Li-ion storage performance and electrochemically induced phase evolution of layer-structured Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ cathode material

Abstract

Li-rich Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ (LMNC) powders were synthesized by a gel-combustion method. The related microstructure, electrochemical performance and electrochemically induced phase evolution were characterized. The 900°C calcined powders have a hexagonal layered structure with high ordered degree and low cationic mixing level. The calcined materials as cathode electrode for Li-ion battery deliver the high electrochemical properties with an initial discharge capacity of 243.5 mA·h·g^–1 at 25 mA·g^–1 and 249.2 mA·h·g^–1 even after 50 cycles. The electrochemically induced phase evolution investigated by a transmission electron microscopy indicates that Li⁺ ions deintercalated first from the LiMO₂ (M= Mn, Co, Ni) component and then from Li₂MnO₃ component in the LMNC during the charge process, while Li⁺ ions intercalated into Li_1–xMO₂ component followed by into MnO₂ component during the discharge process.

Keywords

Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ / gel-combustion synthesis / phase evolution / Li-storage capacity / electrochemical reaction

References

[1] Thackeray M M, Wolverton C, Isaacs E D. Electrical energy storage for transportation-approaching the limits of, and going beyond, lithium-ion batteries. Energy & Environmental Science, 2012, 5(7): 7854–7863

[2] Rusdi R, Kamarulzaman N, Elong K, . Electrochemical performance of overlithiated Li_1+xNi_0.8Co_0.2O₂: structural and oxidation state studies. Frontiers of Materials Science, 2015, 9(2): 199–205

[3] Gao Y X, Wang X P, Sun Q X, . Electrical properties of garnet-like lithium ionic conductors Li_5+xSr_xLa_3-xBi₂O₁₂ fabricated by spark plasma sintering method. Frontiers of Materials Science, 2012, 6(3): 216–224

[4] Sun Y K, Lee M J, Yoon C S, . The role of AlF₃ coatings in improving electrochemical cycling of Li-enriched nickel‒manganese oxide electrodes for Li-ion batteries. Advanced Materials, 2012, 24(9): 1192–1196

[5] Wang J, Yuan G, Zhang M, . The structure, morphology, and electrochemical properties of Li_1+xNi_1/6Co_1/6Mn_4/6O_2.25+x/2 (0.1≤x≤0.7) cathode materials. Electrochimica Acta, 2012, 66: 61–66

[6] Qi H, Cao G S, Xie J, . Enhanced cycle stability of spinel LiMn₂O₄ by a melting impregnation method. Frontiers of Materials Science, 2008, 2(3): 291–294

[7] Zheng J, Zhu D, Yang Y, . The effects of N-methyl-N-butylpyrrolidinium bis (trifluoromethylsulfonyl) imide-based electrolyte on the electrochemical performance of high capacity cathode material Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂. Electrochimica Acta, 2012, 59: 14–22

[8] Liu J, Manthiram A. Functional surface modifications of a high capacity layered Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ cathode. Journal of Materials Chemistry, 2010, 20(19): 3961–3967

[9] Zheng J M, Wu X B, Yang Y. A comparison of preparation method on the electrochemical performance of cathode material Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ for lithium ion battery. Electrochimica Acta, 2011, 56(8): 3071–3078

[10] Yang P, Zhang S, Wei X, . Comparison of electrochemical properties for lithium-rich cathode material Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ prepared by two methods. International Journal of Electrochemical Science, 2015, 10(11): 9424–9432

[11] Lee E, Koritala R, Miller D J, . Aluminum and gallium substitution into 0.5Li₂MnO₃·0.5Li(Ni_0.375Mn_0.375Co_0.25)O₂ layered composite and the voltage fade effect. Journal of the Electrochemical Society, 2015, 162(3): A322–A329

[12] Wei X, Zhang S, Du Z, . Electrochemical performance of high-capacity nanostructured Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ cathode material for lithium ion battery by hydrothermal method. Electrochimica Acta, 2013, 107: 549–554

[13] Li Y, Bettge M, Polzin B, . Understanding long-term cycling performance of Li_1.2Ni_0.15Mn_0.55Co_0.1O₂-graphite lithium-ion cells. Journal of the Electrochemical Society, 2013, 160(5): A3006–A3019

[14] Lu Z, Dahn J R. Understanding the anomalous capacity of Li/Li[Ni_xLi_(1/3-2x/3)Mn_(2/3-x/3)]O₂ cells using in situ X-ray diffraction and electrochemical studies. Journal of the Electrochemical Society, 2002, 149(7): A815–A822

[15] Lim J H, Bang H, Lee K S, . Electrochemical characterization of Li₂MnO₃‒Li[Ni_1/3Co_1/3Mn_1/3]O₂‒LiNiO₂ cathode synthesized via co-precipitation for lithium secondary batteries. Journal of Power Sources, 2009, 189(1): 571–575

[16] Amarilla J M, Rojas R M, Pico F, . Nanosized LiM_yMn_2-yO₄ (M= Cr, Co and Ni) spinels synthesized by a sucrose-aided combustion method. Journal of Power Sources, 2007, 174(2): 1212–1217

[17] Wang Y, Zhang H, Chen W, . Gel-combustion synthesis and electrochemical performance of LiNi_1/3Mn_1/3Co_1/3O₂ as cathode material for lithium-ion batteries. RSC Advances, 2014, 4(70): 37148–37156

[18] Ma Z, Zhang H, Zhang Y, . Electrochemical characteristics of nanostructured NiO plates hydrothermally treated on nickel foam for Li-ion storage. Electrochimica Acta, 2015, 176: 1427–1433

[19] Chen W, Zhang H, Wang Y, . In-situ microstructural investigations by electron-beam irradiation induced crystallization of amorphous MoO_x thin films with high performance for Li-ion storage. Electrochimica Acta, 2014, 144: 369–375

[20] Chen W, Zhang H, Ma Z, . High electrochemical performance and lithiation‒delithiation phase evolution in CuO thin films for Li-ion storage. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2015, 3(27): 14202–14209

[21] Ouyang P, Zhang H, Chen W, . Electrochemical and microstructural characterization of magnetron-sputtered ATO thin films as Li-ion storage materials. Materials Research Bulletin, 2015, 61: 9–15

[22] Liu Y, Zhang H, Ouyang P, . High electrochemical performance and phase evolution of magnetron sputtered MoO₂ thin films with hierarchical structure for Li-ion battery electrodes. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2014, 2(13): 4714–4721

[23] Chen W, Zhang H, Liu Y, . Facile method for investigating electrochemically induced products in films deposited directly on grids as working electrodes. Materials Letters, 2015, 157: 1–3

[24] Hsieh C T, Mo C Y, Chen Y F, . Chemical-wet synthesis and electrochemistry of LiNi_1/3Co_1/3Mn_1/3O₂ cathode materials for Li-ion batteries. Electrochimica Acta, 2013, 106: 525–533

[25] Lee S B, Cho S H, Cho S J, . Synthesis of LiFePO₄ material with improved cycling performance under harsh conditions. Electrochemistry Communications, 2008, 10(9): 1219–1221

[26] Tintignac S, Baddour-Hadjean R, Pereira-Ramos J P, . Electrochemical properties of high rate bias sputtered LiCoO₂ thin films in liquid electrolyte. Journal of Power Sources, 2014, 245: 76–82

[27] Yu H, Zhou H. High-energy cathode materials (Li₂MnO₃‒LiMO₂) for lithium-ion batteries. The Journal of Physical Chemistry Letters, 2013, 4(8): 1268–1280

[28] Wang Z, Liu E, He C, . Effect of amorphous FePO₄ coating on structure and electrochemical performance of Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ as cathode material for Li-ion batteries. Journal of Power Sources, 2013, 236: 25–32

[29] Martha S K, Nanda J, Veith G M, . Electrochemical and rate performance study of high-voltage lithium-rich composition: Li_1.2Mn_0.525Ni_0.175Co_0.1O₂. Journal of Power Sources, 2012, 199: 220–226

[30] Kim S, Kim C, Noh J K, . Synthesis of layered-layered xLi₂MnO₃·(1-x)LiMO₂ (M= Mn, Ni, Co) nanocomposite electrodes materials by mechanochemical process. Journal of Power Sources, 2012, 220: 422–429

Acknowledgements

The authors acknowledge the support of the National Nature Science Foundation of China (Grant No. 51172287) and the Laboratory Research Fund by the State Key Laboratory of Powder Metallurgy, Central South University, China.

RIGHTS & PERMISSIONS

2014 Higher Education Press and Springer-Verlag Berlin Heidelberg