CN115241541A - 一种原位热聚合固态锂硫电池的制备方法 - Google Patents
一种原位热聚合固态锂硫电池的制备方法 Download PDFInfo
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Abstract
本发明公开一种原位热聚合固态锂硫电池的制备方法,属于锂硫电池领域。该方法采用原位热聚合的方式,实现了固态聚合物电解质和固态锂硫电池的同步制备,解决了固态锂硫电池极化大、容量衰减快、制备过程繁琐和生产成本高的问题。该方法将组装好的注有固态聚合物电解质前驱体溶液的锂硫电池进行加热,通过热聚合反应使聚合物电解质前驱体溶液中低分子量的单体聚合固化,同时得到固态聚合物电解质及其相应的固态锂硫电池。本发明有效解决了固态锂硫电池中电解质隔膜与电池正、负电极间固/固界面接触差的难题,方法工艺简单,且实施时无需改变现有电池制备的工艺流程,适合于该类固态电池的规模化生产。
Description
技术领域
本发明公开一种原位热聚合固态锂硫电池的制备方法,属于锂硫电池领域。
背景技术
锂硫电池的理论比能量高达2500Wh/kg,是传统锂离子电池的十倍以上。因此,锂硫电池被认为是下一代储能设备最有前途的体系之一。常规的锂硫电池使用液态电解质,存在泄漏的风险,使电池不安全。聚合物电解质是将电解液吸收在聚合物基体中制备得到,相比于液态电解质,具有无泄露性、良好的热稳定性和伸展性等优点,为锂硫电池的安全问题提供了一种新的解决方案。
为此,研究人员采用相转化法(Electrochimica Acta 2007,52,2075-2082)、热压法(Angewandte Chemie International Edition 2010,49,2371-2374)和静电纺丝法(Journal of Power Sources 2012,212,179-185)制备了锂硫电池用聚合物电解质隔膜。但这些固态锂硫电池普遍存在容量衰减快和极化大的问题,此外,受聚合物电解质机械强度影响,隔膜难以大面积制备,且预先制得隔膜而后组装成固态电池的工艺流程相对复杂,这些也严重限制了聚合物电解质在固态锂硫电池中的应用。本发明通过原位热聚合的方式,实现了固态聚合物电解质和固态锂硫电池的同步制备,有效解决了固态锂硫电池中电解质隔膜与电池正、负电极间固/固界面接触差的难题。本发明方法工艺简单,且实施时无需改变现有电池制备的工艺流程,特别适合于该类固态电池的规模化生产。
发明内容
本发明的目的是解决固态锂硫电池固/固界面接触差、容量衰减快和制备过程复杂等问题,提供一种原位热聚合固态锂硫电池的制备方法。
本发明解决上述问题采用的的技术方案,一种原位热聚合固态锂硫电池的制备方法步骤如下:
在充满氩气的手套箱中,将正极、隔离膜1、负极依次叠加放置,组成正极/隔离膜/负极结构,然后将聚合物电解质前驱体溶液2注入电池中,封装组成液态电池;对组装好的液态电池在40~80℃下加热处理3时间为0.5~10h,使聚合物电解质前驱体溶液固化,同时得到固态聚合物电解质及其相应的固态锂硫电池4;其中:正极为硫正极5,负极为金属锂;
所述硫正极5为单质硫、硫基复合正极中的一种以上,其中:硫基复合正极由活性物质硫与导电剂混合制备得到,质量百分比为:活性物质硫为51~99%,导电剂为1~49%;所述导电剂为活性炭、介孔碳、纳米碳纤维、多壁碳纳米管、石墨烯、聚丙烯腈、聚苯胺、聚吡咯、聚噻吩中的一种以上;
所述固态聚合物电解质前驱体溶液2由聚合物单体6、引发剂7、液态电解质8混合得到,质量百分比为:聚合物单体为3~60%,引发剂为0.01~5%,液态电解质为35~95%;
所述聚合物单体6为丙烯酸、环氧乙烷、丙烯腈、偏氟乙烯中的一种以上;
所述引发剂7为过氧化合物引发剂、偶氮类引发剂、氧化还原引发剂中的一种以上;过氧化合物引发剂为过氧化氢、过硫酸铵、过硫酸钾、过氧化苯甲酰、过氧化苯甲酰叔丁酯或过氧化甲乙酮;偶氮类引发剂为偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁脒盐酸盐或偶氮二异丁咪唑啉盐酸盐;氧化还原引发剂的水溶性氧化剂为过氧化氢、过硫酸盐或氢过氧化物,水溶性还原剂为二价铁离子、亚硫酸钠或亚硫酸氢钠;油溶性的氧化剂为过氧化环己酮、过氧化甲乙酮或过氧化二苯甲酞,油溶性的还原剂为环烷酸钻、锰、钒或铁盐,或叔胺类化合物;
所述液态电解质8由有机溶剂和锂盐组成,有机溶剂为碳酸酯类、醚类中的一种以上,碳酸酯类为碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯碳酸乙酯、碳酸甲乙酯或碳酸甲丙酯;醚类为四氢呋喃、2-甲基四氢呋喃、1,3-二氧环戊烷、二甲氧基甲烷、1,2-二甲氧基乙烷或二甘醇二甲醚;
锂盐为六氟磷酸锂、四氟硼酸锂、二氟磷酸锂、二草酸硼酸锂、草酸二氟硼酸锂、双氟磺酰亚胺锂、双三氟甲基磺酰亚胺锂中的一种以上;锂盐浓度为0.6~2.5mol/L。
所述隔离膜1为织造膜、非织造膜、微孔膜、复合膜、隔膜纸、碾压膜中的一种以上。
所述加热处理3为热辐射加热、红外线加热、电炉加热、烘箱加热、水浴加热、油浴加热或沙浴加热,其中热辐射波长范围为2~50μm,红外波长范围为0.75~3μm。
所述固态锂硫电池4为固态扣式电池、固态圆柱电池、固态方形电池或固态软包电池。
本发明提出的原位热聚合固态锂硫电池制备方法的原理:
按照现有电池组装工艺流程,组装得到常规锂硫电池结构,而后以聚合物电解质前驱体溶液替代常规电解液,注入到电池中,最后通过加热处理,使聚合物电解质前驱体溶液中低分子量的单体聚合固化,将液态电解质限定在聚合物基体中得到固态聚合物电解质,并同时得到固态锂硫电池。
本发明的有益效果:原位热聚合方法实现了固态聚合物电解质和固态锂硫电池的一步制备,大大简化了电池组装步骤。此外,原位制备方法保证了电极和电解质间的良好界面接触,大大减小了电池的极化。测得聚乙二醇二丙烯酸酯基固态聚合物电解质组装的固态锂硫电池室温下0.2C循环170圈的容量保持率为80%。
附图说明
图1室温下固态锂硫电池于0.2C倍率下的充放电循环性能图
图中:纵坐标为放电比容量,单位为mAh/g;横坐标为充放电循环圈数。
图2固态锂硫电池结构示意图
图中:1、负极壳,2、负极,3、隔膜,4、正极,5、固态聚合物电解质,6、正极壳。
具体实施方式
下面结合附图和实施例对本发明作进一步说明。
实施例1
室温下在充满氩气的手套箱中,将固态聚合物电解质前驱体溶液注入电池中组装电池,电池结构为正极/固态聚合物电解质/负极,其中正极为硫化聚丙烯腈,负极为金属锂,固态聚合物电解质前驱体溶液由1.003g聚乙二醇二丙烯酸酯单体、10.002g液态电解质(有机溶剂为碳酸乙烯酯和碳酸二乙酯,锂盐为六氟磷酸锂,锂盐浓度为1.0mol/L和0.101g偶氮二异丁腈组成。
将上述电池静置3h,使聚乙二醇二丙烯酸酯基固态聚合物电解质前驱体溶液充分浸润电极材料,而后将电池置于60℃的水溶锅中加热反应50min,热聚合同时得到固态聚乙二醇二丙烯酸酯基聚合物电解质及其相应的固态锂硫电池。
将上述固态锂硫电池在室温下,0.2C倍率和1.0~3.0V电压范围内进行充放电循环性能测试。如图1测试得到的充放电循环图所示,聚乙二醇二丙烯酸酯基固态锂硫电池在室温下0.2C倍率下循环170圈的容量保持率为80%。
以上实施例中,通过原位热聚合的方式,实现了固态聚合物电解质和固态锂硫电池的同步制备,简化了固态电池的组装步骤,有效解决了固态锂硫电池中电解质隔膜与电池正、负电极间固/固界面接触差的难题。该方法工艺简单,且实施时无需改变现有电池制备的工艺流程,特别适合于该类固态电池的规模化生产。
Claims (4)
1.一种原位热聚合固态锂硫电池的制备方法,其特征在于该制备方法步骤如下:
在充满氩气的手套箱中,将正极、隔离膜(1)、负极依次叠加放置,组成正极/隔离膜/负极结构,然后将聚合物电解质前驱体溶液(2)注入电池中,封装组成液态电池;对组装好的液态电池在40~80℃下加热处理(3)0.5~10h,使聚合物电解质前驱体溶液固化,同时得到固态聚合物电解质及其相应的固态锂硫电池(4);其中:正极为硫正极(5),负极为金属锂;
所述硫正极(5)为单质硫、硫基复合正极中的一种以上,其中:硫基复合正极由活性物质硫与导电剂混合制备得到,质量百分比为:活性物质硫为51~99%,导电剂为1~49%;所述导电剂为活性炭、介孔碳、纳米碳纤维、多壁碳纳米管、石墨烯、聚丙烯腈、聚苯胺、聚吡咯、聚噻吩中的一种以上;
所述固态聚合物电解质前驱体溶液(2)由聚合物单体(6)、引发剂(7)、液态电解质(8)混合得到,质量百分比为:聚合物单体为3~60%,引发剂为0.01~5%,液态电解质为35~95%;
所述聚合物单体(6)为丙烯酸、环氧乙烷、丙烯腈、偏氟乙烯中的一种以上;
所述引发剂(7)为过氧化合物引发剂、偶氮类引发剂、氧化还原引发剂中的一种以上;过氧化合物引发剂为过氧化氢、过硫酸铵、过硫酸钾、过氧化苯甲酰、过氧化苯甲酰叔丁酯或过氧化甲乙酮;偶氮类引发剂为偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁脒盐酸盐或偶氮二异丁咪唑啉盐酸盐;氧化还原引发剂的水溶性氧化剂为过氧化氢、过硫酸盐或氢过氧化物,水溶性还原剂为二价铁离子、亚硫酸钠或亚硫酸氢钠;油溶性的氧化剂为过氧化环己酮、过氧化甲乙酮或过氧化二苯甲酞,油溶性的还原剂为环烷酸钻、锰、钒或铁盐,或叔胺类化合物;
所述液态电解质(8)由有机溶剂和锂盐组成,有机溶剂为碳酸酯类、醚类中的一种以上,碳酸酯类为碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯碳酸乙酯、碳酸甲乙酯或碳酸甲丙酯;醚类为四氢呋喃、2-甲基四氢呋喃、1,3-二氧环戊烷、二甲氧基甲烷、1,2-二甲氧基乙烷或二甘醇二甲醚;
锂盐为六氟磷酸锂、四氟硼酸锂、二氟磷酸锂、二草酸硼酸锂、草酸二氟硼酸锂、双氟磺酰亚胺锂、双三氟甲基磺酰亚胺锂中的一种以上;锂盐浓度为0.6~2.5mol/L。
2.根据权利要求1所述的一种原位热聚合固态锂硫电池的制备方法,其特征在于所述隔离膜(1)为织造膜、非织造膜、微孔膜、复合膜、隔膜纸、碾压膜中的一种以上。
3.根据权利要求1所述的一种原位热聚合固态锂硫电池的制备方法,其特征在于所述加热处理(3)为热辐射加热、红外线加热、电炉加热、烘箱加热、水浴加热、油浴加热或沙浴加热,其中热辐射波长范围为2~50μm,红外波长范围为0.75~3μm。
4.根据权利要求1所述的一种原位热聚合固态锂硫电池的制备方法,其特征在于所述固态锂硫电池(4)为固态扣式电池、固态圆柱电池、固态方形电池或固态软包电池。
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