层状过渡金属氧化物由于其较高的理论比容量和较低的经济成本,被视为一种具有良好应用前景的钠离子电池正极材料。采用溶胶-凝胶法和热处理的方式,制备Ca/Cu共掺杂的铁锰基层状氧化物(O3-Na_(0.9)Ca_(0.05)Fe_(0.45)Mn_(0.45)Cu_(0.1O)_...层状过渡金属氧化物由于其较高的理论比容量和较低的经济成本,被视为一种具有良好应用前景的钠离子电池正极材料。采用溶胶-凝胶法和热处理的方式,制备Ca/Cu共掺杂的铁锰基层状氧化物(O3-Na_(0.9)Ca_(0.05)Fe_(0.45)Mn_(0.45)Cu_(0.1O)_(2))。采用X射线衍射仪(XRD)、场发射扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)等对该O3型铁锰基层状氧化物正极材料进行表征分析。结果表明,在32 mA/g电流密度下该材料具有205.2 m A·h/g的高比容量,循环50圈之后仍具有67.64%的容量保持率,在160 m A/g下循环100圈后依然具有81.4 m A·h/g的放电比容量。由于Ca的掺入,引起Na^(+)空位的增加,并且Cu的掺入提高了Mn的价态,从而提高了Na^(+)的扩散速率,抑制了Mn3+的Jahn-Teller效应,缓解了晶格应力,有效提高了材料的结构稳定性和电化学性能。展开更多
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
文摘层状过渡金属氧化物由于其较高的理论比容量和较低的经济成本,被视为一种具有良好应用前景的钠离子电池正极材料。采用溶胶-凝胶法和热处理的方式,制备Ca/Cu共掺杂的铁锰基层状氧化物(O3-Na_(0.9)Ca_(0.05)Fe_(0.45)Mn_(0.45)Cu_(0.1O)_(2))。采用X射线衍射仪(XRD)、场发射扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)等对该O3型铁锰基层状氧化物正极材料进行表征分析。结果表明,在32 mA/g电流密度下该材料具有205.2 m A·h/g的高比容量,循环50圈之后仍具有67.64%的容量保持率,在160 m A/g下循环100圈后依然具有81.4 m A·h/g的放电比容量。由于Ca的掺入,引起Na^(+)空位的增加,并且Cu的掺入提高了Mn的价态,从而提高了Na^(+)的扩散速率,抑制了Mn3+的Jahn-Teller效应,缓解了晶格应力,有效提高了材料的结构稳定性和电化学性能。
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.
