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Inorganics 2017, 5, 25 12 of 17 Inorganics 2017, 5, 25 12 of 17 Figure 14. Discharge profiles as a function of C-rate for Li//LiNi0.55Co0.45O2 coin-type cells with two Figure 14. Discharge profiles as a function of C-rate for Li//LiNi0.55Co0.45O2 coin-type cells with two cathode materials of 100 nm and 2 μm particle size. 3.4.2. Layered LiNi1/3Mn1/3Co1/3O2 Actually, not even the transition-metal oxides, but also carbon coating is efficient to improve the cycle life of Li-ion batteries with LiN1/3Mn1/3Co1/3O2 (NMC) and LiCoO2 (LCO) as well. An annealing cathode materials of 100 nm and 2 μm particle size. 3.4.2. Layered LiNi1/3Mn1/3Co1/3O2 Actually, not even the transition-metal oxides, but also carbon coating is efficient to improve the effect re-crystallizes the surface layer that is otherwise disordered. This is currently obtained even cycle life of Li-ion batteries with LiN1/3Mn1/3Co1/3O2 (NMC) and LiCoO2 (LCO) as well. An annealing performing a simple heating in the presence of an organic compound. Hashem et al. [44] have studied effect re-crystallizes the surface layer that is otherwise disordered. This is currently obtained even the surface of NMC particles for material synthesized at 900 °C by a two-step process using a mixture performing a simple heating in the presence of an organic compound. Hashem et al. [44] have studied of LiOH·H2O and metal oxalate (Ni1/3Co1/3Mn1/3)C2O4 obtained by co-precipitation. The effect of the the surface of NMC particles for material synthesized at 900 ◦C by a two-step process using a mixture heat treatment at 600 °C with organic substances, i.e. sucrose and starch, was investigated. HRTEM of LiOH·H O and metal oxalate (Ni Co Mn )C O obtained by co-precipitation. The effect of images2 and Raman scattering (RS)1/s3pect1r/a3indic1a/t3e th2at 4the surface of particles has been modified the heat treatment at 600 ◦C with organic substances, i.e. sucrose and starch, was investigated. HRTEM with heating. Any carbon coating was grown with the annealing process but a remarkable imagecsryasntadlliRzatmioannosf ctahtetethringdi(sRoSrd) esrpeedcltaryaeirnodnictahteestuhrafatctehoef sNuMrfaCcwe aosf pearrftoircmleesdh. aTshbe eaennalmysoisdoiffitehde with HRTEM images (Figure 15) evidences the modification of the surface of particles upon calcination at heating. Any carbon coating was grown with the annealing process but a remarkable crystallization of 600 °C. Figure 15a shows the presence of an amorphous-like layer, typically 2.5-nm thick, that covers the thin disordered layer on the surface of NMC was performed. The analysis of the HRTEM images the NMC particle before carbon treatment. The micrograph clearly displays this surface ◦layer that (Figure 15) evidences the modification of the surface of particles upon calcination at 600 C. Figure 15a appears as a greyish region at the edge of the NMC crystallites, while the core of the primary particle shows the presence of an amorphous-like layer, typically 2.5-nm thick, that covers the NMC particle is the dark region. The disappearance of the disordered layer is observed (Figure 15b) after the before carbon treatment. The micrograph clearly displays this surface layer that appears as a greyish annealing process at moderate temperature using an organic substance such as sucrose or starch. As region at the edge of the NMC crystallites, while the core of the primary particle is the dark region. shown in the insert of Figure 15, the edge of the particle displays well-defined diffraction patterns. The disappearance of the disordered layer is observed (Figure 15b) after the annealing process at The beneficial effect has been tested on the electrochemical properties of the NMC cathode materials moderate temperature using an organic substance such as sucrose or starch. As shown in the insert in half lithium cells. For rate performance comparison, the modified Peukert plots, i.e., the specific −1 ofFigcuapreac1it5y,vths.eCe-dragte,oafrethsehopwanrtinclFeigduisrpel1a6y.sAwcaeplla-cditeyfi1n0e7dmdAifhf·rgactiisodnelpivaetrtedrnisn.tThehevobletangefircainagleffect 2.5–4.2 V at a 10 C rate from the cell with surface-modified NMC, while it is only 81 mAh·g−1 with the has been tested on the electrochemical properties of the NMC cathode materials in half lithium cells. non-treated NMC electrode at the same C-rate. For rate performance comparison, the modified Peukert plots, i.e., the specific capacity vs. C-rate, are shown in Figure 16. A capacity 107 mAh·g−1 is delivered in the voltage range 2.5–4.2 V at a 10 C rate from the cell with surface-modified NMC, while it is only 81 mAh·g−1 with the non-treated NMC electrode at the same C-rate. 3.4.3. Rock-Salt Li2MnO3 The layered compound Li2MnO3 (or Li[Li1/3Mn2/3]O2), which has an O3 structure built of close-packed oxygen layers in an ABCABC stacking of atoms (monoclinic structure, space group C2/m) is one of the most interesting compounds from the point of view of its structure and electrochemical behavior [45]. Indeed, in its microcrystalline form, this oxide was initially considered as an electrochemically inactive material in the potential range 2.0–4.4 V because no empty sites are available for Li insertion, and because of the +4 valence state of octahedrally coordinated Mn cations. However, this hypothesis has been disproved by Kalyani et al. [46]. In its nanostructured form, Li2MnO3 can deliver a theoretical capacity as high as 400 mAh·g−1 for total Li extraction. 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