Importance of Lithium Coordination Structure to Lithium-Ion Transport in Polyether Electrolytes with Cyanoethoxy Side Chains: An Experimental and Theoretical Approach

Abstract

Polymer electrolytes (PEs) have been studied as an alternative to the current liquid electrolytes in lithium-ion batteries. Although polyether electrolytes have been developed for more than decades, these electrolytes have limitations such as low ionic conductivity and a small lithium-ion (t Li+ ) transference number. In this work, we combine spectro­(electro)­chemical analyses with molecular dynamics (MD) simulations to understand the complex interaction within the electrolyte, consisting of a polyether having both ether and cyano groups (poly­(3-(2-cyanoethoxymethyl)-3-ethyloxetane), PCEO) mixed with various concentrations of lithium bis­(trifluoromethanesulfonyl)­imide (LiTFSI), to clarify the Li+ coordination structure as well as its relevance to Li+ conductivity. Applicability of MD simulations was validated by high-energy X-ray total scattering measurements. The local coordination structures around Li+ were successfully estimated by the distribution function obtained from MD simulations, which suggested the preferable coordination of the cyano group with Li+ over the other elements, including ether oxygen. Further support came from infrared (IR) spectroscopy, where the estimated coordination number (N) obtained from the IR peak area of the deconvoluted CN stretching vibration (ca. 2250–2280 cm–1) agreed well with the MD result. Arrhenius plots of the ionic conductivity showed a curved shape, indicating that the segmental motion of the polymer main chain was responsible for Li+ transportation in PCEO electrolytes. The Li+ conductivity varied with the salt concentration and was sensitive to the Li+ coordination structure. The highest Li+ conductivity was achieved at an intermediate salt concentration, where Li+ coordinated mostly by the cyano group (N = 2.2), followed by the TFSI anion (N = 1.3), and only a small contribution was from ether oxygen (N = 0.5). The characteristic cocontribution of a cyano group and ether oxygen to the Li+ coordination structure can be responsible for the improved Li+ conduction, by accelerating the interchain Li+ transfer, involving a decoordination process, (short-range Li+ conduction) while maintaining good segmental mobility of the polymer (long-range Li+ conduction). The results emphasize the importance of the coordination structure to the electrolyte property, which can provide additional knobs to improve the ionic conductivity as well as the Li+ transference number, leading to further improvements in the performance of polymer electrolytes.

Coordinating Anions “to the Rescue” of the Lithium Ion Mobility in Ternary Solid Polymer Electrolytes Plasticized With Ionic Liquids

“…In accordance with previous experimental and theoretical studies involving cyano‐moieties in competition with other Li + coordination sites such as O PEO or $${O_{{\rm{TFS}}{{\rm{I}}^ - }}}$$, [ 22,23,24,32 ] we find that the $${N_{{\rm{out}},{\rm{TFSA}}{{\rm{M}}^ - }}}$$ coordination peak superimposes that of the ether oxygens, with the latter being downsized significantly in reference to the TFSI analog mixture. We can thus infer that lithium coordination by the polymer chain is partially superseded by TFSAM.…”

Enhanced Electrochemical Properties of Block Copolymer Electrolytes with Blended End-Functionalized Homopolymers

“…Next, we used FT-IR spectroscopy to examine the intermolecular interactions between Li + ions and the −CN moieties of mPEG-CN, mPEG-(CN) 2 , and CN-PEG-CN. As shown in Figure b, the stretching vibrations of free −CN (ν CN ) and Li + -bound CN (ν CN‑Li + ) were observed at 2250 and 2270 cm –1 , respectively . ν CN was proportional to the number of −CN end-groups, and the relative intensities of the ν CN‑Li + and ν CN bands were 0.21, 0.19, and 0.20 for mPEG-CN, mPEG-(CN) 2 , and CN-PEG-CN ( r = 0.06), respectively.…”

“…As shown in Figure 2b, the stretching vibrations of free −CN (ν CN ) and Li + -bound CN (ν CN-Li + ) were observed at 2250 and 2270 cm −1 , respectively. 53 ν CN was proportional to the number of −CN end-groups, and the relative intensities of the ν CN-Li + and ν CN bands were 0.21, 0.19, and 0.20 for mPEG-CN, mPEG-(CN) 2 , and CN-PEG-CN (r = 0.06), respectively. Almost constant relative intensities imply that the CN-PEG-CN electrolytes provide twice as many −CN•••Li + coordination sites as the mPEG-CN electrolyte, as can be seen from the doubled absorbance at 2270 cm −1 .…”

Quantifying the ion coordination strength in polymer electrolytes

“…12,13 In earlier studies, the CN has mainly been determined for different systems, often by computational methods, but also experimentally by both scattering and spectroscopic methods, although frequently resulting in rather broad CN intervals. [14][15][16][17][18][19][20] Only the CN itself, however, does not provide the whole picture of the coordination strength effect on the ion transport in a system, since the ion-dipole interactions between the cation and the ligand are excluded. The scarcity of coordination strength studies, hampered by a lack of suitable methods to quantify this phenomenon, currently limits our understanding of the role of the coordination chemistry on ion transport in SPEs.…”