CN105200294B - A kind of battery pole plates calcium Al-Pb alloy and preparation method thereof - Google Patents
A kind of battery pole plates calcium Al-Pb alloy and preparation method thereof Download PDFInfo
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- CN105200294B CN105200294B CN201510708206.4A CN201510708206A CN105200294B CN 105200294 B CN105200294 B CN 105200294B CN 201510708206 A CN201510708206 A CN 201510708206A CN 105200294 B CN105200294 B CN 105200294B
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- 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
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- Y02E60/10—Energy storage using batteries
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Abstract
The purpose of patent of the present invention is exactly to make up the deficiencies in the prior art to produce that calcium utilization is higher, calcium aluminium lead intermediate alloy of chemical composition stability substitutes calloy of the prior art there is provided the relatively casual labourer sequence of new making battery pole plates.The battery pole plates cleanliness factor that is made of the alloy is high, electric property is strong, long lifespan, intensity are higher, performance is more stablized.And smelting cost is greatly reduced.To reach the purpose, a kind of battery pole plates calcium Al-Pb alloy of the invention, as the intermediate alloy of manufacture battery pole plates, by calcium, aluminium, three kinds of Material synthesis of lead, wherein the mass percent of each raw material is：Calcium：60% 85%；Aluminium：10% 35%；Lead：3% 12%.Using technique of the present invention, it is final prepare battery lead plate when, add calcium aluminium lead intermediate alloy in configuration lead-calcium alloy process and accomplish once to add, be not required to it is secondary add, while the dissolving of calcium aluminium is abundant, be evenly distributed, the combination property of battery pole plates improved as far as possible.
Description
Technical field
Closed the present invention relates to a kind of intermetallic metal for making battery pole plates, more particularly to a kind of battery pole plates with calcium aluminium lead
Gold and preparation method thereof.
Background technology
Battery pole plates are as the important part of battery, and influence of its combination property to battery is very big.It is domestic at present electric
The production preparation of pond pole plate is most of to use lead-calcium multielement alloy, and lead-calcium alloy composition is similar, preparing process and formula
Also simply slightly has difference.But configuration lead-calcium alloy method of early stage when adding calcium and aluminium is that single addition calcium and aluminium carry out smelting
Refining, was added because the improvement of technique and the demand of yield are used as intermediate alloy using calloy in recent years, but in calcium aluminium
Between alloy preparing, storage, have the shortcomings that during transport and use it is many, such as：
(1) calloy extremely easily oxidation in preparation and storage and transportation process, causes occur lead skim mistake when in use
Many the problem of.Cause certain waste and influence the quality of lead-calcium alloy.
(2) easily there is the unstable situation of calcium Al yield in adition process in calloy, and current conventional method is
First require to add the technique for adding aluminum shot in progress after calloy according to calcium content.Aluminum shot fusion temperature is high, plus two are needed during aluminium
Secondary heating.Smelting cycle is caused to lengthen, while energy resource consumption is increased.And not fusible slag grain is easily caused after benefit aluminium, influence lead
, easily there is burr and disconnected muscle in quality after calcium alloy cast grid.
(3) fusing point of calloy is between 580-650 DEG C, current optimal use temperature is more than 610 DEG C.Lead pan heats up
The cost high consuming time of heating up simultaneously is longer.
In this regard, we reduce the heating-up time to reduce the warming temperature of lead pan, production cost is reduced, it would be desirable to find
A kind of more preferable intermediate alloy, just can produce reaction at a lower temperature.
《Gansu is metallurgical》- 2002 years 4 phases《The development and popularization and application of lead-calcium-aluminium alloy》One is disclosed herein a kind of Pb-
The development process of Ca-Al ternary alloy three-partalloys, and promote the use of in zinc electrolysis, saving with silver compared with traditional handicraft, improving electricity
There is obvious economic benefit in terms of flowing efficiency.But such ternary alloy three-partalloy is designed as final pole plate finished product, it is special
Point is that lead tolerance is very high, and generally more than 90%, and calcium content is less than 1%.With advances in technology, this alloy is made
Pole plate be also eliminated substantially.
The content of the invention：
The purpose of patent of the present invention be exactly make up the deficiencies in the prior art there is provided new making battery pole plates compared with
Casual labourer's sequence produces that calcium utilization is higher, calcium aluminium lead intermediate alloy of chemical composition stability substitutes calcium aluminium of the prior art and closed
Gold.The battery pole plates cleanliness factor that is made of the alloy is high, electric property is strong, long lifespan, intensity are higher, performance is more stablized.
And smelting cost is greatly reduced.
To reach the purpose, a kind of battery pole plates calcium Al-Pb alloy of the invention is used as the centre of manufacture battery pole plates
Alloy, by calcium, aluminium, three kinds of Material synthesis of lead, wherein the mass percent of each raw material is：
Calcium：60%-85%；
Aluminium：10%-35%；
Lead：3%-12%.
It is preferred that, three kinds of raw materials are solid, and the purity of raw material is above 97%.
It is preferred that, the calcium is using being electrolysed calcium, high-purity calcium, going back protocalcium, and its form is calcium block, calcium bits, calcium powder or calcium grain.Gu
The source of body calcium is widely.Generally select and added in the form of calcium block, using in the case of calcium block, it adds temperature can be with
It is somewhat higher.Compared to calcium bits, calcium grain, had the advantage that using calcium block：Bell jar is not needed, can be directly added into, it is easy to operate
Simply, calcium utilization is stable.
Further, present invention additionally comprises a kind of preparation method of battery pole plates with calcium Al-Pb alloy, comprise the following steps：
Step 1：Sorting, selection meets the raw material of purity requirement；
Step 2：Dispensing：Raw material is matched in proportion；
Step 3：Charging：The raw material prepared is loaded into reaction vessels；
Step 4：Fusing：Under the protection of lasting inert gas atmosphere, fine aluminium ingot, pure calcium block are put into induction furnace and mix molten
Change and stir, smelting temperature is controlled at 900 DEG C -1000 DEG C, all after fusing, then by mixed melting in lead pig addition induction furnace simultaneously
Stirring, smelting temperature is controlled at 950 DEG C -1050 DEG C, and stirring 5min-10min is until alloy all melts.Temperature during this
It is too high, alloying element loss increase can be caused；Temperature is too low, then element can not effective alloying in alloy.In addition, mixing time
Also suitable control is wanted, the time of stirring can not be long, is advisable with the complete alloying of the metal added.If overlong time, it can make
Aluminium therein, calcium excessive loss.Mixing time is too short, and alloy easily produces segregation, alloying component heterogeneity.
Step 5：Casting：Finished product after fusing is cast into calcium aluminium lead intermediate alloy；
Step 6：Examine measurement：Whether detection final product quality meets the requirements；
Step 7：Satisfactory product warehousing is preserved.
It is preferred that, inverse whipping step is also included between the step 4 and step 5：Material add after by with stirring side before
Continue to stir 3-5 minutes in the opposite direction.Calcium aluminium lead intermediate alloy composition needed for so obtaining is more stable.
It is preferred that, inert gas uses argon gas in the step 4.
It is preferred that, detection requires that other impurities element total amount is less than 3% in the step 6.Even if three main components
Ratio meets the requirements, if impurity element is excessive, the product still belongs to substandard product.
The of the invention alloy is mainly characterized in that：
(1) aluminium is added in alloy and can reduce oxygen content, makes inclusion conditioning and removal efficiency high, using rare earth, aluminium, calcium
Multielement complex deoxidization removal of impurities, finally can more significantly improve the electric property of battery pole plates；
(2) technological process of the invention is short, can obtain the calcium aluminium utilization rate of stabilization and the chemical composition of stabilization and preferable
The calcium aluminium lead intermediate alloy of presentation quality；
(3) present invention takes directly fusion calcium, aluminium, the technique of metal, can improve the stability of alloy, can improve battery
The combination property of pole plate；
(4) in the present invention, the addition of metallic aluminium is also that, as protective agent, it can be used for protecting added calcium not simultaneously
The quality of final products is influenceed as largely being aoxidized in fusion process；
(5) Adding Way is simple, conveniently during alloy melting, and final calcium aluminium lead intermediate alloy is not pulverized easily, and is preserved
Time is long.
The present invention replaces calcium aluminium intermediate alloy to produce battery pole plates with calcium aluminium lead intermediate alloy, with following advantage：
(1) aluminium and lead protection calcium in calcium Al-Pb alloy, so as to reduce the loss of calcium, the scaling loss of calcium can be reduced to 5%
Below；Oxidation is not likely to produce in storage, transportation simultaneously, while more stablizing compared with calloy, collision is difficult and catches fire, increase
The security for depositing fortune is added.
(2) element of calcium aluminium lead three is uniformly merged in alloy, uniformly can rapidly be melted after the addition and be made lead-calcium alloy
Calcium aluminium content is uniform, the not meltable particle of lead skim and aluminium seldom occurs, can significantly improve the impact flexibility of lead-calcium alloy, intensity, quench
Permeability, while can also improve the liberation of hydrogen overpotential for oxygen evolution of lead-calcium alloy；
(3) higher calcium content and the aluminium and lead mixing intermediate alloy of certain content enhance inclusion modification and removed and imitates
Really；
(4) calcium aluminium lead intermediate alloy is used, without temperature-fall period, while temperature in use reduces 30-60 DEG C, faster can more be filled
The dissolving divided, so as to shorten the production time, reduces heating cost, improves efficiency.One ton of lead liquid heating cost exists
10 yuan every 10 degree.
(5) the beneficial effects of the invention are as follows using gas is protected, because having completely cut off oxygen, so significantly reduce calcium oxide
With the formation of aluminum oxide, slag rate is low in whipping process, can accomplish substantially without slag, so in the industrial production just need not be again
Go to fish for scum silica frost, while improving the utilization rate of calcium；
(6) the calcium Al-Pb alloy of different ratio can be synthesized according to customer requirement, so wide application, can meet difference
Client need, create more preferable economic benefit；
(7) intermediate alloy stable components made from, Tissue distribution is uniform, and alloy flowability is good.
Using technique of the present invention, when finally preparing battery lead plate, calcium aluminium lead is added in configuration lead-calcium alloy process
Intermediate alloy is accomplished once to add, be not required to it is secondary add, while the dissolving of calcium aluminium is abundant, is evenly distributed, battery pole plates improved as far as possible
Combination property.
Embodiment:
The present invention is in preparation process, and the ratio of raw material will not change substantially, therefore the percentage by weight base of raw material
This is identical with the mass percent of each composition in finished product.
Example 1：
Under the protection of lasting argon gas atmosphere, fine aluminium ingot 2.2kg is taken, 900 DEG C are warming up in induction furnace and is melted, then
Add the pure calcium blocks of 6.8kg thereto under stirring, the temperature control of mixed smelting treats that it all melts follow-up at 930 DEG C
Continuous to stir and add 1.0kg leads, the temperature control of mixed smelting is at 950 DEG C, and stirring 8min is until alloy all melts, then
Intermediate alloy is cast into through pouring device, natural cooling and intermediate alloy finished product is made in atmosphere, detection is put in storage after weighing.Its
Composition is with content：Ca:68wt%, Al:22wt%, Pb10wt%.
Example 2：
Under the protection of lasting argon gas atmosphere, fine aluminium ingot 2.5kg is taken, 900 DEG C are warming up in induction furnace and is melted, then
Add the pure calcium blocks of 7.0kg thereto under stirring, the temperature control of mixed smelting treats that it all melts follow-up at 950 DEG C
Continuous to stir and add 0.5kg leads, the temperature control of mixed smelting is at 980 DEG C, and stirring 10min is until alloy all melts, so
Intermediate alloy is cast into by pouring device, natural cooling and intermediate alloy finished product is made in atmosphere, detection is put in storage after weighing.
Its composition is with content：Ca:70wt%, Al:25wt%, Pb:5wt%.
Example 3：
Under the protection of lasting argon gas atmosphere, fine aluminium ingot 1.0kg is taken, 900 DEG C are warming up in induction furnace and is melted, then
Add the pure calcium blocks of 8.2kg thereto under stirring, the temperature control of mixed smelting treats that it all melts follow-up at 980 DEG C
Continuous to stir and add 0.8kg leads, the temperature control of mixed smelting is at 1000 DEG C, and stirring 8min all melts up to alloy, this
The inverse stirrings of Shi Jinhang 3 minutes.Then intermediate alloy is cast into through pouring device, natural cooling and intermediate alloy is made in atmosphere
Finished product, detection is put in storage after weighing.Its composition is with content：Ca:82wt%, Al:13wt%, Pb:5wt%.
Although three kinds of embodiments are from argon gas as protection gas, that is due to the cost performance height in view of argon gas.Right
In the case that Product Precision there are requirements at the higher level, others inert gas may be selected.In order to coordinate inert gas, reacting furnace is typically adopted
Use vacuum reaction stove.
, just can be by former original warm temperature after the calcium Al-Pb alloy of the calloy alternative costs invention in the invention
Less than 600 degree centigrade are reduced to from 670-700.Because being compared with the kalzium metal of prior art, aluminium calcium lead of the present invention
Alloy declines due to adding lead, overall fusing point.And the content of this lead is also what is be worthy of careful study.The too small ratio of lead is nothing
Method realizes the effect of cooling, and ratio is too high can cause temperature and the proportioning of raw material imbalance in preparation process.Pass through the present invention's
Match the intermetallic metal cost performance highest being made.The battery pole plates cleanliness factor that is made of alloy of the present invention is high, electric property is strong,
Long lifespan, intensity are higher, performance is more stablized.And smelting cost is greatly reduced.It is warm in stove during due to pole plate can will be prepared
30-60 degrees Celsius of degree reduction.Often cool 10 degree according to product per ton and save 20 yuan of calculating, often prepare 1 ton of finished product, economically just save
60-120 members are saved, and the actual effect of final finished will also be far above product of the prior art.
Claims (5)
1. a kind of battery pole plates preparation method of calcium Al-Pb alloy, it is characterised in that：Comprise the following steps：
Step 1：Sorting, selection meets the raw material of purity requirement；The mass percent of each raw material is：
Calcium：60%-85%；
Aluminium：10%-35%；
Lead：3%-12%；Three kinds of raw materials are solid, and the purity of raw material is above 97%；
Step 2：Dispensing：Raw material is matched in proportion；
Step 3：Charging：The raw material prepared is loaded into reaction vessels；
Step 4：Fusing：Under the protection of lasting inert gas atmosphere, fine aluminium ingot, pure calcium block are put into induction furnace mixed melting simultaneously
Stirring, smelting temperature is controlled at 900 DEG C -1000 DEG C, all after fusing, then by mixed melting in lead pig addition induction furnace and is stirred
Mix, smelting temperature is controlled at 950 DEG C -1050 DEG C, stirring 5min-10min is until alloy all melts；
Step 5：Casting：Finished product after fusing is cast into calcium aluminium lead intermediate alloy；
Step 6：Examine measurement：Whether detection final product quality meets the requirements；
Step 7：Satisfactory product warehousing is preserved.
2. a kind of preparation method of battery pole plates calcium Al-Pb alloy as claimed in claim 1, it is characterised in that：The step
Also include inverse whipping step between 4 and step 5：Material is continued to stir 3-5 after adding by the direction opposite with mixing direction before
Minute.
3. a kind of preparation method of battery pole plates calcium Al-Pb alloy as claimed in claim 1, it is characterised in that：The step
Inert gas uses argon gas in 4.
4. a kind of preparation method of battery pole plates calcium Al-Pb alloy as claimed in claim 1, it is characterised in that：The step
Detection requires that other impurities element total amount is less than 3% in 6.
5. a kind of preparation method of battery pole plates calcium Al-Pb alloy as claimed in claim 1, it is characterised in that：The calcium makes
With electrolysis calcium, high-purity calcium, protocalcium is gone back, its form is calcium block, calcium bits, calcium powder or calcium grain.
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| CN105200294B true CN105200294B (en) | 2017-08-29 |
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Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4439398A (en) * | 1981-11-13 | 1984-03-27 | Rsr Corporation | Method of alloying calcium and aluminum into lead |
| CN1042190A (en) * | 1989-09-30 | 1990-05-16 | 李庆 | The manufacture method of anti-oxidant high alumina lead base master alloy |
| CN2076712U (en) * | 1990-12-08 | 1991-05-08 | 王关根 | Storage battery having pb-ca-al alloy electrode |
| CN1060532C (en) * | 1996-08-03 | 2001-01-10 | 国营建中化工总公司 | calcium-based ternary alloy |
| CN100497684C (en) * | 2006-06-30 | 2009-06-10 | 上海飞轮有色冶炼厂 | Production method of calcium lead alloy |
| CN101693961A (en) * | 2009-11-03 | 2010-04-14 | 株洲冶炼集团股份有限公司 | Melting method for lead-calcium alloys |
| CN101921927B (en) * | 2010-07-27 | 2012-02-22 | 韦学忠 | Preparation process of Pb-Ca-Sn-Al alloy |
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