Review

Flexible Electrodes www.advancedscience.com

Paper-Based Electrodes for Flexible Energy Storage Devices

Bin Yao, Jing Zhang, Tianyi Kou, Yu Song, Tianyu Liu, and Yat Li*

substrates have obvious drawbacks. The

Paper-based materials are emerging as a new category of advanced electrodes large mass densities of electrochemically
for flexible energy storage devices, including supercapacitors, Li-ion batteries, inactive metals considerably increase the
Li-S batteries, Li-oxygen batteries. This review summarizes recent advances in total device weight. Additionally, they
the synthesis of paper-based electrodes, including paper-supported elec- can be readily oxidized and cause sig-
trodes and paper-like electrodes. Their structural features, electrochemical nificant drop of electrical conductivity.
For the flexible plastic substrates, the
performances and implementation as electrodes for flexible energy storage
weak affinity between active materials
devices including supercapacitors and batteries are highlighted and com- and plastic substrates often leads to the
pared. Finally, we also discuss the challenges and opportunity of paper-based detachment of active materials during
electrodes and energy storage devices. the electrode deformation induced by
cycling, which greatly limits their dura-
bility.[28–31] Therefore, development of
1. Introduction novel and reliable flexible electrodes is urgent and highly
desirable.[12–14,32,33]
Flexible electronics have attracted extensive attention due to Paper, as one of the most ancient flexible products invented
their potential for future hand-held, potable consumer and 2000 years ago and is still used today for information recording
wearable electronics. Electronic or optoelectronic components and packing, is one of the promising alternatives to con-
on flexible substrates enable novel applications, such as flex- ventional flexible substrates.[30] Since 1960s, paper has been
ible display, electronic textile, artificial electronic skin, distrib- researched and employed as substrates for a diverse array of
uted sensors, etc.[1–9] Whilst various flexible electronics are electronics, namely paper electronics,[34] including displays,[35]
commercially available nowadays, the development of flexible sensors,[36,37] transistors,[38] radiofrequency identification
energy and power sources for these devices is slow.[10,11] Such a devices,[39] generators,[40,41] light-emitting diodes,[42] etc. Papers
“rate-limiting step” has greatly impeded the commercialization are promising electrode materials because of their wide avail-
of these electronics. In order to overcome this limiting factor, ability, low cost, light weight, environmental friendliness,
extensive efforts have been devoted to make flexible and high recyclability and bendability.[14,34,43–46] Typical paper electrodes
performance energy storage devices.[12–19] are made by depositing or growing active materials onto tra-
Among all flexible energy storage devices, supercapacitors ditional papers. But due to their poor electrical conductivities
and Li-based batteries (e.g., Li-ion, Li-S and Li-O2 batteries) (1011–1015 Ω sq−1),[34] additional chemical modifications (e.g.,
stand out because of their ease of fabrication, compatibility coating conductive layers for example) are required to make
with other electronic devices and excellent electrochemical them electrically conductive.[12,14,47,48]
performance.[17,20–24] They are typically composed of two elec- Alternatively, a variety of other electrically conductive mate-
trodes (cathode and anode), separator, current collector, elec- rials have been assembled into paper-like film structures.[49–51]
trolyte and packing materials.[20,25–27] The two electrodes are These materials, mainly including carbon-based materials
the essential parts that render high flexibility of the devices. such as carbon nanotube, graphene, and carbon fibers, can be
Traditionally, metal foils (e.g., Cu, Al and Ti foils)[28–30] and directly fabricated into self-supporting paper-like electrodes.
certain plastics (e.g., polyethylene terephthalate)[31] are used Paper-like electrodes not only inherit the superior flexibility
as substrates for making flexible electrodes. However, these from paper-supported electrodes, but also exhibit outstanding
electrochemical performances as the electrode materials are
electrochemically active. In light of the ultra-small electrical
resistance and volume, these paper-like electrodes are prom-
B. Yao, Dr. J. Zhang, T. Y. Kou, Y. Song, T. Y. Liu, Prof. Y. Li ising materials that could achieve ultra-high power density and
Department of Chemistry and Biochemistry
University of California energy density simultaneously.
Santa Cruz, California 95064, United States In this review, we will present the recent advances in syn-
E-mail: [email protected] thesis, characterization and applications of paper-based elec-
© 2017 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, trodes, including both paper-supported electrodes and paper-
Weinheim. This is an open access article under the terms of the Creative like electrodes. Specifically, we will begin with the introduction
Commons Attribution License, which permits use, distribution and on research progress of paper-supported electrodes (Section 2),
reproduction in any medium, provided the original work is properly cited.
which are fabricated by applying active materials onto cel-
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/advs.201700107. lulose papers. Then paper-like electrodes will be discussed in
Section 3, including graphene-based, carbon nanotubes-based,
DOI: 10.1002/advs.201700107 carbon fiber-based and carbon-free paper-like electrodes, which

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are fabricated via the controlled assembly of active materials

into free-standing film structures. Section 4 will focus on the Bin Yao received his B.S. and
applications of these paper-based electrodes for diverse energy M.S. in materials science
storage devices including supercapacitors, Li-ion batteries, Li-S from Wuhan University of
batteries and Li-O2 batteries with an emphasis on the first two Technology (WUT), China.
devices. Conclusions, comments and outlooks will be given in During 2012–2015, he was
the last section (Section 5). a visiting student in Wuhan
National Laboratory for
Optoelectronics (WNLO) and
Huazhong University of Science
2. Paper-Supported Electrodes
and Technology (HUST). He
Paper, which is made of randomly interconnected cellulose is currently a Ph.D. student
fibers, is a product after a three-step treatment of wood cel- in chemistry at University of
lulose pulp suspension: dewatering, pressing and heating. California, Santa Cruz under the supervision of Prof. Yat Li.
Mineral fillers, such as calcium carbonate, chalk and clay, are His research interest includes flexible energy storage and
usually mixed with the cellulose pulps to increase smoothness. conversion devices based on metal oxides and nitrides.
To enhance the brightness of paper, fluorescent whitening
agents (e.g. stilbenes) are added in the process of fabrica- Yat Li received his B.S. and
tion. The mechanical properties of paper can be readily tuned Ph.D. in chemistry from the
by adjusting the length, diameter and physical and chemical University of Hong Kong.
nature of cellulose fibers used for production. In general, He was a postdoctoral research
papers made of longer and wider fibers are more robust than fellow at Harvard University
counterparts composed of shorter and thinner fibers.[34] Var- from 2003 to 2007 under the
ious types of papers with different purposes (daily-use office supervision of Prof. Charles M.
photocopying paper, weighting paper, filter paper, Kimwipes Lieber. He joined the University
paper etc.) are widely used in daily lives. Besides mechanical of California, Santa Cruz in
properties, paper’s optical properties can also be changed. It 2007 and is now an associate
has been reported that by filling inter-fiber space using trans- professor of chemistry. His
parent materials (e.g., wax) with reflective constant that is research focuses on the design
closed to the cellulose (≈1.5), it is able to fabricate transparent and synthesis of semiconductor nanostructures, investiga-
papers.[34] Reducing the diameter of cellulose fibers from tion of their fundamental properties, and exploration of their
micro-meters (≈20 µm) to nanometers (≈20 nm) will increase potential for energy conversion and storage.
paper transparency.[52–54]
Each paper fiber possesses a hierarchical structure as shown
in Figure 1. The surface layer of each fiber, which has a thick-
ness of 1–8 µm, is made of small fibrils bundled together. Each 2.1. Electrode Fabrication
fibril is composed of small microfibril bundles with a diameter
between 3 and 20 nm. Two regions exist in every microfibril: Figure 2 summarizes four main protocols of making paper-
the amorphous regions and the crystalline regions. Hemicel- supported electrodes. (1) Pencil-drawing or printing method.
lulose and lignin fill in the amorphous regions. In the crystal- A thin layer of graphite or other conductive materials is first
line regions, there are thousands of 5 µm long cellulose chains. deposited onto the paper surface, followed by electrodeposition
Cellulose fibers interconnect and weave altogether to form the of other active materials (Figure 2a); (2) Soaking and polymeri-
paper. The typical thickness and areal mass density of a paper zation method. Paper is coated with conducting polymers by in
substrate are ≈100 µm and 80 g m−2, respectively.[34] Fibrils and situ polymerizations of monomers that are pre-soaking paper
microfibrils are held together by hydrogen bonding rendered by substrates in monomer solutions (Figure 2b); (3) Vaporization
surface hydroxyl groups. These hydrogen bonds play a critical method. A thin layer of metal is first deposited to make paper
role in fabricating paper-supported electrodes, by anchoring the substrate more electrically conductive. Conducting polymers
guest materials onto paper surface.[12,30,47,55–58] or metal oxides are subsequently electro-deposited onto the
For making paper-supported electrodes, pre-treatments of metal coated paper substrates (Figure 2c); (4) Vacuum filtra-
paper substrates to eliminate inactive additives and increase tion method. Highly conductive and electrochemically active
porosity are needed. A typical procedure was reported by Yao materials can be directly deposited onto a piece of filter paper
et al.[14]: immerse a piece of printing paper into an aqueous through vacuum filtration. The guest materials can coat on cel-
solution containing 0.3 M hydrochloric acid (HCl) for about lulose fibers and fill the inter-fiber voids (Figure 2d).
10 min, then wash with deionized water thoroughly and let
it dry at room temperature. Pre-treatments usually lead to
reduction on both weight and thickness due to the removal of 2.1.1. Pencil Drawing
mineral fillers and fluorescent whitening agents, and resulting
in a more porous open structure that is often beneficial for Pencil leads, the most accessible graphite products in our daily
paper-supported electrodes. life, are composed of fine graphite particles held together by

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tunable areal conductivity. More specifically,

drawing with 9B pencil lead could achieve
highest conductive film, while using 9H
pencil lead would come out the most infe-
rior conductivity. These traces can be used to
create any arbitrary shape and patterns and
they are quite stable against chemicals, mois-
ture and UV irradiation.[60] This pencil-based
approach has been widely used in making
electrodes for flexible energy storage devices
recently.[14,48]
Pencil-drawing can also couple with other
methods to make composite electrodes.
Zheng et al. used a pure graphite rod to
draw on Xerox cellulose paper to get a sol-
vent-free drawing electrode (Figure 3a).[48] A
Figure 1. Schematic illustration showing the hierarchical structure of cellulose fibers. Reproduced
with permission.[34] fairly low sheet resistance ≈233 Ω sq−1 was
achieved by drawing in orthogonal direction
that can deposit graphite more uniformly on
clay binders. Based on its hardness, pencils are classified on a the paper. An aqueous supercapacitor built via the assembly of
scale from 9B to 9H.[60] Their colors are different due to their two pencil-drawing electrodes can deliver a high capacitance
different fraction of graphite and clay. When pencil traces are of 1.13 mF cm−2 and retain 90% its initial capacitance after
drawn on paper, the friction between pencil lead and paper 15000 cycles. Although the device shows stable performance, its
rubs off graphite particles which in turn adhere to the paper areal capacitance is still relatively small. Later Yao et al. used an
fibers. Thus pencils can be viewed as a deployable form of electrodeposition method to grow polyaniline (PANI) network
ultrafine graphite particles. Pencil traces can be considered as on the pencil-drawing graphite paper.[14] The scanning elec-
conductive films made of percolated graphite particle network tron microscopy (SEM) images showed pencil-drawing process
on paper. Pencil leads with different hardness can result in formed a uniform layer of graphite sheets on the paper surface,

Figure 2. Schematic illustrations of four protocols for making paper-supported electrodes. a) Graphite/polyaniline (PANI)-Paper fabricated by Pencil-
drawing method. Reproduced with permission.[14] Copyright 2013, Elsevier. b) Polypyrrole(PPy)-coated paper fabricated by soaking and polymerization
method. Reproduced with permission.[12] Copyright 2013, Royal Society of Chemistry. c) PANI/Au/paper electrode fabricated by vaporization method.
Reproduced with permission.[32] d) graphene-cellulose paper (GCP) electrode fabricated by vacuum filtration method. Reproduced with permission.[59]

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Figure 3. Microstructures of paper-based electrodes. a) Schematic diagram of drawing conductive electrode on cellulose paper using a graphite
pencil. Reproduced with permission.[48] Copyright 2013, Royal Society of Chemistry. b–e) Scanning electron microscopy images of (b) blank A4 printing
paper, (c, d) graphite paper, (e) G/PANI-Paper with polyaniline deposition time of 120 min. Reproduced with permission.[14] Copyright 2013, Elsevier.
f–g) Scanning electron microscopy images for paper coated by polypyrrole with different polymerization times of 0 and 180 minutes, respectively.
h) Cross-section scanning electron microscopy image of the 180 minutes polypyrrole/paper composite. The inset shows an enlarged polypyrrole-coated
cellulose fiber. i) Polypyrrole-coated paper passes the tape test shows that the strong mechanical property. Reproduced with permission.[12] Copyright 2013,
Royal Society of Chemistry. j,k) SEM images of the filter paper or GCP surfaces with different GNS loading amounts. j) 0 wt% (pristine filter paper), and
k) 7.5 wt%. l) SEM and m) TEM images of a cellulose fiber in a GCP membrane showing GNSs anchored on the fiber surface. Reproduced with permission.[59]

while three dimensional PANI networks were further grown on paper is not problematic but advantageous for energy storage
the graphite paper (Figure 3b–e). The PANI coated paper elec- device such as supercapacitor and Li-ion batteries.[30] According
trode achieved a higher areal capacitance of 355.6 mF cm−2. The to the different equipment used, printing can be classified to
flexible solid-state supercapacitor fabricated by sandwiching ink-jet printing,[64] Mayer rod printing,[30] screen printing,[65]
polyvinyl alcohol (PVA)/H2SO4 gel electrolyte film between two gravure printing,[66] etc. Some untraditional methods like using
PANI/graphite electrodes displayed light-weight characteristic, Chinese brush to deposit solution-based materials on paper
with 219 µm in thickness and 30.8 mg in weight. Feng et al. have also been demonstrated.[30]
further improved the performance by using two asymmetric Selecting and preparing the appropriate ink for printing is
paper electrodes.[61–63] Graphite/Ni/Co2NiO4 paper electrode the key step in making printing-based paper electrode. Hu et al.
was fabricated by pencil drawing, followed by deposition of Ni employed Mayer rod to coat uniformly dispersed CNT ink and
and Co2NiO4 in sequence. Graphite/Ni/active carbon paper Ag ink on ordinary office paper and successfully fabricate a
electrode and Graphite/Ni/Co2NiO4 paper were used as nega- CNT conductive paper.[30,47] This conductive paper reached
tive and positive electrode respectively to assemble an asym- a low sheet resistance around 10 Ω sq−1 for CNT coating and
metric supercapacitor, which achieve a high working voltage 1 Ω sq−1 for Ag nanowire coating. The CNT paper electrode
of 2V. It has an outstanding volumetric energy density of achieved a specific capacitance of 200 F g−1, a specific energy
2.48 mWh cm−3, which is much larger than the value obtained of 30–47 Wh kg−1, a specific power of 200 kW kg−1 and a stable
from other paper-based symmetric devices. cycling life over 40000 cycles. This conductive CNT paper can
also be used as a current collector that has been integrated with
LiMn2O4 (cathode) and Li4Ti5O12 (anode) to assemble a full
2.1.2. Printing Li-ion battery. The LiMn2O4 nanorod and Li4Ti5O12 nanopowder
electrodes achieved initial discharge capacities of 110 mAh g−1
Printing on paper is a facile, fast and highly scalable method and 149 mAh g−1, and capacity retentions of 93% and 96% after
for making flexible paper electronics. A major challenge of 50 cycles, respectively.
using paper for flexible electronics is its rough surface, which To integrate anode, cathode and separator into a single sheet
generally needs planarization by surface treatment or surface of paper and fabricate an integrated device, Hu et al. further
coating before printing.[34] However, this rough surface of demonstrated a high-speed ink-jet printing method to print

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single-wall carbon nanotubes (SWCNT) on both sides of a pre- can be solved by coating a thin layer of polymer materials, such
treated polyvinylidene fluoride (PVDF) paper.[64] The PVDF as PVA or parylene.[32,71]
coating was employed to prevent CNT penetration through Yuan et al. prepared a PVA solution by mixing PVA powder
the micron-sized pores in paper that can cause short circuit with deionized water. Then, a piece of printing paper was
as all the components are integrated onto a single sheet of immersed into the PVA solution until PVA fill the paper
paper. A specific capacity of 33 F g−1 at a high specific power thoroughly. The treated paper was then air dried. A thin gold
of 250 kW kg−1 was achieved in an organic electrolyte. Such a (Au) film (80 nm) was deposited on the PVA treated paper via
lightweight paper-based supercapacitor is promising for pow- E-beam evaporation. This Au paper displayed a low sheet resist-
ering paper electronics such as transistors or displays. ance of 7 Ω sq−1. PANI/Au paper electrodes were fabricated by
electrodeposition of PANI nanowires on Au paper. The paper
electrode showed a high specific capacitance of 560 F g−1, an
2.1.3. Soaking and Polymerization areal capacitance of 0.8 F cm−2 and a high volumetric capaci-
tance of 800 F cm−3 (based on the mass and thickness of active
Conducting polymers, which were discovered in 1976, are material).[32]
one important type of electrode materials for energy storage Wang et al. reported the first flexible micro-supercapacitor
due to their large capacitance, good electrical conductivity, on paper.[71] They evaporated parylene onto a photographic
ease of synthesis and low cost.[25,32,67–69] Over the decades, paper for waterproofing and insulation purposes. 200 nm gold
conducting polymers have received significant attention in interdigital patterns were then directly thermally evaporated
flexible energy storage devices. Among them, polypyrrole onto the parylene passivated paper using hard masks. Coral-like
(PPy), polyaniline (PANI), poly[3,4-ethtylenedioxythiophene] polyaniline-manganese oxide was then electrochemically depos-
(PEDOT) and their derivatives have been widely investigated ited onto the interdigital gold electrode. Employing the PVA/
in supercapacitors due to their large specific capacitance, H3PO4 gel electrolyte, this flexible solid-state interdigital super-
e.g., 480 F g−1 for PPy, 1284 F g−1 for PANI, and 210 F g−1 capacitor displayed a high areal capacitance of 94.73 mF cm−2
for PEDOT.[70] As a 3D porous substrate, paper can be and a high areal energy density of 6.3 µWh cm−2.
easily coated with conducting polymers due to its hydrogen
bonding interaction with polymer monomers, which can
then be polymerized into conducting polymers and form a 2.1.5. Vacuum Filtration
3D conducting network.
Yuan et al. simply soaked the daily printing paper into PPy Vacuum filtration is one of the most popular methods in
monomer solution and then transferred into ferric chloride making paper-supported electrodes because of its fast and
solution with hydrochloric acid to polymerize PPy onto the scalable characteristics. Owing to its intrinsic 3D porous struc-
paper substrate. In this process, ferric chloride works as oxi- ture, paper can be used as a “filter” to block the materials
dation agent and hydrochloric acid acts as doping agent. After with the size larger than its pore size and at the same time
polymerization, the paper became black and conductive. The coat the surface of fibers and fill its pores with these mate-
roughness of the cellulose fibers increased and the connections rials. Vacuum filtration method has been used to prepare
among fibers increased compared with the blank paper sub- carbon based (e.g., graphene, graphite, CNT) paper-supported
strate (Figure 3f and 3g). More importantly, both the exterior electrodes.[58,59,72–75]
and interior of cellulose fibers were coated with PPy uniformly Weng et al. fabricated the graphene paper by simply filtering
(Figure 3h). Mechanical adhesion test showed that no obvious a graphene nanosheets (GNSs) suspension through a filter
PPy could be observed on tape, demonstrating the good adhe- paper.[59] As seen from the SEM images in Figure 3j and 3k,
sion of PPy on the paper (Figure 3i). PPy coated paper electrode the cellulose fiber surfaces and voids of the filter paper were
showed high gravimetric capacitance above 370 F g−1. The flex- covered and filled with GNSs. The strong binding between cel-
ible solid-state supercapacitor fabricated via sandwiching PVA/ lulose fibers and GNSs was ascribed to the strong electrostatic
H3PO4 membrane both as electrolyte and separator displayed interaction between the functional groups on the fibers and the
an areal capacitance of 0.42 F cm−2, a high energy density of negatively charged GNSs. The resistivity of this graphene paper
1 mWh cm−3 at a power density of 0.27 W cm−3 normalized to is 6 Ω·cm and only decrease 6% after being bent 1000 times.
the device volume. The graphene paper electrode displayed a gravimetric capaci-
tance of 120 F g−1 (normalized to the mass of graphene) and
retains more than 99% of its initial capacitance over 5000 cycles.
2.1.4. Thermal Evaporation Jabbour et al. manufacture flexible cellulose-graphite paper
electrode via direct infiltration of the hybrid slurry of graphite
Thermal evaporation is a commonly used method for thin particles and cellulose, which resulted in a flexible free-standing
film deposition. It involves two basic processes: vaporization cellulose-based graphite paper.[58] This graphite paper showed
of source material and condensation of vapor on a substrate. excellent tensile properties with Young moduli ranging between
This evaporation process takes place in vacuum and usually 60 and 450 MPa. When the graphite paper was used as anode
it is directional. Paper is inherently not an ideal substrate for in Li-ion batteries, it exhibited an excellent discharge capacity
depositing continuous film, since its surface is uneven and up to 350 mAh g−1, which is very close to the theoretical limit
rough. Besides, the interconnection between metal particles for graphite electrodes (i.e. 372 mAh g−1). The paper electrode
and paper substrate is relatively weak. However, this problem also has stable performance over 120 cycles.

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2.2. Optimizing Electrical Property of

Paper Electrodes

Electrical conductivity is a critical factor that

can greatly affect the electrochemical perfor-
mance of paper electrodes. The resistance of
the electrodes should be as low as possible.
The total resistance includes the resistance of
the active materials, resistance of the current
collector, and interfacial resistance between
active materials and current collector. Nor-
mally, the resistance of the current collector
is relatively small. Thus, to decrease the
resistance of active materials and interfacial
resistance between electrode material and
current collector is important for enhancing
the electrode performance. A number of
highly conductive materials such as con-
ducting polymers,[12,14,25,67] carbon-based
materials,[76–79] metal nitrides,[80–82] metal car-
bides[51,83] have been employed for fabricating
electrodes. Moreover, various methods have
been developed to improve the electrical con-
ductivity of electrode materials with modest
conductivity such as metal oxides.[84–86] These
approaches include doping,[87,88] introducing
oxygen vacancy,[89,90] introducing low valence
states[91] and synthesizing hybrid electrodes
with high conductive materials.[33,92]
Some metrics can be used to evaluate the Figure 4. Electrical performance of paper electrode. a) Mass loadings of polypyrrole (), sheet
electric properties of paper-based electrodes, resistance () and conductivity () of the fabricated polypyrrole-coated paper with respect to
such as sheet resistance, conductivity, and polymerization time of 5, 20, 60 and 180 minutes. b) Polypyrrole-coated paper as electrical
connections to light a blue LED by a homemade 2.7 V battery. c) Current-time curves of polypyr-
conductance stability under deformations,
[12,14] role-coated paper bent with different curvatures under a constant voltage. The upper insets
etc. Yuan et al. successfully fabricated labeled I, II, III, IV and V reveal the five bending states. The lower left inset shows the current-
highly conductive PPy-coated paper elec- voltage curve of polypyrrole-coated paper without bending. The lower right inset records the
trodes.[12] The electrical conductivity of the current-voltage curves of polypyrrole-coated paper after 20, 50, 80 and 100 cycles of bending.
PPy coated paper electrodes increased with Reproduced with permission.[12] Copyright 2013, Royal Society of Chemistry.
increasing polymerization time and mass
loading of PPy (Figure 4a). Its sheet resist-
ance can be as low as 4.5 Ω sq−1. The high conductivity of the 3. Paper-Like Electrodes
PPy-coated paper (15 S cm−1) assures that it can be used as a
flexible lead to connect all the device components. As shown Most of the electrodes for energy storage devices are generally
in Figure 4b, a homemade 2.7 V button battery light up a blue made by mixing particulate active materials with polymeric
light-emitting-diode (LED) (the lowest operating voltage is binders e.g., polyvinylidene fluoride (PVDF) and polytetrafluor-
2.5 V) by using the PPy-coated paper as a connecting lead. At oethylene (PTFE) and conducting agents (e.g. carbon black)
a fixed voltage of 0.5 V, the PPy-coated paper showed excellent with the help of appropriate solvent. The binders are used
conductance stability at different bending states, even at 180° to glue the active materials and conducting agents as well as
(Figure 4c). Furthermore, the conductance of PPy-coated paper the current collector, whereas the conductive agent network
remained almost constant after 100 cycles, indicating its high helps to transfer electrons from active materials to current col-
stability and flexibility, which is promising for the application lector. Although this process is widely adopted in industry, the
in flexible electronics. introduction of insulated binders increases both the contact
Although paper-supported electrodes have only been devel- resistance between particles as well as the resistance of the
oped in recent years, they have attracted much attention in electrodes. Besides, the binders and additive conductive agents
the research community and shown great potential in flex- make up about 20–40% of the total electrode mass, which are
ible energy storage applications. In addition to the abovemen- seen as ‘dead mass’ because they do not contribute to charge
tioned examples, we also summarized the materials, synthesis storage, but instead decrease the energy density of both the
method, and electrochemical performances of other paper- electrodes and devices.[102]
supported electrodes and their applications in flexible energy Flexible cellulose substrates can be used to support con-
storage devices in Table 1. ductive active materials to achieve high performance in many

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Table 1. Performance of paper-supported electrodes in flexible energy storage devices.

Electrodes Synthesis method Device Performance Ref.

Capacitance/Capacity Power Density Energy Density Cycling Stability
PPy-paper Soaking and polymerization SC* 1.5 F cm−2 0.46 W cm−3 1 mWh cm−3 75.6% after 10000 cycles [12]
370 F g−1
PPy-bacterial cellulose paper Vacuum filtration SC 2.43 F cm−2 – – 94.5% after 5000 cycles [74]
PPy-cladophora cellulose paper Vacuum filtration SC 315 C g−1 2.7 kW kg−1 1.75 Wh kg−1 No loss after 1500 cycles [72]
PANI-paper Electrodeposition SC 160 F g−1 – – 81% after 1000 cycles [55]
PANI-graphite-Paper Pencil-drawing Electrodeposition SC 355.6 mF cm−2 0.054 W cm−3 0.32 mWh cm−3 83% after 10000 cycles [14]
PANI-nylon-cellulose Electrospinning SC 402 F g−1 – – 61% after 1000 cycles [93]
acetate-paper Electrodeposition
PEDOT-paper In situ Polymerization SC 145 F cm−3 1 W cm−3 1 mWh cm−3 91% after 2500 cycles [56]
115 F g−1
PEDOT-paper Spin coating SC 994 μF cm−2* 64.70 W cm−3 1.77 mWh cm−3 No loss after 12000 cycles [94]
16.6 F cm−3 *
CNT-paper Dip and dry SC 115.83 F g−1 – 48.86 Wh kg−1 – [57]
CNT-paper Mayer rod printing SC 200 F g−1 * 200 kW kg−1 47 Wh kg−1 97% after 40000 cycles [47]
CNT-PVDF-paper printing SC 33 F g−1 250 kW kg−1 – 96.9% after 2500 cycles [64]
MnO2-CNT-paper Dip and dry SC 1162 F g−1 4 mW cm−2 4.2 µWh cm−2 97.8% after 20000 cycles [95]
Si-CNT-paper Vacuum filtration PECVD* LIB* 2100 mAh g−1 – – 77% after 100 cycles [96]
PEDOT-CNT-paper Ink-jet printing SC 23.6 F cm−3 89.1 mW cm−3 42 mWh cm−3 92% after 10000 cycles [97]
h-MnO2-CNT-paper Printing SC 1035 F g−1 81 kW kg−1 25.3 Wh kg−1 98.9% after 10000 cycles [98]
91.7 mF cm−2
CNT-MnO2-CNT-paper Dip-and-dry electrodeposition SC 327 F g−1 – – 85% after 50000 cycles [99]
LiMn2O4-CNT-paper Mayer rods printing Pressing LIB 110 mAh g−1 – – 93% after 50 cycles [30]
Li4Ti5O12-CNT-paper LIB 149 mAh g−1 – – 96% after 50 cycles
Graphene-paper Vacuum filtration SC 252 F g−1 2.4 kW kg−1 237 Wh kg−1 – [59]
LIB 540 mAh g−1 – – 22.9% after 45 cycles [75]
Graphite-paper Pencil-drawing SC 2.3 mF cm−2 35 kW kg−1 1.46 Wh kg−1 90% after 15000 cycles [48]
Graphite-paper Vacuum filtration LIB 350 mAh g−1 – – 94.5% after 120 cycles [58]
MnO2-Ni-paper Electroless plating SC 1.9 F cm−2 2.5 mW cm−2 0.8 mWh cm−3 85.1% after 1000 cycles [100]
Electrodeposition
MnO2-Ni-graphite-paper Pencil-drawing Electrodeposition SC 175 mF cm−2 48 mW cm−3 106 mWh cm−3 96% after 6000 cycles [62]
60 kW kg−1 66.2 Wh kg−1
Mn3O4-Ni-graphite-paper Pencil-drawing Electrodeposition SC 432 mF cm−2 33 mW cm−3 0.35 mWh cm−3 83% after 12000 cycles [63]
432 F g−1
Co2NiO4-Ni-graphite-paper Pencil-drawing Electrodeposition SC 734 mF cm−2 0.79 W cm−3 2.48 mWh cm−3 97.6% after 15000 cycles [61]
25.6 kW kg−1 80 Wh kg−1
PANI-Au-paper Evaporation and SC 560 F g−1 3 W cm−3 0.01 Wh cm−3 103% after 10000 cycles [32]
Electrodeposition
0.8 F cm−2
Si-CNTs-CNC film Vacuum filtration LIB 3200 mAh g−1 – – 57.5% after 100 cycles [101]

*Notes: Supercapacitor (SC), Lithium-ion batteries (LIB), Plasma-enhanced chemical vapor deposition (PECVD).

flexible energy storage systems. However, the addition of elec- fabricate paper-like electrodes with active charge storage mate-
trochemically inactive cellulose paper substrate considerably rials can substantially enhance the device specific capacity as
lower the energy density and power density of supercapacitor well as energy density and power density.
device when they are normalized to the total electrode mass/ According to the materials involved, paper-like electrodes
volume. Thus, to eliminate the inactive paper substrate and can be divided into four categories: graphene-based paper-like

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electrodes, CNT-based paper-like electrodes, carbon-fiber paper- The high flexibility and ease of integration with other compo-
like electrodes and carbon-free paper-like electrodes. Here we nents make them ideal candidates for flexible energy storage
summarize and discuss the fabrication methods for each type devices (Figure 5a,b).[50]
of paper-like electrode. Free-standing flexible graphene paper electrodes were first
applied in Li-ion battery and supercapacitor in 2009.[128,129]
When employed as an electrode in Li-ion battery, however,
3.1. Graphene-Based Paper-Like Electrodes an enormous irreversible capacity was observed.[128] The dis-
charge capacity dropped drastically from 680 mAh g−1 in the
Since the first report using micromechanical cleavage method first cycle to 84 mAh g−1 in the second cycle, only 12.4% of
to produce graphene sheet in 2004 by Geim and Novoselov, gra- the initial capacity was retained. It was believed to be due to the
phene and graphene-based nanocomposites have received tre- irreversible reaction between the residual oxygen-containing
mendous attention both for the sake of fundamental research groups in the graphene paper and lithium. When graphene
as well as their great potential for applications in energy storage paper was employed as supercapacitor electrode, it displayed a
and conversion systems.[103] Compared with other materials, gravimetrical capacitance of 147 F g−1 and volumetric capaci-
graphene has unique 2D structure, high electronic mobility tance of 64 F cm−3.[129] Considering the small surface area of
(15000 cm2 V−1 s−1),[103,104] exceptional electric (106 S m−1)[105] 94 m2 g−1 for the graphene paper, this high specific capacitance
and thermal (5300 W m−1 K−1)[106] conductivities, excel- was attributed to the pseudocapacitance of oxygen functional
lent optical transmittance (97.7% in visible region),[107] good groups (14%) on graphene surface. However, most of other gra-
mechanical strength (tensile strength 130 GPa and stiffness phene paper electrodes have capacitance typically smaller than
1.5 × 108 psi)[108] and ultrahigh surface area (≈2630 m2 g−1).[109] 100 F g−1 because of severe restacking of graphene flakes and
Its extraordinarily high surface area enables its high electric the low concentration of surface oxygen-containing functional
double-layer capacitance as high as 550 F g−1 if the entire sur- groups.[123,130,131]
face area can be fully utilized.[102] Rational structural design of graphene paper electrode is crit-
Several physical and chemical methods can be utilized to ical for improving charge storage performance (Figure 5c–h).
synthesize graphene including micromechanical cleavage, Graphene films with open pores allow fast ion diffusion and
chemical vapor deposition, liquid phase exfoliation, reduction help to achieve both high capacitance and high rate capability.
of graphene oxide (GO), thermal deposition of silicon carbide However, when graphene films are packed, the strong π-π inter-
(SiC), and un-zipping carbon nanotubes.[110] To realize the action between graphene sheets tend to restack to graphite-like
commercial potential of graphene, it is essential to develop a powders or films, which severely decrease the accessible sur-
reliable, low-cost and facile process for large-scale fabrication face area and ion diffusion rate, and thus, limiting both gravi-
of high quality graphene materials. Solution processing offers metric capacitances and charge/discharge rates.
a simple yet effective approach for the fabrication of graphene Constructing 3D graphene films with hierarchical pores is
electrodes. To successfully using solution-processing approach an effective way to enhance the energy storage performance.
to fabricate graphene electrodes, there are three steps: first, El-Kady et al. fabricated a laser-scribing graphene film with
preparation of a completely exfoliated GO solution; homoge- open porous structure, which can mitigate these challenges to
neous dispersion of high-quality graphene in a solvent; third, increase the accessible surface area and boost the gravimetric
fabrication of graphene film. In 1958, Hummers et al. invented capacitance up to 276 F g−1.[136] Xu et al. reported a holey gra-
an effective oxidative method to produce GO solution, which is phene framework film with a high packing density, open
later called ‘Hummers method’.[111] In 2008, Li et al. reported a porous structure and efficient ion transport pathway to simul-
facile method to make chemically converted graphene sheets to taneously with a high gravimetric capacitance (298 F g−1) and a
form stable aqueous dispersions.[112] These studies pave a way high volumetric capacitance (212 F cm−3).[137]
for fabricating graphene and graphene-based films. Graphene Heteroatom doping in graphene can also improve the elec-
dispersions or graphene-based hybrid materials suspension trode performance. Doping graphene with oxygen (O), nitrogen
can be well processed into electrodes using various techniques, (N), sulfur (S) and boron (B) have been proved to be effective
including dip coating,[113] rod coating,[114] spray coating,[115] in enhancing the performance of graphene paper for energy
inkjet printing,[116] spin coating,[117] screen printing,[118] gravure storage.[110,138–141] Lu et al. successfully fabricated N-doped gra-
printing,[119] blade coating,[120] electrospinning,[121] electrodepo- phene papers.[139] Due to improved electrical conductivity and
sition,[122] vacuum filtration,[123] drop casting,[124] interfacial extra capacitance contributed from the pyridine-like N dopants,
deposition,[124] Langmiur-Blodgett deposition[125] and layer- the N-doped graphene paper displayed a high specific capaci-
by-layer assembly.[126] Depends on the targeted properties and tance of 280 F g−1, which is much higher than the un-doped
size of the graphene electrode, different approaches should be graphene paper with capacitance only 29 F g−1. Akhter et al.
used.[102] further demonstrated a N-, S- codoped graphene paper elec-
trode, which exhibited an excellent capacitive performance of
305 F g−1.[140]
3.1.1. Graphene Paper-Like Electrodes Although graphene paper can achieve high specific capaci-
tance over 200 F g−1 in supercapacitors, their low mass densi-
Since the first graphite oxide paper reported in 2007 by Ruoff et al. ties (0.05–0.75 g cm−3) make their volumetric capacitance rather
using vacuum filtration method, free-standing paper-like gra- modest (≈10–110 F cm−3).[123] Yang et al. took the advantage
phene-based materials have been extensively investigated.[127] of capillary compression of adaptive graphene gel films in the

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Figure 5. Schematic diagrams of four approaches for making graphene paper electrodes. a) Simple structure, great potential. Shiny and flexible
graphene paper is formed by controlled restacking of graphene sheets. b) In graphene, carbon atoms (green dots) are bonded together through sp2
hybridization (orange lines). Reproduced with permission.[50] Copyright 2008, American Association for the Advancement of Science. c,d) SEM images
of cross sections of the obtained liquid electrolyte-mediated chemically converted graphene films containing (c) 78.9 volume percent (vol. %) and (d)
27.2 vol. % of H2SO4, respectively, corresponding to ρ = 0.42 g cm−3 and ρ = 1.33 g cm−3. Reproduced with permission.[123] Copyright 2013, American
Association for the Advancement of Science. e) Graphene paper was produced via the vacuum filtration of graphene dispersion. Reproduced with
permission.[132] Copyright 2013, American Chemical Society. f) Schematic illustration showing the experimental steps of activated reduced graphene
oxide film. Reproduced with permission.[133] Copyright 2012, American Chemical Society. g) Illustration of the formation process of graphene paper.
Step 1, GO aqueous dispersion. Step 2) GO dispersion frozen at −50 °C. Step 3) GO aerogel obtained by freeze drying. Step 4) Under vacuum. Step 5)
Graphene aerogel obtained by treating Go aerogel at 200 °C in air. Step 6) Mechanical pressing of the graphene aerogel to form graphene paper. Repro-
duced with permission.[134] h) Schematic illustrations of the formation process of graphene–PANI paper. Reproduced with permission.[135] Copyright
2013, Royal Society of Chemistry.

presence of a nonvolatile liquid electrolyte and enabled sub- as conducting polymers and metal oxides. In this part, we will
nanometer scale integration of graphene sheets with electrolytes mainly focus on the different methods in fabricating various
to form highly packed graphene film electrode with a continuous graphene-based composite paper-like electrodes.
ion transport network.[123] This highly packed electrolyte-medi-
ated chemically converted graphene films (1.25–1.33 g cm−3) Vacuum Filtration: Vacuum filtration is a high scalable, low cost
yielded a high volumetric capacitance of 255.5 F cm−3 in aqueous and easy process that has been widely used for making the free-
electrolyte and 261.3 F cm−3 in organic electrolyte. standing paper-like graphene-based films. Vacuum filtration
setup usually consists of Buchner funnel, filter membrane and
vacuum system. Different kinds of filter membrane such as
3.1.2. Graphene-Based Composite Paper-Like Electrodes anodic aluminum oxide (AAO) filter membrane, PVDF mem-
brane, PTFE membrane and cellulose membrane have been
One of the most important approaches to manufacture high per- used in making graphene-based papers.[112,142–144] Free-standing
formance graphene-based electrodes is to synthesize composite graphene-based paper can be produced by peeling off from the
structures of graphene and pseudo-capacitive materials such membrane after filtering and drying.

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Graphene composite electrodes can be fabricated by first graphene/PANI nanofiber composite flexible films by vacuum
filtering a graphene paper and then deposit another pseudo- filtration of the mixed dispersions of both the graphene and
capacitive material on graphene paper using other methods PANI nanofibers (Figure 6h–j). The composite film has a layered
such as electrodeposition or chemical vapor deposition. Alter- structure with PANI nanofibers sandwiched between graphene
natively, the solution suspension of graphene and pseudoca- layers. It showed a high conductivity of 550 S cm−1, which is
pacitive materials can be filtered simultaneously. These two 10 times higher than the pure PANI nanofiber film. This com-
approaches allow easy tuning of the film property by control- posite electrode showed both increased capacitance and enhanced
ling the ratio between components as well as the total mass of stability compared to bare graphene film and PANI film.[146]
active materials. The second approach is more popular recently,
since it enables better mixing of graphene and pseudocapaci- Laser Scribing: Laser scribing is a simple and scalable all-solid-
tive materials. state approach that can convert GO into highly conductive gra-
Cheng et al. fabricated the graphene/PANI composite paper phene.[147] The scribing laser simultaneously reduce and exfo-
by vacuum filtration of the graphene followed by anodic elec- liate GO sheets to yield open porous network of graphene.[136]
tropolymerization of PANI film. This paper displayed a favorable Besides, this method can also precisely control the shape of final
tensile strength of 12.6 MPa and a stable electrochemical capaci- products by designing different patterns, which can be widely
tance of 233 F g−1 and 135 F cm−3 (Figure 6a–c). Hu et al. dem- used in making microscale energy storage devices.[148–150]
onstrated a highly flexible Mn3O4/reduced graphene oxide El-Kady et al. used the commercially available LightScribe
(rGO) nanohybrid paper with high conductivity via vacuum DVD to obtain high conductive graphene film.[136] The graphene
filtration of MnOx/GO mixture and electrochemical reduction film showed an excellent conductivity of 1738 S m−1 and large
process (Figure 6d–g). Asymmetric supercapacitor device based and accessible specific surface area of 1520 m2 g−1. Besides,
on Mn3O4/rGO paper as the cathode and rGO paper as the this 3D porous structure prevents the agglomeration of gra-
anode is assembled and showed a high volumetric capacitance phene sheets which has been the major barrier in realizing the
of 54.6 F cm−3 and a high volumetric energy and power density full potential of graphene-based supercapacitors. The flexible
(5.5 mWh cm−3 and 10.95 W cm−3).[145] Wu et al. prepared the device can work over a wide voltage window of 3 V in organic

Figure 6. Flexible graphene-based hybrid paper electrodes. a) Schematic diagram showing how MnOx nanofibers are embedded among rGO sheets.
b) Pictures of as filtered MnOx/GO nanohybrid paper rolled freely. c) SEM images of MnOx/GO nanohybrid paper: from cross-sectional view. d) TEM
images of MnOx nanofibers embedded in an rGO sheet, with part of the rGO sheet’s edge marked out. Reproduced with permission.[145] Copyright 2010,
American Chemical Society. e) Digital photograph of a flexible graphene/polyaniline nanofiber composite film (G-PNF). f,g) Cross-section SEM images
of G-PNF. Reproduced with permission.[146] Copyright 2010, American Chemical Society. h) Illustrative fabrication process toward graphene/polyaniline
composite paper (GPCP). i) Digital camera images of a flexible G-paper. j) SEM image of the GPCP. Reproduced with permission.[129] Copyright 2009,
American Chemical Society.

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electrolyte and offered a specific capacitance up to 265 F g−1. 3.2. CNT-Based Paper-Like Electrodes
This working window could be even expanded to 4 V under
ionic liquid electrolyte and exhibited as specific capacitance of Carbon nanotubes (CNTs) are well-ordered hollow graphite
276 F g−1. The supercapacitor device delivered a high energy nanomaterials consisted of cylinders of sp2-hybridized carbon
density up to 1.36 mWh cm−3 and power density of 20 W cm−3. atoms. According to the number of layers of graphene sheets
Gao et al. employed the non-toxic direct laser writing to fabri- ‘rolled’ into tubes, CNTs can be classed as sing-walled carbon
cate in-plane supercapacitors with three different geometries.[148] nanotubes (SWCNTs) and multi-walled carbon nanotubes
All of the three structures are consist of the rGO-GO-rGO con- (MWCNTs). Diameters of SWCNTs and MWCNTs are typi-
figuration, where GO is served as a separator and rGO works as cally 0.8 to 2 nm and 2 to 100 nm, respectively. The length of
active electrode materials. The concentric circular pattern gives CNTs ranges from less than 100 nm to several centimeters.[189]
the highest capacitance density over the parallel column and hair CNTs were first discovered by Iijima in 1991.[190,191] Since
brush structures. This in-plane circular design showed an energy then, it has aroused the world-wide research interest due to its
density of 0.43 mWh cm−3 and power density of 9.4 W cm−3 and high aspect ratio, high mechanical strength, large surface area,
kept 70 % of its initial capacitance after 10000 cycles. excellent chemical and thermal stability, and rich electronic and
optical properties.[189,192,193] With their unique physical proper-
Mayer-Rod Coating: Mayer-rod coating is a well-known coating ties, such as high electrical conductivity (104–105 S cm−1) and
technique widely used in the coating industry for making thin good chemical and mechanical stability, CNTs have proven to
films in a continuous and controlled manner. Mayer rod is a be promising for electrochemical energy storage.[11,30,49,194–196]
metal bar with a wire wrapped around that used to draw a solu- Both SWCNTs and MWCNTs have been explored as energy
tion over a substrate surface. The diameter of the wire wound storage electrode materials.
around the bar determines the thickness of the graphene film.
This technique can be used to produce large-area graphene film
with tunable thickness.[114,135,151] 3.2.1. CNTs Paper-Like Electrodes
Liu et al. used Mayer-rod coating method to produce a
free-standing and highly flexible graphene-PEDOT/PSS In 2004, Morris et al. demonstrated a free-standing SWCNTs
film with large size (30 cm × 7 cm) and high mass loading paper electrode and applied them into Li-ion battery for the
(8.49 mg cm−2).[151] The flexible film show high areal capaci- first time.[197] The laboratory cell based on this film is able to
tance of 448 mF cm−2. The assembled solid-state supercapacitor display a specific energy exceeding 600 Wh kg−1 and power
device displayed stable performance over 10000 cycles both density over 3 kW kg−1. In 2005, a CNT ‘buckypaper’ was fab-
under flat and 180° bending states. ricated via filtrating of double-walled CNTs.[198] This paper-like
sheet is flexible and mechanically stable. Thereafter, numerous
Sacrificial template: Sacrificial template method has been widely reports on CNTs and CNTs-based paper electrodes have been
used in the colloid synthesis, which prepare materials on pre- published.
existing templates. Graphene can also be fabricated on various Recently, a free-standing flexible SWCNTs film was prepared
templates, such as metal mesh, calcium carbonate (CaCO3), by a floating chemical vapor deposition method.[199] The spe-
silicon dioxide etc.[26,152–155] After removing the template, free- cific capacitance of supercapacitor based on these films is about
standing hierarchical graphene structure can be obtained. To 35 F g−1. Its power density is 197.3 kW kg−1. Ultrathin MWCNT
make graphene-based flexible films, sacrificial templates, such film was also fabricated via layer-by-layer assembly process.[200]
as nanoporous copper foils and calcium carbonate particles, It achieved a high specific capacitance (159 F g−1) and volu-
have been used.[152,153] metric capacitance (132 F cm−3).
Qin et al. reported the synthesis of a continuous hierar- Introducing pseudocapacitance into carbonaceous mate-
chical nanoporous graphene film by CVD growth of hydro- rials can greatly enhance their overall performance for charge
genated graphite (HG) coating on nanoporous copper, rapid storage. Xiao et al. used vacuum filtration method to fabricate
catalytic pyrolysis of HG using nanoporous copper as catalyst flexible freestanding CNT films and then adopted an electro-
and followed by the removal of these catalysts.[153] The as- chemical method to add redox active functional groups onto
prepared flexible hierarchical graphene film owns a large sur- CNT films (Figure 7).[49] Oxygen-containing groups, espe-
face area (1160 m2 g−1). The symmetric solid-state device shows cially carboxylate (–COOH) group played an important role
a high specific capacitance (38.2 F cm−3), a high energy den- in enhancing the supercapacitor performance. The func-
sity (2.65 mWh cm−3) and power density (20.8 W cm−3) nor- tional CNT film showed an excellent areal capacitance of
malized to volume of the entire device. Meng et al. employed 150 mF cm−2, much larger than the bare CNT films with areal
CaCO3 as sacrificial template to fabricate hierarchical porous capacitance only about 40 mF cm−2. Likewise, the performance
graphene film. PANI/graphene composite film was synthesized of CNT film electrodes can be enhanced by integrating other
via polymerization of aniline monomer. This flexible electrodes high electrochemically active materials.[33,84,96,201]
achieved a high rate capability of 94% from 0.5 to10 A g−1.[152]
In addition to these methods and examples, there are other
approaches for fabricating high-performance graphene-based 3.2.2. CNT-Based Composite Paper-Like Electrodes
flexible electrode for energy storage systems, such as layer-by-
layer self-assembly,[140] pulse-electropolymerization,[156] and One of the most widely adopted strategy to make high-perfor-
screen printing,[118] which have been summarized in Table 2. mance electrodes for energy storage systems is incorporating

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Table 2. Graphene-based paper-like electrodes and their flexible energy storage devices.

Electrodes Synthesis methods Device Performance Ref.

Capacitance/Capacity Power Density Energy Density Cycling Stability
Graphene paper Laser scribing SC 276 F g−1 20 W cm−3 1.36 mWh cm−3 96.5% after 10000 cycles [136]
Graphene paper Frozen and pressing SC 172 F g−1 – – 99% after 5000 cycles [134]
LIB 864 mAh g−1 – – 65.7% after 100 cycles
Mesoporous graphene paper Vacuum filtration Li-S* 1393 mAh g−1 – – 49.5% after 50 cycles [157]
Graphene hydrogel film Hydrothermal reduction SC −1 −1 −1 91.6% after 10000 cycles [158]
187 F g 0.37 kW kg 0.61 Wh kg
Pressing
Porous graphene film Freeze-casting SC 284.2 F g−1 282 kW kg−1 9.9 Wh kg−1 97.6% after 10000 cycles [159]
Holey graphene film Hydrothermal etching SC −1 kg−1 kg−1 95% after 20000 cycles [137]
298 F g 7.46 kW 35.1 Wh
212 F cm−3 10.6 kW L−1 49.2 Wh L−1
Nanoporous graphene film Sacrificial template SC 305 F g−1 20.8 W cm−3 2.65 mWh cm−3 94% after 10000 cycles [153]
−3
95.4 F cm
Porous activated rGO film Vacuum filtration SC 120 F g−1 500 kW kg−1 26 Wh kg−1 95% after 2000 cycles [133]
rGO film Laser writing SC −2 cm−3 cm−3 70% after 10000 cycles [148]
0.51 mF cm 1.7 W 0.43 mWh
rGO film Photo reduction SC 275 F g−1 – – 98% after 100 cycles [160]
N-doped graphene paper Vacuum filtration SC −1 – – 99.4% after 40000 cycles [139]
280 F g
N/S-codoped graphene paper Layer-by-layer Self-assembly SC 305 F g−1 17.76 Wh kg−1 28.44 Wh kg−1 95.4% after 10000 cycles [140]
188 F cm−3
PPy-graphene film Pulse-electropolymerization SC 237 F g−1 1.18 kW kg−1 33 Wh kg−1 – [156]
PANI-graphene paper Vacuum filtration SC 233 F g−1 – – 109% after 1500 cycles [129]
Electrodeposition
135 F cm−3
PANI nanofiber-graphene Vacuum filtration SC 210 F g−1 3.3 kW kg−1 18.8 Wh kg−1 79% after 800 cycles [146]
paper
PANI-graphene paper Vacuum filtration SC 489 F g−1 – – 96% after 500 cycles [161]
Chemical polymerization
PANI-graphene film Screen printing SC 269 F g−1 454 kW kg−1 9.3 Wh kg−1 203% after 1000 cycles [118]
Graphene-PANI-graphene film Vacuum filtration SC −1 kg−1 kg−1 82% after 5000 cycles [162]
390 F g 2.4 kW 10.4 Wh
PANI-MnO2-graphene Vacuum filtration SC 636.5 F g−1 – – 85% after 10000 cycles [131]
Electrodeposition polymerization
PANI-3D-graphene film Sacrificial template SC 385 F g−1 – – 90% after 5000 cycles [152]
polymerization
PEDOT-graphene film Bar-coating SC 448 mF cm−2 3.59 kW kg−1 2.83 Wh kg−1 95% after 10000 cycles [151]
−1
81.9 F g
Si-graphene paper Vacuum filtration LIB 3200 mAh g−1 – – 83% after 150 cycles [163]
Co3O4-graphene paper Vacuum filtration LIB 1356 mAh g−1 – – 61.9% after 40 cycles [164]
Fe2O3-graphene paper Vacuum filtration SC 178.3 F cm−3 6.21 W cm−3 56 mWh cm−3 83.1% after 10000 cycles [165]
Fe3O4-graphene paper Vacuum filtration LIB 1555 mAh g−1 – – 85% after 50 cycles [166]
MnO2-graphene paper Vacuum filtration annealing SC 256 F g−1 – – 74% after 1000 cycles [167]
MnO2-graphene paper Vacuum filtration SC 897 mF cm−2 3.8 mW cm−2 35.1 µWh cm−2 78% after 3600 cycles [168]
Mn3O4-graphene paper Vacuum filtration SC 54.6 F cm−3 10.95 W cm−3 5.5 mWh cm−3 95% after 6000 cycles [145]
SnO2-graphene paper Vacuum filtration LIB 526 mAh g−1 – – 83.4% after 25 cycles [169]
SnO2-N-graphene paper Vacuum filtration LIB 918 mAh g−1 – – 63% after 50 cycles [170]
MoO3-graphene film Vacuum filtration LIB 291 mAh g−1 – – 59.1% after 100 cycles [171]
Mo2N-graphene paper Vacuum filtration NH3 annealing SC 142 mF cm−2 0.035 W cm−3 1.05 mWh cm−3 85.7% after 4000 cycles [172]
MoS2-graphene paper Vacuum filtration SIB 347 mAh g−1 – – 90% after 15 cycles [173]

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Table 2. Continued.

Electrodes Synthesis methods Device Performance Ref.

Capacitance/Capacity Power Density Energy Density Cycling Stability
V2O5-graphene paper Hydrothermal reaction vacuum SC 21.3 F g−1 425 W kg−1 8.5 Wh kg−1 60% after 50 cycles [174]
filtration
V2O5-graphene paper Vacuum filtration SC 512 mF cm−2 625 W kg−1 13.3 Wh kg−1 90% after 8000 cycles [175]
4.17 mW cm−2 89 µWh cm −2

V2O5·H2O-graphene film Vacuum filtration SC 11.7 mF cm−2 10 µW cm−2 1.13 µWh cm−2 95% after 2000 cycles [176]
VOPO4-graphene film Layer-by-layer SC 8.36 mF cm−2 5.2 mW cm−2 1.7 mWh cm−2 96% after 2000 cycles [177]
TiO2-graphene paper Vacuum filtration LIB* 236 mAh g−1 – – 99% after 90 cycles [178]
Nb2O5-graphene paper Vacuum filtration LIC* 160 mAh g−1 32 W kg−1 106 Wh kg−1 110.8% after 1000 cycles [179]
T-Nb2O5-graphene paper Hydrothermal reaction SC 620.5 F g−1 18 W kg−1 47 Wh kg−1 94.8% after 1700 cycles [180]
Vacuum filtration 961.8 F cm−3
CuO-graphene paper Vacuum filtration LIB 782.3 mAh g−1 – – 94.2% after 50 cycles [181]
MnO2-PPy-graphene film Electrodeposition SC 600 F g−1 13 kW kg−1 28 Wh kg−1 92% after 5000 cycles [182]
RuO2-graphene film Laser-scribing SC 1139 F g−1 81.4 kW kg−1 55.3 Wh kg−1 93% after 4000 cycles [147]
158 F cm−3
Ni(OH)2-grapheen paper Vacuum filtration SC 573 F g−1 17 kW kg−1 18 Wh kg−1 158% after 20000 cycles [183]
655 F cm−3
β-Ni(OH)2-graphene film Vacuum filtration SC 660.8 F cm−3 – – 100% after 2000 cycles [184]
3.3 mF cm−2
Co(OH)2-graphene film Vacuum filtration SC 20 F g−1 – – 100% after 5000 cycles [185]
LIB 520 mAh g−1 – – 23.1% after 200 cycles
Li-rGO film Spark reaction LIB 3390 mAh g−1 – – 90% after 100 cycles [186]
Carbon black-graphene paper Vacuum filtration SC 112 F g−1 – – 94% after 3000 cycles [187]
3D CNT-graphene film CVD SC – 10.3 kW kg−1 22.8 Wh kg−1 90.2% after 10000 cycles [188]

*Notes: Lithium-ion capacitor (LIC), Lithium-sulfur batteries (Li-S), Sodium-ion batteries (SIB).

Figure 7. Freestanding functionalized carbon nanotubes (CNTs)-based film. a) Schematic of the fabrication procedure for functionalized freestanding
CNTs films. b) Cross-section SEM image of the functionalized freestanding CNTs film. c) Enlarged cross-section SEM image of the functionalized
freestanding CNTs films. The inset is digital image of a functionalized freestanding CNTs film. Reproduced with permission.[49] Copyright 2014, Elsevier.

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high conductive and stable carbon materials with high specific mixture of VN nanobelts and CNTs (Figure 8).[201] Both VN and
capacity/capacitance materials such as conducting polymers, CNT have excellent electrical conductivity that ensures its appli-
metal oxides, metal nitrides and metal carbides. These compos- cation as electrode in solid-state supercapacitor without the
ites take the advantages of both the high conductivity of carbon need of any current collector. This light-weight device (15 mg
and high theoretical capacity/capacitance of those less conduc- including electrodes, separator and electrolyte) exhibited a high
tive pseudocapacitive materials, which could achieve better per- volume capacitance of 7.9 F cm−3 and energy density and power
formance than each individual component. density of 0.54 mWh cm−3 and 0.4 W cm−3.
The unique high aspect ratio and fast electron migration The performance of the filtered free-standing CNTs-based
along 1D direction of CNTs offer the paper-based 3D CNT con- paper-like composite electrodes can also be engineered by
ductive network great potential in the applications for Li-ion designing the sequence of adding different components. Zhao
storage devices and supercapacitors. Various approaches can et al. proposed a facile route for fabricating flexible and sand-
be used to fabricate CNT-based free-standing flexible paper-like wiched MXene/CNT composite paper electrodes through alter-
electrodes, such as vacuum filtration, doctor blade, chemical nating filtration of MXene and CNT dispersions.[202] They found
vapor deposition, and layer-by-layer assembly, etc. that the sandwiched electrode structure exhibited significantly
enhanced electrochemical performance compared to pure
Vacuum Filtration: Vacuum filtration is not only effective in pro- MXene and randomly mixed MXene/CNT papers (Figure 9).
ducing graphene-based paper-like electrodes with 2D graphene
nanosheets, but also useful in fabrication of paper-like elec- Doctor Blade: Doctor blade, also known as knife coating, is a
trodes with 1D CNTs. By varying the components of the filtration well-established technique for fabricating large-area films over
suspension, different composite films can be obtained. The high rigid or flexible substrates. The method is widely used in the
aspect ratio property of CNTs guaranties the flexibility of the laboratories to make CNT and graphene films for batteries and
film. The 3D conductive network consists of these CNTs allows supercapacitors. In a typical procedure, the active material slurry
effective charge transport and function as a 3D current collector. is transferred to substrate by moving the blade over a flat base.
Besides, this conducing network can also enclose the other active The variable thickness of the films is determined by the gap dis-
materials within this 3D conductive network and achieve a free- tance between the blade and substrate. Recently, this technique
standing flexible electrode without the need of insulated poly- was used for the preparation of flexible free-standing CNT and
meric binders. By eliminating the conducting agents like carbon graphene-based paper-like films.[102,147,203,204]
black and binders, these flexible free-standing CNT-based films Wu et al. presented the fabrication of scalable V2O5/CNT
are anticipate to have higher gravimetric and volumetric capac- freestanding films using a continuous doctor blade coating
ity/capacitance than conventional charge storage devices. process (Figure 10).[33] The process is facile and cost-effective
Xiao et al. reported a free-standing mesoporous VN/CNT while the obtained V2O5/CNT hybrid composite films have
hybrid electrode prepared by vacuum filtration of a solution a high packing density of about 2.5 g cm−3 after pressing

Figure 8. Freestanding mesoporous VN/CNT hybrid film. a) Schematic fabrication procedure of the paper-like freestanding mesoporous VN nanow-
ires/CNT (MVNN/CNT) hybrid electrodes. b) Digital images of paper-like freestanding MVNN/CNT hybrid electrodes. c) Cross-section SEM image
of the freestanding MVNN/CNT hybrid electrode. d) Enlarged cross-section SEM image of freestanding MVNN/CNT hybrid electrode. Reproduced
with permission.[201]

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Figure 9. Flexible MXene/carbon nanotube composite paper. a) Schematic showing the preparation of the sandwich-like MXene/CNT papers used
herein. b,c) Digital photographs showing a flexible and free-standing sandwich-like MXene/CNT paper (b) and wrapping of latter around a 5-mm-
diameter glass rod (c). d,e) Cross-sectional SEM images of sandwich-like Ti3C2Tx/SWCNT (d) and Ti3C2Tx/MWCNT papers (e). Reproduced with
permission.[202]

treatment. These films exhibited high volumetric capacitances with metal catalyst nanoparticles and form 3D nanotube array
around 460 F cm−3 and the symmetric capacitor based on these structures.[192] To produce paper-like free-standing CNT paper,
film electrodes showed a high volumetric energy density of these CNTs should be first dispersed into solution with sur-
41 Wh L−1 within a wide voltage window of 1.6 V. factants, followed by vacuum filtration, doctor blade or other
fabrication process. The presence of surfactants will consider-
Chemical Vapor Deposition: Chemical vapor deposition is most ably lower the electrical conductivity of the integrated CNT film.
commonly used approach for synthesizing CNTs, including Floating catalyst chemical vapor deposition (FCCVD) is a fac-
SWCNTs and MWCNTs. Normally, CNTs grow on the substrate ile method to directly produce CNT film. Compared with the

Figure 10. Scalable free-standing V2O5/CNT film. a) Schematic diagram illustrating the processes for preparing V2O5/CNT free-standing film; b) Optical
image of V2O5/CNT film with length over 13 cm; c) Optical image of highly dense V2O5/CNT film cover the surface of a bottle, inset is the contact
angle of this film; d) SEM image of highly dense V2O5/CNT film; e) EDX mapping images (carbon, oxygen, and vanadium mapping). Reproduced with
permission.[33]

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traditional CVD methods which fix catalysts on substrates, the N-doped carbon nanofibers network with strong cross-linked
catalyst particles in FCCVD method are continuously formed structure between fibers via carbonization of electrospun poly-
in the reactor and catalyst deactivation problem is avoided. acrylonitrile (PAN)/polyvinylpyrrolidone (PVP)/terephthalic
The catalysts are introduced into the hot reaction zone by three acid (TPA) hybrid composite fibers (Figure 11).[228] Compared
methods: 1) a syringe process using catalyst dissolved in carbon to non-cross-linked carbon nanofiber network, the cross-linked
source, 2) sublimation of catalyst at elevated temperatures or 3) a N-doped carbon nanofiber network owns a reduced resistance
gaseous catalyst source such as ferrocene.[205] Recent research and enhanced capacitance (223.8 F g−1). In a more recent study,
showed that the CNTs film produced via FCCVD displays high Cheng et al. reported that TPA can be used as pore forming
electrical conductivity and can be easily integrated with other agent in fabrication of flexible, porous carbon nanofibers
materials to fabricate hybrid electrodes for flexible energy stor- network.[229] This porous carbon fiber network exhibited
age systems.[206,207] increased specific capacitance (257.6 F g−1) and rate capability
Niu et al. demonstrated a ‘skeleton/skin’ SWCNTs/PANI (64.4% from 0.5 A g−1 to 700 A g−1) compared to non-porous
structure by electrochemical polymerization directly on carbon fiber network.
SWCNTs films prepared by FCCVD method. This unique con- Carbide derivation is also an effective approach to develop
tinuous structure ensures these hybrid films have much higher carbon nanofiber network.[231,232] Presser et al. fabricated
conductivity and better electrochemical performance compared carbide-derived carbon (CDC) via electrospinning of titanium
to SWCNTs/PANI composite films prepared by post-deposition carbide (TiC) and the following chlorination to remove Ti at
of PANI on SWCNTs films. The conductivity of these films elevated temperatures.[231] The as-prepared TiC-CDC films show
can reach about 1138 S cm−1. Supercapacitors fabricated using an average pore size of ≈1 nm and high specific surface area
these films can achieve both high energy density (131 Wh kg−1) of 1390 m2 g−1. Besides, these mechanically flexible films can
and power density (62.5 kW kg−1).[207] A recent research further display a high gravimetric capacitance of 110 F g−1 in aqueous
showed that the isotropically buckled CNT film synthesized via electrolyte and 65 F g−1 in organic electrolyte when directly
FCCVD method can be applied to omnidirectionally stretchable used as electrode material for supercapacitor application.
supercapacitors and displays high performance.[206] Carbon-fiber network films are good candidates to deposit
Except for the electrode materials and structures mentioned other high capacity/capacitance active materials due to its open
above, lots of CNT-based and CNT-composite-based electrodes porous structure, high electrical conductivity and high mechan-
have been prepared via various facile methods. A detailed sum- ical stability. Yan et al. used electrospun carbon nanofiber
mary of CNT-based paper-like electrodes and their flexible (CNF) paper as substrate to polymerize polyaniline on its
energy storage devices is depicted in Table 3. surface and successfully fabricated free-standing flexible CNF/
PANI composite paper.[238] This paper electrode demonstrated a
high specific capacitance of 638 F g−1 for CNF/PANI composite
3.3. Carbon-Fiber Paper-Like Electrodes paper electrode, two times higher than the bare CNF paper
electrode (317 F g−1). Miao et al. obtained a flexible porous
Carbon-fiber network consisted of interconnected carbon carbon nanofiber (PCNF)/MoS2 core-shell fiber film through a
fibers with diameters ranging from tens of nanometers to sev- combination of electrospinning of carbon fiber networks and
eral micrometers is another important kind of carbon-based solvothermal coating of MoS2 nanosheet arrays.[239] When the
paper-like electrodes. These carbon fiber network has high spe- highly flexible PCNF/MoS2 composite film is used as a binder-
cific surface area, high electrical conductivity and highly scal- free anode in lithium-ion battery, it exhibits a high specific
able.[227] Several approaches can be used to produce these 3D capacity of 954 mAh g−1 and good cycling stability with almost
cross-linked carbon structures, such as electrospinning, carbide 100% retention after 50 cycles.
derivation, CVD, etc.[28,228–234] Among these methods, electro- The detailed compositions, synthesis methods of carbon
spinning seems to provide the simplest approach in making fiber-based paper-like electrodes and their performances in flex-
nanofibers and microfibers with both solid and hollow inte- ible energy storage devices are summarized in Table 4.
riors that are exceptionally long in length, uniform in diameter
and diversified in composition.[227] Normally, the electronspun
carbon fiber systems are rigid and non-flexible. However, by 3.4. Carbon-Free Paper-Like Electrodes
tuning synthetic conditions, flexible carbon-fiber based paper-
like films can be obtained. Carbon allotropes including amorphous carbon,[246] graphite,[76]
Mechanically flexible films consisting of electronspun carbon fullerene,[247,248] carbon nanotubes,[49] and graphene[123,249]
fibers were prepared by first electrospinning aqueous mixtures have been widely studied as electrode materials for energy
of natural alkali lignin with polyvinyl alcohol (PVA) followed by storage. Different structures such as carbon film,[76,250] carbon
stabilization in air and carbonization in inert atmosphere.[234] foam,[154,251] carbon aerogel,[26,252] carbon hydrogel,[253,254]
This flexible electrode yielded specific capacitance of 64 F g−1 carbon paper,[255,256] and carbon cloth,[80,91] have been devel-
and retained 90% of its initial capacitance after 6000 cycles. oped. Various morphologies like nanodots,[257] nanotubes,[49]
Cross linking of electrospun carbon fibers can help to fur- nanoribbon,[258] nanofiber,[228] nanosheets,[109] have also been
ther increase its electrical conductivity.[235,236] Heteroatom explored to improve their performances. However, the theo-
doping can also contribute to the increased conductivity and the retical capacitance/capacity of carbon materials is relatively low.
added pseudocapacitance for electric double-layer capacitance For example, the theoretical capacitance of graphene for super-
carbon.[237] Cheng et al. successfully fabricated flexible, porous, capacitor is 550 F g−1 and the theoretical capacity of graphite for

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Table 3. CNT-based paper-like electrodes and their flexible energy storage devices.

Electrodes Synthesis methods Device Performance Ref.

Capacitance/Capacity Power Density Energy Density Cycling Stability
SWCNT film FCCVD* SC 35 F g−1 197.3 kW kg−1 43.7 Wh kg−1 – [199]

MWCNT film Layer-by-layer assembly SC −1 – – – [200]

159 F g

132 F cm−3
Functionalized CNT film Vacuum filtration SC 150 mF cm−2 4.2 W cm−3 1.5 mWh cm−3 90% after 10000 cycles [49]

PPy-CNT film CVD SC 494 F g−1 – – 65.6% after 10000 cycles [208]

Electrodeposition 59.3 mF cm−2

PPy-CNT film Vacuum filtration SC 0.28 F cm−2 – – 95% after 10000 cycles [209]
Electrodeposition
PPy-MnO2-CNT film CVD SC 351 F g−1 10 kW kg−1 39.7 Wh kg−1 94.4% after 10000 cycles [210]

In situ polymerization
PANI-CNT paper Vacuum filtration SC 350 F g−1 2.19 kW kg−1 7.1 Wh kg−1 91.9% after 1000 cycles [211]
Electrodeposition
PANI-SWCNT film Electrodeposition SC 236 F g−1 62.5 kW kg−1 131 Wh kg−1 85% after 1000 cycles [207]

PEDOT-SWCNT film Vacuum filtration SC −1 kg−1 kg−1 90% after 1000 cycles [212]
133 F g 825 W 7 Wh
Si-PEDOT-CNT film Vacuum filtration LIB 2180 mAh g−1 – – 90% after 100 cycles [213]

Si-SWCNT paper Vacuum filtration LIB −1 – – 60% after 50 cycles [214]

3000 mAh g
PLD*
AC-CNT paper Vacuum filtration SC 267.6 F g−1 7.3 kW kg−1 22.5 Wh kg−1 97.5% after 5000 cycles [215]

MnO2-CNT film Water-assisted CVD SC 540 F g−1 1.5 kW kg−1 20 Wh kg−1 – [216]

Vacuum filtration
Ti3C2-CNT paper Vacuum filtration SC 390 F cm−3 – – 114.1% after 10000 cycles [202]

Ti3C2-CNT paper Vacuum filtration SIB 421 mAh g−1 – – 109% after 500 cycles [217]

Porous Ti3C2-CNT paper Vacuum filtration LIB 1250 mAh g−1 – – 63.3% after 100 cycles [218]

Nb2C-CNT paper Vacuum filtration LIB 780 mAh g−1 – – 116% after 100 cycles [219]

MoO3–x/CNT paper Vacuum filtration SC 420 F g−1 – – 90% after 5000 cycles [86]
−3
420 F cm
HxMoO3–y/CNT paper Vacuum filtration SC 350 F cm−3 6.8 W cm−3 1.1 mWh cm−3 93.3% after 4000 cycles [84]

KyMoO3–x/CNT paper Vacuum filtration SC 374 F cm−3 6.5 W cm−3 0.91 mWh cm−3 89% after 10000 cycles [220]

V-MnO2-CNT-paper Vacuum filtration SC 439 F g−1 1.6 W cm−3 4.98 mWh cm−3 92% after 10000 cycles [88]

V2O5-CNT film Doctor-blade SC 460 F cm−3 25 kW L−1 41 Wh L−1 79.8% after 5000 cycles [33]

V2O5-CNT film Vacuum filtration SIC* 35 F g−1 45 kW kg−1 38 Wh kg−1 80% after 900 cycles [221]

V2O5-CNT film Hydrothermal reaction vacuum LIB 340 mAh g−1 – – 76.5% after 50 cycles [222]
filtration
VN-CNT film Vacuum filtration SC 7.9 F cm−3 0.4 W cm−3 0.54 mWh cm−3 82% after 10000 cycles [201]

In2O3-CNT film Vacuum filtration SC 64 F g−1 7.48 kW kg−1 1.29 Wh kg−1 82.8% after 500 cycles [223]

rNb2O5-rGO-CNT film Vacuum filtration SC 726.2 C g−1 – – 87% after 3000 cycles [224]

WO3-CNT film Vacuum filtration Evaporation SC 2.6 F cm−3 30.6 mW cm−3 0.59 mWh cm−3 75.8% after 50000 cycles [225]

Ni(OH)2-CNT paper Vacuum filtration Chemical bath SC 1144 F g−1 – – 98% after 1000 cycles [203]
deposition
PMTA/SWCNT-SWCNT film Filtration LIB 163 mAh g−1 – – 86.6% after 200 cycles [204]

Rolling
Graphene-PPy-CNT film Vacuum filtration SC 211 F g−1 – – 95% after 5000 cycles [226]
−3
122 F cm

*Notes: Floating catalyst chemical vapor deposition (FCCVD), Pulsed laser deposition (PLD), Sodium-ion capacitor (SIC).

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Figure 11. Flexible and cross-linked N-doped carbon nanofiber network film. a) Schematic of the preparation of cross-linked carbon nanofibers.
b) Photo image of the CLCF before and under folding; c) SEM and d) HRTEM images of the CLCF. Reproduced with permission.[228] Copyright 2015, Elsevier.

Li-ion battery is 372 mAh g–1.[102,259] These values are consider- MoS2 nanosheets and used vacuum filtration method to get
ably lower than the theoretical values of most pseudocapacitive a free-standing pure MoS2 paper.[260] These paper-like elec-
materials (>1000 F g−1).[13,70,87] Thus, to develop free-standing trodes achieved high volumetric capacitances ranging from
carbon-free paper-like electrodes for energy storage is attrac- 400 to 700 F cm−3 in a variety of aqueous electrolytes. These
tive. Several methods have been reported in making such kind MoS2 paper electrodes achieved an even higher energy density
of electrodes, including vacuum filtration, rolling, electrospin- (0.11 W cm−3) and power density (51 W cm−3) in organic elec-
ning, anodization, electrodeposition, and sacrificial template trolyte with operating working window up to 3.5 V (Figure 12).
methods, etc. MXenes (of the fomula Mn+1XnTx, where M is a transition
High conductive nanomaterials could be used to fabri- metal, X is C and/or N, and Tx denotes surface functionaliza-
cate high-performance flexible free-standing paper without tion) are a relatively young family of two-dimensional (2D)
the need of carbon materials as mechanical support or cur- materials.[51,83] MXenes are of high conductivity and can be
rent collector. Acerce et al. successfully synthesized 1T phase fabricated into free-standing films, which can be directly used

Table 4. Carbon fiber-based paper-like electrodes and their flexible energy storage devices.

Electrodes Synthesis methods Device Performance Ref.

Capacitance/Capacity Power Density Energy Density Cycling Stability
N-carbon fiber paper Electrospinning SC 175 F g−1 1.2 kW kg−1 5.9 Wh kg−1 106% after 20000 cycles [228]
Porous carbon nanofiber film Electrospinning SC 104.5 F g−1 600 W kg−1 3.22 Wh kg−1 94% after 2000 cycles [240]
Porous cross-linked carbon Electrospinning SC 257.6 F g−1 56 kW kg−1 10.2 Wh kg−1 95% after 20000 cycles [229]
fiber paper
Porous carbon nanofiber- ultra- CVD SC 120 F g−1 23 W cm−3 2.4 mWh cm−3 96% after 5000 cycles [28]
thin graphite film
Carbon fiber-graphene paper Electrospinning Vacuum SC 197 F g−1 – – 83.8% after 1500 cycles [241]
filtration
Carbon nanofiber-graphene Electrospinning SC 183 F g−1 – – 92% after 4500 cycles [242]
paper
PANI-carbon fiber paper Electrospinning Polymerization SC 638 F g−1 – – 90% after 1000 cycles [238]
Olivine-carbon nanofiber Electrospinning LIB 152 mAh g−1 – – 98.2% after 100 cycles [243]
V2O5-carbon fiber paper Electrospinning SC 214 F g−1 156 W kg−1 45 Wh kg−1 80% after 1000 cycles [244]
Electrodeposition
MoS2-carbon fiber membrane Electrospinning LIB 954 mAh g−1 – – 100% after 50 cycles [239]
NiS-carbon nanofiber Electrospinning LIB 1149 mAh g−1 – – 84.3% after 100 cycles [245]
membrane

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Figure 12. Chemically exfoliated 1T MoS2 electrodes. a,b) Photographs of electrodes consisting of a thick film of chemically exfoliated 1T MoS2 prepared
by vacuum filtration and transferred onto rigid glass (a) and a flexible polyimide substrate (b). c) Side view of the electrode observed by scanning
electron microscopy (SEM) showing the layered nature of the film made by restacking exfoliated MoS2 nanosheets. d) High-magnification image of
restacked MoS2 nanosheets. e) SEM image of as-exfoliated monolayer 1T phase MoS2 nanosheets. f) High-angle annular dark-field scanning transmis-
sion electron microscope image of monolayer 1T phase MoS2. Inset: Atomic structure of 1T phase MoS2 (Mo and S atoms are displayed in blue and
yellow, respectively). g) XRD of bulk MoS2 compared with as-exfoliated restacked MoS2. h) High-resolution X-ray photoelectron spectrum from the Mo
3d region of as-exfoliated 1T MoS2 (black). Contributions from 1T and 2H phase components in the Mo 3d spectrum are indicated by blue and red
curves, respectively. Reproduced with permission.[260] Copyright 2015, Nature Publishing Group.

as electrodes in Li-ion batteries and supercapacitors. Ghidiu films (Figure 13).[51] The thickness of these films can be tuned.
et al. synthesized highly conductive two-dimensional titanium Their densities are in the range of 2.2–3.8 g cm−3. By employing
carbide ‘clay’ and rolled them into free-standing flexible Ti3C2Tx these films as electrodes in supercapacitor, they showed a high

Figure 13. Free-standing titanium carbide ‘clay’ film. a) Schematic of MXene clay synthesis and electrode preparation. MAX phase is etched in a solu-
tion of acid and fluoride salt (step 1), then washed with water to remove reaction products and raise the pH towards neutral (step 2). The resulting
sediment behaves like a clay; it can be rolled to produce flexible, freestanding films (step 3), moulded and dried to yield conducting objects of desired
shape (step 4), or diluted and painted onto a substrate to yield a conductive coating (step 5). b) When dried samples (left, showing cross-section and
top view) are hydrated (right) they swell; upon drying, they shrink. c) Image of a rolled film. d) ‘Clay’ shaped into the letter M (≈1 cm) and dried, yielding
a conductive solid (labelled with the experimental conductivity of ‘clay’ rolled to 5 mm thickness). The etched material is referred to as Ti3C2Tx, where
the T denotes surface terminations, such as OH, O and F. Reproduced with permission.[51] Copyright 2014, Nature Publishing Group.

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volumetric capacitance over 900 F cm−3 and gravimetrical 4. Applications

capacitance of 245 F g−1. The electrodes also demonstrated no
measurable capacitance losses even after 10000 cycles. The heavy demand of flexible electronics push the develop-
In addition to these highly conductive materials, materials ment of various flexible energy storage devices. Different types
that are less conductive can also be employed as free-standing of energy storage devices have different scopes of application,
paper electrode. Yao et al. reported an ultrathin, transparent, depending on their electrochemical properties and working
molybdenum trioxide (MoO3) nanopaper electrode via vacuum mechanism. For example, supercapacitors are suitable for elec-
filtration.[13] The ultrathin film with only two or three nanobelts tronics that required fast charging and discharging and long
in thickness allows not only efficient ion diffusion but also cycling stability, while lithium-oxygen batteries fit the applica-
effective electron transport even MoO3 is not very conductive tions that require continuously and high energy supply. In this
(Figure 14). This nanopaper electrode delivers an excellent spe- section, four different kinds of flexible paper-based energy stor-
cific capacitance of 1198 F g−1 and long-term cycling stability ages devices, including supercapacitors, Li-ion batteries, Li-S
over 20000 cycles. batteries and Li-O2 batteries, will be introduced and discussed.
Nanoporous metal paper is emerging as a new class of mate-
rial for energy storage.[261] They can be used as a highly con-
ductive substrate for deposition of metal oxide or conducting 4.1. Flexible Supercapacitors
polymers (Figure 15).[262,263] Alternatively, they can also be
transformed into metal oxide, metal nitride, metal carbide or Supercapacitors, also known as ultracapacitors or electrochem-
metal fluoride and are directly employed as electrodes for flex- ical capacitors, have gained much research interest during the
ible energy storage systems.[264] The multifunctional properties past decade. However, the concept of capacitor is not new. In
of nanoporous metal papers make them particularly attractive 1879, Helmholtz first discovered the phenomenon of double-
for carbon-free electrodes. layer capacitance.[277] The first patent on double-layer capacitor
The research on carbon-free paper-like electrodes is just in was filed by Becker in 1957.[278] The first generation of commer-
its infancy, further research on both material selection and cial capacitors were manufactured by Panasonic/Matsushita in
electrode architecture is essential. More carbon-free paper- 1978 and NEC in 1980.[279] Since then, enormous efforts have
like electrodes and their applications in flexible energy storage been devoted to the research on this ultrafast charging and
devices are summarized in Table 5. discharging devices.

Figure 14. Ultrathin transparent MoO3 nanobelts nanopaper. a) SEM image of ultrathin transparent MoO3 nanobelts nanopaper. b) Side view of trans-
parent MoO3 nanopaper. c) Transmittance spectra of MoO3 nanopapers with different mass loading. d) Optical images of transparent MoO3 nanopaper
under different times of folding: Original, one folding, two folding, three folding, four folding, and full recovery. Reproduced with permission.[13]

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Figure 15. Flexible conducting polymer-nanoporous metal film electrode. a) Schematic illustration of the fabrication process of the ultrathin flexible
solid state supercapacitor. b,c) SEM images of nanoporous gold (NPG) and NPG-PPy8s. d) SEM side view of NPG-PPy8s. e,f) Digital pictures of mac-
roscopic NPG and NPG-PPy thin membranes. g) SEM cross sectional image of the as-designed symmetric supercapacitor device. Reproduced with
permission.[263]

According to the different working mechanism, superca- of electrolyte used, supercapacitors can also be classified into
pacitors can be classified into electric double layer capacitors aqueous supercapacitors and solid-state supercapacitors. As for
(EDLC) and pseudocapacitors.[280] EDLCs store energy mainly the flexible solid-state supercapacitors, gel-based electrolytes
by ion absorption at the interface between electrodes and are widely adopted, including PVA/H3PO4, PVA/H2SO4, and
electrolyte. Pseudocapacitors rely on the fast redox reactions PVA/KOH, PVA/LiCl, etc.[12,14,80,282]
at the electrode surface to collect and release charges. Carbo- For paper-based and paper-like electrodes, most of them are
naceous materials are widely explored for EDLCs, while the assembled into sandwich-like supercapacitor configuration.
conducting polymers and metal oxides are mainly used for Yuan et al. assembled the solid-state supercapacitors by sand-
pseudocapacitors. Because of their different charge-storage wiching a PVA/H3PO4 film between two identical PANI-Au
mechanisms, EDLCs typically have excellent cycling stability paper electrodes (Figure 16a,b).[32] PVA/H3PO4 film worked as
(>200, 000 cycles) and power density, but relatively low in spe- both the electrolyte and the separator. This devices displayed
cific capacitance and energy density. Pseudocapacitors, on the good stability under different bending state. Likewise, Yao
other hand, are great in terms of energy density, but inferior et al. fabricated the solid-state supercapacitors via sandwiching
in stability and power density. Due to chemical reactions are a PVA/H2SO4 gel film between two symmetric PANI/graphite
involved in pseudocapacitors, irreversible components will paper electrodes (Figure 16c,d).[14] The cyclic voltammetry
accumulate during cycling, leading to device deterioration.[20] curves of the as-fabricated devices almost did not change under
Recently, a new concept of Li-ion capacitor by integrating EDLC different bending states, showing its excellent flexibility.
electrode as cathode and pseudocapacitors electrode as anode Paper-based planar interdigital supercapacitors hold many
has been proposed. It is anticipated that this kind of capacitors advantages compared with traditional sandwiched structure,
can achieve higher capacitance than EDLCs and better cycling such as the improved ion diffusion and easy integration with
stability than pseudocapacitors. Thus the energy density is other planar flexible electronics devices. Yuan et al. success-
improved without sacrificing the power density.[281] fully fabricated two planar interdigital supercapacitors on one
Supercapacitors can be assembled as sandwich-like devices piece of PPy-coated paper (Figure 17a–b).[12] The two superca-
and planar interdigital devices. On the basis of different types pacitors (denoted as Devices A and Devices B) showed a planar

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Table 5. Carbon-free paper-like electrodes and their flexible energy storage devices.

Electrodes Synthesis methods Device Performance Ref.

Capacitance/Capacity Power Density Energy Density Cycling Stability
Si nanowire paper RFCVD* LIB 2699 mAh g−1 – – 38.4% after 100 cycles [265]
MoO3 nanopaper Vacuum filtration SC 1198 F g−1 10.1 kW kg −1
22.89 Wh kg −1 96.5% after 20000 cycles [13]
h-MoO3 film Vacuum filtration SC 996 C g−1 21.3 W cm−3 0.3 Wh cm−3 92% after 6000 cycles [266]
1100 C cm−3
MoO3–x nanopaper Vacuum filtration SC 652 F cm−3 1.45 kW kg−1 8.3 Wh kg−1 85.7% after 25000 cycles [267]
MoS2 nanopaper Vacuum filtration SC 650 F cm−3 51 W cm −3
0.11 Wh cm−3 93% after 10000 cycles [260]
α-MnO2 paper Vacuum filtration SC 118 F g−1 – – 95.3% after 1000 cycles [268]
TiO2 paper Vacuum filtration LIB 339 mAh g−1 – – 100% after 400 cycles [269]
TiOxNy paper Vacuum filtration SC 120.9 F g−1 – – 88% after 300 cycles [270]
Ti3C2 paper Vacuum filtration SC 900 F cm−3 – – 100% after 10000 cycles [51]
245 F g−1
Ti3C2/PVA paper Vacuum filtration SC 528 F cm−3 – – 85.9% after 10000 cycles [271]
VN@C film Vacuum filtration SC 282 mF cm−2 2.72 W cm−3 0.97 mWh cm−3 91.8% after 12000 cycles [272]
NiO-Ni nanofiber paper Electrospinning LIB 1054 mAh g−1 – – 92.8% after 1500 cycles [273]
NiF2 film Anodization SC 66 mF cm−2 112 kW kg−1 384 Wh kg−1 150% after 10000 cycles [264]
733 F cm−3
358 F g−1
PPy film Sacrificial template SC 316.2 F g−1 – – 30.9% after 500 cycles [274]
PEDOT film Vacuum filtration SC 120 F g−1 16.2 W cm−3 6.8 mWh cm−3 80% after 8000 cycles [275]
NiMn nanoporous metal paper Dealloying SC 4.4 F cm−2 – – 85% after 2000 cycles [261]
887 F cm−3
MnO2-nanoporous gold paper Electrodeposition SC 1145 F g−1 16 kW kg−1 57 Wh kg−1 85% after 1000 cycles [262]
MnO2-nanoporous Au-MnO2 paper Electrodeposition SC 916 F g−1 – – 97.1% after 3000 cycles [276]

Note: *RFCVD: Radio frequency chemical vapor deposition.

structure, both with 2 pairs of interdigital-shaped electrodes rate, and relatively good long-term stability.[10] Recent increasing
and coated with solid-state PVA/H3PO4 electrolyte. By changing demand in flexible electronics and wearable electronics further
the linking between four terminals of A1, A2, B1 and B2, Devices drive the development of light-weight, thin, and flexible Li-ion
A and Devices B exhibited a series or parallel relationship. batteries. However, currently most of the Li-ion batteries are
Comparing the experimental capacitance and the calculated still adopting the conventional rigid, heavy and bulky configura-
capacitance, it was found that these devices roughly obeyed the tion.[283,284] Here we will review the recent progress in making
basic rule of series and parallel connections. Furthermore, Yao flexible paper-based or paper-like anodes and cathodes that are
et al. proposed a novel method to fabricate paper-based planar the key components for Li-ion batteries.
interdigital supercapacitors (Figure 17c–d).[14] First, pencil was Generally, anode and cathode will be fabricated by mixing
used to draw the as-designed patterns on paper, forming a con- powder of active materials with conducting agents such as
ductive interdigital graphite planar supercapacitor. Then PANI carbon black and polymeric binders such as PTFE or PVDF to
networks were electrodeposited on the interdigital electrodes form slurry and then coated onto Cu foil and Al foil, respec-
of each side. The interdigital solid-state planar supercapacitor tively. The main drawback for this electrode configuration is
device was fabricated by coating solid-state PVA/H2SO4 electro- that the active materials are likely to detach from the smooth
lyte on the surface of the interdigital electrodes and the gaps conductive substrates under the bending states.[102] To solve
in between. The symmetrical curves of charging and discharge this problem, developing new electrodes with robust mechan-
parts displayed its good capacitive behavior. ical flexibility is necessary. Graphene and CNTs are two of the
most important carbonaceous materials with excellent electrical
conductivity. Paper-like assembly with 3D porous structure of
4.2. Flexible Li-Ion Batteries graphene flakelets or CNT wires with rough surface have been
widely investigated in recent years. Yet, pure graphene and
Since 1991, the first commercial product released by Sony, CNTs paper often suffer from large irreversible capacity, fast
Li-ion batteries have attracted great interest due to their high capacity fade, low capacities and safety issue due to Li dendrite
energy density, high operation voltage, low self-discharging formation between electrode and separator, resulting in short

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interest. Nanostructured active materials are

uniformly distributed in these 3D conduc-
tive networks and could effectively reduce
the polarization and pulverization associated
with large volume change during lithiation
and delithiation process.[163,164,294]
Zhou et al. reported a Fe2O3/SWCNTs
paper with a ultrahigh Fe2O3 loading of
88 wt% prepared by oxidizing a floating cata-
lyst chemical vapor deposition-assembled Fe/
SWCNT paper.[294] This flexible paper showed
a high reversible capacity of 1243 mAh g−1
at a current density of 50 mA g−1 and a good
cyclic stability over 90 cycles. CNTs can also
be used to fabricate MXene/CNT paper
via vacuum filtration method. The porous
Ti3C2Tx/CNT paper electrode displayed a
high capacity of about 1250 mAh g−1 at 0.1 C
and good rate performance of 330 mA g−1
at 10 C. This excellent performance was
attributed to the highly conductive 3D CNT
network as well as the porous characteristic
of 2D MXene nanoplate.[218] Graphene can
Figure 16. Flexible paper-based solid-state supercapacitors. a) The fabricated solid-state SCs also be used in vacuum filtration to assemble
(upper) and photographs of the SC (down). b) CV scans of the all-solid-state SC at different cur- flexible free-standing paper-like electrodes.
[32]
vature. Reproduced with permission. c) The left part is the optical picture of three solid-state Zhao et al. used acid-sonication treatment to
supercapacitors with 120 minutes PANI depositing graphite/polyaniline-paper (G/PANI-Paper)
electrodes in series to light a red LED. The inset is the enlarged optical picture of the alight LED.
create graphene with carbon vacancies fol-
The right part is optical pictures of the flexible solid-state supercapacitors with 120 minutes lowed by filtration of these porous graphene
PANI depositing G/PANI-Paper electrodes at five bending states with bending angle of 0°, 30°, with Si nanoparticle to make free-standing
45°, 60° and 90°, respectively. b) Cyclic voltammetry of the supercapacitors at the five bending Si/graphene paper. These paper electrodes
states. Reproduced with permission.[14] Copyright 2013, Elsevier. achieved an outstanding reversible capacity
of 3200 mAh g−1 at 1 A g−1 and a good rate
circuit.[128,197] Recent studies showed that hybridizing active capacity of 1100 mAh g−1 at 8 A g−1 as well as good cycling stability
electrode materials with graphene or CNTs to fabricate flexible which repeated up to 99.9% between cycles for over 150 cycles.[163]
and free-standing graphene- or CNTs-based electrodes are effec-
tive in addressing the problem.
Hu et al. employed a doctor blade method to coat CNT ink 4.3. Flexible Li-S Batteries
on stainless steel substrate to form a conducting layer, followed
by the further blade-coating of Li4Ti5O12 (LTO) and LiCoO2 Lithium-ion batteries have achieved a great success in the past
(LCO) separately (Figure 18).[15] The LTO/CNT and LCO/CNT three decades and have been applied for many flexible elec-
films were then easily delaminated from the substrates by tronics devices. However, the state-of-the-art Li-ion batteries
simply immersing them into DI water and peeling off. After are still not able to completely satisfy the increasing demand
that, the LTO/CNT and LCO/CNT films were rolled to the paper for applications such as electric vehicles and grid-level energy
via coating a thin layer of PVDF in between, which the PVDF storage that require extremely high energy density for the
functions as a glue to stick the double layer films on paper. This emerging applications.[295]
is the first demonstration using commercial paper in Li-ion bat- Lithium-sulfur (Li-S) batteries are promising candidates for
teries, where paper is used as both separator and mechanical the next generation rechargeable batteries due to their higher
support. This Li-ion paper battery is thin, about 300 µm in total, theoretical specific capacity (1673 mAh g−1) and energy density
and yielded a discharging capacity of 120 mAh g−1. Besides, (2500 Wh kg−1) compared with Li-ion batteries.[22,295] The key
this device showed excellent self-discharge performance that difference between these two batteries is the charge storage
only 0.54 mV voltage drop was observed for this full cell after mechanism. Li-ion batteries store charges through the inter-
350 hours. calation of lithium ion into layered active materials, such as
Incorporation of materials with high theoretical capacity, graphite or layered metal oxides. Because the lithium ions can
such as Si (4200 mAh g−1),[285] Ge (1600 mAh g−1),[286] only be intercalated topotactically into some specific sites, their
Sn (992 mAh g−1),[287] Fe2O3 (1005 mAh g−1),[288] theoretical capacity and energy density are typically limited to
Co3O4 (890 mAh g−1),[289] MoO2 (838 mAh g−1),[290] 370 mAh g−1 and 420 Wh kg−1.[22] In contrary, Li-S batteries
SnO2 (781 mAh g−1),[291] CuO (674 mAh g−1),[292] V2O5 store charges through a multi-electron electrochemical redox
(294 mAh g−1),[222,293] with graphene or CNTs to make free- reaction (16Li + S8 → 8Li2S) involving the metal plating and
standing paper-like electrodes have attracted considerable stripping on the lithium anode (Li+ + e− → Li) and a conversion

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electrical conductivity of the S electrode and

preventing the dissolution of polysulfides,
including carbon materials, such as carbon
nanotubes,[297,298] graphene,[299,300] carbon
nanofibers,[301,302] porous carbon,[303,304] and
hollow carbon spheres,[305] conducting poly-
mers like polyaniline (PANI),[306] polypyrrole
(PPy)[18,307] and poly(3,4-ethylenedioxythiophne)-
poly(styrenesulfonate) (PEDOT/PSS),[308] metal
oxides, such as TiO2,[309] Ti4O7,[310] MnO2,[311]
indium tin oxide (ITO),[312] Fe2O3,[313]
La2O3,[314] VO2,[315] V2O5,[316] MoO3,[316]
Nb2O5,[317] and metal hydroxides including
Ni(OH)2[318] and Co(OH)2.[319,320] Among these
host materials, graphene, CNTs and carbon
fibers are proved to be very efficient in fab-
ricating flexible Li-S electrodes.[18,157,298,302]
Huang et al. prepared mesoporous gra-
phene-sulfur paper by filtration and sulfur
vapor treatment approach (Figure 19).[157]
Amorphous sulfur was homogeneously distrib-
uted and immobilized in the mesoporous archi-
tectures of porous graphene paper. The free-
standing, binder-free as-prepared mesoporous
graphene-sulfur papers can be directly used
as electrodes in lithium-sulfur batteries, which
Figure 17. Flexible paper-based interdigital solid-state supercapacitors. a) Optical photograph yielded a high specific discharge capacity of
of the as-fabricated planar structured solid-state supercapacitor with polypyrrole-coated paper 1393 mAh g−1 and retain 689 mAh g−1 after
electrodes (polymerization time of 180 minutes). The corresponding schematic diagram is 50 cycles. Li et al. demonstrated a foldable
plotted below. Reproduced with permission.[12] Copyright 2013, Royal Society of Chemistry. lithium-sulfur battery by depositing sulfur on
b) Galvanostatic charge–discharge curves for the as-fabricated planar supercapacitor with the checkerboard patterned super elastic CNT
different device configuration at a fixed current of 1 mA. c) Optical picture of using a pencil to film.[298] This folded lithium-sulfur battery
draw a conductive graphite layer on the as-printed interdigital patterns to obtain an interdigital
substrate. The insert shows the flexible planar interdigital electrodes deposited polyaniline on
could be folded along two mutually ortho­
the interdigital graphite substrate. d) Charge and discharge curves of the planar interdigital gonal directions and showed <12% loss in spe-
supercapacitor with G/PANI-Paper electrodes at different currents. Reproduced with permis- cific capacity over 100 continuous folding and
sion.[14] Copyright 2013, Elsevier. unfolding cycles. Such flexible and foldable
lithium-sulfur batteries show their potential
in powering the flexible and foldable devices
reaction on the sulfur cathode (S8 + 16Li+ + 16e− = 8Li2S). These including laptops, cell phones, tablet computers, surgical tools and
reactions are non-topotactic and therefore lithium anodes and implantable biomedical devices in the future.
sulfur cathodes have excellent theoretical specific capacities of
3860 and 1673 mAh g−1, respectively.[22] Besides, the average of
the lithium-sulfur cell voltage of 2.15 V, they can achieve a theo- 4.4. Flexible Li-O2 Batteries
retical energy density of 2500 Wh kg−1.
Li-S batteries have been first reported in 1962.[296] After dec- Lithium-oxygen (Li-O2) batteries are also one of the most prom-
ades of intensive research, such batteries are still plagued with ising energy storage systems and have attracted worldwide
low discharge capacity and fast capacity decay during cycling. attention owing to its super-large theoretical energy density.[17]
In 2009, Nazar et al. reported a highly ordered nanostructured When an oxygen cathode is coupled with a lithium anode,
carbon-sulfur cathode for Li-S battery by encapsulating sulfur according to the reaction 2Li + O2 → Li2O2, which includes
within the mesopores of mesoporous carbon CMK-3, and a cathodic reaction of 2Li+ + O2 + 2e− → Li2O2 and an anodic
demonstrated its high discharge capacity of 1320 mAh g−1 and reaction of 2Li − 2e− → 2Li+, which could achieve an energy
[16]
stable cycling performance over 20 cycles. Since then, signifi- density of 3600 Wh kg−1 [(capacity of 1200 Ah kg−1) × (operating
cant progress has been made in the field of Li-S batteries. voltage of 3.0 V)], which is nearly one order of magnitude larger
The main problems impeding the application of Li-S than the conventional lithium-ion batteries (420 Wh kg−1). The
batteries include the low electrical conductivity of sulfur first Li-O2 battery, with a structure of Li/organic electrolyte/
(5 × 10−30 S cm−1), the dissolution of intermediate lithium air, was assembled and investigated in 1996.[321] However, this
polysulfides, and the large volume expansion (80%) of sulfur type of device did not receive much attention until Bruce et al.
during lithiation.[22] To overcome these challenges, various demonstrated its rechargeable ability recently.[322] Since the
materials are employed to immobilize S for enhancing the research on rechargeable Li-O2 batteries is still in its infancy,

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Figure 18. Flexible secondary Li-ion paper batteries. a) Schematic of the lamination process: the freestanding film is laminated on paper with a
rod and a thin layer of wet PVDF on paper. b) Schematic of the final paper Li-ion battery device structure, with both LCO/CNT and LTO/CNT laminated
on both sides of the paper substrate. The paper is used as both the separator and the substrate. c) SEM image of the cross section for the laminated
paper Li-ion battery. The layers thicknesses are CNT ≈2 µm, LTO ≈30 µm, paper ≈100 µm, LCO ≈30 µm, and CNT ≈2 µm. d) Galvanostatic charging/
discharging curves of the LTO anode (1.3–1.7 V) half cells with conductive paper current collectors. The mass of the LTO electrode is 1.8 mg. The current
rate is C/5. e) Cycling performance of LTO nanopowder (C/5, 0.063 mA) half cells. f) Flexible Li-ion paper batteries light an LED device. Reproduced
with permission.[15] Copyright 2010, American Chemical Society.

it remains very challenging to fabricate a

high performance Li-O2 battery, so flexible
or foldable Li-O2 batteries have rarely been
demonstrated. However, several groups have
attempted to assemble flexible Li-O2 batteries
in the laboratory and some prototypes have
been successfully developed.[19,323]
Liu et al. adopted an ancient Chinese
brush painting method to deposit the com-
mercial carbon ink on commonly used paper
(Figure 20).[19] This flexible low-cost paper-
ink (PI) cathode can be directly applied in
Li-O2 batteries by combining with lithium
belt anode, glass fiber separator and non-
aqueous electrolyte (1M lithium triflate in
tretraethylene glycol dimethyl ether). The
Li-O2 battery showed a high capacity of
about 6500 mAh g−1 at a current density
of 200 mA g−1 and reached about 50 cycles
with the capacity restricted to 1000 mAh g−1
at a current density of 200 mA g−1. The PI
cathode after bending 1000 cycles did not
show obvious deterioration in performance.
Besides, the electrochemical performance of
the Li-O2 battery can be further improved via
coating Ru nanoparticles on the PI cathode.

Figure 19. Flexible paper-based Li-S battery. a) A schematic illustration for the preparation of
mesoporous graphene paper–sulfur electrodes and application as cathode in lithium–sulfur 5. Conclusions and Outlook
batteries. b,c) Digital photographs of the MGP paper, exhibiting an intact paper-like mor-
phology (b) and flexible property (c). Reproduced with permission.[157] Copyright 2013, Royal The rapid development of flexible electrodes
Society of Chemistry. has open up new opportunities for flexible

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Figure 20. Flexible paper-based Li-O2 battery. a) Schematic representations for the design and preparation of the PI cathode. b) SEM image of pristine
paper. c) Photograph of the obtained flexible PI cathode. d) Enlarged image of (c). e) XRD pattern and f) Raman spectrum of the obtained PI cathode.
Reproduced with permission.[19]

energy storage systems and wearable electronics. Among them, electrode, the capacitance/capacity of the paper-based elec-
paper-based electrodes as a new class of electrode configuration trodes should be calculated based on the total mass/volume of
have attracted a lot attention. In this review, we have summa- the electrodes, including both electrochemically active materials
rized the recent advances in this area, with a particular focus and inactive cellulose paper substrates, instead of the mass or
on the methodology of fabricating these novel functional elec- volume of the active materials. For paper-like or film electrode,
trodes, including paper-supported electrodes and paper-like it is also critical to provide the areal capacitance/capacity of the
electrodes. Finally, in this section, we will discuss some key electrode. Likewise, the energy density and power density of
challenges and opportunities in this fast growing field. First, paper-based supercapacitors should be normalized to the mass,
paper-based electrodes have been widely used in flexible energy areal or volume of the entire device, including electrodes, elec-
storage devices such as supercapacitors and Li-ion batteries. trolyte, separator and packaging materials.
However, their application in Li-S and Li-O2 batteries, as well as Third, paper-based electrodes with high-mass loading of
some new types of energy storage system like Na-ion batteries, active materials (e.g., larger than 10 mg cm−2) should be
Mg-ion batteries has been rarely investigated. In exploring the explored for practical application. Currently, the mass loading
potential use of paper-based electrodes in these areas, some of active materials for paper-based electrodes are still in the
issues should be considered. For example, to use paper-based range of several µg to several mg. This relatively low loading
electrodes for Li-S batteries, the electrode is required to have is difficult to meet the increasing demand for high energy
not only good electrical conductivity and flexibility, but also density device for powering flexible electronics. Higher areal
strong affinity with sulfur. When they are used in Na-ion capacitance/capacity of paper-based electrode can be realized
batteries and Mg-ion batteries, a critical problem would be by simply increasing the film thickness. The challenge is to
whether these paper-based electrodes is mechanically/structur- retain efficient ion diffusion in a thick paper-based electrode,
ally robust that can accommodate large volume change during and thus, achieving high areal capacitance at fast charging/dis-
Na-ion and Mg-ion insertion and desertion, since these ions are charging rate.
much larger than Li-ions. Fourth, electrochemical property and stability of paper-based
Second, we believe that performance standards should be flexible energy storage devices under extreme conditions should
established for paper-based electrodes devices. For instance, be investigated as they are of great importance for some prac-
in order to better evaluate the practicality of supercapacitor tical applications. Previous studies have primarily focused on

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the performance of paper-based flexible energy storage devices T.L. acknowleges the financial support from the Chancellor’s Dissertation
under dry and ambient environment. Their performance under Year Fellowship awarded by Univeristy of California, Santa Cruz.
harsh environments, such as extremely humid conditions and Y.S. acknowledges the financial support from China Scholarship Council.
high/low temperatures, is rarely reported.
Fifth, new materials and fabrication techniques should be
explored for making novel paper-based electrodes. For example, Conflict of Interest
optically transparent paper-based electrodes and flexible energy
The authors declare no conflict of interest.
storage devices can be implemented into all-transparent elec-
tronic devices. Self-healing paper-based electrodes can repair
the damage within the electrodes and extend their lifespan,
which can be critical for certain energy storage devices. Investi- Keywords
gation on new materials as well as fabrication processes could batteries, electrodes, flexible, paper, supercapacitors
open up new opportunities for flexible paper-based energy
storage devices. Received: March 2, 2017
Sixth, new electrolytes should be explored for flexible paper- Revised: March 31, 2017
based energy storage devices. Electrolytes can significantly Published online: May 29, 2017
affect the specific capacitance/capacity, energy density, power
density and the cycling stability of flexible energy storage
devices. An ideal electrolyte used in flexible paper-based energy
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