Ethylene carbonate(EC)is widely used in lithium-ion batteries due to its optimal overall performance with satisfactory conductivity,relatively stable solid electrolyte interphase(SEI),and wide electrochemical window.E...Ethylene carbonate(EC)is widely used in lithium-ion batteries due to its optimal overall performance with satisfactory conductivity,relatively stable solid electrolyte interphase(SEI),and wide electrochemical window.EC is also the most widely used electrolyte solvent in sodium ion batteries.However,compared to lithium metal,sodium metal(Na)shows higher activity and reacts violently with EC-based electrolyte(NaPF_(6)as solute),which leads to the failure of sodium metal batteries(SMBs).Herein,we reveal the electrochemical instability mechanism of EC on sodium metal battery,and find that the com-bination of EC and NaPF_(6) is electrically reduced in sodium metal anode during charging,resulting in the reduction of the first coulombic efficiency,and the continuous consumption of electrolyte leads to the cell failure.To address the above issues,an additive modified linear carbonate-based electrolyte is provided as a substitute for EC based electrolytes.Specifically,ethyl methyl carbonate(EMC)and dimethyl carbon-ate(DMC)as solvents and fluoroethylene carbonate(FEC)as SEI-forming additive have been identified as the optimal solvent for NaFP_(6)based electrolyte and used in Na_(4)Fe_(3)(PO_(4))_(2)(P_(2)O_(7))/Na batteries.The batter-ies exhibit excellent capacity retention rate of about 80%over 1000 cycles at a cut-off voltage of 4.3 V.展开更多
Na_(3)V_(2)(PO_(4))_(3)(NVP)cathode material of the sodium ion battery(1 C=117 mAh g-1)has a NASICON-type structure,which not only facilitates the rapid migration of sodium ions,but also has a small volume deformation...Na_(3)V_(2)(PO_(4))_(3)(NVP)cathode material of the sodium ion battery(1 C=117 mAh g-1)has a NASICON-type structure,which not only facilitates the rapid migration of sodium ions,but also has a small volume deformation during sodium ion de-intercalation and the main frame mechanism remains unchanged,and thus is seen as an energy storage material for a wide range of applications,but has a limited electronic conductivity due to its structure.In this paper,NVP cathode materials with finer primary particles are successfully prepared using a simple hydrothermal treatment-assisted sol-gel method.The increased pore size of the NVP materials prepared under the hydrothermal process allows for more active sites and more effective resistance to the volume deformation of sodium ions during insertion/extraction processes,effectively facilitating the diffusion of ions and electrons.The Na_(3)V_(2)(PO_(4))_(3) material obtained by the optimized process exhibited good crystallinity in XRD characterization,as well as superior electrochemical properties in a series of electrochemical tests.A specific capacitance of 106.3 mAh g^(-1) at 0.2 C is demonstrated,compared to 96.5 mAh g^(-1) for Na_(3)V_(2)(PO_(4))_(3) without hydrothermal treatment,and cycling performance is also improved with 93%capacity retention.The calculated sodium ion diffusion coefficient(DNa=5.68×10^(-14))obtained after EIS curve fitting of the improved sample illustrates that the pore structure is beneficial to the performance of the Na_(3)V_(2)(PO_(4))_(3)cathode material.展开更多
基金supported by the National Natural Science Foundation of China(52172201,51732005,51902118,and 52102249)the China Postdoctoral Science Foundation(2019M662609and 2020T130217)for financial support。
文摘Ethylene carbonate(EC)is widely used in lithium-ion batteries due to its optimal overall performance with satisfactory conductivity,relatively stable solid electrolyte interphase(SEI),and wide electrochemical window.EC is also the most widely used electrolyte solvent in sodium ion batteries.However,compared to lithium metal,sodium metal(Na)shows higher activity and reacts violently with EC-based electrolyte(NaPF_(6)as solute),which leads to the failure of sodium metal batteries(SMBs).Herein,we reveal the electrochemical instability mechanism of EC on sodium metal battery,and find that the com-bination of EC and NaPF_(6) is electrically reduced in sodium metal anode during charging,resulting in the reduction of the first coulombic efficiency,and the continuous consumption of electrolyte leads to the cell failure.To address the above issues,an additive modified linear carbonate-based electrolyte is provided as a substitute for EC based electrolytes.Specifically,ethyl methyl carbonate(EMC)and dimethyl carbon-ate(DMC)as solvents and fluoroethylene carbonate(FEC)as SEI-forming additive have been identified as the optimal solvent for NaFP_(6)based electrolyte and used in Na_(4)Fe_(3)(PO_(4))_(2)(P_(2)O_(7))/Na batteries.The batter-ies exhibit excellent capacity retention rate of about 80%over 1000 cycles at a cut-off voltage of 4.3 V.
文摘Na_(3)V_(2)(PO_(4))_(3)(NVP)cathode material of the sodium ion battery(1 C=117 mAh g-1)has a NASICON-type structure,which not only facilitates the rapid migration of sodium ions,but also has a small volume deformation during sodium ion de-intercalation and the main frame mechanism remains unchanged,and thus is seen as an energy storage material for a wide range of applications,but has a limited electronic conductivity due to its structure.In this paper,NVP cathode materials with finer primary particles are successfully prepared using a simple hydrothermal treatment-assisted sol-gel method.The increased pore size of the NVP materials prepared under the hydrothermal process allows for more active sites and more effective resistance to the volume deformation of sodium ions during insertion/extraction processes,effectively facilitating the diffusion of ions and electrons.The Na_(3)V_(2)(PO_(4))_(3) material obtained by the optimized process exhibited good crystallinity in XRD characterization,as well as superior electrochemical properties in a series of electrochemical tests.A specific capacitance of 106.3 mAh g^(-1) at 0.2 C is demonstrated,compared to 96.5 mAh g^(-1) for Na_(3)V_(2)(PO_(4))_(3) without hydrothermal treatment,and cycling performance is also improved with 93%capacity retention.The calculated sodium ion diffusion coefficient(DNa=5.68×10^(-14))obtained after EIS curve fitting of the improved sample illustrates that the pore structure is beneficial to the performance of the Na_(3)V_(2)(PO_(4))_(3)cathode material.
