CN114045520B - Oxygen electrode for solid oxide electrolysis hydrogen production and preparation method thereof - Google Patents
Oxygen electrode for solid oxide electrolysis hydrogen production and preparation method thereof Download PDFInfo
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Abstract
The inventionBelongs to the field of solid oxide electrolytic cells, and relates to a novel oxygen electrode for producing hydrogen by using a solid oxide electrolytic cell and a preparation method thereof. The oxygen electrode comprises an LSM-YSZ oxygen electrode and LaA x B 1‑ x O 3‑δ ‑La y C 1‑y O 2‑δ Complex of LaA x B 1‑x O 3‑δ ‑La y C 1‑y O 2‑δ The compound is attached to the inner and outer surfaces of the LSM-YSZ oxygen electrode; wherein x is more than or equal to 0.1 and less than or equal to 0.9, y is more than or equal to 0.1 and less than or equal to 0.9, and delta represents an oxygen deficiency value; a and B are respectively selected from one or more of Ce, pr, nd, sm, gd, yb, ni and Fe, and C is one or more of Ce, mn, nd, bi, gd, yb, ni and Fe. Compared with the traditional LSM electrode or the LSM electrode immersed by single components, the novel cobalt-oxygen-free electrode prepared by the invention remarkably improves the performance of the electrolytic cell.
Description
Technical Field
The invention belongs to the field of solid oxide electrolytic cells, and particularly relates to a cobalt-free high-performance oxygen electrode for producing hydrogen by solid oxide electrolysis.
Background
The limited increase in fossil fuel consumption not only creates a serious energy crisis, but also causes environmental problems such as global warming and air pollution. Therefore, the development of renewable clean energy sources such as wind energy, tidal energy, solar energy and the like is promoted. However, due to regional differences and unstable energy supplies, these energy sources need to be stored in more reliable carriers. H 2 The energy storage carrier can be used as an energy carrier for transporting and storing renewable energy sources (such as solar energy and wind energy), and has wide application prospect in the future. Accordingly, a number of hydrogen production techniques have been developed, such as steam reforming. Wherein, the water electrolysis hydrogen production based on the Solid Oxide Electrolytic Cells (SOECs) has the advantages of cleanness, high efficiency, energy conservation, environmental protection and the like. The required electric energy can be from intermittent renewable energy sources such as wind energy, solar energy and the like, and the heat can be from waste heat of a factory. The technology can effectively combine electric energy and heat energy, and is subjected toHas received extensive attention.
In solid oxide cell hydrogen production, the slow kinetics of oxygen release at the anode is a major factor limiting SOEC performance. As a traditional anode material, the strontium-doped lanthanum manganate (LSM-YSZ) composite material has higher chemical and structural stability and higher temperature stability than YSZ (Y) 2 O 3 Stabilized ZrO 2 ) The electrolyte has good compatibility, but its Oxygen Evolution Reaction (OER) activity is insufficient due to its small ionic conductivity. In order to improve the activity of the LSM-YSZ electrode, most of the current improvement methods are to dope cobalt and other elements in the LSM to improve the electronic conductivity of the oxygen electrode, but due to the high thermal expansion coefficient of cobalt elements and chromium poisoning, cobalt-containing materials are generally difficult to ensure the stability of the battery; other materials have also been reported, e.g. BaCo x Fe y Zr m Y 1-x-y-m O 3-δ (BCFZY)，Ba 1-x Sr x Co 1-y Fe y O 3-δ (BSCF), etc., but these materials are not suitable for high temperature electrolytic cells and the hydrogen production efficiency is to be improved.
Disclosure of Invention
Compared with the traditional LSM electrode or single dipping electrode of the LSM, the oxygen electrode prepared by the invention obviously improves the performance of the electrolytic cell.
The technical scheme of the invention is as follows:
an oxygen electrode of solid oxide electrolytic cell comprises an LSM-YSZ oxygen electrode and LaA x B 1-x O 3-δδ -La y C 1-y O 2-δ A complex; said LaA x B 1-x O 3-δ -La y C 1-y O 2-δ The compound is attached to the inner and outer surfaces of the LSM-YSZ oxygen electrode; wherein x is more than or equal to 0.1 and less than or equal to 0.9, y is more than or equal to 0.1 and less than or equal to 0.9, delta represents an oxygen deficiency value, and is a general expression of oxide materials, and delta is more than or equal to 0 and less than or equal to 0.1;
said LaA x B 1-x O 3-δ Wherein A and B are respectively selected from one or more of Ce, pr, nd, sm, gd, yb, ni and Fe, and A and B are different elements; the La is y C 1-y O 2-δ C in (C) is one or more of Ce, mn, nd, bi, gd, yb, ni and Fe; said LaA x B 1-x O 3-δ -La y C 1-y O 2-δ LaA in the Complex x B 1-x O 3-δ And La (La) y C 1-y O 2-δ The molar ratio of (2) is 0.5-2:1; the LSM has a chemical formula of La z Sr 1-z MnO 3-δ Z is more than or equal to 0.1 and less than or equal to 0.9; YSZ has the chemical formula Y m Zr 1-m O 2 ，0.1≤m≤0.9。
In the above technical solution, further, the LaA x B 1-x O 3-δ -La y C 1-y O 2-δ The average particle diameter of the nano particles is 10-50 nm; said LaA x B 1-x O 3-δ The molar ratio of the metal ions A to the metal ions B is 0.1-10:1; the La is y C 1-y O 2-δ The molar ratio of La to C metal ions is 0.1-10:1.
In the technical scheme, the thickness of the oxygen electrode of the solid oxide electrolytic cell is 20-60 mu m; said LaA x B 1-x O 3-δ -La y C 1-y O 2-δ The amount of the compound is 1 to 15 weight percent of the mass of the LSM-YSZ oxygen electrode.
The invention also provides a preparation method of the oxygen electrode of the solid oxide electrolytic cell, which comprises the following steps:
s1, preparing an LSM-YSZ oxygen electrode;
s2, preparation LaA x B 1-x O 3-δ -La y C 1-y O 2-δ Solution: according to chemical formula LaA x B 1-x O 3-δ -La y C 1-y O 2-δ Weighing A, B, C soluble metal salt powder and lanthanum soluble metal salt powder, dissolving in water, adding a complexing agent, heating and stirring, and regulating the pH value of the solution to be less than or equal to 1 after dissolving;
s3, dipping and roasting: and (3) dipping the LSM-YSZ oxygen electrode prepared in the step S1 in the solution prepared in the step S2, and roasting at 700-1000 ℃ for 3-4 hours after dipping to obtain the oxygen electrode of the solid oxide electrolytic cell.
In the above technical solution, in step S2, laA x B 1-x O 3-δ -La y C 1-y O 2-δ In LaA x B 1-x O 3-δ The concentration of the solution is 0.1-2 mol/L, laA x B 1-x O 3-δ -LayC 1-y O 2-δ La in (La) y C 1-y O 2-δ The concentration of the solution is 0.1-2 mol/L, the adding amount of the complexing agent is 0.5-2.7 times of the total metal ion mol, the complexing agent is any one of ammonium citrate, glycine, urea, EDTA and citric acid, the heating temperature is 60-90 ℃, and the stirring time is 2-10 hours; in step S3, the dipping times are 1-5 times.
In the above technical solution, further, the preparation method of the oxygen electrode in the step S1 includes the following steps:
(1) Preparing LSM anode powder:
a. la according to the chemical formula of LSM z Sr 1-z MnO 3-δ Weighing soluble metal salt powder of corresponding metal, dissolving the soluble metal salt powder in water, adding complexing agent with the molar quantity of 0.5-2.7 times of the total metal ions, heating and stirring for 15-20 min at 60-90 ℃, and adjusting the pH value of the solution to be less than or equal to 1 after dissolving; evaporating at 60-90 deg.c until the solution becomes transparent gel liquid;
b. heating the gel substance at 200-500 ℃ for 10-30 min until self-propagating combustion is carried out to form fluffy powder, thus obtaining primary powder; the primary powder is LSM primary powder;
c. calcining the primary powder at 700-1000 ℃ for 5-10 h, grinding and sieving with a 180-mesh steel sieve to obtain secondary powder; the secondary powder is LSM secondary powder;
d. mixing the secondary powder with YSZ powder, adding the solvent A, uniformly mixing, drying the solvent, grinding, and sieving with a 180-mesh steel sieve to obtain mixed powder; the solvent A is one or more of ethanol, terpineol and n-butanol;
(2) Preparing anode slurry: adding the binder into the mixed powder obtained in the step (1), fully grinding, and then coating the mixed powder on a cathode-supported half-electrolytic cell sheet or an electrolyte-supported half-electrolytic cell sheet for natural air drying to obtain the half-electrolytic cell sheet.
(3) Roasting: calcining the semi-electrolytic cell sheet obtained in the step (2) at 700-1000 ℃ for 3-5 h to obtain the oxygen electrode in the step S1.
In the technical scheme, further, the mass ratio of the secondary powder to the YSZ powder is 1:2-2:1; the mass ratio of the mixed powder to the binder is 10:1-2:1.
In the above technical solution, further, the binder is terpineol of 6wt% ethylcellulose.
In the above technical scheme, further, the complexing agent is any one of ammonium citrate, glycine, urea, EDTA and citric acid.
In the above technical scheme, in the cathode-supported semi-electrolytic cell sheet, the cathode support layer is made of Ni-YSZ; in the electrolyte-supported half-cell sheet, the electrolyte supporting layer is made of YSZ.
In the technical scheme, the cathode support or electrolyte support semi-electrolytic cell sheet is prepared by tape casting, calendaring and powder dry pressing.
Advantageous effects
(1) The invention adds the active component LaA into the LSM-YSZ anode x B 1-x O 3-δ -La x C 1-x O 2-δ The nano particles can obviously improve the electrolysis performance of the electrolytic cell. LaA x B 1-x O 3-δ The addition of (2) is beneficial to improving the performance of the electrolytic cell, but the high activity of the particles easily causes agglomeration of the particles so as to lead to the degradation of the cell performance; la (La) y C 1-y O 2-δ The component properties are relatively stable. When it is combined with LaA x B 1-x O 3-δ LaA when added together as an active ingredient to LSM-YSZ x B 1-x O 3-δ And La (La) y C 1-y O 2-δ And the synergistic effect is generated, the coarsening of particles is inhibited, and the stability of the electrode is enhanced. LaA synthesized by the invention x B 1-x O 3-δ -La y C 1-y O 2-δ The nanoparticle will LaA x B 1- x O 3-δ And La (La) y C 1-y O 2-δ Meanwhile, as an immersed active component, the surface oxygen vacancies are more, the lattice oxygen mobility is higher, and the oxygen evolution reaction in a steam electrolysis mode is accelerated. LSM-YSZ@LaA x B 1-x O 3-δ -La y C 1-y O 2-δ The novel oxygen electrode can improve the catalytic activity of the oxygen electrode on the basis of better chemical stability, thereby increasing the electrochemical performance of the battery.
(2) In addition, according to the test comparison of the electrolytic cell, compared with the traditional method without dipping LaA x B 1-x O 3-δ -La y C 1- y O 2-δ LSM electrode of nanoparticle and LSM-YSZ@LaA x B 1-x O 3-δ Or LSM-YSZ@La y C 1-y O 2-δ Such a single component impregnated electrode, LSM-YSZ@LaA in the present invention x B 1-x O 3-δ -La y C 1-y O 2-δ The cobalt-oxygen-free electrode has significantly higher hydrogen production performance in cell testing.
(3) The invention prepares the novel oxygen electrode of the solid oxide electrolytic cell, firstly prepares LSM powder and LaA by adopting an ammonium citrate method x B 1-x O 3-δ -La y C 1-y O 2-δ And preparing a substrate of the oxygen electrode by adopting a slurry coating method or a screen printing method, and finally adding an active component by adopting a permeation method, thereby obtaining the novel oxygen electrode of the solid oxide electrolytic cell for efficiently producing hydrogen.
(4) The anode slurry formula adopted by the invention comprises LSM-YSZ mixed powder and a binder. The LSM and YSZ powder are mixed to manufacture the oxygen electrode so as to improve the compatibility of the electrolyte in the electrolytic cell and effectively solve the problems of heat matching and the like. The binder is added to bond the dispersed particles or clusters together on a submicron scale, which is beneficial to the subsequent calcination forming of the oxygen electrode. The content of the binder is added according to the size of the particle size of the powder, and when the particle size of the powder is smaller, relatively more binder needs to be added to enable the slurry to be fully bonded.
Drawings
FIG. 1 is a cross-sectional SEM image of an LSM-YSZ oxygen electrode of comparative example 1;
FIG. 2 is LSM-YSZ@LaNi of comparative example 2 0.4 Fe 0.6 O 3-δ SEM image of oxygen electrode cross section;
FIG. 3 is LSM-YSZ@La of comparative example 3 0.45 Ce 0.55 O 2-δ SEM image of oxygen electrode cross section;
FIG. 4 is LSM-YSZ- @ LaNi of example 1 0.4 Fe 0.6 O 3-δ -La 0.45 Ce 0.55 O 2-δ SEM image of oxygen electrode cross section;
FIG. 5 is LSM-YSZ, LSM-YSZ@LaNi at 725 ℃ 0.4 Fe 0.6 O 3-δ 、LSM-YSZ@La 0.45 Ce 0.55 O 2-δ 、LSM-YSZ@LaNi 0.4 Fe 0.6 O 3-δ -La 0.45 Ce 0.55 O 2-δ Is a graph of impedance.
FIG. 6 is a chart of LSM-YSZ, LSM-YSZ@LaNi at 800 ℃ 0.4 Fe 0.6 O 3-δ 、LSM-YSZ@La 0.45 Ce 0.55 O 2-δ 、LSM-YSZ@LaNi 0.4 Fe 0.6 O 3-δ -La 0.45 Ce 0.55 O 2-δ Voltage-current density graph of (c).
Detailed Description
The invention is further illustrated below in connection with specific examples, but is not limited in any way. In the following examples and comparative examples, the range of δ was 0.ltoreq.δ.ltoreq.0.1.
Comparative example 1:
the preparation method of the oxygen electrode of the solid oxide electrolytic cell comprises the following steps:
(1) Synthesis of La by ammonium citrate method 0.8 Sr 0.2 MnO 3-δ (0.ltoreq.delta.ltoreq.0.1) anode powder
La was prepared at a molar concentration of 0.5mol/L 3+ 、Sr 2+ 、Mn 3+ The nitrate solution of La is accurately removed according to the proportion of 4:1:5 3+ 、Sr 2+ 、Mn 3+ In a 500ml beaker. Heating and stirring at 60deg.C for 20min to obtain mixed La 3+ 、Sr 2+ 、Mn 3+ Is a nitrate solution of (a). Then according to ammonium citrate: adding ammonium citrate (analytically pure) at a molar ratio of 1.5:1, heating and stirring, regulating pH=8 with ammonia water (analytically pure) to make the solution become clear and transparent, heating and stirring at 70deg.C to evaporate solvent until the solution becomes gel, pouring into 1000ml evaporation pan, heating with electric furnace to make the system self-propagating burn to obtain fluffy powder, collecting the obtained primary powder, roasting in muffle furnace at 1000deg.C for 6 hr, grinding, and sieving with 180 mesh steel sieve to obtain La 0.8 Sr 0.2 MnO 3-δ Anode powder.
(2)La 0.8 Sr 0.2 MnO 3-δ Preparation of YSZ oxygen electrode
La prepared in (1) 0.8 Sr 0.2 MnO 3-δ Anode powder and YSZ powder (8% Y in molar composition 2 O 3 Stabilized ZrO 2 Mixing (Tosho, japan)) according to a mass ratio of 3:2, adding ethanol, grinding to obtain a mixture, drying the mixture under a baking lamp to obtain a solvent, transferring the solvent into a mortar, grinding the mixture by a 180-mesh steel screen, adding a binder (terpineol containing 6wt% of ethyl cellulose), coating 0.0080g of the mixture on a cathode-supported semi-electrolytic cell sheet by a slurry coating method, and sintering the mixture in a muffle furnace at 1000 ℃ for 3 hours to obtain La 0.8 Sr 0.2 MnO 3-δ -YSZ oxygen electrode.
(3) SOEC test: electrolytic tests were performed on self-assembled battery evaluation devices at 700-800 c, and the impedance spectra and voltage-current density curves measured are shown in fig. 5 and 6, respectively.
FIG. 1 shows an SEM of a cross-section of an oxygen electrode of LSM-YSZ in which LSM and YSZ are uniformly distributed and in intimate contact as shown in FIG. 1.
Comparative example 2:
the preparation method of the oxygen electrode of the solid oxide electrolytic cell comprises the following steps:
(1) Synthesis of La by ammonium citrate method 0.8 Sr 0.2 MnO 3-δ Anode powder.
La was prepared at a molar concentration of 0.5mol/L 3+ 、Sr 2+ 、Mn 3+ Accurately transferring and weighing La according to the proportion of 4:1:5 3+ 、Sr 2+ 、Mn 3+ In a 500ml beaker. Heating and stirring at 60deg.C for 20min to obtain mixed La 3+ 、Sr 2+ 、Mn 3+ Is a nitrate solution of (a). Then according to ammonium citrate: adding ammonium citrate (analytically pure) at a molar ratio of 1.5:1, heating and stirring, regulating pH=8 with ammonia water (analytically pure) to make the solution become clear and transparent, heating and stirring at 70deg.C to evaporate solvent until the solution becomes gel, pouring into 1000ml evaporation pan, heating with electric furnace to make the system self-propagating burn to obtain fluffy powder, collecting the obtained primary powder, roasting in muffle furnace at 1000deg.C for 6 hr, grinding, and sieving with 180 mesh steel sieve to obtain La 0.8 Sr 0.2 MnO 3-δ Anode powder.
(2)La 0.8 Sr 0.2 MnO 3-δ Preparation of YSZ oxygen electrode
La prepared in (1) 0.8 Sr 0.2 MnO 3-δ Anode powder and YSZ powder (8% Y in molar composition 2 O 3 Stabilized ZrO 2 Mixing (Tosho, japan)) according to a mass ratio of 3:2, adding ethanol, grinding to obtain a mixture, drying the mixture under a baking lamp to obtain a solvent, transferring the solvent into a mortar, grinding the mixture by a 180-mesh steel screen, adding a binder (terpineol containing 6wt% of ethyl cellulose), coating 0.0080g of the mixture on a cathode-supported semi-electrolytic cell sheet by a slurry coating method, and sintering the mixture in a muffle furnace at 1000 ℃ for 3 hours to obtain La 0.8 Sr 0.2 MnO 3-δ -YSZ oxygen electrode.
(3) Impregnation solution LaNi 0.4 Fe 0.6 O 3-δ Is prepared from
La with a molar concentration of 1mol/L was prepared separately 3+ 、Ni 2+ 、Fe 3+ Accurately transferring and weighing La according to the proportion of 5:2:3 3+ 、Ni 2+ 、Fe 3+ In a 500ml beaker. Heating and stirring at 60deg.C for 20min to obtain mixed La 3+ 、Ni 2+ 、Fe 3+ Is a nitrate solution of (a). Ammonium citrate was then added (analysisPure), ammonium citrate: the total metal cation mole ratio is 1.3, heating and stirring, adjusting pH=1 with nitric acid (analytically pure), clarifying and transparentizing the solution, fixing the solution in 100ml volumetric flask, and LaNi 0.4 Fe 0.6 O 3-δ The concentration of (C) was 0.5mol/L.
(4)LSM-YSZ-LaNi 0.4 Fe 0.6 O 3-δ Oxygen electrode preparation
mu.L of the LaNi formulated in step (3) was taken using a microliter syringe 0.4 Fe 0.6 O 3-δ Injection of the solution into La 0.8 Sr 0.2 MnO 3-δ The surface of the oxygen electrode of YSZ is soaked in vacuum, roasting is carried out for 3 hours at 800 ℃ to enable the soaking solution to enter the inside of the anode, the soaking solution is soaked in the surface and micropores of the oxygen electrode, and finally the LSM-YSZ@LaNi is obtained 0.4 Fe 0.6 O 3-δ An oxygen electrode.
(5) SOEC test: electrolytic tests were performed on self-assembled battery evaluation devices at 700-800 c, and the impedance spectra and voltage-current density curves measured are shown in fig. 5 and 6, respectively.
FIG. 2 shows LSM-YSZ@LaNi 0.4 Fe 0.6 O 3-δ As shown in FIG. 2, in the SEM image of the oxygen electrode section of (C) 0.4 Fe 0.6 O 3-δ In the oxygen electrode, laNi 0.4 Fe 0.6 O 3-δ The nanoparticles uniformly covered the surface of the LSM and YSZ particles.
Comparative example 3:
the preparation method of the oxygen electrode of the solid oxide electrolytic cell comprises the following steps:
(1) Synthesis of La by ammonium citrate method 0.8 Sr 0.2 MnO 3-δ Anode powder.
La was prepared at a molar concentration of 0.5mol/L 3+ 、Sr 2+ 、Mn 3+ Accurately transferring and weighing La according to the proportion of 4:1:5 3+ 、Sr 2+ 、Mn 3+ In a 500ml beaker. Heating and stirring at 60deg.C for 20min to obtain mixed La 3+ 、Sr 2+ 、Mn 3+ Is a nitrate solution of (a). Then according to ammonium citrate: the molar ratio of the total metal ions isAdding ammonium citrate (analytically pure) at a ratio of 1.5:1, heating and stirring, adjusting pH=8 with ammonia water (analytically pure) to make the solution become clear and transparent, heating and stirring at 70deg.C to evaporate the solvent until the solution becomes gel, pouring into 1000ml evaporation pan, heating with electric furnace to self-spread the system and burn to obtain fluffy powder, collecting the obtained primary powder, calcining in muffle furnace at 1000deg.C for 6 hr, grinding, and sieving with 180 mesh steel sieve to obtain La 0.8 Sr 0.2 MnO 3-δ Anode powder.
(2)La 0.8 Sr 0.2 MnO 3-δ Preparation of YSZ oxygen electrode
La prepared in (1) 0.8 Sr 0.2 MnO 3-δ Anode powder and YSZ powder (8% Y in molar composition 2 O 3 Stabilized ZrO 2 Mixing (Tosho, japan)) according to a mass ratio of 3:2, adding ethanol, grinding to obtain a mixture, drying the mixture under a baking lamp to obtain a solvent, transferring the solvent into a mortar, grinding the mixture by a 180-mesh steel screen, adding a binder (terpineol containing 6wt% of ethyl cellulose), coating 0.0080g of the mixture on a cathode-supported semi-electrolytic cell sheet by a slurry coating method, and sintering the mixture in a muffle furnace at 1000 ℃ for 3 hours to obtain La 0.8 Sr 0.2 MnO 3-δ -YSZ oxygen electrode.
(3) Impregnating solution La 0.45 Ce 0.55 O 2-δ Is prepared from
La with a molar concentration of 1mol/L was prepared separately 3+ 、Ce 3+ Accurately transferring and weighing La according to the proportion of 9:11 3+ 、Ce 3+ In a 500ml beaker. Heating and stirring at 60deg.C for 20min to obtain mixed La 3+ 、Ce 3+ Is a nitrate solution of (a). Ammonium citrate (analytically pure) was then added: the total metal cation molar ratio was 1.3, the solution was adjusted to ph=1 with nitric acid (analytically pure) by heating and stirring to make the solution clear and transparent, the solution was fixed to volume in a 100ml volumetric flask, la 0.45 Ce 0.55 O 2-δ The concentration of (C) was 0.5mol/L.
(4)LSM-YSZ-La 0.45 Ce 0.55 O 2-δ Oxygen electrode preparation
mu.L of La prepared in step (3) was taken using a microliter syringe 0.45 Ce 0.55 O 2-δ Injection of the solution into La 0.8 Sr 0.2 MnO 3-δ The surface of the oxygen electrode of the YSZ is soaked in vacuum, roasting is carried out for 3 hours at 800 ℃ to enable the soaking solution to enter the inside of the anode, the soaking solution is soaked into the surface and micropores of the oxygen electrode, and finally the LSM-YSZ@La is obtained 0.45 Ce 0.55 O 2-δ An oxygen electrode.
(5) SOEC test: electrolytic tests were performed on self-assembled battery evaluation devices at 700-800 c, and the impedance spectra and voltage-current density curves measured are shown in fig. 5 and 6, respectively.
FIG. 3 shows LSM-YSZ@La 0.45 Ce 0.55 O 2-δ As shown in FIG. 3, in the SEM image of the oxygen electrode section of (C) 0.45 Ce 0.55 O 2-δ In the oxygen electrode, la 0.45 Ce 0.55 O 2-δ The nanoparticles uniformly covered the surface of the LSM and YSZ particles.
Example 1:
the preparation method of the oxygen electrode of the solid oxide electrolytic cell comprises the following steps:
(1) Synthesis of La by ammonium citrate method 0.8 Sr 0.2 MnO 3-δ Anode powder.
La was prepared at a molar concentration of 0.5mol/L 3+ 、Sr 2+ 、Mn 3+ Accurately transferring and weighing La according to the proportion of 4:1:5 3+ 、Sr 2+ 、Mn 3+ In a 500ml beaker. Heating and stirring at 60deg.C for 20min to obtain mixed La 3+ 、Sr 2+ 、Mn 3+ Is a nitrate solution of (a). Then according to ammonium citrate: adding ammonium citrate (analytically pure) at a molar ratio of 1.5:1, heating and stirring, regulating pH=8 with ammonia water (analytically pure) to make the solution become clear and transparent, heating and stirring at 70deg.C to evaporate solvent until the solution becomes gel, pouring into 1000ml evaporation pan, heating with electric furnace to make the system self-propagating burn to obtain fluffy powder, collecting the obtained primary powder, roasting in muffle furnace at 1000deg.C for 6 hr, grinding, and sieving with 180 mesh steel sieve to obtain La 0.8 Sr 0.2 MnO 3-δ Anode powder.
(2)La 0.8 Sr 0.2 MnO 3-δ Preparation of YSZ oxygen electrode
La prepared in (1) 0.8 Sr 0.2 MnO 3-δ Anode powder and YSZ powder (8% Y in molar composition 2 O 3 Stabilized ZrO 2 Mixing (Tosho, japan)) according to a mass ratio of 3:2, adding ethanol, grinding to uniformly mix, then placing the mixture under a baking lamp, drying the solvent, transferring the solvent into a mortar, grinding the mixture by a 180-mesh steel screen, adding a binder (terpineol containing 6wt% of ethyl cellulose), coating 0.0080g on a cathode-supported semi-electrolytic cell sheet by a slurry coating method, and then placing the semi-electrolytic cell sheet in a muffle furnace for sintering at 1000 ℃ for 3 hours to obtain La 0.8 Sr 0.2 MnO 3-δ -YSZ oxygen electrode.
(3) Impregnation solution LaNi 0.4 Fe 0.6 O 3-δ -La 0.45 Ce 0.55 O 2-δ Is prepared from
La with a molar concentration of 1mol/L was prepared separately 3+ 、Ni 2+ 、Fe 3+ 、Ce 3+ Accurately transferring and weighing La according to the proportion of 145:40:60:55 3+ 、Ni 2+ 、Fe 3+ 、Ce 3+ In a 500ml beaker. Heating and stirring at 60deg.C for 20min to obtain mixed La 3+ 、Ni 2+ 、Fe 3+ 、Ce 3+ Is a nitrate solution of (a). Ammonium citrate (analytically pure) was then added: the total metal cation mole ratio was 1.3, the solution was clarified and transparent by heating and stirring, adjusting the ph=1 of the solution with nitric acid (analytically pure), and the solution was fixed to volume in a 100ml volumetric flask, laNi 0.4 Fe 0.6 O 3-δ The concentration of (2) is 0.5mol/L, la 0.45 Ce 0.55 O 2-δ The concentration of (C) was 0.5mol/L.
(4)LSM-YSZ-LaNi 0.4 Fe 0.6 O 3-δ -La 0.45 Ce 0.55 O 2-δ Oxygen electrode preparation
Lani prepared in step 4. Mu.L (3) was taken using a microliter syringe 0.4 Fe 0.6 O 3-δ -La 0.45 Ce 0.55 O 2-δ Injection of the solution into La 0.8 Sr 0.2 MnO 3-δ The surface of the delta-YSZ oxygen electrode is soaked in vacuum, roasting is carried out for 3 hours at 800 ℃ to enable the soaking solution to enter the inside of the anode, the soaking solution is soaked in the surface and micropores of the oxygen electrode, and finally the LSM-YSZ@LaNi is obtained 0.4 Fe 0.6 O 3-δ -La 0.45 Ce 0.55 O 2-δ An oxygen electrode.
(5) SOEC test: electrolytic tests were performed on self-assembled battery evaluation devices at 700-800 c, and the impedance spectra and voltage-current density curves measured are shown in fig. 5 and 6, respectively.
FIG. 4 shows LSM-YSZ@LaNi 0.4 Fe 0.6 O 3-δ -La 0.45 Ce 0.55 O 2-δ As shown in FIG. 4, in the SEM image of the section of the oxygen electrode, at LSM-YSZ@LaNi 0.4 Fe 0.6 O 3-δ -La 0.45 Ce 0.55 O 2-δ In the oxygen electrode, laNi 0.4 Fe 0.6 O 3-δ -La 0.45 Ce 0.55 O 2-δ The nanoparticles uniformly covered the surface of the LSM and YSZ particles. From the particle size statistics, laNi 0.4 Fe 0.6 O 3-δ -La 0.45 Ce 0.55 O 2-δ The average size of the nanoparticles was about 17nm.
FIG. 5 is LSM-YSZ, LSM-YSZ@LaNi at 725 ℃ 0.4 Fe 0.6 O 3-δ 、LSM-YSZ@La 0.45 Ce 0.55 O 2-δ 、LSM-YSZ@LaNi 0.4 Fe 0.6 O 3-δ -La 0.45 Ce 0.55 O 2-δ Is a graph of impedance. The difference between the high frequency intercept and the low frequency intercept in the figure represents the polarization resistance, and from the figure, LSM-YSZ@LaNi can be seen 0.4 Fe 0.6 O 3-δ -La 0.45 Ce 0.55 O 2-δ Is obviously smaller than LSM-YSZ, LSM-YSZ@LaNi 0.4 Fe 0.6 O 3-δ 、LSM-YSZ@La 0.45 Ce 0.55 O 2-δ Description of LSM-YSZ@LaNi 0.4 Fe 0.6 O 3-δ -La 0.45 Ce 0.55 O 2-δ With higher cellsPerformance.
FIG. 6 is a chart of LSM-YSZ, LSM-YSZ@LaNi at 800 ℃ 0.4 Fe 0.6 O 3-δ 、LSM-YSZ@La 0.45 Ce 0.55 O 2-δ 、LSM-YSZ@LaNi 0.4 Fe 0.6 O 3-δ -La 0.45 Ce 0.55 O 2-δ Voltage-current density graph of (c). As can be seen from the figure, under a voltage of 1-3V, LSM-YSZ@LaNi 0.4 Fe 0.6 O 3-δ -La 0.45 Ce 0.55 O 2-δ Is 1.02A cm -2 Far higher than LSM-YSZ (0.474 Acm -2 )、LSM-YSZ@LaNi 0 . 4 Fe 0.6 O 3-δ (0.485Acm -2 )、LSM-YSZ@La 0.45 Ce 0.55 O 2-δ (0.478A cm -2 ) Thus LSM-YSZ@LaNi 0.4 Fe 0.6 O 3-δ -La 0.45 Ce 0.55 O 2-δ Has remarkably excellent electrochemical properties.
Other examples compared with example 1, only LaA x B 1-x O 3-δ -La y C 1-y O 2-δ The composition of the complexes is different and is detailed in the following table.
| Sequence number | LaA x B 1-x O 3-δ | La y C 1-y O 2-δ |
| Example 2 | LaNi 0.2 Fe 0.8 O 3-δ | La 0.7 Ce 0.3 O 2-δ |
| Example 3 | LaCa 0.4 Fe 0.6 O 3-δ | La 0.8 Pr 0.2 O 2-δ |
EXAMPLE 2 modification of LaNi x Fe 1-x O 3-δ -La y Ce 1-y O 2-δ The element proportion in the compound is that the prepared electrode is LSM-YSZ@LaNi 0.2 Fe 0.8 O 3-δ -La 0.7 Ce 0.3 O 2-δ A current density of 0.753A cm at a voltage of 1.3V -2 Is higher than LSM-YSZ (0.474 Acm -2 )
Example 3 modification LaA x B 1-x O 3-δ -La y C 1-y O 2-δ Element class of the composite, LSM-YSZ@LaCa was prepared 0.4 Fe 0.6 O 3-δ -La 0.8 Pr 0.2 O 2-δ An electrode having a current density of 0.633A cm at a voltage of 1.3V -2 Is higher than LSM-YSZ (0.474 Acm -2 )。
Comparative example 4
The difference from example 1 is only that LaNi 0.4 Fe 0.6 O 3-δ With La 0.45 Ce 0.55 O 2-δ The molar ratio of (2) is 3:1, and lower La is obtained 0.45 Ce 0.55 O 2-δ Impregnating amount of LSM-YSZ@LaNi 0.4 Fe 0.6 O 3-δ -La 0.45 Ce 0.55 O 2-δ An electrode. The current density of the electrode at 1.3V voltage is 0.528A cm -2 With LSM-YSZ@LaNi in example 1 0.4 Fe 0.6 O 3-δ (0.485Acm -2 )、LSM-YSZ@La 0.45 Ce 0.55 O 2-δ (0.478A cm -2 ) Is relatively close to the current density of LSM-YSZ@LaNi in example 1 0.4 Fe 0.6 O 3-δ -La 0.45 Ce 0.55 O 2-δδ (1.02A cm -2 ) Large phase difference, sayMing LaNi 0.4 Fe 0.6 O 3-δ With La 0.45 Ce 0.55 O 2-δ The improvement in performance of the impregnated electrode was less pronounced with a 3:1 molar ratio of the complexes (LaNi in example 1 0.4 Fe 0.6 O 2-δ With La 0.45 Ce 0.55 O 2-δ The molar ratio of (2) is 1:1), can effectively improve the performance of the electrode battery.
As can be seen from the comparative examples and examples, LSM-YSZ@LaNi is superior to either an uninverted LSM or a single component impregnated LSM electrode 0.4 Fe 0.6 O 2-δ -La 0.45 Ce 0.55 O 2-δ Has remarkable performance advantages. The main reason is LaA x B 1-x O 3-δ And La (La) y C 1- y O 2-δ When added together as active ingredients, produce a synergistic effect, laA x B 1-x O 3-δ And La (La) y C 1-y O 2-δ The coarsening of particles can be mutually inhibited, the stability of the electrode is enhanced, and the performance of the oxygen electrode is improved. LaA x B 1-x O 3-δ -La y C 1-y O 2-δ The nanoparticle will LaA x B 1-x O 3-δ And La (La) y C 1-y O 2-δ Meanwhile, as an immersed active component, the surface oxygen vacancies are more, the lattice oxygen mobility is higher, and the oxygen evolution reaction in a steam electrolysis mode is accelerated.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (7)
1. An oxygen electrode of a solid oxide electrolytic cell, characterized in that the oxygen electrode comprises an LSM-YSZ oxygen electrode and LaA x B 1-x O 3-δ -La y C 1-y O 2-δ Complex of LaA x B 1-x O 3-δ -La y C 1-y O 2-δ A composite attached to the inner and outer surfaces of the LSM-YSZ oxygen electrode; wherein x is more than or equal to 0.1 and less than or equal to 0.9, y is more than or equal to 0.1 and less than or equal to 0.9, delta represents an oxygen deficiency value, and delta is more than or equal to 0 and less than or equal to 0.1;
said LaA x B 1-x O 3-δ -La y C 1-y O 2-δ LaA in the Complex x B 1-x O 3-δ Wherein A and B are respectively selected from one or more of Ce, pr, nd, sm, gd, yb, ni and Fe, and A and B are different elements; la (La) y C 1-y O 2-δ C in (C) is one or more of Ce, mn, nd, bi, gd, yb, ni and Fe; said LaA x B 1-x O 3-δ -La y C 1-y O 2-δ LaA in the Complex x B 1-x O 3-δ And La (La) y C 1-y O 2-δ The molar ratio of (2) is 0.5-2:1;
the LSM-YSZ oxygen electrode has a chemical formula of La z Sr 1-z MnO 3-δ Z is more than or equal to 0.1 and less than or equal to 0.9; YSZ has the chemical formula Y m Zr 1-m O 2 ，0.1≤m≤0.9；
The thickness of the oxygen electrode of the solid oxide electrolytic cell is 20-60 mu m; said LaA x B 1-x O 3-δ -La y C 1-y O 2-δ The amount of the compound is 1 to 15 weight percent of the mass of the LSM-YSZ oxygen electrode;
the preparation method of the oxygen electrode of the solid oxide electrolytic cell comprises the following steps:
s1, preparing an LSM-YSZ oxygen electrode;
s2, preparation LaA x B 1-x O 3-δ -La y C 1-y O 2-δ Solution: according to chemical formula LaA x B 1-x O 3-δ -La y C 1-y O 2-δ Weighing A, B, C soluble metal salt powder and lanthanum soluble metal salt powder, adding the soluble metal salt powder and the lanthanum soluble metal salt powder into water, adding a complexing agent after dissolving, heating and stirring, and adjusting the pH value of the solution to be less than or equal to 1 after dissolving;
s3, dipping and roasting: soaking the LSM-YSZ oxygen electrode prepared in the step S1 in the solution prepared in the step S2, and roasting at 700-1000 ℃ for 3-4 hours after soaking to obtain the oxygen electrode of the solid oxide electrolytic cell;
the step S1 includes the steps of:
(1) Preparing LSM anode powder:
a. la according to the chemical formula of LSM z Sr 1-z MnO 3-δ Weighing soluble metal salt powder of corresponding metal, adding water for dissolving, adding complexing agent with the molar weight of 0.5-2.7 times of the total metal ions, heating and stirring for 15-20 min at 60-90 ℃, and adjusting the pH value of the solution to be less than or equal to 1 after dissolving; evaporating at 60-90 deg.c until the solution becomes transparent gel liquid;
b. heating the gel substance at 200-500 ℃ for 10-30 min until self-propagating combustion is carried out to form fluffy powder, thus obtaining LSM primary powder;
c. calcining the primary powder at 700-1000 ℃ for 5-10 h, and grinding to obtain LSM secondary powder;
d. mixing the secondary powder with YSZ powder, adding a solvent, uniformly mixing, drying and grinding to obtain mixed powder; the solvent is one or more of ethanol, terpineol and n-butanol;
(2) Preparing anode slurry: adding a binder into the mixed powder obtained in the step (1), fully grinding, and then coating the mixed powder on a cathode-supported half-electrolytic cell sheet or an electrolyte-supported half-electrolytic cell sheet for natural air drying to obtain the half-electrolytic cell sheet;
(3) Roasting: calcining the semi-electrolytic cell sheet obtained in the step (2) at 700-1000 ℃ for 3-5 h to obtain the LSM-YSZ oxygen electrode in the step S1.
2. The solid oxide electrolysis cell oxygen electrode of claim 1, wherein said LaA x B 1-x O 3-δ -La y C 1-y O 2-δ The average particle diameter of the nano particles of the compound is 10-50 nm; the molar ratio of the metal ions A to the metal ions B is 0.1-10:1; the La is y C 1-y O 2-δ The molar ratio of La to C metal ions is 0.1-10:1.
3. According to the weightsThe solid oxide electrolysis cell oxygen electrode of claim 1, wherein in step S2, laA x B 1- x O 3-δ -La y C 1-y O 2-δ In LaA x B 1-x O 3-δ The concentration of the solution is 0.1-2 mol/L, laA x B 1-x O 3-δ -La y C 1-y O 2-δ La in (La) y C 1- y O 2-δ The concentration of the solution is 0.1-2 mol/L, the adding amount of the complexing agent is 0.5-2.7 times of the total metal ion mol, the complexing agent is any one of ammonium citrate, glycine, urea, EDTA and citric acid, the heating temperature is 60-90 ℃, and the stirring time is 2-10 hours; in step S3, the dipping times are 1-5 times.
4. The solid oxide electrolysis cell oxygen electrode according to claim 1, wherein the mass ratio of the secondary powder to YSZ powder is 1:2-2:1; the mass ratio of the mixed powder to the binder is 10:1-2:1; the binder is terpineol containing 6wt% ethyl cellulose; the complexing agent is any one of ammonium citrate, glycine, urea, EDTA and citric acid.
5. The oxygen electrode of the solid oxide electrolytic cell according to claim 1, wherein the cathode support layer is made of Ni-YSZ; in the electrolyte-supported half-cell sheet, the electrolyte supporting layer is made of YSZ.
6. The solid oxide cell oxygen electrode of claim 1, wherein the cathode-supported half cell sheet or the electrolyte-supported half cell sheet is prepared by casting, calendaring, or powder dry pressing.
7. Use of an oxygen electrode according to any one of claims 1 to 6 in a solid oxide electrolysis cell.
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