Polymer Electrolytes for Lithium-Ion Batteries

By Wolfgang H. Meyer*
The motivation for lithium battery development and a discussion of ion conducting polymers as separators begin this review, which includes a short history of polymer electrolyte research, a summary of the major parameters that determine lithium ion transport in polymer matrices, and consequences for solid polymer electrolyte development. Two major strategies for the application of ion conducting polymers as separators in lithium batteries are identified: One is the development of highly conductive materials via the crosslinking of mobile chains to form networks, which are then swollen by lithium salt solutions (gel electrolytes). The other is the construction of solid polymer electrolytes (SPEs) with supramolecular architectures, which intrinsically give rise to much enhanced mechanical strength. These materials as yet exhibit relatively common conductivity levels but may be applied as very thin films. Molecular composites based on poly(p-phenylene)- (PPP)-reinforced SPEs are a striking example of this direction. Neither strategy has as yet led to a breakthrough with respect to technical application, at least not for electrically powered vehicles. Before being used as separators, the gel electrolytes must be strengthened, while the molecularly reinforced solid polymer electrolytes must demonstrate improved conductivity. siderably supported.[1] The history of the development of secondary lithium batteries has recently been reviewed by Brandt.[3] There are two major arguments for a lithium-ion battery: lithium is the lightest element that can safely be handled in electrochemical processes and it exhibits the highest oxidation potential of any element, properties that make lithium ideally suited for high energy density batteries. However, lithium-metal electrodes in contact with liquid electrolytes cause a variety of problems, which in the worst case can lead to fires and explosions. Therefore, the most promising approach is that of the rocking chair cell, in which the lithium metal is replaced by a lithium-ion source.[4] During charging and discharging of such batteries, lithium ions are rocked between lithium-carbon and lithiummetal oxide intercalation compounds, which act as the electrode couple. A typical example is displayed in Figure 1, in which LixC6 is used as anode and LixMn2O4 (a spinel) as cathode. Insertion compounds as electrode materials for rocking chair Li batteries have recently been reviewed by Scrosati[5] and Koksberg et al.[6] Because of the high oxidation potential of the metal oxide cathodes, these batteries may suffer from decomposition reactions of the liquid organic solutions used as electrolyte. Therefore, the replacement of the liquid electrolyte with a thin polymer membrane would be highly desirable. According to Figure 1, the electrolyte serves as a medium to transport the ions involved in the charging/discharging cycle of the cell. In addition, a separator has to isolate the anode from the cathode electronically. While ceramic or polymeric separators have to be placed between the electrodes when liquid electrolytes are used, both functionsion conduction and separationcan be realized in a single thin membrane when polymer electrolytes are used.
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1. Introduction
At the turn of the millennium the consciousness of the need to use energy more efficiently spread, at least in the developed countries. The efficient use of energy also includes efficient storage of electricity, meaning that one needs to have high energy density batteries that have low energy losses during storage, electrical charging and discharging, and last, but not least, batteries with long lifetimes and a minimum of production and disposal costs. The general motivation for the development of advanced batteries is further augmented by the California zero-emission standard, which requires 2 % of all new vehicles produced by a car manufacturer to be zero emission, i.e., electrically powered, from 1998 onwards. To meet these requirements, the US Advanced Battery Consortium (USABC, a partnership of car manufacturers and the electric utility industry) was formed in 1991 to develop batteries that would allow electric vehicles to perform as well as and be cost competitive with gasoline powered vehicles in the late 1990s.[1] Thus a battery with an energy density of at least 120 W h/kg, a stability of more than 1000 charging/ discharging cycles, a lifetime of at least 5 years and a reasonable cost became the target. In the last decade a number of different battery systems were found to meet the requirements of electric vehicle batteries, among which are the nickel-metal hydride, the sodium-sulfur, and the lithium-ion systems.[2] In the USA besides the nickel system the lithium-ion battery is considered to be most promising and thus its development is con [*] Dr. W. H. Meyer Max-Planck-Institut fr Polymerforschung Ackermannweg 10, D-55128 Mainz (Germany) Adv. Mater. 1998, 10, No. 6

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Fig. 1. Schematic illustration of a lithium rocking chair battery with graphite and spinel as intercalation electrodes and its electrode reactions (after [5]).

However, in batteries to be used for electrically powered vehicles, such a polymer electrolyte membrane ought to exhibit ion conductivities better than 105 S/cm in the temperature range from 20 C to +60 C, and they should be mechanically, thermally, and electrochemically stable at least within that temperature range. A comparison of the electrochemistry of polymer electrolytes and liquid electrolytes was given very recently by Armand and co-workers.[7]

2. Solid Polymer Electrolytes

After P. V. Wright's discovery of ionic conductivity in alkali metal salt complexes of poly(ethylene oxide) (PEO) in 1973,[8] polymer electrolytes were proposed for batteries in 1978 because they combine the advantages of solid-state electrochemistry with the ease of processing inherent to plastic materials.[9] Polymer electrolytes are solid solutions

of alkali metal salts in polymers (not to be mixed up with polyelectrolytes, in which either the cation or the anion is covalently fixed to the polymer repeat unit). Since that time, the number of contributions to the field of SPEs has grown enormously, reflecting progress in the understanding of molecular and supramolecular architecture, which is prerequisite for fast ion transport in polymers (for a historical review read the article by Armand[10]). Initially it was assumed that the crystalline domains are responsible for ion transport, with the ions moving along the PEO helices as the primary mechanism; however, it was soon established that the amorphous phase alone gives rise to ion transport.[11] Oligoethers seem to be a prerequisite for good solubility of alkali salts, since most of the polymer electrolytes contain these moieties as constitutive units either in their main or side chains. This is not surprising, since linear oligo(ethylene oxide)s form complexes with cations, and the cyclic oligomerscrown ethersare well known for their excellent metal-complexing capabilities.[12] In order to facilitate the dissociation of inorganic salts in polymer hosts, the lattice energy of the salt should be low and the dielectric constant (e) of the host polymer should be high. Consequently, the ionic conductivities of amorphous mixtures of Li salts with poly(propylene oxide) (PPO) are considerably smaller compared to equivalent mixtures with PEO because PPO has a lower e and its methyl groups hinder the complexation of Li+. The ionic conductivity can be roughly expressed by s = nem, where n, e, and m are the effective number of mobile ions, the elementary electric charge, and the ion mobility, respectively. Since the fraction of free ions that can be effectively transported is an important parameter, a high degree of dissociation of the salt in the polymer is a prerequisite for high conductivity. The degree of dissociation of the salts dissolved in the polymer host depends, however, on the total concentration of salt in the matrix. Generally, the degree of dissociation decreases with increasing salt concentration. As a consequence, the fraction of free ions has a maximum at an optimal salt concentration, which in many cases is located around Li/O 0.04 (the molar ratio of lithium (salt) over oxygen (of ethylene oxide units)).

Wolfgang H. Meyer earned his Ph.D. at the University of Freiburg, Germany, in 1977 with a thesis on the solid-state photopolymerization of diolefins. From 1978 to 1984 he was a researcher at RCA Laboratories Ltd. in Zurich, Switzerland, with electronically conducting polymers and high-resolution photoresists as his areas of interest. In 1984 he joined the Max Planck Institute for Polymer Research in Mainz, Germany, where he is presently responsible for research in the following fields: ion-containing polymers and networks, surface-active polymers, and thermoanalysis. 440
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Another requirement is a high Li+ transference number, i.e., a high ratio of the charge transported by Li+ compared to the total charge transported. The influence of the ion ion and ionpolymer as well as ionplasticizer interactions on the ion transport in SPEs has been an important subject of research in recent years.[10,13] While in polymer electrolytes both the cations and the anions may contribute to the ion conductivity, polyelectrolytes with the anions fixed to the polymer chain are singleion conductors in which only the cations are mobile. Several kinds of Li+ single-ion conducting polymers have been proposed, but the conductivities of such systems turned out to be only about 1 % that of ordinary SPEs. This is mainly attributed to the insufficient dissociation of Li+ in such materials.[14] To date, no single-ion conducting polymers that possess sufficient conductivities to be useful in Li batteries are known. The thermodynamics of the salt dissociation in PEO has been discussed in detail by Papke et al.[15] Molecular dynamics simulations suggest that the Li+ ions are complexed to PEO through approximately five ether oxygens of a PEO chain, and that the mobility of the cations is decreased considerably by this complexation.[16] Consequently, the mobility of the Li cations is related to the motions of the complexing segments of the PEO chain. Thus, the cation transport is described as the motion of the Li+ species between complexation sites assisted by the segmental motion of the PEO matrix (see Fig. 2). The temperature dependence of the ion conductivity in SPEs scales with the temperature dependence of the segmental motions and thus with the glass transition phenomena. Therefore, the temperature dependence of the ion conductivity is usually discussed in the framework of the free volume model and can be described by the WLF (WilliamsLandelFerry) equation (for a comprehensive discussion of the conduction mechanisms in SPEs and their theoretical treatment see the literature[17]). A consequence of the correlation between the segmental motion of the host polymer and the efficiency of ion transport was the search for low-Tg materials, i.e., host polymers with softening temperatures as low as possible, with the hope to achieve high ion conductivities at ambient temperatures. One approach was the combination of dimethylsiloxane (DMS) units and short PEO segments to form linear chain copolymers (1), as it was expected that the DMS units de-

crease the softening temperature of the copolymers without decreasing the solubility of the Li salts. With a LiClO4 concentration of Li/O = 0.04 these materials exhibit a Tg of 80 C and conductivities of 1.6 104 S/cm (LiClO4) at room temperature (RT)[18] (the chemical structure of the materials 19 is displayed in Table 1).
Table 1. Chemical structure of SPE materials 16 and plasticizers 79.

Fig. 2. Schematic of the segmental motion assisted diffusion of Li+ in the PEO matrix. The circles represent the ether oxygens of PEO. Adv. Mater. 1998, 10, No. 6 WILEY-VCH Verlag GmbH, D-69469 Weinheim, 1998 0935-9648/98/0604-0441 $ 17.50+.50/0

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In addition to linear chain polymers, a variety of combbranched polymers was investigated, in which PEO side chains were attached to a polymer backbone, which itself had a low glass transition temperature and thus giving rise to a more flexible system. Polysiloxanes with PEO side chains were first synthesized by Hall et al.[19] and Smid and co-workers.[20] Later similar systems were investigated by Spindler and Shriver and Ni et al.[21] These systems are liquids at RT with conductivities of the LiClO4 (Li/O 0.04) mixtures of around 104 S/cm (2). However, their chemical stabilities are poor due to the SiOC branched side chains. Smid and co-workers enhanced their chemical stability by connecting the PEO branches via a SiC bond (3).[22] Shriver and coworkers studied comb-branched systems based on polyphosphazene (MEEP) backbones and PEO side chains, which are completely amorphous with glass transition temperatures around 80 C. However, the room-temperature conductivities of the F3CSO3Li salt mixtures with MEEP (Li/O 0.04) did not exceed the 105 S/cm benchmark by much (4).[23] Obviously, some improvements have been achieved with low Tg host polymers compared, for example, to ordinary PEO Li salt mixtures 5, since the conductivities of these materials have become comparable with those of low molecular weight liquid electrolytes such as TEGDME (tetraethylene glycol dimethyl ether, 7). However, the drawbacks of such materials are their complex chemistry and lack of mechanical stability. Besides, a comparison with other comb-type polymers based on less mobile polymethacrylates or polystyrenes shows that conductivities can reach similar values when the PEO side chains are longer or if they are mechanically decoupled from the (stiff) polymer backbone by spacer groups. For example, Inoue et al. reported that polystyrene (PS) derivatives with PEO side chains linked via phosphazene spacers to the PS backbone exhibit conductivities of the LiClO4 salt mixtures (Li/O = 0.035) approaching 105 S/cm at RT (6).[24] In Figure 3, the temperature dependence of the conductivities of some typical low-Tg SPEs are compared with that of the prototype SPE, a PEO Li salt mixture (5), and a low molecular weight liquid analogue. The conductivity data reported in the literature for prototype SPE, however, vary considerably between different authors, which is probably a consequence of the complex phase behavior of PEO salt mixtures. The situation is complicated by the different strategies used to avoid crystallization of PEO, so that materials and data often cannot be directly compared with each other. While Takeoka et al. report a rather strong conductivity decrease of amorphous PEO/F3CSO3Li (5, Fig. 3) with decreasing temperature,[14] Nicholas et al. describe the conductivity of oxymethylenelinked PEO/F3CSO3Li to be much improved and considerably less temperature dependent (the conductivity curve being almost identical with that of 3, Fig. 3).[25] The development of SPEs has been described in detail by different authors recently.[10,14,26] 442
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Fig. 3. Temperature dependence of the conductivities of typical low-Tg SPEs, materials 1, 2, 3, 4, and 6 as compared to the prototype, PEO (5), and to a low molecular weight liquid electrolyte, TEGDME (7), all as Li salts with concentrations of Li/O 0.04 (see Table 1 for the chemical structures).

3. SPE Networks and Gels

Crosslinked polymer electrolytes, SPE networks, do not crystallize and offer the advantage of good mechanical properties, which make them attractive for use in thin films and membranes.[27] Some materials have been prepared in which the formation of a network is based on phase separation, i.e., temporary physical crosslinks, which impart interesting processibility, as is typical of thermoplastic elastomers. However, the disadvantage of this approach is that a considerable volume fraction of the phase-separated materials does not contribute to conductivity, with the overall result of poor performance with respect to conductivity. Therefore, chemically crosslinked SPEs, in which the crosslinks consume only a negligible volume fraction, appeared to be the best choice to optimize conductivity as well as mechanical properties. A variety of chemical SPE networks have been investigated, among which are networks based on hydroxy-terminated polyethers crosslinked with di- or triisocyanates,[27] allyl-terminated polyethers crosslinked with hydrosiloxanes,[28] and polyethertriols crosslinked with diisocyanates or glycidyl ethers or by UV irradiation.[29] In Figure 4, the temperature dependence of the ionic conductivity of some relevant SPE networks are displayed (the chemical structure of the materials 1014 are displayed in Table 2). The glass transition temperature in such SPE networks increases with the crosslink density. In some cases a linear relationship between the reciprocal Tg and the crosslink density is observed.[27] With respect to the mechanical properties of SPE networks, the frequencytemperature superposition applies very well and follows WLF behavior;[30] thus, the mechanical moduli increase with increasing
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Fig. 4. Temperature dependence of the conductivities of some typical dry network SPEs, materials 1014 (see Table 2 for the chemical structure and the composition of the materials).

crosslink density. As the correlation between ionic and segmental motion also holds for the network case, the crosslink density was found to affect the ionic conductivity by restricting the segmental mobility of the host.[31] Therefore, the conductivities of network SPEs are usually some orders of magnitude lower than those of the equivalent uncrosslinked systems. However, Tada et al. have studied polyphosphazenes with oligo(ethylene oxide) side chains that were partly allyl terminated and could be crosslinked by UV irradiation. They did not find any differences between the ionic conductivities of the LiClO4 mixtures before and after
Table 2. Basic network structure and composition of SPE materials 1014.

photocrosslinking.[32] The degree of crosslinking could not be determined exactly, and the high mobility of the phosphazene backbone may also explain the discrepancy between the results of this work and those mentioned earlier. Since the segmental motion of the polymer host matrix has been identified as the main parameter controlling conductivity, it was tempting to use plasticizers, which act as internal lubricants and depress the Tg of the host, to improve the conductivity.[33] To be effective, however, large weight fractions of additives like TEGDME 7, propylene carbonate (PC, 8) or ethylene carbonate (EC, 9), are required, so that the mechanical properties of linear chain SPEs become rather unpractical. In the case of crosslinked SPEs, however, the situation may be different. SPE networks with a low to moderate crosslink density can be swollen with plasticizers to a large extent, which themselves are excellent solvents for Li salts. These gel SPEs combine the mechanical properties of a swollen polymer network with the high ion conductivities of liquid electrolytes. Consequently, the field of gel SPEs has recently become most attractive. In Figure 5 the temperature dependence of the ionic conductivity of the phosphazene-based SPE network described by Tada et al. is displayed as an example of a dry network (15, 6 wt.-% LiClO4, Li/O = 0.028) and the same network swollen with propylene carbonate (16, 11 wt.-% LiClO4, 60 wt.-% PC, Li/O = 0.043) as an example of a gel SPE. Obviously, the effect of the plasticizer is enormous, since the room-temperature conductivities reach almost the upper limit of typical organic liquid/salt solutions, e.g., 102 S/cm for LiClO4 for a dimethyl ether/PC mixture[32] (the chemical structure of the materials 15 and 16 are displayed in Table 3).

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Table 3. Chemical structure of SPE network and composition of materials 15 and 16.

considerable amounts of organic liquids. The electrochemical stability of some of these liquids is rather limited under the working conditions of a rocking chair Li battery, as already discussed. In addition, most separator applications require the processing of the SPE material in the shape of thin films, which may be a problem when SPE networks are the candidates. Processing from linear SPE precursors with subsequent photocrosslinking may result in impurities due to light-induced side reactions, which give rise to the malfunction of the electrochemical cell. Finally, under safety considerations the gel SPEs at present are not optimized for the demanding working conditions of Li batteries in automotive applications, but under less stringent conditions they are useful.

4. Molecularly Reinforced SPE

Fig. 5. Comparison of the temperature dependence of the ionic conductivity of a dry MEEP-based SPE network (15) and the same network swollen with plasticizer (16) (see Table 3 for the chemical structure of the materials).

Since gel SPEs are multicomponent systems, relatively little is known about their structure and the ion transport mechanisms. Recently, MacFarlane et al. presented a comprehensive study on the influence of the plasticizer on the electrochemical and mechanical properties of urethane crosslinked polyethers plasticized with N,N-dimethylformamide (DMF) and PC.[34] It was shown that, in addition to the mere plasticizing effect, DMF and PC increase the concentration of charge carriers. Reiche et al. investigated gel SPEs on the basis of oligo(ethylene glycol)dimethacrylate networks [(EG)23DMA] which had been swollen with various plasticizers.[35] They found that the extent of dissociation of the salt can be improved by the increase of the gel polarity when polar plasticizers are used or when polar comonomers were introduced into the network structure. Polar plasticizers with low molecular weight exhibit high selfdiffusion in the gel and give rise to high ion conductivity, however, with low cationic transference numbers.[36] From the magnitude of the conductivity of gel SPEs it can be concluded that the optimum material for application as separators in solid-state batteries has been found. However, the high conductivities in such systems are based on 444
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SPE materials with high mechanical strength have been obtained using stiff macromolecules as reinforcing backbone moieties and flexible side chains as the liquid matrix for ion transport.[37] The use of such materials as separators in Li batteries offers the advantage of minimizing the separator thickness and thus the internal electrical resistance of a lithium solid-state cell. These materials belong to the class of hairy rod molecules,[38] which have a strong tendency to self-organize into supramolecular architectures when cast from solution. The concept of hairy rod molecules represents one way to overcome the compatibility limitations of rigid and flexible polymer materials and these materials can thus be regarded as molecular composites, where both components are disperse on a molecular level. Lauter et al. used poly(p-phenylene) (PPP) as the rigid backbone with flexible oligo(ethylene oxide) (EO) side chains attached, which form the liquid matrix in which Li salts can be dissolved and in which ionic transport takes place (material 17 in Table 4, the materials are named PPP(EO)x/y with x/y indicating the number of ethylene oxide units in the side chains of a copolymer in which the side chains (EO)x and (EO)y are distributed at random). From thermoanalysis and X-ray investigations it has been confirmed that the self-organization in these materi0935-9648/98/0604-0444 $ 17.50+.50/0 Adv. Mater. 1998, 10, No. 6

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Table 4. Chemical structure of molecular composite SPE and composition of materials 1721.

[a] Only the oxygens of the oligo(ethylene oxide) side chains have been considered. [b] Oxygens of side chains and plasticizer have been considered.

als gives rise to a superstructure in which the PPP backbones are arranged in layers that are separated by the liquid EO matrix, as indicated in Figure 6a. This superstructure, which is responsible for the outstanding mechanical properties of these materials, can be described as a smectic B-type liquid-crystalline phase, which remains unaltered up

Fig. 6. Model of the superstructure of a PPP-reinforced SPE (17) without (a) and with (b) LiCF3SO3 (LiOTf): the PPP backbones (bars) are arranged in layers separated by the EO matrix; the layer distance increases with the introduction of Li salt (LiOTf) (after [37]). Adv. Mater. 1998, 10, No. 6

to temperatures well above 150 C, when a phase transition leads to a liquid-crystalline phase with lower order. Finally, at still higher temperatures an isotropic melt is obtained.[39] The distance between the PPP layers, and hence the volume of the EO matrix, increases with the side chain length. When PPP(EO)x/y films are cast from solution, the PPP layers are preferentially oriented parallel to the film plane. However, since the layered superstructure exists in domains of only nanometer size, the preferential layer orientation does not give rise to a macroscopic anisotropic conductivity behavior.[40] Surprisingly, the softening behavior of the EO matrix is decoupled from the PPP backbone structure. The EO side chain matrix, composed of units as short as (CH2CH2O)3, exhibits a glass transition temperature as low as around 50 C, and the Tg decreases further with increasing side chain length, approaching the Tg of amorphous poly(ethylene oxide) when x + y = 11 (compare Fig. 7). Thus, although the EO side chains are chemically linked to the stiff PPP backbones, their behavior is liquid-like as in amorphous PEO well below room temperature. As can be expected, the glass transition temperature in PPP(EO)x/y increases when Li salts are dissolved in the EO matrix, e.g., from 63 C (no salt) to 16 C (Li/O = 0.10) in PPP(EO)5/6 upon addition of F3CSO3Li (LiOTf) (compare Fig. 7). In addition, the introduction of a salt into the EO matrix leads to an increase of the PPP layer distance and thus to an expansion of the crystallographical c axis (Fig. 6b). From concentration-dependent X-ray investigations it was confirmed, that LiOTf remains in the side chain matrix and affects neither the packing of the PPP backbones nor their
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Fig. 7. Variation of the glass transition temperature (Tg ) in PPP(EO)5/6 (17) with LiCF3SO3 (LiOTf) concentration Li/O (upper x axis) and as a function of the oligo(ethylene oxide) side chain length in PPP(EO)x/y in which x and y have been varied (the sum of x + y are displayed on the lower x axis) (after [40]).

phase transition at elevated temperatures. However, this is not necessarily true in cases when other Li salts are used.[40] In order to prove the accuracy of the concept of preparing molecular composite materials with improved mechanical strength, the viscoelastic behavior of these materials was analyzed. Figure 8 shows the temperature dependence

separators it is even more advantageous that the blending of PPP(EO)5/6 with Li salt gives rise to shear moduli that are about one order of magnitude higher than those of the pure polymer materials. This clearly demonstrates the reinforcing effect of the layered superstructure of the PPP backbones and proves the concept. The ionic conductivities of PPP(EO)x/y materials blended with Li salts are comparable to those of similar SPEs that consist of helical polyglutamate backbones with EO side chains (which, however, lack the desired reinforcing effect).[41] This is not surprising since, depending on the side chain length, the volume fraction of the EO matrix in which the ion transport takes place is only in the range 4060 %. Consequently, the best conductivities are found for materials with the longest EO side chains (as long as crystallization of the PEO matrix can be avoided). However, since the formation of the desired layer structure of the PPP backbones, which is responsible for the reinforcing effect, is lost when the side chain length increases too much, an optimum between best conductivity and best reinforcing effect is found in PPP(EO)5/6. The temperature dependence of the DC conductivity of this material blended with LiOTf is displayed in Figure 9 (material 17). The details of the influence of side chain length, salt type, and salt concentration on the DC conductivities of PPP-reinforced SPEs has been discussed recently.[37] Further improvement of the ionic conductivity of the PPP-reinforced SPEs was attained by plasticizing with TEGDME so that room-temperature conductivities around 104 S/cm were obtained, however, at the expense of the mechanical properties of the materials (Fig. 9, material 18). The same rules hold for PPP backbonereinforced SPEs as for other SPEs: single-ion conductors generally exhibit lower conductivities compared to their multi-ion counter-

Fig. 8. Temperature dependence of the shear moduli G and G of SPE material 17 with and without Li salt (LiCF3SO3, Li/O = 0.04) (after [37]).

of the storage moduli G of PPP(EO)5/6 (material 17) with and without Li salt, as well as the loss moduli G of the same materials. At very low temperatures, in the glassy state of PPP(EO)5/6, the moduli exhibit values of about 109 Pa, and decrease by 12 orders of magnitude as the EO matrix undergoes its glass transition. In the temperature range relevant to application, from about 20 C to well above 100 C, the moduli remain at rather high plateau values between 107 and 106 Pa, which are comparable to that of a hard rubber material. At temperatures above 150 C, a strong decrease of the moduli is observed as a result of the phase transition. For the application of these materials as 446
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Fig. 9. Temperature dependence of the DC conductivities of poly(p-phenylene) based SPE materials 1721 (the chemical structure and composition of the materials is displayed in Table 4).

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parts. This has been nicely demonstrated by a systematic investigation of PPP derivatives with EO side chains plus lithium sulfonate groups attached to the PPP backbones (materials 19 and 20, Table 4).[42] Although the lithium sulfonate to EO side chain molar ratio was chosen such that Li/O 0.04 (material 19), the DC conductivity of such a material was found to be approximately two orders of magnitude lower than that of the corresponding PPP(EO)5/6 / LiOTf blend with the same Li/O ratio (material 17/Fig. 9). The conductivity values become even worse as the sulfonate to EO side chain ratio is increased (Li/O = 0.362, material 20/Fig. 9). Thus, increase of the molar concentration of the Li sulfonate moieties does not automatically lead to higher conductivities, either because the number of free, i.e., mobile, charge carriers is not increased, or because the mobility of the ionic species is drastically reduced owing to the lack of segmental motion of the matrix. Consequently, when the matrix is plasticized by the addition of large amounts of TEGDME (material 21/Fig. 9), the ionic conductivity increases dramatically and becomes comparable to that of the corresponding multi-ion conducting SPE with the same Li/O ratio.[43] Surprisingly, the addition of large quantities of plasticizer (72 wt.-%) does not lead to a liquid-like material, but films prepared from 21 are not even slightly sticky and exhibit surprisingly good mechanical properties. This appears to be the result of the reinforcing effect of the rigid PPP backbones, which again proves the concept of the molecular composite SPE material to be successful. However, one disadvantage of the PPP-based SPEs should not be glossed over: under certain conditions of use as separator the PPP backbones may be electrochemically unstable since they are able to undergo redox reactions owing to their p-conjugated electronic structure. Thus, the concept works with regard to supramolecular architecture but needs to be improved with respect to electrochemical stability.

stability under battery working conditions and have to be improved mechanically, while the reinforced SPEs are mechanically acceptable but have to be improved with respect to their conductivity values. This assessment of the field of SPEs is, of course, a personal view and can neither be objective nor complete. For example, SPEs based on primary chemical structures other than ethylene oxide have not even been mentioned and phase-separated SPEs on the basis of copolymers and blends have not been discussed in this short review. For a comprehensive survey the readers are referred to the literature,[10,14,26] or to the monograph by F. Gray that appeared very recently,[44] or to the proceedings of the International Symposium on Polymer Electrolytes, which are published biennially in Electrochimica Acta.
Received: August 22, 1997 Final version: November 10, 1997 [1] J. Krieger, Chem. Eng. News 1992, 16, 17. [2] For a survey see for example: Solid State Batteries (Eds: C. A. C. Sequeira, A. Hooper), NATO ASI Series E, Vol. 101, Martinus Nijhoff, Dordrecht, The Netherlands 1985. [3] K. Brandt, Solid State Ionics 1994, 69, 173. [4] B. Scrosati, JEC Battery Newsletters 1993, 6, 44, 53. [5] B. Scrosati, in Electrochemistry of Novel Materials (Eds: J. Lipkowski, P. N. Ross), VCH, Weinheim 1994, Ch. 3. [6] R. Koksberg, J. Barker, H. Shi, M. Y. Saidi, Solid State Ionics 1996, 84, 1. [7] D. Baril, C. Michot, M. B. Armand, Solid State Ionics 1997, 94, 35. [8] D. E. Fenton, J. M. Parker, P. V. Wright, Polymer 1973, 14, 589. [9] M. Armand, M. Duclot, French Patent 78 329 76, 1978. [10] M. B. Armand, Solid State Ionics 1994, 69, 309. [11] C. Berthier, W. Gorecki, M. Minier, M. B. Armand, J. M. Chabagno, P. Rigaud, Solid State Ionics 1983, 11, 91. [12] F. Vgtle, E. Weber, in Crown Ethers and Analogs (Eds: S. Patai, Z. Rappoport), Wiley, NewYork 1989, Ch. 4. [13] P. G. Bruce, C. A. Vincent, Faraday Discuss. Chem. Soc. 1989, 88, 43. [14] S. Takeoka, H. Ohno, E. Tsuchida, Polym. Adv. Technol. 1993, 4, 53. [15] B. L. Papke, M. A. Ratner, D. F. Shriver, J. Electrochem. Soc. 1982, 129, 1694. [16] F. Mller-Plathe, W. F. van Gunsteren, J. Chem. Phys. 1995, 103, 4745. [17] M. A. Ratner, in Polymer Electrolyte Reviews-1 (Eds: J. R. MacCallum, C. A. Vincent), Elsevier Applied Science, New York 1987, Ch. 7. [18] K. Nagaoka, H. Naruse, I. Shinohara, M. Watanabe, J. Polym. Sci., Polym. Lett. Ed. 1984, 22, 659. [19] P. G. Hall, G. R. Davis, J. E. McIntyre, I. M. Ward, D. J. Banister, K. M. F. Le Brocq, Polym. Commun. 1986, 27, 98. [20] D. Fish, I. M. Khan, J. Smid, Macromol. Chem. Rapid. Commun. 1986, 7, 115. [21] R. Spindler, D. F. Shriver, J. Am. Chem. Soc. 1988, 10, 3036. J. Ni, Y. Lin, F. Wang, Polym. Adv. Technol. 1993, 4, 80. [22] D. Fish, I. M. Khan, J. Smid, Br. Polym. J. 1988, 20, 281. [23] P. M. Blonsky, D. F. Shriver, P. Austin, H. R. Allcock, J. Am. Chem. Soc. 1984, 106, 6854. [24] K. Inoue, Y. Nishikawa, T. Tanigaki, Macromolecules 1991, 24, 3464. [25] C. V. Nicholas, D. J. Wilson, C. Booth, J. R. M. Giles, Br. Polym. J. 1988, 20, 289. [26] M. Armand, J. Y. Sanchez, M. Gauthier, Y. Choquette, in Electrochemistry of Novel Materials (Eds: J. Lipkowski, P. N. Ross), VCH, Weinheim, 1994, Ch. 2.6. [27] J. F. LeNest, A. Gandini, H. Cheradame, Br. Polym. J. 1988, 20, 253. H. Cheradame, J. F. LeNest, in Polymer Electrolyte Reviews-1 (Eds: J. R. MacCallum, C. A. Vincent), Elsevier Applied Science, New York 1987, Ch. 5. [28] L. Lestel, S. Boileau, H. Cheradame, Proc. 2nd Int. Symp. on Polymer Electrolytes (Ed: B. Scrosati), Elsevier Applied Science, New York 1990, p. 143. [29] M. Kono, K. Furuta, S. Mori, M. Watanabe, N. Ogata, Polym. Adv. Technol. 1993, 4, 85. 0935-9648/98/0604-0447 $ 17.50+.50/0

5. Conclusions
Two major directions have emerged in the development of solid polymer electrolytes in recent years: One is the development of highly conductive materials via the crosslinking of mobile chains to form networks, which are then swollen by lithium salt solutions (gel electrolytes). Thus, the matrix in which the ion transport occurs is liquid-like. The other direction is the construction of SPEs with supramolecular architectures, which intrinsically gives rise to much enhanced mechanical strength. This type of materials usually exhibits relatively common conductivity levels but may be applied as very thin films. Molecular composites based of PPP-reinforced SPEs are a striking example of this direction. However, both directions have to merge: the gel-electrolytes exhibit excellent conductivities but still lack chemical
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U. Lauter, W. H. Meyer, G. Wegner, Macromolecules 1997, 30, 2092. G. Wegner, Mol. Cryst. Liq. Cryst. 1993, 235, 1. U. Lauter, W. H. Meyer, V. Enkelmann, G. Wegner, unpublished. U. Lauter, Ph.D. Thesis, University of Mainz 1997. M. Watanabe, S. Aoki, K. Sanui, N. Ogata, Polym. Adv. Technol. 1993, 4, 179. [42] P. Baum, Diploma Thesis, University of Mainz 1997. [43] P. Baum, W. H. Meyer, G. Wegner, unpublished. [44] F. Gray, Polymer Electrolytes, RSC materials monographs, Royal Society of Chemistry, Cambridge 1997.

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