这项工作在财政联合中心储能研究（JCESR），由能源，科学办公室，基础能源科学，美国能源部资助的能源创新中心的支持。作者也承认期刊材料化学A（化学杂志的英国皇家学会）为最初发布此研究（ <a href="http://pubs.rsc.org/en/content/articlehtml/2016/ta/c6ta01177b">http://pubs.rsc.org/en/content/articlehtml/2016/ta/c6ta01177b</a> ）。 PNNL根据合同DE-AC05-76RL01830能源部巴特尔操作多项目国家实验室。

注意:所有的溶液制剂，循环伏安（CV）测试，和流动池的组装和测试在充满氩气的手套箱中进行的与低于1ppm水和O 2的水平。 1. PTIO流动池的电化学评估<ol><li> CV测试 <ol><li>抛光用0.05微米的γ-氧化铝粉末的玻璃碳电极，用去离子水冲洗它，把它放在真空下，在室温下搅拌过夜，并将其转移到手套箱中。 </li><li>溶解硝酸银（8.5毫克）用MeCN（5mL）中在手套式操作箱， 即 ，10毫硝酸银。将溶液添加到银/硝酸银参比电极的玻璃管中。 </li><li>装配玻璃碳工作电极，石墨毡带对电极，并在一个25毫升三颈梨形烧瓶中的银/硝酸银参比电极。 </li><li>溶解PTIO（52毫克）和四丁基hexafluorophosphate（TBAPF 6，0.87克）在MeCN中（1.10克）， 即 ，0.1M PTIO / 1.0M的TBAPF 6。的溶液添加到该烧瓶浸没三个电极的尖端。 </li><li>电极连接到电化学工作站。测量以100mV / s的扫描速率-1.75-0.75Ⅴ的电压范围内的CV曲线。由两个氧化还原对之间的潜在间隙确定PTIO液流电池的理论电池电压。 注意:应该指出的是，银/银离子参考电极的配置是由它的性质的伪参考电极。其结果是，氧化还原峰可能在长期CV测量移位。然而，这种移位通常具有对氧化还原对之间的电压间隙的疏忽的影响，不会影响电池的电压值。 </li></ol></li><li> 流动池装置 <ol><li>切割的石墨毡，以用刀片的1×10 cm 2的区域。同样，切孔九月arator为3×12 平方厘米的面积。 </li><li>干燥，在真空炉中的液流电池部件（细胞区室，管道，5毫升玻璃小瓶中，石墨毡，和多孔隔板）在70℃下过夜，将它们移入手套箱，并冷却到环境温度。 </li><li>组装在一个端板，铜板电流收集器，一个半电池的顺序流动池部件，石墨毡，垫圈，一个多孔隔板，石墨毡，一个半电池，铜板电流收集器，和一个端板。用抗使用扭矩扳手预先设定在125英寸磅两个端板8螺栓紧固组件。电解质流管路连接到流动池。该电池组件示于图1。 </li></ol></li><li> 对称电化学示范 <ol><li>根据第1.2节装配流动池。在glov溶解PTIO（10毫克）和TBAPF 6（3.3 g）在MeCN中4.4克E盒， 即 5.0毫米PTIO / 1.0M的TBAPF 6。加入4毫升的溶液，以每两个玻璃小瓶。泵电解质用蠕动泵以20毫升/分钟的流速流动。 </li><li>流动池的正，负电流收集器连接到电池测试器。充流动池以5 毫安 /平方厘米，直到电压的恒定电流密度达到1.9五停止充电。泵出电解液到玻璃小瓶中。 </li><li>混合用1毫升负电解质的1毫升正电解质在单独的小瓶中。现在有四电解质:原来，在正，负，和混合。 </li><li>测量上述四个电解液的电子自旋共振（ESR）光谱。 25 <ol><li>与管密封，在两端密封少量（〜10微升）的正和负中的PTFE管（1/16"外径和1/32"标识），然后在一个石英血沉管密封它（4-毫米直径）。 </li><li>安装ESR油管配备了SHQE谐振腔微波频率〜9.85 GHz的（X波段）的ESR光谱仪。 </li><li>收集在1.3.3节的四个电解质的ESR谱。 </li></ol></li></ol></li><li> 流通池测试 <ol><li>组装流通池以下1.2节。 </li><li>溶解PTIO（1.05克）和TBAPF 6（3.50 g）在MeCN中（3.60mmol克）在手套箱中， 即 ，0.5M PTIO / 1.0M的TBAPF 6。加入4毫升的溶液到每玻璃小瓶中。以20毫升/分钟流动的电解质。 </li><li>流动池的正和负集电体连接到电化学工作站。测量在100千赫至1赫兹的频率范围内的流动池在开路电位的阻抗。计算由欧姆电阻（高频阻抗）由流电池的活性面积乘以该特定区域电阻率（ASR）。 </li><li>连接的正和负电流山口流动池的电池测试器的讲师。设置为0.8和2.2伏电压截止和20毫安厘米恒流-2在电池操作的软件。反复充电/放电的PTIO流动池。 </li></ol></li></ol> 2.基于FTIR的SOC测定<ol><li> FTIR可行性验证 <ol><li>制备在手套箱以下三种电解质溶液:（一）的MeCN（0.50克）; （二）TBAPF 6（0.23 g）在MeCN中（0.30克）， 即 ，1.0M TBAPF 6; （三）PTIO（75毫克）和TBAPF 6 0.25克用MeCN（0.26克）， 即 ，0.5M PTIO / 1.0M的TBAPF 6。 </li><li>测量FTIR的三个电解质溶液。 <ol><li>添加各溶液到可密封的FTIR细胞与KBr窗和0.2mm的路径长度的小体积（〜0.05毫升）。密封FTIR细胞。 </li><li>把FTIR细胞到存储容器和将其传送出手套箱中。 </li><li>很快亩NT中的FTIR细胞光谱仪和收集红外光谱。 </li></ol></li><li>组装流通池以下1.2节。 </li><li>溶解PTIO（1.05克）和TBAPF 6（3.50 g）在MeCN中（3.60mmol克）在手套箱中， 即 ，0.5M PTIO / 1.0M的TBAPF 6。加入4毫升的溶液到每玻璃小瓶中。以20毫升/分钟流动的电解质。 </li><li>直到电压达到2.2V。停止充电和泵完全充电流通池。 </li><li>测量的FTIR光谱为正和负的电解质，分别以下在第2.1.2节的方法。 </li><li>在的1.0M TBAPF 6在MeCN中与表1中的组合物中的手套箱准备一系列PTIO溶液（0.05-0.5 M）的。 </li><li>测量红外光谱对每个章节2.1.6的解决方案，按照第2.1.2节的程序。 </li></ol></li><li> SOC的红外测量 <ol><li>组装FO流动池llowing 1.2节。 </li><li>溶解PTIO（2.9克）和TBAPF 6（9.6 g）在MeCN中（9.8克）在手套箱中， 即 ，0.5M PTIO / 1.0M的TBAPF 6。添加11毫升的溶液，以每两个玻璃小瓶。以20毫升/分钟流动的电解质。 </li><li>充以10毫安/厘米2的恒定电流流动池以20毫升/分钟的流速。 </li><li>在0，18，36，54和72分钟的充电时间，停止单元电荷和电解液流，取电解质小等份（0.2mL）中，从阳极液和阴极侧的玻璃小瓶，然后恢复细胞。 </li><li>测量红外光谱对上述五个样本等份，按照第2.1.2节的程序。 </li><li>测量ESR谱为上述五个样品等分，按照第1.3.4的步骤。 </li></ol></li></ol>

<ol>
	<li>Dunn, B., Kamath, H., 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=Electrical+Energy+Storage+for+the+Grid:+A+Battery+of+Choices.">Electrical Energy Storage for the Grid: A Battery of Choices.</a> Science. 334 (6058), 928-935 (2011).</li><li>Yang, Z. G., 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=Electrochemical+Energy+Storage+for+Green+Grid.">Electrochemical Energy Storage for Green Grid.</a> Chem. Rev. 111 (5), 3577-3613 (2011).</li><li>Wang, W., Luo, Q., Li, B., Wei, X., Li, L., Yang, Z. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Recent+Progress+in+Redox+Flow+Battery+Research+and+Development.">Recent Progress in Redox Flow Battery Research and Development.</a> Adv. Funct. Mater. 23 (8), 970-986 (2013).</li><li>Skyllas-Kazacos, M., Chakrabarti, M. H., Hajimolana, S. A., Mjalli, F. S., Saleem, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Progress+in+Flow+Battery+Research+and+Development.">Progress in Flow Battery Research and Development.</a> J. Electrochem. Soc. 158 (5), 55-79 (2011).</li><li>Weber, A. Z., 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=Redox+Flow+Batteries:+A+Review.">Redox Flow Batteries: A Review.</a> J. Appl. Electrochem. 41 (10), 1137-1164 (2011).</li><li>Noack, J., Roznyatovskaya, N., Herr, T., Fischer, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+Chemistry+of+Redox-Flow+Batteries.">The Chemistry of Redox-Flow Batteries.</a> Angew. Chem. Int. Ed. 54 (34), 9775-9808 (2015).</li><li>Soloveichik, G. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Flow+Batteries:+Current+Status+and+Trends.">Flow Batteries: Current Status and Trends.</a> Chem. Rev. 115 (20), 11533-11558 (2015).</li><li>Leung, P., Li, X., de Leon, C. P., Berlouis, L., Low, C. T. J., Walsh, F. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Progress+in+Redox+Flow+Batteries,+Remaining+Challenges+and+Their+Applications+in+Energy+Storage.">Progress in Redox Flow Batteries, Remaining Challenges and Their Applications in Energy Storage.</a> RSC Adv. 2 (27), 10125-10156 (2012).</li><li>Gong, K., Fang, Q., Gu, S., Li, S., Yan, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Nonaqueous+Redox-Flow+Batteries:+Organic+Solvents,+Supporting+Electrolytes,+and+Redox+Pairs.">Nonaqueous Redox-Flow Batteries: Organic Solvents, Supporting Electrolytes, and Redox Pairs.</a> Energy Environ. Sci. 8 (12), 3515-3530 (2015).</li><li>Shin, S. H., Yun, S. H., Moon, S. 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+Review+of+Current+Developments+in+Non-aqueous+Redox+Flow+Batteries:+Characterization+of+Their+Membranes+for+Design+Perspective.">A Review of Current Developments in Non-aqueous Redox Flow Batteries: Characterization of Their Membranes for Design Perspective.</a> RSC Adv. 3 (24), 9095-9116 (2013).</li><li>Cappillino, P. 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=Application+of+Redox+Non-Innocent+Ligands+to+Non-Aqueous+Flow+Battery+Electrolytes.">Application of Redox Non-Innocent Ligands to Non-Aqueous Flow Battery Electrolytes.</a> Adv. Energy Mater. 4 (1), 1300566 (2014).</li><li>Suttil, J. 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=Metal+Acetylacetonate+Complexes+for+High+Energy+Density+Non-aqueous+Redox+Flow+Batteries.">Metal Acetylacetonate Complexes for High Energy Density Non-aqueous Redox Flow Batteries.</a> J. Mater. Chem. A. 3 (15), 7929-7938 (2015).</li><li>Brushett, F. R., Vaughey, J. T., Jansen, A. N. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=An+All-Organic+Non-aqueous+Lithium-Ion+Redox+Flow+Battery.">An All-Organic Non-aqueous Lithium-Ion Redox Flow Battery.</a> Adv. Energy Mater. 2 (11), 1390-1396 (2012).</li><li>Wei, X., 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=Radical+Compatibility+with+Nonaqueous+Electrolytes+and+Its+Impact+on+an+All-Organic+Redox+Flow+Battery.">Radical Compatibility with Nonaqueous Electrolytes and Its Impact on an All-Organic Redox Flow Battery.</a> Angew. Chem. Int. Ed. 54 (30), 8684-8687 (2015).</li><li>Nagarjuna, G., 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=Impact+of+Redox-Active+Polymer+Molecular+Weight+on+the+Electrochemical+Properties+and+Transport+Across+Porous+Separators+in+Nonaqueous+Solvents.">Impact of Redox-Active Polymer Molecular Weight on the Electrochemical Properties and Transport Across Porous Separators in Nonaqueous Solvents.</a> J. Am. Chem. Soc. 136 (46), 16309-16316 (2014).</li><li>Wei, X., 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=TEMPO-Based+Catholyte+for+High-Energy+Density+Nonaqueous+Redox+Flow+Batteries.">TEMPO-Based Catholyte for High-Energy Density Nonaqueous Redox Flow Batteries.</a> Adv. Mater. 26 (45), 7649-7653 (2014).</li><li>Wei, X., 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=Towards+High-Performance+Nonaqueous+Redox+Flow+Electrolyte+Via+Ionic+Modification+of+Active+Species.">Towards High-Performance Nonaqueous Redox Flow Electrolyte Via Ionic Modification of Active Species.</a> Adv. Energy Mater. 5 (1), 1400678 (2015).</li><li>Fan, F. Y., 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=Polysulfide+Flow+Batteries+Enabled+by+Percolating+Nanoscale+Conductor+Networks.">Polysulfide Flow Batteries Enabled by Percolating Nanoscale Conductor Networks.</a> Nano Lett. 14 (4), 2210-2218 (2014).</li><li>Pan, H., 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=On+the+Way+Toward+Understanding+Solution+Chemistry+of+Lithium+Polysulfides+for+High+Energy+Li-S+Redox+Flow+Batteries.">On the Way Toward Understanding Solution Chemistry of Lithium Polysulfides for High Energy Li-S Redox Flow Batteries.</a> Adv. Energy Mater. 5 (16), 1500113 (2015).</li><li>Escalante-Garcia, I. L., Wainright, J. S., Thompson, L. T., Savinell, R. F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Performance+of+a+Non-Aqueous+Vanadium+Acetylacetonate+Prototype+Redox+Flow+Battery:+Examination+of+Separators+and+Capacity+Decay.">Performance of a Non-Aqueous Vanadium Acetylacetonate Prototype Redox Flow Battery: Examination of Separators and Capacity Decay.</a> J. Electrochem. Soc. 162 (3), 363-372 (2015).</li><li>Wei, X., 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=Microporous+Separators+for+Fe/V+Redox+Flow+Batteries.">Microporous Separators for Fe/V Redox Flow Batteries.</a> J. Power Sources. 218, 39-45 (2012).</li><li>Skyllas-Kazacos, M., Kazacos, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=State+of+Charge+Monitoring+Methods+for+Vanadium+Redox+Flow+Battery+Control.">State of Charge Monitoring Methods for Vanadium Redox Flow Battery Control.</a> J. Power Sources. 196 (20), 8822-8827 (2011).</li><li>Brooker, R. P., Bell, C. J., Bonville, L. J., Kunz, H. R., Fenton, 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=Determining+Vanadium+Concentrations+Using+the+UV-Vis+Response+Method.">Determining Vanadium Concentrations Using the UV-Vis Response Method.</a> J. Electrochem. Soc. 162 (4), 608-613 (2015).</li><li>Petchsingh, C., 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=Spectroscopic+Measurement+of+State+of+Charge+in+Vanadium+Flow+Batteries+with+an+Analytical+Model+of+VIV-VV+Absorbance.">Spectroscopic Measurement of State of Charge in Vanadium Flow Batteries with an Analytical Model of VIV-VV Absorbance.</a> J. Electrochem. Soc. 163 (1), 5068-5083 (2016).</li><li>Duan, W., 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=A+Symmetric+Organic-Based+Nonaqueous+Redox+Flow+Battery+and+Its+State+of+Charge+Diagnostics+by+FTIR.">A Symmetric Organic-Based Nonaqueous Redox Flow Battery and Its State of Charge Diagnostics by FTIR.</a> J. Mater. Chem. A. 4 (15), 5448-5456 (2016).</li><li>Potash, R. A., McKone, J. R., Conte, S., Abru&#241;a, H. D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=On+the+Benefits+of+a+Symmetric+Redox+Flow+Battery.">On the Benefits of a Symmetric Redox Flow Battery.</a> J. Electrochem. Soc. 163 (3), 338-344 (2016).</li><li>Kim, H. 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=A+Tetradentate+Ni(II)+Complex+Cation+as+a+Single+Redox+Couple+for+Non-aqueous+Flow+Batteries.">A Tetradentate Ni(II) Complex Cation as a Single Redox Couple for Non-aqueous Flow Batteries.</a> J. Power Sources. 283, 300-304 (2015).</li><li>Shinkle, A. A., Sleightholme, A. E. S., Griffith, L. D., Thompson, L. T., Monroe, C. W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Degradation+Mechanisms+in+The+Non-aqueous+Vanadium+Acetylacetonate+Redox+Flow+Battery.">Degradation Mechanisms in The Non-aqueous Vanadium Acetylacetonate Redox Flow Battery.</a> J. Power Sources. 206, 490-496 (2012).</li><li>Li, Z., 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=Electrochemical+Properties+of+an+All-Organic+Redox+Flow+Battery+Using+2,2,6,6-Tetramethyl-1-Piperidinyloxy+and+N-Methylphthalimide.">Electrochemical Properties of an All-Organic Redox Flow Battery Using 2,2,6,6-Tetramethyl-1-Piperidinyloxy and N-Methylphthalimide.</a> Electrochem. Solid-State Lett. 14 (12), 171-173 (2011).</li><li>Schaltin, 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=Towards+an+All-Copper+Redox+Flow+Battery+Based+on+a+Copper-Containing+Ionic+Liquid.">Towards an All-Copper Redox Flow Battery Based on a Copper-Containing Ionic Liquid.</a> Chem. Commun. 52, 414-417 (2016).</li><li>Luo, Q., 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=Capacity+Decay+and+Remediation+of+Nafion-based+All-Vanadium+Redox+Flow+Batteries.">Capacity Decay and Remediation of Nafion-based All-Vanadium Redox Flow Batteries.</a> ChemSusChem. 6 (2), 268-274 (2013).</li></ol>

The authors have nothing to disclose.

如我们之前显示出，25 FTIR能够非侵入性地检测PTIO液流电池的SOC。作为一种诊断工具，FTIR是因为它拆装方便，响应速度快，成本低，占地面积小，对网上注册成立，没有检测器的饱和，以及相关的结构信息，调查液流电池操作过程中的分子进化的能力，设施的特别有利。 图3E说明了提出的液流电池设备集成在线红外传感器，使得安全运行实时监控SOC。 <p class="jove_...

氧化还原液流电池存储的能量在包含在外部水库和被泵送到内部电极以完成电化学反应液体电解质。储存的能量和动力因此可以分离导致了出色的设计灵活性，可扩展性和模块化。这些优点使液流电池非常适合于集成清洁还间歇性可再生能源的固定能量存储应用，增加格资产利用和效率，和提高能源弹性和安全性。 1，2，3传统的水液流电池从有限的能量密度的困扰，主要是由于狭窄的电压窗口，以避免电解水。 4，5，6，7，8与此相反，非aque基于液流电池的OU电解质因为用于实现高电池电压，高能量密度的潜力被广泛开展。 9，10在这些努力中，各种流量电池化学组成进行了研究，其中包括金属配合物，11，12全有机，13，14的氧化还原活性聚合物，15和锂的混合流动系统。 16，17，18，19 然而，非水液流电池的潜力尚未得到充分展现，由于液流电池相关的条件下，有限的示范的主要技术瓶颈。这个瓶颈是密切多项性能限制性因素有关。第一，大多数电活性材料的小的溶解度的非水流动细胞导致低的能量密度输送。第二，非水液流电池的速率能力主要是由高电解质的粘度和电阻率在相关的氧化还原的浓度限制。第三个因素是缺乏高性能膜。的Nafion和陶瓷膜表现出与非水电解质的低离子传导性。多孔分离器已经证实体面流动池的性能，但是遭受相当大的自放电，因为相对大的孔径。 14，20通常情况下，同时含有阳极电解液和阴极电解液的氧化还原物质的混合反应物电解质（1:1的比例）用于减少氧化还原材料交叉，然而这牺牲了有效的氧化还原浓度，典型地通过一半。 14，21克服上述瓶颈，需要改进母校IALS发现，电池化学设计和流动池结构实现电池相关的循环。 电池状态监测是可靠的操作基本上是很重要的。非正常状态，包括过充电，气体逸出，以及材料的降解可能导致损害电池性能和甚至电池故障。尤其是对于涉及大量电池材料大规模液流电池，这些因素可能会导致严重的安全问题和投资损失。充电状态（SOC），说明电荷或液流电池的放电深度的状态是最重要的电池状态参数中的一个。他们到达危险的水平之前及时SOC的监测可以检测到潜在的风险。然而，该区域似乎是迄今为止下寻址，特别是在非水液流电池。 Spectrophotoscopic方法如紫外可见（UV-VIS）光谱和电解质电导率测量已经在水性流蓄电池装填评价<html> RY的SOC判定。 22，23，24 我们最近引进了基于新的双极的氧化还原物质的新的对称的非水液流电池设计，2-苯基-4,4,5,5- tetramethylimidazoline -1-氧基-3-氧化物（PTIO）。 25此液流电池保持承诺解决非水液流电池前述的挑战。首先，PTIO在乙腈中的电池溶剂（乙腈），该被看好，以使高能量密度的高溶解度（2.6 M）。第二，PTIO呈现被适度分离并因此可以通过本身构成了一个对称电池化学两可逆等的氧化还原对。我们还证明了在FTIR光谱的可分辨的PTIO峰可与未反应的PTIO的流动池中，这导致分光SOC的测定，用ESR结果交叉验证的浓度相关联。姑娘="外部参照"&gt; 26在这里，我们提出了一个协议，以拟定电化学评估和PTIO对称液流电池的基于FTIR的SOC诊断过程。这项工作预计在长期液流电池业务保持了安全性和可靠性，尤其是在现实世界电网应用触发更多的见解。

<table><tbody><tr><td>PTIO</td><td>TCI America</td><td>A5440</td><td>&gt;98.0%</td></tr><tr><td>Tetrabutylammonium hexafluorophosphate</td><td>Sigma-Aldrich</td><td>86879</td><td>electrochemical grade, &amp;ge;99.0%</td></tr><tr><td>MeCN</td><td>BASF</td><td>50325685</td><td>Battery grade</td></tr><tr><td>Silver nitrate</td><td>Sigma-Aldrich</td><td>204390</td><td>99.9999% trace metals basis</td></tr><tr><td>Gamma alumina powder</td><td>CH Instruments</td><td>CHI120</td><td></td></tr><tr><td>Graphite felt</td><td>SGL</td><td>GFD3</td><td>Vacuum-dry at 70 &amp;deg;C for 24 h</td></tr><tr><td>Porous separator</td><td>Daramic</td><td>AA800</td><td>Vacuum-dry at 70 &amp;deg;C for 24 h</td></tr><tr><td>Battery Tester</td><td>Wuhan LAND electronics Co., Ltd.</td><td>Lanhe</td><td>1 A current range</td></tr><tr><td>Electrochemical Workstation</td><td>Solartron Analytical</td><td>ModuLab</td><td></td></tr><tr><td>glove box</td><td>MBRAUN</td><td>Labmaster SP</td><td>oxygen and water levels &amp;lt;1 ppm</td></tr><tr><td>ESR spectrometer</td><td>Bruker&amp;nbsp;</td><td>Elexsys 580&amp;nbsp;</td><td>Equipped with an SHQE resonator with microwave frequency ~9.85 GHz (X band) at 2 mW power, with 100 kHz field modulation</td></tr></tbody></table>

a protocol for electrochemical evaluations and state of charge diagnostics of a symmetric organic redox flow battery

氧化还原液流电池已被认为是用于改善的可再生能源技术的电网和部署的可靠性的最有希望的静止能量存储解决方案之一。在众多的流动化学电池，非水液流电池具有实现的，因为非水电解质的宽电压窗口的高能量密度的潜力。然而，显著技术障碍存在目前限制非水液流电池以证明其全部潜力，如低氧化还原浓度，低工作电流，欠探索电池状态监视等在试图解决这些限制，我们最近报道了基于高度可溶的，氧化还原活性有机氮氧自由基化合物的非水液流电池，2-苯基-4,4,5,5- tetramethylimidazoline -1-氧基-3-氧化物（PTIO）。这种氧化还原材料表现出双极电化学特性，因此可以作为既anolyte和阴极电解液的氧化还原物质，以形成对称的液流电池化学。此外，我们证明了傅里叶变换红外光谱（FTIR）可以测量PTIO浓度PTIO液流电池循环过程中，并提供充电量（SOC）的电池状态的相当准确的检测，如通过电子自旋共振（ESR）的测量交叉验证。在此，我们提出了PTIO对称液流电池的电化学评估和诊断SOC的视频协议。用的详细描述，我们实验证明的路线来实现这样的目的。该协议的目的是引发关于在非水氧化还原液流电池领域的安全性和可靠性更加的兴趣和见解。

对称PTIO液流电池系统的独特的优点是高度归因于PTIO，有机氮氧自由基化合物的电化学性能。 PTIO可以经历电化学歧化反应以形成PTIO +和PTIO - （ 图2a）。这两个氧化还原对是由〜电压间隙适度分开1.7 V（ 图2b），并且可以同时用作阳极电解液和阴极电解液的氧化还原物质中的对称电池化学。使用PTIO作为氧化还原物质可以消除混合反...

Watch this Scientific Journal Video about A Protocol for Electrochemical Evaluations and State of Charge Diagnostics of a Symmetric Organic Redox Flow Battery at JoVE.com

A Protocol for Electrochemical Evaluations and State of Charge Diagnostics of a Symmetric Organic Redox Flow Battery

我们提出的协议电化学评估对称非水有机氧化还原液流电池和用于诊断其用FTIR充电状态。

- 电化学评估和对称有机氧化还原液流电池的充电诊断状态协议

Redox flow batteries have been considered as one of the most promising stationary energy storage solutions for improving the reliability of the power grid ...

a-protocol-for-electrochemical-evaluations-state-charge-diagnostics

Universidad San Sebastian

Research

JoVE Journal

Chemistry

10.4K 次观看.  Joint Center for Energy Storage Research (JCESR). 我们提出的协议电化学评估对称非水有机氧化还原液流电池和用于诊断其用FTIR充电状态。 

视频: A Protocol for Electrochemical Evaluations and State of Charge Diagnostics of a Symmetric Organic Redox Flow Battery

Protocol of Electrochemical Test and Characterization of Aprotic Li-O2 Battery

We demonstrate a method for electrochemical testing of an aprotic Li-O2 battery. An aprotic Li-O2 battery is made of a Li-metal anode, an aprotic electrolyte, and an O2-breathing cathode. The aprotic electrolyte is a solution of lithium salt with aprotic solvent; and porous carbon is commonly used as the cathode substrate. To improve the performance, an electrocatalyst is deposited onto the porous carbon substrate by certain deposition methods, such as atomic layer deposition (ALD) and wet-chemistry reaction. The as-prepared cathode materials are characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray absorption near edge structure (XANES). A Swagelok-type cell, sealed in a glass chamber filled with pure O2, is used for the electrochemical test on a battery test system. The cells are tested under either capacity-controlled mode or voltage controlled mode. The reaction products are investigated by electron microscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, and Raman spectroscopy to study the possible pathway of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). This protocol demonstrates a systematic and efficient arrangement of routine tests of the aprotic Li-O2 battery, including the electrochemical test and characterization of battery materials.

Protocol of Electrochemical Test and Characterization of Aprotic Li-O2 Battery

A protocol for the electrochemical testing of an aprotic Li-O2 battery with the preparation of electrodes and electrolytes and an introduction of the frequently used methods of characterization is presented here.

电化学测试的协议及表征非质子锂的O<sub&gt; 2</sub&gt;电池

We demonstrate a method for electrochemical testing of an aprotic Li-O2 battery. An aprotic Li-O2 battery is made of a Li-metal anode, an aprotic ...

科研

工程学

Electrochemical Impedance Spectroscopy as a Tool for Electrochemical Rate Constant Estimation

Electrochemical impedance spectroscopy (EIS) was used for advanced characterization of organic electroactive compounds along with cyclic voltammetry (CV). In the case of fast reversible electrochemical processes, current is predominantly affected by the rate of diffusion, which is the slowest and limiting stage. EIS is a powerful technique that allows separate analysis of stages of charge transfer that have different AC frequency response. The capability of the method was used to extract the value of charge transfer resistance, which characterizes the rate of charge exchange on the electrode-solution interface. The application of this technique is broad, from biochemistry up to organic electronics. In this work, we are presenting the method of analysis of organic compounds for optoelectronic applications.

Electrochemical impedance spectroscopy (EIS) of species that undergo reversible oxidation or reduction in solution was used for determination of rate constants of oxidation or reduction.

电化学阻抗谱作为电化学速率常数估计的一种工具

Electrochemical impedance spectroscopy (EIS) was used for advanced characterization of organic electroactive compounds along with cyclic voltammetry (CV). ...

化学

Using Cyclic Voltammetry, UV-Vis-NIR, and EPR Spectroelectrochemistry to Analyze Organic Compounds

Cyclic voltammetry (CV) is a technique used in the analysis of organic compounds. When this technique is combined with electron paramagnetic resonance (EPR) or ultraviolet-visible and near-infrared (UV-Vis-NIR) spectroscopies, we obtain useful information such as electron affinity, ionization potential, band-gap energies, the type of charge carriers, and degradation information that can be used to synthesize stable organic electronic devices. In this study, we present electrochemical and spectroelectrochemical methods to analyze the processes occurring in active layers of an organic device as well as the generated charge carriers.

In this article, we describe electrochemical, electron paramagnetic resonance, and ultraviolet-visible and near-infrared spectroelectrochemical methods to analyze organic compounds for application in organic electronics.

利用循环伏安法、紫外-近红外光谱和 EPR 光谱电化学对有机化合物进行分析

Cyclic voltammetry (CV) is a technique used in the analysis of organic compounds. When this technique is combined with electron paramagnetic resonance ...

In Situ Lithiated Reference Electrode: Four Electrode Design for In-operando Impedance Spectroscopy

Extending operating voltage of Li-ion batteries results in higher energy output from these devices. High voltages, however, may trigger or accelerate multiple processes responsible for long-term performance decay. Given the complexity of physical processes occurring inside the cell, it is often challenging to achieve a full understanding of the root causes of this performance degradation. This difficulty arises in part from the fact that any electrochemical measurement of a battery will return the combined contributions of all components in the cell. Incorporation of a reference electrode can solve part of the problem, as it allows the electrochemical reactions of the cathode and the anode to be individually probed. A variation in the voltage range experienced by the cathode, for example, can indicate alterations in the pool of cyclable lithium ions in the full-cell. The structural evolution of the many interphases existing in the battery can also be monitored, by measuring the contributions of each electrode to the overall cell impedance. Such wealth of information amplifies the reach of diagnostic analysis in Li-ion batteries and provides valuable input to the optimization of individual cell components. In this work, we introduce the design of a test cell able to accommodate multiple reference electrodes, and present reference electrodes that are appropriate for each specific type of measurement, detailing the assembly process in order to maximize the accuracy of the experimental results.

The incorporation of reference electrodes in a Li-ion battery provides valuable information to elucidate degradation mechanisms at high voltages. In this article, we present a cell design that accommodates multiple reference electrodes, along with the assembly steps to assure maximum accuracy of the data obtained in electrochemical measurements.

原位锂化参考电极: 四原位阻抗谱的电极设计

Extending operating voltage of Li-ion batteries results in higher energy output from these devices. High voltages, however, may trigger or accelerate ...

Three-electrode Coin Cell Preparation and Electrodeposition Analytics for Lithium-ion Batteries

As lithium-ion batteries find use in high energy and power applications, such as in electric and hybrid-electric vehicles, monitoring the degradation and subsequent safety issues becomes increasingly important. In a Li-ion cell setup, the voltage measurement across the positive and negative terminals inherently includes the effect of the cathode and anode which are coupled and sum to the total cell performance. Accordingly, the ability to monitor the degradation aspects associated with a specific electrode is extremely difficult because the electrodes are fundamentally coupled. A three-electrode setup can overcome this problem. By introducing a third (reference) electrode, the influence of each electrode can be decoupled, and the electrochemical properties can be measured independently. The reference electrode (RE) must have a stable potential that can then be calibrated against a known reference, for example, lithium metal. The three-electrode cell can be used to run electrochemical tests such as cycling, cyclic voltammetry, and electrochemical impedance spectroscopy (EIS). Three-electrode cell EIS measurements can elucidate the contribution of individual electrode impedance to the full cell. In addition, monitoring the anode potential allows the detection of electrodeposition due to lithium plating, which can cause safety concerns. This is especially important for the fast charging of Li-ion batteries in electric vehicles. In order to monitor and characterize the safety and degradation aspects of an electrochemical cell, a three-electrode setup can prove invaluable. This paper aims to provide a guide to constructing a three-electrode coin cell setup using the 2032-coin cell architecture, which is easy to produce, reliable, and cost-effective.

Three-electrode cells are useful in studying the electrochemistry of lithium-ion batteries. Such an electrochemical setup allows the phenomena associated with the cathode and anode to be decoupled and examined independently. Here, we present a guide for construction and use of a three-electrode coin cell with emphasis on lithium plating analytics.

锂离子电池三电极硬币电池制备及电沉积分析

As lithium-ion batteries find use in high energy and power applications, such as in electric and hybrid-electric vehicles, monitoring the degradation and ...

Extending the Lifespan of Soluble Lead Flow Batteries with a Sodium Acetate Additive

In this report, we present a method for the construction of a soluble lead flow battery (SLFB) with an extended cycle life. By supplying an adequate amount of sodium acetate (NaOAc) to the electrolyte, a cycle life extension of over 50% is demonstrated for SLFBs via long-term galvanostatic charge/discharge experiments. A higher quality of the PbO2 electrodeposit at the positive electrode is quantitatively validated for NaOAc-added electrolyte by throwing index (TI) measurements. Images acquired by scanning electron microscopy (SEM) also exhibit more integrated PbO2 surface morphology when the SLFB is operated with the NaOAc-added electrolyte. This work indicates that electrolyte modification can be a plausible route to economically enable SLFBs for large-scale energy storage.

A protocol for the construction of a soluble lead flow battery with an extended lifespan, in which sodium acetate is supplied in the methanesulfonic electrolyte as an additive, is presented.

用醋酸钠添加剂延长可溶性铅流电池的使用寿命

In this report, we present a method for the construction of a soluble lead flow battery (SLFB) with an extended cycle life. By supplying an adequate ...

Evaluating the Electrochemical Properties of Supercapacitors using the Three-Electrode System

The three-electrode system is a basic and general analytical platform for investigating the electrochemical performance and characteristics of energy storage systems at the material level. Supercapacitors are one of the most important emergent energy storage systems developed in the past decade. Here, the electrochemical performance of a supercapacitor was evaluated using a three-electrode system with a potentiostat device. The three-electrode system consisted of a working electrode (WE), reference electrode (RE), and counter electrode (CE). The WE is the electrode where the potential is controlled and the current is measured, and it is the target of research. The RE acts as a reference for measuring and controlling the potential of the system, and the CE is used to complete the closed circuit to enable electrochemical measurements. This system provides accurate analytical results for evaluating electrochemical parameters such as the specific capacitance, stability, and impedance through cyclic voltammetry (CV), galvanostatic charge-discharge (GCD), and electrochemical impedance spectroscopy (EIS). Several experimental design protocols are proposed by controlling the parameter values of the sequence when using a three-electrode system with a potentiostat device to evaluate the electrochemical performance of supercapacitors. Through these protocols, the researcher can set up a three-electrode system to obtain reasonable electrochemical results for assessing the performance of supercapacitors.

The protocol describes the evaluation of various electrochemical properties of supercapacitors using a three-electrode system with a potentiostat device.

使用三电极系统评估超级电容器的电化学性质

The three-electrode system is a basic and general analytical platform for investigating the electrochemical performance and characteristics of energy ...

氧化还原活性 MOF 固态电化学的磁力表征

Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks

Electrochemical energy storage has been a widely discussed application of redox-active metal-organic frameworks (MOFs) in the past 5 years. Although MOFs show outstanding performance in terms of gravimetric or areal capacitance and cyclic stability, unfortunately their electrochemical mechanisms are not well understood in most cases. Traditional spectroscopic techniques, such as X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS), have only provided vague and qualitative information about valence changes of certain elements, and the mechanisms proposed based on such information are often highly disputable. In this article, we report a series of standardized methods, including the fabrication of solid-state electrochemical cells, electrochemistry measurements, the disassembly of cells, the collection of MOF electrochemical intermediates, and physical measurements of the intermediates under the protection of inert gases. By using these methods for quantitatively clarifying the electronic and spin state evolution within a single electrochemical step of redox-active MOFs, one can provide clear insight into the nature of electrochemical energy storage mechanisms not only for MOFs, but also for all other materials with strongly correlated electronic structures.

作者聚焦：氧化还原活性金属有机框架固态电化学中中间体的磁力表征  

Ex situ magnetic surveys can directly provide bulk and local information on a magnetic electrode to reveal its charge storage mechanism step by step. Herein, electron spin resonance (ESR) and magnetic susceptibility are demonstrated to monitor the evaluation of paramagnetic species and their concentration in a redox-active metal-organic framework (MOF).

氧化还原-活性金属-有机骨架固态电化学中中间体的磁力表征

Electrochemical energy storage has been a widely discussed application of redox-active metal-organic frameworks (MOFs) in the past 5 years. Although MOFs ...

- 电化学评估和对称有机氧化还原液流电池的充电诊断状态协议

摘要

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此视频中的章节

电化学测试的协议及表征非质子锂的O

电化学阻抗谱作为电化学速率常数估计的一种工具

利用循环伏安法、紫外-近红外光谱和 EPR 光谱电化学对有机化合物进行分析

原位锂化参考电极: 四原位阻抗谱的电极设计

锂离子电池三电极硬币电池制备及电沉积分析

用醋酸钠添加剂延长可溶性铅流电池的使用寿命

使用三电极系统评估超级电容器的电化学性质

氧化还原-活性金属-有机骨架固态电化学中中间体的磁力表征

氧化还原-活性金属-有机骨架固态电化学中中间体的磁力表征

氧化还原-活性金属-有机骨架固态电化学中中间体的磁力表征