CN106920953B - 具有核壳结构的锂硫电池正极材料及其制备方法 - Google Patents

具有核壳结构的锂硫电池正极材料及其制备方法 Download PDF

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CN106920953B
CN106920953B CN201710312265.9A CN201710312265A CN106920953B CN 106920953 B CN106920953 B CN 106920953B CN 201710312265 A CN201710312265 A CN 201710312265A CN 106920953 B CN106920953 B CN 106920953B
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黄钊文
肖文平
张立荣
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Shunde Vocational And Technical University
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Abstract

本发明公开一种具有核壳结构的锂硫电池正极材料，其特征在于：具有核壳结构，内核为具有纳米尺度的单质硫，内核的数量可以是一个，也可以是多个，次外层为疏松且具备良好导电性的碳纳米管、碳纳米纤维或者两者的混合物，最外层为柠檬酸或沥青裂解碳构成的具有一定硬度的外壳。本发明方法制备简便，成本低廉，且利于规模化生产，有利于实现锂硫电池正极材料的商业化。

Description

具有核壳结构的锂硫电池正极材料及其制备方法
技术领域
本发明涉及锂硫电池正极材料技术领域，更具体地说，是涉及一种具有核壳结构的锂硫电池正极材料及其制备方法。
背景技术
锂硫电池其电极理论容量达到1675mAh/g，电池能量密度高达2600Wh/kg，是在研的各种二次电池所无法比拟的。但是单质硫的导电性较弱，且存在多硫化物在电解液中的溶解，以及充放电过程中存在较大的体积膨胀与收缩，导致其至今无法商业化。
一种较常用的方法是硫与纳米无机金属复合，希望利用纳米无机金属的高比表面积实现对硫的吸附的同时提升硫的导电性，该方法的缺点是大幅降低电极的硫含量，大部分的载流量不足50％，无法体现锂硫电池的优越性；
另一种方法是硫与导电高分子化合物复合，将导电高分子作为硫的基质，并提供导电性，该方法能减少硫在电解液中的溶解，并为硫提供导电基质的作用，但仍无法解决体积膨胀的问题，且不能根本解决多硫化物在电解液中溶解的问题。
还有一种则是采用各种孔径的纳米碳及其衍生物(如石墨烯)与硫复合。由于纳米碳及其衍生物具有较强的导电性及吸附性，且能为硫的体积膨胀预留空间，目前能做出具有较高容量的样品。但其仍未能彻底解决硫的溶解问题。
发明内容
本发明的目的在于提供一种具有核壳结构的锂硫电池正极材料及其制备方法，以克服现有技术中所存在的不足。
本发明解决其技术问题的技术方案是：一种具有核壳结构的锂硫电池正极材料，其特征在于：具有核壳结构，内核为具有纳米尺度的单质硫，内核的数量可以是一个，也可以是多个，次外层为疏松且具备良好导电性的碳纳米管、碳纳米纤维或者两者的混合物，最外层为柠檬酸或沥青裂解碳构成的具有一定硬度的外壳。
一种锂硫电池正极材料的制备方法，其特征在于包括以下步骤：
S1)将单质硫与Ni(NO3)2·6H2O混合，放入纳米球磨机中球磨不少于40小时并充分干燥；
S2)放入通有氮气气氛保护的回转炉中，同时通入乙炔气体，加热使乙炔气体裂解成为碳纳米管或者碳纤维或者两者的混合物；
S3)将步骤S2)所获得的半成品与经有机溶剂溶解的柠檬酸或沥青充分混合；
S4)干燥后放入氮气气氛保护的炉中作热处理，柠檬酸或沥青裂解碳形成具有一定硬度的外壳。
上述具有核壳结构的锂硫电池正极材料的制备方法中，单质硫的总混合物中所占的质量百分比是70％-85％；Ni(NO3)2·6H2O的质量百分比是0.1％～1％；碳纳米管或者碳纤维或者两者的混合物的质量比为3％-10％；外壳质量比为4％～27％。
本发明的有益效果是：
本发明的单质硫具备纳米尺度(单体颗粒不大于100nm)，能有效改变硫绝缘的特点；二是外包覆的疏松且具备良好导电性的碳纳米管或碳纳米纤维及其混合物能有效提升单质硫的导电性，且为硫可能存在的体积膨胀预留空间；三是外包覆具有一定硬度的外壳，彻底解决了多硫化物在电解液中溶解的问题，并将硫的嵌锂反应及体积膨胀控制在核壳结构内，能有效提升该正极材料的循环寿命及稳定性。
另外，本发明方法制备简便，成本低廉，且利于规模化生产，有利于实现锂硫电池正极材料的商业化。
附图说明
图1是本发明具有核壳结构的锂硫电池正极材料的制备方法流程示意图。
具体实施方式
下面详细描述本发明的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，仅用于解释本发明，而不能理解为对本发明的限制。
如图1所示，本发明提供了一种用于锂硫电池的正极材料及其制备方法。正极材料的特征如下：核壳结构正极材料10具有核壳结构11，内核为具有纳米尺度的单质硫内核13，内核的数量可以是一个，也可以是多个，次外层为疏松且具备良好导电性的碳纳米管、碳纳米纤维或者两者的混合物12，最外层为柠檬酸或沥青裂解碳构成的具有一定硬度的外壳。
该结构的优点在于：一是单质硫具备纳米尺度(单体颗粒不大于100nm)，能有效改变硫绝缘的特点；二是外包覆的疏松且具备良好导电性的碳纳米管或碳纳米纤维及其混合物能有效提升单质硫的导电性，且为硫可能存在的体积膨胀预留空间；三是外包覆具有一定硬度的外壳，彻底解决了多硫化物在电解液中溶解的问题，并将硫的嵌锂反应及体积膨胀控制在核壳结构内，能有效提升该正极材料的循环寿命及稳定性。
制备方法：将质量比为70％-85％的单质硫2，与Ni(NO3)2·6H2O硝酸镍1充分混合，Ni(NO3)2·6H2O的质量比为0.1％～1％，后放入纳米球磨机中球磨不少于40小时，球磨在无水乙醇的环境中进行，经充分干燥后放入通有氮气气氛保护的回转炉3中，同时通入乙炔气体，加热使乙炔气体裂解成为碳纳米管或者碳纤维或者两者的混合物，沉积碳纳米管/碳纳米纤维复合层，碳纳米管或者碳纤维或者两者的混合物的质量比为3％-10％，将获得的半成品与经有机溶剂溶解的柠檬酸或沥青4充分混合，干燥后放入氮气气氛保护的炉5中作热处理，形成核壳结构正极材料10柠檬酸或沥青裂解碳形成具有一定硬度的外壳，外壳质量比为4％～27％。
尽管已经示出和描述了本发明的实施例，本领域的普通技术人员应当理解：在不脱离本发明的原理和宗旨的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由权利要求及其等同替换所限定，在未经创造性劳动所作的改进等，均应包含在本发明的保护范围之内。

Claims (2)

1.一种具有核壳结构的锂硫电池正极材料的制备方法，所述正极材料具有核壳结构，内核为具有纳米尺度的单质硫，内核的数量是一个或多个，次外层为疏松且具备良好导电性的碳纳米管或碳纳米纤维或碳纳米管和碳纳米纤维两者的混合物，最外层为柠檬酸或沥青裂解碳构成的具有一定硬度的外壳，其特征在于包括以下步骤：
S1)将单质硫与Ni(NO3)2·6H2O混合，放入纳米球磨机中球磨不少于40小时并充分干燥；
S2)放入通有氮气气氛保护的回转炉中，同时通入乙炔气体，加热使乙炔气体裂解成为碳纳米管或者碳纤维或者两者的混合物；
S3)将步骤S2)所获得的半成品与经有机溶剂溶解的柠檬酸或沥青充分混合；
S4)干燥后放入氮气气氛保护的炉中作热处理，柠檬酸或沥青裂解碳形成具有一定硬度的外壳。
2.一种具有核壳结构的锂硫电池正极材料，其特征在于：由权利要求1所述具有核壳结构的锂硫电池正极材料的制备方法制得。
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