CN111118337A - High-performance corrosion-resistant positive grid alloy of lead-acid storage battery - Google Patents
High-performance corrosion-resistant positive grid alloy of lead-acid storage battery Download PDFInfo
- Publication number
- CN111118337A CN111118337A CN201911303351.9A CN201911303351A CN111118337A CN 111118337 A CN111118337 A CN 111118337A CN 201911303351 A CN201911303351 A CN 201911303351A CN 111118337 A CN111118337 A CN 111118337A
- Authority
- CN
- China
- Prior art keywords
- lead
- alloy
- grid
- corrosion
- storage battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- C22C11/06—Alloys based on lead with tin as the next major constituent
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention relates to a high-performance corrosion-resistant positive grid alloy for a lead-acid storage battery, which is prepared by melting the following materials in percentage by weight: 0.03-0.2% of barium, 0.5-2.5% of tin, 0.005-0.03% of aluminum, 0.003-0.1% of silver, 0.01-0.5% of tellurium, 0.005-0.06% of silicon and the balance of lead. The invention aims to overcome the defects in the prior art and provide the high-performance positive grid alloy which can enhance the mechanical strength of a grid and reduce the intergranular corrosion of the alloy so as to improve the corrosion resistance of the grid.
Description
Technical Field
The invention relates to the technical field of lead-acid storage batteries, in particular to a high-performance corrosion-resistant positive grid alloy for a lead-acid storage battery.
Background
The polar plate is a basic energy unit of the lead-acid storage battery, and the performance of the polar plate directly influences the basic performance and the service life of the lead-acid storage battery. The grid, the most important inactive substance in the lead-acid battery, is the "skeleton" of the plate, which mainly functions to support the active substance and conduct current, and although it does not participate in the flow reaction of the battery, its physical and chemical properties are particularly important for the lead-acid battery.
With the popularization of lead-acid batteries, the application range of the lead-acid batteries is wider and wider, and the performances of the lead-acid batteries are continuously challenged. As the use of the lead-acid storage battery in a high-temperature environment is increased, the corrosion speed of the grid of the lead-acid storage battery is accelerated, and the service life of the battery is influenced to a great extent. The positive grid of the traditional maintenance-free lead-acid storage battery is mainly made of lead-calcium-tin-aluminum alloy, and the positive grid mainly comprises the following general components: 0.04 to 0.2 percent of calcium, 0.8 to 2.5 percent of tin, 0.005 to 0.05 percent of aluminum and the balance of lead. Calcium plays a role in increasing the strength of the grid in the alloy, but the calcium is segregated in the grain boundary in the lead alloy to generate intermetallic compounds such as CaPb3, CaSn3 and the like, and the growth of partial grains is inhibited, so that the grain size is uneven, the local corrosion of the alloy in the grid is serious, and the corrosion resistance of the grid is poor. The lead alloy is modified by a method of adding rare earth elements into the alloy in the industry, the introduction of the rare earth elements can lead alloy grains to be refined, the grid corrosion is uniform, however, crystal grain boundaries are increased due to fine crystal grains, in the process of anode grid alloy corrosion, due to the fact that energy at the crystal grain boundaries is high, corrosion preferentially occurs at the crystal grain boundaries, the growth of a corrosion layer is fast in the long-time corrosion process when the rare earth elements are added into the alloy, the creep elongation of the grid is obvious, active substances are easy to separate from the grid, and the failure of a battery is caused, and the situation is particularly obvious in a high-temperature scene, so that the rare earth additives are not suitable for being used in the corrosion-resistant grid.
In conclusion, the element composition and proportion of the grid alloy have great relation to the grid performance, and the mechanical performance and the electrochemical performance of the grid are directly influenced. Therefore, it is necessary to design a high-performance positive grid alloy which can enhance the mechanical strength of the grid and reduce the intergranular corrosion of the alloy, thereby improving the corrosion resistance of the grid, and the high-performance positive grid alloy is worthy of popularization.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the high-performance positive grid alloy which can enhance the mechanical strength of a grid and reduce the grain boundary corrosion of the alloy so as to improve the corrosion resistance of the grid.
The technical scheme for realizing the purpose of the invention is as follows: prepared by melting the following materials in percentage by weight: 0.03-0.2% of barium, 0.5-2.5% of tin, 0.005-0.03% of aluminum, 0.003-0.1% of silver, 0.01-0.5% of tellurium, 0.005-0.06% of silicon and the balance of lead.
Preferably, the material is prepared by melting the following materials in percentage by weight: 0.06% of barium, 1.5% of tin, 0.015% of aluminum, 0.01% of silver, 0.03% of tellurium, 0.008% of silicon and the balance of lead.
Preferably, the material is prepared by melting the following materials in percentage by weight: 0.08 percent of barium, 2.0 percent of tin, 0.015 percent of aluminum, 0.02 percent of silver, 0.04 percent of tellurium, 0.01 percent of silicon and the balance of lead.
Preferably, the material is prepared by melting the following materials in percentage by weight: 0.09% of barium, 1.8% of tin, 0.01% of aluminum, 0.015% of silver, 0.045% of tellurium, 0.02% of silicon and the balance of lead.
Preferably, the material is prepared by melting the following materials in percentage by weight: 0.07% of barium, 2.2% of tin, 0.02% of aluminum, 0.03% of silver, 0.04% of tellurium, 0.015% of silicon and the balance of lead.
After the technical scheme is adopted, the invention has the following positive effects:
(1) the alloy of the invention is different from the traditional lead-calcium-tin-aluminum alloy, barium is selected to replace calcium which aggravates alloy corrosion, the addition of barium can increase the mechanical strength of the grid, reduce the deformation and scrap of the grid in the production process, in addition, the crystal grain size can be increased while the crystal grain is uniform, because the activity of the alloy crystal grain boundary is stronger, the electrochemical corrosion of the lead alloy in the anode of the lead-acid storage battery is mainly concentrated at the crystal grain boundary, the amount of the grid alloy crystal boundary corrosion can be reduced along with the increase of the crystal grain size, and the purpose of reducing the alloy corrosion rate is achieved.
(2) The aluminum added in the alloy is mainly used for inhibiting the burning loss of barium in alloy configuration and grid casting. The tin added into the alloy mainly increases the mechanical property of the alloy, improves the fluidity of the alloy and the electrochemical property of a grid/lead paste interface, improves the deep cycle performance of a battery, and improves the corrosion resistance of the alloy.
(3) The alloy of the invention also introduces three alloy alterants of silver, tellurium and silicon, wherein the silver has the main functions of improving the creep resistance of the alloy, reducing the sensitivity of electrochemical corrosion passivation of the alloy, improving the conductivity of an alloy corrosion layer and avoiding the occurrence of early capacity loss of a battery; the tellurium mainly has the effects of stabilizing the metallographic structure, improving the casting performance and the mechanical performance of the alloy and solving the problem of heat cracking in the grid casting process; the main function of the silicon is to inhibit the segregation of alloy grain boundaries, improve the electrochemical corrosion inertia of the grains and the grain boundaries and reduce the corrosion of the grains and the grain boundaries. The three alloy modifiers are added simultaneously, so that the stability of alloy grains can be further improved, the mechanical property of the grid is improved, and the conductive property of an alloy corrosion layer is improved.
(4) The positive grid alloy prepared by melting the materials with the components in percentage by weight has a larger and more uniform metallographic structure, has excellent casting characteristics, high mechanical strength, high tensile strength, good thermal stability and good corrosion resistance, and improves the service life and the high-temperature performance of a battery while improving the quality and the production efficiency of the grid.
(5) The grid made of the alloy of the invention is subjected to a high-temperature accelerated floating charge test aiming at detecting the corrosivity of the positive grid, the high-temperature accelerated floating charge service life of the grid can reach 16 times, which is equivalent to 16 years of normal-temperature use, while the high-temperature accelerated floating charge service life of the grid made of the traditional lead-calcium-tin-aluminum alloy is only 8 times, which is equivalent to 8 years of normal-temperature use. In conclusion, the corrosion resistance of the grid made of the alloy is greatly improved, the service life of the battery is doubled, and the service life of the battery is more than 16 years.
Drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the present disclosure taken in conjunction with the accompanying drawings, in which
FIG. 1 is a metallographic morphology diagram of a lead-calcium-tin-aluminum alloy commonly used in a conventional lead-acid storage battery;
FIG. 2 is a metallographic structure diagram of an alloy according to example 1 of the present invention.
Detailed Description
(example 1)
The invention is prepared by melting the following materials in percentage by weight: 0.06% of barium, 1.5% of tin, 0.015% of aluminum, 0.01% of silver, 0.03% of tellurium, 0.008% of silicon and the balance of lead.
(example 2)
The invention is prepared by melting the following materials in percentage by weight: 0.08 percent of barium, 2.0 percent of tin, 0.015 percent of aluminum, 0.02 percent of silver, 0.04 percent of tellurium, 0.01 percent of silicon and the balance of lead.
(example 3)
The invention is prepared by melting the following materials in percentage by weight: 0.09% of barium, 1.8% of tin, 0.01% of aluminum, 0.015% of silver, 0.045% of tellurium, 0.02% of silicon and the balance of lead.
(example 4)
The invention is prepared by melting the following materials in percentage by weight: 0.07% of barium, 2.2% of tin, 0.02% of aluminum, 0.03% of silver, 0.04% of tellurium, 0.015% of silicon and the balance of lead.
FIG. 1 is a comparison item, which is the metallographic morphology of a lead-calcium-tin-aluminum alloy commonly used in the current lead-acid storage battery; FIG. 2 is the metallographic morphology of the alloy of example 1 of the present invention. As can be seen from the figure, compared with the prior art, the alloy of the invention has larger and more uniform metallographic structure.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like 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 high-performance corrosion-resistant positive grid alloy of the lead-acid storage battery is characterized in that: prepared by melting the following materials in percentage by weight: 0.03-0.2% of barium, 0.5-2.5% of tin, 0.005-0.03% of aluminum, 0.003-0.1% of silver, 0.01-0.5% of tellurium, 0.005-0.06% of silicon and the balance of lead.
2. The high-performance corrosion-resistant positive grid alloy of the lead-acid storage battery according to claim 1, wherein: prepared by melting the following materials in percentage by weight: 0.06% of barium, 1.5% of tin, 0.015% of aluminum, 0.01% of silver, 0.03% of tellurium, 0.008% of silicon and the balance of lead.
3. The high-performance corrosion-resistant positive grid alloy of the lead-acid storage battery according to claim 1, wherein: prepared by melting the following materials in percentage by weight: 0.08 percent of barium, 2.0 percent of tin, 0.015 percent of aluminum, 0.02 percent of silver, 0.04 percent of tellurium, 0.01 percent of silicon and the balance of lead.
4. The high-performance corrosion-resistant positive grid alloy of the lead-acid storage battery according to claim 1, wherein: prepared by melting the following materials in percentage by weight: 0.09% of barium, 1.8% of tin, 0.01% of aluminum, 0.015% of silver, 0.045% of tellurium, 0.02% of silicon and the balance of lead.
5. The high-performance corrosion-resistant positive grid alloy of the lead-acid storage battery according to claim 1, wherein: prepared by melting the following materials in percentage by weight: 0.07% of barium, 2.2% of tin, 0.02% of aluminum, 0.03% of silver, 0.04% of tellurium, 0.015% of silicon and the balance of lead.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911303351.9A CN111118337A (en) | 2019-12-17 | 2019-12-17 | High-performance corrosion-resistant positive grid alloy of lead-acid storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911303351.9A CN111118337A (en) | 2019-12-17 | 2019-12-17 | High-performance corrosion-resistant positive grid alloy of lead-acid storage battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111118337A true CN111118337A (en) | 2020-05-08 |
Family
ID=70499358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911303351.9A Pending CN111118337A (en) | 2019-12-17 | 2019-12-17 | High-performance corrosion-resistant positive grid alloy of lead-acid storage battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111118337A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110423917A (en) * | 2018-07-31 | 2019-11-08 | 荷贝克电池有限责任及两合公司 | Metal, electrode and battery |
| CN115772614A (en) * | 2022-11-01 | 2023-03-10 | 天能集团贵州能源科技有限公司 | Storage battery positive grid alloy and preparation method thereof |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1597270A (en) * | 1978-05-26 | 1981-09-03 | Univ Manchester | Lead alloys |
| EP1278256A2 (en) * | 2001-07-19 | 2003-01-22 | Delphi Technologies, Inc. | Lead alloy surface coating for positive lead-acid battery grids and methods of use |
| CN1423354A (en) * | 2001-12-03 | 2003-06-11 | 颜志明 | Manufacture of more excellent new-generation lead-acid battery using 8 element grid alloy material |
| CN101098006A (en) * | 2006-06-26 | 2008-01-02 | 上海飞轮有色冶炼厂 | Alloy for producing lead-acid accumulator grid and manufacturing method thereof |
| CN101237045A (en) * | 2007-02-03 | 2008-08-06 | 江苏双登集团有限公司 | Multi-element alloy for making lead acid accumulator plate grid |
| CN101399334A (en) * | 2007-09-28 | 2009-04-01 | 江苏双登集团有限公司 | Lead acid accumulator pole group manufacturing process |
| CN101675175A (en) * | 2007-03-20 | 2010-03-17 | 北星电池有限责任公司 | Lead-tin-silver-bismuth containing alloy for positive grid of lead acid batteries |
| CN102437342A (en) * | 2011-11-30 | 2012-05-02 | 江苏双登集团有限公司 | Anode grid alloy of lead acid storage battery for energy storage |
| CN104377365A (en) * | 2014-11-20 | 2015-02-25 | 双登集团股份有限公司 | Positive-electrode plate alloy for lead-acid storage battery |
| CN105177354A (en) * | 2015-08-17 | 2015-12-23 | 骆驼集团华中蓄电池有限公司 | Positive electrode grid alloy for maintenance-free lead-acid storage battery |
| CN106099118A (en) * | 2016-06-14 | 2016-11-09 | 界首市南都华宇电源有限公司 | A kind of anode plate for lead acid accumulator grid alloy |
| CN106367632A (en) * | 2016-12-22 | 2017-02-01 | 陈申申 | Positive plate grid alloy for power lead-acid storage battery as well as preparation method of positive plate grid alloy |
| CN108172839A (en) * | 2017-12-18 | 2018-06-15 | 双登集团股份有限公司 | Process for positive slab lattice of lead-acid accumulator high tinalloy and preparation method thereof |
| CN109402419A (en) * | 2018-08-28 | 2019-03-01 | 中国电力科学研究院有限公司 | Slicker solder grid alloy and preparation method |
-
2019
- 2019-12-17 CN CN201911303351.9A patent/CN111118337A/en active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1597270A (en) * | 1978-05-26 | 1981-09-03 | Univ Manchester | Lead alloys |
| EP1278256A2 (en) * | 2001-07-19 | 2003-01-22 | Delphi Technologies, Inc. | Lead alloy surface coating for positive lead-acid battery grids and methods of use |
| CN1423354A (en) * | 2001-12-03 | 2003-06-11 | 颜志明 | Manufacture of more excellent new-generation lead-acid battery using 8 element grid alloy material |
| CN101098006A (en) * | 2006-06-26 | 2008-01-02 | 上海飞轮有色冶炼厂 | Alloy for producing lead-acid accumulator grid and manufacturing method thereof |
| CN101237045A (en) * | 2007-02-03 | 2008-08-06 | 江苏双登集团有限公司 | Multi-element alloy for making lead acid accumulator plate grid |
| CN101675175A (en) * | 2007-03-20 | 2010-03-17 | 北星电池有限责任公司 | Lead-tin-silver-bismuth containing alloy for positive grid of lead acid batteries |
| CN101399334A (en) * | 2007-09-28 | 2009-04-01 | 江苏双登集团有限公司 | Lead acid accumulator pole group manufacturing process |
| CN102437342A (en) * | 2011-11-30 | 2012-05-02 | 江苏双登集团有限公司 | Anode grid alloy of lead acid storage battery for energy storage |
| CN104377365A (en) * | 2014-11-20 | 2015-02-25 | 双登集团股份有限公司 | Positive-electrode plate alloy for lead-acid storage battery |
| CN105177354A (en) * | 2015-08-17 | 2015-12-23 | 骆驼集团华中蓄电池有限公司 | Positive electrode grid alloy for maintenance-free lead-acid storage battery |
| CN106099118A (en) * | 2016-06-14 | 2016-11-09 | 界首市南都华宇电源有限公司 | A kind of anode plate for lead acid accumulator grid alloy |
| CN106367632A (en) * | 2016-12-22 | 2017-02-01 | 陈申申 | Positive plate grid alloy for power lead-acid storage battery as well as preparation method of positive plate grid alloy |
| CN108172839A (en) * | 2017-12-18 | 2018-06-15 | 双登集团股份有限公司 | Process for positive slab lattice of lead-acid accumulator high tinalloy and preparation method thereof |
| CN109402419A (en) * | 2018-08-28 | 2019-03-01 | 中国电力科学研究院有限公司 | Slicker solder grid alloy and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| NONE: ""Alloys satisfactory for use in lead acid electric storage batteries"", 《RESEARCH DISCLOSURE》 * |
| 陈建等: ""Pb-Sn-Me铅酸电池板栅合金的耐腐蚀性能研究"", 《电源技术》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110423917A (en) * | 2018-07-31 | 2019-11-08 | 荷贝克电池有限责任及两合公司 | Metal, electrode and battery |
| CN115772614A (en) * | 2022-11-01 | 2023-03-10 | 天能集团贵州能源科技有限公司 | Storage battery positive grid alloy and preparation method thereof |
| CN115772614B (en) * | 2022-11-01 | 2024-03-29 | 天能集团贵州能源科技有限公司 | Positive grid alloy of storage battery and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101656312B (en) | Alloy material for high-energy accumulator grid and preparation method thereof | |
| CN100588729C (en) | Lead alloy, uses and manufacturing technique thereof | |
| CN111118337A (en) | High-performance corrosion-resistant positive grid alloy of lead-acid storage battery | |
| CN111063894A (en) | Rare earth grid alloy for lead-acid storage battery | |
| CN107881356B (en) | Positive grid alloy for lead-acid storage battery and preparation method thereof | |
| CN102329982B (en) | Lead-antimony rare-earth positive grid alloy and preparation method thereof | |
| CN109786754A (en) | A kind of positive grid of lead-acid accumulator and preparation method thereof of lead calcium tin Cu-RE alloys | |
| US3881953A (en) | Battery electrode grids and method of making same from a lead-calcium-lithium-tin alloy | |
| CN101494289A (en) | Slab lattice of accumulator and manufacturing method and application thereof | |
| JP2000077076A (en) | Lead base alloy for storage battery | |
| CN106684391A (en) | Rare earth grid alloy for lead-acid storage batteries and production method thereof | |
| CN104377365A (en) | Positive-electrode plate alloy for lead-acid storage battery | |
| CN100483811C (en) | Accumulator plate grid alloy with lead, calcium, strontium and rare earth | |
| CN101515645B (en) | Slab lattice of storage battery, production method and application thereof | |
| JP3113895B2 (en) | Lead alloy for storage battery | |
| JP6601654B2 (en) | Control valve type lead acid battery | |
| JP4502346B2 (en) | Lead-based alloys for lead-acid batteries | |
| CN113782747B (en) | High-calcium alloy for lead-acid storage battery grid and preparation method thereof | |
| CN105322179A (en) | Corrosion-resistant green alloy of positive grid for lead-acid storage battery | |
| CN116287858B (en) | Lead-based barium sodium aluminum alloy for negative grid of lead-acid storage battery, and preparation method and application thereof | |
| CN101633988A (en) | Industrial pure lead with liquid oxidation resistance and application thereof | |
| CN116254437A (en) | Alloy for positive grid of maintenance-free lead-acid storage battery and preparation method of alloy | |
| JP2006079951A (en) | Lead-acid storage battery grid body and lead alloy for it | |
| CN114248037A (en) | High-oxidation-resistance lead-free soldering tin material | |
| JP2003151563A (en) | Lead-base alloy for lead storage battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200508 |