A new perspective on the 5 V discharge capacity of Li/Al doped manganese spinels

Abstract

A series of manganese spinels LiMn_2−yMe_yO₄ (Me = Li, Al, Mg) were prepared and examined by XRD and electrochemical methods. The spinels doped with Li or high content of Al can exhibit discharge capacity in the 5 V region, but spinels doped with Mg do not exhibit any 5 V discharge capacity. It is also observed that the 5 V discharge capacity of Li/Al doped spinels will be greatly suppressed once calcinated at temperatures above 900 °C in preparation. It is suggested that the 5 V discharge capacity of Li/Al doped spinels may be originated from the special chemical/structural characteristics of spinel phases containing Li or high content of Al prepared at temperatures below 900 °C.

Keywords

manganese spinels / doping / 5 V discharge capacity / origin

References

[1] Gummow R., Kock A., Thackeray M. Improved Capacity Retention in Rechargeable 4 V Lithium/lithium-manganese Oxide (spinel) Cells[J]. Solid State Ionics, 1994, 69: 59-67.

[2] Tarascon J. M., Mckinnon W. R., Coowar F., . Synthesis Conditions and Oxygen Stoichiometry Effects on Li Insertion into the Spinel LiMn₂O₄[J]. J. Electrochem. Soc., 1994, 141: 1 421-1 431.

[3] Xia Y., Yoshio M. An Investigation of Lithium Ion Insertion into Spinel Structure Li-Mn-O Compounds[J]. J. Electrochem. Soc., 1996, 143: 825-833.

[4] Horiba T., Hironaka K., Matsumura T., . Manganese-based Lithium Batteries for Hybrid Electric Vehicle Applications[J]. J. Power Sources, 2003, 119–121: 893-896.

[5] Xia Y., Sakai T., Fujieda T., . Correlating Capacity Fading and Structural Changes in Li_1+yMn_2−yO4-δ Spinel Cathode Materials: A Systematic Study on the Effects of Li/Mn Ratio and Oxygen Deficiency[J]. J. Electrochem. Soc., 2001, 148: A723-A726.

[6] Sigala C., Guyomard D., Verbaere A., . Positive Electrode Materials with High Operating Voltage for Lithium Batteries: LiCr_yMn_{2 − y}O₄ (0 ≤ y ≤ 1) [J]. Solid State Ionics, 1995, 81: 167-170.

[7] Zhong Q., Bonakdarpour A., Zhang M., . Synthesis and Electrochemistry of LiNi_xMn_2−xO4[J]. J. Electrochem. Soc., 1997, 144: 205-213.

[8] Shigemura H., Sakaebe H., Kageyama H., . Structure and Electrochemical Properties of LiFe_xMn_2−xO₄ Spinel as 5 V Electrode Material for Lithium Batteries[J]. J. Electrochem. Soc., 2001, 148: A730-A736.

[9] Kawai H., Nagata M., Tukamoto H., . High-voltage Lithium Cathode Materials[J]. J. Power Sources, 1999, 81-82: 67-72.

[10] Ohzuku T., Ariyoshi K., Takeda A., . Solid-state Redox Potentials for Li[Me_1/2Mn_3/2]O₄ (Me: 3d-transition Metal) Having Spinel-framework Structures: A Series of 5 Volt Materials for Advanced Lithium-ion Batteries[J]. J. Power Sources, 1999, 81-82: 90-94.

[11] Terada Y., Yasaka K., Nishikawa F., . In Situ XAFS Analysis of Li(Mn,M)₂O₄ (M=Cr, Co, Ni) 5 V Cathode Materials for Lithium-Ion Secondary Batteries[J]. J. Solid State Chemistry, 2001, 156: 286-291.

[12] Ohzuku T., Ariyoshi K., Takeda A., . Synthesis and Characterization of 5 V Insertion Material of Li[Fe_yMn_2−y]O₄ for Lithium-ion Batteries[J]. Electrochimica Acta, 2001, 46: 2 327-2 336.

[13] Shao-Horn Y., Middaugh R. Redox Reactions of Cobalt, Aluminum and Titanium Substituted Lithium Manganese Spinel Compounds in Lithium Cells[J]. Solid State Ionics, 2001, 139: 13-25.

[14] Wang X., Iltchev N., Nakamura H., . A 5 V Region Electrochemical Behavior of Nonstoichiometric Li_1+xMn_2−xO4_±z Spinels[J]. Electrochemical and Solid-State Letters, 2003, 6: A99-A101.

[15] Shin Y., Manthiram A. Origin of the Capacity of Spinel LiMn_2−yLi_yO4±δ in the 5 V Region[J]. Electrochemical and Solid-State Letters, 2003, 6: A249-A254.

[16] Deng B., Nakamura H., Yoshio M. Capacity Fading with Oxygen Loss for Manganese Spinels upon Cycling at Elevated Temperatures[J]. J. Power Sources, 2008, 180: 864-868.