CN100472860C - Anode-supported solid oxide fuel cells using a cermet electrolyte - Google Patents
Anode-supported solid oxide fuel cells using a cermet electrolyte Download PDFInfo
- Publication number
- CN100472860C CN100472860C CNB2004800226341A CN200480022634A CN100472860C CN 100472860 C CN100472860 C CN 100472860C CN B2004800226341 A CNB2004800226341 A CN B2004800226341A CN 200480022634 A CN200480022634 A CN 200480022634A CN 100472860 C CN100472860 C CN 100472860C
- Authority
- CN
- China
- Prior art keywords
- fuel cell
- solid oxide
- oxide fuel
- anode
- tubular body
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 104
- 239000007787 solid Substances 0.000 title claims abstract description 41
- 239000003792 electrolyte Substances 0.000 title claims description 25
- 239000011195 cermet Substances 0.000 title claims description 13
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims description 25
- 210000000038 chest Anatomy 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- 238000010276 construction Methods 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 8
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 229910002076 stabilized zirconia Inorganic materials 0.000 claims description 5
- 238000005728 strengthening Methods 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 2
- 229910021525 ceramic electrolyte Inorganic materials 0.000 claims 2
- 239000002001 electrolyte material Substances 0.000 claims 2
- 238000000465 moulding Methods 0.000 claims 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 2
- 229910000765 intermetallic Inorganic materials 0.000 claims 1
- 229910000314 transition metal oxide Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000012545 processing Methods 0.000 abstract description 9
- 230000001965 increasing effect Effects 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 2
- 230000002787 reinforcement Effects 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004814 ceramic processing Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012457 nonaqueous media Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 102220043159 rs587780996 Human genes 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007569 slipcasting Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003351 stiffener Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Images
Classifications
-
- Y—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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Fuel Cell (AREA)
Abstract
Fuel electrode-anode supported type solid oxide fuel cells (SOFC) comprise novel fuel electrode design with improved mechanical and electrochemical properties. The novel supporting anodes comprise a plurality of internal longitudinal elevations or bosses projecting inwardly into the central bore of the tubular body for structural reinforcement of the entire cell, increasing electrode surface area, optimizing the anode electronic conductivity, and facilitating the mounting of the cell into a SOFC assembly system (e.g., cell stack). The SOFCs of the invention contemplate a range of tubular configurations, including cylindrical and polygonal shapes having at least three surfaces. Low-cost manufacturing routes are also disclosed, whereby the protruding bosses in the anode support do not require additional processing steps compared to conventional forming techniques.
Description
Technical field
The present invention relates generally to fuel cell, more particularly, relate to and have the tubular solid-oxide type fuel cell (SOFC) that improves anode, and manufacture method, wherein said anode strengthens the physics and the electrochemical properties of battery by unique interior geometry system, thereby improves mechanics support, durability and battery performance characteristic.
Background of invention
Developed several different Solid Oxide Fuel Cell constructional devices, comprised tubulose, the plane and all-in-one-piece device, all device recordings are in technical literature.(see, Q.M.Nguyen et al. for example, ＂ Science and Technology of Ceramic Fuel Cells ＂, Elsevier Science, Jan.1995).The SOFC device of described tubulose originate from the sealing problem relevant with the fuel battery on plane (see G.Hoogers, " Fuel Cell TechnologyHandbook ", CRC Press, Aug.2002).Many disclosed patents belong to SiemensWestinghouse Power Corp., Orlando, and FL discloses so-called air electrode load (AES) technology and (has seen for example people's such as Ruka US 5,916,700; The US 5,993,985 of Borglum reaches the US 6,379,485 that also belongs to Borglum).
Although obtained significant technological contribution in the SOFC field of tubulose, the tubular fuel cell of air electrode load is still run into several shortcomings.As one of them, air electrode material is expensive such as lanthanum, strontium, manganite or the like, makes becoming of process economics not noticeable usually.In addition, air electrode is made up of ceramic material, and their mechanical strength and durability are usually less than the mechanical strength and the durability of the fuel electrode of being made by cermet (being pottery and metal composite).
(see Song etc. US 6,436,565) caused the attention that this area is new to (FES) tubular SOFC of fuel electrode load because some economically improvement.
Have openend and at one end closed although AES and FES tube have transform as on the structure, almost not have obviously suggestion the tubular SOFC inner structural features to be changed and cause improvement as the basic tubular structure of the structural intergrity of this class battery of enhancing and operating characteristic device with respect to conventional cylindrical configurations.
Therefore, need to improve tubular SOFC s anode to strengthen support structure, durability and to increase the electron conductivity that surface area is used to optimize battery.
Summary of the invention
Therefore main purpose of the present invention provides the SOFCs with novel supporting construction.The geometry of supporting anodes is given the electrical property that reaches of battery enhanced physical, heat, and more attractive economically.
The other main purpose of the present invention also provides a kind of method with minimum processing step of making described improvement tubular support anode and comprising the SOFCs of described anode.
The anode layer geometry of described novelty comprises that at least one is more preferably longitudinally a plurality of, interior thorax from described anode layer inner surface or i.d. to central opening or tubular body is to projecting inward, with the projection of inner hump or lug boss (and the groove between them) form.General, described protuberance or lug boss can be parallel or coaxial with the longitudinal axis of tubular body, alternatively, for example can reel with the spiral pattern of routine by centre bore, and do not contact other protuberances or the lug boss of tubulose anode surface, perhaps in conjunction with other sections of tubular surface.Described " lug boss " or " supporting anodes " are given improved Mechanical Reliability, durability and are increased the active cell area, strengthen electrochemical performance characteristics by resistance is minimized simultaneously.The present invention also can strengthen the fuel flow rate characteristic of battery, thereby because described inner projection for example can increase mixing by causing turbulent flow or eddy current to mix.Therefore, a main purpose of the present invention provides has the SOFCs that comprises the load galvanic anode that forms the centre bore tubular body, and wherein said tubular body comprises the outstanding load device that centre bore is used for strengthening on the structure whole fuel cell that enters.Preferably, the described outstanding load device that enters described centre bore is main body integrated with sheath.
For purpose of the present invention, like this as appearing at expression in specification and claims as " tubulose " or " tubular body " or its variation, be intended to comprise fuel cell main circle or circular wall, cylindrical shape for example, yet, this invention is intended to also comprise the tubular body of polygon geometric configuration with at least three sides, for example triangle tube, rectangle/square tube, hexagonal tube and variation thereof, such as three similar leg-of-mutton pipes in side, wherein the summit for example is circular or the like.Therefore, although SOFCs of the present invention mainly with cylindrical tubular body explanation, understanding this only is to be intended to purpose easily, rather than is intended to restriction or repels as at those other geometric configurations mentioned above.
Because thinking, the SOFCs of their geometry tubulose is subjected to loss of potential.Supporting anodes that it should be noted that novel convex structure feature provides preferential " lower resistance " electron transport path, so that these minimization of losss.
The another other purpose of the present invention provides the tubular SOFC s of the supporting anodes with novel geometric properties, described SOFCs not only provide enhancing structural intergrity, heat and electrical property, and because the geometry of their uniquenesses, also be convenient to the assembling of SOFC lamination multifunction system, described thus anode lug boss protuberance as guider, guarantees that air flue all keeps uncovered on two limits of described syringe in the fuel arranged injector.
Therefore, the SOFCs with novel sheath supporter that the present invention relates to comprises fuel electrode, more particularly, comprise fuel electrode with inner surface anode construction, described anode construction has and suitable extends the protuberance that inwardly enters centre bore from tubular structure inner surface or radius, has intermediate groove or recess to be used to strengthen the structural strengthening of SOFCs between described protuberance.As the tubular SOFC s that supporting anodes of the present invention is used, supporting anodes of the present invention can be in open at both ends, and is perhaps at one end closed.Described anode support structure is thick relatively wall, because outstanding convex structure is generally non-circular [thorax.Therefore, the geometry of the uniqueness of described anode is given whole fuel cell rigidity and intensity.
On the composition, load fuel electrode of the present invention is by transition metal (for example Ni) and ceramic material (for example stabilized zirconia, doping cerium dioxide or other suitable electrolytes), and promptly cermet is formed.
As former discussion, key breakthrough of the present invention relates to the anode assembly of novel geometric electrode structural change, so its whole fuel cell structure of physical support more that becomes.The hole thorax of described fuel electrode comprises the still circular anode of non-circular interior wall construction that is configured to tubulose, and described interior wall construction has at least one, and more preferably a plurality of the protuberance longitudinally continuously or lug boss is preferably also coaxial at interval with tubular body longitudinal axis symmetry.Described lug boss is preferably arranged along the length direction of tubular body, but also can only be arranged along the part of hollow edged electrode principal length direction.Therefore, by introduce protuberance or lug boss (between them, forming groove) longitudinally along described tubular structure inwall, following several advantage is arranged:
-increase thickness or surface area by fuel electrode, be the height supporting construction of fuel cell thereby make anodic conversion, obtain bigger mechanical strength.Preferably, described internal protrusion portion symmetric arrays, so they are around interior ring equidistant intervals each other, further strengthen the SOFC of whole tubulose on the structure;
The surface area of-the conduction that generation is bigger within battery;
-realize bigger electrochemistry output by the electron conductivity that strengthens anode support;
Fuel battery is promptly operated and be assembled into to-improved fuel cell assembling efficient easily, and the groove between the wherein said protuberance is as the guider of layout and fastening fuel injectors.This minimizing or eliminated destruction and the leakage problems that conventional pipe runs into.
Those of ordinary skill in the art is recognized that the geometric configuration of lug boss/protuberance that the described inside of supporting anodes of the present invention is outstanding is actually unrestricted.Representational protuberance comprises such shape such as circular cone, rectangular, foursquare, circular or semicircle, slightly lifts numerical example.General, their quantity and size are suitable for the fuel injector device introduced subsequently at SOFC lamination assembly process.
The present invention also relates to the method for the described supporting anodes of improved manufacturing.
The manufacture method of supporting anodes is formed directly related with described fuel electrode mixture.Useful extruding technology is generally to extrude those relevant technology with plastics.Have in the internal protrusion portion supporting anodes in manufacturing, they provide improved economic advantages, and especially described internal protrusion portion extends along whole tubular body length direction.Preferred casting and compact technique are used to make complicated more interior shape, and described thus internal anode lug boss is discontinuous, and perhaps with respect to the whole length of anode-supported pipe, length is shorter.
Can realize the fuel cell electrochemical properties is further improved by in the fuel electrode mixture, introducing artificial pore former, so that catalytic activity optimization and limit mass transfer problem.
From above-mentioned open and below describe in detail more, it is evident that for those of ordinary skill in the art to the invention provides a kind of obvious improved tubular fuel cell technology, more particularly, tubular SOFC technology.Be apparent that electromotive force in this respect especially, the invention provides with lower cost production more economically, the fuel cell of high current density, have improved Mechanical Reliability simultaneously.In view of additional features and advantage can be better understood in following more detailed explanation.
The accompanying drawing summary
In the detailed description below the present invention character of the present invention and mode of operation are described more fully in conjunction with the accompanying drawings, wherein:
Fig. 1 is the stereogram that comprises the tubular SOFC of supporting anodes of the present invention, removes the ring/layer of part with the explanation battery, comprises the electrolyte and the cathodic region of battery.
Fig. 2 is the amplification stereogram of Fig. 1 tubular SOFC, show architectural feature of the present invention in greater detail, comprise by on described battery (total length) the inner annular anode as the conical protrusions portion of ridge or protuberance between at interval four stiffeners formed of circular groove longitudinally continuously;
Fig. 3 is the stereogram of the other SOFC execution mode of the present invention, comprises the supporting anodes as Fig. 2 signal, but improved, and wherein said interior conical lug boss only extends along the partial-length of the tubular cell on the inner annular anode (short length).
Fig. 4 is the stereogram of the other SOFC execution mode of the present invention, comprises that ring is gone up the vertically continuous at interval rectangular support protuberance of a plurality of symmetries in the electrode, and forms the support circular anode of spacing convave trough between them;
Fig. 5 is the stereogram of the other SOFC execution mode of the present invention, comprise the support circular anode, be characterised in that a plurality of support components are evenly spaced, the outstanding tubulose body opening thorax that enters of rounded protuberance, and along the extension of cylindrical battery length direction, (total length) has the continuous circular groove between swelling on the interior ring;
Fig. 6 also is the stereogram of the other execution mode of Solid Oxide Fuel Cell of novelty of the present invention, comprise supporting anodes, be characterised in that eight conical support protrusion portions as leave the inside protuberance of inner loop along the tubular cell length direction extend and between them (total length) form continuous groove;
Fig. 7 is the stereogram of the other execution mode of SOFC of the present invention, comprises supporting anodes, is characterised in that inner hump is in spirality or spiral structure;
Fig. 8 is the stereogram that the another other load tubular SOFC of the present invention can be selected execution mode, wherein not cylindrical, described external cathode comprises three surfaces with rounded vertex, and the inner support circular anode has the outstanding inside that enters the battery hole thorax of interval protuberance of balanced configuration;
Fig. 9 is the stereogram of polygon SOFC, more particularly, be the stereogram of fuel cell, wherein outside hollow cathode is hexagon and reinforced by the inner annular anode, and described inner annular anode is characterised in that a plurality of rectangles of leaving the anode inner surface swell the outstanding battery hole thorax that enters at interval.
Figure 10 is the cutaway view of signal tubular SOFC of the present invention, and the SOFC of described manufacturing installs supporting anodes on fuel injector;
Figure 11 is the top plan view that is installed in tubular SOFC on the fuel injector according to Figure 10, and
Figure 12 is the part end-view of extrusion die, is used to be shaped of the present inventionly have from the tubular support anode of the outstanding anode lug boss of interior ring.
The description of preferred implementation
At first forward Fig. 1 to, the full figure of SOFC10 of the present invention be provided, as the cylindrical tubular body that changes inner annular anode 12 to be described best, intermediate electrolyte 14 and outside hollow cathode 16.Described anode 12 forms endoporus 18, has a plurality of protuberances 20 that enter hole thorax protrusion from the anode inwall.
Fig. 2 is the enlarged drawing of Fig. 1 fuel cell, and anode support 12 of the present invention is described best, and wherein the conic convex portion 20 of four form symmetric arrangement is provided with oval groove 22 along the coaxial extension of tubular SOFC 10 total length directions in the middle of lug boss 20.Lug boss 20 provides the surface area and the intensity of increase to fuel cell, be shown as with circular anode 12 be incorporate.
Fig. 3 explanation provides a kind of execution mode of selecting of the general tubular SOFC24 of the present invention as some the identical architectural features among Fig. 2, comprises supporting anodes 26, intermediate electrolyte 28 and external cathode 30.Anode 26 forms the internal holes thorax 32 with the oval groove 34 that is provided with between taper shape protuberance/lug boss 36.Fuel cell 24 features also are the protuberance 38 that shortens, and protuberance 38 is not to extend along battery total length direction, but shorter than tubular body total length.
Fig. 4 illustrates the SOFC40 of cylinder, is the another other selectable execution mode of the present invention, comprises and supports inner annular anode 42, intermediate annular solid electrolyte 44 and outside negative electrode 46.Described inner annular anode 42 comprises and a plurality ofly is arranged on evenly spaced between arc or the groove 50 and swells 48 longitudinally, as the incorporate parts of circular anode shape structure.Protuberance 48 is the rectangular or general square configuration that are provided with in fuel cell hole thorax 52.
Fig. 5 illustrates the other execution mode of the SOFCs that anode of the present invention is reinforced, and tubular fuel cell 54 also has the structure of cylinder.The SOFC54 of described reinforcing comprises inner support circular anode 56, intermediate solid electrolyte 58 and outside hollow cathode 60, wherein said anode interior protuberance comprises circle, evenly spaced lug boss 62, as along the battery partial-length or fully the length longitudinal extension by the enhancing projection of battery hole thorax 64.Preferably, protuberance 62 symmetry interval between the inner circular shaped region 66 of supporting anodes inwall.
Fig. 6 illustrates the other execution mode of tubular SOFC68 of the present invention, has supporting anodes 70, intermediate annular solid electrolyte 72 and outside negative electrode 74.Described supporting anodes 70 is characterized as interior geometry and comprises eight outstanding taper shape protuberances 76 that enter centre bore thorax 80 that whole length are general, the groove 78 that has slightly circular in the middle of protuberance 76.
Fig. 7 illustrates the execution mode with novel interior geometry supporting anodes 84 82 of the other cylinder of tubular SOFC of the present invention, comprise dielectric substrate 86 and hollow cathode 88, wherein the protuberance 90 of supporting anodes 84 is continuous, extends with spiral path along support column length between border circular areas 92.
Fig. 8 and 9 explanation the present invention can select the execution mode of tubulose, and wherein said tubular structure is not circular, and for example cylindrical tube for example can be polygonal still.Fig. 8 illustrates the execution mode of the SOFC92 that the present invention is such, comprises that three main are the external cathode surface 94 of triangle together, and difference is rounded vertex 96 contact surfaces 94.The certain expection of the present invention has the polygonized structure on three or more surfaces, for example triangle, square, pentagon, hexagon or the like.Describe as the present invention, those tubular fuel cell execution mode of image pattern 8 comprises supporting anodes.Fig. 8 fuel cell also comprises inner support anode 98, the cathode construction 94 of three sides of intermediate electrolyte 99 and outside.Described supporting anodes 98 comprises that also the conduct between border circular areas 102 such as description in the past enters the protuberance 100 of described battery endoporus projection.
Fig. 9 is the polygon SOFC104 of the another the present invention of comprising, wherein said battery comprises the electrolyte ring 107 of inner support circular anode 106, intermediate tubular and has the negative electrode of the outside of polygon on six surfaces 108.This execution mode is characterised in that supporting circular anode 106 has the lug boss 110 that a plurality of conducts are arranged on the interval protuberance between circular depressed place or the arc 112.
The specific implementations of Fig. 1-9 is intended to only be used for the illustrative purpose, rather than is intended to be restricted to various for the conspicuous execution mode of selecting of those of ordinary skills, but is intended to comprise all such replacement scheme and variations.
As mentioned before, the main aspect of the present invention is to have the anode that strengthens support performance, novel interior geometry, is used in particular among the SOFCs of tubulose, provides structure to strengthen for whole fuel cell with respect to the sheath of routine.
Use to improve anode and see it is the most useful (see Song etc. US 6,436,565) from the performance characteristics viewpoint as supporting structure.In addition, as former discussion, for the fuel cell of equipment anode of the present invention, wherein interior ring thickness is the 0.2-2.0 millimeter, by increasing electron conductivity and reducing activation overpotential and can realize high current density (referring to because electrochemical charge transfer reaction causes the loss of voltage).
On the composition, be used for the electroactive substance of described anode, cermet supporter, promptly the content of metal based on the volume of described solid, is preferably the about 80.0 volume % of about 30.0-.Be lower than 30 volume % for tenor, described cermet anode compound has the conductivity of minimizing.When the ceramic-metallic tenor of supporting anodes be approximately 30 volume % or more than, among described metal particle, cause the good interface combination, cause the electron conductivity that increases.Tenor up to 80 volume % enough guarantees very high electron conductivity, keeps enough porositys simultaneously so that concentration polarization minimizes.The higher content of the metal in the anode metal pottery causes and the unmatched big thermal coefficient of expansion of coating electrolyte subsequently, cause processing or battery-operated during form the crack.
For strengthening battery performance characteristic, also wish to increase the porosity of anode, therefore concentration polarization (referring to crossing the relevant loss of voltage of porous electrode resistance with air communication) is remained on the bottom line level.A method that realizes this result is by in-situ treatment basically, makes the metal oxide powder reduction become the metal of element under the reducing atmosphere condition, thereby provides anode base material bigger porosity.Therefore, higher metal oxide content is normally preferred in described anode is formed.
Can also make anode produce other porosity by introducing pore former.The representational example of useful pore former comprises carbon powder, starch, polymer globules or the like.When supporting anodes being created complete tubular SOFC structure, during sintering, remove pore former subsequently.Based on described metal ceramic powder, the preferable amount of pore former is up to 50 volume %.Obviously the pore former of high level causes the loss of mechanical strength.
The representative example that is used for the useful ceramic material of cermet fuel anode support of the present invention comprises the stabilized zirconia that is used for high temperature SOFC (700 ℃-1000 ℃).This preferably includes 8mol% yittrium oxide-stabilized zirconia (YSZ), (ZrO
2)
0.92(Y
2O
3)
0.08Useful in addition material is a doping cerium dioxide, is used for moderate temperature SOFC (500 ℃-700 ℃).This preferably includes the ceria (CGO) that gadolinium mixes, (Ce
0.09Gd
0.10) O
1.95Other materials that are suitable for SOFC electrolyte application scenario also are applicable to the present invention.
Usually, the metal that is used for fuel electrode supporter of the present invention reaches the transition metal that the cermet electrolyte belongs to the periodic table of elements mutually, and comprises their alloy or physical mixture.Elemental nickel (Ni) is a preferred metal because it has high electro-chemical activity, high electron conductivity under the reducing atmosphere condition, with and cost efficiency arranged.Metal can be incorporated into by different precursors in anode support and the cermet electrolyte, comprises metal dust, metal oxide powder, slaine (moisture or non-moisture) or the like.Metal oxide powder is normally preferred such as NiO, because their cost benefit and they are to the adaptability of ceramic process.Limited amount very simple metal particle can be introduced by slaine, comprises Ni (NO in water or the alcoholic solution such as being dissolved in moisture and nonaqueous solvents
3)
2This is relevant especially with anode support, wherein wishes closely to contact between the metal particle to be used to strengthen electron conductivity.
The outstanding vertical lug boss of anode support can make the anode gross thickness reduce, because they have increased the intensity and the surface area within the anode of contact gas stream of anode.Therefore, improved supporting anodes is compared with the conventional pipe that does not have such architectural feature, has the architectural characteristic of enhancing.Preferably, be symmetrical arranged inner hump so they and they intermediate groove equidistant intervals each other.This also gives the distribution of weight of tubular support homogeneous.Wish that also this architectural characteristic is used for making the shrinkage amount reduce to minimum during the drying of battery manufacturing and sintering.The groove that crosses the uneven distribution of empty tubular support causes the defective that is harmful to, such as warpage and/or break.The intensity of described support column increases with outstanding lug boss quantity.
The existence of outstanding lug boss also strengthens the chemical property characteristic of supporting anodes.Thereby the activation overpotential of crossing the thick zone of cermet anode by increase electron conductivity and minimizing is realized higher current density.
As mentioned before, vertically outstanding lug boss also provides the excellent ability that battery is assembled into the fuel battery assembly.Figure 10 illustrates the phantom of the SOFC114 of tubulose, comprise the anode support 116 that is installed on the fuel injector 118 of the present invention, described thus anode ridge or swell and 120 be used for syringe 118 location and be fixed on predetermined orientation within the hole thorax of described battery tubulose.Protuberance 120 physics between the circular void 122 keep the center of fuel injector 118, optimize the flow behavior of anode support inside, therefore the better distribution that causes entering anode reaction position fuel.
The processing approach of making the anode support of protuberance depends on that the preparation of above-mentioned discussion comprises the fuel electrode mixture of metal and ceramic compound.Moisture or non-aqueous media can be used to the described granular substance that suspends.Yet moisture medium is normally preferred because their cost benefit and seldom with organic solvent combustibility and the relevant environmental problem of toxicity.Also can use common processing additives (dispersant, binding agent, plasticizer) (to see R.J.Pugh et al. with the mixture that guarantees fully to disperse stable homogeneous, ＂ Surface and Colloid Chemistry in AdvancedCeramics Processing ＂, Marcel Dekker, Oct.1993).The characteristic of these mixtures can change by characteristic or the amount that changes different material such as viscosity.Thereby they transform suitable specific forming process as.
Particularly, when making the uniform section bar of cross section, preferably extrude moisture plastic class material.When hope when the whole length of support column have continuous lug boss, this is appropriate especially.Figure 12 illustrates a kind of part figure of extrusion die 124, and its further groove 126 has been processed into the inner mould 128 that leaves die slot 130.Therefore, described extrudate demonstrates along the outstanding protrusion of tubular support anode inwall, and is consistent with among Fig. 1 those, or the like.
On the other hand, complicated more section bar for example wherein the section bar that is provided with according to spirality (spiral) path of lug boss can pass through foundry engieering (liquid phase processing) or compact technique (dry process) prepares.Foundry engieering comprises slip-casting, spun casting, gel casting or the like.Compact technique comprises dry pressing and isostatic pressing.All such processing approach are known, and record (is seen for example J.S.Reed, ＂ Principles of Ceramic Processing, 2ndEdition ＂, J.Wiley in the literature fully; Sons, Nov.1994).
As mentioned above, other additives be directed in the described structure, such as pore former, to adjust the porosity of fuel electrode supporter.These optional additives were introduced in the cermet mixture in the past at forming operation.
Novel supporting anodes of the present invention can be used for using usually the Solid Oxide Fuel Cell of the plate-load of intermediate solid electrolyte and extraneous air electrode (negative electrode).Fuel electrode loadtype (being plate-load) wherein is positioned at dielectric substrate under the air electrode and is coated on the cermet anode support as film, is well-known in the art.The temperature of fuel cell scheduled operation is depended in the selection of electrolyte and air electrode (negative electrode) material, can comprise very wide scope.
For example, if the SOFC of plate-load operates under 700 ℃ of-1000 ℃ of high temperature, electrolyte is selected from stabilized zirconia so, such as (ZrO
2)
0.92(Y
2O
3)
0.08(YSZ), and if 500 ℃ of-700 ℃ of moderate temperatures operations, electrolyte can be a doping cerium dioxide so, such as (Ce
0.90Gd
0.10) O
1.95
A kind of manufacture method of the SOFC of conventional powder production plate-load of using may further comprise the steps:
Blend electrolyte substance (YSZ) and electroactive substance such as nickel to form fuel electrode.The volume % of electroactive substance is about 80% for about 30-, preferably about 40-about 60%.
Provide following examples in order to describe and to illustrate.This should not be considered to restriction by any way.
Embodiment
The tubular SOFC that has the internal recess supporting anodes by the following steps manufacturing:
Oxide green NiO powder and YSZ powder, so the Ni that introduces in the mixture (after the reduction NiO) content is 30-80vol%.Described paste composition comprises distilled water (solvent), methylcellulose or hydroxypropyl methylcellulose (binding agent) and glycerine or polyethylene glycol (plasticizer) in addition.Suitable paste composition comprises the solid supported amount (NiO+YSZ) of the about 90wt% of 70-; The water of 5-25wt%; The binding agent of 1-15wt%; Plasticizer with 0.1-5wt%.Described composition uses high-shear impeller to mix then under shear conditions, such as ∑ shape blade mixer, therefore forms the plastic mass of homogeneous.
As former description, optional additive comprises pore former (for example carbon powder, starch, polymer globules).
Force to make paste pass through mould 124 (Figure 12) at high pressure (for example 1-30 thousand newton) then and extrude described anode-supported pipe.The cross-sectional geometry of the shape decision extruding pipe of described die head.Figure 12 is illustrated as and produces the support interior geometry of wishing, for example swells or the like, and processing has the suitable die design of mold slots 130 and protrusion 126.
Extruding pipe can be under surrounding air dry several hrs.Realize short drying time by the humidity chamber that the humidity of serviceability temperature/wherein can be controlled.Humidity little by little reduces up to pipe fully dry from high initial set value (90-100%RH).
Use and have suitable solid supported amount (about 20-60wt%) and particle size the electrolyte printing ink of (D50＜1 micron) or slurry on dry supporting body structure, to form dielectric substrate then.By dip coating electrolyte (YSZ) is applied on the drying tube, wherein dip time and ink viscosity are determined last electrolyte thickness, perhaps by spray-on process, its medium speed, X/Y position, spraying distance and other parameters also are used for controlling the thickness of dielectric substrate.Desirable, the electrolyte coating layer thickness of 5-50 micron can be realized fine and close dielectric substrate later on and not break in sintering process.Sintering supporter and electrolyte under 1300 ℃ of-1450 ℃ of high temperature then, described temperature depends on the particle size and the solid supported amount of initial electrolysis matter slurry.
Co-sintering anode support and electrolyte structure are got ready and are applied to negative electrode then.Described negative electrode is made of layer 2-4, compares with described skin, and ground floor directly contacts with the electrolyte of the YSZ that comprises higher volumes %, therefore forms the gradient cathode construction.With suitable solid supported amount (20-about 60%) and particle size (D50=＜2 micron), and the YSZ of appropriate percent volume to volume or perovskite material (LSM of common various doping content) preparation negative electrode printing ink, with the composition of realizing that different layers is wished.Comprise that by various coating technologies dip coating, spraying and silk screen printing apply negative electrode, spraying is preferred.Total is at 1000 ℃ of-1250 ℃ of sintering, to form appropriate interfacial characteristics and the electrode structure of negative electrode then.
Although described the present invention in detail in order to illustrate, be only used for illustration purpose but should understand such details, those of ordinary skill in the art can change therein under the prerequisite that does not deviate from the spirit and scope of the invention that limits in the claim.
Claims (36)
1. Solid Oxide Fuel Cell, be characterised in that and comprise the single tubular body that has as the supporting anodes inwall, described supporting anodes forms the hollow centre bore thorax of described fuel cell, comprise that at least one enters the hollow centre bore thorax of described single tubular body from described inwall is outstanding, is used for strengthening on the structure the solid bracing or strutting arrangement of described fuel cell.
2. according to the Solid Oxide Fuel Cell of claim 1, be characterised in that wherein said bracing or strutting arrangement is incorporate with described anode, and comprise a plurality of protuberances or lug boss.
3. according to the Solid Oxide Fuel Cell of claim 1, be characterised in that wherein said tubular body further comprises dielectric substrate and the cathode layer that combines with described supporting anodes.
4. according to the Solid Oxide Fuel Cell of claim 3, be characterised in that wherein said tubular body is cylinder or polygon.
5. according to the Solid Oxide Fuel Cell of claim 4, be characterised in that wherein said tubular body is polygon and comprises at least three sides.
6. according to the Solid Oxide Fuel Cell of claim 5, be characterised in that wherein said tubular body is a hexagon.
7. according to the Solid Oxide Fuel Cell of claim 5, be characterised in that wherein said tubular body comprises three sides in the combination of rounded vertex place.
8. according to the Solid Oxide Fuel Cell of claim 2, be characterised in that wherein said protuberance or lug boss extend along the whole length direction of described tubular body centre bore thorax basically.
9. according to the Solid Oxide Fuel Cell of claim 2, be characterised in that wherein said protuberance or lug boss are shorter than the length of described tubular body centre bore thorax along the length of tubular body on vertically.
10. according to the Solid Oxide Fuel Cell of claim 2, be characterised in that wherein said protuberance or lug boss comprise along the pattern of the common spiral extension of described centre bore thorax length direction.
11., be characterised in that wherein said outstanding protuberance or lug boss relative to each other are symmetrical arranged within described centre bore thorax according to the Solid Oxide Fuel Cell of claim 2.
12., be characterised in that wherein said protuberance or lug boss are normally conical according to the Solid Oxide Fuel Cell of claim 2.
13., be characterised in that wherein said protuberance or lug boss normally square or rectangle according to the Solid Oxide Fuel Cell of claim 2.
14., be characterised in that wherein said protuberance or lug boss are normally circular according to the Solid Oxide Fuel Cell of claim 2.
15., be characterised in that wherein said tubular body two ends are uncovered, perhaps at one end be closed according to the Solid Oxide Fuel Cell of claim 1.
16., be characterised in that the wherein said outstanding bracing or strutting arrangement that enters described tubular body centre bore thorax comprises the structural material identical with inwall according to the Solid Oxide Fuel Cell of claim 1.
17., be characterised in that the structural material of wherein said anode and bracing or strutting arrangement comprises cermet according to the Solid Oxide Fuel Cell of claim 16.
18., be characterised in that wherein said cermet comprises the stable zirconium dioxide or the ceria of doping according to the Solid Oxide Fuel Cell of claim 17.
19., be characterised in that wherein said stabilized zirconia is to comprise (ZrO according to the Solid Oxide Fuel Cell of claim 18
2)
0.92(Y
2O
3)
0.08Material.
20. according to the Solid Oxide Fuel Cell of claim 18, the ceria that is characterised in that wherein said doping is to comprise (Ce
0.90Gd
0.10) O
1.95Material.
21. according to the Solid Oxide Fuel Cell of claim 17, be characterised in that wherein said ceramic-metallic metal is selected from the transiting metal group of the periodic table of elements mutually, elementary state is selected from metal element, alloy and its mixture.
22., be characterised in that wherein said transition metal is a nickel according to the Solid Oxide Fuel Cell of claim 21.
23. according to the Solid Oxide Fuel Cell of claim 21, the content that is characterised in that wherein said ceramic-metallic metal phase is 30vol%～80vol%.
24., be characterised in that wherein the cathode thickness of sintering state is 0.2 millimeter～2.0 millimeters according to the Solid Oxide Fuel Cell of claim 3.
25., be characterised in that the wherein said outstanding thickness that enters the bracing or strutting arrangement of described centre bore thorax sintering state is 0.1～2.0 millimeter according to the Solid Oxide Fuel Cell of claim 1.
26. a method that is used to make the Solid Oxide Fuel Cell that comprises supporting anodes at least is characterised in that to comprise the steps:
(i) blend ceramic electrolyte material and electro-chemical activity transition metal or transition metal oxide are to form the fuel electrode mixture;
(ii) be single tube shape fuel electrode with hollow centre bore thorax with described fuel electrode mixture forming, described electrode have at least one inwardly outstanding enter the solid longitudinally protuberance of described hollow centre bore thorax or lug boss and
(iii) dry described fuel tube electrode.
27., be characterised in that wherein said ceramic electrolyte material is to be selected from the stable zirconium dioxide and the ceramic powders of doping cerium dioxide according to the method for claim 26.
28., be characterised in that the described electro-chemical activity transition metal of wherein introducing in the described fuel electrode mixture is a metal oxide powder according to the method for claim 26.
29. according to the method for claim 26, be characterised in that wherein said transition metal by making the metallic compound predissolve in moisture or nonaqueous solvents, introduce in the described fuel electrode mixture to small part.
30., comprise being characterised in that pore former being incorporated into step in the described fuel electrode mixture according to the method for claim 26.
31., be characterised in that wherein said fuel electrode mixture is the plastic mass that is suitable for extrusion molding according to the method for claim 26.
32., be characterised in that wherein said fuel electrode mixture is the moisture or non-moisture slurry that is suitable for by moulding by casting according to the method for claim 26.
33., be characterised in that wherein said fuel electrode mixture is the dry blend by the drawing method molding according to the method for claim 26.
34. according to the method for claim 26, comprise other step, be characterised in that:
(iv) dielectric substrate is applied to dry fuel tube electrode;
(v) sintering step fuel electrode-electrolyte structure (iv);
(vi) at least one cathode layer is applied to step (v) fuel electrode-the electrolyte structure of sintering and
(vii) the described fuel electrode-electrolyte of sintering-cathode construction is to form the Solid Oxide Fuel Cell of tubulose.
35. supporting anodes that is used for Solid Oxide Fuel Cell, be characterised in that and comprise that the single tubular body with the inwall that forms hollow centre bore thorax, described inwall comprise that at least one outstandingly enters the bracing or strutting arrangement that described hollow centre bore thorax is used for strengthening on the structure anode.
36., be characterised in that wherein said bracing or strutting arrangement is incorporate with described anode, and comprise a plurality of protuberances or lug boss according to the supporting anodes of claim 35.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US49340903P | 2003-08-07 | 2003-08-07 | |
| US60/493,409 | 2003-08-07 | ||
| US10/910,026 | 2004-08-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1864291A CN1864291A (en) | 2006-11-15 |
| CN100472860C true CN100472860C (en) | 2009-03-25 |
Family
ID=37390873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800226341A Expired - Lifetime CN100472860C (en) | 2003-08-07 | 2004-08-05 | Anode-supported solid oxide fuel cells using a cermet electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100472860C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102301512B (en) * | 2008-12-17 | 2015-09-30 | 圣戈本陶瓷及塑料股份有限公司 | Electrode gas channel support thing and the method for the formation of inner passage |
| CN116581330A (en) * | 2023-06-29 | 2023-08-11 | 山东科技大学 | Oxide fuel cell structure for ship power system |
-
2004
- 2004-08-05 CN CNB2004800226341A patent/CN100472860C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1864291A (en) | 2006-11-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6998187B2 (en) | Solid oxide fuel cells with novel internal geometry | |
| RU2303838C9 (en) | Cathode-electrolyte-anode assembly for solid-oxide fuel cell | |
| CN100495793C (en) | Solid porous supporting body flat-plate series micro solid oxide fuel battery | |
| US20090035635A1 (en) | Combination Structure Between Single Cell and Interconnect of Solid Oxide Fuel Cell | |
| JPH09505684A (en) | Electrochemical device | |
| Liu et al. | Tailoring the pore structure of cathode supports for improving the electrochemical performance of solid oxide fuel cells | |
| KR100776299B1 (en) | A method for production of unit cell for solid oxide fuel cell | |
| US20090130523A1 (en) | Tubular Solid Polymer Fuel Cell Comprising a Rod-Shaped Current Collector With Peripheral Glas Flow Channels and Production Method Thereof | |
| CN100472860C (en) | Anode-supported solid oxide fuel cells using a cermet electrolyte | |
| Suzuki et al. | Development of novel micro flat-tube solid-oxide fuel cells | |
| KR20200083705A (en) | Flat - tubular coelectrolysis cell and method for manufacturing the same | |
| EP2045860A1 (en) | Tube-type solid polymer fuel cell and method for manufacturing tube-type solid polymer fuel cell | |
| CN101107740A (en) | Anode-supported solid oxide fuel cells using a cermet electrolyte | |
| CN209071518U (en) | A kind of fuel cell system of high-output power density | |
| CN109326812A (en) | A kind of fuel cell system and preparation method of high-output power density | |
| CN114940625A (en) | Preparation method of ceramic flat tube support type solid oxide fuel cell/electrolytic cell with self-sealing end | |
| KR101169549B1 (en) | Tube-type unit cell for solid oxide fuel cell and stack using unit cells and method for manufacturing unit cell | |
| JP2000067889A (en) | Method for preparing interconnector film for solid electrolyte fuel cell | |
| KR100833626B1 (en) | Anode-supported solid oxide fuel cells using a cermet electrolyte | |
| JPH11126617A (en) | Solid electrolyte-type fuel cell and its manufacture | |
| KR20140136241A (en) | Direct carbon fuel cell comprising anode tube and preparation method thereof | |
| JP2000182627A (en) | Solid electrolyte fuel cell | |
| JP2000182633A (en) | Solid electrolyte fuel cell | |
| CN114914507A (en) | Conductive flat tube support type solid oxide fuel cell/electrolytic cell, preparation method thereof and cell stack structure | |
| Suzuki et al. | Low temperature operated SOFCs using ceria based electrolyte |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 1097110 Country of ref document: HK |
|
| ASS | Succession or assignment of patent right |
Owner name: NANO DYNAMICS ENERGY INC. Free format text: FORMER OWNER: NANODYNAMICS INC. Effective date: 20080926 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20080926 Address after: American New York Applicant after: NanoDynamics Energy, Inc. Address before: American New York Applicant before: NANODYNAMICS, Inc. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: GR Ref document number: 1097110 Country of ref document: HK |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: NEW YORK, THE USA TO: STATE OF FLORIDA, THE USA |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20110216 Address after: American Florida Patentee after: NANO CP, LLC Address before: American New York Patentee before: NanoDynamics Energy, Inc. |
|
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20090325 |