Conductive member, cell stack, electrochemical module, and electrochemical device
09786927 · 2017-10-10
Assignee
Inventors
Cpc classification
H01M8/2428
ELECTRICITY
Y02E60/50
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H01M8/243
ELECTRICITY
International classification
H01M8/0256
ELECTRICITY
Abstract
To provide a conductive member and a cell stack, where a concave groove of a conductive base substrate can be covered with a cover layer, as well as an electrochemical module and an electrochemical device.
Claims
1. A conductive member comprising: a conductive base substrate comprising an alloy containing Cr; a chromium oxide covering the conductive base substrate; and a cover layer covering the chromium oxide, wherein the conductive base substrate comprises a concave groove extending from the surface toward the inside, the chromium oxide is filled in the concave groove, and the surface of the chromium oxide is covered with the cover layer in the concave groove; and wherein the concave groove comprises: a concave portion present on the surface side of the conductive base substrate; and a crack extending linearly from the concave portion toward the inside of the conductive base substrate in cross-sectional view of the conductive base substrate.
2. The conductive member according to claim 1, wherein the chromium oxide is filled in the concave portion and the crack.
3. The conductive member according to claim 1, wherein the surface of the chromium oxide is dented in the concave portion, and a part of the cover layer digs into the dented portion.
4. The conductive member according to claim 1, wherein the chromium oxide extends linearly in the crack in cross-sectional view of the conductive base substrate.
5. The conductive member according to claim 1, wherein the chromium oxide comprises dots located linearly in the crack in cross-sectional view of the conductive base substrate.
6. The conductive member according to claim 3, wherein no material constituting the cover layer is present in the concave groove 20 μm or more inside from the surface of the conductive base substrate.
7. A cell stack comprising a plurality of electrochemical cells electrically connected to each other with the conductive members according to claim 1 therebetween.
8. An electrochemical module comprising the cell stack according to claim 7 in a storage container.
9. An electrochemical device comprising the electrochemical module according to claim 8 and an accessory machine to operate the electrochemical module in an outer case.
Description
BRIEF DESCRIPTION OF DRAWINGS
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DESCRIPTION OF EMBODIMENTS
(10) To begin with, a cell stack device including a fuel cell collector member as a conductive member will be described with reference to
(11) Then, a plurality of these fuel cells 3 are arranged in a row, a fuel cell collector member (conductive member) 4 (hereafter simply referred to as collector member 4) is disposed between adjacent fuel cells 3 and, thereby, a cell stack 2 is constructed, where fuel cells 3 are electrically connected to each other in series.
(12) The fuel cell 3 and the collector member 4 are bonded with a conductive bonding material 13 therebetween, as described later in detail. Consequently, the cell stack 2 is constructed by electrically and mechanically bonding a plurality of fuel cells 3 to each other through the collector members 4.
(13) A P-type semiconductor layer (not shown in the drawing) may also be disposed on the outer surface of the interconnector 11. The collector member 4 is connected to the interconnector 11 with the P-type semiconductor layer therebetween, so that contact between the two becomes ohmic contact and, thereby, potential drop can be reduced. This P-type semiconductor layer may also be disposed on the outer surface of the oxygen electrode layer 10.
(14) The lower end portion of each of the fuel cells 3 constituting the cell stack 2 is fixed to a gas tank 6 with a seal material, e.g., glass (not shown in the drawing). Consequently, a fuel gas in the gas tank 6 can be fed to the fuel electrode layer 8 of the fuel cell 3 through the gas flow channel 12 in the fuel cell 3.
(15) The cell stack device 1 shown in
(16) The cell stack device 1 has a configuration in which elastically deformable conductive sandwiching members 5 are disposed in such a way as to sandwich the cell stack 2 from both ends in the arrangement direction x of the fuel cells 3 with the collector members 4 therebetween. The lower end portions of the sandwiching members 5 are fixed to the gas tank 6. The sandwiching members 5 include flat board portions 5a disposed at both ends of the cell stack 2 and current lead portions 5b which have a shape extending along the arrangement direction x of the fuel cells 3 toward the outside and which lead the current generated by power generation of the cell stack 2 (fuel cells 3).
(17) The individual members constituting the fuel cell 3 shown in
(18) As for the fuel electrode layer 8, commonly known materials can be used and the fuel electrode layer 8 can be formed from a porous conductive ceramics, e.g., ZrO.sub.2 containing a rare earth element oxide as a solid solution (referred to as stabilized zirconia), and Ni and/or NiO.
(19) The solid electrolyte layer 9 is required to have a function as an electrolyte to serve as a bridge between electrodes in terms of electrons and, at the same time, have gas barrier properties to prevent leakage of the fuel gas and the oxygen-containing gas and is formed from ZrO.sub.2 containing 3 to 15 percent by mole of rare earth element (rare earth element oxide) as a solid solution. In this regard, the solid electrolyte layer 9 may be formed from other materials and the like insofar as the above-described characteristics are provided.
(20) The oxygen electrode layer 10 can be formed from a commonly used material, for example, conductive ceramics made from a so-called ABO.sub.3 perovskite compound oxide, without specific limitation. It is necessary that the oxygen electrode layer 10 have gas permeability and the open porosity can be 20% or more, and in particular within the range of 30% to 50%. As for the oxygen electrode layer 10, for example, at least one type of lanthanum manganite (LaSrMnO.sub.3), lanthanum ferrite (LaSrFeO.sub.3), lanthanum cobaltite (LaSrCoO.sub.3), and the like, where Mn, Fe, Co, or the like is present in B site, can be used.
(21) The interconnector 11 can be formed from conductive ceramics and needs to have the reduction resistance and the oxidation resistance because of contact with the fuel gas (hydrogen-containing gas) and the oxygen-containing gas (air or the like), so that lanthanum chromite (LaCrO.sub.3) can be used. It is necessary that the interconnector 11 be dense to prevent leakage of the fuel gas passing through the plurality of gas flow channels 12 in the conductive support 7 and the oxygen-containing gas passing outside the conductive support 7. Preferably, the relative density is 93% or more, and in particular 95% or more.
(22) The conductive support 7 is required to have the gas permeability to pass the fuel gas to the fuel electrode layer 8 and, in addition, the electrical conductivity to collect currents through the interconnector 11. Therefore, it is necessary that a material satisfying such a requirement be used for the conductive support 7, and conductive ceramics, cermet, and the like can be used, for example.
(23) Meanwhile, in production of the fuel cell 3, in the case where the conductive support 7 is produced by co-firing with the fuel electrode layer 8 or the solid electrolyte layer 9, the conductive support 7 can be formed from an iron group metal component and a specific rare earth element oxide. In order to provide the gas permeability, the conductive support 7 favorably has an open porosity of 30% or more, and in particular within the range of 35% to 50%, and the electrical conductivity thereof may be 50 S/cm or more, 300 S/cm or more, or furthermore 440 S/cm or more.
(24) Examples of P-type semiconductor layer (not shown in the drawing) can include a layer formed from a transition metal perovskite oxide. Specifically, a material having the electron conductivity larger than the electron conductivity of lanthanum chromite constituting the interconnector 11, for example, P-type semiconductor ceramics made from at least one type of lanthanum manganite (LaSrMnO.sub.3), lanthanum ferrite (LaSrFeO.sub.3), lanthanum cobaltite (LaSrCoO.sub.3), and the like, where Mn, Fe, Co, or the like is present in B site, can be used. The thickness of such a P-type semiconductor layer is preferably within the range of 30 to 100 μm in general.
(25) The conductive bonding material 13 connects the fuel cell 3 to the collector member 4 and can be formed by using the conductive ceramics or the like. The same conductive ceramics as that constitutes the oxygen electrode layer 10 can be used. It is preferable that the conductive bonding material 13 be formed from the same components as the components of the oxygen electrode layer 10, because the bonding strength between the oxygen electrode layer 10 and the conductive bonding material 13 is enhanced.
(26) Specifically, LaSrFeO.sub.3, LaSrMnO.sub.3, LaSrCoO.sub.3, and the like can be used. The conductive bonding material 13 may be produced by using a single material among these materials or by combining at least two types.
(27) The conductive bonding material 13 may be formed from different types of materials having different particle diameters or be formed from different types of materials having the same particle diameter. Furthermore, the conductive bonding material 13 may be formed from the same type of materials having different particle diameters or be formed from the same type of materials having the same particle diameter. In the case where different particle diameters are employed, preferably, the diameter of fine particle is specified to be 0.1 to 0.5 μm, and the diameter of coarse particle is specified to be 1.0 to 3.0 μm. In the case where the conductive bonding material 13 is formed by employing the same particle diameter, preferably, the particle diameter is specified to be 0.5 to 3 μm.
(28) The conductive bonding material 13 is produced by using materials having different particle diameters, as described above, so that coarse particles having a large particle diameter can enhances the strength of the conductive bonding material 13 and, in addition, fine particles having a small particle diameter can improve the sinterability of the conductive bonding material 13.
(29) Next, the collector member 4 will be described with reference to
(30) In the fuel cell 3, as described above, the region in which the fuel electrode layer 8 is opposed to the oxygen electrode layer 10 with the solid electrolyte layer 9 therebetween serves as a power generation portion. Therefore, in order to collect the current generated in the power generation portion of the fuel cell 3 efficiently, the length of the collector member 4 along the longitudinal direction of the fuel cell 3 is favorably specified to be more than or equal to the length of the oxygen electrode layer 10 in the fuel cell 3 in the longitudinal direction. The structure of the collector member 4 is not limited to this.
(31) The collector member 4 is exposed to a high-temperature oxidizing atmosphere when the cell stack device 1 is operated and, therefore, is constructed by forming a cover layer 43 all over the surface of a collector substrate (conductive base substrate) 41. Consequently, degradation of the collector member 4 can be reduced. In this regard, in
(32) The collector member 4 is required to have the heat resistance and the electrical conductivity in a high-temperature oxidizing atmosphere, so that the collector substrate 41 can be produced from, for example, an alloy. In particular, the collector member 4 is exposed to a high-temperature oxidizing atmosphere and, therefore, the collector substrate 41 is formed from an alloy containing Cr at a proportion of 4 to 30 percent by mass. The collector substrate 41 can be formed from, for example, Fe—Cr based alloys, Ni—Cr based alloys, and the like. The collector substrate 41 is a conductive base substrate for high temperatures (600° C. to 1,000° C.).
(33) In order to reduce diffusion of Cr in the collector substrate 41 into the fuel cell 3, an oxide of Zn, a perovskite compound oxide containing La and Sr, or the like can be used as the cover layer 43. The cover layer 43 may be a material other than the above-described material insofar as diffusion of Cr is reduced.
(34) As shown in
(35) A plurality of concave grooves 15 are disposed in the second surfaces 4h and the third surfaces 4i of the first collector piece 4a and the second collector piece 4b, and chromium oxide 14 is filled in these concave grooves 15. Put another way, crack-shaped concave grooves 15 are disposed in the surfaces (side surfaces) cut by the shear force during pressing and, thereby, formed in the thickness direction, and chromium oxide 14 is filled in these concave grooves 15. This chromium oxide 14 is formed by oxidizing Cr diffused from the inside of the collector substrate 41 to the surface of the concave grooves 15 of the collector substrate 41 during a heat treatment of the collector substrate 41.
(36) As shown in
(37) Explanations will be made with reference to
(38) As shown in
(39) The structure shown in
(40) Linear dotting toward the inside of the collector substrate 41 may be in the shape a straight line or a curved line. The inner wall surfaces constituting the concave groove 15 are almost closed to such an extent that the inner wall surfaces come into contact with each other, and in these almost closed portions, it seems that the chromium oxide 14 is not present or blocks of chromium oxide 14 dot.
(41) The material constituting the cover layer 43 is not disposed in the concave groove 15 which is 20 μm or more deep from the side surface of the collector substrate 41. That is, chromium oxide 14 is present in the concave groove 15 which is 20 μm or more deep from the side surface of the collector substrate 41, and the cover layer 43 covers all over the surface of the chromium oxide 14 in the concave portion 15a in the concave groove 15. In this regard, the term “20 μm or more deep from the side surface of the collector substrate 41” refers to 20 μm or more deep from the straight line bonding the side surfaces upper and under the concave groove 15 of the collector substrate 41 in the cross section of the collector substrate 41 in the thickness direction.
(42) In
(43) The concave groove 15 is disposed having a depth from the second surface 4h and the third surface 4i of the collector portion 4f toward the inside of 5 to 30 μm (L shown in
(44) Peeling of the cover layer 43 from the collector substrate 41 can be suppressed because the thermal expansion coefficient decreases in the order of the collector substrate 41, the chromium oxide 14, and the cover layer 43 and a material constituting the chromium oxide 14 is present in the concave groove 15 as well.
(45) Next, a method for producing the collector member 4 will be described. As shown in
(46) Then, as shown in
(47) Subsequently, the collector substrate 41 is, for example, heat-treated in the air at 500° C. to 1,000° C. for 0.5 to 5 hours, so that layered chromium oxide 14 is formed on the surface of the collector substrate 41 and, in addition, as shown in
(48) Also, the thickness of the concave groove 15 can be adjusted by adjusting the pressure applied with the lower die 19a2 and the upper die 19b2 shown in
(49) It is possible that the concave groove 15 is not completely filled with the chromium oxide 14 and the chromium oxide 14 is formed in such a way as to be slightly dented from the surface of the concave groove 15 of the collector substrate 41 by controlling the pressure applied with the lower die 19a2 and the upper die 19b2 and controlling the heat treatment condition. In this configuration, the material constituting the cover layer 43 is disposed in the dent of the chromium oxide 14, and peeling of the cover layer 43 from the collector substrate 41 can be suppressed. Also, it is possible to form the chromium oxide 14 to almost equal position of the surface of the collector substrate 41 or form the chromium oxide 14 in such a way as to slightly protrude from the surface of the collector substrate 41 by controlling the pressure applied with the lower die 19a2 and the upper die 19b2 and controlling the heat treatment condition.
(50) Thereafter, as shown in
(51) In the case where the opening portion of the concave groove 15 is wide and shallow, the thickness of the opening portion is hardly decreased by pressurizing the principal surface of the collector substrate 41. However, the chromium oxide 14 in the concave groove 15 can be covered with the cover layer 43 by the sputtering method or the like because the opening portion is wide. Conversely, in the case where the opening portion of the concave groove 15 is wide and deep, the thickness of the deep portion side of the concave groove 15 is decreased by pressing, the chromium oxide 14 is filled in, and as for the opening portion of the concave groove 15, the chromium oxide 14 in the concave groove 15 can be covered with the cover layer 43 by the sputtering method or the like. Meanwhile, in the case where the opening portion of the concave groove 15 is narrow, the opening portion of the concave groove 15 can be covered with the cover layer 43.
(52) In this regard,
(53) In the step shown in
(54) Next, the state of bonding between the collector member 4 and the fuel cell 3 with the conductive bonding material 13 therebetween will be described with reference to
(55) As shown in
(56) That is, in
(57) Next, a fuel cell module 20 in which the cell stack device 1 is in a storage container 21 will be described with reference to
(58) The fuel cell module 20 shown in
(59)
(60) In
(61) Next, a fuel cell device 25 in which the fuel cell module 20 and an accessory machine (not shown in the drawing) to operate the fuel cell module 20 are in an outer case will be described with reference to
(62) The fuel cell device 25 shown in
(63) The partition board 28 is provided with an air flow hole 31 to pass the air in the accessory machine storage chamber 30 to the module storage chamber 29 side and an exhaust vent 32 to exhaust the air in the module storage chamber 29 is disposed in part of the facing board 27 constituting the module storage chamber 29.
(64) Up to this point, the present invention has been explained in detail. However, the present invention is not limited to the above-described embodiments and various modifications, improvements, and the like can be made within the bounds of not departing from the gist of the present invention.
(65) For example, in the above-described embodiments, the fuel cell collector member 4 of the cell stack device 1 is explained as the conductive member according to the present invention. However, the application of the conductive member according to the present invention is not limited to the fuel cell and it is possible to use for applications in a high-temperature oxidizing atmosphere, for example, a conductive member for an oxygen sensor.
(66) In the above-described embodiments, the fuel cell, the fuel cell module, and the fuel cell device are explained. However, the present invention is not limited to them and can also be applied to an electrolysis cell (SOEC) to generate hydrogen and oxygen (O.sub.2) by applying a water vapor and a voltage to the electrolysis cell and electrolyzing the water vapor (water) and an electrolysis module and an electrolysis device including the electrolysis cell.
REFERENCE SIGNS LIST
(67) 1 cell stack device 2 cell stack 3 fuel cell 4 collector member 6 gas tank 13 conductive bonding material 14 chromium oxide 15 concave groove 15a concave portion 15b crack 20 fuel cell module 21 storage container 25 fuel cell device 41 collector substrate 43 cover layer