Electrochimica Acta 51 (2006) 24542462

Composite alkaline polymer electrolytes and its application to

nickelmetal hydride batteries
Anbao Yuan , Jun Zhao
Department of Chemistry, College of Sciences, Shanghai University, Shanghai 200444, China
Received 15 February 2005; received in revised form 12 May 2005; accepted 15 July 2005
Available online 1 September 2005

Abstract
In order to enhance the ionic conductivity of polyethylene oxide (PEO)-KOH based alkaline polymer electrolytes, three types of nanopowders, i.e., TiO2 , -Al2 O3 and SiO2 were added to PEO-KOH complex, respectively, and the corresponding composite alkaline polymer
electrolytes were prepared. The experimental results showed that the prepared polymer electrolytes exhibited higher ionic conductivities at
room temperature, typically 103 S cm1 as measured by ac impedance method, and good electrochemical stability. The electrochemical
stability window of ca. 1.6 V was determined by cyclic voltammetry with stainless steel blocking electrodes. The influence of the film
composition such as KOH, H2 O and nano-additives on ion conductivity was investigated and explained. The temperature dependence of
conductivity was also determined. In addition, polyvinyl alcohol (PVA)-sodium carboxymethyl cellulose (CMC)-KOH alkaline polymer
electrolytes were obtained using solvent casting method. The properties of the polymer electrolytes were characterized by ac impedance,
cyclic voltammetry and differential thermal analysis methods. The ionic conductivity of the prepared PVA-CMC-KOH-H2 O electrolytes can
reach the order of 102 S cm1 . The effect of CMC addition on the alkaline polymer electrolytes was also explained. The experimental results
demonstrated that the PVA-CMC-KOH-H2 O polymer electrolyte could be used in Ni/MH battery.
2005 Elsevier Ltd. All rights reserved.
Keywords: Alkaline polymer electrolyte; Ionic conductivity; PEO; PVA; Nano-additives

1. Introduction
Solid polymer electrolytes, also called ionic conductive
polymers, are of a new type of solid electrolytes, which have
been intensively studied and developed since 1970s. In 1973,
Wright et al. [1,2] firstly reported that polyethylene oxide
(PEO)/salts complexes exhibited ionic conductive property.
In 1979, Armand et al. [3] claimed that the conductivity of
PEO/salts complexes could reach the order of 105 S cm1
at 4060 C, and there would be a potential application in Liion batteries. Thereafter, R&D on polymer electrolytes has
attracted great attention in the world and most of it focused
on Li-ion polymer batteries. However, the studies on polymer electrolytes for alkaline batteries such as Ni/MH, Ni/Cd

Corresponding author. Tel.: +86 21 66134851; fax: +86 21 66133292.

E-mail address: abyuan@staff.shu.edu.cn (A. Yuan).

0013-4686/$ see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2005.07.027

and Ni/Zn, etc., are comparatively fewer. Solid polymer electrolytes can be widely used in different applications, such as
all-solid batteries and supercapacitors.
Alkaline polymer electrolyte, in contrast to conventional
alkaline aqueous electrolyte (i.e., KOH), for use in Ni/MH
batteries, could provide solutions to the problems of high
internal pressure upon charging, alkaline leakage, oxidation of negative electrode (hydrogen storage alloy) upon
charge/discharge cycling and high self-discharge rate. In
addition, soft packaging (using aluminum/plastic laminated
films) could be introduced to replace metallic packaging to
improve safety and specific energy of the batteries. Fauvarque et al. [4] firstly investigated the PEO based alkaline
polymer electrolyte and its application to Ni/Cd secondary
batteries. Concerning the published literature, the alkaline
polymer electrolytes could be divided mainly in three types,
i.e., PEO based [47], polyvinyl alcohol (PVA) based [815]
and hybrid PEOPVA based [16,17] electrolytes. Because of

A. Yuan, J. Zhao / Electrochimica Acta 51 (2006) 24542462

the crystallinity in PEO, the conductivity of PEO-KOH alkaline polymer electrolytes is usually low in view of practical
applications. In order to increase the conductivity, modifications by co-polymerization or blend are usually employed.
However, addition of inorganic nano-particles to PEO-KOH
system is not available in literatures up to now. In the present
study, some nano-powders, i.e., TiO2 , -Al2 O3 and SiO2
were added to PEO-KOH complexes, respectively, in order
to enhance the ionic conductivity, and the corresponding
composite alkaline polymer electrolytes were prepared. The
characteristics of the polymer electrolytes were studied using
ac impedance, cyclic voltammetry, differential thermal analysis and infrared spectroscopic analysis methods.
Compared with PEO based alkaline polymer electrolytes,
the conductivity of PVA based alkaline polymer electrolytes is usually higher. For example, the conductivity of
PVA-KOH-H2 O polymer electrolyte can reach the order of
102 S cm1 . However, the electrolyte film is found to be
easy to dehydrate deeply, which causes it to crimple and
becomes distorted, and the flexibility becomes bad. Nevertheless, addition of hydrophilic sodium carboxymethyl cellulose
(CMC) to PVA could improve the mechanical property and
water retention property of the electrolyte film. Hence, in this
study, the PVA-CMC based alkaline polymer electrolyte films
were prepared by blend of PVA with CMC, and its properties were investigated by ac impedance, cyclic voltammetry
and differential thermal analysis methods. Finally, a polymer
Ni/MH battery with PVA-CMC-KOH-H2 O alkaline polymer
electrolyte was tested in order to evaluate the practical application of the polymer electrolyte.

2. Experimental
2.1. Preparation of PEO based nano-composite alkaline
polymer electrolyte lms
PEO (Mw 100,000) was mixed with nano-TiO2 (10 nm),
nano--Al2 O3 (1020 nm) and nano-SiO2 (50 nm), respectively, in a mortar. Then the mixture was added to a given
concentration of KOH aqueous solution in a beaker and
magnetically stirred to a homogeneous solution. After rested
for some time and no bubble could be observed, the above
solution was poured into a glass plate to evaporate at room
temperature. Thus, the alkaline polymer electrolyte films with
thickness of 0.10.3 mm were prepared.
2.2. Preparation of PVA based alkaline polymer
electrolyte lms
PVA and CMC (with a given mass ratio) were added to
distilled water in a beaker and heated to dissolve. Then a given
concentration of KOH solution was added and magnetically
stirred to a homogeneous solution. After rested for some time
and no bubble could be observed, the solution was poured
into a glass plate to evaporate at room temperature. Thus,

2455

the alkaline polymer electrolyte films with a thickness of ca.

0.5 mm were prepared.
2.3. Determination of ionic conductivity
Test alkaline polymer electrolyte film (with an area of
4 cm2 ) was placed between two stainless steel blocking electrodes, and then subjected to ac impedance measurement (in
the frequency range 105 to 101 Hz) using CHI660A Electrochemical Workstation. According to the formula = l/Rb A
(where, l, Rb and A are the thickness, bulk resistance and area
of the film, respectively), the ionic conductivity of the test
alkaline polymer electrolyte film could be calculated. The
bulk resistance was determined from the cross point of the
ac impedance spectrum at high frequency area and the real
axis.
2.4. Determination of electrochemical stability window
Test alkaline polymer electrolyte film was placed between
two stainless steel blocking electrodes, then cycled in the
voltage region of 1.5 to +1.5 V with a scan rate of 10 mV s1
using CHI660A Electrochemical Workstation to determine
the cyclic voltammetric behavior of the electrolyte. Thus,
the electrochemical stability window of the alkaline polymer
electrolyte could be determined.
2.5. Differential thermal analysis (DTA) and infrared
spectroscopic (IR) analysis
Differential thermal analysis (DTA) curves of the samples were carried out using microcomputer controlled WCT1A differential thermal analysis unit (Beijing, China). The
rate of temperature rise was controlled at 10 C min1
heating from 25 to 250 C, and the mass of the samples
was controlled in the range of 1015 mg. Infrared spectroscopic (IR) analysis for the samples were performed
using an Avatar 360 FT-IR Fourier transformation infrared
spectrometer.
2.6. Preparation and testing of Ni/MH battery with
liquid or polymer electrolyte
Preparation of nickel electrode: a given amount of
Ni(OH)2 was mixed with 5 wt.% cobalt powder and 2 wt.%
acetylene black, then a given amount of polytetrafluoroethylene (PTFE) emulsion was added as binder and mixed again.
The obtained paste was filled into a foamed nickel (with
2 cm 2 cm dimensions), and then dried at 65 C and roll
pressed to a thickness of ca. 0.6 mm.
Preparation of metal hydride electrode: a given amount
of AB5 -type hydrogen storage alloy was mixed with 7 wt.%
nickel powder and 2 wt.% graphite, then a given amount of
polyvinyl alcohol (PVA) solution was added as binder and
mixed again. The obtained paste was filled into a foamed

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A. Yuan, J. Zhao / Electrochimica Acta 51 (2006) 24542462

nickel (with 2 cm 2 cm dimensions), then vacuum dried at

65 C and roll pressed to a thickness of 0.35 mm.
The liquid Ni/MH battery was consisted of a positive
nickel electrode and a negative hydride electrode, and its
capacity being governed by the positive electrode. The battery was cycled three times with C/10 charge/discharge rate
in 6 M KOH solution for activation. After that, the nickel
electrode and the hydride electrode were taken out from the
solution for dryness, and then a Ni/MH battery with polymer electrolyte was assembled. The battery was consisted
of a piece of polymer electrolyte film (with a composition
of m(PVA):m(CMC):m(KOH):m(H2 O) = 13.8:3.5:34.7:48.0
and a thickness of 0.5 mm) sandwiched by an activated nickel
electrode and an activated hydride electrode. The aboveassembled battery was enwrapped with a plastic cloth and
roll pressed again in order to get the electrode/electrolyte
interface contact well.
The charge/discharge performance of the battery was
tested using LAND auto-cycler (China), and the electrochemical impedance spectroscopy (EIS) was carried out using
CHI660A Electrochemical Workstation.

Fig. 2. Conductivity of polymer electrolyte with different wt.% of water.

3. Results and discussion

paratively mild. This indicates that when the concentration

of KOH is lower, the influence of KOH content on conductivity is considerable, and while when the concentration
reaches a given degree, the KOH content becomes not a
crucial factor. Moreover, we found from experiment that
when m(KOH):m(PEO) exceeds 0.5, the homogeneity and
mechanical property of the film become bad. Hence, the
proper value for m(KOH):m(PEO) should be controlled at
ca. 0.4.

3.1. Relationship between conductivity of PEO-KOH

system and KOH content

3.2. Relationship between conductivity of PEO-KOH

system and water content

The conductivity variation of PEO-KOH based alkaline

polymer electrolyte film with KOH content is presented in
Fig. 1. It can be seen from Fig. 1 that with m(KOH):m(PEO)
(mass ratio) increasing, the conductivity of the system
increases gradually. This is because that with increasing
of KOH content, the concentration of conductive ions in
the film increases, and hence the conductivity increases.
Besides, the variation of log() with m(KOH):m(PEO) is
not linear but presents different slops. When the value of
m(KOH):m(PEO) is small, the variation of conductivity with
m(KOH)/m(PEO) is drastic. Nevertheless, when the value of
m(KOH):m(PEO) exceeds 0.4, the variation becomes com-

The conductivity variation of PEO-KOH based alkaline

polymer electrolyte film with water content is shown in Fig. 2.
It can be seen from Fig. 2 that the conductivity of the film
increases with water content increasing. Water content has a
crucial influence on film conductivity. When water content
is less than 8 wt.%, the logarithm of conductivity increases
remarkably with water content increasing. However, when
water content is larger than 10 wt.%, the slop of the curve
becomes less steep relatively. This indicates that when water
content is larger, the influence of it on film conductivity is
inclined to weaken.
3.3. Inuence of inorganic nano-additives on the
conductivity of PEO-KOH system

Fig. 1. Conductivity of polymer electrolyte with different ratios of

m(KOH):m(PEO).

In order to enhance the ionic conductivity of PEO-KOH

based polymer electrolytes at room temperature, three types
of inorganic nano-powders, i.e., TiO2 , -Al2 O3 and SiO2
were added to PEO-KOH complex, respectively. The influence of nano-additives amount on film conductivity was
studied and the tested data are listed in Table 1. Known
from Table 1 that the ionic conductivity increases from
107 S cm1 order of magnitude for the pure PEO-KOH
system to 106 to 105 S cm1 for the nano-composite
polymer electrolytes, i.e., increased 12 orders. It can be
also seen from Table 1 that when m(PEO):m(TiO2 ) or
m(PEO):m(-Al2 O3 ) equals 92.5:7.5, or m(PEO):m(SiO2 )
equals 87.5:12.5, the conductivities exhibit the maximum val-

A. Yuan, J. Zhao / Electrochimica Acta 51 (2006) 24542462

2457

Table 1
Conductivity of polymer electrolytes with different ratios of
m(PEO):m(nano-powder) (water content: 3 wt.%, m(PEO):m(KOH) = 10:4)
m(PEO):m(nano-powder)
(in mass ratio)

Conductivity, (106 S cm1 )

TiO2
(25 C)

-Al2 O3
(20 C)

SiO2
(20 C)

100:0
97.5:2.5
95:5
92.5:7.5
90:10
87.5:12.5
85:15
82.5:17.5
80:20

0.50
1.70
5.67
33.0
27.8
18.9
6.03
2.05
1.91

0.40
0.53
1.10
5.64
4.01
2.81
0.66
0.61
0.59

0.40
0.55
0.59
0.65
1.10
1.90
1.30
0.85
0.83

ues. However, if the electrical and mechanical properties are

considered simultaneously, the most appropriate ratio should
be of 87.5:12.5.
The DTA curves of pure PEO powders, PEO-KOH-H2 O
and PEO-KOH-SiO2 -H2 O polymer electrolytes are shown in
Fig. 3(ac), respectively. The endothermic peak in Fig. 3(a)
(about 62 C) and the first endothermic peak in Fig. 3(b)
(about 57 C) or Fig. 3(c) (about 49 C) are corresponding to
PEO melting. Compared with the pure PEO, the melting temperatures and the peak areas (relating to the enthalpy changes
of the melting processes) for the PEO-KOH-H2 O and PEOKOH-SiO2 -H2 O polymer electrolytes are decreased, especially for the PEO-KOH-SiO2 -H2 O system. This suggests
that the addition of nano-SiO2 to PEO-KOH-H2 O system can
decrease the crystallinity in PEO [18,19], and hence increases
the conductivity. The second endothermic peak in Fig. 3(b
and c) (around 80 C) should be ascribed to water evaporation.
The infrared spectra of PEO and PEO-KOH-SiO2 -H2 O
polymer electrolyte are presented in Fig. 4(a and b),
respectively. The most important of the absorption features presented both in Fig. 4(a and b) appears to be [18]
C O stretching at 1640 cm1 , CH2 asymmetric bending at
1344 cm1 , C O C stretching at 1115 cm1 , CH2 stretching at 2887 cm1 and OH stretching at 3449 cm1 . It can be
found from Fig. 4 that the absorption features presented only
in Fig. 4(b), i.e., the peaks at 1007 cm1 , 703 cm1 , 663 cm1

Fig. 4. IR spectra of PEO and PEO-KOH-SiO2 -H2 O polymer electrolyte.

(a) PEO and (b) PEO-KOH-SiO2 -H2 O polymer electrolyte.

and 467 cm1 are absent in Fig. 4(a). Where the 1007 cm1
position is likely to be ascribed to Si O C or Si O Si
vibration, while the positions at 703 cm1 , 663 cm1 and
467 cm1 are not clear, but possibly are associated with K
and Si in the composite system. Besides, the frequency of OH
stretching is decreased from the acute peak at 3449 cm1 in
Fig. 4(a) to the obtuse peak at 3438 cm1 in Fig. 4(b), which
suggests that the hydrogen bonds in PEO are weakened in the
PEO-KOH-SiO2 -H2 O polymer electrolyte. It could be supposed that the addition of nano-SiO2 to PEO complex plays
the role of isolation, which hinders the formation of hydrogen bonds to a certain degree, and hence decreases the degree
of crystallinity in PEO. This result is in agreement with the
above DTA result.

3.4. Temperature dependence of conductivity for

PEO-KOH based nano-composite polymer electrolytes
Fig. 5 shows the temperature dependence of conductivity for the polymer electrolytes with addition of nano-TiO2 ,
-Al2 O3 and SiO2 , respectively. The conductivity increases
gradually with temperature rise in the temperature range
of 2060 C, and an approximately linear relationship for
log() 1/T could be obtained, which is consistent with the
Arrhenius equation.

Fig. 3. DTA curves of pure PEO and polymer electrolytes. (a) pure PEO; (b) PEO-KOH-H2 O (m(PEO):m(KOH) = 10:4, water content: 10 wt.%); (c) PEOKOH-SiO2 -H2 O (m(PEO):m(KOH) = 10:4, m(PEO):m(SiO2 ) = 87.5:12.5, water content: 10 wt.%).

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A. Yuan, J. Zhao / Electrochimica Acta 51 (2006) 24542462

Fig. 7. DTA curves of pure PVA and PVA-CMC-KOH-H2 O polymer

electrolyte. (a) Pure PVA and (b) m(PVA):m(CMC):m(KOH):m(H2 O) =
13.8:3.5:34.7:48.0 (in mass ratio).
Fig. 5. Conductivity of polymer electrolytes with temperature variation.
(
) m(PEO):m(TiO2 ):m(KOH):m(H2 O) = 57.4:8.1:23.0:11.5; () m(PEO)
:m(Al2 O3 ):m(KOH):m(H2 O) = 51.9:7.3:28.5:12.3; () m(PEO):m(SiO2 ):
m(KOH):m(H2 O) = 52.2:7.5:27.8:12.5.

3.5. Electrochemical stability of alkaline

nano-composite polymer electrolytes
For practical application of polymer electrolytes in batteries, not only high conductivity but also wide electrochemical
stability window should be required. In order to investigate the electrochemical stability of alkaline nano-composite
polymer electrolytes, cyclic voltammetry method (described
detail in Section 2.4) was employed. The results are shown
in Fig. 6. It can be seen from Fig. 6 that the faradaic current
is nearly zero at ca. 0.8 to +0.8 V region. This indicates
that the electrochemical stability window of the electrolytes
is about 1.6 V.
3.6. Differential thermal analysis (DTA) of pure PVA
and PVA-CMC-KOH-H2 O polymer electrolyte
The DTA curves of pure PVA (dried powder) and PVACMC-KOH-H2 O polymer electrolyte are shown in Fig. 7(a
and b), respectively. There is an endothermic peak (226 C)
for pure PVA in the temperature range of 25250 C, which
corresponding to the melting of PVA. Whereas, there are two
endothermic peaks (99 and 195 C) for PVA-CMC-KOHH2 O polymer electrolyte can be observed in the same temperature range. The former peak (99 C) could be attributed
to water evaporation and the later (195 C) corresponding
to the melting of the polymer electrolyte. Compared with
the pure PVA, the decline of melting point suggests that the

Fig. 8. Conductivity of polymer electrolytes with different ratios of

m(KOH):m(PVA + CMC).

crystallinity in PVA is decreased, which is favourable to conductivity improvement of the polymer electrolyte.
3.7. Relationship between conductivity of
PVA-CMC-KOH-H2 O system and KOH content
The relationship between conductivity of PVA-CMCKOH polymer electrolyte film and KOH content is
presented in Fig. 8. The conductivity increases with
m(KOH):m(PVA + CMC) ratio increasing. When the value
of m(KOH):m(PVA + CMC) changes from 0 to 0.5, the conductivity increases sharply from 107 to 102 S cm1 order
of magnitude. However, when m(KOH):m(PVA + CMC)
beyond 0.5, The variation of conductivity becomes
mild comparatively and the variation of log() with
m(KOH):m(PVA + CMC) presents nearly linear relationship.

Fig. 6. Cyclic voltammograph for polymer electrolytes at room temperature (scan rate: 10 mV s1 ). (a) m(PEO):m(TiO2 ):m(KOH):m(H2 O) = 57.4:8.1:
23.0:11.5; (b) m(PEO):m(Al2 O3 ):m(KOH):m(H2 O) = 51.9:7.3:28.5:12.3; (c) m(PEO):m(SiO2 ):m(KOH):m(H2 O) = 52.2:7.5:27.8:12.5.

A. Yuan, J. Zhao / Electrochimica Acta 51 (2006) 24542462

Fig. 9. Conductivity of polymer electrolytes with different wt.% of water.

3.8. Relationship between conductivity of

PVA-CMC-KOH-H2 O system and water content
Fig. 9 shows the relationship between conductivity of
PVA-CMC-KOH-H2 O polymer electrolyte and water content. The conductivity of the film increases gradually with
water content increasing, and water content has a crucial
influence on conductivity. When water content is within
30 wt.%, the conductivity of the film is lower and increases
slowly with water content increasing. While, when water content exceeds 30 wt.%, the conductivity increases rapidly with
water content increasing, and can reaches 8 102 S cm1
as water content increases to 50 wt.%. This can be explained
possibly as follows. Conductive phase and nonconductive
phase can coexist in PVA-CMC-KOH-H2 O polymer electrolyte. When water content is lower, the conductive phase
cannot be formed perfectly, and whereas, when water content reaches a certain extent, the fraction of conductive phase
increases with water content increasing, and hence the ionic
conductivity of the film increases rapidly.
3.9. Inuence of CMC on performance of
PVA-CMC-KOH-H2 O polymer electrolyte lm
According to the literature [20], when the mass ratio of
m(CMC):m(PVA) being 20:80, 50:50 and 80:20, respectively, there would be a good compatibility of CMC with
PVA. Therefore, three types of PVA-CMC based polymer
electrolytes with the above three ratios were prepared, respectively, in this study, and the influence of CMC on performance of PVA-CMC-KOH-H2 O polymer electrolyte film
was investigated. The correlation between film conductivity and CMC content is shown in Fig. 10, wherein the mass
ratio of m(KOH):m(PVA) for the film without CMC addition (i.e., the PVA-KOH-H2 O film) being 1.5:1, whereas the
mass ratio of m(KOH):m(PVA + CMC) for the PVA-CMCKOH-H2 O films being 2:1. It can be seen from Fig. 10
that the conductivity of the film without CMC addition is
of 103 S cm1 order, whereas the conductivity of the films
with CMC addition are all of 102 S cm1 order. That is to

2459

Fig. 10. Conductivity of polymer electrolytes with different ratios of

m(CMC):m(PVA + CMC).

say, increased one order of magnitude. This is because that

the maximum value of m(KOH):m(PVA) for the PVA-KOHH2 O film should be controlled within 1.5. Otherwise, if the
ratio exceeds this value, the KOH would prefer to crystallize out, and hence make the film brittle [10]. Whereas, the
value of m(KOH):m(PVA+CMC) for the PVA-CMC-KOHH2 O film can be increased to 2 without KOH crystallization.
That is to say, the electrolyte film with CMC addition can
dissolve more KOH in it. According to the results described
previously, the film conductivity increases with KOH content increasing, and hence the PVA-CMC-KOH-H2 O films
exhibit higher ionic conductivity.
Among the three polymer electrolytes, the one with
m(CMC):m(PVA + CMC) = 0.2 exhibits the maximum conductivity. When CMC content further increasing, the conductivity of the film decreases slightly. In addition, we found
from experiment that the electrolyte film without CMC addition (PVA-KOH-H2 O film) is easy to lose water deeply in the
atmosphere of air, and hence to crinkle and become brittle.
However, the water retention property, mechanical strength
and flexibility of the film with CMC addition can be improved
considerably.
3.10. Storage stability of PVA-CMC-KOH-H2 O polymer
electrolyte
In order to investigate the storage stability of the
PVA-CMC-KOH-H2 O polymer electrolyte, an as-prepared
electrolyte film with a composition of m(PVA):m(CMC):
m(KOH):m(H2 O) = 13.8:3.5:34.7:48.0 was stored for different periods and examined by ac impedance method. Fig. 11
shows the ac impedance spectra (in the frequency range
105 to 101 Hz) of the polymer electrolyte being stored for
24 h, 7 days and 2 months, respectively. It can be seen from
Fig. 11 that being stored for 2 months, the spectrum changed
somewhat. But the calculated conductivity (according to the
method described in section 2.3) for the three situations
(24 h, 7 days and 2 months) are 6.2 102 , 5.7 102 and
5.2 102 S cm1 , respectively. This suggests that the varia-

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A. Yuan, J. Zhao / Electrochimica Acta 51 (2006) 24542462

rent response in the voltage region of ca. 0.8 V to +0.8 V.

So, the electrochemical stability window of the polymer electrolyte is about 1.6 V, which could meet the requirement of
practical application in Ni/MH battery.
3.12. Performance of Ni/MH battery with
PVA-CMC-KOH-H2 O polymer electrolyte

Fig. 11. The ac impedance spectra of the polymer electrolyte being stored
for different periods (measured at 25 C).

Fig. 12. Cyclic voltammograph of polymer electrolyte at room temperature.

tion of the conductivity with storage time is not considerable.

In other words, the film presents good storage stability.
3.11. Electrochemical stability of PVA-CMC-KOH-H2 O
polymer electrolyte
Electrochemical stability of the alkaline polymer electrolyte with a composition of m(PVA):m(CMC):m(KOH):
m(H2 O) = 13.8:3.5:34.7:48.0 was evaluated by cyclic
voltammetry method. The result is presented in Fig. 12. It
can be seen from Fig. 12 that there is almost no faradaic cur-

The as-prepared Ni/MH battery was cycled three times

with C/10 charge/discharge rate in 6 M KOH solution for
activation, then was subjected to ac impedance test. After
that, the nickel electrode and the hydride electrode were
taken out from the solution for dryness, and subsequently
a polymer Ni/MH battery with PVA-CMC-KOH-H2 O polymer electrolyte instead of 6 M KOH solution was assembled
and subjected to ac impedance test. The Nyquist plots for the
liquid and polymer Ni/MH batteries are presented in Fig. 13,
respectively. The ac impedance test carried out on the batteries at discharged state (0% SOC) and room temperature, and
in the frequency range 105 to 103 Hz. Fig. 13(b) is the close
up view of Fig. 13(a) at high frequency area. It can be seen
from Fig. 13(a) that there is no distinct difference between
the liquid and the polymer Ni/MH batteries. But we can see
from Fig. 13(b) that the ohmic resistance (the real part of
impedance at high frequency) of the polymer Ni/MH battery
is a little big than that of the liquid Ni/MH battery (where
the values of Z and Z are the product of tested resistance
multiplied by the mass of nickel hydroxide in positive electrode). This result reflects the fact that the conductivity of
the polymer electrolyte is a little lower than that of the liquid
electrolyte.
Fig. 14 shows the typical charge/discharge characteristics
of the polymer Ni/MH battery at different rates. The charge
voltage increases with charge rate increasing, and the charge
plateau voltages are about 1.4 V, 1.45 V and 1.55 V, respectively, corresponding to C/10, C/5 and C/2 rates. While the
discharge voltage decreases with discharge rate increasing,
and the discharge plateau voltages are about 1.2, 1.1 and 1 V,
respectively, corresponding to C/10, C/5 and C/2 rates.
In order to evaluate the dischargeability of the polymer
Ni/MH battery, the battery was charged at C/10 rate and discharged at C/10, C/5, C/2 and 1C rates, respectively. The

Fig. 13. Nyquist plots for the liquid and polymer Ni/MH batteries at discharged state.

A. Yuan, J. Zhao / Electrochimica Acta 51 (2006) 24542462

2461

Fig. 14. Charge/discharge curves of the polymer Ni/MH battery at various

discharge rates.
Fig. 16. Discharge specific capacity of the polymer Ni/MH battery charged
at various rates.

Fig. 15. Discharge specific capacity of the polymer Ni/MH at different rates.

results are shown in Fig. 15, from which we can see that
the discharge voltage and specific capacity decrease with
discharge rate increasing. The discharge plateaus are about
1.25, 1.2, 1.1 and 1 V, respectively, corresponding to C/10,
C/5, C/2 and 1C discharge rates. This result demonstrates
that when the discharge rate is not too high, the discharge
behavior is comparable with commonly used liquid Ni/MH
battery. While when the discharge rate exceeds C/2, the discharge voltage and specific capacity are too low to compare
with conventional liquid Ni/MH battery.
The charge-rate dependence of discharge capacity are
shown in Fig. 16, wherein the discharge rate is C/10 and
the charge rates are C/10, C/5, C/2 and 1C, respectively. It
can be seen from Fig. 16 that the discharge capacity and voltage decrease with charge rate increasing, but the influence
is not remarkable compared with that of discharge rate. This
result indicates that the battery can be charged but cannot be
discharged at higher rates.

Fig. 17. Cycle life of the polymer Ni/MH battery at C/5 charge/discharge
rate.

Fig. 17 shows the cycle life of the polymer Ni/MH battery

at C/5 charge/discharge rate. The first-cycle discharge capacity is 171 mAh g1 , and the second-cycle discharge capacity
increased to 188 mAh g1 . This is because that going through
a charge/discharge cycle, the electrode/electrolyte interface
of the polymer Ni/MH battery becomes more compatible and
this is favorable to the subsequent electrode reaction. However, from the fourth cycle, the discharge capacity begins
to decline gradually. This is mainly because of the water
loss in polymer electrolyte upon cycling. In our experiment,
the polymer battery was only enwrapped with a plastic cloth
but not been sealed strictly. This can be further illuminated
with the ac impedance evolution displayed in Fig. 18 (in the

Fig. 18. The ac impedance spectra of the polymer Ni/MH battery cycled at C/5 rate for two and seven cycles.

2462

A. Yuan, J. Zhao / Electrochimica Acta 51 (2006) 24542462

frequency range 105 to 103 Hz), where Fig. 18(b) is the

close up view of Fig. 18(a) at high frequency region. It can
be seen from Fig. 18(a) that the impedance spectra are all
composed of a semicircle and a straight line. The semicircle at the higher frequency region should be attributed to
the charge transfer resistance of electrode/electrolyte interface, and the straight line at the lower frequency region
corresponds to the Warburg diffusion impedance. Undergone seven charge/discharge cycles, the charge transfer resistance increased obviously. Additionally, it can be seen from
Fig. 18(b) that the ohmic resistance of the battery increased
also, which reflects the increase of bulk resistance of the polymer electrolyte. Water loss upon cycling not only induces the
bulk resistance increase for the polymer electrolyte but also
induces the charge transfer resistance increase for the electrode/electrolyte interface.

4. Conclusions
In this study, PEO based and PVA based alkaline polymer
electrolytes were prepared and investigated. The ionic
conductivity of the polymer electrolytes increase with KOH
and H2 O content increasing. Addition of nano-additives to
PEO-KOH system can increase the conductivity of PEO
based polymer electrolyte. Differential thermal analysis and
infrared spectral analysis results revealed that nano-SiO2
added to PEO based polymer electrolyte could decrease the
crystallinity in PEO and hence increase the conductivity
of the system. While, CMC addition to PVA-KOH system
can make the polymer complex to accommodate more KOH
and hence to increase the ionic conductivity. Besides, CMC
addition can improve the water-retention and mechanical
properties of PVA based polymer electrolyte. The room
temperature conductivity of the PEO based nano-composite
polymer electrolytes and the PVA-CMC-KOH-H2 O polymer electrolytes can reach 103 and 102 S cm1 orders of
magnitude, respectively, and the electrochemical stability
window of the alkaline polymer electrolytes is ca. 1.6 V. The
experimental results of the polymer Ni/MH battery with PVA-

CMC-KOH-H2 O alkaline polymer electrolyte demonstrated

that the polymer electrolyte could be applied to Ni/MH batteries, especially under conditions of lower discharge rates.

Acknowledgement
The authors gratefully acknowledge the financial support
of the Shanghai Educational Development Foundation (Grant
No. 02AK50) given by the Shanghai Educational Committee
of China.

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