Accepted Manuscript

NanoCellulose Based Functional Materials for SuperCapacitor Applications

Jasmine Jose, Vinoy Thomas, Vrinda Vinod, Rani Abraham, Susan Abraham

PII: S2468-2179(19)30008-5
DOI: https://doi.org/10.1016/j.jsamd.2019.06.003
Reference: JSAMD 231

To appear in: Journal of Science: Advanced Materials and Devices

Received Date: 8 January 2019

Revised Date: 30 April 2019
Accepted Date: 3 June 2019

Please cite this article as: J. Jose, V. Thomas, V. Vinod, R. Abraham, S. Abraham, NanoCellulose
Based Functional Materials for SuperCapacitor Applications, Journal of Science: Advanced Materials
and Devices, https://doi.org/10.1016/j.jsamd.2019.06.003.

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.
 ACCEPTED MANUSCRIPT

Nano Cellulose Based Functional Materials for Super Capacitor Applications

Jasmine Josea, Vinoy Thomasa * ,Vrinda Vinoda, ,Rani Abrahamb and Susan Abrahamc

a
Centre for Functional Materials , Christian College, Chengannur University of Kerala,– 689122,India
b
Departmetn of Chemistry, Christian College, Chengannur University of Kerala,– 689122,India
c
Departmetn of Economics, Christian College, Chengannur University of Kerala,– 689122,India

PT
*
corresponding author, vinoythoma@gmail.com, ,(91) 9497331753

RI
Jasmine Jose jasminejose764@gmail.com

SC
Vinoy Thomas vinoythoma@gmail.com
Rani Abraham raniabraham@gmail.com
Vrinda Vinod vrindavinod.kk@gmail.com
Susan Abraham susanmi@gmail.com

U
AN
M
D
TE
C EP
AC
 ACCEPTED MANUSCRIPT

1 NanoCellulose Based Functional Materials for SuperCapacitor Applications

2
3
4 Abstract

5 The topic of environmental protection and that of renewable sources for energy conversion and storage

PT
6 remains an important one nowadays. Major challenges of the 21st century that manhood has to face is
7 certainly energy supply; its storage and conversion in a way that essentially protect the environment. It is in this

RI
8 scenario that nanocellulose has come up as a sustainable and promising nanomaterial with its unique
9 structure and remarkable properties such as high specific modulus, excellent stability in most solvents,
10 low toxicity and natural abundance. Its ecofriendly nature, low cost, easy availability and simple

SC
11 synthesis techniques render nanocellulose as a promising candidate for fabrication of green renewable
12 energy storage devices. Herein, we present a comprehensive review of the current research activities that

U
13 focus on the development of nanocellulose materials for energy storage application, particularly on
14 supercapacitors. To begin with we give a brief introduction on the necessity of ecofriendly approaches
AN
15 towards the development of supercapacitors that make use of nanocellulose. We then focus on various
16 investigations that have been carried out to fabricate supercapacitors based on nanocellulose or its
M

17 composites. Finally, we present our outlook on several issues that warrants further investigation in this
18 topic that bears immense potential.
19 Keywords: nanocellulose, supercapacitor
D

20
TE

21 1. Introduction

22 In recent times we have seen considerable improvement in the standard of living which without any doubt
EP

23 could be attributed to the innovation and development of more viable products through more efficient
24 processes. To keep this process moving we need to make use of resources that are renewable and
C

25 sustainable. Moreover, the technologies have reached a new era of information technology and material
26 innovation is experiencing an unpredictable pace of progressing. Numerous types of sensors, electronic
AC

27 devices and so on are built everyday using advanced ceramics, metals, and plastics. The huge
28 advancement of today’s technology is bringing revolutionary changes to our society and along with this
29 arises serious environmental concerns due to the generation of electronic and plastic wastes [1]. The
30 extraordinary growth in portable electronic systems during the past few decades have gained the attention
31 of researchers in developing versatile energy storage devices such as batteries, super capacitors, or fuel
32 cells [2-3]. Super capacitors, also termed as electrochemical double-layer capacitors, have high capacity
33 with fast charge/discharge rate. These interesting properties have made super capacitors capable of filling

1
 ACCEPTED MANUSCRIPT

34 the gap between batteries and conventional capacitors [4]. Currently, polymeric materials for super
35 capacitor applications have gained wide attention because of their properties, such as flexibility,
36 lightweight, and stable cycling performance [5]. Further, redox active polymers due to their recyclability
37 and sustainability are better and safer replacements for heavy metals in battery electrodes [6]. Since the
38 future generation electronics industry needs to be highly sustainable there must be extraordinary and

PT
39 viable efforts for the development of low-cost, lightweight, environment-friendly, high-performance
40 super capacitors and batteries [7]. Among biopolymers, natural polysaccharides are being developed as
41 substitutes to synthetic materials for electrochemical devices [4]. Nanocellulose, is a structural

RI
42 polysaccharide that has gained much attention nowadays due to its renewability, inherent biocompatibility
43 and biodegradability, cost-effectiveness, natural abundance and eco-friendly nature [8]. Cellulose is an

SC
44 odourless, biodegradable, hydrophilic, water insoluble material obtained from plants, animals, or bacteria
45 and the term ‘nanocellulose’ usually refers to the cellulosic extracts or processed materials, having nano-

U
46 scale structural dimensions. Nanocellulose can be classified into three types: (i) cellulose nanocrystals
47 (CNCs)/nanocrystalline cellulose (NCC) and cellulose nanowhiskers (CNWs), (ii) cellulose nanofibrils
AN
48 (CNFs), also referred to as nano-fibrillated cellulose (NFC), and (iii) bacterial cellulose (BC) (Table 1)
49 [9]. Chemically, cellulose consists of linear chains of repeating β-D-glucopyranose units, covalently
50 connected through β-1, 4 glycosidic bonds (figure 1) [10]. A large number of hydrogen bonds exist intra
M

51 and inter molecularly and yield different cellulosic structures. Nano cellulose offer a unique combination
52 of properties including flexible surface chemistry, transparency, low thermal expansion, high elasticity,
D

53 anisotropy and the ability to bind to other conductive materials, enabling extensive application in flexible
TE

54 energy-storage devices [11-12].

55
C EP
AC

56
57 Figure 1: Structure of cellulose

58
59
60
61 Table 1: Primary characterization of cellulose types [13-15]
62

2
 ACCEPTED MANUSCRIPT

Material Crystallinity Surface Young’s Average size

2 −1
area [m g ] Modulus [GPa]
Diameter length
Cellulose micro <60% <1 20–60 10 µm >10 µm
fibres (CMF)

PT
Cellulose nano 50% ≈ 90% ≈100 50–160 10–80 <10 µm
fibres (CNF) nm

RI
Cellulose nano ≈90% ≈200 50–140 5–30 nm ≈100
crystals (CNC) nm
63

SC
64 Extraction of nanocellulose can be done through chemical treatment, mechanical processing, and
65 enzymatic treatments. The different methods of preparation are shown schematically in figure 2.

U
66 Integrating nanocellulose into energy-related devices would definitely elevate research in the area of eco-
67 friendly materials and we find it to be a very promising in addressing the important environmental
AN
68 concerns. In addition, cellulose expresses itself as a low cost material with large-scale promises [17].
69 With cellulose-related materials gaining more and more popularity a number of good review articles have
M

70 appeared in the area of synthesis of nanocellulose and its properties. Several reviews published in the past
71 few years have also focused on the application of cellulose based energy related devices such as batteries,
72 sensors, and other electronic systems [18]. Current focus however seems to be in the field associated with
D

73 cellulose based sustainable supercapacitors which is fast growing with a very high progress rate.
TE

74 Although the interest for designing cellulose based devices for energy storage applications grew fast in
75 the recent past according to Nyholm et al [19] it is quite interesting to note (Figure 3) that investigations
76 in the field has hardly increased since 2012.
EP

77
C
AC

3
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
C EP
AC

78
79 Figure 2: Various preparation methods of nanocellulose [adapted from reference 16]
80
81

4
 ACCEPTED MANUSCRIPT

PT
RI
SC
82
83

U
84 Figure 3: Scopus database for the research output in form of research articles using cellulose and
AN
85 supercapacitors as keywords
86
87 In this review, we essentially focus on the potential application of nanocellulose in energy-related areas
M

88 particularly, in the field of supercapacitors. Our investigations in the area were concentrated in the
89 synthesis of nanocellulose and experimental evaluation of their thermo-optic properties using thermal
D

90 lensing technique. We were able to develop a UV protection system using nanocellulose/ PVA composite.
91 With the current experimental background and information we plan to expand our area of research and
TE

92 focus on the possible applications of nanocellulose in the field of energy-related devices especially in the
93 development of supercapacitors.
EP

94
95 2. Cellulose-based functional Materials
96 Cellulose is one of the most abundant natural organic polymers on the earth and is usually extracted from
C

97 plants, agricultural byproducts, wood etc. [4]. The properties of cellulose and cellulose derived materials
AC

98 can be enhanced by functionalizing it with suitable materials [20] or through structural modifications for
99 specific applications. Cellulose nanofibres (CNF) (<100 nm width) were synthesized very recently in our
100 laboratory using raw cotton as the source material through green techniques (Figure 4). In-depth
101 investigations were carried out to evaluate the thermo optic properties and ultraviolet blocking
102 capabilities. Ultra-sensitive dual beam mode matched thermal lensing technique was used for the
-8
103 measurement of thermo optic properties (Figure 5). The low thermal diffusivity (2.61 x10 m2/s) and
104 thermal conductivity (0.108 W/mK) value of the system indicated its thermal insulation behavior. Further,

5
 ACCEPTED MANUSCRIPT

105 highly transparent Plasmon-enhanced ultraviolet radiation blocking CNF-PVA films (Figure 6) for
106 environmental applications were developed and we found that the UV blocking capability of the
107 synthesized films is almost the same as that of commercial films available in the market. With our current
108 interest being the development of functionalized Nanocellulose based systems for energy storage
109 applications, the development of functionalized Nanocellulose based aerogels for super capacitor

PT
110 applications is underway in our lab. This review therefore has been carried out to bring a fresh picture of
111 nanocellulose based super capacitors, which we believe, is highly significant in the present scenario. .

RI
U SC
AN
112
M

113 Figure 4: HR-TEM image of CNF prepared from cotton, Figure 5: Thermal lensing plot of CNF,
114 Figure 6: UV /Visible spectrum shows transparency of PVA/CNF/AgNP film
D

115
TE

116 3. Cellulose based supercapacitors

117 Supercapacitors, also called ultracapacitors or electrochemical capacitors, offer a promising approach to
EP

118 meet the growing power demands owing to their high power density, superior rate capability, quick
119 charging/discharging rate, long cycle life, simple principles, fast dynamics of charge propagation and low
120 maintenance cost [21]. These supercapacitors are classified into electrical double layer capacitors, which
C

121 store energy through electrostatically accumulated charges at the electrode/electrolyte interface and
AC

122 pseudo capacitors based on fast redox reactions at the electrodes for huge pseudo capacitance [22]. There
123 are also hybrid supercapacitors comprising of both types of electrodes thereby combining both double
124 layer capacitive and pseudocapacitive charging and discharging schemes. Such super capacitors have high
125 energy density, high power density and high cycling stability. With these developments the
126 supercapacitors are adept to bridge the gap between batteries/ fuel cells (with high energy density) and
127 conventional capacitors (with high power density) [23-24]. For electro chemical double layer super
128 capacitors a large specific surface area is favorable as it delivers more space for the adsorption of

6
 ACCEPTED MANUSCRIPT

129 electrolyte ions. Highly porous materials that possess high mechanical strength and large surface area
130 such as aerogels and films, can be synthesized by combining with nanocellulose [25]. This type of porous
131 structures reveal great potential as substrates for flexible supercapacitors [29] and their efficiencies
132 modified by doping with carbon conductive materials like CNTs [26-27] and graphene oxides (GO) [28].

133 Though cellulose-based materials are environmental friendly the chemical processes involved in its

PT
134 preparation indicates a threat to the ecology. Therefore, while designing the green energy storage devices,
135 one has to focus more on to reduce the effect of chemical treatments. Koga and co-workers successfully

RI
136 converted recycled waste pulp-fibres and single-layer GO sheets into a cellulose paper/ Reduced
137 Graphene oxide (RGO) composite using a blend of papermaking process and flash reduction techniques

SC
138 (figure 7). The room temperature, additive free, and millisecond time scale reduction of GO was achieved
139 in the composite by irradiating high intensity pulsed light. This cellulose paper/RGO composite electrode,
140 which gave high specific capacitance of 177 F/g. It was successfully applied for an all-paper based

U
141 flexible supercapacitor that provided a capacitance of 212 F/g [30].
AN
142 .
143
M
D
TE
C EP
AC

144
145 Figure 7: Preparation of the composite derived from single layer GO and recycled cellulose pulp fibres
146 by papermaking and successive flash reduction processes. Adapted from reference 31
147

7
 ACCEPTED MANUSCRIPT

148 The extraction of cellulose fibres from waste paper, and subsequent application in supercapacitor
149 electrodes is proposed as a cost effective route for developing energy storage devices with improved
150 performance [32]. Habio Su et al demonstrated an all solid state symmetric flexible supercapacitor based
151 on the office waste paper fibers/reduced graphene oxide/manganese dioxide (PF/RGO/MnO2) which act
152 as both the positive and negative electrodes. Flexible PF/RGO/MnO2 electrodes with good physical

PT
153 flexibility and excellent mechanical strength were fabricated via a simple solution phase assembly and
154 vacuum filtration method without using any binding agents. Moreover, owing to the advantages of large
155 surface area and microfibers present in paper fiber, the PF based hybrid flexible electrodes show high

RI
156 specific capacitance of 410 Fg− 1 at 0.8 Ag− 1 and retain 93% capacitance over 5000 cycles and display an
157 outstanding electrochemical performance. In addition, the assembled solid-state symmetric

SC
−1 −1
158 supercapacitors exhibit high energy density (19.6 Wh kg at 400 W kg ) and excellent cycling stability
159 of 85.3% retention even after 2000 folding and bending cycles. These investigations thus demonstrate a

U
160 renewable method of turning waste into wealth and deliver a new method to fabricate the sustainable and
161 self-supporting paper-based supercapacitor for application in flexible energy storage devices [33].
AN
162 In a pioneering work, Zhe Weng and his co-workers [34] reported a simple and scalable method to
163 fabricate graphene-cellulose paper (GCP) membranes that act as freestanding and binder-free electrodes
164 for flexible supercapacitors. The electrical conductivity of the GCP membrane shows great stability with
M

165 a reduction of only 6% after being bent 1000 times. This flexible GCP electrode has a high capacitance
−2 −1
166 per geometric area of 81 mFcm , which is equivalent to a gravimetric capacitance of 120 F g of
D

167 graphene, and retains > 99% capacitance over 5000 cycles. Under highly flexible conditions, the
TE

168 supercapacitors exhibit a high capacitance per geometric area of 46 mF cm − 2 for the complete device. All
169 these results indicate that polymer supercapacitors made using GCP membranes are versatile.
170 The fabrication of supercapacitors and lithium ion batteries using commercial paper sheets that were
EP

171 coated with aqueous Carbon Nanotube (CNT) ink using sodium dodecyl benzene sulfonate (SDBS) as
172 surfactant was introduced by Cui and team [35]. The process was based on a simple Meyer rod coating
173 process in line with the main principles of green chemistry. The method implied ways to reduce the
C

174 consumption of organic solvents, usage of low energy intake processes avoiding high temperature or
AC

175 pressure since paper absorbs water easily and binds to CNTs. The resulting conductive paper exhibited
176 flexibility and good mechanical strength as well. Supercapacitors based on CNT conductive paper also
177 displayed a specific capacitance of 200 F g-1 and stable cycling life over 40000 cycles. Later, the same
178 team coated single-walled CNTs (SWCNTs) onto cotton fibres and attained a highly electrically
179 conductive interconnecting network [36]. Supercapacitors made with such electrodes had excellent
180 cycling performance (good capacity retention after 35000 cycles) and a specific capacitance of 70-80 F g-
1
181 . Due to these properties, the combination of cotton/SWCNT electrodes into wearable electronics was

8
 ACCEPTED MANUSCRIPT

182 proposed widely. Kang et al. developed a solid state flexible supercapacitors by coating CNT onto office
183 papers using drop-dry method using gel electrolytes with ionic liquid (i.e. fumed silica nanopowders were
184 mixed with ionic liquid, 1-ethyl-3-methylimidazolium). Even though the supercapacitor exhibited
185 excellent stability, flexibility and specific capacitance of about 135 F g-1, the approach was a pull out from
186 green chemistry principles as the use of ionic liquids is debatable due to their unsafe synthesis [37]. Later,

PT
187 a simple route to obtain three dimensional, lightweight, hybrid aerogels possessing excellent capacitance
188 retention at charge/discharge rates required for a flexible energy storage device was proposed by Xuan
189 yang et al in their work. They demonstrated the use of CNC aerogels as universal substrates by

RI
190 incorporating polypyrrole nanofibers (PPy-NF), polypyrrole-coated carbon nanotubes (PPy-CNT), and
191 spherical manganese dioxide nanoparticles (MnO2-NP), during the aerogel assembly [38].

SC
192 Lee et al demonstrated a new green method of cellulose activation using coffee. In their work they soaked
193 a piece of paper in espresso coffee which acted as a natural activating agent followed by pyrolysis to give

U
194 paper derived carbons (EKACs). Potassium ion being a core ingredient in espresso play an important role
195 in augmenting pyrolysis kinetics and achieving a porous structure and a specific capacitance of 131 F g-1
AN
196 at a scan rate of 1.0 mVs-1 was obtained. All the flexible paper supercapacitors were fabricated by
197 assembling EKAC/CNT mixture embedded paper towel as electrode, PVA/KOH mixture paper towel as
198 electrolyte and polydimethylsiloxane infiltrated paper towel as packing substance. This coffee mediated
M

199 activation of cellulose and the resultant supercapacitor provide a new material and an environmental
200 friendly power source [39].
D

201 Conductive polymers are usually polymers with highly p-conjugated polymeric chains and among these
TE

202 polymers the most widely used ones include polypyrrole (PPy, 0.3–100 S cm−1), polyaniline (PANI, 0.01–
203 5 S cm−1), polyacetylene (PA, 3–1000 S cm−1), polythiophene (PTh, 2–150 S cm−1), poly
204 (phenylenevinylene) (PPV, 10−3- 100 S cm−1) and their derivatives [40]. These conductive polymers have
EP

205 been widely studied for use in sensors, electrochemical capacitors, fuel cell electrodes, batteries, memory
206 devices, and field emission devices [41]. In recent years, significant research efforts have been made to
207 fabricate conductive nanocomposites by combining conductive polymers (especially PPy and PANI) with
C

208 nanocellulose. The major issue that restricts the performance of nanocellulose/conductive polymer
AC

209 composites as supercapacitor electrodes is their low conductivity which lies in the range of 0.02 S cm−1 to
210 5.1 S cm-1 [42]. To surmount this problem, Wang et al. [43] employed well precise core sheath structured
211 conductive nanocomposites by covering a homogeneous layer of PPy on nanocellulose fibers and the as
212 prepared composites achieved an outstanding conductivity about 77 S cm−1 (figure 8). A very general
213 approach of increasing conductivity is to introduce conductive materials into the composites, like carbon
214 based materials. The incorporation of carbon-based conducting components in nanocellulose-based
215 composites is appealing due to their low cost and excellent conductive nature (electrical conductivity upto

9
 ACCEPTED MANUSCRIPT

216 ~ 108 S m−1for graphene [44] and ~105 S m−1for graphite) [45]. NC-based aerogels as substrates of energy
217 devices has drawn great attention [47-49] due to their interesting properties such as high porous structure,
218 large specific surface area and very low density. An interesting example is the Covalently Cross-linked
219 CNF aerogels produced by Zhang et al. [48], which can retain its shape in water due to the interaction
220 between water and cellulose, specifically through hydrogen bonds.

PT
221

RI
U SC
AN
M
D

222
223 Figure 8: PPy polymerization in the presence of equal amounts of pristine CNCs and PVP/CNCs with a
TE

224 cartoon demonstrating the two extremely different morphologies of the end products. Adapted from
225 reference 46
EP

226
227 Flexible solid-state CNF-based aerogel supercapacitors with silver and PANI nanoparticles deposited on
228 aerogel were prepared by Zhang et al [49] and it was observed that the relatively high specific capacitance
C

229 (176 mF cm−2 at 10 mV s−1) of the as fabricated supercapacitors remained the same when they were bent
AC

230 with different bending radius. Exceptionally lightweight aerogels of CNC prepared by Yang et al [50]
231 were considered as universal 3D substrates for nanosized materials in SCs, such as PPy nanofibers, PPy
232 coated CNTs and MnO2 nanoparticles. The resultant composites were lightweight and exhibited great
233 mechanical properties, as indicated in figure 9. It could remain intact when compressed in air or aqueous
234 electrolyte without breaking and recover its original shape on removal of the force making it a promising
235 material for supercapacitor applications.
236

10
 ACCEPTED MANUSCRIPT

PT
RI
237
238 Figure 9: Photograph emphasizing the lightweight nature of a hybrid aerogel resting on top of a feather

SC
239 (left); Photograph of cyclic compression tests in saturated Na2SO4 solution at 0% (middle) and 80%
240 (right) strain. Adapted from reference 50
241

U
242 Carbonization of nanocellulose materials could be yet another tactic of exploiting nanocellulose in
AN
243 supercapacitors. Due to their high conductivities, stability and versatile structures, carbon materials have
244 countless potential in the application as supercapacitor electrode materials [51-53]. In order to increase
245 the accessibility to electrolyte and electrochemical activities, carbon materials of high specific surface
M

246 area, high porosity and containing more oxidative groups are required. This improves its super capacitive
247 behavior, particularly since mesoporous structure of carbon nanofibers improves the uptake of electrolyte
D

248 solution and simplify ion transport kinetics [54]. Compared to polyacrylonitrile or polybenzimidazole,
249 nanocellulose is supposed to be a better source of activated carbon because of its small size, unique
TE

250 porous structure and is sourcing from inexhaustible natural resources [55]. Furthermore, cellulose in
251 nanoscale show features of structural similarity and the ease of graphitization [56].
252 It has been shown that the electrical and chemical properties of carbon nanomaterials can be tailored by
EP

253 heteroatom substitution, most importantly N, P, S and I [57]. These heteroatom-doped nanoscale carbon
254 materials have attracted immense attention in energy storage devices since it could increase surface
C

255 wettability, electrical conductivity and electro-donor tendency [58-59]. Nitrogen, in particular, is
256 considered to be capable of enhancing capacitance since N-containing functional groups can offer more
AC

257 redox pseudo capacitance [60]. A common approach adopted to introduce nitrogen into carbon matrices is
258 the pyrolysis of carbon precursor coated with nitrogen-containing polymer like PPy and PANI. An
259 asymmetric supercapacitor was prepared by Chen et al with bacterial cellulose derived carbon
260 nanofiber/MnO2 and nitrogen-doped carbon nanofiber as electrodes [61]. In their research, the carbon
261 nanofiber obtained by cellulose pyrolysis at 1000 °C was dipped into urea solution at 180 °C for 12 h to
262 develop nitrogen-doped composites. Such a device had an outstanding potential space of 2 V and
263 provided an energy density of 32.91 W h kg−1. Different heteroatoms were further introduced onto

11
 ACCEPTED MANUSCRIPT

264 cellulose derived carbon in their investigations [62]. Cellulose slices were immersed into H2PO4,
265 NH4H2PO4 and H3PO4/ H3BO4 to synthesis P-doped, N, P-co-doped and B, P-co-doped carbon fibers,
266 respectively, via carbonization at 800 °C under N2. All elements were distributed evenly on carbon
267 fibers, as shown in Figure 10. As expected, the corresponding supercapacitors exhibited good super
268 capacitive performance.

PT
RI
SC
269
270 Figure 10: (1) Photograph of a BC pellicle. (2) SEM image of the N,P-co-doped carbon nanofiber surface

U
271 (inset: the typical sample, 2.7×1.2 cm2). (3) SEM image of the inner of N,P-co-doped carbon nanofiber
AN
272 (N,P-CNF). (4) HRTEM image of the N,P-CNF. Adapted from reference 62
273
M

274 The performance of cellulose based supercapacitors based on the previously reported data is summarized
275 in table 2.
D

Electrode material Specific Power Energy Capacitance References

capacitance density density retention
( F g-1)
TE

rGO/CNC hybrid fibre 123.3 at 496.4 mW 5.1 mWh - 63

current density cm-3 cm-3
0.1 A g-1
EP

PEDOT:PSS/SnO2/rGO/ 445 - - - 64
BNC
CNFs/CNTs/PANI/CC 318 - - - 65
C

Cellulose 295 (10 283.63 32. 91 Wh 95.4% 66

Paper/CNTs/ mVs-1 scan kW kg−1 kg−1 capacity
AC

MnO2 (P-CM) rate) retention

96 (200 after
mVs-1) 2000
cycles

Polyester textile/CNTs// - - - 62% at 66

CNT (T- CMC) 12500th
Cycle
Nanocomposite paper 36 1.5 13 100th 67
(CNT cellulose-RTIL) kW kg−1 Wh kg−1 Cycles

12
 ACCEPTED MANUSCRIPT

Graphite/Ni/Co2NiO4- 1737 25.6 80 <4% 68

CP kW kg−1 Wh kg−1 capacita
(cellulose paper) nce loss
(positive electrode) and after
graphite/Ni/AC-CP 20000
(negative electrode) Cycles
N,P-co-doped CNF 204 186 kW 7.76 - 69

PT
kg−1 Wh kg−1
Graphene-cellulose 120 retains > 99% 22
paper (GCP) capacitance

RI
membranes over 5000
cycles
cellulose Nanofibril 252 F g-1 at a 9.5 mW 28.4 µWh >99.5% of 70
(CNF)/reduced discharge cm−2 cm−2 the

SC
graphene oxide current density capacitance
(RGO)/carbon nanotube of 0.5 A g-1 was retained
(CNT) hybrid aerogels after 1000
charge−disch

U
arge cycles at
a current
AN
density of 1
A g-1
Meso-microporous 286 F g-1at a 27 13 W hkg−1 - 71
carbon prepared by the current density kWkg−1
M

combination of a of 0.25 A g-1

template method and
chemical activation with
D

cellulose and
lignosulphonate
TE

Cellulose Nanofibers 916.42 F g-1 8.56 mW 45.7 mW h >98% after 72

(CNFs)/molybdenum cm2 cm2 5000 charge–
EP

disulfide discharge
(MoS2)/reduced cycles at a
graphene oxide (RGO) current
hybrid aerogel density of 0.5
C

mA cm2
276
AC

277 Table 2: Performance of some cellulose based supercapacitors

278 4. Outlooks and Conclusion

279 The main focus of our review was to bring about a broad outlook on the applications of nanocellulose
280 based materials in energy related areas in general and super capacitors in particular. A general picture of
281 cellulose based functional materials is also included in the review. Definitely, challenges do exist and
282 significant research efforts are needed to overcome these challenges in order to develop materials for

13
 ACCEPTED MANUSCRIPT

283 sustainable applications. A basic understanding will definitely reveal the extraordinary application
284 potentials of cellulose nanomaterials in energy and environmental applications. As exemplified in this
285 article, nanocellulose holds incredible value and application potential as super capacitors. With advanced
286 preparation, processing and characterization techniques, cellulose nanomaterials may soon become a
287 significant and potent multifunctional material with huge potential for super capacitor applications.

PT
288 Conflicts of interest
289 The authors declare that there is no conflict of interest regarding the publication of this paper.
290

RI
291 Acknowledgments
292 The authors are thankful to Science Engineering Research Board (SERB, Government of India) for

SC
293 financial assistance in the form of research grant (EMR/2017/000178).

294

295 REFERENCES
U
AN
296 1. K.Tan , S. Heo, M. Foo, I. M. Chew, C. Yoo, An insight into nanocellulose as soft condensed
297 matter: Challenge and future prospective toward environmental sustainability, Sci Total
M

298 Environ 650 (2019) 1309-1326

299 2. B. Dunn, H. Kamath, J.M Tarascon, Electrical energy storage for the grid: a battery of
300 choices, Sci 334 (2011) 928-935
D

301 3. J.M. Tarascon, M. Armand, Issues and challenges facing rechargeable lithium batteries, Nat 414
TE

302 (2001) 359-367

303 4. M.M Pérez-Madrigal , M. G. Edo, and C. Alemán, Powering the future: application of cellulose-
304 based materials for supercapacitors, Green Chem 18 (2016) 5930-5956
EP

305 5. H. Nishide, K. Oyaizu, Toward flexible batteries, Sci 319 (2008) 737-738
306 6. P. Poizot, F. Dolhem, Clean energy new deal for a sustainable world: from non-CO 2 generating
C

307 energy sources to greener electrochemical storage devices, Energy Environ Sci 4 (2011) 2003-
308 2019
AC

309 7. Z.Wang, P. Tammela, M. Strømme, L. Nyholm,Cellulose‐based Supercapacitors: Material and

310 Performance Considerations, Adv Energy Mater 7 (2017) 1700130
311 8. T. Abitbol, A. Rivkin, Y. Cao, Y. Nevo, E. Abraham, T. Ben-Shalom, et al., Nanocellulose, a tiny
312 fiber with huge applications, Curr Opin Biotechnol 39 (2016) 76-88
313 9. X.Wang, C. Yao, F. Wang, Z. Li, Cellulose‐Based Nanomaterials for Energy
314 Applications, Small 14 (2017) 1702240

14
 ACCEPTED MANUSCRIPT

315 10. S. Liu, D. Tao, H. Bai, X. Liu, Cellulose‐nanowhisker‐templated synthesis of titanium

316 dioxide/cellulose nanomaterials with promising photocatalytic abilities, J Appl Polym Sci 126
317 (2012) E282-E290
318 11. M. Pääkkö, J. Vapaavuori, R. Silvennoinen, H. Kosonen, M. Ankerfors, T. Lindström, et al.,
319 Long and entangled native cellulose I nanofibers allow flexible aerogels and hierarchically porous

PT
320 templates for functionalities, Soft Matter 4 (2008) 2492-2499
321 12. L. Hu, G. Zheng, J. Yao, N. Liu, B. Weil, M. Eskilsson, et al., Transparent and conductive paper
322 from nanocellulose fibers, Energy Environ. Sci. 6 (2013) 513-518

RI
323 13. D. Klemm, F. Kramer, S. Moritz, T. Lindström, M. Ankerfors, D. Gray, et al., Nanocelluloses: a
324 new family of nature‐based materials, Angewandte Chemie International Edition 50 (2011) 5438-

SC
325 5466
326 14. X. Yang, E. D. Cranston, Chemically cross-linked cellulose nanocrystal aerogels with shape

U
327 recovery and superabsorbent properties, Chem Mater 26 (2014) 6016-6025
328 15. S. J. Eichhorn, R. J. Young, The Young's modulus of a microcrystalline cellulose, Cellulose 8
AN
329 (2001) 197-207
330 16. J. Rojas, M. Bedoya, Y. Ciro, Current trends in the production of cellulose nanoparticles and
M

331 nanocomposites for biomedical applications, Cellulose-Fundamental Aspects and Current Trends
332 8 (2015) 193-228
333 17. A. Tayeb, E. Amini, S. Ghasemi, M. Tajvidi. Cellulose Nanomaterials—Binding Properties and
D

334 Applications: A Review, Molecules 23 (2018) 2684

TE

335 18. A. Russo, B. Y. Ahn, J. J. Adams, E. B. Duoss, J. T. Bernhard, J. A. Lewis, Pen‐on‐paper

336 flexible electronics, Adv Mater 23 (2011) 3426-3430
337 19. L. Nyholm, G. Nyström, A. Mihranyan, M. Strømme, Toward flexible polymer and paper‐based
EP

338 energy storage devices, Adv Mater 23 (2011) 3751-3769

339 20. D.Klemm, B. Heublein, H.‐P. Fink, A. Bohn, Cellulose: fascinating biopolymer and sustainable
C

340 raw material, Angewandte Chemie International Edition 44 (2005) 3358-3393

341 21. Y. Wang, Y. Song, Y. Xia, Electrochemical capacitors: mechanism, materials, systems,
AC

342 characterization and applications, Chem Soc Rev 45 (2016) 5925-5950

343 22. W. Chen, H. Yu, S.-Y. Lee, T. Wei, J. Li, Z. Fan, Nanocellulose: a promising nanomaterial for
344 advanced electrochemical energy storage, Chem Soc Rev 47 (2018) 2837-2872
345 23. C. Largeot, C. Portet, J. Chmiola, P.-L. Taberna, Y. Gogotsi, P. Simon, Relation between the ion
346 size and pore size for an electric double-layer capacitor, J Am Chem Soc 130 (2008) 2730-2731
347 24. S. G. Kandalkar, D. S. Dhawale, C.-K. Kim, C. D. Lokhande, Chemical synthesis of cobalt oxide
348 thin film electrode for supercapacitor application, synth Met 160 (2010) 1299-1302

15
 ACCEPTED MANUSCRIPT

349 25. J. Cai, S. Liu, J. Feng, S. Kimura, M. Wada, S. Kuga, et al., Cellulose–silica nanocomposite
350 aerogels by in situ formation of silica in cellulose gel,Angewandte Chemie International
351 Edition 51 (2012) 2076-2079
352 26. X. Zhang, Z. Lin, B. Chen, S. Sharma, C. Wong, W. Zhang, et al., Solid-state, flexible, high
353 strength paper-based supercapacitors, J Mater Chem A 1 (2013) 5835-5839

PT
354 27. Y.J. Kang, S. -J. Chun, S.-S. Lee, B.-Y. Kim, J. H. Kim, H. Chung, et al., All-solid-state flexible
355 supercapacitors fabricated with bacterial nanocellulose papers, carbon nanotubes, and triblock-
356 copolymer ion gels, ACS Nano 6 (2012) 6400-6406

RI
357 28. K. Gao, Z. Shao, J. Li, X. Wang, X. Peng, W. Wang, et al., Cellulose nanofiber–graphene all
358 solid-state flexible supercapacitors, J Mater Chem A 1 (2013): 63-67

SC
359 29. X. Lu, M. Yu, G. Wang, Y. Tong, Y. Li, Flexible solid-state supercapacitors: design, fabrication
360 and applications, Energy Environ Sci 7 (2014) 2160-2181

U
361 30. Y. Gao, W. Zhang, Q. Yue, B. Gao, Y. Sun, J. Kong, et al., Simple synthesis of hierarchical
362 porous carbon from Enteromorpha prolifera by a self-template method for supercapacitor
AN
363 electrodes, J POWER SOURCES 270 (2014) 403-410
364 31. H. Koga, H. Tonomura, M. Nogi, K. Suganuma, Y. Nishina, Fast, scalable, and eco-friendly
365 fabrication of an energy storage paper electrode, Green Chem 18 (2016) 1117-1124
M

366 32. Y. N. Sudhakar, D. K. Bhat, M. Selvakumar, Ionic conductivity and dielectric studies of acid
367 doped cellulose acetate propionate solid electrolyte for supercapacitor, POLYM ENG SCI 56
D

368 (2016) 196-203

TE

369 33. H. Su, P. Zhu, L. Zhang, F. Zhou, G. Li, T. Li, et al., Waste to wealth: A sustainable and flexible
370 supercapacitor based on office waste paper electrodes, J Electroanal Chem 786 (2017) 28-34
371 34. Z. Weng, Y. Su, D.‐W. Wang, F. Li, J. Du, H.‐M. Cheng, Graphene–cellulose paper flexible
EP

372 supercapacitors, Adv Energy Mater 1 (2011) 917-922

373 35. L. Hu, J.W. Choi, Y.Yang, S. Jeong, F. La Mantia, L.-F. Cui, et al., Highly conductive paper for
374 energy-storage devices, Proceedings of the National Academy of Sciences 106 (2009) 21490-
C

375 21494
AC

376 36. M. Pasta, F. La Mantia, L. Hu, H.D. Deshazer, Y. Cui, Aqueous supercapacitors on conductive
377 cotton, Nano Res 3 (2010) 452-458
378 37. W. Liu, X. Yan, J. Lang, C. Peng, Q. Xue, Flexible and conductive nanocomposite electrode
379 based on graphene sheets and cotton cloth for supercapacitor, J Mater Chem 22 (2012) 17245-
380 17253
381 38. X. Yang, K. Shi, I. Zhitomirsky, E. D. Cranston, Cellulose nanocrystal aerogels as universal 3D
382 lightweight substrates for supercapacitor materials, Adv Mater 27 (2015) 6104-6109

16
 ACCEPTED MANUSCRIPT

383 39. D. Lee, Y.-G. Cho, H.-K. Song, S.-J. Chun, S.-B. Park, D.-H. Choi, et al., Coffee-Driven Green
384 Activation of Cellulose and Its Use for All-Paper Flexible Supercapacitors. ACS Appl Mater
385 Interfaces 9 (2017) 22568-22577
386 40. Y. Shi, L. Peng, Y. Ding, Y. Zhao, G. Yu, Nanostructured conductive polymers for advanced
387 energy storage, Chem Soc Rev 44 (2015) 6684-6696

PT
388 41. C. Li, H. Bai, G. Shi, Conducting polymer nanomaterials: electrosynthesis and applications,
389 Chem Soc Rev 38 (2009) 2397-2409
390 42. S. Li, D. Huang, J. Yang, B. Zhang, X. Zhang, G. Yang, et al., Freestanding bacterial cellulose–

RI
391 polypyrrole nanofibres paper electrodes for advanced energy storage devices, Nano Energy 9
392 (2014) 309-317

SC
393 43. H. Wang, L. Bian, P. Zhou, J. Tang, W. Tang, Core–sheath structured bacterial
394 cellulose/polypyrrole nanocomposites with excellent conductivity as supercapacitors, J. Mater.

U
395 Chem. A 1 (2013) 578-584
396 44. E.Lago, P. S. Toth, G. Pugliese, V. Pellegrini, F. Bonaccorso, Solution blending preparation of
AN
397 polycarbonate/graphene composite: boosting the mechanical and electrical properties, RSC Adv 6
398 (2016) 97931-97940
399 45. H.O. Pierson, Handbook of Carbon, Graphite, Diamonds and Fullerenes: Processing, Properties
M

400 and Applications. William Andrew, 2012

401 46. X. Wu, J. Tang, Y. Duan, A. Yu, R. M. Berry, K. C. Tam, Conductive cellulose nanocrystals with
D

402 high cycling stability for supercapacitor applications, J Mater Chem. A 2 (2014): 19268-19274
TE

403 47. K. Gao, Z. Shao, X. Wang, Y. Zhang, W. Wang, F. Wang, Cellulose nanofibers/multi-walled
404 carbon nanotube nanohybrid aerogel for all-solid-state flexible supercapacitors, RSC Adv 3
405 (2013) 15058-15064
EP

406 48. W. Zhang, Y. Zhang, C. Lu, Y. Deng, Aerogels from crosslinked cellulose nano/micro-fibrils and
407 their fast shape recovery property in water, J Mater Chem. 22 (2012) 11642-11650
408 49. X. Zhang, Z. Lin, B. Chen, W. Zhang, S. Sharma, W. Gu, Y. Deng, Solid-state flexible
C

409 polyaniline/silver cellulose nanofibrils aerogel supercapacitors, J Power Sources 246 (2014) 283-
AC

410 289
411 50. X. Yang, K. Shi, I. Zhitomirsky, E. D. Cranston, Cellulose nanocrystal aerogels as universal 3D
412 lightweight substrates for supercapacitor materials, Adv Mater 27 (2015) 6104-6109
413 51. L. Dai, D. W. Chang, J.‐B. Baek, W. Lu, Carbon nanomaterials for advanced energy conversion
414 and storage, Small 8 (2012) 1130-1166

17
 ACCEPTED MANUSCRIPT

415 52. L.-F. Chen, X.-D. Zhang, H.-W. Liang, M. Kong, Q.-F. Guan, P. Chen, et al., Synthesis of
416 nitrogen-doped porous carbon nanofibers as an efficient electrode material for
417 supercapacitors, ACS nano 6 (2012) 7092-7102.
418 53. J. Cai, H. Niu, Z. Li, Y. Du, P. Cizek, Z. Xie, et al,, High-performance supercapacitor electrode
419 materials from cellulose-derived carbon nanofibers, ACS Appl Mater Interfaces 7 (2015) 14946-

PT
420 14953
421 54. V. Kuzmenko, A. M. Saleem, H. Staaf, M. Haque, A. Bhaskar, M. Flygare, et al., Hierarchical
422 cellulose-derived CNF/CNT composites for electrostatic energy storage, J Micromech Microeng

RI
423 26 (2016) 124001
424 55. Z.-Y. Wu, C. Li, H.‐W. Liang, J.‐F. Chen, S.‐H. Yu, Ultralight, flexible, and fire‐resistant carbon

SC
425 nanofiber aerogels from bacterial cellulose, Angewandte Chemie 125 (2013) 2997-3001
426 56. L. Deng, R. J. Young, I. A. Kinloch, A. M. Abdelkader, S. M. Holmes, D A. De Haro-Del Rio, et

U
427 al.,, Supercapacitance from cellulose and carbon nanotube nanocomposite fibers, ACS Appl
428 Mater Interfaces 5 (2013) 9983-9990
AN
429 57. D. Jana, C.-L. Sun, L.-C. Chen, Kuei-Hsien Chen, Effect of chemical doping of boron and
430 nitrogen on the electronic, optical, and electrochemical properties of carbon nanotubes, Prog
Mater Sci 58 (2013) 565-635
M

431
432 58. B. Xu, D. Zheng, M. Jia, G. Cao, Y. Yang, Nitrogen-doped porous carbon simply prepared by
433 pyrolyzing a nitrogen-containing organic salt for supercapacitors, Electrochim Acta 98 (2013)
D

434 176-182
TE

435 59. J. Han, G. Xu, B. Ding, J. Pan, H. Dou, D. R. MacFarlane, Porous nitrogen-doped hollow carbon
436 spheres derived from polyaniline for high performance supercapacitors, J Mater Chem A 2 (2014)
437 5352-5357
EP

438 60. X. Y. Chen, C. Chen, Z. J. Zhang, D.H. Xie, X. Deng, Nitrogen-doped porous carbon prepared
439 from urea formaldehyde resins by template carbonization method for
440 supercapacitors, Ind Eng Chem Res 52 (2013) 10181-10188
C

441 61. L. F.Chen, Z.-H. Huang, H.‐W Liang, Q.‐F. Guan, S.‐H. Yu.Bacterial‐Cellulose‐Derived Carbon
AC

442 Nanofiber@ MnO2 and Nitrogen‐Doped Carbon Nanofiber Electrode Materials: An Asymmetric
443 Supercapacitor with High Energy and Power Density, Adv Mater 25 (2013) 4746-4752
444 62. L. F. Chen, Z.‐H. Huang, H.‐W. Liang, H.‐L. Gao, S.‐H. Yu, Three‐dimensional heteroatom‐
445 doped carbon nanofiber networks derived from bacterial cellulose for supercapacitors, Adv Funct
446 Mater 24 (2014) 5104-5111

18
 ACCEPTED MANUSCRIPT

447 63. G. Chen, T. Chen, K. Hou, W. Ma, M. Tebyetekerwa, Y. Cheng, et al., hydrophilic
448 graphene/cellulose nanocrystal fiber-based electrode with high capacitive performance and
449 conductivity, Carbon 127 (2018) 218-227
450 64. K.K. Liu, Q. Jiang, C. Kacica, H.G. Derami, P. Biswas, S. Singamaneni, Flexible solid-state
451 supercapacitor based on tin oxide/reduced graphene oxide/bacterial nanocellulose, RSC Adv 8

PT
452 (2018) 31296-31302
453 65. Y.Yang, C. Chen, D. Li, Electrodes based on cellulose nanofibers/carbon nanotubes networks,
454 polyaniline nanowires and carbon cloth for supercapacitors, Mater Res Express 6 (2018) 035008

RI
455 66. Z. Gui , H. Zhu, E. Gillette, X. Han, G. W. Rubloff, L. Hu, S. B. Lee, Natural cellulose fiber as
456 substrate for supercapacitor, ACS Nano 7 (2013) 6037-6046

SC
457 67. V. L.Pushparaj, M. M. Shaijumon, A, Kumar, S. Murugesan, L.Ci, R. Vajtai, et al., Flexible
458 energy storage devices based on nanocomposite paper, Proc Natl Acad Sci 104 (2007) 13574-

U
459 13577
460 68. J. X.Feng, S. H. Ye, A. L. Wang, X. F. Lu, Y. X. Tong, G. R. Li, Flexible Cellulose Paper‐based
AN
461 Asymmetrical Thin Film Supercapacitors with High‐Performance for Electrochemical Energy
462 Storage, Adv Funct Mater 24 (2014) 7093-7101
M

463 69. L. F.Chen, Z. H. Huang, H. W. Liang, H. L. Gao, S. H. Yu, Three‐dimensional heteroatom‐

464 doped carbon nanofiber networks derived from bacterial cellulose for supercapacitors, Adv Funct
465 Mater 24 (2014) 5104-5111
D

466 70. Q. Zheng, Z. Cai, Z. Ma, S. Gong, Cellulose nanofibril/reduced graphene oxide/carbon nanotube
TE

467 hybrid aerogels for highly flexible and all-solid-state supercapacitors, ACS Appl Mater Interfaces
468 7 (2015) 3263-3271
469 71. Z. Zhao, S.Hao, P. Hao, Y. Sang, A. Manivannan, N. Wu, et al., Lignosulphonate-cellulose
EP

470 derived porous activated carbon for supercapacitor electrode, J Mater Chem A 3 (2015) 15049-
471 15056
72. Y. Lv, L. Li, Y. Zhou, M. Yu, J. Wang, J. Liu, et al., A cellulose-based hybrid 2D material
C

472
473 aerogel for a flexible all-solid-state supercapacitor with high specific capacitance, RSC Adv 7
AC

474 (2017) 43512-43520

19