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Layered Manganese Oxides as Cathodes

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The first commercial lithium-ion batteries used LiCo02 as the cathode active material, and this material continues to be used in most lithium-ion batteries manufactured despite the high cost and safety hazards associated with cobalt. Apart from LiCo02, only the isostructural nickelate LiNi02, and more particularly the Co-substituted nickelate LiCo x Ni1−x 02, have been considered to have sufficient energy density and cycling stability to be of commercial interest. However the nickelates present safety and toxicity concerns which are still greater than LiCo02. Manganese oxides offer lower cost and toxicity than cobalt or nickel, and have been demonstrated to be safer on overcharge. A lithium manganese oxide based cathode should therefore, at least in principle, provide significant technological advantages in a lithium-ion system over LiCo02, LiNi02, or LiCo x Ni1−x 02.

One of the reasons that LiCo02 functions so well as a lithium-ion cathode material is that it has a well-ordered and stable layered crystal structure which is easily prepared and handled in air, and enables a fast and reversible lithium intercalation. Nickelates also have a layered crystal structure, although the synthesis conditions are more difficult, requiring calcination and sintering under a controlled oxygen-rich atmosphere. The most readily prepared lithium manganese oxide is LiMn204, which does not have a layered crystal structure but a spinel structure (refer previous chapters in this volume). Although the spinel crystal structure of LiMn204 permits rapid intercalation of lithium ions, its stoichiometry means that it has a lower capacity than LiCo02. Furthermore, the stoichiometric spinel LiMn204 shows a large capacity fade with cycling. Lithium-rich spinel compositions Li[Li x Mn2−x .]04 or materials substituted with cations such as Co, Cr, Al,

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  1. Pacific Lithium New Zealand Limited, PO Box 90725, Auckland, New Zealand

    B. Ammundsen

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  1. B. Ammundsen
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  1. General Motors R&D and Planning Center, MC 480-102-RCEL, 30500 Mound Road, Warren, MI 48090-9055, USA

    Gholam-Abbas Nazri

  2. Via G. Scalia, Rome, 1000136, Italy

    Gianfranco Pistoia

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Ammundsen, B. (2009). Layered Manganese Oxides as Cathodes. In: Nazri, GA., Pistoia, G. (eds) Lithium Batteries. Springer, Boston, MA. https://doi.org/10.1007/978-0-387-92675-9_13

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  • DOI: https://doi.org/10.1007/978-0-387-92675-9_13

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