Compared to aqueous-phase electrocatalytic nitrogen reduction reaction(NRR),lithium-mediated NRR(Li-NRR)theoretically enhances the intrinsic activity of NH3 production through spontaneous exothermic reactions between ...Compared to aqueous-phase electrocatalytic nitrogen reduction reaction(NRR),lithium-mediated NRR(Li-NRR)theoretically enhances the intrinsic activity of NH3 production through spontaneous exothermic reactions between Li and N_(2).However,the in-situ generated solid electrolyte interphase(SEI)during the reaction slows down the Li^(+)transport and nucleation kinetics,which further hinders the subsequent activation and protonation processes.Herein,a sophisticated amorphous-crystalline heterostructured SEI of Zn-LiF is formed by additive engineering.The concerted electron interplay between amorphous and crystalline domains is prone to generate lithiophobic Zn and lithiophilic LiF sites,where lithiophobic Zn accelerates Li^(+)diffusion within the SEI and avoids high concentration polarization,and lithiophilic LiF ensures homogeneous nucleation of diffused Li^(+)and its participation in subsequent reactions.Therefore,compared to conventional SEI,a more than 8-fold performance improvement is achieved in the additive-engineered heterogeneous lithiophobic-lithiophilic SEI,which exhibits a high NH_(3)yield rate of 11.58 nmol s^(−1)cm^(−2)and a Faradaic efficiency of 32.97%.Thus,exploiting the synergistic effects in heterogeneous lithiophobic-lithiophilic structures to achieve functional complementarity between different components opens a new avenue toward high-performance Li-NRR.展开更多
基金supported by the National Natural Science Foundation of China(22178361,22378402,52302310)the International Partnership Project of CAS(039GJHZ2022029GC)+3 种基金the National Key R&D Program of China(2020YFA0710200)the Foundation of the Innovation Academy for Green Manufacture Institute,Chinese Academy of Sciences(IAGM2022D07)QinChuangYuan Cites High-level Innovation and Entrepreneurship Talent Programs(QCYRCXM-2022-335)the Open Project Program of Anhui Province International Research Center on Advanced Building Materials(JZCL2303KF).
文摘Compared to aqueous-phase electrocatalytic nitrogen reduction reaction(NRR),lithium-mediated NRR(Li-NRR)theoretically enhances the intrinsic activity of NH3 production through spontaneous exothermic reactions between Li and N_(2).However,the in-situ generated solid electrolyte interphase(SEI)during the reaction slows down the Li^(+)transport and nucleation kinetics,which further hinders the subsequent activation and protonation processes.Herein,a sophisticated amorphous-crystalline heterostructured SEI of Zn-LiF is formed by additive engineering.The concerted electron interplay between amorphous and crystalline domains is prone to generate lithiophobic Zn and lithiophilic LiF sites,where lithiophobic Zn accelerates Li^(+)diffusion within the SEI and avoids high concentration polarization,and lithiophilic LiF ensures homogeneous nucleation of diffused Li^(+)and its participation in subsequent reactions.Therefore,compared to conventional SEI,a more than 8-fold performance improvement is achieved in the additive-engineered heterogeneous lithiophobic-lithiophilic SEI,which exhibits a high NH_(3)yield rate of 11.58 nmol s^(−1)cm^(−2)and a Faradaic efficiency of 32.97%.Thus,exploiting the synergistic effects in heterogeneous lithiophobic-lithiophilic structures to achieve functional complementarity between different components opens a new avenue toward high-performance Li-NRR.
