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
The hydrolysis of MgH_(2) delivers high hydrogen capacity(15.2 wt%),which is very attractive for real-time hydrogen supply.However,the formation of a surface passivation Mg(OH)_(2) layer and the large excess of H_(2)O...The hydrolysis of MgH_(2) delivers high hydrogen capacity(15.2 wt%),which is very attractive for real-time hydrogen supply.However,the formation of a surface passivation Mg(OH)_(2) layer and the large excess of H_(2)O required to ensure complete hydrolysis are two key challenges for the MgH_(2) hydrolysis systems.Now,a low-cost method is reported to synthesize MgH_(2)@Mg(BH_(4))_(2) composite via ball-milling MgH_(2) with cheap and widely available B_(2)O_(3)(or B(OH)_(3)).By adding small amounts of B_(2)O_(3),the in-situ formed Mg(BH_(4))_(2) could significantly promote the hydrolysis of MgH_(2).In particular,the MgH_(2)–10 wt%B_(2)O_(3) composite releases 1330.7 mL·g^(−1) H_(2)(close to 80%theoretical hydrogen generation H_(2))in H_(2)O and 1520.4 mL·g^(−1) H_(2)(about 95%)in 0.5 M MgCl_(2) in 60 min at 26℃ with hydrolysis rate of 736.9 mL·g^(−1)·min^(−1) and 960.9 mL·g^(−1)·min^(−1) H_(2) during the first minute of the hydrolysis,respectively.In addition,the MgCl_(2) solution allows repeated use by filtering and exhibits high cycle stability(20 cycles),therefore leading to much reduced capacity loss caused by the excess H_(2)O.We show that by introducing B_(2)O_(3) and recycling the 0.5 M MgCl_(2) solution,the system hydrogen capacity can approach 5.9 wt%,providing a promising hydrogen generation scheme to supply hydrogen to the fuel cells.展开更多
1.27μm波段的氧分子近红外气辉是火星大气最重要的气辉辐射之一,该气辉高光谱分辨辐射传输模型的建立对于研制火星探测载荷,反演火星大气的风场温度场与臭氧浓度,以及研究火星空间物理,有重要的科学价值与工程意义.在研究火星大气O_(2)...1.27μm波段的氧分子近红外气辉是火星大气最重要的气辉辐射之一,该气辉高光谱分辨辐射传输模型的建立对于研制火星探测载荷,反演火星大气的风场温度场与臭氧浓度,以及研究火星空间物理,有重要的科学价值与工程意义.在研究火星大气O_(2)(a^(1)Δ_(g))气辉光化学反应模型的基础上,提出了O_(2)(a^(1)Δ_(g))气辉体辐射率的计算方法,并建立了火星大气气辉辐射传输理论;通过与用于研究火星大气特征的光谱学探测仪(Spectroscopy Spectrograph for the Investigation of Characteristics of the Atmosphere of Mars,SPICAM)的实测数据进行对比,验证了所建立的火星O_(2)(a^(1)Δ_(g))气辉高光谱分辨辐射传输模型的准确性;针对火星与地球大气的O_(2)(a^(1)Δ_(g))气辉,在体辐射率、自吸收效应,以及临边辐射光谱特性三个方面进行了系统深入的比较,对比结果表明,火星大气由于密度低、氧气丰度小,其自吸收效应可以忽略不计,但其O_(2)(a^(1)Δ_(g))气辉辐射强度与地球大气相当,可以用于火星大气的风场温度场与臭氧浓度的探测与反演.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supported by the Basic and Applied Basic Research Foundation of Guangdong Province(No.2022A1515011832 and 2021A1515110676)supported by GDAS’Project of Science and Technology Development(2022GDASZH-2022010104,2022GDASZH-2022030604-04).
文摘The hydrolysis of MgH_(2) delivers high hydrogen capacity(15.2 wt%),which is very attractive for real-time hydrogen supply.However,the formation of a surface passivation Mg(OH)_(2) layer and the large excess of H_(2)O required to ensure complete hydrolysis are two key challenges for the MgH_(2) hydrolysis systems.Now,a low-cost method is reported to synthesize MgH_(2)@Mg(BH_(4))_(2) composite via ball-milling MgH_(2) with cheap and widely available B_(2)O_(3)(or B(OH)_(3)).By adding small amounts of B_(2)O_(3),the in-situ formed Mg(BH_(4))_(2) could significantly promote the hydrolysis of MgH_(2).In particular,the MgH_(2)–10 wt%B_(2)O_(3) composite releases 1330.7 mL·g^(−1) H_(2)(close to 80%theoretical hydrogen generation H_(2))in H_(2)O and 1520.4 mL·g^(−1) H_(2)(about 95%)in 0.5 M MgCl_(2) in 60 min at 26℃ with hydrolysis rate of 736.9 mL·g^(−1)·min^(−1) and 960.9 mL·g^(−1)·min^(−1) H_(2) during the first minute of the hydrolysis,respectively.In addition,the MgCl_(2) solution allows repeated use by filtering and exhibits high cycle stability(20 cycles),therefore leading to much reduced capacity loss caused by the excess H_(2)O.We show that by introducing B_(2)O_(3) and recycling the 0.5 M MgCl_(2) solution,the system hydrogen capacity can approach 5.9 wt%,providing a promising hydrogen generation scheme to supply hydrogen to the fuel cells.
文摘1.27μm波段的氧分子近红外气辉是火星大气最重要的气辉辐射之一,该气辉高光谱分辨辐射传输模型的建立对于研制火星探测载荷,反演火星大气的风场温度场与臭氧浓度,以及研究火星空间物理,有重要的科学价值与工程意义.在研究火星大气O_(2)(a^(1)Δ_(g))气辉光化学反应模型的基础上,提出了O_(2)(a^(1)Δ_(g))气辉体辐射率的计算方法,并建立了火星大气气辉辐射传输理论;通过与用于研究火星大气特征的光谱学探测仪(Spectroscopy Spectrograph for the Investigation of Characteristics of the Atmosphere of Mars,SPICAM)的实测数据进行对比,验证了所建立的火星O_(2)(a^(1)Δ_(g))气辉高光谱分辨辐射传输模型的准确性;针对火星与地球大气的O_(2)(a^(1)Δ_(g))气辉,在体辐射率、自吸收效应,以及临边辐射光谱特性三个方面进行了系统深入的比较,对比结果表明,火星大气由于密度低、氧气丰度小,其自吸收效应可以忽略不计,但其O_(2)(a^(1)Δ_(g))气辉辐射强度与地球大气相当,可以用于火星大气的风场温度场与臭氧浓度的探测与反演.
