Effects of nanoscale SiO2 on the thermal and transport properties of solvent-free, poly(ethylene oxide) (PEO)-based polymer electrolytes

Capiglia, Claudio; Mustarelli, Piercarlo; Quartarone, Eliana; Tomasi, Corrado; Magistris, A.

doi:10.1016/s0167-2738(98)00457-3

Cited by 240 publications

(106 citation statements)

References 9 publications

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“…In pursuit of such materials, several classes of electrolytes have been studied as replacements for conventional liquid electrolytes: polymers, [7][8][9][10][11] polymer composites, [12][13][14][15] hybrids, 16-18 gels, 19,20 ionic liquids, 21 and ceramics.…”

Section: Introductionmentioning

confidence: 99%

Nanoporous hybrid electrolytes

et al. 2011

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Oligomer-suspended SiO 2 -polyethylene glycol nanoparticles are studied as porous media electrolytes. At SiO 2 volume fractions, φ, bracketing a critical value φ y ≈ 0.29, the suspensions jam and their mechanical modulus increase by more than seven orders.For φ > φ y , the mean pore diameter is close to the anion size, yet the ionic conductivity remains surprisingly high and can be understood, at all φ, using a simple effective medium model proposed by Maxwell. SiO 2 -polyethylene glycol hybrid electrolytes are also reported to manifest attractive electrochemical stability windows (0.3-6.3V) and to reach a steady-state interfacial impedance when in contact with metallic lithium. IntroductionLithium ions are the active charge carrying species in the most energy dense secondary batteries of today, those used in electronics and hybrid electric transportation. Currently commercialized lithiated anode materials such as LiC 6 and Li 4 Ti 5 O 12 have relatively low theoretical energy capacities (360 mAh/g and 175 mAh/g, respectively). Advanced secondary battery systems employing electrodes such as LiCoPO 4 , 1 lithium, 2-5 or sulfur 6 require electrolytes with specific properties such as wide electrochemical stability windows, high mechanical strength, and/or inertness or non-solvency towards the electrode materials and their intercalation products.Next-generation lithium ion batteries should also employ electrolytes that are nonflammable, non-volatile, non-leakable, and non-toxic, making them safer both in use and after disposal. In pursuit of such materials, several classes of electrolytes have been studied as replacements for conventional liquid electrolytes: polymers, [7][8][9][10][11] polymer composites, [12][13][14][15] hybrids, 16-18 gels, 19,20 ionic liquids, 21 and ceramics. 22In many cases, mechanical integrity of the electrolyte comes at a cost: namely, a large loss in ionic conductivity, which places undesirable limits on the charge/discharge rate of the cell. Liquid and particulate plasticizers have been used with some success in circumventing this constraint in composite and gel polymer electrolytes. 4,15,19,23 With a mechanically strong framework in place such as a polymer or ceramic, the liquid plasticizer serves as a freely diffusing ionic conduction medium that provides ionic conductivities near that of a pure liquid electrolyte. If a liquid plasticizer with good thermal and electrochemical properties is utilized, safety concerns are reduced. In the case of particulate plasticizers, of either nano-or micron-scale, the particles have been shown to decrease crystallization of the surrounding matrix, thereby enhancing segmental motion of the host polymer and increasing conduction. While nanoparticles have been shown most successful in this area, in typical polymer composites particle aggregation occurs; this reduces the effectiveness of the individual particles in inhibiting crystallization but allows for formation of a percolated particulate network that aids in bulk mechanical strength.Recently, we r...

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Section: Introductionmentioning

confidence: 99%

Nanoporous hybrid electrolytes

et al. 2011

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“…While short chain polyethylene glycol (PEG) oligomers exhibit good ionic conductivity at room temperature as well as chemical and thermal stability, amorphous low molecular weight electrolytes lack mechanical strength. The addition of free inorganic particles [3][4][5][6][7] as well as inorganic networks [8] and inorganic-organic constituents [9][10][11] to polymer electrolytes has been shown to improve both mechanical properties and conductivity.In this communication, we report on a new class of solvent-free, nanoscale organic hybrid materials (NOHMs), which simultaneously manifest superionic conductivities, large electrochemical stability windows (-0.5V to > 5 V, vs Li), good lithium ion transference numbers (~0.45), no volatility and thermal stabilities up to 400 o C, and which offer multiple handles through which near molecular control can be exerted on mechanical properties. All of these features provide unusual opportunities for engineering new families of high-performance, nanoscale hybrid…”

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confidence: 99%

Nanoscale Organic Hybrid Electrolytes

2010

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Significant effort has been devoted by research groups world-wide to the development of polymer and composite polymer electrolytes for use in lithium batteries [1,2] . The best known polymer ionic conductor, polyethylene oxide (PEO), is crystalline and has low conductivity at room temperature. While short chain polyethylene glycol (PEG) oligomers exhibit good ionic conductivity at room temperature as well as chemical and thermal stability, amorphous low molecular weight electrolytes lack mechanical strength. The addition of free inorganic particles [3][4][5][6][7] as well as inorganic networks [8] and inorganic-organic constituents [9][10][11] to polymer electrolytes has been shown to improve both mechanical properties and conductivity.In this communication, we report on a new class of solvent-free, nanoscale organic hybrid materials (NOHMs), which simultaneously manifest superionic conductivities, large electrochemical stability windows (-0.5V to > 5 V, vs Li), good lithium ion transference numbers (~0.45), no volatility and thermal stabilities up to 400 o C, and which offer multiple handles through which near molecular control can be exerted on mechanical properties. All of these features provide unusual opportunities for engineering new families of high-performance, nanoscale hybrid

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“…The conductivity of polymer gel electrolytes increases with the addition of fumed silica, and two maxima have been observed in the conductivity variation at very low concentrations of fumed silica. After the position of second maxima, the conductivity shows a continuous decrease, which is due to higher viscosity of the electrolytes and blocking of conducting pathways by the grains of fumed silica which hinders the motion of mobile ions [21]. The initial increase in conductivity at very low concentration of fumed silica is due to an increase in free ion concentration, which may take place due to the dissociation of ion aggregates present in these gel electrolytes.…”

Section: Resultsmentioning

confidence: 99%

Ion Conducting Behaviour of Nano Dispersed Polymer Gel Electrolytes Containing NH4PF6

Sharma¹,

Sekhon²

2007

Port. Electrochim. Acta

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The effect of addition of nano size fumed silica on the conductivity and viscosity behaviour of polymer gel electrolytes containing polyethylene oxide (PEO), ammonium hexafluorophosphate (NH 4 PF 6 ) and propylene carbonate (PC) has been studied. The addition of PEO increases the viscosity of electrolytes alongwith a small increase in conductivity and polymer gel electrolytes with conductivity higher than the corresponding liquid electrolytes have been obtained. Increase in conductivity with the addition of PEO and fumed silica has been explained to be due to the dissociation of ion aggregates, which is also supported by FTIR results. The thermal stability of polymer gel electrolytes improves marginally with the addition of fumed silica. The conductivity of nano dispersed gels does not show much change over 20-100 o C temperature range and also remains constant with time.

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Effects of nanoscale SiO2 on the thermal and transport properties of solvent-free, poly(ethylene oxide) (PEO)-based polymer electrolytes

Cited by 240 publications

References 9 publications

Nanoporous hybrid electrolytes

Nanoporous hybrid electrolytes

Nanoscale Organic Hybrid Electrolytes

Ion Conducting Behaviour of Nano Dispersed Polymer Gel Electrolytes Containing NH4PF6

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