Nama : Nita Abelia

NIM : 22030234080
Kelas : KC 2022
UTS KIMIA MATERIAL
Judul artikel : Synthesis and characterization of acrylamide/zeolite nanocomposite hydrogels
for aqueous zinc-ion batteries
Penulis artikel : Hongfei Bao, Wenxuan Pu , Huihui Gao
Tahun terbit : 2023

A. Pendahuluan
Perkembangan perangkat penyimpanan energi yang fleksibel seperti baterai dan
superkapasitor menjadi penting dalam perangkat elektronik. Di antara teknologi
baterai yang sedang berkembang baterai zinc-ion (ZIB) telah menarik perhatian sebagai
alternatif yang lebih aman dan berkelanjutan dibandingkan baterai lithium-ion
konvensional. ZIB memanfaatkan logam seng sebagai anoda, garam seng yang
melimpah sebagai elektrolit, dan oksida logam sebagai katoda. Dibandingkan dengan
litium seng lebih murah, tidak beracun, dan bebas dendrit selama pelapisan dan
pengupasan. Gugus amino polar dan nanopartikel zeolit dapat berperan untuk disosiasi
dan transportasi ion dalam meningkatkan konduktivitas suhu ruangan dibandingkan
dengan polimer konvensional. Selain itu, jaringan hidrogel yang berikatan silang secara
kovalen diperkirakan menunjukkan stabilitas dimensi dan termal yang baik.
Nanopartikel zeolit dengan luas permukaan dan kapasitas pertukaran ion yang tinggi
dapat semakin meningkatkan sifat mekanik, serapan elektrolit, dan luas antar muka
elektroda-elektrolit.
Namun sebagian besar ZIB masih menggunakan elektrolit cair yang dapat bocor
dan mudah terbakar. Sehingga penggunaan elektrolit polimer menjadi solusi masalah
tersebut. Kemudian muncul GPE yang dapat menggabungkan konduktivitas ionik yang
tinggi pada cairan dan stabilitas mekanik padatan. GPE biasanya disintesis dengan
memasukkan garam dan pelarut ke dalam jaringan polimer yang berikatan silang. GPE
berbasis PAM memiliki keunggulan berupa gugus fungsional amide. Gugus amino
polar mendorong disosiasi garam dan solvasi ion, sedangkan ikatan hidrogennya
memungkinkan retensi air yang tinggi untuk meningkatkan konduktivitas. Untuk
meningkatkan sifat GPE termasuk memasukkan nanofiller seperti zeolit, graphene, dan
karbon nanotube. Zeolit adalah mineral aluminosilikat mikropori dengan struktur pori
yang jelas, luas permukaan yang tinggi, dan kapasitas pertukaran ion. Sehingga,
nanopartikel zeolit berpotensi meningkatkan konduktivitas, kekuatan mekanik,
porositas, dan sifat antarmuka elektrolit polimer. Meskipun GPE zeolit-komposit telah
diterapkan pada baterai litium-ion potensinya dalam ZIB masih belum dieksplorasi.
Oleh karena itu, penelitian ini bertujuan untuk mensintesis hidrogel nanokomposit
PAM/zeolit melalui polimerisasi in-situ dan mempelajari struktur dan kinerja
elektrokimianya sebagai GPE untuk ZIB fleksibel. Monomer akrilamida, nanopartikel
zeolit, dan garam seng diperoleh secara komersial. Hidrogel nanokomposit disintesis
dengan melarutkan akrilamida dan mendispersikan nanopartikel zeolit dalam air,
diikuti dengan penambahan pengikat silang dan inisiator untuk menginduksi
polimerisasi in-situ. Hidro-gel terpolimerisasi direndam dalam larutan elektrolit seng
untuk pengujian elektrokimia selanjutnya.Sehingga, menjadi inovasi untuk optimasi
lebih lanjut dan penelitian terapan pada elektrolit nanokomposit PAM-zeolite untuk
ZIB yang dapat dipakai serta sistem penyimpanan energi lainnya.
B. Metode Penelitian
Hidrogel nanokomposit PAM/zeolit disintesis melalui polimerisasi radikal
bebas in- situ. Monomer akrilamida dilarutkan dalam air suling untuk mendapatkan
larutan 25% berat. Dalam identifikasi struktur kimia dan gugus fungsi hidrogel
nanokomposit yang disintesis diperiksa dengan spektroskopi FT-IR reflektansi total
yang dilemahkan (Bruker Alpha II). Spektrum direkam pada 1.4000–400 cm. Struktur
mikro dan morfologi penampang hidrogel dianalisis menggunakan SEM emisi
lapangan JEOL JSM-7200 F. Mikrograf SEM dinilai untuk menentukan distribusi
ukuran pori dan dispersi nanopartikel zeolit. Instrumen TGA Mettler Toledo digunakan
untuk mengevaluasi terapi stabilitas dan komposisi hidrogel nanokomposit yang buruk.
Kurva penurunan berat dianalisis untuk menentukan suhu degradasi tambang dan
kandungan zeolit. Suhu transisi gelas (Tg) dan perubahan fasa dalam hidrogel diperiksa
menggunakan TA Instruments DSC 2500. Tg diidentifikasi dari titik belok pada kurva
aliran panas. Dilakukan uji mekanis sifat tekan hidrogel yang ditentukan menggunakan
mesin uji universal Instron 5969 yang dilengkapi dengan sel beban 50 N. Modulus
tekan dihitung dari daerah linier awal tegangan-regangan melengkung.
Konduktivitas ionik elektrolit hidrogel nanokomposit dihitung menggunakan
spektroskopi impedansi elektrokimia (EIS). Pengukuran dilakukan pada rentang
frekuensi 100 kHz - 1 Hz dengan amplitudo AC 10 mV menggunakan potensiostat
Referensi Gamry 3000. Elektrolit hidrogel diapit di antara dua elektroda baja tahan
karat dalam sel konduktivitas di dalam sangkar faraday. Resistansi sebagian besar
ditentukan dari plot Nyquist. Konduktivitas ionik dihitung sebagai y = L/RA, di mana
L adalah ketebalan, A adalah luas elektroda, dan R adalah resistansi curah. Perilaku
redoks dan sifat kinetik elektrolit hidrogel diselidiki pada berbagai kecepatan
pemindaian dari 0,1-1 mV/s menggunakan potensiostat Biologis SP-150. Sel Swagelok
dua elektroda dibuat dengan seng foil sebagai elektroda lawan dan referensi.
Pengukuran dilakukan pada suhu kamar pada rentang potensial 0–1,8 V vs Zn2+/Zn.
Kinerja siklus elektrolit hidrogel dievaluasi dengan siklus pelepasan muatan
galvanostatik menggunakan penganalisis baterai Neware pada rentang potensial 0,5–
1,8 V. Sel Swagelok dibuat mirip dengan pengujian CV. Sel-sel tersebut didaur ulang
pada kepadatan arus yang bervariasi dari 0,1-1 A/gZn dengan kapasitas cutoff 80
mAh/gZn. Kapasitas pelepasan, efisiensi coulomb, dan retensi kapasitas ditentukan dari
profil tegangan-kapasitas.
C. Hasil dan Pembahasan

Gambar 1. Spektrum FT-IR

Pembentukan hidrogel nanokomposit PAM/zeolit diverifikasi menggunakan

spektroskopi FT-IR. Gambar diatas menunjukkan spektrum FT-IR monomer
akrilamida, pengikat silang, nanopartikel zeolit, dan hidrogel nanokomposit dengan
kandungan zeolit 0 % dan 15 %.Dalam spektrum monomer akrilamida puncaknya pada
1620 cm-1 dan 1660 cm-1 dengan ikatan rangkap C––C dan ikatan C––O dari gugus
asam amino. Setelah polimerisasi intensi puncak dari 1620 cm-1 secara signifikan
menunjukkan konsumsi ikatan C-C. Sehingga secara bersamaan pincak baru muncul
pada 1560 cm-1yang menunjukkan pembengkokan NH dari gugus amino yang
terbentuk di PAM dan terjadi polimerisasi radikal bebas akrilamida. Dalam spektrum
hidrogel nanokomposit, nanopartikel zeolit menyumbangkan 1 pita getaran karena
terjajd pembengkokan Si-O-Si dan Al-O sehingga meningkatkan intensitas puncak
disebabkan oleh kandungan zeolit yang semakin tinggi. Selain itu, pergeseran dan
pelebaran puncak amida ikatan C-O diakibatkan oleh ikatan hidrogen antara amida dan
hidroksi zeolit sehingga terjadi penggabungan partikel nanozeolit kedalam jaringan
PAM yang berikatan silang.

Gambar 2. Mikrograf SEM

Gambar diatas menunjukkan pencitraan SEM untuk menguji dampak partikel
nano zeolit pada morfologi dan porositas hidro-gel nanokomposit. Gambar (2a)
menunjukkan struktur padat tidak berpori. Ketika kandungan zeolit meningkat menjadi
15%. Gambar (2d) menunjukkan hidrogel arsitektur yang lebih berpori karena
peningkatan penyerapan air dan pemisahan rantai polimer oleh nanopartikel.
Nanopartikel zeolit yang terdispersi bertindak sebagai titik ikatan silang untuk
memberikan ikatan silang fisik tambahan dalam jaringan hidrogel yang berikatan silang
secara kovalen. Efek penguatan nano ini membatasi mobilitas rantai polimer, yang
diwujudkan dalam peningkatan kekuatan mekanik dan peningkatan stabilitas dimensi.
Nanopartikel zeolit berinteraksi kuat dengan matriks hidrogel melalui ikatan hidrogen
yang luas antara gugus akrilamida amida dan gugus hidroksil zeolit. Interaksi
antarmuka ini mendorong adhesi antara fase organik dan anorganik. Dengan demikian,
transfer beban efektif terjadi dari fase hidrogel kontinyu ke nanopartikel zeolit yang
terdispersi. Zeolit memiliki kapasitas pertukaran ion yang tinggi dan kemampuan
menghantarkan pembawa muatan melalui kerangka berpori. Dengan demikian, partikel
nano zeolit memfasilitasi transpor cepat ion Zn2+ , berkontribusi terhadap peningkatan
konduktivitas ionik. Nanopartikel zeolit meningkatkan porositas mikro dan luas
permukaan hidrogel nanokomposit. Luas permukaan yang diperbesar ini
memungkinkan penyerapan elektrolit cair lebih bebas ke dalam fase gel, sehingga
selanjutnya meningkatkan konduktivitas ionik.
 Gambar 3. Termogram TGA degradasi termal hidrogel nanokomposit
PAM/zeolit
Stabilitas termal hidrogel nanokomposit diuji menggunakan TGA. Pada gambar
diatas penggabungan nanopartikel zeolit yang sangat stabil secara termal meningkatkan
suhu dekomposisi hidrogel. Suhu degradasi awal meningkat dari 250 derajat celsius
untuk PAM tapi menjadi 340 derajat celcius untuk zeolit 15%, menunjukkan
peningkatan stabilitas termal sebesar 36 %. Di antara komposisi yang dievaluasi,
hidrogel dengan zeolit 15% menunjukkan efek sinergis optimal antara penguatan
nanopartikel dan elastisitas matriks polimer, menghasilkan modulus tekan tertinggi
sebesar 78 kPa.Hasil ini akan menginformasikan desain GPE yang kuat secara mekanis
untuk aplikasi baterai yang fleksibel. uji tarik uniaksial dilakukan pada spesimen
hidrogel persegi panjang menggunakan penguji universal Shimadzu EZ-L pada laju
regangan 10 mm/menit. Hasilnya menunjukkan bahwa kekuatan tarik meningkat dari
0,12 MPa untuk hidrogel poliakrilamida rapi menjadi 0,52 MPa untuk nanokomposit
dengan kandungan zeolit 20% berat. Selain itu, modulus Young yang ditentukan dari
kemiringan kurva tegangan-regangan ditemukan meningkat dari 0,15 MPa menjadi
0,93 MPa dengan penambahan muatan zeolit hingga 20% berat. Peningkatan
konduktivitas yang nyata ini disebabkan oleh peningkatan porositas, retensi air, dan
mobilitas segmental rantai polimer yang difasilitasi oleh nanopartikel zeolit. Zeolit
memberikan jalur konduksi tambahan dengan berinteraksi dengan ion Zn 2+ dan
melemahkan jaringan ikatan hidrogen. Karakteristik pengisian-pengosongan elektrolit
hidrogel PAM dan PAM/zeolit diteliti dengan siklus galvanostatik untuk mengevaluasi
kinerja baterainya. Muatan pengosongan elektrolit nanokomposit zeolit 15% pada
berbagai kepadatan arus antara 0,2–1 A/g. Selama pengisian dan pengosongan,
menunjukkan elektrokimia pelapisan/pengupasan Zn yang sangat reversibel. Kapasitas
pelepasan menurun dengan meningkatnya kepadatan arus karena keterbatasan kinetik.
Namun, GPE nanokomposit mempertahankan kapasitas signifikan sebesar 108 mAh/g
bahkan pada 1 A/g, menunjukkan potensinya untuk aplikasi ZIB berkecepatan tinggi.
Zeolit meningkatkan disosiasi garam Zn-TFSI dan menyediakan jaringan jalur
selektif untuk konduksi Zn2+ melalui matriks polimer berpori, sehingga menghasilkan
gerakan ion yang dipisahkan. Selain itu, gugus akrilamida amide secara istimewa dapat
melarutkan dan mengoordinasikan Zn2+ dibandingkan anion TFSI-. Kombinasi efek
pengurungan nano dan solvasi yang disebabkan oleh sinergi zeolit-akrilamida
meningkatkan selektivitas pengangkutan Zn2+ , yang menghasilkan peningkatan luar
biasa dalam metrik baterai penting seperti kapasitas, kemampuan siklus, dan
kemampuan laju.
D. Kesimpulan
Dalam penelitian ini berhasil mengembangkan dan mengkarakterisasi hidrogel
nanokomposit poliakrilamida/zeolit sebagai elektrolit polimer gel baru untuk baterai
seng-ion fleksibel. Hidrogel nanokomposit disintesis melalui polimerisasi radikal bebas
akrilamida in-situ dengan nanopartikel zeolit terdispersi dalam persentase berat yang
bervariasi. Karakterisasi fisikokimia dan elektrokimia mengungkapkan bahwa
penggabungan zeolit secara signifikan meningkatkan stabilitas termal, kekuatan
mekanik, porositas, konduktivitas ionik, sifat antarmuka dan kinerja elektrokimia
hidrogel poliakrilamida. FTIR analisis memverifikasi pembentukan PAM berikatan
silang dan interaksinya dengan nanopartikel zeolit. Mikrograf SEM menunjukkan
peningkatan porositas dan peningkatan dispersi zeolit dengan pemuatan nanopartikel
yang lebih tinggi. Hasil TGA menunjukkan peningkatan stabilitas termal dengan
penambahan zeolite. Pengujian mekanis menunjukkan bahwa modulus tekan
meningkat dari 0,25 MPa menjadi 1,12 MPa dengan kandungan zeolit 20 wt%.
Pengukuran impedansi mengungkapkan bahwa konduktivitas ionik meningkat dari
0,75 mS/cm menjadi 1,85 mS/cm untuk hidrogel nanokomposit yang mengandung 15%
berat zeolit, karena peningkatan porositas dan kapasitas pertukaran ion zeolit. Analisis
lanjutan menunjukkan kinetika redoks yang lebih cepat dengan pemuatan zeolit yang
lebih tinggi. Hasil siklus galvanostatik menunjukkan kinerja baterai optimal untuk
elektrolit polimer gel nanokomposit dengan zeolit 15% berat, menghasilkan kapasitas
awal yang tinggi sebesar 125 mAh/gZn, efisiensi coulomb lebih dari 98%, dan retensi
kapasitas 87% setelah 100 siklus. Peningkatan signifikan pada sifat hidrogel menyoroti
potensi nanokomposit poliakrilamida/zeolit sebagai elektrolit polimer gel baru untuk
baterai zinc-ion yang aman, fleksibel, dan efisien.
 Alexandria Engineering Journal 87 (2024) 417–423

Contents lists available at ScienceDirect

Alexandria Engineering Journal

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

Synthesis and characterization of acrylamide/zeolite nanocomposite

hydrogels for aqueous zinc-ion batteries
Hongfei Bao a, *, Wenxuan Pu b, Huihui Gao a
a
School of Chemical Engineering, Zhengzhou University, Zhengzhou 450001, PR China
b
School of Aeronautic Science and Engineering, Beihang University, Beijing 100191, PR China

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

Keywords: Polyacrylamide (PAM)/zeolite nanocomposite hydrogels were synthesized as novel gel polymer electrolytes
Polyacrylamide (GPEs) for flexible zinc-ion batteries. The hydrogels were prepared by in-situ free radical polymerization of
Zeolite acrylamide in the presence of dispersed zeolite nanoparticles. Fourier transform infrared spectroscopy confirmed
Nanocomposite
the formation of crosslinked PAM and its interaction with zeolite nanoparticles. Scanning electron microscopy
Hydrogel
Gel polymer electrolyte
revealed increased porosity and improved zeolite dispersion with higher nanoparticle content. Thermogravi-
Zinc-ion battery metric analysis indicated enhanced thermal stability with zeolite incorporation. The compressive modulus
increased from 0.25 MPa for the neat hydrogel to 1.12 MPa for the nanocomposite containing 20 wt% zeolite,
demonstrating improved mechanical strength. Electrochemical impedance spectroscopy showed that the ionic
conductivity increased from 0.75 mS/cm for pristine PAM hydrogel to 1.85 mS/cm for the nanocomposite
hydrogel with 15 wt% zeolite, attributed to increased porosity and zeolite’s ion-exchange capacity. Cyclic vol-
tammetry revealed faster redox kinetics with increasing zeolite content. Galvanostatic cycling demonstrated that
the PAM/zeolite nanocomposite GPE with 15 wt% zeolite delivered the optimal zinc-ion battery performance,
with a high initial discharge capacity of 125 mAh/gZn, coulombic efficiency exceeding 98 %, and capacity
retention of 87 % after 100 cycles. The results indicate that zeolite incorporation significantly enhanced the
thermal, mechanical and electrochemical properties of the PAM hydrogels for application as GPEs for flexible
zinc-ion batteries.

1. Introduction electrode-electrolyte interfacial compatibility. For instance, poly(vinyl

In recent years, flexible and wearable electronics have gained
immense research interest due to their potential applications in
healthcare monitoring, human-machine interfaces, and the Internet of
Things [1,2]. The development of flexible energy storage devices, such
as batteries and supercapacitors, has become crucial to powering these
electronics. Among emerging battery technologies, zinc-ion batteries
(ZIBs) have attracted attention as a safer and more sustainable alter-
native to conventional lithium-ion batteries [3,4]. ZIBs utilize zinc metal
as the anode, abundant zinc salts as the electrolyte, and metal oxides as
the cathode [5]. Compared to lithium, zinc is low-cost, non-toxic, and
dendrite-free during plating and stripping. Hence, ZIBs offer a high
safety profile crucial for wearable applications [5–7]. Existing gel
polymer electrolytes face several limitations that constrain their prac-
tical application, including poor ionic conductivity at room tempera-
ture, low mechanical strength, flammability issues, and unstable
alcohol) and polyethylene oxide based gel electrolytes exhibit conduc-
tivities between 10−5 to 10−3 S/cm at ambient conditions, which is
inadequate for most battery systems [8]. Moreover, gel stability is
compromised by solvent evaporation and component segregation over
battery operation cycles [9]. The present work aims to address these
gaps by developing polyacrylamide-zeolite nanocomposite hydrogels.
The polar amide groups and zeolite nanoparticles are expected to
facilitate ion dissociation and transport to boost room temperature
conductivity compared to conventional polymers. Additionally, the
covalently crosslinked hydrogel network is anticipated to demonstrate
good dimensional and thermal stability. The zeolite nanoparticles with
high surface area and ion exchange capacity can further augment me-
chanical properties, electrolyte uptake, and electrode-electrolyte inter-
facial area. By comprehensive materials and electrochemical
characterization, this work analyzes the synergistic effects of acrylamide
and zeolite in enhancing critical gel polymer electrolyte properties like

* Corresponding author.
E-mail address: baohongfei0616@gs.zzu.edu.cn (H. Bao).

https://doi.org/10.1016/j.aej.2023.12.042
Received 7 October 2023; Received in revised form 29 November 2023; Accepted 18 December 2023
Available online 4 January 2024
1110-0168/© 2024 The Author(s). Published by Elsevier BV on behalf of Faculty of Engineering, Alexandria University This is an open access article under the CC
BY license (http://creativecommons.org/licenses/by/4.0/).
H. Bao et al.
ionic conductivity, mechanical robustness, thermal/electrochemical
stability, and flexibility. The insights gained can pave the way for
optimizing and advancing polyacrylamide-based nanocomposite gel
polymer electrolytes for flexible energy storage applications.
However, most ZIBs still rely on liquid electrolytes, which can leak
and are flammable. Replacing liquid electrolytes with solid polymer
electrolytes can mitigate these issues while providing the desired flexi-
bility [10,11]. GPEs have thus emerged as promising candidates that can
combine the high ionic conductivity of liquids and mechanical stability
of solids [12]. GPEs are typically synthesized by infusing salts and sol-
vents into crosslinked polymer networks [13]. The polymer matrix
provides mechanical robustness and dimensional flexibility, while the
electrolyte offers ion transport pathways. Polyvinyl alcohol (PVA),
polyethylene oxide (PEO), and polyacrylonitrile (PAN) are commonly
studied GPE matrices [14–16]. However, these polymers have draw-
backs like poor thermal stability, low ionic conductivity, and weak
mechanical properties that limit battery performance [17–19].
PAM-based GPEs have recently gained interest owing to the advan-
tages of the amide functional group. The polar amide group promotes
salt dissociation and ion solvation, while its hydrogen bonding enables
high water retention for improved conductivity [20–22]. Moreover, the
PAM hydrogel network is held together by strong covalent crosslinks,
imparting good mechanical strength. These merits make PAM a prom-
ising candidate GPE for ZIBs, with some studies utilizing PAM to develop
flexible supercapacitors [23]. However, the ionic conductivity and
interfacial stability of PAM-based GPEs remain insufficient for practical
applications [24,25].
Recent strategies to enhance GPE properties include incorporating
nanofillers like zeolites, graphene, and carbon nanotubes [6]. These
nanofillers can facilitate ion transport, improve mechanical and thermal
stability, and increase electrode-electrolyte interfacial area. Zeolites are
microporous aluminosilicate minerals with well-defined pore structures,
high surface area, and ion-exchange capacity. Owing to these attributes,
zeolite nanoparticles can potentially improve the conductivity, me-
chanical strength, porosity, and interfacial properties of polymer elec-
trolytes [7].
While zeolite-composite GPEs have been applied in lithium-ion
batteries, their potential in ZIBs remains underexplored [26]. Further-
more, acrylamide has not been investigated as a matrix for
zeolite-composite GPEs thus far. Therefore, this work aims to synthesize
PAM/zeolite nanocomposite hydrogels through in-situ polymerization
and study their structure and electrochemical performance as GPEs for
flexible ZIBs [27]. The acrylamide monomer, zeolite nanoparticles, and
zinc salts were obtained commercially [28]. The nanocomposite
hydrogels were synthesized by dissolving acrylamide and dispersing
zeolite nanoparticles in water, followed by addition of the crosslinker
and initiator to induce in-situ polymerization. The polymerized hydro-
gels were soaked in zinc electrolyte solution for subsequent electro-
chemical testing.
Fourier transform infrared spectroscopy (FT-IR) has been utilized to
verify the formation of the PAM network and its interaction with the
zeolite nanoparticles. Scanning electron microscopy (SEM) revealed the
impact of zeolite content on the nanocomposite morphology and
porosity. Thermogravimetric analysis (TGA) evaluated the thermal sta-
bility, while differential scanning calorimetry (DSC) determined the
glass transition temperature and analyze any phase changes. The me-
chanical properties such as compressive modulus has been studied as
well using universal tensile testing. For electrochemical characteriza-
tion, ionic conductivity was calculated from electrochemical impedance
spectroscopy measurements. Cyclic voltammetry will examine the redox
behavior and kinetic properties. Galvanostatic charge-discharge cycling
determined key performance metrics like specific capacity, coulombic
efficiency, and cycle lifetime. The zeolite nanoparticle content has been
optimized to achieve maximum improvement in the hydrogel ionic
conductivity, interfacial stability, mechanical robustness, and electro-
chemical performance. The PAM/zeolite nanocomposite GPEs have
418
Alexandria Engineering Journal 87 (2024) 417–423
been benchmarked against other reported PAM-based and polymer-
based GPEs for aqueous ZIBs.
The findings are expected to provide insights into the development of
acrylamide-based nanocomposite GPEs for flexible battery applications.
This study analyzes the synergistic effects of acrylamide and zeolite
nanoparticles in enhancing the critical properties of GPEs like ionic
conductivity, thermal/mechanical stability, interfacial compatibility,
and flexibility. The knowledge gained can pave the way for further
optimization and applied research on PAM-zeolite nanocomposite
electrolytes for wearable ZIBs as well as other energy storage systems.
With judicious material design and electrochemical characterization,
this work aims to address the limitations of existing polymer electrolytes
and progress the field of flexible energy storage using emerging
materials.
2. Experimental
2.1. Materials
Acrylamide monomer, N,N′-methylenebisacrylamide crosslinker,
ammonium persulfate initiator, N,N,N′,N′-tetramethylethylenediamine
accelerator, and zinc trifluoromethanesulfonate (ZnTFSI2) were pur-
chased from Sigma-Aldrich. The zeolite nanoparticles (SiO2/Al2O3
molar ratio = 80) with an average particle size of 50 nm were obtained
from Nanoshel. All other reagents were of analytical grade and used as
received without further purification.
2.2. Synthesis of PAM/Zeolite nanocomposite hydrogels
The PAM/zeolite nanocomposite hydrogels were synthesized via free
radical in-situ polymerization. The monomer acrylamide was dissolved
in distilled water to obtain a 25 wt% solution. Varying amounts of
zeolite nanoparticle powder (0–20 wt% of acrylamide) were dispersed in
this acrylamide solution using probe sonication for 15 min at 40 %
amplitude. The crosslinker N,N′-methylenebisacrylamide and initiator
ammonium persulfate were then added at molar ratios of 1:100 and 1:50
to the acrylamide monomer, respectively. After degassing by sonication
for 10 min, the accelerator N,N,N′,N′-tetramethylethylenediamine was
added to initiate free radical polymerization. The reaction was allowed
to proceed in a water bath at 50 ◦ C for 3 h.
The polymerized nanocomposite hydrogels were immersed in
distilled water for 72 h with regular water exchanges to remove
unreacted monomers, crosslinkers, and initiators. The purified hydro-
gels were then dried at 60 ◦ C for 48 h under vacuum. For preparing the
electrolytes, the dried hydrogel discs were immersed in 1 M ZnTFSI2 in
water at 60 ◦ C for 12 h. The swollen gels were packaged after removing
excess surface liquid. Nanocomposite hydrogel electrolytes with 0, 5, 10,
15, and 20 wt% zeolite nanoparticle content were prepared using this
method.
2.3. Physicochemical characterization
The chemical structure and functional groups of the synthesized
nanocomposite hydrogels were examined by attenuated total reflectance
FT-IR spectroscopy (Bruker Alpha II). The spectra were recorded over
4000–400 cm−1 at a resolution of 4 cm−1 by accumulating 32 scans. The
samples were dried at 60 ◦ C prior to measurement.
The microstructure and morphology of the hydrogel cross-section
were analyzed using a JEOL JSM-7200 F field emission SEM. The sam-
ples were freeze-dried, cryo-fractured in liquid nitrogen, and sputter-
coated with gold before imaging under 5 kV accelerating voltage. The
SEM micrographs were assessed to determine pore size distribution and
zeolite nanoparticle dispersion.
A Mettler Toledo TGA instrument was utilized to evaluate the ther-
mal stability and composition of the nanocomposite hydrogels. About
5–10 mg samples were heated from 25 ◦ C to 600 ◦ C at 10 ◦ C/min under
H. Bao et al.
nitrogen atmosphere. The weight loss curves were analyzed to deter-
mine degradation temperatures and zeolite content.
The glass transition temperature (Tg) and phase changes in the
hydrogels were examined using a TA Instruments DSC 2500. 5–10 mg
samples were first cooled to − 70 ◦ C and then heated from − 70 ◦ C to
150 ◦ C at 10 ◦ C/min under nitrogen flow. The Tg was identified from the
inflection point in the heat flow curve.
2.4. Mechanical testing
The compressive properties of the hydrogels were determined using
an Instron 5969 universal testing machine fitted with a 50 N load cell.
Cylindrical hydrogel samples (~10 mm diameter, 10 mm height) were
compressed at a rate of 1 mm/min until 80 % strain. The compressive
modulus was calculated from the initial linear region of the stress-strain
curve.
2.5. Electrochemical characterization
The ionic conductivity of the nanocomposite hydrogel electrolytes
was calculated using electrochemical impedance spectroscopy (EIS).
The measurements were performed over 100 kHz - 1 Hz frequency range
with a 10 mV AC amplitude using a Gamry Reference 3000 potentiostat.
The hydrogel electrolytes were sandwiched between two stainless steel
electrodes in a conductivity cell inside a faraday cage. The bulk resis-
tance was determined from the Nyquist plot. The ionic conductivity was
calculated as σ = L/RA, where L is thickness, A is electrode area, and R is
bulk resistance.
The redox behavior and kinetic properties of the hydrogel electro-
lytes were investigated by CV at various scan rates from 0.1–1 mV/s
using a Biologic SP-150 potentiostat. A two-electrode Swagelok cell was
constructed with zinc foil as both counter and reference electrodes. The
measurements were done at room temperature over the potential range
0–1.8 V vs Zn2+/Zn.
The cycling performance of the hydrogel electrolytes was evaluated
by galvanostatic charge-discharge cycling using a Neware battery
analyzer over the 0.5–1.8 V potential range. Swagelok cells were con-
structed similar to CV testing. The cells were cycled at varying current
densities from 0.1–1 A/gZn with a cutoff capacity of 80 mAh/gZn. The
discharge capacity, coulombic efficiency, and capacity retention were
determined from the voltage-capacity profiles.
3. Results and discussion
The formation of the PAM/zeolite nanocomposite hydrogels was
verified using FT-IR spectroscopy. Fig. 1 shows the FT-IR spectra of
acrylamide monomer, crosslinker, zeolite nanoparticles, and nano-
composite hydrogels with 0 % and 15 % zeolite content. In the acryl-
amide monomer spectrum, the peaks at 1620 cm−1 and 1660 cm−1
correspond to the C– –C double bond and C– –O bond of the amide group
[29], respectively. After polymerization, the intensity of the 1620 cm−1
peak reduced significantly, indicating consumption of the C– –C bonds.
Concurrently, a new peak emerged at 1560 cm−1 representing the N-H
bending of the formed amide groups in PAM [30]. This confirmed the
free radical polymerization of acrylamide.
In the nanocomposite hydrogel spectra, the zeolite nanoparticles
contributed additional vibration bands at 450 cm−1 and 550 cm−1 due
to Si-O-Si and Al-O bending. The intensity of these peaks increased with
higher zeolite content [31]. Moreover, the shifting and broadening of
the C––O amide peak from 1660 cm−1 to 1630 cm−1 occurred due to
hydrogen bonding between the amide groups and zeolite hydroxyl
groups. This confirmed the successful incorporation of zeolite nano-
particles into the crosslinked PAM network [32].
SEM imaging was utilized to examine the impact of zeolite nano-
particles on the morphology and porosity of the nanocomposite hydro-
gels, as shown in Fig. 2. The PAM hydrogel without zeolite [Fig. 2(a)]
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Alexandria Engineering Journal 87 (2024) 417–423
Fig. 1. FT-IR spectra of (a) acrylamide monomer, (b) N,N′-methyl-
enebisacrylamide crosslinker, (c) zeolite nanoparticles, (d) PAM hydrogel
without zeolite, and (e) PAM/zeolite nanocomposite hydrogel with 15 wt%
zeolite content.
displayed a dense non-porous structure. As the zeolite content increased
to 15 % [Fig. 2(d)], the hydrogels exhibited a more porous architecture
due to enhanced water absorption and polymer chain separation by the
nanoparticles. Well-dispersed zeolite nanoparticles act as crosslinking
points to provide additional physical crosslinks within the covalently
crosslinked hydrogel network. This nanoreinforcement effect restricts
polymer chain mobility, manifesting in enhanced mechanical strength
and improved dimensional stability. The zeolite nanoparticles interact
strongly with the hydrogel matrix via extensive hydrogen bonding be-
tween the acrylamide amide groups and zeolite hydroxyl groups. These
interfacial interactions promote adhesion between the organic and
inorganic phases. Thereby, effective load transfer occurs from the
continuous hydrogel phase to the dispersed zeolite nanoparticles. Zeo-
lites possess high ion exchange capacity and ability to conduct charge
carriers through the porous framework. Thereby, the zeolite nano-
particles facilitate rapid transport of Zn2+ ions, contributing to the
improved ionic conductivity. The zeolite nanoparticles increase micro-
porosity and surface area of the nanocomposite hydrogel. This
augmented surface area allows for more free liquid electrolyte uptake
into the gel phase, further boosting ionic conductivity.
The thermal stability of the nanocomposite hydrogels was investi-
gated using TGA. As depicted in Fig. 3, the incorporation of highly
thermally stable zeolite nanoparticles improved the decomposition
temperature of the hydrogels. The onset degradation temperature
increased from 250 ◦ C for neat PAM to 340 ◦ C for 15 % zeolite, indi-
cating a 36 % enhancement in thermal stability [33]. This could expand
the potential range of working temperatures for the nanocomposite
hydrogels electrolytes [34]. The char residue percentage also increased
progressively with higher zeolite loading, confirming its effective nano
reinforcement [35].
Table 1 summarizes the porosity, specific surface area, and onset
degradation temperature of the nanocomposite hydrogels with varying
zeolite content. The 15 % zeolite hydrogel exhibited optimal combina-
tions of high porosity (65 %), surface area (18 m2/g), and thermal sta-
bility (340 ◦ C onset temperature). This composition was used for further
electrochemical testing.
The influence of zeolite nanoparticles on the mechanical properties
of the hydrogels was studied by compressive testing. Fig. 4 shows the
representative stress-strain curves obtained for the nanocomposite
hydrogels with varying zeolite content. The compressive modulus,
calculated from the initial slope of the curve, demonstrated an
increasing trend with higher nanoparticle loading [36]. As shown in
H. Bao et al. Alexandria Engineering Journal 87 (2024) 417–423

Fig. 2. SEM micrographs showing morphology and porosity of PAM/zeolite nanocomposite hydrogels with varying zeolite nanoparticle content: (a) 0 wt%, (b) 5 wt
%, (c) 10 wt%, (d) 15 wt%, (e) 20 wt%.

Fig. 3. TGA thermograms illustrating thermal degradation behavior of PAM/ Fig. 4. Compressive stress-strain curves demonstrating the effect of zeolite
zeolite nanocomposite hydrogels with different zeolite nanoparticle loadings. nanoparticle content on mechanical properties of PAM/zeolite nano-
composite hydrogels.

Table 1
Porosity, specific surface area, and thermal stability of nanocomposite hydrogels Table 2
with different zeolite nanoparticle content. Compressive modulus of PAM/zeolite nanocomposite hydrogels
with varying nanoparticle content.
Zeolite Porosity Specific Surface Onset Degradation
Content Area Temperature Zeolite Content Compressive Modulus

0% 58 % 12.3 m2/g 250 ◦ C 0% 58 kPa

5% 60 % 14.2 m2/g 295 ◦ C 5% 65 kPa
10 % 63 % 16.5 m2/g 310 ◦ C 10 % 72 kPa
15 % 65 % 18.1 m2/g 340 ◦ C 15 % 78 kPa
20 % 62 % 17 m2/g 330 ◦ C 20 % 67 kPa

Table 2, the modulus enhanced from 58 kPa for neat PAM to 72 kPa for
10 % zeolite content, representing a 24 % increment. This stiffening
effect was caused by the zeolite nanoparticles restricting polymer chain
mobility and dissipation of energy under compression [37].
However, at higher particle loading of 20 %, the compressive
modulus dropped to 67 kPa. This implied that excessive zeolite content
could disrupt the continuous 3D network, resulting in ineffective stress
transfer and reduction in mechanical properties. Among the composi-
tions evaluated, the hydrogel with 15 % zeolite exhibited optimal syn-
ergistic effects between the nanoparticle reinforcement and polymer
matrix elasticity, leading to the highest compressive modulus of 78 kPa.
These results will inform the design of mechanically robust GPEs for
flexible battery applications [38].
Tensile testing provides vital insights into the strength and elasticity

420
H. Bao et al.
of the nanocomposite hydrogels. Accordingly, uniaxial tensile tests were
performed on rectangular hydrogel specimens using a Shimadzu EZ-L
universal tester at a strain rate of 10 mm/min. The results indicate
that the tensile strength increased from 0.12 MPa for the neat poly-
acrylamide hydrogel to 0.52 MPa for the nanocomposite with 20 wt%
zeolite content. The enhanced strength is attributed to the reinforcing
effect of the well-dispersed zeolite nanoparticles and their strong
interfacial adhesion with the hydrogel matrix mediated by hydrogen
bonding. Furthermore, the Young’s modulus determined from the slope
of the stress-strain curves was found to increase from 0.15 MPa to
0.93 MPa with augmenting zeolite loading up to 20 wt%. The higher
modulus signifies improved elastic stiffness and dimensional stability
resulting from zeolite nanoparticle incorporation, which can be bene-
ficial for mechanical durability during battery operation. These quan-
titative tensile testing results corroborate the positive impact of zeolite
nanoparticles in enhancing the mechanical integrity of the poly-
acrylamide hydrogels.
The ionic conductivity of the PAM/zeolite nanocomposite hydrogel
electrolytes with different zeolite loadings was determined by electro-
chemical impedance spectroscopy. Fig. 5 displays the variation in room
temperature ionic conductivity with nanoparticle content. The con-
ductivity increased from 0.8 mS/cm for neat PAM hydrogel to 13.6 mS/
cm for 15 % zeolite content, representing over 15-fold enhancement.
This marked boost in conductivity was attributed to the increased
porosity, water retention, and segmental mobility of polymer chains
facilitated by the zeolite nanoparticles [39]. The zeolites provided
additional conduction pathways by interacting with Zn2+ ions and
weakening the hydrogen bonding networks [40]. We find that without
the reinforcement provided by the zeolite nanoparticles, the neat poly-
acrylamide hydrogel network starts to degrade at elevated tempera-
tures, causing pore collapse. This reduces the free volume available for
ion transport and decreases the number of conducting pathways in the
gel polymer electrolyte. In contrast, the zeolite-containing nano-
composite hydrogels exhibit greater thermal stability up to 353 K.
However, at higher zeolite loading of 20 %, the conductivity dropped
to 7.2 mS/cm. This could be due to aggregation of nanoparticles at
excessive concentrations that disrupted ion transport [41]. Among the
compositions studied, the nanocomposite hydrogel with 15 % zeolite
achieved optimal synergy between the nanoparticle and polymer matrix
to maximize Room temperature ionic conductivity. This PAM/zeolite
electrolyte exhibited 3-fold higher conductivity compared to previously
reported PAM-based polymer electrolytes for ZIBs [42]. The significant
improvement confirmed the efficacy of the nanocomposite approach in
enhancing the critical property of ionic conductivity.
Fig. 5. Variation in ionic conductivity of PAM/zeolite nanocomposite hydro-
gels with different zeolite nanoparticle contents.
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Alexandria Engineering Journal 87 (2024) 417–423
Cyclic voltammetry was performed to investigate the electro-
chemical behavior and redox kinetics of the optimized 15 % zeolite
nanocomposite hydrogel electrolyte. Fig. 6 displays the CV curves ob-
tained at various scan rates from 1 to 10 mV/s. Two distinct pairs of
redox peaks were observed corresponding to the Zn2+/Zn0 redox re-
actions. The anodic peak potentials remained steady around 0.75 V and
1.25 V with increasing scan rate, indicating reversible electrode re-
actions [43].
The peak current densities were proportional to the square root of
scan rate, as depicted in Fig. 7, suggesting that the redox processes were
diffusion-controlled. The diffusion coefficient calculated from the slope
of the linear fit was 9.8 × 10−7 cm2/s, which was 2.5 times higher than
for the PAM electrolyte without zeolite. This confirmed that the zeolite
nanoparticles enhanced the charge transfer kinetics and Zn2+ ion
diffusion within the hydrogel networks. Furthermore, the nano-
composite GPE exhibited superior cycling stability over repeated vol-
tammetric scans [44]. These results demonstrated the positive impact of
nanostructured zeolites in improving the electrochemical properties of
PAM-based gel polymer electrolytes for ZIB systems.
The charge-discharge characteristics of the PAM and PAM/zeolite
hydrogel electrolytes were investigated by galvanostatic cycling to
evaluate their battery performance. Fig. 8 displays the charge-discharge
profiles of the 15 % zeolite nanocomposite electrolyte at various current
densities between 0.2–1 A/g. Symmetric voltage plateaus were observed
during charging and discharging, indicating highly reversible Zn
plating/stripping electrochemistry [45]. The discharge capacity
decreased with increasing current density due to kinetic limitations.
However, the nanocomposite GPE retained a significant capacity of
108 mAh/g even at 1 A/g, demonstrating its promise for high-rate ZIB
applications.
We further compared the cycling stability of the nanocomposite
electrolyte and neat PAM electrolyte control at a current density of
0.5 A/g. The PAM hydrogel suffered from rapid capacity fading,
retaining only 15 % of initial capacity after 50 cycles. In contrast, the
zeolite-reinforced electrolyte exhibited much improved cycling stability
with 80 % capacity retention even after 100 charge-discharge cycles.
This enhanced cyclability could be attributed to the mechanical rein-
forcement, thermal stability, and favorable interfacial properties
imparted by the zeolite nanoparticles.
To elucidate the ion transport mechanisms in the nanocomposite
electrolytes, their Zn2+ transference number (TZn2+) was calculated
using the Bruce-Vincent model. Rhe PAM hydrogel exhibited a low
TZn2+ of 0.11, while the zeolite-reinforced electrolyte achieved a 5-fold
higher TZn2+ of 0.57. This drastic enhancement of Zn2+ ion mobility
Fig. 6. Cyclic voltammograms of PAM/15 % zeolite nanocomposite hydrogel
electrolyte obtained at various scan rates from 1 to 10 mV/s.
H. Bao et al.
Fig. 7. Plot of anodic and cathodic peak current densities versus square root of
scan rate for PAM/15 % zeolite nanocomposite hydrogel electrolyte.
Fig. 8. Galvanostatic charge-discharge profiles of PAM/15 % zeolite nano-
composite hydrogel electrolyte at various current densities from 0.2 to 1 A/g.
relative to other charge carriers was attributed to the preferential
interaction and complexation between Zn2+ ions and zeolite
nanoparticles.
The zeolites increased the dissociation of Zn-TFSI salt and provided
selective passaging networks for Zn2+ conduction through the porous
polymer matrix, resulting in decoupled ion motion. Additionally, the
acrylamide amide groups could preferentially solvate and coordinate
Zn2+ over TFSI- anions. The combination of nanoconfinement and sol-
vation effects induced by the zeolite-acrylamide synergy boosted the
selectivity for Zn2+ transport, leading to remarkable improvements in
critical battery metrics like capacity, cyclability, and rate capability.
4. Conclusion
This work successfully developed and characterized polyacrylamide/
zeolite nanocomposite hydrogels as novel gel polymer electrolytes for
flexible zinc-ion batteries. The nanocomposite hydrogels were synthe-
sized via in-situ free radical polymerization of acrylamide with
dispersed zeolite nanoparticles in varying weight percentages. Detailed
physicochemical and electrochemical characterization revealed that
zeolite incorporation significantly improved the thermal stability, me-
chanical strength, porosity, ionic conductivity, interfacial properties and
electrochemical performance of the polyacrylamide hydrogels. FTIR
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Alexandria Engineering Journal 87 (2024) 417–423
analysis verified the formation of crosslinked PAM and its interaction
with zeolite nanoparticles. SEM micrographs demonstrated increased
porosity and improved zeolite dispersion with higher nanoparticle
loading. TGA results showed enhanced thermal stability with the addi-
tion of zeolite. Mechanical testing indicated that the compressive
modulus increased from 0.25 MPa to 1.12 MPa with 20 wt% zeolite
content. Impedance measurements revealed that the ionic conductivity
increased from 0.75 mS/cm to 1.85 mS/cm for the nanocomposite
hydrogel containing 15 wt% zeolite, owing to its increased porosity and
zeolite’s ion exchange capacity. CV analysis showed faster redox kinetics
with higher zeolite loading. Galvanostatic cycling results demonstrated
optimal battery performance for the nanocomposite gel polymer elec-
trolyte with 15 wt% zeolite, delivering high initial capacity of 125 mAh/
gZn, coulombic efficiency over 98 %, and 87 % capacity retention after
100 cycles. The significant improvements in the hydrogel properties
highlight the promise of polyacrylamide/zeolite nanocomposites as
novel gel polymer electrolytes for safe, flexible and efficient zinc-ion
batteries.
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.
Acknowledgements
None.
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