WO1999005732A1 - Method for the continuous manufacture of positive battery grids and positive grids obtained by said method - Google Patents
Method for the continuous manufacture of positive battery grids and positive grids obtained by said method Download PDFInfo
- Publication number
- WO1999005732A1 WO1999005732A1 PCT/FR1998/001643 FR9801643W WO9905732A1 WO 1999005732 A1 WO1999005732 A1 WO 1999005732A1 FR 9801643 W FR9801643 W FR 9801643W WO 9905732 A1 WO9905732 A1 WO 9905732A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alloy
- grids
- positive
- relative concentration
- weight
- Prior art date
Links
Classifications
-
- 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
-
- 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
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
-
- 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
Definitions
- the present invention relates generally to grids of lead-acid accumulators for batteries and more particularly to a process for the continuous production of positive grids.
- the content of tin in the lead alloy conditions both the corrosion resistance of the alloy and the conductivity of the interface between the positive metallic grid and the active material (lead oxide) which it supports. This last characteristic is particularly sought after in the case of starter batteries which, throughout their life, experience repeated deeper charge-discharge cycles.
- the solubility of calcium in the lead matrix is however conditioned by the tin content of the alloy.
- the calcium content must be fixed in a low concentration range if one wishes to avoid the premature appearance of the phenomenon of aging.
- Monitoring, which develops at the grain boundaries, is in the form of precipitates (Pb ⁇ - X Sn ⁇ ) 3 Ca, and causes a reduction in the mechanical properties of the affected area which is subject to accelerated corrosion.
- the tin content being fixed, it then completely determines the range of calcium contents.
- Manufacturers of lead - calcium - tin alloys also add a small amount of aluminum, at a relative concentration by weight of between 0.001% and 0.035%, to prevent oxidation of the molten alloy.
- the current trend in the lead-acid battery manufacturing industries is to favor the production of positive grids using continuous development processes. These continuous manufacturing development processes are more productive and provide consistent quality grids.
- the principle of these continuous manufacturing processes of positive grids is to produce a blank from a continuous casting of alloy then, to subject this blank to a more or less significant mechanical deformation, either during cutting and of an expansion of the blank either during rolling to produce the positive grids at the desired thickness.
- blade is understood here to mean the result of the solidification by cooling of the alloy casting.
- the alloy consists of an alternation of layers with fine grains having undergone a significant work hardening (recrystallization zone) and coarse-grained layers, signatures of the casting microstructure.
- the present invention provides a new process for the continuous production of positive grids of lead-acid accumulators, which makes it possible to obtain positive grids having a high hardness, an ability to retain high mechanical properties. level, constant over time, and good corrosion resistance.
- the continuous manufacturing process comprises the following steps: a) a lead alloy is prepared which comprises calcium, at a relative concentration by weight of between 0.04% and 0.12%, tin at a relative concentration by weight of less than 3%, aluminum , at a relative concentration by weight between 0.001% and 0.035%, and barium, at a relative concentration by weight between 0.02% and 0.1%, b) A blank is produced from a continuous casting of said lead alloy, c) mechanically treating said blank to form said positive grids.
- the microstructure of the preform resulting from the continuous casting of lead alloy produced according to the invention supports without deteriorating over time (aging), the mechanical treatment for the final shaping of said positive grids.
- an absence of transformation of the casting microstructure has been observed under the combined effect of temperature, work hardening and time, which gives the positive grids an improved corrosion resistance.
- the corrosion process of said positive grids develops uniformly on the grains of the alloy instead of preferentially attacking the grain boundaries.
- the positive grids obtained according to the process according to the invention which contain barium, retain their mechanical characteristics and their dimensions better than the positive grids of the prior art which are free of barium.
- a lead alloy is prepared whose relative concentration by weight of calcium is between 0.05% and 0.11%, the relative concentration by weight tin is between 0.5% and 2.5% and the relative concentration by weight of aluminum is between 0.0016% and 0.025%.
- a lead alloy is prepared which comprises a relative concentration by weight of calcium equal to approximately 0.11% and a relative concentration by weight of barium equal to approximately 0.084%.
- step b) an alloy strip is formed, the thickness of which corresponds to the thickness of the grids targeted and in step c) said strip d is deployed.
- alloy in a series of positive grids in step b) thick grids are formed and in step c) the grids are laminated to the desired thickness.
- step b) a thick alloy strip is formed and in step c) said alloy strip is laminated to the desired thickness and then said strip is deployed laminated into a series of positive grids.
- the present invention also provides positive grids of lead-acid accumulators manufactured according to the aforementioned process.
- FIG. 1 shows the alloy microstructure of a positive grid of accumulator obtained according to a continuous manufacturing process of the state of the art, seen in transverse and longitudinal sections,
- FIG. 2 shows the alloy microstructure of a positive grid seen in cross section and horizontal, obtained according to the continuous manufacturing process in accordance with the present invention
- FIG. 3 illustrates the corrosion behavior of two alloys, a first free of barium and a second comprising barium (prepared during step a) of the process according to the invention),
- FIG. 4 shows two microstructures of two positive lead alloy grids with and without barium, obtained by continuous casting of an alloy strip, rolling and expansion of the laminated alloy strip,
- FIG. 5 shows the alloy microstructure of a positive grid obtained according to a preferred variant of the method according to the invention.
- the alloys are prepared as follows:
- Figure 1 shows cross and horizontal sections of a positive grid of a lead alloy containing in relative concentration by weight, 0.069% calcium, 1.24% tin and 0.0016% aluminum.
- This grid is obtained according to a process of the prior art continuously from a lead alloy free of barium, by carrying out a continuous casting of a strip of said alloy to the desired thickness and expansion of the strip in the form of a series of grids.
- Figure 2 shows cross sections (microstructure from above) and horizontal (microstructure from below) of an alloy of a positive grid of accumulator produced according to the method according to the invention, and more particularly made of an alloy of lead which contains in relative concentration by weight, 0.071% of calcium, 1.22% of tin and 0.002% of aluminum as well as 0.04% of barium.
- the grid is obtained more particularly by the formation of a continuous casting of said aforementioned lead alloy to form a strip of the desired thickness. Then we deployed in the form of a series of grids, the alloy strip obtained during continuous casting.
- the corrosion facies of the barium-free alloy constituting the positive grid of the prior art is clearly of the intergranular type whereas for the second positive grid obtained according to the process according to the invention, the corrosion of the alloy is uniform. Note, with regard to the grid obtained according to the method according to the invention, the refinement of the grain size of the alloy.
- Figure 4 shows the change in microstructure between a positive grid of a lead alloy
- Example 2 There is not only a reduction in the hardness of the material not doped with barium, but also the higher level of mechanical characteristics of the latter without alteration over time.
- Example 2 There is not only a reduction in the hardness of the material not doped with barium, but also the higher level of mechanical characteristics of the latter without alteration over time.
- the hardness measurement is carried out using a microdurometer (load of 25 grams), under a microscope, in order to measure the hardness of the over-aged areas.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002297768A CA2297768A1 (en) | 1997-07-25 | 1998-07-24 | Method for the continuous manufacture of positive battery grids and positive grids obtained by said method |
AU88681/98A AU8868198A (en) | 1997-07-25 | 1998-07-24 | Method for the continuous manufacture of positive battery grids and positive grids obtained by said method |
KR1020007000753A KR20010022181A (en) | 1997-07-25 | 1998-07-24 | Method for the Continuous Manufacture of Positive Battery Grids and Positive Grids Obtained by Said Method |
EP98940332A EP0996987A1 (en) | 1997-07-25 | 1998-07-24 | Method for the continuous manufacture of positive battery grids and positive grids obtained by said method |
JP2000504614A JP2001511587A (en) | 1997-07-25 | 1998-07-24 | Method for continuously producing a positive grid of a storage battery and a positive grid obtained by such a method |
BR9811290-2A BR9811290A (en) | 1997-07-25 | 1998-07-24 | Continuous manufacturing process of positive grades of lead acid accumulators, and positive grades of lead acid accumulators |
PL98338604A PL338604A1 (en) | 1997-07-25 | 1998-07-24 | Method of continuously manufacturing lattice grids of accumulator positive plates and lattice grid obtained thereby |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR97/09485 | 1997-07-25 | ||
FR9709485A FR2766622B1 (en) | 1997-07-25 | 1997-07-25 | PROCESS FOR THE CONTINUOUS MANUFACTURE OF POSITIVE BATTERY GRIDS, AND POSITIVE GRID OBTAINED ACCORDING TO SUCH A METHOD |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999005732A1 true WO1999005732A1 (en) | 1999-02-04 |
Family
ID=9509629
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR1998/001643 WO1999005732A1 (en) | 1997-07-25 | 1998-07-24 | Method for the continuous manufacture of positive battery grids and positive grids obtained by said method |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0996987A1 (en) |
JP (1) | JP2001511587A (en) |
KR (1) | KR20010022181A (en) |
AU (1) | AU8868198A (en) |
BR (1) | BR9811290A (en) |
CA (1) | CA2297768A1 (en) |
FR (1) | FR2766622B1 (en) |
PL (1) | PL338604A1 (en) |
WO (1) | WO1999005732A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100499227C (en) * | 2002-04-18 | 2009-06-10 | 古河电池株式会社 | Lead-based alloy, lead acid battery substrate and lead-acid battery |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU777119B2 (en) * | 1999-07-30 | 2004-09-30 | Wirtz Manufacturing Co., Inc. | Battery grids |
DE102005038064A1 (en) * | 2005-08-10 | 2007-02-15 | Deutsche Exide Gmbh | electrode grid |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4137378A (en) * | 1977-05-31 | 1979-01-30 | General Battery Corporation | Calcium-strontium-lead grid alloy for use in lead-acid batteries |
EP0040951A1 (en) * | 1980-05-27 | 1981-12-02 | General Motors Corporation | Wrought lead-calcium-strontium-tin (+/- barium) alloy for battery components |
US5604058A (en) * | 1995-04-28 | 1997-02-18 | Wirtz Manufacturing Co., Inc. | Battery grids, method and apparatus |
-
1997
- 1997-07-25 FR FR9709485A patent/FR2766622B1/en not_active Expired - Fee Related
-
1998
- 1998-07-24 PL PL98338604A patent/PL338604A1/en unknown
- 1998-07-24 CA CA002297768A patent/CA2297768A1/en not_active Abandoned
- 1998-07-24 WO PCT/FR1998/001643 patent/WO1999005732A1/en not_active Application Discontinuation
- 1998-07-24 BR BR9811290-2A patent/BR9811290A/en not_active IP Right Cessation
- 1998-07-24 JP JP2000504614A patent/JP2001511587A/en active Pending
- 1998-07-24 KR KR1020007000753A patent/KR20010022181A/en not_active Application Discontinuation
- 1998-07-24 EP EP98940332A patent/EP0996987A1/en not_active Withdrawn
- 1998-07-24 AU AU88681/98A patent/AU8868198A/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4137378A (en) * | 1977-05-31 | 1979-01-30 | General Battery Corporation | Calcium-strontium-lead grid alloy for use in lead-acid batteries |
EP0040951A1 (en) * | 1980-05-27 | 1981-12-02 | General Motors Corporation | Wrought lead-calcium-strontium-tin (+/- barium) alloy for battery components |
US5604058A (en) * | 1995-04-28 | 1997-02-18 | Wirtz Manufacturing Co., Inc. | Battery grids, method and apparatus |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100499227C (en) * | 2002-04-18 | 2009-06-10 | 古河电池株式会社 | Lead-based alloy, lead acid battery substrate and lead-acid battery |
Also Published As
Publication number | Publication date |
---|---|
AU8868198A (en) | 1999-02-16 |
JP2001511587A (en) | 2001-08-14 |
KR20010022181A (en) | 2001-03-15 |
PL338604A1 (en) | 2000-11-06 |
FR2766622A1 (en) | 1999-01-29 |
CA2297768A1 (en) | 1999-02-04 |
EP0996987A1 (en) | 2000-05-03 |
BR9811290A (en) | 2000-08-29 |
FR2766622B1 (en) | 1999-10-22 |
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