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 PDF

Info

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
Authority
CN
China
Prior art keywords
anode
ysz
preparation
moo
nio
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201511004157.2A
Other languages
Chinese (zh)
Inventor
武卫明
阎冬
张长松
张允�
张楠
杜慧
侯绍刚
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Anyang Institute of Technology
Original Assignee
Anyang Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Anyang Institute of Technology filed Critical Anyang Institute of Technology
Priority to CN201511004157.2A priority Critical patent/CN105552384A/en
Publication of CN105552384A publication Critical patent/CN105552384A/en
Pending legal-status Critical Current

Links

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

Landscapes

  • 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

A kind of high activity sulfur poisoning-resistant anode and preparation method
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.
CN201511004157.2A 2015-12-29 2015-12-29 High-activity anode with resistance to sulfur poisoning and preparation method thereof Pending CN105552384A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201511004157.2A CN105552384A (en) 2015-12-29 2015-12-29 High-activity anode with resistance to sulfur poisoning and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201511004157.2A CN105552384A (en) 2015-12-29 2015-12-29 High-activity anode with resistance to sulfur poisoning and preparation method thereof

Publications (1)

Publication Number Publication Date
CN105552384A true CN105552384A (en) 2016-05-04

Family

ID=55831445

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201511004157.2A Pending CN105552384A (en) 2015-12-29 2015-12-29 High-activity anode with resistance to sulfur poisoning and preparation method thereof

Country Status (1)

Country Link
CN (1) CN105552384A (en)

Citations (1)

* Cited by examiner, † Cited by third party
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

Patent Citations (1)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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》 *

Similar Documents

Publication Publication Date Title
Fan et al. Potential low-temperature application and hybrid-ionic conducting property of ceria-carbonate composite electrolytes for solid oxide fuel cells
Huang et al. Development of solid oxide fuel cell materials for intermediate-to-low temperature operation
Xiao et al. Characterization of symmetrical SrFe0. 75Mo0. 25O3− δ electrodes in direct carbon solid oxide fuel cells
CN105940540B (en) Electrochemical energy conversion device, battery, and positive electrode material for same
Yoo et al. LST–GDC composite anode on LaGaO3-based solid oxide fuel cell
Sumi et al. Impact of direct butane microtubular solid oxide fuel cells
Myung et al. Synthesis and characterization of NiO/GDC–GDC dual nano-composite powders for high-performance methane fueled solid oxide fuel cells
KR101934006B1 (en) Solid oxide fuel cell and solid oxide electrolysis cell including Ni-YSZ fuel(hydrogen) electrode, and fabrication method thereof
Yang et al. (La0. 8Sr0. 2) 0.98 MnO3-δ-Zr0. 92Y0. 16O2-δ: PrOx for oxygen electrode supported solid oxide cells
CN105226294A (en) A kind of cathode material for solid-oxide fuel cell and Synthesis and applications thereof
Guo et al. Electrochemical contribution of silver current collector to oxygen reduction reaction over Ba0. 5Sr0. 5Co0. 8Fe0. 2O3− δ electrode on oxygen-ionic conducting electrolyte
CN105839138A (en) Preparing method for high-temperature melting carbonate air electrode of solid oxide electrolytic cell
Li et al. Electrochemical characterization of gradient Sm0. 5Sr0. 5CoO3− δ cathodes on Ce0. 8Sm0. 2O1. 9 electrolytes for solid oxide fuel cells
CN108091885B (en) High-temperature fuel cell cathode and application thereof
Fu et al. Characterization of nanosized Ce0. 8Sm0. 2O1. 9-infiltrated Sm0. 5Sr0. 5Co0. 8Cu0. 2O3− δ cathodes for solid oxide fuel cells
CN106876726A (en) A kind of preparation method of SOFC high-activity cathode steady in a long-term
Xi et al. Enhanced reaction kinetics of BCFZY-GDC-PrOx composite cathode for low-temperature solid oxide fuel cells
Wang et al. Effects of Ni-NCAL and Ni–Ag electrodes on the cell performances of low-temperature solid oxide fuel cells with Sm0. 2Ce0· 8O2-δ electrolyte at various temperatures
Zhang et al. Modification of electrocatalytic activity of BaCe0. 40Sm0. 20Fe0. 40O3− δ with Co3O4 as cathode for proton-conducting solid oxide fuel cell
CN104617308A (en) Anode of medium-low temperature solid oxide fuel cell and preparation method thereof
CN111653790B (en) All-solid-state iron-air battery
Fu Sm0. 5Sr0. 5Co0. 4Ni0. 6O3− δ–Sm0. 2Ce0. 8O1. 9 as a potential cathode for intermediate-temperature solid oxide fuel cells
Ding et al. Development of tubular anode-supported solid oxide fuel cell cell and 4-cell-stack based on lanthanum gallate electrolyte membrane for mobile application
Jin et al. Electrochemical characteristics of an La0. 6Sr0. 4Co0. 2Fe0. 8O3–La0. 8Sr0. 2MnO3 multi-layer composite cathode for intermediate-temperature solid oxide fuel cells
Wang et al. Performance of a novel La (Sr) MnO3-Pd composite current collector for solid oxide fuel cell cathode

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20160504