CN106848359B - 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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- CN106848359B CN106848359B CN201710219407.7A CN201710219407A CN106848359B CN 106848359 B CN106848359 B CN 106848359B CN 201710219407 A CN201710219407 A CN 201710219407A CN 106848359 B CN106848359 B CN 106848359B
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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 being prepared using sol-gel combustion method and has 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 in dry 5%H2Conductivity reaches 1.38 × 10 at 700 DEG C lower with 95%Ar mixed atmosphere‑2S/cm。
Description
Technical field
The invention belongs to the preparation fields of solid electrolyte, and in particular to a kind of intermediate temperature solid oxide fuel cell electrolysis
Matter and preparation method thereof.
Background technique
The discovery of the energy is brought greatly just with using the progress and development for having pushed human civilization to the life of the mankind
Benefit, still, 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 (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 being stored in fuel and oxidant efficiently, be environmentally friendly converted to 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.It has many advantages, such as that the high efficiency of general fuel cell, low pollution are a kind of cleanings
Efficient energy resource system.
The electrolyte for the SOFC being commercially employed at present is Y2O3Stable zirconium oxide (abbreviation YSZ) and operating temperature
Generally all at 1000 DEG C, work at such high temperatures so that SOFC there are many problems: electrode densification, metallic interconnection materials
It is required that the problems such as high, battery hermetization is bad and increased costs.Therefore, it reduces SOFC operating temperature and can be effectively reduced and be
The cost of system simultaneously improves stability.Traditional electrolyte YSZ material has not been suitable for working under medium temperature ring material border, therefore, finds
A kind of electrolyte of the middle low temperature with high conductivity and good stability is particularly important.And proton has small in size and quality
Light advantage has lower 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 high conductivity under medium temperature operating condition, and in CO2And H2O
With good stability, to meet the electrolyte that can be used in middle low temperature SOFC required at present.
Summary of the invention
The purpose of the present invention is to provide one kind to have proton conductivity intermediate temperature solid oxide fuel cell electrolyte, adopts
Na is prepared with collosol and gel-combustion method+Adulterate La2Ce2O7Medium temperature solid oxide electrolyte.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of Na+Adulterate La2Ce2O7Intermediate temperature solid oxide fuel cell electrolyte preparation method, specific steps
Are as follows:
One, La1.85Na0.15Ce2O7-δThe preparation method comprises the following steps:
1) La is pressed1.85Na0.15Ce2O7-δ(0.15 > δ > 0) stoichiometric ratio weighs La (NO3)3·nH2O、Ce(NO3)3·
6H2O、NaNO3, and be that 1:1.5 weighs citric acid by the molar ratio of metal cation and citric acid；
2) by La (NO3)3·nH2O、Ce(NO3)3·6H2O、NaNO3Deionized water dissolving is separately added into citric acid；
3) step 2 acquired solution is successively poured into citric acid solution, and mass concentration is added dropwise into solution and is
The ammonium hydroxide of 15wt%-20wt%, to adjust solution ph as 7；
4) mixed solution for obtaining step 3), 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；
5) gel is moved into evaporating dish, is placed on electric furnace and heats, until self-propagating combustion, which occurs, forms fluffy oxidation
Object powder；
6) gained oxide powder is heated to 800 ± 10 DEG C, keeps the temperature 3 ± 0.1 hours, then natural cooling, formed
La1.85Na0.15Ce2O7-δPowder；
Two, the preparation of the cell electrolyte disk:
By gained La1.85Na0.15Ce2O7-δ(LNC) powder is put into mold, and under the pressure of 300MPa, diameter, which is made, is
Disk is heated to 1500 ± 10 DEG C of heat preservations 5 with 3 DEG C of speed per minute by 13 ± 0.1mm, the disk with a thickness of 0.5 ± 0.1mm
± 0.1 hour, obtain high performance intermediate temperature solid oxide fuel cell electrolyte disk.
Remarkable advantage of the invention is:
Since proton has the advantages that small in size and light weight, there is lower 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,
It is in CO2And H2There is good stability in O, pass through A Na+It is doped with preferable conductivity, is suitble to be used in middle low-temperature solid
Oxide body fuel-cell electrolyte.The present invention is with 0.15mol ratio Na+Adulterate La2Ce2O7, kept the temperature through 1500 ± 10 DEG C
Its relative density of the electrolyte sheet of 5h reaches 99.0%；In dry 5%H2Proton conducting at 700 DEG C lower with 95%Ar mixed atmosphere
Rate reaches 1.38 × 10-2S/cm, and La2Ce2O7In CO2And H2It is with good stability in O, therefore the electrolyte has
Largely effective reduction temperature of fuel cell improves the characteristics of chemical property.
Detailed description of the invention
Fig. 1 La1.85Na0.15Ce2O7-δThe XRD spectrum of sintered sheets；
Fig. 2 La1.85Na0.15Ce2O7-δThe conductivity of piece and the relation curve of test temperature.
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.
La1.85Na0.15Ce2O7-δ(LNC) preparation method:
1) La is pressed1.85Na0.15Ce2O7-δ(0.15 > δ > 0) stoichiometric ratio weighs La (NO3)3、Ce(NO3)3·6H2O、
NaNO3, and be that 1:1.5 weighs citric acid by the molar ratio of metal cation and citric acid；
2) by La (NO3)3、Ce(NO3)3·6H2O、 NaNO3Deionized water dissolving is used respectively with citric acid；
3) step 2 acquired solution is successively poured into citric acid solution, and mass concentration is added dropwise into solution and is
The ammonium hydroxide of 15%-20%, to adjust solution ph as 7；
4) mixed solution for obtaining step 3), 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；
5) gel is moved into evaporating dish, is placed on electric furnace and heats, until self-propagating combustion, which occurs, forms fluffy oxidation
Object powder；
6) gained oxide powder is heated to 800 ± 10 DEG C, keeps the temperature 3 ± 0.1 hours, then natural cooling, formed
La1.85Na0.15Ce2O7-δPowder.
By gained La1.85Na0.15Ce2O7-δ(LNC) powder is put into mold, and under the pressure of 300MPa, diameter, which is made, is
Disk is heated to 1500 ± 10 DEG C of heat preservations 5 with 3 DEG C of speed per minute by 13 ± 0.1mm, the disk with a thickness of 0.5 ± 0.1mm
± 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:1.85 × 324.92=601.102 gram；
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 gram；
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 ammonium hydroxide, which is added dropwise, and adjusts pH value；
(4) mixed solution is put into blender and is heated to 70 DEG C, continuously stirred at 70 DEG C, and led in whipping process
It crosses and adds ammonium hydroxide, the pH value of solution is made to be maintained at 7, until forming gel；
(5) gel immigration evaporating dish is placed on electric furnace and is heated, until self-propagating combustion, which occurs, forms fluffy oxide
Powder；
(6) powder is heated to 800 ± 10 DEG C, keeps the temperature 3 ± 0.1 hours, natural cooling forms La1.85Na0.15Ce2O7-δ
Powder.
The preparation of disk: the La that embodiment 1 is prepared into1.85Na0.15Ce2O7-δPowder is put into mold, 300MPa's
Under pressure, the disk that diameter is 13mm ± 0.1mm, thickness 0.5mm ± 0.1mm is made, by disk with 3 DEG C of heating speed per minute
Degree is heated to 1500 DEG C ± 10 DEG C and keeps the temperature 5 ± 0.1 hours, obtains required electrolyte disk.
The test method of conductivity:
The conductance for alternating current of electrolyte is measured using two-terminal method.By the gained after being sintered 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 then made after 450 DEG C of roasting 2h.With
The silver electrode at both ends is connect by filamentary silver with alternating current impedance instrument.The alternating current impedance instrument used is Shanghai Chen Hua Instrument Ltd. model
Frequency range 1kHz-20MHz is measured, the temperature of conductance for alternating current is measured using current potential 20mV for CHI660E electrochemical workstation
It is 350-700 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 1.38 × 10 at 700 DEG C-2S/cm。
Claims (2)
1. a kind of intermediate temperature solid oxide fuel cell electrolyte preparation method, it is characterised in that: the molecule of the electrolyte
Formula is La1.85Na0.15Ce2O7-δ, 0.15 > δ > 0；Specific preparation method the following steps are included:
1) La is pressed1.85Na0.15Ce2O7-δStoichiometric ratio weighs La (NO3)3·nH2O、Ce(NO3)3·6H2O、NaNO3, and down payment
The molar ratio for belonging to cation and citric acid is that 1:1.5 weighs citric acid；
2) by La (NO3)3·nH2O、Ce(NO3)3·6H2O、NaNO3Deionized water dissolving is separately added into citric acid；
3) step 2 acquired solution is successively poured into citric acid solution, and ammonium hydroxide is added dropwise into solution, to adjust solution
PH value is 7；
4) mixed solution for obtaining step 3), 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；
5) gel is moved into evaporating dish, is placed on electric furnace and heats, until self-propagating combustion, which occurs, forms fluffy oxidate powder
End；
6) gained oxide powder is heated to 800 ± 10 DEG C, keeps the temperature 3 ± 0.1 hours, then natural cooling, formed
La1.85Na0.15Ce2O7-δPowder；
7) by gained La1.85Na0.15Ce2O7-δPowder is put into mold, under the pressure of 300MPa, be made diameter be 13 ±
0.1mm, the disk with a thickness of 0.5 ± 0.1mm, by disk with 3 DEG C of speed per minute be heated to 1500 ± 10 DEG C heat preservation 5 ±
0.1 hour, obtain high performance intermediate temperature solid oxide fuel cell electrolyte disk.
2. preparation method according to claim 1, it is characterised in that: the mass concentration of ammonium hydroxide described in step 3) is 15wt%-
20wt%。
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| 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 |
| CN108987776B (en) * | 2018-07-20 | 2021-10-29 | 福州大学 | Medium-temperature solid oxide fuel cell electrolyte and preparation method thereof |
| CN109638325B (en) * | 2018-12-18 | 2022-03-15 | 福州大学 | Strontium-doped medium-temperature solid oxide fuel cell electrolyte |
| 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)
| Publication number | Priority date | Publication date | Assignee | Title |
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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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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
Non-Patent Citations (2)
| Title |
|---|
| Hydrothermal synthesis,sintering behavior and oxide ionic conductivity of Na-doped lanthanum silicate;Cheng Peng;《J Sol-Gel Sci Technol》;20160517;摘要 |
| La1.95Ca0.05Ce2O7-δ as the electrolyte for intermediate-temperature solid oxide fuel cells;Zetian Tao;《Journal of Power Sources》;20110311;摘要 |
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