Aqueous Solution-Evaporation Route Synthesis and Phase Structural Research of the Li-Rich Cathode Li_1.23Ni_0.09Co_0.12Mn_0.56O₂ by In-Situ XRD

Authors

Chong-Heng SHEN, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Fujian Xiamen 361005;
Shou-Yu SHEN, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Fujian Xiamen 361005;
Zhou LIN, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Fujian Xiamen 361005;
Xiao-Mei ZHENG, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Fujian Xiamen 361005;
Hang SU, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Fujian Xiamen 361005;
Ling HUANG, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Fujian Xiamen 361005;Follow
Jun-Tao LI, School of Energy Research, Xiamen University, Fujian Xiamen 361005;
Shi-Gang SUN, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Fujian Xiamen 361005;

Corresponding Author

Ling HUANG(huangl@xmu.edu.cn)

Abstract

The Li-rich Li_1.23Ni_0.09Co_0.12Mn_0.56O₂ material was synthesized via aqueous solution-evaporation route. The structure and morphology of the material were characterized by means of XRD and SEM. The results indicated that the single particle of the product was polygonal with the size of 330 nm and the structure was layered solid solution with a certain amount of Li₂MnO₃. Electrochemical tests showed that the first discharge capacity of the Li-rich layered material was 250.8 mAh·g^-1 at 0.1C，the capacity retention was 86.5% after 40 cycles. Through in-situ XRD study a new phase Li_0.9MnO₂ which would cause electrochemical properties deteriorated due to its structure transformation from layered to spinel came out with a small amount during the first charge-discharge cycle. Moreover, the value of c-parameter increased first and decreased before 4.54 V, and remained stable till the end of the first charge, and then reduced from the first discharge to the second charge continually. However, the value of a-parameter underwent a falling-steady-rising course. The change in the values of the lattice parameters corresponded to the variation of electrochemical behaviors.

Graphical Abstract

Keywords

Li-ion battery, cathode, aqueous solution-evaporation route, in-situ XRD, structure transformation

DOI Link

https://doi.org/10.13208/j.electrochem.130359

Publication Date

2013-12-28

Online Available Date

2013-12-23

Revised Date

2013-07-01

Received Date

2013-05-31

Recommended Citation

Chong-Heng SHEN, Shou-Yu SHEN, Zhou LIN, Xiao-Mei ZHENG, Hang SU, Ling HUANG, Jun-Tao LI, Shi-Gang SUN. Aqueous Solution-Evaporation Route Synthesis and Phase Structural Research of the Li-Rich Cathode Li_1.23Ni_0.09Co_0.12Mn_0.56O₂ by In-Situ XRD[J]. Journal of Electrochemistry, 2013 , 19(6): 537-543.
DOI: 10.13208/j.electrochem.130359
Available at: https://jelectrochem.xmu.edu.cn/journal/vol19/iss6/6

References

[1] Mohanty D, Kalnaus S, Meisner R A, et al. Structural transformation of a lithium-rich Li1.2Co0.1Mn0.55Ni0.15O2 cathode during high voltage cycling resolved by in situ X-ray diffraction[J]. Journal of Power Sources, 2013, 229: 239-248.

[2] Thackeray M M, Kang S H, Johnson C S, et al. Li2MnO3-stabilized LiMO2 (M = Mn, Ni, Co) electrodes for lithium-ion batteries[J]. Journal of Materials Chemistry, 2007, 17(30): 3112-3125.

[3] Li J, Kl?psch R, Stan M C, et al. Synthesis and electrochemical performance of the high voltage cathode material Li[Li0.2Mn0.56Ni0.16Co0.08]O2 with improved rate capability[J]. Journal of Power Sources, 2011, 196(10): 4821-4825.

[4] Park K S, Song C H, Stephan A M, et al. Influence of solvents on the synthesis and electrochemical properties of Li[Li1/5Ni1/10Co1/5Mn1/2]O2 for the applications in lithium-ion batteries[J]. Journal of Materials Science, 2006, 41(22): 7628-7635.

[5] Zhao Y J, Zhao C S, Sun Z Q, et al. Synthesis and characterization of Li-rich cathode materials Li[Li(1/3-x/3)CoxMn(2/3-2x/3)]O2 by modified pechini method[J]. Acta Chimica Sinica, 2011, 69(2): 117-121.

[6] Hong Y S, Park Y J, Ryu K S, et al.Synthesis and electrochemical properties of nanocrystalline LiNi0.20Li0.20Mn0.60O2. Electrochemical and Solid State Letters, 2003, 6(8): A166-A169.

[7] Du K, Zhou W Y, Hu G R, et al. Synthesis and electrochemical properties of Li[Li0.2Mn0.54Ni0.13Co0.13]O2 as cathode material for Li-ion batteries[J]. Acta Chimica Sinica, 2010, 68(14): 1391-1398.

[8] Du K, Huang X, Hu G R, et al. Synthesis and electrochemical properties of Li[Li0.2Ni0.2Mn0.6]O2 as high capacity cathode material[J]. The Chinese Journal of Nonferrous Metals, 2012, 22(4): 1201-1208.

[9] Yang X Q, Sun X, McBreen J. New findings on the phase transitions in Li1-xNiO2: in situ synchrotron X-ray diffraction studies[J]. Electrochemistry Communications, 1999, 1(6): 227-232.

[10] Yang X Q, Sun X, McBreen J. Structural changes and thermal stability: In situ X-ray diffraction studies of a new cathode material LiMg0.125Ti0.125Ni0.75O2[J]. Electrochemistry Communications, 2000, 2(10): 733-737.

[11] Yang X Q, Sun X, McBreen J.New phases and phase transitions observed in Li1-xCoO2 during charge: In situ synchrotron X-ray diffraction studies[J]. Electrochemistry Communications, 2000, 2(2): 100-103.

[12] Yang X Q, McBreen J, Yoon W S, et al. Crystal structure changes of LiMn0.5Ni0.5O2 cathode materials during charge and discharge studied by synchrotron based in situ XRD[J]. Electrochemistry Communications, 2002, 4(8): 649-654.

[13] Liao P Y, Duh J G, Lee J F, et al. Structural investigation of Li1?xNi0.5Co0.25Mn0.25O2 by in situ XAS and XRD measurements[J]. Electrochimica Acta, 2007, 53(4): 1850-1857.

[14] Liao P Y, Duh J G, Sheu H S. Structural and thermal properties of LiNi0.6?xMgxCo0.25Mn0.15O2 cathode materials[J]. Journal of Power Sources, 2008, 183(2): 766-770.

[15] Nam K W, Yoon W S, Shin H J, et al. In situ X-ray diffraction studies of mixed LiMn2O4-LiNi1/3Co1/3Mn1/3O2 composite cathode in Li-ion cells during charge-discharge cycling[J]. Journal of Power Sources, 2009, 192(2): 652-659.

[16] Yoon W S, Nam K W, Jang D H, et al.The kinetic effect on structural behavior of mixed LiMn2O4-LiNi1/3Co1/3Mn1/3O2 cathode materials studied by in situ time-resolved X-ray diffraction technique[J]. Electrochemistry Communications, 2012, 15(1): 74-77.

[17] Ito A, Li D C, Sato Y, et al. Cyclic deterioration and its improvement for Li-rich layered cathode material Li[Ni0.17Li0.2Co0.07Mn0.56]O2[J]. Journal of Power Sources, 2010, 195(2): 567-573.

[18] Armstrong A R, Holzapfel M, Novak P, et al. Demonstrating oxygen loss and associated structural reorganization in the lithium battery cathode Li[Ni0.2Li0.2Mn0.6]O2[J]. Journal of the American Chemical Society, 2006, 128(26): 8694-8698.

[19] Johnson C S, Li N, Vaughey J T, et al. Lithium-manganese oxide electrodes with layered-spinel composite structures xLi2MnO3·(1-x)Li1+yMn2-yO4 (0

[20] Shao H Y, Hackney S A, Armstrong A R, et al. Structural characterization of layered LiMnO2 electrodes by electron diffraction and lattice imaging[J]. Journal of the Electrochemical Society, 1999, 146(7): 2404-2412.

[21] Armstrong A R, Paterson A J, Dupre N, et al. Structural evolution of layered LixMnyO2: Combined neutron, NMR, and electrochemical study[J]. Chemistry of Materials, 2007, 19(5): 1016-1023.

[22] Johnson C S, Li N C, Lefief C, et al. Synthesis, characterization and electrochemistry of lithium battery electrodes: xLi2MnO3·1-xLiMn0.333Ni0.333Co0.333O2(0 <= x <= 0.7)[J]. Chemistry of Materials, 2008, 20(19): 6095-6106.