CN108666589A - There is one kind low thermal coefficient of expansion solid oxide fuel cell cobalt-based cathode material to prepare and its apply - Google Patents
There is one kind low thermal coefficient of expansion solid oxide fuel cell cobalt-based cathode material to prepare and its apply Download PDFInfo
- Publication number
- CN108666589A CN108666589A CN201810510366.1A CN201810510366A CN108666589A CN 108666589 A CN108666589 A CN 108666589A CN 201810510366 A CN201810510366 A CN 201810510366A CN 108666589 A CN108666589 A CN 108666589A
- Authority
- CN
- China
- Prior art keywords
- cathode
- fuel cell
- cathode material
- oxide fuel
- zro
- 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
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
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
-
- 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
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/881—Electrolytic membranes
-
- 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
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
-
- 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
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
The invention discloses a kind of cathode material for solid-oxide fuel cell BaNb that hot expansibility is excellentyZrxCo1‑x‑yO3‑δ, by BaCoO3‑δIn the positions Co carry out Nb2O5And ZrO2Codope is to reduce BaCoO3‑δBase cathode material coefficient of thermal expansion can obtain small TEC values (＜ 15 × 10‑6K‑1) and further the chemical property of promotion material, ingredient formula are BaNbyZrxCo1‑x‑yO3‑δ, wherein δ indicates oxygen excess amount or shortage amount, 1≤δ≤1；X indicates ZrO2Doping, 0≤x≤0.5；Y indicates Nb2O5Doping, 0≤y≤0.5.The BaNb of the present inventionyZrxCo1‑x‑yO3‑δCompared with traditional Co sills, coefficient of thermal expansion is greatly lowered cathode material, and has good chemical compatibility with GDC.There is good oxygen reduction catalytic activity in 500 850 DEG C of temperature ranges, is suitable for cathode material for solid-oxide fuel cell under middle low temperature.
Description
Technical field
The present invention relates to a kind of preparation method and applications of cathode material for solid-oxide fuel cell, and in particular to
One kind is in B codope Nb2O5And ZrO2To reduce BaCoO3-δCathode material coefficient of thermal expansion and its preparation method and application.
Background technology
Fuel cell is the power generator that the chemical energy of fuel can be converted directly into electric energy, it is in addition to firepower is sent out
The thinking of an innovation except the schemes such as electricity, hydroelectric generation and solar power generation.In the fuel cell of numerous types, Gu
Oxide body fuel cell (Solid Oxide Fuel Cell, SOFC) has apparent advantage：Its requirement to fuel is not
Height, hydrogen, coal gas and various hydrocarbon compounds all can serve as fuel and be used；Anode, electrolyte and the moon of entire battery
The component parts such as pole and connector are all solids, unlike other types of battery needs to carry out leakproof and anti-corrosion operation；Energy turns
It is very high to change efficiency, saves fuel.Currently, SOFC has become international research hotspot.
Part most crucial SOFC is to sinter anode, electrolyte, cathode into sandwiched type structure, from room temperature to
(500~800 DEG C) work under operation temperature.So that SOFC is carried out long-term work, needs to make anode, electrolyte, cathode heat
The coefficient of expansion (TEC) is close, keeps internal stress during temperature-rise period and the work from room temperature to operating temperature small.Currently, logical
Common Y2O3Stable ZrO2(YSZ) or Gd2O3Adulterate CeO2(GDC) do electrolyte, coefficient of thermal expansion be generally (10~12) ×
10-6K-1, anode material NiO-YSZ composite ceramics, coefficient of thermal expansion is generally 10.8 × 10-6K-1, and usually used Co
The coefficient of thermal expansion of based perovskite type cathode material is far longer than the coefficient of thermal expansion of electrolyte, larger coefficient of thermal expansion meeting
It is substantially reduced battery performance.
By literature search, traditional Co sills (LaCoO3、SrCoO3、BaCoO3) general all swollen with larger heat
Swollen coefficient.If Wang et al. is in Novel SrCo1-yNbyO3-δcathodes for intermediate-temperature
Solid oxide fuel cells (novel high-performance intermediate temperature solid oxide fuel cell cathode material SrCo1-yNbyO3-δ,
Journal of Power Sources,2010,195(12):3772-3778.) in a text, find SrCo0.9Nb0.1O3-δ
(SCN) it is 24.2 × 10 in the average TEC of room temperature to 1000 DEG C-6 K-1.Du et al. is in Evaluation ofLa0.3Sr0.7Ti1- xCoxO3As a potential cathode material for solid oxide fuel cells (medium temperature solid oxidations
Object fuel battery cathode material La0.3Sr0.7Ti1-xCoxO3Research, Journal ofMaterials Chemistry A,
2014,2(26):10290-10299.) La is had studied in a text0.3Sr0.7Ti1-xCoxO3-δ300~900 under different Co contents
DEG C coefficient of thermal expansion, it was found that it is respectively 20.7 × 10 in the mean thermal expansion coefficients of x=0.3,0.45 and 0.6-6,
23.6×10-6With 26.3 × 10-6K-1.Wei et al. is in Thermal and Electrical Properties of New
Cathode Material Ba0.5Sr0.5Co0.8Fe0.2O3-δFor Solid Oxide Fuel Cells (middle temperature solid-oxides
Fuel battery cathode material Ba0.5Sr0.5Co0.8Fe0.2O3-δCalorifics and electrical properties) have studied in a text
Ba0.5Sr0.5Co0.8Fe0.2O3-δ(BSCF) 30~1000 DEG C average TEC be 21.6 × 10-6K-1, with electrolyte GDC
It is poor with degree.In addition, Zhou et al. is in Evaluation of A-site cation-deficient (Ba0.5Sr0.5)1- xCo0.8Fe0.2O3-δ(x>0) perovskite as a solid-oxide fuel cell cathode (solid oxide fuels
Battery cathode material (Ba0.5Sr0.5)1-xCo0.8Fe0.2O3-δ(x>0) research) probed into a text different defect levels 50~
750 DEG C of coefficient of thermal expansion, it was found that when the mean thermal expansion coefficients of x=0.03 and 0.09 are respectively 18.0 × 10-6With 17.1
×10-6K-1。
Currently, in order to improve the big problem of above-mentioned Co sills coefficient of thermal expansion, generally use adulterate other cations or
Person prepares the method for composite material to promote the comprehensive performance of Co sills.It retrieves and finds by the prior art, Sc members can be passed through
The doping of element promotes the structural stability and cathode performance of cathode material, if Zhou et al. is in Novel SrSc0.2Co0.8O3-δas
(novel high-performance medium temperature is solid by a cathode material for low temperature solid-oxide fuel cell
Oxide body fuel battery cathode material SrSc0.2Co0.8O3-δ, Electrochemistry Communications, 2008,10
(10):1647-1651.) in have studied in SrCoO3-δSingly influence of the doping Sc elements to its thermal stability of the positions B, find
The doping of Sc can largely reduce the coefficient of thermal expansion of Co sills, in the average thermal expansion system of room temperature to 1000 DEG C
Number is 16.9 × 10-6 K-1.The present invention is in BaCoO3-δMiddle Co progress Nb2O5And ZrO2Codope, to reduce BaCoO3-δ
Base cathode material coefficient of thermal expansion.
Invention content
For the deficiencies in the prior art, the present invention provides a kind of soild oxides that hot expansibility is excellent
Fuel battery cathode material BaNbyZrxCo1-x-yO3-δ, by BaCoO3-δIn the positions B carry out Nb2O5And ZrO2Codope is to drop
Low BaCoO3-δBase cathode material coefficient of thermal expansion can obtain and the matched TEC values (＜ 15 × 10 of electrolyte phase-6K-1) simultaneously
And further promote the chemical property of material.
The purpose of the present invention is what is be achieved through the following technical solutions：
A kind of BaCoO3-δB Nb of base2O5And ZrO2The cathode material for solid-oxide fuel cell of codope has calcium
Titanium ore type structure, ingredient formula are BaNbyZrxCo1-x-yO3-δ, wherein δ indicates oxygen excess amount or shortage amount, -1≤δ≤1；x
Indicate ZrO2Doping, 0<X≤0.5, y indicate Nb2O5Doping, 0<y≤0.5.
Above-mentioned BaCoO3-δB Nb of based perovskite2O5And ZrO2The cathode material for solid-oxide fuel cell of codope is adopted
It is synthesized with solid reaction process or sol-gal process.The specific synthesis step of sol-gal process is as follows：
(1) it using metal nitrate object as raw material, is stoichiometrically weighed according to product formula, is molten with deionized water
Agent is dissolved, and metal-nitrate solutions are prepared.
(2) citric acid water solvent is added with appropriate ammonia solvent ethylenediamine tetra-acetic acid (EDTA) and prepares enveloping agent solution,
Molar ratio is metal ion：EDTA:Citric acid=1:1:2.
(3) metal-nitrate solutions are added in enveloping agent solution, ammonium hydroxide is used in combination to adjust PH to 10~11.
(4) mixed solution is placed in 90 DEG C of thermostat water baths and heats and stir, until solution evaporation is translucent solidifying in pink colour
Glue.
(5) gel, which is placed in baking oven, is dried into gel, is calcined in being transferred to Muffle furnace, and final cathode powder is obtained
Body.
Above-mentioned BaCoO3-δB Nb of based perovskite2O5And ZrO2The cathode of solid oxide fuel cell powder of codope
Preparation method is all made of solid reaction process, and specific and preparation and characterization process include the following steps：
(1) it using source metal as raw material, is stoichiometrically weighed according to product formula, is used by medium of dispersant
Ball mill ball milling.
(2) presoma after drying is calcined for the first time, later with agate mortar grinding powder 10-30min.
(3) it by the powder tabletting after grinding, is finally sintered.
(4) ball milling in high-energy ball milling of the cathode sheets after burning obtains cathode powder eventually.
(5) dry-pressing formed after mixing cathode powder obtained and binder according to a certain percentage, material is measured after calcining
Thermal dilatometry.
(6) with Sm2O3Stablize ZrO2(SSZ) it is electrolyte, in the both sides SSZ using screen-printing deposition GDC as blocking
Layer is calcined after dry.
(7) by BaNbyZrxCo1-x-yO3-δCathode powder has the barrier layers GDC by screen-printing deposition to surface
SSZ electrolyte both sides, calcining prepare Symmetrical cells, test battery performance.
In the above method, source metal described in step (1) is the oxide or carbonate of corresponding element, and dispersant is nothing
Water-ethanol, Ball-milling Time be 20~for 24 hours.
In the above method, first 500~1000 DEG C of calcination temperature, 10~20h of calcination time in step (2)
In the above method, pressure limit is 10~20MPa, 5~10min of tabletting time in step (3), and calcination temperature is
800~1200 DEG C, 10~20h of calcination time.
In the above method, Ball-milling Time is 4~6h in step (4).
In the above method, binder described in step (5) be ethyl cellulose, account for cathode powder mass ratio be 0.5~
3%.
In the above method, GDC, Bi in barrier layer in step (6)2O3It is 1 with ethyl cellulose mass ratio：0.1~0.5：
0.1~0.5,800~1000 DEG C of calcination temperature, calcination time is 1~5h.
In the above method, cathode powder BaNb in step (7)yZrxCo1-x-yO3-δIt is 1 with ethyl cellulose mass ratio:
0.1~0.5,800~1000 DEG C of calcination temperature, calcination time is 1~5h.
The present invention also provides BaNbyZrxCo1-x-yO3-δAnswering in intermediate temperature solid oxide fuel cell cathode material
With.(1) SSZ electrolyte sheets are obtained with the tape casting, detailed process is as follows：Dispersant triethanolamine is dissolved in ethyl alcohol and butanone
In the mixed solvent, be added SSZ powder, first ball milling 18 hours, then successively add polyvinyl butyral (PVB) plasticizer and
Polyethylene glycol (PEG) and diethyl phthalate (PHT) toughener, continue ball milling 18 hours.Taking-up slurry, vacuum defoamation,
The air of the inside is removed, SSZ electrolyte layers are cast, it is drying over night, obtain SSZ electrolyte biscuits.(2) by GDC powders and ethyl
Cellulose, Bi2O3It is blended in organic solvent terpinol, the barrier layers screen-printing deposition GDC, 1200~1400 DEG C are calcined
To fine and close barrier layer.Then cathode powder obtained is mixed in organic solvent with 5~10% ethyl cellulose, is led to
It crosses silk screen print method cathode powder is coated on barrier layer, then be calcined, calcination temperature is 900~1000 DEG C, calcining
Time is 5~12h, you can cathode layer is made.
The present invention has the following effects that：
The BaNb of the present inventionyZrxCo1-x-yO3-δCompared with traditional Co sills, coefficient of thermal expansion reduces cathode material,
It can obtain and matched TEC values (the about ＜ 15 × 10 of electrolyte phase-6K-1), and have good chemical compatibility with GDC.
The hybrid conductive that oxonium ion and electronics are shown in air shows good hydrogen reduction in 500~850 DEG C of temperature ranges
Catalytic activity is suitable for cathode material for solid-oxide fuel cell under middle low temperature.
Specific implementation mode
It is described further below in conjunction with attached drawing technical solution in the embodiment of the present invention, but not limited to this, it is all
It is to be modified or replaced equivalently to technical solution of the present invention, without departing from the spirit of the technical scheme of the invention and range,
It should cover in protection scope of the present invention.
Description of the drawings
Fig. 1 is BaNb prepared by different calcination temperatures0.15Zr0.1Co0.75O3-δXRD spectrum；
Fig. 2 is BaNb prepared by 1100 DEG C of calcining 10h0.15ZrxCo0.85-xO3-δThe XRD spectrum of powder；
Fig. 3 is BaNb0.15Zr0.1Co0.75O3-δThe XRD collection of illustrative plates of 5h is calcined at 950 DEG C with the mixed powder of GDC；
Fig. 4 is BaNb0.15ZrxCo0.85-xO3-δThe thermal dilatometry of powder；
Fig. 5 is BaNb0.15ZrxCo0.85-xO3-δThe impedance spectra that 700 DEG C of cathode Symmetrical cells；
Fig. 6 is Ni-SSZ | SSZ | GDC | and BaNb0.15Zr0.1Co0.75O3-δThe discharge curve of full battery at different temperatures
Figure.
Example 1
This example provides a kind of BaCoO3-δB Nb of base2O5And ZrO2The cathode of solid oxide fuel cell of codope
Material, it is BaNb to have Cubic perovskite structure, ingredient formulayZrxCo1-x-yO3-δ, wherein δ expression oxygen excess amounts or scarce
Weary amount, -1≤δ≤1；X indicates ZrO2Doping, 0≤x≤0.5；Y indicates Nb2O5Doping, 0≤y≤0.5.
As shown in Figure 2 as y=0.15, x=0, BaNb when 0.05,0.10 and 0.150.15ZrxCo0.85-xO3-δIt is vertical
Square phase perovskite structure.
Example 2：
This example provides intermediate temperature solid oxide fuel cell cathode material BaNb0.15ZrxCo0.85-xO3-δPreparation and
Characterizing method specifically includes following steps：
Step 1：Using metal oxide or carbonate as raw material, matches and weigh according to stoichiometric equation, with absolute ethyl alcohol
Dispersant is medium, for 24 hours using high energy ball mill ball milling；
Step 2：By 900 DEG C of calcining 12h of presoma after ball milling；
Step 3:After obtained powder is ground, in pressure 5~10min of lower sheeting of 10~12MPa, then 1100
DEG C eventually burn 10h obtain eventually burn powder.
Step 4：By powder in high energy ball mill ball milling 6h, obtain cathode powder；
Step 5：The ethyl cellulose for accounting for cathode powder quality 0.5~3% is added thereto, 10 in steel casting mould~
20MPa pushes 5~15min moldings, at a temperature of the sample being pressed into is warming up to 900~1000 DEG C in high temperature furnace with 2 DEG C/min
It is calcined 1~3h, prepares densified sample, measures coefficient of thermal expansion.
Step 6：By BaNb obtained0.15ZrxCo0.85-xO3-δThe ethyl cellulose of mass fraction 5~15% is added in powder
Binder is added the terpinol of 1~5 drop as solvent, the both sides on the barrier layers GDC is coated on by the method for silk-screen printing,
It is calcined 2h at 900~1000 DEG C, BaNb is made0.15ZrxCo0.85-xO3-δSymmetry electrode.As shown in figure 5, each component polarization impedance
It is satisfied by the requirement of SOFC.
Example 3：
This example provides a kind of BaNb0.15Zr0.1Co0.75O3-δPreparation and performance characterization scheme, specifically contain
Following experimental procedure：
Step 1：It weighs and analyzes pure barium carbonate 3.9468g, niobium pentaoxide 0.2658g, zirconium oxide 0.2464g and three oxygen
Change two cobalt 1.244g, using 20mL absolute ethyl alcohols as dispersant, using ball mill with the speed ball milling of 500r/min for 24 hours.
Step 2：Obtained presoma is dried, 12h, cooled to room temperature are calcined at air atmosphere, 900 DEG C.
Then the pressure by the presoma after first burn in 10MPa pushes 5min, becomes fine and close sheetlike material.By cathode
Piece is in air atmosphere respectively with 900,1000 and 1100 DEG C of burning 10h, cooled to room temperature.Finally by cathode sheets in high energy
Ball milling 6h obtains cathode powder in ball milling.The XRD spectrum of prepared powder as shown in Figure 1, show cathode powder 900~
Required cubic perovskite structure can be obtained by being prepared at 1100 DEG C.
Step 3：By synthetic cathode powder BaNb0.15Zr0.1Co0.75O3-δWith GDC in mass ratio 1:1 mixing and with grinding
Alms bowl grinding ensures to reach uniformly mixed, is about then 3 DEG C of min in heating rate-1Under conditions of, with 950 DEG C in air atmosphere
5h is calcined, the XRD spectrum of powder is the chemical compatibility that can determine between cathode material and electrolyte after being calcined by measurement
Property.The XRD spectrum of gained mixed powder as shown in figure 3, show cathode powder at 900~1000 DEG C with the chemical compatibility of GDC
Property is good.
Step 4：1% (mass ratio) ethyl-cellulose binder is added after mixing in the cathode powder of synthesis, in steel
It is dry-pressing formed under 15MPa in casting mould, the sample being pressed into is warming up to 950 DEG C of temperature lower calcination 2h in high temperature furnace, prepares and causes
Close sample, using DIL402PC measure material range in 100~900 DEG C thermal expansion such as Fig. 4, calculate its
The mean thermal expansion coefficients of range are 13.972 × 10 in 100~900 DEG C-6K-1。
Step 4：0.2g cathode powders, 0.02g ethyl celluloses are weighed, two drop terpinols are added and prepare after mixing
At slurry, the densification barrier layers GDC both sides, three layers of cathode slurry of repetitive coatings are coated in by the way of silk-screen printing.After drying
It is calcined 2h at 950 DEG C, Symmetrical cells are made.Testing impedance, which is carried out, with Symmetrical cells obtains the polarization such as Fig. 5 at 700 DEG C
Impedance, wherein BaNb0.15Zr0.1Co0.75O3-δPolarization impedance be 0.026 Ω cm2。
Step 4：0.2g cathode powders, 0.02g ethyl celluloses are weighed, two drop terpinols are added and prepare after mixing
At slurry, the densification barrier layers GDC unilateral side is coated in by the way of silk-screen printing, and (GDC is coated in sun by method for printing screen
The electrolyte side of pole support) three layers of cathode slurry of repetitive coatings.It is calcined 2h at 950 DEG C after drying, full battery is made.With complete
Battery carries out discharge test and obtains Fig. 6, as can be drawn from Figure 6 with BaNb0.15Zr0.1Co0.75O3-δFor the full electricity of cathode material
Maximum discharge power density of the pond at 850 DEG C reaches 677mW cm-2。
Example 4：
BaNb0.15ZrxCo0.85-xO3-δ(x=0.05,0.1 and 0.15) the measurement of the coefficient of thermal expansion of material
BaNb is measured using Netsch DIL 402PC thermal dilatometers0.15ZrxCo0.85-xO3-δ(x=0.05,0.1 and
0.15) coefficient of thermal expansion.Bar shaped sample is prepared by dry pressing, 5 × 5 × 10mm of size is obtained by 950 DEG C of sintering 2h
Densified sample, 30~1000K of Range of measuring temp, 5 DEG C/min of heating rate.Test results are shown in figure 4, each component cathode
Mean thermal expansion coefficients of the material in different temperatures section are respectively less than traditional Co sills, and with the electrolyte such as YSZ, GDC
TEC it is close, show that prepared cathode has matched coefficient of thermal expansion with electrolyte.
Claims (3)
1. a kind of cathode material for solid-oxide fuel cell BaNb that hot expansibility is excellentyZrxCo1-x-yO3-δ, by
BaCoO3-δIn the positions Co carry out Nb2O5And ZrO2Codope is to reduce BaCoO3-δBase cathode material coefficient of thermal expansion, can obtain
Small TEC values (＜ 15 × 10-6K-1) and further the chemical property of promotion material, wherein δ indicate oxygen excess amount or shortage
Amount, -1≤δ≤1；X indicates ZrO2Doping, 0≤x≤0.5；Y indicates Nb2O5Doping, 0≤y≤0.5.
2. BaCoO according to claim 13-δB Nb of base2O5And ZrO2The cathode of solid oxide fuel cell of codope
Material, it is characterised in that the y=0.15；X=0.05,0.10 or 0.15.
3. BaCoO according to claim 13-δB Nb of base2O5And ZrO2The cathode of solid oxide fuel cell of codope
Material, it is characterised in that steps are as follows for the method：
Step 1：Using metal oxide or carbonate as raw material, matches and weigh according to stoichiometric equation, disperseed with absolute ethyl alcohol
Agent is medium, for 24 hours using high energy ball mill ball milling；
Step 2：By 900 DEG C of calcining 12h of presoma after ball milling；
Step 3:After obtained powder is ground, in pressure 5~10min of lower sheeting of 10~12MPa, then burn eventually for 1100 DEG C
10h obtains burning powder eventually；
Step 4：By powder in high energy ball mill ball milling 6h, obtain cathode powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810510366.1A CN108666589A (en) | 2018-05-24 | 2018-05-24 | There is one kind low thermal coefficient of expansion solid oxide fuel cell cobalt-based cathode material to prepare and its apply |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810510366.1A CN108666589A (en) | 2018-05-24 | 2018-05-24 | There is one kind low thermal coefficient of expansion solid oxide fuel cell cobalt-based cathode material to prepare and its apply |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108666589A true CN108666589A (en) | 2018-10-16 |
Family
ID=63776575
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810510366.1A Pending CN108666589A (en) | 2018-05-24 | 2018-05-24 | There is one kind low thermal coefficient of expansion solid oxide fuel cell cobalt-based cathode material to prepare and its apply |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108666589A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116014159A (en) * | 2023-02-24 | 2023-04-25 | 中国矿业大学 | Oxygen electrode material of solid oxide battery, preparation method and application |
| CN116666670A (en) * | 2023-08-01 | 2023-08-29 | 成都岷山绿氢能源有限公司 | Lanthanum-niobium co-doped intermediate-temperature SOFC cathode material and preparation method and application thereof |
| CN118099451A (en) * | 2024-04-22 | 2024-05-28 | 成都岷山绿氢能源有限公司 | A-site defect and B-site multielement doped intermediate-temperature SOFC cathode material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0927330A (en) * | 1995-07-11 | 1997-01-28 | Tokyo Gas Co Ltd | Fuel electrode of solid electrolyte fuel cell |
| CN102208663A (en) * | 2011-04-20 | 2011-10-05 | 南京工业大学 | BaFeO doped with transition metal element at B position3-δABO of radicals3Perovskite type fuel cell cathode material and application thereof |
| CN102842722A (en) * | 2011-06-21 | 2012-12-26 | 三星电子株式会社 | Material for solid oxide fuel cell, cathode including the material, and solid oxide fuel cell including the material |
| CN104409742A (en) * | 2014-11-06 | 2015-03-11 | 哈尔滨工业大学 | BaCoO3-delta base B-position Bi2O3-Nb2O5 co-doped cathode material of solid oxide fuel cell, preparation method and applications thereof |
| JP2016085921A (en) * | 2014-10-28 | 2016-05-19 | Ｊｘエネルギー株式会社 | Cell support and solid oxide fuel cell |
-
2018
- 2018-05-24 CN CN201810510366.1A patent/CN108666589A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0927330A (en) * | 1995-07-11 | 1997-01-28 | Tokyo Gas Co Ltd | Fuel electrode of solid electrolyte fuel cell |
| CN102208663A (en) * | 2011-04-20 | 2011-10-05 | 南京工业大学 | BaFeO doped with transition metal element at B position3-δABO of radicals3Perovskite type fuel cell cathode material and application thereof |
| CN102842722A (en) * | 2011-06-21 | 2012-12-26 | 三星电子株式会社 | Material for solid oxide fuel cell, cathode including the material, and solid oxide fuel cell including the material |
| JP2016085921A (en) * | 2014-10-28 | 2016-05-19 | Ｊｘエネルギー株式会社 | Cell support and solid oxide fuel cell |
| CN104409742A (en) * | 2014-11-06 | 2015-03-11 | 哈尔滨工业大学 | BaCoO3-delta base B-position Bi2O3-Nb2O5 co-doped cathode material of solid oxide fuel cell, preparation method and applications thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116014159A (en) * | 2023-02-24 | 2023-04-25 | 中国矿业大学 | Oxygen electrode material of solid oxide battery, preparation method and application |
| CN116666670A (en) * | 2023-08-01 | 2023-08-29 | 成都岷山绿氢能源有限公司 | Lanthanum-niobium co-doped intermediate-temperature SOFC cathode material and preparation method and application thereof |
| CN116666670B (en) * | 2023-08-01 | 2023-10-31 | 成都岷山绿氢能源有限公司 | Lanthanum-niobium co-doped intermediate-temperature SOFC cathode material and preparation method and application thereof |
| CN118099451A (en) * | 2024-04-22 | 2024-05-28 | 成都岷山绿氢能源有限公司 | A-site defect and B-site multielement doped intermediate-temperature SOFC cathode material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhao et al. | Preparation and properties of BaxSr1− xCoyFe1− yO3− δ cathode material for intermediate temperature solid oxide fuel cells | |
| JP2719049B2 (en) | Method for producing lanthanum chromite membrane and method for producing interconnector for solid oxide fuel cell | |
| CN111900449B (en) | Solid oxide fuel cell, method for producing same and use thereof | |
| CN103390739B (en) | A kind of Solid Oxide Fuel Cell ceria-based electrolyte interlayer and preparation thereof | |
| CN104409742A (en) | BaCoO3-delta base B-position Bi2O3-Nb2O5 co-doped cathode material of solid oxide fuel cell, preparation method and applications thereof | |
| CN104388972B (en) | Cathode material and its application for electrolytic tank of solid oxide | |
| CN108666589A (en) | There is one kind low thermal coefficient of expansion solid oxide fuel cell cobalt-based cathode material to prepare and its apply | |
| US20150255821A1 (en) | Highly ionic conductive zirconia electrolyte for high-efficiency solid oxide fuel cell | |
| CN103985880A (en) | BaFeO3-theta-base B-site Bi2O3 doping solid oxide fuel cell cathode material as well as preparation method and application thereof | |
| CN110380066A (en) | A kind of ammonia decomposition hydrogen producing catalyst and the preparation method and application thereof | |
| CN108390071B (en) | Method for modifying surface of cathode of solid oxide fuel cell | |
| Bu et al. | Sintering behaviour of the protonic conductors BaZrxCe0. 8-xLn0. 2O3-δ (x= 0.8, 0.5, 0.1; Ln= Y, Sm, Gd, Dy) during the solid-state reactive-sintering process | |
| Leng et al. | The effect of sintering aids on BaCe0· 7Zr0· 1Y0. 1Yb0. 1O3-δ as the electrolyte of proton-conducting solid oxide electrolysis cells | |
| EP3537524B1 (en) | Composite particle powder, electrode material for solid oxide cell, and electrode for solid oxide cell made thereof | |
| Hao et al. | Co-tape casting fabrication, field assistant sintering and evaluation of a coke resistant La0. 2Sr0. 7TiO3–Ni/YSZ functional gradient anode supported solid oxide fuel cell | |
| Duran et al. | Study of La4BaCu5− xCoxO13+ δ series as potential cathode materials for intermediate-temperature solid oxide fuel cell | |
| CN117049871A (en) | Bismuth oxide based medium-low entropy oxygen ion conductor material and preparation method thereof | |
| CN111584882A (en) | Solid oxide fuel cell with novel structure and preparation method thereof | |
| CN111416138A (en) | Proton ceramic membrane fuel cell and preparation method thereof | |
| CN115692806A (en) | High-entropy perovskite electrolyte, preparation method and application thereof, and battery | |
| KR101100349B1 (en) | Fabrication methods of solid electrolyte of solid oxide fuel cell and solid oxide fuel cell using the same | |
| CN102544559B (en) | Cerium-oxide-based electrolyte for solid oxide fuel cell and manufacturing method thereof | |
| JP6717331B2 (en) | Solid oxide fuel cell | |
| JP2002053374A (en) | Multiple oxide for air pole of solid electrolytic fuel cell and for electric collector raw material, its manufacturing method and solid electrolytic fuel cell | |
| CN113451594A (en) | Cathode material of solid oxide fuel cell and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20181016 |
|
| WD01 | Invention patent application deemed withdrawn after publication |