CN110061248A - Anti-carbon sulfur resistive poisons anode of solid oxide fuel cell and preparation method thereof - Google Patents
Anti-carbon sulfur resistive poisons anode of solid oxide fuel cell and preparation method thereof Download PDFInfo
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- CN110061248A CN110061248A CN201910368882.XA CN201910368882A CN110061248A CN 110061248 A CN110061248 A CN 110061248A CN 201910368882 A CN201910368882 A CN 201910368882A CN 110061248 A CN110061248 A CN 110061248A
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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
- H01M4/88—Processes of manufacture
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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
- H01M4/88—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
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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
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
- H01M4/8885—Sintering or firing
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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
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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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
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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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
- 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
Abstract
The invention discloses a kind of anti-carbon sulfur resistive to poison anode of solid oxide fuel cell and preparation method thereof, copper samarium codope cerium oxide or copper gadolinium codope ceria oxide powder are prepared by copper ion and samarium or gadolinium doped-ceria base oxide, porous ceramics is made by Precursor Powder of doped ceria powder, after hydrogen reducing, part copper is oozed out from lattice to be obtained anti-carbon sulfur resistive and poisons anode of solid oxide fuel cell porous ceramics.The present invention improves the electric conductivity of anode and increases the three-phase reaction interface of anode, has satisfactory texture stability, will not reunite, the performance poisoned with excellent anti-carbon sulfur resistive.Copper is introduced into anode by preparation method of the invention by ion doping and precipitation effect, the solid oxide fuel of anode-supported can be directly prepared using traditional compacting or curtain coating, the method for sintering, the complicated processes containing copper anode for avoiding immersion reduction method preparation, achieve industrialization and are possibly realized.
Description
Technical field
The present invention relates to a kind of anode of fuel cell and preparation method thereof, poison more particularly to a kind of anti-carbon sulfur resistive solid
Oxide body anode of fuel cell and preparation method thereof.
Background technique
Fuel cell technology can make the chemical energy of fuel be converted into electric energy, Neng Gou great by electrochemical reaction process
It is big to reduce pollution, and due to not limited by Carnot cycle, capacity usage ratio is up to 40%~60%, if passing through thermoelectricity
Symbiosis utilizes its thermal energy simultaneously, then the conversion ratio of energy can be up to 80% or more.These advantages make fuel cell technology pole
It is possible that becoming important power supply means in the near future.It is by the final product of the fuel cell of optimum fuel of hydrogen
Water, to environment almost without pollution.However, the acquisition, storage and transport of high-purity hydrogen all need to be solved there is many at present
Problem certainly, thus it is with high costs as the fuel cell of fuel using pure hydrogen, it is difficult large-scale promotion application at present.
Directly using hydrocarbon gas as fuel intermediate temperature solid oxide fuel cell (Solid Oxide Fuel Cell,
SOFC), hydrocarbon gas on the one hand can be made in anode direct oxidation, does not need any reforming process, so as to make full use of
The utilization rate of fuel is greatly improved in thermodynamic efficiency；The storage and transportation problem of hydrogen are also avoided simultaneously；It is low in another aspect
Warm SOFC can reduce battery caused by the sintering degeneration of reaction and electrode in battery between various interfaces at high temperature etc.
The problem of efficiency and stability reduce, meanwhile, also expand battery critical material-electrode, bipolar plates and electrolyte selection model
It encloses.Numerous advantages directly to become current energy field research by the middle low temperature SOFC of fuel cell of hydrocarbon gas
Hot spot.
When directly using hydrocarbon gas or natural gas as fuel, the reactivity of Ni base anode can be because of the production of Carbon deposition
It gives birth to and reduces rapidly.Especially when containing H in fuel2When S, the decaying of battery is more serious.Therefore, for these gases
For the SOFC of fuel, ability that anode must have very strong anti-carbon deposition sulfur resistive to poison.Generally frequently with it is some its
Its metal and oxide replace Ni catalyst.Studies have found that although Co and Fe has preferable catalytic activity, it is same
Carbon deposition is not can avoid and the problems such as sulphur poisons；The performance of the noble metals such as Pt, Ru is fine, but expensive, and cost is excessively high.It is some
Research emphasis is gradually transferred to oxide (the mixed ionic and electronic with ion and electronics mixing conductance
Conductor, MIEC) catalyst as anode, such as doped cerium oxide, merely using oxide as anode, although it
Have excellent electro-chemical activity and anti-carbon deposition sulfur resistive it is poisoning, since its electronic conductivity is lower, be difficult to obtain
Obtain preferable electrical property.Cu is introduced in the preparation of anode due to good conductivity and anti-carbon deposition.But Cu pairs
The catalytic activity ratio Ni of oxidized is poor, and CuOxWith lower molten point (1326 DEG C), it is difficult to be blended with using oxide
It is sintered the method restored and Cu base anode is made.Although there is preferable anti-carbon sulfur resistive to poison work for copper-based anode, cerium base anode
With, but electro catalytic activity is lower or conductivity is lower, research discovery later is drawn Cu and doped cerium oxide by infusion process
Enter into anode the electro catalytic activity that can be obviously improved electrode and anti-carbon deposition sulfur resistive poisons performance, but infusion process is relatively complicated
And repeatability is bad, is unfavorable for being mass produced.
Summary of the invention
The object of the present invention is to provide the preparation method that a kind of anti-carbon sulfur resistive poisons anode of solid oxide fuel cell,
The complicated processes for avoiding the anode containing Cu of immersion reduction method preparation, achieve industrialized production and are possibly realized.Of the invention
Another purpose is to provide a kind of anti-carbon sulfur resistive and poisons anode of solid oxide fuel cell, anti-with excellent anti-carbon
The performance that sulphur poisons.
The technical scheme is that such: a kind of anti-carbon sulfur resistive poisons the system of anode of solid oxide fuel cell
Preparation Method, comprising the following steps:
S1, it cerous nitrate, samaric nitrate or gadolinium nitrate, copper nitrate is dissolved in deionized water is made into nitrate solution, then by ammonia
Guanidine-acetic acid or stearic acid are added in nitrate solution, are stirred evenly and are heated concentration until spontaneous combustion obtains sundown powder
End, finally heat treatment obtains copper samarium codope cerium oxide or copper gadolinium codope ceria oxide powder at 500~800 DEG C；
S2, by powder made from S1 using alcohol or acetone as medium ball milling, then in 50~80 DEG C be dried in vacuo；
S3, by dried powder made from S2 and pore creating material according to the ratio ultrasonic mixing in a dispersion medium of 8:2~9:1,
Then it is dried in vacuo in 50~80 DEG C；
S4, it takes dried powder made from appropriate S3 to be fitted into mold, biscuit piece is suppressed to obtain with the pressure of 100~300MPa,
Then reduction treatment is resisted in hydrogen atmosphere at 550~750 DEG C after sintering and furnace cooling at 1000~1200 DEG C
Carbon distribution sulfur resistive poisons anode of solid oxide fuel cell.
Preferably, the nitrate solution concentration is 0.5~2.0M, wherein mole of cerium ion and samarium ion or gadolinium ion
Than for 4:1.
Preferably, the molar ratio of the amion acetic acid or stearic acid and the nitrate anion in the nitrate solution be 1:2~
2:1。
Preferably, heat treatment time is 2~8h at 500~800 DEG C in the step S1；Ball-milling Time in the step S2
For 24~96h, vacuum drying time is 6~48h；Vacuum drying time is 6~48h in the step S3.
Preferably, 2~6h of sintering time in the step S4, the reduction treatment time in hydrogen atmosphere are 2~8h.
Preferably, the pore creating material can be using the pore creating material insoluble in decentralized medium, such as the polystyrene of submicron order
Mono-dispersion microballoon etc. can also be ethyl alcohol using the pore creating material for dissolving in decentralized medium, such as ethyl cellulose, the dispersing agent
Or acetone.
Another technical solution of the invention are as follows: a kind of anti-carbon sulfur resistive poisons anode of solid oxide fuel cell, by upper
Preparation method is stated to be made.
Further, it includes copper samarium or copper gadolinium codope that the anti-carbon sulfur resistive, which poisons anode of solid oxide fuel cell,
The porous ceramics anode skeleton and oozed out from precipitation in lattice and be anchored at copper on the porous ceramic skeleton that cerium oxide is constituted
The partial size of particle, the copper particle is in nanometer or micro-meter scale.
Further, copper, which is distributed in, in the porous ceramics anode skeleton that the copper samarium or copper gadolinium codope cerium oxide are constituted mixes
On the surface of miscellaneous cerium oxide crystalline or crystal boundary.
Further, the anti-carbon sulfur resistive poisons copper in anode of solid oxide fuel cell and accounts for all metallic elements
Molar content is 5~10%, samarium or gadolinium in the porous ceramics anode skeleton that the copper samarium or copper gadolinium codope cerium oxide are constituted
Doping is a quarter of the amount of the substance of cerium.
The beneficial effect of technical solution provided by the present invention is that the cylinder of nanometer or micro-meter scale is particle anchored in porous pottery
On porcelain body frame, the three-phase reaction interface of anode can also be increased while the electric conductivity for improving anode, and long-term
Operational process has satisfactory texture stability, is not susceptible to reunite.It is excellent that the characteristic of copper and cerium oxide determines that the anode has
The ability that poisons of anti-carbon sulfur resistive make anode to the tool of hydrocarbon gas while using the synergistic effect between copper and cerium oxide
There is higher electro catalytic activity, makes it more suitable for the direct application of hydrocarbon fuel or natural gas.Anti-carbon sulfur resistive of the invention
Poison anode of solid oxide fuel cell preparation method, Cu is introduced into anode using ion doping and precipitation effect, it can
It is low compared with infusion process time saving and energy saving to directly adopt the preparation method for the Ni base anode having been commercialized, it is fully available for industrializing.
Detailed description of the invention
Fig. 1 is Porous Cu samarium codope ceria oxide ceramics profile scanning electron microscope.
Fig. 2 is that anti-carbon sulfur resistive poisons anode of solid oxide fuel cell profile scanning electron microscope.
Fig. 3 is to poison monocell made from anode of solid oxide fuel cell with anti-carbon sulfur resistive of the present invention in constant temperature perseverance
Under voltage conditions, H is added with methane (solid section) or methane2Output characteristics figure when S (hollow parts) is fuel.
Specific embodiment
Below with reference to embodiment, the invention will be further described, but not as a limitation of the invention.
Embodiment 1
Cerous nitrate, samaric nitrate and copper nitrate are dissolved in the nitrate solution that deionized water is made into 1.0M, wherein cerium ion with
The molar ratio of samarium ion is 4:1, and the molar content that copper ion accounts for all metal ions is 10%, is then added to amion acetic acid
In nitrate solution, wherein the molar ratio of amion acetic acid and the nitrate anion in solution is 1:2.At room temperature after mixing evenly in electric furnace
Upper heating, concentration is until spontaneous combustion obtains light brown powder.Then it is heat-treated 4h at 700 DEG C and obtains fallow CSCO
(copper samarium codope cerium oxide) powder, the powder profile scanning electron microscope are shown in Fig. 1.
By CSCO powder ball milling 72h obtained, ball-milling medium is alcohol, then for 24 hours in 60 DEG C of vacuum drying.After ball milling
The polystyrene mono-dispersion microballoon that powder and partial size are 0.3 μm ultrasonic mixing in alcoholic media according to the ratio of mass ratio 8:2
3h, then for 24 hours in 60 DEG C of vacuum drying.
0.45g is taken to be fitted into the stainless steel mould that diameter is 15mm in the powder that vacuum drying obtains, in the pressure of 100MPa
Power pushes sheetmolding, opens the side of mold, then uniformly adds the fluffy powder of 0.05g SDC in open anode substrate side
It is suppressed under the pressure of 200MPa at end, it is ensured that SDC powder and anode substrate are completely combined, by the biscuit piece pressed at 1100 DEG C
The double-layer ceramic of the two-in-one anode-supported of anode-electrolyte is made in lower sintering 4h.Then in double-layer ceramic electrolyte side
The cobalt acid samarium and Sm doped CeO_2 (SSC/SDC) composite cathode of strontium doping are prepared by the method that spin coating is sintered.Finally will
The anode-side of monocell at 700 DEG C in hydrogen atmosphere reductase 12 h to obtaining that there is Cu-SDC porous metalloceramic anode
Monocell, wherein the molar content of copper is 10%, and wherein Cu-SDC porous metalloceramic anode is that anti-carbon sulfur resistive poisons admittedly
Oxide body anode of fuel cell, profile scanning electron microscope are as shown in Figure 2.
As shown in figure 3, operating voltage is in 0.5V at a temperature of 600 DEG C, the output power of this monocell using methane as fuel
For 298mW/cm2, monocell passes through 72h continuous service, and output power is basically unchanged.And it is infused between 30~40h of operation
Enter the H of 50ppm2S, the output characteristics of battery do not occur significantly to change.
Embodiment 2
Cerous nitrate, gadolinium nitrate and copper nitrate are dissolved in the nitrate solution that deionized water is made into 1.0M, wherein cerium ion with
The molar ratio of gadolinium ion is 4:1, and the molar content that copper ion accounts for all metal ions is 10%, is then added to amion acetic acid
In nitrate solution, wherein the molar ratio of amion acetic acid and the nitrate anion in solution is 1:2.At room temperature after mixing evenly in electric furnace
Upper heating, concentration is until spontaneous combustion obtains light brown powder.Then it is heat-treated 5h at 800 DEG C and obtains fallow CGCO
(copper gadolinium codope cerium oxide) powder.
By CGCO powder ball milling 72h obtained, ball-milling medium is alcohol, then in 50 DEG C of vacuum drying 48h.Vacuum is done
After dry powder and ethyl cellulose according to the ratio of mass ratio 9:1 the ultrasonic mixing 6h in alcoholic media, then in 50 DEG C of vacuum
Dry 48h.By obtained powder take 0.6g be fitted into diameter be 20mm stainless steel mould in, 200MPa pressure lower sheeting at
The biscuit piece pressed is sintered the supporting anodes of 4h by type at 1100 DEG C.Then it is made again using silk screen print method containing electrolysis
The monocell of matter layer and cathode layer.Finally by the anode-side of monocell at 750 DEG C in hydrogen atmosphere reductase 12 .5h to
To the monocell with Cu-GDC porous metalloceramic anode, Cu-GDC porous metalloceramic anode is that anti-carbon sulfur resistive poisons
Anode of solid oxide fuel cell.
According to 1 mode of embodiment, this monocell adds H under the conditions of constant temperature constant voltage, with methane or methane2When S is fuel
Output power be basically unchanged.
Embodiment 3
Cerous nitrate, samaric nitrate and copper nitrate are dissolved in the nitrate solution that deionized water is made into 0.5M, wherein cerium ion with
The molar ratio of samarium ion is 4:1, and the molar content that copper ion accounts for all metal ions is 5%, and stearic acid is then added to nitre
In acid salt solution, wherein the molar ratio of stearic acid and the nitrate anion in solution is 2:1.Add on electric furnace after mixing evenly at room temperature
Heat, concentration is until spontaneous combustion obtains light brown powder.Then it is heat-treated 8h at 500 DEG C and obtains fallow CSCO powder.
By CSCO powder ball milling 96h obtained, ball-milling medium is acetone, then in 70 DEG C of vacuum drying 12h.After ball milling
The polystyrene mono-dispersion microballoon that powder and partial size are 0.3 μm ultrasonic mixing in medium-acetone according to the ratio of mass ratio 6:1
1h, then for 24 hours in 70 DEG C of vacuum drying.0.45g is taken to be packed into the stainless steel mold that diameter is 15mm in the powder that vacuum drying obtains
In tool, sheetmolding is pushed in the pressure of 300MPa, the side of mold is opened, is then uniformly added in open anode substrate side
0.05g SDC fluffy powder, is suppressed under the pressure of 300MPa, it is ensured that SDC powder and anode substrate are completely combined, by what is pressed
Biscuit piece is sintered the double-layer ceramic that the two-in-one anode-supported of anode-electrolyte is made in 2h at 1200 DEG C.Then in bilayer
Ceramic electrolyte side prepares the cobalt acid samarium of strontium doping by the method that spin coating is sintered and Sm doped CeO_2 (SSC/SDC) is answered
Close cathode.It is porous with Cu-SDC to obtain that the anode-side of monocell is finally restored to 6h at 600 DEG C in hydrogen atmosphere
The monocell of cermet anode.
According to 1 mode of embodiment, this monocell adds H under the conditions of constant temperature constant voltage, with imitative natural gas or imitative natural gas2S
Output power when for fuel is basically unchanged.
Embodiment 4
Cerous nitrate, gadolinium nitrate and copper nitrate are dissolved in the nitrate solution that deionized water is made into 2.0M, wherein cerium ion with
The molar ratio of samarium ion is 4:1, and the molar content that copper ion accounts for all metal ions is 7.5%, is then added to stearic acid
In nitrate solution, wherein the molar ratio of stearic acid and the nitrate anion in solution is 1:2.At room temperature after mixing evenly on electric furnace
Heating, concentration is until spontaneous combustion obtains light brown powder.Then it is heat-treated 2h at 800 DEG C and obtains fallow CGCO powder
End.
For 24 hours by CGCO powder ball milling obtained, ball-milling medium is acetone, then in 80 DEG C of vacuum drying 6h.Vacuum is done
After dry powder and ethyl cellulose according to the ratio of mass ratio 6:1 the ultrasonic mixing 3h in medium-acetone, then in 80 DEG C of vacuum
Dry 6h.By obtained powder take 0.6g be fitted into diameter be 20mm stainless steel mould in, 200MPa pressure lower sheeting at
The biscuit piece pressed is sintered the supporting anodes of 8h by type at 1000 DEG C.Then it is made again using silk screen print method containing electrolysis
The monocell of matter layer and cathode layer.The anode-side of monocell is finally restored to 8h at 550 DEG C in hydrogen atmosphere to obtain
Monocell with Cu-GDC porous metalloceramic anode.
According to 1 mode of embodiment, this monocell adds H under the conditions of constant temperature constant voltage, with imitative natural gas or imitative natural gas2S
Output power when for fuel is basically unchanged.
Claims (10)
1. the preparation method that a kind of anti-carbon sulfur resistive poisons anode of solid oxide fuel cell, which is characterized in that including following
Step:
S1, it cerous nitrate, samaric nitrate or gadolinium nitrate, copper nitrate is dissolved in deionized water is made into nitrate solution, then by amino second
Acid or stearic acid are added in nitrate solution, are stirred evenly and are heated concentration until spontaneous combustion obtains light brown powder, most
Heat treatment obtains copper samarium codope cerium oxide or copper gadolinium codope ceria oxide powder at 500~800 DEG C afterwards；
S2, by powder made from S1 using alcohol or acetone as medium ball milling, then in 50~80 DEG C be dried in vacuo；
S3, by dried powder made from S2 and pore creating material according to the ratio ultrasonic mixing in a dispersion medium of 8:2~9:1, then
It is dried in vacuo in 50~80 DEG C；
S4, it takes dried powder made from appropriate S3 to be fitted into mold, biscuit piece is suppressed to obtain with the pressure of 100~300MPa, then
Reduction treatment obtains anti-carbon in hydrogen atmosphere at 550~750 DEG C after sintering and furnace cooling at 1000~1200 DEG C
Sulfur resistive poisons anode of solid oxide fuel cell.
2. anti-carbon sulfur resistive according to claim 1 poisons the preparation method of anode of solid oxide fuel cell, special
Sign is that the nitrate solution concentration is 0.5~2.0M, and wherein the molar ratio of cerium ion and samarium ion or gadolinium ion is 4:1.
3. anti-carbon sulfur resistive according to claim 1 poisons the preparation method of anode of solid oxide fuel cell, special
Sign is that the molar ratio of the amion acetic acid or the nitrate anion in stearic acid and the nitrate solution is 1:2~2:1.
4. anti-carbon sulfur resistive according to claim 1 poisons the preparation method of anode of solid oxide fuel cell, special
Sign is that heat treatment time is 2~8h at 500~800 DEG C in the step S1；In the step S2 Ball-milling Time be 24~
96h, vacuum drying time are 6~48h；Vacuum drying time is 6~48h in the step S3.
5. anti-carbon sulfur resistive according to claim 1 poisons the preparation method of anode of solid oxide fuel cell, special
Sign is that 2~6h of sintering time in the step S4, the reduction treatment time in hydrogen atmosphere is 2~8h.
6. anti-carbon sulfur resistive according to claim 1 poisons the preparation method of anode of solid oxide fuel cell, special
Sign is that the dispersing agent is ethyl alcohol or acetone.
7. anti-carbon sulfur resistive made from a kind of preparation method to any one of 6 according to claim 1 poisons soild oxide
Anode of fuel cell.
8. anti-carbon sulfur resistive according to claim 7 poisons anode of solid oxide fuel cell, which is characterized in that described
It includes the porous ceramics that copper samarium or copper gadolinium codope cerium oxide are constituted that anti-carbon sulfur resistive, which poisons anode of solid oxide fuel cell,
Anode skeleton and copper particle on the porous ceramic skeleton, the partial size of the copper particle are oozed out and are anchored at from precipitation in lattice
In nanometer or micro-meter scale.
9. anti-carbon sulfur resistive according to claim 7 poisons anode of solid oxide fuel cell, which is characterized in that described
In the porous ceramics anode skeleton that copper samarium or copper gadolinium codope cerium oxide are constituted copper be distributed in doped cerium oxide crystal surface or
On crystal boundary.
10. anti-carbon sulfur resistive according to claim 7 poisons anode of solid oxide fuel cell, which is characterized in that institute
State anti-carbon sulfur resistive poison copper in anode of solid oxide fuel cell account for all metallic elements molar content be 5~10%,
The doping of samarium or gadolinium is the substance of cerium in the porous ceramics anode skeleton that the copper samarium or copper gadolinium codope cerium oxide are constituted
The a quarter of amount.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101599546A (en) * | 2008-06-06 | 2009-12-09 | 中国科学院大连化学物理研究所 | A kind of cathode material for solid-oxide fuel cell and application |
| US20140287348A1 (en) * | 2011-07-20 | 2014-09-25 | Korea Institute Of Industrial Technology | Method for manufacturing a unit cell of a solid oxide fuel cell |
| CN106450352A (en) * | 2016-12-08 | 2017-02-22 | 常熟理工学院 | Carbon deposition-resistant solid oxide fuel cell anode and preparation method thereof |
-
2019
- 2019-05-05 CN CN201910368882.XA patent/CN110061248A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101599546A (en) * | 2008-06-06 | 2009-12-09 | 中国科学院大连化学物理研究所 | A kind of cathode material for solid-oxide fuel cell and application |
| US20140287348A1 (en) * | 2011-07-20 | 2014-09-25 | Korea Institute Of Industrial Technology | Method for manufacturing a unit cell of a solid oxide fuel cell |
| CN106450352A (en) * | 2016-12-08 | 2017-02-22 | 常熟理工学院 | Carbon deposition-resistant solid oxide fuel cell anode and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| SHOUCHENG HE ET AL.: ""Preparation and characterization of Cu–SDC anodes for low-temperature solid oxide fuel cell"", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| ZHICHENG WANG ET AL.: ""Preparation of Porous NiO-Ce0.8Sm0.2O1.9 Ceramics for Anode-supported Low-temperature Solid Oxide Fuel Cells"", 《JOURNAL OF MATERIAL SCIENCE AND TECHNOLOGY》 * |
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