polymers
Article
Improved Performance of Solid Polymer Electrolyte for
Lithium-Metal Batteries via Hot Press Rolling
Poonam Yadav *, Seyed Hamidreza Beheshti
and Maitane Berecibar






Citation: Yadav, P.; Beheshti, S.H.;
Kathribail, A.R.; Ivanchenko, P.;
Mierlo, J.V.; Berecibar, M. Improved
Performance of Solid Polymer
Electrolyte for Lithium-Metal
Batteries via Hot Press Rolling.
Polymers 2022, 14, 363. https://
doi.org/10.3390/polym14030363
Academic Editor: Vincenzo Baglio
Received: 25 November 2021
Accepted: 11 January 2022
Published: 18 January 2022
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4.0/).
Polymers 2022, 14, 363. https://doi.org/10.3390/polym14030363
, Anish Raj Kathribail , Pavlo Ivanchenko, Joeri Van Mierlo
MOBI Research Group, Department of Electric Engineering and Energy Technology (ETEC),
Vrije Universiteit Brussel, Pleinlaan 2, 1050 Brussels, Belgium; Seyed.Hamidreza.Beheshti@vub.be (S.H.B.);
Anish.Raj.Kathribail@vub.be (A.R.K.); Pavlo.Ivanchenko@vub.be (P.I.); Joeri.Van.Mierlo@vub.be (J.V.M.);
Maitane.Berecibar@vub.be (M.B.)
* Correspondence: Poonam.yadav@vub.be; Tel.: +32-2-629-33-96
Abstract: Solid-state batteries (SSBs) are gaining attention as they promise to provide better safety
and a higher energy density than conventional liquid electrolyte batteries. Solid polymer electrolytes
(SPEs) are promising candidates due to their flexibility providing better interfacial contact between
electrodes and the electrolyte. However, SPEs exhibit very low ionic conductivity at ambient tem-
peratures, which prevents their practical use in batteries. Herein, a simple and effective technique
of hot press rolling is demonstrated to improve ionic conductivity and, hence, the performance
of polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP)-based solid polymer electrolyte.
Applying hot press rolling to the electrolyte membrane induced structural changes in the grain bound-
aries, which resulted in a reduction in the crystallinity of the material and, hence, an increase in the
amorphous phase of the material, which eased the movement of the lithium ions within the material.
This technique also improved the surface of the membrane, making it homogeneous and smoother,
which resulted in better interfacial contact between the electrodes and electrolyte. Electrochemical
tests were carried out on electrolyte membranes treated with and without hot press rolling to evaluate
the effect of the treatment. The hot pressed electrolyte membrane showed significant improvements
in its ionic conductivity and transference number. The cycling performance of the LFP/Li batteries
using a hot press rolled electrolyte was also evaluated, which gave a specific discharge capacity of
134 mAh/g at 0.1 C. These results demonstrate that hot press rolling can have a significant effect on
the electrochemical performance of solid polymer electrolytes.
Keywords: solid polymer electrolyte; hot press rolling; ionic conductivity; PVDF-HFP; crystallinity
of polymer; grain boundary; lithium-metal battery
1. Introduction
Climate change and global warming are real issues that demand immediate attention.
The transportation sector, which operates on fossil fuels, contributes 16.2 percent of carbon
emissions [1]. Replacing fossil fuels with electricity in transport vehicles is a promising
way to reduce carbon emissions. The current battery systems cannot fulfill the demands
of electric vehicles in terms of energy density, power density, and safety. In addition,
conventional batteries contain an organic liquid electrolyte which is flammable and causes
serious safety issues. Solid-state batteries (SSBs) are a promising solution as they result in
fewer safety concerns compared to conventional batteries with liquid electrolytes as solid
electrolytes are thermally more stable [2]. The use of solid electrolytes also paves the way
for the use of lithium metal as the anode, which is not possible with liquid electrolytes
because of their high reactivity with lithium metal [3]. Lithium metal is a favorable anode
material owing to its high energy density (3680 mAh/g), which is 10 times better than the
specific capacity provided by conventional graphite anodes [3,4]. Irrespective of all these
https://www.mdpi.com/journal/polymers
Polymers 2022, 14, 363 2 of 12

advantages, several challenges such as the low ionic conductivity of solid electrolytes, high
interfacial resistance and instability between electrodes and solid electrolytes remain to be
addressed before the use of SSBs becomes practical [5,6].
Generally, solid electrolytes can be classified into three categories: inorganic solid elec-
trolytes (ISEs), solid polymer electrolytes (SPEs), and composite solid polymer electrolytes
(CSPEs) [7]. Each solid electrolyte has its own advantages and challenges to overcome. Inor-
ganic solid electrolytes (sulfides, oxides, phosphates) usually have high ionic conductivity
but face the challenge of high solid–solid interfacial resistance between the electrodes and
electrolyte [8]. The application of pressure at the cellular level is required for batteries using
ceramic solid electrolytes. Solid polymer electrolytes (SPEs) consist of a polymer matrix
and lithium salts, and possess excellent flexibility, good solid–solid interfacial contact,
and easy processability [8,9], but present low ionic conductivity (<10−4 S/cm) in ambient
conditions, as well as having inferior thermal and electrochemical stability [7]. Composite
solid polymer electrolytes (CSPEs) are made by adding inorganic ceramic as filler into solid
polymer electrolytes [10], and they promise to inherit the advantages of both SPEs and
inorganic fillers, such as better ionic conductivity, flexibility, and mechanical strength.
In solid polymer electrolytes (SPEs), PEO is the most extensively studied polymer
matrix, mainly due to its ability to dissolve alkali-metal salts, low glass transition tem-
perature, and non-toxicity [11]. On the other hand, PVDF-HFP is a good candidate for a
polymer matrix due to its low crystallinity, high dielectric constant (ε = 8.4), which helps
to dissolve lithium salts to a greater extent, and good mechanical stability over a wide
range of temperatures [12–15]. However, ionic conductivity is the most important indicator
when evaluating the performance of an electrolyte, which is determined by the mobility
of the charge carriers. The ionic conductivity of solid polymer electrolytes is severely
affected by the large crystalline domains present in the polymer chains [16]. Crystallinity
is a fundamental characteristic of polymeric systems which defines mechanical, thermal,
optical, electronic, and transport properties [17–19]. A high crystallinity limits the move-
ment of lithium ions [20,21] and, hence, enhances the ionic conductivity of SPEs. Several
approaches, such as adding plasticizer and incorporating ceramic filler, have been widely
explored [22–26] and demonstrated to successfully disrupt this crystallinity. However, a
simple processing technique can also greatly influence the quality of the electrolyte. For ex-
ample, Wang et al. [27] used an ultrasonic vibrational technique to suppress the crystallinity
of solid polymer electrolytes, which resulted in improvements in the ionic conductivity of
the electrolytes.
In this work, a solid polymer electrolyte made of a Polyvinylidene fluoride-co-hexafluo-
ropropylene (PVDF-HFP) polymer matrix and a Bis(trifluoromethylsulfonyl)amine (LiTFSI)
lithium salt was studied. A simple and effective technique of hot press rolling was im-
plemented to reduce the crystalline matrix present in the polymer chains and to improve
the performance of the SPE. In solid polymer electrolytes, lithium ions are thought to be
transported through grain boundaries and an amorphous phase [28]. The use of hot press
rolling with maintained pressure and temperature on the solid electrolyte membrane can
break grains and reform grain boundaries, which increases the amorphous region; hence,
it has the potential to be applied to SPEs to reduce the crystallinity of the polymers and
improve the ionic conductivity of the electrolytes. Furthermore, detailed electrochemical
analyses of the hot press rolled and non-hot press rolled SPEs were carried out to evaluate
their performances in lithium-metal battery application.

2. Materials and Methods

2.1. Materials Used
Polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP) (average relative molec-
ular mass Mw of ~455,000), Bis(trifluoromethylsulfonyl)amine (LiTFSI) lithium salt (99.95%),
Lithium iron phosphate (LiFePO4 ), and N-Methyl-2-pyrrolidone (NMP) (99.95%) were
purchased from Sigma-Aldrich and used as received. Carbon (Super-p) was purchased
 2. Materials and Methods
2.1. Materials Used
Polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP) (average relative mo-
Polymers 2022, 14, 363 lecular mass 𝑀𝑤 of ~455,000), Bis(trifluoromethylsulfonyl)amine (LiTFSI) lithium3 ofsalt 12

(99.95%), Lithium iron phosphate (LiFePO4), and N-Methyl-2-pyrrolidone (NMP)

(99.95%) were purchased from Sigma-Aldrich and used as received. Carbon (Super-p) was
from Alfa Aesar.
purchased TheAesar.
from Alfa chemical structuresstructures
The chemical of the polymer and lithium
of the polymer salt used
and lithium saltinused
the
preparation of the solid
in the preparation of thepolymer electrolytes
solid polymer is shown
electrolytes in Figure
is shown 1.
in Figure 1.

Figure 1.
Figure 1. Chemical structures of polymer Polyvinylidene fluoride-co-hexafluoropropylene (PVDF-
HFP) and lithium salt
HFP) and lithium salt Bis(trifluoromethylsulfonyl)amine
Bis(trifluoromethylsulfonyl)amine (LiTFSI)
(LiTFSI) used
used for
for the
the preparation
preparation of
of the
the
solid polymer electrolytes.
solid polymer electrolytes.

2.2. Methods
2.2.1.
2.2.1. Preparation
Preparation of
of Solid
Solid Polymer
Polymer Electrolyte
Electrolyte Membranes
Membranes
The
The solid
solid polymer
polymer electrolyte
electrolyte membranes
membranes were were prepared
prepared by by aa solution casting tech-
solution casting tech-
nique.
nique. The
The polymer
polymer matrix
matrix (PVDF-HFP)
(PVDF-HFP) to to lithium
lithium salt
salt (LiTFSI)
(LiTFSI) ratio
ratio was
was kept
kept constant
constant atat
2:1 wt%. LiTFSI (1.25 g) was dissolved in NMP (10 mL) and stirred
2:1 wt%. LiTFSI (1.25 g) was dissolved in NMP (10 mL) and stirred on a heating plate aton a heating plate at
50 ◦ C for 2 h (Figure 2a,b). Thereafter, PVDF-HFP (2.5 g) was added and stirring continued
50 °C for 2 h (Figure 2a,b). Thereafter, PVDF-HFP (2.5 g) was added and stirring continued
for
for 12
12 h h (Figure
(Figure 2c).
2c). The
The resultant
resultant slurry
slurry was
was poured
poured into
into aa petri
petri dish,
dish, and
and the
the solvent
solvent was
was
allowed to evaporate slowly at room temperature in a dry room
allowed to evaporate slowly at room temperature in a dry room (dew point: −50 (dew point: − 50 ◦°C
C )) for
for
12
12 hh (Figure
(Figure 2d,e).
2d,e).Residual
Residual solvents
solvents were
were further
further removed
removed bybydrying
dryingin in
a vacuum
a vacuum oven
oven at
80 ◦
at 80C °C
forfor
16 h16(Figure 2f). 2f).
h (Figure As aAs result, the solid
a result, polymer
the solid electrolyte
polymer (SPE)(SPE)
electrolyte self-standing films
self-standing
were obtained (Figure 2g). Similarly, the desired amount of SPE was
films were obtained (Figure 2g). Similarly, the desired amount of SPE was fabricated and fabricated and hot
press rolling treatment was performed under controlled conditions. From here onwards,
hot press rolling treatment was performed under controlled conditions. From here on-
the membranes without hot press rolling treatment are named SPE and those with hot
wards, the membranes without hot press rolling treatment are named SPE and those with
press rolling treatment are named R-SPE. The final thicknesses of both types of electrolyte
hot press rolling treatment are named R-SPE. The final thicknesses of both types of elec-
membrane were kept the same, within the range of 85–100 µm. Membranes were then
trolyte membrane were kept the same, within the range of 85–100 μm. Membranes
Polymers 2022, 14, x FOR PEER REVIEW were
4 of 13
cut into circular disks with diameters of 18 mm and were stored in a glovebox for further
then cut into circular disks with diameters of 18 mm and were stored in a glovebox for
testing. The final images of a membrane are shown in Figure 3.
further testing. The final images of a membrane are shown in Figure 3.

Figure 2. (a–g) Preparation method for PVDF-HFP/LiTFSI-based solid polymer electrolytes (SPEs).
Figure 2. (a–g) Preparation method for PVDF-HFP/LiTFSI-based solid polymer electrolytes (SPEs).
Polymers 2022, 14, 363 4 of 12

Figure2.
Figure 2.(a–g)
(a–g)Preparation
Preparationmethod
methodfor
forPVDF-HFP/LiTFSI-based
PVDF-HFP/LiTFSI-basedsolid
solidpolymer
polymerelectrolytes
electrolytes(SPEs).
(SPEs).

Figure3.
Figure 3.PVDF-HFP/LiTFSI-based
PVDF-HFP/LiTFSI-basedsolid
PVDF-HFP/LiTFSI-based solid polymer
solidpolymer electrolyte
polymerelectrolyte (SPE).
electrolyte(SPE).
(SPE).

2.2.2. Hot
2.2.2. Hot
2.2.2. Press
Hot Press Rolling
Press Rolling Treatment
Treatmentof
Rolling Treatment ofSolid
of SolidPolymer
Solid PolymerElectrolytes
Polymer Electrolytes
Electrolytes
The equipment
The equipment
The (Figure
equipment (Figure
(Figure 4) 4) used
4) used to
used to perform
to perform the
perform the hot press
the hot press rolling
rolling treatment
treatment
treatment ofof the
the as-
as-
prepared solid
prepared solid
prepared polymer
solid polymer electrolyte
polymer electrolyte membranes
electrolyte membranes was
membranes wasa Hot Rolling
was aa Hot Press
Hot Rolling(MSK-HRP-MR100DC,
Rolling Press
Press (MSK-HRP-
(MSK-HRP-
MTI).
MR100DC,
MR100DC, The membranes
MTI).The
MTI). Thewere treated under
membranes
membranes controlled
weretreated
were treated conditions
under
under (Temperature
controlled
controlled conditions 60 ◦ C, rolling
conditions=(Temperature
(Temperature
=speed
= 60 = rolling
60 °C,
°C, 4rolling
rpm (speed
speed =display
speed rpmunits
= 44 rpm (speed
(speed indisplay
instrument),
display rolling
units in
units gap = 0.1rolling
in instrument),
instrument), mm). gap
rolling This
gap ==treatment
0.1 mm).
0.1 mm).
of the
This membranes
treatment of is
thethought
membranes to deform
is the
thought grain
to boundaries
deform the of
grainthe
This treatment of the membranes is thought to deform the grain boundaries of the poly- polymer
boundaries structure,
of the as
poly-
shown
mer in Figure
mer structure,
structure, as5,
as and more
shown
shown in grain5,
in Figure
Figure boundaries
5, and more
and are
more graincreated.
grain boundaries are
boundaries are created.
created.

Polymers 2022, 14, x FOR PEER REVIEW 5 of 13

Figure4.
Figure 4.Equipment
Equipmentused
usedfor
forthe
thehot
hotpress
pressrolling
rollingof
ofsolid
solidpolymer
polymerelectrolytes.
electrolytes.
electrolytes.

Figure 5. Grain boundary deformation in a solid polymer electrolyte after hot press rolling.
Figure 5. Grain boundary deformation in a solid polymer electrolyte after hot press rolling.
2.2.3. Catholyte Preparation
2.2.3.Catholyte
Catholyte Preparation
was prepared through a conventional doctor-blade method. A homogeneous
slurryCatholyte
was prepared with the through
was prepared lithium iron phosphatedoctor-blade
a conventional (LFP), carbonmethod.
(Super-P), and solid
A homogene-
polymer
ous slurry was prepared with the lithium iron phosphate (LFP), carbon (Super-P), was
electrolyte (SPE) solution in a mass ratio of 80:10:10. A homogeneous slurry and
prepared and then
solid polymer coated(SPE)
electrolyte on aluminum
solution infoil withratio
a mass the of
help of theAdoctor
80:10:10. blade, with
homogeneous a
slurry
wet
wasslurry thickness
prepared of 200
and then µm.on
coated The electrodefoil
aluminum sheets
withwere driedofatthe
the help room temperature
doctor fora
blade, with
2wet
days and thickness
slurry then cut into 15 µmm
of 200 diameter
m. The disks.
electrode All were
sheets preparations
dried at and
roomelectrode cutting
temperature for
were performed in a dry room with an approximately − 50 ◦ C dew point. The disks were
2 days and then cut into 15 mm diameter disks. All preparations and electrode cutting
were performed in a dry room with an approximately −50 °C dew point. The disks were
finally dried at 100 °C in vacuum for 16 h. The active material (LFP) mass loading of the
as-prepared electrodes was ~3.5 mg/cm2.

2.3. Characterization Methods

Polymers 2022, 14, 363 5 of 12

finally dried at 100 ◦ C in vacuum for 16 h. The active material (LFP) mass loading of the
as-prepared electrodes was ~3.5 mg/cm2 .

2.3. Characterization Methods

2.3.1. Electrochemical Impedance Spectroscopy (EIS)
Electrochemical impedance spectroscopy (EIS) measurements were implemented on a
VSP Biologic in a frequency range of 10 kHz–10 Hz to measure the ionic conductivity of the
hot press rolled and non-hot press rolled solid polymer electrolytes.

2.3.2. Direct Current (DC) Polarization

The lithium ion transference numbers of the SPE and Cal-SPE were measured by
performing AC impedance and DC polarization of a Li/SPE/Li symmetrical cell in a
coin cell (CR2032) setup. EIS measurements were performed before and after the DC
polarization test. The voltage applied for DC polarization was 10 mV.

2.3.3. Linear Sweep Voltammetry (LSV)

The electrochemical window was determined by linear sweep voltammetry (LSV)
using a Li/SPE/SS configuration in a coin cell (CR2032). The tests were carried out at a
scan rate of 0.1 mV/s over a potential range of 0–5.5 V.

2.3.4. Symmetrical Cell Cycling

To see the stability of the electrolyte membranes against Li dendrite propagation,
galvano-static cycling tests were carried out on symmetric cells (Li/SPE/Li), in a coin cell
(CR2032), at constant current densities of 0.1 mA/cm2 , 0.2 mA/cm2 , and 0.5 mA/cm2 at
60 ◦ C.

2.3.5. Galvano-Static Charge–Discharge Cycling

The electrochemical performance of the solid polymer electrolytes was tested with LFP/Li
half cells with as-prepared LFP catholyte and Li metal as the anode. Coin cells (CR2032) were
assembled in an argon-filled glovebox (BRAUN, Germany, H2 O and O2 ≤ 1 ppm). Charge
and discharge tests were carried out over a 2.8–3.8 V voltage range at 60 ◦ C. Two formation
cycles at C/50 were carried out before testing at high C-rates.

3. Results and Discussion

3.1. Ionic Conductivity
To find the ionic conductivity of the solid polymer electrolytes SPE and R-SPE, cells
with the configuration Li/electrolyte/Li in a coin cell setup were fabricated, and EIS tests
were conducted at different temperatures of 10 ◦ C, 20 ◦ C, 30 ◦ C, 40 ◦ C, 50 ◦ C, and 60 ◦ C
(Figure 6).
The bulk resistance values were obtained by fitting the equivalent circuit (Figure 7)
using Z-fit in EC-Lab software. The fitting of the experimental data to this circuit model
allows the estimation of bulk resistances (R2). The results of this fitting demonstrate that
the R-SPE electrolyte showed lower bulk resistance values compared to the SPE electrolyte.
The ionic conductivities (σ) were calculated from Equation (1):

σ = L/RA (1)

where A (cm2 ) is the area, L (cm) is the thickness of the SPE membrane, and R (Ω) is the
bulk resistance.
 3. Results and Discussion
3.1. Ionic Conductivity
To find the ionic conductivity of the solid polymer electrolytes SPE and R-SPE, cells
with the configuration Li/electrolyte/Li in a coin cell setup were fabricated, and EIS tests
Polymers 2022, 14, 363 6 of 12
were conducted at different temperatures of 10 °C, 20 °C, 30 °C, 40 °C, 50 °C, and 60 °C
(Figure 6).

Polymers 2022, 14, x FOR PEER REVIEW 7 of 13

This reduction in the crystallinity enhanced the amorphous region in the material, which
improved the mobility of lithium ions.
electrolytes at
Figure 6. Nyquist plots for SPE and R-SPE electrolytes at different
different temperatures.
temperatures.

The bulk resistance values were obtained by fitting the equivalent circuit (Figure 7)
using Z-fit in EC-Lab software. The fitting of the experimental data to this circuit model
allows the estimation of bulk resistances (R2). The results of this fitting demonstrate that
the R-SPE electrolyte showed lower bulk resistance values compared to the SPE electro-
lyte. The ionic conductivities (σ) were calculated from Equation (1):
𝜎 = 𝐿/𝑅𝐴 (1)
where A (cm2) is the area, L (cm) is the thickness of the SPE membrane, and R (Ω) is the
Figure 7. Equivalent circuit proposed to model the ionic conductivity of the solid polymer electrolytes.
bulk resistance.
Figure 7. Equivalent circuit proposed to model the ionic conductivity of the solid polymer electro-
Impedance and ionic conductivity values at different temperatures for both electro-
lytes. Impedance and ionic conductivity values at different temperatures for both electrolytes
lytes are summarized in Table 1. The ionic conductivities of the SPE ◦at 10 °C and 60 °C
are summarized−6in Table 1. The ionic conductivities
−4 of the SPE at 10 C and 60 ◦ C were
were 9.17 × 10
−6 S/cmand S/cm and 5.75 × 10 S/cm, respectively, whereas the ionic conduc-
Table
9.17 ×1. 10
Impedance andionic × 10−4 S/cm,
5.75conductivity values for SPE and
respectively, R-SPE atthe
whereas different temperatures. of
ionic conductivities
tivities of R-SPE
◦ at 10◦ °C and 60 °C were − 5 1.40 × 10−5 S/cm−4and 6.56 × 10−4 S/cm, re-
R-SPE at 10 C and 60 C were 1.40 × 10 S/cm and 6.56 × 10 S/cm, respectively. These
spectively. These ionic conductivity values are in good agreement Ionic Conductivity
with the literature,
Impedancevalues
ionic conductivity (Ω) are Impedance Ionic Conductivity
in good agreement with the literature, which discusses solid
T (°C) discusses solid polymer electrolytes based on the same materials [29,30].
which (S/cm) These re-
polymer electrolytes
SPE based(Ω)onR-SPE
the same materials(S/cm)[29,30].
SPE These results clearly indicate
sults clearly indicate that the ionic conductivity of the R-SPE electrolyte sR-SPE better than that
that the ionic conductivity of the R-SPE electrolyte s better than that of the SPE. This
of10
the SPE. This improvement 223 in the ionic conductivity −6
of the electrolyte can×be attributed
−5
9.17 × 10
improvement in the ionic conductivity of the electrolyte can be attributed to the10
343 1.40 decrease in
to20
thethe decrease170
crystallinity in the polymer
of the crystallinity
91 of application
by the the polymer1.85ofby the
×hot
10 −5 application of hot press
press rolling. This × 10−5 rolling.
3.44reduction in the
30
crystallinity 60
enhanced 38
the amorphous region in5.21
the × 10−5 which improved
material, the−5mobility
8.28 × 10
of 40
lithium ions.23 16 1.33 × 10−4 1.93 × 10−4
50 The temperature
12 dependence
7 of the ionic2.58conductivity
× 10 −4 of both electrolytes,
4.31 × 10−4SPE and
R-SPE,
60 is shown 5 by Arrhenius4curves (Figure 8). ×The
5.75 10−4plot illustrates a linear
6.56 × 10−4behavior
and follows the Arrhenius relationship. The results demonstrate that both electrolytes
showed similar temperature-dependent
The temperature dependence of the ionic
ionic conductivity
conductivitybehavior, showing increases
of both electrolytes, SPE andin
ionic conductivity with the temperature increase. The increases in ionic conductivity with
R-SPE, is shown by Arrhenius curves (Figure 8). The plot illustrates a linear behavior and
temperature can be attributed to increases in free volume, polymer segmental mobility, and
follows the Arrhenius relationship. The results demonstrate that both electrolytes showed
ionic mobility [31].
similar temperature-dependent ionic conductivity behavior, showing increases in ionic
conductivity with the temperature increase. The increases in ionic conductivity with tem-
perature can be attributed to increases in free volume, polymer segmental mobility, and
ionic mobility [31].
 Table 1. Impedance and ionic conductivity values for SPE and R-SPE at different temperatures.

Ionic Conductivity
Impedance (Ω) Impedance Ionic Conductivity
T (°C) (S/cm)
SPE (Ω) R-SPE (S/cm) SPE
Polymers 2022, 14, 363 R-SPE 7 of 12
−6 −5
10 343 223 9.17 × 10 1.40 × 10
20 170 91 1.85 × 10−5 3.44 × 10−5
30 1. Impedance
Table 60 and ionic conductivity
38 values for
5.21 10−5
SPE×and R-SPE at different × 10−5
temperatures.
8.28
−4
40 23 16 1.33 × 10 1.93 × 10−4
Ionic
50 Impedance
12 (Ω) 7Impedance (Ω)2.58 × 10−4 Ionic
4.31Conductivity
× 10−4
T (◦ C) Conductivity
SPE R-SPE −4 (S/cm) R-SPE
60 5 4 5.75 ×(S/cm)
10 SPE 6.56 × 10−4
10 343 223 9.17 × 10−6 1.40 × 10−5
The temperature dependence of the ionic conductivity of both electrolytes, SPE and
20 170 91 1.85 × 10−5 3.44 × 10−5
R-SPE, is shown by Arrhenius curves (Figure 8). The plot illustrates a linear behavior and
30 the Arrhenius60relationship. The38 −5
5.21 × 10that 8.28 × 10− 5
follows results demonstrate both electrolytes showed
similar
40 temperature-dependent
23 ionic conductivity
16 1.33 × 10−4showing increases
behavior, 1.93 × 10−in
4
ionic
conductivity
50 with the12temperature increase.
7 The increases
2.58 × in ionic
10− 4 conductivity with
4.31 × 10 −4 tem-
perature can be attributed to increases in free volume, polymer segmental mobility, and
60 5 4 5.75 × 10−4 6.56 × 10−4
ionic mobility [31].

Figure 8.
Figure Log σσ versus
8. Log versus 1000/T
1000/Tplot
plotfor
forSPE
SPEand
andR-SPE
R-SPEelectrolytes.
electrolytes.

The activation energies were calculated by the Arrhenius equation:

− Ea
 
σ = σ0 exp (2)
RT

where σ, σ0 , T, Ea , R are the ionic conductivity, pre-exponential factor, temperature, activa-

tion energy, and gas constant, respectively.
The activation energies were calculated as 0.29 eV and 0.31 eV for the R-SPE and
SPE, respectively, being in good agreement with the previously reported values for solid
polymer electrolytes [32]. The low activation energy of the R-SPE is attributed to an increase
in the amorphous region by hot press rolling, which eased lithium-ion movement within
the electrolytes. The lower activation energy indicates that lithium ions needed less energy
to move within the electrolytes [33].

3.2. Direct Current (DC) Polarization and Transference Number

The Li-ion transportation number (t+ Li ) is an important parameter when considering
the transportation of lithium ions in solid polymer electrolytes. Coin cells with the configu-
rations Li/SPE/Li and Li/R-SPE/Li were prepared, and DC polarization was performed
until a steady-state current was reached (Figure 9c). EIS tests were also conducted before
and after the DC polarization for Li/R-SPE/Li and Li/SPE/Li cells (Figure 9a and 9b, re-
 3.2. Direct Current (DC) Polarization and Transference Number
+
The Li-ion transportation number (𝑡𝐿𝑖 ) is an important parameter when considering
the transportation of lithium ions in solid polymer electrolytes. Coin cells with the config-
urations Li/SPE/Li and Li/R-SPE/Li were prepared, and DC polarization was performed
Polymers 2022, 14, 363 until a steady-state current was reached (Figure 9c). EIS tests were also conducted before 8 of 12
and after the DC polarization for Li/R-SPE/Li and Li/SPE/Li cells (Figure 9a and Figure 9b,
+
respectively). Transference numbers (𝑡𝐿𝑖 ) were calculated by using the Bruce–Vincent–
Evans equation [34]: +
spectively). Transference numbers (t Li ) were calculated by using the Bruce–Vincent–Evans
equation [34]: 𝐼𝑆 [∆𝑉 − 𝐼0 𝑅𝑂 ]
+
+ = IS [ ∆V − IO RO ]
𝑡t𝐿𝑖 (3)
= (3)
Li I𝐼O𝑂 [[∆𝑉
∆V −−IS𝐼𝑆RS𝑅]𝑆 ]
where
where∆V ∆Visisthe applied
the appliedpolarization
polarization voltage;𝐼0IOand
voltage; and𝑅R 𝑂Oare
arethe
theinitial
initialcurrent
currentand
andinitial
initial
interfacial resistance values before polarization, respectively;
interfacial resistance values before polarization, respectively; and IS andand 𝐼 and 𝑅 a re the
𝑆 RS are𝑆the steady-
steady-state
state currentcurrent and interfacial
and interfacial resistance
resistance valuesvalues after polarization,
after polarization, respectively.
respectively. The ROThe and
𝑅R𝑂 Sand 𝑅𝑆 for
values values
bothfor
theboth the electrolytes
electrolytes were calculated
were calculated from impedance
from impedance resultsand
results before before
after
and
DCafter DC polarization
polarization (Figure 9a,b).
(Figure 9a,b).

EISof
Figure9.9.EIS
Figure of (a)
(a) Li/R-SPE/Li
Li/R-SPE/Liand
and(b)
(b)Li/SPE/Li
Li/SPE/Li cells
cells before
before and
and afterpolarization,
after polarization,and
and(c)
(c)DC
DC
polarizationcurve.
polarization curve.

At room temperature, the transference numbers for the SPE and R-SPE were calculated
as 0.12 and 0.18, respectively, which are close to the literature values [21]. The t+
Li for the
R-SPE was higher than the transference number of the SPE. The remarkable improvement in
the lithium-ion transference number can be ascribed to an increase in the grain boundaries.
By applying the hot press rolling, the grain boundaries were reformed, which created more
pathways for lithium ions to move along. These results are in good agreement with the
ionic conductivity results as the movement of lithium ions played an important role in the
conductivity improvement.

3.3. Linear Sweep Voltammetry (LSV)

Linear sweep voltammetry (LSV) at 60 ◦ C for both the SPE and R-SPE was performed
to evaluate their voltage stability windows (Figure 10). Both electrolytes showed stability
up to 4.1 V. Slight differences in the results could be due to differences in the OCV values
of the cells; otherwise, no significant effect of hot press rolling on the stability voltages
was observed.
 3.3. Linear Sweep Voltammetry (LSV)
Linear sweep voltammetry (LSV) at 60 °C for both the SPE and R-SPE was performed
to evaluate their voltage stability windows (Figure 10). Both electrolytes showed stability
up to 4.1 V. Slight differences in the results could be due to differences in the OCV values
Polymers 2022, 14, 363 9 of 12
of the cells; otherwise, no significant effect of hot press rolling on the stability voltages
was observed.

10. Linear sweep voltammetry

Figure 10.
Figure voltammetry (LSV)
(LSV) tests
testsfor
forSS/SPE/Li
SS/SPE/Li and SS/R-SPE/Li cellsto
SS/R-SPE/Li cells to evaluate
evaluate
their voltage stability windows.
their voltage stability windows.

3.4. Symmetrical
3.4. Symmetrical Cell
Cell Cycling
Cycling
To further investigate the electrochemical stability of electrolytes with a Li-metal
To further investigate the electrochemical stability of electrolytes with a Li-metal an-
anode, symmetric cells with configurations Li/SPE/Li and Li/R-SPE/Li were fabricated
ode, symmetric cells with configurations Li/SPE/Li and Li/R-SPE/Li were fabricated and
and subsequently implemented for plating/striping tests to measure the stability of the
subsequently implemented for plating/striping tests to measure the stability 2 was of the elec-
electrolytes against lithium dendrite. A current density of 0.1 mA/cm applied for
trolytes against lithium dendrite. A current density of 0.1 mA/cm 2 was applied for the first
the first 500 cycles, followed by 0.2 mA/cm2 for the next 500 cycles, then continuing at2
500 cycles, followed by 0.2 mA/cm2 for the next 500 cycles, then continuing at 0.5 mA/cm
0.5 mA/cm until the cell began to short circuit. This test was performed at 60 ◦ C. Hot
2
until the cell began to short circuit. This test was performed at 60 °C. Hot press rolled
press rolled membranes (R-SPE) showed better stability against lithium dendrite growth
membranes
Polymers 2022, 14, x FOR PEER REVIEW (R-SPE) showed better stability against lithium dendrite growth compared to 10 of 13
compared to non-hot press rolled membranes (SPE). In addition, the Li/R-SPE/Li cell
non-hot press rolled membranes (SPE). In addition, the Li/R-SPE/Li cell performed more
performed more cycles (nearly 100 more) compared to the Li/SPE/Li cell (Figure 11).
cycles (nearly 100 more) compared to the Li/SPE/Li cell (Figure 11).

Cycling
Figure 11.Figure 11.ofCycling
symmetrical cells withcells
of symmetrical configurations of Li/SPE/Li
with configurations and Li/R-SPE/Li.
of Li/SPE/Li and Li/R-SPE/Li.

3.5. Galvano-Static Charge–Discharge

3.5. Galvano-Static Cycling Cycling
Charge–Discharge
The cycling profiles of the LFP/SPE/Li and LFP/R-SPE/Li cells were tested under
The cycling profiles of the LFP/SPE/Li and LFP/R-SPE/Li cells were tested under a
a current density of 0.1 C at 60 ◦ C. For the LFP/R-SPE/Li cell, a first discharge specific
current density of 0.1 C at 60 °C. For the LFP/R-SPE/Li cell, a first discharge specific ca-
capacity of 134.3 mAh/g was achieved, whereas for the LFP/SPE/Li cell it was 118 mAh/g
pacity of 134.3 mAh/g was achieved, whereas for the LFP/SPE/Li cell it was 118 mAh/g
(Figure 12a). The LFP/R-SPE/Li cell retained more than 98.5% coulombic efficiency over
the first 50 cycles (Figure 12c). The improved cycling performance of the LFP/R-SPE/Li
cell can be attributed to the improved ionic conductivity of the electrolyte and interfacial
contact between the electrodes and electrolyte after the application of the hot press rolling
Polymers 2022, 14, 363 10 of 12

(Figure 12a). The LFP/R-SPE/Li cell retained more than 98.5% coulombic efficiency over
the first 50 cycles (Figure 12c). The improved cycling performance of the LFP/R-SPE/Li
cell can be attributed to the improved ionic conductivity of the electrolyte and interfa-
Polymers 2022, 14, x FOR PEER REVIEW 11 of 1
cial contact between the electrodes and electrolyte after the application of the hot press
rolling treatment.

Figure 12. Figure

Cycling12.results
Cycling forresults
LFP/Liforbatteries.
LFP/Li batteries.
(a) First(a)discharge
First discharge
cycles cycles
with SPEwithandSPER-SPE
and R-SPE ele
electrolytestrolytes
at 0.1 C at
and0.160C◦and
C, and60 (b)
°C, with
and (b) with
R-SPE R-SPE electrolytes
electrolytes at C,
at 0.1 C, 0.5 0.1and
C, 0.5
1 C.C,(c)
and 1 C.cycle
Long (c) Long cyc
performance performance
with SPE and with SPE and
R-SPE, andR-SPE, and efficiency
coulombic coulombicfor efficiency
a batteryfor a battery
with R-SPE.with R-SPE.

Figure4. 12b
Conclusions
shows the cycling results of the LFP/R-SPE/Li cell at different C-rates of
0.1 C, 0.5 C, andThe1 C. At high
ionic C-rates, aofdecline
conductivity in the capacity
an electrolyte ofaffected
is greatly the cell can be degree
by the seen. This
of crystallin
is due to the fast degradation of the battery at high C-rates [35].
ity of the polymer matrix. In this work, a simple and effective technique of hot press rol
The results
ing hasevidence that the
been shown hot pressthe
to improve rolling treatmentof
performance improved the electrochemical
solid polymer electrolytes. Rolling a
performancehigh oftemperature
the solid polymer electrolyte.
and pressure causes grain boundary changes in the polymer structur
resulting in an increase in the amorphous region. An unstructured amorphous regio
4. Conclusions
helps the movement of lithium ions within the electrolyte.
The ionic conductivity
A significantofimprovement
an electrolyteinis the
greatly
ionicaffected by the of
conductivity degree of crystallinity
the electrolyte was achieve
of the polymer matrix. In this work, a simple and effective technique of hot press rolling show
by the application of the hot press rolling technique. It has been experimentally
has been that,
shown at to
10 improve the performance
°C, the ionic conductivity of of the
solid polymer increased
electrolyte electrolytes.
fromRolling
9.17 ×at10−6 S/cm
high temperature
to 1.40 × and
10pressure
−5
S/cm, causes grain boundary changes in the polymer structure,
a 53% increase.
resulting in an increase in the amorphous region. An unstructured amorphous region helps
The activation energies for both electrolytes were calculated by plotting an Arrheniu
the movement of lithium ions within the electrolyte.
curve. For SPEs, it was 0.31 eV and, after hot press rolling treatment, it decreased to 0.2
A significant improvement in the ionic conductivity of the electrolyte was achieved
eV. A lower activation energy means easier Li-ion movement within the electrolyte. Larg
by the application of the hot press rolling technique. It has been experimentally shown
grain boundaries are unfavorable for Li-ion transport. By applying hot press rolling, th
that, at 10 ◦ C, the ionic conductivity of the electrolyte increased from 9.17 × 10−6 S/cm to
−grain boundaries are deformed, which creates more pathways for lithium ions to mov
1.40 × 10 5 S/cm, a 53% increase.
along.
The activation energies for both electrolytes were calculated by plotting an Arrhenius
An overall improvement in the electrochemical performance of the solid polyme
curve. For SPEs, it was 0.31 eV and, after hot press rolling treatment, it decreased to 0.29 eV.
electrolyte has been shown. The smooth surface of the electrolyte provided better contac
A lower activation energy means easier Li-ion movement within the electrolyte. Large grain
between the electrode and electrolyte, which improved the performance of the cell. Th
LFP/R-SPE/Li batteries showed a first discharge capacity of 134.3 mAh/g at 0.1C, which
better than the capacity shown by LFP/SPE/Li batteries (118 mAh/g). The homogenou
structure of the membranes has obvious advantages in improving the performance of th
electrolyte.
Polymers 2022, 14, 363 11 of 12

boundaries are unfavorable for Li-ion transport. By applying hot press rolling, the grain
boundaries are deformed, which creates more pathways for lithium ions to move along.
An overall improvement in the electrochemical performance of the solid polymer
electrolyte has been shown. The smooth surface of the electrolyte provided better contact
between the electrode and electrolyte, which improved the performance of the cell. The
LFP/R-SPE/Li batteries showed a first discharge capacity of 134.3 mAh/g at 0.1 C, which
is better than the capacity shown by LFP/SPE/Li batteries (118 mAh/g). The homogenous
structure of the membranes has obvious advantages in improving the performance of
the electrolyte.
All the results show that hot press rolling is an effective technique that is easy to
implement and improves the performance of solid polymer electrolytes for solid-state
lithium-metal batteries.

Author Contributions: M.B. and P.Y. initiated the research. M.B. and J.V.M. supervised the work. P.Y.
prepared the samples. P.Y. and S.H.B. performed experiments. P.Y. wrote the paper with contributions
from A.R.K. and P.I. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by the project “Bridge–Green Chemistry” which received research
grant from INNOVIRIS.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Hannah Ritchie and Max Roser (2020)—“CO2 and Greenhouse Gas Emissions”. Available online: https://ourworldindata.org/
(accessed on 25 November 2021).
2. Wan, J.; Xie, J.; Mackanic, D.; Burke, W.; Bao, Z.; Cui, Y. Status, promises, and challenges of nanocomposite solid-state electrolytes
for safe and high performance lithium batteries. Mater. Today Nano 2018, 4, 1–16. [CrossRef]
3. Kim, H.; Jeong, G.; Kim, Y.-U.; Kim, J.-H.; Park, C.-M.; Sohn, H.-J. Metallic anodes for next generation secondary batteries. Chem.
Soc. Rev. 2013, 42, 9011–9034. [CrossRef] [PubMed]
4. Wang, Q.; Yao, Z.; Zhao, C.; Verhallen, T.; Tabor, D.P.; Liu, M.; Ooms, F.; Kang, F.; Aspuru-Guzik, A.; Hu, Y.-S.; et al. Interface
chemistry of an amide electrolyte for highly reversible lithium metal batteries. Nat. Commun. 2020, 11, 4188. [CrossRef]
5. Albertus, P.; Anandan, V.; Ban, C.; Balsara, N.; Belharouak, I.; Buettner-Garrett, J.; Chen, Z.; Daniel, C.; Doeff, M.; Dudney,
N.J.; et al. Challenges for and Pathways toward Li-Metal-Based All-Solid-State Batteries. ACS Energy Lett. 2021, 6, 1399–1404.
[CrossRef]
6. Lv, F.; Wang, Z.; Shi, L.; Zhu, J.; Edström, K.; Mindemark, J.; Yuan, S. Challenges and development of composite solid-state
electrolytes for high-performance lithium ion batteries. J. Power Sources 2019, 441, 227175. [CrossRef]
7. Li, S.; Zhang, S.; Shen, L.; Liu, Q.; Ma, J.; Lv, W.; He, Y.; Yang, Q. Progress and Perspective of Ceramic/Polymer Composite Solid
Electrolytes for Lithium Batteries. Adv. Sci. 2020, 7, 1903088. [CrossRef]
8. Fergus, J.W. Ceramic and polymeric solid electrolytes for lithium-ion batteries. J. Power Sources 2010, 195, 4554–4569. [CrossRef]
9. Yue, L.; Ma, J.; Zhang, J.; Zhao, J.; Dong, S.; Liu, Z.; Cui, G.; Chen, L. All solid-state polymer electrolytes for high-performance
lithium ion batteries. Energy Storage Mater. 2016, 5, 139–164. [CrossRef]
10. Yu, Q.; Jiang, K.; Yu, C.; Chen, X.; Zhang, C.; Yao, Y.; Jiang, B.; Long, H. Recent progress of composite solid polymer electrolytes
for all-solid-state lithium metal batteries. Chin. Chem. Lett. 2021, 32, 2659–2678. [CrossRef]
11. Jiang, Y.; Yan, X.; Ma, Z.; Mei, P.; Xiao, W.; You, Q.; Zhang, Y. Development of the PEO Based Solid Polymer Electrolytes for
All-Solid State Lithium Ion Batteries. Polymers 2018, 10, 1237. [CrossRef]
12. Zhou, X.; Zhao, X.; Suo, Z.; Zou, C.; Runt, J.; Liu, S. Electrical breakdown and ultrahigh electrical energy density in poly(vinylidene
fuoride-hexafuoropropylene) copolymer. Appl. Phys. Lett. 2009, 94, 162901. [CrossRef]
13. Han, W.; Kim, T.; Yoo, B.; Park, H.-H. Tunable Dielectric Properties of Poly(vinylidenefluoride-co-hexafluoropropylene) Films
with Embedded Fluorinated Barium Strontium Titanate Nanoparticles. Sci. Rep. 2018, 8, 4086. [CrossRef]
14. Mindemark, J.; Lacey, M.J.; Bowden, T.M.; Brandell, D. Beyond PEO—Alternative host materials for Li + -conducting solid
polymer electrolytes. Prog. Polym. Sci. 2018, 81, 114–143. [CrossRef]
15. Fasciani, C.; Panero, S.; Hassoun, J.; Scrosati, B. Novel configuration of poly(vinylidenedifluoride)-based gel polymer electrolyte
for application in lithium-ion batteries. J. Power Sources 2015, 294, 180–186. [CrossRef]
16. Golodnitsky, D.; Strauss, E.; Peled, E.; Greenbaum, S. Review—On Order and Disorder in Polymer Electrolytes. J. Electrochem. Soc.
2015, 162, A2551–A2566. [CrossRef]
Polymers 2022, 14, 363 12 of 12

17. Robbins, A.B.; Minnich, A.J. Crystalline polymers with exceptionally low thermal conductivity studied using molecular dynamics.
Appl. Phys. Lett. 2015, 107, 201908. [CrossRef]
18. Mileva, D.; Tranchida, D.; Gahleitner, M. Designing polymer crystallinity: An industrial perspective. Polym. Cryst. 2018, 1, e10009.
[CrossRef]
19. Tashiro, K. Handbook of Polymer Crystallization; John Wiley & Sons, Ltd.: Hoboken, NJ, USA, 2013; pp. 165–196. [CrossRef]
20. Chang, C.-W.; Lai, W.-C. A strategy for preparing solid polymer electrolytes via the electrospinning process. J. Taiwan Inst. Chem.
Eng. 2020, 116, 279–285. [CrossRef]
21. St-Onge, V.; Cui, M.; Rochon, S.; Daigle, J.-C.; Claverie, J.P. Reducing crystallinity in solid polymer electrolytes for lithium-metal
batteries via statistical copolymerization. Commun. Mater. 2021, 2, 83. [CrossRef]
22. Tarascon, J.-M.; Armand, M. Issues and challenges facing rechargeable lithium batteries. Nature 2001, 414, 359–367. [CrossRef]
23. Croce, F.; Sacchetti, S.; Scrosati, B. Advanced, lithium batteries based on high-performance composite polymer electrolytes. J.
Power Sources 2006, 162, 685–689. [CrossRef]
24. Lee, H.S.; Yang, X.Q.; McBreen, J.; Xu, Z.S.; Skotheim, T.A.; Okamoto, Y. Ionic Conductivity of a Polymer Electrolyte with Modified
Carbonate as a Plasticizer for poly(ethylene oxide). J. Electrochem. Soc. 1994, 141, 886–889. [CrossRef]
25. Zhan, H.; Wu, M. Excellent Performances of Composite Polymer Electrolytes with Porous Vinyl-Functionalized SiO2 Nanoparticles
for Lithium Metal Batteries. Polymers 2021, 13, 2468. [CrossRef]
26. Xu, L.; Li, G.; Guan, J.; Wang, L.; Chen, J.; Zheng, J. Garnet-doped composite polymer electrolyte with high ionic conductivity for
dendrite-free lithium batteries. J. Energy Storage 2019, 24, 100767. [CrossRef]
27. Wang, H.; Cui, X.; Zhang, C.; Gao, H.; Du, W.; Chen, Y. Promotion of Ionic Conductivity of PEO-Based Solid Electrolyte Using
Ultrasonic Vibration. Polymers 2020, 12, 1889. [CrossRef] [PubMed]
28. Wei, Z.; Ren, Y.; Wang, M.; He, J.; Huo, W.; Tang, H. Improving the Conductivity of Solid Polymer Electrolyte by Grain Reforming.
Nanoscale Res. Lett. 2020, 15, 122. [CrossRef] [PubMed]
29. Mathies, L.; Diddens, D. Transport mechanism of lithium ions in non-coordinating P(VdF-HFP) copolymer matrix. Solid State Ion.
2020, 357, 115497. [CrossRef]
30. Wang, F.; Li, L. Influence of additives in PVDF-base solid polymer electrolyte. Sustain. Energy Fuels 2018, 2, 492–498. [CrossRef]
31. Ataollahi, N.; Ahmad, A.; Hamzah, H.; Rahman, M.; Sabirin, M.N. Ionic Conductivity of PVDF-HFP/MG49 Based Solid Polymer
Electrolyte. Adv. Mater. Res. 2012, 501, 29–33. [CrossRef]
32. Gonçalves, R.; Miranda, D.; Almeida, A.M.L.D.F.; Silva, M.; Meseguer-Dueñas, J.M.; Ribelles, J.G.; Lanceros-Méndez,
S.; Costa, C. Solid polymer electrolytes based on lithium bis(trifluoromethanesulfonyl)imide/poly(vinylidene fluoride
-co-hexafluoropropylene) for safer rechargeable lithium-ion batteries. Sustain. Mater. Technol. 2019, 21, e00104. [CrossRef]
33. Leš, K.; Jordan, C.-S. Ionic conductivity enhancement in solid polymer electrolytes by electrochemical in situ formation of an
interpenetrating network. RSC Adv. 2020, 10, 41296–41304. [CrossRef]
34. Colin, J.E.; Vincent, A. Electrochemical measurement of transference numbers in polymer electrolytes. Polymer 1987, 28, 2324–2328.
35. Eftekhari, A. Lithium-Ion Batteries with High Rate Capabilities. ACS Sustain. Chem. Eng. 2017, 5, 2799–2816.