Editorial

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4 pages, 187 KiB

Open AccessEditorial

Composite Electrolyte & Electrode Membranes for Electrochemical Energy Storage & Conversion Devices

by Giovanni Battista Appetecchi

Membranes 2020, 10(11), 359; https://doi.org/10.3390/membranes10110359 - 21 Nov 2020

Cited by 2 | Viewed by 1590

Abstract

[...] Full article

(This article belongs to the Special Issue Composite Electrolyte & Electrode Membranes for Electrochemical Energy Storage & Conversion Devices)

Research

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14 pages, 3129 KiB

Open AccessArticle

The Use of Succinonitrile as an Electrolyte Additive for Composite-Fiber Membranes in Lithium-Ion Batteries

by Jahaziel Villarreal, Roberto Orrostieta Chavez, Sujay A. Chopade, Timothy P. Lodge and Mataz Alcoutlabi

Membranes 2020, 10(3), 45; https://doi.org/10.3390/membranes10030045 - 17 Mar 2020

Cited by 6 | Viewed by 4885

Abstract

In the present work, the effect of temperature and additives on the ionic conductivity of mixed organic/ionic liquid electrolytes (MOILEs) was investigated by conducting galvanostatic charge/discharge and ionic conductivity experiments. The mixed electrolyte is based on the ionic liquid (IL) (EMI/TFSI/LiTFSI) and organic [...] Read more.

In the present work, the effect of temperature and additives on the ionic conductivity of mixed organic/ionic liquid electrolytes (MOILEs) was investigated by conducting galvanostatic charge/discharge and ionic conductivity experiments. The mixed electrolyte is based on the ionic liquid (IL) (EMI/TFSI/LiTFSI) and organic solvents EC/DMC (1:1 v/v). The effect of electrolyte type on the electrochemical performance of a LiCoO₂ cathode and a SnO₂/C composite anode in lithium anode (or cathode) half-cells was also investigated. The results demonstrated that the addition of 5 wt.% succinonitrile (SN) resulted in enhanced ionic conductivity of a 60% EMI-TFSI 40% EC/DMC MOILE from ~14 mS·cm⁻¹ to ~26 mS·cm⁻¹ at room temperature. Additionally, at a temperature of 100 °C, an increase in ionic conductivity from ~38 to ~69 mS·cm⁻¹ was observed for the MOILE with 5 wt% SN. The improvement in the ionic conductivity is attributed to the high polarity of SN and its ability to dissolve various types of salts such as LiTFSI. The galvanostatic charge/discharge results showed that the LiCoO₂ cathode with the MOILE (without SN) exhibited a 39% specific capacity loss at the 50th cycle while the LiCoO₂ cathode in the MOILE with 5 wt.% SN showed a decrease in specific capacity of only 14%. The addition of 5 wt.% SN to the MOILE with a SnO₂/C composite-fiber anode resulted in improved cycling performance and rate capability of the SnO₂/C composite-membrane anode in lithium anode half-cells. Based on the results reported in this work, a new avenue and promising outcome for the future use of MOILEs with SN in lithium-ion batteries (LIBs) can be opened. Full article

(This article belongs to the Special Issue Composite Electrolyte & Electrode Membranes for Electrochemical Energy Storage & Conversion Devices)

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12 pages, 2315 KiB

Open AccessArticle

Composite Nafion Membranes with CaTiO_3−δ Additive for Possible Applications in Electrochemical Devices

by Lucia Mazzapioda, Maria Assunta Navarra, Francesco Trequattrini, Annalisa Paolone, Khalid Elamin, Anna Martinelli and Oriele Palumbo

Membranes 2019, 9(11), 143; https://doi.org/10.3390/membranes9110143 - 31 Oct 2019

Cited by 12 | Viewed by 3507

Abstract

A composite membrane based on a Nafion polymer matrix incorporating a non-stoichiometric calcium titanium oxide (CaTiO_3−δ) additive was synthesized and characterized by means of thermal analysis, dynamic mechanical analysis, and broadband dielectric spectroscopy at different filler contents; namely two concentrations of [...] Read more.

A composite membrane based on a Nafion polymer matrix incorporating a non-stoichiometric calcium titanium oxide (CaTiO_3−δ) additive was synthesized and characterized by means of thermal analysis, dynamic mechanical analysis, and broadband dielectric spectroscopy at different filler contents; namely two concentrations of 5 and 10 wt.% of the CaTiO_3−δ additive, with respect to the dry Nafion content, were considered. The membrane with the lower amount of additive displayed the highest water affinity and the highest conductivity, indicating that a too-high dose of additive can be detrimental for these particular properties. The mechanical properties of the composite membranes are similar to those of the plain Nafion membrane and are even slightly improved by the filler addition. These findings indicate that perovskite oxides can be useful as a water-retention and reinforcing additive in low-humidity proton-exchange membranes. Full article

(This article belongs to the Special Issue Composite Electrolyte & Electrode Membranes for Electrochemical Energy Storage & Conversion Devices)

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7 pages, 2646 KiB

Open AccessArticle

LFP-Based Gravure Printed Cathodes for Lithium-Ion Printed Batteries

by Maria Montanino, Giuliano Sico, Anna De Girolamo Del Mauro and Margherita Moreno

Membranes 2019, 9(6), 71; https://doi.org/10.3390/membranes9060071 - 07 Jun 2019

Cited by 10 | Viewed by 3054

Abstract

Printed batteries have undergone increased investigation in recent years because of the growing daily use of small electronic devices. With this in mind, industrial gravure printing has emerged as a suitable production technology due to its high speed and quality, and its capability [...] Read more.

Printed batteries have undergone increased investigation in recent years because of the growing daily use of small electronic devices. With this in mind, industrial gravure printing has emerged as a suitable production technology due to its high speed and quality, and its capability to produce any shape of image. The technique is one of the most appealing for the production of functional layers for many different purposes, but it has not been highly investigated. In this study, we propose a LiFePO₄ (LFP)-based gravure printed cathode for lithium-ion rechargeable printed batteries and investigate the possibility of employing this printing technique in battery manufacture. Full article

(This article belongs to the Special Issue Composite Electrolyte & Electrode Membranes for Electrochemical Energy Storage & Conversion Devices)

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11 pages, 2300 KiB

Open AccessArticle

Gel Polymer Electrolytes Based on Silica-Added Poly(ethylene oxide) Electrospun Membranes for Lithium Batteries

by Maria Assunta Navarra, Lucia Lombardo, Pantaleone Bruni, Leonardo Morelli, Akiko Tsurumaki, Stefania Panero and Fausto Croce

Membranes 2018, 8(4), 126; https://doi.org/10.3390/membranes8040126 - 05 Dec 2018

Cited by 8 | Viewed by 3710

Abstract

Solid polymer electrolytes, in the form of membranes, offering high chemical and mechanical stability, while maintaining good ionic conductivity, are envisaged as a possible solution to improve performances and safety in different lithium cell configurations. In this work, we designed and prepared systems [...] Read more.

Solid polymer electrolytes, in the form of membranes, offering high chemical and mechanical stability, while maintaining good ionic conductivity, are envisaged as a possible solution to improve performances and safety in different lithium cell configurations. In this work, we designed and prepared systems formed using innovative nanocomposite polymer membranes, based on high molecular weight poly(ethylene oxide) (PEO) and silica nanopowders, produced by the electrospinning technique. These membranes were subsequently gelled with solutions based on aprotic ionic liquid, carbonate solvents, and lithium salt. The addition of polysulfide species to the electrolyte solution was also considered, in view of potential applications in lithium-sulfur cells. The morphology of the electrospun pristine membranes was evaluated using scanning electron microscopy. Stability and thermal properties of pristine and gelled systems were investigated uisng differential scanning calorimetry and thermal gravimetric analysis. Electrochemical impedance spectroscopy was used to determine the conductivity of both swelling solutions and gelled membranes, allowing insight into the ion transport mechanism within the proposed composite electrolytes. Full article

(This article belongs to the Special Issue Composite Electrolyte & Electrode Membranes for Electrochemical Energy Storage & Conversion Devices)

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15 pages, 1707 KiB

Open AccessArticle

Composite Gel Polymer Electrolytes Based on Organo-Modified Nanoclays: Investigation on Lithium-Ion Transport and Mechanical Properties

by Cataldo Simari, Ernestino Lufrano, Luigi Coppola and Isabella Nicotera

Membranes 2018, 8(3), 69; https://doi.org/10.3390/membranes8030069 - 24 Aug 2018

Cited by 33 | Viewed by 4816

Abstract

Composite gel polymer electrolytes (GPEs) based on organo-modified montmorillonite clays have been prepared and investigated. The organo-clay was prepared by intercalation of CTAB molecules in the interlamellar space of sodium smectite clay (SWy) through a cation-exchange reaction. This was used as nanoadditive in [...] Read more.

Composite gel polymer electrolytes (GPEs) based on organo-modified montmorillonite clays have been prepared and investigated. The organo-clay was prepared by intercalation of CTAB molecules in the interlamellar space of sodium smectite clay (SWy) through a cation-exchange reaction. This was used as nanoadditive in polyacrylonitrile/polyethylene-oxide blend polymer, lithium trifluoromethanesulphonate (LiTr) as salt and a mixture of ethylene carbonate/propylene carbonate as plasticizer. GPEs were widely characterized by DSC, SEM, and DMA, while the ion transport properties were investigated by AC impedance spectroscopy and multinuclear NMR spectroscopy. In particular, ⁷Li and ¹⁹F self-diffusion coefficients were measured by the pulse field gradient (PFG) method, and the spin-lattice relaxation times (T₁) by the inversion recovery sequence. A complete description of the ions dynamics in so complex systems was achieved, as well as the ion transport number and ionicity index were estimated, proving that the smectite clay surfaces are able to “solvatate” both lithium and triflate ions and to create a preferential pathway for ion conduction. Full article

(This article belongs to the Special Issue Composite Electrolyte & Electrode Membranes for Electrochemical Energy Storage & Conversion Devices)

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11 pages, 1771 KiB

Open AccessArticle

High Performance Polymer/Ionic Liquid Thermoplastic Solid Electrolyte Prepared by Solvent Free Processing for Solid State Lithium Metal Batteries

by Francisco González, Pilar Tiemblo, Nuria García, Oihane Garcia-Calvo, Elisabetta Fedeli, Andriy Kvasha and Idoia Urdampilleta

Membranes 2018, 8(3), 55; https://doi.org/10.3390/membranes8030055 - 02 Aug 2018

Cited by 30 | Viewed by 5867

Abstract

A polymer/ionic liquid thermoplastic solid electrolyte based on poly(ethylene oxide) (PEO), modified sepiolite (TPGS-S), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and 1-Butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR₁₄TFSI) ionic liquid is prepared using solvent free extrusion method. Its physical-chemical, electrical, and electrochemical properties are comprehensively studied. The investigated [...] Read more.

A polymer/ionic liquid thermoplastic solid electrolyte based on poly(ethylene oxide) (PEO), modified sepiolite (TPGS-S), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and 1-Butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR₁₄TFSI) ionic liquid is prepared using solvent free extrusion method. Its physical-chemical, electrical, and electrochemical properties are comprehensively studied. The investigated solid electrolyte demonstrates high ionic conductivity together with excellent compatibility with lithium metal electrode. Finally, truly Li-LiFePO₄ solid state coin cell with the developed thermoplastic solid electrolyte demonstrates promising electrochemical performance during cycling under 0.2 C/0.5 C protocol at 60 °C. Full article

(This article belongs to the Special Issue Composite Electrolyte & Electrode Membranes for Electrochemical Energy Storage & Conversion Devices)

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14 pages, 4109 KiB

Open AccessArticle

Ionic Liquid-Based Electrolyte Membranes for Medium-High Temperature Lithium Polymer Batteries

by Guk-Tae Kim, Stefano Passerini, Maria Carewska and Giovanni Battista Appetecchi

Membranes 2018, 8(3), 41; https://doi.org/10.3390/membranes8030041 - 10 Jul 2018

Cited by 23 | Viewed by 5064

Abstract

Li⁺-conducting polyethylene oxide-based membranes incorporating N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide are used as electrolyte separators for all-solid-state lithium polymer batteries operating at medium-high temperatures. The incorporation of the ionic liquid remarkably improves the thermal, ion-transport and interfacial properties of the polymer [...] Read more.

Li⁺-conducting polyethylene oxide-based membranes incorporating N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide are used as electrolyte separators for all-solid-state lithium polymer batteries operating at medium-high temperatures. The incorporation of the ionic liquid remarkably improves the thermal, ion-transport and interfacial properties of the polymer electrolyte, which, in combination with the wide electrochemical stability even at medium-high temperatures, allows high current rates without any appreciable lithium anode degradation. Battery tests carried out at 80 °C have shown excellent cycling performance and capacity retention, even at high rates, which are never tackled by ionic liquid-free polymer electrolytes. No dendrite growth onto the lithium metal anode was observed. Full article

(This article belongs to the Special Issue Composite Electrolyte & Electrode Membranes for Electrochemical Energy Storage & Conversion Devices)

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Review

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23 pages, 4508 KiB

Open AccessReview

Review of Recent Nuclear Magnetic Resonance Studies of Ion Transport in Polymer Electrolytes

by Stephen Munoz and Steven Greenbaum

Membranes 2018, 8(4), 120; https://doi.org/10.3390/membranes8040120 - 30 Nov 2018

Cited by 32 | Viewed by 5822

Abstract

Current and future demands for increasing the energy density of batteries without sacrificing safety has led to intensive worldwide research on all solid state Li-based batteries. Given the physical limitations on inorganic ceramic or glassy solid electrolytes, development of polymer electrolytes continues to [...] Read more.

Current and future demands for increasing the energy density of batteries without sacrificing safety has led to intensive worldwide research on all solid state Li-based batteries. Given the physical limitations on inorganic ceramic or glassy solid electrolytes, development of polymer electrolytes continues to be a high priority. This brief review covers several recent alternative approaches to polymer electrolytes based solely on poly(ethylene oxide) (PEO) and the use of nuclear magnetic resonance (NMR) to elucidate structure and ion transport properties in these materials. Full article

(This article belongs to the Special Issue Composite Electrolyte & Electrode Membranes for Electrochemical Energy Storage & Conversion Devices)

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36 pages, 8385 KiB

Open AccessReview

Recent Advances in Poly(vinylidene fluoride) and Its Copolymers for Lithium-Ion Battery Separators

by João C. Barbosa, José P. Dias, Senentxu Lanceros-Méndez and Carlos M. Costa

Membranes 2018, 8(3), 45; https://doi.org/10.3390/membranes8030045 - 19 Jul 2018

Cited by 132 | Viewed by 10784

Abstract

The separator membrane is an essential component of lithium-ion batteries, separating the anode and cathode, and controlling the number and mobility of the lithium ions. Among the polymer matrices most commonly investigated for battery separators are poly(vinylidene fluoride) (PVDF) and its copolymers poly(vinylidene [...] Read more.

The separator membrane is an essential component of lithium-ion batteries, separating the anode and cathode, and controlling the number and mobility of the lithium ions. Among the polymer matrices most commonly investigated for battery separators are poly(vinylidene fluoride) (PVDF) and its copolymers poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), and poly(vinylidene fluoride-cochlorotrifluoroethylene) (PVDF-CTFE), due to their excellent properties such as high polarity and the possibility of controlling the porosity of the materials through binary and ternary polymer/solvent systems, among others. This review presents the recent advances on battery separators based on PVDF and its copolymers for lithium-ion batteries. It is divided into the following sections: single polymer and co-polymers, surface modification, composites, and polymer blends. Further, a critical comparison between those membranes and other separator membranes is presented, as well as the future trends on this area. Full article

(This article belongs to the Special Issue Composite Electrolyte & Electrode Membranes for Electrochemical Energy Storage & Conversion Devices)

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