6 Lithium polymer batteries Bruno Scrosati and Robin J. Neat 6.1 INTRODUCTION The discovery and the characterization of ionically conducting polymeric membranes (see Chapters 1 and 2) have provided the interesting possibility of developing new types of lithium batteries having a thin-layer, laminated structure. Various academic and industrial laboratories [1-5] are presently engaged in the development of this revolutionary type of battery, ic. the so-called Lithium Polymer Battery (LPB). The key component of the LPB is the polymeric ionic membrane which acts both as electrolyte and separator; furthermore, the membrane can be easily fabricated in the form of a thin film (typically 50 am thickness) by a number of convenient casting techniques. For instance, in the common case of a membrane formed by the combination of poly(ethylene oxide) (PEO) and a lithium salt, LiX (see Chapter 1), the laboratory preparation procedure involves the dissolution of the two components in a suitable solvent (e.g. acetonitrile), the mixing and the homogenization of the two in a single solution and the slow evaporation of the solvent (Figure 6.1), This casting procedure, which can be scaled up with the use of automatic lamination machines (sce Section 6.6), is simple and versatile since it allows us to obtain membranes of various desired forms (depending on the shape of the solution holder) and of different thickness (depending on the conditions of casting procedure). The casting procedure illustrated in Figure 6.1 gives polymer membranes which are thin, flexible, processable and ionically conductive. This provides electrolyte: materials which have mechanical properties typical of plastics and electrical properties typical of electrolytes. Such a unique combination allows us to consider revolutionary designs for the realization of advanced electrochemical devices. For instance, if the electrode components can be formed in flexible, thin configurations similar to that of the electrolyticIntroduction 183 PREPARATION OF PEO-LiX POLYMER MEMBRANES CH,CN. ‘CH3CN SOLUTION SOLUTION OF _Lix OF PEO NY MIXED CHjCN SOLUTION PEON CASTING sin (room temperature) \ TEFLON HOLDER PEO =poly(ethilene oxide) LiX =lithium salt Figure 6.1 Schematic illustration of the casting fabrication procedure of a polymer ionic membrane formed by PEO-LiX. membrane, batteries of otherwise impossible geometry can be readily conceived. Figure 6.2 shows a popular drawing proposed in the early 1980s by Harwell Laboratory [6, 7] in which various alternative versions of extended area polymer batteries were envisaged. The fabrication feasibility of these thin-film, revolutionary structures has been demonstrated and this places LPBs among the most promising advanced power sources for a series of applications of crucial importance for our society. Today, the lithium polymer battery is a valid candidate for the consumer electronics market as a replacement for the nickel-cadmium battery (with benefits in environ- mental control), for the electric vehicle as a replacement for the lead-acid battery (with gains in driving range) or the sodium-sulphur battery (with improvements in safety concern). In summary, the LPB is an innovative, all- solid-state battery system which, by combining the versatility of the poly- meric structure with the high energy of the electrodic couples, is capable of providing outstanding performance in terms of energy density, reliability and safety. If successfully developed the LPB can assume a leading role in