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Polyether Single and Double Crystalline Blends and the Effect of Lithium Salt on Their Crystallinity and Ionic Conductivity.

ABSTRACT: In this work, blends of Poly(ethylene oxide), PEO, and poly(1,6-hexanediol), PHD, were prepared in a wide composition range. They were examined by Differential Scanning Calorimetry (DSC), Polarized Light Optical Microscopy (PLOM) and Wide Angle X-ray Scattering (WAXS). Based on the results obtained, the blends were partially miscible in the melt and their crystallization was a function of miscibility and composition. Crystallization triggered phase separation. In blends with higher PEO contents both phases were able to crystallize due to the limited miscibility in this composition range. On the other hand, the blends with higher PHD contents display higher miscibility and therefore, only the PHD phase could crystallize in them. A nucleation effect of the PHD phase on the PEO phase was detected, probably caused by a transference of impurities mechanism. Since PEO is widely used as electrolyte in lithium batteries, the PEO/PHD blends were studied with lithium bis(trifluoromethanesulfonyl) imide (LiTFSI), and the effect of Li-salt concentration was studied. We found that the lithium salt preferentially dissolves in the PEO phase without significantly affecting the PHD component. While the Li-salt reduced the spherulite growth rate of the PEO phase within the blends, the overall crystallization rate was enhanced because of the strong nucleating effect of the PHD component. The ionic conductivity was also determined for the blends with Li-salt. At high temperatures (>70 °C), the conductivity is in the order of ~10^-3 S cm^-1, and as the temperature decreases, the crystallization of PHD was detected. This improved the self-standing character of the blend films at high temperatures as compared to the one of neat PEO.

SUBMITTER: Olmedo-Martinez JL

PROVIDER: S-EPMC8271483 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:The design guidelines of polymer structure to effectively promote lithium-ion conduction within the polymer electrolytes (PEs) are crucial for its practical use. In this study, the electrolyte properties of a simple polyether having alkyl side chains with varied lengths (-(CH2)m-H, m = 1, 2, 4, 6, 8, and 12) were compared and established a valid design strategy based on the properties of the alkyl side chain. Various spectro-electrochemical measurements successfully connected the electrolyte properties and the alkyl side chain length. Steric hindrance of the alkyl side chain effectively suppressed the interaction between ether oxygen and lithium-ion (m ≥ 2), decreasing the glass transition temperature and the activation energy of lithium-ion transfer at the electrode-electrolyte interface. The strong hydrophobic interactions aligned and/or aggregated the extended alkyl group (m ≥ 8), creating a rapid lithium-ion transport pathway and enhancing lithium-ion conductivity. A clear trend was observed for the following three crucial factors determining bulk lithium-ion transport properties along with the extension of the alkyl side chain: 1) salt dissociability decreased due to the non-polarity of the alkyl side chain, 2) segmental mobility of polymer chains increased due to the internal plasticizing effect, and 3) lithium-ion transference number increased due to the inhibition of the bulky anion transport by its steric hindrance. The highest lithium-ion conductivity was confirmed for the PEs with an alkyl side chain of moderate length (m = 4) at 70°C, indicating the optimized balance between salt dissociability, polymer segmental mobility, and selective lithium-ion transfer. The length of an alkyl side chain can thus be a critical factor in improving the performance of PEs, including thermal stability and lithium-ion conductivity. Precise tuning of the alkyl side chain-related parameters such as steric hindrance, polarity, internal plasticizing effect, and self-alignment optimizes the polymer segmental mobility and salt dissociability, which is crucial for realizing high lithium-ion conductivity for PEs.

Project description:Correlations among the structure, thermal properties, and ionic conductivity of solid polymer electrolytes (SPEs) were studied using a ureasil-polyethylene oxide (U-PEO) organic-inorganic hybrid prepared according to a simple sol-gel route, employing a low molecular weight PEO macromer (M w = 1900 g mol-1). The behavior of an amorphous sample loaded with lithium triflate (LiTFSI) at an optimum ratio between ether oxygen and lithium (EO/Li+ = 15) was compared with that of a semicrystalline sample prepared without salt loading. The temperature range investigated by differential scanning calorimetry (DSC), Raman spectroscopy, small angle X-ray scattering (SAXS), and complex impedance spectroscopy covered both the glass transition and the melting temperature of the U-PEO. The gauche to trans conformational transformation of the (O-C-C-O)Li+ sequence showed similarity between the temperature evolution of the semi-crystalline U-PEO and amorphous U-PEO:Li+ samples, providing an indication of the local structural memory of crystalline state in the amorphous SPE. The linear thermal expansion of the average correlation distance between the siloxane crosslink nodes and the long-distance period of the lamellar semi-crystalline edifice were determined by SAXS. Comparison of the expansion curves suggested that although the siloxane nodes were excluded from the PEO crystalline edifice, the sharp expansion of the amorphous region between the lamellae during melting permitted modulation of the free volume of the hybrid network. In addition, the temperature-induced Li+-EO decomplexation observed by Raman spectroscopy explained the change of the average activation energy of the conduction process revealed by the different Arrhenius regimes. These results evidence the key role of the ionic conductivity decoupling from the segmental motion of chain pair channels on the improvement of ion mobility through the free volume between chains. This concept may inspire materials chemistry researchers to design optimized structures of polymer electrolytes with minimized structural memory of crystaline building blocks and improved ionic conductivity.

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Polyether Single and Double Crystalline Blends and the Effect of Lithium Salt on Their Crystallinity and Ionic Conductivity.

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