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

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?...

<ol>
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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 ...

Research

JoVE Journal

Chemistry

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

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

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 ...

Quantifying X-Ray Fluorescence Data Using MAPS

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 ...

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

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

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

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

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

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

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 ...

Biological Samples Preparation for Speciation at Cryogenic Temperature using High-Resolution  X-Ray Absorption Spectroscopy

使用高分辨率X射线吸收光谱在低温下制备生物样品以进行形态分析

The study of elements with X-ray absorption spectroscopy (XAS) is of particular interest when studying the role of metals in biological systems. Sample ...

In situ Grazing Incidence Small Angle X-ray Scattering on Roll-To-Roll Coating of Organic Solar Cells with Laboratory X-ray Instrumentation

通过实验室X射线仪器对有机太阳能电池的滚滚涂层进行现场放牧小角度X射线散射

We present an in-house, in situ Grazing Incidence Small Angle X-ray Scattering (GISAXS) experiment, developed to probe the drying kinetics of roll-to-roll ...