CN106229543A - 一种钛酸锂电池及制作方法 - Google Patents
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Abstract
一种钛酸锂电池,包括正极、负极、间隔于正极和负极之间的隔离膜以及电解液;所述正极包括正极集流片以及正极浆料;所述负极包括负极集流片以及负极浆料;所述电解液包括有机溶剂、添加剂以及锂盐;所述正极浆料包括正极活性物质、导电剂、粘结剂;所述负极浆料包括负极活性物质、导电剂、粘结剂;所述正极活性物质为三元镍钴锰NCM,所述负极活性物为钛酸锂Li4Ti5O12,导电剂为SP和KS‑6的混合物,所述粘结剂为聚偏氟乙烯PVDF;所述正极浆料成分比例为:NCM:SP:KS‑6:PVDF=96:1.5:0.5:2;所述负极浆料成分比例为:Li4Ti5O12:SP:KS‑6:PVDF=93:1.5:0.5:5。
Description
【技术领域】
本发明涉及锂电池领域,特别是一种钛酸锂电池及制作方法。
【背景技术】
钛酸锂由于是零应变材料,当它作为锂电池的负极材料时,具有循环性能良好、使用寿命长等特点,同时它的高扩散系数和高电位性能更是其他材料无法比拟的天然优点。因此,在锂电池应用上有着广阔的发展空间。具体的,它的优点体现在,第一:钛酸锂的化学扩散系数要比碳负极材料高出一个数量级,高扩散系数意味着钛酸锂具备更优的大倍率循环性能;第二:钛酸锂的高电位意味着固体电解质膜(SEI膜)在钛酸锂表面上基本难以形成。因此,在正常电压范围内,钛酸锂表面上也难以生成锂枝晶,避免了锂枝晶在电池内部造成短路的可能,所以采用钛酸锂为负极的锂离子电池的安全性在各种类型的锂离子电池中相对更高;第三:钛酸锂(Li4Ti5O12)本身分子结构也表明可以同时容许3个锂离子脱嵌,钛酸锂电池倍率循环性能相对其它类型锂电池要突出。但是,美中不足的是,目前所制作的钛酸锂电池的能量密度偏低,使得其储能性能较差,且在高温时会导致电解液分解,产生较多的气体,使得其循环胀气比较严重。
鉴于此,实有必要提供一种新型的钛酸锂电池的制作方法来克服以上缺陷。
【发明内容】
本发明的目的在于提供一种钛酸锂电池的制作方法及采用该方法制备出的高能量密度、长循环无胀气的钛酸锂电池。
本发明提供一种钛酸锂电池,包括正极、负极、间隔于正极和负极之间的隔离膜以及电解液;所述正极包括正极集流片以及涂敷于正极集流片上的正极浆料;所述负极包括负极集流片以及涂敷于负极集流片上的负极浆料;所述电解液包括有机溶剂、添加剂以及锂盐;所述正极浆料包括正极活性物质、导电剂、粘结剂;所述负极浆料包括负极活性物质、导电剂、粘结剂;所述正极活性物质为三元镍钴锰NCM,所述负极活性物为钛酸锂Li4Ti5O12,导电剂为SP和KS-6的混合物,所述粘结剂为聚偏氟乙烯PVDF;所述正极浆料成分比例为:NCM:SP:KS-6:PVDF=96:1.5:0.5:2;所述负极浆料成分比例为:Li4Ti5O12:SP:KS-6:PVDF=93:1.5:0.5:5。
在一个优选实施方式中,所述正极活性物质的克容量为162~168mAh/g、粒径分布D50为10~12μm及比表面积为0.8~1.0m2/g;所述负极活性物质的克容量为140~150mAh/g,粒径分布D50为0.8~1.0μm及比表面积为2~5m2/g;所述SP的比表面积为61~67m2/g;所述KS-6的粒径分布D50为3.6~4.4μm及比表面积为39~41m2/g;所述PVDF的密度为1.75~1.77g/cm3分子量为100~120万。
在一个优选实施方式中,所述隔离膜是透气度为227s/100ml、孔隙率为38~42%、膜宽度为62.5mm以及膜厚度为9μm的隔膜。
在一个优选实施方式中,所述电解液中有机溶剂包括EC、EMC、DMC及EA;其比例范围为EC:EMC:DMC:EA=(1.8~2.0):(3.0~3.6):(1.8~2.0):(0.8~1.0);添加剂为PS和LiODFB的混合物,其比例共占0.5~2%;锂盐LiPF6浓度为1.1~1.2mol/L。
在一个优选实施方式中,所述EC:EMC:DMC:EA=2:3.0:2.0:1.0。
本发明还提供一种钛酸锂电池的制作方法,包括以下步骤:
(1)按NCM:SP:KS-6:PVDF=96:1.5:0.5:2进行配料,得到正极浆料,将正极浆料按涂布面密度进行转移式涂布于正极集流片上,然后按压实密度进行对辊压片,最后按宽度进行分切成正极片;
(2)按Li4Ti5O12:SP:KS-6:PVDF=93:1.5:0.5:5比例进行配料,得到负极浆料,将负极浆料按涂布面密度进行转移式涂布于负极集流片上,然后按压实密度进行对辊压片,最后按宽度进行分切成负极片;
(3)将负极片、正极片、隔膜进行卷绕入壳、装配;
(4)将电解液注入电芯中,然后进行封口、化成等后工序。
在一个优选实施方式中,所述正极集流片为铝箔,所述负极集流片为铜箔。
在一个优选实施方式中,所述正极片压实密度为3.3g/cm3;正极涂布面密度为1.45g/100cm2;正极片宽度为58mm;所述负极片压实密度为2.0g/cm3;负极涂布面密度为1.5/100cm2;负极片宽度59.5mm。
本发明的有益技术效果为:本发明通过对正负、隔膜等主材配比及工艺设计优化提升了钛酸锂电池能量密度,再结合最优电解液配方解决了长循环产气的难点,成功制备了高能量密度、长循环无胀气钛酸锂电池。
【说明书附图】
图1为本发明钛酸锂电池制作方法的流程图。
【具体实施方式】
本发明提供了一种钛酸锂电池,包括正极、负极、间隔于正极和负极之间的隔离膜以及电解液;
所述正极包括正极集流片以及涂敷于正极集流片上的正极浆料;所述正极集流片为铝箔,所述正极浆料包括正极活性物质、导电剂、粘结剂。所述正极活性物质为三元镍钴锰NCM,导电剂为SP及KS-6,粘结剂为PVDF。优选的,其比例为:NCM:SP:KS-6:PVDF=96:1.5:0.5:2。
所述负极包括负极集流片以及涂敷于负极集流片上的负极浆料;所述负极集流片为铜箔,所述负极浆料包括负极活性物质、导电剂、粘结剂。所述负极活性物质为钛酸锂Li4Ti5O12,导电剂为为SP及KS-6,粘结剂为PVDF。优选的,其比例为:Li4Ti5O12:SP:KS-6:PVDF=93:1.5:0.5:5。
在本实施方式中,所述正极活性物质的克容量为162~168mAh/g、粒径分布D50为10~12μm及比表面积为0.8~1.0m2/g;所述负极活性物的克容量为140~150mAh/g、粒径分布D50为0.8~1.0μm及比表面积为2~5m2/g;所述SP的比表面积为61~67m2/g;所述KS-6的粒径分布D50为3.6~4.4μm及比表面积为39~41m2/g;所述PVDF的密度为1.75~1.77g/cm3及分子量100~120万。
所述隔离膜将所述正极和负极间隔开。优选的,所述隔离膜为透气度为227s/100ml、孔隙率为38~42%、膜宽度为62.5mm以及膜厚度为9μm的隔膜。所述电解液包括有机溶剂、添加剂以及锂盐。所述电解液中有机溶剂包括EC、EMC、DMC及EA;其比例范围为EC:EMC:DMC:EA=(1.8~2.0):(3.0~3.6):(1.8~2.0):(0.8~1.0);所述添加剂为PS和LiODFB的混合物,其比例共占所述电解液的0.5~2%;所述锂盐LiPF6浓度为1.1~1.2mol/L。在一个优选的实施方式中,所述电解液的组成为EC:EMC:DMC:EA=2:3:2:1;所述添加剂为PS和LiODFB的混合物,其比例共占所述电解液的1.5%;所述锂盐LiPF6浓度1.2mol/L。
如图1所示,本发明还提供一种钛酸锂电池的制作方法,包括以下步骤:
(1)按NCM:SP:KS-6:PVDF=96:1.5:0.5:2进行配料,得到正极浆料,将正极浆料按涂布单面面密度进行转移式涂布于正极集流片上,然后按压实密度进行对辊压片,最后按宽度进行分切成正极片;
(2)按LTO:SP:KS-6:PVDF=93:1.5:0.5:5比例进行配料,得到负极浆料,将负极浆料按涂布单面面密度进行转移式涂布于负极集流片上,然后按压实密度进行对辊压片,最后按宽度进行分切成负极片;
(3)将负极片、正极片、隔膜进行卷绕入壳、装配;
(4)将电解液液入电芯中,然后进行封口、化成等后工序。
在本实施方式中,NCM的克容量、粒径及比表面积分别为165mAh/g、11μm和1.0m2/g;Li4Ti5O12的克容量、粒径及比表面积分别为150mAh/g、1.0μm和5.0m2/g;SP的比表面积为64m2/g;KS-6的粒径及比表面积分别为4.0μm、40m2/g;电解液的组成为EC:EMC:DMC:EA=2:3:2:1,所述添加剂为PS和LiODFB的混合物,其比例共占所述电解液的1.5%,所述锂盐LiPF6浓度1.2mol/L,隔离膜为透气度为227s/100ml、孔隙率为40%、膜宽度为62.5mm以及膜厚度为9μm;所述正极片压实密度为3.3g/cm3;正极涂布单面面密度为1.45g/100cm2;正极片宽度为58mm;所述负极片压实密度为2.0g/cm3;负极涂布单面面密度为1.5/100cm2;负极片宽度59.5mm。
将本发明得到的一组钛酸锂电池进行电性能实验测试,得到如表1所示的一组数据;从表1可以看出,该钛酸锂电池的能量密度大于80.3Wh/Kg超出国家标准要求,且在3C循环1万周的情况下,容量保持率依旧超过80.25%,说明该钛酸锂电池具有优异的倍率循环性能。
在实验测试循环过程中没出现拉断与开启,将所得的钛酸锂电池进行解剖,也没有发现产气现象。
表1钛酸锂电池性能数据
以上是为了使本发明的目的、技术方案和有益技术效果更加清晰明白,结合附图和具体实施方式,对本发明进行进一步详细说明。应当理解的是,本说明书中描述的具体实施方式仅仅是为了解释本发明,并不是为了限定本发明。
Claims (8)
1.一种钛酸锂电池,包括:正极、负极、间隔于正极和负极之间的隔离膜以及电解液;所述正极包括正极集流片以及涂敷于正极集流片上的正极浆料;所述负极包括负极集流片以及涂敷于负极集流片上的负极浆料;所述电解液包括有机溶剂、添加剂以及锂盐;所述正极浆料包括正极活性物质、导电剂、粘结剂;所述负极浆料包括负极活性物质、导电剂、粘结剂;所述正极活性物质为三元镍钴锰NCM,所述负极活性物为钛酸锂Li4Ti5O12,导电剂为SP和KS-6的混合物,所述粘结剂为聚偏氟乙烯PVDF;所述正极浆料成分比例为:NCM:SP:KS-6:PVDF=96:1.5:0.5:2;所述负极浆料成分比例为:Li4Ti5O12:SP:KS-6:PVDF=93:1.5:0.5:5。
2.如权利要求1所述的钛酸锂电池,其特征在于:所述正极活性物质的克容量为162~168mAh/g、粒径分布D50为10~12μm及比表面积为0.8~1.0m2/g;所述负极活性物质的克容量为140~150mAh/g,粒径分布D50为0.8~1.0μm及比表面积为2~5m2/g;所述SP的比表面积为61~67m2/g;所述KS-6的粒径分布D50为3.6~4.4μm及比表面积为39~41m2/g;所述PVDF的密度为1.75~1.77g/cm3分子量为100~120万。
3.如权利要求1所述的钛酸锂电池,其特征在于:所述隔离膜是透气度为227s/100ml、孔隙率为38~42%、膜宽度为62.5mm以及膜厚度为9μm的隔膜。
4.如权利要求1所述的钛酸锂电池,其特征在于:所述电解液中有机溶剂包括EC、EMC、DMC及EA;其比例范围为EC:EMC:DMC:EA=(1.8~2.0):(3.0~3.6):(1.8~2.0):(0.8~1.0);添加剂为PS和LiODFB的混合物,其比例共占0.5~2%;锂盐LiPF6浓度为1.1~1.2mol/L。
5.如权利要求4所述的钛酸锂电池,其特征在于:所述EC:EMC:DMC:EA=2:3.0:2.0:1.0。
6.一种钛酸锂电池的制作方法,包括以下步骤:
(1)按NCM:SP:KS-6:PVDF=96:1.5:0.5:2进行配料,得到正极浆料,将正极浆料按涂布面密度进行转移式涂布于正极集流片上,然后按压实密度进行对辊压片,最后按宽度进行分切成正极片;
(2)按Li4Ti5O12:SP:KS-6:PVDF=93∶1.5∶0.5∶5比例进行配料,得到负极浆料,将负极浆料按涂布面密度进行转移式涂布于负极集流片上,然后按压实密度进行对辊压片,最后按宽度进行分切成负极片;
(3)将负极片、正极片、隔膜进行卷绕入壳、装配;
(4)将电解液注入电芯中,然后进行封口、化成等后工序。
7.如权利要求6所述的钛酸锂电池的制作方法,其特征在于:所述正极集流片为铝箔,所述负极集流片为铜箔。
8.如权利要求6所述的钛酸锂电池的制作方法,其特征在于:所述正极片压实密度为3.3g/cm3;正极涂布面密度为1.45g/100cm2;正极片宽度为58mm;所述负极片压实密度为2.0g/cm3;负极涂布面密度为1.5/100cm2;负极片宽度59.5mm。
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