High selectivity, capacity and stability for electrochemical lithium extraction on boron-doped H1.6Mn1.6O4 by tailoring lattice constant and intercalation energy
Gang Liao, Lanlan Yu, Yufen Xia, Zhimin Wang, Zijun Lu, Jia‐Wei Mei, Huiling Liu, Chengbin Liu
Abstract
A sustainable supply of lithium from salt-lake brines is necessary due to the surge in demand of the lithium-battery market. However, the presence of coexisting ions, particularly Na + , poses a significant challenge due to the similarities in charge, electronic structure, and hydrated size. The electrochemical system with manganese (Mn)-based lithium-ion (Li + ) sieves electrodes is a promising method for Li + recovery, but often suffers from geometric configuration distortion, which reduces their selectivity and capacity. In this work, we developed a boron-modified H 1.6 Mn 1.6 O 4 (HMO-B) material for Li + extraction through hybrid capacitive deionization (HCDI) intercalation. Characterizations and theoretical calculations verified that the formation of the B O bond reduces the lattice constant , significantly inhibiting the Jahn–Teller distortion of Mn 3+ , thereby stabilizing the crystal structure. The transformation of Mn 3+ to Mn 4+ effectively prevents Mn dissolution during the electro-de-intercalation process. B doping narrows the lattice spacing and increases the intercalation energy difference between Li + and Na + . Consequently, HMO-B exhibits an outstanding Li/Na selectivity of 1211.68. The reduction in interface impedance improves current efficiency, while the increase in specific surface area provides abundant recognition sites for Li + , enhancing Li + intercalation performance from 14 mg g −1 day −1 for HMO to 34.94 mg g −1 h −1 for HMO-B. Additionally, Mn dissolution reduces from 7 % for HMO to 1.13 % for HMO-B after 10 cycles. This work holds substantial practical value for the selective Li extraction from salt lake brine and is anticipated to provide a stable Li supply for the burgeoning new energy industry.