Ternary MOF‑Based Redox Active Sites Enabled 3D‑on‑2D Nanoarchitectured Battery‑Type Electrodes for High‑Energy‑Density Supercapatteries

Designing rationally combined metal-organic frameworks(MOFs)with multifunctional nanogeometries is of significant research interest to enable the electrochemical properties in advanced energy storage devices.Herein,we explored a new class of binderfree dual-layered Ni-Co-Mn-based MOFs(NCM-based MOFs)with three-dimensional(3D)-on-2D nanoarchitectures through a polarityinduced solution-phase method for high-performance supercapatteries.The hierarchical NCM-based MOFs having grown on nickel foam exhibit a battery-type charge storage mechanism with superior areal capacity(1311.4μAh cm^−2 at 5 mA cm^−2),good rate capability(61.8%;811.67μAh cm^−2 at 50 mA cm^−2),and an excellent cycling durability.The superior charge storage properties are ascribed to the synergistic features,higher accessible active sites of dual-layered nanogeometries,and exalted redox chemistry of multi metallic guest species,respectively.The bilayered NCM-based MOFs are further employed as a battery-type electrode for the fabrication of supercapattery paradigm with biomass-derived nitrogen/oxygen doped porous carbon as a negative electrode,which demonstrates excellent capacity of 1.6 mAh cm^−2 along with high energy and power densities of 1.21 mWh cm^−2 and 32.49 mW cm^−2,respectively.Following,the MOF-based supercapattery was further assembled with a renewable solar power harvester to use as a self-charging station for various portable electronic applications.     

Atomic Modulation of 3D Conductive Frameworks Boost Performance of MnO2 for Coaxial Fiber‑Shaped Supercapacitors

Coaxial fiber-shaped supercapacitors are a promising class of energy storage devices requiring high performance for flexible and miniature electronic devices.Yet,they are still struggling from inferior energy density,which comes from the limited choices in materials and structure used.Here,Zn-doped CuO nanowires were designed as 3D framework for aligned distributing high mass loading of MnO2 nanosheets.Zn could be introduced into the CuO crystal lattice to tune the covalency character and thus improve charge transport.The Zn–CuO@MnO2 as positive electrode obtained superior performance without sacrificing its areal and gravimetric capacitances with the increasing of mass loading of MnO2 due to 3D Zn–CuO framework enabling efficient electron transport.A novel category of free-standing asymmetric coaxial fiber-shaped supercapacitor based on Zn0.11CuO@MnO2 core electrode possesses superior specific capacitance and enhanced cell potential window.This asymmetric coaxial structure provides superior performance including higher capacity and better stability under deformation because of sufficient contact between the electrodes and electrolyte.Based on these advantages,the as-prepared asymmetric coaxial fiber-shaped supercapacitor exhibits a high specific capacitance of 296.6 mF cm^−2 and energy density of 133.47μWh cm^−2.In addition,its capacitance retention reaches 76.57%after bending 10,000 times,which demonstrates as-prepared device’s excellent flexibility and long-term cycling stability.     

N‑Doped Graphene‑Decorated NiCo Alloy Coupled with Mesoporous NiCoMoO Nano‑sheet Heterojunction for Enhanced Water Electrolysis Activity at High Current Density

Developing highly effective and stable non-noble metalbased bifunctional catalyst working at high current density is an urgent issue for water electrolysis(WE).Herein,we prepare the N-doped graphene-decorated NiCo alloy coupled with mesoporous NiCoMoO nano-sheet grown on 3D nickel foam(NiCo@C-NiCoMoO/NF)for water splitting.NiCo@C-NiCoMoO/NF exhibits outstanding activity with low overpotentials for hydrogen and oxygen evolution reaction(HER:39/266 mV;OER:260/390 mV)at±10 and±1000 mA cm^?2.More importantly,in 6.0 M KOH solution at 60℃ for WE,it only requires 1.90 V to reach 1000 mA cm?2 and shows excellent stability for 43 h,exhibiting the potential for actual application.The good performance can be assigned to N-doped graphene-decorated NiCo alloy and mesoporous NiCoMoO nano-sheet,which not only increase the intrinsic activity and expose abundant catalytic activity sites,but also enhance its chemical and mechanical stability.This work thus could provide a promising material for industrial hydrogen production.