Wenshuai Chen

Chem Soc Rev
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Nanocellulose: a promising nanomaterial for

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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
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
Received 28th December 2017 films/aerogel as flexible substrates, and the pyrolyzation of nanocellulose to carbon materials and
DOI: 10.1039/c7cs00790f 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
rsc.li/chem-soc-rev 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: [email protected] 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 Heilongjiang, China. He received
(2013) in wood science and his BS (2000) and PhD (2005)
technology from Northeast degrees in wood science and
Forestry University, China. Now technology from Northeast Forestry
he is an associate professor at University of China. He started as
Northeast Forestry University. He an Assistant Professor at Northeast
is the winner of the Young Elite Forestry University in 2005, and was
Scientists Sponsorship Program by promoted to Associate Professor and
China Association for Science and Professor in 2007 and 2011,
Technology. His research interests respectively. His research interests
include wood physics, bionano- include wood modification, nano-
Wenshuai Chen composites, nanocellulose, aerogels, Haipeng Yu cellulose and its functional nano-
and development of natural materials, and biomass conversion
nanomaterials for energy storage and conversion as well as technologies.
water purification.
This journal is © The Royal Society of Chemistry 2018 Chem. Soc. Rev., 2018, 47, 2837--2872 | 2837
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Review Article Chem Soc Rev
(such as lithium (sodium)-ion batteries and lithium–sulfur or other plant fibers as building materials, furniture, paper,
batteries) have demonstrated great potential in powering portable clothing, and many other applications. Regardless of its source,
electronics, electric vehicles, hybrid electric vehicles, and even cellulose is a high-molecular-weight homopolymer of b-1,4-linked
huge energy-storage systems.2–10 Except for performance and anhydro-D-glucose units in which every unit is corkscrewed 1801
safety enhancements, the major remaining challenges for the with respect to its neighbors, and the repeat segment is frequently
future development of energy storage devices are the reduction of taken to be a dimer of glucose, known as cellobiose. During
both production and overall device costs, the realization of flexible biosynthesis, van der Waals forces and intermolecular hydrogen
devices, the utilization of green and abundant raw materials, bonding promote the parallel stacking of cellulose chains to
the realization of environmentally friendly processes, and the form nanosized elementary fibrils that further organize into
development of easily recyclable and up-scalable systems.11–15 larger fibrils.31 Within these nanosized cellulose fibers, there
Among numerous candidates, cellulose-derived materials have are regions in which the cellulose chains are arranged in highly
obtained increasing attention as attractive components of crystalline structures, as well as regions containing amorphous
various electrochemical energy storage devices.16–28 structures. The unique structure of these nanofibers, with
Cellulose is the most abundant renewable organic polymer advantageous mechanical properties and a low coefficient of
on earth. The world production of biomass is estimated at thermal expansion, makes them ideal building blocks for
approximately 150–200 billion metric tons a year, most of advanced functional products.32–36 Enormous efforts have been
which is cellulose.29,30 It is used in the form of wood, cotton, made to extract nanofibers from the cell walls of cellulose
Sang-Young Lee is a professor Tong Wei received her PhD in 2003

and a head in School of Energy at the Institute of Coal Chemistry,
and Chemical Engineering at Chinese Academy of Sciences. She
UNIST, Korea. He received BA in became full professor at the College
Chemical Engineering from Seoul of Material Science and Chemical
National University in 1991, MS, Engineering, Harbin engineering
and PhD in Chemical Engineering University, in 2010. Her research
from KAIST in 1993 and 1997. He interests focus on advanced nano-
served as a postdoctoral fellow at materials for energy conversion and
Max-Planck Institute for Polymer storage.
Research from 2001 to 2002.
Before joining UNIST, he worked
Sang-Young Lee at Batteries R&D, LG Chem as a Tong Wei
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 Zhuangjun Fan received his PhD in
wood science from Northeast 2003 at the Institute of Coal
Forestry University in 1987. Now, Chemistry, Chinese Academy of
he is an academician of Chinese Sciences. He became full professor
Academy of Engineering, and at the College of Material Science
professor at College of Material and Chemical Engineering in 2006,
Science and Engineering in and now he is the director of the
Northeast Forestry University. His Institute of Advanced Carbon Based
research interests include a wide Materials at Harbin Engineering
range of wood science such as University. His research interests
wood biomimetic, wood physics, focus on the design and controlled
wood chemistry, wood-based synthesis of carbon nanomaterials
Jian Li composites, and high performance Zhuangjun Fan such as carbon nanotubes and
nanocomposites from lignocellulosic graphene, and their applications
resources. in energy-related areas such as supercapacitors, Li ion batteries and
full cells.
2838 | Chem. Soc. Rev., 2018, 47, 2837--2872 This journal is © The Royal Society of Chemistry 2018
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Chem Soc Rev Review Article

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
Fig. 1 Schematic diagram showing the main topics of this review from the pore structures, which can simultaneously electrically separate
cellulose resources, nanocellulose fabrication, structural and functional the electrodes and facilitate ionic transportation.
design to the energy storage applications. (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
resources such as from higher plants, or the synthesis of nano- that can be further functionalized as high-performance carbon
fibers by bacteria, which gave birth to nanocellulose.26,31,37–52 electrodes for energy storage devices.
Interest in nanocellulose has been growing steadily and nano- (vi) Last but not the least, nanocellulose with various struc-
cellulose has been widely applied in optically transparent tures and surface chemistry properties can be developed from
materials,53–55 reinforced polymer nanocomposites,32,33 biomi- different cellulose sources through various fabrication strategies.
metic materials,56,57 templates,35,58 sensors,59,60 and energy Thus, it is possible to develop multiple kinds of materials or
harvesters.61,62 There are also much more potential application devices motioned in the above 5 points by using various types of
fields for nanocellulose such as in microfluidics channels, as nanocellulose and their hybrids as building blocks.
cell cultivation substrate, or substrate for printed electronics. Thanks to the efforts from many research groups, a series of
Among the multiple applications, the development of nano- nanocellulose-derived materials have recently been developed
cellulose for energy storage (Fig. 1) has received increasing for energy storage applications. Cellulose derivatives have also
attention because nanocellulose displays advantages based on been confirmed as good candidates for the same purpose.64–66
its intrinsic structures and properties, which can be broadly After processing the cellulose derivatives into nanoparticles,
categorized into the following six groups (Fig. 2): these novel materials that having advantages both of nano-
(i) Because nanocellulose has prospective mechanical pro- sized cellulose and new chemical functions from the deriva-
perties including a high Young’s modulus of 138 GPa63 and tives, will build up new opportunity for developing of new type
an estimated strength of 2–3 GPa, it can be utilized to develop of cellulose nanomaterial-based energy storage systems. Over
self-standing and high strength materials for electrodes and the past few years, extensive reviews that have focused on
separators. different aspects in the field of lignocellulosic materials for
(ii) Because it has reactive surfaces containing hydroxyl energy storage have been published and provide great insights
groups, it is possible and convenient for chemical modification to researchers.16,18–21,67–72 As a very promising nanomaterial,
and integration of nanocellulose with active materials. By changing nanocellulose has been included but usually just summarized
the composite strategies and turning the ratios of active materials as a part of some reviews. Recently, several reviews summarized
in the composites, the properties of the nanocellulose-based the utilization of nanocellulose and its derived materials for
composites can be tailored to enhance their electrochemical supercapacitors, LIBs and several energy conversion devices.73–76
performance for specific applications. However, till now, no reviews have specifically focused on, and
(iii) Nanocellulose fibers with a high aspect ratio, such as comprehensive summarized and comparison, the development
those extracted from higher plant or secreted by bacteria form of different types of nanocellulose for various energy storage
entangled web-like structures, can be utilized to fabricate strong systems. It is timely to have a review on this topic to summarize the
film/aerogel substrates for further development of flexible energy recent advances and, more importantly, to provide a systematic
storage devices. understanding of the merits of the use of nanocellulose and its
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derived materials for electrodes, separators, and energy storage hydrogen bonds between hydroxyl groups and oxygens of
devices. This review focuses on the recent advances on putting adjacent molecules promote parallel stacking of fully extended
nanocellulose to work for electrochemical energy storage research cellulose chains, forming elemental fibrils with cross sections
(Fig. 1). We begin with a brief introduction of the structural ranging from 2 to 50 nm. Owing to differences in biosynthetic
features of cellulose nanofibers within the cell walls of various mechanisms, the structure of elementary fibrils differs depending
kinds of cellulose resources. We then focus on a variety of on the source organism. The elementary fibrils are further
methods that have been explored to fabricate various types of assembled into larger fibrils within the cell walls. The intra- and
nanocellulose with different structures and surface chemistry interchain hydrogen bonding network makes cellulose a relatively
properties from a variety of sources. Finally, we review the recent stable polymer, and gives the cellulose fibrils high axial stiffness.31
progress in the development of nanocellulose-derived materials As the skeletal component in cellulose sources, cellulose fibrils
for energy storage applications including supercapacitors, are organized in a cellular hierarchical structure. In combination
lithium-ion batteries (LIBs), lithium–sulfur (Li–S) batteries, with the accompanying substances such as hemicellulose, lignin,
and sodium-ion batteries (NIBs). and pectin, this structure leads to extraordinary properties of
native cellulose materials.
Fig. 3 illustrates the cellulose nanofibers in the cell walls of
2. Cellulose nanofibers in the cell walls wood, bamboo, and cotton. The cellulose molecules organized
in the cell walls in the form of nanofibers have characteristic
Cellulose nanofibers are mainly synthesized by higher plants, orientations (helix angles), which vary depending on the type
but also by algae, fungi, bacteria, and an animal, tunicate. of plant sources and the cell wall layers (Fig. 3b, g and m).
During the biosynthesis, van der Waals and intermolecular 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 within the aggregates and cannot be clearly seen by the SEM
observations of the samples are usually not clear and cannot observation.84 For example, in most higher plants, the diameter
reveal the nanostructure of cellulose fibers. When chemical of single elemental fibrils is reported to be B3 nm.85 Thus, the
purification methods are used to remove the matrix from wood, uniform nanofibers of 12–20 nm within the wood chemically
such as the removal of lignin using acidified sodium chlorite and purified cellulose can be recognized as the B3 nm elemental
the removal of a large amount of hemicellulose using potassium fibril aggregates.82,83
hydroxide (Fig. 3d), the nanofiber characteristics of the cellulose
within the cell walls can be clearly revealed (Fig. 3e).82 Similar
results have also been obtained for chemically purified cellulose 3. Fabrications, structures and
fibers of bamboo (Fig. 3i–k),80 cotton,81 rice straw,83 and potato characteristics of nanocellulose
tuber,83 confirming that the higher plant cell walls are supported
by high aspect ratio cellulose nanofibers. After nanofibrillation Nanocellulose with various structures and surface chemistry pro-
through various mechanical or chemical methods, these cellulose perties can be produced from various sources through different
nanofibers are released from the cell walls, resulting in nano- nanofibrillation and synthesis methods (Table 1).77,82,86–91 On the
cellulose. It should be noted that the uniform nanofibers basis of their structures and fabrication processes, nanocellulose
observed from SEM images in Fig. 3 is elemental fibril aggre- can be classified into three main subcategories. So far, the
gates and single elemental fibrils are parallel align aggregated 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), with a high-speed blender (breaking down the fiber structures)
cellulose nanocrystal (CNC) and bacterial cellulose (BC), because combined with high-pressure homogenization (nanofibrillation).81
they are widely used in the literature. It should be noted that The resultant cotton NFC was found to have a uniform width of
except for the above mentioned nanocellulose, other shapes of approximately 10–30 nm and high aspect ratios. Therefore, it
cellulose nanoparticles can also be developed from different can be confirmed that NFC with high aspect ratio and web-like
precursors through various fabrication strategies. For example, entangled structures can be produced from any kind of higher
spherical shaped cellulose nanoparticles were developed from a plant sources.
series of cellulose derivatives,92–94 while ribbon shaped cellulose Although the above-mentioned mechanical nanofibrillation
nanofibers were produced from cellulose-based precursors methods can be used to fabricate high aspect ratio NFC, a large
through electrospinning technique.95,96 These cellulose nano- amount of nanofiber bundles are still existed.105 To further
particles also have potential to be developed for energy storage improve the nanofibrillation degree and decrease the process
applications. energy consumption, chemical modification of the surface of
cellulose pulps before nanofibrillation is effective. Isogai et al.
3.1. Nanofibrillated cellulose (NFC) pioneered the development of the TEMPO (2,2,6,6-tetramethyl-
The fabrication of NFC was developed by Turbak and his piperidine-1-oxyl radical)-mediated oxidation method to produce
coworkers at ITT Rayonier in the 1980s.97,98 NFC was prepared uniform dispersion of individualized NFC.51,88,106 Significant
by nanofibrillation of wood cellulose pulps in water using a high- amounts of C6 carboxylate groups are formed on each cellulose
pressure homogenizer. During the nanofibrillation process, nanofiber surface. Electrostatic repulsion and/or osmotic effects
cellulose slurry is pumped at high pressure through a spring- working between the anionically charged cellulose nanofibers
loaded valve assembly. The valve is opened and closed in a cause the formation of completely individualized NFC dispersed
reciprocating motion, subjecting the cellulose to a large pressure in water by a gentle mechanical disintegration treatment of TEMPO-
drop of shearing and impact forces.99 This combination of oxidized cellulose fibers. The wood TEMPO-oxidized NFC is 3–4 nm
repeated mechanical forces promotes the disintegration of in width and a few micrometers in length. However, the formation
cellulose fibers into nanosized fibers, which generates NFC. of sodium carboxylate groups from the C6 primary hydroxyls of
The NFC is long with a length greater than 2 mm and displays NFC surfaces leads to a significant decrease of the thermal
web-like entangled structures. stability of the NFC.107,108 Another route toward the preparation
Besides the high-pressure homogenizer, other apparatus of carboxylated NFC suspensions with individualized nanofibers
such as grinder100,101 and high-intensity ultrasonicator102,103 was developed by Wågberg et al. by using high-pressure homo-
can also be directly utilized for nanofibrillation of the cellulose genization of carboxymethylated cellulose fibers followed by
fibers for producing NFC, although the energy required is still ultrasonication and centrifugation.89
large. To reduce the energy requirement and improve the The high aspect ratio and web-like entangled structures of
nanofibrillation degree, removing the matrix from the cellulose NFC are beneficial for developing flexible substrates such as films
sources is critical before nanofibrillation. The as-prepared cellulose and aerogels, for integrating with active materials, or converting
pulps also need to be kept in the water-swollen state during the NFC to carbon materials to develop electrodes and separators
whole chemical purification process. Abe et al. reported the fabrica- for flexible and high strength energy storage devices.
tion of NFC with a uniform width of 15 nm by using chemical
treatment to remove lignin and a large amount of hemicellulose 3.2. Cellulose nanocrystal (CNC)
from wood, followed by nanofibrillation of the cellulose pulps CNC has been produced using an acid hydrolysis approach
using a grinder.82 Using a similar process, NFC with a uniform from a range of cellulose sources. Disordered or paracrystalline
width has been successfully produced from rice straw,83 potato regions of cellulose are preferentially hydrolyzed, whereas
tuber,83 and bamboo.80 Enzymatic hydrolysis combined with crystalline regions that have a higher resistance to acid attack
mechanical nanofibrillation is another route to produce NFC. remain intact. Thus, the CNC is short and displays lower aspect
Pääkkö et al. prepared NFC using enzymatic hydrolysis combined ratios and a larger relative crystallinity compared with that of
with mechanical shearing and high-pressure homogenization.87 NFC. Sulfuric acids have been extensively used for CNC pre-
The resulting NFC mainly consisted of nanofibers with a width of paration. Rånby first reported that colloidal suspensions of
5–6 nm and nanofiber aggregates with a width of approximately cellulose can be obtained by controlled sulfuric acid-catalyzed
10–20 nm. Although high-quality NFC can be produced from degradation of cellulose fibers.109 Marchessault et al. demon-
most cellulose sources, the uniform nanofibrillation of cellulose strated that colloidal suspension of sulfuric acid hydrolyzed
fibers from raw materials with a high cellulose content such as CNC exhibited nematic liquid crystalline alignment.110 The
cotton and flax104 is difficult because a small amount of matrix sulfuric acid reacts with the surface hydroxyl groups of cellulose
can be removed during the chemical purification process, and to yield charged surface sulfate esters that promote dispersion
there are strong interactions between adjacent cellulose nano- of the individual CNC in water. However, the introduction
fibers that have a small amount or no hemicellulose on the of charged sulfate groups decreases the thermal stability of
surfaces within the cell walls. Recently, Chen et al. reported a the CNC. The concentration of sulfuric acid in the hydrolysis
method to individualize NFC from raw cotton by chemical purifica- reactions is usually controlled at a typical value of 65 wt%; this
tion (removal of noncellulosic components) and pretreatment level is determined, on the one hand, by the requirement for
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efficient hydrolysis and sulfate ester formation, and, on the BC is high-purity cellulose with a web-like entangled struc-
other hand, by the requirement to prevent the carbonization of ture and can be utilized to integrate with active materials or
cellulose by dehydration. The structures of CNC obtained by converted to carbon materials to develop flexible energy storage
using similar sulfuric acid hydrolysis methods vary depending materials/devices. However, compared with NFC/CNC, which
on the cellulose sources. For example, CNCs from cotton and can be produced from abundant lignocellulosic resources,
Avicel have a length between 100 and 300 nm, whereas that the cost of BC is relative high, although the industrial-scale
from tunicin is several micrometers long and has a whisker-like production of BC has been achieved.
morphology.90 Hydrochloric acid was also used as a hydrolyzing
agent for producing CNC. It can remove the amorphous area of

cellulose but does not react with the surface hydroxyl groups of 4. Supercapacitors
cellulose, resulting in CNC with large amount of CNC bundles.
For the hydrochloric acid hydrolyzed cotton CNC,86 the single Supercapacitors, also known as ultracapacitors or electro-
CNC in the bundles were 100–400 nm long and 4–9 nm wide, chemical capacitors, offer a promising approach to meet the
with aspect ratios ranging from 11 to 100. The CNC displays high ever-increasing power demand owing to their high power
crystallinity and thermal stability with thermal degradation tem- density, superior rate capability, rapid charging/discharging
peratures of 341.7 1C. Thermally stable CNC can also be produced rate, long cycle life, simple principles, fast dynamics of charge
by other strong acid hydrolysis (such as phosphoric acid). propagation and low maintenance cost.116–118 Supercapacitors
The highly crystalline CNC with high specific surface area can be typically classified into two types: electrical double
are conducive for integrating with active materials or convert- layer capacitors, which store energy through electrostatically
ing to carbon materials to develop electrodes with high specific accumulated charges at the electrode/electrolyte interface, and
surface areas. The chiral nematic structures derived from CNC pseudocapacitors, which are based on rapid redox reactions at
are expected to be utilized for the development of electrodes the electrodes for huge pseudocapacitance.
with novel structures and properties for high-performance Nanocellulose can be integrated with active materials or
energy storage. converted to carbon materials as electrode materials for super-
capacitors. It can also be processed as separator materials
3.3. Bacterial cellulose (BC) for supercapacitors.119,120 The electrochemical performance of
BC is another kind of high aspect ratio nanocellulose that is nanocellulose-derived materials, that were used as electrodes
produced through a microbial fermentation process. BC has and tested under different conditions for supercapacitors, has
long been utilized as the raw material for nata-de-coco, an been compared and summarized in Table 2.121–139 The Ragone plot
indigenous dessert food, for which one centimeter thick gel of supercapacitors fabricated from several typical nanocellulose-
sheets fermented with coconut water are cut into cubes and derived hybrid materials and carbon materials (including porous
immersed in sugar sirup.111 BC is secreted extracellularly by carbon materials and carbon hybrid materials) is shown in
certain bacteria belonging to the genera Acetobacter, Agrobacterium, Fig. 4.123,125,130–133,135–141 The electrochemical properties (such
Alcaligenes, Pseudomonas, Rhizobium, or Sarcina.43,112 In con- as energy density and power density) of those supercapacitors
trast to NFC and CNC, which are mainly extracted from higher are effectively improved by integrating nanocellulose and
plant cellulose sources, BC is fabricated by a biotechnological nanocellulose-derived carbon materials with other active materials.
assembly processes from low-molecular weight carbon sources, Although several supercapacitors exhibit high energy density
such as D-glucose.44 The bacteria are cultivated in common and power density, large space for spontaneously improving the
aqueous nutrient media, and the BC is excreted as exopoly- energy density and power density is still exist. In the ensuing
saccharide at the interface to the air, producing a thick gel sections, we discuss recent progress reported on the develop-
composed of an interconnected 3D porous BC nanofiber net- ment of nanocellulose and its derived materials for super-
work structure and B99% water, called pellicle. The structure capacitor applications.
of the nanofiber network of BC can be controlled by changing
the type of bacterial strain, the additives in the culture medium, 4.1. Flexible supercapacitors based on NFC/BC-derived hybrid
the type and conditions of cultivation, and the drying processes materials
in the post-processing stage.113 There are apparent structural Because of the high aspect ratio and web-like entangled struc-
differences between BC and higher plant derived NFC such as tures, NFC/BC can form hybrids with active materials such as
wood NFC. BC is secreted as a ribbon-shaped fibril of around nanocarbon or conductive polymers to fabricate electrodes for
100 nm in width and around 100 mm in length,114 which flexible supercapacitors. The active materials can be integrated
is composed of 2–4 nm width nanofibrils. BC is free of func- with NFC/BC using different composite approaches such as
tional groups (carbonyl, carboxyl) and is almost pure cellulose extrusion,121 vacuum filtration142 and freeze-drying,125 resulting
containing no lignin and other foreign substances.111 Moreover, in the formation of various structures such as 1D fibers, 2D films/
BC is characterized by very long polymer chain with polymeriza- papers, and 3D aerogels/foams. Owing to the high aspect ratio
tion up to 8000 and displays a distinct crystallinity of up to 90%. and intrinsic mechanical strength, the introduction of NFC/BC
It should be noted that BC can also be utilized as a raw material into the hybrid materials makes the electrodes/supercapacitors
to prepare NFC106 and CNC.115 flexible, which can store energy upon repeated bending, folding
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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This journal is © The Royal Society of Chemistry 2018

Chem Soc Rev
Chem Soc Rev
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:

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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Chem. Soc. Rev., 2018, 47, 2837--2872 | 2845

Review Article
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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
Fig. 4 Ragone plot of supercapacitors fabricated from several typical supercapacitors exhibited reliable electrochemical performance
nanocellulose-derived hybrid materials and carbon materials. The black sym- and good mechanical flexibility. Even after 1000 bending cycles
bols within the light blue background region represent the supercapacitors
with a bending radius of 2.5 mm, the supercapacitors still retained
fabricated from nanocellulose-derived hybrid materials. The red symbols within
the light green background region represent the supercapacitors fabricated their structural integrity without impairing the cell capacitance.
from nanocellulose-derived porous carbon materials and carbon hybrid 3D aerogels/foams for supercapacitor can be fabricated
materials. Data obtained from ref. 123, 125, 130–133 and 135–141. 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
and/or compressing without a dramatic decrease in the electro- porosity, low density, high conductivity, as well as the synergy
chemical performance. effect of NFC/BC and nanocarbons, which makes them good
4.1.1. Hybrids with nanocarbon. NFC/BC can be mixed electrodes for flexible supercapacitors. NFC/reduced GO (RGO)
with nanocarbon materials (Fig. 5) such as carbon nanotubes hybrid aerogels were prepared by supercritical CO2 drying of
(CNTs) and graphene to form uniform solutions. 1D fibers can the corresponding hydrogels.124 Flexible supercapacitors were
be produced from the composite solutions by wet spinning. developed using the hybrid aerogel film as an electrode, and
Macrofiber with a uniform diameter of B50 mm was fabricated exhibited areal capacitance of 158 mF cm 2, and a maximum
by extrusion of NFC/single-walled CNT (SWCNT) suspensions areal energy density of 20 mW h cm 2 at an areal power density
in an ethanol coagulation bath (Fig. 5a) and drying in air under of 15.5 mW cm 2. Aerogels derived from NFC/RGO/CNT were
restricted conditions.121 The SWCNTs were preferentially developed by freeze-drying of aqueous dispersion of NFC/GO
oriented along the axial direction of the macrofiber, whereas nanosheets (GONSs)/CNT, followed by thermal reduction of the
the NFC effectively prevented the aggregation of SWCNTs. The GONSs.125 The supercapacitors assembled by the compressed
as-prepared nonwoven macrofiber mat wearable supercapacitors NFC/RGO/CNT aerogel exhibited a specific capacitance of
exhibited good electrochemical properties (Fig. 5b), outstanding 252 F g 1, an energy density of 8.1 mW h g 1 at a power density
tailorability, and damage reliability. The supercapacitors maintained of 2.7 W g 1, as well as good cyclic stability with more than
96.0% of their initial capacitance after 1500 bending cycles (Fig. 5c). 99.5% capacitance retention after 1000 charge/discharge cycles.
After a fifth extreme deformation, the capacitance retention of Recently, Hamedi et al. pioneered the development of a
the supercapacitors was approximately 93%. layer-by-layer (LBL) assembly technology for coating functional
2D films/papers can be fabricated by mixing NFC/BC and materials onto NFC aerogel surfaces (Fig. 5i).144 Prior to LBL
nanocarbon solutions followed by filtration and drying. Films assembly, covalent crosslinking of the NFC aerogels was con-
containing the covalent intercalation of graphene oxide (GO) ducted to avoid the disintegration of the NFC aerogels during
and BC were fabricated by filtration of the reaction mixture the LBL assembly process. Active materials such as CNTs were
followed by drying.142 The composite films exhibited a tensile assembled onto NFC aerogels by LBL, and enhanced compressive
strength of 18.5 MPa and an elongation at break of 24%. With strength, super elasticity in the wet state, and elastic mechano-
an electrical conductivity of 171 S m 1, the composite films responsive resistance were achieved. A SWCNT-functionalized
demonstrated specific capacitance of 160 F g 1 at 0.4 A g 1. 2D NFC aerogel electrode showed a specific capacitance of 419 F g 1
films/papers can also be fabricated by the deposition of nano- by accounting for the measured weight of the active LBL layer.
carbons on the NFC/BC films/papers. Kang et al. reported the Using similar covalently crosslinked NFC aerogels as scaffolds,
preparation of 2D papers by the deposition of a CNT layer on CNT electrodes and separator were LBL deposited on the NFC
the BC paper through a vacuum filtering process (Fig. 5d–g).123 aerogel surface, resulting in the assembly of 3D supercapacitors
The CNTs were coated on and integrated with the BC paper (Fig. 5j).141 The pore walls of the NFC aerogel were gradually
through hydrogen bonding and van der Waals’ interactions. thickened when the first electrode, the separator, and the second
Flexible supercapacitors fabricated by incorporating ionic liquid electrode were added (Fig. 5k–m). The 3D supercapacitor showed
based polymer gels between two BC papers coated with CNTs stable operation over 400 cycles with a capacitance of 25 F g 1,
showed a specific capacitance of 50.5 F g 1, a specific energy density 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- using these composites as electrodes exhibited a volumetric
mers such as polypyrrole (PPy),145–150 polyaniline (PANI),151 and energy and power densities of 3.1 mW h cm 3 and 3 W cm 3 in
poly(3,4-ethylenedioxythiophene) (PEDOT)127 are usually poly- aqueous electrolyte, respectively. The functionality of the devices
merized in situ and form a homogenous layer around NFC/BC, was maintained even in different mechanically challenging
resulting in composite films/papers with high electrical con- states (Fig. 6c–e). Wang et al. also reported the fabrication of
ductivity. To improve the electrochemical performance, the flexible NFC/PEDOT composite papers by chemical polymeriza-
composites are usually thick with large active mass loadings, tion of 3,4-ethylenedioxythiophene at room temperature in the
which often sacrifice the electrode flexibility. Thus, improving presence of NFC followed by vacuum filtration and drying
the interfacial interaction between nanocellulose and the con- (Fig. 6f).127 A uniform PEDOT coating layer was formed on NFC
ductive polymers, wrapping the nanocellulose with a uniform (Fig. 6g) and the composite papers exhibited a surface area of
and sufficiently thin conductive polymer layer, and decreasing 137 m2 g 1, a sheet resistance of 1.4 O & 1, and an active mass
the electrode thickness are critical for fabricating flexible loading of 7.3 mg cm 2. Symmetric NFC/PEDOT paper-based
electrodes. Wang et al. reported the introduction of quaternary supercapacitors demonstrated high specific electrode capaci-
amine groups on the surface of NFC to prepare NFC with tances (920 mF cm 2) and good cycling stability (93% capacity
cationic (c-NFC) surface charges (Fig. 6a).126 After the polymeriza- retention after 15 000 cycles at 30 mA cm 2) in 1 M H2SO4. Under
tion of pyrrole on the c-NFC (Fig. 6b), the composites delivered high harsh mechanical conditions involving the twisted and bent
normalized gravimetric (127 F g 1) and volumetric (122 F cm 3) states, the device exhibited good stability (Fig. 6h–j) and retained
capacitances at 300 mA cm 2. Symmetrical supercapacitor 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/ several ways to fabricate electrodes for supercapacitors. CNC
BC composite membranes,154 PPy/nickel sulfide/BC composite can be integrated with conductive polymers such as PPy through
membranes,155 PPy/copper sulfide/BC composite membranes,156 electrodeposition methods.163 A cotton CNC was subjected to
and PANI/silver NFC aerogels,157 have all been fabricated as TEMPO-mediated oxidation to convert the surface primary
electrodes for developing flexible supercapacitors. hydroxyls to carboxylate functionalities. Then, the TEMPO-
4.1.3. Hybrids with nanocarbon and conductive polymers. oxidized CNC was electrodeposited with PPy to fabricate
Nanocarbon and conductive polymer can be integrated together with CNC/PPy nanocomposites. A symmetrical supercapacitor using
NFC/BC to fabricate electrode materials for supercapacitors. These CNC/PPy nanocomposites as the electrodes was constructed and
combinations give electrodes enhanced flexibility and mechanical tested at an operating voltage of 1 V. The specific energy density
robustness, and maintained their capacitances.129,158,159 A flexible of the supercapacitor was 8.34 W h kg 1 at 1 mA cm 2. The
BC/RGO/PPy composite film was prepared through an in situ supercapacitor retained 70% of its initial capacitance after
polymerization and filtering method. The assembled symmetric cycling 10 000 times and 47% of its capacitance after an excessive
supercapacitor delivered an areal capacitance of 1.67 F cm 2, an 50 000 cycles. The good cycling stability was mainly attributed to
areal energy density of 0.23 mW h cm 2, and a maximum power the stability of the individual electrodes owing to the highly
density of 23.5 mW cm 2.160 An NFC/GO/PPy composite paper porous structure of the CNC/PPy nanocomposites and the thin
was produced by straightforward polymerization of a PPy layer coating of PPy onto individual CNC, which facilitates the ion and
both on the NFC attached to the GO sheets and the GO itself.161 solvent movements during the charge/discharge cycles and thus
The NFC reinforced the entire electrode yielding a robust and makes the composites with stable volumetrically. CNC can
compact electrode that still contained a sufficient number of also be integrated with conductive polymers through in situ
mesopores to allow the material to undergo fast PPy charge and polymerization methods.164 PPy was readily coated on the
discharge reactions. Symmetrical supercapacitors containing surface of TEMPO-oxidized CNC and formed a conductive shell
NFC/GO/PPy composite paper were flexible, with 485% capaci- on individual CNC through the in situ chemical polymerization
tance retention over 16 000 cycles at 5 A g 1 and high volumetric of pyrrole. The 1D structure of the CNC not only facilitated the
specific capacitance (301 F cm 3 based on PPy). efficient transport of electrons along one controllable direction,
BC/multiwalled CNTs (MWCNTs)/PANI composite films but also provided a very low percolation concentration of
were produced by vacuum filtration of a MWCNTs layer onto CNC/PPy to achieve a conductive network. The electrical conductivity
BC paper followed by electrodeposition of PANI (Fig. 7a–h).162 Owing of the CNC/PPy composites approached 4 S cm 1 with a capacitance
to the porous structure and electrolyte absorption properties of the of 248 F g 1 at 0.01 V s 1, retaining 90% capacitance at up to
BC paper, the flexible BC/MWCNTs/PANI hybrid electrode exhibited 0.1 V s 1. To ensure a uniform PPy coating, PVP was used as a
high specific capacitance (656 F g 1 at 1 A g 1) and good cycling surface modifier through physical adsorption onto the CNC
stability with capacitance loss of less than 0.5% after 1000 cycles at surface prior to the introduction of pyrrole.165 PVP introduced
10 A g 1. Moreover, the electrodes with high mass loading in the hydrophobicity on the CNC surface, making it more favorable for
range of 7–12 mg cm 2 were prepared by using BC/PPy nanofibers the growth of the hydrophobic PPy shell, which acted as a steric
in combination with MWCNTs through a vacuum-filtering method stabilizer preventing further agglomeration of the nanoparticles.
(Fig. 7i–o).128 The as-prepared symmetric supercapacitors exhibited a The CNC/PVP/PPy composites exhibited electronic conductivity
capacitance of 590 mF cm 2 and good cycling stability with 94.5% of of 36.9 S cm 1, a specific capacitance of 322.6 F g 1, and cycling
capacitance retention after 5000 cycles. stability with less than 9 and 13% capacitance loss after 1000
Overall, NFC/BC-derived hybrid electrodes hold great promise and 2000 cycles, respectively.
for flexible supercapacitors. By introducing active materials, Because CNC is short with a low aspect ratio, CNC-derived
the electrochemical performance of the hybrid electrodes can bulk materials such as aerogels are usually mechanically weak86
be increased, whereas the addition of NFC/BC can improve the and easily broken when bent or compressed. Cranston et al.
mechanical and surface properties of the hybrid electrodes developed a chemical crosslinking method to produce CNC
in several ways. The high aspect ratio NFC/BC formed aerogels with tailorable mechanical performance and shape
strong entangled networks with the active materials, which recovery abilities (Fig. 8a–e).166 The CNC aerogels were fabricated
made the hybrid electrodes flexible, bendable, foldable, and based on the chemical crosslinking of aldehyde-modified
compressible without deterioration of the electrochemical CNCs and hydrazide-modified CNCs, which formed covalent
performance. The ratio of active materials plays a critical role hydrazone crosslinks immediately upon contact. These CNC
on the electrode performance. The interface interactions between aerogels acted as universal substrates for a variety of active
the active materials and the NFC/BC should be optimized to nanoparticles, such as PPy nanofibers, PPy-coated CNTs, and
maximize the synergistic effects and enhance the activity of spherical manganese dioxide nanoparticles during the aerogel
supercapacitor and spontaneously maintain its mechanical assembly, offering enough accessible surface area of active
strength and high flexibility. material, which promoted charge storage. The CNC-active nano-
particle hybrid aerogels were strong and remained intact when
4.2. CNC-derived hybrid materials compressed in both air and aqueous electrolytes. Symmetric
CNC, which has a higher specific surface area compared with coin-cell supercapacitors were assembled containing two
that of NFC/BC, can be integrated with active materials in 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- rates and good cyclic stability and capacitance stability during
normalized specific capacitances at 2 mV s 1 for PPy nanofibers, compression and bending cycles.
PPy-coated CNTs, and spherical manganese dioxide nanoparticle Overall, compared with NFC/BC, highly crystalline CNC has
devices were 3.32, 2.42, and 2.14 mF cm 2, respectively. a higher specific surface area to integrate with active materials.
Using similar CNCs as building blocks, an aerogel-based A uniformly, full, and thin coating of an active materials on
current collector composed of crosslinked CNCs and MWCNTs individual CNC fibers is effective for facilitating the ion move-
was produced using bile acid as a dispersant (Fig. 8f–k).167 PPy- ments during the charge/discharge cycles. The CNC-derived bulk
based electrodes with a mass loading up to 17.8 mg cm 2 were materials such as films and aerogels are fragile and easily broken
fabricated based on in situ polymerization of pyrrole inside the when bent or compressed, mainly because of the low aspect ratio
CNC/MWCNT aerogel. The CNC/MWCNT/PPy electrodes were of CNCs, which limits their use in several practical applications
flexible and had good compression stability at 80% compression, such as for the development of flexible supercapacitors. Although
exhibited a capacitance of 2.1 F cm 2 with a mass ratio of active several methods such as chemical crosslinking can be utilized
material/current collector of 0.57. The electrodes and devices to fabricate flexible CNC electrodes, the complicated synthesis
showed good capacitance retention at high charge/discharge 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 The carbon materials possessed an ultralow apparent density, high
thermal degradation temperature of H2SO4-hydrolyzed CNCs specific surface area, and high electric conductivity. Nanocellulose-
hampers the thermal stability of the supercapacitors. Thus, the derived porous carbon materials can be directly utilized as
surface/interface properties and interactions of the CNCs and the electrodes for supercapacitors. The electrochemical properties
active materials should be rationally designed and controlled to of the carbon materials can be further improved through
achieve uniform integration of active materials and CNCs with a activation treatment, doping with heteroatoms, and the formation
high active material loading, and to make composites with high of hybrids with active materials. Recently, nanocellulose-
mechanical strength, flexibility, and thermal stability without derived porous carbon materials and carbon hybrid materials
decreasing the specific surface area of the bulk materials. have been frequently developed as the electrode materials for
supercapacitors.
4.3. Nanocellulose-derived carbon materials 4.3.1. Porous carbon materials. NFC and BC were utilized
High temperature pyrolysis under an inert atmosphere can convert as building blocks to prepare films/aerogels for pyrolysis and
nanocellulose bulk materials into conductive carbon materials. 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 contact resistance. (2) Annealing of heteroatom-containing
after the pyrolysis process and the 3D structure of NFC/BC polymers and NFC/BC composite aerogels/foams. Heteroatom-
aerogels was inherited. Although the carbon aerogels possessed containing polymers such as PANI and PPy can form composites
ultra-low density, extraordinary compressibility, and high electric with NFC/BC aerogels/foams through in situ polymerization or
conductivity, they exhibited low electrochemical properties for electrodeposition methods. After carbonization, the heteroatom-
supercapacitors. For example, the specific capacitance of the doped carbon aerogels/foams were fabricated. BC was used as
BC-derived carbon aerogels was only 77.7 F g 1 at 1 A g 1,135 both a template and precursor for the synthesis of N-doped carbon
mainly because of its relatively low surface area and wettability. networks through the carbonization of PANI-coated BC (Fig. 9e).136
Activation treatment can apparently increase the specific surface KOH activation was conducted to further optimize the pore
areas. The activation of BC-derived carbon aerogels with a mixed structure and improve the specific surface area. N doping
gas of CO2/argon exhibited a high BET surface area of 699.7 m2 g 1 enhances the surface polarity, electric conductivity, and electron-
compared to that of 286.4 m2 g 1 for the carbon aerogels donor tendency of carbon materials. The as-prepared N-doped
without activation.132 The CV curves of the activated carbon porous carbon displayed a high specific capacitance of 296 F g 1 at
aerogel had roughly rectangular shapes and displayed almost 2 mV s 1, higher than that of raw BC-derived carbon (161 F g 1).
mirror images, which demonstrated good capacitive behavior and The N-doped carbon also exhibited excellent rate performance
reversibility. Activation of the carbon aerogels with potassium and cycling stability, which was ascribed to its unique con-
hydroxide130,136,171 or potassium citrate131 is another strategy to ductive networks and energy storage units. An interconnected,
improve the specific surface areas, which ensures more effective well-organized 3D conductive network is beneficial for electron
electroactive sites for charge accommodation and thus improve- transport, and a N-doped porous carbon network with high
ment of the specific capacitance of the carbon aerogels. Potassium surface area can provide more active sites for energy storage
hydroxide was also found to play a critical role for facilitating the and short ion diffusion length during the charge/discharge
crosslinking of BC and acting as a hard template to generate process. (3) Hydrothermal treatment of carbon aerogels with
macropores during the carbonization process. The obtained heteroatom-containing molecules in solution. Because the
carbon aerogels had a 3D interconnected honeycomb-like hier- NFC/BC-derived carbon aerogels have high porosity, an aqueous
archical network structure (Fig. 9c),130 exhibited a high specific solution containing heteroatom molecules such as urea and
surface area of 1533 cm2 g 1, and a high specific capacitance of ammonia can easily permeate through the carbon aerogels.
422 F g 1 in 6 M KOH, as well as good rate capability with N-Doped carbon aerogels were fabricated by Chen et al. using
73.7% of capacitance retention at 500 mV s 1. BC-derived carbon aerogels and urea through a hydrothermal
The electrochemical properties of porous carbon materials reaction under mild conditions.135 The as-prepared N-doped
can be improved by doping with heteroatoms, because the carbon aerogels still maintained a free-standing 3D pellicle with
heteroatom dopants can modulate the physical and chemical interconnected nanofibers and crosslinking pores (Fig. 9f–i).
properties of the carbon material to generate more reactive Owing to the high content of N doping and proper N species,
sites. The doping with heteroatoms has been achieved mainly the interconnected pore structure, and the high specific surface
by three routes: (1) Annealing of NFC/BC aerogels/foams with area of the carbon aerogels, the N-doped carbon aerogels exhibited
heteroatom-rich compounds. Because NFC/BC aerogels/foams a high specific capacitance of 173.3 F g 1, which is apparently
are hydrophilic and exhibit high porosity, the heteroatom-rich higher than that of BC-derived carbon aerogels (77.7 F g 1).
compounds can easily fill with the pores of the aerogels/foams. N-Doped carbon aerogels can also be produced using a hydro-
After high temperature pyrolysis under an inert atmosphere, thermal method with BC-derived carbon aerogels (after activa-
heteroatom doping was achieved. Various doped carbon aerogels tion with a mixed gas of CO2/argon) and aqueous ammonia.132
were produced by Wu et al. through the pyrolysis of BC pellicles An all-solid-state supercapacitor was fabricated by impregnating
that had adsorbed or were dyed with different toxic organic dyes poly(vinyl alcohol)–H2SO4 gel electrolyte into the framework
(Fig. 9d).172 From the sample obtained from methylene blue of N-doped carbon aerogels. The assembled supercapacitor
(C16H18ClN3S), N and S atoms were codoped and homogeneously exhibited good flexibility with a maximum power density of
distributed within the carbon networks. When used as super- 390.5 kW kg 1 and stable cycling stability over 5000 cycles.
capacitor electrodes, the N,S dual-doped carbon aerogels exhibited CNC can also be converted into porous carbon materials that can
better electrochemical properties compared with the raw carbon be further functionalized and utilized for supercapacitors. CNC has
aerogels. In addition, P-doped, N,P-codoped, and B,P-codoped been used as both a carbon source and a template for the controlled-
carbon aerogels were obtained by the pyrolysis of BC immersed growth of the N precursor to form melamine-formaldehyde (MF)
in H3PO4, NH4H2PO4, and H3BO3/H3PO4 aqueous solution, coated CNCs (Fig. 10a).173 The hybrid material was subjected to
respectively.133 The N,P-codoped carbon aerogels as electrodes pyrolysis to fabricate N-doped carbon materials with micro-, meso-,
for supercapacitors showed a maximum power density of and macropores (Fig. 10b). Optimal capacitances of 328.5 F g 1 at
186.03 kW kg 1. The high power density was mainly attributed 0.01 V s 1 and 352 F g 1 at 5 A g 1 were achieved for the carbon
to the codoping of N and P and the 3D porous nanofiber materials in 1 M H2SO4. The carbon materials also exhibited good
network of the carbon aerogels, which ensured good electrical cycling stability (less than 4.6% loss after 2000 cycles) at 20 A g 1.
conductivity while avoiding the use of conducting additives Another strategy for using CNC-derived porous carbon
and polymer binders, which blocks the pores and increases 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- nematic mesoporous carbon are obtained (Fig. 10d–g).176 In a
nize into a chiral nematic phase that can be preserved upon symmetrical capacitor with H2SO4 as the electrolyte, the meso-
slow evaporation, thereby resulting in chiral nematic films porous carbon films display near-ideal capacitor behavior with
(Fig. 10c).34 MacLachlan et al. reported that the evaporation- specific capacitance of 170 F g 1 at 230 mA g 1.
induced self-assembly of CNC with silica precursors can result CNC and NFC can also be integrated together to form
in composite films with chiral nematic structures. Upon pyr- porous carbon materials for supercapacitors (Fig. 10h).177 For
olysis and etching of the silica, freestanding films of chiral the hybrid films, the NFC formed a macroporous framework
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and the CNC was assembled around the NFC framework. By the surface of BC-derived carbon aerogels by oxidizing the
depositing a thin layer of Al2O3 as a protective layer by atomic exterior carbon (Fig. 11a–d).135 The carbon aerogel with high
layer deposition followed by etching away Al2O3 using HCl after graphitization serves as a highly conductive matrix for fast ion
carbonization, a freestanding carbon film with a hierarchical and electron transport, whereas the ultrathin MnO2 film that
porous structure and a specific surface area of over 1200 m2 g 1 is strongly anchored on the surface of carbon aerogels can
was produced. The two-level hierarchical porous structure effectively shorten the diffusion length of electrolyte ions during
derived from NFC and CNC facilitated fast ion transport in the charge/discharge process and provide a large electrochemically
the film. When tested as an electrode material with a mass active surface area for the fast reversible Faradic redox reactions.
loading of 4 mg cm 2 for supercapacitors, the carbon film Asymmetric supercapacitor (ASC) fabricated by using the carbon
exhibited a specific capacitance of 170 F g 1. Even at 50 A g 1, it aerogels/MnO2 with a specific capacitance of 254.6 F g 1 as
still retained 65% of its original specific capacitance. positive electrodes, the N-doped carbon aerogels with a specific
4.3.2. Carbon hybrid materials. To further improve the capacitance of 173.3 F g 1 as negative electrodes, and Na2SO4 as
specific capacitance of nanocellulose-derived carbon, carbon aqueous electrolyte, worked very well at different voltages, even
hybrid materials were developed by integration with active up to 2.0 V. Such an ASC displayed a maximum energy and
materials such as activated carbon, nanocarbon, metal oxides, power density of 32.91 W h kg 1 and 284.63 kW kg 1, respec-
hydroxides, and sulfides, etc. The carbon hybrid materials can tively. Fan et al. decorated N-doped BC-derived carbon with
be prepared by direct pyrolyzation of the composites of nano- flower-like MnO2 (Fig. 11e–k).136 The BC-derived carbon/MnO2
cellulose and carbon materials. Ma et al. reported the prepara- exhibited a high specific capacitance of 273 F g 1 at 2 mV s 1.
tion of N-doped carbon materials/RGO/BC composite paper.134 The as-assembled carbon/MnO2//KOH activated N-doped carbon
The BC was exploited as both a substrate and a biomass pre- ASC exhibited a considerably high energy density of 63 W h kg 1
cursor for N-doped carbon by pyrolysis. The one-step carboniza- in 1 M Na2SO4. The ASC also exhibited good cycling performance
tion treatment not only fabricated the N-doped 3D nanostructured with 92% specific capacitance retention after 5000 cycles.
carbon composite materials but also forms the reduction of the To further improve the specific capacitance, the nanocellulose-
GO sheets at the same time. The symmetric supercapacitor derived carbon materials were used as a scaffold for deposition of
obtained using the composite paper as an electrode showed an metal hydroxyl and sulfide. Lai et al. reported the further deposi-
areal capacitance of 810 mF cm 2 in KOH and 920 mF cm 2 in tion of ultrathin nickel–cobalt layered double hydroxide (Ni–Co
H2SO4, delivered an energy density of 0.11 mW h cm 2 in KOH LDH) nanosheets on N-doped BC-derived carbon nanofibers
and 0.29 mW h cm 2 in H2SO4, and a maximum power density (Fig. 11l and m).137 The composite electrodes exhibited signifi-
of 27 mW cm 2 in KOH and 37.5 mW cm 2 in H2SO4. Free- cantly enhanced specific capacitance (1949.5 F g 1 at 1 A g 1),
standing carbon nanofibers/activated carbon composite films high capacitance retention of 54.7% even at 10 A g 1, and good
were prepared by carbonization of the NFC/activated carbon cycling stability with 74.4% retention after 5000 cycles. ASCs
composite films.178 The carbon nanofibers are ‘welded’ on acti- assembled by using the N-doped carbonized BC@Ni–Co LDH
vated carbon particles and integrated into one piece of carbon. The composites as positive electrode and N-doped carbonized BC as
network of carbonized NFC possessed better electron transport negative electrode exhibited an energy density of 36.3 W h kg 1
efficiency than the activated carbon particles. When tested as at a power density of 800.2 W kg 1. Zuo et al. reported the
supercapacitor electrodes at commercial level mass loading, the uniform decoration of the pore walls of BC-derived carbon
composite films exhibited 2-times-slower capacitance fading at aerogels with NiS particles through a hydrothermal process.139
high current and 3-times-higher maximum power density than The ASCs were constructed utilizing NiS composite carbon aerogels
the bare activated carbon. The carbon hybrid materials can also and carbon aerogels as the positive and negative electrodes,
be prepared by pyrolyzation of the composites of nanocellulose respectively. Through the synergistic effect of the 3D porous
and the carbon precursors. Highly graphitized carbon aerogels structures and conductive networks derived from the carbon
were synthesized based on BC toughened lignin–resorcinol– aerogel and the high capacitive performance of NiS, the ASC
formaldehyde aerogels.179 The as-prepared carbon aerogels, exhibited an energy density of B21.5 W h kg 1 at a power
consisting of a blackberry-like, core–shell structured, and highly density of 700 W kg 1, as well as good cycle stability with
graphitized carbon nanofibers, were able to undergo at least B87.1% specific capacitance retention after 10 000 cycles.
20% reversible compressive deformation. Owing to the unique Overall, the pyrolyzation of nanocellulose-based bulk materials
nanostructure and large mesopore population, the carbon to carbon materials can obviously increase their specific surface
materials exhibited high areal capacitances calculated using area and electrical conductivity. After further functionalization by
the total surface area and the mesopore surface area of 62.2 activation, heteroatom-doping, or the formation of hybrids with
and 78.7 mF cm 2, respectively. other active materials, nanocellulose-derived carbon electrodes
Carbon hybrid materials can be achieved by direct reaction showed good electrochemical performance. Controlling the
between carbon framework and metal precursor under certain morphologies, structures, and ratios of the doping heteroatoms/
conditions. MnO2-decorated carbon aerogels were fabricated by active materials of the nanocellulose-derived carbon materials
employing BC-derived carbon aerogels as a precursor. Based on would be the main challenge in the future. Surface/interface
the redox reaction 4MnO4 + 3C + H2O - 4MnO2 + CO32 + design on nanocellulose/nanocellulose-derived carbon and active
2HCO3 , MnO4 ions were reduced spontaneously to MnO2 on 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 the nonaqueous electrolyte, carrying the current. Nanocellulose
etching process. The ultimate goal is to achieve well-defined can be integrated with other active materials or converted to
bulk-, micro-, nano-, and even atom-scale structures of the carbon materials to be further developed as the electrodes for
carbon materials. The structure–property relationship of the LIBs. The electrochemical performance of nanocellulose-derived
novel developed nanocellulose-derived carbon materials should materials used as electrodes for LIBs has been compared and
be better understand for maximum utilizing the advantageous of summarized in Table 3.184–193 Nanocellulose-derived films/
the carbon materials for high performance supercapacitors. 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
5. Lithium-ion batteries nanocellulose and its derived materials for LIBs.
Since the introduction by Sony Inc. in 1991, LIBs have emerged
as the main power source for portable electronic devices because 5.1. Flexible LIBs based on NFC/BC hybrid materials
of their high energy density, large output voltage, appreciable The high aspect ratio NFC/BC can be used as a flexible substrate
lifespan, and environmentally benign operation.180–183 A LIB and binder material to integrate with active materials to prepare
mainly consists of four functional components: anode, cathode, paper/film electrodes for flexible LIBs. Flexible positive electrodes
electrolyte, and separator. In principle, the charging and dis- were developed by filtration of a water dispersion of NFC,
charging process of a LIB is realized through the insertion/ LiFePO4, and Super-P carbon particles (Fig. 12a–c).184 The elec-
deintercalation of Li ions transporting between the anode and trodes showed good mechanical properties both dry and when
the cathode material. During charging, an external electrical soaked with battery electrolyte. The capacities were 151 mA h g 1
power source forces the current to pass in the reverse direction at C/10 and 132 mA h g 1 at 1C for sample dried at 170 1C.
and enables the migration (diffusion) of Li ions from the Flexible negative electrodes have been obtained by integrating
cathode to the anode through the electrolyte. During the nanocellulose with active materials such as CNTs and silicon.
discharging process, Li ions move back to the anode through Flexible paper anodes were prepared through a paper-making
Chem Soc Rev
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

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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Chem. Soc. Rev., 2018, 47, 2837--2872 | 2857

Review Article
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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 142 mA h g 1 at 10C. TEMPO-oxidized NFC was used as a
building blocks.185 Owing to the uniform distribution and strong binder material to integrate with Li4Ti5O12 and carbon fibers to
adhesion of the silicon nanoparticles to the 3D conductive CNT/ fabricate flexible electrodes for LIBs.195 Even a small amount of
NFC network, the electrodes exhibited good energy storage per- NFC (2 wt%) can be used to prepare the Li4Ti5O12 electrode,
formances with specific capacities of up to 800 mA h g 1 (based which could meet the demands for high gravimetric energy
on the weight of the whole electrode) and good cycling perfor- density applications when a low C rate is acceptable. A full cell
mances. Silicon can also be integrated with CNT/NFC network by assembled using the Li4Ti5O12/carbon fiber/NFC as a negative
deposition of a thin layer of silicon on the NFC/CNT nanopaper electrode and LiFePO4/carbon fiber/NFC as a positive electrode
aerogels through a plasma-enhanced CVD method (Fig. 12d–f).186 exhibited a stable cycling performance with the specific
The open channels of the nanopaper aerogels allow for electrolyte capacity of approximately 125 mA h g 1 after 20 cycles at
accessibility to the surface of silicon. The aerogels performed 0.1C, and a high energy density of approximately 90 W h kg 1
well as anodes with a stable capacity of 1200 mA h g 1 for (for Li4Ti5O12-based batteries). Flexible single-paper LIBs were
100 cycles tested in half-cells. developed by Leijonmarck et al. through sequential filtration of
Other active material such as Li4Ti5O12 has also been water dispersions containing the negative electrode (consisting
integrated with NFC and CNT to prepared flexible paper of graphite, Super-P carbon, and NFC), the separator (consisting
electrodes. The hybrid films had a dual-layer structure consisting of NFC and SiO2), and the positive electrode (contained LiFePO4,
of Li4Ti5O12/CNT/NFC and CNT/NFC.194 The CNT/NFC layer with Super-P carbon, and NFC) (Fig. 12g and h).187 The resulting
a thickness of approximately 10 mm was utilized as a current paper LIB was thin and strong and had good cycling perfor-
collector foil, which reduced the total mass of the electrode while mances. The energy density of the full paper battery at C/10 was
keeping the same areal loading of the active materials. The 188 mW h g 1.
flexible paper-electrodes showed high rate cycling performance, Overall, NFC/BC display great potential for the fabrication
and the specific charge/discharge capacities were up to of flexible LIBs because of their high aspect ratio, web-like
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entangled structures, and high mechanical strength. However, 100 cycles under 100 mA g 1. In addition, the hybrid aerogel
most electrode materials reported so far have been synthesized electrodes exhibited good rate capability. Even at 1 A g 1, a
simply by mixing the active materials with nanocellulose, which specific capacity of approximately 380 mA h g 1 was obtained
leads to relatively low interfacial interactions. Optimizing the on the basis of the total electrode weight, which is higher than
interfaces between the NFC/BC and the active materials using the theoretical capacity of graphite. The high specific capacity
covalent or noncovalent techniques should be considered for and good cycling stability of the carbon hybrid aerogels were
improving the interface interactions, to achieve electrodes/LIBs mainly attributed to the well-dispersed active nanoparticles,
with appropriate and effective mass loading, high flexibility, interconnected conductive carbon nanofibers creating efficient
mechanical strength, and good electrochemical performance. electron conduction pathways at the whole electrode scale, and
The integration of active materials into NFC/BC networks using numerous interconnected voids facilitating the diffusion of
other novel techniques such as ALD or CVD is also suggested. lithium ions.
In summary, the high specific surface area, high electrical
5.2. Nanocellulose-derived carbon materials conductivity and porous structure of the nanocellulose-derived
Nanocellulose-derived carbon materials can be directly used as carbon materials lead to high performances of the carbon
electrodes for LIBs. The utilization of KOH activated BC-derived electrodes for LIBs. Integration with active materials can further
carbon aerogels as anodes for LIBs can deliver a specific improve the electrochemical properties. More attention should
capacity of over 857.6 mA h g 1 after 100 cycles at 100 mA g 1 be paid to the integration of nanocellulose-derived carbon and
and retain a capacity of 325.4 mA h g 1 even cycled at 4 A g 1.189 active materials with high theoretical capacity, such as SnO2 and
The good lithium storage performance of the carbon aerogels Ge, in a rational manner. The morphology and crystallization
can be attributed to its hierarchical micropore–mesopore struc- of active materials anchored on carbon materials should be
ture and high surface area, which can enhance the contact area carefully controlled during the fabrication process, and the
of the electrode–electrolyte, decrease the diffusion resistance of interface interactions between these active components and
the lithium ions, shorten the diffusion length of the lithium electrolytes should also be considered. In addition, the construc-
ions, and provide a solid and continuous pathway for electron tion and optimization of hierarchical micro-/mesoporous struc-
transport. To further improve the electrochemical properties, active tures of nanocellulose-derived carbon materials through pore
materials have been integrated with nanocellulose to develop engineering techniques is expected to introduce additional and
composites for carbonization. Li et al. reported the fabrication suitable positions for lithium storage and shorten the diffusion
of microfibers with a conductivity of 649 60 S cm 1 through a length for ion and charge transport.
wet-spinning method to prepare well-aligned NFC/GO hybrid
fibers followed by carbonization (Fig. 13a–e).190 GO acted as a 5.3. Nanocellulose-derived separators
template for NFC carbonization, which changed the morphology The separator in a LIB prevents the direct contact between the
of the carbonized NFC from microspheres to sheets while positive and negative electrodes while serving as the electrolyte
improving the carbonization of NFC. The as-prepared fibers reservoir to enable the transportation of lithium ions between
were demonstrated as lithium ion battery anodes, with a stable the two electrodes.198 The separator is not directly involved in
discharge capacity of 312 mA h g 1. A carbon hybrid film was any cell reactions, but its structure and properties play a critical
fabricated by integrating NFC with Li4Ti5O12 and CNTs through role in determining the LIB performance, including cycle life,
a papermaking method followed by carbonization (Fig. 13f).196 safety, energy density, and power density by influencing the cell
Owing to the uniform distribution and immobilization of Li4Ti5O12 kinetics. Because nanocellulose-based paper/film is hydrophilic
into the interpenetrating carbonized NFC/CNT conductive network, and exhibits excellent mechanical/thermal properties, utilizing
the carbonized paper anode displayed favorable transport behavior the nanocellulose-derived paper/film as a separator for LIBs has
of the lithium ion, and delivered a reversible discharge capacity gained more interest.
of 160 mA h g 1 and remained at 140 mA h g 1 after 10C with a An NFC film was obtained from densely packed NFC that
Coulombic efficiency of nearly 100%. Nanocellulose-derived exhibited high strength and thermal stability, and was electrolyte-
carbon materials can be employed as versatile conductive porous philic. Therefore, the NFC separator imparted substantial
scaffolds to support active anode materials. SnO2 nanoparticles,191 improvement in the ionic conductivity, electrolyte wettability,
Ge nanoparticles,191 amorphous Fe2O3,197 Fe3O4 nanoparticles192 and thermal shrinkage, as compared with that of the commer-
(Fig. 13g and h) and MoS2 nanoleaves,193 have been successfully cialized PP/PE/PP separators.199 The cladophora NFC separators
synthesized on nanocellulose-derived carbon scaffolds through an have a typical thickness of approximately 35 mm, an average pore
in situ growth method. Wang et al. demonstrated the utilization of size of approximately 20 nm, a Young’s modulus of 5.9 GPa,
BC-derived carbon aerogels as scaffold to support the in situ and an ionic conductivity of 0.4 mS cm 1 after soaking into
assembly of active SnO2 and Ge nanoparticles (Fig. 13i–n).191 1 M LiPF6 ethylene carbonate:diethyl carbonate electrolyte.200
The SnO2 and Ge nanoparticles were uniformly immobilized The NFC separators were thermally stable at 150 1C and were
onto the BC-derived carbon nanofiber surface. The carbon electrochemically inert in the potential range between 0 and
hybrid aerogels showed high specific capacity and good cycling 5 V vs. Li+/Li. A LiFePO4/Li cell containing a NFC separator
stability. The BC-derived carbon–SnO2 hybrid aerogels retained showed good cycling stability with 99.5% of capacity retention
a reversible capacity of approximately 600 mA h g 1 even after 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 because the nanocellulose is usually densely packed within the
layer. The as-fabricated redox-active separator can be used to thin separators. A porous structure with high tortuosity is
enhance the capacity of LIBs.202 expected to prevent the growth of dendritic lithium. Therefore,
Recently, Lee et al. pioneered the development of new kinds efficient pore engineering techniques are needed to adjust
of NFC-based separators. A heterolayered mat battery was the pore structures and sizes as well as the porosity of the
fabricated based on a unitized separator/electrode assembly nanocellulose separators. The integration of nanocellulose
(SEA) architecture (Fig. 14a–c).203 The unitized SEAs consisted membranes and other type of membranes such as electrospun
of NFC separators and solely SWCNT-netted electrode active nonwoven mats should be considered to exploit the synergy
materials (LiFePO4 (cathode) and Li4Ti5O12 (anode) powders effect of the beneficial influences of two or multiple layers.
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- 6. Other batteries
functional roles as electron conductive additives, binders,
current collectors and also non-Faradaic active materials. The 6.1. Lithium–sulfur batteries
SEA allowed significant improvements in the mass loading Li–S batteries have received increasing attention recently because
of active materials, electron transport pathways, electrolyte they can offer high theoretical gravimetric (2500 W h kg 1) and
accessibility, and misalignment-proof of separator/electrode volumetric (2800 W h L 1) energy density and 1 order of
interface. The batteries fabricated by stacking anode SEA and magnitude higher capacity (1675 mA h g 1) than that of
cathode SEA exhibit advances in the electrochemical perfor- conventional LIBs.9,10,206–210 In addition, elemental sulfur is
mances, shape flexibility, and safety tolerance. environmentally friendly, cheap, and abundant, which makes
Using a similar NFC separator in batteries, the electrode was Li–S batteries a particularly attractive and low-cost energy
further modified by using NFC/MWCNT-intermingled hetero- storage device. However, the practical application of Li–S
nets embracing electrode active powders (NM electrodes). The batteries still faces several challenges. First, the volume
multi-stackable NM electrodes were assembled with a NFC changes of sulfur particles during electrochemical cycles lead
separator, leading to a single-unit hetero-nanonet paper cell to structure changes of the active materials and cause low
(composed of one NM cathode/one NFC separator/one NM capacity. Second, sulfur and Li2S are both insulating, resulting
anode) (Fig. 14d and e),204 which provided an increase in the in sluggish electrochemical kinetics. Third, polysulfides are
energy density (226 W h kg 1 at 400 W kg 1 for LiNi0.5Mn1.5O4/ easy to dissolve in the electrolyte, which is the main cause
graphite system). The batteries were flexible and would be of the ‘‘shuttle phenomenon’’.206,208 To solve the problems
folded to fabricate paper crane batteries through an origami mentioned above, various efforts have been made to design and
folding technique. By considering the unwanted byproducts in develop novel electrodes, separators, and electrolytes. Recently,
electrolytes, such as manganese ions (Mn2+) dissolved from several types of nanocellulose materials have been developed to
lithium manganese oxide electrode materials and hydrofluoric construct high performance Li–S batteries, mainly based on
acid (HF) generated by side reactions between residual water their intrinsic structures and properties.
and lithium salts, a heterolayered nanomat-based hierarchical/ Nanocellulose can be integrated with active materials to
asymmetric porous separator was developed.205 The separator fabricate hybrid electrodes for Li–S batteries. Owing to its high
was composed of a terpyridine (TPY)-functionalized NFC nano- aspect ratio, entangled networks, and high abundance hydroxyl
porous thin mat as the top layer and an electrospun polyvinyl- groups on the surfaces, NFC was developed as a flexible building
pyrrolidone (PVP)/polyacrylonitrile (PAN) macroporous thick mat block to fabricate freestanding and sandwich-structured cathode
as the support layer (Fig. 14f–m). The hierarchical/asymmetric materials with high areal mass loading for long-life Li–S batteries
porous structure of the heterolayered nanomat was rationally (Fig. 15a–e).211
designed by considering the trade-off between the leakage Sulfur was impregnated in N-doped graphene and constructed
current and the ion transport rate. The TPY (to chelate Mn2+ as a primary active material, which was further welded in the NFC/
ions) and PVP (to capture hydrofluoric acid)-mediated chemical CNT framework. Interconnected NFC/CNT layers on both sides of
functionalities bring a synergistic coupling in suppressing the active layer were uniquely synthesized to entrap polysulfide
Mn2+-induced adverse effects, thus enabling a substantial species and supply efficient electron transport. The synergistic
improvement in the high-temperature (60 1C) cycling performance effects of the physical encapsulation by carbonaceous materials
(capacity retention B80% after 100 cycles) far beyond that (graphene and CNT/NFC fibers) and chemisorption for lithium
attainable with conventional membrane technologies (5% for polysulfides by chemical functionalization (hetero N-doping
a commercial PP/PE/PP separator). and hydroxyl groups) resulted in good electronic conductivity
Overall, separators constructed with nanocellulose as building and suppression of polysulfide dissolution and migration. The
blocks display high wettability for the electrolyte, are extremely rationally designed structure endowed the electrode with high
thin with strong mechanical strength, are electrochemically, specific capacity and good rate performance. The electrode with
structurally, and thermally stable, and have a porous structure, an areal sulfur loading of 8.1 mg cm 2 exhibited an areal
which makes them promising candidates for LIBs. Precisely capacity of B8 mA h cm 2 and an ultralow capacity fading of
controlling the pore structures and sizes is still challenging 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 and avoid structural collapse upon carbonization) (Fig. 15f).215
sulfur to fabricate a flexible sulfur cathode for Li–S batteries.212 A synergistic effect from N and S heteroatoms modified the
The as-prepared 3D carbon nanofiber networks exhibited high electron density distribution of the host substrate, leading to
electrical conductivity and good mechanical stability. The stronger polysulfide binding than that for non-doped or N
macroporous structure of the carbon aerogels contributed to single-doped carbons. Ab initio calculations based on density
a high sulfur loading of 81 wt% through sulfur precipitation functional theory revealed the strong interactions between Li+
from the CS2 solution. The sulfur species wrapped around the and doped N atoms (Li–N) as well as the polysulfide anions and
carbon nanofibers were well dispersed. Even at such a high doped S atoms (S–S) (Fig. 15g–j). The electrical conductivity of
loading, the S/carbon aerogel composite still contained suffi- N,S-codoped carbon was also greatly improved compared with
cient free space to accommodate the volume expansion of sulfur nondoped carbon, favoring high-rate kinetics. Using this dual-
during lithiation. An ultralight and thin BC-derived carbon doped carbon as sulfur host, the sulfur electrode was able to
aerogel interlayer was inserted between the sulfur cathode and deliver a high capacity of 1370 mA h g 1 at C/20 and charge/
separator to provide an extra conductive framework and some- discharge for 1100 cycles at 2C with a very low capacity fading of
what adsorb the migrating polysulfides. The carbon aerogel 0.052% per cycle. This was attributed to the high pore volume
interlayer can also act as an additional collector for sulfur and and surface area of the host that can provide sufficient active
thus could prevent the over-aggregation of insulated sulfur on sites for chemically adsorbed lithium polysulfides.
the cathode surface. With a thin carbon aerogel interlayer, the Nanocellulose-derived hybrid materials and carbon hybrid
flexible S/carbon aerogel cathode exhibited a high discharge materials with a rational structure design can be used as
capacity (1134 mA h per gSul at 200 mA g 1), long-term cycle separators or electrolytes for Li–S batteries. BC-derived carbon
stability (700 mA h per gSul at 400 mA g 1 over 400 cycles), and materials were mixed with TiO2 to form a composite slurry and
good rate capability. To further improve the electrochemical coated on one side of a separator.216 The carbon materials served
capability, heteroatom doping has attracted attention because as an upper collector and supplied strong physical adsorption of
it is an effective way to tailor the electronic and chemical polysulfides, whereas the TiO2 can chemically adsorbed poly-
properties of the carbon host. N is the most extensively studied sulfides. Thus, the carbon materials/TiO2 modified separator
heteroatom, which could improve the electron conductivity and was efficient restraining the shuttle effect of Li–S batteries. Cells
strongly adsorb polysulfides, endowing a good rate capability with carbon materials/TiO2 modified separator showed an initial
and remarkable cycling stability. N-Doped carbon materials have discharge capacity of 1314 mA h g 1 at 0.2C, and the capacity
been prepared from carbonization and activation (with KOH) the retention was 1048.5 mA h g 1 after 50 cycles. During the rate
aerogels derived from BC hydrogels and its residual medium test, Li–S cells delivered a discharge capacity of 537.1 mA h g 1
with enriched carbon and nitrogen. The S/carbon (with N-doped) at 2C. Nair et al. prepared NFC-laden composite polymer electro-
composites were synthesized through a melt-diffusion method lytes using a thermally induced polymerization process.217 The
and used as the cathode material, which showed an initial NFC mainly acted as a reinforcing agent and provided an
discharge capacity of 1267 mA h g 1 and capacity retention of interpenetrated network for methacrylate-based polymer matrix
995 mA h g 1 after 500 charge/discharge cycles at a rate of 0.1C to fabricate opaque and self-standing polymer electrolyte mem-
with a Coulombic efficiency of 99.0%.213 Recently, Li et al. branes. The activated membrane in the liquid electrolyte showed
developed a N,O-codoped carbon nanofiber aerogel by pyrolysis a high conductivity (41.2 mS cm 1) and a stable interface
a BC aerogel in an ammonia atmosphere.214 O was doped owing towards lithium metal. The final cell with a Li/activated polymer
to the oxygenated species in the cellulose that remained in electrolyte separator/sulphur-activated carbon cell showed good
the aerogel after pyrolysis, whereas N was originated from the cycling stability at above 700 mA h g 1 even at 1C rate and a
N-containing compounds left by culture media and secretions Columbic efficiency of 499% at ambient temperature. The stable
and the ammonia gas used during pyrolysis. The oxygen in the cycling profile was attributed to the reduction of the migration
carbon nanofiber aerogel could further enhance the polysulfide of polysulphide towards the anode by the entrapment of NFC in
retention capacity owing to improved hydrophilicity of the the polymer matrix.
surface. The N,O-codoped carbon nanofiber aerogel was Overall, nanocellulose-derived hybrid materials and carbon
employed to a gel-based sulfur cathode, which simultaneously materials have the potential to be used as electrodes, separators
achieved both high sulfur content and high sulfur loading. With and electrolytes for high performance Li–S batteries. However,
a sulfur loading of 6.4 mg cm 2 and a sulfur content of 90% in challenges still exist such as how to achieve both high content
the whole electrode (including current collector) level, a capacity and high loading of active materials in the same cathode while
of 943 mA h g 1 was achieved, which corresponded to an areal still preserving the flexible, high mechanical strength, and
capacity of 5.9 mA h cm 2. CNC was also utilized as a carbon excellent electronic conductivity of the nanocellulose and
source for dual-atom doping to prepare carbon materials with nanocellulose-derived materials. To alleviate the polysulfide
hierarchical porous structures. N,S-Codoped carbons with a high shuttle with a stable and persistent effect is still challenge for
pore volume and surface area were fabricated from the liquid- the nanocellulose-derived electrodes and separators. Thus, the
crystal-driven self-assembly of CNC coated with polyrhodanine rational designing and optimization of hierarchical porous
followed by pyrolysis and etching of silica (silica precursors were structures and surface/interface properties of nanocellulose-
added into the dispersion to provide a spacer between particles derived hybrid materials and carbon materials is critical for
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constructing high-performance Li–S batteries. Progress in this direc- performance (146.5 mA h g 1 at 1 A g 1), and good cycling
tion is expected to be accomplished through a synergistic combi- stability (148.8 mA h g 1 at 500 mA g 1 over 400 cycles).
nation of theoretical calculations and experimental approaches. Compared to single-atom doping, dual-atom doping in carbon
could exploit the synergistic effects of the advanced features of
6.2. Sodium-ion batteries the two heteroatoms, which takes advantage of the additionally
Over the last few years, NIBs have attracted increasing attention created defect sites and electronic conductivity for sodium storage.
as an important source of energy storage devices largely owing to Recently, Yu et al. synthesized N,O-dual doped carbon networks by
the fact that Na is the sixth most abundant element in the earth’s using the pyrolysis of BC/PANI and subsequent activation with
crust and it is inexpensive and environmentally friendly for KOH (Fig. 16a and b).227 BC acted as a 3D scaffold to deposit PANI
large-scale energy storage.8,218–223 The working principle of NIBs but also formed a conductive carbon network during the carboni-
is similar to that of LIBs. However, several good anode materials zation, whereas the PANI formed large amounts of small N,O-dual
used in LIBs such as graphitic carbon materials exhibited poor doped carbon particles along the interconnected nanofibers in situ.
storage properties for NIBs, mainly because the radius of Na+ is The obtained carbon networks exhibited a high specific capacity
B55% larger than that of Li+; most materials do not possess host (798 mA h g 1), long cycle life (545 mA h g 1 at 100 mA g 1 after
frameworks with larger interstitial spaces for Na ion insertion/ 100 cycles), and high rate capability (240 mA h g 1 at 2 A g 1 after
extraction. Besides the kinetic issue, the larger Na+ radius is 2000 cycles). The carbon materials with 3D well-defined porosity
also relevant for possible structural change during insertion or and N,O-dual doped induced active sites, contributing to the
extraction. Thus, the development of appropriate electrode enhanced sodium storage.
materials is critical for improving the performance of NIBs. B,N-Dual doped carbon materials were developed by fully
Recently, nanocellulose-derived materials have gained interest infiltrating NH4HB4O7H2O into the BC pellicle followed by
for use as electrodes in NIBs. carbonization (Fig. 16c and d).228 The B,N-dual doping created
Nanocellulose can be integrated with active materials to synergistic effects to enlarge the carbon layer spacing for Na+
fabricate electrodes for NIBs. Li et al. reported the use of insertion, and improved the electrochemical activity as well as
TEMPO-oxidized NFC as a dispersant to efficiently disperse electronic conductivity. The obtained carbon materials deliv-
and form a hybrid with 2D materials such as molybdenum ered a specific charge capacity of 581 mA h g 1 at 100 mA g 1
disulfide (MoS2) in aqueous solution.224 The as-prepared NFC/ after 120 cycles and good cycling stability (277 mA h g 1 at
MoS2/CNTs composite films with a weight ratio of 16.5 : 67 : 16.5 10 A g 1 after 1000 cycles). In addition to NFC/BC with a high
can act as flexible electrodes for NIB anodes. The first cycle aspect ratio, Zhu et al. reported the carbonization of short and
discharge capacity was 147 mA h g 1, which was higher than that high specific surface area CNCs at 1000 1C for use in NIBs.229
of the MoS2/CNTs composite anode, even though it had a lower During the carbonization, the CNC was transformed into
MoS2 content. The Coulombic efficiency of the first cycle was porous carbon with an increased short-range ordered lattice
43.8% and increased to 89.7% by the third cycle. and percolated carbon nanofiber (Fig. 16e–h), which exhibited
Nanocellulose-derived carbon materials display advantages a good structure and conductivity for NIB anodes. A starting
such as chemical and thermal stability, high electrical conduc- capacity of 340 mA h g 1 at 100 mA g 1 was achieved, which
tivity, as well as high Na-storage capacity for the development of maintained 88.2% capacity over 400 cycles.
anode materials for NIBs. Luo et al. reported the synthesis Overall, nanocellulose has potential to be developed as an
of carbon nanofibers directly from NFC through a pyrolysis electrode material for NIBs. Nanocellulose can form a hybrid
process.225 The unique morphology of the carbon nanofibers with active materials or be converted to 3D interconnected
facilitated highly reversible ion migration and provided plenty of carbon materials and be further functionalized by doping with
contact area between the electrode and the electrolyte. Thus, when heteroatoms or integrated with active materials. Compared with
utilized as an anode material for NIBs, the carbon nanofibers LIBs, the larger size of sodium ions hampers the kinetics of
delivered not only a high reversible capacity of 255 mA h g 1 at the electrochemical reactions. Therefore, reversible electrodes
40 mA g 1 and a rate capability of 85 mA h g 1 at 2000 mA g 1, derived from nanocellulose-derived materials need to possess
but also a good cycling stability of approximately 180 mA h g 1 large enough channels and/or interstitial sites. The challenge in
at 200 mA g 1 over 600 cycles. To further improve the electro- the future is to design and construct novel hierarchical 3D
chemical performance, engineering the 3D porous carbon fibrous porous structures with appropriate space for Na storage,
materials by heteroatom doping was conducted. Zhang et al. short diffusion distance for ions, high Na+ diffusion coefficients,
synthesized core-sheath structured carbon nanofiber@N-doped and fast electron transport from various types of nanocellulose
porous carbon (CNF@NPC) composite through carbonization of through multiple synthesis strategies.
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 7. Summary and outlook
with a high surface area and an appropriate N doping improved
the reversible capacity. When utilized as an anode material, The past few years have witnessed significant progress in
the CNF@NPC exhibited a high reversible specific capacity the development of nanocellulose for electrochemical energy
(240 mA h g 1 at 100 mA g 1 over 100 cycles), high rate storage owing to its exceptional structures and properties
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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 (5) developing carbon-based porous materials and carbon hybrid
the recent advances in this area, with a particular focus on the materials, (6) constructing multiple kinds of materials or devices
structures and characteristics of nanocellulose within the using various kinds of nanocellulose and their hybrids as building
cell walls of cellulose sources, the fabrication, structural and blocks. The nanocellulose-derived materials exhibit advantages
functional design of nanocellulose, and the application of the for various electrochemical energy storage applications, including
nanocellulose-derived materials for advanced energy storage supercapacitors, LIBs, Li–S batteries, and NIBs.
systems. Thanks to the efforts of many research groups, a rich Although nanocellulose has been successfully developed
variety of nanocellulose materials with various structures and to construct a series of advanced materials/devices for high
surface chemistry performance have been developed from various performance energy storage devices, there are some issues that
sources using multiple fabrication strategies (Table 1),77,82,86–91 need to be addressed in the future.
which provides plenty of building blocks for further development (1) Large-scale fabrication. Although the fabrication of nano-
of high-performance energy storage materials and devices. cellulose has become mature during the past 10 years and mass
Owing to the nanoscale dimension, high specific surface area, production of nanocellulose has been achieved by several
high relative crystallinity, reactive surfaces containing hydroxyl research institutions and companies, the quality such as the
groups, entangled web-like structures, and advantageous structures, nanofibrillation degree, and surface chemical pro-
mechanical and thermal properties, nanocellulose can be perties of nanocellulose is still quite different compared with those
utilized for (1) constructing self-standing and high strength fabricated at a laboratory scale. Thus, it is still difficult to perform
electrodes or separators, (2) integration with other electrochemical large-scale production of nanocellulose with high quality and
active materials, (3) developing flexible substrates/scaffolds uniformity, especially for the large-scale production of high aspect
for flexible devices, (4) designing multifunctional separators, ratio and individualized NFC. We should pay more attention on
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developing and optimizing mechanical processing equipment such (4) Flexibility. Forthcoming smart electronics era necessitates
as large capacity high pressure homogenizer, beads mill, twin screw the development of advanced flexible energy storage devices with
extruder, and high-intensity ultrasonicator to achieve the mass environmentally friendly characteristics, lightweight, low cost,
production of high quality nanocellulose for sustainable supply and advantageous energy storage performance. Nanocellulose
for energy storage development and other applications. Further- meets all the above-mentioned critical requirements and can be
more, limited by the preparation technology and apparatus such as utilized as a building block to construct flexible substrates/
vacuum filter, supercritical dryer, and tube furnace, it is still a big scaffolds or as carbon precursors to fabricate light and flexible
challenge to perform continuous and large-scale fabrication of energy storage devices with shape-conformability, aesthetic
nanocellulose-derived electrodes/separators with a large size for diversity, and advantageous mechanical properties. For the
energy storage devices. separators and electrodes derived from nanocellulose or nano-
(2) Surface/interface engineering. Surfaces and interfaces play cellulose composites, the mechanically robust and entangled
crucial roles in the fabrication and performance of nanocellulose- networks of nanocellulose should be preserved during the whole
derived energy storage materials/devices. Surface/interface fabrication and utilization process. For the nanocellulose-
engineering can induce novel physicochemical properties and strong derived carbon electrodes, the hydrogen bond interaction
synergistic effects for nanocellulose and nanocellulose-derived between the nanocellulose should be removed and the inter-
materials, providing new and efficient strategies to enhance the connected network structures of the nanocellulose should be
energy storage activities. Thus, we should exploit the surface atomic carefully preserved during carbonization, which would ensure
or molecular engineering (e.g., heteroatom-doping, chemical robust mechanical properties with high flexibility of the carbon
modification) to directly utilization or chemical modification electrodes. Furthermore, excellent conductivity and a high
of the surface structures and chemistry of nanocellulose and capacity should be achieved for nanocellulose-derived electro-
nanocellulose-derived carbon materials, and further integrate des by integration with active materials without sacrificing
the materials with other active materials through various inter- the structural integrity and flexibility. It is also necessary to
face engineering routes such as physical and chemical treatment integrate the electrolytes/separators, electrode materials, current
related to weak (e.g., hydrogen bonding, van der Waals inter- collectors, and packaging to maximize the synergistic effect of
action) or strong (e.g., covalent bonding) effects. More alternative the composite structures and utilization of the flexibility derived
methodologies can be inspired from the success work of other from the nanocellulose entangled networks, which make the
similar materials such as polymeric materials.230 We should devices simultaneously exhibit high flexibility and high energy
develop surface/interface engineering technique to provide storage performance.
nanocellulose-derived energy storage materials/devices with (5) New materials and new applications. As nanocellulose
tunable micro-, nano- and even atom-scale structures, tailorable can be fabricated from various sources using different prepara-
physicochemical properties, excellent electronic conductivity, tion methods, new materials/devices for energy storage should
flexibility, advantageous mechanical properties, physical and be explored using different types of nanocellulose and their
chemical stability as well as high energy storage performances. combinations as building blocks, based on the sizes, struc-
(3) Pore engineering. The sizes and structures of the pores tures, and surface chemical performance of nanocellulose. For
and the porosity of the nanocellulose-derived materials critically example, optically transparent and flexible electrodes can be
affect their performance. The pore size of materials can range developed by the integration of TEMPO-oxidized NFC with
from the nanometer to micrometer scale, depending on the transparent conductive materials. Chiral nematic mesoporous
structure of nanocellulose and the active materials as well as the carbon electrodes can be developed by using sulfuric-acid-
processing methods. For the electrodes, hierarchical micropore– hydrolyzed CNC as a template. Investigation of new materials
mesopore structure should be developed to improve the contact as well as the fabrication strategies could open up new oppor-
area of the electrode–electrolyte, decrease the diffusion resis- tunities for a wide range of applications. To date, nanocellulose
tance of electrolyte ions, and shorten the diffusion length of the and its derived materials have been widely used for super-
electrolyte ions. For the separator, the porosity and pore size of capacitors and LIBs, however, a few works were reported for
the nanocellulose film should be designed to achieve the elec- their application in Li–S batteries and NIBs. Moreover, some
trically isolate the electrodes but facilitate the ionic transport. new types of energy storage systems such as Mg(Al,Mn)-ion
However, it is still difficult to precisely control the pore struc- batteries have been rarely explored. Considering that nano-
tures and sizes of the nanocellulose-derived materials. There- cellulose and its derived materials are mechanically robust and
fore, pore engineering that can tune the pore size, especially at with structural, surface/interface chemistry adjustable, they can
the nanometer- and even the atom-scale level is highly desirable. be readily used as a green material solution for newly emerging
It is also suggested to get more inspiration from the research energy storage systems through customized control of their
experience of other similar polymeric materials,231,232 to opti- structure and characteristics.
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 Conflicts of interest
avoid the collapse of web-like structures of the nanocellulose-
derived materials throughout the whole life cycles. There are no conflicts of interest to declare.
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Acknowledgements 22 L. Hu and Y. Cui, Energy Environ. Sci., 2012, 5, 6423–6435.

23 L. Nyholm, G. Nystrom, A. Mihranyan and M. Stromme,
This work was supported in part by the National Natural Science Adv. Mater., 2011, 23, 3751–3769.
Foundation of China (No. 31400495; 51672055; 31770594), Young 24 T. H. Nguyen, A. Fraiwan and S. Choi, Biosens. Bioelectron.,
Elite Scientists Sponsorship Program by CAST (No. 2017QNRC001), 2014, 54, 640–649.
Ten Thousand Talent Program (No. W02020249), Funds supported 25 F. Sharifi, S. Ghobadian, F. R. Cavalcanti and N. Hashemi,
by the Fok Ying-Tong Education Foundation, China (No. 161025), Renewable Sustainable Energy Rev., 2015, 52, 1453–1472.
and Fundamental Research Funds for the Central Universities. We 26 J.-H. Kim, B. S. Shim, H. S. Kim, Y.-J. Lee, S.-K. Min,
would like to acknowledge Prof. Shigenori Kuga, Graduate School D. Jang, Z. Abas and J. Kim, International Journal of Preci-
of Agricultural and Life Sciences, The University of Tokyo, Japan, sion Engineering and Manufacturing-Green Technology, 2015,
for valuable suggestions and revision of the manuscript. 2, 197–213.
27 Y.-Z. Zhang, Y. Wang, T. Cheng, W.-Y. Lai, H. Pang and
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Nanocellulose: a promising nanomaterial for

advanced electrochemical energy storage

Wenshuai Chen received his BS Haipeng Yu was born in

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Sang-Young Lee is a professor Tong Wei received her PhD in 2003

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Fig. 2 Summary of the structural and property advantages of nanocellulose

(iv) Because of the nanometer scale, high specific surface

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Table 1 Categories, fabrications, structures and characteristics of nanocellulose

Schematic Representative SEM/ Surface chemical

Wood Chemical purification + grinder Hydroxyl groups 82

Wood Chemical purification + blender Hydroxyl groups 77

TEMPO-mediated oxidation + Hydroxyl, carboxylate,

Coconut milk, Secreted by

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agent for producing CNC. It can remove the amorphous area of

Sub- Nanocellulose Performance: capacity/energy CRa

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Sub- Nanocellulose Performance: capacity/energy CRa

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Chem. Soc. Rev., 2018, 47, 2837--2872 | 2845

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of 15.5 mW h g 1, and a specific power density of 1.5 W g 1

photonic interwelding of Ag nanowires was introduced onto the

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Electrochemical performance: capacity/rate

This journal is © The Royal Society of Chemistry 2018

Chem. Soc. Rev., 2018, 47, 2837--2872 | 2857

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Acknowledgements 22 L. Hu and Y. Cui, Energy Environ. Sci., 2012, 5, 6423–6435.

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