Solvent-free polymer electrolytes conductivity

Solvent-free polymer-electrolyte-based batteries are still developmental products. A great deal has been learned about the mechanisms of ion conductivity in polymers since the discovery of the phenomenon by Feuillade et al. in 1973 [41], and numerous books have been written on the subject. In most cases, mobility of the polymer backbone is required to facilitate cation transport. The polymer, acting as the solvent, is locally free to undergo thermal vibrational and translational motion. Associated cations are dependent on these backbone fluctuations to permit their diffusion down concentration and electrochemical gradients. The necessity of polymer backbone mobility implies that noncrystalline, i.e., amorphous, polymers will afford the most highly conductive media. Crystalline polymers studied to date cannot support ion fluxes adequate for commercial applications. Unfortunately, even the fluxes sustainable by amorphous polymers discovered to date are of marginal value at room temperature. Neat polymer electrolytes, such as those based on poly(ethyleneoxide) (PEO), are only capable of providing viable current densities at elevated temperatures, e.g., >60°C. 

Glasses and polymer electrolytes are in a certain sense not solid electrolytes but neither are they considered as liquid ones. A glass can be regarded as a supercooled liquid and solvent-free polymer electrolytes are good conductors only above their glass transition temperature (7 ), where the structural disorder is dynamic as well as static. These materials appear macroscopically as solids because of their very high viscosity. A conductivity relation of the Vogel-Tamman-Fulcher (VTF) type is usually... 

Lithium solid-state electrolytes can be roughly divided into three main categories (i) ceramic (CE), (ii) glasses (GL), (iii) solvent-free polymer electrolytes (SPEs). Indeed, the most appealing class is CE, which has been the object of recent good reviews [6-8]. These electrolytes can easily offer a relatively high conductivity (up to 10 cm ), and have the further advantage of a thermal expansion... 

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 S cm at room temperature. These ambient temperature conductivities may be insufficient in some cases for the power required by a lithium battery. Secondly, the interfacial impedances present at both the lithium anode (passivation) and composite cathode (passivation, contact) are in addition to the ohmic losses in the electrolyte. Thirdly, the lowness of cation transference number, although similar to the values in liquid systems, is a major issue since the total conductivity is lower and could limit the use of solvent-free polymer electrolytes except in the form of extremely thin films or above room temperature. 

In conclusion, polymer electrolytes based on phosphazene backbone and containing ether side chains are, after complexation with alkali metal salts, among the highest ionically solvent-free polymer salt complexes, with conductivities in the order of 10" -10" S cm However, these conductivities are still below the value of 10 S cm" which is considered to be the minimum for practical applications. Therefore the design of new polyphosphazenes electrolytes with a higher conductivity and also a higher dimensional stability still remains a challenge for future researchers. 

A HE SEARCH FOR PLASTIC, solvent-free electrolytes for use in solid-state batteries is being actively pursued in several laboratories (1-4). A number of reports have stressed the need for facile motion of the macromolecular chain in order to promote the ion conduction process in the polymer matrix, because this process occurs primarily via a free-volume mechanism (1-4). Comblike polymers with oligooxyethylene side chains constitute effective media for ion conduction of solubilized alkali salts (5-8). The low glass transition temperature (Tg) of poly(dimethylsiloxane) suggests that polysi-loxane could serve as a suitable backbone for such a comb polymer, and recent studies (9-J2) indicate this to be the case indeed. 

The addition of gel-forming components (plasticizers) to polymer electrolytes (see the above) produces gel like structures. Therefore, this type of ion-conducting polymers can also be described as gel polymer electrolytes. Gel polymer electrolytes can also be prepared, if a solution of a salt in an organic solvent is added to a polymer matrix (polyvinyl chloride, polyvinyl fluoride). The solvent dissolves in the polymer matrix and forms a gel like structure. The conductivity as well as the current density and rate of diffusion, etc., are determined by the mobUity of the solvated ions in the polymer matrix. The transport constants are again proportional to the free volume in the polymer. 

We have reviewed safety improvements of organic electrolytes by adding flame retardants, and ILs have also been discussed. A more radical solution would be replacing liquid organic electrolytes with solvent-free lithium conductive-membranes reviewed in [196,197]. The most promising options have been briefly reviewed in [198], in particular membranes based on homopolymers, such as poly(ethylene oxide) hosting a lithium salt. However, the conductivity of these polymers is still too low to make them suitable to batteries operating at ambient temperature [199]. 

Measurement of Ionic Conductivity. The synthesis of solvent-free metal salt complexes of polyethylene oxides prompted detailed electrical measurements with the thought that these materials might prove to be useful electrolytes, in a hydrous environment, for high energy density batteries (13-15). Many fundamental properties of these polymer electrolytes have been examined and a large literature on the subject is available (16-17). We prepared a disk of one of our polyether complexes and measured its conductivity by impedance methods. 

Quasi-solid-state electrolytes include gel polymer electrolytes, ionic liquids, and plastic crystal systems. It is important to distinguish polymer electrolytes and gel polymer electrolytes. In polymer electrolytes, charged cationic or anionic groups are chemically bonded to a polymer chain, while gel polymer electrolytes are solvated by a high dielectric constant solvent and are free to move. In a classical gel electrolyte, polymer and salts are mixed with a solvent, usually having a concentration above 50 wt%, and the role of the polymer is to act as a stiffener for the solvent, creating a three-dimensional network, where cations and anions move freely in the liquid phase [88]. The solid polymer electrolyte includes poly(ethylene oxide) (PEO)-based lithium ion conductors that typically show conductivities of 10 S cm while the gel polymer electrolytes have semisolid character with much higher ionic conductivities of the order 10 —10 S cm . ... 

Polymer-based ion conducting materials have been of great interest to researchers in the field of lithium batteries since Armand et al proposed the use of poly(ethylene oxide) (PEO)-Li salts as a solid polymer electrolyte (SPE). In this application, the polymer electrolyte functions as a mechanical separator between the two electrodes and also as the ionic conductor. Polymer electrolytes are used in the form of thin films and may be either dry (organic solvent-free) or plasticised. A high specific energy density can be reached at medium temperature using a dry polymer electrolyte and lithium metal as the negative electrode. 

The ionic conductivity of polymer electrolytes is affected not only by the ionic mobility, but also by the number of carrier ions. It is unlikely that salts incorporated at such high concentrations dissociate completely in these media of relatively low polarity. Thus, a part of an incorporated salt may dissociate to free ions, which function as carrier ions, but we cannot deny the possibility of the presence of aggregated ions, so-called ionic multiplets. The energetics for the formation of ionic aggregates have been studied as a function of the dielectric constant of the solvent and of the salt concentration in electrolyte solutions [64]. If the incorporated salts are partially dissociated, the number of carrier ions will be influenced by the incorporated salt species, its concentration, temperature, and the polymer structure. 

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