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2 pages, 181 KiB

Open AccessEditorial

Innovative Materials for Batteries

by Oriele Palumbo

Appl. Sci. 2023, 13(13), 7595; https://doi.org/10.3390/app13137595 - 27 Jun 2023

Viewed by 545

Abstract

In the struggle for the reduction of carbon emission, the use of energy storage systems is becoming more and more widespread, and the wider applications require a continuous upgrading of the batteries’ performances [...] Full article

(This article belongs to the Special Issue Innovative Materials for Batteries)

Research

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11 pages, 1947 KiB

Open AccessArticle

Inorganic–Organic Hybrid Electrolytes Based on Al-Doped Li₇La₃Zr₂O₁₂ and Ionic Liquids

by Akiko Tsurumaki, Rossella Rettaroli, Lucia Mazzapioda and Maria Assunta Navarra

Appl. Sci. 2022, 12(14), 7318; https://doi.org/10.3390/app12147318 - 21 Jul 2022

Cited by 6 | Viewed by 1561

Abstract

Organic–inorganic hybrid electrolytes based on Al-doped Li₇La₃Zr₂O₁₂ (LLZO) and two different ionic liquids (ILs), namely N-ethoxyethyl-N-methylpiperidinium bis(fluorosulfonyl)imide (FSI IL) and N-ethoxyethyl-N-methylpiperidinium difluoro(oxalato)borate (DFOB IL), were prepared with the aim of [...] Read more.

Organic–inorganic hybrid electrolytes based on Al-doped Li₇La₃Zr₂O₁₂ (LLZO) and two different ionic liquids (ILs), namely N-ethoxyethyl-N-methylpiperidinium bis(fluorosulfonyl)imide (FSI IL) and N-ethoxyethyl-N-methylpiperidinium difluoro(oxalato)borate (DFOB IL), were prepared with the aim of improvement of inherent flexibilities of inorganic solid electrolytes. The composites were evaluated in terms of thermal, spectroscopical, and electrochemical properties. In the impedance spectra of LLZO composites with 15 wt% ILs, a semi-circle due to grain boundary resistances was not observed. With the sample merely pressed with 1 ton, without any high-temperature sintering process, the ionic conductivity of 10⁻³ S cm⁻¹ was achieved at room temperature. Employing a ternary composite of LLZO, FSI IL, and LiFSI as an electrolyte, all-solid-state lithium metal batteries having LiFePO₄ as a cathode were assembled. The cell exhibited a capacity above 100 mAh g⁻¹ throughout the course of charge–discharge cycle at C/20. This confirms that FSI IL is an effective additive for inorganic solid electrolytes, which can guarantee the ion conduction. Full article

(This article belongs to the Special Issue Innovative Materials for Batteries)

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28 pages, 20774 KiB

Open AccessArticle

Phase Behavior and Ionic Conductivity of Blended, Ion-Condensed Electrolytes with Ordered Morphologies

by Hannah Collins, Jiacheng Liu, Lingyu Yang and Jennifer L. Schaefer

Appl. Sci. 2022, 12(13), 6529; https://doi.org/10.3390/app12136529 - 28 Jun 2022

Cited by 1 | Viewed by 1583

Abstract

In this study, the amphiphilic salt lithium trifluoromethanesulfonylimide octadecane (C18LiTFSI) was used as a basis to investigate the effects of anion density and cation coordination sites within blended electrolytes with strong ionic aggregation. C18LiTFSI was previously reported as a single-component, ion-condensed electrolyte with [...] Read more.

In this study, the amphiphilic salt lithium trifluoromethanesulfonylimide octadecane (C18LiTFSI) was used as a basis to investigate the effects of anion density and cation coordination sites within blended electrolytes with strong ionic aggregation. C18LiTFSI was previously reported as a single-component, ion-condensed electrolyte with a wide layered liquid crystalline phase regime. Three additive molecules with varyingly sized polar sulfonyl groups attached to an octodecane-tail were synthesized and mixed with C18LiTFSI. The thermal properties, morphology, and ionic conductivity of the blended electrolytes were characterized. It was found that the blended electrolytes exhibited layered liquid crystalline morphology over a narrower temperature range than the pure salt, and the ionic conductivity of the blended liquid crystalline electrolytes were generally lower than that of the pure salt. Surprising, the additives were found to have the greatest effect on the bulk ionic conductivity of the semicrystalline phase of the electrolytes. Addition of minor fractions of methylsulfonyloctadecane to C18LiTFSI resulted in increases in conductivity of over two orders of magnitude at room temperature, while addition of ethylsulfonyloctadecane or isopropylsulfonyloctadecane with the larger head group resulted in decreased ionic conductivity over the entire composition space and temperature range investigated. Full article

(This article belongs to the Special Issue Innovative Materials for Batteries)

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11 pages, 2247 KiB

Open AccessArticle

Synthesis, Physical Properties and Electrochemical Applications of Two Ionic Liquids Containing the Asymmetric (Fluoromethylsulfonyl)(Trifluoromethylsulfonyl)imide Anion

by Oriele Palumbo, Giovanni Battista Appetecchi, Giovanna Maresca, Jean-Blaise Brubach, Pascale Roy, Simone Di Muzio, Francesco Trequattrini, Delphine Bordignon, Florine Legrand, Anaïs Falgayrat, Rongying Lin, Sebastien Fantini and Annalisa Paolone

Appl. Sci. 2022, 12(9), 4524; https://doi.org/10.3390/app12094524 - 29 Apr 2022

Cited by 2 | Viewed by 1571

Abstract

Novel ionic liquid (IL) electrolytes based on the asymmetric (fluoromethylsulfonyl)(trifluoromethylsulfonyl)imide (FTFSI)⁻ anion, combined with the N-trimethyl-N-butyl-ammonium (N1114)⁺ and N,N-diethyl-N-methyl-N(2-methoxyethyl)-ammonium (N122(2O1))⁺ cations, were successfully synthesized and investigated in terms of thermal, [...] Read more.

Novel ionic liquid (IL) electrolytes based on the asymmetric (fluoromethylsulfonyl)(trifluoromethylsulfonyl)imide (FTFSI)⁻ anion, combined with the N-trimethyl-N-butyl-ammonium (N1114)⁺ and N,N-diethyl-N-methyl-N(2-methoxyethyl)-ammonium (N122(2O1))⁺ cations, were successfully synthesized and investigated in terms of thermal, vibrational and electrochemical properties. Thermogravimetric measurements revealed that the ionic liquids are stable up to 300 °C (2% mass loss). Differential scanning calorimetry measurements evidenced no phase transition down to −90 °C, suggesting a transition towards a glass state at lower temperatures. Infrared spectroscopy measurements, for the first time performed on ILs containing FTFSI, could not detect any crystallization down to −140 °C. The frequency of the main absorption bands of the ILs are in good agreement with DFT calculations. The FTFSI ionic liquid electrolytes, containing 20% mol of LiTFSI, show no solid-liquid phase transition due to the asymmetry of the FTFSI⁻ anion, increasing the −10 °C conductivity up to 10⁻⁴ S cm⁻¹. These interesting ion transport properties remarkably extend the operative temperature range down to low temperatures. The FTFSI electrolytes exhibit remarkable electrochemical stability up to 4.8 V, this making them appealing for realizing safer and highly reliable lithium battery systems operating at high voltages. Full article

(This article belongs to the Special Issue Innovative Materials for Batteries)

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12 pages, 2518 KiB

Open AccessArticle

Sodium-Conducting Ionic Liquid Electrolytes: Electrochemical Stability Investigation

by Giovanna Maresca, Paolo Casu, Elisabetta Simonetti, Sergio Brutti and Giovanni Battista Appetecchi

Appl. Sci. 2022, 12(9), 4174; https://doi.org/10.3390/app12094174 - 21 Apr 2022

Cited by 6 | Viewed by 1667

Abstract

Sodium-conducting electrolytes, based on the EMIFSI, EMITFSI, N1114FSI, N1114TFSI, N1114IM14, PIP13TFSI and PIP14TFSI ionic liquids, were investigated in terms of electrochemical stability through voltammetry techniques with the aim of evaluating their feasibility in Na-ion devices. Both the anodic and cathodic sides were studied. [...] Read more.

Sodium-conducting electrolytes, based on the EMIFSI, EMITFSI, N1114FSI, N1114TFSI, N1114IM14, PIP13TFSI and PIP14TFSI ionic liquids, were investigated in terms of electrochemical stability through voltammetry techniques with the aim of evaluating their feasibility in Na-ion devices. Both the anodic and cathodic sides were studied. The effect of contaminants, such as water and/or molecular oxygen, on the electrochemical robustness of the electrolytes was also investigated. Preliminary cyclic voltammetry and charge-discharge tests were carried out in Na/hard carbon and Na/α-NaMnO2 half cells using selected ionic liquid electrolytes. The results are presented and discussed in the present paper. Full article

(This article belongs to the Special Issue Innovative Materials for Batteries)

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12 pages, 1662 KiB

Open AccessFeature PaperArticle

Influence of Solvent System on the Electrochemical Properties of a closo-Borate Electrolyte Salt

by Matthew Green, Hovnan Simonyan, Katty Kaydanik and Joseph A. Teprovich, Jr.

Appl. Sci. 2022, 12(5), 2273; https://doi.org/10.3390/app12052273 - 22 Feb 2022

Cited by 1 | Viewed by 1686

Abstract

In this study, the use of a closo-borate salt as an electrolyte for lithium-ion batteries (LIB) was evaluated in a series of solvent systems. The lithium closo-borate salts are a unique class of halogen-free salts that have the potential to offer [...] Read more.

In this study, the use of a closo-borate salt as an electrolyte for lithium-ion batteries (LIB) was evaluated in a series of solvent systems. The lithium closo-borate salts are a unique class of halogen-free salts that have the potential to offer some advantages over the halogenated salts currently employed in commercially available LIB due to their chemical and thermal stability. To evaluate this concept, three different solvent systems were prepared with a lithium closo-borate salt to make a liquid electrolyte (propylene carbonate, ethylene carbonate:dimethyl carbonate, and 1-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide). The closo-borate containing electrolytes were then compared by utilizing them with three different electroactive electrode materials. Their cycle stability and performance at various charge/discharge rates was also investigated. Based on the symmetrical cell and galvanostaic cycling studies it was determined that the carbonate based liquid electrolytes performed better than the ionic liquid electrolyte. This work demonstrates that halogen free closo-borate salts are interesting candidates and worthy of further investigation as lithium salts for LIB. Full article

(This article belongs to the Special Issue Innovative Materials for Batteries)

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14 pages, 3192 KiB

Open AccessFeature PaperArticle

Replacement of Cobalt in Lithium-Rich Layered Oxides by n-Doping: A DFT Study

by Mariarosaria Tuccillo, Lorenzo Mei, Oriele Palumbo, Ana Belén Muñoz-García, Michele Pavone, Annalisa Paolone and Sergio Brutti

Appl. Sci. 2021, 11(22), 10545; https://doi.org/10.3390/app112210545 - 9 Nov 2021

Cited by 4 | Viewed by 1913

Abstract

The replacement of cobalt in the lattice of lithium-rich layered oxides (LRLO) is mandatory to improve their environmental benignity and reduce costs. In this study, we analyze the impact of the cobalt removal from the trigonal LRLO lattice on the structural, thermodynamic, and [...] Read more.

The replacement of cobalt in the lattice of lithium-rich layered oxides (LRLO) is mandatory to improve their environmental benignity and reduce costs. In this study, we analyze the impact of the cobalt removal from the trigonal LRLO lattice on the structural, thermodynamic, and electronic properties of this material through density functional theory calculations. To mimic disorder in the transition metal layers, we exploited the special quasi-random structure approach on selected supercells. The cobalt removal was modeled by the simultaneous substitution with Mn/Ni, thus leading to a p-doping in the lattice. Our results show that cobalt removal induces (a) larger cell volumes, originating from expanded distances among stacked planes; (b) a parallel increase of the layer buckling; (c) an increase of the electronic disorder and of the concentration of Jahn–Teller defects; and (d) an increase of the thermodynamic stability of the phase. Overall p-doping appears as a balanced strategy to remove cobalt from LRLO without massively deteriorating the structural integrity and the electronic properties of LRLO. Full article

(This article belongs to the Special Issue Innovative Materials for Batteries)

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24 pages, 8308 KiB

Open AccessArticle

Structure-Property Relation of Trimethyl Ammonium Ionic Liquids for Battery Applications

by Daniel Rauber, Andreas Hofmann, Frederik Philippi, Christopher W. M. Kay, Tatiana Zinkevich, Thomas Hanemann and Rolf Hempelmann

Appl. Sci. 2021, 11(12), 5679; https://doi.org/10.3390/app11125679 - 19 Jun 2021

Cited by 14 | Viewed by 3258

Abstract

Ionic liquids are attractive and safe electrolytes for diverse electrochemical applications such as advanced rechargeable batteries with high energy densities. Their properties that are beneficial for energy storage and conversion include negligible vapor-pressure, intrinsic conductivity as well as high stability. To explore the [...] Read more.

Ionic liquids are attractive and safe electrolytes for diverse electrochemical applications such as advanced rechargeable batteries with high energy densities. Their properties that are beneficial for energy storage and conversion include negligible vapor-pressure, intrinsic conductivity as well as high stability. To explore the suitability of a series of ionic liquids with small ammonium cations for potential battery applications, we investigated their thermal and transport properties. We studied the influence of the symmetrical imide-type anions bis(trifluoromethanesulfonyl)imide ([TFSI]⁻) and bis(fluorosulfonyl)imide ([FSI]⁻), side chain length and functionalization, as well as lithium salt content on the properties of the electrolytes. Many of the samples are liquid at ambient temperature, but their solidification temperatures show disparate behavior. The transport properties showed clear trends: the dynamics are accelerated for samples with the [FSI]⁻ anion, shorter side chains, ether functionalization and lower amounts of lithium salts. Detailed insight was obtained from the diffusion coefficients of the different ions in the electrolytes, which revealed the formation of aggregates of lithium cations coordinated by anions. The ionic liquid electrolytes exhibit sufficient stability in NMC/Li half-cells at elevated temperatures with small current rates without the need of additional liquid electrolytes, although Li-plating was observed. Electrolytes containing [TFSI]⁻ anions showed superior stability compared to those with [FSI]⁻ anions in battery tests. Full article

(This article belongs to the Special Issue Innovative Materials for Batteries)

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