CN103199263B - A kind of process for positive slab lattice of lead-acid accumulator Alloy And Preparation Method - Google Patents
A kind of process for positive slab lattice of lead-acid accumulator Alloy And Preparation Method Download PDFInfo
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- CN103199263B CN103199263B CN201310102900.2A CN201310102900A CN103199263B CN 103199263 B CN103199263 B CN 103199263B CN 201310102900 A CN201310102900 A CN 201310102900A CN 103199263 B CN103199263 B CN 103199263B
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- 239000000956 alloy Substances 0.000 title claims abstract description 168
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 159
- 239000002253 acid Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 56
- 230000008569 process Effects 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000004332 silver Substances 0.000 claims abstract description 75
- 229910052709 silver Inorganic materials 0.000 claims abstract description 75
- 239000011575 calcium Substances 0.000 claims abstract description 66
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 64
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052718 tin Inorganic materials 0.000 claims abstract description 60
- 239000004411 aluminium Substances 0.000 claims abstract description 59
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 59
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052684 Cerium Inorganic materials 0.000 claims description 43
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 43
- 229910052797 bismuth Inorganic materials 0.000 claims description 35
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 35
- 239000003610 charcoal Substances 0.000 claims description 29
- 238000003860 storage Methods 0.000 claims description 15
- 239000011133 lead Substances 0.000 abstract description 223
- 239000011135 tin Substances 0.000 abstract description 58
- 239000001999 grid alloy Substances 0.000 abstract description 51
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 25
- 239000001257 hydrogen Substances 0.000 abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 24
- 230000007797 corrosion Effects 0.000 abstract description 18
- 238000005260 corrosion Methods 0.000 abstract description 18
- 230000018044 dehydration Effects 0.000 abstract description 13
- 238000006297 dehydration reaction Methods 0.000 abstract description 13
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 238000001556 precipitation Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000002401 inhibitory effect Effects 0.000 abstract description 4
- 230000010287 polarization Effects 0.000 abstract description 4
- 230000002028 premature Effects 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 description 45
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910000464 lead oxide Inorganic materials 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 229910018725 Sn—Al Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 239000002142 lead-calcium alloy Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 2
- 235000013923 monosodium glutamate Nutrition 0.000 description 2
- 239000004223 monosodium glutamate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000796 S alloy Inorganic materials 0.000 description 1
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- 239000002140 antimony alloy Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a kind of process for positive slab lattice of lead-acid accumulator Alloy And Preparation Method, this alloy comprises lead, calcium, tin and aluminium, also comprises silver.Process for positive slab lattice of lead-acid accumulator alloy containing silver contributes to reducing Pb and PbSO
4reduction potential, make Pb
2+more easily be reduced to metal Pb.When constant potential polarization, silver is formed with inhibitory action to PbO, intensity and the creep strength of positive grid alloy can be improved, slow down positive grid alloy overaging effect in use, the interpolation of silver can suppress the growth of positive grid alloy corrosion layer, therefore be conducive to the deep discharge circulation of lead acid accumulator, overcome the generation of premature capacity loss phenomenon.Meanwhile, the interpolation of silver can increase overpotential of hydrogen evolution, suppresses the precipitation of hydrogen on alloy cathode, decrease the problem that battery dehydration is serious, improve the cycle life of battery, and this reasonable offer process is simple.
Description
Technical field
The invention belongs to battery technology field, be specifically related to a kind of process for positive slab lattice of lead-acid accumulator Alloy And Preparation Method.
Background technology
Along with progressively going deep into of new-energy automobile research and development, the requirement of automobile to battery performance also improves further.Lead acid accumulator has a wide range of applications on electric automobile and hybrid vehicle, needs the problem solving cycle life of lead-acid accumulator deficiency at present.Traditional lead acid accumulator uses Pb-Sb-As-Sn-Se-Cu-S alloy as positive grid alloy, this alloy is for containing antimony alloy, it can solve the problem of positive grid alloy poor corrosion resistance, lead acid accumulator is made to have the good deeper cavity life-span, but owing to containing a large amount of antimony in this alloy, antimony a large amount of in the use procedure of lead acid accumulator easily moves to negative plate, thus the overpotential of hydrogen evolution above reduction negative plates, cause lead acid accumulator dehydration serious, service life of lead accumulator is terminated in advance, at present, this alloy has seldom been used to the anode plate grid of lead acid accumulator.
At present, most lead acid accumulator uses Pb-Ca-Sn-Al alloy as positive grid alloy, and use this lead-calcium alloy can reduce lead acid accumulator phenomenon of losing water, after preventing lead acid accumulator dehydration, the life-span terminates in advance.But its poor corrosion resistance, especially in deeper cavity process, the surface of lead-calcium alloy positive grid alloy very easily grows one deck high-resistance anodic attack layer and serious intercrystalline corrosion occurs, cycle life of lead-acid accumulator is reduced, is difficult to reach the requirement of new-energy automobile to battery cycle life.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in prior art, a kind of process for positive slab lattice of lead-acid accumulator Alloy And Preparation Method is provided, this alloy substantially increases the decay resistance of battery, reduce the overpotential of hydrogen evolution of battery, decrease the problem that battery dehydration is serious, improve the cycle life of battery.
The technical scheme that solution the technology of the present invention problem adopts is to provide a kind of process for positive slab lattice of lead-acid accumulator alloy, comprises lead, calcium, tin and aluminium, also comprises silver.
Preferably, described calcium account for alloy gross mass 0.05% ~ 0.10%, described tin account for alloy gross mass 0.8% ~ 1.6%, described aluminium account for alloy gross mass 0.01% ~ 0.05%, described silver accounts for 0.01% ~ 0.1% of alloy gross mass, surplus is described lead.
Preferably, described process for positive slab lattice of lead-acid accumulator alloy, also comprises cerium.
Preferably, described calcium account for alloy gross mass 0.05% ~ 0.10%, described tin account for alloy gross mass 0.8% ~ 1.6%, described aluminium account for alloy gross mass 0.01% ~ 0.05%, described silver account for alloy gross mass 0.01% ~ 0.1%, described cerium accounts for 0.01% ~ 0.1% of alloy gross mass, surplus is described lead.
Preferably, described process for positive slab lattice of lead-acid accumulator alloy, also comprises bismuth.
Preferably, described calcium account for alloy gross mass 0.05% ~ 0.10%, described tin account for alloy gross mass 0.8% ~ 1.6%, described aluminium account for alloy gross mass 0.01% ~ 0.05%, described silver account for alloy gross mass 0.01% ~ 0.1%, described bismuth accounts for 0.01% ~ 0.08% of alloy gross mass, surplus is described lead.
Preferably, described process for positive slab lattice of lead-acid accumulator alloy, also comprises cerium and bismuth.
Preferably, described calcium account for alloy gross mass 0.05% ~ 0.10%, described tin account for alloy gross mass 0.8% ~ 1.6%, described aluminium account for alloy gross mass 0.01% ~ 0.05%, described silver account for alloy gross mass 0.01% ~ 0.1%, described cerium account for alloy gross mass 0.01% ~ 0.1%, described bismuth accounts for 0.01% ~ 0.08% of alloy gross mass, surplus is described lead.
Preferably, described process for positive slab lattice of lead-acid accumulator alloy, described lead acid accumulator is plumbous charcoal storage battery.
The present invention also provides a kind of preparation method of process for positive slab lattice of lead-acid accumulator alloy, comprises the following steps:
(1) the described lead in lead pan is heated to fusing;
(2) lead pan is warmed up to 650 ~ 680 DEG C, adds described cerium;
(3) lead pan is cooled to 600 ~ 650 DEG C, add described silver and described aluminium;
(4) lead pan is cooled to 420 ~ 440 DEG C, remove lead skim, add described tin and described bismuth, obtain process for positive slab lattice of lead-acid accumulator alloy.
The invention provides a kind of process for positive slab lattice of lead-acid accumulator Alloy And Preparation Method, the process for positive slab lattice of lead-acid accumulator alloy containing silver contributes to reducing Pb and PbSO
4reduction potential, make Pb
2+more easily be reduced to metal Pb.When constant potential polarization, silver is formed with inhibitory action to PbO, intensity and the creep strength of positive grid alloy can be improved, slow down positive grid alloy overaging effect in use, the interpolation of silver can suppress the growth of positive grid alloy corrosion layer, therefore be conducive to the deep discharge circulation of lead acid accumulator, overcome the generation of premature capacity loss phenomenon (PCL phenomenon).Meanwhile, the interpolation of silver can increase overpotential of hydrogen evolution, suppresses the precipitation of hydrogen on alloy cathode, decrease the problem that battery dehydration is serious, improve the cycle life of battery, and this reasonable offer process is simple.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
The present embodiment provides a kind of preparation method of process for positive slab lattice of lead-acid accumulator alloy, comprises the following steps:
(1) take the electrolytic lead of lead pan volume 80%, the lead in lead pan is heated to fusing;
(2) lead pan is warmed up to 600 DEG C, silver and aluminium are added in lead pan in proportion, stir after silver and aluminium all melt;
(3) lead pan is cooled to 440 DEG C, remove the lead skim on lead pan surface, tin is joined in lead pan in proportion, stir after tin fusing, then calcium is joined in lead pan in proportion, stir after the fusing of band calcium, obtain process for positive slab lattice of lead-acid accumulator alloy.
The process for positive slab lattice of lead-acid accumulator alloy prepared by above-mentioned preparation method comprises: lead, calcium, tin, aluminium, silver; Wherein, calcium account for alloy gross mass 0.07%, tin account for alloy gross mass 0.8%, aluminium account for alloy gross mass 0.05%, silver accounts for 0.05% of alloy gross mass, surplus is plumbous.
Process for positive slab lattice of lead-acid accumulator alloy containing silver contributes to reducing Pb and PbSO
4reduction potential, make Pb
2+more easily be reduced to metal Pb.When constant potential polarization, silver is formed with inhibitory action to PbO, intensity and the creep strength of positive grid alloy can be improved, slow down positive grid alloy overaging effect in use, the interpolation of silver can suppress the growth of positive grid alloy corrosion layer, is therefore conducive to the deep discharge circulation of lead acid accumulator, overcome the generation of premature capacity loss phenomenon (PCL phenomenon), meanwhile, the interpolation of silver can increase overpotential of hydrogen evolution, suppresses the precipitation of hydrogen on alloy cathode.
Embodiment 2
The present embodiment provides a kind of preparation method of process for positive slab lattice of lead-acid accumulator alloy, comprises the following steps:
(1) take the electrolytic lead of lead pan volume 80%, the lead in lead pan is heated to fusing;
(2) lead pan is warmed up to 650 DEG C, silver and aluminium are added in lead pan in proportion, stir after silver and aluminium all melt;
(3) lead pan is cooled to 420 DEG C, remove the lead skim on lead pan surface, tin is joined in lead pan in proportion, stir after tin fusing, then calcium is joined in lead pan in proportion, stir after the fusing of band calcium, obtain process for positive slab lattice of lead-acid accumulator alloy.
The process for positive slab lattice of lead-acid accumulator alloy prepared by above-mentioned preparation method comprises: lead, calcium, tin, aluminium, silver; Wherein, calcium account for alloy gross mass 0.05%, tin account for alloy gross mass 1.2%, aluminium account for alloy gross mass 0.03%, silver accounts for 0.01% of alloy gross mass, surplus is plumbous.
Embodiment 3
The present embodiment provides a kind of preparation method of plumbous charcoal battery positive voltage grid alloy, comprises the following steps:
(1) take the electrolytic lead of lead pan volume 80%, the lead in lead pan is heated to fusing;
(2) lead pan is warmed up to 625 DEG C, silver and aluminium are added in lead pan in proportion, stir after silver and aluminium all melt;
(3) lead pan is cooled to 430 DEG C, remove the lead skim on lead pan surface, tin is joined in lead pan in proportion, stir after tin fusing, then calcium is joined in lead pan in proportion, stir after the fusing of band calcium, obtain plumbous charcoal battery positive voltage grid alloy.
The process for positive slab lattice of lead-acid accumulator alloy prepared by above-mentioned preparation method comprises: lead, calcium, tin, aluminium, silver; Wherein, calcium account for alloy gross mass 0.1%, tin account for alloy gross mass 1.6%, aluminium account for alloy gross mass 0.01%, silver accounts for 0.1% of alloy gross mass, surplus is plumbous.
Plumbous charcoal storage battery is a kind of novel lead acid accumulator, can improve the large current charge performance of lead acid accumulator, but because the overpotential of hydrogen evolution of Carbon Materials is low, in cyclic process, battery dehydration is serious, and its cycle life is general lower.In the present embodiment, alloy material is used for the decay resistance that plumbous carbon storage battery can improve this battery, reduces the overpotential of hydrogen evolution of battery, reduces the problem that the dehydration of battery is serious, improves the cycle life of battery.
Embodiment 4
The present embodiment provides a kind of preparation method of process for positive slab lattice of lead-acid accumulator alloy, comprises the following steps:
(1) take the electrolytic lead of lead pan volume 80%, the lead in lead pan is heated to fusing;
(2) lead pan is warmed up to 680 DEG C, cerium is added in lead pan in proportion, stir after cerium fusing;
(3) lead pan is cooled to 600 DEG C, silver and aluminium are added in lead pan in proportion, stir after silver and aluminium all melt;
(4) lead pan is cooled to 440 DEG C, remove the lead skim on lead pan surface, tin is joined in lead pan in proportion, stir after tin fusing, then calcium is joined in lead pan in proportion, stir after the fusing of band calcium, obtain process for positive slab lattice of lead-acid accumulator alloy.
The process for positive slab lattice of lead-acid accumulator alloy prepared by above-mentioned preparation method comprises: lead, calcium, tin, aluminium, silver, cerium; Wherein, calcium account for alloy gross mass 0.1%, tin account for alloy gross mass 1.6%, aluminium account for alloy gross mass 0.03%, silver accounts for 0.1% of alloy gross mass, cerium accounts for 0.05% of alloy gross mass, and surplus is plumbous.
Cerium is a kind of additive of monosodium glutamate formula, it is widely used in every field, and cerium and lead can form dystectic metallic compound, and the intergranular that can neutralize some lead-containing alloy tears phenomenon, improve the hot-workability of lead-containing alloy, increase toughness and the creep resistance of lead-containing alloy.Cerium (Ce) has has close comparatively negative electrode current potential with calcium metal (Ca), and cerium has the hardness of more plumbous, calcium, Xi Genggao and more excellent mechanical performance.The impedance operator adding the anode film that can improve lead of cerium, improves the decay resistance of positive grid alloy, and strengthen castability and the mechanical strength of positive grid alloy, that improves maintenance-free lead accumulator fills cycle performance simultaneously deeply.
Embodiment 5
The present embodiment provides a kind of preparation method of process for positive slab lattice of lead-acid accumulator alloy, comprises the following steps:
(1) take the electrolytic lead of lead pan volume 80%, the lead in lead pan is heated to fusing;
(2) lead pan is warmed up to 665 DEG C, cerium is added in lead pan in proportion, stir after cerium fusing;
(3) lead pan is cooled to 650 DEG C, silver and aluminium are added in lead pan in proportion, stir after silver and aluminium all melt;
(4) lead pan is cooled to 430 DEG C, remove the lead skim on lead pan surface, tin is joined in lead pan in proportion, stir after tin fusing, then calcium is joined in lead pan in proportion, stir after the fusing of band calcium, obtain process for positive slab lattice of lead-acid accumulator alloy.
The process for positive slab lattice of lead-acid accumulator alloy prepared by above-mentioned preparation method comprises: lead, calcium, tin, aluminium, silver, cerium; Wherein, calcium account for alloy gross mass 0.07%, tin account for alloy gross mass 1.2%, aluminium account for alloy gross mass 0.05%, silver accounts for 0.05% of alloy gross mass, cerium accounts for 0.01% of alloy gross mass, and surplus is plumbous.
Embodiment 6
The present embodiment provides a kind of preparation method of plumbous charcoal battery positive voltage grid alloy, comprises the following steps:
(1) take the electrolytic lead of lead pan volume 80%, the lead in lead pan is heated to fusing;
(2) lead pan is warmed up to 650 DEG C, cerium is added in lead pan in proportion, stir after cerium fusing;
(3) lead pan is cooled to 625 DEG C, silver and aluminium are added in lead pan in proportion, stir after silver and aluminium all melt;
(4) lead pan is cooled to 420 DEG C, remove the lead skim on lead pan surface, tin is joined in lead pan in proportion, stir after tin fusing, then calcium is joined in lead pan in proportion, stir after the fusing of band calcium, obtain plumbous charcoal battery positive voltage grid alloy.
The process for positive slab lattice of lead-acid accumulator alloy prepared by above-mentioned preparation method comprises: lead, calcium, tin, aluminium, silver, cerium; Wherein, calcium account for alloy gross mass 0.05%, tin account for alloy gross mass 0.8%, aluminium account for alloy gross mass 0.01%, silver accounts for 0.01% of alloy gross mass, cerium accounts for 0.1% of alloy gross mass, and surplus is plumbous.
Plumbous charcoal storage battery is a kind of novel lead acid accumulator, can improve the large current charge performance of lead acid accumulator, but because the overpotential of hydrogen evolution of Carbon Materials is low, in cyclic process, battery dehydration is serious, and its cycle life is general lower.In the present embodiment, alloy material is used for the decay resistance that plumbous carbon storage battery can improve this battery, reduces the overpotential of hydrogen evolution of battery, reduces the problem that the dehydration of battery is serious, improves the cycle life of battery.
Embodiment 7
The present embodiment provides a kind of preparation method of process for positive slab lattice of lead-acid accumulator alloy, comprises the following steps:
(1) take the electrolytic lead of lead pan volume 80%, the lead in lead pan is heated to fusing;
(2) lead pan is warmed up to 650 DEG C, silver and aluminium are added in lead pan in proportion, stir after silver and aluminium all melt;
(3) lead pan is cooled to 420 DEG C, remove the lead skim on lead pan surface, tin and bismuth are joined in lead pan in proportion, stir after tin and bismuth fusing, again calcium is joined in lead pan in proportion, stir after the fusing of band calcium, obtain process for positive slab lattice of lead-acid accumulator alloy.
The process for positive slab lattice of lead-acid accumulator alloy prepared by above-mentioned preparation method comprises: lead, calcium, tin, aluminium, silver, bismuth; Wherein, calcium account for alloy gross mass 0.05%, tin account for alloy gross mass 0.8%, aluminium account for alloy gross mass 0.01%, silver accounts for 0.05% of alloy gross mass, bismuth accounts for 0.08% of alloy gross mass, and surplus is plumbous.
Adding a small amount of bismuth in process for positive slab lattice of lead-acid accumulator alloy can the crystal grain of refinement positive grid alloy, improves the intensity of positive grid alloy, strengthens the resistance to corrosion of positive grid alloy; Meanwhile, also improve hardness and the castability of positive grid alloy, decrease gas evolution in battery charging process, be conducive to battery deep-circulating performance.
Embodiment 8
The present embodiment provides a kind of preparation method of process for positive slab lattice of lead-acid accumulator alloy, comprises the following steps:
(1) take the electrolytic lead of lead pan volume 80%, the lead in lead pan is heated to fusing;
(2) lead pan is warmed up to 625 DEG C, silver and aluminium are added in lead pan in proportion, stir after silver and aluminium all melt;
(3) lead pan is cooled to 430 DEG C, remove the lead skim on lead pan surface, tin and bismuth are joined in lead pan in proportion, stir after tin and bismuth fusing, again calcium is joined in lead pan in proportion, stir after the fusing of band calcium, obtain process for positive slab lattice of lead-acid accumulator alloy.
The process for positive slab lattice of lead-acid accumulator alloy prepared by above-mentioned preparation method comprises: lead, calcium, tin, aluminium, silver, bismuth; Wherein, calcium account for alloy gross mass 0.07%, tin account for alloy gross mass 1.2%, aluminium account for alloy gross mass 0.05%, silver accounts for 0.01% of alloy gross mass, bismuth accounts for 0.05% of alloy gross mass, and surplus is plumbous.
Embodiment 9
The present embodiment provides a kind of preparation method of plumbous charcoal battery positive voltage grid alloy, comprises the following steps:
(1) take the electrolytic lead of lead pan volume 80%, the lead in lead pan is heated to fusing;
(2) lead pan is warmed up to 600 DEG C, silver and aluminium are added in lead pan in proportion, stir after silver and aluminium all melt;
(3) lead pan is cooled to 440 DEG C, remove the lead skim on lead pan surface, tin and bismuth are joined in lead pan in proportion, stir after tin and bismuth fusing, again calcium is joined in lead pan in proportion, stir after the fusing of band calcium, obtain plumbous charcoal battery positive voltage grid alloy.
The process for positive slab lattice of lead-acid accumulator alloy prepared by above-mentioned preparation method comprises: lead, calcium, tin, aluminium, silver, bismuth; Wherein, calcium account for alloy gross mass 0.1%, tin account for alloy gross mass 1.6%, aluminium account for alloy gross mass 0.03%, silver accounts for 0.1% of alloy gross mass, bismuth accounts for 0.01% of alloy gross mass, and surplus is plumbous.
Plumbous charcoal storage battery is a kind of novel lead acid accumulator, can improve the large current charge performance of lead acid accumulator, but because the overpotential of hydrogen evolution of Carbon Materials is low, in cyclic process, battery dehydration is serious, and its cycle life is general lower.In the present embodiment, alloy material is used for the decay resistance that plumbous carbon storage battery can improve this battery, reduces the overpotential of hydrogen evolution of battery, reduces the problem that the dehydration of battery is serious, improves the cycle life of battery.
Embodiment 10
The present embodiment provides a kind of preparation method of plumbous charcoal battery positive voltage grid alloy, comprises the following steps:
(1) take the electrolytic lead of lead pan volume 80%, the lead in lead pan is heated to fusing;
(2) lead pan is warmed up to 660 DEG C, cerium is added in lead pan in proportion, stir after cerium fusing;
(3) lead pan is cooled to 600 DEG C, silver and aluminium are added in lead pan in proportion, stir after silver and aluminium all melt;
(4) lead pan is cooled to 430 DEG C, remove the lead skim on lead pan surface, tin and bismuth are joined in lead pan in proportion, stir after tin and bismuth fusing, again calcium is joined in lead pan in proportion, stir after the fusing of band calcium, obtain plumbous charcoal battery positive voltage grid alloy.
The plumbous charcoal battery positive voltage grid alloy prepared by above-mentioned preparation method comprises: lead, calcium, tin, aluminium, silver, cerium, bismuth; Wherein, calcium account for alloy gross mass 0.1%, tin account for alloy gross mass 1.2%, aluminium account for alloy gross mass 0.05%, silver accounts for 0.01% of alloy gross mass, cerium accounts for 0.05% of alloy gross mass, and bismuth accounts for 0.08% of alloy gross mass, and surplus is plumbous.
Plumbous charcoal battery positive voltage grid alloy containing silver contributes to reducing Pb and PbSO
4reduction potential, make Pb
2+more easily be reduced to metal Pb.When constant potential polarization, silver is formed with inhibitory action to PbO, intensity and the creep strength of positive grid alloy can be improved, slow down positive grid alloy overaging effect in use, the interpolation of silver can suppress the growth of positive grid alloy corrosion layer, is therefore conducive to the deep discharge circulation of plumbous charcoal storage battery, overcome the generation of premature capacity loss phenomenon (PCL phenomenon), meanwhile, the interpolation of silver can increase overpotential of hydrogen evolution, suppresses the precipitation of hydrogen on alloy cathode.
Cerium is a kind of additive of monosodium glutamate formula, it is widely used in every field, and cerium and lead can form dystectic metallic compound, and the intergranular that can neutralize some lead-containing alloy tears phenomenon, improve the hot-workability of lead-containing alloy, increase toughness and the creep resistance of lead-containing alloy.Cerium (Ce) has has close comparatively negative electrode current potential with calcium metal (Ca), and cerium has the hardness of more plumbous, calcium, Xi Genggao and more excellent mechanical performance.The impedance operator adding the anode film that can improve lead of cerium, improves the decay resistance of positive grid alloy, and strengthen castability and the mechanical strength of positive grid alloy, that improves non-maintaining plumbous charcoal storage battery fills cycle performance simultaneously deeply.
Adding a small amount of bismuth in plumbous charcoal battery positive voltage grid alloy can the crystal grain of refinement positive grid alloy, improves the intensity of positive grid alloy, strengthens the resistance to corrosion of positive grid alloy; Meanwhile, also improve hardness and the castability of positive grid alloy, decrease gas evolution in battery charging process, be conducive to battery deep-circulating performance.
Plumbous charcoal battery positive voltage grid alloy simultaneously in embodiment reduces the content of the calcium in alloy on original Pb-Ca-Sn-Al alloy basis, improve the content of tin, reduce the scaling loss that calcium content can reduce casting process, enhance positive grid alloy decay resistance, increase Theil indices and can improve opourability and the mechanical strength of positive grid alloy, improve and recharge ability after battery deep discharge.
Embodiment 11
The present embodiment provides a kind of preparation method of plumbous charcoal battery positive voltage grid alloy, comprises the following steps:
(1) take the electrolytic lead of lead pan volume 80%, the lead in lead pan is heated to fusing;
(2) lead pan is warmed up to 650 DEG C, cerium is added in lead pan in proportion, stir after cerium fusing;
(3) lead pan is cooled to 625 DEG C, silver and aluminium are added in lead pan in proportion, stir after silver and aluminium all melt;
(4) lead pan is cooled to 420 DEG C, remove the lead skim on lead pan surface, tin and bismuth are joined in lead pan in proportion, stir after tin and bismuth fusing, again calcium is joined in lead pan in proportion, stir after the fusing of band calcium, obtain plumbous charcoal battery positive voltage grid alloy.
The plumbous charcoal battery positive voltage grid alloy prepared by above-mentioned preparation method comprises: lead, calcium, tin, aluminium, silver, cerium, bismuth; Wherein, calcium account for alloy gross mass 0.05%, tin account for alloy gross mass 0.8%, aluminium account for alloy gross mass 0.03%, silver accounts for 0.1% of alloy gross mass, cerium accounts for 0.1% of alloy gross mass, and bismuth accounts for 0.01% of alloy gross mass, and surplus is plumbous.
Embodiment 12
The present embodiment provides a kind of preparation method of plumbous charcoal battery positive voltage grid alloy, comprises the following steps:
(1) take the electrolytic lead of lead pan volume 80%, the lead in lead pan is heated to fusing;
(2) lead pan is warmed up to 680 DEG C, cerium is added in lead pan in proportion, stir after cerium fusing;
(3) lead pan is cooled to 650 DEG C, silver and aluminium are added in lead pan in proportion, stir after silver and aluminium all melt;
(4) lead pan is cooled to 440 DEG C, remove the lead skim on lead pan surface, tin and bismuth are joined in lead pan in proportion, stir after tin and bismuth fusing, again calcium is joined in lead pan in proportion, stir after the fusing of band calcium, obtain plumbous charcoal battery positive voltage grid alloy.
The plumbous charcoal battery positive voltage grid alloy prepared by above-mentioned preparation method comprises: lead, calcium, tin, aluminium, silver, cerium, bismuth; Wherein, calcium account for alloy gross mass 0.07%, tin account for alloy gross mass 1.6%, aluminium account for alloy gross mass 0.01%, silver accounts for 0.05% of alloy gross mass, cerium accounts for 0.01% of alloy gross mass, and bismuth accounts for 0.05% of alloy gross mass, and surplus is plumbous.
Plumbous charcoal storage battery is when normally working, and the lead ion in electrolyte oxidation reaction very easily occurs on positive grid alloy and generates lead oxide.Lead oxide is non-conductive, thus greatly reduces the performance of lead carbon battery.The positive grid alloy that the present embodiment provides can stop on positive grid alloy and generates lead oxide, and the metal level that this alloy material is formed is finer and close, substantially improve the structure of alloy material inside, the structure cell crack of alloy inside diminishes, thus improve the electric conductivity of alloy material, substantially increase the decay resistance of alloy material, reduce the overpotential of hydrogen evolution of alloy material surface.
Plumbous charcoal storage battery is a kind of novel plumbous charcoal storage battery, can improve the large current charge performance of plumbous charcoal storage battery, but because the overpotential of hydrogen evolution of Carbon Materials is low, in cyclic process, battery dehydration is serious, and its cycle life is general lower.In the present embodiment, alloy material is used for the decay resistance that plumbous carbon storage battery can improve this battery, reduces the overpotential of hydrogen evolution of battery, reduces the problem that the dehydration of battery is serious, improves the cycle life of battery.
Comparative example 1
This comparative example provides a kind of preparation method of process for positive slab lattice of lead-acid accumulator alloy, comprises the following steps:
(1) take the electrolytic lead of lead pan volume 80%, the lead in lead pan is heated to fusing;
(2) lead pan is warmed up to 600 DEG C, aluminium is added in lead pan in proportion, stirs after aluminium all melts;
(3) lead pan is cooled to 430 DEG C, remove the lead skim on lead pan surface, tin is joined in lead pan in proportion, stir after tin fusing, then calcium is joined in lead pan in proportion, stir after the fusing of band calcium, obtain process for positive slab lattice of lead-acid accumulator alloy.
Respectively constant current corrosion weight loss and overpotential of hydrogen evolution test are carried out to the process for positive slab lattice of lead-acid accumulator alloy of embodiment 10 ~ 12, comparative example 1:
(1) carry out the test of constant current corrosion weight loss to various alloy respectively, experimental technique is conventionally known to one of skill in the art, and experimental result is in table 1:
Table 1 alloy constant current corrosion weight loss test result
As can be seen from table 1 data, the relative corrosion rate of the alloy in embodiment 1,4,7,11 is all lower relative to comparative example 1.Can be found out by embodiment 1,4,7,11, require that according to alloying component in the present invention the relative corrosion rate of the alloy of preparation is all lower, corrosion resistance is strong.Adding of visible silver, cerium, bismuth is conducive to falling low-alloyed relative corrosion rate.
(2) carry out overpotential of hydrogen evolution test to various alloy respectively, experimental technique is conventionally known to one of skill in the art, and experimental result is in table 2:
Show 2-in-1 golden overpotential of hydrogen evolution test result
The rule of table 2 data and table 1 data is similar, can find out that the liberation of hydrogen current density of the alloy in embodiment 1,4,7,11 is all lower relative to comparative example 1.Alloying component in visible the present invention requires that the liberation of hydrogen current density of the alloy of preparation is lower, be conducive to the adding of visible silver, cerium, bismuth the precipitation suppressing hydrogen, and gassing rate is little, and then the generation of the decomposition of water and the self discharge of battery can be stoped, this maintenance-free performance for battery is very favorable.
Therefore, drawn by above two experiments, alloy corrosion speed of the present invention is very little, and corrosion resistance is strong, and gassing rate is little.
Be understandable that, the illustrative embodiments that above execution mode is only used to principle of the present invention is described and adopts, but the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement are also considered as protection scope of the present invention.
Claims (3)
1. a preparation method for process for positive slab lattice of lead-acid accumulator alloy, is characterized in that, comprises the following steps:
(1) lead in lead pan is heated to fusing;
(2) lead pan is warmed up to 650 ~ 680 DEG C, adds cerium;
(3) lead pan is cooled to 600 ~ 650 DEG C, add silver and aluminium;
(4) lead pan is cooled to 420 ~ 440 DEG C, remove lead skim, add tin and bismuth, then add calcium, obtain process for positive slab lattice of lead-acid accumulator alloy.
2. the preparation method of process for positive slab lattice of lead-acid accumulator alloy according to claim 1, it is characterized in that, in described process for positive slab lattice of lead-acid accumulator alloy, described calcium account for alloy gross mass 0.05% ~ 0.10%, described tin account for alloy gross mass 0.8% ~ 1.6%, described aluminium account for alloy gross mass 0.01% ~ 0.05%, described silver account for alloy gross mass 0.01% ~ 0.1%, described cerium account for alloy gross mass 0.01% ~ 0.1%, described bismuth accounts for 0.01% ~ 0.08% of alloy gross mass, surplus is described lead.
3. the preparation method of the process for positive slab lattice of lead-acid accumulator alloy according to claim 1 or 2 any one, is characterized in that, described lead acid accumulator is plumbous charcoal storage battery.
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| CN104131188B (en) * | 2014-05-13 | 2016-06-01 | 超威电源有限公司 | The conjunction technique of a kind of plumbous calcium mother alloy |
| CN105070920A (en) * | 2015-09-22 | 2015-11-18 | 广州丰江实业有限公司 | Long-life lead-acid battery with high temperature and low temperature resistance |
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| CN109518017A (en) * | 2018-10-24 | 2019-03-26 | 山东久力工贸集团有限公司 | A kind of maintenance-free lead accumulator positive plate grid metal and preparation method thereof |
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| CN112786884A (en) * | 2021-01-05 | 2021-05-11 | 浙江南都电源动力股份有限公司 | High-performance graphene storage battery for starting and stopping automobile |
| CN113241445B (en) * | 2021-04-15 | 2022-09-20 | 淄博火炬能源有限责任公司 | Grid alloy for lead-carbon battery and preparation method thereof |
| JP7198890B1 (en) | 2021-09-13 | 2023-01-04 | 古河電池株式会社 | lead acid battery |
| CN114284583A (en) * | 2021-12-27 | 2022-04-05 | 河南超威正效电源有限公司 | Method for reducing EFB power-on and power-off pool water loss |
| CN114790523A (en) * | 2022-03-09 | 2022-07-26 | 安徽力普拉斯电源技术有限公司 | Lead-calcium-tin-aluminum-silver-bismuth positive grid alloy and preparation method thereof |
| CN115198124A (en) * | 2022-06-13 | 2022-10-18 | 风帆有限责任公司 | Process for preparing lead-base rare-earth alloy |
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