CN103199288B - Electrode of solid oxide fuel battery and preparation method for solid oxide fuel battery - Google Patents
Electrode of solid oxide fuel battery and preparation method for solid oxide fuel battery Download PDFInfo
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- CN103199288B CN103199288B CN201310093319.9A CN201310093319A CN103199288B CN 103199288 B CN103199288 B CN 103199288B CN 201310093319 A CN201310093319 A CN 201310093319A CN 103199288 B CN103199288 B CN 103199288B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- 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
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Abstract
The invention provides a solid oxide fuel battery, comprising a cathode layer, an electrolyte layer, an inner anode layer and an outer anode layer, wherein the electrolyte layer is compounded on the cathode layer; the inner anode layer is compounded on the electrolyte layer; the outer anode layer is compounded on the inner anode layer; and the oxygen ion conductor material content of the inner anode layer is higher than that of the outer anode layer. The internal strength of the electrode is lower than the interface bonding strength of electrodes and electrolyte, and the outer anode layer generates cracks preferentially under the action of stress and releases stress, so that the effects of stress buffering and protecting interface bonding of the electrodes and the electrolyte are achieved. The electrode is of a three-dimensional porous structure, and the influence of the cracks in the electrode on the performance of the battery is obviously weaker than that of interface cracks, so that the stability of the battery is improved. In addition, the inner anode layer and the outer anode layer provided by the invention can be sintered together, so that the preparation process is simpler.
Description
Technical field
The present invention relates to Solid Oxide Fuel Cell technical field, particularly relate to electrode of a kind of Solid Oxide Fuel Cell and preparation method thereof.
Background technology
Solid Oxide Fuel Cell (SOFC) is a kind of device fuel chemical energy being converted into electric energy.SOFC is primarily of electrolyte (electrolyte), anode (anode), negative electrode (cathode) composition, and wherein, anode is also fuel electrodes (fuel electrode), and negative electrode is also air pole (air electrode).Anode is the place that oxidation occurs fuel, and negative electrode is the place of oxidant reduction, and catalyst and the oxygen ion conductor material of accelerating electrode electrochemical reaction are all contained in the two poles of the earth.Be equivalent to DC power supply time battery operated, anode is power cathode, and negative electrode is positive source.
Existing SOFC electrode is subject to the effect of stress such as thermal stress under the environment of long term high temperature (600 DEG C ~ 850 DEG C), release stress can be cracked at the effect bottom electrode of stress, if the position that crackle produces is in electrode interior, because electrode itself is three-dimensional porous structure, more not remarkable on the impact of its performance; If crackle results from electrode and electrolyte interface place, then can cause the decline of electrode performance, thus cause electrode long-time stability poor.
In order to solve the problem, Chinese patent CN200510055068.0 discloses a kind of monocell of Solid Oxide Fuel Cell, comprise negative electrode, be compound in the cathode contact layer of cathode surface, be compound in the intermediate layer on cathode contact layer, be compound in the first solid electrolyte layer on intermediate layer, be compound in the positive contact layer of anode surface, described positive contact layer contacts with the first solid electrolyte layer.Wherein positive contact layer is formed by metal dust, cathode contact layer is formed by metal dust and perofskite type oxide powder, due to the existence of positive contact layer and cathode contact layer, the bond strength of electrode interior is made to be different from the bond strength of electrode and electrolyte interface, thus can stress be discharged under the effect of thermal stress, guard electrode; But because intermediate layer is pure dielectric substrate, cause the increase of the Ohmic resistance of battery, thus make the decline of the performance of battery; And electrode need separate with the sintering of contact layer and sinters, cause complicated process of preparation, interface bond strength is not high.
Summary of the invention
In view of this, the object of this invention is to provide a kind of electrode of Solid Oxide Fuel Cell, the good and performance of the long-time stability of Solid Oxide Fuel Cell provided by the invention can not decline.
The invention provides a kind of Solid Oxide Fuel Cell, comprising:
Cathode layer;
Be compound in the dielectric substrate on described cathode layer;
Be compound in the anode internal layer on described dielectric substrate;
The anode be compound on described anode internal layer is outer;
In described anode internal layer, the content of oxygen ion conductor material is higher than the content of oxygen ion conductor material in anode skin.
Preferably, in described anode internal layer, oxygen ion conductor material comprises the one in doped zirconia and doped cerium oxide, and in described anode skin, oxygen ion conductor material comprises the one in doped zirconia and doped cerium oxide.
Preferably, described doped zirconia is the zirconia of Y, Sc, Ce or Al element doping; Described doped cerium oxide is the cerium oxide of Gd, Sm, La or Y doping.
Preferably, described anode internal layer also comprises catalyst, and described catalyst comprises the Raney nickel of Raney nickel or doping; Described anode skin also comprises catalyst, and described catalyst comprises the Raney nickel of Raney nickel or doping.
Preferably, the Raney nickel of described doping is the Raney nickel of Fe, Co, Mn, Cu, Ca, Mg, Ba, Ag, Ru, Au, Pd, Pt, La, Ce, Gd, Pr, Nd or Sm doping.
Preferably, in described anode internal layer, the mass percentage of oxygen ion conductor material is 55% ~ 70%.
Preferably, in described anode skin, the mass percentage of oxygen ion conductor material is 30% ~ 45%.
Preferably, described anode internal layer and the outer field Thickness Ratio of anode are 0.1 ~ 1.
Preferably, described cathode layer comprises the negative electrode internal layer that negative electrode is outer and be compound on described negative electrode skin; Described dielectric substrate is compound on described negative electrode internal layer; In described negative electrode internal layer, the content of oxygen ion conductor material is higher than the content of oxygen ion conductor material in negative electrode skin.
Preferably, described negative electrode internal layer also comprises catalyst, described catalyst is selected from the one in lanthanum strontium manganese, lanthanum strontium cobalt, lanthanum cobalt nickel, lanthanum strontium ferro-cobalt and barium strontium ferro-cobalt, described negative electrode skin also comprises catalyst, and described catalyst is selected from the one in lanthanum strontium manganese, lanthanum strontium cobalt, lanthanum cobalt nickel, lanthanum strontium ferro-cobalt and barium strontium ferro-cobalt.
Compared with prior art, a kind of Solid Oxide Fuel Cell provided by the invention, comprising: cathode layer; Be compound in the dielectric substrate on described cathode layer; Be compound in the anode internal layer on described dielectric substrate; The anode be compound on described anode internal layer is outer; In described anode internal layer, the content of oxygen ion conductor material is higher than the content of oxygen ion conductor material in anode skin.Solid Oxide Fuel Cell Anodic provided by the invention is formed by bilayer, wherein, in anode internal layer, the content of oxygen ion conductor material is higher than the content of oxygen ion conductor material in anode skin, therefore in anode skin the intensity of oxygen ion conductor material lower than the intensity of oxygen ion conductor material in anode internal layer; The effect of stress is subject in battery use procedure, due to the intensity that the intensity of electrode interior combines lower than electrode and electrolyte interface, under the effect of stress, preferentially crack at electrode interior anode skin, release stress, thus play stress buffer, the effect that guard electrode and electrolyte interface combine, because electrode is three-dimensional porous structure, the crackle of electrode interior is obviously weaker than the impact of Interface Crack on the impact of battery performance, therefore refer to the stability of battery; In addition, anode internal layer provided by the invention and anode skin can sinter jointly, and preparation technology is more simple.Experimental result shows, Solid Oxide Fuel Cell provided by the invention can tolerate the thermal cycle electrode complete appearance of more than 50 times and performance without decline.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the monocell anode that the embodiment of the present invention 1 prepares;
Fig. 2 is the I-V curve resolution chart of the monocell that the embodiment of the present invention 1 prepares.
Embodiment
The invention provides a kind of Solid Oxide Fuel Cell, comprising:
Cathode layer;
Be compound in the dielectric substrate on described cathode layer;
Be compound in the anode internal layer on described dielectric substrate;
The anode be compound on described anode internal layer is outer;
In described anode internal layer, the content of oxygen ion conductor material is higher than the content of oxygen ion conductor material in anode skin.
Solid Oxide Fuel Cell provided by the invention comprises cathode layer; Described cathode layer can be that individual layer also can for double-deck, and the present invention is also unrestricted to this; Described monolayer cathodes are preferably formed by perovskite-type oxide catalysts and oxygen ion conductor material; Described two-layer cathode preferably includes the negative electrode internal layer that negative electrode is outer and be compound on described negative electrode skin; Described dielectric substrate is compound on described negative electrode internal layer; In described negative electrode internal layer, the content of oxygen ion conductor material is higher than the content of oxygen ion conductor material in negative electrode skin.Described oxygen ion conductor material preferably includes the one in doped zirconia and doped cerium oxide, described doped zirconia is the zirconia of Y, Sc, Ce or Al element doping, described doped cerium oxide is the cerium oxide of Gd, Sm, La or Y doping, described negative electrode internal layer preferably also comprises catalyst, described catalyst preferably includes but is not limited to lanthanum strontium manganese (LSM), lanthanum strontium ferro-cobalt (LSCF), lanthanum strontium cobalt (LSC), lanthanum cobalt nickel (LCN), with barium strontium ferro-cobalt (BSCF), be more preferably lanthanum strontium manganese (LSM) or lanthanum strontium ferro-cobalt (LSCF), described negative electrode skin preferably also comprises catalyst, described catalyst preferably includes but is not limited to lanthanum strontium manganese (LSM), lanthanum strontium ferro-cobalt (LSCF), lanthanum strontium cobalt (LSC), lanthanum cobalt nickel (LCN) and barium strontium ferro-cobalt (BSCF), be more preferably lanthanum strontium manganese (LSM) or lanthanum strontium ferro-cobalt (LSCF).
Solid Oxide Fuel Cell provided by the invention comprises dielectric substrate, described dielectric substrate is compound on described cathode layer, described dielectric substrate is formed by electrolyte, and described electrolyte preferably includes the one in doped zirconia and doped cerium oxide, is more preferably doped zirconia; Described doped zirconia is the zirconia of Y, Sc, Ce or Al element doping; Described doped cerium oxide is the cerium oxide of Gd, Sm, La or Y doping.
Solid Oxide Fuel Cell provided by the invention comprises the anode internal layer be compound on dielectric substrate, described anode internal layer comprises oxygen ion conductor material, described oxygen ion conductor material preferably includes the one in doped zirconia and doped cerium oxide, is more preferably doped zirconia; Described doped zirconia is the zirconia of Y, Sc, Ce or Al element doping; Described doped cerium oxide is the cerium oxide of Gd, Sm, La or Y doping; Described anode internal layer preferably also comprises catalyst, and described catalyst preferably includes the Raney nickel of Raney nickel or doping; The Raney nickel of described doping is preferably the Raney nickel of Fe, Co, Mn, Cu, Ca, Mg, Ba, Ag, Ru, Au, Pd, Ce, Gd, Pt, La, Pr, Nd or Sm doping, be more preferably the Raney nickel of Fe, Co, Mn, Ba, Cu, Ca, Mg, Ag, Au, Ce, Gd, Pd or Pt doping, most preferably be the Raney nickel of Fe, Co, Mn, Ag, Au or Pt doping; The mass percentage of described anode internal layer oxygen ion conductor material is preferably 55% ~ 70%, is more preferably 58% ~ 68%.Described anode internal layer thickness is preferably 0.5 ~ 4 micron.
The mass percentage of anode internal layer oxygen ion conductor material provided by the invention is preferably 55% ~ 70%, anode internal layer and electrolytical interface bond strength are increased, oxygen ion conduction is smooth and easy, oxygen ion conductor material and catalyst are in the percolation threshold of conductivity, can conduction electron, the internal resistance of battery can not be increased and the performance of battery can be improved.
In the present invention, described Solid Oxide Fuel Cell comprises the anode skin be compound on anode internal layer; Described anode skin comprises oxygen ion conductor material, and in described anode internal layer, the content of oxygen ion conductor material is higher than the content of oxygen ion conductor material in anode skin.Described oxygen ion conductor material preferably includes the one in doped zirconia and doped cerium oxide, is more preferably doped zirconia; Described doped zirconia is the zirconia of Y, Sc, Ce or Al element doping; Described doped cerium oxide is the cerium oxide of Gd, Sm, La or Y doping; Described anode skin preferably also comprises catalyst, and described catalyst preferably includes the Raney nickel of Raney nickel or doping; The Raney nickel of described doping is preferably the Raney nickel of Fe, Co, Mn, Ba, Cu, Ca, Mg, Ag, Ru, Au, Pd, Pt, Ce, Gd, La, Pr, Nd or Sm doping, be more preferably the Raney nickel of Fe, Co, Mn, Ba, Cu, Ca, Mg, Ce, Gd, Ag, Au, Pd or Pt doping, most preferably be the Raney nickel of Fe, Co, Mn, Ag, Au or Pt doping; The mass percentage of the outer oxygen ion conductor material of described anode is preferably 30% ~ 45%, is more preferably 33% ~ 43%; The outer field thickness of described anode is preferably 6 ~ 20 microns, is more preferably 6 ~ 10 microns; Described anode internal layer and the outer field Thickness Ratio of anode are preferably 0.1 ~ 1, are more preferably 0.2 ~ 0.7, most preferably are 0.3 ~ 0.5.
The content of anode internal layer oxygen ion conductor material provided by the invention is higher than the content of the outer electrolyte of anode, and therefore the intensity of the outer oxygen ion conductor material of anode is lower than the intensity of anode internal layer oxygen ion conductor material; The effect of stress is subject in battery use procedure, due to the intensity that the intensity of electrode interior combines lower than electrode and electrolyte interface, under the effect of stress, preferentially crack at electrode inner anode skin, release stress, thus play stress buffer, the effect that guard electrode and electrolyte interface combine; Further, anode is outer field provides high catalytic activity, can conducting ion.
Though anode internal layer provided by the invention and anode are outer variant on component content, sintering property is close, can adopt the mode of co-sintering, and manufacture craft is more simple, and interface binding power is higher.
In the present invention, described Solid Oxide Fuel Cell is preferably prepared in accordance with the following methods:
Prepare the slurry of described anode internal layer and anode skin and negative electrode;
Cathode slurry is printed on electrolyte matrix, prepares cathode layer;
Anode internal layer slurry is printed in the opposite side of electrolyte matrix, prepares anode internal layer;
Outer for anode slurry is printed on anode internal layer, prepares anode skin;
Electrode is sintered.
Described anode internal layer, anode slurry that is outer and negative electrode is preferably prepared in such a way:
The oxygen ion conductor material comprise anode internal layer and catalyst by proportion mixing, add terpinol and ethyl cellulose mixing and ball milling prepares anode internal layer slurry; The oxygen ion conductor material comprise anode skin and catalyst by proportion mixing, add terpinol and ethyl cellulose mixing and ball milling prepares the outer slurry of anode; If negative electrode is individual layer, then the oxygen ion conductor material comprised by negative electrode and catalyst by proportion mixing, add terpinol and ethyl cellulose mixing and ball milling prepares cathode slurry; If negative electrode is double-deck, then the oxygen ion conductor material comprised by negative electrode internal layer and catalyst by proportion mixing, add terpinol and ethyl cellulose mixing and ball milling prepares negative electrode internal layer slurry; The oxygen ion conductor material comprise negative electrode skin and catalyst by proportion mixing, add terpinol and ethyl cellulose mixing and ball milling prepares the outer slurry of negative electrode; Described oxygen ion conductor material preferably includes the one in doped zirconia and doped cerium oxide, is more preferably doped zirconia; Described doped zirconia is the zirconia of Y, Sc, Ce or Al element doping; Described doped cerium oxide is the cerium oxide of Gd, Sm, La or Y doping; Described anode catalyst that is outer and anode internal layer preferably includes the Raney nickel of Raney nickel or doping; The Raney nickel of described doping is preferably the Raney nickel of Fe, Co, Mn, Cu, Ca, Mg, Ba, Ag, Ru, Au, Pd, Ce, Gd, Pt, La, Pr, Nd or Sm doping, be more preferably the Raney nickel of Fe, Co, Mn, Ba, Cu, Ca, Mg, Ag, Ce, Gd, Au, Pd or Pt doping, most preferably be the Raney nickel of Fe, Co, Mn, Ag, Au or Pt doping; The catalyst of described negative electrode is preferably perovskite-type oxide catalysts, preferably include but be not limited to lanthanum strontium manganese (LSM), lanthanum strontium ferro-cobalt (LSCF), lanthanum strontium cobalt (LSC), lanthanum cobalt nickel (LCN) and barium strontium ferro-cobalt (BSCF), being more preferably lanthanum strontium manganese (LSM) or lanthanum strontium ferro-cobalt (LSCF); Described ball milling is specially oxygen ion conductor material, catalyst and terpinol mixing and ball milling 17 ~ 19 hours, adds ethyl cellulose ball milling 5 ~ 7 hours, obtains slurry; The present invention is also unrestricted for described hybrid mode, hybrid mode well known to those skilled in the art.
After preparing slurry, if negative electrode is individual layer, be specially, cathode slurry be printed on electrolyte matrix; If negative electrode is double-deck, be then specially at electrolyte matrix printed cathode slurry: negative electrode internal layer slurry is printed on electrolyte matrix, dry; Outer for negative electrode slurry is printed on negative electrode internal layer, dries; The slurry of anode internal layer is printed on the electrolyte matrix sintered; Anode skin is printed on anode internal layer; Described printing is preferably silk screen printing; Described silk screen is preferably 200 orders; Described printing is preferably afterwards and dries, and the temperature of described oven dry is preferably 50 DEG C ~ 90 DEG C.
After oven dry, sinter electrode, the sintering temperature of described electrode is preferably 1000 DEG C ~ 1500 DEG C.
The present invention does not limit for the source of described oxygen ion conductor material and catalyst, can be commercially available, preferably be prepared according to method disclosed in patent CN101989664A or CN102167403A.
After preparing monocell, the present invention preferably carries out ESEM, I-V curve and thermal cycle test to battery, and wherein, thermal cycle test is preferably tested in accordance with the following methods:
Battery rises to working temperature 830 DEG C through room temperature, is incubated 1 hour, then is cooled to room temperature, is 1 thermal cycle, and it is 10 DEG C/min that temperature rate controls.
After n thermal cycle, whether observation battery outward appearance is complete, and whether electrode comes off, and the test of I-V curve is carried out to the battery after circulation, if battery complete appearance, performance is without obvious decay, then battery can resistance to times of thermal cycle be >n, on the contrary then < n.
In order to further illustrate the present invention, below in conjunction with embodiment, electrode of Solid Oxide Fuel Cell provided by the invention and preparation method thereof is described in detail.
Embodiment 1
Prepare method disclosed in lanthanum strontium manganese (LSM), embodiment 5 according to method disclosed in patent CN102167403A embodiment 1 and prepare scandium oxide doped zirconia (SSZ), according to method disclosed in embodiment 6 prepare gadolinium oxide doping cerium oxide (GDC), prepare nickel oxide (NiO) according to method disclosed in patent CN101989664A embodiment 1.
The cerium oxide (GDC) of the above-mentioned 60g gadolinium oxide doping prepared and 40g nickel oxide are mixed, add 12g terpinol, ball milling added 4g ethyl cellulose after 18 hours, ball milling 6 hours, prepared anode internal layer slurry; Mixed by the 40g GDC of above-mentioned preparation and 60g NiO, add 12g terpinol, ball milling added 4g ethyl cellulose after 18 hours, ball milling 6 hours, prepared the outer slurry of anode; The 50g lanthanum strontium manganese of above-mentioned preparation and 50g scandium oxide doped zirconia (SSZ) are mixed, add 12g terpinol, ball milling added 4g ethyl cellulose after 18 hours, and ball milling 6 hours, prepares cathode slurry.
With 200 object silk screens printed anode internal layer slurry on the electrolyte matrix of 1500 DEG C of sintering, electrolyte layer is the zirconia (8YSZ) of the stabilized with yttrium oxide of 8% mole, in 70 DEG C of oven dry after printing, obtains anode internal layer; The outer slurry of silk screen printing anode on anode internal layer, 70 DEG C of oven dry obtain anode skin; In dielectric substrate opposite side silk screen printing cathode slurry, 70 DEG C of oven dry, obtain cathode layer, thus prepare electrode; Within 2 hours, obtaining structure to 1150 DEG C, electrode sintering is negative electrode/electrolyte/outer field monocell of anode internal layer/anode.
Carry out sem test, the test of I-V curve and thermal cycle test according to the method described above to monocell prepared by embodiment 1, result is as shown in Figure 1, Figure 2 with shown in table 1, and Fig. 1 is the scanning electron microscope (SEM) photograph of the monocell anode that the embodiment of the present invention 1 prepares.Fig. 2 is the I-V curve resolution chart of the monocell that the embodiment of the present invention 1 prepares, and wherein probe temperature is 830 DEG C, and curve a is that the Current density-voltage of monocell measures curve, and curve b is that the current density-power density of monocell measures curve; As shown in Figure 2, the power density at the monocell 830 DEG C that provides of the embodiment of the present invention 1 reaches 0.65W/cm2.Table 1 is the test result of the thickness of electrode of the embodiment of the present invention and comparative example, power density and times of thermal cycle.
Embodiment 2
Prepare method disclosed in lanthanum strontium manganese (LSM), embodiment 5 according to method disclosed in patent CN102167403A embodiment 1 and prepare scandium oxide doped zirconia (SSZ), according to method disclosed in embodiment 6 prepare gadolinium oxide doping cerium oxide (GDC), prepare nickel oxide (NiO) according to method disclosed in patent CN101989664A embodiment 1.
Mixed by the above-mentioned 70g GDC for preparing and 30g NiO, add 12g terpinol, ball milling added 4g ethyl cellulose after 18 hours, ball milling 6 hours, prepared anode internal layer slurry; Mixed by 30gGDC and 70gNiO of above-mentioned preparation, add 12g terpinol, ball milling added 4g ethyl cellulose after 18 hours, ball milling 6 hours, prepared the outer slurry of anode; The 50g lanthanum strontium manganese of above-mentioned preparation and 50g scandium oxide doped zirconia are mixed, add 12g terpinol, ball milling added 4g ethyl cellulose after 18 hours, and ball milling 6 hours, prepares cathode slurry.
With 200 object silk screens printed anode internal layer slurry on the electrolyte matrix of 1500 DEG C of sintering, electrolyte layer is scandium oxide doped zirconia (SSZ), in 75 DEG C of oven dry after printing, obtains anode internal layer; The outer slurry of silk screen printing anode on anode internal layer, 75 DEG C of oven dry, obtain anode skin; In dielectric substrate opposite side silk screen printing cathode slurry, 75 DEG C of oven dry, obtain cathode layer, thus prepare electrode; Within 2 hours, obtaining structure to 1150 DEG C, electrode sintering is negative electrode/electrolyte/outer field monocell of anode internal layer/anode.
Sem test, the test of I-V curve and thermal cycle test are carried out according to the method described above to monocell prepared by the embodiment of the present invention 2, the results are shown in Table 1, table 1 is the test result of the thickness of electrode of the embodiment of the present invention and comparative example, power density and times of thermal cycle.
Embodiment 3
Prepare method disclosed in lanthanum strontium manganese (LSM), embodiment 5 according to method disclosed in patent CN102167403A embodiment 1 and prepare scandium oxide doped zirconia (SSZ), according to method disclosed in embodiment 6 prepare gadolinium oxide doping cerium oxide (GDC), prepare nickel oxide (NiO) according to method disclosed in patent CN101989664A embodiment 1.
Mixed by the above-mentioned 55g SSZ for preparing and 45g NiO, add 12g terpinol, ball milling added 4g ethyl cellulose after 18 hours, ball milling 6 hours, prepared anode internal layer slurry; Mixed by 40gGDC and 60gNiO of above-mentioned preparation, add 12g terpinol, ball milling added 4g ethyl cellulose after 18 hours, ball milling 6 hours, prepared the outer slurry of anode; The 50g lanthanum strontium manganese of above-mentioned preparation and 50g scandium oxide doped zirconia are mixed, add 12g terpinol, ball milling added 4g ethyl cellulose after 18 hours, and ball milling 6 hours, prepares cathode slurry.
With 200 object silk screens printed anode internal layer slurry on the electrolyte matrix of 1500 DEG C of sintering, electrolyte layer is the zirconia (8YSZ) of the stabilized with yttrium oxide of 8% mole, in 65 DEG C of oven dry after printing, obtains anode internal layer; The outer slurry of silk screen printing anode on anode internal layer, 65 DEG C of oven dry, obtain anode skin; In dielectric substrate opposite side silk screen printing cathode slurry, 65 DEG C of oven dry, obtain cathode layer, thus prepare electrode; Within 2 hours, obtaining structure to 1200 DEG C, electrode sintering is negative electrode/electrolyte/outer field monocell of anode internal layer/anode.
Sem test, the test of I-V curve and thermal cycle test are carried out according to the method described above to monocell prepared by the embodiment of the present invention 3, the results are shown in Table 1, table 1 is the test result of the thickness of electrode of the embodiment of the present invention and comparative example, power density and times of thermal cycle.
Embodiment 4
Prepare method disclosed in lanthanum strontium cobalt (LSC), embodiment 5 according to method disclosed in patent CN102167403A embodiment 3 and prepare scandium oxide doped zirconia (SSZ), according to method disclosed in embodiment 6 prepare gadolinium oxide doping cerium oxide (GDC), prepare nickel oxide (NiO) according to method disclosed in patent CN101989664A embodiment 1.
Mixed by the above-mentioned 65g SSZ for preparing and 35g NiO, add 12g terpinol, ball milling added 4g ethyl cellulose after 18 hours, ball milling 6 hours, prepared anode internal layer slurry; Mixed by 30gGDC and 70gNiO of above-mentioned preparation, add 12g terpinol, ball milling added 4g ethyl cellulose after 18 hours, ball milling 6 hours, prepared the outer slurry of anode; Mixed by 50gLSC and the 50g SSZ of above-mentioned preparation, add 12g terpinol, ball milling added 4g ethyl cellulose after 18 hours, and ball milling 6 hours, prepares cathode slurry.
With 200 object silk screens printed anode internal layer slurry on the electrolyte matrix of 1500 DEG C of sintering, electrolyte layer is scandium oxide doped zirconia (SSZ), in 80 DEG C of oven dry after printing, obtains anode internal layer; The outer slurry of silk screen printing anode on anode internal layer, 80 DEG C of oven dry, obtain anode skin; In dielectric substrate opposite side silk screen printing cathode slurry, 80 DEG C of oven dry, obtain cathode layer, thus prepare electrode; Within 2 hours, obtaining structure to 1200 DEG C, electrode sintering is negative electrode/electrolyte/outer field monocell of anode internal layer/anode.
Sem test, the test of I-V curve and thermal cycle test are carried out according to the method described above to monocell prepared by the embodiment of the present invention 4, the results are shown in Table 1, table 1 is the test result of the thickness of electrode of the embodiment of the present invention and comparative example, power density and times of thermal cycle.
Embodiment 5
Prepare method disclosed in lanthanum strontium manganese (LSM), embodiment 5 according to method disclosed in patent CN102167403A embodiment 1 and prepare scandium oxide doped zirconia (SSZ), according to method disclosed in embodiment 6 prepare gadolinium oxide doping cerium oxide (GDC), prepare nickel oxide (NiO) according to method disclosed in patent CN101989664A embodiment 1.
Mixed by the above-mentioned 60g GDC for preparing and 40g NiO, add 12g terpinol, ball milling added 4g ethyl cellulose after 18 hours, ball milling 6 hours, prepared anode internal layer slurry; Mixed by 40gGDC and 60gNiO of above-mentioned preparation, add 12g terpinol, ball milling added 4g ethyl cellulose after 18 hours, ball milling 6 hours, prepared the outer slurry of anode; Mixed by 50gLSM and the 50g SSZ of above-mentioned preparation, add 12g terpinol, ball milling added 0.6g ethyl cellulose after 18 hours, ball milling 6 hours, prepared negative electrode internal layer slurry; Mixed by 55g LSM and 45gGDC of above-mentioned preparation, add 12g terpinol, ball milling added 4g ethyl cellulose after 18 hours, ball milling 6 hours, prepared negative electrode internal layer slurry.
With 200 object silk screens printed anode internal layer slurry on the electrolyte matrix of 1500 DEG C of sintering, electrolyte layer is the zirconia (8YSZ) of the stabilized with yttrium oxide of 8% mole, in 85 DEG C of oven dry after printing, obtains anode internal layer; The outer slurry of silk screen printing anode on anode internal layer, 85 DEG C of oven dry; Obtain anode skin, at dielectric substrate opposite side silk screen printing negative electrode internal layer slurry, in 85 DEG C of oven dry after printing, obtain negative electrode internal layer, the outer slurry of silk screen printing negative electrode on negative electrode internal layer, 85 DEG C of oven dry, obtain negative electrode skin, thus prepare electrode; Within 2 hours, obtaining structure to 1250 DEG C, electrode sintering is negative electrode skin/negative electrode internal layer/electrolyte/outer field monocell of anode internal layer/anode.
Sem test, the test of I-V curve and thermal cycle test are carried out according to the method described above to monocell prepared by the embodiment of the present invention 5, the results are shown in Table 1, table 1 is the test result of the thickness of electrode of the embodiment of the present invention and comparative example, power density and times of thermal cycle.
Embodiment 6
Prepare method disclosed in lanthanum strontium manganese (LSC), embodiment 5 according to method disclosed in patent CN102167403A embodiment 3 and prepare scandium oxide doped zirconia (SSZ), according to method disclosed in embodiment 6 prepare gadolinium oxide doping cerium oxide (GDC), prepare nickel oxide (NiO) according to method disclosed in patent CN101989664A embodiment 1.
Mixed by the above-mentioned 55g SSZ for preparing and 45g NiO, add 12g terpinol, ball milling added 4g ethyl cellulose after 18 hours, ball milling 6 hours, prepared anode internal layer slurry; Mixed by 40gGDC and 60gNiO of above-mentioned preparation, add 12g terpinol, ball milling added 4g ethyl cellulose after 18 hours, ball milling 6 hours, prepared the outer slurry of anode; Mixed by 45gLSC and the 55g SSZ of above-mentioned preparation, add 12g terpinol, ball milling added 4g ethyl cellulose after 18 hours, ball milling 6 hours, prepared negative electrode internal layer slurry; Mixed by the 55g LSM of above-mentioned preparation and 45g GDC, add 12g terpinol, ball milling added 0.6g ethyl cellulose after 18 hours, ball milling 6 hours, prepared negative electrode internal layer slurry.
With 200 object silk screens printed anode internal layer slurry on the electrolyte matrix of 1500 DEG C of sintering, electrolyte layer is scandium oxide doped zirconia (SSZ), in 70 DEG C of oven dry after printing, obtains anode internal layer; The outer slurry of silk screen printing anode on anode internal layer, 70 DEG C of oven dry; Obtain anode skin, at dielectric substrate opposite side silk screen printing negative electrode internal layer slurry, in 70 DEG C of oven dry after printing, obtain negative electrode internal layer, the outer slurry of silk screen printing negative electrode on negative electrode internal layer, 70 DEG C of oven dry, obtain negative electrode skin, thus prepare electrode; Within 2 hours, obtaining structure to 1500 DEG C, electrode sintering is negative electrode skin/negative electrode internal layer/electrolyte/outer field monocell of anode internal layer/anode.
Sem test, the test of I-V curve and thermal cycle test are carried out according to the method described above to monocell prepared by the embodiment of the present invention 6, the results are shown in Table 1, table 1 is the test result of the thickness of electrode of the embodiment of the present invention and comparative example, power density and times of thermal cycle.
Comparative example 1
Prepare method disclosed in lanthanum strontium manganese (LSM), embodiment 5 according to method disclosed in patent CN102167403A embodiment 1 and prepare scandium oxide doped zirconia (SSZ), according to method disclosed in embodiment 6 prepare gadolinium oxide doping cerium oxide (GDC), prepare nickel oxide (NiO) according to method disclosed in patent CN101989664A embodiment 1.
The above-mentioned 40g GDC for preparing and 60g nickel oxide are mixed, add 12g terpinol, ball milling added 4g ethyl cellulose after 18 hours, and ball milling 6 hours, prepares anode slurry; Mixed by 50gLSM and the 50g SSZ of above-mentioned preparation, add 12g terpinol, ball milling added 4g ethyl cellulose after 18 hours, and ball milling 6 hours, prepares cathode slurry.
With 200 object silk screens printed anode slurry on the electrolyte matrix of 1500 DEG C of sintering, electrolyte layer is the zirconia (8YSZ) of the stabilized with yttrium oxide of 8% mole, in 70 DEG C of oven dry after printing, obtains anode layer; In dielectric substrate opposite side silk screen printing cathode slurry, 70 DEG C of oven dry, obtain cathode layer, thus prepare electrode; The monocell that structure is negative electrode/electrolyte/anode is obtained for 2 hours to 1500 DEG C, electrode sintering.
Sem test, the test of I-V curve and thermal cycle test are carried out according to the method described above to monocell prepared by comparative example 1 of the present invention, the results are shown in Table 1, table 1 is the test result of the thickness of electrode of the embodiment of the present invention and comparative example, power density and times of thermal cycle.
The test result of the thickness of electrode of table 1 embodiment of the present invention and comparative example, power density and times of thermal cycle
As shown in Table 1, battery thermal cycling stability provided by the invention is good.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (7)
1. a Solid Oxide Fuel Cell, comprising:
Cathode layer;
Be compound in the dielectric substrate on described cathode layer;
Be compound in the anode internal layer on described dielectric substrate;
The anode be compound on described anode internal layer is outer;
In described anode internal layer, the content of oxygen ion conductor material is higher than the content of oxygen ion conductor material in anode skin, the outer field thickness of described anode is 6 ~ 20 microns, described anode internal layer and the outer field Thickness Ratio of anode are 0.1 ~ 1, in described anode internal layer, the mass percentage of oxygen ion conductor material is 55% ~ 70%, and in described anode skin, the mass percentage of oxygen ion conductor material is 33% ~ 43%.
2. Solid Oxide Fuel Cell according to claim 1, it is characterized in that, in described anode internal layer, oxygen ion conductor material comprises the one in doped zirconia and doped cerium oxide, and in described anode skin, oxygen ion conductor material comprises the one in doped zirconia and doped cerium oxide.
3. Solid Oxide Fuel Cell according to claim 2, is characterized in that, described doped zirconia is the zirconia of Y, Sc, Ce or Al element doping; Described doped cerium oxide is the cerium oxide of Gd, Sm, La or Y doping.
4. Solid Oxide Fuel Cell according to claim 1, is characterized in that, described anode internal layer also comprises catalyst, and described catalyst comprises the Raney nickel of Raney nickel or doping; Described anode skin also comprises catalyst, and described catalyst comprises the Raney nickel of Raney nickel or doping.
5. Solid Oxide Fuel Cell according to claim 4, is characterized in that, the Raney nickel of described doping is the Raney nickel of Fe, Co, Mn, Cu, Ca, Mg, Ba, Ag, Ru, Au, Pd, Pt, La, Ce, Gd, Pr, Nd or Sm doping.
6. Solid Oxide Fuel Cell according to claim 1, is characterized in that, described cathode layer comprises the negative electrode internal layer that negative electrode is outer and be compound on described negative electrode skin; Described dielectric substrate is compound on described negative electrode internal layer; In described negative electrode internal layer, the content of oxygen ion conductor material is higher than the content of oxygen ion conductor material in negative electrode skin.
7. Solid Oxide Fuel Cell according to claim 6, it is characterized in that, described negative electrode internal layer also comprises catalyst, described catalyst is selected from the one in lanthanum strontium manganese, lanthanum strontium cobalt, lanthanum cobalt nickel, lanthanum strontium ferro-cobalt and barium strontium ferro-cobalt, described negative electrode skin also comprises catalyst, and described catalyst is selected from the one in lanthanum strontium manganese, lanthanum strontium cobalt, lanthanum cobalt nickel, lanthanum strontium ferro-cobalt and barium strontium ferro-cobalt.
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