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High Performance, Flexible, Solid-State Supercapacitors

Based on a Renewable and Biodegradable Mesoporous
Cellulose Membrane
Dawei Zhao, Chaoji Chen, Qi Zhang, Wenshuai Chen, Shouxin Liu, Qingwen Wang,
Yixing Liu, Jian Li, and Haipeng Yu*

low cost, miniaturized, light-weight, and

A flexible, transparent, and renewable mesoporous cellulose membrane flexible. Such energy storage systems
(mCel-membrane) featuring uniform mesopores of ≈24.7 nm and high are in urgent need to meet the growing
porosity of 71.78% is prepared via a facile and scalable solution-phase demand for portable consumer electronic
devices.[1] The performance of SCs and
inversion process. KOH-saturated mCel-membrane as a polymer electrolyte
MSCs depends on several components,
demonstrates a high electrolyte retention of 451.2 wt%, a high ionic including the electrode, electrolyte, and
conductivity of 0.325 S cm−1, and excellent mechanical flexibility and separator. Much attention has been given
robustness. A solid-state electric double layer capacitor (EDLC) using activated to electrode materials and structures, in
carbon as electrodes, the KOH-saturated mCel-membrane as a polymer elec- an attempt to improve electrochemical
trolyte exhibits a high capacitance of 110 F g−1 at 1.0 A g−1, and long cycling performance.[2–6] However, much less
attention has been given to the electrolyte
life of 10 000 cycles with 84.7% capacitance retention. Moreover, a highly
and separator.
integrated planar-type micro-supercapacitor (MSC) can be facilely fabricated The electrolyte reportedly plays an
by directly depositing the electrode materials on the mCel-membrane-based important role in determining the max-
polymer electrolyte without using complicated devices. The resulting MSC imum operating voltage, lifetime and
exhibits a high areal capacitance of 153.34 mF cm−2 and volumetric capaci- safety of SCs.[7] Conventional liquid elec-
trolytes include organic and aqueous
tance of 191.66 F cm−3 at 10 mV s−1, representing one of the highest values
electrolytes. The former is easy to catch
among all carbon-based MSC devices. These findings suggest that the fire, thus brings safety issues, while
developed renewable, flexible, mesoporous cellulose membrane holds great the latter has narrow potential window
promise in the practical applications of flexible, solid-state, portable energy that may lower the energy density of the
storage devices that are not limited to supercapacitors. SCs. Recently, polymer electrolytes have
attracted increasing attention due to their
ability to form thin films, their high ionic
conductivity, wide electrochemical window, and service safety.[8–11]
1. Introduction
Incorporating the electrolyte and separator into a single
Supercapacitors (SCs) and micro-supercapacitors (MSCs) have poly­mer membrane has promoted the development of energy
received increasing attention recently in the development storage systems for portable and wearable electronics.[12–14]
of energy storage systems, particularly in systems that are Much effort has been given to preparing high-performance gel
polymer electrolytes[15] and porous polymer electrolytes.[16–19]
For example, a zwitterionic gel electrolyte of propylsulfonate
Dr. D. Zhao, Q. Zhang, Dr. W. Chen, Prof. S. Liu, Prof. Q. Wang,
Prof. Y. Liu, Prof. J. Li, Prof. H. Yu dimethylammonium propylmethacrylamide exhibited good
Key Laboratory of Bio-based Material Science water retention capability, which led to a high capacitance and
and Technology of Ministry of Education cycling stability.[15] A microporous polymer electrolyte from a
Northeast Forestry University poly(ethylene glycol)-grafted poly(arylene ether ketone) com-
Harbin 150040, P. R. China
E-mail: yuhaipeng20000@gmail.com
posite membrane matrix incorporating a chitosan-based LiClO4
Dr. C. Chen
gel was prepared.[18] The polymer electrolyte exhibited good
State Key Laboratory of Advanced Electromagnetic mechanical properties and low leakage, and high cycling sta-
Engineering and Technology bility when incorporated into a solid-state electric double layer
School of Electrical and Electronic Engineering capacitor (EDLC). A graphene-oxide-doped ion gel electro-
Huazhong University of Science and Technology lyte exhibited a high ionic conductivity.[19] This gel electrolyte
Wuhan 430074, P. R. China
was then incorporated into an all-solid-state SC, which exhib-
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/aenm.201700739.
ited high capacitance performance and good cycling stability.
All these works have demonstrated the effectiveness of the
DOI: 10.1002/aenm.201700739 poly­mer electrolytes in EDLCs and solid-state SCs. However,

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the conventional polymer electrolytes are generally neither depositing the electrodes on the mCel-membrane in different
renewable nor biodegradable, or involve complicated prepara- configurations without the using of binder or complicated
tion process, which have restricted their large-scale application. setups. The electrochemical performances of the EDLCs and
Achieving mechanical flexibility and environmental benignity MSCs were investigated and the results were compared with
of electrolytes, while retaining their good electrochemical per- those obtained by using the commercialized NKK-MPF30AC,
formance, remains a challenge. A simple method for preparing NKK-TF4030, and polyvinyl alcohol (PVA).
versatile polymer electrolytes with high ionic conductivity,
renewability, biodegradability, and good mechanical properties
is highly desirable, but also challenging. 2. Results and Discussion
Renewable polymer solutes and appropriate solvents are
essential for fabricating porous polymer electrolyte membrane. 2.1. Preparation and Properties of the mCel-Membrane
Among the numerous optional polymer solutes, cellulose is
the most abundant, renewable, and biodegradable natural Cellulose was dissolved in [Bmim]Cl IL, which yielded a
biopolymer on earth. The use of cellulose for such applica- homogenous solution (denoted as Cel/IL) after stirring for
tions would meet the green/sustainable demand from the 18 min (Figure S1, Supporting Information). The good solu-
public.[20] The properties of cellulose such as low cost, high bility of cellulose in [Bmim]Cl was attributed to the formation
dimensional/thermal/chemical stability, excellent mechanical of hydrogen bonding interactions between the hydroxyl pro-
strength, and flexibility, can meet a number of key require- tons of cellulose and chloride anions/imidazolium cations in
ments for ideal poly­ mer electrolyte separators. Some cellu- [Bmim]Cl.[35] Therefore, the dissolution of cellulose in IL was
lose-based membranes (especially cellulose acetate, methyl considered to be a physical process, and IL was used as a non-
cellulose, and cellulose-based composites) have been used as derivatizing solvent for regenerating the cellulose film.[36] The
separation membranes in energy storage devices.[21–25] How- Cel/IL was viscous, and its viscosity decreased with increasing
ever, their low porosity raises serious concerns over insufficient temperature up to 90 °C, at which point the viscosity reached
electrolyte wettability, which could directly impair ionic trans- a plateau of ≈1500 mPa s. From this result, 85 °C was selected
port through the separators. Thus, high porosity is desirable in as the optimum temperature for Cel/IL treatment. When the
order for the ions to flow back and forth between the electrodes. Cel/IL gel was immersed in distilled water, [Bmim]Cl was sub-
A higher porosity separator can ensure the membrane has an stituted by water which gradually diffused from the surface into
excellent electrolyte retention and an enhanced ionic conduc- the bulk of the gel. This spontaneous molecular self-assembly
tivity, resulting in less heat generated and less energy wasted. process resulted in cellulose chains rearranging, which formed
Recently, nanoporous cellulose electrolyte membranes with an expanded white regenerated cellulose hydrogel. After solidi-
high porosities have been reportedly prepared using cellulose fying and drying, a freestanding mCel-membrane was obtained.
nanofibers (CNFs) and electrospun cellulose mats.[26–29] How- The mCel-membrane with a thickness of 22 μm was highly
ever, the complicated preparation process and limited produc- transparent with a light transmittance of 91.1% at 600 nm
tion restricted their large-scale application in energy storage (Figure 1a,d). The mCel-membrane exhibited a super apparent
devices. The phase-inversion method is typically the most effi- flexibility, which could be processed into different sizes and
cient and techno-economic method for preparing nanoporous shapes, even folded into various forms. High-resolution scan-
membranes.[30–32] Nevertheless, cellulose does not readily dis- ning electron microscopy (SEM) images indicated that the
solve in common organic solvents, so can be difficult to directly mCel-membrane had a macrovoid-free and 3D interconnected
process into nanoporous membranes.[33,34] The facile fabrica- porous structure (Figure 1b,c). The morphology of the mCel-
tion of the nanoporous cellulose electrolyte membrane with membrane surface was very smooth. Abundant uniformly dis-
high ionic conductivity is not straightforward. Detailed studies tributed mesopores with diameters of 5–30 nm (most probable
to in-depth reveal its performance in solid-state SCs and flexible aperture of 24.7 nm) were observed (Figure S2, Supporting
MSCs are also currently necessary. Information). The porosity (Equation S1, Supporting Informa-
Here, a flexible and transparent renewable mesoporous cel- tion) of the mCel-membrane was 71.78%, which was higher than
lulose membrane (hereafter referred to as mCel-membrane) those of nonwoven polypropylene membrane (NKK-MPF30AC)
was fabricated via a phase-inversion method with an ionic (51.08%) and cellulosic separator paper (NKK-TF4030) (29.68%)
liquid (IL) as the solvent. Cellulose can be easily dissolved in (Figure 1e). The high porosity can provide rich ion diffusion
the IL of 1-butyl-3-methylimidazolium chloride ([Bmim]Cl), and channels and enough room for electrolyte uptake. Although
then regenerated into a film with pure water as the nonsolvent. the crystal form of the mCel-membrane was converted to cel-
Two polytetrafluoroethylene (PTFE) millipore membranes were lulose II, the ultimate tensile stress and Young’s modulus of
used as templates, to generate mesopores during the drying the mCel-membrane in a dry state remained at 171.5 MPa and
process. Membrane characteristics of the mCel-membrane, 8.93 GPa, respectively (Figure S1d, Supporting Information).
including flexibility, porous structure, electrolyte uptake, ionic The good thermal stability is an essential requirement for the
conductivity, thermal stability, and mechanical strength, were safety of polymer membranes applying in energy devices. The
evaluated. Based on this comprehensive understanding of the initial thermal degradation temperature of the mCel-membrane
separator properties, solid-state EDLCs were assembled with was about 275 °C (Figure 1f), which was comparable to that of
the potassium hydroxide (KOH)-saturated mCel-membrane NKK-TF4030, but inferior to that of NKK-MPF30AC. The initial
as the polymer electrolyte, and activated carbon as the elec- thermal degradation temperature of mCel-membrane was also
trodes. Flexible MSCs were also facilely fabricated by directly higher than those of most polymer membrane materials, such

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Figure 1.  Morphology and properties of the mCel-membrane. NKK-MPF30AC and NKK-TF4030 were also investigated for comparison. a) Optical
photographs show the transparency, flexibility, and tailorability of the mCel-membrane. b) Surface and c) cross-sectional SEM images. d) Light trans-
mittance (T%). Insets show optical images of the NKK-MPF30AC, NKK-TF4030, and mCel-membrane. e) Porosity and most probable aperture size.
f) Thermogravimetric (TG) curves and their derivative TG (DTG) curves. g) Static contact angles for a droplet of 6 m KOH solution, and absorption–
swelling characteristics. h) Ionic conductivity and electrolyte uptake. i) Tensile stress–strain curves of three types of membranes in a wetting state by
6 m KOH solution.

as the poly (ethylene glycol)–grafted poly (arylene ether ketone) far higher than those of NKK-MPF30AC and NKK-TF4030
(PAEK-g-PEG) membrane (160 °C) and poly(aryl ether sulfone) (Figure 1i). In summary, the above results suggest that the
membrane (200 °C).[18,37] The results indicate that the mCel- mCel-membrane with abundant mesopores, high ionic con-
membrane had a good thermal stability. ductivity, excellent electrolyte retention, and robust mechanical
The static contact angle of the mCel-membrane was 83.15° properties has the potential as an electrolyte separator in energy
for a droplet 6 m KOH solution. This contact angle value storage devices.
resulted from the strong capillary tension of the smooth surface
(Figure 1g). The contact angle value decreased with the time
prolonging, and fell to zero after several minutes (Figure S3, 2.2. KOH Saturated mCel-Membrane as the Polymer Electrolyte
Supporting Information). After soaking in 6 m KOH solu- in Solid-State EDLC
tion for 48 h, the electrolyte uptake and ionic conductivity
(Equations S2 and S3, Supporting Information) of the mCel- A solid-state EDLC was fabricated using the mCel-membrane/
membrane were calculated as 587.5 wt% and 0.325 S cm−1, KOH as a polymer electrolyte, to achieve a portable energy
respectively (Figure 1h). After 48 h of desorption at room tem- storage system. The solid-state EDLC was fabricated by encap-
perature, the electrolyte retention of the mCel-membrane was sulating the EDLC with ethylene vinyl acetate (EVA) hot-melted
451.2 wt%, which was far higher than those of NKK-MPF30AC glue. EDLCs containing NKK-MPF30AC/KOH, NKK-TF4030/
and NKK-TF4030 (Figure S4, Supporting Information). The KOH, and PVA/KOH were prepared similarly for comparison.
tensile strengths of the soppy mCel-membrane in the A and B Their electrochemical properties were measured under typical
directions were 42.98 and 40.22 MPa, respectively. These were atmospheric conditions. Cyclic voltammetry (CV) curves of

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these EDLCs at scan rates of 10, 50, and 300 mV s−1 are shown The equivalent series resistance of the mCel-membrane-based
in Figure 2a–c, respectively. The CV curves had similar pro- EDLC was 0.41 Ω, which was smaller than those of the PVA/
files in wide potential window of 0–1.0 V. The integrated area KOH-based EDLC (0.691 Ω), NKK-MPF30AC-based EDLC
of the CV curve of mCel-membrane-based EDLC was larger (0.892 Ω), and NKK-TF4030-based EDLC (4.949 Ω).
than those of the NKK-MPF30AC, NKK-TF4030, and PVA- All four EDLCs exhibited good specific capacitances and rate
based EDLCs (Figures S5–S7, Supporting Information). This capabilities at current densities of 0.5–10 A g−1 (Figure 2h).
indicated better equivalent EDLC behavior and a higher specific The specific capacitance values for the mCel-membrane-based
capacitance of the solid-state EDLC with a mCel-membrane/ EDLC were 1.4–1.7 times higher than those of the PVA/KOH,
KOH electrolyte. Galvanostatic charge/discharge (GCD) pro- NKK-MPF30AC, and NKK-TF4030-based EDLCs. The value of
files measured at current densities of 0.5, 5, and 10 A g−1 are 120.6 F g−1 at 0.5 A g−1 for the mCel-membrane-based EDLC
shown in Figure 2d–f, respectively. The mCel-membrane-based was also superior to reported values of 92.79 F g−1 for poly(aryl
EDLC exhibited a longer discharge time and a lower voltage ether sulfone) in 6 m KOH,[37] 93 F g−1 for polyethylene oxide in
drop than the other three EDLCs. For example, the discharge 6 m KOH,[38] and 118.63 F g−1 for the PAEK/PAEK-g-PEG/LiClO4
time of the mCel-membrane-based EDLC was 2.3 s at a current gel electrolyte.[18] The capacitance of the mCel-membrane-based
density of 10 A g−1. This was 1.9 times higher than that of the EDLC was 81.4 F g−1 at 10 A g−1, which was equivalent to 74.5%
PVA/KOH-based EDLC (1.2 s), 2.3 times higher than that of the of the capacitance of 110 F g−1 at 1 A g−1, indicating good rate
NKK-MPF30AC-based EDLC (1.0 s), and 3.2 times higher than capability. 84.7% of the initial capacitance of the mCel-mem-
that of the NKK-TF4030-based EDLC (0.7 s). Nyquist plots were brane-based EDLC was retained after 10 000 charge–discharge
obtained by the alternating current impedance method from cycles at 1 A g−1 (Figure 2i). This retention was considerably
0.01 to 105 Hz. The intercept with the real axis at high frequen- higher than those of the EDLCs containing PVA/KOH (65.18%),
cies indicated the series resistance of the EDLC (Figure 2g). NKK-MPF30AC (34.73%), and NKK-TF4030 (4.56%) electrolytes.

Figure 2. Electrochemical properties of the solid-state mCel-membrane-based EDLC. Similar solid-state EDLCs containing NKK-MPF30AC, NKK-
TF4030, and PVA/KOH as electrolyte were also tested for comparison. a–c) CV curves measured at scan rates of 10, 50, and 300 mV s−1, respectively.
d–f) GCD profiles measured at current densities of 0.5, 5, and 10 A g−1, respectively. g) Nyquist plots. h) Specific capacitances measured at different
current densities. i) Cycling performance measured at a current density of 1 A g−1.

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Visual inspection of the mCel-membrane after 10 000 cycles The energy density and power density are important param-
showed that the mCel-membrane remained intact and usable. eters for comparing the performance of EDLCs. The max-
When the same mCel-membrane was reused in a newly assem- imum energy density of the mCel-membrane-based EDLC
bled EDLC, the CV, GCD, and electrochemical impedance spec- was 4.37 Wh kg−1 and power density being 0.249 kW kg−1
troscopy (EIS) curves exhibited similar profiles to those of the at a current density of 0.5 A g−1 (Figure 4a). This value was
initial EDLC. The voltage drop of the newly assembled EDLC 1.56 times higher than that of the NKK-MPF30AC-based EDLC,
was 0.037 V (Figure S8, Supporting Information). In summary, 1.66 times higher than that of the NKK TF4030-based
these results demonstrated that the solid-state mCel-membrane- EDLC, and 1.50 times higher than that of the PVA/KOH-based
based EDLC exhibited excellent electrochemical performance, EDLC. At a current density of 10 A g−1, the energy density of
which was superior to that of the PVA/KOH-based EDLC. This the mCel-membrane-based EDLC was 2.94 Wh kg−1 at a power
was attributed to: 1) the homogeneous mesoporous structure density of 5.031 kW kg−1. Two mCel-membrane-based EDLCs
and abundant active hydroxyl groups imparted high electrolyte could be connected in series or in parallel, to obtain a device
retention and excellent mechanical properties on the mCel- that outputted approximately twice the potential, or twice the
membrane, which improved the ionic conductivity and capaci- current density and charge–discharge time of those of the
tance cycling stability; 2) the high porosity and nanostructure single EDLC (Figure 4b,c). The connected mCel-membrane-
provided abundant ion transport pathways, and abundant elec- based EDLCs were stable in different voltage windows, which
trolyte storage space. This improved the rate capability and indicated their good practical prospects (Figure S9, Supporting
reduced the voltage drop. Information). As shown in Figure 4d and Movie S1 (Supporting
The lifetime stability of the solid-state mCel-membrane-based Information), the 2.0 V light-emitting diodes (LEDs) were pow-
EDLC was evaluated by measuring its electrochemical perfor- ered by two mCel-membrane-based EDLCs in series connection
mance after different time intervals. The CV and GCD curves for a few minutes.
in the scan potential windows of 0–0.5, 0–0.8, and 0–1.0 V
maintained their quasirectangular and symmetrical triangular
profiles, respectively, 24 h after EDLC preparation (Figure 3a,b). 2.3. Flexible Planar-Type mCel-Membrane-Based MSC
This suggested that the EDLC was adaptable to the wide
working potential window. The profiles of the CV curves at a The straightforward preparation and favorable properties of
scan rate of 50 mV s−1 were also well retained after different the mCel-membrane suggested its potential in flexible planar-
time intervals (Figure 3c). Specific capacitances were calculated type MSCs. During the preparation of the mCel-membrane,
from the GCD profiles at a current density of 1 A g−1. The spe- the adhesive properties of Cel/IL because of intermolecular
cific capacitance decreased by 1.3% after 24 h, 6.4% after 72 h, forces and electrostatic interactions were sufficient to adhere
and 11.7% after 96 h (Figure 3d). These results demonstrated to and retain electrodes for preparing a planar-type MSC.
the long lifetime stability of the mCel-membrane-based EDLC. Figure  5a shows that with the aid of a PTFE mask, activated

Figure 3.  Lifetime stability of the solid-state mCel-membrane-based EDLC. a) CV curves measured in different scan potential windows, and at a
scan rate of 50 mV s−1. b) GCD profiles measured in different scan potential windows, and at a current density of 1 A g−1. c) CV curves at 50 mV s−1,
measured at different time intervals. d) Specific capacitances and GCD profiles (at a current density of 1 A g−1) calculated at different time intervals.

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Figure 4.  Application performance of the solid-state mCel-membrane-based EDLC. a) Ragone plots. b) CV curves and c) GCD profiles of two mCel-
membrane-based EDLCs connected in series and in parallel, at a scan rate of 50 mV s−1 and current density of 1 A g−1. d) Photographs of the LEDs
powered by two mCel-membrane-based EDLCs connected in series.

carbon powder was directly deposited on the blank surface of areal capacitance and volumetric capacitance slightly decreased
the Cel/IL. Subsequent immersion in water and drying in an from 84.8 to 79.2 mF cm−2 and from 106 to 99 F cm−3 (93.4%
oven yielded a free-standing mCel-membrane-based MSC. This retention), respectively (Figure 5e). The profile of the 1000th
patterning technique here is free of glue or other additives, CV curve largely overlapped with those of the 1st and 500th CV
making it lower cost, simpler, and more versatile than many curves (Figure 5e, inset), demonstrating the excellent cycling
other patterning techniques such as photolithography,[39] ink- stability of the MSC.
printing,[40] laser scribing or writing,[41] and plasma-scanning.[42] When bent to angles of 0°, 90° or 180°, the MSC did not
Different configurations of interdigitated electrodes could be show any obvious distortion in the CV curves or degradation
fabricated on the mCel-membrane-based MSC, which demon- in its capacitance (Figure 6a). This suggested the potential of
strated the good scalability of the procedure (Figure 5b). The the MSC in flexible wearable devices. Ragone plots in Figure 6b
MSC exhibited excellent flexibility, and could be bent to 180° showed that the MSC delivered a volumetric energy density
without compromising its structural integrity (Figure S10, Sup- of 6.655 mWh cm−3 at a power density of 0.2395 W cm−3, and
porting Information). SEM images showed that the activated 1.545 mWh cm−3 at a power density of 5.561 W cm−3. These
carbon finger electrode was highly integrated with the mCel- values were superior to those of some carbon-based MSCs.[43–46]
membrane (Figures S11 and S12, Supporting Information). No Two MSCs connected in series exhibited twice the operating
obvious potholes or interfacial defects were observed. voltage of the single MSC. Two connected in parallel exhib-
The electrochemical properties of the mCel-membrane-based ited approximately twice the current and discharge time of the
MSC were investigated under typical atmospheric conditions. single MSC (Figure 6c). Either in a plane or in a curved state,
CV curves were measured at scan rates of 10–300 mV s−1 the MSC could power a digital watch for an extended period
(Figure 5c and Figure S13 (Supporting Information)). These (Figure 6d and Movie S2 (Supporting Information)). The MSC
exhibited symmetrical quasirectangular profiles at high scan retained its flexibility and integrity after electrochemical testing,
rates. GCD profiles exhibited triangular profiles without a demonstrating its robust application characteristics (Figure S15,
voltage drop, at a high current density of 1.0 A cm−3 (Figure S14, Supporting Information).
Supporting Information). In different potential windows, the To demonstrate the universality of the mCel-membrane-
CV and GCD curves also exhibited quasirectangular and sym- based polymer electrolyte used in energy storage devices,
metrical triangular profiles, respectively. The mCel-membrane- other electrode materials such as multiwall carbon nanotubes
based MSC exhibited an areal capacitance of 153.34 mF cm−2, (MWCNTs), nanographene and poly(3,4-ethylenedioxythiop­
and a volumetric capacitance of 191.66 F cm−3, at 10 mV s−1 hene):poly(styrenesulfonate) (PEDOT:PSS) were also investigated.
(Figure 5d). These values were far higher than those of some One mCel-membrane-based MSC was assembled by applying
carbon electrode-based MSCs (see Table S1 in the Supporting the MWCNTs as electrodes (Figure S16, Supporting Informa-
Information). After 1000 cycles at a scan rate of 200 mV s−1, the tion). Another mCel-membrane-based MSC was assembled by

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Figure 5.  Electrochemical properties of the mCel-membrane-based MSC. a) Schematic diagram of the preparation. b) Optical photographs of MSCs
with different configuration patterns, and in bent states. c) CV curves measured at scan rates of 10–300 mV s−1. d) Areal and volumetric capacitances
measured at different scan rates. e) Cycling performance measured at a scan rate of 200 mV s−1.

applying the nanographene sheets as the negative electrode polymer electrolyte and active carbon electrode exhibited excel-
and the pseudomaterial PEDOT:PSS as the positive electrode lent electrochemical performance, demonstrated by a high
(Figure S17, Supporting Information). They both exhibited capacitance of 120.6 F g−1, a high rate capability and excellent
excellent flexibility and good electrochemical properties, dem- cyclability with 84.7% retention after 10 000 cycles at 1.0 A g−1.
onstrating the application feasibility of the mCel-membrane as a The maximum energy density of the solid-state mCel-mem-
mesoporous polymer electrolyte for uses in pseudocapacitors. brane-based EDLC was 1.5–1.66 times higher than those of the
NKK-MPF30AC, NKK-TF4030, and PVA/KOH-based EDLCs.
Moreover, we developed a simple yet smart integrated design
3. Conclusions of MSC by directly depositing the electrode materials onto the
mCel-membrane-based polymer electrolyte without the using
In summary, a transparent, flexible, and robust mesoporous cel- of binder or complicated setups. The highly flexible mCel-
lulose membrane, mCel-membrane, was prepared by a simple membrane-based MSC exhibited a high areal capacitance of
dissolution-regeneration process. The developed cellulose 153.34 mF cm−2 and volumetric capacitance of 191.66 F cm−3
membrane processes several advantages such as high flexibility, at 10 mV s−1, representing one of the highest values among all
robust mechanical strength, high transparency, high biodegra- carbon-based MSCs. It also exhibited a maximum volumetric
dability, high electrolyte retention, and high ion conductivity energy density of 6.655 mWh cm−3 at the power density of
when saturated with KOH. To the best of our knowledge, this 0.2395 W cm−3, and a maximum power density of 5.561 W cm−3
is the first time to achieve these fantastic merits have not been at the energy density of 1.545 mWh cm−3. These results
achieved in a single renewable and degradable material. Sym- strongly support that the presented approach represents a
metric solid-state EDLC comprising of mCel-membrane/KOH promising and totally new direction for developing flexible and

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Figure 6.  a) CV curves of the mCel-membrane-based MSC in bent states. b) Ragone plots of the mCel-membrane-based MSC. c) CV curves of two
MSCs in series connection and in parallel connection. d) Optical photographs of a digital watch powered by the mCel-membrane-based MSC.

biodegradable mesoporous membranes and portable energy The areal mass loading of activated carbon for the working electrode
storage devices in an effective, low-cost, and scalable way. is 2.6 mg cm−2. The electrodes and mCel-membrane were immersed
in 6 m KOH aqueous solution for 48 h, and excess electrolyte was
removed from the surface using absorbent tissue paper. The mass
densities of the mCel-membrane before and after KOH saturation were
4. Experimental Section 0.74 and 1.24 g cm−3, respectively. The mCel-membrane-based EDLC
was assembled in a sandwich-like configuration of electrode//mCel-
Materials: Cellulose with an α-cellulose content of ≈90% was membrane/KOH//electrode. The solid-state mCel-membrane-based
purchased from Haojia Cellulose Co., Ltd. (Tianjin, China). The EDLC was encapsulated using EVA hot-melted glue under an ambient
polymerization degree of the cellulose was 1484, with an average atmosphere. Similar EDLCs containing activated carbon electrodes
molecular weight of 240 kDa. NKK-MPF30AC and NKK-TF4030 and NKK-MPF30AC, NKK-TF4030, or PVA/KOH gel as electrolytes were
were purchased from Nippon Kodoshi Corporation (Kochi, Japan). also prepared for comparison. The PVA/KOH polymer electrolyte was
Activated carbon (porous volume: 1.0–1.2 cm3 g−1, specific surface prepared by dissolving PVA powder (3 g) and KOH (3 g) in distilled
area: 2000 ± 100 m2 g−1) was purchased from Sino Tech Investment water (30 mL). The mixture was heated at 80 °C under vigorous stirring,
Management Co., Ltd., Shanghai, China. EVA was purchased from until it became homogeneously clear.
Yongtao Hot Melt Adhesive Co., Ltd., Shanghai, China. Ketjen black was Fabrication of mCel-Membrane-Based MSC: To prepare the planar-type
purchased from Lizhiyuan Sales Department of Batteries, Taiyuan, China. MSC, custom-made PTFE masks were used to define the required MSC
[Bmim]Cl, KOH, and PVA (molecular weight: 88 kDa) were purchased patterns. The Cel/IL gel was cast on a silicon wafer, which was then
from Aladdin Chemistry Co., Ltd., Shanghai, China. All chemicals were of placed in an oven at 90 °C for 45 min. With the aid of the PTFE masks,
analytical grade and used as received. the active carbon electrode material was directly deposited on the blank
Preparation of mCel-Membrane: [Bmim]Cl (50 g, 0.286 m) was added surfaces of the Cel/IL. It was then immersed in distilled water for ≈6 h,
to a three-necked flask (250 mL) with a condenser, which was heated in which formed a hydrogel state MSC. After drying at 60 °C for 8 h, a highly
an oil-bath at 85 °C for 10 min. Cellulose (2.08 g, 4 wt%) was added to integrated planar-type MSC (hereafter referred to as mCel-membrane-
the flask, which was stirred until a homogeneous transparent solution based MSC) was obtained. The areal mass loading of activated carbon
was obtained. The Cel/IL was placed in a vacuum oven (0.01 MPa) for the MSC is 1.52 mg cm−2. Prior to electrochemical testing, the
at 85 °C for 6 h, to remove bubbles and decrease the viscosity. The mCel-membrane-based MSC was impregnated in 6 m KOH solution for
obtained Cel/IL gel was cast on a silicon wafer (diameter >40 mm), using 48 h. Excess electrolyte on the MSC surface was then removed using
a VTC-100 vacuum spin coater (Kejing Instrument Co. Ltd., Shenyang, absorbent tissue paper.
China). After soaking in distilled water at room temperature for 1 h, Characterizations: The light transmittance of the sample was measured
a hydrogel of the mCel-membrane was obtained. The hydrogel was using a TU-1901 spectrophotometer (Purkinje General Instrument Co.,
sandwiched between two PTFE 0.1 μm millipore membranes (Hongqi Beijing, China), with a wavelength range of 400–800 nm. The SEM
Filter Equipment Co., Ltd., Haining, China) with a thickness of 0.03 mm, micromorphology of the sample was characterized using a JSM-7500F
pore size of 0.1 μm, and porosity of 80%. The resulting structure was microscope (Hitachi, Tokyo, Japan), at an operating voltage of 10 kV. TG
then dried at 60 °C for 12 h to generate the mCel-membrane. analysis was performed using a STA 6000 analyzer (Perkin Elmer Inc.,
Fabrication of Solid-State mCel-Membrane-Based EDLC: The working Waltham, MA, USA) in the temperature range of 45–850 °C, at a heating
electrode was prepared with 80 wt% activated carbon, 10 wt% Ketjen rate of 20 °C min−1, under a nitrogen atmosphere (40 mL min−1). The
black, and 10 wt% PTFE, and was dried in an oven at 60 °C for 8 h. aperture of the film was measured by a 3H-2000PB type bubble pressure

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Adv. Energy Mater. 2017, 7, 1700739 1700739  (9 of 9) © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim