Using gel polymer electrolytes (GPEs) for lithium-ion batteries usually encounters the drawback of poor mechanical integrity of the GPEs. This study demonstrates the outstanding performance of a GPE consisting of a commercial membrane (Celgard) incorporated with a poly(ethylene oxide)-co-poly(propylene oxide) copolymer (P(EO-co-PO)) swelled by a liquid electrolyte (LE) of 1 M LiPF6 in carbonate solvents. The proposed GPE stably holds LE with an amount that is three times that of the Celgard-P(EO-co-PO) composite. This GPE has a higher ionic conductivity (2.8×10(-3) and 5.1×10(-4) S cm(-1) at 30 and -20 °C, respectively) and a wider electrochemical voltage range (5.1 V) than the LE-swelled Celgard because of the strong ion-solvation power of P(EO-co-PO). The active ion-solvation role of P(EO-co-PO) also suppresses the formation of the solid-electrolyte interphase layer. When assembling the GPE in a Li/LiFePO4 battery, the P(EO-co-PO) network hinders anionic transport, producing a high Li+ transference number of 0.5 and decreased the polarization overpotential. The Li/GPE/LiFePO4 battery delivers a discharge capacity of 156-135 mAh g(-1) between 0.1 and 1 C-rates, which is approximately 5% higher than that of the Li/LE/LiFePO4 battery. The IR drop of the Li/GPE/LiFePO4 battery was 44% smaller than that of the Li/LE/LiFePO4. The Li/GPE/LiFePO4 battery is more stable, with only a 1.2% capacity decay for 150 galvanostatic charge-discharge cycles. The advantages of the proposed GPE are its high stability, conductivity, Li+ transference number, and mechanical integrity, which allow for the assembly of GPE-based batteries readily scalable to industrial levels.
A polyacrylonitrile (PAN)-interpenetrating cross-linked polyoxyethylene (PEO) network (named XANE) was synthesized acting as separator and as gel polymer electrolytes simultaneously. SEM images show that the surface of the XANE membrane is nonporous, comparing to the surface of the commercial separator to be porous. This property results in excellent electrolyte uptake amount (425 wt %), and electrolyte retention for XANE membrane, significantly higher than that of commercial separator (200 wt %). The DSC result indicates that the PEO crystallinity is deteriorated by the cross-linked process and was further degraded by the interpenetration of the PAN. The XANE membrane shows significantly higher ionic conductivity (1.06-8.21 mS cm(-1)) than that of the commercial Celgard M824 separator (0.45-0.90 mS cm(-1)) ascribed to the high electrolyte retention ability of XANE (from TGA), the deteriorated PEO crystallinity (from DSC) and the good compatibility between XANE and electrode (from measuring the interfacial-resistance). For battery application, under all charge/discharge rates (from 0.1 to 3 C), the specific half-cell capacities of the cell composed of the XANE membrane are all higher than those of the aforementioned commercial separator. More specifically, the cell composed of the XANE membrane has excellent cycling stability, that is, the half-cell composed of the XANE membrane still exhibited more than 97% columbic efficiency after 100 cycles at 1 C. The above-mentioned advantageous properties and performances of the XANE membrane allow it to act as both an ionic conductor as well as a separator, so as to work as separator-free gel polymer electrolytes.
The synthesis of a gelled polymer electrolyte (GPE) using poly(ethylene glycol) blending poly(acrylonitrile) (i.e., PAN‐b‐PEG‐b‐PAN) as a host, dimethyl formamide (DMF) as a plasticizer and LiClO4 as an electrolytic salt for electric double layer capacitors (EDLCs) is reported. The PAN‐b‐PEG‐b‐PAN copolymer in the GPE has a linear configuration for high ionic conductivity and excellent compatibility with carbon electrodes. When assembling the GPE in a carbon‐based symmetric EDLC, the copolymer network facilitates ion motion by reducing the equivalent series resistance and Warburg resistance of the capacitor. This symmetric cell has a capacitance value of 101 F g−1 at 0.125 A g−1 and can deliver an energy level of 11.5 Wh kg−1 at a high power of 10 000 W kg−1 over a voltage window of 2.1 V. This cell shows superior stability, with little decay of specific capacitance after 30 000 galvanostatic charge‐discharge cycles. The distinctive merit of the GPE film is its adjustable mechanical integrity, which makes the roll‐to‐roll assembly of GPE‐based EDLCs readily scalable to industrial levels.
The effects of tetraalkylammonium bromides (TAABs) on the micellization of sodium dodecylsulfate (SDS) are studied using pyrene solubilization and several nuclear magnetic resonance (NMR) techniques. Two-dimensional nuclear Overhauser effect spectroscopy (2D NOESY) experiments confirm that tetraalkylammonium (TAA(+)) ions associate with SDS to form mixed micelles. TAA(+) ions attach to the surface of the mixed micelles and become inserted into the hydrophobic core of the mixed micelles. Because TAA(+) ions appear in the hydrophobic interior of the TAA-SDS mixed micelles, the micropolarity inside the mixed micelles sensed by pyrene might not reflect the true hydrophobicity of the micellar core. Using proton chemical shift analysis, the degree of hydration on the surface of the mixed micelles is determined from the chemical shift change of SDS α-CH2 protons. The self-diffusion coefficients of SDS and TAA(+) ions in the TAAB/SDS/D2O solutions are measured by using pulse-field gradient NMR, and the fraction of TAA(+) ions associated with the SDS to form the mixed micelles is calculated from the self-diffusion data. Moreover, secondary micelle formation for SDS and TAA(+) ions is observed on the basis of (1)H chemical shift analysis and the self-diffusion data. The 2D NOESY experiments also reveal unusual tumbling behavior of SDS alkyl protons. For Pr4NBr/SDS and Bu4NBr/SDS solutions, positive and negative nuclear Overhauser effects are simultaneously observed among the SDS alkyl protons.
The interaction of poly(N-vinylformamide) (PNVF) with anionic surfactant, sodium dodecyl sulfate (SDS), has been studied by pyrene fluorescence and two-dimensional nuclear Overhauser effect spectroscopy (2D NOESY). With use of pyrene as the probe, from low to high concentration of SDS, the pyrene I 1 /I 3 plot exhibits three stages of association of PNVF with SDS. The I 1 /I 3 plot vs [SDS] shows a well-defined plateau (I 1 /I 3 ) 1.47) at SDS concentrations ranging between 3 and 10 mM, indicating that in this range of SDS concentrations the sizes of polymer-bound SDS aggregates are approximately identical. The ambiguity in determining the critical aggregation concentration (cac) of SDS from the I 1 /I 3 plot vs [SDS], which resembles the typical profile of surface tension vs surfactant concentration, has been clarified by the 2D NOESY experiment. Also, just beyond the cac ([SDS] ) 3 mM), definite proof of formation of the PNVF-SDS complex bound on the polymer chain is provided by the 2D NOESY experiments. On the basis of the inter-and intramolecular cross-relaxation between the protons of PNVF and SDS, the microstructure of PNVF-induced SDS aggregates is proposed. Moreover, the association behavior of PNVF with SDS is compared to that of the poly(vinylpyrrolidone) (PVP)/SDS and poly(ethylene oxide) (PEO)/SDS systems.
We report alkyl-poly(l-threonine)/cyclodextrin
(alkyl-PLT/CD)
supramolecular hydrogels with different molecular assemblies. Their
properties are determined by the interplay between host–guest
chemistry and hydrogen-bonding interactions. The gelation process
was mainly dictated by the formation of alkyl chain/CD inclusion complex
and PLT chain conformation. The dodecyl-PLT20/α-CD
hydrogel exhibited laminar packing due to the sheet-to-coil conformational
change upon forming inclusion complex. The hexadecyl-PLT20/β-CD hydrogel exhibited ribbon-like assemblies instead, because
the peptide adopted mainly sheet conformation. The gel-to-sol transition
occurred upon increasing temperature because of the decrease in hydrogen-bonding
interactions and partly conformational change.
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