STRUCTURE OF SPINEL CATHODES: The spinel structure provides the cubic-close-

packed oxygen provides a three dimensional array while the edges of octahedral MnO 6 are
shared with Li-ions. There are vacant tetrahedral and octahedral interstitial sites in the three-
dimensional structure that provides pathways to lithium ion diffusion. The spinel LiMn2O4
has a strong edge-shared [Mn2] O4 octahedral lattice and exhibits good structural stability the
charge-discharge process. LiMn2O4 spinels have shown a lack of robustness in their cycle life
and irreversible loss of capacity that becomes rapid at elevated temperatures Spinel
cathodes are used over layered ones due to their structural stability and robustness. [1]
ELECTROCHEMICALPROPERTIES OF SPINEL CATHODES: The electrochemical
data demonstrate that Li+ ions are extracted from the tetrahedral sites of the Li xMn2O4 spinel
structure at approximately 4 V in a two-stage process, separated by only 150 mV at a
composition Li0.5Mn2O4. At x = 0, the -MnO2 phase (- [Mn2] O4 in the spinel notation) is
formed. The two-step process is due to ordering of the lithium ions on one-half of the
tetrahedral 8a sites. Lithium insertion into LMO occurs at approximately 3 V. During this
process, Li+ ions are inserted into the octahedral 16c sites of the spinel structure. Since the
16c octahedral share faces with the 8a tetrahedral, electrostatic interactions between the Li+
ions on these two sets of sites cause an immediate displacement of the tetrahedral-site Li+
ions into neighbouring vacant 16c octahedral sites. The reaction results in a first-order
transition to Li2Mn2O4 with a stoichiometric rock-salt composition on the surface of the
electrode particle. The electrochemical process at 3 V is thus a two-phase reaction. During
discharge, a reaction front of Li2Mn2O4 moves progressively from the surface of the
LiMn2O4 particle into the bulk. At 3 V, the Li insertion is accompanied by a severe Jahn-
Teller distortion as a result of an increased concentration of Mn3+: d4 ions in the Mn2O4
spinel lattice, which reduces the crystal symmetry from cubic (c/a = 1.0) to tetragonal
symmetry (c/a = 1.16) that results in a 16% increase in the c/a ratio detrimental to the
electrochemical cycling. [1]
APPICATIONS: The spinel cathodes are used mainly in vehicular applications. The high
energy density of this class of cathodes enables us to use if for many high end applications.
Spinel cathodes are generally used over layered ones because of its robust structure and
doesnt degrade easily. They are especially used in Electric vehicles or Hybrid Electric
vehicles. [2]
THERMAL STABILITY OF CATHODES: Generally cathodes operate quite efficiently
but after repeated number of charging and discharging cycles they start degrading.
Degradation can also occur when the battery is operated at high temperatures which leads to
reduction in the mass of the electrode thus hindering the performance of the battery. Upon
reaching the threshold temperature, the oxide cathodes start releasing oxygen which is
dangerous as it cause thermal runaway further damaging the battery leading to fire ignition or
explosion of the battery.
MECHANISM OF THERMAL DEGRADATION: For the stable spinel LiMn2O4, high
temperature is needed to provide enough thermodynamic driving force for its endothermic
decomposition reaction. The fully charged Y -Mn2O4 transforms kinetically into the stable
phase -MnO2 first and then decomposes at elevated temperature into the lower-valence
oxides, -Mn2O3 and Mn3O4. The calculated decomposition heat for the three systems is in
good agreement with experiments. When present, the electrolyte can act as a sink for the
oxygen released from the cathode. Although oxygen release from the cathode is generally
endothermic, its combustion with the electrolyte leads to a highly exothermic reaction. [3]
EXPERIMENTAL EVIDENCE OF THERMAL DEGRADATION OF SPINEL
CATHODES: The thermal stability of LNMO spinel cathodes have been studied. The
LNMO cathodes are generally not that stable when compared to the parent LMO cathode.
The LMO cathode has high voltage and density but it lacks in capacity retention and thermal
degradation. The 25% on the Mn is substituted with Ni to study the behaviour of LNMO
cathodes at elevated temperature. The study suggests that the LNMO cathodes have good
capacity retention and high rate of reaction because of the presence of Ni ions. But at the
same time it is important to study the thermal decomposition of LNMO cathodes. There are
two types: Ordered LNMO and Disordered LNMO (o-LNMO and d-LNMO respectively).
The TR-XRD combined with mass spectroscopy was used to study the structural changes and
the release of the oxygen gas during thermal decomposition.

Figure 1 Figure 2

Figure: (1) In situ XRD patterns combined with simultaneously measured mass spectroscopy (MS) data that trace the
release of gaseous oxygen of charged (a) d-LNMO and (b) o-LNMO during heating up to 375 C. Left, in situ XRD patterns;
right, profile of oxygen release [4] and (2) Schematic of two phase transition pathways of charged LNMO during heating. [4]

Both the charged o-LNMO and d-LNMO were heated up to 375 0C and the results the date
obtained from TR-XRD and mass spectroscopy were plotted as shown in the figure 1. There
was noticeable oxygen release and the phase transition for both type of structure well below
3750C which is in contrast to the parent spinel cathode (LMO). [4] Generally at high
temperature the spinel cathodes transforms to two phases by three reactions. The
LiMn1.5Ni0.5O4 oxidises into Li0.5Mn1.5Ni0.5O4 and then into Mn1.5Ni0.5O4 during charging
phase. During discharge phase the same reactions happen in reverse order. [5] The first
pathway usually takes place in d-LNMO cathodes at high temperatures. There are is one
intermediate phase that takes place where ilmenite NiMnO 3 and -Mn2O3 are formed while
oxygen is being released. Further heating results in the formation of the final structure
NiMN2O4 with more oxygen being released. If the above reaction occurs in early phase then
the cathode material is highly unstable. Usually Ni2+ ions if available from disordering the d-
LNMO material favours early decomposition. [4] The second pathway happens in the thermal
decomposition of o-LNMO cathode material because it does not has a favourable
environment to undergo transformation according to path one. In this process the Mn ions
move from octahedral site to the tetrahedral sites with milder oxygen release to from the final
NiMn2O4 structure. This process usually takes place at higher temperature than the process
one with milder oxygen release in a wide temperature range. [4] In addition to this, the
dissolution of the charged electrode at elevated temperatures takes place with loss of oxygen
and disproportionate reaction at the electrode surface. [6] The reaction (2) shows the
disproportionate reaction the Mn ions that dissolute in the electrolyte.
2Mn3+ Mn4+ + Mn2+ (2)
APPROACHES TO OVERCOME THERMAL DEGRADATION OF SPINEL
CATHODES: Since Li-ion battery are more and more used in todays technologies as an
energy storage device, it is important to develop new approaches to overcome the thermal
runaway problem which leads to degradation of the cathodes further leading to battery
failure, which leads to fire ignition causing the battery to explode. There are several method
proposed few approaches covered in this review paper.
LiMn2O4 BLENDED WITH LiNi0.8Co0.15Al0.05O2 (NCA): Another group investigated the
blending of LiMn2O4 with LiNi0.8Co0.15Al0.05O2 (NCA) and studies their electrochemical and
thermal behaviour. They tested the cathodes separately to investigate their properties and
found out that both LiMn2O4 spinel and NCA (when used alone as active cathode materials)
exhibits one or more characteristics that are rather detrimental for a proper use in batteries
e.g., poor thermal stability and rate capability for NCA, and poor cycle life and poor
electrochemical performance at elevated temperatures due to significant Mn dissolution for
spinel. Blend electrodes having different compositions were morphologically and
electrochemically characterized. The blend containing 33.3% NCA has been found to be the
best among all investigated blends and this not because of any single remarkable property
but, rather, by the combination of several good balanced properties with concomitant
compromises. Its discharge capacity at C/5 is rather low, but at 5 C is significantly higher in
comparison to pure NCA (even though it is slightly lower than that of pure spinel). Blends
containing more than 33.3% NCA behave similar to the pure NCA, i.e., they have a poor
electrochemical performance at high C-rates. Mn dissolution from LiMn 2O4 spinel was
considerably reduced by NCA addition: from 33 ppm in pure spinel up to less than 1 ppm in
the blend containing 33.3% NCA. This could provide a better cycle life as well as better
performance at elevated temperatures. Also, the heat generation for the blend containing
33.3% NCA was significantly lower than that of pure NCA. Oxygen release, even if it takes
place, became less significant. This means there is an improvement in the thermal stability,
even though the stability of pure spinel is better, since it experiences no oxygen evolution in
the investigated temperature range. [7] Fig 3 shows the Mn dissolution against the NCA ratio
blends.
SURFACE COATING OF SPINEL LiMn 2O4 CATHODE ELECTRODE WITH
LITHIUM NICKEL MANAGANESE OXIDE: The surface of the spinel LiMn2O4 was
coated with Lithium Nickel Manganese oxide by RF sputtering method. A preliminary
experiment was performed on the glass in order to determine and control the deposition
thickness of lithium nickelmanganese-oxide by RF sputtering equipment. The thickness
identified by SEM data reveals that the LNMO layer, deposited on the glass for 30 min, was
approximately 183.6 nm in Fig. 4 based on the preliminary experiment, Li-Ni-Mn-O
components were deposited onto the conventionally tape-casted electrode, which consisted of
an active material (LiMn2O4 with spinel structure), a conductive material (carbon black), and
a binder (PVdF) under the sputtering conditions mentioned in the previous section. Figure 5
compares the DSC curves of the bare and LNMO-modified LiMn2O4 electrodes in a fully
charged state. The exothermic reaction of bare and LNMO-modified LiMn 2O4 electrodes
commenced minutely at 168.48 and 170.750C, respectively. After that, exothermic reactions
gradually occur around 2500C. The total heat generated during DSC measurement for the bare
and LNMO-modified LiMn2O4 electrodes, respectively, correspond to 919.3 J g-1 and 815.7 J
g-1. Interestingly, additional shoulder peak around 295 0C is found for the LNMO-modified
LIMn2O4, suggesting that the LNMO coating layer is related the exothermic reaction with
electrolyte. Although both electrodes exhibit similar onset temperatures for the exothermic
reaction with the electrolyte, the LNMO-modified electrode exhibits a reduced exothermic
peak intensity at approximately of 3000C and less total heat flow compared to the bare
electrode, as demonstrated in Fig 5. Based on this, the surface modification of the electrode
provides more stable surface characteristics and protects from electrolyte instability at high
temperatures, resulting in an enhancement in thermal stability for lithium-ion battery
application. [8]

Figure 3 Figure 4 Figure 5

Figure: (3) Concentration of Mn dissolved from different LiMn 2O4 spinel/NCA blend samples stored in LiPF 6 electrolytes at
600C for 2 weeks. [7] (4) SEM images and EPMA mapping of the SEM cross-sectional view for the bare and LNMO-
modified electrodes [8] and (5) DSC profiles of the bare and LNMO-modified LiMn2O4 electrodes. [8]

BINDER PROTECTIVE FILM ON SPINEL CATHODES (LiNi 0.5Mn1.5O4): The

performance of the spinel cathode was investigated combining them with different binders.
The water soluble sodium carboxymethyl cellulose (CMC) and sodium alginate (SA) was
used as a binder when compared to the conventional polyvinylidene difluoride (PvDF)
binder. The experiments show that the performance of the cathode was significantly improved
at high temperature. It was found that at elevated temperatures the cathodes with the PvDF
binder starts fading much faster than the cathode with CMC and SA binder. The water soluble
binder is much more stable than PVdF in the electrolyte. PVdF binder suffers from severe
swelling due to absorb electrolyte solution, leading to the less contact between binder and
other electrode components the solid-electrolyte interface (SEI) resistance (RSEI) and charge
transfer resistance (Rct), respectively. The results show that the use of amorphous binder can
effectively reduce the direct contact area betweenLiNi 0.5Mn1.5O4 powders and electrolyte.
Therefore, the reaction of SEI formation is significantly suppressed. A seriously peeled off of
active material was found in the electrode with PVdF binder. This result also reflects the high
resistance of the cycled electrode with PVdF binder. In addition to this, a great amount of
deposition of dissolved metals was observed on the reference electrode. Although no obvious
failure was found in the electrode with amorphous binder. It implies that the severe metal
dissolution from electrode material is suppressed. The amorphous binder builds a percolating
network that reduces the contact between the electrode and the electrolyte. This network
supresses the dissolution of Ni and Mn ions into the electrolyte and makes this electrode
suitable for high temperature use. [9]
IMPROVEMENT OF THERMAL STABILITY OF LiMn 2O4 BY POLYMER
COATING: The polymer poly (diallyldimethylammoniumchloride) (PDDA) is used for
surface coating of the cathode material and their thermal stability have been studied. The
cathode LiMn2O4 modified by surface adsorption method of polymer. Transmission electron
microscopy was used to characterize the polymer coating on the LiMn2O4 particles. A typical
electron diffraction micrograph is shown in Figure11. The TEM observation revealed the
presence of polymer, although the uniformity of the polymer coating is not clear. The TEM
image shows that the PDDA film embedded the crystalline LiMn2O4 particles, i.e., the
PDDA was not simply mixed with LMO particles but coated on the LMO powder. [10] The
significant improvement in thermal stability of Li-ion batteries by polymer coating of

LiMn2O4 is probably due to the membrane-like

behaviour of the polymer. The coating should protect the LiMn2O4 particle surface from
direct contact with the electrolyte and possibly inhibit surface reactions that are in part
responsible for the capacity fading in Li-ion batteries. [10] The surface coating of the spinel
cathode with the PDDA shows that there is enhanced thermal stability and the capacity fading
also decreased after storage.

Figure 6 Figure 8 Figure 7

Figure: (6) Cycling performance of LiNi0.5Mn1.5O4 electrodes with CMC, SA, and PVdF binders at (a) 25C and (b) 55C
[9]
, (7) TEM image of typical SM-LMO powder indicating crystalline LiMn2O4 region and polymeric film. [10] and (10) Mn
dissolution amount vs. storage time at 550C of the Li [LixAlyMn2-x-y] O4-zFz powders: (a) x = 0, y = 0, z = 0; (b) x = 0.05, y =
0.1, z = 0; (c) x = 0.05, y = 0.1, z = 0.05; and (d) x = 0.05, y = 0.1, z = 0.1. [11]

CATION AND ANION SUBSTITUTON INTO THE SPINEL LiMn 2O4 MATERIAL:
The electrochemical properties of the various Li-Al-Mn-O-F spinel are studied. The DSC
(Differential Scanning Calorimetry) was performed using the various spinel cathode materials
as shown in the fig 8. The onset temperature for the thermal degradation in raised
significantly and the reaction heat is reduced by Li-Al-F substitution. For the
Li1.05Al0.1Mn1.85O3.95F0.05 which was charged to 4.3 V, one major peak is observed at 257 C
whereas for LiMn2O4 one peak was observed at around 240 C. While the positions of the
exothermic peaks are similar in Li1.05Al0.1Mn1.85O4-zFz (z = 0 0.1), the heat which is
associated with each exothermic peak is significantly decreased with increasing fluorine
content: 99.631 W g-1 (z = 0), 79.489 W g-1 (z = 0.05), 49.815 W g-1 (z = 0.1), respectively.
The DCS data shows that the substituted spinel cathode materials show higher thermal
stability than the parent LiMn2O4 spinel cathode. [11]

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