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鈉離子電池層狀氧化物正極材料研究進展

Recent progress on layered oxide cathode materials for sodium-ion batteries

  • 摘要: 鈉離子電池憑借資源和成本優勢在大規模儲能和低速電動車領域展現出極大應用前景。層狀氧化物理論容量較高且易于合成,是目前最具應用潛力的鈉離子電池正極材料之一。如何改善層狀氧化物正極材料的循環穩定性并提升其能量密度是當前的科學前沿問題。首先,綜述了層狀氧化物正極材料的幾種典型改性方法,從組分設計的角度,探討了不同摻雜元素、不同摻雜位點對材料容量和循環壽命的影響,闡述了利用陰離子反應提供額外容量的基本原理,概述了提高陰離子氧化還原可逆性的摻雜策略;從結構設計的角度,介紹了復合相材料的制備、微觀結構的設計和調控等方向的最新進展;從表面設計的角度,討論了金屬氧化物、磷酸鹽等作為包覆層對改善材料穩定性和倍率性能的作用機制。最后,總結了層狀氧化物儲鈉正極材料現階段面臨的挑戰,并對其未來的發展方向進行了展望,提出了新的研究思路。

     

    Abstract: Driven by the national strategic goal of “emission peak and carbon neutrality”, developing grid-scale energy storage systems (ESSs) for high-efficiency utilization of renewable clean energy is of great importance and urgency. Currently, lithium-ion batteries (LIBs) are being widely used in portable electronics and electric vehicles markets due to their high energy density and long cycling life. Nevertheless, the ever-increasing price and uneven distribution of lithium resources limit the further applications of LIBs for large-scale ESS. Recently, sodium-ion batteries (SIBs) have gained tremendous attention as promising large-scale energy storage devices and low-speed electric vehicle power sources, owing to the low-cost and abundant sodium reserves. However, the larger size and heavier mass of Na+ than those of Li+ commonly lead to sluggish reaction kinetics, severe volume expansion, and the undesirable structural failure of electrode materials upon charge/discharge, which hinder the commercial value of SIBs. Leveraging high-performance cathode materials is expected to boost the development of SIBs because cathodes largely determine the cost and electrochemical performance of batteries. Among the reported cathode candidates, layered oxide materials hold great potential due to their high capacity and a facile synthesis process; however, these materials face some challenges such as low capacity retention and poor air stability. Recently, exploring appropriate methods to strengthen the structural stability and further enhance the energy density of layered oxides has become an emerging research hotspot. In this regard, various strategies, such as element composition and relative content manipulation and microstructure and surface/interface modulation, have been proposed. In this review, typical modification methods for improving the Na-storage performance of layered oxide cathodes are comprehensively summarized. From the perspective of component design, the effects of different doping elements and doping sites on the capacity and cycling life are discussed. In addition, the basic principle of anionic redox reaction to offer extra capacity is elucidated, and the doping strategies for enhancing the anionic redox reversibility are outlined. From the perspective of structure design, the recent progresses on the preparation of composite phase materials and microstructures design are introduced. From the perspective of surface design, the functional mechanism of metal oxides and phosphates as coating layers to improve the structural stability and rate performance is explored. Finally, the challenging issues facing layered sodium oxide cathodes and possible remedies in the future are discussed. We believe that this review will shed light on the development of advanced layered oxide cathode materials for SIBs.

     

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