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@ARTICLE{Berlinger:1030116,
      author       = {Berlinger, Sarah A. and Küpers, Verena and Dudenas, Peter
                      J. and Schinski, Devin and Flagg, Lucas and Lamberty,
                      Zachary D. and McCloskey, Bryan D. and Winter, Martin and
                      Frechette, Joelle},
      title        = {{C}ation valency in water-in-salt electrolytes alters the
                      short- and long-range structure of the electrical double
                      layer},
      journal      = {Proceedings of the National Academy of Sciences of the
                      United States of America},
      volume       = {121},
      number       = {31},
      issn         = {0027-8424},
      address      = {Washington, DC},
      publisher    = {National Acad. of Sciences},
      reportid     = {FZJ-2024-05226},
      pages        = {e2404669121},
      year         = {2024},
      note         = {Zudem unterstützt durch NSF-DFG 2223407.},
      abstract     = {Highly concentrated aqueous electrolytes (termed
                      water-in-salt electrolytes, WiSEs) at solid-liquid
                      interfaces are ubiquitous in myriad applications including
                      biological signaling, electrosynthesis, and energy storage.
                      This interface, known as the electrical double layer (EDL),
                      has a different structure in WiSEs than in dilute
                      electrolytes. Here, we investigate how divalent salts [zinc
                      bis(trifluoromethylsulfonyl)imide, Zn(TFSI)2], as well as
                      mixtures of mono- and divalent salts [lithium
                      bis(trifluoromethylsulfonyl)imide (LiTFSI) mixed with
                      Zn(TFSI)2], affect the short- and long-range structure of
                      the EDL under confinement using a multimodal combination of
                      scattering, spectroscopy, and surface forces measurements.
                      Raman spectroscopy of bulk electrolytes suggests that the
                      cation is closely associated with the anion regardless of
                      valency. Wide-angle X-ray scattering reveals that all bulk
                      electrolytes form ion clusters; however, the clusters are
                      suppressed with increasing concentration of the divalent
                      ion. To probe the EDL under confinement, we use a Surface
                      Forces Apparatus and demonstrate that the thickness of the
                      adsorbed layer of ions at the interface grows with
                      increasing divalent ion concentration. Multiple interfacial
                      layers form following this adlayer; their thicknesses appear
                      dependent on anion size, rather than cation. Importantly,
                      all electrolytes exhibit very long electrostatic decay
                      lengths that are insensitive to valency. It is likely that
                      in the WiSE regime, electrostatic screening is mediated by
                      the formation of ion clusters rather than individual
                      well-solvated ions. This work contributes to understanding
                      the structure and charge-neutralization mechanism in this
                      class of electrolytes and the interfacial behavior of
                      mixed-electrolyte systems encountered in electrochemistry
                      and biology.},
      cin          = {IMD-4},
      ddc          = {500},
      cid          = {I:(DE-Juel1)IMD-4-20141217},
      pnm          = {1221 - Fundamentals and Materials (POF4-122) / DFG project
                      509322222 - Struktur, Dynamik und elektrochemische
                      Stabilität von konzentrierten Elektrolyten in begrenzten
                      Umgebungen (509322222)},
      pid          = {G:(DE-HGF)POF4-1221 / G:(GEPRIS)509322222},
      typ          = {PUB:(DE-HGF)16},
      pubmed       = {39047037},
      UT           = {WOS:001412765500001},
      doi          = {10.1073/pnas.2404669121},
      url          = {https://juser.fz-juelich.de/record/1030116},
}