Andrii Varenikov, Mark Gandelman and Matthew S. Sigman*,
{"title":"开发可应用于对称氧化还原流电池的模块化镍renium 双极电解质。","authors":"Andrii Varenikov, Mark Gandelman and Matthew S. Sigman*, ","doi":"10.1021/jacs.4c05799","DOIUrl":null,"url":null,"abstract":"<p >Amid the escalating integration of renewable energy sources, the demand for grid energy storage solutions, including non-aqueous organic redox flow batteries (oRFBs), has become ever more pronounced. oRFBs face a primary challenge of irreversible capacity loss attributed to the crossover of redox-active materials between half-cells. A possible solution for the crossover challenge involves utilization of bipolar electrolytes that act as both the catholyte and anolyte. Identifying such molecules poses several challenges as it requires a delicate balance between the stability of both oxidation states and energy density, which is influenced by the separation between the two redox events. We report the development of a diaminotriazolium redox-active core capable of producing two electronically distinct persistent radical species with typically extreme reduction potentials (<i>E</i><sub>1/2</sub><sup>red</sup> < −2 V, <i>E</i><sub>1/2</sub><sup>ox</sup> > +1 V, vs Fc<sup>0/+</sup>) and up to 3.55 V separation between the two redox events. Structure–property optimization studies allowed us to identify factors responsible for fine-tuning of potentials for both redox events, as well as separation between them. Mechanistic studies revealed two primary decomposition pathways for the neutral radical charged species and one for the radical biscation. Additionally, statistical modeling provided evidence for the molecular descriptors to allow identification of the structural features responsible for stability of radical species and to propose more stable analogues.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4000,"publicationDate":"2024-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Development of Modular Nitrenium Bipolar Electrolytes for Possible Applications in Symmetric Redox Flow Batteries\",\"authors\":\"Andrii Varenikov, Mark Gandelman and Matthew S. Sigman*, \",\"doi\":\"10.1021/jacs.4c05799\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Amid the escalating integration of renewable energy sources, the demand for grid energy storage solutions, including non-aqueous organic redox flow batteries (oRFBs), has become ever more pronounced. oRFBs face a primary challenge of irreversible capacity loss attributed to the crossover of redox-active materials between half-cells. A possible solution for the crossover challenge involves utilization of bipolar electrolytes that act as both the catholyte and anolyte. Identifying such molecules poses several challenges as it requires a delicate balance between the stability of both oxidation states and energy density, which is influenced by the separation between the two redox events. We report the development of a diaminotriazolium redox-active core capable of producing two electronically distinct persistent radical species with typically extreme reduction potentials (<i>E</i><sub>1/2</sub><sup>red</sup> < −2 V, <i>E</i><sub>1/2</sub><sup>ox</sup> > +1 V, vs Fc<sup>0/+</sup>) and up to 3.55 V separation between the two redox events. Structure–property optimization studies allowed us to identify factors responsible for fine-tuning of potentials for both redox events, as well as separation between them. Mechanistic studies revealed two primary decomposition pathways for the neutral radical charged species and one for the radical biscation. Additionally, statistical modeling provided evidence for the molecular descriptors to allow identification of the structural features responsible for stability of radical species and to propose more stable analogues.</p>\",\"PeriodicalId\":49,\"journal\":{\"name\":\"Journal of the American Chemical Society\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":14.4000,\"publicationDate\":\"2024-07-04\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of the American Chemical Society\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/jacs.4c05799\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/jacs.4c05799","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Development of Modular Nitrenium Bipolar Electrolytes for Possible Applications in Symmetric Redox Flow Batteries
Amid the escalating integration of renewable energy sources, the demand for grid energy storage solutions, including non-aqueous organic redox flow batteries (oRFBs), has become ever more pronounced. oRFBs face a primary challenge of irreversible capacity loss attributed to the crossover of redox-active materials between half-cells. A possible solution for the crossover challenge involves utilization of bipolar electrolytes that act as both the catholyte and anolyte. Identifying such molecules poses several challenges as it requires a delicate balance between the stability of both oxidation states and energy density, which is influenced by the separation between the two redox events. We report the development of a diaminotriazolium redox-active core capable of producing two electronically distinct persistent radical species with typically extreme reduction potentials (E1/2red < −2 V, E1/2ox > +1 V, vs Fc0/+) and up to 3.55 V separation between the two redox events. Structure–property optimization studies allowed us to identify factors responsible for fine-tuning of potentials for both redox events, as well as separation between them. Mechanistic studies revealed two primary decomposition pathways for the neutral radical charged species and one for the radical biscation. Additionally, statistical modeling provided evidence for the molecular descriptors to allow identification of the structural features responsible for stability of radical species and to propose more stable analogues.
期刊介绍:
The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.