•  
  •  
 

Corresponding Author

Yong YANG(yyang@xmu.edu.cn)

Abstract

In order to investigate the effects of Al-doping on the structure, morphology and electrochemical performance of Ni-rich layered oxides, the NCA cathode materials with a nominal chemical formula of LiNi0.8Co0.15Al0.05O2 were prepared by two methods with different aluminum sources. One was the solid phase method: the precursor (Ni0.84Co0.16(OH)2) prepared by co-precipitation was mixed with lithium and aluminum source (nano-Al2O3 or Al(NO3)3) thoroughly, and calcined at 780 ℃ for 15 h under an oxygen atmosphere. The other was the co-precipitation method: the NCA precursor (Ni0.8Co0.15Al0.05(OH)2.05) was synthesized by co-pre- cipitation method employing either Al2(SO4)3 or NaAlO2 as an aluminum source, and the NCA precursor was then mixed with lithium source and sintered at 780 ℃ for 15 h under an oxygen atmosphere. The results showed that Al-doping reduced the degree of cation mixing and maintained the stability of the layered structure, thereby reducing the voltage drop and improving its cycle performance. The NCA material prepared by co-precipitation method employing NaAlO2 as the aluminum source revealed the morphology of dense microspheres with a uniform size distribution and a well-layered structure of low Ni2+/Li+ mixing, acheving the best performance. The as-prepared NCA cathode material delivered a high discharge capacity (198 mAh·g-1 at 0.1C) corresponding to 94.6% coulombic efficiency and good cycle stability (a capacity retention of 70% after 200 cycles at 1C) between 3.0 V and 4.3 V.

Graphical Abstract

Keywords

Lithium-ion battery, co-precipitation method, Ni-rich cathode; LiNi0.8Co0.15Al0.05O2, doping

Publication Date

2019-12-28

Online Available Date

2018-05-02

Revised Date

2018-04-23

Received Date

2018-03-28

References

[1] Nitta N, Wu F X, Lee J T, et al. Li-ion battery materials: present and future[J]. Materials Today, 2015,18(5): 252-264.
[2] Li W D, Song B H, Manthiram A. High-voltage positive electrode materials for lithium-ion batteries[J]. Chemical Society Reviews, 2017,46(10): 3006-3059.
[3] Lee W, Muhammad S, Kim T, et al. New insight into Ni-rich layered structure for next-generation Li rechargeable batteries[J]. Advanced Energy Materials, 2017: 1701788.
[4] Makimura Y, Sasaki T, Nonaka T, et al. Factors affecting cycling life of LiNi0.8Co0.15Al0.05O2 for lithium-ion batteries[J]. Journal of Materials Chemistry A, 2016,4(21): 8350-8358.
[5] Mohanty D, Dahlberg K, King D M, et al. Modification of Ni-rich FCG NMC and NCA cathodes by atomic layer deposition: preventing surface phase transitions for high-voltage lithium-ion batteries[J]. Scientific Reports, 2016, 6: 26532.
[6] Muto S, Tatsumi K, Kojima Y, et al. Effect of Mg-doping on the degradation of LiNiO2-based cathode materials by combined spectroscopic methods[J]. Journal of Power Sources, 2012, 205: 449-455.
[7] Liang C P, Kong F T, Longo R C, et al. Site-dependent multicomponent doping strategy for Ni-rich LiNi1-2yCoyMnyO2(y = 1/12) cathode materials for Li-ion batteries[J]. Journal of Materials Chemistry A, 2017, 5(48): 25303-25313.
[8] Dixit M, BorisMarkovsky, Aurbach D, et al. Unraveling the effects of Al doping on the electrochemical properties of LiNi0.5Co0.2Mn0.3O2 using first principles[J]. Journal of The Electrochemical Society, 2017, 164(1): A6359-A6365.
[9] Chen C H, Liu J, Stoll M E, et al. Aluminum-doped lithium nickel cobalt oxide electrodes for high-power lithium-ion batteries[J]. Journal of Power Sources, 2004, 128(2): 278-285.
[10] Hoang K, Johannes M. Defect physics and chemistry in layered mixed transition metal oxide cathode materials: (Ni, Co, Mn) vs (Ni, Co, Al)[J]. Chemistry of Materials, 2016, 28(5): 1325-1334.
[11] Ju S H, Jang H C, Kang Y C. Al-doped Ni-rich cathode powders prepared from the precursor powders with fine size and spherical shape[J]. Electrochimica Acta, 2007, 52(25): 7286-7292.
[12] Kim Y, Kim D. Synthesis of high-density nickel cobalt aluminum hydroxide by continuous coprecipitation method[J]. ACS Applied Materials & Interfaces, 2012, 4(2): 586-589.
[13] Li Y, Xu R, Ren Y, et al. Synthesis of full concentration gradient cathode studied by high energy X-ray diffraction[J]. Nano Energy, 2016, 19: 522-531.
[14] Zhou P F, Meng H J, Zhang Z, et al. Stable layered Ni-rich LiNi0.9Co0.07Al0.03O2 microspheres assembled with nanoparticles as high-performance cathode materials for lithiumion batteries[J]. Journal of Materials Chemistry A, 2017, 5(6): 2724-2731.
[15] Jiang Z J(蒋志军), Zhang Y L(张亚莉), Wang Q(王乾), et al. Continuous synthesis and condition exploration of precursor Ni1/3Co1/3Mn1/3(OH)2 ternary cathode material[J]. Journal of Electrochemistry(电化学), 2016, 22(5): 528-534.
[16] Guan X Y(关小云), Hong C Y(洪朝钰), Zhu J P(朱建平), et al. Synthesis and electrochemical properties of nickel-rich cathode material LiNi0.6Co0.2Mn0.2O2 with high initial coulombic efficiency[J]. Journal of Electrochemistry(电化学), 2018, 24(1): 56-62.
[17] Liu W M, Hu G R, Peng Z D, et al. Synthesis of spherical LiNi0.8Co0.15Al0.05O2 cathode materials for lithium-ion batteries by a co-oxidation-controlled crystallization method[J]. Chinese Chemical Letters, 2011, 22(9): 1099-1102.
[18] Zhou F, Zhao X M, van Bommel A, et al. Coprecipitation synthesis of NixMn1-x(OH)2 mixed hydroxides[J]. Chemistry of Materials, 2010, 22(3): 1015-1021.
[19] Kim J. Synthesis and electrochemical behavior of Li[Li0.1Ni0.35-x/2CoxMn0.55-x/2]O2 cathode materials[J]. Solid State Ionics, 2003, 164(1/2): 43-49.
[20] Zhu X M, Wang Y X, Shang K H, et al. Improved rate capability of the conducting functionalized FTO-coated Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode material for Li-ion batteries[J]. Journal of Materials Chemistry A, 2015, 3(33): 17113-17119.
[21] Liang M, Song D W, Zhang H Z, et al. Improved performances of LiNi0.8Co0.15Al0.05O2 material employing NaAlO2 as a new aluminum source[J]. ACS Applied Materials & Interfaces, 2017, 9(44): 38567-38574.
[22] Hwang S, Chang W, Kim S M, et al. Investigation of changes in the surface structure of LixNi0.8Co0.15Al0.05O2 cathode materials induced by the initial charge[J]. Chemistry of Materials, 2014, 26(2): 1084-1092.
[23] Bettge M, Li Y, Gallagher K, et al. Voltage fade of layered oxides: its measurement and impact on energy density[J]. Journal of The Electrochemical Society, 2013, 160(11): A2046-A2055.
[24] Watanabe S, Kinoshita M, Hosokawa T, et al. Capacity fade of LiAlyNi1-x-yCoxO2 cathode for lithium-ion batteries during accelerated calendar and cycle life tests (surface analysis of LiAlyNi1-x-yCoxO2 cathode after cycle tests in restricted depth of discharge ranges)[J]. Journal of Power Sources, 2014, 258: 210-217.
[25] Huang Y Q, Huang Y H, Hu X L. Enhanced electrochemical performance of LiNi0.8Co0.15Al0.05O2 by nanoscale surface modification with Co3O4[J]. Electrochimica Acta, 2017, 231: 294-299.

Share

COinS
 
 

To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.