CN114824303B - R-P type layered medium-entropy perovskite structure cathode material and preparation method thereof - Google Patents
R-P type layered medium-entropy perovskite structure cathode material and preparation method thereof Download PDFInfo
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- 238000010438 heat treatment Methods 0.000 claims abstract description 26
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
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- 238000000498 ball milling Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
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- 239000000463 material Substances 0.000 description 31
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- 238000007254 oxidation reaction Methods 0.000 description 2
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- 239000007787 solid Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
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- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
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- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
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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
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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
- H01M4/00—Electrodes
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- H01M4/88—Processes of manufacture
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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
- H01M4/00—Electrodes
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- H01M4/90—Selection of catalytic material
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- H—ELECTRICITY
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- H01M8/10—Fuel cells with solid electrolytes
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Abstract
R-P type layered medium-entropy perovskite structure cathode material with molecular formula of La 1.4 Sr 0.6 (Co，Fe，Ni，Mn) 1/4 O 4+δ Wherein δ represents an oxygen vacancy content. The preparation method comprises the following steps: to respectively contain La 3+ 、Sr 2+ 、Co 2+ 、Fe 3+ 、Ni 2+ 、Mn 2+ Weighing the raw materials according to the stoichiometric ratio of the corresponding elements in the molecular formula, respectively adding the raw materials into deionized water, stirring, dissolving and uniformly mixing to obtain solution A; respectively adding citric acid and ethylene glycol into the solution A, heating, stirring, dissolving, transferring into an electric furnace, heating to spontaneous combustion, and continuously heating to form ash to obtain a precursor; and grinding the precursor, and transferring the ground precursor into a horse boiling furnace for heating to obtain cathode powder, namely the R-P type layered medium entropy perovskite structure cathode material. The method can improve the stability and the conductivity of the cathode material and reduce the thermal expansion coefficient of the cathode material.
Description
Technical Field
The invention belongs to the technical field of medium-low temperature SOFC cathode materials, and particularly relates to an R-P layered medium-entropy perovskite structure cathode material and a preparation method thereof.
Background
Solid Oxide Fuel Cells (SOFCs) are considered to be the most promising energy conversion and storage devices, and conventional SOFCs require higher operating temperatures to achieve better results, which in turn place more stringent demands on electrode materials, connection materials, etc., resulting in limited stability and lifetime of the solid oxide fuel cells. In the middle-low temperature operation environment, the SOFC has the problems of larger cathode polarization impedance, serious electrode loss and the like. Accordingly, it has been proposed to develop a material having higher ion-electron mixed conductivity (MIEC) as a cathode to promote an Oxygen Reduction Reaction (ORR) and improve durability performance of a battery. The traditional MIEC material has the problems of poor stability, mismatching of thermal expansion coefficient and common electrolyte, and the like, so the development of the novel cathode material has important significance.
In recent years, ruddlesden-Popper (R-P) type layered perovskite structure materials have been widely focused in SOFC, and the R-P type layered perovskite structure materials have a chemical formula of A n+1 B n O 3n+1 Directly entraining n successive perovskite layers (ABO) from two rock salt layers (AO) 3 ) Is combined. The A site is mainly Ba, la, ca, sr and other alkaline earth metal ions, the B site is mostly Fe, co, ni, mn and other transition group valence-changing metal elements, components among A, B sites can be regulated, and the non-stoichiometric ratio of oxygen is regulated to the maximum extent, so that the internal structure has certain chemical defects, the chemical defects can greatly improve the electrochemical performance of the material, and the material has the advantages of higher ion-electron mixed conductivity, strong oxygen diffusion and surface exchange capacity, high catalytic activity and the like. Chinese patent CN105449227a discloses a layered perovskite fuel cell cathode material and preparation method thereof, the chemical formula of the cathode material is Ln 0.5-1.5 Ba 0.5-1.5 Mn 0.5-2 Mg 0.05-0.2 Co 0.5-2 O 5+δ The cathode material belongs to a B-site ternary novel layered perovskite oxide, and has improved thermal expansion and electrochemical performance, but the cathode material can generate structural transformation when being sintered for a long time at the temperature of more than 700 ℃, so that the stability is poor.
Since the introduction of the high entropy concept into the oxide ceramic field, high construction entropy perovskite oxides have received great attention and some breakthrough advances have been made in the application of SOFC cathode materials. The higher construction entropy in the system can promote the crystal structure to reach a stable state, and the stability of the material is improved. Compared with the traditional perovskite oxide, the oxide with higher construction entropy has better high-temperature oxidation resistance, wear resistance, corrosion resistance and the like, and has potential application value in the fields of ultra-high temperature materials and new energy materials. High construction entropy calciumThe titanium ore oxide is a titanium ore oxide with higher construction entropy (S config ) Including medium entropy perovskite oxides and high entropy perovskite oxides. The high-entropy perovskite oxide is generally prepared by combining 4 elements in the same or similar proportion, and is prepared by combining 5 or more elements in the same or similar proportion. However, the simultaneous doping at A, B to form R-P type medium entropy perovskite oxidation has not been reported so far.
Disclosure of Invention
The invention aims to provide an R-P type layered medium-entropy perovskite structure cathode material and a preparation method thereof, which can improve the stability and the conductivity of the prepared cathode material and reduce the thermal expansion coefficient of the cathode material.
In order to achieve the aim, the invention provides an R-P type lamellar medium entropy perovskite structure cathode material, wherein the composition general formula of the cathode material is A 2 BO 4+δ The molecular formula is La 1.4 Sr 0.6 (Co，Fe，Ni，Mn) 1/4 O 4+δ Wherein δ represents an oxygen vacancy content.
The invention also provides a preparation method of the R-P type layered medium-entropy perovskite structure cathode material, which comprises the following steps:
(1) To contain La 3+ Compound (c) containing Sr 2+ Compound (c) containing Co 2+ Compound (c) containing Fe 3+ Compound (c) containing Ni 2+ Compounds of (1) containing Mn 2+ According to La 1.4 Sr 0.6 (Co，Fe，Ni，Mn) 1/4 O 4+δ Weighing raw materials according to the stoichiometric ratio of the corresponding elements, respectively adding the raw materials into deionized water, stirring, dissolving and uniformly mixing to obtain a solution A;
(2) Adding complexing agent citric acid and burning aid ethylene glycol into the solution A respectively, heating, stirring and dissolving, transferring into an electric furnace at 280-300 ℃ and heating to spontaneous combustion, and continuing heating until ash is formed by combustion, namely obtaining a precursor after the reaction is finished;
(3) Grinding the precursor ash obtained in the step (2), and transferring the ground precursor ash into a horse boiling furnace for heating treatment to obtain cathode powder, namely the R-P type layered medium entropy perovskite structure cathode material.
Preferably, in the step (2), the molar ratio between all metal ions, citric acid and ethylene glycol in the solution a is 1:2:4.
further, the preparation method further comprises the following steps: and (3) sequentially performing ball milling and drying on the cathode powder obtained in the step (3), and sequentially performing drying and grinding to obtain the final cathode powder.
Preferably, the specific ball milling process is that the cathode powder obtained in the step (3) is put into a ball milling tank filled with zirconia balls with different specifications and sizes, ethanol is added, ball milling is carried out for 24 hours in a planetary ball mill with the rotating speed of 80r/min, and the mass ratio among the cathode powder, the zirconia balls and the ethanol in the ball milling tank is 1:6:1.
Preferably, the drying process comprises: and putting the mixture into an oven at 80 ℃ for drying for 24 hours.
Preferably, in step (1), la is contained 3+ The compound of (a) is La (NO) 3 ) 3 ·6H 2 O, containing Sr 2+ The compound of (a) is Sr (NO) 3 ) 2 Contains Co 2+ The compound of (a) is Co (NO) 3 ) 2 ·6H 2 O, containing Fe 3+ The compound of (a) is Fe (NO) 3 ) 3 ·9H 2 O, ni-containing 2+ The compound of (a) is Ni (NO) 3 ) 2 ·6H 2 O, containing Mn 2+ The compound of (C) is Mn (CH) 3 COO 3 ) 2 ·4H 2 O。
Preferably, in the step (3), the temperature increase program of the equine boiler is: raising the temperature from room temperature to 300 ℃ at a heating rate of 3 ℃/min, preserving heat for 3 hours, raising the temperature from 300 ℃ to 1000 ℃ at a heating rate of 3 ℃/min, preserving heat for 4 hours, and naturally cooling to room temperature.
The invention introduces the high construction entropy concept into the R-P type layered perovskite oxide, and successfully prepares the novel SOFC cathode material with good electrochemical performance. The invention is realized by the method that La 2 MO 4+δ La site doping in the main phase to increase the non-stoichiometric number of oxygen, increase the conductivity of the material,simultaneously four transition valence-changing metal elements commonly occupy La 2 MO 4+δ The M position of the (C) is higher in construction entropy, the stability of the material is improved, the thermal expansion coefficient is reduced, and the SOFC cathode material with excellent performance is obtained, so that the cathode material has better electrochemical performance in a medium-low temperature range. The cathode material La provided by the invention 1.4 Sr 0.6 (Co，Fe，Ni，Mn) 1/4 O 4+δ The conductivity of the material is measured to be 114-116S cm in the temperature range of 650-850 DEG C -1 The range, activation energy is: 0.1839eV and a thermal expansion coefficient of 17.3063 ×10 measured in a temperature range of 20 to 1100 DEG C - 6 K -1 The SOFC material can well meet the use requirement of SOFC, and after the SOFC material is kept at the high temperature of 1100 ℃ for 24 hours, the structure of the SOFC material is not changed, other impurity phases are not generated, and the stability of the SOFC material is good.
Drawings
FIG. 1 is an XRD pattern of a sample prepared in accordance with an embodiment of the invention;
FIG. 2 is a comparison of XRD patterns of a sample prepared in accordance with the first embodiment of the present invention, before and after 24 hours of holding at 1100 ℃;
FIG. 3 is a graph showing the relationship between the thermal expansion coefficient and the test temperature of a dense sample strip made from a sample prepared in accordance with the first embodiment of the present invention;
FIG. 4 is a graph of electrical conductivity versus test temperature for a densified sample strip made from a sample made in accordance with an embodiment of the present invention;
FIG. 5 is an Arrhenius diagram of a densified sample strip made from a sample made in accordance with example one of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Example 1
A preparation method of an R-P layered medium-entropy perovskite structure cathode material comprises the following steps:
(1) With La (NO) 3 ) 3 ·6H 2 O、Sr(NO 3 ) 2 、Co(NO 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 O、Ni(NO 3 ) 2 ·6H 2 O、Mn(CH 3 COO 3 ) 2 ·4H 2 O is used as raw material according to La 1.4 Sr 0.6 (Co，Fe，Ni，Mn) 1/4 O 4+δ Weighing raw materials according to the stoichiometric ratio of the corresponding elements, respectively adding the raw materials into deionized water, stirring, dissolving and uniformly mixing to obtain a solution A;
(2) Adding complexing agent citric acid and burning aid ethylene glycol into the solution A respectively, heating, stirring and dissolving, transferring to an electric furnace with the temperature of 280-300 ℃ for heating to spontaneous combustion, and continuing heating until ash is formed by combustion, namely obtaining a precursor after the reaction is finished; the molar ratio among all metal ions, citric acid and ethylene glycol in the solution A is 1:2:4, a step of;
(3) Grinding the precursor ash obtained in the step (2), and transferring the ground precursor ash into a horse boiling furnace for heating treatment to obtain cathode powder, namely the R-P layered medium-entropy perovskite structure cathode material; the temperature-raising program of the muffle furnace is as follows: raising the temperature from room temperature to 300 ℃ at a heating rate of 3 ℃/min, preserving heat for 3 hours, raising the temperature from 300 ℃ to 1000 ℃ at a heating rate of 3 ℃/min, preserving heat for 4 hours, and naturally cooling to room temperature;
(4) Putting the cathode powder obtained in the step (3) into a ball milling tank filled with zirconia balls with different specifications and sizes, adding ethanol, ball milling for 24 hours in a planetary ball mill with the rotating speed of 80R/min, taking out and drying the materials after ball milling, sieving, putting the materials into an oven with the temperature of 80 ℃ for drying for 24 hours, grinding again, and sieving to obtain the final R-P type layered intermediate entropy perovskite structure cathode material; the mass ratio of the cathode powder, the zirconia balls and the ethanol in the ball milling tank is 1:6:1.
Referring to fig. 1, the XRD pattern of the sample prepared in this example is shown. The results show that the prepared materials and La in the database 2 CoO 4 The standard card PDF#:72-0937 of the material is completely matched, no impurity phase appears, and the prepared material is proved to be a pure-phase R-P type layered medium-entropy perovskite structure cathode material.
The final R-P layered medium-entropy perovskite structure cathode material obtained in the embodiment is placed in a high-temperature oven at 1100 ℃ for 24 hours, taken out and ground, XRD is tested for representing the stability of the material, and the test result is shown in figure 2. The temperature program of the high-temperature oven is as follows: raising the temperature from room temperature to 1100 ℃ at a heating rate of 3 ℃/min, preserving the heat for 24 hours, and naturally cooling to the room temperature. As can be seen from FIG. 2, the diffraction lattice of the material is not changed before and after high-temperature calcination, and other impurity peaks are not generated, so that the material prepared by the method has higher stability.
PVB dissolved by ethanol (3% of the mass of the cathode material is added) is added into the final R-P layered mesoperovskite structure cathode material obtained in the embodiment to serve as a binder, and ball milling is carried out for 6 hours in a planetary ball mill with the rotating speed of 80R/min, so that the cathode material and the binder are fully and uniformly mixed. Zirconia balls with different specifications and sizes are added in the ball milling process, and the weight ratio of cathode materials, zirconia balls and ethanol in a ball milling tank is 1:6:1; and after ball milling, taking out the materials, grinding, drying, sieving, granulating, and then putting the materials into an oven at 80 ℃ to dry for 6 hours to obtain mixed powder. Weighing a certain amount of mixed powder, maintaining the pressure for 2min under 300Mpa to prepare rectangular sample strips (the specification is about 0.3cm 0.4cm 1.0 cm), and then preserving the temperature in an air atmosphere 1400 ℃ in a horse boiling furnace for 6h to obtain compact sample strips; the temperature-raising program of the muffle furnace is as follows: raising the temperature from room temperature to 600 ℃ at a heating rate of 1 ℃/min, raising the temperature to 1400 ℃ at a heating rate of 2 ℃/min, preserving the heat for 6 hours, lowering the temperature to 800 ℃ at a cooling rate of 2 ℃/min, and naturally lowering the temperature to the room temperature.
The compact sample strip prepared from the final R-P layered medium-entropy perovskite structure cathode material obtained in the embodiment is placed in an expander with the temperature range of 25-1100 ℃ for thermal expansion coefficient test, the heating rate is 5K/min, the test result is shown in fig. 3, and the thermal expansion coefficient can be obtained in the test temperature range through analysis of fig. 3: 17.3474 ×10 -6 K -1 Thermal expansion coefficient 20×10 lower than that of common Co-based material -6 K -1 。
Ag is respectively tied on two ends of a compact sample strip prepared from the final R-P layered medium-entropy perovskite structure cathode material obtained in the embodimentThe Ag wires are fixed by conductive adhesive, and the conductivity test is carried out by adopting a direct current four-probe method (the lengths of the current sections of the voltage end are respectively 10mm and 12 mm), and the test result is shown in figure 4; as can be seen from the analysis of FIG. 4, the conductivity of the material is 114-116S cm at the temperature of 650-850 DEG C -1 Can well meet the use requirement of the SOFC. Meanwhile, the activation energy of the material is calculated by utilizing an Arrhenii Wu Sigong formula, the result is shown in fig. 5, and the activation energy of the material is obtained by analyzing fig. 5 as follows: 0.1839eV can well meet the use requirements of SOFC.
Claims (8)
1. A cathode material with an R-P layered medium-entropy perovskite structure is characterized in that the composition general formula of the cathode material is A 2 BO 4+δ The molecular formula is La 1.4 Sr 0.6 (Co，Fe，Ni，Mn) 1/4 O 4+δ Wherein δ represents an oxygen vacancy content.
2. A method for preparing the R-P type layered medium entropy perovskite structure cathode material according to claim 1, comprising the steps of:
(1) To contain La 3+ Compound (c) containing Sr 2+ Compound (c) containing Co 2+ Compound (c) containing Fe 3+ Compound (c) containing Ni 2+ Compounds of (1) containing Mn 2+ According to La 1.4 Sr 0.6 (Co，Fe，Ni，Mn) 1/4 O 4+δ Weighing raw materials according to the stoichiometric ratio of the corresponding elements, respectively adding the raw materials into deionized water, stirring, dissolving and uniformly mixing to obtain a solution A;
(2) Adding complexing agent citric acid and burning aid ethylene glycol into the solution A respectively, heating, stirring and dissolving, transferring into an electric furnace at 280-300 ℃ and heating to spontaneous combustion, and continuing heating until ash is formed by combustion, namely obtaining a precursor after the reaction is finished;
(3) Grinding the precursor ash obtained in the step (2), and transferring the ground precursor ash into a horse boiling furnace for heating treatment to obtain cathode powder, namely the R-P type layered medium entropy perovskite structure cathode material.
3. The method for preparing a cathode material with an R-P layered medium-entropy perovskite structure according to claim 2, wherein in the step (2), the molar ratio among all metal ions, citric acid and ethylene glycol in the solution a is 1:2:4.
4. a method for preparing a cathode material of R-P type layered medium entropy perovskite structure according to claim 2 or 3, wherein the preparation method further comprises the steps of: and (3) sequentially performing ball milling and drying on the cathode powder obtained in the step (3), and sequentially performing drying and grinding to obtain the final cathode powder.
5. The preparation method of the R-P type layered medium-entropy perovskite structure cathode material according to claim 4, wherein the specific ball milling process is that the cathode powder obtained in the step (3) is put into a ball milling tank filled with zirconia balls with different specifications and sizes, ethanol is added, ball milling is carried out for 24 hours in a planetary ball mill with the rotating speed of 80R/min, and the mass ratio among the cathode powder, the zirconia balls and the ethanol in the ball milling tank is 1:6:1.
6. The method for preparing the R-P type layered medium-entropy perovskite structure cathode material according to claim 4, wherein the drying process is as follows: and putting the mixture into an oven at 80 ℃ for drying for 24 hours.
7. The method for producing a cathode material of R-P type layered medium entropy perovskite structure according to claim 2 or 3, wherein in step (1), la is contained 3+ The compound of (a) is La (NO) 3 ) 3 ·6H 2 O, containing Sr 2+ The compound of (a) is Sr (NO) 3 ) 2 Contains Co 2+ The compound of (a) is Co (NO) 3 ) 2 ·6H 2 O, containing Fe 3+ The compound of (a) is Fe (NO) 3 ) 3 ·9H 2 O, ni-containing 2+ The compound of (a) is Ni (NO) 3 ) 2 ·6H 2 O、Contains Mn 2+ The compound of (C) is Mn (CH) 3 COO 3 ) 2 ·4H 2 O。
8. The method for preparing a cathode material with an R-P layered medium-entropy perovskite structure according to claim 2 or 3, wherein in the step (3), the temperature-increasing program of the equine boiler is: raising the temperature from room temperature to 300 ℃ at a heating rate of 3 ℃/min, preserving heat for 3 hours, raising the temperature from 300 ℃ to 1000 ℃ at a heating rate of 3 ℃/min, preserving heat for 4 hours, and naturally cooling to room temperature.
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| CN113381041A (en) * | 2021-06-29 | 2021-09-10 | 清华四川能源互联网研究院 | Electrode supporting type solid oxide fuel cell and preparation method thereof |
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