CN101949031A - 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 PDF

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Publication number
CN101949031A
CN101949031A CN2010105100652A CN201010510065A CN101949031A CN 101949031 A CN101949031 A CN 101949031A CN 2010105100652 A CN2010105100652 A CN 2010105100652A CN 201010510065 A CN201010510065 A CN 201010510065A CN 101949031 A CN101949031 A CN 101949031A
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base alloy
metal
sulfuric acid
acid system
porous electrode
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赖延清
蒋良兴
李劼
刘业翔
吕晓军
刘宏专
郝科涛
洪波
李渊
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Central South University
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Central South University
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Priority to CN2010105100652A priority Critical patent/CN101949031A/en
Publication of CN101949031A publication Critical patent/CN101949031A/en
Priority to CN2011103063009A priority patent/CN102352498B/en
Priority to CN2011103061569A priority patent/CN102383145B/en
Priority to CN2011103101091A priority patent/CN102315455B/en
Priority to PCT/CN2011/001722 priority patent/WO2012051797A1/en
Priority to ZA2013/02807A priority patent/ZA201302807B/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0454—Electrochemical coating; Electrochemical impregnation from melts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0483—Processes of manufacture in general by methods including the handling of a melt
    • H01M4/0485—Casting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H01M4/16—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/82—Multi-step processes for manufacturing carriers for lead-acid accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a composite porous electrode for a sulfuric acid system and a preparation method thereof. From inside to outside, the electrode is sequentially provided with an enhanced metal substrate, a Pb or Pb-based alloy (Pb-Me') transition layer and a Pb or Pb-based alloy (Pb-Me'') porous layer. The preparation method for the electrode comprises the following steps of: preparing the transition layer by performing chemical plating and metal melt immersion plating in the molten salts of chlorides or directly by performing the metal melt immersion plating, and preparing the porous layer by adopting an infiltration method or an antigravity infiltration method. Due to the adoption of the transition layer, the enhanced metal substrate and the porous layer in the composite porous electrode are combined more firmly, even electrolyte cannot permeate into and corrode the substrate through the porous layer, and the electrode has longer service life. The method of the invention has the advantages of preparing the composite porous electrode with firm combination among composite layers, strong strength, high corrosion resistance and long service life, and solving the long-term problems of short service life and weak strength of the electrode in the sulfuric acid system, along with simplicity and rational structure.

Description

A kind of sulfuric acid system is with compound porous electrode and preparation method thereof
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 oxide film 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 manufacture method 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 between simple, rational in infrastructure, the prepared compound porous electrode composite bed of a kind of processing method in conjunction with firmly, intensity is high, erosion resistance is strong, the life-span is long sulfuric acid system is with compound porous electrode and preparation method thereof.
The compound porous electrode of a kind of sulfuric acid system of the present invention 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 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 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 described enhancing metal substrate is a kind of in flat, radiation formula, sieve aperture formula or the grid formula; The thickness of described enhancing metal substrate is 0.5mm～8mm.
A kind of sulfuric acid system of the present invention is with in the compound porous electrode, described 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 described transition layer is 0.05～1mm.
A kind of sulfuric acid system of the present invention is with in the compound porous electrode, in described 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 make 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 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 matrix 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 matrix 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 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) strengthened metal matrix 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 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 enhancing metal matrix slab B or enhancing metal matrix 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 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 the 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 gained electrode is placed solvent, apply ultra-sonic oscillation, remove filler grain, promptly obtain the compound porous electrode of sulfuric acid system.
Among the preparation method of a kind of sulfuric acid system of the present invention with compound porous electrode, described 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 described enhancing metal substrate is a kind of in flat, radiation formula, sieve aperture formula or the grid formula; The thickness of described 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, described 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 described 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 described 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, described molten chloride comprises main salt PbCl 2-NaCl-CaCl 2And be selected from AgCl, RECl 2And SnCl 2In at least a auxilliary 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 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, described 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 0.01～3mm, 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, described solvent is selected from Na 2CO 3Solution, NH 4HCO 3At least a in solution, clear water, pressure water, the warm water.
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 with substrate can be in conjunction with firmly.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 displaced 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 by 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.In general, 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 0.01～3mm that the present invention selects the particle diameter of filler grain, can effectively guarantee to form effective seepage flow between filler grain, 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 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 with strengthening metal substrate; help Pb or Pb base alloy porous layer and form metallurgical binding, effectively improve the structural strength of the compound porous electrode of the present invention with strengthening metal substrate.
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 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, 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, and lowers production cost.
In sum, between simple, rational in infrastructure, the prepared compound 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 the sulfuric acid system problem that electrode life is short, intensity is low.Be suitable for industrial applications.
Description of drawings
Accompanying drawing 1 is the sectional view of the compound porous Pb base electrode of the present invention;
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
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 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 made 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 fusion Pb-Ag (0.8wt.%)-Bi (0.3wt.%) alloy and enter the seepage flow chamber with the speed of 0.05m/s, be full of the back naturally cooling, with 50 ℃ of hot water wash methods filler grain is removed then, obtained 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, described 304 stainless steel plate thickness are 0.5mm, described temperature of molten salt is 480 ℃; Flood 20s immediately in 400 ℃ Pb-Nd (0.1wt.%) alloy melt then, obtaining thickness is the Pb-Nd transition layer of 0.1mm.With particle diameter is the K of 1.0mm-1.2mm 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 enters 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 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, driving fusion Pb-Ag (0.3wt.%)-Ca (0.03wt.%)-Sr (0.03wt.%) alloy enters 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 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, driving fusion Pb-Sb (1.3wt.%)-Sn (10.0wt.%)-Ag (0.8wt.%) alloy enters 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 ultrasonic wave 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 is coated with the Pb-Co transition layer on the indoor installation of seepage flow surface Cu sieve tray, particle diameter is the ZnSO of 0.6mm-0.8mm 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 enters 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.%).

Claims (12)

1. the compound porous electrode of sulfuric acid system 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. the compound porous electrode of a kind of sulfuric acid system according to claim 1 is characterized in that: 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 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 described enhancing metal substrate is a kind of in flat, radiation formula, sieve aperture formula or the grid formula; The thickness of described enhancing metal substrate is 0.5mm～8mm.
3. the compound porous electrode of a kind of sulfuric acid system according to claim 2, it is characterized in that: described 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 described transition layer is 0.05～1mm.
4. the compound porous electrode of a kind of sulfuric acid system according to claim 3, it is characterized in that: in described 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.%.
One kind prepare as claim 1,2,3,4 as described in any one sulfuric acid system comprise 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 to strengthen the metal substrate material and make 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 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 matrix 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 matrix 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 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) strengthened metal matrix 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 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 enhancing metal matrix slab B or enhancing metal matrix 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 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 the described porous layer; Described 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 the compound porous electrode of sulfuric acid system.
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: described 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 described metal substrate is a kind of in flat, radiation formula, sieve aperture formula or the grid formula; The thickness of described 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: described 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 described 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 described 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 with the preparation method of compound porous electrode, and 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 auxilliary 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 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 with the preparation method of compound porous electrode, 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 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 with the preparation method of compound porous electrode, it is characterized in that: described solvent is selected from Na 2CO 3Solution, NH 4HCO 3At least a in solution, clear water, pressure water, the warm water.
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