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Nido‐Hydroborate‐Based Electrolytes for All‐Solid‐State Lithium Batteries


Payandeh, SeyedHosein; Rentsch, Daniel; Łodziana, Zbigniew; Asakura, Ryo; Bigler, Laurent; Černý, Radovan; Battaglia, Corsin; Remhof, Arndt (2021). Nido‐Hydroborate‐Based Electrolytes for All‐Solid‐State Lithium Batteries. Advanced Functional Materials, 31(18):2010046.

Abstract

Hydroborate‐based solid electrolytes have recently been successfully employed in high voltage, room temperature all‐solid‐state sodium batteries. The transfer to analogous lithium systems has failed up to now due to the lower conductivity of the corresponding lithium compounds and their high cost. Here LiB11H14 nido‐hydroborate as a cost‐effective building block and its high‐purity synthesis is introduced. The crystal structures of anhydrous LiB11H14 as well as of LiB11H14‐based mixed‐anion solid electrolytes are solved and high ionic conductivities of 1.1 × 10−4 S cm−1 for Li2(B11H14)(CB11H12) and 1.1 × 10−3 S cm−1 for Li3(B11H14)(CB9H10)2 are obtained, respectively. LiB11H14 exhibits an oxidative stability limit of 2.6 V versus Li+/Li and the proposed decomposition products are discussed based on density functional theory calculations. Strategies are discussed to improve the stability of these compounds by modifying the chemical structure of the nido‐hydroborate cage. Galvanostatic cycling in symmetric cells with two lithium metal electrodes shows a small overpotential increase from 22.5 to 30 mV after 620 h (up to 0.5 mAh cm−2), demonstrating that the electrolyte is compatible with metallic anodes. Finally, the Li2(B11H14)(CB11H12) electrolyte is employed in a proof‐of‐concept half cell with a TiS2 cathode with a capacity retention of 82% after 150 cycles at C/5.

Abstract

Hydroborate‐based solid electrolytes have recently been successfully employed in high voltage, room temperature all‐solid‐state sodium batteries. The transfer to analogous lithium systems has failed up to now due to the lower conductivity of the corresponding lithium compounds and their high cost. Here LiB11H14 nido‐hydroborate as a cost‐effective building block and its high‐purity synthesis is introduced. The crystal structures of anhydrous LiB11H14 as well as of LiB11H14‐based mixed‐anion solid electrolytes are solved and high ionic conductivities of 1.1 × 10−4 S cm−1 for Li2(B11H14)(CB11H12) and 1.1 × 10−3 S cm−1 for Li3(B11H14)(CB9H10)2 are obtained, respectively. LiB11H14 exhibits an oxidative stability limit of 2.6 V versus Li+/Li and the proposed decomposition products are discussed based on density functional theory calculations. Strategies are discussed to improve the stability of these compounds by modifying the chemical structure of the nido‐hydroborate cage. Galvanostatic cycling in symmetric cells with two lithium metal electrodes shows a small overpotential increase from 22.5 to 30 mV after 620 h (up to 0.5 mAh cm−2), demonstrating that the electrolyte is compatible with metallic anodes. Finally, the Li2(B11H14)(CB11H12) electrolyte is employed in a proof‐of‐concept half cell with a TiS2 cathode with a capacity retention of 82% after 150 cycles at C/5.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > General Chemistry
Physical Sciences > General Materials Science
Physical Sciences > Condensed Matter Physics
Uncontrolled Keywords:Electrochemistry, Electronic, Optical and Magnetic Materials, General Chemical Engineering, Condensed Matter Physics, Biomaterials
Language:English
Date:1 May 2021
Deposited On:01 Mar 2021 12:56
Last Modified:25 Mar 2024 02:51
Publisher:Wiley-Blackwell Publishing, Inc.
ISSN:1616-301X
OA Status:Hybrid
Free access at:Publisher DOI. An embargo period may apply.
Publisher DOI:https://doi.org/10.1002/adfm.202010046
Project Information:
  • : FunderSNSF
  • : Grant ID200021L_192191
  • : Project TitleMetallic Anodes for Sodium Solid-State Batteries
  • : FunderH2020
  • : Grant ID754364
  • : Project TitleEMPAPOSTDOCS-II - EMPAPOSTDOCS-II MSCA COFUND International, interdisciplinary, inter-sectoral PostDoc Fellowship Programme at Empa
  • Content: Published Version
  • Licence: Creative Commons: Attribution 4.0 International (CC BY 4.0)