Conductivity lithium polymer batteries

In battery applications, new hthium ion batteries called lithium ion polymer batteries (or more simply but misleadingly, lithium polymer batteries) work with a full matrix of ionically conducting polymer, this polymer being present inside the porous electrodes and as a separator between the electrodes. They are offered in attractive flat shapes for mobile applications (mobile phones, notebooks). 

More recently, solid state batteries with lithium conducting polymer electrolytes have been extensively studied. The development has focused on secondary batteries for an electric vehicle, because lithium polymer batteries have a theoretical energy density that approaches 800 W h kg ... 

The potential use of polymeric ion-exchange membranes in the next generation single-ion secondary lithium polymer batteries was shown by Sachan et al 84,85 Conductivities exceeding 10 S/cm with transference numbers of unity were achieved for Nafion converted to the Li+ salt form. 

In lithium polymer batteries, one electrode is lithium foil, or in some cases another electrically conducting material such as graphite, and the other is a reversible intercalation compound as in liquid electrolyte lithium batteries. Compounds used as intercalation electrodes include LiCo02 and VeOis. The cell developed in the Anglo-Danish project, which ran from 1979 to 1995, was... 

The lithium polymer battery (LPB), shown schematically in Fig. 7.21, is an all-solid-state system which in its most common form combines a lithium ion conducting polymer separator with two lithium-reversible electrodes. The key component of these LPBs is the polymer electrolyte and extensive work has been devoted to its development. A polymer electrolyte should have (1) a high ionic conductivity (2) a lithium ion transport number approaching unity (to avoid concentration polarization) (3) negligible electronic conductivity (4) high chemical and electrochemical stability with respect to the electrode materials (5) good mechanical stability (6) low cost and (7) a benign chemical composition. 

Molecular salts of type 65 have also been prepared recently by the reaction of a secondary amine with the linear isomer of hexafluoropropane sultone as depicted in Scheme 18 <2003MI1961>. These lithium polymers exhibit high electrochemical stability and cationic conductivity and therefore are ideally suited for lithium polymer batteries. 

With the use of sohd to gelatinous, polymeric electrolyte layers that ensure electrical separation of the electrodes and the unity of the cell components combined with good conductivity for lithium ions, it is not necessary to employ hquid electrolytes in lithium batteries. This simplifies the production of lithium polymer batteries, which are also safer in operation because the electrolyte is polymeric, not liquid. This battery cell structure facilitates production of thin foil batteries, a favorable form for use in portable devices. The expected performance data correspond to what is obtained with other lithium ion systems. 

Lithium-Doped Conducting Polymer and Lithium-Polymer Batteries... 

The purpose of this chapter is to describe how ionic conductivity has been achieved in ways that retain the advantages of flexibility, processability, ease of handling and relatively low impact on the environment that polymers inherently possess. Electronically conducting polymers are addressed in the next chapter. The reader will also find particular aspects of ion conducting polymers discussed in detail in subsequent parts of this volume these include multivalent polymer electrolytes, key application areas such as lithium polymer batteries and smart windows, and the development of polymer hosts which permit greatly enhanced conductivity at room temperature. 

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, i.e. 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 jum thickness) by a number of convenient casting techniques. 

Arie et al. [116] investigated the electrochemical characteristics of phosphorus-and boron-doped silicon thin-film (n-type and p-type silicon) anodes integrated with a solid polymer electrolyte in lithium-polymer batteries. The doped silicon electrodes showed enhanced discharge capacity and coulombic efficiency over the un-doped silicon electrode, and the phosphorus-doped, n-type silicon electrode showed the most stable cyclic performance after 40 cycles with a reversible specific capacity of about 2,500 mAh/g. The improved electrochemical performance of the doped silicon electrode was mainly due to enhancement of its electrical and lithium-ion conductivities and stable SEI layer formation on the surface of the electrode. In the case of the un-doped silicon electrode, an unstable surface layer formed on the electrode surface, and the interfacial impedance was relatively high, resulting in high electrode polarization and poor cycling performance. 

Arie AA, Chang W, Lee JK (2010) Electrochemical characteristics of semi conductive silicon anode for lithium polymer batteries. J Electroceramics 24 308-312... 

Poly (ethylene oxide) (PEO) - LiX complexes appear to be the most suitable electrolytes for lithium polymer batteries, however, the local relaxation and segmental motion of the polymer chains remain a problem area (Armand et al., 1997). Therefore, the PEO-based electrolytes show an appreciable ionic conductivity only above 100°C (Gorecki et al., 1986). This is, of course, a drawback for applications in the consumer electronic market. On the other hand, the gel polymer electrolytes although offer high ionic conductivity and appreciable lithiiun transport properties it suffers from poor mechanical strength and interfacial properties (Croce et al., 1998 Gray et al., 1986 Kelly et al., 1985 Weston et al., 1982). Recent studies reveal that the nanocomposite polymer electrolytes alone can offer safe and reliable lithium batteries (Appetecchi... 

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... 

C. A. Donnelly, Lithium Polymer Batteries Development for Large Battery Applications, 2nd Int. Meeting on Application of Conducting Polymers, Minneapolis, USA, July 1999. 

The polymer component in these batteries fulfills the function of a medium for ionic transport and a separator. The polymers are polyethers, PEO, or PPO. However, the lithium salts, dissolved in these polymers, have 100-fold lower conductivity than that of a lithium salt dissolved in water. The low conductivity below 70 °C, the reactivity of the interface with the lithium metal electrode, and the issues related to mechanical properties and electrochemical stability need to be resolved before the lithium polymer battery has acceptable performance. The use of inorganic composite membranes, described in a subsequent section, has been shown to result in improved ionic conductivity. 

JANNASCH p (2001), Ion conducting electrolytes based on aggregating comblike poly(propylene oxide) . Polymer, 42 8629-8635 JIANG G, MAEDA S, YANG H, SAITO Y, TANASE S and SAKAI T (2005), All SOlid-State lithium-polymer battery using poly(urethane acrylate)/nano-Si02 composite elec-troiytes , / Power Sources, 141 143-148... 

The ionic conductivity of polymer electrolytes, however, is by far lower than that of liquid phase electrolytes. Gelled polymer electrolytes (GPEs), which are composed of polymer matrices and solvents or plasticizers, have been developed in place of genuine polymer electrolytes to improve ionic conductivity. And in the end of 1990s, LIBswith GPEs, which will be called lithium polymer batteries (LPBs) hereafter for convenience s sake, were put on the market. 

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