The effect of Cr2O3 on the nucleation and crystallization of Na2O-CaO-Al2O3-SiO2-F- glass has been investigated by means of ESR(Electron Spin Resonance), SEM(Scanning Electron Microscope), EDS(Energy Dispersive Specro...The effect of Cr2O3 on the nucleation and crystallization of Na2O-CaO-Al2O3-SiO2-F- glass has been investigated by means of ESR(Electron Spin Resonance), SEM(Scanning Electron Microscope), EDS(Energy Dispersive Specrometer) and so on. Computer pattern recognition is applied to optimize the heat-treatment schedules. The experimental results show that the base glass containing more than 1 .5 % (mass fraction) Cr2O3 can be nucleated internally and converted to spheroidal crystal glass materials. The spheroidal crystal consisted of fibrous wollastonite crystals radiating from a center. The residual glass phase filled in the interstices between the fibers and between the spherulites. During heat treatment process, the valence states ofchromium changed from Cr6- to Cr3-, and the Cr-spinel solidsolution [CaCr2O4] precipitated followed this valence change. At the primary stage of crystallization, the Cr-spinel could act as a nucleating center on which the principal or}stalline phase β-CaSiO3 grew epitaxially.展开更多
Due to its low cost and natural abundance of sodium,Na-ion batteries(NIBs)are promising candidates for large-scale energy storage systems.The development of ultralow voltage anode materials is of great significance in...Due to its low cost and natural abundance of sodium,Na-ion batteries(NIBs)are promising candidates for large-scale energy storage systems.The development of ultralow voltage anode materials is of great significance in improving the energy density of NIBs.Low-voltage anode materials,however,are severely lacking in NIBs.Of all the reported insertion oxides anodes,the Na_(2)Ti_(3)O_(7) has the lowest operating voltage(an average potential of 0.3 V vs.Na^(+)/Na)and is less likely to deposit sodium,which has excellent potential for achieving NIBs with high energy densities and high safety.Although significant progress has been made,achieving Na_(2)Ti_(3)O_(7) electrodes with excellent performance remains a severe challenge.This paper systematically summarizes and discusses the physicochemical properties and synthesis methods of Na_(2)Ti_(3)O_(7).Then,the sodium storage mechanisms,key issues and challenges,and the optimization strategies for the electrochemical performance of Na_(2)Ti_(3)O_(7) are classified and further elaborated.Finally,remaining challenges and future research directions on the Na_(2)Ti_(3)O_(7) anode are highlighted.This review offers insights into the design of high-energy and high-safety NIBs.展开更多
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
To optimize their Al_(2)O_(3)-SiO_(2) raw materials,anorthite based insulation refractories were prepared by the in-situ sintering process combined with the foaming method after sintering at 1350℃for 3 h,using green ...To optimize their Al_(2)O_(3)-SiO_(2) raw materials,anorthite based insulation refractories were prepared by the in-situ sintering process combined with the foaming method after sintering at 1350℃for 3 h,using green and pollution-free kaolin,kyanite,andalusite and sillimanite as Al_(2)O_(3)-SiO_(2) raw materials,respectively,and industrial CaCO_(3) as the CaO source.Effects of Al_(2)O_(3)-SiO_(2) raw material types on the physical properties,phase composition and microstructure were investigated.The results are as follows.All samples prepared by different Al_(2)O_(3)-SiO_(2) raw materials have hexagonal flake anorthite and a small amount of mullite and corundum.Their bulk density and thermal conductivity decrease in the order of using kaolin,andalusite,kyanite and sillimanite as the Al_(2)O_(3)-SiO_(2) raw material,but their apparent porosity increases.Moreover,in the sample with kaolin,the bonding between anorthite crystals on the pore walls is closer than that of the other samples,which is conducive to increasing the cold crushing strength.The bonding between anorthite crystals on pore walls gradually decreases in the order of using kyanite,andalusite and sillimanite as the Al_(2)O_(3)-SiO_(2) raw material,thus their cold crushing strength decreases accordingly.In comprehensive consideration,the properties of the sample from kyanite are the optimal.Its apparent porosity,thermal conductivity and cold crushing strength are 84.6%,0.141 W·m^(-1)·K^(-1) and 1.89 MPa,respectively.展开更多
文摘The effect of Cr2O3 on the nucleation and crystallization of Na2O-CaO-Al2O3-SiO2-F- glass has been investigated by means of ESR(Electron Spin Resonance), SEM(Scanning Electron Microscope), EDS(Energy Dispersive Specrometer) and so on. Computer pattern recognition is applied to optimize the heat-treatment schedules. The experimental results show that the base glass containing more than 1 .5 % (mass fraction) Cr2O3 can be nucleated internally and converted to spheroidal crystal glass materials. The spheroidal crystal consisted of fibrous wollastonite crystals radiating from a center. The residual glass phase filled in the interstices between the fibers and between the spherulites. During heat treatment process, the valence states ofchromium changed from Cr6- to Cr3-, and the Cr-spinel solidsolution [CaCr2O4] precipitated followed this valence change. At the primary stage of crystallization, the Cr-spinel could act as a nucleating center on which the principal or}stalline phase β-CaSiO3 grew epitaxially.
基金supported by the National Natural Science Foundation of China (52307239,52102300,52207234)the Natural Science Foundation of Hubei Province (2022CFB1003,2021CFA025)。
文摘Due to its low cost and natural abundance of sodium,Na-ion batteries(NIBs)are promising candidates for large-scale energy storage systems.The development of ultralow voltage anode materials is of great significance in improving the energy density of NIBs.Low-voltage anode materials,however,are severely lacking in NIBs.Of all the reported insertion oxides anodes,the Na_(2)Ti_(3)O_(7) has the lowest operating voltage(an average potential of 0.3 V vs.Na^(+)/Na)and is less likely to deposit sodium,which has excellent potential for achieving NIBs with high energy densities and high safety.Although significant progress has been made,achieving Na_(2)Ti_(3)O_(7) electrodes with excellent performance remains a severe challenge.This paper systematically summarizes and discusses the physicochemical properties and synthesis methods of Na_(2)Ti_(3)O_(7).Then,the sodium storage mechanisms,key issues and challenges,and the optimization strategies for the electrochemical performance of Na_(2)Ti_(3)O_(7) are classified and further elaborated.Finally,remaining challenges and future research directions on the Na_(2)Ti_(3)O_(7) anode are highlighted.This review offers insights into the design of high-energy and high-safety NIBs.
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This work was supported by the National Natural Science Foundation of China(5180021223)Henan Provice Science&Technology Programs(232102231046 and 232102231051)Cultivation Programme for Yong Backbone Teachers in Henan University to Technology(2142121).
文摘To optimize their Al_(2)O_(3)-SiO_(2) raw materials,anorthite based insulation refractories were prepared by the in-situ sintering process combined with the foaming method after sintering at 1350℃for 3 h,using green and pollution-free kaolin,kyanite,andalusite and sillimanite as Al_(2)O_(3)-SiO_(2) raw materials,respectively,and industrial CaCO_(3) as the CaO source.Effects of Al_(2)O_(3)-SiO_(2) raw material types on the physical properties,phase composition and microstructure were investigated.The results are as follows.All samples prepared by different Al_(2)O_(3)-SiO_(2) raw materials have hexagonal flake anorthite and a small amount of mullite and corundum.Their bulk density and thermal conductivity decrease in the order of using kaolin,andalusite,kyanite and sillimanite as the Al_(2)O_(3)-SiO_(2) raw material,but their apparent porosity increases.Moreover,in the sample with kaolin,the bonding between anorthite crystals on the pore walls is closer than that of the other samples,which is conducive to increasing the cold crushing strength.The bonding between anorthite crystals on pore walls gradually decreases in the order of using kyanite,andalusite and sillimanite as the Al_(2)O_(3)-SiO_(2) raw material,thus their cold crushing strength decreases accordingly.In comprehensive consideration,the properties of the sample from kyanite are the optimal.Its apparent porosity,thermal conductivity and cold crushing strength are 84.6%,0.141 W·m^(-1)·K^(-1) and 1.89 MPa,respectively.
