CN1498434A - 电池阴极 - Google Patents
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- H01M4/00—Electrodes
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- H01M4/06—Electrodes for primary cells
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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
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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
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Abstract
一次碱性电池(10)包括具有阴极活性材料和碳纤维的阴极(12)、阳极(14)、隔板(16)和碱性电解液。碳纤维具有小于约250纳米的直径。
Description
本发明涉及电池。
电池如一次碱性电池通常用作能源。一般地,碱性电池包括阴极、阳极、隔板和电解液。阴极可包括例如作为活性材料的二氧化锰颗粒、增加阴极导电性的石墨颗粒和粘合剂。阳极可以是例如包括锌粒作为活性材料的凝胶。隔板放置在阴极与阳极之间。电解液可以是例如在整个电池中分散的氢氧化物溶液。
理想地,一次碱性电池具有高的放电容量。影响放电容量的一个因素是阴极中的二氧化锰的量。作为通用规则,阴极中二氧化锰越多,电池的放电容量越高。但为了充足的导电性,阴极还必须包括足量的石墨颗粒。因此,可包括在阴极中的二氧化锰的量部分地受到为了充足的导电性所要求的石墨颗粒量的限制。
本发明涉及在一次碱性电池的阴极中使用碳纤维。碳纤维,特别是热处理之后的碳纤维的导电率通常高于石墨或碳颗粒。结果,具有碳纤维的阴极的导电率典型地高于具有石墨或碳颗粒的阴极。此外,由于其增加的导电率和纤维形态,所以为了提供阴极充足的导电率,用于有效的电池性能,在阴极中需要较少的碳纤维。因此,可向阴极加入更多的阴极活性材料,从而增加电池的容量和高的能源效率。
碳纤维通常具有高的表面积和高的表面能。这些性能可提供纤维良好的毛细作用,将电解液吸入到阴极孔径内。例如由于良好的毛细作用导致在阴极中更多的电解液通常会改进阴极内的传质和改进电池的效率。纤维的纤维形态也可起增强介质的作用,机械增强阴极。此外,可便宜地生产碳纤维,这会降低生产电池的成本。
一方面,本发明的特征是一次碱性电池,其包括具有阴极活性材料和碳纤维的阴极、阳极如具有锌作为阳极活性材料的阳极、隔板和碱性电解液。
实施方案可包括一种或多种下述特征。
阴极可包括小于约5wt%的碳纤维,例如小于约4wt%、约3wt%和约2wt%的碳纤维。电池可包括介于约1wt%和约5wt%,例如介于约2wt%和约3wt%的碳纤维。阴极可包括大于约86wt%,例如大于约88wt%、约90wt%和约92wt%的阴极活性材料如二氧化锰。
碳纤维可具有小于约250纳米,例如约60纳米和约100纳米,和小于约60纳米的直径。
可例如在大于约2000℃,例如介于约2600℃和约3100℃的温度下热处理碳纤维。
碳纤维可具有小于约2×105纳米,例如介于约500纳米和约200,000纳米如介于约70,000纳米和约100,000纳米的长度。
碳纤维可包括介于约1和约500层的石墨,例如介于约40和约100层的石墨。
碳纤维可具有介于约10m2/g和约50m2/g的外表面积,和介于约50mJ/m2和约300mJ/m2的表面能。
碳纤维可具有小于约85%的石墨指数(graphitic index)。
碳纤维可具有等于或大于阴极活性材料平均粒度的长度。
阴极可进一步包括表面活性剂如聚乙烯醇(PVA)、乙烯乙烯醇(EVOH)和聚乙烯醇缩丁醛(polyvinylbutyrol)。
另一方面,本发明的特征是一次碱性电池,它具有阴极、阳极、隔板和碱性电解液,其中阴极包括二氧化锰和直径小于约250纳米的热处理过的碳材料。
阴极可包括介于约1wt%和约5wt%,例如介于约2wt%和约3wt%的碳纤维。该阴极的导电率比具有约6%石墨的阴极大至少3倍。
此处所使用的“纤维”是指与长度或高度相比,具有小的周长或宽度的伸长结构体。纤维可具有基本上圆形或基本上非圆形的横截面和/或光滑或粗糙、不规则的表面。纤维通常可直线地或弯曲地延伸。纤维的实例包括线状(thread)、细丝状(filament)和须晶状纤维。
此处所使用的“直径”是指平均直径;和“长度”是指平均长度。
根据附图、说明书和权利要求,本发明的其它特征、目的和优点将变得显而易见。
图是电池的侧面-剖视图。
参考附图,电池10包括阴极12、阳极14、隔板16和圆柱形外壳18。电池10还包括电流集电极20、密封剂22和负金属顶盖24,其中负金属顶盖24充当电池的负电端。阴极12与外壳18接触,和电池10的正电端在与电池10的负电端的反向端点处。电解液分散在整个电池10内。电池10可以是例如AA、AAA、AAAA、C或D电池。
阴极12包括二氧化锰、碳纤维和粘合剂。
二氧化锰可以是电解合成的MnO2(EMD)或化学合成的MnO2(CMD)或EMD与CMD的混合物。二氧化锰的销售者包括KerrMcGee,Co.(Trona D),Chem Metals,Co.,Tosoh,Delta Manganese,Mitsui Chemicals和JMC。优选地,二氧化锰是具有高功率系数的EMD,正如2000年5月1日申请的美国申请No.09/563447中所述,在此引入其全部内容作为参考。一般地,阴极12可包括介于约86wt%和约92wt%,优选介于约88wt%和约91wt%,和更优选介于约89wt%和约91wt%的二氧化锰。
碳纤维是由多层石墨制造的石墨纤维。优选地,碳纤维含有约1到约500层石墨,更优选约40到约100层石墨。随着纤维中的石墨层数量降低,纤维的导电率通常会增加。因此,与具有石墨层数相对高的纤维的阴极相比,具有低层数的纤维的阴极典型地具有高的导电率。优选地,碳纤维具有大于约50%,例如介于约50%和约85%,如约75%的石墨指数。石墨指数是纤维石墨化程度的量度,它定义为gρ=(0.3440-D间距)/(0.3440-0.3354),其中D间距是所测量的碳纤维的D间距,单位是纳米。碳纤维可包括少量如小于60ppm的其它材料如铁、钴和镍。
碳纤维以商品名PYROGRAF-IIITM获自Applied Sciences.Inc.(Cedarville,OH)。在美国专利No.5594060和其中引证的参考文献中公开了制造碳纤维的方法,所有这些文献的全文引入参考。
碳纤维优选具有小于约250纳米,更优选约60到约200纳米,和最优选约60到约100纳米的直径。纤维的长度通常至少与二氧化锰颗粒的大小一样长。例如纤维可以是约500纳米到约200,000纳米长。
优选地,在将碳纤维掺入到阴极内之前热处理碳纤维。在约2600-3100℃,例如在约2900-3000℃下热处理纤维通常会增加纤维的导电率和阴极的导电性,当在后来将纤维掺入其中时。认为当合成纤维时,在纤维的表面上形成导电性差的罩面层或碳层。热处理纤维会将碳层转化成石墨,以改进纤维的导电性。
热处理过的碳纤维通过降低阴极的渗透阈值(percolationthreshold),可增强电池10的效率。渗透阈值是优选加入到阴极中的材料用量,此处为碳纤维用量,以便在电池10中提供阴极有效使用的充足的导电性。在不希望受到任何理论束缚的情况下,认为碳纤维的纤维结构使得纤维在二氧化锰颗粒当中拉伸,从而增加纤维与阴极活性材料之间的接触,和更有效地增加阴极的导电性。因此,可能加入较少的碳纤维(惰性材料),而同时保持阴极所需的导电率。
因此,尽管一些电池优选具有介于约5-7wt%的碳颗粒,但阴极12可包括小于5wt%的碳纤维,例如小于4wt%,或小于3wt%或小于2wt%的碳纤维。有效地,阴极12包括介于约1wt%和约5wt%的碳纤维,更优选介于约2wt%和约3wt%。
可用二氧化锰填充通过在阴极中降低碳的用量而“空出(freedup)”的体积,以增加电池10的容量。此外,因为碳纤维典型地具有不同于阴极活性材料如二氧化锰的密度,所以降低碳纤维的用量有时可允许大于1∶1用量的阴极活性材料替换到阴极内。
作为其纤维结构或形态的特征,碳纤维具有高的表面积和高的表面能。一般地,随着纤维直径的降低,纤维的表面能增加。在一些实施方案中,纤维可具有约10m2/g到约50m2/g的外表面积,和约50mJ/m2到约300mJ/m2的表面能,如约100mJ/m2的表面能。认为纤维的表面积和能量会增加纤维的亲水性。增加的纤维亲水性提供阴极增加的毛细作用,以改进电解液吸收到阴极内的速率和吸收到阴极的电解液量。在阴极内增加的电解液浓度通常改进阴极孔径内的传质和改进电池的效率。
为了进一步增加纤维的亲水性,可将表面活性剂加入到纤维中。表面活性剂的实例包括例如聚乙烯醇(PVA)、乙烯-乙烯醇(EVOH)和聚乙烯醇缩丁醛。
碳纤维的纤维结构也机械地增强阴极。一般地,在将碳纤维掺入到阴极内之后,阴极的强度增加。
粘合剂的实例包括聚乙烯粉末、聚丙烯酰胺、Potland水泥和氟碳树脂,如聚偏-1,1-二氟乙烯(PVDF)和聚四氟乙烯(PTFE)。聚乙烯粘合剂的实例是以商品名Coathylene HA-1681销售的(获自Hoescht)。阴极可包括例如介于0.1wt%到约1wt%的粘合剂。
阴极12可包括其它添加剂。例如在美国专利No.5342712中公开了这些添加剂的实例,在此引入其参考。阴极12可包括例如约0.2wt%到约2wt%的二氧化钛。
电解液也分散在整个阴极12中,和在电解液分散之后,测量以上与以下所提供的重量百分数。
可由在电池阴极内使用的任何标准的锌材料形成阳极14。例如,阳极14可以是锌凝胶,所述锌凝胶包括锌金属颗粒、胶凝剂和少量添加剂,如产气抑制剂。另外,部分电解液分散在整个阳极中。
锌粒可以是在凝胶阳极内常规使用的任何锌粒。锌粒的实例包括在U.S.S.N.08/905254、U.S.S.N.09/115867和U.S.S.N.09/156915(这些申请已委托本申请的代理人和在此引入参考)中所述的那些。阳极可包括例如介于67wt%和71wt%的锌粒。
胶凝剂的实例包括聚丙烯酸、接枝的淀粉材料、聚丙烯酸盐、聚丙烯酸酯、羧甲基纤维素或其结合。这种聚丙烯酸的实例是Carbopol940和934(获自B.F.Goodrich)和Polygel 4P(获自3V)。接枝的淀粉材料的实例是Waterlock A221(获自Grain Processing Corporation,Muscatine,IA)。聚丙烯酸盐的实例是Alcosorb G1(获自CibaSpecialties)。阳极可包括例如0.1wt%到约1wt%的胶凝剂。
产气抑制剂可以是无机材料,如铋、锡、铅和铟。或者产气抑制剂可以是有机化合物如磷酸酯、离子表面活性剂或非离子表面活性剂。离子表面活性剂的实例在例如美国专利No.4777100中被公开,在此引入其参考。
隔板16可具有电池隔板的任何常规设计。在一些实施方案中,可由两层非织造、非膜材料形成隔板16,其中的一层沿另一层的表面排列。为了使隔板16的体积最小,同时提供有效的电池,非织造、非膜材料的各层具有约54g/m2的基重、当干燥时具有约5.4密耳的厚度和当湿润时具有约10密耳的厚度。在这些实施方案中,隔板优选不包括膜材料层或在非织造、非膜材料层之间的粘合剂层。一般地,各层可基本上没有填料如无机颗粒。
在其它实施方案中,隔板16包括具有非织造材料层的玻璃纸外层。隔板也包括另外的非织造材料层。玻璃纸层可邻接阴极12或阳极。优选地,非织造材料含有约78wt%到约82wt%的PVA和约18wt%到约22wt%的人造丝,其中具有痕量表面活性剂。这种非织造材料以商品名PA25获自PDM。
分散在整个电池10中的电解液可以是电池中使用的任何常规的电解液。典型地,电解液是含水的氢氧化物溶液。这种含水氢氧化物溶液包括氢氧化钾溶液(其中包括例如介于33%和38wt%的氢氧化钾)和氢氧化钠溶液。电解液也可包括约2wt%的氧化锌。
外壳18可以是在一次碱性电池中常用的任何常规外壳。外壳典型地包括金属内壁和外部的非导电性材料如可热收缩塑料。任选地,导电材料层可在内壁和阴极12之间排列。这一层可沿壁的内表面、沿阴极12的周围或沿这二者排列二者。可例如由含碳材料形成这层导电层。这种材料包括LB1000(Timcal)、Eccocoat 257(W.R.Grace &Co.)、Electrodag 109(Acheson Colloids Co.)、EIectrodag 112(Acheson)和EB 0005(Acheson)。例如加拿大No.1263697中公开了施加导电层的方法,在此引入其参考。
由合适的金属如黄铜制造电流集电极20。可由例如尼龙制造密封剂22。
下述实施例仅用于阐述目的和不打算限制本发明。
实施例
根据下述步骤制备电池10(AA)的实例。
阴极包括约10.35g二氧化锰(Kerr McGee)、0.345g(3wt%)碳纤维(Applied Sciences)、约0.65g9N氢氧化钾溶液和约0.3wt%的coathylene HA-1681。阳极包括约4.5g锌粒、约3.4g36%氢氧化钾、相对于锌约1260ppm的表面活性剂(RM510,Rhone Poulenc)、约1.96g9N氢氧化钾(具有2%溶解的氧化锌)和约1.6wt%总的胶凝剂(Carbopol940和A221)。
隔板可由一层或两层非织造、非膜材料形成,其中一层沿另一层的表面排列。为了使隔板的体积最小,非织造、非膜材料的各层具有约54g/m2的基重、当干燥时具有约5.4密耳的厚度和当湿润时具有约10密耳的厚度。阳极也包括如上所述配置在阴极和阳极内的约3.17g含水氢氧化钾溶液,其中含有2%溶解的氧化锌(约35.5wt%氢氧化钾),而其余在隔板层内。在电池的外壁与阴极的外周之间排列薄的EB005涂层(Acheson)。
可预计其它实施方案。例如可将以上所述的碳纤维施加到燃料电池上,和其它类电池如金属-空气电池和空气回收电池上。
Claims (34)
1.一种一次碱性电池,其中包括:
含阴极活性材料和碳纤维的阴极;
阳极;
隔板;和
碱性电解液。
2.权利要求1的电池,其中阴极包括小于约5wt%的碳纤维。
3.权利要求1的电池,其中阴极包括小于约4wt%的碳纤维。
4.权利要求1的电池,其中阴极包括小于约3wt%的碳纤维。
5.权利要求1的电池,其中阴极包括小于约2wt%的碳纤维。
6.权利要求1的电池,其中阴极包括介于约1wt%和约5wt%的碳纤维。
7.权利要求1的电池,其中阴极包括介于约2wt%和约3wt%的碳纤维。
8.权利要求1的电池,其中阴极活性材料包括二氧化锰。
9.权利要求1的电池,其中阴极包括大于约86wt%的阴极活性材料。
10.权利要求1的电池,其中阴极包括大于约88wt%的阴极活性材料。
11.权利要求1的电池,其中阴极包括大于约90wt%的阴极活性材料。
12.权利要求1的电池,其中阴极包括大于约92wt%的阴极活性材料。
13.权利要求1的电池,其中碳纤维具有小于约250纳米的直径。
14.权利要求1的电池,其中碳纤维具有介于约60纳米和约100纳米的直径。
15.权利要求1的电池,其中碳纤维具有小于约60纳米的直径。
16.权利要求1的电池,其中碳纤维已被热处理。
17.权利要求16的电池,其中碳纤维在大于约2000℃的温度下进行热处理。
18.权利要求16的电池,其中碳纤维在介于约2600℃和约3100℃的温度下进行热处理。
19.权利要求1的电池,其中碳纤维具有小于约2×105纳米的长度。
20.权利要求1的电池,其中碳纤维具有介于约500纳米和约200,000纳米的长度。
21.权利要求1的电池,其中碳纤维具有介于约70,000纳米和约100,000纳米的长度。
22.权利要求1的电池,其中碳纤维包括介于约1和约500层的石墨。
23.权利要求22的电池,其中碳纤维包括介于约40和约100层的石墨。
24.权利要求1的电池,其中碳纤维具有介于约10m2/g和约50m2/g的外表面积。
25.权利要求1的电池,其中碳纤维具有介于约50mJ/m2和约300mJ/m2的表面能。
26.权利要求1的电池,其中碳纤维具有小于约85%的石墨指数。
27.权利要求1的电池,其中碳纤维具有等于或大于阴极活性材料平均粒度的长度。
28.权利要求1的电池,其中阴极进一步包括表面活性剂。
29.权利要求28电池,其中表面活性剂选自聚乙烯醇、乙烯-乙烯醇和聚乙烯醇缩丁醛。
30.权利要求1的电池,其中阳极包括锌作为阳极活性材料。
31.一种一次碱性电池,其中包括:
阴极,所述阴极包括二氧化锰和直径小于约250纳米的热处理过的碳材料;
阳极;
隔板;和
碱性电解液。
32.权利要求31的电池,其中阴极包括介于约1wt%和约5wt%的碳纤维。
33.权利要求31的电池,其中阴极包括介于约2wt%和约3wt%的碳纤维。
34.权利要求31的电池,其中该阴极的导电率比具有约6%石墨的阴极大至少3倍。
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-
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- 2001-09-05 CN CNB018164307A patent/CN1323448C/zh not_active Expired - Fee Related
- 2001-09-05 AU AU2001288703A patent/AU2001288703A1/en not_active Abandoned
- 2001-09-05 WO PCT/US2001/027426 patent/WO2002021615A2/en active Application Filing
- 2001-09-05 EP EP01968458A patent/EP1338042A2/en not_active Withdrawn
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101192661B (zh) * | 2006-11-21 | 2011-12-28 | 北京中航长力能源科技有限公司 | 一种注入式锌空气金属燃料电池流动态锌胶电极材料 |
CN102859767A (zh) * | 2011-04-18 | 2013-01-02 | 松下电器产业株式会社 | 碱性一次电池 |
CN102859767B (zh) * | 2011-04-18 | 2015-08-05 | 松下电器产业株式会社 | 碱性一次电池 |
CN108183215A (zh) * | 2017-12-27 | 2018-06-19 | 广州鸿森材料有限公司 | 锂离子二次电池负极材料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
JP2004508686A (ja) | 2004-03-18 |
WO2002021615A3 (en) | 2002-06-06 |
WO2002021615A2 (en) | 2002-03-14 |
EP1338042A2 (en) | 2003-08-27 |
CN1323448C (zh) | 2007-06-27 |
AU2001288703A1 (en) | 2002-03-22 |
WO2002021615A8 (en) | 2004-02-26 |
US6858349B1 (en) | 2005-02-22 |
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