CN101242011B - 电池单元 - Google Patents

电池单元 Download PDF

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CN101242011B
CN101242011B CN200810006414XA CN200810006414A CN101242011B CN 101242011 B CN101242011 B CN 101242011B CN 200810006414X A CN200810006414X A CN 200810006414XA CN 200810006414 A CN200810006414 A CN 200810006414A CN 101242011 B CN101242011 B CN 101242011B
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nonaqueous electrolytic
rechargeable nonaqueous
battery
active material
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CN101242011A (zh
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马场泰宪
井町直希
藤谷伸
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Sanyo Electric Co Ltd
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Abstract

本发明的课题在于将多个非水电解质二次电池串联连接而成的电池单元的输出功率维持在高的状态,同时容易地抑制串联连接的非水电解质二次电池变成过充电状态,以获得高的安全性。多个非水电解质二次电池串联连接而成的电池单元,其中,使充电时从正极活性物质中释放锂而电阻上升的电位不同的至少两种非水电解质二次电池A1、B1a串联连接。

Description

电池单元
技术领域
本发明涉及串联连接多个非水电解质二次电池而成的电池单元,特别涉及具有如下特征的电池单元:将电池单元的输出功率维持在高的状态,同时容易地抑制串联连接的非水电解质二次电池变成过充电状态,可获得高的安全性。
背景技术
作为高输出功率、高能量密度的新型二次电池,广泛利用非水电解质二次电池,该非水电解质二次电池使用非水电解液、并使锂离子在正极与负极之间移动而进行充放电。
另外,近年来,将这样的非水电解质二次电池利用于电动工具、电动汽车、混合动力汽车的电源等。
在此,这样将非水电解质二次电池利用于电动工具、电动汽车、混合动力汽车的电源等时,需要非常大的输出功率及容量。
因此,使用将多个如上述那样的非水电解质二次电池串联连接而成的电池单元,可根据需要,制作成将多个这样的电池单元并联连接而成的电池组件。
在此,在上述那样将多个非水电解质二次电池串联连接而成的电池单元或电池组件的状态下使用时,所连接的非水电解质二次电池的数越增加,电池单元、电池组件内的散热性越降低,特别是为得到高输出功率而使用正极活性物质使用钴酸锂LiCoO2、镍酸锂LiNiO2等具有层状结构的锂过渡金属复合氧化物的非水电解质二次电池的情况下,存在充电时处于过充电状态时,电池单元、电池组件的安全性大大降低的问题。
因此,提出了在如上述那样以电池单元、电池组件的状态使用时,设置用于防止过充电的保护电路、或设置用于防止电池温度上升的风扇等设置各种安全机构的方案。
另外,为了应对高输出功率化及高容量化,需要更进一步提高安全化对策,不仅需要开发电池单元、电池组件中的安全机构,还需要开发非水电解质二次电池本身的安全机构。
另外,目前,为了提高非水电解质二次电池的安全性,提出了其正极活性物质使用具有层状结构或尖晶石结构的锂金属复合氧化物和橄榄石型磷酸铁锂LiFePO4等橄榄石型磷酸锂化合物的方案(例如,参照专利文献1、2。)。
然而,这样,使多个正极活性物质包含具有层状结构或尖晶石结构的锂金属复合氧化物和橄榄石型磷酸铁锂LiFePO4等橄榄石型磷酸锂化合物的非水电解质二次电池串联连接用作电池单元的情况下,存在难以获得高的输出功率的问题。
专利文献1:日本特开2002-216755号公报
专利文献2:美国专利公开2006-0019151号公报
发明内容
发明所要解决的问题
本发明的课题在于解决多个非水电解质二次电池串联连接而成的电池单元中的上述问题,其课题还在于在利用于需要高输出功率及高容量的电动工具、电动汽车、混合动力汽车的电源等的情况下,将电池单元的输出功率维持在高的状态,同时容易地抑制串联连接的非水电解质二次电池变成过充电状态,以获得高的安全性。
用于解决问题的方法
在本发明中,为了解决上述问题,提出了一种多个非水电解质二次电池串联连接而成的电池单元,其中,使充电时从正极活性物质中释放锂而电阻上升的电位不同的至少两种非水电解质二次电池串联连接。
在此,作为上述两种非水电解质二次电池,使用充电时从正极活性物质中释放锂而电阻上升的电位高的第1非水电解质二次电池、和充电时从正极活性物质中释放锂而电阻上升的电位低的第2非水电解质二次电池。
并且,充电时从正极活性物质中释放锂而电阻上升的电位高的第1非水电解质二次电池中,其正极活性物质优选使用可获得高输出功率的具有层状结构的锂过渡金属复合氧化物,例如钴酸锂LiCoO2、镍酸锂LiNiO2等包含钴和镍中至少1种的锂过渡金属复合氧化物。
另一方面,充电时从正极活性物质中释放锂而电阻上升的电位低的第2非水电解质二次电池中,正极活性物质优选包含通式LiMPO4(式中、M是选自Fe、Ni、Mn中的至少1种。)所示的橄榄石型磷酸锂化合物或尖晶石型锂锰复合氧化物。
在此,上述第2非水电解质二次电池中,作为用于其正极活性物质中的橄榄石型磷酸锂化合物,可使用例如橄榄石型磷酸铁锂LiFePO4,另外,作为尖晶石型锂锰复合氧化物,可使用例如尖晶石锰酸锂LiMn2O4
另外,上述第2非水电解质二次电池中,除了单独使用如上所述的由橄榄石型磷酸锂化合物或尖晶石型锂锰复合氧化物构成的正极活性物质以外,还可与这些正极活性物质组合使用上述由具有层状结构的锂过渡金属复合氧化物构成的正极活性物质。
另外,这样在第2非水电解质二次电池中,与由橄榄石型磷酸锂化合物或尖晶石型锂锰复合氧化物构成的正极活性物质组合使用上述具有层状结构的锂过渡金属复合氧化物的情况下,优选使用如下正极,即,该正极在正极集电体上层压有正极活性物质由上述橄榄石型磷酸锂化合物或尖晶石型锂锰复合氧化物构成的第1层、和正极活性物质由具有层状结构的锂过渡金属复合氧化物构成的第2层。
另外,上述第2非水电解质二次电池优选设置根据电池的内压上升而工作的电流断路阀。
另外,在上述第1非水电解质二次电池及第2非水电解质二次电池中,除了使用如上所述的正极活性物质以外,可与通常公知的非水电解质二次电池同样地构成,对于用于负极的负极活性物质、用于非水电解液的非水系溶剂和溶质、隔膜等,可使用通常使用的公知物质。
发明效果
本发明的电池单元中,由于如上述那样使充电时从正极活性物质中释放锂而电阻上升的电位不同的至少两种非水电解质二次电池串联连接,因而,对这样的电池单元进行充电时,从正极活性物质中释放锂而电阻上升的电位低的第2非水电解质二次电池的电阻大大上升,抑制了从正极活性物质释放锂而电阻上升的电位高的第1非水电解质二次电池变成过充电状态,获得高安全性。
在此,作为上述第1非水电解质二次电池的正极活性物质,使用具有层状结构的锂过渡金属复合氧化物即钴酸锂LiCoO2或镍酸锂LiNiO2的情况下,即使充电到通常的非水电解质二次电池的上限充电电压4.2V(相对于锂参比电极电位为4.3V)左右,这些正极活性物质中的Li离子也不会全部释放,在使用LiCoO2的情况下,残留50%左右的Li离子,在使用LiNiO2的情况下,残留25%左右的Li离子,当进一步充电到高电压时,Li离子进一步被释放,成为能量上不稳定的过充电状态,热稳定性大大降低。
相对于此,上述第2非水电解质二次电池中,当正极活性物质包含橄榄石型磷酸锂化合物或尖晶石型锂锰复合氧化物时,这些正极活性物质的情况下,若充电到通常非水电解质二次电池的上限充电电压4.2V(相对于锂参比电极电位为4.3V)左右,则结晶中的Li离子全部被释放而电阻大大上升,并使流经该第2非水电解质二次电池的电流大大降低。
因此,将使上述第1非水电解质二次电池和第2非水电解质二次电池串联连接而成的电池单元充电到非水电解质二次电池的上限充电电压4.2V(相对于锂参比电极电位为4.3V)左右时,如上述那样,第2非水电解质二次电池的电阻大大上升,流经电池单元的电流大大降低,抑制第1非水电解质二次电池变成过充电状态,可获得高的安全性。
另外,作为上述第1非水电解质二次电池的正极活性物质,使用具有层状结构的锂过渡金属复合氧化物即钴酸锂LiCoO2或镍酸锂LiNiO2时,通过该第1非水电解质二次电池可获得高输出功率的电池单元。
另外,上述第2非水电解质二次电池的正极活性物质中,与上述橄榄石型磷酸锂化合物或尖晶石型锂锰复合氧化物组合使用上述具有层状结构的锂过渡金属复合氧化物时,与第2非水电解质二次电池的正极活性物质仅使用橄榄石型磷酸锂化合物或尖晶石型锂锰复合氧化物的情况相比,可获得更高输出功率的电池单元。
另外,这样在第2非水电解质二次电池的正极活性物质中,与上述橄榄石型磷酸锂化合物或尖晶石型锂锰复合氧化物组合使用上述具有层状结构的锂过渡金属复合氧化物时,若在正极集电体上层压上述由橄榄石型磷酸锂化合物或尖晶石型锂锰复合氧化物构成的正极活性物质的第1层、和由具有层状结构的锂过渡金属复合氧化物构成的正极活性物质的第2层,则即便使第1层中的包括橄榄石型磷酸锂化合物或尖晶石型锂锰复合氧化物的正极活性物质的量减少,也可以通过与正极集电体接触的该第1层中的橄榄石型磷酸锂化合物或尖晶石型锂锰复合氧化物,有效防止电池单元变成过充电状态,并且,可通过上述第2层中的具有层状结构的锂过渡金属复合氧化物,获得更高输出功率的电池单元。
另外,上述第2非水电解质二次电池中设置根据电池的内压上升而工作的电流断路阀时,即便在电压上升导致非水电解液分解而产生气体并使电池内的压力上升的情况下该电流断路阀工作而遮断电流,进一步抑制变成过充电状态,可获得更高的安全性。
附图说明
图1是本发明的实施例中,非水电解质二次电池A1、B1a、B1b的制作中所使用的电极体的简要主视图和部分截面说明图。
图2是上述非水电解质二次电池A1、B1a、B1b的简要主视图。
图3是本发明的实施例中制作的非水电解液二次电池A2、B2的截面简图。
图4是表示非水电解质二次电池A1和非水电解质二次电池B1a串联连接而成的实施例1的电池单元的说明简图。
图5是表示非水电解质二次电池A1和非水电解质二次电池B1b串联连接而成的实施例1的电池单元的说明简图。
图6是表示2个非水电解质二次电池A1串联连接而成的比较例1的电池单元的说明简图。
图7是表示非水电解质二次电池A2和非水电解质二次电池B2串联连接而成的实施例3的电池单元的说明简图。
图8是表示2个非水电解质二次电池A2串联连接而成的比较例2的电池单元的说明简图。
符号的说明
1正极;1a极集电片;2负极;2a负极集电片;3隔膜;4电极体;5外装体;11极;12负极;13隔膜;14电池罐;15正极片;16正极盖;17负极片;18色缘垫;19极外部端子;A1、B1a、B1b、A2、B2非水电解质二次电池
具体实施方式
实施例
接着,列举实施例对本发明的电池单元进行具体说明,并且,列举比较例,清楚说明本发明的电池单元中可防止变成过充电状态。另外,本发明的电池单元并不限定于下述实施例所示的情况,在不改变其主旨的范围内可适当变更来实施。
在此,作为非水电解质二次电池,使用如下述那样制作的5种非水电解质二次电池。
(非水电解质二次电池A1)
非水电解质二次电池A1使用如下述那样制作的正极、负极和非水电解液。
正极的制作
作为正极活性物质使用钴酸锂LiCoO2,在N-甲基-2-吡咯烷酮溶剂中,以92∶5∶3的质量比混合该正极活性物质、作为导电剂的人工石墨粉末、作为粘结剂的聚偏氟乙烯,调制正极合剂浆料,将该正极合剂浆料涂布到由铝箔形成的正极集电体的两个面上,使其干燥后,压延而制作正极。
负极的制作
在水中,以98∶1∶1的质量比混合作为负极活性物质的石墨、作为粘结剂的丁苯橡胶、作为增稠剂的羧甲基纤维素,调制负极合剂浆料,将该负极合剂浆料涂布到由铜箔形成的负极集电体的两个面上,使其干燥后,压延而制作负极。
非水电解液的制作
作为非水系溶剂,使用以3∶7的体积比混合碳酸乙二酯、碳酸甲乙酯的混合溶剂,在该混合溶剂中溶解作为电解质的LiPF6并使其浓度为1mol/l,从而制作非水电解液。
并且,该非水电解质二次电池A1中,如图1(A)、(B)所示,在上述正极1上安装由铝形成的正极集电片1a,并在上述负极2上安装由镍形成的负极集电片2a,该正极1、负极2夹着由聚乙烯制多孔体形成的隔膜3而相面对地卷绕,制作电极体4,对该电极体4进行挤压使其变扁平。
接着,如图2所示,将上述电极体4插入到由铝层压薄膜构成的外装体5内,另一方面,将上述正极集电片1a和负极集电片2a抽出到外装体5的外部,向该外装体5内加入上述非水电解液,然后,将上述外装体5的开口部封口,得到设计容量为780mAh的扁平的卡型非水电解质二次电池A1。
(非水电解质二次电池B1a)
在非水电解质二次电池B1a中,使用如下述那样制作的正极,除此之外,与上述非水电解质二次电池A1同样地得到设计容量为780mAh的扁平的卡型非水电解质二次电池B1a。
在此,在该非水电解质二次电池B1a中,使用橄榄石型磷酸铁锂LiFePO4作为正极活性物质,在N-甲基-2-吡咯烷酮溶剂中,以85∶10∶5的质量比混合该正极活性物质、作为导电剂的人工石墨粉末、作为粘结剂的聚偏氟乙烯,调制正极合剂浆料,将该正极合剂浆料涂布到由铝箔形成的正极集电体的两个面上,使其干燥后,压延而制作正极。
(非水电解质二次电池B1b)
在非水电解质二次电池B1b中,使用如下述那样制作的正极,除此之外,与上述非水电解质二次电池A1同样地得到设计容量为780mAh的扁平的卡型非水电解质二次电池B1b。
在此,在该非水电解质二次电池B1b中,第1正极活性物质使用橄榄石型磷酸铁锂LiFePO4,在N-甲基-2-吡咯烷酮溶剂中,以85∶10∶5的质量比混合该第1正极活性物质、作为导电剂的人工石墨粉末、作为粘结剂的聚偏氟乙烯,调制第1正极合剂浆料。另外,第2正极活性物质使用钴酸锂LiCoO2,在N-甲基-2-吡咯烷酮溶剂中,以92∶5∶3的质量比混合该第2正极活性物质、作为导电剂的人工石墨粉末、作为粘结剂的聚偏氟乙烯,调制第2正极合剂浆料。
并且,将上述第1正极合剂浆料涂布到由铝箔形成的正极集电体的两个面上,形成包含第1正极活性物质橄榄石型磷酸铁锂LiFePO4的第1层后,在该第1层上涂布第2正极合剂浆料,形成包含第2正极活性物质钴酸锂LiCoO2的第2层,然后,使其干燥,压延而制作正极。
(非水电解质二次电池A2)
非水电解质二次电池A2中,使用如下述那样制作的正极、负极和非水电解液。
正极的制作
正极活性物质使用由具有层状结构的LiNi0.3Co0.3Mn0.3O2形成的锂·镍·钴·锰复合氧化物,在N-甲基-2-吡咯烷酮溶剂中,以94∶3∶3的质量比混合该正极活性物质、作为导电剂的人工石墨粉末、作为粘结剂的聚偏氟乙烯,调制正极合剂浆料,将该正极合剂浆料涂布到由铝箔形成的正极集电体的两个面上,使其干燥后,压延而制作正极。
负极的制作
在水中以98∶1∶1的质量比混合作为负极活性物质的石墨、作为粘结剂的丁苯橡胶、作为增稠剂的羧甲基纤维素,调制负极合剂浆料,将该负极合剂浆料涂布到由铜箔形成的负极集电体的两个面上,使其干燥后,压延而制作负极。
非水电解液的制作
作为非水系溶剂,使用以3∶7的体积比混合碳酸乙二酯、碳酸甲乙酯而成的混合溶剂,在该混合溶剂中溶解作为电解质的LiPF6并使其浓度为1mol/l,制作非水电解液。
并且,该非水电解质二次电池A2中,如图3所示,在上述那样制作的正极11和负极12之间,夹入作为隔膜13的锂离子透过性的聚乙烯制微多孔膜,将它们卷成螺旋状而容纳于电池罐14内,通过正极片15使上述正极11与安装到正极盖16上的正极外部端子19连接,并且,通过负极片17使上述负极12与电池罐14连接后,向该电池罐14内注入上述非水电解液,通过绝缘垫18使电池罐14与正极盖16电隔离,并进行封口,得到设计容量为1300mAh的圆筒型非水电解质二次电池A2。
(非水电解质二次电池B2)
非水电解质二次电池B2中,使用如下述那样制作的正极,除此之外,与上述非水电解质二次电池A2同样地得到设计容量为1300mAh的圆筒型非水电解质二次电池B2。
在此,该非水电解质二次电池B2中,使用橄榄石型磷酸铁锂LiFePO4作为正极活性物质,在N-甲基-2-吡咯烷酮溶剂中以85∶10∶5的质量比混合该正极活性物质、作为导电剂的人工石墨粉末、作为粘结剂的聚偏氟乙烯,调制正极合剂浆料,将该正极合剂浆料涂布到由铝箔形成的正极集电体的两个面上,使其干燥后,压延而制作正极。
并且,实施例1的电池单元中,如图4所示,使上述卡型非水电解质二次电池A1与非水电解质二次电池B1a串联连接,在实施例2的电池单元中,如图5所示,使上述卡型非水电解质二次电池A1与非水电解质二次电池B1b串联连接,在比较例1的电池单元中,如图6所示,使2个上述卡型非水电解质二次电池A1串联连接。
另外,实施例3的电池单元中,如图7所示,使上述圆筒型非水电解质二次电池A2与非水电解质二次电池B2串联连接,在比较例2的电池单元中,如图8所示,使2个上述圆筒型非水电解质二次电池A2串联连接。
并且,对于实施例1、2及比较例1的电池单元以2340mA(780mA×3)的充电电流、另外对于实施例3及比较例2的电池单元以3900mA(1300mA×3)的充电电流,分别充电到电压为24V后,以24V的恒定电压进行恒定电压充电,直到电流不流动,分别对5个电池单元进行过充电试验,求出电池温度大大上升而发生内部短路的电池单元数目,其结果示于下述表1。另外,在上述过充电试验中,为了确认各非水电解质二次电池的过充电状态,与市售的非水电解质二次电池不同,除去隔膜的关闭机构、电流断路阀及保护元件,并排除其他用于确保安全性的装置。
表1
Figure 200810006414XA00800011
其结果是,将2个正极活性物质使用具有层状结构的锂过渡金属复合氧化物LiCoO2的非水电解质二次电池A1串联连接而成的比较例1的电池单元、将2个正极活性物质使用具有层状结构的锂过渡金属复合氧化物LiNi0.3Co0.3Mn0.3O2的非水电解质二次电池A2串联连接而成的比较例2的电池单元,5个电池单元全部变成过充电状态,电池温度大大上升,发生了内部短路。
相对于此,使正极活性物质使用具有层状结构的锂过渡金属复合氧化物LiCoO2的非水电解质二次电池A1与正极活性物质使用橄榄石型磷酸铁锂LiFePO4的非水电解质二次电池B1a串联连接而成的实施例1的电池单元、使上述非水电解质二次电池A1与在集电体上层压有正极活性物质由橄榄石型磷酸铁锂LiFePO4构成的第1层和正极活性物质由钴酸锂LiCoO2构成的第2层的非水电解质二次电池B1b串联连接而成的实施例2的电池单元、正极活性物质使用具有层状结构的锂过渡金属复合氧化物LiNi0.3Co0.3Mn0.3O2的非水电解质二次电池A2与正极活性物质使用橄榄石型磷酸铁锂LiFePO4的非水电解质二次电池B2串联连接而成的实施例3的电池单元中,5个电池单元全部防止了变成过充电状态,没有电池温度大大上升而发生内部短路的情况。
另外,上述实施例中,在上述非水电解质二次电池B1a、B1b、B2中,使用橄榄石型磷酸铁锂LiFePO4作为充电时释放锂而电阻上升的电位低的正极活性物质,使用其他橄榄石型磷酸锂化合物或尖晶石型锂锰复合氧化物的情况下也可获得同样的结果。

Claims (7)

1.一种电池单元,该电池单元由多个非水电解质二次电池串联连接而成,其特征在于,使充电时从正极活性物质中释放锂而电阻上升的且电位不同的至少两种非水电解质二次电池串联连接,
作为所述非水电解质二次电池,使用充电时从正极活性物质中释放锂而电阻上升的电位高的第1非水电解质二次电池、以及充电时从正极活性物质中释放锂而电阻上升的电位低的第2非水电解质二次电池,第1非水电解质二次电池中的正极活性物质使用具有层状结构的锂过渡金属复合氧化物,另一方面,第2非水电解质二次电池中的正极活性物质包含橄榄石型磷酸铁锂LiFePO4或尖晶石型锂锰复合氧化物,
至少在充电时从正极活性物质中释放锂而电阻上升的电位低的第2非水电解质二次电池中,设有根据电池的内压上升而工作的电流断路阀。
2.根据权利要求1所述的电池单元,其特征在于,所述第2非水电解质二次电池中的正极活性物质包含橄榄石型磷酸铁锂LiFePO4或尖晶石锰酸锂LiMn2O4
3.根据权利要求2所述的电池单元,其特征在于,所述第2非水电解质二次电池中的正极活性物质为橄榄石型磷酸铁锂LiFePO4
4.根据权利要求1所述的电池单元,其特征在于,所述第2非水电解质二次电池的正极在正极集电体上层压有第1层和第2层,所述第1层,其正极活性物质由橄榄石型磷酸铁锂LiFePO4或尖晶石型锂锰复合氧化物构成;所述第2层,其正极活性物质由具有层状结构的锂过渡金属复合氧化物构成。
5.根据权利要求4所述的电池单元,其特征在于,所述第1层,其正极活性物质由橄榄石型磷酸铁锂LiFePO4或尖晶石锰酸锂LiMn2O4构成。
6.根据权利要求5所述的电池单元,其特征在于,所述第1层,其正极活性物质为橄榄石型磷酸铁锂LiFePO4
7.根据权利要求1~6任一项所述的电池单元,其特征在于,所述第1非水电解质二次电池中的正极活性物质是含有钴和镍中的至少1种的锂过渡金属复合氧化物。
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