CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 53 (2016) 105115

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CALPHAD: Computer Coupling of Phase Diagrams and

Thermochemistry
journal homepage: www.elsevier.com/locate/calphad

Thermodynamic assessment of the CuLi system and prediction

of enthalpy of mixing of CuLiSn liquid alloys
D. Li a,n, S. Frtauer b, H. Flandorfer b, D.M. Cupid a
a
Karlsruhe Institute of Technology (KIT), Institute for Applied Materials Applied Materials Physics (IAM AWP), Hermann-von-Helmholtz-Platz 1, 76344
Eggenstein-Leopoldshafen, Karlsruhe, Germany
b
Institute of Inorganic Chemistry (Materials Chemistry), University of Vienna, Vienna, Austria

art ic l e i nf o

a b s t r a c t

Article history:
Received 20 November 2015
Received in revised form
14 April 2016
Accepted 14 April 2016

After a comprehensive review of the thermochemical and phase diagram data in the CuLi system, new
experiments were performed to clarify existing contradictions. Several CuLi samples were prepared and
powder X-ray diffraction (XRD) was performed on quenched CuLi alloys. Our experimental work could
not conrm the presence of the intermetallic phase Cu2Li3 which has been recently proposed. Additionally, the results of our high temperature enthalpy of mixing measurements of the liquid phase
indicate that the Li-rich liquidus line is more Cu-rich than presented in previous works. Based on our
experimental data, a Calphad approach was used to obtain a self-consistent thermodynamic description
of the CuLi binary system. Furthermore, a preliminary description of the ternary CuLiSn liquid phase
was developed by combining the new description of the liquid phase in the CuLi system with the description of the liquid phase from our previous CuSn and LiSn assessments. The enthalpies of mixing of
the liquid phase calculated using extrapolations according to the associate, Muggianu, and Toop models
are compared to the enthalpies of mixing reported in the literature. Our work shows that the enthalpies
of mixing calculated using the associate model are in excellent agreement with the literature data, and
no additional ternary interaction parameters are necessary. The contribution of the formation of Li4Sn
associates to the enthalpy of mixing of the ternary liquid was discussed.
& 2016 Elsevier Ltd. All rights reserved.

Keywords:
Phase diagram
Lithium-ion battery
CALPHAD
CuLiSn
Enthalpy of mixing

1. Introduction
Li-ion batteries are considered to be promising power sources for
emission-free vehicles. Although traditionally used carbon-based anode materials exhibit good cyclic stability, at 372 mAh/g, the specic
capacity of such anodes is still too low for future demands. On the
other hand, Sn based metallic anode materials show much higher
specic capacities (992 mAh/g for Li4.4Sn ) but suffer from drastic volume changes during lithium intercalation/de-intercalation processes
which may lead to mechanical failure of the electrode. One method to
increase the service life of Sn-based electrodes is by adding a lithium
inactive element which forms a stabilizing matrix in order to buffer
the volume changes during cycling [1]. Cu is a promising element to
form the matrix phase because of its excellent electrical properties.
Although Cu is considered as lithium inactive, it can participate in the
electro-chemical reactions during charge/discharge. Knowledge of the
phase equilibria in the ternary CuLiSn system is therefore essential
for understanding the performance of electrochemical cells with anode materials based on compounds in the CuSn system. For example,
n

Corresponding author.
E-mail address: Dajian.li@kit.edu (D. Li).

http://dx.doi.org/10.1016/j.calphad.2016.04.003
0364-5916/& 2016 Elsevier Ltd. All rights reserved.

the lithiation process of a CuSn binary electrode having initial composition Cu6Sn5 has been reported as a two-step reaction [2]. However, phase formation during lithiation of CuSn electrodes must be
more complex because of the existence of more compounds. For example, several ternary phases, CuLi2Sn , Cu2LiSn and CuLi2Sn2 , have
been reported in the literature [36]. Some of them were reinvestigated by our group [7,8] and several new structures have been
discovered ( Cu6Li3Sn4 [8], CuLi3Sn and Cu2Li6Sn3 [9]).
Thermodynamic descriptions of the multi-component system obtained using the CALPHAD method [10] can provide not only information on phase reactions during electrochemical cycling but also
on the electrochemical properties of the electrode materials. For example, the open circuit voltage as a function of lithium content,
known as the coulometric titration curve, can be calculated at different operating temperatures. Thermodynamic descriptions for the Cu
Sn and LiSn systems have already been developed by our group in
[11] and [12] respectively. In order to develop a self-consistent thermodynamic description of the ternary CuLiSn system, the phase
equilibria and thermochemical data in the CuLi system should once
again be explored to resolve some contradictions. Based on the experimental results, it was found that the thermodynamic description
of the CuLi system should be updated.

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D. Li et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 53 (2016) 105115

2. Literature review
Only few thermodynamic or phase diagram investigations of
the CuLi system are available in the literature. The liquidus was
determined by Pastorello [13] using thermal analysis on cooling.
He also reported the invariant reaction L (Cu) + (Li) at 453 K as
indistinguishable from the melting point of pure Li. Klemm and
Volavek [14] measured the solubility of Li in fcc-(Cu) by reacting
Li with Cu powder in iron crucibles and characterizing the reacted
samples using XRD and density measurements after partial dissolution of excess Li in water. Mendelsohn et al. [15] annealed
several CuLi alloys in the fcc-(Cu) and liquid two phase region at
various temperatures. Based on this work, Mendelsohn et al. [15]
concluded that the solid solubility of Li in fcc-(Cu) is limited to 6
8 at% at 1123 K. Mikhailovskaya and Sudavtseva [16] measured the
partial mixing enthalpies of CuLi liquid alloys for the xLi < 0.3
composition region at 1373 K. The calculated integral mixing enthalpies show a minimum at around xLi = 0.1 and become endothermic at xLi = 0.23. Gsior et al. [17] performed differential
thermal analysis (DTA) and electromotive force (e.m.f.) measurements in the composition range of 0.1 < xLi < 0.7 and the temperature range 633923 K. Frtauer et al. [18] measured the mixing enthalpies of the liquid phase using drop calorimetry by
dropping Cu into liquid Li at 1073 K.
Old and Trevena [19] proposed the presence of Cu4Li based on
XRD investigations of the reaction surface of Cu with Li. The existence of Cu4Li was accepted by Penaloza et al. [20] and the assessment work of Borgstedt [21]. However, no other experimental
work has indicated the formation of the Cu4Li phase. For example,
no intermetallic phases could be detected by Pastorello [13] using
XRD. Moreover, the lattice parameter of the Cu4Li phase determined by Old and Trevena [19] ts well with the lattice parameters of the fcc-(Cu) phase reported in the previous work of
Klemm and Volavek [14], where the relation between lattice
parameter vs. temperature was given. Therefore, the Cu4Li phase
was considered to be part of the fcc-(Cu) phase and excluded from
the current work.
Based on the results of e.m.f. measurements, Gsior et al. [17]
proposed that a compound with Cu2Li3 stoichiometry exists at
temperatures above approximately 723 K. However, neither the
exact composition of the compound nor the temperature of the
reaction Cu2Li3 (Cu) + (Li) was specied, and Gsior et al.
themselves [17] could not detect any corresponding thermal effect
from the DTA measurements of the CuLi alloys. Additionally, the
sample with 65.1 at% Li in the work of Gsior et al. [17], which
should be located in a Cu2Li3 liquid two phase eld if the Cu2Li3
phase is stable, shows an e.m.f. result similar to that for samples
located in the proposed fcc-(Cu) Cu2Li3 two-phase eld.
Pelton [22] calculated the CuLi phase diagram based on the
work of Pastorello [13] and Klemm and Volavek [14]. Saunders
[23] also assessed the phase diagram and did not include any intermetallic phases. Van de Walle et al. [24] proposed a version of
the CuLi phase diagram based solely on ab-initio calculations in
which the BCC phase is presented as stable in a large concentration and temperature range. Gsior et al. developed a thermodynamic description of the CuLi phase diagram based on their
own experimental results [17]. This version was accepted by
Okamoto [25], regardless of the fact that the existence of the Cu2Li3
phase is still highly questionable. In the present work, XRD was
performed on CuLi samples which were heat-treated and quenched to room temperature in order to detect the Cu2Li3 phase and
to be able to resolve the contradictory literature data.
Not only should the stability of the Cu2Li3 compound be claried, but a new thermodynamic description of the CuLi system
should take into account available data on the enthalpy of mixing
of the liquid phase. Interestingly, previous assessment works
[17,23] did not take the calorimetric data of Mikhailovskaya et al.

[16] into account. However, we could nd no justication to exclude this group of data, such as a contradiction with other data or
obvious experimental errors [16].
Although the CuLi liquidus reported by Pastorello [13] using
the cooling method and that reported by Gsior et al. [17] using
DTA measurements agree with each other, they are in disagreement with the data of Frtauer et al. [18], who performed drop
calorimetric measurements to determine the enthalpies of mixing
of the CuLi system. For example, the smooth enthalpy of mixing
vs. composition prole reported by Frtauer et al. [18] indicates
that the maximum solubility of Cu in liquid Li at 1073 K is higher
than 28 at%. This is in contradiction to the solubility of Cu in liquid
Li reported by Pastorello [13] as 23 at%. These contradictions
therefore suggest that the liquidus in the CuLi system should be
modied.

3. Experimental process and results

3.1. Study of the existence of CuLi compounds
Two samples with composition Cu0.3Li and two with Cu
0.75Li (in molar fraction) were synthesized from pure Cu
(99.98 at%, wire, Goodfellow, Cambridge, UK) and Li (99.8 at%,
wire, Alfa Aesar, Karlsruhe, Germany). After sealing in Ta-crucibles
and induction melting at 1400 K, they were encapsulated in quartz
glass ampoules and annealed for 14 days at 973 K or 35 days at
773 K, respectively (see Table 1). After annealing, all samples were
quenched in cold water and analyzed using powder XRD (Guinier
camera technique). Detailed information on the sample preparation, treatment and analysis methods have been published recently [79,12].
The samples were homogenous on a macroscopic scale, but
quite ductile. For XRD measurements no powder with certain
particle size could be obtained, therefore small pieces of alloy
were extracted from the crucibles after heat treatment and used
for analysis (see Fig. 1). The XRD results are summarized in Table 1,
from which one can see that no other phases besides the solid
solutions (Cu) and (Li) were detected. Despite the small scattering
factor of Li, both phases could be identied reliably (see Fig. 2).
Klemm and Volavek [14] prepared fcc-(Cu) phases saturated
with Li at various temperatures. After quenching, both the compositions and the lattice parameters of the saturated fcc-(Cu)
phase were measured at room temperature. Therefore, the lattice
constants of the fcc-(Cu) phase determined in the present work
could be used with the data from Klemm and Volavek [14] to
determine the composition of the fcc phase in equilibrium with
the Li-rich liquid at the annealing temperatures. The experimental
results of Klemm and Volavek [14] are presented in Fig. 3, along
with the linear regression determined from the experimental data.
The reported lattice parameter for the sample with composition
xLi 0.146 clearly does not t to the other data and is therefore
Table 1
Supplementary samples: heat treatment, XRD and DTA data.
Sample

Heat treatment

XRD

Cu70Li30

973 K/14 days

Cu25Li75

973 K/14 days

Cu70Li30

773 K/35 days

Cu25Li75

773 K/35 days

(Cu)
(Li)
(Cu)
(Li)
(Cu)
(Li)
(Cu)
(Li)

xLi in (Cu)*
a 3.63300(2)
a 3.5004(5)
a 3.63551(5)
a 3.5042(3)
a 3.64327(8)
a 3.5136(4)
a 3.64399(6)
a 3.5095(2)

0.121
0.136
0.177
0.181

Calculation referring to the data reported by Klemm and Volavek [14].

D. Li et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 53 (2016) 105115

107

lattice parameter a/

3.65
3.645
3.64
y=3.6097+0.18927x

3.635
3.63
1958Klemm exp
1958Klemm fit
XRD, 773 K, this work
XRD, 973 K, this work

3.625
3.62
0.08

0.1

0.12

0.14

x Li

0.16

0.18

0.2

Fig. 3. Lattice constant of fcc(Cu) phase against Li content.

Fig. 1. Sample for XRD measurement.

Fig. 4. The calculated CuLi phase diagram with the experimental data from current work and the literature superimposed [1315,17,18].

Fig. 2. XRD measurements of CuLi alloys annealed at 973 K and quenched. (a)
Cu0.70Li0.30 and (b) Cu0.25Li0.75 .

excluded from the analysis. The reliability of the experimental

results can be judged by comparing the lattice constant of pure Cu
extrapolated from the data of Klemm and Volavek (3.6097 )

with the lattice constant of pure Cu (3.6149 ) [26]. The Li contents

of the fcc-(Cu) phase calculated using the lattice constants obtained in the current work are given in Table 1, and shown in Fig. 3
as well as in the calculated CuLi phase diagram (Fig. 4).
The difference in the composition of the fcc (Cu) phase for the
two two-phase CuLi alloys annealed at 773 K is 0.4 at% Li whereas
the difference in the composition of the fcc phase for the alloys
heat treated at 973 K is 1.5 at% Li. Since the lattice parameter determinations were performed at room temperature, the quenching
rate from the annealing temperature has to be considered.
Therefore, small differences can be expected between the lattice
parameters at annealing temperature (in-situ) and those recorded
at room temperature. Accordingly, the difference between the
room temperature lattice parameters for the samples heat treated
and quenched from 973 K is higher than that for samples heat
treated and quenched from 773 K.
The Cu0.3Li and Cu0.75Li alloys were chosen to be located at
different sides of the proposed Cu2Li3 compound ( xLi = 0.6). If the
Cu2Li3 compound [17] exists during the annealing process, it

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D. Li et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 53 (2016) 105115

Additionally, traces of oxygen were gettered by small pieces of

titanium which were placed next to the measurement crucible.
The crucible (inner diameter 9 mm, length 80 mm) was made of
molybdenum. Calibration was done by dropping ve pieces of the
pure Li into the bath of the same element at the start of the
measurement series. The interval between the drops was 40 min
and the heat ow from the measurement crucible through the
thermopile to the calorimeter block was recorded every 0.5 s. After
one drop of Cu into the Li bath, a peck appears on the heat ow
signal. In general, after around 20 min, the heat ow signal goes
back to the original position. Afterward, no endothermic or exothermic effect which indicating the reaction was still in progress
could be observed. Therefore, the 40 min interval between two
drops was found to be sufcient to assure the equilibrium state
has been achieved for the drop calorimetric work on the CuLi
system. The peaks in the heat ow signal which occur as a result of
a drop of Li or Cu pieces into the Li-rich bath located in the calorimeter cell were recorded, integrated and quantied applying
the calorimeter constant, which was determined by the rst ve
calibration drops. For more details see also Ref. [18].The experiments were carried out in a similar way as described previously in
Ref. [18] and the results are given in Table 2 as well as in Fig. 6. The
uncertainty of the measured partial ( mix H Cu ) and integral
( mix HCu ) enthalpies of mixing were estimated based on the error
propagation of the calorimeter constant k and its calculated
standard deviation s(k ). More specically, for the integrated area of
peak of each drop, Ai , the uncertainty was taken as Ai s(k ). For the
integrated enthalpy of mixing, Ai s(k ) was taken as the uncertainty of nal composition. The estimated uncertainties are
given in Table 2. No error bar has been plotted in Fig. 6 because
they are inside the range covered by the symbols.
During the calorimetric investigation, although the nal composition of the mixture was 2.15 at% Cu, no sign indicating entering the liquid FCC two phase region could be observed. Gsior

should be either stable after quenching or, according to the work

of Gsior et al. [17], decompose at around 723 K during quenching.
The similar lattice parameters obtained for the fcc-(Cu) and (Li)
phases from the samples quenched from the same temperature,
regardless of sample composition, indicates that the samples were
in the same phase region during the annealing process at the heattreatment temperature. On the other hand, if we assume that
Cu2Li3 was present at high temperature but unquenchable, then
the measured lattice parameter of the quenched fcc-(Cu) phase for
the Cu0.75Li sample should correspond to that for the fcc-(Cu)
phase stable below the decomposition temperature of Cu2Li3.
Furthermore, according to this, the lattice parameters of the fcc(Cu) phase should be the same for samples with similar composition which were annealed at 973 and 773 K respectively and
quenched. However, this was not observed in our work. Although
Gasior et al. carried out e.m.f. measurements with more comprehensive alloy compositions, further investigations are still required
to clarify the existence, composition and crystal structure of the
proposed Cu2Li3 compound. Therefore, the Cu2Li3 phase was excluded from the CuLi binary phase diagram.
3.2. Calorimetric measurement for the Li-rich CuLi alloys
In order to clarify the contradiction between the reported liquidus [13,17] and the maximum composition reached during the
calorimetric measurement performed at 1073 K [18], drop calorimetric measurements were performed at the Li-rich region at
773 K in an isoperibolic Calvet-type twin calorimeter with two
thermopiles. Each thermopile has more than 200 thermocouples.
This setup enables the detection of T values between the temperature of the calorimeter cell and the constant temperature
calorimeter block of 10  510  4 K. To prevent oxidation, all measurements were performed under Ar ow ( xAr 0.99999, ow
rate 30 ml min  1, usage of an additional gas purication unit).

Table 2
Partial and integral molar enthalpies of mixing of liquid CuLi alloys at 773 K; standard states: pure liquid metals.
Dropped mole nCu (103 mol)

Drop enthalpy Hsignal (J)

Partial molar enthalpy

xCu

mix H Cu/(J mol1)

Starting amount 196.9731  10  3 mol Li; Calibration: 5 drops Li; calibration constant k 0.57925 J(mV s)  1
0.1270
61,949
0.0003
492217 1871
0.1312
35,082
0.0010
223547 1060
0.1340
43,220
0.0016
304917 1305
0.1359
46,891
0.0023
341637 1416
0.1378
33,517
0.0030
207887 1012
0.1418
42,196
0.0037
294677 1274
0.1441
38,285
0.0044
25556 7 1156
0.1494
50,475
0.0052
377467 1525
0.1525
44,786
0.0059
320577 1353
0.1554
41,696
0.0067
28968 7 1259
0.1590
39,366
0.0075
26638 7 1189
0.1636
43,981
0.0083
31252 7 1328
0.1639
35,759
0.0091
230317 1080
0.1659
41,127
0.0099
28398 7 1242
0.1729
33,465
0.0108
207367 1011
0.1749
38,255
0.0117
255277 1155
0.1777
34,588
0.0125
21859 7 1045
0.1780
42,343
0.0134
296147 1279
0.1832
31,830
0.0143
191017 961
0.1861
42,724
0.0152
29996 7 1290
0.1888
33,198
0.0161
20469 7 1003
0.1929
37,928
0.0171
251997 1146
0.1948
34,248
0.0180
21520 7 1034
0.1969
40,259
0.0190
27530 7 1216
0.2009
43,469
0.0199
30740 7 1313
a
b

Average of xCu before and after the drop.

Per mole of binary mixture.

Integral molar enthalpy

xCu b

mix HCu/(J mol1)

0.0006
0.0013
0.0020
0.0027
0.0034
0.0041
0.0048
0.0056
0.0063
0.0071
0.0079
0.0087
0.0095
0.0104
0.0112
0.0121
0.0130
0.0138
0.0147
0.0157
0.0166
0.0175
0.0185
0.0195
0.0204

327 1
477 2
677 3
917 4
1057 4
1267 5
1457 6
1737 7
1987 8
220 7 9
2417 10
2677 11
286 7 12
309 7 13
3277 14
3497 15
3687 16
394 7 17
4117 18
439 7 19
458 7 20
4817 21
502 7 22
528 7 23
559 7 25

D. Li et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 53 (2016) 105115

et al. [17] reported from DTA the liquidus temperature of 2 at% Cu

sample to be 893 K, this is in disagreement with the present calorimetric results. However, their calculated phase diagram shows
a much higher solubility of Cu in liquid Li which is in better
agreement with our results from calorimetry. The determination
of the liquidus by DTA may be difcult since only very small effects
are produced due to the very steep Li-rich liquidus. The determination of liquidus compositions by isothermal calorimetry can be
more accurate in such cases. Therefore, it is clear that the maximum solubility of Cu in liquid Li at 773 K exceeds 2.15 at%.
However, since the liquidus composition was neither reached nor
detected, further experimental work is still required to nd the
exact value.

109

Table 3
experimental data used for current assessment.
Property

Reference

Liquidusa
Liquidusa
Solidus

[13]
[17]
[14]

mix H
mix H
e.m.f.a
Liquidus limitationb
Liquidus limitationb
a
b

Experimental technique

DTA
DTA
reacting Li with Cu powder at 5731073 K
temperature range
[16]
Mixing calorimetry at 1373 K
[18]
Drop calorimetry at 1073 K
[17]
e.m.f.
[18]
Drop calorimetry at 1073 K
Current work Drop calorimetry at 773 K

Partly used.
For comparison.

4. Modeling and assessment process

Based on our review of the literature data as well as on our
current results, no intermetallic Cu2Li3 compound was included in
the current description of the CuLi system. The experimental data
used in the current assessment are listed in Table 3.
Both the liquid and the fcc-(Cu) phases were modeled as substitutional solutions. The Gibbs free energy of the substitutional
solution phase is described as

Gm
= x Cu0GCu
+ xLi0G Li + RT (x Cu ln x Cu + xLi ln xLi)

describing the fcc-(Cu) phase were optimized to t the e.m.f. data

from Gsior et al. [17]. Subsequently, phase diagram data [13,14,17]
were used to optimize the temperature dependence of the Gibbs
energy description of the liquid phase. Special attention was paid
to nd a compromise between the reported liquidus temperatures
[13,17] and the data from the enthalpy of mixing showing a stable
liquid phase at 28 at% Cu at 1073 K and at 2.1 at% Cu at 773 K. Finally, all data were taken into account and all parameters were
rened simultaneously.

+ x CuxLi L Cu,Li(x Cu xLi)

(1)

5. Assessment results and discussion

0
Gi

where
is the Gibbs energy of the pure element in the state ,
the third term is the contribution of the congurational entropy of
mixing to the Gibbs free energy, and the last term is the excess
Gibbs free energy of mixing described using the RedlichKister
polynomials [27]. The thermodynamic descriptions of the pure
elements were taken from the SGTE 5.1 database supplied with the
Thermo-Calcs version S software.
First, the binary interaction parameters describing the liquid
phase were optimized using data on the enthalpy of mixing of the
liquid from [16,18]. Second, the binary interaction parameters

18
16

mix

-1

Hm/(kJmol )

14
12
10

1989Mikhailovskaya 1373 K
2013Frtauer 1073 K
1998Saunders

8
6

1373 K
1073 K

2
0
-2
0

Cu

0.2

0.4

xLi

0.6

0.8

1.0

Li

Fig. 5. Calculated enthalpy of mixing for the CuLi liquid alloys in comparison with
literature data [16,18].

The new thermodynamic description of the CuLi system is

given in Table 4. The calculated phase diagram with superimposed
experimental data [1315,17] is shown in Fig. 4, where a good
agreement between the calculation and experimental results can
be observed. The liquid phase is stable in the composition range
covered by the maximum Cu content obtained from calorimetry at
1073 K [18] and 773 K. A metastable miscibility gap of the liquid
phase is also shown in Fig. 4. The fcc-(Cu) solidus compositions
obtained by XRD in the current work are also presented in Fig. 4.
Fig. 5 shows the calculated enthalpies of mixing of the liquid
phase with experimental data [16,18]. A fair agreement between
the calculation and literature data can be observed. The enthalpies
of mixing calculated using the parameters reported by Saunders
[23] are also plotted in Fig. 5 for comparison.
Fig. 6 shows the enthalpies of mixing of the Li-rich liquid at
773 K obtained in the current work. The maximum difference
between the measured and calculated enthalpy of mixing is approximately 0.150 kJ/mol. The experimentally determined enthalpies of mixing at 1073 K [18] and those calculated using the
thermodynamic parameters reported by Saunders [23] are also
plotted in Fig. 6 for comparison. Since there are no kinks in the
measurements of the enthalpy of mixing at 773 and 1073 K,
Figs. 5 and 6 clearly show that the calorimetric measurements
were performed inside the liquid single phase composition range.
The calculated e.m.f. of alloys with composition xLi 0.1, 0.125,
and 0.15 along with the measured values from Gsior et al. [17] are
shown in Fig. 7. Although Gsior et al. also measured the e.m.f.
values for an alloy with composition xLi 0.175 [17], these results
are not included in Fig. 7 due to several inconsistencies in the
original publication. For example, according to the CuLi phase
diagram proposed by Gsior et al. [17], the xLi 0.175 composition
is either in the fcc-(Cu) Cu2Li3 or in the fcc-(Cu) liquid two
phase eld depending on measurement temperature (between
600 and 900 K). Therefore, the measured e.m.f. values for the
xLi 0.175 composition should be the same as those for other
samples also located in the same two-phase elds. However, the

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D. Li et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 53 (2016) 105115

Table 4
Optimized thermodynamic parameters of the Cu-Li system, the values are given in Jmol-1.
Liquid: Model (Cu,Li)
0 liq
SER
= GLIQCU
GCu HLi
0 liq
SER
= GLIQLI
GLi HLi
0 liq
L Cu,Li = 11794.6115 +

1.78T 2.72360272T ln T

1 liq
L Cu,Li

= 22042.9488 + 29T 1.4T ln T

2 liq
L Cu,Li

= 14500 + 16T 1.15T ln T

fcc-(Cu): Model (Cu,Li)

0 fcc
SER
GCu HCu
= GHSERCU
0 fcc
GLi HLiSER = GFCCLI
0 fcc
L Cu,Li = 34383.0459 70.0863278T
1 fcc
L Cu,Li

+ 11.3754566T ln T

= 204984.122 + 140.574711T

Symbols
298.14K T < 1357.77K :

GHSERCU = 7770.458 + 130.485235T 24.112392T ln T 2.65684 103T 2 +52478T 1

+ 1.29223 107T 3
1357.77K T < 3200K
GHSERCU = 13542.026 + 183.803828T 31.38T ln T + 3.64167 1029T 9
200K T < 453.6K :
GHSERLI = 10583.817 + 217.637482T 38.940488T ln T + 3.5466931 102T 2

1.9869816 105T 3 + 159994T 1

453.6K T < 500K :
GHSERLI = 559579.123 + 10547.8799T 1702.88865T ln T + 2.25832944T 2
5.71066077 104T 3 + 33885874T 1
500K T < 3000K :
GHSERLI = 9062.994 + 179.278285T 31.2283718T ln T + 2.633221 103T 2 4.38058 107T 3 102387T 1
298.15K T < 1357.77K :
GLIQCU = GHSERCU + 12964.735 9.511904T 5.849 1021T7
1357.77K T < 3200.00K
GLIQCU = 46.545 + 173.881484 T 31.38T ln T
200K T < 250K :
GLIQLI = 7883.612 + 211.841861T 38.940488T ln T + 3.5466931 102T 2 +159994T 1
1.9869816 105T 3
250K T < 453.6K :
GLIQLI = 12015.027 362.187078T + 61.6104424T ln T 0.182426463 102T 2 +6.395567 105T 3 559968T 1
453.6K T < 3000K :
GLIQLI = 6057.31 + 172.652183T 31.2283718T ln T + 2.633221 103T 2 102387T 1
4.38058 107T 3
200K T < 3000K :
GFCCLI = GHSERLI 108 + 1.3T

experimental results of Gsior et al. show that the measured e.m.f.

values corresponding to the sample with xLi 0.175 decrease with
increasing temperature whereas those from alloys with higher Li
contents also located in the same two-phase elds increase with
increasing temperature. Therefore, the e.m.f. values of the sample
with xLi 0.175 sample in fact suggest that the alloy should be fcc(Cu) phase throughout the temperature range of the
measurement.
According to the current assessment, the composition
xLi 0.175 is indeed located in the fcc-(Cu) phase eld at 633 K and
773 K. The calculated activities of Li in the Cu rich part of the CuLi
phase diagram at 633, 773 and 873 K are shown in Fig. 8, together
with values reported by Gsior [17]. Since the calculated lithium
activities change drastically with composition for higher lithium
contents, small uncertainties in the determination of the true
composition of the alloy will lead to large uncertainties in the
reported e.m.f. values for the selected composition. Therefore, it is
valid to not include the measured e.m.f. values for composition
xLi 0.175 in the current work.
The activity values reported in Table 2 of Ref. [17] for the

compositions xLi 0.1, 0.125 and 0.15 also show some inconsistences. Although Table 2 and Figure 2 of Ref. [17] state that the
reference state for the Li-activity data is fcc-(Li), in the text itself, it
is written that the activities were calculated directly from the e.m.
f. results. Following the experimental procedure which was performed in the temperature range between 663 and 923 K, it is
clear that the reference state is liquid Li instead of fcc-(Li). Since no
conversion for the reference state to fcc-(Li) was mentioned in the
text, and, moreover, since the fcc structure of pure Li is not stable,
we were forced to assume that the reference state for Li is liquid.

6. Prediction of enthalpy of mixing of CuLiSn liquid alloys

The thermodynamic description of the liquid phase in the CuLi
system produced in this work was combined with the already
developed thermodynamic descriptions for the liquid phases in
the CuSn [11,28] and LiSn [12] systems to generate a rst description of the liquid phase in the ternary CuLiSn system.
Because of the introduction of the Li4Sn associate into the

D. Li et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 53 (2016) 105115

111

1.0

10

0.9
2013Frtauer 1073 K
current work 773 K
current work 773 K
1998Saunders

-1

Hm/(kJmol )

8
6

0.8
633 K
773 K
873 K

0.7
0.6

aLi

0.5

mix

0.4

0.3
0.2

0
0.1

-2
0.95

0.96

0.97

0.98

xLi

0.99

Fig. 6. Enthalpy of mixing of the CuLi liquid phase at the Li-rich part [18,23].

thermodynamic description of the LiSn system [12], the Gibbs

energy of the liquid phase of the CuLiSn system is also described
using the associate model. The molar Gibbs energy can be written
as
liq
=
Gm

ni0Giliq + RT ni ln xi + n xixj Li, j(xi xj)

i

ij

1.00

(2)

where i refers to the species, e.g. Cu, Li, Sn and Li4Sn . n and ni refer
to the total molar numbers of the system and specic species in a
one mole atom system under certain conditions, respectively. x i
refers to the mole fraction of the specie i in the whole system, e.g.
n
x i = ni [29].

x =0.1

this work

x =0.125

2009Gasior

x =0.15

1998Saunders

0.05

0.10

0.15

xLi

0.20

Fig. 8. Activities of Li in comparison with the experimental data [17]. Reference

state: liquid Li.

In this preliminary model of the ternary CuLiSn liquid, neither

interaction parameters between the Li4Sn associates and Cu nor
higher order interactions were modeled. Since the enthalpies of
mixing of the liquid phase along 5 different sections in the CuLiSn
system were measured by Frtauer et al. [18], the ternary enthalpies of
mixing calculated using extrapolations from the binary descriptions
could be compared to the experimental work to judge the quality of
the prediction.
The calculated enthalpies of mixing at 1073 K for the binary
sub-systems of CuLiSn system are summarized in Fig. 9. The
enthalpies of mixing for the CuLi and CuSn systems show similar
S shape proles whereas the enthalpy of mixing of the liquid in
the LiSn system shows a deep minimum. To be able to compare
the predicted enthalpies of mixing of the ternary liquid with the
experimental work of Frtauer et al. [18], both the Muggianu [30]

(E vs. ELi)/mV

mix m

H /(kJ mol-1)

-5
-10
-15
-20

Cu-Li
Cu-Sn
Li-Sn

-25
-30
-35
-40
0

T/K
Fig. 7. Calculated e.m.f. data in comparison with the experimental data [17] and
previous assessment [17,23].

0.1

0.2

0.3

0.4

0.5

xb

0.6

0.7

0.8

0.9

Fig. 9. Calculated enthalpies of mixing of binary systems for CuLiSn ternary

system at 1073 K. xb stands for the mole fraction of Li, Sn, and Sn for CuLi, CuSn
and LiSn systems, respectively. Reference state: liquid Cu, Li, and Sn.

112

D. Li et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 53 (2016) 105115

and Toop [31] extrapolation models as well as an extrapolation

model based on the calculation of the global Gibbs free energy
minimum of the ternary system were used. The Muggianu and
Toop models for an ABC system are given in (Eqs. (3) and 4),
respectively. For the Toop extrapolation method, Cu was chosen as
the A element so that the LiSn system could be treated differently
to the CuSn and CuLi systems. To determine the enthalpies of
mixing of the ternary liquid using the Muggianu and Toop models,
the enthalpies of mixing of the respective binary liquid phase
compositions were rst calculated using the binary descriptions
[11,12] and then input into Eq. (3) or Eq. (4), respectively. A similar
analysis was performed in the work of Frtauer et al. [18], where
the enthalpies of mixing of the binary systems were modeled
using the RedlichKister polynomials, and the ternary extrapolations were performed using either the symmetric Muggianu
model or the extrapolation model according to Chou [32].

HAmix
B C =

4xA xB
(1 + xA xB)(1 xA + xB)
1 + xA xB 1 xA + xB
...
HAmix
,
B

2
2
4xBx C
(1 + xB x C)(1 xB + x C)
1 + xB x C 1 xB + x C
...
HBmix
,
C

2
2
+

4x CxA
(1 + x C xA )(1 x C + xA )
1 + x C xA 1 x C + xA

HCmix
,
A

2
2

(3)

xB
xC
HAmix
HAmix
B(xA , 1 xA ) +
C(xA , 1 xA )...
1 xA
1 xA
x
xC
B
+ (xB + x C)HBmix
,

C
xB + x C xB + x C

(4)

HAmix
B C =

The enthalpies of mixing at 1073 K calculated using the binary

descriptions and various extrapolation methods are compared to
the measured data from Frtauer et al. [18] in Fig. 10. For sections
A, B and C, where Li was dropped into molten CuSn baths, the
enthalpy of mixing behavior is similar to that of the LiSn system,
where a deep minimum is observed. For sections D and E, where
Cu was dropped into the liquid, an S shaped enthalpy of mixing
prole is obtained, which is similar to the enthalpies of mixing in
the CuLi and CuSn systems.
A good agreement to the experimentally determined data can
only be observed for the enthalpies of mixing calculated using the
global Gibbs energy minimum based on the associate model. The
largest deviation of approximately 3 kJ mol  1 appears in section A,
Cu0.5Sn0.5 Li. No ternary interaction parameters are necessary to
model the enthalpies of mixing of the liquid in the CuLiSn system once the associate model with Li4Sn associates is selected.
Meanwhile, extrapolations using the Muggianu and Toop models
result in predictions which are similar to each other and which
would require ternary interaction parameters between Cu, Li, and
Sn to be able to t the experimental data as was observed in
Frtauer et al. [18]. This fundamental difference can be explained
by considering the formation of Li4Sn associates in the liquid.
The amount of Li4Sn associates in a one mole atom system
calculated using the global optimization of the Gibbs free energy
of the system is shown in the upper graphs of Fig. 10. The minima
in the enthalpies of mixing in sections A, B, and C are associated
with maxima in the concentration of Li4Sn associates in the liquid.
The enthalpies of mixing of the CuLiSn liquid alloys largely
originate from the exothermic formation of Li4Sn associates.

Moreover, the formation of Li4Sn associates consumes free Li and

Sn atoms, thereby reducing the contribution to the Gibbs free
energy of the system resulting from the interaction between Cu, Li
and Sn atoms.
In the extrapolations using the Muggianu and Toop models, the
ratio of Li4Sn: Li:Sn in the liquid depends only on the composition
of the liquid in the LiSn binary system selected by the model for
the ternary extrapolation. However, when the associate model
with global minimization is used, the ratio of Li4Sn: Li:Sn depends
on the overall composition of the system. This means that the
presence of Cu in the liquid directly inuences the amount of Li4Sn
associates. Since the enthalpy of mixing between Cu and Li is
positive when the ratio of Cu to Li in the liquid is low (repulsive
interactions between Cu and Li), when Cu is added to the LiSn
liquid, free Li has an increased tendency to form Li4Sn associates
with free Sn. This can clearly be seen in our calculations for the
enthalpy of mixing of the liquid along section D. The initial
amount of Li4Sn associates is small since the starting composition
of the liquid bath is Sn-rich (Li0.8Sn). When Cu is dropped into
the bath, the amount of Li4Sn associates increases, and a maximum
in the amount of associates appears at around 50 at% Cu. However,
in the Muggianu and Toop models, the amount of Li4Sn associates
should decrease with increasing Cu content. In these cases, a
ternary interaction parameter would be required to reproduce the
enthalpy of mixing data of the liquid [18].
The fact that the enthalpies of mixing of CuLiSn liquid compositions could be predicted without the need for ternary interaction parameters shows that the liquid phase in each of the
binary subsystems is well modeled. For example, the experimentally determined enthalpy of mixing data in the CuLi system from
[16] are necessary to produce the S shape of the enthalpy of
mixing for section D in Fig. 10. Moreover, the good agreement
between the experimentally determined enthalpies of mixing and
those calculated using global minimization of the Gibbs free energy based on Li4Sn associates further justies the use of the associate model in the LiSn system, which is based on neutron
diffraction results [33].
The isoenthalpy curves at 1073 K calculated using the current
description of the liquid phase including Li4Sn associates and
those tted by Frtauer et al. [18] by including ternary interaction
parameters between Cu, Li, and Sn are shown in Fig. 11(a) and (b),
respectively. In Fig. 11(a), the calculated spinodal decomposition of
the liquid is indicated in gray. A slight change in the direction of
the isoenthalpy curves can be found at the border to the spinodal
decomposition region in Fig. 11(a). A close comparison between
the results calculated using the present thermodynamic description and those calculated using a t of the experimental results
[18] shows there are changes of directions of the isoenthalpy
curves at similar positions. Therefore, although the presence of a
miscibility gap in the liquid phase has not been proved experimentally, calculations performed using the thermodynamic description show that the presence of a metastable liquid miscibility
gap is highly likely.
Calculated spinodal decomposition regions of CuLiSn liquid
alloys at different temperatures are shown in Fig. 12. The ternary
miscibility gap of the liquid phase in the CuLiSn system ends in
the metastable liquid miscibility gap in the binary CuSn [11] and
LiSn systems [12]. The metastable miscibility gap originating in
the CuLi system extends into the ternary system; however, it does
not meet the miscibility gap appearing in the center of the Gibbs
triangle as shown in Fig. 12.

7. Conclusion
Key experiments were performed in the CuLi binary system to

D. Li et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 53 (2016) 105115

0.2

nLi

-10
-20

-10
-20

0.1

0.2

0.3

0.4

0.5

0.6

xLi

0.7

0.8

0.9

0.2

0.3

0.4

0.5

xLi

0.6

0.7

0.8

0.9

Section D: Li 0.2Sn0.8+Cu

Sn

Section C: Cu 0.2Sn0.8+Li

nLi

0.1

0.1

H /(kJ mol-1)

-10
-20
-30

-20

Toop
Muggianu
Global Minimum
2013Frtauer

-30

Toop
Muggianu
Global Minimum
2013Frtauer

-10

mix m

Sn
4

nLi

0.1

0.2

0.2

H /(kJ mol-1)

Toop
Muggianu
Global Minimum
2013Frtauer

-30
-40

-40

mix m

Toop
Muggianu
Global Minimum
2013Frtauer

-30

0.1

H /(kJ mol-1)

H /(kJ mol-1)

0.1

mix m

Section B: Cu0.4Sn0.6+Li

Sn

Section A: Cu0.5Sn0.5+Li

mix m

nLi

Sn

0.2

113

-40

-40
0

0.1

0.2

0.3

0.4

0.5

0.6

xLi

0.7

0.8

0.9

0.1

0.2

0.3

0.4

0.5

xCu

0.6

0.7

0.8

0.9

nLi

Sn

0.2
Section E: Li0.5Sn0.5+Cu
0.1

-10
-20
Toop
Muggianu
Global Minimum
2013Frtauer

-30

mix m

H /(kJ mol-1)

-40
0

0.1

0.2

0.3

0.4

0.5

xCu

0.6

0.7

0.8

0.9

Fig. 10. Extrapolated intensity of Li4Sn associate and integral molar enthalpies of mixing of liquid CuLiSn alloys at 1073 K in comparison with experimental data [18]. For
the sections: (A) Cu0.5Sn0.5Li; (B) Cu0.4Sn0.6 Li; (C) Cu0.2Sn0.8Li; (D) Li0.2Sn0.8 Cu; (E) Li0.5Sn0.5 Cu. Reference states: pure liquid components.

check the existence of the Cu2Li3 phase as well as the location of

the Li-rich liquidus. The Cu2Li3 compound could not be conrmed
by XRD examination of quenched CuLi alloys, and the CuLi liquidus at the Li rich side had to be modied to higher Cu-compositions following measurements of the enthalpy of mixing of the
liquid phase at 1073 and 773 K. The thermodynamic description of
the CuLi was re-optimized using the CALPHAD method based on
clarications of the CuLi phase diagram performed in this work,
and the new description well reproduces the literature data. The

thermodynamic description of the CuLiSn ternary liquid phase

was extrapolated by combining the description of the liquid phase
developed in this work with previously obtained CuLi and LiSn
descriptions. No ternary interaction parameters were added. The
prediction successfully reproduces reported enthalpies of mixing
in the CuLiSn ternary liquid alloys, showing the validity of the
binary datasets and the importance of proper model selection in
the CuLi and LiSn systems. The calculated miscibility gap for the
CuLiSn liquid phase may require further experimental work to

114

D. Li et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 53 (2016) 105115

Sn
0

1.0
0.8

0.2

0.6

0.4

L+L

0.6

0.4
-35000

0.8
-15000

-10000

-5000

-20000

-25000

Cu

0.2

1.0
0

-30000

0.2

0.4

0.6

0
0.8

1.0

Li

Fig. 11. Isoenthalpy of mixing curves of liquid CuLiSn alloys at 1073 K. (a) Calculated using current dataset and (b) experimental results [18].

References

Sn
0

1.0
473

0.8

0.2
873
1073

0.6

0.4
1273

0.6

0.4

1373

0.2

0.8
473
873

1.0

Cu

0.2

0.4

0.6

0.8

1.0

Li

Fig. 12. Calculated spinodal decomposition ranges for the liquid CuLiSn liquid
phase at different temperatures (T/K) by extrapolating from binary systems.

clarify its existence. Generally however, to be able to develop a

thermodynamic description of the complete CuLiSn system,
more experimental work is required.

Acknowledgment
This work was nancially supported by the German Research
Foundation DFG under the project numbers CU 203/1-1 and FL-730/
1-2 within the DFG priority program SPP 1473 Materials with new
Design for Improved Lithium Ion Batteries WeNDeLIB and by the
Austrian Research Foundation FWF under the Project no. I559-N19.

Appendix A. Supplementary material

Supplementary data associated with this article can be found in
the online version at http://dx.doi.org/10.1016/j.calphad.2016.04.003.

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