CN103985879B - A kind of plumbous calcium stannum aluminum positive grid alloy and preparation method thereof - Google Patents
A kind of plumbous calcium stannum aluminum positive grid alloy and preparation method thereof Download PDFInfo
- Publication number
- CN103985879B CN103985879B CN201410208225.6A CN201410208225A CN103985879B CN 103985879 B CN103985879 B CN 103985879B CN 201410208225 A CN201410208225 A CN 201410208225A CN 103985879 B CN103985879 B CN 103985879B
- Authority
- CN
- China
- Prior art keywords
- calcium
- stannum
- plumbous
- alloy
- melt
- 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.)
- Active
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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/68—Selection of materials for use in lead-acid accumulators
- H01M4/685—Lead alloys
-
- 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)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention discloses a kind of plumbous calcium stannum aluminum positive grid alloy and preparation method thereof.Described alloy is made up of the metallic element of following mass fraction: calcium: 0.05 ~ 0.12%, stannum: 0.5 ~ 2.0%, aluminum: 0.01 ~ 0.1%, plumbous for surplus.Preparation method of the present invention adopts calcium bits and the aluminium foil of sheet lead parcel mix homogeneously, is pressed in melted plumbous liquid, eliminates the fusion process of calcium aluminum foundry alloy.Alloy prepared by the present invention has an excellent comprehensive mechanical property, and can effectively reduce the impedance of oxide-film, and the addition of stannum not only improves discharge and recharge ability to accept and the deep-circulating performance of accumulator, and improves the rotproofness of alloy；The performance requirement of electric bicycle lead-acid accumulator can be substantially met.The present invention is with calcium, stannum, aluminum for the plumbous calcium positive grid alloy of additive preparation, without the severe toxicity element such as cadmium, arsenic, such that it is able to avoid the harm to environment and forefront of the production workman to greatest extent.
Description
Technical field
The invention belongs to field of metallurgy, be specifically related to a kind of plumbous calcium stannum aluminum positive grid alloy and preparation method thereof.
Background technology
Grid is an important ingredient in lead-acid battery, although capacity is not had direct castering action by it, but play the skeletal support effect as active substance and conduction, evenly distributing electric current effect in battery charge and discharge process, these performances directly limit capacity and the cycle life of battery, and the whether superior alloy depended primarily on used by grid of these performances.
The main Pb-Sb-Cd alloy of grid material of traditional lead acid batteries, the casting character of this alloy and mechanical performance all can meet the production of battery and use needs, and the corrosion layer of its formation has good electric conductivity, substantially can suppress PCL phenomenon.But the overpotential of hydrogen evolution of antimony and cadmium is relatively low, the especially dissolving of antimony and transfer in alloy so that both positive and negative polarity analysis oxygen overpotential of hydrogen evolution reduces, and so causes that battery dehydration is accelerated, self discharge increase.And cadmium is severe toxicity metal, environment all can be caused bigger pollution by preparation and recovery at battery, and harm operator's is healthy.
Prohibitting the use of already abroad containing cadmium alloy, domestic explicit stipulation will prohibit the use of to the end of the year 2013 containing cadmium alloy, so Pb-Sb-Cd alloy has had logged out the arena of history, lead-calcium alloy just becomes the study hotspot of lead-acid battery therewith.Lead-calcium alloy resistance is less, close to pure lead；And overpotential of hydrogen evolution is high, so water decomposition is few；Calcium is negative potential simultaneously, will not cause self discharge and toxic gas SbH by solution transfer to negative pole3Precipitation.It is found that the corrosive film poorly conductive that calcium is formed, and calcium also makes alloy rotproofness decline, and the non-antimony effect of generation easily makes lead-acid battery premature capacity loss and life-span termination in advance etc. occur.So Pb-Ca-Sn-Al alloy arises, the addition of stannum can better improve the electric conductivity of corrosive film, thus avoiding the premature capacity loss of battery.Find in actual applications, the battery life that existing Pb-Ca-Sn-Al alloy produces is than short nearly the 1/3 of plumbous antimony cadmium, cause that battery life terminates in advance through dissecting the rotproofness difference finding Pb-Ca-Sn-Al alloy, finding that the grid that Conventional alloys casts out easily produces internal shrinkage in grid " ten " font crosslinking place, this is also the reason causing existing grid rotproofness difference simultaneously.
Summary of the invention
Present invention aims to existing lead-calcium alloy not enough, a kind of plumbous calcium stannum aluminum positive grid alloy is provided, make it have good deep-circulating performance and excellent cycle life, reduce grid and produce the probability of shrinkage cavity, to the various aspects of performance of alloy near or above Pb-Sb-Cd alloy.The preparation method simultaneously providing plumbous calcium stannum aluminum positive grid alloy, reduces calcium scaling loss, improves alloying component concordance, shortens the alloy preparation time, improves production efficiency.
For reaching above-mentioned technical purpose, technical scheme is as follows:
A kind of plumbous calcium stannum aluminum positive grid alloy, is made up of the raw material of following mass percent:
Calcium 0.05～0.12%
Stannum 0.5～2.0%
Aluminum 0.01～0.1%
Surplus is plumbous.
The further improvement project of the present invention is, each raw material accounts for the mass percent of total raw material and is:
Calcium 0.09%
Stannum 1.8%
Aluminum 0.05%
Surplus is plumbous.
The method preparing above-mentioned a kind of plumbous calcium stannum aluminum positive grid alloy, comprises the following steps: by above-mentioned raw materials quality percentage ratio,
(1) lead button accounting for leady raw materials gross mass 80～84% is added in the graphite market pot of intermediate frequency furnace and heat to 670～680 DEG C, lead button is made fully to melt, calcium bits and the aluminium foil of mix homogeneously is wrapped up with sheet lead, it is pressed in melted plumbous liquid, then stir 2～3min and make calcium aluminium element mix homogeneously in plumbous liquid, in the process, keep the temperature of melt between 670～680 DEG C；
(2) stop stirring and heating, add the lead button of residue 15～19%, melt is stirred, in melt, add stannum when temperature is down to 520～540 DEG C, continue stirring 2～3min and make stannum be completely melt and mix homogeneously；
(3) slag-cleaning agent is spread to bath surface, stir 1～2min, then scum silica frost is removed；
(4) cast when melt temperature is down to 480～500 DEG C.
Sheet lead quality accounts for addition leady raw materials gross mass less than the 1% of gross mass.
The bits of calcium described in step (1), aluminium foil are all diameters is the tablet of 3～4mm.
It is convenient reinforced for wrapping up an aspect with sheet lead, additionally prevents calcium bits from contacting with oxygen, reduces calcium bits and aoxidize in atmosphere.
Described graphite market pot has long semielliptical shape inner chamber.Usual market pot is square, and electrical bar heats；Square lead pan has a stirring dead angle, and intermediate frequency heating speed is fast, efficiency is high simultaneously, and heating has from agitating function simultaneously, so can so that the alloying component allotted evenly.
After adopting technique scheme, the invention has the beneficial effects as follows:
1, in Pb-Ca-Sn-Al alloy, in certain content range, Theil indices is more high, and the rotproofness of alloy is more good, and the deep-circulating performance of alloy also can be better.The Theil indices of the present invention is than conventional high by nearly 50%, so the alloy rotproofness of present invention ratio is conventional better, the anodic attack membrane impedance formed is less, is more beneficial for deeper cavity.The addition of high stannum can also prevent the generation of grid " ten " font crosslinking place shrinkage cavity, it is to avoid grid premature failure.The alloying element ratio that the present invention provides can improve the corrosion resistant ability of grid better, and than conventional proportion of lead calcium alloy, there is less corrosive film impedance, reduce premature capacity loss of lead acid battery and thermal runaway tympanites problem, improve the deeper cavity life-span of battery.
2, the present invention is in process for preparation, is considered to be worth doing by the calcium of mix homogeneously and is added simultaneously in plumbous liquid with aluminium foil, eliminates the process of tradition preparation calcium aluminum foundry alloy, so not only avoid a large amount of scaling loss of calcium, and improve production efficiency, saved production cost.
The graphite market pot of the long semielliptical shape inner chamber used by 3 present invention and the intermediate frequency furnace with automatic stirring function, these can make the alloying component uniformity allotted, and improves production efficiency.
Detailed description of the invention
Embodiment one
A kind of plumbous calcium stannum aluminum positive grid alloy preparation method, comprises the following steps:
(1) raw material prepares: lead, calcium, stannum and aluminum, and each raw material accounts for the mass percent of total raw material and is: calcium: 0.08%, stannum: 0.5%, aluminum: 0.03%, plumbous for surplus；
(2) lead button accounting for leady raw materials gross mass 80～84.5% is added in the graphite market pot of intermediate frequency furnace and heat to 670～680 DEG C, lead button is made fully to melt, calcium bits and the aluminium foil of mix homogeneously is wrapped up with sheet lead, and it is pressed in melted plumbous liquid together, then stir 2～3min and make calcium aluminium element mix homogeneously in plumbous liquid, in the process, keep the temperature of melt between 670～680 DEG C；
(3) stop stirring and heating, add the lead button of residue 15～20%, melt is stirred, add stannum when temperature is down to 520～540 DEG C to melt, continue stirring 2～3min and make stannum be completely melt and mix homogeneously；
(4) slag-cleaning agent is spread to bath surface, stir 1～2min, then scum silica frost is removed；
(5) cast when melt temperature is down to 480～500 DEG C.In the present embodiment, sheet lead quality accounts for addition leady raw materials gross mass 0.5%, and calcium bits, aluminium foil are all diameters is the tablet of 3～4mm.Lower same.
Embodiment two
A kind of plumbous calcium stannum aluminum positive grid alloy preparation method, it is characterised in that comprise the following steps:
(1) raw material prepares: lead, calcium, stannum and aluminum, and each raw material accounts for the mass percent of total raw material and is: calcium: 0.09%, stannum: 1.8%, aluminum: 0.05%, plumbous is surplus；
(2) lead button accounting for leady raw materials gross mass 80～84.5% is added in the graphite market pot of intermediate frequency furnace and heat to 670～680 DEG C, lead button is made fully to melt, calcium bits and the aluminium foil of mix homogeneously is wrapped up with sheet lead, and it is pressed in melted plumbous liquid together, then stir 2～3min and make calcium aluminium element mix homogeneously in plumbous liquid, in the process, keep the temperature of melt between 670～680 DEG C；
(3) stop stirring and heating, add the lead button of residue 15～20%, melt is stirred, add stannum when temperature is down to 520～540 DEG C to melt, continue stirring 2～3min and make stannum be completely melt and mix homogeneously；
(4) slag-cleaning agent is spread to bath surface, stir 1～2min, then scum silica frost is removed；
(5) cast when melt temperature is down to 480～500 DEG C.
Embodiment three
A kind of plumbous calcium stannum aluminum positive grid alloy preparation method, it is characterised in that comprise the following steps:
(1) raw material prepares: lead, calcium, stannum and aluminum, and each raw material accounts for the mass percent of total raw material and is: calcium: 0.09%, stannum: 2.0%, aluminum: 0.05%, plumbous is surplus；
(2) lead button accounting for leady raw materials gross mass 80～84.5% is added in the graphite market pot of intermediate frequency furnace and heat to 670～680 DEG C, lead button is made fully to melt, calcium bits and the aluminium foil of mix homogeneously is wrapped up with sheet lead, and it is pressed in melted plumbous liquid together, then stir 2～3min and make calcium aluminium element mix homogeneously in plumbous liquid, in the process, keep the temperature of melt between 670～680 DEG C；
(3) stop stirring and heating, add the lead button of residue 15～20%, melt is stirred, add stannum when temperature is down to 520～540 DEG C to melt, continue stirring 2～3min and make stannum be completely melt and mix homogeneously；
(4) slag-cleaning agent is spread to bath surface, stir 1～2min, then scum silica frost is removed；
(5) cast when melt temperature is down to 480～500 DEG C.
Examples detailed above alloy smear being assembled into experimental cell test, finds that example one alloy life terminated at 250 weeks through deeper cavity test, example two alloy life reaches 375 weeks, and example three alloy life reaches 345 weeks.Theil indices is excessively high can cause that rotproofness reduces on the contrary, so Theil indices should control less than 2%.
Claims (4)
1. a plumbous calcium stannum aluminum positive grid alloy preparation method, it is characterised in that: the mass percent that the described plumbous calcium stannum each raw material of aluminum positive grid alloy accounts for total raw material is:
Calcium 0.05～0.12%
Stannum 0.5～2.0%
Aluminum 0.01～0.1%
Surplus is plumbous；
Specifically include following steps:
(1) lead button accounting for leady raw materials gross mass 80～84% is added in the graphite market pot of intermediate frequency furnace and heat to 670～680 DEG C, lead button is made fully to melt, calcium bits and the aluminium foil of mix homogeneously is wrapped up with sheet lead, it is pressed in melted plumbous liquid, then stir 2～3min and make calcium aluminium element mix homogeneously in plumbous liquid, in the process, keep the temperature of melt between 670～680 DEG C；
(2) stop stirring and heating, add the lead button of residue 15～19%, melt is stirred, in melt, add stannum when temperature is down to 520～540 DEG C, continue stirring 2～3min and make stannum be completely melt and mix homogeneously；
(3) slag-cleaning agent is spread to bath surface, stir 1～2min, then scum silica frost is removed；
(4) cast when melt temperature is down to 480～500 DEG C.
2. plumbous calcium stannum aluminum positive grid alloy preparation method as claimed in claim 1, it is characterised in that: sheet lead quality is less than the 1% of leady raw materials gross mass.
3. plumbous calcium stannum aluminum positive grid alloy preparation method as claimed in claim 1, it is characterised in that: the bits of calcium described in step (1), aluminium foil are all diameters is the tablet of 3～4mm.
4. plumbous calcium stannum aluminum positive grid alloy preparation method as claimed in claim 1, it is characterised in that: described graphite market pot has long semielliptical shape inner chamber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410208225.6A CN103985879B (en) | 2014-05-16 | 2014-05-16 | A kind of plumbous calcium stannum aluminum positive grid alloy and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410208225.6A CN103985879B (en) | 2014-05-16 | 2014-05-16 | A kind of plumbous calcium stannum aluminum positive grid alloy and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103985879A CN103985879A (en) | 2014-08-13 |
| CN103985879B true CN103985879B (en) | 2016-06-29 |
Family
ID=51277771
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410208225.6A Active CN103985879B (en) | 2014-05-16 | 2014-05-16 | A kind of plumbous calcium stannum aluminum positive grid alloy and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103985879B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105098195A (en) * | 2014-06-27 | 2015-11-25 | 浙江天能电池(江苏)有限公司 | Lead-calcium-stannum-aluminum positive grid alloy and preparation method thereof |
| CN104993154B (en) * | 2015-05-23 | 2018-02-16 | 保定金阳光能源装备科技有限公司 | A kind of lead accumulator grid metal containing graphene and preparation method thereof |
| CN105206844B (en) * | 2015-08-28 | 2017-07-28 | 天能电池集团有限公司 | A kind of preparation method of the lead accumulator grid comprising lead graphene composite material |
| CN109004114B (en) * | 2018-08-04 | 2021-12-03 | 佛山赛能新能源有限公司 | Lead-acid storage battery for 4V navigation mark |
| CN109698353A (en) * | 2018-12-26 | 2019-04-30 | 天能电池(芜湖)有限公司 | A kind of accumulator positive alloy avoiding early stage capacitance loss |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050158629A1 (en) * | 2003-05-26 | 2005-07-21 | The Furukawa Battery Co., Ltd. | Lead-based alloy for lead-acid battery, grid for lead-acid battery and lead-acid battery |
| CN100497684C (en) * | 2006-06-30 | 2009-06-10 | 上海飞轮有色冶炼厂 | Production method of calcium lead alloy |
| CN101510609B (en) * | 2009-03-31 | 2011-02-16 | 赵恒祥 | Alloy material for accumulator positive slab lattice and preparation method thereof |
| CN101921927B (en) * | 2010-07-27 | 2012-02-22 | 韦学忠 | Preparation process of Pb-Ca-Sn-Al alloy |
| CN103762388B (en) * | 2014-01-17 | 2016-08-17 | 黄山振龙电源有限公司 | A kind of internal formation process of electric motor car valve-regulated lead-acid battery |
-
2014
- 2014-05-16 CN CN201410208225.6A patent/CN103985879B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103985879A (en) | 2014-08-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103199263B (en) | A kind of process for positive slab lattice of lead-acid accumulator Alloy And Preparation Method | |
| CN103985879B (en) | A kind of plumbous calcium stannum aluminum positive grid alloy and preparation method thereof | |
| CN104835965B (en) | A kind of motorcycle lead carbon battery and preparation method thereof | |
| CN101656312B (en) | Alloy material for high-energy accumulator grid and preparation method thereof | |
| CN106636737B (en) | A kind of power type positive electrode grid of lead storage battery alloy and preparation method | |
| CN102569757B (en) | Process for preparing materials of negative electrodes of copper-silicon-aluminum nano-porous lithium-ion batteries | |
| CN104900876A (en) | A novel graphene anode active compound used for lead-acid storage batteries and a preparing method thereof | |
| CN106099118B (en) | A kind of anode plate for lead acid accumulator grid alloy | |
| CN104073682B (en) | A kind of long lifetime deeper cavity positive grid alloy and preparation method thereof | |
| CN102660697B (en) | Lead-acid battery grid alloy for power | |
| CN103117394B (en) | Manufacturing method for flooded maintenance-free power-type lead-acid storage battery | |
| CN101685863A (en) | Rare-earth alloy lead plate grid material for accumulator | |
| CN102329982B (en) | Lead-antimony rare-earth positive grid alloy and preparation method thereof | |
| CN103280565A (en) | Aluminium alloy anode material and preparation method thereof | |
| CN111705337B (en) | Method for preparing lead-calcium master alloy by molten salt galvanic cell method | |
| CN103805809A (en) | Lead-acid accumulator grid alloy additive and preparation method thereof | |
| CN105024083A (en) | Manufacturing method of lead-carbon positive grid for lead-acid storage battery | |
| CN102427138A (en) | Preparation method for electric bicycle storage battery grid alloy | |
| CN104073683B (en) | A kind of low temperature deeper cavity positive grid alloy and preparation method thereof | |
| CN105098195A (en) | Lead-calcium-stannum-aluminum positive grid alloy and preparation method thereof | |
| CN102709528A (en) | Method for preparing positive plate of lead-acid storage battery | |
| CN107760922A (en) | A kind of high-energy power slab lattice alloy of lead-acid battery and preparation method thereof | |
| CN102403487A (en) | Preparation method of lead-acid storage battery anode for electric bike | |
| CN106025387A (en) | Flooded maintenance-free power-type lead-acid battery and manufacturing method thereof | |
| CN102509805B (en) | High-performance sealed lead-acid storage battery for electric vehicle |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180928 Address after: 223600 Shuyang Industrial Park, Suqian, Jiangsu Patentee after: Shuyang Xintian power supply material Co., Ltd. Address before: 223600 No. 1 Tianneng Road, Shuyang County Industrial Park, Suqian, Jiangsu Patentee before: Zhejiang Tianneng Battery (Jiangsu) Co., Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190918 Address after: 223600, Tian Neng Road 1, Shuyang Industrial Park, Suqian, Jiangsu Patentee after: Zhejiang Tianneng Battery (Jiangsu) Co., Ltd. Address before: 223600 Shuyang Industrial Park, Suqian, Jiangsu Patentee before: Shuyang Xintian power supply material Co., Ltd. |
|
| TR01 | Transfer of patent right |