Electrochemistry of liquids vs. solids: Polymer electrolytes

Baril, Daniel

doi:10.1016/s0167-2738(96)00614-5

Cited by 182 publications

(100 citation statements)

References 44 publications

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“…An increase in ionic conductivity with temperature may be interpreted as a hopping mechanism between coordinating sites together with local structural relaxations and segmental motions of the polymer salt complexes [12]. As temperature increases the polymer chain acquires faster internal modes in which bond rotations produce segmental motion.…”

Section: Resultsmentioning

confidence: 99%

“…SPEs are defined as host polymers with conducting ions under the effect of an electric field [4][5][6].Different host polymers have been used for SPEs, among which poly(ethylene) (PE) [7], poly(propylene) (PP) [8], poly(ethylene oxide) (PEO) [9,10] and poly(acrylonitrile) (PAN) have been the most widely explored [9,11]. Among these PEO seems to have the best properties although the corresponding SPEs present ionic conductivity values [12]. To solve this problem and thus produce PEO-based systems with high ionic conductivities, some strategies, such as the incorporation of plasticizers and the production of polymer blends have been proposed [13,14].…”

Section: Introductionmentioning

confidence: 99%

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Ionically conducting Er3+-doped DNA-based biomembranes for electrochromic devices

Leones¹,

Fernandes²,

Sentanin³

et al. 2014

Electrochimica Acta

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Ionically conducting Er3+-doped DNA-based biomembranes for electrochromic devices

Leones¹,

Fernandes²,

Sentanin³

et al. 2014

Electrochimica Acta

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“…It is also of interest to study materials such as PPG-1025 which is a liquid in order to compare it with the results for related high equivalent weight solid materials. 33 Finally, it has recently been pointed out that the pressure variation of various dynamical phenomena of PPGbased materials exhibits opposite curvature to those based on PEG. 34 In order to gather further information concerning this effect, new high pressure data are presented along with a detailed analysis.…”

Section: Introductionmentioning

confidence: 99%

Pressure and temperature variation of the electrical conductivity of poly(propylene glycol) containing LiCF3SO3

Fontanella

1999

The Journal of Chemical Physics

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Complex impedance and differential scanning calorimetry (DSC) studies have been carried out on poly(propylene glycol) with average molecular weight 1025 (PPG) and PPG containing LiCF3SO3. The impedance studies were made at frequencies from about 1 mHz to 100 MHz at pressures up to 0.3 GPa (3 kbar) over the temperature range 215–365 K. Both the impedance and DSC studies were carried out in vacuum or at atmospheric pressure over a temperature range of about 100–375 K. As a consequence, the impedance studies overlap the DSC glass transition temperature. The inadequacy of the widely used Vogel–Tammann–Fulcher or Williams–Landel–Ferry equations to describe the temperature variation of the vacuum electrical conductivity data is discussed. It is shown that the Bendler–Shlesinger formalism is a better representation of the data, particularly in the region close to the glass transition. The first pressure derivative of the electrical conductivity, and hence apparent activation volume, decreases strongly as temperature increases. In addition, the activation volumes are larger for the low molecular weight liquids than the values reported previously for related, high molecular weight rubbery electrolytes. Next, there appears to be an exponential relationship between the activation volume and the electrical conductivity. Finally, the pressure variation of the electrical conductance exhibits negative curvature which shows that the activation volume increases as pressure increases. A qualitative explanation of each of these results concerning the relationship between conductivity, temperature, and pressure is given in terms of free volume. However, whether free volume can provide a quantitative explanation remains to be determined.

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“…1-3 After the pioneering work by Fenton et al, 4 where poly(ethylene oxide) (PEO) laden with alkali metal salts was shown to possess good ionic conductivity, its application as a polymer electrolyte in a full cell was demonstrated by Armand et al [5][6][7] PEO is a semi-crystalline polymer at room temperature. Ionic transport in PEO electrolytes is linked to segmental motion of the polymer chains, 8,9 and occurs predominantly in the amorphous phase.…”

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confidence: 99%

Failure Mode of Lithium Metal Batteries with a Block Copolymer Electrolyte Analyzed by X-Ray Microtomography

Devaux

Harry

Parkinson

et al. 2015

J. Electrochem. Soc.

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Solid block polymer electrolytes are promising candidates for the development of high energy density rechargeable lithium metal based batteries. All solid-state batteries comprising lithium metal negative electrode and lithium iron phosphate (LiFePO 4 ) composite positive electrode were assembled. A polystyrene-b-poly(ethylene oxide) (SEO) copolymer doped with a lithium salt was used as the electrolyte. After cycling the batteries, the reason for capacity fade and failure was determined by imaging the batteries using synchrotron hard X-ray microtomography. These experiments revealed partial delamination of the lithium foil and the block copolymer electrolyte layer. The void volume between the foil and electrolyte layer obtained after 40 to 90 cycles is comparable to volume change in the battery during one cycle. A simple model to account for the effect of delamination on current density in the battery is presented. Capacity fade and battery failures observed in our experiments are consistent with this model. No evidence of lithium dendrite formation was found. In contrast, cycled lithium-lithium symmetric cells with the same polymer electrolyte at the same current density failed due to dendrite formation. No evidence of delamination was found in these cells. Solid polymer electrolytes are promising candidates for the development of high performance rechargeable batteries comprising a lithium (Li) metal electrode due to their chemical stability toward lithium and their mechanical resistance to dendrite growth.1-3 After the pioneering work by Fenton et al., 4 where poly(ethylene oxide) (PEO) laden with alkali metal salts was shown to possess good ionic conductivity, its application as a polymer electrolyte in a full cell was demonstrated by Armand et al. [5][6][7] PEO is a semi-crystalline polymer at room temperature. Ionic transport in PEO electrolytes is linked to segmental motion of the polymer chains, 8,9 and occurs predominantly in the amorphous phase.10 Thus solid polymer electrolyte based batteries must be operated at temperatures (T) above the PEO melting temperature. However, amorphous PEO is too soft to avoid short circuit due to lithium dendrite growth. 11,12 One approach for resolving this problem is the use of a block copolymer electrolyte. [13][14][15][16][17][18][19][20][21][22] Immiscibility between the blocks induces microphase separation, producing hard insulating phases interspersed with soft, ionically conductive phases. [23][24][25] In studies utilizing block copolymers as solid polymer electrolytes, the mechanical phase is usually made of a high glass transition temperature polymer such as polystyrene. [26][27][28][29] Extensive work on the thermodynamics of polystyrene-b-poly(ethylene oxide) (SEO) diblock copolymers [30][31][32][33] indicate that the tendency for microphase separation is enhanced by the presence of ions. 34,35 For symmetric SEO electrolytes, i.e. copolymers wherein the volume fraction of the conducting phase is above 50%, the ionic conductivity has been shown to increase wit...

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Electrochemistry of liquids vs. solids: Polymer electrolytes

Cited by 182 publications

References 44 publications

Ionically conducting Er3+-doped DNA-based biomembranes for electrochromic devices

Ionically conducting Er3+-doped DNA-based biomembranes for electrochromic devices

Pressure and temperature variation of the electrical conductivity of poly(propylene glycol) containing LiCF3SO3

Failure Mode of Lithium Metal Batteries with a Block Copolymer Electrolyte Analyzed by X-Ray Microtomography

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