CN111370783B - 一种高性能水系氯离子电池及其制备方法 - Google Patents
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Abstract
本发明提供一种高性能水系氯离子电池及其制备方法,属于电池领域。所述高性能水系氯离子电池的正极活性物质为石墨烯、碳纳米管或炭黑,负极材料为锌箔,电解液是饱和四甲基氯化铵水溶液。本发明首次提出将碳材料(石墨烯、碳纳米管、炭黑)作为氯离子电池的正极材料,并将盐包水电解质概念应用到氯离子电池中,当使用金属锌箔作为负极组装成新型的氯离子电池时,电池具有高达2.7V的放电平台。相比于传统的氯离子电池,新型的氯离子电池不存在电极材料在电解质中溶解的问题,电池的寿命有了极大的提高。同时,新型氯离子电池的电极片和电解液制备简单,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,提供一种高性能水系氯离子电池及其制备方法。
背景技术
随着电化学储能技术的快速发展,锂离子电池的能量密度逐渐接近其理论值,再加上地球上的锂资源有限,需要开发新的电池技术以满足大规模储能的需求。氯离子电池由于具有高达2500Wh/L的理论体积能量密度,同时地球上的氯资源储量丰富,而被视为下一代电池的有力竞争者。目前所研究的氯离子电池主要由金属氯化物和金属氯化物正极,离子液体和金属负极组成。其存在电极材料在电解液中溶解的问题,这导致了电池循环稳定性差,电池寿命低,从而制约了其在储能领域的发展。因此,开发性能优异的正极材料以及与其兼容的电解质是氯离子电池发展的关键。
发明内容
基于上述问题,我们提出使用碳材料(石墨烯,碳纳米管和炭黑)作为氯离子电池的正极,金属锌做负极,并应用“盐包水”的概念来扩大氯离子水性电解质的稳定性窗口。在这种“盐包水”电解质体系下,电池的放电平台高达2.7V。同时,碳正极表现出良好的循环稳定性和电化学性能,当炭黑与碳纳米管作为正极材料时,电池的循环寿命为1000次,当石墨烯作为正极材料时,电池在2000次循环后没有明显的容量衰减。其充放电机理为,电池充电时,Cl-离子嵌入到正极碳材料中,发生插层反应;电池放电时,Cl-离子则正极碳材料中脱出并沉积到负极金属锌表面。
为达到上述目的,本发明采用的技术方案是:
一种高性能水系氯离子电池,所述高性能水系氯离子电池的正极活性物质为石墨烯、碳纳米管或炭黑,负极材料为锌箔,电解液是饱和四甲基氯化铵水溶液。
一种高性能水系氯离子电池的制备方法,步骤如下:
(1)用石墨箔做集流体,将正极活性物质和粘结剂按照一定的质量比混合,然后缓慢滴入N-甲基吡咯烷酮(NMP),研磨成均匀的浆料并将其涂抹在石墨箔上,然后放在真空干燥箱中干燥,制得正极片。其中,所述的粘结剂包括聚偏氟乙烯(PVDF)、聚乙烯醇(PVA)、聚四氟乙烯(PTFE);正极活性物质与粘结剂的质量比为10~15:1;正极活性物质与N-甲基吡咯烷酮的质量比为1:5~10;所述的正极活性物质为石墨烯、碳纳米管或炭黑;
(2)用去离子水做溶剂,四甲基氯化铵做溶质,制备的饱和四甲基氯化铵水溶液作为电解液;
(3)用锌箔作为负极片,组装成软包电池。
所述的真空干燥箱中干燥的条件为:温度为50℃~80℃,时间为6~15h。
本发明的有益效果是:本发明首次提出将碳材料(石墨烯、碳纳米管、炭黑)作为氯离子电池的正极材料,并将盐包水电解质概念应用到氯离子电池中,当使用金属锌箔作为负极组装成新型的氯离子电池时,电池具有高达2.7V的放电平台。相比于传统的氯离子电池,新型的氯离子电池不存在电极材料在电解质中溶解的问题,电池的寿命有了极大的提高。同时,新型氯离子电池的电极片和电解液制备简单,电解液绿色、安全,具有很大的应用价值和市场前景。
附图说明
图1为电池的充放电曲线。
图2为石墨烯作为正极材料时,电池的循环寿命。
图3为电池充电完全状态下,氯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)分别为氯、炭、氧三种元素分峰图。
具体实施方式
以下对本发明做进一步说明。
实施例1
将10mg石墨烯和1mg聚偏氟乙烯(PVDF)均匀混合,然后缓慢滴入50mgN-甲基吡咯烷酮(NMP),研磨成均匀的浆料。最后将浆料涂抹在50微米厚,面积为2.5cm*2.5cm的石墨箔上,放在真空干燥箱中60℃干燥12h,制得正极片。将6g四甲基氯化铵溶于10ml去离子水中,配制成饱和溶液作为电解液,选取面积为2.5cm*2.5cm、厚度为50微米的锌箔作为电池的负极,组装成软包电池。
实施例2
将12mg碳纳米管和1mg聚偏氟乙烯(PVDF)均匀混合,然后缓慢滴入60mg N-甲基吡咯烷酮(NMP),研磨成均匀的浆料。最后将浆料涂抹在50微米厚,面积为2.5cm*2.5cm的石墨箔上,放在真空干燥箱中70℃干燥10h,制得正极片。将6g四甲基氯化铵溶于10ml去离子水中,配制成饱和溶液作为电解液,选取面积为2.5cm*2.5cm、厚度为50微米的锌箔作为电池的负极,组装成软包电池。
实施例3
将10mg炭黑和1mg聚偏氟乙烯(PVDF)均匀混合,然后缓慢滴入60mg N-甲基吡咯烷酮(NMP),研磨成均匀的浆料。最后将浆料涂抹在50微米厚,面积为2.5cm*2.5cm的石墨箔上,放在真空干燥箱中60℃干燥12h,制得正极片。将6g四甲基氯化铵溶于10ml去离子水中,配制成饱和溶液作为电解液,选取面积为2.5cm*2.5cm、厚度为50微米的锌箔作为电池的负极,组装成软包电池。
Claims (9)
1.一种高性能水系氯离子电池,其特征在于,所述高性能水系氯离子电池的正极活性物质为石墨烯、碳纳米管或炭黑,负极材料为锌箔,电解液是饱和四甲基氯化铵水溶液。
2.一种高性能水系氯离子电池的制备方法,其特征在于,步骤如下:
(1)用石墨箔做集流体,将正极活性物质和粘结剂按照一定的质量比混合,然后缓慢滴入N-甲基吡咯烷酮,研磨成均匀的浆料并将其涂抹在石墨箔上,然后放在真空干燥箱中干燥,制得正极片;所述的正极活性物质为石墨烯、碳纳米管或炭黑;
(2)用去离子水做溶剂,四甲基氯化铵做溶质,制备的饱和四甲基氯化铵水溶液作为电解液;
(3)用锌箔作为负极片,组装成软包电池。
3.根据权利要求2所述的一种高性能水系氯离子电池的制备方法,其特征在于,所述的粘结剂包括聚偏氟乙烯、聚乙烯醇、聚四氟乙烯。
4.根据权利要求2或3所述的一种高性能水系氯离子电池的制备方法,其特征在于,正极活性物质与粘结剂的质量比为10~15:1。
5.根据权利要求2或3所述的一种高性能水系氯离子电池的制备方法,其特征在于,正极活性物质与N-甲基吡咯烷酮的质量比为1:5~10。
6.根据权利要求4所述的一种高性能水系氯离子电池的制备方法,其特征在于,正极活性物质与N-甲基吡咯烷酮的质量比为1:5~10。
7.根据权利要求2、3或6所述的一种高性能水系氯离子电池的制备方法,其特征在于,所述的真空干燥箱中干燥的条件为:温度为50℃~80℃,时间为6~15h。
8.根据权利要求4所述的一种高性能水系氯离子电池的制备方法,其特征在于,所述的真空干燥箱中干燥的条件为:温度为50℃~80℃,时间为6~15h。
9.根据权利要求5所述的一种高性能水系氯离子电池的制备方法,其特征在于,所述的真空干燥箱中干燥的条件为:温度为50℃~80℃,时间为6~15h。
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