Applied Energy 325 (2022) 119853

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

A state-of-the-art review on the liquid properties regarding energy and

environmental performance in liquid desiccant air-conditioning systems
Jielin Luo *, Hongxing Yang *
Renewable Energy Research Group (RERG), Department of Building Environment and Energy Engineering, The Hong Kong Polytechnic University, Hong Kong, China

H I G H L I G H T S

• Energy saving is achieved by using liquid desiccant in air-conditioning systems.

• Thermodynamic properties of different kinds of liquid desiccant are reviewed.
• Safety issues of liquid desiccant are analyzed in different aspects.
• Current situations and future concerns are concluded for different liquid desiccants.
• Promising candidates of liquid desiccant for next generation are recommended.

A R T I C L E I N F O A B S T R A C T

Keywords: Liquid desiccant air-conditioning system (LDAS) becomes an attractive option for reducing the energy con­
Review sumption of conventional air-conditioning systems. Despite lots of published papers on LDAS in various aspects,
Air-conditioning system there is not yet a comprehensive and up-to-date review on the properties of liquid desiccants, while the selection
Liquid desiccant
of liquid desiccant plays essential role in the overall performance of LDAS. In this paper, a state-of-the-art review
Thermodynamic properties
Safety concerns
on the properties in regard of energy and environmental performance is delivered for present and potential liquid
desiccants, including vapor–liquid equilibrium, specific heat capacity, safety concerns. The current situations and
future concerns of liquid desiccant investigation can be obtained, while different kinds of liquid desiccant
candidates can be compared and evaluated comprehensively. Existing liquid desiccant of halide salt faces severe
drawback of corrosiveness in long-term use. Compared with existing liquid desiccants, the candidates of weak
acid salt, ionic liquid and deep eutectic solvent behave low toxicity and friendly corrosiveness, whereas their
weak moisture absorption ability, high cost or high viscosity is the bottleneck for further applications. Therefore,
the mixture of them can be regarded as a promising candidate in LDAS applications, but the fundamental
properties are urged to be measured. The work in this paper provides momentous reference and guidance for the
exploration of new liquid desiccant as well as the evaluation of future prospect of LDAS.

1.1. Overview of LDAS

1. Introduction For conventional vapor-compression air-conditioning systems, the

To date, energy issues are receiving global attention. Building’s en­
ergy consumption had constituted the proportion of 30 % in the world’s
total energy consumption, reported by International Energy Agency [1].
Among building’s energy consumption, the consumption due to air
conditioning accounted for 40–60 % [2,3]. Moreover, associated with
rising standard of living levels, the usage of air-conditioning system is
increasingly demanded, in which the controls of both temperature and
humidity are emphasized [2].
regulation of humidity is realized through condensation dehumidifica­
tion method, i.e., a group of cooling coil and reheater [4]. Under the
working condition with high latent load, such configuration is proven to
be severely inefficient [4].
The studies on the advance of air-conditioning system are spurred by
the context of energy-saving, and thus the concept of desiccant dehu­
midification is raised and adopted. Compared with conventional
condensation dehumidification, systems with desiccant dehumidifica­
tion are expected to save up to 30 %-50 % of energy consumption in

* Corresponding authors.
E-mail addresses: jielin.luo@polyu.edu.hk (J. Luo), hong-xing.yang@polyu.edu.hk (H. Yang).

https://doi.org/10.1016/j.apenergy.2022.119853
Received 18 May 2022; Received in revised form 27 June 2022; Accepted 15 August 2022
Available online 22 August 2022
0306-2619/© 2022 Elsevier Ltd. All rights reserved.
J. Luo and H. Yang Applied Energy 325 (2022) 119853

the heat releasing effect for liquid desiccant when absorbing moisture,
Nomenclature the involving of cooling source to dehumidification process is obviously
beneficial for maintaining the moisture absorption ability of liquid
Abbreviations desiccant, and thus positive for improving system performance [10].
ANN Artificial neural network Besides, it should be mentioned that the flow path of liquid desiccant
DES Deep eutectic solvent in Fig. 1 only represents the most typical one for explaining the working
HBA Hydrogen bond acceptor principle of LDAS [11]. Among existing studies, researchers put forward
HBD Hydrogen bond donor lots of innovative invention on flow patterns of liquid desiccant and
IAQ Indoor air quality processing air in regards of designation, simulation and experiment
IL Ionic liquid [9,12,13]. By decoupling sensible and latent heat load in dehumidifier
LD50 Lethal dose 50 and air cooler, LDAS exhibits not only better system performance but
LDAS Liquid desiccant air-conditioning system also convenient control strategy in practical applications.
LAMEE Liquid to air membrane energy exchanger The performance of LDAS has been gradually concerned in recent
PM Particulate matters years. The publication situation is investigated through the database of
VOC Volatile organic compound Web of Science with different keywords, including liquid desiccant (LD),
VLE Vapor liquid equilibrium liquid desiccant air-conditioning system (LDAS) and air-conditioning
system (AS). As shown in Fig. 2, the studies on liquid desiccant and
English letters air-conditioning system are significantly increasing. However, up to
P Pressure 2020, compared with the numerous researches on air-conditioning
t Temperature system of more than 80,000, the studies on LDAS are still less than
w Mass fraction 200 despite its increasing trend.

1.2. Contributions of this paper

commercial buildings [5]. According to the phase, desiccants are cate­
gorized as liquid desiccant and solid desiccant. Compared with solid Despite lots of studies on LDAS, it is still necessary to identify the
desiccant, liquid desiccant has better moisture absorption ability, lower existing gaps to enhance motivation of this work.
regeneration temperature, lower system construction cost, better ability Generally, system strategy, component design and working fluid
in filtering microorganism [6,7]. selection are three essential aspects in the construction of LDAS in
The schematic diagram and basic principle of a typical liquid practical application. However, the development of liquid desiccant is
desiccant air-conditioning system (LDAS) can be expressed as shown in always of less attention. In 2016, Abdel-Salam et al. [14] made a
Fig. 1.
As shown in Fig. 1, fresh air is dehumidified to required humidity in
the dehumidifier by liquid desiccant with low vapor pressure, and the
dilution heat of liquid desiccant is taken away by external cooling
source. Then fresh air enters air cooler, in which the sensible heat is
dealt with and the air is cooled to required temperature. For LDAS, the
temperature and humidity of supply air can be independently regulated
in dehumidifier and air cooler.
The liquid desiccant can be recycled when heat source is utilized for
regeneration. Heat source is input to the regenerator to remove water
vapor from diluted liquid desiccant. After regeneration, the concen­
trated solution is able to flow back to dehumidifier to absorb moisture
from air once again. Between dehumidifier and regenerator, a heat
exchanger can be installed for heat recovery. Through the heat
exchanging process between low-temperature diluted solution and high-
temperature concentrated solution, both the cooling and heat source
input for LDAS can be saved.
In Fig. 1, the cooling input to dehumidifier is optional in practical
design, through which the dehumidification process can be classified Fig. 2. Studied trends of different keywords on Web of Science in past 30 years.
into adiabatic one and internally-cooled one [8,9]. In consideration of (AS: air-conditioning system; LD: liquid desiccant).

Fig. 1. Schematic diagram of typical LDAS configuration.

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J. Luo and H. Yang Applied Energy 325 (2022) 119853

classification of the published journal papers about LDAS between 1980
and 2014, whose results indicated that the studies on solution properties
of liquid desiccant only accounted for about 4 % among all the papers.
Moreover, the objective of existing review papers on LDAS is also
surveyed to illustrate the lack of attention to liquid desiccant properties.
Table 1 is a literature survey on the published review papers on LDAS
hereunder, in which their objectives are also concluded. From Table 1, it
can be found that the objectives of these review papers include material,
component, system, application, integration of renewable energy, re­
covery of waste energy. Despite the wide recognition of the importance
of liquid desiccant selection, there is not yet a comprehensive and up-to-
date review on the properties of liquid desiccants.
Table 1
Comparisons between existing review papers on LDAS and this paper.
Authors Years Main objectives and contents
In Table 1, there is only one review regarding the thermodynamics
and economics of liquid desiccants, i.e., Ref [10]. In 2018, Giampieri
et al. [10] conducted a review on typical liquid desiccants, including
aqueous LiCl, LiBr, CaCl2, MgCl2 and HCOOK. However, the present
liquid desiccant is much more than such salt solutions, and the review by
Giampieri et al. focused quite less on the other type of liquid desiccant,
such as glycol, ionic liquid and deep eutectic solvent.
A comparison of the contribution of this paper to the existing reviews
is given in Table 1 as well. The contribution of this paper is different
from the existing surveys as it presents: 1) an overall glimpse of potential
liquid desiccant; 2) a comprehensive survey on different properties
regarding energy and environmental performance in LDAS; 3) the
recommendation of developing direction of the next-generation liquid
desiccant. Such work provides momentous reference and guidance for
exploration for the potential candidate of liquid desiccant, and for
evaluation of future prospect of LDAS.

Daou et al. [15] 2006 Demonstration of the feasibility and the energy 1.3. Research methodology and paper organization
saving effect of desiccant cooling systems
Mei et al. [16] 2008 Techniques, configurations, components, A state-of-the-art review on liquid properties regarding energy and
performance improvement for LDAS
Yao [17] 2010 Ultrasonic dehydrator for the desiccant regeneration
environmental performance in LDAS is delivered in this paper. The
Cheng et al. [18] 2013 Solar regeneration methods for LDAS keywords for searching in database is not only limited in liquid desiccant
Mohammad et al. 2013 Liquid desiccant dehumidification systems combined used in air-conditioning system, but also working substance used in
[19] with evaporative cooling technologies dehumidification, desalination, drying, moisturizing, etc. The publica­
Yin et al. [20] 2014 Models, system configurations, component design
tion years of papers searched in this paper cover from 1935 to 2021.
and renewable energy utilization of LDAS
Luo et al. [8] 2014 Mathematical models for predicting the heat and The structure of this paper is diagrammatized in Fig. 3. The present
mass transfer process in the liquid desiccant and potential liquid desiccants are firstly classified in section 2, and the
dehumidifiers important characteristics for air-conditioning applications are intro­
Buker et al. [21] 2015 Liquid desiccant evaporative cooling systems with duced in section 3. According to the characteristics listed in section 3,
solar-assisted regeneration
Rafique et al. [22] 2015 System configurations, operating modes and current
liquid properties in regard of the energy and environmental perfor­
technology of liquid desiccant based evaporative mance are surveyed and compared for various liquid desiccants, i.e.,
coolers section 4 for vapor–liquid equilibrium, section 5 for specific heat ca­
Abdel-Salam et al. 2016 Classifications of components, systems, material, pacity, section 6 for safety concerns. Besides, some other properties (e.
[14] cooling/heating methods and energy recovery in
g., density, viscosity, cost) are introduced in section 7 to show the
LDAS
Rafique et al. [9] 2016 Applications of commercially available liquid overall situation of potential liquid desiccants. In section 8, a summary is
desiccants and configurations of dehumidifiers conducted to conclude the pros and cons of existing liquid desiccants,
Sahlot et al. [23] 2016 Components used in liquid desiccant systems while the potential candidate for next-generation use is also
Fu et al. [24] 2017 Impact of liquid desiccant dehumidification on emphasized.
indoor air quality
Guo et al. [25] 2017 Photovoltaic thermal (PV/T) heat utilization for
desiccant cooling and dehumidification 2. Category of liquid desiccants
Shukla et al. [26] 2017 Regeneration of liquid desiccant using solar energy
Bai et al. [27] 2018 Modelling methods of membrane-based liquid 2.1. Salt-water
desiccant heat and mass exchanger
Fekadu et al.[7] 2018 Renewable energy utilization for LDAS
Giampieri et al. 2018 Thermodynamics and economics of typical liquid Salt-water pair is one of the earliest proposed liquid desiccants, and it
[10] desiccants in LDAS is still widely applied in present LDAS.
Gómez-Castro 2018 Solar thermal regeneration for liquid desiccant Plenty of researches have been carried out for LDAS applications
et al. [28] systems using aqueous solutions of popular single halide salts, regarding the
Gurubalan et al. 2019 Classifications and developments in components,
[29] materials and mathematical models in LDAS
mathematical model of heat and mass transfer, the control strategy of
Liu et al. [30] 2019 Materials, components, systems and performances of system, the designation of components and multi-objective evaluation
membrane-based liquid desiccant air [33–36]. Typical and conventional halide salts (e.g., LiCl, LiBr, CaCl2,
dehumidification MgCl2) exhibit specific characteristic in favor of applications in LDAS.
Ren et al. [12] 2019 Heat and mass transfer improvement techniques for
LiCl and LiBr are widely adopted in LDAS attributed to their outstanding
dehumidifiers and regenerators in LDAS
Wen et al. [31] 2019 Correlations and enhancement of heat and mass moisture absorption abilities, while the inevitably severe corrosion to
transfer in liquid desiccant dehumidification metal restricts their long-term applications [10]. CaCl2 is regarded as a
Chen et al. [6] 2020 Types of dehumidifiers and the integrations of LDAS less-corrosive and economic alternative to LiCl and LiBr, despite its
with different technologies worse hygroscopicity [9]. MgCl2 is another candidate characterized by
Liu et al. [4] 2020 Electrically driven dehumidification technology in
LDAS
lower toxicity but higher crystallization risk [10]. The properties for
Qi et al. [5] 2020 Optimizations on systems, components and materials typical aqueous salt solutions have been deeply and comprehensively
in liquid desiccant air dehumidification investigated for air-conditioning use, which is introduced in the
Gao et al. [11] 2021 Integration and design of desiccant air-conditioning following sections.
systems for overall performance improvements
Besides, aqueous weak organic acid salts are paid more and more
Gurubalan et al. 2021 Designation and configuration of dehumidifiers and
[13] regenerators in LDAS attention by researchers. For example, potassium formate (HCOOK) and
Salikandi et al. 2021 Applications and regeneration characteristics of potassium acetate (CH3COOK) are regarded as potential solute in
[32] liquid desiccants and the performances in LDAS aqueous solutions for LDAS with low cost, low toxicity, less corrosive­
This paper – Energy-related and Safety-related properties of ness and higher solubility [10,37,38]. The regeneration and dehumidi­
liquid desiccant at present and in the future
fication performances of HCOOK-H2O were studied by Riffat et al.

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J. Luo and H. Yang Applied Energy 325 (2022) 119853

Fig. 3. Illustration of the structure of this paper.

[39–42] to illustrate its application potential. Longo et al. [43–45]
conducted theoretical and experimental assessments of LDAS with
HCOOK-H2O, while heat and mass transfer characteristic, energy saving
effect and annual cost were studied.
Aqueous solutions of mixed salts are also proposed for potential
applications. For instance, Li et al. [46] evaluated different mixing ratios
of LiCl-CaCl2-H2O in LDAS to alleviate the corrosiveness of LiCl and
improve moisture absorption ability of CaCl2, and the application
prospect of such mixture was demonstrated.
cosmetics, whose moisturizing effects are publicized (with keywords
like humectant, water/moisture absorption/retention, etc.), may deliver
enlightenment for the exploration for safety liquid desiccant. However,
since such idea has not yet been experimentally investigated in existing
publications, it will not be detailly presented in this paper.
2.3. IL-water
Room-temperature ionic liquid (IL) is often formed by organic

2.2. Glycol-water
Table 3
Abbreviation, full name and type of ions of IL in this paper.
Glycol-water pair is another kind of the earliest proposed liquid
desiccants. Back in 1955, TEG-H2O was raised as liquid desiccant to be Abbreviation Full name type

used in a cooling system [47]. LDAS using TEG-H2O was investigated in [Bmim] 1-butyl-3-methylimidazolium cation
aspects of system performance, component design, and mathematical [Ch] Choline (2-hydroxy-N,N,N-trimethylethan-1-aminium) cation
[DEMA] diethylmethylammonium cation
modelling, whose mass fraction of TEG used in LDAS was recommended
[Dmim] 1,3-dimethylimidazolium cation
to be 0.9–0.98 [48–51]. According to molecular weight, different [Emim] 1-ethyl-3-methylimidazolium cation
polymers of glycol can be generated for utilization in specific applica­ [Hmim] 1-hexyl-3-methylimidazolium cation
tions (e.g., PEG400, PEG 1000). However, due to its well-known vola­ [Hydemim] 1-(2-hydroxyethyl)-3-methylimidazolium cation
tility, the applications of glycol-H2O in LDAS is extremely limited. [P4441] tributyl(methyl)phosphonium cation
[P4444] tetrabutylphosphonium cation
For simplicity, glycols introduced in this paper are abbreviated as
[BF4] tetrafluoroborate anion
shown in Table 2. Br bromide anion
It should be mentioned that glycol-like substances (e.g., substance [BTI] bis(trifluoromethylsulfonyl)imide anion
with OH group) are also used in cosmetics as humectants, which Cl chloride anion
[DMP] dimethylphosphate anion
emphasize their characteristics of moisture retention and skin affinity.
[ES] ethyl sulfate anion
For example, chitosan and its derivative have been raised as additive in [Glu] glutamate anion
cosmetics with water retention feature and anti-microbial effect, while [Gly] glycinate anion
the influence of specific functional group on water affinity is discussed [HSO4] hydrogen sulfate anion
[52–54]. As composition of cosmetics, the safety issue of such substances I iodide anion
[Lac] lactate anion
are also explored by researchers [52]. Therefore, some additives in
[Lys] lysinate anion
[MS] methyl sulfate anion
Table 2 [OAc]* acetate anion
Abbreviation and full name of glycols in this paper. [OMs] methane sulfate anion
[PF6] hexafluorophosphate anion
Abbreviation Full name Abbreviation Full name [TFA] trifluoroacetate anion
EG Ethylene glycol PG Propylene glycol [TFO] triflate (trifluoromethanesulfonate) anion
DEG Diethylene glycol DPG Dipropylene glycol [Tf2N] bis(trifluoromethanesulfonyl)imide anion
TEG Triethylene glycol TPG Tripropylene glycol *
It should be mentioned that, [Ac] is also used to represent acetate in some
T4EG Tetraethylene glycol T4PG Tetrapropylene glycol
papers. However, commonly [Ac] is the abbreviation for acetyl. In this paper,
PEG Polyethylene glycol PPG Polypropylene glycol
the abbreviation of acetate is uniformed as [OAc].

4
J. Luo and H. Yang
cations and organic or inorganic anions. With different cations and an­
ions, numerous IL can be synthesized. Table 3 depicts the names and the
abbreviations of cations and anions of IL introduced in this paper.
Different kinds of IL behave different characteristics. The thermo­
physical properties of pure IL have been investigated and reviewed in
past few decades [55–57]. The properties of pure IL are reported to be
integrated into a database developed by NIST, through which possible
candidate for LDAS can be selected preliminarily according to its solu­
bility in water and melting point [55]. Fabre et al. [56] reviewed the up-
to-date studies on properties of IL, in which the potential for thermal
application was revealed by the classification of IL.
The water absorption effect of IL has been noticed by researchers,
and IL-H2O is then proposed as potential substitute of existing liquid
desiccant, attributed to its non-volatility and non-corrosiveness. It is
suggested that phosphonium-based IL and ammonium-based IL have
very strong hydrogen bonds, corresponding to the possibility for water
solubility [56]. In respect of anions, it was reported that specific anions
showed hygroscopic characteristic, e.g., [OAc]-based, [Tf2N]-based
[58].
Limited IL-H2O pairs have been investigated for applications in LDAS
in component-wise and system-wise experimentally and theoretically
[59–61]. The comprehensive investigations on properties of IL-H2O,
including specific heat capacity, density and excess enthalpy, for better
evaluation of their application prospect on thermodynamic systems are
still strongly appealed [62].
2.4. Mixture-water
In order to overcome the weakness of specific type of substance, the
working pair of mixture-water is presented. For example, LiBr-TEG-H2O
is raised to alleviate the corrosiveness of LiBr and the volatility of TEG
[7].
In recent year, deep eutectic solvent (DES) is also proposed for
investigation in chemical separation processes, biomass pretreatment
and electrochemical cell applications [37]. They are regarded as eco-
friendly alternative to IL with the characteristics of biodegradable,
biocompatible and non-toxic [63,64]. DES can be simply synthesized
through the mixing of a kind of hydrogen bond donor (HBD) and a kind
of hydrogen bond acceptor (HBA), e.g., EG-[Ch]Cl with molar ratio 2:1
[37,65]. The prices and properties of DES mainly depend on the selec­
tion of HBD and HBA. Compared with its applications in gas capture, the
attempt of DES in LDAS is still scarce. AlOmar et al. [66] synthesized 70
kinds of DES and tested the freezing point, density, viscosity and surface
tension of applicable ones. Despite its low vapor pressure, DES is
designed as solvent and its solubility in water depends on specific HBA
and HBD. Therefore, few of them can be tested for potential application
in LDAS.
2.5. Additives
Some additives are also involved into the above liquid desiccants to
improve the specific characteristic of liquid desiccant.
Nanoparticles (e.g., Al2O3, TiO2) are added into liquid desiccant to
improve heat transfer characteristic, whose influence on solution
properties has been studied [67,68]. Nevertheless, their stability,
corrosiveness, and aggregation effect are still required to be further
investigated [68].
Surfactants are involved into liquid desiccant to improve the
wettability of solution, while the influence on vapor pressures of solu­
tion is investigated as well [69]. However, some of surfactants are
poisonous and odorous, resulting in the risk of their applications in LDAS
[5,13].
The concentration of additive used in liquid desiccant is commonly
very low, e.g., lower than 1 %. Since additives cannot be used solely as
liquid desiccant in LDAS, the content of such issue will not be included in
this paper.
5
Applied Energy 325 (2022) 119853
3. Important characteristics of liquid desiccants for LDAS
Multifarious factors should be taken into consideration for the se­
lection of liquid desiccant. For the sake of long-term and large-scale
application of LDAS, liquid desiccant is expected to possess the char­
acteristics including non-toxic, non-flammable, nonvolatile, odorless,
stable, non-corrosive, economically efficient, outstanding moisture ab­
sorption ability, easy regeneration, good heat transfer performance, etc
[7,32].
Gurubalan et al. [13] and Rafique et al. [9] concluded the weighing
factors of properties for desiccant selection, as shown in Table 4. The
properties of liquid desiccants relevant to specific characteristic are also
given. It should be mentioned that in the original version of this table
given by Studak and Peterson [70], the figure of merit for safety is only
LD50, while it is extended into toxicity and volatility in this paper so that
a thorough investigation can be carried out for existing studies.
From Table 4, it can be found that different weighing factors are
distributed to different characteristics, among which the energy and
environmental performances are emphasized. Environmental parame­
ters of liquid such as toxicity, volatility and corrosion weigh the highest
(i.e., 1.0 or 0.8) in liquid desiccant selection. Successively, the properties
in regard of thermodynamic performance (e.g., VLE, specific heat ca­
pacity) hold a factor of 0.8 or 0.6. The economic concern and heat
transfer properties are relatively less weighed as 0.5 or 0.3.
As a result, the properties in regards of thermodynamics (i.e., VLE
and heat capacity) and safety will be primarily reviewed in the following
sections 4–6 in this paper, while the studies on the other properties are
briefly introduced in section 7.
4. Current studies on the VLE property of liquid desiccants
Vapor-liquid equilibrium (VLE) property is a primary thermophys­
ical property for evaluation of the dehumidification ability of hygro­
scopic solutions, which can be obtained by the measurement of vapor
pressure, boiling point, activity coefficient, osmotic coefficient, etc.
Table 5 depicts the up-to-date studied range of VLE properties of
typical liquid desiccants. It should be noted that only the data under
temperature ranges of LDAS application are included, despite lots of
data points measured for other temperature ranges. Except for desiccant
listed in Table 5, some other potential candidates are introduced
thereinafter, while a comparison between different liquid desiccants in
aspect of VLE is carried out in section 4.6.
4.1. Salt-water
The VLE properties of single inorganic salt solutions have been widely
studied. As shown in Table 5, the studied ranges for VLE properties of
aqueous single halide salts well cover the requirement for LDAS appli­
cation. Gierszewski et al. [83] measured the activity and osmotic coef­
ficient of LiNO3-H2O under the temperature ranging from 25℃ to 350℃
and mass fraction up to 0.5. Giampieri et al. [10] correlated the vapor
Table 4
Important characteristics of liquid desiccants.
Characteristic Weighing factor Relevant properties
[9,13]
Safety 1.0 Toxicity, volatility
Corrosiveness 0.8 Corrosion rate
Mass transfer 0.8 Vapor-liquid equilibrium (VLE)
potential
Heat requirement 0.6 Dilution heat, specific heat
capacity
Cost 0.5 Price
Heat transfer 0.5 Thermal conductivity
potential
Parasitic power losses 0.3 Density, viscosity
J. Luo and H. Yang Applied Energy 325 (2022) 119853

Table 5 kinds of single-electrolyte solutions and 14 kinds of mixed-electrolyte

Studies on VLE of typical liquid desiccants for LDAS applications. solutions, with an average deviation less than 0.26 % [112]. In terms
Desiccant Solute mass Temperature Literature of the advances of thermophysical models, more detailed introduction
fraction (℃) can refer to following section 4.5. Despite sufficient data, it is appealed
LiCl-H2O 0–0.60 0–121 [71–74] to integrate them as property package into common-used air-condi­
LiBr-H2O 0–0.75 0–350 [71,73,75–77] tioning software, which is helpful for further design and development of
CaCl2-H2O 0–0.70 0–350 [71,72,74,78–80] LDAS.
MgCl2-H2O 0–0.30 0–350 [79–81]
LiNO3-H2O 0–0.70 20–350 [82–84]
HCOOK-H2O 0–0.80 − 4–150 [85–87]
4.2. Glycol-water
HCOONa-H2O 0–0.75 − 5–100 [86]
CH3COONa-H2O 0–0.68 − 5–125 [88] The VLE measurement of aqueous glycol was mainly conducted in
LiCl-CaCl2-H2O 0.05–0.4 10–80 [71,89,90] last century, including EG-H2O, DEG-H2O, TEG-H2O, T4EG-H2O, PG-
TEG-H2O 0–1 20–70 [91–94]
H2O, DPG-H2O and TPG-H2O [91–93,113–116].
TPG-H2O 0–1 25–132 [91,95]
PG-H2O 0–1 25–104 [91,95] Some polymers of glycol were also investigated regarding their vapor
[Bmim][BF4]– 0.48–0.91 12–202 [96,97] pressures of aqueous solution. The VLE data of aqueous solutions with
H2O PEG from PEG200 to PEG 6000 were measured by researchers, while
[Dmim][OAc]– 0.19–0.92 20–78 [96] PEG with lower molecular weight showed lower vapor pressure
H2O
[Dmim]Cl-H2O 0–0.85 14–164 [98]
[117–121]. Maali et al. [122] measured the water activities of aqueous
[Emim][OAc]– 0–1 10–150 [62,99,100] solutions of PEG6000, PPG400 and PEG400, which indicated that
H2O aqueous solutions of PEG400 delivered the lowest water activity.
Due to its inevitable volatility, glycol is not recommended to be
solely used as liquid desiccant, so VLE of binary mixture of glycol and
pressure of Ca(NO3)2-H2O and NH4NO3-H2O, which is less corrosive due
water is of less attention in this paper.
to the replacement of halide ions by nitrate ions. Even the VLE properties
of some unpopular salts (e.g., nickel salts, cadmium salts, cesium salts)
4.3. IL-water
have also been studied [101–103].
Besides, the VLE properties of aqueous solution of salts with weak
As typical IL-H2O pairs, the VLE properties of aqueous solutions of
organic acid are also conducted for potential applications in LDAS. Wen
halide-based IL and [BF4]-based IL were studied in last decades, as
et al. [47] measured the vapor pressure of HCOOK-H2O with solute mass
shown above in Table 5. Generally, the strong negative deviation from
fraction from 0.64 to 0.73 under temperature from 20℃ to 40℃, which
the Raoult’s law leads to good potential for absorption systems [123].
shows comparability with LiCl-H2O with solute mass fraction from 0.32
However, studies confirmed the corrosiveness of halide ion and the risk
to 0.38. Vercher et al. [104] measured the vapor pressure of CH3COOK-
of releasing toxic HF for [BF4], so they may be replaced by new kinds of
H2O with isobaric method, while the interaction parameters of NRTL
safety IL.
model were regressed. Apelblat et al. [105] conducted the vapor pres­
To further design new IL, researchers explore the mechanism of hy­
sure measurements of saturated aqueous solutions of sodium and po­
groscopicity varied with ions. For the cations of IL, Fekadu et al. [7] and
tassium acetates, chlorates, and perchlorates from 5℃ to70℃. Beyer
Huddleston et al. [124] pointed out for imidazolium-based IL with the
et al. [86,88] gave the measurement results of vapor pressure, water
same anion, shorter alkyl chain in cation corresponded to lower vapor
activity and osmotic coefficient of HCOOK-H2O, HCOONa-H2O and
pressure. As for the anions of IL, Guo et al. [62] pointed out that IL with
CH3COONa-H2O from 5℃ to 35℃, and the data were correlated with
smaller hydrophilic anions (e.g, Cl-, Br-) possessed better moisture ab­
Pitzer model.
sorption property. Cao et al. [58] pointed out that weaker cation–anion
Apart from aqueous solutions with single salt, VLE properties of
interaction corresponded stronger ion-water interaction and thus
aqueous solutions with mixed salts are also measured [106,107]. Ertas
greater hygroscopicity, through which the design principle of hygro­
et al. [90] measured the vapor pressure of LiCl-CaCl2-H2O under tem­
scopic IL can be obtained. Feng et al. [125] used atomistic molecular
perature and mass fraction ranging from 21℃ to 60℃ and 0.2 to 0.4
dynamics to reveal the effect of chain length and anion type on the
respectively. Based on NRTL model, Zhao et al. [108] obtained the
aggregation behavior and diffusion performance in aqueous IL solution.
correlations of the activity coefficients of LiCl/LiBr-CaCl2/MgCl2-H2O
The results showed that shorter chain length exhibited better water
used in liquid desiccant dehumidification systems. Patil et al. [84]
solubility while Cl- possessed stronger interaction toward water mole­
measured the vapor pressures of LiCl-LiNO3-H2O (salt mole ratio
cule than [BF4].
0.88:0.12) and LiBr-LiNO3-H2O (salt mole ratio 0.7:0.3) under temper­
For imidazolium-based IL, [Emim]-based IL has the shortest alkyl
ature from 30℃ to 100℃, with solute mass fractions up to 0.6. Hassan
chain, while the vapor pressures of some of them within LDAS
et al. [109] carried out the vapor pressure measurement of CaCl2-Ca
requirement range were tested [126–128]. Nakata et al. [129] suggested
(NO3)2-H2O, and the solution with mass fractions of CaCl2 and Ca(NO3)2
that [Emim][TFO]–H2O yielded low vapor pressure nearly in accor­
of 0.5 and 0.2 was suggested to be applied in dehumidification appli­
dance to Raoult’s Law, while [Emim][ES]–H2O behaved negative de­
cations. De Lucas et al. [110] measured the vapor pressures of aqueous
viation to large extent. Considering its decomposition temperature of
mixture of LiBr and weak acid salts from 10℃ to 60℃, in which the
higher than 200℃, [Emim][TFO]–H2O was regarded as candidate for
mixture of LiBr and HCOONa with mass ratio of 2:1 was suggested as
absorption applications. The operation temperature for [Emim][ES] was
potential substitute of LiBr in LDAS, because of the comparative vapor
recommended to be lower than 140℃ by Heym et al. [126], which is
pressure.
also applicable for LDAS. [Emim][OAc]–H2O was also proposed for
In general, attributed to the wide applications of aqueous salt solu­
LDAS application, whose vapor pressures at 20℃ to 80℃ were
tions, the studies on their VLE properties are sufficient, while kinds of
measured under full concentration range [99,100,130]. Abumandour
models are adopted with satisfactory accuracy. For example, Cisternas-
et al. [131] measured the vapor pressures of [Emim][MS]–H2O with
Lam equation was successfully adopted in describing the vapor pressures
static method from 25℃ to 50℃, and their performances on an ab­
of 111 kinds of single-electrolyte solutions and 37 kinds of mixed-
sorption heat transformer were theoretically estimated. Vataščin et al.
electrolyte solutions, and the results of single-electrolyte solutions sug­
[132] compared the VLE of aqueous solution of [Emim][MS] and
gested an average deviation of 0.96 % [111]. A modified Debye-Hückel
[Emim][DMP], and they suggested that [Emim][DMP] had better water
equation was also well adopted to predict the vapor pressures of 144
affinity because of its strong hydrogen bond of water to anion.

6
J. Luo and H. Yang
Because of its environmental friendliness, choline-based IL was also
studied. Wasserscheid et al. [130] showed that 90 % [Ch][OAc]–H2O
yielded lower vapor pressure than 60 % LiBr-H2O. Constantinescu et al.
[133] conducted the VLE measurement of aqueous solutions of [Ch]
[Lac], [Ch][Gly], [Ch][TFO], and described the property with NRTL and
UNIQUAC model with good accuracy. Maekawa et al. [60] measured 7
kinds of quaternary ammonium IL as potential liquid desiccant in LDAS,
among which [Ch][DMP]–H2O yielded the lowest vapor pressure under
temperature from 20℃ to 50℃ and mass fraction from 0.2 to 0.8.
Meanwhile, all of 7 IL-H2O exhibited higher dehumidification capacity
than 30 % LiCl-H2O.
Some other kinds of IL are also tested with the VLE properties for
possible applications. Cao et al. [58] pointed out that amino acid IL had
application potential since they were biocompatible, biodegradable, and
easy to synthesis, and the hygroscopicity was tested. They suggested that
[P4444][Lys] delivered best moisture absorption capacity while the
[P4444][Glu] was the worst in the study. Römich et al. [100] measured
the vapor pressures of [DEMA][OMs]–H2O by Fourier transform
infrared (FTIR) spectroscopy in a dynamic cell, while the data from 20℃
to 80℃ were correlated with NRTL model. Watanabe et al. [134] tested
the dehumidification ratio and ability of several kinds of phosphonium-
based IL, among which [P4441][DMP] and [P4444][OAc] performed the
best.
Since there are lots of choices for the cation and anion of IL, the
exploration of IL-H2O is still of less mature. The mechanism for the
hygroscopicity of IL (or the group contribution of cations and anions)
can be further developed, which is helpful for effective design of liquid
desiccant.
4.4. Mixture-water
Based on the above three categories, their mixture is proposed for
potential applications.
Salt-glycol-H2O is early developed to improve the solubility of salt
and to relieve the volatility of glycol, while some of such mixtures yield
low vapor pressures. Park et al. [135] attempted to lower the vapor
pressure of LiBr-H2O by adding 1,3-propanediol, whose results showed
that the additive increased the solubility of solute and the vapor pressure
was decreased. At temperature from 30℃ to 70℃, Li et al. [136–139]
measured the vapor pressures of aqueous mixtures of typical halide salts
and glycol (e.g., LiCl-TEG-H2O, LiBr-TEG-H2O, LiBr-glycerol-H2O).
Królikowska et al. [140] measured the vapor pressures of LiBr-EG-H2O,
LiBr-DEG-H2O, LiBr-TEG-H2O, LiBr-glycerol-H2O, and COSMO-RS
model was accurately applied from 65℃ to 95℃. Parab et al. [141]
measured the vapor pressures of HCOOK-PG-H2O and HCOOK-glycerol-
H2O at temperature from 40℃ to 180℃.
For salt-IL-H2O, Chen et al. [142–147] conducted vapor pressure
measurements from 30℃ to 160℃ in recent years, in which the solute
included typical halide salt or HCOOK and imidazolium-based IL.
Antoine type equation was adopted for regression for the above solu­
tions, with average absolute relative deviation lower than 0.65 %. It was
found that LiCl displayed better hygroscopicity than LiBr in these mix­
tures, and I- corresponded to lowest vapor pressure among the anions of
IL. Moattar et al. [148] measured the vapor pressures of LiBr-[Bmim]Cl-
H2O and LiBr-[Emim]Cl-H2O at 25℃ under different concentrations. It
was found that the vapor pressure of system with [Emim]Cl was lower
than that with [Bmim]Cl, attributed to the shorter length of hydrocar­
bon chain. Li et al. [149] measured the vapor pressures of ternary sys­
tems salt-IL-H2O, in which LiBr or LiCl was selected as salt and [Dmim]
[Cl] or [Dmim][BF4] was selected as IL. At temperature from 30℃ to
166℃, the ternary solution with solute mass fraction from 0.2 to 0.7
displayed lower pressure than conventional LiBr-H2O and LiCl-H2O. Luo
et al. [150] measured the vapor pressures of LiNO3-[Emim]Cl-H2O and
LiNO3-[Emim]Br-H2O from 25℃ to 200℃, while their performance in
absorption heat pump is simulated.
Some other organic compounds are also mixed as potential substance
7
Applied Energy 325 (2022) 119853
for LDAS. Li et al. [151] tested the isobaric VLE of the addition of
[Bmim][Cl] and [Bmim][BF4] in aqueous acetonitrile solution, indi­
cating better interaction with water of [Bmim][Cl] than [Bmim][BF4].
Wen et al. [152,153] measured the vapor pressure of a mixture of LiCl,
hydroxyethyl urea and water, with the mass fraction of 25 %/39 %/36
%. The vapor pressure was proven comparative to 35 % LiCl-H2O within
the temperature range from 20℃ to 50℃. If the temperature increased,
the lower vapor pressure of the new mixture might lead to the difficulty
on regeneration.
As described in section 2.4, DES is also regarded as a kind of mixture,
and they may be possible candidate for liquid desiccant if soluble. Wu
et al. [154] measured the vapor pressures of 4 kinds of aqueous [Ch]Cl-
based DES from 30℃ to 70℃ at mass fraction from 0.2 to 0.8, whose
hydrogen bond donor was EG, glycerol, malonic acid or urea. The
measured results indicated the reduction effect of DES on the water
activity of aqueous solutions. Souza et al. [155] conducted the isobaric
measurement of VLE of DES-H2O using [Ch]Cl-glycerol from 48℃ to
70℃.
In consideration of the countless combination of solutes, lots of
mixture can be synthesized as possible candidate as liquid desiccant. To
reduce the experimental work for testing, accurate VLE model is
appealed for preliminary screening.
4.5. Models for VLE
As mentioned above, the establishment of accurate model will
effectively accelerate the exploration of new kinds of liquid desiccant.
Besides, with VLE model, solution parameters in regard of energy
requirement can be estimated, e.g., differential dilution heat, excess
properties, partial molar properties, which indicates the primary
importance of the exploration of VLE model [10]. Therefore, a scan of
existing VLE model is conducted in this section.
Because of the long-range and short-range effects, the behavior of
solution is likely in deviation of Raoult’s law. Therefore, except for the
experimental measurements, different models were also raised to
correlate the data and predict the unknown VLE properties within
required range. Typical models include Antoine equation, Pitzer model,
NRTL model, UNIFAC model, LIQUAC model, COSMO model
[72,89,156–159]. They are applied successfully for VLE property
description.
In order to improve accuracy, modifications of conventional VLE
models are raised. Chou and Tanioka [112] modified the expressions of
long-range and short-range contributions of electrolyte solutions, indi­
cating good agreement with experimental data with average relative
deviation less than 0.26 %. In 2011, Afanasev [160] developed a new
theory in account of the dependence of solvation numbers, through
which the limitation of Debye-Hückel method for electrolyte solutions
(i.e., only applicable for low concentration solution) can be solved. In
2013, Zuber et al. [161] applied Mattedi-Tavares-Castier equation of
state to estimate the thermophysical properties of aqueous solutions of
1:1 electrolyte, by which VLE of aqueous solutions of 13 kinds of halide
salts were described with good agreement. In 2016, Yao et al. [71]
compared SMR model and NRTL model for describing VLE property of
LiCl-CaCl2-H2O, in which SMR model was found to be accurate under
mass fraction lower than 0.1, and NRTL model possessed better agree­
ment under mass fraction higher than 0.3. As a result, a modification
was proposed to improve the agreement of prediction under the whole
concentration range. In 2019, Che et al. [89] presented a statistical
model for VLE determination of saturated liquid desiccant by re-
quantifying the weight of interactions between all species in solution,
which was recommended to be applied within the temperature range
from 10℃ to 80℃. In 2020, Che et al. [72] developed a modified
LIQUAC model for single solute liquid desiccant, whose accuracy at high
concentration and temperature was improved compared with conven­
tional NRTL model and LIQUAC model, attributed to its reevaluation to
the middle range interactions.
J. Luo and H. Yang
Molecular analysis (e.g., molecular dynamics) is also adopted in the
analysis of the interaction behavior between ions and water molecule, to
deeply reveal the absorption mechanism of certain functional group or
ions toward water. Yu et al. [162] unraveled the relationship between
microscopic interaction and VLE of aqueous glycol and IL. Atom number
density distributions suggested an increased anisotropy in IL-H2O with
the addition of glycol, which resulted in reduced vapor pressure in
macroscopics. Such theoretical method is anticipated in the estimation
of vapor pressure without lots of experiment.
Moreover, new kinds of simulation approaches are attempted in the
description of VLE. Monte Carlo simulation and artificial neural network
(ANN) is also attempted to predict the vapor pressure with existing data
points. Gandhidasan et al. [163] presented a prediction method for
vapor pressure of aqueous desiccants based on ANN, and the prediction
accuracy was compared with published data of LiCl-H2O, CaCl2-H2O and
LiBr-H2O. However, the establishment of ANN requires lots of experi­
mental data, while its extensionality for range outside the experiment is
still in debate. Karimzadeh et al. [164] used Monte Carlo simulation for
predicting the water activity of aqueous [Emim]-based IL solutions,
while its accuracy under high concentration is still far from satisfaction.
Although lots of VLE models are established based on thermophys­
ical principles, numerous experimental data points are still demanded to
improve their accuracies. Most of existing models can be applied for
fitting but only few of them can predict VLE without experimental data.
The insufficient knowledge of mixing rule and molecular interaction
limits the prediction accuracy, which is essential for conveniently select
the possible candidate of mixture-water pair among countless
combinations.
4.6. Overview
VLE property is essential for the selection of liquid desiccant, since it
is in relation to the absorption and desorption ability to large extent.
Fig. 4 and Fig. 5 show the relationship between vapor pressure and mass
fraction of some liquid desiccants at given temperatures (i.e., 20℃ and
60℃), which correspond to typical dehumidification and regeneration
conditions
[73,74,79,80,84,86–88,96,98,99,114,115,149,154,165,166]. In Fig. 4
and Fig. 5, DES1 represents the mixture of [Ch]Cl and EG with the molar
ratio of 1:2, while DES2 represents the mixture of [Ch]Cl and urea with
the molar ratio of 1:2. For mixture LiBr-LiNO3-H2O, the mixed ratio of
LiBr to LiNO3 is 0.7:0.3 on molar basis [84]. For mixture LiBr-[Dmim]Cl-
H2O, the mixed ratio of LiBr to [Dmim]Cl is 3:1 on mass basis [149].
Fig. 4. Vapor pressures of liquid desiccants varied with mass fraction at 20℃.
8
Applied Energy 325 (2022) 119853
From Fig. 4 and Fig. 5, it can be found that solutions of halide salts
show large vapor pressure gradient with the change of mass fraction,
while the curves of salts with weak acids are relatively smooth. To this
end, when absorbing a certain amount of moisture in air, the liquid
desiccant with larger vapor pressure change requires larger temperature
difference between dehumidification and regeneration. For example, the
regeneration temperature of LiCl-H2O is estimated to be higher than
80℃ while only about 60℃ is needed for CaCl2-H2O [167].
As a result, the selection of liquid desiccant in LDAS cannot focus
only on low vapor pressure during dehumidification. Solution with
lower vapor pressure often corresponds to more difficulty on regenera­
tion. For regeneration process in LDAS, solution with lower vapor
pressure needs to be heated to higher temperature, and extra energy will
be consumed during operation. If external heat source is applied, the
regeneration process will be also restricted by the temperature level of
heat source.
For salts with weak acids, the data of HCOOK-H2O is applicable for
higher concentrations. As shown in Fig. 4, the vapor pressure of HCOOK-
H2O at high concentration is comparative to that of CaCl2-H2O, illus­
trating the potential for HCOOK-H2O in LDAS application. Moreover, for
the sake of the saving of amount of liquid desiccant, the solution with
large concentration range is suitable for LDAS, since the circulating ratio
of liquid desiccant can be reduced.
Besides, some mechanisms about IL-H2O mentioned in the above
sections can be also quantitively demonstrated in Fig. 4 and Fig. 5.
[Emim][OAc]–H2O shows lower vapor pressure than [Dmim][OAc]–
H2O because of its shorter alkyl chain of cation. [Dmim]Cl-H2O shows
lower vapor pressure than [Dmim][OAc]–H2O because of its anion with
better hygroscopicity.
For mixed-solute solutions, it can be found that the vapor pressure
lay between the values of the single-component system. For example,
vapor pressure of LiBr-[Dmim]Cl-H2O is lower than [Dmim]Cl-H2O but
higher than LiBr-H2O at same concentration. Therefore, even though
anti-corrosive composition is suggested to be added into conventional
halide salt solutions, the deterioration of water absorption ability is still
worth concern to avoid the excessively increase of vapor pressure. On
the other hand, in consideration of limited solubility of salt, the addition
of another solute (e.g., IL) is expected to play positive role in increasing
moisture absorption ability at a higher concentration. However, it is
found from existing studies that the vapor pressure of mixed-solute so­
lution in experiment deviate largely with the predicted value obtained
through simple mixed rule (SMR model), so a modified mixed rule is
worthy exploration for predict the vapor pressures of mixed-solute
J. Luo and H. Yang Applied Energy 325 (2022) 119853

Fig. 5. Vapor pressures of liquid desiccants varied with mass fraction at 60℃.

solution without beaucoup experiment [168]. can be derived using Clausius–Clapeyron equation.
As for DES, DES1-H2O may be favorable against DES2-H2O in LDAS Table 6 depicts the up-to-date studied range of specific heat capac­
applications, because DES1-H2O yields low vapor pressure in dehu­ ities of typical liquid desiccants. Only the data with temperature and
midification with the comparative vapor pressure in regeneration, as concentration for LDAS application requirement are included. Except for
shown in Fig. 4 and Fig. 5. desiccant listed in Table 6, some other potential candidates are intro­
In conclusion, solutions with large vapor pressure gradient with the duced thereinafter, while a comparison between different liquid desic­
change of mass fraction is recommended, which correspond to better cants in aspect of specific heat capacity is carried out in section 5.6.
water absorption ability and lower regeneration temperature. Never­
theless, the investigation on VLE of new kind of liquid desiccants (e.g., 5.1. Salt-water
new kind of DES) is appealed in consideration of their prospective
application. Similar to VLE, specific heat capacity of aqueous solution with salt
has been widely investigated, in which the data cover the requirement of
5. Current studies on the heat capacity of liquid desiccants LDAS.
Laliberté [169] reviewed the heat capacity data of 79 single salt so­
Specific heat capacity has essential relationship with moisture ab­ lutions, in which common-used liquid desiccants were included, e.g.,
sorption ability during operation of LDAS. Giampieri et al. [10] sug­ LiCl-H2O, CaCl2-H2O, MgCl2-H2O. Liu et al. [174] suggested that as
gested larger heat capacity of solution corresponded to less temperature typical liquid desiccants, LiBr-H2O displayed lower specific heat ca­
increase during water absorption, which was favorable for liquid pacity than LiCl-H2O under the same vapor pressure. Giampieri et al.
desiccant to maintain better absorption ability. Moreover, heat capacity [10] compared the specific heat capacities of LiCl-H2O, CaCl2-H2O, LiBr-
can be used to determine the sensible heat requirement in practical H2O and HCOOK-H2O at certain concentration. It was found that LiCl-
applications. For example, with the VLE property and heat capacity of H2O delivered the highest specific heat capacity, resulting in most stable
solution, the enthalpy of solution at any temperature and concentration dehumidification process. The specific heat capacity of HCOOK-H2O
was formulated by Ayyagari et al. [38] for applications of water
harvester. Except for common-used salt solutions, the heat capacities of
Table 6
aqueous solutions with unpopular salts are also investigated, e.g., CuCl2-
Studies on specific heat capacity of typical liquid desiccants for LDAS
applications. H2O, NiCl2-H2O [103].
Apart from aqueous solutions with single salt, heat capacities of
Desiccant Solute mass fraction Temperature (℃) Literature
aqueous mixed salts are also measured. Gao et al. [175] measured the
LiCl-H2O 0–0.50 − 10–130 [74,169] heat capacities of LiBr-HCOOK-H2O and LiBr-HCOONa-H2O with salt
LiBr-H2O 0–0.65 0–150 [75]
mass ratio of 2:1 under temperature ranging from 35℃ to 80℃.
CaCl2-H2O 0–0.50 − 15–327 [74,103,169]
MgCl2-H2O 0–0.35 5–120 [169] The results indicate that the heat capacity data of aqueous solutions
LiNO3-H2O 0–0.60 25–100 [82,83] of salts are sufficient for the performance evaluation in LDAS.
HCOOK-H2O 0.50–0.72 10–80 [10,38]
CH3COOK-H2O 0–0.50 20–51 [169]
CH3COONa-H2O 0–0.58 5–120 [88,169]
5.2. Glycol-water
HCOONa-H2O 0–0.17 0–120 [86,169]
CaCl2-MgCl2-H2O 0–0.20/0–0.17 25–100 [103,169] As aforementioned, the attempt on the LDAS application of glyco­
TEG-H2O 0.68–1 30–80 [170] l–water pair is limited by the volatility of glycol, and the related studies
PG-H2O 0.51–1 30–80 [170]
were mainly conducted in last century.
[Bmim]Cl-H2O 0.52–0.94 30–80 [171]
[Bmim]Br-H2O 0.57–0.95 30–80 [171] Gómez et al. [28] reported the isobaric specific heat capacities of 95
[Bmim][BF4]–H2O 0.76–1 30–80 [172] % TEG-H2O under 25℃ and 75℃, which was comparative to common-
[Emim][OAc]– 0–1 20–90 [99,100] used LiCl-H2O, CaCl2-H2O and LiBr-H2O. Li et al. [170] reported the
H2O specific heat capacities of DEG-H2O, TEG-H2O, T4EG-H2O, PG-H2O and
[Emim][ES]–H2O 0–1 10–80 [173]
DPG-H2O under full mole fraction range at temperature from 30℃ to

9
J. Luo and H. Yang
80℃.
5.3. IL-water
The heat capacity of IL-H2O has been somewhat investigated, which
is still not enough for LDAS applications.
Qu et al. [99] gave the specific heat capacity of [Emim][OAc]–H2O
at 20℃ to 90℃ under full concentration range, while a polynomial
function of temperature and mass fraction was applied for regression
with R2 of 99.89 %. He et al. [158] measured the heat capacity of
[Dmim][DMP]–H2O from 25℃ to 50℃, and the excess enthalpy of the
solution was derived through the integration of VLE and heat capacity
properties. Abumandour et al. [131] measured the heat capacities of
[Dmim][MS]–H2O and [Emim][MS]–H2O from 21℃ to 65℃ under full
concentration range, and then the excess heat capacity was also derived.
García-Miaja et al. [176] measured the heat capacities of [Emim][TFO]–
H2O and [Bmim][TFO]–H2O from 20℃ to 45℃ under full concentration
range. Yu et al. [172] measured the heat capacities of [Bmim][BF4]–H2O
and [Bmim][PF6]–H2O from 20℃ to 80℃, and the excess molar heat
capacity was then derived through Redlich-Kister equation. Zuo et al.
[165] measured the heat capacity of [Emim][ES]–H2O at the tempera­
ture from 30℃ to 50℃, whose results showed that the heat capacity of
aqueous solution declined with the addition of IL. Nie et al. [123] pre­
liminarily measured the heat capacity of [Hydemim]Cl-H2O from 25℃
to 85℃, and a polynomial function was applied with 0.38 % deviation
for data correlation.
In 2019, Troncoso [177] reviewed the existing studies on the isobaric
heat capacity of IL in aqueous solution, in which 25 kinds of IL-H2O were
included. Most of them were composed with inorganic or alkylsulfate
anions (e.g., Cl-, Br-, [ES], [MS]) and dialkylimidazolium cations (e.g.,
[Bmim], [Emim]). For most of cases, the data under nearly full con­
centration range were reviewed from room temperature to more than
50℃. Generally speaking, the studies on the specific heat capacity of IL-
H2O is stilled limited in imidazolium-based IL, and the measurements of
other kinds of IL are appealed.
5.4. Mixture-water
Gao et al. [175] measured the heat capacities of LiBr-TEG-H2O and
LiBr-PG-H2O with salt mass ratio of 1:2 from 35℃ to 70℃, in which the
data showed great linearity with temperature under given concentra­
tion. Li et al. [170,178] reported the specific heat capacities of ternary
mixtures of halide salt, glycol and water at temperature from 30℃ to
80℃. Luo et al. [150] measured the heat capacities of LiNO3-[Emim]Cl-
H2O and LiNO3-[Emim]Br-H2O from 25℃ to 100℃, whose results
showed that the heat capacity of former was higher than that of latter.
Leron et al. [179] measured the molar heat capacity of aqueous [Ch]Cl-
based DES solution using a heat flow differential scanning calorimeter,
and the data from 30℃ to 80℃ were obtained.
The heat capacity property of mixture-water is still lack of investi­
gation. The present data mainly focus on salt-glycol–water, while the
heat capacity data of the mixture with IL are scarce.
5.5. Models for heat capacity
Compared with various types of VLE model, the model of specific
heat capacity is relatively simple.
Commonly, it is expressed as a polynomial function of temperature
and concentration, and the accuracy of such function is proven satis­
factory [76,175]. In 2009, based on the weighing average of heat ca­
pacities of solute and solvent, a model for heat capacity calculation was
developed by Laliberté[169], which was able to determine the heat
capacity of solution with an arbitrary number of solutes and at an
arbitrary temperature. The insignificant effect of pressure on heat ca­
pacity was also indicated. The model was examined with heat capacity
data of 79 single solute solutions and 13 multi solute solutions, with the
10
Applied Energy 325 (2022) 119853
average deviation less than 0.003 kJ/kg/℃. The model is also valid for
other systems, e.g., IL-H2O. In 2019, Troncoso [177] correlated the
existing heat capacity data of 25 kinds of IL-H2O with a polynomial
function, through which the excess heat capacity can be well described.
Besides, some models of heat capacity are raised with physical prin­
ciple, such as Helmholtz energy equation of state, generalized equation,
corresponding states equation [180]. Chen et al. [181] adopted molec­
ular dynamics to simulate the heat capacity of LiBr solution, while the
infinite dilution model with three groups of ion parameters was used. In
their study, ions or atoms are assumed to be involved with Van del Waals
interaction and electrostatic interaction. However, the simulation re­
sults indicated that using existing ion models, the maximum deviation
larger than 12 % for specific heat capacity was observed for the appli­
cation range of LDAS for LiBr solution.
Although models from perspective of molecular scale are more
convinced in the prediction of heat capacity of a substance with sparse
datapoints, their accuracy is not satisfactory enough and required to be
further improved. With certain amount of experimental data, the poly­
nomial function is still recommended in industrial and engineering
fields attributed to its simplicity and accuracy.
5.6. Overview
According to the data in Fig. 4 and Fig. 5, the potential component
and concentration of liquid desiccant can be preliminarily obtained.
With given mass fraction, the specific heat capacities of typical liquid
desiccants varied with temperature can be obtained, as shown in Fig. 6
[38,74,75,82,169–173,179]. The mass fraction of liquid desiccant is
shown in the legends of Fig. 6. In Fig. 6, DES1 and DES2 represent the
same substance as those in Fig. 4 and Fig. 5. For mixture LiCl-CaCl2-H2O,
the mixed ratio of LiCl to CaCl2 is 1:1 on mass basis. For mixture LiBr-
TEG-H2O, the mixed ratio of LiBr to TEG is 1:2 on mass basis [170].
As shown in Fig. 6, most of curves show linearity, which indicates the
reasonability of adopting the linear regression for heat capacity model.
It is known that higher specific heat capacity corresponds to less
temperature rise during adiabatic dehumidification, which is favorable
in the maintenance of moisture absorption ability. On the contrary, a
rapid increase of specific heat capacity with the increase of temperature
leads to more heat requirement for regeneration of liquid desiccant. To
this end, the liquid with a curve in Fig. 6 as flat as possible is advanta­
geous in aspect of specific heat capacity.
6. Current studies on the safety concern of liquid desiccants
The safety issues are of great concern for the application of liquid
desiccants. In general, the safety issues include the following topics: 1)
the content in indoor air and its toxicity; 2) the effect on pollutant
removal; 3) crystallization and corrosiveness. The safety characteristics
of liquid desiccant are highly relevant to the feasibility of the solution
and service life of LDAS.
6.1. The content in indoor air and its toxicity
Typically, the content of liquid desiccant diffused in indoor air owes
to the volatility of liquid desiccant and the carryover phenomenon in air
flow. To avoid harmfulness to humankind, the threshold of safety con­
centration in air should be established, while the detection of liquid
entrainment is also appealed.
It has been widely accepted that the volatility of glycol leads to
application difficulty in LDAS [37]. On the contrary, the volatility of salt
or IL is nearly negligible [56]. For common-used salt solution, the
diffusion of ions in the application of LDAS are investigated. Fu et al.
[24] listed the safety thresholds of content of LiBr in air in UK, USA and
China, whose lowest value was specified as 70 μg/m3. The experiment of
LDAS using LiBr-H2O showed that the concentration of Li+ was 20 μg/
m3 in air duct, and no Li+ and Br- were detected in indoor air [182].
J. Luo and H. Yang Applied Energy 325 (2022) 119853

Fig. 6. Specific heat capacity of liquid desiccants varied with temperature.

Meanwhile, an experiment was reported to investigate the carryover of

Table 7
LiBr-H2O, whose results showed that the concentrations of Li+ and Br- at
Oral LD50 for typical solutes in liquid desiccants[193].
sampling points were lower than 4.7 μg/m3 and 33 μg/m3 respectively
[24]. It was found that the ion content in indoor air showed positive Group Material LD50 (mg/kg) Tested animals
correspondence to air flow rate [182]. Wang [183] experimentally Inorganic salt LiCl 1165 mouse
revealed that the increase of solution flow rate led to the increase of Li+ KCl 1500 mouse
and Ca2+ in dehumidified air. LiBr 1840 mouse
CaCl2 1940 mouse
For the non-volatile liquid desiccant, carryover of liquid droplets is MgCl2 7600 mouse
the main reason for the existence of liquid desiccant in air duct or even Salt with organic acid HCOOK 5500 mouse
indoor environment [184]. For traditional packed-bed dehumidifier, the HCOONa 4700 mouse
drawback of droplet entrainment is noticeable due to the direct contact CH3COOK 3250 rat
CH3COONa 25,956 rat
of liquid desiccant and airflow [185]. Conditions of airflow and liquid
Glycol EG 5500 mouse
flow are both vital parameters affecting carryover phenomenon, and DEG 2300 mouse
researchers put forward multiple modification on conventional direct TEG 20,000 mouse
contact dehumidifier, e.g., reducing flow velocity, eliminating apparent PG 20,300 mouse
desiccant film flow, designing specific plate morphology, developing IL [Ch]Cl 3900 mouse

new column plate, adjusting location of liquid distributor [12,186–189].

Lowenstein et al. [190] proposed a zero carryover LDAS by using low-
flow technology, in which the velocity of liquid desiccant could be
remarkably reduced compared with conventional packed-bed tower.
Lyu et al. [191] conducted experiment to investigate the factors of
droplet formation and entrainment, whose results showed that better
flow stability with counterflow pattern was beneficial for alleviate the
problem of carryover for a flat falling-film device.
In addition, developing new material to inhibit the direct contact
between liquid and air is also helpful for eliminate the carryover in
LDAS. Liquid to air membrane energy exchanger (LAMEE) is regarded as
an effective device with the utilization of semi-permeable membrane (i.
e., only permeable to vapor but impermeable to liquid droplet), despite
the inclusion of additional heat and mass transfer resistance of mem­
brane [185,192]. The development of dehumidifier or regenerator for
alleviating or eliminating carryover has been reviewed by Ren et al. [12]
and Gurubalan et al. [13], and here the toxicity of liquid desiccant is
introduced.
For typical chemical material, their safety data, e.g., toxicity and
flammability, can be obtained in the Material Safety Data Sheet (MSDS).
The toxicity of salt or glycol is commonly obtained through animal
experiment. The most common-used criterion is lethal dose 50 (LD50),
which is defined as the amount of a material leading to the death of 50 %
of tested animals. The toxicity data of LD50 for salts or glycols used as
solute in liquid desiccant can be searched in chemical websites or soft­
ware, some of which are listed as follows in Table 7 [193]. According to
the Hodge and Sterner toxicity scale, substance with oral LD50 higher
than 5000 can be regarded as practically non-toxic [194]. In this regard,
promising candidates for future applications can be selected. Except for
the oral test, the effects of inhalation and skin contact should be also
evaluated, and the existing data can be also found in chemical websites
[29,193].
In contrast, the toxicity data of IL-H2O, especially the data relevant to
LDAS working conditions, are scarce. As shown in Table 7, the oral LD50
data of [Ch]Cl can be searched while the other common-used imidazo­
lium-based IL (e.g., [Bmim][BF4]) are missing. Besides, some studies on
toxicity of IL are conducted in other aspects. Zhang et al. [195] tested
the acute toxicity of [Bmim][BF4] and [Bmim]Cl in the liver cells of
zebrafish with different doses on 7 and 14 days. Leitch et al. [196] made
a literature survey on the toxicity of methylimidazolium IL, whose re­
sults indicated that the human health hazards of most of methyl­
imidazolium IL were lack of data. Some specific structures e.g., [BF4]
and [PF6], were reported unstable in aquatic environment with the risk
of releasing toxic HF, so IL composed of halogen-free group was antic­
ipated for future investigations [58,197]. On the other hand, [Ch]-based
IL was well known as safe and economical IL due to its biodegradable
characteristics and high biocompatibility [60].
The thermal stability is also important during operation, especially in
dehumidification and regeneration processes. For instance, through
thermogravimetric measurements, the long-term stability of [Emim]
[ES]–H2O was estimated as 34 years by Heym et al. [126]. Besides,

11
J. Luo and H. Yang
Huddleston et al. [124] listed the thermal decomposition temperatures
and glass transition temperatures of several kinds of IL-H2O, most of
which were higher than 200℃ and lower than − 60℃ respectively.
Similarly, Nakata [129] pointed out that several [Bmim]-based and
[Emim]-based IL were able to be stable up to at least 200℃ and suffered
glass transition under about − 80℃. Merkel et al. [198] tested the mass
loss rates of different IL, through which they found that [Emim] cation
and [TFO] anion showed better thermal stability than [DEMA] cation
and [OAc] anion. However, it should be noted that for potential appli­
cation in LDAS, the stability of specific IL should be evaluated carefully
to avoid danger in daily operation [199].
In 2021, Cho et al. [197] reviewed the toxicities of IL and the
structural effects of IL on toxicity were concluded, as shown in Fig. 7.
In spite of the diversity and complexity of IL, few of them can be
considered as potential liquid desiccant. Fortunately, it is shown in Fig. 7
that most of characteristics favorable for liquid desiccant are low toxic,
e.g., hydrophilic structures. Moreover, cations with short alkyl chain are
likely low toxic, which yield lower vapor pressure in LDAS applications
as well. From Fig. 7, the prospect of IL in application in aspect of toxicity
will be desirable.
6.2. The effect on pollutant removal
The pollutant in air includes volatile organic compound (VOC),
biological pollutants, particulate matters (PM). Due to low concentra­
tion and high diversity, the removal of pollutant in air is always a
difficult but important issue in air-conditioning applications [200].
In consideration of numerous kinds of VOC, the absorption effect of
liquid desiccant depends on the type of VOC. Liquid desiccant plays
effective roles on the removal of water-soluble VOC, such as formalde­
hyde [201]. The different solubilities of different VOC in water resulted
in different characteristics of absorption, while the solubility was also
influenced by the mass fraction of salt. With higher temperature of air,
formaldehyde can be absorbed more easily due to larger Henry’s law
constant [202].
As for VOC insoluble in water, salt solution yields worse removal
ability than aqueous glycol or IL. For instance, it was reported that LiCl-
H2O with mass fraction of 0.4 could remove 20 % of toluene and almost
none of 1,1,1-trichloroethane [24]. As organic solvents, glycol and IL are
expected to possess better ability for removal of VOC. For instance, it is
reported by Chung et al. [203] that nearly 100 % of toluene and 1,1,1-
trichloroethane can be removed by 95 % TEG solution, while 56 % of
CO2 and up to 30 % of formaldehyde can be also absorbed. Chau et al.
[204] investigated the influence of operating parameters on the removal
effect of TEG. It was found that the removal rate and removal efficiency
were influenced significantly by the liquid–gas flow rate ratio. Wu et al.
[205,206] depicted the relationship between TEG concentration and the
absorption rate for methanol, toluene, ethyl ether, and methyl-ethyl
ketone, while the equilibrium process and the surface tension between
Fig. 7. Characteristics of IL related to toxicity.
12
Applied Energy 325 (2022) 119853
TEG-H2O and VOC were also measured. The ability of IL to reduce or
even eliminate the hazards of VOC was also addressed, while more
experimental data are anticipated [58].
Some other gaseous pollutants can be also removed by liquid desic­
cant, e.g., CO2, SOx, NOx [201,207,208]. It is also reported that some
popular aqueous organic solutions, such as MDEA aqueous solution used
for CO2 capture, also delivered low vapor pressure [209,210]. Through
density functional theory (DFT), García et al. [211] analyzed the
mechanism of the removal effect of acid gas (e.g., SO2) for [Ch][Lac]. 12
kinds of IL were raised by Wu et al. [212] for application of absorption
heat pump, because of their good capability on NH3 absorption. Wang
et al. [213] tested the performance of IL (e.g., [Bmim][Tf2N], [Bmim]
[BF4]) for CO2 capture and H2S removal, and the program based on
Aspen Plus software and COSMO-SAC property model was established. It
is suggested that IL can be purposefully designed according to the
interaction mechanism between IL and specific matters (e.g., CO2, H2S).
Biological pollutant, such as bacteria and virus, can be also removed
through the application of liquid desiccant, while conventional
condensation dehumidification system has severe risk for breeding
microorganism [24]. It is convinced by researchers that biological
pollution is an essential factor for sick building syndrome, while liquid
desiccant plays positive roles in filtering, killing or inactivating biolog­
ical pollution to large extent [9]. Typical liquid desiccants, e.g., LiCl-
H2O and LiBr-H2O, were claimed as biocides to kinds of microorganism
(e.g., streptococcus, staphylococcus, anthrax spores, SARS virus),
attributed to the biodegrading phenomenon of genetic material in these
liquid desiccants [24,32]. Skinner et al. [214] experimentally demon­
strated the inhibition on the replication of several DNA and RNA viruses
in LiCl-H2O. Except for salt solutions, TEG solution was also tested and
the results exhibited positive evidence bactericidal effect [215]. If LiCl,
LiBr or TEG is applied as liquid desiccant material directly contacting
with air in LDAS, the percentage of removing bacteria can be expected to
be higher than 90 % [32].
Besides, airborne PM can be also effectively filtered in LDAS. For
common-used tower-based liquid desiccant dehumidifier, e.g., spray
tower or packed tower, the PM removal mechanism is similar to that of
wet dust collector. The PM filtration efficiency of LiBr-H2O was exam­
ined by Liu et al. [216], whose results indicated the filtration efficiency
of PM5 of 20 %-30 %. It was reported that LDAS showed significant
filtering effect on PM when the particle diameter was larger than 5 μm
[24]. However, it should be noted that owing to the carryover of liquid
desiccant, additional PM with lower diameter (e.g., PM0.5) may be
produced. Meanwhile, the corrosion of liquid desiccant may result in the
rust of metal material carried by the air, which is also the source of PM.
6.3. Crystallization and corrosiveness
Typical liquid desiccants with halide salts (e.g., LiCl-H2O, LiBr-H2O,
MgCl2-H2O) face the limitation of the operating range due to
J. Luo and H. Yang Applied Energy 325 (2022) 119853

crystallization risk, which is harmful for both the flow condition and the
mass transfer characteristic [10,217,218]. Giampieri et al. [10] sug­
gested that among typical liquid desiccants, HCOOK-H2O held lower
crystallization risk because of higher saturation concentration and lower
freezing temperature. Królikowska et al. introduced the studies on the
inclusion of anticrystallization additives for LiBr-H2O to increase the
solubility, e.g., crown ethers, glycol, IL [140,219,220]. Parab et al.
[141] suggested the inclusion of PG or glycerol can improve the solu­
bility of HCOOK in water. Królikowska et al. [107] measured the solu­
bility of LiBr-H2O after adding other lithium salts, and it was shown that
the addition of lithium acetate or lithium lactate displayed positive ef­
fect on increasing the solubility and reducing crystallization risk of LiBr-
H2O. Compared with salt, glycol and IL solutes suffer from lower crys­
tallization risk because they are commonly liquid at room temperature.
The aqueous solubilities of typical salts used in LDAS are shown in
Fig. 8 [74,219,221–225]. For mixture LiBr-LiCl-H2O and LiBr-HCOONa-
H2O, the mixed ratio of LiBr to LiCl or HCOONa is 2:1 on mass basis. For
mixture LiBr-TEG-H2O, the mixed ratio of LiBr to TEG is 0.7:0.3 on mass
basis.
As for corrosiveness, it is the main restriction of typical salt-H2O for
further applications, while those of glycol-H2O and IL-H2O can be
significantly improved. It should be noted that with carryover phe­
nomenon in LDAS, corrosiveness may happen at not only the compo­
nents delivering solutions but also the components delivering processed
air. It has been demonstrated that the corrosion rate of metals signifi­
cantly enhanced with the involvement of O2 and CO2 in component
directly contacting with air (e.g., an open regenerator) [226].
Numerous studies and practical applications confirm the severe
corrosion to materials (especially metals) under the application of salt-
H2O as liquid desiccant [9,29]. Since the principle of metal corrosion is
commonly the loss of electron, the pH value of solution becomes an
essential factor influencing the corrosiveness of liquid desiccant [227].
It is well accepted that halogen ions (e.g, Cl-, Br-) behave greater
corrosiveness in solutions under acid environment (i.e., pH less than 7).
The corrosion rate of Cl- was faster than that of Br- attributed to its strong
aggression to metal film [150]. In aspect of material, carbon steel suf­
fered from more severe corrosion in acid environment, while the
corrosion of aluminum showed less correspondence with pH value [10].
Even if some anti-corrosive components are added into solution, the
corrosion can be just alleviated rather than eliminated [152,153].
Moreover, anti-corrosive material such as plastic often possesses poor
wettability as well as low heat and mass transfer efficiency [5]. Mean­
while, corrosion is also highly relevant to the solution temperature that
higher temperature behaves faster corrosion rate [228]. The corrosion
thicknesses of carbon steel and stainless steel 304 in LiBr-H2O and
LiNO3-H2O were investigated by Luo et al. [82] at 453.15 K, in which
obviously less corrosiveness of LiNO3-H2O was observed against LiBr-
H2O. To this end, salts with weak organic acid (e.g., HCOOK) should be
promising alternatives to conventional halide salt, due to its alkaline pH
in aqueous solution and the absence of halogen ions. It can be also
regarded as additive to conventional LiBr-H2O, with significant effect in
reducing corrosiveness [110].
Compared with aqueous salt solution, IL-H2O delivers better char­
acteristic in aspect of corrosiveness. Wasserscheid et al. [130] tested the
corrosion rates of [Emim][OAc]–H2O and [Ch][OAc]–H2O to copper
and steel, which is much lower than LiBr-H2O. Meanwhile, the influence
of solution temperature was also investigated that the corrosion rate at
90℃ was about 10 times of that at 25℃. Maekawa et al. [60] and
Watanabe et al. [134] tested the corrosiveness of 11 kinds of aqueous
solutions of IL, and the weight losses of different metals during 24 h were
weighed to demonstrate to better compatibility of IL-H2O against LiCl-
H2O. The less corrosiveness and lower crystallization risk of IL-H2O
compensated to the lower energy efficiency against conventional LiCl-
H2O to some extent [131].
7. Current studies on other properties of liquid desiccants
Apart from the above important properties, there are some other
factors or properties to be considered in LDAS application. In this sec­
tion, the following studies are to be reviewed: 1) density; 2) viscosity; 3)
cost; 4) others. As introduced in Table 4, these properties are of less
importance in regard of energy and environmental performance than
those introduced in section 4–6, so the review in this section is con­
ducted in a relatively simple way with brief comparison.
7.1. Density
Density of solution is relevant to the power consumption of pump in
practical applications. Table 8 depicts the up-to-date studied range of
densities of typical liquid desiccants. Only the data with temperature
and concentration for LDAS application requirement are included.
Except for desiccants listed in Table 8, some other potential candidates
are introduced thereinafter, while a comparison between different liquid
desiccants in aspect of density is carried out at the end of this subsection.
Similar to VLE and heat capacity, the density of aqueous salt solution
has been widely investigated, in which the data cover the requirement of
LDAS. In 2004, Laliberté and Cooper [229] reviewed the density data of
59 electrolyte solutions, in which common-used liquid desiccants were
included.
As for glycol–water, Gómez et al. [28] reported the densities of 95 %
TEG-H2O under 25℃ and 75℃, which was lower than common-used
LiCl-H2O, CaCl2-H2O and LiBr-H2O. Sun et al. [231,232] gave the den­
sities of EG-H2O, DEG-H2O, TEG-H2O, PG-H2O, DPG-H2O and TPG-H2O

Table 8
Studies on density of typical liquid desiccants for LDAS applications.
Desiccant Solute mass fraction Temperature (℃) Literature

LiCl-H2O 0–0.45 5–95 [229]

LiBr-H2O 0–0.70 − 60–200 [75]
CaCl2-H2O 0–0.51 0–100 [229]
MgCl2-H2O 0–0.33 0–100 [229]
LiNO3-H2O 0–0.62 0–110 [169]
HCOOK-H2O 0–0.78 15–65 [169,230]
HCOONa-H2O 0–0.41 25–45 [169]
CH3COOK-H2O 0–0.60 15–55 [169]
TEG-H2O 0.73–0.96 22–175 [231]
TPG-H2O 0.78–0.97 21–174 [232]
PG-H2O 0.58–0.93 23–172 [232]
[Bmim][BF4]–H2O 0–1 30–80 [233]
[Emim][ES]–H2O 0.75–1 30–50 [165]
[Emim][OAc]–H2O 0–0.95 20–80 [99,100]
Fig. 8. Solubilities of typical salts in water varied with temperature.

13
J. Luo and H. Yang Applied Energy 325 (2022) 119853

with molar fraction from 0.25 to 0.75 at temperature from 17℃ to using weighted harmonic average of densities of solute and solvent,
187℃. whose average deviation with experimental data for single electrolyte
The density of IL-H2O is also investigated. Qu et al. [99] proposed a solution was observed to be less than 0.1 kg/m3. Subsequently, the
polynomial function of temperature and mass fraction to describe the model was modified by Mamontov and Gorbachev [244] by taken into
density of [Emim][OAc]–H2O from 20℃ to 80℃ at full concentration account the ion strength in solutions, through which the calculation
range. Jacquemin et al. [234] suggested the densities of saturated accuracy for mixed strong electrolyte solution was improved.
aqueous solution of [Tf2N]-based IL were more than 30 % higher than Based on the infinite dilution model with three groups of ion pa­
that of pure water at temperature from 20℃ to 70℃. Abumandour et al. rameters, Chen et al. [181] adopted molecular dynamics to simulate the
[131] measured the densities of [Dmim][MS]–H2O and [Emim][MS]– density of LiBr solution. As a static property, density can be accurately
H2O from 20℃ to 50℃ under full concentration range, and the densities predicted by equilibrium molecular dynamics, with deviation less than
of these two IL were significantly higher than that of water. The densities 6 % at mass fraction from 0.4 to 0.6 and temperature from 5℃ to 80℃.
of aqueous solutions of other IL were also measured within the Herrera et al. [245] successfully determined the non-ideality of aqueous
requirement range of LDAS, including [Bmim][DMP], [Dmim][DMP], [Emim]-based or [Ch]-based IL by means of molecular dynamics, whose
[Emim][DMP], [Hydemim]Cl, [DEMA][OMs] [100,123,158,235]. results were consistent with that of Redlich-Kister polynomials. Besides,
For mixture-water pair, Li et al. [136–139] and Królikowska et al. group contribution method or even artificial intelligence were success­
[107,140] measured the densities of various type of mixtures of halide fully attempted to describe or predict the density of mixtures [246].
salt-glycol–water at temperature from 20℃ to 75℃, including LiCl-TEG-
H2O, LiBr-TEG-H2O, LiBr-PG-H2O, MgCl2-TEG-H2O, while an exponen­
tial function was adopted to correlate the data. Parab et al. [141] 7.2. Viscosity
measured the densities of HCOOK-PG-H2O and HCOOK-glycerol-H2O at
30℃ and mass fraction ranging from 0.45 to 0.75. Frouzesh et al. Viscosity represents the flow characteristic of solution, which affects
[236,237] measured the densities of aqueous mixture of lithium salt and flow condition and flow pattern during operation. It is also an essential
halide IL from 25℃ to 45℃ at different concentrations (e.g., LiBr- factor for the pressure drop along pipelines.
[Bmim]Cl-H2O, LiCl-[Emim]Cl-H2O, LiNO3-[Emim]Cl-H2O). The den­ Table 9 depicts the up-to-date studied range of viscosities of typical
sities of aqueous solutions of [Ch]Cl-based DES and glycol-based DES are liquid desiccants. Only the data with temperature and concentration for
also measured within the temperature range of LDAS [238–243].
Based on the concentration shown in Fig. 6, the densities of liquid Table 9
desiccants varied with temperature can be obtained, as shown in Fig. 9 Studies on viscosity of typical liquid desiccants for LDAS applications.
[38,74,75,83,99,140,165,229,231–233,235,242,243]. The mass frac­ Desiccant Solute mass fraction Temperature (℃) Literature
tion of liquid desiccant is shown in the legends. In Fig. 9, DES1 and DES2
LiCl-H2O 0–0.45 0–95 [247]
represent the same substance as those in Fig. 4 and Fig. 5. For mixture LiBr-H2O 0.15–0.65 25–200 [248,249]
LiCl-CaCl2-H2O, the mixed ratio of LiCl to CaCl2 is 1:1 on mass basis. For CaCl2-H2O 0–0.51 0–100 [247]
mixture LiBr-TEG-H2O, the mixed ratio of LiBr to TEG is 0.7:0.3 on mass MgCl2-H2O 0–0.39 15–70 [247]
basis [140]. LiNO3-H2O 0–0.67 0–110 [247]
HCOOK-H2O 0–0.81 1–80 [247,250]
It can be found that except for aqueous LiBr with mass fraction of
CH3COOK-H2O 0–0.60 15–55 [169]
0.45, the other curves in Fig. 9 show little difference, and the density of CH3COONa-H2O 0–0.46 25–55 [247]
high-concentration LiBr solution can be reduced by addition of the other TEG-H2O 0.73–0.96 20–176 [231]
component in Fig. 9 (e.g., LiBr-TEG-H2O). TPG-H2O 0.78–0.97 21–177 [232]
As shown in Fig. 9, the density of aqueous solution can be simply PG-H2O 0.58–0.93 23–177 [232]
[Bmim][BF4]–H2O 0–1 30–80 [233]
expressed as linear function with temperature with satisfactory [Bmim][DMP]–H2O 0.78–1 20–60 [235]
accuracy. [Emim][DMP]–H2O 0.77–1 20–60 [235]
As for the influence of concentration, Laliberté and Cooper [229] [Emim][OAc]–H2O 0.5–0.95 20–80 [99]
developed a simple mixed model which determined the solution density

Fig. 9. Density of liquid desiccants varied with temperature.

14
J. Luo and H. Yang
LDAS application requirement are included. Except for desiccants listed
in Table 9, some other potential candidates are introduced thereinafter,
while a brief comparison of existing viscosity data of liquid desiccants is
carried out at the end of this subsection.
The viscosity of salt-water pair has been investigated by researchers
extensively. Laliberté [247] reviewed the viscosity data of 74 electrolyte
solutions, in which common-used liquid desiccants were included.
Longo et al. [250] found that the viscosity of formate-based salt was
lower than that of acetate-based salt, which is regarded as an advantage
for practical applications [9].
For glycol–water, Gómez et al. [28] reported the dynamic viscosities
of 95 % TEG-H2O under 25℃ and 75℃, which was higher than
common-used LiCl-H2O, CaCl2-H2O and LiBr-H2O. With the addition of
glycol, the viscosity of solution increased significantly [251,252]. Sun
et al. [231,232] gave the viscosities of EG-H2O, DEG-H2O, TEG-H2O, PG-
H2O, DPG-H2O and TPG-H2O under full concentration range at tem­
perature from 17℃ to 187℃.
The viscosity of IL-H2O is also investigated. Qu et al. [99] proposed a
polynomial function of temperature and mass fraction to describe the
viscosity of [Emim][OAc]–H2O from 20℃ to 80℃ at full concentration
range. The temperature dependence on viscosity of quaternary ammo­
nium type IL-H2O was evaluated by Maekawa et al. [60], and additive
liquids were suggested to reduce the viscosity of IL-H2O for employment
in LDAS. The viscosities of aqueous solutions of other IL were also
measured within the requirement range of LDAS, such as [Dmim]
[DMP]–H2O, [DEMA][OMs] [100,158]. To date, all of IL-H2O possess
obviously higher viscosity than common-used salt solution, while the
viscosity exhibits an increasing trend with the increase of solute mass
fraction.
For mixture-water pair, Królikowska et al. [107,140] measured the
dynamic viscosities of LiBr-EG-H2O, LiBr-DEG-H2O, LiBr-TEG-H2O and
LiBr-glycerol-H2O from 25℃ to 75℃. Parab et al. [141] measured the
viscosities of HCOOK-PG-H2O and HCOOK-glycerol-H2O at 30℃ and
mass fraction ranging from 0.45 to 0.75. Moattar et al. [237] measured
the viscosity of LiBr-[Bmim]Cl-H2O from 25℃ to 45℃ under different
concentrations. Takada et al. [253] observed the increment of viscosity
for [Bmim]Cl-H2O when LiCl was dissolved in aqueous solutions. For
DES, its high viscosity is obviously the drawback for application
[254,255]. It has been reported that the addition of water significantly
reduced the viscosity of DES [239,255,256]. In 2021, Oladosu et al. [37]
measured the viscosities of 10 kinds of DES-H2O mixtures at 30℃, in
which EG-based DES was found to yield lower viscosity than ZnCl2-
based DES. Mjalli et al. [257] measured the density of aqueous solutions
of [Ch]Cl-based DES from 20℃ to 80℃ under full concentration range,
Fig. 10. Viscosity of liquid desiccants varied with temperature.
15
Applied Energy 325 (2022) 119853
and it was found that DES-H2O with HBD of glycol (e.g., EG, glycerol)
displayed significantly lower viscosity than that with HBD of urea.
Generally, the inclusion of glycol or IL results in the increase of viscosity
compared with typical salt solutions.
Based on the concentration shown in Fig. 6, the viscosities of typical
liquid desiccants varied with temperature can be obtained, as shown in
Fig. 10 [99,169,231–233,235,250,257]. The mass fraction of liquid
desiccant is shown in the legends. In Fig. 10, DES1 and DES2 represent
the same substance as those in Fig. 4 and Fig. 5. For mixture LiBr-CaCl2-
H2O, the mixed ratio of LiBr to CaCl2 is 1:1 on molar basis [258].
As shown in Fig. 10, the viscosities of different solutions differ
significantly, in which the drawbacks of organic components are
emphasized. Aqueous salt solutions yield lower viscosity, and viscosity
of EG-H2O is the lowest among glycol solutions. The viscosity of IL-H2O
is relatively high, which also leads to the high viscosity of DES-H2O.
Nevertheless, the viscosity of DES depends on the selection of HBD as
well, as mentioned above. Because of the lower viscosity of EG against
urea, DES1 displays much lower viscosity than DES2.
Almed et al. [259] applied simple mixing rule for predicting viscosity
of aqueous salt solutions, whose results demonstrated the necessity of
considering the interaction parameters due to the observation of large
deviation under simple mixing rule. Logarithmic mixing rules were
applied to describe the viscosity of electrolyte solutions, achieving good
agreement with experimental data [169]. Haghbakhsh et al. [260]
tested the accuracies of different kinds of viscosity models (e.g., Redlich-
Kister model, Jones-Dole viscosity model) for calculating the viscosity of
DES-H2O, while all of them showed satisfactory consistence.
In aspect of molecular analysis, Chen et al. [181] adopted molecular
dynamics to simulate the viscosity of LiBr solution with three kinds of
ion models. At high concentration (e.g., 60 %), existing models over­
estimated the viscosity of LiBr solution, while the deviation was even
larger than 100 % at 27℃. The inaccuracy of viscosity prediction was
also reported by Porter et al. [261], who found that for viscous aqueous
IL, dynamic quantities were difficult to be precisely obtained by mo­
lecular dynamics.
7.3. Production and cost
Price is an important factor for large-scale application of liquid
desiccant, while it is commonly influenced by the market demand and
production level.
In 2016, Abdel-Salam et al. [14] gave the price of typical salts
applied as solute of liquid desiccant, including LiCl, CaCl2, LiBr and
MgCl2. The results showed that despite better dehumidification ability,
J. Luo and H. Yang
LiCl and LiBr delivered much higher price than CaCl2 and MgCl2. The
price of LiCl in solid form was more than 25 times higher than that of
CaCl2. In 2018, Giampieri et al. [10] depicted the price per metric ton of
typical desiccant salt, in which LiCl and LiBr still held high price and
HCOOK showed comparative cost with CaCl2 and MgCl2. In 2021, Wen
et al. [47] compared the purchasing cost of 70.3 % HCOOK aqueous
solution and 35 % LiCl aqueous solution, whose results showed that the
prices of these two solutions were 234 USD/100L and 1313 USD/100L
respectively. With time passing, CaCl2 and HCOOK are always
economical candidates in regard of purchasing cost. Moreover, the
combination of water absorption ability and purchasing cost should be
considered. Giampieri et al. [10] gave the definition of cost effectiveness
of desiccant, which was the ratio of dehumidification effect to cost.
Despite worse water absorption ability, CaCl2 still displayed the highest
cost effectiveness among CaCl2, HCOOK, LiBr and LiCl. However,
considering the much higher solubility of HCOOK, it was recommended
as potential economic salt for liquid desiccant applications as well.
As for IL, its high price is an inevitable drawback for large-scale
applications, compared with salts and glycols [30]. Fabre et al. [56]
pointed out that the cost of reagents and the difficulty in synthesis were
the main reasons for the high price of IL, even with the development in
manufacturing. The cost in synthesis process is mainly attributed to the
source of anion. Among all the studied anions, [Tf2N] was the most
expensive one, while [PF6] or [BF4] were relatively cheaper [56]. For
example, Giampieri et al. [10] exampled the prices of [Emim][OAc] and
[Emim][BF4] to be 627 GBP/kg and 6980 GBP/kg in 2018, greatly more
expensive than the abovementioned salts. In 2021, Oladosu et al. [37]
evaluated the cost of 10 kinds of DES, and it can be found that the cost
differed largely with the type of DES. However, compared with salt, the
low corrosiveness of IL may lead to the reduction of operation cost and
maintenance cost of component to some extent. Therefore, its economic
characteristic can be worthy expectation if the large-scale production is
realized and the synthesis cost is reduced.
It can be found that for different kinds of liquid desiccant (e.g.,
inorganic salt and IL), the price differs significantly. Here a brief intro­
duction on the present and future demand of such liquids is conducted,
to give a preliminary understanding on the development and potential of
the application of specific liquid desiccant.
Salts used as solute in liquid desiccant are commonly electrolyte,
while aqueous salt solutions are widely used in multitudinous industrial
processes, such as battery, metallurgy, pharmaceutics. For instance, the
rapid development on lithium battery technology brings up the demand
of lithium salt. The development of ammonia-based chemical systems
promotes the requirement of copper salts, ammonium salts and nitrate
salts. As a kind of substance utilized for centuries, the production and
commercialization of typical salts (e.g., LiBr, CaCl2) are of mature and
they are accessible in most of chemical market. The condition of glycols
is similar that they also have great demand in other industrial fields (e.
g., cosmetics, lubricants, anti-frozen medium, chemical synthesis),
which ensures the stability of product chain for supply/demand and the
related commercialization.
On the contrary, the commercialization of IL and IL-based DES are
still restricted by its limited applications. As aforementioned, the cost of
reagents and the difficulty in synthesis lead to their high price. Mean­
while, these liquids are still lack of wide applications, and thus lack of
large-scale demand. Numerous kinds of IL are in the phase of lab-scale
research and development, and researchers gradually demonstrate
their expected potential in metal processing, bio-transformations,
pollutant capture, etc [63,262]. Attributed to their good environ­
mental characteristics, IL or DES is proposed as next-generation mate­
rial. With convinced research results of better performance than existing
material, the demand of IL or IL-based DES is expected to increase, so
that the commercialization progress will be then promoted.
16
Applied Energy 325 (2022) 119853
7.4. Surface tension and contact angle
Wettability of liquid desiccant on surface plays essential role in heat
and mass transfer in LDAS. The studies on the surface tension and
contact angle of liquid desiccants are briefly introduced here.
Surface tension is numerically equal and physically equivalent to the
specific surface free energy, at a constant temperature and pressure
under equilibrium state [263]. For common-used salt solutions (e.g.,
LiCl-H2O, LiBr-H2O, CaCl2-H2O), surface tension typically increases
with the increase of concentration [264,265]. Matubayasi [265] detailly
concluded previous data on surface tension of salt solution, by which the
influence of different cationic and anionic ions on surface tension vari­
ation was revealed, and the surface tension of mixed-electrolyte solu­
tions could be predicted as well. Neyt et al. [266] compared existing
models on predicting surface tension of salt solutions in terms of mo­
lecular simulations, and Wang et al. [267] proposed an approach for
molecular dynamics simulation to determine the concentration depen­
dence on surface tension. Glycols possess much lower surface tension
than water, so liquid desiccants of glycol-H2O are expected to exhibit
lower surface tension, which can be predicted by Jouyban-Acree model
with satisfactory accuracy [268–270]. As for IL, it was proven that its
long alkyl chain played positive effect on reducing surface tension, while
the negative correspondence between the size of anion and surface
tension was also observed [271–273]. In brief, compared with pure
water, most of salt solutions result in the increase of surface tension,
while most of glycol solution and IL solution lead to the decrease of
surface tension. Meanwhile, it should be noted that in most of present
applications, the decrease of surface tension is realized by the utilization
of little amount of amphiphilic surfactant (commonly at the concen­
tration level of ppm), so that the other liquid properties (e.g., VLE,
specific heat capacity, density) will not be considerably influenced.
Contact angle is a property relevant to both liquid and surface, and it
is well known that with smaller contact angle, wetting area significantly
increases, resulting in better mass transfer performance [274]. Wen
et al. [47] tested the contact angle of 70.3 % HCOOK aqueous solution,
which indicated better wettability than 35 % LiCl aqueous solution of
the solution. Qi et al. [275] measured the contact angles of LiCl and LiBr
solutions on stainless steel surface with different roughness, whose re­
sults showed that contact angle increase with the increase of concen­
tration and empirical formula is fitted to calculate the contact angles of
these two kinds of solutions under different concentrations and surface
roughness. Compared with the influence of liquid type, researchers
found that the variation of surface showed more significant effect on the
change of contact angle, regardless of salt solution or IL solution
[276,277]. Therefore, compared with the modification on liquid side,
the modification of surface is of more attentions and applications. Re­
searchers carried out the studies on innovative surface modifications of
material, structure, texture and morphology (e.g., super-hydrophilic
material, chemical coating, micro-structuration) to improve wetta­
bility, which is not detailly described in this paper [278–281].
8. Conclusion and future concerns
8.1. From perspective of liquid desiccant classification
a) For salt-water pair, the inevitable drawback of corrosiveness
extremely limits the large-scale and long-term application of con­
ventional aqueous halide salts in LDAS, despite their usage at pre­
sent. HCOOK-H2O is attractive and accessible, with better
performance on corrosiveness against halide salt, cheaper cost
against IL, environmental friendliness on IAQ against glycol.
Considering its higher vapor pressure than LiCl-H2O or LiBr-H2O,
additive is suggested to improve water absorption ability. The liquid
desiccant with involvement of weak acid salts can be potential
candidate for future application, whereas the studies on their
aqueous mixture with other type solutes are still scarce.
J. Luo and H. Yang
b) For glycol-based liquid desiccant, its volatility results in harmful ef­
fects on human health, e.g., eye, skin and respiratory irritations.
They can be considered as one of the components in mixtures,
through which the volatility can be controlled, e.g., [Ch]Cl-EG-H2O.
Generally, unless the effective method is raised, the utilization of
glycol in LDAS should be cautious.
c) Non-corrosive water-soluble IL is promising liquid desiccant in the
future, whereas its cost is still excessively high for large-scale
commercialization at present. Except for the price, low mass diffu­
sion coefficient is another drawback of IL-H2O [10]. Based on the
current investigation on the moisture absorption mechanism of cat­
ions and anions, the designation of new kinds of IL is anticipated. IL
with cations of shorter alkyl chain and anions of soluble structure has
better hygroscopicity and lower toxicity, which may provide guid­
ance for purposeful designation in LDAS applications. The utilization
of choline cation is also suggested to be studied, considering its low
cost, good biodegradability and non-toxicity [63].
d) The mixture of different kinds of components is also feasible alter­
natives in the future, through which the drawbacks can be made up
for each other. As eco-friendly substance for next generation, DES-
H2O is worthy of exploration for LDAS applications. DES is proven to
be a low-toxic alternative to conventional IL, while the researches on
their properties are still quite scarce [282]. Therefore, the studies on
the aqueous solution of DES is required to illustrate the prospect of
applications. Meanwhile, countless concentration and composition
can be formed for mixture, which results in the difficulty in inves­
tigation and measurement. To this end, the studies on the mixing
mechanism of different component should be further developed, in
order to predict the required properties of new mixture without a
large number of experiments.
8.2. From perspective of properties
a) For VLE, accurate measurement method has been developed for
aqueous solutions. Solutions with large vapor pressure gradient with
the change of mass fraction is recommended for LDAS applications,
which correspond to better water absorption ability and lower
regeneration temperature. Lots of VLE models are established based
on thermophysical principles, but numerous experimental data
points are still demanded to improve their accuracies. The develop­
ment of mixing rule and molecular interaction is appealed to
improve the prediction accuracy without experiment, so that the
mixture-water pair can be selected with convenience.
b) For specific heat capacity, model with linear regression is reasonable
and accurate for describing specific heat capacity with simplicity.
For LDAS applications, solutions with larger specific heat capacity
correspond to less temperature increase during water absorption,
which is favorable for liquid desiccant to maintain better absorption
ability.
c) For safety concerns, present studies show that liquid desiccant de­
livers significantly better effect on getting rid of VOC, biological
pollutants and PM, compared with solid desiccant and conventional
condensation dehumidification approach. The risk of carryover of
liquid desiccant can be alleviated to large extent through the design
of dehumidifier. The corrosiveness of halide salt can be alleviated by
the addition of glycol and IL, so the mixed liquid desiccant will be
promising in the future. The toxicity differs with the type and the
functionalized group of liquid desiccants, which requires further
investigation before its practical applications.
d) Viscosity is one of the drawbacks of IL and IL-based DES, since
aqueous salt solutions often yield lower viscosity. High viscosity may
result in the nonnegligible pressure drop along the pipe, which is
unfavorable for energy efficiency. As viscosity changes significantly
with the variation of temperature, its measurement within the whole
temperature range in LDAS applications is anticipated for new kinds
of liquid desiccants.
17
Applied Energy 325 (2022) 119853
e) High price of IL is another inevitable drawback for large-scale ap­
plications. However, compared with salt, the low corrosiveness of IL
may lead to the reduction of operation cost and maintenance cost of
component to some extent.
f) In present studies, most of thermophysical models are established
based on experimental measurement, while the accuracy of molec­
ular simulation is still unstable. The existing studies on molecular
dynamics are not universal (i.e., only applicable for certain liquid)
and its further development is anticipated to explore the substantial
mechanism on specific liquid properties.
g) In present studies, the comprehensive comparison between common-
used salt-water liquid desiccant has been well conducted. As for
properties of different kinds of liquid desiccants, lots of studies still
focus on specific aspect rather than comprehensive comparison [13].
Therefore, when a new kind of liquid desiccant is raised, the
comprehensive evaluation of properties are suggested, rather than to
emphasize its advantage on specific aspect.
9. Expectation
Due to the urgent need to reduce carbon emissions from burning
fossil fuels, LDAS application becomes an attractive option for reducing
the energy consumption of conventional air-conditioning systems. The
practicability of LDAS is mainly restricted by the selection of liquid
desiccant, especially its corrosive characteristic and dehumidification
capacity. Even though there are lots of published papers on LDAS in
various aspects, a comprehensive review on the fundamental properties
of liquid desiccants is not yet conducted with great significance.
In this paper, a state-of-the-art review on the properties in regard of
energy and environmental performance is delivered for present and
potential liquid desiccants, including vapor–liquid equilibrium, specific
heat capacity, safety concerns. Current situations and future concerns of
liquid desiccant properties are obtained, while different kinds of liquid
desiccant candidates can be compared and evaluated comprehensively,
as summarized in section 8.
Generally, compared with existing liquid desiccants, the candidates
of weak acid salt, ionic liquid and deep eutectic solvent behave low
toxicity and friendly corrosiveness, whereas their weak moisture ab­
sorption ability, high cost or high viscosity is the bottleneck for further
applications. The mixture of them can be regarded as a promising
candidate in LDAS applications, but the measurement of its fundamental
properties is anticipated.
The work in this paper provides momentous reference and guidance
for the exploration of new liquid desiccant as well as the evaluation of
future prospect of LDAS in terms of energy saving and environmental
concerns.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgements
This study was sponsored by the Postdoctoral Fellowship Scheme of
The Hong Kong Polytechnic University and the Postdoctoral Hub Pro­
gram of the Innovation and Technology Fund, the Hong Kong SAR
Government.
J. Luo and H. Yang Applied Energy 325 (2022) 119853

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