Abstract
The effect of lithium boron oxide (LBO) coating on the electrochemical performance of orthorhombic LiMnO2 (o-LiMnO2) cathode for lithium-ion batteries is investigated. o-LiMnO2 synthesized via solid state synthesis technique is modified with LBO addition. The presence of LBO is identified via Fourier transform infrared spectroscopy analysis. o-LiMnO2 is observed to transform to a spinel-like phase during cycling which undergoes capacity fading. Studies indicate that the presence of 1–2 wt% LBO results in an improved capacity and better capacity retention with cycling. The pristine sample reveals a maximum specific capacity of 172 mAhg−1, whereas the LBO-modified samples display about 189.1 mAhg−1 in the cycling tests conducted at a rate of 50 mAg−1 in the voltage range of 2–4.5 V. After 70 cycles, the LBO-modified LiMnO2 displayed higher capacity retention of 175 mAhg−1 as compared to the pristine sample that exhibited 130 mAhg−1. By analyzing the charge–discharge behavior, it is observed that the capacity obtained from lithium insertion into the tetrahedral sites of the spinel structure is more or less constant throughout the cycling and that the bulk of the capacity loss is resulting when lithium is inserted into the octahedral sites of the spinel structure. Impedance measurement reveals a reduced charge-transfer resistance for the LBO-modified samples suggesting that the presence of LBO is countering capacity loss arising from insertion of lithium into the octahedral sites thus contributing to the overall cycling stability.
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References
Scrosati B, Garche J (2010) Lithium batteries: status, prospects and future. J Power Sources 195:2419–2430
Besselink IJM, Oorschot PF Van, Meinders E, Nijmeijer H (2010) Design of an efficient, low weight battery electric vehicle based on a VW Lupo 3L. 25th World Battery Hybrid Fuel Cell Vehicle Symposium Exhibition, Shenzen China p 32–41. http://www.tue.nl/uploads/media/EVS25-K4U0UV0P.pdf
Gummow RJ, Liles DC, Thackeray MM (1993) Lithium extraction from orthorhombic lithium manganese oxide. Mater Res Bull 28:1249–1256
Ammundsen B, Paulsen J (2001) Novel lithium-ion cathode materials based on layered manganese oxides. Adv Mater 13:943–956
Reimers J, Fuller E, Rossen E, Dahn JR (1993) Synthesis and electrochemical studies of LiMnO2 prepared at low temperatures. J Electrochem Soc 140:3396–3401
Jang DH, Shin YJ, Oh SM (1996) Dissolution of spinel oxides and capacity losses in 4 V Li/LixMn2O4 cells. J Electrochem Soc 143:2204–2211
Gummow R, De Kock A, Thackeray M (1994) Improved capacity retention in rechargeable 4 V lithium/lithium-manganese oxide (spinel) cells. Solid State Ionics 69:59–67
Jang YI, Huang BY, Wang HF, Sadoway DR, Chiang Y-M (1999) Electrochemical cycling-induced spinel formation in high-charge-capacity orthorhombic LiMnO2. J Electrochem Soc 146:3217–3223
Zhang HP, Yang LC, Fu LJ, Cao Q, Sun DL, Wu YP, Holze R (2009) Core-shell structured electrode materials for lithium ion batteries. J Solid State Electrochem 13:1521–1527
Li C, Zhang HP, Fu LJ, Liu H, Wu YP, Rahm E, Holze R, Wu HQ (2006) Cathode materials modified by surface coating for lithium ion batteries. Electrochim Acta 51:3872–3883
Cho J, Kim T-J, Park B (2002) The effect of a metal-oxide coating on the cycling behavior at 55 °C in Orthorhombic LiMnO2 cathode materials. J Electrochem Soc 149:A288
Sahan H, Goktepe H, Patat S, Ulgen A (2008) The effect of LBO coating method on electrochemical performance of LiMn2O4 cathode material. Solid State Ionics 178:1837–1842
Ying J, Wan C, Jiang C (2001) Surface treatment of LiNi0.8Co0.2O2 cathode material for lithium secondary batteries. J Power Sources 102:162–166
Croguennec L, Deniard P, Brec R, Lecerf A (1997) Nature of the stacking faults in orthorhombic LiMnO2. J Mater Chem 7:511–516
Julien CM, Massot M (2003) Lattice vibrations of materials for lithium rechargeable batteries III. Lithium manganese oxides. Mater Sci Eng B 100:69–78
Gautam C, Yadav AK, Singh AK (2012) A review on infrared spectroscopy of borate glasses with effects of different additives. ISRN Ceram 2012:1–17
Zhigadlo N, Zhang M, Salje E (2001) An infrared spectroscopic study of Li2B4O7. J Phys Condens Matter 13:6551–6561
Cho J, Kim YJ, Kim T-J, Park B (2002) Effect of Al2O3-Coated o-LiMnO2 cathodes prepared at various temperatures on the 55 °C cycling behavior. J Electrochem Soc 149:A127
Shaju KM, Rao GVS, Chowdari BVR (2004) Li-ion kinetics and polarization effect on the electrochemical performance of Li(Ni1/2Mn1/2)O2. Electrochim Acta 49:1565–1576
Cheah YL, Gupta N, Pramana SS, Aravindan V, Wee G, Srinivasan M (2011) Morphology, structure and electrochemical properties of single phase electrospun vanadium pentoxide nanofibers for lithium ion batteries. J Power Sources 196:6465–6472
Amatucci GG, Blyr A, Sigala C (2000) Surface treatments of Li1+xMn2−xO4 spinels for improved elevated temperature performance. Solid State Ionics 104:13–25
Dou J, Kang X, Wumaier T (2011) Effect of lithium boron oxide glass coating on the electrochemical performance of LiNi1/3Co1/3Mn1/3O2. J Solid State Electrochem 16:1481–1486
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This work was financially supported by the Singapore National Research Foundation under its Campus for Research Excellence and Technological Enterprise (CREATE) program.
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Arun Nagasubramanian and Denis Yau Wai Yu contributed equally to this paper.
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Nagasubramanian, A., Yu, D.Y.W., Hoster, H. et al. Enhanced cycling stability of o-LiMnO2 cathode modified by lithium boron oxide coating for lithium-ion batteries. J Solid State Electrochem 18, 1915–1922 (2014). https://doi.org/10.1007/s10008-014-2421-3
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DOI: https://doi.org/10.1007/s10008-014-2421-3