CN104377363A - Lead acid battery positive grid alloy and preparation method thereof - Google Patents
Lead acid battery positive grid alloy and preparation method thereof Download PDFInfo
- Publication number
- CN104377363A CN104377363A CN201410527628.7A CN201410527628A CN104377363A CN 104377363 A CN104377363 A CN 104377363A CN 201410527628 A CN201410527628 A CN 201410527628A CN 104377363 A CN104377363 A CN 104377363A
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- alloy
- graphite
- lead
- grid
- acid battery
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Classifications
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- 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
- C22C11/06—Alloys based on lead with tin 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
Abstract
The invention relates to a grid alloy and especially relates to a lead acid battery positive grid alloy and a preparation method thereof. The lead acid battery positive grid alloy contains lead as a main component and comprises, by mass, 0.2-0.8% of tin, 0.02-0.04% of aluminum, 0.2-0.4% of graphite, 0.04-0.1% of copper and the balance lead. The lead acid battery positive grid alloy is a lead-tin-aluminum-copper-graphite alloy and is used for a lead acid battery positive grid. The lead acid battery positive grid prepared from the lead acid battery positive grid alloy has short time efficiency within 2 days. The lead acid battery with the lead acid battery positive grid does not produce PCL-1 effects in use.
Description
Technical field
The present invention relates to a kind of grid alloy, particularly a kind of positive plate grid alloy and preparation method thereof.
Background technology
At present because national policy forbids the production of Qian Ti Cadmium battery, present battery production main flow transfers plumbous calcium series grid to, plumbous calcium series grid alloy, alloy lattice structural instability after casting, grid is softer, can be out of shape in smear process, causes smear scrappage higher, after hardening during point brushing piece because grid is out of shape, frame of pole plate is easily cut partially to cause and is scrapped.So grid will have longer timeliness phase, be generally 4 ~ 7 days, the production cycle is long, so the timeliness phase longly just means that fund overstocks, production cost is higher.Also to take into account the stability of alloy lattice to solve the long problem of grid timeliness in industry, a lot of technical staff has carried out a large amount of exploratory development, mainly contain and change alloying component and high-temperature aging two aspects, but effect is also not obvious, wherein to harden some achievement with high-temperature aging again, but normally high-temperature aging 8 ~ 24h, and then carry out nature and shelve timeliness 3 days, the timeliness phase is still partially long.Plumbous calcium grid alloy battery pole plates interface easily produces barrier layer and causes early stage capacitance loss, be i.e. PCL-1 problem.
Summary of the invention
The invention provides a kind of positive plate grid alloy, the positive grid mechanical strength adopting this alloy to make strengthens, and the timeliness phase is short, and the intensity of grid is suitable for coated plate.
The present invention also provides a kind of preparation method of positive plate grid alloy.
The technical solution adopted for the present invention to solve the technical problems is: a kind of positive plate grid alloy, the main component of grid alloy is plumbous, this alloy comprises following in the component of mass fraction: tin 0.2% ~ 0.8%, aluminium 0.02% ~ 0.04%, graphite 0.2% ~ 0.4%, copper 0.04% ~ 0.1%, surplus is plumbous.What the present invention adopted is slicker solder aluminum bronze graphite alloy, and for positive grid of lead-acid accumulator, graphite alloy does positive grid of lead-acid accumulator, and aging time can foreshorten in 2 days, and battery does not in use produce PCL-1 effect.
This alloy comprises following in the component of mass fraction: tin 0.2%, aluminium 0.028%, graphite 0.4%, copper 0.06%, and surplus is plumbous.
This alloy comprises following in the component of mass fraction: tin 0.79%, aluminium 0.04%, graphite 0.2%, copper 0.04%, and surplus is plumbous.
This alloy comprises following in the component of mass fraction: tin 0.45%, aluminium 0.02%, graphite 0.32%, copper 0.1%, and surplus is plumbous.
A preparation method for described positive plate grid alloy, the method is specially: a, prepare graphite lead alloy, makes the mass fraction of graphite in graphite lead alloy be 2% ~ 3%; B, according to positive slab lattice alloy composition proportion, the lead of remainder is joined in lead melting furnace, be heated to 550 ~ 600 DEG C, then a is walked the graphite lead alloy obtained to join in lead melting furnace and stir, again mock silver and signal bronze are joined in lead melting furnace, abundant fusing also stirs, and obtains positive slab lattice alloy.
Increase graphite in positive slab lattice alloy, change the mechanical strength of grid.The grid that Pb-Ca-Sn-Al alloy makes can As time goes within the timeliness phase, and lattice increases gradually, and the timeliness phase is generally 4 ~ 7 days, and the timeliness phase is long, and this just means that the production cycle is long, and fund pressurization is serious.Graphite is added in grid, the mechanical strength of grid strengthens, and the timeliness phase can shorten in 2 days, and the intensity of grid is suitable for coated plate, and (experienced coated plate employee picks up one end of monolithic grid, the other end can not bend sagging under gravity, can judge to be suitable for coated plate.Note: the hardness number in normal productive process being accident grid).And due to the resistivity of graphite extremely low, add graphite in positive slab lattice alloy, grid resistance is declined, and what is more important grid and active material junction are owing to there being the existence of graphite, avoid the generation of high barrier, avoid early stage capacity early ageing.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail.Should be appreciated that enforcement of the present invention is not limited to the following examples, any pro forma accommodation make the present invention and/or change all will fall into scope.
In the present invention, if not refer in particular to, all parts, percentage are unit of weight, and the equipment adopted and raw material etc. all can be buied from market or this area is conventional.Method in following embodiment, if no special instructions, is the conventional method of this area.The lead adopted in the present invention is 1# electrolytic lead, containing inevitable impurity in alloy.
Brinell hardness test, with reference to national standard (GB231-84), applies test force pressing in sample surface to the sintered carbide ball of certain diameter, and after the regulation retention time, removal test force, measures the impression diameter of specimen surface.Digital display Michael Burawoy hardometer HBRVS-187.5, Selection experiment power F:62.5kg, bulb diameter D:5mm, F/D
2: 2.5.
Tensile strength is tested: the method sample adopting casting, according to the tensile strength of GB 228-87 " metal tensile test method " test sample, and electronic universal tester CMT6503.
Embodiment 1-5:
A kind of preparation method of positive plate grid alloy is specially:
A, prepare graphite lead alloy, make the mass fraction of graphite in graphite lead alloy be 2% ~ 3%;
B, according to positive slab lattice alloy composition proportion, the lead of remainder is joined in lead melting furnace, be heated to 550 ~ 600 DEG C, then a is walked the graphite lead alloy obtained to join in lead melting furnace and stir, again mock silver and signal bronze are joined in lead melting furnace, abundant fusing also stirs, and obtains positive slab lattice alloy.
Sampling direct-reading spectrometer beta alloy composition after alloy preparation, main component should accord with tin 0.2% ~ 0.8%, aluminium 0.02% ~ 0.04%, graphite 0.2% ~ 0.4%, copper 0.04% ~ 0.1%, and surplus is plumbous.After testing, the positive plate grid alloy composition that each embodiment obtains is in table 1, and surplus is plumbous (comprising inevitable impurity).
Table 1
Grid is cast: lead melting furnace temperature setting 510 ~ 525 DEG C, plumbous spoon temperature 520 ~ 535 DEG C, and cover half temperature is set as 140 DEG C ~ 180 DEG C, and dynamic model temperature is set as 140 DEG C ~ 180 DEG C, cast panel speed appropriateness.Carry out examination casting after jet mould, meet formal cast panel after technological requirement until grid presentation quality, thickness and weight etc.The grid of casting shelves 2 days naturally, shelving in ag(e)ing process and will carrying out dust and moisture, checks grid quality and hardness after timeliness, carries out coated plate after qualified, the same normal process of all the other battery production operations.Conventional PbCaSnAl and slicker solder aluminum bronze graphite alloy of the present invention do Brinell hardness and tensile strength comparing result in table 2 and table 3.
Table 2 positive slab lattice alloy Brinell hardness test result (unit: HB (Kg/ (mm)
2)
| Different aging time | 1d | 2d | 3d | 5d | 7d | 10d |
| Conventional PbCaSnAl alloy | 9.06 | 9.77 | 10.1 | 11.0 | ||
| Embodiment 1 | 9.14 | 10.3 | 11.3 | |||
| Embodiment 2 | 9.03 | 10.0 | 11.0 | |||
| Embodiment 3 | 9.10 | 10.1 | 11.1 |
Conventional PbCaSnAl alloy: calcium 0.10%-0.13% aluminium 0.02%-0.04% tin 0.7%-1.4%, surplus is plumbous;
Slicker solder aluminum bronze graphite positive slab lattice alloy of the present invention, the Brinell hardness of natrual ageing after 2 days is suitable with the conventional Pb-Ca-Sn-Al alloy natrual ageing Brinell hardness of 7 days.The aging time that grid hardness reaches applicable full-filling obviously shortens.
Table 3 tensile strength test result
Slicker solder aluminum bronze graphite positive slab lattice alloy of the present invention contrasts in identical natrual ageing condition and the situation of time with routine plumbous calcium tin aluminium grid alloy, and tensile strength is obviously better than conventional plumbous calcium tin aluminium grid alloy.Conventional PbCaSnAl alloy and alloy cell cycle life test comparison data of the present invention are in table 4.
Table 4 conventional PbCaSnAl alloy and alloy cell cycle life test comparison of the present invention
As can be seen from this experimental test correction data, PCL-1 effect (the note: PCL-1: the impact at interface of the equal various degrees of two Battery packs of conventional PbCaSnAl alloy, show that the initial interior battery performance of tens of circulations declines rapidly, because the interface of anode plate grid and active material defines non-conductive layer, create larger resistance, when discharge and recharge, heating makes the expansion of the positive active material near grid lose activity, the early stage capacitance loss of battery is more serious), substantially there is not PCL-1 effect in alloy of the present invention, can find out that positive slab lattice alloy of the present invention has obvious superiority from test data.
Increase graphite in positive slab lattice alloy, the mechanical strength of grid can be changed.The grid that Pb-Ca-Sn-Al alloy makes can As time goes within the timeliness phase, and lattice increases gradually, and the timeliness phase is generally 4 ~ 7 days, and the timeliness phase is long, and this just means that the production cycle is long, and fund pressurization is serious.And the present invention adds graphite in positive grid, the mechanical strength of grid strengthens, and the timeliness phase is short, and the intensity of grid is suitable for coated plate.And due to the resistivity of graphite extremely low, the resistance of grid also can reduce.
Above-described embodiment is one of the present invention preferably scheme, not does any pro forma restriction to the present invention, also has other variant and remodeling under the prerequisite not exceeding the technical scheme described in claim.
Claims (5)
1. a positive plate grid alloy, the main component of grid alloy is plumbous, it is characterized in that this alloy comprises following in the component of mass fraction: tin 0.2% ~ 0.8%, aluminium 0.02% ~ 0.04%, graphite 0.2% ~ 0.4%, copper 0.04% ~ 0.1%, surplus is plumbous.
2. positive plate grid alloy according to claim 1, is characterized in that: this alloy comprises following in the component of mass fraction: tin 0.2%, aluminium 0.028%, graphite 0.4%, copper 0.06%, and surplus is plumbous.
3. positive plate grid alloy according to claim 1, is characterized in that: this alloy comprises following in the component of mass fraction: tin 0.79%, aluminium 0.04%, graphite 0.2%, copper 0.04%, and surplus is plumbous.
4. positive plate grid alloy according to claim 1, is characterized in that: this alloy comprises following in the component of mass fraction: tin 0.45%, aluminium 0.02%, graphite 0.32%, copper 0.1%, and surplus is plumbous.
5. a preparation method for positive plate grid alloy according to claim 1, is characterized in that the method is specially:
A, prepare graphite lead alloy, make the mass fraction of graphite in graphite lead alloy be 2% ~ 3%;
B, according to negative grid alloy composition proportion, the lead of remainder is joined in lead melting furnace, be heated to 550 ~ 600 DEG C, then a is walked the graphite lead alloy obtained to join in lead melting furnace and stir, again mock silver and signal bronze are joined in lead melting furnace, abundant fusing also stirs, and obtains positive slab lattice alloy.
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| CN201410527628.7A CN104377363A (en) | 2014-10-09 | 2014-10-09 | Lead acid battery positive grid alloy and preparation method thereof |
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| CN201410527628.7A CN104377363A (en) | 2014-10-09 | 2014-10-09 | Lead acid battery positive grid alloy and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106011980A (en) * | 2016-06-21 | 2016-10-12 | 天能电池集团有限公司 | Preparation method for lead storage battery grid alloy |
| CN108546845A (en) * | 2018-05-14 | 2018-09-18 | 贵州鑫凯达金属电源有限责任公司 | A kind of Alloy lead for lead acid battery and its production method |
| CN110768269A (en) * | 2019-12-03 | 2020-02-07 | 西安西电电力系统有限公司 | Static synchronous compensation device and control method thereof |
| CN111647769A (en) * | 2020-06-18 | 2020-09-11 | 超威电源集团有限公司 | Storage battery grid alloy and preparation method thereof |
Citations (4)
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| CN102005574A (en) * | 2010-10-29 | 2011-04-06 | 济南兄弟金属科技有限公司 | Light plate grid for lead-acid storage battery and preparation method thereof |
| CN102569818A (en) * | 2010-12-15 | 2012-07-11 | 苏州大学 | Positive plate for high-intensity grid of lead acid storage battery |
| CN102945948A (en) * | 2012-11-07 | 2013-02-27 | 陈欢平 | Novel rare earth lead-acid power cell |
| CN103943865A (en) * | 2014-05-07 | 2014-07-23 | 厦门华天高科电池科技有限公司 | Graphene-lead alloy as well as preparation method and application thereof |
-
2014
- 2014-10-09 CN CN201410527628.7A patent/CN104377363A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102005574A (en) * | 2010-10-29 | 2011-04-06 | 济南兄弟金属科技有限公司 | Light plate grid for lead-acid storage battery and preparation method thereof |
| CN102569818A (en) * | 2010-12-15 | 2012-07-11 | 苏州大学 | Positive plate for high-intensity grid of lead acid storage battery |
| CN102945948A (en) * | 2012-11-07 | 2013-02-27 | 陈欢平 | Novel rare earth lead-acid power cell |
| CN103943865A (en) * | 2014-05-07 | 2014-07-23 | 厦门华天高科电池科技有限公司 | Graphene-lead alloy as well as preparation method and application thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106011980A (en) * | 2016-06-21 | 2016-10-12 | 天能电池集团有限公司 | Preparation method for lead storage battery grid alloy |
| CN108546845A (en) * | 2018-05-14 | 2018-09-18 | 贵州鑫凯达金属电源有限责任公司 | A kind of Alloy lead for lead acid battery and its production method |
| CN110768269A (en) * | 2019-12-03 | 2020-02-07 | 西安西电电力系统有限公司 | Static synchronous compensation device and control method thereof |
| CN111647769A (en) * | 2020-06-18 | 2020-09-11 | 超威电源集团有限公司 | Storage battery grid alloy and preparation method thereof |
| CN111647769B (en) * | 2020-06-18 | 2021-03-30 | 超威电源集团有限公司 | Storage battery grid alloy and preparation method thereof |
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Application publication date: 20150225 |