Probing the Effectiveness in Stabilizing Lithium Metal Anodes through Functional Additives.

A variety of electrolyte additives were comprehensively evaluated to understand their relative capability in stabilizing lithium metal anode. Although the Li||Cu test is an effective test to rule out ineffective additives, a reliable assessment of individual additives cannot be obtained just by a single evaluation method. Therefore, various methods must be combined to truly assess the stabilization of a lithium anode. Moreover, it was also discovered that a significant depletion of electrolytes occurred during the end-of-life of the lithium batteries, which partially contributed to the sudden failure of the lithium batteries during cycling. However, the main culprit of the sudden failure was identified as the significant increase in the resistance of the lithium metal anode. When used as an additive, cyclic fluorinated carbonates are the most effective in stabilizing the lithium anode and improving the cycling performance of lithium batteries among all the common additives. Despite its cost-effectiveness, the additive in the conventional electrolyte approach provides insufficient protection for lithium metal due to the complete consumption of the additive materials, which is necessary to repair the solid-electrolyte interphase (SEI). Therefore, it is suggested that a larger ratio (>15 wt %) of the SEI former should be employed to achieve effective lithium stabilization.

Prelithiation of Lithium Peroxide for Silicon Anode: Achieving a High Activation Rate.

The use of lithium peroxide (Li2O2) as a cost-effective low-weight prelithiation cathode additive was successfully demonstrated. Through a series of studies on the chemical stability of Li2O2 and the activation process of Li2O2 on the cathode, we revealed that Li2O2 is more compatible with conventional electrolyte and cathode laminate slurry than lithium oxide. Due to the significantly smaller size of commercial Li2O2, it can be used directly as a cathode additive. Moreover, the activation of Li2O2 on the cathode leads to the impedance growth of the cathode possibly resulting from the release of dioxygen and evacuation of Li2O2 inside the cathode. With the introduction of a new Li2O2 spread-coating technique on the cathode, the capacity loss was suppressed. Si||NMC full cells using Li2O2 spread-coated cathode demonstrated a highly promising activation rate of Li2O2 and significantly enhanced specific capacity and cycling stability compared to the uncoated full cells.

Chemomechanics of Rechargeable Batteries: Status, Theories, and Perspectives.

Chemomechanics is an old subject, yet its importance has been revived in rechargeable batteries where the mechanical energy and damage associated with redox reactions can significantly affect both the thermodynamics and rates of key electrochemical processes. Thanks to the push for clean energy and advances in characterization capabilities, significant research efforts in the last two decades have brought about a leap forward in understanding the intricate chemomechanical interactions regulating battery performance. Going forward, it is necessary to consolidate scattered ideas in the literature into a structured framework for future efforts across multidisciplinary fields. This review sets out to distill and structure what the authors consider to be significant recent developments on the study of chemomechanics of rechargeable batteries in a concise and accessible format to the audiences of different backgrounds in electrochemistry, materials, and mechanics. Importantly, we review the significance of chemomechanics in the context of battery performance, as well as its mechanistic understanding by combining electrochemical, materials, and mechanical perspectives. We discuss the coupling between the elements of electrochemistry and mechanics, key experimental and modeling tools from the small to large scales, and design considerations. Lastly, we provide our perspective on ongoing challenges and opportunities ranging from quantifying mechanical degradation in batteries to manufacturing battery materials and developing cyclic protocols to improve the mechanical resilience.

Structural Evolution and Transition Dynamics in Lithium Ion Battery under Fast Charging: An Operando Neutron Diffraction Investigation.

Fast charging (<15 min) of lithium-ion batteries (LIBs) for electrical vehicles (EVs) is widely seen as the key factor that will greatly stimulate the EV markets, and its realization is mainly hindered by the sluggish diffusion of Li+ . To have a mechanistic understanding of Li+ diffusion within LIBs, in this study, structural evolutions of electrodes for a Ni-rich LiNi0.6 Mn0.2 Co0.2 O2 (NMC622) || graphite cylindrical cell with high areal loading (2.78 mAh cm-2 ) are developed for operando neutron powder diffraction study at different charging rates. Via sequential Rietveld refinements, changes in structures of NMC622 and Lix C6 are obtained during moderate and fast charging (from 0.27 C to 4.4 C). NMC622 exhibits the same structural evolution regardless of C-rates. For phase transitions of Lix C6 , the stage I (LiC6 ) phase emerges earlier during the stepwise intercalation at a lower state of charge when charging rate is increased. It is also found that the stage II (LiC12 ) → stage I (LiC6 ) transition is the rate-limiting step during fast charging. The LiC12 → LiC6 transition mechanism is further analyzed using the Johnson-Mehl-Avrami-Kolmogorov model. It is concluded as a diffusion-controlled, 1D phase transition with decreasing nucleation kinetics under increasing chargingrates.

Bulk and surface structural changes in high nickel cathodes subjected to fast charging conditions.

A layered oxide cathode, LiNi0.6Mn0.2Co0.2O2, undergoes noticeable crystal expansion by losing significantly higher amounts of Li+ at the end of fast charging cycles. However, the bulk structure of the cycled NMC622 is restored back to its pristine discharged state when intercalated with enough lithium ions during an electrochemical process.