Elements(As,Bi)and(Cu,Fe)exhibiting two typical segregation behavior in liquid Sb alloys were selected as solute atoms for analysis.Ab initio molecular dynamics(AIMD)simulations were employed to study the molten Sb al...Elements(As,Bi)and(Cu,Fe)exhibiting two typical segregation behavior in liquid Sb alloys were selected as solute atoms for analysis.Ab initio molecular dynamics(AIMD)simulations were employed to study the molten Sb alloy at different temperatures.By analyzing its pair correlation function(PCF),bond pairs,bond angle distribution function(BADF),and Voronoi polyhedron(VP),the short-range order(SRO)of the alloy was investigated.In the Sb melt,the solute atoms Cu and Fe,which have smaller distribution coefficients,exhibit a stronger affinity for Sb than the solute atoms As and Bi,which have larger distribution coefficients.The BADF of As and Bi with larger distribution coefficients shows a lower probability of small-angle peaks compared to large-angle peaks,whereas the BADF of Cu and Fe with smaller distribution coefficients exhibits the opposite trend.The BADF reveals that Sb-As and Sb-Bi approach pure Sb melt,while Sb-Cu and Sb-Fe deviate significantly.Compared to Sb-Cu and Sb-Fe,the Sb-As and Sb-Bi systems exhibit more low-index bonds,suggesting weaker interactions and more disorder.The VP fractions around As and Bi atoms are lower than those around Cu and Fe,and the VP face distributions around As and Bi are more complex.There are differences in the VP around different solute atoms,primarily due to the varying bond pair fractions associated with each solute atom.Fe has the smallest diffusion coefficient,primarily due to its compact local structure.展开更多
Antimony(Sb)is recognized as a potential electrode material for sodium-ion batteries(SIBs)due to its huge reserves,affordability,and high theoretical capacity(660 mAh·g^(-1)).However,Sb-based materials experience...Antimony(Sb)is recognized as a potential electrode material for sodium-ion batteries(SIBs)due to its huge reserves,affordability,and high theoretical capacity(660 mAh·g^(-1)).However,Sb-based materials experience significant volume expansion during cycling,leading to comminution of the active substance and limiting their practical use in SIBs.Therefore,the volume expansion issue of Sb-based materials during charging/discharging must be solved to create high-performance SIBs.This paper presents a detailed review of structural engineering of Sb-based electrode materials,focusing on the performance effects of different kinds of structures on advanced performance SIBs.Finally,the future development and the challenges of Sb-based materials are prospected.This paper can provide specific perspectives on the structure construction and optimization of Sb-based anode materials so as to promote the rapid development and practical applications of SIBs.展开更多
The development of sodium-ion(SIBs)and potassium-ion batteries(PIBs)has increased rapidly because of the abundant resources and cost-effectiveness of Na and K.Antimony(Sb)plays an important role in SIBs and PIBs becau...The development of sodium-ion(SIBs)and potassium-ion batteries(PIBs)has increased rapidly because of the abundant resources and cost-effectiveness of Na and K.Antimony(Sb)plays an important role in SIBs and PIBs because of its high theoretical capacity,proper working voltage,and low cost.However,Sb-based anodes have the drawbacks of large volume changes and weak charge transfer during the charge and discharge processes,thus leading to poor cycling and rapid capacity decay.To address such drawbacks,many strategies and a variety of Sb-based materials have been developed in recent years.This review systematically introduces the recent research progress of a variety of Sb-based anodes for SIBs and PIBs from the perspective of composition selection,preparation technologies,structural characteristics,and energy storage behaviors.Moreover,corresponding examples are presented to illustrate the advantages or disadvantages of these anodes.Finally,we summarize the challenges of the development of Sb-based materials for Na/K-ion batteries and propose potential research directions for their further development.展开更多
Potassium-ion batteries(PIBs)have been considered as one of the most promising alternatives to lithiumion batteries(LIBs)in view of their competitive energy density with significantly reduced product cost.Moreover,all...Potassium-ion batteries(PIBs)have been considered as one of the most promising alternatives to lithiumion batteries(LIBs)in view of their competitive energy density with significantly reduced product cost.Moreover,alloy-type materials are expected as a high-performance anode of PIBs thanks to their intrinsic chemical stability as well as high theoretical specific capacity.Unfortunately,the serious incompatibility between alloy-type active materials and electrolytes,especially for the formation of unstable solidelectrolyte interfacial(SEI)films,often leads to insufficient cycle life.Herein,the formation mechanism of SEI films in the K-storage systems based on carbon sphere confined Sb anode(Sb@CS)were investigated in commercially available electrolytes.Physical characterizations and theoretical calculation revealed that the solvents in the dilute electrolyte of 0.8 M KPF_(6)/EC+DEC were excessively decomposed on the interface to generate unstable SEI and thus result in inferior K-storage stability.On the contrary,a salt-concentrated electrolyte(3 M KFSI/DME)can generate inorganic-dominated stable SEI due to the preferential decomposition of anions.As a result,the prepared Sb@CS in the matched 3 M KFSI/DME electrolyte delivered a high reversible capacity of 467.8 m A h g^(-1)after 100 cycles at 100 m A g^(-1),with a slow capacity decay of 0.19%per cycle from the 10th to the 100th cycle.These findings are of great significance for revealing the interfacial reaction between electrodes and electrolytes as well as improving the stability of Sb-based anode materials for PIBs.展开更多
Sb-based materials exhibit considerable potential for sodium-ion storage owing to their high theoretica capacities.However,the bulk properties of Sb-based materials always result in poor cycling and rate performances....Sb-based materials exhibit considerable potential for sodium-ion storage owing to their high theoretica capacities.However,the bulk properties of Sb-based materials always result in poor cycling and rate performances.To overcome these issues,pyridine-regulated Sb@InSbS_(3)ultrafine nanoplates loaded on reduced graphene oxides(Sb@InSbS_(3)@rGO)were designed and synthesized.During the synthesis process,pyridine was initially adopted to coordinate with In^(3+),and uniformly dispersed In_(2)S_(3)ultrafine nanoplates on reduced graphene oxide were generated after sulfidation.Next,partial In^(3+)was exchanged with Sb^(3+),and Sb@InSbS_(3)@rGO was obtained by using the subsequent annealing method.The unique structure of Sb@InSbS_(3)@rGO effectively shortened the transfer path of sodium ions and electrons and provided a high pseudocapacitance.As the anode in sodium-ion batteries,the Sb@InSbS_(3)@rGO electrode demonstrated a significantly higher reversible capacity better stability(445 m Ah·g^(-1)at 0.1 A·g^(-1)after 200 cycles and 212 mAh·g^(-1)at 2 A·g^(-1)after 1200 cycles),and superior rate(210 mAh·g^(-1)at 6.4 A·g^(-1))than the electrode without pyridine(355 mAh·g-1at 0.1 A·g-1after 55 cycles and 109 mAh·g^(-1)at 2 A·g^(-1)after 770 cycles)Furthermore,full cells were assembled by using the Sb@InSbS_(3)@rGO as anode and Na_(3)V_(2)(PO_(4))_(3)as cathode which demonstrated good cycling and rate performances and exhibited promising application prospects.These results indicate that adjusting the microstructure of electrode materials through coordination balance is A·good strategy for obtaining high-capacity,high-rate,and longcycle sodium storage performances.展开更多
文摘Elements(As,Bi)and(Cu,Fe)exhibiting two typical segregation behavior in liquid Sb alloys were selected as solute atoms for analysis.Ab initio molecular dynamics(AIMD)simulations were employed to study the molten Sb alloy at different temperatures.By analyzing its pair correlation function(PCF),bond pairs,bond angle distribution function(BADF),and Voronoi polyhedron(VP),the short-range order(SRO)of the alloy was investigated.In the Sb melt,the solute atoms Cu and Fe,which have smaller distribution coefficients,exhibit a stronger affinity for Sb than the solute atoms As and Bi,which have larger distribution coefficients.The BADF of As and Bi with larger distribution coefficients shows a lower probability of small-angle peaks compared to large-angle peaks,whereas the BADF of Cu and Fe with smaller distribution coefficients exhibits the opposite trend.The BADF reveals that Sb-As and Sb-Bi approach pure Sb melt,while Sb-Cu and Sb-Fe deviate significantly.Compared to Sb-Cu and Sb-Fe,the Sb-As and Sb-Bi systems exhibit more low-index bonds,suggesting weaker interactions and more disorder.The VP fractions around As and Bi atoms are lower than those around Cu and Fe,and the VP face distributions around As and Bi are more complex.There are differences in the VP around different solute atoms,primarily due to the varying bond pair fractions associated with each solute atom.Fe has the smallest diffusion coefficient,primarily due to its compact local structure.
基金financially supported by Zhejiang Province Postdoctoral Research Project(No.ZJ 2023146)the Municipal Key R&D Program of Ningbo(No.2023Z064)。
文摘Antimony(Sb)is recognized as a potential electrode material for sodium-ion batteries(SIBs)due to its huge reserves,affordability,and high theoretical capacity(660 mAh·g^(-1)).However,Sb-based materials experience significant volume expansion during cycling,leading to comminution of the active substance and limiting their practical use in SIBs.Therefore,the volume expansion issue of Sb-based materials during charging/discharging must be solved to create high-performance SIBs.This paper presents a detailed review of structural engineering of Sb-based electrode materials,focusing on the performance effects of different kinds of structures on advanced performance SIBs.Finally,the future development and the challenges of Sb-based materials are prospected.This paper can provide specific perspectives on the structure construction and optimization of Sb-based anode materials so as to promote the rapid development and practical applications of SIBs.
基金financial support by the National Natural Science Foundation of China(Nos.51771130,51531004,and 51422104)the Tianjin Youth Talent Support Program,the Tianjin Natural Science Funds for Distinguished Young(No.17JCJQJC44300)+1 种基金the Tianjin Science and Technology Support Project(No.17ZXCLGX00060)the China Postdoctoral Science Foundation(No.2020M670649)。
文摘The development of sodium-ion(SIBs)and potassium-ion batteries(PIBs)has increased rapidly because of the abundant resources and cost-effectiveness of Na and K.Antimony(Sb)plays an important role in SIBs and PIBs because of its high theoretical capacity,proper working voltage,and low cost.However,Sb-based anodes have the drawbacks of large volume changes and weak charge transfer during the charge and discharge processes,thus leading to poor cycling and rapid capacity decay.To address such drawbacks,many strategies and a variety of Sb-based materials have been developed in recent years.This review systematically introduces the recent research progress of a variety of Sb-based anodes for SIBs and PIBs from the perspective of composition selection,preparation technologies,structural characteristics,and energy storage behaviors.Moreover,corresponding examples are presented to illustrate the advantages or disadvantages of these anodes.Finally,we summarize the challenges of the development of Sb-based materials for Na/K-ion batteries and propose potential research directions for their further development.
基金support from the National Natural Science Foundation of China(21771107,21902077)the Natural Science Foundation of Jiangsu Province(BK20190381,BK20201287)。
文摘Potassium-ion batteries(PIBs)have been considered as one of the most promising alternatives to lithiumion batteries(LIBs)in view of their competitive energy density with significantly reduced product cost.Moreover,alloy-type materials are expected as a high-performance anode of PIBs thanks to their intrinsic chemical stability as well as high theoretical specific capacity.Unfortunately,the serious incompatibility between alloy-type active materials and electrolytes,especially for the formation of unstable solidelectrolyte interfacial(SEI)films,often leads to insufficient cycle life.Herein,the formation mechanism of SEI films in the K-storage systems based on carbon sphere confined Sb anode(Sb@CS)were investigated in commercially available electrolytes.Physical characterizations and theoretical calculation revealed that the solvents in the dilute electrolyte of 0.8 M KPF_(6)/EC+DEC were excessively decomposed on the interface to generate unstable SEI and thus result in inferior K-storage stability.On the contrary,a salt-concentrated electrolyte(3 M KFSI/DME)can generate inorganic-dominated stable SEI due to the preferential decomposition of anions.As a result,the prepared Sb@CS in the matched 3 M KFSI/DME electrolyte delivered a high reversible capacity of 467.8 m A h g^(-1)after 100 cycles at 100 m A g^(-1),with a slow capacity decay of 0.19%per cycle from the 10th to the 100th cycle.These findings are of great significance for revealing the interfacial reaction between electrodes and electrolytes as well as improving the stability of Sb-based anode materials for PIBs.
基金supported by the National Natural Science Foundation of China(Nos.42007138,51772082 and 51804106)the Natural Science Foundation of Hunan Province(No.2023JJ10005).
文摘Sb-based materials exhibit considerable potential for sodium-ion storage owing to their high theoretica capacities.However,the bulk properties of Sb-based materials always result in poor cycling and rate performances.To overcome these issues,pyridine-regulated Sb@InSbS_(3)ultrafine nanoplates loaded on reduced graphene oxides(Sb@InSbS_(3)@rGO)were designed and synthesized.During the synthesis process,pyridine was initially adopted to coordinate with In^(3+),and uniformly dispersed In_(2)S_(3)ultrafine nanoplates on reduced graphene oxide were generated after sulfidation.Next,partial In^(3+)was exchanged with Sb^(3+),and Sb@InSbS_(3)@rGO was obtained by using the subsequent annealing method.The unique structure of Sb@InSbS_(3)@rGO effectively shortened the transfer path of sodium ions and electrons and provided a high pseudocapacitance.As the anode in sodium-ion batteries,the Sb@InSbS_(3)@rGO electrode demonstrated a significantly higher reversible capacity better stability(445 m Ah·g^(-1)at 0.1 A·g^(-1)after 200 cycles and 212 mAh·g^(-1)at 2 A·g^(-1)after 1200 cycles),and superior rate(210 mAh·g^(-1)at 6.4 A·g^(-1))than the electrode without pyridine(355 mAh·g-1at 0.1 A·g-1after 55 cycles and 109 mAh·g^(-1)at 2 A·g^(-1)after 770 cycles)Furthermore,full cells were assembled by using the Sb@InSbS_(3)@rGO as anode and Na_(3)V_(2)(PO_(4))_(3)as cathode which demonstrated good cycling and rate performances and exhibited promising application prospects.These results indicate that adjusting the microstructure of electrode materials through coordination balance is A·good strategy for obtaining high-capacity,high-rate,and longcycle sodium storage performances.
