phase-separated copolymer membranes, often suffer from dramatically declined proton conductivity at low relative humidity (RH), [6-10] because the severe water loss under low RH destructs watermediated hydrogen-bonding networks. [8,11] For decades, great effort has been devoted to reduce the humidity-dependence of conductivity through preserving membrane hydration under low RH, such as incorporating hydrophilic groups [12,13] or hygroscopic porous nanofillers into membranes [7,14] to improve water retention properties, and installing nanovalves to retard water desorption of membranes. [2] However, the water retention remains a daunting challenge due to the "flexible polymer networks" nature of these PEMs. The amorphous, flexible ion nanochannels are prone to shrinking and even breaking upon dehydration, leading to poorly connected water channels and consequently exponential decline in conductivity and fuel cell performance. [6,15] Therefore, the design of electrolyte materials with weakly humidity-dependent proton-conducting feature remains a challenge. Materials with crystalline and rigid nanochannels are able to firmly retain water by capillary forces [16-20] and may promote membrane hydration, thereby facilitating proton transport efficiently over a wide range of humidity. Covalent organic frameworks (COFs), a class of crystalline porous polymers with pre-designable pore structures, hold grand promise. [21-23] Unlike amorphous, flexible crosslinked networks, the crystalline, rigid organic frameworks of COFs are expected to afford well-defined and stable proton-conducting nanochannels, [24-30] as well as good water retention capability. [18] However, leveraging COF materials in the field of COF-based PEMs for practical application remains a great challenge arising from the poor processing ability of COF materials and the poor structural integrity of COF membranes. Moreover, the proton transport mechanism in crystalline and rigid nanochannels of COF membranes remains elusive. Herein, we report a diffusion and solvent co-mediated modulation strategy for the direct synthesis of highly crystalline IPC-COF nanosheets (NUS-9) that can be readily processed into defect-free, robust IPC-COF membranes by subsequent vacuum-assisted self-assembly. These IPC-COF membranes exhibit weakly humidity-dependent conductivity and fuel cell performance over a wide range of humidity (30-98%). We further demonstrate that the crystalline and rigid ion nanochannels render the IPC-COF membranes exceptional State-of-the-art proton exchange membranes (PEMs) often suffer from significantly reduced conductivity under low relative humidity, hampering their efficient application in fuel cells. Covalent organic frameworks (COFs) with pre-designable and well-defined structures hold promise to cope with the above challenge. However, fabricating defect-free, robust COF membranes proves an extremely difficult task due to the poor processability of COF materials. Herein, a bottom-up approach is developed to synthesize intrinsic proton-conducting COF...
Developing new materials for the fabrication of proton exchange membranes (PEMs) for fuel cells is of great significance. Herein, a series of highly crystalline, porous, and stable new covalent organic frameworks (COFs) have been developed by a stepwise synthesis strategy. The synthesized COFs exhibit high hydrophilicity and excellent stability in strong acid or base (e.g., 12 m NaOH or HCl) and boiling water. These features make them ideal platforms for proton conduction applications. Upon loading with H3PO4, the COFs (H3PO4@COFs) realize an ultrahigh proton conductivity of 1.13×10−1 S cm−1, the highest among all COF materials, and maintain high proton conductivity across a wide relative humidity (40–100 %) and temperature range (20–80 °C). Furthermore, membrane electrode assemblies were fabricated using H3PO4@COFs as the solid electrolyte membrane for proton exchange resulting in a maximum power density of 81 mW cm−2 and a maximum current density of 456 mA cm−2, which exceeds all previously reported COF materials.
The emergence of all‐organic frameworks is of fundamental significance, and designing such structures for anion conduction holds great promise in energy conversion and storage applications. Herein, inspired by the efficient anion transport within organisms, a de novo design of covalent organic frameworks (COFs) toward ultrafast anion transport is demonstrated. A phase‐transfer polymerization process is developed to acquire dense and ordered alignment of quaternary ammonium‐functionalized side chains along the channels within the frameworks. The resultant self‐standing COFs membranes exhibit one of the highest hydroxide conductivities (212 mS cm−1 at 80 °C) among the reported anion exchange membranes. Meanwhile, it is found that shorter, more hydrophilic side chains are favorable for anion conduction. The present work highlights the prospects of all‐organic framework materials as the platform building blocks in designing ion exchange membranes and ion sieving membranes.
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