4.3 Article

Lithium doped N-methyl-N-ethylpyrrolidinium bis(trifluoromethanesulfonyl)amide fast-ion conducting plastic crystals

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JOURNAL OF MATERIALS CHEMISTRY
卷 10, 期 10, 页码 2259-2265

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ROYAL SOC CHEMISTRY
DOI: 10.1039/b003168m

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The incorporation of dopant levels of lithium ions (0.5 to 9.3% by mole) in the N-methyl-N-ethylpyrrolidinium bis(trifluoromethanesulfonyl)amide (P(12)TFSA) plastic crystalline phase results in increases in the solid state ionic conductivity of more than 3 orders of magnitude at 298 K. Conductivities as high as 10(-4) S cm(-1) at 323 K have been measured in these doped plastic crystal phases. These materials can therefore be classified as fast-ion conductors. Higher levels of Li only marginally increase the conductivity, up to around 33 mol%, followed by a slight decrease to 50 mol%. Thermal analysis behaviour has allowed the partial development of the binary phase diagram for the LiTFSA-P(12)TFSA system between 0-50 mol% LiTFSA, which suggests the presence of a solid solution single phase at concentrations less than 9.3 mol% LiTFSA. There is also strong evidence of eutectic behaviour in this system with a eutectic transition temperature around 308 K at 33 mol% LiTFSA. A model relating ionic conduction to phase behaviour in this system is presented. The increased conductivity upon doping has been associated with lithium ion motion via Li-7 solid state NMR linewidth measurements.

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