Additional Research Papers

Self-Substitution and the Temperature Effects on the Electrochemical Performance in the High Voltage Cathode System LiMn1.5+xNi0.5−xO4 (x = 0.1)

[+] Author and Article Information
Yun Xu

Department of Materials Science
and Engineering,
Clemson University,
Clemson, SC 29634
e-mail: yxu4@g.clemson.edu

Mingyang Zhao

Department of Materials Science
and Engineering,
Clemson University,
Clemson, SC 29634
e-mail: mingyaz@g.clemson.edu

Syed Khalid

Photon Science Directorate,
Brookhaven National Laboratory,
Upton, NY 11973
e-mail: Khalid@bnl.gov

Hongmei Luo

Department of Chemical &
Materials Engineering,
New Mexico State University,
Las Cruces, NM 88003
e-mail: hluo@nmsu.edu

Kyle S. Brinkman

Department of Materials Science
and Engineering,
Clemson University,
Clemson, SC 29634
e-mail: ksbrink@clemson.edu

1Corresponding author.

Manuscript received January 13, 2017; final manuscript received February 24, 2017; published online May 9, 2017. Assoc. Editor: Kevin Huang.

J. Electrochem. En. Conv. Stor. 14(2), 021003 (May 09, 2017) (4 pages) Paper No: JEECS-17-1008; doi: 10.1115/1.4036386 History: Received January 13, 2017; Revised February 24, 2017

The high voltage cathode material, LiMn1.6Ni0.4O4, was prepared by a polymer-assisted method. The novelty of this work is the substitution of Ni with Mn, which already exists in the crystal structure instead of other isovalent metal ion dopants which would result in capacity loss. The electrochemical performance testing including stability and rate capability was evaluated. The temperature was found to impose a change on the valence and structure of the cathode materials. Specifically, manganese tends to be reduced at a high temperature of 800 °C and leads to structural changes. The manganese substituted LiMn1.5Ni0.5O4 (LMN) has proved to be a good candidate material for Li-ion battery cathodes displaying good rate capability and capacity retention. The cathode materials processed at 550 °C showed a stable performance with negligible capacity loss for 400 cycles.

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Liu, J. , and Manthiram, A. , 2009, “ Understanding the Improved Electrochemical Performances of Fe-Substituted 5 V Spinel Cathode LiMn1.5Ni0.5O4,” J. Phys. Chem. C, 113(33), pp. 15073–15079. [CrossRef]
Shin, D. W. , Bridges, C. A. , Huq, A. , Paranthaman, M. P. , and Manthiram, A. , 2012, “ Role of Cation Ordering and Surface Segregation in High-Voltage Spinel LiMn1.5Ni0.5xMxO4 (M = Cr, Fe, and Ga) Cathodes for Lithium-Ion Batteries,” Chem. Mater., 24(19), pp. 3720–3731. [CrossRef]
Liu, J. , and Manthiram, A. , 2009, “ Improved Electrochemical Performance of the 5 V Spinel Cathode LiMn1.5Ni0.42Zn0.08O4 by Surface Modification,” J. Electrochem. Soc., 156(1), pp. A66–A72. [CrossRef]
Yi, T.-F. , Xie, Y. , Zhu, Y.-R. , Zhu, R.-S. , and Ye, M.-F. , 2012, “ High Rate Micron-Sized Niobium-Doped LiMn1.5Ni0.5O4 as Ultra High Power Positive-Electrode Material for Lithium-Ion Batteries,” J. Power Sources, 211, pp. 59–65. [CrossRef]
Arunkumar, T. A. , and Manthiram, A. , 2005, “ Influence of Lattice Parameter Differences on the Electrochemical Performance of the 5 V Spinel LiMn1.5yNi0.5zMy+zO4 (M = Li, Mg, Fe, Co, and Zn),” Electrochem. Solid-State Lett., 8(8), pp. A403–A405. [CrossRef]
Kunduraci, M. , and Amatucci, G. G. , 2007, “ Effect of Oxygen Non-Stoichiometry and Temperature on Cation Ordering in LiMn2−xNixO4 (0.50 ≥ x ≥ 0.36) Spinels,” J. Power Sources, 165(1), pp. 359–367. [CrossRef]
Liu, H. , Wang, J. , Zhang, X. , Zhou, D. , Qi, X. , Qiu, B. , Fang, J. , Kloepsch, R. , Schumacher, G. , Liu, Z. , and Li, J. , 2016, “ Morphological Evolution of High-Voltage Spinel LiNi0.5Mn1.5O4 Cathode Materials for Lithium-Ion Batteries: The Critical Effects of Surface Orientations and Particle Size,” ACS Appl. Mater. Interfaces, 8(7), pp. 4661–4675. [CrossRef] [PubMed]
Hwang, T. , Lee, J. K. , Mun, J. , and Choi, W. , 2016, “ Surface-Modified Carbon Nanotube Coating on High-Voltage LiNi0.5Mn1.5O4 Cathodes for Lithium Ion Batteries,” J. Power Sources, 322, pp. 40–48. [CrossRef]
Kumar, P. R. , Madhusudhanrao, V. , Nageswararao, B. , Venkateswarlu, M. , and Satyanarayana, N. , 2016, “ Enhanced Electrochemical Performance of Carbon-Coated LiMPO4 (M = Co and Ni) Nanoparticles as Cathodes for High-Voltage Lithium-Ion Battery,” J. Solid State Electrochem., 20(7), pp. 1855–1863. [CrossRef]
Myung, S.-T. , Komaba, S. , Kumagai, N. , Yashiro, H. , Chung, H.-T. , and Cho, T.-H. , 2002, “ Nano-Crystalline LiNi0.5Mn1.5O4 Synthesized by Emulsion Drying Method,” Electrochim. Acta, 47(15), pp. 2543–2549. [CrossRef]
Xu, Y. , Chen, G. , Fu, E. , Zhou, M. , Dunwell, M. , Fei, L. , Deng, S. , Andersen, P. , Wang, Y. , Jia, Q. , and Luo, H. , 2013, “ Nickel Substituted LiMn2O4 Cathode With Durable High-Rate Capability for Li-Ion Batteries,” RSC Adv., 3(40), pp. 18441–18445. [CrossRef]
Rana, J. , Glatthaar, S. , Gesswein, H. , Sharma, N. , Binder, J. R. , Chernikov, R. , Schumacher, G. , and Banhart, J. , 2014, “ Local Structural Changes in LiMn1.5Ni0.5O4 Spinel Cathode Material for Lithium-Ion Batteries,” J. Power Sources, 255, pp. 439–449. [CrossRef]
Mukai, K. , Ikedo, Y. , Kamazawa, K. , Brewer, J. H. , Ansaldo, E. J. , Chow, K. H. , Mansson, M. , and Sugiyama, J. , 2013, “ The Gradient Distribution of Ni Ions in Cation-Disordered Li[Ni1/2Mn3/2]O4 Clarified by Muon-Spin Rotation and Relaxation (μSR),” RSC Adv., 3(29), pp. 11634–11639. [CrossRef]
Chemelewski, K. R. , and Manthiram, A. , 2013, “ Origin of Site Disorder and Oxygen Nonstoichiometry in LiMn1.5Ni0.5–xMxO4 (M = Cu and Zn) Cathodes With Divalent Dopant Ions,” J. Phys. Chem. C, 117(24), pp. 12465–12471. [CrossRef]
Manthiram, A. , Chemelewski, K. , and Lee, E.-S. , 2014, “ A Perspective on the High-Voltage LiMn1.5Ni0.5O4 Spinel Cathode for Lithium-Ion Batteries,” Energy Environ. Sci., 7(4), pp. 1339–1350. [CrossRef]
Samarasingha, P. B. , Andersen, N. H. , Sørby, M. H. , Kumar, S. , Nilsen, O. , and Fjellvåg, H. , 2016, “ Neutron Diffraction and Raman Analysis of LiMn1.5Ni0.5O4 Spinel Type Oxides for Use as Lithium Ion Battery Cathode and Their Capacity Enhancements,” Solid State Ionics, 284, pp. 28–36. [CrossRef]
Yamada, A. , 1996, “ Lattice Instability in Li(LixMn2x)O4,” J. Solid State Chem., 122(1), pp. 160–165. [CrossRef]


Grahic Jump Location
Fig. 1

(a) XRD patterns of LMN(550) and LMN(800) and (b) SEM image of synthesized particles LMN(550) sample

Grahic Jump Location
Fig. 2

(a) Cyclic voltammograms of LMN(550) and LMN(800) scanned from 3.5 V to 5 V and (b) XANES of LMN(550), LMN(800), and Mn foil

Grahic Jump Location
Fig. 3

(a) Charge and discharge profile from 1.75 V to 5 V and (b) cycle performance of LMN(550) and LMN(800) at 4 C

Grahic Jump Location
Fig. 4

(a) Impedance spectra and the fitting result of two LMN prepared at different temperatures, inset is the equivalent circuit used to fit impedance spectra. With fitting parameters listed in the bottom table. (b) Charge and discharge profiles of full cell and half-cell.



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