Anisotropic MRI contrast reveals enhanced ionic transport in plastic crystals

Organic ionic plastic crystals (OIPCs) are attractive as solid-state electrolytes for electrochemical devices such as lithium-ion batteries and solar and fuel cells. OIPCs offer high ionic conductivity, nonflammability, and versatility of molecular design. Nevertheless, intrinsic ion transport behavior of OIPCs is not fully understood, and their measured properties depend heavily on thermal history. Solid-state magnetic resonance imaging experiments reveal a striking image contrast anisotropy sensitive to the orientation of grain boundaries in polycrystalline OIPCs. Probing triethyl(methyl)phosphonium bis(fluorosulfonyl)imide (P1222FSI) samples with different thermal history demonstrates vast variations in microcrystallite alignment. Upon slow cooling from the melt, microcrystallites exhibit a preferred orientation throughout the entire sample, leading to an order of magnitude increase in conductivity as probed using impedance spectroscopy. This investigation describes both a new conceptual window and a new characterization method for understanding polycrystalline domain structure and transport in plastic crystals and other solid-state conductors.

An organic ionic plastic crystal electrolyte for rate capability and stability of ambient temperature lithium batteries

Reliable, safe and high performance solid electrolytes are a critical step in the advancement of high energy density secondary batteries. In the present work we demonstrate a novel solid electrolyte based on the organic ionic plastic crystal (OIPC) triisobutyl(methyl)phosphonium bis(fluorosulfonyl)imide (P1444FSI). With the addition of 4 mol% LiFSI, the OIPC shows a high conductivity of 0.26 mS cm-1 at 22 °C. The ion transport mechanisms have been rationalized by compiling thermal phase behaviour and crystal structure information obtained by variable temperature synchrotron X-ray diffraction. With a large electrochemical window (ca. 6 V) and importantly, the formation of a stable and highly conductive solid electrolyte interphase (SEI), we were able to cycle lithium cells (LiLiFePO4) at 30 °C and 20 °C at rates of up to 1 C with good capacity retention. At the 0.1 C rate, about 160 mA h g-1 discharge capacity was achieved at 20 °C, which is the highest for OIPC based cells to date. It is anticipated that these small phosphonium cation and [FSI] anion based OIPCs will show increasing significance in the field of solid electrolytes.

Severe plastic deformation of TWIP steel

The severe plastic deformation of a Twinning Induced Plasticity (TWIP), 0.61C-22.3Mn-0.19Si-0.14Ni-0.27Cr (wt. %) steel by Equal Channel Angular Pressing (ECAP) at elevated temperatures was used to study the deformation mechanism as a function of accumulated strain and processing parameters. The relationship between the microstructures after different deformation schedules of ECAP at the temperatures of 200, 300 and 400oC, strain hardening behavior and mechanical properties was studied. The best balance between strength and ductility (1702 MPa and 24%) was found after 2 passes at 400oC and 300oC of ECAP. It was due to the formation of deformation microbands and twins in the microstructure. The twinning was observed after all deformation schedules except after 1 pass at 400oC. The important finding was the formation of twins in the ultrafine grains. Moreover, the stacking faults were observed in the subgrains with the size of 50nm. It is also worth mentioning the formation of nano- twins within the micro-twins at the same time. It was found that the deformation schedule affects the dislocation substructure with formation of deformation bands, cells, subgrains, two variants of twins that, in turn, influence the strain-hardening behavior and mechanical properties. Keywords: Twinning Induced Plasticity steels; Equal Channel Angular Pressing; mechanical properties; transmission electron microscopy; micro/nano twins; dislocation substructure.