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Improving the cycling stability of lithium metal anodes using Cu3N-modified Cu foil as a current collector

利用Cu3 N改性铜箔集流体提高锂金属负极的循环稳定性

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Abstract

Lithium (Li) metal anodes have the potential to stimulate the development of secondary batteries due to their high theoretical specific capacities and low redox potentials among all possible solid secondary anode compounds. However, the growth of Li dendrites during repeated Li stripping/plating processes leads to low coulombic efficiencies (CEs) and safety hazards, which significantly hinders their practical application. In this work, commercial Cu foil was modified in situ by Cu3N nanowires (Cu3N NWs/Cu) and used as the current collector for a Li anode. In addition to decreasing the true current density of the anode and alleviating the volume change during the cycles, Cu3N reacted with Li during the initial cycle (3Li + Cu3N → Li3N + 3Cu), which enabled the formation of a Li3N-rich solid electrolyte interphase (SEI). This Li3N-rich SEI with a high ionic conductivity not only boosted Li ion transport but also promoted the homogeneous deposition of Li via increased Li nucleation sites. The improvements in both mass transport and deposition dynamics restrained dendrite growth. As a result, the Cu3N NWs/Cu anode had stable Li plating/stripping over 270 cycles with a high average CE of 98.6% at 1 mA cm−2, with Li capacities of 1 mA h cm−2. A long cycling lifespan of 430 cycles was achieved using a full cell with a high-load LiFePO4 cathode (mass loading: 10 mg cm−2) and a Cu3N NWs/Cu-Li anode (N/P = 2.35), demonstrating the effectiveness and practicality of the Cu3N NWs/Cu current collector in stabilizing the Li anode.

摘要

在二次电池的所有固态负极中, 锂金属负极因其极高的理论比容量和极低的还原电位对促进二次电池的进一步发展具有很大的潜力. 然而, 锂负极在不断脱锂/嵌锂的过程中因锂枝晶的生长导致低库伦效率并存在安全隐患, 严重阻碍了锂金属负极的实际应用. 该研究通过化学方法在商业化的铜箔集流体表面原位修饰Cu3N纳米线得到复合微结构型集流体(Cu3N NWs/Cu). 引入的Cu3N纳米线具有三维结构,不仅可以增大集流体的比表面积、降低集流体表面的电流密度, 还可以容纳锂负极在沉积/脱嵌过程中发生的体积变化. 此外, 在首次锂沉积的过程中, Cu3N与锂金属反应生成Li3N(3Li + Cu3N → Li3N + 3Cu),可以促进稳定的富含Li3N的固态电解质膜(SEI)形成. 富含Li3 N的SEI既能增强锂离子的传输, 又能给锂的沉积提供充足的形核位点, 促进锂金属的均匀沉积, 从而抑制了锂枝晶的生长. 在锂沉积/剥离循环过程中,这种经过Cu3N纳米线修饰的铜箔集流体在电流密度为1 mA cm−2, 锂沉积量为1 mA h cm−2的条件下可以稳定循环270圈, 平均库伦效率为98.6%. 将沉积锂金属后的Cu3N NWs/Cu-Li复合负极与LiFePO4正极(正极活性物质载量: 10 mg cm−2; N/P = 2.35)组装成全电池, 该全电池能稳定循环430圈. 研究表明经Cu3N纳米线修饰的铜箔集流体在提高锂金属负极的循环稳定性方面具有良好的应用前景.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22075091), the Natural Science Foundation of Hubei Province (2021CFA066), and the “Fundamental Research Funds for the Central Universities” (2021yjsCXCY026). The authors thank the technical support from the Analytical and Testing Center of Huazhong University of Science and Technology (HUST) for material characterizations and the State Key Laboratory of Materials Processing and Die & Mould Technology of HUST for SEM tests.

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Authors and Affiliations

  1. State Key Laboratory of Materials Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan, 430074, China

    Danlei Tang  (唐丹雷), Lixia Yuan  (袁利霞), Yaqi Liao  (廖亚祺), Wenxuan Jin  (靳文轩), Jie Chen  (陈杰), Zexiao Cheng  (程泽晓), Xiang Li  (李想), Bin He  (何斌), Zhen Li  (李真) & Yunhui Huang  (黄云辉)

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  1. Danlei Tang  (唐丹雷)
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  2. Lixia Yuan  (袁利霞)
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  3. Yaqi Liao  (廖亚祺)
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  4. Wenxuan Jin  (靳文轩)
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  5. Jie Chen  (陈杰)
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  6. Zexiao Cheng  (程泽晓)
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  7. Xiang Li  (李想)
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  8. Bin He  (何斌)
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  9. Zhen Li  (李真)
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  10. Yunhui Huang  (黄云辉)
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Contributions

Yuan L and Tang D conceived the project. Tang D designed and engineered the samples, Liao Y, Jin W, Chen J, Cheng Z, and He B helped with the characterization. Tang D wrote the paper with support from Yuan L and Huang Y. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Lixia Yuan  (袁利霞) or Yunhui Huang  (黄云辉).

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Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary information

Supporting data are available in the online version of the paper.

Danlei Tang received her BS degree from Nanjing University of Aeronautics and Astronautics (NUAA), China, in 2015. She is currently a Master degree candidate at the School of Materials Science and Engineering, Huazhong University of Science and Technology. Her current research mainly focuses on lithium metal batteries.

Lixia Yuan received her BS, MS, and PhD degrees from Wuhan University. She worked as a post-doctoral researcher at Tsinghua University from 2007 to 2009. She is now a professor at Huazhong University of Science and Technology. Her research interests mainly focus on lithium rechargeable batteries.

Yunhui Huang received his BS, MS, and PhD degrees from Peking University. From 2002 to 2004, he worked as an associate professor at Fudan University. He then worked with Prof. John B. Goodenough at the University of Texas at Austin for more than three years. In 2008, he became a chair professor of materials science at Huazhong University of Science and Technology. His research group works on rechargeable batteries and electrode materials.

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Tang, D., Yuan, L., Liao, Y. et al. Improving the cycling stability of lithium metal anodes using Cu3N-modified Cu foil as a current collector. Sci. China Mater. 65, 2385–2392 (2022). https://doi.org/10.1007/s40843-021-2036-x

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