As research on secondary batteries becomes important, interest in analytical methods to examine the condition of secondary batteries is also increasing. Among these methods, the electrochemical impedance spectroscopy (EIS) method is one of the most attractive diagnostic techniques due to its convenience, quickness, accuracy, and low cost. However, since the obtained spectra are complicated signals representing several impedance elements, it is necessary to understand the whole electrochemical environment for a meaningful analysis. Based on the understanding of the whole system, the circuit elements constituting the cell can be obtained through construction of a physically sound circuit model. Therefore, this mini-review will explain how to construct a physically sound circuit model according to the characteristics of the battery cell system and then introduce the relationship between the obtained resistances of the bulk (R b), charge transfer reaction (R c t), interface layer (R S E I), diffusion process (W) and battery characteristics, such as the state of charge (SOC), temperature, and state of health (SOH).
To advance current Li rechargeable batteries further, tremendous emphasis has been made on the development of anode materials with higher capacities than the widely commercialized graphite. Some of these anode materials exhibit capacities above the theoretical value predicted based on conventional mechanisms of Li storage, namely insertion, alloying, and conversion. In addition, in contrast to conventional observations of loss upon cycling, the capacity has been found to increase during repeated cycling in a significant number of cases. As the internal environment in the battery is very complicated and continuously changing, these abnormal charge storage behaviors are caused by diverse reactions. In this review, we will introduce our current understanding of reported reactions accounting for the extra capacity. It includes formation/decomposition of electrolyte-derived surface layer, the possibility of additional charge storage at sharp interfaces between electronic and ionic sinks, redox reactions of Li-containing species, unconventional activity of structural defects, and metallic-cluster like Li storage. We will also discuss how the changes in the anode can induce capacity increase upon cycling. With this knowledge, new insights into possible strategies to effectively and sustainably utilize these abnormal charge storage mechanisms to produce vertical leaps in performance of anode materials will be laid out.
Amine-containing adsorbents have been extensively investigated for post-combustion carbon dioxide capture due to their ability to chemisorb low-concentration carbon dioxide from a wet flue gas. However, earlier studies have focused primarily on the carbon dioxide uptake of adsorbents, and have not demonstrated effective adsorbent regeneration and long-term stability under such conditions. Here, we report the versatile and scalable synthesis of a functionalized-polyethyleneimine (PEI)/silica adsorbent which simultaneously exhibits a large working capacity (2.2 mmol g−1) and long-term stability in a practical temperature swing adsorption process (regeneration under 100% carbon dioxide at 120 °C), enabling the separation of concentrated carbon dioxide. We demonstrate that the functionalization of PEI with 1,2-epoxybutane reduces the heat of adsorption and facilitates carbon dioxide desorption (>99%) during regeneration compared with unmodified PEI (76%). Moreover, the functionalization significantly improves long-term adsorbent stability over repeated temperature swing adsorption cycles due to the suppression of urea formation and oxidative amine degradation.
Amine-containing solids have been investigated as promising adsorbents for CO2 capture, but the low oxidative stability of amines has been the biggest hurdle for their practical applications. Here, we developed an extra-stable adsorbent by combining two strategies. First, poly(ethyleneimine) (PEI) was functionalized with 1,2-epoxybutane, which generates tethered 2-hydroxybutyl groups. Second, chelators were pre-supported onto a silica support to poison p.p.m.-level metal impurities (Fe and Cu) that catalyse amine oxidation. The combination of these strategies led to remarkable synergy, and the resultant adsorbent showed a minor loss of CO2 working capacity (8.5%) even after 30 days aging in O2-containing flue gas at 110 °C. This corresponds to a ~50 times slower deactivation rate than a conventional PEI/silica, which shows a complete loss of CO2 uptake capacity after the same treatment. The unprecedentedly high oxidative stability may represent an important breakthrough for the commercial implementation of these adsorbents.
Li ion battery (LIB) is one of the most remarkable energy storage devices currently available in various applications. With a growing demand for high-performance batteries, the role of electrochemical analysis for batteries, especially, electrode reactions are becoming very important and crucial. Among various analytical methods, cyclic voltammetry (CV) is very versatile and widely used in many fields of electrochemistry. Through CV, it is possible to know electrochemical factors affecting the reaction voltage and reversibility, and furthermore, quantitative analysis on Li + diffusivity as well as intercalation and capacitive reactions, and also anionic redox reaction. However, the explanation or interpretation of the results of CV is often deficient or controversial. In this mini-review, we briefly introduce the principle of cyclic voltammetry and its applications in LIB to bring a better understanding of the electrochemical reaction mechanisms involved in LIB.
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