The long-standing issue of Li-dendrite formation and growth during repeated plating or stripping processes prevents the practical application of Li-metal anodes for high-specific-energy batteries. Here we develop an approach to control dendrite growth by coating the separator with functionalized nanocarbon (FNC) with immobilized Li ions. During cycling, the Li dendrites grow toward each other simultaneously from both the FNC layer on the separator and the Li-metal anode; when the dendrites meet, the growth changes direction: rather than penetrating the separator, a dense Li layer is formed between the separator and the Li anode. This controlled growth alleviates the solid electrolyte interphase formation, reduces the decomposition of the electrolyte, and improves the cyclability of the Li-metal cell. In a Li/LiFePO4 coin cell with three different electrolytes, we show that this approach enables a long stable cycle life (>800 cycles with 80% retention of the initial capacity) and improved efficiency (>97%). Our method offers promise for application in practical Li-metal batteries, and it may also be useful for tackling dendrite issues for other metals.
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The work was partially supported by the Vehicle Technology Office, US Department of Energy (DOE) (Grant No. 1F-32504/DE-AC02-06CH11357), and the National Science Foundation (NSF) (Grant No. 1511645). We would like to acknowledge the Integrated Nanosystems Development Institute (INDI) for the use of their JEOL7800F field-emission scanning electron microscope, which was awarded through NSF grant MRI-1229514. The authors would like to express their appreciation for C. Renguette’s help with English editing. The in situ TEM work was carried out in the Center for Nanoscale Materials at Argonne National Laboratory, an Office of Science user facility supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. Other TEM work was carried out in part at the Center for Functional Nanomaterials at Brookhaven National Laboratory (US DOE contract DE-AC02-98CH10886). Finally, we also thank D. Tien, program director of the Battery Program, Vehicle Technology Office, US DOE, for his support.
A patent has been filed (patent application number 61/486,946) for controlling the Li dendrite growth via the FNC-coated separator method to make the Li electrode rechargeable.
Supplementary Figures 1–7, Supplementary Table 1, Supplementary Discussion, Supplementary References. (PDF 2016 kb)
Li-dendrite growth process examined using in situ TEM. A specially designed TEM cell consisting of a Li-metal working electrode, a Li2O solid electrolyte and an FNC layer coated on the surface of Li2O solid electrolyte, was employed to observe the Li dendrite growing process. (MP4 2166 kb)
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Liu, Y., Liu, Q., Xin, L. et al. Making Li-metal electrodes rechargeable by controlling the dendrite growth direction. Nat Energy 2, 17083 (2017). https://doi.org/10.1038/nenergy.2017.83
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