Nahm, Seokho Kim, Hyunbin Kim, Mihyun Oh, Kwanyoung Yim, Haena Lee, Somi Hong, Jinseok Kim, Minki Kim, Jeongmin Seo, Yoon Kyung Park, Yun Chang Yuk, Jong Min Yoon, Chong-Seung Choi, Ji-Won Oh, Nuri Yu, Seung-Ho Lee, Seung-Yong 2025-12-19T07:00:19Z 2025-12-19T07:00:19Z 2025-12-19 2026-03 2095-4956 https://pubs.kist.re.kr/handle/201004/153799 The electrolyte additive, lithium nitrate (LiNO3), is widely recognized for suppressing dendritic lithium growth in anode-free lithium metal batteries, yet its stabilizing effect is transient, and the mechanistic origin of this limitation has remained unresolved. Here, we uncover the origin of this behavior through a comprehensive analysis driven by artifact/damage-free direct cryogenic transmission electron microscopy, which enabled one of the most chemically specific and morphologically intuitive visualizations to date of intact solid-electrolyte interphases (SEIs) and lithium growth. Contrary to conventional interpretations centered on nitrogen-rich or single-component SEIs, we reveal that LiNO3 rapidly generates lithium hydroxide (LiOH) and lithium oxide (Li2O) rich interphases, whose complementary functions- ionic transport through LiOH and mechanical robustness from Li2O-synergistically suppress whisker nucleation and favor compact, particle-like growth. Over the extended plating, however, depletion of these species in combination with crystallographically favored orientations drives the particle-to-whisker transition, explaining why the effectiveness of LiNO3 is inherently limited. This direct mechanistic visualization resolves a long-standing ambiguity regarding the transient efficacy of LiNO3 and reframes its function from a nitrogen-driven mechanism to a synergistic dual oxygen-interphase framework. Beyond mechanistic clarification, these findings establish that continuous regeneration of LiOH and Li2O is essential for stable lithium deposition, offering a design principle for the development of durable electrolytes in high-performance anode-free lithium metal batteries. (c) 2025 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights are reserved, including those for text and data mining, AI training, and similar technologies. English Elsevier BV Revealing the mechanisms behind transient whisker suppression by LiNO3 in anode-free lithium metal batteries Article 10.1016/j.jechem.2025.10.037 3 Journal of Energy Chemistry, v.114, pp.485 - 495 Journal of Energy Chemistry 114 485 495 N 001623206900003 2-s2.0-105021879174 Chemistry, Applied Chemistry, Physical Energy & Fuels Engineering, Chemical Chemistry Energy & Fuels Engineering Article COULOMBIC EFFICIENCY NITRATE NUCLEATION WATER Anode-free lithium metal battery Lithium whisker suppression Air-free cryo-TEM LiOH/Li2O SEI LiNO3 electrolyte additive