通过简单的溶胶-凝胶辅助静电纺丝法得到(113)晶面优势导向的Na_3V_2(PO_4)_3/C钠离子电池正极材料,并通过对比最佳纺丝条件下分别用聚乙烯吡咯烷酮(PVP)和聚氧化乙烯(PEO)作为晶面导向剂制备的两种Na_3V_2(PO_4)_3电极材料的电化学性能...通过简单的溶胶-凝胶辅助静电纺丝法得到(113)晶面优势导向的Na_3V_2(PO_4)_3/C钠离子电池正极材料,并通过对比最佳纺丝条件下分别用聚乙烯吡咯烷酮(PVP)和聚氧化乙烯(PEO)作为晶面导向剂制备的两种Na_3V_2(PO_4)_3电极材料的电化学性能,证明静电纺丝有利于实现Na_3V_2(PO_4)_3(113)晶面择优取向。在相同的电流密度(0.1 C)下,NVP-PVP和NVP-PEO的首周放电比容量分别为112.5 m A·h/g和96.3 m A·h/g,电池循环50周后,NVP-PVP仍然有98.1 m A·h/g的可逆容量保持,NVP-PEO仅仅只剩下34 m A·h/g的可逆容量保持,而即使循环100周后,NVP-PVP的可逆容量仍然在88.2 m A·h/g。结果表明,PVP静电纺丝有利于构建特定的纳米纤维结构和均一的导电碳网络骨架,进而提升主体材料Na_3V_2(PO_4)_3的电化学性能。展开更多
Sodium-ion batteries (SIBs) have attracted increasing attention in the past decades, because of high over-all abundance of precursors, their even geographical distribution, and low cost. Na3V2(PO4)3 (NVP), atypi...Sodium-ion batteries (SIBs) have attracted increasing attention in the past decades, because of high over-all abundance of precursors, their even geographical distribution, and low cost. Na3V2(PO4)3 (NVP), atypical sodium super ion conductor (NASlCON)-based electrode material, exhibits pronounced structuralstability, exceptionally high ion conductivity, rendering it a most promising electrode for sodium storage.However. the comparatively low electronic conductivity makes the theoretical capacity of NVP cannot befully accessible even at comparatively low rates, presenting a major drawback for further practical ap-plications, especially when high rate capability is especially important. Thus, many endeavors have beenconformed to increase the surface and intrinsic electrical conductivity of NVP by coating the active mate-rials with a conductive carbon layer, downsizing the NVP particles, combining the NVP particle with vari-ous carbon materials and ion doping strategy. In this review, to get a better understanding on the sodiumstorage in NVP, we firstly present 4 distinct crystal structures in the temperature range of-30℃-225℃ namely α-NVP, β-NVP, β′-NVP and γ-NVP. Moreover, we give an overview of recent approaches to en-hance the surface electrical conductivity and intrinsic electrical conductivity of NVP. Finally, some poten-tial applications of NVP such as in all-climate environment and PHEV, EV fields have been prospected.展开更多
NASICON (Na-super-ionic-conductors)-structured materials have attracted extensive research interest due to their great application potential in secondary batteries. However, the mechanism of capacity fading for NASICO...NASICON (Na-super-ionic-conductors)-structured materials have attracted extensive research interest due to their great application potential in secondary batteries. However, the mechanism of capacity fading for NASICON-structured electrode materials has been rarely studied. In this paper, we synthesized the NASICON-structured Na3V2(PO4)3/C composite by simple sol-gel and high-temperature solid-phase method and investigated its electrochemical performance in Na-Zn hybrid aqueous rechargeable batteries. After characterizing the structure, morphology and composition variations as well as the interfacial resistance changes of Na3V2(PO4)3/C cathode during cycling, we propose a mechanical and interfacial degradation mechanism for capacity fading of NASICON-structured Na3V2(PO4)3/C in Na-Zn hybrid aqueous rechargeable batteries. This work will shed light on enhancing the mechanical and in terfacial stability of NASICON-structured Na3V2(PO4)3/C in Na-Zn hybrid aqueous rechargeable batteries.展开更多
In this paper,we report for the first time the controlled synthesis of lanthanide ion(Ln3+)-doped tetragonal-phase Na3Zr F7nanocrystals(NCs)via a high-temperature co-precipitation approach.The as-synthesized Na3Zr F7N...In this paper,we report for the first time the controlled synthesis of lanthanide ion(Ln3+)-doped tetragonal-phase Na3Zr F7nanocrystals(NCs)via a high-temperature co-precipitation approach.The as-synthesized Na3Zr F7NCs are systematically studied by utilizing the XRD,TEM as well as high-resolution photoluminescence(PL)spectroscopy.The morphology and size for the as-synthesized Na3Zr F7NCs can be finely controlled by changing the experimental parameters such as the amount of precursor,solvent ratio,reaction temperature and time.By utilizing the red-emitting Eu3+ion as an efficient optical/structural probe,the successful hetero-valence doping of Ln3+activators in the lattices of Na3Zr F7NCs is well-established regardless of their different valences and radii between host Zr4+ion and Ln3+dopant.As a result,intense upconversion(UC)luminescence(UCL)ranging from UV to visible and to NIR spectral regions can be readily achieved after the doping of typical UCL couples of Yb3+/Er3+,Yb3+/Tm3+and Yb3+/Ho3+into the lattices of Na3Zr F7NCs when excited by using a 980-nm NIR diode laser.展开更多
Raman spectra of a vanadoborate (Na3VO2B6Oll) crystal from room temperature up to the melting point have been recorded. The main internal vibrational modes of the crystal have been assigned. It was found that all th...Raman spectra of a vanadoborate (Na3VO2B6Oll) crystal from room temperature up to the melting point have been recorded. The main internal vibrational modes of the crystal have been assigned. It was found that all the Raman bands exhibit decreases in frequency and the widths of the Raman bands increase with the increase of temperature. However, no phase transition was observed under 525 ℃. The micro-structure of its melt was studied by quantum chemistry ab initio calculation. The continuous three-dimensional network of the crystal collapsed and transformed into VO4 and VBO6 clusters during the melting process with an isomerization reaction from four-coordinated boron to a three-coordinated species.展开更多
Inhibition mechanism between sodium(Na_3AlF_6) and sulfur on coke reactivity was investigated by simulating petroleum coke with low-impurity pitch coke and by impurity doping. The mechanism was discussed by scanning e...Inhibition mechanism between sodium(Na_3AlF_6) and sulfur on coke reactivity was investigated by simulating petroleum coke with low-impurity pitch coke and by impurity doping. The mechanism was discussed by scanning electron microscopy, energy-dispersive spectrometry, and X-ray powder diffraction. Results show that Na effectively inhibited S catalysis during carbon–air/CO_2 reactions, and S inhibited the catalysis of Na during carbon– air reaction to a certain extent. A stable structure with a Na-to-S atomic ratio of 1.4 and a cyclic reaction system of "Na_2SO_3→ Na_2S→ Na_2CO_3→ Na_2SO_3" were likely the keys to producing this mutual inhibition.展开更多
文摘通过简单的溶胶-凝胶辅助静电纺丝法得到(113)晶面优势导向的Na_3V_2(PO_4)_3/C钠离子电池正极材料,并通过对比最佳纺丝条件下分别用聚乙烯吡咯烷酮(PVP)和聚氧化乙烯(PEO)作为晶面导向剂制备的两种Na_3V_2(PO_4)_3电极材料的电化学性能,证明静电纺丝有利于实现Na_3V_2(PO_4)_3(113)晶面择优取向。在相同的电流密度(0.1 C)下,NVP-PVP和NVP-PEO的首周放电比容量分别为112.5 m A·h/g和96.3 m A·h/g,电池循环50周后,NVP-PVP仍然有98.1 m A·h/g的可逆容量保持,NVP-PEO仅仅只剩下34 m A·h/g的可逆容量保持,而即使循环100周后,NVP-PVP的可逆容量仍然在88.2 m A·h/g。结果表明,PVP静电纺丝有利于构建特定的纳米纤维结构和均一的导电碳网络骨架,进而提升主体材料Na_3V_2(PO_4)_3的电化学性能。
基金financial support from the National Natural Science Foundation of China (No.21501171,51403209,21406221,51177156/E0712)
文摘Sodium-ion batteries (SIBs) have attracted increasing attention in the past decades, because of high over-all abundance of precursors, their even geographical distribution, and low cost. Na3V2(PO4)3 (NVP), atypical sodium super ion conductor (NASlCON)-based electrode material, exhibits pronounced structuralstability, exceptionally high ion conductivity, rendering it a most promising electrode for sodium storage.However. the comparatively low electronic conductivity makes the theoretical capacity of NVP cannot befully accessible even at comparatively low rates, presenting a major drawback for further practical ap-plications, especially when high rate capability is especially important. Thus, many endeavors have beenconformed to increase the surface and intrinsic electrical conductivity of NVP by coating the active mate-rials with a conductive carbon layer, downsizing the NVP particles, combining the NVP particle with vari-ous carbon materials and ion doping strategy. In this review, to get a better understanding on the sodiumstorage in NVP, we firstly present 4 distinct crystal structures in the temperature range of-30℃-225℃ namely α-NVP, β-NVP, β′-NVP and γ-NVP. Moreover, we give an overview of recent approaches to en-hance the surface electrical conductivity and intrinsic electrical conductivity of NVP. Finally, some poten-tial applications of NVP such as in all-climate environment and PHEV, EV fields have been prospected.
基金financially supported by"135"Projects Fund of CAS-QIBEBT Director Innovation Foundationthe Strategic Priority Research Program of the Chinese Academy of Sciences(Grant no.XDA09010105)+4 种基金the National Natural Science Foundation of China(Grant no.51502319)the Think-Tank Mutual Fund of Qingdao Energy Storage Industry Scientific Researchthe Qingdao Science and Technology Program(17-1-1-26-jch)the Youth Innovation Promotion Association CAS(No.2017253)Qingdao Key Lab of Solar Energy Utilization&Energy Storage Technology
文摘NASICON (Na-super-ionic-conductors)-structured materials have attracted extensive research interest due to their great application potential in secondary batteries. However, the mechanism of capacity fading for NASICON-structured electrode materials has been rarely studied. In this paper, we synthesized the NASICON-structured Na3V2(PO4)3/C composite by simple sol-gel and high-temperature solid-phase method and investigated its electrochemical performance in Na-Zn hybrid aqueous rechargeable batteries. After characterizing the structure, morphology and composition variations as well as the interfacial resistance changes of Na3V2(PO4)3/C cathode during cycling, we propose a mechanical and interfacial degradation mechanism for capacity fading of NASICON-structured Na3V2(PO4)3/C in Na-Zn hybrid aqueous rechargeable batteries. This work will shed light on enhancing the mechanical and in terfacial stability of NASICON-structured Na3V2(PO4)3/C in Na-Zn hybrid aqueous rechargeable batteries.
基金supported by the Strategic Priority Research Program of CAS(XDB20000000)the NSFC(Nos.21390392,21473205,and 21731006)+1 种基金Youth Innovation Promotion Association of CASthe Natural Science Foundation of Fujian Province(No.2017J01038)
文摘In this paper,we report for the first time the controlled synthesis of lanthanide ion(Ln3+)-doped tetragonal-phase Na3Zr F7nanocrystals(NCs)via a high-temperature co-precipitation approach.The as-synthesized Na3Zr F7NCs are systematically studied by utilizing the XRD,TEM as well as high-resolution photoluminescence(PL)spectroscopy.The morphology and size for the as-synthesized Na3Zr F7NCs can be finely controlled by changing the experimental parameters such as the amount of precursor,solvent ratio,reaction temperature and time.By utilizing the red-emitting Eu3+ion as an efficient optical/structural probe,the successful hetero-valence doping of Ln3+activators in the lattices of Na3Zr F7NCs is well-established regardless of their different valences and radii between host Zr4+ion and Ln3+dopant.As a result,intense upconversion(UC)luminescence(UCL)ranging from UV to visible and to NIR spectral regions can be readily achieved after the doping of typical UCL couples of Yb3+/Er3+,Yb3+/Tm3+and Yb3+/Ho3+into the lattices of Na3Zr F7NCs when excited by using a 980-nm NIR diode laser.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.51302268 and 51102239)the Natural Science Foundation of Anhui Province,China(Grant No.KJ2015A339)
文摘Raman spectra of a vanadoborate (Na3VO2B6Oll) crystal from room temperature up to the melting point have been recorded. The main internal vibrational modes of the crystal have been assigned. It was found that all the Raman bands exhibit decreases in frequency and the widths of the Raman bands increase with the increase of temperature. However, no phase transition was observed under 525 ℃. The micro-structure of its melt was studied by quantum chemistry ab initio calculation. The continuous three-dimensional network of the crystal collapsed and transformed into VO4 and VBO6 clusters during the melting process with an isomerization reaction from four-coordinated boron to a three-coordinated species.
基金Projects(51374253,51574289)supported by the National Natural Science Foundation of China
文摘Inhibition mechanism between sodium(Na_3AlF_6) and sulfur on coke reactivity was investigated by simulating petroleum coke with low-impurity pitch coke and by impurity doping. The mechanism was discussed by scanning electron microscopy, energy-dispersive spectrometry, and X-ray powder diffraction. Results show that Na effectively inhibited S catalysis during carbon–air/CO_2 reactions, and S inhibited the catalysis of Na during carbon– air reaction to a certain extent. A stable structure with a Na-to-S atomic ratio of 1.4 and a cyclic reaction system of "Na_2SO_3→ Na_2S→ Na_2CO_3→ Na_2SO_3" were likely the keys to producing this mutual inhibition.