Polyoxometalate-based reticular materials for proton conduction: from rigid frameworks to flexible networks.

Proton conductors play a crucial role in energy and electronic technologies, thus attracting extensive research interest. Recently, reticular chemistry has propelled the development of reticular materials with framework or network structures, which can offer tunable proton transport pathways to achieve optimal conducting performance. Polyoxometalates (POMs), as a class of highly proton-conducting units, have been integrated into these reticular materials using various linkers. This leads to the creation of hybrid proton conductors with structures varying from rigid crystalline frameworks to flexible networks, showing adjustable proton transport behaviors and mechanical properties. This Frontier article highlights the advancements in POM-based reticular materials for proton conduction and provides insights for designing advanced proton conductors for practical applications.

Self-Assembled Construction of Ion-Selective Nanobarriers in Electrolyte Membranes for Redox Flow Batteries.

Ion-conducting membranes (ICMs) with high selectivity are important components in redox flow batteries. However it is still a challenge to break the trade-off between ion conductivity and ion selectivity, which can be resolved by the regulation of their nanostructures. Here, polyoxometalate (POM)-hybridized block copolymers (BCPs) are used as self-assembled additives to construct proton-selective nanobarriers in the ICM matrix to improve the microscopic structures and macroscopic properties of ICMs. Benefiting from the co-assembly behavior of BCPs and POMs and their cooperative noncovalent interactions with the polymer matrix, ∼50 nm ellipsoidal functional nanoassemblies with hydrophobic vanadium-shielding cores and hydrophilic proton-conducting shells are constructed in the sulfonated poly(ether ether ketone) matrix, which leads to an overall enhancement of proton conductivity, proton selectivity, and cell performance. These results present a self-assembly route to construct functional nanostructures for the modification of polymer electrolyte membranes toward emerging energy technologies.

Semi-Solid Supramolecular Ionic Network Electrolytes Formed by Zwitterionic Liquids and Polyoxometalate Nanoclusters for High Proton Conduction.

Flexible electrolytes with solid self-supporting properties are highly desired in the fields of energy and electronics. However, traditional flexible electrolytes prepared by doping ionic liquids or salt solutions into a polymer matrix pose a risk of liquid component leakage during device operation. In this work, the development of supramolecular ionic network electrolytes using polyoxometalate nanoclusters as supramolecular crosslinkers to solidify bola-type zwitterionic liquids is reported. The resulting self-supporting electrolytes possess semi-solid features and show a high proton conductivity of 8.2 × 10-4 S cm-1 at low humidity (RH = 30%). Additionally, the electrolytes exhibit a typical plateau region in rheological tests, indicating that their dynamic network structures can contribute mechanical behavior similar to the entangled networks in covalent polymer materials. This work introduces a new paradigm for designing flexible solid electrolytes and expands the concept of reticular chemistry to noncrystalline systems.

Ionic-Nanophase Hybridization of Nafion by Supramolecular Patching for Enhanced Proton Selectivity in Redox Flow Batteries.

Nafion, as the mostly used proton exchange membrane material in vanadium redox flow batteries (VRFBs), encounters serious vanadium permeation problems due to the large size difference between its anionic nanophase (3-5 nm) and cationic vanadium ions (∼0.6 nm). Bulk hybridization usually suppresses the vanadium permeation at the expense of proton conductivity since conventional additives tend to randomly agglomerate and damage the nanophase continuity from unsuitable sizes and intrinsic incompatibility. Here, we report the ionic-nanophase hybridization strategy of Nafion membranes by using fluorinated block copolymers (FBCs) and polyoxometalates (POMs) as supramolecular patching additives. The cooperative noncovalent interactions among Nafion, interfacial-active FBCs, and POMs can construct a 1 nm-shrunk ionic nanophase with abundant proton transport sites, preserved continuity, and efficient vanadium screeners, which leads to a comprehensive enhancement in proton conductivity, selectivity, and VRFB performance. These results demonstrate the intriguing potential of the supramolecular patching strategy in precisely tuning nanostructured electrolyte membranes for improved performance.

Semi-Solid Superprotonic Supramolecular Polymer Electrolytes Based on Deep Eutectic Solvents and Polyoxometalates.

Supramolecular polymers (SPs) exhibit intriguing benefits in functional soft materials due to their dynamic bonding feature. However, most SPs can only exist in the solution state and fail to form bulk materials, which limits their applications. Here, we report the fabrication of semi-solid bulk SP materials by using polyoxometalate (POM) nanoclusters as supramolecular cross-linkers to solidify a deep eutectic solvent (DES). The abundant protons and strong hydrogen bonds afforded by POMs enable these SP materials as superprotonic conductive electrolytes with sufficient mechanical strength, showing a proton conductivity more than 1×10-4  S cm-1 and a breaking strength exceeding 1 MPa at room temperature. Moreover, the thermodynamic reversibility of the SP electrolytes allows them to form a stable electrode-electrolyte interface by a facile melt-infiltration strategy upon mild heating, which leads to improved performance in supercapacitors. This work presents an innovative DES/POM hybrid system as a promising platform to develop functional supramolecular materials for energy and electronic applications.

Hybrid Liquid-Crystalline Electrolytes with High-Temperature-Stable Channels for Anhydrous Proton Conduction.

Modern electrochemical and electronic devices require advanced electrolytes. Liquid crystals have emerged as promising electrolyte candidates due to their good fluidity and long-range order. However, the mesophase of liquid crystals is variable upon heating, which limits their applications as high-temperature electrolytes, e.g., implementing anhydrous proton conduction above 100 °C. Here, we report a highly stable thermotropic liquid-crystalline electrolyte based on the electrostatic self-assembly of polyoxometalate (POM) clusters and zwitterionic polymer ligands. These electrolytes can form a well-ordered mesophase with sub-10 nm POM-based columnar domains, attributed to the dynamic rearrangement of polymer ligands on POM surfaces. Notably, POMs can serve as both electrostatic cross-linkers and high proton conductors, which enable the columnar domains to be high-temperature-stable channels for anhydrous proton conduction. These nanochannels can maintain constant columnar structures in a wide temperature range from 90 to 160 °C. This work demonstrates the unique role of POMs in developing high-performance liquid-crystalline electrolytes, which can provide a new route to design advanced ion transport systems for energy and electronic applications.

Block-copolymer-like self-assembly behavior of mobile-ligand grafted ultra-small nanoparticles.

We use coarse-grained molecular dynamics simulations to study the self-assembly behavior of polyoxometalate (POM) nanoparticles (NPs) decorated with mobile polymer ligands under melt conditions. We demonstrate that due to the mobile nature of the grafted ligands on the NP surface, NPs have the ability to expose a part of their surfaces, leading to a block-copolymer-like self-assembly behavior. The exposed NP surface serves as one block and the grafted ligand polymers as another. This system has a strong ability to self-assemble into long-range ordered structures such as block copolymers due to large incompatibility between POM and ligand polymers, i.e., POM NPs can form lamellar, cylindrical, and spherical structures, which are consistent with previous experimental results. More importantly, these ordered structures are on the sub-10 nm scale, which is an important requirement for many applications. At low graft density, we find a new inverse-cylindrical structure formation where polymers form cylinders and POMs form a continuous network structure. A full self-assembly phase diagram is constructed which illustrates rules to manipulate the self-assembly structures of NPs decorated with mobile polymer ligands. We hope that these computational results will be useful for the new design of nanostructures with improved optical or electronic functions.

Triblock Copolymer/Polyoxometalate Nanocomposite Electrolytes with Inverse Hexagonal Cylindrical Nanostructures.

The primary issue of polymer electrolytes is to achieve high ion conductivity while retaining mechanical properties. A nanocomposite electrolyte with the inverse hexagonal cylindrical phase (three-dimensionally continuous domains for ion conduction and embedded domains for mechanical support) is prepared through the electrostatic self-assembly of a polyoxometalate (H3 PW12 O40 , PW) and a triblock copolymer poly(N-vinyl pyrrolidone)-block-polystyrene-block-poly(N-vinyl pyrrolidone) (PSP). The cylindrical nanocomposite exhibits a conductivity of 1.32 mS cm-1 and a storage modulus of 4.6 × 107  Pa at room temperature. These two values are higher than those of pristine PSP by two orders of magnitudes and a factor of six, respectively. PW clusters are used as multifunctional nano-additives (morphological inducer, proton conductor, and nano-enhancer) and their incorporation achieves the simultaneous improvement in both conductive and mechanical performance.

Multiscale Self-Assembly of Mobile-Ligand Molecular Nanoparticles for Hierarchical Nanocomposites.

Multiscale hierarchical morphologies are greatly desired for fabricating nanocomposites with tunable macroscopic properties, but challenges remain in precisely manipulating the spatial arrangement of nanoparticles in polymer matrices across multiple length scales. Here, we demonstrate a class of mobile-ligand nanoparticle system built upon 1 nm anionic polyoxometalate molecular nanoparticles and cationic terminated polymer chains by electrostatic interaction. The highly rearrangeable polymer chains can serve as mobile ligands to direct the polyoxometalates to align into sub-10 nm anisotropic superlattice-like nanoarrays in the bulk state. Moreover, these nanoarrays can further serve as structural units to assemble into hierarchically ordered morphologies in polymer matrices, e.g., percolated networks over hundreds of micrometers which are comprised of cylindrically packed polyoxometalate superlattices down to sub-10 nm scale. These hierarchical morphologies enable the nanocomposites with reinforced mechanical performance. The presented mobile-ligand approach can provide a paradigm to design functional polymer nanocomposites with improved properties such as mechanical reinforcement and collective optical and electronic functions.