Skip to main content Accessibility help

Operando XRD study of LiMn1.5Ni0.5O4 high-voltage cathode under high-rate charge-discharge reaction

  • T. Konya (a1) (a2), Y. Shiramata (a1) and T. Nakamura (a2)


Structural variation of LiMn1.5Ni0.5O4 spinel cathode during the Li+ extraction/insertion reaction was studied using operando X-ray diffraction. It was found that the reaction in the voltage range from 3.5 to 4.9 V consisted of two consecutive two-phase reactions, where three spinel phases of LiMn1.5Ni0.5O4, Li0.5Mn1.5Ni0.5O4 and Mn1.5Ni0.5O4 were identified and the lattice volume change in the whole reaction was evaluated as 6%. The reactions were symmetric and reversible under low-current conditions, but some asymmetries were detected during high current operation. Furthermore, a two-phase reaction between cubic and tetragonal phases was observed in the low-voltage reaction at 2.1–3.5 V, where the lattice volume change was approximately 4.9%. The rate-determining step was discussed based on these operando results.


Corresponding author

a)Author to whom correspondence should be addressed. Electronic mail:


Hide All
Arai, H., Sato, K., Orikasa, Y., Murayama, H., Takahashi, I., Koyama, Y., Uchimoto, Y., and Ogumi, Z. (2013). “Phase transition kinetics of LiNi0.5Mn1.5O4 electrodes studied by in situ X-ray absorption near-edge structure and X-ray diffraction analysis,” J. Mater. Chem. A1, 10442.
Hanafusa, R., Kotani, K., Ishidzu, K., Oka, Y., and Nakamura, T. (2016). “Electrochemical study of LiMn1.5Ni0.5O4 spinel oxides prepared by two-step process,” Solid State Ionics 288, 180.
Idemoto, Y., Narai, H., and Koura, N. (2003). “Crystal structure and cathode performance dependence on oxygen content of LiMn1.5Ni0.5O4 as a cathode material for secondary lithium batteriesJ. Power Sources 119–121, 125129.
Idemoto, Y., Sekine, H., and Koura, N. (2005). “Crystal structural change during charge–discharge process of LiMn1.5Ni0.5O4 as cathode material for 5 V class lithium secondary batterySolid State Ionics 176, 299306.
Kunduraci, M., and Amatucci, G. G. (2006). “Synthesis and characterization of nanostructured 4.7 V LixMn1.5Ni0.5O4 spinels for high-power lithium-ion batteries,” J. Electrochem. Soc. 153, A1345.
Nakamura, T., Tabuchi, M., and Yamada, Y. (2005). “Magnetic and electrochemical studies on Ni2+-substituted Li–Mn spinel oxides,” J. Appl. Phys. 98, 093905.
Nakamura, T., Konya, T., Shiramata, Y., Kobayashi, Y., and Tabuchi, M. (2018). “Electrochemical and in-situ X-ray diffraction studies of LiMn1.5Ni0.5O4 particles synthesized using two-step preparation,” Solid State Ionics 319, 105.
Takahashi, I., Mori, T., Yoshinari, T., Orikasa, Y., Koyama, Y., Murayama, H., Fukuda, K., Hatano, M., Arai, H., Uchimoto, Y., and Terai, T. (2016). “Irreversible phase transition between LiFePO4 and FePO4 during high-rate charge-discharge reaction by operando X-ray diffraction,” J. Power Sources 309, 122.
Yi, T. F., Mei, J., and Zhu, Y. R. (2016). “Key strategies for enhancing the cycling stability and rate capacity of LiNi0.5Mn1.5O4 as high-voltage cathode materials for high power lithium-ion batteries,” J. Power Sources 85, 316.
Zhong, Q., Bonakdarpour, A., Zhang, M., Gao, Y., and Dahn, J. R. (1997). “Synthesis and electrochemistry of LiNixMn2-xO4,” J. Electrochem. Soc. 144, 205.



Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed