ORCID Profile
0000-0002-2151-2932
Current Organisation
Deakin University - Melbourne Burwood Campus
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)
Functional Materials | Materials Engineering | Physical Chemistry of Materials | Energy Generation, Conversion and Storage Engineering | Macromolecular and Materials Chemistry | Electrochemistry | Renewable Power and Energy Systems Engineering (excl. Solar Cells) | Condensed Matter Physics | Synthesis of Materials | Electrochemistry | Medical Biotechnology not elsewhere classified | Materials Engineering not elsewhere classified | Instruments And Techniques | Functional materials | Mechanical Engineering | Metals and Alloy Materials | Composite and Hybrid Materials | Electrochemical energy storage and conversion | Inorganic materials (incl. nanomaterials) | Interdisciplinary Engineering not elsewhere classified | Physical Chemistry (Incl. Structural) | Nanoscale Characterisation | Nanomanufacturing | Chemical engineering | Materials Engineering Not Elsewhere Classified | Surfaces and Structural Properties of Condensed Matter | Condensed Matter Imaging | Condensed Matter Characterisation Technique Development |
ANZSRC Socio-Economic Objective (SEO)
Energy Storage (excl. Hydrogen) | Expanding Knowledge in Technology | Expanding Knowledge in the Chemical Sciences | Renewable Energy not elsewhere classified | Organic Industrial Chemicals (excl. Resins, Rubber and Plastics) | Fabricated Metal Products not elsewhere classified | Sheet Metal Products | Integrated Circuits and Devices | Coated Metal and Metal-Coated Products | Energy Storage, Distribution and Supply not elsewhere classified | Conservation and efficiency | Energy storage | Management of Greenhouse Gas Emissions from Transport Activities | Metals (composites, coatings, bonding, etc.) | Hydrogen Production from Renewable Energy | Solar-Photovoltaic Energy | Expanding Knowledge in the Physical Sciences | Industrial Chemicals and Related Products not elsewhere classified | Expanding Knowledge in the Biological Sciences | Health status (e.g. indicators of “well-being”) | Environmentally Sustainable Transport not elsewhere classified
Related Links
Publications
New Insights into the Fundamental Chemical Nature of Ionic Liquid Film Formation on Magnesium Alloy Surfaces
Publisher: American Chemical Society (ACS)
Date: 14-04-2009
DOI: 10.1021/AM900023J
Abstract: Ionic liquids (ILs) based on trihexyltetradecylphosphonium coupled with either diphenylphosphate or bis(trifluoromethanesulfonyl)amide have been shown to react with magnesium alloy surfaces, leading to the formation a surface film that can improve the corrosion resistance of the alloy. The morphology and microstructure of the magnesium surface seems critical in determining the nature of the interphase, with grain boundary phases and intermetallics within the grain, rich in zirconium and zinc, showing almost no interaction with the IL and thereby resulting in a heterogeneous surface film. This has been explained, on the basis of solid-state NMR evidence, as being due to the extremely low reactivity of the native oxide films on the intermetallics (ZrO2 and ZnO) with the IL as compared with the magnesium-rich matrix where a magnesium hydroxide and/or carbonate inorganic surface is likely. Solid-state NMR characterization of the ZE41 alloy surface treated with the IL based on (Tf)2N(-) indicates that this anion reacts to form a metal fluoride rich surface in addition to an organic component. The diphenylphosphate anion also seems to undergo an additional chemical process on the metal surface, indicating that film formation on the metal is not a simple chemical interaction between the components of the IL and the substrate but may involve electrochemical processes.
Unveiling the Impact of the Cations and Anions in Ionic Liquid/Glyme Hybrid Electrolytes for Na–O2 Batteries
Publisher: American Chemical Society (ACS)
Date: 12-01-2022
Abstract: A series of hybrid electrolytes composed of diglyme and ionic liquids (ILs) have been investigated for Na-O
A Fundamental Understanding of Sulphur Speciation in Ionic Liquids By in-Situ UV-Vis Method
Publisher: The Electrochemical Society
Date: 30-06-2019
DOI: 10.1149/MA2019-04/10/0491
Abstract: Ionic liquids (ILs) are liquids at room temperature which consist of a large variety of cation and anion. The dipolar and van der waals interactions between the cationic and anionic species govern the physical properties of ILs and their applications. Since last few decades, the potential application of ILs in lithium based battery has increased rapidly as some of the ILs offer wide electrochemical stability window, lithium redox compatibility, fast ionic diffusivity and low flammability [1]. Among other Li based battery systems, lithium sulphur (Li-S) battery is one of the most promising candidates for the next generation high energy density battery with high theoretical capacity of 1675 mAh/g [2]. However, the electrochemical redox reaction in Li-S battery is a complex phenomenon. The reduction of elemental sulphur (S 8 ) proceeds via the formation of various intermediate (S n 2- , n ) polysulphides before reaching the final product S 2- . The stability of these polysulphides are highly dependent on the electrolyte medium [3]. Hence the selection of appropriate electrolyte components play an important role in the overall performance of Li-S battery. The electrochemistry of sulphur-polysulphide system has been well studied in organic solvents, however very less literature is reported on the sulphur reduction mechanism in ILs. In this study, we have investigated the sulphur reduction and speciation in three ionic liquids: N -methyl- N -propylpyrrolidinium bis(fluorosulphonyl)imide (Pyr13 FSI), N -methyl- N -propylpyrrolidinium bis(trifluoromethanesulphonyl)imide (Pyr13 TFSI) , trimethyl(isobutyl)phosphonium bis(fluorosulfonyl)imide (P111i4 FSI). The electrochemical redox reactions of sulphur in these ILs have been studied through cyclic voltammetry (CV) and the polysulphide intermediates are simultaneously investigated by in-situ UV Vis method. These studies showed two reductions and one oxidation peak and the plausible pathways have also been identified. The redox behaviour of sulphur speciation in P111i4 FSI is observed to be very similar to Pyr13 TFSI where glassy carbon is used as working electrode in a three electrode electrochemical cell. On the other hand, the redox process of Pyr13 FSI is found to be distinctively different than Pyr13 TFSI. From the in operando UV-vis study, it is found that Pyr13 FSI electrolyte is responsible for the formation of S3 . - radical anion, whereas the Pyr13 TFSI and P111i4FSI electrolyte do not assist the radical formation during the reduction process. Additionally it can also be stated that, in case of P111i4 FSI, the polysulphides are stabilised by small phosphonium cation which protects the FSI anion from the nucleophilic attack of polysulphides, resulting in the stable sulphur redox cycling in P111i4FSI. Thus, based on molecular reactivity, CV and in-situ UV-vis, we propose that a novel phosphonium cation based ionic liquid (P111i4 FSI) is capable of using in Li-S battery. Therefore, this study brings forward a new concept that both of the cation and anion of an IL cumulatively affect the redox behaviour and sulphur speciation in Li-S battery systems. [1] Hallett, J. P. Welton, T., Room-Temperature Ionic Liquids: Solvents for Synthesis and Catalysis. 2. Chemical Reviews 2011, 111 (5), 3508-3576. [2] Ji, X. Nazar, L. F., Advances in Li-S batteries. Journal of Materials Chemistry 2010, 20 (44), 9821-9826. [3] Zhang, S. S., Liquid electrolyte lithium/sulfur battery: Fundamental chemistry, problems, and solutions. Journal of Power Sources 2013, 231 (Supplement C), 153-162.
Fast Charge and High Stability of Solid‐State Graphite Organic Ionic Plastic Crystal Composite Anodes
Publisher: Wiley
Date: 25-04-2022
Abstract: All‐solid‐state batteries (ASSBs) using organic ionic plastic crystals (OIPCs) are promising candidates to overcome the inherent safety issues of lithium‐ion batteries (LIBs). Although OIPCs have excellent process applicability in the roll‐to‐roll electrode fabrication process, their application as solid electrolytes incorporated in composite electrodes has yet to be demonstrated in detail. Herein, we denote the positive effect of the N ‐ethyl‐ N ‐methylpyrrolidinium bis(fluorosulfonyl)imide ([C 2 mpyr][FSI]) incorporated within a composite graphite anode on the charge rate capability and cycle life. The highest charge capacity ratio (the charge capacity at 2C vs. that measured at 0.1C) was measured for the composite anode with an OIPC composite ratio of 50 wt % (89.5 %, 295.7 mAh/g at 2C charge), almost the same as that of the graphite anode with a liquid electrolyte (85.7 %, 295.9 mAh/g at 2C charge). More favorable lithium‐ion conduction pathways were resolved for the anode with a higher OIPC composite ratio, whereas an excessive amount of OIPC reduced the long‐term cyclability. The most stable discharge capacity retention was obtained for 30 wt % OIPC composite (257.4 mAh/g at the 100th discharge), which showed no signs of discharge capacity fading within 100 cycles. The lithiation/delithiation process of the solid‐state graphite‐[C 2 mpyr][FSI] composite anode was evaluated to be stable and reversible. In addition, the incorporated OIPC composite enhanced the electrolyte/electrode and electrode/current collector contacts. This work highlights multiple advantageous functions of the OIPC in a composite graphite anode, which will broaden our horizons for the use of OIPC composites in ASSBs.
A review of ionic liquid surface film formation on Mg and its alloys for improved corrosion performance
Publisher: Elsevier BV
Date: 11-2013
(Keynote) Solid State Organic Ionic Plastic Crystals and Composite Materials for Energy Storage
Publisher: The Electrochemical Society
Date: 23-07-2018
Abstract: New solid-state materials for energy storage devices are investigated due to their potential to achieve, for ex le, high reliability and safety as well as high energy density. Of the numerous battery chemistries possible, lithium-ion has become one of the most common technologies for portable electronics and is increasingly employed in electric vehicles and stationary storage. We have investigated a range of pyrrolidinium and phosphonium based organic ionic plastic crystals (OIPCs), made entirely of ions, that can be applied as attractive, high safety, solid-state electrolytes for lithium batteries.[1,2] These materials offer attractive stable electrolyte properties and unique interfacial properties,[3] key to the use of high energy density electrodes such as lithium metal. Inherently, OIPCs allow flexibility of design and improve safety due to their advantages as non-volatile components of solid-state devices. In general, the ionic conductivity of OIPCs has been too low for application at ambient temperatures. This presentation will provide an overview of the progress of these materials towards their use in practical solid-state lithium (and sodium) based batteries, including the use of nanoscale polymer composites and the complex role of phase behaviour with addition of lithium and sodium salts.[4-6] Solid-state Li metal | LFP and Li metal | NMC cells with excellent stability and ambient temperature operation are also described.[6,7] References: MacFarlane, D. R., Meakin, P., Sun, J., Amini, N. & Forsyth M., Pyrrolidinium Imides: A New Family of Molten Salts and Conductive Plastic Crystal Phases, Phys. Chem. B , 103 , 4164 (1999). Jin, L., Howlett, P. C., Pringle, J. M., Janikowski, J., Armand, M., MacFarlane, D. R. & Forsyth, M. An organic ionic plastic crystal electrolyte for rate capability and stability of ambient temperature lithium batteries. Energy Environ. Sci. 7, 3352 (2014). Howlett, P. C., Shekibi, Y., MacFarlane, D. R. & Forsyth M., Li-Metal Symmetrical Cell Studies Using Ionic Organic Plastic Crystal Electrolyte, Eng. Mater. , 11 , 1044 (2009). Howlett, P. C., Ponzio, F., Fang, J., Lin, T., Jin, L., Iranipour, N. & Efthimiadis, Thin and Flexible Solid-State Organic Ionic Plastic Crystal-Polymer Nanofibre Composite Electrolytes for Device Applications. Chem. Chem. Phys. 15 , 13784 (2013). Iranipour, N., Gunzelmann, D. J., Seeber, A., Vongsvivut, J., Doherty, C., Ponzio, F., O’Dell, L. A., Hollenk , A. F., Forsyth, M., Howlett, P. C., Ionic Transport Through a Composite Structure of N -ethyl- N -methylpyrrolidinium tetrafluoroborate Organic Ionic Plastic Crystals Reinforced with Polymer Nanofibres. Mater. Chem. A. 3 , 6038 (2015). Zhou, Y. Wang, X. Zhu, H. Armand, M. Forsyth, M. Greene, G. W. Pringle, J. M. Howlett, P. C. N-Ethyl-N-Methylpyrrolidinium Bis(Fluorosulfonyl)Imide-Electrospun Polyvinylidene Fluoride Composite Electrolytes: Characterization and Lithium Cell Studies. Chem. Chem. Phys. , 19, 2225 (2017). Wang, X. Zhu, H. Greene, G. W. Zhou, Y. Yoshizawa-Fujita, M. Miyachi, Y. Armand, M. Forsyth, M. Pringle, J. M. Howlett, P. C. Organic Ionic Plastic Crystal-Based Composite Electrolyte with Surface Enhanced Ion Transport and Its Use in All-Solid-State Lithium Batteries. Mater. Technol. 8, 1700046 (2017).
In-Situ-Activated N-Doped Mesoporous Carbon from a Protic Salt and Its Performance in Supercapacitors
Publisher: American Chemical Society (ACS)
Date: 15-12-2016
Abstract: Protic salts have been recently recognized to be an excellent carbon source to obtain highly ordered N-doped carbon without the need of tedious and time-consuming preparation steps that are usually involved in traditional polymer-based precursors. Herein, we report a direct co-pyrolysis of an easily synthesized protic salt (benzimidazolium triflate) with calcium and sodium citrate at 850 °C to obtain N-doped mesoporous carbons from a single calcination procedure. It was found that sodium citrate plays a role in the final carbon porosity and acts as an in situ activator. This results in a large surface area as high as 1738 m
Reduction of oxygen in a trialkoxy ammonium-based ionic liquid and the role of water
Publisher: Elsevier BV
Date: 04-2016
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.
Lithium Sulfonate Functionalization of Carbon Cathodes as a Substitute for Lithium Nitrate in the Electrolyte of Lithium–Sulfur Batteries
Publisher: Wiley
Date: 06-07-2020
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
Ionic liquids and reactions at the electrochemical interface
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/B923053J
Abstract: Ionic liquids (ILs) represent a fascinating, and yet to be fully understood, medium for a variety of chemical, physical and biological processes. Electrochemical processes form an important subset of these that are particularly of interest, since ILs tend to be good electrochemical solvents and exhibit other properties which make them very useful as electrolytes in electrochemical devices. It is important therefore to understand the extent to which electrochemical reactions and processes behave in a relatively "normal", for ex le aqueous solution, fashion as opposed to exhibiting phenomena more uniquely the product of their organic ionic nature. This perspective examines a range of electrochemical reactions in ionic liquids, in many cases in the context of real world applications, to highlight the phenomena as far as they are understood and where data gaps exist. The important areas of lithium and conducting polymer electrochemistry are discussed in detail.
Application of super-concentrated phosphonium based ionic liquid electrolyte for anode-free lithium metal batteries
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1SE00724F
Abstract: Anode-free lithium metal batteries based on ionic liquid electrolytes offer an excellent pathway to significantly boost the energy density and specific energy over current lithium-ion technology by eliminating the anode material during cell assembly.
Role of Li Concentration and the SEI Layer in Enabling High Performance Li Metal Electrodes Using a Phosphonium Bis(fluorosulfonyl)imide Ionic Liquid
Publisher: American Chemical Society (ACS)
Date: 20-09-2017
Tunable multi-doped carbon nanofiber air cathodes based on a poly(ionic liquid) for sodium oxygen batteries with diglyme/ionic liquid-based hybrid electrolytes
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2TA01586B
Abstract: Multi-doped carbon nanofibers are used as self-standing air cathodes in Na–O 2 batteries. The synergetic effect of multiple heteroatoms greatly enhances oxygen reduction, and diglyme-based hybrid electrolytes remarkably improve cycling performance.
Li-Metal Symmetrical Cell Studies Using Ionic Organic Plastic Crystal Electrolyte
Publisher: Wiley
Date: 12-2009
Rapid I−/I3− Diffusion in a Molecular‐Plastic‐Crystal Electrolyte for Potential Application in Solid‐State Photoelectrochemical Cells
Publisher: Wiley
Date: 21-12-2004
Water-tolerant lithium metal cycling in high lithium concentration phosphonium-based ionic liquid electrolytes
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8SE00159F
Abstract: Cycling stability at high capacities and water-tolerance are two key properties for the operation of high-capacity lithium (Li) metal–air batteries.
Ion interactions and dynamics in pseudohalide based ionic liquid electrolytes containing sodium solutes
Publisher: Elsevier BV
Date: 04-2020
High-Ionicity Electrolytes Based on Bulky Fluoroborate Anions for Stable Na-Metal Cycling
Publisher: American Chemical Society (ACS)
Date: 31-10-2022
Physicochemical characterization of a new family of small alkyl phosphonium imide ionic liquids
Publisher: Elsevier BV
Date: 06-2016
Lithium electrochemistry and cycling behaviour of ionic liquids using cyano based anions
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C3EE23753B
Anodising AZ31 in a Phosphonium Ionic Liquid: Corrosion Protection through Composite Film Deposition
Publisher: The Electrochemical Society
Date: 2012
DOI: 10.1149/2.015212JES
New Solid-State Electrolytes Based on Organic Ionic Plastic Crystals
Publisher: The Electrochemical Society
Date: 23-11-2020
DOI: 10.1149/MA2020-024803MTGABS
Abstract: The development of new solid-state electrolytes for energy storage devices is important for increasing their stability, reliability and safety. Organic ionic plastic crystals (OIPCs) are a relatively new class of material that show increasing promise as solid state electrolytes for devices such as lithium or sodium batteries. [1] OIPCs are crystalline phases found in many of the same organic salt families as ionic liquids but these materials have elevated melting points and exhibit various forms of disorder, which is the origin of their plastic mechanical properties. One of the keys to the development of OIPCs as solid state electrolytes is expanding the range of cations and anions available, and understanding the structure and dynamics of the resultant material. For application in a device, OIPCs are combined with salts of the target ion (e.g. Li + or Na + ), after which detailed analysis of the electrochemical and device parameters is performed. OIPC-based electrolytes can also be combined with polymer nanofibers to further improve their mechanical and transport properties. This presentation will provide an overview of the new OIPC families that we have recently designed and synthesized, and progress of these materials towards their use in practical solid-state lithium and sodium based batteries. We have also investigated the use of nanoscale polymer composites and the combination of OIPCs with very high concentrations of lithium or sodium salts, 2 and the recent work on developing these composite materials will be discussed. References: [1] H. Zhu, D. R. MacFarlane, J. M. Pringle, M. Forsyth Trends in Chemistry , 2019, 1 (1), 126 [2] D. Al-Masri, R. Yunis, H. Zhu, L. Jin, P. Bruce, A. F. Hollenk , J. M. Pringle Journal of Materials Chemistry A , 2019, 7 , 25389-25398
Ionic Liquids and Organic Ionic Plastic Crystals: Advanced Electrolytes for Safer High Performance Sodium Energy Storage Technologies
Publisher: Wiley
Date: 02-05-2018
Ionic Liquids as Antiwear Additives in Base Oils: Influence of Structure on Miscibility and Antiwear Performance for Steel on Aluminum
Publisher: American Chemical Society (ACS)
Date: 14-11-2013
DOI: 10.1021/AM4037614
Abstract: The use of ionic liquids as additives to base oil for the lubrication of steel on aluminum was investigated. The miscibility and wear performance of various phosphonium, imidazolium, and pyrrolidinium ionic liquids in a range of polar and nonpolar base oils was determined. The structure and ion pairing of the ionic liquids was found to be important in determining their miscibility in the base oils. In wear tests, some of the miscible base oil/IL blends reduced the aluminum wear depth when compared to that found with the base oil alone. The nonpolar base oil/IL blends were able to withstand higher wear-test loads than the polar base oil/IL blends. At 10 N, as little as 0.01 mol/kg of IL, or 0.7-0.9 wt %, in the nonpolar base oils was enough to drastically reduce the wear depth on the aluminum. XPS analysis of the wear surfaces suggested that the adsorbing of the IL to the surface, where it can form low-shear layers and also react to form tribofilms, is important in reducing friction and wear. The largest reductions in wear at the highest load tested were found for a mineral oil/P6,6,6,14 (i)(C8)2PO2 blend.
Small quaternary alkyl phosphonium bis(fluorosulfonyl)imide ionic liquid electrolytes for sodium-ion batteries with P2- and O3-Na2/3[Fe2/3Mn1/3]O2 cathode material
Publisher: Elsevier BV
Date: 05-2017
Corrosion of heat treated magnesium alloy ZE41
Publisher: Elsevier BV
Date: 10-2011
Editors’ Choice—Understanding the Superior Cycling Performance of Si Anode in Highly Concentrated Phosphonium-Based Ionic Liquid Electrolyte
Publisher: The Electrochemical Society
Date: 17-08-2020
Energy applications of ionic liquids
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C3EE42099J
The Influence of Water and Metal Ions on the Transport Properties of Trihexyl(tetradecyl)phosphonium Chloride
Publisher: CSIRO Publishing
Date: 2012
DOI: 10.1071/CH12332
Abstract: A recent study indicated that the water-saturated ionic liquid (IL) trihexyl(tetradecyl)phosphonium chloride ([P6,6,6,14][Cl]) provided a viable electrolyte for a Mg-air battery. However, there is limited literature on the properties of IL-water mixtures as battery electrolytes. The physical properties of [P6,6,6,14][Cl] were studied with the addition of both water and metal salts (MgCl2 and LiCl) using conductivity and self-diffusion coefficient measurements. The conductivity of the s les at low water concentrations is surprisingly enhanced by the addition of the metal salt, contrary to lithium IL electrolytes. It was also found that the conductivity of the IL was increased by an order of magnitude by saturation with water. NMR diffusion measurements were used to probe the behaviour of both the cation and the water in the mixtures. It was found that the addition of metal salts to the water-saturated [P6,6,6,14][Cl] did not affect the transport properties of the water or cation.
Sustainable Free‐Standing Electrode from Biomass Waste for Sodium‐Ion Batteries
Publisher: Wiley
Date: 19-07-2022
Abstract: Battery sustainability is often neglected in favor of higher performance and economic efficiency in battery technology. The standard electrode containing the use of binder and toxic solvent has a detrimental impact on the environment. For the first time, a sustainable and free‐standing carbonized silk battery anode is prepared from woven silk biomass waste. The unique mechanical structural properties and surface functionality make this material not only avoid the use of binder and organic solvent, but with the possibility of achieving high energy density batteries. An outstanding initial Coulombic efficiency of 75.6 % and a remarkable capacity retention of 100 % after 100 cycles are achieved for the electrode carbonized at 1300 °C (CS_1300 °C) when using a non‐volatile and non‐flammable superconcentrated ionic liquid electrolyte. A uniformly NaF‐distributed solid electrolyte interphase (SEI) layer is produced on the CS_1300 °C surface to facilitate Na + transfer kinetics, and high capacity utilization. Surface functional groups are elucidated by X‐ray photoelectron spectroscopy (XPS), while density functional theory calculations reveal that these groups accelerate fast Na + ion adsorption on the surface, but hinder Na + intercalation kinetics due to the strong binding energy from the sodiophilic sites. This scalable and cost‐efficient strategy opens up a new avenue for mass‐production of battery anode materials, and proposes an argument for the role of surface functional groups in SEI formation and electrochemical performance.
Extensive Sodium Metal Plating and Stripping in a Highly Concentrated Inorganic−Organic Ionic Liquid Electrolyte through Surface Pretreatment
Publisher: Wiley
Date: 26-04-2017
High-rate formation protocol enables a high ionic conductivity SEI for sodium-ion batteries
Publisher: Elsevier BV
Date: 2023
Ball milling: a green mechanochemical approach for synthesis of nitrogen doped carbon nanoparticles
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C3NR02328A
Abstract: Technological and scientific challenges coupled with environmental considerations have attracted a search for robust, green and energy-efficient synthesis and processing routes for advanced functional nanomaterials. In this article, we demonstrate a high-energy ball milling technique for large-scale synthesis of nitrogen doped carbon nanoparticles, which can be used as an electro-catalyst for oxygen reduction reactions after a structural refinement with controlled thermal annealing. The resulting carbon nanoparticles exhibited competitive catalytic activity (5.2 mA cm(-2) kinetic-limiting current density compared with 7.6 mA cm(-2) on Pt/C reference) and excellent methanol tolerance compared to a commercial Pt/C catalyst. The proposed synthesis route by ball milling and annealing is an effective process for carbon nanoparticle production and efficient nitrogen doping, providing a large-scale production method for the development of highly efficient and practical electrocatalysts.
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.
Ultra-stable all-solid-state sodium-metal batteries enabled by perfluoropolyether-based electrolytes
Publisher: Research Square Platform LLC
Date: 02-04-2021
DOI: 10.21203/RS.3.RS-354912/V2
Abstract: Rechargeable batteries paired with sodium (Na)-metal anodes are considered as one of the most promising high energy and low-cost energy storage systems. However, the use of highly reactive Na metal and the formation of Na dendrites during battery operation have caused significant safety concerns, especially when highly flammable liquid electrolytes are used. Herein, we design and develop a solvent-free solid polymer electrolytes (SPEs) based on a perfluoropolyether (PFPE) terminated polyethylene glycol (PEG)-based block copolymer for safe and stable all-solid-state Na-metal batteries. Compared with traditional poly(ethylene oxide) (PEO) or PEG SPEs, our results suggest that block copolymer design allows for the formation of self-assembled microstructures leading to high storage modulus at elevated temperatures with the PEG domains providing transport channels even at high salt concentration (EO/Na + = 8:2). Moreover, it is demonstrated that the incorporation of PFPE segments enhances the Na + transference number of the electrolyte to 0.46 at 80 o C. Finally, the proposed SPE exhibits highly stable symmetric cell cycling performance with high current density (0.5 mA cm -2 and 1.0 mAh cm -2 , up to 1300 hours). The assembled all-solid-state Na-metal batteries with Na 3 V 2 (PO 4 ) 3 cathode demonstrate outstanding rate performance, high capacity retention and long-term charge/discharge stability (CE = 99.91%) after more than 900 cycles.
Electrochemistry of tris(2,2′-bipyridyl) cobalt(II) in ionic liquids and aprotic molecular solvents on glassy carbon and platinum electrodes
Publisher: Elsevier BV
Date: 10-2015
Ultra-stable all-solid-state sodium-metal batteries enabled by perfluoropolyether-based electrolytes
Publisher: Research Square Platform LLC
Date: 26-03-2021
DOI: 10.21203/RS.3.RS-354912/V1
Abstract: Rechargeable batteries paired with sodium (Na)-metal anodes are considered as one of the most promising high energy and low-cost energy storage systems. However, the use of highly reactive Na metal and the formation of Na dendrites during battery operation have caused significant safety concerns, especially when highly flammable liquid electrolytes are used. Herein, we design and develop a solvent-free solid polymer electrolytes (SPEs) based on a perfluoropolyether (PFPE) terminated polyethylene glycol (PEG)-based block copolymer for safe and stable all-solid-state Na-metal batteries. Compared with traditional poly(ethylene oxide) (PEO) or PEG SPEs, our results suggest that block copolymer design allows for the formation of self-assembled microstructures leading to high storage modulus at elevated temperatures with the PEG domains providing transport channels even at high salt concentration (EO/Na+ = 8:2). Moreover, it is demonstrated that the incorporation of PFPE segments enhances the Na+ transference number of the electrolyte to 0.46 at 80 oC. Finally, the proposed SPE exhibits highly stable symmetric cell cycling performance with high current density (0.5 mA cm-2 and 1.0 mAh cm-2, up to 1300 hours). The assembled all-solid-state Na-metal batteries with Na3V2(PO4)3 cathode demonstrate outstanding rate performance, high capacity retention and long-term charge/discharge stability (CE = 99.91%) after more than 900 cycles.
Highly conductive ionogel electrolytes based on N-ethyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide FSI and NaFSI mixtures and their applications in sodium batteries
Publisher: IOP Publishing
Date: 21-06-2021
Abstract: The development of highly conductive and safe electrolytes for sodium-ion batteries is an emerging field beyond lithium battery technologies. In this work we have developed new ionogel electrolytes consisting of a binary mixture of an organic ionic plastic crystal, N -ethyl- N -methylpyrrolidiniumbis(fluorosulfonyl)imide (C 2 mpyrFSI), mixed with NaFSI supported on a mat of electrospun poly (vinylidene fluoride) nanofibers. The salt mixture near the eutectic composition (35 mol% NaFSI) was selected for further study after a detailed phase diagram analysis and ionogel electrolytes based on this were prepared. The ionic conductivity of the prepared ionogel composite reaches 2.6 × 10 −3 S cm −1 at ambient temperature. This ionogel membrane possessed a relatively high Na-ion transference number of 0.44 at 50 °C and we demonstrate the performance of a Na metal full cell using a NaFePO 4 cathode (1.75–4.0 V). The assembled cells show a good capacity retention with coulombic efficiency close to 100% at various C rates between C/20, C/10 and C/5, achieving 120 mAh g −1 at C/20. The long term charge/discharge performance is also demonstrated. Our study provides a feasible method to prepare highly conductive ionogel electrolytes for future Na-battery applications
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
Poly(Ionic Liquid)s-in-Salt Electrolytes with Co-coordination-Assisted Lithium-Ion Transport for Safe Batteries
Publisher: Elsevier BV
Date: 11-2019
Investigating non-fluorinated anions for sodium battery electrolytes based on ionic liquids
Publisher: Elsevier BV
Date: 10-2016
Highly reversible oxygen to superoxide redox reaction in a sodium-containing ionic liquid
Publisher: Elsevier BV
Date: 2017
An Investigation of a Phosphinate-Based Ionic Liquid for Corrosion Protection of Magnesium Alloy AZ31
Publisher: CSIRO Publishing
Date: 2007
DOI: 10.1071/CH06340
Abstract: This work reports a preliminary exploration of the potential of the ionic liquid trihexyl(tetradecyl)phosphonium bis(2,4,4-trimethylpentyl)phosphinate (P6,6,6,14M3PPh) for use as a conversion coating agent for corrosion protection of magnesium alloy AZ31. Results obtained for the as received IL did not indicate any measureable improvement in protection. However, when the IL was allowed to reach equilibrium/saturation with moisture from the atmosphere, treatment with this ‘wet’ solution resulted in a substantial improvement in corrosion resistance. Preliminary electrochemical, optical, and spectroscopic characterization of the film will be presented along with a possible mechanism for film formation.
The influence of the size and symmetry of cations and anions on the physicochemical behavior of organic ionic plastic crystal electrolytes mixed with sodium salts
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C7CP06971E
Abstract: The influence of cations and anions chemistry on the physicochemical behaviour of OIPCs mixed with Na salts is illustrated.
Fast Charge/Discharge of Li Metal Batteries Using an Ionic Liquid Electrolyte
Publisher: The Electrochemical Society
Date: 2013
DOI: 10.1149/2.022310JES
Proton transport in choline dihydrogen phosphate/H3PO4 mixtures
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/C0CP00156B
Abstract: Mixtures of the plastic crystal material choline dihydrogen phosphate [Choline][DHP] and phosphoric acid, from 4.5 mol% to 18 mol% H(3)PO(4), were investigated and shown to have significantly higher proton conductivity compared to the pure [Choline][DHP]. This was particularly evident from the electrochemical hydrogen reduction reaction and the proton NMR diffusion measurements, in addition to ionic conductivity measured from the impedance spectroscopy. The ionic conductivity was observed to increase by more than an order of magnitude in phase I (i.e. the highest temperature solid phase in [Choline][DHP]) reaching up to 10(-2) S cm(-1). The multinuclear NMR spectroscopy data suggest that, at least on the timescale of the NMR measurement, the H(+) cations and [DHP] anions are equivalent in both phases. The pulsed field gradient NMR diffusion measurements of the 18 mol% acid s le indicate that all three ions are mobile, however the H(+) diffusion coefficient is an order of magnitude higher than for the [Choline] cation or the [DHP] anion, and therefore conduction in these materials is dominated by proton conductivity. The thermal stability, as measured by TGA, is unaffected with increasing acid additions and remains high i.e. no significant mass loss below 200 °C.
Artificial SEI Transplantation: A Pathway to Enabling Lithium Metal Cycling in Water-Containing Electrolytes
Publisher: American Chemical Society (ACS)
Date: 27-11-2019
Water as an Effective Additive for High‐Energy‐Density Na Metal Batteries? Studies in a Superconcentrated Ionic Liquid Electrolyte
Publisher: Wiley
Date: 28-03-2019
Abstract: The effect of water on the properties of superconcentrated sodium salt solutions in ionic liquids (ILs) was investigated to design electrolytes for sodium battery applications with water as an additive. Water was added to a 50 mol % solution of NaFSI [FSI=bis(fluorosulfonyl)imide] in the ionic liquid N-methyl-N-propylpyrrolidinium bis(fluorosulfonyl)imide (C
In Situ MRI of Operating Solid-State Lithium Metal Cells Based on Ionic Plastic Crystal Electrolytes
Publisher: American Chemical Society (ACS)
Date: 15-04-2016
Bi-functional oxygen electrocatalysts based on Palladium oxide-Ruthenium oxide composites
Publisher: Springer Science and Business Media LLC
Date: 2012
Abstract: Bi-functional oxygen electrodes are an enabling component for rechargeable metal-air batteries and regenerative fuel cells, both of which are regarded as the next-generation energy devices with zero emission. Nonetheless, at the present, no single metal oxide component can catalyze both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) with high performance which leads to large overpotential between ORR and OER. This work strives to address this limitation by studying the bi-functional electrocatalytic activity of the composite of a good ORR catalyst compound (e.g. palladium oxide, PdO) and a good OER catalyst compound (e.g. ruthenium oxide, RuO 2 ) in alkaline solution (0.1M KOH) utilizing a thin-film rotating disk electrode technique. The studied compositions include PdO, RuO 2 , PdO/RuO 2 (25wt.%/75wt.%), PdO/RuO 2 (50wt.%/50wt.%) and PdO/RuO 2 (75wt.%/25wt.%). The lowest overpotential (e.g. E (2 mA cm −2 ) - E (-2 mA cm −2 )) of 0.82 V is obtained for PdO/RuO 2 (25wt.%/75wt.%) (versus Ag|AgCl (3M NaCl) reference electrode).
Addition of low concentrations of an ionic liquid to a base oil reduces friction over multiple length scales: a combined nano- and macrotribology investigation
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C5CP07061A
Abstract: The efficacy of ionic liquids (ILs) as lubricant additives to a model base oil has been probed at the nanoscale and macroscale as a function of IL concentration using the same materials.
Controlling the Three‐Phase Boundary in Na–Oxygen Batteries: The Synergy of Carbon Nanofibers and Ionic Liquid
Publisher: Wiley
Date: 09-08-2019
Abstract: A series of electrospun binder-free carbon nanofiber (CNF) mats have been studied as air cathodes for Na-oxygen batteries using a pyrrolidinium-based electrolyte and compared with the commercial air cathode Toray 090. A tenfold increase in the discharge capacity is attained when using CNFs in comparison with Toray 090, affording a discharge capacity of 1.53 mAh cm
Towards Higher Energy Density Redox‐Flow Batteries: Imidazolium Ionic Liquid for Zn Electrochemistry in Flow Environment
Publisher: Wiley
Date: 16-02-2017
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.
On the use of organic ionic plastic crystals in all solid-state lithium metal batteries
Publisher: Elsevier BV
Date: 12-2011
Structure and Transport Properties of a Plastic Crystal Ion Conductor: Diethyl(methyl)(isobutyl)phosphonium Hexafluorophosphate
Publisher: American Chemical Society (ACS)
Date: 29-05-2012
DOI: 10.1021/JA301175V
Abstract: Understanding the ion transport behavior of organic ionic plastic crystals (OIPCs) is crucial for their potential application as solid electrolytes in various electrochemical devices such as lithium batteries. In the present work, the ion transport mechanism is elucidated by analyzing experimental data (single-crystal XRD, multinuclear solid-state NMR, DSC, ionic conductivity, and SEM) as well as the theoretical simulations (second moment-based solid static NMR line width simulations) for the OIPC diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate ([P(1,2,2,4)][PF(6)]). This material displays rich phase behavior and advantageous ionic conductivities, with three solid-solid phase transitions and a highly "plastic" and conductive final solid phase in which the conductivity reaches 10(-3) S cm(-1). The crystal structure shows unique channel-like packing of the cations, which may allow the anions to diffuse more easily than the cations at lower temperatures. The strongly phase-dependent static NMR line widths of the (1)H, (19)F, and (31)P nuclei in this material have been well simulated by different levels of molecular motions in different phases. Thus, drawing together of the analytical and computational techniques has allowed the construction of a transport mechanism for [P(1,2,2,4)][PF(6)]. It is also anticipated that utilization of these techniques will allow a more detailed understanding of the transport mechanisms of other plastic crystal electrolyte materials.
Inorganic-Organic Ionic Liquid Electrolytes Enabling High Energy-Density Metal Electrodes for Energy Storage
Publisher: Elsevier BV
Date: 12-2016
Mixed Phase Solid‐State Plastic Crystal Electrolytes Based on a Phosphonium Cation for Sodium Devices
Publisher: Wiley
Date: 22-09-2016
Ion Transport in Li-Doped Triethyl(methyl)phosphonium Tetrafluoroborate (Li-[P1222][BF4]) Impregnated with PVDF Nanoparticles
Publisher: American Chemical Society (ACS)
Date: 22-02-2022
High Zn Concentration Pyrrolidinium-Dicyanamide-Based Ionic Liquid Electrolytes for Zn2+/Zn0 Electrochemistry in a Flow Environment
Publisher: American Chemical Society (ACS)
Date: 12-09-2018
Exploring corrosion protection of Mg via ionic liquid pretreatment
Publisher: Elsevier BV
Date: 2007
Correction to “Oxygen Reduction Reaction Activity of La-Based Perovskite Oxides in Alkaline Medium: A Thin-Film Rotating Ring-Disk Electrode Study”
Publisher: American Chemical Society (ACS)
Date: 29-11-2012
DOI: 10.1021/JP311372A
Double Layer Structure of Ionic Liquids at the Au(111) Electrode Interface: An Atomic Force Microscopy Investigation
Publisher: American Chemical Society (ACS)
Date: 17-03-2011
DOI: 10.1021/JP200544B
The potential for ionic liquid electrolytes to stabilise the magnesium interface for magnesium/air batteries
Publisher: Elsevier BV
Date: 12-2011
Task-Specific Phosphonium Iongels by Fast UV-Photopolymerization for Solid-State Sodium Metal Batteries
Publisher: MDPI AG
Date: 09-11-2022
DOI: 10.3390/GELS8110725
Abstract: Sodium metal batteries are an emerging technology that shows promise in terms of materials availability with respect to lithium batteries. Solid electrolytes are needed to tackle the safety issues related to sodium metal. In this work, a simple method to prepare a mechanically robust and efficient soft solid electrolyte for sodium batteries is demonstrated. A task-specific iongel electrolyte was prepared by combining in a simple process the excellent performance of sodium metal electrodes of an ionic liquid electrolyte and the mechanical properties of polymers. The iongel was synthesized by fast ( min) UV photopolymerization of poly(ethylene glycol) diacrylate (PEGDA) in the presence of a saturated 42%mol solution of sodium bis(fluorosulfonyl)imide (NaFSI) in trimethyl iso-butyl phosphonium bis(fluorosulfonyl)imide (P111i4FSI). The resulting soft solid electrolytes showed high ionic conductivity at room temperature (≥10−3 S cm−1) and tunable storage modulus (104–107 Pa). Iongel with the best ionic conductivity and good mechanical properties (Iongel10) showed excellent battery performance: Na/iongel/NaFePO4 full cells delivered a high specific capacity of 140 mAh g−1 at 0.1 C and 120 mAh g−1 at 1 C with good capacity retention after 30 cycles.
Electrochemical etching of AA5083 aluminium alloy in trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)amide ionic liquid
Publisher: Elsevier BV
Date: 03-2014
The zwitterion effect in high-conductivity polyelectrolyte materials
Publisher: Springer Science and Business Media LLC
Date: 21-12-2003
DOI: 10.1038/NMAT1044
Understanding of the Electrogenerated Bulk Electrolyte Species in Sodium-Containing Ionic Liquid Electrolytes During the Oxygen Reduction Reaction
Publisher: American Chemical Society (ACS)
Date: 13-10-2017
Electrochemistry of the tris(2,2‘-bipyridine) complex of iron(II) in ionic liquids and aprotic molecular solvents
Publisher: Elsevier BV
Date: 12-2016
Towards high rate Li metal anodes: enhanced performance at high current density in a superconcentrated ionic liquid
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/C9TA12004A
Abstract: Application of high current density demonstrated enhanced cycling efficiency and the formation of a stable and LiF dominated SEI providing a new path to enable fast charge battery technologies.
Understanding the Role of Separator and Electrolyte Compatibility on Lithium Metal Anode Performance Using Ionic Liquid-Based Electrolytes
Publisher: American Chemical Society (ACS)
Date: 16-06-2021
Nanoporous transition metal oxynitrides as catalysts for the oxygen reduction reaction
Publisher: Elsevier BV
Date: 07-2013
A Review of Ionic Liquid Lubricants
Publisher: MDPI AG
Date: 21-01-2013
Lubricin Antiadhesive Coatings Exhibit Size-Selective Transport Properties that Inhibit Biofouling of Electrode Surfaces with Minimal Loss in Electrochemical Activity
Publisher: Wiley
Date: 05-02-2018
Effect of secondary phase on thermal behaviour and solid-state ion conduction in lithium doped N-ethyl-N-methylpyrrolidinium tetrafluoroborate organic ionic plastic crystal
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7TA08653A
Abstract: Microstructural features significantly affecting lithium ion dynamics and conduction within the crystalline structure of pyrrolidinium based organic ionic plastic crystals.
Si Anode in High-Salt Concentration Ionic Liquid Electrolytes Based on Pyrrolidinium and Phosphonium Systems for High-Energy Li-Ion Batteries
Publisher: The Electrochemical Society
Date: 09-2019
Abstract: In order to push further the development of next generation Li-ion batteries (LiBs), high energy density, good capacity retention and increased safety are key features that need to be taken into account when designing energy storage devices. To this date, commercial batteries for portable devices mainly use graphite as anode. However, with the advent of electric vehicles and intelligent power grids, there is an increasing demand for high capacity materials to meet the energy and power requirement of these applications. More recently, Si anode has received considerable attention because of its natural abundance and its ability to deliver high energy density, with a gravimetric capacity of 3579 mAhg -1 which is almost 10 times that of graphite (372 mAhg -1 ) [1-2]. Bearing in mind that commercial LiBs use carbonate electrolytes which are recognized to pose safety issues and have been identified to suffer from degradation during charge-discharge cycles, we explored in this study the performance of Si anode in ionic liquid electrolytes based on phosphonium and pyrrolidinium cations, systems that are currently the most studied in the field of Li batteries [3-4]. Ionic liquid electrolytes are an appealing alternative to carbonates mainly because of their low volatility and better stability. In the recent years, good electrochemical behavior has been observed in ionic liquids with high salt concentration [3-5]. In this work, we were able to demonstrate better electrochemical performance of Si anode in ionic liquid electrolytes with 3.2 m LiFSI compared to conventional carbonate electrolytes in terms of capacity and capacity retention at 50°C. Electrochemical performance obtained in the phosphonium and pyrrolidinium systems are compared for different concentrations and temperatures. Moreover, initial investigation of the SEI using NMR and XPS spectroscopy revealed that less degradation products are formed upon cycling in ionic liquid electrolytes compared to usual carbonates electrolytes. Overall, these results highlight the stability of ionic liquids which translate to good cycling performance and show promising potential of Si anode as a high-capacity material for high-energy and high-temperature applications. Cyclability and capacity retention for the phosphonium and pyrrolidinium system will be discussed in terms of ionic liquids components degradation and SEI formation and evolution, as probed by combined 19 F, 7 Li MAS-NMR, XPS and impedance spectroscopy. References: M. Gauthier, D. Mazouzi, D. Reyter, B. Lestriez, P. Moreau, D. Guyomard, L. Roué, Energy Environ. Sci. 6, 2145 (2013). Z. Karkar, D. Mazouzi, C. Reale Hernandez, D. Guyomard, L. Roué, B. Lestriez, Electrochim. Acta 215, 276 (2016). G.M.A. Girard, M. Hilder, H. Zhu, D. Nucciarone, K. Whitebread, S. Zavorine, M. Moser, M. Forsyth, D.R. MacFarlane, P.C. Howlett, Phys. Chem. Chem. Phys. 17, 8706 (2015) R. Kerr, D. Mazouzi, M. Eftekharnia, B. Lestriez, N. Dupré, M. Forsyth, D. Guyomard, P.C. Howlett, ACS Energy Lett. 2, 1804 (2017) M. Forsyth, G.M.A. Girard, A. Basile, M. Hilder, D.R. MacFarlane, F. Chen, P.C. Howlett, Electrochim. Acta 220, 609 (2016)
Combined Nano- and Macrotribology Studies of Titania Lubrication Using the Oil-Ionic Liquid Mixtures
Publisher: American Chemical Society (ACS)
Date: 05-08-2016
Thin and flexible solid-state organic ionic plastic crystal–polymer nanofibre composite electrolytes for device applications
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C3CP51986D
Abstract: All solid-state organic ionic plastic crystal-polymer nanofibre composite electrolytes are described for the first time. The new composite materials exhibit enhanced conductivity, excellent thermal, mechanical and electrochemical stability and allow the production of optically transparent, free-standing, flexible, thin film electrolytes (10's μms thick) for application in electrochemical devices. Stable cycling of a lithium cell incorporating the new composite electrolyte is demonstrated, including cycling at lower temperatures than previously possible with the pure material.
An Ionic Liquid Surface Treatment for Corrosion Protection of Magnesium Alloy AZ31
Publisher: The Electrochemical Society
Date: 2006
DOI: 10.1149/1.2344826
Structuring PEDOT Hollow Nanosphere Electrodes for High Specific Energy Li-Metal|Polymer Thin-Film Batteries
Publisher: American Chemical Society (ACS)
Date: 02-04-2020
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
An investigation of commercial carbon air cathode structure in ionic liquid based sodium oxygen batteries
Publisher: Springer Science and Business Media LLC
Date: 28-04-2020
DOI: 10.1038/S41598-020-63473-Y
Abstract: In order to bridge the gap between theoretical and practical energy density in sodium oxygen batteries challenges need to be overcome. In this work, four commercial air cathodes were selected, and the impacts of their morphologies, structure and chemistry on their performance with a pyrrolidinium-based ionic liquid electrolyte are evaluated. The highest discharge capacity was found for a cathode with a pore size ca . 6 nm this was over 100 times greater than that delivered by a cathode with a pore size less than 2 nm. The air cathode with the highest specific surface area and the presence of a microporous layer (BC39) exhibited the highest specific capacity (0.53 mAh cm −2 ).
A new Lewis-base ionic liquid comprising a mono-charged diamine structure: A highly stable electrolyte for lithium electrochemistry
Publisher: Elsevier BV
Date: 03-2006
Supported Ionic Liquid Gel Membrane Electrolytes for a Safe and Flexible Sodium Metal Battery
Publisher: American Chemical Society (ACS)
Date: 24-01-2019
Electrolyte Solvent Mixtures for a Symmetric, Non-Aqueous Redox Flow Battery Based on [Fe(bpy)3][Fsi]2
Publisher: The Electrochemical Society
Date: 30-06-2019
DOI: 10.1149/MA2019-04/10/0438
Abstract: Redox flow batteries (RFBs) store energy in liquid redox-active electrolytes which are charged and discharged while flowing through an electrochemical cell. This separation of storage and reaction sites enables flexible scalability of power and energy density. [1] Research suggests that non-aqueous RFB systems offer a promising combination of cost and performance for stationary applications, such as storage of excess renewable energy from domestic- to grid-scale [2]. In this work, we investigate a RFB based on the iron(II)-tris(2,2’-bipyridine) bis(fluorosulfonyl)imide complex, which shows one metal-centred oxidation process and up to three ligand-centred reduction processes, providing 2.4 V cell potential [3]. Using the same active material on both positive and negative sides of the cell mitigates the detrimental effects of cross-over through the separator membrane. These redox processes are solvent-dependent [3] and their electrochemistry was studied in a range of aprotic single and mixed solvents, some already used in lithium-ion batteries [4]. Since energy density is determined by the cell potential and the concentration of the active material, the solubility of the reduced and oxidated states of the complex was examined by UV/vis spectroscopy. Furthermore, conductivity and viscosity were measured over a range of temperatures. In RFBs, the dynamic viscosity of the electrolyte influences not just the conductivity but also affects the power required to pump the electrolyte. Cost, safety and environmental impact were considered as well. References: [1] L. F. Arenas, C. Ponce de León, F. C. Walsh, J. Energy Storage 2017 , 11 , 119-153. [2] R. Dmello, J. D. Milshtein, F. R. Brushett, K. C. Smith, J. Power Sources 2016 , 330 , 261-272. [3] D. M. Cabral, P. C. Howlett, D. R. MacFarlane, Electrochim. Acta 2016 , 220 , 347-353. [4] K. Xu, Chem. Rev. 2004, 104 , 4303-4417. Figure 1
A novel proton conducting ionogel electrolyte based on poly(ionic liquids) and protic ionic liquid
Publisher: Elsevier BV
Date: 06-2020
Potentiostatic Control of Ionic Liquid Surface Film Formation on ZE41 Magnesium Alloy
Publisher: American Chemical Society (ACS)
Date: 30-04-2010
DOI: 10.1021/AM900889N
Abstract: The generation of potentially corrosion-resistant films on light metal alloys of magnesium have been investigated. Magnesium alloy, ZE41 [Mg-Zn-Rare Earth (RE)-Zr, nominal composition approximately 4 wt % Zn, approximately 1.7 wt % RE (Ce), approximately 0.6 wt % Zr, remaining balance, Mg], was exposed under potentiostatic control to the ionic liquid trihexyl(tetradecyl)phosphonium diphenylphosphate, denoted [P(6,6,6,14)][DPP]. During exposure to this IL, a bias potential, shifted from open circuit, was applied to the ZE41 surface. Electrochemical impedance spectroscopy (EIS) and chrono erometry (CA) were used to monitor the evolution of film formation on the metal surface during exposure. The EIS data indicate that, of the four bias potentials examined, applying a potential of -200 mV versus OCP during the exposure period resulted in surface films of greatest resistance. Both EIS measurements and scanning electron microscopy (SEM) imaging indicate that these surfaces are substantially different to those formed without potential bias. Time of flight-secondary ion mass spectrometry (ToF-SIMS) elemental mapping of the films was utilized to ascertain the distribution of the ionic liquid cationic and anionic species relative to the microstructural surface features of ZE41 and indicated a more uniform distribution compared with the surface following exposure in the absence of a bias potential. Immersion of the treated ZE41 specimens in a chloride contaminated salt solution clearly indicated that the ionic liquid generated surface films offered significant protection against pitting corrosion, although the intermetallics were still insufficiently protected by the IL and hence favored intergranular corrosion processes.
Film formation in trihexyl(tetradecyl)phosphonium diphenylphosphate ([P6,6,6,14 ][dpp]) ionic liquid on AA5083 aluminium alloy
Publisher: Elsevier BV
Date: 10-2016
High current density, efficient cycling of Zn2+ in 1-ethyl-3-methylimidazolium dicyanamide ionic liquid: The effect of Zn2+ salt and water concentration
Publisher: Elsevier BV
Date: 2012
Spectroscopic Characterization of the SEI Layer Formed on Lithium Metal Electrodes in Phosphonium Bis(fluorosulfonyl)imide Ionic Liquid Electrolytes
Publisher: American Chemical Society (ACS)
Date: 12-02-2018
Abstract: The chemical composition of the solid electrolyte interphase (SEI) layer formed on the surface of lithium metal electrodes cycled in phosphonium bis(fluorosulfonyl)imide ionic liquid (IL) electrolytes are characterized by magic angle spinning nuclear magnetic resonance (MAS NMR), X-ray photoelectron spectroscopy (XPS), fourier transformed infrared spectroscopy, and electrochemical impedance spectroscopy. A multiphase layered structure is revealed, which is shown to remain relatively unchanged during extended cycling (up to 250 cycles at 1.5 mA·cm
Phosphonium ionic liquids as lubricants for aluminium-steel
Publisher: WIT Press
Date: 22-04-2010
DOI: 10.2495/TD100231
Organic ionic plastic crystals: recent advances
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/B920406G
Stable performance of an all-solid-state Li metal cell coupled with a high-voltage NCA cathode and ultra-high lithium content poly(ionic liquid)s-based polymer electrolyte
Publisher: Springer Science and Business Media LLC
Date: 30-07-2020
Critical evaluation of reference systems for voltammetric measurements in ionic liquids
Publisher: Elsevier BV
Date: 11-2012
Electrochemical, Transport, and Spectroscopic Properties of 1-Ethyl-3-methylimidazolium Ionic Liquid Electrolytes Containing Zinc Dicyanamide
Publisher: American Chemical Society (ACS)
Date: 04-02-2013
DOI: 10.1021/JP311886H
A comparative AFM study of the interfacial nanostructure in imidazolium or pyrrolidinium ionic liquid electrolytes for zinc electrochemical systems
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6CP04299F
Abstract: AFM measurements show that the electrochemical performance of zinc based ionic liquid electrolytes is controlled by ion arrangements at the electrode surface.
Influence of Electrospun Poly(vinylidene difluoride) Nanofiber Matrix on the Ion Dynamics of a Protic Organic Ionic Plastic Crystal
Publisher: American Chemical Society (ACS)
Date: 06-06-2018
(Invited) Tuning the Formation and Structure of the Silicon Electrode/Electrolyte Interphase in Superconcentrated Ionic Liquids
Publisher: The Electrochemical Society
Date: 19-10-2021
Electrochemical Formation in Super-Concentrated Phosphonium Based Ionic Liquid Electrolyte Using Symmetric Li-Metal Coin Cells
Publisher: The Electrochemical Society
Date: 26-08-2020
Poly(ionic liquid)s/Electrospun Nanofiber Composite Polymer Electrolytes for High Energy Density and Safe Li Metal Batteries
Publisher: American Chemical Society (ACS)
Date: 12-07-2019
Passive film formation in dilute ionic liquid solutions on magnesium Alloy AZ31
Publisher: Elsevier BV
Date: 06-2012
Toward Practical Li Metal Batteries: Importance of Separator Compatibility Using Ionic Liquid Electrolytes
Publisher: American Chemical Society (ACS)
Date: 26-08-2019
Improved Li-Ion Transport by DME Chelation in a Novel Ionic Liquid-Based Hybrid Electrolyte for Li–S Battery Application
Publisher: American Chemical Society (ACS)
Date: 06-06-2018
Characterization of the Magnesium Alloy AZ31 Surface in the Ionic Liquid Trihexyl(tetradecyl)phosphonium Bis(trifluoromethanesulfonyl)amide
Publisher: The Electrochemical Society
Date: 2010
DOI: 10.1149/1.3486119
Interphase Control in Lithium Metal Batteries Through Electrolyte Design
Publisher: American Chemical Society (ACS)
Date: 22-03-2021
DOI: 10.26434/CHEMRXIV.14254109
Abstract: Future rechargeable Li metal batteries (LMBs) require a rational electrolyte design to stabilize the interfaces between the electrolyte and both the lithium metal anode and the high voltage cathode. This remains the greatest challenge in achieving high cycling performance in LMBs. We report an ether-aided ionic liquid electrolyte which offers superior Li metal deposition, high voltage (5 V) stability and non-flammability. High performance cycling of LiNi0.8Mn0.1Co0.1O2 (4.4 V) and LiNi0.6Mn0.2Co0.2O2 (4.3 V) cells is demonstrated with high coulombic efficiency ( .5%) at room temperature and elevated temperatures, even at high ractical areal capacity for the latter of 3.8 mAh/cm2 and with a capacity retention of 91% after cycles. The ether-ionic liquid chemistry enables desirable plated Li microstructures with high packing density, minimal ‘dead’ or inactive lithium formation and dendrite-free long-term cycling. Along with XPS studies of cycled electrode surfaces, we use molecular dynamics simulations to demonstrate that changes to the electrolyte interfacial chemistry upon addition of DME plays a decisive role in the formation of a compact stable SEI.
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
Understanding the Capacity Decay of Si/NMC622 Li-Ion Batteries Cycled in Superconcentrated Ionic Liquid Electrolytes: A New Perspective
Publisher: American Chemical Society (ACS)
Date: 17-11-2022
Abstract: Silicon-containing Li-ion batteries have been the focus of many energy storage research efforts because of the promise of high energy density. Depending on the system, silicon generally demonstrates stable performance in half-cells, which is often attributed to the unlimited lithium supply from the lithium (Li) metal counter electrode. Here, the electrochemical performance of silicon with a high voltage NMC622 cathode was investigated in superconcentrated phosphonium-based ionic liquid (IL) electrolytes. As a matter of fact, there is very limited work and understanding of the full cell cycling of silicon in such a new class of electrolytes. The electrochemical behavior of silicon in the various IL electrolytes shows a gradual and steeper capacity decay, compared to what we previously reported in half-cells. This behavior is linked to a different evolution of the silicon morphology upon cycling, and the characterization of cycled electrodes points toward mechanical reasons, complete disconnection of part of the electrode, or internal mechanical stress, due to silicon and Li metal volume variation upon cycling, to explain the progressive capacity fading in full cell configuration. An extremely stable solid electrolyte interphase (SEI) in the full Li-ion cells can be seen from a combination of qualitative and quantitative information from transmission electron microscopy, X-ray photoelectron spectroscopy, electrochemical impedance spectroscopy, and magic angle spinning nuclear magnetic resonance. Our findings provide a new perspective to full cell interpretation regarding capacity fading, which is oftentimes linked almost exclusively to the loss of Li inventory but also more broadly, and provide new insights into the impact of the evolution of silicon morphology on the electrochemical behavior.
Nanofiber-reinforced polymer electrolytes toward room temperature solid-state lithium batteries
Publisher: Elsevier BV
Date: 02-2020
The effect of potential bias on the formation of ionic liquid generated surface films on Mg alloys
Publisher: Elsevier BV
Date: 02-2010
Bi-Functional Water/Oxygen Electrocatalyst Based on PdO-RuO2Composites
Publisher: The Electrochemical Society
Date: 21-11-2012
DOI: 10.1149/2.019302JES
Phosphonium plastic crystal salt alloyed with a sodium salt as a solid-state electrolyte for sodium devices: phase behaviour and electrochemical performance
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C6TA10340E
Abstract: Phase behaviour of a new class of solid state electrolyte with different concentration of Na salt is illustrated for the first time.
Highly Homogeneous Sodium Superoxide Growth in Na-O2 Batteries Enabled by a Hybrid Electrolyte
Publisher: American Chemical Society (ACS)
Date: 19-02-2020
Electrochemical reactivity of trihexyl(tetradecyl)phosphonium bis(2,4,4-trimethylpentyl)phosphinate ionic liquid on glassy carbon and AZ31 magnesium alloy
Publisher: Elsevier BV
Date: 06-2011
Influence of Zn2+and Water on the Transport Properties of a Pyrrolidinium Dicyanamide Ionic Liquid
Publisher: American Chemical Society (ACS)
Date: 24-04-2014
DOI: 10.1021/JP501665G
Abstract: In order to expand our understanding of a potential zinc-based battery electrolyte, we have characterized the physical and transport properties of the ionic liquid (IL) 1-butyl-1-methylpyrrolidinium dicyanamide ([C4mpyr][dca]) containing various levels of both Zn(2+) and H2O. Detailed measurements of density, viscosity, conductivity, and in idual anion and cation diffusion coefficients using pulsed-field-gradient (PFG) NMR combined with NMR chemical shifts and spin-lattice relaxation (T1) NMR experiments provide insights into the motion and chemical environment of all molecular species. We find that the various techniques for probing ion transport and dynamics form a coherent picture as a function of electrolyte composition. Zn(2+) addition causes a moderate reduction in the self-diffusion of the IL anion and cation, whereas the addition of H2O increases ion mobility by increasing the liquid's overall fluidity. Temperature-dependent (13)C T1 experiments of the dca carbon analyzed using Bloembergen-Purcell-Pound fits show monotonic slowing of anion dynamics with Zn(2+) addition, suggesting increased Zn(2+)/dca(-) association. T1 experiments show minimal change in the spin-lattice relaxation of cation or anion upon H2O addition, suggesting that H2O is playing no significant role in Zn(2+) speciation. Finally, we employ a novel electrophoretic NMR technique to directly determine the electrophoretic mobility of the C4mpyr cation, which we discuss in the context of impedance-based conductivity measurements.
Zn Electrochemistry in 1‐Ethyl‐3‐Methylimidazolium and N‐Butyl‐N‐Methylpyrrolidinium Dicyanamides: Promising New Rechargeable Zn Battery Electrolytes
Publisher: Wiley
Date: 18-09-2014
An organic ionic plastic crystal electrolyte for rate capability and stability of ambient temperature lithium batteries
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C4EE01085J
Abstract: For the first time, practical lithium cell performance is achieved at ambient temperature with an organic ionic plastic crystal solid electrolyte.
Solid (cyanomethyl)trimethylammonium salts for electrochemically stable electrolytes for lithium metal batteries
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0TA03502E
Abstract: Organic salts are being considered for the electrolyte solvent in rechargeable lithium-metal batteries (LMBs).
Physical properties of high Li-ion content N-propyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide based ionic liquid electrolytes
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C4CP05333H
Abstract: Electrolytes based on bis(fluorosulfonyl)imide (FSI) with a range of LiFSI salt concentrations were characterized using physical property measurements, as well as NMR, FT-IR and Raman spectroscopy.
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
Optimising organic ionic plastic crystal electrolyte for all solid-state and higher than ambient temperature lithium batteries
Publisher: Springer Science and Business Media LLC
Date: 26-10-2011
N, F and S doped carbon nanofibers generated from electrospun polymerized ionic liquids for metal-free bifunctional oxygen electrocatalysis
Publisher: Elsevier BV
Date: 05-2021
Interphase engineering of reactive metal surfaces using ionic liquids and deep eutectic solvents—from corrosion control to next-generation batteries
Publisher: Springer Science and Business Media LLC
Date: 13-11-2017
DOI: 10.1038/S41529-017-0016-Z
Abstract: Ionic liquids are unique solvents composed entirely of ions and have recently been considered for applications ranging from synthesis, separations, electrochemical devices, tribology and corrosion. In this perspective, we summarise the literature, and look at the future prospects, surrounding the use of ionic liquids in the engineering of interphases to control charge transport thereby leading to improved performance of high-energy density batteries, including Mg, Li and Na metal as well as corrosion protection of reactive engineering alloys, such as aluminium, magnesium and steel alloys. The ability to create task-specific ionic liquids by controlling the chemistry of either the anion or the cation means that interphases can be engineered for specific substrates and applications. Thus far, fluorine containing anions, such as bis(trifluoromethane) sulfonamide and its analogues, have been favoured for controlling the conductive solid–electrolyte interphase layer on Li and Na, while ionic liquids containing organophosphate anions have been used to form nanometre thick protective interphases on Mg alloys. Recently, ionic liquids based on carboxylate anions have also been shown to provide excellent corrosion inhibition for steel. In the search for cost-effective solutions, a relatively new class of ionic liquids, termed deep eutectic solvents, have also been explored as potential media for controlling surface films on reactive metals. The deep eutectic solvents class of ionic liquid materials offers many possible combinations of chemistry that can be targeted to produce desired properties in this context.
Effect of zwitterion on the lithium solid electrolyte interphase in ionic liquid electrolytes
Publisher: Elsevier BV
Date: 09-2008
Electrochemical and physicochemical properties of small phosphonium cation ionic liquid electrolytes with high lithium salt content
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5CP00205B
Abstract: A novel phosphonium ionic liquid as potential candidate for lithium battery electrolytes.
The effect of cation chemistry on physicochemical behaviour of superconcentrated NaFSI based ionic liquid electrolytes and the implications for Na battery performance
Publisher: Elsevier BV
Date: 04-2018
Electrochemical synthesis of polypyrrole in ionic liquids
Publisher: Elsevier BV
Date: 03-2004
Fast ion conduction in an acid doped pentaglycerine plastic crystal
Publisher: Elsevier BV
Date: 15-03-2006
N-methyl-N-alkylpyrrolidinium nonafluoro-1-butanesulfonate salts: Ionic liquid properties and plastic crystal behaviour
Publisher: Royal Society of Chemistry (RSC)
Date: 2006
DOI: 10.1039/B512902H
Ionic liquids and their solid-state analogues as materials for energy generation and storage
Publisher: Springer Science and Business Media LLC
Date: 12-01-2016
Phase behavior and electrochemical properties of solid lithium electrolytes based on N-ethyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide and PVdF composites
Publisher: Elsevier BV
Date: 05-2021
Towards thermally stable high performance lithium-ion batteries: The combination of a phosphonium cation ionic liquid and a 3D porous molybdenum disulfide/graphene electrode
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8CC01460D
Abstract: A lithium battery with excellent performance and thermal stability is realized by using a nanostructured electrode and an ionic liquid.
Rechargeable Zn/PEDOT Battery with an Imidazolium‐Based Ionic Liquid as the Electrolyte
Publisher: Wiley
Date: 08-09-2015
High Coulombic Efficiency Na-O2 Batteries Enabled by a Bilayer Ionogel/Ionic Liquid
Publisher: American Chemical Society (ACS)
Date: 25-10-2019
Ionic Liquids in Electrochemical Devices and Processes: Managing Interfacial Electrochemistry
Publisher: American Chemical Society (ACS)
Date: 18-10-2007
DOI: 10.1021/AR7000952
Abstract: Many ionic liquids offer a range of properties that make them attractive to the field of electrochemistry indeed it was electrochemical research and applications that ushered in the modern era of interest in ionic liquids. In parallel with this, a variety of electrochemical devices including solar cells, high energy density batteries, fuel cells, and supercapacitors have become of intense interest as part of various proposed solutions to improve sustainability of energy supply in our societies. Much of our work over the last ten years has been motivated by such applications. Here we summarize the role of ionic liquids in these devices and the insights that the research provides for the broader field of interest of these fascinating liquids.
Understanding Li creep in Li-metal pouch cells and the role of separator integrity
Publisher: Elsevier BV
Date: 03-2023
A safe Li–Se battery in an ionic liquid-based electrolyte operating at 25–70 °C by using a N,S,O tri-doped mesoporous carbon host material
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/C9SE01074B
Abstract: A Li–Se battery based on a Se-infused N,S,O tri-doped mesoporous carbon cathode is presented. A compatible and tunable ionic liquid electrolyte is introduced and a safer and thermally stable Li–Se battery that can operate up to 70 °C is demonstrated.
Ternary lithium-salt organic ionic plastic crystal polymer composite electrolytes for high voltage, all-solid-state batteries
Publisher: Elsevier BV
Date: 11-2018
Anion effects on the properties of OIPC/PVDF composites
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D0MA00992J
Abstract: Ion dynamics enhancements derived from anion–polymer interactions are proposed in organic ionic plastic crystal–poly(vinylidene fluoride)composite electrolytes.
Formulation and Characterization of PS-Poly(ionic liquid) Triblock Electrolytes for Sodium Batteries
Publisher: American Chemical Society (ACS)
Date: 21-11-2022
High Current Cycling in a Superconcentrated Ionic Liquid Electrolyte to Promote Uniform Li Morphology and a Uniform LiF-Rich Solid Electrolyte Interphase
Publisher: American Chemical Society (ACS)
Date: 02-09-2020
Polymerized Ionic Liquid Block Copolymer Electrolytes for All-Solid-State Lithium-Metal Batteries
Publisher: The Electrochemical Society
Date: 05-01-2020
Abstract: In this work, we present a polymerized ionic liquid block copolymer (PBCP) film where relevant properties such as ionic conductivity and electrochemical parameters are tailored by using a ternary system comprised of poly(styrene-b-1-((2-acryloyloxy)ethyl)−3-butylimidazolium bis(tri-fluoromethanesulfonyl)imide), LiFSI salt and ethylene carbonate (EC) as a cosolvent. It was found that EC efficiently decreases the glass transition temperature of the ionic block, resulting in an improved ionic conductivity and efficient platting/stripping of lithium. By using an optimal ratio of EC/LiFSI at relatively high LiFSI amount, Li∣Li symmetrical cells at 50 °C show an overpotential as low as 70 mV at 0.1 mA.cm −2 along with a high lithium transport number of 0.56 (t Li + ). All-solid-state full cells based on lithium iron phosphate cathode paired with a lithium metal anode reveal a rather stable cycling at both 50 °C and 70 °C. A negligible capacity fading is observed up to 30 cycles where a specific capacity as high as 161 mAh.g −1 is achieved with a coulombic efficiency of 99.9%. Thus, this work demonstrates an important pathway for tailoring the properties of solid state polymer electrolytes for emerging and specially designed block copolymer architectures comprising domains that give both excellent ionic conduction along with desirable mechanical properties.
Insights into the reversible oxygen reduction reaction in a series of phosphonium-based ionic liquids
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C4CP04101A
Abstract: Extensive evidence for the stability of the superoxide anion in phosphonium-based ILs is demonstrated by computational quantum chemistry and NMR.
High-Capacity Retention of Si Anodes Using a Mixed Lithium/Phosphonium Bis(fluorosulfonyl)imide Ionic Liquid Electrolyte
Publisher: American Chemical Society (ACS)
Date: 21-07-2017
In Situ, Real-Time Visualization of Electrochemistry Using Magnetic Resonance Imaging
Publisher: American Chemical Society (ACS)
Date: 27-08-2013
DOI: 10.1021/JZ401415A
Morphological Evolution and Solid-Electrolyte Interphase Formation on LiNi
Publisher: American Chemical Society (ACS)
Date: 11-03-2022
Abstract: Employing high-voltage Ni-rich cathodes in Li metal batteries (LMBs) requires stabilization of the electrode/electrolyte interfaces at both electrodes. A stable solid-electrolyte interphase (SEI) and suppression of active material pulverization remain the greatest challenges to achieving efficient long-term cycling. Herein, studies of NMC622 (1 mAh cm
SEI Formation on Sodium Metal Electrodes in Superconcentrated Ionic Liquid Electrolytes and the Effect of Additive Water
Publisher: American Chemical Society (ACS)
Date: 26-01-2021
Enhanced ionic mobility in Organic Ionic Plastic Crystal – Dendrimer solid electrolytes
Publisher: Elsevier BV
Date: 09-2015
Cover Profile: Fast Charge and High Stability of Solid‐State Graphite Organic Ionic Plastic Crystal Composite Anodes (Batteries & Supercaps 7/2022)
Publisher: Wiley
Date: 23-06-2022
Abstract: Invited for this month's cover picture is the group of Dr. Hiroyuki Ueda and Prof. Patrick C. Howlett at Deakin University (Australia) jointly working with Toyota Motor Corporation (Japan). The cover picture shows the fast lithium‐ion conduction pathways in the graphite anode of all‐solid‐state batteries (ASSBs) enabled by the incorporation of an organic ionic plastic crystal (OIPC) electrolyte. Read the full text of the Research Article at 10.1002/batt.202200057 .
Electrochemical characterization of hexamethylguanidinium bis(fluorosulfonyl)imide [HMG][FSI] based electrolyte and its application in sodium metal batteries
Publisher: IOP Publishing
Date: 09-12-2022
Abstract: With the increasing energy demand for both electronic portable devices and energy storage for fluctuating renewable energy sources, there is a strong need for alternatives beyond lithium batteries. Sodium batteries have been attracting great attention recently due to the abundance and low supply cost of the raw materials. However, they require highly conductive, safe and electrochemically stable electrolytes in order to enable their practical realization. In this work we present the promising physicochemical properties of the electrolyte based on hexamethylguanidinium bis(fluorosulfonyl)imide [FSI] at a sodium concentration of 25 mol% NaFSI. The liquid-state electrolyte supports stable Na plating and stripping at 1 h polarization times at 0.5 mA cm −2 current density in a Na symmetrical coin cell at 50 °C, maintaining a low polarization potential of ≈45 mV throughout 160 cycles. Moreover, this electrolyte is characterized by relatively high Na-ion transference number of 0.36 ± 0.03 at 50 °C. A long cycle life of 300 cycles with 285 mAh g −1 is achieved in a half cell set up with hard carbon. The solid-electrolyte interphase layer on the anode, which contributes to this high capacity, is investigated by x-ray photoelectron spectroscopy and solid-state nuclear magnetic resonance spectroscopy. The long-term cycling performance of Na|NaFePO 4 cell is also demonstrated with a high specific capacity of 106 mAh g −1 and 80% capacity retention after 110 cycles.
Cover Picture: Fast Charge and High Stability of Solid‐State Graphite Organic Ionic Plastic Crystal Composite Anodes (Batteries & Supercaps 7/2022)
Publisher: Wiley
Date: 15-06-2022
A biocompatible ionic liquid as an antiwear additive for biodegradable lubricants
Publisher: Elsevier BV
Date: 09-2014
Synthesis and physical property characterisation of phosphonium ionic liquids based on P(O)2(OR)2− and P(O)2(R)2− anions with potential application for corrosion mitigation of magnesium alloys
Publisher: Elsevier BV
Date: 12-2008
Organic Ionic Plastic Crystal-Based Composite Electrolyte with Surface Enhanced Ion Transport and Its Use in All-Solid-State Lithium Batteries
Publisher: Wiley
Date: 04-05-2017
Extreme properties of double networked ionogel electrolytes for flexible and durable energy storage devices
Publisher: Elsevier BV
Date: 05-2019
N-Methyl-N-Alkylpyrrolidinium Bis(perfluoroethylsulfonyl)amide ([NPf2]–) and Tris(trifluoromethanesulfonyl)methide ([CTf3]–) Salts: Synthesis and Characterization
Publisher: CSIRO Publishing
Date: 2007
DOI: 10.1071/CH06299
Abstract: Novel salts based the pyrrolidinium cation [Cnmpyr]+ (where n denote the number of carbons in the straight alkyl chain) and either the [NPf2]– or [CTf3]– anions have been synthesized and characterized to determine their thermal behaviour, stability, and conductivity. [C1mpyr][NPf2], [C2mpyr][NPf2], and [C1mpyr][CTf3] exhibit behaviour indicative of a plastic crystal phase. Both [C3mpyr][NPf2] and [C4mpyr][NPf2] are RTILs, while all of the [CTf3]– salts, have melting points above 60°C. [C3mpyr][NPf2] exhibited the widest electrochemical window of 5.5 V. The [NPf2]– salt exhibited similar reductive limits to the [NTf2]– anion, –3.2 V versus Fc+|Fc, while [CTf3]– had lower reductive stability. The [CTf3]– salts were more stable towards oxidation, +2.5 V versus Fc+|Fc, compared to the [NPf2]– and [NTf2]– salts.
High Lithium Metal Cycling Efficiency in a Room-Temperature Ionic Liquid
Publisher: The Electrochemical Society
Date: 2004
DOI: 10.1149/1.1664051
Formation of a corrosion-resistant coating on zinc by a duplex plasma electrolytic oxidation and conversion surface treatment
Publisher: Elsevier BV
Date: 08-2020
An ionic liquid based sodium metal-hybrid supercapacitor-battery
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C7SE00547D
Abstract: N/S co-doped mesoporous carbon cathode paired with Na metal anode in a non-flammable electrolyte results in a sustainable and high-performance supercapacitor-battery.
Macrophase-Separated Organic Ionic Plastic Crystals/PAMPS-Based Ionomer Electrolyte: A New Design Perspective for Flexible and Highly Conductive Solid-State Electrolytes
Publisher: American Chemical Society (ACS)
Date: 03-02-2020
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
The anion effect in ternary electrolyte systems using poly(diallyldimethylammonium) and phosphonium-based ionic liquid with high lithium salt concentration
Publisher: Elsevier BV
Date: 12-2018
Corrosion inhibition of 7000 series aluminium alloys with cerium diphenyl phosphate
Publisher: Elsevier BV
Date: 02-2011
Structure and dynamics in an organic ionic plastic crystal, N-ethyl-N-methyl pyrrolidinium bis(trifluoromethanesulfonyl) amide, mixed with a sodium salt
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C3TA15153K
Abstract: We present for the first time, the solid state phase behaviour of the organic ionic plastic crystal (OIPC) N -methyl- N -ethyl-pyrrolidinium bis(trifluoromethanesulfonyl)amide, [C 2 mpyr][NTf 2 ], upon mixing with the sodium salt, Na[NTf 2 ].
Solid-State Lithium Conductors for Lithium Metal Batteries Based on Electrospun Nanofiber/Plastic Crystal Composites
Publisher: Wiley
Date: 21-07-2017
Abstract: Organic ionic plastic crystals (OIPCs) are a class of solid-state electrolytes with good thermal stability, non-flammability, non-volatility, and good electrochemical stability. When prepared in a composite with electrospun polyvinylidene fluoride (PVdF) nanofibers, a 1:1 mixture of the OIPC N-ethyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide ([C
Polyterthiophene/CNT composite as a cathode material for lithium batteries employing an ionic liquid electrolyte
Publisher: Elsevier BV
Date: 11-2009
Sustainable, Dendrite Free Lithium-Metal Electrode Cycling Achieved with Polymer Composite Electrolytes Based on a Poly(Ionic Liquid) Host
Publisher: Wiley
Date: 18-01-2019
Functional Binders Based on Polymeric Ionic Liquids for Sodium Oxygen Batteries Using Ionic Liquid Electrolytes
Publisher: American Chemical Society (ACS)
Date: 11-01-2021
Iron-Based, Symmetric, Non-Aqueous Redox Flow Battery
Publisher: The Electrochemical Society
Date: 30-05-2021
DOI: 10.1149/MA2021-0182098MTGABS
Abstract: The redox flow battery (RFB) is a promising technology for the long-duration storage of energy from domestic- to utility-scale. A RFB stores charge in a liquid electrolyte that is charged and discharged in an electrochemical cell reactor. Since storage and reaction site are separated, energy and power of the system can be scaled independently via electrolyte tank and cell stack dimensions. Iron as one of earth’s most abundant elements is an attractive active material, especially in symmetric RFBs using the same electrolyte on both negative and positive side of the battery. One way to realize such a system is by combining iron with redox-active ligands in non-aqueous solvents. [1],[2] We study the iron tris(2,2’-bipyridine) complex which shows a metal-centred reversible oxidation and three ligand-based reductions that are solvent-dependent. [3] The influence of electrolyte composition on charge and discharge reactions as well as on viscosity and conductivity is further investigated. Charge-discharge cycling experiments are carried out in 3-electrode H-cell and flow cell setups. We determine failure modes for the positive side due to electrode kinetics and for the negative side due to solubility changes. We propose improvements to this non-aqueous RFB system based on the selection of electrode materials and cycling conditions. [1] J. Mun et al. , J. Electrochem. Soc. 2018 , 165 , 215-219. [2] C. X. Cammack et al. , DaltonTrans . 2021 , 50 , 858. [3] D. M. Cabral, P. C. Howlett, D. R. MacFarlane, Electrochim. Acta 2016 , 220 , 347-353.
High-Performance Cycling of Na Metal Anodes in Phosphonium and Pyrrolidinium Fluoro(sulfonyl)imide Based Ionic Liquid Electrolytes
Publisher: American Chemical Society (ACS)
Date: 22-03-2022
Abstract: We have investigated the sodium electrochemistry and the evolution and chemistry of the solid-electrolyte interphase (SEI) upon cycling Na metal electrodes in two ionic liquid (IL) electrolytes. The effect of the IL cation chemistry was determined by examining the behavior of a phosphonium IL (P
Properties of sodium-based ionic liquid electrolytes for sodium secondary battery applications
Publisher: Elsevier BV
Date: 12-2013
Discharge behaviour and interfacial properties of a magnesium battery incorporating trihexyl(tetradecyl)phosphonium based ionic liquid electrolytes
Publisher: Elsevier BV
Date: 2013
Enhancement of ion dynamics in organic ionic plastic crystal/PVDF composite electrolytes prepared by co-electrospinning
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6TA02817A
Abstract: Organic ionic plastic crystal (OIPC) modified poly(vinylidene difluoride) (PVDF) composite fiber membrane with enhanced ion dynamics and almost pure β-PVDF are demonstrated.
Extensive Sodium Metal Plating and Stripping in a Highly Concentrated Inorganic−Organic Ionic Liquid Electrolyte through Surface Pretreatment
Publisher: Wiley
Date: 23-02-2017
Na-Ion Solvation and High Transference Number in Superconcentrated Ionic Liquid Electrolytes: A Theoretical Approach
Publisher: American Chemical Society (ACS)
Date: 21-12-2018
Passivation behaviour of aluminium current collector in ionic liquid alkyl carbonate (hybrid) electrolytes
Publisher: Springer Science and Business Media LLC
Date: 29-03-2018
DOI: 10.1038/S41529-018-0033-6
Abstract: The compatibility of current collectors with the electrolyte plays a major role in the overall performance of lithium batteries, critical to obtain high storage capacity as well as excellent capacity retention. In lithium-ion batteries, in particular with cathodes that operate at high voltage such as lithium nickel cobalt manganese oxide, the cathodic current collector is aluminium and it is subjected to high oxidation potentials ( V vs. Li/Li + ). As a result, the composition of the electrolyte needs to be carefully designed in order to stabilise the battery performance as well as to protect the current collectors against corrosion. This study examines the role of a hybrid electrolyte composed of an ionic liquid ( N -methyl- N -propyl pyrrolidinium bis(trifluoromethanesulfonyl)imide or N -methyl- N -propyl pyrrolidinium bis(fluorosulfonyl)imide) and a conventional electrolyte mixture (LiPF 6 salt and alkyl carbonate solvents) with correlation to their electrochemical behaviour and corrosion inhibition efficiency. The hybrid electrolyte was tested against battery grade aluminium current collectors electrochemically in a three-electrode cell configuration and the treated aluminium surface was characterised by SEM/EDXS, optical profilometry, FTIR, and XPS analysis. Based on the experimental results, the hybrid electrolytes allow an effective and improved passivation of aluminium and lower the extent of aluminium dissolution in comparison with the conventional lithium battery electrolytes and the neat ionic liquids at high anodic potentials (4.7 V vs. Li/Li + ). The mechanism of passivation behaviour is also further investigated. These observations provide a potential direction for developing improved hybrid electrolytes, based on ionic liquids, for higher energy density devices.
Transition in Wear Performance for Ionic Liquid Lubricants under Increasing Load
Publisher: Springer Science and Business Media LLC
Date: 21-09-2010
A sealed optical cell for the study of lithium-electrode|electrolyte interfaces
Publisher: Elsevier BV
Date: 03-2003
Impact of the electrode conductivity on the electrolyte interfacial structuring and its implications to the Na0/+ electrochemical performance
Publisher: Research Square Platform LLC
Date: 23-02-2023
DOI: 10.21203/RS.3.RS-2618698/V1
Abstract: The molecular and ionic assemblies at an electrode/liquid electrolyte interface, i.e., electric double layer (EDL), define battery performance by directing the formation of stable interphases. An unstable interphase can h er metal-cation diffusion, lead to continuous electrolyte consumption, and also promote non-uniform electrochemical processes, like dendrite formation. The co-selection of electrolyte chemistry and initial cycling conditions together are generally considered for the design of desirable interphases. At the same time, the dielectric nature of the electrode material is largely ignored, notwithstanding high unreliability of the assumption that the nature of the EDL and the mechanism of the interphase formation at metallic and semiconductive electrodes are identical. Here we show that the dielectric nature of the charged electrode greatly affects the interfacial metal-anion-solvent composition therefore, different interphase chemistry will be formed, suggesting different initial cycling conditions on a case-by-case basis to form the desired interphase. This phenomenon correlates with the metal ion solvation chemistry and the adsorption of species at the electrified electrode due to competition of van der Waals and Coulombic interactions.
Ionic transport through a composite structure of N-ethyl-N-methylpyrrolidinium tetrafluoroborate organic ionic plastic crystals reinforced with polymer nanofibres
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C4TA07155G
Abstract: Composite plastic crystal electrolytes are shown to exhibit enhanced ion transport due to release of Li + from a second phase into a solid solution.
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
Improving Cycle Life Through Fast Formation Using a Super-Concentrated Phosphonium Based Ionic Liquid Electrolyte for Anode-Free and Lithium Metal Batteries
Publisher: American Chemical Society (ACS)
Date: 06-2021
DOI: 10.26434/CHEMRXIV.14702748
Abstract: ABSTRACT Cell formation of lithium-ion cells impacts the evolution of the solid electrolyte interphase (SEI) and the cell cycle stability. Lithium metal anodes are an important step in the development of high energy density batteries owing to the high theoretical specific capacity of lithium metal. However, most lithium metal battery research has used a conventional lithium-ion formation protocol this is time consuming, costly and does not account for the different properties of the lithium metal electrode. Here, we have used a recently reported promising phosphonium bis(fluorosulfonyl)imide ionic liquid electrolyte coupled with an NMC622 high areal capacity cathode ( .5 mAh/cm2) to investigate the effect of cell formation rates. A faster formation protocol comprised of a pulsed 1.25C current decreased the formation time by 56 % and gave a 38 % greater capacity retention after 50 cycles when compared to formation at C/20. Electrochemical impedance spectroscopy measurements showed that the fast formation gave rise to a lower-resistance SEI. Column-like lithium deposits with reduced porous lithium domains between the particles were observed using scanning electron microscope imaging. To underline the excellent performance of these high energy-density cells, a 56 % greater stack specific energy was achieved compared to the analogous graphite-based lithium-ion cell chemistries.
Beneficial effect of added water on sodium metal cycling in super concentrated ionic liquid sodium electrolytes
Publisher: Elsevier BV
Date: 03-2018
The influence of anion chemistry on the ionic conductivity and molecular dynamics in protic organic ionic plastic crystals
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C7CP07330E
Abstract: Protic organic ionic plastic crystals based on different anions exhibit more than two orders of magnitude difference in conductivity.
Oxygen Reduction Reaction Activity of La-Based Perovskite Oxides in Alkaline Medium: A Thin-Film Rotating Ring-Disk Electrode Study
Publisher: American Chemical Society (ACS)
Date: 22-02-2012
DOI: 10.1021/JP211946N
Lithium doped N,N-dimethyl pyrrolidinium tetrafluoroborate organic ionic plastic crystal electrolytes for solid state lithium batteries
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C0JM04401F
Comparison of the physicochemical and electrochemical behaviour of mixed anion phosphonium based OIPCs electrolytes for sodium batteries
Publisher: Elsevier BV
Date: 12-2017
The influence of interfacial interactions on the conductivity and phase behaviour of organic ionic plastic crystal/polymer nanoparticle composite electrolytes
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/C9TA12827A
Abstract: The interactions between OIPCs and polymer nanoparticles create interfacial layers that control the ion mobility of the resulting composite.
The Zwitterion Effect in Ionic Liquids: Towards Practical Rechargeable Lithium-Metal Batteries
Publisher: Wiley
Date: 17-10-2005
Corrosion of magnesium alloy ZE41 – The role of microstructural features
Publisher: Elsevier BV
Date: 02-2009
UV-Cross-Linked Ionogels for All-Solid-State Rechargeable Sodium Batteries
Publisher: American Chemical Society (ACS)
Date: 23-09-2019
Preparation and characterization of gel polymer electrolytes using poly(ionic liquids) and high lithium salt concentration ionic liquids
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7TA08233A
Abstract: Poly(ionic liquids)-based gel polymer electrolytes containing high lithium salt concentration ionic liquids are demonstrated.
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.
Single‐ion conducting polymer as lithium salt additive in polymerized ionic liquid block copolymer electrolyte
Publisher: Wiley
Date: 02-03-2023
DOI: 10.1002/APP.53809
Abstract: Herein, we describe the use of single‐ion conducting block copolymer (SIC) as an additional lithium salt additive to a ternary solid polymer electrolyte (SPE), consisting of a poly(styrene‐ b ‐1‐((2‐acryloyloxy)ethyl)‐3‐butylimidazolium bis(trifluoromethanesulfo‐nyl)imide) (S‐ImTFSI 64‐16 ) block copolymer, a N ‐propyl‐ N ‐methylpyrrolidinium bis(fluorosulfonyl)imide (C 3 mpyrFSI) ionic liquid (IL) and a lithium bis(fluorosulfonyl) imide (LiFSI) salt. For this purpose, the S‐ImTFSI 64‐16 was substituted by a SIC, based on poly(styrene‐ b ‐((4‐styrenesulfonyl)(trifluoromethanesulfonyl)imide lithium salt)) (S‐STFSILi 64‐16 ), at various molar ratios. The impact of the SIC concentration on the phase behavior and transport properties of the SPEs was investigated by means of differential scanning calorimetry, electrochemical impedance spectroscopy, and diffusion NMR. In addition, the electrochemical performance of the SPEs was assessed in lithium symmetrical cell at 50 and 80°C. Finally, the cycling performance of a selected SPE was also assessed at 80°C in a Li│NMC 111 cell with capacity loading of 1.3 mAh.cm −2 at a C‐rate of 0.1 C. The Li│NMC 111 full cell was able to deliver a stable capacity of 0.94 mAh.cm −2 after 20 cycles, corresponding to a capacity of 117 mAh.g −1 . These results demonstrates that PIL block copolymer—IL—salt composites represent a promising choice of electrolyte for the next generation of solid‐state high energy density lithium metal batteries.
Stable High-Temperature Cycling of Na Metal Batteries on Na3 V2 (PO4 )3 and Na2 FeP2 O7 Cathodes in NaFSI-Rich Organic Ionic Plastic Crystal Electrolytes
Publisher: American Chemical Society (ACS)
Date: 19-02-2020
An Electrochemical Impedance Study of Ionic Liquid Film Formation and Aqueous Corrosion of Magnesium Alloy ZE41
Publisher: Wiley
Date: 12-2008
Abstract: Ionic liquid surface treatments are proposed as a method of controlling corrosion processes on magnesium alloys. An important magnesium alloy, ZE41 (nominally 4% Zn and 1% rare earth), was treated with the ionic liquid trihexyl(tetradecyl)phosphonium diphenylphosphate (P 66614 DPP). Impedance spectra were acquired at intervals during the treatment, indicating the development of a film and allowing a measure of the film formation process to be obtained over time. Mechanically polished and electro‐polished surfaces were prepared these surfaces, treated and untreated, were subsequently exposed to 0.1 M NaCl aqueous solutions. The corrosion behavior of the prepared surfaces were assessed using impedance spectroscopy and optical microscopy. The results indicated a significant role for the method of surface preparation used and, in both cases, the ionic liquid treatment produced a more corrosion‐resistant surface.
Elucidating the Impact of Sodium Salt Concentration on the Cathode–Electrolyte Interface of Na–Air Batteries
Publisher: American Chemical Society (ACS)
Date: 25-05-2018
Anion-Derived Solid-Electrolyte Interphase Enables Long Life Na-Ion Batteries Using Superconcentrated Ionic Liquid Electrolytes
Publisher: American Chemical Society (ACS)
Date: 14-06-2021
Conversion coatings of Mg-alloy AZ91D using trihexyl(tetradecyl) phosphonium bis(trifluoromethanesulfonyl)amide ionic liquid
Publisher: Springer Science and Business Media LLC
Date: 12-07-2012
Enhanced Ion Transport in an Ether Aided Super Concentrated Ionic Liquid Electrolyte for Long-Life Practical Lithium Metal Battery Applications
Publisher: American Chemical Society (ACS)
Date: 02-07-2020
DOI: 10.26434/CHEMRXIV.12588059.V1
Abstract: We explore a novel ether aided superconcentrated ionic liquid electrolyte a combination of ionic liquid, N -propyl- N -methylpyrrolidinium bis(fluorosulfonyl)imide (C 3 mpyrFSI) and ether solvent, 1,2 dimethoxy ethane (DME) with 3.2 mol/kg LiFSI salt, which offers an alternative ion-transport mechanism and improves the overall fluidity of the electrolyte. The molecular dynamics (MD) study reveals that the coordination environment of lithium in the ether aided ionic liquid system offers a coexistence of both the ether DME and FSI anion simultaneously and the absence of ‘free’, uncoordinated DME solvent. These structures lead to very fast kinetics and improved current density for lithium deposition-dissolution processes. Hence the electrolyte is used in a lithium metal battery against a high mass loading (~12 mg/cm 2 ) LFP cathode which was cycled at a relatively high current rate of 1mA/cm 2 for 350 cycles without capacity fading and offered an overall coulombic efficiency of .8 %. Additionally, the rate performance demonstrated that this electrolyte is capable of passing current density as high as 7mA/cm 2 without any electrolytic decomposition and offers a superior capacity retention. We have also demonstrated an ‘anode free’ LFP-Cu cell which was cycled over 50 cycles and achieved an average coulombic efficiency of 98.74%. The coordination chemistry and (electro)chemical understanding as well as the excellent cycling stability collectively leads toward a breakthrough in realizing the practical applicability of this ether aided ionic liquid electrolytes in lithium metal battery applications, while delivering high energy density in a prototype cell.
Ionic Liquid Adsorption and Nanotribology at the Silica–Oil Interface: Hundred-Fold Dilution in Oil Lubricates as Effectively as the Pure Ionic Liquid
Publisher: American Chemical Society (ACS)
Date: 17-11-2014
DOI: 10.1021/JZ5021422
Abstract: The remarkable physical properties of ionic liquids (ILs) make them potentially excellent lubricants. One of the challenges for using ILs as lubricants is their high cost. In this article, atomic force microscopy (AFM) nanotribology measurements reveal that a 1 mol % solution of IL dissolved in an oil lubricates the silica surface as effectively as the pure IL. The adsorption isotherm shows that the IL surface excess need only be approximately half of the saturation value to prevent surface contact and effectively lubricate the sliding surfaces. Using ILs in this way makes them viable for large-scale applications.
Stabilisation of the superoxide anion in bis(fluorosulfonyl)imide (FSI) ionic liquid by small chain length phosphonium cations: Voltammetric, DFT modelling and spectroscopic perspectives
Publisher: Elsevier BV
Date: 06-2021
Ionic liquid effects on the redox potential of ferrocene
Publisher: Elsevier BV
Date: 03-2012
Probing the Interactions and Dynamics in an Ionic Liquid – Organic Solvent Hybrid Electrolyte System for Potential Application in Li-S Batteries
Publisher: The Electrochemical Society
Date: 02-2019
Abstract: The depletion of fossil fuel and strict environmental regulation on carbon footprints has prompted a greater reliability on sustainable energy sources. Batteries represent an important energy storage option due to their wide range of applicability and portability, however, for certain applications such as transportation, a higher energy density battery is required. Beyond the conventional Li-ion battery system, current research is focusing on next-generation cost effective devices. Amongst them, the Li-S battery technology is very promising due to its high theoretical capacity and energy density [1]. However, the chemistry involved in the Li-S battery is a complex process with multiple consecutive electrochemical reactions. Despite having many advantages, its application is still limited by several issues, e.g. , the dissolution and diffusion of intermediate polysulphides, unstable plating and stripping of Li metal, both resulting in rapid capacity fading [2]. Previously, we reported the application of a novel electrolyte system composed of N -propyl- N -methylpyrrolidinium bis(fluorosulfonyl)imide, C 3 mpyrFSI, ionic liquid (IL) and 1,2 dimethoxyethane (DME) in the presence of varying saturated lithium bis(fluorosulfonyl)imide, LiFSI which predominantly suppressed the polysulphide dissolution and diffusion while showing improved lithium plating and stripping behavior [3]. In order to expand our understanding on the role of DME and the lithium salt concentration in this work, we have considered a similar ionic liquid based electrolyte system but at a constant concentration of LiFSI salt. The ionic interactions among different species of the electrolyte system have been extensively studied by nuclear magnetic resonance (NMR) spectroscopy using 1 D chemical shift, PFG-NMR and Heteronuclear Overhauser Effect SpectroscopY (HOESY) measurements. We found that, when increasing the DME concentration in the system, a strong association of Li + cation with the DME occurs due to the electronegative oxygen atoms present in the DME molecules which leads to strong coordination. This leads to a change of the chemical shift of 7 Li nuclei due to them being increasingly de-shielded. Interestingly, we found that the diffusivity of both Li + and DME species are very similar, which also confirms that a Li-DME complex is present with FSI anion associated in the next coordination sphere to counterbalance the positively charged Li complex. MD simulations are underway to better elucidate the molecular shell structure of the system. We have also carried out electrochemical characterizations of these hybrid electrolytes to determine their potential applicability in a lithium sulphur battery. It was apparent using cyclic voltammogram (CV) performed in a three electrode set-up, that an increasing amount of DME increases the ionic conductivity but decreases the lithium plating-stripping efficiency. A coin-cell study of Li/Li symmetrical cycling showed an excellent plating-stripping behaviour for 70%IL-30%DME composition. We have carried out a full cell cycling against sulphur cathode and the optimised electrolyte composition obtained a promising first discharge capacity of 1100mAh/g. Additionally, we have investigated the sulphur speciation in the presence of this ionic liquid in a three-electrode system where platinum mesh has been used as working electrode coupled with in-situ UV-vis spectroscopy. Finally, a time dependent bulk electrolysis study revealed the plausible intermediates formed during the charge-discharge cycle of sulphur redox reaction. From these studies it appears that the composition of this novel hybrid electrolyte system can be tuned to provide a system with improved transport, electrochemical and sulphur speciation properties which lend themselves to a higher performance, next generation lithium sulphur battery technology. References: [1] Ji, X. Nazar, L. F., Advances in Li-S batteries. Journal of Materials Chemistry 2010, 20 (44), 9821-9826. [2] Scheers, J. Fantini, S. Johansson, P., A review of electrolytes for lithium–sulphur batteries.Journal of Power Sources 2014, 255, 204-218. [3] Pal, U. Forsyth, M Improved Li-Ion Transport by DME Chelation in a Novel Ionic Liquid Based Hybrid Electrolyte for Li-S Battery Application. The Journal of Physical Chemistry C, 122 (2018) 14373-14382. Figure 1
A Potential Novel Rapid Screening NMR Approach to Boundary Film Formation at Solid Interfaces in Contact with Ionic Liquids
Publisher: American Chemical Society (ACS)
Date: 15-08-2008
DOI: 10.1021/JP806096W
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.
Electrochemistry at Negative Potentials in Bis(trifluoromethanesulfonyl)amide Ionic Liquids
Publisher: Walter de Gruyter GmbH
Date: 02-0100
DOI: 10.1524/ZPCH.2006.220.10.1483
Abstract: The bis(trifluoromethanesulfonyl)amide (TFSA) anion is widely studied as an ionic liquid (IL) forming anion which imparts many useful properties, notably electrochemical stability. Here we present electrochemical and spectroscopic evidence indicating that reductive decomposition of the bis(trifluoromethanesulfonyl)amide (TFSA) anion begins at ~ −2.0 V vs. Fc + /Fc, well before the reported cathodic limit for many of these ILs. These processes are shown to be dependent upon the electrode substrate and are influenced by the water content of the IL. Supporting ab initio calculations are presented which suggest a possible mechanism for the anion decomposition. The products appear to passivate the electrode surface and the implications of this behaviour are discussed.
Characterization of the Lithium Surface in N-Methyl-N-Alkylpyrrolidinium Bis(trifluoromethanesulfonyl)amide Room-Temperature Ionic Liquid Electrolytes
Publisher: The Electrochemical Society
Date: 2006
DOI: 10.1149/1.2164726
Redox Chemistry of the Superoxide Ion in a Phosphonium-Based Ionic Liquid in the Presence of Water
Publisher: American Chemical Society (ACS)
Date: 17-05-2013
DOI: 10.1021/JZ400715R
Abstract: Stable electrogenerated superoxide ion has been observed for the first time in a phosphonium-based ionic liquid in the presence of water, leading to a chemically reversible O2/O2(•-) redox couple instead of the disproportionation reaction that is usually observed. It appears that the cation solvates the superoxide anion, stabilizing it against the disproportionation reaction. The electrogeneration is studied at various levels of water or other diluents including toluene to explore the limits of stability of the superoxide ion under these conditions.
Stable Deep Doping of Vapor-Phase Polymerized Poly(3,4-ethylenedioxythiophene)/Ionic Liquid Supercapacitors
Publisher: Wiley
Date: 21-06-2016
Abstract: Liquid-solution polymerization and vapor-phase polymerization (VPP) have been used to manufacture a series of chloride- and tosylate-doped poly(3,4-ethylenedioxythiophene) (PEDOT) carbon paper electrodes. The electrochemistry, specific capacitance, and specific charge were determined for single electrodes in 1-ethyl-3-methylimidazolium dicyanamide (emim dca) ionic liquid electrolyte. VPP-PEDOT exhibits outstanding properties with a specific capacitance higher than 300 F g(-1) , the highest value reported for a PEDOT-based conducting polymer, and doping levels as high as 0.7 charges per monomer were achieved. Furthermore, symmetric PEDOT supercapacitor cells with the emim dca electrolyte exhibited a high specific capacitance (76.4 F g(-1) ) and high specific energy (19.8 Wh kg(-1) ). A Ragone plot shows that the VPP-PEDOT cells combine the high specific power of conventional ("pure") capacitors with the high specific energy of batteries, a highly sought-after target for energy storage.
N-ethyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide-electrospun polyvinylidene fluoride composite electrolytes: characterization and lithium cell studies
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C6CP07415D
Abstract: LiFSI doped [C 2 mpyr][FSI]–PVdF composites were developed as solid-state, self-standing electrolyte membranes.
Ionic liquids and organic ionic plastic crystals utilizing small phosphonium cations
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C1JM10417A
Stable cycling of NaFePO4 cathodes in high salt concentration ionic liquid electrolytes
Publisher: Elsevier BV
Date: 12-2018
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
A comparison of phosphorus and fluorine containing IL lubricants for steel on aluminium
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2CP40736A
Abstract: Ionic liquids have been shown to be highly effective lubricants for a steel on aluminium system. This work shows that the chemistry of the anion and cation are critical in achieving maximum wear protection. The performance of the ILs containing a diphenylphosphate (DPP) anion all showed low wear, as did some of the tris(pentafluoroethyl)trifluorophosphate (FAP) and bis(trifluoromethanesulfonyl)amide (NTf(2)) anion containing ILs. However, in the case of the FAP and NTf(2) based systems, a cation dependence was observed, with relatively poor wear resistance obtained in the case of an imidazolium FAP and two pyrrolidinium NTf(2) salts, probably due to tribocorrosion caused by the fluorine reaction with the aluminium substrate. The systems exhibiting poor performance generally had a lower viscosity, which also impacts on their tribological properties. Those ILs that exhibited low wear were shown to have formed protective tribofilms on the aluminium alloy surface.
Unravelling the Role of Speciation in Glyme:Ionic Liquid Hybrid Electrolytes for Na−O2 Batteries
Publisher: Wiley
Date: 10-12-2020
Enabling High Lithium Conductivity in Polymerized Ionic Liquid Block Copolymer Electrolytes
Publisher: Wiley
Date: 13-12-2019
Related Organisations
Related Funding Activities
Discovery Projects - Grant ID: DP0986205
Start Date: 2009
End Date: 12-2013
Amount: $750,000.00
Funder: Australian Research Council
View Funded ActivityLinkage Projects - Grant ID: LP180100674
Start Date: 11-2019
End Date: 12-2022
Amount: $206,100.00
Funder: Australian Research Council
View Funded ActivityLinkage Infrastructure, Equipment And Facilities - Grant ID: LE180100168
Start Date: 2018
End Date: 03-2020
Amount: $264,706.00
Funder: Australian Research Council
View Funded ActivityDiscovery Projects - Grant ID: DP140101535
Start Date: 05-2014
End Date: 12-2017
Amount: $270,000.00
Funder: Australian Research Council
View Funded ActivityLinkage Projects - Grant ID: LP220200583
Start Date: 07-2023
End Date: 06-2026
Amount: $508,018.00
Funder: Australian Research Council
View Funded ActivityLinkage Infrastructure, Equipment And Facilities - Grant ID: LE200100132
Start Date: 2020
End Date: 12-2021
Amount: $1,486,000.00
Funder: Australian Research Council
View Funded ActivityDiscovery Projects - Grant ID: DP160101178
Start Date: 2016
End Date: 12-2019
Amount: $617,000.00
Funder: Australian Research Council
View Funded ActivityDiscovery Projects - Grant ID: DP210101172
Start Date: 03-2021
End Date: 03-2024
Amount: $651,162.00
Funder: Australian Research Council
View Funded ActivityLinkage Infrastructure, Equipment And Facilities - Grant ID: LE120100028
Start Date: 01-2012
End Date: 12-2013
Amount: $600,000.00
Funder: Australian Research Council
View Funded ActivityARC Centres Of Excellence - Grant ID: CE140100012
Start Date: 06-2014
End Date: 06-2021
Amount: $25,000,000.00
Funder: Australian Research Council
View Funded ActivityLinkage Projects - Grant ID: LP120200181
Start Date: 01-2013
End Date: 11-2016
Amount: $330,000.00
Funder: Australian Research Council
View Funded ActivityIndustrial Transformation Research Hubs - Grant ID: IH180100020
Start Date: 07-2019
End Date: 07-2025
Amount: $3,058,152.00
Funder: Australian Research Council
View Funded ActivityIndustrial Transformation Training Centres - Grant ID: IC180100049
Start Date: 05-2019
End Date: 05-2024
Amount: $4,380,454.00
Funder: Australian Research Council
View Funded ActivityLinkage Projects - Grant ID: LP100100066
Start Date: 2010
End Date: 12-2014
Amount: $448,000.00
Funder: Australian Research Council
View Funded Activity