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Electrolyte for aluminum electrolytic capacitor –


effect of carbohydrates
a b
Ming‐Liao Tsai & Hsiu‐Yui Lin
a
Institute of Materials and Chemical Engineering , National Chin Yi Institute of
Technology , Taichung, Taiwan 411, R.O.C. Phone: 886–4–23924505 ext.7510 Fax:
886–4–23924505 ext.7510 E-mail:
b
Institute of Materials and Chemical Engineering , National Chin Yi Institute of
Technology , Taichung, Taiwan 411, R.O.C.
Published online: 04 Mar 2011.

To cite this article: Ming‐Liao Tsai & Hsiu‐Yui Lin (2006) Electrolyte for aluminum electrolytic capacitor – effect of
carbohydrates, Journal of the Chinese Institute of Engineers, 29:1, 153-158, DOI: 10.1080/02533839.2006.9671107

To link to this article: http://dx.doi.org/10.1080/02533839.2006.9671107

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Journal of the Chinese Institute of Engineers, Vol. 29, No. 1, pp. 153-158 (2006) 153

Short Paper

ELECTROLYTE FOR ALUMINUM ELECTROLYTIC CAPACITOR


– EFFECT OF CARBOHYDRATES

Ming-Liao Tsai* and Hsiu-Yui Lin


Downloaded by [University of Western Ontario] at 23:05 13 November 2014

ABSTRACT
In this study, carbohydrates were added to modify the textural characteristics of
electrolytes used in aluminum electrolytic capacitors. The results show that the con-
ductivity and sparking voltage of the electrolytes were strongly affected by the con-
centration of these carbohydrates. In addition, the pH of the electrolyte was only
slightly affected by the concentration of these carbohydrates. In this work, the pa-
rameters of capacitors impregnated with the electrolytes were periodically measured
under storage conditions and loading at 105°C for such quantities as capacitance (Cp),
dissipation factor (DF) and leakage current (Lc). Experimental results show that the
capacitor impregnated with electrolyte, containing 8% dextrose, exhibited satisfac-
tory durability.

Key Words: aluminum electrolytic capacitors, capacitance, carbohydrates, sparking


voltage.

I. INTRODUCTION 2001; Tsai et al., 2002a; Tsai et al., 2002b; Tsai et


al., 2005).
Recent studies on electrolytic aluminum capaci- There are primarily three kinds of issues regarding
tors have attracted much attention since the capaci- the solvent was used for the aluminum electrolytic
tors offer smaller size, higher capacitance, greater capacitors; i.e., ethylene glycol, γ -butyrolactone and
reliability, and more safety. The advantage of alu- solid electrolytes system, respectively (Roland, 1983;
minum electrolytic capacitors is their high capaci- Shoichiro et al., 1988; Niwa, et al., 1988; Ryutaro,
tance despite their small size. High-performance 1994; Nishiyama et al., 1995; Amano et al., 1996;
characteristics have come to be of great importance Yamamoto, et al., 1996,1999; Munehiro, 2000; Naoi
for electrolytic capacitors. The factors, which affect et al., 2000; Akihiko et al., 2001). In general, elec-
the characteristics of electrolytic aluminum trolytes using ethylene glycol/H 2O as the solvent are
capacitors, are materials and surface morphologies of used in lower voltage aluminum electrolytic capaci-
electrodes, composition of electrolytes, assembly of tors (Tsai, 2001; Tsai et al., 2002a; Tsai et al., 2002b;
capacitors and so on. It has been revealed that the Tsai et al., 2005). In addition, γ-butyrolactone is gen-
composition of electrolytes is one of the most impor- erally added for medium or high voltage aluminum
tant factors affecting the textural characteristics of electrolytic capacitors (Ue et al., 1996). Furthermore,
electrolytic aluminum capacitors (Roland,1983; the two types of capacitor on the market which use a
Kazuhiko et al., 1988; Shoichiro et al., 1988; Ryutaro, solid electrolyte are both solid aluminum capacitors,
1994; Munehiro, 2000; Akihiko et al., 2001; Tsai, those using 7,7,8,8-tetra- cyano-1,4-quinodimethane
(TCNQ), and those using a conducting polymer as
the ionic transfer medium, respectively (Niwa and
*Corresponding author. (Tel: 886-4-23924505 ext.7510; Fax: Taketani, 1996; Kudoh et al., 1999).
886-4-23926617; Email: mltsai@chinyi.ncit.edu.tw)
The authors are with the Institute of Materials and Chemical
Some additives are added to promote the per-
Engineering, National Chin Yi Institute of Technology, Taichung, formance of electrolytes that are used for low volt-
Taiwan 411, R.O.C. age aluminum electrolytic capacitors, e.g., ammonium
154 Journal of the Chinese Institute of Engineers, Vol. 29, No. 1 (2006)

salts (Tsai, 2001; Tsai et al., 2002a; Tsai et al., 2005). 1


Not only is the solvent, γ -butyrolactone used, instead
of an ethylene glycol and water system, but also the
additives generally vary when electrolytes are used
in medium or high voltage aluminum electrolytic ca-
pacitors (Ue et al., 1996). 2
A 3
Generally, aluminum electrolytic capacitors are
composed of 8 elements, including (1) aluminum foil, V
(2) connecting wire, (3) electrolytic paper, (4)
electrolyte, (5) packing, (6) aluminum shell, (7) gel
tube and (8) adhesive. Among these elements, elec- 4 5
trolyte with various additives is the most important
factor for to promote the performance of electrolytic
aluminum capacitors (Tsai, 2001; Tsai et al., 2005).
Downloaded by [University of Western Ontario] at 23:05 13 November 2014

6 7
In our previous studies, performance of electro-
lytes used in aluminum electrolytic capacitors was
significantly promoted by adding various additives,
such as Tetra-alkyl ammonium salt and organic Am- 8
monium salts (Tsai, 2001; Tsai et al., 2002a; Tsai et
al., 2005). It is hoped that the conductivity, sparking Fig. 1 The apparatus for the measuring of sparking voltage.
voltage, and the pH value of aluminum electrolytic 1.Power supply; 2. Ampere meter; 3. Volt meter; 4. An-
capacitor may be improved by the addition of these ode 5. Cathode; 6. Electrolyte; 7. Cell; 8. Agitator
salts into the electrolytes when ethylene glycol/H 2O
is used as a solvent. Furthermore, the durability may
be increased in the presence of these various 2. Instruments
additives. Previously, there have been few published
papers showing that the electrolyte in aluminum elec- The pH, conductivity (κ), dissipation factor (DF)
trolytic capacitors becomes more active to improve and leakage current (Lc) of the electrolytes were mea-
performance, when chemicals whose molecules con- sured by pH meter (SUNTEX SP-701), conductivity
tain hydroxyl or carbonyl functional groups are added meter (Mettler Toledo MC 126), LCR meter (Motech
(Tsai et al., 2002b). Hence, in this study, carbohy- MT 4080A) and leakage current tester (Zentech CLC-
drates were added into the raw electrolytes based on 203), respectively. The values of capacity (C) and
an ethylene glycol/H2O mixing solvent to improve the DF were measured at the frequency of 120 Hz, and
characteristics of the electrolytes. The performance the value of Lc was obtained at the loading of 11.5 V
of electrolytic aluminum capacitors using varying for 60 s.
electrolytes was also investigated.
3. Sparking Voltage
II. EXPERIMENTAL
Two aluminum foils (> 99.7% AXX1005) were
1. Materials placed into a suitable volume of electrolyte prepared
as above. A constant current density of 10 mA cm −2
The raw electrolyte solution was supplied by the was applied by a power source (Chroma 6208K-500)
Her Mei Electronic Co. Ltd (Taiwan) (Tsai, 2001). and the cell potential was recorded until sparking
All of the chemicals (e.g. dextrose extra pure grade > occurred at the anodic surface. The experimental set-
99% Wako), lactose (extra pure, Merck), sucrose (extra up for sparking voltage is shown in Fig. 1.
pure grade > 99%, Sigma), fructose (extra pure grade
> 99%, Sigma), and ethylene glycol (100%, J. T. Baker) 4. Capacitor Durability
used in this work were not further purified before use.
The electrolytes were prepared by adding the desired The durability of electrolytes prepared in this work
amount of additives into the commercial electrolyte, was tested under the conditions of low temperature
Her Mei 2001. Comparisons between Her Mei 2001 storage, high temperature storage and high tempera-
were used for measuring characteristics, such as ture with loading. The characteristics of capacitors,
conductivity, pH, and sparking voltage. The capaci- including C, DF and Lc, were periodically measured
tors were prepared by impregnating the condenser under the various conditions described above. For the
element (Her Mei) in the electrolytes under vacuum conditions of low and high temperature storages, the
for 40 min. capacitors impregnated with various electrolytes were
M. L. Tsai and H. Y. Lin: Electrolyte for Aluminum Electrolytic Capacitor–Effect of Carbohydrates 155

40 180
Dextrose 160
35
Lactose
140
30 Fructose

Sparking voltage, V
Conductivity, mS/cm

120
Sucrose
25
100
Dextrose
20 80
Lactose
15 60
Fructose
40 Sucrose
10
20
5 0 2 4 6 8 10 12 14 16
0 2 4 6 8 10 12 14 16 18
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Weight fraction, % Weight fraction, %

Fig. 2 Effect of the concentration of carbohydrates on the Fig. 3 Effect of the concentration of carbohydrates on the spark-
conductivity. Temperature: 299 K ing voltage. Temperature: 299 K

9
placed either in a refrigerator maintained at −4 or in a
105°C oven, respectively. Some of the preparing ca- 8
pacitors were maintained at 105°C with a voltage loading
of 11.5 V to test the capacitors’ durability. 7

III. RESULTS AND DISCUSSION 6


pH

1. Effect of Carbohydrates 5 Dextrose


Lactose
(i) Effect of the Carbohydrates on Conductivity 4
Fructose
3 Sucrose
The relation of the conductivity variation of the
electrolyte in the presence of carbohydrates, i.e.,
2
dextrose, fructose, lactose and sucrose, respectively, 0 2 4 6 8 10 12 14 16
is as shown in Fig. 2. According to the experimental Weight fraction, %
data, the conductivity of electrolytes was decreased Fig. 4 Effect of the concentration of carbohydrates on the pH.
by adding any kind of carbohydrates to the raw Temperature: 299 K
solution, and the conductivity decreased from 31.00
to 13.30 mS/cm when the concentration of lactose
increased from 1.37 to 12.33%. The tendency to de- sparking voltage indicate that the film of aluminum
creasing conductivity of electrolytes with carbohy- oxide becomes stronger at the surface of the alumi-
drates added is apparently due to the fact that the num foil due to the increase of carbohydrates. It has
carbohydrates do not dissociate to produce ions. been reported that the hydroxyl group of dextrose
Further, by adding carbohydrates, the solution has could protect the aluminum oxide film at the anode
become over saturated and will produce precipitates and that also could inhibit the generation of hydro-
in the aqueous solution (Kudoh et al., 1999). gen at the cathode during the charge-discharge pro-
cess (Ryutaro, 1994). Furthermore, the tendencies
(ii) Effect of the Carbohydrates on Sparking Voltage of variations in the sparking voltage are similar in
the presence of other kinds of carbohydrates, e.g.,
Figure 3 shows the effect of the kind of carbo- fructose, dextrose and sucrose, as shown in Fig. 3.
hydrates on the sparking voltage of the ethylene/wa-
ter system. It is apparent from Fig. 3 that the increase (iii) Effect of the Carbohydrates on pH
of sparking voltage is mainly dependent on the con-
centration of carbohydrates, since the sparking volt- Figure 4 shows the variation of pH value accord-
age increases from 50 to 130 V as the concentration ing to the kind of carbohydrate. The pH of electro-
of lactose increases from 1.37 to 5.50%. Increases in lytes for various concentrations of carbohydrates
156 Journal of the Chinese Institute of Engineers, Vol. 29, No. 1 (2006)

Table 1 The properties of electrolytes


Conductivity* Sparking Voltage pH Electrolyte Stability # Capacitor Stability &
Additive
mS/cm V at 269 K at 378 K
Raw electrolyte 22.3 70 6.06 precipitation failure
Dextrose 23.0 137 6.80 clear > 750 h
Lactose 22.5 128 6.78 precipitation failure
Fructose 22.1 128 6.32 precipitation failure
Sucrose 22.3 132 6.88 precipitation failure
*: The conductivity was measured at 299bK.
#: Storing the capacitor impregnated with the preparing electrolyte at 269 K for 7 days tested the stability.
&: Storing the capacitor impregnated with the prepared electrolyte at 378 K. The case of failure means the can
of the capacitor expanded and exploded.
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found from Fig. 4 was nearly neutral, in the range 2.0


storage Dextrose 8.0%
from 6.22 to 6.89. The lowest value of pH decreased
from 6.60 to 6.22 by increasing the fructose concen- Lactose 3.3%
tration from 1 to 10%. Otherwise, the pH value was Lactose 3.9%
1.6
at the highest, about 6.88, in the presence of sucrose, Sucrose 5.2%
Capacity, µ F

and so on. Here, the electrolyte pH did not vary with Sucrose 8.0%
the addition of these carbohydrates because the mol-
ecules of carbohydrates could not dissociate to alter 1.2
the concentration of H + in the solution, as shown in
Fig. 4.
0.8
2. Characteristics and Durability of Capacitor

(i) The Properties of Preparing Electrolyte 0 100 200 300 400 500
Time, h
Table 1 shows electrolyte properties after add- Fig. 5 The variation of capacity for capacitors stored at 378 K
ing the different types of carbohydrates to the raw without loading. Frequency: 120 Hz
solution, as well as the conductivity, pH, sparking voltage
and stability as functions of the kind of carbohydrates.
The results show that the sparking voltage was strongly
affected by adding the carbohydrates to the raw K without voltage loading. In addition, the variation
electrolyte; for example the sparking voltage increased of DF increased from 6.00 to 8.50 with time in the
from 70 V with zero dextrose to 137 V in the pres- storage period, as shown in Fig. 6. On the other hand,
ence of 8% dextrose solution. Furthermore, in this in the capacitors stored at 378 K without voltage
case the values of conductivity and pH of solution loading, the leakage current increased from 44 to 1550
were only slightly changed. On the other hand, the µA with the increase in testing time from 0 to 250 h.
aluminum electrolytic capacitor was more stable over In addition, the leakage current decreased from 1555
750 h by composed of 8% dextrose in the raw electrolyte. to 56 µA as testing time increased from 250 to 500 h
However, the aluminum capacitors using these elec- for capacitors stored at 378 K without loading, as
trolytes were failures. This is shown in Table 1, test- shown in Fig. 7. There are many salts in the raw
ing stability at 269 and 378 K. electrolyte, such as ammonium formate, ammonium
dihydrogen phosphate, and ammonium adiapate and
(ii) High Temperature Storage so on (Tsai, 2001; Tsai et al., 2002a; 2002b). Under
high temperature storage, i.e., 378 K, these salts could
Figure 5 shows the durability of capacitors im- react with ethylene glycol or dextrose to undergo es-
pregnated with electrolyte-containing carbohydrates terification to produce esters after 250 h storage.
tested at 378 K without loading voltage. The capac- Furthermore, the concentration of dextrose decreased
ity of the capacitors containing 8.0% dextrose de- in the raw electrolyte. Hence, the capacitor was stored
creased from 1.400 to 1.180 µF with increase in time without loading, the passive oxide film was attacked
from 0 to 500 h when the capacitor was stored at 378 by electrolyte, and the leakage current increased
M. L. Tsai and H. Y. Lin: Electrolyte for Aluminum Electrolytic Capacitor–Effect of Carbohydrates 157

2.0
10 Storage
Loading
Dextrose 8.0%
1.8 Lactose 3.3%
8 Lactose 3.9%
1.6 Sucrose 5.2%

Capacity, µ F
6 Sucrose 8.0%
1.4
DF

Dextrose 8.0%
4 Lactose 3.3%
1.2
Lactose 3.9%
Sucrose 5.2%
2
Sucrose 8.0% 1.0

0 0.8
0 100 200 300 400 500 600
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Time, h 0 250 500 750 1000


Time, h
Fig. 6 The variation of DF for capacitors stored at 378 K without
loading. Frequency: 120 Hz Fig. 8 The variation of capacity for capacitors stored at 378 K
with loading. Frequency: 120 Hz, loading voltage: 11.5 V

8000
storage 12
Dextrose 8.0%
Loading
Lactose 3.3%
6000 Lactose 3.9%
Sucrose 5.2% 9
Sucrose 8.0%
LC, µ A

4000
DF

2000 Dextrose 8.0%


Lactose 3.3%
3 Lactose 3.9%
Sucrose 5.2%
0
0 100 200 300 400 500 600 Sucrose 8.0%
Time, h
0
0 250 500 750 1000
Fig. 7 The variation of Lc for capacitors stored at 378 K without
Time, h
loading
Fig. 9 The variation of DF for capacitors stored at 378 K with
loading. Frequency: 120 Hz, loading voltage: 11.5 V

(Tsai, 2001; Tsai et al., 2002a; Tsai et al., 2002b;


Tsai et al., 2005). The leakage current decreased from
1555 to 56 µA when the storage time was over 250 h and the leakage current decreased from 36.0 to 12.0
because the esterification is reversible. µA with the increase in testing time from 0 to 750 h
for capacitors stored at 378 K with loading of 11.5
(iii) High Temperature Loading V., as shown in Figs. 9 and 10. Comparison of the
leakage current variation with loading and without
The experimental results of the high tempera- loading show large differences as shown in Figs. 7
ture loading test (11.5 V and 378 K) show perfor- and 10. Leakage current could be up to 1555 µA for
mance of the aluminum electrolytic capacitor as tested a 250 h test without loading at 378 K because the
for 250 h with the addition of different kinds of film of aluminum oxide could not be repaired as shown
carbohydrates, e.g., fructose, lactose and sucrose, to in Fig. 7. Furthermore, the value of leakage current
the raw electrolyte, as shown in Table 1 and Fig. 8. became smaller because the aluminum oxide film could
Furthermore, the aluminum capacitor with 8.0% dextrose be repaired by the loading voltage of 11.5 V. Hence,
in the raw electrolyte was still more stable, and the the lifetime of a capacitor became longer due to the
variation of capacity decreased from 1.380 to 1.200 stronger aluminum oxide film that is renewed in the
µF. In addition, the DF changed from 6.30 to 9.15 loading process.
158 Journal of the Chinese Institute of Engineers, Vol. 29, No. 1 (2006)

100 Solution for Electrolytic Capacitor and Electro-


Loading lytic Capacitor Using the Same,” J. P. Patent 6,
Dextrose 8.0%
80 Lactose 3.3% 288,889, September, 11.
Lactose 3.9% Kazuhiko, I., Shoichiro, M., and Makoto, U., 1988,
Sucrose 5.2% “Electrolyte for Aluminum Electrolytic
60 Sucrose 8.0% Capacitor,” J. P. Patent 4,786,429, November, 22.
LC, µA

Kudoh, Y., Akami, K., and Matsuya, Y., 1999, “Solid


Electrolytic Capacitor with Highly Stable Con-
40
ducting Polymer as a Counter Electrode,” Syn-
thetic Metals, Vol. 102, No. 1-3, pp. 973-974.
20 Munehiro, M., 2000, “Aluminum Electrolytic
Capacitor,” J. P. Patent 6,128,179, October, 03.
Naoi, K., Takede, M., Kanno, H., Sakakura, M.,
0 and Shimada, A., 2000, “Simultaneous Electro-
Downloaded by [University of Western Ontario] at 23:05 13 November 2014

0 250 500 750 1000 chemical Formation of Al 2O 3:Polypyrrole Layers


Time, h
(I): Effect of Electrolyte Anion in Formation
Fig. 10 The variation of Lc for capacitors stored at 378 K with Process,” Electrochimica Acta, Vol. 45, No. 20,
loading. pp. 3413.
Niwa, S., and Taketani, Y., 1996, “Development of New
Series of Aluminium Solid Capacitors with Organic
IV. CONCLUSIONS Semiconductive Electrolyte (OS-CON),” Journal
of Power Source, Vol. 60, No. 2, pp. 165-171.
The preparation and the textural characteristics Roland, F. D., 1983, “Glycol Fill Electrolyte Therefor,”
of electrolyte solutions containing carbohydrates such U.S. Patent 4,408,258, October, 04.
as dextrose, lactose, fructose, or sucrose have been stud- Ryutaro, N., 1994, “Electrolytic Capacitor Solution for
ied and capacitors impregnated with the above elec- Hydrogen Generation,” J. P. Patent 06,124,852.
trolytes have been tested. Experimental results show Shoichiro, M., Kazuhiko, I., and Makoto, U., 1988,
that a capacitor impregnated with an electrolyte con- “Electrolyte for Aluminum Electrolytic
taining dextrose exhibited a satisfactory durability. Capacitor,” J.P. Patent 4,774,011, September, 27.
Comparied with the original commercial electrolyte, Tsai, M. L., 2001, “Aluminum Electrolytic Capacitors,”
the sparking voltage increased by 96% when the elec- ChIChE. Annual Meeting and Conferences, Tung-
trolyte had 8.0% dextrose as additive. The capacity hai University, Taiwan, pp. 165.
of a capacitor impregnated with electrolyte contain- Tsai, M. L., Lin, S. Y., 2005, “Electrolyte for Alumi-
ing 8.0% dextrose increased slightly, and the DF value num Electrolytic Capacitor- Effect of the Organic
increased slightly with the increased storage time, both and Inorganic Ammonium Salts,” Journal of the
with and without voltage loading at 378 K. The leak- Chinese Institute of Chemical Engineers, Vol. 36,
age current increased from 44 to 1550 µ A with the No. 2, 161-167.
increase in testing time from 0 to 250 h and the leak- Tsai, M. L., Lin, S. Y., and Do, J. S., 2002a, “Charac-
age current decreased from 1555 to 56 µ A with the terization of Electrolyte - Effect of the tetra-Alkyl
increase in testing time from 250 to 500 h for capaci- Ammonium Salt Surfactant on the Electrolyte Per-
tors stored at 378 K without loading. In addition, leakage formance of Ethylene Glycol and Water System,”
current decreased from 36.0 to 12.0 µA when the ca- Journal of Technology, Vol. 17, No. 1, pp. 123-32.
pacitor was stored at 378 K with 11.5 V loading. Tsai, M. L., Lu, Y. F., and Do, J. S, 2002b, “ High-
Performance Electrolyte in the Presence of
ACKNOWLEDGMENTS Dextrose and its Derivatives for Aluminum Elec-
trolytic Capacitors,” Journal of Power Sources,
The authors are grateful, for financial support Vol.112, No. 2, pp. 643-648.
from the National Science Council of the Republic Ue., M., Takeda, M., Suzuki, Y., and Mori, S., 1996,
of China (NSC 91-2214-E-167-002), to the Her Mei “Chemical Stability of γ-Butyrolactone-Based Elec-
Electronic Co. Ltd., for their co-operation during the trolytes for Aluminum Electrolytic Capacitors,”
present work, and also to the National Chin-Yi Insti- Journal of Power Sources, Vol. 60, No. 2, pp. 185-
tute of Technology. 190.

REFERENCES Manuscript Received: Aug. 31, 2004


Revision Received: Mar. 25, 2005
Akihiko, K., and Tetsushi, O., 2001, “Electrolytic and Accepted: May 23, 2005

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