Molecular mobility and Li+ conduction in polyester copolymer ionomers based on poly(ethylene oxide)

Fragiadakis, D.; Dou, Shichen; Colby, Ralph H.; Runt, James

doi:10.1063/1.3063659

Cited by 182 publications

(376 citation statements)

References 43 publications

(56 reference statements)

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“…Notice that at high temperatures, approaching 100 • C, the electrolytes containing TFSI-based anions exhibit ionic conductivities of over one order of magnitude greater than that of the sulfonate-based electrolytes; this difference is much diminished at low temperatures. This indicates that the ion pair dissociation and ion mobility have different activation energies [19]. This effect is also made apparent when comparing styrenic and non-styrenic monomers.…”

Section: Introductionmentioning

confidence: 72%

Ion Transport in Solvent-Free, Crosslinked, Single-Ion Conducting Polymer Electrolytes for Post-Lithium Ion Batteries

et al. 2018

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Solvent-free, single-ion conducting electrolytes are sought after for use in electrochemical energy storage devices. Here, we investigate the ionic conductivity and how this property is influenced by segmental mobility and conducting ion number in crosslinked single-ion conducting polyether-based electrolytes with varying tethered anion and counter-cation types. Crosslinked electrolytes are prepared by the polymerization of poly(ethylene glycol) diacrylate (PEGDA), poly(ethylene glycol) methyl ether acrylate, and ionic monomers. The ionic conductivity of the electrolytes is measured and interpreted in the context of differential scanning calorimetry and Raman spectroscopy measurements. A lithiated crosslinked electrolyte prepared with PEG 31 DA and (4-styrenesulfonyl)(trifluoromethanesulfonyl)imide (STFSI) monomers is found to have a lithium ion conductivity of 3.2 × 10 −6 and 1.8 × 10 −5 S/cm at 55 and 100 • C, respectively. The percentage of unpaired anions for this electrolyte was estimated at about 23% via Raman spectroscopy. Despite the large variances in metal cation-STFSI binding energies as predicted via density functional theory (DFT) and large variations in ionic conductivity, STFSI-based crosslinked electrolytes with the same charge density and varying cations (Li, Na, K, Mg, and Ca) were estimated to all have unpaired anion populations in the range of 19 to 29%.

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Section: Introductionmentioning

confidence: 72%

Ion Transport in Solvent-Free, Crosslinked, Single-Ion Conducting Polymer Electrolytes for Post-Lithium Ion Batteries

et al. 2018

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“…The exact overlapping of the fit line and experimental points of the σ′ values of the investigated PNCE materials in the high-frequency region confirms their power law behaviour. The deviation from σ dc (plateau region) value in lower-frequency region of the σ′ spectra is due to the contribution of EP process, which can be analyzed for the estimation of mobile ion concentration and their mobility in the polymer electrolytes [31][32][33]. The n values of the investigated PNCE films were found in the range 0.87 to 0.91, and their σ dc values vary anomalously with the increase of MMT concentration ( Table 1).…”

Section: Resultsmentioning

confidence: 92%

Dielectric spectroscopy and confirmation of ion conduction mechanism in direct melt compounded hot-press polymer nanocomposite electrolytes

Choudhary

Sengwa

2011

Ionics

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Solid-type polymer nanocomposite electrolyte (PNCE) comprising poly(ethylene oxide) (PEO), lithium perchlorate (LiClO 4 ) and montmorillonite (MMT) nanoplatelets were synthesized by direct melt compounded hotpress technique at 70°C under 3 tons of pressure. The spectra of complex dielectric function, electric modulus and alternating current (ac) electrical conductivity, and complex impedance plane plots of these materials were investigated in the frequency range 20 Hz to 1 MHz at ambient temperature. The variation of electrode polarization and ionic conduction relaxation times with MMT concentration up to 20 wt.% confirms their strong correlation with direct current ionic conductivity. The predominance of exfoliated MMT structures in PEO matrix and their effect on cation conduction mechanism and ion pairing were discussed by considering a supramolecular transient cross-linked structure. The normalized ac conductivity as a function of scaled frequency of these PNCE materials obey the universal time-concentration superposition behaviour alike the disordered solid ionic conductors.

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“…Notice that at high temperatures, approaching 100 °C, the electrolytes containing TFSI-based anions exhibit ionic conductivities of over one order of magnitude greater than that of the sulfonate-based electrolytes; this difference is much diminished at low temperatures. This indicates that the ion pair dissociation and ion mobility have different activation energies [19]. Of the investigated tethered anion types, electrolytes containing APTFSI exhibited the highest ionic conductivity over the measured temperature range with SFTSI electrolytes exhibiting just slightly lower conductivities.…”

Section: Resultsmentioning

confidence: 95%

“…The typical molecular structure of the SIPE for a lithium-ion battery is a lithiated ionomer with poly(ethylene oxide) (PEO) functionality and tethered anions [13][14][15][16][17][18][19][20][21]. SIPEs can have very high oxidative stabilities and support higher charge/discharge rates than polymer electrolytes of similar conductivities and non-unity transference numbers [16,22].…”

Section: Introductionmentioning

confidence: 99%

Ion Transport in Solvent-Free, Crosslinked, Single-Ion Conducting Polymer Electrolytes for Post-Lithium Ion Batteries

Elmore¹,

Seidler²,

Ford³

et al. 2018

Preprint

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Solvent-free, single-ion conducting electrolytes are sought after for use in electrochemical energy storage devices. Here, we investigate the ionic conductivity and how this property is influenced by segmental mobility and conducting ion number in crosslinked single-ion conducting polyether-based electrolytes with varying tethered anion and counter-cation types. Crosslinked electrolytes are prepared by the polymerization of poly(ethylene glycol) diacrylate (PEGDA), poly(ethylene glycol) methyl ether acrylate, and ionic monomers. The ionic conductivity of the electrolytes is measured and interpreted in the context of differential scanning calorimetry and Raman spectroscopy measurements. A lithiated crosslinked electrolyte prepared with PEG31DA and STFSI monomers is found to have a lithium ion conductivity of 3.2 × 10 -6 and 1.8 × 10 −5 S/cm at 55 and 100 °C, respectively. The percentage of unpaired anions for this electrolyte was estimated at about 23% via Raman spectroscopy. Despite the large variances in metal cation -STFSI binding energies as predicted via DFT and large variations in ionic conductivity, STFSIbased crosslinked electrolytes with the same charge density and varying cations (Li, Na, K, Mg, and Ca) were estimated to all have unpaired anion populations in the range of 19 to 29%.

show abstract

Molecular mobility and Li+ conduction in polyester copolymer ionomers based on poly(ethylene oxide)

Cited by 182 publications

References 43 publications

Ion Transport in Solvent-Free, Crosslinked, Single-Ion Conducting Polymer Electrolytes for Post-Lithium Ion Batteries

Ion Transport in Solvent-Free, Crosslinked, Single-Ion Conducting Polymer Electrolytes for Post-Lithium Ion Batteries

Dielectric spectroscopy and confirmation of ion conduction mechanism in direct melt compounded hot-press polymer nanocomposite electrolytes

Ion Transport in Solvent-Free, Crosslinked, Single-Ion Conducting Polymer Electrolytes for Post-Lithium Ion Batteries

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