Murata 1995

Elecrrochimico
Pergamon
Arm, Vol. 40. No. 13-14. pp. 2177-2184, 1995

Ekvier Science Ltd.
Printed in Great Britain
@x3-4686/95
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AN OVERVIEW OF THE RESEARCH AND

DEVELOPMENT
OF SOLID POLYMER ELECTROLYTE
BATTERIES
KAZUO MURATA
Central Laboratory, Yuasa Corporation 6-6, Josai-cho, Takatsuki, Osaka 569, Japan
(Received 6 April 1995)
Abstract-A review has been given on the history, status and prospect of solid polymer electrolyte and
batteries using it. It includes the market trend for solid polymer electrolyte batteries, the background and
future prospects of solid polymer electrolyte, and the introduction of film-like solid polymer electrolyte
batteries that Yuasa has developed for electronic applications. The introduction includes the performance
and safety features of the batteries from the standpoint of the application for electronic devices.
Key words: solid polymer electrolyte, ion conductivity, SPE battery, film battery, safety feature
INTRODUCTION
Several research institutes have been developing batteries with solid polymer electrolytes for more than
15 years since Professor Wright discovered the ionic
conduction in polymers in 1975[1], and Dr. Armand
proposed the use of an ionic conductive polymer in
batteries in 1978[2]. Research efforts have been
growing each year, resulting in research projects
such as the United States Advanced Battery Consortium in the United States, and the national program
led by NED0 in Japan.
The sodium-sulfur battery, which the Ford Motor
Company invented in 1966, uses an inorganic solid
electrolyte, and has been under development for
more than 25 years. In Japan, a large market for this
battery for utility load leveling should emerge in a
few years.
In contrast, the solid polymer electrolyte batteries
are expected to appear in the market place within 20
years after their development started.
There will be two major applications for solid
polymer electrolyte batteries. One is electronics
devices, which have become smaller and lighter each
year, the other one is electric vehicles.
This paper reviews the trend of the market in
which the solid polymer electrolyte batteries are
expected to be used, and the present status of the
development of the solid polymer electrolyte battery
technology, including the both primary and secondary solid polymer electrolyte batteries Yuasa has
developed.
MARKET TREND IN ELECTRONIC

DEVICES
Electronic devices have become quite diversified,
and their power consumption rate and weight has
been decreasing considerably. In fact, the batteries
represent a significant fraction of the weight in many
electronic devices today. Thus, there exists a need for

making batteries smaller and lighter. In addition,
battery shape factors are also becoming a concern
since a rectangular battery is often preferable to conventional cylindrical ones due to their more efficient
use of space. Solid polymer electrolyte batteries are
potentially very flexible in terms of their form factor.
It is anticipated that if the power consumption of
electronic devices can be further reduced, then a
film-like battery will be sufficient to power these
devices in the near future.
Such a film-like solid polymer electrolyte battery
is quite promising from the standpoint of both the
battery design and the manufacturing processes. Fig.
1 illustrates the trend of the shape of the existing
batteries, together with the direction which Yuasa
plans to follow.
MARKET TREND
IN ELECTRIC
VEHICLES
The California legislation requiring 2% of the zero

emission vehicles in 1998 has stimulated car manufacturers and battery manufacturers
worldwide.
Today electric vehicles cannot compete with the
internal combustion engine vehicles on a cost performance basis. However, government mandate with
an emphasis on reducing air pollution in major cities
is providing the stimulus for electric vehicles to, at
least partially, displace internal combustion engine
vehicles[3]. The success of this effort is heavily
dependent on advances in battery technology. Also,
the overall efficiency of the utilization of petroleum is
calculated to be higher by approximately 8% when
the petroleum is used to generate electricity at a
power station, which is then used to power the electric vehicle, rather than using the petroleum directly
for the internal combustion engine vehicle. When the
electricity is available from a nuclear power station,
the electric vehicle is ideal.
2177
K. MURATA
2178
rclric
Vehicle
Fig. 1. Trend of shape of batteries.
The requirements that the electric vehicle places

on the batteries are more stringent than the other
applications. The depth-of-discharge is deep, the discharge rate is high, and battery packs containing
from 100 to 200 batteries connected in series, will
require both high performance and high reliability.
Therefore, a technology that can produce each cell
with very little performance variation and yield a
battery which withstands overcharging and overdischarging will be required.
At present, it is generally believed that the leadacid battery and/or the nickel-metal hydride battery
will be used as the power source for electric vehicles
in this century, and the lithium battery is expected to
substitute them in the future. Although each battery
system has its own advantages and disadvantages,

the lithium battery is superior in the energy density.
As to the safety concern, the use of the solid polymer
electrolyte over a liquid electrolyte in lithium batteries should improve its safety. The operating temperature of WC, which will be required for the solid
polymer electrolyte battery, should not be a problem
in electric vehicles.
FEATURES OF SOLID POLYMER

ELECTROLYTE
BATTERY
The history of battery development can be seen as

the history of the material development. However,
Liquid
System
Plasticized
SPE System
Interface lmpedanc
Dry
SPE System
500
1000
Polarization
1500 WI
Voltage
Fig. 2. Comparison
of cell impedance.
2179
Solid polymer electrolyte batteries
35
30
25
20
15
Li + (SPE:PC=O:lOO)
--------
Li + (SPE:PC=50:50)
--------
Li + (SPE:PC=lOO:O)
Normalized Weight 1.OOmg

Programming Rate: 70 Cknin.
10
5
0
-5
100
150
200
250
300
350
Temperature
Fig. 3. Thermal decomposition
the use of new materials does not necessarily mean a

good battery. In this regard, the solid polymer electrolyte has several features that the conventional
liquid electrolyte does not have.
It is generally recognized that the mechanism of
ionic conduction of the present organic solid electrolyte relies on the segmental movement of the
polymer chain and the concentration of carrier ions.
400
CC)
of various electrolytes with Li.
Therefore, no convection can occur in dry polymer

electrolytes. Since diffusion of ions is slow, concentration gradients of ionic species occur in dry solid
polymer electrolyte during discharge, and these concentration gradients result in an increased cell
impedance.
Much research effort has been made in order to
improve the ionic conductivity of the solid polymer
3
MnOr + (SPE:PC=O:lOO)
___-----
MnOz + (SPE:PC=lOO:O
Normalized Weight 1.OOmg

Programming Rate: 10 Urnin.
100
200
300
Temperature
Fig. 4. Thermal decomposition
of various electrolytes with
400
500
(C)
MnO, .
K. MURATA
2180
Positive Current Collector
I
Sealant
Solid Polymer Electrolyte
\ Negative Current Collector
\ Lithium Anode
Fig. 5. Cross-sectional view of film-like battery.
electrolytes, but the best results to date are still far

lower than that of the liquid electrolytes.
Another source of concern in this technology is
the electrode/electrolyte interfacial impedance, which
is higher than the impedance of the electrolyte itself
as shown in Fig. 2. Much effort is likely to be needed
to reduce this interfacial impedance in order to
reduce the total impedance of the battery with the
solid polymer electrolyte.
Some people claim that the solid polymer electrolyte battery is safe because it does not leak electrolyte. However, every battery is, in general, designed
to prevent electrolyte leakage, so this does not
appear to be a positive advantage with the solid
polymer electrolyte battery. High temperature stability, on the other hand, is an advantage of the solid
polymer electrolyte battery. Figures 3 and 4 show
thermal decomposition data of solid polymer electrolytes and liquid electrolyte in the presence of
either lithium or manganese dioxide in differential
scanning calorimetry. The thermal stability of the
solid polymer electrolytes over the liquid electrolyte
is obvious.
cessibility of these materials is questionable at this

time. Another noteworthy strategy is the development of a single-ion conductive solid polymer electrolyte to prevent non-uniform distribution of the
ions. Another approach is incorporation of plasticizer to enhance the ionic conductivity. Yuasa has
been employing this effective approach in the development of the solid polymer electrolyte battery.
PRESENT STATUS OF SOLID POLYMER

ELECTROLYTE BAITERY
Since the beginning of the 198Os, the research on
the solid polymer electrolyte battery has primarily
been carried out in Europe and North America.
Toward the end of the 198Os, research programs in
PROGRESS IN DEVELOPMENT
OF SOLID
POLYMER ELECTROLYTE
For the past 15 years or so, ionically conductive
polymers, with an emphasis on ethylene oxide based
materials, has been the focus of much effort. The
primary focus of this work was to improve the ionic
conductivity of these materials by increasing segmental mobility of the solvating polymer. Two of the
most common strategies employed were the use of
copolymers and the addition of side chains to reduce
the temperature in glass transition. Obviously, the
complexation of ions by the polymer reduces the segmental mobility of the polymer, which adversely
affects the ionic conduction in the polymer salt
complex. Thus, a tradeoff exists between ion content
and segmental mobility. Recently, a solid polymer
electrolyte based on a molten salt concept has been
proposed[4] in which the charge carrier content is
high without the fear of a resultant higher temperature in glass transition. However, the pro-
loo
L-
10
._ -
10
Bobbir? Type
A4 size
_U___L__dL_J&
+i
10 i
10 3
Energy
Dwsity
( w1;/1)
Fig. 6. Performance comparison of various primary batteries.
2181
Solid polymer electrolyte batteries
loo90 g
8070 -
or
60 s
C
d
._
.z
3
Plasticized SPE
Type (Card Size)
50
40
30
20
10
70-4
10 -
10 -2
10 -3
Discharge Rate
(C)
Fig. 7. Discharge characteristics at various temperatures.
other parts of the world were underway. In the

199Os, Hydro Quebec of Canada and Yuasa formed
a joint venture called ACEP, which possessesrelevant patent rights, and promotes the development of
the solid polymer electrolyte battery. In this shared
research effort, Yuasa has been developing small
solid polymer electrolyte batteries for electronics
applications, while Hydro Quebec has been concentrating on the development of large solid polymer
electrolyte batteries. In both cases, Yuasa and Hydro
Quebec will work together to market them.
Yuasa has been developing solid polymer electrolyte batteries[5] primarily for IC cards such as an ID
card, a smart card and a tag. Yuasa plans to supply
a limited quantity of the primary battery to an original equipment manufacturer in August, 1994, and to
begin mass production in 1995. Figure 5 shows the
structure of the battery. Figure 6 compares the performance of Yuasa solid polymer electrolyte battery
with that of other primary batteries. Figure 7 compares discharge characteristics of a solid polymer
electrolyte battery with those of a liquid electrolyte
Table 1. Specifications of film-like primary battery
Volumetric energy density (wh/l)
Weight(g)
86mm
-===T
2.6
E
E
c\!
Dropping cut
cell into water
Crushing
test
Items
No
and
A metal lid bar with a diameter of 13 mm is

placed on a cell, and then pressure is gradually
applied using a hydraulic press
A cell is cut into halves using scissors,

then is dropped into water.
Test condition
battery
No fire
No explosion
No temperature
rise observed
No explosion
No fire
Table 2. Safety test results of film-like primary
At 500 kg/cm2 the cell voltage

suddenly began to decrease and
finally reached nearly 0 V at
loo0 kg/cm2.
The half at the top of the water

was observed to be
bubbling gently.
The other half of the bottom of
the tank was also observed to be
bubbling gently.
Results
Folding test
Fold down a cell
Drill a hole in cell with a Smm-diameter drill
Drilling
x.:.
:-_
.:..
:
::::.:
.........
r-l
A cell is stapled with a stapler

Observe change in cell voltage and temperature
Stapling test
Ditto
No explosion
No fire
Cell temperature
was observed to
rise onlv bv 0.6C
The cell voltage immediately

reached 0 V when fold down.
The cell voltage
recovered to nearly OCV
in 1Omin when the cell had
been unfolded.

reached 0 V.

reached OV due to shorting when
the cell was staoled.
t.l
2184
K. MIJRATA
Temperature
SPE
Plasticized
SPE
Liquid Electrolyte
-6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
4.2
1000/T
Fig. 8. Ionic conductivity of various electrolytes.
battery at various temperatures.

Table 1 summarizes
the specifications
of Yuasa film-like solid polymer
electrolyte primary battery. Various reliability tests
and safety tests have been conducted to confirm the
reliability and safety of the battery. Table 2 sum-
marizes the safety test results. In all the tests, the

battery never exploded or caught fire. Also, when
Yuasa solid polymer electrolyte battery and a conventional button-type lithium battery using liquid
electrolyte were heated on a hot plate, the buttontype battery exploded at 8OC, but the Yuasa solid
polymer electrolyte battery was intact.
Following the marketing of primary batteries,
Yuasa plans to market secondary batteries as well.
Figure 8 compares the ionic conductivity of solid
polymer electrolytes with that of liquid electrolyte.
For the secondary battery for electronics applications, Yuasa uses plasticized solid polymer electrolyte. Yuasa is also working on non-plasticized solid
polymer electrolyte, and is now developing a secondary battery for load leveling use in homes in the
future under NEDOs lo-year research program.
CONCLUSION
The solid polymer electrolyte battery has been
under development since the beginning of the 198Os,
and is expected to find a market in the latter half of
the 1990s. The market will probably start with electronics applications, and is expected to be followed
by electric vehicles application in the 21st century.
REFERENCES
1. P. V. Wright, Br. Polym. J. 7, 319 (1975).
2. M. B. Armand, Annu. Reo. Mater. Sci. 16,245 (1986).
3. H. Onishi and T. Shimoi, NRC Report (in Japanese), 84
(1993).
4. C. A. Angell, C. Liu and E. Sanches, Nature 362, 137
(1993).
5. S. Kate, Y. Yoshihisa, K. Takeuchi and K. Murata,
Power Sources 13,409 (1991).

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Elecrrochimico

Arm, Vol. 40. No. 13-14. pp. 2177-2184, 1995

AN OVERVIEW OF THE RESEARCH AND

MARKET TREND IN ELECTRONIC

electronic devices today. Thus, there exists a need for

The California legislation requiring 2% of the zero

Fig. 1. Trend of shape of batteries.

The requirements that the electric vehicle places

system has its own advantages and disadvantages,

FEATURES OF SOLID POLYMER

The history of battery development can be seen as

Solid polymer electrolyte batteries

Normalized Weight 1.OOmg

the use of new materials does not necessarily mean a

of various electrolytes with Li.

Therefore, no convection can occur in dry polymer

Normalized Weight 1.OOmg

Fig. 4. Thermal decomposition

of various electrolytes with

Positive Current Collector

Solid Polymer Electrolyte

\ Negative Current Collector

Fig. 5. Cross-sectional view of film-like battery.

electrolytes, but the best results to date are still far

cessibility of these materials is questionable at this

PRESENT STATUS OF SOLID POLYMER

Fig. 6. Performance comparison of various primary batteries.

Solid polymer electrolyte batteries

Fig. 7. Discharge characteristics at various temperatures.

other parts of the world were underway. In the

Table 1. Specifications of film-like primary battery

Volumetric energy density (wh/l)

A metal lid bar with a diameter of 13 mm is

A cell is cut into halves using scissors,

Table 2. Safety test results of film-like primary

At 500 kg/cm2 the cell voltage

The half at the top of the water

Fold down a cell

Drill a hole in cell with a Smm-diameter drill

A cell is stapled with a stapler

The cell voltage immediately

The cell voltage immediately

The cell voltage immediately

battery at various temperatures.

marizes the safety test results. In all the tests, the

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