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OCTOBER
~----AND T ~ " ~ - ~ N ~ L . ~ ~" ,, , ~ 1
1981
ABSTRACT
The specific conductivity of 7.32N KOH electrolyte with zincate concen-
trations ranging from 0 to 1.5M has been measured. The electrolyte conductivity
was found to decrease with increasing zincate concentration. This finding is
consistent with predictions based on the mixture rule. The equivalent con-
ductance of 7.32N potassium zincate of 7 • 5 mho 9 cm/equiv, m a y indicate
the formation of neutral associated ion pairs from potassium and zincate ions
in the electrolyte. F u r t h e r calculations indicated that the mixture rule yields
predictions of conductivities for the K F - K O H and K2COa-KOH systems that
are in good agreement with experimental data in the literature.
The p r i m a r y purpose of this study was to obtain spe- where y is the molar fraction of zincate species precipi-
cific conductivity data for 7N KOH electrolyte super- tating to form ZnO. Reaction [4] suggests that the
saturated with zincate. These fundamental data are electrolyte is a ternary system consisting of potassium
needed for engineering analysis of zinc porous elec- hydroxide, potassium zincate, and water.
trodes used in alkaline batteries under development Ternary electrolyte theory developed from the p r i n -
for n e a r - t e r m use in electric vehicles. These data also ciple of irreversible thermodynamics has been de-
provide a baseline for the evaluation of modifications of scribed by Miller (7) and Sunu and Bennion (8). To
b a t t e r y electrolyte. predict the transport properties of a t e r n a r y electrolyte
The electrolyte in Ni/Zn batteries is initially about system by using the theory, one has to estimate the
31% KOH (7N) saturated with ZnO. During cell dis- values of six solvent-fixed ionic transport coefficients.
charge, the concentration of zincate has been observed Miller (7) s empirically that, for seven ternary
to rise by three to four times the chemical solubility of alkali halide mixtures at total concentrations ranging
ZnO in KOH solution (1-3). Furthermore, the conduc- from 0.5 to 3N, the ionic transport coefficients (lij) can
tivity of the electrolyte at a given concentration and be closely approximated using lij data from a p p r o p r i -
temperature has been found to decrease linearly with ate binary systems. These estimated values of t e r n a r y
an increasing amount of dissolved ZnO up to saturation l U yield good estimates of transference numbers, con-
concentration (4-6). We have determined the conduc- ductances, and solvent-fixed thermodynamic diffusion
tivity of the KOH electrolyte with zincate concentra- coefficients. In our system, sufficient conductivity data
tions up to twice chemical saturation. for potassium zincate are lacking. Therefore, this
During the discharge of zinc/nickel oxide cells, the theory cannot be used to analyze our conductivity data.
reactions for the zinc electrode may be written as fol- However, the conductance, A123, of the seven alkali
lows halide mixtures can also be predicted at low concen-
Zn + 4 O H - --> Zn(OH)42- + 2 e - [1] trations by the solution mixture rule (7), which states
that
The zincate species m a y also precipitate to form zinc A123 : X2A12 + X3AIs [B]
oxide according to the reaction
where An (i = 2, 3) is the conductance of the b i n a r y
Zn (OH)42- -) ZnO + H~O + 2 O H - [2] electrolyte at the same total equivalent concentration,
N, of the mixture and where the equivalent fractions,
For the nickel oxide electrode, the reaction is Xi, are given by
NiOOH(s) + H20 -{- e - ~ Ni(OH)2(s) nu O H - [3] Nl
X i = - - i=1,2,3 [6]
N~+N8
Thus, the net reaction of the cell system may be written
as X1 = X2 + X8 = I [7]
Zn -{- 2NiOOH(s) H- (2 -- y) H20 + (2 -- 2y) O H - Substituting Eq. [7] into Eq. [5], one obtains
-# (I -- y) I n ( O H ) 4 ~- + 2Ni(OH)s(s) nu y Z n O ( s ) AI~3 = A13 -- (AI3 -- AI~)X~ [8]
[4] In this study, we found that our conductivity data
* Electrochemical Society Active Member. for the KOH-K~Zn(OH)4 system and the data for the
Present address: D e p a r t m e n t of C h e m i s t r y , U n i v e r s i t y of Wis- K O H - K F system (9) and the KOH-K2CO3 system (10)
c o n s i n , Milwaukee, Wisconsin 53201.
Key words: mixture rule, K O H - K F , KOH-K2Co3. are consistent with the solution mixture rule.
2049
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2050 J. EZectrochem. Soc.: E L E C T R O C H E M I C A L S C I E N C E A N D T E C H N O L O G Y October 1981
I I t "-~ ELECTRODE
- - CE1 RE ,~,.vv~.
I I I
0.6 (
E
~ - - ] = ~ 1 ~ z n ELECTRODE
F-
0.4
(D
C~
Z A DIRKSE, 7.4 N KOH, 25~
RESE / MOM O
0.2_ - - 0 BAKER AND T R A C H T E N B E R G , 6.9 N KOH, 25~ __
(D
U_
[] THORNTON AND CARLSON, 7.1 N KOH~ 26.4~
0 THIS WORK, 7.52 N KOH, 25%
UJ
D_
r
~ - ~ PUMP
o I I t
1 I~ ' ~ - ~ CONSTANT 0.5 1.0 1.5 ~-.0
TEMPERATURE ZINCATE CONCENTRATION, M
BATH
Fig. 2. Specific conductivity of KOH electrolytes as a function of
Fig. 1. Experimental apparatus zincate concentration.
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V o L 128, No. 10 CONDUCTIVITY OF KOH ELECTROLYTE 2051
other workers. This figure also indicates t h a t the of p o t a s s i u m ions p e r 2 e - w e r e t a k e n up from the
conductance of the e l e c t r o l y t e m a y be l i n e a r l y c o r r e - charging cell and r e l e a s e d in the zincate g e n e r a t i n g
lated w i t h zincate concentration. A l i n e a r r e l a t i o n s h i p cell. F o r our m a x i m u m zincate concentration of 1.53M,
for conductivity vs. weight p e r c e n t of ZnO was also the concentration of potassium ions is e s t i m a t e d to
o b s e r v e d b y Dyson et al. (4) up to chemical s a t u r a t i o n increase b y a m a x i m u m of 0.15N or 2% of its original
of ZnO in more concentrated K O H e l e c t r o l y t e (namely, value. Therefore, we m a y assume that the concentra-
35-46% b y w e i g h t or 8.3-11.6N). The l i n e a r r e l a t i o n - tion of potassium ions in t h e e l e c t r o l y t e t h r o u g h o u t
ship shown in Fig. 2, b e t w e e n the specific conductivity, the e x p e r i m e n t did not change. W h e n d i v i d e d b y the
k, and the m o ! a r concentration of zincate, Czn(n), can total e q u i v a l e n t concentration (7.32N), Eq. [9] is
be e x p r e s s e d b y the equation t r a n s f o r m e d to
k ---- (0.637 _+ 0.011) -- (0.159 __ 0.009)Czn(n) m h o / c m A~23 = (87 _+ 2) -- (80 __ 5) X2 mho 9 cm~/equiv. [10]
~
G
sium ions a r e t a k e n up b y nickel o x i d e electrodes d u r - 0 80+5)x z
ing ~he .charge cycle, and r e l e a s e d d u r i n g the discharge 801
cycle. A r e c e n t s t u d y b y B a r n a r d et al. (17), indicates
O
that the t a k e - u p / r e l e a s e of potassium ions depends on Z 0~.
0
o
the crystal s t r u c t u r e of the nickel oxide electrode: 40
0.102 tool p e r 2 e - for fl-NiOOH and 0.47 mol p e r 2 e - Z
for ~-NiOOH. H a r i v e l et al. (18) indicated t h a t the ILl
--I
.h=(69 + 2)-141+4)x 2
f o r m a t i o n of fl- and %,-NiOOH depends upon the c h a r g -
ing rate, the state of charge, a n d the e l e c t r o l y t e con- o , I , r , ', I , [ J
0 0.4 0.8 0 0.4 0.8
centration. In our study, the n i c k e l oxide electrode
KOH K2Zn(OH) 4 KOH K2CO3
was c h a r g e d at 6 m A / c m 2 up to 20% of t h e o r e t i c a l
c a p a c i t y (3 A - h r ) in a cell with fresh electrolyte and EQUIVALENT FRACTION, x 2
then discharged in the zincate g e n e r a t i n g cell. U n d e r Fig. 3. Equivalent conductances of KOH-K2Zn(OH)4 system,
such conditions, o n l y fl-phase m a t e r i a l s a r e e x p e c t e d KOH-KF system and KOH-K2CO.~ system as a function of equiva-
to be formed. Therefore, we estimate t h a t 0.102 mol lent fraction.
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2052 J. EIectrochem. S;oc.: ELECTROCHEMICAL SCIENCE AND TECHNOLOGY October 1981
Table I. Values of A13 and -~la -- A12 obtained from binary system data and least squares
analyses of ternary system data using the mixture rule (Eq. [8])
9Obtained from Ref. (9) and (10) and this work except for the v a l u e o f An f o r KF, which was calculated from the table given in
Ref. (12).
Ref. (9) and (10) [see text for a discussion of the data from R~f. (10)].
b C a l c u l a t c d f r o m o u r data and t h o s e f r o m
Summary REFERENCES
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