Manganese-based cathode materials are considered as a promising candidate for rechargeable aqueous zinc-ion batteries(ZIBs).Suffering from poor conductive and limited structure tolerance,various carbon matrix,especial...Manganese-based cathode materials are considered as a promising candidate for rechargeable aqueous zinc-ion batteries(ZIBs).Suffering from poor conductive and limited structure tolerance,various carbon matrix,especially N-doped carbon,were employed to incorporate with MnO_(2)for greatly promoted electrochemical performances.However,the related underlying mechanism is still unknown,which is unfavorable to guide the design of high performance electrode.Herein,by incorporating layered MnO_(2)with N-doped carbon nanowires,a free-standing cathode with hierarchical core-shell structure(denoted as MnO_(2)@NC)is prepared.Benefiting from the N-doped carbon and rational architecture,the MnO_(2)@NC electrode shows an enhanced specific capacity(325 mAh g^(−1)at 0.1 A g^(−1))and rate performance(90 mAh g^(−1)at 2 A g^(−1)),as well as improved cycling stability.Furthermore,the performance improvement mechanism of MnO_(2)incorporated by N-doped carbon is investigated by X-ray photoelectron spectroscopy(XPS),Raman spectrums and density functional theory(DFT)calculation.The N atom elongates the Mn-O bond and reduces the valence of Mn^(4+)ion in MnO_(2)crystal by delocalizing its electron clouds.Thus,the electrostatic repulsion will be weakened when Zn^(2+)/H^(+)insert into the host MnO_(2)lattices,which is profitable to more cation insertion and faster ion transfer kinetics for higher capacity and rate capability.This work elucidates a fundamental understanding of the functions of N-doped carbon in composite materials and shed light on a practical pathway to optimize other electrode materials.展开更多
基金supported by National Natural Science Foundation of China(Nos.U20A20246,51872108)the Fundamental Research Funds for the Central Universities(Nos.30106200463 and CCNU20TS006)Graduate Education Innovation Grant from Central China Normal University(No.2020CXZZ101).
文摘Manganese-based cathode materials are considered as a promising candidate for rechargeable aqueous zinc-ion batteries(ZIBs).Suffering from poor conductive and limited structure tolerance,various carbon matrix,especially N-doped carbon,were employed to incorporate with MnO_(2)for greatly promoted electrochemical performances.However,the related underlying mechanism is still unknown,which is unfavorable to guide the design of high performance electrode.Herein,by incorporating layered MnO_(2)with N-doped carbon nanowires,a free-standing cathode with hierarchical core-shell structure(denoted as MnO_(2)@NC)is prepared.Benefiting from the N-doped carbon and rational architecture,the MnO_(2)@NC electrode shows an enhanced specific capacity(325 mAh g^(−1)at 0.1 A g^(−1))and rate performance(90 mAh g^(−1)at 2 A g^(−1)),as well as improved cycling stability.Furthermore,the performance improvement mechanism of MnO_(2)incorporated by N-doped carbon is investigated by X-ray photoelectron spectroscopy(XPS),Raman spectrums and density functional theory(DFT)calculation.The N atom elongates the Mn-O bond and reduces the valence of Mn^(4+)ion in MnO_(2)crystal by delocalizing its electron clouds.Thus,the electrostatic repulsion will be weakened when Zn^(2+)/H^(+)insert into the host MnO_(2)lattices,which is profitable to more cation insertion and faster ion transfer kinetics for higher capacity and rate capability.This work elucidates a fundamental understanding of the functions of N-doped carbon in composite materials and shed light on a practical pathway to optimize other electrode materials.
