CN106450352B - A kind of anti-carbon anode of solid oxide fuel cell and preparation method thereof - Google Patents

A kind of anti-carbon anode of solid oxide fuel cell and preparation method thereof Download PDF

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CN106450352B
CN106450352B CN201611122496.5A CN201611122496A CN106450352B CN 106450352 B CN106450352 B CN 106450352B CN 201611122496 A CN201611122496 A CN 201611122496A CN 106450352 B CN106450352 B CN 106450352B
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anode
powder
nitrate
ion
nickel
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CN106450352A (en
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王志成
孙建国
李逍遥
袁瑜含
钱斌
张惠国
冯金福
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Changshu Institute of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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
    • Y02E60/50—Fuel cells

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention discloses a kind of anti-carbon anode of solid oxide fuel cell and preparation method thereof, it is to introduce the corronil nano dot with electro catalytic activity and high anti-carbon performance on the basis of the monel with micro-meter scale microstructure-doped cerium oxide porous metalloceramic anode.The introducing of corronil nano dot selectively forms active corronil nano dot in monel particle surface in the micro-meter scale duct of porous metalloceramic skeleton using second order heat-treating methods under metal ion-urea mixed solution dipping and reducing atmosphere.The anode of micrometer/nanometer structured of the invention has suitable fuel gas diffusion admittance, richer three phase boundary, and the applied field bore area for inhibiting carbon distribution to be formed, therefore have the electro catalytic activity to hydrocarbon gas high, the advantages that having strong anti-carbon capacity is suitable for direct hydrocarbon fuel and operates.

Description

A kind of anti-carbon anode of solid oxide fuel cell and preparation method thereof
Technical field
The invention belongs to the technical fields of new energy materials, are related to a kind of directly hydrocarbon middle low-temperature solid oxide fuel electricity Pool technology, in particular to micrometer/nanometer structured high electrocatalytic active anti-carbon anode of solid oxide fuel cell and Preparation method.
Background technique
Fuel cell is a kind of device for directly converting chemical energy to electric energy, and reaction product is water and titanium dioxide Carbon, therefore have the advantages that energy transformation ratio height and pollute low.Solid oxide fuel cell is a kind of using ceramic material work For the structure of whole solid state of component, therefore (800~1000 DEG C) can be worked at high temperature.The great advantage of hot operation is can be with Hydrocarbon gas is directlyed adopt as fuel, to solve the problems such as hydrogen is produced, stores and transported.
Anode carbon distribution is directly using hydrocarbon gas as the greatest problem of fuel gas.Because of traditional Ni-based anode, While being catalyzed hydrocarbon gas generation electrochemical reaction, it can also be catalyzed hydrocarbon gas and pyrolytic occurs, form Carbon deposition.Carbon distribution The channel of gas diffusion can be hindered, also can be to expand anode, microstructure is by destruction until avalanche.If to fuel Inside reforming is carried out, then needs to mix a large amount of vapor in fuel gas, then needs to consume a large amount of energy, Er Qiehui in this way Anode is set to generate biggish temperature gradient, to generate internal stress.(700 DEG C of <) direct oxidation hydrocarbon gas is under middle low temperature A kind of up-and-coming technology because low-temperature operation can not only weaken the trend of hydrocarbon gas pyrolytic, and can drop Phase counterdiffusion and reaction between low battery material, are additionally favorable for the quick start of battery.But this requires anodes with higher Electro catalytic activity, while also to have good anti-carbon performance, because the uneven decomposition of carbon monoxide can also produce under low temperature Raw carbon distribution.Although copper-based anode, cerium base anode have preferable anti-carbon effect, electro catalytic activity is lower or conductivity It is lower, it is difficult functionization.Therefore being modified to traditional Ni-based anode is a kind of reasonable method of comparison.
Summary of the invention
Goal of the invention of the invention is to provide a kind of micrometer/nanometer structured high electrocatalytic active anti-carbon solid oxygen The composition of compound anode of fuel cell, structure and preparation method thereof.
In order to solve the above technical problems, first aspect present invention provides a kind of anti-carbon anode of solid oxide fuel cell Preparation method comprising following steps:
S1. the nitrate solution for preparing nickel ion, copper ion, is then added to nitrate for amion acetic acid or stearic acid In solution, heating concentration is stirred evenly until obtaining powder, then calcining obtains grey nickel by powder or brown color nickel under high temperature Copper alloy powder；
S2. cerous nitrate and samaric nitrate or gadolinium oxide are dissolved in deionized water and are made into nitrate solution, then by amion acetic acid Or stearic acid is added in nitrate solution, is stirred evenly heating concentration until obtaining powder, is finally calcined at high temperature To flaxen SDC (samarium doping cerium oxide) or GDC (gadolinium doped-ceria) powder；
S3. then dry in 50~80 DEG C of vacuum by powder made from S1 and S2 according to the ratio mixing and ball milling of 5:5~8:2 It is dry to obtain mixed-powder；
S4. by mixed-powder made from S3 and partial size be 0.5~3.0 μm polystyrene mono-dispersion microballoon according to 7:3~ The ratio of 9:1 ultrasonic mixing in alcohol or medium-acetone, is then dried in vacuo；
S5. powder S4 obtained takes to be fitted into stainless steel mould in right amount, suppresses plain with the pressure of 100~500MPa Piece is then sintered at 1000~1300 DEG C, and reductase 12~8h is obtained in hydrogen atmosphere at 500~900 DEG C after furnace cooling The monel of micro-meter scale microstructure-doped cerium oxide porous metalloceramic anode skeleton；
S6. nickel nitrate, copper nitrate and urea are dissolved in obtained solution in deionized water, wherein the molar ratio of ambrose alloy ion It is under vacuum conditions that above-mentioned infusion is more to monel-doped cerium oxide that S5 is prepared is placed with for 1:1~4:1 In the container of mesoporous metal ceramic anode skeleton, after standing a period of time, kept the temperature at 77~100 DEG C after cermet is taken out, so It can be formed afterwards in the monel particle surface in skeleton duct in hydrogen atmosphere in 350~450 DEG C of heat treatment a period of times Equally distributed copper nano dot.Heat treatment temperature is finally risen to 600~900 DEG C and keeps the temperature a period of time, copper nano dot and bone The Ni-based aurification that is harmonious in frame, that is, activate, to form the copper-rich nanostructure with electro catalytic activity, the above process repeats several It is secondary, finally obtain micrometer/nanometer structured high electrocatalytic active anti-carbon anode of solid oxide fuel cell.
Preferably, in the step S1, prepare nickel ion, copper ion nitrate solution, nitrate solution be 0.1~ 2.0M, wherein the molar ratio of copper ion and nickel ion is 0~1:9.
Preferably, in the step S1, wherein the molar ratio of amion acetic acid or stearic acid and the nitrate anion in solution is 1:2~2:1.
Preferably, in the step S1, will heating concentration until obtain powder, be heat-treated 0.5 at 500~800 DEG C~ 8h obtains grey nickel by powder or brown color monel powder.
Preferably, in the step S2, nitrate solution concentration is 0.1~2.0M, wherein cerium ion and samarium ion or gadolinium The molar ratio of ion is 8:2.
Preferably, in the step S2, wherein the molar ratio of amion acetic acid or stearic acid and the nitrate anion in solution is 1:2~2:1.
Preferably, in the step S2, it is finally heat-treated 0.5~8h at 500~800 DEG C and obtains flaxen SDC (samarium Doped cerium oxide) or GDC (gadolinium doped-ceria) powder.
Preferably, in the step S3, by 24~96h of powder mixing and ball milling made from S1 and S2, ball-milling medium is alcohol Or acetone, then mixed-powder is obtained in 50~80 DEG C of 6~48h of vacuum drying.
Preferably, in the step S4, by mixed-powder made from S3 and polystyrene mono-dispersion microballoon in alcohol or 1~6h of ultrasonic mixing in medium-acetone, then in 50~80 DEG C of 6~48h of vacuum drying.
Preferably, in the step S5, the powder that S4 is obtained take 0.2~1.0g be packed into diameter be 1.0~20cm not In steel mold of becoming rusty, plain piece is suppressed to obtain with the pressure of 100~500MPa.
Preferably, in the step S6, nickel nitrate, copper nitrate and urea are dissolved in deionized water, wherein metal ion The solution of 2M~5M is made according to molar ratio 1:5~1:1.5 with urea, wherein the molar ratio of ambrose alloy ion is 1:1~4:1.
The second aspect of the present invention provides a kind of anode of solid oxide fuel cell that the above method is prepared.
Preferably, in the monel of anode-doped cerium oxide porous metalloceramic anode skeleton, the ambrose alloy of anode is closed In gold-doped cerium oxide porous metalloceramic anode skeleton, doped cerium oxide granular size is 0.2~1.0 μm, monel Grain size is 0.2~1.0 μm and connected holes size is 0.5~2.0 μm.
Preferably, in the monel of anode-doped cerium oxide porous metalloceramic anode skeleton, copper contains in monel Amount is 0~10%.
Preferably, in the monel of anode-doped cerium oxide porous metalloceramic anode skeleton, selectively in ambrose alloy Alloying pellet surface has equally distributed corronil nano dot, and the size of nano dot is 5nm~50nm.
Preferably, in the monel of anode-doped cerium oxide porous metalloceramic anode skeleton, corronil nano dot Middle copper content is 50~100%, preferably 50~80%.
Preferably, in the monel of anode-doped cerium oxide porous metalloceramic anode skeleton, corronil nano dot Weight percent is 2.5~10% of metal gross weight in anode.
A kind of micrometer/nanometer structured high electrocatalytic active anti-carbon solid oxide fuel electricity provided by the invention The preparation method of pond anode, comprising the following steps:
1) nickel nitrate, copper nitrate are dissolved in the nitrate solution that deionized water is made into 0.1~2.0M, wherein copper ion and nickel The molar ratio of ion is 0~1:9, then amion acetic acid or stearic acid is added in nitrate solution, wherein amino second The sour molar ratio with the nitrate anion in solution is 1:2~2:1, is heated on electric furnace after mixing evenly at room temperature, and concentration is until certainly Combustion obtain black perhaps grey powder finally at 500~800 DEG C be heat-treated 0.5~8h obtain gray oxide nickel by powder or Brown color copper mixes up nickel oxide powder；
2) cerous nitrate, samaric nitrate or gadolinium nitrate are dissolved in the nitrate solution that deionized water is made into 0.1~2.0M, wherein cerium The molar ratio of ion and samarium ion or gadolinium ion is 8:2, and then amion acetic acid or stearic acid are added in nitrate solution, Wherein the molar ratio of amion acetic acid and the nitrate anion in solution is 1:2~2:1, is heated on electric furnace after mixing evenly at room temperature, Concentration is until spontaneous combustion obtains buff powder, and finally 0.5~8h of heat treatment obtains flaxen SDC (samarium at 500~800 DEG C Doped cerium oxide) or GDC (gadolinium doped-ceria) powder；
1) and 2) 3) by powder made from according to ratio 24~96h of ball milling mixing of 50:50~80:20, ball-milling medium is Then alcohol or acetone obtain mixed-powder in 50~80 DEG C of 6~48h of vacuum drying.
4) by mixed-powder made from 3) and partial size be 0.5~3.0 μm polystyrene mono-dispersion microballoon according to 7:3~9: 1 ratio, 1~6h of ultrasonic mixing in alcohol or medium-acetone, then in 50~80 DEG C of 6~48h of vacuum drying；
5) 0.2~1.0g is taken to be fitted into the stainless steel mould that diameter is 1.0~20cm in the powder 4) obtained, with 100~ The pressure of 500MPa suppresses to obtain plain piece, 2~6h is then sintered at 1000~1300 DEG C, after furnace cooling at 500~900 DEG C Reductase 12~8h obtains monel-doped cerium oxide porous metalloceramic sun of micro-meter scale microstructure in hydrogen atmosphere Pole skeleton；
6) nickel nitrate, copper nitrate and urea are dissolved in deionized water, wherein metal ion and urea are according to molar ratio 1:5 The solution of 2M~5M is made in~1:1.5, and wherein the molar ratio of ambrose alloy ion is 1:1~4:1, under vacuum conditions will be above-mentioned molten Perfusion to being placed in monel-doped cerium oxide porous metalloceramic anode skeleton container, subsequent normal pressure stands 0.5~ 3h keeps the temperature 0.5~3h at 77~100 DEG C after taking out cermet, and in hydrogen atmosphere at 350~450 DEG C of heat 1~4h is managed, equally distributed copper nano dot can be formed in the monel particle surface in skeleton duct, it finally will heat treatment temperature Degree rises to 600~900 DEG C and keeps the temperature 1~4h, the Ni-based aurification that is harmonious in copper nano dot and skeleton activates, to form tool There is the copper-rich nanostructure of electro catalytic activity.The above process repeats 2~4 times, finally obtains the high electricity of micrometer/nanometer structured Catalytic activity anti-carbon anode of solid oxide fuel cell.
In technical solution of the present invention, low-temperature solid in a kind of micrometer/nanometer structured high electrocatalytic active anti-carbon Oxide body anode of fuel cell, the anode using made from polymer microsphere pore creating material with micro-meter scale microstructure On monel-doped cerium oxide porous metalloceramic anode, using metal ion-urea mixed solution dipping and reducing atmosphere Lower second order heat-treating methods introduce the corronil nano dot with electro catalytic activity and high anti-carbon performance.Porous metals pottery Porcelain is prepared using polymer microsphere template.
A kind of micrometer/nanometer structured high electrocatalytic active anti-carbon solid oxide fuel cell sun of the invention Pole, the suitable fuel gas diffusion admittance of skeleton offer of micro-meter scale microstructure, ion, electron-transport path, and Certain mechanical strength.The active nano point on metal phase particles surface, can provide richer three phase boundary in duct, and Form the applied field bore area for inhibiting carbon distribution.Therefore there is this anode low gas concentration to polarize, to hydrocarbon The electro catalytic activity of gas is high, the advantages that having strong anti-carbon capacity, is suitable for direct hydrocarbon fuel and operates.A kind of micron of the invention/ The preparation of nano composite structure high electrocatalytic active anti-carbon anode of solid oxide fuel cell, due to porous metalloceramic Copper content is very low in skeleton, therefore the method that can continue to use traditional compacting or curtain coating, sintering, and guarantees the microcosmic knot of anode Structure is controllable；It is lower additionally, due to the nano dot content of introducing, thus more completely infusion process low temperature preparation will save its preparation process Shi Shengli.
Detailed description of the invention:
Fig. 1 is the anode cross-section morphology figure of preparation of the embodiment of the present invention.
Specific embodiment
The following examples are of the invention to be further described, but the contents of the present invention are without being limited thereto.Present invention explanation Embodiment in book is only used for that the present invention will be described, does not play restriction effect to protection scope of the present invention.This The protection scope of invention is only defined by the claims, and those skilled in the art are in embodiment disclosed by the invention on the basis of institute Any omission, replacement or the modification made fall within protection scope of the present invention.
The present invention by way of example rather than provide the mode of limitation to be illustrated.It should be noted that in present disclosure " one " or "an" embodiment is not necessarily referring to same specific embodiment, and refers at least a kind of.
Various aspects of the invention are described below.However, as will be readily apparent to one of skill in the art, it can Only some or all of aspects according to the present invention implement the present invention.For purposes of illustration, provide herein specific number, material and Configuration, enables one to thoroughly understand the present invention.However, those of skill in the art are evident that, The present invention is without concrete details, that is, implementable.In other examples, many institutes have been omitted or simplified not make the present invention obscure Known feature.
Various operations are successively described as multiple discrete steps, and with the side of the invention most helpful in understanding Formula illustrates；However, in-order description should not be construed as to imply that these operations are necessarily dependent on sequence.
It will illustrate various embodiments according to the reactant of type species.Those of skill in the art will be shown and It is clear to, any number of different types of reactant can be used to implement for the present invention, and be more than those for the purpose of illustration And the reactant provided herein.In addition, also it is evident that, the invention is not limited to any specific mixing to show Example.
Embodiment 1
Nickel nitrate is dissolved in the nitrate solution that deionized water is made into 1.0M, it is molten that amion acetic acid is then added to nitrate In liquid, wherein the molar ratio of amion acetic acid and the nitrate anion in solution is 1:2.It is heated on electric furnace after mixing evenly at room temperature, Concentration is until spontaneous combustion obtains black powder.Then it is heat-treated 4h at 700 DEG C and obtains grey NiO powder.By cerous nitrate, samaric nitrate It is dissolved in the nitrate solution that deionized water is made into 1.0M, wherein the molar ratio of cerium ion and samarium ion is 8:2, then by amino second Acid is added in nitrate solution, and wherein the molar ratio of amion acetic acid and the nitrate anion in solution is 1:2.It stirs evenly at room temperature It is heated on electric furnace afterwards, concentration is until spontaneous combustion obtains buff powder.Then at 700 DEG C be heat-treated 04h obtain it is flaxen SDC powder.
By NiO powder obtained and SDC powder according to the ratio ball milling mixing 72h of 65:35, ball-milling medium is alcohol.So Mixed-powder is obtained for 24 hours in 60 DEG C of vacuum drying afterwards.The polystyrene mono-dispersion microballoon for being 0.54 μm by mixed-powder and partial size According to the ratio of 8:2 in alcoholic media ultrasonic mixing 3h.Then for 24 hours in 60 DEG C of vacuum drying.
It takes 0.45g to be fitted into the stainless steel mould that diameter is 1.5cm in obtained powder, is pressed into 200MPa pressure Piece.Blank is sintered 4h at 1100 DEG C, after furnace cooling, the slurry containing SDC is applied to the side of plain piece by spin-coating method. 4h is sintered at 1200 DEG C, after furnace cooling at 600 DEG C in hydrogen atmosphere reductase 12 h.In the electricity of double-layer ceramic obtained It solves matter side and pastes waterproof sealing adhesive plaster.
Nickel nitrate, copper nitrate and urea are dissolved in the solution that 2.3M is made in deionized water according to molar ratio 1:1.5, true Under empty condition by above-mentioned infusion into the container for being placed with double-layer ceramic, subsequent normal pressure stands 0.5h. and takes out cermet 1.0h is kept the temperature at 80 DEG C afterwards, and in 400 DEG C of heat treatment 2h in hydrogen atmosphere.Heat treatment temperature is then risen to 600 DEG C simultaneously Furnace cooling after heat preservation 2h.Above-mentioned dipping heat treatment process is repeated 2 times.
The cobalt acid samarium and Sm doped CeO_2 (SSC/ of strontium doping are finally prepared by the method for spin coating in electrolyte side SDC) composite cathode.To obtain with Cu0.8Ni0.2Nano dot modifies the micrometer/nanometer structuring of Ni-SDC porous metalloceramic The monocell of anode, wherein the content of nano dot is 5%.
The peak power output of this monocell is 335mW/cm2, the power attenuation after 120h is 2%, the carbon on skeleton surface Relative deposition area is 3.4%.
Embodiment 2
Monocell anode is made according to 1 mode of embodiment, is made using silk screen print method containing electrolyte layer and cathode layer Monocell.
The peak power output of this monocell is 327mW/cm2, the power attenuation after 120h is 2.1%, skeleton surface Carbon phase is 3.9% to depositional area.
Embodiment 3
Nickel nitrate, copper nitrate are dissolved in the nitrate solution that deionized water is made into 2.0M, wherein copper ion and nickel ion Molar ratio is 0.5:9.5, and then amion acetic acid is added in nitrate solution, wherein the nitrate anion in amion acetic acid and solution Molar ratio be 1:1.It is heated on electric furnace after mixing evenly at room temperature, concentration is until spontaneous combustion obtains grey powder.Then 700 It is heat-treated 4h at DEG C and obtains brown color Ni0.95Cu0.05O powder.By Ni obtained0.95Cu0.05O powder and with made from embodiment 1 SDC powder is dry according to 1 mode ball milling mixing of embodiment.Mixed-powder is micro- for 1.14 μm of polystyrene monodisperse with partial size Ball is according to 1 mode combination drying of embodiment.Then it is made to impregnate after double-layer ceramic according to 1 mode of embodiment and be heat-treated, it is different Be second-order heat treatment temperature be 700 DEG C, number of repetition be 4 times.
Finally obtain with 1 mode of embodiment with Cu0.7Ni0.3Nano dot modifies Ni0.95Cu0.05- SDC porous metalloceramic The monocell of micrometer/nanometer structured anode, wherein the content of nano dot is 10%.
The peak power output of this monocell is 350mW/cm2, and the power attenuation after 120h is 1.8%, skeleton surface Carbon phase is 2.1% to depositional area.
Embodiment 4
Double-layer ceramic is made according to 3 mode of embodiment, unlike use partial size for 2.0 μm of polystyrene microsphere conduct Template.Then heat treatment is impregnated according to 2 mode of embodiment, the difference is that second-order heat treatment temperature is 800 DEG C.
It finally obtains modifying Ni0.95Cu0.05-SDC porous metals with Cu0.5Ni0.5 nano dot with 3 mode of embodiment The monocell of ceramic micrometer/nanometer structured anode, wherein the content of nano dot is 10%.
The peak power output of this monocell is 340mW/cm2, and the power attenuation after 120h is 1.0%, skeleton surface Carbon phase is 1.0% to depositional area.
The foregoing examples are merely illustrative of the technical concept and features of the invention, its object is to allow the person skilled in the art to be It cans understand the content of the present invention and implement it accordingly, it is not intended to limit the scope of the present invention.It is all smart according to the present invention The equivalent transformation or modification that refreshing essence is done, should be covered by the protection scope of the present invention.

Claims (8)

1. a kind of preparation method of anti-carbon anode of solid oxide fuel cell comprising following steps: S1. prepare nickel from Amion acetic acid or stearic acid, are then added in nitrate solution, stir by the nitrate solution of son or nickel ion and copper ion Mix and be evenly heated concentration until obtain powder, then calcined under 500 ~ 800 DEG C of high temperature 0.5 ~ 8h obtain gray oxide nickel by powder or Person's brown color Copper-cladding Aluminum Bar nickel oxide powder；S2. cerous nitrate and samaric nitrate or gadolinium oxide being dissolved in deionized water, to be made into nitrate molten Then amion acetic acid or stearic acid are added in nitrate solution by liquid, stir evenly heating concentration until obtaining powder, most 0.5 ~ 8h is calcined under 500 ~ 800 DEG C of high temperature afterwards obtains flaxen samarium doping cerium oxide or gadolinium doped-ceria powder；S3. By powder made from S1 and S2 according to the ratio mixing and ball milling of 5:5 ~ 8:2, mixed powder then is obtained in 50 ~ 80 DEG C of vacuum drying End；S4. by mixed-powder made from S3 and partial size be 0.5 ~ 3.0 μm polystyrene mono-dispersion microballoon according to 7:3 ~ 9:1 ratio Example ultrasonic mixing in alcohol or medium-acetone, is then dried in vacuo；S5. powder S4 obtained is packed into stainless steel mould In, plain piece is suppressed to obtain with the pressure of 100 ~ 500MPa, is then sintered at 1000 ~ 1300 DEG C, in 500 ~ 900 DEG C after furnace cooling Under in hydrogen atmosphere reductase 12 ~ 8h obtain nickel-doped cerium oxide porous metalloceramic anode skeleton of micro-meter scale microstructure Or monel-doped cerium oxide porous metalloceramic anode skeleton；S6. by nickel nitrate, copper nitrate and urea be dissolved in from Obtained solution in sub- water, wherein the molar ratio of ambrose alloy ion is 1:1 ~ 4:1, under vacuum conditions by above-mentioned infusion to putting In the container for the porous metalloceramic anode skeleton for thering is S5 to be prepared, after standing 0.5 ~ 3h, 77 after cermet is taken out ~ It is kept the temperature at 100 DEG C, then in 350 ~ 450 DEG C of 1 ~ 4h of heat treatment, i.e. nickel or monel in skeleton duct in hydrogen atmosphere Particle surface forms equally distributed corronil nano dot, and heat treatment temperature is finally risen to 600 ~ 900 DEG C and keeps the temperature 1 ~ 4h, The Ni-based aurification that is harmonious in corronil nano dot and skeleton, that is, activate, to form the copper-rich nanometer with electro catalytic activity Structure, the above process repeat 2-4 times, finally obtain micrometer/nanometer structured high electrocatalytic active anti-carbon solid oxidation Object anode of fuel cell.
2. preparation method according to claim 1, which is characterized in that in the step S1, the nitrate solution of preparation is 0.1 ~ 2.0M, wherein the molar ratio of copper ion and nickel ion is 0 ~ 1:9.
3. preparation method according to claim 1, which is characterized in that in the step S2, nitrate solution concentration is 0.1 ~ 2.0M, wherein the molar ratio of cerium ion and samarium ion or gadolinium ion is 8:2.
4. preparation method according to claim 1, which is characterized in that in the step S6, by nickel nitrate, copper nitrate and urine Element is dissolved in deionized water, and wherein the solution of 2M ~ 5M is made according to molar ratio 1:5 ~ 1:1.5 for metal ion and urea.
5. the anti-carbon anode of solid oxide fuel cell being prepared such as the method for any one of claim 1-4.
6. anti-carbon anode of solid oxide fuel cell according to claim 5, which is characterized in that the ambrose alloy of anode closes In gold-samarium doping cerium oxide or monel-gadolinium doped-ceria porous metalloceramic anode skeleton, samarium doping cerium oxide or gadolinium Doped cerium oxide granular size is 0.2 ~ 1.0 μm, and monel granular size is 0.2 ~ 1.0 μm and connected holes size is 0.5~2.0μm。
7. anti-carbon anode of solid oxide fuel cell according to claim 5, which is characterized in that the ambrose alloy of anode closes In gold-doped cerium oxide porous metalloceramic anode skeleton, there is equally distributed corronil in monel particle surface Nano dot, the size of nano dot are 5nm ~ 50nm.
8. anti-carbon anode of solid oxide fuel cell according to claim 5, which is characterized in that the ambrose alloy of anode closes In gold-doped cerium oxide porous metalloceramic anode skeleton, corronil nano dot accounts for metal gross weight weight percent in anode It is 2.5 ~ 10%.
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