CN111584890B - In-situ self-stabilization type solid oxide fuel cell cathode, cell and preparation method thereof - Google Patents
In-situ self-stabilization type solid oxide fuel cell cathode, cell and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an in-situ self-stabilized solid oxide fuel cell cathode, a cell and a preparation method thereof, belonging to the field of fuel cells0.6Sr0.4Co0.2Fe0.8O3‑δThe shell layer is a perovskite material La with A-site vacancy1‑xCoO3‑δPerovskite material La with A site lacking1‑xCoO3‑δIs densely coated in La0.6Sr0.4Co0.2Fe0.8O3‑δWherein x is more than 0 and less than or equal to 0.1, and delta is a value for maintaining electroneutrality of the compound. La is formed in situ between the core and shell of the active material1‑xSryCoO3‑δAn interface transition layer, wherein x is more than 0 and less than or equal to 0.1, y is more than 0 and less than or equal to x, and delta is a value for keeping the compound electrically neutral. The invention also provides a preparation method of the catalyst, and compared with the traditional process, the step of carrying out calcination treatment in advance is omitted.
Description
Technical Field
The invention belongs to the field of fuel cells, and particularly relates to an in-situ self-stabilized solid oxide fuel cell cathode, a cell and a preparation method thereof.
Background
The problems of energy shortage and environmental pollution caused by the high-speed running of the world economy and the proliferation of the population are common challenges facing the international society at present. The economic and reasonable promotion of the large-scale application of new energy is an important way for realizing the sustainable development of society. Among a plurality of new energy systems, Solid Oxide Fuel Cells (SOFC) have attracted extensive attention because of their characteristics of high efficiency, cleanliness, silence, and the like. Compare in traditional coal burning thermal power, SOFC can be with the direct conversion of chemical energy to the electric energy, thereby avoids the carnot circulation and reduces fuel energy loss. The industrialization promotion of the SOFC technology is expected to relieve the pressure of energy and environment in China.
The SOFC single cell consists of three parts, namely a porous anode functional layer, a compact electrolyte layer and a porous cathode catalytic layer. In the working state of SOFC, flowing air and O in the air are introduced into the cathode side2Is reduced into oxygen ions under the catalytic action of cathode material, is conducted to the anode through electrolyte and is communicated with fuel gas H introduced into the anode side2、CH4Isoreaction to form H2O、CO2And release electrons, in the whole electrode reaction, oxygen ions are directionally conducted from cathode to anode in electrolyte, and electrons are conducted from anode to cathode in external circuit, and H is used2Fuel it is an example, the overall reaction is: h2+1/2O2→H2O。
The potential difference between the cathode and the anode of the hydrogen SOFC under ideal conditions follows Nernst equation, however, potential loss is inevitably generated on the electrolyte and the electrodes in the actual operation process of the cell, and the potential and the current have a very wide currentThe range exhibits a linear characteristic, whereby the polarization losses of the electrolyte and the electrodes can be simply characterized by the electrolyte resistance Re and the electrode resistances Ra (anode) and Rc (cathode). Under this assumption, the output voltage of the SOFC single cell: v is VNernst-i (Re + Ra + Rc). Therefore, the output power of the SOFC is mainly determined by the polarization impedance of the electrode and the ohmic resistance of the electrolyte, and the ohmic impedance of the dense electrolyte can be effectively reduced by thinning the thickness of the dense electrolyte in an intermediate temperature Interval (IT); but because of the high energy required for the redox reaction, cathode polarization resistance is the most dominant source of overall cell operating resistance. The key for ensuring the SOFC output power is to optimize the components and the structure of the cathode material, and the development of the high-performance cathode material with long-term operation stability is the core for promoting the SOFC technical development.
Based on comprehensive investigation on intrinsic characteristics of numerous SOFC cathode materials, La is considered to be0.6Sr0.4Co0.2Fe0.8O3-δThe (LSCF) cathode has the most promising potential for commercial applications: the LSCF has lower oxygen diffusion activation energy and certain electronic conductivity in a medium temperature interval, and the power density of a single cell taking the LSCF as a cathode is higher than 1.00Wcm in the medium temperature interval-2And LSCF material and intermediate temperature electrolyte material (Gd)0.1Ce0.9O1.95GDC) electrolyte has matched thermal expansion coefficient, simple preparation process and low cost. However, the long-term operational stability of LSCF cathodes remains to be improved.
Wachsman et al have explored the polarization decay mechanism of LSCF cathode, under the effects of high temperature and current, the LSCF cathode surface is apt to precipitate SrO-enriched and occupy the ORR active site on the cathode surface, cause the catalytic reaction efficiency to reduce, cause the electrode performance to attenuate finally; jiang et al investigated the stability of LSCF cathode against Cr poisoning under the condition of using SUS430 as a connector material, and the results showed that LSCF cathode is susceptible to volatilization and deposition poisoning of Cr element in the connector material, so that the surface morphology and phase structure of LSCF cathode is damaged, resulting in a great reduction in electrode performance. In summary, in practical operation of SOFC, the initial performance of LSCF cathode is excellent, and the performance decay gradually generated with time mainly comes from the following two aspects: (1) separating out and enriching Sr element on the surface of the LSCF cathode under current polarization; (2) the Cr element volatilized from the metal connector material is deposited and poisoned.
Aiming at the stability optimization of the LSCF cathode, Liu et al propose that the ORR catalytic activity and the current polarization stability of a cathode system can be improved by injecting the LSM on the surface of the LSCF cathode framework by adopting a solution dipping method, but the LSM material does not have the Cr poisoning resistance, and the cathode of the LSCF-LSM composite structure is not suitable for the practical application of the SOFC; chen et al by reaction of PrNi0.5Mn0.5O3(PNM) is coated on the surface of the LSCF cathode, the Cr poisoning resistance stability of the LSCF cathode system is obviously improved, but the phase forming temperature of the PNM material is relatively high, and Pr is easily decomposed6O11And (3) impurity phase.
From this, it is found that the modification of LSCF in the prior art hardly advances the progress of the industrialization. Therefore, there is a need to develop a new method for optimizing LSCF cathodes to obtain stable SOFC cathodes.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides an in-situ self-stabilized solid oxide fuel cell cathode, a cell and a preparation method thereof, and aims to obtain the in-situ self-stabilized LSCF cell cathode by coating and modifying LSCF by adopting a novel coating material, so that the technical problem of the long-term working stability of the LSCF cathode is solved.
To achieve the above objects, according to one aspect of the present invention, there is provided an in-situ self-stabilized solid oxide fuel cell cathode having a core-shell structure in which a core body is La0.6Sr0.4Co0.2Fe0.8O3-δThe shell layer is a perovskite material La with A-site vacancy1-xCoO3-δPerovskite material La with A site lacking1-xCoO3-δIs densely coated in La0.6Sr0.4Co0.2Fe0.8O3-δWherein x is more than 0 and less than or equal to 0.1, and delta is a value for maintaining electroneutrality of the compound.
Further, the cathodeWith La formed in situ between the core and shell1-xSryCoO3-δAn interface transition layer, wherein x is more than 0 and less than or equal to 0.1, y is more than 0 and less than or equal to x, and delta is a value for keeping the compound electrically neutral.
Furthermore, the core-shell structure cathode is in an element gradient distribution type of LSCF/LSC/LC from inside to outside, the oxygen vacancy concentration of the core-shell structure cathode is also in gradient distribution from inside to outside, the concentration distribution form of each layer of oxygen vacancy is LSCF > LSC > LC, the driving force for cathode oxygen ion conduction is formed by the concentration gradient, and finally the effect of optimizing the oxygen ion conduction process of the cathode can be achieved,
wherein LSCF means La0.6Sr0.4Co0.2Fe0.8O3-δThe LSC means La1-xSryCoO3-δLC refers to the perovskite material La with a vacancy at A position1-xCoO3-δ。
In the invention, the perovskite material La with A-site vacancy is selected1-xCoO3-δThe material (LC for short) is used for carrying out dense coating on the LSCF cathode to construct the LSCF @ LC cathode with a core-shell structure. Compared with other surface-modified coating materials, the LC perovskite oxide has the following characteristics: high ORR activity; b. the electron conductivity is high; b. the phase forming temperature is low; c. resisting Cr poisoning deposition and the like. In addition, the LSCF @ LC core-shell structure cathode provided by the application has unique diffusion self-stabilization characteristics: sr element precipitated on the surface of the LSCF cathode can be absorbed by the shell layer material LC in situ and diffused into A-site vacancy lattice of the LC to form stable-state lattice Sr so as to avoid forming ORR high-resistance phase SrO, and La formed in situ between the core body and the shell layer of the cathode due to the diffusion of Sr element1-xSrxCoO3-δThe interface transition layer, thus the core-shell structure cathode is in an LSCF/LSC/LC element gradient distribution type form from inside to outside, and the oxygen vacancy concentration distribution concentration is that the LSCF layer is larger than the LSC layer and is larger than the LC layer, so that the oxygen vacancy concentration of the core-shell structure cathode from inside to outside is also in gradient distribution, and the concentration gradient becomes the driving force of cathode oxygen ion conduction, and the oxygen ion conduction process of the cathode is optimized. The comprehensive effects make the cathode after coating modification have excellent long-term working stability and electrochemical performanceIs excellent.
According to a second aspect of the present invention there is also provided a battery comprising a cathode as described above.
According to a third aspect of the present invention, there is also provided a method for preparing the cathode of the in-situ self-stabilized solid oxide fuel cell as described above, which comprises an LSCF powder preparation step and an LC shell layer coating step, wherein the LC shell layer coating step specifically comprises:
firstly, dissolving metal nitrate containing lanthanum and cobalt in stoichiometric ratio in isopropanol to obtain a first solution, adding a certain amount of PVP (polyvinylpyrrolidone) and glycine into deionized water to obtain a second solution,
then, slowly mixing the first solution and the second solution, and uniformly stirring the mixture to obtain lanthanum-cobalt impregnation liquid,
then, the impregnation liquid is injected into the LSCF framework, the LSCF framework injected with the impregnation liquid is placed in a negative pressure environment for treatment for 10min to 50min,
concomitantly, the impregnation liquid loaded on the surface of the LSCF skeleton is in-situ phase-formed during the temperature rise process of the battery test, so that the calcination treatment in advance can be omitted.
Further, the negative pressure environment is less than or equal to-8 Mpa.
Further, the preparation steps of the LSCF powder are as follows:
dissolving metal nitrate in a stoichiometric ratio in deionized water, preparing a precursor solution according to the molar ratio of metal ions to EDTA to citric acid of 1: 1.5, adding ammonia water to adjust the pH value to 8-9 after the precursor solution is dissolved and clarified, stirring in an oil bath at 70-90 ℃ until viscous gel is formed, then placing in an oven, preserving the temperature at 160-200 ℃ for 10-14 h to form a porous precursor,
grinding the precursor evenly, calcining at 750-850 ℃ for 3-5 h to obtain LSCF powder,
ball milling and floatation processing are carried out on the powder after the phase formation to obtain LSCF cathode powder of hundred nanometer level,
adding a binder into the obtained LSCF powder and carbon powder according to a certain solid content ratio, grinding the mixture into cathode slurry, printing the cathode slurry on the surface of a compact GDC electrolyte by a screen printing mode, and sintering the cathode slurry into a porous LSCF framework at the temperature of 900-.
In general, the above technical solutions contemplated by the present invention can achieve the following beneficial effects compared with the prior art:
(1) the LC material has the phase forming temperature as low as 600 ℃, and can form a phase in situ in the temperature rise process after the battery is assembled.
(2) The LSCF cathode has lower oxygen diffusion activation energy (Ea is 0.93eV) and higher ORR catalytic activity, but the electronic conductivity is not very ideal under the condition of medium temperature (sigma is 300S/cm at 750 ℃), the LSCF @ LC core-shell structure cathode surface is a conformal coating LC compact conductive layer, and the A-site deficient perovskite material La1-xCoO3-δThe catalyst has excellent electronic conductivity (sigma is 1000S/cm at 750 ℃) under the condition of medium temperature, can quickly collect current on the surface of a cathode and improve the charge conduction efficiency of a cathode system, thereby optimizing the ORR catalytic activity of the cathode.
(3) Research shows that the precipitation amount of Sr element can be reduced to a certain extent by carrying out dense coating on the LSCF porous cathode framework, so that the polarization stability of the cathode is improved. However, the film coating cannot completely inhibit the precipitation and enrichment, and as the polarization time increases, the Sr element can still continuously diffuse from the LSCF bulk to the LSCF surface. In the invention, La with A-position vacancy is used1-xCoO3-δThe LSCF is densely coated, so that Sr element precipitation is inhibited, and a part of Sr element is absorbed to La1- xCoO3-δThe defect lattice of the SOFC is changed into stable lattice Sr, the generation of ORR high-resistance phase surface Sr is further reduced, and compared with single film coating, the LSCF @ LC core-shell structure cathode can ensure the long-term stable operation work of the SOFC to a greater extent.
(4) Through long-time current polarization, Sr element in the cathode with the LSCF @ LC core-shell structure is gradually diffused to an LC shell layer from the LSCF framework and enters the crystal lattice of the LC shell layer, and La is generated in situ at the LSCF/LC interface0.95SrxCoO3-δ(LSC) phase. The cathode system framework and the coating are gradually changed in LSCF/LSC/LC components, the interface element content is in gradient transition, meanwhile, the concentration of cathode oxygen vacancies is in gradient distribution from outside to inside (the oxygen vacancy concentration: LSCF > LSC > LC), and the vacancy concentration gradient is expected to be the driving force for the rapid diffusion of oxygen ions to promote the oxygen ion conduction process of the cathode reaction, so that certain activation effect is achieved on the cathode reaction.
(5) The impregnation liquid loaded on the surface of the LSCF framework is subjected to in-situ phase formation in the temperature rise process of a battery test, so that the step of calcining treatment in advance can be omitted, the preparation method is more environment-friendly and energy-saving, the calcining step is omitted, and great economic benefits can be generated in actual production.
Drawings
Fig. 1 is a schematic structural diagram of the LSCF surface coated with LC in the embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides an in-situ self-stabilized solid oxide fuel cell cathode, which comprises an active material in a core-shell structure, wherein FIG. 1 is a schematic structural diagram that an LSCF surface is coated with LC in the embodiment of the invention, and the core body is La0.6Sr0.4Co0.2Fe0.8O3-δThe shell layer is a perovskite material La with A-site vacancy1-xCoO3-δPerovskite material La with A site lacking1-xCoO3-δIs densely coated in La0.6Sr0.4Co0.2Fe0.8O3-δWherein x is more than 0 and less than or equal to 0.1, and delta is a value for maintaining electroneutrality of the compound. La is formed in situ between the core and shell of the active material1-xSryCoO3-δAn interface transition layer, wherein x is more than 0 and less than or equal to 0.1, y is more than 0 and less than or equal to x, and delta is a value for keeping the compound electrically neutral. The core-shell structure cathode is in element gradient distribution of LSCF, LSC and LC from inside to outside, the oxygen vacancy concentration of the core-shell structure cathode from inside to outside is also in gradient distribution, the concentration distribution form of each layer of oxygen vacancy is LSCF > LSC > LC, the driving force for cathode oxygen ion conduction is formed by the concentration gradient, and finally the effect of optimizing the oxygen ion conduction process of the cathode is achieved, wherein LSCF means La0.6Sr0.4Co0.2Fe0.8O3-δThe LSC means La1-xSryCoO3-δLC refers to the perovskite material La with a vacancy at A position1-xCoO3-δ。
In the present invention, the battery comprising the above cathode has higher long-term stability.
The method for preparing the cathode of the in-situ self-stabilized solid oxide fuel cell mainly comprises an LSCF powder preparation step and an LC shell layer film coating step, wherein:
the LSCF powder preparation steps are as follows:
dissolving metal nitrate in a stoichiometric ratio in deionized water, preparing a precursor solution according to a molar ratio of metal ions to EDTA to citric acid of 1: 1.5, adding ammonia water to adjust the pH value to 8-9 after the precursor solution is dissolved and clarified, stirring in an oil bath at 70-90 ℃ until viscous gel is formed, placing the viscous gel in an oven at 160-200 ℃ for 10-14 h to form a porous precursor, uniformly grinding the precursor, calcining at 750-850 ℃ for 3-5 h to obtain LSCF powder, performing ball milling and flotation treatment on the phase-formed powder to obtain nano-grade LSCF cathode powder, adding a binder into the obtained LSCF powder and carbon powder according to a certain solid content ratio, grinding the mixture into cathode slurry, performing screen printing on the cathode slurry to the surface of a compact GDC electrolyte, and sintering at 900-1100 ℃ to obtain a porous LSCF framework.
The LC shell layer film coating step specifically comprises the following steps:
firstly, dissolving metal nitrate containing lanthanum and cobalt in stoichiometric ratio in a solvent to obtain a first solution, adding a set amount of polyvinylpyrrolidone and glycine into the solvent to prepare a second solution,
then, slowly mixing the first solution and the second solution, and uniformly stirring the mixture to obtain lanthanum-cobalt impregnation liquid,
then, injecting lanthanum-cobalt impregnation liquid into the LSCF framework, and placing the LSCF framework injected with the impregnation liquid in a negative pressure environment for treatment for 10-50 min, wherein the negative pressure environment is less than or equal to-8 Mpa,
concomitantly, the impregnation liquid loaded on the surface of the LSCF skeleton is in-situ phase-formed during the temperature rise process of the battery test, so that the step of performing calcination treatment in advance can be omitted.
The following is illustrated in further detail by specific examples:
example 1
The LSCF powder preparation steps are as follows:
dissolving metal nitrate in a stoichiometric ratio in deionized water, preparing a precursor solution according to a molar ratio of metal ions to EDTA to citric acid of 1: 1.5, adding ammonia water to adjust the pH value to 8 after the precursor solution is dissolved and clarified, stirring in an oil bath at 70 ℃ until viscous gel is formed, placing the viscous gel in an oven at 200 ℃ for 14h to form a porous precursor, uniformly grinding the precursor, calcining at 750 ℃ for 5h to obtain LSCF powder, performing ball milling and flotation treatment on the powder after phase formation to obtain nano-grade LSCF cathode powder, adding a binder into the obtained LSCF powder and carbon powder according to a certain solid content ratio, grinding the mixture into cathode slurry, performing screen printing on the surface of a compact GDC electrolyte, and sintering at 1100 ℃ to obtain a porous LSCF framework.
The LC shell layer film coating step specifically comprises the following steps:
firstly, dissolving metal nitrate containing lanthanum and cobalt in stoichiometric ratio in a solvent to obtain a first solution, adding a set amount of polyvinylpyrrolidone and glycine into the solvent to prepare a second solution,
then, slowly mixing the first solution and the second solution, and uniformly stirring the mixture to obtain lanthanum-cobalt impregnation liquid,
then, injecting lanthanum-cobalt impregnation liquid into the LSCF framework, and placing the LSCF framework injected with the impregnation liquid in a negative pressure environment for treatment for 50min, wherein the negative pressure environment is less than or equal to-8 Mpa,
concomitantly, the impregnation liquid loaded on the surface of the LSCF skeleton is in-situ phase-formed during the temperature rise process of the battery test, so that the step of performing calcination treatment in advance can be omitted.
Example 2
The LSCF powder preparation steps are as follows:
dissolving metal nitrate in a stoichiometric ratio in deionized water, preparing a precursor solution according to a molar ratio of metal ions to EDTA to citric acid of 1: 1.5, adding ammonia water to adjust the pH value to 9 after the precursor solution is dissolved and clarified, stirring in an oil bath at 90 ℃ until viscous gel is formed, placing the viscous gel in an oven at 160 ℃ for 10 hours to form a porous precursor, uniformly grinding the precursor, calcining at 850 ℃ for 3 hours to obtain LSCF powder, performing ball milling and flotation treatment on the powder after phase formation to obtain nano-grade LSCF cathode powder, adding a binder into the obtained LSCF powder and carbon powder according to a certain solid content ratio, grinding the mixture into cathode slurry, performing screen printing on the surface of a compact GDC electrolyte, and sintering at 900 ℃ to obtain a porous LSCF framework.
The LC shell layer film coating step specifically comprises the following steps:
firstly, dissolving metal nitrate containing lanthanum and cobalt in stoichiometric ratio in a solvent to obtain a first solution, adding a set amount of polyvinylpyrrolidone and glycine into the solvent to prepare a second solution,
then, slowly mixing the first solution and the second solution, and uniformly stirring the mixture to obtain lanthanum-cobalt impregnation liquid,
then, injecting lanthanum-cobalt impregnation liquid into the LSCF framework, and placing the LSCF framework injected with the impregnation liquid in a negative pressure environment for treatment for 10min, wherein the negative pressure environment is less than or equal to-8 Mpa,
concomitantly, the impregnation liquid loaded on the surface of the LSCF skeleton is in-situ phase-formed during the temperature rise process of the battery test, so that the step of performing calcination treatment in advance can be omitted.
Example 3
The LSCF powder preparation steps are as follows:
dissolving metal nitrate in a stoichiometric ratio in deionized water, preparing a precursor solution according to a molar ratio of metal ions to EDTA to citric acid of 1: 1.5, adding ammonia water to adjust the pH value to 8.5 after the precursor solution is dissolved and clarified, stirring in an oil bath at 80 ℃ until viscous gel is formed, placing the viscous gel in an oven at 180 ℃ for 12 hours to form a porous precursor, uniformly grinding the precursor, calcining at 800 ℃ for 4 hours to obtain LSCF powder, carrying out ball milling and flotation treatment on the powder after phase formation to obtain nano-grade LSCF cathode powder, adding a binder into the obtained LSCF powder and carbon powder according to a certain solid content ratio, grinding the mixture into cathode slurry, carrying out screen printing on the surface of a compact GDC electrolyte, and sintering at 1000 ℃ to obtain a porous LSCF framework.
The LC shell layer film coating step specifically comprises the following steps:
firstly, dissolving metal nitrate containing lanthanum and cobalt in stoichiometric ratio in a solvent to obtain a first solution, adding a set amount of polyvinylpyrrolidone and glycine into the solvent to prepare a second solution,
then, slowly mixing the first solution and the second solution, and uniformly stirring the mixture to obtain lanthanum-cobalt impregnation liquid,
then, injecting lanthanum-cobalt impregnation liquid into the LSCF framework, and placing the LSCF framework injected with the impregnation liquid in a negative pressure environment for treatment for 40min, wherein the negative pressure environment is less than or equal to-8 Mpa,
concomitantly, the impregnation liquid loaded on the surface of the LSCF skeleton is in-situ phase-formed during the temperature rise process of the battery test, so that the step of performing calcination treatment in advance can be omitted.
Example 4
The LSCF powder preparation steps are as follows:
dissolving metal nitrate in a stoichiometric ratio in deionized water, preparing a precursor solution according to a molar ratio of metal ions to EDTA to citric acid of 1: 1.5, adding ammonia water to adjust the pH value to 8 after the precursor solution is dissolved and clarified, stirring in an oil bath at 80 ℃ until viscous gel is formed, placing the viscous gel in a drying oven at 190 ℃ for 13h to form a porous precursor, uniformly grinding the precursor, calcining at 820 ℃ for 4h to obtain LSCF powder, performing ball milling and flotation treatment on the powder after phase formation to obtain nano-grade LSCF cathode powder, adding a binder into the obtained LSCF powder and carbon powder according to a certain solid content ratio, grinding the mixture into cathode slurry, performing screen printing on the surface of a compact GDC electrolyte, and sintering at 950 ℃ to obtain a porous LSCF framework.
The LC shell layer film coating step specifically comprises the following steps:
firstly, dissolving metal nitrate containing lanthanum and cobalt in stoichiometric ratio in a solvent to obtain a first solution, adding a set amount of polyvinylpyrrolidone and glycine into the solvent to prepare a second solution,
then, slowly mixing the first solution and the second solution, and uniformly stirring the mixture to obtain lanthanum-cobalt impregnation liquid,
then, injecting lanthanum-cobalt impregnation liquid into the LSCF framework, and placing the LSCF framework injected with the impregnation liquid in a negative pressure environment for treatment for 40min, wherein the negative pressure environment is less than or equal to-8 Mpa,
concomitantly, the impregnation liquid loaded on the surface of the LSCF skeleton is in-situ phase-formed during the temperature rise process of the battery test, so that the step of performing calcination treatment in advance can be omitted.
Example 5
The LSCF powder preparation steps are as follows:
dissolving metal nitrate in a stoichiometric ratio in deionized water, preparing a precursor solution according to a molar ratio of metal ions to EDTA to citric acid of 1: 1.5, adding ammonia water to adjust the pH value to 9 after the precursor solution is dissolved and clarified, stirring in an oil bath at 70 ℃ until viscous gel is formed, placing the viscous gel in a drying oven at 180 ℃ for 12 hours to form a porous precursor, uniformly grinding the precursor, calcining at 790 ℃ for 4 hours to obtain LSCF powder, performing ball milling and flotation treatment on the powder after phase formation to obtain nano-grade LSCF cathode powder, adding a binder into the obtained LSCF powder and carbon powder according to a certain solid content ratio, grinding the mixture into cathode slurry, performing screen printing on the surface of a compact GDC electrolyte, and sintering at 1050 ℃ to obtain a porous LSCF framework.
The LC shell layer film coating step specifically comprises the following steps:
firstly, dissolving metal nitrate containing lanthanum and cobalt in stoichiometric ratio in a solvent to obtain a first solution, adding a set amount of polyvinylpyrrolidone and glycine into the solvent to prepare a second solution,
then, slowly mixing the first solution and the second solution, and uniformly stirring the mixture to obtain lanthanum-cobalt impregnation liquid,
then, injecting lanthanum-cobalt impregnation liquid into the LSCF framework, and placing the LSCF framework injected with the impregnation liquid in a negative pressure environment for treatment for 45min, wherein the negative pressure environment is less than or equal to-8 Mpa,
concomitantly, the impregnation liquid loaded on the surface of the LSCF skeleton is in-situ phase-formed during the temperature rise process of the battery test, so that the step of performing calcination treatment in advance can be omitted.
Example 6
Preparing LSCF powder by a sol-gel method, dissolving metal nitrate in a stoichiometric ratio in deionized water, preparing a precursor solution according to a molar ratio of metal ions to EDTA to citric acid of 1: 1.5, dissolving and clarifying the solution, and adding ammonia water to adjust the pH value to 8. Stirring for 10h at 80 ℃ in an oil bath until viscous gel is formed, then placing the viscous gel in an oven, preserving the heat for 12h at 180 ℃ to form a porous precursor, grinding the precursor uniformly, and calcining for 4h at 800 ℃ to obtain the LSCF powder. And performing ball milling and flotation treatment on the powder after the phase formation to obtain hundred-nanometer-level LSCF cathode powder. Adding a binder into the obtained LSCF powder and a small amount of carbon powder (pore-forming agent) according to a certain solid content ratio, grinding the mixture into cathode slurry, printing the cathode slurry on the surface of a compact GDC electrolyte by a screen printing mode, and sintering the cathode slurry into a porous framework at 1000 ℃.
The LC shell layer film is prepared by adopting a solution injection method, metal nitrate with a stoichiometric ratio is dissolved in isopropanol, a certain amount of PVP and glycine are added into a very small amount of deionized water, the two solutions are slowly mixed and uniformly stirred to be used as impregnating solution, then the impregnating solution is injected into an LSCF framework, and a sample is placed in a negative pressure environment to be treated for 20min, wherein the negative pressure environment is less than or equal to-8 Mpa.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. The in-situ self-stabilizing solid oxide fuel cell cathode is characterized in that an active material is in a core-shell structure, and a core body is La0.6Sr0.4Co0.2Fe0.8O3-δThe shell layer is a perovskite material La with A-site vacancy1-xCoO3-δPerovskite material La with A site lacking1-xCoO3-δIs densely coated in La0.6Sr0.4Co0.2Fe0.8O3-δWherein x is more than 0 and less than or equal to 0.1, and delta is a value for maintaining the compound to be electrically neutral,
la is formed in situ between the core and shell of the active material1-xSryCoO3-δInterface transition layer, perovskite material La with A site vacancy1-xCoO3-δAbsorbing a part of Sr element to La1-xCoO3-δIs less than 0, x is less than or equal to 0.1, y is less than or equal to 0, and delta is a value that keeps the compound electrically neutral.
2. The in-situ self-stabilized solid oxide fuel cell cathode according to claim 1, wherein the core-shell structure cathode has a gradient distribution of LSCF, LSC and LC elements from inside to outside, the oxygen vacancy concentration of the core-shell structure cathode from inside to outside is also in a gradient distribution, the oxygen vacancy concentration distribution of each layer is LSCF > LSC > LC, the concentration gradient is used to form the driving force for cathode oxygen ion conduction, and finally the function of optimizing the oxygen ion conduction process of the cathode is achieved,
wherein LSCF means La0.6Sr0.4Co0.2Fe0.8O3-δ，
LSC means La1-xSryCoO3-δ，
LC refers to the perovskite material La with A site lacking1-xCoO3-δ。
3. A solid oxide fuel cell comprising the cathode of any one of claims 1-2.
4. The method for preparing the cathode of the in-situ self-stabilized solid oxide fuel cell according to any one of claims 1 to 2, comprising an LSCF powder preparation step and an LC shell coating step, wherein the LC shell coating step is specifically:
firstly, dissolving metal nitrate containing lanthanum and cobalt in stoichiometric ratio in a solvent to obtain a first solution, adding a set amount of polyvinylpyrrolidone and glycine into the solvent to prepare a second solution,
then, slowly mixing the first solution and the second solution, and uniformly stirring the mixture to obtain lanthanum-cobalt impregnation liquid,
then, injecting lanthanum cobalt impregnation liquid into the LSCF framework, placing the LSCF framework injected with the impregnation liquid in a negative pressure environment for treatment for 10-50 min,
concomitantly, the impregnation liquid loaded on the surface of the LSCF skeleton is in-situ phase-formed during the temperature rise process of the battery test, so that the step of performing calcination treatment in advance can be omitted.
5. The method for preparing the cathode of the in-situ self-stabilized solid oxide fuel cell according to claim 4, which comprises an LSCF powder preparation step and an LC shell layer coating step, wherein in the LC shell layer coating step, the LSCF framework injected with the immersion liquid is placed in a negative pressure environment for treatment for 20-40 min.
6. The method of claim 5, wherein the sub-atmospheric pressure is less than or equal to-8 Mpa.
7. The method of making an in situ self-stabilized solid oxide fuel cell cathode as claimed in claim 6 wherein the LSCF powder is prepared by the steps of:
dissolving metal nitrate in a stoichiometric ratio in deionized water, preparing a precursor solution according to the molar ratio of metal ions, ethylenediamine tetraacetic acid and citric acid of 1: 1.5, adding ammonia water to adjust the pH value to 8-9 after the precursor solution is dissolved and clarified, stirring in an oil bath at 70-90 ℃ until viscous gel is formed, then placing in an oven, preserving the temperature at 160-200 ℃ for 10-14 h to form a porous precursor,
grinding the precursor evenly, calcining at 750-850 ℃ for 3-5 h to obtain LSCF powder,
ball milling and floatation processing are carried out on the powder after the phase formation to obtain LSCF cathode powder of nanometer level,
adding a binder into the obtained LSCF powder and carbon powder according to a certain solid content ratio, grinding the mixture into cathode slurry, printing the cathode slurry on the surface of a compact GDC electrolyte by a screen printing mode, and sintering the cathode slurry into a porous LSCF framework at 900-1100 ℃.
8. The method of preparing an in situ self-stabilized solid oxide fuel cell cathode according to claim 7,
stirring in oil bath at 75-85 deg.c until forming viscous gel, stoving at 170-190 deg.c for 11-13 hr to form porous precursor,
adding a binder into the obtained LSCF powder and carbon powder according to a certain solid content ratio, grinding the mixture into cathode slurry, printing the cathode slurry on the surface of a compact GDC electrolyte by a screen printing mode, and sintering the cathode slurry into a porous LSCF framework at 950-1050 ℃.
9. The method of preparing an in situ self-stabilized solid oxide fuel cell cathode according to claim 8,
adding ammonia water to adjust the pH value to 8-9 after the precursor solution is dissolved and clarified, stirring in an oil bath at 80 ℃ until viscous gel is formed, then placing in an oven, preserving heat at 180 ℃ for 12 hours to form a porous precursor,
grinding the precursor uniformly, calcining at 800 ℃ for 4h to obtain LSCF powder,
adding a binder into the obtained LSCF powder and carbon powder according to a certain solid content ratio, grinding the mixture into cathode slurry, printing the cathode slurry on the surface of a compact GDC electrolyte by a screen printing mode, and sintering the cathode slurry into a porous LSCF framework at 1000 ℃.
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| CN112310419A (en) * | 2020-11-03 | 2021-02-02 | 湖北大学 | Strontium-free and cobalt-free perovskite type composite oxide, preparation method thereof and battery |
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| CN112670521A (en) * | 2020-12-28 | 2021-04-16 | 哈尔滨工业大学 | Method for improving stability of solid oxide fuel cell cathode based on stress design |
| CN114628705B (en) * | 2022-03-21 | 2023-06-02 | 北京单原子催化科技有限公司 | Catalyst containing lanthanum strontium metal oxide with surface deficient strontium, preparation and application |
| CN114824315A (en) * | 2022-04-29 | 2022-07-29 | 华南理工大学 | Solid oxide fuel cell cathode material with high activity and Cr poisoning resistance, and preparation method and application thereof |
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