FR2484145A1 - Lead calcium alloy for lead electrode grids - contg. mischmetal addition to improve grain refinement - Google Patents
Lead calcium alloy for lead electrode grids - contg. mischmetal addition to improve grain refinement Download PDFInfo
- Publication number
- FR2484145A1 FR2484145A1 FR8012602A FR8012602A FR2484145A1 FR 2484145 A1 FR2484145 A1 FR 2484145A1 FR 8012602 A FR8012602 A FR 8012602A FR 8012602 A FR8012602 A FR 8012602A FR 2484145 A1 FR2484145 A1 FR 2484145A1
- Authority
- FR
- France
- Prior art keywords
- lead
- alloy
- content
- calcium
- contg
- 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.)
- Granted
Links
- 239000002142 lead-calcium alloy Substances 0.000 title claims description 7
- 229910001122 Mischmetal Inorganic materials 0.000 title abstract description 8
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 21
- 239000000956 alloy Substances 0.000 claims abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 4
- 150000002910 rare earth metals Chemical class 0.000 abstract description 4
- 229910052718 tin Inorganic materials 0.000 abstract description 4
- 238000005266 casting Methods 0.000 abstract description 2
- 238000007670 refining Methods 0.000 abstract description 2
- 229910052684 Cerium Inorganic materials 0.000 description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 6
- 238000007792 addition Methods 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- -1 cerium for example Chemical class 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/68—Selection of materials for use in lead-acid accumulators
- H01M4/685—Lead 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
- C22C11/02—Alloys based on lead with an alkali or an alkaline earth metal as the next major constituent
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
Description
Perfectionnement au alliages plomb-calcium destinés à la réalisation des supports d'électrodes d'accumulateurs au plomb
La présente invention concerne les alliages à base de plomb et de calcium destinés à la réalisation des supports d'électrodes d'accumulateurs au plomb. Improvement to lead-calcium alloys intended for the production of lead electrode holders
The present invention relates to alloys based on lead and calcium intended for the production of electrode holders for lead accumulators.
Il est déjà connu, notamment par le brevet anglais n0 793 083 déposé le 26 Avril 1956 par la Société The Chroride Electrical Storage
Company Limitez, d'introduire dans ces alliages des petites quantités d'une terre rare, telle que le cérium par exemple, de maniere à diminuer la dimension des grains dans l'alliage.It is already known, in particular by the English patent n ° 793 083 filed on April 26, 1956 by the company The Chroride Electrical Storage
Company Limit, to introduce into these alloys small quantities of a rare earth, such as cerium for example, so as to reduce the size of the grains in the alloy.
Le cérium peut être ajouté soit directement, soit sous forme d'un mélange de terres rares, tel que le Misch Metall par exemple. Cerium can be added either directly or in the form of a mixture of rare earths, such as Misch Metall for example.
Plus précisément, dans le brevet précité, il est indiqué que la teneur en cérium ou en Misch Metaîl dans l'alliage plomb-calcium doit être comprise entre 0,01 et 0,1% autrement dit entre 100 g/tonne (100 ppm) et 1000 g/tonne (1000 ppm). More specifically, in the aforementioned patent, it is indicated that the content of cerium or Misch Metail in the lead-calcium alloy must be between 0.01 and 0.1%, in other words between 100 g / tonne (100 ppm) and 1000 g / tonne (1000 ppm).
Toutefois, la Demanderesse a constaté que, pour pouvoir introduire une telle quantité de cérium ou de Misch Métall, il était nécessaire de porter le four des machines de fonderie à une température supérieure à 420 C. However, the Applicant has found that, in order to be able to introduce such a quantity of cerium or Misch Metall, it was necessary to bring the furnace of foundry machines to a temperature above 420 C.
Or, à partir de #200C, il se produit une oxydation préjudiciable du calcium. However, from # 200C, there is a harmful oxidation of calcium.
La présente invention perinet notamment de remédier à cet inconvé- nient. The present invention in particular makes it possible to remedy this drawback.
Elle a pour objet un alliage plomb-calcium destiné à la réalisation des supports d'électrodes d'accumulateurs au plomb dans lequel la teneur en calcium est supérieure à 0,05%, caractérisé par le fait que ledit alliage comporte en outre un mélange de terres rares, la teneur globale en terres rares étant comprise entre 30 et 95 ppm. It relates to a lead-calcium alloy intended for the production of lead battery electrode supports in which the calcium content is greater than 0.05%, characterized in that the said alloy further comprises a mixture of rare earths, the overall rare earth content being between 30 and 95 ppm.
Avantageusement, ce mélange de terres rares est constitué par du Misch Metall, comprenant un mélange de cérium, de lanthane, de néodyme et de praséodyne, par exemple 50% de cérium, 25% de lanthane, 20% de néodyme et 5% de praséodyne. Advantageously, this mixture of rare earths is constituted by Misch Metall, comprising a mixture of cerium, lanthanum, neodymium and praseodymium, for example 50% of cerium, 25% of lanthanum, 20% of neodymium and 5% of praseodyn .
Le mélange de terres rares, tel que le Misch Metall, permet à ces teneurs un affinage satisfaisant des grains de l'alliage à une température de fabrication du support inférieure à 4200C ; il augmente par ailleurs notablement la résistance et la corrosion. The mixture of rare earths, such as Misch Metall, allows these contents a satisfactory refining of the grains of the alloy at a temperature of manufacture of the support lower than 4200C; it also significantly increases resistance and corrosion.
A titre d'exeiiple, on a mesuré le taux de corrosion de grilles en cyclage formées par des alliages plomb-calcium à 0,06 et 0,12% de calcium. La perte de poids de la grille est diminuée de moitié en présence de 73 ppm de Misch Metall. As an example, the corrosion rate of cycling grids formed by lead-calcium alloys with 0.06 and 0.12% calcium was measured. The weight loss of the grid is halved in the presence of 73 ppm of Misch Metall.
Les conditions d'expérimentation étaient les suivantes :
- densité de l'acide sulfurique 1,26 à 250C
- densité de courant 3,2 mA/cm2
- le courant est anodique pendant 2 mn et cathodique pendant 1 mn. The experimental conditions were as follows:
- density of sulfuric acid 1.26 at 250C
- current density 3.2 mA / cm2
- the current is anodic for 2 min and cathodic for 1 min.
- tempErature dtessai 400 C
On note aussi une diminution importante de la décohésion de la grille.- test temperature 400 C
There is also a significant decrease in the decohesion of the grid.
Par ailleurs après une certaine période de cyclage sur batterie, alors que 401 des grilles plomb-calcium classiques à Oxo6% sont cassés au niveau des cadres, toutes les grilles conformes à l'invention en plomb-calcium-Misch Metall sont entières. Furthermore, after a certain period of cycling on a battery, while 401 of the conventional lead-calcium grids at Oxo6% are broken at the level of the frames, all the grids according to the invention made of lead-calcium-Misch Metall are whole.
De plus, il est possible de prévoir dans l'alliage conforme à l'invention une teneur en calcium supérieure à celle généralement utilisée, ce qui contribue à l'amélioration des propriétés mécaniques dudit support. In addition, it is possible to provide in the alloy according to the invention a calcium content greater than that generally used, which contributes to the improvement of the mechanical properties of said support.
On peut ainsi utiliser une teneur en calcium supérieure à 0,1% et qui peut même atteindre 0,18%. It is thus possible to use a calcium content greater than 0.1% and which can even reach 0.18%.
Un avantage de l'utilisation de l'alliage conforme à l'invention est que, permettant de fabriquer les supports d'électrodes à une température inférieure à celle généralement utilisée, il conduit bien évidemment à une économie d'énergie. An advantage of using the alloy according to the invention is that, making it possible to manufacture the electrode supports at a temperature lower than that generally used, it obviously leads to energy savings.
L'invention est également applicable aux alliages plomb-calcium contenant de l'étain, la teneur en étain étant comprise entre 0,05 et 1%, et/ou de l'aluminium, la teneur en aluminium étant comprise entre 0,001 et 0,03%. The invention is also applicable to lead-calcium alloys containing tin, the tin content being between 0.05 and 1%, and / or aluminum, the aluminum content being between 0.001 and 0, 03%.
L'addition d'étain a pour effet connu d'améliorer la coulabilité de l'alliage. The addition of tin has the known effect of improving the flowability of the alloy.
L'addition d'aluminium a pour effet de protéger, au moment de la coulée, l'alliage de l'oxydation. The addition of aluminum has the effect of protecting the alloy from oxidation at the time of casting.
On peut toutefois constater qu'à ces teneurs, en règle générale, les ajouts d'aluminium ne se retrouvent pas dans le support. It can however be seen that at these contents, as a general rule, the aluminum additions are not found in the support.
L'invention a bien entendu également pour objet les supports d'électrodes constitués par les alliages précédemment définis, les électrodes comportant de tels supports et les accumulateurs comprenant ces électrodes. The invention of course also relates to the electrode supports formed by the alloys defined above, the electrodes comprising such supports and the accumulators comprising these electrodes.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8012602A FR2484145A1 (en) | 1980-06-06 | 1980-06-06 | Lead calcium alloy for lead electrode grids - contg. mischmetal addition to improve grain refinement |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8012602A FR2484145A1 (en) | 1980-06-06 | 1980-06-06 | Lead calcium alloy for lead electrode grids - contg. mischmetal addition to improve grain refinement |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| FR2484145A1 true FR2484145A1 (en) | 1981-12-11 |
| FR2484145B1 FR2484145B1 (en) | 1982-06-11 |
Family
ID=9242785
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR8012602A Granted FR2484145A1 (en) | 1980-06-06 | 1980-06-06 | Lead calcium alloy for lead electrode grids - contg. mischmetal addition to improve grain refinement |
Country Status (1)
| Country | Link |
|---|---|
| FR (1) | FR2484145A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110923488A (en) * | 2019-12-24 | 2020-03-27 | 云南大泽电极科技股份有限公司 | Rare earth adding process for preparing lead alloy at high temperature |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB793083A (en) * | 1956-04-26 | 1958-04-09 | Chloride Electrical Storage Co | Improvements relating to lead-acid accumulators |
| GB1414171A (en) * | 1972-02-09 | 1975-11-19 | Lucas Batteries Ltd | Battery plate grids for lead-acid batteries and alloys for use in the production of such grids |
| JPS5376327A (en) * | 1976-12-17 | 1978-07-06 | Matsushita Electric Industrial Co Ltd | Lead storage battery |
-
1980
- 1980-06-06 FR FR8012602A patent/FR2484145A1/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB793083A (en) * | 1956-04-26 | 1958-04-09 | Chloride Electrical Storage Co | Improvements relating to lead-acid accumulators |
| GB1414171A (en) * | 1972-02-09 | 1975-11-19 | Lucas Batteries Ltd | Battery plate grids for lead-acid batteries and alloys for use in the production of such grids |
| JPS5376327A (en) * | 1976-12-17 | 1978-07-06 | Matsushita Electric Industrial Co Ltd | Lead storage battery |
Non-Patent Citations (1)
| Title |
|---|
| CA1979 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110923488A (en) * | 2019-12-24 | 2020-03-27 | 云南大泽电极科技股份有限公司 | Rare earth adding process for preparing lead alloy at high temperature |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2484145B1 (en) | 1982-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH01211858A (en) | Rechargeable cell | |
| Zhong et al. | Evaluation of lead—calcium—tin—aluminium grid alloys for valve-regulated lead/acid batteries | |
| CN105845884A (en) | Mg-Li-Al alloy electrode modified by cerium-rich mixed rare earth elements for sea cell and preparation method of Mg-Li-Al alloy electrode | |
| JP2002175798A (en) | Sealed lead-acid battery | |
| FR2484145A1 (en) | Lead calcium alloy for lead electrode grids - contg. mischmetal addition to improve grain refinement | |
| JP3113895B2 (en) | Lead alloy for storage battery | |
| CN86103370A (en) | Grid alloy of battery and production method thereof | |
| JP2832228B2 (en) | Zinc alloy powder for alkaline battery and method for producing the same | |
| JP2832227B2 (en) | Zinc alloy powder for alkaline battery and method for producing the same | |
| US4253871A (en) | Alloys for making electrode supports in lead accumulators | |
| FR2483958A1 (en) | IMPROVEMENT OF LEAD-ANTIMONY ALLOYS FOR THE PRODUCTION OF LEAD-ACRYLIC ELECTRODES | |
| JP2794745B2 (en) | Manufacturing method of grid for lead storage battery | |
| JP4793518B2 (en) | Lead acid battery | |
| JPH0420972B2 (en) | ||
| JP2006079951A (en) | Lead-acid storage battery grid body and lead alloy for it | |
| JP2003323881A (en) | Control valve lead-acid battery | |
| JP2008266739A (en) | Lead alloy and lead acid battery for lead acid battery | |
| JP3658871B2 (en) | Lead acid battery | |
| JPS6224911B2 (en) | ||
| JPH09330700A (en) | Lead-acid battery | |
| JPH09167611A (en) | Lead-acid battery | |
| Bolotovsky | Lead calcium alloys in the production of lead/acid batteries | |
| JPH05166507A (en) | Zinc alloy powder for alkaline battery and its manufacture | |
| JP2832230B2 (en) | Zinc alloy powder for alkaline battery and method for producing the same | |
| JPS61203568A (en) | Lead storage battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| ST | Notification of lapse |