The sustainability of lithium-based energy storage or conversion systems, e.g., lithium-ion batteries, can be enhanced by establishing methods of efficient lithium extraction from harsh brines. In this work, we describe a decoupled membrane-free electrochemical cell that cycles lithium ions between iron-phosphate electrodes and features cathode (brine) and anode (fresh water) compartments that are isolated from each other yet electrochemically connected through a pair of silver/silver-halide redox electrodes. This design is compatible with harsh brines having magnesium/lithium molar ratios of up to 3258 and lithium concentrations down to 0.15 millimolar, enabling the production of battery-grade (>99.95% pure) lithium carbonate. Energy savings of up to ~21.5% were realized by efficiently harvesting the osmotic energy of the brines. A pilot-scale cell with an electrode surface area of 33.75 square meters was used to realize lithium extraction from Dead Sea brine with a recovery rate of 84.0%.

3D ionic covalent organic framework (COF) membranes, which are envisioned to be able to break the trade-off between ion conductivity and ion selectivity, are waiting for exploitation. Herein, we report the fabrication of a 3D sulfonic acid-functionalized COF membrane (3D SCOF) for efficient and selective ion transport, using dual acid-mediated interfacial polymerization strategy. The 3D SCOF membranes possess highly interconnected ion transport channels, ultramicroporous pore sizes (0.97 nm), and abundant sulfonate groups (with a high ion exchange capacity of 4.1 mmol g⁻¹), leading to high proton conductivity of 843 mS cm⁻¹ at 90 °C. When utilized in osmotic energy conversion, a high power density of 21.2 W m⁻², and a remarkable selectivity of 0.976 and thus an exceptional energy conversion efficiency of 45.3% are simultaneously achieved. This work provides an alternative approach to 3D ionic COF membranes and promotes the applications of 3D COFs in ion transport and separation.

Biological cell membranes can efficiently switch Na⁺/K⁺ selectivity in response to external stimuli, but achieving analogous functions in a single artificial membrane is challenging. Here, we report highly crystalline covalent organic framework (COF) membranes with well-defined nanochannels and coordinative sites (i. e., amino acid) that act as ion-selective switches to manipulate Na⁺ and K⁺ transport. The ion selectivity of the COF membrane is dynamic and can be switched between K⁺-selective and Na⁺-selective in a single membrane by applying a pH stimulus. The experimental results combined with molecular dynamics simulations reveal that the switchable Na⁺/K⁺ selectivity originates from the differentiated coordination interactions between ions and amino acids. Benefiting from the switchable Na⁺/K⁺ selectivity, we further demonstrate the membrane potential switches by varying electrolyte pH, miming the membrane polarity reversal during neural signal transduction in vivo, suggesting the great potential of these membranes for in vitro biomimetic applications.