CN107230795A - A kind of intermediate temperature solid oxide fuel cell electrolyte for possessing proton conductivity - Google Patents
A kind of intermediate temperature solid oxide fuel cell electrolyte for possessing proton conductivity Download PDFInfo
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- CN107230795A CN107230795A CN201710368348.XA CN201710368348A CN107230795A CN 107230795 A CN107230795 A CN 107230795A CN 201710368348 A CN201710368348 A CN 201710368348A CN 107230795 A CN107230795 A CN 107230795A
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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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- 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
Possess proton conductivity intermediate temperature solid oxide fuel cell electrolyte the invention discloses one kind, belong to the preparation field of fuel-cell electrolyte.The present invention is using La (NO3)3·nH2O、Ce(NO3)3·6H2O, KNO and citric acid are primary raw material, prepare the electrolyte through sol-gel combustion method, its relative density reaches 98.0%.Obtained electrolyte in air atmosphere 800 DEG C when maximum conductivity be 1.76 × 10‑2 S/cm, is drying 5%H2Electrical conductivity is 1.57 × 10 during with lower 700 DEG C of 95%Ar mixed atmospheres‑2 S/cm, and in CO2And H2In O have good stability, therefore the electrolyte have it is largely effective reduction temperature of fuel cell, improve chemical property the characteristics of, be adapted to be used in intermediate temperature solid oxide fuel cell.
Description
Technical field
The invention belongs to the preparation field of fuel-cell electrolyte, and in particular to a kind of middle Wen Gu for possessing proton conductivity
Oxide body fuel-cell electrolyte.
Background technology
The energy is in the basis of human society survival and development, world wide still based on fossil energy, and current
Exist during use and utilize a series of serious problems such as unreasonable, transformation efficiency is low, seriously polluted.Therefore, rationally, efficiently
It is one of difficulty of facing mankind using fossil fuel.
SOFC (Solid Oxide Fuel Cell, abbreviation SOFC) is one kind by fossil fuel
Chemical energy the electrochemical appliance of electric energy is converted directly into by electrode reaction, with efficient, environment-friendly pollution-free, achievable
The advantages of cogeneration, be a kind of energy resource system of clean and effective.
The SOFC applied at present electrolyte is generally Y2O3Stable zirconium oxide（Abbreviation YSZ）, and operating temperature is general all
At 1000 DEG C, work at such high temperatures so that SOFC has many problems：Battery component heat endurance is poor, connector material
The problems such as material requires bad high, battery hermetization and cost increase and bad longtime running stability, seriously hinders
SOFC commercialization process.Therefore, reduction SOFC operating temperatures can be effectively reduced the cost of system and improve stability, it is to avoid
The variety of problems that high-temperature operation is brought.Traditional electrolyte YSZ has not been suitable for working under middle low temperature environment, therefore,
Find a kind of electrolyte with high conductivity and good stability under middle low temperature particularly important.Led compared to oxonium ion
Body, proton conductor has the advantages that small volume and light weight, has relatively low ionic conduction activation energy under middle low temperature, higher
Ionic conductivity, therefore proton conductive oxide is a kind of electrolyte that can be applied to low-temperature working SOFC.The proton of the present invention
Electrolyte can obtain high electrical conductivity under middle temperature condition of work, and in CO2It is good steady with having under water vapor conditions
It is qualitative, the performance requirement in meeting at present needed for low temperature SOFC.
The content of the invention
It is an object of the invention in view of the shortcomings of the prior art, providing a kind of middle temperature solid oxidation for possessing proton conductivity
Thing fuel-cell electrolyte.Electrolyte produced by the present invention in air atmosphere 800 DEG C when maximum conductivity be 1.76 × 10-2
S/cm, is drying 5%H2Electrical conductivity is 1.57 × 10 during with lower 700 DEG C of 95%Ar mixed atmospheres-2 S/cm, is adapted to low in being used in
In temperature solid-oxide fuel battery.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of intermediate temperature solid oxide fuel cell electrolyte for possessing proton conductivity, its chemical formula is La1.80K0.20Ce2O7-δ
Soild oxide, wherein 0 ＜ δ≤0.2；The preparation method of the electrolyte, specifically includes following steps：
（One）La1.80K0.20Ce2O7-δPreparation：
1）By La1.80K0.20Ce2O7-δStoichiometric proportion weighs La (NO3)3·nH2O、Ce(NO3)3·6H2O and KNO3, and down payment
The mol ratio for belonging to cation and citric acid is 1:1.5 weigh citric acid；
2）By La (NO3)3·nH2O、Ce(NO3)3·6H2O 、KNO3Deionized water dissolving, which is separately added into, with citric acid forms molten
Liquid；
3）By step 2）La (the NO of gained3)3·nH2O solution, Ce (NO3)3·6H2O solution and KNO3Solution pours into step successively
2）In the citric acid solution of gained, and the ammoniacal liquor that mass concentration is 15%-20% is added dropwise into solution, to adjust solution ph
For 7；
4）By step 3）Obtained mixed solution, which is put into agitator, is heated to 70 DEG C, is then maintained at 70 DEG C and continuously stirs,
And the ammoniacal liquor that mass concentration is 15%-20% is added in whipping process, the pH value of solution is maintained at 7, until forming gel；
5）By step 4）Obtained gel is moved into evaporating dish, is placed on electric furnace and is heated, until occurring self-propagating combustion forms fluffy
The oxide powder of pine；
6）By step 5）Gained oxide powder is heated to 790-810 DEG C, is incubated 2.9-3.1 hours, then natural cooling, is formed
La1.80K0.20Ce2O7-δ（LKC）Powder；
（Two）The preparation of intermediate temperature solid oxide fuel cell electrolyte：
By step（One）Obtained La1.80K0.20Ce2O7-δPowder is put into mould, under 300MPa pressure, is made a diameter of
13 ± 0.1mm, thickness are 0.5 ± 0.1mm disk, and disk is heated into 1500 ± 1 DEG C of insulations 5 with 3 DEG C per minute of speed
± 0.1 hour, obtain the intermediate temperature solid oxide fuel cell electrolyte disk for possessing proton conductivity.
The beneficial effects of the present invention are：Proton has the advantages that small volume and light weight, has under middle low temperature relatively low
Ionic conduction activation energy, therefore the proton conductive oxide for preparing of the present invention is a kind of electricity that can be applied to low-temperature working SOFC
Xie Zhi；La2Ce2O7As a kind of proton conductor, it is in CO2And H2There is good stability in O, pass through A K+Doping improves it
Electrical conductivity, in air atmosphere 800 DEG C when maximum conductivity be 1.76 × 10-2 S/cm, is drying 5%H2With 95%Ar gaseous mixtures
Electrical conductivity is 1.57 × 10 when atmosphere is lower 700 DEG C-2 S/cm, is adapted to be used in intermediate temperature solid oxide fuel cell.
Brief description of the drawings
Fig. 1 is La under air conditionses1.8K0.2Ce2O7-δElectrical conductivity and test temperature relation curve；
Fig. 2 is the La under 5% hydrogen and 95% argon gas mixed atmosphere1.8K0.2Ce2O7-δElectrical conductivity and test temperature relation curve.
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 La1.80K0.20Ce2O7-δ（LKC）Preparation：
Weigh 1.80 moles of La (NO3)3·nH2O：1.80 × 324.92=584.856 grams
Weigh 0.20 mole of KNO3：0.20 × 84.99=16.998 grams
Weigh 2.00 moles of Ce (NO3)3·6H2O：2.00 × 434.22=868.440 grams
Weigh 6.00 moles of citric acid：6.00 × 210.14=1260.840 grams
By KNO3、Ce(NO3)3·6H2O、La(NO3)3·nH2O and citric acid are respectively with deionized water dissolving formation solution；
By La (NO3)3·nH2O solution, Ce (NO3)3·6H2O solution and KNO3Solution is poured into citric acid solution respectively, is added dropwise
The ammoniacal liquor regulation pH value that mass concentration is 15% is 7；
Mixed solution is put into agitator and is heated to 70 DEG C, is continuously stirred at 70 DEG C, and by adding matter in whipping process
The ammoniacal liquor that concentration is 15% is measured, the pH value of solution is maintained at 7, until forming gel；
Gel immigration evaporating dish is placed on electric furnace and heated, until occurring self-propagating combustion forms fluffy oxide powder；
Powder is heated to 800 DEG C, 3 hours are incubated, natural cooling forms La1.80K0.20Ce2O7-δPowder；
（Two）The preparation of intermediate temperature solid oxide fuel cell electrolyte：
By step（One）The La being prepared into1.80K0.20Ce2O7-δPowder is put into mould, and under 300MPa pressure, diameter is made
For the disk for 13mmmm, thickness 0.5mmmm, disk with 3 DEG C per minute of firing rate is heated to 1500 DEG C of insulations 5 small
When, obtain required electrolyte disk.
The method of testing of electrical conductivity：
The conductance for alternating current of electrolyte is determined using two-terminal method.By the gained after being sintered 5 ± 0.1 hours at 1500 ± 1 DEG C
La1.80K0.20Ce2O7-δ（LKC）Silver paste is coated on electrolyte disk two sides, is then calcined in 450 DEG C after 2h and silver electrode is made.With silver
The silver electrode at two ends is connected by silk with alternating current impedance instrument.The alternating current impedance instrument used is Shanghai Chen Hua Instrument Ltd. model
CHI660E electrochemical workstations, using current potential 30mV, determine frequency range 0.1Hz-1000kHz, its impedance spectrum temperature are surveyed in air
Spend for 350-800 DEG C, as a result as shown in Figure 1；Drying 5%H2It is 350- with its impedance spectrum temperature is surveyed under 95%Ar mixed atmospheres
700 DEG C, as a result as shown in Figure 2；Electrical conductivity is calculated using equation below：
In formula, σ is electrolytic conductivity, S/cm；
H is electrolyte sheet thickness, unit cm；
R is bath resistance, unit Ω；
S is electrolyte sheet cross-sectional area, unit cm2。
From figure 1 it appears that the electrolyte in air atmosphere 800 DEG C when maximum conductivity be 1.76 × 10-2 S/
Cm, from figure 2 it can be seen that the electrolyte is drying 5%H2Electrical conductivity is 1.57 × 10 during with lower 700 DEG C of 95%Ar mixed atmospheres-2 S/cm, and La2Ce2O7In CO2And H2There is good stability in O, therefore the electrolyte has largely effective reduction combustion
The characteristics of expecting battery operating temperature, improve chemical property.
The foregoing is only 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 intermediate temperature solid oxide fuel cell electrolyte for possessing proton conductivity, it is characterised in that：The electrolyte
It is La for chemical formula1.80K0.20Ce2O7-δSoild oxide, wherein 0 ＜ δ≤0.2.
2. a kind of prepare the as claimed in claim intermediate temperature solid oxide fuel cell electrolyte for possessing proton conductivity
Method, it is characterised in that：Specifically include following steps：
（One）La1.80K0.20Ce2O7-δPreparation：
1）By La1.80K0.20Ce2O7-δStoichiometric proportion weighs La (NO3)3·nH2O、Ce(NO3)3·6H2O and KNO3, and by metal
The mol ratio of cation and citric acid is 1:1.5 weigh citric acid；
2）By La (NO3)3·nH2O、Ce(NO3)3·6H2O 、KNO3Deionized water dissolving formation solution is separately added into citric acid；
3）By step 2）La (the NO of gained3)3·nH2O solution, Ce (NO3)3·6H2O solution and KNO3Solution pours into step successively
2）In the citric acid solution of gained, and ammoniacal liquor is added dropwise into solution, to adjust solution ph as 7；
4）By step 3）Obtained mixed solution, which is put into agitator, is heated to 70 DEG C, is then maintained at 70 DEG C and continuously stirs,
And ammoniacal liquor is added in whipping process, the pH value of solution is maintained at 7, until forming gel；
5）By step 4）Obtained gel is moved into evaporating dish, is placed on electric furnace and is heated, until occurring self-propagating combustion forms fluffy
The oxide powder of pine；
6）By step 5）Gained oxide powder is heated to 790-810 DEG C, is incubated 2.9-3.1 hours, then natural cooling, is formed
La1.80K0.20Ce2O7-δPowder；
（Two）The preparation of intermediate temperature solid oxide fuel cell electrolyte：
By step（One）Obtained La1.80K0.20Ce2O7-δPowder is put into mould, under 300MPa pressure, is made a diameter of
13 ± 0.1mm, thickness are 0.5 ± 0.1mm disk, and disk is heated into 1500 ± 1 DEG C of insulations 5 with 3 DEG C per minute of speed
± 0.1 hour, obtain the intermediate temperature solid oxide fuel cell electrolyte disk for possessing proton conductivity.
3. preparation method according to claim 2, it is characterised in that：Step 3）With step 4）Described in ammoniacal liquor quality
Concentration is 15%-20%.
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| CN201710368348.XA CN107230795B (en) | 2017-05-23 | 2017-05-23 | Electrolyte of intermediate-temperature solid oxide fuel cell with proton conductivity |
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| CN201710368348.XA CN107230795B (en) | 2017-05-23 | 2017-05-23 | Electrolyte of intermediate-temperature solid oxide fuel cell with proton conductivity |
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| CN107230795B CN107230795B (en) | 2020-07-07 |
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Cited By (2)
| 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 |
| CN112777624A (en) * | 2021-01-13 | 2021-05-11 | 中国科学技术大学 | Electrolyte material, preparation method and application thereof |
Citations (3)
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|---|---|---|---|---|
| CN102942364A (en) * | 2012-11-02 | 2013-02-27 | 天津大学 | Zinc oxide-carbonate co-doped cerium barium zirconate proton conductor material and preparation method thereof |
| CN104078687A (en) * | 2013-03-25 | 2014-10-01 | 中国科学院物理研究所 | Anode material containing alkali metal or alkaline-earth metal element of solid oxide fuel cell and preparation method and application thereof |
| 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 |
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2017
- 2017-05-23 CN CN201710368348.XA patent/CN107230795B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942364A (en) * | 2012-11-02 | 2013-02-27 | 天津大学 | Zinc oxide-carbonate co-doped cerium barium zirconate proton conductor material and preparation method thereof |
| CN104078687A (en) * | 2013-03-25 | 2014-10-01 | 中国科学院物理研究所 | Anode material containing alkali metal or alkaline-earth metal element of solid oxide fuel cell and preparation method and application thereof |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| ZHIWEN ZHU ET AL: ""La2Ce2O7: A promising proton ceramic conductor in hydrogen economy"", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| 熊月龙 等: "Ce0.8Sm0.2O1.9-BaCe0.8Sm0.2O2.9复合电解质的晶界电导", 《硅酸盐学报》 * |
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 |
| CN108987776B (en) * | 2018-07-20 | 2021-10-29 | 福州大学 | Medium-temperature solid oxide fuel cell electrolyte and preparation method thereof |
| CN112777624A (en) * | 2021-01-13 | 2021-05-11 | 中国科学技术大学 | Electrolyte material, preparation method and application thereof |
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