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The critical role of configurational flexibility in facilitating reversible reactive metal deposition from borohydride solutions

Journal Article · · Journal of Materials Chemistry. A
DOI:https://doi.org/10.1039/D0TA02502J· OSTI ID:1617307
 [1];  [2];  [3];  [4];  [5];  [4];  [2];  [6]
  1. Joint Center for Energy Storage Research; Lemont; USA; Material, Physical and Chemical Sciences Center; Sandia National Laboratories
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States; Univ. of California, Berkeley, CA (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  5. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  6. Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
+ Show Author Affiliations

Development of calcium metal batteries has been historically frustrated by a lack of electrolytes capable of supporting reversible calcium electrodeposition. In this paper, we report the study of an electrolyte consisting of Ca(BH4)2 in tetrahydrofuran (THF) to gain important insight into the role of the liquid solvation environment in facilitating the reversible electrodeposition of this highly reactive, divalent metal. Through interrogation of the Ca2+ solvation environment and comparison with Mg2+ analogs, we show that an ability to reversibly electrodeposit metal at reasonable rates is strongly regulated by dication charge density and polarizability. Our results indicate that the greater polarizability of Ca2+ over Mg2+ confers greater configurational flexibility, enabling ionic cluster formation via neutral multimer intermediates. Increased concentration of the proposed electroactive species, CaBH4+, enables rapid and stable delivery of Ca2+ to the electrode interface. Finally, this work helps set the stage for future progress in the development of electrolytes for calcium and other divalent metal batteries.

Research Organization:
Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC04-94AL85000; AC02-06CH11357; NA0003525
OSTI ID:
1617307
Alternate ID(s):
OSTI ID: 1607830
OSTI ID: 1633064
OSTI ID: 1766488
OSTI ID: 1639080
Report Number(s):
SAND--2019-14382J; 682572
Journal Information:
Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 15 Vol. 8; ISSN 2050-7488; ISSN JMCAET
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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