Structure and Electrochemical Properties of Li-rich Li2+4xMn0.6+2xNi0.6-6xCr0.8O4 Spinel Prepared by Hydrothermal Method†

doi:10.7503/cjcu20130599

Abstract

Abstract:

A series of cathode materials, L $i 2 + 4 x$ M $n 0.6 + 2 x$ N $i 0.6 - 6 x$ Cr_0.8O₄(x=1/30, 1/20, 1/15, 1/12), was prepared via hydrothermal method, and their composition, structure and electrochemical properties were investigated using X-ray diffraction(XRD), inductively coupled plasma-atomic emission spectrometry(ICP-AES), scanning electron microscopy(SEM),X-ray photoelectron spectroscopy(XPS), Fourier transform infrared spectrometry(FTIR), Raman spectrometry and charge-discharge tests. XRD measurements combining with ICP results reveal that the obtained samples are Li-rich type spinel structure. Moreover, XPS results suggest that the valence for Cr is +3 for x=1/15 and 1/12 and no Cr⁶⁺ exist. As to their electrochemical properties, it is found that these materials have a high-voltage plateau near 4.7 V and a low-voltage near 2.7 V. With the increase of x value, both charge and discharge capacities of the samples increase. The sample with x=1/12 shows a good cyclic performance as well as good rate capability.

Key words: Lithium ion battery, Cathode material, Li-rich spinel structure, Hydrothermal method, High-voltage

CLC Number:

TrendMD:

ZHAO Lifang, ZHANG Qian, HE Shici, LIU Weiwei, YANG Yusheng, ZHENG Junwei, PAN Qinmin, LI Decheng. Structure and Electrochemical Properties of Li-rich Li₂₊₄_xMn_0.6+2_xNi_0.6-6_xCr_0.8O₄ Spinel Prepared by Hydrothermal Method^†[J]. Chem. J. Chinese Universities, 2014, 35(2): 362.

Figures/Tables 9

Fig.1 XRD patterns of Li2+4xMn0.6+2xNi0.6-6xCr0.8O4x: a. 1/30; b. 1/20; c. 1/15; d. 1/12.

Fig.2 FTIR spectra of Li2+4xMn0.6+2xNi0.6-6xCr0.8O4x: a. 1/30; b. 1/20; c. 1/15; d. 1/12.

Fig.3 Raman spectra of Li2+4xMn0.6+2xNi0.6-6xCr0.8O4x: a. 1/30; b. 1/20; c. 1/15; d. 1/12.

Table 1 Results of the composition analysis for the Li2+4xMn0.6+2xNi0.6-6xCr0.8O4(x=1/30, 1/20, 1/15, 1/12)

Aimed product	Obtained product
LMn_0.667NCr_0.8O₄	Li_1.077Mn_0.617Ni_0.399Cr_0.82O₄
LMn_0.700NCr_0.8O₄	Li_1.149Mn_0.675Ni_0.293Cr_0.896O₄
LMn_0.733NCr_0.8O₄	Li_1.241Mn_0.751Ni_0.211Cr_0.899O₄
LMn_0.767Ni_0.1Cr_0.8O₄	Li_1.925Mn_0.697Ni_0.129Cr_0.880O₄

Fig.4 XPS spectra of Mn2p(A), Li1s(B), Ni2p(C) and Cr2p(D) of Li2+4xMn0.6+2xNi0.6-6xCr0.8O4x: a. 1/12; b. 1/15.

Fig.5 SEM images of as-prepared Li2+4xMn0.6+2xNi0.6-6xCr0.8O4x: (A) 1/30; (B) 1/20; (C) 1/15; (D) 1/12.

Fig.6 Initial charge(a—d) and discharge(a'—d') curves of Li2+4xMn0.6+2xNi0.6-6xCr0.8O4 at a current density of 20 mA/g in 2.0—5.0 V voltage rangex: a, a'. 1/30; b, b'. 1/20; c, c'. 1/15;d, d'. 1/12.

Fig.7 Cyclic voltammograms of Li2.3333Mn0.7667Ni0.1Cr0.8O4(x=1/12) at a sweep rate of 0.05 mV/s between 2.0 and 5.0 V

Fig.8 Cyclic performance of Li2+4xMn0.6+2xNi0.6-6xCr0.8O4 at a current density of 20 mA/g in 2.0—5.0 V voltage range(A) and rate capabilities of as-prepared Li2+4xMn0.6+2xNi0.6-6xCr0.8O4(B)x: a. 1/12; b. 1/15; c. 1/20; d. 1/30.

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Structure and Electrochemical Properties of Li-rich Li₂₊₄_xMn_0.6+2_xNi_0.6-6_xCr_0.8O₄ Spinel Prepared by Hydrothermal Method^†

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