CN1169598A - 一次电池 - Google Patents
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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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- 239000010406 cathode material Substances 0.000 claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940043430 calcium compound Drugs 0.000 claims abstract description 4
- 150000001674 calcium compounds Chemical class 0.000 claims abstract description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 229910003437 indium oxide Inorganic materials 0.000 claims description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical class [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 claims description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract 1
- 239000011575 calcium Substances 0.000 description 13
- 239000000499 gel Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005187 foaming Methods 0.000 description 6
- 235000011116 calcium hydroxide Nutrition 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003203 everyday effect Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005275 alloying Methods 0.000 description 2
- 230000021523 carboxylation Effects 0.000 description 2
- 238000006473 carboxylation reaction Methods 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002471 indium Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910000337 indium(III) sulfate Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/117—Inorganic material
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- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
- H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
- H01M50/128—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers with two or more layers of only inorganic material
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- H01M50/50—Current conducting connections for cells or batteries
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- H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
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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
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
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) |
1.584 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 |
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
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) |
1.584 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 |
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
搁置时间:MT1
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 |
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
搁置时间MT1
搁置时间ZMT
终止电压:OCV CCV | 0.90Volt(基本负载1)t(min) Q(mAh) A(mWh) |
1.616 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 |
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 |
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。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE19615724.2 | 1996-04-20 | ||
DE19615724A DE19615724A1 (de) | 1996-04-20 | 1996-04-20 | Galvanische Zelle |
Publications (2)
Publication Number | Publication Date |
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CN1169598A true CN1169598A (zh) | 1998-01-07 |
CN1120536C CN1120536C (zh) | 2003-09-03 |
Family
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CN97110563A Expired - Fee Related CN1120536C (zh) | 1996-04-20 | 1997-04-18 | 一次电池 |
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US (1) | US6200699B1 (zh) |
EP (1) | EP0802573B1 (zh) |
JP (1) | JPH1040902A (zh) |
KR (1) | KR100566159B1 (zh) |
CN (1) | CN1120536C (zh) |
BR (1) | BR9701891A (zh) |
CA (1) | CA2203065A1 (zh) |
CO (1) | CO4560529A1 (zh) |
CZ (1) | CZ287382B6 (zh) |
DE (2) | DE19615724A1 (zh) |
HK (1) | HK1005963A1 (zh) |
PL (1) | PL319532A1 (zh) |
SK (1) | SK283207B6 (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 |
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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 |
-
1996
- 1996-04-20 DE DE19615724A patent/DE19615724A1/de not_active Withdrawn
-
1997
- 1997-02-19 EP EP97102640A patent/EP0802573B1/de not_active Expired - Lifetime
- 1997-02-19 DE DE59712649T patent/DE59712649D1/de not_active Expired - Fee Related
- 1997-03-18 KR KR1019970009052A patent/KR100566159B1/ko not_active IP Right Cessation
- 1997-04-10 CZ CZ19971093A patent/CZ287382B6/cs not_active IP Right Cessation
- 1997-04-16 CO CO97019977A patent/CO4560529A1/es unknown
- 1997-04-16 SK SK477-97A patent/SK283207B6/sk unknown
- 1997-04-17 JP JP9099967A patent/JPH1040902A/ja active Pending
- 1997-04-17 PL PL97319532A patent/PL319532A1/xx unknown
- 1997-04-18 US US08/844,214 patent/US6200699B1/en not_active Expired - Fee Related
- 1997-04-18 CA CA002203065A patent/CA2203065A1/en not_active Abandoned
- 1997-04-18 CN CN97110563A patent/CN1120536C/zh not_active Expired - Fee Related
- 1997-04-22 BR BRPI9701891-0A patent/BR9701891A/pt not_active IP Right Cessation
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1998
- 1998-06-10 HK HK98105117A patent/HK1005963A1/xx not_active IP Right Cessation
Also Published As
Publication number | Publication date |
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US6200699B1 (en) | 2001-03-13 |
SK283207B6 (sk) | 2003-03-04 |
KR970072533A (ko) | 1997-11-07 |
MX9702839A (es) | 1997-10-31 |
HK1005963A1 (en) | 1999-02-05 |
SK47797A3 (en) | 1997-11-05 |
CN1120536C (zh) | 2003-09-03 |
EP0802573A2 (de) | 1997-10-22 |
KR100566159B1 (ko) | 2006-09-06 |
PL319532A1 (en) | 1997-10-27 |
CO4560529A1 (es) | 1998-02-10 |
EP0802573A3 (de) | 1999-03-24 |
DE19615724A1 (de) | 1997-10-23 |
JPH1040902A (ja) | 1998-02-13 |
DE59712649D1 (de) | 2006-06-22 |
EP0802573B1 (de) | 2006-05-17 |
CZ287382B6 (en) | 2000-11-15 |
CA2203065A1 (en) | 1997-10-20 |
BR9701891A (pt) | 1998-09-29 |
CZ109397A3 (en) | 1997-12-17 |
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