Fabrication of Single-Ion Conductors Based on Liquid Crystal Polymer Network for Quasi-Solid-State Lithium Ion Batteries.

Single-ion conductive polymer electrolytes can improve the safety of lithium ion batteries (LIBs) by increasing the lithium transference number (tLi+) and avoiding the growth of lithium dendrites. Meanwhile, the self-assembled ordered structure of liquid crystal polymer networks (LCNs) can provide specific channels for the ordered transport of Li ions. Herein, single-ion conductive nematic and cholesteric LCN electrolyte membranes (denoted as NLCN-Li and CLCN-Li) were successfully prepared. NLCN-Li was then coated on commercial Celgard 2325 while CLCN-Li was coated on poly(vinylidene fluoride-hexafluoropropylene) film, coupled with plasticizer, to make NLCN-Li/Cel and CLCN-Li/Pv quasi-solid-state electrolyte membranes, respectively. Their electrochemical properties were evaluated, and it was found that they possessed benign thermal stability and electrolyte/electrode compatibility, high tLi+ up to 0.98 and high electrochemical stability window up to 5.2 V. A small amount (0.5M) of extra Li salt added to the plasticizer could improve the ion conductivity from 1.79 × 10-5 to 5.04 × 10-4 S cm-1, while the tLi+ remained 0.85. The assembled LFP|Li batteries also exhibited excellent cycling and rate performances. The orderliness of the LCN layer played an important role in the distribution and movement of Li ions, thereby affecting the Li deposition and growth of Li dendrites. As the first report of nematic and cholesteric LCN single-ion conductors, this work sheds light on the design and fabrication of ordered quasi-solid-state electrolytes for high-performance and safe LIBs.

Steerable and Agile Light-Fueled Rolling Locomotors by Curvature-Engineered Torsional Torque.

On-demand photo-steerable amphibious rolling motions are generated by the structural engineering of monolithic soft locomotors. Photo-morphogenesis of azobenzene-functionalized liquid crystal polymer networks (azo-LCNs) is designed from spiral ribbon to helicoid helices, employing a 270° super-twisted nematic molecular geometry with aspect ratio variations of azo-LCN strips. Unlike the intermittent and biased rolling of spiral ribbon azo-LCNs with center-of-mass shifting, the axial torsional torque of helicoid azo-LCNs enables continuous and straight rolling at high rotation rates (≈720 rpm). Furthermore, center-tapered helicoid structures with wide edges are introduced for effectively accelerating photo-motilities while maintaining directional controllability. Irrespective of surface conditions, the photo-induced rotational torque of center-tapered helicoid azo-LCNs can be transferred to interacting surfaces, as manifested by steep slope climbing and paddle-like swimming multimodal motilities. Finally, the authors demonstrate continuous curvilinear guidance of soft locomotors, bypassing obstacles and reaching desired destinations through real-time on-demand photo-steering.

Light- and Field-Controlled Diffusion, Ejection, Flow and Collection of Liquid at a Nanoporous Liquid Crystal Membrane.

Liquid manipulation at solid surfaces has attracted plenty of interest yet most of them are limited to one or two direction(s), while transport in three dimensions is largely unexplored. Here, we demonstrate three-dimensionally steered dynamic liquid mobility at nanoporous liquid crystal polymer coatings. To this end, we orchestrate liquid motion via sequential triggers of light and/or electric field. Upon a primary flood exposure to UV light, liquid is ejected globally over the entire coating surfaces. We further reallocate the secreted liquid by applying a secondary electric field stimulus. By doing so, the liquid is transported and collected at pre-set positions as determined by the electrode positions. We further monitor this process in real-time and perform precise analysis. Interestingly, when applying those two triggers simultaneously, we discover a UV-gated liquid-release effect, which decreases threshold voltage as well as threshold frequency.

Tunable Photomechanics in Diarylethene-Driven Liquid Crystal Network Actuators.

The response of soft actuators made of stimuli-responsive materials can be phenomenologically described by a stimulus-deformation curve, depicting the controllability and sensitivity of the actuator system. Manipulating such stimulus-deformation curve allows fabricating soft microrobots with reconfigurable actuation behavior, which is not easily achievable using conventional materials. Here, we report a light-driven actuator based on a liquid crystal polymer network containing diarylethene (DAE) photoswitches as cross-links, in which the stimulus-deformation curve under visible-light illumination is tuned with UV light. The tuning is brought about by the reversible electrocyclization of the DAE units. Because of the excellent thermal stability of the visible-absorbing closed-form DAEs, the absorbance of the actuator can be optically fixed to a desired value, which in turn dictates the efficiency of photothermally induced deformation. We employ the controllability in devising a logical AND gate with macroscopic output, i.e., an actuator that bends negligibly under UV or visible light irradiation, but with profound shape change when addressed to both simultaneously. The results provide design tools for reconfigurable microrobotics and polymer-based logic gating.