CN107230795B - Electrolyte of intermediate-temperature solid oxide fuel cell with proton conductivity - Google Patents
Electrolyte of intermediate-temperature solid oxide fuel cell with proton conductivity Download PDFInfo
- Publication number
- CN107230795B CN107230795B CN201710368348.XA CN201710368348A CN107230795B CN 107230795 B CN107230795 B CN 107230795B CN 201710368348 A CN201710368348 A CN 201710368348A CN 107230795 B CN107230795 B CN 107230795B
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- solution
- fuel cell
- solid oxide
- oxide fuel
- 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
-
- 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
Landscapes
- Fuel Cell (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
Abstract
The invention discloses an electrolyte of a medium-temperature solid oxide fuel cell with proton conductivity, belonging to fuel cell electricityThe field of preparation of a electrolyte. The invention adopts La (NO)3)3·nH2O、Ce(NO3)3·6H2O, KNO and citric acid as main raw materials, and the electrolyte is prepared by a sol-gel combustion method, the relative density of the electrolyte reaches 98.0%, and the maximum conductivity of the prepared electrolyte at 800 ℃ in an air atmosphere is 1.76 × 10‑2S/cm, after drying at 5% H2The electric conductivity of the alloy at 700 ℃ in a mixed atmosphere of the alloy and 95% Ar is 1.57 × 10‑2S/cm and in CO2And H2The electrolyte has good stability, so the electrolyte has the characteristics of effectively reducing the working temperature of the fuel cell and improving the electrochemical performance, and is suitable for being applied to medium and low temperature solid oxide fuel cells.
Description
Technical Field
The invention belongs to the field of preparation of fuel cell electrolytes, and particularly relates to an intermediate-temperature solid oxide fuel cell electrolyte with proton conductivity.
Background
Energy is the basis of human society survival and development, still takes fossil energy as the main worldwide, and has a series of serious problems such as unreasonable utilization, low conversion efficiency, serious pollution and the like in the current use process. Therefore, the rational and efficient utilization of fossil fuels is one of the difficulties facing human beings.
A Solid Oxide Fuel Cell (SOFC) is an electrochemical device which directly converts chemical energy in fossil Fuel into electric energy through electrode reaction, has the advantages of high efficiency, environmental friendliness, no pollution, realization of cogeneration and the like, and is a clean and efficient energy system.
The currently used SOFC typically has Y as the electrolyte2O3Stabilized zirconia (abbreviated as YSZ) and operating temperatures of typically 1000 ℃, operating at such high temperatures makes SOFCs problematic: poor thermal stability of battery components, high requirements for connector materials, and poor battery sealing performanceAnd the problems of increased cost and poor long-term operation stability, and the like, and seriously obstruct the commercialization process of the SOFC. Therefore, lowering the SOFC operating temperature effectively reduces the cost of the system and improves stability, avoiding problems associated with high temperature operation. The traditional electrolyte material YSZ is not suitable for working in medium and low temperature environment, so it is very important to find an electrolyte material with high conductivity and good stability at medium and low temperature. Compared with an oxygen ion conductor, the proton conductor has the advantages of small volume and light weight, has lower ion conduction activation energy and higher ion conductivity at medium and low temperature, so the proton conductive oxide is an electrolyte applicable to the SOFC (solid oxide fuel cell) working at low temperature. The proton electrolyte material can obtain high conductivity under the condition of medium-temperature working and can generate high-temperature CO2And the product has good stability under the condition of water vapor, and can meet the performance requirements of the current medium-low temperature SOFC.
Disclosure of Invention
The invention aims to provide an electrolyte of a medium-temperature solid oxide fuel cell with proton conductivity, aiming at overcoming the defects in the prior art, and the maximum conductivity of the prepared electrolyte is 1.76 × 10 at 800 ℃ in an air atmosphere-2S/cm, after drying at 5% H2The electric conductivity of the alloy at 700 ℃ in a mixed atmosphere of the alloy and 95% Ar is 1.57 × 10-2S/cm, and is suitable for being applied to medium and low temperature solid oxide fuel cells.
In order to achieve the purpose, the invention adopts the following technical scheme:
an intermediate-temperature solid oxide fuel cell electrolyte with proton conductivity has a chemical formula of La1.80K0.20Ce2O7-δWherein delta is more than 0 and less than or equal to 0.2; the preparation method of the electrolyte specifically comprises the following steps:
(I) La1.80K0.20Ce2O7-δThe preparation of (1):
1) according to La1.80K0.20Ce2O7-δStoichiometric weighing of La (NO)3)3·nH2O、Ce(NO3)3·6H2O andKNO3weighing citric acid according to the molar ratio of the metal cations to the citric acid of 1: 1.5;
2) adding La (NO)3)3·nH2O、Ce(NO3)3·6H2O 、KNO3And citric acid are respectively added into deionized water to be dissolved to form solution;
3) the La (NO) obtained in the step 2)3)3·nH2O solution, Ce (NO)3)3·6H2O solution and KNO3The solution is poured into the citric acid solution obtained in the step 2) in sequence, and ammonia water with the mass concentration of 15-20% is added into the solution drop by drop to adjust the pH value of the solution to 7;
4) heating the mixed solution obtained in the step 3) to 70 ℃ in a stirrer, continuously stirring at 70 ℃, adding ammonia water with the mass concentration of 15-20% in the stirring process, and keeping the pH value of the solution at 7 until gel is formed;
5) transferring the gel obtained in the step 4) into an evaporating dish, and placing the evaporating dish on an electric furnace for heating until self-propagating combustion occurs to form fluffy oxide powder;
6) heating the oxide powder obtained in the step 5) to 790-810 ℃, preserving the heat for 2.9-3.1 hours, and then naturally cooling to form La1.80K0.20Ce2O7-δ(LKC) powder;
(II) preparing an electrolyte of the intermediate-temperature solid oxide fuel cell:
the La prepared in the step (one)1.80K0.20Ce2O7-δPutting the powder into a die, preparing a wafer with the diameter of 13 +/-0.1 mm and the thickness of 0.5 +/-0.1 mm under the pressure of 300MPa, heating the wafer to 1500 +/-1 ℃ at the speed of 3 ℃ per minute, and preserving the temperature for 5 +/-0.1 hours to obtain the electrolyte wafer of the intermediate-temperature solid oxide fuel cell with proton conductivity.
The invention has the beneficial effects that: the proton has the advantages of small volume and light weight, and has lower ion conduction activation energy at medium and low temperature, so the proton conductive oxide prepared by the invention is an electrolytic oxide applicable to low-temperature operation SOFCQuality; la2Ce2O7As a proton conductor in CO2And H2Good stability in O, through the A-position K+The doping improves the conductivity of the alloy, and the maximum conductivity is 1.76 × 10 at 800 ℃ in air atmosphere-2S/cm, after drying at 5% H2The electric conductivity of the alloy at 700 ℃ in a mixed atmosphere of the alloy and 95% Ar is 1.57 × 10-2S/cm, and is suitable for being applied to medium and low temperature solid oxide fuel cells.
Drawings
FIG. 1 shows La under air1.8K0.2Ce2O7-δThe relation curve of the conductivity and the test temperature;
FIG. 2 shows La in a mixed atmosphere of 5% hydrogen and 95% argon1.8K0.2Ce2O7-δConductivity versus test temperature curve.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.
Examples
(one) 1mol of La1.80K0.20Ce2O7-δPreparation of (LKC):
1.80 mol of La (NO) was weighed out3)3·nH2O1.80 × 324.92= 584.856 g
Weighing 0.20 mol KNO30.20 × 84.99.99 =16.998 g
2.00 mol of Ce (NO) was weighed3)3·6H22.00 × 434.22=868.440 g
6.00 mol of citric acid 6.00 × 210.14=1260.840 g is weighed
Mixing KNO3、Ce(NO3)3·6H2O、La(NO3)3·nH2Dissolving O and citric acid in deionized water respectively to form a solution;
adding La (NO)3)3·nH2O solution, Ce (NO)3)3·6H2O solution and KNO3The solution is respectively poured into citric acid solution, and the mass concentration is drippedAdjusting the pH value to 7 by 15% ammonia water;
heating the mixed solution to 70 ℃ in a stirrer, continuously stirring at 70 ℃, and keeping the pH value of the solution at 7 by adding ammonia water with the mass concentration of 15% in the stirring process until gel is formed;
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;
heating the powder to 800 ℃, preserving heat for 3 hours, and naturally cooling to form La1.80K0.20Ce2O7-δPowder;
(II) preparing an electrolyte of the intermediate-temperature solid oxide fuel cell:
la prepared in the step (one)1.80K0.20Ce2O7-δPutting the powder into a die, preparing a wafer with the diameter of 13mmmm and the thickness of 0.5mmmm under the pressure of 300MPa, heating the wafer to 1500 ℃ at the heating speed of 3 ℃ per minute, and preserving the heat for 5 hours to obtain the required electrolyte wafer.
Conductivity test method:
the ac conductance of the electrolyte was measured by the two-terminal method. La obtained after sintering at 1500 + -1 deg.C for 5 + -0.1 hr1.80K0.20Ce2O7-δAnd (LKC) electrolyte wafers are coated with silver paste on two sides and then are roasted for 2 hours 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 an electrochemical workstation of Shanghai Chenghua apparatus, Inc. model number CHI660E, the potential is 30mV, the frequency range is 0.1Hz-1000kHz, the temperature of the impedance spectrum is 350-; after drying at 5% H2And the impedance spectrum temperature of the sample is measured to be 350-700 ℃ under the mixed atmosphere of 95% Ar, and the result is shown in figure 2; 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。
As can be seen from FIG. 1, the maximum conductivity of the electrolyte at 800 ℃ in an air atmosphere was 1.76 × 10-2S/cm, as can be seen in FIG. 2, the electrolyte is 5% H on dry2The electric conductivity of the alloy at 700 ℃ in a mixed atmosphere of the alloy and 95% Ar is 1.57 × 10-2S/cm, and La2Ce2O7In CO2And H2O has good stability, so the electrolyte has the characteristics of effectively reducing the working temperature of the fuel cell and improving the electrochemical performance.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (1)
1. An intermediate-temperature solid oxide fuel cell electrolyte having proton conductivity, characterized in that: the electrolyte is La1.80K0.20Ce2O7-δWherein delta is more than 0 and less than or equal to 0.2;
the preparation method of the medium-temperature solid oxide fuel cell electrolyte with proton conductivity specifically comprises the following steps:
(I) La1.80K0.20Ce2O7-δThe preparation of (1):
1) according to La1.80K0.20Ce2O7-δStoichiometric weighing of La (NO)3)3·nH2O、Ce(NO3)3·6H2O and KNO3Weighing citric acid according to the molar ratio of the metal cations to the citric acid of 1: 1.5;
2) adding La (NO)3)3·nH2O、Ce(NO3)3·6H2O 、KNO3And citric acid are respectively added into deionized water to be dissolved to form solution;
3) subjecting the product of step 2)Obtained La (NO)3)3·nH2O solution, Ce (NO)3)3·6H2O solution and KNO3Sequentially pouring the solution into the citric acid solution obtained in the step 2), and dropwise adding ammonia water into the solution to adjust the pH value of the solution to 7;
4) heating the mixed solution obtained in the step 3) to 70 ℃ in a stirrer, continuously stirring at 70 ℃, and adding ammonia water during stirring to keep the pH value of the solution at 7 until gel is formed;
5) transferring the gel obtained in the step 4) into an evaporating dish, and placing the evaporating dish on an electric furnace for heating until self-propagating combustion occurs to form fluffy oxide powder;
6) heating the oxide powder obtained in the step 5) to 790-810 ℃, preserving the heat for 2.9-3.1 hours, and then naturally cooling to form La1.80K0.20Ce2O7-δPowder;
(II) preparing an electrolyte of the intermediate-temperature solid oxide fuel cell:
the La prepared in the step (one)1.80K0.20Ce2O7-δPutting the powder into a die, preparing a wafer with the diameter of 13 +/-0.1 mm and the thickness of 0.5 +/-0.1 mm under the pressure of 300MPa, heating the wafer to 1500 +/-1 ℃ at the speed of 3 ℃ per minute, and preserving the temperature for 5 +/-0.1 hours to obtain the electrolyte wafer of the intermediate-temperature solid oxide fuel cell with proton conductivity;
the mass concentration of the ammonia water in the steps 3) and 4) is 15-20%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710368348.XA CN107230795B (en) | 2017-05-23 | 2017-05-23 | Electrolyte of intermediate-temperature solid oxide fuel cell with proton conductivity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710368348.XA CN107230795B (en) | 2017-05-23 | 2017-05-23 | Electrolyte of intermediate-temperature solid oxide fuel cell with proton conductivity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107230795A CN107230795A (en) | 2017-10-03 |
| CN107230795B true CN107230795B (en) | 2020-07-07 |
Family
ID=59934631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710368348.XA Expired - Fee Related CN107230795B (en) | 2017-05-23 | 2017-05-23 | Electrolyte of intermediate-temperature solid oxide fuel cell with proton conductivity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107230795B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942364A (en) * | 2012-11-02 | 2013-02-27 | 天津大学 | Zinc oxide-carbonate co-doped cerium barium zirconate proton conductor material and preparation method thereof |
| CN104078687B (en) * | 2013-03-25 | 2017-03-15 | 中国科学院物理研究所 | Anode material of SOFC containing alkali metal or alkali earth metal and its production and use |
| CN106684412B (en) * | 2017-01-11 | 2019-04-02 | 福州大学 | One proton conducts intermediate temperature solid oxide fuel cell electrolyte and preparation method |
-
2017
- 2017-05-23 CN CN201710368348.XA patent/CN107230795B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| Ce0.8Sm0.2O1.9-BaCe0.8Sm0.2O2.9复合电解质的晶界电导;熊月龙 等;《硅酸盐学报》;20160131(第1期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107230795A (en) | 2017-10-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105633439B (en) | A kind of intermediate temperature solid oxide fuel cell electrolyte and preparation method thereof | |
| CN106684412B (en) | One proton conducts intermediate temperature solid oxide fuel cell electrolyte and preparation method | |
| CN106848359B (en) | A kind of intermediate temperature solid oxide fuel cell electrolyte and preparation method thereof | |
| CN107230795B (en) | Electrolyte of intermediate-temperature solid oxide fuel cell with proton conductivity | |
| CN108987776B (en) | Medium-temperature solid oxide fuel cell electrolyte and preparation method thereof | |
| CN109742430B (en) | Low-temperature solid oxide fuel cell based on barium stannate/zinc oxide composite material | |
| CN106920979A (en) | One kind of proton conducts intermediate temperature solid oxide fuel cell electrolyte and its preparation | |
| CN107134584B (en) | Medium-temperature solid oxide fuel cell 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 | |
| CN110649300A (en) | Electrolyte of alkaline earth metal doped proton conduction intermediate-temperature solid oxide fuel cell | |
| CN111584882B (en) | Solid oxide fuel cell with novel structure and preparation method thereof | |
| CN108232303A (en) | Oxygen ion conduction intermediate temperature solid oxide fuel cell electrolyte preparation method | |
| CN109687006B (en) | Low-temperature solid oxide fuel cell based on cerium oxide/nickel oxide composite material | |
| CN106505211A (en) | A kind of reduction CeO2Anode material of base SOFC electronic conductance and preparation method thereof | |
| CN106887626A (en) | Intermediate temperature solid oxide fuel cell composite electrolyte and preparation method thereof | |
| CN108270024B (en) | Double-doped medium-temperature solid oxide fuel cell electrolyte and preparation method thereof | |
| CN106711481B (en) | A kind of intermediate temperature solid oxide fuel cell composite electrolyte and preparation method thereof | |
| CN108110289B (en) | Proton-conducting medium-low temperature solid oxide fuel cell electrolyte | |
| CN106935889A (en) | A kind of intermediate temperature solid oxide fuel cell electrolyte of oxygen ion conduction | |
| CN110828873B (en) | Preparation method of oxygen ion conduction medium-temperature solid oxide fuel cell electrolyte | |
| CN107171009B (en) | Electrolyte of double-doped medium-temperature solid oxide fuel cell and preparation thereof | |
| CN114709457B (en) | Double-doped medium-temperature solid oxide fuel cell electrolyte and preparation method thereof | |
| CN109638325B (en) | Strontium-doped medium-temperature solid oxide fuel cell electrolyte | |
| CN104319407A (en) | Electrode material of symmetric intermediate-temperature solid oxide fuel cell 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: 20200707 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |