CN101165951A - Lanthanum chromites base composite connection material for solid oxide fuel battery and its preparation method - Google Patents
Lanthanum chromites base composite connection material for solid oxide fuel battery and its preparation method Download PDFInfo
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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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
This invention relates to a ceramic connection material used in solid oxide fuel cells including a connection material LaCrO3 of 99.5-90wt-% base and an electrolyte material of CeO2 of 0.5-10wt-% base, in which, the preparation method includes: first of all phasing the LaCrO3 base connection material in a high temperature environment of 1000- 1200deg.C and phasing CEO2 powder under 650-800deg.C, 2, mixing them uniformly in terms of the LaCrO3 base connection material: CeO2=(99.5-90wt-%) : (0.5-10wt-%) then drying them for 4-6h, 3, grinding them with a mortar for 3-5h, 4, pressing the grinded powder under 100-600MPa to a shape, which is in high conduction rate, good sintered activity and no thermal stress.
Description
Technical field:
The present invention relates to the pottery connection material field that Solid Oxide Fuel Cell is used.
Background technology:
Solid Oxide Fuel Cell (SOFC) is a kind of high-energy reforming unit, environment amenable energy source device, is considered to the green energy resource of 21 century.At technical difficulty and the requirement of the marketization to reducing cost of high temperature SOFC, temperature changed into the research and development trend into SOFC in the pursuit, and critical material has been proposed requirements at the higher level in recent years.Solid Oxide Fuel Cell is that porous ceramic negative electrode and the anode by the oxygen ion conductor solid electrolyte of densification and its both sides constitutes, and in order to increase power output, need couple together the formation battery pile to a series of monocell with connecting material.The function that connects material is dual: it is the electrical connection between a monocell anode and the contiguous monocell negative electrode on the one hand, and it separates the air oxidation agent of negative electrode and the fuel gas of anode again on the other hand.This just requires to connect material must be fine and close, and it is high that conductivity is wanted, and other assembly of its thermal coefficient of expansion and battery is approaching, in order to avoid excessive thermal stress occurs in making and the operating process.To connect material be the chromic acid lanthanum material that mixes to the maximum pottery of research in the prior art, but its conductivity is very low under mesophilic condition, serious reduction the power of battery pile.And, because its densification sintering temperature is very high, energy consumption is increased, the volatilization of chromium oxide also easily takes place, cause the negative electrode or the anode that burn altogether with it to pollute, battery performance is descended.Therefore, seek the higher connection material of new conductivity, and to reduce its sintering temperature be very urgent research topic.
Connection material in the conventional high-temperature SOFC battery pile is the LaCrO with perovskite structure
3Sill, partly replace La or partly replace Cr with alkaline earth element with other transition elements, can partly change material property, had the material of optimizing composition and gathered " high temperature solid oxide fuel cell-basis; design and application " (the High Temperature Solid Oxide Fuel Cells:Fundamentals that is published in Elsevier publishing houses in 2003, Designand Applications, Edited by subash C Singhal and Kevin Kendall) in the chapter 7 of a book.Nearest W.Z.Zhu, S.C.Deevi more system summary recent progress＜Materials Scienceand Engineering, A348 (2003) 227-243 〉.The common ground of the material that these have been delivered is to use ABO
3The perovskite-based composite oxide material of expressing, its A position all is partly to be replaced by alkaline earth element with La or Y, the Cr of B position is then partly replaced by transition elements such as Fe, Co, Ni, Ti, V, Mn.Though this class material chemically has good stable, their performance characteristics is that conductivity is generally not high.Wherein the material electric conductivity with B position doping Co is the highest, and it can reach 85S/cm 700 ℃ the time in air, but its thermal coefficient of expansion (TEC) is only 14～20 * 10
-6K
-1Between, with solid electrolyte GDC, SDC, YSZ (10～11 * 10
-6K
-1) wait and differ too big, be unsuitable for doing the connection material.For not containing Co, its conductivity is lower, have only 1～15S/cm usually.At H
2In other fuel gas, the oxygen loss reaction all can take place and form the oxygen room in these materials, as the electron hole of main conduction charge carrier, conductivity is further reduced in the consumable material.When utilizing this connection material construction battery pile,, thereby reduced power output because the resistive power loss increases greatly.In the tubular ceramic membrane cell, pottery connection material layer is thicker usually, so this problem becomes more outstanding.On the other hand; for reduce connect material and anode (under the anode support situation) or and negative electrode (under the cathode support body situation) and and electrolyte between thermal and mechanical stress, it is approaching with it or can regulate and (be generally 10-12 * 10 to require to connect the material coefficient of thermal expansion coefficient usually
-6K
-1), this has also increased seeks the new difficulty that connects material.
In the prior art, prepare above-mentioned LaCrO with perovskite structure
3Sill usually adopts traditional powder preparation method, for example citric acid method or glycine method etc., and wherein the citric acid method was published in paper " the Ca-Ti ore type Gd of spontaneous combustion method preparation on " solid-state ionics " magazine in visible 2005
1-xCa
xCrO
3Synthetic and the conductivity of (0＜＜x＜＜0.3) " (Hong-Hai Zhong, Xiao-Liang Zhou, Xing-Qin Liu, Guang-Yao Meng, Synthesis andelectrical conductivity of perovskite Gd
1-xCa
xCrO
3(0＜＜x＜＜0.3) by auto-ignitionprocess, Solid State Ionics 2005,176,1057-1061.); The glycine method was published in " (CeO2) of glycine method preparation on " material news flash " magazine in visible 2002
0.8(Sm2O3)
0.1The sintering of powder and electrical property " (Ranran Peng, Changrong Xia, Qingxi Fu, Guangyao Meng, Dingkun Peng, Sinteringand electrical properties of (CeO2)
0.8(Sm2O3)
0.1Powders prepared byglycine-nitrate process, Mat.Let.2002,56,1043-1047.) paper.
In sum, how to explore high-performance, particularly the pottery of high conductivity connects material, and guarantee that the coupled material of its thermal coefficient of expansion (anode, negative electrode, electrolyte) is close, and fully develop the sintered density that the current material technology of preparing is improved the connection material, be the technical barrier of pendulum in face of the scientific and technical personnel of this area.
Summary of the invention:
Connect the problem that material exists at existing Solid Oxide Fuel Cell pottery, the purpose of this invention is to provide and a kind ofly can improve its conductivity, and its thermal coefficient of expansion NEW TYPE OF COMPOSITE close with continuous material is connected material and preparation method thereof.
Purpose of the present invention realizes in the following manner.
Solid Oxide Fuel Cell lanthanum chromites base composite connection material of the present invention includes LaCrO
3Base connects material, it is characterized in that it also includes CeO
2Base electrolyte material, its content is: LaCrO
3It is 99.5-90wt.-% that base connects material, CeO
2Base electrolyte material is 0.5-10wt.-%.
Described LaCrO
3Base connects material, is meant the LaCrO of doping
3, for example, the LaCrO that the La position is partly replaced by alkaline-earth metal such as Sr or Ca
3, the LaCrO that the Cr position is partly replaced by valence variation elements such as Co, Ni, Mn
3Etc. the class material.
Described CeO
2Base electrolyte material is meant the CeO that Sm, Gd, Y, Tb, Yb, Pr, Nd etc. mix
2Etc. the class material, SDC (Sm for example
0.2Ce
0.8O
1.9), GDC (Gd
0.2Ce
0.8O
1.9) or YDC (Y
0.2Ce
0.8O
1.9).
Solid Oxide Fuel Cell of the present invention comprises with traditional powder preparation method preparing LaCrO with the preparation method of lanthanum chromites base composite connection material
3Base connects material powder and CeO
2The base electrolyte material powder is characterized in that, operating procedure is: (1) is at first with LaCrO
3Base connects the material powder and become phase in 1000 ℃ of-1200 ℃ of hot environment, with CeO
2Powder becomes phase in 650 ℃ of-800 ℃ of hot environments; (2) make the two evenly mix LaCrO in following ratio then
3Base connects material: CeO
2Base electrolyte material=(99.5-90wt.-%): (0.5-10wt.-%), and make the two evenly mix back oven dry 4-6 hour; (3) homogeneous mixture after will drying ground 3-5 hour with mortar; (4) powder after will grinding is at last suppressed in the 100-600Mpa pressure limit with mould and is obtained formed product.
Among the above-mentioned preparation method, described the two even mixing can be realized like this: the two mixture is joined furnishing solution in the volatile solvent, for example be that solvent, the two mixture are solute furnishing solution with the absolute ethyl alcohol, the control solutes content in 5wt.-%～30wt.-% scope, in the Place grinding machine ball milling 24-72 hour again.
Among the above-mentioned preparation method, also can use to contain and form LaCrO
3Sill and CeO
2The soluble-salt of the metal ion of base electrolyte material replaces LaCrO
3Powder and doped Ce O
2Powder, the preparation method of this moment is: (5) at first will form LaCrO
3Sill and CeO
2The soluble-salt of the metal ion of base electrolyte material, for example Ca (NO
3)
24H
2O, Cr (NO
3)
36H
2O, La (NO
3)
3, Ce (NO
3)
36H
2O and Sm (NO
3)
36H
2O etc., formation mixed nitrate solution soluble in water, the amount that wherein adds entry will guarantee to make the nitrate dissolving, in the ie in solution during deposit-free, and the content that makes La, Ca in this aqueous solution, Cr, Ce, Sm is than the metal cation mole ratio that satisfies the pairing soluble-salt of metal cation described in (2); (6) add glycine or citric acid, and make it abundant dissolving, its addition is: the metal cation sum and the mole ratio of glycine or citric acid are controlled in 1: 1.6～2.0 scopes; (7) this mixture of heating is heated to 400～600 ℃ again behind the volatilization evaporate to dryness and makes it high-temp combustion to 60-100 ℃ earlier, obtains the superfine powder that granularity is 50-300nm; (8) superfine powder that obtains is placed Muffle furnace,, remove residual carbon wherein 1000 ℃～1200 ℃ insulations 3-6 hour; (9) continue above-mentioned step (3), (4).
Described composition LaCrO
3The soluble-salt of the metal ion of sill is meant class materials such as metal nitrate, for example La (NO
3)
3, Ca (NO
3)
24H
2O, Cr (NO
3)
36H
2Nitrate such as O.
Described composition CeO
2The soluble-salt of the metal ion of base electrolyte is meant class materials such as metal nitrate, for example La (NO
3)
3, Ca (NO
3)
24H
2O, Cr (NO
3)
36H
2O, Ce (NO
3)
36H
2O, Sm (NO
3)
36H
2Nitrate such as O.
The present invention uses traditional LaCrO
3Base pottery connects the method that material powder and SDC, GDC or YDC powder mix mutually, the perhaps method of directly mixing with nitrate ion, have technology simple, be easy to control, steady performance.Gained new material system, because the interaction and the powder granule of ion conductor and electronic conductor are tiny, so the conductivity height, sintering activity is good, can obtain the material of high-compactness under lower sintering temperature, helps the manufacturing that battery pile connects material layer.And because the doped Ce O2 that adds amount seldom, make the thermal coefficient of expansion of new material close with original chromium-doped hydrochlorate, be that itself and adjacent material (electrode or electrolyte) thermal coefficient of expansion are close, thereby in the battery pile use, can not cause thermal stress, thereby the structural stability and the life-span of pile have been guaranteed.
Embodiment
Below by embodiment the present invention is described further.
Embodiment 1: with LaCrO
3Base connects material LSCM (La
0.75Sr
0.25Cr
0.5Mn
0.5O
3) and GDC (Gd
0.2Ce
0.8O
1.9) be mixed with the present invention mutually and connect material
1. adopt the citric acid method to prepare the GDC powder, raw material is for analyzing pure Ce (NO
3)
36H
2O analyzes pure Gd
2O
3The GDC powder of preparation is incubated 2 hours for 800 ℃ at Muffle furnace, makes it fully to become phase.
2. adopt the method for glycine to prepare the LSCM powder, raw material is for analyzing pure La
2O
3, analyze pure SrCO
3, analyze pure MnCO
3, analyze pure Cr (NO
3)
36H
2O.With the preparation powder in Muffle furnace 1000 ℃ the insulation 4 hours, make it fully to become phase.
3. GDC powder and the LSCM powder with preparation mixes, and makes that the content of GDC is respectively in the mixed powder: 1wt.-%GDC, 2wt.-%GDC, 3wt.-%GDC, 4wt.-%GDC, 5wt.-%GDC, 6wt.-%GDC, 8wt.-%GDC, 10wt.-%GDC, all the other are and the LSCM powder, obtaining 8 kinds of different mixed powders, is solvent with these 8 kinds of mixed powders with anhydrous alcohol respectively, and ball milling is 72 hours behind the furnishing solution, wherein solutes content is 20wt.-%, and two kinds of powders are fully mixed.
4. fully mixed 8 kinds of mixed powders ground 5 hours with mortar respectively after the powder oven dry drying baker oven dry 4 hours again, were pressed into design shape with mould under the pressure of 360MPa respectively at last, promptly got the sample of 8 kinds of different products.
Below 8 kinds of different samples are carried out relevant performance measurement:
5. to above-mentioned sample sintering in Muffle furnace, programming rate was 1 ℃/minute before heating schedule was 500 ℃, was 2 ℃/minute up to 1400 ℃ of programming rates afterwards, 1400 ℃ of insulations 4 hours, was cooled to room temperature afterwards naturally.
6. adopt four-terminal method to measure the sample conductivity of sintering.The temperature range of measuring is 450 ℃-800 ℃, and a secondary data is measured for 50 ℃ in every interval.
7. measure the thermal coefficient of expansion of 8 kinds of heterogeneity samples.
Test result shows, 8 routine samples of present embodiment, and than simple LSCM product, its conductivity all is greatly improved.And in the time of in air, when the GDC content in the sample was 3wt.-%, its conductivity reached maximum: be respectively 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃ maximums: 82.94S/cm, 89.27S/cm, 94.56S/cm, 99.59S/cm, 104.48S/cm.These numerical value all are higher than the aerial conductivity value of LSCM product simple under the relevant temperature far away.The adding of this explanation GDC has improved the conductivity under air conditions.But along with the further increase of GDC content, conductivity can reduce gradually.When the content of GDC is 10wt.-%, the simple aerial conductivity of LSCM under the still a little higher than relevant temperature of the conductivity of sample.In addition, from scanning electron microscope diagram, all samples was at 1400 ℃, 4 hours densified sintering products, and distribution of particles is even.
Learn also that from test result in hydrogen, when the GDC content in the sample was 1wt.-%, conductivity reached maximum.Its maximum in the time of 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃ is respectively: 2.49S/cm, 3.07S/cm, 3.81S/cm, 4.61S/cm, 5.45S/cm.These values all are higher than the aerial conductivity of LSCM product simple under the relevant temperature.This explanation, the adding of a certain amount of GDC has improved the conductivity under the hydrogen condition.But along with the further increase of GDC content, conductivity can decrease.When the content of GDC was 10wt.-%, the conductivity of sample still was higher than the simple conductivity of LSCM product in hydrogen under the relevant temperature.
Embodiment 2: with LaCrO
3Base connects material LCCN (La
0.8Ca
0.2Cr
0.8Ni
0.2O
3) and YDC (Y
0.2Ce
0.8O
1.9) be mixed with mutually
The present invention connects material
1. adopt the glycine method to prepare the GDC powder, raw material is for analyzing pure Ce (NO
3)
36H
2O analyzes pure Y
2O
3The YDC powder of preparation is incubated 3 hours for 650 ℃ at Muffle furnace, makes it fully to become phase.
2. adopt methods of citric acid to prepare the LCCN powder, raw material is for analyzing pure La
2O
3, analyze pure CaCO
3, analyze pure Co (NO
3)
26H
2O analyzes pure Cr (NO
3)
36H
2O.With the preparation powder in Muffle furnace 1200 ℃ the insulation 3 hours, make it fully to become phase.
3. YDC powder and the LCCN powder with preparation mixes, and makes that the content of GDC is respectively in the mixed powder: 1wt.-%YDC, 2wt.-%YDC, 3wt.-%YDC, 4wt.-%YDC, 5wt.-%YDC, 6wt.-%YDC, 8wt.-%YDC, 10wt.-%YDC etc., all the other are and the LSCM powder, obtain 8 kinds of different mixed powders, with these the 8 kinds different powders that mix is that solvent was mixed with behind the solution ball milling 24 hours with anhydrous alcohol respectively, and wherein solutes content is 30wt.-%, and two kinds of powders are fully mixed.
4. fully mixed 8 kinds of mixtures were dried 6 hours in drying baker.Ground 3 hours with mortar powder oven dry back, and last back is pressed into mould powder the strip sample of 8 kinds of different products under 160MPa pressure.
Respectively 8 kinds of different samples are carried out relevant performance measurement below:
5. with 8 kinds of samples sintering in Muffle furnace, programming rate was 1 ℃/minute before heating schedule was 500 ℃, was 2 ℃/minute up to 1400 ℃ of programming rates afterwards, 1400 ℃ of insulations 4 hours, was cooled to room temperature afterwards naturally.
6. adopt four-terminal method to measure the sample conductivity of 8 kinds of sintering.The temperature range of measuring is 450 ℃-800 ℃, and a secondary data is measured for 50 ℃ in every interval.
7. measure the thermal coefficient of expansion of heterogeneity sample.
Test result is: in air, when the YDC content in the sample was 3wt.-%, conductivity reached maximum.Be respectively 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃ maximums: 170.25S/cm, 178.27S/cm, 188.35S/cm, 198.26S/cm, 204.79S/cm.These values all are higher than the aerial conductivity of LCCN under the relevant temperature far away
[4]So the adding of YDC has improved the conductivity of LCCN under the air conditions.Along with the further increase of YDC content, conductivity can progressively reduce.Even but the content of YDC is when being 10wt.-%, the conductivity of sample still is higher than the aerial conductivity of LCCN under the relevant temperature.From scanning electron microscope diagram, 8 kinds of samples were at 1400 ℃, 4 hours densified sintering products, and distribution of particles is even.
In hydrogen, when the YDC content in the sample was 2wt.-%, conductivity reached maximum.To reach maximum different with 3wt.-%YDC under air conditions for these.Be respectively 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃ maximums: 3.22S/cm, 3.91S/cm, 4.70S/cm, 5.64S/cm, 6.92S/cm.The conductivity that all is higher than LCCN under the relevant temperature.The adding of YDC has improved the conductivity under the hydrogen condition.But along with the further increase of YDC content, conductivity progressively reduces.This explanation YDC content reaches after certain value, and YDC plays inhibitory action to the sample conductivity.Experimental data shows that when the content of YDC was 10wt.-%, the conductivity of sample still was higher than the conductivity of LCCN in hydrogen under the relevant temperature.
Embodiment 3: with LCC (La
0.7Ca
0.3CrO
3) and contain SDC (Ce
0.8Sm
0.2O
1.9) the nitric acid salt face of metal cation mix
1. with metal nitrate: analyze pure La (NO
3)
3, analyze pure Ca (NO
3)
24H
2O analyzes pure Cr (NO
3)
36H
2O analyzes pure Ce (NO
3)
36H
2O and the pure Sm (NO of analysis
3)
36H
2O is water-soluble, makes it fully dissolving and forms 8 parts of mixtures.Control Sm in these 8 parts of mixtures
3+, Ce
3+, La
3+, Ca
2+, Cr
3+The molar ratio of metal ion be respectively: 2: 8: 51.8: 22.2: 74,2: 8: 66.5: 28.5: 95,2: 8: 77.7: 33.3: 111,2: 8: 90.3: 38.7: 129,2: 8: 109.9: 47.1: 157,2: 8: 138.6: 59.4: 198,2: 8: 186.9: 80.1: 267,2: 8: 282.8: 121.2: 404, the amount that is equivalent to SDC in 8 kinds of samples was respectively 1wt.-%, 2wt.-%, 3wt.-%, 4wt.-%, 5wt.-%, 6wt.-%, 7wt.-%, 8wt.-%.
2. in 8 kinds of mixtures of 1, add glycine (perhaps citric acid), and make that the amount ratio of metal cation sum and glycine was controlled at 1: 2.0 in each part, stir 15 minutes (180 rev/mins) and make it abundant dissolving;
3. heat this mixture to 60-100 ℃, the evaporate to dryness that progressively volatilizees, and then add hot mixt and make it to obtain the superfine powder that granularity is 50-300nm at 400 ℃ of high-temp combustions.
4. the superfine powder that obtains is placed Muffle furnace,, remove residual carbon wherein 1000 ℃ of insulations 4 hours.
5. ball milling was dried after 72 hours, fully ground 5 hours with mortar again, with mould powder was pressed into the strip sample under 200MPa pressure at last.
Respectively 8 kinds of different samples are carried out relevant performance measurement then:
6. with sample sintering in Muffle furnace, programming rate was 1 ℃/minute before heating schedule was 500 ℃, was 2 ℃/minute up to 1400 ℃ of programming rates afterwards, 1400 ℃ of insulations 4 hours, was cooled to room temperature afterwards naturally.
7. adopt four-terminal method to measure the sample conductivity of sintering.The temperature range of measuring is 450 ℃-800 ℃, and a secondary data is measured for 50 ℃ in every interval.
8. measure the thermal coefficient of expansion of heterogeneity sample.
Adopt the sample of method for preparing, conductivity improves a lot: in air, LCC is 18S/cm 700 ℃ conductivity, and LCC+3wt.-%SDC is respectively 187S/cm and 93S/cm 700 ℃ and 800 ℃ of conductivity in this test; LCC+4wt.-%SDC is respectively 341S/cm and 111S/cm 700 ℃ and 800 ℃ of conductivity; LCC+5wt.-%SDC is respectively 146S/cm and 687S/cm 700 ℃ and 800 ℃ of conductivity; LCC+6wt.-%SDC is respectively 128S/cm and 71S/cm 700 ℃ and 800 ℃ of conductivity.So the adding of SDC has improved the conductivity under the air conditions.Along with the increase of SDC content, conductivity progressively raises.When the content of SDC reached 5wt.-%, conductivity reached maximum.When the content progress of SDC increased, conductivity progressively descended.This explanation SDC content reaches after certain value, and electricity has been led inhibitory action.Experimental result can repeat.At 1400 ℃, 4 hours densified sintering products, and distribution of particles was even from the scanning electron microscope diagram sample.
In hydrogen, when the SDC content in the sample was 3wt.-%, conductivity reached maximum.This has maximum different with 5wt.-%SDC under air conditions.Be respectively 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃ maximums: 4.17S/cm, 4.76S/cm, 5.32S/cm, 5.96S/cm, 7.06S/cm.The conductivity that all is higher than LCC under the relevant temperature.The adding of SDC has improved the conductivity under the hydrogen condition.But along with the further increase of SDC content, conductivity progressively reduces.This explanation SDC content reaches after certain value, and conductivity is played inhibitory action.Experimental data shows that when SDC content was 10wt.-%, conductivity still was higher than the conductivity of pure LCC.
LCC, LSCM, the aerial thermal coefficient of expansion of LCCN (TEC) are respectively 11.12 * 10
-6K
-1, 10.1 * 10
-6K
-1, 11.3 * 10
-6K
-1Experimental result shows that along with the increase of SDC, GDC, YDC content, the thermal coefficient of expansion of sample all has increase in various degree.But because the addition of doped cerium oxide is little, make that TEC amplification is very little, particularly, the thermal coefficient of expansion that has a sample of maximum conductivity changes little, thus with the adjacent materials (LaFeO that mixes of YSZ electrolyte, Sr for example
3, Ni-SDC or Ni-YSZ anode) thermal coefficient of expansion mate fine mutually.The stress that when operation of fuel cells thermal cycle is arranged like this and produce is very little, can not influence battery performance.
Claims (10)
1. a Solid Oxide Fuel Cell lanthanum chromites base composite connection material includes LaCrO
3Base connects material, it is characterized in that it also includes CeO
2Base electrolyte material, its content is: LaCrO
3It is 99.5-90wt.-% that base connects material, CeO
2Base electrolyte material is 0.5-10wt.-%.
2. composite bonding material as claimed in claim 1 is characterized in that, described LaCrO
3Base connects material, is meant the LaCrO that the La position is partly replaced by alkaline-earth metal such as Sr or Ca
3, the LaCrO that the Cr position is partly replaced by valence variation elements such as Co, Ni, Mn
3The class material.
3. composite bonding material as claimed in claim 1 is characterized in that, described CeO
2Base electrolyte material is meant the CeO that Sm, Gd, Y, Tb, Yb, Pr, Nd etc. mix
2The class material.
4. the Solid Oxide Fuel Cell of preparation claim 1 is characterized in that with the method for lanthanum chromites base composite connection material, comprises with traditional powder preparation method preparing LaCrO
3Base connects material powder and CeO
2The base electrolyte material powder is characterized in that, operating procedure is: (1) is at first with LaCrO
3Base connects the material powder and become phase in 1000 ℃ of-1200 ℃ of hot environment, with CeO
2Powder becomes phase in 650 ℃ of-800 ℃ of hot environments; (2) make the two by following mixed, LaCrO then
3Base connects material: CeO
2Base electrolyte material=(99.5-90wt.-%): (0.5-10wt.-%), and make the two evenly mix back oven dry 4-6 hour; (3) homogeneous mixture after will drying ground 3-5 hour with mortar; (4) powder after will grinding is at last suppressed in the 100-600Mpa pressure limit with mould and is obtained formed product.
5. described preparation method as claimed in claim 4 is characterized in that, described LaCrO
3Base connects material, is meant the LaCrO that the La position is partly replaced by alkaline-earth metal such as Sr or Ca
3, the LaCrO that the Cr position is partly replaced by valence variation elements such as Co, Ni, Mn
3The class material.
6. preparation method as claimed in claim 5 is characterized in that, described CeO
2Base electrolyte material is meant the CeO that Sm, Gd, Y, Tb, Yb, Pr, Nd etc. mix
2The class material.
7. described preparation method as claimed in claim 4, it is characterized in that, describedly the two is evenly mixed like this realize: the two mixture is joined furnishing solution in the volatile solvent, the control solutes content in the 5wt.-%30wt.-% scope, in the Place grinding machine ball milling 24-72 hour again.
8. described preparation method as claimed in claim 4 is characterized in that, uses to contain and forms LaCrO
3Sill and CeO
2The soluble-salt of the metal ion of base electrolyte material replaces LaCrO
3Powder and doped Ce O
2Powder, the preparation method of this moment is: (5) at first will form LaCrO
3Sill and CeO
2The soluble-salt of the metal ion of base electrolyte material, formation mixed nitrate solution soluble in water, the amount that wherein adds entry will guarantee to make nitrate dissolving, and the content that makes La, Ca in this aqueous solution, Cr, Ce, Sm is than the metal cation mole ratio that satisfies the pairing soluble-salt of metal cation described in (2); (6) add glycine or citric acid, and make it abundant dissolving, its addition is: the metal cation sum and the mole ratio of glycine or citric acid are controlled in 1: 1.6～2.0 scopes; (7) this mixture of heating is heated to 400～600 ℃ again behind the volatilization evaporate to dryness and makes it high-temp combustion to 60-100 ℃ earlier, obtains the superfine powder that granularity is 50-300nm; (8) superfine powder that obtains is placed Muffle furnace,, remove residual carbon wherein 1000 ℃～1200 ℃ insulations 3-6 hour; (9) step (3), (4) in the continuation claim 4.
9. preparation method as claimed in claim 8, described composition LaCrO
3The soluble-salt of the metal ion of sill is meant metal nitrate class material.
As claim 4 or 8 the preparation method, described composition CeO
2The soluble-salt of the metal ion of base electrolyte is meant metal nitrate class material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102108023A (en) * | 2009-12-29 | 2011-06-29 | 淮南师范学院 | Composite ceramic jointing material |
| CN112490475A (en) * | 2020-10-28 | 2021-03-12 | 西安交通大学 | Method for synthesizing electrolyte powder based on complexation-freeze drying method and obtained electrolyte powder |
| CN114105629A (en) * | 2020-08-27 | 2022-03-01 | 厦门稀土材料研究所 | Preparation method and application of rare earth chromate based porous conductive high-entropy ceramic |
| CN117024168A (en) * | 2023-08-16 | 2023-11-10 | 内蒙古工业大学 | SiO utilization method 2 Preparation of LaCrO from powder 3 Method for joining materials |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0896821A (en) * | 1994-09-27 | 1996-04-12 | Mitsubishi Heavy Ind Ltd | Interconnector for solid electrolytic electrochemical cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0896821A (en) * | 1994-09-27 | 1996-04-12 | Mitsubishi Heavy Ind Ltd | Interconnector for solid electrolytic electrochemical cell |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102108023A (en) * | 2009-12-29 | 2011-06-29 | 淮南师范学院 | Composite ceramic jointing material |
| CN102108023B (en) * | 2009-12-29 | 2013-04-24 | 淮南师范学院 | Composite ceramic jointing material |
| CN114105629A (en) * | 2020-08-27 | 2022-03-01 | 厦门稀土材料研究所 | Preparation method and application of rare earth chromate based porous conductive high-entropy ceramic |
| CN114105629B (en) * | 2020-08-27 | 2023-04-07 | 厦门稀土材料研究所 | Preparation method and application of rare earth chromate based porous conductive high-entropy ceramic |
| CN112490475A (en) * | 2020-10-28 | 2021-03-12 | 西安交通大学 | Method for synthesizing electrolyte powder based on complexation-freeze drying method and obtained electrolyte powder |
| CN117024168A (en) * | 2023-08-16 | 2023-11-10 | 内蒙古工业大学 | SiO utilization method 2 Preparation of LaCrO from powder 3 Method for joining materials |
| CN117024168B (en) * | 2023-08-16 | 2024-04-05 | 内蒙古工业大学 | SiO utilization method 2 Preparation of LaCrO from powder 3 Method for joining materials |
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