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Title: Unveiling the transport properties of protic ionic liquids: Lithium ion dynamics modulated by the anion fluorine reservoir

Journal Article · · Electrochimica Acta
 [1];  [2];  [2];  [3];  [4];  [4];  [5];  [5];  [5];  [6];  [7];  [2]
  1. Politecnico di Milano (Italy); Hunter College (CUNY), New York, NY (United States)
  2. Politecnico di Milano (Italy)
  3. University of Campinas (Brazil)
  4. University of Münster (Germany)
  5. Hunter College (CUNY), New York, NY (United States)
  6. Istituto Struttura della Materia (ISM), Rome (Italy)
  7. ENEA (Italian National Agency for New Technologies, Energy and Sustainable Economic Development), Rome (Italy)
+ Show Author Affiliations

Protic ionic liquids (PILs) show great potential as electrolyte components for energy storage devices. A comprehensive understanding of their transport properties must be achieved to optimize the design of safer and efficient electrolytes. This study focuses on a series of PILs based on the DBUH+ cation (protonated 1,8-diazabicyclo[5,4,0]–undec-7-ene superbase) and three anions derived from strong acids: TFO– (triflate), IM14– (perfluorobutyl-trifluoromethylsulfonylimide) and TFSI– (bis(trifluoromethylsulfonyl)imide). Neat PILs and PILs doped with LiTFO, LiIM14, and LiTFSI were studied using temperature-dependent NMR diffusion and relaxation techniques. The ionicity of these systems was also evaluated. Results revealed that the dynamic behaviour of lithium ions, as well as ionicity, strongly depend on the structural features of the anions, particularly in the case of IM14–, whose main feature is the uneven distribution of the fluorinated sidegroups. The 19F relaxation rates in IM14– provide insights into the rotational reorientation of that anion. DBUH-IM14 exhibited diffusion coefficients lower than the expected ones on the basis of its viscosity, likely due to fluorophilic intermolecular interactions involving the fluorinated terminal groups. The presence of Li+ in the DBUH-IM14 electrolyte led to unexpected and relatively faster translational mobility of Li+ ions, resulting in a higher lithium apparent transference number. However, the trends observed in ionicity indicate a more complex interplay between intermolecular interactions and ion correlations. While DBUH-TFSI showed minimal effect of Li+ addition, DBUH-TFO and DBUH-IM14 exhibited a significant decrease in ionicity, possibly attributed to strong interactions between ions.

Research Organization:
Case Western Reserve Univ., Cleveland, OH (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0019409
OSTI ID:
2311106
Alternate ID(s):
OSTI ID: 2329403
Journal Information:
Electrochimica Acta, Vol. 475; ISSN 0013-4686
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

25 ENERGY STORAGE
Electrolytes
Protic ionic liquids
NMR relaxation
Diffusivity
Fluorinated domains
Ionicity