Crosstalk, the exchange of chemical species between battery electrodes, significantly accelerates thermal runaway (TR) of lithium-ion batteries. To date, the understanding of their main mechanisms has centered on single-directional crosstalk of oxygen (O2) gas from the cathode to the anode, underestimating the exothermic reactions during TR. However, the role of multidirectional crosstalk in steering additional exothermic reactions is yet to be elucidated due to the difficulties of correlative in situ analyses of full cells. Herein, the way in which such crosstalk triggers self-amplifying feedback is elucidated that dramatically exacerbates TR within enclosed full cells, by employing synchrotron-based high-temperature X-ray diffraction, mass spectrometry, and calorimetry. These findings reveal that ethylene (C2H4) gas generated at the anode promotes O2 evolution at the cathode. This O2 then returns to the anode, further promoting additional C2H4 formation and creating a self-amplifying loop, thereby intensifying TR. Furthermore, CO2, traditionally viewed as an extinguishing gas, engages in the crosstalk by interacting with lithium at the anode to form Li2CO3, thereby accelerating TR beyond prior expectations. These insights have led to develop an anode coating that impedes the formation of C2H4 and O2, to effectively mitigate TR.
Increasing lithium contents within the lattice of positive electrode materials is projected in pursuit of high-energy-density batteries. However, it intensifies the release of lattice oxygen and subsequent gas evolution during operations. This poses significant challenges for managing internal pressure of batteries, particularly in terms of the management of gas evolution in composite electrodes-an area that remains largely unexplored. Conventional assumptions postulate that the total gas evolution is estimated by multiplying the total particle count by the quantities of gas products from an individual particle. Contrarily, this investigation on overlithiated materials-a system known to release the lattice oxygen-demonstrates that loading densities and inter-particle spacing in electrodes significantly govern gas evolution rates, leading to distinct extents of gas formation despite of an equivalent quantity of released lattice oxygen. Remarkably, this study discoveres that O2 and CO2 evolution rates are proportional to 1O2 concentration by the factor of second and first-order, respectively. This indicates an exceptionally greater change in the evolution rate of O2 compared to CO2 depending on local 1O2 concentration. These insights pave new routes for more sophisticated approaches to manage gas evolution within high-energy-density batteries.
O2-type lithium-rich layered oxides, known for mitigating irreversible transition metal migration and voltage decay, provide suitable framework for exploring the inherent properties of oxygen redox. Here, we present a series of O2-type lithium-rich layered oxides exhibiting minimal structural disordering and stable voltage retention even with high anionic redox participation based on the nominal composition. Notably, we observe a distinct asymmetric lattice breathing phenomenon within the layered framework driven by excessive oxygen redox, which includes substantial particle-level mechanical stress and the microcracks formation during cycling. This chemo-mechanical degradation can be effectively mitigated by balancing the anionic and cationic redox capabilities, securing both high discharge voltage (~ 3.43 V vs. Li/Li+) and capacity (~ 200 mAh g-1) over extended cycles. The observed correlation between the oxygen redox capability and the structural evolution of the layered framework suggests the distinct intrinsic capacity fading mechanism that differs from the previously proposed voltage fading mode.
During solid-state calcination, with increasing temperature, materials undergo complex phase transitions with heterogeneous solid-state reactions and mass transport. Precise control of the calcination chemistry is therefore crucial for synthesizing state-of-the-art Ni-rich layered oxides (LiNi1-x-y Cox Mny O2 , NRNCM) as cathode materials for lithium-ion batteries. Although the battery performance depends on the chemical heterogeneity during NRNCM calcination, it has not yet been elucidated. Herein, through synchrotron-based X-ray, mass spectrometry microscopy, and structural analyses, it is revealed that the temperature-dependent reaction kinetics, the diffusivity of solid-state lithium sources, and the ambient oxygen control the local chemical compositions of the reaction intermediates within a calcined particle. Additionally, it is found that the variations in the reducing power of the transition metals (i.e., Ni, Co, and Mn) determine the local structures at the nanoscale. The investigation of the reaction mechanism via imaging analysis provides valuable information for tuning the calcination chemistry and developing high-energy/power density lithium-ion batteries.
SiOx (x ≈ 1) is one of the most promising anode materials for application in secondary lithium-ion batteries because of its high theoretical capacity. Despite this merit, SiOx has a poor initial Coulombic efficiency, which impedes its widespread use. To overcome this limitation, in this work, we successfully demonstrate a novel synthesis of Mg-doped SiOx via a mass-producible physical vapor deposition method. The solid-state reaction between Mg and SiOx produces Si and electrochemically inert magnesium silicate, thus increasing the initial Coulombic efficiency. The Mg doping concentration determines the phase of the magnesium silicate domains, the size of the Si domains, and the heterogeneity of these two domains. Detailed electron microscopy and synchrotron-based analysis revealed that the nanoscale homogeneity of magnesium silicates driven by cycling significantly affected the lifetime. We found that 8 wt % Mg is the most optimized concentration for enhanced cyclability because MgSiO3, which is the dominant magnesium silicate composition, can be homogeneously mixed with silicon clusters, preventing their aggregation during cycling and suppressing void formation.
Understanding the cycling rate-dependent kinetics is crucial for managing the performance of batteries in high-power applications. Although high cycling rates may induce reaction heterogeneity and affect battery lifetime and capacity utilization, such phase transformation dynamics are poorly understood and uncontrollable. In this study, synchrotron-based operando X-ray diffraction is performed to monitor the high-current-induced phase transformation kinetics of LiNi0.6 Co0.2 Mn0.2 O2 . The sluggish Li diffusion at high Li content induces different phase transformations during charging and discharging, with strong phase separation and homogeneous phase transformation during charging and discharging, respectively. Moreover, by exploiting the dependence of Li diffusivity on the Li content and electrochemically tuning the initial Li content and distribution, phase separation pathway can be redirected to solid solution kinetics at a high charging rate of 7 C. Finite element analysis further elucidates the effect of the Li-content-dependent diffusion kinetics on the phase transformation pathway. The findings suggest a new direction for optimizing fast-cycling protocols based on the intrinsic properties of the materials.
