Metallic lithium is the most competitive anode material for next‐generation lithium (Li)‐ion batteries. However, one of its major issues is Li dendrite growth and detachment, which not only causes safety issues, but also continuously consumes electrolyte and Li, leading to low coulombic efficiency (CE) and short cycle life for Li metal batteries. Herein, the Li dendrite growth of metallic lithium anode is suppressed by forming a lithium fluoride (LiF)‐enriched solid electrolyte interphase (SEI) through the lithiation of surface‐fluorinated mesocarbon microbeads (MCMB‐F) anodes. The robust LiF‐enriched SEI with high interfacial energy to Li metal effectively promotes planar growth of Li metal on the Li surface and meanwhile prevents its vertical penetration into the LiF‐enriched SEI from forming Li dendrites. At a discharge capacity of 1.2 mAh cm−2, a high CE of >99.2% for Li plating/stripping in FEC‐based electrolyte is achieved within 25 cycles. Coupling the pre‐lithiated MCMB‐F (Li@MCMB‐F) anode with a commercial LiFePO4cathode at the positive/negative (P/N) capacity ratio of 1:1, the LiFePO4//Li@MCMB‐F cells can be charged/discharged at a high areal capacity of 2.4 mAh cm−2for 110 times at a negligible capacity decay of 0.01% per cycle.
Lithium is the most attractive anode material for high-energy density rechargeable batteries, but its cycling is plagued by morphological irreversibility and dendrite growth that arise in part from its heterogeneous “native” solid electrolyte interphase (SEI). Enriching the SEI with lithium fluoride (LiF) has recently gained popularity to improve Li cyclability. However, the intrinsic function of LiF—whether chemical, mechanical, or kinetic in nature—remains unknown. Herein, we investigated the stability of LiF in model LiF-enriched SEIs that are either artificially preformed or derived from fluorinated electrolytes, and thus, the effect of the LiF source on Li electrode behavior. We discovered that the mechanical integrity of LiF is easily compromised during plating, making it intrinsically unable to protect Li. The ensuing in situ repair of the interface by electrolyte, either regenerating LiF or forming an extra elastomeric “outer layer,” is identified as the more critical determinant of Li electrode performance. Our findings present an updated and dynamic picture of the LiF-enriched SEI and demonstrate the need to carefully consider the combined role of ionic and electrolyte-derived layers in future design strategies.
more » « less- Award ID(s):
- 1804247
- NSF-PAR ID:
- 10127687
- Publisher / Repository:
- Proceedings of the National Academy of Sciences
- Date Published:
- Journal Name:
- Proceedings of the National Academy of Sciences
- Volume:
- 117
- Issue:
- 1
- ISSN:
- 0027-8424
- Page Range / eLocation ID:
- p. 73-79
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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