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Advanced Materials for Use in Soft Self-Healing Devices

Tan-Phat Huynh,* Prashant Sonar, and Hossam Haick*

acting as energy generators and/or weight

Devices integrated with self-healing ability can benefit from long-term use as trackers,[6,7] contact lenses that measure
well as enhanced reliability, maintenance and durability. This progress report intraocular pressure,[8] amongst many
reviews the developments in the field of self-healing polymers/composites others.
and wearable devices thereof. One part of the progress report presents and Wearable devices should preferably be
inexpensive, flexible, lightweight, easy-
discusses several aspects of the self-healing materials chemistry (from non-
to-make, biocompatible and versatile
covalent to reversible covalent-based mechanisms), as well as the required sensing systems.[1,9–11] Much attention is
main approaches used for functionalizing the composites to enhance their being focused on how to endow wearable
electrical conductivity, magnetic, dielectric, electroactive and/or photoactive devices with as many new functions as
properties. The second and complementary part of the progress report links possible.[1,3,9,10,12–14] Attention is also being
the self-healing materials with partially or fully self-healing device technolo- paid to their durability and flexibility,
because these devices may break down
gies, including wearable sensors, supercapacitors, solar cells and fabrics.
due to mechanical fracture during defor-
Some of the strong and weak points in the development of each self-healing mation with time or accidental damage
device are clearly highlighted and criticized, respectively. Several ideas in their practical applications. Wearable
regarding further improvement of soft self-healing devices are proposed. devices that can correct the detrimental
effects of scratching and/or mechanical
damage and restore the mechanical/elec-
trical/chemical properties are therefore of particular interest for
1. Introduction
real-world applications. This property being referred to as the
The next generation of “smart living” is based on advanced “self-healing” capability.
applications of smart wearable devices,[1–3] e.g., from the Apple Technically, a self-healing wearable device is a merger of
Watch to Google Glass and Microsoft’s HoloLens. Such wear- two fast developing research areas, i.e., self-healing materials
able devices are becoming an inseparable part of our lives and and wearable devices. Self-healing materials have recently
hail a new revolution in flexible and printed electronics. One developed as a branch of smart materials, designed to self-heal
could imagine, for instance, how uncomfortable it is to go mostly mechanical damage without using external stimuli.[15,16]
out of house without a Bluetooth headset, Apple watch, smart Therefore, one should differentiate between materials that are
phone or a similar device. More and more wearable devices healing with the help of electrical[17] or thermal[18] trigger and
are being developed to improve the convenience and security self-healing at ambient conditions without the need for any
of our lives; wearable sensors on earrings (Ear-O-Smart) for trigger or external stimuli.[19] Largely due to several outstanding
tracking body temperature or replacing a Bluetooth headset, a organic and material scientists, a range of self-healing materials
shirt that monitors the body’s physiology,[4,5] devices on shoes have been developed and exploited in different research areas,
because of their flexibility, biocompatibility and ease of func-
tionalization, see ref. [20–24]. This Progress Report provides
Dr. T.-P. Huynh
Department of Chemical Engineering an update on the current status of advanced materials for use
Technion – Israel Institute of Technology in soft self-healing devices, with the main focus on wearable
Haifa 3200003, Israel devices (Figure 1). It introduces the first self-healing materials,
E-mail: tanphathuynh84@gmail.com including the main composites and their healing mechanisms.
Dr. T.-P. Huynh It then presents and discusses recent advances in devices
Department of Chemistry and iNANO
Aarhus University having self-healing characteristics, such as chemical sensors
Gustav Wieds Vej 14, 8000 Aarhus C, Denmark and e-skins – important components for medical and environ-
Prof. P. Sonar mental control. Self-healing supercapacitors, batteries and solar
School of Chemistry, Physics and Mechanical Engineering cells as cost-effective and convenience-effective devices are also
Queensland University of Technology (QUT) demonstrated and discussed.
2 George Street, Brisbane QLD-4001, Australia
Prof. H. Haick
The Department of Chemical Engineering and
The Russell Berrie Nanotechnology Institute 2. Self-Healing Polymers
Technion – Israel Institute of Technology
Haifa 3200003, Israel Inspired by the wound healing properties of natural skin,[27] self-
E-mail: hhossam@technion.ac.il healing polymers are dramatically moving towards overcoming
DOI: 10.1002/adma.201604973 mechanical failure of materials or devices due to wear and tear.

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Instead of mimicking the complexity of the healing processes
in human skin (which can take weeks for full recovery), the Tan-Phat Huynh received his
healing mechanism of this novel polymer is simpler than in PhD in Physical Chemistry in
nature.[28] Three kinds of self-healing polymers have been cat- 2014 from Institute of Physical
egorized (Figure 2a–c), i.e., capsule-based, vascular-based and Chemistry, Polish Academy
intrinsic self-healing polymers.[19] Self-healing of the first two of Sciences. He has been a
polymers is based on the release of monomers and a catalyst postdoctoral fellow in the
stored inside capsules (Figure 2a) or vessels (Figure 2b) and pre- Laboratory of Nanomaterial-
sent inside the polymer matrix, which immediately release after Based Devices from 2014 to
damage. By mixing, they start polymerizing to help heal the 2016, focusing on the develop-
cut.[28] Even though large-volume self-healing can be achieved ment of self-healing chemical
(Figure 2d), the disadvantages are the slow and single-time sensors. His interests include
(for capsule-based polymer) healing, and their complicated supramolecular polymers and
fabrication processes (encapsulation of monomer and catalyst, their applications in chemical sensing. He continues in
followed by their dispersion inside the polymer). his second postdoc position to work on mussel-inspired
In contrast to the capsule-based or vascular-based self- materials at Department of Chemistry, Aarhus University,
healing polymers, intrinsic self-healing polymer (Figure 2c) Denmark.
based on molecular interactions (e.g., hydrogen bonding, π–π
stacking, and metal–ligand coordination)[30] is characterized Prashant Sonar did his
by functionalization of the polymer with different self-healing doctoral work at Max-Planck
groups[30–32] and multi-time reversible healing. Figure 2e Institute of Polymer Research
shows the supramolecular rubber, L,[29] self-healing by means (Mainz, Germany) and
of hydrogen bonds formed among acid and urea groups. awarded PhD in 2004. After
Another benefit of using an intrinsic polymer is the fast healing a postdoctoral period at ETH
(Figure 2d) because of the absence of diffusion and polymeri- in 2006, A/Prof Sonar moved
zation control steps, which is a crucial factor in their applica- to the Institute of Materials
tions in wearable devices, where signal interruption because Research and Engineering
of damage has to be avoided as much as possible. Moreover, (IMRE), Agency of Science,
due to the demand of extending the potential uses, intrinsic Technology and Research
self-healing polymers have been variously modified to achieve (A*STAR), where he served
high flexibility, fast self-healing, biocompatibility, and many as a Research Scientist. Dr Sonar was recently appointed as
physical (e.g., electrical, electronic, and thermal) and chemical Associate Professor in July 2014 at Queensland University
(e.g., electrochemical and photochemical) properties.[33] Due to of Technology (QUT), Brisbane, Australia. His research
these advantages, this Progress Report focuses mainly on the interests include the design and synthesis of novel func-
importance of intrinsic self-healing polymers and composites tional materials for printed electronics, (OFETs, OLEDs,
with special functions suitable for wearable devices. OPVs, OLETs, OPDs, and Sensors), bioelectronics and
supramoleculecular electronic applications.

Hossam Haick, Prof. at the

3. Self-Healing Polymers/Composites for Technion – Israel Institute of
Wearable Devices Technology, is an expert in
This section discusses the different strategies that scientists the field of nanotechnology
have used to incorporate self-healing properties of polymers in and smart sensors. He is the
potentially wearable devices, such as chemiresistors, field-effect founder and leader of several
transistors (FETs), solar cells and electrochemical sensors, and European consortiums for
their applications in different fields, e.g., health, energy, and the the development of advanced
environment. Table 1 summarizes recent self-healing materials, generations of nanosensors
specifying their composition, healing mechanism, and poten- for disease diagnosis. His
tial applications in wearable devices. For the sake of convenient research interests include
presentation and discussion, the devices have been categorized nanomaterial-based chemical
under two main sub-categories – electronic and electrochemical (flexible) sensors, electronic skin, nanoarray devices for
devices. Some of the examples are detailed and further dis- screening, diagnosis, and monitoring of disease, breath
cussed below. analysis, volatile biomarkers, and molecular electronic
devices.

3.1. Self-Healing Materials for Electronic Devices

self-healing polymers have to be prepared because most of them
To create self-healing and electronic properties in one layer, are insulating. The most straightforward application of self-
composites of these organic semi-conducting materials with healing polymers in electronics is as a protective coating or layer

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processed, reused and recycled. Simplicity

of its synthesis, availability from renewable
resources and the low cost of raw ingredi-
ents bode well for future applications. It is
noteworthy that the sandwich architecture for
electronic circuits only conductively self-heal
after reconnecting two parts of the cut circuits
to recreate electron flow. Therefore, while
these healing concepts and design are good
for demonstration, they are extremely chal-
lenging for micro- or nano-devices, because
of the lack of compatible manipulators that
could be used together with them.
Bao et al.[37] provided the first example of
a self-healing conductive composite using the
host polymer, L, which has a urea group for
hydrogen networking and nickel micropar-
ticles (µNi) as filler (Figure 3a). Hydrogen
bonding was enhanced within a µNi polymer
network by a thin native oxide layer covered
µNi; the 31% by volume nickel can be added
without any agglomeration. Conductivity of
Figure 1. Present and future applications of self-healing materials for different wearable 40 S cm could be reached by adding +15%
–1

devices. They include self-healing chemical sensors and e-skin that are important for medical volume fraction of the µNi and composite,
and environmental control; for instance, surgery for healing or replacing a medical sensor is which have both electrical and mechanical
eliminated with the help of self-healing. In energy applications, self-healing supercapacitors, self-healing abilities at room temperature.
batteries and solar cells are cost-effective and convenience-effective, thereby attracting invest- The composite is highly responsive to the
ment. Last but not least, self-healing coatings for devices are straightforward in preparation, healing process, and this can occur to 90%
but crucial for long-term elegance of devices. (Image “Supercapacitor” reproduced with per-
mission.[25] Copyright 2011 ACS Publications and image “Electronic skin (e-skin)” reproduced
of its original conductivity within 15 sec
[26]
with permission. Copyright 2010 Nature Publishing Group). at room temperature. The use of this self-
healing conductor for Light Emitting Diodes
of an inner electrical wire or a metallic circuit through sandwich (LEDs) has been successfully demonstrated (Figure 3b). One
architecture, where the self-healing polymer is on both sides of of the most important aspects of this self-healing conductive
the circuit.[34–36] A self-healing polymer was synthesized by the nanocomposite and its performance is due to the flower-like
method of Leibler.[29] Leibler’s self-healing polymer, L, derived nanostructure of µNi. The thin oxide layer of this nanostruc-
from fatty acids and urea, is now marketed under the name tured filler provides good wetting behavior and an appropriate
ReverlinkTM. This polymer, with recoverable extensibility up to surface area to assist self-healing, whereas the nanostructure
several hundred percent and little creep under load, can be easily greatly enhances quantum tunneling for high conductivity.

Figure 2.  Demonstration of self-healing with a) capsule-based, b) vascular-based, and c) intrinsic polymers. d) Performance map for self-healing
materials. Each polymer has demonstrated healing for different volumes of damage. e) Chemical formula of the self-healing supramolecular rubber,
L, derived from fatty acids and urea. (Figure 2a–d reproduced with permission.[28] Copyright 2010 by Annual Reviews and Figure 2e reproduced with
permission.[29] Copyright 2008 Nature Publishing Group).

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Table 1.  Summary of recent self-healing materials including their composition, healing mechanism, and potential applications in wearable devices.

Self-healing material Composition Healing mechanism Application ref.

Self-healing materials for electronic devices
Self-healing polymer Supramolecular rubber L[29] Hydrogen bonding Protective layer for circuit [34–36]
board
Self-healing conductor µNi/L composite Hydrogen bonding E-skin [37]
Self-healing conductor PHEMA-CNT-(β-CD) Inclusion chemistry between β-CD and HEMA E-skin [38]
Self-healing conductor rGO/PBS composite Dynamic dative bonds between boron and Flexion sensor [39]
the oxygen in the Si-O groups
Self-healing conductor Graphite/PEI Hydrogen bonding Strain sensor [40]
Fully self-healing Self-healing polyurethane Hydrogen and reversible covalent disulfide bonding Pressure/strain, VOC, [2,41]
chemiresistor of substrate and electrode, and “induced” and temperature sensors
self-healing of AuNP film
Self-healing conductor L fiber Hydrogen bonding and “induced” Capacitor [42]
self-healing of CNT film
Self-healing dielectric PPMA/PEI Hydrogen bonding OFET [43]
Self-healing dielectric BNNs/L Hydrogen bonding OFET [44]
Self-healing dielectric 2+ Zn2+) Coordination bonding OFET [45]
Pyridine-functionalized PDMS/(Fe or
Self-healing dielectric Fe-Hpdca-PDMS Coordination bonding Dielectric actuator [46]
Self-healing coating Coumarin-functionalized triarm PIB Photo-assisted reversibly cross-linked reaction Solar cell [47]
Self-healing sealant Perovskite/PEG Humid absorption of PEG Perovskite solar cell [48]
Self-healing materials for electrochemical devices
Self-healing subtrate TiO2/L composite Hydrogen bonding for substrate Supercapacitor [49]
and “induced” self-healing of CNT film
Self-healing electrode Self-healing polyurethane Hydrogen bonding Supercapacitor [50]
Self-healing insulator Composite of PEVA and Mn-Zn ferrite Magnetic attraction Coating [51]
nanoparticle filler
Self-healing electrode µSi/L composite Hydrogen bonding Battery [52]
Self-healing anode (Graphite/Si)/L composite Hydrogen bonding Battery [53]
Self-healing electrode Hexyl-acetate healing agent Release of healing agent from a fracture capsule Electrochemical sensor [54]
Self-healing electrode GOx/gelation Reversible bonding between gelatin and GOx/ Biosensor [55]
gelatin
Self-healing electrode EMIMTCB and tannic acid Reversible electrochemical reaction FET [56]
Self-healing ionic Supramolecular ionic polymers based on Hydrogen bonding Electrolyte for electrochemical [57]
conductor (di-/tri-) carboxylic acids and (di-/tri-) alkyl devices
amines
Self-healing proton Oxalic-based metallogel Coordination bonding Electrolyte for electrochemical [58]
conductor devices
Self-healing coating Bilayered PPy, inner layer is doped with Release of available Corrosion protection [59]
heteropolyanions of PMo12O403; the outer MoO42– ions to
layer is doped with dodecylsulfate the defect zone

Carbon nanotube (CNT) material is a favorite amongst
chemists trying to develop a hybrid CNT/polymer mate-
rial due to the unique properties, e.g., high electron con-
ductivity,[60] well-developed routes of functionalization,[61,62]
and low percolation threshold of CNT-based composites.[63]
Unsurprisingly, the self-healing polymer could also incor-
porate CNTs to form a composite for humidity and touch
sensing.[38] First, pyrene-modified β-cyclodextrin (β-CD)
is attached to the surface of CNTs by π–π stacking (step 1,
Figure 4). Second, a self-healing conductive composite
can be formed through inclusion (host-guest) chemistry
of poly(2-hydroxyethyl methacrylate) (PHEMA) and β-CD
(step 2, Figure 4), and this is followed by polymerization
(step 3, Figure 4). This host-guest interaction is also effec-
tive under water because of its hydrophobicity. Even though
this composite has a higher conductive (approx. 60 S cm–1)
than a µNi/L composite and a wide linear range of response
to humidity (from 30–90%), its percolation threshold
(7–11 wt%) is quite high, causing an increase in the glass
transition temperature of the composite. As a result, the
material becomes stiffer, making self-healing inefficient
because of restricted movement of the polymer chains.

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Figure 3.  a) Self-healing conductor based on a composite of self-healing branched polymers with urea groups at the end and nickel microparticle;
b) Demonstration of the healing process using a self-healing electrical conductor based on a composite with an LED in series with: 1) an undamaged
conductor; 2) a completely severed conductor (open circuit); 3) an electrical healing, and 4) a healed film being flexed with original mechanical strength.
Reproduced with permission.[37] Copyright 2012, Nature Publishing Group.

Along with CNTs, reduced graphene oxide (rGO) is another
promising conductive material for preparation of composite.[39]
Networks of rGO were infiltrated with a solution of polydi-
methylsiloxane (PDMS) and boron oxide nanoparticles by
vacuum casting. The rGO/polyborosiloxane (rGO/PBS) com-
posite was formed by in situ cross-linking at 200 °C.[64] PBS
is a supramolecular polymer of an intrinsic self-healing char-
acter because of the dynamic dative bonds between boron
and oxygen in the Si–O groups and hydrogen bonds between
residual OH groups at the end of some unreacted polymer
chains. The resulting composites comprise an rGO continuous
network confining PBS (Figure 5a). The first highlight of this
hybrid material is the very high electron conductivity of ≈8 ×
103 S cm–1, probably the highest conductive self-healing com-
posite ever developed because of its high density and the uni-
form honeycomb structure of rGO (Figure 5a). Second is the
low percolation threshold (0.5 wt%) of rGO used in this com-
posite, which is difficult to achieve by normal dispersion tech-
niques. Therefore, self-healing of this polymer is efficient with
almost 100% recovery (Figure 5b), and the composite film is
manifested as a sensitive flexion sensor (Figure 5c). In con-
trast, another self-healing composite prepared by mixing and
grinding graphite and polyethylenimine (PEI) creates sev-
eral challenges[40] – a very high percolation threshold (65 wt%
graphite), and a lower conductivity (1.98 S cm–1) compared to
the rGO/PBS composite.
A multifunctional self-healing sensing device has been
reported by Huynh et al.[41] (Figure 6). The substrate and elec-
trodes were made from self-healing materials, the main self-
healing component being a newly synthesized polyurethane
derivative. The self-healing mechanism is based on reforma-
tion of hydrogen and disulfide bonds between polymer chains
at two sides of the cut (Figure 6b). Healing time and efficiency
of this polyurethane depends on the density of hydrogen bonds
created by the urea groups of polyurethane, and on disulfide
bonds and the flexibility of the polymer chains. The polymer
has been used as a self-healing substrate; the composite with
silver particles (in micrometer size) works as self-healing

Figure 4.  Schematic preparation of conductive self-healing composite, PHEMA-CNT-(β-CD), using inclusion chemistry between β-CD and HEMA.
Reproduced with permission.[38] Copyright 2015, Wiley–VCH.

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Figure 5.  a) rGO/PBS networks contain microscopic channels (PBS) separated by thin walls (rGO), which are packed to form a honeycomb cross-
section with residual porosity in the composite of <1%. Scale bar = 20 µm. b) Optical images of deeply scratched composites obtained with high and
low molecular-weight (HMw and LMw, respectively) polymer immediately after cutting, followed by 24 h healing. Scale bar = 1 mm. c) Dependence
of relative resistance change of self-healing rGO/PBS film on flexion change. The film recovers its initial resistivity after relaxation. Reproduced with
permission.[39] Copyright 2015, Wiley–VCH.

Figure 6.  a) Schematic and photograph of the self-healing chemiresistor consisting of a transparent (yellowish) self-healing substrate, a jelly like
self-healing electrode, and a pliable induced self-healing AuNP film. b) Optical images from top to bottom row of the self-healing substrate, the self-
healing electrode, and the ethoxyphenyl-capped AuNP film coated on the self-healing substrate before and after cutting and then healing at 20 °C. Scale
bar is 200 µm for the self-healing substrate, and 100 µm for the self-healing electrode and induced self-healing AuNP film. c) Resistance responses
and calibration plots of relative resistance response of the ethoxyphenyl-capped AuNP chemiresistor in c1) bending experiments before (1) and after
electrode-cut (2) and electrode&AuNP-cut (3); c2) stretching experiments (1) before (1) and after (2) electrode-cut (2) and AuNP-cut (3). c3) Exposure
to n-octanol at different concentrations before (1) and after electrode-cut (2), second electrode-cut at the same (3) and a different position (4), and an
additional AuNP-cut (5). Reproduced with permission.[41] Copyright 2016, Wiley–VCH.

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Figure 7.  a) Chemical structure of self-healing polymers; b) image of self-healing process due to hydrogen bonding of PHPMA/PEI blend; c) optical
tracking of PHPMA/PEI blend film healing process upon cracks made with a blade; d) self-healing organic field-effect transistors. Reproduced with
permission.[43] Copyright 2015 Wiley–VCH.
electrode of a chemiresistor. The role of the electrode is to pass
electrical current through the sensing layer, which is made of
organic-capped gold nanoparticles (AuNP), which has an elec-
trical resistance in the range of hundreds of kΩ to a few MΩ.
The resistance of this layer varies with changes in the imme-
diate environment (pressure, temperature, presence of gaseous
compounds, etc.). So far, the organic-capped AuNP layer does
not have intrinsic self-healing properties; however, an “induced”
process achieves the healing process because of the self-healing
process of the polymeric substrate laying beneath it. To dem-
onstrate the device’s functions, the self-healing chemiresistor
was exposed to different environments (Figure 6c), pressure or
strain (Figure 6c1–2), and volatile organic compounds (VOCs)
(Figure 6c3)[2,41] known to have an important role as a “pri-
mary prevention” strategy for diseases through breath or skin
sampling.[2,65,66]
Another approach to “induced” self-healing is based on
healing conductive wire-based CNTs.[42] When the broken
parts are brought back into contact, hydrogen bonds are
formed between the two sections of fiber made of self-healing
polymer, L,[29] to reunite them. At the same time, the aligned
CNTs between the two cross-sections are reconnected by van
der Waals forces[67] during the self-healing process of the fiber.
A strong adhesive force is produced between aligned CNT
arrays and different substrates by van der Waals interactions;
although these forces are weak, their collective effect within
a density range of 1010–1011 cm–2 produces a strong adhesive
force.
With increasing challenges, researchers have partially
inserted a self-healing layer in organic FETs (OFET) towards
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implementation in various applications, such RFID tags,
chemical sensors and many others.[68–72] Up to now, develop-
ment of the self-healing property for OFET has been limited in
the dielectric (insulator) layer because of the single-component
chemistry and ease of construction. A poly(2-hydroxypropyl
methacrylate)/poly(ethyleneimine) (PHPMA/PEI) blend as
a self-healable dielectric layer was produced by Katz et al.[43]
PHPMA was sucessfully used as a dielectric material for
OFET devices, but this polymer has no self-healing ability due
to its lack of dynamic bonding; thus a new dielectric material
with such bonding is required. PHPMA and PEI copolymers
(Figure 7a) were selected because of the interaction between
both polymer chains through many hydrogen bonds (Figure 7b).
PEI polymer additives with PHPMA also reduce the glass tran-
sition temperature of the blend, i.e., polymer chains become
more dynamic, which is an efficient way of inducing hydrogen
bond formation at room temperature. The blend system is also
soluble in inexpensive environment-friendly ethanol, which is
an orthogonal solvent of many organic semiconductors. The
PHPMA/PEI (1:1, w:w) blend film 10–11 µm thickness scratch
had excellent self-healing properties after slight heating, as
monitored by optical microscopy (Figure 7c). This self-healing
copolymer blend with a carbon paint was used as a gate elec-
trode in a flexible (polyethylene terephthalate)-based top gate
OFET device, with poly(3-hexylthiophene) as an active semicon-
ductor. Before cutting, on cutting and after cut healing, the top
gate OFET device showed excellent transistor behavior at a low
gate voltage (Figure 7d). On cutting, the mobility and drain cur-
rent decreased, but these parameters recovered to near the orig-
inal values after healing at room temperature in air for 10 h.
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Using a different approach, surface functionalized boron
nitride nanosheets (BNNs) could become incorporated in the
self-healing polymer, L,[29] yielding stable dielectric and mechan-
ical properties relative to the pristine polymer (Figure 8a–c).[44]
BNNs, the structural analogs of graphenes, are not conductive
and have good dielectric properties.[73] This polymer nanocom-
posite retains many properties, including greater electrical
resistivity, improved thermal conductivity, greater mechanical
strength, higher breakdown strength, and very well stabilized
dielectric properties after mechanical damage. A unique feature
of this nanocomposite is that the recovery condition remains
the same after sequential cycles of cutting and healing, which
clearly suggests that the nanocomposite does not age with
mechanical breakdown (images of the cutting and healing
process are shown in Figure 8b). Repeatable healing is clearly
desirable for microelectronic devices and their applications. The
integration of self-healing-based material significantly increases
its functional longevity under harsh conditions, e.g., abrupt
temperature change, repeated mechanical distortion and high
voltage arcing. This indicates the enormous scope of self-heal-
able supramolecular materials for flexible electronic devices,
expanding from conductive units to an insulation regime.
In addition to hydrogen bonding, metal-ligand coordination,
i.e., between 2,2′-bipyridine-5,5′-dicarboxylic amide of func-
tionalized PDMS and Fe2+ or Zn2+ of dispersed metal salts,
has been used to prepare a self-healing dielectric elastomer of
PROGRESS REPORT
OFET.[45] The self-healing ability of the polymer is primarily
determined by the kinetic ability of the (Fe2+/Zn2+)-pyridine
coordination bonds. Metal salts also enhanced the dielectric
constant of the self-healing polymer, while maintaining the
stable capacitance without introducing undesirable ionic
effects. This dielectric elastomer has stable transfer character-
istics and low gate leakage current after 1000 cycles at 100%
strain. Another example is PDMS functionalized with 2,6-pyri-
dinedicarboxamide, forming a coordination complex with
Fe3+.[46] These reversible coordination bonds have a self-healing
ability even at low temperature (-20 °C). More interestingly,
this elastomer has been applied to a dielectric actuator, i.e., a
device that transforms electric energy into mechanical work.
When a high electric field of 17.2 MV m–1 is applied, an area
expansion of 3.6% was recorded without damage.
Tri-arm polyisobutylene (PIB) was functionalized with cou-
marin to perform photo-assisted self-healing, based on a revers-
ible cross-linked reaction between two groups of coumarin at
a wavelength of 365 nm (Figure 9).[47] This coating proved to
be an excellent layer for preserving the transparency of solar
cells, which directly influences incident photon-to-current effi-
ciency[74,75] Besides its optical transparency, PIB has high flex-
ibility, strong adhesion to the substrate, good barrier properties,
thermal stability and good chemical resistance. Nevertheless,
to assure operation under real-world conditions, the effect of
harmful moisture on the operation and efficiency of the solar

Figure 8.  a) BNNSs-CONH2 being introduced into a polymer network to form hydrogen bonded supramolecular polymer nanocomposites (left);
photograph of the nanocomposites (right). b,c) Development of a flexible electronic material that self-heals and restores many functions, even after
multiple breaks. b) Sample cut in the middle, and then the two portions put in contact with each other; upon heating they healed completely. The healed
material can still be stretched and hold weight; c) large stretching of healed composite. Reproduced with permission.[44] Copyright 2016, Wiley–VCH.

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Figure 9.  a) Reversibly cross-linked network formation by photodimerization/photocleavage of coumarin functionalized PIB. b) Possible self-healing
mechanism. Reproduced with permission.[47] Copyright 2015, ACS Publications.
cells – mainly a perovskite solar cell (PSC)[76] that suffers from
degradation of perovskite CH3NH3PbX3 – have to be elucidated.
To this end, Zhao et al.[48] used polyethylene glycol (PEG) as a
self-healing moisture absorber to prevent moisture reaching the
perovskite solar cell (PSC). Perovskite film without PEG decom-
posed into PbI2 and irreversibly turned yellow (Figure 10a). In
contrast, the PEG scaffold perovskite film showed yellowing
at first and recovered to black in 45 s after removal from the
spray (Figure 10a). Self-healing was also observed by measuring
the current–voltage curve of PSC; this effect can be ascribed to
the excellent hygroscopicity of PEG molecules and their strong
interaction with perovskite. The omnipresent PEG molecules
can also efficiently absorb water to form a compact moisture-
barrier around perovskite crystal grains, with little water pen-
etrating into the film (Figure 10c). In short, a self-healing PIB
coating or PEG absorber are both organic-based substances that
can be readily adapted to wearable devices.
3.2. Self-Healing Materials for Electrochemical Devices
In this section, we explore different types of electrochemical
devices that can generate electrical energy either from chem-
ical reactions (electrochemical solar cell and capacitor, fuel cell,
etc.) or by facilitating chemical reactions from applied electrical
energy (electrochemical sensor).[77–79] Therefore, self-healing
polymers or composites in these devices require different
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functions from electronic devices, such as electroactivity, ion or
redox conductivity, or double-layer capacity.
The first example is a supercapacitor with self-healing ability.
Sometimes called an ultracapacitor or electric double-layer
capacitor, it is an electrochemical capacitor with capacitance
values much higher than other capacitors (but lower voltage
limits).[78] A supercapacitor usually has double-layer capaci-
tance, a non-faradaic process, and therefore, supercapacitors
are sometimes classified as electronic devices. The first attempt
was a self-healing substrate for a supercapacitor prepared from
a self-healing polymer, L,[29] filled with a hierarchical TiO2
nanoflower (≈400 nm), simply by vigorous stirring followed
by thermal crosslinking with urea.[49] A layer of CNT deposited
on the top of substrate has the property of induced self-healing
(as previously mentioned). The experiments showed a high
recovery (87.5%) of specific capacitance after the 5th healing
from 35 to 30 F g–1. A more efficient approach with a yarn-based
supercapacitor (Figure 11) can self-heal under two consecutive
processes; magnetic assistance from yarn to attract two cut-
ting parts, and then the outside layer is made by self-healable
polyurethane (Figure 11c). Self-healing is based on hydrogen
bonds between carboxylate groups of the polymer chains.[50]
This technique is an improvement for precise self-healing for
nano- or micro-scale circuit (see Section 3.1) because two cut-
ting pieces can find each other by magnetic attraction instead
of being manually connected. In a similar way to magnetic-
assisted self-healing, magnet–polymer composite consists of
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PROGRESS REPORT
Figure 10.  a) Photographs of perovskite films with and without PEG, showing the color changes after water-spraying for 60 s and in ambient air over
45 s. b) J–V curves of PSCs before and after water-spraying show complete recovery of the cells within 1 min of returning to ambient air. c) Schematic
diagram to show mechanisms of the self-healing properties in PSC: Absorption of water on perovskite (1), hydrolysis of perovskite into PbI2 (2) and
CH3NH3I·H2O, restraint of CH3NH3I by reacting PEG with nearby PbI2 to form perovskite once again after water has evaporated (3). PEG has a strong
interaction with CH3NH3I, preventing it from evaporating; subsequently MAI and PbI2 react in situ to form perovskite after the film had been removed
from the vapor source. Reproduced with permission.[48] Copyright 2016, Nature Publishing Group.

a magnetic Mn–Zn ferrite nanoparticle filler in a commercial healing functionalities of commercial polymers. The mag-
poly(ethylene-co-vinyl acetate) (PEVA) thermoplastic matrix. netic filler can trigger actuation, self-healing and multiple cycle
The magnetic filler can trigger healing by locally heating the damage sensing.
composite with an external alternating magnetic field.[51] The By using different fillers, i.e., silicon microparticles (µSi)
thermoplastic matrix ensures multiple strain sensing cycles and self-healing polymer L, self-healing rechargeable batteries
and self-healing through a memory-shape mechanism. The have been developed.[52] A µSi anode in this case provides high
novelty here lies in the development of damage sensing and capacity, but it usually suffers from fractures due to expan-
sion and contraction of µSi during lithia-
tion and delithiation processes, respectively.
Therefore, L plays an important role in self-
healing composites by increasing the life-
time of the high-capacity anode through the
ability to limit mechanical fractures gener-
ated during the cycling process. The same
self-healing polymer has also been used to
protect the structure of the graphite/Si anode
of a battery.[53] Although a very high specific
capacity was achieved (≈584 mAh g–1) and
retention (81%) for a 1:4 volume ratio, this
hybrid material suffered under low mechan-
ical strength (only 50% recovery of tensile
strength and strain after healing), due to the
high percentage of (graphite/Si)/polymer
(>25%) in the composite.
A film of a capsule-based self-healing
polymer has been used in electrochemical
sensors as self-healing working electrodes
(Figure 12a) for voltammetric determina-
Figure 11.  a) Schematic illustration of the self-healing process of a yarn-based supercapacitor.
Magnetic alignment can assist the reconnection of the fibers in the broken yarn electrodes when tion of sodium using 10 mM ferricyanide in
they are brought together; see inset. b) SEM image of the electrode. c) Chemical formula of 1 M phosphate buffer (pH 7.0) as the redox
self-healing polyurethane. Reproduced with permission.[50] Copyright 2015, ACS Publications. probe.[54] After mechanical damage, the

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PROGRESS REPORT

Figure 12.  a) Schematic diagram showing the preparation of the self-healing carbon ink and screen-printing procedure (top), and the self-healable
process occurring when a self-healing printed electrode is mechanically damaged (bottom), along with a typical voltammetric response at the different
stages. Reproduced with permission.[54] Copyright 2015, Wiley–VCH. b) Layout of the field effect device, and the chemical structure of ionic liquid and
polyphenol. EMIMTCB: redox of the electrolyte, α-ZnO: solution processed amorphous zinc oxide. Reproduced with permission.[56] Copyright 2015,
Wiley–VCH.

capsules in the polymer film are ruptured, releasing the hexyl-
acetate healing agent in the crack. This agent dissolves locally
the acrylic binder, leading to redistribution of the filler particles
and restoration of the conductive pathway. Even though this
approach has been successful in producing a self-healing con-
ductive ink,[80,81] the main drawback, as also of capsule-based
self-healing materials, is single-time self-healing. This means
that if the cut reappeared in the same location, healing would
be inefficient or fail. Moreover, this technique cannot be applied
under flow conditions because the carrier solution dilutes down
the healing agents.
In a glucose biosensor,[55] reversibility of cross-linking
between gelatin and glucose-oxidase (GOx) functionalized
gelatin can be healed at low temperature, because tempera-
tures >37 °C can break the physical bonds between gelatin
and GOx/gelation. There are two benefits of this approach, i.e.,
self-healing occurs at low temperature (a limitation of most
self-healing materials), and is highly reversible. Furthermore,
one could imagine the use of this approach as a humidity
sensor because of its high volume swelling.
A self-healing composite with electroactive species can be
used as electrochemical gate of a FET to manipulate the source-
drain current by electrochemical processes. An ionic liquid
gate containing 1-ethyl-3-methylimidazolium tetracyanoborate
(EMIMTCB) and tannic acid can self-heal by using a revers-
ible electrochemical reaction with an oxygen-deficient α-ZnO
thin film (Figure 12b).[56] During operation of the transistor by
applying a voltage to the liquid gate, α-ZnO is degraded, based
on the cathodic reduction of the thin film and the production
of oxygen species, such as superoxide. Tannic acid is an oxygen
scavenger that traps radicals, acting at the same time as a
source of oxygen to heal the highly conductive reduced α-ZnO
surface.
Unlike electronic conductivity, ionic conductivity[82,83] is
important in electrochemical processes. Ion conductivity of a
composite polymer and an ionic conductor (usually called an
electrolyte) is based on the migration of cations and anions ions
in a polymer network. Indeed, ions in a polymer are good for
self-healing processes because of the electrostatic interaction
between cations and anions. A new family of supramolecular
ionic polymers has been synthesized by a straightforward
method using commercially available (di-/tri-) carboxylic acids
and (di-/tri-)alkyl amines.[57] Apart from their self-healing
ability, these supramolecular ionic polymers have unique
rheological properties, such as a sharp transition between a
viscoelastic gel and a viscous liquid, resulting in acceptable
ionic conductivity (10–5 S cm–1). This chemistry could poten-
tially be used to develop a self-healing electrolyte for wearable
electrochemical devices. Similarly, a unique proton conductive
oxalic-based metallogel made by mixing solutions of copper(II)
acetate hydrate Cu(OAc)2·H2O and oxalic acid dehydrated
at room temperature proved to have self-healing properties
(Figure 13).[58] The self-healing mechanism of this system
remains unclear, but rapid desolvation/resolvation of (copper
oxalate)-based 1D coordination oligomers at the interface might
be induced. Due to physical stress and subsequent relaxation,
this allows rapid restoration of the multicomponent supramo-
lecular network without necessarily disassembling the coordi-
nation complexes. In addition, the high-conductivity composite
could readily be prepared by blending the metallogel with CNTs
(as in Figure 13a). Remarkably, the system could also impart
the induced self-healing ability to other gel networks lacking
this capacity (Figure 13b). For these reasons, this metallogel
Figure 13.  a) Demonstration of the restoration of bulk conductivity of the
oxalic-based metallogel/multi-wall CNTs composite gel used to bridge
an electrical circuit. b) A “LEGO-car” fabricated by using 1) oxalic-based
metallogel and with 2) rhodamine B, 3) with lanasol, and 5) with multi-
wall CNTs (1 wt%); 4) is diaminocyclohexane bis(amine) gel. Reproduced
with permission.[58] Copyright 2016, ACS Publications.

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and the derivatives will be of interest in the development of
fully self-healing devices.
An ion-permselective conducting membrane made from
a 4.2 mm thick conducting polypyrrole (PPy) coating with a
bipolar structure on carbon steel without any additional bar-
rier-type top-coat possesses a self-healing ability in aggressive
3.5 wt% NaCl solution.[59] The ability of the coating to self-heal
is controlled by the oxidizing properties of PPy and the amount
of available MoO42– ions, which can be released directly from
the inner layer to the defective zone. Dissolved iron then reacts
with MoO42– ions to form iron molybdate inside the defect,
thereby blocking iron dissolution. The general concept of the
controlled release of healing ions to the defect zone during the
self-healing event might also be suitable for other active metals.
4. Conclusions and Perspectives
This Progress Report reviews the developments in the field
of self-healing polymers/composites and the wearable devices
thereof. One part of the report presents and discusses many
aspects of the chemistry of self-healing materials (from non-
covalent to reversible covalent based mechanisms), and the
approaches used for functionalization of the composites to
enhance their electrical conductivity, magnetic, dielectric, elec-
troactive or photoactive properties. The second and comple-
mentary part of the report links the self-healing materials with
partially or fully self-healing device technologies, including
wearable sensors, supercapacitors, solar cells and fabrics.
Although very promising advances have been made so far,
there is still a long way to go to implement self-healing wearable
devices in real-world conditions or in commercial avenues. This
is because of one or a combination of the following challenges:
• Integration of self-healing devices into circuit board remains
challenging, mainly as to how making them comparable in
size so they can fit the architecture of the board; and in how
to provide metallization to ultrathin organic films (compare
ref. [84,85]).
• Flexibility of the self-healing substrates might introduce par-
asitic responses in some applications, e.g., chemical or bio-
logical sensing. Rigid self-healing materials, therefore, have
to be developed.
• The electrical conductivity, chemical or biological sensitivity,
or photochemical properties of the self-healing polymers are
lagging behind comparable non-healing materials.
• Self-healing polymers are usually more expensive than com-
mercial polymers, mainly because they require more synthet-
ic steps and chemical modification processes.
To overcome these challenges, important aspects have to be
addressed and developed further. These include, but are not
confined to:
• Development of high-resolution 3D-printing approach for
the auto-construction of small-scale multilayer self-healing
devices.[86–88] This would help to solve the first and second
problems above.
• Development of self-healing ceramics[89] or metals[90] to ob-
tain rigid self-healing materials or devices with minimal
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PROGRESS REPORT
parasitic side effects.
• Synthesis of self-healing polymers that are intrinsically con-
ductive, for example, by a polymer having electron/hole con-
ductivity in its backbone and self-healing in its functional
side-chains.
• Integration of self-healing polymers with deliberately con-
trolled (semi)conducting inorganic nanomaterials, such as
molecularly modified Si nanowires, without carrier donating
or carrier withdrawing side-groups,[91–94] or TiO2.[95]
More innovations in self-healing materials are anticipated
in the near future. Towards this end, self-healing materials
should come down to three main features, namely fast healing,
biocompatibility and cost-efficiency, so that one could see self-
healing devices in real-world conditions or the market within
a short time. With this prospect, one can imagine self-healing
devices or sensors that are implanted in human body or tat-
tooed on the skin to allow continuous health monitoring, with
only once-in-a-lifetime surgery for implantation/installation of
the device/sensor.
Acknowledgements
This research received funding from the Phase-II Grand Challenges
Explorations award of the Bill and Melinda Gates Foundation (grant ID:
OPP1109493). H.H. thanks the Alexander von Humboldt Foundation
for a senior research fellowship in the Max-Planck Institute for Polymer
Research (Mainz, Germany). P.S. thanks the Australian Research
Council (ARC) for a sponsored Future Fellowship (FT130101337) and
Queensland University of Technology (QUT). The authors thank Drs.
Yunfeng Deng and Weiwei Wu for reviewing and making comments on
the manuscript.
Received: September 15, 2016
Revised: November 21, 2016
Published online: February 23, 2017
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