AAA-2000-2935

HIGH PULSE POWER SYSTEM THROUGH ENGINEERING I3ATTERYCAPACITOR COMBINATION

Zheng Chen
Space Power Institute, 231 Leach Center, Auburn University, Auburn, AL 368,49,USA
Tel./Fax: 334-844-59061334-844-5900, e-mail: chenzhe @auburn.edU,

ABSTRACT*
The advancing technology of thin, lightweight, and
high power uitracapacitor- has been one of the most
exciting and important developments in electronic
components.
The technology provides a new
dimension for engineers and designers to manage the
power and energy used in electronic products. The
batteries will not have to be oversized to accommodate
a peak power demand. A combination of battery and
ultracapacitor (hybrid power system) can improve the
battery capability for power peak and also extend
battery lifetime. In this paper, author will present an
ultra-thin
hydra-amorphous
ruthenium
oxide
ultracapacitor.
The
unique
electrochemical
characteristics of ultracapacitor are able to provide a
much higher pulse current capability over the battery
system. The ultracapacitor with O.lcm thick, 14"
size, and 2.6g weight has the capability to deliver over
30W pulse peak. By combination of ultracapacitor and
battery, the pulse performance of traditional alkaline
primary battery can be significantly improved.

INTRODUCTION

.t

"18

Fig. 1 Ragone plot for three energy systems

other is named ultracapacitoi:, which stores energy

through a redox reaction. The redox reaction is a
reversible process between multiple oxidation states of
electrode materials. For an example, the capacitance of
ruthenium oxide (RuO2) arise: in part from multiple
oxidation states of ruthenium (i.e. Ru'" and Ru") and in
part from proton mobility between the oxide and
hydroxyl sites in the system, which includes RuOz
electrodes[2] and its aqueous electrolyte (i.e. H2S04).
The redox reaction of RuOpand its electrolyte can be
explained by the reversible reactions of the overlapping
redox couples Ru'", Ru", Ruvn", and possible Ru".
'

In a wide range of electronic and electrical devices

there is an increasing demand to produce products that
maintain high energy density while providing greater
power density, higher charging and discharging rate,
and longer cycle life. An electrochemical capacitor is a
technology that can provide high power density as well
as good energy density. A simple Ragone plot is shown
in Fig. 1 for three different energy systems, which are
battery, electrochemical capacitor, and electrolytic
capacitor. Clearly, electrochemical capacitor has the
best combination of power and energy density.
Electrochemical capacitors are mainly divided into two
types of capacitors based on their charge storage
mechanisms[11. One is supercapacitor that stores
charges using resulting double layers along the
interfaces between the electrodes and electrolyte. The
capacitance from the double layers is electrostatic
although some Faradaic processes can happen due to
impurities brought in by electrode or electrolyte
materials. It is unlikely that these processes play a
significant role in carbon-based supercapacitors. The
* Copyright 0 2000 The American Institute of
Aeronautics and Astronautics Inc. All right reserved.

Ru'm Ru('+I)+e-

(1)

In addition, the RU"'/RU'~redox reaction is coupled

with a proton shift between oxide and hydroxide site as
pointed early.

+I+
OH-@ 02-

(2)

Under oxidizing conditions protons are removed from

the OH sites and vice versa under reducing conditions.
However, the observed Capacitance of ruthenium oxide
is quite dependent on its physical state. In particular, it
has been recognized that high capacitance requires that
ruthenium oxide is in an amorphous state with an
appropriate degree of hydration [3,4]. Therefore, in
hydrated ruthenium oxide (HRO), which is an
amorphous structure, the redox reaction(s) take(s) place
much faster than those in its crystal structure. More
precisely, the redox reaction in HRO ultracapacitors is
an electronic and proton intercalation or electrosorption

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process. As a result, the charge movement in the

electrosorption process is very faster with litter
resistance.
From discussion above, the energy storage mechanism
for electrochemical capacitor, either double layer or
redox process, is a simple process. In contrast to
electrochemical capacitor (an energy storage device),
battery is an energy conversion device and involves
much more complicated processes such as multiple
steps of Faradaic processes. These processes can be
slow and generate heat q inside the battery when it
delivers or receives the current I[5]:

dE"
q = I(?-)+ ZR)+ I[----T]
dT

(3)

where q is the cell polarization (overpotential), R is

the ohmic (electronic and electrolytic) resistance,
and E" the thermodynamically defined equilibrium
cell voltage (cell potential). The second term of the
right side of the equation (3) is the reversible heat, a
entropy effect. It may account for 10-20% of the
electrical energy produced in the discharge. The first
term of the equation is the irreversible heat, which is
resulted from the battery voltage loss under the
current flow I. At high discharge rate, such as pulse
current, the heat generated inside battery is
significant. This not only reduces the efficiency of
the electrical energy generation, but also causes
deleterious effects (i.e. shortened cycle life and
raised internal resistance). With an electrochemical
capacitor, it would be ex ected that only a minimal
heat is generated from IR!
Clearly, electrochemical
capacitors should have high efficiency even at a fast
discharging rate.
Therefore, for pulse power
applications, the electrochemical capacitor should
help battery to deliver higher power in a much
efficient manner.

HYBRID POWER SYSTEM

The obstacle for capacitor-battery hybrid application is
the low power density and low chargingldischarging
rates of the existing carbon-based supercapacitor. The
advantage of this combination vanishes when the
significant volume of a carbon supercapacitor is added
to the system due to inefficient utilization of electrode
materials. For an example, when an advanced carbonbased supercapacitor is operated at a high
chargeldischarge rate (i.e. 250Hz) pulse, its effective
capacitance at this rate is only 40 mF and 0.5% of its
rated capacitance. It is obvious that the electrode
material efficiency is very low for this capacitor. As a
result, high volume and low efficiency is inevitable for
carbon-based capacitors. Moreover, the level of the
power delivered by a capacitor is determined by the

capacitor internal resistance, which is named equivalent

series resistance (ESR), and its capacitance at the
specific pulsed frequency during discharging. The
power PLdelivered to a load RLis described as:
(4)
where R,, C, RL, V,, and t are ESR, capacitance, load
resistance, working voltage, and discharging time,
respectively. Low ESR and small RC constant give the
capacitor high pulse power performance. Most of the
carbon-based supercapacitors use high surface area
carbon powders or fibers with non-aqueous electrolytes
to storage the electrical charges. Therefore, the high
ESR is inherited due to the resistance caused by the
difficulty for the ions in electrolyte to access small pore
structure in the carbon structure, and the low
conductivity of non-aqueous electrolytes. In order to
lower the resistance (ESR), the typical method is to
increase the electrode area, which results in the extra
capacitance. The extra capacitance is no need in most
applications. As a result, the RC constant will remain
the same for the same type of electrode materials.
Moreover, the resistance of non-aqueous electrolytes is
about 10 times higher than aqueous electrolytes. Low
power efficiency and low frequency response are
inevitable for carbon-based supercapacitor.
In this study, a 5V hydrous ruthenium oxide (HRO)
ultracapacitor was manufactured by KTI, Inc and the
Space Power Institute at Auburn University [6-81 and
used to study its pulse performance in a
batterykapacitor hybrid power system. The batteries
used were a three AAA alkaline primary battery
package (three in series). The ultracapacitor has 6 cells
in series and weights 2.6 g and has a dimension of 3.5 x
4.5 x 0.1 cm. The ultracapacitor consists of about 28
mg HRO.
The Impedance spectrum and the
capacitance response plot of the ultracapacitor are
shown in figure 2a and b. The capacitor has ESR about
45 m51 at 1 kHz and shows a fast frequency response.
At 250 Hz, the capacitor has a capacitance about 50 mF
and 46% of its rated capacitance compared to 0.5% for
a commercial available carbon based supercapacitor
mentioned early.
The data indicate that the
ultracapacitor should have good pulse performance.
Inputting these data into eq. (4), we are able to see the
power capability of this capacitor during its delivering 5
millisecond pulse powers at various load conditions,
1.5, 2.0 and 2.8 51 (Fig. 3). Compared to the carbonbased supercapacitor at the same load conditions,
respectively, it is obvious that the ultracapacitor has
much better pulse performance at fast discharge rates.
The HRO ultracapacitor also shows great
chargingldischargingefficiency at 99%.

753

0.00

1.00

2.00

4.00

3.00

(ohm)

0.01

1.00

10.00

100.00

batterykapacitor configuration (hybrid), which is 3

batteries (in series) paralleled with the HRO
ultracapacitor. The voltage and current at batteries were
monitored and recorded. Therefore, the delivered pulse
power from these two configurations can be calculated
and compared. The delivered pulse powers from these
two power sources were plotted vs. running-time (Fig.
4), respectively. The data show that the hybrid power
source delivered the pulse power between 6 to 5 W over
about a hour. The battery only source delivered the
pulse power between 4 and 3.5 W at the same period
time. The reason for shorter running-time in the hybrid
source is because it delivered a higher pulse power
during the running-time than battery only source did.
Both tests were conducted on tlhe same circuit, which is
a constant pulse load. Our test results also show that
the hybrid power can increase battery deliverable pulse
power by about 40% under fast discharge rates.
Moreover, the hybrid source can boost the maximum
pulse power of three AAA alkaline primary battery
package (4.5V) from about c151W (voltage at pulse less
2.2V) to 35W (voltage at pulse >3.0V).

1wo.00

Fngu.ncy (W

b
Fig. 2 Impedance spectrum and frequency
response curve from a 5V 0.14FHRO
ultracauacitor.

Supercapacitor-Dashedlines

12 1

0.0325

120

Fig. 4 Delivered pulse powers; were measured

from battery only and hybrid power sources,
respectively. The solid line represents the hybrid
source and dashed-line is from the battery only
source.

0.10

80
tmin.

a
0.16

40

0.005

0.WE

0.01

SUMMARY

nmerc.

Fig. 3 Calculated deliverable pulse powers at

three load condition. Solid lines and dashed lines
represent the HRO ultracapacitor and a
commercial carbon-based supercapacitor,
A 0.5 ms pulse profile was generated by a designed
electrical circuit, which has a solid-state switcher
controlled by a functional generator. 6 AAA alkaline
primary batteries were used for this experiment. The
pulse circuit tested using two different configurations: a
battery only configuration (3 batteries in series) and a

754

By adding approximately 9% weight and 10% volume

to a 4.5V AAA alkaline primary battery package, the
HRO ultracapacitor increases the pulse power level of
the battery pack by above 40%. The pulse power
performance of the battery/c:apacitor hybrid power
source shows its superior over the battery only source.
The thin and flat HRO capacitor with only less 3.0 g
weight and little less 1.8 cm3 volume can provide over a
35 W pulse peak to the 0.5 ms pulse at a 250 Hz rate.
The HRO material used for the ultracapacitor is
approximate 28 mg and cost about 6 cents. The HRO

capacitor demonstrates that it is a very exciting

technology to improve battery pulse power
performance.

ACKNOWLEDGMENT
This research was partially supported by the Center for
Space Power and Advanced -Electronics, located at
Auburn University, with funds from NASA
Cooperative Agreement NCC3-5 11, Auburn University,
and the Centers industrial partners.

REFERENCES
B.E. Conway, Some Basic electrochemical principles
involved in supercapacitor operation and develpment,
Proceedings of 3h Intl Seminar on Double Layer
capacitors and Similar Energy Storage Devices,
Deerfield Beach, FL, 1993
2B.E. Conway,
(1991).

J. Electrochem. Chem., 138, 1539

3JP. Zheng and T.R. Jow, J. Electrochem. Soc.,

142(1),L6 (1995).
4J.P. Zheng and T.R. Jow, J. Power Sources, 62 (1996)
155-159.
LRedey, B 1 Proceedings Volume: Batteries for
Portable Applications and Electrical Vehicles,
Electrochemical Society-ISE meeting, Paris, France,
August 31-September 5, 1997.
6Zheng Chen and S.A. Merryman, Study of the
influence of separators and binder concentration on the
performance of thin amorphous Ru02xHzO electrode
capacitor, Proceedings of 81h Intl Seminar on Double
Layer capacitors and Similar Energy Storage Devices,
Deerfield Beach, FL, 1998.
Zheng Chen and S.A. Merryman, The performance of
thin amorphous Ru020xH20capacitor, Proceedings of
9lh Intl Seminar on Double Layer capacitors and
Similar Energy Storage Devices, Deerfield Beach, FL,
1999.
8M.F. Rose, S.A. Merryman, and Zheng. Chen Cell
Phone Performance Enhancement through the use of
Advanced Electrochemical capacitors, Proceedings of
8 Intl Seminar on Double Layer capacitors and
Similar Energy Storage Devices, Deerfield Beach, FL,
1998.

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