The sample La_ 0.3Ca_ 0.7Mn_ 0.96W_ 0.04O_3 was prepared by the solid-state method. Magnetic properties of La_ 0.3Ca_ 0.7Mn_ 0.96W_ 0.04O_3 was studied through the measurement of M-T curve, M-H curves and ESR curves o...The sample La_ 0.3Ca_ 0.7Mn_ 0.96W_ 0.04O_3 was prepared by the solid-state method. Magnetic properties of La_ 0.3Ca_ 0.7Mn_ 0.96W_ 0.04O_3 was studied through the measurement of M-T curve, M-H curves and ESR curves of the sample. The results show that: charge ordering (CO) phase forms at 265 K; the system exhibits paramagnetism when T>265 K; it exhibits long-range anti-ferromagnetism (there is a little FM component in AFM background) and the coexistence of a little FM phase and AFM/CO phase forms when T<225 K; the system transforms from paramagnetism to antiferromagnetism in charge-ordering state with temperature decreasing from 265 to 225 K. The width of ESR spectrum line of the sample La_ 0.3Ca_ 0.7Mn_ 0.96W_ 0.04O_3 was measured, and the value of the line width of paramagnetic resonance ΔH_ PP increases with temperature decreasing, which indicates that ferromagnetic connection of the sample strengthens with temperature decreasing.展开更多
Due to its high operational voltage and energy density,P2-type Na_(0.67)Ni_(0.3)Mn_(0.7)O_(2) has become a leading cathode material for sodium-ion batteries(SIBs),which is an ideal option for large-scale energy storag...Due to its high operational voltage and energy density,P2-type Na_(0.67)Ni_(0.3)Mn_(0.7)O_(2) has become a leading cathode material for sodium-ion batteries(SIBs),which is an ideal option for large-scale energy storage.However,the practical application of P2-type Na_(0.67)Ni_(0.3)Mn_(0.7)O_(2) is limited by the capacity constraints and unwanted phase transitions,presenting significant challenges to the widespread application of SIBs.To address these challenges and optimize the electrochemical properties of the P2 phase cathode material,this study proposes a Cu and Zn co-doped strategy to improve the electrochemical performance.The incorporation of Cu/Zn can stabilize the P2-phase structure against P2-O2 phase transitions,thus enhancing its electrochemical properties.The as-obtained P2-type Na0.67[Ni_(0.3)Mn_(0.58)Cu_(0.09)Zn_(0.03)]O_(2) cathode material shows an impressive cycling stability,maintaining 80%capacity retention after 1000 cycles at 2 C.The cyclic voltammetry(CV)tests show that the Cu^(2+)/Cu^(3+)redox reaction is also involved in charge compensation during the charge/discharge process.展开更多
P2-type layered oxides have been considered as promising cathode materials for Na-ion batteries,but the capac-ity decay resulting from the Na+/vacancy ordering and phase transformation limits their future large-scale ...P2-type layered oxides have been considered as promising cathode materials for Na-ion batteries,but the capac-ity decay resulting from the Na+/vacancy ordering and phase transformation limits their future large-scale applica-tions.Herein,the impact of Li-doping in different layers on the structure and electrochemical performance of P2-type Na_(0.7)Ni_(0.35)Mn_(0.65)O_(2) is investigated.It can be found that Li ions successfully enter both the Na and transition metal layers.The strategy of Li-doping can improve the cycling stability and rate capability of P2-type layered oxides,which promotes the development of high-performance Na-ion batteries.展开更多
A new model material of Na[Mg(Ⅱ)Mn(Ⅳ)]O, with only Mgand Mnin the transition metal layers, is synthesized for the research of anionic redox reaction. The material delivers a capacity of ～130 mAh/g with a long plate...A new model material of Na[Mg(Ⅱ)Mn(Ⅳ)]O, with only Mgand Mnin the transition metal layers, is synthesized for the research of anionic redox reaction. The material delivers a capacity of ～130 mAh/g with a long plateau at ～4.2 V in the initial charge profile, indicating anionic redox reaction(ARR) involved during the initial desodiation process. In the following cycles, the reversible capacity can reach a high value of ～210 mAh/g, which is probably derived from the participation of both ARR and Mn/Mnredox couples, further proving the charge compensation from ARR during the initial charge and following cycles. The designed cathode material without Mnhelps avoid the influence of oxygen activity from transition metals, enabling the investigation of ARR without other distractions.展开更多
The spent lithium-ion batteries recovery has been brought into focus widely for its environmental imperatives and potential profits from the metal components,such as lithium,cobalt,nickel and manganese.However,the wea...The spent lithium-ion batteries recovery has been brought into focus widely for its environmental imperatives and potential profits from the metal components,such as lithium,cobalt,nickel and manganese.However,the weaker pollution and fewer profits of LiMn_(2)O_(4) cathode dispel the enthusiasm and responsibility of industry companies.Thus,a simplified and efncient method to regenerate the sodium-ion cathode materials and separate Li from spent LiMn_(2)O_(4) materials for the profit improvement is proposed.In detail,adjusting the parameters of carbothermal reduction process appropriately,the LiMn_(2)O_(4) spinel structure is destroyed within a short period time and transformed into simple metal oxide.As anticipated,nearly 95 wt.%lithium can be obtained and recovered during the water leaching,while 99 wt.%of manganese can be extracted in acid solution.Noted that the leaching residue can return to the carbothermic reduction,leading to a closed-loop economic recycling process.The regenerated Na_(0.67)Ni_(0.3)Mn_(0.7)O_(2) cathode displays excellent electrochemical performance with superior cycling stability(the initial capacity reaches 95.9 mAh·g^(-1),and the retention rate reached 98.3%after 100 cycles at 1 C).The delicate strategy of sodium-ion cathode material regenerated from spent LiMn_(2)O_(4) aims to realize lithium separation and material utilization of manganese simultaneously,providing the instructive suggestion to rise up the recycling profits of spent batteries.展开更多
文摘The sample La_ 0.3Ca_ 0.7Mn_ 0.96W_ 0.04O_3 was prepared by the solid-state method. Magnetic properties of La_ 0.3Ca_ 0.7Mn_ 0.96W_ 0.04O_3 was studied through the measurement of M-T curve, M-H curves and ESR curves of the sample. The results show that: charge ordering (CO) phase forms at 265 K; the system exhibits paramagnetism when T>265 K; it exhibits long-range anti-ferromagnetism (there is a little FM component in AFM background) and the coexistence of a little FM phase and AFM/CO phase forms when T<225 K; the system transforms from paramagnetism to antiferromagnetism in charge-ordering state with temperature decreasing from 265 to 225 K. The width of ESR spectrum line of the sample La_ 0.3Ca_ 0.7Mn_ 0.96W_ 0.04O_3 was measured, and the value of the line width of paramagnetic resonance ΔH_ PP increases with temperature decreasing, which indicates that ferromagnetic connection of the sample strengthens with temperature decreasing.
基金supported by the National Natural Science Foundation of China(Nos.22179077,51774251,21908142)Shanghai Science and Technology Commission’s“2020 Science and Technology In-novation Action Plan”(No.20511104003)Natural Science Foundation in Shanghai(No.21ZR1424200)。
文摘Due to its high operational voltage and energy density,P2-type Na_(0.67)Ni_(0.3)Mn_(0.7)O_(2) has become a leading cathode material for sodium-ion batteries(SIBs),which is an ideal option for large-scale energy storage.However,the practical application of P2-type Na_(0.67)Ni_(0.3)Mn_(0.7)O_(2) is limited by the capacity constraints and unwanted phase transitions,presenting significant challenges to the widespread application of SIBs.To address these challenges and optimize the electrochemical properties of the P2 phase cathode material,this study proposes a Cu and Zn co-doped strategy to improve the electrochemical performance.The incorporation of Cu/Zn can stabilize the P2-phase structure against P2-O2 phase transitions,thus enhancing its electrochemical properties.The as-obtained P2-type Na0.67[Ni_(0.3)Mn_(0.58)Cu_(0.09)Zn_(0.03)]O_(2) cathode material shows an impressive cycling stability,maintaining 80%capacity retention after 1000 cycles at 2 C.The cyclic voltammetry(CV)tests show that the Cu^(2+)/Cu^(3+)redox reaction is also involved in charge compensation during the charge/discharge process.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.12105372 and 51991344)President's Foundation of China Institute of Atomic Energy(Grant No.16YZ202212000201)Chinese Academy of Sciences(Grant No.XDB33000000).
文摘P2-type layered oxides have been considered as promising cathode materials for Na-ion batteries,but the capac-ity decay resulting from the Na+/vacancy ordering and phase transformation limits their future large-scale applica-tions.Herein,the impact of Li-doping in different layers on the structure and electrochemical performance of P2-type Na_(0.7)Ni_(0.35)Mn_(0.65)O_(2) is investigated.It can be found that Li ions successfully enter both the Na and transition metal layers.The strategy of Li-doping can improve the cycling stability and rate capability of P2-type layered oxides,which promotes the development of high-performance Na-ion batteries.
基金supported by funding from Science and Technology Project of the State Grid Corporation of China("research on key technology of low-strain layered oxides for long-life Na-ion batteries",No.DG71-16-027)
文摘A new model material of Na[Mg(Ⅱ)Mn(Ⅳ)]O, with only Mgand Mnin the transition metal layers, is synthesized for the research of anionic redox reaction. The material delivers a capacity of ～130 mAh/g with a long plateau at ～4.2 V in the initial charge profile, indicating anionic redox reaction(ARR) involved during the initial desodiation process. In the following cycles, the reversible capacity can reach a high value of ～210 mAh/g, which is probably derived from the participation of both ARR and Mn/Mnredox couples, further proving the charge compensation from ARR during the initial charge and following cycles. The designed cathode material without Mnhelps avoid the influence of oxygen activity from transition metals, enabling the investigation of ARR without other distractions.
基金supported by the National Natural Science Foundation of China(52070194,52073309)the Natural Science Foundation of Hunan Province(2022JJ20069)。
文摘The spent lithium-ion batteries recovery has been brought into focus widely for its environmental imperatives and potential profits from the metal components,such as lithium,cobalt,nickel and manganese.However,the weaker pollution and fewer profits of LiMn_(2)O_(4) cathode dispel the enthusiasm and responsibility of industry companies.Thus,a simplified and efncient method to regenerate the sodium-ion cathode materials and separate Li from spent LiMn_(2)O_(4) materials for the profit improvement is proposed.In detail,adjusting the parameters of carbothermal reduction process appropriately,the LiMn_(2)O_(4) spinel structure is destroyed within a short period time and transformed into simple metal oxide.As anticipated,nearly 95 wt.%lithium can be obtained and recovered during the water leaching,while 99 wt.%of manganese can be extracted in acid solution.Noted that the leaching residue can return to the carbothermic reduction,leading to a closed-loop economic recycling process.The regenerated Na_(0.67)Ni_(0.3)Mn_(0.7)O_(2) cathode displays excellent electrochemical performance with superior cycling stability(the initial capacity reaches 95.9 mAh·g^(-1),and the retention rate reached 98.3%after 100 cycles at 1 C).The delicate strategy of sodium-ion cathode material regenerated from spent LiMn_(2)O_(4) aims to realize lithium separation and material utilization of manganese simultaneously,providing the instructive suggestion to rise up the recycling profits of spent batteries.
