Authors: Kisuk Kang
Source: ECS Meeting Abstracts (article, 2019-09-01)
Field: Materials Science — Materials Chemistry

(Invited) Preserving a High Energy Density of the Lithium-Rich Layered Oxides (LLO) and New Lithium Diffusion Model for Llo Lithium-rich layered oxides (LLOs) are considered promising cathode materials for lithium-ion batteries because of their high reversible capacity, which is attributed to the exploitation of the novel anionic redox in addition to the conventional cationic redox process. Cobalt-free layered lithium-rich nickel manganese oxides, Li[Li x Ni y Mn 1 − x − y ]O 2 , are one of the promising positive electrode materials for lithium rechargeable batteries because of their high energy density and low materials cost. However, substantial voltage decay is inevitable upon electrochemical cycling, which makes this class of materials less practical. It has been proposed that undesirable voltage decay is linked to irreversible structural rearrangement involving irreversible oxygen loss and cation migration. In the first part of my talk, we demonstrate that the voltage decay of the electrode is correlated to Mn 4+ /Mn 3+ redox activation and subsequent cation disordering, which can be remarkably suppressed via simple compositional tuning to induce the formation of Ni 3+ in the pristine material. By implementing our new strategy, the Mn 4+ /Mn 3+ reduction is subdued by an alternative redox reaction involving the use of pristine Ni 3+ as a redox buffer, which has been designed to be widened from Ni 3+ /Ni 4+ to Ni 2+ /Ni 4+ , without compensation for the capacity in principle. Negligible change in the voltage profile of modified LLO is observed upon extended cycling, and manganese migration into the lithium layer is significantly suppressed. In the second part of the talk, I will discuss about transition metal (TM) migration, which is now understood to be the critical factor triggering the anionic redox as well as the phase transition, although the origin is still under debate. A better understanding of the specific TM migration behavior and its effect during charge/discharge would thus enable further development of this class of materials. I will show that the unique TM migration during charge/discharge significantly alters the lithium diffusion mechanism/kinetics of LLO cathodes. I present clear evidence of the much more sluggish lithium diffusion occurring during discharge (lithiation) than during charge (de-lithiation), which contrasts with the traditional lithium diffusion model based on simple topotactic lithium intercalation/deintercalation in the layered framework. The reversible but asymmetric TM migration in the structure, which originates from the non-equivalent local environments around the TM during the charge and discharge processes, is shown to affect the lithium mobility. This correlation between TM migration and lithium mobility led us to propose a new lithium diffusion model for layered structures and suggests the importance of considering TM migration in designing new LLO cathode materials. Redox ; Lithium (medication) ; Manganese ; Materials science ; Electrochemistry ; Cathode ; Nickel ; Diffusion ; Chemical engineering ; Cobalt ; Inorganic chemistry ; Electrode ; Chemistry ; Physical chemistry ; Metallurgy ; Thermodynamics Catalytic Processes in Materials Science