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ARTICLE IN PRESS+ModelOWER 8852 1–12

Journal of Power Sources xxx (2007) xxx–xxx

A model for the silver–zinc battery during high rates of discharge

Murali Venkatraman, J.W. Van Zee ∗Department of Chemical Engineering, University of South Carolina, Columbia, SC 29208, United States

Received 3 October 2006; received in revised form 13 December 2006; accepted 14 December 2006

bstract

A transient one-dimensional mathematical model is developed and used to study the performance and thermal behavior of the silver–zinc celluring discharge. The model considers the negative (zinc) electrode, separator, and positive (silver) electrode and describes the simultaneouslectrochemical reactions in the positive electrode, mass transfer limitations, and heat generation. Changes in porosity and electrolyte compositionue to electrochemical reactions, local reaction rates, diffusion, and migration of electrolyte are reported. Emphasis is placed on understanding theovement of the reaction front in the negative electrode during discharge and its correlation to the useful capacity of the cell. The sensitivity of

D P

his capacity to changes in the values of initial electrolyte, exchange current densities, and tortuosity are presented. It is shown that under certainonditions, in a system employing 25% KOH as the electrolyte, the useful capacity of the cell could be limited to 55.6% of its rated capacity whenhe discharge rate is increased from 1C to 2C. The temperature rise in a single cell was predicted and observed to agree with the experimentalalues.

2007 Published by Elsevier B.V.

trode

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eywords: Silver–zinc battery; Model; Constant current discharge; Porous elec

. Introduction

Even though the silver–zinc battery has a high cost, it is one ofhe more important secondary batteries available today becausef its high discharge rate capability and because of its largepecific energy density on both a mass and a volumetric basis1]. As discussed below, the shape change effects have limitedhe robustness of this rechargeable system. The most impor-ant characteristic of this battery is that initially the impedances very low but it can vary considerably with factors such asischarge current density, state-of-discharge, operational tem-erature, active material composition, cell ageing, and cell size2]. It is rechargeable with little overcharge but it has low cycleife primarily resulting from zinc-electrode shape change. Thealendar life is also short due to the degradation of the separatorn alkaline conditions, but new separator materials have beeneveloped to offer stability [3]. A physical description of the

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ilver–zinc battery, with design specifications and calculations,as been provided by Himy [4]. A wealth of experimental infor-ation is available on the behavior of silver–zinc cells [5–10],

∗ Corresponding author. Tel.: +1 803 777 7555; fax: +1 803 777 8142.E-mail address: vanzee@engr.sc.edu (J.W. Van Zee).

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378-7753/$ – see front matter © 2007 Published by Elsevier B.V.oi:10.1016/j.jpowsour.2006.12.064

s; Multiple electrode reactions

ut models that describe these cells are scarce in literature andave been focused on only part of the cell as discussed later. Asfirst step towards understanding the behavior of a rechargeableg–Zn battery during cycles, we present here a time-dependentne-dimensional model to explain the distribution of reactantsnd the thermal behavior of a silver–zinc cell during high ratesf discharge. This discharge behavior at high rates establishes aasis for future analyses of the recharge behavior which requiresnitial conditions corresponding to the end of discharge con-entration and temperature profiles, and which is performed atuch slower rates due to chemical complexities of the sys-

em (including zinc-electrode shape change mechanisms) notmportant during discharge.

The first reproducible and stable silver-silver oxide electrodeas prepared by Hamer and Craig [11,12]. Dirkse [13] has

xtensively reviewed the electrochemistry of the silver electrode.ales and Burbank [14,15] conducted galvanostatic and poten-

iostatic studies along with X-ray diffraction. They concludedrom their X-ray diffraction patterns that the major compo-ents of a silver electrode are Ag, AgO, and Ag2O. No higher

r Sources (2007), doi:10.1016/j.jpowsour.2006.12.064

xide could be observed. Dirkse [16] showed that the OCVs of 59

ilver–zinc cells in the neighborhood of 1.66 V correspond to 60

he presence of Ag/Ag2O/OH− system in the silver electrode, 61

nd those near 1.93 V correspond to AgO/Ag2O/OH− system. 62

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ARTICLE IN+ModelPOWER 8852 1–12

2 M. Venkatraman, J.W. Van Zee / Journal o

Nomenclature

aAg specific surface area of silver electrodeaZn specific surface area of zinc electrodecp,i specific heat capacity of species i (J K−1 kg−1)C concentration of OH− ions (kmol m−3)Cref reference concentration of OH− ions (kmol m−3)C0 initial concentration of OH− ions (kmol m−3)D diffusivity of KOH (m2 s−1)Di diffusivity of species i (m2 s−1)F Faraday’s constant (96,487 C)inj transfer current of the jth reaction the silver elec-

trode (A m−2)i1 matrix current density (A m−2)i2 solution current density (A m−2)i0j equilibrium exchange current density for jth reac-

tion (A m−2)ki thermal conductivity of species i (W m−1 K−1)mi mass fraction of species i on an electrolyte free

basisMi molar density of species i (kmol m−3)Mw

i molecular weight of species i (kg kmol−1)nj number of electrons transferred in reaction jNi flux of species i (mol m−2 s−1)Q total heat source term in energy equation

(J m−3 s−1)Qkin kinetic heat source term in energy equation

(J m−3 s−1)Qohm joule heating term in energy equation (J m−3 s−1)R universal gas constant, 8.314 (J mol−1 K−1)Sa,i stoichiometric coefficient of species ‘a’ in ith

reactiont time (s)T temperature (K)T0 initial temperature (K)Uθ

j equilibrium potential of jth electrochemical reac-tion (V)

VAg volume of silver electrodeVZn volume of zinc electrodewi mass fraction of species i (electrolyte included)Zi charge of species i

Greek lettersαai anodic transfer coefficient for reaction iαci cathodic transfer coefficient for reaction iεr porosity of region rηj overpotential for jth reaction (V)θ1 initial mass ratio of zinc to silver in the cellθ2 initial mass ratio of silver in Ag2O to silver in

AgOκr conductivity of region r (mho m−1)ρi density of species i (kg m−3)σi electrical conductivity of the species i (mho m−1)φ1 matrix potential (V)φ2 solution potential (V)� differential operator

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PRESSf Power Sources xxx (2007) xxx–xxx

ntermediate potentials are mixed potentials due to the presencef all the three. Gagnon and Austin [17] have examined theischarge mechanism of a porous silver-oxide electrode at lowemperature in a KOH electrolyte.

The zinc electrode is one of the most researched electrodesn the literature since it forms the anode for many battery sys-ems, such as the Ag–Zn, Zn–Br2, Zn–MnO2 (i.e., alkaline zinc)nd the zinc-air and a comprehensive listing of the relevant lit-rature has been provided by McLarnon and Cairns [18]. Mostf the literature on zinc electrodes focuses on the shape changeffects, and this is relevant for the Ag–Zn battery since, asiderom initial material costs, the shape changes are the major dif-culty in recharging this battery and therefore limit its cycle

ife, ubiquitous use, and cost/cycle. Choi et al. [19,20] weremong the first to analyze the shape change effect that is asso-iated with zinc electrode. Shape change, the redistribution ofctive material over the zinc electrode surface as a result ofell cycling, was hypothesized to be caused by convective flowsriven primarily by membrane pumping. They proposed a modelnd showed that shape change can be eliminated if the con-ective flow in the zinc electrode compartment parallel to thelectrode surface is stopped. Hamby and Wirkkala [21] also havehown deformation of zinc electrode during oxidation. Theoret-cal [22] and experimental [23] work on transient and failurenalyses was done by Sunu and Bennion, who reported that theepletion of electrolyte was the major cause of incomplete dis-harge in zinc electrode. Skelton and Serenyi [24] have discussedhe use of BiO2 as an additive to the zinc electrode to preventhe deleterious effects of shape change which lead to loss ofctive material during cycling. Cheh’s group has also treated then anode as part of their nine papers on the alkaline-zinc cell

25].The model presented in this paper is based on porous elec-

rode theory [26,27] follows the isothermal single cell model oflanton et al. [28], is based on the literature for the predictionf the thermal behavior of batteries [29–35] and it features aypical silver–zinc cell whose specifications are based in Ref.4] and on the advice of Moden [36]. The results are consistentith Moden’s extensive experience with these batteries and his

ransient lumped-parameter spreadsheet model which captureshanges in the cell voltage and cell temperature rise that areonsistent with his experiments.

. Model

The schematic of a silver–zinc cell is given in Fig. 1. It fea-ures a cathode made of silver–silver(I) oxide–silver(II) oxideAg–Ag2O–AgO) supported by a silver grid. The silver griderves as a current collector and it is non-reactive, typically. Theeparator material used is a combination of nylon, cellophanend FRSC, with a wrap of each material one above the otherorming a three-layer structure. For modeling purposes, the sep-rator is considered a single entity with average properties. The

r Sources (2007), doi:10.1016/j.jpowsour.2006.12.064

node is made of zinc–zinc oxide (Zn–ZnO). The anode, sepa- 114

ator and cathode are porous. Himy [4] provides a description of 115

he preparation of the two electrodes observing that it is difficult 116

o achieve reproducibility in case of zinc electrode preparation. 117

D

ARTICLE IN+ModelPOWER 8852 1–12

M. Venkatraman, J.W. Van Zee / Journal o

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ig. 1. Schematic representation of a silver–zinc cell. All the regions except theurrent collectors are porous and filled with KOH solution as the electrolyte.or the results presented here lAg = 0.1067 cm, lsep = 0.05 cm, and lZn = 0.4 cm.

n discharge, the following reactions are assumed to occur athe cathode:

g2O + H2O + 2e− = 2Ag + 2OH−, Uθ1 = 0.604 V (1)

AgO + H2O + 2e− = Ag2O + 2OH−, Uθ1 = 0.604 V (2)

nd at the anode:

n + 2OH− = ZnO + H2O + 2e−, Uθ3 = −1.305 V (3)

he zinc electrode operates according to aissolution–precipitation reaction mechanism. The reactionechanism is as follows:

n + 4OH− � Zn(OH)42− + 2e− (4)

n(OH)42− � ZnO + 2OH− + H2O, Keq = 2.32 × 10−2

(5)

lthough the model presented here is concerned with dischargeimitations during a single cycle and thus shape change effectsue to ZnO precipitation are not considered, a brief discussionill yield a useful perspective. During discharge, zinc is oxi-ized to soluble zincate Zn(OH)4

2−, which is precipitated asnO when the solubility limit of zinc oxide is exceeded. Prob-

ems associated with these solid particles of ZnO are manifoldecause they affect not only the shape of the electrode (in thelane perpendicular to that shown in Fig. 1), but also the ther-al and electrical conductivities adversely. Their high specific

ravity causes an uneven distribution of precipitated ZnO andesults in non-uniform current distribution which affects the abil-ty to charge the cell uniformly. Also, during discharge, the

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oncentration of OH−, decreases in the anode and increasesn the cathode and limits the discharge capacity and the sol-bility of Zn. For this discharge model we consider that theolution is saturated with Zn(OH)4

2− at a concentration which

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PRESSf Power Sources xxx (2007) xxx–xxx 3

s much lower than the alkali concentration and thus use reac-ion (3) rather than reactions (4) and (5). However, we do assumehat ZnO precipitation alters the porosity, thermal and electricalonductivities.

In a silver–zinc cell, the conductivities of the materialsnvolved are very high and thus to a first approximation, a sand-ich or one-dimensional model on the thickness is adequate.hen we use Newman’s macro-homogenous model of porouslectrodes along with the constitutive laws of a binary diluteolution [37], to predict the profiles of various variables. Theomplete set of equations can be found in [38] and those tablesave been omitted for brevity here. As an overview, a materialalance for species i in the solution phase is given by:

∂(εCi)

∂t= ajin − ∇ · Ni (6)

here Ni is the flux of species i in the pore solution averaged overhe cross sectional area of the electrode and ajin represents theransfer rate of species i from the solid phases to the pore solutioner unit electrode volume. The electrolyte is highly concentratedn K+ and OH−, relative to the zincate ion and hence the zincateon’s contribution is neglected and the solution is treated as ainary electrolyte of K+ and OH−. This is also consistent withhe assumption of using only reaction (3) at the anode. Anyonvection inside the cell is considered negligible due mainlyo the tight packing and hence only the diffusion and migrationuxes contribute to the movement of species in the cell. Hence,

he respective flux equations are:

K+ = − ε

τ

(DK+∇CK+ − DK+FzK+CK+

RT∇φ2

)(7)

OH− = − ε

τ

(DOH−∇COH− − DOH−FzOH−COH−

RT∇φ2

)(8)

he binary electrolyte approximation along with electro-eutrality yields:

K+ = COH− = C (9)

his leads to a single concentration equation devoid of the poten-ial term:

∂(εC)

∂t= −∇ ·

(− ε

τD∇C

)+(

D

2DOH−

)ajin (10)

here

= 2DK+DOH−

DK+ + DOH−(11)

Note that, we have used the dilute binary electrolyte theory37] in the formulation of the above equations. These equationsre consistent with those formulated from concentrated solutionheory [27] equations because in the Ag–Zn system the partial

r Sources (2007), doi:10.1016/j.jpowsour.2006.12.064

olar volume of the electrolyte and the transference number of 190

he cation (K+) do not change with concentration. These approx- 191

mations are consistent with the parameters and concentrated 192

olution model of Chen and Cheh [25]. Also, D was found to be 193

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ARTICLE IN+ModelPOWER 8852 1–12

4 M. Venkatraman, J.W. Van Zee / Journal o

Table 1Transport and electrode parameters (references in braces)

Parameter Value Source

aAg 50 m−1 AssumedaZn 50 m−1 [42]DOH− 5.26 × 10−9 (m2 s−1) [37] (p. 55)DK+ 1.96 × 10−9 (m2 s−1) [37] (p. 55)n1 2 Reaction (1)n2 2 Reaction (2)n3 2 Reaction (3)sOH−,1 2 Reaction (1)sOH−,2 2 Reaction (2)sOH−,3 2 Reaction (3)sAg,1 2 Reaction (1)sAgO,2 −2 Reaction (2)sAg2O,1 −1 Reaction (1)sAg2O,2 1 Reaction (2)sZn,3 2 Reaction (3)VAg 7.3 × 10−6 m3 [36]VZn 27.5 × 10−6 m3 [36]zK+ 1 –zOH− −1 –αa1 0.65 Assumedαc1 0.35 Assumedαa2 0.75 Assumedαc2 0.25 Assumedαa3 0.5 [42]αc3 0.5 [42]ε0

Ag 0.322 [36]εsep 0.5 [36]ε0

Zn 0.731 [36]θ1 0.866 [36]θ

ξ

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2 0.333 [36]1.5 [29]

constant for the range of concentrations employed in this studysee Table 1) and therefore the spatial variation of transferenceumber of the solvent is also 0 [27].

In case of solid species, the mass balance does not involve aux term. Thus, Eq. (6) simplifies as:

∂Mk

∂t= ajin (12)

here Mk is the molar density of the solid species k. In case ofilver–zinc cell, the products and reactants are solids. Hence,n overall mass balance on the solid phases in each individuallectrode is applicable:

athode : 2MAg2O + MAgO + MAg = MtotAg (13)

node : MZnO + MZn = MtotZn (14)

inj = i0j,ref

(∏i

(Ci

Ci,ref

)pi∏k

(

( ) (

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Please cite this article in press as: M. Venkatraman, J.W. Van Zee, J. Powe

n addition, the superficial current density in the pore solutions due to the movement of the ions:

−∏

i

Ci

Ci,ref

qi ∏k

Mk

Mk,ref

Ft

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PRESSf Power Sources xxx (2007) xxx–xxx

2 = F∑

ziNi = −κ∇φ2 − εF (DK+ − DOH− )∇C (15)

here

= εF2

RT

∑z2i DiCi = εF2

RT(DK+DOH− )C (16)

he second term in the RHS is the diffusion potential termhich would vanish for DK+ = DOH− . However, our modelses different values for DK+ and DOH− . The charge conserva-ion equation for the matrix and solution phases would requirehe divergence of the total current to be 0:

· i1 + ∇ · i2 = 0 (17)

or j simultaneous reactions of the form:

i

sijXzii → nje− (18)

araday’s law can be expressed as:

jin = −∑

j

sij

njFainj (19)

he transfer current per unit electrode volume �·i2 is related tohe individual average transfer current densities by:

· i2 =∑

j

ainj (20)

he movement of electrons in the matrix phase is governed byhm’s law:

1 = −σavg∇Φ1 (21)

here σavg is the effective electrical conductivity of the matrixnd φ1 is the potential in the matrix. The effective electricalonductivity of the matrix is obtained by considering parallelonduction paths and is given as:

avg =∑

σkmξk (22)

here mk is the mass fraction (defined over solid phase only) ofhe solid species k and ξ being an empirical constant. A valuef 1.5 was taken for ξ, as has been conventional in the literature29].

Polarization equations are needed to express the dependencef the local rate of each reaction on the various concentrationsnd on the potential difference driving force at the reaction inter-ace. In case of silver–zinc cells, since all the products andeactants except OH− are solids, appropriate capacity correc-ion factors must be used in the Butler–Volmer expressions sohat the polarization equations take the form:

k

,ref

)pk

exp

(αajnjF

RT(ϕ1 − ϕ2 − Uj,ref)

)

)qk(−αcjnjF

))

r Sources (2007), doi:10.1016/j.jpowsour.2006.12.064

expRT

(ϕ1 − ϕ2 − Uj,ref) (23) 243

or the silver and zinc electrodes the capacity correction fac- 244

ors Mk/Mk,ref are obtained by normalizing the molar densities 245

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M. Venkatraman, J.W. Van Zee / Journal of Power Sources xxx (2007) xxx–xxx 5

Table 2Densities and thermal parameters (references in braces)

Material Parameter

cp (J K−1 kg−1) σ (mho m−1) k (W m−1 K−1) M0 (kmol m−3)

Ag 234 [43] 6.28 × 107 [13] 430 [43] 0.0 [36]AgO 343 [36] 8.33 × 104 [13] 20.7 [43] 3.0 [36]Ag2O 343 [36] 10−6 [13] 20.7 [43] 0.5 [36]Electrolyte (KOH) 2520 [36] – 2.0 [4] See Table 3, for value of C0

Cellophane separator 1340 [36] 0 (assumed) 0.24 [43] –Zn 389 [36] 1.83 × 107 [42] 120 [43] 1.5 [36]Z 20.7 [43] 0.0 [36]

o246

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T252

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I254

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(256

k257

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Q264

265

t266

T267

d268

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s270

f271

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a275

Table 3Perturbed parameters (references for base case values in braces)

Parameter Figurenumber

Curvenumber

Value

T0 All All 298 K

C0 2, 12 1, 4 45% KOH2, 12 2, 5 35% KOH2, 12 3, 6 25% KOH [36]3, 5–11, 13 All 25% KOH [36]4 All 45% KOH

τAg = τsep = τZn 4 1, 4 1.04 2, 5 2.04 3, 6 3.02, 3, 5–13 All 1.0

i01 1–9, 11, 12 All 2 × 10−3 A cm−2

10, 13 1, 4 2 × 10−3 A cm−2

10, 13 2, 5 2 × 10−4 A cm−2

10, 13 3, 6 2 × 10−5 A cm−2

i03 1–9, 11, 12 All 1.75 × 10−3 A cm−2 [18]

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nO 2910 [36] 1.0 [42]

f solid species against the total silver and zinc content of thelectrodes, respectively. Similar expressions for silver electrodeave been reported in literature [28].

The porosity equation is obtained calculating the volumehange in the electrode as the discharge progresses:

∂ε

∂t=⎛⎝ ∑

solid phases k

skMwk

ρknF∇ · i2

⎞⎠ (24)

he energy equation may be written as:

ρcp)avg∂T

∂t= −∇ · (kavg · ∇T ) + Q (25)

n the above equation, ρ, cp and kavg are instantaneous valuesveraged on the composite material:

ρcp)avg = cp,lρlε + (1 − ε)∑

cp,sρsMws Ms (26)

avg =∑

all solids

ks[(1 − ε)ws]ξ +

∑all liquids

kl[εwl]ξ (27)

here s denotes the solid phase and l denotes the electrolyte.he source term Q, comprises of the heating from ohmic andinetic phenomena. In a half-cell a part of the reaction enthalpyoes to heat up the system and the rest goes out as the electricower of the system [39]. The source term in the energy balancean be written [32]:

=∑

j

aij

(ηj − T

∂Uj,ref

∂T

)+(

i1 × i1

σavg+ i2 × i2

κ

)(28)

Numerical solution of the system of equations was obtainedhrough the finite element software FEMLAB [40] (version 2.1).he FEMLAB engine is designed to solve a set of coupledifferential–algebraic equations of second order. The conver-ence criterion was that the difference between two successiveolutions at all mesh points be less than 10−5 (relative tolerance)or all variables.

. Results and discussion

U

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An important capability of a battery model is the ability to pre-ict the dependence of cell voltage on state of discharge (SOD)nd the maximum state of discharge (MSOD) beyond which the

t

c

10, 13 7, 9 1.75 × 10−2 A cm−2

10, 13 8, 10 1.75 × 10−3 A cm−2

oltage is so low at a fixed current that battery stops discharg-ng. Depending on the rate of discharge the MSOD may not bequal to the capacity and it is the purpose of this paper to explainhis behavior in the silver–zinc cell. In this section, we presenthe effects of various parameters on the discharge characteristicsf the silver–zinc cell, transient electrolyte concentration distri-utions, the reaction rate and current density profiles, porosityariations and predicted temperature rise in the cell during dis-harge. The values for the parameters are listed in Tables 1–3nd also in the nomenclature where appropriate. Note that theiterature is devoid of many of the critical parameters requiredy the model and that these tables are consistent with the datarom Refs. [4,36,41].

The 1C and 2C1 rates of discharge for the silver–zinc cellnder study correspond to 0.36 A (0.02 A cm−2) and 0.71 A0.04 A cm−2), respectively. These rates were chosen to illus-

r Sources (2007), doi:10.1016/j.jpowsour.2006.12.064

he parameters of Tables 1–3. 293

1 A 1C rate is the current required to charge or discharge the cell in 1 h (asalculated based on the limiting reactant).

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6 M. Venkatraman, J.W. Van Zee / Journal of Power Sources xxx (2007) xxx–xxx

Fig. 2. Effect of initial concentration (%KOH) on cell voltage. For curves(1)–(6), see Table 3, for the parameter values. The encircled regions indicateta1

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he change in the behavior of the the silver electrode at t = 800 and 400 s for 1Cnd 2C rate discharges, respectively. The solid and dashed lines correspond toC and 2C, respectively.

.1. Effect of initial and transient electrolyte compositions

As a baseline for future studies of transient cycles, the depen-ence of the discharge characteristics of the cell on the initiallectrolyte concentration, C0, is illustrated in Fig. 2, for 1C andC rates with the other parameters held constant. The solid linesorrespond to 1C rate and the dotted lines correspond to 2Cate discharges. Three values of C0: 25, 35, and 45% KOHere studied and help quantify that the cell-voltage increasesy approximately 0.02 V for every 10% rise in initial KOHoncentration. The MSOD for 1C rate is approximately 94%rrespective of C0 but C0 strongly affects the capacity utilizationt 2C. The curves 4–6 in Fig. 2 illustrate that with 25, 35, and5% KOH, the MSOD is 55.6, 77.7, and 94.4%, respectively, for2C rate discharge (i.e., 1000, 1400, and 1700 s, respectively).his is because, at 1C rate discharge, the rate of diffusion isomparable to the rate of OH− production but at a 2C rate,he diffusion process is not fast enough to replenish and com-ensate the continuous consumption of OH− in the negativelectrode during discharge. Consequently this leads to a fasterocal depletion of OH− ions in the anode and stops the cell fromischarging further, leading to low capacity utilization and hencelow value of MSOD. However, when a higher concentration ofOH is used, the amount of OH− ions available increases lead-

ng to a higher MSOD. The circled regions show the changes inhe electrochemical phenomena for silver electrode as discussedelow.

The initial OH− concentration affects the SOD because theate of transport of OH− from the positive to the zinc electrodeimits the battery. This limitation is best shown with the tran-ient concentration profiles of OH− ions for 1C and 2C rates.n Fig. 3, the solid lines show the extremes, namely 0% SODnd MSOD. The dotted lines show the variation of the profilef C across the cell in the x direction at various times. Thus,ven though there is available Zn, the changes in the local con-

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entration directly influence the extent of local utilization of thective material and hence the Nernst relationship for the cellotential. At high rates of discharge, the rate of consumption ofH− ions is not matched by the diffusion and hence a concen-

vatr

ig. 3. Concentration profiles of OH− ion during discharge at various times fora) 1C rate and (b) 2C rate, respectively. Note that the local concentration ofH− goes to 0 at 0.34 and 0.25 cm for 1C and 2C rates, respectively.

ration profile develops and diffusion aids migration. A linearoncentration gradient is established across the separator thatorresponds to the flux of the OH− ions needed for the speci-ed current density. This suggests that a reservoir if placed at

he separator–cathode interface, could attenuate the local deple-ion of OH− ions thereby ensuring a greater depth of discharger higher active mass utilization. Fig. 3 also shows that higherhe discharge rate higher the concentration of OH− ions in theilver electrode and lower in the zinc electrode. In other wordshe difference between the average concentrations of both thelectrodes is higher for a higher discharge rate.

.2. Effect of tortuosity (τ)

The transport rates could be changed by adjusting the tortu-sity of the materials in the cell since these adjust the diffusionoefficient directly. Fig. 4 shows the discharge curves for 1Cnd 2C rates for three values of τ. See Table 3, for the values ofarameters that correspond to the curves. An increase in tortu-sity corresponds to a increased path length for diffusion whichecreases the effective diffusivity. This reduction in diffusivityeads to a faster local depletion of the OH− ions thus decreasinghe MSOD considerably. Unlike C0, τ has a considerable influ-nce in the low rates (1C) also. Curves 1, 2, and 3 show MSOD

r Sources (2007), doi:10.1016/j.jpowsour.2006.12.064

alues 97.2, 94.4, and 88.8%, respectively, for 1C rate discharge 354

s τ is increased from 1.0 to 2.0 and then to 3.0. For the 2C rate 355

he curves 4, 5, and 6 show MSOD values 94.4, 61.1, and 38.9%, 356

espectively. Thus, at higher rates, the larger tortuosity leads to 357

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M. Venkatraman, J.W. Van Zee / Journal of Power Sources xxx (2007) xxx–xxx 7

FT

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Fig. 5. Distribution profiles of zinc during discharge at various times for (a) 1Cred

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ig. 4. Effect of tortuosity (τ) on cell performance. For curves (1)–(6), seeable 3, for the parameter values.

onsiderably low capacity utilization. The effects of C0 and τ

uggest that if a silver–zinc cell be subjected to high dischargeates from an incompletely charged battery, the concentration ofOH be made sufficiently high, to ensure maximum utilizationf capacity. However beyond a certain concentration, the dif-usion coefficients may show a very strong dependence on theoncentration [42] and may decrease with an increase in concen-ration. A higher temperature of operation may be used in suchcase. Before we present the effects of changes in the kinetic

arameters such as the exchange current densities, it is importanto understand the reaction distribution in both the electrodes.

.3. Reaction profiles

.3.1. Zinc electrodeFig. 5 shows the fraction of active material unutilized within

he zinc electrode, at several discharge times for 1C and 2C rates.t 1000 s for 1C there is 31% of the original Zn available at the

eparator (i.e., x = 0.1567 cm). This fraction is 0 at 2000 s at theeparator and the position at which this zero fraction moves to is= 0.1567 + lp, where lp = 0.17 cm at the end of discharge (i.e.,500 s). At the 2C rate there is 44% of the original Zn availablet the separator at 300 s, about 1.7% at the separator at 600 s andhe position at which this zero fraction moves to lp = 0.07 cm.

To understand the physical phenomena leading to theserofiles, Fig. 6 shows the corresponding reaction rate distri-ution in the negative electrode for 1C and 2C rates as theischarge progresses. There is clearly a front that moves from theeparator (x = lAg + lsep = 0.1567 cm) towards the anode currentollector (x = lAg + lsep + lZn = 0.5567 cm). As a result, a highlyon-uniform reaction distribution, dominated by mass-transferffects, is observed. Initially a not-so sharp reaction front isestricted to the separator–zinc interface because of high matrixonductivity. Hence, the reaction distribution, shown in Fig. 6 islmost uniform at the beginning of discharge (t = 0). As the dis-harge progresses, the local reaction rate at the separator–zincnterface rises initially to 0.23 and 0.67 A cm−3 at 500 and 200 sor 1C and 2C, respectively. The high reaction rate depletes the

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ctive material locally. As a result, the reaction rate shows a max-mum after the initial rise corresponding to the region which isich in the active material. Thus, a reaction front with a distincteak moves from the separator–zinc interface towards the anode

tfua

ate and (b) 2C rate. The reaction and penetration depths are also shown. Formphasis, the dashed line on the extreme left of the figures corresponds to theistance lAg + lsep, i.e., the interface between Zn electrode and the separator.

urrent collector. The curves at 1000 and 1500 s in Fig. 6(a)how the initial stages of the development of this reaction front.t 1500 s the peak of the front has formed and at 2000 s, theevelopment of front is practically complete. Between 2000nd 3500 s (end of discharge) the front moves further to thenterior of the zinc electrode consuming more active materialnd also growing steeper. The movement of the front stops withhe end of discharge caused by the local depletion of OH− ionssee Fig. 3(a)). Similar behavior is shown for the 2C rate inigs. 6(b) and 3(b).

The phenomena behind the formation of the front are inter-sting. Fig. 3 shows that at any given time, the concentration ofH− ion decreases along the zinc electrode. However, Fig. 5

hows that at any given time, the fraction of zinc left increaseslong the positive x direction. Apart from the concentration ofH− ion and the fraction of zinc left, the anodic overpotential

lso varies over the zinc electrode. The exponential of this over-otential increases with x (see Eq. (23)), which is consistent withhe occurrence of high reaction rate initially at the separator–zincnterface. Eq. (23) suggests that the Butler–Volmer expressionnvolving all these three variables would attain a maximum dueo the monotonic behavior of these functions. This explains thexistence of a maximum in reaction rate and the movement ofhe reaction front. In other words, the current density of reac-

r Sources (2007), doi:10.1016/j.jpowsour.2006.12.064

ion (3) goes to low values to the left of the maxima since the 422

raction of zinc approaches zero. Once again it goes to low val- 423

es to the right of the maxima, since the concentration of OH−424

pproaches zero. As the reaction front moves through the elec- 425

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8 M. Venkatraman, J.W. Van Zee / Journal of Power Sources xxx (2007) xxx–xxx

Fig. 6. Reaction distribution in the zinc electrode at various times during dis-charge for (a) 1C and (b) 2C rates. Note that a distinct reaction front progressesfed

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rom the separator–zinc interface into the zinc electrode in both the cases. Formphasis, the dashed line on the extreme left of the figures corresponds to theistance lAg + lsep, i.e., the interface between Zn electrode and the separator.

rode consuming more active material, the overpotential requiredor the reaction becomes more positive. Fig. 6 also shows that,he value of the maxima increases with time after the front isully formed. This is because, the rate at which the exponentialerm involving the overpotential changes is much higher than theate at which the terms involving concentration or the fraction ofctive material change. Hence, the value of the maximum reac-ion rate increases with time as the front moves in the positive xirection.

We define two quantities to understand the distribution ofctive material in the electrode. Penetration depth (lp), is defineds the distance from the separator at which the local fraction ofinc left is 0.01 at the end of discharge. For 1C rate it is close to.15 cm and for 2C rate it is 0.07 cm (see Fig. 5). The penetrations a measure of the electrode that was “completely” utilizeduring discharge and this would correspond to the “dead” regionf the cell at the beginning of the charging process. Reactionepth (lr), is defined as the distance from the separator, where theatio of the local fraction of Zn left, to the fraction of Zn left at thenode current collector end (x = lAg + lsep + lZn = 0.5567), is 0.99.rom Fig. 5, it may be seen that the reaction depth for 1C rate is.34 cm and for 2C rate it is approximately 0.2 cm. The reaction

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epth gives an idea about how much of the electrode has beenpractically active” during discharge. The difference (lp − lr)enotes the area where a highly non-uniform distribution of theinc is observed. A ratio of reaction depth (lr) to the length of

npti

ig. 7. Reaction distribution in the silver electrode during discharge at variousimes for (a) 1C and (b) 2C rates. No reaction front is observed in both the cases.ote that the silver electrode ends at 0.1067 cm.

he zinc electrode (lZn) gives the fraction of area of the electrodective during discharge. It is 85% for 1C rate and 50% for 2C rate.enetration depth and reaction depth along with θ1 (initial massatio of zinc to silver in the cell) and θ2 (initial mass ratio of silvern Ag2O to silver in AgO) may be used only as “status indicators”f the electrode. Towards the end of discharge the operatingonditions start to favor the reverse reactions (charging), and theinetic resistance is very high. Hence, the cell stops dischargingbruptly.

.3.2. Silver electrodeThe corresponding reaction distributions for the positive elec-

rode are presented in Fig. 7. Unlike the zinc electrode, a sharpeaction front is not observed in the silver electrode. The localeaction rate is lower in the positive electrode as can be seen byomparing Figs. 6 and 7. This is because unlike zinc electrode,he reactions at the silver electrode are characterized by prod-cts of high electrical conductivity and subsequently a higheratrix current flows in the positive electrode. Apart from this,

he production of OH− ions happens at the positive electrodehich increase the conductivity of the electrolyte locally thus

acilitating a more uniform consumption of the active material.lthough the maximum is not apparent, Fig. 7 shows that the

eaction rate distribution is extremely non-uniform at the begin-

r Sources (2007), doi:10.1016/j.jpowsour.2006.12.064

ing of discharge and tends to become uniform as the discharge 475

roceeds. At the beginning of discharge, similar to the nega- 476

ive electrode, the reaction rate is high near the silver–separator 477

nterface (x = lAg = 0.1067 cm) and decreases towards the end of 478

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ARTICLEOWER 8852 1–12

M. Venkatraman, J.W. Van Zee / Jour

ischarge. For the 1C rate (see Fig. 7(a)), the rate of reaction isigh at the current collector end (x = 0) and low at the separa-or end (x = lAg = 0.1067 cm). However, the rate profile invertss discharge proceeds and this behavior is observed in the 2Cate. Fig. 7 shows that around 56% SOD (2000 s for 1C rate and000 s for 2C rate) the rate profile is uniform and the reaction ratet 2C rate is approximately twice that of 1C. Ref. [38] discussesurther the relative ratio of the distribution of these rates.

To facilitate the understanding of the dynamics of the simul-aneous reactions in the positive electrode, we define twouantities f, the spatial average of the fraction of current con-ributed by Ag2O (i.e., reaction (1)), and g, the spatial averagef the dimensionless net rate of production of Ag2O:

== 1

lAg

∫ lAg

0

in1

in1 + in2

dx (29)

= 1

lAg

∫ lAg

0

(((−aAgin1sAg2O,1/n1F ) + (−aAgin2sAg2O,2/n

((−aAgin1sAg2O,1/n1F ) + (−aAgin2sAg2O,2/n2

The variation of f and g with time are plotted in Fig. 8(a)nd (b), respectively. Fig. 8(a) shows that initially f is close to 1nd as discharge proceeds it falls and reaches 0.5. This implieshat reaction (1) is much faster than reaction (2) at the beginningf discharge and that slows and becomes equal to the rate of

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eaction (2). This was observed experimentally by Dirkse [13],ho has attributed this to the partial reversibility of reaction (2).he increase in the concentration of OH− at the cathode drives

eaction (2) back. Fig. 8(b) shows that as f approaches 0.5, g

ig. 8. Variation of (a) average rate of reaction (1) (normalized) and (b) aver-ge rate of production of Ag2O (normalized) with time in the silver electrode.ote that both 1C and 2C rates are featured in the same graph. See Fig. 2, for

omparison.

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PRESSf Power Sources xxx (2007) xxx–xxx 9

|tt=0

)dx (30)

pproaches 0. At this juncture, the positive electrode may beiewed as having just one overall reaction in which AgO getsonverted to Ag without the intermediate Ag2O. The fraction ofilver remaining as Ag2O is plotted in Fig. 9. The profiles forhe 1C and 2C rates are the same in Fig. 9 and it is interestingo note that, the Ag2O becomes locally depleted at 22.2% SODhich is after 800s for 1C rate and after 400 s for 2C rate (seeig. 8). This is again is a result of the overall rate being sety the reaction (2), so that as Ag2O is produced by reactions2) and (1) consumes it immediately. The local depletion ofg2O happening much earlier than the end of discharge is also

onsistent with the cell-voltage behavior circled in Fig. 2. Thexchange current densities i01 and i02 of reactions (1) and (2)ave a significant influence on the times at which the depletionf occurs. This is discussed in the following section.

.4. Effect of exchange current density

Because the kinetic parameters are difficult to measure inhis system and not reported, we consider perturbations fromhose used above. Specifically, we are interested in the interac-ion of the reactions (1) and (2), and how the kinetic parametersf those reactions affect the behavior of the time-dependent celloltage. Similarly the movement of the front in the zinc elec-rode also is influenced by the kinetic parameters of the system.wo exchange current densities, namely i01 and i03 were var-

ed here while i02 was kept constant. Fig. 10(a) and (b) showshe effect of i01 and i03 exchange currents densities on the cell-oltage behavior. Three values of i01: 2 × 10−3, 2 × 10−4, and× 10−5 A cm−2, were used to study the behavior of the cell

see Table 3, for values of parameters). i01 has a pronounced

r Sources (2007), doi:10.1016/j.jpowsour.2006.12.064

ffect on the cell voltage. Fig. 10(a) shows that, the OCV drops 532

y approximately 0.05 V for an order of magnitude drop in i01. 533

comparison between curves 1 and 4 in Fig. 10(a) shows that 534

he model has captured the sharp fall in the cell voltage. This 535

ig. 9. Profiles of distribution of Ag2O over the silver electrode during dis-harge. At a given SOD, the profiles obtained at 1C and 2C rates do not showsignificant difference between them. Note that the silver electrode ends at

.1067 cm.

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Fig. 10. Effect of exchange current density (a) i01 and (b) i03 on cell performance.Fi2

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Fig. 11. Typical porosity distribution profiles in a silver–zinc cell during dis-cAd

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or curves (1)–(10), see Table 3, for the parameter values. The encircled regionsndicate the change in the behavior of the curves at t = 800 and 400 s for 1C andC rate discharges, respectively. See Fig. 2, for comparison.

grees well with the experimentally measured value of 1.45 Vor the initial cell voltage reported by Moden [36] for 1C rate.n the low rate studies (0.1C), a stable potential of 1.55 V wasredicted by the model (not shown), which once again agreesery well with the experimentally observed value of 1.59 V perell of Moden [36]. Thus, silver oxide materials with a highxchange current density for reaction (1) are bound to yieldigher cell voltage and also withstand higher rates of discharge.t is also notable that for a value of 2 × 10−3 A cm−2 for i01, aonsiderable decrease in the slope happens for both 1C and 2Cates at 800 and 400 s, respectively (marked by dotted circlesn Figs. 2 and 10). This change in curve behavior is consistentith the local depletion of Ag2O as discussed in the previous

ection and also Fig. 2. However, at a lower value of i01, theepletion of Ag2O is delayed and happens at a higher SOD.or example, for i01 values 2 × 10−4 and 2 × 10−5 A cm−2, theOD at which depletion of Ag2O happens are 66.7 and 88.9%,espectively. A lower value of i01 reduces the rate of reaction1) and hence a slower depletion of Ag2O. At an i01 value of× 10−5 A cm−2 the rate of reaction (1) is slowed down greatly

hat an initial increase in Ag2O due to the contribution of reaction2) is observed. Thus, Ag2O reaches a maximum concentrationnd falls off thereafter due to the increased consumption by reac-ion (1). Further details about profiles of Ag2O may be obtained

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rom Ref. [38].The effect of i03 on cell voltage is similar to i01. Fig. 10(b)

hows that the cell voltage drops by 0.05 V for an order of mag-itude drop in i03. A higher exchange current density thus would

t

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harge at various SOD: (1) 0%, (2) 27.7%, (3) 55.4%, (4) 83.3%, and (5) 97.2%.t a given SOD, the profiles obtained at 1C and 2C rates do not show a significantifference between them. However, MSOD for 2C rate is 55.4%.

ead to a higher cell voltage. A value of 1.75 × 10−4 A cm−2 didot allow the cell to discharge since kinetic resistance of the cellecame high. Both the exchange current densities have almosto effect on MSOD. This is because under normal operatingonditions with high rate discharges the system is usually underass-transfer control. It is the local non-availability of the OH−

ons that leads to the abrupt end of discharge thereby loweringSOD.

.5. Porosity distribution

Fig. 11 shows the variation of porosity over the electrode atifferent times at the 1C rate. The y axis of the plot is the ratiof instantaneous porosity to the initial porosity in the respectiveegions. The separator porosity is a constant since no reactionakes place in that region and no clogging of the separator byeaction solids is assumed. The porosity of both electrodes do notary appreciably during discharge. This may obviate the needo include the porosity equations during a solution of the three-imensional equations. Apart from reducing the bandwidth ofhe system of equations, it also attenuates the difficulty in solvinghe concentration equations since a constant porosity reduces theon-linearity to a good extent.

.6. Temperature rise and profiles

The present model includes a thermal energy equation (referq. (25)), accounting for the reversible, kinetic, and joule heating

erms involved in heating of a cell during discharge. Since, theonductivities of the materials in a silver–zinc cell are high, aow discharge rate (i.e., <1C) does not effect a local temperatureise and even at the 2C rate for a single cell, the temperature at aiven instant of time does not vary appreciably over x. Hence, alot of average temperature rise versus time would be sufficiento understand the thermal behavior of the system. By average

r Sources (2007), doi:10.1016/j.jpowsour.2006.12.064

emperature rise, we mean: 595

avg(t) − T0 = 1

lAg + lsep + lZn

∫ lAg+lsep+lZn

0(T (x, t) − T0) dx 596

(31) 597

ARTICLE IN+ModelPOWER 8852 1–12

M. Venkatraman, J.W. Van Zee / Journal o

FF

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599

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633

ig. 12. Effect of initial concentration (%KOH) on average temperature rise.or curves (1)–(6), see Table 3, for the parameter values.

The effect of initial concentration, C0, on the average temper-ture rise is shown in Fig. 12. Concentration affects the averageemperature-rise by affecting the discharge time and the ther-

al and electrical properties of the electrolyte. Thus, a longerischarge time implies a longer heating and a higher maxi-um temperature although the average temperature decreasesith an increase in initial concentration. Moden [36] observed

n average temperature rise of 0.22 and 0.54 K min−1 for 1Cnd 2C rate of discharge, respectively. An inspection of Fig. 12hows that the average temperature-rise reaches approximately

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4 K at 1C rate at end of discharge (∼0.23 K min−1) and shows.48 K min−1 for the 2C rate. This difference between thebserved and predicted rise could be a result of different externaloundary conditions or kinetic parameters.

ig. 13. Effect of exchange current density (a) i01 and (b) i03 on average tem-erature rise. For curves (1)–(10), see Table 3, for the parameter values.

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Fig. 13 shows that, at 2C, decreasing i01 two orders of mag-itude removes the changes in the initial slope so that the rise isore linear, however the final temperature difference is insignif-

cant. On the other hand, a larger value of i03 lowers the averageemperature rise in the cell.

. Conclusions

A mathematical model has been developed and used totudy the time-dependent and position-dependent performancend thermal behavior of the silver–zinc cell during discharge.pecies and reaction distributions have been predicted. Theodel predicts that the discharge may reach an abrupt end at

igh discharge rates, because of mass transfer limitations. Theimultaneous reactions in the positive electrode influence theehavior of the cell voltage–time curve considerably. Porosityariations were not found to be important. The temperature riseas predicted and found to be agreeable with reported experi-ental values. A high concentration of the alkali electrolyte andell-prepared electrodes with high exchange current densities

nd low tortuosity could increase the capacity utilization.

cknowledgement

The authors gratefully acknowledge support for this workrom ONR grant N00014-98-1-0554.

eferences

[1] A.P. Karpinski, B. Makovetski, S.J. Russell, J.R. Serenyi, D.C. Williams,J. Power Sources 80 (1999) 53–60.

[2] B. Hariprakash, S.K. Martha, A.K. Shukla, J. Power Sources 117 (2003)242–248.

[3] O. Hasvold, N. Storkersen, J. Power Sources 96 (2001) 252.[4] A. Himy, Silver–Zinc Battery—Phenomena and Design Principles, 1st ed.,

Vantage Press, New York, 1986.[5] P. Suresh, D.H. Nagaraju, A.K. Shukla, N. Munichandraiah, Electrochim.

Acta 50 (2005) 3262–3272.[6] H.L. Lewis, T. Danko, A. Himy, W. Johnson, J. Power Sources 80 (1999)

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