CN112002934B - 一种可充电硫离子电池及其制备方法 - Google Patents
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Abstract
本发明提供一种可充电硫离子电池及其制备方法,所述硫离子电池的正极活性物质为炭黑,负极材料为锌箔,电解液的溶质为硫化钠,溶剂为乙二醇。本发明首次提出基于硫离子吸附/解吸原理的硫基电池,当使用金属锌箔作为负极组装成新型的硫离子电池时,循环比容量为121mAh/g并且寿命高达1000次。相比于传统的金属‑硫电池,新型硫离子电池有效避免了硫绝缘性以及多硫化物溶解等问题,有机体系对电池的寿命也扮演着重要的角色。同时,新型硫离子电池的电极片和电解液制作简单,电解液绿色、安全,具有很大的应用价值和市场前景。
Description
技术领域
本发明属于电池领域,提供一种新型硫离子电池及其制备方法。
背景技术
近年来,锂离子电池(LIB)已在能源应用中得到越来越广泛的应用。但是,现有的锂离子电池远远低于商业要求。这激发了人们对高性能电池的极大兴趣。由于地球上的硫储量丰富,价格低廉,环境友好,其材料理论比容量高达1675mAh/g,因此硫电池是非常有前途的电池。目前所研究的硫基电池主要是由碳硫复合材料正极,金属负极和有机电解液组成。硫的绝缘性、充放电过程中体积膨胀以及多硫化物的“穿梭效应”导致电池循环性能差,电池寿命低,从而制约了其在储能领域的发展。因此,开发性能稳定的电解液体系以及解决硫自身性质所产生的问题是硫离子电池发展的关键要素。
发明内容
本发明为了解决上述问题,我们采用廉价炭黑作为硫离子电池的正极活性材料,石墨片为集流体。在负极材料的选取方面,通过大量实验我们采用锌箔这种金属材料作为硫离子电池的负极,并且展现了较好的稳定性。在电解液的选取方面,我们用乙二醇作为溶剂,硫化钠作为溶质,配制不同浓度的电解液。在锌片作为硫离子电池负极充电过程中,硫离子相互聚合,形成多硫化物,最终形成长链状硫,炭黑对硫具有吸附作用,放电时长链硫离子断裂为短链硫离子,被负极金属锌箔吸附,这样一来就形成了硫离子电池(见附图1)。同时乙二醇体系的电解液相比水系的电解液没有析氢析氧反应,从而具有更稳定的循环寿命。该电池成本低廉也使其具有广阔的应用前景。
为达到上述目的,本发明采用的技术方案是:
一种基于硫离子传导的离子电池,所述硫离子电池的正极活性物质为炭黑,负极材料为锌箔,电解液的溶质为硫化钠,电解液的溶剂为乙二醇。
所述电解液中硫化钠的浓度为0.5~2mol/L。进一步的,所述电解液中硫化钠的浓度为2mol/L。
一种硫离子电池的制备方法,首先将炭黑和粘结剂按照比例混合,然后缓慢滴入N-甲基吡咯烷酮NMP,研磨成浆料;之后将浆料涂抹在石墨片集流体上,真空干燥,制得正极片;最后将硫化钠溶于乙二醇,配制电解液,用锌箔作为负极,组装成软包电池。
所述的炭黑和粘结剂的质量混合比例为90~70:10~30。优选的为80:20。
所述的粘结剂为聚偏氟乙烯PVDF或聚四氟乙烯PTFE,优选的为聚偏氟乙烯PVDF。
所述的炭黑与N-甲基吡咯烷酮的质量比为1:5~10,优选的为1:5。
所述的真空干燥的条件为60℃~70℃下干燥12~15h,优选温度为60℃下干燥12h。
本发明的有益效果是:本发明提出了锌箔金属材料作为硫离子电池的负极,展现了稳定的开路电压和良好的循环稳定性。并且采用了乙二醇体系的电解液,相对于水系的电解液,避免了析氢析氧反应对电极的腐蚀,从而极大地提高了硫离子电池的循环寿命。由于硫离子电池所采用的电极材料以及电解液成本低廉,同时也具备绿色、环保等优点,因此具有很大的应用价值和市场前景。
附图说明
图1中(a)、(b)分别为硫离子电池的原理图和充电过程中硫离子插层碳中的示意图。
图2为充电完全下,硫离子插层正极炭黑材料的X射线光电子能谱分析(XPS)图。其中(a)为主图,(b)、(c)、(d)分别为硫、碳、氧三种元素分峰图。
图3为锌箔作为硫离子电池负极时的循环曲线。
图4为锌箔作为硫离子电池负极时的循环寿命。
具体实施方式
以下对本发明做进一步说明。
实施例1
正极由炭黑和粘结剂(聚偏氟乙烯PVDF)制成,其质量比为炭黑/PVDF=24mg:6mg,然后缓慢滴入120mg的N-甲基吡咯烷酮(NMP),研磨制浆。最后将浆料涂抹在50微米厚的石墨片上,放在真空干燥箱中60℃干燥12h,制得正极片。将0.38g硫化钠溶于10ml乙二醇中,配制成0.5mol/L的电解液,选取面积为3cm*3cm、厚度为50微米的锌箔作为硫离子电池的负极,组装成软包电池。
实施例2
正极由炭黑和粘结剂(聚偏氟乙烯PVDF)制成,其质量比为炭黑/PVDF=24mg:6mg,然后缓慢滴入120mg的N-甲基吡咯烷酮(NMP),研磨制浆。最后将浆料涂抹在50微米厚的石墨片上,放在真空干燥箱中60℃干燥12h,制得正极片。将0.76g硫化钠溶于10ml乙二醇中,配制成1mol/L的电解液,选取面积为3cm*3cm、厚度为50微米的锌箔作为硫离子电池的负极,组装成软包电池。
实施例3
正极由炭黑和粘结剂(聚偏氟乙烯PVDF)制成,其质量比为炭黑/PVDF=24mg:6mg,然后缓慢滴入120mg的N-甲基吡咯烷酮(NMP),研磨制浆。最后将浆料涂抹在50微米厚的石墨片上,放在真空干燥箱中60℃干燥12h,制得正极片。将1.52g硫化钠溶于10ml乙二醇中,配制成2mol/L的电解液,选取面积为3cm*3cm、厚度为50微米的锌箔作为硫离子电池的负极,组装成软包电池。
Claims (9)
1.一种可充电硫离子电池,其特征在于,所述可充电硫离子电池的正极活性材料为炭黑,负极材料为锌箔,电解液的溶质为硫化钠,电解液的溶剂为乙二醇;
所述电解液中硫化钠的浓度为0.5~2mol/L。
2.根据权利要求1所述的一种可充电硫离子电池,其特征在于,所述电解液中硫化钠的浓度为2mol/L。
3.一种可充电硫离子电池的制备方法,其特征在于,首先将炭黑和粘结剂按照比例混合,然后缓慢滴入N-甲基吡咯烷酮NMP,研磨成浆料;之后将浆料涂抹在石墨片集流体上,真空干燥,制得正极片;最后将硫化钠溶于乙二醇,配制成浓度为0.5~2mol/L的电解液,用锌箔作为负极,组装成软包电池。
4.根据权利要求3所述的一种可充电硫离子电池的制备方法,其特征在于,所述的炭黑和粘结剂的质量混合比例为90~70:10~30。
5.根据权利要求3或4所述的一种可充电硫离子电池的制备方法,其特征在于,所述的粘结剂为聚偏氟乙烯PVDF或聚四氟乙烯PTFE。
6.根据权利要求3或4所述的一种可充电硫离子电池的制备方法,其特征在于,所述的炭黑与N-甲基吡咯烷酮的质量比为1:5~10。
7.根据权利要求5所述的一种可充电硫离子电池的制备方法,其特征在于,所述的炭黑与N-甲基吡咯烷酮的质量比为1:5~10。
8.根据权利要求3、4或7所述的一种可充电硫离子电池的制备方法,其特征在于,所述的真空干燥的条件为:60℃~70℃下干燥12~15h。
9.根据权利要求8所述的一种可充电硫离子电池的制备方法,其特征在于,所述的炭黑和粘结剂的质量混合比例为80:20;所述的炭黑与N-甲基吡咯烷酮的质量比为1:5;所述的真空干燥的条件为:60℃下干燥12h。
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