Intragranular cracking as a critical barrier for high-voltage usage of layer-structured cathode for lithium-ion batteries
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Open Access
- 16 January 2017
- journal article
- research article
- Published by Springer Science and Business Media LLC in Nature Communications
- Vol. 8 (1), 14101
- https://doi.org/10.1038/ncomms14101
Abstract
LiNi1/3Mn1/3Co1/3O2-layered cathode is often fabricated in the form of secondary particles, consisting of densely packed primary particles. This offers advantages for high energy density and alleviation of cathode side reactions/corrosions, but introduces drawbacks such as intergranular cracking. Here, we report unexpected observations on the nucleation and growth of intragranular cracks in a commercial LiNi1/3Mn1/3Co1/3O2 cathode by using advanced scanning transmission electron microscopy. We find the formation of the intragranular cracks is directly associated with high-voltage cycling, an electrochemically driven and diffusion-controlled process. The intragranular cracks are noticed to be characteristically initiated from the grain interior, a consequence of a dislocation-based crack incubation mechanism. This observation is in sharp contrast with general theoretical models, predicting the initiation of intragranular cracks from grain boundaries or particle surfaces. Our study emphasizes that maintaining structural stability is the key step towards high-voltage operation of layered-cathode materials.Keywords
This publication has 55 references indexed in Scilit:
- Atomic‐Scale Structure Evolution in a Quasi‐Equilibrated Electrochemical Process of Electrode Materials for Rechargeable BatteriesAdvanced Materials, 2015
- Probing the Degradation Mechanism of Li2MnO3 Cathode for Li-Ion BatteriesChemistry of Materials, 2015
- Evolution of Lattice Structure and Chemical Composition of the Surface Reconstruction Layer in Li1.2Ni0.2Mn0.6O2 Cathode Material for Lithium Ion BatteriesNano Letters, 2014
- Origin of voltage decay in high-capacity layered oxide electrodesNature Materials, 2014
- Structural Changes in Li2MnO3 Cathode Material for Li‐Ion BatteriesAdvanced Energy Materials, 2013
- Corrosion/Fragmentation of Layered Composite Cathode and Related Capacity/Voltage Fading during Cycling ProcessNano Letters, 2013
- Formation of the Spinel Phase in the Layered Composite Cathode Used in Li-Ion BatteriesACS Nano, 2012
- Identifying surface structural changes in layered Li-excess nickel manganese oxides in high voltage lithium ion batteries: A joint experimental and theoretical studyEnergy & Environmental Science, 2011
- Capacity-Fading Mechanisms of LiNiO[sub 2]-Based Lithium-Ion BatteriesJournal of the Electrochemical Society, 2009
- Changes in the structure and physical properties of the solid solution LiNi1–xMnxO2 with variation in its compositionJournal of Materials Chemistry, 2003