CN101465428B - Method for improving solid-oxide fuel battery performance - Google Patents
Method for improving solid-oxide fuel battery performance Download PDFInfo
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- CN101465428B CN101465428B CN2009100451128A CN200910045112A CN101465428B CN 101465428 B CN101465428 B CN 101465428B CN 2009100451128 A CN2009100451128 A CN 2009100451128A CN 200910045112 A CN200910045112 A CN 200910045112A CN 101465428 B CN101465428 B CN 101465428B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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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
SOFC (SOFC) works in high temperature (650～1000 ℃); Can be directly changed into electric energy to the chemical energy of fuel; System effectiveness high (＞70%), environmental pollution is low, and 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 SOFC generally includes: the powder that (1) will prepare battery is mixed in certain organic solvent, and Ball milling is even, processes slurry; (2) this slurry is adopted certain method, process the biscuit of battery like curtain coating etc.; (3) with this biscuit at high temperature, as 1400 the degree above sintering; (4) battery that conforms with designing requirement is polished, is engraved as to burned biscuit.The preparation SOFC 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 SOFC is required, in electrode the part of responsible 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 (like hydrogen molecule, H
2) with conduct the ion that comes mutually from ionic conduction (like oxonium ion O
2-) combine, 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 there is a kind of electrode material can possess ionic conduction ability and electron conduction ability simultaneously 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 quilt extensively adopts 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 State Ionics, 134 (2000) 3-20], Ni is the electron conduction phase, YSZ is the ionic conduction phase.When SOFC just baked, its anode was the 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 in anode, introducing CeO 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 the preparation process; Whole anode is very fine and close, is 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 (like 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 SOFC, 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 in anode of solid oxide fuel cell, introduce the short-cut method of the better material of performance, this method can improve the performance of SOFC significantly.
A kind of method that improves solid-oxide fuel battery performance is characterized in that improving the electrical property of battery through in the anode of SOFC, introducing material.Its step comprises: (1) preparation waits to introduce the precursor solution of material; (2) with the anode high temperature reduction of SOFC; (3) battery electrode after will reducing is immersed in the solution of step 1 preparation, in the anode of battery, will be dipped into the presoma of waiting to introduce material; (4) the battery electrode heat treatment after will flooding in heat treatment process, decomposes the presoma of immersion, and generations needs the material of introducing;
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 gets into 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; Like hydrogen or carbon monoxide.
Description of drawings
Fig. 1 is the sketch map 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
In the anode of SOFC, immerse cerium oxide, improve its performance, concrete steps are following:
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 compared through the performance of the SOFC of dipping with not through the discharge performance of the SOFC of dipping, can find, process oxide impregnation cerium, the performance of SOFC obtained significant raising.
Immersion is different from the cerium oxide concentration shown in the embodiment 1 in the anode of SOFC, improves its performance, and concrete steps are following:
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 in the anode of SOFC, immerses cerium oxide is identical with embodiment 2, but last heat treatment temperature is different, and to improve its performance, concrete steps are following:
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
In the anode of SOFC, immerse cerium oxide, improve its performance, concrete steps are following:
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
In the anode of SOFC, immerse cerium oxide, improve its performance, concrete steps are following:
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
In the anode of SOFC, immerse SDC (SDC refers to samarium (Sm) doping of cerium oxide (CeO), down together), improve its performance, concrete steps are following:
The first step, stoichiometric coefficient proportioning is as required used cerous nitrate and samaric nitrate compound concentration samarium doping of cerium oxide (SDC) solution as 0.5M, and 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 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 SOFC obtained bigger raising.
Embodiment 7
In the anode of SOFC, immerse SDC (SDC refers to samarium (Sm) doping of cerium oxide (CeO), down together), improve its performance, concrete steps are following:
The first step, stoichiometric coefficient proportioning is as required used cerous nitrate and samaric nitrate compound concentration samarium doping of cerium oxide (SDC) solution as 0.5M, and 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 (5)
1. a method that improves solid-oxide fuel battery performance is characterized in that in the NiO-YSZ of SOFC anode, introducing material, the steps include:
(a) preparation oxidation-containing cerium or mix the solution of samarium cerium oxide precursor body, 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.
2. by the described a kind of method that improves solid-oxide fuel battery performance of claim 1, that it is characterized in that high temperature reduction uses among the step b is H
2Or CO atmosphere.
3. by the described a kind of method that improves solid-oxide fuel battery performance of claim 1, it is characterized in that the time of step c dipping is 1～2 minute.
4. by the described a kind of method that improves solid-oxide fuel battery performance of claim 1, it is characterized in that the steps d heat treatment time is 0.5～1.5 hour.
5. by the described a kind of method that improves solid-oxide fuel battery performance of claim 1, the molar concentration rate of molar concentration and principal phase Ce ion that it is characterized in that samarium doped ion among the step a is between 1: 5～1: 1.
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| 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 |
| 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 |
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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 |