ORCID Profile
0000-0002-8004-1720
Current Organisation
Deakin University
Does something not look right? The information on this page has been harvested from data sources that may not be up to date. We continue to work with information providers to improve coverage and quality. To report an issue, use the Feedback Form.
Research Topics
In Research Link Australia (RLA), "Research Topics" refer to ANZSRC FOR and SEO codes. These topics are either sourced from ANZSRC FOR and SEO codes listed in researchers' related grants or generated by a large language model (LLM) based on their publications.
Top 5 Research Topics
ANZSRC Field of Research (FoR)
Physical Chemistry of Materials | Functional Materials | Energy Generation, Conversion and Storage Engineering | Materials Engineering
ANZSRC Socio-Economic Objective (SEO)
Energy Storage (excl. Hydrogen) | Expanding Knowledge in Technology |
Related Links
Publications
Interphase control for high performance lithium metal batteries using ether aided ionic liquid electrolyte
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D1EE02929K
Abstract: A non-flammable ionic liquid-ether based hybrid electrolyte shows a robust Li deposition morphology and a very stable cycling of NMC|Li metal cell facilitated by a beneficial interphase formation at the anode surface.
Non‐fluorinated Zinc Anions: A Low‐Cost Environmental Approach for Reversible Zinc Electrochemistry
Publisher: Wiley
Date: 23-11-2023
Abstract: Rechargeable zinc batteries (RZBs) are of immense interest as low‐cost and sustainable energy storage devices. However, formation of Zn dendrites, Zn corrosion, and undesired side reactions in aqueous electrolytes as well as the use of costly fluorinated salts in organic electrolytes, have hindered the commercialization of RZBs. In this work, a cost‐efficient and environmentally friendly, non‐aqueous electrolyte comprised of zinc dicyanamide (Zn(dca) 2 ) in dimethyl sulfoxide (DMSO) is shown to support the electrochemical cycling of zinc. Fourier‐transform infrared (FT‐IR) spectroscopy complemented with theoretical studies suggest that the solvation of Zn 2+ is stabilized with both [dca] − anions and DMSO molecules at high concentrations (≥1.0 M) of the zinc salt content. Stable charge/discharge cycles in zinc symmetrical cells with low overpotentials (0.05 V) were especially observed for 1.0 M Zn(dca) 2 /DMSO over 90 cycles at 1.0 mA cm −2 with scanning electron microscopy (SEM) images confirming the formation of a dense and smooth zinc morphology on metal anode surface post‐cycling. X‐ray photoelectron spectroscopy (XPS) also shows that the presence of zinc nitride (Zn 3 N 2 ) helps form a stable SEI layer in the presence of 1.0 M and 2.5 M systems, making [dca]‐based electrolytes highly promising candidates in rechargeable zinc batteries.
Methylation of zebularine investigated using density functional theory calculations
Publisher: Wiley
Date: 03-05-2011
DOI: 10.1002/JCC.21785
Abstract: Deoxyribonucleic acid (DNA) methylation is an epigenetic phenomenon, which adds methyl groups into DNA. This study reveals methylation of a nucleoside antibiotic drug 1-(β-D-ribofuranosyl)-2-pyrimidinone (zebularine or zeb) with respect to its methylated analog, 1-(β-D-ribofuranosyl)-5-methyl-2-pyrimidinone (d5) using density functional theory calculations in valence electronic space. Very similar infrared spectra suggest that zeb and d5 do not differ by types of the chemical bonds, but distinctly different Raman spectra of the nucleoside pair reveal that the impact caused by methylation of zeb can be significant. Further valence orbital-based information details on valence electronic structural changes caused by methylation of zebularine. Frontier orbitals in momentum space and position space of the molecules respond differently to methylation. Based on the additional methyl electron density concentration in d5, orbitals affected by the methyl moiety are classified into primary and secondary contributors. Primary methyl contributions include MO8 (57a), MO18 (47a), and MO37 (28a) of d5, which concentrates on methyl and the base moieties, suggest certain connection to their Frontier orbitals. The primary and secondary methyl affected orbitals provide useful information on chemical bonding mechanism of the methylation in zebularine.
Water as a catalyst for ion transport across the electrical double layer in ionic liquids
Publisher: American Physical Society (APS)
Date: 04-2020
Molecular dynamics study of the effect of tetraglyme plasticizer on dual-cation ionomer electrolytes
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7CP02129A
Abstract: MD shows that tetraglyme could chelate ions and disconnect them from ion clusters in ionomers, which could compromise tetraglyme's plasticization effect.
Corrosion behavior of bulk amorphous Zr55Al10Cu30Ni5−xPdx alloys
Publisher: Elsevier BV
Date: 03-2004
Inorganic-Organic Ionic Liquid Electrolytes Enabling High Energy-Density Metal Electrodes for Energy Storage
Publisher: Elsevier BV
Date: 12-2016
Tuning Sodium Interfacial Chemistry with Mixed-Anion Ionic Liquid Electrolytes
Publisher: American Chemical Society (ACS)
Date: 08-11-2019
Abstract: The interphase layer that forms on either the anode or the cathode is considered to be one of the critical components of a high performing battery. This solid-electrolyte interphase (SEI) layer determines the stability of the electrode in the presence of a given electrolyte as well as the internal resistance of a battery, and hence the overpotential of a cell. In the case of lithium ion batteries where carbonate based electrolytes are used, additives including hexafluorophosphate (PF
New insights into ordering and dynamics in organic ionic plastic crystal electrolytes
Publisher: Elsevier BV
Date: 05-2016
Atomistic simulation of structure and dynamics of the plastic crystal diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate
Publisher: AIP Publishing
Date: 25-06-2013
DOI: 10.1063/1.4811179
Abstract: Molecular dynamics simulations have been performed to investigate the interrelations between structures, transport mechanisms, and phase transitions of an organic ionic plastic crystal material, diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate ([P1,2,2,4][PF6]), in both solid and liquid phases. Examination of the temperature dependence of supercell parameters and radial distribution functions provides evidence of plastic phase transitions. Nonlinear increments of cell size within the temperature range 123–413 K are consistent with the plastic phase transitions identified from experimental analysis. The time- and temperature-dependent microstructure and dynamics have been intensively studied through analysis of trajectory files. The rotational motion and diffusion of the matrix ions are quantitatively analysed via rotational correlation functions and mean square displacements. We present new information on the evolution of molecular motions in different phases, and compare and contrast our findings with previously reported hypotheses based on nuclear magnetic resonance results. This work provides valuable information at an atomistic level to explain the experimental observations, which helps further understanding of the molecular motions underlying the plastic phase transitions.
Suppressed Mobility of Negative Charges in Polymer Electrolytes with an Ether-Functionalized Anion
Publisher: Wiley
Date: 05-08-2019
The impact of electrode conductivity on electrolyte interfacial structuring and its implications on the Na0/+ electrochemical performance
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D3EE00864A
Abstract: Is solid-electrolyte interphase formation affected by electrode conductivity?
Electronic Structure of the Azide Group in 3¢-Azido-3¢-deoxythymidine (AZT) Compared to Small Azide Compounds
Publisher: MDPI AG
Date: 22-07-2009
Insight into local structure and molecular dynamics in organic solid-state ionic conductors
Publisher: Wiley
Date: 18-09-2014
Abstract: Elucidating the rate and geometry of molecular dynamics is particularly important for unravelling ion-conduction mechanisms in electrochemical materials. The local molecular motions in the plastic crystal 1-ethyl-1-methylpyrrolidinium tetrafluoroborate ([C2 mpyr][BF4 ]) are studied by a combination of quantum chemical calculations and advanced solid-state nuclear magnetic resonance spectroscopy. For the first time, a restricted puckering motion with a small fluctuation angle of 25° in the pyrrolidinium ring has been observed, even in the low-temperature phase (-45 °C). This local molecular motion is deemed to be particularly important for the material to maintain its plasticity, and hence, its ion mobility at low temperatures.
Toward High‐Energy‐Density Lithium Metal Batteries: Opportunities and Challenges for Solid Organic Electrolytes
Publisher: Wiley
Date: 21-01-2020
Abstract: With increasing demands for safe, high capacity energy storage to support personal electronics, newer devices such as unmanned aerial vehicles, as well as the commercialization of electric vehicles, current energy storage technologies are facing increased challenges. Although alternative batteries have been intensively investigated, lithium (Li) batteries are still recognized as the preferred energy storage solution for the consumer electronics markets and next generation automobiles. However, the commercialized Li batteries still have disadvantages, such as low capacities, potential safety issues, and unfavorable cycling life. Therefore, the design and development of electromaterials toward high-energy-density, long-life-span Li batteries with improved safety is a focus for researchers in the field of energy materials. Herein, recent advances in the development of novel organic electrolytes are summarized toward solid-state Li batteries with higher energy density and improved safety. On the basis of new insights into ionic conduction and design principles of organic-based solid-state electrolytes, specific strategies toward developing these electrolytes for Li metal anodes, high-energy-density cathode materials (e.g., high voltage materials), as well as the optimization of cathode formulations are outlined. Finally, prospects for next generation solid-state electrolytes are also proposed.
Na-Ion Solvation and High Transference Number in Superconcentrated Ionic Liquid Electrolytes: A Theoretical Approach
Publisher: American Chemical Society (ACS)
Date: 21-12-2018
Ultra-stable all-solid-state sodium metal batteries enabled by perfluoropolyether-based electrolytes
Publisher: Springer Science and Business Media LLC
Date: 04-07-2022
DOI: 10.1038/S41563-022-01296-0
Abstract: Rechargeable batteries paired with sodium metal anodes are considered to be one of the most promising high-energy and low-cost energy-storage systems. However, the use of highly reactive sodium metal and the formation of sodium dendrites during battery operation have caused safety concerns, especially when highly flammable liquid electrolytes are used. Here we design and develop solvent-free solid polymer electrolytes (SPEs) based on a perfluoropolyether-terminated polyethylene oxide (PEO)-based block copolymer for safe and stable all-solid-state sodium metal batteries. Compared with traditional PEO SPEs, our results suggest that block copolymer design allows for the formation of self-assembled nanostructures leading to high storage modulus at elevated temperatures with the PEO domains providing transport channels even at high salt concentration (ethylene oxide/sodium = 8/2). Moreover, it is demonstrated that the incorporation of perfluoropolyether segments enhances the Na
Highly Homogeneous Sodium Superoxide Growth in Na-O2 Batteries Enabled by a Hybrid Electrolyte
Publisher: American Chemical Society (ACS)
Date: 19-02-2020
Cationic polymer-in-salt electrolytes for fast metal ion conduction and solid-state battery applications
Publisher: Research Square Platform LLC
Date: 25-05-2021
DOI: 10.21203/RS.3.RS-532893/V1
Abstract: Polymer electrolytes provide a safe solution for all-solid-state high energy density batteries. Materials that meet the simultaneous requirement of high ionic conductivity and high transference number remain a challenge, in particular for new battery chemistries beyond Lithium such as Na, K and Mg. Herein, we demonstrate the versatility of a polymeric ionic liquid (PolyIL) as a solid-state solvent to achieve this goal for both Na and K. Using molecular simulations, we predict and elucidate fast metal ion transport in PolyILs through a structural diffusion mechanism in a polymer-in-salt environment, facilitating a high transference number. Experimental validation of these computational designed Na and K polymer electrolytes gives high ionic conductivities of 1.010 -3 S cm-1 at 80 o C and an exceptional Na + transference number of ~0.57. Electrochemical cycling of a sodium anode also demonstrates an ultra-low overpotential of 40 mV and stable long term performance of more than 100 hours in a symmetric cell. PolyIL-based polymer-in-salt strategies for novel solid-state electrolytes thus offer a promising route to design high performance next generation sustainable battery chemistries.
Polymer architecture effect on sodium ion transport in PSTFSI-based ionomers: A molecular dynamics study
Publisher: Elsevier BV
Date: 05-2016
Atomistic modelling approaches to understanding the interfaces of ionic liquid electrolytes for batteries and electrochemical devices
Publisher: Elsevier BV
Date: 10-2022
Insights into the transport of alkali metal ions doped into a plastic crystal electrolyte
Publisher: American Chemical Society (ACS)
Date: 26-03-2015
Novel Na+ Ion Diffusion Mechanism in Mixed Organic–Inorganic Ionic Liquid Electrolyte Leading to High Na+ Transference Number and Stable, High Rate Electrochemical Cycling of Sod
Publisher: American Chemical Society (ACS)
Date: 18-02-2016
Unraveling Ion Dynamics and Interactions in an Ionic Liquid Electrolyte with a Protonated Anion for Lithium Batteries
Publisher: American Chemical Society (ACS)
Date: 30-06-2021
Probing Ionic Liquid Electrolyte Structure via the Glassy State by Dynamic Nuclear Polarization NMR Spectroscopy
Publisher: American Chemical Society (ACS)
Date: 13-02-2018
DOI: 10.1021/ACS.JPCLETT.8B00022
Abstract: Dynamic nuclear polarization (DNP)-enhanced solid-state NMR spectroscopy has been used to study an ionic liquid salt solution (N-methyl-N-propyl-pyrrolidinium bis(fluorosulfonyl)imide, C
A reflection on polymer electrolytes for solid-state lithium metal batteries
Publisher: Springer Science and Business Media LLC
Date: 12-08-2023
DOI: 10.1038/S41467-023-40609-Y
Abstract: Before the debut of lithium-ion batteries (LIBs) in the commodity market, solid-state lithium metal batteries (SSLMBs) were considered promising high-energy electrochemical energy storage systems before being almost abandoned in the late 1980s because of safety concerns. However, after three decades of development, LIB technologies are now approaching their energy content and safety limits imposed by the rocking chair chemistry. These aspects are prompting the revival of research activities in SSLMB technologies at both academic and industrial levels. In this perspective article, we present a personal reflection on solid polymer electrolytes (SPEs), spanning from early development to their implementation in SSLMBs, highlighting key milestones. In particular, we discuss the SPEs’ characteristics taking into account the concept of coupled and decoupled SPEs proposed by C. Austen Angell in the early 1990s. Possible remedies to improve the physicochemical and electrochemical properties of SPEs are also examined. With this article, we also aim to highlight the missing blocks in building ideal SSLMBs and stimulate research towards innovative electrolyte materials for future rechargeable high-energy batteries.
Quantitative Investigation of Ion Clusters in a Double Salt Ionic Liquid by Both Vibrational Spectroscopy and Molecular Dynamics Simulation
Publisher: American Chemical Society (ACS)
Date: 20-04-2020
Tuning the Formation and Structure of the Silicon Electrode/Ionic Liquid Electrolyte Interphase in Superconcentrated Ionic Liquids
Publisher: American Chemical Society (ACS)
Date: 11-06-2021
Molecular Dynamics Study of a Dual-Cation Ionomer Electrolyte
Publisher: Wiley
Date: 19-12-2017
Abstract: The poly(N
Stable and Efficient Lithium Metal Anode Cycling through Understanding the Effects of Electrolyte Composition and Electrode Preconditioning
Publisher: American Chemical Society (ACS)
Date: 23-12-2021
Predicting gas selectivity in organic ionic plastic crystals by free energy calculations
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1RA01844B
Abstract: The free energy calculation shows the different free energy changes of the adsorption and absorption of gas molecules into an organic ionic plastic crystal, successfully predicting the gas selectivity of this new type of gas separation material.
Solvent effects on blue shifted improper hydrogen bond of C–H⋯O in deoxycytidine isomers
Publisher: Elsevier BV
Date: 11-2010
Effect of cetrimonium carrier micelles on bacterial membranes and extracellular DNA, an in silico study
Publisher: Springer Science and Business Media LLC
Date: 17-05-2023
DOI: 10.1038/S41598-023-32475-X
Abstract: Microorganisms do not live as dispersed single cells but rather they form aggregates with extracellular polymeric substances at interfaces. Biofilms are considered efficient life forms because they shield bacteria from biocides and collect dilute nutrients. This is a big concern in industry since the microorganisms can colonize a wide range of surfaces, accelerating material deterioration, colonizing medical devices, contaminating ultrapure drinking water, increasing energy costs and creating focus of infection. Conventional biocides that target a specific component of the bacteria are not effective in the presence of biofilms. Efficient biofilm inhibitors are based on a multitarget approach interacting with the bacteria and the biofilm matrix. Their rationale design requires a thorough understanding of inhibitory mechanisms that are still largely lacking today. Herein we uncover via molecular modelling the inhibition mechanism of cetrimonium 4-OH cinnamate (CTA-4OHcinn). Simulations show that CTA-4OH micelles can disrupt symmetric and asymmetric bilayers, representative of inner and outer bacterial membranes, following three stages: adsorption, assimilation, and defect formation. The main driving force for micellar attack is electrostatic interactions. In addition to disrupting the bilayers, the micelles work as carriers facilitating the trapping of 4OH cinnamate anions within the bilayer upper leaflet and overcoming electrostatic repulsion. The micelles also interact with extracellular DNA (e-DNA), which is one of the main components of biofilms. It is observed that CTA-4OHcinn forms spherical micelles on the DNA backbone which hinders their ability to pack. This is demonstrated by modelling the DNA along the hbb histone-like protein, showing that in the presence of CTA-4OHcinn, DNA does not pack properly around hbb. The abilities of CTA-4OHcinn to cause cell death through membrane disruption and to disperse a mature, multi-species biofilm are also confirmed experimentally.
Protic organic ionic plastic crystals based on a difunctional cation and the triflate anion: a new solid-state proton conductor
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6CC07154F
Abstract: A new family of ammonium based organic ionic plastic crystals exhibits exciting solid-state proton conductivity.
Modelling cetrimonium micelles as 4-OH cinnamate carriers targeting a hydrated iron oxide surface
Publisher: Elsevier BV
Date: 03-2022
DOI: 10.1016/J.JCIS.2021.11.139
Abstract: Molecular interactions between 4-OH-cinnamate and cetrimonium in solution result in improved adsorption of the cinnamate on mild steel, developing a protective mechanism against the diffusion of corrosive chloride to the oxide surface. Fundamental understanding of this mechanism should allow new design routes for the development of eco-friendly corrosion inhibitors. Via classic molecular dynamics, simulations were carried out for cetrimonium and 4-OH-cinnamate in aqueous solutions at different ionic strengths and the results were validated with experimental SAXS data. Self-aggregation of cetrimonium 4-OH-cinnamate on a hydrated hematite surface was then simulated and results were compared with cryo-TEM imaging for the same compound. Finally, the effect of the adsorbed aggregates on chloride diffusion to the oxide surface was modelled. Simulations showed the encapsulation of 4-OH-cinnamate into cetrimonium micelles, consistent with experiments. The newly formed micelles adsorb onto a hydrated iron oxide surface by forming hydrogen bonds between their carboxylate outer-shell groups and the surface hydroxyls. As the adsorbate concentrations increase, there is a morphological transition from spherical to wormlike adsorbed aggregates. The wormlike structure can block chloride ions, demonstrating a synergistic inhibitory mechanism between both cetrimonium and 4-OH-cinnamate. Encapsulation and delivery of active compounds to certain targets, such as carcinogenic tumors, have been well studied in biochemistry research, we demonstrate that the same mechanism can be applied to the design of efficient corrosion inhibitors, optimizing their delivery to the metal surface.
Dynamic heterogeneity and ionic conduction in an organic ionic plastic crystal and the role of vacancies
Publisher: American Chemical Society (ACS)
Date: 20-11-2013
DOI: 10.1021/JZ402222J
Factors controlling the physical properties of an organic ionic plastic crystal
Publisher: Elsevier BV
Date: 2022
Molecular dynamics study of atomic transport properties in rapidly cooling liquid copper
Publisher: AIP Publishing
Date: 22-01-2004
DOI: 10.1063/1.1636452
Abstract: Based on Mei’s embedded atom model [Mei et al., Phys. Rev. B 43, 4653 (1991)] molecular dynamics simulations have been performed to investigate the rapidly cooling processes of Cu. The atomic transport property, namely the self-diffusion coefficient, is computed in the liquid state, and the results near the melting point of Cu are in good agreement with experimental data and other computational values. The atom diffusion movements during the long period of relaxation have been also studied around the solidification temperature Tc. To describe the complex microstructural evolutions during the rapidly cooling processes and the long relaxation processes, the pair correlation function and the pair analysis technique are used. It is demonstrated that the crystallization of amorphous Cu is caused by the atomic diffusion.
Ionic Liquid and Polymer‐Based Electrolytes for Sodium Battery Applications
Publisher: Wiley
Date: 09-12-2022
Correlating Intermolecular Cross-Relaxation Rates with Distances and Coordination Numbers in Ionic Liquids
Publisher: American Chemical Society (ACS)
Date: 05-11-2018
DOI: 10.1021/ACS.JPCLETT.8B03021
Abstract: The HOESY NMR experiment is commonly used to probe ion associations in ionic liquids and their mixtures. The parameter measured in this experiment is the heteronuclear cross-relaxation rate σ, which has dimensions of s
Enhanced ion transport in an ether aided super concentrated ionic liquid electrolyte for long-life practical lithium metal battery applications
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0TA06344D
Abstract: We explore a superconcentrated electrolyte comprising N -propyl- N -methylpyrrolidinium bis(fluorosulfonyl)imide, 1,2 dimethoxyethane and 3.2 mol kg −1 LiFSI. It offers an alternative ion-transport mechanism, improved fluidity and ultra-stable Li metal battery performance.
Molecular insights: structure and dynamics of a Li ion doped organic ionic plastic crystal
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C3CP53604A
Abstract: A molecular-level understanding of why the addition of lithium salts to Organic Ionic Plastic Crystals (OIPCs) produces excellent ionic conductivity is described for the first time. These materials are promising electrolytes for safe, robust lithium batteries, and have been experimentally characterised in some detail. Here, molecular dynamics simulations demonstrate the effects of lithium ion doping on both the structure and dynamics of an OIPC matrix (tetramethylammonium dicyanamide [TMA][DCA]) and illustrate a molecular-level transport model: in the plastic crystal phase lithium ions can form clusters with [DCA](-), and this clustering then in turn creates free volume or defect paths in the remainder of the lattice, which enhances ion conduction.
Elucidation of transport mechanism and enhanced alkali ion transference numbers in mixed alkali metal-organic ionic molten salts
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6CP01411A
Abstract: This work reveals how structure facilitates diffusion of the Li/Na ion in ionic liquids with the high Li/Na concentration.
Molecular dynamics simulations of pyrrolidinium and imidazolium ionic liquids at graphene interfaces
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7CP03389C
Abstract: MD simulations of ionic liquids support AFM data and point towards a likely relationship between interfacial structures and electrochemical performance.
Cationic polymer-in-salt electrolytes for fast metal ion conduction and solid-state battery applications
Publisher: Springer Science and Business Media LLC
Date: 28-07-2022
DOI: 10.1038/S41563-022-01319-W
Abstract: Polymer electrolytes provide a safe solution for future solid-state high-energy-density batteries. Materials that meet the simultaneous requirement of high ionic conductivity and high transference number remain a challenge, in particular for new battery chemistries beyond lithium such as Na, K and Mg. Herein, we demonstrate the versatility of a polymeric ionic liquid (PolyIL) as a polymer solvent to achieve this goal for both Na and K. Using molecular simulations, we predict and elucidate fast alkali metal ion transport in PolyILs through a structural diffusion mechanism in a polymer-in-salt environment, facilitating a high metal ion transference number simultaneously. Experimental validation of these computationally designed Na and K polymer electrolytes shows good ionic conductivities up to 1.0 × 10
Polar Organic Cations at Electrified Metal with Superconcentrated Ionic Liquid Electrolyte and Implications for Sodium Metal Batteries
Publisher: American Chemical Society (ACS)
Date: 09-09-2022
Engineering high-energy-density sodium battery anodes for improved cycling with superconcentrated ionic-liquid electrolytes
Publisher: Springer Science and Business Media LLC
Date: 04-05-2020
Engineering High Energy Density Sodium Battery Anodes for Improved Cycling with Superconcentrated Ionic Liquid Electrolytes
Publisher: American Chemical Society (ACS)
Date: 30-01-2020
DOI: 10.26434/CHEMRXIV.11691714.V2
Abstract: Non-uniform metal deposition and dendrite formation in high density energy storage devices reduces the efficiency, safety, and life of batteries with metal anodes. Superconcentrated ionic liquid (IL) electrolytes (e.g. 1:1 IL:alkali ion) coupled with anode preconditioning at more negative potentials can completely mitigate these issues, and therefore revolutionize high density energy storage devices. However, the mechanisms by which very high salt concentration and preconditioning potential enable uniform metal deposition and prevent dendrite formation at the metal anode during cycling are poorly understood, and therefore not optimized. Here, we use atomic-force microscopy and molecular dynamics simulations to unravel the influence of these factors on the interface chemistry in a sodium electrolyte, demonstrating how a molten salt like structure at the electrode surface results in dendrite free metal cycling at higher rates. Such a structure will support the formation of a more favorable solid electrolyte interphase (SEI) accepted as being a critical factor in stable battery cycling. This new understanding will enable engineering of efficient anode electrodes by tuning interfacial nanostructure via salt concentration and high voltage preconditioning.
Engineering High Energy Density Sodium Battery Anodes for Improved Cycling with Superconcentrated Ionic Liquid Electrolytes
Publisher: American Chemical Society (ACS)
Date: 23-01-2020
DOI: 10.26434/CHEMRXIV.11691714.V1
Abstract: Non-uniform metal deposition and dendrite formation in high density energy storage devices reduces the efficiency, safety, and life of batteries with metal anodes. Superconcentrated ionic liquid (IL) electrolytes (e.g. 1:1 IL:alkali ion) coupled with anode preconditioning at more negative potentials can completely mitigate these issues, and therefore revolutionize high density energy storage devices. However, the mechanisms by which very high salt concentration and preconditioning potential enable uniform metal deposition and prevent dendrite formation at the metal anode during cycling are poorly understood, and therefore not optimized. Here, we use atomic-force microscopy and molecular dynamics simulations to unravel the influence of these factors on the interface chemistry in a sodium electrolyte, demonstrating how a molten salt like structure at the electrode surface results in dendrite free metal cycling at higher rates. Such a structure will support the formation of a more favorable solid electrolyte interphase (SEI) accepted as being a critical factor in stable battery cycling. This new understanding will enable engineering of efficient anode electrodes by tuning interfacial nanostructure via salt concentration and high voltage preconditioning.
Poly(Ionic Liquid)s-in-Salt Electrolytes with Co-coordination-Assisted Lithium-Ion Transport for Safe Batteries
Publisher: Elsevier BV
Date: 11-2019
Molecular dynamics study of ammonium based co-cation plasticizer effect on lithium ion dynamics in ionomer electrolytes
Publisher: Elsevier BV
Date: 03-2018
Nanoscale modelling of polymer electrolytes for rechargeable batteries
Publisher: Elsevier BV
Date: 04-2021
Cation effect on small phosphonium based ionic liquid electrolytes with high concentrations of lithium salt
Publisher: AIP Publishing
Date: 30-01-2018
DOI: 10.1063/1.5016460
Abstract: Ionic liquid electrolytes with high alkali salt concentrations have displayed some excellent electrochemical properties, thus opening up the field for further improvements to liquid electrolytes for lithium or sodium batteries. Fundamental computational investigations into these high concentration systems are required in order to gain a better understanding of these systems, yet they remain lacking. Small phosphonium-based ionic liquids with high concentrations of alkali metal ions have recently shown many promising results in experimental studies, thereby prompting us to conduct further theoretical exploration of these materials. Here, we conducted a molecular dynamics simulation on four small phosphonium-based ionic liquids with 50 mol. % LiFSI salt, focusing on the effect of cation structure on local structuring and ion diffusional and rotational dynamics—which are closely related to the electrochemical properties of these materials.
Anion-cation interactions in novel ionic liquids based on an asymmetric sulfonimide anion observed by NMR and MD simulations
Publisher: Elsevier BV
Date: 04-2021
Atomistic Simulation of Gas Uptake and Interface-Induced Disordering in Solid Phases of an Organic Ionic Plastic Crystal
Publisher: American Chemical Society (ACS)
Date: 20-08-2018
Abstract: Organic ionic plastic crystals (OIPCs) are a unique class of materials that exhibit a short-range disorder on the molecular level but are ordered at higher length scales. Recent experiments in our group have shown that the OIPC methyl(diethyl)isobutylphosphonium hexafluorophosphate ([P
Molecular simulation study of CO2 and N2 absorption in a phosphonium based organic ionic plastic crystal
Publisher: AIP Publishing
Date: 28-09-2017
DOI: 10.1063/1.4993654
Abstract: An organic ionic plastic crystal (OIPC), methyl(diethyl)isobutylphosphonium hexafluorophosphate [P122i4][PF6], was investigated for CO2 and N2 absorption using molecular simulations. Ab initio calculations showed that both the cation and anion exhibit larger binding energy for CO2 compared with N2. The CO2 absorption, as calculated from classical molecular dynamics simulations, increased by a factor of 7.5 from 275 K to 325 K, while that of N2 showed low absorption at both temperatures. The simulations suggest that the significant increase in CO2 absorption at 325 K is attributed to a higher degree of disorder and increase in the free volume due to the gas/solid interfaces. While the ab initio calculations were helpful in identifying specific interaction sites on the constituent ions, the classical MD simulations elucidated the importance of interfaces in gas absorption studies in this material. The results show that the OIPC can be a promising material for CO2 separations from CO2/N2 mixture.
Modelling ion-pair geometries and dynamics in a 1-ethyl-1-methylpyrrolidinium-based ion-conductive crystal
Publisher: Wiley
Date: 21-08-2014
Abstract: Full conformational and energy explorations are conducted on an organic ionic plastic crystal, 1-ethyl-1-methylpyrrolidium tetrafluoroborate [C2mpyr][BF4]. The onsets of various stages of dynamic behaviour, which appear to account for low-temperature solid-solid phase transitions, are investigated by using quantum-chemical simulations. It is suggested that pseudorotation of the pyrrolidine ring occurs in the first instance the partial rotation of the entire cation subsequently occurs and may be accompanied by reorientation of the ethyl chain as the temperature increases further. A cation-anion configuration, whereby BF4(-) interacts with the C2 mpy cation from the side of the ring, is the most likely structure in the low-temperature phase IV region. These interpretations are supported by (13)C nuclear magnetic resonance chemical-shift analysis.
Blue shifted intramolecular C−H···O improper hydrogen bonds in conformers of zidovudine
Publisher: Elsevier BV
Date: 06-2010
Overscreening and crowding in electrochemical ionic liquid systems
Publisher: American Physical Society (APS)
Date: 12-09-2019
Conformational Dynamics in an Organic Ionic Plastic Crystal
Publisher: American Chemical Society (ACS)
Date: 16-05-2017
Abstract: Understanding the short-range molecular motions of organic ionic plastic crystals is critical for the application of these materials as solid-state electrolytes in electrochemical devices such as lithium batteries. However, the theory of short-range-motions was originally developed for simple molecular plastic crystals and does not take account of strong interionic interactions that are present in organic ionic plastic crystals. Here we report a fundamental investigation of the dynamic behavior of an archetypal ex le triethyl(methyl)phosphonium bis(fluorosulfonyl)amide ([P
Improving Cycle Life through Fast Formation Using a Superconcentrated Phosphonium Based Ionic Liquid Electrolyte for Anode-Free and Lithium Metal Batteries
Publisher: American Chemical Society (ACS)
Date: 02-07-2021
Unravelling the Role of Speciation in Glyme:Ionic Liquid Hybrid Electrolytes for Na−O2 Batteries
Publisher: Wiley
Date: 10-12-2020
Computational Investigation of Mixed Anion Effect on Lithium Coordination and Transport in Salt Concentrated Ionic Liquid Electrolytes
Publisher: American Chemical Society (ACS)
Date: 13-11-2019
DOI: 10.1021/ACS.JPCLETT.9B02416
Abstract: The use of high concentrations of alkali metal ion salts in ionic liquids (ILs) has been demonstrated to significantly improve electrolyte performance, increase alkali metal ion transference numbers, and promote the formation of favorable SEI structures enabling long-term stable cycling. One challenge in using this material is the overall low ionic conductivity, which is a common effect of increased salt concentration. This simulation work first investigated the strategy of using mixed anions to tune the ionic conductivity in a concentrated IL (or "ionic liquid-in-salt") system having 50 mol % lithium salt. The effects of binding strength, size, and mobility of selected anions on coordination and dynamics of lithium ions were discussed. The results confirm its feasibility and provide general guidance for the selection of anions to improve the ionic conductivity of salt-concentrated electrolyte systems based on ionic liquids and other solvent systems.
Related Organisations
Related Funding Activities
Discovery Projects - Grant ID: DP210101172
Start Date: 03-2021
End Date: 03-2024
Amount: $651,162.00
Funder: Australian Research Council
View Funded Activity