ISSN 1070-4272, Russian Journal of Applied Chemistry, 2015, Vol. 88, No. 11, pp. 1737−1749. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © A.G. Morachevskii, 2015, published in Zhurnal Prikladnoi Khimii, 2015, Vol. 88, No. 11, pp. 1521−1533.
Lithium–Antimony Alloys: Phase Diagram,
Thermodynamic Properties, Electrochemical Behavior
in Molten and Nonaqueous Electrolytes,
and Use in Lithium–Ion Batteries
A. G. Morachevskii
Peter the Great St. Petersburg State Polytechnic University, ul. Politekhnicheskaya 29/1, St. Petersburg, 195251 Russia
Received July 24, 2015
Abstract—Data on the phase diagram of the lithium–antimony system and on the thermodynamic properties
of lithium–antimony alloys and their electrochemical behavior in molten and nonaqueous electrolytes are sum-
marized and analyzed. The possibility of using antimony and its alloys with various metals as anode material in
lithium–ion batteries is discussed.
Twenty-ﬁ ve years passed since the time when the
commercial production of lithium–ion batteries was
started, but wide-scale search for more effective ma-
terials for their electrodes is still being continued. As
judged from the number of the published papers, this
problem became one of the main problems of the mod-
ern applied electrochemistry [1–6]. Particular attention
is paid to searching for optimum anode materials, in-
cluding metals and alloys [7–16]. Antimony and its al-
loys with various metals show promise for this purpose
. Lead alloys are also promising for liquid metal
chemical current sources [18, 19] and for other energy
In this review, the major attention is paid to electro-
chemical methods for determining the thermodynamic
properties of solid phases in the lithium–antimony sys-
tem. Cathodic polarization of antimony in various media
containing lithium ions is considered for this purpose.
Available data on the use of antimony alloys as anode
material in lithium–ion batteries are also discussed.
OF THE LITHIUM–ANTIMONY SYSTEM
It is indicated in handbooks [20, 21] that the phase
diagram of the lithium–antimony system has not been
determined. Data are available only on the parameters of
the crystal structure of Li
Sb and Li
Sb. It is also noted
that the melting point of Li
Sb, according to data of some
authors, is between 1150 and 1300°С, and according to
other data, above 950°C.
The phase diagram of the Li–Sb system presented
in  is largely based on analogies between the Li–
Sb system, on the one hand, and the Na–Sb, K–Sb, and
Li–Вi systems, on the other hand. The results of pre-
parative studies performed in the beginning of the XX
century were taken into account. The composition of the
assumed compounds, congruently melting Li
Sb melting with decomposition, is beyond question,
but the temperatures of the liquidus line and phase tran-
sitions are indicated only approximately (Fig. 1).
The phase diagram of the Li–Sb system, obtained by
Fedorov , is essentially different. Fedorov notes that
the alloys were not subjected to preliminary annealing,
and therefore the diagram cannot be considered as
equilibrium to a full extent. Alloys were prepared by
electrolysis of the molten LiCl–KСl eutectic mixture
with a liquid antimony cathode. The possibility that
potassium can get into the alloy is not discussed in .
According to , two congruently melting compounds
are formed in the Li–Sb system: Li