CN1169598A - 一次电池 - Google Patents

一次电池 Download PDF

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CN1169598A
CN1169598A CN97110563A CN97110563A CN1169598A CN 1169598 A CN1169598 A CN 1169598A CN 97110563 A CN97110563 A CN 97110563A CN 97110563 A CN97110563 A CN 97110563A CN 1169598 A CN1169598 A CN 1169598A
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CN1120536C (zh
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H·U·何塞
H·J·费斯纳
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WALTA BATTERY AG
VARTA Batterie AG
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    • H—ELECTRICITY
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Abstract

发明涉及一种具有含无汞锌粉末的阳极胶滞体、碱性电解质和通过一个分隔器与电解质隔离的、含二氧化锰的阴极材料的一次电池,其特征在于,阴极材料含有固态的盐状钙化合物。

Description

一次电池
本发明涉及一种一次电池，该一次电池具有含无汞锌粉的阳极胶滞体、碱性电解质和通过一个分隔器与碱性电解质隔离的、含二氧化锰的阴极材料。
公开的、上述类型的电池称为碱性锰一次电池。通过出于环保原因放弃向锌粉中附加汞，上述类型的电池的阳极材料具有较高的腐蚀性，该较高的腐蚀性的具体表现是较高的自放水平率和随之而来的、较高的起泡率。为了避免这些负面效果，已经进行了大量的试验，譬如向作为锌粉而采用的锌中附加了合金金属铋、铟、铝和钙(见US-A5209995)。此外，也已公开的是，向阳极胶滞体内添加无机的起泡抑制剂，如氢氧化钡(见US-A4418130)。此外，EP-A582293还公开了向电解质中附加铟盐。
出于成本原因并为了改善放电性能和提高电池的容量，需要进一步减少起泡率。
本发明的任务在于为上述问题提供解决方案。
按照发明，解决以上任务的技术方案在于，上述类型电池的阴极材料包含固态的盐状钙化合物。
在从属权利要求中公开了发明主题的其它优选的实施形式。
发明的附加物Ca(OH)2和/或CaSO4在与所用的锌类别及其中所包含的合金成分几乎无关的情况下发挥其作用。以往，在采用含有电解质的阴极材料时发现电池的起泡率有所增加。产生这种效果的根源在于模具磨损和磨掉的重金属进入阴极材料。通过发明的附加物，起泡率被降回到公知的水平上。此外，还表明，通过发明的附加物，经过部分放电的电池的起泡率有所减少并且电池的放电能力有所改善。无论是在连续放电的情况下，还是在间歇发电的情况下，可从电池中提取的容量有所提高。
下面借助附图和实施例详细说明本发明。附图所示为：
图1和2在新生产的电池，即搁置时间NO表示未经搁置的电池3.9Ω每天间歇放电两次一小时(2×1h/d)的条件下，比较例1和实施例1的放电曲线。
图3和4在电池在70℃的温度下搁置时间一个月(MT1)后，在上述相同的放电条件下，比较例1和实施例1的放电曲线。
图5和6在电池在70℃的温度下搁置7天(7MT)后，在2Ω连续放电的条件下，比较例3和实施例3的放电曲线。
实施例1：
按以下配方制作40个LR14型试验电池：
阴极材料：
具有8500克MnO2、850克石墨、50克Ca(OH)2、600克电解质(500％强KOH)的温材料
阳极胶滞体：
680.0克锌粉沫、5.0克增稠剂(羧化了的纤维素)、0.25克氧化铟、0.04克Ca(OH)2、314.71克电解质
电解质：
760.0克50％强KOH、20.0克ZnO、220.0克H2O
分隔器：
由聚醋酸乙烯酯纤维网(PVA纤维网)构成的蜂房式分隔器。
每个电池用32.7克阴极材料、4.0克用于浸渍分隔器的电解质和16克阳极胶滞体。作为电池杯，采用具有厚0.2μm的镍垫片和厚0.2μm的钴垫片的钢杯。
比较例1：
模拟实施例1制作了试验电池，在这些试验电池的阴极材料中不含有氢氧化钙。
表1和2列出了按实施例1和比较例1制作的试验电池的放电特性对照。在表中分别列出了未经搁置的电池(搁置时间NO＝新生产的)和在70℃温度下搁置时间为一个月(28天)＝MT1的电池的对照值。其中，表1中的试验电池的放电方式为R＝6.8Ω每天两次一小时(2×1h/d)间歇放电。该放电方式是便携式磁带录音机中的放电条件的典型。
表2中的试验电池的放电是在R＝3.9Ω每天8小时内4分钟放电15分钟间歇(4’/15’8h/d)的间歇条件下进行的。这种放电方式是照明放电的典型。
实施例2
按以下配方制作LR20型试验电池：
阴极材料：
8500克MnO2、850克石墨、600克电解质(50％强KOH)
阳极胶滞体：
680.0克锌粉末、5.0克增稠剂(羧化了的纤维素)、0.25克氧化铟、0.04克Ca(OH)2、314.71克电解质(38％强KOH+2％ZnO)
分隔器：
由PVA纤维网构成的蜂房式分隔器。
每个电池用69克阴极材料、9.0克用于浸渍分隔器的电解质和37.5克阳极胶滞体。作为电池杯，采用具有厚0.2μm的镍垫片和厚0.2μm的钴垫片的钢杯。
比较例2
模拟实施例2制作了试验电池，在这些电池的阴极材料中不含有氢氧化钙。
表3列出了作为磁带录音机放电典型的、3.9Ω和2.2Ω每天两次一小时(2×1h/d)间歇放电情况下的放电特性，其中，列出了未经搁置的电池(NO)与在70℃温度下搁置了一个月(MT1)的电池及与在45℃温度下搁置了三个月(T3)的电池的对照比较。
实施例3：
按以下配方制作LR14型试验电池：
阴极材料：
具有600克电解质、8500克MnO2和850克石墨、50克氢氧化钙的湿材料；
阳极胶滞体：
680克锌粉末、5.0克增稠剂、0.25克氧化铟、0.13克硫酸铟、3.4克水、0.12克氢氧化钙、311.10克电解质；
电解质：
760克50％的强KOH、40.0克ZnO、200.0克水，
分隔器：
用4.0克电解质浸渍了的蜂房式分隔器。
每个电池用32.1克阴极材料和16克阳极胶滞体，作为电池容器，采用具有厚0.2μm的镍垫片和厚0.4μm的钴垫片的钢杯。
表4列出了搁置时间为NO、7MT和MT1的试验电池在2Ω连续放电情况下的放电特性。
发明的附加物的有利作用特别是表现在间歇发电的情况下并且有利地表现在经过搁置(搁置时间为7MT、MT1或T3)后的电池上。其中，容量差别可高达20％。
            6.8Ω2×1h/d间歇放电情况下的放电特性比较    表1在阴极中，Ca(OH)2占0％                                                                       在阴极中，Ca(OH)2占0.5％搁置时间：NO
终止电压：OCV      CCV*            0.90(V)t(h)    Q(Ah)    A(Wh)             0.80(V)t(h)    Q(Ah)    A(Wh)
    1.584    1.4091.584    1.3931.586    1.3971.586    1.3871.584    1.405     17.00    4.81    5.3616.08    4.53    5.0217.01    4.77    5.2616.07    4.53    5.0316.07    4.57    5.11     18.05    5.04    5.5518.06    4.98    5.4118.06    5.00    5.4618.06    4.98    5.4218.04    5.00    5.48
  X1.585    1.398S  0.001    0.009     16.45    4.64    5.160.51    0.14    0.15     18.05    5.00    5.470.01    0.03    0.06
          0.90(V)t(h)     Q(Ah)    A(Wh)            0.80(V)t(h)    Q(Ah)   A(Wh)
    16.83    4.78    5.3316.92    4.75    5.2416.08    4.57    5.1116.10    4.54    5.0316.28    4.64    5.20     19.03    5.25    5.7419.04    5.21    5.6318.07    5.01    5.4918.08    4.97    5.4019.03    5.24    5.71
    16.44    4.65    5.180.40    0.11    0.12     18.65    5.14    5.600.53    0.13    0.14
搁置时间：MT1
终止电压：OCV      CCV*            0.90(V)t(h)    Q(Ah)    A(Wh)            0.80(V)t(h)    Q(Ah)    A(Wh)
    1.556    1.4231.558    1.4111.558    1.4251.556    1.4171.556    1.415     12.06    3.55    4.1212.04    3.54    4.1013.04    3.79    4.3413.01    3.79    4.3513.04    3.81    4.38     14.06    3.99    4.5014.07    3.99    4.4915.05    4.23    4.7215.04    4.23    4.7315.05    4.25    4.76
  X1.557    1.418S  0.001    0.006     12.64    3.70    4.260.53    0.54    0.14     14.65    4.14    4.640.14    0.54    0.13
          0.90(V)t(h)    Q(Ah)   A(Wh)             0.80(V)t(h)    Q(Ah)    A(Wh)
    15.90    4.62    5.2915.79    4.60    5.2815.56    4.52    5.1615.46    4.46    5.0815.49    4.50    5.16     17.50    4.97    5.5818.16    5.12    5.7217.45    4.93    5.5217.42    4.90    5.4517.36    4.91    5.51
    15.64    4.54    5.190.19    0.07    0.09     17.58    4.97    5.560.33    0.09    0.10
                                表2
           3.9Ω4′15′8h/d间歇放电情况下的放电特性比较在阴极中，Ca(OH)2占0％                                                                         在阴极中，Ca(OH)2占0.5％搁置时间：NO
终止电压：OCV      CCV*           1.00(V)t(h)    Q(Ah)    A(Wh)            0.90(V)t(h)    Q(Ah)   A(Wh)
    1.584    1.4051.586    1.4051.584    1.4311.584    1.4351.584    1.397     14.00    4.10    4.7113.53    3.93    4.4913.40    3.94    4.5613 93    4.09    4.7314.17    4.14    4.75     17.10    4.87    5.4517.09    4.82    5.3417.07    4 84    5.4217.07    4.87    5.4717.07    4.86    5.45
  X1.584    1.415S  0.001    0.017     13.81    4.04    4.650.33    0.10    0.12     17.08    4.85    5.430.02    0.02    0.05
           1.00(V)t(h)    Q(Ah)    A(Wh)            0.90(V)t(h)    Q(Ah)    A(Wh)
    13.47    4.00    4.6513.53    4.00    4.6413.43    3.92    4.4713.80    4.06    4.6813.47    3.97    4.60     17.07    4.88    5.4917.08    4.87    5.4717.09    4.82    5.3417.10    4.87    5.4717.09    4.86    5.45
    13.54    3.99    4.610.15    0.05    0.08     17.09    4.86    5.440.01    0.02    0.06
搁置时间：MT1
    终止电压：OCV      CCV*           1.00(V)t(h)    Q(Ah)   A(Wh)           0.90(V)t(h)     Q(Ah)   A(Wh)
    1.558    1.4171.558    1.4191.558    1.4111.558    1.4311.556    1.431    9.99    3.07    3.7110.03    3.09    3.7310.55    3.23    3.8910.65    3.25    3.9010.63    3.24    3.89   12.33    3.64    4.2512.33    3.65    4.2612.33    3.66    4.3012.33    3.66    4.2712.33    3.66    4.27
  X1.558    1.422S  0.001    0.009   10.37    3.18    3.820.33    0.09    0.10   12.33    3.65    4.270.00    0.01    0.02
         1.00(V)t(h)    Q(Ah)    A(Wh)           0.90(V)t(h)    Q(Ah)    A(Wh)
  14.04    4.25    5.0513.97    4.22    5.0114.16    4.28    5.0814.03    4.25    5.0614.31    4.32    5.11   16.18    4.77    5.5516.28    4.79    5.5616.32    4.81    5.5916.15    4.77    5.5516.41    4.84    5.61
  14.10    4.26    5.060.14     0.04    0.04   16.27    4.80    5.570.11    0.03    0.03
             3.9Q2×1h/d间歇放电情况下的放电特性比较    表3在阴极中，Ca(OH)2占0％                                                    在阴极中，Ca(OH)2占0.5％搁置时间NO
终止电压：OCV      CCV*          0.90(V)t(h)    Q(Ah)    A(Wh)
    1.584    1.3421.584    1.3721.584    1.3281.584    1.3701.584    1.370   38.9    11.13    12.5738.9    11.28    12.9038.9    11.21    12.7438.9    11.27    12.8638.9    11.15    12.61
  X1.584    1.356S  0.000    0.020   38.9    11.21    12.740.0     0.07     0.15
终止电压：OCV      CCV*           0.90(V)t(h)    Q(Ah)    A(Wh)
  1.594    1.4351.592    1.3771.594    1.4391.594    1.405   40.2    11.55    13.0640.1    11.49    12.9640.1    11.42    12.8141.3    11.94    13.61
  1.594    1.4140.001    0.029   40.5    11.60    13.110.6     0.23     0.35
搁置时间：MT1
终止电压：           0.90(V)t(h)    Q(Ah)  A(Wh)
    1.558    1.4451.556    1.4491.556    1.4431.554    1.4431.556    1.443     24.2    7.36    8.8325.1    7.55    8.9923.0    6.87    8.1224.1    7.24    8.6325.2    7.61    9.10
  X1.556    1.445S  0.001    0.003     24.3    7.32    8.740.9    0.30    0.39
终止电压：CCV      CCV*           0.90(V)t(h)    Q(Ah)    A(Wh)
  1.660    1.4671.566    1.4631.566    1.4571.568    1.4611.556    1.451   35.4    10.49    12.2835.6    10.54    12.3336.4    10.70    12.4536.0    10.65    12.4535.6    10.54    12.35
  1.565    1.4600.003    0.006   35.8    10.58    12.370.4     0.09     0.07
                                                       2.2Ω搁置时间：T3
终止电压：OCV      CCV*          0.90(V)t(m)   Q(Ah)   A(Wh)
    1.572    1.4051.572    1.4251.574    1.3751.572    1.3891.572    1.485     766    6.59    7.59768    6.56    7.49768    6.59    7.57707    6.19    7.27704    6.20    7.30
  X1.572    1.416S  0.001    0.043     743    6.43    7.4434    0.21    0.15
    终止电压：OCV      CCV*          0.90(V)t(m)    Q(Ah)   A(Wh)
  1.582    1.4751.580    1.4671.582    1.4711.584    1.4771.582    1.469   1065    9.09    10.401040    8.98    10.371045    8.95    10.271128    9.60    10.951068    9.07    10.32
  1.582    1.4720.001    0.004   1069    9.14    10.4635    0.27     0.28
                                       2Ω连续放电情况下的放电特性比较    表4在阴极中，Ca(OH)2占0％                                                         在阴极中，Ca(OH)2占0.5％搁置时间NO
终止电压：OCV      CCV       0.90Volt(基本负载1)t(min)    Q(mAh)     A(mWh)
    1.616    1.3691 616    1.4001.616    1.3451.616    1.3801.615    1.326  443.33    3770.87    3875.12452.86    3892.77    4047.64413.75    3424.92    3421.98436.67    3700.39    3790.16411.25    3399.73    3393.99
  X1.616    1.364S  0.000    0.029  431.57    3637.73    3705.7818.36     217.16     287.41
终止电压：OCV      CCV     0.90Voit(基本负载)t(min)  Q(mAh)   A(mWh)
 1.606    1.4641.606    1.4561.606    1.4431.606    1.4551.605    1.413  412.86  3676.22  3960.85410.71  3648.71  3920.27405.00  3596.06  3860.81412.50  3658.03  3923.31374.00  3287.53  3487.49
 1.606    1.4460.000    0.020  403.01  3573.31  3830.5516.52   162.51   195.09
搁置时间MT1
终止电压：OCV      CCV        0.90Volt(基本负载)t(min)    Q(mAh)     A(mWh)
    1.608    1.3611.608    1.3601.608    1.3281.608    1.3661.608    1.390   259.29    2283.64    2433.04256.67    2242.46    2371.75225.11    1964.22    2062.86251.67    2197.90    2325.63276.25    2435.61    2603.26
X 1.608    1.361S   0.000    0.022   254.00    2224.77    2359.3118.12     170.91     196.29
  终止电压：OCV     CCV      0.90Volt(基本负载)t(min)  Q(mAh)   A(mWh)
 1.593    1.4031.593    1.4101.593    1.4301.593    1.4311.593    1.413  320.33  2865.11  3095.49320.00  2864.67  3097.46314.79  2860.29  3141.83314.40  2860.80  3147.50335.13  3013.38  3275.05
 1.593    1.4170.000    0.013  320.93  2892.85  3151.468.41    67.41    73.20
搁置时间ZMT
终止电压：OCV      CCV           0.90Volt(基本负载1)t(min)    Q(mAh)     A(mWh)
    1.588    1.3701.588    1.3701.588    1.3711.588    1.3521.588    1.369   169.44    1498.27    1606.99176.82    1577.87    1707.27166.25    1479.81    1597.73167.86    1467.60    1556.17186.00    1626.17    1725.27
  X1.588    1.366S 0.000    0.008   173.27    1529.94    1638.698.18      68.85      73.64
终止电压：OCV    CCV      0.90Volt(基本负载)t(min)  Q(mAh)   A(mWh)
 1.571   1.4301.570   1.4311.571   1.4331.571   1.4341.571   1.422  222.13  2064.89  2319.22238.04  2201.73  2461.91217.44  2027.18  2283.30236.44  2184.97  2440.73221 67  2055.32  2302.42
 1.571   1.4300.000   0.005  227.14  2106.82  2361.519.41    80.42    83.30

Claims (6)

1.具有含无汞锌粉末的阳极胶滞体、碱性电解质和通过一个分隔器与电解质隔离的、含二氧化锰的阴极材料的一次电池，其特征在于，阴极材料含有固态的盐状钙化合物。
2.按照权利要求1所述的一次电池，其特征在于，阴极材料含有0.1至0.5％(重量)的硫酸钙和/或氢氧化钙。
3.按照权利要求1所述的一次电池，其特征在于，阴极材料含有0.3至0.8％(重量)的氢氧化钙。
4.按照权利要求1至3中的一项或多项所述的一次电池，其特征在于，阴极材料含有其粒度为0.1μm至30μm的盐状钙化合物。
5.按照权利要求1至4中的一项或多项所述的一次电池，其特征在于，在阳极胶滞体内的锌成分中含有0.0010至0.5％(重量)的氢氧化钙。
6.按照权利要求1至5中的一项或多项所述的一次电池，其特征在于，在阳极胶滞体中含有50至500ppm氧化铟和/或硫酸铟。
CN97110563A 1996-04-20 1997-04-18 一次电池 Expired - Fee Related CN1120536C (zh)

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US6428766B1 (en) * 1998-10-27 2002-08-06 Toda Kogyo Corporation Manganese oxide, lithium manganese complex oxide and cobalt-coated lithium manganese complex oxide, and preparation processes thereof
US20030200991A1 (en) * 2002-04-29 2003-10-30 Kimberly-Clark Worldwide, Inc. Dual texture absorbent nonwoven web
EP1930971A1 (en) 2005-09-27 2008-06-11 Matsushita Electric Industrial Co., Ltd. Alkaline dry cell
US8168321B2 (en) * 2008-02-29 2012-05-01 The Gillette Company Alkaline battery having a protective layer

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4418130A (en) 1981-06-10 1983-11-29 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Additive for zinc electrodes
JPS6251164A (ja) * 1985-08-29 1987-03-05 Fuji Elelctrochem Co Ltd アルカリ電池用正極合剤
US4913898A (en) * 1988-04-06 1990-04-03 Altobella Hair Products Inc. Hair treatment composition and method
CA2002348A1 (en) * 1989-11-06 1991-05-06 Klaus Tomantschger Zinc anodes for alkaline galvanic cells and cells containing them
US5108852A (en) * 1990-03-23 1992-04-28 Battery Technologies Inc. Manganese dioxide cathode for a rechargeable alkaline cell, and cell containing the same
CA2046148C (en) * 1990-08-14 1997-01-07 Dale R. Getz Alkaline cells that are substantially free of mercury
JP3215448B2 (ja) 1991-03-12 2001-10-09 三洋電機株式会社 亜鉛アルカリ電池
JPH0738306B2 (ja) * 1991-04-22 1995-04-26 松下電器産業株式会社 亜鉛アルカリ電池
JP3018715B2 (ja) * 1992-02-26 2000-03-13 松下電器産業株式会社 亜鉛アルカリ電池の製造法
US5424145A (en) * 1992-03-18 1995-06-13 Battery Technologies Inc. High capacity rechargeable cell having manganese dioxide electrode
JP3553104B2 (ja) 1992-08-04 2004-08-11 株式会社エスアイアイ・マイクロパーツ アルカリ電池
JP2899180B2 (ja) * 1992-09-01 1999-06-02 キヤノン株式会社 像加熱装置及び像加熱用ヒーター
RU2050637C1 (ru) * 1992-12-30 1995-12-20 Государственное научно-производственное предприятие "Квант" Катодная масса для химического источника тока с водно-солевым электролитом
JP3265673B2 (ja) * 1993-01-29 2002-03-11 松下電器産業株式会社 マンガン乾電池
US5342712A (en) * 1993-05-17 1994-08-30 Duracell Inc. Additives for primary electrochemical cells having manganese dioxide cathodes
US5626988A (en) * 1994-05-06 1997-05-06 Battery Technologies Inc. Sealed rechargeable cells containing mercury-free zinc anodes, and a method of manufacture
US5532085A (en) * 1995-08-22 1996-07-02 Duracell Inc. Additives for alkaline electrochemical cells having manganese dioxide cathodes

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JPH1040902A (ja) 1998-02-13
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EP0802573B1 (de) 2006-05-17
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BR9701891A (pt) 1998-09-29
CZ109397A3 (en) 1997-12-17

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