CN1147703A - 包括添加剂的电化学电池阴极 - Google Patents
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Abstract
本发明提出可用于包括阳极和电解质的电化学电池的阴极。该阴极包括二氧化锰活性材料和包括SnO2，Fe2O3TiO2，TiO2(P-25)，BaTiO3，K2TiO3，Nb2O5或SnO中的至少一种的添加剂，本发明阴极尤其适用于包括锌阳极和碱性电解质的电化学电池。
Description
广义地讲，本发明涉及包括阴极添加剂的电化学电池，特别是阴极由二氧化锰，一或多种氧化物添加剂及其他阴极组分构成的一次碱性电化学电池。
典型碱性电池包括圆筒形钢管壳体，其阴极在钢管壳体内表面形成并且包括二氧化锰作为活性材料，阳极位于电池中央并且包括锌，阳极和阴极间有隔膜，而碱性电解质同时接触阳极，阴极和隔膜。将导电的阳极集电装置插入阳极活性材料中并且用密封装置封住钢管壳体的开口端。
设计碱性电池的主要目标是提高电池的使用性能或者说延长电池的使用寿命。使用寿命或使用性能就是电池在给定负荷下放电到该电池不再能够用于达到其预期目的电压为止的时间区间。延长使用寿命的一种方法是增大电池内部体积以增加电池内活性材料量。但是，工商业用的电池外部尺寸是固定的，因此限制了增加电池内活性材料量的能力。为了在电池内包容更具活性的材料并同时保持电池外部尺寸，常规碱性电池的钢标牌已换成较薄的金属化塑料膜制成的标牌。因此，钢管壳体可扩大以提供更大的内部体积。通过采用更薄的塑料标牌，可明显延长典型减性电池的使用寿命。
延长电池使用寿命的另一方法是更好地利用电极材料。该方法已在US5,342,712(Mieczkowska et al.)中作了说明，其中提出采用锐钛矿二氧化钛作为加入以二氧化锰作为活性材料的阴极中的添加剂。尽管过去已努力延长了使用寿命，但寻求延长使用寿命的新方法仍是电池设计人员的主要目标。
本发明目的就是延长碱性电池的使用寿命，其中向阴极活性材料中加入一或多种氧化物添加剂。为了获得这种及其他优越性，并且根据本文具体说明和广泛描述的本发明目的，本发明电化学电池的阴极包括二氧化锰活性材料和包括SnO2，Fe2O3-TiO2，TiO2(P-25)，BaTiO3，K2TiO3，Nb2O5，Al2O3，WO3，CoTiO3，SrTiO3，SnO或V2O5中的一或多种的添加剂。本发明阴极尤其适用于包括锌阳极和碱性电解质的电化学电池中。
实施本发明的人员及本技术领域里的普通技术人员从以下的说明和权利要求书并结合说明书附图可以清楚地看出本发明的上述及其他特征，目的和优点。
图1为具有本发明结构的电化学电池实施例的剖面透视图。
图2为阴极中无添加剂的标准碱性电池与本发明在阴极中加添加剂的电化学电池的使用寿命比较图。
图3为阴极中无添加剂的标准碱性电池与本发明在阴极中加添加剂的电化学电池的使用寿命比较图。
图4为阴极中无添加剂的标准碱性电池与本发明在阴极中加添加剂的电化学电池的使用寿命比较图。
图5为阴极中无添加剂的标准碱性电池与本发明在阴极中加添加剂的电化学电池的使用寿命比较图。
图1示出了典型圆柱体碱性电池10的剖面图。碱性电池10包括圆筒形钢管壳体15，其一端敞开。金属化的塑料膜标牌16绕钢管壳体15外表面形成，只是钢管壳体15的端部除外。在钢管壳体15的闭口端是优选由有镀层的钢板构成的正极盖17。在正极盖17的周边上也有薄膜标牌16。
阴极20优选由二氧化锰，石墨，45％氢氧化钾溶液，去离子水，TEFLONTM溶液和添加剂构成，该阴极绕钢管壳体15的内侧表面形成。优选由非织造织物构成并用于防止任何固体颗粒在电池中迁移的隔膜30绕阴极20的内表面设置。由氢氧化钾构成的电解质40放在隔膜30的内部。优选由锌粉，胶凝剂和其他添加剂构成的阳极50放在电解质40内并使其与可由黄铜制成的集电装置60接触。
集电装置60与钢管壳体15开口端形成的黄铜铆钉70接触。在钢管壳体15开口端形成尼龙密封71以防止钢管壳体15中所含的活性成分漏出。尼龙密封71与金属垫圈72和优选用钢制成的电池内盖74接触。优选用有镀层的钢板制成的负极盖75的放置位置使其可与电池内盖74和经尼龙密封71中形成的孔与集电装置60接触的黄铜铆钉70接触。尼龙密封71使负极盖75与钢管壳体15之间电绝缘。
本发明的D尺寸或规格电池阴极优选由约71.76-81.66wt％(重量百分比，下同)MnO2，约8.52wt％石墨，约7.87wt％碱性溶液如45％KOH溶液，约0.36wt％去离子水，约1.49wt％粘合剂材料如TEFLONTM溶液和约0.1-10wt％添加剂构成。更优选的是，MnO2的Vt％在约76.76和80.76之间并且添加剂的Vt％在1和5之间以使MnO2和添加剂组合的wt％达到优选约81.76的常数。阴极中所用碱性溶液量同粘合剂材料量一样根据电池尺寸或规格变化。优选的是，添加剂是SnO2，但也可包括SnO，BaTiO3，K2TiO3，Al2O3，Fe2O3-TiO2，TiO2(P-25)，WO3，SrTiO3，CoTiO3，Nb2O5或V2O5。TiO2(P-25)是可从Degussa Corporation得到的煅制二氧化钛。与用沉淀技术制成的二氧化钛的大多数形式不同的是，TiO2(P-25)是在O2和H2存在下TiCl4经高温(＞1200℃)火焰水解而得到的。初级粒子从燃烧器出来后，在达到最终颗粒尺寸或粒径和分布的冷却过程中，会进行凝结。一系列的旋风分离器将固体材料与反应气体分开。然后将该产物进行蒸汽处理以除去作为反应副产物的HCl。TiO2(P-25)是无孔隙的，其颗粒形状基本上为立方体，其边缘是园的。TiO2(P-25)的结晶研究表明其中存在无定形，锐钛矿和金红石形式的多相。锐钛矿与金红石之比为70∶30和80∶20之间。
称量出所需材料并混入MnO2，添加剂和石墨后将其掺混起来而获得均匀混合物，即可制成阴极。然后，将去离子水，TEFLONTM溶液和KOH溶液与这些无水的阴极组分混合制成均匀阴极混合物。之后，将该阴极混合物放在钢管壳体15内并模制成环绕圆筒形状。
如上所述，已发现加入少量上面所列添加剂即可明显延长碱性电化学电池的使用寿命。以下比较例说明了本发明获得的优点。
比较例1
按上述制成对比碱性D尺寸电池，只是在阴极中不包括添加剂，而其wt％由另外的MnO2提供。再制成阴极中包括1.6wt％SnO2的D尺寸第一试验电池，阴极中包括Fe2O3-TiO2添加剂的D尺寸第二试验电池和阴极中包括TiO2(P-25)添加剂的D尺寸第三试验电池。四种电池连续与1.0欧姆负荷相连并在一段时间内测定电池电压。图2示出了四种电池的时间与放电电压的关系线图。在0.75伏断电电压下，包括SnO2添加剂的第一试验电池的使用寿命比对比电池要长24％，包括Fe2O3-TiO2添加剂的第二试验电池和包括TiO2(P-25)添加剂的第三试验电池的使用寿命比对比电池要长9％。
比较例2
在制成无添加剂的对比电池的同时，制成包括BaTiO3添加剂的D尺寸第四试验电池和包括K2TiO3添加剂的D尺寸第五试验电池。每天将这三种电池与2.2欧姆负荷连接1小时。图3表明了三种电池经过的时间与放电电压的关系线图。对于1.00伏断电电压，包括K2TiO3添加剂的第五试验电池的使用寿命比对比电池要长10％，包括BaTiO3添加剂的第四试验电池的使用寿命比对比电池要长8％。而在O.80伏断电电压下，包括K2TiO3添加剂的第五试验电池的使用寿命要比对比电池长13％，第四试验电池的使用寿命要比对比电池长10％。
比较例3
制成包括Nb2O5添加剂的D尺寸第六试验电池和不包括添加剂的对比电池并用其进行2.2欧姆的轻负载断续闪光(LIF)试验，其中每天连续8小时内每小时将各电池与2.2欧姆负荷连接4分钟。图4表明了第六试验电池和对比电池经过的时间与放电电压的关系线圈。在1.00伏断电电压下，第六试验电池的使用寿命与对比电池相比并没有改进或延长。但是，在0.90伏断电电压下，第六试验电池的使用寿命比对比电池要长7％。
比较例4
按上述采用同于对比D尺寸电池的wt％制成对比碱性AA尺寸电池，只是阴极中不包括添加剂，而其wt％由另外的MnO2提供。再制成阴极中包括1.6wt％SnO2的AA尺寸第七试验电池和包括TiO2添加剂的AA尺寸第八试验电池。用三种电池进行IEC闪光试验，其中将各电池与1.8欧姆负荷相连并进行15秒ON和45秒OFF循环试验(即每一循环等于1分钟)，ON/OFF循环期间测定电池电压。图5表明了三种电池循环次数与电池放电电压的关线线图。在0.9伏的断电电压下，包括SnO2添加剂的第七试验电池的使用寿命比对比电池要长25％，包括TiO2添加剂的第八试验电池的使用寿命比对比电池要长15％。正如以上比较例所述，用SnO2，Fe2O3-TiO2，TiO2(P-25)，BaTiO3，K2TiO3和Nb2O5添加剂可使碱性电化学电池的使用寿命明显延长或者说使其使用性能明显提高。而且，采用SnO，AL2O3，WO3，SrTiO3，CoTiO3和V2O5也已明显延长了使用寿命。
虽然以上比较例是按D和AA尺寸的电池进行说明的，但本技术领域里的普通技术人员会看到：使用寿命的延长或使用性能的提高与电池尺寸是没有关系的。由于上列添加剂中某些添加剂在连续试验中要比其他添加剂的使用性能好，而在断续试验中其他添加剂的使用性能又好，因此将这些添加剂组合起来以延长电化学电池连续和断续使用时的总体使用寿命或者说提供其总体使用性能也是符合要求的。
对实施本发明的人员和本技术领域里的普通技术人员而言，在本发明构思范围内还可作出各种改进和变化。因此，本发明的范围应由权利要求书并依据法律规定的解释范围界定。
Claims (9)
1.包括阳极，阴极和电解质的电化学电池，其中所述阴极包括二氧化锰活性材料和包括Fe2O3-TiO2的添加剂。
2.权利要求1的电化学电池，其中所述阳极包括锌并且所述电解质为碱性电解质。
3.权利要求1的电化学电池，其中所述添加剂构成所述阴极的约0.1-10wt％。
4.包括阳极，阴极和电解质的电化学电池，其中所述阴极包括二氧化锰活性材料和包括煅制TiO2的添加剂。
5.包括阳极，阴极和电解质的电化学电池，其中所述阴极包括二氧化锰活性材料和包括锐钛矿和金红石TiO2组合物的添加剂。
6.权利要求5的电化学电池，其中所述锐钛矿和金红石TiO2组合物中包括至少20％金红石TiO2。
7.包括阳极，阴极和电解质的电化学电池，其中所述阴极包括二氧化锰活性材料和包括Nb2O5的添加剂。
8.权利要求7的电化学电池，其中所述添加剂构成所述阴极的约0.1-10wt％。
9.包括阳极，阴极和电解质的电化学电池，其中所述阴极包括二氧化锰活性材料和包括SnO的添加剂。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/485,424 US5599644A (en) | 1995-06-07 | 1995-06-07 | Cathodes for electrochemical cells having additives |
| US485424 | 1995-06-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1147703A true CN1147703A (zh) | 1997-04-16 |
Family
ID=23928117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96106837A Pending CN1147703A (zh) | 1995-06-07 | 1996-06-07 | 包括添加剂的电化学电池阴极 |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5599644A (zh) |
| EP (1) | EP0747982B1 (zh) |
| JP (1) | JP4015716B2 (zh) |
| KR (1) | KR970000136A (zh) |
| CN (1) | CN1147703A (zh) |
| CA (1) | CA2178423A1 (zh) |
| DE (1) | DE69606352T2 (zh) |
| HK (1) | HK1007408A1 (zh) |
| SG (1) | SG68585A1 (zh) |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1098540C (zh) * | 1996-04-20 | 2003-01-08 | 瓦尔达电池股份公司 | 用于碱性原电池的阴极添加剂 |
| CN100490218C (zh) * | 2000-03-31 | 2009-05-20 | 索尼株式会社 | 隔片、凝胶电解质、非水电解质、电极和使用它们的电池 |
| CN103636031A (zh) * | 2012-06-25 | 2014-03-12 | 松下电器产业株式会社 | 碱性电池 |
| CN103636031B (zh) * | 2012-06-25 | 2016-06-22 | 松下知识产权经营株式会社 | 碱性电池 |
| CN108778500A (zh) * | 2016-03-08 | 2018-11-09 | 国立研究开发法人科学技术振兴机构 | 催化剂及其应用 |
| US11045791B2 (en) | 2016-03-08 | 2021-06-29 | Japan Science And Technology Agency | Catalyst and use of same |
| CN108281607A (zh) * | 2018-02-08 | 2018-07-13 | 中银（宁波）电池有限公司 | 改性电解二氧化锰及其制备方法 |
| CN108281607B (zh) * | 2018-02-08 | 2020-09-08 | 中银（宁波）电池有限公司 | 改性电解二氧化锰及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4015716B2 (ja) | 2007-11-28 |
| DE69606352T2 (de) | 2000-08-24 |
| KR970000136A (ko) | 1997-01-21 |
| SG68585A1 (en) | 1999-11-16 |
| EP0747982B1 (en) | 2000-01-26 |
| HK1007408A1 (en) | 1999-04-09 |
| JPH09106811A (ja) | 1997-04-22 |
| CA2178423A1 (en) | 1996-12-08 |
| EP0747982A1 (en) | 1996-12-11 |
| DE69606352D1 (de) | 2000-03-02 |
| US5599644A (en) | 1997-02-04 |
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