CN101366133B - 安全性强化的电化学装置 - Google Patents
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Abstract
本发明涉及一种电极,其包括电极活性材料粒子、导电粒子、粘合剂和蜡,其中电极活性材料粒子通过导电粒子的网络互相连接,而连接电极活性材料的导电粒子的路径被蜡部分或全部固定。此外,本发明提供包含所述电极的电化学装置。通过使用具有低熔融粘度的蜡,以部分或完全地固定将隔开的电极活性材料粒子互相连接的导电粒子的路径,本发明可改进电化学装置的可加工性及安全性。
Description
技术领域
本发明涉及一种电极,其包括电极活性材料粒子、导电粒子、粘合剂和蜡,制造所述电极的方法,以及使用所述电极的电化学装置。
背景技术
近来,对能量储存技术的兴趣骤增。特别是,电化学装置的应用已延伸至移动电话、可携式摄像机、手提电脑、计算机以及电动车辆,因此发展此类电化学装置的努力和尝试日益实现。基于此点,电化学装置领域受到高度关注,尤其是有很多兴趣集中在可再充电二次电池的发展。在现今使用的二次电池中,在1990年代早起发展出的锂离子二次电池,因为其工作电压及能量密度高于使用含水溶液电解质的传统电池,如镍氢电池、镍镉电池及硫酸铅电池,因而受到关注。
然而,当电池在充满电状态下,其电池温度会因环境的变化,如受到压力、钉、镊子等外力撞击、环境温度上升、过度充电等而升高,锂离子二次电池可能会因电极活性材料与电极反应而发生膨胀,或更糟的是爆炸或燃烧。
特别是,阴极活性材料对电压敏感。所以,在电池被充电时使电压的上升,使阴极与电解质反应度增加,阴极的表面会被溶解,导致电解质的氧化。因此,使得燃烧及爆炸可能性增高。
“高温过度充电”是危险事件,可能会造成锂离子电池变成最坏的情况。例如:若锂离子电池在高于4.2V过度充电,其电解质开始溶解,如果温度增加至燃点,则发生燃烧的可能性就会增加。
安全问题亟需解决,因为电池,尤其是非水电解质二次电池,如锂离子二次电池被设计为具有高电容量与高能量密度。
发明内容
本发明目的是提供一种电化学装置,其中安全性通过依靠电阻中断电流而提升,所述电阻对装置内的温度增加迅速响应而增加。
本发明提供一种电极,包括电极活性材料粒子、导电粒子、粘合剂和蜡,其中电极活性材料粒子通过导电粒子的网络互相连接,而连接电极活性材料的导电粒子的路径被蜡部分或全部固定;以及包括所述电极的电化学装置。
另外,本发明提供一种制造电化学装置的方法,其包括下列步骤:
(a)制备浆料,其中将(i)电极活性材料粒子、(ii)导电粒子、(iii)粘合剂和(iv)蜡,分散在溶剂中;
(b)将所述浆料涂覆在集流体上,并干燥和压制所述浆料以提供电极;以及
(c)组装电化学装置,其包括由步骤(b)所得电极,以及注入非水电解质至该装置内。
以下,将对本发明作详细描述。
蜡是一种低聚物,容易被熔化并具有非常低的熔融粘度,不像聚合物具有高粘度。这样的蜡为一种油膏状(unctuous)固体,具有可滑动性及可塑性,并具有500至10,000范围的低分子量。
本发明的特征在于隔开的电极活性材料粒子通过导电粒子的网络互相连接,而连接电极活性材料的导电粒子的路径被蜡部分或全部固定(见如图1)。
作为电子导电通道时,彼此相互连接的导电粒子,连接隔开的导电活性材料。
电化学装置具有前述特征时,可使装置内安全性有所提升(见图3及图5)。特别是,若电化学装置内的温度因过度充电等而超过蜡的熔点时,蜡会熔解及流动遍及电极内形成的孔。因此,用蜡固定的导电粒子彼此间会分开(如图1),因而电极的电阻增加而使得电流中断。于是,该装置内部温度不再增加。
例如,当电池过度充电时,电池内的温度会增加。结果,电极中的蜡熔化因而增加电极的电阻,使得过量充电立即停止以避免电池的爆炸及燃烧。
同时,当相较于聚合物时,蜡是一种寡聚物,具有很低的熔融粘度,并在熔化时具有优异的流动性(mobility)。因此,当蜡熔化时可迅速地分散,可有效地使电极中导电粒子分开。由于其对电化学装置内的温度增加反应时间短,可获得装置内的安全性有效达成。
蜡的熔融粘度优选范围在10-1,000mPa.s,更优选400mPa.s或更低。另外,优选当装置内部温度增加至一定程度时,蜡会具有前述熔融粘度,以使电流中断。
如熔融粘度低于10mPa.s,蜡所具有的分子量会过低,以致于导电粒子的网络无法有效地分开。在这种情况下,安全性的有效提升无法达成。如熔融粘度高于1,000mPa.s,高熔融粘度导致流动性的降低,会使得导电粒子的网络无法被迅速分开。
蜡的分子量优选等于或小于10,000。分子量太大引起粘度等的增加而流动性降低,会使得因温度增加引起的电极电阻增加的反应速度降低。蜡的分子量下限值可由如上述熔融粘度下限值来决定。
聚偏氟乙烯(PVdF)通常用作电极中的粘合剂,其熔点为175℃。另一方面,蜡具有80至130℃的熔点,其是用来达成电化学装置如电池对抗温度的安全性的适当范围。
蜡优选聚烯烃基蜡。聚烯烃基蜡因缺乏官能基,所以在电池内不会发生任何反应。
聚烯烃基蜡的实例为聚乙烯蜡、聚丙烯蜡等。
蜡的粒径优选20μm或更小,粒径过大会造成蜡分散的问题,以及进一步会造成电极涂层擦伤。
蜡的用量优选占电极(不计集流体的质量)的0.1wt.%至10wt.%。如果蜡的使用量过少会无法执行它应有的功能;如果蜡使用量过多,会有容量及电池效能等问题。
导电粒子的非限制性实例,包括乙炔黑或炭黑。如电极为阴极时,导电粒子在电极中的使用量为0.5至10wt.%,如电极为阳极时,导电粒子在电极中的使用量为小于10wt.%。
本发明可以分别或同时应用在阴极及阳极上,以及对电化学装置中的锂二次电池特别有效。
一般来说,锂二次电池包括:可吸收及释放锂离子的阴极,可吸收及释放锂离子的阳极,非水电解质,和隔膜。
锂复合氧化物用作构成阴极的阴极活性材料。根据非限制性实例,锂复合氧化物以含锂嵌入材料为主要组成,例如镁酸锂(lithiatedmagnesium oxide)、钴酸锂(lithiated cobalt oxide)、镍酸锂(lithiated nickel oxide)或由前述氧化物组合而成的复合氧化物。
接着,阴极活性材料粘结至阴极集流体,如铝箔、镍箔或其组合而构成阴极。阴极活性材料的量优选80至99wt.%。
构成阳极的阳极活性材料包含作为主要组成的锂嵌入材料,例如锂金属、锂合金、碳、石油焦、活性炭、石墨或各种形式的碳等。阳极活性材料粘结至阳极集流体,如铜、金、镍或铜合金、或其组合制成的箔,以构成阳极。阳极活性材料的量优选80至99wt.%。
本发明所使用粘合剂的非限制性实例是选自下列组群的至少一种:聚四氟乙烯、聚偏氟乙烯、聚氟乙烯、聚丙烯腈、丁腈橡胶、聚丁二烯、聚苯乙烯、丁苯橡胶、聚硫橡胶、丁基橡胶、加氢丁苯橡胶、硝化纤维素和羧甲基纤维素。粘合剂的量优选0.1至15wt.%。
隔膜可具有微孔结构,并可为聚乙烯、聚丙烯或由其组合制备的多层膜、或用于固体聚合物电解质或凝胶型聚合物电解质的聚合物膜,例如聚偏氟乙烯、聚氧乙烯、聚丙烯腈或聚偏氟乙烯六氟丙烯共聚物。
电解质可包含具有A+B-结构的盐类,其中A+包括碱金属阳离子,如Li+、Na+和K+或其组合,以及B-包括如PF6 -、BF4 -、Cl-、Br-、I-、ClO4 -、ASF6 -、CH3CO2 -、CF3SO3 -、N(CF3SO2)2 -和C(CF2SO2)3 -或其组合的阴离子。特别地,电解质所指为锂盐在有机溶剂中分解或分离,有机溶剂如碳酸亚丙酯(PC)、碳酸亚乙酯(EC)、碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸二丙酯(DPC)、二甲亚砜、乙腈、二甲氧基乙烷、二乙氧基乙烷、四氢呋喃、N-甲基吡咯烷酮(NMP)、碳酸甲乙酯(EMC)、γ-丁内酯或其混合物。
根据本发明电化学装置之制造方法包含以下步骤:(a)制备浆料,其中将(i)电极活性材料粒子、(ii)导电粒子、(iii)粘合剂和(iv)蜡,分散 在溶剂中;(b)将所述浆料涂覆在集流体上,干燥并压制该浆料以提供电极;以及(c)组装电化学装置,其包括由步骤(b)所得的电极,以及注入非水电解质至该装置内。
用于浆料的溶剂没有限制。一般而言,N-甲基吡咯烷酮(NMP)可同时用于阳极和阴极,蒸馏水可用于水性阳极。
分散在溶剂中的蜡以粉状形式(powder form)注入,其状态介于固态与液态之间。
当制造上述电极时,通过混合而彻底分散,在涂覆于电极之后,导电粒子分布以使隔开的电极活性材料互相连接。
如有需要,在制造电极时可使用热处理方式使溶剂蒸发。
换句话说,依据可分散性,颗粒的尺寸会密切影响到混合与涂覆的过程。具有低熔融粘度的蜡可在干燥电极时有效改进可分散性。因此,如果使用具有小粒径及低熔融粘度的蜡,能改进可加工性。
附图说明
图1是在根据本发明的电极中,电极活性材料粒子、导电粒子、粘合剂和蜡的关系示意图。
图2是根据实施例1,由扫描电子显微镜拍摄的包含蜡的电极照片。
图3是实施例1及比较例1中的电池,在100℃至120℃温度范围内电阻变化的曲线图。
图4是实施例1中,由扫描电子显微镜拍摄当温度上升至150℃时,蜡熔化的电极照片。
图5是实施例2及比较例2在12V/1C过度充电测试时,温度及电压变化的示意图。
具体实施方式
以下,本发明将由实施例更详细说明。下述实施例仅为了方便说明举例而已,而非用于限制本发明。
实施例1(纽扣电池的制造)
为了制备浆料,钴酸锂∶作为导电粒子的碳黑∶聚偏氟乙烯∶聚乙烯蜡以重量比93∶3∶2∶2分散于N-甲基吡咯烷酮(NMP)中。所述浆料涂覆在铝箔上,于150℃烘干并压制以形成阴极。压制后阴极的涂覆的厚度为70μm,铝箔不计。用作电阻粘合剂的聚乙烯蜡,具有10μm的粒径、90℃的熔点以及140mPa.s或更小的熔融粘度。至于阳极则使用金属锂。使用Cell Guard的A250作为隔膜。含有1M浓度LiPF6的EC/EMC(1∶2,基于重量分数)液态电解质用作电解质以提供纽扣电池。
比较例1
重复实施例1以提供纽扣电池,除了使用钴酸锂∶作为导电剂的碳黑∶聚偏氟乙烯重量百分比为94∶3∶3来制备浆料。
(评估)
图3的图显示了根据实施例1及比较例1所制造电池当表面温度从室温上升到140℃时之电阻变化。对于实施例1,电池的电阻在95℃时开始增加,并在约105℃有效地增加了5倍,或在120℃时比原始电阻增加了更多倍。电阻在约130℃时会增加到100倍或更多倍,其因隔离膜的孔洞被阻塞而导致隔离膜闭合。至于比较例1为一般电池,电阻会持续减少直到温度上升到约120℃,在约130℃时因隔离膜闭合,电阻会增加到100倍或更多倍。
实施例2(全电池(Full cell)的制造)
阴极使用与实施例1中纽扣电池相同成分比例来制造。另外,阳极通过阳极浆料制备,所述浆料通过使用人造石墨∶导电剂∶聚偏氟乙烯重量百分比为93∶1∶6获得。使用Cell Guard A250作为隔离膜。注入含1M浓 度LiPF6的EC/EMC(1∶2,基于重量分数)液态电解质,并用一般的堆栈及折叠方式来制造ICP 383562全电池(电容量为800mAh)。
比较例2
阴极通过使用与比较例1中纽扣电池相同的成分比例来制造。其它制造ICP 383562全电池(电容量为800mAh)步骤与实施例2所用方法相同。
(评估)
图5为根据实施例2和比较例2制造的电池,在过量充电至12V/1C时温度及电压的变化。如图5所示,根据比较例2的电池在过量充电时会燃烧及爆炸。然而,根据实施例2包含聚烯烃蜡的电池即使在表面温度上升至约120℃时都是安全的,不会发生燃烧或爆炸。
产业实用性
本发明通过使用具有低熔融粘度的蜡部分或完全地固定用来连接隔开的电极活性材料粒子的导电粒子的路径,可改进电化学装置的可加工性及安全性。
Claims (9)
1.一种电极,其包括:电极活性材料粒子、导电粒子、粘合剂和蜡,
其中所述电极活性材料粒子通过所述导电粒子的网络互相连接,而连接电极活性材料的导电粒子的路径被所述蜡部分地或全部地固定,
其中所述蜡的熔融粘度范围为10~400mPa.s,以及所述蜡的分子量为10,000或更小。
2.如权利要求1所述的电极,其中所述蜡为聚烯烃基蜡。
3.如权利要求1所述的电极,其中所述蜡的粒径为20μm或更小。
4.如权利要求1所述的电极,其中所述蜡的熔点范围为80至130℃。
5.如权利要求1所述的电极,其中不计集流体的质量,所述蜡在电极中的使用量为0.1wt.%至10wt.%。
6.一种电化学装置,其包括:阴极、阳极和电解质,
其中所述阴极或所述阳极,或所述阴极与所述阳极两者,为如权利要求1至5中任一项所述的电极。
7.如权利要求6所述的电化学装置,其中当所述电化学装置内的温度超过所述蜡的熔化温度时,所述蜡会熔化及流动,使被所述蜡固定的导电粒子彼此分开。
8.如权利要求6所述的电化学装置,其中所述电化学装置为锂二次电池。
9.一种制造权利要求6的电化学装置的方法,其包括下列步骤:
(a)制备浆料,其中将(i)电极活性材料粒子、(ii)导电粒子、(iii)粘合剂和(iv)蜡分散于溶剂中;
(b)将所述浆料涂覆在集流体上,干燥并压制所述浆料以提供电极;以及
(c)组装电化学装置,其包括由步骤(b)所得到的电极,以及注入非水电解质至所述装置内。
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