CN101465428A - Method for improving solid-oxide fuel battery performance - Google Patents
Method for improving solid-oxide fuel battery performance Download PDFInfo
- Publication number
- CN101465428A CN101465428A CNA2009100451128A CN200910045112A CN101465428A CN 101465428 A CN101465428 A CN 101465428A CN A2009100451128 A CNA2009100451128 A CN A2009100451128A CN 200910045112 A CN200910045112 A CN 200910045112A CN 101465428 A CN101465428 A CN 101465428A
- Authority
- CN
- China
- Prior art keywords
- anode
- oxide fuel
- battery
- solid
- solution
- 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.)
- Granted
Links
Images
Classifications
-
- 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 relates to a method for improving the performance of solid oxide fuel batteries and belongs to the field of the solid oxide fuel batteries. The method is characterized in that: (1) the fired battery anode is deoxidized by reducing gas (such as H2 or Co), the NiO-YSZ (YSZ is zirconia which is stabilized by yttrium) system in the anode is deoxidized into a Ni-YSZ system. As NiO is deoxidized into Ni, 25 percent of volume is changed, therefore, after the anode of the fired battery is deoxidized, the quite a bit of clearance is left in the anode; (2) the deoxidized anode of the battery is immersed in the solution of to-be-introduced material or precursor solution; at the moment, as the anode is deoxidized, the structure is loosened, and the to-be-introduced material or the precursor can be easily immersed into the whole anode; (3) heat treatment is carried out on the immersed battery anode and the precursor is decomposed, thus obtaining the material needed to be introduced into the battery anode.
Description
Technical field
The present invention relates to a kind of method that improves solid-oxide fuel battery performance, belong to field of solid oxide fuel.
Background technology
Solid Oxide Fuel Cell (SOFC) works in high temperature (650～1000 ℃), can be directly changed into electric energy to the chemical energy of fuel, system effectiveness height (〉 70%), environmental pollution is low, fuel source is extensive, just because of SOFC has above technology and economic advantages, so be a kind of energy converting apparatus that has very much commercial viability.
The step of preparation process of Solid Oxide Fuel Cell generally includes: the powder that (1) will prepare battery is mixed in certain organic solvent, and Ball milling is even, makes slurry; (2) this slurry is adopted certain method, make the biscuit of battery as curtain coating etc.; (3) with this biscuit at high temperature, as 1400 the degree above sintering; (4) burned biscuit is polished, is engraved as the battery that conforms with designing requirement.The preparation Solid Oxide Fuel Cell requires the hot expansibility of its each assembly to mate, otherwise, will occur in the cell preparation process of high temperature that electrode comes off or the phenomenon of cell fracture, can not make the battery that needs.
It is to possess electronic conduction ability and ionic conduction ability simultaneously that the electrode material of Solid Oxide Fuel Cell is required, the part of in electrode, being responsible for conduction electron and conducting ion be called electron conduction mutually with ionic conduction mutually.The operation principle of SOFC electrode can be consulted Fig. 1, and gas diffuses to three phase boundary (TPB) and locates in the electrode of SOFC, here, gas molecule (as hydrogen molecule, H
2) with conduct the ion that comes mutually from ionic conduction (as oxonium ion O
2-) combination, electrochemical reaction takes place, the electronics that reaction is emitted is derived battery according to legend by electron conduction, externally acting.Obviously, if the electronic conduction ability of electrode material is good more, the ionic conduction ability is good more, and prepared battery performance is just good more, if having a kind of electrode material can possess the ionic conduction ability simultaneously and the electron conduction ability is just better.But, can satisfy simultaneously that the electron conduction ability is good, the ionic conduction ability is good and material that the aforementioned matched coefficients of thermal expansion of mentioning requires seldom.
SOFC anode material disclosed and that be widely adopted is by Ni, [1.S.P.Jiang, S.H.Chan, J.Materials Science, 39 (2004) 4405-4439 that YSZ (zirconia that yttrium is stable) is composited; 2.B.C.H.Steele, Solid StateIonics, 134 (2000) 3-20], Ni is the electron conduction phase, YSZ is the ionic conduction phase.When SOFC just baked, its anode was NiO-YSZ system, need be before battery uses with reducing atmosphere the NiO of anode be reduced to Ni.With regard to the ionic conduction ability, there are a lot of materials will be higher than YSZ.With cerium oxide (CeO) is example, though its ionic conduction ability is better than YSZ, and possesses certain electron conduction ability, but its thermal coefficient of expansion and entire cell do not match, and therefore, are difficult to CeO directly as the anode of SOFC, usually the method for introducing CeO in anode is that anode is flooded in the solution of cerous nitrate, then it heating and decomposition is become CeO[S.P.Jiang, Electrochemical and Solid-State Letters ,].But as previously mentioned, high temperature sintering more than SOFC has spent through 1400 in preparation process, whole anode is very fine and close, be difficult to immerse cerous nitrate, for guaranteeing certain immersion amount, the anode of having to soak pernitric acid cerium dipping once more after middle high temperature (as 600 degree) resolves into cerium oxide, this process that repeatedly circulates is until reaching certain CeO immersion amount.Dipping repeatedly, the method that multiple high temp decomposes obviously be one very loaded down with trivial details, very power consumption, time-consuming procedure, this shortens the production cycle for the production cost that reduces Solid Oxide Fuel Cell, it is very unfavorable to accelerate commercial applications.
Summary of the invention
In order to address the above problem, the object of the present invention is to provide a kind of method that improves solid-oxide fuel battery performance, also promptly introduce the short-cut method of the better material of performance in anode of solid oxide fuel cell, this method can improve the performance of Solid Oxide Fuel Cell significantly.
A kind of method that improves solid-oxide fuel battery performance is characterized in that improving the electrical property of battery by introduce material in the anode of Solid Oxide Fuel Cell.Its step comprises: (1) preparation waits to introduce the precursor solution of material; (2) with the anode high temperature reduction of Solid Oxide Fuel Cell; (3) battery electrode after will reducing is immersed in the solution of step 1 preparation, will be dipped into the presoma of waiting to introduce material in the anode of battery; (4) the battery electrode heat treatment after will flooding in heat treatment process, decomposes the presoma of immersion, and generating needs the material introduced;
Described galvanic anode is the NiO-YSZ system, is reduced to the Ni-YSZ system, follows therebetween and 25% change in volume, therefore after step 2 high temperature (700～800 ℃) reduction, will stay a considerable amount of holes in the anode; It is more loose that structure becomes, and the immersion thing behind the dipping enters whole anode easily, and again through heat treatment, the presoma of dipping decomposes, and obtains needing to introduce the material of galvanic anode.
The method of raising solid-oxide fuel battery performance provided by the invention is characterized in that the anode for NiO-YSZ, the steps include:
(a) the preparation oxidation-containing cerium or or mix the solution of the cerium oxide precursor body of samarium, the molar concentration of solution is 0.1～0.5M;
(b) the anode high temperature reduction of battery, temperature is 700～800 ℃;
(c) electrode behind the step b high temperature reduction is immersed in the solution that contains presoma of step a preparation;
(d) the battery electrode heat treatment between 500～700 ℃ after will flooding;
For NiO-YZS system anode material, the presoma that uses is the CeO of CeO or samarium doping; The ratio of the concentration of the samarium ion that mixes and the concentration of principal phase cerium ion is between 1:5～1:1;
The time of described step c dipping is 1～2 minute;
Described steps d heat treatment time is 0.5～1.5 hour;
What described battery high-temperature reduced usefulness is any gas with reducing property; As hydrogen or carbon monoxide.
Description of drawings
Fig. 1 is the schematic diagram of SOFC electrode reaction;
Fig. 2 is oxide impregnation cerium (CeO), SOFC after the dipping samarium doping of cerium oxide (SDC) and the performance comparison of not passing through the SOFC of dipping;
Embodiment
Below in conjunction with the description of embodiment, further specify substantive distinguishing features of the present invention and obvious improvement.
Embodiment 1
Immerse cerium oxide in the anode of Solid Oxide Fuel Cell, improve its performance, concrete steps are as follows:
The first step, configuration concentration are the cerous nitrate solution of 0.5M;
Second step, the SOFC battery sheet that bakes was reduced 1 hour in 800 ℃ hydrogen, the NiO in its anode fully is reduced to Ni;
The 3rd step, the battery sheet after the reduction was immersed in the cerous nitrate solution of 0.5M 1 minute, take out then, dry;
The 4th step, the heat treatment 1 hour under 600 ℃ of air atmospheres of the battery after will drying, the cerous nitrate in this moment anode is a cerium oxide with natural decomposition, and is dispersed in the whole anode.
Fig. 2 has compared through the performance of the SOFC of dipping with not through the discharge performance of the SOFC of dipping, can find, and process oxide impregnation cerium, the performance of Solid Oxide Fuel Cell obtained significant raising.
Immersion is different from the cerium oxide concentration shown in the embodiment 1 in the anode of Solid Oxide Fuel Cell, improves its performance, and concrete steps are as follows:
The first step, configuration concentration are the cerous nitrate solution of 0.1M;
Second step, the SOFC battery sheet that bakes was reduced 1 hour in 800 ℃ hydrogen, the NiO in its anode fully is reduced to Ni;
The 3rd step, the battery sheet after the reduction was immersed in the cerous nitrate solution of 0.1M 2 minutes, take out then, dry;
In the 4th step, the battery after will drying was 600 ℃ of heat treatments 1 hour, and the interior cerous nitrate of anode this moment is a cerium oxide with natural decomposition, and is dispersed in the whole anode.
Embodiment 3
The concentration that immerses cerium oxide in the anode of Solid Oxide Fuel Cell is identical with embodiment 2, but last heat treatment temperature difference, to improve its performance, concrete steps are as follows:
The first step, configuration concentration are the cerous nitrate solution of 0.1M;
Second step, the SOFC battery sheet that bakes was reduced 1 hour in 800 ℃ hydrogen, the NiO in its anode fully is reduced to Ni;
The 3rd step, the battery sheet after the reduction was immersed in the cerous nitrate solution of 0.1M 2 minutes, take out then, dry;
In the 4th step, the battery after will drying was 700 ℃ of heat treatments 0.5 hour, and the interior cerous nitrate of anode this moment is a cerium oxide with natural decomposition, and is dispersed in the whole anode.
Embodiment 4
Immerse cerium oxide in the anode of Solid Oxide Fuel Cell, improve its performance, concrete steps are as follows:
The first step, configuration concentration are the cerous nitrate solution of 0.1M;
Second step, the SOFC battery sheet that bakes was reduced 1 hour in 800 ℃ carbon monoxide (CO), the NiO in its anode fully is reduced to Ni;
The 3rd step, the battery sheet after the reduction was immersed in the cerous nitrate solution of 0.1M 2 minutes, take out then, dry;
In the 4th step, the battery after will drying was 700 ℃ of heat treatments 1 hour, and the interior cerous nitrate of anode this moment is a cerium oxide with natural decomposition, and is dispersed in the whole anode.
Embodiment 5
Immerse cerium oxide in the anode of Solid Oxide Fuel Cell, improve its performance, concrete steps are as follows:
The first step, configuration concentration are the cerous nitrate solution of 0.1M;
In second step, with the SOFC battery sheet that bakes reductase 12 hour in 700 ℃ hydrogen, the NiO in its anode fully is reduced to Ni;
The 3rd step, the battery sheet after the reduction was immersed in the cerous nitrate solution of 0.1M 2 minutes, take out then, dry;
In the 4th step, the battery after will drying was 700 ℃ of heat treatments 1.5 hours, and the interior cerous nitrate of anode this moment is a cerium oxide with natural decomposition, and is dispersed in the whole anode.
Embodiment 6
Immerse SDC (SDC refers to samarium (Sm) doping of cerium oxide (CeO), down together) in the anode of Solid Oxide Fuel Cell, improve its performance, concrete steps are as follows:
The first step, stoichiometric coefficient proportioning as required is samarium doping of cerium oxide (SDC) solution of 0.5M with cerous nitrate and samaric nitrate compound concentration, wherein the ratio of Sm and Ce is 1:4, (is Ce
0.8Sm
0.2(NO
3)
x);
The 3rd step, the SOFC battery sheet that bakes was reduced 1 hour in 800 ℃ hydrogen, the NiO in its anode fully is reduced to Ni;
The 4th step, the battery sheet after the reduction was immersed in the SDC solution of 0.5M 2 minutes, take out then, dry;
In the 5th step, the battery after will drying was 600 ℃ of heat treatments 1 hour, and the interior cerous nitrate samarium of anode this moment is the samarium doping of cerium oxide SDC that meets ratio requirement with natural decomposition, and is dispersed in the whole anode.
Fig. 2 has compared through the performance of the SOFC of dipping with not through the discharge performance of the SOFC of dipping, can find that through flooding SDC, the performance of Solid Oxide Fuel Cell obtained bigger raising.
Embodiment 7
Immerse SDC (SDC refers to samarium (Sm) doping of cerium oxide (CeO), down together) in the anode of Solid Oxide Fuel Cell, improve its performance, concrete steps are as follows:
The first step, stoichiometric coefficient proportioning as required is samarium doping of cerium oxide (SDC) solution of 0.5M with cerous nitrate and samaric nitrate compound concentration, wherein the ratio of Sm and Ce is 2:3, (is Ce
0.6Sm
0.4(NO
3)
x);
Second step, the SOFC battery sheet that bakes was reduced 1 hour in 800 ℃ hydrogen, the NiO in its anode fully is reduced to Ni;
The 3rd step, the battery sheet after the reduction was immersed in the SDC solution of 0.5M 2 minutes, take out then, dry;
In the 4th step, the battery after will drying was 600 ℃ of heat treatments 1 hour, and the interior cerous nitrate samarium of anode this moment is the samarium doping of cerium oxide SDC that meets ratio requirement with natural decomposition, and is dispersed in the whole anode.
Claims (6)
1, a kind of method that improves solid-oxide fuel battery performance is characterized in that improving the electrical property of battery by introduce material in the anode of Solid Oxide Fuel Cell.Its step comprises: (a) preparation waits to introduce the precursor solution of material; (b) anode with Solid Oxide Fuel Cell reduces; (c) battery electrode after will reducing is immersed in the solution of step (a) preparation, makes in the anode of battery to immerse the presoma of waiting to introduce material; (d) the battery electrode heat treatment after will flooding is decomposed the presoma of immersion, generates the introducing material that needs.
2, by the method for the described raising solid-oxide fuel battery performance of claim 1, it is characterized in that anode, the steps include: for NiO-YSZ
(a) the preparation oxidation-containing cerium or or mix the solution of the cerium oxide precursor body of samarium, the molar concentration of solution is 0.1～0.5M;
(b) the anode high temperature reduction of battery, temperature is 700～800 ℃;
(c) electrode behind the step b high temperature reduction is immersed in the solution that contains presoma of step a preparation;
(d) the battery electrode heat treatment between 500～700 ℃ after will flooding.
3, by the method for claim 1 or 2 described raising solid-oxide fuel battery performances, that it is characterized in that high temperature reduction uses among the step b is H
2Or Co atmosphere.
4,, it is characterized in that the time of step c dipping is 1～2 minute by the method for the described raising solid-oxide fuel battery performance of claim 2.
5, by the method for the described raising solid-oxide fuel battery performance of claim 2, it is characterized in that the steps d heat treatment time is 0.5～1.5 hour.
6, by the method for the described raising solid-oxide fuel battery performance of claim 2, the concentration ratio that it is characterized in that the concentration of samarium doped ion among the step a and principal phase Ce ion is between 1:5～1:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100451128A CN101465428B (en) | 2009-01-09 | 2009-01-09 | Method for improving solid-oxide fuel battery performance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100451128A CN101465428B (en) | 2009-01-09 | 2009-01-09 | Method for improving solid-oxide fuel battery performance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101465428A true CN101465428A (en) | 2009-06-24 |
| CN101465428B CN101465428B (en) | 2012-08-08 |
Family
ID=40805873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100451128A Active CN101465428B (en) | 2009-01-09 | 2009-01-09 | Method for improving solid-oxide fuel battery performance |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101465428B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106876719A (en) * | 2015-12-12 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of anode material of high-temperature fuel cell and its preparation and application |
| CN108360010A (en) * | 2018-01-26 | 2018-08-03 | 济南大学 | A kind of preparation method of novel solid oxide electrolysis cells electrode catalyst coating |
| CN109037698A (en) * | 2017-06-08 | 2018-12-18 | 中国科学院宁波材料技术与工程研究所 | It is a kind of can energy storage high-temperature solid oxide fuel cell |
-
2009
- 2009-01-09 CN CN2009100451128A patent/CN101465428B/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106876719A (en) * | 2015-12-12 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of anode material of high-temperature fuel cell and its preparation and application |
| CN109037698A (en) * | 2017-06-08 | 2018-12-18 | 中国科学院宁波材料技术与工程研究所 | It is a kind of can energy storage high-temperature solid oxide fuel cell |
| CN108360010A (en) * | 2018-01-26 | 2018-08-03 | 济南大学 | A kind of preparation method of novel solid oxide electrolysis cells electrode catalyst coating |
| CN108360010B (en) * | 2018-01-26 | 2019-09-06 | 济南大学 | A kind of preparation method of solid oxide electrolysis cell electrode catalyst coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101465428B (en) | 2012-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101485018B (en) | Ceramic material combination for an anode of a high-temperature fuel cell | |
| CN101295791B (en) | Ternary complex cathode material of intermediate/low temperature solid-oxide fuel battery | |
| Liu et al. | Fabrication and characterization of micro-tubular cathode-supported SOFC for intermediate temperature operation | |
| CN106848358B (en) | Doped cerium oxide based solid oxide fuel cell and preparation method thereof | |
| CN103811788A (en) | Preparation method for middle-temperature and low-temperature solid oxide fuel battery | |
| CN104103838A (en) | Anode protection layer for solid oxide fuel cell, and preparation method and application of anode protection layer | |
| CN102104153A (en) | Preparation method of cathode of low-medium temperature solid oxide fuel cell | |
| CN113745548B (en) | High-entropy ceramic material based on spinel structure and preparation method and application thereof | |
| KR20130047534A (en) | Solid oxide fuel cell and solid oxide electrolysis cell including ni-ysz fuel(hydrogen) electrode, and fabrication method thereof | |
| CN108390087B (en) | Composite solid electrolyte and preparation method thereof | |
| CN101465428B (en) | Method for improving solid-oxide fuel battery performance | |
| Yoon et al. | Characteristics of nano La0. 6Sr0. 4Co0. 2Fe0. 8O3− δ-infiltrated La0. 8Sr0. 2Ga0. 8Mg0. 2O3− δ scaffold cathode for enhanced oxygen reduction | |
| Zhang et al. | Modification of electrocatalytic activity of BaCe0. 40Sm0. 20Fe0. 40O3− δ with Co3O4 as cathode for proton-conducting solid oxide fuel cell | |
| CN102208662A (en) | Rare-earth element-doped BaFeO3-delta-based ABO3 type perovskite fuel cell cathode material and application thereof | |
| CN116082028B (en) | Proton ceramic fuel cell anode material, preparation method and application thereof in direct ammonia fuel cell | |
| US11342564B2 (en) | Three-dimensional architectured anode, a direct carbon fuel cell including the three-dimensional architectured anode, and related methods | |
| CN112952171B (en) | Barium cerate substrate sub-conductor-based integrated fully-symmetrical solid oxide fuel cell electrode material and preparation and application thereof | |
| CN102593467B (en) | High-conductivity double-perovskite-type anode material and preparation method thereof | |
| KR20100108955A (en) | Cathode material for solid oxide fuel cell and manufacturing method of the same | |
| Peng et al. | A promising Ruddlesden–Popper oxide cathode for both proton-conducting and oxygen ionic-conducting solid oxide fuel cells | |
| CN101510612A (en) | Method for preparing stephanoporate anode support body using paper fabric a pore-forming agent | |
| CN111244515B (en) | Perovskite type LaNiO containing calcium3Composite electrolyte, fuel cell and preparation method thereof | |
| CN103227332A (en) | Cathode material for medium temperature solid oxide fuel battery, and preparation thereof | |
| CN110336041B (en) | Ruthenium-nickel composite electrode and preparation method and application thereof | |
| Chen et al. | Cycling performance and interface stability research of tubular protonic reversible solid oxide cells with air electrodes by different manufacturing processes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210208 Address after: 215400 No.6 Liangfu Road, Chengxiang Town, Taicang City, Suzhou City, Jiangsu Province Patentee after: Zhongke sikas (Suzhou) Technology Development Co.,Ltd. Address before: 200050 No. 1295 Dingxi Road, Shanghai Patentee before: SHANGHAI INSTITUTE OF CERAMICS, CHINESE ACADEMY OF SCIENCES |
|
| TR01 | Transfer of patent right |