The preparation process of sodium molybdate has the disadvantages of high energy consumption,low thermal efficiency,and high raw material requirement of molybdenum trioxide,in order to realize the green and efficient ...The preparation process of sodium molybdate has the disadvantages of high energy consumption,low thermal efficiency,and high raw material requirement of molybdenum trioxide,in order to realize the green and efficient development of molybdenum concentrate resources,this paper proposes a new process for efficient recovery of molybdenum from molybdenum concentrate and preparation of sodium molybdate by microwave-enhanced roasting and alkali leaching.Thermodynamic analysis indicated the feasibility of oxidation roasting of molybdenum concentrate.The effects of roasting temperature,holding time,and power-to-mass ratio on the oxidation product and leaching product sodium molybdate (Na_(2)MoO_(4)·2H_(2)O) were investigated.Under the optimal process conditions:roasting temperature of 700℃,holding time of 110 min,and power-to-mass ratio of 110 W/g,the molybdenum state of existence was converted from MoS_(2) to Mo O3.The process of preparing sodium molybdate by alkali leaching of molybdenum calcine was investigated,the optimal leaching conditions include a solution concentration of 2.5 mol/L,a liquid-to-solid ratio of 2 mL/g,a leaching temperature of 60℃,and leaching solution termination at pH 8.The optimum conditions result in a leaching rate of sodium molybdate of 96.24%.Meanwhile,the content of sodium molybdate reaches 94.08wt%after leaching and removing impurities.Iron and aluminum impurities can be effectively separated by adjusting the pH of the leaching solution with sodium carbonate solution.This research avoids the shortcomings of the traditional process and utilizes the advantages of microwave metallurgy to prepare high-quality sodium molybdate,which provides a new idea for the highvalue utilization of molybdenum concentrate.展开更多
Following publication of the original article[1],the authors reported that the author Hun-Gi Jung should be affiliated as 3,4 and 5 instead of 4 and 5.The author’s name“A.-Yeon Kim”needed to be updated to“A-Yeon ...Following publication of the original article[1],the authors reported that the author Hun-Gi Jung should be affiliated as 3,4 and 5 instead of 4 and 5.The author’s name“A.-Yeon Kim”needed to be updated to“A-Yeon Kim”,removing the period.The correct author’s name and affiliation have been provided in this Correction.The original article[1]has been corrected.展开更多
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
This study explores the impact of introducing vacancy in the transition metal layer of rationally designed Na_(0.6)[Ni_(0.3)Ru_(0.3)Mn_(0.4)]O_(2)(NRM)cathode material.The incorporation of Ru,Ni,and vacancy enhances t...This study explores the impact of introducing vacancy in the transition metal layer of rationally designed Na_(0.6)[Ni_(0.3)Ru_(0.3)Mn_(0.4)]O_(2)(NRM)cathode material.The incorporation of Ru,Ni,and vacancy enhances the structural stability during extensive cycling,increases the operation voltage,and induces a capacity increase while also activating oxygen redox,respectively,in Na_(0.7)[Ni_(0.2)V_(Ni0.1)Ru_(0.3)Mn_(0.4)]O_(2)(V-NRM)compound.Various analytical techniques including transmission electron microscopy,X-ray absorption near edge spectroscopy,operando X-ray diffraction,and operando differential electrochemical mass spectrometry are employed to assess changes in the average oxidation states and structural distortions.The results demonstrate that V-NRM exhibits higher capacity than NRM and maintains a moderate capacity retention of 81%after 100 cycles.Furthermore,the formation of additional lone-pair electrons in the O 2p orbital enables V-NRM to utilize more capacity from the oxygen redox validated by density functional calculation,leading to a widened dominance of the OP4 phase without releasing O_(2) gas.These findings offer valuable insights for the design of advanced high-capacity cathode materials with improved performance and sustainability in sodium-ion batteries.展开更多
The widespread interest in layered P2-type Mn-based cathode materials for sodium-ion batteries(SIBs)stems from their cost-effectiveness and abundant resources.However,the inferior cycle stability and mediocre rate per...The widespread interest in layered P2-type Mn-based cathode materials for sodium-ion batteries(SIBs)stems from their cost-effectiveness and abundant resources.However,the inferior cycle stability and mediocre rate performance impede their further development in practical applications.Herein,we devised a wet chemical precipitation method to deposit an amorphous aluminum phosphate(AlPO_(4),denoted as AP)protective layer onto the surface of P2-type Na_(0.55)Ni_(0.1)Co_(0.7)Mn_(0.8)O_(2)(NCM@AP).The resulting NCM@5AP electrode,with a 5 wt%coating,exhibits extended cycle life(capacity retention of78.4%after 200 cycles at 100 mA g^(-1))and superior rate performance(98 mA h g^(-1)at 500 mA g^(-1))compared to pristine NCM.Moreover,our investigation provides comprehensive insights into the phase stability and active Na^(+)ion kinetics in the NCM@5AP composite electrode,shedding light on the underlying mechanisms responsible for the enhanced performance observed in the coated electrode.展开更多
Sodium-ion batteries(SIBs)have rapidly risen to the forefront of energy storage systems as a promising supplementary for Lithium-ion batteries(LIBs).Na_(3)V_(2)(PO_(4))_(2)F_(3)(NVPF)as a common cathode of SIBs,featur...Sodium-ion batteries(SIBs)have rapidly risen to the forefront of energy storage systems as a promising supplementary for Lithium-ion batteries(LIBs).Na_(3)V_(2)(PO_(4))_(2)F_(3)(NVPF)as a common cathode of SIBs,features the merits of high operating voltage,small volume change and favorable specific energy density.However,it suffers from poor cycling stability and rate performance induced by its low intrinsic conductivity.Herein,we propose an ingenious strategy targeting superior SIBs through cross-linked NVPF with multi-dimensional nanocarbon frameworks composed of amorphous carbon and carbon nanotubes(NVPF@C@CNTs).This rational design ensures favorable particle size for shortened sodium ion transmission pathway as well as improved electronic transfer network,thus leading to enhanced charge transfer kinetics and superior cycling stability.Benefited from this unique structure,significantly improved electrochemical properties are obtained,including high specific capacity(126.9 mAh g^(-1)at 1 C,1 C=128 mA g^(-1))and remarkably improved long-term cycling stability with 93.9%capacity retention after 1000 cycles at 20 C.The energy density of 286.8 Wh kg^(-1)can be reached for full cells with hard carbon as anode(NVPF@C@CNTs//HC).Additionally,the electrochemical performance of the full cell at high temperature is also investigated(95.3 mAh g^(-1)after 100 cycles at 1 C at 50℃).Such nanoscale dual-carbon networks engineering and thorough discussion of ion diffusion kinetics might make contributions to accelerating the process of phosphate cathodes in SIBs for large-scale energy storages.展开更多
The development of high-energy and long-lifespan NASICON-type cathode materials for sodium-ion batteries has always been a research hotspot but a daunting challenge.Although Na_(4)MnCr(PO_(4))_(3)has emerged as one of...The development of high-energy and long-lifespan NASICON-type cathode materials for sodium-ion batteries has always been a research hotspot but a daunting challenge.Although Na_(4)MnCr(PO_(4))_(3)has emerged as one of the most promising high-energy-density cathode materials owing to its three-electron reactions,it still suffers from serious structural distortion upon repetitive charge/discharge processes caused by the Jahn-Teller active Mn^(3+).Herein,the selective substitution of Cr by Zr in Na_(4)MnCr(PO_(4))_(3)was explored to enhance the structural stability,due to the pinning effect of Zr ions and the≈2.9-electron reactions,as-prepared Na_(3.9)MnCr_(0.9)Zr_(0.1)(PO_(4))_(3)/C delivers a high capacity retention of 85.94%over 500 cycles at 5 C and an ultrahigh capacity of 156.4 mAh g^(-1)at 0.1 C,enabling the stable energy output as high as 555.2 Wh kg^(-1).Moreover,during the whole charge/discharge process,a small volume change of only 6.7%was verified by in situ X-ray diffraction,and the reversible reactions of Cr^(3+)/Cr^(4+),Mn^(3+)/Mn^(4+),and Mn^(2+)/Mn^(3+)redox couples were identified via ex situ X-ray photoelectron spectroscopy analyses.Galvanostatic intermittent titration technique tests and density functional theory calculations further demonstrated the fast reaction kinetics of the Na_(3.9)MnCr_(0.9)Zr_(0.1)(PO_(4))_(3)/C electrode.This work offers new opportunities for designing high-energy and high-stability NASICON cathodes by ion doping.展开更多
基金financially supported by the National Natural Science Foundation of China (No.51964046)。
文摘The preparation process of sodium molybdate has the disadvantages of high energy consumption,low thermal efficiency,and high raw material requirement of molybdenum trioxide,in order to realize the green and efficient development of molybdenum concentrate resources,this paper proposes a new process for efficient recovery of molybdenum from molybdenum concentrate and preparation of sodium molybdate by microwave-enhanced roasting and alkali leaching.Thermodynamic analysis indicated the feasibility of oxidation roasting of molybdenum concentrate.The effects of roasting temperature,holding time,and power-to-mass ratio on the oxidation product and leaching product sodium molybdate (Na_(2)MoO_(4)·2H_(2)O) were investigated.Under the optimal process conditions:roasting temperature of 700℃,holding time of 110 min,and power-to-mass ratio of 110 W/g,the molybdenum state of existence was converted from MoS_(2) to Mo O3.The process of preparing sodium molybdate by alkali leaching of molybdenum calcine was investigated,the optimal leaching conditions include a solution concentration of 2.5 mol/L,a liquid-to-solid ratio of 2 mL/g,a leaching temperature of 60℃,and leaching solution termination at pH 8.The optimum conditions result in a leaching rate of sodium molybdate of 96.24%.Meanwhile,the content of sodium molybdate reaches 94.08wt%after leaching and removing impurities.Iron and aluminum impurities can be effectively separated by adjusting the pH of the leaching solution with sodium carbonate solution.This research avoids the shortcomings of the traditional process and utilizes the advantages of microwave metallurgy to prepare high-quality sodium molybdate,which provides a new idea for the highvalue utilization of molybdenum concentrate.
文摘Following publication of the original article[1],the authors reported that the author Hun-Gi Jung should be affiliated as 3,4 and 5 instead of 4 and 5.The author’s name“A.-Yeon Kim”needed to be updated to“A-Yeon Kim”,removing the period.The correct author’s name and affiliation have been provided in this Correction.The original article[1]has been corrected.
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supported by Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Education,Science and Technology(NRF-2020R1A6A1A03043435,NRF-2023R1A2C2003210,and NRF-2022M3H4A1A04096478)by Technology Innovation Program(Alchemist Project,20012196,Al based supercritical materials discovery)funded by the Ministry of Trade,Industry&Energy,Korea.support from the“Bundesministerium fur Bildung und Forschung”(BMBF)and the computing time granted through JARA-HPC on the supercomputer JURECA at Forschungszentrum Julich.
文摘This study explores the impact of introducing vacancy in the transition metal layer of rationally designed Na_(0.6)[Ni_(0.3)Ru_(0.3)Mn_(0.4)]O_(2)(NRM)cathode material.The incorporation of Ru,Ni,and vacancy enhances the structural stability during extensive cycling,increases the operation voltage,and induces a capacity increase while also activating oxygen redox,respectively,in Na_(0.7)[Ni_(0.2)V_(Ni0.1)Ru_(0.3)Mn_(0.4)]O_(2)(V-NRM)compound.Various analytical techniques including transmission electron microscopy,X-ray absorption near edge spectroscopy,operando X-ray diffraction,and operando differential electrochemical mass spectrometry are employed to assess changes in the average oxidation states and structural distortions.The results demonstrate that V-NRM exhibits higher capacity than NRM and maintains a moderate capacity retention of 81%after 100 cycles.Furthermore,the formation of additional lone-pair electrons in the O 2p orbital enables V-NRM to utilize more capacity from the oxygen redox validated by density functional calculation,leading to a widened dominance of the OP4 phase without releasing O_(2) gas.These findings offer valuable insights for the design of advanced high-capacity cathode materials with improved performance and sustainability in sodium-ion batteries.
基金financially supported by the Australian Research Council(ARC) through the Future Fellowship(FT180100705)the financial support from China Scholarship Council+3 种基金the support from UTS-HUST Key Technology Partner Seed Fundthe support from Open Project of State Key Laboratory of Advanced Special Steel,the Shanghai Key Laboratory of Advanced Ferrometallurgy,Shanghai University(SKLASS 2021-04)the Science and Technology Commission of Shanghai Municipality(22010500400)“Joint International Laboratory on Environmental and Energy Frontier Materials”and“Innovation Research Team of High–Level Local Universities in Shanghai”in Shanghai University。
文摘The widespread interest in layered P2-type Mn-based cathode materials for sodium-ion batteries(SIBs)stems from their cost-effectiveness and abundant resources.However,the inferior cycle stability and mediocre rate performance impede their further development in practical applications.Herein,we devised a wet chemical precipitation method to deposit an amorphous aluminum phosphate(AlPO_(4),denoted as AP)protective layer onto the surface of P2-type Na_(0.55)Ni_(0.1)Co_(0.7)Mn_(0.8)O_(2)(NCM@AP).The resulting NCM@5AP electrode,with a 5 wt%coating,exhibits extended cycle life(capacity retention of78.4%after 200 cycles at 100 mA g^(-1))and superior rate performance(98 mA h g^(-1)at 500 mA g^(-1))compared to pristine NCM.Moreover,our investigation provides comprehensive insights into the phase stability and active Na^(+)ion kinetics in the NCM@5AP composite electrode,shedding light on the underlying mechanisms responsible for the enhanced performance observed in the coated electrode.
基金financially supported by Science and Technology Foundation of Guizhou Province(QKHZC[2020]2Y037)the Science and Technology Innovation Program of Hunan Province(2020RC4005,2019RS1004)+2 种基金Research start-up funding from Central South University(202044019)Innovation Mover Program of Central South University(2020CX007)National Natural Science Foundation of China(U21A20284)
文摘Sodium-ion batteries(SIBs)have rapidly risen to the forefront of energy storage systems as a promising supplementary for Lithium-ion batteries(LIBs).Na_(3)V_(2)(PO_(4))_(2)F_(3)(NVPF)as a common cathode of SIBs,features the merits of high operating voltage,small volume change and favorable specific energy density.However,it suffers from poor cycling stability and rate performance induced by its low intrinsic conductivity.Herein,we propose an ingenious strategy targeting superior SIBs through cross-linked NVPF with multi-dimensional nanocarbon frameworks composed of amorphous carbon and carbon nanotubes(NVPF@C@CNTs).This rational design ensures favorable particle size for shortened sodium ion transmission pathway as well as improved electronic transfer network,thus leading to enhanced charge transfer kinetics and superior cycling stability.Benefited from this unique structure,significantly improved electrochemical properties are obtained,including high specific capacity(126.9 mAh g^(-1)at 1 C,1 C=128 mA g^(-1))and remarkably improved long-term cycling stability with 93.9%capacity retention after 1000 cycles at 20 C.The energy density of 286.8 Wh kg^(-1)can be reached for full cells with hard carbon as anode(NVPF@C@CNTs//HC).Additionally,the electrochemical performance of the full cell at high temperature is also investigated(95.3 mAh g^(-1)after 100 cycles at 1 C at 50℃).Such nanoscale dual-carbon networks engineering and thorough discussion of ion diffusion kinetics might make contributions to accelerating the process of phosphate cathodes in SIBs for large-scale energy storages.
基金Financial support from the National Natural Science Foundation of China(22075016 and 22103057)Fundamental Research Funds for the Central Universities(FRF-TP-20-020A3 and QNXM20220060)+1 种基金Interdisciplinary Research Project for Young Teachers of USTB(FRF-IDRY-21-011)111 Project(B170003 and B12015)
文摘The development of high-energy and long-lifespan NASICON-type cathode materials for sodium-ion batteries has always been a research hotspot but a daunting challenge.Although Na_(4)MnCr(PO_(4))_(3)has emerged as one of the most promising high-energy-density cathode materials owing to its three-electron reactions,it still suffers from serious structural distortion upon repetitive charge/discharge processes caused by the Jahn-Teller active Mn^(3+).Herein,the selective substitution of Cr by Zr in Na_(4)MnCr(PO_(4))_(3)was explored to enhance the structural stability,due to the pinning effect of Zr ions and the≈2.9-electron reactions,as-prepared Na_(3.9)MnCr_(0.9)Zr_(0.1)(PO_(4))_(3)/C delivers a high capacity retention of 85.94%over 500 cycles at 5 C and an ultrahigh capacity of 156.4 mAh g^(-1)at 0.1 C,enabling the stable energy output as high as 555.2 Wh kg^(-1).Moreover,during the whole charge/discharge process,a small volume change of only 6.7%was verified by in situ X-ray diffraction,and the reversible reactions of Cr^(3+)/Cr^(4+),Mn^(3+)/Mn^(4+),and Mn^(2+)/Mn^(3+)redox couples were identified via ex situ X-ray photoelectron spectroscopy analyses.Galvanostatic intermittent titration technique tests and density functional theory calculations further demonstrated the fast reaction kinetics of the Na_(3.9)MnCr_(0.9)Zr_(0.1)(PO_(4))_(3)/C electrode.This work offers new opportunities for designing high-energy and high-stability NASICON cathodes by ion doping.
