A Three-Dimensional Silicon-Diacetylene Porous Organic Radical Polymer

Radical-containing porous organic polymers(POPs)have drawn great interest in various applications.However,the synthesis of radical POPs remains challenging due to the unstable nature of organic radicals.Here,a persistent and stable three-dimensional silicon-diacetylene porous organic radical polymer was synthesized via a classic Eglinton homocoupling reaction of tetraethynylsilane.The presence of carbon radicals in this material was confirmed by electron paramagnetic resonance,and its paramagnetic behavior was analyzed by a superconducting quantum interference device.This unique material has a low-lying lowest unoccupied molecular orbital(LUMO)energy level(−5.47 eV)and a small energy gap(ca.1.46 eV),which shows long-term cycling stability and excellent rate capability as an anode material for lithium-ion batteries,demonstrating potential application in energy fields.

Novel 3D grid porous Li_(4)Ti_(5)O_(12) thick electrodes fabricated by 3D printing for high performance lithium-ion batteries

Three-dimensional(3D)grid porous electrodes introduce vertically aligned pores as a convenient path for the transport of lithium-ions(Li-ions),thereby reducing the total transport distance of Li-ions and improving the reaction kinetics.Although there have been other studies focusing on 3D electrodes fabricated by 3D printing,there still exists a gap between electrode design and their electrochemical performance.In this study,we try to bridge this gap through a comprehensive investigation on the effects of various electrode parameters including the electrode porosity,active material particle diameter,electrode electronic conductivity,electrode thickness,line width,and pore size on the electrochemical performance.Both numerical simulations and experimental investigations are conducted to systematically examine these effects.3D grid porous Li_(4)Ti_(5)O_(12)(LTO)thick electrodes are fabricated by low temperature direct writing technology and the electrodes with the thickness of 1085μm and areal mass loading of 39.44 mg·cm^(−2) are obtained.The electrodes display impressive electrochemical performance with the areal capacity of 5.88 mAh·cm^(−2)@1.0 C,areal energy density of 28.95 J·cm^(−2)@1.0 C,and areal power density of 8.04 mW·cm^(−2)@1.0 C.This study can provide design guidelines for obtaining 3D grid porous electrodes with superior electrochemical performance.

Ball-flower-like carbon microspheres via a three-dimensional replication strategy as a high-capacity cathode in lithium–oxygen batteries

The robust porous architectures of active materials are highly desired for oxygen electrodes in lithium–oxygen batteries to enable high capacities and excellent reversibility. Herein, we report a novel three-dimensional replication strategy to fabricate three-dimensional architecture of porous carbon for oxygen electrodes in lithium–oxygen batteries. As a demonstration, ball-flower-like carbon microspheres assembled with tortuous hollow carbon nanosheets are successfully prepared by completely replicating the morphology of the nanostructured zinc oxide template and utilizing the polydopamine coating layer as the carbon source.When used as the active material for oxygen electrodes, the three-dimensional porous architecture of the prepared ballflower-like carbon microspheres can accommodate the discharge product lithium peroxide and simultaneously maintain the ions and gas diffusion paths. Moreover, their high degrees of defectiveness by nitrogen doping provide sufficient active sites for oxygen reduction/evolution reaction.Thus the prepared ball-flower-like carbon microspheres demonstrate a high capacity of 9,163.7 mA h g-1 and excellent reversibility. This work presents an effective way to prepare three-dimensional architectures of porous carbon by replicating the controllable nanostructures of transition metal oxide templates for energy storage and conversion applications.