CN106684412A - Proton conduction intermediate-temperature solid oxide fuel cell electrolyte and preparation method thereof - Google Patents
Proton conduction intermediate-temperature solid oxide fuel cell electrolyte and preparation method thereof Download PDFInfo
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- CN106684412A CN106684412A CN201710017232.1A CN201710017232A CN106684412A CN 106684412 A CN106684412 A CN 106684412A CN 201710017232 A CN201710017232 A CN 201710017232A CN 106684412 A CN106684412 A CN 106684412A
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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
The invention provides proton conduction intermediate-temperature solid oxide fuel cell electrolyte and a preparation method thereof. Composition of the electrolyte is La1.85Mo0.15Ce2O<7+>delta, wherein delta is less than 0.1 and more than 0, a sol-gel combustion method is adopted for preparing the proton conduction intermediate-temperature solid oxide fuel cell electrolyte with high conductivity, and relative density reaches 99.9%; and the conductivity of the electrolyte reaches 0.057S/cm at the temperature of 700 DEG C in dry mixed atmosphere containing 5% of H2 and 95% of Ar.
Description
Technical field
The invention belongs to the electrolyte field of battery, and in particular to temperature solid-oxide fuel electricity in kind of proton conduction
Pond electrolyte and preparation method.
Background technology
With the explosive growth and the continuous improvement of human lives' quality of mankind's quantity, demand of the people for the energy
Also cumulative year after year is measured, the environmental problem for thus triggering more has influence on the life of people, the life for even threatening people is good for
Health.Therefore, how rationally, efficiently utilize fossil fuel is one of difficulty of facing mankind.
SOFC（SOFC）Make the chemical energy in fossil class A fuel A direct by electrochemical reaction process
Electric energy is converted into, due to without burning and mechanical process, drastically increasing energy conversion efficiency, it is to avoid or reduced poison gas
The generation of the pollutant such as body and dust；The operating temperature of SOFC at 500 DEG C ~ 1000 DEG C, its byproduct be high-quality heat and
Vapor, in the case of heat-CCHP, capacity usage ratio is up to 80% or so, is a kind of energy resource system of clean and effective.
The operating temperature of the SOFC being commercially employed at present is general all at 1000 DEG C, works at such high temperatures
So that SOFC there are problems that it is many：Electrode is densified, metallic interconnection materials requirement is high and battery hermetization is bad etc..Therefore,
The reduction of SOFC operating temperatures can be effectively reduced the cost of system and improve stability.Traditional electrolyte is uncomfortable
For being worked under middle temperature environment, and proton has the advantages that small volume and light weight, and there is relatively low ion to pass under middle low temperature
Activation energy is led, therefore proton conductive oxide is a kind of electrolyte that can be applied to low-temperature working SOFC.Proton electricity of the invention
Solution material can obtain electrical conductivity high under middle temperature condition of work, and in CO2And H2There is good stability under O environment, with
The electrolyte that can be used in middle low temperature SOFC needed for meeting at present.
The content of the invention
In order to improve the performance of intermediate temperature solid oxide fuel cell electrolyte, prepared using collosol and gel-combustion method
New Mo6+Doping La1.85Mo0.15Ce2O7+δ, 99.9% is reached through electrolyte sheet its relative density of 1500 DEG C of insulation 5h；5%
H2Electrical conductivity reaches 0.057S/cm at 700 DEG C lower with 95%Ar mixed atmospheres, and the electrolyte has largely effective reduction fuel electricity
The characteristics of pond operating temperature.
Preparation method：
1. La1.85Mo0.15Ce2O7+δPreparation method be：
1）By La1.85Mo0.15Ce2O7+δ（0.1>δ>0）Stoichiometric proportion weighs La (NO3)3、Ce(NO3)3·6H2O、MoO3, and press
Metal cation is 1 with the mol ratio of citric acid:1.5 weigh citric acid；
2）With the weak aqua ammonia that mass concentration is 10%-15% by MoO3Dissolving；
3）Respectively in La (NO3)3、Ce(NO3)3·6H2Distillation water dissolves are added in O and citric acid；
4）By step 2）With step 3）Resulting solution pours into step 3 successively）Citric acid solution in, and to being added dropwise in solution
Mass concentration is the ammoniacal liquor of 15%-20%, to adjust solution ph as 7；
5）By step 4）The mixed solution for obtaining is heated to 70 DEG C in being put into agitator, is continuously stirred at being then maintained at 70 DEG C,
And ammoniacal liquor is added in whipping process, the pH value of solution is maintained at 7, until forming gel；
6）By in gel immigration evaporating dish, it is placed on electric furnace and heats, until self-propagating combustion occurs forms fluffy oxidate powder
End；
7）Gained oxide powder is heated to 800 ± 10 DEG C, 3 ± 0.1 hours is incubated, then natural cooling, is formed
La1.85Mo0.15Ce2O7+δPowder；
2. by gained La1.85Mo0.15Ce2O7+δPowder is put into mould, under the pressure of 300MPa, is made disk, by disk with
3 DEG C per minute of speed is heated to 1500 ± 10 DEG C and is incubated 5 ± 0.1 hours, obtains required electrolyte disk.
The electrolyte is used for SOFC, and the operating temperature of the battery is：700℃.
The beneficial effects of the present invention are：
1st, advantage：Proton has the advantages that small volume and light weight, has relatively low ionic conduction activation energy under middle low temperature, because
This proton conductive oxide is a kind of electrolyte that can be applied to low-temperature working SOFC.La2Ce2O7As a kind of proton conductor, its
In CO2And H2There is good stability, by A Mo in O6+Preferable electrical conductivity is doped with, is adapted to be used in middle low-temperature solid
Oxide body fuel-cell electrolyte.
2nd, composite electrolyte relative density prepared by the present invention reaches 99.9%；In 5%H2Under 95%Ar mixed atmospheres
Electrical conductivity reaches 0.057S/cm at 700 DEG C.
3rd, purposes：It is used for intermediate temperature solid oxide fuel cell as electrolyte.
Specific embodiment
In order that content of the present invention easily facilitates understanding, with reference to specific embodiment to of the present invention
Technical scheme is described further, but the present invention is not limited only to this.
Embodiment 1
La1.85Mo0.15Ce2O7+δ（LMC）Preparation method
1. La1.85Mo0.15Ce2O7+δPreparation method be：
1）By La1.85Mo0.15Ce2O7+δ（0.1>δ>0）Stoichiometric proportion weighs La (NO3)3、Ce(NO3)3·6H2O、MoO3, and press
Metal cation is 1 with the mol ratio of citric acid:1.5 weigh citric acid；
2）With the weak aqua ammonia that mass concentration is 10%-15% by MoO3Dissolving；
3）Respectively in La (NO3)3、Ce(NO3)3·6H2Distillation water dissolves are added in O and citric acid；
4）By step 2）With step 3）Resulting solution is poured into citric acid solution successively, and to being added dropwise over mass concentration in solution
It is the ammoniacal liquor of 15%-20%, to adjust solution ph as 7；
5）By step 4）The mixed solution for obtaining is heated to 70 DEG C in being put into agitator, is continuously stirred at being then maintained at 70 DEG C,
And ammoniacal liquor is added in whipping process, the pH value of solution is maintained at 7, until forming gel；
6）By in gel immigration evaporating dish, it is placed on electric furnace and heats, until self-propagating combustion occurs forms fluffy oxidate powder
End；
7）Gained oxide powder is heated to 800 ± 10 DEG C, 3 ± 0.1 hours is incubated, then natural cooling, is formed
La1.85Mo0.15Ce2O7+δPowder.
2. by gained La1.85Mo0.15Ce2O7+δ（LMC）Powder is put into mould, under the pressure of 300MPa, is made disk,
Disk is heated to 1500 ± 10 DEG C with 3 DEG C per minute of speed and is incubated 5 ± 0.1 hours, obtain high performance middle temperature solid oxygen
Compound fuel cell proton electrolyte disk.
Specifically：
1 mole of La1.85Mo0.15Ce2O7+δ（LMC）Preparation：
Weigh 1.85 moles of La (NO3)3：601.102 grams of 1.85 × 324.92=
Weigh 0.15 mole of MoO3：0.15 × 143.95=21.593 grams
Weigh 2 moles of Ce (NO3)3·6H2O：2 × 434.22=868.440 grams
Weigh 6 moles of citric acid：6 × 210.14=1260.840 grams
It is 10% weak aqua ammonia by MoO with mass concentration3Dissolving；
Respectively in Ce (NO3)3·6H2O、La(NO3)3Water dissolves are distilled with being added in citric acid；
Above-mentioned all solution are poured into citric acid solution respectively, it is that 15% ammoniacal liquor regulation pH value is 7 that mass concentration is added dropwise；
Mixed solution is put into 70 DEG C are heated in agitator, continuously stirred at 70 DEG C, and pass through ammonification in whipping process
Water, 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 occurs forms fluffy oxide powder；
Powder is heated to 800 DEG C, 3 hours are incubated, natural cooling forms La1.85Mo0.15Ce2O7+δPowder.
The preparation of disk：The La that will be prepared into1.85Mo0.15Ce2O7+δPowder is put into mould, under the pressure of 300MPa,
Disk is made, disk is heated into 1500 DEG C with 3 DEG C per minute of firing rate is incubated 5 hours, the electrolyte circle needed for obtaining
Piece.
The method of testing of electrical conductivity：
The conductance for alternating current of electrolyte is determined using two-terminal method.Will gained of the sintering after 5 hours at 1500 DEG C
La1.85Mo0.15Ce2O7+δSilver paste is coated on electrolyte disk two sides, and silver electrode is obtained after being then calcined 2h in 450 DEG C.Will with filamentary silver
The silver electrode at two ends is connected with alternating current impedance instrument.The alternating current impedance instrument for using is Shanghai Chen Hua Instrument Ltd. model
CHI660E electrochemical workstations, using current potential 20mV, determine frequency range 1kHz-20MHz, and the temperature for determining conductance for alternating current is
700 DEG C, drying 5%H2Determined with 95%Ar mixed atmospheres.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。
Ionic conductivity is 0.057S/cm at 700 DEG C.
Purposes：It is used for intermediate temperature solid oxide fuel cell as electrolyte.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modification, should all belong to covering scope of the invention.
Claims (3)
1. kind of proton conduction intermediate temperature solid oxide fuel cell electrolyte, it is characterised in that the composition of the electrolyte is
La1.85Mo0.15Ce2O7+δ, 0.1>δ>0.
2. it is a kind of to prepare the method that proton as claimed in claim 1 conducts intermediate temperature solid oxide fuel cell electrolyte, its
It is characterised by, preparation method comprises the following steps：
1）By La1.85Mo0.15Ce2O7+δ, 0.1>δ>0, stoichiometric proportion weighs La (NO3)3、Ce(NO3)3·6H2O、MoO3, and press
Metal cation is 1 with the mol ratio of citric acid:1.5 weigh citric acid；
2）With the weak aqua ammonia that mass concentration is 10%-15% by MoO3Dissolving；
3）Respectively in La (NO3)3、Ce(NO3)3·6H2Distillation water dissolves are added in O and citric acid；
4）By step 2）With step 3）Resulting solution pours into step 3 successively）Citric acid solution in, and to being added dropwise in solution
Mass concentration is the ammoniacal liquor of 15%-20%, to adjust solution ph as 7；
5）By step 4）The mixed solution for obtaining is heated to 70 DEG C in being put into agitator, is continuously stirred at being then maintained at 70 DEG C,
And ammoniacal liquor is added in whipping process, the pH value of solution is maintained at 7, until forming gel；
6）By in gel immigration evaporating dish, it is placed on electric furnace and heats, until self-propagating combustion occurs forms fluffy oxidate powder
End；
7）Gained oxide powder is heated to 800 ± 10 DEG C, 3 ± 0.1 hours is incubated, then natural cooling, is formed
La1.85Mo0.15Ce2O7+δPowder；
8）By gained La1.85Mo0.15Ce2O7+δPowder is put into mould, under the pressure of 300MPa, is made disk, by disk with
3 DEG C per minute of speed is heated to 1500 ± 10 DEG C and is incubated 5 ± 0.1 hours, obtains required electrolyte disk.
3. the application of electrolyte obtained in the preparation method according to claim 2, it is characterised in that：For solid oxidation
Thing fuel cell, the operating temperature of the battery is 700 DEG C.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107230795A (en) * | 2017-05-23 | 2017-10-03 | 福州大学 | A kind of intermediate temperature solid oxide fuel cell electrolyte for possessing proton conductivity |
| CN108232303A (en) * | 2018-01-17 | 2018-06-29 | 福州大学 | Oxygen ion conduction intermediate temperature solid oxide fuel cell electrolyte preparation method |
| CN108270024A (en) * | 2018-01-22 | 2018-07-10 | 福州大学 | A kind of codope intermediate temperature solid oxide fuel cell electrolyte and preparation method thereof |
| 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 |
| CN116063079A (en) * | 2023-01-18 | 2023-05-05 | 中稀(凉山)稀土有限公司 | Rare earth cold pigment of molybdenum cerium acid and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107230795A (en) * | 2017-05-23 | 2017-10-03 | 福州大学 | A kind of intermediate temperature solid oxide fuel cell electrolyte for possessing proton conductivity |
| CN108232303A (en) * | 2018-01-17 | 2018-06-29 | 福州大学 | Oxygen ion conduction intermediate temperature solid oxide fuel cell electrolyte preparation method |
| CN108270024A (en) * | 2018-01-22 | 2018-07-10 | 福州大学 | A kind of codope intermediate temperature solid oxide fuel cell electrolyte and preparation method thereof |
| CN108270024B (en) * | 2018-01-22 | 2020-05-08 | 福州大学 | Double-doped medium-temperature solid oxide fuel cell electrolyte and preparation method thereof |
| 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 |
| CN116063079A (en) * | 2023-01-18 | 2023-05-05 | 中稀(凉山)稀土有限公司 | Rare earth cold pigment of molybdenum cerium acid and preparation method thereof |
| CN116063079B (en) * | 2023-01-18 | 2024-04-30 | 中稀(凉山)稀土有限公司 | Rare earth cold pigment of molybdenum cerium acid and preparation method thereof |
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| CN106684412B (en) | 2019-04-02 |
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