CN110993959A - Negative plate alloy preparation process - Google Patents

Negative plate alloy preparation process Download PDF

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Publication number
CN110993959A
CN110993959A CN201911242246.9A CN201911242246A CN110993959A CN 110993959 A CN110993959 A CN 110993959A CN 201911242246 A CN201911242246 A CN 201911242246A CN 110993959 A CN110993959 A CN 110993959A
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China
Prior art keywords
alloy
negative plate
lead
cooling
release agent
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CN201911242246.9A
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CN110993959B (en
Inventor
张利棒
李超雄
陶云兴
江小珍
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ANHUI HONGDA ELECTRICAL SOURCE CO LTD
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ANHUI HONGDA ELECTRICAL SOURCE CO LTD
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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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/68—Selection of materials for use in lead-acid accumulators
    • H01M4/685—Lead alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C3/00—Selection of compositions for coating the surfaces of moulds, cores, or patterns
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D7/00—Casting ingots, e.g. from ferrous metals
    • B22D7/005—Casting ingots, e.g. from ferrous metals from non-ferrous metals
    • 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
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • 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
    • C22C11/08—Alloys based on lead with antimony or bismuth as the next major constituent
    • C22C11/10—Alloys based on lead with antimony or bismuth as the next major constituent with tin
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

The invention discloses a negative plate alloy preparation process, and relates to the technical field of storage batteries. The negative plate alloy comprises the following components: 0.1-0.5% of Ca, 1-3% of Sb, 0.05-0.1% of Sn, 0.05-0.1% of As, 0.02-0.05% of Al, 0.01-0.025% of S, 0.1-0.3% of Cd, 0.05-0.2% of Ag, 0.05-0.2% of Cu and the balance of lead; the preparation process comprises the steps of sequentially adding high-calcium master alloy and electrolytic lead-lead particles into a reactor, controlling the temperature to 800-; 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 and cooling for 1h, taking out and drying to obtain the negative grid alloy. The negative plate alloy material has excellent mechanical property, corrosion resistance and high H precipitation overpotential; the manufacturing process of the alloy is simple and easy to implement.

Description

Negative plate alloy preparation process
Technical Field
The invention belongs to the technical field of storage batteries, and particularly relates to a negative plate alloy preparation process.
Background
With the development of lead acid battery technology, therefore, for the key components in the battery: a great deal of research has been conducted on the alloy materials of grids. At present, Pb-Ca-Sn-Al alloy widely used at home and abroad is used for manufacturing a grid and assembling a sealed lead-acid storage battery. The alloy has the following defects: the alloy has low mechanical strength and can not meet the requirement of large storage batteries, and the negative grid made of the alloy generates sulfated lead on the surface to cause deformation and expansion of the grid, thereby easily causing short circuit in the battery and causing short service life of the battery. Therefore, a new technical solution is needed to solve the above technical problems.
Disclosure of Invention
The invention aims to provide a negative plate alloy preparation process to solve the problems in the background technology.
In order to solve the technical problems, the invention is realized by the following technical scheme:
the invention relates to a preparation process of a negative plate alloy, which comprises the following components in percentage by weight: 0.1-0.5% of Ca, 1-3% of Sb, 0.05-0.1% of Sn, 0.05-0.1% of As, 0.02-0.05% of Al, 0.01-0.025% of S, 0.1-0.3% of Cd, 0.05-0.2% of Ag, 0.05-0.2% of Cu and the balance of lead;
the preparation process comprises the following steps:
s1, sequentially adding high-calcium master alloy and electrolytic lead and lead particles into the reactor;
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 and cooling for 1h, taking out and drying to obtain the negative grid alloy.
Further, the preparation of the high-calcium master alloy comprises the following steps:
ca, Sb, Sn, Al, Cd, Ag, Cu and S with the purity of 99.98 percent are mixed and forged.
Further, in the step S3, a release agent is sprayed in the ingot mold, and the release agent mainly reduces the heat conduction of the molten lead, so that the heat of the molten lead after entering the mold cavity is not easily absorbed by the steel mold, and good fluidity is maintained in a moment, and the mold is easily released. After the lead liquid is solidified in the die cavity, the release agent is attached to the die surface, so that the vacuum degree of the lead on the die surface is greatly reduced, and the lead is easy to release.
Further, the release agent comprises 700g of cork powder, 350ml of sodium silicate, 150g of bentonite and 10kg of water which are uniformly stirred and mixed.
Further, the preparation of the release agent comprises:
firstly, 3kg of water and 120g of bentonite are taken from 1 and put into a stirrer to be stirred and mixed for 1.5 hours; then adding 7kg of water, 600g of cork powder and 300ml of sodium silicate in sequence, and continuing stirring for 5 min.
Furthermore, in the spraying process of the release agent, the position of the rib and the tab with a large amount of lead is wiped by a scraper, and the unit area of the release agent at the position of the rib and the tab is kept to be 1/3-2/3 of the rest positions.
Further, in the step S3, the temperature of the ingot mold is raised and maintained at 110-130 ℃.
Further, in the step S3, the alloy liquid needs to be cooled to 310-330 ℃.
The addition of Cd reduces gaps generated by filling, and avoids the phenomenon of generating cracks; the Sn can improve the microstructure of the alloy surface and active substance joint, improves the fluidity of alloy liquid, is beneficial to casting and has high casting qualification rate; a1 is to form an anti-oxidation film in melting, which has certain effect on reducing the burning loss of Ca and the penetrating corrosion of the grid; the S is used as a metal or nonmetal for nucleation, so that the overpotential for hydrogen precipitation is improved;
the negative plate alloy material has excellent mechanical property, corrosion resistance and high H precipitation overpotential; the alloy material can be used for manufacturing closed lead-acid storage batteries assembled by grids, and all technical indexes of the closed lead-acid storage batteries can meet the requirements of production standards.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Detailed Description
A negative plate alloy preparation process comprises the following components in percentage by weight: 0.35% of Ca0.35%, 2.5% of Sb, 0.075% of Sn0.065%, 0.05% of Al, 0.015% of S, 0.2% of Cd, 0.1% of Ag, 0.1% of Cu0.1% and the balance of lead;
the preparation process comprises the following steps:
s1, sequentially adding high-calcium master alloy and electrolytic lead and lead particles into the reactor;
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 and cooling for 1h, taking out and drying to obtain the negative grid alloy.
Wherein, the preparation of the high-calcium master alloy comprises the following steps:
ca, Sb, Sn, Al, Cd, Ag, Cu and S with the purity of 99.98 percent are mixed and forged.
Wherein, in the step S3, a release agent is sprayed in the ingot mould.
Wherein, the preparation of the release agent comprises the following steps:
firstly, 3kg of water and 120g of bentonite are taken from 1 and put into a stirrer to be stirred and mixed for 1.5 hours; then adding 7kg of water, 600g of cork powder and 300ml of sodium silicate in sequence, and continuing stirring for 5 min.
During the spraying process of the release agent, the ribs and the tabs with a large amount of lead are scraped by a scraper, and the unit area of the release agent at the ribs and the tabs is kept to be 1/3-2/3 of the rest parts.
Wherein, in the step S3, the ingot mould is heated and kept at 120 ℃.
In the step S3, the alloy liquid needs to be cooled to 320 ℃.
The performance of the negative plate alloy prepared by the method is compared with that of the existing storage battery:
item Resistivity of capacity/Ah Specific energy/(Wh kg)-1) Corrosion resistance (sky)
Existing storage battery 1 11.35 29.7 8.5
Example 1 0.75 12.65 32.5 12.7
As can be seen from the table above, the comprehensive performance of the storage battery prepared by adopting the negative plate alloy of the invention is superior to that of the existing battery.
The negative grid alloy of the existing storage battery is a medium-tin high-calcium alloy and comprises the following components in percentage by weight: 0.08 to 0.12 percent of calcium; 0.05 to 0.07 percent of tin; 0.03 to 0.05 percent of aluminum; 0.05 to 0.08 percent of silver; 0.05 to 0.08 percent of copper; 0.005-0.01% selenium; the balance being lead.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims (8)

1. A negative plate alloy preparation process is characterized by comprising the following steps: the negative plate alloy comprises the following components in percentage by weight: 0.1-0.5% of Ca, 1-3% of Sb, 0.05-0.1% of Sn, 0.05-0.1% of As, 0.02-0.05% of Al, 0.01-0.025% of S, 0.1-0.3% of Cd, 0.05-0.2% of Ag, 0.05-0.2% of Cu and the balance of lead;
the preparation process comprises the following steps:
s1, sequentially adding high-calcium master alloy and electrolytic lead and lead particles into the reactor;
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 and cooling for 1h, taking out and drying to obtain the negative grid alloy.
2. The negative plate alloy formulation process of claim 1, wherein the preparing of the high calcium master alloy comprises mixing:
ca, Sb, Sn, Al, Cd, Ag, Cu and S with the purity of 99.98 percent are mixed and forged.
3. The process of claim 1, wherein the step of S3 is performed by spraying a release agent into the ingot mold.
4. The negative plate alloy preparation process as claimed in claim 3, wherein the release agent comprises cork powder 500-700g, sodium silicate 250-350ml, bentonite 100-150g and water 10 kg.
5. The negative plate alloy formulation process of claim 4, wherein the preparation of the release agent comprises:
firstly, 3kg of water and 120g of bentonite are taken from 1 and put into a stirrer to be stirred and mixed for 1.5 hours; then adding 7kg of water, 600g of cork powder and 300ml of sodium silicate in sequence, and continuously stirring for 5 min.
6. The process for preparing a negative electrode plate alloy according to claim 1, wherein the release agent is sprayed onto the tab and the bar having a large amount of lead by a scraper, and the release agent is sprayed onto the tab and the bar in a unit area of 1/3 to 2/3.
7. The process of claim 1, wherein the step S3 is carried out by heating the ingot mold and maintaining the temperature at 110-130 ℃.
8. The negative plate alloy formulation process of claim 1, wherein the step of S3 is carried out by cooling the alloy liquid to 310-330 ℃.
CN201911242246.9A 2019-12-06 2019-12-06 Negative plate alloy preparation process Active CN110993959B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1045199A (en) * 1989-02-25 1990-09-05 中科院长春应用化学研究所 The preparation method of slab lattice alloy of lead-acid battery
CN1063582A (en) * 1991-01-23 1992-08-12 曹清亮 The multicomponent alloy of battery grid and process for making
CN1560944A (en) * 2004-02-18 2005-01-05 北京天睿力迈科技有限公司 High-energy full-closed lead-acid battery for communication system

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1045199A (en) * 1989-02-25 1990-09-05 中科院长春应用化学研究所 The preparation method of slab lattice alloy of lead-acid battery
CN1063582A (en) * 1991-01-23 1992-08-12 曹清亮 The multicomponent alloy of battery grid and process for making
CN1560944A (en) * 2004-02-18 2005-01-05 北京天睿力迈科技有限公司 High-energy full-closed lead-acid battery for communication system

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