CN105552384A - High-activity anode with resistance to sulfur poisoning and preparation method thereof - Google Patents
High-activity anode with resistance to sulfur poisoning and preparation method thereof Download PDFInfo
- Publication number
- CN105552384A CN105552384A CN201511004157.2A CN201511004157A CN105552384A CN 105552384 A CN105552384 A CN 105552384A CN 201511004157 A CN201511004157 A CN 201511004157A CN 105552384 A CN105552384 A CN 105552384A
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- anode
- ysz
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- nio
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Classifications
-
- 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
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
-
- 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
-
- 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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
-
- 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 & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Composite Materials (AREA)
- Inert Electrodes (AREA)
Abstract
The invention discloses a high-activity anode with resistance to sulfur poisoning and a preparation method thereof. The anode is composited of NiO, MoO3, CeO2 and an yttria-doped yttria material. The anode has the advantages that the poisoning effect of sulfocompounds on the anode can be reduced effectively, the polarization resistance of the anode is lowered, and the medium and low-temperature performance of a battery and the long-term stability of the battery can be improved effectively.
Description
Technical field
The present invention relates to field of solid oxide fuel, is a kind of preparation and application thereof of the high activity sulfur poisoning-resistant anode material for intermediate temperature solid oxide fuel cell specifically.
Background technology
Solid Oxide Fuel Cell is a kind of energy conversion device efficiently, can convert the chemical energy in fuel gas to electric energy, adopt structure of whole solid state, low emission low noise, can be applicable to dispersion power station and concentrated power station.
For traditional Ni-based anode, when Solid Oxide Fuel Cell with natural gas or hydrocarbon compound for fuel time, the trace sulfide in fuel can produce very serious poisoning effect to Ni-based anode, causes the catalytic activity of anode to fuel sharply to reduce.Therefore, be necessary the anode developing highly active sulfur poisoning-resistant, to improve with the catalytic activity of natural gas or the hydrocarbon compound anode of solid oxide fuel cell that is fuel and anti-sulfur poisonous performance, improve the long-time stability of battery.
Oxide containing cerium, molybdenum and tungsten effectively can weaken the poisoning effect of sulfur-containing compound antianode, improves catalytic activity and the anti-sulfur poisonous performance of anode, thus improves performance and the long-time stability of Solid Oxide Fuel Cell.
Summary of the invention
In order to the anti-sulfur poisonous performance of the catalytic activity and anode that improve anode of solid oxide fuel cell, improve the performance of Solid Oxide Fuel Cell, the object of the present invention is to provide a kind of high activity composite anode containing molybdenum, tungsten oxide, effectively can improve the sulfur poisoning resistance of anode, reduce the anode polarization resistance of battery, improve battery performance steady in a long-term.
This anode be used for in natural gas or the hydrocarbon compound Solid Oxide Fuel Cell that is fuel time, effectively can reduce the impact of sulfur-containing compound on battery performance.
For achieving the above object, technical scheme of the present invention is:
1. by mixing a certain proportion of NiO, YSZ, CeO
2, WO
3and MoO
3powder, adds
Appropriate organic bond, at 1100-1500
osinter at the temperature of C on zirconia (YSZ) electrolyte of Yttrium oxide doping, or with YSZ electrolyte co-sintering, be then prepared from by the method for hydrogen reducing.Wherein, the zirconia (YSZ) of Yttrium oxide doping is Zr
xy
1-xo
2-d, 0.7≤x≤0.95; 0≤d≤0.15.
Described anode gross thickness is between 20 nanometer-2 millimeters; The method preparation that anode adopts high temperature sintering then to reduce in hydrogen.
Excellent results of the present invention is:
By adopting the anode containing cerium, molybdenum and tungsten oxide material, effectively can reduce the poisoning effect of the sulfide antianode in fuel, improve the performance of the sulfur poisoning-resistant of battery, to fuel, there is higher catalytic activity, significantly improve the long-time stability of battery and the tolerance performance to sulfide.
1. adopt Solid Oxide Fuel Cell prepared by the present invention, with NiO, YSZ, CeO
2, WO
3
With MoO
3composite material, as anode material, effectively improves the catalytic activity of anode to fuel, and effectively raises the ability of the sulfur poisoning-resistant of anode.
2. the present invention can be used for the Solid Oxide Fuel Cell of the multiple configurations such as plate, cast.
3. the present invention can be applied to the Solid Oxide Fuel Cell of anode-supported, cathode support or electrolyte-supported.
4. the present invention is applicable to multiple intermediate temperature solid oxide fuel cell application, as dispersion power station, compact power, vehicle-mounted accessory power supply.
Embodiment
Embodiment 1
Ni-W-Mo-YSZ-CeO
2the preparation of composite anode.
By NiO:YSZ:CeO
2: WO
3: MoO
3=45:50:1:2:2 (counting in mass ratio) mechanical mixture, mixes rear interpolation binding agent, is then coated to the La of cathode support
0.1sr
0.9mnO
2+d(LSM) on-YSZ/YSZ battery component, at 1100 DEG C of roasting 2h, obtaining anode thickness is 30 μm.By 800
oc hydrogen reducing anode.
Anode-side ventilating methane, cathode side leads to oxygen, tests the battery performance of 800-650 DEG C.800 DEG C time, maximum power is 0.67W.cm
-2, 650 DEG C time, maximum power is 0.11W.cm
-2, battery operation 240h power is not significantly decayed.The H that volume content is 0.015% is added in the methane gas of anode-side
2after S, battery performance has no obvious decay, and after running 24h, battery performance kept stable.
Embodiment 2
Ni-W-Mo-YSZ-CeO
2the preparation of composite anode.
By NiO:YSZ:CeO
2: WO
3: MoO
3=48:45:1:3:3 (in mass ratio count) mechanical mixture, mixes rear interpolation binding agent, roller-compaction, by 1350
othe method of C co-sintering prepares the NiO-YSZ-CeO of anode-supported
2-WO
3-MoO
3/ YSZ battery component, the thickness of YSZ dielectric film is 20 μm.Then on the battery component of anode-supported, La is applied
0.1sr
0.9mnO
2+d(LSM)-YSZ composite cathode, at 1060 DEG C of roasting 2h, obtaining cathode thickness is about 40 μm.800
oc hydrogen reducing anode.
Anode-side ventilating methane gas, cathode side leads to oxygen, tests the battery performance of 600 DEG C.600 DEG C time, maximum power is 0.29W.cm
-2, battery is 600
oc has no obvious decay after running 200 hours.The H that volume content is 0.01% is added in the methane gas of anode-side
2after S, battery performance has no obvious decay, and after running 48h, battery performance kept stable.
Claims (9)
1. a high activity sulfur poisoning-resistant anode, is characterized in that: anode material is by zirconia (YSZ), the CeO of NiO, Yttrium oxide doping
2with MoO
3, WO
3in one or both be composited.
2. anode according to claim 1, is characterized in that: Yttrium oxide doping
Zirconia (YSZ) is Zr
xy
1-xo
2-d, 0.7≤x≤0.95; 0≤d≤0.15.
3. anode according to claim 1, is characterized in that: the mass content of NiO between 30-70%, the content of the quality sum of YSZ between 25-65%, CeO
2mass content between 0.01-3%.
4. anode according to claim 1, is characterized in that: containing MoO in anode
3, WO
3in one or both, and MoO
3with WO
3mass content all between 0.1-5%.
5. anode according to claim 1, is characterized in that: described anode gross thickness is between 20 nanometer-2 millimeters.
6. the preparation method of a kind of high activity sulfur poisoning-resistant anode according to claim 1, is characterized in that: composite anode adopts high temperature sintering, then passes through H
2the method preparation of at high temperature reducing.
7. preparation method according to claim 6, is characterized in that: NiO, CeO
2, the first fully mixing of YSZ powder, then with MoO
3and/or WO
3abundant mixing, at 1100-1500
ounder the high temperature of C after sinter molding, at 600-800
oh is passed through at the temperature of C
2the method preparation of reduction.
8. anode according to claim 1, is characterized in that: the particle diameter of described oxide powder is all at below 500nm.
9. the application of anode according to claim 1, is characterized in that: described anode uses as electrode on YSZ electrolyte.
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Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104617308A (en) * | 2015-02-02 | 2015-05-13 | 安阳工学院 | Anode of medium-low temperature solid oxide fuel cell and preparation method thereof |
-
2015
- 2015-12-29 CN CN201511004157.2A patent/CN105552384A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104617308A (en) * | 2015-02-02 | 2015-05-13 | 安阳工学院 | Anode of medium-low temperature solid oxide fuel cell and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
BYEONG WAN KWON等: "Nickel-based anode with microstructured molybdenum dioxide internal reformer for liquid hydrocarbon-fueled solid oxide fuel cells", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
MARTA MARIA NATILE等: "WO3/CeO2/YSZ nanocomposite as a potential catalyst for methanol reforming", 《JOURNAL OF POWER SOURCES》 * |
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Application publication date: 20160504 |