Abstract: Given concerns about the low earth abundance of Li in Li-ion batteries, there is growing interest in developing a beyond-Li materials basis for rechargeable batteries. Divalent batteries based on calcium (Ca) have received attention due to their ~2000-fold higher concentration in the earth’s crust along with attractive theoretical metrics if Ca is used as the metallic anode. When most common battery electrolytes come into contact with Ca, however, a passivating solid electrolyte interphase (SEI) forms that prevents Ca 2+ transport. 1 At present, only a small number of nonaqueous electrolytes have been identified that form sufficiently Ca 2+ -conductive SEIs for Ca electrodeposition, limiting the design space for Ca battery development. Thus, learning how to tailor Ca SEI formation is of central importance to identify handles for next-generation battery design. Several methods of modifying SEI to improve Ca 2+ transport have been reported, including synthesizing an ex situ artificial layer, 2 or the introduction of boron-containing electrolyte additives that form beneficial SEI compounds. 3 Ca electrolyte modification faces a unique challenge, however, as the large size and divalent nature of Ca 2+ leads to large coordination environments (up to 7 solvating molecules) in solution. 4 Recent studies have begun to identify that co-reduction of these coordinating molecules has a significant impact on Ca electrochemistry. For example, strong coordination between Ca 2+ and the anion TFSI - has been demonstrated to deactivate Ca plating behavior via TFSI - decomposition. 5,6 However, competition between coordinating molecules can be exploited to favor specific Ca 2+ speciation (i.e. BH 4 - displaces bidentate TFSI - --Ca 2+ in favor of BH 4 - --Ca 2+ interactions) and unlock Ca plating behavior. 6 Further mechanistic understanding is needed to identify the specific connections between Ca 2+ coordination, SEI formation, and anode performance (beyond just a binary toggling of plating behavior). To address this, we have systematically introduced chelating glyme-based solvents into a baseline electrolyte, investigating the subsequent changes in SEI composition and electrochemical behavior. This study investigates the preferential coordination of Ca 2+ by glymes in the baseline electrolyte 1 M Ca(BH 4 ) 2 in tetrahydrofuran (THF). THF is systematically replaced by 1,2-dimethoxyethane (G1) or bis(2-methoxyethyl) ether (G2) over a range of Gx/Ca 2+ molar ratios. Microcalorimetry measurements demonstrate that the introduction of both G1 and G2 to the electrolyte is enthalpically favorable, as each glyme displaces THF from the Ca 2+ coordination sphere and modulates Ca 2+ --BH 4 - speciation, as indicated by NMR and Raman spectroscopy. Addition of a small amount of each glyme (1:1 Gx/Ca 2+ ) increases electrolyte ionic conductivity by nearly half; however, glyme addition systematically increases the overpotentials of both Ca plating and stripping while decreasing Coulombic efficiency. The presence of glymes increases the amount of carbon present in both chemically- and electrochemically-formed SEI as indicated through XPS. We further find increased evidence of fragmentation of strongly Ca 2+ -coordinating molecules (G2, BH 4 - ) within the SEI formed during Ca deposition as compared to formed chemically. Calcium-based olefins as well as ionic phases (CaCO 3 , CaC 2 ) are detected in electrochemically-formed SEI through titration gas chromatography. This work reveals factors that modulate both Ca 2+ coordination and subsequent SEI formation, highlighting preferential coordination as a novel approach for Ca-based electrolyte design. 1 Aurbach, D., Skaletsky, R. & Gofer, Y. The Electrochemical Behavior of Calcium Electrodes in a Few Organic Electrolytes. Journal of The Electrochemical Society 138 , 3536-3545 (1991). 2 Hou, Z., Zhou, R., Min, Z., Lu, Z. & Zhang, B. Realizing Wide-Temperature Reversible Ca Metal Anodes through a Ca 2+ -Conducting Artificial Layer. ACS Energy Letters , 274-279 (2022). 3 Bodin, C. et al. Boron-Based Functional Additives Enable Solid Electrolyte Interphase Engineering in Calcium Metal Battery. Batteries & Supercaps n/a , e202200433 (2022). 4 Tchitchekova, D. S. et al. On the Reliability of Half-Cell Tests for Monovalent (Li + , Na + ) and Divalent (Mg 2+ , Ca 2+ ) Cation Based Batteries. Journal of The Electrochemical Society 164 , A1384-A1392 (2017). 5 Hahn, N. T. et al. Influence of Ether Solvent and Anion Coordination on Electrochemical Behavior in Calcium Battery Electrolytes. ACS Applied Energy Materials 3 , 8437-8447 (2020). 6 Melemed, A. M., Skiba, D. A. & Gallant, B. M. Toggling Calcium Plating Activity and Reversibility through Modulation of Ca 2+ Speciation in Borohydride-Based Electrolytes. The Journal of Physical Chemistry C 126 , 892-902 (2022).