CN103199263A - Positive grid alloy of lead-acid battery and manufacturing method of alloy - Google Patents
Positive grid alloy of lead-acid battery and manufacturing method of alloy Download PDFInfo
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- CN103199263A CN103199263A CN2013101029002A CN201310102900A CN103199263A CN 103199263 A CN103199263 A CN 103199263A CN 2013101029002 A CN2013101029002 A CN 2013101029002A CN 201310102900 A CN201310102900 A CN 201310102900A CN 103199263 A CN103199263 A CN 103199263A
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- 239000000956 alloy Substances 0.000 title claims abstract description 143
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 134
- 239000001999 grid alloy Substances 0.000 title claims abstract description 102
- 239000002253 acid Substances 0.000 title claims abstract description 74
- 238000004519 manufacturing process Methods 0.000 title abstract 3
- 239000011133 lead Substances 0.000 claims abstract description 284
- 239000004332 silver Substances 0.000 claims abstract description 77
- 229910052709 silver Inorganic materials 0.000 claims abstract description 77
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000011575 calcium Substances 0.000 claims abstract description 69
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 67
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000011135 tin Substances 0.000 claims abstract description 65
- 229910052718 tin Inorganic materials 0.000 claims abstract description 65
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 63
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000004411 aluminium Substances 0.000 claims description 62
- 229910052684 Cerium Inorganic materials 0.000 claims description 46
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 46
- 229910052797 bismuth Inorganic materials 0.000 claims description 38
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 38
- 238000002360 preparation method Methods 0.000 claims description 34
- 239000003610 charcoal Substances 0.000 claims description 33
- 238000003860 storage Methods 0.000 claims description 15
- 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 22
- 238000000034 method Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 230000002401 inhibitory effect Effects 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 abstract description 2
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 abstract 1
- 229910052924 anglesite Inorganic materials 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000005562 fading Methods 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 45
- 230000007797 corrosion Effects 0.000 description 17
- 238000005260 corrosion Methods 0.000 description 17
- 238000005303 weighing Methods 0.000 description 13
- 230000018044 dehydration Effects 0.000 description 12
- 238000006297 dehydration reaction Methods 0.000 description 12
- 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
- 125000004122 cyclic group Chemical group 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910000464 lead oxide Inorganic materials 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 230000002028 premature Effects 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
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000002142 lead-calcium alloy Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 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
- 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
- 239000000155 melt Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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 discloses a positive grid alloy of a lead-acid battery and a manufacturing method of the alloy. The alloy includes lead, calcium, tin, aluminum and silver. The positive grid alloy containing silver of the lead-acid battery is helpful to the reduction of reduction potentials of Pb and PbSO4, thereby enabling Pb2+ to be easily reduced into metal Pb. The silver has an inhibiting effect on the formation of PbO when a constant potential is polarized, the intensity and the creeping strength of the positive grid alloy are improved, and an over-aging effect of the positive grid alloy in a use process is slowed down; and the addition of the sliver can inhibit the increase of a corrosive layer of the positive grid alloy, thereby facilitating the deep discharge cycle of the lead-acid battery, and preventing capacity fading phenomena in the early stage. Meanwhile, through the addition of the sliver, hydrogen evolution overpotentials are enhanced, the separation of hydrogen on a cathode of the alloy is inhibited, the problem of serious water loss of the battery is reduced, and the cycle life of the battery is prolonged. Moreover, the manufacturing process of the alloy is simple.
Description
Technical field
The invention belongs to the battery technology field, be specifically related to a kind of anode plate for lead acid accumulator grid Alloy And Preparation Method.
Background technology
Along with progressively going deep into of new-energy automobile research and development, automobile also further improves the requirement of battery performance.Lead acid accumulator has a wide range of applications at electric automobile and hybrid vehicle, needs to solve the problem of lead acid accumulator cycle life deficiency at present.Traditional lead acid accumulator uses the 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, make lead acid accumulator that well dark cycle life be arranged, but owing to contain a large amount of antimony in this alloy, antimony a large amount of in the use of lead acid accumulator are moved to negative plate easily, thereby the overpotential of hydrogen evolution above the reduction negative plates, cause the lead acid accumulator dehydration serious, service life of lead accumulator is finished in advance, at present, this alloy seldom has been used to the anode plate grid of lead acid accumulator.
At present, mostly lead acid accumulator uses the Pb-Ca-Sn-Al alloy as positive grid alloy, uses this lead-calcium alloy can reduce the lead acid accumulator phenomenon of losing water, prevent the lead acid accumulator dehydration after the life-span finish in advance.But its poor corrosion resistance, especially in dark cyclic process, very easily the grow high-resistance anodic attack layer of one deck and serious intercrystalline corrosion takes place of the surface of lead-calcium alloy positive grid alloy, make lead acid accumulator cycle life reduce, be difficult to reach new-energy automobile to the requirement of battery cycle life.
Summary of the invention
Technical problem to be solved by this invention is at above shortcomings in the prior art, a kind of anode plate for lead acid accumulator grid Alloy And Preparation Method is provided, this alloy has improved the decay resistance of battery greatly, reduced the overpotential of hydrogen evolution of battery, reduce the serious problem of battery dehydration, improved the cycle life of battery.
The technical scheme that solution the technology of the present invention problem adopts provides a kind of anode plate for lead acid accumulator grid alloy, comprises lead, calcium, tin and aluminium, also comprises silver.
Preferably, described calcium account for the alloy gross mass 0.05%～0.10%, described tin account for the alloy gross mass 0.8%～1.6%, described aluminium account for the 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 anode plate for lead acid accumulator grid alloy also comprises cerium.
Preferably, described calcium account for the alloy gross mass 0.05%～0.10%, described tin account for the alloy gross mass 0.8%～1.6%, described aluminium account for the alloy gross mass 0.01%～0.05%, described silver account for the 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 anode plate for lead acid accumulator grid alloy also comprises bismuth.
Preferably, described calcium account for the alloy gross mass 0.05%～0.10%, described tin account for the alloy gross mass 0.8%～1.6%, described aluminium account for the alloy gross mass 0.01%～0.05%, described silver account for the 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 anode plate for lead acid accumulator grid alloy also comprises cerium and bismuth.
Preferably, described calcium account for the alloy gross mass 0.05%～0.10%, described tin account for the alloy gross mass 0.8%～1.6%, described aluminium account for the alloy gross mass 0.01%～0.05%, described silver account for the alloy gross mass 0.01%～0.1%, described cerium account for the 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 anode plate for lead acid accumulator grid alloy, described lead acid accumulator are plumbous charcoal storage battery.
The present invention also provides a kind of preparation method of anode plate for lead acid accumulator grid alloy, may further comprise the steps:
(1) the described lead in the lead pan is heated to fusing;
(2) lead pan is warmed up to 650～680 ℃, adds described cerium;
(3) lead pan is cooled to 600～650 ℃, add described silver and described aluminium;
(4) lead pan is cooled to 420～440 ℃, remove lead skim, add described tin and described bismuth, obtain anode plate for lead acid accumulator grid alloy.
The invention provides a kind of anode plate for lead acid accumulator grid Alloy And Preparation Method, the anode plate for lead acid accumulator grid alloy that contains silver helps to reduce Pb and PbSO
4Reduction potential, make Pb
2+The easier metal Pb that is reduced to.When constant potential polarization, silver is to the inhibitory action that is formed with of PbO, can improve intensity and the creep strength of positive grid alloy, 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).Simultaneously, the interpolation of silver can increase overpotential of hydrogen evolution, suppresses separating out of hydrogen on the alloy cathode, has reduced the serious problem of battery dehydration, improved the cycle life of battery, and this alloy preparation 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
Present embodiment provides a kind of preparation method of anode plate for lead acid accumulator grid alloy, may further comprise the steps:
(1) takes by weighing the electrolytic lead of lead pan volume 80%, the lead in the lead pan is heated to fusing;
(2) lead pan is warmed up to 600 ℃, silver and aluminium are added in the lead pan in proportion, treat to stir after silver and aluminium all melt;
(3) lead pan is cooled to 440 ℃, remove the lead skim on lead pan surface, tin is joined in the lead pan in proportion, treat to stir after the tin fusing, again calcium is joined in the lead pan in proportion, stir after the fusing of band calcium, obtain anode plate for lead acid accumulator grid alloy.
The anode plate for lead acid accumulator grid alloy that is prepared by above-mentioned preparation method comprises: lead, calcium, tin, aluminium, silver; Wherein, calcium account for the alloy gross mass 0.07%, tin account for the alloy gross mass 0.8%, aluminium account for the alloy gross mass 0.05%, silver accounts for 0.05% of alloy gross mass, surplus is plumbous.
The anode plate for lead acid accumulator grid alloy that contains silver helps to reduce Pb and PbSO
4Reduction potential, make Pb
2+The easier metal Pb that is reduced to.When constant potential polarization, silver is to the inhibitory action that is formed with of PbO, can improve intensity and the creep strength of positive grid alloy, slow down positive grid alloy overaging effect in use, the interpolation of silver can suppress the growth of positive grid alloy corrosion layer, therefore is conducive to the deep discharge circulation of lead acid accumulator, overcome the generation of premature capacity loss phenomenon (PCL phenomenon), simultaneously, the interpolation of silver can increase overpotential of hydrogen evolution, and hydrogen separates out on the inhibition alloy cathode.
Embodiment 2
Present embodiment provides a kind of preparation method of anode plate for lead acid accumulator grid alloy, may further comprise the steps:
(1) takes by weighing the electrolytic lead of lead pan volume 80%, the lead in the lead pan is heated to fusing;
(2) lead pan is warmed up to 650 ℃, silver and aluminium are added in the lead pan in proportion, treat to stir after silver and aluminium all melt;
(3) lead pan is cooled to 420 ℃, remove the lead skim on lead pan surface, tin is joined in the lead pan in proportion, treat to stir after the tin fusing, again calcium is joined in the lead pan in proportion, stir after the fusing of band calcium, obtain anode plate for lead acid accumulator grid alloy.
The anode plate for lead acid accumulator grid alloy that is prepared by above-mentioned preparation method comprises: lead, calcium, tin, aluminium, silver; Wherein, calcium account for the alloy gross mass 0.05%, tin account for the alloy gross mass 1.2%, aluminium account for the alloy gross mass 0.03%, silver accounts for 0.01% of alloy gross mass, surplus is plumbous.
Embodiment 3
Present embodiment provides a kind of preparation method of plumbous charcoal battery positive voltage grid alloy, may further comprise the steps:
(1) takes by weighing the electrolytic lead of lead pan volume 80%, the lead in the lead pan is heated to fusing;
(2) lead pan is warmed up to 625 ℃, silver and aluminium are added in the lead pan in proportion, treat to stir after silver and aluminium all melt;
(3) lead pan is cooled to 430 ℃, remove the lead skim on lead pan surface, tin is joined in the lead pan in proportion, treat to stir after the tin fusing, again calcium is joined in the lead pan in proportion, stir after the fusing of band calcium, obtain plumbous charcoal battery positive voltage grid alloy.
The anode plate for lead acid accumulator grid alloy that is prepared by above-mentioned preparation method comprises: lead, calcium, tin, aluminium, silver; Wherein, calcium account for the alloy gross mass 0.1%, tin account for the alloy gross mass 1.6%, aluminium account for the 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 raw material of wood-charcoal material is low, in the cyclic process battery dehydration serious, its cycle life is generally lower.Alloy material is used for the decay resistance that plumbous carbon storage battery can improve this battery in the present embodiment, reduces the overpotential of hydrogen evolution of battery, reduces the serious problem of dehydration of battery, improves the cycle life of battery.
Embodiment 4
Present embodiment provides a kind of preparation method of anode plate for lead acid accumulator grid alloy, may further comprise the steps:
(1) takes by weighing the electrolytic lead of lead pan volume 80%, the lead in the lead pan is heated to fusing;
(2) lead pan is warmed up to 680 ℃, cerium is added in the lead pan in proportion, treat to stir after the cerium fusing;
(3) lead pan is cooled to 600 ℃, silver and aluminium are added in the lead pan in proportion, treat to stir after silver and aluminium all melt;
(4) lead pan is cooled to 440 ℃, remove the lead skim on lead pan surface, tin is joined in the lead pan in proportion, treat to stir after the tin fusing, again calcium is joined in the lead pan in proportion, stir after the fusing of band calcium, obtain anode plate for lead acid accumulator grid alloy.
The anode plate for lead acid accumulator grid alloy that is prepared by above-mentioned preparation method comprises: lead, calcium, tin, aluminium, silver, cerium; Wherein, calcium account for the alloy gross mass 0.1%, tin account for the alloy gross mass 1.6%, aluminium account for the alloy gross mass 0.03%, silver accounts for 0.1% of alloy gross mass, cerium accounts for 0.05% of alloy gross mass, surplus is plumbous.
The rare earth cerium is a kind of additive of monosodium glutamate formula, it is widely used in every field, and cerium and lead can form the high-melting point metal compound, and the intergranular of some lead-containing alloy that can neutralize is torn phenomenon, improve the hot-workability of lead-containing alloy, increase toughness and the creep resistance of lead-containing alloy.Rare earth cerium (Ce) has and calcium metal (Ca) has closely to the negative electrode current potential, and cerium has the hardness of lead, calcium, Xi Genggao and better mechanical performance.The adding of cerium can improve the impedance operator of plumbous anode film, improves the decay resistance of positive grid alloy, strengthens castability and the mechanical strength of positive grid alloy, and that improves maintenance-free lead accumulator simultaneously fills cycle performance deeply.
Embodiment 5
Present embodiment provides a kind of preparation method of anode plate for lead acid accumulator grid alloy, may further comprise the steps:
(1) takes by weighing the electrolytic lead of lead pan volume 80%, the lead in the lead pan is heated to fusing;
(2) lead pan is warmed up to 665 ℃, cerium is added in the lead pan in proportion, treat to stir after the cerium fusing;
(3) lead pan is cooled to 650 ℃, silver and aluminium are added in the lead pan in proportion, treat to stir after silver and aluminium all melt;
(4) lead pan is cooled to 430 ℃, remove the lead skim on lead pan surface, tin is joined in the lead pan in proportion, treat to stir after the tin fusing, again calcium is joined in the lead pan in proportion, stir after the fusing of band calcium, obtain anode plate for lead acid accumulator grid alloy.
The anode plate for lead acid accumulator grid alloy that is prepared by above-mentioned preparation method comprises: lead, calcium, tin, aluminium, silver, cerium; Wherein, calcium account for the alloy gross mass 0.07%, tin account for the alloy gross mass 1.2%, aluminium account for the alloy gross mass 0.05%, silver accounts for 0.05% of alloy gross mass, cerium accounts for 0.01% of alloy gross mass, surplus is plumbous.
Embodiment 6
Present embodiment provides a kind of preparation method of plumbous charcoal battery positive voltage grid alloy, may further comprise the steps:
(1) takes by weighing the electrolytic lead of lead pan volume 80%, the lead in the lead pan is heated to fusing;
(2) lead pan is warmed up to 650 ℃, cerium is added in the lead pan in proportion, treat to stir after the cerium fusing;
(3) lead pan is cooled to 625 ℃, silver and aluminium are added in the lead pan in proportion, treat to stir after silver and aluminium all melt;
(4) lead pan is cooled to 420 ℃, remove the lead skim on lead pan surface, tin is joined in the lead pan in proportion, treat to stir after the tin fusing, again calcium is joined in the lead pan in proportion, stir after the fusing of band calcium, obtain plumbous charcoal battery positive voltage grid alloy.
The anode plate for lead acid accumulator grid alloy that is prepared by above-mentioned preparation method comprises: lead, calcium, tin, aluminium, silver, cerium; Wherein, calcium account for the alloy gross mass 0.05%, tin account for the alloy gross mass 0.8%, aluminium account for the alloy gross mass 0.01%, silver accounts for 0.01% of alloy gross mass, cerium 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 raw material of wood-charcoal material is low, in the cyclic process battery dehydration serious, its cycle life is generally lower.Alloy material is used for the decay resistance that plumbous carbon storage battery can improve this battery in the present embodiment, reduces the overpotential of hydrogen evolution of battery, reduces the serious problem of dehydration of battery, improves the cycle life of battery.
Embodiment 7
Present embodiment provides a kind of preparation method of anode plate for lead acid accumulator grid alloy, may further comprise the steps:
(1) takes by weighing the electrolytic lead of lead pan volume 80%, the lead in the lead pan is heated to fusing;
(2) lead pan is warmed up to 650 ℃, silver and aluminium are added in the lead pan in proportion, treat to stir after silver and aluminium all melt;
(3) lead pan is cooled to 420 ℃, remove the lead skim on lead pan surface, join tin and bismuth in the lead pan in proportion, treat to stir after the fusing of tin and bismuth, again calcium is joined in the lead pan in proportion, stir after the fusing of band calcium, obtain anode plate for lead acid accumulator grid alloy.
The anode plate for lead acid accumulator grid alloy that is prepared by above-mentioned preparation method comprises: lead, calcium, tin, aluminium, silver, bismuth; Wherein, calcium account for the alloy gross mass 0.05%, tin account for the alloy gross mass 0.8%, aluminium account for the alloy gross mass 0.01%, silver accounts for 0.05% of alloy gross mass, bismuth accounts for 0.08% of alloy gross mass, surplus is plumbous.
Add the crystal grain that a small amount of bismuth can the refinement positive grid alloy in the anode plate for lead acid accumulator grid alloy, improve the intensity of positive grid alloy, strengthen the resistance to corrosion of positive grid alloy; Simultaneously, also improve hardness and the castability of positive grid alloy, reduced in the battery charging process gas and separated out, be conducive to the battery deep-circulating performance.
Embodiment 8
Present embodiment provides a kind of preparation method of anode plate for lead acid accumulator grid alloy, may further comprise the steps:
(1) takes by weighing the electrolytic lead of lead pan volume 80%, the lead in the lead pan is heated to fusing;
(2) lead pan is warmed up to 625 ℃, silver and aluminium are added in the lead pan in proportion, treat to stir after silver and aluminium all melt;
(3) lead pan is cooled to 430 ℃, remove the lead skim on lead pan surface, join tin and bismuth in the lead pan in proportion, treat to stir after the fusing of tin and bismuth, again calcium is joined in the lead pan in proportion, stir after the fusing of band calcium, obtain anode plate for lead acid accumulator grid alloy.
The anode plate for lead acid accumulator grid alloy that is prepared by above-mentioned preparation method comprises: lead, calcium, tin, aluminium, silver, bismuth; Wherein, calcium account for the alloy gross mass 0.07%, tin account for the alloy gross mass 1.2%, aluminium account for the alloy gross mass 0.05%, silver accounts for 0.01% of alloy gross mass, bismuth accounts for 0.05% of alloy gross mass, surplus is plumbous.
Embodiment 9
Present embodiment provides a kind of preparation method of plumbous charcoal battery positive voltage grid alloy, may further comprise the steps:
(1) takes by weighing the electrolytic lead of lead pan volume 80%, the lead in the lead pan is heated to fusing;
(2) lead pan is warmed up to 600 ℃, silver and aluminium are added in the lead pan in proportion, treat to stir after silver and aluminium all melt;
(3) lead pan is cooled to 440 ℃, remove the lead skim on lead pan surface, join tin and bismuth in the lead pan in proportion, treat to stir after the fusing of tin and bismuth, again calcium is joined in the lead pan in proportion, stir after the fusing of band calcium, obtain plumbous charcoal battery positive voltage grid alloy.
The anode plate for lead acid accumulator grid alloy that is prepared by above-mentioned preparation method comprises: lead, calcium, tin, aluminium, silver, bismuth; Wherein, calcium account for the alloy gross mass 0.1%, tin account for the alloy gross mass 1.6%, aluminium account for the alloy gross mass 0.03%, silver accounts for 0.1% of alloy gross mass, bismuth accounts for 0.01% 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 raw material of wood-charcoal material is low, in the cyclic process battery dehydration serious, its cycle life is generally lower.Alloy material is used for the decay resistance that plumbous carbon storage battery can improve this battery in the present embodiment, reduces the overpotential of hydrogen evolution of battery, reduces the serious problem of dehydration of battery, improves the cycle life of battery.
Embodiment 10
Present embodiment provides a kind of preparation method of plumbous charcoal battery positive voltage grid alloy, may further comprise the steps:
(1) takes by weighing the electrolytic lead of lead pan volume 80%, the lead in the lead pan is heated to fusing;
(2) lead pan is warmed up to 660 ℃, cerium is added in the lead pan in proportion, treat to stir after the cerium fusing;
(3) lead pan is cooled to 600 ℃, silver and aluminium are added in the lead pan in proportion, treat to stir after silver and aluminium all melt;
(4) lead pan is cooled to 430 ℃, remove the lead skim on lead pan surface, join tin and bismuth in the lead pan in proportion, treat to stir after the fusing of tin and bismuth, again calcium is joined in the 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 that is prepared by above-mentioned preparation method comprises: lead, calcium, tin, aluminium, silver, cerium, bismuth; Wherein, calcium account for the alloy gross mass 0.1%, tin account for the alloy gross mass 1.2%, aluminium account for the alloy gross mass 0.05%, silver accounts for 0.01% of alloy gross mass, cerium accounts for 0.05% of alloy gross mass, bismuth accounts for 0.08% of alloy gross mass, surplus is plumbous.
The plumbous charcoal battery positive voltage grid alloy that contains silver helps to reduce Pb and PbSO
4Reduction potential, make Pb
2+The easier metal Pb that is reduced to.When constant potential polarization, silver is to the inhibitory action that is formed with of PbO, can improve intensity and the creep strength of positive grid alloy, slow down positive grid alloy overaging effect in use, the interpolation of silver can suppress the growth of positive grid alloy corrosion layer, therefore is conducive to the deep discharge circulation of plumbous charcoal storage battery, overcome the generation of premature capacity loss phenomenon (PCL phenomenon), simultaneously, the interpolation of silver can increase overpotential of hydrogen evolution, and hydrogen separates out on the inhibition alloy cathode.
The rare earth cerium is a kind of additive of monosodium glutamate formula, it is widely used in every field, and cerium and lead can form the high-melting point metal compound, and the intergranular of some lead-containing alloy that can neutralize is torn phenomenon, improve the hot-workability of lead-containing alloy, increase toughness and the creep resistance of lead-containing alloy.Rare earth cerium (Ce) has and calcium metal (Ca) has closely to the negative electrode current potential, and cerium has the hardness of lead, calcium, Xi Genggao and better mechanical performance.The adding of cerium can improve the impedance operator of plumbous anode film, improves the decay resistance of positive grid alloy, strengthens castability and the mechanical strength of positive grid alloy, and that improves non-maintaining plumbous charcoal storage battery simultaneously fills cycle performance deeply.
Add the crystal grain that a small amount of bismuth can the refinement positive grid alloy in the plumbous charcoal battery positive voltage grid alloy, improve the intensity of positive grid alloy, strengthen the resistance to corrosion of positive grid alloy; Simultaneously, also improve hardness and the castability of positive grid alloy, reduced in the battery charging process gas and separated out, be conducive to the battery deep-circulating performance.
Plumbous charcoal battery positive voltage grid alloy among the embodiment has reduced the content of the calcium in the alloy on original Pb-Ca-Sn-Al alloy basis simultaneously, improved the content of tin, reduce the scaling loss that calcium content can reduce casting process, strengthened the positive grid alloy decay resistance, increase opourability and mechanical strength that tin content can improve positive grid alloy, improved the ability that recharges behind the battery deep discharge.
Embodiment 11
Present embodiment provides a kind of preparation method of plumbous charcoal battery positive voltage grid alloy, may further comprise the steps:
(1) takes by weighing the electrolytic lead of lead pan volume 80%, the lead in the lead pan is heated to fusing;
(2) lead pan is warmed up to 650 ℃, cerium is added in the lead pan in proportion, treat to stir after the cerium fusing;
(3) lead pan is cooled to 625 ℃, silver and aluminium are added in the lead pan in proportion, treat to stir after silver and aluminium all melt;
(4) lead pan is cooled to 420 ℃, remove the lead skim on lead pan surface, join tin and bismuth in the lead pan in proportion, treat to stir after the fusing of tin and bismuth, again calcium is joined in the 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 that is prepared by above-mentioned preparation method comprises: lead, calcium, tin, aluminium, silver, cerium, bismuth; Wherein, calcium account for the alloy gross mass 0.05%, tin account for the alloy gross mass 0.8%, aluminium account for the alloy gross mass 0.03%, silver accounts for 0.1% of alloy gross mass, cerium accounts for 0.1% of alloy gross mass, bismuth accounts for 0.01% of alloy gross mass, surplus is plumbous.
Embodiment 12
Present embodiment provides a kind of preparation method of plumbous charcoal battery positive voltage grid alloy, may further comprise the steps:
(1) takes by weighing the electrolytic lead of lead pan volume 80%, the lead in the lead pan is heated to fusing;
(2) lead pan is warmed up to 680 ℃, cerium is added in the lead pan in proportion, treat to stir after the cerium fusing;
(3) lead pan is cooled to 650 ℃, silver and aluminium are added in the lead pan in proportion, treat to stir after silver and aluminium all melt;
(4) lead pan is cooled to 440 ℃, remove the lead skim on lead pan surface, join tin and bismuth in the lead pan in proportion, treat to stir after the fusing of tin and bismuth, again calcium is joined in the 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 that is prepared by above-mentioned preparation method comprises: lead, calcium, tin, aluminium, silver, cerium, bismuth; Wherein, calcium account for the alloy gross mass 0.07%, tin account for the alloy gross mass 1.6%, aluminium account for the alloy gross mass 0.01%, silver accounts for 0.05% of alloy gross mass, cerium accounts for 0.01% of alloy gross mass, bismuth accounts for 0.05% of alloy gross mass, surplus is plumbous.
Plumbous charcoal storage battery is when operate as normal, and the lead ion in the electrolyte very easily at positive grid alloy oxidation reaction takes place and generates lead oxide.Lead oxide is non-conductive, thereby greatly reduces the performance of lead carbon battery.The positive grid alloy that present embodiment provides can stop and generates lead oxide on the positive grid alloy, and the metal level that this alloy material forms is finer and close, improved the structure of alloy material inside greatly, the structure cell crack of alloy inside diminishes, thereby improved the electric conductivity of alloy material, improve the decay resistance of alloy material greatly, reduced the overpotential of hydrogen evolution on 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, and still the overpotential of hydrogen evolution because of the raw material of wood-charcoal material is low, in the cyclic process battery dehydration serious, its cycle life is generally lower.Alloy material is used for the decay resistance that plumbous carbon storage battery can improve this battery in the present embodiment, reduces the overpotential of hydrogen evolution of battery, reduces the serious problem of dehydration of battery, improves the cycle life of battery.
Comparative Examples 1
This Comparative Examples provides a kind of preparation method of anode plate for lead acid accumulator grid alloy, may further comprise the steps:
(1) takes by weighing the electrolytic lead of lead pan volume 80%, the lead in the lead pan is heated to fusing;
(2) lead pan is warmed up to 600 ℃, aluminium is added in the lead pan in proportion, treat to stir after aluminium all melts;
(3) lead pan is cooled to 430 ℃, remove the lead skim on lead pan surface, tin is joined in the lead pan in proportion, treat to stir after the tin fusing, again calcium is joined in the lead pan in proportion, stir after the fusing of band calcium, obtain anode plate for lead acid accumulator grid alloy.
Anode plate for lead acid accumulator grid alloy to embodiment 10～12, Comparative Examples 1 carries out constant current corrosion weight loss and overpotential of hydrogen evolution test respectively:
(1) respectively various alloys are carried out the test of constant current corrosion weight loss, experimental technique is conventionally known to one of skill in the art, and experimental result sees Table 1:
Table 1 alloy constant current corrosion weight loss test result
By table 1 data as can be seen, the relative corrosion rate of the alloy among the embodiment 1,4,7,11 is all lower with respect to Comparative Examples 1.By embodiment 1,4,7,11 as can be seen, all lower according to the relative corrosion rate of the alloy of alloying component requirement preparation among the present invention, corrosion resistance is strong.As seen the adding of silver, cerium, bismuth is conducive to reduce the relative corrosion rate of alloy.
(2) respectively various alloys are carried out the overpotential of hydrogen evolution test, experimental technique is conventionally known to one of skill in the art, and experimental result sees Table 2:
Table 2 alloy overpotential of hydrogen evolution test result
The rule of table 2 data and table 1 data is similar, and the liberation of hydrogen current density of the alloy among the embodiment 1,4,7,11 is all lower with respect to Comparative Examples 1 as can be seen.As seen the liberation of hydrogen current density of the alloy of the requirement of the alloying component among the present invention preparation is lower, as seen the adding of silver, cerium, bismuth is conducive to suppress separating out of hydrogen, and gassing rate seldom, and then can stop the generation of the self discharge of the decomposition of water and battery, this maintenance-free performance for battery is very favorable.
Therefore, draw by above two experiments, alloy corrosion speed of the present invention is very little, and corrosion resistance is strong, and gassing rate seldom.
Be understandable that above execution mode only is the illustrative embodiments that adopts for principle of the present invention is described, yet 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 also are considered as protection scope of the present invention.
Claims (10)
1. an anode plate for lead acid accumulator grid alloy comprises lead, calcium, tin and aluminium, it is characterized in that, also comprises silver.
2. anode plate for lead acid accumulator grid alloy according to claim 1, it is characterized in that, described calcium account for the alloy gross mass 0.05%～0.10%, described tin account for the alloy gross mass 0.8%～1.6%, described aluminium account for the alloy gross mass 0.01%～0.05%, described silver accounts for 0.01%～0.1% of alloy gross mass, surplus is described lead.
3. anode plate for lead acid accumulator grid alloy according to claim 1 is characterized in that, also comprises cerium.
4. anode plate for lead acid accumulator grid alloy according to claim 3, it is characterized in that, described calcium account for the alloy gross mass 0.05%～0.10%, described tin account for the alloy gross mass 0.8%～1.6%, described aluminium account for the alloy gross mass 0.01%～0.05%, described silver account for the alloy gross mass 0.01%～0.1%, described cerium accounts for 0.01%～0.1% of alloy gross mass, surplus is described lead.
5. anode plate for lead acid accumulator grid alloy according to claim 1 is characterized in that, also comprises bismuth.
6. anode plate for lead acid accumulator grid alloy according to claim 5, it is characterized in that, described calcium account for the alloy gross mass 0.05%～0.10%, described tin account for the alloy gross mass 0.8%～1.6%, described aluminium account for the alloy gross mass 0.01%～0.05%, described silver account for the alloy gross mass 0.01%～0.1%, described bismuth accounts for 0.01%～0.08% of alloy gross mass, surplus is described lead.
7. anode plate for lead acid accumulator grid alloy according to claim 1 is characterized in that, also comprises cerium and bismuth.
8. anode plate for lead acid accumulator grid alloy according to claim 7, it is characterized in that, described calcium account for the alloy gross mass 0.05%～0.10%, described tin account for the alloy gross mass 0.8%～1.6%, described aluminium account for the alloy gross mass 0.01%～0.05%, described silver account for the alloy gross mass 0.01%～0.1%, described cerium account for the alloy gross mass 0.01%～0.1%, described bismuth accounts for 0.01%～0.08% of alloy gross mass, surplus is described lead.
9. according to any described anode plate for lead acid accumulator grid alloy of claim 1～8, it is characterized in that described lead acid accumulator is plumbous charcoal storage battery.
10. the preparation method of the described anode plate for lead acid accumulator grid of claim 7 alloy is characterized in that, may further comprise the steps:
(1) the described lead in the lead pan is heated to fusing;
(2) lead pan is warmed up to 650～680 ℃, adds described cerium;
(3) lead pan is cooled to 600～650 ℃, add described silver and described aluminium;
(4) lead pan is cooled to 420～440 ℃, remove lead skim, add described tin and described bismuth, obtain anode plate for lead acid accumulator grid alloy.
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