Date of Award


Document Type


Degree Name

Doctor of Philosophy (PhD)

Legacy Department

Mechanical Engineering

Committee Chair/Advisor

Qiao, Rui

Committee Member

Gao , Bruce

Committee Member

Miller , Richard

Committee Member

Saylor , John


At present, electrochemical capacitors (ECs) are emerging as a novel type of energy storage devices and have attracted remarkable attention, due to their key characteristics, such as high power density and excellent durability. However, the moderate energy density of ECs restricts their widespread deployment in everyday technology. To surmount this limitation, four strategies are adopted: (1) to reduce the total system mass, (2) to increase the specific surface area of electrodes, (3) to enhance normalized capacitance, and (4) to expand the range of potentials applied on electrodes. The implementation of these approaches critically relies on the fundamental understanding of physical processes underlying the energy storage mechanisms hinging on the electrical double layers (EDLs) in ECs.
In this dissertation, to gain the fundamentals of EDLs in ECs, based on the strategies described above, we studied the structure, capacitance, and dynamics of EDLs in different electrolytes near electrodes featuring different pores using atomistic simulations. The pores of electrodes are categorized into macropores, mesopores, and micropores, following the decreasing order of pore size. The chosen electrolytes fall into aqueous electrolytes, organic electrolytes, and ionic liquids (ILs), listed by the increasing order of their decomposition voltages.
For the aqueous electrolytes, we explored the water and ion distributions inside electrified micropores (< 2nm) using molecular dynamics (MD) simulations. The results showed that the ion distribution differs qualitatively from that described by classical EDL theories. Based on such exceptional phenomenon, a new sandwich capacitance model was developed to describe the EDLs inside micropores, which is capable of predicting the sharp increase of capacitance that has been experimentally observed in micropores.
For the organic electrolytes, we examined the ion solvation and the EDL structure, capacitance, and dynamics in the electrolyte of tetraethylammonium tetrafluoroborate (TEABF4) in the aprotic solvent of acetonitrile (ACN). Firstly, the solvation of TEA+ and BF4– ions is found to be much weaker than that of small inorganic ions. This characteristic accounts for the rich structure of EDLs near the electrodes. In particular, near charged electrodes, the ion distribution cannot be explained by the traditional EDL models. Secondly, the computed capacitances of EDLs agree well with those inferred from experimental measurements. Finally, we probed the dynamics of EDLs in organic electrolytes by analyzing the rotational dynamics of solvent and the self diffusion coefficients of ion/solvent.
For the ILs, we performed the MD simulations of EDLs at the interface between an IL of 1-butyl-3-methylimidazolium nitrate ([BMIM][NO3]) and planar electrodes. The results revealed that the structure of the EDL is significantly affected by the liquid nature of the IL, the short-range ion–electrode and ion–ion interactions, and the charge delocalization of ions. We showed that the differential capacitance is a quantitative measure of the response of the EDL structure to a change of electrode surface charge density, and the concave-shaped capacitance–potential (C–V) curve is in good agreement with that in the literature.
To further acquire the theoretical understanding of EDLs in ILs, we investigated the effects of ion size and electrode curvature on the EDLs in ILs of 1-butyl-3-methylimidazolium chloride ([BMIM][Cl]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]). The results indicated that the ion size considerably affects the ion distribution and orientation structure of EDLs, and the EDL capacitances follow a certain order of the ion size. It was also found that the EDL capacitance increases as the electrode curvature increases. Based on the insights gained from the EDL structure and capacitance, a “Multiple Ion Layers with Overscreening” (MILO) model was proposed for EDLs in ILs. The capacitance predicted by the MILO model agrees well with that computed from the MD simulation.



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