Bismuth has drawn widespread attention as a prospective alloying-type anode for sodium-ion batteries(SIBs)and potassium-ion batteries(PIBs)due to its large volumetric capacity.However,such material encounters drastic ...Bismuth has drawn widespread attention as a prospective alloying-type anode for sodium-ion batteries(SIBs)and potassium-ion batteries(PIBs)due to its large volumetric capacity.However,such material encounters drastic particle pulverization and overgrowth of solid-electrolyte interphase(SEI)upon repeated(de)alloying,thus causing poor rate and cycling degradation.Herein,we report a unique structure design with bismuth nanorods confined in hollow N,S-codoped carbon nanotubes(Bi@NS-C)fabricated by a solvothermal method and in-situ thermal reduction.Ex-situ SEM observations confirm that such a design can significantly suppress the size fining of Bi nanorods,thus inhibiting the particle pulverization and repeated SEI growth upon charging/discharging.The as achieved Bi@NS-C demonstrates outstanding rate capability for SIBs(96.5%capacity retention at 30 A g^(-1) vs.1 A g^(-1)),and a record high rate performance for PIBs(399.5 m Ah g^(-1)@20 A g^(-1)).Notably,the as constructed full cell(Na_(3)V_(2)(PO_(4))_(3)@C|Bi@NS-C)demonstrates impressive performance with a high energy density of 219.8 W h kg^(-1) and a high-power density of 6443.3 W kg^(-1)(based on the total mass of active materials on both electrodes),outperforming the state-of-the-art literature.展开更多
The electrochemical performance of hard carbon(HC)materials is closely related to the electrolyte used in the sodium ion batteries(SIBs).Conventional electrolytes carbonate(EC)demonstrates low initial Columbic efficie...The electrochemical performance of hard carbon(HC)materials is closely related to the electrolyte used in the sodium ion batteries(SIBs).Conventional electrolytes carbonate(EC)demonstrates low initial Columbic efficiency(ICE)and poor rate performance,which is one of the main bottlenecks that limits the practical application of HCs.Ether electrolyte(diglyme)was reported to improve the rate performance of HCs.Nevertheless,the underlying mechanism for the excellent rate capability is still lack of in-depth study.In this work,the differences of sodium-ion diffusion between ether and carbonate-base electrolytes in HCs are analyzed layer by layer.Firstly,when sodium-ions are diffused in electrolyte,the diffusion coefficient of sodium-ion in ether electrolyte is about 2.5 times higher than that in ester electrolytes by molecular dynamics(MD)simulation and experimental characterization.Furthermore,when the solvated sodium-ions are diffused into the solid electrolyte interphase(SEI)interface and the HCs material,the enhanced charge transfer kinetics(thin SEI layer(4.6 vs.12 nm)and low RSEI(1.5 vs.24Ω))at the SEI combined with low desolvation energy(0.248 eV)are responsible for high-rate performance and good cycling stability of HC in ether electrolyte.Therefore,high diffusion coefficient,low desolvation energy,and good interface are the intrinsic reasons for enhanced rate performance in ether electrolyte,which also has guiding significance for the design of other high-rate electrolytes.展开更多
基金supported by the National Natural Science Foundation of China(22179077,51774251)the Shanghai Science and Technology Commission’s"2020 Science and Technology Innovation Action Plan"(20511104003)+2 种基金the Natural Science Foundation in Shanghai(21ZR1424200)the Hebei Natural Science Foundation for Distinguished Young Scholars(B2017203313)the Scientific Research Foundation for the Returned Overseas Chinese Scholars(CG2014003002)。
文摘Bismuth has drawn widespread attention as a prospective alloying-type anode for sodium-ion batteries(SIBs)and potassium-ion batteries(PIBs)due to its large volumetric capacity.However,such material encounters drastic particle pulverization and overgrowth of solid-electrolyte interphase(SEI)upon repeated(de)alloying,thus causing poor rate and cycling degradation.Herein,we report a unique structure design with bismuth nanorods confined in hollow N,S-codoped carbon nanotubes(Bi@NS-C)fabricated by a solvothermal method and in-situ thermal reduction.Ex-situ SEM observations confirm that such a design can significantly suppress the size fining of Bi nanorods,thus inhibiting the particle pulverization and repeated SEI growth upon charging/discharging.The as achieved Bi@NS-C demonstrates outstanding rate capability for SIBs(96.5%capacity retention at 30 A g^(-1) vs.1 A g^(-1)),and a record high rate performance for PIBs(399.5 m Ah g^(-1)@20 A g^(-1)).Notably,the as constructed full cell(Na_(3)V_(2)(PO_(4))_(3)@C|Bi@NS-C)demonstrates impressive performance with a high energy density of 219.8 W h kg^(-1) and a high-power density of 6443.3 W kg^(-1)(based on the total mass of active materials on both electrodes),outperforming the state-of-the-art literature.
基金supported by the National Natural Science Foundation of China(Nos.22179077,51774251,and 21908142)Shanghai Science and Technology Commission’s“2020 Science and Technology In-novation Action Plan”(No.20511104003)Natural Science Foundation in Shanghai(No.21ZR1424200).
文摘The electrochemical performance of hard carbon(HC)materials is closely related to the electrolyte used in the sodium ion batteries(SIBs).Conventional electrolytes carbonate(EC)demonstrates low initial Columbic efficiency(ICE)and poor rate performance,which is one of the main bottlenecks that limits the practical application of HCs.Ether electrolyte(diglyme)was reported to improve the rate performance of HCs.Nevertheless,the underlying mechanism for the excellent rate capability is still lack of in-depth study.In this work,the differences of sodium-ion diffusion between ether and carbonate-base electrolytes in HCs are analyzed layer by layer.Firstly,when sodium-ions are diffused in electrolyte,the diffusion coefficient of sodium-ion in ether electrolyte is about 2.5 times higher than that in ester electrolytes by molecular dynamics(MD)simulation and experimental characterization.Furthermore,when the solvated sodium-ions are diffused into the solid electrolyte interphase(SEI)interface and the HCs material,the enhanced charge transfer kinetics(thin SEI layer(4.6 vs.12 nm)and low RSEI(1.5 vs.24Ω))at the SEI combined with low desolvation energy(0.248 eV)are responsible for high-rate performance and good cycling stability of HC in ether electrolyte.Therefore,high diffusion coefficient,low desolvation energy,and good interface are the intrinsic reasons for enhanced rate performance in ether electrolyte,which also has guiding significance for the design of other high-rate electrolytes.