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journal article·2025-03Open access

Reduction‐Induced Oxygen Loss: the Hidden Surface Reconstruction Mechanism of Layered Oxide Cathodes in Lithium‐Ion Batteries

Seungyun Jeon, Gukhyun Lim, Hoseok Lee, Hyunyoung Park, Min Kyung Cho, Chan Kim, YeEun Lee, Jaehoon Kim, Minhyung Kwon, Jung‐Keun Yoo, Hyangsoo Jeong, Jinwoo Kim, Seung‐Ho Yu, Minah Lee, Jongsoon Kim, Jihyun Hong

Advanced Energy Materials· Volume 15· Issue 12
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Source abstract

Abstract

Abstract The surface reconstruction from the layered to rocksalt‐type phase represents a primary deterioration pathway of layered‐oxide cathodes in lithium‐ion batteries, involving irreversible oxygen loss and transition metal migration. This degradation mechanism has primarily been attributed to the oxidative instability of highly delithiated cathodes at high voltages (>4.3 V vs Li/Li+). However, the battery degradation also occurs under seemingly stable voltage ranges, the origin of which remains unclear. Herein, a hidden mechanism to induce surface reconstruction and oxygen loss is proposed, termed the “quasi‐conversion reaction”, which is revealed to occur during electrochemical reduction (discharge) processes just below 3.0 V (vs Li/Li+). Combined experiments and first‐principles calculations unveil that the oxygens at the surface can be extracted from the cathode lattice by forming lithium oxides and oxygen vacancies, at significantly higher potentials than conventional conversion reaction, due to the instability of surface oxygens coordinated with fewer cations than in the bulk. The chemical incompatibility between lithium oxides and commercial carbonate‐based electrolytes results in electrolyte decomposition, forming an organic‐rich blocking layer and gaseous byproducts, which further increases the cell impedance. This study emphasizes the necessity of a thorough understanding of surface instability upon reduction to develop long‐lasting batteries.
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Research context

Energy storage

OpenAlex topics: Advancements in Battery Materials · Advanced Battery Technologies Research · Semiconductor materials and devices

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Department of Battery Engineering Graduate Institute of Ferrous & Eco Materials Technology Pohang University of Science and Technology (POSTECH) Pohang 37667 Republic of Korea

Center for Hydrogen Energy Materials Korea Institute of Science and Technology (KIST) Seoul 02792 Republic of Korea

Department of Chemical and Biological Engineering Korea University Seoul 02841 Republic of Korea

Department of Energy Science Sungkyunkwan University Suwon 16419 Republic of Korea

SKKU Institute of Energy Science and Technology (SIEST) Sungkyunkwan University Suwon 16419 Republic of Korea

Advanced Analysis and Data Center Korea Institute of Science and Technology (KIST) Seoul 02792 Republic of Korea

Center for Hydrogen and Fuel Cells Korea Institute of Science and Technology Seongbuk‐gu Seoul 02792 Republic of Korea

Energy Storage Research Center Korea Institute of Science and Technology (KIST) Seoul 02792 Republic of Korea

Division of Energy and Environment Technology KIST School Korea University of Science and Technology Seongbuk‐gu Seoul 02792 Republic of Korea

KHU‐KIST Department of Converging Science and Technology Kyung Hee University Dongdaemun‐gu Seoul 02447 Republic of Korea

Funding

Korea Institute for Advancement of Technology · National Research Foundation of Korea

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