Lithium solid-electrolyte/metal salt batteries

The Other Five Candidates. All the molten salt SBs reviewed above have either a Li anode or a lithium alloy, one in which Li prevails quantitatively. As to the other 5 light metals they are seldom mentioned in the literature as candidates for anodes in these SBs, except Al. In (82) it is stated that molten salt batteries with Ca or Mg anodes yield only a small proportion of their theoretical energy because (a) Ca anodes react chemically with the electrolyte, and (b) both Ca and Mg anodes are passivated at high current drains, becoming coated with resistive films of solid salts. In a melt containing Li salts, Ca replaces Li ions by the displacement reaction Ca + 2LiCl = CaCl2 + 2Li. 

Cases exist, however, where for fundamental reasons aqueous solutions cannot be used. One such case is devices in which electrochemical processes take place at elevated temperatures (above 180-200 C), for instance, the electrowinning of aluminum is performed at temperatures close to 1000°C. Another case is devices in which electrodes consisting of alkali metals are used, which are unstable in aqueous solutions. An example is the batteries with a lithium negative electrode. For this reason, other kinds of electrolytes are used in addition to aqueous solutions, viz, non-aqueous solutions of salts, salt melts, and a variety of solid electrolytes. 

Lithium-Metal Salt secondary batteries are analogous to the Lithium-seawater primary battery [3]. A Li -ion solid electrolyte separates a nonaqueous anolyte and an aqueous cathode. For example, a Lithium anode with a carbonate anolyte and an aqueousFe(CN)g /Fe(CN)g cathode has been shown to give aflat voltage F 3.4 V with an efficiency that increases with the molar ratio of iron cyanide in the cathode solution [27]. This promising approach requires development of a Li-ion solid electrolyte having a (Tli > 10 8/cm at room temperature that is stable to an acidic cathode solution and is not reduced by contact with a Li° dendrite on the anode side. 

Polymer electrolytes (e.g., poly(ethylene oxide), poly(propylene oxide)) have attracted considerable attention for batteries in recent years. These polymers form complexes with a variety of alkali metal salts to produce ionic conductors that serve as solid electrolytes. Its use in batteries is still limited due to poor electrode/ electrolyte interface and poor room temperature ionic conductivity. Due to its rigid structure it can also serve as the separator. Polymer electrolytes are discussed briefly in the section Separators for Lithium-Ion Batteries. 

It is now well established that solvent-free films can be cast from solutions of polyethers (such as poly(ethylene oxide)) and alkali metal salts, and that these films can display high ionic conductivity. Most of the effort devoted to this field has been based on the potential of such materials as solid-state electrolytes for battery applications. In this context, from viewpoints of both ionic mobility and weight, lithium salts in PEO have attracted the most intensive research and appear to offer the most promise such materials are discussed elsewhere. The preparation of materials displaying both electronic and ionic conductivity raises interesting possibilities both in the field of batteries and sensors and is beginning to attract attention (16). 

Lithium alloy/metal sulfide batteries employ a molten-salt electrolyte and solid porous electrodes. Depending on electrolyte composition, they operate over a temperature range of 375 to 500°C. Operation at these temperatures with molten-salt electrolytes achieves high power densities, due to the high electrolyte conductivities and fast electrode kinetics. A shift from prismatic battery designs to bipolar designs enhances the power characteristics further by reducing the battery impedance. 

Electrodes and cell components must be thin to minimise the internal resistance of the batteries the total cell can be less than 0.2 mm thick. Figure 12.11 shows the construction of a multi-layer film, rechargeable lithium polymer battery, using a solid polymer electrolyte. A thin lithium metal foil acts as an anode. The electrolyte is polyethylene oxide containing a lithium salt, and the cathode is a composite of the electrolyte and a... 

In this case, we have an electrolyte identical to that which is present in lithium-polymer batteries, made of poly(ethylene oxide) (or PEO) in the presence of a lithium salt, solid at ambient temperature, and which needs to be heated above ambient temperature in order for the battery to work (T > 65°C for PEO). Thus, the electrolyte, in its molten state, exhibits sufficient ionic conductivity for the lithium ions to pass. This type of electrolyte can be used on its own (without a membrane) because it ensures physical separation of the positive and negative electrodes. This type of polymer electrolyte needs to be differentiated from gelled or plasticized electrolytes, wherein a polymer is mixed with a lithium salt but also with a solvent or a blend of organic solvents, and which function at ambient temperature. In the case of a Li-S battery, dry polymer membranes are often preferred because they present a genuine all solid state at ambient temperature, which helps limit the dissolution of the active material and therefore self-discharge. Similarly, in the molten state (viscous polymer), the diffusion of the species is slowed, and there is the hope of being able to contain the lithium polysulfides near to the positive electrode. In addition, this technology limits the formation of dendrites on the metal lithium... 

Rechargeable lithium-ion polymer cells incorporate the polymer as part of the electrochemical operation of the battery and these cells are widely used to power such portable consumer products as laptop computers and mobile phones. Lithium-metal-polymer is a relatively new technology from Avestor in Canada. It uses a solid polymeric electrolyte obtained by dissolving a lithium salt in an appropriate co-polymer. The metallic oxide cathode is made from a plastic composite material. 

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. 

A polymer electrolyte is also referred to as a solid solvent that possesses ion transport properties similar to that of the common liquid ionic solution. It usually comprises a polymer matrix and electrolyte, wherein the electrolyte such as a lithium salt dissolves in a polymer matrix. The research and development of polymer electrolytes have drawn great attention in the last three decades as they are applied in many electrochemical devices such as hthium batteries, nickel - metal hydride (Ni/MH) batteries, fuel cells/direct methanol fuel cells, supercapadtors, electrochromic devices and the like (Gray, 1991 Stephan, 2006). 

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