CN109841846A - A kind of method of modifying of cathode of solid oxide fuel cell - Google Patents

A kind of method of modifying of cathode of solid oxide fuel cell Download PDF

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Publication number
CN109841846A
CN109841846A CN201711221197.1A CN201711221197A CN109841846A CN 109841846 A CN109841846 A CN 109841846A CN 201711221197 A CN201711221197 A CN 201711221197A CN 109841846 A CN109841846 A CN 109841846A
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cathode
based perovskite
powder
phase
value
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程谟杰
尚磊
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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 present invention provides a kind of method of modifying of solid oxide fuel cell Co/Fe based perovskite cathode.This method prepares one layer of porous C o/Fe based perovskite transition zone being made of nano particle using superconducting RF between Co/Fe based perovskite cathode and electrolyte.The use of the transition zone effectively improves the interfacial contact of Co/Fe based perovskite cathode and electrolyte, increases Cathodic oxygen reduction three phase boundary, not only increases battery performance, and improves the long-time stability and reliability of battery.

Description

A kind of method of modifying of cathode of solid oxide fuel cell
Technical field
The present invention relates to cathode of solid oxide fuel cell, specifically a kind of solid oxide fuel cell Co/ The method of modifying of Fe based perovskite cathode
Background technique
Solid oxide fuel cell (SOFCs) is that the chemical energy being stored in fuel and oxidant is directly translated into electricity The energy conversion device of energy, compared with traditional energy output technology, with capacity efficiency height, cleanliness without any pollution has a wide range of application The features such as, it is one of current most promising clean energy technology.SOFC running temperature is reduced to 800 DEG C below based on can make It uses cheap stainless steel as connector, reduces SOFC operating cost；And the reaction between each component of battery can be suppressed, is solved close The problems such as envelope and battery component thermal degradation, therefore become one of the main direction of development of current SOFC.
Co/Fe based perovskite material (such as LaxSr1-xCoyFe1-yO3-δ(LSCF), BaxSr1-xCoyFe1-yO3-δ(BSCF)) Based on good surface exchange characteristic, it is the widest to become current application for higher body phase electronic conductivity and oxygen ionic conductivity Low-temperature cathode material in general SOFC.Co/Fe can effectively be prevented by preparing one layer of cerium base electrolyte interlayer in YSZ bath surface Pyroreaction between based perovskite material and YSZ electrolyte maintains high-performance (the Solid State of middle low temperature SOFC Ionics 179(2008) 919-923).There is document to show the catalysis of cathode oxygen when cell operating temperature is at 650 DEG C or less Active site focuses primarily upon limited cathode/cerium base electrolyte interlayer/O2Three phase boundary (Journal of Power Sources 269(2014)180-188).Traditional slurry coating high temperature sintering prepares cell cathode and easily causes electrode particle Roughening is grown up, and the loss of electrode effecting reaction three phase boundary is serious, causes battery performance lower.Therefore this patent proposition passes through radio frequency Reactive magnetron sputtering prepares one layer of Co/Fe based perovskite phase Porous transition layer, the transition zone on cerium base electrolyte interlayer surface Grain partial size is smaller, and large specific surface area contacts well with cerium base electrolyte barrier interface, hence it is evident that increases active electrode reaction three-phase Interface length, therefore significantly improve cryogenic property in battery.
Summary of the invention
The present invention proposes a kind of method of modifying of solid oxide fuel cell Co/Fe based perovskite cathode, specific implementation Steps are as follows:
1) electrode powder synthesizes: by the metal ion nitric acid salt powder containing Co/Fe based perovskite phase based on required chemistry Amount ratio is added to stirring and dissolving in beaker, and the complexing agent of 0.5~1.5 times of mole of metal ion is added after dissolution, uses ammonium hydroxide Or nitric acid tune pH value of solution, heating stirring solution.Evaporation solvent waits for solution into clear viscous shape, and being transferred to heating in evaporating dish makes it Self-propagating combustion obtains Perovskite Phase powder just powder.First powder is transferred in Muffle furnace, 800~1000 DEG C are fired into phase.
2) it configures cathode slurry: will uniformly add afterwards glue configuration electricity with mortar grinder at the Co/Fe based perovskite phase powder of phase Pool cathode slurry.
3) preparation of Co/Fe based perovskite nano transition layer: in anode/electrolyte/three-in-one base of cerium base electrolyte interlayer On bottom or cerium base electrolyte film substrate, one layer of porous C o/Fe based perovskite nano transition layer is prepared by rf magnetron sputtering, and And made annealing treatment between 400~1000 DEG C, annealing time is 0.5~4h.
4) the sintering preparation of cell cathode: being coated in porous C o/Fe based perovskite nano transition layer surface for cathode slurry, From room temperature to 800~1100 DEG C, and in 800~1100 DEG C of 1~10h of sintering at cell cathode.
The Perovskite Phase general formula of cathode synthesized by this method are as follows: (Ln1-xZx)(M1-yNy)O3-d, wherein A Ln be La, Any one in Sm, Ba, Pr, Z are one or both of doped chemical Sr, Ca in A Ln, wherein x value between 0~ 0.5；B M and N are any one in Co, Fe, and wherein y value is between 0~0.5,0≤d≤0.1764.Selected network Mixture is any one of urea, glycine, ammonium citrate, EDTA+ citric acid.PH value of solution can by be added molar concentration be It is that 14.2M nitric acid is adjusted to pH value (0-1) that 14.8M concentrated ammonia liquor, which is adjusted to pH value (8-9) or molar concentration is added,.
Target used in superconducting RF is Co/Fe based alloy target, and wherein the preparation of alloy target material is by corresponding institute It needs the metal powder of ratio to mix, melt, then suppresses.The porous C o/Fe base calcium titanium of superconducting RF preparation Mine mutual-through type are as follows: (Ln1-xZx)(M1-yNy)O3-d, wherein A Ln are any one in La, Sm, Ba, Pr, and Z is in A Ln One or both of doped chemical Sr, Ca, wherein x value is between 0~0.5；B M and N are any one in Co, Fe Kind, wherein y value is between 0~0.5,0≤d≤0.1764.Sputtering parameter are as follows: target-substrate distance is 5~9cm, and the revolving speed of chip bench is 1 ~20 circles/minute, sputtering pressure are 0.1Pa~1.5Pa, Sputtering power density P=3~15W/cm2, oxygen flow and argon gas stream Amount sputters base reservoir temperature at 250~500 DEG C than being 1/2~1/20；Sputter the porous C o/Fe based perovskite phase thickness control of preparation System is between 10nm~1 μm.
Present invention has an advantage that
The present invention uses superconducting RF, is prepared for one layer of porous C o/Fe base on cerium base electrolyte interlayer surface Nano particle transition zone, the transition zone grain diameter is smaller, large specific surface area, contacts well with cerium base electrolyte barrier interface, Significantly increase active electrode reaction three phase boundary length.Compared with the battery of not transition zone, not only increase low in battery Warm nature energy, and the long-term running stability of battery is good.
Specific embodiment
Embodiment 1:
La is synthesized using ammonium citrate method0.6Sr0.4Co0.2Fe0.8O3-δCathode powder, wherein La0.6Sr0.4Co0.2Fe0.8O3-δTake 0.05mol.Weigh 12.9872gLa (NO3)3·6H2O (analysis is pure), 4.2325gSr (NO3)2(analysis is pure), 2.9105gCo (NO3)2·6H2O (analysis is pure), 16.16gFe (NO3)3·9H2O (analysis is pure) is in beaker Stirring dissolves it all after middle addition deionized water.Then according to ammonium citrate: metal ion molar ratio is the ratio of 1.5:1 36.483g ammonium citrate (analysis is pure) is added, so that solution is become clear with the pH=1 that nitric acid (analysis is pure) adjusts solution, so Heating stirring evaporation solvent pours into evaporating dish after solution becomes viscous sol form afterwards, and electricity consumption stove heating fires system self- propagating It burns, the first powder collected 1000 DEG C of roastings in Muffle furnace obtain Perovskite Phase powder.
Embodiment 2:
(NiO-YSZ/YSZ/GDC) sputtering is porous in anode/electrolyte/three-in-one substrate of cerium base electrolyte interlayer La0.6Sr0.4Co0.2Fe0.8O3-δTransition zone, by the three-in-one magnetic control sputtering device that is put into of anode/electrolyte/cerium base electrolyte interlayer In vacuum chamber, adjusting target-substrate distance is about 6cm, and using lanthanum/strontium/cobalt/ferroalloy materials as target, metal molar ratio is 3:2:1: 4.It is evacuated to 5 × 10-4Then Pa heats base station and is warming up to 300 DEG C, being passed through argon flow is 10.0sccm, and oxygen flow is 1.5sccm, sputtering power 5W/cm2, sputtering pressure 1.0Pa, the revolving speed of base station is 10 circles/minute.It is obtained after sputtering 1h Crossing thickness degree is about 60nm, obtains La after 900 DEG C of annealing 2h0.6Sr0.4Co0.2Fe0.8O3-δPerovskite Phase porous layer.
Embodiment 3:
Such as the La prepared in embodiment 10.6Sr0.4Co0.2Fe0.8O3-δPowder, be added 50wt% cathode glue (added glue at It is divided into terpinol (90wt%) solution of ethyl cellulose dissolved (10wt%)) configuration cathode slurry, coating 0.0080g is to strictly according to the facts Porous transition layer surface obtained in example 2 is applied, obtains La after 900 DEG C of roasting 2h0.6Sr0.4Co0.2Fe0.8O3-δCathode.It will full electricity Pond on the cell evaluation device of self assembly at 600 DEG C, 0.5A/cm2Constant-current discharge under current density, discharge voltage can be with Reach 0.9125V.

Claims (9)

1. a kind of method of modifying of cathode of solid oxide fuel cell, which is characterized in that the method specific implementation step is such as Under:
1) the metal ion nitric acid salt powder containing Co/Fe based perovskite phase is added in beaker by required stoichiometric ratio and is stirred Dissolution is mixed, the complexing agent of 0.5~1.5 times of mole of metal ion is added after dissolution, uses ammonium hydroxide or nitric acid tune pH value of solution, heating Stirring evaporation solvent waits for solution into clear viscous shape, and being transferred to heating in evaporating dish makes its self-propagating combustion obtain Perovskite Phase powder The first powder of body, first powder is transferred in Muffle furnace, 800~1000 DEG C are fired into phase, obtain the Perovskite Phase of cathode；
2) in anode/electrolyte/three-in-one substrate of cerium base electrolyte interlayer or cerium base electrolyte film substrate, pass through radio frequency magnetron Sputtering one layer of porous C o/Fe based perovskite nano transition layer, that is, Co/Fe based perovskite phase of preparation；
3) glue is added to configure cell cathode slurry the Co/Fe based perovskite phase powder in step 1) at phase；
4) the configured cathode slurry of step 3) is coated in porous C o/Fe based perovskite nano transition layer surface, is opened from room temperature Beginning, which is warming up at 800~1100 DEG C, is sintered 1~10h into cell cathode.
2. the method as described in claim 1, which is characterized in that in the Perovskite Phase and step 2) of cathode synthesized by step 1) Sputter the Co/Fe based perovskite mutual-through type of preparation are as follows: (Ln1-xZx)(M1-yNy)O3-d, wherein Ln is one in La, Sm, Ba, Pr Kind, Z is one or both of doped chemical Sr, Ca in Ln, and wherein x value is between 0~0.5；M and N is one of Co, Fe It but cannot simultaneously be same element, wherein y value is between 0~0.5,0≤d≤0.1764.
3. the method as described in claim 1, which is characterized in that selected complexing agent be urea, glycine, ammonium citrate or One of EDTA and citric acid mixture.
4. the method as described in claim 1, which is characterized in that pH value of solution can be adjusted to pH value by concentrated ammonia liquor in step 1) Being adjusted to pH value for 8-9 or addition nitric acid is 0-1.
5. the method as described in claim 1, which is characterized in that anode/electrolyte described in step 1) can pass through curtain coating Molding, calendering formation or powder dry pressuring forming process are prepared.
6. the method as described in claim 1, which is characterized in that cerium base electrolyte interlayer described in step 1) can pass through slurry Expect coating, magnetron sputtering, pulse laser deposition or evaporation process preparation.
7. the method as described in claim 1, which is characterized in that the sputtering parameter of superconducting RF described in step 2) Are as follows: target-substrate distance is 5~9cm, and for the revolving speed of chip bench in 1~20 circle/minute, sputtering pressure is 0.1Pa~1.5Pa, sputtering power Density P=3~15W/cm2, oxygen flow and argon flow ratio are 1/2~1/20, sputter base reservoir temperature at 250~500 DEG C；It splashes The porous C o/Fe based perovskite phase thickness for penetrating preparation controls between 10nm~1 μm.
8. the method as described in claim 1, which is characterized in that target used in Radiofrequency muti-hook probe described in step 2) is Co/Fe based alloy target, wherein metal powder mixing, the fusing of the preparation of alloy target material ratio needed for corresponding, are then suppressed It forms.
9. the method as described in claim 1, which is characterized in that the Co/Fe base that in step 2) prepared by superconducting RF Perovskite porous layer needs are made annealing treatment between 400~1000 DEG C, and annealing time is 0.5~4h.
CN201711221197.1A 2017-11-29 2017-11-29 A kind of method of modifying of cathode of solid oxide fuel cell Pending CN109841846A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110635103A (en) * 2019-08-29 2019-12-31 天津工业大学 Flexible nano porous metal oxide cathode for secondary battery and preparation method thereof
CN112663079A (en) * 2020-12-04 2021-04-16 中国科学院大连化学物理研究所 Tubular solid oxide electrolytic cell and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101304093A (en) * 2007-05-11 2008-11-12 中国科学院大连化学物理研究所 Low temperature solid-oxide fuel battery three-in-one component MEA and preparation thereof
CN104600324A (en) * 2015-02-02 2015-05-06 安阳工学院 Perovskite cathode film and preparation method thereof
CN106887631A (en) * 2015-12-12 2017-06-23 中国科学院大连化学物理研究所 A kind of method for improving perovskite oxide cathodic stability

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101304093A (en) * 2007-05-11 2008-11-12 中国科学院大连化学物理研究所 Low temperature solid-oxide fuel battery three-in-one component MEA and preparation thereof
CN104600324A (en) * 2015-02-02 2015-05-06 安阳工学院 Perovskite cathode film and preparation method thereof
CN106887631A (en) * 2015-12-12 2017-06-23 中国科学院大连化学物理研究所 A kind of method for improving perovskite oxide cathodic stability

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
A. A. SOLOVYEV ET AL.: "Magnetron-sputtered La0.6Sr0.4Co0.2Fe0.8O3 nanocomposite interlayer for solid oxide fuel cells", 《J. NANOPART. RES.》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110635103A (en) * 2019-08-29 2019-12-31 天津工业大学 Flexible nano porous metal oxide cathode for secondary battery and preparation method thereof
CN112663079A (en) * 2020-12-04 2021-04-16 中国科学院大连化学物理研究所 Tubular solid oxide electrolytic cell and preparation method and application thereof
CN112663079B (en) * 2020-12-04 2023-12-26 中国科学院大连化学物理研究所 Tubular solid oxide electrolytic cell and preparation method and application thereof

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Application publication date: 20190604