Highly disordered amorphous Li-battery electrolytes

Yuntong Zhu, Zachary D. Hood, Haemin Paik, Pedro B. Groszewicz, Steffen P. Emge, Farheen N. Sayed, Chengjun Sun, Moran Balaish, David Ehre, Lincoln J. Miara, Anatoly I. Frenkel, Igor Lubomirsky, Clare P. Grey, Jennifer L.M. Rupp

Research output: Contribution to journalArticlepeer-review

2 Scopus citations

Abstract

“Medium-entropy” highly disordered amorphous Li garnets, with ≥4 unique local bonding units (LBUs), hold promise for use as solid-state electrolytes in hybrid or all-solid-state batteries owing to their grain-boundary-free nature and low-temperature synthesis requirement. Through this work, we resolved the local structure of amorphous Li garnet and understood their implication for Li dynamics. These medium-entropy amorphous structures possess unique characteristics with edge- and face-sharing LBUs, not conforming to the classic Zachariasen glass formation rules, and can be synthesized in a wide but processing-friendly temperature range (<680°C). Within these amorphous structures, Li and Zr are identified as the network formers and La as network modifier, with maxima in Li dynamics observed for smaller Li–O and Zr–O coordination; this structure understanding serves as a baseline for identifying additional network formers to further modulate Li transport. Our insight provides fundamental guidelines for the structure and phase design for amorphous Li garnets and paves the way for their integration in next-generation batteries.

Original languageEnglish
Pages (from-to)500-522
Number of pages23
JournalMatter
Volume7
Issue number2
DOIs
StatePublished - 7 Feb 2024
Externally publishedYes

Bibliographical note

Publisher Copyright:
© 2023 Elsevier Inc.

Funding

Y.Z. acknowledges financial support provided by the MIT Energy Initiative fellowship offered by ExxonMobil. Y.Z. and Z.D.H. acknowledge financial support provided by Samsung Electronics. M.B. acknowledges financial support provided by the US-Israel Fulbright Program, the Zuckerman Israeli Postdoctoral Scholar Program, and the MIT-Technion Postdoctoral Fellowship. P.B.G. acknowledges financial support provided by the German Academic Exchange Service (DAAD) for the PRIME fellowship and the Dutch Research Council (NWO) for the ECCM Tenure Track funding under project number ECCM.006. F.N.S. would like to acknowledge the Faraday Institution CATMAT project (grant number FIRG016) for the funding. S.P.E. acknowledges funding provided by ERC project no. 835073 (BATNMR). Data analysis of X-ray absorption spectroscopy by A.I.F. was supported by NSF grant number DMR-1911592. I.L. acknowledges the BSF program grant 2018717 for his contribution to the these studies. These grants are the two parts of the NSF-BSF grant awarded to A.I.F. and I.L. respectively. J.L.M.R. thanks the Thomas Lord Foundation for financial support. M.B. and J.L.M.R. wish to thank the Bavarian Ministry of Economic Affairs, Regional Development and Energy for funding the research project “Industrialisierbarkeit von Festkörperelektrolytzellen.” This research was performed in part at the Center for Nanoscale Systems (CNS), a member of the National Nanotechnology Coordinated Infrastructure Network, which was supported by the National Science Foundation under NSF award no. 1541959. CNS is a part of Harvard University. This research used resources of the Advanced Photon Source, an Office of Science User Facility operated for the US Department of Energy (DOE) Office of Science by Argonne National Laboratory, and was supported by the US DOE under contract no. DE-AC02-06CH11357, and the Canadian Light Source and its funding partners. The TEM characterization was performed at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility. The authors would also like to thank Prof. Christopher A. Schuh's lab at MIT for offering access and providing support for the DSC experiments. Y.Z. and J.L.M.R. proposed the concept of “medium-entropy” amorphous Li-ion conductors and the classification of existing and newly identified amorphous Li-ion conductors. Y.Z. and J.L.M.R. designed the experiments. Y.Z. Z.D.H. L.J.M. and J.L.M.R. discussed the ceramic processing and phase evolution data. Y.Z. and H.P. performed the EIS measurements. Z.D.H. collected the HR-TEM images. Y.Z. and C.S. performed the XAS experiments. Y.Z. I.L. J.L.M.R. and A.I.F. discussed and performed the data analysis for the XAS experiments. S.P.E. P.B.G. F.N.S. and C.P.G. designed and performed the NMR experiments and analysis. Y.Z. and J.L.M.R. wrote the manuscript with the help of all co-authors. J.L.M.R. is on the advisory board of Matter. Y.Z. acknowledges financial support provided by the MIT Energy Initiative fellowship offered by ExxonMobil. Y.Z. and Z.D.H. acknowledge financial support provided by Samsung Electronics . M.B. acknowledges financial support provided by the US-Israel Fulbright Program, the Zuckerman Israeli Postdoctoral Scholar Program, and the MIT- Technion Postdoctoral Fellowship. P.B.G. acknowledges financial support provided by the German Academic Exchange Service ( DAAD ) for the PRIME fellowship and the Dutch Research Council ( NWO ) for the ECCM Tenure Track funding under project number ECCM.006. F.N.S. would like to acknowledge the Faraday Institution CATMAT project (grant number FIRG016 ) for the funding. S.P.E. acknowledges funding provided by ERC project no. 835073 (BATNMR). Data analysis of X-ray absorption spectroscopy by A.I.F. was supported by NSF grant number DMR-1911592. I.L. acknowledges the BSF program grant 2018717 for his contribution to the these studies. These grants are the two parts of the NSF-BSF grant awarded to A.I.F. and I.L., respectively. J.L.M.R. thanks the Thomas Lord Foundation for financial support. M.B. and J.L.M.R. wish to thank the Bavarian Ministry of Economic Affairs , Regional Development and Energy for funding the research project “Industrialisierbarkeit von Festkörperelektrolytzellen.” This research was performed in part at the Center for Nanoscale Systems ( CNS ), a member of the National Nanotechnology Coordinated Infrastructure Network, which was supported by the National Science Foundation under NSF award no. 1541959. CNS is a part of Harvard University. This research used resources of the Advanced Photon Source, an Office of Science User Facility operated for the US Department of Energy ( DOE ) Office of Science by Argonne National Laboratory , and was supported by the US DOE under contract no. DE-AC02-06CH11357, and the Canadian Light Source and its funding partners. The TEM characterization was performed at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility. The authors would also like to thank Prof. Christopher A. Schuh’s lab at MIT for offering access and providing support for the DSC experiments.

FundersFunder number
Bavarian Ministry of Economic Affairs , Regional Development and Energy
Center for Nanophase Materials Sciences
MIT Energy Initiative
MIT-Technion
NSF-BSF
Technion Postdoctoral Fellowship
Thomas Lord Foundation
US-Israel
Zuckerman Israeli Postdoctoral Scholar Program
National Science FoundationDMR-1911592, 1541959
U.S. Department of EnergyDE-AC02-06CH11357
Bloom's Syndrome Foundation2018717
Samsung
Office of Science
Argonne National Laboratory
Massachusetts Institute of Technology
Harvard University
Canadian Light Source
Faraday InstitutionFIRG016
Engineering Research Centers835073
German Academic Exchange Service
Deutscher Akademischer Austauschdienst
Nederlandse Organisatie voor Wetenschappelijk OnderzoekECCM.006
Bayerisches Staatsministerium für Wirtschaft, Infrastruktur, Verkehr und Technologie
ExxonMobil Foundation

    Keywords

    • LLZO
    • Li-ion conductors
    • LiLaZrO
    • MAP 3: Understanding
    • amorphous Li garnets
    • amorphous oxides
    • medium-entropy oxides
    • solid electrolytes
    • solid-state batteries

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