细菌纤维素衍生的三维碳集流体用于无枝晶的锂金属负极

doi:10.3866/PKU.WHXB202008088

物理化学学报 >> 2021, Vol. 37 >> Issue (2): 2008088.doi: 10.3866/PKU.WHXB202008088

所属专题：金属锂负极

细菌纤维素衍生的三维碳集流体用于无枝晶的锂金属负极

张云博¹, 林乔伟², 韩俊伟², 韩志远², 李曈², 康飞宇¹^,², 杨全红³, 吕伟²^,*()

¹ 清华大学清华-伯克利深圳学院，广东深圳 518055
² 清华大学深圳国际研究生院，深圳盖姆石墨烯研究中心，广东深圳 518055
³ 天津大学化工学院，化学工程联合国家重点实验室(天津大学)，天津 300072

收稿日期:2020-08-31 录用日期:2020-09-30 发布日期:2020-10-19
通讯作者: 吕伟 E-mail:lv.wei@sz.tsinghua.edu.cn
基金资助:
国家重点研发计划(2018YFE0124500);国家自然科学基金(51972190);广东省杰出青年自然科学基金(2017B030306006);深圳市科技计划基础研究(学科布局)项目(JCYJ20180508152037520)

Bacterial Cellulose-Derived Three-Dimensional Carbon Current Collectors for Dendrite-Free Lithium Metal Anodes

Yunbo Zhang¹, Qiaowei Lin², Junwei Han², Zhiyuan Han², Tong Li², Feiyu Kang¹^,², Quan-Hong Yang³, Wei Lü²^,*()

¹ Tsinghua-Berkeley Shenzhen Institute (TBSI), Tsinghua University, Shenzhen 518055, Guangdong Province, China
² Shenzhen Geim Graphene Center, Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen 518055, Guangdong Province, China
³ State Key Laboratory of Chemical Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China

Received:2020-08-31 Accepted:2020-09-30 Published:2020-10-19
Contact: Wei Lü E-mail:lv.wei@sz.tsinghua.edu.cn
About author:Wei Lü, Email: lv.wei@sz.tsinghua.edu.cn; Tel.: +86-755-86964142
Supported by:
the National Key Research and Development Program of China(2018YFE0124500);the National Natural Science Foundation of China(51972190);the Guangdong Natural Science Funds for Distinguished Young Scholars(2017B030306006);Shenzhen Basic Research Project(JCYJ20180508152037520)

摘要/Abstract

摘要：

锂金属是下一代高能量密度电池的关键负极，然而其实用化面临着一系列问题，主要包括循环过程中体积变化大、枝晶生长等。使用三维集流体是解决这些问题的有效方法，然而现有大多数三维集流体存在重量大、体积大、表面亲锂性差、成本高等问题。针对上述问题，本文以低成本的细菌纤维素为前驱体，通过直接碳化制备出具有连通网络的轻质三维碳集流体，其表面均匀分布的含氧官能团可以促进锂离子的均匀成核和沉积，有效抑制了枝晶生长。值得注意的是，该集流体的面密度仅为0.32 mg·cm^-2，在3 mAh·cm^-2比容量的锂金属负极中质量占比仅为28.8%。电化学测试结果表明，该集流体在3 mA·cm^-2的高电流密度或4 mAh·cm^-2的高循环容量的工作条件下，稳定循环超过150次，并且在对称电池或与LiNi_0.8Co_0.15Al_0.05匹配的全电池中也表现出良好的电化学性能。

关键词: 锂金属负极, 细菌纤维素, 三维集流体, 锂枝晶, 含氧官能团

Abstract:

Lithium (Li) metal anodes are critical components for next-generation high-energy density batteries, owing to their high theoretical specific capacity (3800 mAh·g^-1) and low voltage (-3.040 V versus the standard hydrogen electrode). However, their applications are hindered by dendrite growth, which potentially induces inner short circuit and leads to safety issues. Employing three-dimensional (3D) current collectors is an effective strategy to suppress dendrite growth by decreasing the local current density. However, many of the reported 3D current collectors have a lithiophobic surface, which leads to non-uniform Li⁺ ion deposition. Thus, a complicated modification process is required to increase the lithiophilic property of the current collectors. In addition, they have a large weight or volume, which greatly lowers the energy density of the entire anode. In this work, we report a lightweight 3D carbon current collector with a lithiophilic surface by employing the direct carbonization of low-cost bacterial cellulose (BC) biomass. The current collector is composed of electrically conductive, robust, and interconnected carbon nanofiber networks, which provide sufficient void space to accommodate a large amount of Li and buffer the volume changes during Li plating and stripping. More importantly, homogeneously distributed oxygen-containing functional groups on the nanofiber surface are retained by controlling the carbonization temperature. These functional groups serve as uniform nucleation sites and help realize uniform and dendrite-free Li deposition. Notably, the areal mass density of the 3D carbon current collector was only 0.32 mg·cm^-2 and its mass ratio in the whole anode was 28.8%, with a capacity of 3 mAh·cm^-2. This 3D carbon current collector facilitates the stable working of the half cells for 150 cycles under a high current density of 3 mA·cm^-2 or a high capacity of 4 mAh·cm^-2. Symmetric cells exhibit a steady cycling life as long as 600 h under a current density of 1 mA·cm^-2 and a capacity of 1 mAh·cm^-2. Moreover, appreciable cycling performance was realized in the full cells when the anodes were paired with LiNi_0.8Co_0.15Al_0.05 cathodes. Furthermore, the low-cost raw materials and the simple preparation method promise significant potential for the future applications of the proposed 3D current collectors.

Key words: Lithium metal anode, Bacterial cellulose, Three-dimensional current collector, Lithium dendrite, Oxygen-containing functional group

MSC2000:

O646

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张云博, 林乔伟, 韩俊伟, 韩志远, 李曈, 康飞宇, 杨全红, 吕伟. 细菌纤维素衍生的三维碳集流体用于无枝晶的锂金属负极[J]. 物理化学学报, 2021, 37(2): 2008088.

Yunbo Zhang, Qiaowei Lin, Junwei Han, Zhiyuan Han, Tong Li, Feiyu Kang, Quan-Hong Yang, Wei Lü. Bacterial Cellulose-Derived Three-Dimensional Carbon Current Collectors for Dendrite-Free Lithium Metal Anodes[J]. Acta Phys. -Chim. Sin., 2021, 37(2): 2008088.

图/表 4

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细菌纤维素衍生的三维碳集流体用于无枝晶的锂金属负极

Bacterial Cellulose-Derived Three-Dimensional Carbon Current Collectors for Dendrite-Free Lithium Metal Anodes

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