P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phas...P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phases remains a necessity.Herein,we design a P2/O3-type Na_(0.76)Ni_(0.31)Zn_(0.07)Mn_(0.50)Ti_(0.12)0_(2)(NNZMT)with high chemical/electrochemical stability by enhancing the coupling between the two phases.For the first time,a unique Na*extraction is observed from a Na-rich O3 phase by a Na-poor P2 phase and systematically investigated.This process is facilitated by Zn^(2+)/Ti^(4+)dual doping and calcination condition regulation,allowing a higher Na*content in the P2 phase with larger Na^(+)transport channels and enhancing Na transport kinetics.Because of reduced Na^(+)in the O3 phase,which increases the difficulty of H^(+)/Na^(+) exchange,the hydrostability of the O3 phase in NNZMT is considerably improved.Furthermore,Zn^(2+)/Ti^(4+)presence in NNZMT synergistically regulates oxygen redox chemistry,which effectively suppresses O_(2)/CO_(2) gas release and electrolyte decomposition,and completely inhibits phase transitions above 4.0 V.As a result,NNZMT achieves a high discharge capacity of 144.8 mA h g^(-1) with a median voltage of 3.42 V at 20 mA g^(-1) and exhibits excellent cycling performance with a capacity retention of 77.3% for 1000 cycles at 2000 mA g^(-1).This study provides an effective strategy and new insights into the design of high-performance layered-oxide cathode materials with enhanced structure/interface stability forSIBs.展开更多
The oxidation process of low-grade vanadium slag in the presence of Na2CO3 was investigated by XRD,SEM/EDS and TG-DSC techniques.The results show that the vanadium slag is oxidized in a temperature range from 273 to 7...The oxidation process of low-grade vanadium slag in the presence of Na2CO3 was investigated by XRD,SEM/EDS and TG-DSC techniques.The results show that the vanadium slag is oxidized in a temperature range from 273 to 700 °C.Olivine phases and spinel phases are completely decomposed at 500 and 600 °C,respectively.Most of water-soluble sodium vanadates are formed between 500 and 600 °C.When roasting temperature reaches above 700 °C,the vanadium-rich phases of sodium vanadates can be obviously observed.However,at temperature above 800 °C,the samples are sintered.Most of the vanadium is enwrapped by glassy phase compounds which lead to the decrease of the leaching rate of vanadium.At the same time,the effect of roasting temperature on extraction of vanadium and characterization of leach residues were discussed.展开更多
基金supported by the National Natural Science Foundation of China (22169002)the Chongzuo Key Research and Development Program of China (20220603)the Counterpart Aid Project for Discipline Construction from Guangxi University(2023M02)
文摘P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phases remains a necessity.Herein,we design a P2/O3-type Na_(0.76)Ni_(0.31)Zn_(0.07)Mn_(0.50)Ti_(0.12)0_(2)(NNZMT)with high chemical/electrochemical stability by enhancing the coupling between the two phases.For the first time,a unique Na*extraction is observed from a Na-rich O3 phase by a Na-poor P2 phase and systematically investigated.This process is facilitated by Zn^(2+)/Ti^(4+)dual doping and calcination condition regulation,allowing a higher Na*content in the P2 phase with larger Na^(+)transport channels and enhancing Na transport kinetics.Because of reduced Na^(+)in the O3 phase,which increases the difficulty of H^(+)/Na^(+) exchange,the hydrostability of the O3 phase in NNZMT is considerably improved.Furthermore,Zn^(2+)/Ti^(4+)presence in NNZMT synergistically regulates oxygen redox chemistry,which effectively suppresses O_(2)/CO_(2) gas release and electrolyte decomposition,and completely inhibits phase transitions above 4.0 V.As a result,NNZMT achieves a high discharge capacity of 144.8 mA h g^(-1) with a median voltage of 3.42 V at 20 mA g^(-1) and exhibits excellent cycling performance with a capacity retention of 77.3% for 1000 cycles at 2000 mA g^(-1).This study provides an effective strategy and new insights into the design of high-performance layered-oxide cathode materials with enhanced structure/interface stability forSIBs.
基金Project (2008AA031104) supported by the National High-tech Research and Development Program of China Project (2010063003) supported by the Sharing Fund of Large-scale Equipment of Chongqing University,China
文摘The oxidation process of low-grade vanadium slag in the presence of Na2CO3 was investigated by XRD,SEM/EDS and TG-DSC techniques.The results show that the vanadium slag is oxidized in a temperature range from 273 to 700 °C.Olivine phases and spinel phases are completely decomposed at 500 and 600 °C,respectively.Most of water-soluble sodium vanadates are formed between 500 and 600 °C.When roasting temperature reaches above 700 °C,the vanadium-rich phases of sodium vanadates can be obviously observed.However,at temperature above 800 °C,the samples are sintered.Most of the vanadium is enwrapped by glassy phase compounds which lead to the decrease of the leaching rate of vanadium.At the same time,the effect of roasting temperature on extraction of vanadium and characterization of leach residues were discussed.
