CN106816615A - A kind of new middle low temperature SOFC electrolytes and preparation method thereof - Google Patents
A kind of new middle low temperature SOFC electrolytes and preparation method thereof Download PDFInfo
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- CN106816615A CN106816615A CN201611058882.2A CN201611058882A CN106816615A CN 106816615 A CN106816615 A CN 106816615A CN 201611058882 A CN201611058882 A CN 201611058882A CN 106816615 A CN106816615 A CN 106816615A
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- low temperature
- middle low
- gel
- citric acid
- ethylene glycol
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- 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
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
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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
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Abstract
A kind of middle low temperature SOFC electrolytes have been directly obtained using the auto-combustion method of collosol and gel one.Formation of the pH value of the consumption and precursor solution of citric acid and ethylene glycol to colloidal sol and gel has a great impact.Citric acid and silester it is mixed under obtain uniform colloidal sol and gel, silicon and lanthanum is reached uniform mixing on a molecular scale.The mol ratio of nitrate anion and fuel citric acid and ethylene glycol is the key factor for influenceing spontaneous combustion reaction in reaction system.The powder of the synthesis by self-combustion of collosol and gel one has single-phase apatite-type crystal structure, and particle size is about 100 ~ 300nm, specific surface area for 5.40 ~ 5.60m2/g.Powder has good sintering activity, and density is can obtain when 10h is sintered for 1500 DEG C for 4.92 ~ 4.80 g/cm3Ceramic sintered bodies, this sintered body 800 DEG C electrical conductivity be 2 × 10s/cm.
Description
Technical field
The present invention relates to Material Field, and in particular to a kind of middle low temperature SOFC electrolytes and preparation method thereof.
Technical background
The middle low temperature of SOFC (SOFC) is the inexorable trend of SOFC commercialized developments, and in middle low temperature
Solid electrolyte material with oxygen ionic conductivity high is to realize the crucial of low temperature in SOFC therefore, Recent study and
The Novel electrolytic material explored suitable for middle low temperature SOFC has turned into one of the study hotspot in SOFC fields, wherein with low work
Changing can receive people's extensive concern with the apatite-type lanthanum silicate system oxide of oxygen ionic conductivity high.
At present, the powder needed for preparing the lanthanum silicate electrolyte with apatite structure is mostly by conventional high-temperature solid phase
Reaction method synthesis is obtained, and its process is ground often with lanthana and silica as raw material by mechanical mixture, then anti-through high temperature solid-state
Target product should be obtained however, incomplete, the high-temperature solid phase reaction method conjunction of the inhomogeneities and solid phase reaction due to mechanical mixture
The generation of insulation phase La2Si207 is often accompanied by during into lanthanum silicate, the performance of electrolyte is have impact on additionally, lanthanum silicate powder belongs to
In hard-to-sinter material, with the powder of solid reaction process preparation because particle is big and size distribution is uneven, generally require 1700
Sintering could meet the requirement of compactness for a long time more than DEG C, and very big being stranded is brought to preparations of high-quality electrolyte
Difficult is unfavorable for common burning of the electrolyte with other battery components simultaneously, also.Therefore, how to synthesize and prepare sintering activity ultra-fine, high
Single-phase lanthanum silicate powder body material turned into lanthanum silicate electrolyte preparation important step.
The content of the invention
Purpose of the invention is to provide a kind of middle low temperature SOFC electrolytes and preparation method thereof.
In order to solve problem above, adopted the technical scheme that：
A kind of middle low temperature SOFC electrolytes, it is characterised in that the raw material comprising following molar fraction part：Lanthanum nitrate 10 ~
18%, silester 5 ~ 15%, citric acid 20 ~ 40%, ethylene glycol 40 ~ 60%.
Preferably, a kind of middle low temperature SOFC electrolytes, it is characterised in that the raw material comprising following molar fraction part：
Lanthanum nitrate 13 ~ 16%, silester 10 ~ 15%, citric acid 25 ~ 30%, ethylene glycol 45 ~ 50%.
Preferably, a kind of middle low temperature SOFC electrolytes, it is characterised in that the raw material comprising following molar fraction part：
Lanthanum nitrate 15.5%, silester 12%, citric acid 26%, ethylene glycol 46.5%.
Preferably, ammonium nitrate is added in gel rubber system, as the oxidant needed for combustion system, makes what spontaneous combustion was reacted
Degree, thermal discharge, ignition temperature are improved.
Preferably, gel rubber system is being prepared, using absolute ethyl alcohol as solvent, is preventing intermediate products from hydrolyzing.
A kind of preparation method of middle low temperature SOFC electrolytes, comprises the following steps：
（1）Good various raw materials are weighed in portions by mole；
（2）Citric acid and ethylene glycol are dissolved in appropriate ethanol；
（3）Silester is added, stirring obtains transparent solution；
（4）Lanthanum nitrate is added, 80 ~ 100 DEG C are heated to, stirring to ammonium nitrate is completely dissolved；
（5）Add ammonium nitrate；
（6）It is added dropwise between ammoniacal liquor regulation PH to 2.5 ~ 2.9；
（7）Heating stirring extremely forms colloidal sol and gel；
（8）Colloidal sol and gel are dried in 80 DEG C of baking ovens；
（9）Gained xerogel is placed in Muffle furnace, 350 DEG C of generations of induction spontaneous combustion process are heated to, loose powder is obtained
Last shape product.
Beneficial effect
Middle low temperature SOFC electrolytes made by the present invention, powder has single-phase apatite-type crystal structure, particle size
About 150 ~ 300nm, specific surface area are 5.54m2/g.Powder has good sintering activity, in 1500 DEG C of sintering knot 10h
The ceramic sintered bodies that relative density is 90% are can obtain, this sintered body is 2 × 10 in 800 DEG C of electrical conductivity-3S/cm, conductance activation
Can be 0.73eV.
Specific embodiment
Below by specific embodiment, technical scheme is described in further detail, but the present invention is not limited
In these examples.
Embodiment one
（1）Following raw material are taken in portions by mole：Lanthanum nitrate 15.5%, silester 12%, citric acid 26%, ethylene glycol
46.5%；
（2）Citric acid and ethylene glycol are dissolved in appropriate ethanol；
（3）Silester is added, stirring obtains transparent solution；
（4）Lanthanum nitrate is added, 80 ~ 100 DEG C are heated to, stirring to ammonium nitrate is completely dissolved；
（5）Add ammonium nitrate；
（6）It is added dropwise between ammoniacal liquor regulation PH to 2.5 ~ 2.9；
（7）Heating stirring extremely forms colloidal sol and gel；
（8）Colloidal sol and gel are dried in 80 DEG C of baking ovens；
（9）Gained xerogel is placed in Muffle furnace, 350 DEG C of generations of induction spontaneous combustion process are heated to, loose powder is obtained
Last shape product.
The powdery product that will be obtained carries out electron-microscope scanning, observes the granule size of powder granule, and by vacuum outgas
After test specific surface area, after being sintered 10h at 1500 DEG C, test density, electrical conductivity.
Embodiment two
（1）Following raw material are taken in portions by mole：Lanthanum nitrate 10%, silester 15%, citric acid 25%, ethylene glycol 50%；
（2）Citric acid and ethylene glycol are dissolved in appropriate ethanol；
（3）Silester is added, stirring obtains transparent solution；
（4）Lanthanum nitrate is added, 80 ~ 100 DEG C are heated to, stirring to ammonium nitrate is completely dissolved；
（5）Add ammonium nitrate；
（6）It is added dropwise between ammoniacal liquor regulation PH to 2.5 ~ 2.9；
（7）Heating stirring extremely forms colloidal sol and gel；
（8）Colloidal sol and gel are dried in 80 DEG C of baking ovens；
（9）Gained xerogel is placed in Muffle furnace, 350 DEG C of generations of induction spontaneous combustion process are heated to, loose powder is obtained
Last shape product.
The powdery product that will be obtained carries out electron-microscope scanning, observes the granule size of powder granule, and by vacuum outgas
After test specific surface area, after being sintered 10h at 1500 DEG C, test density, electrical conductivity.
Embodiment three
（1）Following raw material are taken in portions by mole：Lanthanum nitrate 18%, silester 12%, citric acid 30%, ethylene glycol 40%；
（2）Citric acid and ethylene glycol are dissolved in appropriate ethanol；
（3）Silester is added, stirring obtains transparent solution；
（4）Lanthanum nitrate is added, 80 ~ 100 DEG C are heated to, stirring to ammonium nitrate is completely dissolved；
（5）Add ammonium nitrate；
（6）It is added dropwise between ammoniacal liquor regulation PH to 2.5 ~ 2.9；
（7）Heating stirring extremely forms colloidal sol and gel；
（8）Colloidal sol and gel are dried in 80 DEG C of baking ovens；
（9）Gained xerogel is placed in Muffle furnace, 350 DEG C of generations of induction spontaneous combustion process are heated to, loose powder is obtained
Last shape product.
The powdery product that will be obtained carries out electron-microscope scanning, observes the granule size of powder granule, and by vacuum outgas
After test specific surface area, after being sintered 10h at 1500 DEG C, test density, electrical conductivity.
Example IV
The present embodiment using the middle low temperature SOFC electrolytes prepared by the method for embodiments of the invention 1 ~ 3 to being tested.
The performance test results of the present embodiment are as follows：
Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than to the scope of the present invention
Limitation, although being elaborated to the present invention with reference to preferred embodiment, it will be understood by those within the art that, can
Modified or equivalent with to technical scheme, without deviating from the spirit and scope of technical solution of the present invention.
Claims (6)
1. a kind of new middle low temperature SOFC electrolytes, it is characterised in that the raw material comprising following molar fraction part：Lanthanum nitrate
10 ~ 18%, silester 5 ~ 15%, citric acid 20 ~ 40%, ethylene glycol 40 ~ 60%.
2. new middle low temperature SOFC electrolytes of one kind according to claim 1, it is characterised in that comprising following mole
Raw material in portions：Lanthanum nitrate 13 ~ 16%, silester 10 ~ 15%, citric acid 25 ~ 30%, ethylene glycol 45 ~ 50%.
3. new middle low temperature SOFC electrolytes of one kind according to claim 1, it is characterised in that comprising following mole
Raw material in portions：Lanthanum nitrate 15.5%, silester 12%, citric acid 26%, ethylene glycol 46.5%.
4. a kind of new middle low temperature SOFC electrolytes according to claim 1 or 2 or 3, it is characterised in that using molten
Glue gel-auto-combustion method method is prepared, and comprises the steps of：
（1）Good various raw materials are weighed in portions by mole；
（2）Citric acid and ethylene glycol are dissolved in appropriate ethanol；
（3）Silester is added, stirring obtains transparent solution；
（4）Lanthanum nitrate is added, 80 ~ 100 DEG C are heated to, stirring to ammonium nitrate is completely dissolved；
（5）Add ammonium nitrate；
（6）It is added dropwise between ammoniacal liquor regulation PH to 2.5 ~ 2.9；
（7）Heating stirring extremely forms colloidal sol and gel；
（8）Colloidal sol and gel are dried in 80 DEG C of baking ovens；
（9）Gained xerogel is placed in Muffle furnace, 350 DEG C of generations of induction spontaneous combustion process are heated to, loose powder is obtained
Last shape product.
5. a kind of new middle low temperature SOFC electrolytes according to claim 1 or 2 or 3, it is characterised in that addition nitre
Sour ammonium is the oxidant of combustion system.
6. a kind of new middle low temperature SOFC electrolytes according to claim 1 or 2 or 3, it is characterised in that use nothing
Water-ethanol is used as solvent.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611058882.2A CN106816615A (en) | 2016-11-28 | 2016-11-28 | A kind of new middle low temperature SOFC electrolytes and preparation method thereof |
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| CN201611058882.2A CN106816615A (en) | 2016-11-28 | 2016-11-28 | A kind of new middle low temperature SOFC electrolytes and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109264729A (en) * | 2018-11-27 | 2019-01-25 | 烟台工程职业技术学院 | A kind of preparation facilities and method of lanthanum silicate nano-powder |
| CN112928317A (en) * | 2019-12-05 | 2021-06-08 | 宁波行殊新能源科技有限公司 | Preparation method of cerium oxide-based electrolyte material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101572322A (en) * | 2009-06-04 | 2009-11-04 | 武汉工程大学 | Rare-earth doped lanthanum silicate oxyapatite solid electrolyte and preparation method thereof |
| CN103199287A (en) * | 2013-04-14 | 2013-07-10 | 北京科技大学 | Method for promoting densification of silicon-based apatite through doping Cu |
| CN103346342A (en) * | 2013-06-19 | 2013-10-09 | 武汉工程大学 | Aluminum-silicon-doped apatite-type lanthanum silicate solid electrolyte, and preparation method thereof |
| CN104201408A (en) * | 2014-07-31 | 2014-12-10 | 北京科技大学 | Cu-doped silicon-based apatite electrolyte material and preparation method of Cu-doped silicon-based apatite electrolyte material |
-
2016
- 2016-11-28 CN CN201611058882.2A patent/CN106816615A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101572322A (en) * | 2009-06-04 | 2009-11-04 | 武汉工程大学 | Rare-earth doped lanthanum silicate oxyapatite solid electrolyte and preparation method thereof |
| CN103199287A (en) * | 2013-04-14 | 2013-07-10 | 北京科技大学 | Method for promoting densification of silicon-based apatite through doping Cu |
| CN103346342A (en) * | 2013-06-19 | 2013-10-09 | 武汉工程大学 | Aluminum-silicon-doped apatite-type lanthanum silicate solid electrolyte, and preparation method thereof |
| CN104201408A (en) * | 2014-07-31 | 2014-12-10 | 北京科技大学 | Cu-doped silicon-based apatite electrolyte material and preparation method of Cu-doped silicon-based apatite electrolyte material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109264729A (en) * | 2018-11-27 | 2019-01-25 | 烟台工程职业技术学院 | A kind of preparation facilities and method of lanthanum silicate nano-powder |
| CN112928317A (en) * | 2019-12-05 | 2021-06-08 | 宁波行殊新能源科技有限公司 | Preparation method of cerium oxide-based electrolyte material |
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Application publication date: 20170609 |