无钴镍基正极材料LiNi0.7Mn0.3O2 氟掺杂改性研究

doi:10.11896/j.issn.1005-023X.2018.14.001

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Abstract The F-doped LiNi_0.7Mn_0.3O_2-xF_x(x=0,0.01,0.02,0.03) cathode materials were synthesized by calcining the mixtures of LiOH·H₂O,LiF and Ni_0.7Mn_0.3(OH)₂ precursor formed through a simple continuous co-precipitation method. The effects of F doping on the crystal structure and electrochemical properties of LiNi_0.7Mn_0.3O₂ were investigated systematically by X-ray diffraction (XRD),scanning electron microscope(SEM) and various electrochemical measurement. The XRD results showed that with the increasing F doping amount, the cell volume of the F-doped LiNi_0.7Mn_0.3O₂ samples were slightly larger than that of pure LiNi_0.7-Mn_0.3O₂, and F doping did not change the basic α-NaFeO₂ layered structure. SEM results indicated F-doped samples showed slightly larger primary particle size and uniform morphology than pristine sample. X-ray photoelectron spectroscopy (XPS) test results showed that the content of divalent nickel in the material increased and the valence of other elements kept constant after F doping.Moreover, F-doping could improve the crystallinity of LiNi_0.7Mn_0.3O₂.EIS and CV test revealed that the charge transfer resistance(R_ct) and electrode polarization were reduced by F-doping. In spite of initial decreased discharge capacity, the columbic efficiency and cycle performance also improved.

Key words： cathode materials LiNi_0.7Mn_0.3O₂ electrochemical properties F-doping lithium ion battery

Published: 31 July 2018

CLC number:	TB321
	O64

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	Articles by authors
	LI Zhifeng
	LUO Chuiyi
	WANG Chunxiang
	ZHONG Shengwen
	ZHANG Qian

Cite this article:

LI Zhifeng,LUO Chuiyi,WANG Chunxiang, et al. Synthesis and Property of F-doped LiNi_0.7Mn_0.3O₂ Cobalt-free Nickel-rich Cathode Material for Li-ion Battery[J]. Materials Reports, 2018, 32(14): 2329-2334.

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http://www.mater-rep.com/EN/10.11896/j.issn.1005-023X.2018.14.001 OR http://www.mater-rep.com/EN/Y2018/V32/I14/2329

1 Schipper F, Erickson E M, Erk C, et al. Review—recent advances and remaining challenges for lithium ion battery cathodes: I. Nickel-rich, LiNi_xCo_yMn_zO₂[J]. Journal of the Electrochemical Society,2017,164(1):A6220.
2 Dou S. Review and prospect of layered lithium nickel manganese oxide as cathode materials for Li-ion batteries[J]. Journal of Solid State Electrochemistry,2013,17(4):911.
3 Hwang I, Lee C W, Kim J C, et al. Particle size effect of Ni-rich cathode materials on lithium ion battery performance[J]. Materials Research Bulletin,2012,47(1):73.
4 Song D, Hou P, Wang X, et al. Understanding the origin of enhanced performances in core-shell and concentration-gradient layered oxide cathode materials[J]. ACS Applied Materials & Interfaces,2015,7(23):12864.
5 Sun Y K, Lee B R, Noh H J, et al. A novel concentration-gradient Li[Ni_0.83Co_0.07Mn_0.10]O₂ cathode material for high-energy lithium-ion batteries[J]. Journal of Materials Chemistry,2011,21(27):10108.
6 Du Ke, Huang Jinlong, Hu Guorong, et al. Research on synthesis and performance of composite cathode material Li[Ni_0.92Co_0.04-Mn_0.04]O₂ with gradient-coating layers as lithium ion battery[J]. Chinese Journal of Inorganic Chemistry,2013,29(5):1031(in Chinese).
杜柯,黄金龙,胡国荣,等.梯度包覆镍酸锂材料Li[Ni_0.92Co_0.04-Mn_0.04]O₂的合成与研究[J].无机化学学报,2013,29(5):1031.
7 Wang D, Li X, Wang Z, et al. Co-modification of LiNi_0.5Co_0.2Mn_0.3-O₂, cathode materials with zirconium substitution and surface polypyrrole coating: Towards superior high voltage electrochemical performances for lithium ion batteries[J]. Electrochimica Acta,2016,196:101.
8 Xu Y, Liu Y, Lu Z, et al. The preparation and role of Li₂ZrO₃, surface coating LiNi_0.5Co_0.2Mn_0.3O₂, as cathode for lithium-ion batteries[J]. Applied Surface Science,2016,361:150.
9 Li L, Ming X, Qi Y, et al. Alleviating surface degradation of nickel-rich layered oxide cathode material by encapsulating with nanoscale Li-ions/electrons superionic conductors hybrid membrane for advanced Li-ion batteries[J]. ACS Applied Materials & Interfaces,2016,8(45):30879.
10 Duan J, Hu G, Cao Y, et al. Enhanced electrochemical performance and storage property of LiNi_0.815Co_0.15 Al_0.035O₂, via Al gradient doping[J]. Journal of Power Sources,2016,326:322.
11 Tang Z F, Wu R, Huang P F, et al. Improving the electrochemical performance of Ni-rich cathode material LiNi_0.815Co_0.15Al_0.035O₂ by removing the lithium residues and forming Li₃PO₄ coating layer[J]. Journal of Alloys & Compounds,2016,693:1157.
12 Zhao R, Yang Z, Liang J, et al. Understanding the role of Na-doping on Ni-rich layered oxide LiNi_0.5Co_0.2Mn_0.3O₂[J]. Journal of Alloys & Compounds,2016,689:318.
13 Schipper F, Dixit M, Kovacheva D, et al. Stabilizing nickel-rich layered cathode materials by a high-charge cation doping strategy: Zirconium-doped LiNi_0.6Co_0.2Mn_0.2O₂[J]. Journal of Materials Chemistry A,2016,4(41):16073.
14 Kang K, Carlier D, Reed J, et al. Synthesis and electrochemical properties of layered Li_0.9Ni_0.45Ti_0.55O₂[J]. Chemistry of Mate-rials,2003,15(23):4503.
15 Zhong S, Lai M, Yao W, et al. Synthesis and electrochemical pro-perties of LiNi_0.8Co_xMn_0.2-xO₂, positive-electrode material for lithium-ion batteries[J]. Electrochimica Acta,2016,212:343.
16 Saavedra-Arias J J, Rao C V, Shojan J, et al. A combined first-principles computational/experimental study on LiNi_0.66Co_0.17Mn_0.17O₂ as a potential layered cathode material[J]. Journal of Power Sources,2012,211(211):12.
17 Zhang L, Dong T, Yu X, et al. Synthesis and electrochemical performance of LiNi_0.7Co_0.15Mn_0.15O₂, as gradient cathode material for lithium batteries[J]. Materials Research Bulletin,2012,47(11):3269.
18 Mudit Dixit, Boris Markovsky, Doron Aurbach,et al. Unraveling the effects of Al doping on the electrochemical properties of LiNi_0.5-Co_0.2Mn_0.3O₂ using first principles[J]. Journal of the Electrochemical Society,2017,164(1): A6359.
19 Ceder G, Ven A V D. Phase diagrams of lithium transition metal oxides: Investigations from first principles[J]. Electrochimica Acta,1999,45(1-2):131.
20 Liu W J, Zhang Y, Wang F, et al. Synthesis and electrochemical properties of Li_1.03Co _0.1Mn_1.9F_zO_4-z material for lithium-ion batte-ries[J]. Transactions of Nonferrous Metals Society of China,2013,23(8):2312.
21 Li Xinhai, He Fangyong, Guo Huajun, et al. Synthesis and electrochemical performance of LiMn₂O₄ doped with F^-[J].The Chinese Journal of Nonferrous Metals,2008,18(1):54(in Chinese).
李新海,何方勇,郭华军,等.F^-掺杂LiMn₂O₄的合成及电化学性能[J].中国有色金属学报,2008,18(1):54.
22 Xia Junlei, Zhao Shixi, Liu Hanxing, et al. Study on the mechanism of influence on LiMn₂O₄ by F-dopant[J].Journal of Functional Materials,2004,35(1):74(in Chinese).
夏君磊,赵世玺,刘韩星,等.F掺杂影响LiMn₂O₄性能的机理研究[J].功能材料,2004,35(1):74.
23 Yi T, Hu X, Wang D, et al. Effects of Al, F dual substitutions on the structure and electrochemical properties of lithium manganese oxide[J]. Journal of University of Science and Technology Beijing,2008,15(2):182.
24 Su R, Dai C. Synthesis and electrochemical behavior of Mg, F dual substitutions spinel LiMg_0.1Mn_1.9O_3.95F_0.05[J]. Rare Metal Mate-rials & Engineering,2007,36(5):182.
25 Meng Mianwu, Liao Qinhong, Jiang Enyuan, et al. Effects of doping elements lanthanum and fluorine on structure and electrochemical performance of spinel LiMn₂O₄ cathode material[J]. Rare Metal Materials and Engineering,2009,38(6):995(in Chinese).
蒙冕武,廖钦洪,江恩源,等.掺杂元素La、F对尖晶石LiMn₂O₄材料结构及性能的影响[J].稀有金属材料与工程,2009,38(6):995.
26 He Y S, Pei L, Liao X Z, et al. Synthesis of LiNi_1/3Co_1/3Mn_1/3-O_2-zF_z, cathode material from oxalate precursors for lithium ion battery[J]. Journal of Fluorine Chemistry,2007,128(2):139.
27 Masaya Kageyama, Decheng Li, Koichi Kobayakawa, et al. Structural and electrochemical properties of LiNi_1/3Mn_1/3Co_1/3O_2-xF_x, prepared by solid state reaction[J]. Journal of Power Sources,2006,157:494.
28 Zheng J, Wu X, Yang Y. Improved electrochemical performance of Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂, cathode material by fluorine incorporation[J]. Electrochimica Acta,2013,105(26):200.
29 Woo S U, Park B C, Yoon C S, et al. Improvement of Electroche-mical performances of Li[Ni_0.8Co_0.1Mn_0.1]O₂ cathode materials by fluorine substitution[J]. Journal of the Electrochemical Society,2007,154(7):A649.
30 Zhang H, Song T. Synthesis and performance of fluorine substituted Li_1.05(Ni_0.5Mn_0.5)_0.95O_2-xF_x, cathode materials modified by surface coating with FePO₄[J]. Electrochimica Acta,2013:116.
31 Zhang X, Mauger A, Qi L, et al. Synthesis and characterization of LiNi_1/3Mn_1/3Co_1/3O₂, by wet-chemical method[J]. ECS Transactions,2010,55(22):6440.
32 Konishi H, Yoshikawa M, Hirano T. The effect of thermal stability for high-Ni-content layer-structured cathode materials, LiNi_0.8-Mn_0.1-xCo_0.1Mo_xO₂(x=0,0.02,0.04)[J]. Journal of Power Sources,2013,244(4):23.
33 Kou Y, Han E, Zhu L Z, et al. The effect of Ti doping on electrochemical properties of Li_1.167Ni_0.4Mn_0.383 Co_0.05O₂, for lithium-ion batteries[J]. Solid State Ionics,2016,296:154.
34 Fu C, Li G, Luo D, et al. Nickel-rich layered microspheres ca-thodes: Lithium/nickel disordering and electrochemical performance[J]. ACS Applied Materials & Interfaces,2014,6(18):15822.