JP5090800 (B2) 2012-12-05

INTER-CONNECTOR AND SOLID OXIDE FUEL CELL

ARAI SO, ; SUGITA SATOSHI, ; YOSHIDA YOSHIAKI, ; CHIBA
REIICHI, ; KOMATSU TAKESHI, ; ARAKAWA MASAYASU
Applicant(s): NIPPON TELEGR & TELEPH CORP <NTT>
- international: H01M4/86; H01M8/02; H01M8/12
Classification:
- cooperative: Y02E60/521; Y02E60/525
Application
JP20070166089 20070625
number:
Priority
JP20070166089 20070625
number(s):
Also published
JP2009004297 (A)
as:
Inventor(s):

Abstract of JP2009004297 (A)

PROBLEM TO BE SOLVED: To provide a solid oxide fuel cell in which deterioration by
oxidation of an interconnector can be suppressed by using a protection film made of a
material with high conductivity even in a high temperature state such as power generation
operation of the solid oxide fuel cell. ;SOLUTION: A protection film 108 made of
lanthanum nickel ferrite is coated at least on the surface on air electrode side of the air
electrode side interconnector 107. In other words, the surface which is exposed on an
oxidant gas on at least the air electrode side of the air electrode side interconnector 107 is
covered with the protection film 108 made of lanthanum nickel ferrite (LNF).

DESCRIPTION JP5090800
Interconnector and the solid oxide fuel cell

[0001]
[0001] The present invention relates to a solid oxide fuel cell using the interconnector and
which protected with a protective film.

[0002]
[0002] In recent years, as a generator means that high efficiency can be obtained
regardless of the scale of large and small, fuel cell has been attracting attention. Fuel
cells, oxygen is a cell using a chemical reaction between the oxidizing agent gas and the
fuel gas such as hydrogen, such as, it is constructed by sandwiching an electrolyte layer
out with a fuel electrode (fuel electrode) and an oxidant electrode (air electrode) , by
supplying the fuel gas and oxidizer gas, in which the power generation by utilizing as the
main reaction the reverse reaction of electrolysis of water. For example, reforming
methane gas and hydrogen is used as fuel gas, such as oxygen or air is used as the oxidant
gas. In such a fuel cell, power generation efficiency is 45% or more as high as the solid
oxide fuel cell.

[0003]
[0003] Solid oxide fuel cells, that operate at 400~1000 C and the high temperature, high
ion conductivity of the cell electrolyte, and a prone state redox reaction at the electrodes,
the internal resistance and reaction resistance by reducing the loss of power due to, and
obtain the high power generation efficiency as described above. In order to obtain
practically sufficient power generation amount (voltage), the fuel electrode - is used as a
stack structure in which electrically connecting units power generating element composed
of a cathode (single cell) into a plurality series - electrolyte.

[0004]
[0004] When forming such a stack structure, a connecting member called interconnector
between adjacent single cells are used. Interconnector, sometimes each provided on the
fuel electrode side and the air electrode side of the unit cell, and may have been formed in
these other integrally. Further, to each electrode side of the interconnector, the passage for
supplying the fuel gas or oxidant gas (including a groove) is provided in each electrode.
Further, in some cases, such as the reaction product gas and unreacted gas generated as a
result of power generation reaction, it is passage for discharging exhaust gas is provided.

[0005]
[0005] Such interconnector, firstly, in order to electrically connect the adjacent unit cell,
it is necessary that the electric conductivity. Further, in the high temperature generator
operation is performed, when the fuel gas and oxidizer gas in direct contact, so that the
reaction which does not contribute to power generation fuel proceeds are wasted.
Therefore, in the stack structure in which the one of the fuel electrode side and the other
on the air electrode side of the unit cell adjacent are connected to face, the interconnector,
the fuel gas supplied to the fuel electrode of one unit cell, functions as a separator to
allow the oxidizing gas does not intersect supplied to the air electrode of the other unit
cell is required. Further, the interconnector, even in a high temperature state as described
above, even when exposed to the fuel gas and the oxidizing gas, it is required not to also
deteriorate without modification.

[0006]
[0006] In this manner, electron conductivity, function as a partition wall, and the
interconnector stability at high temperatures is required, and heat-resistant metallic
material such as ferritic stainless steel, a conductive ceramic material is used . In
particular, ferritic stainless steel, excellent in workability, complex shapes, including a
flow path of the gas can be easily formed, the mechanical strength is also better, also, in
general because it is less expensive than the ceramic, interconnector It is mainly used as a
material (see Patent Document 1).

[0007]
[0007] However, even in the interconnector which is composed of ferritic stainless steel,
because of a long period exposed environments such as the oxygen-containing gas and
high-temperature steam, there such as an oxide film is formed on the surface oxidation
occurs, such as , problems such as the connection resistance gradually deteriorated to
increase occurs. In contrast, coated with a layer of conducting oxide on the surface of the
interconnector, thereby suppressing the deterioration in the oxidizing atmosphere as
described above has been proposed. Interconnector protective film is coating of
conductive oxide, so that the surface of the metal is prevented from being directly
exposed to the oxidizing gas.

[0008]
[0008] Fuel single cell of the battery, the connection layer provided on each electrode or
the electrode and the like is composed of ceramic (sintered body) of a metal oxide, will it
be interconnector is connected. Here, the unprotected film is formed on the
interconnector, comes into contact and a metal and a metal oxide, a metal portion affected

by the oxidizing gas is deteriorated, such as connection resistance increases adverse effect
occurs. Also, if you are using a connection layer, the surface of the interconnector is to be
covered by the connection layer, the connection layer is porous state is formed by
sintering a conductive paste, the interconnector not been from that completely covers the
surface. Therefore, in the state of covering the connection layer, a state in which the
oxidizing gas reaches the surface of the interconnector can not prevent the deterioration
of the surface of the interconnector, thereby impairing the characteristics of the fuel cell
as a result .

[0009]
[0009] with respect to the above, when the protective film is coated, now oxidant gas is
prevented from directly contacting the surfaces of the interconnector, the portion where
the interconnector is connected to the electrode and the connection layer in will be
contact between the metal oxide and metal oxide. Thus, if the connection between the
metal oxide (contact), small influence of the oxidizing gas, as a result, it is possible to
suppress a certain degradation of the fuel cell.

[0010]
[0010] The protective film to be coated for preventing deterioration of the interconnector
described above, is stable to oxidation at the operating temperature of at least the fuel
cell, it is high electron conductivity are required, such as Do oxide material, lanthanum
chromite, and the partially substituted material has been proposed (see non-Patent
Document 1). Further, (see Non-Patent Document 2) as a material of the protective film
to be coated, lanthanum strontium manganite and the partially substituted material has
been proposed to prevent deterioration of the interconnector.

[0011]
[0011] JP 2005-174884 JP C.Johnson, et al., "PEROVSKITE BACED PROTECTIVE
COATINGS FOR SOLID OXIDE FUEL CELL METALLIC INTERCONNECTS",
Electrochemical Society Proceedings, Vol.2005-07, pp.1842-1850, 2005. L.Mikkelsen, et
al., "INTERFACE RESISTANCE BETWEEN FeCr ALLOYS AND
La0.85Sr0.15MnO3", Electrochemical Society Proceedings, Vol.2005-07, pp.1832-1841,
2005.

[0012]
[0012] However, the conventional protective film material described above, there is a
problem similar to the one shown below. First, the thermal expansion coefficient of the
compound of lanthanum chromite is significantly different from the thermal expansion
coefficient of the ferritic stainless which is a general heat-resistant metal. Therefore,

during the power generating operation to become a high temperature, is easily enter such
as the formation and cracks in the protective film, there is a problem that it is difficult to
protect the interconnector from the oxidant gas. Further, the compounds of lanthanum
chromite system, because it contains chromium, which is in contact directly to the air
electrode, there is a problem of damaging the so-called chromium poisoning to the air
electrode.

[0013]
[0013] On the other hand, in the material of lanthanum strontium manganite system, the
electron conductivity is not very high, the resistance component of the interconnector is
increased, the characteristics of the fuel cell stack structure is lowered. Further, the
material of the lanthanum strontium manganite-based, has high reactivity with chromium,
if the interconnector is composed of ferritic stainless steel, the protective film during the
power generation operation chromium contained therein is a high temperature diffusion
and react with components of the protective film, there is a problem of causing
deterioration.

[0014]
[0014] The present invention has been made to solve the above problems, a protective
film conductivity is composed of a material having a high, high-temperature conditions
such as during power generation operation of the solid oxide fuel cell in also aims to
allow suppressing deterioration due to oxidation of the interconnector.

[0015]
[0015] interconnector according to the present invention, a fuel electrode, disposed
electrolyte layer over the anode, and a plurality of unit cells composed of arranged air
electrode over the electrolyte layer are laminated It is disposed between the unit cells
adjacent stack structure, a interconnector formed of stainless steel, made of lanthanum
nickel ferrite which is formed to cover the entire area of the interconnector to the surface
on the side of at least the air electrode protection is obtained by the so comprises a film.

[0016]
[0016] The above interconnector, for example, may be composed of a ferritic stainless
steel. In addition, the protective film of the interconnector, for example, may iron mol
number / nickel mol number is composed of 9 or less of lanthanum nickel ferrite.

[0017]

[0017] Further, the solid oxide fuel cell according to the present invention is a solid oxide
fuel cell using the interconnector described above, the fuel electrode, disposed electrolyte
layer over the anode, and the electrolyte layer and a plurality of single cells stacked
consists disposed air electrode over, comprising at least a interconnectors disposed
between the unit cells adjacent, the air electrode, composed of lanthanum nickel ferrite it
is obtained by the as.

[0018]
[0018] In the solid oxide fuel cell, a single cell, it is preferable is a flat plate type. Further,
the single cells may When it is a fuel electrode support type in which the fuel electrode
and the support.

[0019]
[0019] As described above, according to the present invention, on the side of at least the
air electrode interconnector, since such a protective film made of lanthanum nickel
ferrite, protective film conductivity is a material having high used even in high
temperature conditions such as during power generation operation of the solid oxide fuel
cell, an excellent effect of suppressing the deterioration due to oxidation of the
interconnector can be obtained.

[0020]
[0020] Hereinafter, will be described with reference to the drawings exemplary
embodiments of the present invention. Figure 1 is a sectional view showing a
configuration example of a solid oxide fuel cell according to an embodiment of the
present invention. The solid oxide fuel cell, first, the fuel electrode side connection layer
102, fuel electrode 103, an electrolyte layer 104, cathode 105 and an air electrode-side
connection layer 106, is provided with a respective single cells are laminated in this order
. Further, the solid oxide fuel cell is a stacked structure in which a plurality of unit cells
are stacked, comprises a fuel electrode interconnector 101 and the air electrode
interconnector 107 is disposed between adjacent unit cells there.

[0021]
[0021] fuel electrode interconnector 101 and the air electrode interconnector 107, for
example, is formed from a well-known ferritic stainless steels. Further, for example,
single cell and each interconnector is formed in plan view circular. Further, the fuel
electrode side connection layer 102 and the air electrode-side connection layer 106 may
be provided as necessary, a layer of metal formed on a porous body or mesh made of
sintered body of fine particles having a conductive property, such as constructed from,

provided with a conductive it is to transmit the gas. By using the connecting layer, it can
be reduced connection resistance between each electrode and the interconnector.

[0022]
[0022] Here, the air electrode 105 is, for example, lanthanum nickel ferrite (La (Ni, Fe) O
3: LNF), lanthanum strontium manganate ((La, Sr) MnO 3: LSM), lanthanum strontium
cobaltite ( (La, Sr) CoO 3: LSC), lanthanum strontium ferrite ((La, Sr) FeO 3: LSF), and
samarium strontium cobaltite ((Sm, Sr) CoO 3: SSC), such as, a conductive metal those
composed of a sintered body of an oxide.

[0023]
[0023] Further, the electrolyte layer 104 is yttria-stabilized zirconia (YSZ), samaria
stabilized zirconia (SSZ), scandia stabilized zirconia (ScSZ), cobalt doped lanthanum
gallate-based oxide (LSGMC) be constructed from such it is. Further, the fuel electrode
103 is, for example, a nickel-doped yttria-stabilized zirconia (Ni-YSZ), such as nickeldoped scandia stabilized zirconia (Ni-ScSZ), metallic nickel are mixed oxide material
constituting the electrolyte layer 104 those were.

[0024]
[0024] Further, on the side of the fuel electrode 103 of the fuel electrode interconnector
101, the fuel gas passage 111 is provided, on the side of the air electrode 105 of the air
electrode-side interconnector 107, oxidizing gas channel 171 It is provided. Although not
shown, the fuel electrode side interconnector 101, the fuel gas supply pipe and the fuel
gas exhaust pipe is connected, each of these pipes, in the fuel electrode side
interconnector 101 of the fuel gas passage 111 and it communicates with the provided
pipe. Similarly, although not shown, the air electrode side interconnector 107, the
oxidizing agent gas supply pipe is connected, this pipe, conduit provided inside the air
electrode interconnector 107 of the fuel gas passage 111 It communicates with.

[0025]
[0025] Further, on the side of the fuel electrode 103 of the fuel electrode interconnector
101, a concave portion is provided, the fuel electrode side connection layer 102 of the
unit cell in this recess, a fuel electrode 103, and the portion of the electrolyte layer 104 It
is housed. In the recess of the fuel electrode interconnector 101, between the fuel
electrode 103 (the electrolyte layer 104) and the fuel electrode interconnector 101 by a
ring-shaped sealing portion 109, sealed space is formed. With this structure, the fuel gas
supplied to the side of the fuel electrode 103, the contact between the oxidant gas
supplied to the side of the air electrode 105 is suppressed.

[0026]
[0026] Additionally, in the solid oxide fuel cell of this embodiment, at least the air
electrode-side surface of the air electrode-side interconnector 107, a protective film 108
made of lanthanum nickel ferrite is formed (coated) It was so. In other words, the surface
exposed to at least the air electrode side of the oxidant gas in the air electrode
interconnector 107, and the like are covered with a protective film 108 made of
lanthanum nickel ferrite (LNF).

[0027]
[0027] lanthanum nickel ferrite is a double oxide represented by the chemical
composition formula LaNi 1-x Fe x O 3-d (although 0 <="" div="">

[0028]
[0028] Lanthanum nickel ferrite, 0 <="" div="">

[0029]
[0029] Further, lanthanum nickel ferrite is stronger resistance to chromium, also in
contact with the chromium contained in ferritic stainless steel of the interconnector,
hardly occurs deterioration, as seen in lanthanum strontium manganite. Further, because
it does not contain chromium lanthanum nickel ferrite itself, it does not give the
chromium poisoning to the air electrode.

[0030]
[0030] lanthanum nickel ferrite having the features as described above, can be formed by
well-known methods. For example, lanthanum oxide, nickel oxide, and iron oxide were
mixed in the desired mol ratio, it is possible to form a protective film 108 made of
lanthanum nickel ferrite by firing the mixture at a temperature of 900~1400 .

[0031]
[0031] Incidentally, the fuel electrode side interconnector 101 and the air electrode
interconnector 107 can be formed from well-known metal materials used as
interconnectors for solid oxide fuel cells, in particular, corrosion resistance it may be used
high metal material (stainless steel). For example, ferritic stainless steel, austenitic
stainless steel, like a small amount of additive chromium-based alloy were added. Ferritic
stainless steel and minor amounts of additives to chromium-based alloy obtained by

adding the lanthanum nickel ferrite and thermal expansion coefficient close to, is suitable
as a material of the interconnector. Air electrode-side interconnector 107, when
configured with a chromium-based alloy obtained by adding a ferrite-based stainless steel
and minor amounts of additives, good adhesion between the protective film 108 made of
lanthanum nickel ferrite, solid with the use of these so attained is further life of the oxide
fuel cell.

[0032]
[0032] As a forming (coating) method of the protective film 108 against the air electrode
side interconnector 107 may be used a well known technique to form a coating of oxide.
For example, plasma spraying, slurry coating, spin coating, dip coating, electron beam
deposition, AC sputtering, magnetron sputtering, electrodeposition (electrodeposition),
and thermal spraying are applicable.

[0033]
[0033] The formation positions of the protective film 108 of the air electrode
interconnector 107 (area) is previously polished, blasting, dissolution, and good idea
pretreated by a method such as degreasing. By keeping perform these pre-processing, the
protective film 108 can be formed in a good adhesion state. The protective film 108 may
be formed in a region where the air electrode side of the oxidant gas in the air electrode
interconnector 107 is in contact. The thickness of the protective film 108 is thinner, it is
desirable to the extent that sufficient denseness is obtained, 100m or less, preferably
50m or less, particularly preferably not more than 10m or less.

[0034]
[0034] protective layer 108, in view of the electrical resistance, thinner good, but if too
thin, such as pinholes are generated, the function of the oxidizing gas contact prevention
against interconnector is reduced. Therefore, to create a plurality of test samples with
different thicknesses, changes in the resistance of the interconnector in the power
generation state each was measured, than the thickness conditions of the protective film
in the test sample that increase is not confirmed in the resistance, the protective film 108
the film thickness lower limit may be determined of.

[0035]
[0035] In addition, the air electrode 105, and consist of the same lanthanum nickel ferrite
and the protective film 108, the higher the connectivity between the air electrode side
interconnector 107 (protective film 108), in terms of output characteristics and life
characteristics particularly advantageous. If a single cell is flat type, the output

characteristic is advantageous in that high. Furthermore, unit cells, when a so-called fuel
electrode support type, has the advantage that particularly high output characteristics.

[0036]
[0036] Here will be briefly explained the characteristics of the fuel electrode support
type. The solid oxide fuel cell that is a stack structure obtained by combining a plurality
of single cells, the structure is large in the cell, as are classified into a cylindrical type and
plate type are well known, in terms of cell performance , seen many plate-type cell of an
air electrode or the fuel electrode support and the electrode-supporting. An advantage of
the electrode support type cell is a layer of least resistance of greater electrolyte in the
constituent material of the cell can be as thin as several m~ several tens m. Since the
internal resistance of the cell is reduced when the electrolyte layer is reduced, improving
the output is to be expected. The electrode support type cell, although none of the air
electrode or the fuel electrode can be applied as a support electrode, towards the anode is
more low resistance containing metal nickel as the electrode material, suppression of the
IR resistance when applied to a substrate it is advantageous to.

[0037]
[0037] Incidentally, the protective film 108 is not required to be formed of a single layer
made of lanthanum nickel ferrite, the surface of the protective film 108 made of
lanthanum nickel ferrite, stronger and more oxidation resistant, less reactive it may be
covered with a material. Further, two layers made of lanthanum nickel, may be
configured so as to sandwich a layer of less expensive materials. Protective film 108 is, at
least, are formed on the surfaces in need of air electrode interconnector 107 (covered)
need only include a film made of lanthanum nickel ferrite.

[0038]
[0038] Incidentally, interconnector film of lanthanum nickel ferrite described above is
formed is not limited to a solid oxide fuel cell, for example, it is also applicable to
hydrogen production by water electrolysis at high temperature conditions. This hydrogen
production is substantially similar to the operating conditions of the solid oxide fuel cell
having the configuration shown in FIG.

[0039]
[0039] is a sectional view showing a configuration example of a solid oxide fuel cell
according to an embodiment of the present invention.
Description of the code
[0040] 101 ... fuel electrode interconnector, 102 ... fuel electrode side connection layer,
103 ... fuel electrode, 104 ... electrolyte layer, 105 ... air electrode, 106 ... air electrode

connection layer, 107 ... air electrode side interconnector, 108 ... protective film, 109 ...
seal unit, 111 ... fuel gas passage, 171 ... oxidizing gas channel.

CLAIMS JP5090800

1.
1. The fuel electrode, disposed electrolyte layer over the anode, and between the unit cells
in which a plurality of unit cells composed of arranged air electrode over the electrolyte
layer adjacent stack structure laminated is arranged, a interconnector formed of stainless
steel, Comprising at least a protective film formed of the interconnector lanthanum nickel
ferrite which is formed to cover the entire area of the surface on the side of the air
electrode Interconnector, characterized in that.

2.
2. In interconnector according to claim 1, The interconnector is composed of ferritic
stainless Interconnector, characterized in that.

3.
3. In interconnector according to claim 1 or 2, The protective layer, iron mol number /
nickel mol number is composed of 9 or less of lanthanum nickel ferrite Interconnector,
characterized in that.

4.
4. A solid oxide fuel cell using the inter-connector according to any one of claims 1 to 3,
Fuel electrode, and the disposed electrolyte layer over the anode, and a plurality of single
cells stacked consists disposed cathode over the electrolyte layer, Wherein adjacent said
interconnector disposed between the unit cells and With at least, The air electrode, and a
lanthanum nickel ferrite Solid oxide fuel cell which is characterized in that.

5.
Five. In the solid oxide fuel cell according to claim 4, The unit cell, the solid oxide fuel
cell, which is a flat plate type.
6. Method according to claim 4 or 5, the solid oxide fuel cell according, The unit cell, the
solid oxide fuel cell, which is a fuel electrode support type in which the fuel electrode
and the support.