CN1150647C - Composite ceramic material for middle-temperature oxide fuel cell - Google Patents
Composite ceramic material for middle-temperature oxide fuel cell Download PDFInfo
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- CN1150647C CN1150647C CNB001122282A CN00112228A CN1150647C CN 1150647 C CN1150647 C CN 1150647C CN B001122282 A CNB001122282 A CN B001122282A CN 00112228 A CN00112228 A CN 00112228A CN 1150647 C CN1150647 C CN 1150647C
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- Prior art keywords
- oxide
- lithium
- carbonate
- ceria
- fuel cell
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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 relates to an electrolyte material of a solid fuel cell, which is characterized in that the electrolyte material is a two-phase or multiphase composite material prepared by mixing cerium dioxide or ion doping cerium dioxide and an inorganic salt. The present invention has the advantages that the electrolyte material greatly lowers the manufacturing cost of the solid fuel cell; compared with the traditional solid electrolyte material, the electrolyte material of the present invention enhances a plurality of orders of the magnitude of electric conductivity and enhances times of fuel cell efficiency; the electrolyte material provides a good business opportunity for the development of abundant rare earth resources in China.
Description
Technical field
The present invention relates to a kind of electrolyte of solid fuel cell.
Background technology
Solid fuel cell research was since the zirconic high temperature oxygen ionic conduction of this special discovery of energy in 1900, and the thirties, scientist just carried out the research based on the solid fuel cell of Zirconia electrolytic.Traditional solid fuel cell is subjected to the restriction of doped zirconia material, and needs nearly 1000 ℃ high temperature; Use high-temperature material, the price height.In order to reduce cost, the research tendency of solid fuel cell is a temperatureization in realizing in the world at present, and promptly temperature range is: 400-800 ℃.
Summary of the invention
The objective of the invention is to: provide a kind of and can reduce the Solid Oxide Fuel Cell cost greatly, and improve the novel composite ceramic electrolyte of the intermediate temperature fuel cell of its fuel battery performance simultaneously.
The technical solution that realizes above-mentioned purpose is such.
In the composite ceramic material of warm oxide fuel cell, comprising: ceria or ion doping ceria is characterized in that: it is that raw material by following component mixes, or obtains at short time sintering below 700 ℃:
Ceria or ion doping ceria 55%～85%,
More than one inorganic salts or oxyhydroxide 1%～45%,
More than one other oxide or doping oxide 0～45%;
Wherein said inorganic salts are: lithium chloride, sodium chloride, strontium chloride, lithium fluoride, calcirm-fluoride, barium fluoride, lithium carbonate, sodium carbonate, potash, calcium carbonate, magnesium carbonate, brium carbonate, strontium carbonate, cesium nitrate, rubidium nitrate, lithium sulfate, magnesium sulfate, calcium sulfate, lithium phosphate, calcium phosphate, potassium phosphate;
Wherein said oxyhydroxide is: lithium hydroxide, NaOH, potassium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide;
Wherein said other oxide is: bismuth oxide, aluminium oxide, zirconia, silica, calcium oxide, strontium oxide strontia, barium monoxide, magnesium oxide, samarium oxide, gadolinium oxide, yittrium oxide, scandium oxide, gallium oxide, lanthana;
Wherein said doping oxide is the oxide that above-mentioned oxide forms through ion doping.
The present invention has the beneficial effect of following several respects:
One, the electrolyte of Solid Oxide Fuel Cell of the present invention is compared with traditional doped zirconia electrolyte with its cost of making solid fuel cell and is reduced greatly, makes solid fuel cell realize that low-cost commercialization becomes possibility.
Two, the electrolyte of Solid Oxide Fuel Cell of the present invention has the conductivity than traditional high several magnitude of doped zirconia electrolyte under 400 ℃ to 600 ℃ medium temperature condition, promptly conductivity is 0.4-1.0Scm
-1Simultaneously, the also high several times of its fuel cell efficiency, operand power is 300-600mWcm
-2
Three, China has extremely abundant rare earth resources, and the invention of the electrolyte of intermediate temperature solid oxide fuel cell is for the exploitation of the rich rare earth resources of China provides good business opportunity.
Description of drawings
Fig. 1 is the X-x ray diffration pattern x of material of the present invention,
Fig. 2 is the ionic conductivity-temperature curve comparison diagram of material of the present invention and traditional material,
Fig. 3 is current density and cell voltage characteristic curve diagram.
Embodiment
Below by embodiment, in conjunction with the accompanying drawings the present invention is done to describe further.
The present invention uses ceria, or ceria oxide powder that mixes and the evenly mixing according to a certain percentage of inorganic salts powder, just can be used as electrolyte after the grinding and is used for fuel cell.Compound also can use through grinding after calcining.Also a certain proportion of other oxides can be added on the above-mentioned material basis as required, as aluminium oxide, zirconia, silica, magnesium oxide, calcium oxide, bismuth oxide.
Embodiment 1
Get the ceria 84% (2 gram) of doping, as Gd-CeO,
Lithium carbonate 16% (0.38 gram),
It is fully mixed, grinds, can use; Or materials mixed put into Muffle furnace, and 680 ℃ of calcinings 1 hour, take out, grind standby.
Embodiment 2
Get the ceria 84% (2 gram) of doping,
Lithium carbonate 6% (0.14 gram),
Sodium carbonate 20.5% (0.2),
Concrete operations are the same.
Get the ceria 73.5% (1 gram) of doping,
Lithium carbonate 6% (0.14),
Potash 20.5% (0.22),
Concrete operations are the same.
Get the ceria 74.6% (2 gram) of doping,
Lithium chloride 22.4% (0.6 gram),
Concrete operations are the same.
Get the ceria 66.7% (1 gram) of doping,
NaOH 33.3% (0.15),
Concrete operations are the same.
Embodiment 6
Get doping of cerium oxide oxide 87.7% (2 gram),
Lithium hydroxide 4.4% (0.1 gram),
Sodium carbonate 7.9% (0.18 gram),
Concrete operations are the same.
Embodiment 7
Get the ceria oxide 85.5% (2 gram) of doping,
Lithium carbonate 6% (0.14),
Sodium carbonate 8.5% (0.2)
Concrete operations are the same.
Embodiment 8
Get the ceria oxide 55.6% (1.5 gram) of doping
Aluminium oxide 29.6% (0.8)
Lithium carbonate 6.7% (0.18)
Sodium carbonate 8.1% (0.22)
Concrete operations are the same.
Embodiment 9
Get the ceria oxide 55.6% (1.5) of doping
Aluminium oxide 29.6% (0.8)
Lithium carbonate 6.7% (0.18)
Sodium carbonate 8.1% (0.22)
Concrete operations are the same.
Embodiment 10
Get the ceria oxide 70% of doping
Lithium carbonate 10%
Calcium carbonate 8%
Zirconia 6%
Calcium oxide 6%
Concrete operations are the same.
Embodiment 11
Get the ceria oxide 65% of doping
Lithium carbonate 20%
Concrete operations are the same.
Embodiment 12
Get the ceria oxide 60% of doping
Lithium carbonate 20%
Brium carbonate 8%
Alundum (Al 12%
Concrete operations are the same.
Embodiment 13
Get the ceria oxide 60% of doping
Lithium carbonate 16%
Strontium carbonate 8%
Bismuth oxide 8%
Calcium oxide 8%
Concrete operations are the same.
Embodiment 14
Get the ceria oxide 50% of doping
Lithium sulfate 25%
NaOH 10%
Alundum (Al 5%
Concrete operations are the same.
Embodiment 15
Get the ceria oxide 55% of doping
Lithium sulfate 20%
Calcium sulfate 10%
Zirconia 10%
Concrete operations are the same.
Embodiment 16
Get the ceria oxide 55% of doping
Cesium nitrate 15%
Rubidium nitrate 10%
Alundum (Al 10%
Concrete operations are the same.
Embodiment 17
Get the ceria oxide 55% of doping
NaOH 15%
Calcium hydroxide 10%
Alundum (Al 10%
Concrete operations are the same.
Embodiment 18
Get the ceria oxide 60% of doping
Lithium phosphate 20%
Calcium phosphate 10%
Concrete operations are the same.
Embodiment 19
Get the ceria oxide 55% of doping
Lithium phosphate 10%
Potassium phosphate 15%
Zirconia 15%
Concrete operations are the same.
Embodiment 20
Get the ceria oxide 60% of doping
Lithium fluoride 15%
Calcirm-fluoride 10%
Alundum (Al 10%
Concrete operations are the same.
Embodiment 21
Get the ceria oxide 55% of doping
Lithium fluoride 15%
Barium fluoride 10%
Alundum (Al 15%
Concrete operations are the same.
Embodiment 22
Get the ceria oxide 55% of doping
Sodium chloride 15%
Strontium chloride 10%
Alundum (Al 15%
Concrete operations are the same.
Embodiment 23
Get the ceria oxide 50% of doping
Lithium carbonate 20%
Lithium chloride 10%
Alundum (Al 15%
Concrete operations are the same.
Embodiment 24
Get pure ceria powder 58.8% (5 gram), immerse 0.03M nitric acid, and add 0.03MY (NO
3) 3 solution, fully stir.Add lithium carbonate 23.5% (2 gram) and sodium carbonate 17.7% (1.5 gram) stirring again, mix.After fully mixing, put into baking oven, 150 ℃ are baked to drying, grind standby.Put into 680 ℃ of calcinings of Muffle furnace 1 hour, take out and grind, 820 ℃ of calcinings 1-2 hour, take out again, grind standby.
This material only gets final product by the ground and mixed of machinery; But, the material that obtains through calcining has better ceramics strength than the material of not calcining.
Can obviously see by Fig. 1, separately the ceria oxide of self-existent doping and sodium chloride mutually, alundum (Al does not have the reason of its diffraction maximum to be in the drawings: one exists mutually with non-setting; Two its content can not be reflected very little.Fig. 1 result shows two-phase or multiphase compound feature of this material.
Figure 2 shows that GDC-Li
2CO
3-Na
2CO
3Composite ceramics its ionic conductivity under 400～600 ℃ middle temperature is 0.4-1Scm
-1, and traditional yttrium-stabile zirconium dioxide (YSZ) is lower than 10 in the time of 600 ℃
-5Scm
-1, do not have practical value.Even pure carbon hydrochlorate composite electrolyte (GDC) also has only 10
-2Scm
-1Following ionic conductivity, and GDC is unsettled in hydrogen, application difficult.
Fuel battery performance shown in Figure 3 is 300～600mWcm 400～650 ℃ middle temperature operand power
-2, (be 200mWcm at about 1000 ℃ usually than the high several times of conventional high-temperature Solid Oxide Fuel Cell (SOFC)
-2).
Novel composite ceramic electrolyte of the present invention, as the composite electrolyte of GDC-carbonate based, fuel battery assembled can steady in a long-term be generated electricity under heavy load power.
Claims (1)
1, the composite ceramic material of middle temperature oxide fuel cell comprises: ceria or ion doping ceria is characterized in that: it is to be formed by the simple and mechanical ground and mixed of the raw material of following component, or obtains at short time sintering below 700 ℃:
Ceria or ion doping ceria 55%～85%,
More than one inorganic salts or oxyhydroxide 1%～45%,
More than one other oxide or doping oxide 0～45%;
Wherein said inorganic salts are: lithium chloride, sodium chloride, strontium chloride, lithium fluoride, calcirm-fluoride, barium fluoride, lithium carbonate, sodium carbonate, potash, calcium carbonate, magnesium carbonate, brium carbonate, strontium carbonate, cesium nitrate, rubidium nitrate, lithium sulfate, magnesium sulfate, calcium sulfate, lithium phosphate, calcium phosphate, potassium phosphate;
Wherein said oxyhydroxide is: lithium hydroxide, NaOH, potassium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide;
Wherein said other oxide is: bismuth oxide, aluminium oxide, zirconia, silica, calcium oxide, strontium oxide strontia, barium monoxide, magnesium oxide, samarium oxide, gadolinium oxide, yittrium oxide, scandium oxide, gallium oxide, lanthana;
Wherein said doping oxide is the oxide that above-mentioned oxide forms through ion doping.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001122282A CN1150647C (en) | 2000-02-16 | 2000-04-21 | Composite ceramic material for middle-temperature oxide fuel cell |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00112085.9 | 2000-02-16 | ||
| CN00112085 | 2000-02-16 | ||
| CNB001122282A CN1150647C (en) | 2000-02-16 | 2000-04-21 | Composite ceramic material for middle-temperature oxide fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1269613A CN1269613A (en) | 2000-10-11 |
| CN1150647C true CN1150647C (en) | 2004-05-19 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB001122282A Expired - Fee Related CN1150647C (en) | 2000-02-16 | 2000-04-21 | Composite ceramic material for middle-temperature oxide fuel cell |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2400486B (en) * | 2003-04-09 | 2006-05-10 | Ceres Power Ltd | Densification of ceria based electrolytes |
| CN100466348C (en) * | 2004-06-22 | 2009-03-04 | 旭硝子株式会社 | Liquid composition, method for producing the same, and method for producing membrane electrode assembly for solid polymer fuel cell |
| CN100336256C (en) * | 2005-06-17 | 2007-09-05 | 清华大学 | Electrolyte composed of zinc doped cerium oxide and inorganic salt in use for fuel cell of solid oxide in low temperature |
| CN103378364A (en) * | 2012-04-13 | 2013-10-30 | 上海中聚佳华电池科技有限公司 | Composite electrolyte material based on zirconium oxide based oxide |
| CN104852070B (en) * | 2015-06-02 | 2017-06-06 | 福州大学 | A kind of solid-oxide fuel battery electrolyte and its preparation method and application |
| CN105140526B (en) * | 2015-07-22 | 2017-09-29 | 中国地质大学（武汉） | A kind of preparation method of fuel cell and fuel cell |
| KR102169225B1 (en) * | 2016-08-08 | 2020-10-23 | 모리무라 에스오에프씨 테크놀로지 가부시키가이샤 | Electrochemical reaction single cell and electrochemical reaction cell stack |
| CN106207238A (en) * | 2016-09-30 | 2016-12-07 | 福州大学 | A kind of molten salts compound intermediate temperature solid oxide fuel cell electrolyte |
| CN110600778B (en) * | 2018-06-12 | 2023-03-10 | 阜阳师范学院 | MgO and Y 2 O 3 Double-doped ZrO 2 -alkali metal salt complex and process for producing the same |
| CN109437903B (en) * | 2018-12-20 | 2022-01-18 | 云南大学 | Method for improving sintering activity of doped cerium oxide electrolyte |
| CN110165269B (en) * | 2019-05-28 | 2022-06-24 | 盐城市新能源化学储能与动力电源研究中心 | Solid oxide fuel cell composite electrolyte and preparation method thereof |
| CN113410497B (en) * | 2021-06-17 | 2022-10-11 | 华能国际电力股份有限公司 | Electrolyte of molten carbonate fuel cell, fuel cell and preparation method |
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