Chemical Engineering Science 260 (2022) 117932

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Chemical Engineering Science

journal homepage: www.elsevier.com/locate/ces

A composite phase change material possessing antileakage performance

for battery thermal management by constructing a nanoscale polymer
framework
Zhubin Yao, Guohua Ye, Runye Huang, Xiaoru Xu, Guoqing Zhang, Xiaoqing Yang ⇑
School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, PR China

h i g h l i g h t s

 A novel CPCM with antileakage property for battery thermal management is prepared.
 A nanoscale framework is constructed to replace micron-scale framework in CPCM.
 The nanoscale framework stacks into a developed mesoporous structure to adsorb PEG.
 The obtained CPCM presents excellent antileakage property and thermal stability.
 The obtained CPCM shows outstanding cooling performance for the battery module.

a r t i c l e i n f o a b s t r a c t

Article history: To solve the leakage issue of phase change material (PCM)-based battery thermal management (BTM)
Received 21 May 2022 technology, a novel composite PCM (CPCM) is prepared herein by constructing a nanoscale resorcinol–
Received in revised form 9 July 2022 formaldehyde (RF) framework to replace the classical micron-scale polymer framework. The three-
Accepted 18 July 2022
dimensional (3D) nanoscale RF framework stacks into a 3D continuous mesoporous structure with a pore
Available online 22 July 2022
size of  30 nm and thereby results in intensive adsorbability toward polyethylene glycol, delivering an
excellent antileakage property under long-term heat treatment up to 120 °C. The obtained CPCM pos-
Keywords:
sesses a thermal conductivity, latent heat and phase change temperature region of 1.26 W
m 1
K 1,
Battery thermal management
Phase change material
103.13 J
g 1 and 35–60 °C, respectively. Consequently, superior temperature-control performances for
Leakage the battery module can be obtained. Even at high discharge rates of 2 and 3C for 10 cycles, the maximum
Heat dissipation temperature and temperature difference can be maintained below 39.7 and 2.4 °C and 41.7 and 2.3 °C,
Safety respectively.
Ó 2022 Elsevier Ltd. All rights reserved.

1. Introduction problems of energy shortages and environmental pollution. The

With the continuous promotion of the strategic concept of sus-
tainable development all over the world (Omahne et al., 2021),
people are paying greater attention to the increasingly prominent
Abbreviations: EVs, electric vehicles; BTM, battery thermal management; PCM,
phase change material; CPCM, composite phase change material; EG, expanded
graphite; PA, paraffin; LDPE, low-density polyethylene; DBS, 1,3:2,4-Dibenzylidene
sorbitol; PEG, polyethylene glycol; PCT, phase change temperature; UPR, unsatu-
rated polyester resin; F, formaldehyde; CTAB, cetyltrimethyl ammonium bromide;
R, resorcinol; XRD, X-ray diffraction; FTIR, Fourier transform infrared; SEM,
Scanning electron microscope; BET, Brunauer- Emmett-Teller; DSC, differential
scanning calorimetry; ER, epoxy resin.
⇑ Corresponding author.
E-mail address: yangxiaoqing@gdut.edu.cn (X. Yang).
large amount of tail gas emitted by traditional fuel vehicles is
one of the main environmental pollution sources, leading to acid
rain, haze and greenhouse effects (Gireesh Kumar et al., 2021).
Thus, most countries have been focusing on the development of
electric vehicles (EVs) in recent years, and periodical achievements
have been made (Bais et al., 2022). In addition to endurance mile-
age and service life, another important factor that restricts the
mass application of EVs is the frequent occurrence of thermal
safety issues with lithium-ion battery modules/packs (Deng et al.,
2022; Liang et al., 2022; Weng et al., 2021). One of the effective
ways to alleviate capacity degradation and prevent thermal haz-
ards is to construct an effective thermal management system for
power battery packs, with which the operating temperature and
temperature gradient of the battery packs can be controlled within

https://doi.org/10.1016/j.ces.2022.117932
0009-2509/Ó 2022 Elsevier Ltd. All rights reserved.
Z. Yao, G. Ye, R. Huang et al.
Nomenclature
RF resorcinol–formaldehyde
EG-RF gel EG-modified RF gel
nano-RF-CPCM CPCM with a nanoscaled RF framework
nano-RF aerogel nanoscaled RF/EG aerogel
LDPE-CPCM LDPE/EG/PEG-based CPCM
ER-CPCM ER/EG/PEG-based CPCM
micron-RF-CPCM CPCM with a micron-scaled RF framework
Greek symbols
D difference
r error
optimal and safe ranges (Chen et al., 2021; Wu et al., 2020; Zhao
et al., 2022).
Currently, the mainstream battery thermal management (BTM)
technologies for power battery modules include forced air cooling
and liquid cooling (Akbarzadeh et al., 2021; Tran et al., 2022).
Despite the simple structure and low cost, forced air cooling suffers
from low heat dissipation performance and poor temperature uni-
formity (Wu et al., 2021). Although liquid cooling possesses high
heat dissipation efficiency and temperature uniformity, challenges
still remain with this complex and high-cost cooling structure, as
well as the leakage risk of the coolants (Xiao et al., 2020). In recent
years, phase change material (PCM) cooling (Liu et al., 2020; Lv
et al., 2020) has been considered to be the next-generation BTM
technology in EVs by virtue of its high cooling performance and
simple cooling structure (Wu et al., 2016). Fig. 1.
Research on PCM cooling technology has primarily focused on
physically modifying pure PCM to make it suitable for BTM appli-
cations (Wang et al., 2013; Wu et al., 2022). First, metallic and/or
carbonaceous fillers (Kant et al., 2021; Sheng et al., 2020; Zhang
et al., 2021) are usually blended with PCMs to obtain composite
PCMs (CPCMs) with enhanced thermal conductivity. The most
commonly used thermal conductive fillers are expanded graphite
(EG) (Li et al., 2021; Lin et al., 2021), graphene (Yu et al., 2021),
metallic foam (Ali et al., 2022), metallic powders (Barthwal et al.,
2021), etc. Second, fire retardants such as ammonium polyphos-
phate (Sittisart and Farid et al., 2011), polyurethane (Amaral
et al., 2020), and magnesium hydroxide (Idumah et al., 2018) and
insulating fillers such as AlN (Rao et al., 2014) and SiC (Chen
et al., 2020) are incorporated to enhance the flame retardant and
insulating properties, respectively. More importantly, for practical
application, a considerable amount of polymer component needs
to be blended in the obtained CPCM to guarantee the shape stabil-
ity and processability of the CPCM modules. Lv et al. (Lv et al.,
2016) developed a ternary CPCM based on EG, paraffin (PA) and
low-density polyethylene (LDPE) for BTM. The testing results
showed that the constructed LDPE framework could not only
Fig. 1. Schematic diagram of constructing a nanoscale RF framework with a mesoporous structure to enhance the anti-leakage performance of the CPCM.
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Chemical Engineering Science 260 (2022) 117932
Subscripts
T temperature (℃)
Tmax maximum temperature (℃)
SBET BET specific surface area
DT temperature difference (℃)
DTmax maximum DT (℃)
enhance the mechanical properties of the structure but also allevi-
ate the leakage phenomenon of the CPCM to a certain extent. Lai
et al. (Lai et al., 2021) utilized 1,3:2,4-dibenzylidene sorbitol
(DBS) with a nanofiber structure, which could self-assemble into
a network structure in a polymer solvent to blend with polyethy-
lene glycol (PEG), thus obtaining DBS/PEG CPCM. The testing
results showed that the dimensional deformation of DBS/PEG
CPCM was less than 5% at 60 °C above the phase change tempera-
ture (PCT). Bing et al. (Bing et al., 2021) reported a form-stable
CPCM using unsaturated polyester resin (UPR), polyethylene glycol
(PEG) and EG as the shape-stabilized component, phase change
component and thermal conductivity additive, respectively. The
testing results showed that the porous structure of EG and the net-
work structure formed by UPR effectively adsorbed PEG. After 50
melting-freezing cycles, the CPCM still maintained its shape
stability.
However, a challenge that greatly restricts the practical applica-
tion of PCM-based BTM technology remains, namely, the PCM leak-
age phenomenon (Rao et al., 2018). Although the previously
introduced polymer skeleton in the CPCM can restrict the flow of
the liquid-state PCM above the PCT during a short time period,
gradual migration of the PCM inside the CPCM is still inevitable
under the influence of gravity and inertial force (Xu et al., 2022).
This is because the current micron-level polymer frameworks, such
as LDPE (Lv et al., 2016), UPR (Çaylı and Küsefoğlu et al., 2006),
styrene–butadienestyrene (Hu et al., 2022), and polypyrrole
(Silakhori et al., 2014), cannot provide sufficient adsorption inten-
sity toward the PCM. In an actual CPCM module with a high PCM
amount, precipitation and leakage of the PCM on the module sur-
face will undoubtedly occur after long-term operation (Dong et al.,
2021). This means that the thermal absorbing capability of the
CPCM module will gradually decrease, and safety problems may
occur because most organic PCMs are highly flammable (Zhang
et al., 2020).
As we know, the adsorption ability toward the liquid-state PCM
derived from capillary condensation is inversely proportional to
Z. Yao, G. Ye, R. Huang et al.
the diameter of the adsorbing pores (Cychosz Struckhoff et al.,
2020). Therefore, it can be speculated that tailoring the polymer
skeleton to the nanoscale may effectively prevent PCM migration
because the nanoscale pores derived from the nanoscale skeleton
can provide intensive adsorbability toward the PCM (Feng et al.,
2019). Herein, a novel type of CPCM with excellent antileakage
capability is successfully fabricated by constructing a nanoscale
resorcinol–formaldehyde (RF) framework through a simple
microemulsion-templated sol–gel method to replace the conven-
tional polymer skeleton (Wu et al., 2006). By simply adding the
cetyltrimethyl ammonium bromide (CTAB) as the emulsifier with
a resorcinol (R)/CTAB of 125, the radial size of the RF framework
can be controlled uniformly at 20–30 nm, delivering a mesopore
size of  30 nm. After adsorbing the PCM of PEG, it provides a great
adsorbing intensity toward PEG and thus prevents PEG leakage
with a mass loss ratio lower than 0.31 wt% under the simulated
working temperature of 60 °C for 12 h. This value is negligible
and much lower than those of CPCMs with conventional polymer
skeletons. Combining the excellent antileakage performance with
a thermal conductivity of 1.26 W
m 1
K 1 and latent heat of
103.13 J
g 1, the Tmax and DTmax of the battery module with such
CPCM can be controlled stable below 41.7 and 2.3 °C at the highest
discharge rate of 3C, respectively.
2. Experimental materials and steps
2.1. Materials
The experimental materials were used as received without fur-
ther purification. R was purchased from Shanghai Macklin Bio-
chemical Co., Ltd. Formaldehyde (F) was purchased from
Guangdong Guangshi Reagent Technology Co., Ltd. CTAB was pur-
chased from Tianjin Fuchen Chemical Reagent Factory. Polyethy-
lene glycol (PEG, PM = 1500) was purchased from Shanghai
Aladdin Biochemical Technology Co., Ltd. Expanded graphite (EG)
was obtained by heat treatment of natural graphite (Qingdao teng-
shengda carbon Machinery Co., Ltd.) in a muffle furnace at 850 °C
for 10 min.
2.2. Material preparation
As shown in Fig. 2, 62 mL of deionized water, 22.75 g of R and
0.60 g CTAB were added into a beaker successively under magnetic
stirring until the R and CTAB were completely dissolved, forming a
clear and homogeneous solution. Then, EG with different propor-
Fig. 2. (a) Schematic diagram and (b) actual photo of the preparation procedure of the nano-RF-CPCM.
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Chemical Engineering Science 260 (2022) 117932
tions was added slowly into the solution under continuous stirring
for 30 min. Subsequently, 30.42 mL of F (37%) was added into the
obtained slurry, and after stirring for 5 min, the resultant mixture
was immediately transferred into a specific sealed mold at 85 °C
and cured for 9 h, obtaining EG-modified RF gel (EG-RF gel). Deion-
ized water accounted for 70 wt% of the total mass fraction. The
molar ratio of R to F was 0.5, and the molar ratio of R to CTAB
was 125. The proportions of EG were 0, 1, 3 and 5 wt%. The resul-
tant EG-RF gel was then placed in melted PEG at 120 °C under mag-
netic stirring to allow the RF gel to adsorb PEG. The obtained CPCM
with a nanoscale RF framework was denoted as nano-RF-CPCM.
Another group of EG-RF gels was directly dried in an oven at
100 °C for 4 h, obtaining nanoscale RF/EG aerogels (denoted as
nano-RF aerogel). In the control groups, three reference samples
were prepared. First, a micron-scale RF gel was prepared through
similar processes without adding the emulsifier CTAB to adsorb
PEG, and the resultant CPCM with 5 wt% EG was denoted as
micron-RF-CPCM. On the other hand, two CPCMs with classical
micron-scale LDPE and epoxy resin (ER) frameworks were also pre-
pared according to our previous works (Lv et al., 2016; Wu et al.,
2018). The corresponding mass ratios of LDPE:PEG and ER:PEG
were both 3:7. These two samples with 5 wt% EG were denoted
as LDPE-CPCM and ER-CPCM, respectively. The densities of the
nano-RF-CPCM, micron-RF-CPCM, LDPE-CPCM and ER-CPCM were
1.05, 0.91, 0.87 and 0.99 g cm 3, respectively.
2.3. Characterizations of phase change composites
A Rigaku Ultima III X-ray diffractometer (XRD) with a Cu-Ka
radiation source (k = 1.54 Å) was used to characterize the chemical
structure of the prepared samples in the scan range of 10-80° with
a scan rate of 10° min 1. A Nicolet 6700 Fourier transform infrared
(FTIR) spectrophotometer was used to characterize and analyze the
FTIR spectra of the samples in the wavenumber range of 700–
4000 cm 1.
A Hitachi TM3030 cold field emission scanning electron micro-
scope (SEM) was used to observe the morphology of the samples
under a 15-kV accelerating voltage. Nitrogen adsorption tests of
the samples were taken using an ASAP 2046 surface area and
porosity analyzer (Micromeritics Instrument Corporation). The
Brunauer–Emmett–Teller (BET) method was utilized to calculate
the BET surface area (SBET) using adsorption data in a relative pres-
sure (P/P0) range from 0.05 to 0.21. The pore size distribution curve
was obtained using density functional theory. A Mettler Toledo
DSC differential scanning calorimeter was used to measure the
Z. Yao, G. Ye, R. Huang et al.
differential scanning calorimetry (DSC) curves of the samples from
0 to 80 °C with a heating rate of 10 °C min 1 in a nitrogen atmo-
sphere. For the thermal conductivity test, the sample was pro-
cessed into a standardized cylindrical specimen with dimensions
of U37 mm  10 mm, and the thermal conductivity of the speci-
men was tested by using a laser thermal conductivity instrument
with an accuracy of ± 5%.
To evaluate the antileakage performance of the obtained CPCM,
we conducted the following three groups of experiments:
Group 1: Cylindrical CPCM specimens were placed on a heating
stage (JFTOI 996D produced by Weitieke Electronics Co., Ltd.) with
a heating temperature of 120 °C for 12 h. Then, digital photos of the
cylindrical specimens were taken every 2 h.
Group 2: CPCM specimens were placed under 60 °C above the
PCT for 12 h, and the mass loss of the samples was weighed by
an electronic balance (BSM 320.3 produced by Shanghai Zhuojing
Electronic Technology Co., Ltd.) with an interval of 2 h. Then, the
specimens were placed on the heating stage and heated with step-
wise heating temperatures of 80, 100 and 120 °C for 4 h at each
temperature. The mass loss of the samples at each temperature
was also recorded.
Group 3: The CPCM specimens were placed in a thermostat
whose temperature was set as 30 °C for 30 min and then increased
to 70 °C for 30 min with a heating rate of 5 °C min 1. A total of 100
endothermic-exothermic cycles were executed.
2.4. Assembly and test of the battery module
The battery modules used for the temperature-control perfor-
mance tests were assembled using five pouch cells and six CPCM
boards installed alternatively (Fig. 2a). The specific parameters of
the battery are shown in Table 1. Omega K-type thermocouples
(TT-K-30-SLE) with an accuracy of ± 1 °C were installed on the sur-
face of the center and positive and negative electrodes of each cell,
and the temperature data were collected using an Agilent acquisi-
tion unit (Fig. 3). Because the cell in the center of the module
always possesses the highest temperature during the charge–dis-
Table 1
Basic parameters of the pouch cells.
Parameters Value/Material
Cathode LiCoO2
Anode Graphite
Electrolyte LiPF6
Quality (g) 300.0 ± 5.0
Nominal capacity (Ah) 16
Nominal voltage (V) 3.7
Open-circuit voltage (V) 4.2
Fig. 3. (a) Actual photo and (b) schematic diagram of the experimental system.
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Chemical Engineering Science 260 (2022) 117932
Table 2
Parameters of the charge–discharge protocols of the battery module.
Process Step Current Voltage (V)
Charge constant current constant 1C Cutoff current Cutoff voltage
voltage of 1 A of 21
Rest 10 min —— ——
Discharge constant current 0.5, 1, 2, 3C Cutoff voltage
of 15
Rest 10 min —— ——
charge process, its temperature was adopted to represent the tem-
perature variation of the entire module, and the difference
between the highest temperature and the lowest temperature of
the entire module was used to reflect the temperature difference
(DT) inside the module. The battery modules were placed under
a constant ambient temperature of 25 °C provided by a Dongguan
BellBTH1000C thermostat. After achieving thermal equilibrium,
they were charged with a constant current-constant voltage mode
and then discharged with a constant current mode using a
Newarebts-60 V/100A battery test system. Detailed charge–dis-
charge parameters are shown in Table 2. During a typical
charge–discharge cycle, the battery module was charged with a
constant-current mode of 1C to 21 V (C-rate is the measurement
of the charge and discharge current with respect to its nominal
capacity) and then with a constant voltage mode at 21 V until
the current dropped to 1 A. After rest for 10 min, the module
was then discharged with constant-current modes at different
rates of 0.5, 1, 2 or 3C until the voltage dropped to 15 V.
3. Results and discussion
Fig. 4a displays the FTIR spectra of the raw materials and
obtained composites. By comparing the spectra of the nano-RF
aerogel and nano-RF-CPCM with those of F and R, the newly gener-
ated characteristic peaks at 1220 and 1100 cm 1 of the nano-RF
aerogel and nano-RF-CPCM can be assigned to the stretching vibra-
tion absorption of -C-O-C- (Khan et al., 2004), and the characteris-
tic peaks at 1470 and 2930 cm 1 are the bending vibration
absorption and stretching vibration absorption of C-H in –CH2-
(Khan et al., 2004), respectively. These new peaks indicate that F
and R are successfully crosslinked into the RF framework. In the
spectrum of PEG, the characteristic peaks at 2880, 960 and
840 cm 1 correspond to the tensile vibration absorption peak of
–C-H, tensile vibration absorption peak of –COH, and deformation
vibration absorption peak of -C-H (Wu et al., 2018). The above
characteristic peaks can be observed in the nano-RF-CPCM sample,
indicating that the RF framework successfully adsorbs PEG.
Z. Yao, G. Ye, R. Huang et al.
Fig. 4. FTIR (a) and XRD (b) spectra of samples and raw materials.
Fig. 5. SEM images of (a, b) micron-RF aerogel, (c) nano-RF aerogel (d) nano-RF-CPCM, (e) LDPE-CPCM and (f) RF-CPCM; (g) N2 adsorption–desorption isotherms of the
polymer frameworks; (h) pore size distribution of nano-RF aerogel.
The crystallization property, as an important index to evaluate
the performance of PCMs, was analyzed by XRD. As displayed in
Fig. 4b, PEG demonstrates sharp characteristic diffraction peaks
at 19.04° and 23.28°, which are indexed to the (1 1 0) and (2 0 0)
crystal planes of PEG (Wu et al., 2018). The strong peak at 26.4°
_
of EG corresponds to the (0 0 2) crystal planes of graphite (ÇElIK
and Kurt et al., 2021). The RF aerogel is a completely amorphous
material, and thus, no obvious characteristic peak in the XRD pat-
tern can be observed. The aforementioned characteristic peaks of
PEG and EG can be clearly observed in the resultant nano-RF-
CPCM sample, implying that EG is incorporated into the RF skele-
ton and the PEG is successfully adsorbed in the nanopores of the
RF framework.
Fig. 5a-5f present the SEM images of the samples. It can be
vividly seen that in the RF aerogel without using CTAB (Fig. 5a
and 5b), lm-scale particles interconnect into a micron-scale skele-
ton, forming many micron-scale pores. As expected, after adopting
CTAB as the emulsifier during the sol–gel process, nanoparticles
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Chemical Engineering Science 260 (2022) 117932
with diameters of 20–30 nm stack into grape-like aggregates in
the obtained nano-RF aerogel (Fig. 5c). These aggregates intercon-
nect in different directions, and thus, a unique 3D continuous poly-
mer framework is successfully constructed. The 3D nanoscale
polymer skeleton provides numerous continuous nanoscale pores
in the range of mesopores, which is very important for the intensive
adsorption of the PCM because the adsorption ability of the pores
derived from capillary condensation is inversely proportional to
the diameter of the adsorbing pores. After adsorption, these pores
are filled with PEG, forming a compact structure, but a relatively
rough surface morphology is observed due to the irregular 3D con-
tinuous polymer skeleton (Fig. 5d). For comparison, after removing
the adsorbed PEG from the LDPE-CPCM and ER-CPCM samples by
multiple ethanol washing, the resultant LDPE and EG skeletons
are both in micron scale (Fig. 5e and 5f) and deliver micron-scale
pores for PEG adsorption as the micron-RF aerogel does.
To quantitatively confirm the nanoscale structure of the
obtained RF framework, N2 adsorption tests were carried out to
Z. Yao, G. Ye, R. Huang et al. Chemical Engineering Science 260 (2022) 117932

Table 3 tively, whereas the as-designed nano-RF aerogel delivers a devel-

SBET and mesopore volume calculated from the N2 adsorption tests. oped nanostructure with a mesopore volume and SBET of
Sample SBET (m2 g 1
) Mesopore Volume (cm3 g 1
) 0.50 cm3 g 1 and 103.31 m2 g 1, respectively. The calculated meso-
nano-RF-CPCM 103.31 0.50 pore size is centered at  30 nm.
micron-RF-CPCM 5.71 – The main purpose of nanosizing the polymer framework to con-
ER-CPCM 0.94 – struct nanoscale pores is to provide intensive adsorbability to
LDPE-CPCM 2.81 – strictly limit the migration of the PCM, thus preventing the leakage
phenomenon. Fig. 6a shows pictures of nano-RF-CPCM, micron-RF-
CPCM, ER-CPCM and LDPE-CPCM taken with an interval of 2 h at
analyze the pore structure of the obtained polymer skeletons. As 120 °C. We can see that the three ER-CPCM, nano-RF-CPCM and
seen from the N2 adsorption–desorption isotherms presented in micron-RF-CPCM specimens show excellent shape stability with-
Fig. 5g, all the micron-scale polymer skeletons observed from the out any deformation during the entire heat-treatment process.
above SEM images, including the micron-RF aerogel, LDPE and ER Nonetheless, a serious leakage trace is observed on the filter paper
skeleton, possess extremely low adsorption amounts within the under the ER-CPCM and micron-RF-CPCM, which is fully infiltrated
P/P0 range from 0 to 1, indicative of their little nanoporosity. For by the melting PEG after 4 h of heat-treatment at 120 °C. By stark
the nano-RF aerogel, an obvious uptake appears at the high P/P0, contrast, only a slight leakage trace is observed on the filter paper
suggesting the typical mesoporous structure constructed by the under the micron-RF-CPCM specimen. On the other hand, LDPE-
nanoscale framework (Xu et al., 2017). According to the isotherms, CPCM begins to soften after 2 h, and serious deformation is
pore size distribution curves and pore structure parameters are observed after heating for 4 h. This is attributed to the thermoplas-
calculated, and the results are shown in Fig. 5h and Table 3. tic property of the LDPE skeleton, which may not be suitable for
Undoubtedly, because of the much larger micron-scale pores, the BTM applications.
SBET of the micron-RF aerogel, LDPE and ER framework is as low Quantitatively, it can be seen from Fig. 6b that during the
as 5.71, 0.94 and 2.81 m2 g 1 without any mesoporosity, respec- heat-treatment of 60 °C, the mass of ER-CPCM decreases sharply,

Fig. 6. (a) Shape stability and leakage tests of the CPCMs at 120 °C; comparison of the mass loss rate of the CPCMs at 60 °C with those reported in the literature (Hu et al.,
2021; Huang et al., 2020; Li et al., 2022; Liang et al., 2021; Wang et al., 2022; Wei et al., 2019); (c) mass loss rate of the CPCMs at 80, 100 and 120 °C for 4 h.

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Table 4 In addition, simulating endothermic-exothermic cycles

The tested latent heat of the nano-RF-CPCM and ER-CPCM specimens before and after between 30 and 70 °C were carried out on the nano-RF-CPCM
the simulated endothermic-exothermic cycles at 30–70 °C.
and ER-CPCM for 100 cycles. After that, some samples were
Sample Latent heat before cycles Latent heat after cycles scratched from the upper and bottom surfaces, and their latent
(J
g 1) (J
g 1) heat calculated from the DSC test results is shown in Table 4 to
nano-RF- 103.13 100.20 (upper surface) compare it with that before the endothermic-exothermic cycles.
CPCM 100.55 (bottom surface) It can be seen that the latent heat of the ER-CPCM on the upper
ER-CPCM 101.87 110.14 (upper surface)
144.2 (bottom surface)
and bottom surfaces increases from 101.87 to 110.14 and
144.20 J g 1, respectively, implying that serious migration of PEG
toward the specimen surface appears in the micron-scale ER
framework during the simulated working process. By stark con-
Table 5
The tested latent heat and thermal conductivity of the nano-RF-CPCM with different
trast, the nano-RF-CPCM shows comparable latent heat before
EG contents. and after the endothermic-exothermic processes, both on the
1
upper and bottom surfaces, suggesting the uniform distribution
Sample Latent heat (J
g ) Thermal conductivity
(W
m 1
K 1)
of PEG in the RF framework without obvious migration and
leakage.
nano-RF-CPCM (0 wt% EG) 110.34 0.28
nano-RF-CPCM (1 wt% EG) 108.84 0.42
The tested thermal conductivities of nano-RF-CPCM with differ-
nano-RF-CPCM (3 wt% EG) 106.38 0.91 ent EG contents are listed in Table 5. The results show that the
nano-RF-CPCM (5 wt% EG) 103.13 1.26 thermal conductivity of nano-RF-CPCM without EG is only
ER-CPCM (5 wt% EG) 101.87 1.14 0.28 W m 1 K 1. Such a low thermal conductivity undoubtedly
leads to low heat transfer efficiency inside the CPCMs, and thereby
achieving a mass loss rate of 5.56 wt%, whereas the micron-RF- cannot meet the heat dissipation demand of the battery module
CPCM sample demonstrates a lower mass loss rate of 2.26 wt%, under high-power discharge. With increasing EG content, the ther-
which results from the 3D continuous RF framework that better mal conductivity of the CPCM increases obviously. In detail, when
encapsulates PEG. To our delight, the nano-RF-CPCM sample shows the EG content increases to 1, 3 and 5 wt%, the thermal conductiv-
a negligible mass loss rate of 0.31 wt% after 12 h of heat-treatment ity increases to 0.42, 0.91 and 1.26 W m 1 K 1, respectively. The
at 60 °C. It should be highlighted that this value, is much lower relatively higher thermal conductivity of nano-RF-CPCM compared
than those reported previously (Fig. 6b). Fig. 6c demonstrates the with that of ER-CPCM with the same EG content of 5 wt% can be
mass loss rate of the different CPCM samples under extremely attributed to the homogeneous and continuous thermal conductive
harsh environments during the stepwise heating process at 80, network resulting from the in-situ polymerization in the presence
100 and 120 °C. We can intuitively see that, as consistent with of EG.
the above tests, the mass loss rate of nano-RF-CPCM is much lower Fig. 7 shows the DSC curves of the nano-RF-CPCM and ER-CPCM
than those of micron-RF-CPCM and ER-CPCM at all temperatures. samples. All the samples present a similar PCT region from 35 to
For example, the mass loss rates of the nano-RF-CPCM, micron- 60 °C, which is due to the same PCM component of PEG. The calcu-
RF-CPCM and ER-CPCM are 0.77, 3.9 and 5.7 wt% at 80 °C, 0.87, lated latent heat listed in Table 4 suggests that the latent heat
4.80 and 6.30 wt% at 100 °C, and 0.99, 5.7 and 7.2 wt% at 120 °C, slightly decreases with increasing EG content, and the nano-RF-
respectively. CPCM with 5 wt% EG delivers comparable latent heat to the

Fig. 7. DSC curves of the nano-RF-CPCM and ER-CPCM samples.

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Z. Yao, G. Ye, R. Huang et al. Chemical Engineering Science 260 (2022) 117932

Fig. 8. Temperature variation and DT variation curves of the RF module and ER module during 10 charge–discharge cycles with different discharge rates of 0.5, 1, 2 and 3C.

8
Z. Yao, G. Ye, R. Huang et al.
Fig. 9. Digital photos of the RF and ER modules after the cyclic tests.
ER-CPCM with the same EG content. Generally speaking, according
to the thermal management requirements of the PCM proposed in
previous reports, i.e., sufficient latent heat > 80–90 J g 1, high ther-
mal conductivity > 1.0 W m 1 K 1, as well as a suitable PCT of 40–
50 °C, the nano-RF-CPCM and ER-CPCM samples with 5 wt% EG
meet the temperature-control requirements of BTM applications.
Therefore, charge–discharge tests of the assembled battery mod-
ules were carried out with different discharge rates of 0.5, 1, 2
and 3C under an ambient temperature of 25 °C. For convenience,
the battery modules installed with nano-RF-CPCM and ER-CPCM
boards were denoted as the RF module and the ER module,
respectively.
As shown in Fig. 8, at lower discharge rates, the two types of
CPCMs provide similar heat-absorbing performance toward the
batteries. For example, the RF module and ER module demonstrate
a Tmax of 32.2 and 31.7 °C at 0.5C, and 35.2 and 35.6 °C at 1C,
respectively. Such a temperature does not reach the PCT region
of the CPCMs, and thus the similar specific capacity of nano-RF-
CPCM and ER-CPCM (1.64 v.s. 1.47 J kg 1 K 1) is responsible for
the similar cooling performance at lower discharge rates. In addi-
tion, the temperature gradient of the RF module is apparently
smaller than that of the ER module, leading to a lower DTmax of
1.5 and 2.4 °C at discharge rates of 0.5 and 1C in comparison to that
of the ER module (2.4 and 3.1 °C), respectively. This better temper-
ature uniformity originates from the relatively higher thermal con-
ductivity of the nano-RF-CPCM boards, which can rapidly balance
the temperature distribution of the entire module.
When we further increase the discharge rate to 2 and 3C, the
much faster heat generation rate results in a much higher temper-
ature rise in the battery modules. The latent heat of the two CPCMs
starts to work at temperatures above 35 °C. Consequently, the Tmax
of the RF module and ER module is controlled below 39.7 and
40.9 °C at a discharge rate of 2C, and 41.7 and 43.1 °C at a discharge
rate of 3C, respectively. This comparable cooling performance is
undoubtedly ascribed to the comparable latent heat of the nano-
RF-CPCM and ER-CPCM samples resulting from the same PEG con-
tent. However, the higher thermal conductivity of the nano-RF-
CPCM still endows the RF module with higher heat transfer ability,
resulting in a much lower DT of the entire module. The most
important phenomenon is that after we continue to charge–dis-
charge the battery modules for another 10 cycles under 40 °C at
a discharge rate of 3C, an obvious leakage phenomenon can be
clearly observed in the ER module, whereas the surface of the RF
module remains clean (Fig. 9). This result convincingly confirms
that the excellent anti-leakage performance of the nano-RF-CPCM
provided by the RF nanoframework is favorable for greatly enhanc-
ing the safety of the battery module, and meets the engineering
requirements in practical applications.
9
Chemical Engineering Science 260 (2022) 117932
4. Conclusions
We successfully prepare a novel CPCM with superior antileak-
age performance for BTM applications, which is realized by tailor-
ing the RF framework to the nanoscale through a microemulsion
sol–gel polymerization method. Benefiting from the developed
mesoporous structure stacked by the nanoscale polymer frame-
work, i.e., an SBET of 103.31 m2
g 1, a mesopore volume of 0.50 cm3-

g 1 and a mesopore size of  30 nm, the obtained RF-based CPCM
presents superior antileakage performance with negligible leakage
rates of 0.31, 0.77, 0.87 and 0.99 wt% under long-term and high-
temperature treatment at 60, 80, 100 and 120 °C, respectively. In
addition, the RF-based CPCM incorporated with 5 wt% EG pos-
sesses a high thermal conductivity of 1.26 W
m 1
K 1, a sufficient
latent heat of 103.13 J
g 1 and a suitable PCT region of 35–60 °C for
BTM applications. As a result, the nano-RF-CPCM boards not only
effectively control the temperature and DT below 41.7 and
2.3 °C, respectively, even at a high discharge rate of 3C, but also
demonstrate leakage-proof properties during the harsh cyclic
charge–discharge tests. This approach provides a new concept for
preventing PCM leakage by nanosizing the polymer framework,
which is expected to be a promising strategy for the development
of highly reliable PCM-based BTM systems.
CRediT authorship contribution statement
Zhubin Yao: Investigation, Data curation, Software, Writing –
original draft. Guohua Ye: Investigation, Data curation, Software.
Runye Huang: Investigation, Data curation. Xiaoru Xu: Investiga-
tion. Guoqing Zhang: Supervision, Resources, Validation, Project
administration. Xiaoqing Yang: Supervision, Methodology, Writ-
ing – review & editing, Project administration.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgement
This work was supported by the National Natural Science Foun-
dation of China (NNSFC, 21875046) and Natural Science Founda-
tion of Guangdong Province (2019A1515011525).
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