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advanced electrochemical energy storage

Cite this: Chem. Soc. Rev., 2018,
47, 2837
Wenshuai Chen,†a Haipeng Yu, †a Sang-Young Lee, b
Tong Wei,c Jian Lia and
Zhuangjun Fan *c

Received 28th December 2017
DOI: 10.1039/c7cs00790f
rsc.li/chem-soc-rev
Nanocellulose has emerged as a sustainable and promising nanomaterial owing to its unique structures,
superb properties, and natural abundance. Here, we present a comprehensive review of the current
research activities that center on the development of nanocellulose for advanced electrochemical
energy storage. We begin with a brief introduction of the structural features of cellulose nanofibers
within the cell walls of cellulose resources. We then focus on a variety of processes that have been
explored to fabricate nanocellulose with various structures and surface chemical properties. Next, we
highlight a number of energy storage systems that utilize nanocellulose-derived materials, including
supercapacitors, lithium-ion batteries, lithium–sulfur batteries, and sodium-ion batteries. In this
section, the main focus is on the integration of nanocellulose with other active materials, developing
films/aerogel as flexible substrates, and the pyrolyzation of nanocellulose to carbon materials and
their functionalization by activation, heteroatom-doping, and hybridization with other active materials.
Finally, we present our perspectives on several issues that need further exploration in this active
research field in the future.

1. Introduction
a
Key laboratory of Bio-based Material Science and Technology, Ministry of
Education, Northeast Forestry University, Harbin 150040, P. R. China Because of the rapid development of modern society, the fast-
b
Department of Energy Engineering, School of Energy and Chemical Engineering, growing demand for energy because of worldwide power
Ulsan National Institute of Science and Technology (UNIST), Ulsan 689-798, consumption has become a serious issue and will continue to
South Korea
c
be into the future. Interest in the sustainable development of
Key Laboratory of Superlight Materials and Surface Technology,
Ministry of Education, Harbin Engineering University, Harbin 150040,
advanced, low-cost, and environmentally friendly energy storage
P. R. China. E-mail: fanzhj666@163.com devices has been growing steadily.1 Electrochemical energy
† These authors contributed equally to this work. storage systems in terms of supercapacitors and batteries

Wenshuai Chen received his BS Haipeng Yu was born in

degree (2008) and PhD degree
(2013) in wood science and
technology from Northeast
Forestry University, China. Now
he is an associate professor at
Northeast Forestry University. He
is the winner of the Young Elite
Scientists Sponsorship Program by
China Association for Science and
Technology. His research interests
include wood physics, bionano-
Wenshuai Chen composites, nanocellulose, aerogels,
and development of natural
nanomaterials for energy storage and conversion as well as
water purification.
Heilongjiang, China. He received
his BS (2000) and PhD (2005)
degrees in wood science and
technology from Northeast Forestry
University of China. He started as
an Assistant Professor at Northeast
Forestry University in 2005, and was
promoted to Associate Professor and
Professor in 2007 and 2011,
respectively. His research interests
include wood modification, nano-
Haipeng Yu cellulose and its functional nano-
materials, and biomass conversion
technologies.

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Review Article
(such as lithium (sodium)-ion batteries and lithium–sulfur
batteries) have demonstrated great potential in powering portable
electronics, electric vehicles, hybrid electric vehicles, and even
huge energy-storage systems.2–10 Except for performance and
safety enhancements, the major remaining challenges for the
future development of energy storage devices are the reduction of
both production and overall device costs, the realization of flexible
devices, the utilization of green and abundant raw materials,
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the realization of environmentally friendly processes, and the
development of easily recyclable and up-scalable systems.11–15
Among numerous candidates, cellulose-derived materials have
obtained increasing attention as attractive components of
various electrochemical energy storage devices.16–28
Cellulose is the most abundant renewable organic polymer
on earth. The world production of biomass is estimated at
approximately 150–200 billion metric tons a year, most of
which is cellulose.29,30 It is used in the form of wood, cotton,
Sang-Young Lee is a professor
and a head in School of Energy
and Chemical Engineering at
UNIST, Korea. He received BA in
Chemical Engineering from Seoul
National University in 1991, MS,
and PhD in Chemical Engineering
from KAIST in 1993 and 1997. He
served as a postdoctoral fellow at
Max-Planck Institute for Polymer
Research from 2001 to 2002.
Before joining UNIST, he worked
Sang-Young Lee at Batteries R&D, LG Chem as a
principal research scientist in the
development of safety-reinforcing separators (‘‘SRS’’). His research
interests are focused on cellulose-based paper batteries, printed
power sources, flexible/wearable batteries, advanced separator
membranes and polymer electrolytes.
Jian Li obtained his PhD degree in
wood science from Northeast
Forestry University in 1987. Now,
he is an academician of Chinese
Academy of Engineering, and
professor at College of Material
Science and Engineering in
Northeast Forestry University. His
research interests include a wide
range of wood science such as
wood biomimetic, wood physics,
wood chemistry, wood-based
Jian Li composites, and high performance
nanocomposites from lignocellulosic
resources.
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or other plant fibers as building materials, furniture, paper,
clothing, and many other applications. Regardless of its source,
cellulose is a high-molecular-weight homopolymer of b-1,4-linked
anhydro-D-glucose units in which every unit is corkscrewed 1801
with respect to its neighbors, and the repeat segment is frequently
taken to be a dimer of glucose, known as cellobiose. During
biosynthesis, van der Waals forces and intermolecular hydrogen
bonding promote the parallel stacking of cellulose chains to
form nanosized elementary fibrils that further organize into
larger fibrils.31 Within these nanosized cellulose fibers, there
are regions in which the cellulose chains are arranged in highly
crystalline structures, as well as regions containing amorphous
structures. The unique structure of these nanofibers, with
advantageous mechanical properties and a low coefficient of
thermal expansion, makes them ideal building blocks for
advanced functional products.32–36 Enormous efforts have been
made to extract nanofibers from the cell walls of cellulose
Tong Wei received her PhD in 2003
at the Institute of Coal Chemistry,
Chinese Academy of Sciences. She
became full professor at the College
of Material Science and Chemical
Engineering, Harbin engineering
University, in 2010. Her research
interests focus on advanced nano-
materials for energy conversion and
storage.
Tong Wei
Zhuangjun Fan received his PhD in
2003 at the Institute of Coal
Chemistry, Chinese Academy of
Sciences. He became full professor
at the College of Material Science
and Chemical Engineering in 2006,
and now he is the director of the
Institute of Advanced Carbon Based
Materials at Harbin Engineering
University. His research interests
focus on the design and controlled
synthesis of carbon nanomaterials
Zhuangjun Fan such as carbon nanotubes and
graphene, and their applications
in energy-related areas such as supercapacitors, Li ion batteries and
full cells.
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Chem Soc Rev
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Fig. 1 Schematic diagram showing the main topics of this review from the
cellulose resources, nanocellulose fabrication, structural and functional
design to the energy storage applications.
resources such as from higher plants, or the synthesis of nano-
fibers by bacteria, which gave birth to nanocellulose.26,31,37–52
Interest in nanocellulose has been growing steadily and nano-
cellulose has been widely applied in optically transparent
materials,53–55 reinforced polymer nanocomposites,32,33 biomi-
metic materials,56,57 templates,35,58 sensors,59,60 and energy
harvesters.61,62 There are also much more potential application
fields for nanocellulose such as in microfluidics channels, as
cell cultivation substrate, or substrate for printed electronics.
Among the multiple applications, the development of nano-
cellulose for energy storage (Fig. 1) has received increasing
attention because nanocellulose displays advantages based on
its intrinsic structures and properties, which can be broadly
categorized into the following six groups (Fig. 2):
(i) Because nanocellulose has prospective mechanical pro-
perties including a high Young’s modulus of 138 GPa63 and
an estimated strength of 2–3 GPa, it can be utilized to develop
self-standing and high strength materials for electrodes and
separators.
(ii) Because it has reactive surfaces containing hydroxyl
groups, it is possible and convenient for chemical modification
and integration of nanocellulose with active materials. By changing
the composite strategies and turning the ratios of active materials
in the composites, the properties of the nanocellulose-based
composites can be tailored to enhance their electrochemical
performance for specific applications.
(iii) Nanocellulose fibers with a high aspect ratio, such as
those extracted from higher plant or secreted by bacteria form
entangled web-like structures, can be utilized to fabricate strong
film/aerogel substrates for further development of flexible energy
storage devices.
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Fig. 2 Summary of the structural and property advantages of nanocellulose
for energy storage applications.
(iv) Because of the nanometer scale, high specific surface
area, thermal stability, and easy processing, it is possible to
fabricate thermally stable nanoporous separators with controlled
pore structures, which can simultaneously electrically separate
the electrodes and facilitate ionic transportation.
(v) Nanocellulose has desired constituents with relatively high
carbon content. Therefore, it is an ideal precursor for fabricating
carbon-based porous materials or carbon hybrid materials
that can be further functionalized as high-performance carbon
electrodes for energy storage devices.
(vi) Last but not the least, nanocellulose with various struc-
tures and surface chemistry properties can be developed from
different cellulose sources through various fabrication strategies.
Thus, it is possible to develop multiple kinds of materials or
devices motioned in the above 5 points by using various types of
nanocellulose and their hybrids as building blocks.
Thanks to the efforts from many research groups, a series of
nanocellulose-derived materials have recently been developed
for energy storage applications. Cellulose derivatives have also
been confirmed as good candidates for the same purpose.64–66
After processing the cellulose derivatives into nanoparticles,
these novel materials that having advantages both of nano-
sized cellulose and new chemical functions from the deriva-
tives, will build up new opportunity for developing of new type
of cellulose nanomaterial-based energy storage systems. Over
the past few years, extensive reviews that have focused on
different aspects in the field of lignocellulosic materials for
energy storage have been published and provide great insights
to researchers.16,18–21,67–72 As a very promising nanomaterial,
nanocellulose has been included but usually just summarized
as a part of some reviews. Recently, several reviews summarized
the utilization of nanocellulose and its derived materials for
supercapacitors, LIBs and several energy conversion devices.73–76
However, till now, no reviews have specifically focused on, and
comprehensive summarized and comparison, the development
of different types of nanocellulose for various energy storage
systems. It is timely to have a review on this topic to summarize the
recent advances and, more importantly, to provide a systematic
understanding of the merits of the use of nanocellulose and its
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Review Article Chem Soc Rev

derived materials for electrodes, separators, and energy storage
devices. This review focuses on the recent advances on putting
nanocellulose to work for electrochemical energy storage research
(Fig. 1). We begin with a brief introduction of the structural
features of cellulose nanofibers within the cell walls of various
kinds of cellulose resources. We then focus on a variety of
methods that have been explored to fabricate various types of
nanocellulose with different structures and surface chemistry
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hydrogen bonds between hydroxyl groups and oxygens of
adjacent molecules promote parallel stacking of fully extended
cellulose chains, forming elemental fibrils with cross sections
ranging from 2 to 50 nm. Owing to differences in biosynthetic
mechanisms, the structure of elementary fibrils differs depending
on the source organism. The elementary fibrils are further
assembled into larger fibrils within the cell walls. The intra- and
interchain hydrogen bonding network makes cellulose a relatively

properties from a variety of sources. Finally, we review the recent
progress in the development of nanocellulose-derived materials
for energy storage applications including supercapacitors,
lithium-ion batteries (LIBs), lithium–sulfur (Li–S) batteries,
and sodium-ion batteries (NIBs).
2. Cellulose nanofibers in the cell walls
Cellulose nanofibers are mainly synthesized by higher plants,
but also by algae, fungi, bacteria, and an animal, tunicate.
During the biosynthesis, van der Waals and intermolecular
stable polymer, and gives the cellulose fibrils high axial stiffness.31
As the skeletal component in cellulose sources, cellulose fibrils
are organized in a cellular hierarchical structure. In combination
with the accompanying substances such as hemicellulose, lignin,
and pectin, this structure leads to extraordinary properties of
native cellulose materials.
Fig. 3 illustrates the cellulose nanofibers in the cell walls of
wood, bamboo, and cotton. The cellulose molecules organized
in the cell walls in the form of nanofibers have characteristic
orientations (helix angles), which vary depending on the type
of plant sources and the cell wall layers (Fig. 3b, g and m).
Because the cellulose nanofibers are embedded in matrix such

Fig. 3 The cellulose nanofibers in the cell walls of wood, bamboo, and cotton. From left to right are the (a, f and l) digital photos of cellulose sources,
(b, g and m) cell wall models,29,77,78 (b) is reproduced with permission from ref. 77. Copyright 2010 American Chemical Society. (g) is reproduced
with permission from ref. 78. Copyright 2015 Springer Nature. (m) is reproduced with permission from ref. 29. Copyright 2005 Wiley-VCH. SEM images of
(c, h and n) raw materials,79–81 (c) is reproduced with permission from ref. 79. Copyright 2012 Scientia Silvae Sinicae. (h) is reproduced with permission
from ref. 80. Copyright 2009 Springer. (n) is reproduced with permission from ref. 81. Copyright 2014 Springer. (d, i and o) chemical purified cellulose
fibers after removal of the matrix,80–82 (d) is reproduced with permission from ref. 82. Copyright 2007 American Chemical Society. (i) is reproduced with
permission from ref. 80. Copyright 2009 Springer. (o) is reproduced with permission from ref. 81. Copyright 2014 Springer. (e, j, k and p) cellulose
nanofibers within the chemically purified cellulose fibers.80–82 (e) is reproduced with permission from ref. 82. Copyright 2007 American Chemical
Society. (j and k) is reproduced with permission from ref. 80. Copyright 2009 Springer. (p) is reproduced with permission from ref. 81. Copyright 2014
Springer. The image (j) and (k) are the high-magnification FE-SEM images of fiber and parenchyma cells, respectively, as shown in image (i).

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as hemicellulose and lignin of wood, the high-magnification SEM
observations of the samples are usually not clear and cannot
reveal the nanostructure of cellulose fibers. When chemical
purification methods are used to remove the matrix from wood,
such as the removal of lignin using acidified sodium chlorite and
the removal of a large amount of hemicellulose using potassium
hydroxide (Fig. 3d), the nanofiber characteristics of the cellulose
within the cell walls can be clearly revealed (Fig. 3e).82 Similar
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within the aggregates and cannot be clearly seen by the SEM
observation.84 For example, in most higher plants, the diameter
of single elemental fibrils is reported to be B3 nm.85 Thus, the
uniform nanofibers of 12–20 nm within the wood chemically
purified cellulose can be recognized as the B3 nm elemental
fibril aggregates.82,83

results have also been obtained for chemically purified cellulose
fibers of bamboo (Fig. 3i–k),80 cotton,81 rice straw,83 and potato
tuber,83 confirming that the higher plant cell walls are supported
by high aspect ratio cellulose nanofibers. After nanofibrillation
through various mechanical or chemical methods, these cellulose
nanofibers are released from the cell walls, resulting in nano-
cellulose. It should be noted that the uniform nanofibers
observed from SEM images in Fig. 3 is elemental fibril aggre-
gates and single elemental fibrils are parallel align aggregated
3. Fabrications, structures and
characteristics of nanocellulose
Nanocellulose with various structures and surface chemistry pro-
perties can be produced from various sources through different
nanofibrillation and synthesis methods (Table 1).77,82,86–91 On the
basis of their structures and fabrication processes, nanocellulose
can be classified into three main subcategories. So far, the
nomenclature of nanocellulose has not been fully established.

Table 1 Categories, fabrications, structures and characteristics of nanocellulose

Schematic Representative SEM/ Surface chemical

Type Sub-clarification illustration Source TEM/AFM image Fabrication method group Ref.

Wood Chemical purification + grinder Hydroxyl groups 82

Wood Chemical purification + blender Hydroxyl groups 77

Containing nanofiber
bundles
Chemical purification +
Wood Hydroxyl groups 86
high intensity ultrasonicator
NFC
Enzymatic hydrolysis + refiner +
Wood Hydroxyl groups 87
high-pressure homogenizer

TEMPO-mediated oxidation + Hydroxyl, carboxylate,

Wood 88
magnetic stirring aldehyde groups
Individual
nanofibers
Carboxymethylated + Hydroxyl, carboxyl
Wood 89
high-pressure homogenizer groups

Containing
Cotton Hydrochloric acid hydrolysis Hydroxyl groups 86
CNC bundles

CNC Hydroxyl,
Cotton Sulfuric acid hydrolysis 86
sulfate groups
Individual CNC
Hydroxyl,
Tunicate Sulfuric acid hydrolysis 90
sulfate groups

Coconut milk, Secreted by

BC — — Hydroxyl groups 91
sucrose Acetobacter xylinum FF-88

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In this review, we use the terms nanofibrillated cellulose (NFC),
cellulose nanocrystal (CNC) and bacterial cellulose (BC), because
they are widely used in the literature. It should be noted that
except for the above mentioned nanocellulose, other shapes of
cellulose nanoparticles can also be developed from different
precursors through various fabrication strategies. For example,
spherical shaped cellulose nanoparticles were developed from a
series of cellulose derivatives,92–94 while ribbon shaped cellulose
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nanofibers were produced from cellulose-based precursors
through electrospinning technique.95,96 These cellulose nano-
particles also have potential to be developed for energy storage
applications.
3.1. Nanofibrillated cellulose (NFC)
The fabrication of NFC was developed by Turbak and his
coworkers at ITT Rayonier in the 1980s.97,98 NFC was prepared
by nanofibrillation of wood cellulose pulps in water using a high-
pressure homogenizer. During the nanofibrillation process,
cellulose slurry is pumped at high pressure through a spring-
loaded valve assembly. The valve is opened and closed in a
reciprocating motion, subjecting the cellulose to a large pressure
drop of shearing and impact forces.99 This combination of
repeated mechanical forces promotes the disintegration of
cellulose fibers into nanosized fibers, which generates NFC.
The NFC is long with a length greater than 2 mm and displays
web-like entangled structures.
Besides the high-pressure homogenizer, other apparatus
such as grinder100,101 and high-intensity ultrasonicator102,103
can also be directly utilized for nanofibrillation of the cellulose
fibers for producing NFC, although the energy required is still
large. To reduce the energy requirement and improve the
nanofibrillation degree, removing the matrix from the cellulose
sources is critical before nanofibrillation. The as-prepared cellulose
pulps also need to be kept in the water-swollen state during the
whole chemical purification process. Abe et al. reported the fabrica-
tion of NFC with a uniform width of 15 nm by using chemical
treatment to remove lignin and a large amount of hemicellulose
from wood, followed by nanofibrillation of the cellulose pulps
using a grinder.82 Using a similar process, NFC with a uniform
width has been successfully produced from rice straw,83 potato
tuber,83 and bamboo.80 Enzymatic hydrolysis combined with
mechanical nanofibrillation is another route to produce NFC.
Pääkkö et al. prepared NFC using enzymatic hydrolysis combined
with mechanical shearing and high-pressure homogenization.87
The resulting NFC mainly consisted of nanofibers with a width of
5–6 nm and nanofiber aggregates with a width of approximately
10–20 nm. Although high-quality NFC can be produced from
most cellulose sources, the uniform nanofibrillation of cellulose
fibers from raw materials with a high cellulose content such as
cotton and flax104 is difficult because a small amount of matrix
can be removed during the chemical purification process, and
there are strong interactions between adjacent cellulose nano-
fibers that have a small amount or no hemicellulose on the
surfaces within the cell walls. Recently, Chen et al. reported a
method to individualize NFC from raw cotton by chemical purifica-
tion (removal of noncellulosic components) and pretreatment
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with a high-speed blender (breaking down the fiber structures)
combined with high-pressure homogenization (nanofibrillation).81
The resultant cotton NFC was found to have a uniform width of
approximately 10–30 nm and high aspect ratios. Therefore, it
can be confirmed that NFC with high aspect ratio and web-like
entangled structures can be produced from any kind of higher
plant sources.
Although the above-mentioned mechanical nanofibrillation
methods can be used to fabricate high aspect ratio NFC, a large
amount of nanofiber bundles are still existed.105 To further
improve the nanofibrillation degree and decrease the process
energy consumption, chemical modification of the surface of
cellulose pulps before nanofibrillation is effective. Isogai et al.
pioneered the development of the TEMPO (2,2,6,6-tetramethyl-
piperidine-1-oxyl radical)-mediated oxidation method to produce
uniform dispersion of individualized NFC.51,88,106 Significant
amounts of C6 carboxylate groups are formed on each cellulose
nanofiber surface. Electrostatic repulsion and/or osmotic effects
working between the anionically charged cellulose nanofibers
cause the formation of completely individualized NFC dispersed
in water by a gentle mechanical disintegration treatment of TEMPO-
oxidized cellulose fibers. The wood TEMPO-oxidized NFC is 3–4 nm
in width and a few micrometers in length. However, the formation
of sodium carboxylate groups from the C6 primary hydroxyls of
NFC surfaces leads to a significant decrease of the thermal
stability of the NFC.107,108 Another route toward the preparation
of carboxylated NFC suspensions with individualized nanofibers
was developed by Wågberg et al. by using high-pressure homo-
genization of carboxymethylated cellulose fibers followed by
ultrasonication and centrifugation.89
The high aspect ratio and web-like entangled structures of
NFC are beneficial for developing flexible substrates such as films
and aerogels, for integrating with active materials, or converting
NFC to carbon materials to develop electrodes and separators
for flexible and high strength energy storage devices.
3.2. Cellulose nanocrystal (CNC)
CNC has been produced using an acid hydrolysis approach
from a range of cellulose sources. Disordered or paracrystalline
regions of cellulose are preferentially hydrolyzed, whereas
crystalline regions that have a higher resistance to acid attack
remain intact. Thus, the CNC is short and displays lower aspect
ratios and a larger relative crystallinity compared with that of
NFC. Sulfuric acids have been extensively used for CNC pre-
paration. Rånby first reported that colloidal suspensions of
cellulose can be obtained by controlled sulfuric acid-catalyzed
degradation of cellulose fibers.109 Marchessault et al. demon-
strated that colloidal suspension of sulfuric acid hydrolyzed
CNC exhibited nematic liquid crystalline alignment.110 The
sulfuric acid reacts with the surface hydroxyl groups of cellulose
to yield charged surface sulfate esters that promote dispersion
of the individual CNC in water. However, the introduction
of charged sulfate groups decreases the thermal stability of
the CNC. The concentration of sulfuric acid in the hydrolysis
reactions is usually controlled at a typical value of 65 wt%; this
level is determined, on the one hand, by the requirement for
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efficient hydrolysis and sulfate ester formation, and, on the
other hand, by the requirement to prevent the carbonization of
cellulose by dehydration. The structures of CNC obtained by
using similar sulfuric acid hydrolysis methods vary depending
on the cellulose sources. For example, CNCs from cotton and
Avicel have a length between 100 and 300 nm, whereas that
from tunicin is several micrometers long and has a whisker-like
morphology.90 Hydrochloric acid was also used as a hydrolyzing
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agent for producing CNC. It can remove the amorphous area of
cellulose but does not react with the surface hydroxyl groups of
cellulose, resulting in CNC with large amount of CNC bundles.
For the hydrochloric acid hydrolyzed cotton CNC,86 the single
CNC in the bundles were 100–400 nm long and 4–9 nm wide,
with aspect ratios ranging from 11 to 100. The CNC displays high
crystallinity and thermal stability with thermal degradation tem-
peratures of 341.7 1C. Thermally stable CNC can also be produced
by other strong acid hydrolysis (such as phosphoric acid).
The highly crystalline CNC with high specific surface area
are conducive for integrating with active materials or convert-
ing to carbon materials to develop electrodes with high specific
surface areas. The chiral nematic structures derived from CNC
are expected to be utilized for the development of electrodes
with novel structures and properties for high-performance
energy storage.
3.3. Bacterial cellulose (BC)
BC is another kind of high aspect ratio nanocellulose that is
produced through a microbial fermentation process. BC has
long been utilized as the raw material for nata-de-coco, an
indigenous dessert food, for which one centimeter thick gel
sheets fermented with coconut water are cut into cubes and
immersed in sugar sirup.111 BC is secreted extracellularly by
certain bacteria belonging to the genera Acetobacter, Agrobacterium,
Alcaligenes, Pseudomonas, Rhizobium, or Sarcina.43,112 In con-
trast to NFC and CNC, which are mainly extracted from higher
plant cellulose sources, BC is fabricated by a biotechnological
assembly processes from low-molecular weight carbon sources,
such as D-glucose.44 The bacteria are cultivated in common
aqueous nutrient media, and the BC is excreted as exopoly-
saccharide at the interface to the air, producing a thick gel
composed of an interconnected 3D porous BC nanofiber net-
work structure and B99% water, called pellicle. The structure
of the nanofiber network of BC can be controlled by changing
the type of bacterial strain, the additives in the culture medium,
the type and conditions of cultivation, and the drying processes
in the post-processing stage.113 There are apparent structural
differences between BC and higher plant derived NFC such as
wood NFC. BC is secreted as a ribbon-shaped fibril of around
100 nm in width and around 100 mm in length,114 which
is composed of 2–4 nm width nanofibrils. BC is free of func-
tional groups (carbonyl, carboxyl) and is almost pure cellulose
containing no lignin and other foreign substances.111 Moreover,
BC is characterized by very long polymer chain with polymeriza-
tion up to 8000 and displays a distinct crystallinity of up to 90%.
It should be noted that BC can also be utilized as a raw material
to prepare NFC106 and CNC.115
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BC is high-purity cellulose with a web-like entangled struc-
ture and can be utilized to integrate with active materials or
converted to carbon materials to develop flexible energy storage
materials/devices. However, compared with NFC/CNC, which
can be produced from abundant lignocellulosic resources,
the cost of BC is relative high, although the industrial-scale
production of BC has been achieved.
4. Supercapacitors
Supercapacitors, also known as ultracapacitors or electro-
chemical capacitors, offer a promising approach to meet the
ever-increasing power demand owing to their high power
density, superior rate capability, rapid charging/discharging
rate, long cycle life, simple principles, fast dynamics of charge
propagation and low maintenance cost.116–118 Supercapacitors
can be typically classified into two types: electrical double
layer capacitors, which store energy through electrostatically
accumulated charges at the electrode/electrolyte interface, and
pseudocapacitors, which are based on rapid redox reactions at
the electrodes for huge pseudocapacitance.
Nanocellulose can be integrated with active materials or
converted to carbon materials as electrode materials for super-
capacitors. It can also be processed as separator materials
for supercapacitors.119,120 The electrochemical performance of
nanocellulose-derived materials, that were used as electrodes
and tested under different conditions for supercapacitors, has
been compared and summarized in Table 2.121–139 The Ragone plot
of supercapacitors fabricated from several typical nanocellulose-
derived hybrid materials and carbon materials (including porous
carbon materials and carbon hybrid materials) is shown in
Fig. 4.123,125,130–133,135–141 The electrochemical properties (such
as energy density and power density) of those supercapacitors
are effectively improved by integrating nanocellulose and
nanocellulose-derived carbon materials with other active materials.
Although several supercapacitors exhibit high energy density
and power density, large space for spontaneously improving the
energy density and power density is still exist. In the ensuing
sections, we discuss recent progress reported on the develop-
ment of nanocellulose and its derived materials for super-
capacitor applications.
4.1. Flexible supercapacitors based on NFC/BC-derived hybrid
materials
Because of the high aspect ratio and web-like entangled struc-
tures, NFC/BC can form hybrids with active materials such as
nanocarbon or conductive polymers to fabricate electrodes for
flexible supercapacitors. The active materials can be integrated
with NFC/BC using different composite approaches such as
extrusion,121 vacuum filtration142 and freeze-drying,125 resulting
in the formation of various structures such as 1D fibers, 2D films/
papers, and 3D aerogels/foams. Owing to the high aspect ratio
and intrinsic mechanical strength, the introduction of NFC/BC
into the hybrid materials makes the electrodes/supercapacitors
flexible, which can store energy upon repeated bending, folding
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Table 2 Examples of different nanocellulose-derived materials for supercapacitor electrodes reported in the literature

Sub- Nanocellulose Performance: capacity/energy CRa

Classification classification type Nanocellulose process Electrode Electrolyte density/power density Cycles [%] Ref.
Review Article

Flexible supercapacitors With nanocarbon TEMPO-oxidized Hybrid with SWCNTs NFC/SWCNT hybrid H3PO4-poly-(vinyl Area capacitance is about 5000 97.0 121
based on nanocellulose- NFC nonwoven macrofiber mat alcohol) gel 6.0 mF cm 2 at 0.02 mA cm 2; the
derived hybrid materials energy density is 0.7 mW h cm 2 at
a power density of 2.4 mW cm 2
Wood TEMPO- Hybrid with MWCNTs NFC/MWCNT hybrid H2SO4-poly-(vinyl Specific capacitance is up to 1000 99.9 122
oxidized NFC aerogel film alcohol) gel 178.0 F g 1 at 5 mV s 1; areal
energy density: 20.0 mW h cm 2;
maximum power density: about
13.6 mW cm 2
BC Hybrid with CNTs CNT-coated BC paper Ionic liquid based Specific capacitance is 50.5 F g 1 5000 B99.5 123
polymer gel at 1 A g 1; the energy density is
15.5 mW h g 1 at a power density

2844 | Chem. Soc. Rev., 2018, 47, 2837--2872

of 1.5 W g 1
TEMPO-oxidized Hybrid with RGO NFC/RGO hybrid aerogel H2SO4-poly-(vinyl Specific capacitance is 203.0 F g 1 5000 99.1 124
NFC film alcohol) gel at 0.7 mA cm 2; the maximum
areal energy density is
20.0 mW h cm 2 at an areal power
density of 15.5 mW cm 2
Wood NFC Hybrid with RGO NFC/RGO/CNT hybrid H2SO4-poly-(vinyl Areal capacitance can be 216.0 mF 1000 499.5 125
and CNTs aerogel film alcohol) gel cm 2; the areal energy density is
28.4 mW h cm 2 at an areal power
density of 9.5 mW cm 2
With conductive Cladophora NFC Hybrid with PPy NFC/PPy composite 2 M NaCl The volumetric capacitance is 5000 93.0 126
polymer with quaternary 122.0 F cm 3 at 300 mA cm 2; the
amine groups on volumetric energy and power
the surface densities are 3.1 mW h cm 3 and
3.0 W cm 3, respectively
Cladophora NFC Hybrid with PEDOT NFC/PEDOT composite 1 M H2SO4 The volumetric energy and power 15 000 93.0 127
paper densities are 1.1 mW h cm 3 and
900.0 mW cm 3, respectively
With nanocarbon BC Hybrid with PPy BC/PPy/MWCNTs hybrid 2 M LiCl Areal capacitance can be 5000 94.5 128
and conductive and MWCNTs membrane 590.0 mF cm 2 at 1 mA cm 2
polymer BC Hybrid with PANI BC/PANI/graphene 1 M H2SO4 The areal capacitance is 1.9 F 5000 B53.6 129
and graphene composite film cm 2 at 0.25 mA cm 2; the
maximum energy density is about
0.2 mW h cm 2 at a power density
of about 0.1 mW cm 2
Supercapacitors based Porous carbon BC Pyrolyzation and NiCoAl-layered double 6 M KOH The maximum energy density is 10 000 113.0 130
on nanocellulose-derived materials activated by KOH hydroxide as the positive 100.0 W h kg 1 at a power density
carbon materials electrode; activated of 451.0 W kg 1
BC-derived carbon as the
negative electrode
BC Hybrid with potassium BC-Derived carbon 1 M Na2SO4 The energy density is 10 000 94.8 131
citrate followed by nanofiber-bridged porous 20.4 W h kg 1 at a power
pyrolyzation and acid carbon nanosheet density of 81.8 W kg 1
washing
BC Pyrolyzation and Activated N-doped H2SO4-poly-(vinyl Maximum energy density: 5000 B95.9 132
activated by mixed gas BC-derived carbon alcohol) gel 6.1 W h kg 1; maximum power
of CO2/argon; N-doped nanofiber density: 390.5 kW kg 1
via a hydrothermal
synthesis
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Table 2 (continued)

Sub- Nanocellulose Performance: capacity/energy CRa

Classification classification type Nanocellulose process Electrode Electrolyte density/power density Cycles [%] Ref.
Supercapacitors based Porous carbon BC Hybrid with NH4H2PO4 N,P codoped BC-derived 2 M H2SO4 The maximum power density 4000 — 133
on nanocellulose-derived materials followed by carbon nanofibers is 186.0 kW kg 1
carbon materials pyrolyzation
Carbon hybrid BC Hybrid with PPy and N-Doped BC-derived 6 M KOH/1 M Areal maximum energy density: 10 000 B99.6 134
materials GO followed by carbon nanofiber/RGO/BC H2SO4 0.1 mW h cm 2 in KOH and
pyrolyzation 0.3 mW h cm 2 in H2SO4; areal
maximum power density:

This journal is © The Royal Society of Chemistry 2018

27.0 mW cm 2 in KOH and
37.5 mW cm 2 in H2SO4
BC Pyrolyzation; coated BC-derived carbon 1 M Na2SO4 The maximum energy density is 2000 B95.4 135
with MnO2; N-doped via nanofibers coated with 32.9 W h kg 1; the maximum
a hydrothermal method MnO2 as the positive power density is 284.6 kW kg 1
electrode; N-doped BC-
derived carbon nanofibers
as the negative electrode
BC Hybrid with PANI fol- N-Doped BC-derived 1 M Na2SO4 Specific capacitance is 113.0 F g 1 5000 92.0 136
lowed by pyrolyzation; carbon coated with MnO2 at 2 mV s 1; the maximum energy
coated with MnO2; as the positive electrode; density is 63.0 W h kg 1 at a
activated with KOH KOH activated N-doped power density of 227.0 W kg 1
BC-derived carbon as the
negative electrode
BC Hybrid with PANI fol- N-Doped BC-derived 6 M KOH The maximum energy density is 2500 89.3 137
lowed by pyrolyzation; carbon nanofiber@LDH 36.3 W h kg 1 at a power
deposition of nickel– composites as the positive density of 800.2 W kg 1
cobalt layered double electrode; N-doped BC-
hydroxide (Ni–Co LDH) derived carbon nanofibers
nanosheets as the negative electrode
BC Pyrolyzation; growing BC-derived carbon 2 M KOH Specific capacitance is 56.6 F g 1 2500 97.0 138
Ni3S2 nanoparticles via nanofiber coated Ni3S2 at 1 A g 1; the energy density is
a hydrothermal method nanoparticles as positive 25.8 W h kg 1 at a power
electrode; BC-derived density of 425.0 W kg 1
carbon nanofiber as
negative electrode
BC Dissolution/gelation/ NiS/BC-derived carbon 2 M KOH The energy density is 10 000 B87.1 139
carbonization; in situ aerogel composite as posi- B21.5 W h kg 1 at a power
growth of NiS particles tive electrode; BC-derived density of 700.0 W kg 1
via a hydrothermal carbon aerogel as negative
method electrode
a
CR = capacitance retention.
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Fig. 4 Ragone plot of supercapacitors fabricated from several typical
nanocellulose-derived hybrid materials and carbon materials. The black sym-
bols within the light blue background region represent the supercapacitors
fabricated from nanocellulose-derived hybrid materials. The red symbols within
the light green background region represent the supercapacitors fabricated
from nanocellulose-derived porous carbon materials and carbon hybrid
materials. Data obtained from ref. 123, 125, 130–133 and 135–141.
and/or compressing without a dramatic decrease in the electro-
chemical performance.
4.1.1. Hybrids with nanocarbon. NFC/BC can be mixed
with nanocarbon materials (Fig. 5) such as carbon nanotubes
(CNTs) and graphene to form uniform solutions. 1D fibers can
be produced from the composite solutions by wet spinning.
Macrofiber with a uniform diameter of B50 mm was fabricated
by extrusion of NFC/single-walled CNT (SWCNT) suspensions
in an ethanol coagulation bath (Fig. 5a) and drying in air under
restricted conditions.121 The SWCNTs were preferentially
oriented along the axial direction of the macrofiber, whereas
the NFC effectively prevented the aggregation of SWCNTs. The
as-prepared nonwoven macrofiber mat wearable supercapacitors
exhibited good electrochemical properties (Fig. 5b), outstanding
tailorability, and damage reliability. The supercapacitors maintained
96.0% of their initial capacitance after 1500 bending cycles (Fig. 5c).
After a fifth extreme deformation, the capacitance retention of
the supercapacitors was approximately 93%.
2D films/papers can be fabricated by mixing NFC/BC and
nanocarbon solutions followed by filtration and drying. Films
containing the covalent intercalation of graphene oxide (GO)
and BC were fabricated by filtration of the reaction mixture
followed by drying.142 The composite films exhibited a tensile
strength of 18.5 MPa and an elongation at break of 24%. With
an electrical conductivity of 171 S m 1, the composite films
demonstrated specific capacitance of 160 F g 1 at 0.4 A g 1. 2D
films/papers can also be fabricated by the deposition of nano-
carbons on the NFC/BC films/papers. Kang et al. reported the
preparation of 2D papers by the deposition of a CNT layer on
the BC paper through a vacuum filtering process (Fig. 5d–g).123
The CNTs were coated on and integrated with the BC paper
through hydrogen bonding and van der Waals’ interactions.
Flexible supercapacitors fabricated by incorporating ionic liquid
based polymer gels between two BC papers coated with CNTs
showed a specific capacitance of 50.5 F g 1, a specific energy density
2846 | Chem. Soc. Rev., 2018, 47, 2837--2872
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Chem Soc Rev
of 15.5 mW h g 1, and a specific power density of 1.5 W g 1
(measured at 1 A g 1). Owing to the good interfacial quality
between the three different layers, the supercapacitor performance
was generally maintained over 200 bending cycles to a bending
radius of 3 mm. Recently, Lee et al. reported the fabrication
of all-inkjet-printed, solid-state flexible supercapacitors on paper
(Fig. 5h).143 A NFC-mediated nanomat was inkjet-printed as a
primer layer to enable high-resolution images. CNT-assisted
photonic interwelding of Ag nanowires was introduced onto the
CNT/activated carbon electrodes to improve the electrical conduc-
tivity. The ([BMIM][BF4]/ETPTA) solid-state electrolyte was applied
to the inkjet-printed electrodes through inkjet printing, after which
the UV-crosslinking process was performed. The inkjet-printed
supercapacitors exhibited reliable electrochemical performance
and good mechanical flexibility. Even after 1000 bending cycles
with a bending radius of 2.5 mm, the supercapacitors still retained
their structural integrity without impairing the cell capacitance.
3D aerogels/foams for supercapacitor can be fabricated
through freeze–drying/critical point drying/supercritical drying
of mixtures of NFC/BC and nanocarbons. The as-developed
aerogels/foams exhibited web-like entangled structures, high
porosity, low density, high conductivity, as well as the synergy
effect of NFC/BC and nanocarbons, which makes them good
electrodes for flexible supercapacitors. NFC/reduced GO (RGO)
hybrid aerogels were prepared by supercritical CO2 drying of
the corresponding hydrogels.124 Flexible supercapacitors were
developed using the hybrid aerogel film as an electrode, and
exhibited areal capacitance of 158 mF cm 2, and a maximum
areal energy density of 20 mW h cm 2 at an areal power density
of 15.5 mW cm 2. Aerogels derived from NFC/RGO/CNT were
developed by freeze-drying of aqueous dispersion of NFC/GO
nanosheets (GONSs)/CNT, followed by thermal reduction of the
GONSs.125 The supercapacitors assembled by the compressed
NFC/RGO/CNT aerogel exhibited a specific capacitance of
252 F g 1, an energy density of 8.1 mW h g 1 at a power density
of 2.7 W g 1, as well as good cyclic stability with more than
99.5% capacitance retention after 1000 charge/discharge cycles.
Recently, Hamedi et al. pioneered the development of a
layer-by-layer (LBL) assembly technology for coating functional
materials onto NFC aerogel surfaces (Fig. 5i).144 Prior to LBL
assembly, covalent crosslinking of the NFC aerogels was con-
ducted to avoid the disintegration of the NFC aerogels during
the LBL assembly process. Active materials such as CNTs were
assembled onto NFC aerogels by LBL, and enhanced compressive
strength, super elasticity in the wet state, and elastic mechano-
responsive resistance were achieved. A SWCNT-functionalized
NFC aerogel electrode showed a specific capacitance of 419 F g 1
by accounting for the measured weight of the active LBL layer.
Using similar covalently crosslinked NFC aerogels as scaffolds,
CNT electrodes and separator were LBL deposited on the NFC
aerogel surface, resulting in the assembly of 3D supercapacitors
(Fig. 5j).141 The pore walls of the NFC aerogel were gradually
thickened when the first electrode, the separator, and the second
electrode were added (Fig. 5k–m). The 3D supercapacitor showed
stable operation over 400 cycles with a capacitance of 25 F g 1,
and was fully functional even at compressions up to 75%.
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Fig. 5 The hybrid of NFC/BC with nanocarbon for supercapacitors. (a–c) The hybrid of NFC with SWCNT to fabricate 1D fibers:121 (a) photograph of the
wet NFC/SWCNT hybrid nonwoven macrofiber mat; (b) three nonwoven macrofiber mat wearable supercapacitors connected in series can illuminate a
LED light; (c) the durability test of the nonwoven macrofiber mat wearable supercapacitor undergoing 1500 bending cycles. (a–c) are reproduced with
permission from ref. 121. Copyright 2014 Royal Society of Chemistry. (d–h) The hybrid of NFC/BC with nanocarbon to fabricate 2D films/papers:123,143
(d) fabrication process of BC papers coated with CNTs; SEM images of (e) a BC paper and (f) CNTs coated on a BC paper; (g) cross-sectional view of a BC/
CNTs paper; (d–g) are reproduced with permission from ref. 123. Copyright 2012 American Chemical Society. (h) Schematic illustration of the stepwise
fabrication procedure of the inkjet-printed supercapacitors using NFC mediated nanoporous mats as a primer layer. Reproduced from ref. 143. Copyright
2016 Royal Society of Chemistry. (i–m) The hybrid of NFC with nanocarbon to fabricate 3D aerogels:141,144 (i) representations of the crosslinking in NFC,
and aerogel construction and the LBL assembly on aerogels; Reproduced from ref. 144. Copyright 2013 Wiley-VCH. (j) Schematics of the LBL process
used to assemble 3D devices in an NFC aerogel and cross-section SEM images of (k) the first PEI/CNT electrode, (l) the PEI/CNT electrode with separator,
and (m) the full device. Scale bars in (k–m) are 2 mm. (j–m) are Reproduced from ref. 141. Copyright 2015 Springer Nature.

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4.1.2. Hybrids with conductive polymers. Conductive poly-
mers such as polypyrrole (PPy),145–150 polyaniline (PANI),151 and
poly(3,4-ethylenedioxythiophene) (PEDOT)127 are usually poly-
merized in situ and form a homogenous layer around NFC/BC,
resulting in composite films/papers with high electrical con-
ductivity. To improve the electrochemical performance, the
composites are usually thick with large active mass loadings,
which often sacrifice the electrode flexibility. Thus, improving
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using these composites as electrodes exhibited a volumetric
energy and power densities of 3.1 mW h cm 3 and 3 W cm 3 in
aqueous electrolyte, respectively. The functionality of the devices
was maintained even in different mechanically challenging
states (Fig. 6c–e). Wang et al. also reported the fabrication of
flexible NFC/PEDOT composite papers by chemical polymeriza-
tion of 3,4-ethylenedioxythiophene at room temperature in the
presence of NFC followed by vacuum filtration and drying

the interfacial interaction between nanocellulose and the con-
ductive polymers, wrapping the nanocellulose with a uniform
and sufficiently thin conductive polymer layer, and decreasing
the electrode thickness are critical for fabricating flexible
electrodes. Wang et al. reported the introduction of quaternary
amine groups on the surface of NFC to prepare NFC with
cationic (c-NFC) surface charges (Fig. 6a).126 After the polymeriza-
tion of pyrrole on the c-NFC (Fig. 6b), the composites delivered high
normalized gravimetric (127 F g 1) and volumetric (122 F cm 3)
capacitances at 300 mA cm 2. Symmetrical supercapacitor
(Fig. 6f).127 A uniform PEDOT coating layer was formed on NFC
(Fig. 6g) and the composite papers exhibited a surface area of
137 m2 g 1, a sheet resistance of 1.4 O & 1, and an active mass
loading of 7.3 mg cm 2. Symmetric NFC/PEDOT paper-based
supercapacitors demonstrated high specific electrode capaci-
tances (920 mF cm 2) and good cycling stability (93% capacity
retention after 15 000 cycles at 30 mA cm 2) in 1 M H2SO4. Under
harsh mechanical conditions involving the twisted and bent
states, the device exhibited good stability (Fig. 6h–j) and retained
96.5% of its initial specific capacitance after 1200 cycles.

Fig. 6 The hybrid of NFC with conductive polymers for supercapacitors. (a–e) The hybrid of NFC with PPy:126 (a) photograph of NFC paper and the
molecular structure of unmodified and modified NFC; (b) SEM image of PPy/c-NFC composite; (c) photo of a red LED powered by three flexible PPy/
c-NFC-based supercapacitors coupled in series for a bending angle of B3401; (d) charge/discharge profiles for the in-series supercapacitors under flat
and bending conditions for an applied current of 20 mA as well as (e) the corresponding current responses owing to potential steps to 2.4 and 0 V,
respectively. (a–e) are reproduced with permission from ref. 126. Copyright 2015 American Chemical Society. (f–j) The hybrid of NFC with PEDOT:127
(f) schematic illustration of the manufacturing of PEDOT nanocomposite paper electrodes; (g) SEM image of PEDOT nanopaper; (h) conductivity of
PEDOT nanopaper in various geometrical states; (i) resistance (R) of PEDOT nanopaper in different bending states normalized with respect to the
resistance (R0) of the flat PEDOT nanopaper, in which L0 is the length of the flat paper and L is the distance between the two paper ends in the different
bending states; (j) the cycling stability during 1200 cycles for the flexible device under different bending conditions, in which the insets show photographs
of the device for the different test conditions. (f–j) are reproduced with permission from ref. 127. Copyright 2016 Royal Society of Chemistry.

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Moreover, PPy/BC composite membranes,152,153 PPy/cobalt sulfide/
BC composite membranes,154 PPy/nickel sulfide/BC composite
membranes,155 PPy/copper sulfide/BC composite membranes,156
and PANI/silver NFC aerogels,157 have all been fabricated as
electrodes for developing flexible supercapacitors.
4.1.3. Hybrids with nanocarbon and conductive polymers.
Nanocarbon and conductive polymer can be integrated together with
NFC/BC to fabricate electrode materials for supercapacitors. These
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combinations give electrodes enhanced flexibility and mechanical
robustness, and maintained their capacitances.129,158,159 A flexible
BC/RGO/PPy composite film was prepared through an in situ
polymerization and filtering method. The assembled symmetric
supercapacitor delivered an areal capacitance of 1.67 F cm 2, an
areal energy density of 0.23 mW h cm 2, and a maximum power
density of 23.5 mW cm 2.160 An NFC/GO/PPy composite paper
was produced by straightforward polymerization of a PPy layer
both on the NFC attached to the GO sheets and the GO itself.161
The NFC reinforced the entire electrode yielding a robust and
compact electrode that still contained a sufficient number of
mesopores to allow the material to undergo fast PPy charge and
discharge reactions. Symmetrical supercapacitors containing
NFC/GO/PPy composite paper were flexible, with 485% capaci-
tance retention over 16 000 cycles at 5 A g 1 and high volumetric
specific capacitance (301 F cm 3 based on PPy).
BC/multiwalled CNTs (MWCNTs)/PANI composite films
were produced by vacuum filtration of a MWCNTs layer onto
BC paper followed by electrodeposition of PANI (Fig. 7a–h).162 Owing
to the porous structure and electrolyte absorption properties of the
BC paper, the flexible BC/MWCNTs/PANI hybrid electrode exhibited
high specific capacitance (656 F g 1 at 1 A g 1) and good cycling
stability with capacitance loss of less than 0.5% after 1000 cycles at
10 A g 1. Moreover, the electrodes with high mass loading in the
range of 7–12 mg cm 2 were prepared by using BC/PPy nanofibers
in combination with MWCNTs through a vacuum-filtering method
(Fig. 7i–o).128 The as-prepared symmetric supercapacitors exhibited a
capacitance of 590 mF cm 2 and good cycling stability with 94.5% of
capacitance retention after 5000 cycles.
Overall, NFC/BC-derived hybrid electrodes hold great promise
for flexible supercapacitors. By introducing active materials,
the electrochemical performance of the hybrid electrodes can
be increased, whereas the addition of NFC/BC can improve the
mechanical and surface properties of the hybrid electrodes
in several ways. The high aspect ratio NFC/BC formed
strong entangled networks with the active materials, which
made the hybrid electrodes flexible, bendable, foldable, and
compressible without deterioration of the electrochemical
performance. The ratio of active materials plays a critical role
on the electrode performance. The interface interactions between
the active materials and the NFC/BC should be optimized to
maximize the synergistic effects and enhance the activity of
supercapacitor and spontaneously maintain its mechanical
strength and high flexibility.
4.2. CNC-derived hybrid materials
CNC, which has a higher specific surface area compared with
that of NFC/BC, can be integrated with active materials in
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several ways to fabricate electrodes for supercapacitors. CNC
can be integrated with conductive polymers such as PPy through
electrodeposition methods.163 A cotton CNC was subjected to
TEMPO-mediated oxidation to convert the surface primary
hydroxyls to carboxylate functionalities. Then, the TEMPO-
oxidized CNC was electrodeposited with PPy to fabricate
CNC/PPy nanocomposites. A symmetrical supercapacitor using
CNC/PPy nanocomposites as the electrodes was constructed and
tested at an operating voltage of 1 V. The specific energy density
of the supercapacitor was 8.34 W h kg 1 at 1 mA cm 2. The
supercapacitor retained 70% of its initial capacitance after
cycling 10 000 times and 47% of its capacitance after an excessive
50 000 cycles. The good cycling stability was mainly attributed to
the stability of the individual electrodes owing to the highly
porous structure of the CNC/PPy nanocomposites and the thin
coating of PPy onto individual CNC, which facilitates the ion and
solvent movements during the charge/discharge cycles and thus
makes the composites with stable volumetrically. CNC can
also be integrated with conductive polymers through in situ
polymerization methods.164 PPy was readily coated on the
surface of TEMPO-oxidized CNC and formed a conductive shell
on individual CNC through the in situ chemical polymerization
of pyrrole. The 1D structure of the CNC not only facilitated the
efficient transport of electrons along one controllable direction,
but also provided a very low percolation concentration of
CNC/PPy to achieve a conductive network. The electrical conductivity
of the CNC/PPy composites approached 4 S cm 1 with a capacitance
of 248 F g 1 at 0.01 V s 1, retaining 90% capacitance at up to
0.1 V s 1. To ensure a uniform PPy coating, PVP was used as a
surface modifier through physical adsorption onto the CNC
surface prior to the introduction of pyrrole.165 PVP introduced
hydrophobicity on the CNC surface, making it more favorable for
the growth of the hydrophobic PPy shell, which acted as a steric
stabilizer preventing further agglomeration of the nanoparticles.
The CNC/PVP/PPy composites exhibited electronic conductivity
of 36.9 S cm 1, a specific capacitance of 322.6 F g 1, and cycling
stability with less than 9 and 13% capacitance loss after 1000
and 2000 cycles, respectively.
Because CNC is short with a low aspect ratio, CNC-derived
bulk materials such as aerogels are usually mechanically weak86
and easily broken when bent or compressed. Cranston et al.
developed a chemical crosslinking method to produce CNC
aerogels with tailorable mechanical performance and shape
recovery abilities (Fig. 8a–e).166 The CNC aerogels were fabricated
based on the chemical crosslinking of aldehyde-modified
CNCs and hydrazide-modified CNCs, which formed covalent
hydrazone crosslinks immediately upon contact. These CNC
aerogels acted as universal substrates for a variety of active
nanoparticles, such as PPy nanofibers, PPy-coated CNTs, and
spherical manganese dioxide nanoparticles during the aerogel
assembly, offering enough accessible surface area of active
material, which promoted charge storage. The CNC-active nano-
particle hybrid aerogels were strong and remained intact when
compressed in both air and aqueous electrolytes. Symmetric
coin-cell supercapacitors were assembled containing two
hybrid aerogels separated by a porous polyethylene membrane
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Fig. 7 The hybrid of BC with nanocarbon and conductive polymers for supercapacitors. (a–h) The hybrid of NFC with MWCNTs and PANI:162 (a) schematic of the
fabrication process of BC/MWCNTs/PANIx freestanding paper electrodes; (b and c) digital image of BC/MWCNTs paper and BC/MWCNTs/PANI paper electrode;
SEM images of (d) BC paper, (e) BC/MWCNTs paper and (f) BC/MWCNTs/PANI paper electrode; the optical images of (g) flexible supercapacitor device based on
BC/MWCNTs/PANI and (h) a red LED lighted by such devices. (a–h) are reproduced with permission from ref. 162. Copyright 2014 Wiley-VCH. (i–o) The hybrid of
NFC with MWCNTs and PPy:128 (i) schematic of the synthesis procedure of BC/MWCNTs/PPy hybrid membrane; optical images of (j) BC/MWCNTs/PPy membrane
and (k) the bending state; SEM images of (l) BC membrane, (m) BC/PPy membrane, and (n) BC/MWCNTs/PPy hybrid membrane; (o) optical image of a red LED lit by
three charged supercapacitors connected in series. (i–o) are reproduced with permission from ref. 128. Copyright 2014 Springer.

immersed in saturated Na2SO4 aqueous electrolyte. The area-
normalized specific capacitances at 2 mV s 1 for PPy nanofibers,
PPy-coated CNTs, and spherical manganese dioxide nanoparticle
devices were 3.32, 2.42, and 2.14 mF cm 2, respectively.
Using similar CNCs as building blocks, an aerogel-based
current collector composed of crosslinked CNCs and MWCNTs
was produced using bile acid as a dispersant (Fig. 8f–k).167 PPy-
based electrodes with a mass loading up to 17.8 mg cm 2 were
fabricated based on in situ polymerization of pyrrole inside the
CNC/MWCNT aerogel. The CNC/MWCNT/PPy electrodes were
flexible and had good compression stability at 80% compression,
exhibited a capacitance of 2.1 F cm 2 with a mass ratio of active
material/current collector of 0.57. The electrodes and devices
showed good capacitance retention at high charge/discharge
rates and good cyclic stability and capacitance stability during
compression and bending cycles.
Overall, compared with NFC/BC, highly crystalline CNC has
a higher specific surface area to integrate with active materials.
A uniformly, full, and thin coating of an active materials on
individual CNC fibers is effective for facilitating the ion move-
ments during the charge/discharge cycles. The CNC-derived bulk
materials such as films and aerogels are fragile and easily broken
when bent or compressed, mainly because of the low aspect ratio
of CNCs, which limits their use in several practical applications
such as for the development of flexible supercapacitors. Although
several methods such as chemical crosslinking can be utilized
to fabricate flexible CNC electrodes, the complicated synthesis
routes and sacrificing of the specific surface area of the bulk

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Fig. 8 CNC-derived hybrid materials for supercapacitors.166,167 (a) Schematic representation of the aerogel components, including functionalized CNC
and capacitive nanoparticles that form the initial suspension of crosslinked clusters. (b) The sol–gel process used to prepare aerogels. (c) Photograph of
the final hybrid aerogels. (d) Photograph emphasizing the lightweight nature of a hybrid aerogel resting on top of a feather. (e) Schematic showing
the fabrication of symmetric supercapacitor cells. (a–e) are reproduced with permission from ref. 166. Copyright 2015 Wiley-VCH. (f) Chemical
structures and (g) MWCNT dispersion mechanisms of SDS and TCH. (h) Scheme of CNC/MWCNT aerogel fabrication method. (i) Aerogel with a density of
21  3 mg cm 3 attached to a weighing dish through static electricity. (j) Electrochemical supercapacitor cell: as fabricated and under bending, twisting,
and partially compressing stress; (k) wearable cells that are connected in series are able to power LED bulbs. (f–k) are reproduced with permission from
ref. 167. Copyright 2016 Wiley-VCH.

materials is still a problem that should not be ignored. The low
thermal degradation temperature of H2SO4-hydrolyzed CNCs
hampers the thermal stability of the supercapacitors. Thus, the
surface/interface properties and interactions of the CNCs and the
active materials should be rationally designed and controlled to
achieve uniform integration of active materials and CNCs with a
high active material loading, and to make composites with high
mechanical strength, flexibility, and thermal stability without
decreasing the specific surface area of the bulk materials.
4.3. Nanocellulose-derived carbon materials
High temperature pyrolysis under an inert atmosphere can convert
nanocellulose bulk materials into conductive carbon materials.
The carbon materials possessed an ultralow apparent density, high
specific surface area, and high electric conductivity. Nanocellulose-
derived porous carbon materials can be directly utilized as
electrodes for supercapacitors. The electrochemical properties
of the carbon materials can be further improved through
activation treatment, doping with heteroatoms, and the formation
of hybrids with active materials. Recently, nanocellulose-
derived porous carbon materials and carbon hybrid materials
have been frequently developed as the electrode materials for
supercapacitors.
4.3.1. Porous carbon materials. NFC and BC were utilized
as building blocks to prepare films/aerogels for pyrolysis and
conversion to porous carbon aerogels (Fig. 9a and b).168–170

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Fig. 9 NFC/BC-derived porous carbon materials for supercapacitors. The fabrication of carbon aerogels from (a) wood NFC169 and (b) BC.168 (a) is
reproduced with permission from ref. 169. Copyright 2016 Wiley-VCH. (a) is reproduced with permission from ref. 168. Copyright 2012 Springer Nature.
The carbon aerogels show high flexibility. (c) Schematic illustration of the synthesis of hierarchically structured carbon from BC by a one-step
carbonization/activation.130 Reproduced with permission from ref. 130. Copyright 2016 Royal Society of Chemistry. (d) The fabrication process of doped
carbon aerogels by annealing BC aerogels with different toxic organic dyes.172 Reproduced with permission from ref. 172. Copyright 2014 Springer.
(e) Schematic illustration of the synthesis of N-doped carbon by annealing BC/PANI composite aerogels followed by activation.136 Reproduced with
permission from ref. 136. Copyright 2014 Wiley-VCH. (f–i) The fabrication of N-doped carbon aerogels by hydrothermal treatment of BC-derived carbon
aerogels and urea:135 (f) SEM image and photograph (inset) of N-doped carbon aerogels; (g) typical EFTEM image of N-doped carbon aerogels; (h and i)
corresponding elemental mapping images of (h) C and (i) N. (f–i) are reproduced with permission from ref. 135. Copyright 2013 Wiley-VCH.

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The as-fabricated carbon aerogels shrank in three dimensions
after the pyrolysis process and the 3D structure of NFC/BC
aerogels was inherited. Although the carbon aerogels possessed
ultra-low density, extraordinary compressibility, and high electric
conductivity, they exhibited low electrochemical properties for
supercapacitors. For example, the specific capacitance of the
BC-derived carbon aerogels was only 77.7 F g 1 at 1 A g 1,135
mainly because of its relatively low surface area and wettability.
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Activation treatment can apparently increase the specific surface
areas. The activation of BC-derived carbon aerogels with a mixed
gas of CO2/argon exhibited a high BET surface area of 699.7 m2 g 1
compared to that of 286.4 m2 g 1 for the carbon aerogels
without activation.132 The CV curves of the activated carbon
aerogel had roughly rectangular shapes and displayed almost
mirror images, which demonstrated good capacitive behavior and
reversibility. Activation of the carbon aerogels with potassium
hydroxide130,136,171 or potassium citrate131 is another strategy to
improve the specific surface areas, which ensures more effective
electroactive sites for charge accommodation and thus improve-
ment of the specific capacitance of the carbon aerogels. Potassium
hydroxide was also found to play a critical role for facilitating the
crosslinking of BC and acting as a hard template to generate
macropores during the carbonization process. The obtained
carbon aerogels had a 3D interconnected honeycomb-like hier-
archical network structure (Fig. 9c),130 exhibited a high specific
surface area of 1533 cm2 g 1, and a high specific capacitance of
422 F g 1 in 6 M KOH, as well as good rate capability with
73.7% of capacitance retention at 500 mV s 1.
The electrochemical properties of porous carbon materials
can be improved by doping with heteroatoms, because the
heteroatom dopants can modulate the physical and chemical
properties of the carbon material to generate more reactive
sites. The doping with heteroatoms has been achieved mainly
by three routes: (1) Annealing of NFC/BC aerogels/foams with
heteroatom-rich compounds. Because NFC/BC aerogels/foams
are hydrophilic and exhibit high porosity, the heteroatom-rich
compounds can easily fill with the pores of the aerogels/foams.
After high temperature pyrolysis under an inert atmosphere,
heteroatom doping was achieved. Various doped carbon aerogels
were produced by Wu et al. through the pyrolysis of BC pellicles
that had adsorbed or were dyed with different toxic organic dyes
(Fig. 9d).172 From the sample obtained from methylene blue
(C16H18ClN3S), N and S atoms were codoped and homogeneously
distributed within the carbon networks. When used as super-
capacitor electrodes, the N,S dual-doped carbon aerogels exhibited
better electrochemical properties compared with the raw carbon
aerogels. In addition, P-doped, N,P-codoped, and B,P-codoped
carbon aerogels were obtained by the pyrolysis of BC immersed
in H3PO4, NH4H2PO4, and H3BO3/H3PO4 aqueous solution,
respectively.133 The N,P-codoped carbon aerogels as electrodes
for supercapacitors showed a maximum power density of
186.03 kW kg 1. The high power density was mainly attributed
to the codoping of N and P and the 3D porous nanofiber
network of the carbon aerogels, which ensured good electrical
conductivity while avoiding the use of conducting additives
and polymer binders, which blocks the pores and increases
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contact resistance. (2) Annealing of heteroatom-containing
polymers and NFC/BC composite aerogels/foams. Heteroatom-
containing polymers such as PANI and PPy can form composites
with NFC/BC aerogels/foams through in situ polymerization or
electrodeposition methods. After carbonization, the heteroatom-
doped carbon aerogels/foams were fabricated. BC was used as
both a template and precursor for the synthesis of N-doped carbon
networks through the carbonization of PANI-coated BC (Fig. 9e).136
KOH activation was conducted to further optimize the pore
structure and improve the specific surface area. N doping
enhances the surface polarity, electric conductivity, and electron-
donor tendency of carbon materials. The as-prepared N-doped
porous carbon displayed a high specific capacitance of 296 F g 1 at
2 mV s 1, higher than that of raw BC-derived carbon (161 F g 1).
The N-doped carbon also exhibited excellent rate performance
and cycling stability, which was ascribed to its unique con-
ductive networks and energy storage units. An interconnected,
well-organized 3D conductive network is beneficial for electron
transport, and a N-doped porous carbon network with high
surface area can provide more active sites for energy storage
and short ion diffusion length during the charge/discharge
process. (3) Hydrothermal treatment of carbon aerogels with
heteroatom-containing molecules in solution. Because the
NFC/BC-derived carbon aerogels have high porosity, an aqueous
solution containing heteroatom molecules such as urea and
ammonia can easily permeate through the carbon aerogels.
N-Doped carbon aerogels were fabricated by Chen et al. using
BC-derived carbon aerogels and urea through a hydrothermal
reaction under mild conditions.135 The as-prepared N-doped
carbon aerogels still maintained a free-standing 3D pellicle with
interconnected nanofibers and crosslinking pores (Fig. 9f–i).
Owing to the high content of N doping and proper N species,
the interconnected pore structure, and the high specific surface
area of the carbon aerogels, the N-doped carbon aerogels exhibited
a high specific capacitance of 173.3 F g 1, which is apparently
higher than that of BC-derived carbon aerogels (77.7 F g 1).
N-Doped carbon aerogels can also be produced using a hydro-
thermal method with BC-derived carbon aerogels (after activa-
tion with a mixed gas of CO2/argon) and aqueous ammonia.132
An all-solid-state supercapacitor was fabricated by impregnating
poly(vinyl alcohol)–H2SO4 gel electrolyte into the framework
of N-doped carbon aerogels. The assembled supercapacitor
exhibited good flexibility with a maximum power density of
390.5 kW kg 1 and stable cycling stability over 5000 cycles.
CNC can also be converted into porous carbon materials that can
be further functionalized and utilized for supercapacitors. CNC has
been used as both a carbon source and a template for the controlled-
growth of the N precursor to form melamine-formaldehyde (MF)
coated CNCs (Fig. 10a).173 The hybrid material was subjected to
pyrolysis to fabricate N-doped carbon materials with micro-, meso-,
and macropores (Fig. 10b). Optimal capacitances of 328.5 F g 1 at
0.01 V s 1 and 352 F g 1 at 5 A g 1 were achieved for the carbon
materials in 1 M H2SO4. The carbon materials also exhibited good
cycling stability (less than 4.6% loss after 2000 cycles) at 20 A g 1.
Another strategy for using CNC-derived porous carbon
for supercapacitors is the development of chiral nematic
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Fig. 10 CNC-derived porous carbon materials for supercapacitors. (a) Schematic of the synthesis of CNC-derived N-doped carbon nanorods.173 (b) TEM
image of the CNC-derived N-doped carbon nanorods.173 (a and b) are reproduced with permission from ref. 173. Copyright 2015 Royal Society of
Chemistry. (c) Schematic of the chiral nematic ordering present in CNC, along with an illustration of the half-helical pitch P/2 (B150–650 nm).34
Reproduced with permission from ref. 34. Copyright 2010 Springer Nature. (d) Schematic illustration of the synthesis of chiral nematic mesoporous carbon
by the evaporation induced self-assembly of CNC with silica precursors, followed by pyrolysis and etching of the silica.176 (e) A photograph of a sample of
the chiral nematic mesoporous carbon (scale bar: 2 cm).176 (f) TEM image of chiral nematic mesoporous carbon (scale bar: 200 nm).176 (g) SEM image of
chiral nematic mesoporous carbon (scale bar: 500 nm).176 (d–g) are reproduced with permission from ref. 176. Copyright 2011 Wiley-VCH. (h) Schematic
illustration of the fabrication process for carbonized hybrid CNC and NFC.177 Reproduced with permission from ref. 177. Copyright 2017 Springer.

mesoporous carbon.174,175 In water, suspensions of CNC orga-
nize into a chiral nematic phase that can be preserved upon
slow evaporation, thereby resulting in chiral nematic films
(Fig. 10c).34 MacLachlan et al. reported that the evaporation-
induced self-assembly of CNC with silica precursors can result
in composite films with chiral nematic structures. Upon pyr-
olysis and etching of the silica, freestanding films of chiral
nematic mesoporous carbon are obtained (Fig. 10d–g).176 In a
symmetrical capacitor with H2SO4 as the electrolyte, the meso-
porous carbon films display near-ideal capacitor behavior with
specific capacitance of 170 F g 1 at 230 mA g 1.
CNC and NFC can also be integrated together to form
porous carbon materials for supercapacitors (Fig. 10h).177 For
the hybrid films, the NFC formed a macroporous framework

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and the CNC was assembled around the NFC framework. By
depositing a thin layer of Al2O3 as a protective layer by atomic
layer deposition followed by etching away Al2O3 using HCl after
carbonization, a freestanding carbon film with a hierarchical
porous structure and a specific surface area of over 1200 m2 g 1
was produced. The two-level hierarchical porous structure
derived from NFC and CNC facilitated fast ion transport in
the film. When tested as an electrode material with a mass
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loading of 4 mg cm 2 for supercapacitors, the carbon film
exhibited a specific capacitance of 170 F g 1. Even at 50 A g 1, it
still retained 65% of its original specific capacitance.
4.3.2. Carbon hybrid materials. To further improve the
specific capacitance of nanocellulose-derived carbon, carbon
hybrid materials were developed by integration with active
materials such as activated carbon, nanocarbon, metal oxides,
hydroxides, and sulfides, etc. The carbon hybrid materials can
be prepared by direct pyrolyzation of the composites of nano-
cellulose and carbon materials. Ma et al. reported the prepara-
tion of N-doped carbon materials/RGO/BC composite paper.134
The BC was exploited as both a substrate and a biomass pre-
cursor for N-doped carbon by pyrolysis. The one-step carboniza-
tion treatment not only fabricated the N-doped 3D nanostructured
carbon composite materials but also forms the reduction of the
GO sheets at the same time. The symmetric supercapacitor
obtained using the composite paper as an electrode showed an
areal capacitance of 810 mF cm 2 in KOH and 920 mF cm 2 in
H2SO4, delivered an energy density of 0.11 mW h cm 2 in KOH
and 0.29 mW h cm 2 in H2SO4, and a maximum power density
of 27 mW cm 2 in KOH and 37.5 mW cm 2 in H2SO4. Free-
standing carbon nanofibers/activated carbon composite films
were prepared by carbonization of the NFC/activated carbon
composite films.178 The carbon nanofibers are ‘welded’ on acti-
vated carbon particles and integrated into one piece of carbon. The
network of carbonized NFC possessed better electron transport
efficiency than the activated carbon particles. When tested as
supercapacitor electrodes at commercial level mass loading, the
composite films exhibited 2-times-slower capacitance fading at
high current and 3-times-higher maximum power density than
the bare activated carbon. The carbon hybrid materials can also
be prepared by pyrolyzation of the composites of nanocellulose
and the carbon precursors. Highly graphitized carbon aerogels
were synthesized based on BC toughened lignin–resorcinol–
formaldehyde aerogels.179 The as-prepared carbon aerogels,
consisting of a blackberry-like, core–shell structured, and highly
graphitized carbon nanofibers, were able to undergo at least
20% reversible compressive deformation. Owing to the unique
nanostructure and large mesopore population, the carbon
materials exhibited high areal capacitances calculated using
the total surface area and the mesopore surface area of 62.2
and 78.7 mF cm 2, respectively.
Carbon hybrid materials can be achieved by direct reaction
between carbon framework and metal precursor under certain
conditions. MnO2-decorated carbon aerogels were fabricated by
employing BC-derived carbon aerogels as a precursor. Based on
the redox reaction 4MnO4 + 3C + H2O - 4MnO2 + CO32 +
2HCO3 , MnO4 ions were reduced spontaneously to MnO2 on
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the surface of BC-derived carbon aerogels by oxidizing the
exterior carbon (Fig. 11a–d).135 The carbon aerogel with high
graphitization serves as a highly conductive matrix for fast ion
and electron transport, whereas the ultrathin MnO2 film that
is strongly anchored on the surface of carbon aerogels can
effectively shorten the diffusion length of electrolyte ions during
the charge/discharge process and provide a large electrochemically
active surface area for the fast reversible Faradic redox reactions.
Asymmetric supercapacitor (ASC) fabricated by using the carbon
aerogels/MnO2 with a specific capacitance of 254.6 F g 1 as
positive electrodes, the N-doped carbon aerogels with a specific
capacitance of 173.3 F g 1 as negative electrodes, and Na2SO4 as
aqueous electrolyte, worked very well at different voltages, even
up to 2.0 V. Such an ASC displayed a maximum energy and
power density of 32.91 W h kg 1 and 284.63 kW kg 1, respec-
tively. Fan et al. decorated N-doped BC-derived carbon with
flower-like MnO2 (Fig. 11e–k).136 The BC-derived carbon/MnO2
exhibited a high specific capacitance of 273 F g 1 at 2 mV s 1.
The as-assembled carbon/MnO2//KOH activated N-doped carbon
ASC exhibited a considerably high energy density of 63 W h kg 1
in 1 M Na2SO4. The ASC also exhibited good cycling performance
with 92% specific capacitance retention after 5000 cycles.
To further improve the specific capacitance, the nanocellulose-
derived carbon materials were used as a scaffold for deposition of
metal hydroxyl and sulfide. Lai et al. reported the further deposi-
tion of ultrathin nickel–cobalt layered double hydroxide (Ni–Co
LDH) nanosheets on N-doped BC-derived carbon nanofibers
(Fig. 11l and m).137 The composite electrodes exhibited signifi-
cantly enhanced specific capacitance (1949.5 F g 1 at 1 A g 1),
high capacitance retention of 54.7% even at 10 A g 1, and good
cycling stability with 74.4% retention after 5000 cycles. ASCs
assembled by using the N-doped carbonized BC@Ni–Co LDH
composites as positive electrode and N-doped carbonized BC as
negative electrode exhibited an energy density of 36.3 W h kg 1
at a power density of 800.2 W kg 1. Zuo et al. reported the
uniform decoration of the pore walls of BC-derived carbon
aerogels with NiS particles through a hydrothermal process.139
The ASCs were constructed utilizing NiS composite carbon aerogels
and carbon aerogels as the positive and negative electrodes,
respectively. Through the synergistic effect of the 3D porous
structures and conductive networks derived from the carbon
aerogel and the high capacitive performance of NiS, the ASC
exhibited an energy density of B21.5 W h kg 1 at a power
density of 700 W kg 1, as well as good cycle stability with
B87.1% specific capacitance retention after 10 000 cycles.
Overall, the pyrolyzation of nanocellulose-based bulk materials
to carbon materials can obviously increase their specific surface
area and electrical conductivity. After further functionalization by
activation, heteroatom-doping, or the formation of hybrids with
other active materials, nanocellulose-derived carbon electrodes
showed good electrochemical performance. Controlling the
morphologies, structures, and ratios of the doping heteroatoms/
active materials of the nanocellulose-derived carbon materials
would be the main challenge in the future. Surface/interface
design on nanocellulose/nanocellulose-derived carbon and active
materials/precursors is crucial for controlling the interface
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Fig. 11 Carbon hybrid materials for supercapacitors. (a–d) Hybrid BC-derived carbon aerogels with MnO2:135 STEM images of the BC-derived carbon
aerogels/MnO2 with corresponding elemental mapping images of (b) C, (c) Mn, and (d) O. (a–d) are reproduced with permission from ref. 135. Copyright
2013 Wiley-VCH. (e–k) Hybrid N-doped BC-derived carbon with MnO2:136 (e and f) SEM and TEM images of the N-doped BC-derived carbon/
MnO2 composite; (g) high resolution TEM image of the N-doped BC-derived carbon/MnO2 composite; (h–k) STEM images of the N-doped BC-derived
carbon/MnO2 composite with corresponding elemental mapping images of (i) Mn, (j) O, and (k) C in the dashed square region of (h). (e–k) are reproduced
with permission from ref. 136. Copyright 2014 Wiley-VCH. (l and m) Hybrid BC-derived carbon aerogels with CBC-N@LDH:137 (l) schematic for the
preparation of CBC-N@LDH composites; (m) FESEM image of a CBC-N@LDH composite. (l and m) are reproduced with permission from ref. 137.
Copyright 2016 Wiley-VCH.

interactions during the preparation, pyrolyzation, activation, and
etching process. The ultimate goal is to achieve well-defined
bulk-, micro-, nano-, and even atom-scale structures of the
carbon materials. The structure–property relationship of the
novel developed nanocellulose-derived carbon materials should
be better understand for maximum utilizing the advantageous of
the carbon materials for high performance supercapacitors.
5. Lithium-ion batteries
Since the introduction by Sony Inc. in 1991, LIBs have emerged
as the main power source for portable electronic devices because
of their high energy density, large output voltage, appreciable
lifespan, and environmentally benign operation.180–183 A LIB
mainly consists of four functional components: anode, cathode,
electrolyte, and separator. In principle, the charging and dis-
charging process of a LIB is realized through the insertion/
deintercalation of Li ions transporting between the anode and
the cathode material. During charging, an external electrical
power source forces the current to pass in the reverse direction
and enables the migration (diffusion) of Li ions from the
cathode to the anode through the electrolyte. During the
discharging process, Li ions move back to the anode through
the nonaqueous electrolyte, carrying the current. Nanocellulose
can be integrated with other active materials or converted to
carbon materials to be further developed as the electrodes for
LIBs. The electrochemical performance of nanocellulose-derived
materials used as electrodes for LIBs has been compared and
summarized in Table 3.184–193 Nanocellulose-derived films/
papers can also be designed as separators for LIBs after carefully
controlling the micro/nanostructures. In the following sections,
we discuss recent advances related to the development of
nanocellulose and its derived materials for LIBs.
5.1. Flexible LIBs based on NFC/BC hybrid materials
The high aspect ratio NFC/BC can be used as a flexible substrate
and binder material to integrate with active materials to prepare
paper/film electrodes for flexible LIBs. Flexible positive electrodes
were developed by filtration of a water dispersion of NFC,
LiFePO4, and Super-P carbon particles (Fig. 12a–c).184 The elec-
trodes showed good mechanical properties both dry and when
soaked with battery electrolyte. The capacities were 151 mA h g 1
at C/10 and 132 mA h g 1 at 1C for sample dried at 170 1C.
Flexible negative electrodes have been obtained by integrating
nanocellulose with active materials such as CNTs and silicon.
Flexible paper anodes were prepared through a paper-making

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Table 3 Examples of different nanocellulose-derived materials for LIB electrodes reported in the literature

Electrochemical performance: capacity/rate

Nanocellulose type Nanocellulose process Electrode performance/energy density/Columbic efficiency Cyclic stability Ref.
1
TEMPO-oxidized Hybrid with LiFePO4 and NFC/LiFePO4/Super-P car- The coulombic efficiency for the samples dried at The cycling performance was 151 mA h g 184
NFC Super-P carbon particles bon particle composite 110 1C is around 97% during the first ten cycles, at C/10 and 132 mA h g 1 at 1C for samples
paper as cathode whereas the samples stored at 170 1C produced dried at 170 1C
efficiencies of around 99%
Cladophora NFC Hybrid with silicon nano- NFC/silicon nanoparticle/ The areal capacities is up to 2.5 mA h cm 2 and the The capacity is 1840 mA h g 1 (based on the 185

This journal is © The Royal Society of Chemistry 2018

particles and CNTs CNT composite paper as specific capacities is 3200 mA h g 1 (based on the weight of the Si) after 100 cycles at 1 A g 1
anode weight of the Si) corresponding to electrode specific
capacities of up to 800 mA h g 1 at 200 mA g 1;
Coulombic efficiency: 49%
1
Wood carboxy- Hybrid with SWCNTs and NFC/SWCNT nanopaper The first charge has a specific capacity of B5000 mA h The capacity is 1200 mA h g for 186
methylated NFC silicon aerogel deposited with a g 1 Si; the first discharge reveals the reversible capacity 100 cycles in half-cells
thin layer of silicon as to be B2100 mA h g 1; Coulombic efficiency: 43%
anode
TEMPO-oxidized Hybrid with graphite, NFC/graphite/Super-P An energy density of full paper battery is 188 mW h g 1 The reversible capacities is 146 mA h g 1 187
NFC Super-P carbon, LiFePO4, carbon composite layer as at C/10; the Coulombic efficiency readings were LiFePO4 at C/10 and 101 mA h g 1 LiFePO4
SiO2 anode; NFC/LiFePO4/ consistent in the range 99.5–100%, with the exception at 1C
Super-P carbon composite of the first cycles for each new C rate
layer as cathode
BC Pyrolyzation BC-derived carbon aerogel The initial discharge and charge capacities at After 100 cycles, the charge capacity showed 188
as anode 75 mA g 1 were 797 and 386 mA h g 1, respectively a slight decrease to 359 mA h g 1
BC Pyrolyzation and activated KOH activated BC-derived The initial discharge/charge delivers specific capacities The electrode delivers a specific capacity of 189
by KOH carbon nanofiber as anode of 1948.5 and 1091.4 mA h g 1, respectively, based on over 857.6 mA h g 1 after 100 cycles at
the total mass of the electrode 100 mA g 1 and retain a capacity of
325.4 mA h g 1 when cycled at 4000 mA g 1
Wood TEMPO- Hybrid with GO followed NFC/GO composite derived The second cycle has an initial discharge capacity at The discharge capacity remains 190
oxidized NFC by pyrolyzation carbon microfiber as anode 317.3 mA h g 1, with a Columbic efficiency of 62.2% 312 mA h g 1 at the 63rd cycle
BC Pyrolyzation; in situ BC-derived carbon loaded The specific capacity is ca. 380 mA h g 1 under 1 A g 1, The reversible capacity is ca. 600 mA h g 1 191
assembly of SnO2 with SnO2 as anode based on the total mass of the electrode; average after 100 cycles under 100 mA g 1
nanoparticles Coulombic efficiency: over 98.5%
BC Hybrid with Fe2O3 followed BC-derived carbon aerogel The discharge capacity is 410 mA h g 1 at 1 A g 1 The electrode delivers a reversible 192
by pyrolyzation decorated with nano-Fe3O4 capacity of 754 mA h g 1 after 100 cycles
as anode at 100 mA g 1
1
BC Hybrid with MoS2 followed BC-derived carbon nano- A reversible capacity is 935 mA h g 1 at 0.1 A g The capacity is 581 mA h g 1 after 193
by pyrolyzation fiber loaded with MoS2 (267 mA h g 1 at 4 A g 1), with a Coulombic 1000 cycles at 1 A g 1
nanoleaves efficiency of 66%
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Fig. 12 Flexible LIBs based on NFC hybrid materials. (a–c) Fabrication of flexible positive electrodes:184 (a) digital image of a flexible single-layered LiFePO4
paper electrode; (b) SEM image showing the top-side of a LiFePO4 paper electrode; (c) SEM image showing the carbon (bright particles)/NFC (dark surfaces)
side of a bi-layered electrode paper. (a–c) are reproduced with permission from ref. 184. Copyright 2013 Springer. (d–f) Fabrication of Si-conductive
nanopaper anode:186 (d) digital image of conductive nanopaper coated with Si sitting on a silicon wafer; (e and f) SEM images of the surface morphology of
the Si-conductive nanopaper. (d–f) are reproduced with permission from ref. 186. Copyright 2013 Springer. (g and h) Fabrication of single-paper LIB cells:187
(g) an illustration of the sequential filtration steps during the production of a paper battery cell; (h) digital image of a paper battery and SEM image of a paper
battery cross-section. (g and h) are reproduced with permission from ref. 187. Copyright 2013 Royal Society of Chemistry.

process using NFC, silicon nanoparticles and CNTs as the
building blocks.185 Owing to the uniform distribution and strong
adhesion of the silicon nanoparticles to the 3D conductive CNT/
NFC network, the electrodes exhibited good energy storage per-
formances with specific capacities of up to 800 mA h g 1 (based
on the weight of the whole electrode) and good cycling perfor-
mances. Silicon can also be integrated with CNT/NFC network by
deposition of a thin layer of silicon on the NFC/CNT nanopaper
aerogels through a plasma-enhanced CVD method (Fig. 12d–f).186
The open channels of the nanopaper aerogels allow for electrolyte
accessibility to the surface of silicon. The aerogels performed
well as anodes with a stable capacity of 1200 mA h g 1 for
100 cycles tested in half-cells.
Other active material such as Li4Ti5O12 has also been
integrated with NFC and CNT to prepared flexible paper
electrodes. The hybrid films had a dual-layer structure consisting
of Li4Ti5O12/CNT/NFC and CNT/NFC.194 The CNT/NFC layer with
a thickness of approximately 10 mm was utilized as a current
collector foil, which reduced the total mass of the electrode while
keeping the same areal loading of the active materials. The
flexible paper-electrodes showed high rate cycling performance,
and the specific charge/discharge capacities were up to
142 mA h g 1 at 10C. TEMPO-oxidized NFC was used as a
binder material to integrate with Li4Ti5O12 and carbon fibers to
fabricate flexible electrodes for LIBs.195 Even a small amount of
NFC (2 wt%) can be used to prepare the Li4Ti5O12 electrode,
which could meet the demands for high gravimetric energy
density applications when a low C rate is acceptable. A full cell
assembled using the Li4Ti5O12/carbon fiber/NFC as a negative
electrode and LiFePO4/carbon fiber/NFC as a positive electrode
exhibited a stable cycling performance with the specific
capacity of approximately 125 mA h g 1 after 20 cycles at
0.1C, and a high energy density of approximately 90 W h kg 1
(for Li4Ti5O12-based batteries). Flexible single-paper LIBs were
developed by Leijonmarck et al. through sequential filtration of
water dispersions containing the negative electrode (consisting
of graphite, Super-P carbon, and NFC), the separator (consisting
of NFC and SiO2), and the positive electrode (contained LiFePO4,
Super-P carbon, and NFC) (Fig. 12g and h).187 The resulting
paper LIB was thin and strong and had good cycling perfor-
mances. The energy density of the full paper battery at C/10 was
188 mW h g 1.
Overall, NFC/BC display great potential for the fabrication
of flexible LIBs because of their high aspect ratio, web-like

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entangled structures, and high mechanical strength. However,
most electrode materials reported so far have been synthesized
simply by mixing the active materials with nanocellulose, which
leads to relatively low interfacial interactions. Optimizing the
interfaces between the NFC/BC and the active materials using
covalent or noncovalent techniques should be considered for
improving the interface interactions, to achieve electrodes/LIBs
with appropriate and effective mass loading, high flexibility,
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mechanical strength, and good electrochemical performance.
The integration of active materials into NFC/BC networks using
other novel techniques such as ALD or CVD is also suggested.
5.2. Nanocellulose-derived carbon materials
Nanocellulose-derived carbon materials can be directly used as
electrodes for LIBs. The utilization of KOH activated BC-derived
carbon aerogels as anodes for LIBs can deliver a specific
capacity of over 857.6 mA h g 1 after 100 cycles at 100 mA g 1
and retain a capacity of 325.4 mA h g 1 even cycled at 4 A g 1.189
The good lithium storage performance of the carbon aerogels
can be attributed to its hierarchical micropore–mesopore struc-
ture and high surface area, which can enhance the contact area
of the electrode–electrolyte, decrease the diffusion resistance of
the lithium ions, shorten the diffusion length of the lithium
ions, and provide a solid and continuous pathway for electron
transport. To further improve the electrochemical properties, active
materials have been integrated with nanocellulose to develop
composites for carbonization. Li et al. reported the fabrication
of microfibers with a conductivity of 649  60 S cm 1 through a
wet-spinning method to prepare well-aligned NFC/GO hybrid
fibers followed by carbonization (Fig. 13a–e).190 GO acted as a
template for NFC carbonization, which changed the morphology
of the carbonized NFC from microspheres to sheets while
improving the carbonization of NFC. The as-prepared fibers
were demonstrated as lithium ion battery anodes, with a stable
discharge capacity of 312 mA h g 1. A carbon hybrid film was
fabricated by integrating NFC with Li4Ti5O12 and CNTs through
a papermaking method followed by carbonization (Fig. 13f).196
Owing to the uniform distribution and immobilization of Li4Ti5O12
into the interpenetrating carbonized NFC/CNT conductive network,
the carbonized paper anode displayed favorable transport behavior
of the lithium ion, and delivered a reversible discharge capacity
of 160 mA h g 1 and remained at 140 mA h g 1 after 10C with a
Coulombic efficiency of nearly 100%. Nanocellulose-derived
carbon materials can be employed as versatile conductive porous
scaffolds to support active anode materials. SnO2 nanoparticles,191
Ge nanoparticles,191 amorphous Fe2O3,197 Fe3O4 nanoparticles192
(Fig. 13g and h) and MoS2 nanoleaves,193 have been successfully
synthesized on nanocellulose-derived carbon scaffolds through an
in situ growth method. Wang et al. demonstrated the utilization of
BC-derived carbon aerogels as scaffold to support the in situ
assembly of active SnO2 and Ge nanoparticles (Fig. 13i–n).191
The SnO2 and Ge nanoparticles were uniformly immobilized
onto the BC-derived carbon nanofiber surface. The carbon
hybrid aerogels showed high specific capacity and good cycling
stability. The BC-derived carbon–SnO2 hybrid aerogels retained
a reversible capacity of approximately 600 mA h g 1 even after
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100 cycles under 100 mA g 1. In addition, the hybrid aerogel
electrodes exhibited good rate capability. Even at 1 A g 1, a
specific capacity of approximately 380 mA h g 1 was obtained
on the basis of the total electrode weight, which is higher than
the theoretical capacity of graphite. The high specific capacity
and good cycling stability of the carbon hybrid aerogels were
mainly attributed to the well-dispersed active nanoparticles,
interconnected conductive carbon nanofibers creating efficient
electron conduction pathways at the whole electrode scale, and
numerous interconnected voids facilitating the diffusion of
lithium ions.
In summary, the high specific surface area, high electrical
conductivity and porous structure of the nanocellulose-derived
carbon materials lead to high performances of the carbon
electrodes for LIBs. Integration with active materials can further
improve the electrochemical properties. More attention should
be paid to the integration of nanocellulose-derived carbon and
active materials with high theoretical capacity, such as SnO2 and
Ge, in a rational manner. The morphology and crystallization
of active materials anchored on carbon materials should be
carefully controlled during the fabrication process, and the
interface interactions between these active components and
electrolytes should also be considered. In addition, the construc-
tion and optimization of hierarchical micro-/mesoporous struc-
tures of nanocellulose-derived carbon materials through pore
engineering techniques is expected to introduce additional and
suitable positions for lithium storage and shorten the diffusion
length for ion and charge transport.
5.3. Nanocellulose-derived separators
The separator in a LIB prevents the direct contact between the
positive and negative electrodes while serving as the electrolyte
reservoir to enable the transportation of lithium ions between
the two electrodes.198 The separator is not directly involved in
any cell reactions, but its structure and properties play a critical
role in determining the LIB performance, including cycle life,
safety, energy density, and power density by influencing the cell
kinetics. Because nanocellulose-based paper/film is hydrophilic
and exhibits excellent mechanical/thermal properties, utilizing
the nanocellulose-derived paper/film as a separator for LIBs has
gained more interest.
An NFC film was obtained from densely packed NFC that
exhibited high strength and thermal stability, and was electrolyte-
philic. Therefore, the NFC separator imparted substantial
improvement in the ionic conductivity, electrolyte wettability,
and thermal shrinkage, as compared with that of the commer-
cialized PP/PE/PP separators.199 The cladophora NFC separators
have a typical thickness of approximately 35 mm, an average pore
size of approximately 20 nm, a Young’s modulus of 5.9 GPa,
and an ionic conductivity of 0.4 mS cm 1 after soaking into
1 M LiPF6 ethylene carbonate:diethyl carbonate electrolyte.200
The NFC separators were thermally stable at 150 1C and were
electrochemically inert in the potential range between 0 and
5 V vs. Li+/Li. A LiFePO4/Li cell containing a NFC separator
showed good cycling stability with 99.5% of capacity retention
after 50 cycles at 0.2C. Because NFC separators were usually
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Fig. 13 Nanocellulose-derived carbon materials for LIBs. (a–e) The fabrication of NFC/GO-derived hybrid carbon fibers:190 (a and b) schematic to show the
morphology of NFC changed from fibers (before carbonization) to sphere particles after carbonization. In the carbonized (GO + NFC) microfiber, only
sheets formed after carbonization as shown in (c and d); (e) is the structure of a carbonized (GO + NFC) microfiber. (a–e) are reproduced with permission
from ref. 190. Copyright 2014 Wiley-VCH. (f) Schematic illustration of preparation the flexible single-layer paper electrode by using a papermaking
method.196 Reproduced with permission from ref. 196. Copyright 2016 American Chemical Society. (g and h) Fabrication of BC-derived carbon nanofiber/
Fe3O4 composites:192 (g) schematic illustration of the fabrication of BC-derived carbon nanofiber/Fe3O4 composites; (h) sequential photographs of the
BC-derived carbon nanofiber/Fe3O4 composite during repeated bending and compressing demonstrating the excellent flexibility. (g and h) are reproduced
with permission from ref. 192. Copyright 2015 Royal Society of Chemistry. (i–n) Fabrication of BC-derived carbon aerogel/active nanoparticle composites:191
(i) the digital image of the carbon aerogel; (j) SEM image of the carbon aerogel; (k) in situ assembly of active nanoparticles into interwelded carbon nanofibers
as LIB electrode; (l) TEM image of the carbon aerogel/SnO2 composites; (m) comparison of cycling performances of carbon aerogel/SnO2 composites and
aggregated SnO2 nanoparticles over 100 cycles at 100 mA g 1; (n) comparison of cycling performances of carbon aerogel/Ge composites and aggregated
Ge nanoparticles over 100 cycles at 100 mA g 1. (i–n) are reproduced with permission from ref. 191. Copyright 2013 Wiley-VCH.

hard in providing highly porous structures owing to the densely varying the SiO2 content in the NFC suspension. The as-prepared
packing of NFC, SiO2 nanoparticles have been introduced as a separator exhibited high ionic conduction, thus contributing
NFC ‘‘disassembling’’ agent to facilitate the evolution of a more to good cell performance. Wang et al. developed a bilayered
porous structure.201 The porous structure can be tuned by nanocellulose-based separator, which contains a mesoporous

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insulating NFC layer and a redox-active PPy-containing support
layer. The as-fabricated redox-active separator can be used to
enhance the capacity of LIBs.202
Recently, Lee et al. pioneered the development of new kinds
of NFC-based separators. A heterolayered mat battery was
fabricated based on a unitized separator/electrode assembly
(SEA) architecture (Fig. 14a–c).203 The unitized SEAs consisted
of NFC separators and solely SWCNT-netted electrode active
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materials (LiFePO4 (cathode) and Li4Ti5O12 (anode) powders
were chosen as model systems). The NFC separator played a
critical role in securing the tightly interlocked electrode–
separator interface, whereas the SWCNTs exhibited multi-
functional roles as electron conductive additives, binders,
current collectors and also non-Faradaic active materials. The
SEA allowed significant improvements in the mass loading
of active materials, electron transport pathways, electrolyte
accessibility, and misalignment-proof of separator/electrode
interface. The batteries fabricated by stacking anode SEA and
cathode SEA exhibit advances in the electrochemical perfor-
mances, shape flexibility, and safety tolerance.
Using a similar NFC separator in batteries, the electrode was
further modified by using NFC/MWCNT-intermingled hetero-
nets embracing electrode active powders (NM electrodes). The
multi-stackable NM electrodes were assembled with a NFC
separator, leading to a single-unit hetero-nanonet paper cell
(composed of one NM cathode/one NFC separator/one NM
anode) (Fig. 14d and e),204 which provided an increase in the
energy density (226 W h kg 1 at 400 W kg 1 for LiNi0.5Mn1.5O4/
graphite system). The batteries were flexible and would be
folded to fabricate paper crane batteries through an origami
folding technique. By considering the unwanted byproducts in
electrolytes, such as manganese ions (Mn2+) dissolved from
lithium manganese oxide electrode materials and hydrofluoric
acid (HF) generated by side reactions between residual water
and lithium salts, a heterolayered nanomat-based hierarchical/
asymmetric porous separator was developed.205 The separator
was composed of a terpyridine (TPY)-functionalized NFC nano-
porous thin mat as the top layer and an electrospun polyvinyl-
pyrrolidone (PVP)/polyacrylonitrile (PAN) macroporous thick mat
as the support layer (Fig. 14f–m). The hierarchical/asymmetric
porous structure of the heterolayered nanomat was rationally
designed by considering the trade-off between the leakage
current and the ion transport rate. The TPY (to chelate Mn2+
ions) and PVP (to capture hydrofluoric acid)-mediated chemical
functionalities bring a synergistic coupling in suppressing
Mn2+-induced adverse effects, thus enabling a substantial
improvement in the high-temperature (60 1C) cycling performance
(capacity retention B80% after 100 cycles) far beyond that
attainable with conventional membrane technologies (5% for
a commercial PP/PE/PP separator).
Overall, separators constructed with nanocellulose as building
blocks display high wettability for the electrolyte, are extremely
thin with strong mechanical strength, are electrochemically,
structurally, and thermally stable, and have a porous structure,
which makes them promising candidates for LIBs. Precisely
controlling the pore structures and sizes is still challenging
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because the nanocellulose is usually densely packed within the
thin separators. A porous structure with high tortuosity is
expected to prevent the growth of dendritic lithium. Therefore,
efficient pore engineering techniques are needed to adjust
the pore structures and sizes as well as the porosity of the
nanocellulose separators. The integration of nanocellulose
membranes and other type of membranes such as electrospun
nonwoven mats should be considered to exploit the synergy
effect of the beneficial influences of two or multiple layers.
6. Other batteries
6.1. Lithium–sulfur batteries
Li–S batteries have received increasing attention recently because
they can offer high theoretical gravimetric (2500 W h kg 1) and
volumetric (2800 W h L 1) energy density and 1 order of
magnitude higher capacity (1675 mA h g 1) than that of
conventional LIBs.9,10,206–210 In addition, elemental sulfur is
environmentally friendly, cheap, and abundant, which makes
Li–S batteries a particularly attractive and low-cost energy
storage device. However, the practical application of Li–S
batteries still faces several challenges. First, the volume
changes of sulfur particles during electrochemical cycles lead
to structure changes of the active materials and cause low
capacity. Second, sulfur and Li2S are both insulating, resulting
in sluggish electrochemical kinetics. Third, polysulfides are
easy to dissolve in the electrolyte, which is the main cause
of the ‘‘shuttle phenomenon’’.206,208 To solve the problems
mentioned above, various efforts have been made to design and
develop novel electrodes, separators, and electrolytes. Recently,
several types of nanocellulose materials have been developed to
construct high performance Li–S batteries, mainly based on
their intrinsic structures and properties.
Nanocellulose can be integrated with active materials to
fabricate hybrid electrodes for Li–S batteries. Owing to its high
aspect ratio, entangled networks, and high abundance hydroxyl
groups on the surfaces, NFC was developed as a flexible building
block to fabricate freestanding and sandwich-structured cathode
materials with high areal mass loading for long-life Li–S batteries
(Fig. 15a–e).211
Sulfur was impregnated in N-doped graphene and constructed
as a primary active material, which was further welded in the NFC/
CNT framework. Interconnected NFC/CNT layers on both sides of
the active layer were uniquely synthesized to entrap polysulfide
species and supply efficient electron transport. The synergistic
effects of the physical encapsulation by carbonaceous materials
(graphene and CNT/NFC fibers) and chemisorption for lithium
polysulfides by chemical functionalization (hetero N-doping
and hydroxyl groups) resulted in good electronic conductivity
and suppression of polysulfide dissolution and migration. The
rationally designed structure endowed the electrode with high
specific capacity and good rate performance. The electrode with
an areal sulfur loading of 8.1 mg cm 2 exhibited an areal
capacity of B8 mA h cm 2 and an ultralow capacity fading of
0.067% per cycle over 1000 charge/discharge cycles at C/2 rate,
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Fig. 14 Nanocellulose-derived separators for LIBs. (a–c) The fabrication of NFC/SWCNT-based SEAs:203 (a) schematic representation of the overall
fabrication procedure for unitized SEA; (b) a photograph of a h-nanomat full cell and a schematic illustration describing the electron transport pathways
and electrolyte accessibility; (c) a photograph showing the electrochemical activity of a h-nanomat cell after the repeated twisting/untwisting
deformation. (a–c) are reproduced with permission from ref. 203. Copyright 2014 American Chemical Society. (d and e) Development of hetero-
nanonet rechargeable paper batteries using NFC separator:204 (d) a conceptual representation of a single-unit cell and its contribution to the energy
density of cells; (e) a photograph showing the operation of a mini toy car installed with the single-unit hetero-nanonet paper cell. (d and e) are
reproduced with permission from ref. 204. Copyright 2015 Wiley-VCH. (f–m) Development of hierarchical/asymmetric porous membrane for smart
battery separator:205 (f) schematic depiction of the overall fabrication procedure of the separator; (g) schematic and pore size distribution of the PVP/PAN
electrospun mat, TPY/NFC, and TPY/NFC on PVP/PAN mat; (h–m) Mn2+ ion binding capability of TPY-NFC. B3LYP/6-31G(d,p)-optimized geometries of
(h) Mn2+(PP3), (i) Mn2+(Glc), and (j) Mn2+(TPY) complexes with the relative binding energies from DFT calculations at B3LYP/6-311+G(2d,2p) level,
including BSSE corrections. Equilibrium morphologies after a 400 ns MD simulation at 333 K and normalized z-axis position probability of Mn2+ ions for
the last 100 ns on the surface of (k) PP, (l) cellulose, and (m) TPY-cellulose. Violet beads represent the Mn2+, and the ethylene carbonate solvent is shown
as a transparent surface. (f–m) are reproduced with permission from ref. 205. Copyright 2016 American Chemical Society.

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Fig. 15 Nanocellulose-derived materials for Li–S batteries. (a–e) NFC-derived materials:211 (a) Schematic illustration of the freestanding electrode
preparation using NFC as one of the building blocks; digital photographs of (b) the electrode and (c) its flexibility; (d) 3D XRM image of the electrode with
8.1 mg of sulfur per cm2. To get a stark contrast, sulfur in yellow, carbon in gray, and white in the outmost two layers and middle layer, respectively;
(e) experimental demonstration showing that the prototype soft pack battery can light up three blue LEDs under bent states. (a–e) are reproduced with
permission from ref. 211. Copyright 2017 Wiley-VCH. (f–j) CNC-derived materials:215 (f) schematic illustration of the synthesis of CNC-derived N/S-doped
carbon; Ab initio calculations illustrating the most stable Li2S2 binding configurations after full relaxation for carbon substrates (g) with no doping and
doped with (h) 1N doping, (i) 1N + 1S, and (j) 1N + 2S per supercell (bottom right for side view). Insets on the top left are the 2D deformation charge
distributions of the corresponding substrates only without Li2S2 (red for accepting electrons, blue for donating electrons), with the magnified versions
(around the heteroatoms) shown on the bottom left. Gray, blue, purple, and yellow balls represent C, N, Li, and S atoms, respectively. (f–j) are reproduced
with permission from ref. 215. Copyright 2015 Wiley-VCH.

whereas the average Coulombic efficiency was approximately Nanocellulose-derived carbon materials exhibit good perfor-
97.3%, indicating good electrochemical reversibility. mance as electrodes for Li–S batteries. Huang et al. reported the

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utilization of BC-derived carbon aerogels as a 3D framework for
sulfur to fabricate a flexible sulfur cathode for Li–S batteries.212
The as-prepared 3D carbon nanofiber networks exhibited high
electrical conductivity and good mechanical stability. The
macroporous structure of the carbon aerogels contributed to
a high sulfur loading of 81 wt% through sulfur precipitation
from the CS2 solution. The sulfur species wrapped around the
carbon nanofibers were well dispersed. Even at such a high
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loading, the S/carbon aerogel composite still contained suffi-
cient free space to accommodate the volume expansion of sulfur
during lithiation. An ultralight and thin BC-derived carbon
aerogel interlayer was inserted between the sulfur cathode and
separator to provide an extra conductive framework and some-
what adsorb the migrating polysulfides. The carbon aerogel
interlayer can also act as an additional collector for sulfur and
thus could prevent the over-aggregation of insulated sulfur on
the cathode surface. With a thin carbon aerogel interlayer, the
flexible S/carbon aerogel cathode exhibited a high discharge
capacity (1134 mA h per gSul at 200 mA g 1), long-term cycle
stability (700 mA h per gSul at 400 mA g 1 over 400 cycles), and
good rate capability. To further improve the electrochemical
capability, heteroatom doping has attracted attention because
it is an effective way to tailor the electronic and chemical
properties of the carbon host. N is the most extensively studied
heteroatom, which could improve the electron conductivity and
strongly adsorb polysulfides, endowing a good rate capability
and remarkable cycling stability. N-Doped carbon materials have
been prepared from carbonization and activation (with KOH) the
aerogels derived from BC hydrogels and its residual medium
with enriched carbon and nitrogen. The S/carbon (with N-doped)
composites were synthesized through a melt-diffusion method
and used as the cathode material, which showed an initial
discharge capacity of 1267 mA h g 1 and capacity retention of
995 mA h g 1 after 500 charge/discharge cycles at a rate of 0.1C
with a Coulombic efficiency of 99.0%.213 Recently, Li et al.
developed a N,O-codoped carbon nanofiber aerogel by pyrolysis
a BC aerogel in an ammonia atmosphere.214 O was doped owing
to the oxygenated species in the cellulose that remained in
the aerogel after pyrolysis, whereas N was originated from the
N-containing compounds left by culture media and secretions
and the ammonia gas used during pyrolysis. The oxygen in the
carbon nanofiber aerogel could further enhance the polysulfide
retention capacity owing to improved hydrophilicity of the
surface. The N,O-codoped carbon nanofiber aerogel was
employed to a gel-based sulfur cathode, which simultaneously
achieved both high sulfur content and high sulfur loading. With
a sulfur loading of 6.4 mg cm 2 and a sulfur content of 90% in
the whole electrode (including current collector) level, a capacity
of 943 mA h g 1 was achieved, which corresponded to an areal
capacity of 5.9 mA h cm 2. CNC was also utilized as a carbon
source for dual-atom doping to prepare carbon materials with
hierarchical porous structures. N,S-Codoped carbons with a high
pore volume and surface area were fabricated from the liquid-
crystal-driven self-assembly of CNC coated with polyrhodanine
followed by pyrolysis and etching of silica (silica precursors were
added into the dispersion to provide a spacer between particles
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and avoid structural collapse upon carbonization) (Fig. 15f).215
A synergistic effect from N and S heteroatoms modified the
electron density distribution of the host substrate, leading to
stronger polysulfide binding than that for non-doped or N
single-doped carbons. Ab initio calculations based on density
functional theory revealed the strong interactions between Li+
and doped N atoms (Li–N) as well as the polysulfide anions and
doped S atoms (S–S) (Fig. 15g–j). The electrical conductivity of
N,S-codoped carbon was also greatly improved compared with
nondoped carbon, favoring high-rate kinetics. Using this dual-
doped carbon as sulfur host, the sulfur electrode was able to
deliver a high capacity of 1370 mA h g 1 at C/20 and charge/
discharge for 1100 cycles at 2C with a very low capacity fading of
0.052% per cycle. This was attributed to the high pore volume
and surface area of the host that can provide sufficient active
sites for chemically adsorbed lithium polysulfides.
Nanocellulose-derived hybrid materials and carbon hybrid
materials with a rational structure design can be used as
separators or electrolytes for Li–S batteries. BC-derived carbon
materials were mixed with TiO2 to form a composite slurry and
coated on one side of a separator.216 The carbon materials served
as an upper collector and supplied strong physical adsorption of
polysulfides, whereas the TiO2 can chemically adsorbed poly-
sulfides. Thus, the carbon materials/TiO2 modified separator
was efficient restraining the shuttle effect of Li–S batteries. Cells
with carbon materials/TiO2 modified separator showed an initial
discharge capacity of 1314 mA h g 1 at 0.2C, and the capacity
retention was 1048.5 mA h g 1 after 50 cycles. During the rate
test, Li–S cells delivered a discharge capacity of 537.1 mA h g 1
at 2C. Nair et al. prepared NFC-laden composite polymer electro-
lytes using a thermally induced polymerization process.217 The
NFC mainly acted as a reinforcing agent and provided an
interpenetrated network for methacrylate-based polymer matrix
to fabricate opaque and self-standing polymer electrolyte mem-
branes. The activated membrane in the liquid electrolyte showed
a high conductivity (41.2 mS cm 1) and a stable interface
towards lithium metal. The final cell with a Li/activated polymer
electrolyte separator/sulphur-activated carbon cell showed good
cycling stability at above 700 mA h g 1 even at 1C rate and a
Columbic efficiency of 499% at ambient temperature. The stable
cycling profile was attributed to the reduction of the migration
of polysulphide towards the anode by the entrapment of NFC in
the polymer matrix.
Overall, nanocellulose-derived hybrid materials and carbon
materials have the potential to be used as electrodes, separators
and electrolytes for high performance Li–S batteries. However,
challenges still exist such as how to achieve both high content
and high loading of active materials in the same cathode while
still preserving the flexible, high mechanical strength, and
excellent electronic conductivity of the nanocellulose and
nanocellulose-derived materials. To alleviate the polysulfide
shuttle with a stable and persistent effect is still challenge for
the nanocellulose-derived electrodes and separators. Thus, the
rational designing and optimization of hierarchical porous
structures and surface/interface properties of nanocellulose-
derived hybrid materials and carbon materials is critical for
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constructing high-performance Li–S batteries. Progress in this direc-
tion is expected to be accomplished through a synergistic combi-
nation of theoretical calculations and experimental approaches.
6.2. Sodium-ion batteries
Over the last few years, NIBs have attracted increasing attention
as an important source of energy storage devices largely owing to
the fact that Na is the sixth most abundant element in the earth’s
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crust and it is inexpensive and environmentally friendly for
large-scale energy storage.8,218–223 The working principle of NIBs
is similar to that of LIBs. However, several good anode materials
used in LIBs such as graphitic carbon materials exhibited poor
storage properties for NIBs, mainly because the radius of Na+ is
B55% larger than that of Li+; most materials do not possess host
frameworks with larger interstitial spaces for Na ion insertion/
extraction. Besides the kinetic issue, the larger Na+ radius is
also relevant for possible structural change during insertion or
extraction. Thus, the development of appropriate electrode
materials is critical for improving the performance of NIBs.
Recently, nanocellulose-derived materials have gained interest
for use as electrodes in NIBs.
Nanocellulose can be integrated with active materials to
fabricate electrodes for NIBs. Li et al. reported the use of
TEMPO-oxidized NFC as a dispersant to efficiently disperse
and form a hybrid with 2D materials such as molybdenum
disulfide (MoS2) in aqueous solution.224 The as-prepared NFC/
MoS2/CNTs composite films with a weight ratio of 16.5 : 67 : 16.5
can act as flexible electrodes for NIB anodes. The first cycle
discharge capacity was 147 mA h g 1, which was higher than that
of the MoS2/CNTs composite anode, even though it had a lower
MoS2 content. The Coulombic efficiency of the first cycle was
43.8% and increased to 89.7% by the third cycle.
Nanocellulose-derived carbon materials display advantages
such as chemical and thermal stability, high electrical conduc-
tivity, as well as high Na-storage capacity for the development of
anode materials for NIBs. Luo et al. reported the synthesis
of carbon nanofibers directly from NFC through a pyrolysis
process.225 The unique morphology of the carbon nanofibers
facilitated highly reversible ion migration and provided plenty of
contact area between the electrode and the electrolyte. Thus, when
utilized as an anode material for NIBs, the carbon nanofibers
delivered not only a high reversible capacity of 255 mA h g 1 at
40 mA g 1 and a rate capability of 85 mA h g 1 at 2000 mA g 1,
but also a good cycling stability of approximately 180 mA h g 1
at 200 mA g 1 over 600 cycles. To further improve the electro-
chemical performance, engineering the 3D porous carbon
materials by heteroatom doping was conducted. Zhang et al.
synthesized core-sheath structured carbon nanofiber@N-doped
porous carbon (CNF@NPC) composite through carbonization of
PPy coated BC.226 The inner carbon nanofiber cores pyrolyzed
from BC ensured the high electronic conductivity and the supply
of a 3D matrix, whereas the outer NPC layers derived from PPy
with a high surface area and an appropriate N doping improved
the reversible capacity. When utilized as an anode material,
the CNF@NPC exhibited a high reversible specific capacity
(240 mA h g 1 at 100 mA g 1 over 100 cycles), high rate
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performance (146.5 mA h g 1 at 1 A g 1), and good cycling
stability (148.8 mA h g 1 at 500 mA g 1 over 400 cycles).
Compared to single-atom doping, dual-atom doping in carbon
could exploit the synergistic effects of the advanced features of
the two heteroatoms, which takes advantage of the additionally
created defect sites and electronic conductivity for sodium storage.
Recently, Yu et al. synthesized N,O-dual doped carbon networks by
using the pyrolysis of BC/PANI and subsequent activation with
KOH (Fig. 16a and b).227 BC acted as a 3D scaffold to deposit PANI
but also formed a conductive carbon network during the carboni-
zation, whereas the PANI formed large amounts of small N,O-dual
doped carbon particles along the interconnected nanofibers in situ.
The obtained carbon networks exhibited a high specific capacity
(798 mA h g 1), long cycle life (545 mA h g 1 at 100 mA g 1 after
100 cycles), and high rate capability (240 mA h g 1 at 2 A g 1 after
2000 cycles). The carbon materials with 3D well-defined porosity
and N,O-dual doped induced active sites, contributing to the
enhanced sodium storage.
B,N-Dual doped carbon materials were developed by fully
infiltrating NH4HB4O7
H2O into the BC pellicle followed by
carbonization (Fig. 16c and d).228 The B,N-dual doping created
synergistic effects to enlarge the carbon layer spacing for Na+
insertion, and improved the electrochemical activity as well as
electronic conductivity. The obtained carbon materials deliv-
ered a specific charge capacity of 581 mA h g 1 at 100 mA g 1
after 120 cycles and good cycling stability (277 mA h g 1 at
10 A g 1 after 1000 cycles). In addition to NFC/BC with a high
aspect ratio, Zhu et al. reported the carbonization of short and
high specific surface area CNCs at 1000 1C for use in NIBs.229
During the carbonization, the CNC was transformed into
porous carbon with an increased short-range ordered lattice
and percolated carbon nanofiber (Fig. 16e–h), which exhibited
a good structure and conductivity for NIB anodes. A starting
capacity of 340 mA h g 1 at 100 mA g 1 was achieved, which
maintained 88.2% capacity over 400 cycles.
Overall, nanocellulose has potential to be developed as an
electrode material for NIBs. Nanocellulose can form a hybrid
with active materials or be converted to 3D interconnected
carbon materials and be further functionalized by doping with
heteroatoms or integrated with active materials. Compared with
LIBs, the larger size of sodium ions hampers the kinetics of
the electrochemical reactions. Therefore, reversible electrodes
derived from nanocellulose-derived materials need to possess
large enough channels and/or interstitial sites. The challenge in
the future is to design and construct novel hierarchical 3D
fibrous porous structures with appropriate space for Na storage,
short diffusion distance for ions, high Na+ diffusion coefficients,
and fast electron transport from various types of nanocellulose
through multiple synthesis strategies.
7. Summary and outlook
The past few years have witnessed significant progress in
the development of nanocellulose for electrochemical energy
storage owing to its exceptional structures and properties
Chem. Soc. Rev., 2018, 47, 2837--2872 | 2865
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Fig. 16 Nanocellulose-derived materials for NIBs. (a and b) Fabrication of BC-derived N,O-dual doped carbon:227 (a) schematic illustration of the
fabrication process of the N,O-dual doped carbon network composite; (b) schematic illustration of the transportation process of Na-ion and electron in
the N,O-dual doped carbon network composite. (a and b) are reproduced with permission from ref. 227. Copyright 2016 Wiley-VCH. (c and d) Fabrication
of BC-derived B,N-dual doped carbon:228 (c) schematic illustration of the fabrication process of B,N-dual doped carbon; (d) elemental mapping images
of B,N-dual doped carbon electrode. (c and d) are reproduced with permission from ref. 228. Copyright 2016 Wiley-VCH. (e–h) Fabrication of CNC-
derived carbon:229 (e) HRTEM images of CNC; (f) TEM image of the CNC derived carbon (front-on); (g) higher magnification HRTEM image of the area
contained in the red squared in (f); (h) higher magnification HRTEM image of the area contained in the red squared in (g) with the Fourier transform shown
in the inset. (e–h) are reproduced with permission from ref. 229. Copyright 2017 Springer.

as well as its sustainability. In this review, we have summarized
the recent advances in this area, with a particular focus on the
structures and characteristics of nanocellulose within the
cell walls of cellulose sources, the fabrication, structural and
functional design of nanocellulose, and the application of the
nanocellulose-derived materials for advanced energy storage
systems. Thanks to the efforts of many research groups, a rich
variety of nanocellulose materials with various structures and
surface chemistry performance have been developed from various
sources using multiple fabrication strategies (Table 1),77,82,86–91
which provides plenty of building blocks for further development
of high-performance energy storage materials and devices.
Owing to the nanoscale dimension, high specific surface area,
high relative crystallinity, reactive surfaces containing hydroxyl
groups, entangled web-like structures, and advantageous
mechanical and thermal properties, nanocellulose can be
utilized for (1) constructing self-standing and high strength
electrodes or separators, (2) integration with other electrochemical
active materials, (3) developing flexible substrates/scaffolds
for flexible devices, (4) designing multifunctional separators,
(5) developing carbon-based porous materials and carbon hybrid
materials, (6) constructing multiple kinds of materials or devices
using various kinds of nanocellulose and their hybrids as building
blocks. The nanocellulose-derived materials exhibit advantages
for various electrochemical energy storage applications, including
supercapacitors, LIBs, Li–S batteries, and NIBs.
Although nanocellulose has been successfully developed
to construct a series of advanced materials/devices for high
performance energy storage devices, there are some issues that
need to be addressed in the future.
(1) Large-scale fabrication. Although the fabrication of nano-
cellulose has become mature during the past 10 years and mass
production of nanocellulose has been achieved by several
research institutions and companies, the quality such as the
structures, nanofibrillation degree, and surface chemical pro-
perties of nanocellulose is still quite different compared with those
fabricated at a laboratory scale. Thus, it is still difficult to perform
large-scale production of nanocellulose with high quality and
uniformity, especially for the large-scale production of high aspect
ratio and individualized NFC. We should pay more attention on

2866 | Chem. Soc. Rev., 2018, 47, 2837--2872 This journal is © The Royal Society of Chemistry 2018

Chem Soc Rev
developing and optimizing mechanical processing equipment such
as large capacity high pressure homogenizer, beads mill, twin screw
extruder, and high-intensity ultrasonicator to achieve the mass
production of high quality nanocellulose for sustainable supply
for energy storage development and other applications. Further-
more, limited by the preparation technology and apparatus such as
vacuum filter, supercritical dryer, and tube furnace, it is still a big
challenge to perform continuous and large-scale fabrication of
Published on 21 March 2018. Downloaded by Instituto Politecnico Nacional on 10/25/2019 9:23:18 PM.
nanocellulose-derived electrodes/separators with a large size for
energy storage devices.
(2) Surface/interface engineering. Surfaces and interfaces play
crucial roles in the fabrication and performance of nanocellulose-
derived energy storage materials/devices. Surface/interface
engineering can induce novel physicochemical properties and strong
synergistic effects for nanocellulose and nanocellulose-derived
materials, providing new and efficient strategies to enhance the
energy storage activities. Thus, we should exploit the surface atomic
or molecular engineering (e.g., heteroatom-doping, chemical
modification) to directly utilization or chemical modification
of the surface structures and chemistry of nanocellulose and
nanocellulose-derived carbon materials, and further integrate
the materials with other active materials through various inter-
face engineering routes such as physical and chemical treatment
related to weak (e.g., hydrogen bonding, van der Waals inter-
action) or strong (e.g., covalent bonding) effects. More alternative
methodologies can be inspired from the success work of other
similar materials such as polymeric materials.230 We should
develop surface/interface engineering technique to provide
nanocellulose-derived energy storage materials/devices with
tunable micro-, nano- and even atom-scale structures, tailorable
physicochemical properties, excellent electronic conductivity,
flexibility, advantageous mechanical properties, physical and
chemical stability as well as high energy storage performances.
(3) Pore engineering. The sizes and structures of the pores
and the porosity of the nanocellulose-derived materials critically
affect their performance. The pore size of materials can range
from the nanometer to micrometer scale, depending on the
structure of nanocellulose and the active materials as well as the
processing methods. For the electrodes, hierarchical micropore–
mesopore structure should be developed to improve the contact
area of the electrode–electrolyte, decrease the diffusion resis-
tance of electrolyte ions, and shorten the diffusion length of the
electrolyte ions. For the separator, the porosity and pore size of
the nanocellulose film should be designed to achieve the elec-
trically isolate the electrodes but facilitate the ionic transport.
However, it is still difficult to precisely control the pore struc-
tures and sizes of the nanocellulose-derived materials. There-
fore, pore engineering that can tune the pore size, especially at
the nanometer- and even the atom-scale level is highly desirable.
It is also suggested to get more inspiration from the research
experience of other similar polymeric materials,231,232 to opti-
mize the pore engineering technique of nanocellulose-derived
materials. In the future, we should design all possible pathways
to maximize generate and control the porous structures and
avoid the collapse of web-like structures of the nanocellulose-
derived materials throughout the whole life cycles.
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(4) Flexibility. Forthcoming smart electronics era necessitates
the development of advanced flexible energy storage devices with
environmentally friendly characteristics, lightweight, low cost,
and advantageous energy storage performance. Nanocellulose
meets all the above-mentioned critical requirements and can be
utilized as a building block to construct flexible substrates/
scaffolds or as carbon precursors to fabricate light and flexible
energy storage devices with shape-conformability, aesthetic
diversity, and advantageous mechanical properties. For the
separators and electrodes derived from nanocellulose or nano-
cellulose composites, the mechanically robust and entangled
networks of nanocellulose should be preserved during the whole
fabrication and utilization process. For the nanocellulose-
derived carbon electrodes, the hydrogen bond interaction
between the nanocellulose should be removed and the inter-
connected network structures of the nanocellulose should be
carefully preserved during carbonization, which would ensure
robust mechanical properties with high flexibility of the carbon
electrodes. Furthermore, excellent conductivity and a high
capacity should be achieved for nanocellulose-derived electro-
des by integration with active materials without sacrificing
the structural integrity and flexibility. It is also necessary to
integrate the electrolytes/separators, electrode materials, current
collectors, and packaging to maximize the synergistic effect of
the composite structures and utilization of the flexibility derived
from the nanocellulose entangled networks, which make the
devices simultaneously exhibit high flexibility and high energy
storage performance.
(5) New materials and new applications. As nanocellulose
can be fabricated from various sources using different prepara-
tion methods, new materials/devices for energy storage should
be explored using different types of nanocellulose and their
combinations as building blocks, based on the sizes, struc-
tures, and surface chemical performance of nanocellulose. For
example, optically transparent and flexible electrodes can be
developed by the integration of TEMPO-oxidized NFC with
transparent conductive materials. Chiral nematic mesoporous
carbon electrodes can be developed by using sulfuric-acid-
hydrolyzed CNC as a template. Investigation of new materials
as well as the fabrication strategies could open up new oppor-
tunities for a wide range of applications. To date, nanocellulose
and its derived materials have been widely used for super-
capacitors and LIBs, however, a few works were reported for
their application in Li–S batteries and NIBs. Moreover, some
new types of energy storage systems such as Mg(Al,Mn)-ion
batteries have been rarely explored. Considering that nano-
cellulose and its derived materials are mechanically robust and
with structural, surface/interface chemistry adjustable, they can
be readily used as a green material solution for newly emerging
energy storage systems through customized control of their
structure and characteristics.
Conflicts of interest
There are no conflicts of interest to declare.
Chem. Soc. Rev., 2018, 47, 2837--2872 | 2867

Review Article
Acknowledgements
This work was supported in part by the National Natural Science
Foundation of China (No. 31400495; 51672055; 31770594), Young
Elite Scientists Sponsorship Program by CAST (No. 2017QNRC001),
Ten Thousand Talent Program (No. W02020249), Funds supported
by the Fok Ying-Tong Education Foundation, China (No. 161025),
and Fundamental Research Funds for the Central Universities. We
Published on 21 March 2018. Downloaded by Instituto Politecnico Nacional on 10/25/2019 9:23:18 PM.
would like to acknowledge Prof. Shigenori Kuga, Graduate School
of Agricultural and Life Sciences, The University of Tokyo, Japan,
for valuable suggestions and revision of the manuscript.
References
1 S. Chu and A. Majumdar, Nature, 2012, 488, 294–303.
2 B. Dunn, H. Kamath and J.-M. Tarascon, Science, 2011, 334,
928–935.
3 L. Ji, Z. Lin, M. Alcoutlabi and X. Zhang, Energy Environ.
Sci., 2011, 4, 2682–2699.
4 N.-S. Choi, Z. Chen, S. A. Freunberger, X. Ji, Y.-K. Sun,
K. Amine, G. Yushin, L. F. Nazar, J. Cho and P. G. Bruce,
Angew. Chem., Int. Ed., 2012, 51, 9994–10024.
5 K. Xu, Chem. Rev., 2004, 104, 4303–4417.
6 Y. Gogotsi, ACS Nano, 2014, 8, 5369–5371.
7 V. Palomares, P. Serras, I. Villaluenga, K. B. Hueso,
J. Carretero-Gonzalez and T. Rojo, Energy Environ. Sci.,
2012, 5, 5884–5901.
8 V. Palomares, M. Casas-Cabanas, E. Castillo-Martinez, M. H.
Han and T. Rojo, Energy Environ. Sci., 2013, 6, 2312–2337.
9 H.-J. Peng, J.-Q. Huang, X.-B. Cheng and Q. Zhang, Adv.
Energy Mater., 2017, 1700260.
10 R. Fang, S. Zhao, Z. Sun, D.-W. Wang, H.-M. Cheng and
F. Li, Adv. Mater., 2017, 1606823.
11 D. Larcher and J. M. Tarascon, Nat. Chem., 2015, 7, 19–29.
12 Z. Yang, J. Zhang, M. C. W. Kintner-Meyer, X. Lu, D. Choi,
J. P. Lemmon and J. Liu, Chem. Rev., 2011, 111, 3577–3613.
13 R. C. Armstrong, C. Wolfram, K. P. de Jong, R. Gross,
N. S. Lewis, B. Boardman, A. J. Ragauskas, K. Ehrhardt-
Martinez, G. Crabtree and M. V. Ramana, Nat. Energy,
2016, 1, 15020.
14 A. S. Arico, P. Bruce, B. Scrosati, J. M. Tarascon and W. Van
Schalkwijk, Nat. Mater., 2005, 4, 366–377.
15 P. Simon and Y. Gogotsi, Nat. Mater., 2008, 7, 845–854.
16 S. Dutta, J. Kim, Y. Ide, J. H. Kim, M. S. A. Hossain,
Y. Bando, Y. Yamauchi and K. C. W. Wu, Mater. Horiz.,
2017, 4, 522–545.
17 S. Ummartyotin and H. Manuspiya, Renewable Sustainable
Energy Rev., 2015, 50, 204–213.
18 L. Jabbour, R. Bongiovanni, D. Chaussy, C. Gerbaldi and
D. Beneventi, Cellulose, 2013, 20, 1523–1545.
19 Z. Wang, P. Tammela, M. Stromme and L. Nyholm, Adv.
Energy Mater., 2017, 7, 1700130.
20 M. M. Perez-Madrigal, M. G. Edo and C. Aleman, Green
Chem., 2016, 18, 5930–5956.
21 G. Zheng, Y. Cui, E. Karabulut, L. Wagberg, H. Zhu and
L. Hu, MRS Bull., 2013, 38, 320–325.
2868 | Chem. Soc. Rev., 2018, 47, 2837--2872
View Article Online
Chem Soc Rev
22 L. Hu and Y. Cui, Energy Environ. Sci., 2012, 5, 6423–6435.
23 L. Nyholm, G. Nystrom, A. Mihranyan and M. Stromme,
Adv. Mater., 2011, 23, 3751–3769.
24 T. H. Nguyen, A. Fraiwan and S. Choi, Biosens. Bioelectron.,
2014, 54, 640–649.
25 F. Sharifi, S. Ghobadian, F. R. Cavalcanti and N. Hashemi,
Renewable Sustainable Energy Rev., 2015, 52, 1453–1472.
26 J.-H. Kim, B. S. Shim, H. S. Kim, Y.-J. Lee, S.-K. Min,
D. Jang, Z. Abas and J. Kim, International Journal of Preci-
sion Engineering and Manufacturing-Green Technology, 2015,
2, 197–213.
27 Y.-Z. Zhang, Y. Wang, T. Cheng, W.-Y. Lai, H. Pang and
W. Huang, Chem. Soc. Rev., 2015, 44, 5181–5199.
28 B. Yao, J. Zhang, T. Kou, Y. Song, T. Liu and Y. Li, Adv. Sci.,
2017, 4, 1700107.
29 D. Klemm, B. Heublein, H. P. Fink and A. Bohn, Angew.
Chem., Int. Ed., 2005, 44, 3358–3393.
30 M. Balat and G. Ayar, Energy Sources, 2005, 27, 931–940.
31 R. J. Moon, A. Martini, J. Nairn, J. Simonsen and
J. Youngblood, Chem. Soc. Rev., 2011, 40, 3941–3994.
32 J. R. Capadona, K. Shanmuganathan, D. J. Tyler, S. J. Rowan
and C. Weder, Science, 2008, 319, 1370–1374.
33 J. R. Capadona, O. Van Den Berg, L. A. Capadona,
M. Schroeter, S. J. Rowan, D. J. Tyler and C. Weder, Nat.
Nanotechnol., 2007, 2, 765–769.
34 K. E. Shopsowitz, H. Qi, W. Y. Hamad and M. J. MacLachlan,
Nature, 2010, 468, 422–425.
35 R. T. Olsson, M. A. S. A. Samir, G. Salazar-Alvarez, L. Belova,
V. Strom, L. A. Berglund, O. Ikkala, J. Nogues and U. W. Gedde,
Nat. Nanotechnol., 2010, 5, 584–588.
36 B. Wicklein, A. Kocjan, G. Salazar-Alvarez, F. Carosio,
G. Camino, M. Antonietti and L. Bergstrom, Nat. Nanotechnol.,
2015, 10, 277–283.
37 S. J. Eichhorn, Soft Matter, 2011, 7, 303–315.
38 J. P. F. Lagerwall, C. Schutz, M. Salajkova, J. Noh, J. H. Park,
G. Scalia and L. Bergstrom, NPG Asia Mater., 2014, 6, e80.
39 Y. Habibi, L. A. Lucia and O. J. Rojas, Chem. Rev., 2010,
110, 3479–3500.
40 Y. Habibi, Chem. Soc. Rev., 2014, 43, 1519–1542.
41 B. L. Peng, N. Dhar, H. L. Liu and K. C. Tam, Can. J. Chem.
Eng., 2011, 89, 1191–1206.
42 N. Lavoine, I. Desloges, A. Dufresne and J. Bras, Carbohydr.
Polym., 2012, 90, 735–764.
43 I. Siro and D. Plackett, Cellulose, 2010, 17, 459–494.
44 D. Klemm, F. Kramer, S. Moritz, T. Lindstrom, M. Ankerfors,
D. Gray and A. Dorris, Angew. Chem., Int. Ed., 2011, 50,
5438–5466.
45 S. Kalia, S. Boufi, A. Celli and S. Kango, Colloid Polym. Sci.,
2014, 292, 5–31.
46 W. Hamad, Can. J. Chem. Eng., 2006, 84, 513–519.
47 S. J. Eichhorn, A. Dufresne, M. Aranguren, N. E. Marcovich,
J. R. Capadona, S. J. Rowan, C. Weder, W. Thielemans,
M. Roman, S. Renneckar, W. Gindl, S. Veigel, J. Keckes,
H. Yano, K. Abe, M. Nogi, A. N. Nakagaito, A. Mangalam,
J. Simonsen, A. S. Benight, A. Bismarck, L. A. Berglund and
T. Peijs, J. Mater. Sci., 2010, 45, 1–33.
This journal is © The Royal Society of Chemistry 2018

Chem Soc Rev
48 M. A. S. Azizi Samir, F. Alloin and A. Dufresne, Biomacro-
molecules, 2005, 6, 612–626.
49 S. Eyley and W. Thielemans, Nanoscale, 2014, 6, 7764–7779.
50 A. Isogai, J. Wood Sci., 2013, 59, 449–459.
51 A. Isogai, T. Saito and H. Fukuzumi, Nanoscale, 2011, 3,
71–85.
52 A. Dufresne, Mater. Today, 2013, 16, 220–227.
53 H. Yano, J. Sugiyama, A. N. Nakagaito, M. Nogi,
Published on 21 March 2018. Downloaded by Instituto Politecnico Nacional on 10/25/2019 9:23:18 PM.
T. Matsuura, M. Hikita and K. Handa, Adv. Mater., 2005,
17, 153–155.
54 M. Nogi, S. Iwamoto, A. N. Nakagaito and H. Yano, Adv.
Mater., 2009, 21, 1595–1598.
55 M. Nogi and H. Yano, Adv. Mater., 2008, 20, 1849–1852.
56 A. J. Svagan, M. A. S. A. Samir and L. A. Berglund, Adv.
Mater., 2008, 20, 1263–1269.
57 P. Laaksonen, A. Walther, J.-M. Malho, M. Kainlauri,
O. Ikkala and M. B. Linder, Angew. Chem., Int. Ed., 2011,
50, 8688–8691.
58 J. T. Korhonen, P. Hiekkataipale, J. Malm, M. Karppinen,
O. Ikkala and R. H. A. Ras, ACS Nano, 2011, 5, 1967–1974.
59 S. Rajala, T. Siponkoski, E. Sarlin, M. Mettänen, M. Vuoriluoto,
A. Pammo, J. Juuti, O. J. Rojas, S. Franssila and S. Tuukkanen,
ACS Appl. Mater. Interfaces, 2016, 8, 15607–15614.
60 R. Mangayil, S. Rajala, A. Pammo, E. Sarlin, J. Luo,
V. Santala, M. Karp and S. Tuukkanen, ACS Appl. Mater.
Interfaces, 2017, 9, 19048–19056.
61 C. Yao, A. Hernandez, Y. Yu, Z. Cai and X. Wang, Nano
Energy, 2016, 30, 103–108.
62 B. Chen, N. Yang, Q. Jiang, W. Chen and Y. Yang, Nano
Energy, 2018, 44, 468–475.
63 I. Sakurada, Y. Nukushina and T. Ito, J. Polym. Sci., 1962,
57, 651–660.
64 T. C. Nirmale, I. Karbhal, R. S. Kalubarme, M. V. Shelke,
A. J. Varma and B. B. Kale, ACS Appl. Mater. Interfaces, 2017,
9, 34773–34782.
65 J. Wan, J. Zhang, J. Yu and J. Zhang, ACS Appl. Mater.
Interfaces, 2017, 9, 24591–24599.
66 L. Deng, R. J. Young, I. A. Kinloch, A. M. Abdelkader,
S. M. Holmes, D. A. De Haro-Del Rio and S. J. Eichhorn,
ACS Appl. Mater. Interfaces, 2013, 5, 9983–9990.
67 R. J. White, N. Brun, V. L. Budarin, J. H. Clark and M.-M.
Titirici, ChemSusChem, 2014, 7, 670–689.
68 L. Zhang, Z. Liu, G. Cui and L. Chen, Prog. Polym. Sci.,
2015, 43, 136–164.
69 M.-M. Titirici, R. J. White, N. Brun, V. L. Budarin, D. S. Su,
F. del Monte, J. H. Clark and M. J. MacLachlan, Chem. Soc.
Rev., 2015, 44, 250–290.
70 H. Zhu, W. Luo, P. N. Ciesielski, Z. Fang, J. Y. Zhu,
G. Henriksson, M. E. Himmel and L. Hu, Chem. Rev.,
2016, 116, 9305–9374.
71 T. C. Nirmale, B. B. Kale and A. J. Varma, Int. J. Biol.
Macromol., 2017, 103, 1032–1043.
72 L.-F. Chen, Y. Feng, H.-W. Liang, Z.-Y. Wu and S.-H. Yu,
Adv. Energy Mater., 2017, 7, 1700826.
73 Z.-Y. Wu, H.-W. Liang, L.-F. Chen, B.-C. Hu and S.-H. Yu,
Acc. Chem. Res., 2016, 49, 96–105.
This journal is © The Royal Society of Chemistry 2018
View Article Online
Review Article
74 F. Hoeng, A. Denneulin and J. Bras, Nanoscale, 2016, 8,
13131–13154.
75 X. Du, Z. Zhang, W. Liu and Y. Deng, Nano Energy, 2017,
35, 299–320.
76 X. Wang, C. Yao, F. Wang and Z. Li, Small, 2017, 1702240.
77 K. Uetani and H. Yano, Biomacromolecules, 2011, 12,
348–353.
78 U. G. K. Wegst, H. Bai, E. Saiz, A. P. Tomsia and
R. O. Ritchie, Nat. Mater., 2015, 14, 23–36.
79 Y. Sun, J. Qi, G. Yang, J. Pang and F. Du, Sci. Silvae Sin.,
2012, 48, 180–186.
80 K. Abe and H. Yano, Cellulose, 2010, 17, 271–277.
81 W. Chen, K. Abe, K. Uetani, H. Yu, Y. Liu and H. Yano,
Cellulose, 2014, 21, 1517–1528.
82 K. Abe, S. Iwamoto and H. Yano, Biomacromolecules, 2007,
8, 3276–3278.
83 K. Abe and H. Yano, Cellulose, 2009, 16, 1017–1023.
84 N. Terashima, K. Kitano, M. Kojima, M. Yoshida,
H. Yamamoto and U. Westermark, J. Wood Sci., 2009, 55,
409–416.
85 C. Somerville, S. Bauer, G. Brininstool, M. Facette,
T. Hamann, J. Milne, E. Osborne, A. Paredez, S. Persson,
T. Raab, S. Vorwerk and H. Youngs, Science, 2004, 306,
2206–2211.
86 W. Chen, Q. Li, Y. Wang, X. Yi, J. Zeng, H. Yu, Y. Liu and
J. Li, ChemSusChem, 2014, 7, 154–161.
87 M. Pääkkö, M. Ankerfors, H. Kosonen, A. Nykänen, S. Ahola,
M. Österberg, J. Ruokolainen, J. Laine, P. T. Larsson,
O. Ikkala and T. Lindström, Biomacromolecules, 2007, 8,
1934–1941.
88 T. Saito, S. Kimura, Y. Nishiyama and A. Isogai, Biomacro-
molecules, 2007, 8, 2485–2491.
89 L. Wagberg, G. Decher, M. Norgren, T. Lindstroem,
M. Ankerfors and K. Axnaes, Langmuir, 2008, 24, 784–795.
90 S. Elazzouzi-Hafraoui, Y. Nishiyama, J.-L. Putaux, L. Heux,
F. Dubreuil and C. Rochas, Biomacromolecules, 2008, 9, 57–65.
91 S. Ifuku, M. Nogi, K. Abe, K. Handa, F. Nakatsubo and
H. Yano, Biomacromolecules, 2007, 8, 1973–1978.
92 P. R. Sharma and A. J. Varma, Chem. Commun., 2013, 49,
8818–8820.
93 P. R. Sharma and A. J. Varma, Carbohydr. Polym., 2014, 114,
339–343.
94 S. Hornig and T. Heinze, Biomacromolecules, 2008, 9,
1487–1492.
95 M. N. Nosar, M. Salehi, S. Ghorbani, S. P. Beiranvand,
A. Goodarzi and M. Azami, Cellulose, 2016, 23, 3239–3248.
96 O. J. Rojas, G. A. Montero and Y. Habibi, J. Appl. Polym. Sci.,
2009, 113, 927–935.
97 A. F. Turbak, F. W. Snyder and K. R. Sandberg, Microfibrillated
cellulose, a new cellulose product: properties, uses, and commer-
cial potential, ITT Rayonier Inc., Shelton, WA, 1983.
98 F. W. Herrick, R. L. Casebier, J. K. Hamilton and
K. R. Sandberg, Microfibrillated cellulose: morphology and
accessibility, ITT Rayonier Inc., Shelton, WA, 1983.
99 A. N. Nakagaito and H. Yano, Appl. Phys. A: Mater. Sci.
Process., 2005, 80, 155–159.
Chem. Soc. Rev., 2018, 47, 2837--2872 | 2869

Review Article
100 S. Iwamoto, A. N. Nakagaito and H. Yano, Appl. Phys. A:
Mater. Sci. Process., 2007, 89, 461–466.
101 S. Iwamoto, A. N. Nakagaito, H. Yano and M. Nogi, Appl.
Phys. A: Mater. Sci. Process., 2005, 81, 1109–1112.
102 H.-P. Zhao, X.-Q. Feng and H. Gao, Appl. Phys. Lett., 2007,
90, 073112.
103 Q. Cheng, S. Wang and T. G. Rials, Composites, Part A,
2009, 40, 218–224.
Published on 21 March 2018. Downloaded by Instituto Politecnico Nacional on 10/25/2019 9:23:18 PM.
104 W. Chen, H. Yu, Y. Liu, Y. Hai, M. Zhang and P. Chen,
Cellulose, 2011, 18, 433–442.
105 W. Chen, Q. Li, J. Cao, Y. Liu, J. Li, J. Zhang, S. Luo and
H. Yu, Carbohydr. Polym., 2015, 117, 950–956.
106 T. Saito, Y. Nishiyama, J.-L. Putaux, M. Vignon and
A. Isogai, Biomacromolecules, 2006, 7, 1687–1691.
107 H. Fukuzumi, T. Saito, Y. Okita and A. Isogai, Polym.
Degrad. Stab., 2010, 95, 1502–1508.
108 H. Fukuzumi, T. Saito, T. Wata, Y. Kumamoto and
A. Isogai, Biomacromolecules, 2009, 10, 162–165.
109 B. G. Rånby, Discuss. Faraday Soc., 1951, 11, 158–164.
110 R. H. Marchessault, F. F. Morehead and N. M. Walter,
Nature, 1959, 184, 632–633.
111 M. Iguchi, S. Yamanaka and A. Budhiono, J. Mater. Sci.,
2000, 35, 261–270.
112 H. El-Saied, A. H. Basta and R. H. Gobran, Polym.-Plast.
Technol. Eng., 2004, 43, 797–820.
113 P. Gatenholm and D. Klemm, MRS Bull., 2010, 35, 208–213.
114 F. G. Torres, S. Commeaux and O. P. Troncoso, J. Funct.
Biomater., 2012, 3, 864–878.
115 M. Roman and W. T. Winter, Biomacromolecules, 2004, 5,
1671–1677.
116 Y. Wang, Y. Song and Y. Xia, Chem. Soc. Rev., 2016, 45,
5925–5950.
117 J. Yan, Q. Wang, T. Wei and Z. Fan, Adv. Energy Mater.,
2014, 4, 1300816.
118 F. Wang, X. Wu, X. Yuan, Z. Liu, Y. Zhang, L. Fu, Y. Zhu,
Q. Zhou, Y. Wu and W. Huang, Chem. Soc. Rev., 2017, 46,
6816–6854.
119 K. Torvinen, S. Lehtimäki, J. T. Keränen, J. Sievänen,
J. Vartiainen, E. Hellén, D. Lupo and S. Tuukkanen,
Electron. Mater. Lett., 2015, 11, 1040–1047.
120 S. Tuukkanen, S. Lehtimäki, F. Jahangir, A. P. Eskelinen,
D. Lupo and S. Franssila, Proceedings of the 5th Electronics
System-integration Technology Conference (ESTC), 2014.
121 Q. Niu, K. Gao and Z. Shao, Nanoscale, 2014, 6, 4083–4088.
122 K. Gao, Z. Shao, X. Wang, Y. Zhang, W. Wang and F. Wang,
RSC Adv., 2013, 3, 15058–15064.
123 Y. J. Kang, S.-J. Chun, S.-S. Lee, B.-Y. Kim, J. H. Kim, H. Chung,
S.-Y. Lee and W. Kim, ACS Nano, 2012, 6, 6400–6406.
124 K. Gao, Z. Shao, J. Li, X. Wang, X. Peng, W. Wang and
F. Wang, J. Mater. Chem. A, 2013, 1, 63–67.
125 Q. Zheng, Z. Cai, Z. Ma and S. Gong, ACS Appl. Mater.
Interfaces, 2015, 7, 3263–3271.
126 Z. Wang, D. O. Carlsson, P. Tammela, K. Hua, P. Zhang,
L. Nyholm and M. Strømme, ACS Nano, 2015, 9, 7563–7571.
127 Z. Wang, P. Tammela, J. Huo, P. Zhang, M. Stromme and
L. Nyholm, J. Mater. Chem. A, 2016, 4, 1714–1722.
2870 | Chem. Soc. Rev., 2018, 47, 2837--2872
View Article Online
Chem Soc Rev
128 S. Li, D. Huang, J. Yang, B. Zhang, X. Zhang, G. Yang,
M. Wang and Y. Shen, Nano Energy, 2014, 9, 309–317.
129 R. Liu, L. Ma, S. Huang, J. Mei, J. Xu and G. Yuan, RSC Adv.,
2016, 6, 107426–107432.
130 D. Shan, J. Yang, W. Liu, J. Yan and Z. Fan, J. Mater. Chem.
A, 2016, 4, 13589–13602.
131 Y. Jiang, J. Yan, X. Wu, D. Shan, Q. Zhou, L. Jiang, D. Yang
and Z. Fan, J. Power Sources, 2016, 307, 190–198.
132 L.-F. Chen, Z.-H. Huang, H.-W. Liang, W.-T. Yao, Z.-Y. Yu
and S.-H. Yu, Energy Environ. Sci., 2013, 6, 3331–3338.
133 L.-F. Chen, Z.-H. Huang, C. H.-W. Liang, H.-L. Gao and
S.-H. Yu, Adv. Funct. Mater., 2014, 24, 5104–5111.
134 L. Ma, R. Liu, H. Niu, L. Xing, L. Liu and Y. Huang, ACS
Appl. Mater. Interfaces, 2016, 8, 33608–33618.
135 L.-F. Chen, Z.-H. Huang, H.-W. Liang, Q.-F. Guan and
S.-H. Yu, Adv. Mater., 2013, 25, 4746–4752.
136 C. Long, D. Qi, T. Wei, J. Yan, L. Jiang and Z. Fan, Adv.
Funct. Mater., 2014, 24, 3953–3961.
137 F. Lai, Y.-E. Miao, L. Zuo, H. Lu, Y. Huang and T. Liu,
Small, 2016, 12, 3235–3244.
138 W. Yu, W. Lin, X. Shao, Z. Hu, R. Li and D. Yuan, J. Power
Sources, 2014, 272, 137–143.
139 L. Zuo, W. Fan, Y. Zhang, Y. Huang, W. Gao and T. Liu,
Nanoscale, 2017, 9, 4445–4455.
140 Q. Zheng, A. Kvit, Z. Cai, Z. Ma and S. Gong, J. Mater. Chem.
A, 2017, 5, 12528–12541.
141 G. Nyström, A. Marais, E. Karabulut, L. Wågberg, Y. Cui
and M. M. Hamedi, Nat. Commun., 2015, 6, 7259.
142 Y. Liu, J. Zhou, E. Zhu, J. Tang, X. Liu and W. Tang,
J. Mater. Chem. C, 2015, 3, 1011–1017.
143 K.-H. Choi, J. Yoo, C. K. Lee and S.-Y. Lee, Energy Environ.
Sci., 2016, 9, 2812–2821.
144 M. Hamedi, E. Karabulut, A. Marais, A. Herland,
G. Nyström and L. Wågberg, Angew. Chem., Int. Ed., 2013,
52, 12038–12042.
145 H. Wang, L. Bian, P. Zhou, J. Tang and W. Tang, J. Mater.
Chem. A, 2013, 1, 578–584.
146 Z. Wang, P. Tammela, P. Zhang, J. Huo, F. Ericson,
M. Strømme and L. Nyholm, Nanoscale, 2014, 6, 13068–13075.
147 Z. Wang, P. Tammela, P. Zhang, M. Strømme and
L. Nyholm, J. Mater. Chem. A, 2014, 2, 7711–7716.
148 Z. Wang, P. Tammela, P. Zhang, M. Strømme and
L. Nyholm, J. Mater. Chem. A, 2014, 2, 16761–16769.
149 D. O. Carlsson, G. Nyström, Q. Zhou, L. A. Berglund,
L. Nyholm and M. Strømme, J. Mater. Chem., 2012, 22,
19014–19024.
150 A. Razaq, L. Nyholm, M. Sjödin, M. Strømme and
A. Mihranyan, Adv. Energy Mater., 2012, 2, 445–454.
151 H. Wang, E. Zhu, J. Yang, P. Zhou, D. Sun and W. Tang,
J. Phys. Chem. C, 2012, 116, 13013–13019.
152 F. Wang, H.-J. Kim, S. Park, C.-D. Kee, S.-J. Kim and
I.-K. Oh, Compos. Sci. Technol., 2016, 128, 33–40.
153 J. Xu, L. Zhu, Z. Bai, G. Liang, L. Liu, D. Fang and W. Xu,
Org. Electron., 2013, 14, 3331–3338.
154 S. Peng, Q. Xu, L. Fan, C. Wei, H. Bao, W. Xu and J. Xu,
Synth. Met., 2016, 222, 285–292.
This journal is © The Royal Society of Chemistry 2018

Chem Soc Rev
155 S. Peng, L. Fan, C. Wei, H. Bao, H. Zhang, W. Xu and J. Xu,
Cellulose, 2016, 23, 2639–2651.
156 S. Peng, L. Fan, C. Wei, X. Liu, H. Zhang, W. Xu and J. Xu,
Carbohydr. Polym., 2017, 157, 344–352.
157 X. Zhang, Z. Lin, B. Chen, W. Zhang, S. Sharma, W. Gu and
Y. Deng, J. Power Sources, 2014, 246, 283–289.
158 C. Yang, C. Chen, Y. Pan, S. Li, F. Wang, J. Li, N. Li, X. Li,
Y. Zhang and D. Li, Electrochim. Acta, 2015, 182, 264–271.
Published on 21 March 2018. Downloaded by Instituto Politecnico Nacional on 10/25/2019 9:23:18 PM.
159 N. Li, X. Li, C. Yang, F. Wang, J. Li, H. Wang, C. Chen,
S. Liu, Y. Pan and D. Li, RSC Adv., 2016, 6, 86744–86751.
160 L. Ma, R. Liu, H. Niu, F. Wang, L. Liu and Y. Huang,
Electrochim. Acta, 2016, 222, 429–437.
161 Z. Wang, P. Tammela, M. Strømme and L. Nyholm,
Nanoscale, 2015, 7, 3418–3423.
162 S. Li, D. Huang, B. Zhang, X. Xu, M. Wang, G. Yang and
Y. Shen, Adv. Energy Mater., 2014, 4, 1301655.
163 S. Y. Liew, D. A. Walsh and W. Thielemans, RSC Adv., 2013,
3, 9158–9162.
164 X. Wu, V. L. Chabot, B. K. Kim, A. Yu, R. M. Berry and
K. C. Tam, Electrochim. Acta, 2014, 138, 139–147.
165 X. Wu, J. Tang, Y. Duan, A. Yu, R. M. Berry and K. C. Tam,
J. Mater. Chem. A, 2014, 2, 19268–19274.
166 X. Yang, K. Shi, I. Zhitomirsky and E. D. Cranston, Adv.
Mater., 2015, 27, 6104–6109.
167 K. Shi, X. Yang, E. D. Cranston and I. Zhitomirsky, Adv.
Funct. Mater., 2016, 26, 6437–6445.
168 H.-W. Liang, Q.-F. Guan, Z. Zhu, L.-T. Song, H.-B. Yao,
X. Lei and S.-H. Yu, NPG Asia Mater., 2012, 4, e19.
169 W. Chen, Q. Zhang, K. Uetani, Q. Li, P. Lu, J. Cao, Q. Wang,
Y. Liu, J. Li, Z. Quan, Y. Zhang, S. Wang, Z. Meng and
H. Yu, Adv. Mater. Interfaces, 2016, 3, 1600004.
170 J. Virtanen, A. Pammo, J. Keskinen, E. Sarlin and
S. Tuukkanen, Cellulose, 2017, 24, 3387–3397.
171 X. Wang, D. Kong, B. Wang, Y. Song and L. Zhi, Sci. China:
Chem., 2016, 59, 713–718.
172 Z.-Y. Wu, H.-W. Liang, C. Li, B.-C. Hu, X.-X. Xu, Q. Wang,
J.-F. Chen and S.-H. Yu, Nano Res., 2014, 7, 1861–1872.
173 X. Wu, Z. Shi, R. Tjandra, A. J. Cousins, S. Sy, A. Yu, R. M. Berry
and K. C. Tam, J. Mater. Chem. A, 2015, 3, 23768–23777.
174 M. Giese, L. K. Blusch, M. K. Khan and M. J. MacLachlan,
Angew. Chem., Int. Ed., 2015, 54, 2888–2910.
175 J. A. Kelly, M. Giese, K. E. Shopsowitz, W. Y. Hamad and
M. J. MacLachlan, Acc. Chem. Res., 2014, 47, 1088–1096.
176 K. E. Shopsowitz, W. Y. Hamad and M. J. MacLachlan,
Angew. Chem., Int. Ed., 2011, 50, 10991–10995.
177 Z. Li, K. Ahadi, K. Jiang, B. Ahvazi, P. Li, A. O. Anyia,
K. Cadien and T. Thundat, Nano Res., 2017, 10, 1847–1860.
178 Z. Li, J. Liu, K. Jiang and T. Thundat, Nano Energy, 2016,
25, 161–169.
179 X. Xu, J. Zhou, D. H. Nagaraju, L. Jiang, V. R. Marinov,
G. Lubineau, H. N. Alshareef and M. Oh, Adv. Funct. Mater.,
2015, 25, 3193–3202.
180 H. Li, Z. Wang, L. Chen and X. Huang, Adv. Mater., 2009,
21, 4593–4607.
181 V. Etacheri, R. Marom, R. Elazari, G. Salitra and D. Aurbach,
Energy Environ. Sci., 2011, 4, 3243–3262.
This journal is © The Royal Society of Chemistry 2018
View Article Online
Review Article
182 W. Li, B. Song and A. Manthiram, Chem. Soc. Rev., 2017, 46,
3006–3059.
183 Y. Tang, Y. Zhang, W. Li, B. Ma and X. Chen, Chem. Soc.
Rev., 2015, 44, 5926–5940.
184 S. Leijonmarck, A. Cornell, G. Lindbergh and L. Wagberg,
Nano Energy, 2013, 2, 794–800.
185 Z. Wang, C. Xu, P. Tammela, J. Huo, M. Stromme,
K. Edstrom, T. Gustafsson and L. Nyholm, J. Mater.
Chem. A, 2015, 3, 14109–14115.
186 L. Hu, N. Liu, M. Eskilsson, G. Zheng, J. McDonough,
L. Wagberg and Y. Cui, Nano Energy, 2013, 2, 138–145.
187 S. Leijonmarck, A. Cornell, G. Lindbergh and L. Wagberg,
J. Mater. Chem. A, 2013, 1, 4671–4677.
188 L. Wang, C. Schutz, G. Salazar-Alvarez and M.-M. Titirici,
RSC Adv., 2014, 4, 17549–17554.
189 W. Wang, Y. Sun, B. Liu, S. Wang and M. Cao, Carbon,
2015, 91, 56–65.
190 Y. Li, H. Zhu, F. Shen, J. Wan, X. Han, J. Dai, H. Dai and
L. Hu, Adv. Funct. Mater., 2014, 24, 7366–7372.
191 B. Wang, X. Li, B. Luo, J. Yang, X. Wang, Q. Song, S. Chen
and L. Zhi, Small, 2013, 9, 2399–2404.
192 Y. Wan, Z. Yang, G. Xiong and H. Luo, J. Mater. Chem. A,
2015, 3, 15386–15393.
193 F. Zhang, Y. Tang, Y. Yang, X. Zhang and C.-S. Lee,
Electrochim. Acta, 2016, 211, 404–410.
194 S. Cao, X. Feng, Y. Song, X. Xue, H. Liu, M. Miao, J. Fang and
L. Shi, ACS Appl. Mater. Interfaces, 2015, 7, 10695–10701.
195 H. Lu, J. Hagberg, G. Lindbergh and A. Cornell, Nano
Energy, 2017, 39, 140–150.
196 S. Cao, X. Feng, Y. Song, H. Liu, M. Miao, J. Fang and
L. Shi, ACS Appl. Mater. Interfaces, 2016, 8, 1073–1079.
197 Y. Huang, Z. Lin, M. Zheng, T. Wang, J. Yang, F. Yuan,
X. Lu, L. Liu and D. Sun, J. Power Sources, 2016, 307,
649–656.
198 H. Lee, M. Yanilmaz, O. Toprakci, K. Fu and X. Zhang,
Energy Environ. Sci., 2014, 7, 3857–3886.
199 S.-J. Chun, E.-S. Choi, E.-H. Lee, J. H. Kim, S.-Y. Lee and
S.-Y. Lee, J. Mater. Chem., 2012, 22, 16618–16626.
200 R. Pan, O. Cheung, Z. Wang, P. Tammela, J. Huo, J. Lindh,
K. Edstrom, M. Stromme and L. Nyholm, J. Power Sources,
2016, 321, 185–192.
201 J.-H. Kim, J.-H. Kim, E.-S. Choi, H. K. Yu, J. H. Kim, Q. Wu,
S.-J. Chun, S.-Y. Lee and S.-Y. Lee, J. Power Sources, 2013,
242, 533–540.
202 Z. Wang, R. Pan, C. Ruan, K. Edström, M. Strømme and
L. Nyholm, Adv. Sci., 2017, 1700663.
203 K.-H. Choi, S.-J. Cho, S.-J. Chun, J. T. Yoo, C. K. Lee,
W. Kim, Q. Wu, S.-B. Park, D.-H. Choi, S.-Y. Lee and
S.-Y. Lee, Nano Lett., 2014, 14, 5677–5686.
204 S.-J. Cho, K.-H. Choi, J.-T. Yoo, J.-H. Kim, Y.-H. Lee,
S.-J. Chun, S.-B. Park, D.-H. Choi, Q. Wu, S.-Y. Lee and
S.-Y. Lee, Adv. Funct. Mater., 2015, 25, 6029–6040.
205 J.-H. Kim, M. Gu, D. H. Lee, J.-H. Kim, Y.-S. Oh, S. H. Min,
B.-S. Kim and S.-Y. Lee, Nano Lett., 2016, 16, 5533–5541.
206 L. Mai, X. Tian, X. Xu, L. Chang and L. Xu, Chem. Rev.,
2014, 114, 11828–11862.
Chem. Soc. Rev., 2018, 47, 2837--2872 | 2871

Review Article
207 H.-J. Peng, J.-Q. Huang and Q. Zhang, Chem. Soc. Rev.,
2017, 46, 5237–5288.
208 Z. W. Seh, Y. Sun, Q. Zhang and Y. Cui, Chem. Soc. Rev.,
2016, 45, 5605–5634.
209 Y.-X. Yin, S. Xin, Y.-G. Guo and L.-J. Wan, Angew. Chem.,
Int. Ed., 2013, 52, 13186–13200.
210 A. Manthiram, Y. Fu, S.-H. Chung, C. Zu and Y.-S. Su,
Chem. Rev., 2014, 114, 11751–11787.
Published on 21 March 2018. Downloaded by Instituto Politecnico Nacional on 10/25/2019 9:23:18 PM.
211 M. Yu, J. Ma, M. Xie, H. Song, F. Tian, S. Xu, Y. Zhou, B. Li,
D. Wu, H. Qiu and R. Wang, Adv. Energy Mater., 2017,
7, 1602347.
212 Y. Huang, M. Zheng, Z. Lin, B. Zhao, S. Zhang, J. Yang,
C. Zhu, H. Zhang, D. Sun and Y. Shi, J. Mater. Chem. A,
2015, 3, 10910–10918.
213 Y. Quan, D. Han, Y. Feng, S. Wang, M. Xiao and Y. Meng,
Int. J. Electrochem. Sci., 2017, 12, 5984–5997.
214 S. Li, T. Mou, G. Ren, J. Warzywoda, Z. Wei, B. Wang and
Z. Fan, J. Mater. Chem. A, 2017, 5, 1650–1657.
215 Q. Pang, J. Tang, H. Huang, X. Liang, C. Hart, K. C. Tam
and L. F. Nazar, Adv. Mater., 2015, 27, 6021–6028.
216 F. Li, G. Wang, P. Wang, J. Yang, K. Zhang, Y. Liu and
Y. Lai, J. Electroanal. Chem., 2017, 788, 150–155.
217 J. R. Nair, F. Bella, N. Angulakshmi, A. M. Stephan and
C. Gerbaldi, Energy Storage Materials, 2016, 3, 69–76.
218 S.-W. Kim, D.-H. Seo, X. Ma, G. Ceder and K. Kang,
Adv. Energy Mater., 2012, 2, 710–721.
219 H. Che, S. Chen, Y. Xie, H. Wang, K. Amine, X.-Z. Liao and
Z.-F. Ma, Energy Environ. Sci., 2017, 10, 1075–1101.
2872 | Chem. Soc. Rev., 2018, 47, 2837--2872
View Article Online
Chem Soc Rev
220 W. Luo, F. Shen, C. Bommier, H. Zhu, X. Ji and L. Hu, Acc.
Chem. Res., 2016, 49, 231–240.
221 H. Kim, H. Kim, Z. Ding, M. H. Lee, K. Lim, G. Yoon and
K. Kang, Adv. Energy Mater., 2016, 6, 1600943.
222 H. Pan, Y.-S. Hu and L. Chen, Energy Environ. Sci., 2013, 6,
2338–2360.
223 J.-Y. Hwang, S.-T. Myung and Y.-K. Sun, Chem. Soc. Rev.,
2017, 46, 3529–3614.
224 Y. Li, H. Zhu, F. Shen, J. Wan, S. Lacey, Z. Fang, H. Dai and
L. Hu, Nano Energy, 2015, 13, 346–354.
225 W. Luo, J. Schardt, C. Bommier, B. Wang, J. Razink,
J. Simonsen and X. Ji, J. Mater. Chem. A, 2013, 1,
10662–10666.
226 Z. Zhang, J. Zhang, X. Zhao and F. Yang, Carbon, 2015, 95,
552–559.
227 M. Wang, Z. Yang, W. Li, L. Gu and Y. Yu, Small, 2016, 12,
2559–2566.
228 M. Wang, Y. Yang, Z. Yang, L. Gu, Q. Chen and Y. Yu, Adv.
Sci., 2017, 4, 1600468.
229 H. Zhu, F. Shen, W. Luo, S. Zhu, M. Zhao, B. Natarajan,
J. Dai, L. Zhou, X. Ji, R. S. Yassar, T. Li and L. Hu, Nano
Energy, 2017, 33, 37–44.
230 J. O. Zoppe, N. C. Ataman, P. Mocny, J. Wang, J. Moraes
and H.-A. Klok, Chem. Rev., 2017, 117, 1105–1318.
231 H.-Y. Hsueh, C.-T. Yao and R.-M. Ho, Chem. Soc. Rev., 2015,
44, 1974–2018.
232 A. Zhang, Q. Zhang, H. Bai, L. Li and J. Li, Chem. Soc. Rev.,
2014, 43, 6938–6953.
This journal is © The Royal Society of Chemistry 2018