Anodic Oxidation of Conductive Carbon and Ethylene Carbonate in High-Voltage Li-Ion Batteries Quantified by On-Line Electrochemical Mass Spectrometry
Anodic Oxidation of Conductive Carbon and Ethylene Carbonate in High-Voltage Li-Ion Batteries Quantified by On-Line Electrochemical Mass Spectrometry
复制标题
DOI：
10.1149/2.0951506jes
复制
发表时间：
2015
影响因子：
3.9
通讯作者：
M. Metzger;C. Marino;J. Sicklinger;Dominik Haering;H. Gasteiger
中科院分区：
文献类型：
--
作者：
M. Metzger;C. Marino;J. Sicklinger;Dominik Haering;H. Gasteiger
电池组件如导电炭黑（Super C65）和共溶剂碳酸亚乙酯（EC）的阳极氧化稳定性具有很大的相关性，特别是关于高电压阴极材料。在这项研究中，我们使用在线电化学质谱（OEMS）去卷积的CO和CO2的阳极氧化的碳和电解质的演变，通过使用完全13 C-同位素标记的电解质的基础上碳酸亚乙酯与2 M LiClO 4。我们提出了一种新开发的两室电池，该电池通过固体Li+离子传导隔膜在阳极和阴极室之间提供紧密密封，从而使我们能够在高电位（> 4.5 V）和10至60 ℃下研究微量水对碳（12 C）和碳酸乙烯酯（13 C）阳极氧化的影响。此外，我们报告的温度依赖性的水驱动的水解碳酸亚乙酯伴随着CO2的演变。最后，通过量化5.0 V时CO/CO2和CO/CO2的析出速率，我们证明了碳和电解质的阳极氧化可以是实质性的，特别是在高温和微量水的存在下，这对5 V阴极材料的实现提出了重大挑战。版权所有作者2015.由ECS发布。这是一篇开放获取的文章，根据知识共享署名非商业性禁止衍生4.0许可证（CC BY-NC-ND，http：//creativecommons.org/licenses/by-nc-nd/4.0/）的条款分发，该许可证允许在任何媒体上进行非商业性的重用，分发和复制，前提是原始作品没有以任何方式改变并正确引用。如需商业再利用许可，请发送电子邮件至oa@electrochem.org。[DOI：10.1149/2.0951506jes]保留所有权利。
The anodic oxidation stability of battery components like the conductive carbon black (Super C65) and the co-solvent ethylene carbonate (EC) is of great relevance, especially with regards to high-voltage cathode materials. In this study, we use On-line Electrochemical Mass Spectrometry (OEMS) to deconvolute the CO and CO2 evolution from the anodic oxidation of carbon and electrolyte by using a fully 13C-isotope labeled electrolyte based on ethylene carbonate with 2 M LiClO4. We present a newly developed two-compartment cell, which provides a tight seal between anode and cathode compartment via a solid Li+-ion conducting separator, and which thus allows us to examine the effect of trace amounts of water on the anodic oxidation of carbon (12C) and ethylene carbonate (13C) at high potentials (> 4.5 V) and 10 to 60◦C. Moreover, we report on the temperature dependence of the water-driven hydrolysis of ethylene carbonate accompanied by CO2 evolution. Finally, by quantifying the evolution rates of CO/CO2 and CO/CO2 at 5.0 V, we demonstrate that the anodic oxidation of carbon and electrolyte can be substantial, especially at high temperature and in the presence of trace water, posing significant challenges for the implementation of 5 V cathode materials. © The Author(s) 2015. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution Non-Commercial No Derivatives 4.0 License (CC BY-NC-ND, http://creativecommons.org/licenses/by-nc-nd/4.0/), which permits non-commercial reuse, distribution, and reproduction in any medium, provided the original work is not changed in any way and is properly cited. For permission for commercial reuse, please email: oa@electrochem.org. [DOI: 10.1149/2.0951506jes] All rights reserved.