P. Philipp M. Schleker, Rüdiger-A. Eichel, Josef Granwehr
{"title":"通过\\(T_1\\) NMR弛豫揭示锂离子在固体-电解质界面上的平衡","authors":"P. Philipp M. Schleker, Rüdiger-A. Eichel, Josef Granwehr","doi":"10.1007/s00723-023-01609-9","DOIUrl":null,"url":null,"abstract":"<div><p>Battery fast charging is pivotal for broader acceptance of electric mobility. While demonstrated for lithium titanate <span>\\((\\text {Li}_4\\text {Ti}_5\\text {O}_{12},\\)</span> LTO) anodes, the underlying mechanisms are still poorly understood. Recently, NMR <span>\\(T_1\\)</span> relaxation time constants of <span>\\({}^7\\text {Li}\\)</span> in the bulk of LTO were found to change if the surrounding electrolyte was altered. It was explained by interdiffusion of mobile lithium ions between the two phases, facilitated by unpinning of polarons from surface defects and leading to a pseudocapacitive effect that potentially influences fast charging. This effect is explored further by systematically varying the lithium salt concentration in an aprotic electrolyte in contact with LTO. Spectrally resolved <span>\\({}^7\\text {Li}\\)</span> <span>\\(T_1\\)</span> NMR relaxation times were used as a measure for bulk concentration changes of paramagnetic polaronic charges in LTO. Correlation of electrolyte concentration and <span>\\({}^7\\text {Li}\\)</span> <span>\\(T_1\\)</span> showed qualitatively different behavior above and below a salt concentration of about 5 mM, leading to a relaxation dispersion maximum in the LTO bulk. At intermediate concentrations, relaxation was consistent with a <span>\\({}^7\\text {Li}\\)</span> exchange equilibrium between LTO and electrolyte. Upon contact of the two phases, yet without insertion into an electrochemical cell or applying an external potential, lithium ions redistributed between LTO bulk and liquid electrolyte. The results can be understood analogously to the distribution of mobile lithium ions between two phases separated by a <span>\\(\\text {Li}^{+}\\)</span> permeable membrane. This is the first demonstration of such an equilibrium for non-faradaic lithium exchange at an interface between a solid ceramic electrode and a liquid electrolyte outside an electrochemical cell, substantiating our previous hypothesis of a polaron-supported mechanism. This study provides a basis for more quantitative (surface)-defect engineering, which is key to optimize battery fast-charging properties.</p></div>","PeriodicalId":469,"journal":{"name":"Applied Magnetic Resonance","volume":null,"pages":null},"PeriodicalIF":1.1000,"publicationDate":"2023-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s00723-023-01609-9.pdf","citationCount":"0","resultStr":"{\"title\":\"Revealing the Equilibrium of Lithium Cations Across a Solid–Electrolyte Interface by \\\\(T_1\\\\) NMR Relaxation\",\"authors\":\"P. Philipp M. Schleker, Rüdiger-A. Eichel, Josef Granwehr\",\"doi\":\"10.1007/s00723-023-01609-9\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Battery fast charging is pivotal for broader acceptance of electric mobility. While demonstrated for lithium titanate <span>\\\\((\\\\text {Li}_4\\\\text {Ti}_5\\\\text {O}_{12},\\\\)</span> LTO) anodes, the underlying mechanisms are still poorly understood. Recently, NMR <span>\\\\(T_1\\\\)</span> relaxation time constants of <span>\\\\({}^7\\\\text {Li}\\\\)</span> in the bulk of LTO were found to change if the surrounding electrolyte was altered. It was explained by interdiffusion of mobile lithium ions between the two phases, facilitated by unpinning of polarons from surface defects and leading to a pseudocapacitive effect that potentially influences fast charging. This effect is explored further by systematically varying the lithium salt concentration in an aprotic electrolyte in contact with LTO. Spectrally resolved <span>\\\\({}^7\\\\text {Li}\\\\)</span> <span>\\\\(T_1\\\\)</span> NMR relaxation times were used as a measure for bulk concentration changes of paramagnetic polaronic charges in LTO. Correlation of electrolyte concentration and <span>\\\\({}^7\\\\text {Li}\\\\)</span> <span>\\\\(T_1\\\\)</span> showed qualitatively different behavior above and below a salt concentration of about 5 mM, leading to a relaxation dispersion maximum in the LTO bulk. At intermediate concentrations, relaxation was consistent with a <span>\\\\({}^7\\\\text {Li}\\\\)</span> exchange equilibrium between LTO and electrolyte. Upon contact of the two phases, yet without insertion into an electrochemical cell or applying an external potential, lithium ions redistributed between LTO bulk and liquid electrolyte. The results can be understood analogously to the distribution of mobile lithium ions between two phases separated by a <span>\\\\(\\\\text {Li}^{+}\\\\)</span> permeable membrane. 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Revealing the Equilibrium of Lithium Cations Across a Solid–Electrolyte Interface by \(T_1\) NMR Relaxation
Battery fast charging is pivotal for broader acceptance of electric mobility. While demonstrated for lithium titanate \((\text {Li}_4\text {Ti}_5\text {O}_{12},\) LTO) anodes, the underlying mechanisms are still poorly understood. Recently, NMR \(T_1\) relaxation time constants of \({}^7\text {Li}\) in the bulk of LTO were found to change if the surrounding electrolyte was altered. It was explained by interdiffusion of mobile lithium ions between the two phases, facilitated by unpinning of polarons from surface defects and leading to a pseudocapacitive effect that potentially influences fast charging. This effect is explored further by systematically varying the lithium salt concentration in an aprotic electrolyte in contact with LTO. Spectrally resolved \({}^7\text {Li}\)\(T_1\) NMR relaxation times were used as a measure for bulk concentration changes of paramagnetic polaronic charges in LTO. Correlation of electrolyte concentration and \({}^7\text {Li}\)\(T_1\) showed qualitatively different behavior above and below a salt concentration of about 5 mM, leading to a relaxation dispersion maximum in the LTO bulk. At intermediate concentrations, relaxation was consistent with a \({}^7\text {Li}\) exchange equilibrium between LTO and electrolyte. Upon contact of the two phases, yet without insertion into an electrochemical cell or applying an external potential, lithium ions redistributed between LTO bulk and liquid electrolyte. The results can be understood analogously to the distribution of mobile lithium ions between two phases separated by a \(\text {Li}^{+}\) permeable membrane. This is the first demonstration of such an equilibrium for non-faradaic lithium exchange at an interface between a solid ceramic electrode and a liquid electrolyte outside an electrochemical cell, substantiating our previous hypothesis of a polaron-supported mechanism. This study provides a basis for more quantitative (surface)-defect engineering, which is key to optimize battery fast-charging properties.
期刊介绍:
Applied Magnetic Resonance provides an international forum for the application of magnetic resonance in physics, chemistry, biology, medicine, geochemistry, ecology, engineering, and related fields.
The contents include articles with a strong emphasis on new applications, and on new experimental methods. Additional features include book reviews and Letters to the Editor.