CN102352498B - Method for preparing Al/Pb lamellar composite materials - Google Patents

Method for preparing Al/Pb lamellar composite materials Download PDF

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CN102352498B
CN102352498B CN2011103063009A CN201110306300A CN102352498B CN 102352498 B CN102352498 B CN 102352498B CN 2011103063009 A CN2011103063009 A CN 2011103063009A CN 201110306300 A CN201110306300 A CN 201110306300A CN 102352498 B CN102352498 B CN 102352498B
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alloy
salt
metal bath
manufacture method
fused salt
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CN102352498A (en
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赖延清
蒋良兴
吕晓军
郝科涛
李劼
刘业翔
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KUNMING HENDERA SCIENCE AND TECHNOLOGY Co.,Ltd.
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Central South University
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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 relates to a method for preparing Al/Pb composite materials, which comprises three steps of base body surface pretreatment, surface chemical plating and metal bathing. An Al base body adopts a molten salt method for surface pretreatment for removing oil and oxides on the base body surface, and the fresh surface is protected form being oxidized again; the molten salt chemical plating is carried out in chloride molten salt containing lead elements, in addition, a certain amount of auxiliary salt is added into the molten salt for optimizing the alloy composition of a plating layer, and a transition layer is formed at the interface of the Al/Pb composite material; the metal bathing treatment is carried out in a Pb alloy melt body for many times after the chemical plating, and the ingredient and the thickness of the plating layer are controlled; and then, the heat treatment is carried out, the mutual diffusion of bonding interface elements is promoted, the stress of the plating layer is eliminated, the completeness of the plating layer is ensured, and the ingredient uniformity of the plating layer is improved. The method has the advantages that the operation of each work procedure is simple, the firm metallurgical bonding is formed between the Al/Pb composite materials, the Pb plating layer is compact and flat, and the thickness and the ingredients are controllable.

Description

A kind of preparation method of Al/Pb stratified composite
Technical field
The present invention relates to a kind of Al/Pb composite manufacture method, particularly a kind of preparation method of Al/Pb stratified composite belongs to metallic substance and fused salt chemistry field.
Background technology
Metal Pb and alloy thereof be because its excellent corrosion resistance and electrocatalysis ability, and be widely used in the electrochemical field such as hydrometallurgy, lead-acid cell, organic synthesis.But because lead density is large, poor electric conductivity, physical strength are low, it can increase labour intensity, improve the electrode resistance volts lost and creep, buckling deformation easily occur in actual application, electrochemical process is had a negative impact.Therefore, improve specific conductivity and the physical strength of Pb alloy electrode, the weight that reduces whole electrode seems particularly important.
With respect to metal Pb, metal A l has following advantage: (1) Al conducts electricity very well, and electric conductivity is 7 times of Pb; (2) physical strength of Al is high, and tensile strength is more than 5 times of Pb; (3) Al is the metal of extensive industrialization, and material is easy to get and low price; 4) Al's is lightweight, and density only is 24% of Pb.Therefore, if can prepare in metal A l both sides well-set Pb layer, form the Al/Pb matrix material, advantage that can comprehensive two kinds of metals improves the performance of Pb electrode comprehensively.Yet metal A l and Pb are divided awkward miscible system in thermodynamic system, and metal A l very easily forms the sull of one deck densification in air, are difficult to forming one deck densification, atresia, and the good Pb coating of basal body binding force at the Al matrix surface.
Traditional aluminium plated surface splicer skill, generally need to be coated with transition layer on the aluminum substrate surface first, announced a kind of preparation method of lead-aluminum composite anode plate such as patent 200710065927.3, utilized the method for dipping to plate in advance other metal of one deck in surface of aluminum plate, then at surface casting one deck Pb alloy.Patent 01135605.7 has been announced a kind of production method of lead-coated light high conducting slab lattice, need to surface of aluminum plate in advance immersion plating zinc or copper as transition layer.Patent 200910094290.X has announced the method for a kind of aluminium and aluminum alloy surface Direct Electroplating lead, and aluminum substrate will pass through mechanical grinding, oil removing, alkaline etching, pickling process before lead plating, and also has electric clean, activation procedure between alkaline etching and pickling process.Although this method has been saved the step of preplating transition layer, required pre-treatment step is many and complicated, and can only obtain pure lead-coat, and non-metallurgical binding between coating and the matrix is unfavorable for its practical application.Muscovite L.A.Yolshina immerses metal A l in the molten chloride that contains the Pb constituent element and carries out electroless plating Pb, has obtained the good Pb coating of bonding force.The method operation is simple, and matrix is the process of a consumption in the process of electroless plating, can guarantee that matrix is a unsalted surface forever, does not have zone of oxidation, and this can improve the bonding force of Al and Pb greatly.But, contain LiCl and KCl in the used fused salt, and the LiCl price is more expensive, the KCl suction is serious, and this has increased preparation cost and difficulty.Add this molten salt system and can only be coated with pure Pb coating, and be difficult to realize Pb coating to the complete covering of Al matrix, there is hole in coating, does not form metallurgical binding between the Al/Pb, has had a strong impact on the application of Al/Pb matrix material.Contriver early stage is to improving molten salt system, and increased the metal bath step after the fused salt chemistry plating, though can make coating complete, and the bonding force increase, also there are the following problems: 1) auxiliary salt SnCl 2Though adding can promote the mutual diffusion of element, do not find in the metallograph significantly to cross coating, and the fused salt surface blistering is serious, very unfavorable to being coated with process; 2) although the metal bath step can be controlled Coating composition, the thinner thickness of coating, circulation time under lead-acid cell positive and negative electrode operating voltage will soon peeling, comes off; 3) substrate pretreated is mechanical grinding, matrix that can not deal with complex shapes.Although and aqueous solution pre-treatment is to the base shape no requirement (NR), the drying process of handling matrix well can make the again oxidation of fresh matrix, to coating and matrix in conjunction with totally unfavorable; 4) because whole process time is shorter, and the mutual diffusion of element is insufficient, the bonding force of coating and matrix is inadequate.
Therefore, need to also need further improvement to the method.
Summary of the invention
The present invention is directed to the deficiency of traditional fused salt chemistry electroplating method, molten salt system and technique carried out major tuneup, and its concrete technology parameter is described, make gained Al/Pb matrix material in conjunction with firmly, thickness and composition be controlled.
A kind of Al/Pb composite manufacture of the present invention method comprises the steps:
The first step: matrix surface pre-treatment
Al or Al alloy substrate are soaked in the fused salt mixt that comprises at least a kind of muriate and a kind of fluorochemical; The metallic element of described muriate and fluorochemical is at least a among Al, Na, K, Ca, Mg, the Li; Described fused salt mixt temperature is 250-600 ℃, and soak time is 30s～10min;
Second step: surface chemical plating
Al or Al alloy substrate that the first step is obtained place PbCl 2-NaCl-CaCl 2Fused salt in, described temperature of molten salt is 350 ℃～550 ℃, the electroless plating time is 30s～5min; At Al or Al alloy substrate coating surface one deck ternary alloy transition layer;
The 3rd step: metal bath
The test specimen that second step is obtained places Pb or Pb alloy (Pb-Me) melt, carries out at least the one-time surface metal bath, and the temperature of described Pb or Pb alloy (Pb-Me) melt is 320～550 ℃, and the time of a described metal bath is 3～60s; Namely obtain the Al/Pb matrix material.
In a kind of Al/Pb composite manufacture of the present invention method, in the fused salt of described surface chemical plating, the quality percentage composition of each component is PbCl 250%～90%, NaCl 5%～30%, CaCl 21%～20%;
In a kind of Al/Pb composite manufacture of the present invention method, also include in the fused salt of described surface chemical plating and account for described PbCl 2-NaCl-CaCl 2Mass percent be 0～10% the auxiliary salt of halogenide, the auxiliary salt of described halogenide is muriate or the fluorochemical of at least a element among Sn, Cu, Na, K, Ag, Al, the RE.
In a kind of Al/Pb composite manufacture of the present invention method, the alloying element Me in described Pb or Pb alloy (Pb-Me) melt is selected from least a among Ag, Ca, RE, Bi, Cu, Sn, Sb, the Al.
In a kind of Al/Pb composite manufacture of the present invention method, described metal bath number of times is 1～5 time, selects according to the requirement to thickness of coating.
A kind of Al/Pb composite manufacture of the present invention method, the Al/Pb matrix material that described metal bath obtains are incubated 30min～5h, furnace cooling in 100～300 ℃.
A kind of Al/Pb composite manufacture of the present invention method comprises the steps:
The first step: substrate pretreated and surface chemical plating
Al or Al alloy substrate are placed PbCl 2-NaCl-CaCl 2In the auxiliary salt of main salt and halogenide, the auxiliary salt of described halogenide is for comprising at least the fused salt mixt of a kind of muriate and a kind of fluorochemical; Described muriatic metallic element is at least a among Sn, Al, Ag, Cu, the RE, and the metallic element of fluorochemical is at least a among Na, K, Mg, the Li; The quality percentage composition of the auxiliary salt of described halogenide is 0～10%; The temperature of described fused salt is 350 ℃～550 ℃, and the fused salt treatment time is 30s～20min; At Al or Al alloy substrate coating surface one deck ternary alloy transition layer;
Second step: metal bath
The test specimen that the first step is obtained places Pb or Pb alloy (Pb-Me) melt, carries out at least the one-time surface metal bath, and the temperature of described Pb or Pb alloy (Pb-Me) melt is 320～550 ℃, and the time of a described metal bath is 3～60s; Namely obtain the Al/Pb matrix material.
The present invention has carried out major tuneup to traditional molten electroless plating Pb method, and technological process and gained Al/Pb matrix material have following advantage:
(1) the surface preparation step of matrix, utilize partially halogenated thing fused salt can with Al 2O 3The characteristics of reaction, greasy dirt and the oxide film of removing aluminum alloy surface.Realize oil removing and finish except one step of oxide compound, and avoided the mechanical grinding method can not process the defective that complicated substrate and the aqueous solution are processed the again oxidation of post-drying process.Simultaneously, the fused salt pre-treatment can be carried out effective preheating and activation with matrix, is conducive to improve homogeneity and the difform Al/Pb matrix material of preparation of Al surface chemical plating reaction;
(2) adopt PbCl 2-NaCl-CaCl 2Fused salt carries out surface chemical plating, can guarantee fresh Al surface not by again oxidation, and Al is combined firmly with Pb.Particularly at PbCl 2-NaCl-CaCl 2Fused salt in add the auxiliary salt (CuCl of a small amount of halogenide 2, NaF, AgCl and RECl 2), not only can effectively promote Al/Pb interface formation ternary alloy transition layer, and the appearance that can stop fused salt surfactant foam layer, make easy and simple to handle;
(3) the employing metal bath after the fused salt chemistry plating is processed, and under the temperature lower than fused salt, carry out repeatedly metal bath, can effectively regulate and control composition and the thickness of coating, and repair the hole in the coating in the electroless plating process, make coating smooth, smooth, complete, satisfy application requiring;
(4) the Al/Pb matrix material of preparation carried out 100～300 ℃ insulation annealing, can promote the mutual diffusion of bonding interface element, form obvious transition layer, thereby further improve the bonding force of coating and matrix.
In sum, processing method of the present invention is simple, and is easy to operate, to the shape no requirement (NR) of matrix, is conducive to form at the Al of complexity matrix the Pb alloy layer of complete and even thickness.Simultaneously, formed firmly metallurgical binding between gained Al/Pb composite layer and the matrix, Pb coating is fine and close, smooth, thickness and composition are controlled.Be suitable for industrial applications.
Embodiment
With the following Examples content of the present invention is elaborated.
Embodiment 1:
Take metal A l as matrix, at 250 ℃ AlCl 3Surface preparation 20min in the-KF melt takes out matrix, and immerses PbCl 2(50wt.%)-NaCl (30wt.%)-CaCl 2(20wt.%) carry out surface chemical plating in the melting salt, temperature of molten salt is 550 ℃; Behind the 30s matrix is taken out from fused salt, immerse immediately temperature and be and carry out surface metal in 550 ℃ Pb-Sb (15wt.%) alloy melt and bathe, take out behind the 20s, at 100 ℃ of lower thermal treatment 5h, obtaining thickness of coating is the Al/Pb-Sb stratified composite of 40um with sample.
Embodiment 2:
Take porous metal Al-Sn (5wt.%) alloy as matrix, at 600 ℃ NaF-CaCl 2Surface preparation 30s in the-NaCl melt takes out matrix, and immerses PbCl 2(80wt.%)-NaCl (10wt.%)-CaCl 2(8wt.%)-CuCl 2(2wt.%) carry out surface chemical plating in the melting salt, temperature of molten salt is 450 ℃.Behind the 4min matrix is taken out from fused salt, immerse immediately temperature and be and carry out surface metal among 320 ℃ the Pb-Sn (3wt.%)-Ca (0.4wt.%) alloy melt and bathe, take out behind the 3s, repeat metal bath 5 times, at 200 ℃ of lower thermal treatment 2.5h, obtaining thickness of coating is the Al-Sn/Pb-Sn-Ca composite porous material of 250um with sample.
Embodiment 3:
Take metal A l-Cu (0.3wt.%)-Si (5wt.%) alloy as matrix, surface preparation 10min in 400 ℃ KF-KCl melt takes out matrix, and immerses PbCl 2(92wt.%)-NaCl (5wt.%)-CaCl 2(1.5wt.%)-and carrying out surface chemical plating in NaF (0.5wt.%)-AgCl (1wt.%) melting salt, temperature of molten salt is 360 ℃; Behind the 5min matrix is taken out from fused salt, immerse immediately temperature and be and carry out surface metal among 350 ℃ the Pb-Ag (1wt.%)-Nd (0.05wt.%) alloy melt and bathe, take out behind the 60s, repeat metal bath 3 times, at 300 ℃ of lower thermal treatment 30min, obtaining thickness of coating is the Al-Cu-Si/Pb-Ag-Nd matrix material of 170um with sample.
Embodiment 4:
Take metal A l rod as matrix, it is immersed PbCl 2(82wt.%)-NaCl (10wt.%)-CaCl 2(5.5wt.%)-NaF (0.5wt.%)-CeCl 2(2wt.%) carry out surface preparation and electroless plating in the melting salt, temperature of molten salt is 430 ℃.Behind the 3min matrix is taken out from fused salt, immerse immediately temperature and be and carry out surface metal among 350 ℃ the Pb-Sb (2wt.%)-Ce (0.05wt.%) alloy melt and bathe, take out behind the 30s, repeat metal bath 3 times, at 300 ℃ of lower thermal treatment 20min, obtaining thickness of coating is the Al/Pb-Sb-Ce matrix material of 170um with sample.

Claims (10)

1. an Al/Pb composite manufacture method comprises the steps:
The first step: matrix surface pre-treatment
Al or Al alloy substrate are soaked in the fused salt mixt that comprises at least a kind of muriate and a kind of fluorochemical; The metallic element of described muriate and fluorochemical is at least a among Al, Na, K, Ca, Mg, the Li; Described fused salt mixt temperature is 250-600 ℃, and soak time is 30s～10min;
Second step: surface chemical plating
Al or Al alloy substrate that the first step is obtained place PbCl 2-NaCl-CaCl 2Fused salt in, described temperature of molten salt is 350 ℃～550 ℃, the electroless plating time is 30s～5min; At Al or Al alloy substrate coating surface one deck ternary alloy transition layer;
The 3rd step: metal bath
The test specimen that second step is obtained places Pb or Pb alloy Pb-Me melt, carries out at least the one-time surface metal bath, and the temperature of described Pb or Pb alloy Pb-Me melt is 320～550 ℃, and the time of a described metal bath is 3～60s; Namely obtain the Al/Pb matrix material.
2. a kind of Al/Pb composite manufacture method according to claim 1, it is characterized in that: in the fused salt of described surface chemical plating, the quality percentage composition of each component is PbCl 250%～90%, NaCl5%～30%, CaCl 21%～20%;
3. a kind of Al/Pb composite manufacture method according to claim 2 is characterized in that: also include in the fused salt of described surface chemical plating and account for described PbCl 2-NaCl-CaCl 2Mass percent be 0～10% the auxiliary salt of halogenide, the auxiliary salt of described halogenide is muriate or the fluorochemical of at least a element among Sn, Cu, Na, K, Ag, Al, the RE.
4. a kind of Al/Pb composite manufacture method according to claim 3 is characterized in that: the alloying element Me in described Pb or the Pb alloy Pb-Me melt is selected from least a among Ag, Ca, RE, Bi, Cu, Sn, Sb, the Al.
5. a kind of Al/Pb composite manufacture method according to claim 4, it is characterized in that: described metal bath number of times is 1～5 time.
6. a kind of Al/Pb composite manufacture method according to claim 5 is characterized in that: the Al/Pb matrix material that described metal bath obtains is in 100～300 ℃, insulation 30min～5h, furnace cooling.
7. an Al/Pb composite manufacture method comprises the steps:
The first step: substrate pretreated and surface chemical plating
Al or Al alloy substrate are placed PbCl 2-NaCl-CaCl 2In the auxiliary salt of main salt and halogenide, the auxiliary salt of described halogenide is for comprising at least the fused salt mixt of a kind of muriate and a kind of fluorochemical; Described muriatic metallic element is at least a among Sn, Al, Ag, Cu, the RE, and the metallic element of fluorochemical is at least a among Na, K, Mg, the Li; The quality percentage composition of the auxiliary salt of described halogenide is 0～10%; The temperature of described fused salt is 350 ℃～550 ℃, and the fused salt treatment time is 30s～20min; At Al or Al alloy substrate coating surface one deck ternary alloy transition layer;
Second step: metal bath
The test specimen that the first step is obtained places Pb or Pb alloy Pb-Me melt, carries out at least the one-time surface metal bath, and the temperature of described Pb or Pb alloy Pb-Me melt is 320～550 ℃, and the time of a described metal bath is 3～60s; Namely obtain the Al/Pb matrix material.
8. a kind of Al/Pb composite manufacture method according to claim 7, it is characterized in that: in the fused salt of described surface chemical plating, the quality percentage composition of each component is PbCl 250%～90%, NaCl5%～30%, CaCl 21%～20%;
9. a kind of Al/Pb composite manufacture method according to claim 8, it is characterized in that: described metal bath number of times is 1～5 time.
10. the described a kind of Al/Pb composite manufacture method of any one according to claim 1-9 is characterized in that: the Al/Pb matrix material that described metal bath obtains is in 100～300 ℃, insulation 30min～5h, furnace cooling.
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CN102352498A (en) 2012-02-15
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