CN106848359A - A kind of intermediate temperature solid oxide fuel cell electrolyte and preparation method thereof - Google Patents
A kind of intermediate temperature solid oxide fuel cell electrolyte and preparation method thereof Download PDFInfo
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- CN106848359A CN106848359A CN201710219407.7A CN201710219407A CN106848359A CN 106848359 A CN106848359 A CN 106848359A CN 201710219407 A CN201710219407 A CN 201710219407A CN 106848359 A CN106848359 A CN 106848359A
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- fuel cell
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- solid oxide
- oxide fuel
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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
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/126—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing cerium oxide
-
- 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
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
-
- 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
- H01M2300/0074—Ion conductive at high temperature
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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
Abstract
The present invention relates to a kind of intermediate temperature solid oxide fuel cell electrolyte and preparation method thereof.One kind is prepared using sol-gel combustion method and possesses proton conductivity intermediate temperature solid oxide fuel cell electrolyte, the molecular formula of the electrolyte is La1.85Na0.15Ce2O7‑δ, 0.15 ＞ δ ＞ 0.Its relative density reaches 99.0%；The electrolyte is drying 5%H2Electrical conductivity reaches 1.38 × 10 at 700 DEG C lower with 95%Ar mixed atmospheres‑2S/cm。
Description
Technical field
The invention belongs to the preparation field of solid electrolyte, and in particular to a kind of intermediate temperature solid oxide fuel cell electrolysis
Matter and preparation method thereof.
Background technology
The discovery of the energy is brought greatly just with using the progress and development for having promoted human civilization to the life of the mankind
Profit, but, 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 (Solid Oxide Fuel Cell, abbreviation SOFC) belongs to third generation fuel cell,
Be it is a kind of under high temperature directly by the chemical energy in being stored in fuel and oxidant efficiently, environmentally friendly change into electric energy
All solid state chemical generated device.Being generally considered can equally obtain extensively in future with Proton Exchange Membrane Fuel Cells (PEMFC)
A kind of fuel cell of general popularization and application.The advantages of it has the high efficiency of general fuel cell, low stain, is a kind of cleaning
Efficient energy resource system.
The electrolyte of the SOFC being commercially employed at present is Y2O3The zirconium oxide of stabilization（Abbreviation YSZ）And operating temperature
It is general all at 1000 DEG C, work at such high temperatures so that SOFC there are problems that it is many：Electrode densification, metallic interconnection materials
It is required that the problems such as high, battery hermetization is bad and cost increases.Therefore, SOFC operating temperatures are reduced and can be effectively reduced and be
The cost of system simultaneously improves stability.Traditional electrolyte YSZ material have not been suitable for being worked under middle Wen Huancai borders, therefore, find
A kind of middle low temperature has the electrolyte of high conductivity and good stability particularly important.And proton has small volume and quality
Light advantage, has relatively low ionic conduction activation energy under middle low temperature, therefore proton conductive oxide is that one kind can be applied to
The electrolyte of low-temperature working SOFC.
Proton electrolyte material of the invention can obtain electrical conductivity high under middle temperature condition of work, and in CO2And H2O
With good stability, with the electrolyte that can be used in middle low temperature SOFC needed for meeting at present.
The content of the invention
Possess proton conductivity intermediate temperature solid oxide fuel cell electrolyte it is an object of the invention to provide one kind, adopt
Na is prepared with collosol and gel-combustion method+Doping La2Ce2O7Middle temperature solid-oxide electrolyte.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of Na+Doping La2Ce2O7Intermediate temperature solid oxide fuel cell electrolyte preparation method, it is concretely comprised the following steps：
First, La1.85Na0.15Ce2O7-δPreparation method be：
1）By La1.85Na0.15Ce2O7-δ（0.15 ＞ δ ＞ 0）Stoichiometric proportion weighs La (NO3)3·nH2O、Ce(NO3)3·6H2O、
NaNO3, and be 1 by the mol ratio of metal cation and citric acid:1.5 weigh citric acid；
2）By La (NO3)3·nH2O、Ce(NO3)3·6H2O、NaNO3Deionized water dissolving is separately added into citric acid；
3）By step 2）Resulting solution is poured into citric acid solution successively, and is 15wt%- to mass concentration is added dropwise in solution
The ammoniacal liquor of 20wt%, to adjust solution ph as 7；
4）By step 3）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；
5）By in gel immigration evaporating dish, it is placed on electric furnace and heats, until self-propagating combustion occurs forms fluffy oxidate powder
End；
6）Gained oxide powder is heated to 800 ± 10 DEG C, 3 ± 0.1 hours is incubated, then natural cooling, is formed
La1.85Na0.15Ce2O7-δPowder；
2nd, the preparation of the cell electrolyte disk：
By gained La1.85Na0.15Ce2O7-δ（LNC）Powder is put into mould, under the pressure of 300MPa, it is made a diameter of 13 ±
0.1mm, thickness for 0.5 ± 0.1mm disk, by disk with 3 DEG C per minute of speed be heated to 1500 ± 10 DEG C insulation 5 ±
0.1 hour, obtain high performance intermediate temperature solid oxide fuel cell electrolyte disk.
Remarkable advantage of the invention is：
Because proton has the advantages that small volume and light weight, there is relatively low ionic conduction activation energy under middle low temperature, therefore
Proton conductive oxide is a kind of electrolyte that can be applied to low-temperature working SOFC.La2Ce2O7As a kind of proton conductor, its
CO2And H2There is good stability, by A Na in O+Preferable electrical conductivity is doped with, is adapted to be used in middle low-temperature solid oxygen
Compound fuel-cell electrolyte.The present invention is with 0.15mol ratios Na+Doping La2Ce2O7, it is incubated 5h's through 1500 ± 10 DEG C
Electrolyte sheet its relative density reaches 99.0%；Drying 5%H2Proton conductivity reaches at 700 DEG C lower with 95%Ar mixed atmospheres
To 1.38 × 10-2S/cm, and La2Ce2O7In CO2And H2There is good stability in O, therefore the electrolyte has very
The characteristics of effectively reducing temperature of fuel cell, improve chemical property.
Brief description of the drawings
Fig. 1 La1.85Na0.15Ce2O7-δThe XRD spectrum of sintered sheets；
Fig. 2 La1.85Na0.15Ce2O7-δThe electrical conductivity of piece and the relation curve of test temperature.
Specific embodiment
In order that content of the present invention easily facilitates understanding, with reference to specific embodiment to technology of the present invention
Scheme is described further, but the present invention is not limited only to this.
La1.85Na0.15Ce2O7-δ（LNC）Preparation method：
1）By La1.85Na0.15Ce2O7-δ（0.15 ＞ δ ＞ 0）Stoichiometric proportion weighs La (NO3)3、Ce(NO3)3·6H2O、NaNO3,
And by the mol ratio of metal cation and citric acid be 1:1.5 weigh citric acid；
2）By La (NO3)3、Ce(NO3)3·6H2O、 NaNO3Deionized water dissolving is used respectively with citric acid；
3）By step 2）Resulting solution is poured into citric acid solution successively, and is 15%- to mass concentration is added dropwise in solution
20% ammoniacal liquor, to adjust solution ph as 7；
4）By step 3）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；
5）By in gel immigration evaporating dish, it is placed on electric furnace and heats, until self-propagating combustion occurs forms fluffy oxidate powder
End；
6）Gained oxide powder is heated to 800 ± 10 DEG C, 3 ± 0.1 hours is incubated, then natural cooling, is formed
La1.85Na0.15Ce2O7-δPowder.
By gained La1.85Na0.15Ce2O7-δ（LNC）Powder is put into mould, under the pressure of 300MPa, is made a diameter of
13 ± 0.1mm, thickness are the disk of 0.5 ± 0.1mm, and disk is heated into 1500 ± 10 DEG C of insulations 5 with 3 DEG C per minute of speed
± 0.1 hour, obtain high performance intermediate temperature solid oxide fuel cell proton electrolyte disk.
Embodiment 1
（1）1 mole of La1.85Na0.15Ce2O7-δ（LNC）Preparation：
Prepare 0.01mol La1.85Na0.15Ce2O7-δ：
Weigh 1.85 moles of La (NO3)3·nH2O：601.102 grams of 1.85 × 324.92=；
Weigh 0.15 mole of NaNO3：0.15 × 84.99=12.749 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；
（2）By NaNO3、Ce(NO3)3·6H2O、La(NO3)3Deionized water dissolving is used respectively with citric acid；
（3）Above-mentioned all solution are poured into citric acid solution respectively, it is 7 that ammoniacal liquor regulation pH value is added dropwise；
（4）Mixed solution is put into 70 DEG C are heated in agitator, continuously stirred at 70 DEG C, and by adding in whipping process
Ammoniacal liquor, makes the pH value of solution be maintained at 7, until forming gel；
（5）Gel immigration evaporating dish is placed on electric furnace and is heated, until self-propagating combustion occurs forms fluffy oxide powder；
（6）Powder is heated to 800 ± 10 DEG C, 3 ± 0.1 hours are incubated, natural cooling forms La1.85Na0.15Ce2O7-δPowder.
The preparation of disk：The La that embodiment 1 is prepared into1.85Na0.15Ce2O7-δPowder is put into mould, 300MPa's
Under pressure, a diameter of 13mm ± 0.1mm, the disk of thickness 0.5mm ± 0.1mm are made, by disk with 3 DEG C per minute of heating speed
Degree is heated to 1500 DEG C ± 10 DEG C and is incubated 5 ± 0.1 hours, obtains required electrolyte disk.
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 ± 0.1 hours at 1500 ± 1 DEG C
La1.85Na0.15Ce2O7-δ（LNC）Silver paste is coated on electrolyte disk two sides, and silver electrode is obtained after being then calcined 2h in 450 DEG C.With silver
With alternating current impedance instrument be connected the silver electrode at two ends by silk.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
350-700 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 1.38 × 10 at 700 DEG C-2S/cm。
Claims (3)
1. a kind of intermediate temperature solid oxide fuel cell electrolyte, it is characterised in that：The molecular formula of the electrolyte is
La1.85Na0.15Ce2O7-δ, 0.15 ＞ δ ＞ 0.
2. a kind of method for preparing intermediate temperature solid oxide fuel cell electrolyte as claimed in claim 1, it is characterised in that：
1）By La1.85Na0.15Ce2O7-δStoichiometric proportion weighs La (NO3)3·nH2O、Ce(NO3)3·6H2O、NaNO3, and down payment
Category cation is 1 with the mol ratio of citric acid:1.5 weigh citric acid；
2）By La (NO3)3·nH2O、Ce(NO3)3·6H2O、NaNO3Deionized water dissolving is separately added into citric acid；
3）By step 2）Resulting solution is poured into citric acid solution successively, and to ammoniacal liquor is added dropwise in solution, to adjust solution
PH value is 7；
4）By step 3）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；
5）By in gel immigration evaporating dish, it is placed on electric furnace and heats, until self-propagating combustion occurs forms fluffy oxidate powder
End；
6）Gained oxide powder is heated to 800 ± 10 DEG C, 3 ± 0.1 hours is incubated, then natural cooling, is formed
La1.85Na0.15Ce2O7-δPowder；
7）By gained La1.85Na0.15Ce2O7-δPowder is put into mould, under the pressure of 300MPa, it is made a diameter of 13 ±
0.1mm, thickness for 0.5 ± 0.1mm disk, by disk with 3 DEG C per minute of speed be heated to 1500 ± 10 DEG C insulation 5 ±
0.1 hour, obtain high performance intermediate temperature solid oxide fuel cell electrolyte disk.
3. preparation method according to claim 2, it is characterised in that：Step 3）The mass concentration of the ammoniacal liquor is 15wt%-
20wt%。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108346812A (en) * | 2018-02-07 | 2018-07-31 | 福州大学 | A kind of A is adulterated 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 |
| 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 |
| CN112777624A (en) * | 2021-01-13 | 2021-05-11 | 中国科学技术大学 | Electrolyte material, preparation method and application thereof |
Citations (1)
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| CN103746134A (en) * | 2014-01-24 | 2014-04-23 | 福州大学 | Electrolyte for solid oxide fuel cell and preparation method thereof |
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2017
- 2017-04-06 CN CN201710219407.7A patent/CN106848359B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103746134A (en) * | 2014-01-24 | 2014-04-23 | 福州大学 | Electrolyte for solid oxide fuel cell and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| CHENG PENG: "Hydrothermal synthesis,sintering behavior and oxide ionic conductivity of Na-doped lanthanum silicate", 《J SOL-GEL SCI TECHNOL》 * |
| ZETIAN TAO: "La1.95Ca0.05Ce2O7-δ as the electrolyte for intermediate-temperature solid oxide fuel cells", 《JOURNAL OF POWER SOURCES》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108346812A (en) * | 2018-02-07 | 2018-07-31 | 福州大学 | A kind of A is adulterated intermediate temperature solid oxide fuel cell electrolyte and preparation method thereof |
| CN108346812B (en) * | 2018-02-07 | 2020-09-01 | 福州大学 | A-site 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 |
| 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 |
| 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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Granted publication date: 20190709 |