CN101107740A - Anode-supported solid oxide fuel cells using a cermet electrolyte - Google Patents
Anode-supported solid oxide fuel cells using a cermet electrolyte Download PDFInfo
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- CN101107740A CN101107740A CNA2004800358247A CN200480035824A CN101107740A CN 101107740 A CN101107740 A CN 101107740A CN A2004800358247 A CNA2004800358247 A CN A2004800358247A CN 200480035824 A CN200480035824 A CN 200480035824A CN 101107740 A CN101107740 A CN 101107740A
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Abstract
Novel solid oxide fuel cell (SOFC) article and method of manufacture with improved properties at lower costs. The structural features and methods involve fabricating an anode (i.e., fuel electrode); applying a cermet electrolyte, which includes a mixture of ceramic and electrochemically active substances, and applying a cathodic layer. The cermet electrolyte containing a small amount of transition metal reduces the thermal expansion mismatch with the anode, and allows for a graded structure of the electrochemically active substances across the anode/electrolyte structure. Under operating conditions, a dense electrolyte and metal oxide sub-layer exist on the oxidized side (cathode side); while the other side of the electrolyte (reducing side) is made of a porous sub-layer containing transition metal. The tailoring of the amounts of metal present in the anode and the cermet electrolyte allows for greater power output and enhanced electrochemical performance, while maintaining the structural integrity and reliability of the SOFC.
Description
Invention field
The present invention relates generally to fuel cell, more particularly, relate to the Solid Oxide Fuel Cell or the SOFCs of anode-supported, and manufacture method, wherein by using the cermet electrolyte, this fuel cell has the physical property that comprises chemical property of enhancing.
Background technology
Several different Solid Oxide Fuel Cell structural designs have been developed, comprise tubulose, the plane and design monolithic, all in technical literature all documented (for example, Q.M.Nguyen et al., " Science and Technology of Ceramic Fuel Cells ", Elsevier Science, Jan.1995).The SOFC of tubulose design derive from the Welding Problems of plane fuel cell set associative system (see G.Hoogers, " Fuel Cell Technology Handbook ", CRC Press, Aug.2002).Typical tubular SOFC comprises the ceramic membrane that is used to conduct oxygen-ion, thereon Chen Ji air electrode (being negative electrode) and fuel electrode (being anode).Be converted into oxonium ion at negative electrode oxygen, it diffuses through this film, and at anode and fuel reaction.The electronics that produces at anode is moved to the connection circuit by external load then.
Usually follow three types structure, to form above-mentioned structural design:
A) electrolyte-support, wherein Zhi Mi electrolyte is used as carrier, applies anode and negative electrode in every side of this layer and (sees people's such as people's such as Aitken United States Patent (USP) 5,273,837 and Badding United States Patent (USP) 6,428,920;
B) (as the negative electrode-support) of air electrode-support, wherein the porous lanthanum manganite matrix of mixing forms negative electrode, it is coated with airtight dielectric substrate, subsequently the coated anode layer (see, for example, the United States Patent (USP) 5,108,850 of Carlson et al.; And the United States Patent (USP) 5,989,634 of Isenberg; With
C) (as the anode-supported) of fuel electrode-support, wherein the cermet anode carrier is coated with the dielectric substrate film, subsequently coated cathode layer (see the United States Patent (USP) 5,998,056 of Divisek et al., reach the United States Patent (USP) 6,228,521 of Kim et al.).
For obtaining higher efficient and/or lower working temperature, the dielectric substrate of the SOFC of electrolyte-support must be fine and close, airtight and extremely thin (preferred several microns).The technology of the electrolytic thin-membrane of deposition of thin is developed at present and (is seen H.P.Buchkremer et al. on porous electrode matrix (perhaps negative electrode or anode), " Advances in Manufacturing andOperation of Anode; Supported SOFC Cells and Stacks ", Proceedings ofthe Third European Solid Oxide Fuel Cell Forum, June 1998, p.143-149).
Authorize Siemens Westinghouse Power Corp., Orlando, (AES) technology of the so-called air electrode of a lot of patent disclosures of FL-support (is for example seen people's United States Patent (USP)s such as Ruka 5,916,700; United States Patent (USP) with people such as Borglum; United States Patent (USP) 6,379,485 with people such as Borglum).Although obtain significant technology achievement in the SOFC field of tubulose, the fuel cell of negative electrode-support has several shortcomings.Especially, cathode material is doped with the lanthanum manganite of strontium, is very expensive.Their intensity of being made up of ceramic material of negative electrode is lower than by cermet to be made, that is, and and the compound of pottery and metal.The SOFCs of typical negative electrode-support does not have advantage economically, because need the intermediate processing of great amount of investment, such as electrochemical vapour deposition (seeing people's such as Carlson United States Patent (USP) 5,108,850 and the United States Patent (USP) 5989634 of Isenberg).
Therefore, the SOFCs of anode-supported gains attention gradually, keeps high mechanical structure intensity simultaneously and high power density (seeing people's such as Song United States Patent (USP) 6,436,565) is provided because they can low-cost be made.Yet still there is the shortcoming that lacks excellent electrochemical properties and structural reliability in the SOFCs of anode-supported.This mainly is because the thermal coefficient of expansion between anode metal pottery and the conventional ceramic electrolyte does not match, and this or can cause battery failures during fabrication in operation.
Therefore, need improvedly, be easy to adapt to and economic SOFCs and be manufactured on the method for the SOFC of the anode-supported that has good physics and chemical property under the operating condition.
Summary of the invention
The present invention relates to Solid Oxide Fuel Cell (SOFC) widely, it comprises that inner fuel electrode (anode) is as carrier, middle cermet electrolyte and air outside electrode (negative electrode), wherein the cermet electrolyte comprises the less metal phase that is scattered in whole ceramic material.An aspect of of the present present invention, SOFC also can comprise electrode current collector.
Anode can be made by transition metal (as preferred Ni) and pottery (as the stable zirconia or the ceria of doping), i.e. cermet, and it also can be entire cell physical support is provided.The conductivity of anode is based on tenor.By in electrolyte, introduce the transition metal of (as many as 15vol%) (perhaps as being used for identical metal of anode or other active transition metal) and ceramic on a small quantity (as stable zirconia, the ceria that mixes), thus be reduced in mismatch in coefficient of thermal expansion between anode and the cermet dielectric substrate widely.This makes the tenor of anode increase (as many as 80.0vol%), and therefore increases conductivity.
Another aspect of the present invention is scattered in transiting metal group, their alloy, the physical mixture of their element or the physical mixture of uncombined state that whole anode and the electrolytical metal of cermet can be selected from the periodic table of elements mutually.The typical example of useful transition metal includes but not limited to Ni, Co, Cu, Ag and W.Often preferred nickel also can use the noble metal such as the catalytic activity of platinum and ruthenium.
If at high-temperature operation SOFC, be used for the preferably stable zirconia of the electrolytical ceramic electrolyte material of cermet anode and cermet so, for example: (ZrO
2)
0.92(Y
2O
3)
0.08If, be used for the ceria that the electrolytical ceramic electrolyte material of cermet anode and cermet preferably mixes so, as (Ce at moderate temperature (500 °-700 ℃) operation SOFC
0.90Gd
0.10) O
0.195Yet various materials can be used for wide temperature range, select material based on design constraint.
The present invention relates to typical solid oxide fuel cell structural design, comprise tubulose, the designing of plane with monoblock.In fact " monoblock " may comprise, neither tubulose is not again those any structure forms on plane, as elongation, flat tubular type; Spiral-shaped dome, or also can relate to battery structure on third party's backing material.Therefore, the present invention also relates to several versions widely, comprises the method for using the cermet electrolyte to make the SOFC of anode-supported.Each comprises several preferred production technologies in the middle of these designs, determines its applicability by technology and economic factor.For example, preferably make the matrix of tubulose, preferably make planar substrate by casting or Sheet Metal Forming Technology by extrusion technique.
Therefore, other purpose of the present invention provides the method for making improved SOFC, compares with the fuel cell configurations method of routine, has less treatment step and lower cost.Particular importance a bit be that the present invention can obtain the high power density fuel cell at lower cost, keep Mechanical Reliability simultaneously.
According to the present invention, one of these methods with the electrolytical SOFC of cermet of making anode-supported may further comprise the steps:
(i) anode slurry is formed anode layer;
(ii) in the first slurry coating procedure, on anode layer, apply the cermet electrolyte slurry, obtain the anode of cermet electrolyte-coating;
(iii) in the second slurry coating procedure, on the anode of this cermet electrolyte-coating, apply at least a cathode slurry, with obtain cathode layer and
(iv) sintered anode layer, cermet dielectric substrate and at least a cathode layer.
In these manufacture methods, the particle of nano-scale can be used to prepare the SOFC with the electrolytical anode-supported of cermet.For this execution mode, by using ceramic powders (for example: stable zirconia, the ceria of doping) conventional or nano-scale, or use two kinds simultaneously, metal or electrolyte substance can be introduced the fuel electrode mixture.
In addition, the cermet electrolyte slurry of nano-scale can be moisture or anhydrous (promptly based on organic solvent, preferred alcohols and/or ketone).Can under oxidizing atmosphere, carry out the cermet electrolyte of sintering fuel electrode, nano-scale and the step of air electrode about 1050 ℃～about 1300 ℃ temperature range, up to the cermet electrolyte densification fully of nanoscale.
In the other execution mode of the inventive method,, can carry out the step of the anode of sintering metal ceramic electrolyte-coating step applying after the cermet electrolyte slurry (ii).
For these manufacture methods, also can be by using conventional for example ceramic powders, stable zirconia, or the ceria that mixes are introduced anode mixture and cermet electrolyte slurry with electrolyte substance.Active material can be metal or metal oxide.Preferably by using metal oxide powder (being reduced to metallic element subsequently under the SOFC operating condition), the metal in the active material is introduced fuel electrode mixture and/or cermet electrolyte slurry, the scheme as accompanying drawing 3 below is described in further detail.Simultaneously, the cermet electrolyte slurry can be moisture or anhydrous (promptly based on organic solvent preferred alcohols and/or ketone).Can under oxidizing atmosphere, carry out the sintering of the fuel electrode of cermet electrolyte-coating from about 1200 ℃～about 1600 ℃ temperature range, up to the complete densification of this cermet electrolyte.At last, can carry out the sintering of negative electrode about 1000 ℃～about 1200 ℃ temperature range.
For any method of the present invention, by metallic compound, preferable alloy salt, be dissolved in moisture in advance or anhydrous solvent in, metal is partly introduced fuel electrode mixture and/or cermet electrolyte slurry.Randomly, pore former (as carbon dust, starch, polymer drops etc.) can be introduced this fuel electrode mixture to regulate the porosity of electrode.
Manufacturing has in the method for SOFC of the electrolytical fuel electrode of cermet-support, is generally the China ink of conduction or the anode collector of slurry and can be coated on the fuel electrode cermet carrier, eliminates necessity (for the design of tubulose) that physics inserts metal.Cathode collector also for the China ink or the slurry of conduction, for example, can be coated on the negative electrode.
According to the present invention, the SOFC of anode-supported can have the intermediate layer of the deposition between fuel electrode carrier and cermet electrolyte in addition.
Equally, the present invention can be included in the intermediate layer that deposits between cermet electrolyte and the negative electrode in addition.
By before open or more detailed description afterwards, to those skilled in the art, the present invention provides important progress to the Solid Oxide Fuel Cell technology.
With reference to accompanying drawing and following more detailed description, to those skilled in the art, be more readily understood these and other purpose of the present invention, feature, and advantage.
Description of drawings
Following with reference to Reference numeral and detailed description of the invention, further describe essence of the present invention and operational mode, wherein
Figure 1A is the stereogram of the SOFC of sheath of the present invention-support, for description architecture feature is more easily removed part-structure;
Figure 1B is the stereogram of the SOFC of planar anode of the present invention-support, for description architecture feature is more easily removed part-structure;
Fig. 2 illustrates the subgrade under operating condition for the cutaway view of SOFC of the present invention;
Fig. 3 is a block diagram, and the method according to this invention is described, uses conventional size precursor, makes the sequence of steps of the SOFC with the electrolytical anode-supported of cermet;
Fig. 4 is a block diagram, and the precursor that uses nano-scale is described, according to the present invention, make the SOFC with the electrolytical anode-supported of cermet sequence of steps and
Fig. 5 is adapted to the stereogram of electric current collection design of the SOFC of sheath-support, for architectural feature of the present invention more easily is described, removes part-structure.
Detailed description of the invention
Should understand the present invention and be not limited to described special method, material and change, itself can change certainly.Should understand the term that is used for the present invention and only be for putting down in writing special execution mode, being not intended to limit scope of the present invention, scope of the present invention is only limited by additional claim.
Unless otherwise defined, all technology and scientific terminology among the present invention, equivalent in meaning with those skilled in the art's common sense.Though any method of those that put down in writing among the present invention, similarly device and material or equivalent can be used to implement or the advance copy invention, following preferable methods, device and the material only put down in writing.
Following term and expression, as in specification and the appended claim, has the following meaning: " routine " or " stock size " and variant thereof, the solid material of expression dry powdered form, have wherein＞75% particle more than or equal to the particle size distribution of 300nm, specific area is less than 50m
2/ g and
" nano-scale " or its variant, the solid material of expression dry powdered form, have wherein＞75% particle is less than or equal to the particle size distribution of 300nm, and specific area is greater than about 50m
2/ g.
Be explanation and the open material that for example is recorded in publication, structure and method, all publications of mentioning are integrated with the present invention as a reference, and with record of the present invention the present invention are described.The above-mentioned publication that discusses and its are open, only refer to disclosing before the present patent application day.The inventor knows that these are disclosed before the present invention among the present invention.
For accompanying drawing, Figure 1A is the skeleton diagram of the Solid Oxide Fuel Cell (SOFC) 10 of sheath of the present invention-support, and cylindrical tubular goods for a change are with the inner anode layer 12 of better explanation, middle cermet electrolyte 13 and outside negative electrode 14.Anode 12 limits inner pore 15.
Figure 1B, the skeleton diagram of the SOFC16 that planar anode of the present invention supports, the bluff body of flat shape for a change is with the inner anode layer 17 of better explanation, middle cermet electrolyte 18 and outside negative electrode 19.
Thick cermet fuel electrode (being anode) provides Mechanical Reliability and persistence, and the cermet electrolyte makes thermal expansion match better and obtains better chemical property simultaneously.From performance and method, use anode in the fuel cell as supporting construction, for the most useful.General about 0.2～about other anode of 1.0mm level of thickness can be realized high power density by increasing conductivity and reducing activation overpotential (that is, because the loss of voltage of electrochemical charge transfer reaction).Because too frangible not enough with conductivity of carrier, thinner matrix is impracticable.
The inclusion of the electroactive substance in the cermet is preferably metal.When being used for anode, based on the total solid loadings, the preferably about 30vol%～80vol% of tenor.Tenor is less than 30vol% the time, and the cermet anode conducting is poor.The tenor of cermet anode is greater than 30vol% the time, makes to cause conductivity to increase by good interfacial adhesion between metallic.
For improving battery performance, can increase the porosity of anode, make concentration polarization (that is, crossing the loss of voltage that the porous electrode resistance interrelates) remain on floor level with air communication.Under reducing atmosphere, metal oxide powder is reduced to metal, produces porosity in anode substrate, so needs the metal oxide of high level in the fuel electrode mixture.
By using artificial pore former (as carbon dust, starch, polymer drops), during sintering, burn subsequently.The pore creating material of maximum based on the total solid loadings, is fixed as about 50vol%, because too high ratio causes bad mechanical strength.Therefore find, during the about 80vol% of the tenor as many as of cermet anode, guarantee that very high conductivity keeps enough porosity to minimize concentration polarization simultaneously.Amount of metal higher in the cermet anode can cause big thermal coefficient of expansion, with the coating the cermet electrolyte do not match, cause processing or battery-operated during crackle appears.Below at length discuss the ceramic material of cermet anode.
When tenor is too high in the anode, between anode carrier and typical pottery (that is, 100% pottery) electrolyte, exist excessive thermal coefficient of expansion not match usually.Usually the amount that is present in the metal of anode by restriction is avoided these adverse effects, for example about 50vol% (seeing people's such as Song United States Patent (USP) 6,436,565), or the anode construction by the use classification (seeing people's such as Kim United States Patent (USP) 6,228,521).Anode of the present invention comprises a large amount of metals, specifically greater than 50vol%.From the technology viewpoint, the SOFC that thin dielectric substrate is applied to the single layer anode support is more feasible equally.
Metal is with relatively little amount electrolyte structure the time, about 0.1vol%～15.0vol%, and the thermal coefficient of expansion that can be reduced in widely between anode and the electrolyte does not match.Therefore, can on the supporting anodes of highly conductive, form thin cermet dielectric substrate, and the structural intergrity of battery is not had adverse effect.
If it is enough little to introduce the amount of electrolytical metal, metal is dispersed in ceramic substrate mutually well, and electrolytical conductance can be sufficiently low, to avoid short circuit.Under normal SOFC operating condition, the metal in the electrolyte is present in fuel-side with its element (reduction) form; The air of cathode side existence simultaneously remains metal oxide (oxidation) form (see figure 2) with metal.These metals: pottery and metal oxide: the thickness of ceramic subgrade depends on the dividing potential drop of fuel and oxidant (air).Metal oxide: the ceramic electrolyte subgrade must be fine and close and airtight in order to avoid fuel and oxidant gas mix.
Under operating condition, the metal that is present in the electrolyte subgrade of described reduction causes the anode construction classification of anode interior, and its restriction anode interfacial resistance is also improved adhesion between these layers.Improve chemical property equally by increasing the three-phase boundary area.On the other hand, be present in the metal oxide of described oxidization electrolysis matter subgrade, produce the extremely thin and fine and close electrolyte structure that higher efficient and lower working temperature need.Be described in more detail above-mentioned behavior with reference to figure 2.
Fig. 2 ordinary representation supporting anodes layer 20, " porous " dielectric substrate 22, fine and close cermet dielectric substrate 24 and cathode layer 26.Under the SOFC operating condition, the metal (as NiO) in the fine and close cermet dielectric substrate 24 is oxidized, simultaneously the metal in " porous " cermet dielectric substrate 22 be reduced (as, Ni).By the electrolyte subgrade, specifically, metal: pottery and metal oxide: the existence of ceramic layer makes the raising of chemical property.The metal of reduction: ceramic subgrade, promptly " porous " cermet dielectric substrate 22, become electrolyte/anodic interface effectively.Because a large amount of ceramic masses is contained at this interface, activation polarization is lowered.
Strengthen electrochemical reaction equally by increasing the three-phase boundary territory.Dividing potential drop metal oxide based on fuel and oxidant: ceramic subgrade, that is, fine and close cermet dielectric substrate 24, extremely thin (less than 10 microns) can become.If metal oxide mutually sufficiently low (＜15vol%) and be dispersed in ceramic substrate well, can realize densification, approach and airtight metal oxide: ceramic structure.The electrolytical ionic conductivity of cermet directly gets state and metal oxide electro-chemical activity mutually based on dispersion.The thickness of the cermet dielectric substrate 24 by being reduced in the densification under the operating condition (by reducing the metal oxide of fuel-side), same described electrolytical resistance is lower.Therefore, if, can compensate by the minimum resistance loss because the conduction of non-ionic or hybrid ionic time looks (as metal oxide) causes any loss of the ionic conductivity of the cermet dielectric substrate 24 by densification.
Fig. 3 and 4 public use respectively " stock size " and " nano-scale " powder the time the processing block diagram.Based on the material of nickel and 8mol% yittrium oxide-processing stage that stable zirconia being used for illustrating, but as above-mentioned, can use those other transition metal and the ceramic material known to those skilled in the art.
The process route that shows in the Figure 4 and 5 depends on the anode mixture that preparation contains metal and ceramic compound.Moisture or non-aqueous media can be used to suspended particles.Yet often the preferred water medium is because their cost benefit and the environmental consideration that relates to organic solvent inflammability and toxicity.Common treatment additive (the dispersant of same use, bond, plasticizer), guarantee to disperse well, homogeneity (see R.J.Pugh et al. with stable mixture, " Surface andColloid Chemistry in Advanced Ceramics Processing ", Marcel Dekker, Oct.1993).Can change the feature of these mixtures, such as viscosity by changing different raw-material amount or performance.They are adapted to concrete forming step then.
Be used for the fuel electrode carrier and electrolytical ceramic material can be stable zirconia, be preferred for high temperature SOFC (700～1000 ℃).These preferably include 8 moles of yittrium oxide-stable zirconium dioxide (" Y8SZ "), (ZrO
2)
0.92(Y
2O
3)
0.08Other useful materials are the cerias that mix, and are preferred for the SOFC (500 ℃～700 ℃) of moderate temperature.These preferably include the ceria (" CGO ") of gadolinium-doping, (Ge
0.90Gd
0.10) O
1.95Yet each in these materials all can be used in very wide temperature range.Certainly, can be and consider to use, known to those skilled in the art, other be suitable for the material that the SOFC electrolyte is used.
Be used for cermet fuel electrode (anode) and preferably belong to the transiting metal group of the periodic table of elements, their alloy or physical mixture with the electrolytical metal of cermet mutually.Because under reducing atmosphere, have higher conductivity and its cost benefit, preferred nickel (Ni).Metal can be introduced the fuel electrode and the cermet electrolyte of described support by different precursors, described precursor known to those skilled in the art such as metal dust, metal oxide powder, and slaine (moisture or anhydrous).Metal oxide powder, such as preferred green NiO often, this is because their cost benefit and its adaptability to ceramic process.Use the pure metal oxides powder for the special recommendation of cermet electrolyte method, this can remain oxidation because of metal under the SOFC operating condition.
Metal in the cermet anode is about 30vol%～80vol% mutually.The thickness of the cermet anode of sintering state is based on the master-plan of fuel cell.For example, anode thickness can be about 0.2mm～about 1.0mm in the fuel cell of minor diameter tubulose.
Metal in the cermet electrolyte is about 0.1vol%～about 15vol% mutually.The electrolytical thickness of the cermet of sintering state preferably remains on below 500 microns, and is preferred below 100 microns, more preferably below 50 microns, and 5～30 micron thickness most preferably.The actual (real) thickness part is based on the size and the design of fuel cell.
Use thick anode carrier, can be with after-applied extremely thin electrolyte and cathode.The reduction of electrolyte and cathode thickness can improve heat resistanceheat resistant acute degeneration and chemical property.The remarkable increase of battery performance and stability also makes battery to operate under lower temperature.This can be used for battery pile with cost-effective material (as stainless steel) conversely, (as, the battery manifolding).
Aforesaid method also makes the intermediate layer of between electrode and electrolyte structure deposition of thin, need not influence the number of times of sintering circulation.Between anode and electrolyte, between electrolyte and the negative electrode, or apply the advantage that the intermediate thin rete has possibility simultaneously.These layers can increase battery performance, for example: by the use catalyst material, or prevent opposite chemical reaction during sintering.These intermediate layers are chosen wantonly among the present invention, shown in Fig. 3 and 4.The intermediate layer can be made up of catalyst.Typical example comprises CGO, i.e. ceria gadolinium oxide as the aforementioned, and consumption is the Ni and the Ru of about 40～60vol% and aequum.The stable zirconium dioxide of other comprised strontium is SSZ, uses with Ni and Ru.The metal of other catalytic activity also can be contained in the intermediate layer, and as Pt, Pd and Rh slightly lift numerical example.
The geometry of anode carrier can both ends open tubulose, the tubulose of end sealing, plane, or the known structure of other prior art.Especially, the plastic substance of extruding is preferred for making cast (in both ends open or sealing at one end).The U.S. Patent application 10/910,026 of the application in 3 days Augusts in 2004 of common pending trial, " SOLID OXIDE FUEL CELLSWITH NOVEL INTERNAL GEOMETRY " provides the various examples of making tubular type, and it is all also as the present invention.
On the other hand, preferably use foundry engieering (being liquid processes) or process for stamping (being dry method) casting flat shape.Foundry engieering comprises slip-casting, spun casting, gel casting, banded casting etc.
Process for stamping comprises dry-pressing and balanced compacting.All these process routes record (is seen J.S.Reed for example, " Principles of Ceramic Processing, 2nd Edition ", J.Wiley﹠amp in the literature; Sons, Nov.1994), it is incorporated herein by reference.
Anode mixture can be the ductile material by the Any shape of extrusion technique molding.Anode mixture can be moisture or anhydrous slurry, by the foundry engieering casting, and preferred slip-casting, centrifugal casting, gel casting, and band shape-casting.In addition, anode mixture can be by process for stamping, preferred dry-pressing and wait (quiet) pressure to suppress the dry state mixture of casting.
Can improve the chemical property of fuel cell in addition by the additive of introducing other, specifically, the artificial pore former in the electrode layer (perhaps anode, or negative electrode or while) is with the porosity of adjusting electrode, and their catalytic activity of optimization.
For the cermet electrolyte, the moisture or anhydrous cermet electrolyte slurry that contains a small amount of described transistion metal compound is used to unsintered shaping anode carrier (tubulose or plane).Before the coating electrolyte, can partially sinter supporting anodes, but this chooses wantonly.Can use the typical slurry coating technique known to those skilled in the art.These include but not limited to, spraying, and dip-coating, silk screen printing, impression is smeared, transfer printing, etc.The coating technique that is fit to is based on the thickness of the shape and the coating of fuel electrode matrix.Need thin uniform and well-bonded structure, to guarantee the loss of best performance and minimum resistance.
Applying cermet electrolyte coating (on unsintered anode carrier) before, similar techniques can be used for applying thin intermediate layer (＜20 microns).Yet this is an optional step.
In a kind of execution mode, be used to use cermet electrodes to make the method for the SOFC of anode-supported, described cermet electrodes depends on uses conventional ceramic powders, conventional metal and/or metal oxide powder, and other metallic compounds, comprise slaine.Do not match by the thermal coefficient of expansion that is reduced between anode carrier and the cermet electrolyte coating, can realize the sintering (up to dielectric substrate densification fully) of these two kinds of layers, to the structural intergrity of fuel cell without any harmful damage.This and the fuel cell processing method of establishing differ widely, wherein electrode substrate partly be sintering or at (the seeing the U.S. Patent application 6,436,565 of Songet al) that apply sintering before the electrolyte coating.The feasible only sintering of sintered cathode layer (＜1200 ℃) is twice subsequently.
If " routine " powder is used for described manufacture method, such as shown in Figure 3, under oxidizing atmosphere, the anode of cermet electrolyte-coating is than higher temperature sintering, about 1200 ℃～about 1600 ℃, to realize the complete densification of described cermet electrolyte coating.
" air electrode slurry ", i.e. cathode slurry contains the mixture of cathode material and ceramic electrolyte material, uses conventional slurry coating processes to be applied on the airtight cermet electrolyte then.Second air electrode contains single-phase cathode material, is applied to then on the dry main cathode.Use dual cathode construction to make thermal coefficient of expansion match with described electrolyte well, improve chemical property.Preferred cathode material is selected from following perovskite: LaSrMnO
3, LaSnFeO
3, (LaSr) (CoFe) O
3, LaCaMnO
3(LaCa) (CoFe) O
3Then usually at relative low temperature, usually less than 1200 ℃ of sintering air electrode coatings.Because the chemical reactivity at high temperature cathode/electrolyte interface increases usually, so use lower sintering temperature, its possibility that causes forming the less important phase of opposing conversely (is seen P.J.Gellings et al., " The CRCHandbook of Solid State Electrochemistry ", CRC Press, Dec.1996).Between the electrolyte and first negative electrode, use the intermediate layer, can help to prevent the formation of the compound of these opposings under the high temperature, yet in this execution mode, the intermediate layer is chosen wantonly.
Other execution mode record is used to use described cermet electrolyte to make the method for the SOFC of described anode-supported, described cermet electrolyte depends on use " nano-scale " ceramic powders, " nano-scale " metal and/or metal oxide powder, and other metallic compounds, comprise slaine.The powder of nano-scale is better than conventional ceramic powders, and this is because their high surfaces area makes them in low relatively sintering temperature densification.Therefore, use the pottery and the metal dust of nano-scale can reduce the electrolytical densification fully of described cermet significantly.In this execution mode, negative electrode can be applied on the described unsintered electrolyte coating, and entire cell (being anode carrier, cermet electrolyte and negative electrode) can be in the temperature co-sintered below 1200 ℃ in single cycle.
Fig. 4 represents to be used for a kind of manufacture method of the present invention, is used for the metal and the ceramic powders of the nano-scale of anode and cermet electrolyte structure (as mentioned above).The powder of introducing nano-scale in described cermet electrolyte can reduce the temperature of sintering significantly.Very high surface area (as＞100m
2/ g) metal oxide (as green NiO) and the pottery (as Y8SZ) powder can reduce as described in the electrolytical sintering temperature of cermet to being lower than 1200 ℃.Therefore, cathode layer (as above record) can be applied on the anode of unsintered cermet electrolyte-coating, and at a plurality of layer of sintering below 1200 ℃, make the complete densification of electrolyte.In the manufacturing of the fuel electrode that supports, the use of the powder of nano-scale is chosen wantonly, and also can part and the merging of " routine " powder.The material of optional nano-scale helps to minimize production cost, simultaneously optimization conductivity and mechanical stability.Therefore, compare with the traditional many or three sintering stages that need in many SOFC manufacture methods, the single hop sintering that the present invention makes among the SOFC of anode-supported provides the important techniques progress.
In Fig. 3 and the 4 described execution modes,, after electrolyte and the cathode layer, can apply current-collector to finish the manufacturing of fuel cell at sintered anode.For this reason, often use the China ink or the slurry of highly conductive, preferably contain silver.
Fig. 5 is the skeleton diagram of the Solid Oxide Fuel Cell (SOFC) 50 of sheath of the present invention-support, and its cylindrical tubular goods for a change are to illustrate inner anode layer 52 well, middle cermet electrolyte 54 and outside negative electrode 56.Anode 52 limits internal holes 57.The anode and cathode collector 58 and 59 that also show silk screen printing in this execution mode respectively.
In typical tubular design, the collection of anode current depends on usually uses metal gasket (not showing).The higher conductivity of metal gasket makes electronics shift by a plurality of physics contact points from anode.Yet the main shortcoming of this method is, with the time bar of relative prolongation, keeps good physics contact between metal gasket and anodic coating under reducing atmosphere.Usually, because under operating condition, the unsteadiness of metal gasket, physics contact loss in time.On the contrary, use the supporting anodes that is rich in the highly conductive metal to make, China ink or the slurry that conducts electricity directly is applied on the fuel electrode, not be used in any physics insert (see figure 5) of use in the pipe.This is of value to the chemical property of battery conversely, because physical obstacle does not hinder fuel supply, and fuel is assigned to the anode reaction site more equably.
Similarly, use the cermet anode carrier of highly conductive also beneficial to the design of simplified anode current acquisition.Usually in the design of tubulose, under operating condition, metal gasket is used for drawing electronics from anode.Yet, be easy to dimensional instability at these metal gaskets of working temperature, and if do not have to keep physics well to contact, the efficient of current-collector reduces.The China ink or the slurry of the stable conduction of therefore preferred use directly are applied on the fuel electrode of highly conductive.
Following embodiment be used to explain book and accompanying drawing.Do not think restriction in any case.The variation of a lot of aspects of the present invention, displacement and combination are also within the spirit and scope shown in claim of the present invention.
Embodiment 1-is by the fuel electrode carrier of extrusion tectonics tubulose
Preferably by extrude the fuel electrode carrier that slurry is a ductile material molding tubulose (see J.Benbow et al., " Paste Flow and Extrusion ", Clarendon Press, Jan.1993).
Oxide green, the NiO powder, with the Y8SZ powder, the feasible NiO that reduces subsequently, the amount of introducing the Ni of mixture is 30～80vol%.
Paste compound further comprises distilled water (carrier fluid), methylcellulose or hydroxypropyl methylcellulose (adhesive) and glycerine or polyethylene glycol (plasticizer).
Suitable paste compound can comprise 70～90wt%'s (NiO+Y8SZ), 5～25wt% water, 1～15wt% adhesive and 0.1～5wt% plasticizer.Use high-shear mixer then,, under high shear conditions, mix described composition, so that form the ductile material of homogeneous such as sigma-blade mixer.
Optional additive comprises the pre-water-soluble Ni (NO of pore former (for example: carbon dust, starch, and polymeric beads)
3)
2Solution.
Then by (under as 1～50kN), making slurry pass through punch die, extrude anode tube at high pressure.The shape of punch die is determined the geometric shape in the cross section of extruding pipe.For example, successfully extrude the pipe of external diameter 5mm internal diameter 4mm, and be used for electrochemical property test.
The pipe of extruding can be in surrounding air dry several hours.Realize shorter drying time by the temperature/humidity chamber of using controlled humidity.Initial set point 90～100%RH from high little by little reduces humidity, and is fully dry up to pipe.
The described cermet electrolyte slurry of the electrolytical preparation of embodiment 2-cermet and coating/sintering is a multicomponent system, especially contain solvent (20～60wt%), inorganic phase (40～80wt%), dispersant (0.1～3wt%), adhesive (1～15wt%), and plasticizer (1～15wt%).
Solvent divides divided powder, and guarantees to dissolve organic component.Water is preferred medium, but by using organic media often to realize easier method, such as pure and mild ketone.
Described inorganic by main Y8SZ phase and less important green NiO phase composition, so that reduce NiO subsequently, the amount of introducing the Ni of mixture is 0.1～15.0vol%.The performance that obtaining the desirable sinterable powder of theoretical dense coating needs is, small particle diameter (promptly 0.1～1.0 micron), narrow particle size distribution, a shape that waits spool and the state of non-cohesion.
Must have dispersant (dispersant), obtaining Y8SZ and NiO particle good stable UA dispersion in solvent, and stablely have a high solids content: the suspension of organic substance ratio.Commercial dispersant easily obtains, and should test the efficient of the solvent that is used for needs.For example, verified " KD2 " (deriving from ICI) is Y8SZ and NiO effective dispersant in acetone.
Adhesive (adhesive) is added described slurry to improve the intensity of unsintered coating.Adhesive forms organic bridge, produces firm adhesion after the evaporating solvent.Polyvinyl alcohol (PVA) and polyvinyl butyral resin (PVB) are respectively to be used for moisture slurry and based on the suitable adhesive of the slurry of organic media.Also can use the suitable adhesive known to those skilled in the art in addition.
Plasticizer (plasticizer) is joined described slurry, reducing the glass transition of adhesive, so that use and store.But the present invention considers is not limited to common plasticizer is used for PVA, such as polyethylene glycol, and glycerine and atmospheric water.Similarly, the common plasticizer that is used for PVB includes but not limited to, dibutyl phthalate (DBP) and polyethylene glycol (PEG).
The additive that other are optional, homogeneous agent and antifoaming agent such as routine can optionally add as required.
The special effective method that pottery and metal oxide powder are scattered in solvent is to mill and mix.This ends the cohesion of generation naturally in the start powder, and promotes the absorption of dispersant.Modal grinding method is a ball milling, but preferred stronger method for grinding, for example vibratory milling, and guaranteeing that described powder is more effective does not condense.
This need use abrasive media, preferred stable zirconium oxide bead.
Because different organic additive competitive Adsorption on powder, is important so add the order of organic additive.Therefore, carry out slurry process in two stages.At first, powder was dipped in the solvent as many as 24 hours, and sneaked into dispersant.Be uniformly mixed thing and described particle when suitably disperseing, mill/blend step for second, add adhesive and plasticizer, carried out as many as again 24 hours.Add before other organic compounds, add dispersant to prevent the competitive Adsorption on particle surface.
In case that obtain concentrating and steady suspension, but the described cermet electrolyte slurry of anode carrier pipe dip-coating.Coating layer thickness directly depends on the viscosity of described slurry.Use utmost point low viscosity slurry, usually＜50mPa-s the time, obtain thin layer.
After the drying, the anode carrier of the described cermet electrolyte of sintering-coating between 1200 ℃～1600 ℃ is up to the complete densification of described cermet electrolyte.Should keep relatively low (as＜2 ℃/minute) from the rate of heat addition of room temperature, to avoid owing to the uneven any of shortage that in final products, produces that burns of organic compound up to 600 ℃.In case reach sintering temperature, and keep this temperature, preferred 0.5～4.0 hour of the time of staying.
The preparation and the coating of embodiment 3-air electrode
Prepare cathode mix with the same method of cermet electrolyte slurry record among the embodiment 2.First cathode layer is the mixture of cathode material (as 50wt%) and Y8SZ (as 50wt%).Preferred cathode material is La
1-xSr
xMnO
3And La
1-xSn
xFeO
3, wherein x is 0.1～0.5.Second electrode is single-phase cathode material, is used to improve conductivity, is become by above-mentioned preferred cathode material usually.
Air electrode can be smeared or spray, and for example uses spray gun, yet the known additive method of prior art is suitable equally.After the drying, low relatively temperature sintering they, be usually less than 1200 ℃, preferred 0.5～4.0 hour of the time of staying.
Though put down in writing the present invention in order to describe in detail, should understand these explanations and only be used for understanding, those skilled in the art need not leave the spirit and scope that claim of the present invention limits, can change.
Claims (39)
1. Solid Oxide Fuel Cell is characterized by and comprises:
Anode layer,
At least one cathode layer and
Place the dielectric substrate between described anode layer and the cathode layer,
Wherein said dielectric substrate further comprises the cermet electrolyte.
2. Solid Oxide Fuel Cell as claimed in claim 1 is characterized in that, as composite construction, wherein said anode layer is inner layer, and described cathode layer is outside layer, and described dielectric substrate places between described anode layer and the described cathode layer.
3. Solid Oxide Fuel Cell as claimed in claim 1 is characterized in that, wherein the cermet electrolyte comprises:
Be selected from stable zirconia, the ceria of doping and the ceramic material of its mixture and
The metal phase that comprises at least a metal of periodic table of elements transiting metal group.
4. Solid Oxide Fuel Cell as claimed in claim 3 is characterized in that wherein stable zirconia is (ZrO
2)
0.92(Y
2O
3)
0.08, the ceria of doping is (Ce
0.90Gd
0.10) O
1.95
5. Solid Oxide Fuel Cell as claimed in claim 3 is characterized in that wherein transition metal is selected from Ni, Co, Cu, Ag, W, Pt and Ru.
6. Solid Oxide Fuel Cell as claimed in claim 3 is characterized in that, in the wherein said cermet electrolyte, the tenor of described metal phase is about 0.1vol%～about 15.0vol%.
7. Solid Oxide Fuel Cell as claimed in claim 3 is characterized in that wherein the thickness of the dielectric substrate of sintered state is less than 0.1mm.
8. Solid Oxide Fuel Cell as claimed in claim 1 is characterized in that, wherein said anode layer further comprises:
Be selected from stable zirconia, the ceria of doping and the ceramic material of its mixture and
The metal phase that comprises at least a metal of periodic table of elements transiting metal group.
9. Solid Oxide Fuel Cell as claimed in claim 8 is characterized in that wherein stable zirconia is (ZrO
2)
0.92(Y
2O
3)
0.08, the ceria of doping is (Ce
0.90Gd
0.10) O
1.95
10. Solid Oxide Fuel Cell as claimed in claim 8 is characterized in that wherein transition metal is selected from Ni, Co, Cu, Ag and W.
11. Solid Oxide Fuel Cell as claimed in claim 8 is characterized in that, the tenor of the metal phase of wherein said anode metal pottery is about 30vol%～about 80vol%.
12. Solid Oxide Fuel Cell as claimed in claim 8 is characterized in that, the thickness of the anode layer of wherein said sintered state is about 0.2mm～about 1.0mm.
13. Solid Oxide Fuel Cell as claimed in claim 1 is characterized in that, wherein said cathode layer comprises:
Comprise first cathode material and be selected from the ceria of stable zirconia, doping and first cathode layer of the negative electrode ceramic material of its mixture and
Second cathode layer that comprises second cathode material.
14. the Solid Oxide Fuel Cell as claim 13 is characterized in that, wherein stable zirconia is (ZrO
2)
0.92(Y
2O
3)
0.08, the ceria of doping is (Ce
0.90Gd
0.10) O
1.95
15. the Solid Oxide Fuel Cell as claim 13 is characterized in that, wherein said first and second cathode materials are independently selected from La
1-xSr
xMnO
3And La
1-xSn
xFeO
3And wherein x is 0.1～0.5.
16. Solid Oxide Fuel Cell as claimed in claim 1 is characterized by and further comprises and place adjacent described anode layer and/or described at least one cathode layer, and at least one intermediate layer of the improved fuel battery performance between the described dielectric substrate.
17. the Solid Oxide Fuel Cell as claim 16 is characterized in that, the intermediate layer of wherein said raising performance comprises catalyst material.
18. Solid Oxide Fuel Cell as claimed in claim 1, it is characterized by comprise tubulose and at both ends open, tubulose and at one end opening, plane or monoblock structure construction, wherein said structure construction comprises anode and cathode collector.
19. a fuel battery is characterized by and comprises as Solid Oxide Fuel Cell as described in claim 18 a plurality of.
20. the method by following steps manufacturing Solid Oxide Fuel Cell is characterized in that described step comprises:
(i) anode slurry is formed anode layer;
(ii) in the first slurry coating procedure, on anode layer, apply the cermet electrolyte slurry, to obtain the anode of cermet electrolyte-coating;
(iii) in the second slurry coating procedure, at least a cathode slurry is coated on the anode of cermet electrolyte-coating, with obtain cathode layer and
The (iv) described anode layer of sintering, described cermet electrolyte slurry and described at least one cathode layer.
21. the method as claim 20 is characterized in that, wherein:
Described anode slurry comprises the ceria that is selected from stable zirconia, doping and first ceramic material of its mixture, with first metal of at least a metal that comprises periodic table of elements transiting metal group mutually;
Described cermet electrolyte slurry comprises the ceria that is selected from stable zirconia, doping and second ceramic material of its mixture, with second metal of at least a metal that comprises periodic table of elements transiting metal group mutually; Described at least a cathode slurry comprises and is selected from La
1-xSr
xMnO
3And La
1-xSn
xFeO
3Cathode material, wherein x is 0.1～0.5.
22. the method as claim 21 is characterized in that, wherein said at least a cathode slurry further comprises the ceria that is selected from stable zirconia, doping and the negative electrode ceramic material of its mixture.
23., it is characterized in that wherein as the method for claim 21:
First ceramic material comprises the ceramic powders of stock size and the ceramic powders of nano-scale, with first metal comprise mutually the metal dust of stock size and nano-scale metal dust and
Second ceramic material comprises the ceramic powders of nano-scale, comprises the metal dust of nano-scale mutually with second metal.
24., it is characterized in that wherein anode slurry further comprises pore-forming material as the method for claim 21.
25., it is characterized in that wherein metal being introduced in described anode slurry and the described cermet electrolyte slurry by metal oxide and/or slaine as the method for claim 21.
26. the method as claim 20 is characterized in that, wherein by extrude, casting or Sheet Metal Forming Technology form anode layer.
27., it is characterized in that wherein said cathode material is selected from LaSrMnO as the method for claim 23
3, LaSnFeO
3, (LaSr) (CoFe) O
3, LaCaMnO
3(LaCa) (CoFe) O
3
28. as the method for claim 20, it is characterized by and comprise other step, it comprises and is adjacent to described anode layer and/or described cathode layer and described dielectric substrate that deposition improves at least one intermediate layer of fuel battery performance.
29. as the method for claim 20, it is characterized by and comprise other step, it comprises: (v) to described anode layer and described at least one cathode layer, apply anode collector and cathode collector.
30. as the method for claim 20, it is characterized by and comprise other step, its be included in step (ii) apply after the described cermet electrolyte slurry anode of the described cermet electrolyte of sintering-coating.
31. the method as claim 30 is characterized in that, wherein:
Described anode slurry comprises the ceria that is selected from stable zirconia, doping and first ceramic material of its mixture, with first metal of at least a metal that comprises periodic table of elements transiting metal group mutually;
Described cermet electrolyte slurry comprises second cermet material of the cathode material of the ceria that is selected from stable zirconia, doping and its mixture, with second metal of at least a metal of the transiting metal group that comprises the periodic table of elements mutually;
Described at least a cathode slurry comprises and is selected from La
1-xSr
xMnO
3And La
1-xSn
xFeO
3Cathode material, wherein x is 0.1～0.5.
32. the method as claim 33 is characterized in that, wherein said at least a cathode slurry further comprises the ceria that is selected from stable zirconia, doping and the negative electrode ceramic material of its mixture.
33. the method as claim 31 is characterized in that, wherein first and second ceramic materials are ceramic powders of stock size.
34. the method as claim 31 is characterized in that, wherein said anode slurry further comprises pore-forming material.
35., it is characterized in that wherein metal being introduced in described anode slurry and the described cermet electrolyte slurry by metal oxide and/or slaine as the method for claim 30.
36. the method as claim 30 is characterized in that, wherein by extrude, casting or Sheet Metal Forming Technology form anode layer.
37. the method as claim 31 is characterized in that, wherein said cathode material is selected from LaSrMnO
3, LaSnFeO
3, (LaSr) (CoFe) O
3, LaCaMnO
3(LaCa) (CoFe) O
3
38. as the method for claim 30, it is characterized by and comprise other step, it comprises and is adjacent to described anode layer and/or described cathode layer and described dielectric substrate that deposition improves at least one intermediate layer of fuel battery performance.
39. as the method for claim 30, it is characterized by and comprise other step, it comprises: (v) to described anode layer and described at least one cathode layer, apply anode collector and cathode collector.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US52639803P | 2003-12-02 | 2003-12-02 | |
| US60/526,398 | 2003-12-02 | ||
| US10/910,026 | 2004-08-03 | ||
| USPCT/US04/025233 | 2004-08-05 | ||
| US10/999,735 | 2004-11-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101107740A true CN101107740A (en) | 2008-01-16 |
Family
ID=39000628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004800358247A Pending CN101107740A (en) | 2003-12-02 | 2004-12-01 | Anode-supported solid oxide fuel cells using a cermet electrolyte |
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| CN (1) | CN101107740A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102317506A (en) * | 2009-01-07 | 2012-01-11 | 法国原子能及替代能源委员会 | Manufacturing comprises the high temperature electrolyser of elementary cell heap or the method for high-temperature fuel cell |
| CN103779526A (en) * | 2012-10-25 | 2014-05-07 | 中央大学 | Ceramic metal film, method for producing same and use thereof |
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| CN104025352A (en) * | 2011-10-24 | 2014-09-03 | 丹麦技术大学 | High performance fuel electrode for a solid oxide electrochemical cell |
| CN103779526A (en) * | 2012-10-25 | 2014-05-07 | 中央大学 | Ceramic metal film, method for producing same and use thereof |
| CN103779526B (en) * | 2012-10-25 | 2016-05-11 | 中央大学 | Ceramic metal film, method for producing same and use thereof |
| CN113394439A (en) * | 2015-02-06 | 2021-09-14 | 赛瑞斯知识产权有限公司 | Method of forming an electrolyte |
| CN108292769A (en) * | 2015-10-08 | 2018-07-17 | 低排放资源公司 | The tubular solid-oxide electrochemical cell of electrode supporting |
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| CN109841844A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of lanthanum manganate base cathode support solid oxide fuel cell and its application |
| CN110230028B (en) * | 2019-06-14 | 2021-06-29 | 深圳市致远动力科技有限公司 | Preparation method of solid film fuel cell |
| CN110230028A (en) * | 2019-06-14 | 2019-09-13 | 深圳市致远动力科技有限公司 | The preparation method of solid film fuel cell |
| CN113394434A (en) * | 2020-03-10 | 2021-09-14 | 太阳诱电株式会社 | Solid oxide fuel cell and method for manufacturing same |
| CN113394434B (en) * | 2020-03-10 | 2024-03-22 | 太阳诱电株式会社 | Solid oxide fuel cell and method for manufacturing same |
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