CN104073683B - A kind of low temperature deeper cavity positive grid alloy and preparation method thereof - Google Patents

A kind of low temperature deeper cavity positive grid alloy and preparation method thereof Download PDF

Info

Publication number
CN104073683B
CN104073683B CN201410298050.2A CN201410298050A CN104073683B CN 104073683 B CN104073683 B CN 104073683B CN 201410298050 A CN201410298050 A CN 201410298050A CN 104073683 B CN104073683 B CN 104073683B
Authority
CN
China
Prior art keywords
calcium
low temperature
melt
zinc
tin
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
Application number
CN201410298050.2A
Other languages
Chinese (zh)
Other versions
CN104073683A (en
Inventor
王晶
陈飞
马换玉
周燕
方明学
杨惠强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianneng Group Jiangsu Technology Co Ltd
Original Assignee
Tianneng Group Jiangsu Technology Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tianneng Group Jiangsu Technology Co Ltd filed Critical Tianneng Group Jiangsu Technology Co Ltd
Priority to CN201410298050.2A priority Critical patent/CN104073683B/en
Publication of CN104073683A publication Critical patent/CN104073683A/en
Priority to PCT/CN2014/088342 priority patent/WO2015196624A1/en
Application granted granted Critical
Publication of CN104073683B publication Critical patent/CN104073683B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C11/00Alloys based on lead
    • C22C11/06Alloys based on lead with tin as the next major constituent

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Coating With Molten Metal (AREA)

Abstract

The invention discloses a kind of low temperature deeper cavity positive grid alloy, be made up of: calcium 0.05 ~ 0.12%, tin 0.2 ~ 2.0%, aluminium 0.01 ~ 0.1%, zinc 0.01 ~ 0.2% raw material of following mass percent, surplus is plumbous.The low-temperature performance that the alloy that the present invention provides has had, forms the impedance of anodic corrosion film under reducing low temperature.Zinc element clearly can improve the deep-circulating performance of battery, even under cryogenic, because the good conductivity of PbZnO type oxide.

Description

A kind of low temperature deeper cavity positive grid alloy and preparation method thereof
Technical field
The invention belongs to lead acid cell field, relate to a kind of low temperature deeper cavity process for positive slab lattice of lead-acid accumulator Alloy And Preparation Method.
Background technology
In lead-acid cell field, the low-temperature performance of battery is always unsatisfactory.It has been generally acknowledged that what the mainly negative plate affecting low-temperature performance determined, but find that positive plate also limits the low-temperature performance of battery in reality test, find further simultaneously, the resistance of the anodic corrosion film that conventional cathode grid Pb-Ca-Sn-Al alloy is formed at low temperatures is relatively large, thus limit battery deep-circulating performance at low temperatures.
Summary of the invention
The object of the invention is to, the alloy low-temperature performance for existing routine plumbous calcium tin aluminium is not enough, provides a kind low temperature deeper cavity positive grid alloy, can close to performance under normal temperature to battery performance under low temperature.The technical problem that simultaneously will solve is, provides the index method of this positive grid alloy.
For reaching above-mentioned technical purpose, technical scheme of the present invention is as follows:
A kind of low temperature deeper cavity positive grid alloy, is made up of the raw material of following mass percent:
Calcium 0.05 ~ 0.12%
Tin 0.2 ~ 2.0%
Aluminium 0.01 ~ 0.1%
Zinc 0.01 ~ 0.2%
Surplus is plumbous.
As the preferred alloying element mass percent of one be: calcium: 0.09%, tin: 1.8%, aluminium: 0.05%, zinc: 0.08%, plumbous is surplus.
A preparation method for low temperature deeper cavity positive grid alloy, comprises the following steps: by the mass percent of above-mentioned raw materials,
(1) lead button accounting for leady raw materials total mass 80 ~ 85% is added in the graphite market pot of intermediate frequency furnace intermediate frequency furnace and be heated to 670 ~ 680 DEG C, lead button is fully melted, with the sheet lead accounting for leady raw materials total mass 0.5 ~ 1%, wrap up the calcium bits and aluminium foil that mix, and be pressed in the plumbous liquid of melting together, then stirring 2 ~ 3min makes calcium aluminium element mix in plumbous liquid, in the process, keeps the temperature of melt between 670 ~ 680 DEG C;
(3) stop stirring and heating, add remaining lead button, melt is stirred, add tin and zinc when temperature is down to 520 ~ 540 DEG C to melt, then stir 2 ~ 3min and make tin and zinc melt completely and mix;
(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.
The flap of the bits of calcium described in step (1), aluminium foil to be all diameters be 3 ~ 4mm.
It is convenient reinforced for wrapping up an aspect with sheet lead, prevents calcium from considering to be worth doing in addition and contacts with oxygen, reduces calcium bits and is oxidized in atmosphere.
Described graphite market pot has vertical long semielliptical shape inner chamber.Usual market pot is square, and calrod heats; Square lead pan has stirring dead angle, and simultaneously intermediate frequency heating speed is fast, efficiency is high, and heating has from agitating function simultaneously, the alloying constituent allotted can be made like this evenly.
After have employed technique scheme, the invention has the beneficial effects as follows:
1, the low-temperature performance that the alloy that the present invention provides has had, forms the impedance of anodic corrosion film under reducing low temperature.Zinc element clearly can improve the deep-circulating performance of battery, even under cryogenic, because the good conductivity of PbZnO type oxide.
2, the present invention is in process for preparation, and the calcium bits mixed are joined in plumbous liquid with aluminium foil simultaneously, eliminates the process of tradition preparation calcium aluminium mother alloy, so not only avoids a large amount of scaling loss of calcium, and enhance productivity, saved production cost.
3, the long semielliptical shape inner chamber that the present invention is used graphite market pot with there is the intermediate frequency furnace of automatic stirring function, these can make to allot the alloying constituent uniformity come, and improve production efficiency.
Accompanying drawing explanation
Fig. 1 is example one and the impedance spectrum schematic diagram of example two alloy under 0.8V.Found by impedance spectrum contrast, the anonite membrane impedance that example two is formed is much smaller than example one.
Embodiment
The applicant have submitted plumbous calcium tin aluminium positive grid alloy and preparation method thereof patent application on the same day, and this part of patent application provides, and alloy corrosion resisting alloy element preferred mass is than being calcium: 0.09%, tin: 1.8%, aluminium: 0.05%.In the application, conveniently compare the impact of zinc alloy low-temperature performance, therefore, the alloying element proportioning outside the embodiment of the present application 1-3 zinc remains unchanged.
Embodiment one
A kind of low temperature deeper cavity positive grid alloy preparation method, is characterized in that comprising the following steps:
(1) raw material prepares: lead, calcium, tin and aluminium, and the mass percent that each raw material accounts for total raw material is: calcium: 0.09%, tin: 1.8%, aluminium: 0.05%, zinc: 0.01%, plumbous is surplus;
(2) lead button accounting for leady raw materials total mass 85% is added in the graphite market pot of intermediate frequency furnace and be heated to 670 ~ 680 DEG C, lead button is fully melted, with the sheet lead accounting for leady raw materials total mass 0.5%, wrap up the calcium bits and aluminium foil that mix, and be pressed in the plumbous liquid of melting together, then stirring 2 ~ 3min makes calcium aluminium element mix in plumbous liquid, in the process, keeps the temperature of melt between 670 ~ 680 DEG C;
(3) stop stirring and heating, add remaining lead button, melt is stirred, add tin and zinc when temperature is down to 520 ~ 540 DEG C to melt, then stir 2 ~ 3min and make tin and zinc melt completely and mix;
(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 two
A kind of low temperature deeper cavity positive grid alloy preparation method, is characterized in that comprising the following steps:
(1) raw material prepares: lead, calcium, tin and aluminium, and the mass percent that each raw material accounts for total raw material is: calcium: 0.09%, tin: 1.8%, aluminium: 0.05%, zinc: 0.08%, plumbous is surplus;
(2) lead button accounting for leady raw materials total mass 85% is added in the graphite market pot of intermediate frequency furnace and be heated to 670 ~ 680 DEG C, lead button is fully melted, with the sheet lead accounting for leady raw materials total mass 0.5%, wrap up the calcium bits and aluminium foil that mix, and be pressed in the plumbous liquid of melting together, then stirring 2 ~ 3min makes calcium aluminium element mix in plumbous liquid, in the process, keeps the temperature of melt between 670 ~ 680 DEG C;
(3) stop stirring and heating, add remaining lead button, melt is stirred, add tin and zinc when temperature is down to 520 ~ 540 DEG C to melt, then stir 2 ~ 3min and make tin and zinc melt completely and mix;
(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 low temperature deeper cavity positive grid alloy preparation method, is characterized in that comprising the following steps:
(1) raw material prepares: lead, calcium, tin and aluminium, and the mass percent that each raw material accounts for total raw material is: calcium: 0.09%, tin: 0.5%, aluminium: 0.05%, zinc: 0.2%, plumbous is surplus;
(2) lead button accounting for leady raw materials total mass 85% is added in the graphite market pot of intermediate frequency furnace and be heated to 670 ~ 680 DEG C, lead button is fully melted, with the sheet lead accounting for leady raw materials total mass 0.5%, wrap up the calcium bits and aluminium foil that mix, and be pressed in the plumbous liquid of melting together, then stirring 2 ~ 3min makes calcium aluminium element mix in plumbous liquid, in the process, keeps the temperature of melt between 670 ~ 680 DEG C;
(3) stop stirring and heating, add remaining lead button, melt is stirred, add tin and zinc when temperature is down to 520 ~ 540 DEG C to melt, then stir 2 ~ 3min and make tin and zinc melt completely and mix;
(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.
Above-mentioned example one, example two alloy smear are assembled into the test of 12V12Ah experimental cell, low temperature deeper cavity work system is: the charging stage, store battery is in the environment of-15 DEG C ± 1 DEG C in temperature, with single store battery average voltage for 15V(current limliting 3A) constant voltage trickle charge 8h maybe when charging latter stage current stabilization 3h constant, be now and be full of electricity; Discharge regime, after store battery is full of electricity, in the environment of-15 DEG C ± 1 DEG C, discharges into when accumulator voltage reaches 10.50V with 6A and stops.Through deeper cavity test find example one alloy cell at low temperatures deeper cavity capacity at about 6Ah, example two alloy cell at low temperatures deeper cavity capacity at about 10Ah,
The interpolation of zinc improves the low temperature deep-circulating performance of battery well.

Claims (4)

1. a low temperature preparation method for deeper cavity positive grid alloy, is characterized in that being made up of the raw material of following mass percent:
Calcium 0.05 ~ 0.12%
Tin 0.2 ~ 2.0%
Aluminium 0.01 ~ 0.1%
Zinc 0.01 ~ 0.2%
Surplus is plumbous;
Comprise the following steps: by the mass percent of above-mentioned raw materials,
(1) lead button accounting for leady raw materials total mass 80 ~ 85% is added in the graphite market pot of intermediate frequency furnace and be heated to 670 ~ 680 DEG C, lead button is fully melted, with the sheet lead accounting for leady raw materials total mass 0.5 ~ 1%, wrap up the calcium bits and aluminium foil that mix, and be pressed in the plumbous liquid of melting together, then stirring 2 ~ 3min makes calcium aluminium element mix in plumbous liquid, in the process, keeps the temperature of melt between 670 ~ 680 DEG C;
(3) stop stirring and heating, add remaining lead button, melt is stirred, add tin and zinc when temperature is down to 520 ~ 540 DEG C to melt, then stir 2 ~ 3min and make tin and zinc melt completely and mix;
(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.
2. the preparation method of a kind of low temperature deeper cavity positive grid alloy as claimed in claim 1, is characterized in that: calcium: 0.09%, tin: 1.8%, aluminium: 0.05%, zinc: 0.08%, plumbous is surplus.
3. the preparation method of a kind of low temperature deeper cavity positive grid alloy as claimed in claim 1, is characterized in that: the flap of the bits of calcium described in step (1), aluminium foil to be all diameters be 3 ~ 4mm.
4. the preparation method of a kind of low temperature deeper cavity positive grid alloy as claimed in claim 1, is characterized in that: described graphite market pot has vertical long semielliptical shape inner chamber.
CN201410298050.2A 2014-06-27 2014-06-27 A kind of low temperature deeper cavity positive grid alloy and preparation method thereof Active CN104073683B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201410298050.2A CN104073683B (en) 2014-06-27 2014-06-27 A kind of low temperature deeper cavity positive grid alloy and preparation method thereof
PCT/CN2014/088342 WO2015196624A1 (en) 2014-06-27 2014-10-11 Gate alloy for low-temperature deep-cycle positive electrode plate, and preparation method therefor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410298050.2A CN104073683B (en) 2014-06-27 2014-06-27 A kind of low temperature deeper cavity positive grid alloy and preparation method thereof

Publications (2)

Publication Number Publication Date
CN104073683A CN104073683A (en) 2014-10-01
CN104073683B true CN104073683B (en) 2016-02-10

Family

ID=51595281

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410298050.2A Active CN104073683B (en) 2014-06-27 2014-06-27 A kind of low temperature deeper cavity positive grid alloy and preparation method thereof

Country Status (2)

Country Link
CN (1) CN104073683B (en)
WO (1) WO2015196624A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104073683B (en) * 2014-06-27 2016-02-10 天能集团江苏科技有限公司 A kind of low temperature deeper cavity positive grid alloy and preparation method thereof
CN107287470B (en) * 2017-05-25 2019-02-15 天能电池集团有限公司 A kind of lead storage battery grid alloy and preparation method comprising nanometer tungsten carbide material

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995015587A1 (en) * 1993-11-30 1995-06-08 Shi Xue Dou Improved grid alloy for lead-acid battery
BR9505372A (en) * 1995-12-07 1997-10-28 Microlite S A Lead alloy - calcium - tin - aluminum - silver for the manufacture of electric battery grids
US20040112486A1 (en) * 1996-03-01 2004-06-17 Aust Karl T. Thermo-mechanical treated lead and lead alloys especially for current collectors and connectors in lead-acid batteries
CN1198599A (en) * 1997-05-05 1998-11-11 陈有孝 High specific energy fully closed maintenanceless lead acid accumulator
DE19823147A1 (en) * 1998-05-23 1999-11-25 Vb Autobatterie Gmbh Electrode grid for lead accumulators
CN101656312B (en) * 2009-07-08 2011-09-21 张天任 Alloy material for high-energy accumulator grid and preparation method thereof
CN102517471A (en) * 2011-12-19 2012-06-27 河南豫光金铅股份有限公司 Production method of adding calcium in lead
CN102703755B (en) * 2012-06-21 2016-08-31 上海锦众信息科技有限公司 The preparation method of lead-acid accumulator grid alloy material
CN102709528A (en) * 2012-06-21 2012-10-03 上海锦众信息科技有限公司 Method for preparing positive plate of lead-acid storage battery
CN102938465B (en) * 2012-11-11 2015-08-19 骆驼集团华南蓄电池有限公司 Lead-acid storage battery grid lead alloy
CN103107310B (en) * 2012-11-11 2015-07-22 广西天鹅蓄电池有限责任公司 Manufacturing method of storage battery green plate
CN104073683B (en) * 2014-06-27 2016-02-10 天能集团江苏科技有限公司 A kind of low temperature deeper cavity positive grid alloy and preparation method thereof

Also Published As

Publication number Publication date
CN104073683A (en) 2014-10-01
WO2015196624A1 (en) 2015-12-30

Similar Documents

Publication Publication Date Title
CN101656312B (en) Alloy material for high-energy accumulator grid and preparation method thereof
CN104073682B (en) A kind of long lifetime deeper cavity positive grid alloy and preparation method thereof
CN105177354B (en) A kind of maintenance-free lead accumulator positive grid alloy
CN106099118B (en) A kind of anode plate for lead acid accumulator grid alloy
CN103985879B (en) A kind of plumbous calcium stannum aluminum 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
CN104073683B (en) A kind of low temperature deeper cavity positive grid alloy and preparation method thereof
CN105024083B (en) A kind of preparation method of Lead-acid Storage Battery carbon anode plate grid
CN102329982A (en) Lead-antimony rare-earth positive grid alloy and preparation method thereof
CN101510610A (en) Positive slab lattice alloy for power lead acid battery and preparation method thereof
CN103805809A (en) Lead-acid accumulator grid alloy additive and preparation method thereof
CN103762388B (en) A kind of internal formation process of electric motor car valve-regulated lead-acid battery
CN110993897B (en) Positive electrode additive for prolonging service life of valve-controlled sealed lead-acid battery and application thereof
CN105098164A (en) Silicon-lithium anode material and preparation method thereof
CN102427138A (en) Preparation method of storage battery grid alloy of electric bicycle
CN112281024A (en) Lead-calcium-tin-copper rare earth grid alloy, positive grid and lead-acid storage battery
CN105098195A (en) Lead-calcium-stannum-aluminum positive grid alloy and preparation method thereof
CN105671362A (en) Lanthanum mother alloy for positive electrode grid of lead-acid storage battery and preparation process
CN106784858A (en) Lead accumulator grid additive, preparation method, grid and high connductivity lead accumulator
CN101994027A (en) Direct production method for lead calcium rare earth alloy
CN108808010A (en) A kind of Moped Scooter positive electrode grid of lead storage battery alloy and preparation method thereof
CN100386457C (en) Process for preparing Pb-base mixed rare earth slab lattice alloy
CN102403487A (en) Preparation method of lead-acid storage battery anode for electric bicycle
CN103627926A (en) Tubular traction storage battery positive grid alloy formula and tubular traction storage battery positive grid alloy preparation method
CN115132960A (en) Aluminum-air battery cathode and preparation method thereof

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