CN103299449A - 无汞纽扣电池的外壳 - Google Patents
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- 239000010949 copper Substances 0.000 claims abstract description 42
- 229910052802 copper Inorganic materials 0.000 claims abstract description 41
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 24
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010959 steel Substances 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052738 indium Inorganic materials 0.000 claims abstract description 14
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052718 tin Inorganic materials 0.000 claims abstract description 13
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 11
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
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Abstract
本发明涉及制备用于无汞纽扣电池（100）外壳的在内侧设置有铜合金（111）的碗状外壳半部（101）的方法。在该方法中，镀有一层镍（109）、一层铜和位于其中间的一层钢或优质钢（101）的复合材料在铜一侧设置有由至少一种选自锡、锌、铟和铋的金属形成的附加层。由该复合材料形成碗状外壳半部（101），其中所述镍层形成所述碗状外壳半部（101）的外侧，而附加层形成所述碗状外壳半部（101）的内侧。随后对如此形成的外壳半部（101）进行热处理。其中调节温度使得所述至少一种来自附加层的金属与相邻的铜层形成合金。此外还描述了根据该方法可以制备的外壳半部（101）和具有这些外壳半部(101)的纽扣电池(101)。
Description
本发明涉及制备无汞纽扣电池外壳的在内侧设置有铜合金的碗状外壳半部的方法，以及根据该方法可以制备的外壳半部和具有这些外壳半部的纽扣电池。
纽扣电池通常具有由两个外壳半部，即一个通常以碗状的形式形成的电池杯和一个通常同样以碗状的形式形成的电池盖组成的外壳。举例来说，其可以由作为冲拉部件的镀镍的深拉金属片制备。但是更经常地，作为外壳材料使用镀有一层镍、一层铜和位于其中间的一层钢或优质钢的复合材料（所谓的三金属）。三金属的外壳半部例如见于JP 61061364 A1。在外壳半部之间配置的塑料环通常同时用作密闭层和用作隔离层，其将外壳半部在空间和电学上相互分开。通常将纽扣电池的电池杯正极化，而将电池盖负极化。这样的电池的液体密封大多通过将电池杯的边缘卷边而实现。
作为负电极，纽扣电池通常含有由锌粉构成的糊或凝胶。作为正的相反电极，则考虑例如气体扩散电极（对于锌/空气-电池）或替代性地例如氧化锰或氧化银。
在上述电化学体系中，作为电解液通常使用碱性电解液，特别是浓缩的水性氢氧化钾。碱性电解液的存在既有优点，也有缺点。缺点特别在于，锌可以在碱性环境中非常容易地与水反应而生成氢气。由于产生氢气，可以将电池不可逆地损坏掉。如今，通过加入汞来调节锌与水在碱性锌电池中的反应。但是，由于汞的毒性和环境有害性，在将来不再采用这种做法。
在现有技术中已知无汞纽扣电池，其中用铜锡合金层、铜锌合金层或铜铟合金层覆盖纽扣电池盖的内侧，以便提高氢过电压，并且在不存在汞的情况下也将氢气产生保持在可接受的程度。但是，所述合金具有低的可锻性，因此不可能在没有破坏合金层的情况下制备深拉伸的盖。
具有权利要求1特征的本方法提供了一种简单和巧妙的可能途径来避免这些问题。本发明方法的优选实施方式在从属权利要求2和3中给出。此外，本发明也包括具有权利要求4特征的碗状外壳半部和具有权利要求5特征的纽扣电池。所有权利要求的措辞都与本描述的内容相关。
本发明的方法用于制备无汞（不含汞）纽扣电池外壳的在内侧设置有铜合金的碗状外壳半部。其通常包括下列步骤：
（1）在一个步骤中提供了有镀层的复合材料，其中该复合材料包括一层镍、一层铜和位于其中间的一层钢或优质钢。在该复合材料的铜一侧设置有由金属锡、锌、铟和铋的一种或这些金属的合金形成的附加层。该附加层优选镀在铜层上。
镀层是指金属加工中的一种做法，其中将一种金属用另一种通常相对较贵重的金属覆盖住。在上述的复合材料的情况中，将钢层用镍和酮覆盖住。其中，金属之间的连接应该尽可能地不可分离。为此使用多种不同的技术，例如轧制或焊接金属箔或电化学沉积金属析出物。后者的情况称为电镀。
作为复合材料，根据本发明优选使用前面已经提到的三金属。三金属是特别为纽扣电池的外壳研制出的特殊镀层。通常，低碳钢或不生锈的优质钢的薄膜用作载体。复合材料的厚度优选在0.05-0.25μm的范围。其中镍层通常占据了复合材料厚度的1-15%，铜层占据了5-30%。相应地，钢膜在复合材料的厚度中的比例为55-94%。
此外当然还有所提及的由金属锡、锌、铟和铋的一种或这些金属的合金形成的层。优选通过电镀的方法将其施加到复合材料的铜一侧上，即通过电镀层的方法。在优选的实施方式中，其平均厚度为0.5-2μm。
（2）根据（1）提供的、在铜一侧涂覆的复合材料优选以无端条带的形式存在。在第二步骤中，由该复合材料形成碗状外壳半部，其中与介绍的现有技术的实施方式相一致，所述镍层形成所述碗状外壳半部的外侧，而由金属锡、锌、铟和铋的一种或这些金属的合金组成的附加层形成所述碗状外壳半部的内侧。所述碗状外壳半部优选通过深拉方法或冲压方法而形成。
（3）作为另外的步骤，本发明的方法包括热处理根据（2）形成的外壳半部。根据本发明，其在一定的温度下进行，其中在该温度下由金属锡、锌、铟和铋的一种或这些金属的合金形成的附加层与铜层的铜形成合金。
所述热处理优选的温度为至少100℃。进行所述热处理的最低温度特别优选为200℃。特别优选的热处理温度在200-400℃的范围。在该温度下，金属锡、锌、铟和/或铋可以扩散到铜层中，相应地形成相应金属的铜合金。因为所述铜合金在形成所述碗状外壳半部之后才产生，其较低的可锻性没有负面作用。
在所述金属扩散到复合材料的铜层时，铜层和所描述的附加层之间的界限变得模糊。在该过程中，所述铜层和所描述的附加层统一成新的层。
但是，所述新的层优选不是由具有均匀的、统一组层的合金组成的。替代性地，根据热处理时所选择的参数（特别是“温度”和“时间”的参数），在上述扩散过程中可以形成浓度梯度。通过相应地分析热处理过的外壳半部可以证明该梯度的存在。
从上述的最低温度100℃，优选为200℃起，所述金属锡、锌、铟和铋才以值得注意的程度扩散到铜层中。低于上述温度时过于强烈地抑制了扩散动力学。
所述热处理优选在1-10小时的时间范围进行。
通过本发明的方法可以制备碗状外壳半部，该外壳半部由镀层的包括一层镍、一层钢或优质钢和一层与至少一种选自锡、锌、铟和铋的金属形成合金的铜的复合材料而制备，其中所述镍层形成所述碗状外壳半部的外侧，而铜合金层形成所述碗状外壳半部的内侧。本发明也包括这些外壳半部。
正如已经提及的，在优选的实施方式中，在形成内侧的层的内部绝对不可能找到到处相同浓度的元素锡、锌、铟和/或铋。相应地，本发明的外壳半部的特点也特别在于，在形成内侧的层的内部，铜的浓度随着与钢层距离的增加而减小，而至少一种选自锡、锌、铟和铋的元素的浓度在相同方向上增加。
换句话说，在铜合金层的内部，铜在向着钢层的方向富集，而在向着杯内部的方向贫化。富集这里是指，在钢层附近的局部铜含量大于该层中的平均铜含量，而贫化是指，朝向杯内部的局部铜含量低于在该层中的平均铜含量。其中，所述平均铜含量由在该层中的铜含量与层中所有含量的总和的重量比例乘以系数100而得到。
本发明的碗状外壳半部优选是指纽扣电池的电池盖。
本发明的纽扣电池包含具有这样的外壳半部，特别是这样的电池盖的外壳。此外，该外壳还包括对应于本发明的外壳半部的第二外壳半部，其中该第二外壳半部优选是电池杯。
本发明的纽扣电池优选是具有含锌阳极（Anode）的纽扣电池，特别是锌/空气-纽扣电池。其中，特别是在本发明的碗状外壳半部中配置了含锌阳极。
本发明的其它特征由下面的附图描述而得到，借此再次具体地阐述本发明。此处明确强调，在本发明的实施方式中可以在每种情况下以其本身或连同一种或多种其它描述的特征来实现在本申请中描述的所有任选的本发明方法和其它本发明主题的方面。下面描述的优选实施方式仅仅用于说明和用于更好地理解本发明，而不能受限制地理解。
图1a展示了本发明的纽扣电池100的实施方式的横截面示意图。其具有电池盖101，该电池盖101以碗状外壳半部的形式而形成，并按照上述方法而制备。此外，其以对应于电池盖101的外壳半部的形式包含同样碗状的电池杯102。这些一起形成了该纽扣电池100的外壳。在电池盖101中，配置了锌糊103作为负极活性物料。其不含有汞。密封层104使电池套101和电池杯102彼此隔离开，并同时对外密闭了外壳。它围住了电池盖101的切边105。在电池杯102的底部区域配置了气体扩散电极106。其通过隔膜107与锌糊103分开。电池杯102的底部具有空气进入开口108。所描绘的纽扣电池相应地是锌/空气-纽扣电池。
图1b展示了在图1a中描绘的的钮扣电池100的放大剪切图。以剪切图的形式描绘了电池杯102和电池盖101以及密封层104、锌糊103、气体扩散电极106和隔膜107。电池盖101由包括一层镍109、一层钢110和一个包含铜和铜锡合金的层111的复合材料而组成。每个层只有在放大的示意图中描绘。
具有铜和铜锡合金的层111形成了电池盖101的内侧，并与锌糊103直接接触。镍层109形成了电池盖的外侧。
电池盖101由在铜一侧设置了附加锡层的三金属而制备。在由这种材料冲压出电池盖101之后，将其在约200℃的温度加热两个小时。在此过程中，由三金属的铜一侧和其上配置的附加锡层形成了包含铜和铜锡合金的层111。通过扩散在产生的(共同)层111内部形成了浓度落差。已经确定，在层111内部铜在向着钢层的方向上富集。与此相反，在向着碗内部的方向锡的浓度增加。在紧贴层10和层111之间的边界处甚至仍然可以发现未形成合金的铜。因此解释了为什么使用表述层111“包含铜和由铜锡合金组成”。在三金属的铜一侧上的锡层在热处理前的厚度在0.2-5μm的范围。锡层通过电镀技术沉积在三金属上。
Claims (5)
1. 制备用于无汞纽扣电池外壳的在内侧设置有铜合金的碗状外壳半部的方法，其包括下列步骤
（1）提供镀有一层镍、一层铜和位于其中间的一层钢或优质钢的复合材料，其在铜一侧设置有包含至少一种选自锡、锌、铟和铋的金属的附加层，
（2）由所述复合材料形成碗状外壳半部，其中所述镍层形成所述碗状外壳半部的外侧，而附加层形成所述碗状外壳半部的内侧，
（3）在其中所述至少一种选自锡、锌、铟和铋的金属与铜层的铜形成合金的温度下热处理所述外壳半部。
2. 根据权利要求1的方法,其特征在于,所述热处理的温度为至少100℃，优选在200-400℃的范围。
3. 根据权利要求1或2的方法,其特征在于,所述热处理在1-10小时的时间范围进行。
4. 用于无汞纽扣电池外壳的碗状外壳半部，其由包括一层镍、一层钢和一层与至少一种选自锡、锌、铟和铋的金属形成合金的铜的复合材料组成，其中所述镍层形成所述碗状外壳半部的外侧，而铜合金层形成所述碗状外壳半部的内侧，其特征在于，在形成碗状外壳半部的内侧的层的内部铜的浓度随着与钢层距离的增加而减小，而所述至少一种选自锡、锌、铟和铋的元素的浓度在相同方向上增加。
5. 具有包括根据权利要求4的外壳半部的外壳的纽扣电池。
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| DE102010062001.7 | 2010-11-25 | ||
| DE102010062001A DE102010062001A1 (de) | 2010-11-25 | 2010-11-25 | Gehäuse für quecksilberfreie Knopfzellen |
| PCT/EP2011/070635 WO2012069449A1 (de) | 2010-11-25 | 2011-11-22 | Gehäuse für quecksilberfreie knopfzellen |
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| EP (1) | EP2643868B1 (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103866359A (zh) * | 2014-03-25 | 2014-06-18 | 株洲永盛电池材料有限公司 | 一种无汞扣式电池负极盖材料及其制备方法 |
| CN110364645A (zh) * | 2019-06-18 | 2019-10-22 | 深圳清华大学研究院 | 无汞纽扣电池负极盖材料及其制备方法和应用 |
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| JP6484829B2 (ja) * | 2016-01-12 | 2019-03-20 | パナソニックＩｐマネジメント株式会社 | コイン形リチウム電池 |
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- 2011-11-22 US US13/885,528 patent/US20130230763A1/en not_active Abandoned
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| CN110364645A (zh) * | 2019-06-18 | 2019-10-22 | 深圳清华大学研究院 | 无汞纽扣电池负极盖材料及其制备方法和应用 |
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| DE102010062001A1 (de) | 2012-05-31 |
| EP2643868B1 (de) | 2015-07-22 |
| EP2643868A1 (de) | 2013-10-02 |
| US20130230763A1 (en) | 2013-09-05 |
| WO2012069449A1 (de) | 2012-05-31 |
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