Electrochemical and NMR characterizations of mixed polymer electrolytes based on oligoether sulfate and imide salts

Chauvin, Christophe; Alloin, Fannie; Judeinstein, Patrick; Foscallo, D.; Sanchez, Jean‐Yves

doi:10.1016/j.electacta.2006.07.023

Cited by 18 publications

(16 citation statements)

References 19 publications

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“…Alloin et al [59] impregnated a 3D perfluorosulfonate based single Li-conducting polymer by LiTFSI to assess the possibility of stopping the TFSI anion mobility, but the cationic transference number, T + , was only doubled. On the other hand, Chauvin et al [60] mixed a Li-conducting ionic liquid made of an oligo(oxyethylene) end-capped by a lithium sulfate ester moiety with LiTFSI and roughly tripled T + , while maintaining conductivity closed to the known optimal. Using crystalline forms of highly concentrated POE complexes, Bruce et al [61] reported that an isovalent doping of only 5% of TFSI anion produced a conductivity gain of about 1.5 orders of magnitude.…”

Section: Polymer Electrolyte Based On Sodium Salts Blendsmentioning

confidence: 99%

Development of sodium-conducting polymer electrolytes: comparison between film-casting and films obtained via green processes

Martínez-Cisneros

Levenfeld

Várez

et al. 2016

Electrochimica Acta

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Sodium-conducting solvent-free polymer electrolytes based on commercially available and inexpensive materials poly(oxyethylene), POE, and three different sodium salts (NaI, NaCF 3 SO 3 and NaClO 4 ) were prepared and exhaustively characterized. In order to minimize the environmental impact related to conventional film processing based on casting, a combination of lyophilization and hot-pressing was successfully applied. Contrary to film-casting, this new approach led to very homogeneous and pore-free films. This study suggests the obtained polymer electrolyte films as a promising route to enhance not only ionic conductivity but also mechanical properties. Furthermore, a preliminary work on salt blends hosted by POE shows that they strongly decrease melting point and crystallinity of the polymer electrolytes and paves the way for enhanced sodium-conducting materials.

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Section: Polymer Electrolyte Based On Sodium Salts Blendsmentioning

confidence: 99%

Development of sodium-conducting polymer electrolytes: comparison between film-casting and films obtained via green processes

Martínez-Cisneros

Levenfeld

Várez

et al. 2016

Electrochimica Acta

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“…This equation describes conductivity in dilute solutions where anions and cations are fully dissociated. The ratio of measured conductivity to that calculated with the Nernst-Einstein equation can be used as a rough approximation of the degree of dissociation in the material [8,9]. Reduced dissociation indicates ion pairing or clustering and results in a reduction in the number of effective charge carriers.…”

Section: Methodsmentioning

confidence: 99%

Nuclear Magnetic Resonance (NMR) Characterization of a Polymerized Ionic Liquid Electrolyte Material

et al. 2012

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Solid electrolyte materials have the potential to improve performance and safety characteristics of lithium-ion batteries by replacing conventional solvent-based electrolytes. A candidate solid polymer electrolyte, AMLi/PEGDM, has been synthesized by crosslinking an anionic monomer AMLi, with poly(ethylene glycol) dimethacrylate. The main goal of the synthesis is to produce a single-ion conducting polymer network where lithium cations can move freely and fluorinated anions are immobilized as part of the polymer network. A comprehensive characterization of anion and cation mobility in the resulting material is therefore required. Using pulsed-field gradient nuclear magnetic resonance (PFG-NMR), we are able to measure and quantify the individual diffusion coefficients of mobile species in the material ( 19 F and 7 Li) and confirm the extent to which the fluorinated anionic component is immobilized. We have characterized dry (σ~3.0 x10 -7 S/cm at 30°C) and propylene carbonate (PC) saturated gel (σ~1.0x10 -4 S/cm at 30°C) samples. Experimental results include NMR spin-spin and spin-lattice relaxation times in addition to diffusion coefficient measurements over a temperature range up to 100°C. Practically, the diffusion measurements are extremely challenging, as the spin-spin (T 2 ) relaxation times are very short, necessitating the development of specialized pulsed-field gradient apparatus. Diffusion coefficients for the most mobile components of the lithium cations and fluorinated anions at 100°C in dry membranes have been found to be 3.4 x10 -8 cm 2 /s and 2.1 x10 -8 cm 2 /s respectively. These results provide valuable insight into the conduction mechanisms in these materials, and will drive further optimization of solid polymer electrolytes.

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“…27 However, in the general case (typically in the case of polyvalent ions), the mobility of ion i depends on three parameters: (i) z i , charge of the ion, (ii) solvated radius of the ion (through self diffusion coefficient D i ) and (iii) C i , concentration of the ion. In accordance with the Nernst-Einstein law, these three parameters appear in the expression of ionic conductivity (Eq.…”

Section: Calculation Of the Lithium Cation Transference Numbermentioning

confidence: 99%

“…Typically, t + of LiTFSI roughly ranges from 0.3 to 0.5 in molecular solvents 26 (note that it barely exceeds 0.1 in high MW PEO). 27 However, in the general case (typically in the case of polyvalent ions), the mobility of ion i depends on three parameters: (i) z i , charge of the ion, (ii) solvated radius of the ion (through self diffusion coefficient D i ) and (iii) C i , concentration of the ion.…”

Section: Calculation Of the Lithium Cation Transference Numbermentioning

confidence: 99%

What use for polysilsesquioxane lithium salts in lithium batteries?

et al. 2016

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Electrochemical and NMR characterizations of mixed polymer electrolytes based on oligoether sulfate and imide salts

Cited by 18 publications

References 19 publications

Development of sodium-conducting polymer electrolytes: comparison between film-casting and films obtained via green processes

Development of sodium-conducting polymer electrolytes: comparison between film-casting and films obtained via green processes

Nuclear Magnetic Resonance (NMR) Characterization of a Polymerized Ionic Liquid Electrolyte Material

What use for polysilsesquioxane lithium salts in lithium batteries?

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