Journal of Power Sources 195 (2010) 5442–5451

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Journal of Power Sources

journal homepage: www.elsevier.com/locate/jpowsour

Review

Research progress in high voltage spinel LiNi0.5 Mn1.5 O4 material

R. Santhanam, B. Rambabu ∗
Solid State Ionics and Surface Sciences Lab, Department of Physics, Southern University and A&M College, Baton Rouge, LA 70813, USA

a r t i c l e i n f o a b s t r a c t

Article history: Lithium-ion batteries are now considered to be the technology of choice for future hybrid electric and
Received 25 February 2010 full electric vehicles to address global warming. LiCoO2 has been the most widely used cathode material
Received in revised form 22 March 2010 in commercial lithium-ion batteries. Since LiCoO2 has economic and environmental issues, intensive
Accepted 23 March 2010
research has been directed towards the development of alternative low cost, environmentally friendly
Available online 27 March 2010
cathode materials as possible replacement of LiCoO2 . Among them, spinel LiNi0.5 Mn1.5 O4 material is one
of the promising and attractive cathode materials for next generation lithium-ion batteries because of its
Keywords:
high voltage (4.7 V), acceptable stability, and good cycling performance. Research advances in high voltage
Spinel LiNi0.5 Mn1.5 O4
High voltage
spinel LiNi0.5 Mn1.5 O4 are reviewed in this paper. Developments in synthesis, structural characterization,
Cathode material effect of doping, and effect of coating are presented. In addition to conventional synthesis methods, several
Lithium-ion batteries alternative synthesis methods are also summarized. Apart from battery performance, the application of
spinel LiNi0.5 Mn1.5 O4 material in asymmetric supercapacitors is also discussed.
© 2010 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5442
2. Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5444
2.1. Solid state method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5444
2.2. Sol–gel method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5444
2.3. Co-precipitation method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5444
2.4. Other methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5444
3. Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5446
4. Effect of doping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5446
5. Effect of coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5448
6. Cathode for asymmetric supercapacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5449
7. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5449
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5450
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5450

1. Introduction
gasoline engine powered vehicles by hybrid electric vehicles, plug-
Sony Corporation first introduced the concept of lithium-ion in hybrid vehicles and electric vehicles (HEV, PHEV and EVs). In this
batteries in early 1990s using LiCoO2 and graphite as positive and regard, lithium-ion batteries are attractive power source devices
negative electrode materials, respectively. Since then, worldwide due to their high energy density. However, the deficiencies of cur-
research and development have been performed enormously on rent lithium-ion battery for pure EV applications are mainly energy
lithium-ion batteries to meet increasing demand for power sources and cost, and possibly safety. For HEV and PHEV applications, the
to use in portable electronic devices. Recently, energy and envi- main deficiency is cost and possibly safety and life. In this regard,
ronmental challenges have stimulated great interest to replace many studies have been focused on the development of the cath-
ode materials that make the energy density, power density, cycle
life and safety more effective than that of LiCoO2 . Most of the
∗ Corresponding author at: Solid State Ionics and Surface Sciences Lab, Depart-
commercial cathode materials are lithium intercalation materi-
ment of Physics, Southern University and A&M College, James Hall, Baton Rouge, LA
als with layered, spinel and olivine structures [1–4]. Fig. 1 shows
70813, USA. Tel.: +1 225 771 4130; fax: +1 225 771 2310. the charge and discharge curves of commercially important inter-
E-mail address: [email protected] (B. Rambabu). calation materials studied for advanced lithium-ion batteries [5].

0378-7753/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jpowsour.2010.03.067
 R. Santhanam, B. Rambabu / Journal of Power Sources 195 (2010) 5442–5451 5443

Fig. 2. The spinel structure of LiNi0.5 Mn1.5 O4 (Fd3m) showing diffusion path of
lithium [31].

Fig. 1. Charge and discharge curves of (a) Li[Ni0.5 Mn1.5 ]O4 , (b) LiMn2 O4 -based mate-
rial of lithium aluminum manganese oxide (LAMO), (c) LiCo1/3 Ni1/3 Mn1/3 O2 , (d)
LiFePO4 , and (e) Li[Li1/3 Ti5/3 ]O4 in nonaqueous lithium cells [5].
sites and O ions are occupied in the 8c and 24e sites [30]. In
Among the numerous transition metal oxides, manganese-based this case, Ni and Mn atoms are ordered regularly. The disordered
oxides are particularly attractive as cathode materials because of LiNi0.5 Mn1.5 O4−ı spinel was found to have better electrochemical
their low cost and non-toxicity. Among them, LiMn2 O4 spinel and performance than ordered spinel LiNi0.5 Mn1.5 O4 [30]. Ceder and co-
its derivatives have been extensively studied as promising cathode workers presented the diffusion path of lithium in the disordered
materials due to their easy preparation, abundance, low cost, and LiNi0.5 Mn1.5 O4−ı spinel as shown in Fig. 2 [31]. The theoretical
non-toxicity [6–12]. Pure LiMn2 O4 has face-centered spinel struc- capacity of LiNi0.5 Mn1.5 O4 is calculated to be 147 mA h g−1 when
ture with Fd3m space group in which the Mn, Li and O ions are in the all lithium-ions can be extracted from this material. The main
16d octahedral sites, 8a tetrahedral sites and 32e sites, respectively. issues with this spinel material are as follows: (i) the redox couple
The isotropic structure of spinel LiMn2 O4 provides a 3D network for (NiIII /NiIV ) is at the potential of decomposition of the conventional
lithium-ion diffusion, and hence, this material is suitable for fast battery electrolyte (1.0 M LiPF6 in ethylene carbonate/diethyl car-
lithium insertion and deinsertion reactions [12–18]. However, it bonate) and (ii) it is difficult to prepare of pure spinel LiNi0.5 Mn1.5 O4
suffers from poor cycling behavior at elevated temperature [19,20]. due to the formation of Lix Ni1−x O as a second phase. The decom-
In order to overcome this problem, many research groups have been position of electrolyte occurs at around 4.6 and 5.1 V vs. Li in half
focused on substitution of other transition metals for Mn to make cell and full cell at room temperature, respectively. The formation
LiMx Mn2−x O4 (M = Co, Cr, Ni, Fe, Cu, etc.) [21–25]. of Lix Ni1−x O deteriorates the electrochemical performance of the
Sigala et al. suggested that much of the reduced capacity of Cr- spinel LiNi0.5 Mn1.5 O4 material [26].
doped spinel appears in 4.9 V plateau and the size of the plateau Recently, excellent reviews have been published on materials
increases with Cr content [21]. Zhong et al. reported that all the for lithium-ion batteries [4,32–34]. Chen and Cheng reported the
metal doped spinels should be reinvestigated for the intercala- combination of light weight elements and nanostructured mate-
tion behavior in the high voltage region [26]. During the course rials for developing advanced lithium-ion batteries [32]. Fergus
of investigations, it has been found that a Ni-doped spinel oxide, reviewed recent developments of cathode materials for lithium
LiNi0.5 Mn1.5 O4 is the most promising and attractive one because batteries and compared the performance of promising cathode
of its good cycling behavior and relatively high capacity with one materials and approaches for improving their performances [4].
dominant plateau at around 4.7 V whereas other materials exhib- Kim and Cho reviewed recent research advances on reversible and
ited two plateaus at around 4.0 and 5.0 V [26–28]. Great attention high capacity nanostructured electrode materials for lithium-ion
has been given to spinel LiNi0.5 Mn1.5 O4 because it provides access batteries [33]. Synthesis procedures of LiFePO4 powders, along with
to redox couple (NiIII /NiIV ) below 4.8 V vs. Li. Since these redox cou- doped and coated derivatives, have been systematically reviewed
ples are pinned at the top of the O–2p bands, a step between them by Jugovic and Uskokovic [34]. In the case of spinel materials,
is not observed in the spinel LiNi0.5 Mn1.5 O4 [29]. LiNi0.5 Mn1.5 O4 Amatucci and Tarascon reported the optimization of LiMn2 O4 in
spinel is fundamentally different from pure spinels as all redox their review [35] and Yi et al. [36] reviewed recent developments
activity takes place on Ni and Mn remains in 4+ state. This spinel has in the surface modifications of LiMn2 O4 for lithium-ion batteries.
two different crystal structures of the space groups of Fd3m (non- Very recently, Nazar and co-workers published an excellent review
stoichiometric disordered LiNi0.5 Mn1.5 O4−ı ) in which Mn ions are on positive electrode materials for lithium-ion and lithium batter-
present in mainly Mn4+ and little Mn3+ , and P43 32 (stoichiomet- ies [37]. They overviewed the developments of positive electrode
ric ordered LiNi0.5 Mn1.5 O4 ) in which Mn ions are only present in materials in the past decade and highlighted the ultrahigh capac-
Mn4+ . The non-stoichiometric LiNi0.5 Mn1.5 O4−ı has face-centered ity systems such as Li–S and Li–air batteries for the future. Here,
cubic spinel structure with Fd3m space group in which, like pure we tried to make a review specifically on spinel LiNi0.5 Mn1.5 O4
spinel LiMn2 O4 , the Ni and Mn, Li and O atoms are occupied in cathode material since this material has the highest voltage (4.7 V)
the 16d octahedral sites, 8a tetrahedral sites and 32e sites, respec- among all other layered cathode materials for lithium battery appli-
tively. In this case, Ni and Mn atoms are randomly distributed cations. This article provides an overview of selected developments
in the 16d sites. However, the stoichiometric LiNi0.5 Mn1.5 O4 has on spinel LiNi0.5 Mn1.5 O4 on synthesis, characterization, effect of
primitive simple cubic structure with P43 32 space group in which doping and effect of coating on the battery performance and the
the Ni, Mn, and Li atoms are occupied in the 4a, 12d, and 4c application in asymmetric supercapacitors for the past decade.
5444 R. Santhanam, B. Rambabu / Journal of Power Sources 195 (2010) 5442–5451

2. Synthesis

2.1. Solid state method

This is the most common method in which stoichiometric mix-

ture of starting materials is ground or ball-milled together and
the resultant mixture is heat-treated in a furnace. In the case of
spinel LiNi0.5 Mn1.5 O4 , appropriate amounts of starting materials,
NiCl2 ·xH2 O and MnCl2 ·xH2 O, are thoroughly mixed in the ratio of
1:3. Subsequently, 20% excess (NH4 )2 C2 O4 ·H2 O is added to the mix-
ture and then the mixture is ground to ensure complete reaction.
After drying, the mixture is calcined at 400 ◦ C to form the precur-
sor containing Ni–Mn. Stoichiometric amount of Li2 Co3 is added
and mixed thoroughly. Then the mixture containing Ni–Mn–Li is
calcined at different temperatures ranging from 700 to 900 ◦ C [38].
The purity of the material depends on the starting materials, cal-
cination temperature and time. The effect of various Ni precursors
on the electrochemical performance has been investigated and the
results show that the best electrochemical performance is obtained
from Ni(NO3 )2 ·6H2 O precursor [39]. An improved solid state reac-
tion is reported using Li2 Co3 , NiO and electrolytic MnO2 [40]. The
morphology of the spinel LiNi0.5 Mn1.5 O4 material prepared by solid
state method is shown in Fig. 3a [40]. However, this method has
some disadvantages such as inhomogeneity, uncontrollable parti-
cle growth and agglomeration.

2.2. Sol–gel method

The sol–gel method can overcome some disadvantages of

conventional solid state method because of its low processing tem-
perature, high chemical homogeneity, possibility of controlling size
and morphology of the particles. Sol–gel method is used to pre-
pare spinel LiNi0.5 Mn1.5 O4 by various research groups [41–45]. To
prepare LiNi0.5 Mn1.5 O4 stoichiometric amounts of lithium acetate
[Li(CH3 COO)·2H2 O], manganese acetate [Mn(CH3 COO)2 ·4H2 O],
and nickel acetate [Ni(CH3 COO)2 ·4H2 O], are dissolved in an appro-
priate quantity of distilled water at room temperature. The solution
is stirred at 50 ◦ C and the citric acid is added to the solution which
acts as chelating agent in the polymeric matrix. The pH of the
solution is adjusted to 7.0 by slowly dropping ammonium hydrox-
ide drop wise and continued stirring for 4 h. The temperature of
the solution is raised to 80–90 ◦ C and continued stirring till the
solution turned into high-viscous gel. The resulted gel is dried at
80 ◦ C for 24 h in a temperature controlled oven of an accuracy
Fig. 3. SEM images of the spinel LiNi0.5 Mn1.5 O4 synthesized by (a) solid state, (b)
of ±1 ◦ C. The LiNi0.5 Mn1.5 O4 precursor powder is ground to fine sol–gel, and (c) co-precipitation methods [40,41,46].
powder and calcined at 450 ◦ C under oxygen flowing conditions
with a constant heating followed by cooling rate at 4 ◦ C min−1 to
decompose organic constituents. The calcined powder is ground to peratures to get LiNi0.5 Mn1.5 O4 powders. This powder is prepared
a fine powder and re-sintered at different temperatures and time by co-precipitation using different precursors such as metal sulfate,
under oxygen flowing conditions. The morphology of the spinel metal carbonate, and metal chlorides [46–48]. A representative
LiNi0.5 Mn1.5 O4 powder obtained from sol–gel method is presented image of the LiNi0.5 Mn1.5 O4 material prepared by co-precipitation
in Fig. 3b [41]. is shown in Fig. 3c [46].

2.3. Co-precipitation method 2.4. Other methods

Co-precipitation procedure can easily be handled and the High rate capability was achieved by the nano-rod like
precipitates are generated simultaneously and uniformly dis- LiNi0.5 Mn1.5 O4 spinel powder prepared by polymer assisted (PA)
persed throughout the solution. To synthesize LiNi0.5 Mn1.5 O4 synthesis in which polyethylene glycol (PEG 400) was used as sac-
powders, the precursor (Ni0.5 Mn1.5 )(OH)2 is firstly prepared rificial template [49]. Homogeneous mixing of starting materials
by dissolving stoichiometric amounts of Ni(CH3 COO)2 ·4H2 O, at the atomic scale was achieved by radiated polymer gel (RPG)
and Mn(CH3 COO)2 ·4H2 O in distilled water (cationic ratio of method in which the solution containing starting materials and
Ni:Mn = 1:3). The aqueous solution is then precipitated by adding acrylic acid to synthesize LiNi0.5 Mn1.5 O4 spinel. The solution is
NaOH/NH4 OH solution along with continued stirring to obtain polymerized under the condition of Co60 ␥-ray irradiation (inten-
mixed hydroxide precipitate. After filtering, washing and drying sity 55–75 Gy min−1 ) [50]. 50 nm sized LiNi0.5 Mn1.5 O4 having the
in a vacuum oven at 50–60 ◦ C overnight, the obtained precursor is Fd3m cubic spinel structure is readily prepared by the emulsion
mixed with required amount of LiOH and calcined at various tem- drying (ED) method which can intermix cations (Li, Mn and Ni) on
 R. Santhanam, B. Rambabu / Journal of Power Sources 195 (2010) 5442–5451 5445

Fig. 4. TEM images of the spinel LiNi0.5 Mn1.5 O4 synthesized by (a) polymer assisted,
(b) radiated polymer gel, and (c) emulsion drying methods [49–51].

the atomic scale [51]. The TEM images of LiNi0.5 Mn1.5 O4 material
prepared by PA, RPG and ED methods are shown in Fig. 4a–c, respec-
tively [49–51]. Oh et al. employed mechanochemical process, to
synthesize LiNi0.5 Mn1.5 O4 material, in which planetary-type ball
mill was adopted for the mechanical activation of the starting
materials [52]. This method is a common method which uses high
energy ball milling to prepare highly homogeneous powders of
different species by mechanical activation. The frictional energy Fig. 5. SEM images of the spinel LiNi0.5 Mn1.5 O4 synthesized by (a) mechanochemi-
cal, (b) and (c) molten salt, and (d) carbon combustion methods [52,61,62,65].
formed by the balls and powders and rotation of the bowl would
initiate some reactions between the raw materials [53,54]. The
morphology of the material prepared by mechanochemical method
is shown in Fig. 5a [52]. Fang et al. reported a combinational anneal-
ing method to prepare the spinel LiNi0.5 Mn1.5 O4 material [55].
Since high temperature calcination results in oxygen loss, Ni defi-
5446 R. Santhanam, B. Rambabu / Journal of Power Sources 195 (2010) 5442–5451

ciency and formation of impurity phases, the cycling performance

of the material would be deteriorated. Oxygen loss can be recov-
ered by low rate cooling or low temperature annealing [56,57].
Therefore, in the combinational annealing method, the mixed pre-
cursors were heated to high temperature and then quickly cooled
down to low temperature for isothermal annealing treatment. In
this way, LiNi0.5 Mn1.5 O4 material can be prepared with minimum
oxygen loss, reduced impurity to obtain good electrochemical per-
formance.
The main disadvantages of wet methods are high cost and com-
plicated synthetic procedure. Molten salt (MS) method is a simple
technique to prepare complex oxide materials. This method is
based on the use of a salt with low melting point such as alkali metal
sulfates, hydroxides, carbonates and chlorides. Highly pure mate-
rials can be prepared at relatively low temperatures in MS method
due to relatively higher diffusion rates between reaction compo-
nents. Various lithium salts are used to prepare lithium manganese
oxides and lithium cobalt oxide using MS method [58–60]. Spher-
ical and well-ordered highly crystalline LiNi0.5 Mn1.5 O4 materials
are prepared by MS method by different research groups [61,62].
The SEM images of highly crystalline and spherical LiNi0.5 Mn1.5 O4
materials prepared by MS method are shown in Fig. 5b and c [61,62].
Combustion reaction method is also used for the preparation of
various oxide materials [63,64]. Zhang et al. used carbon combus-
tion method (CCS) to prepare cubic LiNi0.5 Mn1.5 O4 material with a
space group of Fd3m using carbon as fuel [65]. In this CCS method,
the structure and particle size could be adjusted by the amount
of carbon used for combustion. A representative SEM image of the
LiNi0.5 Mn1.5 O4 material prepared by CCS method is shown in Fig. 5d Fig. 6. Rietveld refinement profiles of XRD data for (a) LiNi0.5 Mn1.5 O4−ı , and (b)
[65]. LiNi0.5 Mn1.5 O4 powders [30].

3. Characterization Cyclic voltammetry is an excellent electrochemical technique

to study the redox reactions and it has been widely used by
It is known that the synthesis of pure phase of LiNi0.5 Mn1.5 O4 electrochemists in various research fields. This technique was con-
is somewhat difficult due to the presence of unwanted impurities veniently used to characterize the spinel LiNi0.5 Mn1.5 O4 material
such as NiO and Lix Niy O. As mentioned earlier, Sun and co-workers by different research groups [31,41,46]. A typical cyclic voltam-
successfully synthesized the ordered and disordered spinels by mogram of disordered spinel LiNi0.5 Mn1.5 O4−ı is shown in Fig. 8
molten salt method [30]. To prepare the disordered spinel, the pre- [31]. Three well-defined reversible peaks were observed during
cursors were mixed and calcined at 900 ◦ C for 3 h in a covered charge and discharge. The appearance of 4 V peak was due to Mn3+
alumina crucible. The disordered spinel powders thus obtained ions which were formed by the oxygen loss during high tem-
were oxidized to ordered spinel by heating at 700 ◦ C for 48 h in perature calcinations. The two major peaks appearing between
air. The ordered (LiNi0.5 Mn1.5 O4 ) and disordered (LiNi0.5 Mn1.5 O4−ı ) 4.5 and 5 V during charge and discharge cycling were due to the
forms of the spinel material could be differentiated by X-ray diffrac- redox couples Ni2+ /Ni3+ and Ni3+ /Ni4+ or ordering of lithium and
tion (XRD) measurements. Rietveld analysis was performed on the vacancies at x = 0.5 [69,70]. For ordered spinel, the 4 V peaks were
XRD patterns to identify the ordered and disordered structures of absent because oxidation states of Ni and Mn were +2 and +4,
the spinel material. Rietveld refinement profiles are shown in Fig. 6 respectively [30]. Charge and discharge measurements were used
[30]. Small peaks representing superstructure were observed for to characterize and differentiate ordered and disordered spinel
ordered spinel but these peaks were absent in the case of disor- LiNi0.5 Mn1.5 O4−ı materials. The first two cycles of charge and dis-
dered spinel. Similar results were also observed for other spinels charge voltage profiles of two different spinels are shown in Fig. 9
such as LiMg0 .5 Mn1.5 O4 and LiZn0.5 Ti1.5 O4 [66,67]. Recently, Shaju [68]. The difference in charge capacity between first and second
and Bruce synthesized nanosized ordered and disordered forms of cycle was due to electrolyte oxidation [71,72]. The voltage step
the spinel using resorcinol–formaldehyde route [68]. These authors appearing around 4.7 V was more clear in the case of disordered
used lattice parameters obtained from XRD analysis to differen- spinel [71–73]. This difference in the voltage plateau could be used
tiate the two forms of the spinel material. In the ordered spinel, to identify if the spinel material was ordered or disordered. A small
the oxidation states of Ni and Mn are +2 and +4, respectively, step appearing around 4 V in the disordered material was associ-
whereas a small amount of oxygen loss in the disordered spinel ated with the Mn3+/4+ redox couple [71–73].
is compensated by the formation of Mn3+ . Since the size of Mn3+ is
bigger than Mn2+ , the cubic lattice parameter is larger in disordered 4. Effect of doping
(8.1733 Å) than that of ordered spinel (8.1677 Å). Interestingly,
transmission electron microscopy (TEM) was used to observe the Many different elements can be doped into the high voltage
structural differences between ordered LiNi0.5 Mn1.5 O4 and disor- LiNi0.5 Mn1.5 O4 spinel structure, and they impact the structure, its
dered LiNi0.5 Mn1.5 O4−ı spinels and the results are shown in Fig. 7 stability on lithium insertion/deinsertion, and the capacity reten-
[30]. The disordered spinel showed electron diffraction pattern of tion on cycling. The use of high voltage material may have adverse
a typical spinel and however, the ordered spinel showed extra effects such as possible electrolyte decomposition which may
diffraction spots (superlattice pattern) in addition to the spots increase capacity fading on cycling. To improve the high volt-
observed for pure spinel. age electrochemical performance of LiNi0.5 Mn1.5 O4 spinel, various
 R. Santhanam, B. Rambabu / Journal of Power Sources 195 (2010) 5442–5451 5447

Fig. 9. Charge and discharge voltage profiles for the first and second cycles at 30 ◦ C
and 75 mA h g−1 between 3.5 and 5.0 V for (a) the disordered phase and (b) the
ordered phase [68].

dopants have been proposed by different research groups. Titanium

(Ti) was added as a dopant in the LiNi0.5 Mn1.5 O4 spinel structure
[74,75]. Ti doping improved the disordering of the transition met-
als and consequently lowers the symmetry from primitive simple
Fig. 7. Electron diffraction patterns of (a) LiNi0.5 Mn1.5 O4−ı and (b) LiNi0.5 Mn1.5 O4
cubic structure (P43 32) to face-centered spinel (Fd3m). In addition,
phases in the [99] zone [30].
the Ti doped LiNi0.5 Mn1.5−x Tix O4 spinel exhibited higher operat-
ing voltage, faster lithium diffusion and better rate capability than
undoped spinel. However, the capacity was decreased on doping
of larger amount of Ti due to blocking of migration pathway of
electrons in octahedral sites. Voltage profiles of LiNi0.5 Mn1.5−x Tix O4
spinel with various amounts of Ti doping are shown in Fig. 10 [74].
Alcantara et al. also reported that the doping of small amounts of
Ti improved the electrochemical performance whereas a deterio-
ration of the reversible capacity was observed for large amounts
of Ti [75]. Iron (Fe) was used as a dopant for LiNi0.5 Mn1.5 O4
spinel and it was shown to improve the electrochemical perfor-
mance [76,77]. The presence of Fe in the tetrahedral sites of the
structure stabilizes the solid during extended cycling. The electro-
chemical performance of LiNi0.5 Mn1.5 O4 spinel was also studied by
double substitution with Ti and Fe [78]. The material containing
0.05Fe + 0.05Ti showed a two phase mechanism of lithium extrac-
tion and in contrast, the material containing 0.10Fe + 0.10Ti showed
only one phase. It was suggested that the best capacity retention
could be achieved by using the LiFe0.10 Ti0.10 Ni0.45 Mn1.35 O4 com-
position associated with single phase mechanism combined with
structural stabilization by Ti.
Chromium (Cr) could be added to the LiNi0.5 Mn1.5 O4 spinel
Fig. 8. Cyclic voltammogram of LiNi0.5 Mn1.5 O4 electrode cycled between 3.5 and structure as a dopant [79–81]. The influence of Cr content on the
5 V vs. Li/Li+ at 0.2 mV s−1 scan rate [30]. electrochemical performance of the spinel was studied in detail.
It was reported that the particle size depended on Cr content.
5448 R. Santhanam, B. Rambabu / Journal of Power Sources 195 (2010) 5442–5451

Fig. 10. Voltage profiles of LiNi0.5 Mn1.5−x Tix O4 with various amounts (x) of Ti doping: (a) x = 0, (b) x = 0.05, (c) x = 0.1, (d) x = 0.2, (e) x = 0.3, and (f) x = 0.5 [74].

Moreover, Cr-doped spinel delivered higher discharge capacity and was significantly improved. This result was due to fine-structure
capacity retention than that of undoped spinel. Another element arising from fluorine doping.
that was used as a dopant for LiNi0.5 Mn1.5 O4 spinel was ruthenium
(Ru) [82]. The rate capability and cycling performance were sig- 5. Effect of coating
nificantly improved by Ru doping. High capacity of the Ru doped
spinel was due to minimized polarization and improved electrical It should be noted that lithium transition metal oxides can
conductivity. The enhanced rate capability and cyclability resulted react with the electrolyte and lead to safety issues. Significant
from improved structural stability of LiNi0.5 Mn1.5 O4 spinel by Ru. efforts have made by different research groups to increase the sta-
Zirconium (Zr) and aluminum (Al) also have similar effects like bility of lithium metal oxides. It was shown that better stability
other dopants. From Raman spectra, Oh et al. found that the struc- can be achieved by coating the materials with stabilizing surface
ture of the Al and Zr doped materials was ordered spinel and Cr layer. Lithium metal oxides were coated with various oxides and
doped spinel was disordered. They believed that the excellent elec- phosphates and demonstrated improved capacity retention dur-
trochemical properties of the Cr-doped spinel might be due to ing cycling. Surface modifications of LiNi0.5 Mn1.5 O4 spinel material
high electrical conductivity, chemical and structural stability [83]. by coating various oxides and phosphates such as ZnO [87–90],
Magnesium (Mg) doping was shown to improve the performances SnO2 [91], Li3 PO4 [92], and different metal treatments such as Zn
of LiNi0.5 Mn1.5 O4 spinel [84]. LiMg0 .07 Ni0.43 Mn1.5 O4 material was [93], Au [94], Ag [95] have been widely investigated. In the case
prepared by solid state, sol–gel and xerogel methods and the elec- of ZnO-coated LiNi0.5 Mn1.5 O4 , the ZnO-coated electrode delivered
trochemical performances were compared. It was found that the the capacity of 137 mA h g−1 without any capacity loss even after
spinel materials prepared by sol–gel and xerogel methods were 50 cycles at 55 ◦ C as shown in Fig. 11 [88]. LiNi0.5 Mn1.5 O4 sur-
better than solid state method. This was due to sub-micron sized face was protected by ZnO coating, suppressed Mn dissolution and
particles of single crystals together with nanoparticles obtained increased the structural stability. ZnO played an important role
from sol–gel and xerogel methods. in reducing the HF content in the electrolyte. The ZnO coating
Another dopant that could be occupied in the anion site is layer was acted like a scavenger of fluoride anions from HF gen-
fluorine which was a common dopant in the field of lithium-ion bat- erated from the decomposition of LiPF6 salt in the electrolyte by
teries. The reversible capacity of high voltage LiNi0.5 Mn1.5 O4 spinel transforming HF to ZnF2 [87–90]. Similarly, SnO2 coating on the
material was improved by fluorine doping (LiNi0.5 Mn1.5 O3 .975 F0.05 ) surface of the LiNi0.5 Mn1.5 O4 improved capacity retention and the
[85]. It was reported that the performance improvement was improvement enhanced with increased SnO2 content. Based on the
mainly because of suppression of the formation of NiO impu- X-ray photoelectron spectroscopy results, Fan et al. showed that
rity during synthesis. Fluorine doping in the oxygen sites of the the main reason for the electrochemical stability was due to rela-
spinel could change the lattice parameters and bonding energy as tively low content of LiF in the SnO2 coated LiNi0.5 Mn1.5 O4 [91].
reported by Du et al. [86]. They prepared the spinel material with In a similar manner, Li3 PO4 coating protects the surface of the
different fluoring contents. For the materials with fluorine beyond LiNi0.5 Mn1.5 O4 material and function as a solid electrolyte interface
0.1 instead of oxygen, the capacity decreased but the cyclability between LiNi0.5 Mn1.5 O4 and solid polymer electrolyte (SPE) to pre-
 R. Santhanam, B. Rambabu / Journal of Power Sources 195 (2010) 5442–5451 5449

Fig. 12. Charge/discharge curves of the LiNi0.5 Mn1.5 O4 /AC hybrid supercapacitor at
Fig. 11. Specific discharge capacity of (a) the as-prepared LiNi0.5 Mn1.5 O4 and (b) different discharge current densities in 1MLiPF6 in EC/DMC electrolyte between 1.0
ZnO-coated LiNi0.5 Mn1.5 O4 electrodes at 55 ◦ C at constant current densities of and 3.0 V [109].
0.4 mA cm−2 [88].

as electrode materials in asymmetric supercapacitors [105–108].

vent the degradation of SPE [92]. Metals such Zn, Au and Ag were Recently, Zhao et al. studied the pseudocapacitance properties of
also coated on spinel LiNi0.5 Mn1.5 O4 material and improvements activated carbon/LiNi1/3 Co1/3 Mn1/3 O2 asymmetric supercapacitor
in the electrochemical performance were demonstrated [93–95]. in aqueous electrolyte [109]. This system exhibited an excellent
Arrebola et al. studied the effect of Au coating on the performance cycling performance. Among the various battery cathode materials,
of LiNi0.5 Mn1.5 O4 and the coating had a beneficial effect and it spinel LiNi0.5 Mn1.5 O4 material was a promising 5 V cathode mate-
significantly increased the capacity. The role of the Au was to hin- rial. The possibility of using this high voltage intercalation material
der the unwanted reactions and simultaneously prevent the active as the positive electrode in combination with activated carbon
material particles from reacting with decomposition products such negative electrode to fabricate an asymmetric supercapacitor was
HF which was the main reason for Mn dissolution [94]. The same exploited by Rambabu and co-workers [110] and Li et al. [111]. The
authors studied the adverse effect of Ag treatment on the electro- charge and discharge curves of the LiNi0.5 Mn1.5 O4 /AC hybrid super-
chemical performance of LiNi0.5 Mn1.5 O4 . Ag treatment had only capacitor at different current densities are presented in Fig. 12.
limited benefit at low current densities and at moderate and high This system exhibited excellent capacity retention even after 1000
current densities the capacity delivered was relatively low for Ag- cycles [110]. In this system, the faradaic lithium-ion intercalation
treated spinel than that of untreated spinel [95]. Recently, Kang et reaction and non-faradaic lithium-ion adsorption/desorption reac-
al. coated the spinel LiNi0.5 Mn1.5 O4 with BiOF and studied the elec- tion occurred in LiNi0.5 Mn1.5 O4 and activated carbon, respectively.
trochemical performance [96]. Spinel LiNi0.5 Mn1.5 O4 powders were High energy density and power density asymmetric supercapacitor
coated with BiOF to improve their electrochemical performances. could be achieved by this new technology of using high potential
The BiOF-coated LiNi0.5 Mn1.5 O4 showed significantly improved lithium intercalation compound as the positive electrode and the
capacity retention than that of the uncoated one. The rate capability active carbon as the negative electrode.
of the BiOF-coated LiNi0.5 Mn1.5 O4 was also significantly enhanced.
It was suggested that the improved electrochemical performance 7. Conclusions
was attributed to the scavenging HF by BiOF layer from the elec-
trolyte. Very recently, Amine’s group has reported a remarkable From this review, it can be suggested that modified high volt-
improvement in cycling stability at 55 ◦ C by coating the spinel age spinel LiNi0.5 Mn1.5 O4 is one of the promising cathode materials
LiNi0.5 Mn1.5 O4 particles with ZrO2 . The ZrO2 coating also improved for next generation lithium-ion batteries since they show excellent
the thermal stability of LiNi0.5 Mn1.5 O4 cathode due to the suppres- performances such as good cyclability, rate capability, and thermal
sion of interfacial resistance between cathode and electrolyte by stability. Metal dopings on LiNi0.5 Mn1.5 O4 lead to excellent cycling
protecting the electrolyte reactivity with cathode surface [97]. due to prevention of phase transformation and structural stabi-
lization by dopants. Surface coatings by metal oxides protect the
6. Cathode for asymmetric supercapacitors surface of the LiNi0.5 Mn1.5 O4 by acting like a scavenger of fluo-
ride ions from HF generated from the electrolyte. It is reasonable
Electrochemical supercapacitors are attractive and new energy to suggest that the doping and surface coatings play an impor-
storage devices due to their high power density, long cycle life, tant role in improving electrochemical performance of the spinel
low self-discharge and high safety [98]. Electrochemical capac- LiNi0.5 Mn1.5 O4 . Since this spinel cathode material has high nominal
itors are divided as electrochemical double layer capacitor and voltage of 4.7 V, Ohzuku’s group have successfully demonstrated a
redox capacitor depending on the electrode materials used and the 3 V lithium-ion cell with LiNi0.5 Mn1.5 O4 with zero-strain insertion
charge storage mechanism [99–101]. Recently, asymmetric super- material Li[Li1/3 Ti5/3 ]O4 and the cell showed a quite flat operat-
capacitors have received considerable attention because they offer ing voltage of 3.2 V with excellent cyclability [112]. In addition, by
advantages of both supercapacitors and batteries [102,103]. This selecting the high voltage LiNi0.5 Mn1.5 O4 material as the positive
type of electrochemical system combines faradaic battery electrode electrode in combination with an activated carbon negative elec-
and a double layer capacitor electrode [104]. Various battery mate- trode could provide a new technology to achieve a high energy and
rials including LiMn2 O4 , LiCoO2 and LiNi1/3 Co1/3 Mn1/3 O2 were used power density asymmetric electrochemical supercapacitor.
5450 R. Santhanam, B. Rambabu / Journal of Power Sources 195 (2010) 5442–5451

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