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Thermochimica Acta
journal homepage: www.elsevier.com/locate/tca
A R T I C L E I N F O
A B S T R A C T
Article history:
Received 24 June 2014
Received in revised form 31 October 2014
Accepted 2 November 2014
Available online 4 November 2014
The enthalpies of formation of Li1+xMn2xO4 (0 < x < 0.1) spinel phases were measured using high
temperature oxide solution calorimetry in a sodium molybdate solvent at 701 C. One commercially
available LiMn2O4 powder and two Li1+xMn2xO4 samples synthesized using the solgel method were
used for the measurements. The enthalpies of formation of the spinels from the binary constituent oxides
and from the elements become more exothermic with increasing lithium content and increasing average
oxidation state of the manganese cation in the range 0 < x < 0.1. Additionally, the lithium-rich boundary
of the Li1+xMn2xO4 phase for 0 < x < 0.1 was re-investigated using differential thermal analysis
combined with thermogravimetric analysis.
2014 Elsevier B.V. All rights reserved.
Keywords:
Li1+xMn2xO4
Spinel
Oxide solution calorimetry
Enthalpy of formation
Lithium-ion battery
1. Introduction
The lithiummanganeseoxygen system is a key materials
system for the development of advanced cathodes for lithium-ion
batteries. In particular, the Li1+xMn2xO4 cubic spinels (Fd3m
spacegroup) are attractive because they are considered environmentally friendly, are stable against Li extraction, have a high
electrode potential of approximately 4 V versus lithium, and
because the cost of Mn is lower than that of Co which is required for
LiCoO2 production.
The Li1+xMn2xO4 cubic spinels contain a three-dimensional
network of occupied tetrahedral (8a) and vacant interstitial
octahedral (16c) sites. During charge and discharge, the lithium
ions diffuse from the 8a sites to adjacent 16c sites and from these
16c sites to neighboring 8a sites. The reversible capacity of the
cubic spinels originates from the Mn3+/Mn4+ redox pair, in which
the oxidation state of the transition metal cation oscillates
between +3 and +4 during lithium insertion and extraction.
The enthalpies of formation of Li1+xMn2xO4d spinels have
been measured by Wang and Navrotsky [1] using high temperature
oxide solution calorimetry and by Idemoto et al. [2,3] using acid
solution calorimetry. Both Wang and Navrotsky [1] and Idemoto
et al. [2,3] report that the enthalpies of formation of the
Li1+xMn2xO4d spinels become more exothermic with increasing
lithium content (increasing x in Li1+xMn2xO4d up to x = 1/4).
According to Wang and Navrotsky [1], this trend results from the
oxidation of Mn3+ to Mn4+ (an exothermic process) which occurs
* Corresponding author. Tel.: +49 7216 822258; fax: +49 7216 824567.
E-mail address: damian.cupid@kit.edu (D.M. Cupid).
http://dx.doi.org/10.1016/j.tca.2014.11.003
0040-6031/ 2014 Elsevier B.V. All rights reserved.
36
Table 1
Sample table.
Chemical name
Source
Purication method
Alfa Aesar
AppliChem
Merck Schuchardt OHG
Merck KGaA
Merck KGaA
MTI
Alfa Aesar
Alfa Aesar
Air Liquide
basi Schberl GmbH & Co
0.99
0.99
0.99
0.995
0.99
0.995
0.99997
0.9999
0.9999g
0.1985O2h
none
none
none
none
none
none
none
none
none
none
a
b
c
d
e
g
h
LiOOCCH32H2O.
(CH3COO)2Mn4H2O.
C6H10O4.
Na2MoO42H2O.
MoO3.fMoO2.
Purity expressed in mole fraction.
The concentration of O2 in Ar/20 volume% O2 is given in volume fraction. The standard uncertainty is u = 0.0040.
37
Table 2
Expected and measured compositionsa of the Li1+xMn2xO4 spinel samples. The lithium and manganese compositions were measured using ICP-OES. The Li1+xMn2xO4
(x = 0.1 and 0.2) samples were prepared by the solgel method using the starting compounds Li-acetate, Mn-acetate, and adipic acid. The origin and purities of the starting
chemicals are given in Table 1.
Nominal stoichiometry
LiMn2O4
Li1.1Mn1.9O4
Li1.2Mn1.8O4
Measured data
Calculated stoichiometry
Li mass%
Mn mass%
Li
Mn
Li/Mn
4.00 0.01
4.34 0.07
4.81 0.01
60.38 0.07
60.39 0.66
58.10 0.07
1.032 0.002
1.088 0.019
1.188 0.003
1.968 0.002
1.912 0.019
1.812 0.003
0.524 0.002
0.569 0.013
0.656 0.002
The number following the symbol is the expanded uncertainty U, calculated as U = ku for the measured data and U = kuc for the calculated stoichiometries, where u and uc
are the standard and combined uncertainties respectively. A coverage factor k = 2 was used, corresponding to a condence interval of 95 percent.
38
LiMn2O4
Li1.1Mn1.9O4
Li1.2Mn1.8O4
Transformation temperatures ( C)
T1
T2
T3
757 3
691 3
612 3
934 1
932 1
932 1
1047 4
1062 2
1055 1
The standard uncertainties for T1 are u(T1) = 3 C and are assigned based on the
uncertainty in selecting the temperature at which the rst derivative of the mass
change with time deviates from the steady-state baseline as shown in Figs. 5 and 6.
The number following the symbol for the T2 and T3 temperatures is the expanded
uncertainty U, calculated as U = ku where u is the standard uncertainty and a
coverage factor k = 2 was used, corresponding to a condence interval of 95 percent.
b
The standard uncertainty in p is u(p) = 5 kPa.
a
39
Table 4
Enthalpies of drop solutiona at p = 0.1 MPab of the samples measured in this work.
Approximately 28 g of sodium molybdate (3Na2O4MoO3) solvent was used for the
high temperature oxide melt drop solution calorimetry. The solvent was maintained
at a temperature of 701 C inside the platinum crucibles in the calorimeter. Each
sample weighed between 5 and 6 mg and the recorded heat effects for each sample
were between 5 and 10 J. The enthalpy of drop solution is the sum of the enthalpy
increment from 298 to 974 K and the enthalpy of dissolution of the samples in
sodium molybdate at 974 K.
Nominal stoichiometry
Mn2O3
LiMn2O4
Li1.1Mn1.9O4
Li1.2Mn1.8O4
165.32 1.61
249.25 2.08
253.71 2.53
261.28 1.78
8
14
11
12
a
The number following the symbol is the expanded uncertainty U, calculated
as U = ku where u is the standard uncertainty and a coverage factor k = 2 was used,
corresponding to a condence interval of 95 percent.
b
The standard uncertainty in p is u(p) = 5 kPa
DHdsLi2O
MnO2(s,
Li1+xMn2xO4(s,
DHdsMn2O3
DHdsMnO2
DHdsLi1+xMn2xO4
1 x
1 3x
Li2 O
Mn2 O3
2
2
1 2x MnO2 ! Li1x Mn2x O4
1 x
1 3x
DHds Li2 O
DHds Mn2 O3
2
2
1 2x DHds MnO2 DHds Li1x Mn2x O4
Fig. 8. Enthalpy of drop solution for one commercial (lled triangle) and two
self-prepared (lled diamonds) Li1+xMn2xO4 spinels compared to the data of
Wang and Navrotsky (open squares) [1].
40
Table 5
Enthalpy of formationa of LiMnO compounds measured using high temperature oxide melt drop solution calorimetry at p = 0.1 MPab.
Nominal
stoichiometry
LiMn2O4
Li1.1Mn1.9O4
Li1.2Mn1.8O4
85.36 2.67
91.86 3.06
103.09 2.57
12.19 0.38
13.12 0.44
14.73 0.37
1381.65 2.85
1382.88 3.24
1384.64 2.83
197.38 0.41
197.55 0.46
197.81 0.40
a
The number following the symbol is the expanded uncertainty U, calculated as U = kuc where uc is the standard combined uncertainty and a coverage factor k = 2 was
used, corresponding to a condence interval of 95 percent.
b
The standard uncertainty in p is u(p) = 5 kPa.
Fig. 9. Enthalpy of formation from the oxides for one commercial (lled triangle)
and two self-prepared (lled diamonds) Li1+xMn2xO4 spinels compared to the data
of Wang and Navrotsky (open squares) [1].
4. Discussion
The enthalpies of formation of the Li1+xMn2xO4 spinels
measured in this work are in better agreement with the work of
Wang and Navrotsky [1] than with that of Idemoto et al. [3]. For
example, our value for the enthalpy of formation of Li1.1Mn1.9O4
from the binary oxides is 91.86 3.06 kJ/mol. Wang and
Navrotsky [1] report a value of 91.83 2.55 kJ/mol whereas
Idemoto et al. [3] show values of 67.5 1.2, 82.6 1.4, and
93.6 1.0 kJ/mol for samples which were annealed in Ar, 1 atm
O2, and 20 atm O2, respectively. Additionally, we report a value
for the enthalpy of formation from the constituent binary
oxides for Li1.03Mn1.97O4 (the commercial sample with the
nominal composition LiMn2O4) of 85.36 2.67 kJ/mol, whereas
Idemoto et al. [3] report the values 64.1 1.9, 69.1 1.2, and
77.3 1.3 kJ/mol for the sample with composition Li1.03Mn1.97O4
annealed in Ar, 1 atm O2, and 20 atm O2 respectively. Although
Wang and Navrotsky [1] did not measure a sample of this
composition, their values for the LiMn2O4 and Li1.05Mn1.95O4
samples indicate that the enthalpy of formation for Li1.03Mn1.97O4
from the binary oxides should be between 82.47 1.79 (for
LiMn2O4) and 89.92 2.06 kJ/mol (for Li1.05Mn1.95O4). However,
the large deviation in the measured enthalpies of formation for
samples of the same composition but heat treated at different
conditions as detailed in Idemoto et al. [3] show that the resulting
crystal chemistry inuences the measured enthalpy of formation.
Generally, the enthalpies of formation of the Li1+xMn2xO4
(0 < x < 0.1) spinels from the binary constituent oxides and from
the elements decrease with increasing lithium content as shown
in Figs. 9 and 10, respectively. The spinel compounds are more
stable than their constituent binary oxides and elements, and this
Fig. 10. Enthalpy of formation from the elements for one commercial (lled
triangle) and two self-prepared (lled diamonds) Li1+xMn2xO4 spinels compared
to the data of Wang and Navrotsky (open squares) [1].
41
to our work, the values of Wang and Navrotsky [1] are more
reliable. The enthalpies of formation of the Li1+xMn2xO4 spinels
from the binary oxides and from the elements for the composition
range 0 < x < 0.1 become more exothermic with increasing lithium
content. The main factor inuencing the enthalpy of formation of
the spinels from the binary oxides could be the average oxidation
state of the manganese cation. Additionally, the lithium-rich
boundary of the Li1+xMn2xO4 cubic spinel phase was once
again conrmed using differential thermal analysis combined
with thermogravimetric analysis. These phase diagram and
thermochemical data are essential for the advanced thermodynamic modeling of the LiMnO system using the CALPHAD
method. The thermochemical and phase stability data presented in
this work could eventually be combined with electrochemical
testing to make clear statements on the cycling stabilities of
electrode materials.
Acknowledgements
Fig. 11. Enthalpy of formation from the oxides against average manganese
oxidation state of one commercial (lled triangle) and two self-prepared (lled
diamonds) Li1+xMn2xO4 spinels compared to the data of Wang and Navrotsky
(open squares) [1].
The authors would like to thank Dr. Thomas Bergfeldt for the
ICP-OES measurements and Dr. Johannes Prll for providing the
commercial powder and the intensive discussions. This work was
funded by the German Research Foundation (DFG) Priority
Program 1473 WeNDeLIB Materials with New Design for
Improved Lithium Ion Batteries and the Helmholtz Association
through the Young Investigator Group VH-NG-1057.
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