Xiaoyu Zhao,Shuo Yang,Xiuli Song,Yushuang Wang,Hui Zhang,Muhan Li,Yanfei Wang
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 4 ) 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 4 crystal, thereby improving Li + selectivity, and further investigating the prelithiation effect with particle size and morphology control. The results indicate that the Li (4C-40%) FePO 4 // Activated carbon(AC) system enhances selectivity of lithium. The Li (4C-40%) FePO 4 with size diameter of 2500 nm demonstrates an energy consumption of 0.79 Wh mol −1 and a purity of 97.94% for lithium extraction at a unit lithium extraction of 5.93 mmol g −1 in simulated brine. Li (4C-40%) FePO 4 -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.
Jian Lu,Yingying Qin,Qi Zhang,Yilin Wu,Jiuyun Cui,Chunxiang Li,Liang Wang,Yongsheng Yan
High-selective multilayered Li + -imprinted membranes (Li-IIMs) with enhanced hydrophilicity and stability were developed based on polyether sulfone substrate membranes. The multilayered structure was prepared with polydopamine (pDA) as the interfacial adhesion layer, SiO 2 nanoparticles as the hydrophilic layer and Li + -imprinted polymers as the imprinted layer. The selective “Li + -recognition sites” were formed using 12-crown-4 (12C4) as the adsorbing units. The optimal relative selectivity coefficients (α) of Li + /Na + and Li + /K + reached up to 1.85 and 2.07 with the imprinting factor ( β ) of 2.51, and the high permselectivity factors ( γ ) of Na + /Li + (7.39) and K + /Li + (9.86) were achieved on Li-IIMs. The Langmuir isotherm model and the pseudo-second-order kinetics model best fitted the rebinding data of Li-IIMs, as well as the rebinding capacities reached up to 90.3% of initial binding after 5 cycles of adsorption/desorption and just declined to 88.1% after another 5 cycles a month later. Therefore, the as-prepared Li-IIMs would have potential applications for the separation of lithium ions from salt lake brines.
Erhui Zhang,Weifeng Liu,Qi Liang,Xuguang Liu,Zongbin Zhao,Yongzhen Yang
To meet the requirements of industrial lithium extraction from the simulated acidic leaching solution of fly ash, one novel ion-imprinted graphene-based hybrid aerogel (LIIP@N-CMS/GA) has been developed by a combination of pulse electropolymerization and surface ion imprinting technique. The imprinted film consists of polypyrrole (PPy), graphene oxide (GO), benzo-12-crown 4-ether (B12C4) and nitrogen-doped carbon microspheres/graphene aerogel (N-CMS/GA). By integrating the electric field driving and specific recognition of B12C4 towards Li + , the LIIP@N-CMS/GA electrode achieves excellent ionic separation performance, including high adsorption capacity of 41.05 mg g −1 with superior retention ratio (keeping 91.7% of the initial value even experiencing 10 cycles of electrochemical adsorption–desorption), short equilibration time less than 2 h, and relatively high selectivity separation factor of 51.99, 19.66, 14.37 and 12.40 against Na + , K + , Mg 2+ and Al 3+ , respectively. These performances originate from the synergistic effects of the porous structure of N-CMS/GA with excellent conductivity, specific recognition of B12C4 towards Li + , and electric field driving which accelerates ion transport as well as electron transfer. Therefore, LIIP@N-CMS/GA can act as an outstanding candidate for lithium extraction in acidic environment.
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