CN102683720A - Gradient composite cathode for solid oxide fuel cell and preparation method thereof - Google Patents
Gradient composite cathode for solid oxide fuel cell and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a cathode for a solid oxide fuel cell and a preparation method thereof. A gradient composite cathode for the solid oxide fuel cell comprises a barrier layer, an activating layer and a current collection layer, wherein the barrier layer is made of an LNF-doped CeO2 material; the activating layer is located on the barrier layer and is made of the LNF-doped CeO2 material; and the current collection layer is located on the activating layer and is made of an LNF material. The preparation method for the gradient composite cathode comprises the following steps of: 1) attaching slurry of the barrier layer to an electrolyte and drying, thereby obtaining the barrier layer; 2) attaching the slurry of the activating layer to the barrier layer and drying, thereby obtaining the activating layer; 3) attaching the slurry of the current collection layer to the activating layer and drying, thereby preparing into the current collection layer and obtaining a blank; and 4) sintering the blank. The gradient composite cathode for the solid oxide fuel cell prepared according to the preparation method provided by the invention is excellent in electrochemical catalysis property. The preparation method for the gradient composite cathode is simple; the preparation period is short; and the gradient composite cathode is low in cost and is suitable for industrial application.
Description
Technical field
The present invention relates to a kind of negative electrode of SOFC, relate in particular to a kind of LNF gradient composite cathode of SOFC, the invention still further relates to the preparation method of this SOFC LNF gradient composite cathode.
Background technology
At present, (Solid Oxide Fuel Cell, in evolution SOFC), People more and more is recognized the importance that reduces battery operated temperature at SOFC.If can battery operated temperature be reduced to middle temperature (700～800 ℃), then can improve the stability of electrode, reduce thermal stress, extending battery life also can use the bipolar plate material of cheap metal alloy as battery.But along with the reduction of battery operated temperature, (yttria stabilized zirconia, ionic conductivity YSZ) and the catalytic activity of electrode reduce rapidly the zirconia of traditional electrolyte stabilized with yttrium oxide, thereby cause the performance of battery to descend rapidly.Reduce to have than the material of high ionic conductivity such as the zirconia of scandia stabilized (scandia stabilized zirconia under the low temperature in electrolytical thickness or the employing; ScSZ), gadolinium oxide doping of cerium oxide (gadolinium oxide-doped ceria; GDC), samarium oxide doping of cerium oxide (samarium oxide-doped ceria; SDC) and the perovskite compound
with oxygen room structure (LSGM) etc., the problem that bath resistance increases under the low temperature in can solving.Lanthanum manganate (La, Sr) MnO of traditional Ca-Ti ore type strontium doping
3(LSM) be to know at present and the best cathode material of YSZ matching that under the high temperature about 1000 ℃, LSM has higher electronic conductance and catalytic activity and good chemical stability.These advantages make LSM become the highest cathode material of present level of application.But, can reduce and descend rapidly with temperature as the catalytic activity of the LSM material of negative electrode, thereby increase electrochemical activation polarization overpotential on the negative electrode, thereby reduce the output performance of battery.Therefore, solving cathode material is exactly to seek other cathode material that under middle low temperature, has higher catalytic activity in one of approach of poor-performing under the middle low temperature.
Find that through the document retrieval people such as Reiichi Chiba deliver " An investigation of LaNi
L-xFe
xO
3As a cathode material for solid oxide fuel cells " (cathode material for solid-oxide fuel cell LaNi
L-xFe
x0
3Research) literary composition, see " Solid State Ionics " (solid-state ionics) 124 (3-4) (1999) 281-288.This article is introduced: as a kind of perofskite type oxide, and the nickel acid lanthanum LaNi that iron mixes
0.6Fe
0.4O
3(LNF) belong to orthorhombic system, 800 ℃ conductivity is 580 S/cm, is conventional cathode material La
0.8Sr
0.2MnO
3(180 S/cm) three times.LNF is 11.4 * 10 from the thermal coefficient of expansion (TEC) of room temperature to 1000 ℃
-6K
-1, than conventional cathode material La
0.8Sr
0.2MnO
3(12.0 * 10
-6K
-1) more near the thermal coefficient of expansion 10.0 * 10 of YSZ
-6K
-1Under battery operated temperature, have than conventional cathode material La
0.8Sr
0.2MnO
3Higher catalytic activity to the oxygen electrochemical reducting reaction.However, La (Ni, Fe) O
3Under identical sintering temperature, than (La, Sr) MnO of classics
3More be prone to and ZrO
2Base electrolyte reaction, when being higher than 1000 ℃ in temperature, LaNi
0.6Fe
0.4O
3Promptly and ZrO
2Base electrolyte reacts and generates the La of insulation
2Zr
2O
7, significantly reduce its battery performance.On the other hand, because the characteristic of LNF material itself, like LNF cathode material reoxidizing and the decline of subsequently oxygen vacancy concentration under working temperature; The initial performance that causes the LNF negative electrode is not finely (to see S.I.Hashimoto; K.Kammer, P.H.Larsen, F.W.Poulsen; M.Mogensen, Solid State Ionics 176 (2005) 1013).Therefore, La (Ni, Fe) O
3As the middle low-temperature cathode material that has application prospect, its performance also needs further to improve.
Summary of the invention
Because the above-mentioned defective of prior art the invention provides gradient composite cathode of a kind of SOFC and preparation method thereof.
Particularly, the present invention adopts the method for LNF composition gradient structural design, with the present known cathode material LaNi that catalytic performance is good, electronic conductivity is high, physical and chemical stability is excellent
0.6Fe
0.4O
3-δ(LNF) and catalytic performance good, the mixed nanometer CeO with outstanding oxonium ion storage, release and transmittability
2These two kinds of combinations of materials get up; Make the multiple requirement of high-performance SOFC negative electrode is born by different composition gradient cathode layers; And each layer cooperatively interacted; Utilize synergy to reach the effect of mutual supplement with each other's advantages, significantly improve the oxygen reduction kinetics of LNF composition gradient composite cathode, thereby reach the purpose that improves the SOFC performance.
The present invention solves the problems of the technologies described above through following technical scheme:
On the one hand, the present invention provides a kind of gradient composite cathode of SOFC, and this gradient composite cathode comprises:
Barrier layer, the material on said barrier layer are LNF-doped Ce O
2Active layer, the material of said active layer are LNF-doped Ce O
2, said active layer is positioned on the said barrier layer; Current collection layer, the material of said current collection layer are LNF, and said current collection layer is positioned on the said active layer.
In embodiment of the present invention, said doped Ce O
2Be doped Ce O
2Nano particle; Said LNF is preferably LaNi
0.6Fe
0.4O
3The material of said dielectric substrate is preferably ScSZ.
In concrete technical scheme of the present invention, the LNF-doped Ce O of barrier layer or active layer
2In doped Ce O
2, its dopant ion is Gd
3+Or/and Sm
3+Preferably, the dopant ion mol ratio is (Gd+Sm): Ce=2: 8, i.e. and doped Ce O
2Nano material be Gd
0.2Ce
0.8O
2Or/and Sm
0.2Ce
0.8O
2
Wherein, said LaNi
0.6Fe
0.4O
3The preparation method be: with mol ratio is La: Ni: Fe=1: 0.6: 0.4 La (NO
3)
36H
2O, Ni (NO
3)
2And Fe (NO
3)
39H
2O is dissolved in the distilled water; In solution, dissolve in the citric acid of stoichiometric proportion then, and add ammoniacal liquor solution is transferred to neutrality,, directly obtain the xerogel of brown at 120 ℃ of transpiring moistures; Xerogel is put in the crucible furnace (is preheating to 300 ℃), the xerogel burning of smoldering rapidly fully obtains the black powder after the burning; Again products therefrom was calcined 2 hours down at 650 and 1100 ℃ respectively, obtained LaNi
0.6Fe
0.4O
3, its particle diameter is respectively 0.05 ~ 0.08 μ m and 0.5 ~ 0.8 μ m.
Said Gd
0.2Ce
0.8O
2Or Sm
0.2Ce
0.8O
2The preparation method be: with mol ratio is Gd or Sm: Ce=0.2: 0.8 Gd (NO
3)
36H
2O or Sm (NO
3)
36H
2O and Ce (NO
3)
36H
2O is dissolved in the distilled water; In solution, dissolve in the citric acid of stoichiometric proportion then, and add ammoniacal liquor solution is transferred to neutrality,, directly obtain flaxen xerogel at 110 ℃ of transpiring moistures; Xerogel is put in the crucible furnace (is preheating to 450), the xerogel burning of smoldering rapidly fully obtains faint yellow powder after the burning; Again products therefrom was calcined 2 hours down at 600 ℃, obtained Gd
0.2Ce
0.8O
2Or Sm
0.2Ce
0.8O
2, its particle diameter is 0.05 ~ 0.06 μ m.
In said barrier layer, LNF-doped Ce O
2Middle LNF and doped Ce O
2Mass ratio be preferably 6 ~ 7: 4 ~ 3.In said active layer, LNF-doped Ce O
2Middle LNF and doped Ce O
2Mass ratio be preferably 7 ~ 8: 3 ~ 2.
In embodiment of the present invention, preferably, the thickness on said barrier layer is 8 ~ 10 microns, and the thickness of said active layer is 8 ~ 10 microns, and the thickness of said current collection layer is 8 ~ 10 microns.
On the other hand, the present invention also provides a kind of preparation method of gradient composite cathode of above-mentioned SOFC.This method prepares large scale high-performance solid oxidate fuel cell LNF composition gradient composite cathode applicable to suitability for industrialized production, specifically may further comprise the steps:
Step 1 is with LNF powder and doped Ce O
2Mixture and terpinol be mixed into slurry, this slurry is deposited on the electrolyte, and processes LNF-doped Ce O after 0.5 hour in 110 ℃ of dryings
2The barrier layer;
Step 2 is with LNF powder and doped Ce O
2Mixture and terpinol be mixed into slurry, this slurry is deposited on LNF-doped Ce O
2On the barrier layer, and process LNF-doped Ce O after 0.5 hour in 110 ℃ of dryings
2Active layer;
Step 3 is that 1: 1 LNF powder and terpinol is mixed into slurry with mass ratio, and this slurry is deposited on LNF-doped Ce O
2On the active layer, and process the LNF current collection layer after 0.5 hour, obtain the base substrate of SOFC gradient composite cathode in 110 ℃ of dryings;
Step 4 with above-mentioned prepared blank sintering, obtains the gradient composite cathode of SOFC after the cooling.
Slurry among the present invention all uses silk screen print method general in the prior art, is printed on respectively on dielectric substrate, barrier layer or the active layer.
The sintering that the present invention mentioned is a sintering in air.The temperature of said sintering is 1050 ℃ ~ 1100 ℃, and the time of said sintering is 2 h ~ 3 hours.Preferably, with prepared base substrate 1100 ℃ of sintering 2 hours.
In preferred embodiments of the present invention, in the step 1, said LNF and doped Ce O
2Mass ratio be 6 ~ 7: 4 ~ 3.In the step 2, said LNF and doped Ce O
2Mass ratio be 7 ~ 8: 3 ~ 2.
In the preparation method of gradient composite cathode of the present invention, in the step 1, two, said LNF and doped Ce O
2Mixture and the mass ratio of terpinol be 1: 1.
Stoichiometric proportion among the preparation method of gradient composite cathode according to the invention is calculated through following principle:
LaNi
0.6Fe
0.4O
3, doped Ce O
2(Gd
0.2Ce
0.8O
2Or Sm
0.2Ce
0.8O
2) needed raw material proportioning metering adopted the thermochemical theory that advances chemistry: people such as Jain (S.R.Jain; K.C.Adiga, V.R.P.Vemeker, A new approach to thermochemical calculation of condensed fuel-oxidizer mixtures; Combustion and Flame; 1981,40 (1): 71-76.) defined a kind of straightforward procedure of calculating the redox reaction characteristic, suppose all elements all with it at product (like CO
2, H
2O and N
2Deng) in the valence state that exists calculate, so the valence state of reproducibility Elements C and H be respectively+4 and+1, the valence state of oxidizability element O is-2, the valence state of element N is considered to 0.This notion is extrapolated, and the product ceramic oxide (like ZnO, Bi
2O
3And ZrO
2Deng) in metallic element Zn, Bi and Zr can be used as the reproducibility element, its valence state is respectively+2 ,+3 and+4; Citric acid C
6H
8O
7H
2The valence state of O is+18; Total chemical valence of divalent metal nitrate is-10; Total chemical valence of the metal nitrate of trivalent is-15; Whether the existence of the crystallization water does not influence the calculating of total chemical valence of nitrate.With synthetic LaNi
0.6Fe
0.4O
3-δBe example, needed La (NO
3)
36H
2O, Ni (NO
3)
2And Fe (NO
3)
39H
2The mol ratio of O is 1: 0.6: 0.4, and their total oxidation valency is-15 * 1+ (10 * 0.6)+(15 * 0.4)=-27; As being fuel with the citric acid, then total also original cost is+18 valencys in the raw material, so the mol ratio of oxidant and citric acid is 18: 27=2: 3, i.e. n (La (NO
3)
36H
2O): n (Ni (NO
3)
2): n (Fe (NO
3)
39H
2O): n (C
6H
8O
7H
2O)=and 1: 0.6: 0.4: 1.5.With synthetic Gd
0.2Ce
0.8O
2Be example, needed Gd (NO
3)
36H
2O and Ce (NO
3)
36H
2The mol ratio of O is 0.2: 0.8, and their total oxidation valency is-15 * 0.2+ (15 * 0.8)=-15; As being fuel with the citric acid, then total also original cost is+18 valencys in the raw material, so the mol ratio of oxidant and citric acid is 18: 15=6: 5, i.e. n (Gd (NO
3)
36H
2O): n (Ce (NO
3)
36H
2O): n (C
6H
8O
7H
2O)=0.2: 0.8: (5/6).
In embodiment of the present invention, said electrolyte is to be applicable to any electrolyte known in the field of solid oxide fuel, preferably, is the zirconia (ScSZ) of scandia stabilized.
The LNF composition gradient composite cathode of SOFC of the present invention can with the arbitrarily anode of the SOFC use of arranging in pairs or groups jointly in the prior art.
In another preferred embodiments of the present invention, the gradient composite cathode of SOFC of the present invention and anode are the use of arranging in pairs or groups jointly of NiO-YSZ/ScSZ composite membrane.The preparation method that its anode NiO-YSZ/ScSZ supports composite membrane comprises the steps, below each component all represent with mass fraction:
Step 1,10 parts of ScSZ powders are joined in 8 parts of butanone and the 4 parts of ethanol mixed solvent, add 0.5 part of dispersant then, preferred triethanolamine; And 2 hours degree with the control powder reuniting of ball milling, obtain high-quality stable suspension, powder is dispersed in the slurry; Add 0.4 part of binding agent polyvinyl butyral resin, 1.5 parts of plasticizer polyethylene glycol in the mixed slurry behind first time ball milling; And once more ball milling 2 hours so that powdery pulp has best rheological behavior when flow casting molding; The slurry that ball milling is good keeps 10 minutes in a vacuum to eliminate the bubble in the slurry, obtains casting slurry one;
Step 2, zirconia (YSZ) mixed powder of 50 parts of nickel oxide (NiO) and 50 parts of stabilized with yttrium oxide is joined in 48 parts of butanone and the 24 parts of ethanol mixed solvent; Add 3 parts of dispersants then; And 2 hours degree of ball milling with the control powder reuniting; Obtain high-quality stable suspension, powder is dispersed in the slurry; Add 10 parts of binding agent polyvinyl butyral resins, 13.5 parts of plasticizer polyethylene glycol in the mixed slurry behind first time ball milling, and once more ball milling 2 hours so that powdery pulp has best rheological behavior when flow casting molding; The slurry that ball milling is good keeps 10 minutes bubbles of eliminating in the slurry in a vacuum, obtains casting slurry two;
Step 3, homogeneous, stable casting slurry one poured into flow casting molding in the feed bin of casting machine, treat its drying after, casting slurry two poured into carries out Secondary Flow on it and prolong moulding; Make NiO-YSZ/ScSZ anodic composite film biscuit through dry, section, biscuit in 600 ℃ of heat treatment 3h with the burn off biscuit in organic substance; In 1350～1450 ℃ of sintering 3h, obtain the NiO-YSZ/ScSZ anodic composite film at last.
The average grain diameter of the zirconia (ScSZ) of the raw material nickel oxide of wherein, being selected for use (NiO), the zirconia (YSZ) of stabilized with yttrium oxide, scandia stabilized is the 0.5-10 micron.
Beneficial effect of the present invention:
Constitute the material LaNi of each functional layer of gradient composite cathode of SOFC among the present invention
0.6Fe
0.4O
3-δAnd doped Ce O
2All be to adopt low-temperature combustion method synthetic, being applied to of this method success permitted more than 1 simple or complicated compound systems, and under lower temperature, get final product easy and prepare the oxide superfine powder efficiently, be that a kind of advanced ceramics of novelty prepares approach.The present invention adopts the synthetic oxide LaNi of low-temperature combustion method
0.6Fe
0.4O
3-δPowder and doped Ce O
2Powder, its particle size be nanoscale (＜100nm), the specific area of powder is big.Like this, each functional layer of SOFC gradient composite cathode can keep loose structure and preferable oxygen reduction kinetics performance preferably like 1000～1100 ℃ of sintering at a lower temperature.
SOFC gradient composite cathode of the present invention is analyzed from function, and LNF has higher conductivity and to the catalytic activity of oxygen electrochemical reducting reaction, splendid physical and chemical stability; Doped Ce O
2Mix, increased the ionic conductivity of cathode material, especially the less doped Ce O of particle diameter
2Powder is wrapped in and carries out on the bigger LNF powder granule of particle diameter (1100 times sintering) forming the ion-electron conductive path in negative electrode inside behind the sintering.Suppressed LNF and electrolyte ScSZ on the one hand the La that chemical reaction generates insulation has taken place
2Zr
2O
7, cause the negative electrode Ohmic resistance to increase; Also increase the three-phase reaction interface of LNF and electrolyte ScSZ on the other hand, made cathodic polarization resistance significantly reduce, thereby improved the electrochemical catalysis performance of LNF.Therefore, doped Ce O
2Relative amount, LNF and doped Ce O
2Sintering temperature, LNF and doped Ce O
2Crystallite dimensions etc. have determined the catalytic activity of this layer, and this just requires LNF and doped Ce O
2Mass ratio, LNF and doped Ce O
2Technological parameters such as sintering temperature be optimized.Change CeO
2In dopant ion, thereby adjust its oxygen ionic conductivity etc., also be one of catalytic activity optimization approaches.
For improving LNF-doped Ce O
2The electrochemical catalysis performance on barrier layer and with the chemical compatibility of electrolyte ScSZ, in this barrier layer, doped Ce O
2Be preferably 3～4 with the mass ratio of LNF: 7 ~ 6, the sintering temperature of LNF powder is preferably 1100 ℃, doped Ce O
2The sintering temperature of powder is preferably 600 ℃, LNF powder and doped Ce O
2The average grain size ratio of powder is preferably 9 ~ 16.LNF-doped Ce O
2The sintering temperature on barrier layer is preferably 1100 ℃.LNF had both had very high ionic conductivity; Have sufficiently high electron conduction again, and have very high activity, but owing to it at high temperature can react with electrolyte ScSZ; The present invention is placed on the top of composition gradient layer, mainly brings into play the effect of its high conductivity.For improving the performance of LNF current collection layer, in this functional layer, the sintering temperature of LNF powder is preferably 1100 ℃.For LNF-doped Ce O
2Active layer, its polarization overpotential is little, and reactivity is strong, and the present invention is placed on LNF-doped Ce O
2Under the protection on barrier layer, to give full play to LNF-doped Ce O
2Electrochemical catalysis performance to the oxygen reduction reaction.For improving LNF-doped Ce O
2The electrochemical catalysis performance of active layer, in this functional layer, doped Ce O
2Be preferably 2～3 with the mass ratio of LNF: 8 ~ 7, the sintering temperature of LNF powder is preferably 700 ℃, doped Ce O
2The sintering temperature of powder is preferably 600 ℃, LNF-doped Ce O
2The sintering temperature of active layer is preferably 1100 ℃.
The gradient composite cathode of the SOFC of the present invention's preparation has excellent electrochemical catalysis performance, is convenient to improve the power density of fuel cell, guarantees the stable operation of fuel cell.The uniform large-area solid oxide fuel cell of the technology ability Forming Quality gradient composite cathode that is adopted, its technology is simple, and manufacturing cycle is short, and is with low cost, is suitable for commercial application.
Embodiment
Among the embodiment used raw material as follows (reagent in the following raw materials according, unreceipted purity, be analyze pure):
ScSZ powder: Zr
0.89Sc
0.1Ce
0.01O
2(ScSZ, Daiichi Kigenso Kagaku Kogyo, Japan),
YSZ：Zr
0.92Y
0.08O
2(YSZ，Daiichi?Kigenso?Kagaku?Kogyo，Japan)，
Polyvinyl butyral resin: aviation-grade, butyraldehyde base 45% ~ 49%, manufacturer is a Chemical Reagent Co., Ltd., Sinopharm Group,
Polyethylene glycol: chemical pure, mean molecule quantity 190 ~ 210, manufacturer is a Chemical Reagent Co., Ltd., Sinopharm Group,
Terpinol: analyze pure, purity >=99%, manufacturer is a Chemical Reagent Co., Ltd., Sinopharm Group,
Butanone: analyze pure, purity >=99%,
Ethanol: analyze pure, purity >=99.7%,
Triethanolamine, NiO, La (NO
3)
36H
2O, Ni (NO
3)
2, Fe (NO
3)
39H
2O, Gd (NO
3)
36H
2O, Sm (NO
3)
3, Ce (NO
3)
36H
2O, citric acid C
6H
8O
7H
2O: manufacturer is Chemical Reagent Co., Ltd., Sinopharm Group.
Silk screen print method among the embodiment is: powder and the composite slurry of terpinol are printed on respectively on dielectric substrate ScSZ, barrier layer and the active layer through 80 purpose screen clothes get final product.
Embodiment 1:
With weight is the ScSZ powder of 10 grams; Add in the butanone and 4 gram ethanol mixed solvent of 8 grams; Added triethanolamine 0.5 gram ball mill mixing then 2 hours, and added 0.4 gram polyvinyl butyral resin again, 1.5 gram polyethylene glycol also continue that ball milling was stablized in 2 hours, the slurry of homogeneous; The slurry that ball milling is good keeps 10 minutes bubbles of eliminating in the slurry under 100 millibars of conditions of vacuum degree, this is a slurry one;
50g NiO and 50g YSZ mixed powder are joined in the butanone and 24 gram ethanol mixed solvent of 48 grams; Added 3 gram triethanolamine ball mill mixing then 2 hours; Add 10 gram polyvinyl butyral resins again; 13.5 restrain polyethylene glycol and continue that ball milling was stablized in 2 hours, the slurry of homogeneous, the slurry that ball milling is good keeps 10 minutes bubbles of eliminating in the slurry under 100 millibars of conditions of vacuum degree, this is a slurry two;
Homogeneous, stable slurry one are poured into flow casting molding in the feed bin of casting machine, treat its drying after, slurry two poured into carries out Secondary Flow on it and prolong moulding; Make NiO-YSZ/ScSZ anodic composite film biscuit through dry, section, biscuit in 600 ℃ of heat treatment 3h with the burn off biscuit in organic substance, in 1350 ℃ of sintering 3h, obtain the NiO-YSZ/ScSZ anodic composite film at last.
With 0.6g LNF powder and 0.4g Gd doped Ce O
2(Gd
0.2Ce
0.8O
2, GDC) mixture of powder and 1g terpinol are mixed into slurry, are deposited on the ScSZ dielectric substrate and in 110 ℃ of dryings through the silk screen printing method and after 0.5 hour, promptly process the LNF-GDC barrier layer, and the thickness on barrier layer is 8 ~ 10 microns;
Then; The mixture and the 1g terpinol of 0.7g LNF powder and 0.3g GDC powder are mixed into slurry; Be deposited on the LNF-GDC barrier layer and in 110 ℃ of dryings through the silk screen printing method and after 0.5 hour, promptly process the LNF-GDC active layer, the thickness of active layer is 8 ~ 10 microns;
At last, 1g LNF powder and 1g terpinol are mixed into slurry, are deposited on the LNF-GDC active layer and in 110 ℃ of dryings through the silk screen printing method and after 0.5 hour, promptly process the LNF current collection layer, the thickness of current collection layer is 8 ~ 10 microns; The base substrate of the gradient composite cathode of the SOFC that obtains 1100 sintering 2 hours, is promptly obtained the LNF composition gradient composite cathode of SOFC.
The base substrate of the gradient composite cathode of the SOFC that present embodiment makes has excellent electrochemical catalysis performance, and its cathodic polarization face resistance at 750 ℃ is merely 0.52 Ω cm
2And for pure LNF negative electrode, its cathodic polarization face resistance at 750 ℃ is 0.70 Ω cm
2
Embodiment 2:
Identical among the preparation method of NiO-YSZ/ScSZ anodic composite film and the embodiment 1.
With 0.6g LNF powder and 0.4g Sm doped Ce O
2(Sm
0.2Ce
0.8O
2, SDC) mixture of powder and 1g terpinol are mixed into slurry, are deposited on the ScSZ dielectric substrate and in 110 ℃ of dryings through the silk screen printing method and after 0.5 hour, promptly process the LNF-SDC barrier layer, and the thickness on barrier layer is 8 ~ 10 microns;
Then; The mixture and the 1g terpinol of 0.7g LNF powder and 0.3g SDC powder are mixed into slurry; Be deposited on the LNF-SDC barrier layer and in 110 ℃ of dryings through the silk screen printing method and after 0.5 hour, promptly process active layer LNF-SDC, the thickness of active layer is 8 ~ 10 microns;
At last, 1g LNF powder and 1g terpinol are mixed into slurry, are deposited on the LNF-SDC active layer and in 110 ℃ of dryings through the silk screen printing method and after 0.5 hour, promptly process the LNF current collection layer, the thickness of current collection layer is 8 ~ 10 microns; The base substrate of the SOFC gradient composite cathode that obtains 1100 ℃ of sintering 2 hours, is promptly obtained the LNF composition gradient composite cathode of SOFC.
The SOFC gradient composite cathode of present embodiment preparation also has excellent electrochemical catalysis performance, and its cathodic polarization face resistance at 750 ℃ is merely 0.46 Ω cm
2
Embodiment 3:
Identical among the preparation method of NiO-YSZ/ScSZ anodic composite film and the embodiment 1.
The mixture and the 1g terpinol of 0.6g LNF powder, 0.2g GDC powder and 0.2g SDC powder are mixed into slurry; Be deposited on the ScSZ dielectric substrate and in 110 ℃ of dryings after 0.5 hour through the silk screen printing method; Promptly process the LNF-GDC-SDC barrier layer, the thickness on barrier layer is 8 ~ 10 microns;
Then; The mixture and the 1g terpinol of 0.7g LNF powder, 0.15g GDC powder and 0.15g SDC powder are mixed into slurry; Be deposited on the LNF-GDC-SDC barrier layer and in 110 ℃ of dryings after 0.5 hour through the silk screen printing method; Promptly process the LNF-GDC-SDC active layer, the thickness of active layer is 8 ~ 10 microns;
At last, 1g LNF powder and 1g terpinol are mixed into slurry, are deposited on the LNF-GDC-SDC active layer and in 110 ℃ of dryings through the silk screen printing method and after 0.5 hour, promptly process the LNF current collection layer, the thickness of current collection layer is 8 ~ 10 microns; The SOFC gradient composite cathode that obtains was promptly obtained the LNF composition gradient composite cathode of SOFC in 2 hours at 1100 ℃ of sintering.
The SOFC gradient composite cathode of present embodiment has electrochemical catalysis performance preferably, and its cathodic polarization face resistance at 750 ℃ is merely 0.48 Ω cm
2
More than describe preferred embodiment of the present invention in detail.The ordinary skill that should be appreciated that this area need not creative work and just can design according to the present invention make many modifications and variation.Therefore, all technical staff in the art all should be in the determined protection range by claims under this invention's idea on the basis of existing technology through the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (10)
1. the gradient composite cathode of a SOFC is characterized in that, comprising:
Barrier layer, the material on said barrier layer are LNF-doped Ce O
2
Active layer, the material of said active layer are LNF-doped Ce O
2, said active layer is positioned on the said barrier layer;
Current collection layer, the material of said current collection layer are LNF, and said current collection layer is positioned on the said active layer;
Said CeO
2In dopant ion be Gd
3+Or/and Sm
3+
2. the gradient composite cathode of SOFC as claimed in claim 1, wherein, in the said barrier layer, said LNF-doped Ce O
2Middle LNF and doped Ce O
2Mass ratio be 6 ~ 7: 4 ~ 3.
3. the gradient composite cathode of SOFC as claimed in claim 1, wherein, in the said active layer, said LNF-doped Ce O
2Middle LNF and doped Ce O
2Mass ratio be 7 ~ 8: 3 ~ 2.
4. the gradient composite cathode of SOFC as claimed in claim 1 is characterized in that, said CeO
2In the dopant ion mol ratio be (Gd+Sm): Ce=2: 8.
5. a method for preparing the gradient composite cathode of SOFC as claimed in claim 1 is characterized in that, may further comprise the steps:
Step 1, with LNF and doped Ce O
2Mixture and terpinol be mixed into slurry, this slurry is attached on the electrolyte, and after 110 dry 0.5 hour drying, promptly processes said barrier layer;
Said LNF and said doped Ce O
2Mass ratio be 6 ~ 7: 4 ~ 3;
Step 2, with LNF and doped Ce O
2Mixture and terpinol be mixed into slurry, this slurry is attached on the said barrier layer, and after 0.5 hour drying of 110 ℃ of dryings, promptly processes said active layer;
Said LNF and said doped Ce O
2Mass ratio be 7 ~ 8: 3 ~ 2;
Step 3, LNF and terpinol are mixed into slurry, this slurry is attached on the said active layer, and after 110 dry 0.5 hour drying, promptly process said current collection layer, obtain the base substrate of SOFC gradient composite cathode;
Step 4, with the base substrate of said SOFC gradient composite cathode 1100 ℃ of sintering 2 hours, obtain the gradient composite cathode of said SOFC after the cooling.
6. the preparation method of gradient composite cathode as claimed in claim 5, wherein, LNF and doped Ce O in the said step 1
2Mixture and said terpinol, said step 2 in LNF and doped Ce O
2Mixture and said terpinol or said step 3 in the mass ratio of LNF and terpinol be 1: 1.
7. the preparation method of gradient composite cathode as claimed in claim 5, wherein, the slurry method on said active layer, dielectric substrate or the barrier layer that is attached to is a silk screen print method in the said step.
8. a SOFC is characterized in that, the negative electrode of said SOFC is each described gradient composite cathode of claim 1-4.
9. SOFC as claimed in claim 8 is characterized in that, the material of said dielectric substrate is ScSZ.
10. SOFC as claimed in claim 8 is characterized in that, the anode of said SOFC is the NiO-YSZ/ScSZ composite membrane.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103199269A (en) * | 2013-03-21 | 2013-07-10 | 上海交通大学 | Preparation method of functional gradient cathode of intermediate low temperature solid oxide fuel cell |
| CN103346330A (en) * | 2013-07-17 | 2013-10-09 | 上海交通大学 | Composite cathode of chromium-pollution-resistant solid oxide fuel battery and preparation method thereof |
| CN107658486A (en) * | 2017-08-13 | 2018-02-02 | 长沙小新新能源科技有限公司 | A kind of preparation method of solid oxide fuel cell electrolyte film |
| CN109841841A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of high-temperature fuel cell cathode material and its preparation and application |
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| US20090280376A1 (en) * | 2005-11-25 | 2009-11-12 | Reiichi Chiba | Solid Oxide Fuel Cell |
| CN102420332A (en) * | 2011-11-04 | 2012-04-18 | 上海交通大学 | Chromium poisoning-resistant doped CeO2-coated LaNi0.6Fe0.4O3-delta cathode of solid oxide fuel cell and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090280376A1 (en) * | 2005-11-25 | 2009-11-12 | Reiichi Chiba | Solid Oxide Fuel Cell |
| CN102420332A (en) * | 2011-11-04 | 2012-04-18 | 上海交通大学 | Chromium poisoning-resistant doped CeO2-coated LaNi0.6Fe0.4O3-delta cathode of solid oxide fuel cell and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103199269A (en) * | 2013-03-21 | 2013-07-10 | 上海交通大学 | Preparation method of functional gradient cathode of intermediate low temperature solid oxide fuel cell |
| CN103346330A (en) * | 2013-07-17 | 2013-10-09 | 上海交通大学 | Composite cathode of chromium-pollution-resistant solid oxide fuel battery and preparation method thereof |
| CN107658486A (en) * | 2017-08-13 | 2018-02-02 | 长沙小新新能源科技有限公司 | A kind of preparation method of solid oxide fuel cell electrolyte film |
| CN109841841A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of high-temperature fuel cell cathode material and its preparation and application |
| CN109841841B (en) * | 2017-11-29 | 2021-08-31 | 中国科学院大连化学物理研究所 | High-temperature fuel cell cathode material and preparation and application thereof |
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