LiNi0.5Mn0.5-xCoxO2(0≤x≤0.12)正极材料的制备及其电化学性能

doi:10.11901/1005.3093.2018.357

材料研究学报

2018, Vol. 32

Issue (7): 487-494 DOI: 10.11901/1005.3093.2018.357

研究论文

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LiNi_0.5Mn_0.5-_xCo_xO₂(0≤x≤0.12)正极材料的制备及其电化学性能

钟盛文¹(

), 张华军¹, 姚文俐^1,²(

), 张骞¹, 付宇坤¹, 唐小冬¹

1 江西理工大学材料科学与工程学院江西省动力电池及其材料重点实验室赣州 341000
2 江西省钨与稀土研究院赣州 341000

Preparation and Electrochemical Performance of LiNi_0.5Mn_0.5-_xCo_xO₂(0≤x≤0.12) Cathode Materials

Shengwen ZHONG¹(

), Huajun ZHANG¹, Wenli YAO^1,²(

), Qian ZHANG¹, Yukun FU¹, Xiaodong TANG¹

1 Jiangxi Key Laboratory of Power Battery and Material, School of Materials Science and Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, China
2 Jiangxi Reserach Institue of Tungsten and Rare Earths, Ganzhou 341000, China

引用本文:

钟盛文, 张华军, 姚文俐, 张骞, 付宇坤, 唐小冬. LiNi_0.5Mn_0.5-_xCo_xO₂(0≤x≤0.12)正极材料的制备及其电化学性能[J]. 材料研究学报, 2018, 32(7): 487-494.
Shengwen ZHONG, Huajun ZHANG, Wenli YAO, Qian ZHANG, Yukun FU, Xiaodong TANG. Preparation and Electrochemical Performance of LiNi_0.5Mn_0.5-_xCo_xO₂(0≤x≤0.12) Cathode Materials[J]. Chinese Journal of Materials Research, 2018, 32(7): 487-494.

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摘要:

将简单共沉淀与高温固相法相结合制备了LiNi_0.5Mn_0.5-_xCo_xO₂(0<x≤0.12)正极材料,使用XRD、SEM、EDS和XPS等手段表征其物相结构、形貌、各元素的含量和价态,根据恒电流充放电和电化学交流阻抗谱表征其电化学性能。结果表明,LiNi_0.5Mn_0.5-_xCo_xO₂正极材料具有α-NaFeO₂型层状结构;成功地将Co引入到材料的晶格内部分替代了Mn;Ni和Mn的价态分别为+2和+4,Co的价态为+3,引入Co使材料出现氧缺失。引入Co可明显改善材料的倍率性能、循环稳定性和低温性能。在2.75~4.35 V和0.2C条件下x=0.12的电极材料其首次放电比容量为180.8 mAh·g^-1,100次循环后容量保持率为92.3%,-20℃的放电比容量为25℃放电比容量的66.3%。

关键词 ：无机非金属材料, LiNi_0.5Mn_0.5-_xCo_xO₂正极材料, 共沉淀法, 电化学阻抗, 低温性能, 锂离子电池

Abstract：

Cathode materials of LiNi_0.5Mn_0.5-_xCo_xO₂(0<x≤0.12) were synthesized via simple co-precipitation and high-temperature solid-state reaction processes. The prepared materials were characterized by SEM, XRD, EDS and XPS. Their electrochemical performance was examined by galvanostatic charge-discharge tests, electrochemical impedance spectroscopy. Results show that all of the doped samples have a typical α-NaFeO₂ layered structure with partial substitution of Co-atom for Mn-atom in the crystal lattice. XPS analysis showed that there is oxygen deficiency in the doped materials and the valence states of Ni, Mn and Co were mainly +2, +4 and +3, respectively. It has been found that the Co-doped LiNi_0.5Mn_0.5O₂ shows better cycling stability, rate capacity and low-temperature property than LiNi_0.5Mn_0.5O₂ without Co doping. For cycled at 25oC in the voltage range of 2.75~4.35 V, the LiNi_0.5Mn_0.5-_xCo_0.12O₂ delivered initial discharge specific capacity of 180.8 mAh·g^-1 and kept capacity retention rate of 92.3% after 100 cycles. The discharge specific capacity for the corresponding electrode cycled at -20oC is about 66.3% of its initial discharge specific capacity cycled at 25oC.

Key words： inorganic non-metallic materials LiNi_0.5Mn_0.5-xCo_xO₂cathode material co-precipitation method electrochemical impedance spectroscopy low-temperature property lithium-ion batteries

收稿日期: 2017-11-04

ZTFLH:

TB221

基金资助:国家自然科学基金(51372104),江西省教育厅(GJJ160601),江西理工大学博士启动基金(jxxjbs16025),赣市财教字[2017]197号,江西省对外科技合作(20123BDH80016)

作者简介:

作者简介钟盛文,男,1963年生,教授

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https://www.cjmr.org/CN/10.11901/1005.3093.2018.357 或 https://www.cjmr.org/CN/Y2018/V32/I7/487

图1 LiNi0.5Mn0.5-xCoxO2的XRD图谱

表1 LiNi0.5Mn0.5-xCoxO2的晶胞参数

图2 LiNi0.5Mn0.5-xCoxO2的SEM照片

图3 引入量0.12样品的EDS图

表2 引入量0.12样品的元素含量

图4 引入Co样品的XPS图谱

图5 LiNi0.5Mn0.5-xCoxO2的循环曲线

图6 LiNi0.5Mn0.5-xCoxO2在不同倍率下的循环曲线

图7 LiNi0.5Mn0.5-xCoxO2在-20℃,0.2C倍率下的放电曲线

图8 LiNi0.5Mn0.5-xCoxO2的循环伏安曲线

图9 LiNi0.5Mn0.5-xCoxO2的EIS图谱

[1]	Li C D, Yao Z L, Li J, et al.Preparation and electrochemical performance of LaF3-coated Li[Li0.2Mn0.54Ni0.13Co0.13]O2 as cathode Material for lithium-ion batteries[J]. Chin. J. Mater. Res ., 2017, 31(5): 394(李成冬, 姚志垒, 李举等. LaF3表面修饰Li[Li0.2Mn0.54Ni0.13Co0.13]O2的制备及其电化学性能[J]. 材料研究学报, 2017, 31(5): 394)
[2]	Zhong S, Chen P, Yao W.Ni-rich layered oxide Li1.05(Ni0.7Mn0.3)O2 as a highly reversible cathode material for lithium-ion batteries[J]. ECS Electrochem. Lett ., 2015, 4(6): A45
[3]	Goodenough J B, Kim Y.Challenges for rechargeable batteries[J]. J. Power Sources, 2010, 196(7): 6688
[4]	Ariyoshi K, Ichikawa T, Ohzuku T.Structural change of LiNi0.5-Mn0.5O2 during charge and discharge in nonaqueous lithium cells[J]. J. Phys. Chem. Solids, 2008, 69: 1238
[5]	Lu H Q, Wu F, Su Y F, et al.Electrochemical performance of LiNi0.5-Mn0.5O2 as cathode material for lithium-ion batteries prepared by oxalate co-precipitation method[J]. Acta Phys.-Chim. Sin ., 2010, 26(1): 51(卢华权, 吴锋, 苏岳锋等. 草酸共沉淀法制备锂离子电池正极材料LiNi0.5Mn0.5O2及其电化学性能[J]. 物理化学学报, 2010, 26(1): 51)
[6]	Luo C Y, Li Z F, Peng W W, et al.First principles study on electronic structure of LixNi0.5Mn0.5O2 cathode material for lithium ion batteries[J]. Nonferrous Met. Sci. Eng ., 2016, 7(4): 45(罗垂意, 李之锋, 彭弯弯等. 锂离子电池正极材料LixNi0.5Mn0.5O2电子结构的第一性原理研究[J]. 有色金属与工程, 2016, 7(4): 45
[7]	Yang X, Xia Y.The effect of oxygen pressures on the electrochemical profile of lithium/oxygen battery[J]. J. Solid State Electrochem ., 2010, 14(1): 109
[8]	Johnson C S, Kim J S, Kropf A J, et al.Structural characterization of layered LixNi0.5Mn0.5O2 (0<x≤2) oxide electrodes for Li batteries[J]. Chem. Mater ., 2003, 15(37): 2313
[9]	Li D, Sasaki Y, Kageyama M, et al.Structure, morphology and electrochemical properties of LiNi0.5Mn0.5-xCoxO2 prepared by solid state reaction[J]. J. Power Sources, 2005, 148(2): 85
[10]	Ohzuku T, Makimura Y.Layered lithium insertion material of LiNiMnO2: A possible alternative to LiCoO2 for advanced lithium-ion batteries[J]. Chem. Lett ., 2001, 30(8): 744
[11]	Sakamoto K, Hirayama M, Konishi H.et al.Structural changes in surface and bulk LiNi0.5Mn0.5O2 during electrochemical reaction on epitaxial thin-film electrodes characterized by in situ X-ray scattering[J]. Phys. Chem. Chem. Phys ., 2010, 12: 3815
[12]	Li J, Wan L, Cao C.A high-rate and long cycling life cathode for rechargeable lithium-ion batteries: hollow LiNi0.5Mn0.5O2 nano/micro hierarchical microspheres[J]. Electrochim. Acta, 2016, 191: 974
[13]	Kang S H, Kim J, Stoll M E, et al.Layered Li(Ni0.5-xMn0.5-xM2x′)O2 (M′=Co, Al, Ti; x=0, 0.025) cathode materials for Li-ion rechargeable batteries[J]. J. Power Sources, 2002, 112(1): 41
[14]	Gwon H, Kim S W, Park Y U, et al.Ion-exchange mechanism of layered transition-metal oxides: case study of LiNi0.5Mn0.5O2[J]. Inorg. Chem ., 2014, 53: 8083
[15]	Dou S, Wang W, Li H, et al.Synthesis and electrochemical performance of LiNi0.475Mn0.475Al0.05O2 as cathode material for lithium-ion battery from Ni-Mn-Al-O precursor[J]. J. Solid State Electrochem ., 2011, 15(4): 747
[16]	Li D C, Noguchi H, Yoshio M.Electrochemical characteristics of LiNi0.5-xMn0.5-xCo2xO2(0<x≤0.1) prepared by spray dry method[J]. Electrochimica Acta, 2004, 50(2-3): 427
[17]	Yoon W S, Balasubramanian M, Yang X Q, et al.Soft X-ray absorption spectroscopic study of a LiNi0.5Mn0.5O2 cathode during charge[J]. J. Electrochem. Soc ., 2004, 151(2): A246
[18]	Dou S, Wang W, Synthesis and electrochemical properties of layered LiNi0.5-xMn0.5-xCo2xO2 for lithium-ion battery from nickel manganese cobalt oxide precursor[J]. J. Solid State Electrochem ., 2011, 15(2): 399
[19]	Chen P, Mei W J, Zhong S W, et al.Effect of sintering atmosphere on electrochemical performance of cobalt free nickel rich LiNi0.7Mn0.3-O2 as cathode material[J]. Nonferrous Met. Sci. Eng ., 2015, 6(4): 54(陈鹏, 梅文捷, 钟盛文等. 烧结气氛对无钴镍基正极材料LiNi0.7Mn0.3O2性能的影响[J]. 有色金属与工程, 2015, 6(4): 54)
[20]	Ohzuku T, Ueda A, Nagayama M.Electrochemistry and structural chemistry of LiNiO2(R3m) for 4 volt secondary lithium cells[J]. J. Electrochem. Soc ., 1993, 140(7): 1862
[21]	Sun Y K, Lee B R, Noh H J, et al.A novel concentration-gradient Li[Ni0.83Co0.07Mn0.10]O2 cathode material for high-energy lithium-ion batteries[J]. J. Mater. Chem ., 2011, 21(27): 10108
[22]	Wang Y, Zhang H, Chen W, et al.Gel-combustion synthesis and electrochemical performance of LiNi1/3Mn1/3Co1/3O2 as cathode material for lithium-ion batteries[J]. Rsc Advances, 2011, 4(70): 37148
[23]	S. Zhong, M. Lai, W. Yao, Z. Li, Synthesis and electrochemical properties of LiNi0.8CoxMn0.2-xO2 positive-electrode material for lithium-ion batteries[J]. Electrochim. Acta, 2016, 212: 343
[24]	Li L, Zhang X, Chen R, et al.Synthesis and electrochemical performance of cathode material Li1.2Co0.13Ni0.13Mn0.54O2 from spent lithium-ion batteries[J]. J. Power Sources, 2014, 249(3): 28
[25]	Quinlan R A, Lu Y C, Yang S H, et al.XPS Studies of surface chemistry changes of LiNi0.5Mn0.5O2 electrodes during high-voltage cycling[J]. J. Electrochem. Soc ., 2013, 160(4): A669
[26]	Yu C, Li G, Guan X, et al.Composites Li2MnO3·LiMn1/3Ni1/3Co1/3O2 optimized synthesis and applications as advanced high-voltage cathode for batteries working at elevated temperatures[J]. Electrochim. Acta, 2012, 81: 283
[27]	Matsuda Y, Suzuki K, Hirayama M, et al.High-pressure synthesis of lithium-rich layered rock-salt Li2(Mn3/8Co1/4Ni3/8)O3-x for lithium battery cathodes[J]. Solid State Ionics, 2014, 262: 88
[28]	Huang C K, Sakamoto J S, Wolfenstine J, et al.The limits of low-temperature performance of Li-ion cells[J]. J. Electrochem. Soc ., 2000, 147(8): 2893
[29]	Smart M C, Ratnakumar B V, Surampudi S.Use of organic esters as cosolvents in electrolytes for lithium-ion batteries with improved low temperature performance[J]. J. Electrochem. Soc ., 2002, 149: A361
[30]	Zhang S S, Xu K, Jow T R.The low temperature performance of Li-ion batteries, J. Power Sources[J]. 2003, 115(1): 137
[31]	Lu Z, Beaulieu L Y, Donaberger R A, et al.Synthesis, structure, and electrochemical behavior of Li[NixLi1/3-2x/3Mn2/3-x/3]O2[J]. J. Electrochem. Soc ., 2002, 149(6): A778
[32]	Martha S K, Nanda J, Veith G M, et al.Surface studies of high voltage lithium rich composition: Li1.2Mn0.525Ni0.175 Co0.1O2[J]. J. Power Sources, 2012, 216(11): 179
[33]	Chen Y, Chen Z, Xie K.Effect of annealing on the first-cycle performance and reversible capabilities of lithium-rich layered oxide cathodes[J]. J. Phys. Chem. C, 2014, 118(22): 11505
[34]	Liu J, Reeja-Jayan B, Manthiram A.Conductive surface modification with aluminum of high capacity layered Li[Li0.2Mn0.54Ni0.13-Co0.13]O2 cathodes[J]. J. Phys. Chem. C, 2010, 114(20): 9528
[35]	Liu J, Jiang R, Wang X, et al.The defect chemistry of LiFePO4, prepared by hydrothermal method at different ph values[J]. J. Power Sources, 2009, 194(1): 536

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