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Eutectics: formation, properties, and applications

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Cite this: Chem. Soc. Rev., 2021,
50, 8596
Received 26th April 2021
DOI: 10.1039/d1cs00404b
rsc.li/chem-soc-rev
Dongkun Yu,a Zhimin Xue *b and Tiancheng Mu *a
Various eutectic systems have been proposed and studied over the past few decades. Most of the
studies have focused on three typical types of eutectics: eutectic metals, eutectic salts, and deep
eutectic solvents. On the one hand, they are all eutectic systems, and their eutectic principle is the
same. On the other hand, they are representative of metals, inorganic salts, and organic substances,
respectively. They have applications in almost all fields related to chemistry. Their different but
overlapping applications stem from their very different properties. In addition, the proposal of new
eutectic systems has greatly boosted the development of cross-field research involving chemistry,
materials, engineering, and energy. The goal of this review is to provide a comprehensive overview of
these typical eutectics and describe task-specific strategies to address growing demands.

1. Introduction
The word ‘‘eutectic’’ originated in metallurgy. Many eutectics
have gradually gained popularity over the past few decades and
a
Department of Chemistry, Renmin University of China, Beijing 100872,
play important roles in electronic devices, semiconductor engi-
P. R. China. E-mail: tcmu@ruc.edu.cn
b
Beijing Key Laboratory of Lignocellulosic Chemistry, College of Materials Science
neering, chemical engineering, and separation technology.1–5
and Technology, Beijing Forestry University, Beijing 100083, P. R. China. However, many researchers still believe that eutectics is an area
E-mail: zmxue@bjfu.edu.cn of interest only to physicochemical experts and not attractive

Dongkun Yu received his MSc Dr Zhimin Xue received her PhD

degree from Renmin University degree from Renmin University
of China in 2020 under the of China in 2014 under the
supervision of professor co-supervision of Academician
Tiancheng Mu. He is currently a Buxing Han, Professor Jianling
PhD candidate at KTH Royal Zhang, and Professor Tiancheng
Institute of Technology, with the Mu. From 2017 to 2018, she was
support from China Scholarship a visiting associate professor in
Council. His research focuses on the University of Tennessee,
non-covalent interactions and novel Knoxville, cooperated with
eutectics. He has co-authored over a Professor Sheng Dai. She is
dozen publications. currently an associate professor
Dongkun Yu Zhimin Xue in the College of Materials
Science and Technology, Beijing
Forestry University. Her research interests cover treatment and
conversion of biomass, design, and applications of green solvents.
She has co-authored over 75 peer-reviewed scientific publications
and three chapters. Now she also serves as a member of the Ionic
Liquids Professional Committee of the Chemical Industry and
Engineering Society of China and a member of a council of
Beijing Thermal Analysis Association. She was selected as the
Top Youth talents of National Forestry and Grassland
Administration in 2020.

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Fig. 1 Significance of eutectics in broadening the solvent systems (A). Comparison of three different eutectics (B).

enough to general chemistry readers. Although a considerable
number of reviews have been made on eutectics, most of them
Dr Tiancheng Mu received his
PhD in physical chemistry from
the Institute of Chemistry, the
Chinese Academy of Sciences.
Then, he worked in the Depart-
ment of Industrial Chemistry,
Oldenburg University (Germany)
as a postdoctoral researcher.
He is currently a full professor
in the Department of Chemistry,
Renmin University of China. His
research interests involve solution
Tiancheng Mu chemistry and green chemistry. He
has authored over 160 scientific
publications. Furthermore, he was awarded the Prize of Liangxi
Forestry Science and Technology Award (2019) and Science and
Technology Award of the China Association for Instrumental
Analysis (2016). Now he serves as an associate editor for RSC
Advances, editorial board member for The Chinese Journal of
Process Engineering, vice director of Beijing Thermal Analysis
Society, a member of ionic liquids professional committee of
Chemical Industry and Engineering Society of China, and a member
of the green chemistry professional committee of Chinese Chemical
Society.
profoundly summarize a kind of eutectic system. Eutectic
systems vary greatly in properties and applications. For exam-
ple, to the best of our knowledge, there have been many studies
on eutectic metals in the field of electronics but little review
and research work on those in dissolution and separation;
moreover, there are many publications about the use of eutectic
salts in energy storage but those on their role in environmental
science are fewer.6–8 In fact, deep eutectic solvents (DESs) have
shown great promise for applications in the fields of environ-
mental science and separation science.9,10 In some fields,
including battery technology, there are cross-linked applica-
tions of these eutectics.11,12 Therefore, it was necessary to
review the diverse eutectics and the related research progress.
This work is intended to contribute to the development
of interdisciplinary studies in fields such as chemistry and
industry, chemistry and materials, and chemistry and the
environment.
A famous example that demonstrates the application of
eutectics is the Hall–Héroult process.13 Aluminium electrolysis
from Al2O3 (melting point 2072 1C) can be carried out at around
960 1C by the formation of a eutectic system with Na3AlF6
(melting point 1010 1C). In addition, this lowering of the
melting point led to the development of soldering technology.
Another important significance of eutectics is that they can
broaden conventional mixed solvent systems (under certain
temperature and pressure conditions). Thus, a two-solid system
could also be designed as a solvent (Fig. 1A). The most
commonly used DES is a eutectic mixture composed of choline

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chloride (ChCl) and urea at a molar ratio of 1 : 2.14 The melting
point of this eutectic system is 13 1C, whereas the melting
points of ChCl and urea are much higher than 25 1C.
Through this strategy, a liquid system can be designed to suit
specific requirements. For example, a dimethyl sulfoxide-
aqueous system with a freezing point lower than 130 1C was
developed as an ultra-low temperature electrolyte for sodium
ion batteries.15
In this review, three typical but distinct eutectics (eutectic
metals, eutectic salts, and DESs) are discussed to introduce
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readers to eutectics and eutectic systems. As their names
suggest, they are all eutectic systems, although their melting
points are very different. This work mainly introduces their
applications in the liquid state. On the one hand, they have
similarities in forming eutectic systems. On the other hand,
they represent metals, inorganic salts, and organic substances,
and their main interactions are metal bonds, ionic bonds, and
van der Waals forces, respectively. These different structures
and interactions indicate their different properties. For exam-
ple, a eutectic metal is always an electric conductor, whereas
eutectic salts and DESs are conductive because of freely moving
ions.16 However, their huge latent heat during phase change
allows all of them to be used for energy storage. Therefore, they
are very representative (Fig. 1B). The researchers will be enligh-
tened with a full understanding of different eutectics, and such
interdisciplinary knowledge will also stimulate innovation. The
relevant historical background, important properties, and
applications are introduced and summarized in the following
sections. We also present some new views on eutectics and
consider future directions.
2. An overview of eutectics
The original meaning of eutectics is ‘‘easy to melt’’, which we
interpret as ‘‘reducing the melting point after mixing’’. In most
of the systems discussed here, under certain temperature and
pressure conditions, the single components are in the solid
state whereas the eutectic systems are in the liquid state. In
general, most substances are composed of atoms, ions, or
molecules. The types of binary systems that can be formed
are shown in Table 1. Metals are atomic in nature, so eutectic
metals can be regarded as eutectic mixtures of atoms. A metal
can also be understood as being composed of fixed nuclei and
free electrons; thus, a eutectic metal is a system of cations and
electrons (Fig. 1B). Both salts and eutectic salts are systems
Table 1 All kinds of binary systems, composed of atoms, ions, and molecules
Type Category (nature)
A + A Eutectic metal (eutectic atomic mixture)
B + B Eutectic salt (eutectic ionic mixture)
C + C Eutectic molecular mixture
B + C DES (eutectic ionic and molecular mixture)
A + B Metal in salt (eutectic atomic and ionic mixture)
A + C —
A: Metal (atoms); B: salt (ions); C: molecular compound.
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composed of anions and cations; however, the latter contain
more types of ions than the former. In the same way, the
composition of eutectic molecular liquids is easy to under-
stand. DESs are actually a class of mixtures of ions and
molecules. The most interesting system is Bi–BiCl3, which is
called a metal in salt.17 According to the principle of (Pauling)
electronegativity, BiCl3 is a covalent compound (wBi: 2.02, wCl:
3.16). The ‘‘medium’’ property appears to allow a Bi-based salt
to form a eutectic system with the Bi element. Elements such as
Li cannot form a eutectic system with their salts.18 Moreover,
the crystal structure of BiCl3 verifies this point: the triangular
pyramidal molecules are arranged regularly in space. However,
some properties such as electrical conductivity indicate that
it is an ionic compound. This ‘‘metal–salt’’ example is in fact
neither common nor typical, because the formed eutectic
system can be regarded as a combination of two salts. The
properties of different eutectics can be inferred from their
respective compositions. For example, a system containing ions
possesses ionic conductivity, whereas the one containing free
electrons possesses electronic conductivity. Although the com-
position is different, the eutectic principle is the same. In the
following sections, the formation of eutectics will be discussed
in depth.
2.1 Formation of eutectics
In a binary phase diagram, the eutectic process is described
as a three-phase transformation that occurs at a certain
temperature and pressure. Generally, the effect of pressure
is negligible during solid–liquid phase transition. The
relationship between state functions and temperature can be
established.
2.1.1 Entropy change. Entropy represents the degree of
chaos in a system. Under a constant temperature and pressure,
two different solids are mixed to form a liquid. For all eutectics,
the entropy of the system increases during this process. It is
simple and easy to understand by the entropy increase process,
and to explain the depression of melting point.
If a phase transition occurs at the eutectic point, DG = 0.
According to Gibbs equation, the following equation can be
obtained,

DHfus
Tm ¼  (1)
DSfus
where Tm is the melting point of a pure substance, DHfus*
and DSfus* are enthalpy and entropy changes of melting,
Example Ref.
Pb–Sn 19
LiCl–KCl 20
Benzophenone–diphenylamine 21
ChCl–urea 14
Bi–BiCl3 17
— —
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respectively. If there is a eutectic system, eqn (2) can be

rewritten as,

DHe
Te ¼ (2)
DSe

where the subscript e represents the physical quantity of the

eutectic system. The species in the solid have a small range
of motion in the body phase, so the difference in entropy
between pure solids and impure solids is small. However, the
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difference in entropy between pure liquid and impure liquid

is greater because the species in impure liquid is more
disordered.22 For most eutectic systems, compared to entropy
change, the enthalpy change is much less. Therefore, the
change in entropy of melting an impure solid into an impure
liquid is greater than that of melting a pure solid into a pure
liquid.
The comparison of eqn (1) and (2) becomes simple. Both
numerators on the right side of the equations do not change
much, while the denominator of eqn (2) becomes much larger.
Therefore, it can be understood that the melting point of the
eutectic system is lower than that of a single component. For
cocrystals which will be introduced below, a large enthalpy
change makes their melting point relatively high.23 For the
same reason, increasing the entropy change and decreasing the
enthalpy change can be considered as a strategy to lower
the melting point (or glass transition temperature) of the
target mixture. Recently, Mason and coworkers have reported
a series of metal–bis(acetamide) frameworks with low melting
temperatures (Fig. 2A).24 Apart from Coulomb interactions,
the hydrogen bonding and coordination interactions are
believed to play an important role in affecting the enthalpy
and entropy changes. The strength of the interaction deter-
mines the degree of change in enthalpy and entropy during
phase transition. The corresponding relationship is shown in
Fig. 2B.
However, the above interpretations and inferences are shallow, Fig. 2 The strategy by which low melting temperature (Tm) is achieved by
which just help readers quickly understand the thermodynamic minimizing the fusion enthalpy DHfus, and maximizing the entropy of
fusion, DSfus. (A) Illustration of design principles to promote the formation
principles behind eutectics.
of coordination network-forming liquids with low Tm. (B) Comparison of
2.1.2 Chemical potential. The chemical potential is con- DHfus, DSfus, and Tm for selecting metal–bis(acetamide) frameworks. The
sidered a good site to explain eutectics. The concept of symbol shape identifies the series of compounds, while the symbol colour
chemical potential originates from potential energy, and it is designates the metal, and the border colour designates the anion.24
applicable to most chemical reactions, and even physical Reproduced with permission from ref. 24. Copyright 2021 American
Chemical Society.
processes. It is also very specific, and the phase transition or
equilibrium can be discussed by fixing factors such as tem-
perature. Under a constant temperature and pressure, the the equilibrium can be described as,25
chemical potential of component i can be obtained from its
   
mole fraction and the chemical potential of pure substance i, Dfus Hi 1 1 Dm Cp;i Tm;i Tm;i
lnðwi gi Þ ¼  þ  ln 1
R Tm;i T R T T
mi = mideal
i + mexcess
i = mi* + RT ln wi + RT ln gi (3)
(4)
where wi is the mole fraction of component i, and gi is the
activity coefficient which represents correction of interactions where DmCp,i denotes the difference in isobaric heat capacity of
between different species. i in solid and liquid phases, and DfusHi is the enthalpy of fusion
First, consider a solid–liquid transition around a eutectic of pure i. Given the small temperature difference between
temperature, and assume that the solid pure substance is transition temperature and eutectic temperature, DmCp,i is
precipitated, the heat capacity change remains constant, so negligible, thus eqn (4) can be rewritten as the following

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equation:
 
Dmi ðwi Þ Dfus Hi 1 1
¼ lnðwi gi Þ ¼  (5)
RT R Tm;i T

Second, when considering the composition of solid, T, the

chemical potential of component i in the equilibrium of solid
(msi ) and liquid (mli) phases, can be expressed as,
msi ¼ ms
i þ RT ln X i;s Gi;s (6)
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mli ¼ ml
i þ RT ln wi;l gi;l (7)

where ms l
i and mi are chemical potentials of pure i in solid and
liquid, wi,l and Xi,s are the mole fractions of component i in
liquid and solid, and gi,l and Gi,s are activity coefficients of
component i in liquid and solid, respectively. At equilibrium, msi
and mli are equal, and the following equation is obtained.
  Fig. 3 Simulation boxes (ball and stick model) of urea–betaine system.
wi;l gi;l Urea in orange and betaine in green.32 Reproduced with permission from
ms
i  m l
i ¼ RT ln (8) ref. 32. Copyright 2021 Royal Society of Chemistry.
X i;s Gi;s

By combining entropy and capacity changes, the following

equation is obtained.26
   
wi;l gi;l Dfus Hi T  Tm;i  
RT ln ¼ þ Dm Cp;i Tm;i  T
X i;s Gi;s Tm;i
  (9)
T
þ TDm Cp;i ln
Tm;i
The form of eqn (9) is the same as that of 4, with the addition of
state in solid. Note that the above formula has undergone some
approximate transformations and is not a strictly universal
formula.
The chemical potential has a good relationship between the
temperature and the composition of the eutectic system. It also
explains the phase equilibrium at the eutectic point. However,
no more information is given about the non-ideal part of the
chemical potential, that is, the interaction between different
species.
2.1.3 Interactions. Interactions exist widely in the chemical
world. Based on electrostatic force, the chemical bond theory
was established. The Coulomb interaction between oppositely
charged ions is called ionic bond, and covalent bond is the
interaction between atoms by sharing electron pairs (electron
cloud overlap). Metal bonds are similar to covalent bonds in
nature. Modified covalent bond theory and energy band theory
have perfected the structure of metals. The non-covalent inter-
actions between molecules also cover a wide range. With
in-depth exploration, the boundary between covalent and ionic
bonds and the boundary between covalent and non-covalent
interactions have become blurred.27 In recent years, some new
chemical bonds have also even been discovered.28
In the description of chemical potential, the deviation of a
non-ideal system comes from the interaction between different
species. The interaction between metal and salt is relatively
simple because the structure of the species that compose them
is relatively simple.29,30 Moreover, the interaction between
metal atoms also involves the transfer of outer electrons, which
will be mentioned later. The formation of DESs is best
explained by interaction. For DESs, strong interactions (such
as hydrogen bonds) between species are considered to be the
cause for the drop in melting point. This is widely used to
explain the decrease in the melting point of DESs.31
Although widely adopted, this explanation is simplistic and
not rigorous. Because two strong interaction will cause the
break of old chemical bond and the formation of new bond
(chemical reaction), eutectic is essentially a physical process.
In addition, this interpretation overemphasizes the factor of
unit species. In bulk environment, every species is surrounded
by a number of others, both orientation and interaction are
complex.32 A central molecule rotates and moves in three-
dimensional space, and causes the surrounding molecules to
change simultaneously (Fig. 3). Therefore, strong interaction is
only a necessary condition for eutectic to occur and cannot be
used for quantification.
2.1.4 Vibration and diffusion mechanism. There have been
some descriptions for eutectic reactions (physical processes)
from the perspective of dynamics. But most of them have been
focused on the transformation from a liquid (single-phase)
to solids (two-phase) under a constant temperature and
pressure.33 As mentioned above, the original meaning of the
term eutectics is ‘‘easy to melt’’, instead of ‘‘crystallizing below
the crystallization point of each single component’’. Therefore,
the authors will discuss the process by which two solids
produce liquids below their melting points. When the above
discussions on entropy change, chemical potential and inter-
action explain why eutectic process occurs, the diffusion
mechanism reveals how it occurs.
The study of melting began with single substances because
their structure is simple. It has been proved that the melting
process begins on the surface of the crystal. The coordination
number of surface atoms (or molecules, ions) is fewer than that
in bulk (Fig. 4A). Therefore, surficial atoms have high energy at
the same temperature, which can also be used to explain the

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Fig. 4 (A) Schematic of contact between two crystals. The crystal atoms (labelled by *) on the surface have a low coordination number and can be
regarded as activated atoms. (B) Diagram illustrates how a ‘‘liquid’’ atom is generated. (C) Photograph of benzophenone (left) and diphenylamine (right).
(D) Eutectic liquid formed along the interface of benzophenone and diphenylamine.21 Reproduced with permission from ref. 21. Copyright 2007 Royal
Society of Chemistry. (E) Image of diazobenzene (upper) and acenaphthene (lower) placed at 47.6 1C. (F) Progressive accumulation of eutectic droplets
and melting of solid components at 50.6 1C.38 Reproduced with permission from ref. 38. Copyright 1952 American Chemical Society. (G) A complete
phase diagram with the axis of pressure.

surface energy of solids. According to Lindemann, melting occurs
when the thermal vibration amplitude of an atom becomes large
enough to cause atomic collision.34 On this basis, Galvarry
proposes the formula,35
hu2i1/2 = red
2 1/2
where hu i is the r.m.s. amplitude of atomic vibration, re is
the atomic apace under equilibrium, and d is the constant
of the oscillator at melting point. Experiments with cubic
elements have proved that the melting relationship may be
valid for alkali halide crystals.36 If it is a mixed system, the
situation will become complicated. Fig. 4B sets metal as an
example to describe how a ‘‘liquid atom’’ appears.
(1) Surface atoms are more active, and have higher vibration
amplitudes.
(2) When the two solid monomers of the eutectic system
contact, the distance between different atoms is also reduced.
At this point, atom A tends to interact with atom B (new
coordination) to reduce its energy.
(3) This penetration behaviour intensifies, and atom A
continues to approach the other B. At the same time, it is
accompanied by the breaking of old bonds and the generation
of new bonds.
(4) When atom A has completely moved away from the
(10)
lattice A, the first ‘‘liquid atom’’ appears.
The above process occurs between other atoms A and B, as
long as their vibration amplitude reaches a threshold (at
eutectic temperature). Thus, the eutectic process is produced
from a macro perspective. The above principles can also be
used to explain the growth of pure small crystals at high
temperature. As shown in the second step in Fig. 4B, atom A1
will contact atom A2 of another crystal, and a new interaction
will be formed to reach a stable state, instead of conti-
nuous diffusion. Therefore, a small grain will grow at high
temperature.
It is worth mentioning that the eutectic process of ion and
molecular compounds can also be explained using this
principle of diffusion.37 Fig. 4C and D show benzophenone

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and diphenylamine form a eutectic liquid along the interface
at ambient temperature.21 For eutectic salt and DES, the
mechanism is the same. The units of vibration are ions and
molecules, and the situation is more complicated. The phase
transition principle of molecular compounds is very compli-
cated, which is a challenge for the research of molecule-based
eutectic systems.
2.1.5 Vapor–liquid–solidA–solidB phase mechanism. In a
general binary phase diagram, the eutectic point represents the
solidA–solidB–liquid-equilibrium. The situation of the system
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can be described using Gibbs phase rule,
f* = 2  F + 1
where f * is the degree of freedom at constant pressure. Many
eutectic systems are discussed under constant pressure
because the vapor pressure of solids is relatively low. However,
this does not mean the gas phase of a system should be
ignored. Durand et al. studied the non-contact equilibrium
fusion around the eutectic temperature.38 The eutectic tem-
perature of diazobenzene (Tm = 67 1C) and acenaphthene (Tm =
90 1C) is 48.6 1C. Without contact, two crystals were placed at
47.6 1C (lower than eutectic temperature), and no obvious
phenomenon occurred after 1 hour (Fig. 4E). While at 50.6 1C,
many droplets occurred in the adjacent part (Fig. 4F). Petrucci
explained the above experiment and proposed a ‘‘vapor–
liquid–solidA–solidB’’ four-phase equilibrium mechanism,
vapor–liquid–solidA–solidB.
As described by Petrucci, the reason why this mechanism
has not received widespread adoption might be due to its
incompatibility with the condensed systems. In contrast with
molecular crystals, most atomic and ionic crystals have negli-
gible vapor pressure before melting. However, there are studies
on eutectic systems under different pressure conditions.39
Therefore, the authors remind researchers not to ignore
the gas phase (pressure) when studying eutectic systems. The
complete phase diagram is shown in Fig. 4G.
Fig. 5 A binary phase diagram with two eutectic points. (A) The cocrystal resides between the two eutectic points, with a certain stoichiometric ratio of
substances A and B. (B) Hypoeutectic and hypereutectic regions are on both sides of eutectic composition.
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2.2 Eutectics and cocrystal
Researchers who are not familiar with crystals get easily con-
fused with the terms ‘‘eutectics’’ and ‘‘cocrystal’’. Even some
professionals sometimes cross the borderline between them.
In 2012, Zaworotko et al. proposed the definition and classifi-
cation of a eutectic system from the perspective of active
pharmaceutical ingredients: cocrystals are solids that are
crystalline single phase materials composed of two or more
different molecular and/or ionic compounds generally in a
stoichiometric ratio.40 However, this definition has its limita-
tions. For example, it does not include host–guest inclusion
compounds. Although some multi salt systems are thought to
(11) form coordination complexes, the above definition can be used
as a simple definition of cocrystals.41
Stahly proposed a simple insight between eutectics and
cocrystal.42 A binary system which forms a cocrystal exhibits
two eutectics, between which resides the cocrystal (Fig. 5A).
At the eutectic point, mixed crystals are precipitated by cooling.
In addition, the melting point of the cocrystal is not necessarily
lower than the melting point of each monomer. However,
according to the geometric relationship, the melting point of
the eutectic system is higher than the two adjacent eutectic
temperatures.
2.3 Hypoeutectic and hypereutectic
The scope of the terms ‘‘hypoeutectic’’ and ‘‘hypereutectic’’ is
quite limited. In a simple eutectic system (usually with one
eutectic point), they are used to describe the comparison of a
solid component and the eutectic component. The area to the
left of the eutectic component will form a hypoeutectic, which
means that the content of the component A is less than that of
the eutectic component (Fig. 5B). Conversely, the ratio(A) greater
than the eutectic ratio is hypereutectic. Although these solids
are mixed crystals, strength differs from composition to
composition.43 It is worth mentioning that the judgment of
hypoeutectic and hypereutectic depends on the position of
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substances A and B in a phase diagram, which is usually
determined by conventions.
3. Eutectic metals
A eutectic metal (eutectic alloy) is a mixture of metals with a
melting point lower than that of any of its components. The
history of the Bronze Age in various regions is not clear because
of subsequent intentional or unintentional acts of sabotage.
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Africa is considered the earliest region to use bronze smelting,
in about 4000 B.C., and bronze decorated with obsidian has
been found in Europe along the Aegean Sea.44,45
Bronze was produced by mixing 25 wt% tin into copper, so
that the melting point of the mixture would decrease from
1083 1C to around 800 1C.46 This is a typical example of mixing
metals to decrease the operating temperature and increase
wear resistance and chemical stability. Although bronze is not
an example of a eutectic system (Fig. 6A), it provides some
inspiration to explore this useful phenomenon. Eutectic alloys,
including lead–tin, silver–copper, and gallium–indium–tin
alloys, have gradually been discovered (Fig. 6B).19,47,48
Fig. 6 Phase diagram of the Cu–Sn system (A).51 Reproduced with
permission from ref. 51. Copyright 2012 Institute of Electrical and Electro-
nics Engineers. Phase diagram of the Pb–Sn system under the atmospheric
pressure (B).52 Reproduced with permission from ref. 52. Copyright 2019
Multidisciplinary Digital Publishing Institute.
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In the solid state, the melting point of a metal depends on
several factors, including the number of electrons involved in
the metal bonds, the degree of ionization, and the crystal
structure. The relatively low melting points of zinc-group
elements are believed to result from complete filling of
electrons in the d and s shells. The same is true for some
post-transition metals, where completely filled d shells and
partially filled p shells are responsible for their low melting
points.
Gallium, whose melting point is the lowest in post transition
metals is the most common component in the formation of
eutectic metals. Heine studied the distances, covalency and the
axial ratios of Ga crystal. Result showed that the number of near
neighbours makes Ga pseudo hexagonal about the A axis as
well as pseudo tetragonal about the C axis.49 In addition,
studies have shown that dimer molecules exist in crystalline
gallium.50 These intrinsic characters result in the low melting
point of gallium, and make Ga exhibit both covalent and
metallic bonding in the solid state. When gallium and other
metals are mixed at the atomic level, the larger distance
between atoms constitutes a significant structural anisotropy.
This indicates that the binding force is weak, which promotes
the rupture of the crystal structure at low temperatures, resulting
in eutectics (decrease in melting point).
It is necessary to mention that the phrase ‘‘liquid metals’’ is
more common used in research articles than ‘‘eutectic metals’’.
Among them, some refer to pure gallium, some are eutectic
alloys, and others are non-eutectic alloys. In this review, all
liquid metals denote eutectic liquid metals.
3.1 Properties of eutectic metals
Eutectic metals, especially gallium alloys, have a low viscosity
and a high surface tension as ‘liquid’, while they have high
thermal and electrical conductivities as ‘metal’. In recent years,
a series of eutectic liquid alloys have caught people’s eyes. In
particular, the gallium based alloys have excellent properties
and have been widely used in various fields.48 Consequently, it
is of great value to investigate the thermophysical properties of
eutectic liquid alloys to develop new applications.
The physical properties (i.e. melting point) of gallium,
eutectic Ga–In alloy, Ga–In–Sn alloy and mercury are given in
Table 2.
3.1.1 Density and rheological properties. Mozgovoi studied
some Pb eutectic liquids from both theoretical and experi-
mental standpoints.55,56 For Pb–Li alloy, the density could be
given by the following equations:
rsolid = 10.69(1  80  106T) (12)
rliquid = 10.47(1  110  106T) (13)
where rsolid and rliquid are in g cm3 and T is in K.
Gancarz et al. studied the density and viscosity of the Ga–Sn
system and the ternary system (with Zn added).57 The results
showed that there is a good linear relationship between density
data and temperature. Compared with the Ga–Sn system, the
density after adding Zn increases, which is related to the high
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Table 2 Physical properties of Ga, Hg, water and some eutectics53,54

Parameter Ga EGaIn Galinstan Na27K73 Mercury Water@21.85 1C

a
Melting point (1C) 29.76 15.5 13.2 11 38.8 0
Density at 20 1C (g cm3) 5.90 6.280 6.440 0.8682 13.533 998.0
Heat capacity (J kg1 K1) 410 404 295 982.1 140 4181
Viscosity (Pa s) 1.37  103 1.99  103 2.4  103 0.77  103 1.53  103 0.96  103
Thermal conductivity (W m1 K1) 29.3 26.6 16.5 21.8 8.5 0.606
Electrical conductivity (W m1 K1) 6.73  106 3.40  106 3.46  106 2.878  106 1.04  106 5.5  106
a
Note: this value is often confused with the freezing point (19.0 1C).3
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density of Zn (6.819 g cm3 at 750 K). The comparison between
Gancarz’s work and other publications is shown in Fig. 7.58–61
Physicochemical properties like rheology and viscosity play a
significant role in smelting alloys, as well as in some other
applications. A great deal of research work has been carried out
over the decades. Greer and coworkers collected some empiri-
cal correlations for the viscosity of pure liquid elements, and
extended to the cases of intermetallic compounds and
eutectics.62 They discussed, further, the available formulae
attempting to describe the viscosity as a function of composi-
tion and temperature, with particular attention to glass-
forming alloys.
The Andrade formula for the melting point viscosity, Z(Tm),
of liquids has been reassessed by analyzing a great quantity of
thermodynamic data on metallic elements and eutectic alloys:
pffiffiffiffiffiffiffiffiffiffiffiffiffiffi
A  Tm
ZðTm Þ ¼ CA (14)
V 2=3

where CA is an estimated value of 1.655  107 ( J K1 mol1/3)1/2,

A is the atomic weight, and V is the molar volume at Tm.
If the diffusivity of an atom in liquid phase is known,
Stokes–Einstein relation can be used to calculate the viscosity
of elements. In a binary alloy, the composition-dependence of
isothermal viscosity is not strong. The Z(T) of systems which are
easy to form the glass state is non-Arrhenius while best fitted by
the Vogel–Fulcher–Tammann equation:
 Y 
ZðTÞ ¼ Ge TT 0 (15)

where G and Y are constants, and T 0 is the temperature at

Fig. 7 Temperature dependences of density (A) and viscosity (B) for
Ga–Sn eutectic based alloys with Zn additions.57 Reproduced with permis-
sion from ref. 57. Copyright 2018 Elsevier.
which the excess configurational entropy or the free volume
is zero.
Whitesides et al. reported the rheological behaviour of the
eutectic liquid metal (75% Ga and 25% In by weight, melting
point: 15.5 1C) as it is injected into microfluidic channels to
form stable microstructures of liquid metal.63
3.1.2 Melting point. So far, all metals except mercury are
solid at room temperature (25 1C). Among them, gallium is
particularly special. Ga possesses a melting point of 29.76 1C,
and some of Ga-based alloys possess a lower melting point
and therefore have a larger temperature range in liquid
applications.48,64 In addition, Ga is considered to be environ-
mentally friendly, so it is expected that Ga and its alloys could
replace transition metals in the field of materials.48
In another work, thermodynamic properties of uranium
were studied in the (U + Ga), (U + Sn) and (U + Ga + Sn)
systems.65 It was verified that the activity of uranium in
(Ga + Sn + U), (Ga + U) and (Sn + U) alloys is close. However,
the activity coefficients of uranium in liquid Ga and (Ga + Sn)
eutectics are lower than those in alloys with tin, and lowering
the temperature will make the difference more significant.
Furthermore, pressure can induce crystallization of Ga–In eutectic
alloy.66 Jiang et al. reported a quaternary alloy (Ga–In–Sn–Zn) with

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a low melting point, which has pushed the boundaries a little
further reaching a melting point below 10 1C.67
3.1.3 Surface tension. The surrounding environment of the
molecules on the surface of the substance is different from that
of the internal molecules, so the characteristics of the surface
are different from the inside. Molecules on the gas–liquid
interface are subject to little force from gas phase molecules,
and greater force from liquid phase molecules, so they are
subjected to a pulling force directed to the inside of the liquid.
Free deformable surfaces are characteristic of the liquid phase,
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so the liquid surface has the tendency to automatically shrink
to a minimum.
The measurements of surface tension are important. Ozawa
et al. reviewed the experimental progress and theoretical frame-
work in the past few years.68 They summarized three main
methods for measuring the surface tension of liquid metals:
the sessile drop technique, pendant/sessile drop combined
method, and levitated drop method (electromagnetic levitation,
drop oscillations, and microgravity experiments). The methods
they proposed are contributing to measure the surface tension
of high-temperature melts while ensuring their stability.
In another work, Dickey et al. introduced a method which
controlled the interfacial tension of metals by electrochemistry
and electrocapillarity, thereby quickly (in microseconds)
changing and adjusting the size of liquid metal droplets.69
The use of electric potential is easy to operate, and the method
is expected to be applied to some technology such as micro-
fluidics. In addition, the surface tension of the liquid alloy can
be controlled by controlling surface oxidation.70
3.1.4 Thermal and electrical conductivities. Eutectic Ga–
In–Sn alloy, often called EGaInSn and Galinstan, is widely used
in various fields. Novakovic et al. used raw materials with a
purity of 99.999% to thoroughly study the thermodynamic
properties of EGaInSn in a large temperature range.71 The
temperature dependence of conductivity (291 to 723 K) can be
approximated using the following equation,
s(T) = s0  49.8(T  Tm) + 0.0476(T  Tm)2 (16)
where s0 = 33 170 O1 cm1 is the electrical conductivity at
291 K. The research result was compared with the related
publications and database. This work not only corrected the
inaccurate data in the past, but also contributed to the popu-
larization of EGaInSn. Rykaczewski and coworkers reported a
method for preparing chemically stable solid–liquid metal
mixtures with enhanced thermal interfaces.72 Metal particles
(tungsten) were shear mixed with EGaInSn in a mortar
to produce a paste-like mixture. A stepped-bar apparatus
following the ASTM D5470 standard and the Hot Disk transient
plane source method was constructed. The outcome showed
that the thermal conductivity can be up to 2 times compared
with that of EGaInSn. As the proportion of tungsten increases,
the morphology of the mixture gradually changes from a paste-
like morphology to a powder. These thermal interface materials
synthesized using EGaInSn are expected to be applied in
wearable devices and soft robots.
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The resistivity of the Sn–Bi alloy shows a significant tem-
perature dependence. Moreover, as the content of Bi increases,
the resistivity increases, which may be related to the larger
intrinsic resistivity of Bi.73 Interestingly, for Sn–Bi alloys (Bi 63
wt% and 58 wt%), the resistance and temperature dependence
below 220 1C are similar to those of semiconductors. The result
along with that of magnetic susceptibility obtained give support
to the statement that the eutectic Sn–Bi alloy differs signifi-
cantly in its electron structure from hypo and hyper eutectic
alloys.
3.2 Applications of eutectic metals
Compared to mercury, these liquid metal alloys are much safer
for they have a negligible vapour pressure and low toxicity,
which make them good candidates for various electronic appli-
cations. Furthermore, unique properties show potential usage
in materials science and semiconductor engineering. For exam-
ple, some gallium liquid alloys can rapidly form an atomically
thin layer gallium oxide over their surface when exposed to
oxygen. They have even been considered as potential coolants
in nuclear power plants which will replace the status of Na.
Finally, combining with many other materials can greatly expand
their applications.
3.2.1 Eutectic for preparing nano materials. Nanotechnology
has penetrated every aspect of modern life, and the preparation of
nanomaterials has gained importance. Vapour–liquid–solid, the
triple phase coordination is supposed to be the process of
preparing metal nanowires.74 Kodambaka and coworkers found
that the kinetic enrichment of the eutectic alloy composition
might be the reason for nanowires to grow below the eutectic
temperature (Fig. 8A–C). Fig. 8A shows a series of images of a
single Ge wire acquired at times t = 0, 309, and 618 s (from left to
right, respectively) during growth using the vapour–liquid–solid
mechanism at 340 1C and 4.6  106 torr Ge2H6. The rate of
growth is 9.9  102 nm s1. Fig. 8B shows a series of image for a
second wire growing at the same temperature and pressure but
with a solid catalyst at t = 0, 1340 and 1824 s (from left to right,
respectively). The growth rate for this mode is 1.3  102 nm s1.
The result also showed that in the process of using Au to grow Ge
wire, the state of catalyst may be lower than Te which may be
either solid or liquid. The state of catalyst depends not only on
temperature, but also on the pressure and history of Ge2H6.
Moreover, their work could provide reference value for other
nanowires.
Although eutectic liquid metal is liquid at room tempera-
ture, it does not spontaneously return to the shape with the
lowest interfacial free energy like Hg and H2O. The eutectics
can form metastable, non-spherical structures (e.g., cones and
filaments with a diameter of 1 mm). These desirable properties
make eutectic metal useful for forming electrodes for thin-film
devices. In another work, Daeneke and coworkers developed
two efficient methods to synthesize desired metal oxide
nanosheets using eutectic gallium-based alloys as the reaction
solvent.75 In the first method, a pristine liquid metal droplet is
first exposed to an environment with oxygen. Then touching
the liquid metal with a solid substrate allows the transfer of the
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Fig. 8 (A) Series of images of a single Ge wire growth at 340 1C and 4.6 
106 torr Ge2H6, t = 0, 309, and 618 s. (B) Another image series for a
second wire growing at the same temperature and pressure, t = 0, 1340
and 1824 s. (C) Binary phase diagram of Au and Ge.74 Reproduced with
permission from ref. 74. Copyright 2009 The American Association for the
Advancement of Science. (D) Schematic representation of the touch-print
method. (E) Schematic representation of air-bubble method.75 Repro-
duced with permission from ref. 75. Copyright 2017 The American Asso-
ciation for the Advancement of Science.
interfacial oxide layer. The whole process is called van der
Waals exfoliation technique (Fig. 8D). The second method
relies on oxygen-contained bubbles to produce metal oxide
nanosheets by injecting pressurized air into the eutectic liquid
metal (Fig. 8E). This pioneering work provided good methods
for preparing 2D materials at room temperature, and metal
nitrides can be prepared in the same way.76 Maldonado et al.
used an electrochemical liquid–liquid–solid method to control
the morphology of micro–nanowires.77 Compared with
pure Ga, a liquid Ga–In alloy can make Ge wires grow more
uniformly.
3.2.2 Flexible electronics and microfluidics. Electric devices
have gained increasing popularity. The demand for electronic
components such as battery electrodes, battery diaphragms and
self-repairable conductors is unprecedentedly high. Copper along
with silver wires are generally used as conductors. They have good
electrical conductivity but are easy to break permanently. The
combination of liquid metal and other materials can solve the
drawbacks of poor tensile properties and non-self-healing nature
of collectors. Lee and coworkers presented a self-healing conduc-
tor that is composed of nickel flakes, eutectic gallium indium
particles and carboxylated polyurethane.78 Self-healing can be
achieved when the damaged regions are electrically restored by
the flow of liquid metal, and mechanically healing can be
activated by the interfacial hydrogen bonding of polymer. Park
et al. found that eutectic gallium–indium can diffuse on the
surface of an alkanol-based hydrogel while maintaining good
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stretchability (Fig. 9A).79 The prepared composite electrode can
be stretched by 1500%. It was then cut, and after recovering under
environmental conditions for 5 minutes, its new maximum
elongation is about 900% (Fig. 9B). At the same time, the
resistance change of the electrode is negligible. Moreover, the
pattern of the electrode can be designed (Fig. 9C).
Goodenough and coworkers reported a room-temperature
liquid alloy based anode membrane with the immobilized
organic liquid electrolyte.80 No self-discharge was observed
since the liquid Na–K did not dissolve into the liquid carbonate
electrolytes. Dendrite growth and serious interface issues are
still fundamental challenges for the practical application of
alkali metal batteries. In another work, Yu and coworkers
reported a highly stable Na–K alloy–graphene composite elec-
trode, which realized alkali metal anode with a high energy
density and low redox potential.81 Moreover, the immiscibility
with organic compounds makes eutectic metals a class of good
candidates for incorporation into functional, packaged organic
devices.82 In the future, this would be a useful technique for
complex large areal stretchable printed electronic systems.
Virtual reality (VR) has been widely used for training and
games, and the value of VR as a contactless technology is
constantly increasing. In a recent work, Bea et al. developed a
multi-modal sensing and feedback glove.83 The manufacturing
steps of the thermal sensor layer are shown in Fig. 9D. Before
directly writing the eutectic Ga–In alloy (EGaIn) traces, an
organic silicon layer is formed by a blade coating process.
A flexible flat cable (FFC) is connected to the silicone layer,
which is placed according to the written EGaIn traces. The FFC
and EGaIn traces are connected by a direct ink writing 3D
printing method. The writing trace is encapsulated by the
second silicone resin layer. After curing, all unnecessary parts
of the silicone film are removed. The sensor was prepared as
fabric-covered gloves and tested in a VR environment. There are
eight heating elements embedded in the heating plate (five for
each finger and three for the palm), which can be controlled
independently, as shown in Fig. 9E. As shown in Fig. 9F and G,
the flexion and extension movements of the five fingers are
captured by the sensor sheet attached to the back of the hand.
Therefore, animation of hand can be reconstructed (Fig. 9H
and I). In another work, the same research group prepared a
soft electrode system by using contact sensing of a eutectic
metal.84 A wearable sensor can be prepared by writing EGaIn
wires on a silicone substrate to measure the ground reaction
force (Fig. 9J and K). As shown in Fig. 9L, the signal shows a
repetitive pattern during walking. During walking, only 6
sensors (sensors 2, 3, 5, 8, 9, and 10) of the 10 sensors on the
soles of the feet had significant changes. As the heel touched the
ground, sensors 8, 9 and 10 in the heel were activated sequentially
from the back of the heel. When the centre of pressure moved
from the back of the foot to the front of the foot, sensors 2, 3 and 5
were activated, and the resistance changed more widely. The
higher resistance change is attributed to the concentrated load
generated by the bone structure of the foot.
Brand et al. reported a more exciting technology about all-soft
and high-density electronic devices based on a eutectic metal.85
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Fig. 9 Eutectic metals for soft and stretchable electronics. (A) Photographs of latertally stretched micropatterned high-density EGaIn electrodes.
(B) Stress–strain curves of a pristine composite electrode and a self-healed electrode following cutting. (C) Photograph of micropatterned electrode on
alkanol-based hydrogel.79 Reproduced with permission from ref. 79. Copyright 2020 John Wiley and Sons. (D) Fabrication process of a heater sheet by
the direct ink writing method of EGaIn. (E) Photograph of assembled glove. (F) Optical camera and (G) IR camera image of the hand in glove. (H) Image of
hand posture and (I) reconstructed animation in VR environment.83 Reproduced with permission from ref. 83. Copyright 2020 John Wiley and Sons.
(J) Soft sensing insole measuring ground reaction forces connected by an electroless nickel immersion gold finished flexible flat cable. (K) Soft sensing
insole attached below the foot using medical tapes. (L) Sensing signals recorded during three gait cycles.84 Reproduced with permission from ref. 84.
Copyright 2019 American Chemical Society.

The hybrid lithography process is applied to dual-phase structures
to create soft nano/microstructures embedded in elastomeric
materials. Using this extremely high-resolution EGaIn patterning
technology, a submicron EGaIn thin film pattern with a feature
size as small as 180 nm and a line pitch of 1 mm can be realized.
The resulting stretchable EGaIn pattern provided a currently
unparalleled combination of resolution, electrical conductivity,
and electronic/wiring density. It is hoped that the developed
EGaIn nanofabrication technique based on hybrid lithography
plays an important role in the field of bio-integrated electronics.
Motivated by the increasing demand of flexible electronic
products, liquid metal microfluidics have developed greatly in
recent years, which can be traced back to the field of micro-
fluidic channels.86 Elastic materials are often used as a shell for
encapsulating the liquid metal to protect the continuous phase
of the liquid metal. The composite material in the droplet is
usually an insulator, but the liquid metal packaged in the
elastomer becomes a conductor due to its continuous phase,
and its electrical conductivity and thermal conductivity can be
adjusted.
He et al. studied the movement of Galinstan and liquid gallium
micromachines under a direct-current electric field.87 The liquid
metal Galinstan micromachine was pushed to the positive elec-
trode by the surface tension gradient, while the liquid pure gallium
micromachine was pushed to the negative electrode by the gene-
rated hydrogen bubbles. These works provide new possibilities for
the motion control of micromachines in the channel.
Petit and coworkers reported a numerical model and some
experiments of a micro-channel liquid metal cooler.88 A numer-
ical study on the effect of thermal conductivity of cooler
materials was carried out, and a discussion on the correlation
of using classical convection heat transfer was presented.
By the cooling experiment of silicon chips, liquid metal showed
a strong advantage compared with water. This work is expected
to provide a good heat dissipation strategy for high power
density electronic devices. Furthermore, the liquid metal micro-
fluidics based electronic systems are found to have potential in
deformable antennas, soft diodes, transient circuits, etc.
3.2.3 Motion robots. Robots based on eutectic metals have
attracted attention because they can respond to electricity,

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magnetism, and light. In Zhang’s work, a wheeled robot using
a room temperature liquid metal droplet as the core of the
driving system was developed.89 The metal droplets inside the
robot were driven by voltage to change the centre of gravity,
thus generating a rolling torque (Fig. 10A–C). The driving
module in this robot was relatively lightweight and facile to
replace. Therefore, the study is expected to expand the research
of liquid metal based actuators and to accelerate the develop-
ment of future complex robotic systems. In another work, Liu
et al. prepared a eutectic metal based micromotor by a simple
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facilitate the micromotor to have broad potentials in chemical
induction and artificial intelligence, which cannot be achieved by
rigid micro-robots. A photochemically induced motion of liquid
metal marbles was reported by Mitchell and coworkers.91 The
addition of WO3 nanoparticles allows the eutectic alloy to generate
H2O2 bubbles under UV light, which thereby generate a propulsion
force (Fig. 10H). Fig. 10I shows the movement of a WO3 coated
marble for 240 seconds, and the time–displacement curve is
shown in Fig. 10J.
Liu et al. studied the coloration of a eutectic alloy.92 This liquid

general-purpose ice-assisted transfer printing method.90 The
micro-swimmer showed effective propulsion under an elliptical
polarized magnetic field (Fig. 10D and E). The force and motion
analysis of liquid motors of different shapes is shown in
Fig. 10F and G. Moreover, the micromotor can undergo drastic
morphological transformation in an aqueous environment under
the irradiation of an alternating magnetic field. These properties
metal soft robot is bio-inspired and has adjustable structural colour.
In different electrolytes, the colour of the alloy droplets can be tuned
by changing the substrate. Further research show that the colour
change is related to the Ga2O3 film formed on the surface of eutectic
alloy and the iridescence was triggered by film interference.
3.2.4 Catalysis. Metals and their compounds are usually
used for catalysis, so are eutectic metals, especially gallium

Fig. 10 Soft robots driven by electricity, magnetism, and light. (A) Structure and composition of a wheel robot. (B) Schematic of the driving module and
the working mechanism. (C) Sequential snapshots for actuating an actual wheeled robot at a steady speed, the inset shows the time–displacement plot.89
Reproduced with permission from ref. 89. Copyright 2018 John Wiley and Sons. (D) Schematic of the magnetic propulsion of liquid metal micromotors.
(E) Time lapse images depicting swimming of a micromotor. (F) Mechanical analysis and swimming mechanism of the bowling-pin-like liquid metal
microswimmer in an elliptically polarized magnetic field. (G) The dependence of average speed V upon the polarization of the applied magnetic field Hmax
(Hmin = 10 mT).90 Reproduced with permission from ref. 90. Copyright 2019 John Wiley and Sons. (H) Schematic of the experimental setup showing the
motion mechanism of the EGaInSn marble. The light beam passes through an objective lens (also used for imaging) and is focused onto one side of the
marble. (I) Sequential snapshots of the motion of a 2 mm diameter sphere marble in 15% H2O2 solution when a light intensity of 100% is approaching
the marble from the left-hand side at a constant speed of 4.5 mm min1. The visible purple spot is the light beam. (J) Time displacement plots for both the
light spot and the marble.91 Reproduced with permission from ref. 91. Copyright 2013 American Institute of Physics.

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alloys. On one hand, the melting point of gallium is pretty low;
on the other hand, gallium is relatively active. The EGaInSn
droplets of macro size can be used for current displacement to
produce silver and gold.93 In principle, this allows one to
recover precious metal ions from solution in their metallic
form, which are immobilized on the liquid metal and therefore
easy to recover. Additionally, eutectic alloys can be used in
other reactions, such as dehydrogenation of propane and
methylcyclohexane.94,95
O’Mullane introduced a simple method for preparing cata-
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lytically active materials from eutectic alloys.96 The EGaInSn
droplets were sonicated in an alkaline solution or treated in a
reducing medium to form In/Sn-rich solid microspheres with
reductive catalytic activity. In another work, Kalantar-Zadeh
et al. reported a method for synthesizing metal foams with
inherent catalytic properties based on eutectic metals.97 With
indium as the additive, low-cost Bi–Sn alloy was processed
into nano-structured metal foams. At a current density of
25 mA cm2 (1.2 V vs. RHE), a high CO2 electrical conver-
sion efficiency (82%) can be achieved. This work is considered
important for the design of heterogeneous catalytic reactions
and reactors.
Existing research indicates that there are many kinds of
eutectic metals with desirable properties. Alloying is not only a
general method to lower the application temperature, but also
a strategy to prepare task-specific systems. This inspires
researchers to develop new eutectic systems.
4. Eutectic salts
In the 1940s, Glauber’s salt (Na2SO410H2O) was used as a
medium to store solar energy.99,100 Later, research was focused
on the thermophysical properties (including viscosity, surface
tension, and density) of the equal molar mixture NaNO3–KNO3
in the temperature range of 300–600 1C in oxygen and argon.101
Compared with the surface tension and viscosity, density of this
salt mixture is mainly affected by the presence of nitrite. The
fundamental research on molten salts might be beneficial to
Fig. 11 Schematic representation of a ‘‘Solar Two’’ plant. EPGS for electric power generation system.98
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the implementation of the project ‘‘Solar Two’’.98,102 Although
eutectic salts possess high melting enthalpy and low melting
points, their engineering technology requires optimization.
In ‘‘Solar Two’’, eutectic salts were used as energy storage
materials to achieve high-quality energy storage and conversion
(Fig. 11).
During operation, a cold (285 1C) molten salt is withdrawn
from the cold salt tank and passed through a receiver where it
is heated to 565 1C. It then flows under gravity to the hot salt
tank, where it is stored until steam is needed to drive
the turbine. When needed, it is pumped through the steam
generator, generating a 512 1C steam for the electric power
generation system (EPGS), and then sent back to the cold box to
repeat the cycle.103 Molten salts can also store energy in large
containers for future use, such as at night or a cloudy day. The
‘‘Solar Two’’ has enough capacity to run continuously for three
hours after sunset. The commercial plant, called ‘‘Solar
Tres’’ built in Spain combined ‘‘Solar One’’ and ‘‘Solar Two’’
technologies.104 Although there is no improvement in energy
storage medium, the plant is able to work 24 h per day in
summer.
Eutectic salts were customarily called ‘‘molten salts’’.
In some circumstances, their melting properties have been of
more interest, while their eutectic properties were ignored. The
principle of eutectic causes the melting point of a salt mixture
lower than that of its single component, which intensifies the
promotion of the term ‘‘molten salt’’. Molten salt has a wider
scope than eutectic salt and includes single substances and
other non-eutectic systems. Although there are differences
between eutectic salts and molten salts, most of the molten
salts mentioned in this review are eutectic systems.
4.1 Properties of eutectic salts
The properties of eutectic salts, especially their thermodynamic
properties, have been studied in depth. The density of a
eutectic salt determines the strength and size of the container,
and its melting point has a strong relationship with the
operating temperature. However, the most important property
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is enthalpy, that is, the latent heat of the eutectic salt. This is
the key element for energy storage, because a high melting
enthalpy can increase the energy storage efficiency, with
consequent economic benefits. Therefore, a great deal of
measurement work for specific systems has been performed,
and many empirical and semi-empirical prediction equations
have been established. Last but not least, the stability of
eutectic salts under high temperature or carbon dioxide condi-
tions has been investigated.
4.1.1 Density. The density of a molten salt is crucial to its
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usage because it is related to the size and strength of the energy
storage devices. The density measurement of a molten salt is no
longer a major problem, and its microscopic exploration and
prediction of density are the focus of current research.
As mentioned above, the mixture of NaNO3 and KNO3 is known
as solar salt, which has been commercialized. Bonk’s work
introduced semi-empirical estimates of the density of solar salt
and other molten salt mixtures at low melting temperatures in
the range of 70 1C to 140 1C.105 Excitingly, the density of a
ternary even a multicomponent mixture can be predicted from
the concentration of the addition. The density of other types
of eutectic salts and their multiple systems has also been
studied.106
The density of eutectic salts can be derived from the product
function of the coordinated properties of anions and cations,
respectively.107 Moreover, the results are highly accurate and
stable. This method is the theoretical development of a eutectic
salt, which avoids some measurement operations under
extreme temperature. Understanding the microscopic proper-
ties of eutectic salts is essential for their applications. For
example, the pyrometallurgical process can be used to process
scrap metal nuclear fuel. Vaden et al. reported a model for
determining the density of molten salt, electro-refining uranium
metal in the LiCl–KCl system.108 The basis for the correction
factor is knowing the chloride ion coordination chemistry of U3+.
After applying the correction factor, the accuracy can be improved
greatly.
4.1.2 Melting point. Measuring the melting point of a
eutectic salt is usually not a difficult task, thanks to the
development of technologies such as differential scanning
calorimetry. Tang et al. measured the melting point of the
eutectic Na2CO3–NaCl binary salt mixture.109 An exponential
relationship between viscosity and temperature is observed,
and the vapor pressure increases significantly as the tempera-
ture increases. Melting point is usually studied together with
other properties, such as viscosity and conductivity. Tasaka
et al. developed a simulation technique, calculation of phase
diagram and thermodynamics method, to estimate ion con-
ductivity and melting point of LiF–LiCl–LiBr-based quaternary
systems.110 These molten salts have the potential as electrolytes
in high temperature batteries; hence, the simulation of their
ionic conductivities and melting points is of great significance.
Furthermore, numerous research work has been done to pre-
dict the melting point of halide and nitrate eutectic salts.111–113
As a typical example of a ternary eutectic mixture, the LiF–
NaF–KF system is of interest because it is a good solvent and
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Fig. 12 Structure of salt tank coupled with heaters and temperature
sensors.115 Reproduced with permission from ref. 115. Copyright 2019
Elsevier.
low-pressure heat-transfer medium.114 This eutectic salt pos-
sesses good solvent properties, high thermal stability, and
extended liquid range from 500 to 700 1C.
In industry, the use of molten salt is in large-scale. Storage
tanks are generally covered with thick rock wool insulation
during operation; the insulation of storage vessels is a big
challenge. In Li’s work, the dissolution process of over 24 tons
of molten salt was studied (Fig. 12).115 Manual and automatic
heating methods are used to heat the salt tank to achieve fast
and safe operation. The temperature change is most obvious in
the first 38 hours after the start. During the whole melting
process (314 h), there is a large temperature difference between
the heights of 325 to 825 mm across the entire tank, which is
108 1C. Salt near the bottom area in the tank must be well
heated. In this manner, the economic operation mode of
molten salt heat storage tank is obtained.
The melting points of other multicomponent mixtures have
also been explored. However, as a class of energy storage
materials, the latent heat of the fusion (melting enthalpy) of
eutectic salts is worthy of more attention.116
4.1.3 Heat capacity and enthalpy. Heat capacity and
enthalpy are both important properties because they determine
the amount of energy stored in molten salts. After fully studying
the phase diagram of binary eutectic salts, the isobaric heat
capacities of many systems have been reported. In Zaikov’s
work, the isobaric heat capacity of some chloride and bromide
based eutectic salts was measured with high accuracy.117
It showed that the molar heat capacity of these mixtures is
close to that of the pure salt in the same state. Kumkov et al.
studied the isobaric molar heat capacities of a library of binary
and ternary halide mixed salts.118 This is a very systematic
work, and its error is extremely low (less than 5%). The molar
heat capacity of a molten halide mixture is the sum of the heat
capacities of each single component plus a certain value
proportional to the enthalpy of mixing. Moreover, the molar
heat capacity of the mixture is the sum of the heat capacities of
the components if the mixing enthalpy is negligible. Gaune and
coworkers measured the mixing enthalpy of a ternary system
by direct calorimetry.119 Pure NdCl3 was added to eutectic
LiCl–KCl at 1100 K, and the amount of NdCl3 was varied from
0.021 to 0.950 (in molar ratio). When the ratio is 0.400, the
maximum enthalpy change is 7.10 kJ mol1. Compared to
earlier research, the value of enthalpy change is related to the
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cation radius. It is conjectured that the larger cation is more
likely to coordinate with CI than the smaller one. Both
macroscopic laws and microscopic reasons have been studied,
which are of great help in predicting the thermophysical
properties of molten salts.
Apart from measuring, research has been done on predict-
ing the molten salts’ fusion latent heat based on the properties
of each single component. Kosa et al. proposed a method based
on the assumption that the entropy of a binary eutectic is equal
to the entropy of the individual components.120,121 The following
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its corrosion behaviour was also investigated. This eutectic salt
shows good thermal stability without degradation after cycling
1000 times between 600 and 650 1C.
As eutectic molten salts are increasingly used for thermal
energy storage, one problem is highlighted: containment mate-
rials for storing these eutectic salts. In view of the oxidation
of molten salts on alloys, their corrosion effects have been
studied.125,126 Steel alloys are considered as economic candi-
dates for containment materials in thermal energy storage
systems. Eutectic compositions of molten chlorides, nitrates,

equations are proposed: carbonates, and fluorides are the most popular storage media.
   An oxygen containing anion (such as carbonate) possesses a
DHfus Aq Br ; Tfus Aq Br
larger thermal capacity compared with chloride. This eutectic
( " ð Tfus ðAq Br Þ #
  DCp;fus ðA; TÞ salt has attracted much attention because of its high energy
¼ Tfus Aq Br q DSfus ðA; Tfus ðAÞÞ þ dT density and less corrosive behaviour. The furnace test is a
Tfus ðAÞ T
simple and feasible method.127 Salt containers are placed in
" ð Tfus ðAq Br Þ #
DCp;fus ðB; TÞ the furnace at room temperature and then gradually heated to
þ r DSfus ðB; Tfus ðBÞÞ þ dT the final temperature. Once the salt melts and the chamber
Tfus ðBÞ T
conditions are stable, the coupons will be immersed. Then, the
  
DHmix;melt Aq Br ; Tfus Aq Br top half of sample can be exposed to the air and the bottom half
þ   submerged into the molten salt. The samples were exposed to
Tfus Aq Br
molten salts until they were removed after 120 hours. This
2    39
q ln a A; melt; Tfus Aq Br = method allows researchers to compare both the corrosion of
 R4    5; salts and oxygen. It was also found that the decomposition
þr ln a B; melt; Tfus Aq Br
gases of salt can increase the corrosive impact of the atmo-
(17) sphere. In addition, the corrosivity of molten salt on high-
density graphite electrodes and their zirconia coatings has been
where Aq/(q+r)Br/(q+r) represents the two components of 1 mole binary
studied.128
mixture, Tfus is the melting temperature of the eutectic in K, a is the
However, salt systems with high redox activity are valuable
activity coefficient of the component, DSfus and DCp,fus are
in some cases because of their unique physicochemical proper-
the difference of entropy and heat capacity of the component,
ties. Sagara et al. prepared a redox-active ionic liquid (RAIL) by
respectively, and DH is the heat of the mixing process.
mixing two distinct ionic liquids.129 Charge transfer (CT) was
The equation can be modified to apply to n-component
conducted by choosing a carbazole based ionic liquid
eutectic mixture, which is given by:121
([CzC4ImC1][TFSI]) as the donor and a viologen-based ionic
X n  ð Tfus 
liquid ([C4VC7][TFSI]2) as the acceptor (Fig. 13A). The electro-
 DCp
DHfus ¼ Tfus DSf;i þ dT  Rxi lnðai xi Þ chemical reaction of neat CT-IL is shown in Fig. 13B. Among
i Ti T
þ DHmix (18) them, the second circle attracted the attention of researchers.
Cyclic voltammetry curves of viologen in region A in Fig. 13B
where DSf,i is the entropy change of fusion for component i, and produced peaked diffusion-limited waveforms due to semi-
ai is the activity coefficient of component i. Useful thermo- infinite planar diffusion to the electrode surface. Further
dynamic properties of eutectic salts have been extensively analysis proved that these cyclic voltammetry curves can be
studied and some of them can be found in reference books.122 regarded as electrochemically reversible responses.
4.1.4 Stability and reactivity. Eutectic salts are applied in There is a lot of research work on molten salts. However, the
various technological processes because they are quite stable at data and conclusions obtained by different researchers are not
high temperature. They exhibit strong inertness in terms of always consistent. One of the reasons is the preparation
thermal stability and reactivity. Some eutectic salts showed method of the eutectic salt. Tie et al. used 6 preparation
no decomposition under CO2 atmosphere, and little decom- methods to study the relationship between the preparation of
position (0.15% weight loss) under N2 atmosphere up to NaNO3–KNO3 binary molten salt and its thermophysical prop-
700 1C.123,124 This makes eutectic salts to be reliable phase erties, including latent heat, decomposition temperature and
change materials used in the power cycle based on supercritical melting range.130 The study showed that the static melting
carbon dioxide, which promotes the development of commer- method, stirring evaporation method, boiling evaporation
cial thermal energy storage. Bruno et al. explored the use of a method, tap water dissolution method, and grinding method
eutectic NaCl–Na2CO3 salt as a reliable high temperature phase can be used to prepare a binary system with good thermo-
change material.123 The eutectic salt was been thermally cycled physical properties. However, the dissolution method may
up to 1000 times. Its thermophysical properties were measured cause uneven distribution of compositions. In Castro’s review,
before and after it had been subjected to thermal cycling, and it is revealed that there are still large discrepancies between

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Fig. 13 Preparation of a redox-active ionic liquid with charge transfer
interaction from carbazole-based and viologen-based RAILs (A). Overview
of the electrochemical reaction of neat CT-IL (B).129 Reproduced with
permission from ref. 129. Copyright 2021 Royal Society of Chemistry.
different sets of data for the same salt systems.131 The impact of
these discrepancies has been discussed. Currently, it may be
difficult to recommend reference data/measuring methods that
can guide the reader toward the selection of the best systems.
Therefore, although the research on the properties of molten
salts seems to be a cliché, thermodynamic research on molten
salts is still going on.132,133
4.2 Applications of eutectic salts
The applications of eutectic salts can be broadly divided into
traditional energy storage and preparation of emerging materials.
Relatively mature technologies using eutectic salts for thermal
energy storage and as thermoelectric conversion media have
already been developed. There have been successful examples,
as evidenced by the various patents that have been granted.
Moreover, the emerging applications focusing on the preparation
of nanomaterials have enriched the use of eutectic salts.
4.2.1 Eutectic salts for energy storage. In 1968, Dijkhuis
and coworkers summarized the physicochemical properties of
a series of molten salts and evaluated their application in
electromotive force equilibrium cells (Table 3).134 Though they
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Table 3 Examples of a binary eutectic mixture as electrolyte (with
common anion)134
Component 1 Component 2
AgCl MCln (M = Li, Na, K, Pb)
AgBr MBrn (M = Li, Na, K, Rb, Pb)
CdCl2 MCln (M = Li, Na, K, Ba)
CdBr2 KBr
CeCl3 MCln (M = Na, K, Ca)
MgCl2 MCln (M = Li, Na, K, Rb)
NaCl MCln (M = Ca, Ba, Sr)
PbCl2 MCln (M = Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn)
PbBr2 MBrn (M = Na, Zn)
ZnCl2 MCln (M = Li, Na, K, Rb, Cs, Ba)
did not pay attention to eutectics (actually they called it ‘‘low-
melting mixture’’), some of the mixtures were proved to be
eutectic systems in other works.135
When converting solar energy into thermal energy, a key
issue is the conversion efficiency of the devices. Among them,
the part that directly receives solar energy is of vital importance
because it dominates the first step in energy conversion. In a
solar energy project, Tamaura and coworkers developed a
molten salt based solar energy receiver.136 A cavity-shaped
receiver for a beam-down solar concentrating system was
proposed. A simulation program was applied for using the heat
flux distribution of solar radiation, and the properties of the
constituent materials were set as input data to display the
temperature distribution of the receiver and molten salt.
The conversion efficiency of radiation to heat is calculated based
on the input solar energy and the heat transferred to the molten
salt. Under ideal experimental conditions, the conversion
efficiency of the designed receiver is about 90%.
The cover of the tank is the first barrier to block sunlight.
On one hand, we need it to block impurities and prevent the
evaporation of molten salt; on the other hand, it will block part
of the sunlight and reduce the light conversion rate. Tetreault
et al. designed a solar receiving system composed of floating
hollow fused silica balls.137 The high light transmission char-
acteristics make it possible to reduce convection and radiation
losses, and to minimize the surface area available for evapora-
tion losses. The improvement in this work is believed to reduce
the heat loss by up to 51%, while reducing light efficiency by
less than 5%. The independent spheres are easy to replace, and
their size can be adjusted according to different equipment
(Fig. 14A). This transparent cover layer has the potential to
achieve a higher solar energy efficiency, and it can also be used
in other high-temperature industrial applications. Additionally,
other improvements have also been investigated, such as the
use of metal foam to enhance the heat recovery process.139
A model was developed for investigating energy discharge from
a thermocline thermal energy storage system using a eutectic
salt as the heat transfer media.140 The temperature profiles
were systematically investigated, as well as the discharge
efficiency of the storage tank. During the discharge process,
the heat exchange zone expands with increase in time and
Reynolds number, and its propagation speed is constant.
Furthermore, the discharge efficiency of the energy storage
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Fig. 14 (A) Simplified diagram of the experimental setup used for evalu-
ating the thermal insulation performance of the floating spheres, and 3D
representation of the simulated section. An infrared camera is used to
measure the photon flux losses from the surface of a heated beaker filled
with molten salt, with and without floating spheres.137 Reproduced with
permission from ref. 137. Copyright 2018 Elsevier. (B) Cost of some molten
salts as phase change materials for supercritical CO2 cycles.138 Repro-
duced with permission from ref. 138. Copyright 2020 Elsevier.
tank increases with the height of the tank and decreases with
the increase in the Reynolds number.
Tamaura et al. studied the use of a mixture of K2CO3 and
Na2CO3 to convert solar energy into chemical energy.141 At
1123 K, the product CO is obtained through Boudouard reaction
(C + CO2 - 2CO), which is finally converted to methanol by
hydrogenation. The sources of hydrogen and carbon are
methane, which has a wide range of sources and low prices.
This work provides a way for coupling reactions to produce
energy. Apart from electrothermal conversion, molten salts can
be used in new batteries.142,143
In industrial applications, model-based simulation is very
important. Feasibility analysis was carried out from both scien-
tific and economic standpoints.138,144 In Polten’s work, massive
available thermodynamic and phase equilibrium data for the
(NaCl + KCl + AlCl3) system were critically evaluated to obtain
optimized parameters of models for all condensed phases and
relevant gaseous species.144 The models can be used along with
the Gibbs free energy minimization software to interpolate and
extrapolate, and to calculate all thermodynamic properties,
such as vapour pressures and phase diagram sections at all
compositions and even over extended ranges of temperature
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and pressure. Chartrand and coworker evaluated and optimized
the thermodynamic properties of the (NaCl + KCl + MgCl2 + CaCl2 +
ZnCl2) system.145 They discovered that the model parameters of
thermodynamic properties and phase equilibria obtained for the
binary and ternary systems can be used to predict those for
the multicomponent (44) system. In addition to thermodynamic
properties such as melting point, heat capacity, and enthalpy
change, the price per kilogram was also considered as an important
factor in evaluating the economics of energy storage.138 Fig. 14B
shows the cost price per kilogram and per kilojoule. From the
perspective of energy storage per unit price, molten salt NaCl–KCl–
NaF is almost the same as NaCl–Na2SO4 and NaCl–Na2CO3. In term
of energy density, the higher latent heat of NaCl–KCl–NaF makes
the container smaller, and the concentrated solar power system is
more compact. Therefore, the NaCl–KCl–NaF system is considered a
good phase change material for energy storage. As a relatively
mature field, there are many databases and patents on molten salt
energy storage, which provides a good platform for researchers from
both academia and industry.146,147
4.2.2 Fabrication and synthesis. Although most of the
applications of eutectic salts are focused on energy storage,
there are some applications in fabrication of materials. Covalent
organic framework (COF) has received extensive attention due
to its excellent crystallinity and high modularity. Lotsch et al.
reported the ion-thermal synthesis of crystals and porous
polyimide-linked COF in a mixture of zinc chloride and eutectic
salt.148 This method overcomes the shortcomings of the conven-
tional solvothermal one, whose reversibility is very poor in a ring-
closing reaction. Moreover, the synthesis does not require soluble
precursors, and the reaction time is significantly reduced. Inter-
estingly, some COFs must be synthesized by using eutectic salts,
which is believed due to the Lewis acidity of the ion-thermal
environment (Fig. 15A).
There have been reports that a single-component molten salt
can be used to prepare metals, carbon, and other materials.150–152
The eutectic salt can be used for the preparation of various
materials thanks to its multiple properties. Teshima et al. reported
a strategy for fabricating Ta3N5 photoanodes by utilizing a mixture
of NaCl and Na2CO3.153 The molar ratio of this system was very
different (99.9 : 0.1), so the effect of eutectic may not be obvious.
However, in Qu’s work, the morphology of tin-based oxide
hierarchical structures was tuned by changing the ratio of NaCl :
Na2CO3 from 1 : 1 to 1 : 4.154 The obtained materials were con-
sidered to have potential to be applied as anodes in the battery
industry. In Jin’s work, Mg powder, TiO2, SiO2 (20 : 5 : 3 in molar
ratio), and KCl–LiCl eutectic salt were ground for 15 min.155 The
mixture was then heated (700 1C) in a box furnace for 2 hours.
After washing and drying, electron microscopy images showed the
formation of uniform TiSi5 nanoparticles.
Graphene based carbon materials can also be prepared by
using a molten salt. Amorphous carbon is regarded as a
valuable alternative to commercial graphite as anodes for
lithium ion batteries because it can reversibly store a lot of
lithium ions. Wu and coworkers introduced a simple route for
the synthesis of ultrathin amorphous carbon nanosheets from
petroleum asphalt in large scale.156 The carbon nanosheets
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Fig. 15 Eutectic metals for preparing materials. (A) Synthesis of PMDA based COFs in a eutectic salt mixture, TT–PMDA: 2,4,6-tris(4-aminophenyl)–
triazine pyromellitic dianhydride, TAPA–PMDA: 2,4,6-tris(4aminophenyl)–amine pyromellitic dianhydride.148 Reproduced with permission from ref. 148.
Copyright 2020 John Wiley and Sons. (B) Sectional schematic of the vertical driving force and horizontal liquid transport. (C) When sulphur vapor was
introduced early, the Na2Mo2O7 precursor rapidly formed the MoS2 seed layer when exposed on the surface. (D) When sulphur vapor was introduced
later, the MoS2 seed layer was formed at the solid–liquid interface, thus leaving a droplet of the liquid precursor on top of the interface. Optical image of
monolayer (E) and bilayer (F) MoS2. Scale bar is 50 mm.149 Reproduced from ref. 149 with permission from the Springer Nature, copyright 2020.

prepared in this work were high performance anode materials
for lithium ion batteries. The electrodes delivered a high
reversible capacity, outstanding rate capability, and superior
cycling performance (579 and 396 mA h g1 at 2 and 5 A g1
after 900 cycles). This research not only paved the way for the
synthesis of carbon electrode for battery industry, but also
expanded the application of molten salt in advanced field.
Chen et al. reported a gas–liquid–solid method to prepare
micron-sized MoS2 films.149 A eutectic mixture in liquid is
formed by mixing MoO3 and NaF, which is then sulfided into
MoS2 (Fig. 15B). The formed MoS2 seed crystal acts as a cover-
ing layer, which can reduce nucleation density and promote
lateral growth. By adjusting the driving force of the reaction
(timing of introducing sulphur vapour), large single/double-
layer flakes can be grown on a centimeter-level substrate
(Fig. 15C–F). The field-effect transistor made of the full-
coverage film showed high mobility. This method overcomes
the bottleneck of conventional chemical vapor deposition reaction
and is expected to realize the preparation of two-dimensional
materials in large scale.
Different from the previous HF etching method of Mxene
precursor, Gogotsi et al. proposed a method of using molten salt
synthesis.157 A KF–NaF–LiF system was used to etch the aluminium
atomic layer in Ti4AlN3 under an argon atmosphere at 550 1C. The
resulting MXene was further stripped to produce several-layer
nanosheets and monolayer films of Ti4N3Tx. This method can
avoid the use of corrosive acids and is safer during operation.
Eutectic salts can also act as solvents or catalysts for gas
synthesis and conversion. Methane reforming and methane
pyrolysis are currently important sources of hydrogen. In
McFarland’s work, a ternary salt system (FeCl3–NaCl–KCl) was
found to be catalytic for methane decomposition (Fig. 16A).158
It is believed that the reduction of activation energy is due to
the presence of Fe species, which facilitate the pyrolysis of
methane.
The reduction of nitrogen to ammonia has been a hot topic
in recent years.160,161 However, the catalytic reactions in aqueous
solutions are facing a major challenge, that is, the hydrogen
evolution reaction. Tsang et al. reported a method to directly
reduce nitrogen to ammonia in a molten salt electrolyte, which
provides a new idea for the development of this field.159 Li3N
in the eutectic salt will promote the spontaneous chemical dis-
proportionation of H2 into H and H+, resulting in the release of
the product, NH3. The catalytic cycle is shown schematically in
Fig. 16B.
Du et al. described a strategy from the changes of the
vanadium valence state and mineral phase, and the promotion
of vanadium oxidation by molten salt was realized.162 In addition,
synthesis of silicate and zirconate powders by molten salts was
also reported.163,164
4.3 Liquid metal batteries
In foregoing paragraphs, eutectic alloys and eutectic salts were
introduced. By coupling eutectic metal and eutectic salt, all-liquid

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Fig. 16 (A) Photo and schematic diagram of device for methane
pyrolysis.158 Reproduced with permission from ref. 158. Copyright 2020
American Chemical Society. (B) Catalytic cycle proposed for electro-
chemical NH3 synthesis in molten LiCl–KCl–LiH. Species added to the
reaction are shown in blue, remaining species in black are generated
in situ, sole product NH3 is shown in green. Red dashed lines indicate
opportunities for unproductive side reactions.159 Reproduced with
permission from ref. 159. Copyright 2019 John Wiley and Sons.
electrical cells can be achieved. More excitingly, they do not
require any membrane. A liquid metal battery consists of two
liquid metal electrodes separated by a molten salt electrolyte that
self-segregates into three layers based upon density and immisci-
bility (Fig. 17).11,165 Metals A and B can form eutectic alloys, which
can reduce the working temperature. At this temperature, eutectic
molten salts between electrodes act as both conductors and
metallic suppliers. For example, alloying Sb with Pb has been
known to achieve significant reductions in the melting point of
the positive electrode as well as the cell operating temperature
without an attendant decrease in cell voltage. The process not only
lowers the cost of Li–Sb–Pb batteries, increasing their attractive-
ness for stationary applications, but also serves as an example of
how to broaden the selection of positive-electrode materials for
liquid metal batteries. Sadoway and coworkers described a Li–Sb–
Pb liquid metal battery that potentially meets the performance
specifications for stationary energy storage applications.166 This
Li–Sb–Pb battery consists of a liquid lithium negative electrode, a
molten salt electrolyte, and a liquid Sb–Pb alloy (18 : 82 in molar
ratio, Tm is 253 1C) positive electrode, which self-segregates by
density into three distinct layers owing to the immiscibility of the
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Fig. 17 Schematic diagram of a liquid metal battery upon (A) discharging
and (B) charging.11
contiguous salt and metal phases. The all-liquid construction
confers the advantages of higher current density, longer cycle life
and simpler manufacturing of large-scale storage systems
(because no membranes or separators are involved) compared
to those of conventional batteries. At a charge–discharge current
density of 275 mA cm2, the cells cycled at 450 1C with 98%
coulombic efficiency and 73% round-trip energy efficiency.
In Sadoway’s review, electrodes and electrolytes with
the desired characteristics are constrained according to the
following requirements (Table 4).11
5. Deep eutectic solvents
Water is the most common solvent, and aqueous solutions
indeed represent a widely used class of polar solvents with
excellent properties. However, in certain environments, water-
based solvents have disadvantages. For example, the use of
water-based solvents will result in hydrogen evolution side-
reactions during the electrodeposition process, and some
organic reactions require an anhydrous environment. There-
fore, the development of non-aqueous solvent systems has
attracted increasing attention.
DESs are a family of environmentally friendly solvents that
are composed of an ionic compound such as a quaternary
ammonium salt and a molecular compound such as a polyol.14
They have been applied in various fields since they were
proposed by Abbott et al. in 2003.14,167 When components that
constitute the DESs are primary metabolites, the DESs are so
called NADES (meaning natural DESs). The versatility of NADES
is comparable to that of ionic liquids with their great advan-
tages being their much lower cost and high sustainability.168
Therefore, NADES are called the solvents for the 21st century.
In 2014, Abbott et al. redefined four types of DESs (Table 5).169
The third type is the most popular category because of its
excellent properties and diversity. Owing to increasing demand,
a large number of DESs have been prepared for different
applications. It is necessary to study their properties.
5.1 ILs and DESs
At first, ionic liquids (ILs) referred to pure salts or eutectic salts
in molten state. With the deepening of research, ILs have
gradually evolved into different types (Fig. 18A).170 Room
temperature ionic liquids (RTILs) are regarded as the missing
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Table 4 The selection of properties in liquid metal batteries11
Electrodea
 Tb 4 25 1C, Tm o 1000 1C
 Electrically conductive, with a minimum electronic conductivity
greater than the ionic conductivity of a typical molten
salt electrolyte (s 4 1 S cm1)
 Nonradioactive
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a
In this part, the candidates of electrode materials are pure metals.
Table 5 General formula for the classification of DESs169
Type General formula
+ 
Type I Cat X zMClx
Type II Cat+XzMClxyH2O
Type III Cat+XzRZ
Type IV MClx+RZ = MClx1+RZ + MClx+1
link between aqueous/organic solutions and high temperature
molten salts.171 Their high thermal stability and wide electro-
chemical windows make them good candidates for application
in in electrochemistry, biochemistry, engineering, physical
chemistry, and analytical chemistry.172 Many properties of ILs
can be tuned by changing the combination of anions and
cations according to their applications. In addition, chemical
modification of ions (usually cations) improves their perfor-
mance as task-specific solvents. A longer alkyl chain in cation is
believed to be beneficial for lowering its melting point. ILs with
long side chains exhibit a bicontinuous morphology, one
region consists of polar moieties and the other of apolar, alkyl
tails (Fig. 18B).173 As analogues of RTILs, DESs also possess
polar and apolar domains in nanoscale. Studies have shown
that the applications of DESs almost cover those of ILs in many
fields. What’s more, the preparation process of DESs is much
simpler than that of ILs. Therefore, DESs can also be regarded
as the development of eutectic salts.
Fig. 18 (A) The evolution of ionic liquids. (B) Comparison of ionic liquid
and DES.
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Electrolyte
 Low melting temperature
 A density intermediate between the positive and negative
electrodes to facilitate the self-segregation of three liquid layers
 Minimal metal solubility
 No irreversible side reactions of spectator ions within
the operating voltage window
 High ionic conductivity for high-rate capability and energy efficiency
Terms
M = Zn, Sn, Fe, Al, Ga, In
M = Cr, Co, Cu, Ni, Fe
Z = CONH2, COOH, OH
M = Al, Zn and Z = CONH2, OH
5.2 Formation of deep eutectic solvents
Researchers claim that hydrogen bonding interaction in DESs
is the reason for the formation of eutectic systems.31 It can be
interpreted that the hydrogen bonding interaction between
hydrogen in molecules and anions hinders the crystallization
of the whole system. Although this seems to be a generally
accepted explanation, it is ambiguous as well. When increasing
the strength of hydrogen bonds between the hydrogen bond
donors (HBDs) and hydrogen bond acceptors (HBAs), it seems
that negative charge will spread more from the anions to the
organic compounds, whereas the positive charge will locate
more strongly around the cations. However, in Mollenhauer’s
work, it showed that the negative charge transferred from
chloride to urea in choline chloride urea mixtures was
negligible.174 Thus, they raised a question: is the charge delo-
calization occurring through hydrogen bonding between the
halide anion (the HBA) and the organic compound (the HBD)
responsible for eutectic? This inspired researchers to continue
to explore the intrinsic reasons for the formation of eutectics.
Nonetheless, hydrogen bonding interaction is widely
believed to be one of the reasons for eutectics. Almost all
researchers will conduct experiments to verify the formation
of a eutectic system after preparing a DES. Common character-
ization studies are IR, nuclear magnetic resonance (NMR), and
differential scanning calorimetry (DSC).175–178 For example, the
displacement and change of characteristic peaks in the IR
spectra are supposed to be an evidence for the formation of
hydrogen bonding interaction, and the principle of NMR is the
same. These microscopic spectra combined with macroscopic
information such as melting point and phase diagram are
believed sufficient to explain the formation of the eutectic
system. However, with the achievement of instruments and
simulation methods, some more profound topics are studied.
In Zahn’s work, the ab initio molecular dynamics simula-
tions of reline (ChCl : urea = 1 : 2) reveal similar hydrogen
bonding interactions in spatial distribution between both
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Fig. 19 Spatial distribution function of Cl (green, isosurface 20 nm3)
and Ourea (red, isosurface 20 nm3) close to choline (A) and urea (B).179
Reproduced with permission from ref. 179. Copyright 2017 Royal Society
of Chemistry. (C) A hypothetical diagram of eutectic mechanism, balls in
blue and red represent different molecules.
constituents (Fig. 19A).179 In addition, chloride anions and the
oxygen atoms of urea also show a similar spatial distribution
around the cationic core of choline (Fig. 19B). There are
undetectable cluster migration which is induced by multiple
similar interactions, and fast hydrogen bonding dynamics
facilitated by the hydrogen atoms contributes to the low melt-
ing point of reline. In pure substance (salt), the anions and
cations combine with each other; in DES, this combination is
broken by the molecular compound, that is, cations and
hydrogen compete for anions.
In addition to the formation of hydrogen bonding interaction,
the increase in entropy is considered to be another important
change in the mixed system. In a pure substance, molecules or
ions (simplified as balls with different colour) arrange regularly;
while in DES, molecules or ions are disordered (Fig. 19C). When
forming a new mixing system, the microenvironment around the
original molecules becomes more complex. Marcus studied
the entropy change of DES formation.180 It has been proved that
the mixing entropies are positive, due to the increased amount
and kinds of hydrogen bonds present in the DESs compared to
those in the components. The standard entropy DSy of a DES is
derived from the densities or crystal structures of HBA and HBD.
These values are compared with those of single components
(according to the molar ratio) to obtain the standard entropies
of DES formation DSf. It seems that the formation of new
hydrogen bonding interactions and the increase of entropy are
not contradictory, but are mutually responsible. This sort of
noncovalent interaction (i.e. hydrogen bonding interaction) is so
strong that it leads to the low-selectivity of molecular binding.
This low-selectivity makes the mixture system difficult to form
crystals, so the solidification point will be reduced.
There is also a study that shows that DESs are able to form
ionic hydrogen bonds.181 Evidence has been found for a
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tripodal CH  Cl doubly ionic H-bond motif. In reline, the
strongest H-bond forms between urea and choline, rather than
the hydrogen bond between urea and chloride anions. In Hunt’s
work, an ‘‘alphabet soup’’ model was proposed. It was also found
that there are different types of H-bonds (OH  OQC,
NH  OQC, OH  Cl, NH  Cl, OH  NH, CH  Cl, CH  OQC,
NH  OH and NH  NH) in reline, which exhibited high diversity.
It is anticipated that these noncovalent interactions will have a
significant impact on the entropy of the system, and, thus could
play an important role in the formation of the eutectic system.
No essential structural change has been detected from
liquid to solid, demonstrating that the solidification of the
DES (molar ratio ChCl : malic acid = 1 : 1) is a glass transition
rather than a first order phase change.182 Quasi elastic neutron
scattering (QENS) data support this by showing a gradual
change in solvent dynamics rather than a step change. The
finding of structure in DESs will help to further understand the
mechanism of these green solvents on a molecular scale during
the chemical processes, and, the role of natural DESs in plant
physiology.
5.3 Properties of DESs
In this part, the heterogeneity of DESs is discussed, which may
be helpful to unravel the intrinsic mechanism of their excellent
solubility properties. Thanks to advanced neutron scattering
technology and molecular dynamics simulation, the complex
hydrogen bonding networks in DESs have been studied.
In general, measuring the physical properties such as density
and viscosity of DESs is the basis for their industrial use.183
Compared with water and some volatile organic solvents, DESs
possess a relatively high viscosity. However, it is very instructive
that adding a certain proportion of water may not affect the
microstructure of DESs, which implies that the viscosity of
the solvent system can be reduced by dilution. For a particular
DES, the proportion of water can be as high as 83%.184 This
suggests that dilution can greatly reduce the costs in industrial
applications.
In addition, thermodynamic properties such as enthalpy
change, entropy change, and melting point are also discussed.
Thermal stability is a key property for DESs because it deter-
mines the maximum operating temperature. Some existing
thermal stability laws are summarized, and a new test method
is also given to test the thermal stability of DESs under long-
term heating. Apart from measuring and testing, there are
physical and chemical properties such as melting point predic-
tion through formula derivation and machine learning.185,186
The results of simulation data show excellent correlation with
those of some testing experiments.
Finally, the electrochemical properties of DESs are dis-
cussed, which contribute to the development of a battery. DESs
have good conductivity and wide electrochemical windows, and
are expected to make breakthroughs in this field.
5.3.1 Heterogeneous structure in nanoscale. Once we have
determined the existence and function of hydrogen bonds in
DESs, an important question arises. We know that there are
hydrogen-bonding interactions in each eutectic system, but in
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what form? This depends on the internal structure of the DES,
which is important for further applications. Edler et al. carried
out a liquid phase neutron diffraction experiment on reline.189
A hydrogen-deuterium isotope substitution was used to obtain
cross-sections of differential neutron scattering, and a cor-
rected empirical potential energy structure model was fitted
based on experimental data. The result of the radial distribu-
tion function revealed the existence of a hydrogen-bonding
network in DESs. These networks exist not only between urea
and chloride but also between all species in DESs with impor-
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tant and orderly interactions. The hydroxyl group in choline
was found to play a decisive role in the bonding network.
In addition to the hydrogen-bonding network, strong ion pairs
were also proved to exist in some non-choline DESs.190 Does
this simply mean that DES is closer to ionic solvents? Hapiot‘s
work negated this question. From the results of electron trans-
port kinetics, ethaline (choline chloride : ethylene glycol = 1 : 2)
seems to be more similar to a molecular solvent than an IL or
an aqueous solution.187 The electron transfer in ethaline is
relatively faster than in most of the ILs, while similar to that in
water. Kinetic rate constant in ethaline is more than 1 order of
magnitude larger than its estimation from the longitudinal
relaxation times (Fig. 20A).
Fig. 20 (A) The deviation of Ethaline DES from the aqueous solution and
classical ionic liquids, BMF-TFSI: 1-butyl-1-methylpyrrolidinium bis-(tri-
fluoromethylsulfonyl)imide, EMIM-BF4: 1-ethyl-3-methylimidazolium
tetrafluoroborate.187 Reproduced with permission from ref. 187. Copyright
2020 American Chemical Society. (B) A schematic representation showing
different domains/regions in DESs and possible locations of various solutes
in these regions.188 Reproduced with permission from ref. 188. Copyright
2018 Royal Society of Chemistry.
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Despite the formation of a ubiquitous hydrogen bonding
network, a DES as liquid phase is inevitably heterogeneous at
nanoscale (Fig. 20B). In other words, on the nanometer scale,
there are high-polarity regions and low-polarity regions in a
DES. Samanta et al. studied the structure and dynamics of some
carefully chosen systems.188 The results showed that, when the
chain length of one of these solvents increases, both spatial and
dynamic heterogeneity increases. However, with the change of
hydroxyl position, no obvious heterogeneity was observed.
Kashyap et al. studied lithium perchlorate based DESs using
X-ray and neutron scattering.191 The scattering structure func-
tions and correlation between the ion species reveal that the
nano-heterogeneity in DESs increases with increasing tempera-
ture. This heterogeneity in nanostructure helps people under-
stand the excellent solubility of DESs, which will be discussed
in the following paragraph.
The excellent solubility of DESs is believed to originate from
this nano-inhomogeneity. Golgoun et al. compared the solubi-
lity of 6 drugs (acetaminophen, naproxen, celecoxib, piroxicam,
meloxicam and betamethasone) in water and different DESs at
a certain temperature range, and used dynamic light scattering
measurement and polarized optical microscopy to gain an
in-depth understanding of the interactions between drugs
and each single component of DESs.192 The results showed
that the solubility of drugs in DESs is significantly improved
compared with that in water. Hansen solubility parameter is
used to evaluate the performance of DESs during the solubili-
zation process. This method is hoped to be useful in studying
the solvent behaviour in other fields.
b-Cyclodextrin (b-CD) is a typical amphiphilic molecule; the
hydrophobic part of the inner cavity can accommodate oily
molecules, thereby increasing its dispersion in polar solvents.
In addition, b-CD can be used for targeted drug delivery. Small
angle X-ray scattering proved that quite a large amount of b-CD
(at most 800 mg mL1) can be dissolved in reline, which is
much larger than 18 mg mL1 in water.193 At the micro level,
hydrogen bonding and hydrophobic interaction determine the
solvation of b-CD, which is also a strong proof of the hetero-
geneity in DESs. The above typical developments benefit drug
design and delivery. The results of small angle X-ray scattering,
dynamic light scattering, and transmission electron micro-
scopy demonstrated that DESs can be an alternative choice
for the growth of nanoparticles restricted by water.194 This
characteristic helps to prepare some nanomaterials with special
morphology.195
The results of some other small-angle scattering experi-
ments showed that some DESs are excellent solvents for macro-
molecules such as proteins and polymers.196–198 They can even
provide the environment where proteins can retain their
specific structure.
5.3.2 Solvation and interface properties. The microenvir-
onment and solute–solvent interactions in DESs are critical for
their potential applications, such as extraction and separation.
Therefore, in addition to the heterogeneity which has already
been described above, solvent kinetics of DESs has been
studied. Amphiphilic nanostructure (i.e. microheterogeneity)
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in liquid is important for dissolution. Atkin and coworkers
revealed that the cation alkyl chain is the signature of amphi-
philic liquid nanostructure in tetra-alkyl ammonium based
DESs.199 The ability to form amphiphilically nanostructured
DESs highlighted the possibility that other interfacial proper-
ties of ionic liquids could be extended to the field of DESs.
In another work, Kashyap and coworkers used molecular
dynamics simulations to investigate the structural morphology
of molecule in bulk and at the graphene interface (neutral and
charged).200 It revealed that there is not only a complex
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structure in bulk DES, but also a layered structure on the
surface of the electrode, and the latter varies significantly with
the size of the charge carried by the electrode. This conclusion
contributes to the electrochemical application in DESs.
Bagchi et al. used single molecule based fluorescence corre-
lation spectroscopy techniques and set based time resolved
fluorescence anisotropy measurement methods to study the
translational and rotational diffusion dynamics of species in
the eutectic system.175 The results showed that the spatial and
dynamic heterogeneity of these DES becomes more prominent
in cation systems with longer alkyl chain length, which is
consistent with Atkin’s experimental results. The results also
showed that as the chain length increases, the kinetics of the
solvent decreases monotonously, which leads to an increase in
viscosity.201
DESs can be used to prepare dynamic soft templates because
they can guide the growth of nanoparticles with limited size or
shape in water restricted media.202 It is also reported that the
aggregation of surfactants is attributed to the hydrophobic
interaction between them and the alkyl chain of DESs.203
In addition to commonly used surfactants, Warr et al. studied
the chain melting temperature of phospholipids by X-ray
scattering.204 Chain melting is most sensitive to the length of
the alkyl chain of the cation, which is consistent with the
experimental results of solvation kinetics.
5.3.3 Density and viscosity. In recent years, there have been
few publications solely on density and viscosity of DESs.
Instead, some experiments on density and viscosity (if any)
are placed in front of application experiments as less important
content.205,206 These physical properties are not meaningless,
they are more important in industrial research. While in
academic research, they are usually studied in combination
with other microscopic dynamics. According to Pandey’s work,
the density of reline decreases with increasing temperature,
following a quadratic expression.207 It was found that at all
temperatures and compositions, the molar volume of the
excess linear aqueous mixture is negative. Generally, as the
temperature increases from 293.15 K to 323.15 K, the absolute
excess molar volume decreases. Hydrogen bond is suggested to
be the cause of this phenomenon. It is further proved that the
HBDs dominate the interaction in DESs and their aqueous
solutions, and the important role of HBDs has been fully
emphasized. In addition, most experimental data showed that
the density of DESs has a good linear relationship with tem-
perature, and the viscosity fits the commonly used Arrhenius
equation.208 Contrary to density and viscosity, conductivity and
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excess molar volume ratio show a tendency to increase with
increasing temperature.209 Understanding the laws of these
volume properties is of great guiding significance for indus-
trialization practice.
Buchner et al. studied the density and viscosity of reline
under ultra-dry conditions.210 At 298.15 K, when the water
content is 0.81%, the density decreases by 0.14%, while the
viscosity decreases by 36%. This shows that water has different
effects on different properties. By dilution, some properties can
be adjusted without changing other properties. Although DESs
have emerged as designable solvents for many applications
such as catalysis and separation engineering, their high visc-
osity may hinder their usage in the field of bioactive
components.211,212 An efficient method to reduce viscosity is
dilution. Because the internal structure (especially in nano-
scale) may vary remarkably, studying the whole system is
important.213,214
It has been proved that some DES–H2O systems have better
performance and lower cost.215 With the help of advanced
experimental technology, the internal nanostructure of hydrated
DESs with complexed interaction mechanism can be studied. In
Edler’s work, the nanostructure of a series of ChCl/urea/water
mixtures across a wide hydration range were characterized
by neutron total scattering and empirical potential structure
refinement.184 The result showed that the nanostructure of reline
is retained at a pretty high level of water (ca. 42 wt%), while at 51
wt% or 83 mol% H2O, the structure of reline is disrupted. Under
high hydration conditions, water–water and DES–water interac-
tions dominated instead of the inner interactions between single
components (Fig. 21). Consequently, they proposed that at and
above 83 mol% H2O, the DES–water mixture can be best described
as an aqueous solution.
The above work has a great significance for proving the role
of water in DESs, and it draws a line between DES and their
aqueous solutions. However, one of the shortcomings is that
it only studied one DES (reline), while the properties of
different eutectic systems vary greatly. For example, Kashyap
et al. applied a molecular dynamics simulation research on
ethaline.216 The result showed that the change of ethaline from
a ternary system to an aqueous solution is a step change. When
the water content exceeded 40 mol%, hydrogen bonding
between ethylene glycol and each hydrogen bonding acceptor
was sharply destroyed. Similar to Edler’s work, the research
result of Kashyap et al. showed that the effect of water on the
structure of DES is nonlinear. Above a certain critical water
content, the hydrogen bonding network between the two
monomers of DES begins to break. In reline, the critical water
content is 42 mol%, while in ethaline this number is 40 mol%.
However, there are still certain differences. The dividing line of
aqueous solution in reline is 83 mol%, while in ethaline, it is
62.5–76.9 mol%. Since the above two DESs have the same HBA,
quantifying the effects of water on different HBDs is worth for
further investigation.
5.3.4 Enthalpy and entropy change. As mentioned above,
entropy change is an important reason for the formation of
DESs. The process of mixing the two monomer compounds
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Fig. 21 Spatial density function plots describing the 3D nanostructure of
DES with water. Isosurfaces represent urea (lilac), chloride (green), choline
(yellow), and water (blue) molecules at the 7.5% probability level.
T‘he central molecules from left to right are choline, urea, and choline
respectively. ChCl : urea : water 1 : 2 : 1 and 1 : 2 : 15 in molar correspond to
the top (1w) and bottom (15w) respectively.184 Reproduced with permis-
sion from ref. 184. Copyright 2017 John Wiley and Sons.
increases the entropy, which makes the eutectic system more
stable. One of the most important prerequisites for applying
DESs is to understand their phase behaviour. The non-ideality
of the phase behaviour is determined by the contribution of
excess entropy and enthalpy. Although the total Gibbs free
energy change of the mixing process can be inferred from the
solid–liquid phase behaviour, the contribution of entropy and
enthalpy is difficult to be distinguished, respectively. With et al.
proposed two entropy models in non-ideal situations in order to
predict the phase behaviour of DESs.217 They found that the ideal
mixing entropy underestimates the entropy contribution of the
components in a mixture, and the molar volume employed has a
significant impact on the entropy and enthalpy changes during
the mixing process. Recent research has shown that the formation
processes of some common DESs are an endothermic process
(DH 4 0).218 The corresponding molar enthalpy change ranges
from 1.90 to 5.35 kJ mol1. A deeper conclusion is that, non-
covalent interactions between the molecules in pure components
are stronger than those in eutectics. Interestingly, this work
reported the decisive roles of HBA in affecting the entropy change.
Lu et al. studied the enthalpy change of the hydration
process of 3 ratios of choline chloride/urea eutectic systems
at 308.15 K and 318.15 K.219 As the water content increases,
ChCl/urea (1 : 2.5) showed endothermal behaviour over the
entire range; while ChCl/urea (1 : 1.5) and ChCl/urea (1 : 2)
showed endothermic behaviour first, which then changed to
be exothermic (Fig. 22). This result showed that when there is a
lot of water in the mixture, the intermolecular interaction
between DES–DES and water–water is stronger than that of
DES–water. As the content of DES in the mixture increases, the
DES–water interaction changes to take the dominant role, and
the eutectic system shows an exothermic behaviour.
All in all, the entropy change and the enthalpy change are
critical to assess their potential in practical applications on an
industrial scale.
5.3.5 Melting point and thermal stability. Almost all the
research on DESs include the characterization of the melting
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Fig. 22 Molar enthalpy of mixing Hm (with water) for ChCl/urea at
different molar ratios (1 : 2.5, 1 : 2, 1 : 1.5). Blue points are experimental data
at 308.15 K: (E) 1 : 2.5, (m) 1 : 2, and (K) 1 : 1.5; black points, experimental
data at 318.15 K: (}) 1 : 2.5, (n) 1 : 2, and (J) 1 : 1.5. Curves: calculated
results from nonrandom two-liquid model.219 Reproduced with permis-
sion from ref. 219. Copyright 2016 American Chemical Society.
point (phase transition point) of the eutectic system. A phase
diagram is required to prove the formation of a eutectic system,
or at least to verify that the melting point of the mixed system is
lower than that of each single component. However, different
researchers hold different views about the melting point in the
definition of DESs. Some people have a strict definition of
DESs: the melting point of the mixed system must be lower
than the melting point of any pure component, and lower than
25 1C. Others claim that the melting point of DES only needs to
lower than every single component. Here, authors advocate that
it may be helpful to review the history of RTILs. In the early
days, researchers referred to ILs with a melting point below
25 1C as RTILs. However, with the deepening of research
and applications, the definition of RTILs has been enlarged
(melting points below 100 1C). Therefore, the broad definition
of DESs related to the melting point is beneficial to their
development.
The characterization of melting point is usually conducted
by DSC, supplemented by optical microscope and other instru-
ments. A phase diagram is completed by linking the phase
transition points on DSC curves. This series of operations is not
difficult. However, it is worth mentioning that a number of
DESs do not possess a real melting point, but have a glass
transition temperature.220,221 The reason for this phenomenon
is still under study, and hydrogen bonding is believed to hinder
the crystallization of the eutectic systems. Therefore, some
DESs are called low-transition temperature mixtures.222
DESs as the analogue of ionic liquids are considered to be
less volatile. However, it is still necessary to study their thermal
stability. Research has shown that DESs have low but detectable
vapour pressure under ambient conditions.223 The essence of
vapour pressure is considered to be the result of volatilization
of one or all components in DESs. A systematic research on the
thermal stability of 40 DESs by thermal gravimetric analysis
(TGA) was carried out.224 It was found that the decomposition
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process of DESs is different from that of ionic liquids.225 DESs
are multi-component systems, although there is a strong inter-
action between each single component. When heated, DESs
will undergo a two-stage decomposition process. First, the
relatively volatile molecular components (usually hydrogen
bond donors) will evaporate, followed by the decomposition
of the remaining components. The strength of the hydrogen
bond determines the volatilization rate of the HBD, and thus
the onset decomposition temperatures (Tonset). The thermal
stability of DESs is largely affected by the thermal stability of
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HBD. In addition to TGA, FT-IR and 2D-IR were used to study
the volatility and long-term volatility of DESs.226,227 It was
demonstrated that some DESs are volatile under ambient
temperature and pressure, and it is necessary to pay attention
to the tightness of the container in industrial scale.
In a recent work, the thermal stability of 8 ChCl-based DESs
(of which the HBDs are levulinic acid, malonic acid, glycerol,
ethylene glycol, phenylacetic acid, phenylpropionic acid, urea,
and glucose, respectively) has been studied using thermal
gravimetric analysis/Fourier transform infrared-attenuated
total reflectance spectroscopy (TGA–FT-IR-ATR) techniques
under isothermal conditions.228 By this method, the structural
transition, temperature, and duration of DESs can be con-
firmed, respectively. The Tonset of DESs obtained using TGA
was significantly lower than those obtained using TG–FT-IR-ATR.
It is worth thinking about using traditional TGA to analyse
the application (especially long-term application) temperature
of DESs.
These research work can help understand the decomposing
dynamics of DESs and provide guidance for designing DESs
with appropriate thermal stability.
5.3.6 Electrochemical properties. DESs are also supposed
to be a class of ideal candidates for electrochemical systems
due to their ionic conductivity, and environmentally friendly
and relatively stable nature.169
In electrochemical research, transport properties such as
viscosity and conductivity are of vital importance. Recent
reports have shown that the displacements associated with
the localized diffusive motions are actually larger for choline
when the diffusion dynamics are analysed on the sub-
nanoscale.229 Loidl and coworkers did a thorough research on
reorientational relaxation dynamics and the ionic charge trans-
port of 3 DESs by broadband dielectric spectroscopy.230 The
experiments cover a broad temperature range from low viscosity
liquid to the deeply super cooled state, which allowed them to
investigate the significant influence of glassy freezing on the ionic
charge transport in these systems. Moreover, they threw light
on a close coupling of the ionic conductivity in these materials
to reorientational dipolar motions, which should be consi-
dered when designing DESs optimized for electrochemical
applications.
DESs have been proven to have very good electrical conduc-
tivity, so they are considered for the preparation of flexible
electronic devices. Soin et al. synthesized polymer electro-
lytes by electrospinning technology, and then immersed them
in a series of DESs to enhance the electrical conductivity of the
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composite.231 After being immersed in DES (N,N-diethyl-
ethanolammonium chloride : ethylene glycol = 1 : 2), the con-
ductivity of the membrane increases nearly 10 000 times. Cyclic
voltammetry experiments show that the linear diffusion is
common in DESs.232 In addition, semi-integrative voltammetry
has proved to be a good tool for studying simple electrochemi-
cal systems in DESs.233
Although some of their properties were well studied, the
interfacial especially the electrified confined properties have
barely been investigated. To benefit the applications of DESs in
the electrochemistry field, Proft and coworkers illustrated the
electrical double layer structures of reline by atomistic mole-
cular dynamics simulations.234 The result showed that urea
molecules are adsorbed on both positive and negative electro-
des. Whereas choline ions tend to adsorb on the negative
electrode, chloride ions tend to adsorb on the positive electrode
(Fig. 23A). More than this, urea tends to be perpendicular to
negatively charged graphene, while being parallel to positively
charged graphene (Fig. 23B). This may result in the first layer of
the negative electrode being thicker than that of the positive
electrode. The conclusion of this study provided new insights
into the electrical double layer structures of DESs. The inter-
facial structure can be tuned at the molecular level.
5.4 Applications of DESs
Understanding the properties of DESs is conducive to utilizing
them, and then, extending new applications. As a class of green
solvents, they are widely used for dissolution and separation.
Many natural products can be dissolved in DESs. By designing a
task-specific system, the target product can be dissolved in it,
while the impurities are insoluble. In this way, the purified
target product can be obtained simply by effective filtering.
Moreover, the filtrate can be used directly to carry out a series of
chemical reactions, such as the conversion of cellulose to
5-hydroxymethylfurfural.238–241 In addition, many DESs possess
good electrical conductivity and can be used as electrolytes in
batteries and electrocatalytic reactions. Inspired by the hydro-
thermal and solvothermal methods, DESs have also been used
to synthesize nanomaterials. In some reactions, DES only serves
as a solvent; while in other reactions, DES participates in
synthesizing materials by decomposition.
5.4.1 Absorption, dissolution, and separation. DESs are
considered as promising absorbents for carbon dioxide,
sulphur dioxide, and other gases, thus contributing to environ-
mental protection.242–244 There are many studies that aimed at
exploring the design and preparation of effective eutectic
absorbents.245 The synergistic effect of anions and cations
has proved to be crucial for capturing CO2. In addition, the
protonated super base plays a key role in the absorption
process. The same with carbon dioxide, and sulphur dioxide
is an acid gas. Therefore, the nitrogen atoms in DESs were
considered to be the binding sites for sulfur dioxide.246,247
Wang et al. used FT-IR and NMR to study the absorption
performance of piperazine-based DES at different SO2 concen-
trations and absorption temperatures. It has been found that
the 1,4-dimethyl-piperazinium bromide/glycerol = 1 : 1 system
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(Fig. 24A). For example, an emulsion was formed when mixing

olive oil and the imidazole/ethylene glycol system. After bub-
bling CO2, the emulsion can be separated into two transparent
phases (Fig. 24B and C).235 Spectral studies have shown that the
intrinsic reason for this phase transition is H2CO3. The acidity
of H2CO3 is stronger than HBDs, leading to the destruction of
the original hydrogen bond in DESs. In this way, the extraction
of soluble substances in water can be achieved. In another
work, Andanson et al. proposed a thermo-switchable DES based
on oleic acid and lidocaine.236 This phase separation was
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believed to be caused by decrease in hydrophilicity. The

Fig. 23 The behaviour of molecules on electrodes. (A) A single and
double adsorption layer on positive and negatively charged electrodes.
Gray clusters represent urea molecules, blue clusters represent choline
cations, and green balls represent chloride ions. (B) The orientation of urea
on positive and negative electrodes (blue represents the graphene elec-
trode with negative charge, red represents the graphene electrode with
positive charge).234 Reproduced with permission from ref. 234. Copyright
2018 American Chemical Society.
can obtain 4.28 mol SO2 per mole of DES at 20 1C and 1 bar. The
tertiary amine groups in DESs were the main interaction sites
for SO2, and this kind of interaction is considered the chemical
bonding. By mixing organic bases and alcohols, CO2-switchable
systems can be prepared.235,248 Alternate blowing of CO2 and N2
can realize the reversible soluble–insoluble phase transition
selected system can accurately achieve phase separation at
26 1C (Fig. 24D and E). Although there is no light-switchable
DES reported till now, authors hold the view that such DESs will
be proposed in the near future. The breakthrough of ionic
liquid provides guidance for designing DESs.249
In Qi’s work, a eutectic system was designed with reference
to the solubility of reactants and products.237 The esterification
reaction of isobutyric acid and isobutanol proceeds in the DES
phase, and isobutyl isobutyrate enters the upper ester phase as
a product.
Metal oxides exist in the form of ore in nature, and sulfate
acid is usually used to dissolve them in industrial hydrometal-
lurgy. However, studies have shown that DES can be a good
substitute for H2SO4.205,206,250,251 In a recent work, Hartley and

Fig. 24 (A) The photos of the initial imidazole/EG–olive oil emulsion. (B) The laser scanning confocal microscopy image of the initial emulsion. (C) The
laser scanning confocal microscopy image of lower phase after CO2 bubbling for 30 min.235 Reproduced with permission from ref. 235. Copyright 2021
Royal Society of Chemistry. (D) Schematic diagram of thermo-switchable DES in water. (E) Evolution of the liquid–liquid phase observed by optical
microscopy of a sample with 50 wt% water and 50 wt% DES, from 25 to 26 1C.236 Reproduced with permission from ref. 236. Copyright 2020 American
Chemical Society. (F) Schematic view of reaction and separation process in DES.237 Reproduced with permission from ref. 237. Copyright 2019 John
Wiley and Sons.

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coworkers studied the effect of acidity and coordination on the
dissolution of metal oxides in DESs.250 Metal oxides turned to
dissolve more in HBDs with stronger coordinating ability. The
surface reaction was accelerated by the subsequent ligand
exchange reaction in liquid. It has also been proved that the
leaching process of metal oxides is selective, and its solubility
largely depends on the lattice energy and the Gibbs energy of
metal oxides. The good solubility of metal oxides in DESs is the
cornerstone for the metal electrodeposition mentioned below.
DESs, especially NADESs, are often used to treat biomass.252
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Gonzalez-Miquel et al. compared the performance of ionic
liquids, organic solvents, biobased solvents and NADESs for
the recovery of biobased organic acids.253 Furthermore, a
reasonable screening method was established to identify sui-
table solvents for the recovery of biobased acids with different
structures. Finally, this work provided guidance for the design
of sustainable separation process of such organic acids. In
another work, Zhang et al. investigated the acidity of various
acid-containing NADESs.254 Chitin in shrimp shells was sepa-
rated by acid–base reaction and hydrogen bond interaction.
This method has replaced the conventional one, which needs
acid, alkali, catalyst, and acylation reagent. A multi-step transi-
tion including decalcification, deproteinization and acylation
can be carried out simultaneously. The results showed that
nano-components, experimental temperature and reaction
time have important effects on the purity and substitution of
o-acylated chitin.
It is well known that hydrogen bonding is one of the most
important intermolecular interactions, and it plays a key role in
the structure of biomass. As mentioned above, the intrinsic
mechanism of dissolving biomass is usually to destroy their
original hydrogen bond network structures. This can explain
why it is necessary to use strong acids or alkalis during the pre-
treatment of biomass in the traditional processes. In a recent
work, Xu et al. have developed an experimental method to
determine the value of hydrogen-binding energy (EHB) as a
function of chemical shift (d) through a linear equation, given
by,271
EHB
ln d þ sd ¼  þA (19)
RT
where d is the chemical shift of hydrogen, sd is the compen-
sated term, and A is a constant. It was found that EHB acts as a
driving force for controllably reconstructing hydrogen bonding
interactions with molecular scissors, which is consistent with
previous studies.272
We have summarized a series of resources, from water to
bitumen, and from metals to organic nutrients, that can be
recycled using DESs (Table 6).
Furthermore, the applications of DESs in the fields of
polymer science and engineering have made great progress,
which comprises the fundamentals studies involving synthesis,
extraction, modification of polymer, and the early develop-
ments on the formulation of DES–polymer products.273 The
combination of DESs and polymers has a high prospect in the
preparation of polymer materials with sustainability. There is
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Table 6 Different resources recycled by DESs
Water255 Sea water, waste water
Metals256 Flue dust
Protein257,258 Oilseed cakes, cod skins
Lipid259 Microalga P. tricornutum
Lignin260 Switchgrass
Chitin254,261 Crustacean shells
Vitamins262 Button mushroom
Rutin263 Sophora japonica
Astaxanthin264 Shrimp byproducts
Flavone265 Chinese herbal medicines
Anthocyanins266 Wine lees
Curcumin267 Herbal tea
Polyphenols268 Chlorella vulgaris
Polygodial269 Pseudowintera colorata leaves
Bitumen270 Oil sands
plenty of room for development in this field, which will be
introduced in Section 5.6.
5.4.2 DESs for batteries. As described above, the electro-
chemical and interfacial properties of DESs make them good
electrolytes to be used for electrodeposition and in batteries.
The electrodeposition process is considered an excellent
method for the selective extraction of minor metals from
complex mixtures. Owing to developments in technology, elec-
trodeposition is not only used to prepare plastics, metals, and
alloys but can also be used to prepare thin-layer materials with
nanostructures. Water is the most common solvent for metal
electro-treatment. However, its narrow electrochemical window
is a hindrance in the electrochemical process. Aqueous solutions
and their related techniques are limited to niche markets and
high-value products because of the high capital investment and
significant costs involved. Therefore, a more ideal electrolyte
should have the following properties: non-flammability, low cost,
low ohmic loss, high solubility of metal compounds, high con-
ductivity, high-quality transfer rate, and a wide electrochemical
window. The solubility of metal-containing compounds in DESs is
higher, and many DESs possess an electrochemical window much
wider than that of water.176,205,274 These two advantages mean
that DESs are excellent solvents for electroplating and other
processes.
Tu et al. reported a method for electrodeposition of Ni films
in DES (ChCl : ethylene glycol = 1 : 2).275 Three voltage profiles
(very high voltage, pulsed voltage and reverse pulsed voltage)
have been tried to prepare films with specific structures on the
nanoscale. Regular nanosheets, aligned nanoribbons, and hier-
archical flowers can be achieved by controlling the operation
modes. Interestingly, the Ni nano-films prepared by electro-
deposition in DES exhibit superhydrophobic surfaces. Further-
more, nickel layer with special morphology showed a relatively
lower corrosion potential during the electrochemical measure-
ments. Brighteners can be added to the electrolyte to improve
the surface finish. Compared with the systems without additives,
nicotinic acid can significantly change the nucleation and growth
mechanism.276 Gold, copper, and other metals can also be
electrodeposited from their salt solutions.277,278
Silva et al. studied the effect of an electric double layer
on the electrodeposition of Zn in two DESs.279 The results of
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Fig. 25 Scanning electron microscopy (SEM) images of Zn deposits
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obtained from 0.3 M ZnCl2 in (A) 1 : 2 ChCl : U and (B) 1 : 2 ChCl : EG at
50 1C, on mild steel at I = 3 mA cm2.279 Reproduced with permission from
ref. 279. Copyright 2011 Royal Society of Chemistry.
extended X-ray absorption fine structure showed that changing
the concentration of the solute could affect the physical proper-
ties of the liquid, although it could hardly influence the
morphology of the deposited Zn. Double layer capacitance
studies indicated that there are differences between these two
DESs, which were believed to be due to the adsorption of
chloride on the electrode. The deposition of platelet-like crystal
in glycol-based DES is attributed to blocking of certain crystal
faces (Fig. 25).
DESs are generally considered non-toxic. However, some
carboxylic acid-based DESs have proven to be ‘‘moderately
toxic’’. This may be related to the protons ionized by acids
because toxicity is dominated by acidity.280 Cordeiro et al.
showed that the toxicity of some DESs cannot be ignored,
and their toxicity can be initially predicted.281 Binnemans
et al. studied the thermal stability and long-term stability of
carboxylic acid–choline chloride DESs.282 They found that DESs
degraded due to the esterification reaction, which mainly
occurred between the carboxylic acid and alcohol parts of ChCl.
The rate of esterification is slow at room temperature, and the
reaction tends to accelerate at high temperature, which is
accompanied by a decarboxylation reaction (generation of
CO2). Fully understanding these properties makes it possible
to design an electrolyte with low toxicity, high stability, and
high conductivity.
Yu et al. demonstrated a low-cost and high-energy Fe–Al
hybrid battery, taking advantage of the desirable properties of
DESs.12 The lattice energy was reduced by forming a eutectic
system, thus the solidification point was depressed. Dissociating
the iron complexes in Fe(126) enabled full charging and dischar-
ging of the battery with a long cycle life. Fe(126) means the DES
with the molar ratio of FeCl36H2O/urea/ethylene glycol is 1 : 2 : 6,
and the same is true for Fe(210) DES. At the same time, Al can be
stripped and deposited stably. When using a 5 mol L1 Fe(210) as
the catholyte, the Fe–Al battery can achieve delivering approxi-
mately 166 W h L1 with an average operating voltage of 1.41 V.
Furthermore, by adding the iron complexes in Fe(126) DES, the
battery achieved the full charge and discharge over 60 cycles
without any apparent degradation. It further provided a new
platform for the development of sustainable redox substances
based on eutectic theory (Fig. 26). Similarly, aluminium-based
DESs can be used as the anolyte in redox flow batteries.283
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Fig. 26 The schematic diagram of the Fe–Al hybrid liquid battery
concept.12 Reproduced with permission from ref. 12. Copyright 2017 Cell
Press Elsevier.
Apart from high efficiency, extreme operating environment,
like ultra-low temperature is another research topic of batteries.
Shahbaz and coworkers used ChCl and ethylene glycol to form
a eutectic system with a melting point of 66 1C.284 The
purpose of their work was to separate glycerol from palm oil-
based biodiesel. In order to lower the viscosity, an amine
compound was used. In another work, ChCl and lactic acid
were mixed (with the molar ratio of 1 : 2) to produce a DES.285
The eutectic system does not possess a melting point in the
strict sense, but a glass transition temperature as low as
77 1C. Although both of above works used DESs for biomass
processing, such low phase transition temperatures, combined
with ionic conductivity, make these DESs promising for low
temperature electrolytes. Recently, Tao et al. reported an ultra-
low temperature electrolyte with a melting point below 130 1C
based on the concept of eutectic.15 In a water/DMSO mixed
electrolyte, the dominated conformation of hydrogen bonds are
formed between OSQO in DMSO and HO–H in water. Therefore,
when temperature drops, the intermolecular hydrogen bond
between DMSO and water prevents the formation of the tetra-
hedral structure of ice. Furthermore, the battery test results
show that the capacity at 50 1C is about 60% of that at 25 1C.
DESs can also be used for recycling metals in batteries.
Lithium ion batteries are alternatives to lead–acid batteries
and are increasingly used in electronic products. Recovering
lithium and related metals efficiently from batteries has become
an important issue for avoiding resource waste. A method to
extract valuable metals in lithium ion batteries by using DESs was
introduced by Ajayan et al.286 According to this method, more
than 90% of lithium and cobalt can be obtained from lithium
cobalt(III) oxide. Other components in battery, such as aluminium
and polymers can be recovered separately. Therefore, DESs are
expected to be applied in industrial scale for extracting valuable
metals from batteries in the future. In addition to substance
separation, the application of DESs in the degradation of white
pollution has also been noted.287
5.4.3 Synthesis and catalysis. Although volatile organic
solvents easily cause environmental pollution and safety
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problems, they are still widely used in production activities.288
DESs are expected to replace these organic solvents due to their
higher designability and less environmental impact. This is the
basis for their use in synthesis and catalytic reactions.
In Srivastava’s work, condensation of benzaldehyde with
active methylene compound was carried out in DES (ChCl :
PEG200 = 1 : 2 in molar ratio, where PEG is polyethylene
glycol).289 Compared to the control group (pure chlorine chloride
and PEG200), yield of the test group can be increased by about
70% (up to 92%). Moreover, the temperature of reaction can be
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researchers to discard the previous highly toxic solvents and
provides an idea for C–H activation based on green and low-
cost solvents.
D’anna et al. reported the ultra-sound assisted Diels–Alder
reaction in DES.297 The combination of ultrasound activation
and DES reduces the reaction time greatly with a good yield,
which is believed to reduce the energy consumption by more
than 99% compared to silent reaction. Furthermore, DESs can
also be used as solvents for bacterial photosynthesis reaction
centres. The reaction centre in DESs can maintain its normal

decreased from 100 to 80 1C. The remaining 28 products can also
be synthesized based on optimized reaction conditions with a
yield of 70–92%. DES can be recycled for 5 times without
significant loss in yield, which showed the possibility of reuse.
Furthermore, DESs can be used for oxidation, esterification of
alcohols, and the synthesis of other compounds.290–292 For exam-
ple, ChCl-based DESs are able to control the reactivity of organic
lithium reagents at room temperature, thus providing a mild
reaction environment.293–295 It is also reported that DESs can
achieve chemical selective addition of inactive imines and quino-
lines at room temperature and in air. This shatters the long-held
dogma that organolithium chemistry needs to be performed
under inert atmospheres. It is safer and more sustainable to use
DESs rather than volatile organic compounds as solvents.
The C–H bond activation reactions can efficiently construct
compounds, and improve reaction efficiency and atomic econ-
omy, and have received numerous attentions in recent years.
Organometallic reagents are usually used in direct arylation
and are sensitive to air and moisture and expensive. The
difficulty of this type of reaction is the choice of solvent. Highly
polar and highly toxic compounds such as N,N-dimethyl-
formamide, N,N-dimethylacetamide, and N-methyl-2-pyrro-
lidone are the common choices. Farinola and coworkers
reported a thiophene–aryl coupling reaction via direct C–H
bond activation in DES for the first time.296 This strategy allows
function and even perform its natural photocycle.298
5.4.4 Preparation of materials. Materials science is a sub-
ject concerned with human life. From daily necessities to
spacecrafts, materials science has made a great deal of success.
Recent works related to the preparation of materials espe-
cially nanomaterials by using DESs were sorted out (Table 7).
In addition to simple preparation, the application of DES-
obtained materials has been studied.299,301 For example, Sn/
SnO2@C can be used for supercapacitors, while Ni2P@G for
electrochemical overall water splitting. Despite the large number,
the materials summarized in Table 7 follow the following logic:
from carbon materials to carbon composites, from other non-
metallic materials to metals and alloys, and from metal oxides to
metal complexes.
Duarte et al. demonstrated the possibility of using NADESs
as polymer plasticizing agents to develop 3-dimensional porous
materials.317 These materials are supposed to have applications
in a wide variety of fields, which makes this work contribute a
lot to the fields of green chemistry and chemical engineering.
An interesting phenomenon has been noticed. Sometimes,
the molar ratio of two components was tunable.299,306,309,314
That is to say, not all the liquids used were eutectic mixtures.
There are also liquids with a molar ratio different from that at
the eutectic point.304 But all these efforts were aimed at
synthesizing target materials. Moreover, the liquids used in

Table 7 Materials synthesized using DESs

Materials synthesized Molar ratio DES Ref.

a
Ni2P@graphene 1:3 NiCl26H2O : malonic acid 299
S,N doped reduced graphene oxide 1:2 ChCl : Na2S 300
Sn/SnO2@C 1:2 ChCl : SnCl2 301
N doped and N,P-codoped porous carbon 1:3 AHCl : ethylene glycol 302
CuO/g-C3N4 1:2 ChCl : urea 303
Nanoporous Au 1 : 3.5 ZnCl2 : urea 304
Co films 1:2 ChCl : PEG200 305
SmCo films 1 : 2a ChCl : ethylene glycol 306
Various Sn–Se crystalline species 1:2 ChBr : urea 307
CeO2 nanoparticles 1:1 CTAB : acetic acid 308
g-Fe2O3 1 : 2a D-L-Menthol : pyruvic acid 309
BaTiO3 1:1 ChCl : malonic acid 310
Layered zinc phosphates 1:1 ChCl : oxalic acid 311
(VO)2P2O7 1:1 ChCl : oxalic acid/glucose 312
CdS@CeO2 — Thiourea : PEG200 313
Zeolitic imidazolate framework-8 6 : 4a TBAB : 2-Mim 314
Zeolite analogues 1:2 ChCl : urea 315
2D-[Co(NH3)4CO3]Cl 5 : 18.3 CoCl26H2O : urea 316

Abbreviations: AHCl: anilinium chloride; TBAB: tetrabutylammonium bromide; CTAB: cetyltrimethylammonium bromide; and 2-Mim: 2-
methylimidazole. a Represents more than one ratio.

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the preparation have the eutectic properties (i.e. melting point
is lower than that of each single component). Therefore, DESs
need not be used always at the specific proportion. Controversy
over the definition of DESs has always existed.318,319 Although
the focus of contention is the difference between ionic liquids
and DES, it can be inferred that if DESs are successfully used
to achieve the purpose, their definition can be reasonably
extended. Consequently, apart from several conventional
terms, eutectics is expected to be used to refer to a system with
a melting point lower than that of each single component. This
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can make the whole field more diverse.
5.4.5 Biological applications. DESs can be applied in bio-
logical science thanks to their biocompatibility. The ecotoxico-
logical profile of DESs was studied through the Microtoxs
acute toxicity test.320 The low toxicity of DESs makes them
desirable for biological applications. DESs have been used for
analysis of genetic material structure.321 The structure of
human telomere sequence (HTS) DNA has attracted much
attention due to the role of telomeres in aging and cancer. In
reline, HTS DNA tends to form a Gquadruplex with the parallel-
stranded (propeller) fold. Further studies showed that this
dynamic transition is related to the viscosity of the whole
solvent system. Another work reported that nucleic acids can
form several secondary structures that reversibly denature with
heating in an anhydrous DES.322 In some cases, the nucleic acid
sequences showed different relative stabilities and secondary
structures in DES comparing to those in aqueous solutions.
In addition, DES has been proved to significantly maintain
the integrity and viability of bacteria through freeze-drying
technology.323 The findings opened up bright prospects for
the application of microorganisms in the biocatalytic process in
non-aqueous systems. Furthermore, the possibility of eutectics
as improved pharmaceutical materials was discussed.324 DESs
have shown good applicability in the intersection of biology
and chemistry and are expected to be applied in DNA-based
nanotechnology.
5.5 Eutectic molecular liquids
Apart from coulombic interaction between ions, the main
interaction in DESs is hydrogen bonding, which belongs to
noncovalent interaction. This intrinsic nature determines that
DES has good effect in dissolving some polar polymers, such as
cellulose.252 However, there are few reports about dissolving
low-polar substances, such as plastics. Therefore, it is necessary
to develop new solvents to tackle this issue.
In recent years, other noncovalent interactions including
halogen (group VIIA elements), chalcogen (group VIA elements),
pnicogen (group VA elements), tetrel (group IA elements) and even
aerogen (group VIIIA elements) bonding have been discovered
and studied.325–331 Mu et al. proposed eutectic molecular liquids
(EMLs), which are composed of two molecular compounds
based on various noncovalent interactions.332 Fig. 27 shows the
differences between DES and EML from component to inter-
action. Here, the most typical DES was chosen. DES (binary for
example) is composed of an ionic compound and a molecular
compound, while EML is composed of two molecular compounds.
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Fig. 27 Differences between DESs and EMLs. Various ‘‘bonds’’ shown in
the right side are bonding interactions.
Furthermore, a large number of EMLs can be strategically
designed and prepared by simply mixing two molecular compo-
nents based on noncovalent interactions. These interactions
include hydrogen bonding interactions; p–p stacking; and s-hole
(halogen, chalcogen, pnicogen, tetrel bonds), p-hole, k-hole, and
m-hole bonding interactions. In this way, the eutectic liquid
systems can be enriched greatly.
Interestingly, Coutinho and coworkers also noticed non-
ionic eutectics. In their recent work, molecular compounds
(like thymol and menthol) were mixed to produce diverse
eutectics.333 In the thymol–menthol system, a strong molecular
interaction was identified among them. The tremendous acid-
ity difference between the phenolic and aliphatic hydroxyl
groups was conceived to be the reason for the forming of
eutectics. Actually, this interaction is hydrogen bonding inter-
action according to a review work.334 Consequently, they called
these eutectics non-ionic ‘‘the type V DES’’. Although the name
is different from EML, it is essentially a kind of eutectic system
formed by two molecular compounds. This also reflects from
the side that it is of significance to propose EMLs.
Semiconductor films have received a great deal of attention
due to their usage in the field of optoelectronics. However, the
thorny problem is that they are insoluble in common solvents.
Brutchey and coworker described a novel binary mixture (1,2-
ethanedithiol : 1,2-ethylenediamine = 1 : 10 in volume) which
possesses the remarkable ability to dissolve a series of bulk
V2VI3 chalcogenides (V = As, Sb, Bi; VI = S, Se, Te) under mild
conditions.335 In addition, the method they proposed has been
broadened to over 65 bulk precursors, which can be utilized to
develop new routes to functional chalcogenide materials.336
Although Brutchey et al. did not pay attention to the name of
this binary mixture, the authors hold the view that the solvent
they used was a eutectic complex (i.e. EML).
EMLs, as a family of new solvents, have been applied in
synthesizing 2-dimensional materials. Mu and coworkers
synthesized CoSx from EML (1,2-ethanethiol : n-butylamine =
4 : 1 in volume) at room temperature by compressing carbon
dioxide as an assistant.337 The nano sized CoSx achieved a
current density of 10 mA cm2 at an overpotential of 271 mV
for the oxygen evolution reaction. Moreover, the method they
proposed can be used to prepare other transition metal
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Fig. 28 (A) Photographs of EML and 2D materials dispersed after peering
in EML. Abbreviations: G for graphene, BSb for black antimony. (B) Tyndall
phenomenon of 5 mixtures. (C) Photographs of EML and polymers
dissolved in EML. Abbreviations: Ori for original EML, Lig for lignin, PS for
polystyrene, PEG for polyethylene glycol, TPIP for trans-1,4-polyisoprene,
PMMA for polymethyl methacrylate, PC for polycarbonate. (D) Three kinds
of typically waste plastic in daily life. (E) A complete sketch of CD recovery
process.339 Reproduced with permission from ref. 339. Copyright 2019
John Wiley and Sons.
chalcogenides. In another work, a solvothermal method for
synthesizing nanostructured Fe3S4 was reported.338 The
as-obtained Fe3S4 catalyst was capable of electrochemically
reducing N2 to NH3 under ambient conditions, which exhibited
a high NH3 yield (75.4 mg h1 mg1 cat.) and faradaic efficiency
(6.45%) at 0.4 V vs. a reversible hydrogen electrode.
Mu and coworkers reported a series of EMLs based on
hydrogen bonding and p–p stacking.339 These liquids possess
a relatively higher thermal stability than conventional volatile
organic compounds and can be used for multiple tasks. As is
shown in Fig. 28, the EML can be used to exfoliate 2D materials
and dissolve polymers. In addition, they proposed a process to
recycle three typical waste materials: plastic foam, acrylic, and
CD dish.
5.6 Supramolecular systems with the concept of eutectic
As mentioned above, DESs can be used as electrolytes owing to
their excellent conductivity. The leakage of electrolytes remains
a challenging issue. More seriously, the compatibility between
DES electrolytes and lithium is poor, which reduces the rever-
sible capacity and cycle life of the battery. It has been shown
that the scope of eutectics can be extended beyond liquids.
Eutectogels, first proposed by Joos et al., are a class of eutectic
systems that are composed of ionic and molecular substances
with a supramolecular structure.340 Normally, the system con-
tains a certain amount of polymer, and there are non-covalent
interactions between various species. These materials are expected
to become new anhydrous or low-water media, with important
roles in the field of electrolytes.
Lithium ion batteries and lithium metal batteries with high
capacity and long life at room temperature or even high
temperature are expected all the time. However, the dendrite
growth of lithium has hindered further development. The lack
of stable, environmentally friendly electrolytes has also stalled
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these high-energy density devices. Joos et al. reported a solid
composite electrolyte based on DES with a high conductivity
(1.46 mS cm1), and thermal and electrochemical stability
(4.8 V).340 These insights enlarged the scope of electrolytes,
thus improving the development of more performant batteries
with high safety and durability. More importantly, the strategy
can be extended to other ion batteries. In Smith’s work, a series
of eutectogel were formed by self-assembly based on non-
covalent interactions.341 The addition of 1,3:2,4-dibenzylidene-D-
sorbitol (DBS) gave the systems a gel-like property (Fig. 29A).
Electron microscopy and X-ray diffraction indicated DBS networks
in eutectogel, and DSC showed that the eutectic solvent properties
of the liquid phase were retained (Fig. 29B). The eutectogel was
tolerant to lithium salts, and the result showed the electromigra-
tion of ions was not affected in it compared with that in DESs.
The eutectogel prepared by Liu et al. possesses high thermal
stability and excellent electrochromic activity.342 The colour of
the eutectogel changed from pristine to blue as the potential
increased from 0 V to 0.7 V (Fig. 29C). Moreover, slight
bending did not affect the electrochromic performance. These
bio-based gels are expected to be candidates for the develop-
ment of next-generation flexible electronic products with less
environmental impact. In addition, He et al. reported a series of
eutectic elastomers by in situ polymerization of acrylic acid
based DESs.343–345 The synthesized supramolecular materials
possess good mechanical, electrical and optical properties.
Wang et al. reported a lithium metal battery based on
eutectogel.346 The electrolyte was easily prepared by in situ
copolymerization of acrylic acid derivatives, with fluoroethylene
carbonate as an additive. The gel-like electrolyte possesses both
high ionic conductivity and electrochemical stability. Polymer
networks in this eutectogel act as mesh structures to make the
distribution of Li ions more uniform, thereby inhibiting the
generation of branch crystals (Fig. 29D). Further experiments
have proved that this electrolyte can significantly increase the
capacity of the battery.
In addition to the above systems, some electrically neutral
system with the concept of eutectics has also been
reported.347,348 Yu et al. proposed a new material by combining
the concepts of shape memory and photochemical phase
transition.348 As showed in Fig. 29E, the whole system was
composed of a photoresponsive (azobenzene based) mesogen
and a eutectic (phenyl benzoate based) mesogen. The polymer
fibre can realize light-driven contraction and is expected to be
used in fields of soft robots and bionic muscles (Fig. 29F).
Study has also shown that the state of the polymer in a
binary eutectic system changes with its molar ratio.349 Control
of the morphology of polymers in a supramolecular system is
conducive to the design of eutectics with good chemical,
mechanical and electrical properties.
6. Outlooks and conclusions
Although various valuable eutectic systems have emerged, over-
coming their intrinsic shortcomings remains a challenge. In
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Fig. 29 (A) Deep eutectic solvents formed by mixing an organic salt and a hydrogen bond donor (1 : 2 ratio) can be turned into gel-phase materials by
the addition of 1,3:2,4-dibenzylidene-D-sorbitol (DBS, 5% wt/vol), which self-assembles into nanofibers, forming a new class of ‘supramolecular
eutectogels’. (B) SEM image of supramolecular eutectogel made in DES (ChCl:EG), then solvent exchanged with water and cryo-dried prior to imaging.341
Reproduced with permission from ref. 341. Copyright 2019 John Wiley and Sons. (C) Photos of the flexible electrochromic device at 0.7 V for colouring
and 0 V for bleaching.342 Reproduced with permission from ref. 342. Copyright 2020 John Wiley and Sons. (D) Numerical simulations of the Li ion flux
distribution on the Li metal anode surfaces for DES electrolyte with glass fibre membrane and DES-based self-healing polymer electrolyte.346
Reproduced with permission from ref. 346. Copyright 2020 John Wiley and Sons. (E) Molecular structure of a newly designed linear liquid crystal
polymer. (F) Photographs showing light-driven contraction up to 81% of the polymer fibre upon irradiation with a 470 nm light (100 mW cm2).348
Reproduced with permission from ref. 348. Copyright 2020 John Wiley and Sons.

the case of DESs, their high viscosity and relatively low thermal
stability may hinder their industrial applications. Fortunately,
these problems can be solved by diluting and sealing opera-
tions. As discussed in the previous sections, dilution of DESs
with a certain amount of water does not change their proper-
ties. However, some deeper problems cannot be easily solved.
On the other hand, developing new eutectic systems with
excellent properties is a good target; moreover, in order to
effectively use these superior systems, industrial optimization
will be essential. Machine learning will play an increasingly
important role in these processes.
6.1 In-depth exploration of eutectics
6.1.1 Mechanisms of eutectics. The study of eutectics
started with research on the melting properties of single sub-
stances. Neutron scattering and Monte Carlo simulation are the
two most representative research methods. Later, as mentioned
above, a series of theories emerged to explain the mechanisms

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of eutectics. The increase in entropy change simply explains the
eutectic mechanism, the interaction explains the driving force
of the eutectic from a molecular point of view, and the chemical
potential explains the determination of the eutectic tempera-
ture from an energy perspective. However, there has been no
systematic work to integrate these principles. Owing to the
complexity of molecular compounds, eutectic systems are very
complicated, which creates a major difficulty for mechanism
research. Therefore, research in this area needs to continue.
On the other hand, the microscopic dynamic process of
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eutectics remains unclear. Much research on their thermo-
dynamics and kinetics date back to decades ago, and research
in recent years has been devoted to their applications. Conse-
quently, more in-depth research is needed in the future.
6.1.2 Development of new systems. From ancient eutectic
metals to newly emerging DESs, eutectic systems continue to
flourish. In order to meet different needs, task-specific systems
have been designed and applied. Eutectic salts originated from
the need for high-temperature phase-change materials, and the
demand for non-aqueous and green solvents brought about
DESs. Eutectic molecular liquids based on non-covalent inter-
actions other than hydrogen bonds have also been shown
to have potential for dissolution and separation. New systems
could be designed and prepared based on halogen bonds,
chalcogen bonds, etc. From the perspective of composition, a
eutectogel incorporates a polymer compound into the eutectic
system, which greatly enriches the system. In particular, eutec-
togels have an important role in stretchable materials and solid
electrolytes. Therefore, the design of new eutectic systems
should consider both internal interaction and composition to
meet specific application needs.
6.1.3 New combinations. In Section 4.3, we introduced the
liquid metal battery, which is a battery composed of eutectic
alloys and eutectic salts. Although it is based on two known
eutectics, the liquid metal battery is a new concept that is
receiving increasing attention. It is foreseeable that composite
materials combining eutectic metals and eutectogels will be
proposed in the near future. Compared with general polymer
materials, eutectogels have good electrical conductivity, which
makes their composite materials both ionic conductors and
electronic conductors. Compared with the combinations with
hydrogels, the eutectic phase of these materials has a lower
melting point (or Tg) and higher stability. This greatly enlarges
the application scope of the eutectic metal–eutectogel systems.
6.2 Technical optimizations
Eutectics systems have a few shortcomings, so attention should
be paid on their optimization. At present, the scientific commu-
nity is mainly concerned with the feasibility of these systems,
while in industrialization and deeper economics level, there is less
research. Although great progress has been made in the indus-
trialization of eutectic salts, this is limited to certain types of
eutectic salts, and their use is relatively single. It may also be
related to the early start of its scientific research.350,351 DESs have
made significant progress in dissolution and transformation of
biomass. However, most of the experiments stay at ‘‘get products’’
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Chem Soc Rev
rather than ‘‘get pure products’’. The differences between these
two targets involve the separation and purification process, which
may contain significant obstacles. Although the preparation
process of DESs is simpler than that of ILs, the purification of
DESs is more difficult. Because a DES is composed of at least two
components, HBA and HBD, and the boiling point of each
component can be very different. It is difficult to obtain original
DES after distillation, but the compounds with low thermal
stability will be obtained. For example, reline is a common DES
which is composed of ChCl and urea at a molar radio of 1 : 2. The
boiling point of urea is about 184 1C, while the melting point of
ChCl is over 240 1C. When reline is purified by distillation, the
pure phase collected is likely to be urea, and the liquid will be
enriched in ChCl (Fig. 30A). Compared with H2O, organic sol-
vents, and even some ionic liquids, DESs have great disadvantages
in terms of purification. However, this does not indicate that DESs
are of little significance. Mu et al. reported a strategy in which the
product could be separated from the reaction system by self-
precipitation (Fig. 30B).272 In this work, a FeCl3 based DES acts as
both catalyst and solvent for the transition of cellulose to gluconic
acid. Moreover, the gluconic acid will precipitate from DES
because of the extremely low solubility. As the consequence,
complexed separation processes could be avoided, and the cata-
lytic DES could be reused by filtration. Although this method is an
individual case, it smartly realizes the integration of solvents
and catalysts, as well as reaction and separation. It is a green
and sustainable method and has great potential in industrial
applications.
Mostly, it would be uneconomical for gallium based eutectic
metals to be used in large scale, owning to their relatively high
prices. But in a ‘‘micro scale’’, it is very useful in microelec-
tronic devices and soft materials. Microfluidic electronics facil-
itate the integration of electronic components, and flexible
electronic materials have made breakthroughs in wearable
devices. One huge problem that needs attention is that the
surface of a eutectic metal can get easily oxidized, and the
tightness of the equipment must be fully guaranteed. However,
controlling the oxidation process of metal droplets can produce
a variety of two-dimensional nanosheets for use in semicon-
ductor devices or catalytic reactions. To achieve long-term
development in academia and industry, it is necessary to
explore new applications. Microelectronics or micro-smart
devices are supposed to be introduced to some possible fields,
such as biological and medical devices.
There is a wide spectrum of maturity for eutectic salts,
ranging from energy storage to material synthesis. However,
the high operating temperature brings huge challenges to
equipment safety and cost. In view of this, current energy
storage research needs to explore eutectic salts with greater
energy storage density and higher stability. Moreover, the
corrosion mechanism of various salts has not been completely
resolved, and the effects of different species are still ambig-
uous. It is also imperative to develop electrodes and containers
with high chemical stability. For industry, more attentions
should be paid on equipment and process optimization, such
as more efficient reflectors and thermal insulation materials.
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Fig. 30 Purification mode of conventional reaction (A) and self-precipitation reaction (B).

6.3 Machine learning

The basic principle of machine learning is to use algorithms to
parse data, learn from it, and then make decisions and predic-
tions about events in the real world. Research and applications
based on algorithms have become increasingly pervasive and
deeply entrenched components of modern technology, and
machine learning has also made significant advances in var-
ious fields.352–355 Compared with pure substances, the mixed
eutectic systems possess an exponentially greater degree of
complexity. At the same time, exploration and screening based
on human efforts are undoubtedly time-consuming and ineffi-
cient. In order to conform to trends in development and
multidisciplinary interaction, the design of eutectic systems Fig. 31 The role of machine learning in the development of eutectics.
should make use of machine learning and big data. Double arrow indicates a mature interaction between industry and
academia. Solid arrows indicate that machine learning needs data from
Taking DES as an example, future research can be consi-
practical applications and scientific experiments, while dash arrows repre-
dered from two perspectives. In terms of basic research, sent the feedback.
machine learning could be used to explore the structure of
hydrogen-bonding networks in DESs and to design new DESs
based on various non-covalent interactions (including halogen Machine learning in chemistry is so far still in its infancy.
and chalcogen bonding); in terms of application research, It requires input of a large amount of data from both industry
solvent systems could be designed according to the character- and academia (solid arrows in Fig. 31). Machine learning
istic properties needed for practical purposes. As in the model models have emerged to solve some basic problems. However,
shown in Fig. 31, the solubility of the reactant and product in a it is mostly used as an auxiliary or alternative method, rather
solvent is very distinct, allowing the product to automatically than the best method. By now, industry and academia can
separate from the reaction solution. Recent research progress gradually get feedback from machine learning (the dotted line
has proved the feasibility of this approach. Machine learning- in Fig. 31). It is hoped that one day in the future, this increasing
based models will make it possible to correct some of feedback will guide and dominate the development of science
the problems that plague many common approximations in and technology.
traditional computing.356 Besides, molecular dynamics and
electron-density-based solution studies provide new means of 7. Conclusions
exploring binary fluids.357–359 The progress described above has
laid the foundation for practical applications including predicting In conclusion, eutectics has been a rapidly developing field
and selecting the solvent systems. from ancient times to the present. The main purpose of this

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Review Article
review was to introduce the significant research progress that
has been made regarding three typical eutectics: DESs, eutectic
metals, and eutectic salts. DESs are considered to be environ-
mentally friendly solvents and are expected to be used in
sustainable development. Gallium based eutectic metals are
relatively expensive, so they are suitable for use in small parts
and sophisticated smart devices. Most of the applications of
eutectic salts remain limited to the field of thermal energy
conversion. Eutectic molecular liquids and eutectogels supple-
ment existing eutectic systems from the perspectives of inter-
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action and composition, respectively. Future work should focus
on in-depth exploration of eutectic principles and the develop-
ment of new systems. Eutectic system design and industrial
process optimization based on machine learning will be essential
in the future.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
The authors thank Dr. Zhenghui Liu for his help in proof-
reading. This work was supported by the National Natural
Science Foundation of China (22073112, 21873012, 21773307),
and the China Scholarship Council (202006360037).
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