Iron‐based pyrophosphates are attractive cathodes for sodium‐ion batteries due to their large framework,cost‐effectiveness,and high energy density.However,the understanding of the crystal structure is scarce and on...Iron‐based pyrophosphates are attractive cathodes for sodium‐ion batteries due to their large framework,cost‐effectiveness,and high energy density.However,the understanding of the crystal structure is scarce and only a limited candidates have been reported so far.In this work,we found for the first time that a continuous solid solution,Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2)(0≤α≤1,could be obtained by mutual substitution of cations at center‐symmetric Na3 and Na4 sites while keeping the crystal building blocks of anionic P_(2)O_(7) unchanged.In particular,a novel off‐stoichiometric Na_(3)Fe(2.5)(P_(2)O_(7))_(2)is thus proposed,and its structure,energy storage mechanism,and electrochemical performance are extensively investigated to unveil the structure–function relationship.The as‐prepared off‐stoichiometric electrode delivers appealing performance with a reversible discharge capacity of 83 mAh g^(−1),a working voltage of 2.9 V(vs.Na^(+)/Na),the retention of 89.2%of the initial capacity after 500 cycles,and enhanced rate capability of 51 mAh g^(−1)at a current density of 1600 mA g^(−1).This research shows that sodium ferric pyrophosphate could form extended solid solution composition and promising phase is concealed in the range of Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2),offering more chances for exploration of new cathode materials for the construction of high‐performance SIBs.展开更多
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
针对高放废液硼硅酸盐玻璃固化体易析出辉石晶相的问题,本文采用P_(2)O_(5)部分替代硼硅酸盐基础玻璃配方中的MgO和CaO,研究了P_(2)O_(5)掺量(质量分数为0~8%)对玻璃固化体析晶和抗浸出性能的影响。结果表明,当P_(2)O_(5)掺量为0~3%时,...针对高放废液硼硅酸盐玻璃固化体易析出辉石晶相的问题,本文采用P_(2)O_(5)部分替代硼硅酸盐基础玻璃配方中的MgO和CaO,研究了P_(2)O_(5)掺量(质量分数为0~8%)对玻璃固化体析晶和抗浸出性能的影响。结果表明,当P_(2)O_(5)掺量为0~3%时,样品为无定形态,在850℃热处理6 h后,P_(2)O_(5)掺量为0~2%的样品主要析出辉石晶相,而P_(2)O_(5)掺量为3%的样品析出了少量硅酸钙晶相,辉石晶相基本消失;当P_(2)O_(5)掺量高于3%时,样品析出球形Na_(3)Ca_(6)(PO_(4))_(5)晶体,且析晶度随P_(2)O_(5)掺量的增加而升高。29 Si MAS NMR和^(11)B MAS NMR分析表明,随着P_(2)O_(5)掺量的增加,玻璃网络结构中Q^(3)、Q^(4)和BO_(3)结构单元含量逐渐增加。静态浸泡法(MCC-1)试验结果表明,样品的抗浸出性能随P_(2)O_(5)掺量的增加而逐渐提高,其中P_(2)O_(5)掺量为3%的样品浸泡28 d后,Si、B、Na和Cs元素的归一化浸出率分别为0.508、0.468、0.533、0.280 g/(m^(2)·d)。展开更多
基金National Natural Science Foundation of China,Grant/Award Numbers:21972108,U20A20249,U22A20438Changzhou Science and Technology Bureau,Grant/Award Number:CM20223017Innovation and Technology Commission(ITC)of Hong Kong,The Innovation&Technology Fund(ITF)with Project No.ITS/126/21。
文摘Iron‐based pyrophosphates are attractive cathodes for sodium‐ion batteries due to their large framework,cost‐effectiveness,and high energy density.However,the understanding of the crystal structure is scarce and only a limited candidates have been reported so far.In this work,we found for the first time that a continuous solid solution,Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2)(0≤α≤1,could be obtained by mutual substitution of cations at center‐symmetric Na3 and Na4 sites while keeping the crystal building blocks of anionic P_(2)O_(7) unchanged.In particular,a novel off‐stoichiometric Na_(3)Fe(2.5)(P_(2)O_(7))_(2)is thus proposed,and its structure,energy storage mechanism,and electrochemical performance are extensively investigated to unveil the structure–function relationship.The as‐prepared off‐stoichiometric electrode delivers appealing performance with a reversible discharge capacity of 83 mAh g^(−1),a working voltage of 2.9 V(vs.Na^(+)/Na),the retention of 89.2%of the initial capacity after 500 cycles,and enhanced rate capability of 51 mAh g^(−1)at a current density of 1600 mA g^(−1).This research shows that sodium ferric pyrophosphate could form extended solid solution composition and promising phase is concealed in the range of Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2),offering more chances for exploration of new cathode materials for the construction of high‐performance SIBs.
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.
文摘针对高放废液硼硅酸盐玻璃固化体易析出辉石晶相的问题,本文采用P_(2)O_(5)部分替代硼硅酸盐基础玻璃配方中的MgO和CaO,研究了P_(2)O_(5)掺量(质量分数为0~8%)对玻璃固化体析晶和抗浸出性能的影响。结果表明,当P_(2)O_(5)掺量为0~3%时,样品为无定形态,在850℃热处理6 h后,P_(2)O_(5)掺量为0~2%的样品主要析出辉石晶相,而P_(2)O_(5)掺量为3%的样品析出了少量硅酸钙晶相,辉石晶相基本消失;当P_(2)O_(5)掺量高于3%时,样品析出球形Na_(3)Ca_(6)(PO_(4))_(5)晶体,且析晶度随P_(2)O_(5)掺量的增加而升高。29 Si MAS NMR和^(11)B MAS NMR分析表明,随着P_(2)O_(5)掺量的增加,玻璃网络结构中Q^(3)、Q^(4)和BO_(3)结构单元含量逐渐增加。静态浸泡法(MCC-1)试验结果表明,样品的抗浸出性能随P_(2)O_(5)掺量的增加而逐渐提高,其中P_(2)O_(5)掺量为3%的样品浸泡28 d后,Si、B、Na和Cs元素的归一化浸出率分别为0.508、0.468、0.533、0.280 g/(m^(2)·d)。
