Advances in reactive co-precipitation technology for preparing high-performance cathodes

Zhenzhen Wang , Li Yang , Chunliu Xu , Jingcai Cheng , Junmei Zhao , Qingshan Huang , Chao Yang
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Abstract

Reactive crystallization plays an essential role in the synthesis of high-quality precursors with a narrow particle size distribution, dense packing, and high sphericity. These features are beneficial in the fabrication of high-specific-capacity and long-cycle-life cathodes for lithium-ion and sodium-ion batteries. However, in industrial production, designing and scaling-up crystallizers involves the use of semi-empirical approaches, making it challenging to satisfactorily meet techno-economic requirements. Furthermore, there is still a lack of in-depth knowledge on the theoretical models and technical calculations of the current co-precipitation process. This review elaborates on critical advances in the theoretical guidelines and process regulation strategies using a reactive crystallizer for the preparation of precursors by co-precipitation. The research progress on the kinetic models of co-precipitation reactive crystallization is presented. In addition, the regulation strategies for the reactive crystallization process of lithium-ion ternary cathodes are described in detail. These include the influence of different reactive crystallizer structures on the precursor's morphology and performance, the intelligent online measurement of efficient reactive crystallizers to ensure favorable conditions of co-precipitation, and preparing the precursor with a high tap density by increasing its solid holdup. A controllable reactive crystallization process is described in terms of the structural design with concentration gradient materials and bulk gradient doping of advantageous elements (such as magnesium ion) in lithium-ion cathodes and the fabrication of sodium-ion cathodes with three typical materials—Prussian blue analogues, transition metal oxides, and polyanionic phosphate compounds being involved.

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制备高性能阴极的反应共沉淀技术的进展
反应结晶在合成具有窄粒度分布、致密堆积和高球形度的高质量前驱体方面发挥着至关重要的作用。这些特点有利于制造高特异性容量和长循环寿命的锂离子和钠离子电池阴极。然而,在工业生产中,结晶器的设计和放大需要使用半经验方法,因此要满足技术经济要求具有挑战性。此外,人们对当前共沉淀工艺的理论模型和技术计算仍缺乏深入了解。本综述阐述了使用反应结晶器通过共沉淀制备前驱体的理论指导和工艺调节策略方面的重要进展。文中介绍了共沉淀反应结晶动力学模型的研究进展。此外,还详细介绍了锂离子三元正极反应结晶过程的调节策略。这些策略包括不同反应结晶器结构对前驱体形态和性能的影响、智能在线测量高效反应结晶器以确保共沉淀的有利条件,以及通过增加固体容纳量来制备高锥密度的前驱体。从锂离子阴极的浓度梯度材料结构设计和优势元素(如镁离子)的批量梯度掺杂,以及钠离子阴极的制造三个方面介绍了可控反应结晶过程,其中涉及三种典型材料--普鲁士蓝类似物、过渡金属氧化物和聚阴离子磷酸盐化合物。
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