Polymer electrolyte conducting

Table 1. Some imide ions and carbanions used in salts to enhance polymer electrolyte conductivity and reduce crystallinity...

Polymer Repeat unit Glass-transition temperature, Ts (°C) Melting point, Tm (°C) Typical polymer electrolyte Conductivity (S/cm at 25°C)... 

Polymer electrolytes conduct cations by segmental motions of the polymer backbone that carry the cations from one complexation site to the next.60-62 Since this requires significant fluidity, the polymers are conductive only in the amorphous state, i.e. above the crystalline to gel transition temperature. For the bulk polymer of PHB, this temperature is in the range of 0° to 10 °C. Accordingly, single molecules of PHB dissolved in fluid lipid bilayers should be capable of considerable segmental motions at physiological temperatures. 

In synthesis, the peformance of the laminated ECDs becomes comparable to that of the liquid electrolyte ECDs only at temperatures higher than 65°C. This may consistently limit the widespread application of these solid-state displays, unless improved polymer electrolytes, having higher conductivity at ambient temperature, are used as an alternative. It is interesting to point out, however, that even with the PEO-based configuration, the laminated ECDs may find some unique applications. In fact, the drastic thermal dependence of the polymer electrolyte conductivity may be conveniently exploited for the realization of new optical devices directed to specific uses. For instance, considering the memory effect typical of the... 

Doyle et al. [2] examine the tradeoffs involved with using a higher salt concentration in polymer electrolytes. Conductivity in polymer electrolytes generally displays a maximum at about 1 to 15 M salt concentration. One might then choose to use a salt concentration which yields this maximum conductivity. 

Polymer Electrolyte Fuel Cell. The electrolyte in a PEFC is an ion-exchange (qv) membrane, a fluorinated sulfonic acid polymer, which is a proton conductor (see Membrane technology). The only Hquid present in this fuel cell is the product water thus corrosion problems are minimal. Water management in the membrane is critical for efficient performance. The fuel cell must operate under conditions where the by-product water does not evaporate faster than it is produced because the membrane must be hydrated to maintain acceptable proton conductivity. Because of the limitation on the operating temperature, usually less than 120°C, H2-rich gas having Htde or no (

The successfiil synthesis of a transparent soHd polymer electrolyte (SPE) based on PEO and alkoxysilanes has been reported (41). The material possessed good mechanical properties and high electrical conductivity (around 1.8 x 10 S/cm at 25°C) dependent on the organic—inorganic ratio and PEO chain length. 

A second class of important electrolytes for rechargeable lithium batteries are soHd electrolytes. Of particular importance is the class known as soHd polymer electrolytes (SPEs). SPEs are polymers capable of forming complexes with lithium salts to yield ionic conductivity. The best known of the SPEs are the lithium salt complexes of poly(ethylene oxide) [25322-68-3] (PEO), —(CH2CH20) —, and poly(propylene oxide) [25322-69-4] (PPO) (11—13). Whereas a number of experimental battery systems have been constmcted using PEO and PPO electrolytes, these systems have not exhibited suitable conductivities at or near room temperature. Advances in the 1980s included a new class of SPE based on polyphosphazene complexes suggesting that room temperature SPE batteries may be achievable (14,15). 

Figure 11.9. Conductivity vs temperature plot for two ionically conducting crystals and for a polymer electrolyte, LiTf-aPtO40, which is based on amorphous poly(ethylene) oxide (after Ratner...

The first use of ionic liquids in free radical addition polymerization was as an extension to the doping of polymers with simple electrolytes for the preparation of ion-conducting polymers. Several groups have prepared polymers suitable for doping with ambient-temperature ionic liquids, with the aim of producing polymer electrolytes of high ionic conductance. Many of the prepared polymers are related to the ionic liquids employed for example, poly(l-butyl-4-vinylpyridinium bromide) and poly(l-ethyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide [38 1]. 

Noda and Watanabe [42] reported a simple synthetic procedure for the free radical polymerization of vinyl monomers to give conducting polymer electrolyte films. Direct polymerization in the ionic liquid gives transparent, mechanically strong and highly conductive polymer electrolyte films. This was the first time that ambient-temperature ionic liquids had been used as a medium for free radical polymerization of vinyl monomers. The ionic liquids [EMIM][BF4] and [BP][Bp4] (BP is N-butylpyridinium) were used with equimolar amounts of suitable monomers, and polymerization was initiated by prolonged heating (12 hours at 80 °C) with benzoyl... 

Ren, X. Springer, T. E. and Gottesfeld, S. (1998). Direct Methanol Fuel Cell Transport Properties of the Polymer Electrolyte Membrane and Cell Performance. Vol. 98-27. Proc. 2nd International Symposium on Proton Conducting Membrane Euel Cells. Pennington, NJ Electrochemical Society. 

A plasticized electrolyte, usually obtained by the addition of small amounts of a liquid of high dielectric constant to a solving polymer electrolyte in order to enhance its conductivity. 

A membrane ionomer, in particular a polyelectrolyte with an inert backbone such as Nation . They require a plasticizer (typically water) to achieve good conductivity levels and are associated primarily, in their protonconducting form, with solid polymer-electrolyte fuel cells. 

Figure 1 shows the temperature variation of the ionic conductivities for several polymer-electrolyte systems. At room temperature they are typically 100 to 1000 times less than those exhibited by a liquid or the best ceramic- or glass-based electrolytes [6,8], Although higher conductivities are preferable, 100-fold or 1000-fold... 

Figure 1. Temperature variation of the conductivity for a cross-section of polymer electrolytes. PESc, poly (ethylene succinate) PEO, polyethylene oxide) PPO, polypropylene oxide) PEI, poly(ethyleneimine) MEEP, poly(methoxyethoxy-ethoxyphosphazene) aPEO, amorphous methoxy-linked PEO PAN, polyacrylonitrile PC, propylene carbonate EC, ethylene carbonate.

The polymer electrolytes discussed so far suffer from a number of disadvantages. Firstly, they exhibit low conductivities in comparison with liquid or solid (crystalline or glassy) electrolytes at or below room temperature. The best all-amorphous systems have conductivities less than 10"4 S cm-1 at room temperature. These ambient... 

Addition of both ion-conducting and inert ceramics enhances the conductivity of a polymer electrolyte. This increase is attributed to an increase in volume fraction of the amorphous phase [133-136]. No... 

The classical example of a soUd organic polymer electrolyte and the first one found is the poly(ethylene oxide) (PEO)/salt system [593]. It has been studied extensively as an ionically conducting material and the PEO/hthium salt complexes are considered as reference polymer electrolytes. However, their ambient temperature ionic conductivity is poor, on the order of 10 S cm, due to the presence of crystalUne domains in the polymer which, by restricting polymer chain motions, inhibit the transport of ions. Consequently, they must be heated above about 80 °C to obtain isotropic molten polymers and a significant increase in ionic conductivity. 

Polyphosphazenes bearing crown ethers (12-crown-4,15-crown-5 and 18-crown-6) as single or as mixed substituents with trifluoroethoxy or methoxy-ethoxyethoxy groups were synthesized by Cowie [601,602] and Allcock [484] and their conductivity studied because it was shown that the incorporation of crown ether molecules into a polymer electrolyte could increase their ionic conductivity. In these macromolecules, the crown ether units were linked to the backbone through oxymethylene spacer groups. 

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