Charging P2-Na_(2/3)Ni_(1/3)Mn_(2/3)O_(2)to 4.5 V for higher capacity is enticing.However,it leads to severe capacity fading,ascribing to the lattice oxygen evolution and the P2-O2 phase transformation.Here,the Mg Fe_...Charging P2-Na_(2/3)Ni_(1/3)Mn_(2/3)O_(2)to 4.5 V for higher capacity is enticing.However,it leads to severe capacity fading,ascribing to the lattice oxygen evolution and the P2-O2 phase transformation.Here,the Mg Fe_(2)O_(4) coating and Mg,Fe co-doping were constructed simultaneously by Mg,Fe surface treatment to suppress lattice oxygen evolution and P2-O2 phase transformation of P2-Na_(2/3)Ni_(1/3)Mn_(2/3)O_(2)at deep charging.Through ex-situ X-ray diffraction(XRD)tests,we found that the Mg,Fe bulk co-doping could reduce the repulsion between transition metals and Na+/vacancies ordering,thus inhibiting the P2-O2 phase transition and significantly reducing the irreversible volume change of the material.Meanwhile,the internal electric field formed by the dielectric polarization of Mg Fe_(2)O_(4) effectively inhibits the outward migration of oxidized O^(a-)(a<2),thereby suppressing the lattice oxygen evolution at deep charging,confirmed by in situ Raman and ex situ XPS techniques.P2-Na NM@MF-3 shows enhanced high-voltage cycling performance with capacity retentions of 84.8% and 81.3%at 0.1 and 1 C after cycles.This work sheds light on regulating the surface chemistry for Na-layered oxide materials to enhance the high-voltage performance of Na-ion batteries.展开更多
The Nickel-rich layered cathode materials have been considered as promising cathode for lithium-ion batteries(LIBs),which due to it can achieve a high capacity of than 200 mAh g^(-1)under a high cutoff voltage of4.5 V...The Nickel-rich layered cathode materials have been considered as promising cathode for lithium-ion batteries(LIBs),which due to it can achieve a high capacity of than 200 mAh g^(-1)under a high cutoff voltage of4.5 V.However,the nickel-rich layered cathode materials show severely capacity fading at high voltage cycling,induced by the hybrid O anion and cation redox promote O^(α-)(α<2)migration in the crystal lattice under high charge voltage,lead to the instability of the oxygen skeleton and oxygen evolution,promote the phase transition and electrolyte decomposition.Here,Li_(1-x)TMO_(2-y)/Li_(2)SO_(4) hybrid layer is designed by a simple pyrolysis method to enhance the high voltage cycle stability of NCM.In such constructed hybrid layer,the inner spinel structure of Li_(1-x)TMO_(2-y)layer is the electron-rich state,which could form an electron cloud coupling with the NCM with surface oxygen vacancies,while Li_(2)SO_(4) is p-type semiconductors,thus constructing a heterojunction interface of Li_(1-x)TMO_(2-y)//Li_(2)SO_(4) and Li_(1-x)TMO_(2-y)//NCM,thereby generating internal self-built electric fields to inhibit the outward migration of bulk oxygen anions.Moreover,the internal self-built electric fields could not only strengthen the bonding force between the Li_(1-x)TMO_(2-y)/Li_(2)SO_(4) hybrid layer and host NCM material,but also boost the charge transfer.As consequence,the modified NCM materials show excellent electrochemical performance with capacity retention of 97.7%and 90.1%after 200 cycles at 4.3 V and 4.5 V,respectively.This work provides a new idea for the development of high energy density applications of Nickel-rich layered cathode materials.展开更多
基金supported by the Special Project for the Central Government to Guide Local Technological Development (GUIKE ZY20198008)the Guangxi Technology Base and talent Subject (GUIKE AD20238012,AD20297086)+5 种基金the Natural Science Foundation of Guangxi Province (2021GXNSFDA075012)the National Natural Science Foundation of China (51902108,52104298,22169004)the National Natural Science Foundation of China (U20A20249)the Regional Innovation and Development Joint Fundthe Guangxi Innovation Driven Development Subject (GUIKE AA19182020,19254004)the Special Fund for Guangxi Distinguished Expert。
文摘Charging P2-Na_(2/3)Ni_(1/3)Mn_(2/3)O_(2)to 4.5 V for higher capacity is enticing.However,it leads to severe capacity fading,ascribing to the lattice oxygen evolution and the P2-O2 phase transformation.Here,the Mg Fe_(2)O_(4) coating and Mg,Fe co-doping were constructed simultaneously by Mg,Fe surface treatment to suppress lattice oxygen evolution and P2-O2 phase transformation of P2-Na_(2/3)Ni_(1/3)Mn_(2/3)O_(2)at deep charging.Through ex-situ X-ray diffraction(XRD)tests,we found that the Mg,Fe bulk co-doping could reduce the repulsion between transition metals and Na+/vacancies ordering,thus inhibiting the P2-O2 phase transition and significantly reducing the irreversible volume change of the material.Meanwhile,the internal electric field formed by the dielectric polarization of Mg Fe_(2)O_(4) effectively inhibits the outward migration of oxidized O^(a-)(a<2),thereby suppressing the lattice oxygen evolution at deep charging,confirmed by in situ Raman and ex situ XPS techniques.P2-Na NM@MF-3 shows enhanced high-voltage cycling performance with capacity retentions of 84.8% and 81.3%at 0.1 and 1 C after cycles.This work sheds light on regulating the surface chemistry for Na-layered oxide materials to enhance the high-voltage performance of Na-ion batteries.
基金supported by the National Natural Science Foundation of China(51902108,51762006,51964013)the Special Projects for Central Government to Guide Local Technological Development(GUIKE ZY20198008)+2 种基金the Guangxi InnovationDriven Development Subject(GUIKE AA19182020,GUIKE AA19254004)the Guangxi Technology Base and Talent Subject(GUIKE AD18126001,GUIKE AD20999012,GUIKE AD20297086)the Special Fund for Guangxi Distinguished Expert。
文摘The Nickel-rich layered cathode materials have been considered as promising cathode for lithium-ion batteries(LIBs),which due to it can achieve a high capacity of than 200 mAh g^(-1)under a high cutoff voltage of4.5 V.However,the nickel-rich layered cathode materials show severely capacity fading at high voltage cycling,induced by the hybrid O anion and cation redox promote O^(α-)(α<2)migration in the crystal lattice under high charge voltage,lead to the instability of the oxygen skeleton and oxygen evolution,promote the phase transition and electrolyte decomposition.Here,Li_(1-x)TMO_(2-y)/Li_(2)SO_(4) hybrid layer is designed by a simple pyrolysis method to enhance the high voltage cycle stability of NCM.In such constructed hybrid layer,the inner spinel structure of Li_(1-x)TMO_(2-y)layer is the electron-rich state,which could form an electron cloud coupling with the NCM with surface oxygen vacancies,while Li_(2)SO_(4) is p-type semiconductors,thus constructing a heterojunction interface of Li_(1-x)TMO_(2-y)//Li_(2)SO_(4) and Li_(1-x)TMO_(2-y)//NCM,thereby generating internal self-built electric fields to inhibit the outward migration of bulk oxygen anions.Moreover,the internal self-built electric fields could not only strengthen the bonding force between the Li_(1-x)TMO_(2-y)/Li_(2)SO_(4) hybrid layer and host NCM material,but also boost the charge transfer.As consequence,the modified NCM materials show excellent electrochemical performance with capacity retention of 97.7%and 90.1%after 200 cycles at 4.3 V and 4.5 V,respectively.This work provides a new idea for the development of high energy density applications of Nickel-rich layered cathode materials.
