CN114361540A - High-conductivity lanthanum molybdate-based composite electrolyte material and preparation method thereof - Google Patents
High-conductivity lanthanum molybdate-based composite electrolyte material and preparation method thereof Download PDFInfo
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- 239000002001 electrolyte material Substances 0.000 title claims abstract description 13
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- 239000000446 fuel Substances 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 6
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- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 5
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 5
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Abstract
A high-conductivity lanthanum molybdate based composite electrolyte material and a preparation method thereof relate to the technical field of solid electrolyte ceramic materials, and the chemical formula is as follows: la1.73Ca0.02Sm0.10Y0.15Mo1.9‑ xMn0.1AlxO9‑δ(x is 0.1 to 0.4). La in lanthanum molybdate-based electrolyte3+Bit and Mo6+Multi-component composite doping is carried out, phase change is inhibited through multi-component synergistic action and lattice distortion effect, and the performance of the material is improved. The invention can inhibit La by composite doping2Mo2O9The phase change behavior of the material is improved, so that the electrical property of the material is improved, and the material can be applied as an electrolyte of a solid oxide fuel cell. The prepared La is proved by experiments1.73Ca0.02Sm0.10Y0.15Mo1.7Mn0.1Al0.2O9‑δHaving the highest electrical conductance and low activation energy for conduction.
Description
Technical Field
The invention relates to the technical field of solid electrolyte ceramic materials, in particular to a high-conductivity lanthanum molybdate-based composite electrolyte material and a preparation method thereof.
Background
As is well known, a Solid Oxide Fuel Cell (SOFC) is a novel, efficient and clean power generation device that directly converts chemical energy into electric energy, and the energy conversion efficiency of cogeneration is as high as 80% or more, which is known as a novel green chemical energy in the 21 st century. The traditional SOFC adopting YSZ as electrolyte needs to operate at high temperature of 900-1000 ℃, and has many problems in use, including easy reaction among all parts of the fuel cell, poor stability, high cost, short service life and the like. When the SOFC reduces the working temperature to 800 ℃ or below, the stability of the SOFC in long-time working can be improved, the material selection range is enlarged, and the SOFC cost is reduced. At present, the main research focus of SOFC is to reduce the SOFC working temperature so that the SOFC can work at medium temperature or even low temperature. The electrolyte, which is the core component of the SOFC, is the primary factor that determines the SOFC operating temperature.
In recent years, a novel lanthanum molybdate-based electrolyte (La) having high oxygen ion conductivity2Mo2O9) Is widely concerned by people. But pure lanthanum molybdate based electrolyte (La)2Mo2O9) The transformation process from high-temperature cubic phase to low-temperature monoclinic phase occurs at about 580 ℃, and the conductivity of the electrolyte is reduced by two orders of magnitude through the phase transformation process. How to avoid the high-temperature phase transition of the lanthanum molybdate-based electrolyte and improve the electrical property of the material has become an important subject in the research field of the SOFC electrolyte. At the same time, the common use of the existing multicomponent materialsIn the conventional preparation method, the defects of difficult uniform distribution of all components, difficult accurate control of the proportion, high temperature for synthesizing and sintering materials, long time and the like easily occur, so that the defects also need to be overcome in a targeted manner.
Disclosure of Invention
Lanthanum molybdate based electrolyte (La) of the present invention2Mo2O9) La of (5)3+Bit and Mo6+Multi-component composite doping is carried out, phase change is inhibited through multi-component synergistic action and lattice distortion effect, and the performance of the material is improved. In addition, aiming at the defects that the multicomponent material is easy to appear in the conventional preparation method, the invention firstly leads the raw materials to be fully dissolved, dispersed and mixed in the solution by ultrasonic stirring, then constructs a three-dimensional network with uniform size and structure by combining the sol-gel process, leads all the elements to be uniformly distributed in the ion or molecular size, and finally synthesizes the electrolyte powder with uniform components, small particles and high sintering activity at low temperature by utilizing the characteristics of uniform and rapid heating reaction of a microwave heating combustion-supporting method.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a high-conductivity lanthanum molybdate-based composite electrolyte material has a chemical formula as follows:
La1.73Ca0.02Sm0.10Y0.15Mo1.9-xMn0.1AlxO9-δwherein x is 0.1-0.4.
A preparation method of a high-conductivity lanthanum molybdate-based composite electrolyte material adopts an ultrasonic-assisted microwave combustion method and comprises the following steps:
according to La1.73Ca0.02Sm0.10Y0.15Mo1.9-xMn0.1AlxO9-δWeighing the required ammonium molybdate, calcium nitrate, samarium nitrate, yttrium nitrate, lanthanum nitrate, manganese sulfate and aluminum nitrate according to the stoichiometric ratio, adding deionized water, and uniformly stirring and dissolving to obtain a solution A;
preparing a mixed solution of citric acid, EDTA and glycol to obtain a solution B;
thirdly, mixing the solution A and the solution B prepared in the first step and the second step, then ultrasonically stirring, and adjusting the pH value of the solution to be alkalescent to obtain a solution C;
fourthly, heating and stirring the solution C until the solution C becomes gel, and drying the gel to obtain dry gel;
grinding the dry gel, placing the ground dry gel in a microwave oven for microwave heating combustion, and carrying out heat treatment on the powder obtained by combustion to remove residual organic matters in the sample;
sixthly, after natural cooling, adding a proper amount of PVA solution as an adhesive to carry out grinding granulation;
seventhly, weighing a proper amount of granulated powder, performing die-filling pressing on the powder to form a circular sheet, and sintering the circular sheet at high temperature to prepare La1.73Ca0.02Sm0.10Y0.15Mo1.9-xMn0.1AlxO9-δAnd (4) an electrolyte ceramic wafer to obtain the high-conductivity lanthanum molybdate-based composite electrolyte material.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
the molar ratio of the citric acid, the EDTA and the ethylene glycol in the step II to the total amount of all the metal ions in the step I is 1: 1.4: 3: 1.
And step three, ultrasonically stirring for 30-60 min, and adjusting the pH value of the solution to 7-8 by using ammonia water.
Heating and stirring for 2-4 hours on a magnetic stirrer, wherein the heating temperature is 60-90 ℃; and drying the gel for 5-10 hours at 80-110 ℃ to obtain dry gel.
And fifthly, transferring the powder obtained by combustion into a muffle furnace, and carrying out heat preservation treatment at 450-550 ℃ for 120-180 min to remove the residual organic matters in the sample.
Seventhly, putting the round thin sheet into a muffle furnace, and sintering at 800-1000 ℃ for 3-8 hours to prepare La1.73Ca0.02Sm0.10Y0.15Mo1.9-xMn0.1AlxO9-δAn electrolyte ceramic sheet.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts ultrasonic wave auxiliary microwave combustion method to prepare various productsElement-doped lanthanum molybdate-based composite electrolyte material La1.73Ca0.02Sm0.10Y0.15Mo1.9-xMn0.1AlxO9-δ(x is 0.1 to 0.4). Adopting proper process conditions and method to lead Ca, Sm and Y to replace La and lead Al and Mn to replace Mo to enter La2Mo2O9Lattice, low-temperature synthesis of cubic phase electrolyte La1.73Ca0.02Sm0.10Y0.15Mo1.9-xMn0.1AlxO9-δ(x is 0.1 to 0.4); the powder synthesized by the method has good sintering performance, and the densification of the electrolyte material can be realized at a lower temperature. La can be suppressed by composite doping2Mo2O9The phase change behavior of the material is improved, so that the electrical property of the material is improved, and the material can be applied as an electrolyte of a solid oxide fuel cell. The prepared La is proved by experiments1.73Ca0.02Sm0.10Y0.15Mo1.7Mn0.1Al0.2O9-δHaving the highest electrical conductance and low activation energy for conduction.
Drawings
FIG. 1 shows the preparation of La under different pH conditions1.73Ca0.02Sm0.10Y0.15Mo1.6Mn0.1Al0.3O9-δXRD pattern of (a).
FIG. 2 shows the different compositions La1.73Ca0.02Sm0.10Y0.15Mo1.9-xMn0.1AlxO9-δXRD pattern of (a).
FIG. 3 shows the composition La1.73Ca0.02Sm0.10Y0.15Mo1.9-xMn0.1AlxO9-δRelative density of (d).
FIG. 4 shows the composition La1.73Ca0.02Sm0.10Y0.15Mo1.9-xMn0.1AlxO9-δIs plotted against temperature.
FIG. 5 shows the composition La1.73Ca0.02Sm0.10Y0.15Mo1.9-xMn0.1AlxO9-δArrhenius curve of the electrical conductivity of (a).
FIG. 6 shows the composition La1.73Ca0.02Sm0.10Y0.15Mo1.9-xMn0.1AlxO9-δActivation energy of (a) is plotted against doping amount x.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
According to La1.73Ca0.02Sm0.10Y0.15Mo1.9-xMn0.1AlxO9-δAccording to the stoichiometric ratio of (A), x is 0.1, 0.2, 0.3 and 0.4 respectively, the required ammonium molybdate, calcium nitrate, samarium nitrate, yttrium nitrate, lanthanum nitrate, manganese sulfate and aluminum nitrate are weighed and put into a beaker, deionized water is added, and the solution A is obtained after uniform stirring and dissolution.
Preparing a mixed solution of citric acid, EDTA and glycol to obtain a solution B. The mol ratio of the citric acid, the EDTA and the ethylene glycol to the total amount of the metal ions in all the steps is 1: 1.4: 3: 1.
Thirdly, mixing the solution A and the solution B prepared in the first step and the second step, performing ultrasonic treatment in an ultrasonic cleaning machine for 40min, and adding ammonia water while performing ultrasonic treatment to adjust the pH value of the solution to 6.5-8.5 to obtain a solution C.
And fourthly, transferring the solution C to a magnetic stirrer, heating and stirring for 3 hours at the temperature of 75 ℃ until the solution C becomes gel, transferring the gel into a drying oven, and drying for 8 hours at the temperature of 100 ℃ to obtain dry gel.
And fifthly, grinding the dry gel, placing the ground dry gel in a microwave oven for microwave heating combustion, transferring the powder obtained by combustion to a muffle furnace, and carrying out heat preservation treatment at 500 ℃ for 150min to remove residual organic matters in the sample.
Sixthly, after natural cooling, adding a proper amount of 5 wt% PVA solution as a bonding agent for grinding and granulation.
Seventhly, weighing 1g of granulated powder, die-filling and pressing, pressing into a round sheet under the condition that the gauge pressure of a tablet press is 9MPa, putting the round sheet into a muffle furnace, and keeping the temperature of 900 ℃ to burnObtaining La after 5 hours1.73Ca0.02Sm0.10Y0.15Mo1.9- xMn0.1AlxO9-δAn electrolyte ceramic sheet.
And eighthly, polishing, cleaning and drying the two surfaces of the prepared ceramic chip, coating silver paste as an electrode, roasting at the temperature of 700 ℃ for 2 hours, and measuring the electrical property of the sample by adopting a bipolar method.
Example 1 preparation of electrolyte powder and characterization of sintered body properties.
1. XRD pattern
FIG. 1 shows the preparation of La under different pH conditions1.73Ca0.02Sm0.10Y0.15Mo1.6Mn0.1Al0.3O9-δXRD spectrum of the sample. The graph shows that when the pH value is 7-8, each characteristic peak is sharp and smooth, and the graph shows that the crystallinity of the sample is good, and the positions of diffraction peaks and the cubic phase La2Mo2O9(JCPDS 28-0509) shows that the doping element is fused into La2Mo2O9Cubic phase solid solutions are formed in the crystal lattice of the matrix. And when the pH value is 6.5 and 8.5, the prepared powder contains impurity phases, which shows that the adjustment of the pH value in the preparation process of the powder has important influence on the purity of the sample.
FIG. 2 shows the different compositions La1.73Ca0.02Sm0.10Y0.15Mo1.9-xMn0.1AlxO9-δ(x is 0.1, 0.2, 0.3, 0.4) XRD spectrum of powder (prepared under pH 7.5). The graph shows that the sample has better crystallinity, 4 stronger diffraction peaks are arranged in the range of 20-60 degrees of 2 theta, are respectively positioned at 24.92 degrees, 27.88 degrees, 30.58 degrees and 47.41 degrees and pass through the La phase and the cubic phase2Mo2O9Standard card reference, corresponding to cubic phase La respectively2Mo2O9The (200), (210), (211), and (321) diffraction planes of (b). The Ca, Sm and Y replace La, and Mn and Al replace Mo to enter La2Mo2O9Lattice of La forming a cubic phase structure1.73Ca0.02Sm0.10Y0.15Mo1.9-xMn0.1AlxO9-δThe solid solution shows that the invention can realize multi-element composite doping through proper powder preparation method and process conditions, inhibit phase change and enable La2Mo2O9The cubic phase of (b) was stabilized to room temperature.
2. Density test
FIG. 3 shows the composition La1.73Ca0.02Sm0.10Y0.15Mo1.9-xMn0.1AlxO9-δAs can be seen from the graphs, the relative densities of the samples obtained by sintering at 900 ℃ for 5 hours were all 95% or more in the relative densities of (x ═ 0, 0.1, 0.2, 0.3, and 0.4) (prepared under the condition of pH 7.5). The relative density is increased and then decreased along with the increase of the doping amount of Al, wherein La1.73Ca0.02Sm0.10Y0.15Mo1.7Mn0.1Al0.2O9-δ(x ═ 0.2) the relative density reached the highest (98.3%), indicating that the ultrasonic-assisted microwave combustion method produced La1.73Ca0.02Sm0.10Y0.15Mo1.9-xMn0.1AlxO9-δThe sample has good sintering activity. Compared with the traditional solid phase reaction method, the sintering temperature is greatly reduced, and the low sintering temperature can reduce the energy consumption. Meanwhile, the low sintering temperature is beneficial to realizing the co-firing of the electrode and the electrolyte, thereby reducing the preparation cost of the solid oxide fuel cell.
3. Electrical Performance testing and analysis
FIG. 4 shows the composition La1.73Ca0.02Sm0.10Y0.15Mo1.9-xMn0.1AlxO9-δ(x is 0, 0.1, 0.2, 0.3, 0.4) (prepared under the condition of pH 7.5) as a graph showing the relationship between the electrical conductivity and the temperature, and La is known from the graph1.73Ca0.02Sm0.10Y0.15Mo1.9- xMn0.1AlxO9-δThe series of samples all have higher conductivity, and the conductivity increases along with the increase of the temperature. Wherein, La is at 800 DEG C1.73Ca0.02Sm0.10Y0.15Mo1.7Mn0.1Al0.2O9-δConductance of electricityThe highest rate (up to 0.084S/cm).
FIG. 5 shows the composition La1.73Ca0.02Sm0.10Y0.15Mo1.9-xMn0.1AlxO9-δArrhenius plot of conductivity (prepared at pH 7.5) and data showing a linear relationship between 1000/T and ln (. sigma.T) indicate that La1.73Ca0.02Sm0.10Y0.15Mo1.9-xMn0.1AlxO9-δThe relationship between the conductivity value and the temperature is applicable to the Arrhenius relationship. Meanwhile, the Arrhenius curve has no obvious turn, which indicates that La is treated2Mo2O9The La and Mo sites are subjected to multi-component composite doping to inhibit phase change, and the phase change process of converting a high-temperature cubic phase into a low-temperature monoclinic phase is not generated.
FIG. 6 shows the composition La1.73Ca0.02Sm0.10Y0.15Mo1.9-xMn0.1AlxO9-δ(prepared under the condition of pH value of 7.5) and doping amount x, as can be seen from FIG. 6, the activation energy is gradually reduced firstly with the increase of the doping amount x, when x is 0.2, the activation energy is minimum (1.18ev), and when x is continuously increased, the activation energy is gradually increased. The change in activation energy and conductivity may be due to the presence of attraction between the doped cations and oxygen vacancies.
Since the quality of the electrical properties of the electrolyte is related to its conductivity and activation energy, a high conductivity and low activation energy electrolyte can produce a better battery. In general, the La can be improved by proper composite doping2Mo2O9Properties of electrolyte, specifically, sample La was prepared when x ═ 0.21.73Ca0.02Sm0.10Y0.15Mo1.7Mn0.1Al0.2O9-δHas the highest conductivity (0.084S/cm) and the lowest activation energy (1.18eV), and is suitable for being used as a candidate material of the solid oxide fuel cell electrolyte.
Example 2
According to La1.73Ca0.02Sm0.10Y0.15Mo1.6Mn0.1Al0.3O9-δAccording to the stoichiometric ratio, the required ammonium molybdate, calcium nitrate, samarium nitrate, yttrium nitrate, lanthanum nitrate, manganese sulfate and aluminum nitrate are weighed and placed into a beaker, deionized water is added, and the solution A is obtained after uniform stirring and dissolution.
Preparing a mixed solution of citric acid, EDTA and glycol to obtain a solution B. The mol ratio of the citric acid, the EDTA and the ethylene glycol to the total amount of the metal ions in all the steps is 1: 1.4: 3: 1.
Thirdly, mixing the solution A and the solution B prepared in the first step and the second step, and then carrying out ultrasonic treatment in an ultrasonic cleaning machine for 40min, adding ammonia water while carrying out ultrasonic treatment to adjust the pH value of the solution to 7.5, thus obtaining a solution C.
And fourthly, transferring the solution C to a magnetic stirrer, heating and stirring for 4 hours at the temperature of 70 ℃ until the solution C becomes gel, transferring the gel into a drying oven, and drying for 5 hours at the temperature of 110 ℃ to obtain dry gel.
And fifthly, grinding the dry gel, placing the ground dry gel in a microwave oven for microwave heating combustion, transferring the powder obtained by combustion into a muffle furnace, and carrying out heat preservation treatment at 450 ℃ for 180min to remove residual organic matters in the sample.
Sixthly, after natural cooling, adding a proper amount of 5 wt% PVA solution as a bonding agent for grinding and granulation.
Seventhly, weighing 1g of granulated powder, die-filling and pressing, pressing into a round sheet under the condition that the gauge pressure of a tablet press is 9MPa, putting the round sheet into a muffle furnace, and sintering at 850 ℃ for 8 hours to prepare La1.73Ca0.02Sm0.10Y0.15Mo1.6Mn0.1Al0.3O9-δAn electrolyte ceramic sheet.
Example 3
According to La1.73Ca0.02Sm0.10Y0.15Mo1.5Mn0.1Al0.4O9-δAccording to the stoichiometric ratio, the required ammonium molybdate, calcium nitrate, samarium nitrate, yttrium nitrate, lanthanum nitrate, manganese sulfate and aluminum nitrate are weighed and placed into a beaker, deionized water is added, and the solution A is obtained after uniform stirring and dissolution.
Preparing a mixed solution of citric acid, EDTA and glycol to obtain a solution B. The mol ratio of the citric acid, the EDTA and the ethylene glycol to the total amount of the metal ions in all the steps is 1: 1.4: 3: 1.
Thirdly, mixing the solution A and the solution B prepared in the first step and the second step, and then carrying out ultrasonic treatment in an ultrasonic cleaning machine for 40min, adding ammonia water while carrying out ultrasonic treatment to adjust the pH value of the solution to 8, thus obtaining a solution C.
And fourthly, transferring the solution C to a magnetic stirrer, heating and stirring for 2 hours at the temperature of 80 ℃ until the solution C becomes gel, transferring the gel into a drying oven, and drying for 9 hours at the temperature of 85 ℃ to obtain dry gel.
And fifthly, grinding the dry gel, placing the ground dry gel in a microwave oven for microwave heating combustion, transferring the powder obtained by combustion into a muffle furnace, and carrying out heat preservation treatment at 550 ℃ for 120min to remove residual organic matters in the sample.
Sixthly, after natural cooling, adding a proper amount of 5 wt% PVA solution as a bonding agent for grinding and granulation.
Seventhly, weighing 1g of granulated powder, die-filling and pressing, pressing into a round sheet under the condition that the gauge pressure of a tablet press is 9MPa, putting the round sheet into a muffle furnace, and sintering at 1000 ℃ for 3 hours to prepare La1.73Ca0.02Sm0.10Y0.15Mo1.5Mn0.1Al0.4O9-δAn electrolyte ceramic sheet.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (10)
1. A high-conductivity lanthanum molybdate-based composite electrolyte material is characterized by having a chemical formula as follows:
La1.73Ca0.02Sm0.10Y0.15Mo1.9-xMn0.1AlxO9-δwherein x is 0.1-0.4.
2. A method for preparing the high-conductivity lanthanum molybdate-based composite electrolyte material as defined in claim 1 by using an ultrasonic-assisted microwave combustion method, which is characterized by comprising the following steps:
according to La1.73Ca0.02Sm0.10Y0.15Mo1.9-xMn0.1AlxO9-δWeighing the required ammonium molybdate, calcium nitrate, samarium nitrate, yttrium nitrate, lanthanum nitrate, manganese sulfate and aluminum nitrate according to the stoichiometric ratio, adding deionized water, and uniformly stirring and dissolving to obtain a solution A;
preparing a mixed solution of citric acid, EDTA and glycol to obtain a solution B;
thirdly, mixing the solution A and the solution B prepared in the first step and the second step, then ultrasonically stirring, and adjusting the pH value of the solution to be alkalescent to obtain a solution C;
fourthly, heating and stirring the solution C until the solution C becomes gel, and drying the gel to obtain dry gel;
grinding the dry gel, placing the ground dry gel in a microwave oven for microwave heating combustion, and carrying out heat treatment on the powder obtained by combustion to remove residual organic matters in the sample;
sixthly, after natural cooling, adding a proper amount of PVA solution as an adhesive to carry out grinding granulation;
seventhly, weighing a proper amount of granulated powder, performing die-filling pressing on the powder to form a circular sheet, and sintering the circular sheet at high temperature to prepare La1.73Ca0.02Sm0.10Y0.15Mo1.9-xMn0.1AlxO9-δAnd (4) an electrolyte ceramic wafer to obtain the high-conductivity lanthanum molybdate-based composite electrolyte material.
3. The method of claim 2, wherein the molar ratio of citric acid, EDTA, ethylene glycol in step (ii) to the total amount of all metal ions in step (i) is 1: 1.4: 3: 1.
4. The method of claim 2, wherein the ultrasonic stirring time in the third step is 30-60 min.
5. The method of claim 2, wherein the pH of the solution in step (c) is adjusted to 7 to 8.
6. The method of claim 2 or 5, wherein the pH of the solution in step (c) is adjusted with ammonia.
7. The method according to claim 2, wherein in the step (iv), the magnetic stirrer is heated and stirred for 2 to 4 hours at a temperature of 60 to 90 ℃; and drying the gel for 5-10 hours at 80-110 ℃ to obtain dry gel.
8. The method as claimed in claim 2, wherein in the fifth step, the powder obtained by burning is transferred to a muffle furnace, and the residual organic matters in the sample are removed by heat treatment at 450-550 ℃ for 120-180 min.
9. The method of claim 2, wherein in step (c), the round thin sheet is sintered in a muffle furnace at 800-1000 ℃ for 3-8 hours to obtain La1.73Ca0.02Sm0.10Y0.15Mo1.9-xMn0.1AlxO9-δAn electrolyte ceramic sheet.
10. The use of the high conductivity lanthanum molybdate-based composite electrolyte material as claimed in claim 1 as an electrolyte for a solid oxide fuel cell.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110051955A (en) * | 2009-11-11 | 2011-05-18 | 한국과학기술연구원 | Method of non-shrinkage fabrication of metal oxide thin film for solid oxide fuel cell by low temperature |
| US20130095408A1 (en) * | 2011-10-14 | 2013-04-18 | Samsung Electronics Co. Ltd. | Anode material for solid oxide fuel cell, and anode and solid oxide fuel cell including anode material |
| US20140011100A1 (en) * | 2012-07-06 | 2014-01-09 | Samsung Electronics Co., Ltd. | Solid ion conductor, solid electrolyte including the same, lithium battery including solid electrolyte, and method of manufacturing lithium battery |
| CN107129304A (en) * | 2017-05-17 | 2017-09-05 | 合肥学院 | A kind of method of the combustion-supporting lanthanum molybdate-based electrolyte of method one-step synthesis of microwave |
-
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- 2022-01-06 CN CN202210013527.2A patent/CN114361540A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110051955A (en) * | 2009-11-11 | 2011-05-18 | 한국과학기술연구원 | Method of non-shrinkage fabrication of metal oxide thin film for solid oxide fuel cell by low temperature |
| US20130095408A1 (en) * | 2011-10-14 | 2013-04-18 | Samsung Electronics Co. Ltd. | Anode material for solid oxide fuel cell, and anode and solid oxide fuel cell including anode material |
| US20140011100A1 (en) * | 2012-07-06 | 2014-01-09 | Samsung Electronics Co., Ltd. | Solid ion conductor, solid electrolyte including the same, lithium battery including solid electrolyte, and method of manufacturing lithium battery |
| CN107129304A (en) * | 2017-05-17 | 2017-09-05 | 合肥学院 | A kind of method of the combustion-supporting lanthanum molybdate-based electrolyte of method one-step synthesis of microwave |
Non-Patent Citations (3)
| Title |
|---|
| G NARSINGA RAO ET AL.: "Enhanced magnetoresistance and Griffiths phase induced by Mo substitution in La0.7Ca0.15Sr0.15Mn1-xMoxO3", JOURNAL OF PHYSICS D-APPLIED PHYSICS, vol. 42, no. 9, 7 May 2009 (2009-05-07), pages 095003, XP020149513, DOI: 10.1088/0022-3727/42/9/095003 * |
| XIAO LIU ET AL.: "High oxide ion conducting solid electrolytes of bismuth and niobium co-substituted La2Mo2O9", INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, vol. 39, no. 31, 16 September 2014 (2014-09-16), pages 17819 - 17827, XP029048047, DOI: 10.1016/j.ijhydene.2014.08.110 * |
| 郭中一等: "钼酸镧基电解质材料的研究进展", 稀有金属材料与工程, vol. 38, 15 December 2009 (2009-12-15), pages 712 - 715 * |
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