0.6wt.%)-compound porous electrode of Ce (0.1wt.%).
Embodiment 6
The Pb-Ag that 2mm is thick (0.8wt.%) strengthens metal substrate and is installed in 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 the speed entering seepage flow chamber of fusion Pb-Ag (0.8wt.%) alloy with 0.03m/s; Be full of the back naturally cooling, with high pressure water filler grain rinsed well then, obtain Pb-Ag (0.8wt.%)/compound porous electrode of Pb-Ag (0.8wt.%).
Claims (13)
1. a sulfuric acid system is used compound porous electrode, comprises three parts, it is characterized in that: be followed successively by from inside to outside and strengthen metal substrate, Pb or Pb base alloy (Pb-Me ') transition layer, Pb or Pb base alloy (Pb-Me ") porous layer.
2. a kind of sulfuric acid system according to claim 1 is used compound porous electrode, it is characterized in that: said 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 the Cu base alloy (Cu-Me); Wherein alloying element Me is selected from least a among Ag, Ca, Ba, Ce, Nd, Cr, Sn, Ni, Ti, Al, Zn, Fe, Si, the Mg; The quality percentage composition of alloy constituent element Me is 0～50%; The structure of said enhancing metal substrate is a kind of in flat, radiation formula, sieve aperture formula or the grid formula; The thickness of said enhancing metal substrate is 0.5mm～8mm.
3. a kind of sulfuric acid system according to claim 2 is used compound porous electrode; It is characterized in that: said transition layer Pb or Pb base alloy (Pb-Me ') in; Alloying element Me ' is selected from least a among Co, Ag, Nd, Al, Ce, the Sn; Alloying element content is 0wt.%～30wt.%, and the thickness of said transition layer is 0.05～1mm.
4. a kind of sulfuric acid system according to claim 3 is used compound porous electrode; It is characterized in that: in said porous layer Pb or the Pb base alloy (Pb-Me "); alloying element Me " be at least a among Ag, Ca, Sn, Sr, Sb, Ti, Al, Zn, Ce, Ba, Tl, Si, Mn, Co, Fe, the Bi, alloying element content is 0wt.%～49.9wt.%.
5. one kind prepares like claim 1,2,3, the 4 any said sulfuric acid systems method with compound porous electrode, comprises the steps:
The first step: strengthen the preparation of metal substrate
By the enhancing metal substrate component and the structure of design, select to strengthen the metal substrate material and process corresponding enhancing metal-based slab A; Said 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 the Cu base alloy (Cu-Me); Wherein alloying element Me is selected from least a among Ag, Ca, Ba, Ce, Nd, Cr, Sn, Ni, Ti, Al, Zn, Fe, Si, the Mg; The quality percentage composition of alloy constituent element Me is 0～50%;
Second step: on the metal-based slab, prepare transition layer
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-based slab A, and to immerse temperature be 3～60s in 320～550 ℃ Pb or Pb base alloy (the Pb-Me ') melt; Obtain the enhancing metal-based 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) strengthened metal-based slab A and place the molten chloride that contains Pb to carry out electroless plating; Immerse temperature and be 3～60s in 320～550 ℃ Pb or Pb base alloy (the Pb-Me ') melt; Obtain the enhancing metal-based slab C that the surface is coated with Pb or Pb base alloy (Pb-Me ') transition layer; Said electroless plating temperature is 350～550 ℃, and the time is 30s～5min;
The 3rd step: THROUGH METHOD prepares porous layer
The second step gained enhancing metal-based slab B or enhancing metal-based slab C are placed center, seepage flow chamber, and periphery is filled full filler grain, is heated to 180～310 ℃; Then, with Pb or Pb base alloy (Pb-Me ") heat fused, inject the seepage flow chamber, naturally cooling; Obtain strengthening metal-based slab B or strengthening the electrode that metal-based slab C surface coverage has Pb or Pb base alloy (Pb-Me ") porous layer; Be filled with a large amount of filler grains in the said porous layer; Said Pb or Pb base alloy (Pb-Me ") temperature of fusion is 300～600 ℃;
The 4th step: the removal of filler grain
The 3rd step gained electrode is placed solvent, apply ultra-sonic oscillation, remove filler grain, promptly obtain sulfuric acid system and use compound porous electrode.
6. a kind of sulfuric acid system according to claim 5 is with the preparation method of compound porous electrode; It is characterized in that: said THROUGH METHOD prepares porous layer and adopts Pb or Pb base alloy (Pb-Me ") heat fused; the alloy melt pressurization is injected the seepage flow chamber from bottom, seepage flow chamber along the antigravity direction, and the alloy melt injection speed is 0.01～0.2m/s.
7. a kind of sulfuric acid system according to claim 6 is characterized in that with the preparation method of compound porous electrode: the structure of said metal substrate is a kind of in flat, radiation formula, sieve aperture formula or the grid formula; The thickness of said enhancing metal substrate is 0.5mm～8mm.
8. a kind of sulfuric acid system according to claim 7 is with the preparation method of compound porous electrode; It is characterized in that: said transition layer Pb or Pb base alloy (Pb-Me ') in; Alloying element Me ' is selected from least a among Co, Ag, Nd, Al, Ce, the Sn; Alloying element content is 0wt.%～30wt.%, and the thickness of said transition layer is 0.05～1mm.
9. a kind of sulfuric acid system according to claim 8 is with the preparation method of compound porous electrode; It is characterized in that: in said porous layer Pb or the Pb base alloy (Pb-Me "); alloying element Me " be at least a among Ag, Ca, Sn, Sr, Sb, Ti, Al, Zn, Ce, Ba, Tl, Si, Mn, Co, Fe, the Bi, alloying element content is 0wt.%～49.9wt.%.
10. a kind of sulfuric acid system according to claim 9 is characterized in that with the preparation method of compound porous electrode: said molten chloride comprises main salt PbCl
2-NaCl-CaCl
2And be selected from AgCl, RECl
2And SnCl
2In at least a auxilliary salt; Said main salt PbCl
2-NaCl-CaCl
2The quality percentage composition of each component is followed successively by 50%～90%, 5%～30%, 1%～20%; Said auxilliary salt AgCl, RECl
2And SnCl
2The quality percentage composition of each component is followed successively by 0～5%, 0～5% and 0～10%.
11. a kind of sulfuric acid system according to claim 10 is characterized in that with the preparation method of compound porous electrode: said filler grain is selected from CaSO
4, Na
2SO
4, K
2SO
4, MgSO
4, ZnSO
4, CaCl
2, at least a among NaCl and the KCl; The particle diameter of filler grain is 0.01～3mm; Filler grain is shaped as spherical or cylindrical.
12. a kind of sulfuric acid system according to claim 11 is characterized in that with the preparation method of compound porous electrode: said solvent is selected from Na
2CO
3Solution, NH
4HCO
3At least a in solution, clear water, pressure water, the warm water.
13. a sulfuric acid system comprises the steps: with the method for compound porous electrode
The first step: strengthen the preparation of metal substrate
By the 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 among Ag, Ca, Ba, Ce, Nd, Cr, Sn, Ni, Ti, the 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-based slab place 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 the seepage flow chamber, naturally cooling; Obtain the electrode of Pb or Pb base alloy (Pb-Me ") porous layer being arranged strengthening metal-based slab surface coverage; Be filled with a large amount of filler grains in the said porous layer; Said Pb or Pb base alloy (Pb-Me ") temperature of fusion is 300～600 ℃;
The 3rd step: the removal of filler grain
The second step gained electrode is placed solvent, apply ultra-sonic oscillation, remove filler grain, promptly obtain sulfuric acid system and use compound porous electrode.
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2012051797A1 (en) | 2012-04-26 |
| ZA201302807B (en) | 2014-05-26 |
| CN102315455B (en) | 2013-08-14 |
| CN102352498A (en) | 2012-02-15 |
| CN102315455A (en) | 2012-01-11 |
| CN101949031A (en) | 2011-01-19 |
| CN102383145B (en) | 2013-11-06 |
| CN102352498B (en) | 2013-01-02 |
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