Broadband impedance spectroscopy of Li4Ti5O12: from nearly constant loss effects to long-range ion dynamics

Publikation: Beitrag in FachzeitschriftArtikelForschungPeer-Review

Autoren

  • Bernhard Gadermaier
  • Katharina Hogrefe
  • Paul Heitjans
  • H. Martin R. Wilkening

Externe Organisationen

  • Technische Universität Graz
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Details

OriginalspracheEnglisch
Seiten (von - bis)2167-2171
Seitenumfang5
FachzeitschriftZeitschrift fur Anorganische und Allgemeine Chemie
Jahrgang647
Ausgabenummer22
Frühes Online-Datum11 Juni 2021
PublikationsstatusVeröffentlicht - 12 Nov. 2021

Abstract

Li4Ti5O12 (LTO) is known as one of the most robust and long-lasting anode materials in lithium-ion batteries. As yet, the Li-ion transport properties of LTO are, however, not completely understood. Here, we used broadband impedance spectroscopy spanning a wide temperature range to investigate the full electrical response of LTO over a wide frequency range. It turned out that the isotherms recorded entail information about two relaxation processes. While at high temperatures the isotherms show a frequency independent plateau that corresponds to poor long-range ion transport (<10−11 S cm−1 (298 K), 0.79 eV), they reveal a second region, seen at lower temperatures and higher frequencies, which we attribute to short-range ion dynamics (10−8 S cm−1) with a significantly reduced activation energy of ca. 0.51 eV. At even lower temperatures, the isotherms are fully governed by nearly constant loss behavior, which has frequently been explained by cage-like dynamics. The present results agree with those earlier presented by 7Li NMR spin-lattice relaxation measurements being sensitive to dynamic processes taking place on quite different length scales. Our findings unveil complex Li+ ion dynamics in LTO and help understand its superior electrochemical properties.

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Broadband impedance spectroscopy of Li4Ti5O12: from nearly constant loss effects to long-range ion dynamics. / Gadermaier, Bernhard; Hogrefe, Katharina; Heitjans, Paul et al.
in: Zeitschrift fur Anorganische und Allgemeine Chemie, Jahrgang 647, Nr. 22, 12.11.2021, S. 2167-2171.

Publikation: Beitrag in FachzeitschriftArtikelForschungPeer-Review

Gadermaier B, Hogrefe K, Heitjans P, Wilkening HMR. Broadband impedance spectroscopy of Li4Ti5O12: from nearly constant loss effects to long-range ion dynamics. Zeitschrift fur Anorganische und Allgemeine Chemie. 2021 Nov 12;647(22):2167-2171. Epub 2021 Jun 11. doi: 10.1002/zaac.202100143
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abstract = "Li4Ti5O12 (LTO) is known as one of the most robust and long-lasting anode materials in lithium-ion batteries. As yet, the Li-ion transport properties of LTO are, however, not completely understood. Here, we used broadband impedance spectroscopy spanning a wide temperature range to investigate the full electrical response of LTO over a wide frequency range. It turned out that the isotherms recorded entail information about two relaxation processes. While at high temperatures the isotherms show a frequency independent plateau that corresponds to poor long-range ion transport (<10−11 S cm−1 (298 K), 0.79 eV), they reveal a second region, seen at lower temperatures and higher frequencies, which we attribute to short-range ion dynamics (10−8 S cm−1) with a significantly reduced activation energy of ca. 0.51 eV. At even lower temperatures, the isotherms are fully governed by nearly constant loss behavior, which has frequently been explained by cage-like dynamics. The present results agree with those earlier presented by 7Li NMR spin-lattice relaxation measurements being sensitive to dynamic processes taking place on quite different length scales. Our findings unveil complex Li+ ion dynamics in LTO and help understand its superior electrochemical properties.",
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AU - Gadermaier, Bernhard

AU - Hogrefe, Katharina

AU - Heitjans, Paul

AU - Wilkening, H. Martin R.

N1 - Funding Information: We thank the Deutsche Forschungsgemeinschaft (DFG) for financial support in the frame of the former research unit FOR 1277 (2010–2017) “Mobilität von Lithiumionen in Festkörpern (molife)” (WI 3600 2‐1). Furthermore, financial support by the FFG project safe battery is gratefully acknowledged. P.H. is grateful to the State of Lower Saxony (Germany) for the Niedersachsen Professorship “Mobility of Ions in Solids”.

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N2 - Li4Ti5O12 (LTO) is known as one of the most robust and long-lasting anode materials in lithium-ion batteries. As yet, the Li-ion transport properties of LTO are, however, not completely understood. Here, we used broadband impedance spectroscopy spanning a wide temperature range to investigate the full electrical response of LTO over a wide frequency range. It turned out that the isotherms recorded entail information about two relaxation processes. While at high temperatures the isotherms show a frequency independent plateau that corresponds to poor long-range ion transport (<10−11 S cm−1 (298 K), 0.79 eV), they reveal a second region, seen at lower temperatures and higher frequencies, which we attribute to short-range ion dynamics (10−8 S cm−1) with a significantly reduced activation energy of ca. 0.51 eV. At even lower temperatures, the isotherms are fully governed by nearly constant loss behavior, which has frequently been explained by cage-like dynamics. The present results agree with those earlier presented by 7Li NMR spin-lattice relaxation measurements being sensitive to dynamic processes taking place on quite different length scales. Our findings unveil complex Li+ ion dynamics in LTO and help understand its superior electrochemical properties.

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