Materials Today  Volume 18, Number 5  June 2015
Flexible fiber energy storage and
integrated devices: recent progress and
perspectives
Xianfu Wang1, Kai Jiang2,* and Guozhen Shen1,*
1
State Key Laboratory for Superlattices and Microstructures, Institution of Semiconductors, Chinese Academy of Science, Beijing 100083, China
2
Institute & Hospital of Hepatobiliary Surgery, Key Laboratory of Digital Hepatobiliary Surgery of Chinese PLA, Chinese PLA Medical School, Chinese PLA General
Hospital, Beijing 100853, China
Flexible fiber-shaped energy storage devices have been studied and developed intensively over the past
few years to meet the demands of modern electronics in terms of flexibility, weavability and being
lightweight. In this review, fiber electrodes and flexible fiber energy storage devices containing solid-
state supercapacitors (SCs) and lithium-ion batteries (LIBs) are carefully summarized with particular
emphasis on their electrode fabrication, structure design and flexibility. In addition, emerging wire-
shaped integrated energy systems, combined energy storage and solar cells, as well as other electronic
devices to realize self-charging and self-powered integrated systems are specifically highlighted.
Introduction
As two important energy storage devices, supercapacitors (SCs)
[1–3] and lithium-ion batteries (LIBs) [4–7] have attracted consid-
erable interest in recent years and are widely used in our daily lives.
With the development of flexible electronics, such as foldable
displays [8], soft photodetectors [9] and bendable field effect
transistors [10], flexible solid-state SCs and LIBs, which have been
shown to be promising candidates to power portable and flexible
electronic devices, have also been extensively fabricated to satisfy
the demands of being lightweight, flexible, and possessing high
power and energy density [11–21]. However, most of the currently
fabricated flexible SCs and LIBs have appeared in a planar format
with large volume and structure limitations, which may limit their
potential applications in future electronic devices that require
lighter, smaller and omni-directional flexibility [22,23]. To this
end, solid-state SCs and LIBs with fiber shapes reveal unique and
promising properties and drawn great attention in the past few
years. A lot of effort has been made toward developing new
materials and fabricating novel structures with a wire shape to
realize fiber SCs and LIBs with high energy density and omni-
directional flexibility [24–26]. As with conversional flexible energy
storage devices, mechanical robustness is also an important
consideration for fiber-shaped SCs and LIBs. To improve the
*Corresponding authors:. Jiang, K. (jiangk301@126.com), Shen, G. (gzshen@semi.ac.cn)
1369-7021/ß 2015 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/). http://dx.doi.org/10.1016/
j.mattod.2015.01.002
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RESEARCH: Review
mechanical stability, several routes have been explored; including
many flexible substrates containing carbon nanotube (CNT) fibers
and graphene fibers (GFs), binder-free electrodes grown nanostruc-
tured active materials directly on the fibers, and polymer based
packaging materials including polydimethylsiloxane and silicone.
In this review, we will briefly introduce the very recent develop-
ment of fiber-shaped SCs and LIBs with particular focus on the
fabrication of flexible fiber electrodes, and the structural design of
devices. The emerging integrated wire shaped energy system, for
the simultaneous realization of energy conversion and energy
storage, as well as the combination of energy storage with other
electronic devices, will be specially highlighted.
Fiber electrodes
The electrochemical performance of energy storage devices
depends largely on the active materials and electrode structures.
Over the past few decades, a lot of active materials with nanos-
tructures, such as CNTs [27–29], graphene [30–33], metal oxide
[34–37], metal sulfide [38–41] and their composites [42–45], have
been extensively studied as electrodes for SCs and LIBs, most of
which showed favorable properties. Just as with conventional SCs
and LIBs, it is necessary to design and develop novel electrodes
with a wire shape to fabricate wire devices that can store energy.
Accordingly, a lot of nanostructured materials have recently been
made into fiber electrodes for energy storage. The obvious example
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may be CNTs because of their inherent flexibility, lightweight,
extremely high surface area (1600 m2 g 1 for single-walled CNTs)
and high electrical conductivity of 105 S cm 1 [46]. When CNTs
are assembled into continuous fibers in which CNTs are highly
aligned, excellent mechanical properties, much stronger and stif-
fer than various engineering fibers can be achieved, and the
conductivity can reach a level of 103 S cm 1 [47], permitting use
as electrodes for dye-sensitized solar cells [48,49] or as promising
electromechanical actuators with the conversion of electrical en-
ergy into mechanical energy [50]. Figure 1a shows a SEM image of
RESEARCH: Review
an aligned CNT fiber with a uniform diameter of 60 mm. The CNT
fibers are lightweight, flexible, strong (tensile strength of 102–
103 MPa) and conductive (electrical conductivity of 102–
103 S cm 1). In 2012, Guo et al. fabricated a CNT fiber by first
synthesizing CNTs using a chemical vapor deposition method
followed with a spin-drawing process [51]. The CNT fiber can
produce a stress over 100 times that of the strongest natural
skeletal muscle with high reversibility, good stability, high work
density, extremely low functioning electric field, and application
to various media. However, the CNT fiber electrodes showed low
capacities when used as the electrodes for fiber energy storage
devices. To this end, some conjugated polymers such as polyani-
line (PANI) nanowire arrays [52] have been introduced onto the
surface of the CNT fibers to improve the electrochemical perfor-
mance of the corresponding fiber energy storage devices (Fig. 1b
FIGURE 1
SEM images of fiber electrodes: (a) CNT fiber. Reprinted with permission
from Ref. [49]. Copyright 2013, American Chemical Society. (b and c)
CNT@PANI composite yarn. Reprinted with permission from Ref. [52].
Copyright 2013, Wiley. (d) GF@3D graphene framework. Reprinted with
permission from Ref. [62]. Copyright 2013, Wiley. (e) RGO@CMC fiber.
Reprinted with permission from Ref. [64]. Copyright 2014, Macmillan
Publishers Limited. (f ) ZnCo2O4 nanowires on carbon fiber. Reprinted with
permission from Ref. [65]. Copyright 2013, Wiley.
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Materials Today  Volume 18, Number 5  June 2015
and c). For example, the capacitance of pure CNT yarn-based SCs is
only 2.3 mF cm 2. However, after being composited with PANI
nanowire arrays, the fiber SC showed a capacitance of 38 mF cm 2,
representing a 16-fold improvement [52]. Meanwhile, some other
fiber electrodes based on CNT fiber and metal oxide, such as CNT
fiber/MnO2 [53,54], CNT fiber/TiO2 [55], CNT/LiMn2O4 yarn [56],
CNT/Li4Ti5O12 yarn [57], CNT/Fe3O4 composite fiber [58], were
also fabricated, which can be used as electrodes for fiber-shaped
SCs, LIBs and solar cells.
GF, with high strength, electrical and thermal conductivities,
represents the other novel type of fiber electrode of practical
importance. GF not only possess the common characteristics of
fibers, such as the mechanical flexibility for textiles, but also
provides unique properties such as low cost, lightweight and ease
of functionalization in comparison with conventional carbon
fibers [59–61]. However, the successful fabrication of GF has only
become a reality because of the challenge of assembling two-
dimensional graphene sheets in a fiber structure. Recently, Dong
et al. developed a facile one-step dimensionally confined hydro-
thermal strategy to fabricate neat graphene fibers from cost-effi-
cient aqueous graphite oxide (GO) suspensions [61]. On the basis
of this work, graphene core-sheath fibers, in which a core of GF is
covered with a sheath of 3D porous network-like graphene frame-
work (Fig. 1d), was further fabricated [62]. This hybrid fiber elec-
trode can simultaneously use the high electronic conduction of
the core GF and the highly exposed surface areas of a 3D graphene
network, which can be used as flexible electrodes for fiber-based
electrochemical SCs. As with CNT composite fibers, other hybrid
electrodes based on GF were also studied to improve their perfor-
mance. For example, bismuth oxide nanotubes were combined
with GF as an additional electrochemical component to enhance
the capacitance of wet-spun GF based SCs [63]. Very recently, Kou
et al. proposed a coaxial wet-spinning assembly approach to
continuously spin sodium carboxymethyl cellulose (CMC)-
wrapped graphene core-sheath fibers [64]. The as-fabricated com-
posite fibers can be used directly as safe electrodes to assemble yarn
SCs because CMC is an ionically conductive while electrically
insulative polyelectrolyte.
In addition to CNT fibers, GFs that assembled by themselves and
their composite fiber electrodes, another method of fabricating
wire electrodes is to directly grow active materials on the fiber
conductive current collectors. Carbon fiber, nickel fiber and tita-
nium fiber are the common fiber conductive substrates, and the
metal oxide such as ZnCo2O4, NiCo2O4, Co3O4 and Ni(OH)2 [65–68]
are usually used as the active materials for energy storage. Figure 1f
shows an SEM image of a fiber electrode based on a ZnCo2O4
nanowire array grown on carbon fiber [65]. The as-synthesized
electrode exhibits high flexibility, and can also use both the high
conductivity of carbon fiber and the high active surface of the three-
dimensional ZnCo2O4 nanowire array, which are favorable to en-
hance the electrochemical properties when used as the electrodes
for fiber energy storage devices.
Many fiber electrodes have been successfully developed. To
realize fiber energy storage devices with high capacities and high
mechanical robustness, flexible binder-free composite fiber elec-
trodes using nanostructured metal oxide as active materials, CNT
fibers and GFs as substrates are promising choices. Of course, more
effort is needed in searching for new structured active materials
Materials Today  Volume 18, Number 5  June 2015
with high electron conductivity, high electrochemical sites and
novel fiber current collectors with strong mechanical stability
and ultra-high flexibility to develop fiber-shaped flexible energy
storage devices and wire-based integrated energy systems with
excellent performances.
Flexible fiber SCs
Fiber SCs have drawn great attention in the past few years. Com-
pared with conventional solid-state SCs appearing in planar for-
mat, fiber SCs exhibit some unique benefits in terms of flexibility,
lightweight and structural varieties. Excitingly, they also show
large specific volume power density that the planar SCs cannot
reach. For fiber SCs, the structures are numerous and a lot of effort
has been made on designing novel constructions of devices. One
simple design consists simply of placing two fiber electrodes
coated with gel electrolyte in parallel, with a space, on a flexible
substrate. For instance, a fiber SC was fabricated by using two
poly(3,4-ethylenedioxythiophene) (PEDOT) coated MWNTs yarn
threads as electrodes [69]. The yarn SC had an average power
density of 40 W cm 3, which is about four times higher than that
for commercial 25 mF SCs. It is easy to imagine that the number of
electrodes is a crucial factor affecting the performance of the fiber
SC. To study the distributed-capacitance effect caused by the num-
ber of electrodes, Liu et al. fabricated fiber SCs using electrodes based
on ZnCo2O4 nanowire array/carbon fiber, with different numbers in
parallel [65]. Figure 2a and b shows the schematic illustration of a
fiber SC with four electrodes and a photograph of a device with
fourteen composite fibers. They found that the specific capacitances
FIGURE 2
Planar-shaped fiber SCs. (a) Schematic illustration and (b) photograph of a
fiber SC based on ZnCo2O4 nanowires. Reprinted with permission from Ref.
[65]. Copyright 2013, Wiley. (c–f ) Assembly of multiple microfibers in micro-
SCs and their performance. Reprinted with permission from Ref. [71].
Copyright 2014, Macmillan Publishers Limited.
RESEARCH
present a significant rising trend with increased fiber number due
to the interaction among the nonadjacent opposite fiber electrodes.
The same phenomenon was also demonstrated with fiber SCs
based on MnO2/carbon fiber electrodes and hierarchically struc-
tured carbon microfiber electrodes made of a single-walled carbon
nanotube (SWNT)/nitrogen-doped rGO sheet [70,71].
The other feature of fiber SCs with this construction is that it is
easy to integrate the single fiber SC in series, or in parallel, which
can enhance the current and potential to meet the power and
energy requirements for practical microelectronics. Recently,
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SWNTs and carbon composite yarn were fabricated by carbonizing
SWNT and chitosan (CHI) fiber obtained by a wet-spinning meth-
od [72]. The flexible and all-carbon based yarn micro-SCs based on
the SWNT@C composite yarn can be operated well in the potential
range between 0.0 and 0.8 V using PVA–H2SO4 as the electrolyte.
When four yarn SCs were assembled in parallel, the output current
can be increased four times. For the four devices in series assembly,
the voltage can be increased to 3.2 V. Very recently, wet-spun
SWNT/rGO fibers were also developed as electrodes for flexible
fiber SCs with a potential of 0.0 – 1.0 V based on PVA–H3PO4 gel
electrolyte. The device connected three fiber SCs in series and
exhibited a 3 V potential window (Fig. 2c and d). The current of the
parallel micro-SC assembly increased by a factor of three and its
discharge time is three times that of a single fiber SC when
operated at the same current density (Fig. 2e and f).
Although the above mentioned SCs exhibit many merits, rigor-
ously, they are not true fiber SCs because the planar substrates are
commonly used as a support. Real fiber SCs should be presented as
a single wire architecture. Recently, a flexible fiber SC was explored
by assembling two nickel fiber/NiCo2O4 nanosheet fibers with one
wound around the other and a PVA–KOH gel electrolyte filling in
the middle (Fig. 3a) [66]. The electrochemical performance can be
FIGURE 3
Flexible fiber SCs: (a) photos of fiber SCs and (b) CV curves at 80 mV/s in
straight and bending states, respectively. Reprinted with permission from
Ref. [66]. Copyright 2014, Elsevier Ltd. Cable-type SCs: (c) schematic
diagram and (d) bending text of a coaxial SC cable based on
CuO@AuPd@MnO2 NWs electrode. Reprinted with permission from Ref. [75].
Copyright 2014, Wiley.
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 RESEARCH Materials Today  Volume 18, Number 5  June 2015

maintained even when bent because of the unique structure, being

similar to a spring (Fig. 3b). However, it can be imagined that the
get electrolyte might be destroyed and the two electrodes might
separate from each other during bending due to the stress between
the metal current collectors. Therefore, optimized structures
should be made to increase the mechanical stability.
To enhance the mechanical stability of fiber SCs, cable-type SCs
using plastic fiber and carbon fiber instead of metal fiber to support
the active materials have been developed [73,74]. Cable-type fiber
SCs based on commercial pen ink coated on plastic fiber showed an
RESEARCH: Review

area capacitance of 11.9–19.5 mF cm 2 and can be bent to a degree

of 3608 exhibiting high flexibility [73]. Using PPy-MnO2/SWCNTs
on carbon fibers as electrodes, fiber SCs also exhibited excellent
mechanical stability [74]. The shortcoming of this construction is
that the two parallel aligned electrodes go against the most effi-
cient use of the active materials, resulting in a low capacitance.
Therefore, architectures that use active materials to their maxi-
mum level should be developed. To this end, a novel type fiber SC
with coaxial structure possessing the highest contact area between
active materials has drawn tremendous interest. Yu et al. designed
a coaxial SC using CuO@AuPd@MnO2 core–shell nanowhiskers
grown on copper wire and foil as inner and outer electrodes,
respectively (Fig. 3c) [75]. The as-fabricated coaxial SCs can take
full advantage of both the inner and outer active materials, thus
providing many more electrochemically active sites for the revers-
ible redox reactions. Importantly, high flexibility was also exhib-
ited and electrochemical performance could be well retained when
tested under different bending angles, ranging from 08 to 1808
(Fig. 3d). To further enhance the mechanical stability, elastic fiber
and MWCNTs fiber were applied to replace the metal wire and
CNT sheets as well as CNF film were used to substitute copper foil
[76,77]. For instance, a fiber stretchable coaxial SC was developed by
using elastic fiber as the support and aligned CNT sheets wrapped on
an elastic fiber as two electrodes. Both of the support and active
materials are high flexible and stretchable which render the as-
fabricated device to be operated under a strain of 75% without
obvious structural damage and performance degradation [76].
In the development of flexible fiber SCs, lightweight is also a
crucial objective that should be pursued. However, the used of
supports in fiber SCs is always an addition to the whole weight of
devices whether they are metal fibers, elastic fibers or carbon fibers.
Therefore, a lot of work has been put into developing self-sup-
ported fiber electrodes which can be used as both support and
active electrodes, thus reduce the device weight a large extent
[53,62,78]. For example, GF@3D-G electrodes were fabricated as
all-graphene core-sheath microfibers for fibriform SCs (Fig. 4a).
The device was assembled by two intertwined GF@3D-G electrodes
solidified in a PVA–H2SO4 gel electrolyte without any other addi-
tions exhibiting excellent flexibility (Fig. 4b) [62]. Fiber SCs based
on self-supported CNT/MnO2 composite yarn was also studied
without obvious performance degradation after 1000 bending
cycles [53]. Meanwhile, coaxial SC using CNT fibers and CNT
sheets as self-supported electrodes have also been designed with
a maximum discharge capacitance of 32.09 F cm 3, much higher
than that of fiber devices consisting of two twisted CNT fibers [79].
As mentioned above, to meet the energy requirement for prac-
tical microelectronics, assembling SCs in series to increase the
operating voltage is an efficient method, outside of improving the
FIGURE 4
Twisted fiber SCs: (a) Schematic illustration and (b) charge–discharge curves
of a symmetric GF@3D-G fiber SC. Reprinted with permission from Ref. [62].
Copyright 2013, Wiley. (c) Optical image of CNT/MnO2 composite yarn
(CMY) electrodes and (d) bending test of the SC fabricated using two CMY
electrodes. Reprinted with permission from Ref. [53]. Copyright 2014, Wiley.
(e) Photograph and (f ) CV curves of the asymmetric fiber SC based on
Co3O4 NWs and graphene. Reprinted with permission from Ref. [67].
Copyright 2014, Wiley.
capacitance of the electrodes. For fiber SCs, connecting devices in
series is a common method to improve the operating voltage.
However, the large volume of devices in series poses a thorny
problem. The other promising alternative to increase the cell
voltage is to develop asymmetric SCs consisted of a battery-type
Faradic electrode as an energy source and a capacitor-type elec-
trode as a power source, which have the advantages of both SCs
and advanced batteries [23]. Recently, asymmetric fiber SCs using
aqueous electrolytes have been successfully explored. Using Co3O4
nanowires grown on nickel fiber as the cathode and graphene
coated on carbon fibers as the anode, Wang et al. fabricated a
flexible fiber asymmetric SC (Fig. 4e) which can be operated well in
the potential window of 0.0–1.5 V (Fig. 4f) [67]. The energy storage
and power delivery increased at least by 1860% compared with the
device operated in voltage between 0.0 and 0.6 V. Other asym-
metric fiber SCs based on CNT–MnO2//CNT yarn and Ni(OH)2
nanowires fiber//ordered mesoporous carbon fiber have also been
explored and can be tested in the potential range of 0.0–2.0 V and
0.0–1.5 V, respectively [53,68]. Both of them exhibited high me-
chanical stability and could be operated well under bending.
In this section, flexible fiber SCs containing planar-shaped,
cable-type, twisted and coaxial type fiber SCs are systematically
summarized, among which, coaxial architecture show better me-
chanical stability. By contrast, to improve the stored energy,
flexible fiber-shaped asymmetric SCs provide an alternative way
to meet the demands of electronic devices.

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Materials Today  Volume 18, Number 5  June 2015 RESEARCH

Flexible fiber LIBs

Along with the development of flexible planar LIBs, increasing
interest has recently been devoted to exploring flexible fiber-
shaped LIBs to power rapidly developing portable and miniature
electronic devices. Until now, several works on fibriform half-cell
using lithium fiber as counter electrode have been demonstrated.
Using MWCNT/Si composite fiber that can effectively and simul-
taneously exploit the high specific capacity of the silicon and high
electrical conductivity of the MWCNTs as an electrode, a fiber
half-cell has been demonstrated. Figure 5a shows the schematic

RESEARCH: Review
of an as-assembled cell formed by twisting the composite fiber as
the working electrode and lithium wire as the counter electrode
[80]. Besides, CNT@a-Si yarn has also been designed (Fig. 5b) to
serve as a fiber electrode [81]. The fiber cell demonstrated high
first charge and discharge capacities of 2440 and 2200 mAh/g
with coulombic efficiency of 90% at a rate of C/5 in the potential
range of 0.1–1.0 V versus Li+/Li (Fig. 5c). Other composite fibers
formed by combining CNT fiber with metal oxides have also
been developed to fabricate fiber batteries. For instance, Ren
et al. designed a microbattery by using composite fiber incorpo-
rated MnO2 nanoparticles into the MWCNT fiber as a positive
electrode and the construction is illustrated in Fig. 5d [82]. The
microbattery achieved a specific capacity of 218.32 mAh/g at a
current of 5  10 4 mA.
To enhance the flexibility and practical application of fiber
batteries, an alternative approach is to develop novel fiber electro-
des to replace lithium wire. Therefore, significant effort should be
FIGURE 6
invested in designing fiber-shaped full batteries with excellent Fiber full LIBs. (a) Side view and (b) electrochemical performance under
flexibility. In 2012, a cable-type full battery was fabricated by bending state of a cable battery. Reprinted with permission from Ref. [83].
using a hollow spiral, spring-like anode (comprising nickel/tin- Copyright 2012, Wiley. (e and f ) Performance of a fiber cell based on (c)
coated copper wires), LiCoO2 cathode, and a modified polyethyl- CNT-Si and (d) CNT-LMO composite yarn. Reprinted with permission from
ene terephthalate (PET) nanowoven separator membrane [83,84]. Ref. [56]. Copyright 2014, American Chemical Society. (g and h) Photograph
and (i) charge–discharge curves of a fiber battery assembled using
Figure 6a shows the cross-sectional structure of the cable- MWCNT/LTO and MWCNT/LMO composite yarn electrodes. Reprinted with
type battery. When tested under bending states, the variation of permission from Ref. [57]. Copyright 2014, Wiley.

discharge properties is negligible indicating the high mechanical

FIGURE 5
Fiber half-cells. (a) Schematic illustration of MWCNT/Si composite fiber-
based cell. Reprinted with permission from Ref. [80]. Copyright 2014, Wiley.
(b) Schematic and SEM image and (c) electrochemical performances of
CNT@a-Si composite yarns. Reprinted with permission from Ref. [81].
Copyright 2013, Elsevier Ltd. (d) Schematic illustration of a half-cell based
on MWCNT/MnO2 composite fiber. Reprinted with permission from Ref. [82].
Copyright 2013, Wiley.
stability (Fig. 6b). Very recently, a CNT/LiMn2O4 yarn was synthe-
sized by directly depositing LiMn2O4 particles onto the aligned
CNT sheet followed by a scrolling process [56]. Using CNT/Si fiber
and CNT/LiMn2O4 yarn as the anode and cathode (Fig. 6c and d), a
fiber full battery was fabricated with an average voltage of 3.4 V
(Fig. 6e). The capacity retained 87% after 100 cycles (Fig. 6f) showing
the excellent cycling stability. Using a similar method, fiber full
batteries were also fabricated from CNT/Li4Ti5O12 yarn and CNT/
LiMn2O4 yarn [57]. The wire-shaped battery was flexible and could
be deformed into various shapes without physical damage (Fig. 6g
and h) and with negligible performance loss even after bending
1000 times (Fig. 6i). Excitingly, high stretchability was also demon-
strated when the battery was fabricated on an elastic substrate,
revealing its potential applications in stretchable electronics.
The challenge of developing fiber LIBs is the design of fiber
electrodes, especially the cathode, which are commonly coated on
some fiber substrates that may suffer from weak contact and high
internal resistance. Therefore, fiber cathodes that are directly
grown on flexible fiber current collectors are still needed. Further-
more, soft packaging materials are also desired to fabricate fully
flexible fiber LIBs.

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 RESEARCH
Flexible fiber integrated energy system
Integrated energy systems have been studied extensively as a
promising direction in recent years. Actually, a complete energy
system should contain energy conversion (solar cells, nanogen-
erator, among others), energy storage (LIBs, SCs, among others)
and the powering of some sensors (photodetectors, pressure sen-
sors, magnetic sensors and so on). However, because of the com-
plex fabrication involved in realizing integration and the
challenges of achieving multiple functions, until now, only a
few simple integrated energy devices that just simultaneously
RESEARCH: Review
realize both energy conversion and energy storage, or as the power
source for other electronic devices, such as photodetectors and
sensors, have been successfully explored [23,67]. In the past few
years, integrated energy system with planar structures, such as self-
charged LIBs [85,86], self-charged SCs [87,88], LIBs or SC powered
photodetectors [89,90], and smart windows [91–93], have been
successfully designed and demonstrated. As for integrated energy
systems with a fiber structure, the simplest integration may be
connecting fiber energy storage devices with other electronics by
the wires. For example, fiber SCs can be charged by a conventional
silicon solar cell (Fig. 7a), and can also be used to power a light-
emitting diode (LED) (Fig. 7b) [72]. Besides, fiber SCs can also serve
as the power for photodetectors [71,90]. Figure 7c shows the
schematic of a SC powered TiO2 based photodetector [71]. Using
the integrated micro SC as the external power source, the photo-
detector has a steady response to ultraviolet light irradiation with
wavelength of 254 nm.
To realize true fiber-shaped integrated energy system, all parts of
the devices should be fabricated into a fiber structure. In other
words, all parts including energy conversion, energy storage and
sensors should be achieved on a single fiber. In 2012, an integrated
energy wire simultaneously realizing both photoelectric conver-
sion and energy storage was developed. In this system, titanium
wire was coated with photoactive materials for photoelectric
conversion in one part and a gel electrolyte for energy storage
FIGURE 7
Integrated fiber energy system connected using wires. (a) Solar cells
charging for the yarn micro-SCs which can power a red light-emitting
diode (b). Reprinted with permission from Ref. [72]. Copyright 2014, Wiley.
(c) Schematic of a self-powered photodetector powered by a fiber micro-SC
and (d) the photoresponse of the nanosystem. Reprinted with permission
from Ref. [71]. Copyright 2014, Macmillan Publishers Limited.
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Materials Today  Volume 18, Number 5  June 2015
in another part. Then aligned CNT fibers were twisted with both
parts to form the self-charging energy system with an overall
photoelectric conversion and storage efficiency of 1.5% [94].
Following with that, a much higher overall energy conversion
efficiency of 2.1% was obtained by integrating energy wire with
PANI//PANI and PANI//TiO2 coated on stainless steel wire as SC
and dye-sensitized solar cell [95]. For the integrated fiber energy
system based on solar cells and electrochemical SCs, recently, a
coaxial construction was designed. Figure 8a shows the schematic
of the system where a polymer solar cell based on P3HT:PCBM was
fabricated on one part of a titanium oxide nanotube-modified
titanium wire, and SC was made from MWCNT sheets attached on
other part [96]. The SC can be fast charged to 0.4 V in a short time,
demonstrating a high energy conversion efficiency (Fig. 8b).
Two devices on one fiber to realize two different functions is
common to the integrated energy systems mentioned above. Very
recently, devices on a single fiber to achieve different roles have
designed [67,97]. A fiber device was fabricated by twisting titanium
wire modified with titanium dioxide nanotubes and CNT fibers,
followed with the incorporation of a redox electrolyte containing
an I3 /I redox ion couple (Fig. 8c) [97]. Under illumination, the
device serves as a dye-sensitized solar cell to convert solar energy to
electric energy (Fig. 8c1), while it can also function as an electric
double-layer capacitor to store the electric energy when a direct
current is connected to the two electrodes (Fig. 8c2).
FIGURE 8
Integrated energy system on a fiber. (a) Schematic diagram and (b) charging–
discharging curve of a self-charged fiber SC. Reprinted with permission from
Ref. [96]. Copyright 2014, Wiley. (c) Structure and working mechanism of the
wire-shaped energy device to realize energy conversion and storage
simultaneously. Reprinted with permission from Ref. [97]. Copyright 2014,
Wiley. (d) Photographs of flexible fiber self-powered system. (e) Schematic
illustration and (f) current response of the integrated energy fiber. Reprinted
with permission from Ref. [67]. Copyright 2014, Wiley.
Materials Today  Volume 18, Number 5  June 2015 RESEARCH

TABLE 1
Summary of flexible fiber energy storage devices discussed in this review.
Fiber Fiber Assembled Capacities Flexibility Ref
devices electrodes method
Fiber SCs PEDOT coated MWNTs yarn In parallel Can be weaved into a glove [69]
3 3
SWNT/rGO fibers In parallel 45.0 F cm at 26.7 mA cm Retains more than 97% after [71]
bending 1000 times
SWNT@C yarn In parallel 37.1 mF cm 2 at 0.05 mA cm 2
Can be bended [72]
CNT/MnO2 composite yarn Twisted 25.4 F cm 3 at 10 mV/s No significant capacitance drop [53]
after 1000 bending cycles

RESEARCH: Review
GF@3D-G Twisted 30–40 mF at 2 mA Can be bended and made into [62]
spring
2 2
RGO@CMC Coaxial 127 mF cm at 0.1 mA cm Up to 111% at 1000 times of [64]
bending
3
Nickel fiber/NiCo2O4 nanosheets Coaxial 10.3 F cm at 0.08 mA Over 90% retention after 500 [66]
bending cycles
CuO@AuPd@MnO2 NWs Coaxial Remained at 93.4% after folding at [75]
1808 for 100 times
1 1
CNT nanosheets Coaxial 19.2 F g at 0.1 A g Maintained more than 95% after [76]
stretched 100 cycles at a strain of
75%
2 2
CNF film Coaxial 71.1 mF cm at 0.38 mA cm Not changed much up to 1808 [77]
bending
3 7
CNT fiber and sheet Coaxial 32.09 F cm at 1.00  10 A Maintained by 97.2% after bending [79]
at 1808 for over 100 cycles
Pen ink Cable-type 19.5 mF cm 2 at 0.083 mA cm 2 Can be bent to 3608 [73]
PPy-MnO2/SWCNTs Cable-type 1.49 F cm 2 at a 1 mV s 1 Little influence at bending states [74]
Co3O4 nanowires Asymmetric 1.59 F cm 3 at 40 mA cm 3 Can be bent into different states [67]
Ni(OH)2-nanowire Asymmetric 35.67 mF cm 2 at the current of 0.1 mA Can be severe bending [68]
Fiber LIBs CNT@a-Si yarn Half-cell First discharge capacity of 2200 mAh/g at C/5 [81]
MnO2/MWCNT fiber Half-cell 218.32 mAh/g at a current of 5  10 4 mA [82]
Nickel/tin-coated copper//LiCoO2 Full-cell 1 mAh cm 1 at 0.1 C High mechanical stability [83]
CNT/Si fiber//CNT/LiMn2O4 yarn Full-cell 106.5 mAh g 1 at 1 C Can be woven into a textile [56]
CNT/Li4Ti5O12 yarn//CNT/LiMn2O4 yarn Full-cell 138 mAh g 1 at 0.01 mA High stretchability [57]

In addition, very recently a single fiber device which can act as
both SC and photodetector, was successfully designed and real-
ized. In the fiber integrated system, Co3O4 nanowires grown on
titanium wire acted as the cathode, and graphene coated on
carbon fibers served as both the anode and photo-sensitive mate-
rial [67]. Figure 8d shows the as-fabricated fiber device with
different bending states, revealing its excellent mechanical stabili-
ty. Using PVA–KOH as gel electrolyte and separator, the device can
function as an asymmetric SC. When under illumination, the
leakage current of the device will increase due to the enhanced
ion transport driven by the charge resulting from the light
(Fig. 8e). Therefore, a photodetector can be realized at the same
time by monitoring the leakage current under illumination and
dark (Fig. 8f). Compared with traditional integrated power sys-
tems, these integrated energy wires are flexible, lightweight and
suitable for special applications.
These fiber integrated devices can either achieve self-charging
by assembling solar cells with SCs, or realize both energy storage
and photodetecting, which contribute greatly to the development
of fiber integrated energy systems.
Conclusion
Flexible fiber energy storage devices including electrochemical
capacitors and LIBs, as well as integrated wire-shaped energy
systems that have arisen in the past several years have been
summarized systematically, with special emphasis on the design
of fiber electrodes, structure construction, electrochemical prop-
erties and mechanical stability of the whole devices, as summa-
rized in Table 1. Although lots of fiber energy storage devices have
been developed with acceptable overall performance, some short-
comings and challenges still exist which need to be overcome. For
example, most of the current fiber electrodes for electrochemical
capacitors are carbon-based materials, such as MWCNT fibers, GF
and CNT/graphene composite fiber, causing the relative low ca-
pacities of devices, no matter of their high inherent flexibility and
high electrical conductivity. To this end, composite fiber electro-
des based on CNT fibers and GFs combined with other nanostruc-
tured metal oxide should be extensively explored to take full
advantage of both the excellent mechanical properties, high con-
ductivity of CNTs or GFs and high capacities of metal oxides. By
contrast, studies on fiber electrodes for wire-shaped LIBs are not
going well, except for CNT/Si fibers, CNT/LiMn2O4 yarn and CNT/
Li4Ti5O12 yarn. Therefore, flexible fiber electrodes with superior
conductivity and high capacities for wire-based LIBs require more
attention.
In addition to exploring fiber electrodes with high capacities,
designing novel structures that can make full use of the active
materials is a promising alternative way to improve the capacities
of fiber energy storage devices. For instance, coaxial architecture is
a good choice that can take full advantage of both inner electrodes
and outer electrodes to enhance the effective electrochemical
surface. Until now, coaxial SCs on a fiber have been fabricated,

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