Zhao Xiaoyu, Yang Shuo, Song Xiuli, Wang Yushuang, Zhang Hui, Li Muhan, Wang Yanfei
State Key Laboratory of Biobased Fiber Manufacturing Technology, Tianjin University of Science and Technology, Tianjin, 300457, China.
Tianjin Key Laboratory of Brine Chemical Engineering and Resource Eco-utilization, College of Chemical Engineering and Materials Science, Tianjin University of Science and Technology, Tianjin, 300457, China.
Adv Sci (Weinh). 2024 Nov;11(41):e2405176. doi: 10.1002/advs.202405176. Epub 2024 Sep 17.
Extracting lithium resources from seawater and brine can promote the development of the new energy materials industry. The electrochemical method is green and efficient. Iron phosphate (FePO) crystal, with its 1D ion channel, holds significant potential as a primary lithium extraction electrode material. Li encounters a substantial concentration disadvantage in brines, and the co-intercalation of Na diminishes Li selectivity. To address this issue, this work enhances the energy barrier for Na insertion through prelithiation strategies applied to the 1D channels of FePO crystal, thereby improving Li selectivity, and further investigating the prelithiation effect with particle size and morphology control. The results indicate that the LiFePO// Activated carbon(AC) system enhances selectivity of lithium. The LiFePO with size diameter of 2500 nm demonstrates an energy consumption of 0.79 Wh mol and a purity of 97.94% for lithium extraction at a unit lithium extraction of 5.93 mmol g in simulated brine. LiFePO-nanoplates demonstrate the most optimal lithium extraction performance among the three morphologies due to their lamellar structure's short ion diffusion path in the [010] channel, favoring Li diffusion. The diffusion energy barriers of Li and Na are calculated using Density Functional Theory (DFT) before and after prelithiation, showing good agreement with experimental results.
从海水和卤水中提取锂资源能够推动新能源材料产业的发展。电化学方法绿色高效。具有一维离子通道的磷酸铁（FePO）晶体作为一种主要的锂提取电极材料具有巨大潜力。锂在卤水中存在显著的浓度劣势，并且钠的共嵌入会降低锂的选择性。为了解决这个问题，本工作通过对FePO晶体的一维通道应用预锂化策略来提高钠嵌入的能垒，从而提高锂的选择性，并进一步研究粒径和形貌控制对预锂化效果的影响。结果表明，LiFePO//活性炭（AC）体系提高了锂的选择性。在模拟卤水中，粒径为2500 nm的LiFePO在单位锂提取量为5.93 mmol g时，锂提取的能耗为0.79 Wh mol，纯度为97.94%。LiFePO纳米片在三种形貌中表现出最优的锂提取性能，这是由于其层状结构在[010]通道中离子扩散路径短，有利于锂的扩散。利用密度泛函理论（DFT）计算了预锂化前后锂和钠的扩散能垒，结果与实验结果吻合良好。
