Transient and Failure Analyses of the Porous

Zinc Electrode
I. Theoretical

W. G. Sunu*'1 and D. N. Bennion*,s

School of Engineering and Applied Sciences, University of California, Los Angeles, California 90024

ABSTRACT
A ,mathematical model which describes the t r a n s i e n t b e h a v i o r of porous
zinc electrodes has been developed on the basis of concentrated t e r n a r y elec-
trolyte theory. The model predicts the c u r r e n t distribution, potentials in the
solution, concentrations of hydroxide ion a n d zincate ion, porosity, and vol-
ume fractions of zinc and zinc oxide as a function of time and position per-
p e n d i c u l a r to the surface of the electrode. Numerical techniques were used
to predict zinc electrode behavior during galvanostatic operation of the cell
with and w i t h o u t a m e m b r a n e . D u r i n g discharge of the cell w i t h o u t a m e m -
brane, m u c h of the discharge product, zincate ions, are lost into the counter-
electrode compartment. For the cell with a m e m b r a n e , this zincate loss is effec-
tively restricted, b u t the utilization of zinc is severely limited b y depletion of
hydroxide ions w i t h i n the zinc electrode compartment. I n both cases, the re-
action profiles are highly n o n u n i f o r m and the reaction zone, located near the
electrode surface, is very thin. This highly n o n u n i f o r m reaction d i s t r i b u t i o n
accentuates the failure due to electrolyte depletion in the i n t e r i o r of the
porous electrode, resulting in the low discharge capacity. On repeated cycling,
the difference i n anodic and cathodic reaction distribution causes the redistri-
b u t i o n of solid zinc a n d zinc oxide species.

The zinc electrode has been c o m m o n l y used as a
negative electrode i n p r i m a r y cells such as Leclanchd
dry cells and alkaline zinc m a n g a n e s e dioxide cell.
It also has received considerable attention, d u r i n g
the last decade, as a negative plate i n secondary b a t -
teries, e.g., zinc-nickel, zinc-silver oxide, z i n c - b r o -
mine, a n d zinc-chlorine cells. The use of zinc elec-
trodes in secondary batteries is attractive because of
its availability, its low cost, and its ability to deliver
high energy and power density. However, secondary
batteries using zinc electrodes have poor cycle life,
limited by zinc electrode failure. A n y i m p r o v e m e n t s
on the cycle life of the a l k a l i n e zinc electrode can be
applicable to its use i n Z n - N i O O H or Z n - A g O re-
chargeable batteries, which are potential systems for
use in electric vehicle propulsion or aerospace.
F a i l u r e of the zinc electrode can be a t t r i b u t e d to a
variety of causes. Two m a j o r causes of failure are
zinc dendrite formation a n d shape change. The zinc
dendrites which are formed d u r i n g charge penetrate
the separator and cause short circuits to the c o u n t e r -
electrode. Much of the work to date on i m p r o v i n g
zinc electrode behavior d u r i n g charge has been as-
sociated with zinc deposit morphology, deposit ad-
herency, and m e c h a n i s m of dendrite growth (1-5).
These studies have suggested that the use of low
charge rate, pulse charging, and metallic or organic
additives have some beneficial effects on p r e v e n t i n g
the formation of dendritic zinc deposits. The detri-
m e n t a l dendrite penetration, however, has been suc-
cessfully reduced by use of a n appropriate m e m b r a n e
m a t e r i a l (6) such as commercially available grafted
polyethylene ion exchange m e m b r a n e .
A n o t h e r failure k n o w n as shape change is the re-
d i s t r i b u t i o n of solid zinc species over the electrode
surface during cycling, which e v e n t u a l l y decreases
the effective surface area and thus cell capacity of
the zinc electrode. Previous investigators (7-9) have
* E l e c t r o c h e m i c a l Society Active M e m b e r .
1 P r e s e n t address: Gould Incorporated, Gould Laboratories--En-
e r g y R e s e a r c h , Rolling Meadows, Illinois 60008.
2 Present address: Chemical Engineering Department, Brigham
Y o u n g U n i v e r s i t y , P r o v o , U t a h 84602.
K e y w o r d s : p o r o u s zinc e l e c t r o d e s , m a t h e m a t i c a l m o d e l i n g ,
c u r r e n t d i s t r i b u t i o n , f a i l u r e mechanism.
indicated that the solid species moves from the top
and sides to the bottom and center of the zinc elec-
trode d u r i n g cycling and that loose packing, com-
pared to tight packing, of the cell promotes more
rapid redistribution of zinc.
A m e c h a n i s m based on g r a v i t a t i o n a l effects has
been proposed (10), b u t this m e c h a n i s m is not con-
sistent with the fact that shape change is i n d e p e n -
dent of cell orientation. Other investigators (7, 9, 11)
suggested concentration cell effects as a mechanism
of shape change. McBreen (7) has suggested that a
concentration cell is generated b y the difference in
the c u r r e n t distribution during charge a n d discharge.
Recently, C h o i e t al. (12, 13) have proposed that the
m a i n reason for the shape change is the concentra-
tion cell caused b y the difference i n the convective
flow p a t t e r n d u r i n g cycling, i.e., flow of s u p e r s a t u -
rated zincate solution toward the zinc electrode cen-
ter d u r i n g discharge and flow of u n s a t u r a t e d zincate
solution toward the electrode edge or solution reser-
voir d u r i n g charge. They confirmed that sealing or
tight packing of the cell, p r e v e n t i n g convection, suc-
cessfully e l i m i n a t e d the shape change.
The simple approaches m e n t i o n e d above have been
effective in e x t e n d i n g cycle life, b u t the resulting
cycle life appears still to be limited b y other factors.
I n i t i a l loss of cell capacity as well as rapid decrease
in cell capacity with continued cycling were observed
even for the sealed cells for which chemical analysis
for the zinc species confirmed no shape change (13).
This indicates that there are f u r t h e r reasons for cell
failure to be explained a n d m i n i m i z e d i n order to
gain f u r t h e r cycle improvements. The first step
towards disclosing other failure modes and mecha-
nism is to u n d e r s t a n d and be able to predict the zinc
behavior w i t h i n the porous electrode.
Various m a t h e m a t i c a l models have been proposed
to describe the behavior of porous electrodes as
s u m m a r i z e d by N e w m a n and T i e d e m a n n (14). Winsel
(15) described b a t t e r y discharge b y considering a
single pore electrode of constant porosity and u n i -
form concentration. N e w m a n a n d Tobias (16) i n -
cluded the effects of a m a t r i x resistance and concen-
t r a t i o n changes in their s t e a d y - s t a t e analysis of a

2007

Downloaded on 2014-05-12 to IP 183.221.12.205 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
 2008 J. Electrochem. 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 S e p t e m b e r 1980

one-dimensional, homogeneous m i x t u r e model. A n I n a concentrated KOH solution saturated with

a t t e m p t to consider s t r u c t u r a l changes i n the pores
was initiated b y Alkire et al. (17). D u n n i n g et al.
(18) proposed a m a t h e m a t i c a l model which predicted
discharge and cycling behavior of an Ag/AgC1 elec-
ZnO, it is possible for the following complexes of zinc
species to be present as i n t e r m e d i a t e compounds:
Zn ++, Z n ( O H ) +, Zn(OH)2, Z n ( O H ) 3 - , Z n ( O H ) 4 =
9 Z n ( O H ) n 2-n. Based on the e q u i l i b r i u m constants
. .

trode i n NaC1 solution. Recently, G u et al. (19) ex- reported b y Butler (35), Boden et al. (36) concluded
tended the model of D u n n i n g et al. to include surface that the only species present to a n y appreciable ex-
diffusion of the adsorbed complex ion a n d realistic tent in KOH solution was Z n ( O H ) 4 = ion. Other w o r k -
active surface area based on their e x p e r i m e n t a l m e a - ers (37-39) also confirmed that the p r e d o m i n a n t spe-
surements. Simonsson (20,21) applied his model to cies was zincate ion. Therefore, in the present work,
predict the failure mode of the positive electrode of the electrolytic solution was considered as a four
the lead-acid battery. He showed that the discharge component system containing K +, O H - , Z n ( O H ) 4 =,
of the positive lead dioxide electrode at high c u r r e n t and H~O.
load failed b y the severe depletion of sulfuric acid
Description o] the model.--A o n e - d i m e n s i o n a l
at the pore mouth, while Gidaspow a n d Baker (22)
m a t h e m a t i c a l model of a porous zinc electrode has
emphasized the pore plugging as a m a j o r cause of
been proposed which predicts O H - concentration c3,
discharge failure.
Z n ( O H ) 4 = concentration c2, superficial c u r r e n t den-
In the present work, a m a t h e m a t i c a l model is de-
sity i n the solution i2, transfer c u r r e n t density j,
veloped to describe the t r a n s i e n t behavior of the
porosity e, superficial volume average velocity v, po-
porous zinc electrode on the basis of concentrated
tential in the solution r a n d potentials i n the m a t r i x
t e r n a r y electrolyte theory. The discharge product
r as a f u n c t i o n of time a n d position p e r p e n d i c u l a r
ZnO is highly soluble i n KOH solution, resulting in
to the electrode surface. The geometric feature of
the potassium h y d r o x i d e - p o t a s s i u m z i n c a t e - w a t e r
the model is quite similar to that of previous studies
t e r n a r y mixture. It was also reported that the solu-
(16, 19). A backing plate is located at x ---- 0 and the
tion near the discharging zinc surface could become
m e m b r a n e or b o u n d a r y layer at x ---- L. The porous
supersaturated with zincate (23). Therefore, f u n d a -
electrode is treated as a homogeneous m i x t u r e of
m e n t a l equations developed for describing the con-
ionically conducting solution phase a n d a n electri-
centrated t e r n a r y solution (24) were applied to the
cally conducting m a t r i x phase. The solid m a t r i x
pre~ent model.
m i g h t contain zinc, ZnO, a n d i n e r t conducting m a t e -
The model presented here consists of Ohm's law in
rials (e.g., graphite) or a n y combination of the three.
the solution phase, Ohm's law in the m a t r i x phase,
The macroscopic averaging technique (14, 40) was
kinetic rate expression, conservation of charge, and
applied to the p r e s e n t model by disregarding the ac-
conservation equations of O H - ion, zincate ion,
tual geometric details of the pores. For example,
water, a n d solid species. The effect of local mass
consider ci as the concentration of species i averaged
transfer b e t w e e n the electrode active surface and the
over the volume of solution i n the pores. T h e n the
bulk solution i n the pores, changes in porosity, v a r i -
superficial concentration, averaged over the u n i t
ations of active surface area, and convection arising
volume of the electrode, is eci where ~ is the porosity
from the difference in molar volumes of reactants
of the electrode. If Ni is defined by the superficial
and products were included. The effect of the m e m -
b r a n e separator a n d the solution reservoir on the zinc flux based on the u n i t cross-sectional area of the
electrode, Nile represents the flux t h r o u g h the u n i t
electrode performance was also included in the model
area of solution phase i n the pores. Similarly, v/e is
to predict m a t h e m a t i c a l l y behavior u n d e r conditions
the velocity in the solution phase if v is a super-
similar to a practical b a t t e r y system. The results of
ficial b u l k fluid velocity.
the n u m e r i c a l solution were used to suggest certain
modes of failure and performance limitations of the With these average quantities (Ni/e, if~e, and v/e),
transport equations developed for the concentrated
zinc electrode.
t e r n a r y solution (24) were applied to the p r e s e n t
The Mathematical Model four component system on the basis of reaction
mechanism [A] and [B]. The results are w r i t t e n as
Zinc electrode reaction.--The process occurring i n
the zinc electrode in alkaline solution has been de- N2 dCA dCB t2
scribed by a dissolution-precipitation m e c h a n i s m -~ --DAAel+t --DAB el+t -~ ' -~ CAr
(25, 26) ~ dX dx Z2vfAF~2
Z n -5 4 O H - <-->Z n ( O H ) 4 = -5 2e- [A] [1]
Z n ( O H ) 4 = <-->Z n O + 2 O H - -5 H 2 0 [B] N3 dCA dCB t3
_ _ --- __ DBAel+t -- D B B e I + t ~ -5 Z3~3BF{2 -5 CBV
Discharge of the zinc electrode produces supersatu- v~B dx dx
rated zincate solution by electrochemical reaction [2]
[A], from which Z n O precipitates by a chemical re-
action [B]. The reverse process occurs d u r i n g charge. dcA dCB
No -- DoAEl + t -5 DOB~l+t -5 CoY [3]
Previous investigators (26, 27) have attempted to dx dx
determine the rate of the precipitation reaction. How- where
ever, values of rate constants are not precisely known.
The kinetic m e c h a n i s m of reaction [A] has b e e n DU ---~(Du)~ - - Doj(ci/Co) ; i,j : - A,B
studied in alkaline media using both zinc a m a l g a m
electrodes (28-30) a n d p u r e solid zinc electrodes (31- Doj : - ~ coV'-k(Dkj) o ; j,k -- A,B
34). The mechanism proposed by Bockris et al. (34)
[4]
was considered i n the present work to estimate ki-
ti ~ ( t i ) ~ - - Zicito ; i ~- 1,2,3
netic parameters
V~(t~)o V2(t2)o Vs(t~)o
Zn -5 O H - <-> Z n ( O H ) -5 e - [C]
to - - - ~ - - - + - -
Zl Z2 Z3
Z n ( O H ) -5 O H - <-->Z n ( O H ) 2 - [D] where subscripts 1, 2, 3, A, B, and o represent K +
ion, Z n ( O H ) 4 = ion, O H - ion, potassium zincate, potas-
Z n ( O H ) 2 - -5 O H - <-> Z n ( O H ) ~ - -5 e - [El sium hydroxide, and water, respectively, Ni iS the
Z n ( O H ) 3 - -5 O H - <-> Z n ( O H ) 4 = [F] flux of species i, Vi is the partial molar volume of
species i, ci is the concentration of species i, zi is the
where reaction step [El is the r a t e - c o n t r o l l i n g step. charge n u m b e r of species i, i2 is the c u r r e n t density

Downloaded on 2014-05-12 to IP 183.221.12.205 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
 Vol. I27, No. 9 POROUS ZINC ELECTRODE 2009

i n the solution phase, t is the tortuosity factor, and v
is the volume average velocity. T h e diffusion coef-
ficients Dij(i,j -- A,B) a n d the transference n u m b e r s
t~(i _-- 1,2,3) are defined with respect to the volume
average velocity v, while those with superscripts "o"
are referred to the solvent reference velocity Vo. The
vu is the n u m b e r of ionic species i per. molecule of
electrolyte "j."
E l e c t r o n e u t r a l i t y requires Z~V~A -t- Z2~2A : 0, Z ~ B
-t- z ~ s -- 0, a n d zlcl -{- z2c2 -t- zsc3 -- 0. For the sol-
vent velocity reference frame, the p a r a m e t e r s DOA,
DOB, and to disappear from the above equations. The
p a r a m e t e r s Dij, ti, and v should be replaced with
(Dij) ~ (ti) ~ a n d Vo, respectively, to represent the
flux equations referred to the solvent velocity Vo. The
effective diffusion coefficients Dije l+t account for the
tortuosity correction. Schofield and D a k s h i n a m u r t i
(41) have suggested that the effective diffusion coef-
ficients are proportional to ~1.5 (or t = 0.5). The
p a r a m e t e r to was t a k e n as zero (or ti ---- ti ~ b y defini-
tion [see Ref. (24) ].
O h m ' s l a w in t h e solution p h a s e . - - A modified Ohm's
l a w applied to the t e r n a r y electrolyte solution is given
b y the following equation
+t d~b2 /Cel%t ( 82 nt2 So
is - - K~ + - - CA
dx n F ~ ~2A Z2P2A Co ]
,d#A gel+t ( Ss -~- __nt3 So d/~BcB
) [5]
d~ nF P3B Z3P3B Co -~
where r is the potential of a reference electrode of
the same k i n d as the working electrode placed in the
b u l k solution w i t h i n the pores of the porous electrode,
is the conductivity of solution at concentration ci,
and #i is the chemical potential of species i. The si
is the stoichiometric coefficient of species i for the
electrode reaction given b y
~ s~Mi=~ = h e -
where ~/i is the symbol r e p r e s e n t i n g the chemical
f o r m u l a of species i, zi is the charge n u m b e r of species
i, a n d n is the n u m b e r of electrons transferred b y
the electrode reaction.
The effective solution conductivity corrected for
tortuosity is represented by K~1+t. Meredith and Tobias
(42) and G a g n o n (43) suggested t as 0.5, while t = 2
was observed b y Ksenzhek et al. (44). Simonsson
(20) a n d Romanova and Selitsky (45) observed an
effective conductivity which was only o n e - t e n t h of
the conductivity of the free electrolytic solution. They
a t t r i b u t e d this large reduction to the gas generated
in the pores.
R e d o x e l e c t r o c h e m i c a l rate e x p r e s s i o n . - - T h e rate of
charge transfer reaction [A] at the solid-solution i n t e r -
face and the conservation of charge can be r e p r e -
sented b y the following e q u a t i o n
solution interface area per u n i t v o l u m e of electrode
which acts as active sites for reaction [A]. The t r a n s -
fer c u r r e n t j was related to the gradient of the c u r r e n t
density/2 b y the charge conservation equation.
The concentration of zincate ion (C2s) a n d hydroxide
ion (css) at the reacting metal surface can be d e t e r -
m i n e d ~rom the following equations
di~. nF
-- -- akA(css -- ca) [8]
dx Sg.
di~ nF
-- -- akB (css -- c3) [9]
dx sa
where a is the solid-solution interface area per u n i t
volume of the electrode a n d ki is the mass transfer
coefficient of species i t r a n s f e r r i n g from the b u l k
solution in the pores to the reaction sites which are
active for charge transfer reaction [A] or vice versa.
The potential at the metal surface, ~2s, was assumed
to be the same as the potential of the b u l k solution
i n the pores, ~2. The mass transfer coefficients /CA
a n d kB a n d the active surface area am change with
time and the state of charge. True values of these
parameters are difficult to determine. Consequently,
the mathematical forms described in A p p e n d i x B
were assumed in this work. The constants ~, L aa,
and at, corresponding to the reaction m e c h a n i s m of
Bockris et al. (34), are 0.75, 0, 1.5, a n d 0.5, respectively.
The exchange c u r r e n t density, ioo, reported by pre-
vious investigators (29, 31, 34, 46) has values i n the
range of 10-300 m A / c m 2.
Species conservation e q u a t i o n . - - T h e use of appro-
priate averaging quantities yields the following con-
servation equation
Oeci dNl
, = - -- + Ri [10]
Ot dx
where Ri represents production or consumption of
[6]
species i due to the electrode reaction. D u r i n g dis-
charge, zincate ion is produced b y charge transfer
reaction [A] and consumed b y precipitation reaction
[B]. On the other hand, hydroxide ion is consumed
by reaction [A] and produced by reaction [B]. The
reaction source term J% can be w r i t t e n as
si di2
Ri : }- s i * a k s * ( c 2 -- C2e) [11]
nF dx
where ks,, d u r i n g discharge, is defined by the rate
constant combining mass transfer of zincate ions from
bulk solution in the pores to the reaction sites with
chemical rate constant for precipitation of ZnO, C2e
is the e q u i l i b r i u m or saturation concentration of zin-
cate ion at the solid-solution interface which is active
for reaction [B], and si and si. are the stoichiometric
coefficients of species i for the reaction [A] a n d for
the reaction [B], respectively, defined b y Eq. [6].
S u b s t i t u t i o n of Eq. [11] into Eq. [10] yields

0~c2 dN2 1 di2

am = -- aks,(Cz -- C2e) [12]
( a.F C~cF($1-~b2,)) Ot d x "~ n F dx
(c#1-~2s) --
e RT -- e RT [7] Oecs dN3 4 dis
Ot = -- d x nF d---x -t- 2 a k s . ( c s - - cte) [13]
where ~a and ac are the effective anodic and cathodic
transfer coefficients, respectively, j is the local t r a n s - 0eCo dNo
fer c u r r e n t per u n i t area of active zinc surface which - - -- - - ~- aks.(C~ - - cse) [14]
acts as active sites for reaction (A), ioo is the exchange Ot dx
c u r r e n t density evaluated at reference concentrations
Car and C~r, 7 and ~ are the orders of dependence of where s2 ----- -- s2. ---- -- 1, s3 ---- 4, s~. ---- -- 2, So ---- 0,
the exchange c u r r e n t density on zincate and hydroxide and so, = -- 1 have been substituted.
concentrations, respectively, r is the potential of the Overall conservation e q u a t i o n . - - T h e porosity of the
m a t r i x phase, r is the potential of the reference electrode will increase as zinc dissolves and decrease
electrode of the same kind as the working electrode as ZnO precipitates. A m a t e r i a l b a l a n c e on the solid
located 3ust outside the double layer, am is the solid- species shows how the porosity varies with time as

Downloaded on 2014-05-12 to IP 183.221.12.205 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
 2010 J. Electrochem. 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 September 1980
d~
,Oe = 1 ~i --Visi~di2 -{- ~i ~isi, aks,(c2 -- c ~ ) [ 1 5 ] i2 ~ __ gel + t -- Ke - -
~t nF dx dx
where Vi is the p a r t i a l m o l a r volume of species i and dis (aa -{- ac)F
= araioO (~bl -- r = R e ( e l -- ~b2)
the species i represents the solid species, namely, zinc dx RT
a n d ZnO.
Similarly, a m a t e r i a l balance on the ionic species d~bl dct
it = ~ - - i 2 = --r
leads to the following e l e c t r o l y t e c o n t i n u i t y equation dx dx
VB% YAs2 VBs3 [21]
"~ ~ =- Z2~2A Z3Y3B T~V2A ~Y3B The solution of Eq. [21] becomes as follows, e.g., for
current distribution
+ --aks, --+--+~oSo* di2 IQ [ coshQy coshQ(1--y) ]
n Fdx vY~A YSB -- 0"e ~ ge ;
dy Ke --~ O'e sinh Q sinh Q
(C2 - - C2e) [16]
This equation is obtained b y a d d i n g Eq. [12], [13], Q=L~/Re(~_e + o'el) [22]
and [14] which h a v e been m u l t i p l i e d b y VA/r2A, VB/r~B,
and Vo, respectively, and using the relations of cA-VA w h e r e y is the dimensionless distance from the b a c k -
ing plate (x/L) ; L is the electrode thickness.
~- CBV---B"~ CoVo = 1, VADAA -~- "VBDBA -- VoDoA = 0, The b o u n d a r y conditions at x = 0 are as follows
and V~ADAB + VBDBB -- -VoDoB = 0. The last two
relations for DoA and DOB can be d e r i v e d from Eq. [4]. dr dc~. dc3
F r o m Eq. [15] and [16], the convective b u l k flow =0 (ori2=0), =0, =0, v--0, r
dx dx dx
motion in the porous electrode can be described b y [23]
the following overall continuity equation
The b o u n d a r y conditions at x -- L are
--d~) 1 [ V'Zn + 4V"B - - VA -- 2 ' -}- is - - I }
dx nF ViA ~'IB ~(Vci)
di2
--=A(Ni)L--A(Ni)ra; i=2,3 [24]
0t
-~- a/cs*[VZnO -{- Vo -~- 2VB -- VA] (C2 -- C2e) [17]
dx w h e r e I is the a p p l i e d c u r r e n t density, A is the cross-
sectional a r e a of the electrode, and V is the v o l u m e
The second b r a c k e t t e r m is the volume change of
of the solution reservoir located b e t w e e n the electrode
r e a c t i o n [B]. The first b r a c k e t t e r m r e p r e s e n t s the
surface and the m e m b r a n e . The (N{)L and (Ni)m
volume change of reaction [A], i.e., (t2V--A/rlA + tS~rB/ r e p r e s e n t fluxes of species i across the b o u n d a r y x = L
~IB) = V1, if the transference n u m b e r to, defined in and across the m e m b r a n e , respectively. If a solution
Eq. [4], is chosen as zero. reservoir is absent (i.e., V = 0), the above b o u n d a r y
Ohm's law in the solid matrix.--Ohm's l a w in the conditions s i m p l y r e p r e s e n t the conservation of fluxes
solid m a t r i x can be w r i t t e n as at the boundary, i.e., (N2)L = (N2)m and (N3)L =
(N3) m.
dr The fluxes (N2)L and (N3)L are Eq. [1] and [2],
ii "- I -- i2 = -- ~ " m [18] a p p l i e d to the b o u n d a r y x = L, respectively. The
dx
fluxes (N2)m and (N3)m a r e w r i t t e n as
w h e r e St is the potential of the solid m a t r i x and em
is the v o l u m e of conducting m a t e r i a l p e r unit volume (N2)..__~m_ (DAA)m (C2L--C2o)"~- (t2)m I -~- C2mVm ]
Z2r2AF
of the electrode (not necessarily equal to 1 -- ,). V2A d
The superficial c u r r e n t density in the solid phase it
a n d that in the solution phase i2 a r e r e l a t e d to the (N3)m __ (DBB)m (C3L - - C3o) -}" (tS)ra I + C3mVm
Z3v3BF
total a p p l i e d c u r r e n t density I as il + i2 = I. The v3B d
conductivity of the solid m a t r i x is a p p r o x i m a t e d b y
[25]
~" = O'Zn(eZn) t* --~ O'ZnO(eZnO)t* -~- ~'i (ei) t* [19]
w h e r e d is the thickness of the m e m b r a n e and s u b -
scripts "m", "L", and "o" r e p r e s e n t values t a k e n at
where r ~zno, and ~I a r e the conductivities of the
the m e m b r a n e , r e s e r v o i r solution, and the c o u n t e r -
zinc metal, zinc oxide, a n d inert m a t e r i a l in the p u r e
electrode c o m p a r t m e n t , respectively.
solid phase, respectively, and ezn, 'zno, and ,z a r e the
The six equations w e r e l i n e a r i z e d a b o u t a t r i a l
v o l u m e fractions of the corresponding solid species.
solution, p u t into finite difference forms, and solved
Computation procedures.--The six equations; two b y the n u m e r i c a l technique d e v e l o p e d b y N e w m a n
s e c o n d - o r d e r equations [12] and [13] and four first- (47) s u b j e c t to the initial conditions [20] and [21]
o r d e r equations [5], [7], [17], and [18]; form a set and the b o u n d a r y conditions [23] t h r o u g h [25]. The
of n o n l i n e a r coupled differential equations. The six C r a n k - N i c o l s o n implicit m e t h o d (48) was used for
u n k n o w n v a r i a b l e s a r e i2, r c2, ca, v, and r which a v e r a g i n g t i m e derivatives in Eq. [I2] and [13]. The
a r e functions of time and position. The six equations resulting six finite difference equations a r e correct
can be solved b y use of a n u m e r i c a l technique w i t h to second order, h 2 and (At) 2, w h e r e h and At a r e
the following initial and b o u n d a r y conditions. the mesh sizes of distance and time. The convergence
I n i t i a l conditions at time = 0 a r e criterion used was 10 -5 which is defined b y the ratio
of the difference b e t w e e n the two successive solutions
c2 = C2o, ca=C3o, v----0 [20] to the p r e s e n t solution. The details of the n u m e r i c a l
procedures as w e l l as the c o m p u t e r p r o g r a m h a v e
F o r the o t h e r variables, the following a p p r o x i m a t e been described b y Sunu (49). The physical and c h e m -
equations w e r e solved to e s t i m a t e the initial profiles ical p a r a m e t e r s used for n u m e r i c a l calculations a r e
of i2, Ct, and s u m m a r i z e d in A p p e n d i x A. The n u m e r i c a l calculations

Downloaded on 2014-05-12 to IP 183.221.12.205 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
 VoL 127, No. 9 POROUS ZINC ELECTRODE 2011

were carried out i n double precision using a n IBM TYPE I MEMBRANE BOUNDARY
360/91 computer.
Result
The m a t h e m a t i c a l model described i n the previous CBo - - - ' ~ _
section was solved u n d e r the following conditions; the
initial solution of 8M KOH -- 0.66M K2Zn(OH)4 and _ A
the electrode i n i t i a l l y composed of 40% void volume,
50% zinc, a n d 10% ZnO b y volume (~ = 0.4, ~zn = 0.5,
~ZnO = 0.1, a n d e[ -- 0). The total capacity of this elec- 6
B
trode estimated from the a m o u n t of zinc is 17.6 A - r a i n iJl
and corresponds to a discharge for 352 m i n at 50 m A / -J 5
o
cm 2. This capacity is r e f e r r e d to as "100% depth of =E
D
discharge" or as "100% utilization" througout this 4
paper. The capacity e q u i v a l e n t to the hydroxide ions
of the pore solution is only 1.03 A - m i n or 5.85% u t i l i - 0
zation. This n u m b e r is s u r p r i s i n g l y small. Three
b o u n d a r y cases were considered using the p a r a m e t e r s o 0.8
shown in Table I. They include the type I m e m b r a n e
b o u n d a r y (second c o l u m n ) , solution b o u n d a r y (third
c o l u m n ) , a n d type II m e m b r a n e b o u n d a r y which is
e q u i v a l e n t to the use of one layer of RAI P2291 cation
exchange m e m b r a n e . The results on discharge are
~ 0.6
- CAo
A
d_
shown i n Fig. 1 to 5 a n d those on cycling are s u m -
marized i n Fig. 6 a n d 7. 8
F i g u r e 1 shows how concentrations of KOH (top
curves) and potassium zincate (bottom curves) v a r y 0.4
with time d u r i n g discharge. I n i t i a l concentration was
shown b y dotted lines. After 1 rain polarization, h y -
droxide concentration decreases to 7.6M, a v a l u e a v e r -
0.2 ] I I I
aged over the entire pore solution, a n d zincate becomes
s u p e r s a t u r a t e d (curve A). On f u r t h e r discharge, h y - x=0 0.02 0.04 0.06 0.08 0.1
droxide concentration drops r a t h e r slowly because a DISTANCE FROM BACKING PLATE (cm)
large a m o u n t of hydroxide ions which are t r a n s f e r r i n g
from the counterelectrode also participate i n the elec- Fig. 1. Concentration profiles during constant current discharge
trode reaction. For example, at 30% depth of discharge for type I membrane boundary (I -- ,50 mA/cm 2, A for 1 rain
(or 5.28 A - r a i n ) , only 0.43 A - m i n is corresponding to polarization and B, C, and D for 10%, 20%, and 30% depth of
the decrease of O H - concentration of pore solution discharge, respectively).
from 8M to 4.7M, and the r e m a i n i n g 4.85 A - m i n is
resulting from the hydroxide ions supplied from the
counterelectrode compartment. This indicates that the The charge transfer current, j (mA/cm2), is plotted
as a function of distance i n Fig. 3. Initially, the reac-
m e m b r a n e affects significantly the utilization of active
tion distribution is shown as curve A, h a v i n g a m a x i -
zinc p a r t i c u l a r l y of the cell having a limited a m o u n t
m u m at the face of the electrode. As discharge con-
of electrolyte. E q u i l i b r i u m concentration of zincate de-
tinues to 10% depth, KOH concentration, porosity, and
creases with KOH concentration and therefore zincate
therefore the conductivity of the solution decreases.
concentration also decreases as discharge continues.
This effect shifts the reaction toward the front face
However, there is always some degree of s u p e r s a t u r a -
tion with a m a x i m u m being located near the electrode
face.
t I t I
The effect of the m e m b r a n e is c l e a r l y shown i n Fig.
2 where profiles of KOH concentration obtained with 9
three types of boundaries are presented. The average
KOH concentration obtained after 10% depth of dis- CBo
E s
charge was 7.5M for the solution boundary, 5.3M for uJ
p.
the type I m e m b r a n e boundary, and 2M for the type II A
m e m b r a n e boundary. A similar calculation showed that SOLUTION
a cell with two layers of type II (RAI P2291 cation o
exchange) m e m b r a n e was completely depleted of h y - 6
droxide ions after only 8% depth of discharge. Clearly, 3:
O
J
discharge of the cell h a v i n g a type II m e m b r a n e as a v 5
B
separator could fail due to KOH depletion. P, TYPE I MEMBRANE
z
o_ 4
Table I. Transport parameters applied to the various
boundary layers ~3
Type I T y p e II 82
membrane Solution membrane C
boundary boundary ( R A I P2291) * TYPE II MEMBRANE
1
(tl) m 0.5 0.23 0.5
(t2)m 0.0 0.05 0.0 0 I I I I
(ts)m 0.5 0.72 0,5 x=0
(DAA)m (cm2/sec) 2.5 x 10 -e 6.0 x 10-e 1.0 x 10 -s 0.02 0.04 0.06 0.08 0.1
(DBB),a (em-~ 2.5 • 10-~ 2.0 • 10-s 7.5 • 10 -s
d (cm) 0.0025 0.005 0.0025
(LAA)m (cm/sec) 1.0 x 10 -3 0.0012 4.0 • 10 -8 DISTANCE FROM BACKING PLATE (cm)
(LBB)m (cm/sec) 1.0 • 10-3 0.004 3.0 x 10 -z
Fig. 2. Profiles of KOH concentration after 10% depth of dis-
charge (I = 50 mA/cm 2 and A, B, and C for solution boundary,
* T r a n s p o r t p a r a m e t e r s f o r R A I P2291 m e m b r a n e w e r e t a k e n
f r o m t h e d a t a of S i n h a a n d B e n n i o n (50). T h e p a r a m e t e r ( L i i ) m type I membrane boundary, and type II membrane boundary,
i s d e f i n e d by (D,l)m/d ( r e f e r to Eq. [25]). respectively).

Downloaded on 2014-05-12 to IP 183.221.12.205 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
 2012 J. EZectrochem. Sac.: 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 September I980

1.o 1 9 1 I
TYPE I MEMBRANE BOUNDARY

I I I
0.8

rA
5O

~ 0,6-- ,
E
'- 40-
>-
I-
~~
~
u. 0.4
Z
LU
Q
p. 30-
z
gJ
0.2
r
2O
l,u
u.
O0
Z
o ~~176 , , ~ J} /
,r x=0 0.02 0.04 0.06 0.08
P- lO DISTANCE FROM BACKING PLATE (cm)

Fig. 4. Distribution of Zn and ZnO plotted as volume fractions

for type I membrane boundary (I ~ 50 mA/cm ~, and A, B, C, and
o] I ~ I E D represent 10%, 20%, 30%, and 40% depth of discharge, re-
x=O 0.02 0.04 0.06 0.08 0.1 spectively).

DISTANCE FROM BACKING PLATE (cm)

active zinc area (see curves B of Fig. 4). This reduced
Fig. 3. Distribution of local charge transfer current, j (mA/cm~), zinc area at the electrode face prohibits the transfer
for type I membrane boundary (I ~ 50 mA/cm 2, L = 0.1 cm, and reaction on charge a n d shifts the reaction toward the
A, B, C, and D represent 0%, 10%, 20%, and 40% depth of dis- backing plate, resulting in curve A. If sufficient a m o u n t
charge, respectively). of zinc forms and serves as n u c l e a t i o n sites for f u r -
ther zinc deposition reaction, c u r r e n t distribution
which is similar i n shape to that of discharge will re-
a n d the reaction profile becomes less u n i f o r m as shown sult (curves B and C).
in curve B. W h e n the electrode is discharged f u r t h e r I n Fig. 7, the volume fractions of zinc and zinc oxide
beyond 20% depth, the reaction at the electrode face d u r i n g two cycles are plotted as a function of the
starts decreasing due to the depleted active zinc metal distance from the b a c k i n g plate. After each complete
(curve C). After 40% depth of discharge, all the zinc cycling, the solid zinc species (Zn and ZnO) have not
n e a r the front face is used up as shown in curve D. reformed i n their original positions. This is due to the
The overpotentials rose substantially when only 40% difference in the c u r r e n t distribution d u r i n g discharge
of the initial zinc metal was utilized. The reaction pro- a n d charge. The r e d i s t r i b u t i o n of zinc and zinc oxide
file is highly n o n u n i f o r m and the effective reaction becomes less u n i f o r m as cycling continues. Numerical
zone moves step by step from the face of the electrode predictions obtained with a cell h a v i n g no m e m b r a n e
toward the backing plate. Similar trends were obtained
with the other two boundaries. 1.0 I I " I I |
The d i s t r i b u t i o n of solid zinc a n d ZnO, in terms of
volume fractions, is plotted in Fig. 4 for the type I
m e m b r a n e and in Fig. 5 for the solution boundary. The /
total a m o u n t of zinc dissolution into zincate at a spe-
cified time, i.e., the integrated area b e t w e e n the dotted
line denoted by (~zn)o and the curve ezn at time t, are
the same for both cases. However, the total a m o u n t 08v08
of ZnO precipitated, i.e., the integrated area of ZnO
profiles, is smaller for the solution case than for the
m e m b r a n e case. For example, after 40% depth of dis-
charge, the a m o u n t of precipitated ZnO obtained from
Fig. 4 and 5 are 95% and 55%, respectively, of the
total a m o u n t of the zinc consumed d u r i n g the same O 0.4
period of 141 min. The missing zinc oxide is lost into 5
the counterelectrode c o m p a r t m e n t as a soluble species,
zincate ion, before precipitation occurs.
T h e electrode initially composed of 40% liquid filled
pores, 50% zinc, and 10% ZnO by volume was cycled
n u m e r i c a l l y with a constant c u r r e n t density of 50
m A / c m 2. Each cycle consisted of 20% depth of dis- (ezra) ~ "
charge and 20% depth of charge. The c u r r e n t distribu-
tion predicted d u r i n g one cycle is presented in Fig. 6 x=0 0,02
,,[
0.04
,
0.06
11)1
0.08 0.1
for the type I m e m b r a n e case. It shows that c u r r e n t
distribution becomes more u n i f o r m on charging than DISTANCE FROM BACKING PLATE (cm}
on discharging, in particular, n e a r the b e g i n n i n g of
charge (curve A). When charge starts, the solid-solu- Fig. 5. Distribution of Zn and ZnO plotted as volume fractions
tion interfacial area near the electrode face contains for solution boundary (I ~ 50 mA/cm 2, and A, B, C, and D rep-
m a i n l y the area of ZnO precipitates and a very small resent 10%, 20%, 30%, and 40% depth of discharge, respectively).

Downloaded on 2014-05-12 to IP 183.221.12.205 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
 VoL I27, No. 9 POROUS ZINC ELECTRODE 2013

FI RST CYCLE
P DISCHARGE CHARGE
Discussion
60 Failure during discharge.--Zinc electrode behavior
I
occurring d u r i n g discharge has been predicted b y a
m a t h e m a t i c a l model. The model predicts that dis-
charge of the zinc electrode having a porosity of 0.4

i
4O
cc a n d one layer of type I m e m b r a n e could fail after only
40% utilization due to the decrease in pore size (block-
age of the first kind) as shown in Fig. 4. The p r i m a r y
effect of the decreased pore size is, as in the lead posi-
tive electrode (20), the restricted diffusion of electro-
"~ 20 lytes into the interior of the porous electrode, causing
electrolyte depletion at the reaction sites. If the
porosity falls below a certain limit, the resistance
across the pore solution rises s u b s t a n t i a l l y and serves
~ 0 as a factor in limiting f u r t h e r utilization.
z
The model predicts that the reaction distribution is
highly n o n u n i f o r m , and the effective reaction zone is
very thin (Fig. 3). The reaction distribution or the
m -20 p e n e t r a t i o n depth has been characterized b y certain
UJ
U.
dimensionless parameters (14). I n the case of u n i f o r m
z concentration and low activation polarization, two pa-
< rameters, ~'e/Ke and Q of Eq. [22], could determine the
n,,.
c shape of distribution. The reaction d i s t r i b u t i o n be-
I- - 40
comes less u n i f o r m as the p a r a m e t e r Q increases. The
ratio ~e/ge determines the shape of d i s t r i b u t i o n curves,
namely, the position h a v i n g a m a x i m u m utilization.
M a x i m u m utilization would occur at the electrode face
I I
for ~e > Ke and at the backing plate for Ke > ~e. Con-
x=0 0.05 0.1 0.05 0.1
centration polarization and the decrease of pore size
DISTANCE FROM BACKING PLATE (cm) have an effect of increasing the effective resistance of
-pore solution and thus promoting the degree of n o n -
Rg. 6. Distribution of local charge transfer current density, uniformity. This effect was illustrated i n Fig. 3 (com-
j (mA/cm2), during the first cycle for type I membrane boundary pare curves A and B). This n o n u n i f o r m reaction dis-
(I - - 50 mA/cm 2, L = 0.1 cm, and A, B, and C represent 0 % , t r i b u t i o n will accelerate the failure due to pore plug-
I 0 % , and 20% depth of discharge or charge, respectively). ging at the electrode surface. The zinc metal n e a r the
backing plate serves simply as an inert m a t r i x and
showed greater degree of redistribution of solid species does not contribute to the cell capacity.
(49). The loss of ZnO species into the counterelectrode
c o m p a r t m e n t d u r i n g discharge was v e r y large for cells
without a m e m b r a n e (see Fig. 5), while for the cell
-= FIRST CYCLE ~= with a m e m b r a n e (Fig. 4), mass transfer of zincate
DlSCHARG E CHARGE
ion into the counterelectrode c o m p a r t m e n t was r e -
0.6 stricted. However, KOH concentration was depleted
T I
significantly d u r i n g discharge of a cell having one l a y e r
0.5 of RAI P2291 cation exchange m e m b r a n e as was pre-
dicted i n Fig. 2 (curve C). With two layers of RAI
0.4 eZn P2291 membrane, only 8% utilization resulted in the
complete depletion of hydroxide ions inside the zinc
0.3 electrode c o m p a r t m e n t (54).
O
e- Discharge failure m e n t i o n e d above could be i n t e r -
N
0.2 preted by a single process, i.e., the limited mass t r a n s -
s fer of soluble species to and from the dissolving zinc
z surfaces. For the p l a n a r zinc electrode, discharge fail-
< 0.1
c
ure has been interpreted as a p h e n o m e n o n called "pas-
0 L_ L sivation" which was described by a limited diffusion
x=0 0.05 0.1 0.05 0.1 of product species, zincate ions, away from the dis-
z solving surfaces (51-53). Discharge of the porous elec-
o
trode involves more complicated and i n t e r r e l a t e d
0.6 L. SECOND CYCLE" >1
phenomena, and therefore it appears to be valuable to
<
u. divide the limiting process into several s u b - m e c h a -
0.5 nisms having more precise meaning, i.e., passivation,
pore plugging, and depletion of electrolyte. Each
-4 0.4 mechanism is defined as follows.
o>
Consider a test electrode c o m p a r t m e n t which c o n -
0.3 t a i n s solution inside the porous electrode (designated
as "pore solution"), and solution outside the pores b u t
0.2 - / within that c o m p a r t m e n t ("reservoir solution"). Solu-
tion outside the test electrode c o m p a r t m e n t on the
0.1 other side of the m e m b r a n e separator which is u s u a l l y
contained in the counterelectrode c o m p a r t m e n t is de-
noted by "external solution." Discharge of the porous
0.05 0.1 0.05 0.1 electrode m a y fail in three ways:
(i) If the reservoir solution is severely depleted of
DISTANCE FROM BACKING PLATE (cm) hydroxide ions due to the limited transfer of O H - ions
Fig. 7. Distribution of Zn and ZnO plotted as volume fractions across the m e m b r a n e , then the pore solution is also
daring two cycles for type I membrane boundary (I ---- 50 mA/cm 2, depleted of electrolyte KOH, as was predicted w i t h a
L ----- 0.1 cm, eo ~ 0.4, (eZn)o ~ 0.5, (eZnO)o ~- 0.1). cell having one layer of RAI P2291 m e m b r a n e (curve

Downloaded on 2014-05-12 to IP 183.221.12.205 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
 2014 J. Electrochem. 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
C of Fig. 2). This causes passivation at the active zinc
surfaces due to a decrease in solubility of ZnO and a
rapid increase in the rate of ZnO precipitation, in addi-
tion to increased resistance losses. This p h e n o m e n o n is
defined as the electrolyte depletion. To reduce this ef-
fect, sufficient a m o u n t of electrolytes should be pro-
vided i n the solution reservoir. Proper choice of the
m e m b r a n e , which leads to a m a x i m a l supply of O H -
ions from the eounterelectrode c o m p a r t m e n t a n d also
a m i n i m a l chance for zinc dendrite penetration, is also
important.
(it) The reservoir solution could r e t a i n the electro-
lyte concentration at a fairly constant level t h r o u g h o u t
the discharging process, provided that the reservoir
has a large volume. But the pore solution still can be
depleted of electrolyte due to the limited mass transfer
across the reaction zone located near either side of
the electrode surfaces, which has smaller pores. The
consequences will be the depletion of electrolytes at
discharging zinc surfaces, resulting in passivation.
This is defined as pore plugging and can be eliminated
by using high porosity electrodes. Discharge failure
predicted with the solution b o u n d a r y and type I m e m -
b r a n e b o u n d a r y are a t t r i b u t e d to pore plugging (see
Fig..4 and 5).
(iii) Even if the KOH concentration of the pore
solution as well as the reservoir solution remains ap-
preciably high, passivation could occur by the physical
blocking of the active zinc surface by a precipitated
ZnO film, which forms due to the depleted hydroxide
ion or due to the excess zincate at the zinc surface.
This p h e n o m e n o n is defined as passivation, having the
same m e a n i n g as was used for p l a n a r electrodes.
Passivation of this type could occur u n d e r very high
c u r r e n t load. Electrodes with high active surface area
and with u n i f o r m c u r r e n t distribution would reduce
local transfer c u r r e n t density and thus the chance for
passivation.
Failure during cyc~ing.--Zinc electrode failure occur-
ring after m a n y cycles can be referred to as a phe-
n o m e n o n called "redistribution of solid zinc species
(Zn and ZnO)." I n a b i l i t y of reforming the solid zinc
species in their original position d u r i n g cycling causes
zinc dendrite p e n e t r a t i o n and shape change. High solu-
bility of ZnO in KOH solution accentuates the redis-
t r i b u t i o n of zinc species from one part of the electrode
to the other.
Figure 5 shows that for the cell having no m e m b r a n e
only 55% of the discharge product (zincate ions) pre-
cipitates as ZnO and the r e m a i n i n g half diffuses into
the counterelectrode c o m p a r t m e n t before precipitation
occurs. On charge, once the zincate source in the zinc
electrode c o m p a r t m e n t is depleted, zinc deposits will
grow towards additional zincate which is t r a n s f e r r i n g
from the counterelectrode compartment. This type of
mass transport leads to zinc dendrite formation which
e v e n t u a l l y causes short circuits to the counterelectrode.
On the other hand, if a m e m b r a n e is used as a separa-
tor, 95% of the discharge product precipitates as ZnO
as shown in Fig. 4. Use of a m e m b r a n e restricts zincate
m o v e m e n t away from the test electrode. Charge of this
electrode is less likely to cause dendrite growth
t h r o u g h the separator because the source of zincate
ions remains in the zinc test electrode. Comparison of
these two examples shows the m a i n reason why in-
dustrial cells having appropriate m e m b r a n e s success-
fully reduce dendrite formation a n d short circuits.
These m e m b r a n e s could also p r e v e n t zinc metal d e n -
drite n u c l e a t i o n w i t h i n themselves.
Redistribution of solid zinc and zinc oxide from one
p a r t of the electrode to the other can occur through
the m o v e m e n t of zincate ions. The process involving
zincate movement, e.g., on discharging, include the
charge transfer reaction which produces zincate ions,
mass transfer of zincate, and chemical precipitation of
ZnO which consumes zincate. Therefore, c u r r e n t dis-
t r i b u t i o n which characterizes the charge transfer re-
Downloaded on 2014-05-12 to IP 183.221.12.205 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
S e p t e m b e r I980
action, degree of super- (or u n - ) saturation which
determines precipitation or dissolution of ZnO, and
mass transfer modes (diffusion, migration, and convec-
tion) will govern the redistribution of solid zinc
species.
Shape change is the redistribution process of the
solid zinc species in the direction parallel to the elec-
trode surface (y-direction). Choi et al. (12) have pro-
posed that the shape change was caused b y convective
flows d r i v e n p r i m a r i l y b y m e m b r a n e electro-osmotic
effects, while McBreen (7) has emphasized the effect
of the difference in the y - d i r e c t i o n c u r r e n t distribu-
tion d u r i n g charge and discharge. Choi et al. (13) con-
firmed e x p e r i m e n t a l l y that sealing or tight packing of
the cell, which was designed to p r e v e n t convective
flow, successfully reduced the shape change. This ob-
servation favors the convection model over McBreen's
model.
Discharge of a zinc electrode induces convective flow
toward the counterelectrode, resfilting in a decrease of
the total volume of electrolytic solution in the zinc
electrode compartment. If the electrode is vented, the
solution in the top reservoir will flow downward. The
solution picks up zincate ions along the flow path
causing greater precipitation rates in the direction of
flow. On the other hand, on charge the increase of
total volume of electrolytic solution caused by electro-
osmotic flow will push the u n s a t u r a t e d solution toward
the reservoir. The reservoir solution now becomes u n -
saturated and greater dissolution is expected n e a r the
vent or reservoir. Repeated cycling causes m o v e m e n t
of solid zinc species from near the reservoir portion of
the electrode to positions remote from the reservoir.
If the electrode is sealed, convective flow, and thus
shape change, will be limited.
Similar t r e a t m e n t can be applied to the redistribu-
tion of solid zinc in the x-direction p e r p e n d i c u l a r to
the electrode surface. The present work deals with a
sealed electrode to minimize the convective flow d r i v e n
b y a m e m b r a n e . U n d e r this condition, the convective
flow arising from the volume changes due to the overall
electrode reaction is on the order of 10 -7 cm/sec and
is considered negligible.
The reaction or c u r r e n t distribution in the x-direc-
tion during discharge is highly n o n u n i f o r m as shown
in Fig. 3. On the other hand, c u r r e n t distribution on
charging is more u n i f o r m compared to that on dis-
charging, since precipitated ZnO reduces the effective
zinc surface area near the electrode face and shifts the
reaction toward the backing plate (see Fig. 6). On
repeated cycling, this difference of anodic and cathodic
c u r r e n t distributions together with differences in the
degree of super- (or u n - ) saturation causes the redis-
t r i b u t i o n of solid zinc species and thus significant dis-
tortion of the electrode structure. The distorted struc-
ture is shown in Fig. 7. This mechanism is similar to
that described by McBreen. Similar structure was also
observed e x p e r i m e n t a l l y by S u n u and B e n n i o n (54).
If convective flow due to m e m b r a n e p u m p i n g is al-
lowed, more serious redistribution is expected. Simi-
larly, allowing free m o v e m e n t of zincate ion into the
counterelectrode, by e l i m i n a t i n g the membrane,
showed a greater degree of redistribution (49). This
m o v e m e n t of solid zinc species in the x-direction could
contribute to the loss in the cell capacity on cycling
service.
Other factors such as effects of gas generation and
changes in morphologies and the active surface area
with cycling were excluded from this work. The re-
sults of this work can be applied to the design of zinc
electrodes to improve their utilization and cycle life.
The results also point out areas where f u r t h e r research
should be emphasized in order to gain f u r t h e r per-
formance improvement.
Acknowledgments
The authors acknowledge the support of this work
provided by the U.S. Air Force Systems C o m m a n d
 Vol. I27, No. 9 POROUS ZINC ELECTRODE 2015

u n d e r Contract No. F 44620-76-C-0098 and the U n i - diffusion coefficients of K O H and K2Zn(OH)4, respec-
v e r s i t y of California, Los Angeles. tively.
Th e area am and as r e p r e s e n t the interracial areas
M a n u s c r i p t s u b m i t t e d Nov. 26, 1979; r e v is e d m a n u - w h i ch are active for electrochemical reaction [A] and
script r e c e i v e d Feb. 15, 1980. for chemical reaction [B], respectively. T h e y w e r e
a p p r o x i m a t e d as follows. It is assumed that the m a c r o -
A n y discussion of this p a p e r will appear in a Dis- scopic a v e r a g e d particles w i t h u n i f o r m radius a r e
cussion Section to be published in the J u n e 1981 a r r a n g e d in face centered cubic closed packed posi-
JOURNAL. All discussions for the J u n e 1981 Discussion tions. For a g i v en r e f e r e n c e porosity eo and radius Ro,
Section should be submitted by Feb. 1, 1981. the solid-solution i n t er f ace area ao p er unit v o l u m e
Publication costs of this article were assisted by of the electrode can be estimated f r o m the relation
the U.S. Government. of ao ---- 3(1 -- ,o)/Ro. The specific surface area of the
electrode at any state h a v i n g porosity of e can be
r el at ed to the r e f e r e n c e area ao as a/ao ---- (1 -- , ) R o /
APPENDIX A [1 -- ~o)R]. Since the ratio R/Ro is eq u al to (a/ao) ~
Parameters Used in the Numerical Calculations 3 the. specific area a can be r e p r e s e n t e d as
ao -- 50 cm2/cm 3 a__ao( 1 - - e ) 2/3
C3o -- 0.008 m o l e s / c m a
C2o -- 0.000~6 m o m s / c m a 1 -- e0

DAA -- 5.86 X 10 -6 cm2/sec In the absence of the i n e r t conducting material, the

DBB -- see ~ area am and as become azn (zinc area) and azno (ZnO
DAB -- DBA ---- 0.0 area), respectively. T h e y are a p p r o x i m a t e d by the
iO~ -- 0.06 A / c m 2 following e q u a t i o n
kAo -- 0~001 c m / s e c
kBo -- 0.003 c m / s e c az~(or am) = a -- az=o(or as)
kXTL -- 0.005 cm/sec (~Zn - - ~Zn*) p
L -- 0.1em --a
81 - - 81. --- 0.0 (eZn - - eZn*) p -~ (eZnO) q
82 -" - - 8 2 . --" - - 1 . 0
sa : --2s~. = 4.0 w h e r e p and q are the constants r e l a t i n g v o l u m e
to surface area (p ---- q = 2/3 was assumed for cubical
So -- 0.0 or spherical crystals), and ezn* represents the v o l u m e
So* -- -- 1.0 fractions of nonactive zinc w h i ch can be caused by
t =t* : 0.5 pore plugging (blockage of the first kind) and by
ti 0.23
--
complete coverage on zinc surface b y ZnO (usually
ts -- 0.72 at 10M K O H
called passivation or blockage of the second k i n d ) .
VA -- 67.0 cm~/mole The ezn* is a p p r o x i m a t e d by
VB - - 17.8 cm3/mole
Vo -- 18.07 c m 3 / m o l e eZn* --" eZnmlug "~ ~,(eZn,max - - eZnmlug)
Vzn -- 9.15 c m a / m o l e The m e a n i n g of the various v o l u m e fractions is e x -
Vzao -- 14.51 cm3/mole plained by using the following example.
V -- 0.0 cm 3 (definition in Eq. [24]) Let us consider a local section of the electrode h a v -
Vm -- 0.0 c m / s e c ing porosity of 0.3, 60% Zn, and 10% ZnO b.y volume.
aa -" 1.5 The p ar t i al m o l a r volumes of zinc and zlnc oxide
ac = 0.5 are 9.15 and 14.51 cruZ/mole, respectively. Due to the
7 -- 0.75 difference in the partial m o l a r volume, 85.3% con-
~' = 0.0 version of Zn into ZnO results in pore plugging, i.e.,
'o = 0.4 e = 0, eZn = 0 . 0 8 8 , and ezno : 0.912. The r e m a i n i n g
('Zn)o = 0.5 Zn cannot be c o n v e r t e d into ZnO and is denoted by
('ZnO)o = 0.1 eZn.,lu~ ( : 0 . 0 8 8 ) . On the other hand, if all ZnO is
(,I)o = 0.0 c o n v e r t e d into Zn d u r i n g a local deep charge, an
K -" see 3 electrode h a v i n g ~zn : 0.663, ezno : 0, and ~ : 0.337
l ---- 0.0 will result. This zinc content is the m a x i m a l a m o u n t
aZn -- 2 X 1 0 5 m h O / c m of zinc available in the fully ch ar g ed state and denoted
~zno ----- 0.01 m h o / c m by eZn,max (=0.663). Then the quantity, eZn.max
~I _-- 100.0 m h o / c m eZn.,Iuz : 0.575, can be i n t e r p r e t e d by the m a x i m a l
a m o u n t of active zinc which can be utilized. The f r a c -
APPENDIX B tional constant P, is defined based on this q u a n t i t y to
describe the nonactive zinc caused b y passivation.
Mass Transfer Coetficients (kA, km ks*) and Active 5urtace
Areas (a, am, as) L I S T OF S Y M B O L S
The mass t r a n s f e r coefficients kA, kB, and ks* d e- a specific surface area per unit v o l u m e of t he
fined in Eq. [8], [9], and [11] are a p p r o x i m a t e d by electrode, cm2/cm 8
the following equations [see Ref. (49) for derivation] am, as specific active surface area for charge t r a n s f e r
reaction [A] and that for precipitation or
Dii a -- am dissolution of ZnO, c m e / c m 3
aki: ; i:A,B
ci co n cen t r at i o n of species i, m o l e / c m 3
~ ln(#) Cio initial concentration of species i, m o l e / c m 3
Cis concentration of species i at the active m e t a l
surface, m o l e / c m 3
1 1 1 Dij diffusion coefficients w i t h respect to v o l u m e
a v e r a g e velocity, cm2/sec
aks, / DAA "~ ( a - a s) askxTL (DiDo diffusion coefficients w i t h respect to s ol ve nt
velocity, cm2/sec
F F a r a d a y ' s constant, 96,487 C / e q u i v .
xas / I superficial applied c u r r e n t density, A / c m 2
il superficial c u r r e n t density in the m a t r i x phase,
w h e r e 5 is the characteristic diffusion length b e t w e e n A/cm2
t h e active m e t a l surface and the bulk within the i2 superficial c u r r e n t density in the solution
pores, kXTL is the chemical rate constant for p r e c i p i t a - phase, A / c m 2
tion or dissolution of ZnO, and DAA and DBB are the ioo e x c h a n g e c u r r e n t density, A / c m 2
T h e c o n d u c t i v i t y of e l e c t r o l y t i c solution, k, (55), s o l u b i l i t y of j local t r a n s f e r cu r r en t density p er unit area
Z n O in K O H s o l u t i o n (56), a c t i v i t y c o e f f i c i e n t s of K O H a n d p o t a s - of active zinc surface, A / c m 2
s i u m z i n c a t e (57, 58), a n d d i f f u s i o n coefficients o f p o t a s s i u m hy- ki mass t r a n s f e r coefficient of species i f r o m
d r o x i d e , DB~, (59) w e r e e x p r e s s e d as a f u n c t i o n of c o n c e n t r a t i o n active sites to b u l k in the pores or vice versa,
b a s e d on t h e v a r m u s r e p o r t e d data [ s e e Ref. (49) f o r t h o s e e q u a -
t i o n s and r e f e r e n e e s ] . cm/sec

Downloaded on 2014-05-12 to IP 183.221.12.205 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
 2016 J. E~ectrochem. Soc.: ELECTROCHEMICAL SCIENCE AND TECHNOLOGY
ks. rate constant combining mass transfer of
zincate, kA, with the rate constant for pre-
cipitation or dissolution of ZnO, cm/sec
L electrode thickness, cm
Nl flux of species i in the x-direction, mole/cm~-
see
RT gas constant multiplied by absolute tempera-
ture, J/mole
Rl production or consumption of species i in
Eq. [11], mole/cm3-sec
Re defined in Eq. [21] as amio~ -}- ~c)F/RT
si, si. stoichiometric numbers of species i defined
by Eq. [6]
t, t* tortuosity factor
ti, (ti)o transference number of species i with respect
to volume average velocity and that with
respect to solvent velocity
"~i partial molar volume of species i, cmS/mole
v superficial volume average velocity, cm/sec
x distance from the backing plate, cm
zi charge number of species i
Greek Symbols
aa an anodic kinetic parameter
ac a cathodic kinetic parameter
exponent in zincate concentration dependence
of the exchange current density
9 porosity of the electrode
ei volume fraction of solid species i
f exponent in O H - concentration dependence of
the exchange current density
conductivity of solution, mho/cm
?~ik number of ionic species i per molecule of
electrolyte "k"
~l chemical potential of ionic species i, J/mole
~l conductivity of solid species i, mho/cm
~1 potential in the matrix phase, V
~2 potential in the solution phase, V
Subscripts
i any arbitrary species i; 1 for potassium ion,
2 for zincate ion, 3 for hydroxide ion, A for
potassium zincate, and B for potassium hy-
droxide
o solvent or initial values or values referred
to the solvent velocity
REFERENCES
1. H. G. Oswin and K. F. Blurton, in "Zinc-Silver Ox-
ide Batteries," A. Fleischer and J. J. Lander,
Editors, pp. 63-85, John Wiley & Sons, Inc., New
York (1971).
2. J. O'M. Bockris and G. A. Razumney, "Fundamental
Aspects of Electrocrystallization," Chap. 6,
Plenum Press, New York (1967).
3. R. D. Naybour, Electrochim. Acta, 13, 763 (1968).
4. J. E. Oxley and C. W. Fleischmann, First Quarterly
Report, contract NAS5-9591, N66-13568, 21 pp.
(September 1965).
5. S. Arouete, K. F. Blurton, and H. G. Oswin, This
Journal, 116, 166 (1969).
6. H. K. Farmery and W. A. Smith, in "Batteries,"
D. H. Collins, Editor, p. 179, Pergamon Press, Inc.,
New York (1963).
7. J. McBreen, This Journal, 119, 1620 (1972).
8. J. J. Lander, in "Zinc-Silver Oxide Batteries," A.
Fleischer and J. J. Lander, Editors, pp. 457-469,
John Wiley & Sons, Inc., New York (1971).
9. G. A. Dalin, in "Zinc-Silver Oxide Batteries," A.
Fleischer and J. J. Lander, Editors, pp. 87-95,
John Wiley & Sons, Inc., New York (1971).
10. D. P. Boden, V. J. Spera, and R. B. Wiley, Paper
13, presented at The Electrochemical Society
Meeting, Detroit, Michigan, October 5-9, 1969.
11. J. McBreen and G. A. Dalin, Paper 45 presented at
The Electrochemical Society Meeting, Philadel-
phia, Pennsylvania, Oct. 9-14, 1966.
12. K. W. Choi, D. N. Bennion, and J. Newman, This
Journal, 123, 1616 (1976).
13. K. W. Choi, D. Hamby. D. N. Bennion, and J.
Newman, ibid., 123, 1628 (1976).
14. J. Newman and W. Tiedemann, Am. Inst. Chem.
Eng. J., 21, 25 (1975).
15. A. Winsel, Z. Elektrochem., 66, 287 (1962).
16. J. Newman and C. W. Tobias, This Journal, 109,
Downloaded on 2014-05-12 to IP 183.221.12.205 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
September 1980
1183 (1962).
17. R. C. Alkire, E. A. Grens II, and C. W. Tobias,
ibid., 116, 1328 (1969).
18. J. S. Dunning, D. N. Bennion, and J. Newman, ibid.,
120, 906 (1973).
19. H. Gu, D. N. Bennion, and J. Newman, ibid., 123,
1364 (1976).
20. D. Simonsson, ibid., 120, 151 (1973).
21. D. Simonsson, J. Appl. Electrochem., 3, 261 (1973).
22. D. Gidaspow and B. S. Baker, This Journal, 120,
1005 (1973).
23. T. P. Dirkse, ibid., 102, 497 (1955).
24. W. G. Sunu, D. N. Bennion, and J. Newman, To
be published. Also see Ref. (49).
25. T. P. Dirkse, in "Zinc-Silver Oxide Batteries," A.
Fleischer and J. J. Lander, Editors, pp. 19-28,
John Wiley & Sons, Inc., New York (1971).
26. T. P. Dirkse, L. A. Vander Lugt, and N. A. Hamp-
son, This Journal, 118, 1606 (1971).
27. D. D. Justice and R. M. Hurd, ibid., 118, 1417 (1971).
28. H. Gerischer, Z. Phys. Chem., 202, 302 (1953).
29. J. P. G. Farr and N. A. Hampson, J. ElectroanaL
Chem. Interracial Electrochem., 18, 407 (1968).
30. D. A. Payne and A. J. Bard, This Journal, 119,
1665 (1972).
31. J. P. G. Farr and N. A. Hampson, J. Electroanal.
Chem. Interracial Electrochem., 13, 433 (1967).
32. J. P. G. Farr and N. A. Hampson, Trans. Faraday
Soc., 62, 3493 (1966).
33. R. D. Armstrong and G. M. Bullman, J. Electroanal.
Chem. Interracial Electrochem., 25, 121 (1970).
34. J. O'M. Bockris, Z. Nagy, and A. Damjanovic, This
Journal, 119, 285 (1972).
35. J. N. Butler, "Ionic Equilibrium--A Mathematical
Approach," p. 285, Addison-Wesley Publ. Co.
Inc., Reading, Mass. (1964).
36. D. P. Boden, R. B. Wylie, and V. J. Spera, This
Journal, 118, 1298 (1971).
37. T. P. Dirkse, C. Postmus, Jr., and R. Vandenbosch,
J. Am. Chem. Soc., 76, 6022 (1954).
38. A. O. Gubeli and J. Ste-Marie, Can. J. Chem., 45,
827 (1967).
39. W. Van Doorne and T. P. Dirkse, This Journal,
112, 1 (1975).
40. J. S. Dunning, P h . D . Dissertation, University of
California, Los Angeles (1971).
41. R. K. Schofield and C. Dakshinamurti, Discuss.
Faraday Soc., 3, 56 (1948).
42. R. E. Meredith and C. W. Tobias, Adv. Electrochem.
Electrochem. Eng., 2, 15 (1962).
43. E. G. Gagnon, This Journal, 120, 1052 (1973).
44. O. S. Ksenzhek, E. A. Kalinovskii, and E. L. Baskin,
Zh. Prik. Khim., 37, 1045 (1964).
45. I. L. Romanova and I. A. Selitsky, Elektrokhimiya,
6, 1776 (1970).
46. T. P. Dirkse and N. A. Hampson, Electrochim. Acta,
17, 383 (1972).
47. J. Newman, Ind. Eng. Chem., Fundam., 7, 514
(1968).
48. J. Crank and P. Nicolson, Camb. Phil. Soc. Proc.,
43, 50 (1947).
49. W. G. Sunu, Ph.D. Dissertation, University of Cal-
ifornia, Los Angeles (1978).
50. M. Sinha and D. N. Bennion, This Journal, 125,
556 (1978).
51. N. A. Hampson and M. J. Tarbox, ibid., llO, 95
(1963).
52. M. Eisenberg, H. F. Bauman, and D. M. Brettner,
ibid., 108, 909 (1961).
53. N. A. Hampson, P. E. Shaw, and R. Taylor, Br.
Corr. J., 4, 207 (1969).
54. W. G. Sunu and D. N. Bennion, This Journal, 127,
2017 (1980).
55. D. N. Bennion, Ph.D. Dissertation, University of
California, Berkeley, Table A (1964).
56. W. F. Linke, "Solubilities of Inorganic and Metal
Organic Compound," Vol. II, 4th ed., pp. 1672-
1676, Amer. Chem. Soc., Washington, D.C. (1965).
57. R. A. Robinson and R. H. Stokes, "Electrolytic
Solutions," 2nd ed., p. 501, Butterworths, London
(1959).
58. J. Newman. "Electrochemical Systems," pp. 91-95,
Prentice-Hall Inc., Englewood Cliffs, N.J. (1973).
59. J. Newman, D. N. Bennion, and C. W. Tobias, Bet.
Bunsenges., 69, 608 (1965).