富锂锰表面超临界CO<sub>2</sub>辅助包覆磷酸锰锂及其电化学性能

doi:10.11896/j.issn.1005-023X.2018.23.007

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Abstract Li-rich layered metal oxides Li[Li_0.2Mn_0.54Co_0.13Ni_0.13]O₂(LMCN) are recognized as one of the most ideal cathode materials for high energy density lithium-ion batteries. Nevertheless, LMCN suffers from high irreversible capacity for the first time, short cycling life and serious voltage attenuation caused by structure collapse. Consequently, an effective strategy, namely a process of coating LiMnPO₄ (LMP) by assistance of supercritical CO₂ was put forward to enhance the property of LMCN. The impact of LMP coating content on the structure and electrochemical lithium-storage properties of LMP-LMCN samples are explored. It could be found that the LMP3-LMCN sample with 3wt% LMP presented high initial Coulombic efficiency of 81.1%, favorable capacity retention of 79.2% with low voltage fading of 0.47 V after 100 cycles at 30 mA·g^-1, and excellent rate capacity of 88.76 mAh·g^-1 even at a high current density of 1 500 mA·g^-1, which is much better than pristine LMCN.

Key words： Li-ion battery Li-rich layered metal oxide LiMnPO₄ supercritical CO₂ surface modification

Published: 20 December 2018

CLC number:

O646

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	Articles by authors
	HUANG Hui
	HAN Jianfeng
	WANG Yishun
	XIA Yang
	ZHANG Jun
	GAN Yongping
	LIANG Chu
	ZHANG Wenkui

Cite this article:

HUANG Hui,HAN Jianfeng,WANG Yishun, et al. Supercritical CO₂ Assisting Cladding of LiMnPO₄ on the Surface of Li[Li_0.2-Mn_0.54Co_0.13Ni_0.13]O₂ and Its Electrochemical Properties[J]. Materials Reports, 2018, 32(23): 4072-4078.

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http://www.mater-rep.com/EN/10.11896/j.issn.1005-023X.2018.23.007 OR http://www.mater-rep.com/EN/Y2018/V32/I23/4072

1 Armand M, Tarascon J M.Building better batteries[J].Nature,2008,451:652.
2 Fan J, Li G, Luo D, et al.Hydrothermal-assisted synthesis of Li-rich layered oxide microspheres with high capacity and superior rate-capability as a cathode for lithium-ion batteries[J].Electrochimica Acta,2015,173:7.
3 Croy J R, Abouimrane A, Zhang Z.Next-generation lithium-ion batteries: The promise of near-term advancements[J].MRS Bulletin,2014,39:407.
4 Li J W, Li Y, Kong Y Z.Recent progress in core-shell ternary cat-hode material for lithium-ion battery[J].Materials Review,2016,30(Z1):187(in Chinese).
李佳玮,厉英,孔亚州.核壳结构三元锂离子电池正极材料研究进展[J].材料导报,2016,30(Z1):187.
5 Liu H, Fell C R, An K, et al.In-situ neutron diffraction study of the xLi₂MnO₃·(1-x)LiMO₂(x=0,0.5;M=Ni,Mn,Co) layered oxide compounds during electrochemical cycling[J].Journal of Power Sources,2013,240:772.
6 Goodenough J B, Kim Y.Challenges for rechargeable Li batteries[J].Chemistry of Materials,2010,22(3):587.
7 Xue J Y, Hou B, Mo Y, et al.PVDF-HFP based gel electrolyte for lithium-ion battery with LiNi_0.5Co_0.2Mn_0.3O₂ cathode[J].Materials Review B:Research Papers,2017,31(6):6(in Chinese).
薛景元,侯博,莫岩,等.PVDF-HFP基凝胶电解质用于LiNi_0.5Co_0.2-Mn_0.3O₂三元正极锂离子电池[J].材料导报:研究篇,2017,31(6):6.
8 Xia Q B, Zhao X F, Xu M Q, et al.A Li-rich layered@spinel@carbon heterostructured cathode material for high capacity and high rate lithium-ion batteries fabricated via an in situ synchronous carbonization-reduction method[J].Journal of Materials Chemistry A,2015,3(7):3995.
9 Arunkumar T A, Wu Y, Manthiram A.Factors influencing the irreversible oxygen loss and reversible capacity in layered Li[Li_1/3-Mn_2/3]O₂-Li[M]O₂(M=Mn_0.5-_yNi_0.5-_yCo₂_y and Ni₁-_yCo_y) solid solutions[J].Chemistry of Materials,2007,19(12):3067.
10 Xu M, Fei L, Lu W, et al.Engineering hetero-epitaxial nanostructures with aligned Li-ion channels in Li-rich layered oxides for high-performance cathode application[J].Nano Energy,2017,35:271.
11 Thackeray M M, Kang S H, Jnhnson C S, et al.Comments on the structural complexity of lithium-rich Li₁+_xM₁-_xO₂ electrodes (M=Mn, Ni, Co) for lithium batteries[J].Electrochemistry Communications,2006,8(9):1531.
12 Croy J R, Balasubramanian M, Galagher K G, et al.Review of the U.S. department of energy’s "deep dive" effort to understand vol-tage fade in Li- and Mn-rich cathodes[J].Accounts of Chemical Research,2015,48(11):2813.
13 Kim T, Song B H, Lunt A J G, et al. In operando X-ray absorption spectroscopy study of charge rate effects on the atomic environment in graphene-coated Li-rich mixed oxide cathode[J].Materials & Design,2016,98:231.
14 Gan Y P, Lin P P, Huang H, et al.Effects of surfactants on Al₂O₃-modified Li-rich layered metal oxide cathode materials for advanced Li-ion batteries[J].Acta Physico-Chimica Sinica,2017,33(6):1189(in Chinese).
甘永平,林沛沛,黄辉,等.表面活性剂对氧化铝修饰富锂锰基正极材料的影响[J].物理化学学报,2017,33(6):1189.
15 Qin C C, Cao J L, Chen J, et al.Improvement of electrochemical performance of nickel rich LiNi_0.6Co_0.2Mn_0.2O₂ cathode active material by ultra thin TiO₂ coating[J].Dalton Transactions,2016,45(23):9669.
16 Shi S J, Tu J P, Zhang Y J, et al.Effect of Sm₂O₃ modification on Li[Li_0.2Mn_0.56Ni_0.16Co_0.08]O₂ cathode material for lithium ion batteries[J].Electrochimica Acta,2013,108:441.
17 Cho W, Kim S M, Song J H, et al.Improved electrochemical and thermal properties of nickel rich LiNi_0.6Co_0.2Mn_0.2O₂ cathode materials by SiO₂ coating[J].Journal of Power Sources,2015,282:45.
18 Sun Y K, Lee M J, Yoon C S, et al.The role of AlF₃ coatings in improving electrochemical cycling of Li-enriched nickel-manganese oxide electrodes for Li-ion batteries[J].Advanced Materials,2012,24:1192.
19 Liu S, Wu H, Huang L, et al.Synthesis of Li₂Si₂O₅-coated LiNi_0.6-Co_0.2Mn_0.2O₂ cathode materials with enhanced high-voltage electrochemical properties for lithium-ion batteries[J].Journal of Alloys and Compounds,2016,674:447.
20 Li G, Azuma H, Tohda M.Optimized LiMn_yFe₁-_yPO₄ as the cat-hode for lithium batteries[J].Journal of the Electrochemical Society,2002,149(6):A743.
21 Wang C, Li S, Han Y, et al.Assembly of LiMnPO₄ nanoplates into microclusters as a high-performance cathode in lithium-ion batte-ries[J].ACS Applied Materials & Interfaces,2017,9(33):27618.
22 Choi D, Wang D, Bae I T, et al.LiMnPO₄ nanoplate grown via solid-state reaction in molten hydrocarbon for Li-ion battery cathode[J].Nano Letters,2010,10(8):2799.
23 Qiao Q Q, Zhang H Z, Li G R, et al.Surface modification of Li-rich layered Li(Li_0.17Ni_0.25Mn_0.58)O₂ oxide with LiMnPO₄ as the cathode for lithium-ion batteries[J].Journal of Materials Chemistry A,2013,1:5262.
24 Leeke G A, Lu T, Bridson R H, et al.Application of nano-particle coatings to carrier particles using an integrated fluidized bed supercritical fluid precipitation process[J].The Journal of Supercritical Fluids,2014,91:7.
25 Liu J, Wang Q, Reeja-jayan B, et al. Carbon-coated high capacity layered Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ cathodes[J].Journal of Mate-rials Chemistry,2010,12(6):750.
26 Hwang B J, Tsai Y W, Carlier D, et al.A combined computational/experimental study on LiNi_1/3Co_1/3Mn_1/3O₂[J].Chemistry of Materials,2003,15(19):3676.
27 Wang M, Luo M, Chen Y, et al.A new approach to improve the electrochemical performance of Li-rich cathode material by precursor pretreatment[J].Journal of Alloys and Compounds,2017,696:891.
28 Jiang X Y, Chu S Y, Chen Y B, et al.LiNi_0.29Co_0.33Mn_0.38O₂ polyhedrons with reduced cation mixing as a high-performance cathode material for Li-ion batteries synthesized via a combined co-precipitation and molten salt heating technique[J].Journal of Alloys and Compounds,2017,691:206.
29 Chu S Y, Wei S Y, Chen Y B, et al.Optimal synthesis and new understanding of P2-type Na_2/3Mn_1/2Fe_1/4Co_1/4O₂ as an advanced cat-hode material in sodium-ion batteries with improved cycle stability[J].Ceramics International,2018,44:5184.
30 Lu Z, Beaulieu L Y, Donaaberger R A, et al.Synthesis, structure, and electrochemical behavior of Li-[Ni_xLi_1/3-2_x_/3Mn_2/3-_x_/3]O₂[J].Journal of the Electrochemical Society,2002,149(6):A778.
31 Chen S, Zheng Y, Lu Y, et al.Enhanced electrochemical perfor-mance of layered lithium-rich cathode materials by constructing spinel-structure skin and ferric oxide islands[J].ACS Applied Materials & Interfaces,2017,9(10):8669.
32 Zhang X, Luo D, Li G, et al.Self-adjusted oxygen-partial-pressure approach to the improved electrochemical performance of electrode Li[Li_0.14Mn_0.47Ni_0.25Co_0.14]O₂ for lithium-ion batteries[J].Journal of Materials Chemistry A,2013,1(34):9721.