Density functional complexation study of metal ions with (amino) polycarboxylic acid ligands

Sillanpää, Atte; Aksela, Reijo; Laasonen, Kari

doi:10.1039/b303234p

Cited by 37 publications

(46 citation statements)

References 29 publications

(27 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The solvent effect is included in both optimization and single point calculations through the polarized continuum using the conductor polarizable continuum model (CPCM) [57][58][59][60][61] with tetrahydrofuran (THF) dielectric. Density functional theory calculations are performed with hybrid parameter B3LYP as implemented in Gaussian 09W.…”

Section: Computational Detailsmentioning

confidence: 99%

The Role of Carbonate and Sulfite Additives in Propylene Carbonate-Based Electrolytes on the Formation of SEI Layers at Graphitic Li-Ion Battery Anodes

Bhatt¹,

O’Dwyer²

2014

J. Electrochem. Soc.

View full text Add to dashboard Cite

Density functional theory (DFT) was used to investigate the effect of electrolyte additives such as vinylene carbonate (VC), vinyl ethylene carbonate (VEC), vinyl ethylene sulfite (VES), and ethylene sulfite (ES) in propylene carbonate (PC)-based Li-ion battery electrolytes on SEI formation at graphitic anodes. The higher desolvation energy of PC limits Li + intercalation into graphite compared to solvated Li + in EC. Li + (PC) 3 clusters are found to be unstable with graphite intercalation compounds and become structurally deformed, preventing decomposition mechanisms and associated SEI formation in favor of co-intercalation that leads to exfoliation. DFT calculations demonstrate that the reduction decomposition of PC and electrolyte additives is such that the first electron reduction energies scale as ES > VES > VEC >PC. The second electron reduction follows ES > VES > VEC > VC > PC. The reactivity of the additives under consideration follows ES > VES > VEC > VC. The data demonstrate the supportive role of certain additives, particularly sulfites, in PC-based electrolytes for SEI film formation and stable cycling at graphitic carbon-based Li-ion battery anodes without exfoliation or degradation of the anode structure. The lithium ion battery has been one of the primary power sources driving the digital age, and witnessed a resurgence in interest with the advent of nanoscale materials and advances in cell performance. [1][2][3][4][5][6] Much of the processes and mechanisms underpinning carbonate-based electrolytes in Li-ion batteries, particularly at the anode, still need to be resolved. 7,8 Some commonly used organic solvents are ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC) etc. These organic electrolytes are decomposed during intercalation of lithium ions into graphite anode, resulting in the formation of the crucial solid electrolyte interphase (SEI) film. [9][10][11] This film plays an important role in determining capacity retention, cycle life and safety concerns in lithium ion batteries.12,13 SEI films typically comprise Li 2 O, Li 2 CO 3 and related carbonates, LiF (depending on salt used), and polymer phases together with olefins.14 Effective SEI films provide stable surface passivation without significant reduction in electron conduction (higher transfer resistance). On carbon (graphite) anodes, stable SEI films are crucial for stable cycling and are formed below ∼0.8 V vs. Li + /Li. In practical applications of lithium-ion batteries, the selection of the electrode material is critical, particularly when using high surface area nanomaterials. 15 Enhanced chemical stability against electrolyte oxidation and reduction, high ionic conductivity, high boiling points, and low melting points are required, as well as the ability to solvate a wide range of lithium salts such as LiPF 6 , LiBF 4 or LiClO 4 , 16-21 in aprotic and organic solvents such as ethylene carbonate (EC), propylene carbonate (PC), their mixtures, and ...

show abstract

Section: Computational Detailsmentioning

confidence: 99%

The Role of Carbonate and Sulfite Additives in Propylene Carbonate-Based Electrolytes on the Formation of SEI Layers at Graphitic Li-Ion Battery Anodes

Bhatt¹,

O’Dwyer²

2014

J. Electrochem. Soc.

View full text Add to dashboard Cite

show abstract

“…In particular, for the Fe atom we applied the COSMO radius of 1.393Å from Ref. [50]. The molecular structures were visualized with the program Molden [51].…”

Section: Methodsmentioning

confidence: 99%

Targeting Intermediates of [FeFe]-Hydrogenase by CO and CN Vibrational Signatures

Greco

Bruschi

et al. 2011

Inorg. Chem.

View full text Add to dashboard Cite

In this work we employ density functional theory to assign vibrational signatures of [FeFe]-hydrogenase intermediates to molecular structures. For this purpose, we perform an exhaustive analysis of structures and harmonic vibrations of a series of CN and CO containing model clusters of the [FeFe]-hydrogenase enzyme active site considering also different charges, counter ions and solvents. The pure density functional BP86 in combination with a triple-zeta polarized basis set produce reliable molecular structures as well as harmonic vibrations. Calculated CN and CO stretching vibrations are analyzed separately. Our results are discussed in close comparison to previous studies. Finally, we apply the scaled vibrational frequencies to assign intermediates in [FeFe]-hydrogenase's reaction cycle.

show abstract

“…In a previous study [16], we investigated complexation of metal ions with (amino)polycarboxylic acid ligands using DFT-COSMO and Car-Parrinello ab initio molecular dynamics. As a result, a fast and straightforward computational method for evaluating the performance of complexing agents was developed.…”

Section: Introductionmentioning

confidence: 99%

Density functional complexation study of metal ions with poly(carboxylic acid) ligands. Part 1. Poly(acrylic acid) and poly(α-hydroxy acrylic acid)

Pesonen¹,

Sillanpää²,

Aksela³

et al. 2005

Polymer

Self Cite

View full text Add to dashboard Cite

Density functional complexation study of metal ions with (amino) polycarboxylic acid ligands

Cited by 37 publications

References 29 publications

The Role of Carbonate and Sulfite Additives in Propylene Carbonate-Based Electrolytes on the Formation of SEI Layers at Graphitic Li-Ion Battery Anodes

The Role of Carbonate and Sulfite Additives in Propylene Carbonate-Based Electrolytes on the Formation of SEI Layers at Graphitic Li-Ion Battery Anodes

Targeting Intermediates of [FeFe]-Hydrogenase by CO and CN Vibrational Signatures

Density functional complexation study of metal ions with poly(carboxylic acid) ligands. Part 1. Poly(acrylic acid) and poly(α-hydroxy acrylic acid)

Contact Info

Product

Resources

About