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@ARTICLE{Wettstein:1024592,
      author       = {Wettstein, Alina and Diddens, Diddo and Heuer, Andreas},
      title        = {{C}ontrolling {L}i + transport in ionic liquid electrolytes
                      through salt content and anion asymmetry: a mechanistic
                      understanding gained from molecular dynamics simulations},
      journal      = {Physical chemistry, chemical physics},
      volume       = {24},
      number       = {10},
      issn         = {1463-9076},
      address      = {Cambridge},
      publisher    = {RSC Publ.},
      reportid     = {FZJ-2024-02266},
      pages        = {6072 - 6086},
      year         = {2022},
      note         = {Unterstützt durch den MWIDE Grant: “GrEEn” project
                      (funding code: 313-W044A)},
      abstract     = {In this work, we report the results from molecular dynamics
                      simulations of lithium salt-ionic liquid electrolytes (ILEs)
                      based either on the symmetric
                      bis[(trifluoromethyl)sulfonyl]imide (TFSI−) anion or its
                      asymmetric analogue
                      2,2,2-(trifluoromethyl)sulfonyl-N-cyanoamide (TFSAM−).
                      Relating lithium's coordination environment to anion mean
                      residence times and diffusion constants confirms the
                      remarkable transport behaviour of the TFSAM−-based ILEs
                      that has been observed in recent experiments: for increased
                      salt doping, the lithium ions must compete for the more
                      attractive cyano over oxygen coordination and a fragmented
                      landscape of solvation geometries emerges, in which lithium
                      appears to be less strongly bound. We present a novel, yet
                      statistically straightforward methodology to quantify the
                      extent to which lithium and its solvation shell are
                      dynamically coupled. By means of a Lithium Coupling Factor
                      (LCF) we demonstrate that the shell anions do not constitute
                      a stable lithium vehicle, which suggests for this
                      electrolyte material the commonly termed “vehicular”
                      lithium transport mechanism could be more aptly pictured as
                      a correlated, flow-like motion of lithium and its
                      neighbourhood. Our analysis elucidates two separate causes
                      why lithium and shell dynamics progressively decouple with
                      higher salt content: on the one hand, an increased sharing
                      of anions between lithium limits the achievable LCF of
                      individual lithium-anion pairs. On the other hand, weaker
                      binding configurations naturally entail a lower dynamic
                      stability of the lithium-anion complex, which is
                      particularly relevant for the TFSAM−-containing ILEs.},
      cin          = {IEK-12},
      ddc          = {540},
      cid          = {I:(DE-Juel1)IEK-12-20141217},
      pnm          = {1221 - Fundamentals and Materials (POF4-122)},
      pid          = {G:(DE-HGF)POF4-1221},
      typ          = {PUB:(DE-HGF)16},
      pubmed       = {35212346},
      UT           = {WOS:000760909900001},
      doi          = {10.1039/D1CP04830A},
      url          = {https://juser.fz-juelich.de/record/1024592},
}