CN107814964A - 一种水性浆料及制备方法、电池隔膜与锂离子电池 - Google Patents
一种水性浆料及制备方法、电池隔膜与锂离子电池 Download PDFInfo
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Abstract
本发明公开一种水性浆料及制备方法、电池隔膜与锂离子电池,按重量百分比计,所述水性浆料含有5‑40%的树脂纳米粒子,0‑4%的辅助分散剂,和60‑95%水性连续相。本发明所述水性浆料具有环保无污染的优点,其中的高性能树脂纳米粒子还能显著提高电池隔膜的耐热性能,即使在150℃也不会发生电池隔膜热收缩和电池短路现象,因而本发明提供的电池隔膜特别适用于大容量电池和动力锂离子电池中,进而大幅提高电池的安全性能。
Description
技术领域
本发明涉及锂离子电池技术领域,尤其涉及一种水性浆料及制备方法、电池隔膜与锂离子电池。
背景技术
近年来,锂离子电池频繁出现冒烟,着火,爆炸,甚至造成人员受伤等安全隐患,特别是前段时间发生多起三星note7手机电池爆炸事件,使得高容量和动力锂离子电池的广泛应用受到制约和影响,所以提高锂离子电池安全性能是研发高能量密度锂离子二次电池的核心关键问题。
现在常用的电池隔膜如聚乙烯(PE),聚丙烯(PP),由于熔化温度低于150℃,在某些情况下,例如外部温度过高,放电电流过大或者电解液受热过程中的热惯性的情况下,电池的温度也有可能继续升高,因此隔膜可能完全被破坏而导致电池短路,从而导致电池爆炸或着火。另外,单向拉伸PP隔膜,在横向上的拉伸强度也比纵向上拉伸强度差很多,在电池叠片或受到意外冲击的情况下,存在膜破裂的隐患。因此,采用纯PE隔膜和纯PP隔膜的安全性较低。
高容量和高功率电池内部热量增大和温度升高的因素很多,因此提高电池的耐高温性能变得尤其重要。采用纯PE隔膜和纯PP隔膜的安全性能已经不能满足这种需要,因而需要耐热性能更好的高性能隔膜材料。目前提高隔膜耐热性能采用的措施有隔膜表面改性及涂布、调整聚烯烃的组成成分以及各种复合类隔膜等。其中隔膜表面改性及涂布是工业上采用的主流方法,一是可提升隔膜的热稳定性、改善其机械强度;二是增强隔膜的保液性,从而延长电池循环寿命;三是提升隔膜的润湿性。另外,陶瓷涂层中含有陶瓷颗粒,可以使隔膜具有优异的抗异物颗粒性能。目前应用最多的陶瓷材料是氧化铝(Al2O3)。如盈创-德固赛(Evonik-Degussa)公司主要采用在无纺布隔膜上双面涂布水性陶瓷材料;日本旭化成(Asahi)公司推出面向高输出功率用途的无机-有机复合隔膜IBS(Inorganic-blendedseparator)技术;日本帝人将芳纶、氟系化合物涂覆于聚乙烯基材之上,开发出“LIELSORT”隔膜。国内一般采用热喷涂技术,陶瓷Al2O3涂布主要是采用凹版工艺。另外还有浸涂和窄缝工艺,取决于下游应用需求不同(3C电池、动力电池)。国产设备已经具备单层、前后双层涂布技术,而双向涂布技术目前仍在研发中。陶瓷涂覆容易被误解为简单的喷涂及黏贴工艺,其实整个锂离子电池体系是一个系统工程,从基膜选择(通常用的隔膜直接涂覆效果并非理想,严格说,需要配合电池体系,单独开发),到高精度涂布设备、陶瓷颗粒的选择、涂布工艺控制与电池系统匹配等都需要经过严格的验证和试验才能保障获得较好的涂覆效果。
非水性浆料涂布过程中使用了大量的有机溶剂,采用溶剂交换或热挥发成孔物质方法来造孔,一是污染环境,威胁生产人员身体健康;二是容易造成爆炸着火等安全事故;三是大量使用溶剂,价格昂贵,生产和回收成本高。另一方面,目前水性陶瓷浆料由于陶瓷粒子重量密度大,在存放时和涂布时极容易出现沉降和沉底,严重影响涂布工艺和涂布质量,而且涂布后粘结性差,容易掉粉;目前国内陶瓷涂布技术还存在涂层粘结性、均一性及吸液性差,静电大等问题。
因此,现有技术仍有待于改进和发展。
发明内容
鉴于上述现有技术的不足,本发明的目的在于提供一种水性浆料及制备方法、电池隔膜与锂离子电池,旨在解决现有电池隔膜可能完全被破坏而导致电池短路,从而导致电池爆炸或着火的问题。
本发明的技术方案如下:
一种水性浆料,其中,按重量百分比计,所述水性浆料含有5-40%的树脂纳米粒子,0-4%的辅助分散剂,和60-95%水性连续相。
所述的水性浆料,其中,所述树脂纳米粒子包括聚芳醚酮纳米粒子、聚芳纶纳米粒子、聚酰亚胺纳米粒子、聚苯并咪唑纳米粒子或聚对苯撑苯并二噁唑纳米粒子中的一种。
所述的水性浆料,其中,所述辅助分散剂包括羧甲基纤维素钠、海藻酸钠或聚丙烯酸钠中的一种或两种。
所述的水性浆料,其中,所述水性连续相为水和醇的混合物,所述醇包括乙醇、正丙醇、异丙醇中的一种。
所述的水性浆料,其中,所述水和醇的混合质量比例范围为100:0-50:50。
一种如上所述的水性浆料的制备方法,其中,包括以下步骤:
A、将树脂纳米粒子、辅助分散剂和水性连续相混合,并搅拌均匀,得到混合溶液;
B、将所述混合溶液放置于砂磨机中进行砂磨处理,得到水性浆料。
一种电池隔膜,其中,包括基膜,及通过涂布工艺涂布在所述基膜表面的涂布层,所述涂布层的材料为如上任一项所述水性浆料。
所述的电池隔膜,其中,所述涂布层的厚度为1-10微米。
所述的水性浆料涂布电池隔膜的方法,其中,所述基膜包括聚丙烯隔膜、聚乙烯隔膜、纤维法无纺布膜中的一种。
一种锂离子电池,其中,包括如上所述电池隔膜。
有益效果:本发明提供的所述水性浆料具有环保无污染的优点,其中的高性能树脂纳米粒子还能显著提高电池隔膜的耐热性能,即使在150℃也不会发生电池隔膜热收缩和电池短路现象,因而本发明提供的电池隔膜特别适用于大容量电池和动力锂离子电池中,进而大幅提高电池的安全性能。
具体实施方式
本发明提供一种水性浆料及制备方法、电池隔膜与锂离子电池,为使本发明的目的、技术方案及效果更加清楚、明确,以下对本发明进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
本发明提供一种水性浆料较佳实施例,其中,按重量百分比计,所述水性浆料含有5-40%的树脂纳米粒子,0-4%的辅助分散剂,和60-95%水性连续相。
优选地,所述树脂纳米粒子包括聚芳醚酮(PEEK)纳米粒子、聚芳纶(PA)纳米粒子、聚酰亚胺(PI)纳米粒子、聚苯并咪唑(PBI)纳米粒子或聚对苯撑苯并二噁唑(PBO)纳米粒子等中的一种。本发明树脂纳米粒子的粒子尺寸范围为50-800纳米。本发明上述树脂纳米粒子具有优异的耐热性能。
优选地,所述辅助分散剂包括羧甲基纤维素钠、海藻酸钠或聚丙烯酸钠等中的一种或两种。
优选地,所述水性连续相为水和醇的混合物,其中所述醇为低级醇,例如包括乙醇、正丙醇、异丙醇等中的一种。更优选地,所述水和醇的混合质量比例范围为100:0-50:50。
本发明还提供一种如上所述的水性浆料的制备方法较佳实施例,其中,包括以下步骤:
A、将树脂纳米粒子、辅助分散剂和水性连续相混合,并搅拌均匀,得到混合溶液;
B、将所述混合溶液放置于砂磨机中进行砂磨处理,砂磨处理的时间为2-4小时,得到水性浆料。
本发明还提供一种电池隔膜,其中,包括基膜,及通过涂布工艺涂布在所述基膜表面的涂布层,所述涂布层的材料为如上任一项所述水性浆料。
优选地,所述基膜包括干法制备的聚丙烯隔膜、湿法制备的高分子量聚乙烯隔膜、纤维法无纺布膜等中的一种。
优选地,所述涂布工艺包括凹版涂、浸涂和蘸涂等涂布工艺中的一种。
本发明所述涂布层的厚度为1-10微米,电池隔膜的透气率为10-500秒,平均孔径范围为50-100纳米,拉伸强度为50-150兆帕。
本发明所述水性浆料具有环保无污染的优点,其中的高性能树脂纳米粒子还能显著提高电池隔膜的耐热性能,即使在150℃也不会发生电池隔膜热收缩和电池短路现象,因而本发明提供的电池隔膜特别适用于大容量电池和动力锂离子电池中,进而大幅提高电池的安全性能。
本发明还提供一种锂离子电池,其中,包括如上所述电池隔膜。
下面通过实施例对本发明进一步说明。
实施例1
取聚酰亚胺纳米粒子30克,羧甲基纤维素钠1.0克和纯净水269克混合后搅拌均匀,然后放在砂磨机中研磨2小时,形成均匀分散的悬浮液,即为水性浆料,其固含量为10.3%。在凹版涂布机上,把上述水性浆料涂布在湿法聚乙烯基膜的一个表面,得到单面涂层厚度2.0微米的聚酰亚胺表面改性隔膜。
实施例2
实施例2的操作步骤与实施例1大体相同,不同之处是取聚芳纶纳米粒子30克,海藻酸钠1.0克和纯净水269克混合后搅拌均匀,然后放在砂磨机中研磨2小时,形成均匀分散的悬浮液,即为水性浆料,其固含量为10.3%。其他涂布步骤同实施例1,得到单面涂层厚度2.0微米的聚芳纶表面改性隔膜。
实施例3
实施例3的操作步骤与实施例1大体相同,不同之处是取聚芳醚酮纳米粒子30克,聚丙烯酸钠1.0克,纯净水259克和10克乙醇混合后搅拌均匀,然后放在砂磨机中研磨2小时,形成均匀分散的悬浮液,即为水性浆料,其固含量为10.3%。其他涂布步骤同实施例1,得到单面涂层厚度2.0微米的聚芳醚酮表面改性隔膜。
实施例4
取聚酰亚胺纳米粒子60克,羧甲基纤维素钠1.0克和纯净水239克混合后搅拌均匀,然后放在砂磨机中研磨4小时,形成均匀分散的悬浮液,即为水性浆料,其固含量为20.3%。在浸没式涂布机上,把上述水性浆料涂布在湿法聚乙烯基膜的两个表面上,得到双面涂层厚度2.0微米的聚酰亚胺双面表面改性隔膜。
实施例5
实施例5的操作步骤与实施例4大体相同,不同之处是取聚苯并咪唑纳米粒子60克,聚丙烯酸钠1.0克,纯净水229克和10克乙醇混合后搅拌均匀,然后放在砂磨机中研磨4小时,形成均匀分散的悬浮液,即为水性浆料,其固含量为20.3%。浸没式涂布步骤同实施例4,得到双面涂层厚度2.0微米的聚苯并咪唑双面改性隔膜。
实施例6
实施例6的操作步骤与实施例4大体相同,不同之处是取聚对苯撑苯并二噁唑粒子60克,聚丙烯酸钠1.0克,纯净水229克和10克乙醇混合后搅拌均匀,然后放在砂磨机中研磨4小时,形成均匀分散的悬浮液,即为水性浆料,其固含量为20.3%。浸没式涂布步骤同实施例4,得到双面涂层厚度2.0微米的聚对苯撑苯并二噁唑双面改性隔膜。
对比例1
采用商业化的湿法聚乙烯基膜作为对比,以进一步阐明本实施例中所述的表面改性隔膜的优点。
对上述实施例1-6和对比例1中的隔膜性能进行表征:
红外光谱:用傅立叶变换红外光谱仪(Nicolet iN10)来表征隔膜的表面化学结构。
扫描电镜:用冷场发射扫描电子显微镜来观察膜的表面和横断面的形貌,以及部分孔径大小。
透气性:采用Gurley 4110N透气仪(USA)来测量膜样品的透气性。
膜厚度:采用千分尺测试隔膜的厚度,任意取样品上的5个点,并取平均值。
孔隙率:采用下列测试方法,把隔膜浸泡在正丁醇中2小时,然后根据公式计算孔隙率:
其中,ρa和ρp是正丁醇的密度和隔膜的干密度,ma和mp是膜吸入的正丁醇的质量和隔膜自身的质量。
拉伸强度:采用GB1040-79的塑料拉伸实验法来测试隔膜的拉伸强度和伸长率。
所得结果列于表1。从表1的结果可以看出,采用本实施例提供的水性涂布浆料所制备的电池隔膜具有较高的孔隙率,透气性和机械强度,符合锂离子电池隔膜对孔径的要求,从实施例1-6与对比例1的测试结果可以看出,改性后的隔膜比聚烯烃基膜热收缩率明显变小,耐热性能显著提高。
测试电池性能
1)正极的制备
首先将5.55克正极活性物质LiCoO2,0.29克导电剂乙炔黑混合均匀,接着再加入6.10克质量分数为5%的聚偏氟乙烯(PVDF)溶液(溶剂为N-甲基-2-吡咯烷酮),搅拌形成均匀的正极料浆。
将该正极料浆均匀的涂布在铝箔上,然后120℃下烘干,辊压,冲片制得半径为12毫米和厚度为80微米的圆形正极片,其中含有16.9毫克活性成分LiCO2。
2)负极的制备
将4.61克负极活性物质天然石墨,0.09克导电剂乙炔黑混合均匀,接着再加入2.52克质量分数为10%的聚偏氟乙烯(PVDF)溶液(溶剂为N-甲基-2-吡咯烷酮),搅拌形成均匀的负极料浆。
将负极浆料均匀地涂布在铜箔上,然后在120℃下烘干,辊压,冲片制得半径为14毫米和厚度为65微米的圆形负极片,其中含有11.2毫克活性成分的天然石墨。
3)用电池隔膜组装锂离子二次电池
将上述得到的正极,负极与隔膜依次叠层并装入扣式电池中(电池型号2032),所述的隔膜分别为实施例1-6中改性隔膜和对比例1中的聚烯烃基膜。
将混合溶剂(碳酸亚乙酯:甲基乙基碳酸酯(EC/EMC)的体积比为1:1)中含有1摩尔六氟磷酸锂(LiPF6)的电解液约145毫克注入上述电池中,并按照常规方法陈化,密封电池壳即得到锂离子二次电池。
4)锂离子二次电池耐高温性能测试
测试方法如下:将锂离子二次电池进行1C充电到100%充电态,放置在烘箱中,烘箱温度以5/分钟从室温升高到150℃及180℃,其中电池电压跌落大于0.2伏视为短路。
5)锂离子二次电池寿命测试
测试方法如下:在25±5℃下,将电池进行循环充放电250次,记录剩余电量,剩余电量越高,电池寿命越长。
将用实施例1-6所制得改性隔膜和对比例1中基膜制作成电池,按照上述测试方法进行电池耐高温性能和寿命测试,所得到的结果列于表2中。
从表2的结果可以看出,用本发明的改性隔膜作为电池隔膜制备的锂离子电池具有更好的安全性能和更长的使用寿命。
表1
表2
综上所述,本发明提供的一种水性浆料及制备方法、电池隔膜与锂离子电池,本发明所述水性浆料具有环保无污染的优点,其中的高性能树脂纳米粒子还能显著提高电池隔膜的耐热性能,即使在150℃也不会发生电池隔膜热收缩和电池短路现象,因而本发明提供的电池隔膜特别适用于大容量电池和动力锂离子电池中,进而大幅提高电池的安全性能。
应当理解的是,本发明的应用不限于上述的举例,对本领域普通技术人员来说,可以根据上述说明加以改进或变换,所有这些改进和变换都应属于本发明所附权利要求的保护范围。
Claims (10)
1.一种水性浆料,其特征在于,按重量百分比计,所述水性浆料含有5-40%的树脂纳米粒子,0-4%的辅助分散剂,和60-95%水性连续相。
2.根据权利要求1所述的水性浆料,其特征在于,所述树脂纳米粒子包括聚芳醚酮纳米粒子、聚芳纶纳米粒子、聚酰亚胺纳米粒子、聚苯并咪唑纳米粒子或聚对苯撑苯并二噁唑纳米粒子中的一种。
3.根据权利要求1所述的水性浆料,其特征在于,所述辅助分散剂包括羧甲基纤维素钠、海藻酸钠或聚丙烯酸钠中的一种或两种。
4.根据权利要求1所述的水性浆料,其特征在于,所述水性连续相为水和醇的混合物,所述醇包括乙醇、正丙醇、异丙醇中的一种。
5.根据权利要求4所述的水性浆料,其特征在于,所述水和醇的混合质量比例范围为100:0-50:50。
6.一种如权利要求1-5任一项所述的水性浆料的制备方法,其特征在于,包括以下步骤:
A、将树脂纳米粒子、辅助分散剂和水性连续相混合,并搅拌均匀,得到混合溶液;
B、将所述混合溶液放置于砂磨机中进行砂磨处理,得到水性浆料。
7.一种电池隔膜,其特征在于,包括基膜,及通过涂布工艺涂布在所述基膜表面的涂布层,所述涂布层的材料为权利要求1-5任一项所述水性浆料。
8.根据权利要求7所述的电池隔膜,其特征在于,所述涂布层的厚度为1-10微米。
9.根据权利要求7所述的水性浆料涂布电池隔膜的方法,其特征在于,所述基膜包括聚丙烯隔膜、聚乙烯隔膜、纤维法无纺布膜中的一种。
10.一种锂离子电池,其特征在于,包括权利要求7-9任一项所述电池隔膜。
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