作者感谢 Marc 斯蒂恩和露易丝布雷特为他们的优秀支持审查这份手稿。

注: 在这项工作中遵循的协议详细解释了. 39. 下面介绍了重要步骤的摘要。
1. 邮袋细胞的制备和形成
<ol><li>制作 B5 格式的邮袋单元, 其尺寸为250毫米 x 164 毫米, 厚度约为4毫米, 以人造石墨为阳极材料, 磷酸铁锂 (LFP) 为阴极材料, 25-µm 厚聚丙烯分离器。</li>
	<li>使用80克电解质: 1 米 LiPF6在碳酸乙烯: 碳酸二乙酯 (2:3 w/w) 含1% 乙炔碳酸酯。 注: 囊细胞制作是在半自动工业试验生产线上进行的, 包括以下步骤: i) 一种含下列活性材料的浆料制备: 用于阴极的阳极和 LFP 的石墨、粘合剂和导电添加剂在实验室规模的搅拌机 ii.) 在当前收集器 (铝箔和铜箔, 分别为阴极和阳极电极) 上的浆料涂层, iii. 一种优化电极性能的压延,如电极密度, 孔隙度, 厚度, 电子电导率和阻抗, 其次为 iv) 的组装, 电解质灌装和密封。</li>
	<li>进行细胞的形成。使用以下步骤创建带有电池循环仪软件的循环协议。<ol>
<li>使用电池循环仪软件的生成测试功能。单击新文件图标 (请参阅辅助文件 1a中的蓝色箭头)。</li>
		<li>协议代码中的每一行都是指循环的参数 (例如, 休息时间和截止电压) (补充文件 1b)。按要求填写每个步骤, 执行两步恒流电压 (CC CV) 充电 0.1 C 至 3.6 V, 10 毫安截止电流和 CC 放电 0.1 C 至 2.5 v。在形成步骤之后, 向电池充电30% 的充电状态 (SOC)。单击 "保存" 按钮并提供一个文件名。</li>
		<li>通过单击相应的通道来选择要循环的单元格 (请参见辅助文件 2中的蓝色箭头 1)。该通道在 "状态" 列中标记为 "选定"。然后单击 "运行" 按钮 (参见工具栏顶部的 "辅助文件 2中的蓝色箭头2号")。</li>
		<li>选择协议 (请参阅辅助文件 3中的蓝色箭头 1), 设置单元格的容量 (Ah) (请参见辅助文件 3中的蓝色箭头 2) 并分配一个分庭 (参见补充文件 3中的蓝色箭头 3)。定义一个有效的文件名, 然后单击 "开始" 按钮。</li>
	</ol>
</li>
</ol>2. 电化学测试前的细胞夹具
<ol><li>将每个单元格放置在相应的支架上, 由两个刚性板组成 (宽度和长度分别为300毫米 x 300 毫米, 厚度为12毫米) 由聚碳酸酯制成。</li>
	<li>将热电偶放在每个单元格的一侧的中心, 以监测表面温度变化。</li>
	<li>将细胞和固定装置放置在温度室中, 以控制整个实验过程中的环境温度。在同一温度室中, 将两个单元格置于相同的协议后面。</li>
	<li>通过与循环仪的4线连接连接单元格。</li>
</ol>3. 电化学循环
<ol><li>
细胞调理
	<ol>
<li>设置温度在25摄氏度在环境室。至少允许12小时以确保热量平衡。</li>
		<li>使用电池循环仪执行三充电/放电循环。<ol>
<li>根据步骤1.3.1 和 1.3.2, 为电池循环仪创建协议。在这种情况下, 将协议步骤调整为 0.1 c (从额定容量) 到 3.7 V (cv 阶段直到 0.01 c 或 1 h) 的 cc CV 充电, 然后 cc 放电在 0.1 c 直到 2.7 v 在每个循环步骤之后使用30分钟的休息时间。</li>
			<li>执行通道和协议选择的步骤1.3.3 和1.3.4。</li>
			<li>当两个单元格放置在同一温度室 (两个单元格遵循相同的协议) 时, 同时选择两个相应的通道。这保证了两个单元的循环和燃烧室温度条件的同步。</li>
		</ol>
</li>
		<li>执行参考周期 (步骤 3.2), 并使用它来评估初始容量 (Ci) (表 1)。</li>
	</ol>
</li>
	<li>
参考循环
	<ol>
<li>作为单元格调节 (步骤 3.1.3) 和周期性间隔 (即25 长期老化周期) 的一部分执行参考循环, 见下文)。</li>
		<li>设置温度的房间在25°c, 当测试是在不同的温度执行, 并允许足够的时间, 热稳定 (< 1 的-1)。</li>
		<li>使用电池循环仪执行两个 CC 充电/放电循环。<ol>
<li>按照1.3.1 的步骤, 为电池循环仪创建协议。和1.3.2。在这种情况下, 将协议步骤调整为 CC 充放电 0.3 C (如IEC 62660-1: 2011)13。每个循环步骤后, 允许额外的时间来稳定温度 (< 1 的-1)。</li>
			<li>执行通道和协议选择的步骤1.3.3 和1.3.4。</li>
			<li>当两个单元格放置在同一温度室 (两个单元格遵循相同的协议) 时, 同时选择两个相应的通道。这保证了两个单元的循环和燃烧室温度条件的同步。</li>
		</ol>
</li>
	</ol>
</li>
	<li>
长期 (老化)
	<ol>
<li>执行100充电/放电周期。按照1.3.1 和1.3.2 的步骤, 为电池循环仪创建协议。在这种情况下, 将协议步骤调整为 1 c 至 3.7 V (cv 阶段直到 0.1 c 或 1 h) 的 cc-cv 充电, 并在充电 (Tc) 和放电期间 (Td) 中以恒定的温度将 1 C 电流的 cc 放电至 2.7 V。</li>
		<li>执行通道和协议选择的步骤1.3.3 和1.3.4。</li>
		<li>在温度范围从-20 °c 到30°c (见表 1中的测试矩阵), 在几个温度组合 (10) 上进行长期老化, 从步骤3.3.1 的100充电/放电循环中, 通过 DOE D 优化36(预测的最小误差)。在Tc和Td相同 (测试1和2、3和4、9和10、13和14以及19和20、表 1) 后, 在每次充电或卸货步骤后的测试协议中设置一个休息时间。然而, 当Tc和Td是不同的 (测试11和 12, 5 和 6, 7 和 8, 15 和 16, 17 和 18,表 1), 设置一个休息时间, 直到温度稳定在 1.</li>
		<li>在每组25个周期之后执行一个引用循环 (请参见步骤 3.2)。</li>
		<li>重复每个测试一次在不同的新鲜细胞, 以评估其重复性。</li>
	</ol>
</li>
	<li>
降解率
	<ol>
<li>评估细胞退化 [容量保留 (CR)] 使用: i) 最新的参考周期和第一参考周期, CRref (见步骤 3.2) 和 ii) 与第一周期相比的长期容量保留, cr长期(请参见步骤 3.3) 和以下等式 (1 和 2): (1)<img alt="Equation 1" src="/files/ftp_upload/57501/57501eq1.jpg"> (2)<img alt="Equation 2" src="/files/ftp_upload/57501/57501eq2.jpg"><ol>
<li>使用电池循环仪客户端软件访问循环数据。首先, 选择可视化模板 (在辅助文件 4中打开文件), 并在适当的地方选择步骤3.1.2 或3.2.3 中定义的文件名。 注:补充文件 5显示了循环数据的一个示例, 其容量保留作为循环号 (辅助文件 5、顶部图) 和电位变化的函数, 以及当前和温度作为函数的时间 (补充文件 5, 下图)。方程组 (1) 和 (2) 可以直接从地块中使用软件功能确定。</li>
		</ol>
</li>
		<li>使用CRref 和总周期数 (即参考周期和长期周期), 假设DR依赖于电荷Tc , 以适应降解率(dr) 和放电Td 温度由二次期限和相互作用在那些之间温度如下在等式 (3): (3)<img alt="Equation 3" src="/files/ftp_upload/57501/57501eq3.jpg"> 注: 参数 Ai 及其统计意义由最小二乘拟合和方差分析确定, 假设测量不确定度 (err) 与σ方差跟随正态分布。后者应该从剩余的适当的分配被证实。<ol>
<li>为此, 请使用具有 "适合模型" 功能的软件。选择逐步选项 (辅助文件 6中的蓝色箭头 1), 然后选择最大 K 折 RSquare函数 (辅助文件 6中的蓝色箭头 2), 然后单击 "转到"。这会将数据集拆分为一个等效的训练子集, 并且在每个子集上分别完成管接头。选择最佳整体 RSquare 值以避免 overfitting。</li>
			<li>点击制作模型。辅助文件 7显示了管接头的结果。它还计算每个参数 (i) 的意义 (PValue)。在 "效果摘要" 表中, 删除最不重要的参数。在这种情况下,4 (放电温度的二次依赖性) 被证明不重要。因此, 它被取消了进一步的分析。辅助文件 8显示了与实际数据的最终匹配。</li>
		</ol>
</li>
	</ol>
</li>
</ol>4. 验尸分析
<ol><li>拆卸细胞。在手套箱内执行这一步骤 (< 5 ppm 用于 O2和 H2o), 以避免空气中的污染。用陶瓷剪刀切开小袋细胞。切割阳极和阴极电极的小部分 (5 毫米 x 5 毫米), 并将其安装在扫描电镜 (SEM) 样品存根上。</li>
	<li>通过将 SEM 样品持有者放置在密封容器中, 并直接将其转移到 sem 样品室中, 以避免污染, 例如使用附着在充满惰性气体的腔室入口处的手套袋。<ol>
<li>为了减少暴露在空气中, 保持一个超压的惰性气体在手套袋。</li>
	</ol>
</li>
	<li>为了深入检查电极在循环前后的形貌, 对二次电子的两个探测器进行 SEM 成像: 透镜式探测器和标准二次电子探测器。用于透镜内检测器和二次电子探测器的加速电压分别为1伏和15伏。</li>
	<li>对于每个样品, 特征至少五不同的样品表面的位置有代表性 SEM 显微照片和辨认表面的潜在的不均匀性。对于每个位置, 在以下放大执行 SEM 成像: 1 kX、3 kX、5 kX、10 kX、20 kX、50 kX、75 kX、100 kX、150 kX 和 200 kX。</li>
	<li>用能量色散 X 射线 (EDX) 光谱仪分析每个电极的化学成分, 用80毫米2硅漂移探测器 (SDD)。<ol>
<li>使用15伏的加速电压和13毫米的工作距离, 使用二次电子图像进行元素分析。</li>
		<li>选择每个材料至少五个不同的位置在标本表面和分析至少5点产生光谱。</li>
		<li>使用不同的放大, 范围从 2 kX 到 25 kX, 进行半定量分析, 并更好地针对任何特定粒子或结构变化。因此, 对于每个样本, 收集至少 25 EDX 光谱, 以调查元素组成。</li>
		<li>在对试样的给定位置开始化学分析之前, 用铜进行光谱标定。最后, 在每个样本的不同位置测量的平均值, 对于 EDX 映射, 使用2小时的采集时间。</li>
	</ol>
</li>
</ol>

<ol><li>Conte, M., et al. <a target="_blank" href="https://www.yumpu.com/en/document/view/6741426/ageing-testing-procedures-on-lithium-batteries-in-an-international-">Ageing testing procedures on lithium batteries in an international collaboration context.</a> 25th World Battery, Hybrid and Fuel Cell Electric Vehicle Symposium & Exhibition. , November 5 - 8, 2010 (2010).</li>
<li>Barré, A., et al. <a target="_blank" href="https://www.sciencedirect.com/science/article/pii/S0378775313008185">A review on lithium-ion battery ageing mechanisms and estimations for automotive applications.</a> Journal of Power Sources. 241, 680-689 (2013).</li>
<li>Danzer, M., Liebau, V., Maglia, F. <a target="_blank" href="http://scholar.google.com/scholar?hl=en&safe=off&q=author%3aDanzer%2C+M+%22Aging+of+Lithium-ion+Batteries+for+Electric+Vehicles%22">Aging of Lithium-ion Batteries for Electric Vehicles</a>. , Woodhead Publishing. Amsterdam, The Netherlands. (2015).</li>
<li>International Energy Agency (IEA). <a target="_blank" href="https://refman.energytransitionmodel.com/publications/156">Technology Roadmap. Electric and Plug-in Hybrid Electric Vehicles</a>. , Economic Co-operation and Development Publishing. Paris, France. (2011).</li>
<li>Battery R&D Roadmap 2030. Battery Technology for Vehicle Applications. Eurobat E-Mobility. , Available from: 
 <a target="_blank" href="http://www.eurobat.org/sites/default/files/eurobat_emobility_roadmap_lores_2.pdf">http://www.eurobat.org/sites/default/files/eurobat_emobility_roadmap_lores_2.pdf</a> (2015).</li>
<li>SET Plan Secretariat. European Commission. Issues Paper No. 7 "Become competitive in the global battery sector to drive e-mobility forward". , Available from: 
 <a target="_blank" href="http://setis.ec.europa.eu/system/files/integrated_set-plan/action7_issues_paper.pdf">http://setis.ec.europa.eu/system/files/integrated_set-plan/action7_issues_paper.pdf</a> (2016).</li>
<li>Shi, W., et al. <a target="_blank" href="https://www.sciencedirect.com/science/article/pii/S0013468616304625">Analysis of thermal aging paths for large-format LiFePO4/graphite battery.</a> Electrochimica Acta. 196, 13-23 (2016).</li>
<li>Wang, J., et al. <a target="_blank" href="https://www.sciencedirect.com/science/article/pii/S0378775310021269">Cycle-life model for graphite-LiFePO4 cells.</a> Journal of Power Sources. 196 (8), 3942-3948 (2011).</li>
<li>Steffke, K., Inguva, S., Van Cleve, D., Knockeart, J. SAE J1548: accelerated life test methodology for Li-ion batteries in automotive applications. SAE 2013 World Congress & Exhibition. , Detroit, MI (April 16 - 18, 2013) (2013).</li>
<li>Ecker, M., et al. <a target="_blank" href="https://www.sciencedirect.com/science/article/pii/S0378775312008671">Development of a lifetime prediction model for lithium-ion batteries based on extended accelerated aging test data.</a> Journal of Power Sources. 215, 248-257 (2012).</li>
<li>Ramadass, P., Haran, B., White, R., Popov, B. N. <a target="_blank" href="https://www.sciencedirect.com/science/article/pii/S0378775302004743">Capacity fade of Sony 18650 cells cycled at elevated temperatures: Part I. Cycling performance.</a> Journal of Power Sources. 112 (2), 606-613 (2002).</li>
<li>Omar, N., et al. <a target="_blank" href="https://www.sciencedirect.com/science/article/pii/S0306261913007393">Lithium iron phosphate based battery - Assessment of the aging parameters and development of cycle life model.</a> Applied Energy. 113, 1575-1585 (2014).</li>
<li>International Electrotechnical Commission. <a target="_blank" href="https://webstore.iec.ch/publication/7331">Secondary lithium-ion cells for the propulsion of electric road vehicles - Part 1: performance testing</a>. , Geneva, Switzerland. IEC 62660-1 (2011).</li>
<li>International Organization for Standardization. <a target="_blank" href="https://www.iso.org/standard/51414.html">Electrically propelled road vehicles - Test specification for lithium-ion traction battery packs and systems - Part 1: high-power applications</a>. , Geneva, Switzerland. ISO 12405-1 (2011).</li>
<li>International Organization for Standardization. <a target="_blank" href="https://www.iso.org/standard/55854.html">Electrically propelled road vehicles - Test specification for lithium-ion traction battery packs and systems - Part 2: high-energy applications</a>. , Geneva, Switzerland. ISO 12405-2 (2012).</li>
<li>The Engineering Society for Advancing Mobility Land Sea Air and Space International. <a target="_blank" href="https://www.sae.org/standards/content/j2288_199701/">Life Cycle Testing of Electric Vehicle Battery Modules</a>. , Warrendale, PA. SAE J2288 (2008).</li>
<li>The Engineering Society for Advancing Mobility Land Sea Air and Space International. <a target="_blank" href="https://www.sae.org/standards/content/j1798_200807/">Recommended Practice for Performance Rating of Electric Vehicle Battery Modules</a>. , Warrendale, PA. SAE J1798 (2008).</li>
<li>Idaho National Laboratory. <a target="_blank" href="https://digital.library.unt.edu/ark:/67531/metadc842027/">Battery Calendar Life Estimator Manual: Modeling and Simulation</a>. , Idaho Falls, ID. INL-EXT-08-15136. Rev 1 (2012).</li>
<li>Idaho National Laboratory. <a target="_blank" href="https://digital.library.unt.edu/ark:/67531/metadc830392/">Battery Technology Life Verification Test Manual Revision 1</a>. , Idaho Falls, ID. INL-EXT-12-27920 (2012).</li>
<li>United States Advanced Battery Consortium LLC. <a target="_blank" href="https://avt.inl.gov/sites/default/files/pdf/battery/usabc_manual_rev2.pdf">USABC Electric Vehicle Battery Test Procedures Manual Revision 2</a>. , Southfield, MI. (1996).</li>
<li>Jalkanen, K., et al. <a target="_blank" href="https://www.sciencedirect.com/science/article/pii/S0306261915005735">Cycle aging of commercial NMC/graphite pouch cells at different temperatures.</a> Applied Energy. 154, 160-172 (2015).</li>
<li>Ruiz, V., et al. <a target="_blank" href="https://www.sciencedirect.com/science/article/pii/S1364032117308250">A review of international abuse testing standards and regulations for lithium ion batteries in electric and hybrid electric vehicles.</a> Renewable and Sustainable Energy Reviews. 81, Part I 1427-1452 (2017).</li>
<li>Inaba, M., Tomiyasu, H., Tasaka, A., Jeong, S. -K., Ogumi, Z. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Atomic+force+microscopy+study+on+the+stability+of+a+surface+film+formed+on+a+graphite+negative+electrode+at+elevated+temperatures%5BTitle%5D)+AND+%22Langmuir%22%5BJournal%5D)">Atomic force microscopy study on the stability of a surface film formed on a graphite negative electrode at elevated temperatures.</a> Langmuir. 20 (4), 1348-1355 (2004).</li>
<li>Richard, M. N., Dahn, J. R. <a target="_blank" href="http://jes.ecsdl.org/content/146/6/2068.short">Accelerating rate calorimetry study on the thermal stability of lithium intercalated graphite in electrolyte. I. Experimental.</a> Journal of the Electrochemical Society. 146 (6), 2068-2077 (1999).</li>
<li>Broussely, M., et al. <a target="_blank" href="https://www.sciencedirect.com/science/article/pii/S0378775305005082">Main aging mechanisms in Li ion batteries.</a> Journal of Power Sources. 146 (1-2), 90-96 (2005).</li>
<li>Burns, J. C., Stevens, D. A., Dahn, J. R. <a target="_blank" href="http://jes.ecsdl.org/content/162/6/A959.full">In-situ detection of lithium plating using high precision coulometry.</a> Journal of the Electrochemical Society. 162 (6), 959-964 (2015).</li>
<li>Fleischhammer, M., Waldmann, T., Bisle, G., Hogg, B. -I., Wohlfahrt-Mehrens, M. <a target="_blank" href="https://www.sciencedirect.com/science/article/pii/S037877531401489X">Interaction of cyclic ageing at high-rate and low temperatures and safety in lithium-ion batteries.</a> Journal of Power Sources. 274, 432-439 (2015).</li>
<li>Vetter, J., et al. <a target="_blank" href="https://www.sciencedirect.com/science/article/pii/S0378775305000832">Ageing mechanisms in lithium-ion batteries.</a> Journal of Power Sources. 147 (1), 269-281 (2005).</li>
<li>Arora, P., White, R. E., Doyle, M. <a target="_blank" href="http://jes.ecsdl.org/content/145/10/3647.abstract">Capacity fade mechanisms and side reactions in lithium-ion batteries.</a> Journal of the Electrochemical Society. 145 (10), 3647-3667 (1998).</li>
<li>Spotnitz, R., Franklin, J. <a target="_blank" href="https://www.sciencedirect.com/science/article/pii/S0378775302004883">Abuse behavior of high-power, lithium-ion cells.</a> Journal of Power Sources. 113 (1), 81-100 (2003).</li>
<li>Broussely, M., et al. <a target="_blank" href="https://www.sciencedirect.com/science/article/pii/S0378775301007224">Aging mechanism in Li ion cells and calendar life predictions.</a> Journal of Power Sources. 97-98, 13-21 (2001).</li>
<li>Niikuni, T., Koshika, K., Kawai, T. <a target="_blank" href="https://www.researchgate.net/publication/292084509_Evaluation_of_the_influence_of_JC08-based_cycle_stress_on_batteries_in_plug-in_hybrid_electric_vehicle">Evaluation of the influence of JC08-based cycle stress on batteries in plug-in hybrid electric vehicle.</a> EVS25 (World Battery, Hybrid and Fuel Cell Electric Vehicle Symposium). , Shenzhen, China, November 5 - 9, 2010 (2010).</li>
<li>Betzin, C., Wolfschmidt, H., Luther, M. <a target="_blank" href="https://www.sciencedirect.com/science/article/pii/S187661021631075X">Long time behavior of LiNi0.80Co0.15Al0.05O2 based lithium-ion cells by small depth of discharge at specific state of charge for primary control reserve in a virtual energy storage plant.</a> Energy Procedia. 99, 235-242 (2016).</li>
<li>Schmalstieg, J., Käbitz, S., Ecker, M., Sauer, D. U. <a target="_blank" href="https://www.sciencedirect.com/science/article/pii/S0378775314001876">A holistic aging model for Li(NiMnCo)O2 based 18650 lithium-ion batteries.</a> Journal of Power Sources. 257, 325-334 (2014).</li>
<li>Belt, J., Utgikar, V., Bloom, I. <a target="_blank" href="https://www.sciencedirect.com/science/article/pii/S0378775311016107">Calendar and PHEV cycle life aging of high-energy, lithium-ion cells containing blended spinel and layered-oxide cathodes.</a> Journal of Power Sources. 196 (23), 10213-10221 (2011).</li>
<li>Atkinson, A., Donev, A., Tobias, R. <a target="_blank" href="http://scholar.google.com/scholar?hl=en&safe=off&q=author%3aAtkinson%2C+A+%22Optimum+Experimental+Designs%2C+with+SAS%22">Optimum Experimental Designs, with SAS</a>. , Oxford University Press. Oxford, UK. (2007).</li>
<li>Forman, J. C., Moura, S. J., Stein, J. L., Fathy, H. K. <a target="_blank" href="https://ecal.berkeley.edu/pubs/DSCC12-BattOED.pdf">Optimal experimental design for modeling battery degradation.</a> ASME 2012 5th Annual Dynamic Systems and Control Conference Joint with the JSME 2012 11th Motion and Vibration Conference. 1, DSCC 2012-MOVIC 2012 309-318 (2012).</li>
<li>Muenzel, V., De Hoog, J., Brazil, M., Vishwanath, A., Kalyanaraman, S. <a target="_blank" href="https://dl.acm.org/citation.cfm?id=2768532">A multi-factor battery cycle life prediction methodology for optimal battery management.</a> e-Energy 2015 - Proceedings of the 2015 ACM 6th International Conference on Future Energy Systems. , 57-66 (2015).</li>
<li>Ruiz, V., et al. <a target="_blank" href="https://www.sciencedirect.com/science/article/pii/S0013468617306060">Degradation studies on lithium iron phosphate - graphite cells. The effect of dissimilar charging - discharging temperatures.</a> Electrochimica Acta. 240, This is an open access article under the CC BY license (http://creativeccommons.org/Licenses/by/4.0 495-505 (2017).</li>
<li>Eddahech, A., Briat, O., Vinassa, J. M. <a target="_blank" href="https://www.sciencedirect.com/science/article/pii/S0013468613020719">Lithium-ion battery performance improvement based on capacity recovery exploitation.</a> Electrochimica Acta. 114, 750-757 (2013).</li>
<li>Zhang, S., Xu, K., Jow, T. <a target="_blank" href="https://link.springer.com/article/10.1007/s10008-002-0300-9">Low-temperature performance of Li-ion cells with a LiBF4-based electrolyte.</a> Journal of Solid State Electrochemistry. 7 (3), 147-151 (2003).</li>
<li>Fan, J., Tan, S. <a target="_blank" href="http://jes.ecsdl.org/content/153/6/A1081.short">Studies on charging lithium-ion cells at low temperatures.</a> Journal of the Electrochemical Society. 153 (6), 1081-1092 (2006).</li>
<li>Franco, A. A., Doublet, M. L., Bessler, W. G. <a target="_blank" href="http://scholar.google.com/scholar?hl=en&safe=off&q=author%3aFranco%2C+AA+%22Physical+Multiscale+Modeling+and+Numerical+Simulation+of+Electrochemical+Devices+for+Energy+Conversion+and+Storage%22">Physical Multiscale Modeling and Numerical Simulation of Electrochemical Devices for Energy Conversion and Storage</a>. , Springer-Verlag. London, UK. (2016).</li>
<li>Padhi, A. K., Nanjundaswamy, K. S., Goodenough, J. B. <a target="_blank" href="http://jes.ecsdl.org/content/144/4/1188">Phospho-olivines as positive-electrode materials for rechargeable lithium batteries.</a> Journal of the Electrochemical Society. 144 (4), 1188-1194 (1997).</li>
<li>Dubarry, M., Liaw, B. Y. <a target="_blank" href="https://www.sciencedirect.com/science/article/pii/S0378775309009604">Identify capacity fading mechanism in a commercial LiFePO4 cell.</a> Journal of Power Sources. 194 (1), 541-549 (2009).</li>
<li>Kassem, M., et al. <a target="_blank" href="https://www.sciencedirect.com/science/article/pii/S0378775312004284">Calendar aging of a graphite/LiFePO4 cell.</a> Journal of Power Sources. 208, 296-305 (2012).</li>
<li><a target="_blank" href="http://scholar.google.com/scholar?hl=en&safe=off&q=%22Physical+Multiscale+Modeling+and+Numerical+Simulation+of+Electrochemical+Devices+for+Energy+Conversion+and+Storage%22">Physical Multiscale Modeling and Numerical Simulation of Electrochemical Devices for Energy Conversion and Storage</a>. Franco, A. A., Doublet, M. L., Bessler, W. G. , Springer. London, UK. (2016).</li>
<li>Zheng, Y., et al. <a target="_blank" href="https://www.sciencedirect.com/science/article/pii/S0013468615300098">Deterioration of lithium iron phosphate/graphite power batteries under high-rate discharge cycling.</a> Electrochimica Acta. 176, 270-279 (2015).</li>
<li>Lu, W., et al. <a target="_blank" href="http://jes.ecsdl.org/content/159/5/A566.abstract">Overcharge effect on morphology and structure of carbon electrodes for lithium-ion batteries.</a> Journal of the Electrochemical Society. 159 (5), 566-570 (2012).</li>
<li>Stark, J. K., Ding, Y., Kohl, P. A. <a target="_blank" href="http://jes.ecsdl.org/content/160/9/D337.short">Nucleation of electrodeposited lithium metal: dendritic growth and the effect of co-deposited sodium.</a> Journal of the Electrochemical Society. 160 (9), 337-342 (2013).</li>
<li>Honbo, H., Takei, K., Ishii, Y., Nishida, T. <a target="_blank" href="https://www.sciencedirect.com/science/article/pii/S0378775308016856">Electrochemical properties and Li deposition morphologies of surface modified graphite after grinding.</a> Journal of Power Sources. 189 (1), 337-343 (2009).</li>
<li>Bach, T. C., et al. <a target="_blank" href="https://www.sciencedirect.com/science/article/pii/S2352152X16300032">Nonlinear aging of cylindrical lithium-ion cells linked to heterogeneous compression.</a> Journal of Energy Storage. 5, 212-223 (2016).</li>
<li>Klett, M., et al. <a target="_blank" href="https://www.sciencedirect.com/science/article/pii/S0378775314001529">Non-uniform aging of cycled commercial LiFePO4//graphite cylindrical cells revealed by post-mortem analysis.</a> Journal of Power Sources. 257, 126-137 (2014).</li>
<li>Amine, K., Liu, J., Belharouak, I. <a target="_blank" href="https://www.sciencedirect.com/science/article/pii/S1388248105001177">High-temperature storage and cycling of C-LiFePO4/graphite Li-ion cells.</a> Electrochemistry Communications. 7 (7), 669-673 (2005).</li>
<li>Koltypin, M., Aurbach, D., Nazar, L., Ellis, B. <a target="_blank" href="https://www.sciencedirect.com/science/article/pii/S0378775307012657">More on the performance of LiFePO4 electrodes-The effect of synthesis route, solution composition, aging, and temperature.</a> Journal of Power Sources. 174 (2), 1241-1250 (2007).</li>
</ol>

作者迪斯特罗和丹妮拉是 Lithops 纳丹 l 的员工, 生产了本文使用的电池单元。其他作者没有什么可透露的。

循环的行为在 (-20 °c,-20 °c) (图 1a) 可以归因于 (i) 动力学制约在充电期间 (一个减少的离子扩散, 一个被剥夺的电荷转移抵抗在电极/电解质的接口41, a降低离子电导率, 电荷不平衡等) 和/或 (ii) 锂电镀时, 低温充电可以迅速扩散时, 在高温循环42。当温度恢复到25摄氏度时, 离子扩散增加, 平衡态有平衡。这将导致容量恢复。在文献中没有发现类似的行为。对于受调查的细胞类型, 由于在室温下一定的恢复时间后, 由于容量的快速衰减, 不建议对连续循环进行这种温度组合。
另一方面, 循环在 (12 °c, 30 °c) 的细胞被不良影响的中断周期的参考评估 (这无疑延长了整个测试时间) (图 1a)。这些样品在循环开始后遭受退化, 当与 < 12 °c 循环的样品进行比较时, 它们更容易受到额外的降解。
长期老化与Tc = Td显示了接近二阶多项式关系在容量和测试温度之间 (为-5 °c 的范围到30°c,图 1b)。奥马尔等。12显示了相似的行为 (在温度范围从-18 °c 到40°c)。价值在 (-20 °c,-20 °c) 没有被考虑由于它的行为与一般趋向是极大地不同的。从CRref的容量测量, 似乎自行车在范围-20 °c 到15°c 造成少许退化 (图 1b)。crref 和cr长期表现出的不同行为可以解释为在不同温度和不同的C 速率下进行的试验计算。因此, 它们对不同的过程是敏感的: 不可逆转的衰老 (退化的后果是永久的)12,43和可逆老化 [老化的后果可以恢复 (例如, 延长的休息次)]。可以认为, 一方面, crref 对不可逆转的退化敏感, 另一方面, cr长期对可逆和不可逆转的退化都很敏感。
长期试验中的放电剖面保持可比性 (图 2a);主要的区别是 > 3 Ah (卸货能力下降)8。对于参考循环 (图 2b), 三个高原可以观察在范围 3.15-3.30 V, 对应于阴极之间的电压差 (3.43 V 对应于氧化还原夫妇 Fe3 +/Fe2 +)44和阳极45,46的插层相。当骑自行车时, 由于 cyclable 锂的消耗, 或由于老化47而导致的物质退化, 有一种降低容量值的位移。
在给定的 Tc 上骑车时,发现较低的Td的长期稳定性较高。这与高温导致更高的降解的一般趋势是一致的。这是观察到的三对组合评估和显示在图 3a - 3c。因此, 在td = 30 °c 的骑车导致比Td =-5 °c 更高的降解, Tc是相同的。同样, td = 12 °c 比td =-10 °c 时, Tc是相同的 (12 °c)。
在某些情况下, 参考循环的退化趋势与长期循环所显示的相反。这是情况为 (30 °c,-5 °c) vs (30 °c, 30 °c) 和 (12 °c,-10 °c) vs (12 °c, 12 °c) 自行车。参考周期评估只显示不可逆转的退化, 而长期老化受不可逆转和可逆效应的影响。此外, 1 C 循环导致更高的欧姆下降 (在较低的温度较高)。如果被测试的细胞的行为 (30 °c,-5 °c) 被测试在 (-5 °c, 30 °c) 的细胞, 它可以得出结论, 在两种情况下有一个可比较的退化 [CR长期大约 90% (表 1)]。然而, CRref 显示较低的退化在 (-5 °c, 30 °c)。在这些条件下 (即一个给定的Td), 较高的Tc意味着更多的退化, 如图 4a和4b所示。tc = 30 °c 循环贬低细胞比Tc =-5 °c (当Td是相同的)。这与以前讨论过的其他循环条件的数据的解释是一致的。
总结, 它可以被结束自行车在 (-5 °c,-5 °c), (0 °c,-20 °c), (5 °c, 5 °c), (12 °c,-10 °c) 和 (15 °c,-20 °c) 100 个周期导致几乎没有退化。在Td =-20 °c 测试的样品被证明是稳定的 (容量的恢复在 +25 °c,图 4C), 使这些样品适合分室温度应用。当增加Tc时, 这种容量恢复就不那么令人印象深刻了。这组样本所显示的行为表明, 在低温 (动能成分) 下, 有一个很大的可逆降解成分。
阳极材料 (石墨) 表面的初始条件通常是平滑的 (图 6a和6d)。骑单车后, 表面使火柴, 也由他人观察48。与电极的中心部分 (图 6c和6f) 相比, 碰撞区 (图6b和6e) 的形态学变化更明显。当放大倍数增加时, 半球状粒子在碰撞区可见 (图 6e)。这些结构的平均直径为35至175纳米, 其他49、50、51也有观察到。在这些研究中, 他们被分配到电镀颗粒状金属锂粒子49,50 , 其中 SEI 层增长50。可能的解释为这茨可以被分配到: (i) 某一程度的充电如被描述的路等。49 (10% overlithiation) 或 (ii) 对电极的非均匀压缩, 如巴赫研究。52。
二次电子扫描电镜描述了在循环阳极中分布的明亮粒子 (图 6i)。这些粒子在波纹区 (辅助数据、图S1) 中的可见性较小, 在凹凸区中不可见 (图 6h)。EDX 调查确定了这些微粒作为金属铜 (参见图 6的插入和图 S2的补充数据)。铜 (电流收集器) 可能溶解和沉淀在电极上 (例如, 电流收集器腐蚀是由于反应性与电解质, 当阳极电位是太积极与锂/ 锂+)28. 在被撞击的区域, 有浓度高于背景信号的铜迹也 abserved。可以推测, 由于某种原因, 该区的条件不利于 Cu 的沉淀。最后, 还测量了铁的痕迹。这可能归因于铁的溶解从阴极材料 (LiFePO4), 由其他48,53,54确定。LiPF6基于电解质 (HF 踪影)55, 对循环阴极的评估显示没有变动与新鲜的材料相比 (补充材料,图 S3)。进一步实验正在进行, 以便进一步描绘这些阴极材料。
用CRref 计算出的表 1中的降解率 (DRs)与测试温度 (充放电) 进行了对比, 然后用最小二乘法 (2D) 进行了拟合。图 7显示了所生成的曲面拟合, 其中点是被测量的DRs。数据集被划分为拟合的学习和验证数据集。选择了多项式函数 (最佳 R2)。红色代表条件与低drs和蓝色代表条件以更高的drs。结果模型方程为:
(4)<img alt="Equation 4" src="/files/ftp_upload/57501/57501eq4.jpg"><img alt="Equation 5" src="/files/ftp_upload/57501/57501eq5.jpg">
方差分析证实的多项式系数的统计意义, 导致了DR与Tc的二次关系, 与Td的线性关系。
如果需要选择合适的应用, 其他的观察可能会有帮助: 当Tc约15 摄氏度时, DR不依赖Td;当Tc < 15 °c, 更高的退化发生在更高的Td;当Tc > 15 °c 时, 更低的降解发生在更高的Td;最低的DR对应于 (Tc =-7 °c, Td =-20 °c);最高的DR对应于 (tc = 30 °c, Td =-20 °c) 或 (Tc =-20 °c, Td = 30 °c)。
在这项工作中提出的结果可能与未来标准和规章的设计有关, 以代表更现实的情况。为了找到最佳的操作范围, 需要使用其他化学试剂进行进一步的实验, 以找出根据应用的结果。额外的工作将评估日历老化的影响。

耐久性已成为锂离子电池 (LIB)1、2、3研究的重要课题之一, 不忽视安全行为、性能和成本。电池的退化对电子移动应用程序尤其具有挑战性, 因为与其他应用程序相比, 需要的寿命相对较长4、5、6 (例如, 使用者数年电子)。由于电化学和日历老化, 库的初始性能 (例如, 在容量和电阻方面) 随着时间的推移而恶化。许多因素 (例如, 电极材料、环境条件、电流负载和截止电压) 在降解中可能是决定性的。文献将温度确定为影响电极活性物质降解的主要因素之一, 电极-电解质侧反应7。尽管大量的出版物在文献处理电池耐久性在不同的温度1,8,9,10,11,12, 这些研究只表示所使用的特定单元格、方法和设置。因此, 对其他细胞的外推并不微不足道, 使得不同研究之间的定量比较很难。
可以预见, 不同充放电过程中的循环对电池的降解行为有一定的影响, 因为许多导致降解的工艺都是温度依赖性的。此外, 在一些应用中, 不同的充电和放电温度代表了一个更令人信服的场景 [例如, 在温度控制的环境 (室内) 充电的电子自行车的电池和自行车单车 (即, 排出) 在不同的温度 (室外);在许多应用中, 季节性和每日的温度波动是有经验的)。然而, 在文献中发表的老化试验结果通常是研究相同温度下的充放电步骤。另外, 相关标准13、14、15、16、17和测试方法手册18、19、20使用相同的温度。我们在文献发现了自行车的一个例子在不同的温度 (例如, 45 °c, 65 °c)21为充电和放电。这项工作的作者描述了在较高的放电温度下的容量更高的褪色, 这归因于固体电解质界面 (SEI) 层生长和锂电镀21。在符合实际情况的情况下, 评估电池的退化情况是可取的。未来的标准和法规可能会得益于这项工作中提出的测试, 在不同的温度22的电荷和放电。
通常情况下, 较高的测试温度会加速降解1、11、12, 提高 sei11、23、24的增长, 并促进 sei的变化。11,23。另一方面, 低温循环导致不太可能的挑战: 电镀和枝晶生长促进 (慢锂离子扩散)25,26,27,28。锂金属可以进一步的反应与电解质导致降低耐久性和降低安全度28,29。
王等。8出版了退色在容量跟随了幂法律关系与充电吞吐量 (温度在15°c 和60°c 之间)。其他作者描述了时间关系的平方根, 在容量10、30、31、32、33、34中褪色。这是由于30,31 , 活性锂消耗的 SEI 的增长所造成的不可逆转的容量损失。容量退化也可能有一个份额的线性退化与时间33,34,35。最后, 通过实验结果验证了在不同温度下的容量衰减的一些模拟, 数据显示了退化和温度8、10的指数依赖性。
在这项工作中, 描述了不同的电荷和放电温度对用于亚环境温度的磷酸铁锂 (LFP)/石墨电池降解行为的影响。使用实验设计 (DOE) 方法36可最大限度地减少可能的温度组合数;通常在工业优化过程中使用的一种方法。该方法也适用于领班等。37 ) 研究电池的退化, 提供最小预测误差 (d-最优)。或者, Muenzel等。38开发了一种多因素生命预测模型, 利用奥马尔等数据进行重用。12. 数据已拟合, 并获得了退化矩阵。
在目前的工作中, 所获得的数据由非线性最小二乘法拟合 (多项式), 其中包括电荷和放电温度之间的一阶相互作用。采用方差分析法对多项式的系数和度进行了评价。该方法有助于了解电荷和放电温度的影响及其可能的相互作用。这些信息可以与支持建立未来符合目的和现实的协议和标准相关。

<table><tbody><tr><td>artificial graphite&amp;nbsp;</td><td>IMERYS</td><td></td><td>D50 about 6&amp;nbsp;&amp;micro;m. Catalog number cannot be disclosed for propietary reasons</td></tr><tr><td>lithium iron phosphate</td><td>BASF</td><td></td><td>D50 about 11&amp;nbsp;&amp;micro;m. Catalog number cannot be disclosed for propietary reasons</td></tr><tr><td>Cu foil&amp;nbsp; &amp;nbsp;</td><td>Schlenk</td><td></td><td>16&amp;nbsp;&amp;micro;m thickness. Catalog number cannot be disclosed for propietary reasons&amp;nbsp;</td></tr><tr><td>Al foil</td><td>Showa Denko</td><td></td><td>20&amp;nbsp;&amp;micro;m thickness. Catalog number cannot be disclosed for propietary reasons&amp;nbsp;</td></tr><tr><td>separator&amp;nbsp;</td><td>Celgard</td><td></td><td>separator. Catalog number cannot be disclosed for propietary reasons</td></tr><tr><td>Maccor cycler</td><td>Maccor</td><td>Maccor Series 4000&amp;nbsp;</td><td>Battery cycler</td></tr><tr><td>BIA chamber</td><td>BIA</td><td>BIA MTH 4.46&amp;nbsp;</td><td>environmental temperature chambers</td></tr><tr><td>SEM</td><td>Carl Zeiss, Germany</td><td>ZEISS SUPRA 50</td><td>Scanning Electron Microscope</td></tr><tr><td>EDAX</td><td>Oxford Instruments, UK</td><td>&amp;nbsp;Oxford X-MaxN 80&amp;nbsp;</td><td>Energy Dispersive X-ray spectrometer</td></tr><tr><td>SDD</td><td>Oxford Instruments, UK</td><td>AZtec software</td><td>Drift detector&amp;nbsp;</td></tr></tbody></table>

the effect of charging and discharging lithium iron phosphate-graphite cells at different temperatures on degradation

系统地评价了不同温度下的磷酸铁锂-石墨电池的充放电对其降解的影响。通过使用10的充电和放电温度排列, 从-20 °c 到30摄氏度, 对细胞的降解进行评估。这可以分析电荷和放电温度对衰老及其关联的影响。总共进行了100个充电/放电循环。每25周期进行一个参考周期, 以评估可逆和不可逆转的容量退化。采用多因素方差分析方法, 实验结果拟合显示: i) 降解速率与电荷温度的二次关系, 二) 与放电温度的线性关系, iii。电荷与放电温度的关系。结果发现, 温度组合为 +30 °c 和放电在-5 °c 导致最高的退化率。另一方面, 循环在温度范围从-20 °c 到15°c (与不同的充电和放电温度的组合), 导致一个更低的退化。另外, 当电荷温度为15摄氏度时, 发现降解速率 nondependent 在放电温度上。

囊细胞 (操作电压范围在 2.50-3.70 V 之间) 的额定容量为 6 Ah 已用于本研究。其电化学特性的结果分为三个部分: i) 循环在相同的充放电温度 (步骤 1.1), ii) 循环在不同的排放温度 (和相同的充电温度) (步骤1.2) 和 iii) 循环在不同的充电温度 (和相同的放电温度) (步骤 1.3)。
当Tc = Td显示在图 1a中时, 容量保留与总循环数.每25个周期 (4 个周期) 对应于参考循环测试, 就可以观察到间隙。另外一个基于图的观察是在Tc = Td在-20 °c 测试情况下相当罕见的行为。在每块25个周期之后, 有一个剧烈的衰减容量, 然后恢复在参考循环期间 (做在25°c)。对于图中显示的其他温度组合, 将观察到容量中的衰减。这是最明显的为 (30 °c, 30 °c) 组合。同样, 参考循环也影响了长期试验的退化趋势。CR下降 0.5-1.0% 后, 参照循环测试是 > 12 °c 和增加轻微时, 循环是 < 12 °c。
总体而言, CR长期遵循的顺序 (重复测试的平均值) 从更低的破坏性, 与电池的启动性能相比: 86% (30 °c, 30 °c), 90% (-20 °c,-20 °c), 96% (12 °c, 12 °c), 97% (5 °c, 5 °c), 100% (-5 °c,-5 °c)。在考虑参考周期测试时, 退化跟随命令: 86% (30 °c, 30 °c), 94-95% (5 °c, 5 °c), (12 °c, 12 °c), 并且 (-5 °c,-5 °c) 和 96.5% (-20 °c,-20 °c) (桌 1)。
图 1b显示在容量保留方面的老化 (%)对所有样品的循环温度, 当Tc = Td。根据方程 (3) 显示了参考循环和长期老化, 并将其拟合为二度多项式方程。与CR长期对应的结果 (-20 °c,-20 °c) 由于观察到的特殊行为而被丢弃, 这显然不遵循趋势。
图 2a在长期循环期间显示放电外形。在低C 速率[0.3 C (参考循环) 相比, 1 c (长期循环)] 和更高的温度 [25 °c (参考循环) 相比-5 °c (长期循环)], 额外的特征出现在放电曲线 (图 2b), 三个高原范围为3.15 至 3.30 v。当循环演变时, 有一个运动的高原, 以降低容量和小修改的电压的高原潜力。
图 3a显示17和18和19号和20单元的循环能力演变, 其中Tc = 30 °c 和Td =-5 °c 和30°c 分别。重复测试的数据被提出, 目的是证明重复性。对于重复项也观察到类似的行为, 因此在以下情况下, 只显示一个测试结果, CR值引用平均值。长期循环使细胞的容量减少为二个温度组合, 以更高的退化在 (30 °c, 30 °c) 比较 (30 °c,-5 °c), 86% 与90% 相比 (表 1)。当比较参考周期 [19 和 20 (30 °c, 30 °c) 在86% 和细胞17和 18 (30 °c,-5 °c) 在 82%,表 1] 时, 发现相反的趋势。在自行车运动结束时, 17 和18号细胞出现了一些颠簸。对17号细胞采集的样品进行了验尸后评估, 以了解这些肿块的性质。结果在结果中显示和讨论。需要注意的是, 颠簸在时间过程中发展, 并且在不同的温度组合测试的其他几个细胞中也可见 (此处不显示)。
图 3b显示与3号和5号单元对应的结果, 其中Tc为-5 °c, 另外Td =-5 °c 和30°c 分别。在100个周期以后, 容量保留 (分别100% 和 91%) 是高在 (-5 °c,-5 °c) 比在 (-5 °c, 30 °c)。当使用相同Tc和不同Td时所执行的测试显示在图 3c [单元格 11 (12 °c,-10 °c) 和 13 (12 °c, 12 °c)] 中。在100个循环之后, 容量保留显示第一个单元格的几乎没有退化, 第二个电池的96%。
当使用相同的Td (30 °c) 和不同Tc (-5 °c 和30°c) 时, 容量显示图 4a中显示的行为 (5 和19号单元格)。在100次循环后, 在不同温度下循环的细胞 (大约 91%) 的容量保持率较高 (约为 86%)(表 1)。
一个长期评估在Td =-5 °c 和Tc = 30 °c 和-5 °c 分别 (细胞3和 17) 在图 4b显示。在同一个Td, tc = 30 °c 比Tc =-5 °c 更破坏性, 如前所述。保留在容量在100个周期以后是接近100% 为自行车在 (-5 °c,-5 °c) 和90% 为自行车在 (30 °c,-5 °c) (桌 1)。
最后, 当Td =-20 °c 显示在图 4C (细胞 1, 7, 和15与Tc =-20 °c, 0 °c, 15 °c 分别) 的性能。在 (-20 °c,-20 °c) 循环的数据之前解释过。一个相当相似的结果出现在这个数字, 但在较低的程度。其他40也发现了这种效果。在容量范围内的保留率为 90-102% 相对于cr 的长期和∼96% 相对于crref。
17号细胞 (Tc = 30 °c, Td =-5 °c) 的目视检查显示出显著的大凹凸部分 (图 5a和5b中的白色箭头)。此外, 在袋和石墨电极底部有波纹结构的区域 (红色圆圈,图 5a和5b)。该细胞的降解速率最高, 相对于CRref 的容量保持率最低 (表 1)。
从阳极和阴极电极的样品在3个单独的区域被收获了;颠簸, 波纹, 和中央区域 (后者没有明显的缺陷)。新鲜细胞 (在形成之后) 也被打开和调查为比较目的。
图 6显示了所收获的阳极材料的 SEM 图像。从这个数字, 很明显, 不同的形态学特征是区分的。
<img alt="Figure 1" class="xfigimg" src="/files/ftp_upload/57501/57501fig1.jpg"> 图 1.容量保留.(a) 本小组显示在相同电荷和放电温度100循环后的容量保留。(b) 本小组显示容量保留 (相对于长期老化和参考循环)与温度的关系。细胞测试: no 1 (-20 °c,-20 °c), 3 (-5 °c,-5 °c), 9 (5 °c, 5 °c), 13 (12 °c, 12 °c), 19 (30 °c, 30 °c)。这个数字已经被修改了. 39.<a href="https://www.jove.com/files/ftp_upload/57501/57501fig1large.jpg" target="_blank">请点击这里查看这个数字的更大版本.</a>
<img alt="Figure 2" class="xfigimg" src="/files/ftp_upload/57501/57501fig2.jpg"> 图 2。细胞放电剖面: no 17 (30 °c,-5 °c)。(a) 本小组显示长期循环 (c 速率为 1 c, 温度为-5 摄氏度)。(b) 此面板显示参考循环 (c 速率为 0.3 c, 温度为25摄氏度)。这个数字已经被修改了. 39.<a href="https://www.jove.com/files/ftp_upload/57501/57501fig2large.jpg" target="_blank">请点击这里查看这个数字的更大版本.</a>
<img alt="Figure 3" class="xfigimg" src="/files/ftp_upload/57501/57501fig3.jpg"> 图 3。具有相同的单元格的容量保留Tc和不同Td。这些面板显示的容量保留和不同的放电温度的细胞 (a) no 17 和 18 (30 °c,-5 °c) 和19和 20 (30 °c, 30 °c), (b) 3 (-5 °c,-5 °c) 和5号 (-5 °c, 30 °c), (c) 11 号 (12 °c,-10 °c) 和13号 (12 °c, 12 °c)。这个数字已经被修改了. 39.<a href="https://www.jove.com/files/ftp_upload/57501/57501fig3large.jpg" target="_blank">请点击这里查看这个数字的更大版本.</a>
<img alt="Figure 4" class="xfigimg" src="/files/ftp_upload/57501/57501fig4.jpg"> 图 4。具有不同的单元格的容量保留Tc和相同Td. 这些面板显示了容量保留和变化的细胞电荷温度的影响 (a) 5 (-5 °c, 30 °c) 和19号 (30 °c, 30 °c), (b) 3 (-5 °c,-5 °c) 和17号 (30 °c,-5 °c) 和 (C) 1 (-20 °c,-20 °c), 7 号 (0 °c,-20 °c), 15 号 (15 °c,-20 °c)。这个数字已经被修改了. 39.<a href="https://www.jove.com/files/ftp_upload/57501/57501fig4large.jpg" target="_blank">请点击这里查看这个数字的更大版本.</a>
<img alt="Figure 5" class="xfigimg" src="/files/ftp_upload/57501/57501fig5.jpg"> 图 5。17 号牢房的验尸评估。这些面板显示 (a) 100 循环后的囊细胞, (b) 打开/收割后的阳极电极。白色箭头表示凹凸测试, 红色圆圈表示波纹区域。这两种特性都是在电化学测试中产生的。袋单元的外部尺寸为250毫米 x 164 毫米。这个数字已经被修改了. 39.<a href="https://www.jove.com/files/ftp_upload/57501/57501fig5large.jpg" target="_blank">请点击这里查看这个数字的更大版本.</a>
<img alt="Figure 6" class="xfigimg" src="/files/ftp_upload/57501/57501fig6.jpg"> 图 6。SEM 成像。这些面板显示在低和高放大的扫描电镜成像 (a) 在 (b) 凹凸带和 (c) 中心区的新鲜阳极 (17 号电池), 以及 (d) 在 (e) 凹凸带上收获的阳极 (17 号细胞) 和 (f) 中心地带。下一个面板显示二电子 SEM 成像为 (g) 一个新鲜和为收获的阳极从细胞17在 (h) 碰撞区域和 (i) 中央区域 (插入: 与 EDX 的映射表明富含铜的纳米粒子)。这个数字已经被修改了. 39.<a href="https://www.jove.com/files/ftp_upload/57501/57501fig6large.jpg" target="_blank">请点击这里查看这个数字的更大版本.</a>
<img alt="Figure 7" class="xfigimg" src="/files/ftp_upload/57501/57501fig7.jpg"> 图 7.曲面拟合 [eq (4)] 和实验计算的从参考周期 (R2 = 0.92) 的电荷/放电温度空间的退化率 (点).n = 循环数。红色表示降解率较低, 蓝色的降解率较高。这个数字已经被修改了. 39.<a href="https://www.jove.com/files/ftp_upload/57501/57501fig7large.jpg" target="_blank">请点击这里查看这个数字的更大版本.</a>
<table fo:keep-together.within-page="1"><tbody>
<tr>
<td>单元格测试 No</td>
			<td>Tc/°c</td>
			<td>Td/°c</td>
			<td>ΔT/°c</td>
			<td>C1 /Ah</td>
			<td>长期CR (%)</td>
			<td>C我/啊</td>
			<td>R@1000Hz/欧姆</td>
			<td>CRref (%)</td>
			<td>博士 (ah n-1)/啊</td>
		</tr>
<tr>
<td>1</td>
			<td>-20</td>
			<td>-20</td>
			<td>0</td>
			<td>3.00</td>
			<td>89.86</td>
			<td>5.60</td>
			<td>0.90</td>
			<td>96.45</td>
			<td>-0.00208</td>
		</tr>
<tr>
<td>2</td>
			<td>-20</td>
			<td>-20</td>
			<td>0</td>
			<td>3.00</td>
			<td>90.21</td>
			<td>5.61</td>
			<td>0.93</td>
			<td>96.46</td>
			<td>-0.00208</td>
		</tr>
<tr>
<td>3</td>
			<td>-5</td>
			<td>-5</td>
			<td>0</td>
			<td>4.52</td>
			<td>98.10</td>
			<td>5.62</td>
			<td>0.93</td>
			<td>94.44</td>
			<td>-0.00349</td>
		</tr>
<tr>
<td>4</td>
			<td>-5</td>
			<td>-5</td>
			<td>0</td>
			<td>4.51</td>
			<td>102.00</td>
			<td>5.72</td>
			<td>1.00</td>
			<td>96.40</td>
			<td>-0.00235</td>
		</tr>
<tr>
<td>5</td>
			<td>-5</td>
			<td>30</td>
			<td>35</td>
			<td>5.26</td>
			<td>91.66</td>
			<td>5.74</td>
			<td>0.91</td>
			<td>88.95 *</td>
			<td>-0.00627</td>
		</tr>
<tr>
<td>6</td>
			<td>-5</td>
			<td>30</td>
			<td>35</td>
			<td>5.29</td>
			<td>90.82</td>
			<td>5.72</td>
			<td>0.82</td>
			<td>89.14 *</td>
			<td>-0.00642</td>
		</tr>
<tr>
<td>7</td>
			<td>0</td>
			<td>-20</td>
			<td>20</td>
			<td>3.03</td>
			<td>101.54</td>
			<td>5.62</td>
			<td>0.85</td>
			<td>96.42</td>
			<td>-0.00219</td>
		</tr>
<tr>
<td>8</td>
			<td>0</td>
			<td>-20</td>
			<td>20</td>
			<td>3.04</td>
			<td>99.00</td>
			<td>5.65</td>
			<td>0.93</td>
			<td>96.22</td>
			<td>-0.00223</td>
		</tr>
<tr>
<td>9</td>
			<td>5</td>
			<td>5</td>
			<td>0</td>
			<td>5.33</td>
			<td>97.27</td>
			<td>5.67</td>
			<td>0.93</td>
			<td>94.08</td>
			<td>-0.00239</td>
		</tr>
<tr>
<td>10</td>
			<td>5</td>
			<td>5</td>
			<td>0</td>
			<td>5.35</td>
			<td>97.00</td>
			<td>5.64</td>
			<td>0.84</td>
			<td>94.31</td>
			<td>-0.00233</td>
		</tr>
<tr>
<td>11</td>
			<td>12</td>
			<td>-10</td>
			<td>22</td>
			<td>4.02</td>
			<td>100.36</td>
			<td>5.49</td>
			<td>0.92</td>
			<td>91.83</td>
			<td>-0.00335</td>
		</tr>
<tr>
<td>12</td>
			<td>12</td>
			<td>-10</td>
			<td>22</td>
			<td>4.03</td>
			<td>99.30</td>
			<td>5.51</td>
			<td>0.90</td>
			<td>90.41</td>
			<td>-0.00379</td>
		</tr>
<tr>
<td>13</td>
			<td>12</td>
			<td>12</td>
			<td>0</td>
			<td>5.53</td>
			<td>95.47</td>
			<td>5.65</td>
			<td>0.90</td>
			<td>94.51</td>
			<td>-0.00331</td>
		</tr>
<tr>
<td>14</td>
			<td>12</td>
			<td>12</td>
			<td>0</td>
			<td>5.51</td>
			<td>96.09</td>
			<td>5.64</td>
			<td>0.88</td>
			<td>94.90</td>
			<td>-0.00299</td>
		</tr>
<tr>
<td>15</td>
			<td>15</td>
			<td>-20</td>
			<td>35</td>
			<td>3.03</td>
			<td>102.21</td>
			<td>5.77</td>
			<td>0.94</td>
			<td>95.68 *</td>
			<td>-0.00379</td>
		</tr>
<tr>
<td>16</td>
			<td>15</td>
			<td>-20</td>
			<td>35</td>
			<td>3.01</td>
			<td>102.11</td>
			<td>5.72</td>
			<td>0.95</td>
			<td>95.60 *</td>
			<td>-0.00406</td>
		</tr>
<tr>
<td>17</td>
			<td>30</td>
			<td>-5</td>
			<td>35</td>
			<td>4.61</td>
			<td>90.80</td>
			<td>5.55</td>
			<td>0.92</td>
			<td>81.85</td>
			<td>-0.00994</td>
		</tr>
<tr>
<td>18</td>
			<td>30</td>
			<td>-5</td>
			<td>35</td>
			<td>4.62</td>
			<td>90.00</td>
			<td>5.60</td>
			<td>0.95</td>
			<td>81.20</td>
			<td>-0.01027</td>
		</tr>
<tr>
<td>19</td>
			<td>30</td>
			<td>30</td>
			<td>0</td>
			<td>5.50</td>
			<td>85.50</td>
			<td>5.61</td>
			<td>0.92</td>
			<td>85.42</td>
			<td>-0.00794</td>
		</tr>
<tr>
<td>20</td>
			<td>30</td>
			<td>30</td>
			<td>0</td>
			<td>5.48</td>
			<td>86.00</td>
			<td>5.57</td>
			<td>0.90</td>
			<td>86.09</td>
			<td>-0.00766</td>
		</tr>
<tr>
<td colspan="10">* 95 循环后, 灰色区域表示测试协议, 其中 Tc = Td</td>
		</tr>
</tbody></table>表 1.在不同温度组合下测试的细胞的额定和计算参数.[Tc/°c: 充电温度, Td/°c: 放电温度, ΔT/°c: |Td Tc |, C1/Ah: 第一周期的长期老化能力, CR长期 (%): 相对于第一个周期的容量保留, Ci/o: 初始容量计算由参考周期, CRref (%): 相对于第一个参考周期的容量保留, DR (ah n-1)/啊: 从参考周期计算100周期后的降解率 (假设的线性趋势),n = 循环数。
<img alt="Supplementary Files" src="/files/ftp_upload/57501/57501supfig1.jpg"> 补充文件。软件使用的截图.<a href="https://www.jove.com/files/ftp_upload/57501/Screenshot_Lithops_JOVE-rev_2.docx" target="_blank">请单击此处下载此文件.</a>

Watch this Scientific Journal Video about The Effect of Charging and Discharging Lithium Iron Phosphate-graphite Cells at Different Temperatures on Degradation at JoVE.com

The Effect of Charging and Discharging Lithium Iron Phosphate-graphite Cells at Different Temperatures on Degradation

本文介绍了不同的充电/放电温度对磷酸铁锂-石墨袋细胞降解的影响, 旨在模拟接近真实情况的情况。总的, 10 温度组合在范围-20 到30°c 被调查为了分析温度对退化的影响。

不同温度下的磷酸铁锂-石墨电池充放电对降解的影响

The effect of charging and discharging lithium iron phosphate-graphite cells at different temperatures on their degradation is evaluated systematically. ...

the-effect-charging-discharging-lithium-iron-phosphate-graphite-cells

Research

JoVE Journal

Chemistry

15.4K 次观看.  European Commission, Joint Research Centre (JRC). 本文介绍了不同的充电/放电温度对磷酸铁锂-石墨袋细胞降解的影响, 旨在模拟接近真实情况的情况。总的, 10 温度组合在范围-20 到30°c 被调查为了分析温度对退化的影响。

视频: The Effect of Charging and Discharging Lithium Iron Phosphate-graphite Cells at Different Temperatures on Degradation

Isolation and Chemical Characterization of Lipid A from Gram-negative Bacteria

Lipopolysaccharide (LPS) is the major cell surface molecule of gram-negative bacteria, deposited on the outer leaflet of the outer membrane bilayer. LPS can be subdivided into three domains: the distal O-polysaccharide, a core oligosaccharide, and the lipid A domain consisting of a lipid A molecular species and 3-deoxy-D-manno-oct-2-ulosonic acid residues (Kdo). The lipid A domain is the only component essential for bacterial cell survival. Following its synthesis, lipid A is chemically modified in response to environmental stresses such as pH or temperature, to promote resistance to antibiotic compounds, and to evade recognition by mediators of the host innate immune response. The following protocol details the small- and large-scale isolation of lipid A from gram-negative bacteria. Isolated material is then chemically characterized by thin layer chromatography (TLC) or mass-spectrometry (MS). In addition to matrix-assisted laser desorption/ionization-time of flight (MALDI-TOF) MS, we also describe tandem MS protocols for analyzing lipid A molecular species using electrospray ionization (ESI) coupled to collision induced dissociation (CID) and newly employed ultraviolet photodissociation (UVPD) methods. Our MS protocols allow for unequivocal determination of chemical structure, paramount to characterization of lipid A molecules that contain unique or novel chemical modifications. We also describe the radioisotopic labeling, and subsequent isolation, of lipid A from bacterial cells for analysis by TLC. Relative to MS-based protocols, TLC provides a more economical and rapid characterization method, but cannot be used to unambiguously assign lipid A chemical structures without the use of standards of known chemical structure. Over the last two decades isolation and characterization of lipid A has led to numerous exciting discoveries that have improved our understanding of the physiology of gram-negative bacteria, mechanisms of antibiotic resistance, the human innate immune response, and have provided many new targets in the development of antibacterial compounds.

Isolation and characterization of the lipid A domain of lipopolysaccharide (LPS) from gram-negative bacteria provides insight into cell surface based mechanisms of antibiotic resistance, bacterial survival and fitness, and how chemically diverse lipid A molecular species differentially modulate host innate immune responses.

隔离和脂质A的化学表征革兰氏阴性菌

Lipopolysaccharide (LPS) is the major cell surface molecule of gram-negative bacteria, deposited on the outer leaflet of the outer membrane bilayer. LPS ...

科研

化学

Solid-state Graft Copolymer Electrolytes for Lithium Battery Applications

Battery safety has been a very important research area over the past decade. Commercially available lithium ion batteries employ low flash point (&lt;80 &deg;C), flammable, and volatile organic electrolytes. These organic based electrolyte systems are viable at ambient temperatures, but require a cooling system to ensure that temperatures do not exceed 80 &deg;C. These cooling systems tend to increase battery costs and can malfunction which can lead to battery malfunction and explosions, thus endangering human life. Increases in petroleum prices lead to a huge demand for safe, electric hybrid vehicles that are more economically viable to operate as oil prices continue to rise. Existing organic based electrolytes used in lithium ion batteries are not applicable to high temperature automotive applications. A safer alternative to organic electrolytes is solid polymer electrolytes. This work will highlight the synthesis for a graft copolymer electrolyte (GCE) poly(oxyethylene) methacrylate (POEM) to a block with a lower glass transition temperature (Tg) poly(oxyethylene) acrylate (POEA). The conduction mechanism has been discussed and it has been demonstrated the relationship between polymer segmental motion and ionic conductivity indeed has a Vogel-Tammann-Fulcher (VTF) dependence. Batteries containing commercially available LP30 organic (LiPF6 in ethylene carbonate (EC):dimethyl carbonate (DMC) at a 1:1 ratio) and GCE were cycled at ambient temperature. It was found that at ambient temperature, the batteries containing GCE showed a greater overpotential when compared to LP30 electrolyte. However at temperatures greater than 60 &deg;C, the GCE cell exhibited much lower overpotential due to fast polymer electrolyte conductivity and nearly the full theoretical specific capacity of 170 mAh/g was accessed.

Lithium ion batteries employ flammable and volatile organic electrolytes that are suitable for ambient temperature applications. A safer alternative to organic electrolytes are solid polymer batteries. Solid polymer batteries operate safely at high temperatures (&gt;120 &deg;C), thus making them applicable to high temperature applications such as deep oil drilling and hybrid electric vehicles. This paper will discuss (a) the polymer synthesis, (b) the polymer conduction mechanism, and (c) provide temperature cycling for both solid polymer and organic electrolytes.

接枝共聚物固态电解质的锂离子电池的应用

Battery safety has been a very important research area over the past decade. Commercially available lithium ion batteries employ low flash point (&lt;80 ...

工程学

Sedimentation Equilibrium of a Small Oligomer-forming Membrane Protein: Effect of Histidine Protonation on Pentameric Stability

Analytical ultracentrifugation (AUC) can be used to study reversible interactions between macromolecules over a wide range of interaction strengths and under physiological conditions. This makes AUC a method of choice to quantitatively assess stoichiometry and thermodynamics of homo- and hetero-association that are transient and reversible in biochemical processes. In the modality of sedimentation equilibrium (SE), a balance between diffusion and sedimentation provides a profile as a function of radial distance that depends on a specific association model. Herein, a detailed SE protocol is described to determine the size and monomer-monomer association energy of a small membrane protein oligomer using an analytical ultracentrifuge. AUC-ES is label-free, only based on physical principles, and can be used on both water soluble and membrane proteins. An example is shown of the latter, the small hydrophobic (SH) protein in the human respiratory syncytial virus (hRSV), a 65-amino acid polypeptide with a single &#945;-helical transmembrane (TM) domain that forms pentameric ion channels. NMR-based structural data shows that SH protein has two protonatable His residues in its transmembrane domain that are oriented facing the lumen of the channel. SE experiments have been designed to determine how pH affects association constant and the oligomeric size of SH protein. While the pentameric form was preserved in all cases, its association constant was reduced at low pH. These data are in agreement with a similar pH dependency observed for SH channel activity, consistent with a lumenal orientation of the two His residues in SH protein. The latter may experience electrostatic repulsion and reduced oligomer stability at low pH. In summary, this method is applicable whenever quantitative information on subtle protein-protein association changes in physiological conditions have to be measured.&#160;&#160;

Sedimentation equilibrium (SE) can be used to study protein-protein interactions in a physiological environment. This manuscript describes the use of this technique to determine the effect of pH on the stability of a homo-pentamer formed by the small hydrophobic (SH) protein encoded by the human syncytial respiratory virus (hRSV).

小型低聚物形成膜蛋白的沉降平衡:组氨酸质子对五聚体稳定性

Analytical ultracentrifugation (AUC) can be used to study reversible interactions between macromolecules over a wide range of interaction strengths and ...

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 ...

Non-aqueous Electrode Processing and Construction of Lithium-ion Coin Cells

Research into new and improved materials to be utilized in lithium-ion batteries (LIB) necessitates an experimental counterpart to any computational analysis. Testing of lithium-ion batteries in an academic setting has taken on several forms, but at the most basic level lies the coin cell construction. In traditional LIB electrode preparation, a multi-phase slurry composed of active material, binder, and conductive additive is cast out onto a substrate. An electrode disc can then be punched from the dried sheet and used in the construction of a coin cell for electrochemical evaluation. Utilization of the potential of the active material in a battery is critically dependent on the microstructure of the electrode, as an appropriate distribution of the primary components are crucial to ensuring optimal electrical conductivity, porosity, and tortuosity, such that electrochemical and transport interaction is optimized. Processing steps ranging from the combination of dry powder, wet mixing, and drying can all critically affect multi-phase interactions that influence the microstructure formation. Electrochemical probing necessitates the construction of electrodes and coin cells with the utmost care and precision. This paper aims at providing a step-by-step guide of non-aqueous electrode processing and coin cell construction for lithium-ion batteries within an academic setting and with emphasis on deciphering the influence of drying and calendaring.

Non-aqueous electrode processing is central to the construction of coin cells and the evaluation of new electrode chemistries for lithium-ion batteries. A step-by-step guide to the basic practices needed as an electrochemical engineer working with batteries in an academic experimental setting is furnished.

锂离子纽扣电池的非水电极加工和施工

Research into new and improved materials to be utilized in lithium-ion batteries (LIB) necessitates an experimental counterpart to any computational ...

Synthesis of Ionic Liquid Based Electrolytes, Assembly of Li-ion Batteries, and Measurements of Performance at High Temperature

The chemical instability of the traditional electrolyte remains a safety issue in widely used energy storage devices such as Li-ion batteries. Li-ion batteries for use in devices operating at elevated temperatures require thermally stable and non-flammable electrolytes. Ionic liquids (ILs), which are non-flammable, non-volatile, thermally stable molten salts, are an ideal replacement for flammable and low boiling point organic solvent electrolytes currently used today. We herein describe the procedures to: 1) synthesize mono- and di-phosphonium ionic liquids paired with chloride or bis(trifluoromethane)sulfonimide (TFSI) anions; 2) measure the thermal properties and stability of these ionic liquids by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA); 3) measure the electrochemical properties of the ionic liquids by cyclic voltammetry (CV); 4) prepare electrolytes containing lithium bis(trifluoromethane)sulfonamide; 5) measure the conductivity of the electrolytes as a function of temperature; 6) assemble a coin cell battery with two of the electrolytes along with a Li metal anode and LiCoO2 cathode; and 7) evaluate battery performance at 100 &#176;C. We additionally describe the challenges in execution as well as the insights gained from performing these experiments.

Here, we describe protocols to prepare phosphonium-based ionic liquid and lithium bis(trifluoromethane)sulfonimide salt electrolytes, and assemble a non-flammable and high temperature functioning lithium-ion coin cell battery.

离子液体基电解质的合成，装配锂离子电池，并在高温性能的测量

The chemical instability of the traditional electrolyte remains a safety issue in widely used energy storage devices such as Li-ion batteries. Li-ion ...

In Situ Monitoring of the Accelerated Performance Degradation of Solar Cells and Modules: A Case Study for Cu(In,Ga)Se2 Solar Cells

The levelized cost of electricity (LCOE) of photovoltaic (PV) systems is determined by, among other factors, the PV module reliability. Better prediction of degradation mechanisms and prevention of module field failure can consequently decrease investment risks as well as increase the electricity yield. An improved knowledge level can for these reasons significantly decrease the total costs of PV electricity. 
In order to better understand and minimize the degradation of PV modules, the occurring degradation mechanisms and conditions should be identified. This should preferably happen under combined stresses, since modules in the field are also simultaneously exposed to multiple stress factors. Therefore, two 'Combined Stress test with in situ measurement' setups have been designed and constructed. These setups allow the simultaneous use of humidity, temperature, illumination, and electrical biases as independently controlled stress factors on solar cells and minimodules. The setups also allow real-time monitoring of the electrical properties of these samples. This protocol presents these setups and describes the experimental possibilities. Moreover, results obtained with these setups are also presented: various examples about the influence of both deposition and degradation conditions on the stability of thin film Cu(In,Ga)Se2 (CIGS) as well as Cu2ZnSnSe4 (CZTS) solar cells are described. Results on the temperature dependency of CIGS solar cells are also presented.

In Situ Monitoring of the Accelerated Performance Degradation of Solar Cells and Modules: A Case Study for CuIn,GaSe2 Solar Cells

Two &#39;Combined Stress test with in situ measurement&#39; setups, which allow real-time monitoring of accelerated degradation of solar cells and modules, were designed and constructed. These setups allow the simultaneous use of humidity, temperature, electrical biases, and illumination as independently controlled stress factors. The setups and various experiments executed are presented.

就地太阳能电池和模块加速性能退化的监测: 铜 (in, Ga) Se2太阳能电池的实例研究

The levelized cost of electricity (LCOE) of photovoltaic (PV) systems is determined by, among other factors, the PV module reliability. Better prediction ...

Accelerating Rate Calorimetry and Complementary Techniques to Characterize Battery Safety Hazards

The hazards associated with lithium-based battery chemistries are well-documented due to their catastrophic nature. Risk is typically qualitatively assessed through an engineering risk matrix. Within the matrix, potentially hazardous events are categorized and ranked in terms of severity and probability to provide situational awareness to decision makers and stakeholders. The stochastic nature of battery failures, particularly the lithium-ion chemistry, makes the probability axis of a matrix difficult to properly assess. Fortunately, characterization tools exist, such as accelerated rate calorimetry (ARC), that characterize degrees of battery failure severity. ARC has been used extensively to characterize reactive chemicals but can provide a new application to induce battery failures under safe, controlled experimental conditions and quantify critical safety parameters. Due to the robust nature of the extended volume calorimeter, cells may be safely taken to failure due to a variety of abuses: thermal (simple heating of cell), electrochemical (overcharge), electrical (external short circuit), or physical (crush or nail penetration). This article describes the procedures to prepare and instrument a commercial lithium-ion battery cell for failure in an ARC to collect valuable safety data: onset of thermal runaway, endotherm associated with polymer separator melting, pressure release during thermal runaway, gaseous collection for analytical characterization, maximum temperature of complete reaction, and visual observation of decomposition processes using a high temperature borescope (venting and cell can breach). A thermal &#8220;heat-wait-seek&#8221; method is used to induce cell failure, in which the battery is heated incrementally to a set point, then the instrument identifies heat generation from the battery. As heat generates a temperature rise in the battery, the calorimeter temperature follows this temperature rise, maintaining an adiabatic condition. Therefore, the cell does not exchange heat with the external environment, so all heat generation from the battery under failure is captured.

<meta charset="utf8"></head><body>加速速率量热法和补充技术表征电池安全隐患

A method to characterize the potential failure hazards of lithium batteries is achieved with accelerating rate calorimetry. Heat and pressure release, visual observation of the failure event, and the capture of evolved gases are collected in this experiment to identify the worst credible threats of batteries taken to failure.

加速速率量热法和补充技术表征电池安全隐患

The hazards associated with lithium-based battery chemistries are well-documented due to their catastrophic nature. Risk is typically qualitatively ...

Identification and Quantification of Decomposition Mechanisms in Lithium-Ion Batteries; Input to Heat Flow Simulation for Modeling Thermal Runaway

The risks and possible accidents related to the normal use of lithium-ion batteries remain a serious concern. In order to get a better understanding of thermal runaway (TR), the exothermic decomposition reactions in anode and cathode were studied, using a Simultaneous Thermal Analysis (STA)/Gas Chromatography-Mass Spectrometry (GC-MS)/Fourier Transform Infrared (FTIR) spectrometer system. These techniques allowed the identification of the reaction mechanisms in each electrode, owing to the analysis of evolved gaseous species, the amount of heat released and mass loss. These results provided insight into the thermal events happening within a broader temperature range than covered in previously published models. This allowed the formulation of an improved thermal model to depict TR. The heat of reaction, activation energy, and frequency factor (thermal triplets) for each major exothermic process at material level were investigated in a Lithium Nickel-Manganese-Cobalt-Oxide (NMC (111))-Graphite battery cell. The results were analyzed, and their kinetics were derived. These data can be used to successfully simulate the experimental heat flow.

This work aims at determining the reaction kinetics of Li-ion battery cathode and anode materials undergoing thermal runaway (TR). Simultaneous Thermal Analysis (STA)/Fourier Transform Infrared (FTIR) spectrometer/Gas Chromatography Mass Spectrometry (GC-MS) were used to reveal thermal events and to detect evolved gases.

锂离子电池分解机理的鉴定和量化;用于模拟热失控的热流仿真输入

The risks and possible accidents related to the normal use of lithium-ion batteries remain a serious concern. In order to get a better understanding of ...

不同温度下的磷酸铁锂-石墨电池充放电对降解的影响

摘要

探索更多视频

隔离和脂质A的化学表征革兰氏阴性菌

接枝共聚物固态电解质的锂离子电池的应用

小型低聚物形成膜蛋白的沉降平衡:组氨酸质子对五聚体稳定性

原位中子衍射用特制的锂离子电池

锂离子纽扣电池的非水电极加工和施工

离子液体基电解质的合成，装配锂离子电池，并在高温性能的测量

就地太阳能电池和模块加速性能退化的监测: 铜 (in, Ga) Se₂太阳能电池的实例研究

加速速率量热法和补充技术表征电池安全隐患

加速速率量热法和补充技术表征电池安全隐患

锂离子电池分解机理的鉴定和量化;用于模拟热失控的热流仿真输入