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Inorganics 2017, 5, 25 15 of 17 In the case of olivine materials LiMPO4 (M = Fe, Mn, Co, Ni), the increase of rate capability (for use in hybrid electric vehicles, for instance) is achieved by decreasing as much as possible the size of the particles (L ≈ 40 nm) to improve the effective surface. Since the electronic and ionic conductivity of olivine frameworks are small (σe<<10-12 S·cm−1), the nanosize is expected to be beneficial to the performance, especially at high C-rates. It is remarkable that the power-grade powders retained 75% of the initial capacity at 10C rate. Typical examples describing the particle size effect of layered materials are provided by LiNi0.55Co0.45O2 (NCO) and LiN1/3Mn1/3Co1/3O2 (NMC) cathodes. However, improvement of the electrochemical performance (cycling stability) requests a modification of the surface of particles (coating by metal oxide) to prevent the transition-metal ion dissolution. The beneficial effect has been tested on the properties of the NMC cathode materials in half cells. It was shown that the electrochemical activity of the nanocrystalline Li2MnO3 electrodes depends upon the particles morphology, specific surface area, and annealing temperature of the as-prepared material, while microcrystalline powders are electrochemically inactive. Acknowledgments: The authors thank the Université Pierre et Marie Curie (Paris 6) for financial support. Author Contributions: Xiaoyu Zhang and Ana-Gabriela Porras-Gutierrez performed the synthesis and accomplished the measurements of materials; Henri Groult and Alain Mauger contributed to interpretation and finalized the manuscript; and Christian M. Julien led the over-arching research project. Conflicts of Interest: There is no conflict of interest related to this document. References 1. Julien, C.M.; Mauger, A.; Vijh, A.; Zaghib, K. Lithium Batteries: Science and Technology; Springer: Heidelberg, Germany, 2016. 2. Zaghib, K.; Mauger, A.; Julien, C.M. Rechargeable Batteries; Zhang, Z., Zhang, S.S., Eds.; Springer: Heidelberg, Germany, 2015. 3. Yamada, A.; Chung, S.C.; Hinokuma, K. Optimized LiFePO4 for lithium battery cathodes. J. Electrochem. Soc. 2001, 148, A224–A229. [CrossRef] 4. Okubo, M.; Hosono, E.; Kim, J.; Enomoto, M.; Kojima, N.; Kudo, T.; Zhou, H.; Honma, I. Nanosize effect on high-rate Li-ion intercalation in LiCoO2 electrode. J. Am. Chem. Soc. 2007, 129, 7444–7452. [CrossRef] [PubMed] 5. Castro-Couceiro, A.; Castro-Garcia, S.; Senaris-Rodriguez, M.A.; Soulette, F.; Julien, C. Effects of the aluminum doping on the microstructure and morphology of LiNi0.5Co0.5O2 oxides. Ionics 2002, 8, 192–200. [CrossRef] 6. Vediappan, K.; Guerfi, A.; Gariépy, V.; Demopoulos, G.P.; Hovington, P.; Trottier, J.; Mauger, A.; Julien, C.M.; Zaghib, K. Stirring effect in hydrothermal synthesis of nano C-LiFePO4. J. Power Sources 2014, 266, 99–106. [CrossRef] 7. Dominko, R.; Bele, M.; Gaberscek, M.; Remskar, M.; Hanzel, D.; Goupil, J.M.; Pejovnik, S.; Jamnik, J. Prorous olivine composites synthesized by sol–gel technique. J. Power Sources 2006, 153, 274–280. [CrossRef] 8. Wang, Y.; Sun, B.; Park, J.; Kim, W.S.; Kim, H.-S.; Wang, G. Morphology control and electrochemical properties of nanosize LifePO4 cathode material synthesized by co-precipitation combined with in situ polymerization. J. Alloys Compd. 2011, 509, 1040–1044. [CrossRef] 9. Brochu, F.; Guerfi, A.; Trottier, J.; Kopec, M.; Mauger, A.; Groult, H.; Julien, C.M.; Zaghib, K. Structure and electrochemistry of scalling nano C-LiFePO4 synthesized by hydrothermal route: complexing agent effect. J. Power Sources 2012, 214, 1–6. [CrossRef] 10. Doherty, C.M.; Caruso, R.A.; Smarsly, B.M.; Drummond, C.J. Colloidal crystal templating to produce hierarchically porous LiFePO4 electrode materials for high power lithium ion batteries. Chem. Mater. 2009, 21, 2895–2903. [CrossRef] 11. Zaghib, K.; Charest, P.; Dontigny, M.; Guerfi, A.; Lagacé, M.; Mauger, A.; Kopec, M.; Julien, C.M. LiFePO4: From molten ingot to nanoparticles with high-rate performance in Li-ion batteries. J. Power Sources 2010, 195, 8280–8288. [CrossRef]PDF Image | Nanotechnology of Positive Electrodes for Li-Ion Batteries
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