CN1326594A - 用于二氧化锰阴极电化学电池的钛添加剂 - Google Patents
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Abstract
公开了一种阴极(12),该阴极(12)包括二氧化锰和优选硫酸氧钛的钛氧盐。具有阴极(12)的电池(10)有好的性能特性。例如,电池(10)很好地应用在包括如玩具的间歇电耗方面。而且在此公开的电化学电池包括阴极(12)、阳极(14)和设置在阴极和阳极之间的隔板(16)。阴极包括二氧化锰和钛氧盐。
Description
本发明涉及电池。
通常把例如碱性电池的电池用作能源。一般地,碱性电池具有阴极、阳极、隔板和碱性电解质溶液。阴极通常由二氧化锰、碳颗粒、碱性电解质溶液和粘合剂形成。阳极由包括碱性电解质溶液和锌颗粒的胶体形成。分散在整个电池中的电解质溶液可以是氢氧化物溶液例如氢氧化钾。
本发明涉及例如碱性电池的电池,具有包括二氧化锰和优选硫酸氧钛(TiOSO4)的钛氧盐的阴极。这些电池具有优良的性能特性。例如,这些电池很好地应用在包括间歇电耗如玩具(IEC Test@3.9欧姆,1小时/天)、闪光灯(IEC and ANSI Tests@3.9欧姆,4分钟/小时,8小时/天)和磁带录音机(IEC Test@6.8欧姆,1小时/天)等方面。电池具有各种工业标准尺寸如AA、AAA、AAAA、C或D。一方面,本发明的特征在于包括二氧化锰和钛氧盐的阴极。
另一方面,本发明的特征在于包括阴极、阳极和位于阴极与阳极之间的隔板的电化学电池。该阴极包括二氧化锰和钛氧盐。
优选实施方案包括一个或多个如下特征。钛氧盐是硫酸氧钛(TiOSO4)。阴极包括基于阴极活性材料总重的0.1%-5%的钛氧盐。该阴极还包括导电颗粒。
从优选实施例和权利要求的描述,本发明的其它特征和优点将显而易见。
附图是电池的横截面图。
优选的电池是碱性电池,具有由二氧化锰,从碳、石墨和其混合物构成的组中选择的导电颗粒,钛氧盐如硫酸氧钛(TiOSO4),以及任选地一定数量的碱性电解质和粘合剂形成的阴极。
参照附图,所示出的电池10具有阴极12、阳极14、隔板16、与阴极12外径接触的外壁18、和绝缘层26。电池10还包括穿过密封件22并进入阳极14的阳极集电体20。阳极集电体20的上端连接到负极端盖帽24,盖帽24起电池10的负极外端子的作用。绝缘层26由非导电材料如热收缩塑料形成。此外,电解质溶液分散在整个电池10中。
阴极12是单个材料圆片。另一方面,阴极12能由相互层叠在顶面上的大量阴极圆片形成。在另一情况下,首先通过混合二氧化锰、导电颗粒、钛氧盐、以及任选的电解质溶液和粘合剂来制备阴极圆片。对于使用多于一个圆片的实施例,能压制该混合物形成圆片。使用标准工艺把圆片装在电池10中。例如,在一个方法中,把芯棒放置在电池10的中心空腔中,然后使用冲床对圆片的最上部加压。在使用该方法时,壁18的里面具有绕壁18圆周间隔开的一个或多个垂直脊。这些脊有助于保持电池10内的阴极12就位。
在由单个圆片形成阴极12的实施例中,粉末能直接放置在电池10内。使扣环就位,并且挤压棒穿过扣环,使粉末致密并形成阴极12。
阴极12包括二氧化锰、石墨和/或碳颗粒、和钛氧盐。当电池阴极中包含钛氧盐时,适当的钛氧盐是通过改变放电过程和阴极产物来延长电池使用寿命的那些盐。优选的钛氧盐是从Aldrich Chemical市售的TiOSO4,产品号Product No.33398-0。其它适当的钛氧盐包括La2Ti4O4(SO4)7,δTi2O1.3(PO4)1.6,(TiO)2P2O7,Cd2TiNbO6F,PbBi2TiNbO8F,α-SrTiOF4,Na(1-x)ZnxTi2O6F1.8,TiOCl2,CaTi2O4(OH)2VTiO3(OH),CeTi2(O,OH)6。基于阴极中活性材料总重,优选包含钛盐的数量为约0.1-5wt%。如果使用更多的钛盐,由于MnO2的稀释,将降低低漏电性能,而同时如果使用太少的钛盐,对电池性能几乎没有影响。
能使用用于电池的任何传统形式的二氧化锰如EMD或CMD。该二氧化锰的分销商包括Kerr McGee,Co.,Broken Hill Proprietary,ChemMetals,Co.,Tosoh,Delta Manganese,Mitsui Chemicals,JMC,Sedema和Chuo Denki。
导电颗粒从碳粉末、石墨和其混合物构成的组中选择。适当的导电颗粒给阴极材料赋予导电性,而不有害地影响电池的其它性能。阴极优选地含有基于阴极活性材料总重的约4-15%的导电颗粒。更高含量会不利地降低电池中的活性材料数量,而太低的含量没有足够的导电性。
在一些实施例中,阴极12还包括添加电解质溶液和/或粘合剂。如下讨论电解质溶液。用于阴极12的粘合剂例子包括聚乙烯粉末、聚丙烯酰胺、波特兰水泥和碳氟树脂如PVDF和PTFE。
在一定实施例中,阴极12包括以商标名称coathylene HA-1681(Hoechst)出售的聚乙烯粘合剂。当阴极12包括粘合剂时,粘合剂优选占阴极12的少于约1wt%,更优选约0.1wt%-约0.5wt%,最优选约0.3wt%。
阴极12能包括其它添加剂。这些添加剂的例子在美国专利No.5342712中公开,在此引用供参考。
在一定实施例中,导电材料层设置在外壳壁18和阴极12之间。导电材料层可以沿壁18的内表面、沿阴极12的外圆周或沿它们两者布置。通常,该导电层由碳素物和任选粘合剂形成。该材料包括LB1000(Timcal)、Eccocoat257(W.R.Grace&Co.),Electrodag109(AchesonIndustries,Inc.),Electrodag112(Acheson)和EB005(Acheson)。涂覆导电层的方法在例如加拿大专利No.1263697中公开,在此引用供参考。
在壁18和阴极12之间使用导电层,尤其是Electrodag109或EB005,能降低在电池10内形成阴极12时所需要的压力。因此,在电池10内形成阴极12时,能使阴极12的密度相对高,而不会导致圆片粉碎或断裂。然而,如果阴极12的密度太高,没有足够数量的电解质溶液分散在阴极12内,降低电池10的效率。例如,对于通常的C型电池,阴极12的孔隙率为约18%-约28%,更优选约22%-约27%,最优选25%。这里,孔隙率指为电解质提供的空间,表示成阴极总几何体积的体积百分比。
阳极14由电池阳极中使用的任何标准锌材料形成。通常,阳极14由锌膏形成,锌膏包括锌金属颗粒、碱性电解质、胶凝剂和如金属镀覆、无机和有机的气体抑制剂的少量添加剂。
阳极14中使用的胶凝剂包括聚丙烯酸、接枝的淀粉材料、聚丙烯酸酯、聚丙烯酸盐、羧甲基纤维素或羧甲基纤维素钠或其组合。该聚丙烯酸的例子是Carbopol 940(B.F.Goodrich)和Polygel 4P(3V),接枝淀粉材料的例子是Waterlock A221(Grain Processing Corporation,Muscatine,IA)。聚丙烯酸盐的例子是Alcosorb Gl(Allied Colloids)。在一些实施例中,阳极14优选包括约0.2wt%-约1wt%的总胶凝剂,更优选约0.4wt%-约0.8wt%的总胶凝剂,最优选约0.55wt%-约0.75wt%的总胶凝剂。这些重量百分比与电解质溶液分散在阳极14中时相对应。
气体抑制剂可以是无机材料,如铋、锡、铅和铟。另一方面,气体抑制剂也可以是有机化合物,如磷酸酯、离子表面活性剂或非离子表面活性剂。离子表面活性剂的例子在例如美国专利No.4777100中公开,在此引用供参考。
隔板16具有用于电池隔板的任何传统设计。
分散在整个电池10中的电解质溶液是在电池中使用的任何传统电解质溶液。通常,电解质溶液是氢氧化物水溶液。该氢氧化物水溶液包括例如氢氧化钾溶液和氢氧化钠溶液。在一些实施例中,电解质溶液是包括约30wt%-约45wt%氢氧化钾的氢氧化钾水溶液。该氢氧化物水溶液任选包含少量溶解的锌氧化物,通常在约1-4wt%的范围内。
实施例I
用传统的阴极和阳极活性材料、电解质和隔膜构成传统的一次Zn/MnO2碱性C电池。阳极材料呈胶体混合物形式,含有Zn合金粉末、KOH水溶液、胶凝剂(从B.F.Goodrich提供的丙烯酸共聚物)、超吸收剂(从Grain Processing Corp.提供的Waterlock A221)和表面活性剂(从Rhone Poulenc提供的有机磷酸酯RM510)。隔板是层叠在玻璃纸上的传统电解质渗透聚乙烯醇/人造丝无纺布。电解质是含35wt%KOH和2wt%ZnO的KOH水溶液。
阴极活性材料具有如下组分:电解二氧化锰(84.8wt%)、石墨(8.5wt%)、聚乙烯粘合剂(0.16wt%)和9N KOH溶液(6.54wt)。
除了含有1.5wt%TiOSO4,并且电解二氧化锰的数量相应降低1.5wt%之外,与标准电池一样构成实验C型电池。在标准和实验电池中阴极总重相等。
在放电期间,实验电池显示比标准电池明显的优点。对于间歇ANSI和IEC实验如玩具实验(3.9欧姆,1小时/天)、闪光灯实验(3.9欧姆,4分钟/小时,8小时/天)和磁带录音机实验(6.8欧姆,1小时/天),观察到了主要优点(4.5-6.5%)。其它实施方案包含在权利要求书内。
Claims (12)
1.电化学电池,包括:含有二氧化锰和钛氧盐的阴极;阳极;和设置在阴极和阳极之间的隔板。
2.根据权利要求1的电化学电池,其中所述钛氧盐是硫酸氧钛。
3.根据权利要求1的电化学电池,其中阴极包括基于阴极活性材料总重的约0.1-5.0wt%所述钛氧盐。
4.根据权利要求1的电化学电池,其中电化学电池是碱性电池。
5.根据权利要求1的电化学电池,其中电化学电池是从C型电池和D型电池构成的组中选择。
6.根据权利要求1的电化学电池,其中阴极的孔隙率为约18%-约28%。
7.根据权利要求1的电化学电池,其中阳极包括锌颗粒。
8.根据权利要求1的电化学电池,还包括电解质溶液。
9.一种阴极,包括:
二氧化锰;和
钛氧盐。
10.根据权利要求9的阴极,其中所述钛氧盐是硫酸氧钛。
11.根据权利要求9的阴极,其中阴极包括基于阴极活性材料总重的约0.1-5.0wt%所述钛氧盐。
12.根据权利要求9的阴极,其中阴极的孔隙率为约18%-约28%。
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US09/176,500 | 1998-10-21 | ||
US09/176,500 US6143446A (en) | 1998-10-21 | 1998-10-21 | Battery cathode |
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CN1326594A true CN1326594A (zh) | 2001-12-12 |
CN1203567C CN1203567C (zh) | 2005-05-25 |
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US (1) | US6143446A (zh) |
EP (1) | EP1125336B1 (zh) |
JP (1) | JP2002528865A (zh) |
CN (1) | CN1203567C (zh) |
AR (1) | AR020926A1 (zh) |
AT (1) | ATE257278T1 (zh) |
AU (1) | AU1125200A (zh) |
CA (1) | CA2347739A1 (zh) |
DE (1) | DE69913979T2 (zh) |
WO (1) | WO2000024071A1 (zh) |
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-
1999
- 1999-10-20 WO PCT/US1999/024471 patent/WO2000024071A1/en active IP Right Grant
- 1999-10-20 DE DE69913979T patent/DE69913979T2/de not_active Expired - Lifetime
- 1999-10-20 AT AT99955061T patent/ATE257278T1/de not_active IP Right Cessation
- 1999-10-20 JP JP2000577723A patent/JP2002528865A/ja not_active Ceased
- 1999-10-20 AU AU11252/00A patent/AU1125200A/en not_active Abandoned
- 1999-10-20 CN CNB998132764A patent/CN1203567C/zh not_active Expired - Fee Related
- 1999-10-20 CA CA002347739A patent/CA2347739A1/en not_active Abandoned
- 1999-10-20 EP EP99955061A patent/EP1125336B1/en not_active Expired - Lifetime
- 1999-10-21 AR ARP990105314A patent/AR020926A1/es unknown
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101600668B (zh) * | 2006-08-02 | 2013-05-01 | 萨克特本化学有限责任公司 | 含钛添加剂 |
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EP1125336A1 (en) | 2001-08-22 |
AU1125200A (en) | 2000-05-08 |
WO2000024071A1 (en) | 2000-04-27 |
CN1203567C (zh) | 2005-05-25 |
DE69913979D1 (de) | 2004-02-05 |
DE69913979T2 (de) | 2004-11-11 |
CA2347739A1 (en) | 2000-04-27 |
US6143446A (en) | 2000-11-07 |
EP1125336B1 (en) | 2004-01-02 |
ATE257278T1 (de) | 2004-01-15 |
WO2000024071A9 (en) | 2001-12-13 |
AR020926A1 (es) | 2002-06-05 |
JP2002528865A (ja) | 2002-09-03 |
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