Polymer and composite electrolytes

Hallinan, Daniel T.; Villaluenga, Irune; Balsara, Nitash P.

doi:10.1557/mrs.2018.212

Cited by 63 publications

(73 citation statements)

References 56 publications

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“…9 but not Eqn. 10 can be found in ref 63 . Next, we define normalized transport coefficients, denoted by a subscript , in Eqns.…”

Section: Resultsmentioning

confidence: 98%

“…SAXS data across this concentration range shows no discernable change in morphology. It is useful to define and for model nanostructured electrolytes and use these definitions to normalize our data 11,16,63 . We define a model nanostructured electrolyte as one where salt does not interact with the polystyrene chains and the PEO-rich nanodomains can be approximated as homopolymer electrolytes.…”

Section: Resultsmentioning

confidence: 99%

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Measurement of Three Transport Coefficients and the Thermodynamic Factor in Block Copolymer Electrolytes with Different Morphologies

et al. 2020

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The design and engineering of composite materials is one strategy to satisfy the materials needs of systems with multiple orthogonal property requirements. In the case of rechargeable batteries with lithium metal anodes, the system requires a separator with fast lithium ion transport and good mechanical strength. In this work, we focus on the system polystyrene-blockpoly(ethylene oxide) (SEO) with bis(trifluoromethane)sulfonimide lithium salt (LiTFSI). Ion transport occurs in the salt-containing poly(ethylene oxide)-rich domains. Mechanical rigidity arises due to the glassy nature of polystyrene (PS). If we assume that the salt does not interact with the PS-rich domains, we can describe ion transport in the electrolyte by three transport parameters (ionic conductivity, , salt diffusion coefficient, , and cation transference number, + 0) and a thermodynamic factor, f. By systematically varying the volume fraction of the conducting phase, c between 0.29 and 1.0, and chain length, between 80 and 8000, we elucidate the role of morphology on ion transport. We find that is the strongest function of morphology, varying by three full orders of magnitude, while is a weaker function of morphology. To calculate + 0 and f , we measure the current fraction, + , and the open circuit potential, , of concentration cells. We find that + and follow universal trends as a function of salt concentration, regardless of chain length, morphology, or c , allowing us to calculate + 0 for any SEO/LiTFSI or PEO/LiTFSI mixture when and are known. The framework developed in this paper enables predicting the performance of any block copolymer electrolyte in a rechargeable battery. MAIN TEXT

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“…9 but not Eqn. 10 can be found in ref 63 . Next, we define normalized transport coefficients, denoted by a subscript , in Eqns.…”

Section: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%

Measurement of Three Transport Coefficients and the Thermodynamic Factor in Block Copolymer Electrolytes with Different Morphologies

et al. 2020

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“…As a comparison, SPEs have low ionic conductivity and low elastic modulus not enough to prevent Li dendrite growth, but they are more flexible and have excellent adhesive properties along with better thermal, mechanical, and electrochemical stability. Therefore, they have received worldwide attention in generating high‐performance LIBs and LMBs . So far, SPEs have not been applied in commercial batteries due to their low room temperature ionic conductivities .…”

Section: Methodsmentioning

confidence: 99%

Simultaneously Boosting the Ionic Conductivity and Mechanical Strength of Polymer Gel Electrolyte Membranes by Confining Ionic Liquids into Hollow Silica Nanocavities

Thapaliya

Do‐Thanh

Jafta

et al. 2019

Batteries & Supercaps

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A central problem of solid polymer electrolytes is their inability to achieve robust mechanical strength with fast ionic conductivities required for commercialization of lithium metal batteries (LMBs). At present, state-of-the-art offers superiority of one at the expense of the other. Here, this dilemma has been solved by fabricating mechanically robust solid composite polymer electrolytes (SCPEs) with superior ionic conductivity (0.5 mS cm À 1 at 20°C) by confining ionic liquids (ILs) in the hollow scaffold offered by hollow silica (HS) nanospheres with unique architecture. Mechanical robustness was verified by the performance of a Li j j Li symmetric cell cycling for extended hours without short-circuiting. In addition, SCPEs with HS have higher thermal and electrochemical stabilities than those without HS, due to strong interaction and coordination of HS nanoparticles with polymer and ionic liquids. Electrode compatibility and flexibility of the membrane could advance the LMBs technology.The replacement of graphite by Li metal boosts the energy density of the current lithium-ion batteries (LIBs) because of high theoretical capacity (~3860 mAh g À 1 or 2061 mAh cm À 3 ) and the lowest electrochemical potential (À 3.04 V) of Limetal. [1] However, challenges of the lithium anode such as Li dendritic growth, dead lithium, and rapid capacity degradation have hampered its commercialization. [1b,e] Different approaches such as using liquid electrolytes with additives, [2] morphological modification of anodes, [1b,2d, 3] and volume minimization [1b,4] have been explored, but could not completely solve the lithium dendrite problem as well as the accompanying safety concerns.

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“…19 The conductivity of P( pP-EO 4 )-20 was also comparable to SEO doped with LiTFSI which have recorded conductivities between 3.5 × 10 −4 and 5 × 10 −4 S cm −1 at 90°C. 44,45 In another piece of work, Bergfelt et al prepared triblock copolymers containing a oligo(ethylene oxide) methyl ether methacrylate center block and two benzyl methacrylate end blocks. 46 After addition of LiTFSI, the electrolyte with [EO]/[Li] = 8 exhibited the highest ionic conductivity at 80°C, Table 2).…”

Section: Ionic Conductivitymentioning

confidence: 99%

Poly(p-phenylene)s tethered with oligo(ethylene oxide): synthesis by Yamamoto polymerization and properties as solid polymer electrolytes

Nederstedt

Jannasch

2020

Polym. Chem.

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rsc.li/polymers Poly( p-phenylene)s tethered with oligo(ethylene oxide): synthesis by Yamamoto polymerization and properties as solid polymer electrolytes † Hannes Nederstedt and Patric Jannasch * Salt-containing supramolecular assemblies of rigid-rod polymers tethered with flexible ion-solvating side chains represent a synthetic pathway towards thin ion-conducting solid electrolyte membranes with high dimensional stability. In the present work we have synthesized poly( p-phenylene)s (PpPs) carrying di-, triand tetra(ethylene oxide) side chains, respectively. p-Dichlorophenyl oligo(ethylene oxide) monomers were polymerized by Ni-mediated Yamamoto polymerization via in situ reduction of Ni(II). This gave PpPs with an average degree of polymerization reaching 60, where each phenylene ring carried one oligo (ethylene oxide) side chain. Results from calorimetry and X-ray scattering measurements clearly showed the formation of molecular composites, i.e., bicontinuous morphologies with mechanically reinforcing layers of the stiff PpP backbones separated by the flexible oligo(ethylene oxide) side chains. This morphology was retained after adding lithium bis(trifluoromethane)sulfonimide (LiTFSI) to form salt-inpolymer electrolytes, but with an increased distance between adjacent backbones. Furthermore, upon addition of salt the order-to-disorder transition (ODT) region increased from ∼50-170°C to ∼75-200°C at [EO]/[Li] = 20. Increasing salt concentrations also revealed a maximum in the ODT enthalpy at [EO]/[Li] = 40. At 80 and 160°C, the ionic conductivity reached 1.1 × 10 −4 and 1.0 × 10 −3 S cm −1 , respectively. Finally, we demonstrate that ionic conductivity of the polymer electrolytes can be significantly increased by additions of triglyme. † Electronic supplementary information (ESI) available: 13 C and HMQC NMR spectra of P( pP-EO 3 ), molar mass distributions of the polymers, additional thermal data for neat polymers and electrolyte membranes, photographs of P( pP-EO 2 ) films, frequency dependence of the ionic conductivity of the P( pP-EO 3 )-30 membrane. See

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Polymer and composite electrolytes

Abstract: Abstract

Cited by 63 publications

References 56 publications

Measurement of Three Transport Coefficients and the Thermodynamic Factor in Block Copolymer Electrolytes with Different Morphologies

Measurement of Three Transport Coefficients and the Thermodynamic Factor in Block Copolymer Electrolytes with Different Morphologies

Simultaneously Boosting the Ionic Conductivity and Mechanical Strength of Polymer Gel Electrolyte Membranes by Confining Ionic Liquids into Hollow Silica Nanocavities

Poly(p-phenylene)s tethered with oligo(ethylene oxide): synthesis by Yamamoto polymerization and properties as solid polymer electrolytes

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