Increased ion conduction in dual cation [sodium][tetraalkylammonium] poly[4-styrenesulfonyl(trifluoromethylsulfonyl)imide-co-ethylacrylate] ionomers

Li, Jiaye; Zhu, Haijin; Wang, Xiaoen; MacFarlane, Douglas R.; Armand, Michel; Forsyth, Maria

doi:10.1039/c5ta04407c

Cited by 22 publications

(17 citation statements)

References 39 publications

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“…Subsequently, we extended our interest to different polymer backbones including the copolymer of PAMPS with poly vinyl sulfonate (PVS) (20) and the copolymer of polystyrenesulfonyl(trifluoromethylsulfonyl)imide with ethyl acrylate. (21) We observed similar evidence of decoupling in all of these systems. However, the ionic conductivities measured in these systems were still too low for application in practical devices.…”

Section: Figure 2 Schematic Of a Mixed Co-cation Conductor And The Chemical Structures Of The Bulky Quaternary Ammonium Cations Describedsupporting

confidence: 69%

Innovative Electrolytes Based on Ionic Liquids and Polymers for Next-Generation Solid-State Batteries

et al. 2019

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Electrolytes based on organic solvents used in current Li-ion batteries are not compatible with the next-generation energy storage technologies including those based on Li metal. Thus, there has been an increase in research activities investigating solid-state electrolytes, ionic liquids (ILs), polymers, and combinations of these. This Account will discuss some of the work from our teams in these areas. Similarly, other metal-based technologies including Na, Mg, Zn, and Al, for example, are being considered as alternatives to Libased energy storage. However, the materials research required to effectively enable these alkali metal based energy storage applications is still in its relative infancy. Once again, electrolytes play a significant role in enabling these devices, and research has for the most part progressed along similar lines to that in advanced lithium technologies. Some of our recent contributions in these areas will also be discussed, along with our perspective on future directions in this field. For example, one approach has been to develop single-ion conductors, where the anion is tethered to the polymer backbone, and the dominant charge conductor is the lithium or sodium countercation. Typically, these present with low conductivity, whereas by using a copolymer approach or incorporating bulky quaternary ammonium co-cations, the effective charge separation is increased thus leading to higher conductivities and greater mobility of the alkali metal cation. This has been demonstrated both experimentally and via computer simulations. Further enhancements in ion transport may be possible in the future by designing and tethering more weakly associating anions to the polymer backbone. The second approach considers ion gels or composite polymer electrolytes where a polymerized ionic liquid is the matrix that provides both mechanical robustness and ion conducting pathways. The block copolymer approach is also demonstrated, in this case, to simultaneously provide mechanical properties and high ionic conductivity when used in combination with ionic-liquid electrolytes. The ultimate electrolyte material that will enable all high-performance solid-state batteries will have ion transport decoupled from the mechanical properties. While inorganic conductors can achieve this, their rigid, brittle nature creates difficulties. On the other hand, ionic polymers and their composites provide a rich area of chemistry to design and tune high ionic conductivity together with ideal mechanical properties.

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Section: Figure 2 Schematic Of a Mixed Co-cation Conductor And The Chemical Structures Of The Bulky Quaternary Ammonium Cations Describedsupporting

confidence: 69%

Innovative Electrolytes Based on Ionic Liquids and Polymers for Next-Generation Solid-State Batteries

et al. 2019

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“…A similar approach has been proposed by Forsyth and co‐workers, [ 185–187 ] by preparing a “polyelectrolyte” with a backbone functionalized by sulfonyl(tri‐fluoromethanesulfonyl)imide anion groups, and quaternary ammonium counter‐ions (Figure 12c), obtaining a conductivity of ≈10 −6 S cm −1 at 90 °C (Figure 12d). The immobilization of the anion on the polymer chain makes the cation the only ionic mobile species in this class of electrolytes, thus minimizing the concentration gradient effect since the ion transference number can approach unity.…”

Section: Electrolytes For Na‐based Rechargeable Batteriesmentioning

confidence: 94%

Electrolytes and Interphases in Sodium‐Based Rechargeable Batteries: Recent Advances and Perspectives

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Elia

Armand

et al. 2020

Advanced Energy Materials

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technologies. Unlike lithium, whose market is already very tight, sodium mineral deposits are almost infinite, evenly distributed worldwide, much easier to extract and thereby attainable at low cost. [1][2][3][4] If the realization of Na-rechargeable batteries could be practically possible, there will be nearly three orders of magnitude relaxation in the constraints on lithium-based resources, accompanied by sustainability, improved environmental benevolence, and cost reduction ( Table 1). Even more appealing is the possible use of the widely available and lighter aluminum, rather than copper, as negative current collector and hard carbon from renewable sources instead of graphite for the negative electrode. Finally, the stability of sodium-ion batteries (SIBs) in the fully discharged state would significantly enhance the safety associated with the shipment of large-format SIBs worldwide.These beneficial features of sodiumbased cells revived the research work on Na-based rechargeable batteries and accordingly captured the attention of both the academic research and industry sectors. However, similar to LIB, most of the research work in Na-based batteries have focused on the development and elaboration of negative and positive For sodium (Na)-rechargeable batteries to compete, and go beyond the currently prevailing Li-ion technologies, mastering the chemistry and accompanying phenomena is of supreme importance. Among the crucial components of the battery system, the electrolyte, which bridges the highly polarized positive and negative electrode materials, is arguably the most critical and indispensable of all. The electrolyte dictates the interfacial chemistry of the battery and the overall performance, having an influence over the practical capacity, rate capability (power), chemical/thermal stress (safety), and lifetime. In-depth knowledge of electrolyte properties provides invaluable information to improve the design, assembly, and operation of the battery. Thus, the full-scale appraisal of both tailored electrolytes and the concomitant interphases generated at the electrodes need to be prioritized. The deployment of large-format Na-based rechargeable batteries also necessitates systematic evaluation and detailed appraisal of the safety-related hazards of Na-based batteries. Hence, this review presents a comprehensive account of the progress, status, and prospect of various Na + -ion electrolytes, including solvents, salts and additives, their interphases and potential hazards.

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“…This decoupled transport presents an opportunity to access conductivity in glassy, more mechanically robust SIC polymers. Decoupled ion transport is most commonly reported experimentally in anion-conducting polymerized ionic liquids (PILs), − but it has also been found in several types of metal cation conductors, including single-cation conducting PILs, , nearly precise carboxylate polyethylene ionomers, and random sulfonate copolymers. − Without adding solvents, salts, or other polymers to increase ion dissociation, systems with decoupled transport have significantly lower conductivity than conventional liquid- or melt-state SPEs. Accessing faster ion transport in SICs in the glassy regime is an important step toward designing mechanically robust and safer electrolytes for batteries.…”

Section: Introductionmentioning

confidence: 99%

Percolated Ionic Aggregate Morphologies and Decoupled Ion Transport in Precise Sulfonated Polymers Synthesized by Ring-Opening Metathesis Polymerization

et al. 2020

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We describe a set of precise single-ion conducting polymers that form self-assembled percolated ionic aggregates in glassy polymer matrices and have decoupled transport of metal cations. These precise single-ion conductors (SICs), synthesized by a scalable ring-opening metathesis polymerization, consist of a polyethylene backbone with a sulfonated phenyl group pendant on every fifth carbon and are fully neutralized by a counterion X+ (Li+, Na+, or Cs+). Experimental X-ray scattering measurements and fully atomistic molecular dynamics (MD) simulations are in good agreement. The MD simulations show that the ionic groups nanophase separate from the polymer backbone to form percolating ionic aggregates. Using graph theory, we find that within the Li+- and Na+-neutralized polymers the percolated aggregates exhibit planar and ribbon-like configurations at intermediate length scales, while the percolated aggregates within the Cs+-neutralized polymers are more isotropic. Electrical impedance spectroscopy measurements show that the ionic conductivities exhibit Arrhenius behavior, with conductivities of 10–7 to 10–6 S/cm at 180 °C. In the MD simulations, the cations move between sulfonate groups in the percolated aggregates, larger ions travel further, and overall cations travel further than the polymer backbones, indicating a decoupled ion-transport mechanism. Thus, the percolated ionic aggregates in these polymers can serve as pathways to facilitate decoupled ion motion through a glassy polymer matrix.

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Increased ion conduction in dual cation [sodium][tetraalkylammonium] poly[4-styrenesulfonyl(trifluoromethylsulfonyl)imide-co-ethylacrylate] ionomers

Abstract: Three dual-cation polymeric ionomers that contain tetraalkylammonium ions and sodium ions have been synthesized and exhibited higher conductivity than the analogous single sodium ion polymers.

Cited by 22 publications

References 39 publications

Innovative Electrolytes Based on Ionic Liquids and Polymers for Next-Generation Solid-State Batteries

Innovative Electrolytes Based on Ionic Liquids and Polymers for Next-Generation Solid-State Batteries

Electrolytes and Interphases in Sodium‐Based Rechargeable Batteries: Recent Advances and Perspectives

Percolated Ionic Aggregate Morphologies and Decoupled Ion Transport in Precise Sulfonated Polymers Synthesized by Ring-Opening Metathesis Polymerization

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