Selective NMR observation of the SEI–metal interface by dynamic nuclear polarisation from lithium metal

Michael A. Hope; Bernardine L.D. Rinkel; Anna B. Gunnarsdóttir; Katharina Märker; Svetlana Menkin; Subhradip Paul; Ivan V. Sergeyev; Clare P. Grey

doi:10.1038/s41467-020-16114-x

Selective NMR observation of the SEI–metal interface by dynamic nuclear polarisation from lithium metal

Michael A. Hope
, Bernardine L.D. Rinkel
, Anna B. Gunnarsdóttir
, Katharina Märker
, Svetlana Menkin
, Subhradip Paul
, Ivan V. Sergeyev
, Clare P. Grey

University of Iceland

University of Iceland

Research output: Contribution to journal › Article › peer-review

Abstract

While lithium metal represents the ultimate high-energy-density battery anode material, its use is limited by dendrite formation and associated safety risks, motivating studies of the solid–electrolyte interphase layer that forms on the lithium, which is key in controlling lithium metal deposition. Dynamic nuclear polarisation enhanced NMR can provide important structural information; however, typical exogenous dynamic nuclear polarisation experiments, in which organic radicals are added to the sample, require cryogenic sample cooling and are not selective for the interface between the metal and the solid–electrolyte interphase. Here we instead exploit the conduction electrons of lithium metal to achieve an order of magnitude hyperpolarisation at room temperature. We enhance the ⁷Li, ¹H and ¹⁹F NMR spectra of solid–electrolyte interphase species selectively, revealing their chemical nature and spatial distribution. These experiments pave the way for more ambitious room temperature in situ dynamic nuclear polarisation studies of batteries and the selective enhancement of metal–solid interfaces in a wider range of systems.

Original language	English
Article number	2224
Journal	Nature Communications
Volume	11
Issue number	1
DOIs	https://doi.org/10.1038/s41467-020-16114-x
Publication status	Published - 1 Dec 2020

Bibliographical note

Funding Information: This work was supported by the Faraday Institution [grant number FIRG001]. M.A.H. and A.B.G. acknowledge support from the Royal Society (RP/R1/180147). M.A.H. is also grateful to the Oppenheimer foundation and A.B.G. acknowledges EPSRC-EP/M009521/1. B.L.D.R. was supported by NECCES, an Energy Frontier Research Centre funded by the U.S. Department of Energy, under Award No. DE-SC0012583. C.P.G. thanks the EU ERC for an Advanced Fellowship DLV-835073. S.M. thanks the Blavatnik Cambridge Fellowships. The Nottingham DNP MAS NMR Facility is funded by the University of Nottingham and EPSRC (EP/L022524/1, EP/R042853/1). We would like to thank Remington Carey and Prof. H. Sirringhaus (University of Cambridge) for the acquisition of X-band EPR spectra of lithium metal, Prof. Lauren Marbella (Columbia University) for providing additional samples for experiments in the U.S., and Dr. Melanie Rosay and Dr. Ralph Weber (Bruker Billerica, U.S.) for helpful discussions, assistance setting up the experiments at 9.4 T, and measuring the Li T1e. Publisher Copyright: © 2020, The Author(s).

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Cite this

@article{b1768c407029492daba50153ae62dd08,

title = "Selective NMR observation of the SEI–metal interface by dynamic nuclear polarisation from lithium metal",

abstract = "While lithium metal represents the ultimate high-energy-density battery anode material, its use is limited by dendrite formation and associated safety risks, motivating studies of the solid–electrolyte interphase layer that forms on the lithium, which is key in controlling lithium metal deposition. Dynamic nuclear polarisation enhanced NMR can provide important structural information; however, typical exogenous dynamic nuclear polarisation experiments, in which organic radicals are added to the sample, require cryogenic sample cooling and are not selective for the interface between the metal and the solid–electrolyte interphase. Here we instead exploit the conduction electrons of lithium metal to achieve an order of magnitude hyperpolarisation at room temperature. We enhance the 7Li, 1H and 19F NMR spectra of solid–electrolyte interphase species selectively, revealing their chemical nature and spatial distribution. These experiments pave the way for more ambitious room temperature in situ dynamic nuclear polarisation studies of batteries and the selective enhancement of metal–solid interfaces in a wider range of systems.",

author = "Hope, \{Michael A.\} and Rinkel, \{Bernardine L.D.\} and Gunnarsd{\'o}ttir, \{Anna B.\} and Katharina M{\"a}rker and Svetlana Menkin and Subhradip Paul and Sergeyev, \{Ivan V.\} and Grey, \{Clare P.\}",

note = "Funding Information: This work was supported by the Faraday Institution [grant number FIRG001]. M.A.H. and A.B.G. acknowledge support from the Royal Society (RP/R1/180147). M.A.H. is also grateful to the Oppenheimer foundation and A.B.G. acknowledges EPSRC-EP/M009521/1. B.L.D.R. was supported by NECCES, an Energy Frontier Research Centre funded by the U.S. Department of Energy, under Award No. DE-SC0012583. C.P.G. thanks the EU ERC for an Advanced Fellowship DLV-835073. S.M. thanks the Blavatnik Cambridge Fellowships. The Nottingham DNP MAS NMR Facility is funded by the University of Nottingham and EPSRC (EP/L022524/1, EP/R042853/1). We would like to thank Remington Carey and Prof. H. Sirringhaus (University of Cambridge) for the acquisition of X-band EPR spectra of lithium metal, Prof. Lauren Marbella (Columbia University) for providing additional samples for experiments in the U.S., and Dr. Melanie Rosay and Dr. Ralph Weber (Bruker Billerica, U.S.) for helpful discussions, assistance setting up the experiments at 9.4 T, and measuring the Li T1e. Publisher Copyright: {\textcopyright} 2020, The Author(s).",

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AU - Märker, Katharina

AU - Menkin, Svetlana

AU - Paul, Subhradip

AU - Sergeyev, Ivan V.

AU - Grey, Clare P.

N1 - Funding Information: This work was supported by the Faraday Institution [grant number FIRG001]. M.A.H. and A.B.G. acknowledge support from the Royal Society (RP/R1/180147). M.A.H. is also grateful to the Oppenheimer foundation and A.B.G. acknowledges EPSRC-EP/M009521/1. B.L.D.R. was supported by NECCES, an Energy Frontier Research Centre funded by the U.S. Department of Energy, under Award No. DE-SC0012583. C.P.G. thanks the EU ERC for an Advanced Fellowship DLV-835073. S.M. thanks the Blavatnik Cambridge Fellowships. The Nottingham DNP MAS NMR Facility is funded by the University of Nottingham and EPSRC (EP/L022524/1, EP/R042853/1). We would like to thank Remington Carey and Prof. H. Sirringhaus (University of Cambridge) for the acquisition of X-band EPR spectra of lithium metal, Prof. Lauren Marbella (Columbia University) for providing additional samples for experiments in the U.S., and Dr. Melanie Rosay and Dr. Ralph Weber (Bruker Billerica, U.S.) for helpful discussions, assistance setting up the experiments at 9.4 T, and measuring the Li T1e. Publisher Copyright: © 2020, The Author(s).

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N2 - While lithium metal represents the ultimate high-energy-density battery anode material, its use is limited by dendrite formation and associated safety risks, motivating studies of the solid–electrolyte interphase layer that forms on the lithium, which is key in controlling lithium metal deposition. Dynamic nuclear polarisation enhanced NMR can provide important structural information; however, typical exogenous dynamic nuclear polarisation experiments, in which organic radicals are added to the sample, require cryogenic sample cooling and are not selective for the interface between the metal and the solid–electrolyte interphase. Here we instead exploit the conduction electrons of lithium metal to achieve an order of magnitude hyperpolarisation at room temperature. We enhance the 7Li, 1H and 19F NMR spectra of solid–electrolyte interphase species selectively, revealing their chemical nature and spatial distribution. These experiments pave the way for more ambitious room temperature in situ dynamic nuclear polarisation studies of batteries and the selective enhancement of metal–solid interfaces in a wider range of systems.

AB - While lithium metal represents the ultimate high-energy-density battery anode material, its use is limited by dendrite formation and associated safety risks, motivating studies of the solid–electrolyte interphase layer that forms on the lithium, which is key in controlling lithium metal deposition. Dynamic nuclear polarisation enhanced NMR can provide important structural information; however, typical exogenous dynamic nuclear polarisation experiments, in which organic radicals are added to the sample, require cryogenic sample cooling and are not selective for the interface between the metal and the solid–electrolyte interphase. Here we instead exploit the conduction electrons of lithium metal to achieve an order of magnitude hyperpolarisation at room temperature. We enhance the 7Li, 1H and 19F NMR spectra of solid–electrolyte interphase species selectively, revealing their chemical nature and spatial distribution. These experiments pave the way for more ambitious room temperature in situ dynamic nuclear polarisation studies of batteries and the selective enhancement of metal–solid interfaces in a wider range of systems.

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M1 - 2224

ER -

Selective NMR observation of the SEI–metal interface by dynamic nuclear polarisation from lithium metal

Abstract

Bibliographical note

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