Interfacial structure and differential capacitance of ionic liquid/graphite interface: A perturbed-chain SAFT density functional theory study

Shen, Gulou; Sun, Yunhao; Wang, Yu; Lü, Xiaohua; Ji, Xiaoyan

doi:10.1016/j.molliq.2020.113199

Cited by 18 publications

(14 citation statements)

References 54 publications

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“…Moreover, the ionic shape in ILs is often non-spherical and needs to be accounted for in DFT. Interestingly, there have been developments in DFT to account for chain-like ions and molecules [60], and these have been applied to some extent to study ILs [9][10][11][12][13][14]. Besides chain-like ions, another approach to implement shape and polarizability is via molecular DFT [61][62][63][64].…”

Section: Discussion Conclusion and Outlookmentioning

confidence: 99%

“…MD simulations might be considered as 'exact' and provide dynamics at the molecular scale but are computationally expensive. DFT calculations [8][9][10][11][12][13][14] and MD simulations are extensively used to study double layers in ILs and aqueous electrolytes [15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33]. As an alternative to the MD simulation method, BD is less accurate but computationally cheaper.…”

Section: Introductionmentioning

confidence: 99%

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Capacitance and Structure of Electric Double Layers: Comparing Brownian Dynamics and Classical Density Functional Theory

et al. 2021

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We present a study of the structure and differential capacitance of electric double layers of aqueous electrolytes. We consider electric double layer capacitors (EDLC) composed of spherical cations and anions in a dielectric continuum confined between a planar cathode and anode. The model system includes steric as well as Coulombic ion-ion and ion-electrode interactions. We compare results of computationally expensive, but “exact” , Brownian Dynamics (BD) simulations with approximate, but cheap, calculations based on classical Density Functional Theory (DFT). Excellent overall agreement is found for a large set of system parameters, including variations in concentration, ionic size- and valency-asymmetries, applied voltages and electrode separation, provided the differences between the canonical ensemble of the BD simulations and the grand-canonical ensemble of DFT are properly taken into account. In particular, a careful distinction is made between the differential capacitance $$C_N$$ C N at fixed number of ions and $$C_\mu $$ C μ at fixed ionic chemical potential. Furthermore, we derive and exploit their thermodynamic relations. In the future these relations will also be useful for comparing and contrasting experimental data with theories for supercapactitors and other systems. The quantitative agreement between simulation and theory indicates that the presented DFT is capable of accounting accurately for coupled Coulombic and packing effects. Hence it is a promising candidate to cheaply study room temperature ionic liquids at much lower dielectric constants than that of water.

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Section: Discussion Conclusion and Outlookmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Capacitance and Structure of Electric Double Layers: Comparing Brownian Dynamics and Classical Density Functional Theory

et al. 2021

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Section: Introductionmentioning

confidence: 99%

Capacitance and Structure of Electric Double Layers: Comparing Brownian Dynamics and Classical Density Functional Theory

Cats,

Sitlapersad,

Otter

et al. 2021

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We present a study of the structure and differential capacitance of electric double layers of aqueous electrolytes. We consider Electric Double Layer Capacitors (EDLC) composed of spherical cations and anions in a dielectric continuum confined between a planar cathode and anode. The model system includes steric as well as Coulombic ion-ion and ion-electrode interactions. We compare results of computationally expensive, but "exact", Brownian Dynamics (BD) simulations with approximate, but cheap, calculations based on classical Density Functional Theory (DFT). Excellent overall agreement is found for a large set of system parameters -including variations in concentrations, ionic size-and valency-asymmetries, applied voltages, and electrode separation -provided the differences between the canonical ensemble of the BD simulations and the grand-canonical ensemble of DFT are properly taken into account. In particular a careful distinction is made between the differential capacitance C N at fixed number of ions and C µ at fixed ionic chemical potential. Furthermore, we derive and exploit their thermodynamic relations. In the future these relations are also useful for comparing and contrasting

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“…Moreover, the ionic shape in ILs is often non-spherical and needs to be accounted for in DFT. Interestingly, there have been developments in DFT to account for chain-like ions and molecules [153], and these have been applied to some extent to study ILs [118,119,120,121,122,123]. Besides chain-like ions, another approach to implement shape and polarizability is via molecular DFT [154,155,156,157].…”

Section: Discussion Conclusion and Outlookmentioning

confidence: 99%

“…MD simulations might be considered as 'exact' and provide dynamics at the molecular scale but are computationally expensive. DFT calculations [117,118,119,120,121,122,123] and MD simulations are extensively used to study double layers in ILs and aqueous electrolytes [124,125,126,127,128,129,130,131,132,133,134,135,136,137,138,139,140,141,142]. As an alternative to the MD simulation method, BD is less accurate but computationally cheaper.…”

Section: F2 Msac Decay Lengthmentioning

confidence: 99%

The Electrode-Electrolyte Interface from the perspective of Density Functional Theory

Cats¹

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Odin, the chief of the Aesir (Norse gods), has many names and is often portrayed as an old man, dressed in grey, with a wide-brimmed hat, and one eye. Odin is constantly in pursuit of gaining knowledge and wisdom, often in exchange of a sacrifice; he gave his eye to drink from the well of Mimir, which contains much wisdom, and even hung himself at Yggdrasil (the world tree) pierced by his own spear Gungnir for nine days and nights in order to understand the runes, which also contained wisdom and knowledge. He does not seek knowledge and wisdom only for himself, but he wants to learn anything that might prevent catastrophe at Ragnarok. Moreover in the poem Hávamál (part of the Edda), meaning "words of the high one" (a reference to Odin), he gives wisdom and advice on how to live a good life, e.g. never stop learning, and do not drink too much alcohol.

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Interfacial structure and differential capacitance of ionic liquid/graphite interface: A perturbed-chain SAFT density functional theory study

Cited by 18 publications

References 54 publications

Capacitance and Structure of Electric Double Layers: Comparing Brownian Dynamics and Classical Density Functional Theory

Capacitance and Structure of Electric Double Layers: Comparing Brownian Dynamics and Classical Density Functional Theory

Capacitance and Structure of Electric Double Layers: Comparing Brownian Dynamics and Classical Density Functional Theory

The Electrode-Electrolyte Interface from the perspective of Density Functional Theory

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