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CHAPTER 1

INTRODUCTION

Supercapacitors, also called as ultracapacitors or electrochemical capacitors,

have drawn a lot of attentions in these years since they can bridged the gap between
traditional capacitors and batteries with a balanced power density and energy density .
As one of the most attractive energy storage devices, supercapacitors exhibit a long
cycle lifetime, quick charge-discharge rate, and could deliver relatively high power
and energy densities, which can be used in various electrical and electric equipments.
The performance characteristics of this device depend on the active material,
electrolyte, separator, packaging technique, and so on. Most of the researches recently
focus on the effects of active material, including carbon materials, metal oxides,
conducting polymer and their composites. Devices fabricated with these materials
were commonly realized by electro-deposition, lithography, and spray-coating
techniques, which were either expensive or incompatible with large-scale process ,
leading to high cost of the fabrication. Thus, there is an urgent need to develop large-
scale and low cost technologies.

Herein, we proposed an all-printed paper based supercapacitor, which

aimed at withstanding reflow soldering process when surface mounted into
microelectronic systems. The key to the fabrication of such devices lies in both
electronic packaging techniques and materials. In this paper, screen and stencil
printing processes were used to precisely construct the cofferdams, electrodes and
contact pads, which could offer an approach for low cost and large-scale production
of this device . Furthermore, the interconnect ways between the electrodes and
contact pads by printing can endure high levels of strain without failure. Accordingly,
the present study aims to investigate the use of printing technique to develop low-cost
and high performance supercapacitor.

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Surface mountable devices are generally integrated into microelectronic systems, and
solder reflow is the key process to realize the integration. This process is performed by
attaching the components onto a PCB with solder paste, aiming to solder-join contacts
together and to avoid damaging the surface mountable component simultaneously. It
proposed an ultra-small integrated 3D micro-supercapacitor fabricated with through-via
bottom electrode contact and electrochemical deposition which targeted to practically
apply in microsystems.

In this work, a paper-based surface mountable supercapacitor (SMS) was fabricated

by all-printed techniques (including screen printing and stencil printing). The low cost,
eco-friendly, 3-dimentional hierarchical properties and resistance to temperature shock
nature of the paper enables its promising application as the substrate in the future energy
storage devices. Futhermore, combining with printing technologies, the SMS could be
prepared in mature production line, which is compatible with large-scale fabrication
techniques. The electrochemical performances of the device before and after reflow
soldering were also investigated, aiming to demonstrate the possibility of application in
microelectronic systems.

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CHAPTER 2
MATERIALS AND INSTRUMENTS

The cellulose paper (thickness of 35 µm) was from Yimeng Paper Corporation, China.
The polyester based screen-printed ink (9100P) and conductive carbon ink (JELCON
CH-8) were both got from Jujo Chemical Co., Japan. Activated carbon (AC, YP50F) was
from Kuraray, Japan. 1-ethyl-3- methylimidazolium tetrafluoroborate ([C2MIm]BF4) was
bought from Monils Chem. China. Silicone glue (Silgard 184) was bought from Dow
Corning, USA. Reflow Oven (T937M) was from Tai'an Puhui Electric Technology Co.,
China.

2.1 CELLULOS PAPER

Cellulose paper intrinsically possesses unique porous bulk structure and
absorptive surface properties, which can enable usage in various electronics with a
reasonably good performance. Moreover, the inexpensive and environmental-friendly
nature of the paper offers many opportunities for us to utilize it as the substrate of a
supercapacitor . Our group recently investigated, for the first time, the life cycle
assessment of the cellulose paper to quantify a paper-based printed-circuit-board’s
(PCB’s) environmental impacts , and confirmed that paper-based device was beneficial
for the environment at the regional or global production level.

2.2 METHYLIMIDAZOLIUM TETRAFLUOROBORATE ([C2MIM]BF4)

However, the usage of liquid crystal polymer substrate and H2SO4-PVA polymer
electrolyte limited the integation process of reflow soldering. Chen et al. introduced a
surface mountable micro- supercapacitor, employing parylene-C as the substrate , which
showed good flexible property. Similarly, the involvement of solid electrolyte (PVA-
H3PO4) in the device was disadvantageous for the reflow soldering requirement. A team in
NEC TOKIN Co. has developed an electric double-layer capacitor, showing good
compatibility with lead-free solder reflow conditions .The device fabrication used a series

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of reliable but complicated packaging procedures. Recently, Brachet et al. put forward a
solder-reflow resistant solid-state supercapacitor,using ionogel as the electrolyte, by
which realized the fabriction of high-performance surface-mount type device in a real
sense.

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CHAPTER 3

FABRICATION PROCEDURE

Fabrication procedure of the paper-based SMS is shown in Figure 1.

The cellulose paper was used as the substrate of the supercapacitor. Firstly, the
polyester ink was screen printed into the paper as the cofferdam, the size of the outline
border was 32 mm × 25 mm with the width of ca. 0.2 mm. Then the AC slurry was
stencil printed in the cofferdam of the paper as the active material, the printing
thickness was 0.2 mm before the slurry drying and shrinking. Each size of the slurry
was 12 mm × 20 mm, the space between the two electrodes was 0.4 mm to prevent
short out happening caused by the flow of the slurry. The conductive carbon ink was
then screen printed onto the active material as the contact pads (current collector).

Figure 3.1 Sectional view of the fabrication

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After drying, [C2MIm]BF4 was added dropwise as the electrolyte. Standing for a
while till the electrolyte immersed into the active material, silicone glue was coated
over the device, leaving the current collector out of the surround of the glue.

3.1 CHARACTERIZATION

Scanning electron microscopy (SEM, SUPRA 55, ZEISS, Germany) was

performed to investigate the morphological characteristics of the materials.
Thermogravimetry (TG) of the cellulose paper was studied on thermal analysis
(STA449F3, NETZSCH, Germany). Cyclicvoltammetry (CV), galvanostatic
charging/discharging (GCD) of the as-prepared samples were investigated on an
electrochemical station (VMP3, Bio-Logic, France). The applied potential window of
CV and GCD was in the range of 0-2.5 V with the [C2MIm]BF4 ionic liquid
electrolyte. The specific capacitance (Cm) was calculated from the CV or GCD curves
according to the equations below.

3.1.1 THERMOGRAVIMETRIC ANALYSIS (TGM)

The dynamic thermogravimetric analysis was used to investigate the thermal

stability of cellulose paper under the nitrogen atmosphere. As shown in Figure 2, the
dynamic runs carried out at 20 °C/min in the temperature range of 25 - 260 oC.

The first step of mass loss observed in the first cycle was caused by the evaporation
of water absorbed in the cellulose. Besides, only 3.04% of the total weight loss was

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recorded after four cycles of thermal shocks, even the processing time was almost 70
min, which was far more than the standard solder reflow time. The TG test proved
that the cellulose paper showed excellent thermal stability.

Figure 3.2. TG procedure of processing the paper

3.1.2 SCANNING ELECTRON MICROSCOPY

To further investigate the performance characteristics of the paper-based

substrate, SEM was used to study the morphological changes before and after printing
the resin cofferdam (Figure 3). As we can see in Fig3ure 3a, the part between the two
red lines was screen printed with resin, with a width of about 200 µm. The enlarged
bare part of the sample is shown in Figure 3b, and pores with various sizes are
presented in the whole area. Figure 3c and Figure 3d shows the top view and cross-
section view of the cofferdam part, respectively. A continuous compact structure was
formed after screen printing with the ink, which was used to hold the electrolyte in the
box.

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Figure 3.3 SEM images of the paper before and after printing the resin cofferdam. (a)
the resin cofferdam (between the two red lines) with a width of ca. 200 µm; (b) the
bare part of the sample; (c) the cofferdam part of the sample; (d) the cross section of
the cofferdam part, which shows that the resin penetrates into the porous paper.

3.1.3 DIPPING BLACK INK

A simple prove-of-concept experiment was carried out to test the effect of the
cofferdams. After fabrication of the cofferdams, several drops of black (mainly due to
black pigment molecules) ink were dropped into them. Figure 4a shows the digital photo
of the screen-printed cofferdams on a piece of paper, Figure 4b is the picture of the ink-
processed sample. As we can see, there was no ink diffusing out of the box, confirming
the excellent insulating performance of the cofferdam. Both the TG, SEM analysis and
the proven experiment confirmed that the cellulose paper was suitable as the substrate of
surface mountable device.

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Figure 3.4 Digital photos of the cofferdams before (a) and after (b) dipping with the
black ink

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CHAPTER 4

ELECTROCHEMICAL PERFORMANCE

To find electrochemical performance of supercapacitors CV(current density Vs

potential ) and GCD curve (Galvanostatic Charge Discharge) is plotted using the
measured values.

4.1 CV AND GCD CURVES

To investigate the electrochemical performance of the AC electrode, CV was

tested firstly in 0.5 M Na2SO4 at the voltage window of 0-0.8 V (vs. Hg/HgO), as
shown in Figure, under the scan rates ranging from 2 mV/s to 200 mV/s. Typical
rectangle shapes of the curves proved that the AC material exhibits good electronic
double layer effects when storing charges. The material exhibited a Cm value of 70.1
F/g at 2 mV/s based on the total mass of active material, calculated by equation (1).
With the increase of the scan rate, the specific capacity decreased slightly, but 75.4%
of the retained capacity was still obtained as the scan rate increased from 2 to 50
mV/s. GCD characterization of the electrode was performed at the current densities
ranging from 0.2 to 5 A/g, with a working potential window of 0-0.8 V. Besides, the
GCD curves, shown as Figure 5b, exhibited typical isosceles triangle shapes. The
calculated Cm from equation (2) was 101 and 90 F/g at the current densities of 0.2
and 2 A/g, respectively, nearly 90% of the retained capacity was obtained with 10
times increase in current density.

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Figure 3.5 Electrochemical performance of the AC electrode.

a) CV; b) GCD

The AC material was stencil printed inside the cofferdams to fabricate symmetrical
supercapacitors. To enlarge the potential window and withstand the thermal shock of the
solder reflow, [C2MIm] BF4 ionic liquid was selected as the electrolyte of the SMS. The
CV and GCD performances of the device were studied with the potential window of 0-
2.5 V, as shown in Figure 6. The SMS could exhibit a Cm value of 21 F/g at the san
rate of 10 mV/s, calculated by equation (1), the retained capacity was ca. 50% when the
san rate reached 200 mV/s. From the GCD curves, as shown in Figure 6b, we can

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calculate that the SMS could achieve a Cm of 17.5 F/g at the current density of 0.5 A/g.
The total capacity of the device was 14 mF, obtain by the CV curve at the scan rate of 2
mV/s.

Figure 3.6 Electrochemical performance of the SMS. (a) CV; (b) GCD

Figure 3.6 shows the digital photos of the paper-based SMS. The thickness of the
device, tested by a micrometer caliper, is shown in Figure 7b as 0.175 mm, and the
volume of the total device is 3.2 mm × 2.5 mm × 0.175 mm. Because of the small
size of the contact pads, a micro-positioning technique was used to connect the contact
pads of the SMS to the electrochemical workstation, as shown in Figure 3.6.

Figure 3.7 shows the solder reflow curves of the test. The solid line depicted the
procedure set on the equipment, and the dash line represented the actual operation
curve. Typically, the program includes two steps: an initial preheating step for 120 s
with the temperature ranging from 150 to 180 °C, followed by a soldering temperature

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with a peak at about 255 °C for 40 s.

Figure 3.7 Digital photos of the SMS (a), thickness of the SMS (b) and electrochemical

test of the SMS under probe station (c)

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Figure 3.8 Reflow curves of the test (solid line represents the programmed curve, and
the dash line is the actual curve). Inset is the digital photo of the reflow equipment.

The electrochemical performance of the paper-based SMS before and after the reflow
soldering process was investigated. Figure 9 shows the comparison of CV curves at the
scan rate of 500 mV/s, as we can see, there was no obvious change in the shape after the
thermal shock of the solder reflow, which means insignificant impact to the
performance characteristics of the SMS.

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Figure 3.8 CV curves of the paper-based SMS before and after the solder

Table 1 shows a comparison of the parameters between some typical commercial

SMSs (products from ELNA, NEC- Tokin, SEIKO and ROSWIN) and our paper-
based SMS. All of the working potentials were in the range of 2.5-3.5 V. The paper-
based SMS exhibited a specific volumetric capacity of 10 mF/mm3, which was at
least 3 times higher than the counterparts. Based on the all-printed techniques, our
device could show a smaller size and a higher Cv value than the commercial ones.

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Cv
TYPE WORKING Capacit Volume (mm3)
(mF/m
POTENTIAL y (mF) m3)

DSK3R3H703T 3.3 70 84.8*1.4

414-HLL 2.67

(ELNA)

3.5 100
80-FCS0V10
810.8*5.
4ZFTBR24 5 0.2
(NEC-Tokin)

CPX3225A752D
3.6 75 3.2*2.5* 1.04
(SEIKO) 0.9

RW-AC332Z 3 25 3.5*2.5*0.9 3.47

(ROSWIN)

PAPER BASED 2.5 14 3.2*2.5*0.175 10

SMS

TABLE 3.1 Comparison between the paper-based SMS and some typical commercial
SMSs

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CHAPTER 5

ADVANTAGES

Each day brings a new technical innovations,and the demand for smaller,more portable
and more functional electronics.This puts pressure on power supplies to be light and
small, run along periods of time and meet the demands of multiple high current loads.
Simply put,these demands cannot be met any one portable power supply.Supercapacitors
will be a critical enabling technology for the IOT,offering a unique combination of high
power and high energy in a thin ,a flat and a very small package which can be used in
microelectronic systems. Other advantages are

 Light weight
 Low cost
 Eco friendly
 Small size since minimize space requirements
 The specific volumetric capacity was superior than most of the
commercial SMS devices.
 The capacity of the supercapacitor could reach 14 mf at the
device volume of 3.2 Χ 2.5 Χ .175 mm

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CHAPTER 6

CONCLUSION

The device proposed in this paper was packaged through “top-down”

microfabrication process, and small size of which could achieve ultracompact
supercapacitor modules. Mature all-printed processing techniques provided the
possiblity of low cost and large-scale fabrication. The usage of cellulose paper
substrate, ionic liquid electrolyte and AC active material could render it withstand the
thermal shock of solder reflow. This technology enables versatile design and
fabrication of the SMS with potential practical applications. The high electrochemical
performance of this device furtherly proved it a promising candidate for application in
the microelectronic systems and wearable devices.

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