湖泊沉积物作为重要的环境演化记录载体,其矿物组合特征蕴含了丰富的古环境信息。然而,由于沉积物中晶质和非晶质组分的复杂共存关系,以及多相矿物体系的相互干扰效应,其精确定量分析一直是沉积学研究中的技术难点。该研究以西藏中部封...湖泊沉积物作为重要的环境演化记录载体,其矿物组合特征蕴含了丰富的古环境信息。然而,由于沉积物中晶质和非晶质组分的复杂共存关系,以及多相矿物体系的相互干扰效应,其精确定量分析一直是沉积学研究中的技术难点。该研究以西藏中部封闭咸水湖泊巴木错沉积物为研究对象,系统分析、评估了参比强度比(RIR)法和Rietveld全谱拟合法在复杂沉积物矿物定量分析中的可靠性和应用效果。文章采用高纯度刚玉作为内标物质,设计了1∶1、3∶7和1∶9三组不同配比的混合样品,通过X射线衍射(XRD)分析获取了完整的衍射数据。基于COD晶体结构数据库,分别采用RIR值法和Rietveld全谱拟合法进行定量计算,并结合非晶含量测定方法,构建了完整的矿物定量分析体系。研究结果表明,Rietveld全谱拟合法表现出优异的分析精度和稳定性:对于含量大于20%的主量相,相对标准偏差(RSD,Relative Standard Deviation)控制在3%以内;含量在5%~20%之间的次量相,RSD值保持在5%~10%范围内;即使对于含量低于5%的微量相,其定量结果也显著优于RIR值法。特别是在处理非均质样品时,Rietveld法表现出良好的适应性,各矿物相含量与混合比例呈现显著的线性相关性(R^(2)>0.95)。相比之下,RIR值法在高含量内标条件下(50%和30%)表现出显著的不稳定性,定量结果的相对偏差超出了SY/T5163-2018标准规定的允许范围。这种局限性主要源于其对单个衍射峰强度比值的过度依赖,易受样品基体效应和优势相干扰的影响。此外,通过非晶含量计算,获得了原始沉积物样品中约31%的非晶态物质含量,三组混合样品计算结果的高度一致性(RSD<3%)进一步验证了Rietveld法的可靠性。该研究不仅系统评估了两种定量方法的适用性,而且在复杂湖泊沉积物分析中首次实现了晶质矿物和非晶质组分的协同定量。研究结果对完善湖泊沉积物矿物定量分析方法,提高环境重建的准确性具有重要意义和应用价值。展开更多
The effectiveness of dual-doping as a method of improving the conductivity of sulfide solid electrolytes(SEs)is not in doubt;however,the atomic-level mechanisms underpinning these enhancements remain elusive.In this s...The effectiveness of dual-doping as a method of improving the conductivity of sulfide solid electrolytes(SEs)is not in doubt;however,the atomic-level mechanisms underpinning these enhancements remain elusive.In this study,we investigate the atomic mechanisms associated with the high ionic conductivity of the Li_(7)P_(3)S_(11)(LPS)SE and its response to Ag/Cl dual dopants.Synthesis and electrochemical characterizations show that the 0.2 M AgCl-doped LPS(Li_(6.8)P_(3)Ag_(0.1)S_(10.9)Cl_(0.1))exhibited an over 80%improvement in ionic conductivity compared with the undoped LPS.The atomic-level structures responsible for the enhanced conductivity were generated by a set of experiment and simulation techniques:synchrotron X-ray diffractometry,Rietveld refinement,density functional theory,and artificial neural network-based molecular dynamics simulations.This thorough characterization highlights the role of dual dopants in altering the structure and ionic conductivity.We found that the PS_(4) and P_(2)S_(7) structural motifs of LPS undergo transformation into various PS_(x) substructures.These changes in the substructures,in conjunction with the paddle-wheel effect,enable rapid Li migration.The dopant atoms serve to enhance the flexibility of PS_(4)–P_(2)S_(7) polyhedral frameworks,consequently enhancing the ionic conductivity.Our study elucidates a clear structure–conductivity relationship for the dual-doped LPS,providing a fundamental guideline for the development of sulfide SEs with superior conductivity.展开更多
在 X 射线衍射定性分析的基础上，结合 Rietveld 全谱拟合方法对不同龄期磷酸镁水泥样品的水化产物晶相含量进行了定量研究。结果表明，龄期为10 min、1 h 及1 d 的磷酸镁水泥样品中水化产物 MgKPO4·6H2 O 的相对含量分别为12.39%...在 X 射线衍射定性分析的基础上，结合 Rietveld 全谱拟合方法对不同龄期磷酸镁水泥样品的水化产物晶相含量进行了定量研究。结果表明，龄期为10 min、1 h 及1 d 的磷酸镁水泥样品中水化产物 MgKPO4·6H2 O 的相对含量分别为12.39%、15.77%和18.38%，拟合的 Rwp因子为9.73%-12.8%，说明该方法能准确、直观、快速的确定不同龄期样品中各晶相的组成及相对含量，并获得各相的相关晶体学结构参数，同时结合相关理论对磷酸镁水泥的水化及性能作出客观分析，为加深对水泥材料的认识提供了一种可行的研究方法。展开更多
文摘湖泊沉积物作为重要的环境演化记录载体,其矿物组合特征蕴含了丰富的古环境信息。然而,由于沉积物中晶质和非晶质组分的复杂共存关系,以及多相矿物体系的相互干扰效应,其精确定量分析一直是沉积学研究中的技术难点。该研究以西藏中部封闭咸水湖泊巴木错沉积物为研究对象,系统分析、评估了参比强度比(RIR)法和Rietveld全谱拟合法在复杂沉积物矿物定量分析中的可靠性和应用效果。文章采用高纯度刚玉作为内标物质,设计了1∶1、3∶7和1∶9三组不同配比的混合样品,通过X射线衍射(XRD)分析获取了完整的衍射数据。基于COD晶体结构数据库,分别采用RIR值法和Rietveld全谱拟合法进行定量计算,并结合非晶含量测定方法,构建了完整的矿物定量分析体系。研究结果表明,Rietveld全谱拟合法表现出优异的分析精度和稳定性:对于含量大于20%的主量相,相对标准偏差(RSD,Relative Standard Deviation)控制在3%以内;含量在5%~20%之间的次量相,RSD值保持在5%~10%范围内;即使对于含量低于5%的微量相,其定量结果也显著优于RIR值法。特别是在处理非均质样品时,Rietveld法表现出良好的适应性,各矿物相含量与混合比例呈现显著的线性相关性(R^(2)>0.95)。相比之下,RIR值法在高含量内标条件下(50%和30%)表现出显著的不稳定性,定量结果的相对偏差超出了SY/T5163-2018标准规定的允许范围。这种局限性主要源于其对单个衍射峰强度比值的过度依赖,易受样品基体效应和优势相干扰的影响。此外,通过非晶含量计算,获得了原始沉积物样品中约31%的非晶态物质含量,三组混合样品计算结果的高度一致性(RSD<3%)进一步验证了Rietveld法的可靠性。该研究不仅系统评估了两种定量方法的适用性,而且在复杂湖泊沉积物分析中首次实现了晶质矿物和非晶质组分的协同定量。研究结果对完善湖泊沉积物矿物定量分析方法,提高环境重建的准确性具有重要意义和应用价值。
基金National Research Foundation of Korea,Grant/A ward Numbers:MEST,NRF-2021R1A2C2009596Engineeringand Physical Sciences Research Council,Grant/A ward Numbers:EP/R029431,EP/P020194,EP/T022213+1 种基金Korea government(Ministry of Science and ICT,MSIT),Grant/Award Number:RS-2023-00236572European Research Council,ERC,Grant/Award Numbers:EP/R029431,EP/P020194,EP/T022213。
文摘The effectiveness of dual-doping as a method of improving the conductivity of sulfide solid electrolytes(SEs)is not in doubt;however,the atomic-level mechanisms underpinning these enhancements remain elusive.In this study,we investigate the atomic mechanisms associated with the high ionic conductivity of the Li_(7)P_(3)S_(11)(LPS)SE and its response to Ag/Cl dual dopants.Synthesis and electrochemical characterizations show that the 0.2 M AgCl-doped LPS(Li_(6.8)P_(3)Ag_(0.1)S_(10.9)Cl_(0.1))exhibited an over 80%improvement in ionic conductivity compared with the undoped LPS.The atomic-level structures responsible for the enhanced conductivity were generated by a set of experiment and simulation techniques:synchrotron X-ray diffractometry,Rietveld refinement,density functional theory,and artificial neural network-based molecular dynamics simulations.This thorough characterization highlights the role of dual dopants in altering the structure and ionic conductivity.We found that the PS_(4) and P_(2)S_(7) structural motifs of LPS undergo transformation into various PS_(x) substructures.These changes in the substructures,in conjunction with the paddle-wheel effect,enable rapid Li migration.The dopant atoms serve to enhance the flexibility of PS_(4)–P_(2)S_(7) polyhedral frameworks,consequently enhancing the ionic conductivity.Our study elucidates a clear structure–conductivity relationship for the dual-doped LPS,providing a fundamental guideline for the development of sulfide SEs with superior conductivity.
文摘在 X 射线衍射定性分析的基础上，结合 Rietveld 全谱拟合方法对不同龄期磷酸镁水泥样品的水化产物晶相含量进行了定量研究。结果表明，龄期为10 min、1 h 及1 d 的磷酸镁水泥样品中水化产物 MgKPO4·6H2 O 的相对含量分别为12.39%、15.77%和18.38%，拟合的 Rwp因子为9.73%-12.8%，说明该方法能准确、直观、快速的确定不同龄期样品中各晶相的组成及相对含量，并获得各相的相关晶体学结构参数，同时结合相关理论对磷酸镁水泥的水化及性能作出客观分析，为加深对水泥材料的认识提供了一种可行的研究方法。
