Journal
ENERGY STORAGE MATERIALS
Volume 47, Issue -, Pages 51-60Publisher
ELSEVIER
DOI: 10.1016/j.ensm.2022.01.054
Keywords
Lithium ion battery safety; Cathode; Oxygen vacancy; Thermal degradation
Funding
- National Natural Science Foundation of China [51976209, U1932211]
- Synchrotron Radiation Joint Fund of the University of Science and Technology of China [KY2320000024]
- Youth Innovation Promotion Association CAS [Y201768]
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This study focuses on the secondary particles of different Li(NixCoyMnz)O-2 cathodes, investigating the formation and condensation of oxygen vacancies on the surface, as well as the concentration distribution of oxygen vacancies inside the particles after thermal failure. The results show that increasing the Ni content promotes the diffusion of oxygen vacancies from the surface to the bulk, leading to an increase in oxygen vacancy concentration and the release of more oxygen. When the Ni content reaches 0.8, both the surface layer and bulk of the secondary particles exhibit high oxygen vacancy concentrations, resulting in overall failure. Furthermore, the formation and evolution of intergranular cracks inside the secondary particles depend on the oxygen vacancy concentration gradient.
It is generally believed that an increase in Ni content will severely reduce the lattice structure stability of the cathode material, causing it to release more oxygen during thermal induction. However, the thermal degradation mechanism at the microscopic level remains unclear, which hinders the safety design of cathodes. In this work, we focus on the secondary particles of different Li(NixCoyMnz)O-2 cathodes, report the formation and condensation of oxygen vacancies on the surface in detail, and quantitatively analyze the oxygen vacancy concentration distribution inside the particles after thermal failure. The results reveal that the increase of Ni content promotes the oxygen vacancies to diffuse deeply from the surface of the secondary particles to the bulk under thermal induction, resulting in an increase of oxygen vacancy concentration in the bulk of the secondary particles and the release of more oxygen. When the Ni content x in Li(NixCoyMnz)O-2 increases to 0.8, both the surface layer and bulk exhibit high oxygen vacancy concentrations, leading to an overall failure of the secondary particles. Furthermore, we suggest that the formation and evolution of intergranular cracks inside the secondary particles depend on the oxygen vacancy concentration gradient. Our work provides a new idea for future research on the thermal stability of cathode and the thermal safety design of Ni-rich cathode materials.
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