SINGLE CELL SEAWATER BATTERIES
Myles Walsh
Cape Cod Research, Inc.
P. 0. Box 600
Buzzards Bay, MA 02532
Abstract
Many i n s t r u m e n t s and d e v i c e s used i n t h e ocean
r e q u i r e power o v e r p e r i o d s of service r a n g i n g from a
few days t o s e v e r a l y e a r s . While seawater b a t t e r i e s
have advantages t h a t make them i d e a l f o r most of t h e s e
a p p l i c a t i o n s , a v a i l a b l e seawater b a t t e r i e s are a l l
m u l t i c e l l , high-power, s h o r t - l i v e d d e v i c e s .
This paper e x p l o r e s t h e f e a s i b i l i t y of p r o v i d i n g
watts of power f o r y e a r s w i t h a s i n g l e c e l l approach
b u i l t around aluminum anodes and oxygen consuming o r
hydrogen e v o l v i n g cathodes. R e s u l t s are p r e s e n t e d
which s u g g e s t s p e c i f i c energy d e n s i t i e s of over 440
Wh/kg (200 Wh/lb) can be achieved w i t h o u t t h e r i s k s
i n h e r e n t w i t h lithium-based systems.
INTRODUCTION
I n r e c e n t y e a r s aluminum h a s l a r g e l y r e p l a c e d
z i n c and magnesium as t h e m e t a l of c h o i c e f o r m i s s i o n s
r e q u i r i n g months o r y e a r s . The p r e s e n c e of t h e
i n s u l a t i n g o x i d e f i l m on aluminum h a s been s u c c e s s f u l l y
overcome through u s i n g 99.999% aluminum a l l o y e d w i t h
small amounts of o t h e r metals. The c h o i c e of a l l o y
depends on t h e l e n g t h of t h e mission and on t h e d e s i r e d
t r a d e o f f between coulombic e f f i c i e n c y and o p e r a t i n g
anode v o l t a g e .
Commercial a l l o y s (Alupower, I n c . , B e m a r d s v i l l e ,
N J ) o p e r a t e [ l ] a t about -1.4 V v s SCE i n salt water
from open c i r c u i t a l l t h e way t o 200 mA/cm2. This
e x c e l l e n t performance i s t y p i c a l l y i n s e n s i t i v e t o b o t h
water temperature and p r e s s u r e . The c o r r o s i o n rate of
t h e a l l o y is t y p i c a l l y d i r e c t l y proportional t o the
operating c u r r e n t density. This is r e f e r r e d t o i n t h e
l i t e r a t u r e as t h e "negative d i f f e r e n c e e f f e c t . " The
l i n e a r n a t u r e of t h i s e f f e c t makes coulombic e f f i c i e n c y
independent of o p e r a t i n g c u r r e n t d e n s i t y . Coulombic
e f f i c i e n c i e s between 60 and 90% have been r e a l i z e d i n
p r a c t i c e f o r c e l l s o p e r a t i n g f o r many months.
While t h e a v a i l a b l e energy i s set p r i m a r i l y by t h e
amount of aluminum i n t h e b a t t e r y , t h e power o u t p u t i s
s e t almost e n t i r e l y by t h e cathode d e s i g n . Seawater
i n most l o c a t i o n s of i n t e r e s t c o n t a i n s d i s s o l v e d oxygen.
The l i m i t i n g d i f f u s i o n c u r r e n t t o a s u r f a c e consuming
d i s s o l v e 2 oxygen by f o u r e l e c t r o n r e d u c t i o n i s about
0.5 mA/cm2. Thus, p r a c t i c a l seawater b a t t e r i e s
designed t o p a s s i v e l y consume oxygen must have l a r g e
geometric cathode a r e a s o p e r a t i n g a t v e r y low c u r r e n t
density.
Inexpensive o r g a n i c c a t a l y s t s are a v a i l a b l e which
when s u p p o r t e d on g r a p h i t e f i b e r consume oxygen from
s e a w a t e r a t about 0.0 V v s SCE a t c u r r e n t d e n s i t i e s of
a b o u t 0.1 mA/cm2. Thus , aluminum/dissolved oxygen
c e l l s can be designed which o p e r a t e f o r y e a r s a t o v e r
one v o l t .
There are m i s s i o n s which i n v o l v e bottom deployment
i n r e g i o n s where t h e supply of d i s s o l v e d oxygen i s
inadequate. Under t h e s e c o n d i t i o n s , hydrogen e v o l u t i o n
cathodes are r e q u i r e d . While t h e hydrogen e v o l u t i o n
r e a c t i o n (HER) under p r i s t i n e l a b o r a t o r y c o n d i t i o n s i s
w e l l s t u d i e s , much work i s needed t o develop s t r u c t u r e s
which o p e r a t e f o r long p e r i o d s of t i m e i n 4OC seawater
poisoned by unknown o r g a n i c and/or i n o r g a n i c m a t e r i a l s .
SINGLE CELL CONCEPT
I n s t e a d of connecting c e l l s t o g e t h e r i n t h e u s u a l
manner t o form a b a t t e r y , a s i n g l e c e l l can power
9OCH2863-9/9orwxxM11~1.000 1990 IEEE
T
numerous s m a l l DC/DC c o n v e r t e r s which t o g e t h e r p r o v i d e
u s e f u l v o l t a g e and c u r r e n t from a s i n g l e low v o l t a g e
source.
R e l i a b i l i t y , c o n s t a n t v o l t a g e o u t p u t and ease of
c o n s t r u c t i o n are t h e advantages of t h i s approach. The
d i s a d v a n t a g e s a r e loss of about 30% of t h e energy i n
t h e DC/DC c o n v e r t e r s and s l i g h t l y h i g h e r c o s t .
R e l i a b i l i t y i s a major concern f o r marine d e v i c e s .
M u l t i c e l l c o n f i g u r a t i o n s submerged i n seawater a r e
v e r y s u s c e p t i b l e b o t h t o s h u n t c u r r e n t s which tend t o
unevenly l o a d one of t h e c e l l s and t o t h e c o r r o s i o n of
i n t e r c e l l c o n n e c t o r s . These l e a d t o r a p i d f a i l u r e of
the battery. Shunt c u r r e n t s can a l s o l e a d t o c o r r o s i o n
and f a i l u r e of t h e housing of t h e d e v i c e b e i n g powered.
For b a t t e r i e s r e l y i n g on t h e d i f f u s i o n of g a s e s ,
s e a l i n g one c e l l from t h e n e x t i s n o t always p o s s i b l e
and e l e c t r o l y t e p a t h s from c e l l t o c e l l a r e a f a c t of
l i f e . Thus, r e l i a b l e m u l t i c e l l c o n f i g u r a t i o n s u s i n g
d i s s o l v e d oxygen o r hydrogen e v o l u t i o n are v e r y h a r d t o
achieve i n p r a c t i c e .
These problems are l a r g e l y e l i m i n a t e d by u s i n g a
s i n g l e c e l l . Redundancy i s b u i l t i n t o t h e concept.
S i n g l e c e l l s can be crushed o r c u t i n h a l f . A s long a s
a t least one DC/DC c o n v e r t e r i s connected t o t h e
remaining s t r u c t u r e , power keeps flowing. DC/DC con-
v e r t e r s a r e designed s o t h a t t h e y f a i l as a n open
c i r c u i t . Thus, f a i l u r e of any one DC/DC c o n v e r t e r does
n o t reduce t h e b a t t e r y l s power o u t p u t .
All m u l t i c e l l b a t t e r i e s decay. S i n g l e c e l l s w i t h
DC/DC c o n v e r t e r s o u t p u t o v e r t h e e n t i r e l i f e of t h e
b a t t e r y w i t h i n 1%t h e d e s i r e d v o l t a g e . Numerous o u t p u t
v o l t a g e s a r e p o s s i b l e from t h e same i n p u t c e l l and t h e
o u t p u t s can be s h o r t e d w i t h o u t any damage t o t h e
battery.
ROPE BATTERIES
One of t h e major mechanical d e s i g n problems i s how
t o a c h i e v e deployment of a l a r g e s u r f a c e a r e a cathode
and y e t s t o r e t h e undeployed b a t t e r y i n a s m a l l volume.
T h i s has been achieved by d e s i g n i n g t h e s i n g l e c e l l
l i k e a w i r e rope ( F i g u r e 1). The i n n e r c o r e of t h e
rope t y p i c a l l y c o n t a i n s a s t r e n g t h member and t h e DC/DC
converters. T h i s i s e n c l o s e d i n a porous s e p a r a t o r
which i n t u r n i s sewed t o c a t a l y z e d g r a p h i t e c l o t h .
S i n g l e c e l l Rope B a t t e r i e s t m of t h e t y p e shown i n
F i g u r e 1 w e r e b u i l t i n 1989. These b a t t e r i e s are
designed t o p r o v i d e a c t u a l s p e c i f i c e n e r g i e s of 290
Wh/lb. Each c o n t a i n s about 200 pounds of aluminum
which p r o v i d e s 9 watt-years of energy. The DC/DC con-
v e r t e r s s e l f - s t a r t a t 0 . 8 V and p r o v i d e 1 8 watts f o r
s i x months a t 14.3 V. They a r e designed t o l o a d s h a r e
and should one f a i l , t h e o t h e r t a k e s over and p r o v i d e s
f u l l l o a d . The d r y weight of t h i s b a t t e r y i s about
275 pounds which i n c l u d e s a 25,000 pound s t r e n g t h
member and s u f f i c i e n t epoxy t o p r o t e c t t h e DC/DC con-
v e r t e r s t o a h y d r o s t a t i c p r e s s u r e of 5,000 p s i . T h i s
design o p e r a t e s by consuming oxygen from t h e ocean.
The cathode has an a r e a of 70 s q u a r e y a r d s and i s
designed t o e f f i c i e n t l y c o l l e c t 36 A worth of oxygen
from c o l d seawater f o r a y e a r .
Improvements i n DC/DC c o n v e r t e r d e s i g n s i n c e 1989
now a l l o w a r e d u c t i o n i n weight of about t e n pounds
and a 10% improvement i n DC/DC conversion e f f i c i e n c y .
These improvements should t r a n s l a t e i n t o f u t u r e
v e r s i o n s having energy d e n s i t i e s of i n e x c e s s of 320
Wh/lb.
 BRANTNER CONNECTOR
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F " G T A I L ~ ~ - p ,
STRENGTH MEMBER
yFT +

4oFT
VOLTAGE MAX 50 FT
CONVERTERS MAX

CATHODE __c

Fig. 1. Rope Batterytm

1
BOTTOM DEPLOYMENT

I t i s l i k e l y t h a t hydrogen e v o l u t i o n cathodes w i l l
be needed f o r s i n g l e c e l l c o n f i g u r a t i o n s which o p e r a t e
on t h e ocean f l o o r . The most t h a t can be hoped f o r
thermodynamically i s about 0.8 v o l t s a t open c i r c u i t
and about 0.5 v o l t s on load. This low v o l t a g e p u t s
heavy demands on t h e DC/DC c o n v e r t e r s . S i x t y p e r c e n t
e f f i c i e n t power conversion i s probably i n t h e n e a r
term t h e b e s t t h a t can be achieved. A c e l l voltage
of 0.5 v o l t s and power conversion e f f i c i e n c y of 60%
t o g e t h e r imply t h a t about 30 pounds of aluminum a r e
needed t o produce one watt-year of u s e f u l power. This
r e s u l t i s insensitive t o battery configuration.
Assuming t h a t t h e sum of cathode, DC/DC c o n v e r t e r
and b a t t e r y case weights can be kept t o about 6 pounds
o r about 1 7 % of t h e t o t a l b a t t e r y weight, t h e proposed
seawater b a t t e r y would have a s p e c i f i c energy d e n s i t y
of about 240 Wh/lb (530 Wh/kg).

CONCLUSIONS

Seawater b a t t e r i e s have always been a d e s i r a b l e

choice because of t h e i r high r e l i a b i l i t y , s a f e t y and
long s h e l f l i f e . A s a r e s u l t of advances i n DC/DC
c o n v e r t e r technology, aluminum a l l o y s , and oxygen
r e d u c t i o n c a t a l y s t s , s i n g l e c e l l b a t t e r i e s powered by
oxygen d i s s o l v e d i n t h e ocean a r e capable of y i e l d i n g
i n excess of 290 watt-hours p e r pound of b a t t e r y .
While hydrogen e v o l u t i o n systems cannot thermo-
dynamically match t h i s l e v e l , t h e i r p r o j e c t e d l e v e l s
a r e s t i l l high enough t o exceed primary l i t h i u m
systems p r o t e c t e d from h y d r o s t a t i c p r e s s u r e . For
systems deployed f o r long p e r i o d s of time on t h e ocean
f l o o r , they warrant a c l o s e r look.

REFERENCES

[l] E . Budevski, I. I l i e v , A. Kaisheva, A. Despic,

and K . Krsmanovic, J . Applied Electrochem., 19,
323 ( 1 9 8 9 ) .

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