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K-gradient doping to stabilize the spinel structure of Li1.6Mn1.6O4 for Li+ recovery
Fangren Qian1, Bing Zhao1, Min Guo2
1Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resources, Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008, China. liuzhong@isl.ac.cn and Key Laboratory of Salt Lake Resources Chemistry of Qinghai Province, Xining 810008, China and University of Chinese Academy of Sciences, Beijing 100049, China.
Abstract:
Lithium-rich spinel lithium manganese oxide (LMO) compounds are one kind of promising adsorbents for lithium recovery from brine due to their high capacity and low Mn dissolution; Li1.6Mn1.6O4 is one of them. However, Mn3+ exists in the Li1.6Mn1.6O4 precursor due to incomplete reaction during syntheses, and the disproportionation reaction of Mn3+ inevitably results in Mn dissolution during lithium adsorption and desorption. The stable recycling and structural stability of Li1.6Mn1.6O4 were improved in aqueous lithium resources through K-gradient doping (LMO-K). The dissolution of Mn is reduced to 4.0% from 5.4% (before doping) and the adsorption capacity is kept at high capacity (31.6 mg g-1) at a low Li+ concentration of 12 mmol L-1. In addition, first-principles calculations further confirm that K substitutes for Li at 16d sites, leading to the stabilization of the Mn cations in the compound. With the help of K doping, the undesired dissolution of Mn in the cycle process is inhibited, which may be due to the reduction in the content of Mn3+ and improvement in the structural stability of the adsorbent.
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