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
Sodium superionic conductors(NASICONs)show significant promise for application in the development of cathodes for sodium-ion batteries(SIBs).However,it remains a major challenge to develop the desired multi-electron r...Sodium superionic conductors(NASICONs)show significant promise for application in the development of cathodes for sodium-ion batteries(SIBs).However,it remains a major challenge to develop the desired multi-electron reaction cathode with a high specific capacity and energy density.Herein,we report a novel NASICON-type Na_(3.5)MnCr_(0.5)Ti_(0.5)(PO_(4))_(3)cathode obtained by combining electrospinning and stepwise sintering processes.This cathode exhibits a high discharge capacity of 160.4 mAh g^(−1)and operates at a considerable medium voltage of 3.2 V.The Na_(3.5)MnCr_(0.5)Ti_(0.5)(PO_(4))_(3)cathode undergoes a multi-electron redox reaction involving the Cr^(3+/4+)(4.40/4.31 V vs.Na/Na^(+)),Mn^(3+/4+)(4.18/4.03 V),Mn^(2+/3+)(3.74/3.41 V),and Ti^(3+/4+)(2.04/2.14 V)redox couples.This redox reaction enables a three-electron transfer during the Na+intercalation/de-intercalation processes.As a result,the Na_(3.5)MnCr_(0.5)Ti_(0.5)(PO_(4))_(3)demonstrates a significant enhancement in energy density,surpassing other recently reported SIB cathodes.The highly reversible structure evolution and small volume changes during cycling were demonstrated with in-situ X-ray diffraction,ensuring outstanding cyclability with 77%capacity retention after 500 cycles.Furthermore,a NMCTP@C//Sb@C full battery was fabricated,which delivered a high energy density of 421 Wh kg−1 and exhibited good cyclability with 75.7%capacity retention after 100 cycles.The rational design of composition regulation with multi-metal ion substitution holds the potential to unlock new possibilities in achieving high-performance SIBs.展开更多
Rare earth mineral fast ion conductors of Li 1+2 x+3y Al x Sc y Zn y Ti 2- x-2y Si x P 3- x O 12 system based on LiTi 2(PO 4) 3 were prepared by solid phase reaction at hig...Rare earth mineral fast ion conductors of Li 1+2 x+3y Al x Sc y Zn y Ti 2- x-2y Si x P 3- x O 12 system based on LiTi 2(PO 4) 3 were prepared by solid phase reaction at high temperature (1000～1300 ℃) for about 30 h using refined natural kaolinite and Sc 2O 3. The X ray diffraction analysis shows that a Nasicon like structure with R3c space group can be found in the composition range of x =0.1, 0.2, y ≤0.2. The maximum lithium ion conductivity is 1.19×10 -4 S·cm -1 for the composition with x =0.1, y =0.08 at room temperature, and its activation energy is 30.6 kJ·mol -1 in the temperature range of 150～300 ℃. The systems with these compositions have high conductivity of about 10 -2 S·cm -1 at 300 ℃.展开更多
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supported by the National Natural Science Foundation of China(52302304,52102299,52102295)the Guangdong Basic and Applied Basic Research Foundation(2021A1515110059)+3 种基金the Natural Science Foundation of Hubei Provincial(2023AFB999)the Fundamental Research Funds for the Central Universities(WUT:2021IVA034B,2022-xcs4)Hainan Provincial Joint Project of Sanya Yazhou Bay Science and Technology City(520LH055)the Sanya Science and Education Innovation Park of Wuhan University of Technology(2021KF0019).
文摘Sodium superionic conductors(NASICONs)show significant promise for application in the development of cathodes for sodium-ion batteries(SIBs).However,it remains a major challenge to develop the desired multi-electron reaction cathode with a high specific capacity and energy density.Herein,we report a novel NASICON-type Na_(3.5)MnCr_(0.5)Ti_(0.5)(PO_(4))_(3)cathode obtained by combining electrospinning and stepwise sintering processes.This cathode exhibits a high discharge capacity of 160.4 mAh g^(−1)and operates at a considerable medium voltage of 3.2 V.The Na_(3.5)MnCr_(0.5)Ti_(0.5)(PO_(4))_(3)cathode undergoes a multi-electron redox reaction involving the Cr^(3+/4+)(4.40/4.31 V vs.Na/Na^(+)),Mn^(3+/4+)(4.18/4.03 V),Mn^(2+/3+)(3.74/3.41 V),and Ti^(3+/4+)(2.04/2.14 V)redox couples.This redox reaction enables a three-electron transfer during the Na+intercalation/de-intercalation processes.As a result,the Na_(3.5)MnCr_(0.5)Ti_(0.5)(PO_(4))_(3)demonstrates a significant enhancement in energy density,surpassing other recently reported SIB cathodes.The highly reversible structure evolution and small volume changes during cycling were demonstrated with in-situ X-ray diffraction,ensuring outstanding cyclability with 77%capacity retention after 500 cycles.Furthermore,a NMCTP@C//Sb@C full battery was fabricated,which delivered a high energy density of 421 Wh kg−1 and exhibited good cyclability with 75.7%capacity retention after 100 cycles.The rational design of composition regulation with multi-metal ion substitution holds the potential to unlock new possibilities in achieving high-performance SIBs.
文摘Rare earth mineral fast ion conductors of Li 1+2 x+3y Al x Sc y Zn y Ti 2- x-2y Si x P 3- x O 12 system based on LiTi 2(PO 4) 3 were prepared by solid phase reaction at high temperature (1000～1300 ℃) for about 30 h using refined natural kaolinite and Sc 2O 3. The X ray diffraction analysis shows that a Nasicon like structure with R3c space group can be found in the composition range of x =0.1, 0.2, y ≤0.2. The maximum lithium ion conductivity is 1.19×10 -4 S·cm -1 for the composition with x =0.1, y =0.08 at room temperature, and its activation energy is 30.6 kJ·mol -1 in the temperature range of 150～300 ℃. The systems with these compositions have high conductivity of about 10 -2 S·cm -1 at 300 ℃.
