Note: Descriptions are shown in the official language in which they were submitted.
CA 02558801 2002-12-04
70691-22D
FUEL CELL METALLIC SEPARATOR AND METHOD
FOR MANUFACTURING SAME
This is a divisional application of Canadian
Patent Application Serial No. 2,913,558 filed
December 4, 2002.
;'> Background of the Invention
Field of the Invention
The present invention relates to a metallic
separatorwhichisinstalledinaproton-exchangemembrane
fuel cell and a method for manufacturing the same metallic
separator
Description of the Related Art
In a proton-exchange membrane fuel cell, a laminated
body in which separators are laminated on both sides of
a flat plate-like membrane electrode assembly (MEA)is
made to be one unit, and a plurality of units are stacked
together to form a fuel cell stack . The membrane electrode
assembly is of a three-layer construction in which an
electrolyticmembranecomprisinganion-exchangingresin
is held between a pair of gas diffusion electrodes which
constitute a positive pole (cathode) and a negative pole
(anode) . The gas diffusion electrode is such that a gas
diffusion layer is formed on the outside of an electrode
catalyst layer which contacts the electrolytic membrane.
In addition, the separator is laminated in such a manner
as to be brought into contact with the gas diffusion
1
CA 02558801 2002-12-04
electrode of the membrane electrode assembly, whereby
a gas flow path through which gas is allowed to flow and
a coolant flow path are formed between the separator so
laminated and the gas diffusion electrode. According to
the fuel cell, for example, when hydrogen gas which is
fuel is allowed to flow through a gas flow path which
faces the gas diffusion electrode on the negative pole
side, whereas oxide gas such as oxygen or air is allowed
to flow trough a gas flow path which faces the gas diffusion
1U electrode on the positive pole side, an electrochemical
reaction occurs and current is generated.
The separators need to have a function to supply
electrons generated through a catalytic reaction of
hydrogen gas on the negative pole side to an outside circuit,
15 as well as a function to supply electrons from the outside
circuit to the positive pole side . To this end, conductive
materials, such as graphite and metallic materials, are
used for the separators. In particular, the metallic
materials are considered to be advantageous in that they
ZO have superior mechanical strength and that they can be
formed into a thin plate which can eventually provide
a separator light in weight and small in size. As the
metallic separator, there is a separator which is
manufactured by rolling stainless steel containing
~~5 conductive inclusions which are deposited and/or
2
CA 02558801 2002-12-04
dispersed therein into a thin plate, and forming by
pressing the thin plate so as to have a cross section
constituted by alternate ridges and grooves so that the
grooves formed on front and back: surfaces of the thin
plate are used for the gas flow paths and coolant flow
paths. The conductive inclusions are such as to
contribute to the improvement in power generating
performance by forming a conductive path.
With the metallic separators so constructed, the
ridges surfaces are brought into contact with gas
diffusion electrodes of the membrane electrode assembly
in a state in which the separators are assembled to the
membrane electrode assembly. The ridged portions are
formed into, a trapezoid having sides which are slightly
inclined so that the separator can easily be removed from
the did after pressing. In addition, corners which are
transitional portions from the surface of the ridged
portion to the sides are inevitably formed into a round
shape (R-shape) by bending. These constitute
restrictions on the enlargement of actual contact areas
to the membrane electrode assembly at the surfaces of
the ridged portions . A reduction in contact area of the
separator to the membrane electrode assembly leads to
an increase in contact resistance and prevents the
improvementofpower generatingperformance. Therefore,
3
CA 02558801 2002-12-04
the enlargement of the contact area is desired. In
addition, some of separator, the surfaces of the ridged
portions are each close to the round shape as a whole
and hence their flattened surfaces become limited. As
o this occurs, it is difficult to ensure that a desired
surface pressure is obtained at the surfaces the ridged
portions which are in contact with the membrane electrode
assembly, this also leading to an increase in contact
resistance.
Further, when stainless steel in which conductive
inclusions are deposited and/or dispersed is rolled into
a thin plate, there may be caused a case where an abnormal
layer is produced on the surface of the thin plate in
which conductive inclusions which are broken extremely
finely by rolling are caused to aggregate. In case a fuel
cell is constituted by separators in which the abnormal
layers exist on the surfaces thereof and is then put in
operation, the conductive inclusions existing in the
abnormal layers drop, which leads to deterioration in
ZO power generating performance.
Moreover, in the manufacture of separators as has
been described above, since there exists a surface
rolling-affected layer on a stainless steel plate, the
steps are required of grinding to remove the surface
rolling-affected layer so as to allow good conductive
4
CA 02558801 2002-12-04
inclusions that have not been affected by rolling to be
exposed on the surface of a base metal and, furthermore,
allowing the exposed conductive inclusions to protrude
so as to reduce the contact resistance. However, there
has existed a problem that a naturally oxidized film is
formed on the surface of the base metal between the step
of grinding and removing the surface rolling-affected
layer and the step of allowing the conductive inclusions
to protrude. Once a naturally oxidized film is formed
on the surface of the base metal, even if the step of
allowing the conductive inclusions to protrude is
implemented thereafter, the effect on the improvement
in conductivity by the step of allowing the conductive
inclusion to protrude cannot be obtained sufficiently
due to the existence of the naturally oxidized film. Owing
to this, in order to obtain sufficient conductivity, a
complicated step must be implemented further, leading
to another problem that the production costs are
increased.
~0 Further, after the process of grinding to remove
thesurfacerolling-affectedlayerssothattheconductive
inclusions are allowed to protrude in the vicinity of
the surfaces of the stainless steel plate to thereby reduce
the contact resistance, a process is conducted of
'~5 applying to newly produced surfaces of the stainless steel
5
CA 02558801 2002-12-04
plate a treatment for providing corrosion resistance
thereto. In related art, the passivation treatment has
been used for providing the corrosion resistance to the
newly produced surfaces. However, there has been
existing a problem that a naturally oxidized film is formed
on the newly produced surface during the passivation
treatment. The naturally oxidized film is inferior to
a film in a passive state in corrosion resistance, and
therefore, a further provision of corrosion resistance
has been required. However, even if the passivation
treatment is implemented after a naturally oxidized film
has been formed, the naturally oxidized film interrupts
the passivation of the newly produced surface, and
therefore, the corrosion resistance improvement effect
by the passivation 'treatment cannot be attained
sufficiently. Due to this, in order to obtain a sufficient
corrosion resistance, a further complicated step has to
be implemented, this leading to another problem that the
production costs are increased.
~0
Summary of the Invention
A first object of the present invention is to provide
a fuel cell metallic separator formed by pressing so as
to have a cross section constituted by alternate ridges
?5 and grooves wherein contact areas of surfaces of ridged
6
CA 02558801 2002-12-04
portions to a membrane electrode are enlarged to secure
adesiredsurfacepressure,wherebythecontactresistance
is reduced to thereby improve the power generating
performance and a method for manufacturing the same
separator.
A second obj ect of the present invention i s to provide
a fuel cell metallic separator manufactured by rolling
ametallicmaterialhavingconductiveinclusions,wherein
the fuel cell metallic separator is not affected by
abnormal layers of conductive inclusions produced on the
surfaces thereof by rolling, whereby its power generating
performance is attempted to be improved, as a result,
and a method for manufacturing the same separator,
A third object of the present invention is to provide
a method for manufacturing a fuel cell metallic separator
in which grinding a surface rolling-affected layer on
a base metal and allowing conductive inclusions to
protrude can be implemented in a single step.
A fourth obj ect of the present invention i s to provide
~0 a method for manufacturing a fuel cell metallic separator
in which a passivation treatment can be applied to newly
produced surfaces obtained by grinding on a base metal
at the same time as the grinding to remove surface
rolling-affected layers.
~5 In order to accomplish the first object above, the
7
CA 02558801 2002-12-04
following means are adopted. According to a first aspect
of the present invention, there is provided a fuel cell
metallic separator comprising:
a metallic plate having alternatively ridges and
grooves in a cross section which are formed by pressing,
each of the ridge portions having a flattened surface
which is brought into contact with a membrane electrode
assembly, the flattened surface being formed by removing
a part of the ridged portion after pressing.
In the fuel cell metallic separator, it is preferable
that a removed amount of the surface of the ridged portion
is 3~.~m or larger.
Further, according to a second aspect of the present
invention, there is also provided a method for
I5 manufacturing a fuel cell metallic separator comprising:
forming a metallic plate having alternatively
ridges and grooves in a cross section, by pressing, and;
removing a part of each of the ridged portions so that
each of the ridge portions has a flattened surface. In
this method, it is preferable that a removed amount of
the surface of the ridged portionis equal to or larger
than 3~m. As a method for removing the surface of the
ridged portion, there are an electrochemical method such
as electrolytic etching, a chemical method such as etching
and a physical method such as cutting or sandblasting.
8
CA 02558801 2002-12-04
Further, the inventor came to }:now that the thickness
of the abnormal layer produced on the surfaces of the
separator by rolling is something like in the order of
2' o~ the total thickness, and therefore the present
invention was eventually completed based on this ):nowledge .
Namel y, in order to accomplish the second object above,
according to a third aspect of the present invention,
there is provided a fuel cell metallic separator formed
by rolling a metallic material having conductive
inclusions and removing a surface of the metallic material
after rolling by an amount corresponding to 2~ or more
of a thickness of the metallic material after rolling
so that the conductive inclusions are allowed to protrude
from the surface of the metallic material after rolling.
According to the fuel cell metallic separator of
the third aspect of the present invention, since the
surfaces of the separator are removed by 2~ or more of
the thickness of the metallic material after the material
has been rolled, abnormal layers produced on the surfaces
z0 of the metallic material by rolling are removed.
Therefore, the surfaces of the metallic material are made
good and the conductive inclusions are allowed to protrude
therefrom. Due to this, when the metallic separators so
manufactured are incorporated in a fuel cell, the contact
resistance relative to a membrane electrode assembly is
9
CA 02558801 2002-12-04
reduced to thereby improve its po4aer generating
performance.
Further, according to a forth aspect of the present
invention, there is also provided a method for
o manufacturing fuel cell metallic separator comprising:
obtaining a blank by rolling a metallic material
having conductive inclusions, and;
removing a surface of the blank by an amount corresponding
to 2~ or more of a thickness of the blank so that the
conductive inclusions are allowed to protrude from the
surface of the blank. As a method for removing the
surfaces, there are an electrochemical method such as
electrolytic etching, a chemical method such as etching
and a physical method such as cutting or sandblasting.
In addition, in a case where the blank is formed
into a final separator shape by pressing the blank in
such a manner as to form alternate ridges and grooves
on the blank, the surface removing step may be implemented
either before or after the blank is pressed. For the
ZO separator so pressed, since surfaces of ridged portions
constitute contact portions to the membrane electrode
assembly, the present invention may be limited such that
the surface removing process according to the present
invention is applied only to the surfaces of the ridged
portions . Furthermore, in order to improve the corrosion
CA 02558801 2002-12-04
v
resistance,apassivationtreatmentmayfinally beapplied
to the surfaces of the separator.
In order to accomplish the third object above,
according to a fifth aspect of the present invention,
there is provided a method for manufacturing a fuel cell
metallic separator having conductive inclusions in its
metallic texture, comprising:
blasting a liquid containing two or more kinds of abrasives
having different particle diameters to a blank that has
been rolled.
There exists, in its metal texture of a blank for
a metallic separator, conductive inclusions having a
hardness higher than that of a base metal. Therefore,
normally, a method for manufacturing a fuel cell metallic
separator requires steps of grinding the surface of the
base metal for removing the conductive inclusions as well
as the parent phase and grinding only the surface of the
base metal so as to allow the conductive inclusions to
protrude . A wet-blasting method is used as one of common
means used in these steps . In general, this is a method
for blasting a liquid containing a single kind of abrasives
from a slit-like injection port to a body to be ground.
In the step of grinding to remove the surface of the base
metal, abrasives having a large particle diameter are
'~5 used which can produce kinetic energywhich is large enough
11
CA 02558801 2002-12-04
in magnitude to grind conductive inclusions as well as
the parent phase. In contrast, in the step of allowing
the conductive inclusions to protrude, abrasives having
a small particle diameter are used which can produce
kinetic energywhich is small but large enough in magnitude
to grind only the surface of the base metal.
On the contrary to this, the method for manufacturing
a fuel cell metallic separator according to the present
invention uses a specific wet blasting method for blasting
a liquid containing two or more kinds of abrasives having
different particle diameters to a separator.
Consequently, according to the present invention, not
only the parent phase but also the conductive inclusions
are ground to be removed by the abrasives having a large
particle diameter, and at the same time as this occurs,
only the surface of the base metal is ground by the
abrasives having a small particle diameter. Therefore,
allowing the conductive inclusions to protrude as well
as grinding and removing the surface of the base metal
can be implemented in a single step, whereby the formation
of a naturally oxidized film on the surface of the base
metal can be prevented and a superior conductivity
improving effect can be obtained. In addition, according
to the present invention, since the related-art
?5 complicated steps are no more required, there can be
22
CA 02558801 2002-12-04
provided an advantage that the production costs can be
reduced to a lower level. Furthermore, in the fuel cell
using the separators, a superior power generating voltage
can be exhibited.
In addition, the step of blasting the liquid
containing two or more kinds of abrasives having different
particle diameters may be carried out after the separator
blank has been pressed or before the pressing is completed.
Furthermore, in the manufacturing method according to
the present invention, a passivation treatment is
preferably applied to the surface of the separator blank,
and this passivation treatment applying step may be
implemented in any step after the wet-blasting step has
been completed. In addition, any passivation treatment
liquid may be used provided that the liquid can form a
passive-state film on the surface of the base metal of
the separator.
Further, in order to accomplish the fourth object
above, according to the sixth aspect of the present
invention, there is provided a method for manufacturing
a fuel cell metallic separator having conductive
inclusions in its metal texture, the method comprising:
blasting a passivation treatment liquid mixed with
abrasives to the separator.
Z5 As a common method far grinding a fuel cell metallic
13
CA 02558801 2002-12-04
separator using a wet-blasting process, there is a method
in which a separator body to be ground is ground by blasting
water mixed with'abrasives to the separator body from
a slit-like injection port. On the other hand, in the
method for manufacturing a fuel cell metallic separator
according to the present invention, a unique wet-blasting
process is used in which a passivation treatment liquid
mixed with abrasives is blasted to the separator.
According to this method, the surface rolling-affected
layers of the separator be ground can be removed by blasting
the abrasives to the separator surfaces so that the
conductive inclusions can be exposed. Further, at the
same time as this grinding process takes place, a
passivation treatment can be applied to newly produced
surfaces of the separator which results from the grinding
by blasting the passivation treatment liquid.
There is no limitation on the passivation treatment
liquid that is used in the method for manufacturing a
fuel cell metallic separator according to the present
invention provided that a film in a passive state can
be formed on the surface of the base metal of the separator.
In the present invention, however, the passivation
treatment liquid is preferably nitride acid. In addition,
the process of blasting the passivation treatment liquid
mixed with the abrasives of the present invention may
14
CA 02558801 2002-12-04
70691-22D
be implemented after the separator blank has been pressed or
before the pressing.
In another aspect of the present invention, there
is provided a fuel cell metallic separator formed by rolling
a metallic material having conductive inclusions and
removing a surface of the metallic material after rolling by
an amount corresponding to 2% or more of a thickness of the
metallic material after rolling so that the conductive
inclusions are allowed to protrude from the surface of the
metallic material after rolling, wherein, after removal of
the surface of the surface blank, a surface of the metallic
material is applied with a passivation treatment.
In a further aspect of the present invention,
there is provided a method for manufacturing a fuel cell
metallic separator comprising: obtaining a blank by rolling
a metallic material having conductive inclusions, and:
removing a surface of the blank by an amount corresponding
to 2% or more of a thickness of the blank so that the
conductive inclusions are allowed to protrude from the
surface of the blank, further comprising, after removal of
the surface of the blank, applying a passivation treatment
to a surface of the blank.
In a further aspect of the present invention,
there is provided a fuel cell comprising: a membrane
electrode assembly; and a metallic separator including a
metallic plate having alternatively ridges and grooves in a
cross section which are formed by pressing, each of the
ridge portions having a flattened surface which is brought
into contact with the membrane electrode assembly, the
flattened surface being formed by removing a part of the
ridged portion after pressing.
CA 02558801 2002-12-04
' 7069-22
r ..
~r~=f Descripmon o= the Drawyngs
;> F iG . 1 is a C~laCfraIC~ sC!oWi ng the CGT':C~l:it' G_ a .5'~.~~ar c tOr
~CC~rdln~ t0 tree preSeilt "_Y1V~T'it~GT:;
Fig. ' is an image of a separator that ?-eprescnts
separators manuzactured in exaruples of the iresent
invention;
1C) Fig . 3 is a sectional view of a current coil ect i ng
portion (a portion where alternate ridges and grooves
are formed) of the separators manufactured in the examples;
Fig. 4 is.a graph showing the results of contact
resistances measured in the examples;
15 Fig. 5 is an image of a separator that is to be
manufactured in examples of the present invention;
Fig. 6 is an image of the surface of the separators
of the~examples of the present invention;
Fig. 7 is an image of the surface of separators of
'~0 Comparison Examples which correspond to those of the
invention;
Fig. 8 is a graph showing measured contact
res~~stances of the examples of the present invention;
Fig. 9 is a graph showing measured corrosion current
'5 densities of the examples of the present invention;
15a
CA 02558801 2002-12-04
Fig. 10 is a diagram showing a relationship between
power generating current density and power generating
voltage in a fuel 'cell using separators according to the
present invention and a comparison example; and
Fig. 11 is a diagram showing the relationship between
power generating voltage and power generating time in
a fuel cell using the separators of the example of the
present invention or the comparison example.
Detailed Description of the Invention
Fig. 1 illustrates the concept of a separator
according to a first embodiment of the present invention,
in which a surface 11 of a ridged portion 10 is removed
and a flattened surface 12 is newly formed. In Fig. I,
a shaded portion denotes a portion that is removed,- and
a range indicated by "a" or the surface 12 constitutes
a contact surface which is brought into contact with a
membrane electrode assembly. Incidentally, "b" denotes
a contact area to the membrane electrode assembly in a
state in which the surface 11 is not removed or of the
related-art ridged portion 10.
As is clear in Fig. 1, the contact surface is enlarged
by removing the surface of the ridge portion, and due
to this, a desired surface pressure relative to the
membrane electrode assembly is ensured, and the contact
16
CA 02558801 2002-12-04
resistance is reduced to thereby improve the power
generating performance. In a state in which the surface
of the ridge portion is removed, in case the round shape
of the corner portions generated by pressing is removed,
the contact area is enlarged further, which is preferable .
Stainless steel is preferably used for the separator
according to the present invention. Since stainless
steel in which nonmetal conductive inclusions which
constitute a conductive path are dispersed into the
metallic texture exhibits good conductivity, it is
especially preferable as a material for fuel cell
separators. With such stainless steel being applied to
the present invention, the conductive inclusions are
allowed to protrude from the surface when the surface
of the ridge portion is removed, whereby the improvement
in function as the separator can be attempted. In case
an amount of the surface that is removed after pressing
lowers below Sum, the effect of reducing the contact
resistance relative to the membrane electrode assembly
cannot be obtained largely, and therefore, the removal
amount is preferably equal to or larger than 3~m.
[Examples]
Next, examples of the present invention will be
described.
A. Manufacture of Separator
17
CA 02558801 2002-12-04
[Examples 1 to 10]
An austenite stainless steel plate having a
thickness of 0.2mm'was pressed to obtain a required number
of square separator blanks of 92mm wide and 92mm long.
Fig. 2 shows these separator blanks each have a current
collecting portion having a cross section formed to have
alternate ridges and grooves at the center thereof and
a flat edge portion around the periphery of the current
collecting portion. Fig. 3 illustrates part of the cross
section and dimensions of the current collecting portion
of the separator blank. Next, masking was applied to
interior surfaces of the grooves on both sides of the
separator blank, and only surfaces of ridged portions
on the sides of the separator blank were removed by
electrolytic etching to thereby flatten the surfaces.
As shown in Table 1, amounts (thicknesses) of the surfaces
that were removed were lam, 2~m, 3~.m, 4~m, 5~m, 6~m, 7~tm,
10~m, 20~m and 50um, whereby 10 kinds of separators which
differ in removed amount were manufactured and they are
represented by Examples 1 to 10, respectively. Note that
an adhesive tape produced by Fleon Industries Co., Ltd.
under the trade name of F-7034 (0.8mm thick) was used
as a masking material. In addition, a phosphoric acid
electrolytic etching liquid produced by Jusco Co., Ltd.
under the trade name of 6C016 was used. Then electrolytic
18
CA 02558801 2002-12-04
etching was carried out in the following conditions;
temperature was 50 degrees centigrade and current density
was 0.125A/cm~ .
[Comparison Example]
The separator blank in which the surfaces of the
ridged portions are not removed was made a separator of
comparison example.
[Table 1]
Removed Amounts Contact
(~~m) Resistance
to MEA (mS2/cm-)
Comparison 0 68
Example
Example 1 1 30
Example 2 2 27
Example 3 3 16
Example 4 4 17
Example 5 5 16
Example 6 6 ~15
Example 7 7 15
Example 8 10 14
Example 9 20 14
Example 10 50 14
B. Measuring Contact Resistances
Next, fuel cell units were manufactured using the
separators of Examples 1 to 10 and the comparison example,
respectively, in which the separators of each example
were laminated on sides of a membrane electrode assembly
as an unit, and the units for each example were activated
to generate power to measure contact resistances of the
19
CA 02558801 2002-12-04
separators of those examples relative to the membrane
electrode assemblies. The results of the measurement
were also shown ir1 Table l, and the relationship between
the removed amount of the surface of the ridged portion
'3 and contact resistance axe graphed in Fig. 9.
As is clear from Fig. 4, it was verified that the
contact resistances of the separators of Examples 1 to
are far lower than that of the separator of the
comparison example and that flattening the surface of
10 the ridged portion by removing part thereof contributed
to the improvement of the power generating performance.
In particular, the contact resistance reduced remarkably
with the removed amount of the surface of the ridged portion
being 3~.m. Then, it was confirmed that same reduction
effect was expected by a further increase in removed
amount.
Next, the metallic separator according to a second
embodiment of the present invention will be explained.
An austenite stainless steel plate having conductive
~0 inclusions is raised as a material for the separator
according to the second embodiment of the present
invention. Specifically speaking, an austenite
stainless steel plate is used which contains respective
components shown in Table 2 and in the remaining portion
thereof Fe, B and unavoidable impurities and in which
CA 02558801 2002-12-04
Cr, Mo and B satisfy the following expression ( 1 ) . B is
deposited on the surface as a boride of M B or MB type
and a boride of Ni (C, B):. type, and these borides are
conductive inclusions which form a conductive path on
the surface of the separator.
Cr(wt'-:)+3xMo(wt-:)-2.5xB(wt-:)~17 . . . (1)
[Table 2]
C Si Mn P S A1
0.15 0. 01~'1 0. 01~-2 c 0. 035 ~ 0. 0. 001~-
. 5 . 5 O1
0.2
N Cu Ni Cr Mo
c 0. 3 0~-3 7~-50 17~-30 0~-7
(per cent by weight)
[Examples)
Next, examples of the present invention will be
described.
A. Manufacture of Blank
A thin plate having a thickness of 0 . 2mm was obtained
by cold rolling a stainless steel containing respective
components shown in Table 3, as well as Fe and unavoidable
impurities in the remaining portion thereof with an
annealing process being suitably carried out during
pressing. Next, a required number of square blanks of
100mm wide and 100mm long were obtained by cutting them
out of the thin plate so obtained.
21
CA 02558801 2002-12-04 ~,_.x
[Table 3]
C Si Mn ,P S Cu Ni Cr
0.073 0.28 0.13 0.015 0.001 0.11 10.1 20.9
Mo Nb Ti A1 N B
2.03 - - 0.08 0.030 0.60
(per cent by weight)
B. Surface Removing Process and Pressing
[Example 11]
The following wet-blasting process was applied to
both surfaces of the blank to thereby remove the surfaces
by 4~.m. Alumina particles (produced by Fuj i Seisakusho
1U Co., Ltd. under trade name of Fujirandom WA#300) having
a particle diameter of 0.3mm was mixed into water as
grinding particles, and this grinding particles mixed
water was blasted to the surfaces at a blasting pressure
of 1kg/cm' for 20 seconds . Next, this blank was pressed
15 into a predetermined separator shape to thereby obtain
a separator of Example 11.
[Example 12]
After the blank was pressed into a predetermined
separator shape, the same wet-blasting process as that
?0 carried out for Example 11 was applied to both surfaces
of the blank to thereby obtain a separator of Example
12 in which the surfaces were removed by 4~.m.
[Example 13]
22
CA 02558801 2002-12-04
After the blank was pressed into a predetermined
separator shape, the same sand blasting process as that
carried out for Example 15 was applied to both surface
of the blank so as to remove the surfaces by lU~~m to thereby
obtain a separator of Example 16.
[Comparison Example 11]
The blank was only pressed into a predetermined
separator shape and no surface removing process was
carried out, the blank being made to be a separator of
Comparison Example 11.
[Comparison Example 12]
A separator of Comparison Example 12 was obtained
in the similar manner as Example 11 except that both
surfaces were removed by 1.5~m in amount.
[Comparison Example 13]
A separator of Comparison Example 13 was obtained
in the similar manner as Example 12 except that both
surfaces were removed by 1.5~.~m in amount.
(Comparison Example 14]
~0 A separator of Comparison Example 14 was obtained
in the similar manner as Example 11 except that both
surfaces were removed by 2.5~m in amount.
[Comparison Example 15]
A separator of Comparison Example 15 was obtained
~5 in the similar manner as Example 12 except that both
24
CA 02558801 2002-12-04
surfaces were removed by 2.5E~m in amount.
Note that Fig. 5 shows a pressed separator which
is something like those obtained in the examples of the
present invention and the comparison examples, and this
separator has at the center thereof a current collecting
portion which is pressed so as to have a cross section
constituted by alternate ridges and grooves and a flat
edge portion around the periphery of the current
collecting portion.
C. Observation of Surfaces
The surfaces of the separators of Example 11 and
Comparison Example 11 were observed by a microscope . Fig.
6 is an image of the surface of the separator of Example
11 . Fig. , 7 is an image of the surface of the separator
of Comparison Example 11. It is observed that unbroken
good conductive inclusions having a particle diameter
of in the order of 5~m were allowed to protrude from the
surface of the separator of Example 11 . On the other hand,
it is observed that finely broken conductive inclusions
~0 aggregated on the surface of the separator of Comparison
Example 11.
D. Measurement of Power Generating Voltage
Using the respective separators of Examples 11 to
16 and Comparison Example 11 to 15, respectively, fuel
cell units were manufactured in which the separators were
CA 02558801 2002-12-04
laminated to both sides of a membrane electrode assembly
(MEA) , and the fuel cell units so manufactured were then
activated to generate power to measure power generating
voltages when a current of 0.5A/cm2 was generated at such
timings at an initial point in time (0 hour) and points
in time; 10 hours has elapsed, 100 hours has elapsed,
2000 hours has elapsed and 3000 hours has elapsed,
respectively. The results were shown in Tables 4A and
4B together with manufacture processes (order of surface
removing process and pressing) and surface removed
amounts.
[Table 4A]
Manufacture Processes Surface Removed
Amounts (~tm)
Example 11 wet-blasting -> pressing 4
Example 12 pressing -> wet-blasting 4
Example 13 nitro-hydrofluoric acid 5
etching -> pressing
Example 14 pressing -> 5
nitro-hydrofluoric acid
etching
Example 15 sand blasting -> pressing 10
Example 16 pressing -> sand blasting 10
Comparison pressing only 0
Example 11
Comparison wet-blasting -> pressing 1.5
Example 12
Comparison pressing -> wet-blasting 1.5
Example 13
Comparison wet-blasting -> pressing 2.5
Example 14
Comparison pressing -> wet-blasting 2.5
Example 15
26
CA 02558801 2002-12-04
[Table 9B]
Powez
Generating
Voltage
(V)
when
a Current
of 0.5A/cm
is generated
Ohour IO 100 1000 2000 3000
hours hours hours hours hours
Example 11 0.7 0.7 0.7 0,7 U.7 0,7
Example 12 0.7 0.7 0.7 0.7 0.7 0.7
Example 13 0.7 0.7 0.7 0.7 0.7 0.7
Example 14 0.7 0.7 0.7 0.7 0.7 0.7
Example 15 0.7 0.7 0.7 0.7 0.7 0.7
Example 16 0.7 0.7 0.7 0.7 0.7 0.7
Comparison 0.7 0.65 0.63 0.55 0.43 0.24
Example 11
Comparison 0.7 0.69 0.66 0.63 0.59 0.55
Example 12
Comparison 0.7 0.68 0.66 0.64 0.59 0.55
Example 13
Comparison 0.7 0.69 0.68 0.66 0.65 0.63
Example 14
Comparison 0.7 0.68 0.66 0.65 0.64 0.61
Example 15
As is clear from Table 2, with the separators of
the examples of the present invention, a power generating
voltage at the initial point in time was still maintained
even at the point in time when 3000 hours had elapsed,
whereas with the separators of Comparison Examples, it
is observed that the initial power generating voltage
was reduced with time, this verifying the effectiveness
of the present invention.
E. Effect of Passivation Treatment
Next, the verification was made with respect to the
superiority resulting when a passivation treatment was
27
CA 02558801 2002-12-04
finally applied to the surfaces of the separator.
[Example 17]
An electrolytic etching process was applied to the
surfaces of the bland: so as to remove the surfaces by
4ym. A phosphoric acid electrolytic etching liquid
(produced by Jusco Co. , Ltd. under the trade name of 6C016)
was held at 50 degrees centigrade, a current having a
current density of 0.125A/cmv was conducted through the
etching liquid, and the blank was submerged in the etching
bath for 10 minutes. Next, the blank was then pressed
into a predetermined separator shape. Finally, the
pressed separator was submerged for 10 minutes in a liquid
bath containing 50 per cent by weight of nitride acid
for passivation treatment of the surfaces to thereby
obtain a separator of Example 17.
[Comparison Example 16]
The same passivation treatment as done for Example
17 was applied to the separator of Comparison Example
11 to thereby obtain a separator of Example 16.
Z0 The separators of Example 17, Comparison Example
11 and Comparison Example 16 were brought into contact
with membraneelectrodeassembly,respectivelytomeasure
contact resistances of the respective separators. The
results of the measurements were shown in Fig. 8. In
Z5 addition, corrosion current densities of the separators
28
CA 02558801 2002-12-04
t
of Example 17, Comparison Example 11 and Comparison
Example 16 were measured. The results of the measurements
were shown in Fig: 9. As is clear from the results, the
separator of Example 17, to the surfaces of which the
o passivation treatment was applied, showed the lowest
values for both contact resistance and corrosion current
density. Consequently, it can be expected that a
separator to the surfaces of which a passivation treatment
isappliedexhibitsahigherpowergeneratingperformance.
Next, the metallic separator according to a third
embodiment of the present invention will be explained.
An austenite stainless steel plate having conductive
inclusions is raised as a material for the separator
according to the third embodiment of the present invention,
as is the case with that of the second embodiment of the
presentinvention. Thatis, anaustenitestainlesssteel
plate is used which contains respective components shown
in Table 2 above and in the remaining portion thereof
Fe, B and unavoidable impurities and in which Cr, Mo and
ZO B satisfy the above-mentioned expression (1), B is
deposited on the surface as a boride of M;.B or MB type
and a boride of M~.3(C, B)~ type, and these borides are
conductive inclusions which form a conductive path on
the surface of the separator.
[Example]
29
CA 02558801 2002-12-04
Next, the effectiveness of the present invention
will be described in detail using an example of the present
invention.
A. Manufacture of Separator
<Example>
An austenite stainless steel plate containing
respective components shown in Table 5 and in the remaining
portion thereof Fe and unavoidable impurities was cut
into a square shape which is 100mm wide and 100mm long
1U to thereby obtain a blank for a separator . Next, tap water
mixed with 33.3 per cent by weight of two kinds of alumina
particles whose particle diameters are 60~.~m and 180~m,
respectively, at a weight ratio of 1 to 1 as grinding
particles and held at a temperature of 30 degrees
centigrade was sprayed to both sides of the blank from
a spray nozzle at a spraying pressure of lkg/cm- for 30
seconds, whereby grinding the parent phase and allowing
conductive inclusions to protrude were implemented using
the wet-blasting method. Next, the blank was rinsed and
~0 after it dried out, the blank was pressed with a press
load of 50 tons and a separator according to the example
was obtained.
CA 02558801 2002-12-04
[Table 5]
IC iSi ~Mn ~P ~S ~A1 ~N
X0.073 0.28 0.13 0.015 0.001 0.08 0.03 r0.11
Ni Cr Mo B
10.1 20.9 2.03 0.60
(per cent by weight)
<Comparison Example.
Next, tap water mixed with 33.3 per cent by weight
of alumina particles whose particle diameters is 180(,~m
as grinding particles and held at a temperature of 30
degrees centigrade was sprayed to both sides of a separator
blank which was similar to one used for the example from
a spray nozzle at a spraying pressure of lkg/cm- for 30
seconds, whereby grinding by the wet-blasting method was
implemented. Next, the blank was rinsed and after it dried
out, the blank was pressed with a press load of 50 tons
and a separator according to the example was obtained.
Next, tap water mixed with 33.3 per cent by weight of
alumina particles whose particle diameters is 60~~m as
grinding particles and held at a temperature of 30 degrees
centigrade was sprayed to the sides of the separator blank
from the spray nozzle at the spraying pressure of lkg/cm'
for 30 seconds, whereby allowing conductive inclusions
toprotrudewasimplemented usingthewet-blasting method.
Thereafter, the blank was rinsed and after it dried out,
the blank was pressed with a press load of 50 tons and
31
CA 02558801 2002-12-04
a separator according to the comparison example was
obtained.
B. Deterioration~with Age of Power Generating Voltage
Manufactured using the separators of the example
i of the present invention and the comparison example which
were obtained as has been described above were fuel cell
units in each of which the separators were laminated on
sides of a membrane electrode assemble (MEA), and the
units were activated so as to generate power and
deteriorations in power generating voltage as the power
generating current densityincreasesweremeasured. The
results of the measurement are shown in Fig. 20.
As is clear from Fig. 10, with the fuel cell unit
using the separators of the example of the present
invention which was manufactured by implementing the steps
of grinding a surface rolling-affected layer and allowing
conductive inclusions to protrude at the same time, the
deterioration in power generating voltage as the power
generating current density increases was extremely low
ZO when compared with the fuel cell unit using the separators
of the comparison example which was manufactured by
implementing the steps of grinding a surface
rolling-affected layer and allowing conductive
inclusions to protrude sequentially.
Next, the metallic separator according to a fourth
32
CA 02558801 2002-12-04
embodiment of the present invention will be explained.
An austenite stainless steel plate having conductive
inclusions is raised as a material for the separator
according to the third embodiment of the present invention,
as is the case with that of the second embodiment of the
present invention. That is, an austenite stainless steel
plate is used which contains respective components shown
in Table 2 and in the remaining portion thereof Fe, B
and unavoidable impurities and in which Cr, Mo and B satisfy
1.0 the above-mentioned expression (1), B is deposited on
the surface as a boride of M-B or MB type and a boride
of M_3(C, B)type, and these borides are conductive
inclusions which form a conductive path on the surface
of the separator.
15 [Example]
Next, the effectiveness of the present invention
will be described in detail using an example of the present
invention.
A. Manufacture of Separator
20 <Example>
An austenite stainless steel plate containing
respective components shown in Table 6, as well as Fe
and unavoidable impurities in the remaining portion
thereof and having a thickness of 0.2mm was cut into a
25 square separator of 100mm wide and 100mm long to thereby
33
CA 02558801 2002-12-04
obtain a separator blank. Next, 5 per cent by weight of
nitride acid mixed with 33.3 per cent by weight of alumina
particles having a particle diameter of 60~~m as grinding
particles and held at 50 degrees centigrade was blasted
to both surfaces of the blank at a blasting pressure of
lkg/cm- for 30 seconds so that grinding and passivation
treatmentusingthewet-blastingprocesswerethuscarried
out . Next, after it was rinsed and dried, the blank was
pressed with a press load of 50 tons to thereby obtain
a separator of an example of the present invention.
[Table 6]
C Si Mn P S A1 - N Cu
0.073 0.28 0.13 0.015 0.001 0.08 0.03 0.11
Ni Cr Mo -
10.1 20.9 '2.03 0.60-
(per cent by weight)
<Comparison Example>
Tap water mixed with 33.3 per cent by weight of
alumina particles having a particle diameter of 60~tm as
grinding particles and held at 30 degrees centigrade was
blasted to both surfaces of the same blank as used for
the above example at a blasting pressure of lkg/cm= for
?0 30 seconds and grinding using the wet-blasting process
was thus carried out. Next, the blank was submerged in
5 per cent by weight of nitride acid which was held at
50 degrees centigrade for 3 minutes and a passivation
34
CA 02558801 2002-12-04
treatment was thus carried out . Next, after it was rinsed
and dried, the blank was pressed with a press load of
50 tons to therei~y obtain a separator of a comparison
example.
B. Deterioration with Time of Power Generating Voltage
Fuel cell units were manufactured using the
separators of the example of the present invention and
the comparison example, respectively, which were obtained
as has been described above in which the separators are
laminated on both sides of a membrane electrode assembly
(MEA), and the units were activated to generate power,
whereby a deterioration in power generating voltage as
power generating time elapses when a current of 0.5A/cm'
was measured for each example. The results of the
measurements were shown in Fig. 11.
As is clear from Fig. 11, with the fuel cell unit
using the separators of the example of the present
invention in which no naturally oxidized film but a film
in a passive state was formed on the surfaces of the
ZO separator and which is superior in corrosion resistance,
there was extremely little deterioration in power
generating voltage even if power was generated over a
long period of time . In contrast, with the fuel cell unit
using the separator of the comparison example in which
a film in a passive state was formed on the surfaces of
CA 02558801 2002-12-04
the separator via a naturally oxidized film, it was found
that the power generating voltage was reduced as the power
generating time elapsed.
Thus, as has been described heretofore, according
to the present invention, in the fuel cell metallic
separator formed by pressing so as to have a cross section
constituted by alternate ridges and grooves, the contact
area at the surface of the ridged portion is enlarged
by removing the surface of the ridged portion that is
brought into contact with the membrane electrode assembly
after pressing so as to make the flattened surface.
Therefore, the desired surface pressure can be ensured,
whereby the contact resistance relative to the membrane
electrode assembly is reduced, and as a result, there
can be provided an advantage that the power generating
performance is improved.
As has been described heretofore, according to the
present invention, the abnormal layers produced on the
surfaces of the metallic material when it is rolled are
removed by removing the surfaces of the metallic material
by 2 0 or more of the thickness of the metallic material
after the material has been rolled, and the resulting
surfaces become good and the conductive inclusions are
allowed to protrude therefrom. Thus, there can be
provided an advantage that the contact resistance relative
36
CA 02558801 2002-12-04
to the entirety of the membrane electrode assembly is
reduced, whereby the improvement in power generating
performance can be attempted.
As has been described above, according to the present
invention, since grinding the surface rolling-affected
layer of a base metal and allowing conductive inclusions
to protrude can be implemented simultaneously by using
the unique wet-blasting method in which the liquid
containing two or more kinds of abrasives having different
1U particle diameters is blasted to a blank_ after the blank
has been rolled, the formation of a naturally oxidized
film on the surface of the base metal can be prevented
to thereby obtain a superior conductivity improvement
effect, and a fuel cell using the separators so
manufactured can exhibit a superior power generating
voltage.
As has been described heretofore, according to the
present invention, by using the unique wet-blasting
process in which the passivation treatment liquid mixed
with abrasives is blasted to the separator, the surface
rolling-affected layers of the separator can be ground
to be removed to thereby allow conductive inclusions to
be exposed by the abrasives so blasted, and at the same
time as this occurs, the passivation treatment can be
applied to newly produced surfaces of the separator which
37
r
CA 02558801 2002-12-04
result from the grinding through blasting the passivation
treatment liquid to the separator.
38
