Developing an effective method to synthesize high-performance high-voltage LiCoO_(2) is essential for its industrialization in lithium batteries(LIBs).This work proposes a simple mass-produced strategy for the first t...Developing an effective method to synthesize high-performance high-voltage LiCoO_(2) is essential for its industrialization in lithium batteries(LIBs).This work proposes a simple mass-produced strategy for the first time,that is,negative temperature coefficient thermosensitive Pr_(6)O_(11) nanoparticles are uniformly modified on LiCoO_(2) to prepare LiCoO_(2)@Pr_(6)O_(11)(LCO@PrO)via a liquid-phase mixing combined with annealing method.Tested at 274 mA g−1,the modified LCO@PrO electrodes deliver excellent 4.5 V high-voltage cycling performance with capacity retention ratios of 90.8%and 80.5%at 25 and 60℃,being much larger than those of 22.8%and 63.2%for bare LCO electrodes.Several effective strategies were used to clearly unveil the performance enhancement mechanism induced by Pr_(6)O_(11) modification.It is discovered that Pr_(6)O_(11) can improve interface compatibility,exhibit improved conductivity at elevated temperature,thus enhance the Li^(+)diffusion kinetics,and suppress the phase transformation of LCO and its resulting mechanical stresses.The 450 mAh LCO@PrO‖graphite pouch cells show excellent LIB performance and improved thermal safety characteristics.Importantly,the energy density of such pouch cell was increased even by~42%at 5 C.This extremely convenient technology is feasible for producing high-energy density LIBs with negligible cost increase,undoubtedly providing important academic inspiration for industrialization.展开更多
The presence of oxygen vacancies and hydroxyl groups are both favorable for the methanol electrooxidation on Pt-based catalysts.Understanding and differentiating the enhancing mechanism between oxygen vacancies and hy...The presence of oxygen vacancies and hydroxyl groups are both favorable for the methanol electrooxidation on Pt-based catalysts.Understanding and differentiating the enhancing mechanism between oxygen vacancies and hydroxyl groups for high activity of Pt catalysts in methanol oxidation reaction(MOR)is essential but still challenging.Herein,we developed two kinds of co-catalyst for Pt/CNTs,Pr_(6)O_(11)is rich in oxygen vacancies but contains substantially no hydroxyl groups,while Pr(OH)_(3) possesses abundant hydroxyl groups without oxygen vacancies.After a seque nce of designed experiments,it can be found that both oxygen vacancies and hydroxyl groups can improve the performance of Pt/CNTs electrocatalysts,but the enhancing mechanism and improving degree of oxygen vacancies and hydroxyl groups for the MOR are different.Since the oxygen vacancies are more conducive to increasing the intrinsic activity of the Pt catalyst,and the hydroxyl groups play a decisive role in dehydrogenation and deproto nation of methanol,the co-catalysts with both oxygen vacancies and hydroxyl groups mixed with Pt/CNTs have higher catalytic performance.Therefore,hydroxyl-rich Pr_(6)O_(11)·xH_(2)O was prepared and used as MOR electrocatalyst after mixed with Pt/CNTs.Benefiting from the synergistic effect of oxygen vacancies and hydroxyl groups,the Pr_(6)O_(11)·xH_(2)O/Pt/CNTs shows a high peak current density of 741 mA/mg,which is three times higher than that of Pt/CNTs.These new discoveries serve as a promising strategy for the rational design of MOR catalysts with low cost and high activity.展开更多
基金jointly supported by the Natural Science Foundations of China(Nos.22179020,12174057)Fujian Natural Science Foundation for Distinguished Young Scholars(Grant No.2020J06042)+2 种基金Foreign science and technology cooperation project of Fuzhou Science and Technology Bureau(No.2021-Y-086)Natural Science Foundation of Fujian Province(Grant No.2018J01660)Cultivation plan of outstanding young scientific research talents of Fujian Education Department(Grant No.J1-1323).
文摘Developing an effective method to synthesize high-performance high-voltage LiCoO_(2) is essential for its industrialization in lithium batteries(LIBs).This work proposes a simple mass-produced strategy for the first time,that is,negative temperature coefficient thermosensitive Pr_(6)O_(11) nanoparticles are uniformly modified on LiCoO_(2) to prepare LiCoO_(2)@Pr_(6)O_(11)(LCO@PrO)via a liquid-phase mixing combined with annealing method.Tested at 274 mA g−1,the modified LCO@PrO electrodes deliver excellent 4.5 V high-voltage cycling performance with capacity retention ratios of 90.8%and 80.5%at 25 and 60℃,being much larger than those of 22.8%and 63.2%for bare LCO electrodes.Several effective strategies were used to clearly unveil the performance enhancement mechanism induced by Pr_(6)O_(11) modification.It is discovered that Pr_(6)O_(11) can improve interface compatibility,exhibit improved conductivity at elevated temperature,thus enhance the Li^(+)diffusion kinetics,and suppress the phase transformation of LCO and its resulting mechanical stresses.The 450 mAh LCO@PrO‖graphite pouch cells show excellent LIB performance and improved thermal safety characteristics.Importantly,the energy density of such pouch cell was increased even by~42%at 5 C.This extremely convenient technology is feasible for producing high-energy density LIBs with negligible cost increase,undoubtedly providing important academic inspiration for industrialization.
基金Project supported by the National Natural Science Foundation of China(21875125,21801140,21561023)the Natural Science Foundation of Inner Mongolia Autonomous Region of China(2017JQ03,2018BS05013)Program of Higher-level Talents of Inner Mongolia University(21300-5165155,21300-5155104)。
文摘The presence of oxygen vacancies and hydroxyl groups are both favorable for the methanol electrooxidation on Pt-based catalysts.Understanding and differentiating the enhancing mechanism between oxygen vacancies and hydroxyl groups for high activity of Pt catalysts in methanol oxidation reaction(MOR)is essential but still challenging.Herein,we developed two kinds of co-catalyst for Pt/CNTs,Pr_(6)O_(11)is rich in oxygen vacancies but contains substantially no hydroxyl groups,while Pr(OH)_(3) possesses abundant hydroxyl groups without oxygen vacancies.After a seque nce of designed experiments,it can be found that both oxygen vacancies and hydroxyl groups can improve the performance of Pt/CNTs electrocatalysts,but the enhancing mechanism and improving degree of oxygen vacancies and hydroxyl groups for the MOR are different.Since the oxygen vacancies are more conducive to increasing the intrinsic activity of the Pt catalyst,and the hydroxyl groups play a decisive role in dehydrogenation and deproto nation of methanol,the co-catalysts with both oxygen vacancies and hydroxyl groups mixed with Pt/CNTs have higher catalytic performance.Therefore,hydroxyl-rich Pr_(6)O_(11)·xH_(2)O was prepared and used as MOR electrocatalyst after mixed with Pt/CNTs.Benefiting from the synergistic effect of oxygen vacancies and hydroxyl groups,the Pr_(6)O_(11)·xH_(2)O/Pt/CNTs shows a high peak current density of 741 mA/mg,which is three times higher than that of Pt/CNTs.These new discoveries serve as a promising strategy for the rational design of MOR catalysts with low cost and high activity.
