CN100423325C - 具有无机保护膜的隔板及使用它的锂电池 - Google Patents
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Abstract
本发明提供一种具有无机保护膜的隔板和使用该隔板的锂电池。该隔板抑制自放电并减少内短路。
Description
技术领域
本发明涉及一种具有无机保护膜的隔板及使用它的锂电池,更具体地,本发明涉及一种抑制自放电并减少内短路的具有无机保护膜的隔板及使用它的锂电池。
背景技术
随着重量轻,多功能的便携式电子设备如摄录机,便携式电话,笔记本电脑等的发展,作为其驱动电源的电池已经得到了广泛的研究。特别是可充电锂电池更引人注目,其发展非常迅速,因为它们的能量密度几乎是常规电池如Ni-Nd电池,Ni-H电池或Ni-Zn电池的三倍,并且能够迅速充电。
电池的电化学单元基本上包括阴极,阳极和置于其间的隔板。在放电过程中,阳极发生氧化反应,阴极发生还原反应。在氧化和还原过程中产生的锂离子通过浸渍于隔板微孔中的电解液进行迁移。阴极和阳极通过隔板彼此没有电接触,所以电子不能直接在阳极和阴极之间运动。
电池中所使用的多孔隔板在电解质溶液中应该是化学稳定的,且其可使用的实例包括聚烯烃如聚乙烯或聚丙烯,玻璃纤维过滤纸或陶瓷材料。特别地,在隔板需要盘绕成圆形的圆柱形电池中,隔板必须具有足够的柔韧性。同时,伴随着高能量密度趋势,隔板须在降低厚度时也具有足够的机械强度。
在阴极活性物质易溶于电解质溶液中进而易于移动的情况下,必须安装具有封闭阴极活性物质的功能的隔板。具体地,在锂-硫电池中,用作阴极活性物质的硫形成多硫化锂,其在充放电过程中容易溶解在电解质溶液中。多硫化锂迁移到阳极并与锂金属反应形成副反应物,降低电池的贮存特性。换句话说,存在严重的自放电问题。
在这种情况下,通过封闭多硫化锂的运动可以显著地抑制由于自放电而引起的容量下降。为此,可以将聚合物如聚(氧化乙烯),聚(氧化丙烯),聚(偏二氟乙烯),聚(四氟乙烷)或聚(丙烯腈)涂布在隔板的表面上,从而一定程度上阻止阴极活性物质的移动。由于所使用的聚合物的膨胀,所以活性物质的封闭受到一定的限制。为了克服该问题,可以使用不导致膨胀的聚合物。然而,在这种情况下,离子的渗透性也受到抑制,使其难于实现电池的性能。
发明内容
本发明提供一种使用具有无机保护膜的隔板的锂电池,该无机保护膜可以通过抑制阴极活性物质的移动来降低自放电(self discharge)。
本发明一方面提供一种锂电池,其包括阴极,阳极,及置于阴极与阳极之间的隔板,其中在隔板的至少一个表面上形成了无机保护膜。
在本发明的实施方案中,无机保护膜是具有锂离子传导性的单离子导电玻璃。
无机保护膜可以选自下列中的至少一种:氮化锂,硅酸锂,硼酸锂,铝酸锂,磷酸锂,锂磷氧氮化物(lithium phosphorus oxynitride),锂硅硫化物,锂锗硫化物,锂镧氧化物,锂钛氧化物,锂硼硫化物,锂铝硫化物,锂磷硫化物,及它们的混合物。
优选地,该无机保护膜是氮化锂,磷酸锂,或者锂磷氧氮化物。
该无机保护膜可以具有0.01~5μm的厚度。优选地,该无机保护膜可以具有0.1~1μm的厚度。
该无机保护膜可以通过气体反应,热沉积,溅射,化学气相沉积,等离子体增强化学气相沉积,激光增强的化学气相沉积,离子镀,阴极弧,喷射气相沉积或激光烧蚀而形成。
该隔板可以是聚乙烯隔板,聚丙烯隔板,聚乙烯/聚丙烯双层隔板,聚乙烯/聚丙烯/聚乙烯三层隔板,聚丙烯/聚乙烯/聚丙烯三层隔板,玻璃纤维过滤纸或陶瓷隔板。
附图说明
通过参照附图详述其优选实施方案,本发明的上述方面和优点将会更加显而易见,在附图中:
图1是具有无机保护膜的电解液的断面图,该无机保护膜形成于阴极活性物质与多孔隔板之间,所述阴极活性物质形成于基材上;
图2是形成于浸渍了电解液的多孔隔板表面的无机保护膜的断面图;
图3是具有无机保护膜的电解液的断面图,该无机保护膜形成于阳极活性物质与多孔隔板之间,所述阳极活性物质形成于基材上;
图4示出了在实施例1和对比例中制备的电池的放电曲线;及
图5示出了在实施例2中制备的电池的放电曲线。
具体实施方式
本发明涉及用于锂电池的隔板,其中在隔板的表面形成无机保护膜,进而形成隔板/无机膜结构,从而抑制阴极活性物质的移动。如果隔板/无机膜结构阻止阴极活性物质的移动,则可以抑制电池的自放电和容量下降。
电池中使用的隔板阻止电子直接从阴极到阳极或从阳极到阴极的移动,并提供离子通过的空间。一般地,隔板具有很多微孔,且电解质溶液浸渍到这些微孔中,同时允许离子容易通过电解质溶液而移动。然而,如果阴极活性物质溶解在电解质溶液中,则微孔隔板就不能阻止阴极活性物质的移动及其与阳极物质的反应,导致电池容量下降。
根据本发明的无机保护膜至少形成于隔板的一个表面上,并抑制阴极活性物质的移动,进而抑制电池的自放电和容量下降。无机保护膜可以形成于隔板的两个或一个表面上。当无机保护膜仅形成于隔板的一个表面上时,其可位于阴极与隔板之间,如图1所示,或者位于阳极与隔板之间,如图3所示。
在隔板/无机膜结构中,隔板赋予无机保护膜以柔韧性和强度。换句话说,无机保护膜本身是非常薄弱的,所以在操作过程中很容易碎裂或损坏。然而,存在于隔板/无机保护膜结构中的隔板明显地补偿了这个弱点。同时,隔板/无机保护膜结构在隔板与无机保护膜之间具有优良的粘附作用,这归因于多孔隔板的微孔与无机保护膜之间的互锁作用。
与常规的聚合物不同,无机保护膜具有若干优点:在很少发生膨胀的同时,它还充当抑制阴极活性物质移动并且仅允许锂离子通过的单离子导体。同时,无机保护膜在电解质溶液中是稳定的。
因此,无机保护膜应根据多种因素来选择,可用于本发明的无机保护膜的实例包括各种具有良好锂离子传导性的材料,例如氮化锂,硅酸锂,硼酸锂,铝酸锂,磷酸锂,锂磷氧氮化物,锂硅硫化物,锂锗硫化物,锂镧氧化物,锂钛氧化物,锂硼硫化物,锂铝硫化物,锂磷硫化物,及它们的混合物。具体地,优选氮化锂,磷酸锂,或者锂磷氮氧化物。特别优选使用氮化锂(Li3N),因为它具有非常高的离子电导率(10-3 S/cm),允许加工成较厚的层,进而抑制针孔(pinhole)的产生。
无机保护膜在隔板上形成0.01~5μm,优选0.1~1μm的厚度。如果无机保护膜的厚度小于0.01μm,由于产生针孔,不能合适地进行表面涂布。如果无机保护膜的厚度大于5μm,则内阻不合乎需要地增加,能量密度降低,无机保护膜变得更脆,使其在弯曲过程中容易破损。
可以通过采用任何合适的方法将上述具有高锂离子传导性的材料在隔板上形成无机保护膜,如气体反应,热沉积,反应溅射法,化学气相沉积,等离子体增强化学气相沉积,激光增强的化学气相沉积,离子镀,阴极弧,喷射气相沉积或激光烧蚀。
可以通过气体反应,热沉积或溅射在隔板上形成无机保护膜。
作为选择,在隔板上形成无机保护膜可以采纳的方法包括:
1)在隔板上沉积锂金属;和
2)将沉积了锂金属的隔板与N2,SO2,CO2或O2接触,形成无机保护膜。
采用两步工艺可以防止隔板因受热而损坏。
现在将更详细地阐述采用两步工艺形成无机保护膜的方法。
首先,将锂金属沉积在隔板上,得到隔板/沉积锂产物,将所得产物暴露于氮气,引起气体反应,从而形成Li3N。形成Li3N的速度随氮气的压力而变化。当氮气压力增加时,形成速度也增加。因此,从形成无机保护膜的速度来看,较高的氮气压力是有利的。
可用于本发明的隔板的实例包括但不限于聚乙烯隔板,聚丙烯隔板,聚乙烯/聚丙烯双层隔板,聚乙烯/聚丙烯/聚乙烯三层隔板,聚丙烯/聚乙烯/聚丙烯三层隔板,玻璃纤维过滤纸或陶瓷隔板。
根据本发明的具有无机保护膜的隔板可以应用于各种普通锂电池。本文中,锂电池一般是指锂原电池或锂二次电池,如锂离子电池,锂聚合物电池,锂硫电池等。此外,从形状来看,还可以应用于圆柱形电池和矩形电池。
现在详细阐述根据本发明实施方案的制造锂电池的方法。
首先,分别根据制备锂电池的一般方法制备阴极和阳极。阴极包括选自锂复合氧化物,单质硫,具有Li2Sn(n≥1)溶解于其中的阴极电解液,有机硫和(C2Sx)y(x是2.5~20的数。且y≥2)中的至少一种。阳极优选锂金属电极或锂金属合金电极。
其后,将根据本发明的具有无机保护膜的隔板插在阴极和阳极之间,然后进行盘绕或堆叠,进而形成电极组件。将所得的结构放入电池壳中,从而完成电池的安装。
然后,向装有电极组件的电池壳中注入含有锂盐和有机溶剂的电解液,进而完成锂电池。
作为电解质溶液中的锂盐,可以使用制备锂电池时通用的任何锂盐,其具体实例至少一种选自于高氯酸锂(LiClO4),四氟硼酸锂(LiBF4),六氟磷酸锂(LiPF6),三氟甲磺酸锂(LiCF3SO3),二(三氟甲磺酰)胺锂(LiN(CF3SO2)2)的锂盐,其浓度范围为0.5~2.0M。如果锂盐浓度超出上述范围,则不能显示出良好的离子传导性。
形成本发明的电解质溶液的有机溶剂的实例包括选自下列中的至少一种:多甘醇二醚(polyglyme)化合物,二氧戊环化合物,碳酸酯化合物,2-氟苯,3-氟苯,4-氟苯,二甲氧基乙烷和二乙氧基乙烷。
多甘醇二醚化合物的实例包括选自下列中的至少一种:二乙二醇二甲醚(CH3(OCH2CH2)2OCH3,也称作二甘醇二甲醚(DGM)),二乙二醇二乙醚(C2H5(OCH2CH2)2OC2H5),三乙二醇二甲醚(CH3(OCH2CH2)3OCH3),三乙二醇二乙醚(C2H5(OCH2CH2)3OC2H5)。
二氧戊环化合物的实例包括至少一种选自下列的化合物:1,3-二氧戊环,4,5-二乙基-二氧戊环,4,5-二甲基-二氧戊环,4-甲基-1,3-二氧戊环,及4-乙基-1,3-二氧戊环。
碳酸酯化合物的实例包括至少一种选自下列的化合物:碳酸亚乙酯,碳酸异丙烯酯,碳酸二乙酯,碳酸二甲酯,γ-丁内酯,碳酸甲乙酯和碳酸亚乙烯酯。
有机溶剂的实例包括碳酸亚乙酯(EC),碳酸异丙烯酯(PC),碳酸二甲酯(DMC),碳酸甲乙酯(EMC)及其混合物;以及二乙二醇二甲醚(DGM,也称作二甘醇二甲醚),二甲氧基乙烷(DME),1,3-二氧戊环(DOX)及其混合物。
现将通过下列实施例描述本发明,但本发明并不受其限制。
-阴极的制备
向乙腈中加入67.5%重量的单质硫,11.4%重量的Ketjen碳黑,21.1%重量的聚氧化乙烯,并进行均质化,得到浆液。将所获得的浆液涂布在碳涂布的铝集电体上,干燥除去乙腈并辊压成型。这里,单位面积的能量密度为1.1mAh/cm2。最终制得阴极。
-阳极的制备
为了用作阳极,将锂沉积在铜箔上至20μm的厚度。
-电解质溶液的制备
电解质溶液中使用的有机溶剂是体积比为4∶4∶2的二甲氧基乙烷/二甘醇二甲醚/二氧戊环的混合溶剂,锂盐为1.15M的LiCF3SO3。
实施例1
在40℃的真空干燥箱中,干燥厚度为25μm的聚丙烯隔板超过一天,并且将其用作隔板。将包含于钼船中的金属锂放在沉积室中,减压至10-6 Torr,然后在隔板表面进行锂的热沉积。为了调节厚度,使用厚度监测器。沉积厚度设置为沉积完金属锂之后,向沉积室中注入氮气,直到沉积室的内压达到10 Torr。注入氮气之后,从厚度监测器中立刻看到重量的增加,表明氮与锂发生反应,生成氮化锂(Li3N)。当厚度监测器显示重量不再进一步增加时,使反应继续进行大约1分钟。然后,取出隔板/沉积的氮化锂结构,通过肉眼观察其表面,确认形成了均匀的红色氮化锂。然后,采用预先制备的阴极,阳极,隔板/Li3N和电解液制备电池。
实施例2
采用与实施例1相同的方法制备电池,所不同的是使用沉积了锂氧氮化物(LiPON)膜的隔板(隔板/LiPON)作为隔板。隔板/LiPON的制备如下:使用直径4英寸的Li3PO4靶,在氮气氛下于厚度为25μm的聚丙烯隔板上沉积厚的LiPON,条件是5mTorr的压力,200W RF Power沉积2小时。
对比例
采用与实施例1相同的方法制备电池,所不同的是使用聚丙烯隔板代替隔板/氮化锂。
实验例:自放电的抑制
利用在实施例1和2以及对比例中制备的电池,研究自放电抑制效应。电池的充电/放电条件如下:每个电池以0.2C充电,直到充电容量达到120%,然后以0.1C放电,直到放电电压达到1.5V。
在制得实施例1的电池之后测量的开路电压(OCV)为3.17V,然后将电池充放电二次,并将其在室温下放置一周。然后,测量自放电速率。也就是说,在将电池在室温放置一周后,对电池进行放电,以测量其容量的减少。结果表明容量下降20%。
与在室温放置一周之前相比,在实施例2中制备的电池的容量减少了约24%。
在对比例中,容量减少了约50%。
图4示出了在实施例1和对比例中制备的电池的放电曲线,其中A1和A2是在对比例中制备的电池的放电曲线,B1和B2是在实施例1中制备的电池的放电曲线。具体地,A1和B1是电池在室温放置一周之前的放电曲线,而A2和B2是电池在室温放置一周后的放电曲线。使用隔板/氮化锂的电池和使用普通隔板的电池之间的放电电压变化不大,表明由于氮化锂而产生的内阻是可以忽略的。
图5示出了在实施例2制备的电池在室温下放置一周前后的放电曲线,分别用C1和C2表示。参见图5,与仅使用在对比例中使用的隔板的电池相比(图4中的A1和A2),在实施例2中制备的电池的放电电压略微下降。
根据本发明,在隔板表面形成无机保护膜,得到隔板/无机保护膜结构,进而抑制阴极活性物质的移动。如果隔板/无机保护膜结构阻止阴极活性物质的移动,那么就能够抑制电池的自放电和容量下降。因此,本发明能够更有效地应用于锂电池。
Claims (10)
1. 一种锂电池,包括:
阴极;
阳极;
电解液;和
置于所述阴极与阳极之间的隔板,其中该隔板的至少一个表面上形成了无机保护膜。
2. 根据权利要求的1的锂电池,其中所述无机保护膜是具有锂离子传导性的单离子导电玻璃。
3. 根据权利要求1的锂电池,其中所述无机保护膜为选自下列中的至少一种:氮化锂,硅酸锂,硼酸锂,铝酸锂,磷酸锂,锂磷氧氮化物,锂硅硫化物,锂锗硫化物,锂镧氧化物,锂钛氧化物,锂硼硫化物,锂铝硫化物,锂磷硫化物,及它们的混合物。
4. 根据权利要求1的锂电池,其中所述无机保护膜的厚度为0.01~5μm。
5. 根据权利要求1的锂电池,其中所述无机保护膜是通过气体反应,热沉积,溅射,化学气相沉积,等离子体增强的化学气相沉积,激光增强的化学气相沉积,离子镀,阴极弧,喷射气相沉积或激光烧蚀形成的。
6. 根据权利要求1的锂电池,其中所述隔板为聚乙烯隔板,聚丙烯隔板,聚乙烯/聚丙烯双层隔板,聚乙烯/聚丙烯/聚乙烯三层隔板,聚丙烯/聚乙烯/聚丙烯三层隔板,玻璃纤维过滤纸或陶瓷隔板。
7. 一种形成隔板的无机保护膜的方法,包括:
在隔板上沉积锂金属,即将金属锂放在沉积室中,减压至10-6Torr,在隔板上热沉积锂金属;及
将其上沉积了锂金属的隔板与N2接触,即向沉积室中注入氮气,直至沉积室的内压达到10Torr,进而形成无机保护膜。
8. 根据权利要求7的方法,其中所述无机保护膜为氮化锂。
9. 根据权利要求7的方法,其中所述无机保护膜的厚度为0.01~5μm。
10. 根据权利要求7的方法,其中所述隔板是聚乙烯隔板,聚丙烯隔板,聚乙烯/聚丙烯双层隔板,聚乙烯/聚丙烯/聚乙烯三层隔板,聚丙烯/聚乙烯/聚丙烯三层隔板,玻璃纤维过滤纸或陶瓷隔板。
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US7175937B2 (en) | 2007-02-13 |
KR100467705B1 (ko) | 2005-01-24 |
CN1494173A (zh) | 2004-05-05 |
JP2004158453A (ja) | 2004-06-03 |
JP4477856B2 (ja) | 2010-06-09 |
US20040106037A1 (en) | 2004-06-03 |
KR20040039568A (ko) | 2004-05-12 |
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