Jianming Tao,Lang Wen,Qinghao Liu,Yanhuang Cai,Yanmin Yang,Feng Qi,Yingbin Lin
Solid-state Li metal batteries equipped with polymer electrolytes are highly coveted for their flexibility and remarkable energy density; however, their advancement is hindered by limited ionic conductivity and poor interfacial stability. Herein, we report that protein additives can significantly improve the performance of poly(ethylene oxide)-based solid electrolytes and elucidate the ion-conducting mechanism by comparing proteins with different charged groups (CGs). Positive CGs can anchor anions in Li salts to increase ion transference number but also adsorb polymer chains resulting in a decrease in ionic conductivity. Negative CGs promote the dissociation of Li salts and Li+ conduction; however, it depends on the long-range protein chains. In comparison to the α-amylase with more negative CGs and bovine serum albumin (BSA) with more positive CGs, the casein with balanced groups enables the solid electrolyte to have a significantly higher Li+ transference number of 0.45 and superior mechanical properties. Furthermore, it can also promote uniform Li plating and stripping, as well as the formation of a stable solid electrode–electrolyte interphase. When paired with the LiNi0.8Co0.1Mn0.1O2 cathode, the batteries can still maintain a high specific capacity of 97.7 mA h g–1 after 200 cycles at a 1 C-rate, highlighting the efficacy of utilizing CGs-balanced proteins as additives in solid-state batteries.
In order to investigate the effect of charged groups present in hydrophilic monolithic stationary phases on their chromatographic properties, three charged hydrophilic monomers, i.e. N,N -dimethyl- N -acryloyloxyethyl- N -(3-sulfopropyl)ammonium betaine (SPDA), [2-(acryloyloxy)ethyl]trimethylammonium chloride (AETA), and 3-sulfopropyl acrylate potassium salt (SPA) were co-polymerized with the crosslinker N,N '-methylenebisacrylamide (MBA), respectively. The physicochemical properties of the three resulting charged hydrophilic monolithic columns were evaluated using scanning electron microscopy, ζ-potential analysis and micro-HPLC. High column efficiency was obtained on the three monolithic columns at a linear velocity of 1 mm/s using thiourea as test compound. Comparative characterization of the three charged HILIC phases was then carried out using a set of model compounds, including nucleobases, nucleosides, benzoic acid derivatives, phenols, β-blockers and small peptides. Depending on the combination of stationary phase/mobile phase/solute, both hydrophilic interaction and other potential secondary interactions, including electrostatic interaction, hydrogen-bonding interaction, molecular shape selectivity, could contribute to the over-all retention of the analytes. Because of the strong electrostatic interaction provided by the quaternary ammonium groups in the poly (AETA- co -MBA) monolith, this cationic HILIC monolith exhibited the strongest retention for benzoic acid derivatives and small peptides with distorted peak shapes and the weakest retention for basic β-blockers. The sulfonyl groups on the poly (SPA- co -MBA) hydrophilic monolith could provide strong electrostatic attraction and hydrogen bonding for positively charged analytes and hydrogen-donor/acceptor containing analytes, respectively. Therefore, basic drugs, nucleobases and nucleotides exhibited the strongest retention on this anionic monolith. Because of the weak but distinct cation exchange properties of the zwitterionic poly (SPDA- co -MBA) hydrophilic monolith, it exhibited the best separation for most test analytes (including phenols, β-blockers and small peptides) in terms of selectivity, peak shape and analysis time. The poly (AETA- co -MBA) hydrophilic monolithic column provides the best separation of nucleobases and nucleosides. These results could guide the selection and application of these charged HILIC monoliths in the future.
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