CN1147702A - 阴极包括二氧化锡添加剂的碱性电池 - Google Patents

阴极包括二氧化锡添加剂的碱性电池 Download PDF

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CN1147702A
CN1147702A CN96106836A CN96106836A CN1147702A CN 1147702 A CN1147702 A CN 1147702A CN 96106836 A CN96106836 A CN 96106836A CN 96106836 A CN96106836 A CN 96106836A CN 1147702 A CN1147702 A CN 1147702A
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battery
negative electrode
additive
electrochemical cell
alkaline
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W·M·施韦尔布特
J·C·纳迪
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Edgewell Personal Care Brands LLC
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Eveready Battery Co Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/06—Electrodes for primary cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0014—Alkaline electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Primary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

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

阴极包括二氧化锡添加剂的碱性电池
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，二氧化锡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二氧化锡添加剂。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％SnO2添加剂构成。更优选的是，MnO2的wt％在约76.76和80.76之间并且SnO2的wt％在1和5之间以使MnO2和SnO2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。
称量出所需材料并混入MnO2，SnO2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。两种电池连续与1.0欧姆负荷相连并在一段时间内测定电池电压。图2示出了两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％。
比较例2
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尺寸第二试验电池。用两种电池进行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3表明了两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添加剂的第二试验电池的使用寿命比对比电池要长25％。
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。
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 (5)

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SnO2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.权利要求3的电化学电池，其中所述添加剂构成所述阴极的约1-5wt％。
5.权利要求4的电化学电池，其中所述添加剂构成所述阴极的约1-2wt％。
CN96106836A 1995-06-07 1996-06-07 阴极包括二氧化锡添加剂的碱性电池 Pending CN1147702A (zh)

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US479590 1995-06-07
US08/479,590 US5501924A (en) 1995-06-07 1995-06-07 Alkaline cell having a cathode including a tin dioxide additive

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JP (1) JPH09106810A (zh)
KR (1) KR970004128A (zh)
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CA (1) CA2178421A1 (zh)
DE (1) DE69603671T2 (zh)
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JPH09106810A (ja) 1997-04-22
KR970004128A (ko) 1997-01-29
DE69603671T2 (de) 2000-03-23
HK1007406A1 (en) 1999-04-09
DE69603671D1 (de) 1999-09-16
US5501924A (en) 1996-03-26
EP0747983A1 (en) 1996-12-11
TW302560B (zh) 1997-04-11
EP0747983B1 (en) 1999-08-11
CA2178421A1 (en) 1996-12-08

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