Surface engineering is a critical technique for improving the performance of lithium-ion batteries (LIBs). Here, we introduce a novel vapor-based technique, namely, chemical vapor deposition polymerization, that can engineer nanoscale polymer thin films with controllable thickness and composition on the surface of battery electrodes. This technique enables us to, for the first time, systematically compare the effects of a conducting poly(3,4-ethylenedioxythiophene) (PEDOT) polymer and an insulating poly(divinylbenzene) (PDVB) polymer on the performance of a LiMnO electrode in LIBs. Our results show that conducting PEDOT coatings improve both the rate and the cycling performance of LiMnO electrodes, whereas insulating PDVB coatings have little effect on these performances. The PEDOT coating increases 10 C rate capacity by 83% at 25 °C (from 23 to 42 mA h/g) and by 30% at 50 °C (from 64 to 83 mA h/g). Furthermore, the PEDOT coating extends the high-temperature (50 °C) cycling life of LiMnO by over 60%. A model is developed, which can precisely describe the capacity degradation exhibited by the different types of cells, based on the aging mechanisms of Mn dissolution and solid-electrolyte interphase growth. Results from X-ray photoelectron spectroscopy suggest that chemical or coordination bonds form between Mn in LiMnO and O and S in the PEDOT film. These bonds stabilize the surface of LiMnO and thus improve the cycling performance. In contrast, no bonds form between Mn and the elements in the PDVB film. We further demonstrate that this vapor-based technique can be extended to other cathodes for advanced LIBs.
Thermal rectification is an exotic thermal transport phenomenon which allows heat to transfer in one direction but block the other. We demonstrate an unusual dual-mode solidstate thermal rectification effect using a heterogeneous "irradiated-pristine" polyethylene nanofiber junction as a nanoscale thermal diode, in which heat flow can be rectified in both directions by changing the working temperature. For the nanofiber samples measured here, we observe a maximum thermal rectification factor as large as~50%, which only requires a small temperature bias of <10 K. The tunable nanoscale thermal diodes with large rectification and narrow temperature bias open up new possibilities for developing advanced thermal management, energy conversion and, potentially thermophononic technologies.
Electromagnetic (EM) fields can trigger a range of surprising responses in materials. Microwave radiation (MWR), a type of EM field in the frequency range of 0.3–300 GHz, can lower the synthesis temperature required for ceramics such as TiO2 and induces mixed amorphous–crystalline phase compositions. To better understand the effects of MWR on matter, structural changes during microwave heating and MWR‐assisted synthesis using in situ synchrotron X‐ray diffraction are studied. Anisotropic expansion–contraction of lattice parameters under microwave‐radiation is observed, which contradicts the results from conventional thermal heating. When as‐received TiO2 powders are heated with MWR, an instantaneous decrease in the intensities of diffraction peaks indicates decrystallization/amorphization. High‐resolution electron microscopy supports these observations. Raman spectroscopy and X‐ray photoemission spectroscopy indicate increased defect‐generation under microwave exposure. Molecular dynamics simulations on the anatase phase of TiO2 suggests that introducing an oxygen vacancy can lead to the formation of an interstitial–vacancy pair resulting in anisotropic expansion–contraction of the lattice. These unique responses of ceramics under externally applied fields provide direct evidence for nonthermal coupling between EM fields and matter. Understanding such nonthermal, field‐driven processes has implications in engineering low‐temperature processes for integrating ceramics with polymers for flexible electronics, energy harnessing, and storage applications.
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