Intragranular cracking as a critical barrier for high-voltage usage of layer-structured cathode for lithium-ion batteries

By P. Yan, Jianming Zheng, M. Gu, Jie Xiao, Ji‐Guang Zhang, Chong-Min Wang. Nature Communications, 2017

850 citations recorded by the source corpus.

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. Cycling-induced fracture can limit conditions for stable operation for various lithium-ion electrode materials. Here, the authors characterize fracture in nickel-manganese-cobalt oxide microscopically and provide evidence for dislocation-assisted, intragranular fracture operating above a critical voltage threshold.

Subfields: Atomic and Molecular Physics, and Optics, Electrical and Electronic Engineering

View Paper: https://www.semanticscholar.org/paper/7d767a34163013273c4149bcb5c1f5f6252f8ea0

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Citations in the corpus

• Li-Rich Layered Oxides and Their Practical Challenges: Recent Progress and Perspectives (2019, background): “In addition, the formation of cracks or porogenic behaviours on the surface or in the bulk of LLO materials has also been proposed and is directly related to high strain and high-voltage cycling [185, 188].”
• A review of the degradation mechanisms of NCM cathodes and corresponding mitigation strategies (2023, background): “Hence rather than being a function of operational voltage, cracking in NCM materials is perhaps best viewed as a function of lithium content or SoC[66].”