In conventional ethylene carbonate(EC)/propylene carbonate(PC)electrolyte,sodium metal reacts spontaneously and deleteriously with solvent molecules.This significantly limits the practical feasibility of high-voltage ...In conventional ethylene carbonate(EC)/propylene carbonate(PC)electrolyte,sodium metal reacts spontaneously and deleteriously with solvent molecules.This significantly limits the practical feasibility of high-voltage sodium metal batteries based on Na metal chemistry.Herein,we present a sodium metal alloy strategy via introducing NaIn and Na_(2)In phases in a Na/In/C composite,aiming at boosting Na ion deposition stability in the common EC/PC electrolyte.Symmetric cells with Na/In/C electrodes achieve an impressive long-term cycling capability at 1 mA cm^(-2)(>870 h)and 5 mA cm^(-2)(>560 h),respectively,with a capacity of 1 mAh cm^(-2).In situ optical microscopy clearly unravels a stable Na ion dynamic deposition process on the Na/In/C composite electrode surface,attributing to a dendrite-free and smooth morphology.Furthermore,theoretical simulations reveal intrinsic mechanism for the reversible Na ion deposition behavior with the composite Na/In/C electrode.Upon pairing with a highvoltage NaVPOF cathode,Na/In/C anode illustrates a better suitability in SMB s.This work promises an alternative alloying strategy for enhancing Na metal interfacial stability in the common EC/PC electrolyte for their future applications.展开更多
P2-Na_(0.67)Ni_(0.33)Mn_(0.67)O_(2)(NNMO)is promising cathode material for sodium-ion batteries(SIBs)due to its high specific capacity and fast Na+diffusion rate.Nonetheless,the irreversible P2-O_(2)phase transformati...P2-Na_(0.67)Ni_(0.33)Mn_(0.67)O_(2)(NNMO)is promising cathode material for sodium-ion batteries(SIBs)due to its high specific capacity and fast Na+diffusion rate.Nonetheless,the irreversible P2-O_(2)phase transformation,Na+/vacancy ordering,and transition metal(TM)dissolution seriously damage its cycling stability and restrict its commercialization process.Herein,Na occupation manipulation and interface stabilization are proposed to strengthen the phase structure of NNMO by synergistic Zn/Ti co-doping and introducing lithium difluorophosp(LiPO_(2)F_(2))film-forming electrolyte additive.The Zn/Ti co-doping regulates the occupancy ratio of Nae/Nafat Na sites and disorganizes the Na+/vacancy ordering,resulting in a faster Na+diffusion kinetics and reversible P2-Z phase transition for P2-Na_(0.67)Ni_(0.28)Zn_(0.05)Mn_(0.62)Ti_(0.05)O_(2)(NNZMTO).Meanwhile,the LiPO_(2)F_(2)additive can form homogeneous and ultrathin cathode-electrolyte interphase(CEI)on NNZMTO surface,which can stabilize the NNZMTO-electrolyte interface to prevent TM dissolution,surface structure transformation,and micro-crack generation.Combination studies of in situ and ex situ characterizations and theoretical calculations were used to elucidate the storage mechanism of NNZMTO with Li PO_(2)F_(2)additive.As a result,the NNZMTO displays outstanding capacity retention of 94.44%after 500 cycles at 1C with 0.3 wt%Li PO_(2)F_(2),excellent rate performance of 92.5 mA h g^(-1)at 8C with 0.1 wt%Li PO_(2)F_(2),and remarkable full cell capability.This work highlights the important role of manipulating Na occupation and constructing protective film in the design of layered materials,which provides a promising direction for developing high-performance cathodes for SIBs.展开更多
基金This work was supported by the NSFC/RGC Joint Research Scheme 2020/21(Project No:N_CityU104/20)National Natural Science Foundation of China(Grant No.U1804132)+1 种基金Zhongyuan Youth Talent support program of Henan province(Grant No.ZYQR201912152)Zhengzhou University Youth Talent Start-up Grant.
文摘In conventional ethylene carbonate(EC)/propylene carbonate(PC)electrolyte,sodium metal reacts spontaneously and deleteriously with solvent molecules.This significantly limits the practical feasibility of high-voltage sodium metal batteries based on Na metal chemistry.Herein,we present a sodium metal alloy strategy via introducing NaIn and Na_(2)In phases in a Na/In/C composite,aiming at boosting Na ion deposition stability in the common EC/PC electrolyte.Symmetric cells with Na/In/C electrodes achieve an impressive long-term cycling capability at 1 mA cm^(-2)(>870 h)and 5 mA cm^(-2)(>560 h),respectively,with a capacity of 1 mAh cm^(-2).In situ optical microscopy clearly unravels a stable Na ion dynamic deposition process on the Na/In/C composite electrode surface,attributing to a dendrite-free and smooth morphology.Furthermore,theoretical simulations reveal intrinsic mechanism for the reversible Na ion deposition behavior with the composite Na/In/C electrode.Upon pairing with a highvoltage NaVPOF cathode,Na/In/C anode illustrates a better suitability in SMB s.This work promises an alternative alloying strategy for enhancing Na metal interfacial stability in the common EC/PC electrolyte for their future applications.
基金supported by the Natural Science Foundation of Shandong Province (ZR2023MB017,ZR2021QB055,ZR2020QB014,ZR2022JQ10)the National Natural Science Foundation of China (21901146,220781792,52007110)the Taishan Scholar Foundation (tsqn201812063)。
文摘P2-Na_(0.67)Ni_(0.33)Mn_(0.67)O_(2)(NNMO)is promising cathode material for sodium-ion batteries(SIBs)due to its high specific capacity and fast Na+diffusion rate.Nonetheless,the irreversible P2-O_(2)phase transformation,Na+/vacancy ordering,and transition metal(TM)dissolution seriously damage its cycling stability and restrict its commercialization process.Herein,Na occupation manipulation and interface stabilization are proposed to strengthen the phase structure of NNMO by synergistic Zn/Ti co-doping and introducing lithium difluorophosp(LiPO_(2)F_(2))film-forming electrolyte additive.The Zn/Ti co-doping regulates the occupancy ratio of Nae/Nafat Na sites and disorganizes the Na+/vacancy ordering,resulting in a faster Na+diffusion kinetics and reversible P2-Z phase transition for P2-Na_(0.67)Ni_(0.28)Zn_(0.05)Mn_(0.62)Ti_(0.05)O_(2)(NNZMTO).Meanwhile,the LiPO_(2)F_(2)additive can form homogeneous and ultrathin cathode-electrolyte interphase(CEI)on NNZMTO surface,which can stabilize the NNZMTO-electrolyte interface to prevent TM dissolution,surface structure transformation,and micro-crack generation.Combination studies of in situ and ex situ characterizations and theoretical calculations were used to elucidate the storage mechanism of NNZMTO with Li PO_(2)F_(2)additive.As a result,the NNZMTO displays outstanding capacity retention of 94.44%after 500 cycles at 1C with 0.3 wt%Li PO_(2)F_(2),excellent rate performance of 92.5 mA h g^(-1)at 8C with 0.1 wt%Li PO_(2)F_(2),and remarkable full cell capability.This work highlights the important role of manipulating Na occupation and constructing protective film in the design of layered materials,which provides a promising direction for developing high-performance cathodes for SIBs.
