Pramanik Atin, Manche Alexis G, Clulow Rebecca, Lightfoot Philip, Armstrong A Robert
School of Chemistry, University of St Andrews, KY16 9ST, Scotland, UK.
The Faraday Institution, Quad One, Harwell Science and Innovation Campus, Didcot, OX11 0RA, UK.
Dalton Trans. 2022 Aug 23;51(33):12467-12475. doi: 10.1039/d2dt01447e.
The fundamental understanding of electrochemical reaction kinetics for lithium/sodium-ion batteries (LIBs & NIBs) is a significant criterion for advancing new-generation electrode materials. Herein, we demonstrate a novel lithium-rich perovskite oxalate KLiFe(CO) (KLFC) cathode with the combination of cation and anion redox delivering discharge capacities of 86 and 99 mA h g after 100 cycles for a LIB and NIB, respectively, with good cyclability. Experimental Raman spectroscopy analysis combined with DFT calculations of charged/discharged samples illustrate the oxalate anion redox activity. Further, first-principles calculations of the partial density of states and Bader charges analysis have also characterised the redox behaviour and charge transfer during the potassium extraction processes.
对锂/钠离子电池（LIBs和NIBs）电化学反应动力学的基本理解是推进新一代电极材料的重要标准。在此，我们展示了一种新型富锂钙钛矿草酸盐KLiFe(CO)（KLFC）阴极，通过阳离子和阴离子氧化还原的结合，分别在LIB和NIB中循环100次后提供86和99 mA h g的放电容量，具有良好的循环稳定性。实验拉曼光谱分析结合充放电样品的DFT计算说明了草酸盐阴离子的氧化还原活性。此外，态密度的第一性原理计算和巴德电荷分析也表征了钾提取过程中的氧化还原行为和电荷转移。
