CN101295792A - Compound anode of solid-oxide fuel battery and method for producing the same - Google Patents
Compound anode of solid-oxide fuel battery and method for producing the same 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
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- Y02E60/30—Hydrogen technology
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Abstract
The invention relates to a solid oxide fuel cell, in particular to a composite anode of the solid oxide fuel cell and a preparation method thereof. According to weight percentage, the weight composition of the composite anode comprises 30 to 69.9 percent of NiO, 0.1 to 35 percent of rare earth materials and 30 to 69.9 percent of zirconia YSZ with stable yttrium oxide. The composite anode of the solid oxide fuel cell is compounded by adding the rare earth materials to the traditional anode of nickel oxide and zirconia with stable yttrium oxide, and the rare earth materials are added to the anode so as to improve the performance of the anode; the composite anode has the advantages of even distribution of electrode structure, tight interface contact between nickel and YSZ, low polarization impedance, high activity, etc., thus improving the output performance of the cell. The novel composite anode can be applied to flat type, tube type and flat tube type solid oxide fuel cells.
Description
Technical field
The present invention relates to Solid Oxide Fuel Cell, a kind of compound anode of solid-oxide fuel battery and preparation method thereof specifically, by adopting rare earth material mutually compound with the conventional anode material, it is even that the composite anode that obtains has distribution of material, network connects characteristics such as tight between electrode material, reduce the polarization impedance of battery, improve the output performance of battery, improve the performance of battery hydrocarbon fuels such as methane.Directly the application for hydrocarbon fuels such as natural gases has great importance to the development of application technology for promoting the Solid Oxide Fuel Cell technology.
Background technology
Solid Oxide Fuel Cell is the energy conversion device that chemical energy is converted into electric energy, adopt structure of whole solid state, having the generating efficiency height, can directly adopting hydrocarbons such as natural gas is characteristics such as fuel, applied range, be desirable dispersion generating and concentrate power station technology, also can be applied to vehicle accessory power supply, compact power etc.Solid Oxide Fuel Cell mainly is made up of negative electrode, dielectric film, anode three parts.What anode mainly adopted at present is the Ni-YSZ porous metalloceramic, realizes the functions such as gas transfer, electrical conductivity, ionic conduction, catalytic reforming and electrocatalytic reaction of anode.Electrolyte adopts the zirconia (YSZ) of stabilized with yttrium oxide usually, also can be the zirconia (ScSZ) of doping of cerium oxide, scandia stabilized, the lanthanum gallate (LSGM) of mixing etc.Electrocatalyst for cathode generally adopts perovskite oxide and electrolyte to constitute composite cathode, as widely used LSM-YSZ composite cathode, also can be perovskites such as cobalt acid lanthanum, cobalt acid strontium samarium.
Have great importance for the application of hydrocarbon fuels such as natural gas development for the Solid Oxide Fuel Cell technical applicationization, therefore the various anode materials that are adapted to hydrocarbon fuels such as natural gas have obtained broad research, mainly comprise: Ni-based anode, copper base anode, cerium base anode, Ca-Ti ore type anode and precious metal anode etc.Though wherein copper base anode, cerium base anode and Ca-Ti ore type anode have anti-carbon effect preferably, have problems such as activity is very low, be difficult to realize application development; Precious metal anode activity and anti-carbon aspect all have greatly improved, but its cost is very high, are not easy to use.Ni-based anode is the anode material that present Solid Oxide Fuel Cell generally adopts; but because battery needs high temperature sintering (＞1300 ℃ obtain fine and close dielectric film) in preparation process; cause the nickel-base catalyst sintering serious; and be difficult between nickel-base catalyst and the zirconia-based material soaking into; it is not strong to interact; cause in the high temperature reduction process nickel particle also can constantly grow up, thereby cause the anode activity lower, carbon distribution is comparatively serious.
Summary of the invention
In order to overcome the shortcoming of conventional composite anode, the object of the present invention is to provide a kind of compound anode of solid-oxide fuel battery and preparation method thereof, by the rare earth modified novel composite anode of preparing, has good electrode structure, improve the activity of anode, thereby improve the output performance of battery, improve the activity of hydrocarbon fuels such as electrode pair natural gas, suppress carbon distribution.
For achieving the above object, the technical solution used in the present invention is:
A kind of compound anode of solid-oxide fuel battery, by weight percentage, the weight of composite anode consists of, NiO accounts for 30-69.9%, rare earth material accounts for 0.1-35% (can account for 2-25% usually, better account for 5-15), and the zirconia of stabilized with yttrium oxide (YSZ) accounts for 30-69.9%.This compound anode of solid-oxide fuel battery is to add rare earth material to be composited in traditional nickel oxide and the zirconia of stabilized with yttrium oxide (YSZ), and the rare earth material that wherein is used for modification is one or more mixing of rare earth elements such as lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium.Composite anode of the present invention is modified the interface contact that has improved between electrode material by rare earth material, reduces polarization impedance, improves characteristics such as electrode activity, improves the output performance of battery, and has improved the output performance of battery to hydrocarbon fuels such as methane.
The molar content of yittrium oxide is generally 5-12% in the zirconia of described stabilized with yttrium oxide; Described rare earth material is one or more mixing of rare earth oxide, as: the lanthanum of lanthanide series, cerium, praseodymium, neodymium, hard iron, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, yttrium, one or more mixtures of their oxides.
That this novel composite anode can be applicable to is plate, cast and flat-tube type Solid Oxide Fuel Cell.
The preparation process of described composite anode is as follows:
1) A. can adopt earlier rare earth material is compound with nickel oxide and then mix with YSZ, must composite anode materials;
Being divided into of the slaine that the process that rare earth material and nickel oxide is compound can be by nickel or the slaine of oxide and rare earth element or oxide separated, co-precipitation, dipping, mechanical mixture and/or high temperature solid state reaction are finished, and wherein slaine can be nickel or nitrate of rare earth element, carbonate, acetate and/or oxalates;
B. or earlier rare earth material is compound with YSZ and then mix with nickel oxide, must composite anode materials;
The process that rare earth material and YSZ is compound can adopt precipitation, dipping, mechanical mixture and/or high temperature solid state reaction to finish, and wherein rare earth material can be oxide, hydroxide, nitrate, carbonate, acetate and/or the oxalates of rare earth element;
Or directly that the mixture of rare earth material and nickel oxide and YSZ is compound, get composite anode materials;
Directly the process that the mixture of rare earth material and nickel oxide and YSZ is compound can adopt precipitation, dipping, mechanical mixture and/or high temperature solid state reaction to finish, and wherein rare earth material can be oxide, hydroxide, nitrate, carbonate, acetate and/or oxalates;
2) adopt dry-pressing to prepare the thick composite anode substrate of 0.5-2mm,, obtain composite anode at 1000 ℃ of-1700 ℃ of sintering 2-10h.
That the structure of the applicable Solid Oxide Fuel Cell membrane electrode of described composite anode can adopt is plate, cast, flat-tube type and other various makes; Battery can adopt multiple structures such as dielectric film self-cradling type, cathode support type, anode support type; Solid oxide fuel battery electrolyte diaphram can adopt Zirconia electrolytic or doping of cerium oxide electrolyte or other Ca-Ti ore type electrolyte of doping.Electrolyte preparation method can adopt various preparation of inorganic methods such as high temperature sintering, vapour deposition, sol-gel, plasma spraying, and the thickness of electrolyte membrance is 100 nanometers-100 micron.
Adopt the battery MEA of composite anode of the present invention to prepare according to the following procedure:
1) preparation method of compound anode of solid-oxide fuel battery is then that YSZ mixes or first with rare earth material and the compound method that is that then nickel oxide mixes of YSZ for adopting earlier with rare earth material and nickel oxide are compound, also can adopt directly with rare earth material and nickel oxide and YSZ composite methods, the composite anode materials that obtains.
2) adopt dry-pressing to prepare the thick composite anode substrate of 0.5-2mm,, obtain composite anode at 1000 ℃ of-1700 ℃ of sintering 2-10h; Apply one deck thereon and contain the slurry that thickness is 5-50 μ m YSZ.At 1200 ℃ of-1700 ℃ of sintering 2-10h, obtain the anode assembly;
Or, adopt dry-pressing to prepare the thick composite anode substrate of 0.5-2mm, apply one deck thereon and contain the slurry that thickness is 5-50 μ m YSZ; At 1200 ℃ of-1700 ℃ of sintering 2-10h, obtain the anode assembly;
3) after LSM eelctro-catalyst and YSZ mix (by weight 50: 50), adopt silk screen print method to prepare composite cathode, 1000 ℃ of-1300 ℃ of sintering 1-5h.
The test condition of battery: adopt hydrogen (80ml/min) or methane (20ml/min) as anode fuel gas at 800 ℃, oxygen (40ml/min) is as cathode gas.
The invention has the advantages that rare earth material is added in the anode in order to improve anode performance.Improved anode intergranular interface contact greatly by modifying, make electrode have good electrode microstructure, increased the length of three phase boundaries, improved the activity of anode greatly, improved the output performance of battery, and interact with anode catalyst, improved the catalytic reforming activity of electrode, thereby obviously improved the output performance of battery when adopting hydrocarbon fuels such as methane.Characteristics such as this composite anode has also that electrode structure is evenly distributed in addition, nickel contacts closely with interface between the YSZ, hypopolarization impedance, high activity.This composite anode and conventional anode have relatively obviously improved the output performance of battery.It can be applicable to plate, cast and flat-tube type Solid Oxide Fuel Cell.
Embodiment
Embodiment is provided below, and the present invention will be further described:
Embodiment 1
The compound anode of solid-oxide fuel battery of lanthanum modification preparation is to the influence of battery performance
Adopt nitrate to be divided into the method (800 ℃ of decomposition) of separating, obtain the nickel oxide that lanthanum is modified.Select the nickel oxide that lanthanum modifies (Ni: La=1 wherein: 0.08 for use, mol ratio) as anode catalysis material, wherein 8YSZ (molar content of yittrium oxide is 8% among the YSZ) accounts for 40% (weight ratio), adopt dry-pressing to prepare the thick composite anode substrate of 0.7mm, at 1200 ℃ of sintering 5h, obtain composite anode; Apply one deck thereon and contain the slurry that thickness is 10 μ m YSZ.At 1600 ℃ of sintering 3h, obtain the anode assembly; After LSM eelctro-catalyst and YSZ mix (by weight 50: 50), adopt silk screen print method to prepare composite cathode, at 1100 ℃ of sintering 5h.
Traditional Ni-YSZ anode cell battery as a comparison.When being fuel gas with hydrogen, the battery performance that lanthanum is modified and traditional Ni-YSZ anode cell performance relatively, when 800 ℃ of operations battery performance improve about 15%, 700 ℃ of performances raisings about 25%.When adopting methane to be fuel gas, the nickel oxide anode cell that lanthanum is modified in the time of 800 ℃ improves about 100% than traditional Ni-YSZ anode cell performance, and the nickel oxide anode cell of modifying at 700 ℃ of lanthanums improves about 180% than traditional Ni-YSZ anode cell performance.
Embodiment 2
Directly the compound anode of solid-oxide fuel battery that lanthana and nickel oxide and YSZ are mixed with is to the influence of battery performance
Adopt the method for directly lanthana, nickel oxide and 8YSZ (molar content of yittrium oxide is 8% among the YSZ) being mixed to prepare composite anode, the preparation battery, the modification of battery the results are shown in Table 1.
Table 1
As can be seen from Table 1, along with the increase battery performance of lanthanum content increases before this gradually, but when the content of lanthanum is higher the battery performance variation.
Embodiment 3
When the composite anode of lanthanum modification is used for tubular solid oxide fuel cells to the influence of battery performance
Adopt nitrate to be divided into the method (800 ℃ of decomposition) of separating, obtain the nickel oxide that lanthanum is modified.Select for use nickel oxide that lanthanum modifies as anode catalysis material (Ni: La=1 wherein: 0.1, mol ratio), mix (by weight 50: 50) with 8YSZ (molar content of yittrium oxide is 8% among the YSZ), adopt the inoranic membrane technology to prepare the cast anode support, apply one deck thereon and contain the slurry that thickness is 50 μ m YSZ.After the drying,, obtain the anode assembly at 1600 ℃ of sintering 2h.After LSM eelctro-catalyst and YSZ mix (weight ratio 50: 50), preparation composite cathode, 1300 ℃ of sintering 3h.Traditional Ni-YSZ anode tubular cells battery as a comparison.When being fuel gas with hydrogen, the battery performance that lanthanum is modified and traditional Ni-YSZ anode cell performance relatively, when 800 ℃ of operations battery performance improve about 12%, 700 ℃ of performances raisings about 20%.When adopting methane to be fuel gas, the nickel oxide anode cell that lanthanum is modified in the time of 800 ℃ improves about 80% than traditional Ni-YSZ anode cell performance, and the nickel oxide anode cell of modifying at 700 ℃ of lanthanums improves about 150% than traditional Ni-YSZ anode cell performance.
Embodiment 4
Earlier mix the influence of the compound anode of solid-oxide fuel battery that obtains in YSZ again with cerium and nickel oxide are compound to battery performance
Adopt nitrate to be divided into the method (700 ℃ of decomposition) of separating, obtain the nickel oxide that cerium is modified.Select the nickel oxide that cerium modifies (Ni: Ce=1 wherein: 0.01 for use, mol ratio) as anode catalysis material, mix with 5YSZ (molar content of yittrium oxide is 5% among the YSZ), wherein YSZ accounts for 70% (weight ratio), adopt dry-pressing to prepare the thick composite anode substrate of 0.4mm, at 1300 ℃ of sintering 10h, obtain composite anode; Apply one deck thereon and contain the slurry that thickness is 5 μ m YSZ.At 1400 ℃ of sintering 6h, obtain the anode assembly; After LSM eelctro-catalyst and YSZ mix (by weight 50: 50), adopt silk screen print method to prepare composite cathode, at 1100 ℃ of sintering 5h.
Traditional Ni-YSZ anode cell battery as a comparison.When being fuel gas with hydrogen, the battery performance that cerium is modified nickel oxide and traditional Ni-YSZ anode cell performance relatively, when 800 ℃ of operations battery performance improve about 3%, 650 ℃ of performances raisings about 7%.When adopting methane to be fuel gas, the nickel oxide anode cell that cerium is modified in the time of 800 ℃ improves about 20% than traditional Ni-YSZ anode cell performance, and the nickel oxide anode cell of modifying at 650 ℃ of ceriums improves about 60% than traditional Ni-YSZ anode cell performance.
Embodiment 5
Earlier mix the influence of the compound anode of solid-oxide fuel battery that obtains in nickel oxide again with cerium and YSZ are compound to battery performance
Adopt the method (600 ℃ of decomposition) of cerous nitrate dipping, compound with cerium and 10YSZ, then this material is mixed (by weight percentage with nickel oxide, nickel oxide accounts for 40%, cerium oxide accounts for 10%, 10YSZ (molar content of yittrium oxide is 10% among the YSZ) accounts for 50%), adopt dry-pressing to prepare the thick composite anode substrate of 2mm, apply one deck thereon and contain the slurry that thickness is 20 μ m YSZ; At 1300 ℃ of sintering 10h, obtain the anode assembly; After LSM eelctro-catalyst and YSZ mix (by weight 50: 50), adopt silk screen print method to prepare composite cathode, 1000 ℃ of sintering 5h.
Traditional Ni-YSZ anode cell battery as a comparison.When being fuel gas with hydrogen, cerium modified battery performance and traditional Ni-YSZ anode cell performance relatively, battery performance improves approximately 5% when 800 ℃ of operations, improves about 15% 650 ℃ of performances.When adopting methane to be fuel gas, cerium modified battery improves approximately 50% than traditional Ni-YSZ anode cell performance in the time of 800 ℃, and improves about 100% at 650 ℃ of cerium modified batteries than traditional Ni-YSZ anode cell performance.
Embodiment 6
The compound anode of solid-oxide fuel battery of praseodymium modification preparation is to the influence of battery performance
Adopt nitrate to be divided into the method (900 ℃ of decomposition) of separating, obtain the nickel oxide that praseodymium is modified.Select the nickel oxide that praseodymium modifies (Ni: Pr=1 wherein: 0.02 for use, mol ratio) as anode catalysis material, mix with 8YSZ (molar content of yittrium oxide is 8% among the YSZ), wherein YSZ accounts for 30% (weight ratio), adopt dry-pressing to prepare the thick composite anode substrate of 1mm, apply one deck thereon and contain the slurry that thickness is 50 μ mYSZ; At 1300 ℃ of sintering 10h, obtain the anode assembly; After LSM eelctro-catalyst and YSZ mix (by weight 50: 50), adopt silk screen print method to prepare composite cathode, 1300 ℃ of sintering 1h.
Traditional Ni-YSZ anode cell battery as a comparison.When being fuel gas with hydrogen, the nickel oxide anode cell performance that praseodymium is modified and traditional Ni-YSZ anode cell performance relatively, when 750 ℃ of operations battery performance improve about 10%, 650 ℃ of performances raisings about 20%.When adopting methane to be fuel gas, the nickel oxide anode cell that praseodymium is modified in the time of 750 ℃ improves about 100% than traditional Ni-YSZ anode cell performance, and the nickel oxide anode cell of modifying at 650 ℃ of praseodymiums improves about 200% than traditional Ni-YSZ anode cell performance.
Embodiment 7
The compound anode of solid-oxide fuel battery of neodymium modification preparation is to the influence of battery performance
Adopt nitrate to be divided into the method (800 ℃ of decomposition) of separating, obtain the nickel oxide that neodymium is modified.Select the nickel oxide that neodymium modifies (Ni: Nd=1 wherein: 0.2 for use, mol ratio) as anode catalysis material, mix with 8YSZ (molar content of yittrium oxide is 8% among the YSZ), wherein YSZ accounts for 40% (weight ratio), adopt dry-pressing to prepare the thick composite anode substrate of 1.5mm, apply one deck thereon and contain the slurry that thickness is 10 μ mYSZ; At 1450 ℃ of sintering 5h, obtain the anode assembly; After LSM eelctro-catalyst and YSZ mix (by weight 60: 40), adopt silk screen print method to prepare composite cathode, 1250 ℃ of sintering 2h.
Traditional Ni-YSZ anode cell battery as a comparison.When being fuel gas with hydrogen, the nickel oxide anode cell performance that neodymium is modified and traditional Ni-YSZ anode cell performance relatively, when 800 ℃ of operations battery performance improve about 3%, 650 ℃ of performances raisings about 8%.When adopting methane to be fuel gas, the nickel oxide anode cell that neodymium is modified in the time of 800 ℃ improves about 10% than traditional Ni-YSZ anode cell performance, and the nickel oxide anode cell of modifying at 650 ℃ of neodymiums improves about 50% than traditional Ni-YSZ anode cell performance.
Embodiment 8
The compound anode of solid-oxide fuel battery of samarium modification preparation is to the influence of battery performance
Adopt nitrate to be divided into the method (850 ℃ of decomposition) of separating, obtain the nickel oxide that samarium is modified.Select the nickel oxide that samarium modifies (Ni: Sm=1 wherein: 0.1 for use, mol ratio) as anode catalysis material, wherein 10YSZ (molar content of yittrium oxide is 10% among the YSZ) accounts for 60% (weight ratio), adopt dry-pressing to prepare the thick composite anode substrate of 0.7mm, at 1200 ℃ of sintering 10h, obtain composite anode; Apply one deck thereon and contain the slurry that thickness is 30 μ m YSZ.At 1600 ℃ of sintering 3h, obtain the anode assembly; After LSM eelctro-catalyst and YSZ mix (by weight 50: 50), adopt silk screen print method to prepare composite cathode, at 1100 ℃ of sintering 5h.
Traditional Ni-YSZ anode cell battery as a comparison.When being fuel gas with hydrogen, the nickel oxide anode cell performance that samarium is modified and traditional Ni-YSZ anode cell performance relatively, when 800 ℃ of operations battery performance improve about 18%, 700 ℃ of performances raisings about 55%.When adopting methane to be fuel gas, the nickel oxide anode cell that samarium is modified in the time of 800 ℃ improves about 110% than traditional Ni-YSZ anode cell performance, and the nickel oxide anode cell of modifying at 700 ℃ of samariums improves about 210% than traditional Ni-YSZ anode cell performance.
Embodiment 9
The compound anode of solid-oxide fuel battery of gadolinium modification preparation is to the influence of battery performance
Adopt nitrate to be divided into the method (750 ℃ of decomposition) of separating, obtain the nickel oxide that gadolinium is modified.Select the nickel oxide that gadolinium modifies (Ni: Gd=1 wherein: 0.15 for use, mol ratio) as anode catalysis material, mix with 6YSZ (molar content of yittrium oxide is 6% among the YSZ), wherein YSZ accounts for 40% (weight ratio), adopt dry-pressing to prepare the thick composite anode substrate of 1.5mm, apply one deck thereon and contain the slurry that thickness is 10 μ mYSZ; At 1450 ℃ of sintering 5h, obtain the anode assembly; After LSM eelctro-catalyst and YSZ mix (by weight 50: 50), adopt silk screen print method to prepare composite cathode, 1250 ℃ of sintering 2h.
Traditional Ni-YSZ anode cell battery as a comparison.When being fuel gas with hydrogen, the battery performance that gadolinium is modified and traditional Ni-YSZ anode cell performance relatively, when 800 ℃ of operations battery performance improve about 17%, 700 ℃ of performances raisings about 60%.When adopting methane to be fuel gas, the nickel oxide anode cell that gadolinium is modified in the time of 800 ℃ improves about 120% than traditional Ni-YSZ anode cell performance, and the nickel oxide anode cell of modifying at 700 ℃ of gadoliniums improves about 200% than traditional Ni-YSZ anode cell performance.
Embodiment 10
The compound anode of solid-oxide fuel battery of the common modification preparation of samarium and gadolinium is to the influence of battery performance
Adopt nitrate to be divided into the method (800 ℃ of decomposition) of separating, obtain the nickel oxide that samarium and gadolinium are modified.Select the nickel oxide that samarium and gadolinium modify (Ni: Sm: Gd=1 wherein: 0.05: 0.05 for use, mol ratio) as anode catalysis material, mix with 6YSZ (molar content of yittrium oxide is 6% among the YSZ), wherein YSZ accounts for 30% (weight ratio), adopt dry-pressing to prepare the thick composite anode substrate of 1.5mm, apply one deck thereon and contain the slurry that thickness is 10 μ m YSZ; At 1450 ℃ of sintering 5h, obtain the anode assembly; After LSM eelctro-catalyst and YSZ mix (by weight 50: 50), adopt silk screen print method to prepare composite cathode, 1250 ℃ of sintering 2h.
Traditional Ni-YSZ anode cell battery as a comparison.When being fuel gas with hydrogen, the battery performance that samarium and gadolinium are modified and traditional Ni-YSZ anode cell performance relatively, when 800 ℃ of operations battery performance improve about 15%, 700 ℃ of performances raisings about 40%.When adopting methane to be fuel gas, the nickel oxide anode cell that samarium and gadolinium are modified in the time of 800 ℃ improves about 130% than traditional Ni-YSZ anode cell performance, and improves about 180% at the nickel oxide anode cell of 700 ℃ of samariums and gadolinium modification than traditional Ni-YSZ anode cell performance.
Claims (9)
1. compound anode of solid-oxide fuel battery, it is characterized in that: by weight percentage, the weight of composite anode consists of, and NiO accounts for 30-69.9%, and rare earth material accounts for 0.1-35%, and the zirconia YSZ of stabilized with yttrium oxide accounts for 30-69.9%.
2. according to claims 1 described compound anode of solid-oxide fuel battery, it is characterized in that: described rare earth material accounts for 2-25%.
3. according to claims 1 described compound anode of solid-oxide fuel battery, it is characterized in that: described rare earth material accounts for 5-15.
4. according to claims 1 described compound anode of solid-oxide fuel battery, it is characterized in that: the molar content of yittrium oxide is 5-12% in the zirconia of described stabilized with yttrium oxide.
5. according to claims 1 described compound anode of solid-oxide fuel battery, it is characterized in that: described rare earth material is one or more mixing of lanthanum, cerium, praseodymium, neodymium, hard iron, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium or the yttrium oxide of lanthanide series rare-earth elements.
6. the preparation method of claims 1 described compound anode of solid-oxide fuel battery is characterized in that:
1) can adopt earlier rare earth material is compound with nickel oxide and then mix with YSZ, must composite anode materials;
Or earlier that rare earth material is compound with YSZ and then mix with nickel oxide, must composite anode materials;
Or directly that the mixture of rare earth material and nickel oxide and YSZ is compound, get composite anode materials;
2) adopt dry-pressing to prepare the thick composite anode substrate of 0.5-2mm,, obtain composite anode at 1000 ℃ of-1700 ℃ of sintering 2-10h.
7. according to the preparation method of the described compound anode of solid-oxide fuel battery of claim 6, it is characterized in that: being divided into of the slaine that the process that rare earth material and nickel oxide is compound can be by nickel or the slaine of oxide and rare earth element or oxide separated, co-precipitation, dipping, mechanical mixture and/or high temperature solid state reaction are finished, and wherein slaine can be nickel or nitrate of rare earth element, carbonate, acetate and/or oxalates.
8. according to the preparation method of the described compound anode of solid-oxide fuel battery of claim 6, it is characterized in that: the process that rare earth material and YSZ is compound can adopt precipitation, dipping, mechanical mixture and/or high temperature solid state reaction to finish, and wherein rare earth material can be oxide, hydroxide, nitrate, carbonate, acetate and/or the oxalates of rare earth element.
9. according to the preparation method of the described compound anode of solid-oxide fuel battery of claim 6, it is characterized in that: directly the process that the mixture of rare earth material and nickel oxide and YSZ is compound can adopt precipitation, dipping, mechanical mixture and/or high temperature solid state reaction to finish, and wherein rare earth material can be oxide, hydroxide, nitrate, carbonate, acetate and/or oxalates.
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