Property-Relaxation Correlations in 3D-Siloxane/Polyether Hybrid Polymer Electrolytes

Boaretto, Nicola; Joost, Christine; Lorrmann, Henning; Vezzù, Keti; Pace, Giuseppe; Noto, Vito Di

doi:10.1021/acs.jpcc.6b01631

Cited by 6 publications

(5 citation statements)

References 21 publications

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“…Progress in the field of solid polymer electrolytes (SPEs) with respect to ionic conductivity (at 298 K) and t Li + . All values are taken from the literature (see bracketed numbers of refs , , , , − , − ).…”

Section: Results and Discussionmentioning

confidence: 99%

High Ion Conducting Nanohybrid Solid Polymer Electrolytes via Single-Ion Conducting Mesoporous Organosilica in Poly(ethylene oxide)

et al. 2017

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A novel mesoporous silica-based single-ion conductor for lithium-ion batteries was prepared via two-step selective functionalization of designated silica precursors into the inner pore wall of mesoporous silica. 2-[(Trifluoromethanesulfonylimido)-N-4sulfonylphenyl]ethyl (TFSISPE) group was first incorporated as a silica precursor having an anionic weak-binding imide group, and a dense brush of oligo-poly(ethylene glycol) (oligo-PEG) moieties, solvating Li + , was cografted to produce functionalized mesoporous silica (FMS-TFSISPE) nanoparticles. FMS-TFSISPE showed a 2D hexagonal nanopore structure and a regular spherical shape with an average diameter of 50 nm. Poly(ethylene oxide) (PEO) was used to form a dispersion of the mesoporous silica nanoparticles into the polymer matrix. This new polymer−mesoporous silica nanohybrid solid electrolyte with the sole mobile Li ions (FMS-TFSISPE-PEO) exhibits attractive electrical, mechanical, and electrochemical properties. The ionic conductivity and storage modulus both increase simultaneously upon addition of FMS-TFSISPE nanoparticles. A 30 wt % amount of FMS-TFSISPE nanoparticles leads to the highest ionic conductivity (σ DC ∼ 10 −3 S/cm at 25 °C) and storage modulus (G′ ∼ 10 4 Pa at 30 °C) with a high lithiumion transference number (t Li + ∼ 0.9). Compared to conventional nonporous silica nanoparticles-incorporated PEO matrix (SiO 2 -TFSISPE-PEO), FMS-TFSISPE-PEO exhibits 2 orders of magnitude higher ionic conductivity with lower activation energy, suggesting that the facile transportation of lithium ions is achieved through the continuous weak-binding and solvating nanopore channel of the mesoporous silica retaining a high surface area and pore volume.

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Section: Results and Discussionmentioning

confidence: 99%

High Ion Conducting Nanohybrid Solid Polymer Electrolytes via Single-Ion Conducting Mesoporous Organosilica in Poly(ethylene oxide)

et al. 2017

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“…The temperature is controlled with a cryostat equipped with a gaseous nitrogen heating–cooling system. Circular samples of 13 mm diameter are compressed between two platinum cylindrical electrodes . The reproducibility of the BES results was tested by measuring the spectra on three different samples for each material.…”

Section: Methodsmentioning

confidence: 99%

“…Circular samples of 13 mm diameter are compressed between two platinum cylindrical electrodes. 25 The reproducibility of the BES results was tested by measuring the spectra on three different samples for each material. The spectra were perfectly coincident, which indicates that the results were reproducible and thus representative of the electric response of each obtained material.…”

Section: Methodsmentioning

confidence: 99%

Electric Response and Conductivity Mechanism of Blended Polyvinylidene Fluoride/Nafion Electrospun Nanofibers

et al. 2019

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The electrical relaxation and polarization phenomena of electrospun PVDF (P)/Nafion (N) blended fiber mats ([P/N0.9]M and β–[P]M) and membranes ([P/N0.9]MM) are compared with those of the solvent-cast membrane of identical composition ([N]C and [P/N0.9]C). The nature of the interactions between the two blended polymer components, that plays a pivotal role in the electrical nature of the resulting materials, is found to be governed by the fabrication method, with those materials obtained via electrospinning undergoing a “reciprocal templating” phenomenon that renders their electrical behavior (especially when in the dry state) significantly different from that of the blended membrane obtained via solvent casting. Broadband Electrical Spectroscopy (BES) demonstrates that the electric response of the blended materials is modulated by polarization phenomena and by α, β, and γ dielectric relaxation events of Nafion domains supported on β-PVDF. The coupling between the relaxations of β-PVDF with those of Nafion matrix is directly correlated to the “reciprocal templating” effect, which modulates the interactions between Nafion and PVDF in electrospun membranes. Two types of conductivity mechanisms characterize the H+ migration within the polymer blends: (1) interdomain H+ migration events by “charge-exchange” phenomena along percolation pathways and (2) H+ exchange between delocalization bodies (DBs) at binding sites at the interface between domains with different ε, size, and morphology. The electrical response of the electrospun membranes also suggests that they do not comprise water clusters with a large size such as those typically observed in pristine Nafion. Rather, the adsorbed H2O molecules, under wet conditions, form thin solvation shells wrapping the polar side chains of the Nafion component. At T = 80 °C, the conductivity of the studied materials decreases in the order [N]C (0.043 S·cm–1) ≈ [P/N0.9]C (0.042 S·cm–1) > [P/N0.9]M (0.031 S·cm–1) > [P/N0.9]MM (0.011 S·cm–1).

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“…[ 132,133 ] Recently, organosilicon‐functionalized PEO has been evaluated as a reliable electrolyte owing to higher flashpoint, lower vapor pressure, better ionic conductivity, wider operating voltage, and higher thermal stability than pristine PEO and the traditional alkylcarbonates. [ 51,134–138 ] The performance improvement after functionalization originates from the finely tuned interactions among PEO, alkali salt and organosilicon, and the particular characteristics of organosilicon. For example, the integration of organosilicon reduces the T g of PEO, whose ion transport is thus effectively promoted due to improved segmental mobility.…”

Section: Overview Of Organosiliconmentioning

confidence: 99%

Organosilicon‐Based Functional Electrolytes for High‐Performance Lithium Batteries

Wang

Chen

et al. 2021

Advanced Energy Materials

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Nowadays excessive consumption of fossil fuels due to population growth and industrial development induced serious energy and environmental crisis. To alleviate the ecological crisis and comply with the ever-increasing energy demand, developingThe electrolyte has been considered as a key factor toward higher energy density for Li-ion and Li-metal batteries. However, conventional electrolytes suffer from uncontrolled interfacial reactions and irreversible decomposition causing performance deterioration and potential safety hazard. Organosilicon compounds have attracted great interest as promising electrolyte components due to facile chemical modifications, low glass transition temperatures (T g ), superior chemical, and thermal stabilities. Considerable investigation efforts have been devoted to developing better overall performance of organosilicon-based electrolytes in the past few years. Herein, the recent research progress of organosilicon-based functional electrolytes for the development of liquid, gel, and solid state electrolytes in Li-ion and Li-metal batteries is summarized. Attention is devoted to various types of organosilicon such as silane, siloxane, polysiloxane, and polyhedral oligomeric silsesquioxanes in terms of molecular design, ionic conductivity, functions shown in batteries, thermal, chemical, electrochemical stability, safety, etc. The feasible strategies are also discussed that may promote the comprehensive electrochemical performances of organosilicon-based electrolytes in different types of electrolytes and batteries. Finally, the challenges facing organosilicon-based electrolytes and proposed their possible solutions are presented alongside promising development directions.

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Property-Relaxation Correlations in 3D-Siloxane/Polyether Hybrid Polymer Electrolytes

Cited by 6 publications

References 21 publications

High Ion Conducting Nanohybrid Solid Polymer Electrolytes via Single-Ion Conducting Mesoporous Organosilica in Poly(ethylene oxide)

High Ion Conducting Nanohybrid Solid Polymer Electrolytes via Single-Ion Conducting Mesoporous Organosilica in Poly(ethylene oxide)

Electric Response and Conductivity Mechanism of Blended Polyvinylidene Fluoride/Nafion Electrospun Nanofibers

Organosilicon‐Based Functional Electrolytes for High‐Performance Lithium Batteries

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