Rechargeable aluminum batteries(RABs)are attractive cadidates for next-generation energy storage and conversion,due to the low cost and high safety of Al resources,and high capacity of metal Al based on the three-elec...Rechargeable aluminum batteries(RABs)are attractive cadidates for next-generation energy storage and conversion,due to the low cost and high safety of Al resources,and high capacity of metal Al based on the three-electrons reaction mechanism.However,the development of RABs is greatly limited,because of the lack of advanced cathode materials,and their complicated and unclear reaction mechanisms.Exploring the novel nanostructured transition metal and carbon composites is an effective route for obtaining ideal cathode materials.In this work,we synthesize porous CoSnO_(3)/C nanocubes with oxygen vacancies for utilizing as cathodes in RABs for the first time.The intrinsic structure stability of the mixed metal cations and carbon coating can improve the cycling performance of cathodes by regulating the internal strains of the electrodes during volume expansion.The nanocubes with porous structures contribute to fast mass transportation which improves the rate capability.In addition to this,abundant oxygen vacancies promote the adsorption affinity of cathodes,which improves storage capacity.As a result,the CoSnO_(3)/C cathodes display an excellent reversible capacity of 292.1 mAh g^(-1) at 0.1 A g^(-1),a good rate performance with 109 mAh g^(-1) that is maintained even at 1 A g^(-1) and the provided stable cycling behavior for 500 cycles.Besides,a mechanism of intercalation of Al^(3+)within CoSnO_(3)/C cathode is proposed for the electrochemical process.Overall,this work provides a step toward the development of advanced cathode materials for RABs by engineering novel nanostructured mixed transition-metal oxides with carbon composite and proposes novel insights into chemistry for RABs.展开更多
In this work, we report a facile route for the synthesis of Li3V2(PO4)3/C cathode material via freezedrying and then calcination. The effect of calcination temperature on the electrochemical properties of the Li3V2(PO...In this work, we report a facile route for the synthesis of Li3V2(PO4)3/C cathode material via freezedrying and then calcination. The effect of calcination temperature on the electrochemical properties of the Li3V2(PO4)3/C is also investigated. When used as a lithium-ion battery cathode, the optimized Li3V2(PO4)3/C (LVP-800) through calcination at 800 ℃ exhibits a high initial charge and discharge capacity. The excellent electrochemical performance of LVP-800 is attributed to the good crystallinity and uniform morphology of the electrode material. In addition, the residual carbon can also improve the conductivity and buffer the volume expansion during the Li-ion extraction/reinsertion. Meanwhile, charge compensation also plays an important role in excellent electrochemical performance.展开更多
Li4Ti5012 (LTO) with rich R-TiO2 (17.06, 23.69, and 34.42 wt%), namely, R-TiO2@Li4Ti5O12 composites, were synthesized using the hydrothermal method and tetrabutyl titanate (TBT) as the precursor. Rietveld refinement o...Li4Ti5012 (LTO) with rich R-TiO2 (17.06, 23.69, and 34.42 wt%), namely, R-TiO2@Li4Ti5O12 composites, were synthesized using the hydrothermal method and tetrabutyl titanate (TBT) as the precursor. Rietveld refinement of X-ray diffraction (XRD) results show that the proportion of Li occupying 16d sites is extraordinary low and the lattice constants of LTO and R-TiO2 change with the ritanium dioxide content. EIS measurements showed that with in creasing R-TiO2 content, both its charge transfer impedance (Rct) and lithium ion diffusion coefficient (DLi) decreased. The changes of Rct and DLi caused by the increase of titanium dioxide content have synergic-antagonistic effects on the rate and cycle properties of Li4Ti5012. The rate performance is positively related to DLi, while the cycle property is negatively correlated with Rct, indicati ng that the rate performs nee is mainly related to DLi, while Rct more significantly affects the cycle performance. LTO-RT-17.06% exhibited excellent rate properties, especially under a high current density (5.0 C, 132.5 mAh/g) and LTO-RT-34.42% showed superior long-term cycle performance (0.012% capacity loss per cycle) compared to that of LTO-RT-17.06% and LTO-RT-23.69%.展开更多
Rechargeable aluminum ion battery(AIB) with high theoretical specific capacity, abundant elements and low cost engages considerable attention as a promising next generation energy storage and conversion system. Nevert...Rechargeable aluminum ion battery(AIB) with high theoretical specific capacity, abundant elements and low cost engages considerable attention as a promising next generation energy storage and conversion system. Nevertheless, to date, one of the major barriers to pursuit better AIB is the limited applicable cathode materials with the ability to store aluminum highly reversibly. Herein, a highly reversible AIB is proposed using mesoporous TiO2 microparticles(M-TiO2) as the cathode material. The improved performance of Ti O2/Al battery is ascribed to the high ionic conductivity and material stability, which is caused by the stable architecture with a mesoporous microstructure and no random aggregation of secondary particles. In addition, we conducted detailed characterization to gain deeper understanding of the Al^(3+) storage mechanism in anatase Ti O2 for AIB. Our findings demonstrate clearly that Al^(3+)can be reversibly stored in anatase TiO2 by intercalation reactions based on ionic liquid electrolyte. Especially, DFT calculations were used to investigate the accurate insertion sites of aluminum ions in M-Ti O2 and the volume changes of M-TiO2 cells during discharging. As for the controversial side reactions in AIBs, in this work, by normalized calculation, we confirm that M-Ti O2 alone participate in the redox reaction. Moreover, cyclic voltammetry(CV) test was performed to investigate the pseudocapacitive behavior.展开更多
基金supported by the National Natural Science Foundation of China (Grant No.22075028).
文摘Rechargeable aluminum batteries(RABs)are attractive cadidates for next-generation energy storage and conversion,due to the low cost and high safety of Al resources,and high capacity of metal Al based on the three-electrons reaction mechanism.However,the development of RABs is greatly limited,because of the lack of advanced cathode materials,and their complicated and unclear reaction mechanisms.Exploring the novel nanostructured transition metal and carbon composites is an effective route for obtaining ideal cathode materials.In this work,we synthesize porous CoSnO_(3)/C nanocubes with oxygen vacancies for utilizing as cathodes in RABs for the first time.The intrinsic structure stability of the mixed metal cations and carbon coating can improve the cycling performance of cathodes by regulating the internal strains of the electrodes during volume expansion.The nanocubes with porous structures contribute to fast mass transportation which improves the rate capability.In addition to this,abundant oxygen vacancies promote the adsorption affinity of cathodes,which improves storage capacity.As a result,the CoSnO_(3)/C cathodes display an excellent reversible capacity of 292.1 mAh g^(-1) at 0.1 A g^(-1),a good rate performance with 109 mAh g^(-1) that is maintained even at 1 A g^(-1) and the provided stable cycling behavior for 500 cycles.Besides,a mechanism of intercalation of Al^(3+)within CoSnO_(3)/C cathode is proposed for the electrochemical process.Overall,this work provides a step toward the development of advanced cathode materials for RABs by engineering novel nanostructured mixed transition-metal oxides with carbon composite and proposes novel insights into chemistry for RABs.
基金supported by the National Key R&D Program of China(No.2016YFB0100500)
文摘In this work, we report a facile route for the synthesis of Li3V2(PO4)3/C cathode material via freezedrying and then calcination. The effect of calcination temperature on the electrochemical properties of the Li3V2(PO4)3/C is also investigated. When used as a lithium-ion battery cathode, the optimized Li3V2(PO4)3/C (LVP-800) through calcination at 800 ℃ exhibits a high initial charge and discharge capacity. The excellent electrochemical performance of LVP-800 is attributed to the good crystallinity and uniform morphology of the electrode material. In addition, the residual carbon can also improve the conductivity and buffer the volume expansion during the Li-ion extraction/reinsertion. Meanwhile, charge compensation also plays an important role in excellent electrochemical performance.
基金financially supported by the National Natural Science Foundation of China(No.51641206)Shandong Natural Science Foundation Project(No.ZR2015EM013)+1 种基金Special Funds for Independent Innovation and Transformation of Achievements in Shandong Province(No.2014CGZH0911)National Key R&D Program of China(No.2016YFB0100508)
文摘Li4Ti5012 (LTO) with rich R-TiO2 (17.06, 23.69, and 34.42 wt%), namely, R-TiO2@Li4Ti5O12 composites, were synthesized using the hydrothermal method and tetrabutyl titanate (TBT) as the precursor. Rietveld refinement of X-ray diffraction (XRD) results show that the proportion of Li occupying 16d sites is extraordinary low and the lattice constants of LTO and R-TiO2 change with the ritanium dioxide content. EIS measurements showed that with in creasing R-TiO2 content, both its charge transfer impedance (Rct) and lithium ion diffusion coefficient (DLi) decreased. The changes of Rct and DLi caused by the increase of titanium dioxide content have synergic-antagonistic effects on the rate and cycle properties of Li4Ti5012. The rate performance is positively related to DLi, while the cycle property is negatively correlated with Rct, indicati ng that the rate performs nee is mainly related to DLi, while Rct more significantly affects the cycle performance. LTO-RT-17.06% exhibited excellent rate properties, especially under a high current density (5.0 C, 132.5 mAh/g) and LTO-RT-34.42% showed superior long-term cycle performance (0.012% capacity loss per cycle) compared to that of LTO-RT-17.06% and LTO-RT-23.69%.
基金supported by the National Basic Research Program of China (Grant No. 2015CB251100)the Shell Global Solutions International B.V. (Agreement No. PT76419)。
文摘Rechargeable aluminum ion battery(AIB) with high theoretical specific capacity, abundant elements and low cost engages considerable attention as a promising next generation energy storage and conversion system. Nevertheless, to date, one of the major barriers to pursuit better AIB is the limited applicable cathode materials with the ability to store aluminum highly reversibly. Herein, a highly reversible AIB is proposed using mesoporous TiO2 microparticles(M-TiO2) as the cathode material. The improved performance of Ti O2/Al battery is ascribed to the high ionic conductivity and material stability, which is caused by the stable architecture with a mesoporous microstructure and no random aggregation of secondary particles. In addition, we conducted detailed characterization to gain deeper understanding of the Al^(3+) storage mechanism in anatase Ti O2 for AIB. Our findings demonstrate clearly that Al^(3+)can be reversibly stored in anatase TiO2 by intercalation reactions based on ionic liquid electrolyte. Especially, DFT calculations were used to investigate the accurate insertion sites of aluminum ions in M-Ti O2 and the volume changes of M-TiO2 cells during discharging. As for the controversial side reactions in AIBs, in this work, by normalized calculation, we confirm that M-Ti O2 alone participate in the redox reaction. Moreover, cyclic voltammetry(CV) test was performed to investigate the pseudocapacitive behavior.
