CN106684412B - One proton conducts intermediate temperature solid oxide fuel cell electrolyte and preparation method - Google Patents
One proton conducts intermediate temperature solid oxide fuel cell electrolyte and preparation method Download PDFInfo
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- CN106684412B CN106684412B CN201710017232.1A CN201710017232A CN106684412B CN 106684412 B CN106684412 B CN 106684412B CN 201710017232 A CN201710017232 A CN 201710017232A CN 106684412 B CN106684412 B CN 106684412B
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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 present invention provides proton conduction intermediate temperature solid oxide fuel cell electrolyte and preparation method, the group of the electrolyte becomes La1.85Mo0.15Ce2O7+δ, 0.1 > δ > 0 prepares one kind using sol-gel combustion method and has high conductivity proton and conduct intermediate temperature solid oxide fuel cell electrolyte, and relative density reaches 99.9%；The electrolyte is in dry 5%H2Conductivity reaches 0.057S/cm at 700 DEG C lower with 95%Ar mixed atmosphere.
Description
Technical field
The invention belongs to the electrolyte fields of battery, and in particular to a proton conducts medium temperature solid oxide fuel electricity
Pond electrolyte and preparation method.
Background technique
With the explosive growth of mankind's quantity and the continuous improvement of human lives' quality, demand of the people for the energy
Also cumulative year after year, the environmental problem thus caused more influence people's lives to amount, and the life for even threatening people is strong
Health.Therefore, how rationally, efficiently utilize one of difficulty that fossil fuel is facing mankind.
Solid oxide fuel cell (SOFC) keeps the chemical energy in fossil class A fuel A direct by electrochemical reaction process
It is converted into electric energy, due to not having burning and mechanical process, energy conversion efficiency is greatly improved, has avoid or reduced poison gas
The generation of the pollutants such as body and dust；The operating temperature of SOFC at 500 DEG C ~ 1000 DEG C, byproduct be high-quality heat and
Vapor, in the case where heat-electricity supply, capacity usage ratio is up to 80% or so, is a kind of energy resource system of clean and effective.
The operating temperature for the SOFC being commercially employed at present works at such high temperatures generally all at 1000 DEG C
So that there are many problems by SOFC: electrode densification, metallic interconnection materials require high and battery hermetization bad etc..Therefore,
The reduction of SOFC operating temperature can be effectively reduced the cost of system and improve stability.Traditional electrolyte is uncomfortable
For working under medium temperature environment, and proton has the advantages that small in size and light weight, under middle low temperature there is lower ion to pass
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 high conductivity under medium temperature operating condition, and in CO2And H2There is good stability under O environment, with
Meet the electrolyte that can be used in middle low temperature SOFC required at present.
Summary of the invention
In order to improve the performance of intermediate temperature solid oxide fuel cell electrolyte, prepared using collosol and gel-combustion method
Novel Mo6+Adulterate La1.85Mo0.15Ce2O7+δ, electrolyte sheet its relative density for keeping the temperature 5h through 1500 DEG C reaches 99.9%；5%
H2Conductivity reaches 0.057S/cm at 700 DEG C lower with 95%Ar mixed atmosphere, which has largely effective reduction fuel electricity
The characteristics of pond operating temperature.
Preparation method:
1. La1.85Mo0.15Ce2O7+δThe preparation method comprises the following steps:
1) La is pressed1.85Mo0.15Ce2O7+δ(0.1 > δ > 0) stoichiometric ratio weighs La (NO3)3、Ce(NO3)3·6H2O、MoO3,
And citric acid is weighed for 1:1.5 by the molar ratio of metal cation and citric acid；
2) weak aqua ammonia for being 10%-15% with mass concentration is by MoO3Dissolution；
3) respectively in La (NO3)3、Ce(NO3)3·6H2Distilled water dissolution is added in O and citric acid；
4) step 2 and step 3) acquired solution are successively poured into the citric acid solution of step 3), and dropwise into solution
The ammonium hydroxide that mass concentration is 15%-20% is added, to adjust solution ph as 7；
5) mixed solution for obtaining step 4), which is put into blender, 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；
6) gel is moved into evaporating dish, is placed on electric furnace and heats, until self-propagating combustion, which occurs, forms fluffy oxidation
Object powder；
7) gained oxide powder is heated to 800 ± 10 DEG C, keeps the temperature 3 ± 0.1 hours, then natural cooling, formed
La1.85Mo0.15Ce2O7+δPowder；
2. by gained La1.85Mo0.15Ce2O7+δPowder is put into mold, and under the pressure of 300MPa, disk is made, and will be justified
Piece is heated to 1500 ± 10 DEG C with 3 DEG C of speed per minute and keeps the temperature 5 ± 0.1 hours, electrolyte disk required for obtaining.
The electrolyte is used for solid oxide fuel cell, the operating temperature of the battery are as follows: 700 DEG C.
The beneficial effects of the present invention are:
1, advantage: proton has the advantages that small in size and light weight, has the activation of lower ionic conduction under middle low temperature
Can, therefore proton conductive oxide is a kind of electrolyte that can be applied to low-temperature working SOFC.La2Ce2O7It is led as a proton
Body, in CO2And H2There is good stability in O, pass through A Mo6+Be doped with preferable conductivity, be suitble to be used in it is low
Temperature solid-oxide fuel battery electrolyte.
2, composite electrolyte relative density prepared by the present invention reaches 99.9%；In 5%H2Under 95%Ar mixed atmosphere
Conductivity reaches 0.057S/cm at 700 DEG C.
3, purposes: intermediate temperature solid oxide fuel cell is used for as electrolyte.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution 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+δThe preparation method comprises the following steps:
1) La is pressed1.85Mo0.15Ce2O7+δ(0.1 > δ > 0) stoichiometric ratio weighs La (NO3)3、Ce(NO3)3·6H2O、MoO3,
And citric acid is weighed for 1:1.5 by the molar ratio of metal cation and citric acid；
2) weak aqua ammonia for being 10%-15% with mass concentration is by MoO3Dissolution；
3) respectively in La (NO3)3、Ce(NO3)3·6H2Distilled water dissolution is added in O and citric acid；
4) step 2 and step 3) acquired solution are successively poured into citric acid solution, and quality is added dropwise into solution
Concentration is the ammonium hydroxide of 15%-20%, to adjust solution ph as 7；
5) mixed solution for obtaining step 4), which is put into blender, 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；
6) gel is moved into evaporating dish, is placed on electric furnace and heats, until self-propagating combustion, which occurs, forms fluffy oxidation
Object powder；
7) gained oxide powder is heated to 800 ± 10 DEG C, keeps the temperature 3 ± 0.1 hours, then natural cooling, formed
La1.85Mo0.15Ce2O7+δPowder.
2. by gained La1.85Mo0.15Ce2O7+δ(LMC) powder is put into mold, and under the pressure of 300MPa, disk is made,
Disk is heated to 1500 ± 10 DEG C with 3 DEG C of speed per minute and keeps the temperature 5 ± 0.1 hours, obtains high performance medium temperature solid oxygen
Compound fuel cell proton electrolyte disk.
It is specific:
1 mole of La1.85Mo0.15Ce2O7+δ(LMC) preparation:
Weigh 1.85 moles of La (NO3)3: 1.85 × 324.92=601.102 grams
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 gram
Weigh 6 moles of citric acid: 6 × 210.14=1260.840 grams
It is 10% weak aqua ammonia by MoO with mass concentration3Dissolution；
Respectively in Ce (NO3)3·6H2O、La(NO3)3It is dissolved with distilled water is added in citric acid；
Above-mentioned all solution are poured into citric acid solution respectively, dropwise addition mass concentration is that 15% ammonium hydroxide adjusting pH value is 7；
Mixed solution is put into blender and is heated to 70 DEG C, is continuously stirred at 70 DEG C, and pass through in whipping process
Add ammonium hydroxide, the pH value of solution is made to 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 oxidate powder
End；
Powder is heated to 800 DEG C, keeps the temperature 3 hours, natural cooling forms La1.85Mo0.15Ce2O7+δPowder.
The preparation of disk: the La that will be prepared into1.85Mo0.15Ce2O7+δPowder is put into mold, under the pressure of 300MPa,
Disk is made, disk is heated to 1500 DEG C with 3 DEG C of heating speed per minute and keeps the temperature 5 hours, obtains required electrolyte circle
Piece.
The test method of conductivity:
The conductance for alternating current of electrolyte is measured using two-terminal method.It is resulting after being sintered 5 hours at 1500 DEG C
La1.85Mo0.15Ce2O7+δSilver paste is coated on electrolyte disk two sides, and silver electrode is then made after 450 DEG C of roasting 2h.It will with filamentary silver
The silver electrode at both ends is connect with alternating current impedance instrument.The alternating current impedance instrument used is Shanghai Chen Hua Instrument Ltd. model
CHI660E electrochemical workstation measures frequency range 1kHz-20MHz using current potential 20mV, and the temperature for measuring conductance for alternating current is
700 DEG C, in dry 5%H2It is measured under 95%Ar mixed atmosphere.Conductivity is calculated using following formula:
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: intermediate temperature solid oxide fuel cell is used for as electrolyte.
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, is all covered by the present invention.
Claims (2)
1. a proton conducts intermediate temperature solid oxide fuel cell electrolyte, which is characterized in that the group of the electrolyte becomes
La1.85Mo0.15Ce2O7+δ, 0.1 > δ > 0；
Preparation method includes the following steps:
1) La is pressed1.85Mo0.15Ce2O7+δ, 0.1 > δ > 0, stoichiometric ratio weighs La (NO3)3、Ce(NO3)3·6H2O、MoO3, and press
The molar ratio of metal cation and citric acid is that 1:1.5 weighs citric acid；
2) weak aqua ammonia for being 10%-15% with mass concentration is by MoO3Dissolution；
3) respectively in La (NO3)3、Ce(NO3)3·6H2Distilled water dissolution is added in O and citric acid；
4) step 2 and step 3) acquired solution are successively poured into the citric acid solution of step 3), and is added dropwise into solution
Mass concentration is the ammonium hydroxide of 15%-20%, to adjust solution ph as 7；
5) mixed solution for obtaining step 4), which is put into blender, is heated to 70 DEG C, is then maintained at 70 DEG C and continuously stirs,
And ammonium hydroxide is added in whipping process, so that the pH value of solution is maintained at 7, until forming gel；
6) gel is moved into evaporating dish, is placed on electric furnace and heats, until self-propagating combustion, which occurs, forms fluffy oxidate powder
End；
7) gained oxide powder is heated to 800 ± 10 DEG C, keeps the temperature 3 ± 0.1 hours, then natural cooling, formed
La1.85Mo0.15Ce2O7+δPowder；
8) by gained La1.85Mo0.15Ce2O7+δPowder is put into mold, and under the pressure of 300MPa, disk is made, by disk with
3 DEG C of speed per minute is heated to 1500 ± 10 DEG C and keeps the temperature 5 ± 0.1 hours, electrolyte disk required for obtaining.
2. the application of the electrolyte according to claim 1, it is characterised in that: be used for solid oxide fuel cell, the electricity
The operating temperature in pond is 700 DEG C.
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| CN107230795B (en) * | 2017-05-23 | 2020-07-07 | 福州大学 | Electrolyte of intermediate-temperature solid oxide fuel cell with 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 |
| 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 |
| 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 |
| 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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| CN101271981A (en) * | 2007-03-23 | 2008-09-24 | 中国科学院大连化学物理研究所 | Low temperature solid-oxide fuel battery three-in-one component MEA and preparation thereof |
| JP2008243708A (en) * | 2007-03-28 | 2008-10-09 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery and manufacturing method of the same |
| CN101662033A (en) * | 2008-08-25 | 2010-03-03 | 中国科学院物理研究所 | Solid oxide fuel cell and preparation method thereof |
| US8986894B2 (en) * | 2011-02-09 | 2015-03-24 | Toyota Jidosha Kabushiki Kaisha | Solid electrolyte including layered metal oxide, fuel cell including thereof, production method for solid electrolyte, and production method for electrode catalyst |
| CN102420332A (en) * | 2011-11-04 | 2012-04-18 | 上海交通大学 | Chromium poisoning-resistant doped CeO2-coated LaNi0.6Fe0.4O3-delta cathode of solid oxide fuel cell and preparation method thereof |
| CN103219525B (en) * | 2012-01-19 | 2015-08-19 | 中国科学院上海硅酸盐研究所 | low-temperature solid oxide fuel cell and preparation method thereof |
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