劳伦斯伯克利国家实验室 (LBNL) 的高级光源 (ALS) 由美国能源部科学办公室主任, 根据合同编号支持。DE-AC02-05CH11231。Q.L. 感谢中国奖学金理事会 (CSC) 在中国111项目的基础上进行合作, 提供财务支持。B13029。R.Q. 感谢 LBNL LDRD 计划的支持。西西杰克森感谢 ALS 博士奖学金的支持。

1. 实验计划
注意: 虽然 sXES 可以用实验室设备进行, 但 sXAS 和 RIXS 是基于同步辐射的实验, 需要访问同步加速器设备的 beamtime。在不同的设施中, 申请 beamtime 和运行实验的程序可能不同, 但它们都遵循类似的基本程序。
<ol><li>检查光束线目录 (例如、https://als.lbl.gov/beamlines/) 的设施网站, 或与负责有关光束线的科学家联系, 以确定科学需要的适当光束线.</li>
	<li>通过在线提交系统在 https://als.lbl.gov/users/user-guide/上提交 beamtime 的建议, 光束线先进的光源 (ALS)。 注: beamtime 的建议将根据同步辐射设施的政策进行审查, 成功的提案的作者将被通知为实验性调度的设施。</li>
	<li>安全控制, 根据设备的要求完成必要的安全培训。报告化学品、样品和试验所需的特殊设备, 并进行检查以保证安全。</li>
	<li>到达 beamtime 前的设施, 以获得关于实验设置和示例加载的基本想法, 特别是作为新用户的设施/光束线。</li>
</ol>2. 样品准备
<ol><li>综合了自由和同胞材料的样品, 电化学循环到不同的电荷状态 (SOC)。</li>
	<li>
对空气敏感样品执行以下步骤:
	<ol>
<li>处理空气敏感的样品, 不暴露空气,即打开样品容器, 并用剪刀和镊子将样品切割成一个在惰性气体环境下拟合实验系统的尺寸。</li>
		<li>在惰性气体环境下使用双面导电胶带, 将合适尺寸的样品装在样品持有者上。 注: 如果要测量碳或氧的边缘, 使用软金属如铟粘附粉末样品, 以避免导电胶带中有机化合物的背景 C 和 O 信号。</li>
	</ol>
</li>
	<li>
对非空气敏感样品执行以下步骤:
	<ol>
<li>切割样品以匹配实验系统的特定样品持有者。</li>
		<li>使用双面导电胶带将合适尺寸的样品装入样品持有者。在收集功率样品的碳和氧信号时使用铟箔。</li>
	</ol>
</li>
	<li>对于原位示例, 请使用通常实现软 x 射线膜的特定单元格准备原位示例。在进入实验系统之前, 检查电气连接和电池完整性。 注意: 有关就地单元格的详细信息超出了此工作的范围, 但可以在以前的出版物35、36、37中找到。</li>
</ol>3. 装载和定位样品
注: 由于超高真空对软 x 射线光谱学实验的要求, 试样加载通常在进入主实验室之前, 通过缓冲真空室进行多个步骤。
<ol><li>停止真空泵, 在样品 loadlock 和主实验室之间关闭真空阀, 并排气样品 loadlock, 通常直接连接到带有 N2气体的实验系统。</li>
	<li>使用自制的样品采集器或大镊子抓取样品持有人, 并加载到 loadlock。</li>
	<li>开始抽 loadlock。等待, 直到真空压力表显示足够低的真空, 以打开 loadlock 到主实验室, 通常大约在10中旬-7乇。</li>
	<li>打开 loadlock 和主腔之间的阀门。使用转移臂将样品持有人转移到主室的主机械手上。</li>
	<li>打开主实验室与光束线之间的阀门。通过观察可见光荧光的参考样品来确定光斑。</li>
	<li>通过改变实验实验站的样本机械手的坐标, 将试样定位到光斑上。</li>
</ol>4. 设置 X 射线能量和分辨率
<ol><li>通过计算机程序或手动调节旋钮更改光束线单色仪的狭缝值, 以控制入射 X 射线光束的能量分辨率。</li>
	<li>将入射光束能量设置为访问感兴趣元素的吸收边缘所需的值,例如, 290 ev 用于 C k, 530 ev 用于 O k 边缘38。</li>
	<li>连接 X 射线束通量 (I-0) 显示器的信号电缆, 通常是光束路径中的一个干净的金网。</li>
	<li>修正了光束线单色仪的机构, 并在波荡间隙收集束流强度。为最大可能的光束通量确定特定的波荡间隙值。 注: 由于 sXAS 需要一个大的能量范围为不同的边缘, 一个优化的波荡隙, 以获得最大可能的光束通量往往是必要的。</li>
</ol>5. 收集 sXAS 数据
注: 通过记录采样电流 (泰) 和 channeltron 或光电二极管 (TFY) 的信号强度, 收集总收益 sXAS 数据。部分屈服信号通常通过门控 channeltron 和固态探测器收集。由于 RIXS 系统是在这里介绍的, 并且 RIXS 包括所有种类的部分荧光率 (PFY) 信号, 包括 PFY 和逆 PFY (iPFY), 在本次会议中只描述了泰和 TFY 数据收集的典型协议。
<ol><li>将样品连接到当前放大器, 并将采样电流信号 (泰) 送到计算机计数器。</li>
	<li>打开 channeltron 或光电二极管的电源和控制器, 将 TFY 信号送到计算机计数器。</li>
	<li>启动 LabVIEW sXAS 数据采集 grogram BL 控制主到达软件界面 (图 2), 然后单击菜单按钮扫描 |单电机扫描(图 2)。</li>
	<li>单击菜单按钮扫描安装程序(图 3), 设置事件 (光束线) X 射线光子的扫描范围, 以匹配感兴趣的 sXAS 边缘, 例如, 为 C K 边缘提供 280-300 eV. </li>
	<li>单击按钮开始扫描(图 3), 在扫描入射 X 射线光子能量时, 记录 (i) 泰 (ii) TFY 和 (iii) I-0 通道同时进行的强度信号。 注意: 在入射 X 射线光子能量上, 通常会有几个 eV 的小位移。在收集电池材料样品之前, 要进行校准, 收集一个或多个典型参考样品的 sXAS 数据。</li>
</ol>6. 收集 sXES 和 RIXS 数据
注: 由于 sXES 技术上是在非共振 (高) 能量范围内的 RIXS 切割, 所以数据收集设备和过程基本上是相同的。
<ol><li>收集 sXAS 首先定义励磁能量范围和校准能量值 (参考协议步骤 5)。</li>
	<li>打开 sXES/RiXS 系统光谱仪探测器的电源, 并冷却软 x 射线探测器, 以减少背景噪音, 每个制造商的建议。</li>
	<li>启动 LabVIEW sXES/RiXS 数据采集 grogram BL 控制主以到达软件接口 (图 4)。</li>
	<li>单击菜单按钮马达(图 4) 设置光谱仪的光学参数, 以便探测器覆盖感兴趣的元素和边缘的能量范围 (图 5)。</li>
	<li>单击菜单按钮扫描(图 4) |CCD 仪器扫描(图 6)。</li>
	<li>单击菜单按钮扫描安装程序(图 6), 以设置事件 (光束线) X 射线光子能量的扫描范围。如果收集 sXES, 将其设置为大约 20-30 eV 以上的 sXAS 吸收边缘的单一值;否则, 如果收集 RiXS, 将入射 X 射线 (光束线) 能量设置为覆盖 sXAS 吸收边缘的范围。</li>
	<li>选择图标应用宇宙射线滤镜(图 6), 从原始 RIXS 2D 图像中取出宇宙射线信号, 一旦从光谱仪探测器采集到它们。</li>
	<li>单击按钮开始扫描(图 6) 以收集荧光信号, 它们由光栅衍射和能量解析, 以2D 图像的形式由探测器上的每个激发能量组成。</li>
</ol>7. sXAS 数据处理
注: 实验数据, 包括 sXAS 以及 sXES 和 RiXS, 都是在伊戈尔 Pro 程序中处理的。
<ol><li>将 sXAS 泰和 TFY 信号正常化为同时收集的 I-0 信号。</li>
	<li>计算参考样品所收集的 sXAS 与标准之间的能量误差;根据计算出的能量误差来校准 sXAS 信号。</li>
</ol>8. sXES 和 RIXS 数据处理
<ol><li>通过对沿角度调整的发射-能量通道的光子计数进行汇总, 将原始2D 图像的强度综合起来, 生成单个 sXES 或 RIXS 谱。</li>
	<li>将集成的 1D RIXS 频谱正常化为在数据收集过程中实时监视的入射光束流量, 以及收集时间 (以秒为单位)。</li>
	<li>按颜色缩放格式绘制规范化的1D 频谱。</li>
	<li>对于 RiXS 数据, 对每个激发能量重复步骤 8.1-8.3, 在发射能量通道上获得一系列 1D RiXS 谱;然后, 将所有颜色缩放的 1D RIXS 光谱一对一地叠加成2D 图像图, 用一个轴沿励磁能量, 另一轴显示发射能量通道。</li>
	<li>使用 sXAS 校准, 通常通过参考样本 (参见协议步骤 7.2) 校准 sXES 频谱或 RIXS 映射的励磁能量值。</li>
	<li>选择一组点 (x = 通道号、 y = 能量值) 沿 RIXS 地图上的弹性特征, 其中激发和发射能量相同;用点集进行线性曲线拟合, 达到每通道的形式能量值;根据关系, 缩放从通道到能量的x轴。</li>
</ol>

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href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Direct+Experimental+Probe+of+the+Ni(II)/Ni(III)/Ni(IV)+Redox+Evolution+in+LiNi0.5Mn1.5O4Electrodes.">Direct Experimental Probe of the Ni(II)/Ni(III)/Ni(IV) Redox Evolution in LiNi0.5Mn1.5O4Electrodes.</a> The Journal of Physical Chemistry C. 119 (49), 27228-27233 (2015).</li><li>Pasta, M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Manganese-cobalt+hexacyanoferrate+cathodes+for+sodium-ion+batteries.">Manganese-cobalt hexacyanoferrate cathodes for sodium-ion batteries.</a> J. Mater. Chem. A. 4 (11), 4211-4223 (2016).</li><li>Jeyachandran, Y. L., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Investigation+of+the+Ionic+Hydration+in+Aqueous+Salt+Solutions+by+Soft+X-ray+Emission+Spectroscopy.">Investigation of the Ionic Hydration in Aqueous Salt Solutions by Soft X-ray Emission Spectroscopy.</a> J Phys Chem B. 120 (31), 7687-7695 (2016).</li><li>Jeyachandran, Y. L., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ion-Solvation-Induced+Molecular+Reorganization+in+Liquid+Water+Probed+by+Resonant+Inelastic+Soft+X-ray+Scattering.">Ion-Solvation-Induced Molecular Reorganization in Liquid Water Probed by Resonant Inelastic Soft X-ray Scattering.</a> The Journal of Physical Chemistry Letters. 5 (23), 4143-4148 (2014).</li><li>Fuchs, O., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=High-resolution,+high-transmission+soft+x-ray+spectrometer+for+the+study+of+biological+samples.">High-resolution, high-transmission soft x-ray spectrometer for the study of biological samples.</a> Rev Sci Instrum. 80 (6), 063103 (2009).</li><li>Chuang, Y. -. D., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Modular+soft+x-ray+spectrometer+for+applications+in+energy+sciences+and+quantum+materials.">Modular soft x-ray spectrometer for applications in energy sciences and quantum materials.</a> Review of Scientific Instruments. 88 (1), 013110 (2017).</li><li>Qiao, R., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=High-efficiency+in+situ+resonant+inelastic+x-ray+scattering+(iRIXS)+endstation+at+the+Advanced+Light+Source.">High-efficiency in situ resonant inelastic x-ray scattering (iRIXS) endstation at the Advanced Light Source.</a> Review of Scientific Instruments. 88 (3), 033106 (2017).</li><li>Liu, X., Yang, W., Liu, Z. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Recent+Progress+on+Synchrotron-Based+In-Situ+Soft+X-ray+Spectroscopy+for+Energy+Materials.">Recent Progress on Synchrotron-Based In-Situ Soft X-ray Spectroscopy for Energy Materials.</a> Adv Mater. 26 (46), 7710-7729 (2014).</li><li>Guo, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+development+of+in+situ+photon-in/photon-out+soft+X-ray+spectroscopy+on+beamline+7.0.1+at+the+ALS.">The development of in situ photon-in/photon-out soft X-ray spectroscopy on beamline 7.0.1 at the ALS.</a> Journal of Electron Spectroscopy and Related Phenomena. 188, 71-78 (2013).</li><li>Blum, M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Solid+and+liquid+spectroscopic+analysis+(SALSA)-a+soft+x-ray+spectroscopy+endstation+with+a+novel+flow-through+liquid+cell.">Solid and liquid spectroscopic analysis (SALSA)-a soft x-ray spectroscopy endstation with a novel flow-through liquid cell.</a> Review of Scientific Instruments. 80 (12), 123102 (2009).</li><li>Williams, G. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> X-RAY DATA BOOKLET. , (2009).</li><li>Achkar, A. J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Bulk+sensitive+x-ray+absorption+spectroscopy+free+of+self-absorption+effects.">Bulk sensitive x-ray absorption spectroscopy free of self-absorption effects.</a> Physical Review B. 83 (8), 081106 (2011).</li><li>Qiao, R., Chin, T., Harris, S. J., Yan, S., Yang, W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Spectroscopic+fingerprints+of+valence+and+spin+states+in+manganese+oxides+and+fluorides.">Spectroscopic fingerprints of valence and spin states in manganese oxides and fluorides.</a> Current Applied Physics. 13 (3), 544-548 (2013).</li></ol>

作者没有什么可透露的。

提高储能材料性能的艰巨挑战需要先进的工具来直接探测电池化合物在电化学操作过程中的化学演化。软 x 射线核级光谱学, 如 sXAS、sXES 和 RIXS, 是检测在库和同胞中所涉及的阴离子和阳离子的临界价态的一种选择工具。
核心级光谱学技术涉及在偶极子选择规则之后, 核心电子对未占用状态的强烈激发。与硬 X 射线相比, 软 X 射线的低能量使对低 Z 阴离子元素 (如 C、N 和 O K 边)...

开发高性能电池是实现具有环保资源和设备的现代能源应用的关键要求之一。开发高效、低成本、可持续的储能设备已经成为电动汽车和电网的关键, 在这个十年中, 预计的蓄能市场将扩大十倍。无处不在的锂离子电池 (LIB) 技术仍然是高能量密度和高能量存储解决方案1的一个有希望的候选者, 而 Na-离子电池 (同胞) 有望实现绿色电网的低成本稳定存储。应用程序2。但是, 电池技术的总体水平远远低于需要满足这一新阶段的大中型能源存储1,3。
开发高性能储能系统面临的紧迫挑战来自于电池操作的复杂机械和电子特性。广泛的工作重点是材料合成和机械性能。然而, 电池电极中特定元素的化学状态的演变往往是新开发的电池材料的积极辩论。一般而言, 在电荷和放电过程中, 库和同胞都与电子和离子的传输所触发的不断变化的电子元件操作, 从而导致特定元素的氧化和还原 (氧化还原) 反应。电池阴极作为许多性能参数的瓶颈, 在研究和开发中得到了很大的关注4,5。一种实用的电池阴极材料通常是一个3d过渡金属 (TM) 氧化物, 具有特定的离子扩散结构通道。传统上, 氧化还原反应仅限于 TM 元素;然而, 最近的结果表明, 氧气可能被用于可逆电化学循环6。氧化还原机理是了解电化学操作的最关键的信息之一, 因此, 对具有元素灵敏度的电池电极的化学状态进行直接探针是非常可取的。
同步辐射, 软 x 射线光谱学是一种先进的技术, 检测在费米水平附近的电池材料的价电子状态7。由于软 x 射线光子对特定元素和轨道的电子具有很高的灵敏度, 软 x 射线光谱学可以作为电池电极8或电池接口中的临界电子状态的直接探针。9. 此外, 与硬 x 射线相比, 软 x 射线在3d TMs10中的低 Z 元素、例如、C、N、O 和2p到3d激发的能量和覆盖激发上较低。
软 x 射线光谱的激发首先是通过从软 x 射线光子吸收能量, 从一个特定的核心状态到未占用状态的电子跃迁。因此, 这种软 x 射线吸收光谱的强度对应于未占用 (传导带) 状态的密度 (DOS) 与激发的核心孔的存在。X 射线吸收系数可以通过检测在衰变过程中发射的光子或电子的总数量来测量。总电子屈服 (泰) 计数发射电子的总数量, 并且因而是光子在电子出 (PIEO) 检测模式。泰有几纳米的浅探针深度, 因此相对表面敏感, 由于电子的浅逸出深度。然而, 作为光子在光子出 (PIPO) 检测模式, 总荧光率 (TFY) 测量发射光子的总数量在 sXAS 过程中。它的探针深度大约是上百纳米, 比泰深。由于探针深度的不同, 泰与 TFY 的对比可以为材料的表面和体积的比较提供重要的信息。
sXES 是一种 PIPO 技术, 对应于退出状态的衰变, 以填充核心孔, 从而导致 X 射线光子在特征能量下的发射。如果核心电子对离 sXAS 阈值很远的连续电子状态感到兴奋, 它是一个非共振 x 射线荧光过程, 对应于被占领 (价带) 电子到核心孔的衰变,即, sXES 反映 DOS的价带状态。否则, 如果核心电子共振激发到精确的吸收阈值, 则产生的发射谱具有强的激发能量依赖性。对于这种情况, 光谱学实验被称为共振非弹性 x 射线散射 (RIXS)。
由于 sXAS 和 sXES 对应于未占用的 (传导带) 和被占领 (价带) 电子状态, 它们分别提供了有关在电池中参与还原和氧化反应的电子状态的互补信息。电化学操作后的电极11。对于低 Z 元素, 特别是 C12、13、N14和 O15、16、17, sXAS 已被广泛用于研究与电子相对应的临界电子态。传输12,13和化学成分15,16,17。对于3d TMs, tm L 边缘的 sXAS 已成功证明是对 V18、锰19、20、21、22的 tm 氧化还原反应的有效探针, 23, Fe23,24,25,26, Co20,27, 和 Ni20,28。由于 tm L sXAS 功能由定义良好的 multiplet 效果控制, 对不同 TM 氧化的敏感度18,19,20,21,22 ,24,25,26,27, 28 和自旋状态14, 29, TM sXAS 数据可以实现甚至定量LIB 和同胞电极中 TM 氧化还原对的分析27。
与 sXAS 在电池材料研究中的流行就业相比, 由于获得与电池性能有关的有意义的信息10的实验和数据解释的复杂性, RIXS 很少被使用。然而, 由于 RIXS 的化学态选择性极高, RIXS 对电池材料中的化学态演化具有内在的元素敏感性有潜在的敏感性。最近的 sXES 和 RIXS 报告 Jeyachandran et., 已经展示了 RIXS 对特定化学结构的高度敏感性在 sXAS30,31之外的离子溶剂化系统中。随着最近快速发展的高效 RIXS 系统32,33,34, RIXS 迅速从一个基本的物理工具转移到一个强大的电池研究技术, 偶尔成为在电池化合物中阳离子和负离子演化的具体研究的选择工具。
在这项工作中, 介绍了 sXAS、sXES 和 RIXS 实验的详细协议。我们涵盖了实验计划的细节、进行实验的技术程序, 更重要的是对不同光谱技术的数据处理。此外, 在电池材料研究中有三个代表性的结果显示了这三软 x 射线光谱学技术的应用。我们注意到, 这些实验的技术细节在不同的终端站和/或设施中可能是不同的。此外, "原位" 和原位实验由于对软 X 射线光谱学35的超高真空的严格要求, 对采样处理有非常不同的设置过程。但是这里的协议代表了典型的程序, 可以作为在不同实验系统中的软 x 射线光谱学实验的共同参考。

<table border="0" cellpadding="0" cellspacing="0" style="width:833px;" width="834">
	<colgroup>
		<col />
		<col />
		<col />
		<col />
	</colgroup>
	<tbody>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Material</td>
			<td style="width:144px;"></td>
			<td style="width:119px;"></td>
			<td style="width:355px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Electrode active materials</td>
			<td style="width:144px;">various</td>
			<td style="width:119px;"></td>
			<td>Synthesized in-house or obtained from various suppliers.</td>
		</tr>
		<tr height="63">
			<td height="63" style="height:63px;">Lithium foil</td>
			<td style="width:144px;">Sigma-Aldrich</td>
			<td>320080</td>
			<td style="width:355px;">Anode for half cells. Store and handle in an inert atmosphere glovebox under Ar. (www.sigmaaldrich.com)</td>
		</tr>
		<tr height="63">
			<td height="63" style="height:63px;">Sodium foil</td>
			<td style="width:144px;">Sigma-Aldrich</td>
			<td style="width:119px;">282065</td>
			<td style="width:355px;">Anode for half cells. Store and handle in an inert atmosphere glovebox under Ar. (www.sigmaaldrich.com)</td>
		</tr>
		<tr height="63">
			<td height="63" style="height:63px;">Electrolyte solutions</td>
			<td style="width:144px;">BASF</td>
			<td style="width:119px;">Contact vendor for desired formulations</td>
			<td style="width:355px;">http://www.catalysts.basf.com/p02/USWeb-Internet/catalysts/en/content/microsites/catalysts/prods-inds/batt-mats/electrolytes</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Synthetic flake graphite</td>
			<td style="width:144px;">Timcal</td>
			<td style="width:119px;">SFG-6</td>
			<td style="width:355px;">Conductive additive for electrodes. (www.timcal.com)</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;">Indium foil</td>
			<td style="width:144px;">Sigma-Aldrich</td>
			<td style="width:119px;">357308</td>
			<td style="width:355px;">Used if collecting Carbon and Oxygen signals of power samples</td>
		</tr>
		<tr height="63">
			<td height="63" style="height:63px;width:216px;">Argon gas</td>
			<td style="width:144px;">Air Products</td>
			<td style="width:119px;">Custom order, contact vendors</td>
			<td style="width:355px;">Argon used to fill glovebox where to assemble and store air-sensitive samples. (http://www.airproducts.com/products/gases.aspx)</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Eqiupment</td>
			<td style="width:144px;"></td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="84">
			<td height="84" style="height:84px;width:216px;">CCD</td>
			<td style="width:144px;">iKon-L</td>
			<td style="width:119px;">DO936N</td>
			<td style="width:355px;">Used to capture the emission photons when carrying out the sXES or RiXS experiment (http://www.andor.com/scientific-cameras/ikon-xl-and-ikon-large-ccd-series/ikon-l-936)</td>
		</tr>
		<tr height="63">
			<td height="63" style="height:63px;width:216px;">Inert atmosphere glovebox</td>
			<td style="width:144px;">MBRAUN</td>
			<td style="width:119px;">MB200B</td>
			<td style="width:355px;">Used during air-sensitive samples assembly and storage. (http://www.mbraun.com/products/glovebox-workstations/mb200b-mod)</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Battery Charge &#38; Discharge Tester</td>
			<td style="width:144px;">Bio-Logic</td>
			<td style="width:119px;">VMP3</td>
			<td style="width:355px;">Used to electrochemical cycling of battery materials. (https://www.bio-logic.net/en/)</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Swagelok cell</td>
			<td style="width:144px;">MTI</td>
			<td style="width:119px;">EQ-HSTC</td>
			<td style="width:355px;">Used to contain the battery for electrochemical cycling</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Sample holder</td>
			<td style="width:144px;">manufactured in lab</td>
			<td style="width:119px;"></td>
			<td>Used to hold the samples in the experiment</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;">Hardware tools</td>
			<td style="width:144px;">various</td>
			<td style="width:119px;"></td>
			<td style="width:355px;">Including tweezers, scissors (used to assemble samples), tongs (used to transfer sample holders), etc.&#160;</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Carbon and Copper tape</td>
			<td style="width:144px;">3M</td>
			<td style="width:119px;">Custom order, contact vendors</td>
			<td>Used to paste the samples onto sample holders</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Igor Pro</td>
			<td style="width:144px;">WaveMetrics</td>
			<td style="width:119px;">7.06</td>
			<td style="width:355px;">Used to process the experiment data. (https://www.wavemetrics.com/index.html)</td>
		</tr>
	</tbody>
</table>

elemental-sensitive detection of the chemistry in batteries through soft x-ray absorption spectroscopy and resonant inelastic x-ray scattering

能源储存已成为当今可持续能源应用的一个限制因素, 包括电动汽车和基于挥发性太阳能和风力来源的绿色电网。开发高性能电化学储能解决方案的迫切需求,即电池, 依靠学院和工业界的基本理解和实际发展。开发成功的电池技术所面临的巨大挑战源于不同的能源存储应用的不同要求。能量密度、功率、稳定性、安全性和成本参数都必须在电池中平衡, 以满足不同应用的要求。因此, 需要开发和优化基于不同材料和机制的多电池技术。能够直接探测各种电池材料中化学反应的尖锐工具, 对于推进该领域超越常规的试错方法至关重要。在这里, 我们提出了软 x 射线吸收光谱 (sXAS)、软 x 射线发射光谱 (sXES) 和共振非弹性 x 射线散射 (RIXS) 实验的详细协议, 它们是过渡金属固有的元素敏感探针。3d和负离子2p在电池化合物中的状态。通过这些软 x 射线光谱学技术, 我们提供了有关电池材料中关键化学状态的实验技术和演示的详细信息。

示例持有者和粘贴的示例显示在图 1中。图 7是一个典型的 RIXS 图像, 在特定的励磁能量中收集, 光谱仪设置为感兴趣的边缘。此处显示的图像是在电池电极材料上收集的, 林妮0.33Co0.33锰0.33O2, 其励磁能量为 858 ev, 探测器设置在约 500-900 ev 范围内, 以覆盖 O K、锰 l、Co 和镍 L, 如<strong cla...

Watch this Scientific Journal Video about Elemental-sensitive Detection of the Chemistry in Batteries through Soft X-ray Absorption Spectroscopy and Resonant Inelastic X-ray Scattering at JoVE.com

Elemental-sensitive Detection of the Chemistry in Batteries through Soft X-ray Absorption Spectroscopy and Resonant Inelastic X-ray Scattering

软 x 射线吸收光谱和共振非弹性 x 射线散射法检测电池化学成分的元素敏感度

本文提出了软 X 射线吸收光谱 (sXAS) 和共振非弹性 x 射线散射 (RIXS) 的典型实验的协议, 并在电池材料研究中的应用。

Energy storage has become more and more a limiting factor of today's sustainable energy applications, including electric vehicles and green electric grid ...

elemental-sensitive-detection-chemistry-batteries-through-soft-x-ray

Research

JoVE Journal

Chemistry

12.6K 次观看.  Stanford University. 本文提出了软 X 射线吸收光谱 (sXAS) 和共振非弹性 x 射线散射 (RIXS) 的典型实验的协议, 并在电池材料研究中的应用。

视频: Elemental-sensitive Detection of the Chemistry in Batteries through Soft X-ray Absorption Spectroscopy and Resonant Inelastic X-ray Scattering

Preparing Adherent Cells for X-ray Fluorescence Imaging by Chemical Fixation

X-ray fluorescence imaging allows us to non-destructively measure the spatial distribution and concentration of multiple elements simultaneously over large or small sample areas. It has been applied in many areas of science, including materials science, geoscience, studying works of cultural heritage, and in chemical biology. In the case of chemical biology, for example, visualizing the metal distributions within cells allows us to study both naturally-occurring metal ions in the cells, as well as exogenously-introduced metals such as drugs and nanoparticles. Due to the fully hydrated nature of nearly all biological samples, cryo-fixation followed by imaging under cryogenic temperature represents the ideal imaging modality currently available. However, under the circumstances that such a combination is not easily accessible or practical, aldehyde based chemical fixation remains useful and sometimes inevitable. This article describes in as much detail as possible in the preparation of adherent mammalian cells by chemical fixation for X-ray fluorescent imaging.

Here, we present a protocol on how to determine the quantity and distribution of metals in a sample using synchrotron X-ray fluorescence. We focus on adherent cells, and describe the chemical fixation method to prepare this sample. We then describe how to mount and image the sample using synchrotron X-rays.

化学固定准备贴壁细胞的X射线荧光成像

X-ray fluorescence imaging allows us to non-destructively measure the spatial distribution and concentration of multiple elements simultaneously over ...

科研

化学

X-ray Powder Diffraction in Conservation Science: Towards Routine Crystal Structure Determination of Corrosion Products on Heritage Art Objects

The crystal structure determination and refinement process of corrosion products on historic art objects using laboratory high-resolution X-ray powder diffraction (XRPD) is presented in detail via two case studies.
The first material under investigation was sodium copper formate hydroxide oxide hydrate, Cu4Na4O(HCOO)8(OH)2&#8729;4H2O (sample 1) which forms on soda glass/copper alloy composite historic objects (e.g., enamels) in museum collections, exposed to formaldehyde and formic acid emitted from wooden storage cabinets, adhesives, etc. This degradation phenomenon has recently been characterized as &#34;glass induced metal corrosion&#34;.
For the second case study, thecotrichite, Ca3(CH3COO)3Cl(NO3)2&#8729;6H2O (sample 2), was chosen, which is an efflorescent salt forming needlelike crystallites on tiles and limestone objects which are stored in wooden cabinets and display cases. In this case, the wood acts as source for acetic acid which reacts with soluble chloride and nitrate salts from the artifact or its environment.
The knowledge of the geometrical structure helps conservation science to better understand production and decay reactions and to allow for full quantitative analysis in the frequent case of mixtures.

Modern high resolution X-ray powder diffraction (XRPD) in the laboratory is used as an efficient tool to determine crystal structures of long-known corrosion products on historic objects.

X射线粉末衍射在保护科学:迈向文物艺术品腐蚀产物的常规晶体结构测定

The crystal structure determination and refinement process of corrosion products on historic art objects using laboratory high-resolution X-ray powder ...

Synthesis of Protein Bioconjugates via Cysteine-maleimide Chemistry

The chemical linking or bioconjugation of proteins to fluorescent dyes, drugs, polymers and other proteins has a broad range of applications, such as the development of antibody drug conjugates (ADCs) and nanomedicine, fluorescent microscopy and systems chemistry. For many of these applications, specificity of the bioconjugation method used is of prime concern. The Michael addition of maleimides with cysteine(s) on the target proteins is highly selective and proceeds rapidly under mild conditions, making it one of the most popular methods for protein bioconjugation.
We demonstrate here the modification of the only surface-accessible cysteine residue on yeast cytochrome c with a ruthenium(II) bisterpyridine maleimide. The protein bioconjugation is verified by gel electrophoresis and purified by aqueous-based fast protein liquid chromatography in 27% yield of isolated protein material. Structural characterization with MALDI-TOF MS and UV-Vis is then used to verify that the bioconjugation is successful. The protocol shown here is easily applicable to other cysteine - maleimide coupling of proteins to other proteins, dyes, drugs or polymers.

Synthesis of Protein Bioconjugates via Cysteine-maleimide Chemistry

This protocol details the important steps required for the bioconjugation of a cysteine containing protein to a maleimide, including reagent purification, reaction conditions, bioconjugate purification and bioconjugate characterization.

蛋白质生物缀合物的合成<em&gt;通过</em&gt;半胱氨酸马来酰亚胺化学

The chemical linking or bioconjugation of proteins to fluorescent dyes, drugs, polymers and other proteins has a broad range of applications, such as the ...

Quantifying X-Ray Fluorescence Data Using MAPS

The quantification of X-ray fluorescence (XRF) microscopy maps by fitting the raw spectra to a known standard is crucial for evaluating chemical composition and elemental distribution within a material. Synchrotron-based XRF has become an integral characterization technique for a variety of research topics, particularly due to its non-destructive nature and its high sensitivity. Today, synchrotrons can acquire fluorescence data at spatial resolutions well below a micron, allowing for the evaluation of compositional variations at the nanoscale. Through proper quantification, it is then possible to obtain an in-depth, high-resolution understanding of elemental segregation, stoichiometric relationships, and clustering behavior.
This article explains how to use the MAPS fitting software developed by Argonne National Laboratory for the quantification of full 2-D XRF maps. We use as an example results from a Cu(In,Ga)Se2 solar cell, taken at the Advanced Photon Source beamline 2-ID-D at Argonne National Laboratory. We show the standard procedure for fitting raw data, demonstrate how to evaluate the quality of a fit and present the typical outputs generated by the program. In addition, we discuss in this manuscript certain software limitations and offer suggestions for how to further correct the data to be numerically accurate and representative of spatially resolved, elemental concentrations.

Here, we demonstrate the use of the X-ray fluorescence fitting software, MAPS, created by Argonne National Laboratory for the quantification of fluorescence microscopy data. The quantified data that results is useful for understanding the elemental distribution and stoichiometric ratios within a sample of interest.

利用地图量化 X 射线荧光数据

The quantification of X-ray fluorescence (XRF) microscopy maps by fitting the raw spectra to a known standard is crucial for evaluating chemical ...

Total Internal Reflection Absorption Spectroscopy (TIRAS) for the Detection of Solvated Electrons at a Plasma-liquid Interface

The total internal reflection absorption spectroscopy (TIRAS) method presented in this article uses an inexpensive diode laser to detect solvated electrons produced by a low-temperature plasma in contact with an aqueous solution. Solvated electrons are powerful reducing agents, and it has been postulated that they play an important role in the interfacial chemistry between a gaseous plasma or discharge and a conductive liquid. However, due to the high local concentrations of reactive species at the interface, they have a short average lifetime (~1 &#181;s), which makes them extremely difficult to detect. The TIRAS technique uses a unique total internal reflection geometry combined with amplitude-modulated lock-in amplification to distinguish solvated electrons&#39; absorbance signal from other spurious noise sources. This enables the in situ detection of short-lived intermediates in the interfacial region, as opposed to the bulk measurement of stable products in the solution. This approach is especially attractive for the field of plasma electrochemistry, where much of the important chemistry is driven by short-lived free radicals. This experimental method has been used to analyze the reduction of nitrite (NO2-(aq)), nitrate (NO3-(aq)), hydrogen peroxide (H2O2(aq)), and dissolved carbon dioxide (CO2(aq)) by plasma-solvated electrons and deduce effective rate constants. Limitations of the method may arise in the presence of unintended parallel reactions, such as air contamination in the plasma, and absorbance measurements may also be hindered by the precipitation of reduced electrochemical products. Overall, the TIRAS method can be a powerful tool for studying the plasma-liquid interface, but its effectiveness depends on the particular system and reaction chemistry under study.

Total Internal Reflection Absorption Spectroscopy TIRAS for the Detection of Solvated Electrons at a Plasma-liquid Interface

This article presents a total internal reflection absorption spectroscopy (TIRAS) method for measuring short-lived free radicals at a plasma-liquid interface. In particular, TIRAS is used to identify solvated electrons based on their optical absorbance of red light near 700 nm.

全内反射吸收光谱法 (拉斯) 在等离子体-液体界面上检测溶剂电子

The total internal reflection absorption spectroscopy (TIRAS) method presented in this article uses an inexpensive diode laser to detect solvated ...

Microfluidic Chips for In Situ Crystal X-ray Diffraction and In Situ Dynamic Light Scattering for Serial Crystallography

This protocol describes fabricating microfluidic devices with low X-ray background optimized for goniometer based fixed target serial crystallography. The devices are patterned from epoxy glue using soft lithography and are suitable for in situ X-ray diffraction experiments at room temperature. The sample wells are lidded on both sides with polymeric polyimide foil windows that allow diffraction data collection with low X-ray background. This fabrication method is undemanding and inexpensive. After the sourcing of a SU-8 master wafer, all fabrication can be completed outside of a cleanroom in a typical research lab environment. The chip design and fabrication protocol utilize capillary valving to microfluidically split an aqueous reaction into defined nanoliter sized droplets. This loading mechanism avoids the sample loss from channel dead-volume and can easily be performed manually without using pumps or other equipment for fluid actuation. We describe how isolated nanoliter sized drops of protein solution can be monitored in situ by dynamic light scattering to control protein crystal nucleation and growth. After suitable crystals are grown, complete X-ray diffraction datasets can be collected using goniometer based in situ fixed target serial X-ray crystallography at room temperature. The protocol provides custom scripts to process diffraction datasets using a suite of software tools to solve and refine the protein crystal structure. This approach avoids the artefacts possibly induced during cryo-preservation or manual crystal handling in conventional crystallography experiments. We present and compare three protein structures that were solved using small crystals with dimensions of approximately 10-20 &#181;m grown in chip. By crystallizing and diffracting in situ, handling and hence mechanical disturbances of fragile crystals is minimized. The protocol details how to fabricate a custom X-ray transparent microfluidic chip suitable for in situ serial crystallography. As almost every crystal can be used for diffraction data collection, these microfluidic chips are a very efficient crystal delivery method.

Microfluidic Chips for In Situ Crystal X-ray Diffraction and In Situ Dynamic Light Scattering for Serial Crystallography

This protocol describes in detail how to fabricate and operate microfluidic devices for X-ray diffraction data collection at room temperature. Additionally, it describes how to monitor protein crystallization by dynamic light scattering and how to process and analyze obtained diffraction data.

用于原位晶体 x 射线衍射和原位的微流控芯片系列晶体学的动态光散射

This protocol describes fabricating microfluidic devices with low X-ray background optimized for goniometer based fixed target serial crystallography. The ...

Essential Metal Uptake in Gram-negative Bacteria: X-ray Fluorescence, Radioisotopes, and Cell Fractionation

We demonstrate a scalable method for the separation of the bacterial periplasm from the cytoplasm. This method is used to purify periplasmic protein for the purpose of biophysical characterization, and measure substrate transfer between periplasmic and cytoplasmic compartments. By carefully limiting the time that the periplasm is separated from the cytoplasm, the experimenter can extract the protein of interest and assay each compartment individually for substrate without carry-over contamination between compartments. The extracted protein from fractionation can then be further analyzed for three-dimensional structure determination or substrate-binding profiles. Alternatively, this method can be performed after incubation with a radiotracer to determine total percent uptake, as well as distribution of the tracer (and hence metal transport) across different bacterial compartments. Experimentation with a radiotracer can help differentiate between a physiological substrate and artefactual substrate, such as those caused by mismetallation.
X-ray fluorescence can be used to discover the presence or absence of metal incorporation in a sample, as well as measure changes that may occur in metal incorporation as a product of growth conditions, purification conditions, and/or crystallization conditions. X-ray fluorescence also provides a relative measure of abundance for each metal, which can be used to determine the best metal energy absorption peak to use for anomalous X-ray scattering data collection. Radiometal uptake can be used as a method to validate the physiological nature of a substrate detected by X-ray fluorescence, as well as support the discovery of novel substrates.

A protocol for the extraction of a periplasmic transition metal chaperone in the context of its native binding partners, and biophysical characterization of its substrate contents by X-ray fluorescence and radiometal uptake is presented.

革兰氏阴性菌的基本金属摄取: x 射线荧光、放射性同位素和细胞分馏

We demonstrate a scalable method for the separation of the bacterial periplasm from the cytoplasm. This method is used to purify periplasmic protein for ...

Analysis of Minerals Produced by hFOB 1.19 and Saos-2 Cells Using Transmission Electron Microscopy with Energy Dispersive X-ray Microanalysis

This video presents the use of transmission electron microscopy with energy dispersive X-ray microanalysis (TEM-EDX) to compare the state of minerals in vesicles released by two human bone cell lines: hFOB 1.19 and Saos-2. These cell lines, after treatment with ascorbic acid (AA) and &#946;-glycerophosphate (&#946;-GP), undergo complete osteogenic transdifferentiation from proliferation to mineralization and produce matrix vesicles (MVs) that trigger apatite nucleation in the extracellular matrix (ECM).
Based on Alizarin Red-S (AR-S) staining and analysis of the composition of minerals in cell lysates using ultraviolet (UV) light or in vesicles using TEM imaging followed by EDX quantitation and ion mapping, we can infer that osteosarcoma Saos-2 and osteoblastic hFOB 1.19 cells reveal distinct mineralization profiles. Saos-2 cells mineralize more efficiently than hFOB 1.19 cells and produce larger mineral deposits that are not visible under UV light but are similar to hydroxyapatite (HA) in that they have more Ca and F substitutions.
The results obtained using these techniques allow us to conclude that the process of mineralization differs depending on the cell type. We propose that, at the cellular level, the origin and properties of vesicles predetermine the type of minerals.

We present a protocol to compare the state of minerals in vesicles released by two human bone cell lines: hFOB 1.19 and Saos-2. Their mineralization profiles were analyzed by Alizarin Red-S (AR-S) staining, ultraviolet (UV) light visualization, transmission electron microscopy (TEM) imaging and energy dispersive X-ray microanalysis (EDX).

透射电镜 hFOB 1.19 和 Saos-2 细胞产生的能量色散 X 射线显微分析

This video presents the use of transmission electron microscopy with energy dispersive X-ray microanalysis (TEM-EDX) to compare the state of minerals in ...

Ligand-Mediated Nucleation and Growth of Palladium Metal Nanoparticles

The size, size distribution and stability of colloidal nanoparticles are greatly affected by the presence of capping ligands. Despite the key contribution of capping ligands during the synthesis reaction, their role in regulating the nucleation and growth rates of colloidal nanoparticles is not well understood. In this work, we demonstrate a mechanistic investigation of the role of trioctylphosphine (TOP) in Pd nanoparticles in different solvents (toluene and pyridine) using in situ SAXS and ligand-based kinetic modeling. Our results under different synthetic conditions reveal the overlap of nucleation and growth of Pd nanoparticles during the reaction, which contradicts the LaMer-type nucleation and growth model. The model accounts for the kinetics of Pd-TOP binding for both, the precursor and the particle surface, which is essential to capture the size evolution as well as the concentration of particles in situ. In addition, we illustrate the predictive power of our ligand-based model through designing the synthetic conditions to obtain nanoparticles with desired sizes. The proposed methodology can be applied to other synthesis systems and therefore serves as an effective strategy for predictive synthesis of colloidal nanoparticles.

The main goal of this work is to elucidate the role of capping agents in regulating the size of palladium nanoparticles by combining in situ small angle x-ray scattering (SAXS) and ligand-based kinetic modeling.

配体介导成核与钯金属纳米粒子的生长

The size, size distribution and stability of colloidal nanoparticles are greatly affected by the presence of capping ligands. Despite the key contribution ...

Improving High Viscosity Extrusion of Microcrystals for Time-resolved Serial Femtosecond Crystallography at X-ray Lasers

High-viscosity micro-extrusion injectors have dramatically reduced sample consumption in serial femtosecond crystallographic experiments (SFX) at X-ray free electron lasers (XFELs). A series of experiments using the light-driven proton pump bacteriorhodopsin have further established these injectors as a preferred option to deliver crystals for time-resolved serial femtosecond crystallography (TR-SFX) to resolve structural changes of proteins after photoactivation. To obtain multiple structural snapshots of high quality, it is essential to collect large amounts of data and ensure clearance of crystals between every pump laser pulse. Here, we describe in detail how we optimized the extrusion of bacteriorhodopsin microcrystals for our recent TR-SFX experiments at the Linac Coherent Light Source (LCLS). The goal of the method is to optimize extrusion for a stable and continuous flow while maintaining a high density of crystals to increase the rate at which data can be collected in a TR-SFX experiment. We achieve this goal by preparing lipidic cubic phase with a homogenous distribution of crystals using a novel three-way syringe coupling device followed by adjusting the sample composition based on measurements of the extrusion stability taken with a high-speed camera setup. The methodology can be adapted to optimize the flow of other microcrystals. The setup will be available for users of the new Swiss Free Electron Laser facility.

The success of a time-resolved serial femtosecond crystallography experiment is dependent on efficient sample delivery. Here, we describe protocols to optimize the extrusion of bacteriorhodopsin microcrystals from a high viscosity micro-extrusion injector. The methodology relies on sample homogenization with a novel three-way coupler and visualization with a high-speed camera.

改进 x 射线激光时分辨序列飞秒晶体学微晶的高粘度挤出

High-viscosity micro-extrusion injectors have dramatically reduced sample consumption in serial femtosecond crystallographic experiments (SFX) at X-ray ...