FT-Raman spectroscopic and density functional theory studies on ion preferential solvation and ion association of lithium tetrafluoroborate in 4-methoxymethyl ethylene carbonate-based mixed solvents

Qiao, Hongwei; He-lin, Luan; Fang, Xiangpeng; Zhou, Zhiming; Wen, Yao; Wang, Xin; Li, Jimei; Chen, Chang; Tian, Ye

doi:10.1016/j.molstruc.2007.08.010

Cited by 8 publications

(10 citation statements)

References 15 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…While pure FEC solvent only shows a single peak centered at 730 cm ‐1 , which is assigned to ring skeletal deformation of FEC molecule, [ 25 ] this peak height decreases with the emergence of a new peak centered at 745 cm −1 when increasing salt concentrations from 1 to 3 m . The peak at 745 cm −1 is attributed to a Li‐FEC coordination structure, [ 26,27 ] which suggests an incremental interaction between Li + and FEC solvent in FEC electrolytes with increasing LiTFSI concentration; and the result is consistent with our MD results (Figure S2, Supporting Information).…”

Section: Resultssupporting

confidence: 86%

Engineering Solvation Complex–Membrane Interaction to Suppress Cation Crossover in 3 V Cu‐Al Battery

Wang

Sun

et al. 2020

Small

View full text Add to dashboard Cite

utilize Earth-abundant metal elements as battery anodes, such as Zn, Mg, Al, Fe, and Ca, are attracting much attention due to their advantages in cost and capacity. [7-11] However, these metal anode systems are typically coupled with cathode materials that requires special and expensive engineering to accommodate the metal cation, [12-16] raising the capital and energy cost of the battery. Along this line, metal batteries that utilize low-cost cathodes with eco-efficient fabrication process are appealing for stationary applications. In our previous work, we proposed a novel 3 V metal-metal system that uses low-cost and Earth-abundant Cu and Al metal foils directly as the cathode and anode, respectively, without any additional active material coating and structural engineering. [17] During cycling, the stripping/ plating of Cu at the cathode is accompanied with the alloying/de-alloying of AlLi at the anode in a Li +-containing carbonate electrolyte with electrochemical reactions at each electrode shown below Cathode : Cu (s) Cu e ↔ +

show abstract

Section: Resultssupporting

confidence: 86%

Engineering Solvation Complex–Membrane Interaction to Suppress Cation Crossover in 3 V Cu‐Al Battery

Wang

Sun

et al. 2020

Small

View full text Add to dashboard Cite

show abstract

“…Molecular dynamics simulations and density functional theory as well as quantum chemical calculations have been employed to understand the nature of the interaction between the lithium cation and the carbonate solvent. These studies not only complement the experimental findings but have enabled the determination of thermodynamic parameters associated with such an interaction. ,,− By and large, all of the studies on neat and mixed electrolytes reported thus far are mostly solvent-focused and invariably studied in the solvent-rich regime (<1.4 M). Although information on the nature of primary and secondary solvation and the determination of solvent coordination number are provided, information about the anion–solvent interaction and ion-pairing is hard to discern if the studies are restricted to low concentrations of the electrolyte.…”

Section: Introductionmentioning

confidence: 83%

“…An understanding of the nature of interaction between the lithium salt and the organic carbonate solvent is of paramount importance. Li-ion complexation in nonaqueous carbonate solvents has been examined by several techniques such as Raman, − vibrational, infrared, , and molecular rotation spectroscopies . Nuclear magnetic resonance (NMR) spectroscopy ,− has also been used to glean valuable atomic level insights from the observed changes in the chemical shifts of 13 C and 17 O of the solvent molecule upon complexation with the lithium cation.…”

Section: Introductionmentioning

confidence: 99%

Lithium Speciation in the LiPF₆/PC Electrolyte Studied by Two-Dimensional Heteronuclear Overhauser Enhancement and Pulse-Field Gradient Diffusometry NMR

et al. 2019

View full text Add to dashboard Cite

Electrolytic dissociation of lithium hexafluorophosphate (LiPF6) in the nonaqueous cyclic propylene carbonate (PC) has been investigated in the wide range of concentration (0.05–3.5 M) by 7Li solution-state nuclear magnetic resonance (NMR) spectroscopy. Two-dimensional heteronuclear Overhauser enhancement spectroscopy NMR experiments have not only enabled the cation solvation and ion-pairing to be directly monitored but additionally evidence anion–solvent interaction at higher concentrations (>1.2 M) of the PC electrolyte. Preliminary analysis of kinetic nOe data has been made to determine site-dependent cross-relaxation rates for the spatial interaction of the solvent with the Li+ cation and the PF6 – anion. The concentration dependence of the 7Li NMR self-diffusion coefficient (D self), determined using very strong pulsed magnetic field gradients (∼1700 Gauss/cm), depicts two breaks to mark the solvation and ion-pairing events in a distinct manner. This in turn has aided the determination of solvent coordination number and average sizes of solvated and ion-paired clusters. Our results indicate that in the contact ion pair (CIP)-dominated electrolyte (>2 M), lithium-ion mobility across the solvated and ion-paired environments appears to be inhibited which makes the spectral distinction of solvated and ion-paired environments possible. The concentration dependence of the 7Li NMR spectral and diffusometry data is in striking correspondence with that of bulk conductivity measurements and point to the detrimental effect of CIP aggregates in impeding the ionic conductivity at high salt concentrations. These results have significance in understanding the structure and dynamics of lithium-ion solvates that are ubiquitous in the working environment of a lithium-ion battery.

show abstract

“…The majority of the data are for symmetrical univalent electrolytes, particularly alkali halides, in pure nonaqueous (Hoshina et al, 2004;Kameche et al, 2005;Wurm et al, 2005) and mixed aqueous-organic solvents. In comparison, little information was available for symmetric polyvalent (Molinou and Tsierkezos, 2001;Molinou, 2000, 2006) and unsymmetric electrolytes (K 2 SO 4 , Na 2 SO 4 , Cd(NO 3 ) 2 , CdCl 2 , CaCl 2 , Ca(NO 3 ) 2 , CoCl 2 , and Zn(NO 3 ) 2 ) in nonaqueous (e.g., Gibson et al, 2006;Pura, 2007) or mixed solvents (Fujii et al, 2006;Qiao et al, 2008). In mixed nonaqueous solvents, the study of complexation were almost limited to symmetric univalent electrolytes in binary mixtures containing PC and selected dipolar aprotic solvents such as THF (Al-Najar et al, 1992), EC (Srivastava and Samant, 1994), DMSO (Srivastava and Shankar, 1998), AN (Barthel et al, 1999), and so forth.…”

Section: Downloaded By [Northeastern University] At 07:36 27 Novembermentioning

confidence: 99%

“…In mixed nonaqueous solvents, the study of complexation were almost limited to symmetric univalent electrolytes in binary mixtures containing PC and selected dipolar aprotic solvents such as THF (Al-Najar et al, 1992), EC (Srivastava and Samant, 1994), DMSO (Srivastava and Shankar, 1998), AN (Barthel et al, 1999), and so forth. Qiao et al (2008) determined the ion association of LiBF 4 in MEC + DMC and MEC + AN, and Fujii et al (2006) measured the formation constants of cobalt chloride ion pairs (CoCl + , CoCl − 3 , CoCl 2− 4 , CoCl (2−n)+ n , n = 1-4) in DMF + NMF. In ternary solvent mixtures, such data was virtually nonexistent.…”

Section: Downloaded By [Northeastern University] At 07:36 27 Novembermentioning

confidence: 99%

Solution Properties of Inorganic Contamination in Mixed Solvents: Theory, Progress, and Limitations

Srour¹,

McDonald

2011

Critical Reviews in Environmental Science and Technology

View full text Add to dashboard Cite

Most of what is known about the environmental fate and transport of contaminants comes from studies of dilute, aqueous solutions. Theoretical and practical aspects of hydrophobic organic contaminants in aqueous mixtures of organic solvents are well developed, but relatively little attention has been paid to those situations where inorganic contaminants such as metals, water, and organic solvents occur simultaneously. The authors discuss changes in solution properties accompanying the addition of organic solvents. They review more than 500 references to available data on ion solvation, solubility, activity, acidity, pairing, and pH in electrolyte and electrolyte-free solvent mixtures and tabulate selected experimental values. Whenever available, equations developed to estimate these properties are given and their applications and limitations described. The implications of the progress in mixed-solvents solution chemistry on contaminant behavior and transport are described. Major limitations to the study of inorganic contamination in mixed solvents include the absence of complete and comprehensive data (e.g., type of ionic species, activity coefficients, solubility constants) that characterize solute and solvent properties in these mixtures and the indefinite number of possible solute and solvent combinations. The generation of models predicting such data from easily measured benchmark solute and solvent properties is a major challenge. The availability of such database and models may open the field for environmental engineers and soil scientists to study the basic chemical processes and mechanisms of metal contamination in complex multicomponent systems.

show abstract

FT-Raman spectroscopic and density functional theory studies on ion preferential solvation and ion association of lithium tetrafluoroborate in 4-methoxymethyl ethylene carbonate-based mixed solvents

Cited by 8 publications

References 15 publications

Engineering Solvation Complex–Membrane Interaction to Suppress Cation Crossover in 3 V Cu‐Al Battery

Engineering Solvation Complex–Membrane Interaction to Suppress Cation Crossover in 3 V Cu‐Al Battery

Lithium Speciation in the LiPF₆/PC Electrolyte Studied by Two-Dimensional Heteronuclear Overhauser Enhancement and Pulse-Field Gradient Diffusometry NMR

Solution Properties of Inorganic Contamination in Mixed Solvents: Theory, Progress, and Limitations

Contact Info

Product

Resources

About

FT-Raman spectroscopic and density functional theory studies on ion preferential solvation and ion association of lithium tetrafluoroborate in 4-methoxymethyl ethylene carbonate-based mixed solvents

Cited by 8 publications

References 15 publications

Engineering Solvation Complex–Membrane Interaction to Suppress Cation Crossover in 3 V Cu‐Al Battery

Engineering Solvation Complex–Membrane Interaction to Suppress Cation Crossover in 3 V Cu‐Al Battery

Lithium Speciation in the LiPF6/PC Electrolyte Studied by Two-Dimensional Heteronuclear Overhauser Enhancement and Pulse-Field Gradient Diffusometry NMR

Solution Properties of Inorganic Contamination in Mixed Solvents: Theory, Progress, and Limitations

Contact Info

Product

Resources

About

Lithium Speciation in the LiPF₆/PC Electrolyte Studied by Two-Dimensional Heteronuclear Overhauser Enhancement and Pulse-Field Gradient Diffusometry NMR