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Rational design of thermally stable polymorphic layered cathode materials for next generation lithium rechargeable batteries
Affiliation:1. State Key Laboratory of Powder Metallurgy, College of Chemistry and Chemical Engineering, Central South University, Changsha, China;2. Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL, USA;3. Material Science and Engineering, Stanford University, Stanford, CA, USA;4. Division of Chemistry and Environmental Science, Manchester Metropolitan University, Manchester, M1 5GD, UK;1. State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China;2. Shanghai Key Laboratory of Magnetic Resonance, School of Physics and Electronic Science, East China Normal University, Shanghai 200241, China;3. Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China;4. College of Materials, Xiamen University, Xiamen 361005, China;5. Fujian Science and Technology Innovation Laboratory for Energy Materials of China (Tan Kah Kee Innovation Laboratory), Xiamen 361005, China
Abstract:Classical layered transition metal oxides have remained the preferred cathode materials for commercial lithium-ion batteries. Variation in the transition metal composition and local ordering can greatly affect the structure stability. In classical layered cathodes, high concentrations of electrochemically inert Mn elements usually act as a pillar to stabilize the structure. When excess amount of Li and Mn are present in the layered structure, the capacity of the Li-rich layered oxide (molar ratio of lithium over transition metal is larger than one by design) can exceed that expected from transition metal redox. However, the over lithiation in the classical layered structure results in safety issues, which remains challenging for the commercialization of Li-rich layered oxides. To characterize the safety performance of a series of Li-rich layered cathodes, we utilize differential scanning calorimeter and thermal gravimetric analysis; this is coupled with local structural changes using in situ temperature dependent synchrotron X-ray diffraction and X-ray adsorption spectroscopy. These methods demonstrate that the gradual decrease of the Mn–M (M = Ni, Co, Mn and Li) coordination number directly reduces structural stability and accelerates oxygen release. For safety characterization tests in practice, we evaluate the thermal runaway process through accelerating rate calorimeter in 1.0 Ah pouch cells to confirm this trend. Using the insights obtained in this work, we design a polymorphic composition to improve the thermal stability of Li-rich layered cathode material, which outperforms Ni-rich layered oxides in terms of both electrochemical and safety performances.
Keywords:Li-ion batteries  Li-rich layered cathode  Thermal stability  Local structure modulation  Polymorphic composition design
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