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Shah, Neel J.

Publications and source records attributed to Shah, Neel J..

Nanosecond solvation dynamics in a polymer electrolyte for lithium batteries

Solvation dynamics critically affect charge transport. Spectroscopic experiments and computer simulations show that these dynamics in aqueous systems occur on a picosecond timescale. In the case of organic electrolytes, however, conflicting values ranging from 1 to several 100 picoseconds have been reported. We resolve this conflict by studying mixtures of an organic polymer and a lithium salt. Lithium ions coordinate with multiple polymer chains, resulting in temporary crosslinks. Relaxation of these crosslinks, detected by quasielastic neutron scattering, are directly related to solvation dynamics. Simulations reveal a broad spectrum of relaxation times. The average timescale for solvation dynamics in both experiment and simulation is one nanosecond. Here we present the direct measurement of ultraslow dynamics of solvation shell break-up in an electrolyte.

25 ENERGY STORAGE↗

Effect of Added Salt on Disordered Poly(ethylene oxide)-Block-Poly(methyl methacrylate) Copolymer Electrolytes

In this report we studied the effect of salt addition on a diblock copolymer system with a negative Flory-Huggins interaction parameter, χ, indicative of attractive interactions between the two blocks. The system studied is poly(ethylene oxide)-block-poly(methyl methacrylate) (PEO-PMMA) with added lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. We studied two asymmetric block copolymers, PEO-PMMA(10-33) and PEO-PMMA(10-64), where the numbers refer to the molar masses of the blocks in kg mol -1 . The small-angle X-ray scattering (SAXS) profiles for PEO-PMMA(10-33) were featureless at all salt concentrations. In contrast, PEO-PMMA(10-64) exhibited SAXS peaks when the salt concentration was between 0.22 ≤ m (mol Li/kg polymer) ≤ 0.44. The appearance of SAXS peaks only in PEO-PMMA(10-64) is consistent with the predictions of ionic self-consistent field theory developed by de la Cruz and co-workers, which predicts that in systems with negative χ, ordered phases are only found when the volume fraction of the ionic block is about 10%.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗