Name: failure analysis of batteries using synchrotron-based hard x-ray microtomography
Uploaded: 2015-08-26T16:00:00.000+00:00
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Description: Watch this Scientific Journal Video about Failure Analysis of Batteries Using Synchrotron-based Hard X-ray Microtomography at JoVE.com

Primary funding for the work was provided by the Electron Microscopy of Soft Matter Program from the Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. The battery assembly portion of the project was supported by the BATT program from the Vehicle Technologies program, through the Office of Energy Efficiency and Renewable Energy under U.S. DOE Contract DE-AC02-05CH11231. Hard X-ray microtomography experiments were performed at the Advanced Light Source which is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. Katherine J. Harry was supported by a National Science Foundation Graduate Research Fellowship.

1.电解液制备<ol><li>合成240千克/摩尔- 260个千克/摩尔的聚（苯乙烯） -使用阴离子聚合的聚（环氧乙烷）共聚物（SEO） - 块 。 <ol><li>请在氩手套箱里的水和氧气水平控制的所有额外的样品制备和保持&lt;5ppm的。 </li><li>溶解0.3克聚合物的无水N-甲基-2-吡咯烷酮（NMP）与干燥的锂，双（三氟甲烷）磺酰亚胺（的LiTFSI）盐。使用的LiTFSI盐0.275 SEO质量比和NMP的搜索引擎优化的13.13质量比。 注:聚合物的这个数量将产生的膜足够大，以使大约20个样本。 </li><li>使用刮刀15厘米投下所有的步骤中制备的聚合物和盐的混合物的上述一个到约15厘米见方的片镍箔。干燥所得到的薄膜在60℃CO / N。 </li><li>干燥后，从镍箔剥离该膜，并允许在真空下于9进一步干燥0℃。 </li><li>在手套箱供以后使用包裹在镍箔和存储所得到的独立式膜内部的气密箱。 </li></ol></li></ol> 2.锂 - 锂对称细胞的制备<ol><li>使用直径的7/16，圆形金属冲，切出从99.9％，电池级锂金属箔卷两块锂金属电极。 </li><li>使用1/2英寸直径的金属冲头切出一块高分子电解质膜构成。 注意:锂金属是更柔软，更容易冲比高分子电解质。 </li><li>夹持两块锂金属电极之间的聚合物电解质膜，然后按镍片上的电极。 </li><li>真空密封在样品中的气密袋由聚丙烯和尼龙衬里铝。 注意:一个锂电极的容易交换与阴极如果想研究一个完整的电池。 </li></ol> 3.对称细胞周期<html> G <ol><li>将真空密封样品放入使用电化学循环设备在90℃和循环保持的烘箱。循环以实现通过电解质膜合理离子电导率期间加热样品。为安全起见，确保样品不接近180℃的锂金属的熔点。 </li><li>传递0.175毫安/厘米2的电流密度通过样品4小时，并按照与45分钟的休息。接着，传递-0.175毫安/厘米2的电流密度通过样品4小时，并按照与45分钟的休息。根据需要重复这个循环程序多次。 </li><li>观察为通过30微米厚的SEO电解质通过，并与图 1中所示比较该电流密度的电压响应。停止循环例程当电池电压响应下降到0.00伏，因为电池未能通过短路指示生长锂枝晶的。 </li></ol>书名"&gt; 4。同步硬X射线微断层成像<ol><li>后对称细胞循环，把它放回手套箱并从袋中取出。 </li><li>使用1/8英寸冲金属切出cell.Vacuum的中心部分在小袋材料密封该单元的中心部分和从手套箱取出运输到同步加速器设施。 注意:通过成像的样品与一个减小的直径，材料的视X射线检测器的领域外的量减少。这提高了通过减少由此引起的额外的材料噪声图像的整体质量。此外，通过去除高X射线吸收镍集电体是必要的，对于该特定袋设计，以得到清晰的X射线图像。 </li><li>一旦在束线中，使用聚酰亚胺胶带贴上样品到样品台。如果需要的话，带的小金属标记在样品上，以辅助对准的顶部。放置金属标记大致在SAMP中心乐以纪念其周围的样本将轮换一次对准的位置。 </li><li>使用20千电子伏的X射线图像的样品与用于系统优化曝光时间。通过平衡扫描时间和每图像计数的数量优化曝光时间。由所收集的图像数乘以曝光时间估计的总扫描时间。 <ol><li>这里，使用300毫秒的曝光时间，从而在5至10分钟的扫描时间。 </li></ol></li><li>测量与所述光学透镜在每个beamtime移的开始相关联的像素大小。 注意:对于用于采取图 2中所示的图像的4倍透镜，像素大小为1.61微米/像素。更高的放大倍率透镜（10倍和20倍）也可以使用。 </li><li>位置和对准上的旋转台的样品相对于该检测系统，使之保持在视检测器的领域，因为它转过180°。 </li><li>样品接近定位检测器是可能的，同时确保样品不击中探测器在任何旋转角度。 注意:作为样品到检测器距离的增加，菲涅尔相衬将成为重建图像更加明显。这可以掩盖的功能，并导致较差的分辨率。为袋状电池，样品检测器距离通常为3厘米远离探测器的顺序。 </li><li>一旦对准，执行扫描包括收集0和180°之间旋转样品1025的图像。收集"明场"（也称为"平场"或"背景"）通过移动样品从视场的图像。此外，通过拍摄图像而梁是断收"暗场"的图像。使用这些规范化的样本图像的光照不均匀，闪烁体响应和CCD相机的响应。 </li></ol> 5.图像重建<ol><li> Tomographically重建集1025 X光片堆叠成图像，其中每个图像表示中使用以下步骤的体积的切片。 <ol><li>首先，从X光片图像和"亮场"画面，不管是减去"暗场"图像正常化的图像。划分所产生的X光片图像所产生的"明场"图像分割。 </li><li>接着，进行断层摄影重建，通过该系列投影角度被转换成3D图像的过程中，上，根据制造商的协议的标准化X射线照片的图像。 注意:重​​建软件输出一系列图像，每个代表通过sample.When一个水平片段堆叠，这组重建图像的形成样品的三维X射线吸收图。 </li></ol></li><li>可视化的个别切片或三维空间的样本，看看有什么样的样子在里面。</li></ol> 6，数据可视化和处理<ol><li>使用可用于数据可视化和分析大量的商业和开源图像处理软件包中的一个。22，23 </li><li>在与所希望的软件开重建图像的堆叠，创建orthoslices来显示XY，XZ和重构数据的YZ观点。 </li><li>平移，通过这些图像和搜 ​​索感兴趣的功能，如在图2所示的锂枝晶。 </li><li>接下来，使用分割（数字标记）和3D渲染工具来呈现的以三维感兴趣的特征。 </li><li>以数字方式分割图像，创建一个标签字段并使用阈值工具来选择相应的材料样品的地区。 </li><li>要重新创建这样的图像，如图2B中所示 ，标号的暗像素锂和亮像素电解质。标签中所含的锂枝晶分别从顶部和底部锂电极。 <ol><li>渲染树枝状锂的橙色和蓝色的高分子电解质。呈现灰色的顶部和底部锂金属电极和调整透明度值以显示橙色树枝状锂。这个旋转三维重建，从多角度观看的结构。 </li></ol></li></ol>

<ol>
	<li>Bruce, P. G., Freunberger, S. A., Hardwick, L. J., Tarascon, J. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Li-O-2+and+Li-S+batteries+with+high+energy+storage.">Li-O-2 and Li-S batteries with high energy storage.</a> Nat Mater. 11, 19-29 (2012).</li><li>Balsara, N. P., Newman, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Comparing+the+Energy+Content+of+Batteries,+Fuels,+and+Materials.">Comparing the Energy Content of Batteries, Fuels, and Materials.</a> J Chem Educ. 90, 446-452 (2013).</li><li>Girishkumar, G., McCloskey, B., Luntz, A. C., Swanson, S., Wilcke, W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Lithium+-+Air+Battery:+Promise+and+Challenges.">Lithium - Air Battery: Promise and Challenges.</a> J Phys Chem Lett. 1, 2193-2203 (2010).</li><li>Selim, R., Bro, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Some+observations+on+rechargeable+lithium+electrodes+in+a+propylene+carbonate+electrolyte.">Some observations on rechargeable lithium electrodes in a propylene carbonate electrolyte.</a> J Electrochem Soc. 121, 1457-1459 (1974).</li><li>Aurbach, D., Zinigrad, E., Cohen, Y., Teller, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+short+review+of+failure+mechanisms+of+lithium+metal+and+lithiated+graphite+anodes+in+liquid+electrolyte+solutions.">A short review of failure mechanisms of lithium metal and lithiated graphite anodes in liquid electrolyte solutions.</a> Solid State Ionics. 148, 405-416 (2002).</li><li>Monroe, C., Newman, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Dendrite+Growth+in+Lithium/Polymer+Systems.">Dendrite Growth in Lithium/Polymer Systems.</a> J Electrochem Soc. 150, A1377 (2003).</li><li>Barton, J. L., Bockris, J. O. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+Electrolytic+Growth+of+Dendrites+from+Ionic+Solutions.">The Electrolytic Growth of Dendrites from Ionic Solutions.</a> Proc R Soc Ser A. 268, 485-505 (1962).</li><li>Bhattacharyya, 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=In+situ+NMR+observation+of+the+formation+of+metallic+lithium+microstructures+in+lithium+batteries.">In situ NMR observation of the formation of metallic lithium microstructures in lithium batteries.</a> Nat Mater. 9, 504-510 (2010).</li><li>Chandrashekar, S., 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=7Li+MRI+of+Li+batteries+reveals+location+of+microstructural+lithium.">7Li MRI of Li batteries reveals location of microstructural lithium.</a> Nat Mater. 11, 311-315 (2012).</li><li>Arora, P., White, R. E., Doyle, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Capacity+fade+mechanisms+and+side+reactions+in+lithium-ion+batteries.">Capacity fade mechanisms and side reactions in lithium-ion batteries.</a> J Electrochem Soc. 145, 3647-3667 (1998).</li><li>Ebner, M., Marone, F., Stampanoni, M., Wood, V. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Visualization+and+Quantification+of+Electrochemical+and+Mechanical+Degradation+in+Li+Ion+Batteries.">Visualization and Quantification of Electrochemical and Mechanical Degradation in Li Ion Batteries.</a> Science. 342, 716-720 (2013).</li><li>Qi, Y., Harris, S. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=In+Situ+Observation+of+Strains+during+Lithiation+of+a+Graphite+Electrode.">In Situ Observation of Strains during Lithiation of a Graphite Electrode.</a> J Electrochem Soc. 157, A741-A747 (2010).</li><li>Eastwood, D. S., 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=Three-dimensional+characterization+of+electrodeposited+lithium+microstructures+using+synchrotron+X-ray+phase+contrast+imaging.">Three-dimensional characterization of electrodeposited lithium microstructures using synchrotron X-ray phase contrast imaging.</a> Chem Commun. , (2014).</li><li>Shui, J. -. 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=Reversibility+of+anodic+lithium+in+rechargeable+lithium&#8211;oxygen+batteries.">Reversibility of anodic lithium in rechargeable lithium&#8211;oxygen batteries.</a> Nat commun. 4, (2013).</li><li>Harry, K. J., Hallinan, D. T., Parkinson, D. Y., MacDowell, A. A., Balsara, N. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Detection+of+subsurface+structures+underneath+dendrites+formed+on+cycled+lithium+metal+electrodes.">Detection of subsurface structures underneath dendrites formed on cycled lithium metal electrodes.</a> Nat Mater. 13, 69-73 (2014).</li><li>Baruchel, 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=Advances+in+synchrotron+hard+X-ray+based+imaging.">Advances in synchrotron hard X-ray based imaging.</a> Cr Phys. 9, 624-641 (2008).</li><li>Flannery, B. P., Deckman, H. W., Roberge, W. G., D'Amico, K. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Three-Dimensional+X-ray+Microtomography.">Three-Dimensional X-ray Microtomography.</a> Science. 237, 1439-1444 (1987).</li><li>Singh, 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=Effect+of+molecular+weight+on+the+mechanical+and+electrical+properties+of+block+copolymer+electrolytes.">Effect of molecular weight on the mechanical and electrical properties of block copolymer electrolytes.</a> Macromolecules. 40, 4578-4585 (2007).</li><li>Monroe, C., Newman, 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+Impact+of+Elastic+Deformation+on+Deposition+Kinetics+at+Lithium/Polymer+Interfaces.">The Impact of Elastic Deformation on Deposition Kinetics at Lithium/Polymer Interfaces.</a> J Electrochem Soc. 152, A396-1149 (2005).</li><li>Stone, G. 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=Resolution+of+the+Modulus+versus+Adhesion+Dilemma+in+Solid+Polymer+Electrolytes+for+Rechargeable+Lithium+Metal+Batteries.">Resolution of the Modulus versus Adhesion Dilemma in Solid Polymer Electrolytes for Rechargeable Lithium Metal Batteries.</a> J Electrochem Soc. 159, A222-A227 (2012).</li><li>Panday, A., 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=Effect+of+Molecular+Weight+and+Salt+Concentration+on+Conductivity+of+Block+Copolymer+Electrolytes.">Effect of Molecular Weight and Salt Concentration on Conductivity of Block Copolymer Electrolytes.</a> Macromolecules. 42, 4632-4637 (2009).</li><li>Schneider, C. A., Rasband, W. S., Eliceiri, K. W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=NIH+Image+to+ImageJ:+25+years+of+image+analysis.">NIH Image to ImageJ: 25 years of image analysis.</a> Nat methods. 9, 671-675 (2012).</li><li>Henke, B. L., Gullikson, E. M., Davis, J. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=X-Ray+Interactions+-+Photoabsorption,+Scattering,+Transmission+and+Reflection+at+E=50-30,000+Ev,+Z=1-92+(Vol+54,+Pg+181,+1993).">X-Ray Interactions - Photoabsorption, Scattering, Transmission and Reflection at E=50-30,000 Ev, Z=1-92 (Vol 54, Pg 181, 1993).</a> Atom Data Nucl Data. 55, 349-349 (1993).</li></ol>

The authors have nothing to disclose.

Hard X-ray microtomography is especially well-suited for air-sensitive samples, like many electrochemically active materials, since the X-rays can penetrate through protective pouch material, enabling facile imaging of the sample without exposure to air. Perhaps the most valuable characteristic of this imaging technique is that the penetrating X-rays allow the user to see inside of the sample without destroying it. Most common imaging techniques, like scanning electron microscopy and traditional optical microscopy, can o...

Researchers are actively investigating battery chemistries with theoretical energy densities over an order of magnitude larger than traditional lithium-ion batteries.1,2 These high-energy-density batteries will make electric vehicles more competitive with their gasoline-powered counterparts.3 However, these new chemistries have several failure modes that preclude their use in commercial technologies. For example, these battery chemistries require a lithium metal anode to achieve large enhancements in energy density; unfortunately, lithium metal is prone to dendrite growth as lithium ions are reduced at the anode surface during charging.4-9 Additionally, breakage of active particles in the cathode and poor adhesion within the battery can cause cell failure.10
Many modes of battery failure occur on the micrometer scale. However, most battery materials are air sensitive making sample preparation for analysis by electron microscopy and traditional optical microscopy difficult. Synchrotron hard X-ray microtomography allows one to visualize the interior of a battery without disassembly.11-14 Furthermore, the technique produces a three-dimensional (3D) reconstruction of the assembled cell making it easy to find locations of failure.15 Finding robust techniques that enable researchers to develop the scientific understanding required to accurately predict the lifetime of a battery is critical for the design of next generation battery technologies. The procedure discussed herein will specifically demonstrate how one can prepare and image model batteries to study the growth of lithium metal dendrites through solid polymer electrolyte membranes.
Computed tomography (CT) scanning is not a new technique and has been used frequently for failure analysis in industry. Synchrotron-based X-ray microtomography is advantageous because the high brightness and flux of the source allow collection of images with high resolution and good signal to noise in a much shorter amount of time.16 Additionally, one can take advantage of the X-ray energy resolution to image at energies around a chemical species&#8217; absorption edge, causing the components containing that chemical species to be identified.17 It was found that the synchrotron source provides sufficient flux to achieve good contrast between lithium metal and solid polymer electrolyte membranes enabling one to image lithium metal dendrites.15
The study discussed herein uses a high modulus, block copolymer electrolyte membrane.18 These high modulus membranes suppress lithium dendrite growth, lengthening the lifetime of batteries.19,20 However, dendrites still eventually puncture the membrane causing the battery to fail by short-circuit. It is important to understand the nature of dendrite formation and growth in these high modulus electrolyte membranes in order to design strategies to prevent their growth.

<table><tbody><tr><td>Anhydrous N-methyl-2-pyrrolidone&amp;nbsp;</td><td>MILLIPORE</td><td>MX1396-7</td><td></td></tr><tr><td>Lithium bis(trifluoromethane)sulfonamide</td><td>MILLIPORE</td><td>8438730010</td><td></td></tr><tr><td>Lithium metal</td><td>FMC Lithium</td><td>None</td><td>Lectro Max 100</td></tr><tr><td>Pouch material</td><td>MTI Corporation</td><td>EQ-alf-400-7.5M</td><td></td></tr><tr><td>Nickel tabs</td><td>MTI Corporation</td><td>EQ-PLiB-NTA3</td><td></td></tr></tbody></table>

failure analysis of batteries using synchrotron-based hard x-ray microtomography

Imaging morphological changes that occur during the lifetime of rechargeable batteries is necessary to understand how these devices fail. Since the advent of lithium-ion batteries, researchers have known that the lithium metal anode has the highest theoretical energy density of any anode material. However, rechargeable batteries containing a lithium metal anode are not widely used in consumer products because the growth of lithium dendrites from the anode upon charging of the battery causes premature cell failure by short circuit. Lithium dendrites can also form in commercial lithium-ion batteries with graphite anodes if they are improperly charged. We demonstrate that lithium dendrite growth can be studied using synchrotron-based hard X-ray microtomography. This non-destructive imaging technique allows researchers to study the growth of lithium dendrites, in addition to other morphological changes inside batteries, and subsequently develop methods to extend battery life.

When the symmetric lithium-lithium cells described above are cycled at 90 &#176;C, the voltage response looks like that shown in Figure 1. Eventually, lithium dendrites will grow through the electrolyte and cause the cell to fail by short circuit. When this happens, the voltage response to the applied current will drop down to 0.00 V. Dendrites, like the one shown in Figure 2 appear in samples that have failed by short circuit. Non-electrolyte spanning dendrites are also found in the sam...

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Failure Analysis of Batteries Using Synchrotron-based Hard X-ray Microtomography

Synchrotron-based hard X-ray microtomography is used to image the electrochemical growth of dendrites from a lithium metal electrode through a solid polymer electrolyte membrane.

电池的使用同步为基础的硬X射线微断层故障分析

Imaging morphological changes that occur during the lifetime of rechargeable batteries is necessary to understand how these devices fail. Since the advent ...

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8.8K 次观看.  University of California Berkeley. Synchrotron-based hard X-ray microtomography is used to image the electrochemical growth of dendrites from a lithium metal electrode through a solid polymer electrolyte membrane.

视频: Failure Analysis of Batteries Using Synchrotron-based Hard X-ray Microtomography

Characterization of Electrode Materials for Lithium Ion and Sodium Ion Batteries Using Synchrotron Radiation Techniques

Intercalation compounds such as transition metal oxides or phosphates are the most commonly used electrode materials in Li-ion and Na-ion batteries. During insertion or removal of alkali metal ions, the redox states of transition metals in the compounds change and structural transformations such as phase transitions and/or lattice parameter increases or decreases occur. These behaviors in turn determine important characteristics of the batteries such as the potential profiles, rate capabilities, and cycle lives. The extremely bright and tunable x-rays produced by synchrotron radiation allow rapid acquisition of high-resolution data that provide information about these processes. Transformations in the bulk materials, such as phase transitions, can be directly observed using X-ray diffraction (XRD), while X-ray absorption spectroscopy (XAS) gives information about the local electronic and geometric structures (e.g.&#160;changes in redox states and bond lengths). In situ experiments carried out on operating cells are particularly useful because they allow direct correlation between the electrochemical and structural properties of the materials. These experiments are time-consuming and can be challenging to design due to the reactivity and air-sensitivity of the alkali metal anodes used in the half-cell configurations, and/or the possibility of signal interference from other cell components and hardware. For these reasons, it is appropriate to carry out ex situ experiments (e.g.&#160;on electrodes harvested from partially charged or cycled cells) in some cases. Here, we present detailed protocols for the preparation of both ex situ and in situ samples for experiments involving synchrotron radiation and demonstrate how these experiments are done.

We describe the use of synchrotron X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) techniques to probe details of intercalation/deintercalation processes in electrode materials for Li-ion and Na-ion batteries. Both in situ and ex situ experiments are used to understand structural behavior relevant to the operation of devices

正极材料的同步辐射技术锂离子和钠离子电池表征

Intercalation compounds such as transition metal oxides or phosphates are the most commonly used electrode materials in Li-ion and Na-ion batteries. ...

科研

工程学

In Situ Neutron Powder Diffraction Using Custom-made Lithium-ion Batteries

Li-ion batteries are widely used in portable electronic devices and are considered as promising candidates for higher-energy applications such as electric vehicles.1,2 However, many challenges, such as energy density and battery lifetimes, need to be overcome before this particular battery technology can be widely implemented in such applications.3 This research is challenging, and we outline a method to address these challenges using in situ NPD to probe the crystal structure of electrodes undergoing electrochemical cycling (charge/discharge) in a battery. NPD data help determine the underlying structural mechanism responsible for a range of electrode properties, and this information can direct the development of better electrodes and batteries.
We briefly review six types of battery designs custom-made for NPD experiments and detail the method to construct the &#8216;roll-over&#8217; cell that we have successfully used on the high-intensity NPD instrument, WOMBAT, at the Australian Nuclear Science and Technology Organisation (ANSTO). The design considerations and materials used for cell construction are discussed in conjunction with aspects of the actual in situ NPD experiment and initial directions are presented on how to analyze such complex in situ data.

In Situ Neutron Powder Diffraction Using Custom-made Lithium-ion Batteries

We describe the design and construction of an electrochemical cell for the examination of electrode materials using in situ neutron powder diffraction (NPD). We briefly comment on alternate in situ NPD cell designs and discuss methods for the analysis of the corresponding in situ NPD data produced using this cell.

原位中子衍射用特制的锂离子电池

Li-ion batteries are widely used in portable electronic devices and are considered as promising candidates for higher-energy applications such as electric ...

Using Synchrotron Radiation Microtomography to Investigate Multi-scale Three-dimensional Microelectronic Packages

Synchrotron radiation micro-tomography (SR&#181;T) is a non-destructive three-dimensional (3D) imaging technique that offers high flux for fast data acquisition times with high spatial resolution. In the electronics industry there is serious interest in performing failure analysis on 3D microelectronic packages, many which contain multiple levels of high-density interconnections. Often in tomography there is a trade-off between image resolution and the volume of a sample that can be imaged. This inverse relationship limits the usefulness of conventional computed tomography (CT) systems since a microelectronic package is often large in cross sectional area 100-3,600 mm2, but has important features on the micron scale. The micro-tomography beamline at the Advanced Light Source (ALS), in Berkeley, CA USA, has a setup which is adaptable and can be tailored to a sample&#39;s properties, i.e., density, thickness, etc., with a maximum allowable cross-section of 36 x 36 mm. This setup also has the option of being either monochromatic in the energy range ~7-43 keV or operating with maximum flux in white light mode using a polychromatic beam. Presented here are details of the experimental steps taken to image an entire 16 x 16 mm system within a package, in order to obtain 3D images of the system with a spatial resolution of 8.7 &#181;m all within a scan time of less than 3 min. Also shown are results from packages scanned in different orientations and a sectioned package for higher resolution imaging. In contrast a conventional CT system would take hours to record data with potentially poorer resolution. Indeed, the ratio of field-of-view to throughput time is much higher when using the synchrotron radiation tomography setup. The description below of the experimental setup can be implemented and adapted for use with many other multi-materials.

For this study synchrotron radiation micro-tomography, a non-destructive three-dimensional imaging technique, is employed to investigate an entire microelectronic package with a cross-sectional area of 16 x 16 mm. Due to the synchrotron&#39;s high flux and brightness the sample was imaged in just 3 min&#160;with an 8.7 &#181;m spatial resolution.

利用同步辐射微断层调查的多尺度三维微电子封装

Synchrotron radiation micro-tomography (SR&#181;T) is a non-destructive three-dimensional (3D) imaging technique that offers high flux for fast data ...

Non-invasive 3D-Visualization with Sub-micron Resolution Using Synchrotron-X-ray-tomography

Little is known about the internal organization of many micro-arthropods with body sizes below 1 mm. The reasons for that are the small size and the hard cuticle which makes it difficult to use protocols of classical histology. In addition, histological sectioning destroys the sample and can therefore not be used for unique material. Hence, a non-destructive method is desirable which allows to view inside small samples without the need of sectioning.
We used synchrotron X-ray tomography at the European Synchrotron Radiation Facility (ESRF) in Grenoble (France) to non-invasively produce 3D tomographic datasets with a pixel-resolution of 0.7&micro;m. Using volume rendering software, this allows us to reconstruct the internal organization in its natural state without the artefacts produced by histological sectioning. These date can be used for quantitative morphology, landmarks, or for the visualization of animated movies to understand the structure of hidden body parts and to follow complete organ systems or tissues through the samples.

We used synchrotron X-ray tomography at the European Synchrotron Radiation Facility (ESRF) to non-invasively produce 3D tomographic datasets with a pixel-resolution of 0.7&micro;m. Using volume rendering software, this allows the reconstruction of internal structures in their natural state without the artefacts produced by histological sectioning.

非侵入性的三维可视化与亚微米分辨率使用同步加速器X射线断层扫描

Little is known about the internal organization of many micro-arthropods with body sizes below 1 mm. The reasons for that are the small size and the hard ...

生物学

Dynamic Pore-scale Reservoir-condition Imaging of Reaction in Carbonates Using Synchrotron Fast Tomography

Underground storage permanence is a major concern for carbon capture and storage. Pumping CO2 into carbonate reservoirs has the potential to dissolve geologic seals and allow CO2 to escape. However, the dissolution processes at reservoir conditions are poorly understood. Thus, time-resolved experiments are needed to observe and predict the nature and rate of dissolution at the pore scale. Synchrotron fast tomography is a method of taking high-resolution time-resolved images of complex pore structures much more quickly than traditional &#181;-CT. The Diamond Lightsource Pink Beam was used to dynamically image dissolution of limestone in the presence of CO2-saturated brine at reservoir conditions. 100 scans were taken at a 6.1 &#181;m resolution over a period of 2 hours. The images were segmented and the porosity and permeability were measured using image analysis and network extraction. Porosity increased uniformly along the length of the sample; however, the rate of increase of both porosity and permeability slowed at later times.

Synchrotron fast tomography was used to dynamically image dissolution of limestone in the presence of CO2-saturated brine at reservoir conditions. 100 scans were taken at a 6.1 &#181;m resolution over a period of 2 h.

用同步快速反应层析成像动态孔隙规模油藏条件下成像碳酸盐

Underground storage permanence is a major concern for carbon capture and storage. Pumping CO2 into carbonate reservoirs has the potential to dissolve ...

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

Energy storage has become more and more a limiting factor of today's sustainable energy applications, including electric vehicles and green electric grid based on volatile solar and wind sources. The pressing demand of developing high-performance electrochemical energy storage solutions, i.e., batteries, relies on both fundamental understanding and practical developments from both the academy and industry. The formidable challenge of developing successful battery technology stems from the different requirements for different energy-storage applications. Energy density, power, stability, safety, and cost parameters all have to be balanced in batteries to meet the requirements of different applications. Therefore, multiple battery technologies based on different materials and mechanisms need to be developed and optimized. Incisive tools that could directly probe the chemical reactions in various battery materials are becoming critical to advance the field beyond its conventional trial-and-error approach. Here, we present detailed protocols for soft X-ray absorption spectroscopy (sXAS), soft X-ray emission spectroscopy (sXES), and resonant inelastic X-ray scattering (RIXS) experiments, which are inherently elemental-sensitive probes of the transition-metal 3d and anion 2p states in battery compounds. We provide the details on the experimental techniques and demonstrations revealing the key chemical states in battery materials through these soft X-ray spectroscopy techniques.

Here, we present a protocol for typical experiments of soft X-ray absorption spectroscopy (sXAS) and resonant inelastic X-ray scattering (RIXS) with applications in battery material studies.

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

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

化学

Synchrotron X-ray Microdiffraction and Fluorescence Imaging of Mineral and Rock Samples

In this report, we describe a detailed procedure for acquiring and processing&#160;x-ray microfluorescence (&#956;XRF), and Laue and powder microdiffraction two-dimensional (2D) maps at beamline 12.3.2 of the Advanced Light Source (ALS), Lawrence Berkeley National Laboratory. Measurements can be performed on any sample that is less than 10 cm x 10 cm x 5 cm, with a flat exposed surface. The experimental geometry is calibrated using standard materials (elemental standards for XRF, and crystalline samples such as Si, quartz, or Al2O3 for diffraction). Samples are aligned to the focal point of the x-ray microbeam, and raster scans are performed, where each pixel of a map corresponds to one measurement, e.g., one XRF spectrum or one diffraction pattern. The data are then processed using the in-house developed software XMAS, which outputs text files, where each row corresponds to a pixel position. Representative data from moissanite and an olive snail shell are presented to demonstrate data quality, collection, and analysis strategies.

We describe a beamline setup meant to carry out rapid two-dimensional x-ray fluorescence and x-ray microdiffraction mapping of single crystal or powder samples using either Laue (polychromatic radiation) or powder (monochromatic radiation) diffraction. The resulting maps give information about strain, orientation, phase distribution, and plastic deformation.

矿物和岩石样品的同步辐射 x 射线 Microdiffraction 和荧光成像

In this report, we describe a detailed procedure for acquiring and processing&#160;x-ray microfluorescence (&#956;XRF), and Laue and powder ...

X-ray Beam Induced Current Measurements for Multi-Modal X-ray Microscopy of Solar Cells

X-ray beam induced current (XBIC) measurements allow mapping of&#160;the nanoscale performance of electronic devices such as solar cells. Ideally, XBIC is employed simultaneously with other techniques within a multi-modal X-ray microscopy approach. An example is given herein combining XBIC with X-ray fluorescence to enable point-by-point correlations of the electrical performance with chemical composition. For the highest signal-to-noise ratio in XBIC measurements, lock-in amplification plays a crucial role. By this approach, the X-ray beam is modulated by an optical chopper upstream of the sample. The modulated X-ray beam induced electrical signal is amplified and demodulated to the chopper frequency using a lock-in amplifier. By optimizing low-pass filter settings, modulation frequency, and amplification amplitudes, noise can efficiently be suppressed for the extraction of a clear XBIC signal. A similar setup can be used to measure the X-ray beam induced voltage (XBIV). Beyond standard XBIC/XBIV measurements, XBIC can be measured with bias light or bias voltage applied such that outdoor working conditions of solar cells can be reproduced during in-situ and operando measurements. Ultimately, the multi-modal and multi-dimensional evaluation of electronic devices at the nanoscale enables new insights into the complex dependencies between composition, structure, and performance, which is an important step towards solving the materials&#39; paradigm.

A setup for X-ray beam induced current measurements at synchrotron beamlines is described. It unveils the nanoscale performance of solar cells and extends the suite of techniques for multi-modal X-ray microscopy. From wiring to signal-to-noise optimization, it is shown how to perform state-of-the-art XBIC measurements at a hard X-ray microprobe.

太阳能电池多模态X射线显微镜的X射线光束诱导电流测量

X-ray beam induced current (XBIC) measurements allow mapping of&#160;the nanoscale performance of electronic devices such as solar cells. Ideally, XBIC is ...

Visualization of Failure and the Associated Grain-Scale Mechanical Behavior of Granular Soils under Shear using Synchrotron X-Ray Micro-Tomography

The rapid development of X-ray imaging techniques with image processing and analysis skills has enabled the acquisition of CT images of granular soils with high-spatial resolutions. Based on such CT images, grain-scale mechanical behavior such as particle kinematics (i.e., particle translations and particle rotations), strain localization and inter-particle contact evolution of granular soils can be quantitatively investigated. However, this is inaccessible using conventional experimental methods. This study demonstrates the exploration of the grain-scale mechanical behavior of a granular soil sample under triaxial compression using synchrotron X-ray micro-tomography (&#956;CT). With this method, a specially fabricated miniature loading apparatus is used to apply confining and axial stresses to the sample during the triaxial test. The apparatus is fitted into a synchrotron X-ray tomography setup so that high-spatial resolution CT images of the sample can be collected at different loading stages of the test without any disturbance to the sample. With the capability of extracting information at the macro scale (e.g., sample boundary stresses and strains from the triaxial apparatus setup) and the grain scale (e.g., grain movements and contact interactions from the CT images), this procedure provides an effective methodology to investigate the multi-scale mechanics of granular soils.

The protocol describes procedures to acquire high-spatial resolution computed tomography (CT) images of a granular soil during triaxial compression, and to apply image processing techniques to these CT images to explore the grain-scale mechanical behavior of the soil under loading.

使用同步加速器 X 射线微断层扫描技术，在剪切下对颗粒土壤的故障和相关的颗粒级机械性能进行可视化

The rapid development of X-ray imaging techniques with image processing and analysis skills has enabled the acquisition of CT images of granular soils ...

Nanoscale Characterization of Liquid-Solid Interfaces by Coupling Cryo-Focused Ion Beam Milling with Scanning Electron Microscopy and Spectroscopy

Physical and chemical processes at solid-liquid interfaces play a crucial role in many natural and technological phenomena, including catalysis, solar energy and fuel generation, and electrochemical energy storage. Nanoscale characterization of such interfaces has recently been achieved using cryogenic electron microscopy, thereby providing a new path to advancing our fundamental understanding of interface processes.
This contribution provides a practical guide to mapping the structure and chemistry of solid-liquid interfaces in materials and devices using an integrated cryogenic electron microscopy approach. In this approach, we pair cryogenic sample preparation which allows stabilization of solid-liquid interfaces with cryogenic focused ion beam (cryo-FIB) milling to create cross-sections through these complex buried structures. Cryogenic scanning electron microscopy (cryo-SEM) techniques performed in a dual-beam FIB/SEM enable direct imaging as well as chemical mapping at the nanoscale. We discuss practical challenges, strategies to overcome them, as well as protocols for obtaining optimal results. While we focus in our discussion on interfaces in energy storage devices, the methods outlined are broadly applicable to a range of fields where solid-liquid interface play a key role.

Cryogenic Focused Ion Beam (FIB) and Scanning Electron Microscopy (SEM) techniques can provide key insights into the chemistry and morphology of intact solid-liquid interfaces. Methods for preparing high quality Energy Dispersive X-ray (EDX) spectroscopic maps of such interfaces are detailed, with a focus on energy storage devices.

通过冷冻聚焦离子束铣削与扫描电子显微镜和光谱学耦合，对液固界面进行纳米级表征

Physical and chemical processes at solid-liquid interfaces play a crucial role in many natural and technological phenomena, including catalysis, solar ...