Phosphorus is the potential anode material for emerging potassium-ion batteries(PIBs)owing to the highest specific capacity and relatively low operation plateau.However,the reversible delivered capacities of phosphoru...Phosphorus is the potential anode material for emerging potassium-ion batteries(PIBs)owing to the highest specific capacity and relatively low operation plateau.However,the reversible delivered capacities of phosphorus-based anodes,in reality,are far from the theoretical capacity corresponding to the formation of K3P alloy.And,their underlying potassium storage mechanisms remain poorly understood.To address this issue,for the first time,we perform high-resolution solid-state31P NMR combined with XRD measurements,and density functional theory calculations to yield a systemic quantitative understanding of(de)potassiation reaction mechanism of phosphorus anode.We explicitly reveal a previously unknown asymmetrical nanocrystalline-to-amorphous transition process via rP←→(K_(3)P_(11),K_(3)P_(7),beta-K_(4)P_(6))←→(alpha-K4P6)←→(K_(1-x)P,KP,K_(4-x)P3,K_(1+x)P)←→(amorphous K4P3,amorphous K3P)that are proceed along with the electrochemical potassiation/depotassiation processes.Additionally,the corresponding KP alloys intermediates,such as the amorphous phases of K_(4)P_(3),K_(3)P,and the nonstoichiometric phases of“K_(1-x)P”,“K_(1+x)P”,“K_(4-x)P_(3)”are experimentally detected,which indicating various complicated K-P alloy species are coexisted and evolved with the sluggish electrochemical reaction kinetics,resulting in lower capacity of phosphorus-based anodes.Our findings offer some insights into the specific multi-phase evolution mechanism of alloying anodes that may be generally involved in conversion-type electrode materials for PIBs.展开更多
Current studies of cathodes for potassium batteries(PBs) mainly focus on the intercalation-type materials.The conversion-type materials that possess much higher theoretical capacities are rarely discussed in previous ...Current studies of cathodes for potassium batteries(PBs) mainly focus on the intercalation-type materials.The conversion-type materials that possess much higher theoretical capacities are rarely discussed in previous literatures.In this work,carbon fluoride(CF_x) is reported as a high capacity conversion-type cathode for PBs for the first time.The material delivers a remarkable discharge capacity of>250 mAh g^(-1) with mid-voltage of 2.6 V at 20 mA g^(-1).Moreover,a highly reversible capacity of around 95 mAh g^(-1) is achieved at 125 mA g^(-1) and maintained for 900 cycles,demonstrating its excellent cycling stability.The mechanism of this highly reversible conversion reaction is further investigated by nuclear magnetic resonance spectra,X-ray diffraction,and transmission electron microscopy studies.According to the analyses,the C-F bond in the cycled material is different from that in the pristine state,which presents relatively higher reversibility.This finding offers important insights for further improving the performance of the CF_x.This work not only demonstrates the CF_x as a high performance cathode for PBs,but also paves a new avenue of exploring conversion-type cathodes for high energy density PBs.展开更多
The synthesis of active electrode materials at room temperature is one of the effective strategies to reduce the fabrication cost of sodium ion batteries(SIBs).Herein,a layered material(Na_(2)[(VO)_(2)(HPO_(4))_(2)C_(...The synthesis of active electrode materials at room temperature is one of the effective strategies to reduce the fabrication cost of sodium ion batteries(SIBs).Herein,a layered material(Na_(2)[(VO)_(2)(HPO_(4))_(2)C_(2)O_(4)]·2H_(2)O,abbreviated as NVPC followingly)with open-framework structures has been successfully prepared at room temperature under ambient conditions and is evaluated as a cathode for SIBs.It is revealed that NVPC cathode can deliver a maximum reversible capacity of ca.70 mAh/g at 10 mA/g,and exhibit superior rate capability and cycling performance:at 50 mA/g,maximum reversible capacity ca.50 m Ah/g with capacity retention of 88.4%over 250 cycles corresponds to only 0.046%capacity decay per cycle;at 100 mA/g,a maximum reversible capacity of 35 mAh/g with capacity retention of60.9%over 500 cycles.This study demonstrates a practical example of a low-cost synthesis of the cathode materials for SIBs.At the same time,the systematic electrochemical research results also show promising prospects for long lifespan low-cost SIBs.展开更多
基金financially supported by National Nature Science Foundation of China(Grant No.22272175,21805278,52072323,52122211)the Fujian Science and Technology Planning Projects of China(2020T3022,2022T3067)+3 种基金the National Key R&D Program of China(No.2021YFB3500400)the Future-prospective and Stride-across Programs of Haixi Institutes,Chinese Academy of Sciences(No.CXZX-2022-GH02)the Youth Innovation Foundation of Xiamen City(Grant No.3502Z20206083)the Opening Project of PCOSS,Xiamen University(Grant No.202014)。
文摘Phosphorus is the potential anode material for emerging potassium-ion batteries(PIBs)owing to the highest specific capacity and relatively low operation plateau.However,the reversible delivered capacities of phosphorus-based anodes,in reality,are far from the theoretical capacity corresponding to the formation of K3P alloy.And,their underlying potassium storage mechanisms remain poorly understood.To address this issue,for the first time,we perform high-resolution solid-state31P NMR combined with XRD measurements,and density functional theory calculations to yield a systemic quantitative understanding of(de)potassiation reaction mechanism of phosphorus anode.We explicitly reveal a previously unknown asymmetrical nanocrystalline-to-amorphous transition process via rP←→(K_(3)P_(11),K_(3)P_(7),beta-K_(4)P_(6))←→(alpha-K4P6)←→(K_(1-x)P,KP,K_(4-x)P3,K_(1+x)P)←→(amorphous K4P3,amorphous K3P)that are proceed along with the electrochemical potassiation/depotassiation processes.Additionally,the corresponding KP alloys intermediates,such as the amorphous phases of K_(4)P_(3),K_(3)P,and the nonstoichiometric phases of“K_(1-x)P”,“K_(1+x)P”,“K_(4-x)P_(3)”are experimentally detected,which indicating various complicated K-P alloy species are coexisted and evolved with the sluggish electrochemical reaction kinetics,resulting in lower capacity of phosphorus-based anodes.Our findings offer some insights into the specific multi-phase evolution mechanism of alloying anodes that may be generally involved in conversion-type electrode materials for PIBs.
基金financially supported by the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB20000000)the Key Program of Frontier Science, CAS (QYZDJ-SSW-SLH033)+4 种基金the National Natural Science Foundation of China (21603231, 21805278, 21875252 and 21521061)the Leading Project Foundation of Science Department of Fujian Province (2018H0034)the Natural Science Foundation of Fujian Province (2017J05039, 2006L2005)the FJIRSM&IUE Joint Research Fund (No. RHZX-2018-002)FJIRSM Project (CXZX-2017-T04)。
文摘Current studies of cathodes for potassium batteries(PBs) mainly focus on the intercalation-type materials.The conversion-type materials that possess much higher theoretical capacities are rarely discussed in previous literatures.In this work,carbon fluoride(CF_x) is reported as a high capacity conversion-type cathode for PBs for the first time.The material delivers a remarkable discharge capacity of>250 mAh g^(-1) with mid-voltage of 2.6 V at 20 mA g^(-1).Moreover,a highly reversible capacity of around 95 mAh g^(-1) is achieved at 125 mA g^(-1) and maintained for 900 cycles,demonstrating its excellent cycling stability.The mechanism of this highly reversible conversion reaction is further investigated by nuclear magnetic resonance spectra,X-ray diffraction,and transmission electron microscopy studies.According to the analyses,the C-F bond in the cycled material is different from that in the pristine state,which presents relatively higher reversibility.This finding offers important insights for further improving the performance of the CF_x.This work not only demonstrates the CF_x as a high performance cathode for PBs,but also paves a new avenue of exploring conversion-type cathodes for high energy density PBs.
基金financially supported by the National Natural Science Foundation of China(No.21805278)。
文摘The synthesis of active electrode materials at room temperature is one of the effective strategies to reduce the fabrication cost of sodium ion batteries(SIBs).Herein,a layered material(Na_(2)[(VO)_(2)(HPO_(4))_(2)C_(2)O_(4)]·2H_(2)O,abbreviated as NVPC followingly)with open-framework structures has been successfully prepared at room temperature under ambient conditions and is evaluated as a cathode for SIBs.It is revealed that NVPC cathode can deliver a maximum reversible capacity of ca.70 mAh/g at 10 mA/g,and exhibit superior rate capability and cycling performance:at 50 mA/g,maximum reversible capacity ca.50 m Ah/g with capacity retention of 88.4%over 250 cycles corresponds to only 0.046%capacity decay per cycle;at 100 mA/g,a maximum reversible capacity of 35 mAh/g with capacity retention of60.9%over 500 cycles.This study demonstrates a practical example of a low-cost synthesis of the cathode materials for SIBs.At the same time,the systematic electrochemical research results also show promising prospects for long lifespan low-cost SIBs.
