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 single phase La2（CO3）3·3.4H2 O was synthesized by hydrothermal method. The thermal decomposition and intermediates and final solid products of La2（CO3）3·3.4H2O from 30 to 1000 °C were characteri...The single phase La2（CO3）3·3.4H2 O was synthesized by hydrothermal method. The thermal decomposition and intermediates and final solid products of La2（CO3）3·3.4H2O from 30 to 1000 °C were characterized by XRD, FTIR and DTA-TG. The kinetics of dehydration of La2（CO3）3·3.4H2O in the temperature range of 30-366 °C was investigated under non-isothermal conditions. Flynn-Wall-Ozawa and Friedman isoconversion methods were used to calculate the activation energy and analyze the reaction steps; multivariate non-linear regression program was applied to determine the most probable mechanism and the kinetic parameters. The results show that the thermal dehydration of La2（CO3）3·3.4H2O is a kind of three-step competitive reaction, and controlled by an n-order initial reaction followed by n-order competitive reaction（FnFnFn model）. The activation energy matching with the most probable model is close to value obtained by Friedman method. The fitting curves match the original TG-DTG curves very well.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(201011005-5)supported by the National Land and Resources Public Welfare Scientific Research Project of ChinaProject(41030426)supported by the National Natural Science Foundation of China+1 种基金Project(20095122110015)supported by Specialized Research Fund for the Doctoral Program of Higher Education of ChinaProject(2010-32)supported by Scientific Research Foundation of the Education Ministry for Returned Chinese Scholars,China
文摘The single phase La2（CO3）3·3.4H2 O was synthesized by hydrothermal method. The thermal decomposition and intermediates and final solid products of La2（CO3）3·3.4H2O from 30 to 1000 °C were characterized by XRD, FTIR and DTA-TG. The kinetics of dehydration of La2（CO3）3·3.4H2O in the temperature range of 30-366 °C was investigated under non-isothermal conditions. Flynn-Wall-Ozawa and Friedman isoconversion methods were used to calculate the activation energy and analyze the reaction steps; multivariate non-linear regression program was applied to determine the most probable mechanism and the kinetic parameters. The results show that the thermal dehydration of La2（CO3）3·3.4H2O is a kind of three-step competitive reaction, and controlled by an n-order initial reaction followed by n-order competitive reaction（FnFnFn model）. The activation energy matching with the most probable model is close to value obtained by Friedman method. The fitting curves match the original TG-DTG curves very well.
