CN1271731C - 锂离子电池用高熔融完整性的电池隔板 - Google Patents

锂离子电池用高熔融完整性的电池隔板 Download PDF

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CN1271731C
CN1271731C CNB2004100616626A CN200410061662A CN1271731C CN 1271731 C CN1271731 C CN 1271731C CN B2004100616626 A CNB2004100616626 A CN B2004100616626A CN 200410061662 A CN200410061662 A CN 200410061662A CN 1271731 C CN1271731 C CN 1271731C
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L·施
K·J·哈勒森
余大华
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Abstract

锂电池用的电池隔板是由有高温熔融完整性的非织物平片材料，有低温断路特性的微孔膜，和可粘结非织物平片与微孔膜并适于在接触电解液时可溶胀的粘合剂而制作的。

Description

锂离子电池用高熔融完整性的电池隔板
                       发明的领域
本发明涉及供锂电池使用的隔板
                       发明的背景
在便携式电源的应用中锂二次电池(或电池)已得到广泛使用。便携式电源的应用涉及到包括如膝上型计算器，蜂窝电话和其他便携式装置的应用。这些装置要求用相当小的电池，一种产业标准是“18650”电池，它具有65mm×18mm标称尺寸。此外，由于它们的高能容量和相当低的重量，锂二次电池(又叫锂再充电电池或二次离子电池)也特别适合于大尺寸设备如电动车辆的应用。
不过，电动车辆应用或其他应用的锂二次电池要求具有大的能量，因而有很大的尺寸(即体积)。这是因为这种电池将被使用来例如作为推动机车的电动马达的能源。因为推动电动机车的能量远比上述便携装置所需的能量更大，机车电池的体积尺寸就更大。
涉及锂电池的一个问题是锂为高活性金属，它在约160℃温度可以燃烧。这些电池通常是由包装的部件其中包括载有锂的部件密封于金属盒而制成的。阳极与阴极材料间的短路(即直接接触)可使密封盒损坏。为防止短路或尽量减低它的后果，在阳极与阴极之间放置电池隔板以防它们直接接触。
市售的锂电池(如18650电池)由于尺寸小而容易散热，工作(放电或充电)产生的热并非大问题。然而，当电池容积增大时，从电池中散热便是一个大问题。市售电池(如18650)的隔板通常是由微孔的聚烯烃薄膜制作的，它有收缩的趋势，这部分是由于制作微孔薄膜时需要的拉伸所致。
另外，大电池需要有尺寸更稳定(或高温熔融完整性(meltintegrity))的隔板，因为如有短路出现时，由于大电池含有的锂量多，电池的损坏是很严重的。
在该领域中，将微孔薄膜与非织物并合形成电池隔板是众所周知的。可参见美国专利6,511,774号的“背景技术”和市售产品如从Charlotte，NC的Celgard公司得的CELGARD4000和5000系列产品。这些产品是将非织物直接层压(如用光滑的或带有图样的夹辊热压)于薄膜而制作的。不过，这些产品只能在不超过167℃(聚丙烯非织物和膜组分的熔点)具有尺寸上的稳定性。另外，层压时它们的离子迁移通路受到闭塞，因而降低了电池的效率。
因此，需要找到一种将具有高熔融完整性的非织物和微孔薄膜结合在一起的方法，它应不妨碍阳极与阴极间的离子流动并在167℃以上温度可保持其尺寸的稳定性。
                        发明的概要
电池隔板是由有高温熔融完整性的非织物平片状材料，有低温断路特性的微孔膜，和能将非织物平片与微孔膜粘接并适于在与电解液接触时溶胀的粘合剂而制作的。
                        发明的详述
蓄电池(或电池)常包括阳极、阴极，电解液和隔板。阳极、阴极和隔板通常是在以未卷缠并重叠在一起的带状物卷形物的形式提供。未卷绕物可作成“胶质卷”(jelly roll)(筒形)或“折叠”(棱柱形)状。阳极与阴极是常规的。电解液通常在层压后加入，以便电池在要求使用前是非活性的。
高温熔融完整性的隔板包括微孔膜和非织物的平片，它们是用与电解液接触时可溶胀的粘合剂结合在一起的。优选的隔板厚度在2密耳(50微米)或2密耳以下，最好优选在1.5密耳(38微米)或1.5密耳以下。隔极的MacMullen数优选在10或10以下。MacMullen数最好优选在6或6以下。高温溶融完整性意指隔板至少在温度200℃优选在约380℃以下基本上可保持它的尺寸的稳定性和强度。低温断路意指在130℃以下的温度由于孔的闭塞而能基本上中止阳极与阴极间的离子流动。下面对电池各个组件予以详细讨论。
微孔膜指的是任一种微孔膜。该膜可以是对称膜或非对称膜。膜可以由热塑性聚合物制作的。热塑性聚合物包括但不限于聚苯乙烯，聚氯乙烯，聚丙烯酸类，聚缩醛，聚酰胺，聚碳酸酯，聚酯，聚醚酰亚胺，聚酰亚胺，聚酮，聚亚苯醚，聚亚苯硫，聚砜。聚烯烃是被优选的。聚烯烃的实例包括但不限于聚乙烯(PE，包括LDPE，LIDPE和HDPE)，超高分子量的聚乙烯(UHMWPE)，聚丙烯(PP)，聚甲基戊烯(PMP)，前述任一种的共聚物，和它们的混合物。膜的制备可通过适当的方法包括但不限于干拉伸法(也称做CELGARD法)，或溶剂法(也称凝胶挤出法，或相分离或萃取法，或湿法)，或结网(netting)(孔隙)法(膜流延在冷却辊上，辊上有压花于膜上的花纹，然后将有压花的膜拉伸(MD/TD)，由此沿着压花的花纹上形成大量的孔)。优选有下列特性的膜：空气阻力(Gurley：在2.3厘米汞柱下10cc空气通过1平方英寸膜的时间(秒))不大于40秒(优选9-35秒，最优选少于20秒)；厚度范围在5至500微米(μ)，(优选10至100微米，最优选10至50微米)；孔径范围在0.01至10微米(优选0.02至5微米，最优选0.02至0.5微米)；孔隙率范围在35至85％(优选40至80％)。膜可以是单层膜，三层膜(如PP/PE/PP或PE/PP/PE)，或多层膜。优选的膜是断路隔板，例如参见美国专利号4,650,730；4,731,304；5,281,491；5,240,655；5,565,281；5,667,911；美国申请系列号08/839,664(1997年4月15日申请)；日本专利号2642206和日本专利申请号98395/1994(1994年5月12日申请)；7/56320(1995年3月15日申请)；和英国专利申请号9604055.5(1996年2月27日)，所有这些在此结合作为参考。这些膜可市售于：CELGARD公司，Charlotte，美国北卡罗拉州；Asahi化学工业有限公司，日本东京；Tonen公司，日本东京；Ube工业公司，日本东京；和Nitto Denko K.K.，日本大阪。
非织物平片指的是许多纤维，它们用各种方法如纤维的热熔、树脂、溶剂结合，或机械连结，有时同时采用挤压而结合在一起。非织物平片包括用如干的，湿的或气流成网法，针刺法，纺粘法，或熔融吹制法，和水织交缠等方法制备的纤维结构物。纤维可以定向地或无序地排布。非织物通常不包括纸，对于本应用则包括纸。纤维可由热塑性聚合物，纤维素类和/或陶瓷材料制备。热塑性聚合物包括但不限于聚苯乙烯，聚氯乙烯，聚丙烯酸类，聚缩醛，聚酰胺，聚碳酸酯，聚酯，聚醚酰亚胺，聚亚胺，聚酮，聚亚苯醚，聚亚苯硫，聚砜。纤维素类包括但不限于纤维素(如棉花或其它天然存在的资源)，再生纤维素(如人造丝)和乙酸纤维素(如乙酸纤维素和三乙酸纤维素)。陶瓷材料包括但不限于各种类型的玻璃和氧化铝，二氧化硅和氧化锆的化合物(如硅酸铝)。
另外，非织物或非织物纤维可被涂敷或经表面处理以改进非织物的功能性。例如涂敷或表面处理可改进非织物或它的纤维的粘附性，改进非织物高温熔融的完整性，和/或改进非织物的浸润性。至于改进高温熔融完整性，非织物和/或它的纤维可用陶瓷材料涂敷或表面处理。这些陶瓷材料包括但不限于氧化铝，二氧化硅和氧化锆的化合物，及它们的组合物。
在本发明中，微孔膜与非织物平片的结合是特别关键的，这是为了获得阳极与阴极间电解液离子的自由移动以维持高放电速度的需要。离子的移动一般以电阻(ER)或MacMullen数(NMAC)量度。MacMullen数是电解液饱和的孔介质的电阻r与等量体积电解液电阻r0之比(NMAC＝r/r0)。见美国专利号4,464,238，在此作为参考。为了保证离子的自由移动，仅仅层压微孔膜于非织物平片的作法，由于层压要求足以(或至少部分地)熔化膜的加热与加压，可能具有闭塞(或封闭)微孔膜的孔的问题，因此要求粘结平片于膜的物质不减低通过隔板的离子的移动(或增加其电阻)。为了解决这个问题，有必要寻求一种粘合剂，它在与电解液接触时能溶胀，因而在非织物平片与微孔膜之间形成桥(或通道)。粘合剂的溶胀是电解液吸收入粘合剂的结果。电解液是提供离子的盐和溶剂的溶液(盐也称为溶质)。一旦电解液使粘合剂溶胀，离子便可相对自由地通过粘合剂。
粘合剂是可溶胀的聚合物。粘合剂优选以溶液的形式施加在膜或非织物或二者之上(但优选在非织物上)。溶液按重量计是如2，4，6或8％的稀溶液，4％的被优选。另外，粘合剂也可包括浸润剂。此后，将隔板(膜、非织物和粘合剂溶液)进行层压(温度：不高于155℃，优选120-135℃；压力不大于750Psi，优选约500Psi，施加于一种金属和另一种非金属的夹辊之间；速度：每分钟约1米)，和非必需的溶剂洗涤。溶剂可以是溶解可溶胀聚合物和浸润剂如丙酮的任一溶剂。
粘合剂或可溶胀的聚合物可选自但不限于聚偏氟乙烯(PVDF)；聚氨基甲酸酯；聚环氧乙烷(PEO)；聚丙烯腈(PAN)；聚丙烯酸甲酯(PMA)；聚甲基丙烯酸甲酯(PMMA)；聚丙烯酰胺；聚乙酸乙烯酯；聚乙烯吡咯烷酮；聚四乙二醇二丙烯酸酯；上述任一种的共聚物和它们的结合物。共聚用单体选择的一个标准是共聚用单体的调整均聚物表面能的能力。表面能至少影响：共聚物的溶解度，因而影响共聚物在膜上的涂敷；共聚物在膜上的粘附，因而影响电池的制造和相继的使用性能；涂敷物的浸润性，因而影响电解液在隔板上的吸收。适宜的共聚用单体包括但不限于六氟丙烯，八氟-1-丁烯，八氟异丁烯和四氟乙烯。共聚用单体含量范围按重量计优选3至20％，最为优选7至15％。粘合剂或可溶胀的聚合物优选的是聚偏氟乙烯共聚物。PVDF共聚物优选聚偏氟乙烯与六氟丙烯的共聚物(PVDF∶HFP)，最为优选的PVDF∶HFP的比为91∶9。PVDF共聚物可购自Elf Atochem，美国费城，PA；Solvay SA，比利时布鲁塞尔和Kureha化学工业有限公司，日本Ibaraki。优选的PVDF∶HFP共聚物是ELf Atochem的KYNAR 2800。
浸润剂选自与可溶胀的聚合物相容的(即可混溶的或不会相分离的)物质，它在少量(如可溶胀聚合物的10-20％)时对电池的化学性能没有有害的影响(如含有砜，硫酸盐和氮的浸润剂)，它在室温是液体或有＜50℃的Tg(玻璃化转变温度)。浸润剂选自但不限于基于邻苯二甲酸酯的酯类，环状碳酸酯，聚合型碳酸酯和它们的混合物。基于邻苯二甲酸酯的酯类选自但不限于邻苯二甲酸二丁酯(DBP)。环状碳酸酯选自碳酸亚乙酯(EC)，碳酸亚丙酯(PC)，碳酸亚丁酯(BC)和它们的混合物。聚合型碳酸酯选自但不限于聚碳酸亚乙烯基酯和线形碳酸亚丙酯。
本发明可用以下实例进一步说明。
                        实例
隔板是由微孔膜(单层，PE)、纸(Alpharetta，GA的Schweitzer-Mauduit公司出品的Schweitzer-Mauduit级13LF)和含有丙酮、按丙酮量计的4％PVDF与8％DBP的溶液而制作的。隔板的厚度2.1密耳，电阻5.25Ω-cm2，MacMullen数8.8，维持尺寸稳定的温度达380℃。
本发明可在不违背它的精神和基本特征的条件下采取其它形式实施，相应地，应参照所附的权利要求书而非上述说明书来指示本发明范围。

Claims (17)

1.用于锂电池的隔板，包括：
有高温熔融完整性的非织物平片；
有低温断路特性的微孔膜；和
将所述非织物平片与所述微孔膜粘结并适于在与电解液接触时溶胀的粘合剂。
2.权利要求1的隔板，其中所述的粘合剂是与电解液接触时可溶胀的聚合物。
3.权利要求2的隔板，其中所述可溶胀的聚合物选自聚偏氟乙烯；聚氨基甲酸酯；聚环氧乙烷；聚丙烯腈；聚丙烯酸甲酯；聚甲基丙烯酸甲酯；聚丙烯酰胺；聚乙酸乙烯酯；聚乙烯吡咯烷酮；聚四乙二醇二丙烯酸酯；上述任何的共聚物和它们的结合物。
4.权利要求1的隔板，其中所述粘合剂是与电解液接触时可溶胀的聚合物和浸润剂。
5.权利要求4的隔板，其中所述的可溶胀的聚合物选自聚偏氟乙烯；聚氨基甲酸酯；聚环氧乙烷；聚丙烯腈；聚丙烯酸甲酯；聚甲基丙烯酸甲酯；聚丙烯酰胺；聚乙酸乙烯酯；聚乙烯吡咯烷酮；聚四乙二醇二丙烯酸酯；上述任何的共聚物和它们的结合物。
6.权利要求4的隔板，其中所述的浸润剂选自基于邻苯二甲酸酯的酯类，环状碳酸酯，聚合型碳酸酯，和它们的混合物。
7.权利要求1的隔板，其中所述的微孔膜是由热塑性聚合物制作的。
8.权利要求7的隔板，其中所述的热塑性聚合物选自聚苯乙烯，聚氯乙烯，聚丙烯酸类，聚缩醛，聚酰胺，聚碳酸酯，聚酯，聚醚酰亚胺，聚酰亚胺，聚酮，聚亚苯醚，聚亚苯硫，聚砜。
9.权利要求1的隔板，其中所述的非织物平片是由选自热塑性聚合物，纤维素类和/或陶瓷材料的纤维而制备的。
10.权利要求1的隔板，其中所述的非织物平片还包括涂敷或表面处理。
11.权利要求10的隔板，其中所述的涂敷或表面处理是用陶瓷材料。
12.权利要求11的隔板，其中所述的陶瓷材料选自氧化铝，二氧化硅，氧化锆的化合物和它们的结合物。
13.用权利要求1的隔板制作的锂电池。
14.制作用于锂电池的隔板的方法，包括以下步骤：
提供非织物平片，
提供微孔膜，
提供包含溶剂和与电解液接触时可溶胀聚合物的粘合剂溶液，
用粘合剂溶液涂敷所述的平片或所述的膜或所述的平片与膜二者，
将非织物平片和膜层压在一起，和
由此形成隔板。
15.权利要求14的方法，其中粘合剂溶液包含溶剂、与电解液接触时可溶胀的聚合物和浸润剂。
16.权利要求14的方法，其中层压还包括使用约120-135℃的温度。
17.权利要求14的方法，还包括用溶剂洗涤层压的隔板。
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EP1507299A2 (en) 2005-02-16
CA2468218A1 (en) 2005-01-15
TW200509441A (en) 2005-03-01
US20050014063A1 (en) 2005-01-20
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US7087343B2 (en) 2006-08-08
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