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Structurally stabilized composites are promising for using phase change materials in high‐temperature thermal energy storage (TES). However, conventional skeleton materials, which typically comprise 30–50 wt% of the composite, mainly provide sensible heat storage and contribute minimally to overall energy density. This study introduces a new class of redox‐active oxide‐molten salt (ROMS) composites that overcome this limitation by combining sensible, latent, and thermochemical heat storage in a single particle. Specifically, porous, redox‐active Ca₂AlMnO_5+δ(CAM) complex oxide particles were demonstrated as a suitable support matrix, with the pores filled by eutectic NaCl/CaCl₂salt. X‐ray diffraction confirms excellent phase compatibility between CAM and the salt. Scanning electron microscopy/energy dispersive X‐ray spectroscopy and nano X‐ray tomography show good salt infiltration and wettability within the CAM pores. Thermogravimetric analysis reveals that a 60 wt% CAM/40 wt% salt composite achieves an energy density of 267 kJ kg⁻¹over a narrow 150 °C window, with ≈50 kJ kg⁻¹from thermochemical storage. Additionally, the composite shows higher thermal conductivity than salt alone, enabling faster energy storage and release. ROMS composites thus represent a novel and efficient solution for high‐performance TES. 

This study introduces a new family of redox-active oxide molten salt (ROMS) composites for high-capacity thermal energy storage. Porous perovskite oxides serve as active support materials, facilitating thermochemical energy storage... 

Abstract Understanding thermal transport mechanisms in polymeric composites allows us to expand the boundaries of thermal conductivity in them, either increasing it for more efficient heat dissipation or decreasing it for better thermal insulation. But, these mechanisms are not fully understood. Systematic experimental investigations remain limited. Practical strategies to tune the interfacial thermal resistance (ITR) between fillers and polymers and the thermal conductivity of composites remain elusive. Here, we studied the thermal transport in representative polymer composites, using polyethylene (PE) or polyaniline (PANI) as matrices and graphite as fillers. PANI, with aromatic rings in its backbone, interacts with graphite through strong noncovalent π–π stacking interactions, whereas PE lacks such interactions. We can then quantify how π–π stacking interactions between graphite and polymers enhance thermal transport in composites. PE/graphite and PANI/graphite composites with the same 1.5% filler volume fractions show a ∼22.82% and ∼34.85% enhancement in thermal conductivity compared to pure polymers, respectively. Calculated ITRs in PE/graphite and PANI/graphite are ∼6×10−8 m2 K W−1 and ∼1×10−8 m2 K W−1, respectively, highlighting how π–π stacking interactions reduce ITR. Molecular dynamics (MD) simulations suggest that π–π stacking interactions between PANI chains and graphite surfaces enhance alignment of PANI's aromatic rings with graphite surfaces. This allows more carbon atoms from PANI chains to interact with graphite surfaces at a shorter distance compared to PE chains. Our work indicates that tuning the π–π stacking interactions between polymers and fillers is an effective approach to reduce the ITR and enhance the thermal conductivity of composites. 

To push upper boundaries of thermal conductivity in polymer composites, understanding of thermal transport mechanisms is crucial. Despite extensive simulations, systematic experimental investigation on thermal transport in polymer composites is limited. To better understand thermal transport processes, we design polymer composites with perfect fillers (graphite) and defective fillers (graphite oxide), using polyvinyl alcohol (PVA) as a matrix model. Measured thermal conductivities of ~1.38 ± 0.22 W m⁻¹K⁻¹in PVA/defective filler composites is higher than those of ~0.86 ± 0.21 W m⁻¹K⁻¹in PVA/perfect filler composites, while measured thermal conductivities in defective fillers are lower than those of perfect fillers. We identify how thermal transport occurs across heterogeneous interfaces. Thermal transport measurements, neutron scattering, quantum mechanical modeling, and molecular dynamics simulations reveal that vibrational coupling between PVA and defective fillers at PVA/filler interfaces enhances thermal conductivity, suggesting that defects in polymer composites improve thermal transport by promoting this vibrational coupling. 

For heat conduction along polymer chains, a decrease in the axial thermal conductivity often occurs when the polymer structure changes from one-dimensional (1D) to three-dimensional (3D). For example, a single extended aliphatic chain (e.g., polyethylene or poly(dimethylsiloxane)) usually has a higher axial thermal conductivity than its double-chain or crystal counterparts because coupling between chains induces strong interchain anharmonic scatterings. Intuitively, for chains with an aromatic backbone, the even stronger π–π stacking, once formed between chains, should enhance thermal transport across chains and suppress the thermal conductivity along the chains. However, we show that this trend is the opposite in poly(p-phenylene) (PPP), a typical chain with an aromatic backbone. Using molecular dynamics simulations, we found that the axial thermal conductivity of PPP chains shows an anomalous dimensionality dependence where the thermal conductivity of double-chain and 3D crystal structures is higher than that of a 1D single chain. We analyzed the probability distribution of dihedral angles and found that π–π stacking between phenyl rings restricts the free rotation of phenyl rings and forms a long-range order along the chain, thus enhancing thermal transport along the chain direction. Though possessing a stronger bonding strength and stabilizing the multiple-chain structure, π–π stacking does not lead to a higher interchain thermal conductance between phenyl rings compared with that between aliphatic chains. Our simulation results on the effects of π–π stacking provide insights to engineer thermal transport in polymers at the molecular level.