Constructing stable lithium metal anodes using a lithium adsorbent with a high Mn³⁺/Mn⁴⁺ ratio

Abstract

Lithium (Li) metal batteries (LMBs) have emerged as the most prospective candidates for post-Li-ion batteries. However, the practical deployment of LMBs is frustrated by the notorious Li dendrite growth on hostless Li metal anodes. Herein, a protonated Li manganese (Mn) oxide with a high Mn³⁺/Mn⁴⁺ ratio is used as a Li adsorbent for constructing highly stable Li metal anodes. In addition to the Mn³⁺ sites with high Li affinity that afford an ultralow Li nucleation overpotential, the decrease in the average Mnⁿ⁺ oxidation state also induces a disordered adsorbent structure via the Jahn-Teller effect, resulting in improved Li transfer kinetics with a significantly reduced Li electroplating overpotential. Based on the mutually improved Li diffusion and adsorption kinetics, the Li adsorbent is used as a versatile host to enable dendrite-free and stable Li metal anodes in LMBs. Consequently, a modified Li||LiNi_0.8Mn_0.1Co_0.1O₂ (NMC811) coin cell with a high NMC811 loading of 4.3 mAh cm^-2 delivers a high Coulombic efficiency of 99.85% over 200 cycles and the modified Li||NMC811 pouch cell also achieves a remarkable improvement in electrochemical performance. This work demonstrates a novel approach for the preparation of highly efficient Li protection structures for safe LMBs with long lifespans.

Keywords

Lithium metal batteries / lithium metal anodes / dendrites / protonated lithium manganese oxide

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