KyuJung Jun, Yihan Xiao, Wenhao Sun, Young-Woon Byeon, Haegyeom Kim and Gerbrand Ceder
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Nitride Lithium-ion Conductors with Enhanced Oxidative Stability
It is desirable to develop solid electrolytes that have both excellent reductive stability against lithium metal and oxidative stability against high-voltage cathodes. However, no inorganic superionic conductors reported thus far satisfy these criteria. Nitrides exhibit intrinsically superior stability against reduction but are often readily oxidized at voltages as low as 0.6 V. In this article, we investigated all nitride-based compounds to search for materials with improved oxidative stabilities over 2.0 V while retaining their intrinsic stability against Li metal. We found two compounds, LiPN2 and Li2CN2, with high oxidative stability > 2.0 V and low vacancy migration energies. Using fine-tuned CHGNet machine-learning interatomic potential, we found that upon introducing aliovalent dopants to introduce vacancies in Li2CN2, the dopant and vacancy strongly anchor with each other to result in trapped vacancies, which lowers ionic conductivity. In contrast, vacancies and dopants have minimal interactions in LiPN2, resulting in a high ionic conductivity. These two compounds were synthesized, but their ionic conductivities were not successfully measured because of the challenges in densification. With improved processing conditions, these compounds may serve as anode-side separators in dual-separator-type all-solid-state batteries or anode buffer layer materials interfaced with lithium metal.
期刊介绍:
The Journal of The Electrochemical Society (JES) is the leader in the field of solid-state and electrochemical science and technology. This peer-reviewed journal publishes an average of 450 pages of 70 articles each month. Articles are posted online, with a monthly paper edition following electronic publication. The ECS membership benefits package includes access to the electronic edition of this journal.