4.8 Article

Nitrate Additives Coordinated with Crown Ether Stabilize Lithium Metal Anodes in Carbonate Electrolyte

Journal

ADVANCED FUNCTIONAL MATERIALS
Volume 31, Issue 28, Pages -

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/adfm.202102128

Keywords

carbonate electrolytes; crown ether; high voltage cathodes; lithium metal batteries; nitrate additives

Funding

  1. National Key Research and Development Program of China [2018YFE0124500]
  2. National Natural Science Foundation of China [51972190, 51932005, 52022041]
  3. Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program [2017BT01N111]
  4. Guangdong Natural Science Funds for Distinguished Young Scholars [2017B030306006]
  5. China Postdoctoral Science Foundation [2019M660628]

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By adding rubidium nitrate additive coordinated with 18-crown-6 crown ether to the carbonate electrolyte, the stability of lithium metal anodes can be improved, leading to higher Coulombic efficiency and better battery performance.
Lithium metal anodes (LMAs) are promising for next-generation batteries but have poor compatibility with the widely used carbonate-based electrolytes, which is a major reason for their severe dendrite growth and low Coulombic efficiency (CE). A nitrate additive to the electrolyte is an effective solution, but its low solubility in carbonates is a problem that can be solved using a crown ether, as reported. A rubidium nitrate additive coordinated with 18-crown-6 crown ether stabilizes the LMA in a carbonate electrolyte. The coordination promotes the dissolution of NO3- ions and helps form a dense solid electrolyte interface that is Li3N-rich which guides uniform Li deposition. In addition, the Rb (18-crown-6)(+) complexes are adsorbed on the dendrite tips, shielding them from Li deposition on the dendrite tips. A high CE of 97.1% is achieved with a capacity of 1 mAh cm(-2) in a half cell, much higher than when using the additive-free electrolyte (92.2%). Such an additive is very compatible with a nickel-rich ternary cathode at a high voltage, and the assembled full battery with a cathode material loading up to 10 mg cm(-2) shows an average CE of 99.8% over 200 cycles, indicating a potential for practical use.

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