Corrosion testing of nickel, cobalt, nickel cobalt alloy, borides, and other fuel cell catalyst samples for activity in oxidation of hydrazin

Matsuda, S.

Sullivan, B. P.

English

NASA Technical Reports Server

TEST EVALUATION OF FUEL CELL CATALYSTS 
C o n t r a c t  NASW-1527 
20  December  1 9 6 7  
Q u a r t e r l y  R e p o r t  No.  3 
1 6  A u g u s t  - 1 5  N O V P ~ ~ P ~  1 9 6 7  
P r e p a r e d  By 
S .  M a t s u d a  a n d  B .  P .  S u l l i v a n  
P r e p a r e d  F o r  
N a t i o n a l  A e r o n a u t i c s  a n d  S p a c e  A d m i n i s t r a t i o n  
H e a d q u a r t e r s  
W a s h i n g t o n ,  D . C .  , 2 0 5 4 6  
MONSANTO R E S E A R C H  C O R P O R A T I O N  
B O S T O N  LABORATORY 
E v e r e t t ,  M a s s a c h u s e t t s  0 2 1 4 9  
https://ntrs.nasa.gov/search.jsp?R=19680006958 2020-03-12T09:22:52+00:00Z
T A B L E  OF CONTENTS 
Page  
I . Summary . . . . . . . . . . . . . . . . . . . . . . .  
I1 . I n t r o d u c t i o n  . . . . . . . . . . . . . . . . . . . .  
I11 . P r e p a r a t i o n  of E l e c t r o d e s  . . . . . . . . . . . . . .  
I V  . T e s t  R e s u l t s  . . . . . . . . . . . . . . . . . . . .  
A . C o r r o s i o n  T e s t i n g  . . . . . . . . . . . . . . . .  
B . N2H4 E l e c t r o d e  T e s t i n g  . . . . . . . . . . . . .  
ii 
I .  SUMMARY 
During  t h e  t h i r d  q u a r t e r  o f  t h e  c o n t r a c t ,  t h e  t h i r d  
group of  compounds s u p p l i e d  by  t h e  U .  S .  Bureau o f  Mines was 
t e s t e d  f o r  c a t a l y t i c  a c t i v i t y  i n  t h e  o x i d a t i o n  of  N2H4. A l l  
compounds showed r e l a t i v e l y  h igh  a c t i v i t i e s  f o r  t h e  r e a c t i o n .  
Among t h e  c a t a l y s t s ,  a group of b o r i d e s  was s i g n i f i c a n t l y  more 
a c t i v e  t h a n  t h e  o t h e r s ,  reduced  metals,  a l l o y s  and t h e i r  c a r b i d e s  
and n i t r o c a r b i d e s .  However, all compounds showed s e v e r e  c o r r o s i o n  
i n  5M KOH s o l u t i o n ,  and l e s s ,  bu t  a p p a r e n t ,  c o r r o s i o n  i n  5M KOH 
added w i t h  2M N 2 H 4 .  
1 
11. I N T R O D U C T I O N  
The objective of this contract is to determine certain 
essential properties of non-noble metal compounds as electrode 
catalysts for fuel cells. Properties of major interest include: 
polarization characteristics of the electrodes containing these 
compounds; and the chemical stability of these electrodes in pre- 
scribed test environments. 
The work originally undertaken at Monsanto Research Cor- 
poration is to investigate the electrocatalytic activity of the 
compounds for oxidation of dextrose and hydrazine, 
tests for dextrose oxidation were waived after the first quarter, 
because of the relatively poor chemical stability of these com- 
pounds in the specific testing environment for the dextrose oxi- 
dation. Since the dextrose electrode is to be used in an im- 
plantable fuel cell for an artificial heart, even the slightest 
contamination of the electrolyte system is not permissible. 
iron, namely, carbide, nitride, carhonitride and nitrocarbide 
leached Raney alloys of Ni, Co and Ag, and their carbides and 
nitrocarbides were tested for N2H4 oxidation, although the major- 
ity of these compounds were badly corroded in 5M KOH electrolyte 
and less, but still significantly attacked by KOH solution with 
However, 
During the first two quarters, interstitial compounds of 
N2H4. 
During this quarter, the third batch of catalysts prepared 
by the U. S. Bureau of Mines was examined. These catalysts were 
Ni, Co and their alloys prepared from various compounds by reduc- 
tion and the Ni and Co carbides, nitrocarbides and borides, shown 
in Table 1. 
2 
T a b l e  1 
SAMPLE N U M B E R S  FOR CATALYSTS TESTED D U R I N G  THE THIRD QUARTER 
- N i  R e d u c e d  C a r b i d e  N i  t r o c a r b i d e  
p r e p a r e d  f r o m  t h e  f o r m a t e  54R 5 4 c  39NC 
p r e p a r e d  f r o m  t h e  h y d r o x i d e  56R 56C 41NC 
c o  
p r e p a r e d  f r o m  t h e  h y d r o x i d e  59R 5 9 c  43NC 
-
3 N i  : 1 Co 
p r e p a r e d  f r o m  t h e  h y d r o x i d e s  6 1  R 6 1  C 45NC 
p r e p a r e d  f r o m  t h e  n i c k e l  f o r m a t e ,  
c o b a l t  a c e t a t e  58C 36NC 
1 N i : l A g  
p r e p a r e d  f r o m  t h e  h y d r o x i d e s  53R 5 3 c  38NC 
1 N i  : 1 Ag : 1 Au 
p r e p a r e d  f r o m  t h e  h y d r o x i d e s  60C 44NC 
B o r i d e s  
( p r e p a r e d  f r o m  t h e  r e a c t i o n  o f  NaBH4 a n d  t h e  s u l f a t e  o f  t h e  
t r a n s i t i o n a l  m e t a l s )  
N i  
c o  
1 N i  : 1 Co 
1 N i  :3Co 
3 N i  : 1 Co 
B - 6  
B - 7  
8 - 1 8  
B - 2 0  
B - 9  
3 
111. P R E P A R A T I O N  OF E L E C T R O D E S  
A l l  catalysts were preconditioned according to the pro- 
cedure described in the first quarterly report. 
A l l  catalysts were ground and sieved to -400 mesh in a 
chemically pure argon atmosphere prior to the final precondition- 
ing process. 
* All electrodes prepared were type B . These electrodes 
contain a network of macropores in a micro-porous matrix and are 
considered very suitable for the present study. 
Catalyst loading was approximately 0.7 g/inch2. 
The method for preparing this type electrode is Monsanto 
Research Proprietary. 
* 
4 
I V .  T E S T  R E S U L T S  
A .  C O R R O S I O N  T E S T I N G  
Weighed samples  ( a b o u t  0.5 gram e a c h )  were soaked  ove r -  
n i g h t  i n  50 cc  of 5M KOH i n  a c o n s t a n t  t e m p e r a t u r e  b a t h  a t  70OC. 
A l l  c a t a l y s t s  showed c o r r o s i o n ,  as i n d i c a t e d  by s i g n i f i c a n t  d i s -  
c o l o r a t i o n  o f  t h e  t e s t  s o l u t i o n .  S i n c e  f o r m a t i o n  of  h y d r o x i d e s  
was also o b v i o u s ,  no weight  d e t e r m i n a t i o n  was made a f t e r  t h e  
t e s t s .  A d d i t i o n  of  N 2 H 4  t o  t h e  KOH s o l u t i o n  d i d  n o t  s t o p  t h e  
c o r r o s i o n .  The appea rance  of  t h e  v a r i o u s  t e s t  s o l u t i o n s  a re  shown 
i n  T a b l e  2. 
B. N 3 H b  E L E C T R O D E  T E S T I N G  
Although t h e  c o r r o s i o n  t e s t s  r e v e a l e d  t h a t  a l l  c a t a l y s t s  
i n  t h e  t h i r d  group were a t t a c k e d  i n  some d e g r e e  by t h e  t e s t  
e l e c t r o l y t e  (5M KOH + 2M N2H4), t h e  p o l a r i z a t i o n  data  f o r  N2H4 
o x i d a t i o n  was t a k e n  i n  t h e  manner d e s c r i b e d  i n  t h e  p r e v i o u s  re -  
p o r t .  
I R  f r e e  e l e c t r o d e  p o t e n t i a l s  v s  t h e  s a t u r a t e d  ca lomel  
e l e c t r o d e  a t  v a r i o u s  c u r r e n t  d e n s i t i e s  above 1 0  mA/cm2 ( a p p a r e n t  
d e n s i t i e s )  are  g i v e n  i n  Tab le  3 .  
R e s u l t s  i n d i c a t e  t ha t  the  e l e c t r o d e  p o t e n t i a l s  o f  t h e s e  
c a t a l y s t s  a r e  more a c t i v e  even  a t  1 0 0  mA/cm2 t h a n  t h a t  o f  t h e  
r e v e r s i b l e  hydrogen e l e c t r o d e  i n  t h e  same e l e c t r o l y t e .  Among t h e  
c a t a l y s t s ,  a group o f  b o r i d e s  a r e  s i g n i f i c a n t l y  more a c t i v e  t h a n  
t h e  o t h e r s .  The v e r y  s t r o n g  odor  of  N H 3  was d e t e c t e d  i n  e x h a u s t  
g a s  o n l y  from t h e  e l e c t r o d e s  made of  t h e  b o r i d e s .  
5 
T a b l e  2 
S a m p l e  No.  
54R 
5 4 c  
39NC 
56R 
56C 
41NC 
59R 
5 9 c  
43NC 
61R 
61 C 
45NC 
58C 
36NC 
53R 
5 3 c  
38NC 
60C 
44NC 
B-6 
B-7 
B-18 
B-20 
B-9 
CORROSION T E S T S  
T e s t i n g  S o l u t i o n :  5M K O H  a t  7OoC 
A p p e a r a n c e  
b l u e  c o l o r  
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brown c o l o r  a n d  d e p o s i t  
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I . . .  
01 STRIBUTION L I S T  -
C h i e f ,  S o l a r  8( C h e m i c a l  Power Systems 
Code RNW 
NASA H e a d q u a r t e r s  
W a s h i n g t o n ,  0.C. 20546 ( 8 )  
hew T e c h n o l o g y  R e p r e s e n t a t i v e  
O f f i c e  o f  T e c h n o l o g y  U t i l i z a t i o n  - Code UT 
NASA H e a d q u a r t e r s  
W a s h i n g t o n ,  U.C. 20546 
S c i e n t i f i c  and  T e c h n i c a l  I n f o r m a t i o n  F a c i l i t i e s  
P. 0. Box 33 
C o l l e g e  P a r k ,  M a r y l a n d  20740 
A t t e n t i o n :  N A S A  R e p r e s e n t a t i v e  
E r n s t  M. Cohn 
Code RNW 
N A S A  H e a d q u a r t e r s  
W a s h i n g t o n ,  D.C. 20546 
k l r .  0. B i e n s t o c k  
B u r e a u  o f  M i n e s  
4800 F o r b e s  Avenue 
P i t t s b u r g h ,  Pa. 15213  
ilr. A .  M a k r i d e s  
TY C O  L a b o r a t o r i  es 
Gear  H i l l  
k ' a l t h a m ,  Mass. 02154  
O r .  0.  P o u l i  
A1 l i s - C n a l m e r s  t l f g .  Co. 
1100 s. 7 0 t h  S t .  
M i  l w a u k e e ,  W i s c o n s i n  5321 4 
O r .  S e i g o  N a t s u d a  
Monsan to  R e s e a r c h  C o r p o r a t i o n  
1101 1 7 t h  S t . ,  N.W. 
w a s h i n g t o n ,  D.C. 20036 
ur. George  E. Evans 
U n i o n  C a r b i d e  C o r p o r a t i o n  
E l e c t r o n i c s  U i v i s i o n  
P. 0. L o x  6116 
C l e v e l a n d ,  b h i o  44101 
U r .  11. J. G o l d s m i t h  
C a t a l y s t  R e s e a r c h  C o r p o r a t i o n  
6101  F a l l s  Road 
B a l t i m o r e ,  M a r y l a n d  21209 
Elr. R o b e r t  J .  F l a n n e r y  
91U S o u t h  b i i c h i g a n  Avenue 
C h i c a g o  80, I l l i n o i s  
O r .  C. E. H e a t h  
E s s o  R e s e a r c h  & E n g i n e e r i n g  C O .  
P .  0. Box 8 
L i n d e n ,  fiew J e r s e y  07036 


Test evaluation of fuel cell catalysts Quarterly report, Aug. 16 - Nov. 15, 1967

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