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Ca-dimers, solvent layering, and dominant electrochemically active species in Ca(BH4)2 in THF

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  • Ana Sanz Matias

    (Lawrence Berkeley National Laboratory
    Lawrence Berkeley National Laboratory)

  • Fabrice Roncoroni

    (Lawrence Berkeley National Laboratory
    Lawrence Berkeley National Laboratory)

  • Siddharth Sundararaman

    (Lawrence Berkeley National Laboratory
    Lawrence Berkeley National Laboratory)

  • David Prendergast

    (Lawrence Berkeley National Laboratory
    Lawrence Berkeley National Laboratory)

Abstract

Divalent ions (Mg, Ca, and Zn) are being considered as competitive, safe, and earth-abundant alternatives to Li-ion electrochemistry, but present challenges for stable cycling due to undesirable interfacial phenomena. We explore the formation of electroactive species in the electrolyte Ca(BH4)2∣THF using molecular dynamics coupled with a continuum model of bulk and interfacial speciation. Free-energy analysis and unsupervised learning indicate a majority population of neutral Ca dimers and monomers with diverse molecular conformations and an order of magnitude lower concentration of the primary electroactive charged species – the monocation, $${\rm{CaBH}}_{4}^{+}$$ CaBH 4 + – produced via disproportionation of neutral complexes. Dense layering of THF molecules within ~1 nm of the electrode surface strongly modulates local electrolyte species populations. A dramatic increase in monocation population in this interfacial zone is induced at negative bias. We see no evidence for electrochemical activity of fully-solvated Ca2+. The consequences for performance are discussed in light of this molecular-scale insight.

Suggested Citation

  • Ana Sanz Matias & Fabrice Roncoroni & Siddharth Sundararaman & David Prendergast, 2024. "Ca-dimers, solvent layering, and dominant electrochemically active species in Ca(BH4)2 in THF," Nature Communications, Nature, vol. 15(1), pages 1-12, December.
  • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-45672-7
    DOI: 10.1038/s41467-024-45672-7
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    References listed on IDEAS

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    1. Yanliang Liang & Hui Dong & Doron Aurbach & Yan Yao, 2020. "Publisher Correction: Current status and future directions of multivalent metal-ion batteries," Nature Energy, Nature, vol. 5(10), pages 822-822, October.
    2. Hui Dong & Oscar Tutusaus & Yanliang Liang & Ye Zhang & Zachary Lebens-Higgins & Wanli Yang & Rana Mohtadi & Yan Yao, 2020. "High-power Mg batteries enabled by heterogeneous enolization redox chemistry and weakly coordinating electrolytes," Nature Energy, Nature, vol. 5(12), pages 1043-1050, December.
    3. Yanliang Liang & Hui Dong & Doron Aurbach & Yan Yao, 2020. "Current status and future directions of multivalent metal-ion batteries," Nature Energy, Nature, vol. 5(9), pages 646-656, September.
    4. Xin He & Jonathan M. Larson & Hans A. Bechtel & Robert Kostecki, 2022. "In situ infrared nanospectroscopy of the local processes at the Li/polymer electrolyte interface," Nature Communications, Nature, vol. 13(1), pages 1-10, December.
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