CN1074949A - 免维护密闭铅酸蓄电池超低锑板栅合金材料 - Google Patents
免维护密闭铅酸蓄电池超低锑板栅合金材料 Download PDFInfo
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- CN1074949A CN1074949A CN92100587A CN92100587A CN1074949A CN 1074949 A CN1074949 A CN 1074949A CN 92100587 A CN92100587 A CN 92100587A CN 92100587 A CN92100587 A CN 92100587A CN 1074949 A CN1074949 A CN 1074949A
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- 239000000956 alloy Substances 0.000 title claims abstract description 32
- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 11
- 239000002253 acid Substances 0.000 title claims abstract description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 10
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 239000011159 matrix material Substances 0.000 claims abstract description 7
- 229910052718 tin Inorganic materials 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 238000005728 strengthening Methods 0.000 claims abstract description 6
- 229910052745 lead Inorganic materials 0.000 claims description 6
- 239000002141 low-antimony alloy Substances 0.000 claims description 6
- 238000012423 maintenance Methods 0.000 claims description 6
- 230000002787 reinforcement Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 4
- 229910052782 aluminium Inorganic materials 0.000 abstract description 4
- 238000005266 casting Methods 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 239000001999 grid alloy Substances 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 description 17
- 239000002131 composite material Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000003623 enhancer Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic 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
本发明是一种免维护密闭铅酸蓄电池超低锑板
栅合金材料。该合金材料由Pb-0.3~0.75%Sb和强
化基体元素组成,其强化基体元素可以是K,Na,Li,
Sn,S,Ag,Cu,Al中的至少一种,其中K,Na,Li的
含量分别为0.05~2%,Sn,S,Ag,Cu,Al含量分别
为0.01~0.9%。该合金材料具有良好的机械性能、
耐腐蚀性、铸造工艺性和优良的电化学性能。用其可
以组装4V8Ah至12V40Ah的系列蓄电池,电池的
各项性能指标均超过标准要求。
Description
本发明涉及一种铅基合金材料,特别是用于免维护密闭铅酸蓄电池的超低锑板栅合金材料。
铅酸蓄电池中所使用的铅基含锑板栅合金,其锑含量一般高于6%。这种合金的机械强度较高,而且由于Sb的含量较高,使得合金的耐腐蚀性差,析氢量高,因而无法在密闭蓄电池中使用,近年来,国内外在此项研究中,采用含锑量为1.8~4%的低锑合金,然而随着Sb含量的降低,合金的实际凝固范围变宽,形成很宽的双相区,合金表现出流动性的急剧下降,甚至在凝固过程中产生微观裂纹,造成合金机械强度下降。为此,人们加入以As为主的变晶剂,生产Pb-Sb-Aa合金,而As及其氧化物是剧毒物质,受到环境保护的严格限制,同时As的加入又严重地影响了合金的韧性,使材料的工艺性下降。
本发明的目的即为提供一种Sb含量低,强化基体元素不含有毒物质的超低锑板栅合金材料方案,以满足免维护密闭铅酸蓄电池对板栅材料的要求。
本发明的目的是这样实现的。
免维护密闭酸蓄电池超低锑板栅合金材料由Pb,Sb和强化基体元素组成。其中:
(a)Sb含量为0.3~0.75%
(b)强化基体元素为:K,Na,Li,Sa,S,Ag,C1或Al中的至少一种,K,Na,Ll的含量分别为0.05~2%;Sn,S,Ag,Cu,Al的含量分别为0.01~0.9%。
(c)其余为Pb。
该合金材料板栅可以通过下述方法制得:将Pb和Sb入坩锅内,用电炉加热至480~500℃,形成合金溶液,然后再将由Na.Ca.Sn.K.Ll.S.Ag或Al组成的复合强化剂加入,进行配制,并保温11分钟,然后将合金溶液浇入石墨模具制成板栅,再经过3-5天的化成时间,即可用来组装蓄电池。
本发明中的复合强化剂是以变晶,强化,增加流动性为一体的三元金属化合物,当溶于0.3~0.75%的Pb-Sb合金溶液时,复合强化剂与Pb,Sb是一个重结合过程。微量的变质元素Cu,S或Ag与Pb可形成难溶化物析出,在溶液中形成大量的固相质点作为异形核核心,所选择的变质元素Cu,S,Ag与Pb同属一种晶格类型,并且匹配度、变质效果好,从而赋予合金以良好的韧性,使合金组织致密细化,提高了抗腐蚀力;复合强化剂中强化元素Li,K或Na可与铅基体存在着一定的固溶度,部分元素进入铅晶格,形成固溶体,固溶原子大于Pb的八面体间隙而产生畸变,造成材料的强化。
强化相元素的选择是根据应变能力与固溶体稳定性的关系,较小原子半径的元素进入铅基体,才能进行较稳定的固溶体,在合金冷却时部分溶质元素析出,使金属化合物点分布于铅基体,所形成的PbA3型化合物的硬度远远大于纯Pb,晶界析出物是影响晶界移迁的主要因素,加入锡可以影响铅的晶界移动速度,随着锡在铅中的含量增加,晶界移动速度随之降低,从而晶界的钉扎使材料的强度明显提高。由于锑的含量很小,也使得合金具有较高的析氢过电位。另外经过X射线光电子谱分析证明,合金的腐蚀产物为活性物质接触良好的PbO2腐蚀膜,而不含PbSO4。
本发明所提供的免维护密闭铅酸蓄电池超低锑板栅合金,具有良好的机械性能,耐腐蚀性,铸造工艺性以很少的析氢量等优良的电化学性能。用其组装成12VAh的密闭电池经实测证明,它的容量达107.3;高速放电达31小时,密封反应效率达99.3%;深循环寿命高达420次。
本发明的合金材料可以有多种实施方案,如下表所列:
采用上述实施例中的合金经熔化浇铸完成的正、负极栅板,可以组装从4V8Ah至12V40Ah的系列密闭免维护蓄电池,其技术指标均可达到:容量98~106;高速放电28~31小时;密闭反映效率93~99%;寿命360~405小时。
Claims (5)
1、一种免维护密闭铅酸蓄电池超低锑板栅合金材料,其特征在于合金材料由Pb,Sb和强化基体元素组成,其中:
(a)Sb含量为0.3~0.75%;
(b)强化基体元素为:K,Na,Li,Sn,S,Ag,Cu或Al中的至少一种:K,Na,Li的含量分别为0.05~2%;Sn,S,Ag,Cu,Al的含量分别为0.01~0.9%;
(c)其余为Pb。
2、按照权利要求1所述的合金材料,其合金材料组成的特征在于:Pb-0.4%Sb-0.08Ll-0.02%S。
3、按照权利要求1所述的合金材料,其合金材料组成的特征在于:Pb-0.6%Sb-0.04%K-0.05%Na-0.2%Sa。
4、按照权利要求1所述的合金材料,其合金材料组成的特征在于:Pb-0.4%Sb-0.1%Na-0.05%Cu。
5、按照权利要求1所述的合金材料,其合金材料组成的特征在于:Pb-0.75%Sb-0.02%Ag-0.05%Na。
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CN92100587A CN1028439C (zh) | 1992-01-31 | 1992-01-31 | 免维护密闭铅酸蓄电池超低锑板栅合金材料 |
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---|---|---|---|
CN92100587A CN1028439C (zh) | 1992-01-31 | 1992-01-31 | 免维护密闭铅酸蓄电池超低锑板栅合金材料 |
Publications (2)
Publication Number | Publication Date |
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CN1074949A true CN1074949A (zh) | 1993-08-04 |
CN1028439C CN1028439C (zh) | 1995-05-17 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1039922C (zh) * | 1995-12-22 | 1998-09-23 | 陈有孝 | 超钙合金材料 |
CN110144494A (zh) * | 2019-06-06 | 2019-08-20 | 江苏海瑞电源有限公司 | 一种高性能护套用铅基合金及其制备方法 |
-
1992
- 1992-01-31 CN CN92100587A patent/CN1028439C/zh not_active Expired - Fee Related
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1039922C (zh) * | 1995-12-22 | 1998-09-23 | 陈有孝 | 超钙合金材料 |
CN110144494A (zh) * | 2019-06-06 | 2019-08-20 | 江苏海瑞电源有限公司 | 一种高性能护套用铅基合金及其制备方法 |
CN110144494B (zh) * | 2019-06-06 | 2021-08-06 | 江苏海瑞电源有限公司 | 一种高性能护套用铅基合金及其制备方法 |
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CN1028439C (zh) | 1995-05-17 |
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