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Endogenous Dynamic Nuclear Polarization for Sensitivity Enhancement in Solid-State NMR of Electrode Materials

[Image: see text] Rational design of materials for energy storage systems relies on our ability to probe these materials at various length scales. Solid-state NMR spectroscopy is a powerful approach for gaining chemical and structural insights at the atomic/molecular level, but its low detection sen...

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Autores principales: Harchol, Adi, Reuveni, Guy, Ri, Vitalii, Thomas, Brijith, Carmieli, Raanan, Herber, Rolfe H., Kim, Chunjoong, Leskes, Michal
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2020
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7133110/
https://www.ncbi.nlm.nih.gov/pubmed/32273937
http://dx.doi.org/10.1021/acs.jpcc.0c00858
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author Harchol, Adi
Reuveni, Guy
Ri, Vitalii
Thomas, Brijith
Carmieli, Raanan
Herber, Rolfe H.
Kim, Chunjoong
Leskes, Michal
author_facet Harchol, Adi
Reuveni, Guy
Ri, Vitalii
Thomas, Brijith
Carmieli, Raanan
Herber, Rolfe H.
Kim, Chunjoong
Leskes, Michal
author_sort Harchol, Adi
collection PubMed
description [Image: see text] Rational design of materials for energy storage systems relies on our ability to probe these materials at various length scales. Solid-state NMR spectroscopy is a powerful approach for gaining chemical and structural insights at the atomic/molecular level, but its low detection sensitivity often limits applicability. This limitation can be overcome by transferring the high polarization of electron spins to the sample of interest in a process called dynamic nuclear polarization (DNP). Here, we employ for the first time metal ion-based DNP to probe pristine and cycled composite battery electrodes. A new and efficient DNP agent, Fe(III), is introduced, yielding lithium signal enhancement up to 180 when substituted in the anode material Li(4)Ti(5)O(12). In addition for being DNP active, Fe(III) improves the anode performance. Reduction of Fe(III) to Fe(II) upon cycling can be monitored in the loss of DNP activity. We show that the dopant can be reactivated (return to Fe(III)) for DNP by increasing the cycling potential window. Furthermore, we demonstrate that the deleterious effect of carbon additives on the DNP process can be eliminated by using carbon free electrodes, doped with Fe(III) and Mn(II), which provide good electrochemical performance as well as sensitivity in DNP-NMR. We expect that the approach presented here will expand the applicability of DNP for studying materials for frontier challenges in materials chemistry associated with energy and sustainability.
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spelling pubmed-71331102020-04-07 Endogenous Dynamic Nuclear Polarization for Sensitivity Enhancement in Solid-State NMR of Electrode Materials Harchol, Adi Reuveni, Guy Ri, Vitalii Thomas, Brijith Carmieli, Raanan Herber, Rolfe H. Kim, Chunjoong Leskes, Michal J Phys Chem C Nanomater Interfaces [Image: see text] Rational design of materials for energy storage systems relies on our ability to probe these materials at various length scales. Solid-state NMR spectroscopy is a powerful approach for gaining chemical and structural insights at the atomic/molecular level, but its low detection sensitivity often limits applicability. This limitation can be overcome by transferring the high polarization of electron spins to the sample of interest in a process called dynamic nuclear polarization (DNP). Here, we employ for the first time metal ion-based DNP to probe pristine and cycled composite battery electrodes. A new and efficient DNP agent, Fe(III), is introduced, yielding lithium signal enhancement up to 180 when substituted in the anode material Li(4)Ti(5)O(12). In addition for being DNP active, Fe(III) improves the anode performance. Reduction of Fe(III) to Fe(II) upon cycling can be monitored in the loss of DNP activity. We show that the dopant can be reactivated (return to Fe(III)) for DNP by increasing the cycling potential window. Furthermore, we demonstrate that the deleterious effect of carbon additives on the DNP process can be eliminated by using carbon free electrodes, doped with Fe(III) and Mn(II), which provide good electrochemical performance as well as sensitivity in DNP-NMR. We expect that the approach presented here will expand the applicability of DNP for studying materials for frontier challenges in materials chemistry associated with energy and sustainability. American Chemical Society 2020-03-06 2020-04-02 /pmc/articles/PMC7133110/ /pubmed/32273937 http://dx.doi.org/10.1021/acs.jpcc.0c00858 Text en Copyright © 2020 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
spellingShingle Harchol, Adi
Reuveni, Guy
Ri, Vitalii
Thomas, Brijith
Carmieli, Raanan
Herber, Rolfe H.
Kim, Chunjoong
Leskes, Michal
Endogenous Dynamic Nuclear Polarization for Sensitivity Enhancement in Solid-State NMR of Electrode Materials
title Endogenous Dynamic Nuclear Polarization for Sensitivity Enhancement in Solid-State NMR of Electrode Materials
title_full Endogenous Dynamic Nuclear Polarization for Sensitivity Enhancement in Solid-State NMR of Electrode Materials
title_fullStr Endogenous Dynamic Nuclear Polarization for Sensitivity Enhancement in Solid-State NMR of Electrode Materials
title_full_unstemmed Endogenous Dynamic Nuclear Polarization for Sensitivity Enhancement in Solid-State NMR of Electrode Materials
title_short Endogenous Dynamic Nuclear Polarization for Sensitivity Enhancement in Solid-State NMR of Electrode Materials
title_sort endogenous dynamic nuclear polarization for sensitivity enhancement in solid-state nmr of electrode materials
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7133110/
https://www.ncbi.nlm.nih.gov/pubmed/32273937
http://dx.doi.org/10.1021/acs.jpcc.0c00858
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