ORIGINAL RESEARCH

published: 25 September 2018

doi: 10.3389/fchem.2018.00443

Portable High Voltage Integrated

Harvesting-Storage Device
Employing Dye-Sensitized Solar
Module and All-Solid-State
Electrochemical Double Layer
Capacitor
Alberto Scalia 1,2,3 , Alberto Varzi 1,2*, Andrea Lamberti 3 , Timo Jacob 1,2,4 and
Stefano Passerini 1,2*
1
Helmholtz Institute Ulm (HIU), Ulm, Germany, 2 Karlsruhe Institute of Technology (KIT), Karlsruhe, Germany, 3 Department of
Applied Science and Technology, Politecnico di Torino, Turin, Italy, 4 Institute of Electrochemistry, Ulm University, Ulm,
Germany
Edited by:
Alberto Mittiga,
Agenzia Nazionale per le Nuove A dye-sensitized solar module (DSSM) and a high voltage all-solid-state electrochemical
Tecnologie, L’energia e lo Sviluppo double layer capacitor (EDLC) are, for the first time, implemented in a compact
Economico Sostenibile (ENEA), Italy
Harvesting-Storage (HS) device. Conductive glass is employed as current collecting
Reviewed by:
Thuat Thanh Trinh,
substrate for both DSSM and EDLC, leading to a robust and portable final structure. The
Norwegian University of Science and photovoltaic section is constituted by a 4 series cells W-type module, while in the storage
Technology, Norway section an EDLC employing an ionic liquid-based polymeric electrolyte (a mixture of
Ankit Gujral,
Intel (United States), United States polyethylene oxide and N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide,
*Correspondence: PEO-Pyr14 TFSI) and activated carbon electrodes is used. The solid state EDLC is
Stefano Passerini first characterized individually to determine its electrochemical performance before
[email protected]
Alberto Varzi
successfully proving the integration with the DSSM. The harvesting-storage properties
[email protected] of the integrated photo-capacitor are evaluated through photo-charge and subsequent
discharge protocols performed at two different discharge currents, showing that in this
Specialty section:
configuration the EDLC unit can be effectively charged up to 2.45 V.
This article was submitted to
Physical Chemistry and Chemical Keywords: supercapacitor, dye sensitized solar cell, integrated device, portable device, polymer electrolyte,
Physics, harvesting-storage device
a section of the journal
Frontiers in Chemistry

Received: 26 July 2018 INTRODUCTION

Accepted: 07 September 2018
Published: 25 September 2018 Fossil fuels are the worldwide most employed energy source. In the past, their relative abundance
Citation: has promoted their use in several contexts: automotive, residential heating, industry, power plants,
Scalia A, Varzi A, Lamberti A, Jacob T etc. However, the increasing level of pollution, poor air quality and global warming caused by
and Passerini S (2018) Portable High their excessive employment is forcing the international community to shift toward greener and
Voltage Integrated Harvesting-Storage
renewable alternatives, such as photovoltaic (PV) power generation (Gonçalves et al., 2008; El
Device Employing Dye-Sensitized
Solar Module and All-Solid-State
Chaar et al., 2011; Parida et al., 2011). In the emerging PV technology framework, different
Electrochemical Double Layer technologies have been proposed. Among these, dye-sensitized solar cells (DSSCs) possess the
Capacitor. Front. Chem. 6:443. lowest fabrication cost and the smallest payback time (Wongcharee et al., 2007; Zardetto et al.,
doi: 10.3389/fchem.2018.00443 2013; Liu et al., 2015a,b; He et al., 2017; Hwang et al., 2017; Li et al., 2017). In addition, after years

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Scalia et al. Portable High Voltage Powerpack

of research they have reached appreciable efficiency and turn in to cell explosion. Solid-state polymer electrolytes have
reliability (Jung and Lee, 2013; Gerosa et al., 2016). been proposed also to overcome this risk (Fic et al., 2018).
However, the intermittent nature of the incident solar Furthermore, the encapsulation of the IL electrolyte into a
radiation makes an uninterrupted power supply impossible. polymeric matrix would represent a further step toward a leak-
Thus, for many applications, a storage media able to accumulate less ELDC with the twofold advantage of: (i) reducing the overall
the converted solar radiation is mandatory in order to stabilize IL content and (ii) avoiding the need of additional packaging
the electrical output of the PV section and, therefore, the input (Ayalneh Tiruye et al., 2015).
for the user (Ng et al., 2015; Luo et al., 2017). Recently, the idea Moreover, with respect to literature(Scalia et al., 2018),
to directly connect the PV harvester with a storage unit in a employing a polymer as electrolyte yield the subsequent sealing
monolithic integrated device is widely considered (Schmidt et al., with a specific sealant unnecessary.
2016). This integration is needed to drive users, such as electronic To the best of our knowledge we present the integration
devices or sensors, (Volkov et al., 2017; Yang et al., 2017; of the aforementioned dye-sensitized solar module (DSSM)
Garcia-Hernandez et al., 2018; Sorvin et al., 2018) particularly and an all-solid-state EDLC for the first time (Figure 1). The
when the access to the electric grid is denied. Electrochemical two devices are first tested separately while their integration is
double layer capacitors (EDLCs) are particularly suitable for examined afterwards. The DSSM provides an open circuit voltage
integration with PV technology. This is mainly due to their of 2.57 V. Thus, the final voltage of the EDLC during photo-
outstanding cycling stability. In fact, EDLCs can sustain a rather charge approached this value. Both the DSSM and the EDLC are
high number of charge–discharge cycles (even above 1,000,000) fabricated onto glass substrates, paving also the way to a possible
(Zhang and Pan, 2015) without an appreciable change of their future integration in window facades.
capacitance nominal value. To date, batteries have not shown
the same longevity (Zhang and Pan, 2015). Furthermore, they MATERIALS AND METHODS
are less sensitive to the voltage output of the harvesting section
than batteries, which, depending on the chemistry, require a Materials
well-defined operative voltage to be charged. Last, EDLCs can Activated carbon (AC, P4) was provided by SGL Carbon
withstand wide current ranges being definitely more versatile (Germany). Sodium carboxymethyl cellulose (CMC, Walocell
(Choudhury et al., 2009; Zhong et al., 2015; González et al., 2016; CRT 2000) was purchased from Dow Wolff Cellulosics.
Lin et al., 2018). Conductive carbon (CC, Super C65) was purchased from
Most of the integrated devices presented in literature(Wei Imerys Graphite & Carbon. The ionic liquid Pyr14 TFSI (99.9%,
et al., 2017; Yun et al., 2018) deal with a single solar cell connected Solvionic) was dried under high vacuum (10−7 mbar) for 24 h at
to an electrochemical double layer capacitor (EDLC) or a battery 120◦ C. Its water content after drying, determined by Karl Fischer
(Xu et al., 2014; Kim et al., 2017; Scalia et al., 2017). Thus, the final titration (Mettler Toledo), was below 10 ppm. Benzophenone (for
voltage obtained in the storage section is generally lower than synthesis, ≥99.0%, Merck) was dried under vacuum for 48 h at
1 V (Chen et al., 2012; Skunik-Nuckowska et al., 2013; Yang et al., 40◦ C. Poly(ethylene oxide) (PEO, Mv = 100,000, Dow Chemical)
2013; Cohn et al., 2015; Li et al., 2016). Recently, however, the was dried under vacuum for 48 h at 50◦ C. The sensitizing dye,
feasibility of photocapacitors with a harvesting section composed cis-bis(isothiocyanato)(2,2’-bipyridyl-4,4’-dicarboxylato)(4,4’-
by more solar cells in series has been demonstrated. In a previous di-nonyl-2’bipyridyl) ruthenium (II) (Z907, Ruthenizer 520-DN)
work, (Scalia et al., 2018) a voltage well beyond 2 V was obtained was purchased from Solaronix. TiO2 Paste DSL 18NR-AO
using a highly stable ionic liquid electrolyte in the storage was purchased from Dyesol. The Meltonix 1170-60 (60 µm)
section, thus guaranteeing an impressive discharge capacity sealant was purchased from Solaronix. Solar cells electrolyte
of 0.1 mAh·cm−2 subsequent to photo-charge. The N-butyl- components, sodium iodide (NaI) and iodine (I2 ) were purchased
N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide from Sigma-Aldrich (Milan, Italy). 4-tert-butylpyridine (TBP)
(Pyr14 TFSI) ionic liquid demonstrated stability during charge– and methoxypropionitrile (CH3 OCH2 CH2 CN) were purchased
discharge protocols lasting for several hours. In addition, the from Merck. 7  sq−1 sheet resistance fluorine-doped tin oxide
discharge capacity measured after 1 h rest period subsequent (FTO)-coated glass was purchased by Solaronix.
to photo-charge (i.e., no external current applied to the EDLC
section) was found to be roughly the same as that obtained All-Solid-State EDLC Fabrication
without this resting period, demonstrating the excellent capacity FTO-coated glass was at first cut in 7.5 × 6 cm2 plates by
retention (i.e., low self-discharge) of the EDLC section. The means of a diamond glass-cutter. These plates were then used as
photovoltaic module in the above-mentioned work (Scalia et al., substrates and current collector for the EDLC electrodes. Before
2018) was composed of 4 serially-connected DSSCs as in this depositing the active material slurry, these FTO glasses were
present work. rinsed with acetone and ethanol in an ultrasonic bath for 10 min
Regarding EDLCs, solid-state polymer electrolytes were to clean the surface. The slurry was prepared by dispersing the
recently proposed as a valuable alternative to liquid electrolytes electrode components (100 mg of dry mass) in 5 mL ultrapure
because reliability, safety and bending features are mandatory (milliQ) H2 O with the appropriate ratio. The composition of the
for miniaturized and smart applications. Moreover, unusual dry electrodes was: 90 wt% of activated carbon (AC), 5 wt% of
operating conditions may lead liquid electrolytes-based EDLCs conductive carbon and 5 wt% binder (CMC). The slurry was then
to overpressure inside the device, which can sporadically deposited onto the conductive side glass substrate coating a 4 ×

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Scalia et al. Portable High Voltage Powerpack

Benzophenone was first dissolved in Pyr14TFSI. Then, PEO

was hand-mixed together until the formation of a solid material.
Afterwards, the electrolyte was vacuum sealed in a pouch bag and
annealed for 12 h at 100◦ C. Subsequently, small electrolyte pieces
were sandwiched between two Mylar foils (PPI) and hot-pressed
(Servitec Polystat 200T) at 100◦ C to obtain films of thickness
below 100 µm. The electrolyte was then cross-linked in a UV
chamber (Uvacube 100) for 6 min (Kim et al., 2010). Finally,
the polymer electrolyte was sandwiched between the two glass-
supported electrodes and pressed by means of a hot press. The
preparation of the electrolyte as the assembly of the device was
carried out in dry room (dew point < −60◦ C).

Dye-Sensitized Solar Module Fabrication

FTO glass plates were used as DSSM substrates. The forward
plate was a 4 × 4 cm2 FTO glass plate while the backward
plate was cut into a 4 × 5 cm2 rectangular shape, in order to
have additional space for the electrodes’ contacts. Four holes
(1 mm diameter) were drilled in the backward plate, one for
every DSSC, for electrolyte filling. The conductive FTO layers
were appropriately patterned with a diamond tip in order
to electrically separate a photo-anode from the cathode of a
contiguous solar cell. Glass plates were rinsed in acetone and
ethanol in an ultrasonic bath for 10 min. Afterwards, dissimilar
Pt layers were deposited onto the cathode regions of the forward
and backward plates of the glass substrates, respectively, 3 and
10 nm thick, by means of sputtering technique (EM ACE 600,
LEICA). Sputtering parameters were set to 30 mA current and
0.04 nm/s deposition rate. Of course, different deposition times
were adopted for the front or back irradiated cells. In order to
deposit the semiconductor paste layer, adhesive tapes (80 µm
thick) with circular holes were placed on the glass plates. For
the front side and backside irradiated cells the hole diameters
were set to 10 and 12 mm respectively. The paste was deposited
onto the adhesive mask by means of the doctor blade technique.
The FTO-glasses with TiO2 paste were calcined at a temperature
of 510◦ C for 30 min. The sintered electrodes were then soaked
for 15 h in the 0.3 mM Z907 solution in ethanol. The devices
were sealed by means of a hot press utilizing 2 × 60-µm-
thick Meltonix films. The temperature of the hot press was
set to 120◦ C. The liquid electrolyte was inserted by vacuum
backfilling through the 4 holes previously drilled. Electrolyte
composition was a 0.45 M sodium iodide, 0.056 M iodine and
0.55 M 4-tert-butylpyridine dissolved in methoxypropionitrile
FIGURE 1 | (A) Pictures of the polymer electrolyte EDLC, (B) Picture of the (MPN).
DSSM section, (C) integrated HS device front view.

Integration of the DSSM and

All-Solid-State EDLC
4.5 cm2 deposition area by means of the doctor blade technique. DSSM and EDLC were integrated in a single structure by means
Symmetrical mass loadings were chosen for the two electrodes. of a hot press. Two Meltonix films (each 60 µm thick) were
Finally, the coated electrodes were pre-dried overnight at 80◦ C placed between the DSSM and the EDLC cathode, leaving the
and then under vacuum conditions for 12 h at 130◦ C. DSSM contacts region outside the EDLC surface in order to easily
The polymer electrolyte, PEO:Pyr14 TFSI (2:1 mol/mol) + 5 connect harvesting and storage contacts during photocharge.
wt% benzophenone (the latter percentage is relative to the weight With this method also a proper sealing of the backward DSSM
of PEO), was prepared as reported in Sharova et al. (2016). holes was ensured.

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Scalia et al. Portable High Voltage Powerpack

Photo-Electrochemical Characterization important performance, since a huge number of photo-charge

For the evaluation of the DSSM performance a HelioSim- discharge cycles are to be expected for this kind of harvesting-
CL60 (Voss Electronics) solar simulator and a PG510/590 storage devices. Figure 2B shows the capacitance retention of the
(Heka) potentiostat were used in order to measure the photo- EDLC section. More than 10,000 GCD cycles were performed at
generated current under simulated solar radiation with an an imposed current of 20 mA (1.11 mA cm−2 ). After an initial
AM1.5 spectrum. During this phase, the potenstiostat terminals phase (3,000 cycles) where a small decrease is observed, the
were connected to the PV section electrodes of the HS capacitance stabilizes at almost 90% of the initial value. After
device. The EDLC performance was evaluated by means 5,000 cycles the capacity slowly increased indicating that the
of galvanostatic constant current (GCC) cycling and cyclic EDLC section posseses outstanding reliability upon long-term
voltammetry (CV) executed on a programmable multi-channel cycling.
potentiostat-galvanostat (VMP3, Biologic Science Instruments, Electrochemical impedance spectroscopy (EIS) of the PEO-
France). The tests were performed at 20◦ C in a climatic chamber Pyr14 TFSI-based EDLC was performed, which results are
(Binder, KBF-115). Electrochemical impedance spectra (EIS) reported in the Nyquist plot of Figure 2C. As suggested by
was recorded at Voc, by means of an Impedance/Gain-Phase Zhang et al., (Zhang and Pan, 2015) the equivalent series
Analyzer 1260 (Solartron Analytical) between 0.1 MHz and 1 resistance (ESR) was evaluated by the real part of the impedance
mHz, with an AC amplitude of 10 mV. Upon photo-charge, at 1 kHz, yielding a value of 33.8 . Almost the same value
the voltage of the EDLC was measured with a potentiostat PG was found, evaluating the ESR by the voltage drop of the
510/590 (Heka), while the HS device was irradiated by the solar CD reported in Figure 2A (36 ). Even if a consistent part
simulator. of the ESR is ascribable to the FTO resistance, the increase
of the ESR with respect to our previous work (Scalia et al.,
RESULTS AND DISCUSSION 2018) featuring pure IL (26.8 ), suggests that the polymer
electrolyte provides an important contribution to the overall
The electrochemical performance of the all-solid-state EDLC is ESR. In the intermediate frequency region, a linear behavior
summarized in Figure 2. Figure 2A shows a typical galvanostatic with a slightly lower slope with respect to the usual 45◦
charge-discharge (GCD) voltage profile for an imposed current Warburg trend is observable. This region can be ascribed to
of 2 mA (0.11 mA cm−2 ). A deviation from the ideal capacitive the limited ion diffusion in the electrodes pore structure, once
response can be clearly noticed due to the poor conductivity of more associated to the use of the all-solid-state electrolyte.
the FTO glass conductive substrate, but also the moderate ionic Finally, the values at low frequencies are not parallel to
conductivity of the PEO-Pyr14 TFSI electrolyte in comparison the imaginary axis, meaning that the response of the SC
with the previously used neat IL (Scalia et al., 2018). Since the deviates from that of an ideal capacitor in agreement with the
charging and discharging behavior is non-linear, the average voltage profile upon GCD (see Figure 2A). Again, the limited
capacitance (CA ) was evaluated directly from the SC discharging conductivity of the polymer electrolyte certainly plays a relevant
energy, via the following formula: role here. Figure 2D shows the coulombic efficiency related
Z to the long-term stability test (see Figure 2B) of the all-solid-
tf .d
1 2 state EDLC via GCD at 20 mA (1.11 mA cm−2 ). After the
C A VM =i V dt = EEDLC (1)
2 ti.d initial activation the coulombic efficiency was always higher
than 99%, showing relevant electrical double layer capacitance
Here V M is the maximum voltage reached during the GCD features.
(2.5 V), V is the EDLC voltage, i is the imposed discharge Figure 3 shows the current-voltage characteristic of the
constant current, t i.d is the initial discharge time, t f.d is the final DSSM. It was obtained under 1 sun (1,000 Wm−2 ) illumination
discharge time, and EEDLC is the EDLC energy evaluated during conditions. In the inset the most relevant photovoltaic
discharge phase. The CA value of 0.16 F was calculated, namely parameters (photovoltaic efficiency, fill factor, short circuit
providing a normalized capacitance of 9 mF·cm−2 . Impressively, current, and open circuit voltage) are reported. Additional
such a polymer electrolyte-based EDLC offers a capacitance information regarding the DSSMs herein investigated are
value almost four times higher than that of the liquid (organic) available in our previous work (Scalia et al., 2018).
electrolyte EDLC proposed by Chien et al. (2015), which is one Figure 4 displays the photo-charge and subsequent discharge
of the very few examples of photo-capacitor with a PV section curves of the integrated HS device. In the first part of the
composed by a module (series connected cells) instead of a photo-charge the EDLC voltage rapidly rises until about 2 V
single solar cell. This further demonstrates the highly remarkable and then evolves into a plateau above 2.3 V. This trend is
performance of the storage device developed in this work. In due to the EDLC voltage approaching the open circuit voltage
addition, the polymer electrolyte-based EDLC does not show sign of the DSSM, resulting in a lower current supplied to the
of electrolyte degradation, which are indeed well evidenced by the EDLC. Nonetheless, the photo-charge was limited to 2.45 V
voltage plateau observed at about 2 V upon GCD measurement in for practical reasons. Upon discharge, two different negative
the work of Chien et al. (Chien et al., 2015). It testifies that the all- current values were applied, namely 1 and 2 mA (0.056 and 0.11
solid-state glass-based EDLC possesses a stability in the chosen mA·cm−2 ). A remarkable capacity value over 0.017 mAh·cm−2
voltage window, difficult to find in literature for high voltage PV was found for the imposed discharge current of 1 mA. Although
harvester-EDLC integrated devices. Such a high stability is rather lower than that obtained for the EDLC employing the neat IL

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Scalia et al. Portable High Voltage Powerpack

FIGURE 2 | Electrochemical performance of the all-solid-state capacitor employing a PEO-Pyr14 TFSI polymer electrolyte. (A) Typical voltage profile recorded for
charge/discharge at 2 mA (0.11 mA cm−2 ). (B) Capacitance retention test performed at 20 mA (1.11 mA cm−2 ), (C) EIS spectrum (Nyquist plot) collected between 1
mHz and 1 MHz with a 10 mV amplitude, (D) Cycling stability test (coulombic efficiency) performed at 20 mA (1.11 mA cm−2 ) for 11,000 cycles.

electrolyte (Scalia et al., 2018), this value is still higher than linearly with time. Then, the OPECSE gradually decreased
the majority of liquid-based electrolyte storage section photo- since the provided incoming electromagnetic energy was kept
capacitors reported in the literature (Xu et al., 2014, 2016; Chien constant while the EDLC voltage asymptotically approached
et al., 2015). the DSSM VOC , limiting the energy stored in the EDLC
The galvanostatic discharge after limiting the photo-charge to section. The inset in Figure 5A shows the OPECSE variation
2 V was also studied in order to probe the performance of the during the initial 50 s of photo-charge. Interestingly, for this
HS device upon shorter photo-charging time. This experiment charging step, in which the EDLC reaches a voltage of 1.7 V,
is highly significant for real HS applications where rather short a still remarkable efficiency corresponding to 60% of the
photo-charging time maybe available to cope with subsequent maximum OPECSE is achieved. Figure 5B shows the OPECSE
user requests. as a function of the EDLC voltage reached during photo-
The overall photon to electrical conversion and storage charge. This analysis is crucial since, as stated before, the
efficiency (OPECSE) was evaluated with the following formula: voltage output of an integrated device needs to be higher than
(Xu et al., 2014, 2016; Kim et al., 2017) 1 V in order to drive electronic utilizers. After reaching the
maximum value around 0.6 V, the OPECSE decreases linearly.
1
2 CA V 2 Ideally, the maximum OPECSE should be reached at a voltage
η (OPECSE) = (2) higher than 1 V and/or its value should remain constant
GtS
up to voltages close to the DSSM’s V OC . Nevertheless, the
Here CA (0.16 F) is the average capacitance evaluated from EEDLC almost linear decrease (rather than an abrupt decrease) of
during the discharge phase, V is the EDLC voltage, G is the the OPECSE vs. increasing voltages is still considered to be a
impinging electromagnetic density radiation (100 mW·cm−2 ), t good compromise. Additionally, the number of the cells in the
is the photo-charge time and S is the active surface area of the DSSM can be adjusted to optimize the OPECSE to the utilizers’
DSSM. requirements.
Figure 5A shows the OPECSE value as a function of the Overall, further improvement could be foreseen in a
photo-charging time. The obtained profile is in accordance future work. The EDLC section could probably bear a
with the literature and presents a maximum of 1.67% in the higher voltage, given the stability of the ionic liquid up to
very first part of the photo-charge when the voltage varies 3.5 V (Varzi et al., 2014). Thus, a DSSM with 5 serially

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Scalia et al. Portable High Voltage Powerpack

FIGURE 3 | Current–voltage curve of the DSSM performed under 1 sun

illumination condition (100 mW cm−2 ). In the inset, the photovoltaic peculiar
parameters of the DSSM are reported.

FIGURE 5 | (A) OPECSE values plotted as a function of the photo-charging

time (in the inset, the values corresponding to the first 50 s of photo-charge are
plotted), (B) OPECSE values plotted as a function of the EDLC voltage.

into a DSSM and an all-solid-state EDLC. The system

FIGURE 4 | Storage performance of the HS device. The photo-charge was
achieved a highly remarkable photo-charging potential of
performed under 1 sun radiation conditions while the discharge curves were
recorded under constant current conditions. 2.45 V, never obtained before for a HS device including a
solid-state electrolyte storage section. The DSSM and EDLC
sections were fabricated onto glass substrates and finally
integrated into a compact structure. The EDLC storage
connected cells (expected 3.1 V) could more exploit better section employing PEO-Pyr14 TFSI as electrolyte, allowed
the whole potential of the ELDC. However, as it was long photo-charge/discharge cycling life. Additionally, the
designed in this work, the DSSM required an even number use of the solid-state electrolyte facilitates the sealing of the
of cells. If employing 6 cells, the open circuit voltage of whole structure, still providing appealing performance above
the DSSM would instead exceed stability window of the the state-of-the-art reported in the literature. A remarkable
electrolyte. capacity value over 0.017 mAh·cm−2 was achieved upon
discharging the cell at 1 mA after photo-charge, proving the
CONCLUSIONS suitable characteristics of the HS for applications of practical
interest.
In summary, here we have reported a novel high voltage A further increment of PV efficiency and, as a consequence,
photo-capacitor composed by a 4 serially connected cells of the OPECSE could be foreseen by tuning the electrolyte layer

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Scalia et al. Portable High Voltage Powerpack

thickness or by designing a Z-type DSSM. This would render this ACKNOWLEDGMENTS

type of HS device a really competitive technology able to satisfy a
variety of energy storage applications. AS, AV, and SP acknowledge the financial support of
the Helmholtz Association. Layal Daccache and Julius
AUTHOR CONTRIBUTIONS Gröne are acknowledged for supporting the solar
simulator studies. Last but not least, the authors would
AS and AV designed the experimental work. AS performed the like to thank SGL Carbon, Imerys Graphite & Carbon
experimental work. All authors analyzed the results and and Dow Wolff Cellulosics for kindly providing their
contributed to write the manuscript. materials.

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polar TiO2 nanotube arrays with selective one-side plasma-assisted conducted in the absence of any commercial or financial relationships that could
hydrogenation (Adv. Funct. Mater. 13/2014). Adv. Funct. Mater. 24:1814. be construed as a potential conflict of interest.
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sensors: materials, sensing mechanisms, and device performance. Mater. Sci. article distributed under the terms of the Creative Commons Attribution License (CC
Eng. R Reports 115, 1–37. doi: 10.1016/j.mser.2017.02.001 BY). The use, distribution or reproduction in other forums is permitted, provided
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device for both photoelectric conversion and energy storage based on free- publication in this journal is cited, in accordance with accepted academic practice.
standing and aligned carbon nanotube film. J. Mater. Chem. A 1, 954–958. No use, distribution or reproduction is permitted which does not comply with these
doi: 10.1039/C2TA00113F terms.

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