Gel polymer batteries

Figure 14. Scanning electron micrographs of Celgard PVdF coated separators used in lithium gel polymer batteries (a) surface SEM, (b) cross-section SEM of coated trilayer, and (c) cross section of PVdF coating.

The reason why the progress of gel-polymer battery is rather slow is the slow technological progress in the area of functional electrolytes. The following discussion presents the history of electrolyte and additive development as well as the process followed in the design of LIB electrolyte. 

Sony is number one worldwide in production of lithium-ion gel polymer batteries, especially the relatively small-sized (below 1 Ah) battery. Sanyo-GS (Japan) and Samsung SDI (Korea) also are producing this kind of battery. Recently, a Chinese manufacturer started to produce lithium-ion gel polymer battery. ATL, one of the largest battery manufacturers, is producing a polymer battery based on Bellcore technologies. However, those manufacturers still continue their production in the small-sized battery field. 

A. Guerfi, M. Gontigny, Y. Kobayashi, A. 5jh, K. Zaghib, J. Solid State Electrochem. 2009, 13,1003-1014. Investigations on some electrochemical aspects of lithium-ion ionic hquid/gel polymer battery systems. 

The electrochemically active electrode materials in Li-ion batteries are a lithium metal oxide for the positive electrode and lithiated carbon for the negative electrode. These materials are adhered to a metal foil current collector with a binder, typically polyvinylidene fluoride (PVDF) or the copolymer polyvinylidene fluoride-hexafluroropropylene (PVDF-HFP), and a conductive diluent, typically a high-surface-area carbon black or graphite. The positive and negative electrodes are electrically isolated by a microporous polyethylene or polypropylene separator film in products that employ a liquid electrolyte, a layer of gel-polymer electrolyte in gel-polymer batteries, or a layer of solid electrolyte in solid-state batteries. 

Since the commercialization of Li-ion batteries by Sony in 1990, a broad array of variants has been introduced. One type, gel-polymer Li-ion batteries, utilizes the same active materials as products that employ liquid electrolytes, but in a different construction that enables the fabrication of cells with a thin form factor. Gel-polymer batteries, also referred to as polymer Li-ion batteries in the marketplace, are products where the microporous separator film used in conventional batteries is substituted by a layer of PVDF-HFP, or other polymer, impregnated with liquid electrolyte and the solid current collector foil is typically substituted with an open expanded metal current collector grid. In gel-polymer cells, the positive, separator, and negative layers are bound by the polymer, typically PVDF-HFP, and can be laminated together to form a monolithic device. Despite these differences, the active cell chemistry may remain identical to that in cylindrical or prismatic Li-ion batteries. 

Lithium-Ion Cel Polymer Battery The Hthium-ion gel polymer batteries offer better performance than that of solid polymer electrolyte batteries. The gel electrolyte is a polymer matrix swollen with a liquid electrolyte, and the batteries that employ gel electrolyte are known as gel polymer batteries. The detailed information on this type of battery can be found in other chapters of this book and in a review [33]. Most of the gel electrolytes have been made employing PEO, poly(acrylonitrile) (PAN) [34], poly(methyl methacrylate) (PMMA) [35, 36], and PVdF [37, 38]. The poor mechanical properties of polymer and gel polymer electrolytes have led to an alternative approach where microporous membranes are impregnated with gel polymer electrolytes [39-42]. The process builds upon the work of Abraham et al. who saturated commercial polyolefin separators with a solution of lithium salt in a photopolymerizable monomer and a nonvolatile... 

Many think the future moves toward solvent free systems Scrosati presents a chapter on polymer electrolytes, most of which are solvent-containing gel-polymers in practical systems, and Nishi discusses gel-polymer battery properties and production. Webber and Blomgren give extensive treatment of ionic hquids (otherwise known as ambient-temperature molten salts) and their use in lithium-ion and other battery systems. 

These types of separators consist of a solid matrix and a liquid phase, which is retained in the microporous structure by capillary forces. To be effective for batteries, the liquid in the microporous separator, which generally contains an organic phase, must be insoluble in the electrolyte, chemically stable, and still provide adequate ionic conductivity. Several types of polymers, such as polypropylene, polysulfone, poly(tetrafluoroethylene), and cellulose acetate, have been used for porous substrates for supported-liquid membranes. The PVdF coated polyolefin-based microporous membranes used in gel—polymer lithium-ion battery fall into this category. Gel polymer... 

Lithium secondary batteries can be classified into three types, a liquid type battery using liquid electrolytes, a gel type battery using gel electrolytes mixed with polymer and liquid, and a solid type battery using polymer electrolytes. The types of separators used in different types of secondary lithium batteries are shown in Table 1. The liquid lithium-ion cell uses microporous polyolefin separators while the gel polymer lithium-ion cells either use a PVdF separator (e.g. PLION cells) or PVdF coated microporous polyolefin separators. The PLION cells use PVdF loaded with silica and plasticizer as separator. The microporous structure is formed by removing the plasticizer and then filling with liquid electrolyte. They are also characterized as plasticized electrolyte. In solid polymer lithium-ion cells, the solid electrolyte acts as both electrolyte and separator. 

Development efforts are under way to displace the use of microporous membranes as battery separators and instead use gel electrolytes or polymer electrolytes. Polymer electrolytes, in particular, promise enhanced safety by eliminating organic volatile solvents. The next two sections are devoted to solid polymer and gel polymer type lithium-ion cells with focus on their separator/electrolyte requirements. 

The solid polymer electrolyte approach provides enhanced safety, but the poor ambient temperature conductivity excludes their use for battery applications. which require good ambient temperature performance. In contrast, the liquid lithium-ion technology provides better performance over a wider temperature range, but electrolyte leakage remains a constant risk. Midway between the solid polymer electrolyte and the liquid electrolyte is the hybrid polymer electrolyte concept leading to the so-called gel polymer lithium-ion batteries. Gel electrolyte is a two-component system, viz., a polymer matrix... 

Gel polymer lithium-ion batteries replace the conventional liquid electrolytes with an advanced polymer electrolyte membrane. These cells can be packed in lightweight plastic packages as they do not have any free electrolytes and they can be fabricated in any desired shape and size. They are now increasingly becoming an alternative to liquid-electrolyte lithium-ion batteries, and several battery manufacturers. such as Sanyo. Sony, and Panasonic have started commercial production.Song et al. have recently reviewed the present state of gel-type polymer electrolyte technology for lithium-ion batteries. They focused on four plasticized systems, which have received particular attention from a practical viewpoint, i.e.. poly(ethylene oxide) (PEO). poly (acrylonitrile) (PAN). ° poly (methyl methacrylate) (PMMA). - and poly(vinylidene fluoride) (PVdF) based electrolytes. ... 

To overcome the poor mechanical properties of polymer and gel polymer type electrolytes, microporous membranes impregnated with gel polymer electrolytes, such as PVdF. PVdF—HFP. and other gelling agents, have been developed as an electrolyte material for lithium batteries.Gel coated and/ or gel-filled separators have some characteristics that may be harder to achieve in the separator-free gel electrolytes. For example, they can offer much better protection against internal shorts when compared to gel electrolytes and can therefore help in reducing the overall thickness of the electrolyte layer. In addition the ability of some separators to shutdown... 

Because of the importance of high-performance secondary batteries, the techniques of the secondary lithium batteries are still making rapid progresses. Lithium polymer secondary batteries, having gel-polymer electrolytes, are advantageous in that the rigid metal container is not essential. Thus, all-plastic thin lithium secondary batteries are now available. 

In the case of ion conductive polymers, gel polymer electrolytes which consist of a polymer matrix, organic solvents and supporting electrolyte, were introduced as novel nonaqueous electrolyte systems in electrochemical applications, such as rechargeable batteries and electric double layer capacitors [3-5], Recently, considerable attention has been devoted to the application of gel poly-... 

As mentioned above, a coin type Li polymer battery has high performance. In particular, the PMMA gel electrolyte is very stable toward lithium anodes. 

PANI-NFA 2O5 is promising nanocomposite material for utilization as a cathode for ion-Li batteries [292,293]. PANI-NFs have been used as a cathode material for rechargeable Li-polymer cells assembled with a gel polymer electrolyte [152], and in an aqueous PANI-Zn rechargeable battery [261]. Dispersions of dedoped PANI-NFs in poly(vinyhdene fluoride-hexafluoropropylene)-based gel polymers can be used as electrolyte membranes for rechargeable Li batteries [513]. PANI-NF and PANI-NT arrays, which show superior electrochemical properties to the bulk counterpart, can be applied to Li-polymer thin-film batteries, which are shape-flexible and specifically suitable for powering integrated circuit cards and microelectromechanical systems [514,515]. 

Sivakkumar, S., Kim, D.-W., 2007. Polyanfline/carbon nano tube composite cathode for rechargeable lithium polymer batteries assembled with gel polymer electrolyte. J. Electrochem. Soc. 154, A134-A139. 

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