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Cellulose Nanomaterials www.small-journal.com

Cellulose-Based Nanomaterials for Energy Applications

Xudong Wang,* Chunhua Yao, Fei Wang, and Zhaodong Li

leads to a more and more serious envi­

Cellulose is the most abundant natural polymer on earth, providing a sustain- ronmental issue on electronic and plastic
able green resource that is renewable, degradable, biocompatible, and cost wastes. While paper is still mostly playing
effective. Recently, nanocellulose-based mesoporous structures, flexi­ble thin its traditional role currently, it is maybe
films, fibers, and networks are increasingly developed and used in photo- about the time that the plant-based mate­
rials stand out again to pay the debt that
voltaic devices, energy storage systems, mechanical energy harvesters, and
human civilization owes to the environ­
catalysts components, showing tremendous materials science value and ment and make our technology evolution
application potential in many energy-related fields. In this Review, the most more sustainable.
recent advancements of processing, integration, and application of cellulose Cellulose, as the most abundant natural
nanomaterials in the areas of solar energy harvesting, energy storage, and polymer on earth, provides a sustainable
mechanical energy harvesting are reviewed. For solar energy harvesting, green resource that is renewable, degra­
dable, biocompatible, and cost-effective.[1–3]
promising applications of cellulose-based nanostructures for both solar cells
It is directly generated from natural
and photoelectrochemical electrodes development are reviewed, and their plant such as wood, cotton, and hemp or
morphology-related merits are discussed. For energy storage, the discussion from microbes such as bacteria, algae, and
is primarily focused on the applications of cellulose-based nanomaterials in fungi. Among them, wood-origin cellulose
lithium-ion batteries, including electrodes (e.g., active materials, binders, and isc the most common one, and is usually
used in the form of wood pulp.[4] Chemi­
structural support), electrolytes, and separators. Applications of cellulose
cally, cellulose consists of linear chains
nanomaterials in supercapacitors are also reviewed briefly. For mechanical of repeating β-D-glucopyranose units
energy harvesting, the most recent technology evolution in cellulose-based covalently linked through β-1,4 glycosidic
triboelectric nanogenerators is reviewed, from fundamental property tuning bonds.[2] A large number of hydrogen
to practical implementations. At last, the future research potential and oppor- bonds exist intra- and intermolecularly
tunities of cellulose nanomaterials as a new energy material are discussed. and yield different configurations of cellu­
lose structure. The nanoscale structures of
cellulose (e.g., nanofibrils or nanocrystals)
offer a unique combination of proper­
1. Introduction ties including flexible surface chemistry, transparency, low
thermal expansion, high elasticity, and anisotropy. While most
Invention and utilization of paper marked an important mile­ study on cellulose were centered around cellulose-to-fuel con­
stone in human civilization. Such a revolutionary use of natural version, contemporary research recently began to address the
fibers brought in an affordable, abundant, and renewable sub­ functionalization and engineering of cellulose nanostructures
stance to human race, which significantly facilitated the heri­ for electronic and energy applications. With its unique struc­
tage and evolution of knowledge, technology, and humanity. tural and chemical features, cellulose can be assembled into
Today, as our technology entering a new era of information various nanoscale configurations to meet the design needs of
technology, materials innovation is experiencing an unprec­ the energy devices. Currently, nanocellulose-based mesoporous
edented pace of progressing. Machines, vehicles, computers, structures, flexible thin films, fibers, and networks are devel­
display panels, memory devices, batteries, solar cells, and oped and used in photovoltaic (PV) devices, energy storage sys­
numerous types of sensors are built everyday using advanced tems, mechanical energy harvesters, and catalysts components.
ceramics, metals, and plastics. The explosive advancement of Inclusion of nanocellulose in those energy-related devices
modern technology is bringing revolutionary changes to the largely raises the portion of eco-friendly materials and is very
human society in recent decades; meanwhile, however, it also promising in addressing the relevant environmental concerns.
Furthermore, cellulose manifests itself in the low cost and
Prof. X. Wang, C. Yao, Dr. F. Wang, Dr. Z. Li
large-scale promises. As the cellulose-related materials become
Department of Materials Science and Engineering more and more popular, many quality review articles have been
University of Wisconsin-Madison published.[2,5–7] Most of them, however, are still in the area of
Madison, WI 53706, USA processing cellulose molecule for chemical fuel production. A
E-mail: xudong@engr.wisc.edu few most recent ones begin to address contemporary applica­
The ORCID identification number(s) for the author(s) of this article tions such as cellulose-based electronics[8] and electronics from
can be found under https://doi.org/10.1002/smll.201702240.
wood-based materials.[9] To address the emergent applications
DOI: 10.1002/smll.201702240 of cellulose nanomaterials in energy-related areas, this review

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article discusses the most current advancements of processing,
integration, and application of cellulose nanomaterials in the
areas of solar energy harvesting, mechanical energy harvesting,
and energy storage.
2. Cellulose Nanostructures for Solar
Energy Harvesting
Solar energy-harvesting devices typically prefer high surface
area and good charge transport properties so that photons can
be effectively absorbed and converted into electrical energy.
3D mesoporous structures composed of cellulose nanofibrils
(CNFs) offer a very large surface area, and present mechanical
properties (e.g., Young’s modulus and tensile strength) com­
parable to other fibrous materials (e.g., carbon fibers and glass
fibers).[10] Therefore, CNFs are often considered as an attrac­
tive template/matrix for processing functional 3D nanostruc­
tures for photoelectrode development.[11] In addition, 3D CNF
network or compact CNF films could bring unique optical
properties that are beneficial to photon absorption. In this sec­
tion, promising applications of CNF-based nanostructures for
both solar cells and photoelectrochemical (PEC) electrodes
development are reviewed, and their morphology-related merits
are discussed.
2.1. Nanocellulose-Based Paper Substrate
for Solar Cell Development
Since cellulose intrinsically is an insulator, the most common
application of CNF in solar cell development is the transparent
substrate. In order to maximize the photon absorption, both
high optical transparency and high optical haze (the percentage
of light diffusely scattered from a transparent surface) are
desired for solar cell substrates. Regular paper substrates offer
good optical haze but typically have low transmittance.[12,13]
Therefore, organic solar cells built on paper substrates usu­
ally exhibited a fairly low power conversion efficiency (PCE,
<1.4%).[14–16] As for nanocellulose (e.g., CNF and cellulose
nanocrystal (CNC)), because their sizes are much less than
the wavelength of visible light, paper made from nanocellulose
could be highly transparent with significant scattering along
the light transport direction.[17] Thus, nanocellulose paper could
be an ideal substrate for supporting the photoactive compo­
nents of solar cells.
Hu et al. fabricated a carboxymethylated nanocellulose paper
and studied its optical properties and subsequent organic solar
cell application.[17] The nanocellulose paper (≈40 µm thick) was
fabricated by compressing carboxymethylated cellulose pulp in
a sheet-former at 70 °C and 1 bar. The as-fabricated nanocellu­
lose paper was highly transparent to a closely contacted object,
but was hazy when the object was ≈2 inches away due to sig­
nificant light scattering of the porous cellulose film (Figure 1a).
Angular reflection and transmittance revealed that the nano­
cellulose paper did not have strong angle-dependent reflection
and transmission, which is drastically different from regular
transparent substrates. This nanocellulose paper was then
applied as the substrate for organic bulk heterojunction solar
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Xudong Wang is a pro-
fessor in the department
of Materials Science and
Engineering at University
of Wisconsin-Madison. His
research focuses on studying
the growth and assembly
of nanoscale materials,
including 1D nanowires and
2D nanosheets, with applica-
tion potential in the areas
of nanogenerators and solar
energy conversion. His research group first time demon-
strated the functionalization of cellulose nanomaterials for
triboelectric nanogenerator development.
Chunhua Yao received her
bachelor’s degree in Wood
Science and Engineering
from Central South University
of Forestry and Technology,
China. She is currently pur-
suing her Ph.D. under super-
vision of Prof. Xudong Wang
in Department of Materials
Science and Engineering,
University of Wisconsin-
Madison. Her research
focuses on the development of functional materials and
energy-harvesting devices from bio-based materials.
cells that were composed of poly(3,4-ethylenedioxythiophene):
poly(styrene sulfonate) (PEDOT:PSS), poly(3-hexylthiophene)
(P3HT), and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM).
Although the optical property of the nanocellulose paper sub­
strate was superior, the PV performance of the solar cell did
not excel due to the large sheet resistance of indium tin oxide
(ITO) coating and other fabrication-related issues. As shown in
Figure 1b, the short-circuit current (Jsc) and open-circuit voltage
(Voc) were ≈2.4 mA cm−2 and of ≈0.4 V, respectively, revealing a
PCE of only ≈0.2%.
Zhou et al. demonstrated organic solar cells on CNC
substrates which yielded higher efficiencies and excellent
rectification behaviors (Figure 1c,d).[18] The CNC substrates
offered similar optical properties as the CNF papers, while the
better performance was mainly attributed to the utilization of
highly conductive Ag electrode and better fabrication strategy.
However, the low transmittance of the Ag electrode capped the
efficiency at ≈2.7%. Zhou et al. further fabricated such organic
solar cells on recyclable CNC substrates and the efficiency
reached almost 4.0% by using polyethylenimine-modified Ag
electrode. The dry lamination transfer process of PEDOT:PSS
to the CNC substrate could avoid the damage of cellulose from
typi­cal aqueous-based processes, and thus led to very low reverse
saturation current and good diode rectification of the device.[19]
Most recently, Fang et al. further improved the nanocellulose
paper using a tetramethylpiperidine-1-oxy (TEMPO)-oxidized
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Figure 1.  Solar cells built on nanocellulose-based paper substrate. a) Photographs of a transparent nanocellulose paper made from carboxymethyla-
tion of softwood cellulose fiber showing the scattering effect. b) I–V curve of an organic solar cell built on the nanocellulose paper. Inset is a photo
of the organic solar cell. Reproduced with permission.[17] Copyright 2013, Royal Society of Chemistry. c) Schematic illustration and photograph of an
organic solar cell built on CNC substrate. d) I–V curve of the organic solar cell. Reproduced with permission.[18] Copyright 2013, Creative Commons
Attribution 4.0 International License. e) Photograph showing the high transparency and high haze of a nanocellulose paper obtained from TEMPO
oxidization. f) PV performance of organic solar cells built with and without this nanocellulose paper. Reproduced with permission.[13] Copyright 2013,
American Chemical Society.

cellulose as the building block. This paper had a high fragment
content and fewer hollow structures, which led to a higher
packing density and thus exhibited excellent optical transpar­
ency (≈96%) and ultrahigh haze (≈60%) (Figure 1e).[13] By
simply laminating a piece of such paper on an ITO glass, the
haze effect enhanced the incident angle independency of the
solar cell device. When the angle of the incident light was larger
than 7°, the photocurrents of the nanocellulose paper-attached
solar cell started to excel. Over ≈15% photocurrent improve­
ment was observed within the incident angle range of 60°–87°
(Figure 1f), which was a result of the reduced light reflection
and broadened angular distribution of incident light due to the
haze effect of the nanocellulose paper.[13]
In general, nanocellulose paper can offer enhanced photon
absorption at oblique incidence, therefore they are superior in
collecting ambient light with greater effectiveness compared
to regular glass substrates. The optical properties are directly
related to the fiber length, packing density, and processing
techniques. With further material and processing optimization,
nanocellulose papers may take a dominating role in fabricating
high-efficiency solar cells.
2.2. CNF-Templated Mesoporous Structure
as Solar Cell Electrodes
The very large surface area offered by the CNF network is a
general structural merit to achieve high photocurrent density
in solar cell design. Nevertheless, due to the intrinsic insulating
property of CNF, using CNF networks as the scaffold for solar

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cell electrode development was less popular compared to sub­
strate renovation. The mostly practiced strategy is to use CNF
networks as a template to fabricate mesoporous structure of
a functional material that is photoactive and conductive. TiO2
was frequently used to coat CNF template, followed by high-
temperature calcination to remove the CNF template, forming
a hollow nanofiber network with a very high porosity.[20] Due
to the excellent hydrophilicity of CNF, aqueous solution-based
approaches have been found very effective in producing a uni­
form coating with tens of nanometer thickness (Figure 2a).
Such a crosslinked TiO2 network yielded improved electron
transport properties than mesoporous films assembled from
TiO2 nanoparticles. Therefore, the CNF-templated TiO2
nanofibers could provide structural advantages in photon
interaction and charge transport. In a typical demonstration,
the nanofibers were directly cast on a transparent conducting
glass substrate with designed thickness to serve as the photo­
electrode of a dye-sensitized solar cell (DSSC). It was expected
that the high surface area could largely improve the loading of
dye molecules and thus yield high photocurrent density and
high incident photon-to-current conversion efficiency. Com­
pared to nanoparticle-based DSSC with the same thickness,
the nanofiber-based devices, however, showed a slightly lower
photocurrent density but higher open-circuit voltage (Voc,
Figure 2b). The relatively low roughness factor of the fiber
network was believed to be responsible for the lower current
density, which was not odd in many fiber- or nanowire-based
electrodes. The higher Voc of fiber-based DSSC was attributed
to the higher photoelectron density (1017 cm−3) compared to
the nanoparticle electrode (Figure 2c). The higher electron den­
sity at a constant Voc is a result of the lowering of the conduc­
tion band.[20,21] By comparing the Voc difference at the same
photoelectron density, the recombination lifetime of electrons
(τrec) in the 6 µm-thick fibrous electrode was ≈3 times higher
than that of the nanoparticle-based photoelectrode (Figure 2d).
The TiO2 hollow fibers also exhibited 2–3 times shorter elec­
tron collection time (τn) compared to the TiO2 nanoparticles
networks with the same film thickness (Figure 2e). Although
no specific reason was given by the literature, better charge
transport property of the nanocellulose-templated TiO2 could
be attributed to the residue carbon in the TiO2 lattice, which
facilitated electron transport. These merits are beneficial to
solar cell performance. Further improving the surface area den­
sity (i.e., the nanocellulose packing density) without losing the

Figure 2.  Solar cell electrodes from CNF-templated TiO2 mesoporous structure. a) Scanning electron microscopy (SEM) image of TiO2 fibers template
by CNF networks. b) J–V characteristics of DSSCs based on fibrous photoanodes. c) Open-circuit voltage at different charge density levels for DDSCs
made of TiO2 nanoparticles or fibers. d) Electron recombination lifetime τrec and e) electron collection time τn extracted from transient open circuit
photovoltage. Reproduced with permission.[20] Copyright 2010, American Chemical Society.

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porosity could eventually raise the overall PV performance of
nanocellulose-templated solar cells.
2.3. Nanocellulose in PEC Cell Development
PEC water splitting is a promising strategy for directly con­
verting solar energy into hydrogen fuels.[22] It shares much
similarity with solar cell development, including rapid charge
generation and separation, large surface area for redox reac­
tions, and broadband light absorption.[11,23] Therefore, PEC
cells can also benefit from the structural merits offered by
nanocellulose-based 3D structures.[11,24–27] In addition, the
hydrophilic mesopores within the cellulose film could serve as
an ideal host matrix for the embeddment of the nanoparticle
catalysts with minimized agglomeration. As a representative
example, Ke et al. immobilized photoactive cadmium sulfide
(CdS) nanoparticles in mesoporous nanocellulose films by
sequentially immersing a nanocellulose film in CdCl2 solution
and Na2S solution.[25] Pt nanoparticles were then photochemi­
cally deposited on the CdS/cellulose nanocomposite film for
photocatalytic H2 evolution. The mesoscale pores in the cellu­
lose matrix offered large light scattering, uniform high-density
CdS coating, and good charge and mass transport. Thus, a
high H2 production rate of 1.323 mmol g−1 h−1 was achieved,
evidencing a promising role of porous nanocellulose films in
photocatalyst loading.
The mesoporous cellulose films were also used as a sup­
porting framework for encapsulating photosynthetic mate­
rials,[26,28] which could support the photoactive materials,
organize the guest redox couples, and protect them by pro­
viding a stable microenvironment.[29] Lee et al. reported
an integrated artificial photosynthetic system in which a
mesoporous lignocellulosic composite was used as a support to
immobilize light-harvesting pigments.[26] The porphyrins were
embedded in the lignocellulosic matrix and interacted with
lights to perform photochemical reactions, regenerate pyridine
nucleotide cofactors, and synthesize enzymes. Furthermore, the
presence of redox-active lignin component on the mesoporous
lignocellulosic composite surfaces could further enhance the
photosynthesis activity.
Taking the advantage of the excellent hydrophilicity of
cellulose, Li et al. developed a capillary PEC system using
CNF-templated TiO2 nanostructures that can uniquely perform
PEC water splitting reactions outside of the electrolyte body.[11]
A mesoporous CNF film was used to template the fabrication of
anatase TiO2 nanofibrous 3D structure via atomic layer deposi­
tion (ALD) followed by high-temperature annealing (Figure 3a).
A CNF strip was then attached to the TiO2 nanostructure, which
acted as the photoanode and was placed outside of the electro­
lyte facing a light source. The electrolyte was supplied through
the nano/microchannels in the CNF film driven by the capillary
force (Figure 3b). By comparing to regular in-electrolyte PEC
setup, the capillary PEC exhibited a superior performance with
a photocurrent density (Jph) of 0.87 mA cm−2, which was 107%
higher than that of the in-electrolyte setup. The PEC perfor­
mance enhancement of the capillary design was attributed to
the less light scattering from minimal electrolyte coating and
higher interfacial charge transport kinetics.
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Li et al. further showed that the CNF template was able to
modulate the chemical composition of the TiO2 coating.[11] By
annealing the TiO2-coated CNF structures in vacuum instead
of in O2 atmosphere, the final structure appeared black while
the fibrous morphology was still well preserved (Figure 3c).
The black color was a result of appreciable amount of carbon
element preserved in the TiO2 lattices, suggesting significant
visible light absorption. This “black” cellulose-templated TiO2
nanostructure exhibited appreciable photoactivity under visi­ble
light illumination and further improved the PEC performance
of the capillary design. The enhancements Jph and PEC effi­
ciency (η) were as large as ≈767% and ≈800% under visible
light illumination (Figure 3d). This comparison clearly shows
that the CNF-enabled capillary PEC is able to provide signifi­
cant additional enhancement of the PEC performance to those
achieved by other strategies, such as optimizations of light
absorption, surface/interface properties, and charge transport.
In addition to templating low-temperature ALD film coating,
mesoporous CNF was also used as templates for high-tempera­
ture nanorods (NRs) growth. Li et al. adapted the surface-reac­
tion-limited pulsed chemical vapor deposition technique[30–32]
for synthesizing high-density TiO2 NR branches within
mesoporous CNF templates.[24] The CNF framework was well
preserved under high deposition temperature (≈600 °C) by
first introducing a ZnO overcoating. The ZnO layer interacted
with TiCl4 vapor and was quickly converted into polycrystalline
TiO2 thin films following the Kirkendall effect,[33] seeding the
growth of TiO2 NRs while the CNF framework was burned off
(Figure 3e). This 3D heterostructure offers long optical paths,
high-quality charge transport channels, and a super large elec­
trolyte–semiconductor interface area. When used as a PEC
photoanode, its efficiency could be more than 200% higher
than those of CNF-templated TiO2 nanofibrous 3D structure.
3. Cellulose Nanostructures for Energy
Storage Applications
Lithium-ion batteries (LIBs) are broadly used as an energy
storage device in automobiles and portable electronic devices.
Rapid expansion of these industries generates a growing need
for LIBs with greater safety, lower manufacture cost, higher
energy density, and power density. Environmental concerns
also demand LIBs to use environmental-friendly materials. To
manufacture LIBs with these desirable properties, the devel­
opment of new materials and innovative structural design for
LIBs seems imminently inevitable. Cellulose, with its intrinsic
chemical and physical properties as well as advantages arising
from its microstructures, starts to draw a considerable amount
of attention from researchers.[34] For example, the good solu­
bility of cellulose in water allows the utilization of aqueous
electrolyte in place of hazardous organic solvents, and the
safety concern of LIBs can therefore be greatly alleviated. The
nanostructured cellulose and assemblies can bring in some
unique advantages and even another dimension in designing
battery electrodes. To date, various forms of cellulose, including
wood CNFs, wood CNCs, and bacterial nanocellulose (BNC),
have been applied in all components of LIBs. In this section,
we will primarily focus our discussion on the applications of
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Figure 3.  PEC electrodes based on CNF-templated TiO2 nanostructure. a) SEM image of CNF film coated with TiO2. b) Schematic illustration and
photograph of the capillary PEC water splitting setup. c) Photograph of the CNF films before and after TiO2 coating, and after annealing in vacuum and
oxygen atmosphere. d) Performance comparison of capillary PEC and normal PEC using CNF-templated TiO2 photoanodes. Reproduced with permis-
sion.[11] Copyright 2014, WILEY-VCH Verlag GmbH & Co. KGaA. e) Schematic synthesis procedure (left) and SEM image (right) of CNF-templated 3D
TiO2 fiber–nanorods heterostructure. Reproduced with permission.[24] Copyright 2014, IOP Publishing Ltd.

cellulose-based nanomateriales in LIBs, including electrodes
(e.g., active materials, binders, and structural support), electro­
lytes, and separators. Contemporary applications of cellulose
nanomaterials in supercapacitors, which share much similarity
in materials requirements, will also be reviewed briefly.
3.1. Paper-Based LIBs
Conventional LIB electrodes employ lithium intercalation
materials in both cathodes and anodes. These electrode mate­
rials are usually coated onto a metal foil serving as a current
collector and structural support. The lithium-ion storage
materials, or the active materials, are used in conjunction
with binders and electronic conductivity-enhancing materials
(e.g., carbon black). In the form of paper sheets, cellulose can
be used as the substrates for LIB electrodes in place of the
metal foil current collectors. In this regard, the technique
of coating current collector and electrode materials onto
cellulose paper sheets is critical. Hu et al. first exercised a
simple Meyer rod coating method to coat carbon nanotubes
(CNTs) and silver nanowires onto commercial Xerox papers
and achieved sheet resistance as low as 1 ohm per square.[35]
Compared with plastics, the authors demonstrated that cel­
lulose paper substrates could dramatically improve the film
adhesion, and thereby simplify the coating process and lower
the cost. It was also pointed out that the porous structure of
cellulose paper could lead to more conformal coating of the
conductive materials as it provides strong capillary force,
which enabled large contacting surface area between flexible
nanotubes/nanowires and cellulose paper after the solvent
was absorbed and dried out.
Since cellulose paper sheets can be used as both separa­
tors and electrode substrates, there has been a new research
frontier where LIBs are completely built on paper sheets.[36]
Such paper-based LIBs are thin and flexible in nature and
therefore can unlock a number of applications where conven­
tional LIBs would fail to deliver success. These applications

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Figure 4.  A thin, flexible paper-based LIB. a) Schematic fabrication process of free-standing double-layer thin films. b) (Left) 5 in. × 5 in. LTO/CNT
double-layer film coated on stainless steel substrate; (middle) the double-layer film can be easily separated from the substrate by immersing in water;
(right) the final free-standing film after drying. c) Schematic of the lamination process. d) Schematic of the final paper LIB structure. e) Photograph of
the Li-ion paper battery before encapsulation for measurement. Reproduced with permission.[37] Copyright 2010, American Chemical Society.

include batteries for bendable electronics and those where
irregular-shaped batteries are needed to fill the void spaces
such as in the chassis of electric vehicles. Hu et al. later
demonstrated a lamination process that could integrate all
components of a LIB into a single paper sheet.[37] The pro­
cess began with assembling a CNT current collector layer
and active material layer on a stainless steel substrate, fol­
lowed by transferring this double-layer structure to a cellu­
lose paper coated with polyvinylidene fluoride (PVDF) as the
glue. Figure 4 illustrates the lamination process. The CNT
layer was coated by a doctor blade method using an aqueous
ink containing CNTs and dodecylbenzenesulfonate; while
the active materials layer was coated by a slurry containing
Li4Ti5O12 (LTO, anode material)/LiCoO2 (LCO, cathode mate­
rial), with active carbon and PVDF as binder. The anode and
cathode double-layer structures could be peeled off and glued
to both sides of the cellulose paper, which served as a sepa­
rator membrane as well as a mechanical support. Compared
to directly coating the double-layer structure onto the cellu­
lose paper, the lamination process could provide excellent
mechanical integrity of the electrode materials and prevented
leaking through the paper separator. Similar configuration
can be applied to zinc–air batteries, too. Hilder et al. success­
fully fabricated flexible zinc–air batteries by printing zinc/
carbon/polymer composite anode on one side and poly(3.4-
ethylenedioxythiophene) on the other side of a cellulose
paper.[38]
3.2. Binders
An important application of cellulose in LIBs is the binder in
both cathodes and anodes for electrode materials including
layered oxides,[39] lithium iron phosphate (LFP),[40,41]
sulfur,[42,43] TiO2(B),[44] graphite,[45–47] and silicon.[47–52]
Although binders are not the most essential component
in LIBs, they can greatly affect the properties of electrodes,
particularly their mechanical and electrochemical perfor­
mances.[43,49,53] Current LIB technology uses PVDF as binders
and requires the use of volatile and toxic solvents for pro­
cessing, such as N-methyl-pyrrolidone (NMP). Both PVDF
and NMP are expensive materials and difficult to recycle. The
use of organic solvents can lead to hazardous events, such as
explosion. Therefore, fluorine-free aqueous binder replace­
ment is desired to address the economic, environmental, and
safety concerns, paving the way toward safer and greener
LIBs. In this regard, water-soluble carboxymethyl cellulose
(CMC), a derivative of linear polymeric cellulose with substi­
tutional anionic carboxymethyl groups in various degrees, is
frequently used. Typically, sodium CMC is often applied in
conjunction with styrene-butadiene rubber (SBR) by a weight
ratio.[54]
Studies have shown that CMC may not only be a safer,
cheaper, and more environmental-friendly alternative to
PVDF as binders, but it also enhances the performance of
the electrodes. Despite its high stiffness and a small strain

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at fracture, CMC could yield better bonding with the elec­
trode materials and the electrode substrates. This can be
intuitively attributed to the large number of carboxylmethyl
groups on cellulose chains. Munao et al. compared the per­
formance of PVDF and CMC when using a nanoporous sil­
icon material as the cathode.[49] They found that the sample
with CMC had a much longer cycle life than that with PVDF,
where both have similar initial capacity (1153 mAh g−1 for
35 cycles). This agrees with previous findings by Li et al.,
where a specific capacity about 1100 mAh g−1 for 70 cycles
was obtained.[52] Figure 5a schematically illustrates the pro­
posed cycling failure mechanism of both binder materials.
Compared with PVDF, CMC was much more adherent to the
Si particle surfaces and the structure of the composite elec­
trode materials thus had a much better stability upon cycling.
The specific bonding between CMC and Si was proposed
to be the carboxylic groups on CMC and the OH groups on
the surface oxide of Si. Liu et al. reported that SBR, together
with sodium CMC, can provide great adhesion between the
electrode materials and the copper substrate. The cycle life
of the LIB was thus improved nearly 10 times for Si-based
cathode and 100 times for graphite-based cathode.[50] Signifi­
cant improvement in the cyclability of the specific capacity
was also discovered when sulfur was used as the cathode
material.[42]
Natural cellulose without any modification can also be used
as binders. However, ionic liquids have to be used as solvents
in this case as natural cellulose is not soluble in water. Jeong
et al. prepared natural cellulose in 1-ethyl-3-methylimidazolium
acetate (EMIMAc) and mixed active materials (graphite and
LFP, respectively, for anode and cathode) into the solution.[55]
After coating the slurry on metal foils, the electrodes were
immediately immersed in water to extract EMIMAc (Figure 5b).
Water is a good solvent for EMIMAc but not for cellulose. In
this phase-inversion process, EMIMAc is completely recyclable.
Unlike most above-mentioned work where a single electrode
was tested against a lithium-foil counter electrode, full coin
cells were tested and a maximum capacity of 140 mAh g−1
(LFP) was obtained at the 55th cycle, and 85% of that capacity
was retained up to 120 cycles.

Figure 5.  Cellulose-based materials as binders in LIBs. a) Proposed capacity-fading mechanisms for Si composite LIB electrodes when using CMC
and PVDF as binder. Reproduced with permission.[49] Copyright 2010, Elsevier B.V. b) Production process of LIB electrodes with natural cellulose/ionic
liquid binders. Reproduced with permission.[55] Copyright 2011, Elsevier B.V.

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3.3. LIB Separators
Cellulose paper sheets are widely used in commercial alka­
line batteries thanks to their excellent wettability, low cost and
weight, high porosity, and good mechanical properties. Their
use in LIBs is very limited primarily because of the lack of a
thermal shutdown mechanism that closes the pores and ter­
minates the ionic flow at high temperature.[56] The hydrophilic
nature of cellulose papers is another concern as too much
water can cause degradation of lithium salts. However, recent
work by Jabbour et al. and Leijonmarck et al. suggested that
prolonged thermal treatment of cellulose papers can largely
alleviate this problem.[57,58] It is estimated that the cost of the
separator can be over 20% of the total cost of a LIB, and the
majority of which comes from the manufacturing process.[59]
The low cost of cellulose has driven continuous efforts on
using cellulose papers and cellulose composite papers for
LIB separators as a cheap alternative to existing polyethylene
(PE)/polypropylene (PP) membranes especially for low-power
applications.[60–63]
Zhang et al. for the first time reported the use of a commer­
cial rice paper as a separator in LIBs. The cellulose fibers in
the rice papers were about 5–40 µm in diameter. The perfor­
mance of such separators was compared to a commercial PP/
PE/PP Celgard membrane and a lower ionic resistance was
discovered.[64] Kim et al. prepared cellulose nanofiber papers
with pore size tuned by incorporating SiO2 nanoparticles and
nonconductive spacer particles. Such cellulose composite
papers were prepared by vacuum filtering a suspension con­
sisting of cellulose powders and SiO2 nanoparticles and sub­
sequently drying between two filter papers under 1 MPa in a
80 °C oven.[65,66] They found that 5 wt% SiO2 content yielded
the highest ionic conduction due to a balanced combina­
tion of nanoporous structure and the proper separator thick­
ness. Figure 6 shows the SEM images and an illustration of
the composite separator structure. Increasing content of SiO2
nanoparticles raised the pore size of the separator membrane
and thus the ionic conductivity. Thus, a significantly lower
MacMullin number could be achieved compared to the com­
mercial PP/PE/PP separators. Xu et al. prepared cellulose/
polydopamine (CPD) membrane simply using a paper-making
machine instead of a vacuum-filtration system.[67] A complete
lithium cobalt oxide/graphite cell was fabricated using CPD
separator, and better cycling stability and rate capability were
observed compared to commercial PP separator and pristine
cellulose separator. Alternating-current impedance of the cell
with CPD separator showed only a minor variation of 9 Ω after
100 cycles indicating an excellent interfacial stability. Zhang
et al. developed a nonwoven cellulose composite membrane
that contains cellulose, sodium alginate, flame retardant,
and silica using a paper-making machine as well, and a com­
plete lithium iron phosphate/lithium cell was fabricated and
tested using such separators.[68] In addition to good mechan­
ical strength, improved electrolyte uptake and ionic conduc­
tivity, such composite separators showed stable cyclability and
thermal dimensional stability at 120 °C owing to the addition
of the flame retardant. The addition of sodium alginate and
silica also enhanced the bonding between cellulose fibers and
thus the tensile strength of the separators.
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3.4. LIB Electrolyte
In current LIBs, mixtures of ethylene carbonate and a linear
carbonate are most commonly used as electrolytes. Such polar
electrolytes raised safety concerns as they are volatile and flam­
mable. Water and ionic liquids have also been used as elec­
trolytes. In general, liquid electrolytes can suffer from leaking
problems which threatens the life time of LIBs. Researchers
have adapted polymer electrolytes where liquid electrolytes are
trapped inside a polymer matrix to prevent leakage and allow the
development of flexible LIBs. Cellulose and cellulose derivatives
are studied for this purpose. In the simplest case, cellulose can
be used as filler materials to reinforce the mechanical strength
of polymer electrolytes. Nair et al. used a natural cellulose hand-
sheet in a methacrylic-based thermos-set gel-polymer electro­
lyte.[69] To enhance its compatibility with the polymer matrix,
cellulose was modified by grating poly(ethylene glycol) methyl
ether methacrylate under UV. The cellulose composite exhibited
excellent mechanical properties and preserved the good electro­
chemical performance. Azizi Samir et al. conducted a series of
study on the tunicin cellulose whisker-reinforced crosslinked
poly(oxyethylene) (POE) electrolyte. They were able to obtain
higher ionic conductivity over a wide temperature range and
better mechanical properties compared to POE without tunicin
cellulose whiskers. The reinforcing effect was more prominent
at high temperature.[70–73] In addition, the cellulose filler could
provide a thermal stabilization effect to the polymer electrolyte
above the melting point of poly(oxyethylene).[71] Willgert et al.
developed poly(ethylene glycol) (PEG) electrolyte reinforced
with CNF paper. The CNF paper was made from never-dried
softwood dissolving pulp and was modified by acryloyl chloride
and propionyl chloride via reactions with the OH groups on cel­
lulose, before their polymerization with the PEG methacrylate
oligomers.[74] Therefore, covalent bonds were created between
the PEG and cellulose phase, which improved the ionic conduc­
tivity when the composite was swelled with liquid electrolyte.
An ionic conductivity of 5 × 10−5 S cm−1 and an elastic modulus
around 400 MPa at 25 °C were obtained.
Cellulose and cellulose derivatives alone can be used as the
polymer matrix for electrolytes. Lee et al. reported a composite
polymer gels made of cellulose triacetate (CTA), N-methyl-N’-
propylpyrrolidinium bis(trifluoromethanesulfonyl)imide,
and lithium bis(trifluoromethanesulfonylimide with a ratio
of 1:3:1.5.[75] They demonstrated a significant enhancement
in ionic conductivity owing to the strong interaction between
lithium ions and the carbonyl group of CTA. Other cellulose
derivatives have been used as well, with similar motivations of
solvation and complexation of lithium ions to improve the ionic
conductivity.[76,77] Grafting anionic side chains to the polymer
backbones is another way of improving the ionic conductivity
as the translational mobility of negative charges can be reduced
so that positive lithium ions can have a significant mobility.[78,79]
Paracha et al. grafted lithium salts of 2-acrylamido-2-methylpro­
pane sulfonic acid on ethyl cellulose, and then copolymerized
methyl methacrylate (MMA) with a crosslinking agent to
form a semi-interpenetrating network for LIB electrolyte.[80]
1.33 mS cm−1 was obtained in conductivity tests and the
mechanical strength of the gels could be controlled by the con­
centration of MMA and ethyl cellulose.
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Figure 6.  Cellulose-based paper sheet as LIB separator. a) Molecular and crystalline structure of cellulose fibers. b–d) SEM images of the Si-cellulose
nanofibers papers with 0%, 1 wt%, and 5 wt% SiO2 content, respectively. e) Schematic illustrations of the structure of the composite paper. Reproduced
with permission.[65] Copyright 2013, Elsevier B.V.

3.5. As-Grown Template for Complex Electrode Structures
The fibrous form factor of cellulose nanofibers also contributes
to the development of novel LIBs as it allows tubular-nanostru­
crture growth of electrode materials using cellulose nanofibers
as templates. Guo et al. took the advantage of the morpholog­
ical hierarchy of filter papers made from natural cellulose, and
applied a surface sol–gel process and subsequent calcination
process to prepare nanotubular hollow SiOx.[81] The authors
argued that the nanotubes possessed firm framework and
prevented the electrodes from pulverizing in the charge–dis­
charge process while having sufficient voids to accommodate
the volume change. Wang et al. reported a templated growth
of TiO2 nanotubes from cellulose filter papers. They first had
Ti(OBu)4 sufficiently adsorbed into filter papers in ethanol and
then calcinated the paper at 500 °C.[82] Compared with other
templated growth of TiO2 nanotubes, this method is cheaper,
simpler, and more capable of being integrated into the fabrica­
tion of LIBs. Cellulose can also be easily converted to carbon,
a common anode material. Wang et al. reported that they
prepared carbon aerogel from bacterial nanocellulose (BNC)
aerogels, which was obtained by freeze-drying BNC hydro­
gels.[83] After calcination, the 3D open network of bacterial
nanocellulose hydrogels was preserved and carbon aerogels

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composed of about 20 nm nanofibers were produced. A much
better capacity retention behavior than mesoporous carbon was
observed due to the higher surface area of the aerogel electrode.
3.6. Supercapacitors
Similar to LIBs, cellulose papers can also be used as substrates
for supercapacitors. Compared to conventional metal sub­
strates, cellulose substrate renders capacitors good flexiblity,
which is desired to meet the varying design and power needs
of gadgets. Gui et al. developed cellulose paper/CNTs/MnO2/
CNTs supercapacitor electrodes (Figure 7a).[84] The cellulose
fibers in the paper not only provided a high surface area but also
acted as an interior electrolyte reservoir. The devices had dual
ion diffusion and electron transfer pathways so they work as
both double-layer capacitor and pseudocapacitors. Comparisons
were made between electrodes with cellulose paper replaced by
Al2O3-coated polyester textile, showing cellulose paper-based
ones had better ionic and electron conductivity and a better
capacitance retention up to 50k cycles. Surface area is a critical
factor for supercapacitors, where cellulose paper-based superca­
pacitors can find its unique advantages. BNC, typically obtained
from bacterial synthesis for low molecular weight sugars and
alcohols, has drawn much attention as BNC fibers are much
smaller (20–100 nm) and have better mechanical strength,
superior chemical stability, and can be made thinner.[4,84–87] For
example, Kim et al. made BNC papers from cultured glucon­
acetobacter xylinum and prepared CNT/BNC composite papers
(Figure 7b).[88] The supercapacitor showed an excellent specific
capacity of about 20 mF cm−2 with a reduction of smaller than
0.5% over 5k cycles at a current density of 10 A g−1. They were
also tested against bending and the performance was retained
through 200 bending cycles. In addition to CNTs, graphene
and conducting polymers are often used to form the composite
too.[89–91] A new advance in this area was made when Liew et al.
reported their polypyrrole/cellulose nanocrystals composite
supercapacitors.[92] Unlike other laboratory models where very
thin films were used and thus their area specific capacitance
was too small for commercial applications, this work fabricated
films over 100 µm thick, which yielded a high capacitance of
240 F g−1. A highest area specific capacitance of 1.54 F cm−2
was demonstrated before electrolyte diffusion reaches its limi­
tation in thicker electrodes.
Rather than using premade cellulose papers, Pushparaj et al.
developed cellulose/CNTs composite paper supercapacitors by
embedding cellulose in vertically aligned multiwalled carbon
nanotube (MWNT) array on Si substrates (Figure 7c).[93]
Unmodified plant cellulose in an ionic liquid (1-butyl,3-methy­
limidazolium chloride) was infiltrated into the MWNT to form
a uniform film of cellulose and the ionic liquid was removed
by solidification of the film on dry ice and immersing it in eth­
anol for extraction. This thin film was then peeled off from the
Si substrate and exhibited excellent mechanical flexibility and
integrity during operation. An intriguing feature of such nano­
composite paper-based supercapacitors was the flexible choice
of electrolyte. In addition to water and ionic liquid electrolytes,
the device could operate with a suite of electrolytes based on

Figure 7.  Cellulose-based supercapacitors. a) Schematic structure and SEM image of a paper/CNTs/MnO2/CNTs supercapacitor electrode. Red arrows
indicate location of CNTs. Reproduced with permission.[84] Copyright 2013, American Chemical Society. b) SEM image (top) and a cross-sectional
image (bottom) of a CNT-coated BNC paper supercapacitor electrode. Inset is a photo of the CNT-coated BNC paper. Reproduced with permission.[88]
Copyright 2012, American Chemical Society. c) Supercapacitor assembled using cellulose/CNTs composite paper units. Top left is a schematic illus-
tration showing the structure of the nanocomposite paper units. Top right are photos of the nanocomposite units. Bottom is a cross-sectional SEM
image of the nanocomposite paper showing MWNT protruding from the cellulose-RTIL thin films. Reproduced with permission.[93] Copyright 2007,
The National Academy of Sciences of the USA.

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body fluids, such as sweat, blood, allowing body implant or use
under special circumstances.[94]
Cellulose can be used as binders and separators in superca­
pacitors just like in LIBs. Testing in conventional active carbon-
based double-layer capacitors, Varzi et al. demonstrated that
cellulose fiber binders enabled superior performance retention
under float tests at high voltage compared to PVDF. This is a
merit particularly important in double-layer capacitor electrodes
with ionic liquids as electrolytes. Their work demonstrated
that the improvement was more significant at the negative
electrode.[95]
4. Cellulose Nanomaterials for Nanogenerator
Developments
Mechanical energy from the environment (e.g., ambient vibra­
tions or activities of human body)[96,97] represents a unique
and sustainable energy source that perfectly suits for powering
portable electronics and unattended devices.[97–99] In 2012, the
triboelectric nanogenerator (TENG) was first reported[100] as a
new type of technology that converts environment mechanical
energy to electrical energy.[13] Compared to other technolo­
gies, TENG is advantageous in terms of high efficiency, high
power density, light weight, low cost, and great manufactur­
ability.[97,101–103] TENG operates based on the coupling effects
of contact electrification and electrostatic induction. The
working principle requires two dissimilar surfaces to be oppo­
sitely charged upon contact. Positive (polyamides,[104] metals[97])
and negative (fluorinated ethylene propylene (FEP),[105,106]
polytetrafluoroethylene (PTFE),[104] and polyethylene terephtha­
late (PET)[104,107–109]) triboelectric materials are typically used in
pairs in TENGs due to their opposite tendencies to gain or lose
charges upon contact. Cellulose, the most abundant natural
polymer on Earth, can also be a good candidate as a triboelectric
material, bringing unprecedented natural degradability, recycla­
bility and biocompatibility to TENG systems. As a result, CNF
thin films are increasingly explored in TENG developments
in recent a couple of years. Here, we review the most recent
technology evolution in CNF-based TENGs, from fundamental
property tuning to practical implementations of CNF materials
in TENG systems. Cellulose-based piezoelectric nanogenerators
(PENGs) are also briefly reviewed as an alternative for mechan­
ical energy harvesting.
4.1. Cellulose Nanostructure-Based TENGs
Natural cellulose is a slightly triboelectric positive material. In
order to effectively generate triboelectric output, it was typically
paired with strong triboelectric negative materials to fabricate
a TENG device. The first CNF-based TENG was demonstrated
by Yao et al. by pairing a CNF mesoporous film with a FEP
film.[110] The CNF film surface exhibited a clear fibrous feature
and a surface roughness of ≈300 nm, offering a large surface
area for contact and electrostatic charge generation (Figure 8a).
The as-prepared film also showed excellent transparency and
flexibility, and the entire TENG device is flexible and trans­
parent (inset of Figure 8b). The average triboelectric output
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under regular mechanical force reached ≈5 V (Figure 8b),
which were comparable to the performance of TENGs made
of typical synthetic polymer pairs such as Kapton-PET[100],
PTFE-polyamide.[104] External load matching test indicated the
optimal power was 0.56 mW at ≈1 MΩ.
Successful development of TENG using CNF film opened
a possibility of creating power-harvesting boards using wood-
extracted fibers. CNF-based TENG was integrated with a
fiberboard made from recycled cardboards as a practical dem­
onstration. Figure 8c shows the large-scale manufacturing
process of the triboelectric fiberboard. This board was able to
generate electricity as high as ≈10–30 V and ≈10–90 µA, when
subjected to repeated steps from a person of average weight.
The amount of electricity generated from one single step could
light up 35 green LEDs that were connected in series (panel 6
in Figure 8c), demonstrating the promise of powering commer­
cial electronics from foot traffic. This research fully exploited
the merits of mechanical flexibility and nanostructured surface
features contributed by the NC films.
Following this work, cellulose nanomaterials were more and
more frequently used in TENG developments. Kim et al.[111]
regenerated bacteria cellulose to obtain a uniform, flexible, and
transparent cellulose film. Since the chemistry of bacteria cel­
lulose is nearly the same as wood cellulose, their dielectric and
triboelectric polarizations are generally the same, and thus the
triboelectric output remained at the same level as the previous
report. When the cellulose film was assembled with Cu to form
a vertical contact-separation mode TENG, the typical voltage
output from a 5 × 5 cm2 TENG under a compressing force of
16.8 N at 1 Hz was ≈13 V (Figure 9a), where a curved cellu­
lose film was found favorable for higher output. Uddin et al.[112]
also fabricated pure-cellulose-based TENG by assembling two
flexible cellulose films made from hydrolyzed microcrystalline
cellulose with a polyimide-Al-PET-Al-polyimide corrugated-core
structure (inset of Figure 9b). The TENG showed a maximum
output voltage of 142–153 V and output current of 3.2–3.9 µA at
a frequency of 3 Hz under a series of forces ranging from 3 to
10.1 N. This TENG device also exhibited a H2-gas respon­
sive output: when the TENG was exposed to 0.1 vol% H2 gas,
the voltage output decreased remarkably, from ≈142 to ≈41 V
(Figure 9b). This force-independent output response was pos­
sibly owing to the strong interaction between cellulose fibrils
and H2 molecules, showing a promising application potential
of self-powered gas sensing.
In addition to pure cellulose films, cellulose composites were
also developed for TENG applications. Chandrasekhar et al.
fabricated polydimethylsiloxane (PDMS)/cellulose composite
films with improved flexibility and mechanical integrity.[113]
By pairing this composite film with Al film, the TENG gener­
ated a voltage output of 28 V at a force of 32.16 N. A similar
cellulose composite film was created by mixing cellulose
nanocrystal flakes in a PDMS matrix (Figure 9c).[114] Under
a compressing force of 20–40 N at a frequency of 10 Hz, the
TENGs assembled from the composite film against Al showed
voltage output of 150–320 V (Figure 9d), which was 4–10 times
higher than its pure PDMS counterpart. This output was also
much higher than the other cellulose composite films, which
might be related to the internal polarization from the cellulose
nanocrystal flakes.
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Figure 8.  TENG fabricated from CNF films. a) AFM topography image and roughness of a CNF film surface. b) Voltage output of a TENG fabricated
from a CNF-FEP pair. Inset is a photograph of the TENG. c) Manufacturing process of the triboelectric fiberboard: a CNF-FEP TENG is embedded in a
fiber mat and the entire piece is then cold-pressed and dried to obtain the final fiberboard. The bottom right photograph shows the fiberboard lighting
up LED lights when stepped on. Reproduced with permission.[110] Copyright 2016, Elsevier Ltd.

4.2. Polarity Tuning of Cellulose Nanomaterials
Above pioneer work on cellulose TENG opened a new exciting
material engineering direction for TENG development using
natural and recyclable materials. However, all of them still
included synthetic polymers and/or other electrode materials
to pair with cellulose for effective charge separation. The weak
polarization tendency of natural cellulose limits its capability of
generating surface charge, which keeps their performance low
compared to those synthetic polymers. Inclusion of synthetic
polymers would also reduce the recyclability and eco-friendli­
ness, as well as raise the cost. In order to realize all-cellulose
TENGs, the electric property of CNF fibers needs to be tuned.
Thus, both TENG active layers can be made from CNF thin
films. Taking advantage of the abundant hydroxyl groups on
cellulose molecules, CNF can be functionalized via simple
wet-chemistry reactions.[115–117] Their electrical properties
could then be drastically tuned by the new chemical functional
groups. For example, nitro groups (NO3) can largely raise the
electron affinity of cellulose molecules; while methyl groups
(CH3) can improve cellulose’s capability of donating electrons.
Recently, Yao et al. employed wet-chemical reaction
approaches to introduce nitro groups and methyl groups, to
rationally tune the triboelectric polarity of CNF for TENG
application.[118] Nitro-CNF was achieved by treating CNFs with
nitration acid mixture comprising HNO3, H2SO4, and water.
Methyl-CNF was obtained by reacting mercerized CNF with
dimethyl sulfate. The as-prepared nitro- and methyl-CNF films
were both flexible and transparent, showing the chemical func­
tionalization imposed negligible influences on the film’s other
physical properties. Triboelectric figure of merit (FOM) charac­
terization was performed on these CNF thin films by quanti­
fying the surface charge density upon contacting with standard
Ga-In eutectic liquid metal electrode. Measurements revealed
the charge densities from pristine CNF, nitro-CNF, methyl-
CNF, and FEP were −13.3, 85.8, −62.5, and 120.9 µC m−2,
respectively (Figure 10). The negative sign indicates that elec­
trons were transferred from the testing film to the electrode
upon contact. FEP is the most tribo-negative material and
was used as a reference here (FOM = 1). It can be seen that,
after the methylation and nitration, the charge density of CNF
exhibi­ted 5–10 times enhancement toward the same and oppo­
site charge transfer directions, respectively. The charge den­
sity of nitro-CNF raised to nearly 80% of FEP. Corresponding
FOMs of nitro-CNF and methyl-CNF were calculated to be 0.51
and 0.28, respectively.These are comparable to other commonly

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Figure 9.  TENGs developed based on cellulose films. a) Schematic structure of a BNC-Cu TENG and the voltage output from the TENGs with different
active surface area. Reproduced with permission.[111] Copyright 2017, Elsevier Ltd. b) Photograph of a microcrystalline cellulose film-polyimide TENG
and its voltage output under various compression force when exposed to H2 and air. Reproduced with permission.[112] Copyright 2017, Elsevier B.V.
c) Schematic synthesis process and SEM image of PDMS/CNC composite. Center image shows the film adhered to a glove surface, demonstrating
its good flexibility. d) The voltage output of TENGs fabricated from the PDMS/CNC films with different CNC concentrations. Reproduced with permis-
sion.[114] Copyright 2017, The Royal Society of Chemistry.

used synthetic polymers such as Kapton (0.60), PVDF (0.45),
polyethylene (0.43).
The remarkable triboelectric polarity tuning allowed the
creation of all-CNF-based TENGs with both triboelectric func­
tional layers being CNF materials. TENGs with the vertical
contact mode were assembled with different pairs of pristine
and functionalized CNF and their voltage and current output
were characterized. The two chemically functionalized CNF
films both showed enhanced output when paired with the pris­
tine CNF film. Because nitro- and methyl-functionalization
shifted the triboelectric polarization toward opposite directions,
when these two materials were paired together, the output
was further raised to an average voltage and current value of
8 V and 9 µA. It is important to notice that output from the
nitro-CNF-methyl-CNF pair was approaching that of the FEP-
CNF pair (9 V and 10.5 µA); whereas the FEP-methyl-CNF pair
showed an even higher output (12 V and 10.5 µA) due to the
more positive methyl functionalization. Since this polariza­
tion tuning was based on molecular-level functionalization, the
enhanced output was fairly stable. Long-term test of the nitro-
CNF-methyl-CNF TENG revealed no output signal decay after
5 × 105 cycles. These experiments evidenced the great potential
for replacing commercial synthetic polymers by renewable and
biodegradable CNF-based films with comparable or even supe­
rior triboelectric performance.
4.3. Flexible, Transparent, and Conductive CNF Paper
Most recently, Yang et al. presented a development of flexible
and nature degradable transparent electrodes based on CNF
paper.[119] In their work, an aluminum-doped zinc oxide (AZO)
thin film was grown by ALD on a CNF paper as the transparent
conductive oxide (TCO) layer. While the deposition temperature
was only 150 °C to preserve the structural and chemical integ­
rity of the CNF paper, the AZO film showed excellent crystal­
linity, conformality, and a very low surface roughness (≈2 nm,
Figure 11a). By optimizing the Al concentration, the highest
resistivity of the AZO-coated CNF paper was found to be
2.7 × 10−3 Ω.cm at 3.7 at% Al. Meanwhile, the AZO-CNF papers
showed a high transmittance of >84% in the visible range of
400–760 nm, which allowed them for TCOs applications like
displays and solar cell windows. The AZO film with 3.7 at%
Al also exhibited the best resistivity and transparency combina­
tion, which was at the same level as the reported values of ITO
and graphene (Figure 11b).[120,121]

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Figure 10.  Surface charge property of triboelectric films a–d) current flow measured during one contact-separation event when electric contact was
made between Ga-In eutectic liquid metal and the triboelectric film of CNF a), FEP b), nitro-CNF, and methyl-CNF. Inset in (a) is the setup that can
move vertically for making the contacts. Insets in (c) and (d) are the molecular structure of nitro-CNF and methyl-CNF, respectively. Reproduced with
permission.[118] Copyright 2017, WILEY-VCH Verlag GmbH & Co. KGaA.

The relative open structure of the CNF paper was believed
to facilitate the strong binding of oxide layer. Cross-sectional
energy disperse spectrum (EDS) mapping (inset of Figure 12a)
showed that appreciable amount of Zn presented within the
CNF film, indicating successful infiltration of the precursor into
the CNF paper porous structure. Growth of AZO, a certain dis­
tance into the CNF paper, could enhance the binding strength
between the AZO layer and the CNF surface (Figure 12a) and
improve its mechanical integrity. As a result, the sheet resist­
ance of the AZO–CNF papers exhibited an excellent stability
within a range of 135–180 Ω sq−1 under compressive strain
from −0.057 to −0.457% (Figure 12b). This stable strain region
of the AZO-CNF film was comparable to typical ITO-based
flexible transparent films, suggesting its potential as a competi­
tive flexible transparent substrate.
One unique merit of AZO-CNF paper that distinguishes it
from other synthetic flexible polymer substrates is the excellent
degradability and recyclability. As shown in Figure 12c, one piece
of AZO-CNF paper was placed into a warm city water (70 °C).
After 60-min stirring, the AZO-CNF paper was completely dis­
solved into the water. The final solution was clear. It became a
CNF gel with a small amount of Zn and Al ions coming from
the AZO coating. Using AZO as the TCO component ensures
complete dissolving of all the film components. This solution
can thus be further concentrated and filtered to produce CNF
film again, whic indicates the excellent recyclability.
A pair of AZO-CNF paper with chemically tuned polarity
was then used to fabricate a nature degradable TENG device
(Figure 12d). Because metal contact was no longer used in this
TENG assembly, the entire device was also completely water
degradable. When the TENG was under a constant 10 Hz
impact, the maximum voltage was ≈1–6 V under a series of
external load resistance (Figure 12e). The maximum power of
≈0.5 mW was obtained at 1 MΩ load resistance, comparable to
other cellulose-based TENG devices. This is the first report of
flexible, transparent, and metal-free TENG that is completely
nature degradable. With a reasonably high electrical output and
operational life span, it offers a unique solution for developing
green, biocompatible, and self-degradable powering units for
self-sustainable electronic systems.
4.4. Cellulose-Based PENGs
PENG is another widely applied technology for mechanical
energy harvesting using piezoelectric nanomaterials.[122]

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Figure 11.  Transparent conductive AZO-CNF papers. a) Left is AFM image of an AZO-coated
CNF surface. Right are optical images of an as-fabricated CNF paper from the CNF gel (top)
and an AZO-coated CNF paper (bottom). b) Transmittance (at 550 nm) and sheet resistance
of AZO-CNF in comparison with other typical flexible transparent electrode materials. Repro-
duced with permission.[119] Copyright 2017, Creative Commons Attribution 4.0 International
License, Nature Publication Group.
Crystalline cellulose is a well-known polymeric piezoelectric
material, and its piezoelectric polarity arises from the align­
ment of the glucose units through glycosidic linkage linearly
along the C2 monoclinic lattice, a non-centrosymmetric crys­
tallographic structure. While the piezoelectric property has
been observed over half century ago from natural wood,[123]
isolated cellulose was not investigated as a piezoelectric
material until 2006 when Kim et al. published their pioneer
work on a cellulose paper (which was termed as EAPap,
standing for cellulose electro-active paper) demonstrating an
actuation phenomenon.[124] This cellulose paper was a film
of regenerated cellulose fabricated from xanthate cellulose
solution, and morphologically consisted of ordered and dis­
ordered regions. This paper exhibited appreciable mechan­
ical deflection under relatively small electrical potential, and
this response was also very sensitive to humidity. Oriented
CNC film was expected to generate more significant piezoe­
lectricity due to their highly ordered crystal structure. Csoka
et al. fabricated an ordered CNC film by a combination of
shear and electric fields.[125] Atomic force microscopy (AFM)
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measurements revealed the piezoelectric
constant d25 of such a highly ordered CNC
film to be 2.1 Å V−1.
However, so far there is no work
reporting directly using crystalline cel­
lulose for PENG development, possibly
because of its relatively weak piezoelectric
effect and high processing requirements.
Instead, cellulose-based composites were
successfully explored as a promi­sing PENG
structure. Zhang and coworkers reported
a piezoelectric composite paper based on
ferroelectric BaTiO3 (BTO) nanoparticles
and bacterial cellulose.[126] This composite
paper exhibited remarkably enhanced
piezoelectric output with a peak voltage of
14 V and a peak current density of
190 nA cm−2. The maximum power den­
sity reached 0.64 µW cm−2. This output was
nearly ten times higher than that of piezo­
electric composite paper made from the
same BTO nanoparticles in a PDMS matrix.
The enhancement was attributed to the
extremely uniform distribution of BTO nano­
particles in the cellulose matrix in contrast
to more agglomerations in PDMS media.
This advantage was intuitive since cellulose
offers preferable hydrophilicity and strong
surface charge to stabilize nanoparticle
suspension during composite processing.
It should be noted that this output power
was still much lower than cellulose-based
TENG devices. It may be promising to inte­
grate both bulk-related piezoelectric effect
and surface-related triboelectric effect in
cellulose nanostructures to further improve
mechanical energy-harvesting capability.
5. Conclusion and Remarks
In general, this article reviews the most recent developments
and contemporary applications of cellulose nanomaterials in
energy-related areas, including LIBs, supercapacitors, solar
cells, PEC electrodes, and nanogenerators. Compared to the
conventional application of cellulose in bio-fuel generation,
these applications emphasize the polymeric material nature of
cellulose. As we addressed in the introduction part, cellulose
possesses many unique features and advantages as a polymer
and presents a unique combination of chemical, structural,
dielectric, and optical properties that can be rarely found in
other polymer systems. In this regard, using cellulose nanoma­
terial as a functional component in modern energy devices and
systems may lead to a new paradigm of materials innovation.
Therefore, we can highlight the studies reviewed in this article
as functional cellulose nanomaterials development. Although it
just emerged in recent years, these unprecedented application
potentials have been seen in various directions. It is foreseeable
that functional cellulose nanomaterials are going to take on a
© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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www.advancedsciencenews.com www.small-journal.com

Figure 12.  AZO-CNF papers for TENG development. a) A cross-sectional SEM image of the AZO-CNF paper. Inset is the corresponding EDS mapping
of the Zn elements showing substantial Zn signal within the CNF paper. b) Change of sheet resistance and resistivity as a function of bending radii
when the AZO film was under compressive strains. c) A series of photographs showing the process of dissolving AZO-CNF paper in city water at 70 °C.
The AZO-CNF paper is completely dissolved after 60-min stirring. d) Schematic image and photograph of the all-transparent TENG made from a pair
of AZO-CNF papers. e) The long-term stability of the AZO-CNF TENG. Reproduced with permission.[119] Copyright 2017, Creative Commons Attribution
4.0 International License, Nature Publication Group.

more and more important role in the family of energy mate­
rials. Certainly, challenges also exist and require substantial
research efforts to overcome.
First, synthesis of cellulose nanomaterials with well-con­
trolled degree-of-polymerization. This is the fundamental
requirement for us to obtain reliable understanding of the
property and structure relationships in cellulose nanomaterials
and predict their functionality.
Second, molecular-level understanding of how cellulose
molecules arrange into different phases, i.e., how the mole­
cular chains organize and interact with each other in short-
and long-range ordered fashion. Although many cellulose
polymorphs have been found, how they can be controlled, and
thus tune the macroscopic property is mostly still a mystery.
This understanding will essentially uncover the unprecedented
application potentials of cellulose nanomaterials as an essen­
tial functional component in many modern energy and elec­
tronic systems.
Third, new approaches to functionalization, modification,
and assembly of cellulose nanomaterials in different length
scale. This capability, which is currently lacking, is an essential
step leading the fundamental and conceptual studies of cellu­
lose nanomaterials toward practical applications.
To conclude, study of functional cellulose nanomaterials is
just at the beginning. As reviewed in this article, it possesses
tremendous materials science value and application potential
in many energy-related fields. With advanced synthesis, pro­
cessing and characterization techniques, and the talents from
different scientific disciplines, cellulose nanomaterials may
soon become a powerful multifunctional material platform that
nature offered to us to bring our energy materials technology to
a new horizon.

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Acknowledgements
This publication was supported by the National Institute of Biomedical
Imaging and Bioengineering of the National Institutes of Health under
Award # R01EB021336, Department of Energy (DOE), Office of Science,
Basic Energy Sciences (BES), under Award # DE-SC0008711, and the
National Science Foundation under Award # CMMI-1148919. Figures 1–12
were inverted when this article was first published in an online issue.
This was corrected on November 24, 2017.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
cellulose nanomaterials, lithium-ion batteries, nanogenerators,
photoelectrochemical devices, solar cells
Received: July 1, 2017
Revised: August 1, 2017
Published online: September 13, 2017
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