Lithium insertion/extraction

This review focuses on the structural stability of transition metal oxides to lithium insertion/extraction rather than on their electrochemical performance. The reader should refer to cited publications to access relevant electrochemical data. Because of the vast number of papers on lithium metal oxides that have been published since the 1970s, only a selected list of references has been provided. 

Goodenough, J. B., Thackeray, M. M., David, W. I. F. Bruce, P. G. (1984). Lithium insertion/extraction reactions with manganese oxides. Revue de Chimie Minerale, 21, 435-55. 

To improve the cyclability of LiMn O in the 4-V region, many studies have been made using doped manganese-substituted spinels such as LiM n O (M = Co, Ni, Cr, Al,. ..). It has been reported that the capacity failure was suppressed by the replacement of a part of manganese with another metal ion because of the doped manganese-substituted spinels inhibited the decay of its original structure in lithium insertion/extraction process. Next we show our investigation of the LiM n O compound (M = Co, Ni, X is from 0.0 to 0.5). 

XRR has been applied to the study of EEIs on several systems [201-205]. The technique was found to be sensitive not only to the formation of reaction layers but also to mass loss at the electrode surface due to processes of corrosion (dissolution) [201]. Of particular interest is the application of high energy synchrotron beams as sources, as their deep penetration capabilities enables the design of operando cells (Fig. 7.10a) [203], Therefore, uncertainty due to equilibration in the absence of an electrochemical potential is eliminated. The structural and chemical stability of EEIs during the lithium insertion/extraction processes have thus been evaluated (Fig. 7.10b) [201-204]. The dependence of these irreversible reactions on the crystal facet of the electrode material forming the EEI was established. It was found that electrolyte decomposition processes were coupled with the redox process occurring in the bulk of the electrode, which is a critical piece of information when designing materials that bypass such layer formation. 

Obrovac MN, Christensen L (2004) Structural changes in silicon anodes during lithium insertion/extraction. Electrochem Solid-State Lett 7 A93-A96... 

GOO 84] Goodenough J.B., Thackeray M.M., David W.I.F. et al.. Lithium Insertion/Extraction Reactions with Manganese Oxides, Gauthier-Villars, Paris, France, 1984. 

Panero S, Reale P, Ronci F, Scrosati B, Perfetti P, Rossi Albertini V (2001) Refined, in-situ EDXD structural analysis of the Li[Lii/3Ti5/3]04 electrode under lithium insertion-extraction. Phys Chem Chem Phys 3 845-847. doi 10.1039/B008703N... 

Wei-Jun Zhang, Lithium insertion/extraction mechanism in alloy anodes for lithium-ion batteries , J. Power Sources, 196, 877-885,2011. 

Mixed-conducting lithium-ion-doped emeraldine polyaniline (PAni)-PEO blends have been developed in order to achieve optimal electronic-ionic conductivity balance in nano-tin composite anodes. They found that the SEI impedance of the composite anodes increases with a decrease in PEO content and is much lower in pressed than in cast electrodes. Nano-Sn, AlSi , and Li Sn powders were studied by EIS to determine the electrochemical kinetics and intrinsic resistance during initial lithium insertion-extraction. It was shown that the SEI formed on particle surfaces, together with particle pulverization are responsible for the high contact resistance. 

Bramnik NN, Nikolowski K, Baehtz C, Bramnik KG, Ehrenberg H (2007) Phase transition occurring upon lithium insertion-extraction of LiCoP04. Chem Mater 19 908-915... 

Chen JS, Lou XW (2009) Anatase Ti02 nanosheet an ideal host stnicture for fast and efficient lithium insertion/extraction. Electrochem Common 11 2332-2335... 

Rechargeable lithium batteries involve a reversible insertion/extraction of lithium ions into/from a host electrode material during the charge-discharge process. The lithium insertion/extraction process, which occurs with a flow of ions through the electrolyte, is accompanied by an oxidation/reduction (redox) reaction of the host matrix assisted by a flow of electrons through the external circuit (Figure 12.2). 

The lithium insertion/extraction reaction should be reversible, with minimal or no change in structure, leading to good cycle life. 

The lithium insertion/extraction process should be reversible with no or minimal changes in the host structure over the entire range x of lithium insertion/extraction in order to provide good cycle life for the cell. 

The redox energy of the cathode in the entire range x of lithium insertion/ extraction should lie within the band gap of the electrolyte to prevent any unwanted oxidation or reduction of the electrolyte. 

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