Review

Functional Hydrogels for Next-Generation

Batteries and Supercapacitors
Youhong Guo,1,2 Jiwoong Bae,1,2 Fei Zhao,1 and Guihua Yu1,*

Functional hydrogels are an attractive material platform for energy-storage Highlights

technologies. Thus, the development of hydrogels with enhanced physico- Functional hydrogels are an emerging
chemical properties (e.g., improved mechanical strength, flexibility, and charge material platform for advanced energy-
storage technologies.
transport) offers new opportunities for next-generation batteries and super-
capacitors. Armed with a deeper understanding of gelation chemistry, Gelation chemistry enables the inte-
gration of hydrogels with a variety of
researchers have made significant strides toward fabricating hydrogels that functional materials to realize desired
are stimulus responsive, self-healing, and highly stretchable. In this short structures and compositions.
review, we highlight how hydrogels have been integrated into batteries and
The diversity of hydrogel materials
supercapacitors and provide exciting examples that demonstrate the versatility allows them to be used as various
of hydrogels; namely, tailorable architectures, conductive nanostructures, 3D components in energy-storage sys-
tems, including electrodes, functional
frameworks, and multifunctionalities. It is anticipated that creative and combi-
binders, and electrolytes.
natorial approaches used in the design of functional hydrogels will continue to
yield materials with great potential in the field of energy storage.

Hydrogels: Emerging Energy-Storage Materials

The rapid development of mobile and portable electronics, from smartphones to electric
vehicles, demands smaller and lighter energy-storage devices with yet higher energy densities
and power outputs. Generally, these devices comprise two electrodes (cathode and anode)
that are separated electronically by a separator and an ionically conducting electrolyte.
Because the electrochemical reactions occur at the electrode/electrolyte interface, tunability
of both ion and electron conductivity is critical [1]. In addition, materials for next-generation
energy-storage devices must also satisfy other key design criteria, including fast charge-carrier
transport, large specific surface area, high chemical stability, and excellent tolerance to
volumetric expansion/contraction [2]. Over the past two decades, advances in nanotechnology
have significantly improved the specific capacity, rate capability, and long-term stability of
energy-storage devices [3]. For example, reducing the feature size of active materials and
combining them with functional frameworks has dramatically improved overall ionic and
electronic conductivity due to shortened diffusion lengths and increased reaction surface area
[4,5]. Nevertheless, current composite electrodes still struggle with relatively weak mechanical
binding, nanoparticle agglomeration, poor component contact, and fracture/delamination
during cycling due to large volume change [6]. As research has expanded in this area, scientists 1
Materials Science and Engineering
have looked beyond traditional nanomaterials (e.g., carbon- or silicon-based nanomaterials, Program and Department of
metallic nanostructures) to improve the performance of these devices. Mechanical Engineering, The
University of Texas at Austin, Austin,
TX 78712, USA
Hydrogels are an emerging material platform for electrochemical devices that have attracted 2
These authors contributed equally to
significant fundamental and applied interest. Hydrogels are 3D networks of crosslinked polymer this work

chains that readily imbibe water and swell without dissolving [7,8]. Due to their highly tunable
mechanical, thermodynamic, and transport properties, hydrogels have significant applications in *Correspondence
diverse areas such as tissue engineering [9,10], drug delivery [11,12], water purification [13–17], ghyu@austin.utexas.edu (G. Yu).

Trends in Chemistry, June 2019, Vol. 1, No. 3 10.1016/j.trechm.2019.03.005 335

© 2019 Elsevier Inc. All rights reserved.
and biomedical engineering [18–22]. Gelation chemistry provides a versatile approach to the
rational design of hydrogels to meet the demanding requirements of electrodes, conductive
binders, and electrolytes in energy-storage devices through building block tailoring, topological
structure adjustment [23], and functional additive integration (Figure 1). With the remarkable
tunability of each element, hydrogels are capable of providing high ionic conductivity, electronic
conductivity [24], electrochemical activity [25], structural flexibility [26], and electrolyte permeability
[2] to improve energy-storage device performance. In this minireview, we discuss the unique ways
in which hydrogels have been employed as key materials in energy-storage devices, such as alkali-
metal batteries and supercapacitors. Recent progress on hydrogel-based tunable architectures,
conductive nanostructures, 3D frameworks, and multifunctional materials is summarized with
examples to reveal their vital role in next-generation energy-storage devices.

Hydrogel Synthesis and Gelation Chemistry

Hydrogels are synthesized from monomers and/or polymers through the formation of cross-
linked networks in an aqueous medium via chemical or physical interactions including physical
entanglement, electrostatic interactions, metal coordination, or covalent crosslinking

Polymer interacƟons FuncƟonal groups

Crosslinker Aqueous electrolytes

Polymer/monomer FuncƟonal materials

Transport enhancement SƟmulus responsive

Stable molecular framework self-healing,
Volume accommodaƟon 3D interconnected network flexible/stretchable
organic–inorganic hybrid

Energy storage devices

(Electrode, conducƟve binder, electrolyte)

Figure 1. Tunable Elements in Gelation Chemistry Beneficial for Energy-Storage Devices. Key elements
include polymer-chain chemistry, crosslinking type and density, polymer interactions with polymer/ions/electrolyte,
aqueous electrolytes, and added functional materials.

336 Trends in Chemistry, June 2019, Vol. 1, No. 3

 (A) (C)
Crosslinking
in aqueous soluƟon CarbonizaƟon

Polymer/monomer and Hydrogel with 3D conducƟve support

aqueous soluƟon GelaƟon Heat treatment Carbon framework for acƟve materials
charge carriers

(B)

In situ Sintering
cross-linking

Polymer/monomer and FuncƟonal materials 3D organic–inorganic

funcƟonal materials Oxide framework
embedded in hydrogel hybrid materials

Figure 2. Schematic Illustration of Synthesis and Applications of Hydrogels in Energy Storage. (A) Crosslinking
hydrogel in aqueous solution where salts for charge carrier are dissolved. (B) Crosslinking hydrogel in the presence of
functional materials that can be coated by hydrogel through in situ crosslinking. (C) Nanostructured hydrogel-derived
inorganic frameworks by carbonization (top) and sintering (bottom).

(Figure 2A) [27]. The primary factors affecting hydrogel gelation include monomer/polymer
functional-group and backbone chemistry, crosslinking-agent chemistry and density, func-
tional additives, and synthesis environment (e.g., temperature, pH, ionic strength) [28,29].
Typically, hydrogels are synthesized in an aqueous electrolyte that can be an acid, alkaline, or
neutral solution, where desired salts [e.g., sulfuric acid (H2SO4), potassium hydroxide (KOH),
sodium sulfate (Na2SO4) for supercapacitors] are dissolved in water as the solvent [24]. The
resulting gels contain highly polar functional groups (e.g., -OH, -COOH, -COO
, -CONH2) that
strongly interact with water molecules to promote aqueous solubility [18]. The degree of
swelling is determined largely by the balance between the increased entropy due to mixing
the polymer with a solution and the elastic retractive force resulting from the reduction in the
number of possible chain conformations as the polymer network swells [30]. In the case of ionic
gels containing charged functional groups, electrostatic interactions also contribute signifi-
cantly to gel swelling (i.e., Donnan equilibrium). The highly tailorable synthesis and the abun-
dance of potential postsynthetic modifications of hydrogels enables a variety of applications in
energy-storage devices with favorable properties including electrochemical stability, ionic/
electronic conductivity, and mechanical strength.

In addition to ionically conductive hydrogels that are often used as electrolytes due to their high
ionic conductivity stemming from high water content, electronically conductive hydrogels with
hierarchical pores enable mixed ionic and electronic conductors (MIECs). Electronically con-
ducting polymers are conjugated molecules with backbone chains containing alternating single
and double bonds. Typically, undoped conjugated polymers are semiconductors or insulators
with very low conductivities (from 10
5 to 10
10 S cm
1). However, doping (even at very low
levels) enables significantly increased electronic conductivities (from 1 to 10
4 S cm
1) [31].
Figure 2B shows an exemplary synthesis process for a conductive hydrogel electrode for
batteries where electronically conductive polymers are dissolved in an aqueous electrolyte
together with functional nanomaterials (active electrode particles). Following hydrogel synthe-
sis, the functional nanomaterials are embedded in the crosslinked hydrogels. Depending on the
application, the hydrogel is then dried and swollen by a desired liquid electrolyte (e.g., organic
electrolyte). In these conductive hydrogels, electronically conductive polymer chains are cross-
linked to enable a continuous electron transport pathway. Meanwhile, the hierarchical

Trends in Chemistry, June 2019, Vol. 1, No. 3 337

hydrophilic pores facilitate ion diffusion and liquid transport. Therefore, the functional nano-
particles embedded in the hydrogel matrix have access to both electrons (e
) and ions (A+) that
are highly favorable for redox reactions in most of the electrodes for energy-storage systems.

Hydrogels can also be used as precursors or templates. Owing to their hierarchically porous
structure, hydrogels are excellent templates for the fabrication of 3D interconnected inorganic
frameworks by pyrolysis, thermal annealing, or other thermal methods. Figure 2C provides two
representative examples utilizing hydrogels as a precursor. Hydrophilic polymer chains are
crosslinked in aqueous solution along with nanoparticles or precursors, such as active electrode
precursors [e.g., lithium sulfate (Li2SO4)] [32,33] or metal-oxide salts {e.g., lithium nitrate (LiNO3),
lanthanum(III) nitrate hexahydrate [La(NO3)3]6H2O} [34,35]. In the case of carbon frameworks, a
crosslinked hydrogel is heat treated under an inert or a reducing atmosphere such as argon (Ar),
nitrogen (N2), or Ar/N2 + hydrogen (H2) [32,33]. Since the polymers are a carbon source, heat
treatment of the hydrogel in reducing environment results in a 3D hierarchically porous carbon
framework where functional nanomaterials are embedded as shown at the top of Figure 2C
[32,33]. 3D porous metal-oxide or ceramic frameworks can be derived via heat treatment of
hydrogels in an oxidizing atmosphere [34,35]. During hydrogel synthesis, metal ions can be
uniformly mixed and stabilized within a covalently crosslinked polymer network [36]. The hydrogels
containing precursors are then typically dried and heat treated in an oxidizing atmosphere (often in
ambient air) as shown at the bottom of Figure 2C. The oxide framework can be made with a
conventional solid-state electrolyte as well as electrode materials for batteries, which can be
synthesized in an oxidizing atmosphere [e.g., lithium cobalt oxide (LiCoO2)] or in a reducing
atmosphere [e.g., lithium iron phosphate (LiFePO4)] [34,35,37].

Fabrication methods are not limited to the examples introduced in this section. One can modify
the aforementioned synthetic processes to produce a variety of hydrogels for energy-storage
applications, such as incorporating block copolymers [38], forming interpenetrating polymer
networks [39], changing the level of doping or concentration of charge carriers [40,41], or
adjusting crosslinking density [42]. Overall, gelation chemistry and various synthetic
approaches provide significant opportunity to rationally design hydrogels to meet the demand-
ing requirements of energy-storage devices.

Hydrogels in Batteries and Supercapacitors

Hydrogels as Electrolytes
A primary application for hydrogels in energy-storage devices is as the ionically conducting electro-
lyte. Due to their high ionic conductivity and dimensional stability, various energy-storage devices
have utilized hydrogel electrolytes, including supercapacitors and batteries. For example, Wang and
colleagues reported a chemically crosslinked polyvinyl alcohol (PVA) hydrogel electrolyte for super-
capacitors [43]. Prior to hydrogel-based electrolytes, commercial separators [e.g., polyethylene (PE),
polypropylene (PP)] suffered from limited ionic conductivity [44]. Here, however, the PVA hydrogel
electrolyte exhibited a high ionic conductivity of 8.2  10
2 S cm
1, close to that of a typical aqueous
H2SO4 electrolyte (10
1 S cm
1) (Figure 3A) [43]. Recently, hydrogel electrolytes were also
employed in batteries [45,46]. For example, Li and colleagues reported a hierarchical polymer
electrolyte fabricated by grafting polyacrylamide (PAM) onto gelatin chains that filled in a polyacrylo-
nitrile (PAN) nanofiber matrix (Figure 3B) [45]. The resulting ionic conductivity (1.76  10
2 S cm
1) is
significantly greater than those of conventional zinc-ion gel electrolytes (10
3  10
8 S cm
1) and
close to those of liquid electrolytes (10
1  10
2 S cm
1) [47,48]. In addition to high ionic conduc-
tivity, hydrogels exhibit highly tunable mechanical properties (e.g., elasticity, flexibility) that can
improve the performance of energy-storage devices. Lopez and colleagues fabricated highly elastic
hydrogel electrolytes via a double-network design [46]. In this design, covalent crosslinks provide

338 Trends in Chemistry, June 2019, Vol. 1, No. 3

 (A) (B)
(S1) PVA-H2SO4 (S2) PVA-H2SO4 GelaƟn K2S2O6
PAN membrane
mixed soluƟon chemical hydrogel
HPE
SƟrred at 80°C SƟrred at 40°C
Heated at 60°C
Chemical
crosslinking

: GelaƟn chain : Acrylamide : PAM chain : PAN fiber

(C) (D)

CaƟonic monomer

Anionic monomer

(E) (F) (H)

(G) 200
C·LFP control
C·LFP/C·PPy
0.2 C
Discharge capacity (mAh/g)

160 0.5C 0.5C

1C
2C Polypyrrole
120
5C
10 C
80 20 C
30 C
CuPcTs
40

0 TetrafuncƟonal groups
0 10 20 30 40 50
Cycle

Figure 3. Ionically or Electronically Conductive Hydrogels in Energy Storage. (A) Crosslinked polyvinyl alcohol (PVA)-H2SO4 (sulfuric acid) hydrogel electrolyte.
Reproduced, with permission, from [43]. (B) Synthesis process for the hierarchical polymer electrolyte. Reproduced, with permission, from [45]. (C) Structure of
polyampholyte hydrogel fabricated by cationic and anionic monomers. Reproduced, with permission, from [41]. (D) Schematic illustration of the zwitterionic hydrogel
electrolyte. Reproduced, with permission, from [50]. (E) Schematic illustration of mixed ionic and electronic conduction in nanostructured hydrogels. (F) Scanning
transmission electron microscopy (STEM) images of nanostructured hydrogel with active particles. (G) Rate performance of lithium-ion batteries with the conventional
cathode (C-LFP control) and nanostructured hydrogel cathode (C-LFP/C-PPy). Reproduced, with permission, from [52]. (H) The molecular structure of polypyrrole (PPy)
crosslinked by CuPcTs (copper phthalocyanine-3,40 ,400 ,4000 -tetra sulfonic acid tetrasodium salt). Reproduced, with permission, from [42]. Abbreviations: HPE,
hierarchical polymer electrolyte; PAM, polyacrylamide; PAN, polyacrylonitrile.

Trends in Chemistry, June 2019, Vol. 1, No. 3 339

elasticity while hydrogen bonds between amide groups can dissipate the stress generated from
stretching or bending. The resulting solid polymer electrolyte shows a high ionic conductivity that is
several orders higher than conventional lithium-ion polymer electrolytes with a high resilience that is
comparable with that of Kevlar-based polymer electrolytes [49].

To enhance hydrogel ionic conductivity further, ionizable functional groups are often introduced
into the polymer network, typically referred to as polyelectrolyte (either positively or negatively
charged), polyampholyte (both positively and negatively charged), or zwitterionic (with mono-
mers possessing both positively and negatively charged groups) networks. Figure 3C shows a
cartoon structure of polyampholyte hydrogel that was polymerized by both cationic and anionic
monomers creating a network containing oppositely charged functional groups [41]. Due to
electrostatic and hydrogen-bonding interactions, the polyampholyte hydrogel exhibits self-
healing and mechanical stability. In addition, the existing counter ions (along with high water
retention) in charged polymers enable a high conductivity. Zwitterions have also been used to
synthesize a hydrogel electrolyte where the polymers have separate positively and negatively
charged groups (Figure 3D) [50].

Hydrogels as Electrodes and Binders

To be suitable for electrodes or binders in batteries and supercapacitors, both ionic and
electronic conductivity are required to facilitate the transport of all species involved in the
electrochemical reactions. To achieve this end, hydrogels may be synthesized via crosslinking
conductive monomers/polymers, such that electron transport occurs along the conductive
polymer chains while ions are conducted through the liquid electrolyte within the hydrogel
meshes [51]. Shi and colleagues reported a conductive hydrogel binder for lithium-ion batteries
[52]. As shown in Figure 3E, the 3D hierarchical structure of the conductive hydrogel network
provides continuous electron conduction pathways through the interconnected conductive
polymer chains. Meanwhile, the water- and ion-rich meshes of the hydrogel facilitate the
diffusion of ions (Figure 3F). Conductive hydrogel binders can perform as both ionic and
electronic conductors, improving the rate performance of lithium-ion batteries up to 30C (i.e.,
30 times of discharge in 1 h) (Figure 3G). In addition to improved charge transport, the 3D
porous nanostructure and improved elasticity of the hydrogel binder can accommodate volume
changes of active materials during charge/discharge exhibiting long-term cycling stability.

Through rational selection of crosslinking agent type and density, unique morphologies and
electrochemical properties can be obtained. Wang and coworkers reported nanostructured
conductive hydrogels with polypyrrole (PPy) as the conductive polymer and a disk-shaped
liquid crystal [i.e., copper phthalocyanine-3,40 ,400 ,4000 -tetra sulfonic acid tetrasodium salt
(CuPcTs)] that functions as a dopant and crosslinking agent (Figure 3H) [42]. Due to the steric
and electrostatic interaction between PPy and CuPcTs, PPy favorably forms 1D chains.
However, these 1D chains are crosslinked by CuPcTs (CuPcTs-doped PPy), further forming
a 3D interconnected hydrogel. CuPcTs-doped PPy shows more than two orders of magnitude
enhancement in conductivity (7.8 S cm
1) compared with that of pure PPy (7  10
2 S cm
1).
The dopant CuPcTs not only crosslinks 1D PPy chains but also enhances interchain charge
transport between 1D chains leading to significantly enhanced conductivity.

Although the high elasticity and mechanical strength of hydrogels have enabled their use in
flexible devices, the mechanical and electrochemical properties often conflict with each other.
Regarding the electrochemical performance, the hydrogel-based materials demonstrated
limited better performance compared with conventional materials. To further improve hydro-
gel-based materials, deep understanding of phase structure is required. In particular, the

340 Trends in Chemistry, June 2019, Vol. 1, No. 3

properties of MIEC hydrogels are complicated to evaluate since the ionic and electronic
conduction and the electrochemical properties in the hydrogel can be studied only empirically
by measuring cell performance. For future studies, advanced characterization is required to
elucidate the exact mechanism of ionic and electronic conduction in the polymer, liquid, or
polymer–liquid interphase.

Hydrogels as Templates for 3D Inorganic Frameworks

Inorganic nanomaterials (e.g., conductive carbon or oxide nanoparticles) have been widely
used in energy-storage devices, especially as composite electrode materials. However, typical
mixing of nanoparticles with base materials such as polymers often results in agglomeration of
nanoparticles and, consequently, decreased surface area and connectivity. To address this
issue, previous studies modified the fabrication process of the composite materials, such as
electric-field alignment of nanoparticles [53], the ice-templating method [54], or using high-
aspect-ratio (1D or 2D) nanofillers [55]. Despite these improvements, the most effective way is
to form a 3D network of the desired materials. Hydrogels have a 3D interconnected nano/
microstructure with water imbibed within the hydrogel matrix that can dissolve precursors.
Recent studies show that various 3D inorganic frameworks can be derived from the heat
treatment of a mixture of a hydrogel with functional materials or precursors; this demonstrates
significant advantages over conventional discrete particles of lower dimension.

Electrode materials have been prepared by heat treatment of a hydrogel to form uniformly
distributed active materials in the carbon framework. For the cathode material of a lithium-sulfur
(Li-S) battery, Zhang and colleagues fabricated an N,P-codoped carbon framework from a
hydrogel [32]. In their work, prefabricated Li2SO4 nanoparticles with carbon (Li2SO4/C) were
mixed with phytic acid-doped polyaniline (P-PANI). After in situ polymerization, the hydrogel was
coated on a substrate followed by heat treatment in a reducing atmosphere (Figure 4A). As a result
of the carbothermic reduction of Li2SO4 and carbonization of P-PANI, a hierarchically porous
carbon framework was obtained where Li2S nanoparticles are embedded; the 3D hierarchical
structure enables exceptional ion and electron transport (Figure 4B). In addition to providing a
carbon source, P-PANI also functions as source for N and P dopants. Importantly, N,P doping can
improve the electrochemical reaction kinetics and reduce undesired dissolution of polysulfides
through the strong interaction between S and P. For the anode material of a lithium-ion battery, Shi
and colleagues developed Sn-Fe alloys in a 3D carbon framework (Sn-Fe@C framework) from a
double-network nanostructured hydrogel [33]. Figure 4C shows the fabrication process that
includes metal salts dissolved in the hydrogel, freeze drying to form an aerogel, and pyrolysis at
high temperature. The ternary product of the Sn, Fe, and C elements is well distributed over each
1D nanodendrite building unit in the entire 3D hierarchical Sn-Fe@C framework, leading to
enhanced cycling stability, reversible capacity, and rate capability (Figure 4D).

Metal-oxide frameworks have also been prepared for several energy-storage devices. Bae
and coworkers developed a facile method to fabricate 3D Li0.35La0.55TiO3 (LLTO) ceramic
frameworks for composite polymer electrolytes [34]. Conventional particle-based compos-
ite polymer electrolytes suffer from agglomeration of particles that leads to low ionic
conductivity. Here, however, the 3D interconnected ceramic framework formed a continu-
ous ion-conducting pathway without agglomeration of particles (Figure 4E). The 3D hydro-
gel framework containing evenly distributed metal-salts precursors resulted in LLTO
nanoframeworks with an interconnected structure (left image of Figure 4F). The composite
electrolyte with 3D framework shows a bicontinuous structure of LLTO and poly(ethylene
oxide) (PEO) leading to high lithium-ion conductivity ( 10
4 S cm
1 at room temperature)
(right image of Figure 4F). Hasegawa and colleagues applied inorganic-organic hybrid gels

Trends in Chemistry, June 2019, Vol. 1, No. 3 341

 (A) (B)

900°C

Li2SO4/C/P-PANI Li2S/N,P-C

(C) (D)

Freeze drying

Sn–Fe/C–G Sn–Fe/C–G
double-network hydrogel double-network aerogel

Pyrolysis
Sn–Fe alloy

Sn–Fe@C
framework electrode

(E) (F)

ConƟnuous
interphase

ConducƟon via interphase μ μ

ConducƟon via PEO matrix

Figure 4. Hydrogels as a Template or Precursor for 3D Inorganic Frameworks. (A) Synthesis process and (B) Scanning electron microscope (SEM) image of
Li2S/N,P-C framework for electrode of Li-S battery. Reproduced, with permission, from [32]. (C) Synthesis process and (D) Scanning transmission electron microscopy
(STEM) image with elemental mapping of the Sn-Fe@C framework for an electrode of the lithium-ion battery. Reproduced, with permission, from [33]. (E) Conduction
mechanism in composite polymer electrolyte with a 3D ceramic framework. (F) SEM images of the 3D ceramic framework (left) and its composite polymer electrolyte with
poly(ethylene oxide) (PEO) (right) for the electrolyte of a lithium-ion battery. Reproduced, with permission, from [34]. Abbreviations: LLTO, Li0.35La0.55TiO3; PANI, phytic
acid-doped polyaniline.

as a precursor for 3D electrode fabrication [37]. A commonly used cathode material in

lithium-ion batteries, LiFePO4, has low lithium ion diffusion and poor electronic conductivity
that prevents the utilization of active material and impairs rate performance. In their work,
the monolithic LiFePO4/carbon composite was fabricated by applying two different types of
polymers, PEO and poly(vinylpyrrolidone) (PVP), where PEO works as a phase separation
while PVP plays a role as an N-doped carbon source. The well-defined microporous

342 Trends in Chemistry, June 2019, Vol. 1, No. 3

structure and uniform mixing of LiFePO4 and carbon provide high specific surface area as
well as efficient mass transport and electron conduction.

Functional Hydrogels in Energy-Storage Electronics

Hydrogels have incredible tunability through modification of functional groups and the incorpo-
ration of functional materials [27,56,57]. Thus, hydrogels can be synthesized that possess
important features including stimulus responsiveness [58–61], self-healing [62,63], and extreme
flexibility [64–68] and stretchability [69,70]. Over the past few years, functional hydrogels have
been investigated to address the failure modes of energy-storage devices (e.g., lithium-ion
batteries, supercapacitors) that remain prevalent [71–73]. Recently, thermal runaway associated
with these devices was addressed using a thermoresponsive polymer with a sol–gel or phase
transition at the relevant temperature [74–78]. For example, Yu and colleagues introduced a new
electrolyte based on a thermoplastic elastomer with a reversible sol–gel transition [79]. This
thermoresponsive Pluronic-based electrolyte inhibits ion transport by transitioning to a gel above
a tunable operating temperature, triggering shutdown to protect the device (Figure 5A). The
transition temperature can be adjusted by tuning the concentration and average molecular weight
of the polymer to meet specific device requirements. Cyclic voltammetry measurements of
supercapacitors using this electrolyte demonstrate high and stable capacitance with excellent
reversibility, suggesting its practicality in lithium-ion batteries and fuel cells.

Similar to the above sol–gel transition mechanism, Bao and coworkers reported a reversible
thermoresponsive polymer that could incorporate into electrodes to prevent thermal runaway [80].
When the battery is overheated, the current collector (coated with a thin thermoresponsive
polymer) increases resistance by separating conductive particles via the expansion of polymer
matrix (Figure 5B). On cooling, the battery resumes normal function as the polymer shrinks to
recover conductive pathways. The designs incorporated with polymer gels provide a reliable
strategy to achieve safer, improved performance. Conductive, interpenetrating network hydrogels
that are extremely sensitive to changes in temperature were developed by Yu and coworkers [81].
This interpenetrating network inhibited the aggregation of polymer particles and provides contin-
uous conduction pathways for electron transport, thus achieving high electrical conductivity.

In addition to stimulus responsiveness, self-healing hydrogels are also attractive for electrochemical
energy-storage devices [82–86]. A hybrid hydrogel comprising metal-ligand supramolecules and
PPy was reported with efficient self-healing behavior at room temperature without any external
stimulus [87]. Figure 5C demonstrates that the combination of dynamic intermolecular interaction
and coordination can drive the reassembly of supramolecules to self-heal cracks. Here, the lightbulb
can light again when the circuit is reestablished, owing to the dynamic assembly or disassembly of
the supramolecular matrix. Another work from Zhi and coworkers reported an electrolyte comprising
polyacrylic acid dual crosslinked by hydrogen bonding and vinyl hybrid silica nanoparticles (VSNPs-
PAA), which also exhibits self-healing properties [88]. This self-healing feature is due to the formation
of abundant reversible intermolecular hydrogen bond crosslinks. The broken hydrogen bonds
recombine through the coordination of carboxyl groups on the PAA polymer chains. A facile
supercapacitor made from this new hydrogel electrolyte provides a hint for future portable and
wearable energy-storage devices. Overall, self-healing of hydrogel potentially enhances stability,
increases lifetime, and reduces the safety hazards associated with energy-storage devices [63,88].

To enable next-generation wearable and portable energy-storage electronics, significant research

effort has been expended toward the development of scalable methods of fabricating self-
standing and flexible electrode-based hydrogels [1,25,89–91]. A recent research study con-
ducted by Yu and colleagues reported self-standing conductive polymer/graphene hydrogels for

Trends in Chemistry, June 2019, Vol. 1, No. 3 343

 (A)

PPO segment PEO segment Electrode segment Ion

(B) TRPS safe LIB

Polymer GrNi

Cooling

OverheaƟng
Recovery of Loss of percolaƟon pathway
percolaƟon pathway

(C) Intermolecular
interacƟon c

(D) (E)

(See figure legend on the bottom of the next page.)

344 Trends in Chemistry, June 2019, Vol. 1, No. 3

 dly
Pain

rien
tabl

Biof
e

Ela
sƟ fe
c r-sa
ity pe
Su
Transparent

Customized structural energy storage Transparent aƩachable energy storage

Digital health analyzer ArƟficial organ

Mobile appliance

Weavable

Ultrathin and flexible Wearable devices

Figure 6. Prospective Hydrogels for Future Energy-Storage Applications.

fiber-shaped supercapacitors [92]. The 3D hybrid hydrogel-based supercapacitor exhibits excel-

lent mechanical flexibility and robustness due to the strong intermolecular interaction between the
PANI, phytic acid, and graphene. Figure 5D shows that the fiber-shaped hydrogel can be knotted,
twisted randomly without fracture, and maintain its decent current density, making it possible to
construct integrated energy-storage yarns. Another study by Shi and colleagues reported a highly
conductive poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) hydrogel
(880 S m
1) with excellent performance, stability, and flexibility (Figure 5E) [93]. Prepared by

Figure 5. Smart Hydrogels for Energy-Storage Devices. (A) Schematic illustration of a thermally responsive gel electrolyte, showing a reversible sol–gel transition
that inhibits ion conduction at high temperature. Reproduced, with permission, from [79]. (B) Thermal switching mechanism of the thermoresponsive polymer layer for
current collectors in a battery before and after heating. Reproduced, with permission, from [80]. (C) Schematic illustration of mechanism for self-healing behavior of
supramolecular gels. Reproduced, with permission, from [87]. (D) Scanning electron microscope (SEM) images of the polyaniline/graphene oxide (PANI/GO) fiber-
based supercapacitor with strong mechanical properties. Reproduced, with permission, from [92]. (E) Digital pictures of poly(3,4-ethylenedioxythiophene) polystyrene
sulfonate (PEDOT:PSS) hydrogels; bars, 1 cm. Reproduced, with permission, from [93]. Abbreviations: GrNi, graphene-coated nano-spiky Ni particles; LIB, lithium ion
battery; PEO, poly(ethylene oxide); PPO, polypropylene oxide; TRPS, thermoresponsive polymer switching.

Trends in Chemistry, June 2019, Vol. 1, No. 3 345

partially removing the PSS component using thermal treatment in sulfuric acid, the PEDOT Outstanding Questions
hydrogel can be fabricated into any arbitrary shape or size. Super-stretchable and compressible Do any approaches from gelation
hydrogel supercapacitors were also developed by Huang and colleagues. Here, PAM hydrogel chemistry exist to combine electrodes
and an electrolyte together for a safety-
networks crosslinked by vinyl hybrid silica nanoparticles were able to stretch up to an unprec-
guaranteed, all-in-one device?
edented 1000% strain with enhanced performance [94].
How can we resolve the limitations set
Concluding Remarks by using hydrogels as aqueous elec-
Functional hydrogels are an emerging class of materials that exhibit several unique advantages trolytes, such as the decomposition of
water?
over conventional nanomaterials. Importantly, hydrogels exhibit well-formed interconnected
networks with enhanced connectivity, high surface area, and mechanical strength. Due to How can the drawback of a small
strong interaction with water molecules, hydrogels also have high retention capacity for range of operational temperatures for
aqueous electrolytes, often affording high ionic conductivity. Besides facilitating charge/mass hydrogel-based energy-storage devi-
transport, interconnected polymers with hierarchical pores can also accommodate large ces be overcome?

volume changes of the active material in the electrode during the charge/discharge process.
What are the optimal strategies for
It is also possible for hydrogels to be used as templates for the fabrication of a versatile suite of simultaneous increase of the ionic
inorganic frameworks. Additionally, an abundant selection of polymers, dopants, and functional and electronic conductivity of hydro-
components can be incorporated into hydrogels to satisfy a wide variety of design needs. gel-based materials?

Can hydrogel materials serve as print-

Several key challenges remain for hydrogel materials to be optimized for energy-storage devices
able batteries for automobiles?
(see Outstanding Questions). While hydrogels function as aqueous electrolytes, the electrochemi-
cal reaction is limited since the stable voltage window is constrained. In addition, the use of water
as a solvent inhibits a wide range of operational temperatures. Improvement of electrochemical
properties along with higher mechanical stability remains to be fully investigated. Fundamental
understanding of hydrogels is also required, including surface-chemistry effects on charge
transport and electrochemical kinetics at the hybrid interface of polymer, electrolyte, and inorganic
materials. With the development of novel gelation strategies and advanced functional elements,
we anticipate that hydrogel-based materials will play an even greater role in energy-storage
applications in the near future (Figure 6). The combination of these properties (Figure 6) can provide
further opportunities for portable, wearable, and clinical innovations. Ultimately, advances in
hydrogel materials should aim to achieve optimal designs to solve the performance, cost, and
ecofriendliness challenges in next-generation energy-storage technologies.

Acknowledgments
G.Y. acknowledges the funding support from the Center for Mesoscale Transport Properties, an Energy Frontier Research Center
supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award No. DE-SC0012673.

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