Poly(ethylene glycol) nanocomposites of sub-nanometer metal oxide clusters for dynamic semi-solid proton conductive electrolytes

Abstract

EDGE ARTICLEPanchao Yin et al. Poly(ethylene glycol) nanocomposites of sub-nanometer metal oxide clusters for dynamic semi-solid proton conductive electrolytes Sub-nm-scale metal oxide clusters (PW 12 O 40 3À) show high solubility in the melt of poly(ethylene glycol) (PEG) and the obtained semi-solid nanocomposites show promising proton conductivities under ambient conditions. Suggested from scattering studies, the clusters are homogeneously dispersed in the PEG melt at the molecular scale with high loading amounts (70 wt%) and the formed real solutions can be stable for months with no aggregation or phase separation. The conductivities of the nanocomposites which are governed by the concentrations of H 3 PW 12 O 40 can reach as high as 1.01 Â 10 À2 S cm À1 at the highest concentration. Due to the dynamic cross-linking hydrogen bonding between clusters and PEG, the nanocomposites behave like solids with negligible flow at high concentrations of clusters. Upon the application of high-speed shear forces (>32 s À1 ), the composites can flow with continuously decreasing viscosities. The shear thinning properties of the nanocomposites enable their convenient processing into required morphologies and the wettability of electrolytes to electrodes under typical high shear rate processing conditions and the safety of the produced devices can be ensured by their solid-like properties in the static state. † Electronic supplementary information (ESI) available: Details of the d-cals calculation method, IR and impedance spectra, ow curves, relationship between the shear rate and stress, viscosities and volume fraction of POMs, cyclic curves of shear rate and shear stress, E a of the nanocomposites, DLS data and the tting curves of ow curves. See

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“…These peaks reflect the distribution distance between PW clusters in polymer matrices. 58 In these samples, the contents of POMs are the same, but the volume fractions of PVP are increased. The increasing distribution distance of PW reflects that PW clusters are dispersed more and more sparsely when the PVP domains become larger.…”

“…[48][49][50] Recently, the excellent proton conductivity, electrochemical stability, and water-retention ability of POMs have attracted special interest to develop POM-polymer composite electrolytes for proton conduction. [51][52][53][54][55][56][57][58][59][60][61] However, it is difficult to manipulate the distribution of POMs in polymer electrolytes to form well-connected proton conductive pathways, as the strong electrostatic interaction easily induces the disordered aggregation of POMs. Recently, Guiver and co-workers reported a breakthrough they obtained: one-dimensional (1D) POM-based protonconducting channels in a homopolymer electrolyte matrix through an external magnetic field alignment.…”

Polyoxometalate–Polymer Hybrid Materials as Proton Exchange Membranes for Fuel Cell Applications

“…For example, Uchida and Yin et al dissolved H 3 PW 12 O 40 ·nH 2 O, PEG1000 and CsNO 3 into water and obtained highly efficient proton-conducting POM–PEG crystalline hybrid materials, in which a single PEG chain was confined in the one-dimentional nanochannels defined by the frameworks of POMs [59,60]. Besides water, polar organic solvents such as alcohols and N, N-dimethylformamide which are able to make POMs and polymers a homogeneous solution, are also widely used in solution blending [61,62,63]. It should be noted that when dealing with water-insoluble polymers which cannot directly blend with POMs, solution swelling is also a constructive way to achieve the hybridization process.…”

Poly(triethylene glycol methyl ether methacrylate) hydrogel as a carrier of phosphotungstic acid for acid catalytic reaction in water

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