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.

Insight into local structure and molecular dynamics in organic solid-state ionic conductors

Elucidating the rate and geometry of molecular dynamics is particularly important for unravelling ion-conduction mechanisms in electrochemical materials. The local molecular motions in the plastic crystal 1-ethyl-1-methylpyrrolidinium tetrafluoroborate ([C2 mpyr][BF4 ]) are studied by a combination of quantum chemical calculations and advanced solid-state nuclear magnetic resonance spectroscopy. For the first time, a restricted puckering motion with a small fluctuation angle of 25° in the pyrrolidinium ring has been observed, even in the low-temperature phase (-45 °C). This local molecular motion is deemed to be particularly important for the material to maintain its plasticity, and hence, its ion mobility at low temperatures.

Anisotropic hardening model based on non-associated flow rule and combined nonlinear kinematic hardening for sheet materials

 A material model for more effective analysis of plastic deformation of sheet materials is presented in this paper. The model is capable of considering the following aspects of plastic deformation behavior of sheet materials: the anisotropy in yielding stresses in different directions by using a quadratic yield function (based on Hill’s 1948 model and stress ratios), the anisotropy in work hardening by introducing non-constant flow stress hardening in different directions, the anisotropy in plastic strains in different directions by using a quadratic plastic potential function and non-associated flow rule (based on Hill’s 1948 model and plastic strain ratios, r-values), and finally some of the cyclic hardening phenomena such as Bauschinger’s effect and transient behavior for reverse loading by using a coupled nonlinear kinematic hardening (so-called Armstrong-Frederick-Chaboche model). Basic fundamentals of the plasticity of the model are presented in a general framework. Then, the model adjustment procedure is derived for the plasticity formulations. Also, a generic numerical stress integration procedure is developed based on backward-Euler method (so-called multistage return mapping algorithm). Different aspects of the model are verified for DP600 steel sheet. Results show that the new model is able to predict the sheet material behavior in both anisotropic hardening and cyclic hardening regimes more accurately. By featuring the above-mentioned facts in the presented constitutive model, it is expected that more accurate results can be obtained by implementing this model in computational simulations of sheet material forming processes. For instance, more precise results of springback prediction of the parts formed from highly anisotropic hardened materials or that of determining the forming limit diagrams is highly expected by using the developed material model.

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.