CN100541877C - 用于锂离子电池的多相、含硅电极 - Google Patents
用于锂离子电池的多相、含硅电极 Download PDFInfo
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Abstract
一种用于锂离子电池的电极组合物,包括具有1μm至50μm范围内的平均颗粒尺寸的颗粒。该颗粒包括共享公共相界的电化学活性相和电化学非活性相。电化学活性相包括元素硅,以及电化学非活性相包括以金属间化合物、固体溶液或其组合物的形式的至少两种金属元素。在循环之前,该相的每一种没有大于1000埃的晶粒。此外,在通过锂离子电池中的一次完全充电-放电循环该电极被循环之后,电化学活性相是非晶的。
Description
技术领域
本发明涉及对锂离子电池有用的电极组合物。
背景技术
各种各样的金属、类金属(metalloid)以及合金已被研究,用于用作锂离子电池的活性阳极组合物。这些材料是吸引人的,因为它们与碳和石墨相比潜在地具有较高的重量和体积容量,目前碳和石墨两者都用作锂离子电池中的阳极。但是,利用这些材料的一个问题是,由于锂化和去锂化,在电池工作过程中它们经历大的体积膨胀。该体积膨胀又导致该材料被损坏,因此限制循环寿命(cycle life)。此外,用来制备这些材料的方法一直不容易大规模制造。
发明内容
本发明提供适于锂离子电池使用的电极组合物,其中该电极组合物显示出高的电容量和良好的循环寿命。此外,该电极组合物和引入该电极组合物的电池被容易地制造。
为了获得这些目的,本发明的特点在于,在第一方面,电极组合物包括具有1μm至50μm范围内的平均颗粒尺寸的颗粒,其中该颗粒包括共享至少一个公共相界的电化学活性相和电化学非活性相。电化学活性相包括元素硅,以及电化学非活性相包括以金属间化合物、固体溶液或其组合物的形式的至少两种金属元素。在某些实施例中,电化学非活性相还包括硅。该相的每一种在循环之前没有大于1000埃的晶粒。而且,电化学活性相在锂离子电池中通过一次完全充电-放电周期循环该电极之后是非晶的。优选,在附加充电-放电周期过程中,当电压大于70mV vs.Li/Li+时,更优选大于50mV vs.Li/Li+时,电化学活性相保持非晶。
“电化学活性”材料是在锂离子电池中的充电和放电过程中典型地相遇的条件下与锂起反应的材料。“电化学非活性”材料是在那种条件下不与锂起反应的材料。
“非晶”材料是通过x-射线衍射或透射电子显微镜观察缺乏结晶材料的长距离原子排序特性的材料。
该电极组合物可以根据工艺来制备,该工艺包括(a)在惰性气氛中将元素硅和两种以上的附加金属元素熔化在一起,以形成晶锭(ingot);(b)在惰性气氛中熔化该晶锭,以形成熔化流;(c)在转轮的表面上快速地淬火该熔化流,以形成带状物;以及(d)研磨该带状物,以形成具有1μm至50μm范围内的平均颗粒尺寸的颗粒。
在下面的附图和说明书中将阐述本发明的一个或多个实施例的细节。由本说明书及附图以及由权利要求将明白本发明的其他特点、目的和优点。
附图说明
图1是例1中所述的熔纺(melt-spun)硅-铝-铁粉末的x-射线衍射分布图。
图2依据容量vs.循环次数说明基于例1中所述的熔纺和非熔纺硅-铝-铁粉末的半电池的循环性能。
图3是例1中所述的熔纺硅-铝-铁粉末的扫描电子显微镜(SEM)图片。
图4说明基于例1中所述的熔纺硅-铝-铁粉末的半电池的不同容量(differential capacity)vs.电压。
图5是在循环之前和在35次循环之后例1中所述的熔纺硅-铝-铁粉末的x-射线衍射分布图。
图6是例2所述的粉末的容量vs.循环次数的曲线。
各个图中的相同参考符号表示相同的元素。
具体实施方式
下面将描述特别对锂离子电池的阳极有用的电极组合物。该电极组合物以电化学活性相和电化学非活性相为特点,电化学活性相包括元素硅,以及电化学非活性相包括两种以上的金属元素,以及优选硅。适合的金属元素的例子包括铁、铝、镍、锰、钴、铜、银,以及铬,铁、铜和铝是特别优选的。该两种相具有上面的发明内容中描述的显微结构。
该电极组合物优选通过冷铁熔纺工艺(chill block melt spinningprocess)来制备。例如在″Amorphous Metallic Alloys″F.E.Luborsky,ed.,Chapter 2,Butterworth&Co.,Ltd.(London),1983中大致地描述了这种工艺。根据该工艺,在射频场中熔化包含硅和两种以上的金属元素的晶锭,然后通过喷嘴喷射在旋转金属轮(例如,铜轮)的表面上。因为铜轮的表面温度充分地低于与轮的表面接触的熔料的温度,因此淬火该熔料。淬火防止形成对电极性能有害的大晶粒。
该电极组合物特别有用于锂离子电池的阳极。为了制备电池,该电极与电解液和阴极(反电极)结合。电解液可以以液体、固体或凝胶的形式。固体电解质的例子包括聚合的电解液如聚环氧乙烷、聚四氟乙烯、含氟的共聚物以及其组合物。液体电解质的例子包括碳酯乙烯、碳酸二乙酯、碳酸丙烯以及其组合物。该电解液设有锂电解质盐。适合的盐的例子包括LiPF6、LiBF4和LiClO4。适合的阴极组合物的例子包括LiCoO2、LiCo0.2Ni0.8O2和LiMn2O4。
例子
例1
在称重盘中称量6.34g的铝粒,12.10g的硅薄片和6.56g的铁薄片(所有是99.9%或更好的纯度),然后放入电弧炉中。在Ti池(pool)氧气吸气剂存在的情况下,在Ar气氛中熔化该混合物,以产生具有组合物Si55Al30Fe15的25g的晶锭,其中所有量都用原子百分数。
该晶锭被打碎成为小于15mm直径的碎片。在以0.035mil(0.89μm)直径喷嘴中结束的石英管内放入10g的这种材料。在该管中还插入薄碳套筒,作为射频耦合器,以开始晶锭的熔化。该管被放入超过200mm直径铜轮的熔纺器的室中,以便从喷嘴口到轮表面的距离是10mm。然后该室被抽空到80mTorr,并用He再充气到200Torr。然后在射频场中熔化该晶锭。当熔料达到1150℃时,在80Torr He过压下,将熔化的液体喷射在以35rn/秒的表面速度旋转的铜轮上,以淬火该熔料和形成带状碎片。收集约9g的带状碎片。
在行星式碾磨机(planetary mill)中,在含水泥浆中,通过球磨粉碎该带状碎片1小时,以形成粉末。在80℃下,在烘箱中风干之后,通过具有53微米、32微米和20微米的孔径尺寸的筛子筛分,将粉末分级。32和53微米之间的碎片被选择,用于进一步研究。使用装备有铜靶x-射线管和衍射束单色仪的Siemens Model Kristalloflex 805D500衍射计收集其x-射线衍射图形。在图1中示出了该结果。峰宽的分析表示元素硅相的494埃的晶粒尺寸以及铁和含铝相的415埃的晶粒尺寸。
图3是分级的粉末的扫描电子显微镜(SEM)图片。如图3所示,粉末的显微结构以元素硅的分立区为特点,元素硅的分立区共享具有硅-铝-铁三元合金的区域的相界。
未经受熔纺的剩余晶锭材料被类似地研磨,以形成粉末并被分级,以及测量32和53微米之间的碎片的x-射线衍射图形。峰宽的分析表示元素硅的1243埃的晶粒尺寸和剩余组合物的732埃的晶粒尺寸。因此,熔纺导致形成具有显著地较小的晶粒尺寸的材料。
为了制备用于电化学循环的电极,在1g的N-甲基-2-吡咯烷酮(NMP)中悬浮0.8g的每种粉末。接下来,按1∶1重量的NMP和聚偏二氟乙烯(Kynar461,可以由Elf Atochem获得)中的3.6g的超级P碳(可以由MMM获得,比利时)的6%固体悬浮体被添加到该粉末悬浮体。在高剪切下下搅拌所得的悬浮体5分钟,然后涂敷在具有切口条的12mil(0.305mm)铜箔上,以提供80%活性、10%聚偏二氟乙烯、10%超级P碳涂层。在150℃下在真空中干燥该涂层4小时,以形成电极。通过使它与金属锂阳极结合,该电极用于构成2325个硬币(coin)电池,双层的Cellgard 2400作为隔板,以及用碳酯乙烯和碳酸二乙酯的1∶2混合物中的1M LiPF6作为电解质。
对于第一循环,在0.9V和0.025V之间的0.125mA恒定电流下,使用MACCOR周期计循环该电池,以及对于所有附加循环,在0.9V和0.050V或0.005V之间的0.5mA的恒定电流下循环该电池。在图2中示出了该结果。如该图所示,具有较小晶粒的熔纺材料(黑色三角形)的性能优于非熔纺材料(黑色菱形)的性能。此外,观察超过约50mV的电压的增强性能。具体地,当循环到50mV(黑色三角形)时,熔纺材料显示出99.3%的平均库仑(coulombic)效率。但是,当该材料被循环到5mV(开口正方形)时,那些值下降到98.2%。
图4的不同电容量曲线包含三个曲线。曲线(a)表示在一次循环之后获得的结果。曲线(b)表示在两次循环之后获得的结果。曲线(c)表示当锂化(lithiation)被限制为50mV时获得的结果。该结果说明当锂化被限制为约50mV时,熔纺材料的非晶硅相保持非晶。另一方面,在50mV以下的值,导致晶体硅的形成。
图5比较第一循环(迹线(a))之前和35次循环(迹线(b))之后阳极的x-射线衍射图形。如图所示,在35次循环之后,硅相是非晶的,但是硅-铝-铁相的晶粒尺寸基本上保持不变。
例2
如例1所述制备、研磨并分级熔纺的Si55Al30Fe15带。32和20微米之间的碎片被隔离。根据Krause人2001年6月18日申请的、名称为″Electrode Compositions Having Improved Cycling Behavior,″、转让给本申请的相同受让人的U.S.S.N.09/883,865描述的方法,用Ag的多孔层涂敷部分碎片。重量上升10%。银-涂敷的颗粒被分散在甲基乙基酮中以及通过摇动进一步与3-氨丙基三甲氧基硅烷(aminopropyltrimethyoxysilane)(Aldrich Chemical)(每1g的粉末,60mg硅烷)起反应8小时。
处理的粉末用于制备如例1所述的电极,除了粘合剂是可以由Dyneon LLC中获得的名称为FC-2179的含氟化合物弹性体,碳是超级S碳之外,最终的涂敷组合物包含80%活性粉末、14%碳和6%粘合剂。在图6中示出了依据容量vs.循环次数,引入这些电极的半电池的性能。如例1所述,制备该半电池。如图6所示,该电池显示出良好的循环性能。
例3
在称重盘中称量6.98g的铝粒,14.80g的硅薄片和8.22g的铜粒(所有都是99.9%或更好的纯度),然后放入电弧炉中。在Ti池(pool)氧气吸气剂的存在情况下,在Ar气氛中熔化该混合物,以产生具有组合物Si57Al28Cu14的30g晶锭,所有量都用原子百分数。
该晶锭被打碎成小于15mm直径的碎片。在0.030mil(0.76m)直径喷嘴中结束的碳管内放入10g的这种材料。该管被放入超过200mm直径铜轮的熔纺器的室中,以便从喷嘴口到轮表面的距离是10mm。然后该室被抽空到80mTorr,并用He再充气到200Torr。然后在射频场中熔化该晶锭。当熔料达到1200℃时,在80Torr He过压下将熔化的液体喷射在以35m/sec的表面速度旋转的铜轮上,以淬火该熔料和形成带状碎片。收集约9g的带状碎片。
通过在研钵和研杵中碾磨而粉碎该带状碎片。通过具有53微米、32微米和20微米孔径尺寸的筛子的筛分将该粉末分级。32和53微米之间的碎片被选择用于进一步研究。使用装备有铜靶x-射线管和衍射束单色仪的Siemens Model Kristalloflex 805D500衍射计收集其x-射线衍射图形。该XRD图形说明仅仅相Si和Al2Cu的存在。峰宽的分析表示元素硅相的395埃的晶粒尺寸和Al2Cu相的270埃的晶粒尺寸。
该粉末样品被制成涂层电极,引入电化学电池中,并循环,如例1中的粉末样品所述。对于第一循环,通过0.9V和0.05V之间的恒定电流(0.25mA)充电和放电,执行该循环,对于所有附加循环0.9V和0.070之间的恒定电流充电和放电,执行该循环。该电池具有1680mAh/g的第一放电容量和具有不同的电容量曲线,仅仅表明第一循环之后完全地非晶硅的性能。
为了证实Al2Cu相是电化学非活性的,9.18g的铝和10.82g的铜(所有是99.9%或更好的纯度)被放入电弧炉中。在Ti池(pool)氧气吸气剂存在的情况下,在Ar气氛中熔化该混合物,以产生具有组合物Al2Cu的20g晶锭。用研钵和研杵研磨该锭,以及通过具有53微米、32微米和20微米的孔径尺寸的筛子的筛分分级。32和53微米之间的碎片被选择用于进一步研究。如上所述收集其x-射线衍射图形,对应于Al2Cu相。
该粉末样品被制成涂层电极,引入电化学电池中,以及如上所述循环。通过0.9V和0.005V之间的恒定电流(0.25mA)充电和放电执行循环。该电池表明没有来自Al2Cu相的电容量,证实它是电化学非活性的。
上面已经描述了本发明的大量实施例。然而,应当理解在不脱离本发明的精神和范围的条件下可以进行各种改进。由此,其他实施例在以下权利要求的范围内。
Claims (6)
1.一种用于锂离子电池的电极组合物,包括具有1μm至50μm范围内的平均颗粒尺寸的颗粒,
所述颗粒包括共享至少一个公共相界的电化学活性相和电化学非活性相,所述电化学活性相包括元素硅,以及所述电化学非活性相包括以金属间化合物、固体溶液、或其组合物的形式的至少两种金属元素,所述至少两种金属元素包括铝和铜,或者所述电化学非活性相包括硅、铝和铁,其中
(a)在充电/放电循环之前,所述相的每一种没有大于1000埃的晶粒,以及
(b)当所述电极组合物包含在锂离子电池中,并且通过一次完全充电-放电循环时,所述电化学活性相是非晶的。
2.根据权利要求1的电极组合物,其中,当所述至少两种金属元素包括铝和铜时,所述电化学非活性相还包括硅。
3.一种锂离子电池,包括:
(a)阳极,该阳极包括具有1μm至50μm范围内的平均颗粒尺寸的颗粒,
所述颗粒包括共享至少一个公共相界的电化学活性相和电化学非活性相,所述电化学活性相包括元素硅,以及所述电化学非活性相包括以金属间化合物、固体溶液、或其组合物的形式的至少两种金属元素,所述至少两种金属元素包括铝和铜,或者所述电化学非活性相包括硅和作为所述至少两种金属元素中的两种金属的铝和铁,其中
(i)在充电/放电循环之前,所述相的每一种没有大于1000埃的晶粒,以及
(ii)当所述电极组合物包含在锂离子电池中,并且通过一次完全充电-放电循环时,所述电化学活性相是非晶的;
(b)阴极;以及
(c)将阳极和阴极隔开的电解质。
4.根据权利要求3的电极组合物,其中,当所述至少两种金属元素包括铝和铜时,所述电化学非活性相还包括硅。
5.一种用于制备锂离子电池用的电极组合物的方法,包括:
(a)在惰性气氛中将元素硅和两种或更多种的附加金属元素熔化在一起,以形成晶锭;
(b)在惰性气氛中熔化该晶锭,以形成熔化流;
(c)在转轮的表面上快速地淬火该熔化流,以形成带状物;以及
(d)研磨该带状物,以形成具有1μm至50μm范围内的平均颗粒尺寸的颗粒,
所述颗粒包括共享至少一个公共相界的电化学活性相和电化学非活性相,所述电化学活性相包括元素硅,以及所述电化学非活性相包括以金属间化合物、固体溶液、或其组合物的形式的至少两种金属元素,所述至少两种金属元素包括铝和铜,或者所述电化学非活性相包括硅和作为所述至少两种金属元素中的两种金属的铝和铁,以及
(e)将电极组合物集成到锂离子电池中并且通过至少一个充电-放电循环来循环该电池,其中在充电/放电循环之前,所述相的每一种没有大于1000埃的晶粒,并且当所述电极组合物包含在锂离子电池中,并且通过一次完全充电/放电循环时,所述电化学活性相是非晶的。
6.根据权利要求5的方法,其中,当所述至少两种金属元素包括铝和铜时,所述电化学非活性相还包括硅。
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- 2004-07-30 WO PCT/US2004/024971 patent/WO2005018026A2/en active Application Filing
- 2004-07-30 KR KR1020067002612A patent/KR101120692B1/ko active IP Right Grant
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CN1842932A (zh) | 2006-10-04 |
JP2012004130A (ja) | 2012-01-05 |
EP1652249B1 (en) | 2008-06-11 |
KR101120692B1 (ko) | 2012-03-23 |
JP4865556B2 (ja) | 2012-02-01 |
EP1652249A2 (en) | 2006-05-03 |
WO2005018026A3 (en) | 2006-02-23 |
KR20060054430A (ko) | 2006-05-22 |
DE602004014384D1 (de) | 2008-07-24 |
JP5616298B2 (ja) | 2014-10-29 |
WO2005018026A2 (en) | 2005-02-24 |
CA2535006A1 (en) | 2005-02-24 |
JP2007502004A (ja) | 2007-02-01 |
US7498100B2 (en) | 2009-03-03 |
US20050031957A1 (en) | 2005-02-10 |
ATE398339T1 (de) | 2008-07-15 |
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