CN107171009B - Electrolyte of double-doped medium-temperature solid oxide fuel cell and preparation thereof - Google Patents
Electrolyte of double-doped medium-temperature solid oxide fuel cell and preparation thereof Download PDFInfo
- Publication number
- CN107171009B CN107171009B CN201710308677.5A CN201710308677A CN107171009B CN 107171009 B CN107171009 B CN 107171009B CN 201710308677 A CN201710308677 A CN 201710308677A CN 107171009 B CN107171009 B CN 107171009B
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- fuel cell
- oxide fuel
- solid oxide
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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 invention belongs to the field of preparation of solid electrolytes, and particularly relates to a double-doped medium-temperature solid oxide fuel cell electrolyte and a preparation method thereof. The invention adopts a nitrate gel combustion method to prepare the electrolyte of the intermediate-temperature solid oxide fuel cell, and the molecular formula is Ce0.85La0.11Cd0.04O2‑α0 < α < 0.095, relative density up to 98%, and ion conductivity up to 1.45X 10 at 700 deg.C in air‑2S/cm。
Description
Technical Field
The invention belongs to the field of preparation of solid electrolytes, and particularly relates to a double-doped medium-temperature solid oxide fuel cell electrolyte and a preparation method thereof.
Background
With the development of global industry and the rapid growth of population, the resources on the earth will be in more and more shortage. The united states Energy Information Agency (EIA) statistical structure shows that world energy demand has reached 106 million ton oil equivalent in 2010, and it is predicted that 136.5 million ton oil equivalent will be reached in 2025. Most of the conventional power generation methods convert chemical energy in fossil energy such as petroleum and natural gas into heat energy through combustion, and then the heat energy pushes mechanical equipment to generate mechanical energy, which is finally converted into electric energy. The energy conversion is not only limited by Carnot cycle, but also generates a large amount of dust, carbon dioxide, nitrogen oxides, sulfides and other harmful substances and noise; the solid oxide fuel cell has the advantages of wide fuel adaptability, high energy conversion efficiency, all solid state, modular assembly, zero pollution and the like, and can directly use various hydrocarbon fuels such as hydrogen, carbon monoxide, natural gas, liquefied gas, coal gas, biomass gas and the like. The power supply system is used as a fixed power station in civil fields such as large-scale centralized power supply, medium-scale power distribution, small-scale household combined heat and power supply and the like, and as a power supply of ships, vehicles and the like, and has wide application prospect.
The traditional SOFC has higher output power only at the operating temperature of more than 800 ℃, the high operating temperature has very high requirements on the connection sealing of the cell, the generation of side reactions among cell components is accelerated, the cell performance decay rate is increased, the cost of the cell is high, and the commercial development of the SOFC is greatly limited. Therefore, in order to develop SOFC commercially, the SOFC operation temperature is lowered, and development of low and medium temperature SOFC is a necessary trend. In SOFC systems, the electrolyte is the core of the cell, and the properties of the electrolyte directly determine the operating temperature and performance of the SOFC cell. Conventional electrolytes have not been suitable for use under medium and low temperature conditions, and therefore, an electrolyte having high conductivity at medium and low temperature has to be sought. The composite electrolyte has high conductivity and can meet the use conditions of medium and low temperature.
Disclosure of Invention
In order to improve the performance of the electrolyte of the medium-temperature solid oxide fuel cell, novel Ce is prepared by adopting a nitrate gel combustion method0.85La0.11Cd0.04O2-α(CLCO) composite electrolyte, the relative density of which reaches 98%; the conductivity at 700 deg.C under air atmosphere is 1.45 × 10-2S/cm。
Ce0.85La0.11Cd0.04O2-α(0 < α ≤ 0.095) the preparation method comprises:
1) raw material Ce (NO) was weighed in a stoichiometric ratio3)3·6H2O、La(NO3)3·nH2O、Cd(NO3)2·4H2The O complexing agent citric acid is prepared by the following steps of [ n (CA): n (metal cation) =1.5:1]Weighing;
2）Ce(NO3)3·6H2O、La(NO3)3·nH2O、Cd(NO3)2·4H2dissolving O and citric acid in deionized water respectively, mixing the above solutions, and stirring;
3) dropwise adding ammonia water (the concentration of the ammonia water is 15wt% -20 wt%) to adjust the pH value to 7;
4) heating the mixed solution obtained in the step 3) to 45 ℃ in a stirrer, continuously stirring at 45 ℃, and adding ammonia water in the stirring process to keep the pH value of the solution at 7 until gel is formed;
5) transferring the gel into an evaporating dish, putting the evaporating dish on an electric furnace, and heating until self-propagating combustion occurs to form fluffy oxide powder;
6) calcining at 600 ℃ for 30 minutes to remove organic matters, and then calcining at 800 +/-10 ℃ for 3 +/-0.1 hours to form Ce0.85La0.11Cd0.04O2-α(CLCO) powder.
Putting the prepared CLCO powder into a die, preparing a wafer under the pressure of 300MPa, heating the wafer to 1350 +/-10 ℃ at the heating speed of 3 ℃ per minute, and preserving the heat for 4 +/-0.1 hours to obtain the required electrolyte wafer.
The invention has the following remarkable advantages:
1. the advantages are that: the use temperature is in the middle temperature (600-800 ℃) range, and the conductivity and the power density are higher.
2. The application is as follows: the electrolyte is used for an intermediate-temperature solid oxide fuel cell.
Drawings
FIG. 1 is a graph of the relationship between the conductivity and the test temperature of the electrolyte CLCO after sintering at 1350 ℃ for 4 h.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
Ce0.85La0.11Cd0.04O2-α（0<Preparation method of α ≦ 0.095) (CLCO)
1) Weighing the following raw materials in a stoichiometric ratio: e (NO)3)3·6H2O,La(NO3)3·nH2O,Cd(NO3)2·4H2O，
The complexing agent citric acid is weighed according to the ratio of [ n (CA) =1.5:1 ].
2）Ce(NO3)3·6H2O,La(NO3)3·nH2O，Cd(NO3)2·4H2Dissolving O and citric acid in deionized water respectively;
3) mixing the above solutions, and stirring
4) Heating the mixed solution obtained in the step 3) to 45 ℃ in a stirrer, continuously stirring at 45 ℃, and adding ammonia water in the stirring process to keep the pH value of the solution at 7 until gel is formed;
5) transferring the gel into an evaporating dish, putting the evaporating dish on an electric furnace, and heating until self-propagating combustion occurs to form fluffy oxide powder;
6) calcining at 600 deg.C for 30min to remove organic matter, and then calcining at 800 deg.C + -10 deg.C for 3 + -0.1 hr to form CLCO powder.
Specifically, the method comprises the following steps:
1 mol of Ce0.85La0.11Cd0.04O2-αPreparation of (CLCO):
0.85 mol of Ce (NO) is weighed3)3·6H2O: 0.85 × 434.22 =369.08 g
0.11 mol of La (NO) was weighed out3)3·nH2O: 0.11 × 324.92=35.74 g
0.04 mol of Cd (NO) was weighed3)2·4H2O: 0.04 × 308.48=12.34 g
Weigh 1.5 moles of citric acid: 1.5 × 210.14=315.21 g
Ce(NO3)3·6H2O,La(NO3)3·nH2O,Cd(NO3)2·4H2Dissolving O and citric acid in deionized water respectively; mixing the above solutions and stirring; heating to 45 deg.C in water bath, continuously stirring at 45 deg.C, and adding ammonia water during stirring to maintain pH of the solution at 7 until gel is formed; transferring the gel into evaporating dish, heating in electric furnace until self-propagating combustion occurs to form fluffy oxide powder；
The powder was calcined at 600 ℃ for 30min to remove organics and then calcined at 800 ℃. + -. 10 ℃ for 3. + -. 0.1 hours to form CLCO powder.
Example 2
Preparation of the wafer: the CLCO powder prepared in the example 1 is put into a die, a wafer with the diameter of 13mm +/-0.1 mm and the thickness of 0.5mm +/-0.1 mm is prepared under the pressure of 300MPa, and the wafer is heated to 1350 ℃ at the heating speed of 3 ℃ per minute and is kept warm for 4 hours, so that the required electrolyte wafer is obtained.
Conductivity test method:
the ac conductance of the electrolyte was measured by the two-terminal method. The obtained Ce is sintered for 4 plus or minus 0.1 hours at 1350 plus or minus 10 DEG C0.85La0.11Cd0.04O2-αCoating silver paste on two sides of the electrolyte wafer, and then roasting for 2h at 450 ℃ to obtain the silver electrode. Silver electrodes at two ends are connected with an alternating current impedance instrument by silver wires. The AC impedance meter is electrochemical workstation CHI660E of Shanghai Chenghua apparatus, Inc., and has potential of 10mV, frequency range of 1kHz-20MHz, AC conductance temperature of 700 deg.C, measurement in air atmosphere, and measurement in air atmosphere. The conductivity is calculated using the following formula:
wherein, sigma is electrolyte conductivity, S/cm;
h is the thickness of the electrolyte sheet in cm;
r is electrolyte resistance with unit omega;
s is the cross-sectional area of the electrolyte sheet in cm2。
Claims (2)
1. A double-doped medium-temperature solid oxide fuel cell electrolyte is characterized in that: the molecular formula of the electrolyte is Ce0.85La0.11Cd0.04O2-αThe content of the compound is more than 0 and less than or equal to α and less than or equal to 0.095, and the preparation method comprises the following specific steps:
1) raw material Ce (NO) was weighed in a stoichiometric ratio3)3·6H2O、La(NO3)3·nH2O、Cd(NO3)2·4H2O; weighing citric acid according to the molar ratio of the metal cations to the citric acid of 1: 1.5;
2) adding Ce (NO)3)3·6H2O、La(NO3)3·nH2O、Cd(NO3)2·4H2Dissolving O and citric acid in deionized water respectively, mixing the above solutions, and stirring;
3) dropwise adding ammonia water into the mixed solution obtained in the step (2) to adjust the pH value to 7;
4) putting the mixed solution obtained in the step (3) into a stirrer, heating to 45 ℃, continuously stirring at 45 ℃, and adding ammonia water during stirring to keep the pH value of the solution at 7 until gel is formed;
5) transferring the gel into an evaporating dish, putting the evaporating dish on an electric furnace, and heating until self-propagating combustion occurs to form fluffy oxide powder;
6) calcining the powder obtained in the step (5) at 600 ℃ for 30 minutes to remove organic matters, and then calcining at 800 +/-10 ℃ for 3 +/-0.1 hours to form Ce0.85La0.11Cd0.04O2-αPowder;
7) the obtained Ce0.85La0.11Cd0.04O2-αPutting the powder into a die, preparing a wafer under the pressure of 300MPa, heating the wafer to 1350 +/-10 ℃ at the heating speed of 3 ℃ per minute, and preserving the heat for 4 +/-0.1 hours to obtain the required electrolyte wafer.
2. The electrolyte of a double-doped intermediate-temperature solid oxide fuel cell according to claim 1, wherein: the concentration of the ammonia water is 15wt% -20 wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710308677.5A CN107171009B (en) | 2017-05-04 | 2017-05-04 | Electrolyte of double-doped medium-temperature solid oxide fuel cell and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710308677.5A CN107171009B (en) | 2017-05-04 | 2017-05-04 | Electrolyte of double-doped medium-temperature solid oxide fuel cell and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107171009A CN107171009A (en) | 2017-09-15 |
| CN107171009B true CN107171009B (en) | 2020-06-12 |
Family
ID=59813808
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710308677.5A Expired - Fee Related CN107171009B (en) | 2017-05-04 | 2017-05-04 | Electrolyte of double-doped medium-temperature solid oxide fuel cell and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107171009B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106935889B (en) * | 2017-05-04 | 2019-09-13 | 福州大学 | A kind of intermediate temperature solid oxide fuel cell electrolyte of oxygen ion conduction |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005310737A (en) * | 2004-03-23 | 2005-11-04 | Toto Ltd | Solid oxide fuel cell |
| CN105633439A (en) * | 2016-01-08 | 2016-06-01 | 福州大学 | Electrolyte for intermediate-temperature solid oxide fuel cell and preparation method of electrolyte |
-
2017
- 2017-05-04 CN CN201710308677.5A patent/CN107171009B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005310737A (en) * | 2004-03-23 | 2005-11-04 | Toto Ltd | Solid oxide fuel cell |
| CN105633439A (en) * | 2016-01-08 | 2016-06-01 | 福州大学 | Electrolyte for intermediate-temperature solid oxide fuel cell and preparation method of electrolyte |
Non-Patent Citations (2)
| Title |
|---|
| 《Polyol Synthesis and Investigation of Ce1-xRExO2-x/2 (RE = Sm, Gd, Nd, La, 0 ≤ x ≤ 0.25) Electrolytes for IT-SOFCs》;Gӧknur Dӧnmez et al.;《Journal of the American Ceramic Society》;20150228;第98卷(第2期);正文第501-506页、表2、图5d * |
| Gӧknur Dӧnmez et al..《Polyol Synthesis and Investigation of Ce1-xRExO2-x/2 (RE = Sm, Gd, Nd, La, 0 ≤ x ≤ 0.25) Electrolytes for IT-SOFCs》.《Journal of the American Ceramic Society》.2015,第98卷(第2期),第501-506页、表2、图5d. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107171009A (en) | 2017-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108649236A (en) | A kind of the air pole material and preparation method of intermediate temperature solid oxide fuel cell | |
| CN105633439B (en) | A kind of intermediate temperature solid oxide fuel cell electrolyte and preparation method thereof | |
| CN107134584B (en) | Medium-temperature solid oxide fuel cell electrolyte and preparation method thereof | |
| CN108039495B (en) | Non-metal element modified layered perovskite oxide oxygen reduction electrode material | |
| CN113839054A (en) | Reversible proton ceramic battery electrode material and preparation method and application thereof | |
| CN112408490B (en) | Hydrothermal synthesis of Ba doped Sr2Fe1.5Mo0.5O6Method for preparing double perovskite nano material | |
| CN108987776B (en) | Medium-temperature solid oxide fuel cell electrolyte and preparation method thereof | |
| CN107171009B (en) | Electrolyte of double-doped medium-temperature solid oxide fuel cell and preparation thereof | |
| CN110649300A (en) | Electrolyte of alkaline earth metal doped proton conduction intermediate-temperature solid oxide fuel cell | |
| CN106887626B (en) | Intermediate temperature solid oxide fuel cell composite electrolyte and preparation method thereof | |
| CN108346812B (en) | A-site doped medium-temperature solid oxide fuel cell electrolyte and preparation method thereof | |
| CN108365244B (en) | Yttrium-doped proton conduction medium-temperature solid oxide fuel cell electrolyte | |
| CN108232303A (en) | Oxygen ion conduction intermediate temperature solid oxide fuel cell electrolyte preparation method | |
| CN105655618B (en) | One kind melts mixed type intermediate temperature solid oxide fuel cell electrolyte admittedly | |
| CN106711481B (en) | A kind of intermediate temperature solid oxide fuel cell composite electrolyte and preparation method thereof | |
| CN107230795B (en) | Electrolyte of intermediate-temperature solid oxide fuel cell with proton conductivity | |
| CN106207238A (en) | A kind of molten salts compound intermediate temperature solid oxide fuel cell electrolyte | |
| CN108110289B (en) | Proton-conducting medium-low temperature solid oxide fuel cell electrolyte | |
| CN106935889B (en) | A kind of intermediate temperature solid oxide fuel cell electrolyte of oxygen ion conduction | |
| CN107171011A (en) | A kind of In doping intermediate temperature solid oxide fuel cell electrolyte | |
| CN115241471A (en) | Solid oxide fuel cell cathode material and preparation method and application thereof | |
| CN110828873B (en) | Preparation method of oxygen ion conduction medium-temperature solid oxide fuel cell electrolyte | |
| CN110931809A (en) | Doped medium-low temperature SOFC cathode material, preparation method and application thereof, and SOFC cathode material | |
| CN111974397A (en) | Thermo-electric coupled phase water oxidation catalyst for recycling low-grade waste heat | |
| CN114709457B (en) | Double-doped medium-temperature solid oxide fuel cell electrolyte and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200612 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |