Aqueous batteries, separator

Composite structures that consist of carbon particles and a polymer or plastic material are useful for bipolar separators or electrode substrates in aqueous batteries. These structures must be impermeable to the electrolyte and electrochemical reactants or products. Furthermore, they must have acceptable electronic conductivity and mechanical properties. The physicochemical properties of carbon blacks, which are commonly used, have a major effect on the desirable properties of the conductive composite structures. Physicochemical properties such as the surface... 

The aqueous batteries use water based electrolytes (e.g., KOH electrolyte for NiCd and NiMH and H2-SO4 electrolyte for lead acid), which are less resistive then nonaqueous electrolytes. Polyolefin materials are generally suitable for use in the manufacture of separators for these batteries, but they are not inherently wettable by aqueous electrolytes. Such electrolytes are therefore unable to penetrate the pores of a separator formed from such a material, so that ion migration through the pores in solution will not occur without modification. This problem is sometimes overcome by treating the polyolefin material with a surfactant, which allows an aqueous electrolyte to wet the material. However, such surfactant can be removed from the surfaces of the polyolefin material when electrolyte is lost from the device, for example during charging and discharging cycles, and it is not subsequently replaced on the material when the electrolyte is replenished. 

This subsequent section discusses different types of aqueous batteries and the separators used in those batteries. The recent work in the development of new separators for aqueous batteries will also be discussed in detail. 

The reaction of lithium with the electrolyte to form a surface film significantly modifies its behaviour. On the one hand, the film confers chemical stability and useful shelf life on the system. On the other, it is responsible for greatly depressed exchange currents and the consequent phenomenon of voltage delay, as discussed in Chapter 3 in connection with magnesium aqueous batteries. It is convenient to discuss separately film formation with insoluble and with liquid and soluble cathode systems. 

Some battery separators are swollen by battery electrolyte solutions and function as a solid polymer matrix with mobile conducting ions. In the last few years a number of alkali metal containing polymers, usually based upon poly(ethylene oxide) or derivatives thereof, have been described for use with non-aqueous Li based batteries. 

In addition, the various types of polymer ionics can be easily fabricated into flexible thin films with large surface areas where the ions are free to move and can conduct electricity as in conventional liquid electrolytes. This has opened the challenging possibility of replacing the difficult to handle, often hazardous, liquid solutions by chemically inert, thin-layer membranes for the fabrication of advanced electrochemical devices. Particularly relevant in this respect has been the technological goal of replacing liquid electrolytes in lithium, non-aqueous batteries by a thin film of a solid polymer electrolyte which would act both as electrode separator and as a medium for ionic... 

As discussed in previous chapters, the separators are an integral part of liquid electrolyte batteries including nonaqueous batteries such as lithium-ion, lithium-polymer, hthium-ion gel polymer, and aqueous batteries such as zinc-carbon, zinc-manganese oxide, lead-acid, nickel-based batteries, and zinc-based batteries. 

The kinetics are not very sensitive to the electrolyte so the choice is largely dependent on safety, toxicity, and cost. The relatively slow kiaetics of the system has necessitated the use of thin electrodes ia order to obtain sufficient current carrying capabiUty and these cells are designed as coia cells (Fig. 23a) or as jelly roUs (Fig. 23b) with alternating anode, separator, cathode, and another separator layer. These 3-V batteries are made ia sizes not used for aqueous 1.5-V cells to help prevent their iasertion ia circuits designed for 1.5 V. 

The lead—acid battery is comprised of three primary components the element, the container, and the electrolyte. The element consists of positive and negative plates connected in parallel and electrically insulating separators between them. The container is the package which holds the electrochemically active ingredients and houses the external connections or terminals of the battery. The electrolyte, which is the Hquid active material and ionic conductor, is an aqueous solution of sulfuric acid. 

The organization of the Handbook of Battery Materials is simple, dividing between aqueous electrolyte batteries and alkali metal batteries and further in anodes, cathodes, electrolytes and separators. There are also three more general chapters about thermodynamics and mechanistics of electrode reactions, practical batteries and the global competition of primary and secondary batteries. 

Phase behavior 1n concentrated aqueous electrolyte systems is of interest for a variety of applications such as separation processes for complex salts, hydrometal 1urgical extraction of metals, interpretation of geological data and development of high energy density batteries. Our interest in developing simple thermodynamic correlations for concentrated salt systems was motivated by the need to interpret the complex solid-liquid equilibria which occur in the extraction of sodium nitrate from complex salt mixtures which occur in Northern Chile (Chilean saltpeter). However, we believe the thermodynamic approach can also be applied to other areas of technological interest. 

All lithium based batteries use nonaqueous electrolytes because of the reactivity of lithium in aqueous solution and because of the electrolyte s stability at high voltage. The majority of these cells use microporous membranes made of polyolefins. In some cases, nonwovens made of polyolefins are either used alone or with microporous separators. This section will mainly focus on separators used in secondary lithium batteries followed by a brief summary of separators used in lithium primary batteries. 

Lithium polymer electrolytes formed by dissolving a lithium salt LiX (where X is preferably a large soft anion) in poly(ethylene oxide) PEO can find useful application as separators in lithium rechargeable polymer batteries.Thin films must be used due to the relatively high ionic resistivity of these polymers. For example, the lithium-ion conductivity of PEO—Li salt complexes at 100 °C is still only about Viooth the conductivity of a typical aqueous solution. 

Various materials have been used as separators in zinc—bromine cells. Ideally a material is needed which allows the transport of zinc and bromide ions but does not allow the transport of aqueous bromine, polybromide ions, or complex phase structures. Ion selective membranes are more efficient at blocking transport then nonselective membranes.These membranes, however, are more expensive, less durable, and more difficult to handle then microporous membranes (e.g., Daramic membranes).The use of ion selective membranes can also produce problems with the balance of water between the positive and negative electrolyte flow loops. Thus, battery developers have only used nonselective microporous materials for the separator. 

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