尖晶石/層狀異質結構xLiM2O4？(1-x)LiNi1/3Co1/3Mn1/3O2鋰離子電池正極材料的制備及電化學性能

尖晶石/層狀異質結構xLiM2O4？(1-x)LiNi1/3Co1/3Mn1/3O2鋰離子電池正極材料的制備及電化學性能Preparation and characterization of spinel/layered heterostructured xLiM2O4？(1-x)LiNi1/3Co1/3Mn1/3O2 cathodes for Li-ion battery and its electrochemical properties

采用原位誘導法制備得到了一系列xLiM2O4？(1-x)LiNi1/3Co1/3Mn1/3O2(M=Ni, Co, Mn; x=0, 0.1, 0.2, 0.3, 0.4, 0.5)尖晶石/層狀異質結構復合材料。借助X射線衍射、掃描電鏡、差示掃描量熱儀、恒電流間歇滴定技術和恒電流充放電測試表征手段對材料的晶體結構、微觀形貌和電化學性能進行了研究。電化學性能結果表明：x=0.2材料的倍率性能和循環性能最佳，在2.7~4.3 V、1C下循環100次后，放電比容量為137 mA？h/g，容量保持率為93%；10C時的放電比容量為112 mA？h/g，相比于原始LiNi1/3Co1/3Mn1/3O2材料在10C的放電比容量(95 mA？h/g)有較大提高。此外，快充慢放能力測試也證實了該材料的結構穩定，其在5C充、1C放的充放電機制下，循環100次后的放電比容量還能高達120 mA？h/g，容量保持率為87%。恒電流間歇滴定技術(GITT)的結果表明。x=0.2材料的DLi+值比原始LiNi1/3Co1/3Mn1/3O2材料的要高出一個數量級，說明尖晶石相的引入從根本上改善了材料的電化學性能。

A series of heterostructured spinel/layered xLiM2O4？(1-x)LiNi1/3Co1/3Mn1/3O2 (M=Ni, Co, Mn; x=0, 0.1, 0.2, 0.3, 0.4, 0.5) cathodes were prepared by in-situ induced coating method. Powder X-ray diffractometry (XRD), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), galvanostetic intermittent titration technique (GITT) and galvanostatic charge-discharge tests were employed to analyze the crystal structure, micromorphology and electrochemical properties of the as prepared materials. Electrochemical results indicate that the x=0.2 sample has the best rate performance and long-term cycling stability. It delivers a discharge capacity of 137 mA？h/g at 2.7-4.3 V and 1C after 100 cycles, with the outstanding capacity retention being 93%. At 10C, the specific capacity of the material is 112 mA？h/g, which is improved greatly when compared with the pristine LiNi1/3Co1/3Mn1/3O2 (95 mA？h/g at 10C). Additionally, the fast-charging test results are indicative of the fact that this cathode has sufficiently stable structure, because it can still deliver a discharge capacity higher than 120 mA？h/g after 100 cycles with capacity retention of 87% at 5C charge and 1C discharge. Galvanostatic intermittent titration technique (GITT) results show that DLi+ of x=0.2 sample is higher by one order of magnitude than the pristine LiNi1/3Co1/3Mn1/3O2, indicating that the introduced spinel phase could fundamentally enhance the electrochemical performance for cathodes.

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