Evaluation of Energy storing methods used in smart textiles

Ushani Navodya-151025K
Department of textile and clothing technology, University of Moratuwa

Abstract

Smart textile is a new application field for microelectronic devices that integrated sensors, data processing,
communication, and power units to stimuli external conditions in a predetermined way. The growing
demand for smart textiles has led to enhanced focusing development of sensing, energy harvesting, and
energy storing techniques based on renewable and ambient sources but still lacking solutions.
Supercapacitors and lithium batteries are conventional energy storage systems that are typically rigid and
limited by their lifespan, not satisfying the requirements. This perspective seeks to provide some critical
insights into the challenges facing the development and adoption of energy-storing methods in possible
future applications of smart textiles to make them small size, high flexible, and adaptable to comfort
frequent deformations during usage. Expected future products in the fabrication and application of textile-
based energy storage will be discussed.

Introduction
Conventional batteries and capacitors are used to powered notable wearable technologies, including Nike
Fit, Adidas MiCoach, Cute- circuit Galaxy Dress and T-shirts, “Hi-call” Bluetooth enabled phone-glove,
Google Glass, and Apple Smart Watch. To date fully developed textile energy storage device does not exist,
nor does a streamlined manufacturing process integrating the various components. Papers from the smart
garment and energy storage communities point out the need for wearable, flexible batteries, and
supercapacitors. In this review, we discuss the evolution of energy textiles, various techniques, and
processes used to fabricate them as well as their electrochemical performance. We also identify key metrics
that are needed so that lab prototypes can be scaled up and mass-produced.

There are three main electrochemical energy storing technologies used in wearable systems ranging from
high power to high energy, respectively electrical double-layer capacitors (EDLCs), pseudocapacitors, and
batteries. Both double layers and pseudocapacitors are commonly called "supercapacitors." (Fig. 1). EDLCs
store charge in an electrostatic double layer between the surface of a charged electrode material and its
respective counter ions (Fig. 1a). Pseudocapacitors are devices that have a double-layer capacitance and fast
surface redox or intercalation. It increases the energy density while maintaining fast charge and discharge
times comparable to an EDLC (Fig. 2b). Batteries store charge through the conversion of electrical energy
into chemical energy (Fig. 1c). Rechargeable secondary batteries use reversible reactions (e.g., lithium-ion
intercalation into graphite). It should be noted that asymmetric cells are also viable systems for wearable
energy applications.

Fig 1:

All of these devices typically consist of electrode material, current collector, separator, and electrolyte.
 a) Electrode material

Reduction and oxidation reactions take place in the electrode, and the surface of the electrode material
should highly conductive to conduct electric that carries electric current. They can be classified as an electric
double-layer capacitor (EDLC) materials and pseudocapacitors materials because of their different charge-
storage mechanisms. EDLC materials are carbon material having high electric conductivity, high specific
surface area, low cost, and chemical stability. Pseudocapacitor materials usually are divided into two kinds
as metal oxides (such as MnO2, NiO, RuO2, Co3O4) and conductive polymers (such as polypyrrole (PPy),
polyaniline (PANI) and polythiophene). The metal oxide materials showed higher capacitance and energy
density, larger than conventional carbon materials, and higher stability than the conductive polymers, which
stored energy by faradaic pseudocapacitance. It takes advantages of low cost, high working potential, and
high specific capacitance, but suffers from high resistance and low cycling stability.

b) Current collector

Current collectors ensure the good current transfer, which should rapidly collect and transfer the charge.
They should have good chemical stability, good connection with the substrates, and active electrode
materials to decrease the contact resistance and high conductivity to decrease the internal resistance.

c) Electrolyte

They offer ions, accelerate ion transfer, and adhesion electrode particles. The electrolyte can be divided into
the liquid electrolyte and solid electrolyte. Liquid electrolytes are still not safe enough due to the risk of
leakage and need high-cost packaging materials and techniques, resulting in difficulty in fabricating
miniaturized flexible wearable electronic devices. So, solid state electrolytes are a good choice for SCs,
which also exhibits good cycling performance, excellent mechanical flexibility, and safety. Usually, solid-
state electrolytes are prepared by mixing the acids, alkalis, or salts with polymer matrix, such as
PVA/H3PO4, PVA/KOH, and PVA/Na2SO4 electrolytes. Furthermore, solid-state electrolytes exhibit great
flexibility and stretchability while suffering from relatively low ionic conductivity.

The development of energy-storing textiles has been systematically approached and can be categorized into
the following phases.

A. Coated energy-storing textiles

Researchers began by coating cotton or polyester textiles, either woven, knitted, or non-woven, with various
carbon or redox-active electrode materials by Dip-coating, screen-printing, and painting. Manufacturing
challenges were to be overcome for coated full fabrics as multiple layers of the electrode, current collector,
separator, and encasement have to be incorporated into a single piece of fabric or a multilayered garment.

Yi Cui's group reported the first textile batteries and supercapacitors at Stanford University, which focused
on coating single-walled carbon nanotubes (SWCNTs) onto cotton fabrics (Fig 2a-b). Hu et al., assembled
SWCNT-fabrics into stacked electrode sandwiches with a separator, encased with a typical battery
electrolyte (LiPF6) having excellent performance, as well as high capacitances. However, it had a few
negative concerns, mainly toxicity (e.g., LiPF6 electrolyte) so, a later study replaced the LiPF6 with non-
toxic aqueous-based Na2SO4 and Li2SO4. In 2011, activated carbon was screen printed onto mass-produced
cotton and polyester woven fabrics because the shape of the electrode in the application screen could be
masked, requiring no further steps to remove a resist from the fabric after dying. Bao et al. carbonized cotton
t-shirts into highly porous activated carbon fabrics and coated pseudocapacitive MnO2 particles to increase
its capacitance per area. This work developed a novel material system, but like many works, it still used
solid metal current collectors and a liquid electrolyte.
 Fig.2

Larger scale laser printed waterproof graphene supercapacitors of dimension 100 cm2 fabricated in 3
minutes on textiles with excellent water stability. This was an excellent example of common clothing
materials being transformed for wearable supercapacitor applications. Further, a demonstration is given for
the textile integrated solar energy storage with stable performance for up to 20 days to reach half of the
maximum output potential. These cost-effective self-reliant on-chip charging units can become an integral
part of the future electronic and optoelectronic textiles.

Printed flexible solid-state supercapacitors for portable and wearable energy storage were developed. Printed
electronics (PEs) are considered as an emerging field that meets the demands of preparing stacks of micro/
nanoscale devices in a more straightforward, faster, and cost-effective way with the controlled functional
area. PEs technology is employed and used in flexible solid-state SCs, including screen printing, inkjet
printing, and roll-to-roll (R2R) printing. However, there are challenges which are; the corresponding
functional inks are deserved to be developed to match the printing process, which should be well printable
for various flexible substrates and stable at ambient conditions or controlled storage temperature and
humidity for months. Moreover, the resolution of each printing technique should be considered in practical
applications based on demands, resulting in printed flexible solid-state SCs with better architectures and
electrochemical performance. Finally, the scalable production ability of printing techniques should be
reasonably utilized for low cost flexible solid-state SCs. At present, the metal current collectors are used
widely for printed flexible solid-state SCs, such as gold and silver. For example, Hu et al. used a printed
gold current collector to fabricate flexible SCs, as obtained SCs exhibited high voltage and excellent
mechanical flexibility.

Electrospinning of TiC-CDC28 and PEDOT29 nanofibres also showed favorable results, and TiC- CDC
nanofibres demonstrate particular promise for high power supercapacitors. Other researchers have also
explored electrospinning PAN (polyacrylonitrile) nanofibres that were subsequently carbonized to act as
high surface area nanofibre electrodes. Electrospun coatings can be applied onto the surfaces of fabrics in
order to mechanically stabilize the material. The main challenges electrospinning faces are attributed to time
and cost to fabricate these materials.

B. Fiber Shaped Energy Storage Devices

Compared with other types of energy storage systems such as batteries, supercapacitors often reveal in a less
complicated construction and require a less strict fabrication process. These featured supercapacitor fibers
can make functional or smart energy storage devices in fiber format for more desirable and environmental
adaptable during usage. Supercapacitor fibers fabrication process consists of preparing the fiber substrate,
incorporating active materials, coating the electrolyte, and assembling as prepared fiber electrodes into a
device. As a simplification of the above preparation process, the synchronous deposition strategy to
continuously fabricate supercapacitor fibers was designed and achieved. The production line integrated the
procedures within five minutes, which are depositing active materials (including manganese dioxide,
polyaniline, and polypyrrole), polymerization, and device assembly. The scale-up production may bring the
technology from the lab to commercialization for weaving supercapacitor fibers into power textiles in a
continuous manner.

Several types of fiber current collectors are developed in the past years, mainly including plastic fibers,
ultrafine metal fibers, CNT or graphene fibers/yarns, polymer fibers, and composite fibers. In order to
achieve fiber SCs with excellent flexibility, good electrochemical performance, and lightweight, carbon-
based fibers (CNT yarns, graphene fibers, CNT/polymer composite yarns) are later widely used as the
current collectors to fabricate high-performance fiber SCs. Many of recent works employed hybrid
composites such as MWCNTs/MnO2, CNTs/PANI, PANI/graphene/ CNTs, CNTs/MoS2,
Cu2O/CuO/Co3O4, Ni3S2CoS. As the electrodes for fiber SCs to take advantage of both carbon-based
materials and metal oxides or conducting polymer-based materials, thus can increase the capacitance and
energy density of the fiber SCs. Using different materials synthesis strategies or device fabrication
techniques, researchers developed fiber SCs with varied electrochemical performances with different types
of hybrid composites as the electrodes. As the key component to construct fiber shaped energy storage
systems, fiber electrodes are required to accommodate various deformations such as bending, stretching, and
twisting under the premise of relatively high electrical conductivity and mechanical properties. Another
important component of fiber SCs is the electrolyte. Usually, gel electrolytes are used as they are
nonflammable, low toxicity, easy to handle, and avoids both the leakage problem and the short circuit that
occurred for devices with liquid electrolytes. There are two types of gel electrolytes for fiber SCs, including
acid electrolytes and alkaline electrolytes. The most common gel polymers include poly (vinyl alcohol)
(PVA), polyacrylate (PAA), and poly (vinylidene fluoride) (PVDF). The device structures such as parallel,
twisted, coaxial, and large area woven SCs can help to achieve improved electrochemical performance.
Also, they can make the devices achieve some smart, functional properties, such as stretchable, self-healing,
implantable, fluorescent and shape memory.

Single Kevlar fibers, coated in gold, and then grew ZnO nanowires from the gold, with one electrode
wrapped (twisted) around the other, have comparable capacitance and scale to micro supercapacitors and
some ceramic capacitors which had developed by Wang research group. In 2012, D. Zou's group from
Peking University reported a highly flexible fiber supercapacitor (Fig. 3a–c) with utilized graphitic pen ink
as electrode materials, one wrapped with non-conductive wire to act as the separator. The two filaments
were then encased in a plastic tube 1.8 mm in diameter and filled with H2SO4, Na2SO4, or PVA–H3PO4
electrolytes, which was the first demonstration in flexibility testing, with devices suitable for many flexible
electronic applications which showed excellent electrochemical properties, operating with good
performance. Unfortunately, the thickness and tubing used in this make these filaments fiber supercapacitors
prohibitive to process on industrial equipment. Meng et al. developed "graphene-fiber" in their previous
work, and electrochemically electrolyzed graphene oxide solution onto the surface, making the core and
sheath covalently bonded to each other (Fig. 3d–f). The fiber stores a magnitude lower than the previously
discussed work but reports higher capacitance per surface area of the yarn, and the yarn is thinner, which
would be practical for micro supercapacitor applications. It is also possible that multiple strands of this fiber
can be plied/ twisted together to increase the capacitance. Ray Baughman's group reported a unique
PEDOT–CNT bi-scrolled yarn made entirely of active material and scrolled with electrolyte (Fig. 3g–i). It
was reported capacitances of 0.5 mF cm-1, and show good electrochemical performances at fast scan rates
and when bent. The yarn is also stitched into a glove and woven into a fabric, and mass loadings of 5.7 mg
of CNT and PEDOT per cm, with thicknesses of 20 mm was reported. Cotton–CNT supercapacitor yarn was
reported (Fig. 3j–l), which was informed by previous works. The authors "dip-coat" cotton yarn into an
SWCNT solution, assemble the yarn into a plastic tube with one electrode wrapped in a separating mesh,
then filled with a PVA–H3PO4 electrolyte. MnO2 is grown on the fiber surface to increase the capacitance of
the device. However, this new CNT–cotton yarn had high capacitance. This is an impressive capacitance for
an energy-storing yarn.

Fig.3

Reduced graphene oxide (RGO)/conducting polymer composite fibers with high interfacial areas were
synthesized. The hollow structures were produced by the released gases during the GO reduction reaction,
contributing to an excellent charge storage capacity of 27.1 µWh cm−2 for the resulting supercapacitors.
Directly fabricating components of energy storage systems on the stretchable fibrous substrate has been
developed. The stretchable supercapacitor is first prepared by winding aligned CNT sheet incorporated with
polyaniline (PANI) onto pre-stretched polydimethylsiloxane (PDMS) wire as an inner electrode, then coated
with a thin layer of gel electrolyte, and enwrapped by another PANI/CNT composite sheet to form an outer
electrode. The electrochemical performances of the stretchable fiber remained almost unchanged at a strain
of up to 300%. Another method for stretchable fiber electronics has recently been upgraded by designing
intrinsically stretchable fiber electrodes and electrolytes. In representative work, intrinsically stretchable
fiber electrodes comprising of interconnected, self-standing 3D Nanostructured conductive PANI/RGO
(reduced graphene oxide) hydrogels are prepared by the self-assembly synthesis and then molded into fiber
electrodes. Two hydrogel fibers coated with gel electrolyte were assembled into a stretchable all gel state
supercapacitor fiber, which can bear the strain up to 40%. In this kind of paradigms, stretchability and
capacity are mainly limited by the conductivity as well as the actual material content of the gel fiber
electrodes.

Supercapacitors in series were constructed on a single elastic fiber based on aligned CNT with tunable
output voltage in a wireless manner. Aligned CNT sheets along the axial direction were separated with equal
intervals and share the same elastic fiber substrate as electrodes. Gel electrolyte was then coated to connect
each separated electrode, forming an integrated in-series connected supercapacitor fiber with tunable
working voltage up to 1000 V.
In recent years, Lithium-ion batteries (LIBs) were successfully made into fiber shapes to fit for flexible
textile electronic devices. Among the few works on fabric or yarn batteries, Kwon et al. demonstrated a
highly flexible lithium-ion battery cable. This multilayered cable also showed good electrochemical
performance which designed similar to a coaxial cable. The electrode materials consisted of Ni–Sn coated
Cu wire for the anode and a graphitic carbon mixed with LiCoO2 and poly-(ethylene terephthalate) cathode
with Al current collector. The electrolyte was a standard 1 M lithium hexafluorophosphate (LiPF6), which
provides the main source of lithium for cathodic intercalation. This is one of the few papers making
headway towards achieving comparable capacities and electrochemical performances to conventional Li-ion
batteries. Unfortunately, relatively complicated procedures are needed to fabricate fiber LIBs. Besides, the
power densities of fiber LIBs are still quite low for practical applications. Compared with LIBs,
supercapacitors offer higher power delivery capability, faster charge/discharge rates, long cycle livers, and
bridging functions for the power-energy gap between traditions dielectric capacitors and batteries. These
features make SCs ideal power suppliers for wearable and textile electronics.

C. Custom weaved and knitted fabrics

Gorgutsa et al. initially reported a fiber capacitor with strands of their yarn woven into a full fabric for
capacitive touch sensing. This fiber capacitor stored energy on par with small ceramic capacitors ideal for
electronic applications like touch sensing, but not larger-scale energy storage. A later paper from the group
describes lithium polymer battery strips (1 × 10 cm) composed of a LiFePO4 cathode and Li4Ti5O12 anode.
The reported strips of battery fabric were woven into a larger fabric (Fig. 4a and b) that incorporated the
anode, cathode, current collectors, and electrolyte into the structure. The devices operate at 3.3 V vs. Li/Li+
and have a specific capacity of 170 mAh g-1 of LiFePO4.

Additionally, unlike their fiber counterparts, it would be difficult to process these battery strips on industrial
machinery. Lastly, this paper demonstrates knitting as a fabrication technique for textile supercapacitors
(Fig. 4c–f). Their ultimate goal is to make textile energy storage devices with comparable capacitance per
area as conventionally large supercapacitors. Thus activated carbon was the choice material. Carbon fiber
yarn into 3 cm × 3 cm patches embedded in larger sheets of wool was knitted and then activated carbon was
screen printed into the carbon fiber "current collectors." The result was a flexible, comparable to an
activated carbon film supercapacitor conductive knit fabric. Also, a polymer electrolyte was employed to
eliminate the possibility of leaking and used no metal components in the system. However, this work still
requires layering two electrodes on top of each other, making for a thicker device. The knitting of
interdigitated electrodes (Fig. 4f) can help to eliminate this problem.

Fig.4
Key metrics of Energy storing textile design and electrochemical performance

a) Device design and its compatibility with clothes

Sandwiched devices would only be optimal for outerwear applications that have sufficient layering and
thickness to accommodate many of the proposed devices. This is where designing a textile from the ground-
up can lead to unified structures that incorporate all the current collecting, electrode, separator, and
electrolyte materials in one piece of fabric. Such materials constructed with jacquard weaves and double
knits present possible solutions to this challenge as they are multilayered textile construction methods, made
as single continuous sheets of fabric.

b) Large-scale manufacturability

Many authors test small devices, meaning that when larger devices are made, their properties and
performance may also change. To help explain the feasibility of their new devices, researchers need to
explain how their manufacturing techniques are scalable, and if possible, demonstrate the testing of larger
devices to confirm their hypotheses.

c) Safety

Toxicity is an issue brought up by many concerned researchers. This primarily depends on the electrolyte
material, as many supercapacitors (TEA-BF4 in acetonitrile) and battery electrolytes (LiPF6 in propylene
carbonate) are toxic and liquid. Several researchers have focused on using non-toxic electrolytes, as well as
non-toxic gel/solid polymer electrolytes, that can also double as the separator.

d) Washing

Polymer coatings may protect wearable devices from moisture, allowing them to be cleaned. Different types
of fabrics and garments are labeled "dry clean only" and require special care. The first generation of
wearable electronics will likely fall into that category of care, and new cleaning protocols will likely need to
be established to ensure that the feel, breathability, and electrical function is retained. In literatures,
washable energy-storing textile was not found, primarily because most of the PVA and water-based gel
electrolytes dissolve in water.

e) Mechanical and flexibility testing

Mechanical testing paired with the electrochemical performance of a fabric demonstrates the real-world
durability of devices and gives readers an idea of how long a garment device may last. This is especially
important for textiles made from energy-storing yarns and fibers to determine if they can be woven or
knitted.

f) Long term cyclability

Ideally, an energy storage device would not need to be replaced, and it may be impossible to do so if it is
integrated into the garment structure. Supercapacitors are promising energy storage devices for this very
reason. Conventional devices are rated for hundreds of thousands of cycles, and often outlast the lifetime of
the equipment they power. Though some applications require higher energy densities, device lifetime will be
one of the most pressing challenges to the development of textile batteries.
Conclusion
This field continues to grow quickly, showing demand for commercially viable devices. These technologies
are complementary to one another, and demonstrating ways to charge smart textiles without having to
"plugin" the garment is an important aspect to consider for the practical applications of wearable energy
storage. Future energy textiles will focus on printed electrodes and the development of energy yarns.
Whether it is from body movements, body heat, or sunlight, integrating energy harvesting and power
generation technologies combined with energy storage systems will also become the next research frontier.
One of the key challenges to the field is creating scalable material systems, and most reports show the
production of only a small amount of materials. If authors could discuss how their process is scalable for
industrial use, it would help to understand the real world implications of their research. Research in textile
energy storage is an exciting field presenting viable solutions for wearable devices in an array of
applications.

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