Sulfur-bridged bonds enabled structure modulation and space confinement of MnS for superior sodium-ion capacitors.

Manganese sulfide (MnS) is a promising converion-type anode for sodium storage, owing to the virtues of high theoretical capacity, coupled with it crustal abundance and cost-effectiveness. Nevertheless, MnS suffers from inadequate electronic conductivity, sluggish Na+ reaction kinetics and considerable volume variation during discharge/charge process, thereby impeding its rate capability and capacity retention. Herein, a novel lamellar heterostructured composite of Fe-doped MnS nanoparticles/positively charged reduced graphene oxide (Fe-MnS/PG) was synthesized to overcome these issues. The Fe-doping can accelerate the ion/electron transfer, endowing fast electrochemical kinetics of MnS. Meanwhile, the graphene space confinement with strong MnSC bond interactions can facilite the interfacial electron transfer, hamper volume expansion and aggregation of MnS nanoparticles, stabilizing the structural integrity, thus improving the Na+ storage reversibility and cyclic stability. Combining the synergistic effect of Fe-doping and space confinement with strong MnSC bond interactions, the as-produced Fe-MnS/PG anode presents a remarkable capacity of 567 mAh/g at 0.1 A/g and outstanding rate performance (192 mAh/g at 10 A/g). Meanwhile, the as-assembled sodium-ion capacitor (SIC) can yield a high energy density of 119 Wh kg-1 and a maximum power density of 17500 W kg-1, with capacity retention of 77 % at 1 A/g after 5000 cycles. This work offers a promising strategy to develop MnS-based practical SICs with high energy and long lifespan, and paves the way for fabricating advanced anode materials.

Effect of fluorine on the photovoltaic properties of 2,1,3-benzothiadiazole-based alternating conjugated polymers by changing the position and number of fluorine atoms.

Fluorination is one of the most effective ways to manipulate molecular packing, optical bandgap and molecular energy levels in organic semiconductor materials. In this work, different number of fluorine atoms was introduced into the acceptor moiety 2,2'-dithiophene linked 2,1,3-benzothiadiazole, utilizing the alkylthiophene modified dithieno[2,3-d:2',3'-d']benzo[1,2-b:4,5-b] (DTBDT) as the donor unit, three polymers: PDTBDT-0F-BTs, PDTBDT-2F-BTs and PDTBDT-6F-FBTs were synthesized. With the number of fluorine atoms in each repeat unit of polymers varying from 0 to 2 and then up to 6, PDTBDT-0F-BTs, PDTBDT-2F-BTs and PDTBDT-6F-FBTs exhibited gradually downshifted energy levels and improved dielectric constants (εr) from 3.4 to 4.3 to 5.8, further successively increased charge transport mobilities. As a result, the power conversion efficiency (PCE) of the bulk heterojunction organic photovoltaic devices (BHJ-OPV) from the blend films of aforementioned polymers paired with PC71BM were gradually increased from 1.69 for PDTBDT-0F-BTs to 1.89 for PDTBDT-2F-BTs and then to 5.28 for PDTBDT-6F-FBTs. The results show that the continuous insertion of fluorine atoms into the repeating units of the benzothiadiazole conjugated polymer leads to the deepening of HOMO energy level, the increase of εr and the increase of charge mobility, which improve the efficiency of charge transfer and electron collection, thus improving the photovoltaic performance of BHJ-OPV.