喷雾热解制备高能量密度尖晶石LiCr0.2Ni0.4Mn1.4O4正极材料

doi:10.15541/jim20130656

摘要/Abstract

摘要：

以喷雾热解法制备出了能量密度高, 电化学性能优异的LiCr_0.2Ni_0.4Mn_1.4O₄正极材料。采用热重分析、X射线衍射、扫描电镜、循环伏安、交流阻抗等手段进行了测试与表征, 并且在现有市售高电压电解液耐受条件下, 对不同截止电压(3.6~5.0 V, 3.6~5.2 V)的电化学特性做了详细的研究。结果表明: 此法所得材料峰形尖锐结晶良好, 且无杂质相生成, 粒度分布较为均一, 为微米-亚微米级颗粒。在5.2 V充电截止电压下, 0.5C倍率下首次放电容量高达142.9 mAh/g, 且0.5C及1C下二者的能量密度均在600 Wh/kg以上。当截止电压为5.2 V, 放电深度增大, 低倍率比容量提高, 但大倍率容量, 循环稳定性及放电电压工作平台下降均较为明显。

关键词: 喷雾热解, 尖晶石LiCr0.2Ni0.4Mn1.4O4, 截止电压, 电化学性能

Abstract:

Cathode material of LiCr_0.2Ni_0.4Mn_1.4O₄ with high energy density and superior electrochemical properties was fabricated by means of spray pyrolysis. The material was characterized via thermogravimetric analysis (TG), X-ray diffraction (XRD), scanning electron microscope (SEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in detail, and within the tolerance of current available electrolyte the discrepancy of different cut-off voltages (3.6-5.0 V, 3.6-5.2 V) was investigated. The results demonstrate that the obtained material is crystallized well without any formation of impurities, and a relative uniform particle size distribution is within micron and sub-micron. In the voltage window of 3.6-5.2 V, the initial discharge capacity can reach as high as 142.9 mAh/g at 0.5C, and its values of energy densitiy at 0.5C and 1C surpass 600 Wh/kg. If the cut-off voltage is set at 5.2 V, the degree of discharge and low-rate capacity are increased, while its high-rate capacity, cycling stability and working voltage platform are deteriorated seriously.

Key words: spray pyrolysis, spinel LiCr0.2Ni0.4Mn1.4O4, cut-off voltage, electrochemical property

中图分类号:

TQ152

陈明哲, 郭孝东, 钟本和, 闫慧敏, 张继斌, 刘俊. 喷雾热解制备高能量密度尖晶石LiCr_0.2Ni_0.4Mn_1.4O₄正极材料[J]. 无机材料学报, 2014, 29(9): 917-923.

CHEN Ming-Zhe, GUO Xiao-Dong, ZHONG Ben-He, YAN Hui-Min, ZHANG Ji-Bin, LIU Ju. High Energy Density Spinel LiCr_0.2Ni_0.4Mn_1.4O₄ Cathode Material Prepared by Spray Pyrolysis Method[J]. Journal of Inorganic Materials, 2014, 29(9): 917-923.

图/表 7

图1 所得前驱体的TG-DTG-DTA曲线

Fig. 1 TG-DTG-DTA curve of as-prepared percursor

图2 前驱体样品(a)、煅烧后样品(b)与未掺Cr样品(c) (35°~40°)的XRD图谱

Fig. 2 XRD patterns of precursor sample (a), sintered sample (b) and the comparative sample of non-doped of Cr (c)

图3 煅烧后材料不同放大倍数的SEM照片(a~c)及粒度分布曲线(d)

Fig. 3 Different magnification SEM images of calcined sample (a-c) and corresponding particle size histogram (d)

图4 材料在不同电压区间(3.6~5.0 V与3.6~5.2 V, 下同)电池的倍率性能(a), 1C及10C下二者的循环稳定性(b)、放电容量曲线(c)和能量-功率密度图(d)

Fig. 4 Rate performances of as-fabricated cells (3.6-5.0 V and 3.6-5.2 V, similarly hereinafter) at different discharge rates(a), cyclic stability performances of two batteries at 1C and 10C(b), discharge curves at different rates of two cells(c) and Ragone plots for both batteries (d)

图5 不同电压区间下的循环伏安(CV)曲线

Fig. 5 Cyclic voltammetry (CV) curves of two batteries

图 6 不同电压区间电池的交流阻抗图谱(a)与低频区域实部阻抗值及其Li+扩散系数(b)

Fig. 6 A C impedance spectra of two cells (a) and the relationship between impedance and low frequency region, and the diffusion coefficients of Li+ of both (b)

表1 计算所得不同电阻值及Li+扩散系数

Table 1 The calculated values of different resistances and diffusion coefficients of Li+

Cut-off voltage	R₁/Ω	R₂/Ω	D_Li⁺/(cm²?s^-1)
5.0 V	4.15	32.15	2.990×10^-11
5.2 V	3.62	89.67	1.435×10^-12

参考文献 28

[1]	KRAYTSBERG A, HIGHEREIN-ELI Y, STRONGER BETTER. A review of 5 volt cathode materials for advanced lithium-ion batteries. Adv. Energy Mater., 2012, 10(2): 922-939.
[2]	CLARK J M, NISHIMURA S, YAMADA A, et al. High-voltage pyrophosphate cathode: insights into local structure and lithium- diffusion pathways. Angew. Chem., 2012, 51(5): 13149-13153.
[3]	ETACHERI V, MAROM R, ELAZARI R, et al. Challenges in the development of advanced Li-ion batteries: a review. Energy Environ. Sci., 2011, 9(4): 3243-3262.
[4]	XIAO J, CHEN X L, SUSHKO P V, et al. High-performance LiNi0.5Mn1.5O4 spinel controlled by Mn3+ concentration and site disorder. Adv. Mater., 2012, 24(16): 2109-2116.
[5]	SONG J, SHIN D W, LU Y, et al. Role of oxygen vacancies on the performance of Li[Ni0.5-xMn1.5+x]O4(x= 0, 0.05, and 0.08) spinel cathodes for lithium-ion batteries. Chem. Mater., 2012, 24(15): 3101-3109.
[6]	CABANA J, CASAS-CABANAS M, OMENYA F O, et al. Composition-structure relationships in the Li-ion battery electrode material LiNi0.5Mn1.5O4. Chem. Mater., 2012, 24(15): 2952-2964.
[7]	NIE X, ZHONG B H, CHEN M Z, et al. Synthesis of LiCr0.2Ni0.4Mn1.4O4 with superior electrochemical performance via a two-step thermo polymerization technique. Electrochim. Acta, 2013, 97(1): 184-191.
[8]	SUN Q, LI X H, WANG Z X, et al. Synthesis and electrochemical performance of 5 V spinel LiNi0.5Mn1.5O4 prepared by solid-state reaction. Trans. Nonferrous Met. Soc. China, 2009, 19(1): 176-181.
[9]	ZHU Z, YAN H, ZHANG D, et al. Preparation of 4.7 V cathode material LiNi0.5Mn1.5O4 by an oxalic acid-pretreated solid-state method for lithium-ion secondary battery. J. Power Sources, 2013, 224(1): 13-19.
[10]	ZHANG X L, CHENG F Y, ZHANG K, et al. Facile polymer-assisted synthesis of LiNi0.5Mn1.5O4 with a hierarchical micro-nano structure and high rate capability. RSC Adv., 2012, 13(2): 5669-5675.
[11]	FENG J J, HUANG Z P, GUO C, et al. An organic coprecipitation route to synthesize high voltage LiNi0.5Mn1.5O4. ACS Appl. Mater. Interfaces, 2013, 5(20): 10227-10232.
[12]	ZHAO SHI-XI, LI YING-DA, DING HAO, et al. Structure and electrochemical performance of LiFePO4/C cathode materials coated with nano Al2O3 for lithium-ion battery. Journal of Inorganic Materials, 2013, 28(11): 136-140.
[13]	PARK S H, SUN Y K. Synthesis and electrochemical properties of 5V spinel LiNi0.5Mn1.5O4 cathode materials prepared by ultrasonic spray pyrolysis method. Electrochim. Acta, 2004, 50(2): 431-434.
[14]	KIM J H, MYUNG S T, SUN Y K. Molten salt synthesis of LiNi0.5Mn1.5O4 spinel for 5 V class cathode material of Li-ion secondary battery. Electrochim. Acta, 2004, 49(2): 219-227.
[15]	ZHANG WEN-HUA, HE WEI, PEI FENG, et al. Improved electrochemical properties of Al3+-doped 0.5Li2MnO3- 0.5LiCo1/3Ni1/3Mn1/3O2 cathode for lithium ion batteries. Journal of Inorganic Materials, 2013, 28(11): 114-117.
[16]	SUN Y C, WANG Z X, HUANG X J, et al. Synthesis and electrochemical performance of spinel LiMn2-x-yNixCryO4 as 5 V cathode materials for lithium ion batteries. J. Power Sources, 2004, 132(1): 161-165.
[17]	SUSHKO P V, ROSSO K M, ZHANG J G, et al. Oxygen vacancies and ordering of d-levels control voltage suppression in oxide cathodes: the case of spinel LiNi0.5Mn1.5O4-δ. Adv. Funct. Mater., 2013(1): 205-210.
[18]	WANG L, LI H, HUANG X, et al. A comparative study of Fd-3m and P4332 “LiNi0.5Mn1.5O4”. Solid State Ionics, 2011, 193(1): 32-38.
[19]	ZHANG X L, CHENG F Y, YANG J G, et al. LiNi0.5Mn1.5O4 porous nanorods as high-rate and long-life cathodes for Li-ion batteries. Nano Lett., 2013, 13(6): 2822-2825.
[20]	AKLALOUCH M, ROJAS R M, ROJO J M, et al. The role of particle size on the electrochemical properties at 25 and at 55℃ of the LiCr0.2Ni0.4Mn1.4O4 spinel as 5 V-cathode materials for lithium-ion batteries. Electrochim. Acta, 2009, 54(28): 7542-7550.
[21]	AURBACH D, MARKOVSKY B, TALYOSSEF Y, et al. Studies of cycling behavior, ageing, and interfacial reactions of LiNi0.5Mn1.5O4 and carbon electrodes for lithium-ion 5 V cells. J. Power Sources, 2006, 162(2): 780-789.
[22]	SHA O, TANG Z Y, WANG S L, et al. The multi-substituted LiNi0.475Al0.01Cr0.04Mn1.475O3.95F0.05 cathode material with excellent rate capability and cycle life. Electrochim. Acta, 2012, 77(5): 250-255.
[23]	AKLALOUCH M, AMARILLA J M, ROJAS R M, et al. Sub-micrometric LiCr0.2Ni0.4Mn1.4O4 spinel as 5 V-cathode material exhibiting huge rate capability at 25 and 55℃. Electrochem. Commun., 2010, 12(4): 548-552.
[24]	PATOUX S, DANIEL L, BOURBON C, et al. High voltage spinel oxides for Li-ion batteries: From the material research to the application. J. Power Sources, 2009, 189(1): 344-352.
[25]	ZHONG G B, WANG Y Y, ZHANG Z C, et al. Effects of Al substitution for Ni and Mn on the electrochemical properties of LiNi0.5Mn1.5O4. Electrochim. Acta, 2011, 56(18): 6554-6561.
[26]	ZHONG G B, WANG Y Y, YU Y Q, et al. Electrochemical investigations of the LiNi0.45M0.10Mn1.45O4 (M=Fe, Co, Cr) 5 V cathode materials for lithium ion batteries. J. Power Sources, 2012, 205(1): 385-393.
[27]	SHIN D W, MANTHIRAM A. Surface-segregated, high-voltage spinel LiMn1.5Ni0.42Ga0.08O4 cathodes with superior high-tempera-ture cyclability for lithium-ion batteries. Electrochem. Commun., 2011, 13(11): 1213-1216.
[28]	JU B W, WANG X Y, WEI Q L, et al. Synthesis and electrochemical performance of spherical high-voltage LiNi0.5Mn1.5O4. The Chinese Journal of Nonferrous Metals, 2013, 23(6): 1633-1639.

喷雾热解制备高能量密度尖晶石LiCr_0.2Ni_0.4Mn_1.4O₄正极材料

High Energy Density Spinel LiCr_0.2Ni_0.4Mn_1.4O₄ Cathode Material Prepared by Spray Pyrolysis Method

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