CN110224141B - Preparation method of negative grid alloy of all-lead-carbon battery - Google Patents

Preparation method of negative grid alloy of all-lead-carbon battery Download PDF

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CN110224141B
CN110224141B CN201910410651.0A CN201910410651A CN110224141B CN 110224141 B CN110224141 B CN 110224141B CN 201910410651 A CN201910410651 A CN 201910410651A CN 110224141 B CN110224141 B CN 110224141B
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lead
alloy
grid
negative grid
carbon battery
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CN110224141A (en
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戴德兵
邓德年
乔卫建
张文泉
付定华
李忠明
杨飞
王永
吴国强
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Xupai Power Supply Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C22C1/1047—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C11/00—Alloys based on lead
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0084—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ carbon or graphite as the main non-metallic constituent
    • 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
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H01M4/662—Alloys
    • 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
    • H01M4/68—Selection of materials for use in lead-acid accumulators
    • H01M4/685—Lead alloys
    • 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
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/73—Grids for lead-acid accumulators, e.g. frame plates
    • 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
    • H01M4/84—Multi-step processes for manufacturing carriers for lead-acid accumulators involving casting
    • 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

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a preparation method of a negative grid alloy of an all-lead carbon battery, which comprises the following steps: sequentially adding superfine graphite and graphene into a reactor, adding pure lead chips or pure lead particles, and then covering sodium chloride on the uppermost layer of the added raw materials; controlling the temperature to 800 ℃ for 500 plus materials, shaking or stirring for 1h, continuously heating to 1100 ℃ for 800 plus materials, shaking or stirring for 1h, then continuously heating to 1150 ℃ for 1050 plus materials, shaking or stirring for 3h, and preparing the alloy liquid; cooling the prepared alloy liquid, and pouring the cooled alloy liquid into an ingot mold; and cooling to room temperature, putting the prepared alloy ingot into water, soaking for 1h, taking out and drying to obtain the all-lead carbon battery negative grid alloy. The grid prepared from the negative grid alloy provided by the invention can be well combined with negative lead carbon formula lead plaster, the grid has the advantages of good strength, high hardness and good corrosion resistance, the grid can be directly filled, a continuous casting and continuous coating technology can be realized, and the processing is convenient.

Description

Preparation method of negative grid alloy of all-lead-carbon battery
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a preparation method of a negative grid alloy of an all-lead carbon battery.
Background
The grid in the lead-acid battery is used for supporting positive and negative electrode active substances and conducting current, and is the key for determining the performance of the battery, so the development of grid alloy materials is always an important direction for the research of storage batteries. The carbon material can be used as a current collector of the lead-acid battery, so that the weight of the lead-acid battery is reduced. At present, the existing negative plate is not a true all-lead carbon alloy, only carbon materials are adopted in lead paste on a negative grid plate, and common negative grid alloys mainly comprise the following forms (1) low-antimony alloy: antimony is easy to transfer to the positive electrode, so that the oxygen evolution overpotential of the positive electrode is reduced, but water is easy to lose in the battery charging process, and the antimony is not suitable for a negative plate grid material of a valve-controlled lean-solution lead-acid storage battery; (2) lead-calcium-tin-aluminum alloy: however, during casting, the negative grid is thin and soft, the hardness is not enough, and at least 5 days of age hardening are needed, so that the efficiency is low, the production period is long, the capital occupation is large, the strength is not enough, active substances are difficult to fill, the polar plate is easy to deform, 0.2-0.4% of tin is needed to increase the fluidity during casting, the material cost is increased, the calcium content is 0.08-0.13%, the aluminum content is 0.02-0.04%, the lead-calcium alloy has relatively large internal resistance, the calcium is easy to form corrosion among crystal grains, and the corrosion resistance of the manufactured grid is relatively poor. Therefore, a preparation method of the all-lead carbon battery negative grid alloy capable of solving the existing problems is urgently needed.
Disclosure of Invention
The invention aims to provide a preparation method of a negative grid alloy of an all-lead carbon battery aiming at the defects of the prior art, the grid prepared by the negative grid alloy can be well combined with negative lead carbon formula lead plaster, the all-lead carbon battery with real significance is realized, the grid has good strength, high hardness and good corrosion resistance, the grid can be directly filled without longer time effect, the continuous casting and continuous coating technology can be realized, and the processing is convenient.
The invention provides the following technical scheme:
a preparation method of an all-lead-carbon battery negative grid alloy comprises the following steps:
s1, sequentially adding graphite and graphene into the reactor, adding pure lead chips or pure lead particles, and then covering sodium chloride on the uppermost layer of the added raw materials;
s2, controlling the temperature to 800-;
s3, cooling the alloy liquid prepared in the step S2, and pouring the cooled alloy liquid into an ingot mold;
and S4, cooling to room temperature, putting the prepared alloy ingot into water, soaking for 1h, taking out and drying to obtain the lead-carbon battery negative grid alloy.
Preferably, the material adopted by the reactor is stainless steel.
Preferably, the mass ratio of graphite, graphene, lead and sodium chloride in the step S1 is: 0.5-5: 0.05-0.1: 5-25: 30.
Preferably, the particle size of the ultrafine graphite in the step S1 is 2-20 μm.
Preferably, the graphene in the S1 step is 3-10 layers.
Preferably, the particle size of the pure lead particles in the step S1 is 1-20 mm.
Preferably, the temperature of the alloy liquid is cooled to 310-330 ℃ in the step of S3, and the temperature is close to the freezing point of the alloy liquid.
The invention has the beneficial effects that:
according to the preparation method of the negative grid alloy of the all-lead carbon battery, the negative grid is cast by the lead carbon alloy, so that the negative grid and the negative lead carbon formula lead paste form good combination, and the real all-lead carbon battery is realized, namely the grid and the lead paste are all lead carbon components; the lead-carbon alloy formed by the adopted superfine graphite, the graphene and the lead has uniform and stable components, and the grid prepared by the negative grid alloy has good strength and high hardness, so that the problem that the negative grid is thin, soft and easy to deform is solved; in the preparation process of the negative grid alloy, sodium chloride is low in density, covers graphite, graphene and lead, can prevent lead slag from generating and burning loss at high temperature, is high in melting point, is beneficial to forming stable and uniform lead-carbon alloy after being melted at high temperature, and can be separated out after being dissolved in water; the cast grid has good corrosion resistance, can be directly filled without longer aging, can realize a continuous casting and continuous coating technology, is convenient to process, and solves the problems of long aging, long production period and large fund occupation.
Detailed Description
Example 1
S1, sequentially adding 100g of ultrafine graphite and 5g of graphene into a 10L stainless steel reactor, adding 1500g of pure lead chips, and covering 3000g of sodium chloride on the uppermost layer of the added raw materials, wherein the particle size of the ultrafine graphite is 2-20 microns, and the graphene is 3-7 layers;
s2, controlling the temperature to 700 ℃, stirring for 1h, continuously heating to 950 ℃, stirring for 1h, then continuously heating to 1050 ℃, shaking or stirring for 3h to obtain alloy liquid;
s3, cooling the alloy liquid prepared in the step S2 to the temperature of 310 ℃ and 330 ℃, wherein the temperature is close to the solidifying point of the alloy, and then pouring the alloy liquid into an ingot mold;
and S4, cooling to room temperature, putting the prepared alloy ingot into water, soaking for 1h, taking out and drying to obtain the lead-carbon battery negative grid alloy.
Example 2
S1, sequentially adding 200g of ultrafine graphite and 10g of graphene into a 10L stainless steel reactor, adding 2000g of pure lead chips, and covering 3000g of sodium chloride on the uppermost layer of the added raw materials, wherein the particle size of the ultrafine graphite is 2-20 microns, and the graphene is 3-7 layers;
s2, controlling the temperature to 780 ℃, stirring for 1h, continuously heating to 1050 ℃, stirring for 1h, then continuously heating to 1100 ℃, shaking or stirring for 3h to prepare alloy liquid;
s3, cooling the alloy liquid prepared in the step S2 to 320-330 ℃, wherein the range is close to the solidifying point of the alloy, and then pouring the alloy liquid into an ingot mold;
and S4, cooling to room temperature, putting the prepared alloy ingot into water, soaking for 1h, taking out and drying to obtain the lead-carbon battery negative grid alloy.
Example 3
S1, sequentially adding 300g of ultrafine graphite and 10g of graphene into a 10L stainless steel reactor, adding 1500g of pure lead chips, and covering 3000g of sodium chloride on the uppermost layer of the added raw materials, wherein the particle size of the ultrafine graphite is 2-20 microns, and the graphene is 3-7 layers;
s2, controlling the temperature to 780 ℃, stirring for 1h, continuously heating to 1050 ℃, stirring for 1h, then continuously heating to 1100 ℃, shaking or stirring for 3h to prepare alloy liquid;
s3, cooling the alloy liquid prepared in the step S2 to the temperature of 310 ℃ and 330 ℃, wherein the temperature is close to the solidifying point of the alloy, and then pouring the alloy liquid into an ingot mold;
and S4, cooling to room temperature, putting the prepared alloy ingot into water, soaking for 1h, taking out and drying to obtain the lead-carbon battery negative grid alloy.
The performance of the negative grid alloys prepared in examples 1 to 3 was tested and mainly included age hardness and corrosion resistance, with the specific results shown in table 1:
aging hardness: after the alloy is aged for 8h, the Vickers hardness value is detected by adopting an experimental force of 0.098N and keeping the time for more than 30 s.
Corrosion resistance: under the condition of 50 ℃, lead dioxide is used as a positive electrode, alloy is used as a negative electrode, a negative plate is prepared by coating lead plaster containing graphite on a grid made of the alloy, the constant current is 0.8A, the heavy pulling force is 550g, and the corrosion breaking time of an alloy sample is recorded.
Table 1 negative plate grid alloy performance test results
Age hardness (HV0.01) Corrosion resistance (sky)
Comparative example 4.6 3.5
Example 1 10.1 8.9
Example 2 15.8 14.5
Example 3 12.7 10.6
In the comparative example, the negative plate grid prepared by adopting the lead-calcium-tin-aluminum alloy is aged for 5 days, wherein the calcium content is 0.09%, the aluminum content is 0.03%, the tin content is 0.25%, and the balance is lead, and the prepared plate grid is coated with lead paste containing graphite to form the negative plate. From table 1, it can be seen that the negative grid alloy prepared by the method has significantly improved age hardness and corrosion resistance.
Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the invention as defined by the appended claims. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (5)

1. The preparation method of the negative grid alloy of the all-lead-carbon battery is characterized by comprising the following steps of:
s1, sequentially adding superfine graphite and graphene into the reactor, adding pure lead chips or pure lead particles, and then covering sodium chloride on the uppermost layer of the added raw materials; wherein: the mass ratio of the graphite to the graphene to the lead to the sodium chloride is as follows: 0.5-5: 0.05-0.1: 5-25: 30, of a nitrogen-containing gas; the grain size of the superfine graphite is 2-20 mu m;
s2, controlling the temperature to 800-;
s3, cooling the alloy liquid prepared in the step S2, and pouring the cooled alloy liquid into an ingot mold;
and S4, cooling to room temperature, putting the prepared alloy ingot into water, soaking for 1h, taking out and drying to obtain the all-lead carbon battery negative grid alloy.
2. The method for preparing the negative grid alloy of the all-lead-carbon battery according to claim 1, wherein the reactor is made of stainless steel.
3. The method for preparing the negative grid alloy of the all-lead-carbon battery according to claim 1, wherein the graphene in the step S1 is 3-10 layers.
4. The method for preparing the negative grid alloy of the all-lead-carbon battery according to claim 1, wherein the grain size of the pure lead particles in the step S1 is 1-20 mm.
5. The method for preparing the negative grid alloy of the all-lead-carbon battery according to claim 1, wherein the step of S3 is to cool the alloy liquid to 310-330 ℃.
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CN106058267A (en) * 2016-08-04 2016-10-26 超威电源有限公司 Preparation method of graphene-lead grid alloy for plumbic acid cell
CN106784858A (en) * 2015-11-25 2017-05-31 衡阳瑞达电源有限公司 Lead accumulator grid additive, preparation method, grid and high connductivity lead accumulator
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CN106784858A (en) * 2015-11-25 2017-05-31 衡阳瑞达电源有限公司 Lead accumulator grid additive, preparation method, grid and high connductivity lead accumulator
CN105463228A (en) * 2015-12-04 2016-04-06 福建省闽华电源股份有限公司 Metal melting protective agent with chloride as body and preparing method of metal melting protective agent
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