Revisiting the t 0.5 Dependence of SEI Growth

SEI growth in lithium-ion batteries is commonly assumed to scale with t 0.5, in line with simple models of diffusion-limited surface layer growth. As a result, this model is widely used for empirical predictions of capacity fade in lithium-ion batteries. However, the t 0.5 model is generally not theoretically sufficient to describe all of the various SEI growth modes. Furthermore, previous literature has not convincingly demonstrated that this model provides the best fit to measurements of SEI growth. In this work, we discuss the theoretical assumptions of the t 0.5 model, evaluate claims of t 0.5 dependence in six previously published datasets and one new dataset, and compare the performance of this model to that of other models. We find that few of the purported t 0.5 fits in literature are statistically justified, although t 0.5 generally describes SEI growth during storage better than SEI growth during cycling. Finally, we evaluate how the fitted exponents in the power-law models vary as a function of time, and we illustrate the limitations of using t 0.5 for prediction without validating its applicability to a particular dataset. This work illustrates the theoretical and empirical limitations of the t 0.5 model and highlights alternatives for more accurate estimates and predictions of SEI growth

Fingerprint oxygen redox reactions in batteries through high-efficiency mapping of resonant inelastic X-ray scattering

Realizing reversible reduction-oxidation (redox) reactions of lattice oxygen in batteries is a promising way to improve the energy and power density. However, conventional oxygen absorption spectroscopy fails to distinguish the critical oxygen chemistry in oxide-based battery electrodes. Therefore, high-efficiency full-range mapping of resonant inelastic X-ray scattering (mRIXS) has been developed as a reliable probe of oxygen redox reactions. Here, based on mRIXS results collected from a series of Li Ni Co Mn O electrodes at different electrochemical states and its comparison with peroxides, we provide a comprehensive analysis of five components observed in the mRIXS results. While all the five components evolve upon electrochemical cycling, only two of them correspond to the critical states associated with oxygen redox reactions. One is a specific feature at 531.0 eV excitation and 523.7 eV emission energy, the other is a low-energy loss feature. We show that both features evolve with electrochemical cycling of Li Ni Co Mn O electrodes, and could be used for characterizing oxidized oxygen states in the lattice of battery electrodes. This work provides an important benchmark for a complete assignment of all mRIXS features collected from battery materials, which sets a general foundation for future studies in characterization, analysis, and theoretical calculation for probing and understanding oxygen redox reactions. 1.17 0.21 0.08 0.54 2 1.17 0.21 0.08 0.54

Effect of defects on reaction of NiO surface with Pb-contained solution

In order to understand the role of defects in chemical reactions, we used two types of samples, which are molecular beam epitaxy (MBE) grown NiO(001) film on Mg(001) substrate as the defect free NiO prototype and NiO grown on Ni(110) single crystal as the one with defects. In-situ observations for oxide-liquid interfacial structure and surface morphology were performed for both samples in water and Pb-contained solution using high-resolution X-ray reflectivity and atomic force microscopy. For the MBE grown NiO, no significant changes were detected in the high-resolution X-ray reflectivity data with monotonic increase in roughness. Meanwhile, in the case of native grown NiO on Ni(110), significant changes in both the morphology and atomistic structure at the interface were observed when immersed in water and Pb-contained solution. Our results provide simple and direct experimental evidence of the role of the defects in chemical reaction of oxide surfaces with both water and Pb-contained solution.ope

Influence of surface atomic structure demonstrated on oxygen incorporation mechanism at a model perovskite oxide

Perovskite oxide surfaces catalyze oxygen exchange reactions that are crucial for fuel cells, electrolyzers, and thermochemical fuel synthesis. Here, by bridging the gap between surface analysis with atomic resolution and oxygen exchange kinetics measurements, we demonstrate how the exact surface atomic structure can determine the reactivity for oxygen exchange reactions on a model perovskite oxide. Two precisely controlled surface reconstructions with (4 × 1) and (2 × 5) symmetry on 0.5 wt.% Nb-doped SrTiO3(110) were subjected to isotopically labeled oxygen exchange at 450 °C. The oxygen incorporation rate is three times higher on the (4 × 1) surface phase compared to the (2 × 5). Common models of surface reactivity based on the availability of oxygen vacancies or on the ease of electron transfer cannot account for this difference. We propose a structure-driven oxygen exchange mechanism, relying on the flexibility of the surface coordination polyhedra that transform upon dissociation of oxygen molecules.Austrian Science Fund (SFB “ Functional Oxide Surfaces and Interfaces ” - FOXSI, Project F 45)European Research Council Advanced Grant (“OxideSurfaces” (Project ERC-2011-ADG_20110209))National Science Foundation (U.S.). Division of Materials Research (CAREER Award Grant No. 1055583

Evaluation of technical quality and periapical health of root-filled teeth by using cone-beam CT

Objective This study aimed to assess the quality of root fillings, coronal restorations, complications of all root-filled teeth and their association with apical periodontitis (AP) detected by cone-beam computed tomography (CBCT) images from an adult Turkish subpopulation. Material and Methods The sample for this study consisted of 242 patients (aging from 15 to 72 years) with 522 endodontically treated teeth that were assessed for technical quality of the root canal filling and periapical status of the teeth. Additionally, the apical status of each root-filled tooth was assessed according to the gender, dental arch, tooth type and age classification, undetected canals, instrument fracture, root fracture, apical resorption, apical lesion, furcation lesion and type and quality of the coronal structure. Statistical analysis was performed using percentages and chi-square test. Results The success rate of the root canal treatment was of 54.4%. The success rates of adequate and inadequate root canal treatment were not significantly different (p>0.05). Apical periodontitis was found in 228 (45.6%) teeth treated for root canals. Higher prevalence of AP was found in patients aging from 20 to 29 years [64 (27%) teeth] and in anterior (canines and incisors) teeth [97 (41%) teeth]. Conclusions The technical quality of root canal filling performed by dental practitioners in a Turkish subpopulation was consistent with a high prevalence of AP. The probable reasons for this failure are multifactorial, and there may be a need for improved undergraduate education and postgraduate courses to improve the clinical skills of dental practitioners in endodontics

Benefits of Fast Battery Formation in a Model System

Lithium-ion battery formation affects battery cost, energy density, and lifetime. An improved understanding of the first cycle of solid-electrolyte interphase (SEI) growth on carbonaceous negative electrodes could aid in the design of optimized formation protocols. In this work, we systematically study SEI growth during the formation of carbon black negative electrodes in a standard carbonate electrolyte. We show that the initial ethylene carbonate (EC) reduction reaction occurs at ∼0.5-1.2 V during the first lithiation, except under fast lithiation rates (≥10C). The products of this EC reduction reaction do not passivate the electrode; only the SEI formed at lower potentials affects the second-cycle Coulombic efficiency. Thus, cycling quickly through the voltage regime of this reaction can decrease both formation time and first-cycle capacity loss, without an increase in subsequent-cycle capacity loss. We also show that the capacity consumed by this reaction is minimized at low temperatures and low salt concentrations. Finally, we discuss the mechanism behind our experimental results. This work reveals the fundamental processes underlying initial SEI growth on carbonaceous negative electrodes and provides insights for both optimizing the battery formation process and enabling novel electrolytes

Electrochemical kinetics of sei growth on Carbon Black: Part I. experiments

Growth of the solid electrolyte interphase (SEI) is a primary driver of capacity fade in lithium-ion batteries. Despite its importance to this device and intense research interest, the fundamental mechanisms underpinning SEI growth remain unclear. In Part I of this work, we present an electroanalytical method to measure the dependence of SEI growth on potential, current magnitude, and current direction during galvanostatic cycling of carbon black/Li half cells.We find that SEI growth strongly depends on all three parameters; most notably, we find SEI growth rates increase with nominal C rate and are significantly higher on lithiation than on delithiation. We observe this directional effect in both galvanostatic and potentiostatic experiments and discuss hypotheses that could explain this observation. This work identifies a strong coupling between SEI growth and charge storage (e.g., intercalation and capacitance) in carbon negative electrodes