Andrés Ramírez Aguilera, , , Isobel Tigerlily Jager, , , Florin Marica, , , C. Adam Dyker, , and , Bruce J. Balcom*,
{"title":"低磁场便携式磁体1H MR弛豫法测量钒氧化还原液流电池的电荷状态。","authors":"Andrés Ramírez Aguilera, , , Isobel Tigerlily Jager, , , Florin Marica, , , C. Adam Dyker, , and , Bruce J. Balcom*, ","doi":"10.1021/acs.analchem.5c04254","DOIUrl":null,"url":null,"abstract":"<p >Vanadium redox flow batteries offer a promising solution for medium- to large-scale energy storage applications. Accurately monitoring the state of charge (SOC) of these batteries is crucial for optimizing long-term performance and ensuring effective battery control. Electrolyte crossover and side reactions can degrade battery performance, but traditional electrochemical techniques are often inadequate for diagnosing these issues. This study introduces a novel <sup>1</sup>H magnetic resonance approach to estimate the SOC by analyzing the bulk relaxation times, <i>T</i><sub>1</sub> and <i>T</i><sub>2</sub>, in the electrolyte. The basis of the measurement is the paramagnetic relaxation enhancement effect of vanadium ions on the bulk solution. The four different vanadium oxidation states in the redox flow battery have very different effects on the bulk relaxation times. The different relaxivities of these four species permit the determination of concentration. The measurement employs two MR devices, one measuring the cathode electrolyte and one measuring the anode electrolyte. The magnets are small inexpensive, permanent magnets, Proteus magnets, with a <sup>1</sup>H resonance frequency of 20 MHz. To the best of our knowledge, this is the first analytical MR measurement employing two discrete MR magnets in close proximity. The prospect exists for simultaneous measurement with the two MR devices, although measurements are sequential in this study. We demonstrate how 2D maps correlating <i>T</i><sub>1</sub> with <i>T</i><sub>1</sub>, <i>T</i><sub>2</sub> with <i>T</i><sub>2</sub>, and <i>T</i><sub>1</sub> with <i>T</i><sub>2</sub>, measured from both sides of the battery, can effectively “map” the SOC during operation.</p>","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"97 40","pages":"22174–22183"},"PeriodicalIF":6.7000,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"State of Charge in a Vanadium Redox Flow Battery Measured via 1H MR Relaxation with Low Field Portable Magnets\",\"authors\":\"Andrés Ramírez Aguilera, , , Isobel Tigerlily Jager, , , Florin Marica, , , C. Adam Dyker, , and , Bruce J. Balcom*, \",\"doi\":\"10.1021/acs.analchem.5c04254\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Vanadium redox flow batteries offer a promising solution for medium- to large-scale energy storage applications. Accurately monitoring the state of charge (SOC) of these batteries is crucial for optimizing long-term performance and ensuring effective battery control. Electrolyte crossover and side reactions can degrade battery performance, but traditional electrochemical techniques are often inadequate for diagnosing these issues. This study introduces a novel <sup>1</sup>H magnetic resonance approach to estimate the SOC by analyzing the bulk relaxation times, <i>T</i><sub>1</sub> and <i>T</i><sub>2</sub>, in the electrolyte. The basis of the measurement is the paramagnetic relaxation enhancement effect of vanadium ions on the bulk solution. The four different vanadium oxidation states in the redox flow battery have very different effects on the bulk relaxation times. The different relaxivities of these four species permit the determination of concentration. The measurement employs two MR devices, one measuring the cathode electrolyte and one measuring the anode electrolyte. The magnets are small inexpensive, permanent magnets, Proteus magnets, with a <sup>1</sup>H resonance frequency of 20 MHz. To the best of our knowledge, this is the first analytical MR measurement employing two discrete MR magnets in close proximity. The prospect exists for simultaneous measurement with the two MR devices, although measurements are sequential in this study. We demonstrate how 2D maps correlating <i>T</i><sub>1</sub> with <i>T</i><sub>1</sub>, <i>T</i><sub>2</sub> with <i>T</i><sub>2</sub>, and <i>T</i><sub>1</sub> with <i>T</i><sub>2</sub>, measured from both sides of the battery, can effectively “map” the SOC during operation.</p>\",\"PeriodicalId\":27,\"journal\":{\"name\":\"Analytical Chemistry\",\"volume\":\"97 40\",\"pages\":\"22174–22183\"},\"PeriodicalIF\":6.7000,\"publicationDate\":\"2025-10-02\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Analytical Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.analchem.5c04254\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, ANALYTICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Analytical Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.analchem.5c04254","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ANALYTICAL","Score":null,"Total":0}
State of Charge in a Vanadium Redox Flow Battery Measured via 1H MR Relaxation with Low Field Portable Magnets
Vanadium redox flow batteries offer a promising solution for medium- to large-scale energy storage applications. Accurately monitoring the state of charge (SOC) of these batteries is crucial for optimizing long-term performance and ensuring effective battery control. Electrolyte crossover and side reactions can degrade battery performance, but traditional electrochemical techniques are often inadequate for diagnosing these issues. This study introduces a novel 1H magnetic resonance approach to estimate the SOC by analyzing the bulk relaxation times, T1 and T2, in the electrolyte. The basis of the measurement is the paramagnetic relaxation enhancement effect of vanadium ions on the bulk solution. The four different vanadium oxidation states in the redox flow battery have very different effects on the bulk relaxation times. The different relaxivities of these four species permit the determination of concentration. The measurement employs two MR devices, one measuring the cathode electrolyte and one measuring the anode electrolyte. The magnets are small inexpensive, permanent magnets, Proteus magnets, with a 1H resonance frequency of 20 MHz. To the best of our knowledge, this is the first analytical MR measurement employing two discrete MR magnets in close proximity. The prospect exists for simultaneous measurement with the two MR devices, although measurements are sequential in this study. We demonstrate how 2D maps correlating T1 with T1, T2 with T2, and T1 with T2, measured from both sides of the battery, can effectively “map” the SOC during operation.
期刊介绍:
Analytical Chemistry, a peer-reviewed research journal, focuses on disseminating new and original knowledge across all branches of analytical chemistry. Fundamental articles may explore general principles of chemical measurement science and need not directly address existing or potential analytical methodology. They can be entirely theoretical or report experimental results. Contributions may cover various phases of analytical operations, including sampling, bioanalysis, electrochemistry, mass spectrometry, microscale and nanoscale systems, environmental analysis, separations, spectroscopy, chemical reactions and selectivity, instrumentation, imaging, surface analysis, and data processing. Papers discussing known analytical methods should present a significant, original application of the method, a notable improvement, or results on an important analyte.