CN108232303A - Oxygen ion conduction intermediate temperature solid oxide fuel cell electrolyte preparation method - Google Patents
Oxygen ion conduction intermediate temperature solid oxide fuel cell electrolyte preparation method Download PDFInfo
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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- H01M10/0568—Liquid materials characterised by the solutes
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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
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a kind of oxygen ion conduction intermediate temperature solid oxide fuel cell electrolyte preparing methods, belong to the preparation field of cell electrolyte.The present invention uses Sr (NO3)2、KNO3, tetraethyl orthosilicate, GeO2It is primary raw material with citric acid, the electrolyte is made through sol-gel combustion method.Conductivity reaches 0.021S/cm to electrolyte produced by the present invention at 700 DEG C under dry air atmosphere, has the characteristics that largely effective reduction temperature of fuel cell, is suitble to be used in intermediate temperature solid oxide fuel cell electrolyte.
Description
Technical field
The invention belongs to the preparation fields of fuel-cell electrolyte, and in particular to a kind of oxygen ion conduction medium temperature solid oxidation
The preparation method of object fuel-cell electrolyte.
Background technology
The energy is the main resource during human development, it has food, clothing, housing and transportation of the mankind etc. decisive
Influence.Main energy sources in the world are still with fossil energy at present（Coal, natural gas, oil）Based on.Due to conventional fossil
The deposit of the energy is limited and the pollution of caused global ecological environment, countries in the world take one after another practical measures environmental protection,
It taps a new source of energy.China is an energy-consuming big country, and energy shortage is particularly problematic, is more utilized there is an urgent need to develop efficient
The relevant technologies and method of fuel.
Solid oxide fuel cell（SOFC）The chemical energy that can be will be present in fuel and oxidant is converted into
Electric energy.The difference lies in its fuel and oxidant not to be previously stored inside battery for fuel cell and conventional batteries, and
It is from external supply, as long as constantly providing it fuel and oxidant, it is possible to constantly generate electricity.Due to reacting
It is not related to burning in journey, the chemical energy in fuel efficiently can be changed into electric energy by it, while substantially reduce the row of pollutant
It puts.The operating temperature of SOFC is at 500 DEG C ~ 1000 DEG C, and by-product is the heat and vapor of high-quality, in the situation of cogeneration
Under, capacity usage ratio is up to 80% or so, is a kind of energy resource system of clean and effective.Therefore, fuel cell is considered as 21 century
Most efficient, energy-saving and environmental protection the generation modes of future.
Traditional SOFC operating temperatures at 1000 DEG C or so, hot operation environment easily make electrode and electrolyte, electrode with
Interfacial reaction occurs between bipolar plates, causes the attenuation of battery performance, influences the service life of battery.Simultaneously also to sealing and connecting
The requirement that material proposition is just carved, greatly reduces the range of choice of material, seriously improves manufacture cost, constrain the business of SOFC
Change development.Therefore, the reduction of SOFC operating temperatures can be effectively reduced the cost of system and improve stability.For low temperature in realization
Change purpose, the novel solid electrolyte for needing research and probe oxygen ion conduction rate under middle cryogenic conditions high.The present invention's
Oxonium ion electrolyte can obtain high conductivity under the conditions of middle low-temperature working, can be used in so that satisfaction is required at present
The electrolyte of middle low temperature SOFC.
Invention content
It is an object of the invention in view of the shortcomings of the prior art, providing a kind of oxygen ion conduction medium temperature solid oxide fuel
The preparation method of cell electrolyte.Conductivity reaches electrolyte produced by the present invention at 700 DEG C under dry air atmosphere
0.021S/cm has the characteristics that largely effective reduction temperature of fuel cell.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of oxygen ion conduction intermediate temperature solid oxide fuel cell electrolyte preparation method, the chemical formula of the electrolyte are
Sr0.8K0.2Si0.5Ge0.5O2.9, preparation method specifically includes following steps：
（One）Sr0.8K0.2Si0.5Ge0.5O2.9Preparation：
1）By Sr0.8K0.2Si0.5Ge0.5O2.9Stoichiometric ratio weighs Sr (NO3)2、KNO3, tetraethyl orthosilicate (SiC8H12O8)、
GeO2, and be 1 by the molar ratio of metal cation and citric acid:1.5 weigh citric acid；
2）V (SiC by volume8H12O8):V(C2H5OH)=1:Tetraethyl orthosilicate is dissolved in absolute ethyl alcohol by 3；
3）By GeO2It adds in distilled water, stirring and condensing reflux 2h under the conditions of 100 DEG C of oil baths；
4）By Sr (NO3)2And KNO3It adds in distillation water dissolution and forms nitrate solution, citric acid is added in distillation water dissolution forms
Citric acid solution；
5）By step 2）Acquired solution is poured slowly into step 3）In acquired solution, 30min is stirred, is then slowly dropped into step 4）Institute
Nitrate solution is obtained, then instills citric acid solution, and the ammonium hydroxide that mass concentration is 15%-20% is added dropwise into solution, to adjust
It is 7 to save solution ph；
6）By step 5）Obtained mixed solution, which is put into magnetic stirring apparatus, is heated to 70 DEG C, is then maintained at 70 DEG C and continuously stirs
It mixes, and the ammonium hydroxide that mass concentration is 15%-20% is added in whipping process, the pH value of solution is made to be maintained at 7, until being formed solidifying
Glue；
7）Gel is moved into evaporating dish, is placed on electric furnace and heats, until self-propagating combustion, which occurs, forms fluffy oxidate powder
End；
8）Gained oxide powder is heated to 600 ± 10 DEG C of heat preservations 1 ± 0.1 hour to eliminate residual organic matter, Ran Hou
1000 ± 10 DEG C keep the temperature 10 ± 0.1 hours, and natural cooling forms Sr0.8K0.2Si0.5Ge0.5O2.9Powder；
（Two）The preparation of intermediate temperature solid oxide fuel cell electrolyte：
By step（One）Gained Sr0.8K0.2Si0.5Ge0.5O2.9Powder is put into mold, under the pressure of 200MPa, is pressed into circle
Disk is heated to 1050 ± 10 DEG C with 3 DEG C per minute of speed and keeps the temperature 10 ± 0.1 hours, obtains required electrolyte by piece
Disk.
The beneficial effects of the present invention are：The crystal structure of apatite-type SiGe base electrolyte belongs to hexagonal crystal system, it is
A kind of oxide of pure oxygen ion conductance has the features such as conductivity does not change with partial pressure of oxygen, do not change with atmosphere moisture.In
Low-temperature range, oxygen ionic conductivity are higher than traditional electrolyte matter.The present invention is prepared using sol-gal process with high oxonium ion
The Sr of conductivity0.8K0.2Si0.5Ge0.5O2.9Electrolyte is suitble to be used in intermediate temperature solid oxide fuel cell electrolyte.
Description of the drawings
Fig. 1 is Sr prepared by the present invention0.8K0.2Si0.5Ge0.5O2.9The XRD spectrum of powder.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited only to these embodiments.
Embodiment
（One）1mol Sr0.8K0.2Si0.5Ge0.5O2.9Preparation：
Weigh 0.8 mole of Sr (NO3)2：0.8 × 211.6299=169.303 grams
Weigh 0.2 mole of KNO3：0.2 × 101.10=20.22 grams
Weigh 0.5 mole of SiC8H12O8：0.5 × 208.33=104.165 grams
Weigh 0.5 mole of GeO2：0.5 × 104.63=52.315 grams
Weigh 3 moles of citric acid：3 × 210.14=630.42 grams
V (SiC by volume8H12O8):V(C2H5OH)=1:Tetraethyl orthosilicate is dissolved in absolute ethyl alcohol by 3；
By GeO2It adds in distilled water, stirring and condensing reflux 2h, are dissolved in water under the conditions of 100 DEG C of oil baths；
By Sr (NO3)2And KNO3It adds in distillation water dissolution and forms nitrate solution, citric acid is added in distillation water dissolution forms lemon
Lemon acid solution；
By tetraethyl orthosilicate solution and GeO2Aqueous solution is mixed evenly, and is slowly dropped into metal-nitrate solutions, Ran Houhuan
Slow to add in citric acid solution, it is 7 that the ammonium hydroxide that mass concentration is 15%, which is finally added dropwise, and adjusts pH value；
Mixed solution is put into magnetic stirring apparatus and is heated to 70 DEG C, is continuously stirred at 70 DEG C, and pass through in whipping process
The ammonium hydroxide that mass concentration is added to be 15%, makes the pH value of solution be maintained at 7, until forming gel；
Gel immigration evaporating dish is placed on electric furnace and is heated, until self-propagating combustion, which occurs, forms fluffy oxide powder；
Gained oxide powder is heated to 600 DEG C of heat preservations 1 hour to eliminate residual organic matter；Then 1000 DEG C are again heated to,
Heat preservation 10 hours, natural cooling form Sr0.8K0.2Si0.5Ge0.5O2.9Powder.
（Two）The preparation of intermediate temperature solid oxide fuel cell electrolyte：By step（One）It is prepared into
Sr0.8K0.2Si0.5Ge0.5O2.9Powder is put into mold, under the pressure of 200MPa, is pressed into disk, by disk with per minute 3
DEG C speed be heated to 1050 DEG C keep the temperature 10 hours, obtain required electrolyte disk.
The test method of conductivity：
The conductance for alternating current of electrolyte is measured using two-terminal method.Gained after 1050 ± 10 DEG C are sintered 10 ± 0.1 hours
Sr0.8K0.2Si0.5Ge0.5O2.9Silver paste is coated on electrolyte disk two sides, and silver electrode is made after then roasting 2h in 450 DEG C.Use filamentary silver
The silver electrode at both ends is connect with alternating current impedance instrument.The alternating current impedance instrument used is U.S. GAMRY electrochemical apparatus company model
For the electrochemical workstation of Interface 1000E, AC amplitude current potential 10mV, measurinng frequency range 0.1Hz-1MHz are measured
The temperature of ac impedance spectroscopy is 350-700 DEG C, is measured in dry air atmosphere is flowed.Conductivity is calculated using equation below：
In formula, σ is electrolytic conductivity, S/cm；
L is electrolyte sheet thickness, unit cm；
R is bath resistance, unit Ω；
S be electrolyte sheet cross-sectional area, unit cm2。
Ionic conductivity is 0.021S/cm, i.e. Sr when measuring 700 DEG C0.8K0.2Si0.5Ge0.5O2.9It is suitable for as electrolyte
Intermediate temperature solid oxide fuel cell.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification should all belong to the covering scope of the present invention.
Claims (3)
1. a kind of oxygen ion conduction intermediate temperature solid oxide fuel cell electrolyte preparation method, it is characterised in that：The electricity
The chemical formula for solving matter is Sr0.8K0.2Si0.5Ge0.5O2.9, preparation method specifically includes following steps：
（One）Sr0.8K0.2Si0.5Ge0.5O2.9Preparation：
1）By Sr0.8K0.2Si0.5Ge0.5O2.9Stoichiometric ratio weighs Sr (NO3)2、KNO3, tetraethyl orthosilicate and GeO2, and down payment
The molar ratio for belonging to cation and citric acid is 1:1.5 weigh citric acid；
2）Tetraethyl orthosilicate is dissolved in absolute ethyl alcohol；
3）By GeO2It adds in distilled water, stirring and condensing reflux 2h under the conditions of 100 DEG C of oil baths；
4）By Sr (NO3)2And KNO3It adds in distillation water dissolution and forms nitrate solution, citric acid is added in distillation water dissolution forms
Citric acid solution；
5）By step 2）Acquired solution is poured slowly into step 3）In acquired solution, 30min is stirred, is then slowly dropped into step 4）Institute
Nitrate solution is obtained, then instills citric acid solution, and ammonium hydroxide is added dropwise into solution, to adjust solution ph as 7；
6）By step 5）Obtained mixed solution, which is put into magnetic stirring apparatus, is heated to 70 DEG C, is then maintained at 70 DEG C and continuously stirs
It mixes, and ammonium hydroxide is added in whipping process, the pH value of solution is made to be maintained at 7, until forming gel；
7）Gel is moved into evaporating dish, is placed on electric furnace and heats, until self-propagating combustion, which occurs, forms fluffy oxidate powder
End；
8）Gained oxide powder is heated to 600 ± 10 DEG C of heat preservations 1 ± 0.1 hour to eliminate residual organic matter, Ran Hou
1000 ± 10 DEG C keep the temperature 10 ± 0.1 hours, and natural cooling forms Sr0.8K0.2Si0.5Ge0.5O2.9Powder；
（Two）The preparation of intermediate temperature solid oxide fuel cell electrolyte：
By step（One）Gained Sr0.8K0.2Si0.5Ge0.5O2.9Powder is put into mold, under the pressure of 200MPa, is pressed into circle
Disk is heated to 1050 ± 10 DEG C with 3 DEG C per minute of speed and keeps the temperature 10 ± 0.1 hours, obtains required electrolyte by piece
Disk.
2. a kind of preparation side of oxygen ion conduction intermediate temperature solid oxide fuel cell electrolyte according to claim 1
Method, it is characterised in that：Step（5）And step（6）The mass concentration of the ammonium hydroxide is 15%-20%.
3. a kind of preparation side of oxygen ion conduction intermediate temperature solid oxide fuel cell electrolyte according to claim 1
Method, it is characterised in that：Step 2）The volume ratio of middle tetraethyl orthosilicate and absolute ethyl alcohol is 1:3.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108987776A (en) * | 2018-07-20 | 2018-12-11 | 福州大学 | A kind of intermediate temperature solid oxide fuel cell electrolyte and preparation method thereof |
| CN109638325A (en) * | 2018-12-18 | 2019-04-16 | 福州大学 | A kind of intermediate temperature solid oxide fuel cell electrolyte of strontium doping |
| CN110581295A (en) * | 2019-09-24 | 2019-12-17 | 福州大学 | medium-temperature solid oxide fuel cell electrolyte and preparation method thereof |
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| CN105633439A (en) * | 2016-01-08 | 2016-06-01 | 福州大学 | Electrolyte for intermediate-temperature solid oxide fuel cell and preparation method of electrolyte |
| CN106684412A (en) * | 2017-01-11 | 2017-05-17 | 福州大学 | Proton conduction intermediate-temperature solid oxide fuel cell electrolyte and preparation method thereof |
| CN106711481A (en) * | 2017-01-11 | 2017-05-24 | 福州大学 | Medium-temperature solid oxide fuel battery composite electrolyte and preparation method thereof |
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2018
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Patent Citations (3)
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|---|---|---|---|---|
| CN105633439A (en) * | 2016-01-08 | 2016-06-01 | 福州大学 | Electrolyte for intermediate-temperature solid oxide fuel cell and preparation method of electrolyte |
| CN106684412A (en) * | 2017-01-11 | 2017-05-17 | 福州大学 | Proton conduction intermediate-temperature solid oxide fuel cell electrolyte and preparation method thereof |
| CN106711481A (en) * | 2017-01-11 | 2017-05-24 | 福州大学 | Medium-temperature solid oxide fuel battery composite electrolyte and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| PREETAM SINGH ET AL.: ""Sr1-xKxSi1-yGeyO3-0.5x：a new family of superior oxide-ion conductors"", 《ENERGY ＆ ENVIRONMENTAL SCIENCE》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108987776A (en) * | 2018-07-20 | 2018-12-11 | 福州大学 | A kind of intermediate temperature solid oxide fuel cell electrolyte and preparation method thereof |
| CN108987776B (en) * | 2018-07-20 | 2021-10-29 | 福州大学 | Medium-temperature solid oxide fuel cell electrolyte and preparation method thereof |
| CN109638325A (en) * | 2018-12-18 | 2019-04-16 | 福州大学 | A kind of intermediate temperature solid oxide fuel cell electrolyte of strontium doping |
| CN109638325B (en) * | 2018-12-18 | 2022-03-15 | 福州大学 | Strontium-doped medium-temperature solid oxide fuel cell electrolyte |
| CN110581295A (en) * | 2019-09-24 | 2019-12-17 | 福州大学 | medium-temperature solid oxide fuel cell electrolyte and preparation method thereof |
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Application publication date: 20180629 |