CN111910201A - Hydrogen electrode of solid oxide electrolytic cell, preparation method of hydrogen electrode and solid oxide electrolytic cell - Google Patents
Hydrogen electrode of solid oxide electrolytic cell, preparation method of hydrogen electrode and solid oxide electrolytic cell Download PDFInfo
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Abstract
The application belongs to the technical field of solid oxide electrolytic cells, and particularly relates to a hydrogen electrode of a solid oxide electrolytic cell, a preparation method of the hydrogen electrode and the solid oxide electrolytic cell. The preparation method comprises the following steps: step 1, mixing NiO, yttria-stabilized zirconia, a second pore-forming agent and a solvent to obtain a second mixture, arranging the second mixture on the surface of a hydrogen electrode support, drying and presintering to obtain a pre-hydrogen electrode; wherein the mass ratio of NiO to yttria-stabilized zirconia is (0.6-2.3) to 1; and 2, arranging the nano particles on the pre-hydrogen electrode, and sintering to obtain the hydrogen electrode of the solid oxide electrolytic cell. The application discloses a hydrogen electrode of a solid oxide electrolytic cell and a preparation method thereof, which can effectively solve the technical problems of poor uniformity and controllability of the pore structure and porosity of the existing Ni-YSZ porous metal ceramic.
Description
Technical Field
The application belongs to the technical field of solid oxide electrolytic cells, and particularly relates to a hydrogen electrode of a solid oxide electrolytic cell, a preparation method of the hydrogen electrode and the solid oxide electrolytic cell.
Background
The solid oxide electrolytic cell (hereinafter referred to as SOEC) is a solid oxide fuel cell operated in reverse, and electrolyzes H by applying voltage and high temperature2O, production of H2And O2And converting the electric energy and the heat energy into chemical energy.
Decomposition of water vapor to produce H2The hydrogen electrode is used as a catalyst to accelerate the reaction speed, reduce the overpotential and provide channels for the transmission of electrons and ions. Therefore, the hydrogen electrode material should satisfy the following requirements: the structure and the components are stable under the high-temperature and high-humidity condition, and the long-term operation can be realized; the catalyst has good electronic conductivity and oxygen ion conductivity to ensure the transmission of electrons and oxygen ions, and has good catalytic activity on the decomposition reaction of water vapor; the porous structure can ensure the supply of water vapor and the discharge of hydrogen products required by electrolysis; matched with the thermal expansion coefficient of the electrolyte and does not chemically react.
Ni-YSZ porous metal ceramic is the preferred hydrogen electrode material of the high-temperature SOEC at present. At high temperature, Ni is not only a good catalyst for reforming catalytic reaction and hydrogen electrochemical oxidation reaction, but also has lower cost compared with Co, Pt, Pd and the like, and has economical efficiency. YSZ is used as a substrate of Ni, Ni and YSZ are not fused or interacted with each other in a wide temperature range, Ni can provide electrical conductivity and catalytic activity, and YSZ plays a role of a structural framework, improves thermal compatibility, can conduct oxygen ions and widens a three-phase interface. However, the uniformity and controllability of the pore structure and porosity of the existing Ni-YSZ porous metal ceramic are poor, so that the nano-scale catalyst is easy to agglomerate under the high-temperature long-term operation, the three-phase interface is reduced, and the stability is relatively poor.
Disclosure of Invention
In view of the above, the application discloses a hydrogen electrode of a solid oxide electrolytic cell and a preparation method thereof, which can effectively solve the technical problems that the uniformity and controllability of the pore structure and the porosity of the existing Ni-YSZ porous metal ceramic are poor, so that a nano-scale catalyst is easy to agglomerate under high-temperature long-term operation, the three-phase interface is reduced, and the stability of the hydrogen electrode is reduced.
In a first aspect, the present application provides a method for preparing a hydrogen electrode of a solid oxide electrolytic cell, comprising the steps of:
and 2, arranging the nano particles on the pre-hydrogen electrode, and then sintering to obtain the hydrogen electrode of the solid oxide electrolytic cell.
Preferably, the second pore-forming agent is selected from one or more of polystyrene microspheres, polymethyl methacrylate and starch; the addition amount of the second pore-forming agent is 0-20% of the mass sum of the NiO and the yttria-stabilized zirconia.
More preferably, the second pore-forming agent is selected from polystyrene microspheres, and the particle size of the polystyrene microspheres is 1-5 μm.
Preferably, in step 2, the nanoparticles are selected from GDC, SDC, TiO2、Bi2O3、Fe2O3、SrTiO3And LaTiO3One or more of; the particle size of the nano particles is 1-100 nm; the nanoparticles are disposed by impregnation, coating, physical blending or vapor depositionOn the pre-hydrogen electrode; the loading amount of the nanoparticles is 1-10 wt.%.
More preferably, in step 2, the nanoparticles are selected from TiO2。
Preferably, the hydrogen electrode support is selected from one of a NiO yttria-stabilized zirconia support or a NiO yttria support.
Preferably, the preparation method of the NiO-yttria-stabilized zirconia support body comprises the following steps:
mixing NiO, yttria-stabilized zirconia and a first pore-forming agent to prepare a first mixture;
and placing the first mixture into a mold for molding, and then sintering to obtain the NiO-yttria stabilized zirconia support.
Preferably, the first pore-forming agent is selected from one or more of graphite, starch and polystyrene, and the dosage of the first pore-forming agent is 10-30% of the total mass of NiO and yttria-stabilized zirconia.
Wherein the second mixture is provided to the surface of the hydrogen electrode support by one method selected from the group consisting of casting, screen printing, slurry coating, and spraying.
In a second aspect, the present application provides a hydrogen electrode of a solid oxide electrolytic cell, including a hydrogen electrode of a solid oxide electrolytic cell prepared by the preparation method.
The third aspect of the application provides a solid oxide electrolytic cell, which comprises a hydrogen electrode of the solid oxide electrolytic cell prepared by the preparation method or a hydrogen electrode, an electrolyte and an oxygen electrode of the solid oxide electrolytic cell;
the hydrogen electrode of the solid oxide electrolytic cell, the electrolyte and the oxygen electrode of the solid oxide electrolytic cell are arranged in sequence.
In a fourth aspect, the present application provides a method of making a solid oxide electrolytic cell, comprising the steps of:
mixing NiO, yttria-stabilized zirconia and a pore-forming agent to obtain a first mixture, arranging the first mixture on the surface of a hydrogen electrode support, drying and presintering to obtain a pre-hydrogen electrode; wherein the mass ratio of the NiO to the yttria-stabilized zirconia is (0.6-2.3) to 1;
secondly, arranging the nano particles on the pre-hydrogen electrode, and then sintering to prepare a hydrogen electrode of the solid oxide electrolytic cell;
mixing an electrolyte material of the solid oxide electrolytic cell with a binder to obtain a second mixture, placing the second mixture on a hydrogen electrode of the solid oxide electrolytic cell, and then sequentially drying and sintering to obtain a sintered product;
and step four, mixing the oxygen electrode material of the solid oxide electrolytic cell with a binder to prepare a third mixture, placing the third mixture on the side of the second mixture of the sintered product, and then, sequentially drying and sintering to prepare the solid oxide electrolytic cell.
Preferably, in the third step, the electrolyte material of the solid oxide electrolytic cell is selected from one or more of yttria-stabilized zirconia, scandia-stabilized zirconia and gadolinium oxide-doped ceria; in step four, the oxygen electrode material of the solid oxide electrolytic cell is selected from LSC (La)0.8Sr0.2CoO3)、LSCF(La0.6Sr0.4Co0.2Fe0.8O3)、LSM(La0.8Sr0.2MnO3)、LSF(La0.8Sr0.2FeO3) Or BSCF (Ba)0.5Sr0.5Co0.8Fe0.2O3-) One or more of; in the third step and the fourth step, the binder is selected from one or more of polyvinyl butyral ester, polyethylene glycol, dioctyl phthalate, polyvinyl alcohol and terpineol solution of ethyl cellulose.
Specifically, in the first step, the pre-sintering temperature is 1000-1500 ℃, and the pre-sintering time is 2-4 hours.
Specifically, in the second step, the sintering temperature is 1000-1500 ℃, and the sintering time is 2-4 hours.
Specifically, in the third step, the sintering temperature is 1200-1600 ℃, and the sintering time is 2-5 hours.
Specifically, in the fourth step, the sintering temperature is 1000-1400 ℃, and the sintering time is 2-6 hours.
Specifically, in the third step, the mass ratio of the electrolyte material of the solid oxide electrolytic cell to the binder is (1-2): 1.
specifically, in the third step and the fourth step, the binder is an organic binder.
More preferably, in step three, the binder is selected from PVB.
More preferably, in step four, the binder is selected from a terpineol solution of ethyl cellulose. The mass percent of the terpineol solution of the ethyl cellulose is 5-15%.
Specifically, in the fourth step, the dosage of the binder is 20-50% of the mass of the oxygen electrode material of the solid oxide electrolytic cell.
Specifically, the mixing mode of the steps is ball milling mixing.
Specifically, the drying in the steps is heating drying, the drying temperature is 120 ℃, and the drying time is 1 h.
The purpose of the application is to solve the technical problems that the uniformity and controllability of the pore structure and the porosity of Ni-YSZ porous metal ceramic in the prior art are poor. The application provides a hydrogen electrode of a solid oxide electrolytic cell, a preparation method thereof and the solid oxide electrolytic cell, wherein the volume of NiO is reduced into metal Ni by adjusting the content of NiO in a hydrogen electrode functional layer, so that the porosity of the electrolytic cell after reduction is higher, the size and distribution of pores are more uniform, the gas diffusion performance of the hydrogen electrode functional layer is improved by adding a pore-forming agent, the linear density of a three-phase interface is improved, and the charge transfer impedance is reduced.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a sectional SEM photograph of sample 3 provided by an embodiment of the present application; wherein, the frame is a hydrogen electrode functional layer area;
FIG. 2 is a sectional SEM photograph of sample 1 provided by an embodiment of the present application; wherein, the frame is a hydrogen electrode functional layer area;
FIG. 3 is a sectional SEM photograph of sample 2 provided by an embodiment of the present application; wherein, the frame is a hydrogen electrode functional layer area;
FIG. 4 shows NiO surface deposited TiO of the electrode functional layer of sample 3 provided in the examples of the present application2The morphology of the nanoparticles;
FIG. 5 is a graph of the AC impedance of an electrolytic cell constructed with different hydrogen electrodes as provided in the examples of the present application;
FIG. 6 is an I-V curve of sample 1 and sample 3 under SOEC electrolyzed water conditions as provided in the examples herein;
FIG. 7 is an SEM back scattering picture of the hydrogen electrode area of the cross section of sample 1 and sample 3 provided by the example of the application;
FIG. 8 is a comparison of the voltage for 1000h of constant current electrolysis runs for sample 1 and sample 3 provided in the examples of the present application.
Detailed Description
The application provides a hydrogen electrode of a solid oxide electrolytic cell, a preparation method thereof and the solid oxide electrolytic cell, which are used for solving the technical defects that in the prior art, the uniformity and controllability of the pore structure and the porosity of Ni-YSZ porous metal ceramic are poor, so that a nano-scale catalyst is easy to agglomerate under the high-temperature long-term operation, the three-phase interface is reduced, and the stability of the hydrogen electrode is reduced.
The technical solutions in the embodiments of the present application will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The preparation method of the solid oxide electrolytic cell comprises the following steps:
1) preparation of SOEC hydrogen electrode support containing NiO and YSZ (yttria stabilized zirconia): ball-milling NiO and YSZ powder and a first pore-forming agent for 6-12 h, uniformly mixing, putting a proper amount of mixed powder into a mold, carrying out warm-pressing molding to obtain a mixture with the thickness of 100-1000 mu m, and then pre-sintering at 1000-1500 ℃ for 2h, wherein a hydrogen electrode support also serves as a support of the whole battery;
2) the hydrogen electrode of the solid oxide electrolytic cell is a hydrogen electrode functional layer, and the preparation method comprises the following steps: uniformly mixing NiO, YSZ powder, a second pore-forming agent and a solvent, coating the mixture on the surface of a hydrogen electrode support body with the thickness of 5-25 mu m, fully drying the mixture in air at 100-150 ℃, then pre-sintering the mixture for 2-4 h at 1000-1500 ℃, then introducing reactants along with carrier gas by using a gas phase method, and depositing metal oxide particles by using the gas phase method to prepare a hydrogen electrode functional layer;
3) preparation of electrolyte layer: ball-milling YSZ powder and an organic binder for 1-3 h, uniformly mixing, coating the mixture on the surface of a hydrogen electrode functional layer, wherein the thickness of the mixture is 5-30 mu m, and fully drying in air;
4) sintering of electrolyte and hydrogen electrode portions: sintering the hydrogen electrode support body-hydrogen electrode functional layer-electrolyte layer prepared in the step at 1200-1600 ℃ for 2-5 h;
5) preparation of the SOEC oxygen electrode: and (3) ball-milling and uniformly mixing the LSCF powder and the organic binder, coating the mixture on the surface of the electrolyte layer obtained in the step 4), wherein the thickness of the mixture is 5-50 mu m, fully drying the mixture, and sintering the mixture for 2-6 hours at 1000-1400 ℃ to obtain the solid oxide electrolytic cell.
Specifically, the mass ratio of NiO to YSZ in the preparation process in the step 1) is (0.5-2): 1, the first pore-forming agent is selected from at least one of graphite, starch, polystyrene and the like, and the dosage of the first pore-forming agent is 10-30% of the total mass of NiO and YSZ.
Specifically, the mass ratio of NiO to YSZ in the preparation process in the step 2) is (0.6-2.3): 1, and the second pore-forming agent is polystyrene microspheres with different sizes.
Specifically, the metal oxide nanoparticles in the preparation process of step 2) are selected from GDC, SDC and TiO2、Bi2O3、Fe2O3、SrTiO3、LaTiO3And the particle size of the metal oxide nano particles is 1-100 nm, and the deposition method can also adopt dipping, coating, physical blending, vapor deposition and the like.
Specifically, the grain diameter of the YSZ powder used in the step 1), the step 2) and the step 3) is 60-100 nm.
Specifically, the coating method of the hydrogen electrode functional layer, the electrolyte layer and the SOEC oxygen electrode in the above step 2), step 3) and step 5) is selected from one of a casting method, screen printing, slurry coating and spray coating.
Specifically, the porosity of the hydrogen electrode support body after high-temperature sintering and reduction is 25% -55%, and the porosity of the hydrogen electrode functional layer after high-temperature sintering and reduction is 20% -50%.
Specifically, in the preparation process in the step 3), the organic binder is at least one selected from polyvinyl butyral (PVB), polyethylene glycol (PEG), dioctyl phthalate (DOP), polyvinyl alcohol (PVA), and terpineol solution of ethyl cellulose, and the amount of the organic binder is 20-50% of the mass of the LSCF powder.
The raw materials and reagents used in the following examples are commercially available or self-made.
Example 1
The embodiment provides a solid oxide electrolytic cell, which comprises the following specific steps:
1) first, a SOEC hydrogen electrode support containing NiO and yttria-stabilized zirconia (hereinafter, YSZ) was prepared: ball-milling NiO and YSZ powder and a graphite pore-forming agent for 10 hours and uniformly mixing according to the mass ratio of 1:1:0.2 to obtain a first mixture, putting the mixed first mixture into a mold, carrying out warm-pressing molding to obtain a square sheet-shaped support body with the side length of 7cm and the thickness of 300 mu m, and then presintering for 2 hours at 1200 ℃ to obtain a hydrogen electrode support body; wherein, the hydrogen electrode support also serves as the support of the whole solid oxide electrolytic cell;
2) preparing a hydrogen electrode functional layer: mixing NiO and YSZ powder in a mass ratio of 2:1, wherein the grain diameter of the YSZ powder is 60-100 nm, ultrasonically dispersing the NiO and the YSZ powder in isopropanol uniformly to obtain a second mixture, coating the second mixture on the surface of a hydrogen electrode support body with the thickness of 8 mu m, and fully drying the hydrogen electrode support body in the air at 150 ℃; then sintering at 1100 ℃ for 3h, and depositing TiO on the support of the solid oxide electrolytic cell by adopting a gas phase oxidation method2The nano-particle functional layer is prepared by introducing preheated TiCl with nitrogen as carrier gas4Gas and oxygen react at 1400 deg.C, and TiO is vapor deposited2Nanoparticles, TiO2The particle size of the nano-particles is 1-100 nm, and TiO is generated2The nano particles are uniformly deposited on the hydrogen electrode support body to form a hydrogen electrode functional layer;
3) preparation of electrolyte layer: ball-milling YSZ powder and PVB for 2h according to the mass ratio of 1:0.3, uniformly mixing, dispersing by using a proper amount of isopropanol, blade-coating on the surface of a hydrogen electrode functional layer with the thickness of 10 mu m, and fully drying in the air;
4) sintering of electrolyte and hydrogen electrode portions: sintering the hydrogen electrode support body-hydrogen electrode functional layer-electrolyte layer prepared in the step at 1500 ℃ for 4 h;
5) preparation of the SOEC oxygen electrode: ball-milling and uniformly mixing LSCF powder and an organic binder according to the mass ratio of 2:1, wherein the organic binder is terpineol solution of ethyl cellulose (the mass percentage of the ethyl cellulose is 8%), coating the surface of the electrolyte layer obtained in the step 4) by a screen printing method, the thickness of the electrolyte layer is 20 mu m, and the effective area of the electrolyte layer is 36cm2And fully drying and sintering at 1100 ℃ for 3h to obtain the cell of the sample 3. The porosity of the hydrogen electrode support body after high-temperature sintering and reduction is 50%, and the porosity of the hydrogen electrode functional layer after high-temperature sintering and reduction is 30%.
Comparative example 1
The difference between the comparative example and the example 1 is that the ratio of NiO and YSZ powder is adjusted on the preparation of the hydrogen electrode functional layer, and the hydrogen is addedPolystyrene microspheres are not added in the preparation of the electrode functional layer, and TiO is not deposited on the hydrogen electrode functional layer2The method comprises the following specific steps of:
1) firstly, preparing a SOEC hydrogen electrode support body containing NiO and YSZ: ball-milling NiO and YSZ powder and a graphite pore-forming agent for 10 hours and uniformly mixing according to the mass ratio of 1:1:0.2 to obtain a first mixture, putting the mixed first mixture into a mold, carrying out warm-pressing molding to obtain a square sheet-shaped support body with the side length of 7cm and the thickness of 300 mu m, and then presintering for 2 hours at 1200 ℃ to obtain a hydrogen electrode support body; wherein, the hydrogen electrode support also serves as the support of the whole solid oxide electrolytic cell;
2) preparing a hydrogen electrode functional layer: uniformly mixing NiO and YSZ powder in a ratio of 1:1, ultrasonically dispersing the NiO and YSZ powder uniformly in isopropanol, spraying the mixture on the surface of a support with the thickness of 8 mu m, fully drying the mixture in an air atmosphere at 150 ℃, and then presintering the mixture for 3 hours at 1100 ℃ to form a hydrogen electrode functional layer;
3) preparation of electrolyte layer: ball-milling YSZ powder and PVB at a ratio of 1:0.3 for 2h, uniformly mixing, dispersing with appropriate amount of isopropanol, blade-coating on the surface of the hydrogen electrode functional layer with a thickness of 10 μm, and fully drying in air;
4) sintering of electrolyte and hydrogen electrode portions: sintering the hydrogen electrode support body-hydrogen electrode functional layer-electrolyte layer prepared in the step at 1500 ℃ for 4 h;
5) preparation of the SOEC oxygen electrode: ball-milling and uniformly mixing LSCF powder and an organic binder according to the mass ratio of 2:1, wherein the organic binder is terpineol solution of ethyl cellulose (the mass percentage of the ethyl cellulose is 8%), coating the surface of the electrolyte layer obtained in the step 4) by a screen printing method, the thickness of the electrolyte layer is 20 mu m, and the effective area of the electrolyte layer is 36cm2And sintering at 1100 ℃ for 3h after full drying to obtain the cell sheet of the sample 1, wherein the porosity is 20% after the hydrogen electrode functional layer is sintered at high temperature and reduced.
Comparative example 2
The difference between the comparative example and the example 1 is that the ratio of NiO powder and YSZ powder is adjusted on the preparation of the hydrogen electrode functional layer, and TiO is not deposited on the hydrogen electrode functional layer2The specific steps of the nano-particles are as follows：
1) Firstly, preparing a SOEC hydrogen electrode support body containing NiO and YSZ: ball-milling NiO and YSZ powder and a graphite pore-forming agent for 10 hours and uniformly mixing according to the mass ratio of 1:1:0.2 to obtain a first mixture, putting the mixed first mixture into a mold, carrying out warm-pressing molding to obtain a square sheet-shaped support body with the side length of 7cm and the thickness of 300 mu m, and then presintering for 2 hours at 1200 ℃ to obtain a hydrogen electrode support body; wherein, the hydrogen electrode support also serves as the support of the whole solid oxide electrolytic cell;
2) preparing a hydrogen electrode functional layer: uniformly mixing NiO and YSZ powder in a mass ratio of 1:1, adding a PS spherical pore-forming agent, wherein the mass of the pore-forming agent is 10% of the total mass of NiO and YSZ, ultrasonically dispersing the mixture uniformly in isopropanol, spraying the mixture on the surface of a support body, wherein the thickness of the mixture is 8 microns, fully drying the mixture in an air atmosphere at 150 ℃, and then presintering the mixture for 2 hours at 1100 ℃ to form a hydrogen electrode functional layer;
3) preparation of electrolyte layer: ball-milling YSZ powder and PVB for 2h according to the mass ratio of 1:0.3, uniformly mixing, dispersing by using a proper amount of isopropanol, blade-coating on the surface of a hydrogen electrode functional layer with the thickness of 10 mu m, and fully drying in the air;
4) sintering of electrolyte and hydrogen electrode portions: sintering the hydrogen electrode support body-hydrogen electrode functional layer-electrolyte layer prepared in the step at 1500 ℃ for 4 h;
5) preparation of the SOEC oxygen electrode: ball-milling LSCF powder and organic binder at a mass ratio of 2:1, uniformly mixing, wherein the organic binder is terpineol solution of ethyl cellulose (the mass percentage of the ethyl cellulose is 8%), coating the mixture on the surface of an electrolyte layer by a screen printing method, the thickness of the electrolyte layer is 20 mu m, and the effective area of the electrolyte layer is 36cm2And sintering at 1100 ℃ for 3h after full drying to obtain the cell sheet of the sample 2, wherein the porosity is 40% after the hydrogen electrode functional layer is sintered at high temperature and reduced.
Example 2
In this example, the samples 1, 2 and 3 prepared in example 1 and comparative examples 1 to 2 were subjected to scanning electron microscope detection and performance detection. Table 1 shows the hydrogen electrode functional layer structural characteristics of sample 1, sample 2, and sample 3.
TABLE 1
1. Scanning electron microscope detection is carried out on the cross sections of the sample 1, the sample 2 and the sample 3, the results are shown in fig. 1-4, and fig. 1 is a cross section SEM picture of the sample 3 provided by the embodiment of the present application; wherein, the frame is a hydrogen electrode functional layer area; FIG. 2 is a sectional SEM photograph of sample 1 provided by an embodiment of the present application; wherein, the frame is a hydrogen electrode functional layer area; FIG. 3 is a sectional SEM photograph of sample 2 provided by an embodiment of the present application; wherein, the frame is a hydrogen electrode functional layer area; FIG. 4 shows NiO surface deposited TiO of the electrode functional layer of sample 3 provided in the examples of the present application2Morphology of the nanoparticles.
As shown in fig. 1 to 4, the hydrogen electrode functional layer was dense after the preparation of sample 1 of comparative example 1, pores were generated during the reduction in the electrolytic cell, and the hydrogen electrode support was prepared using a sheet-like pore-forming agent. The hydrogen electrode functional layer of sample 2 of comparative example 2 used a PS spherical pore former, and the unreduced sample had a porosity of 20%, and after reduction, 40% pores were generated, and comparative example 2 obtained a relatively uniform porosity distribution.
The content ratio of NiO in the hydrogen electrode functional layer was increased in sample 3 of example 1, the density of the sintered sample 3 was increased by the adjustment process to be the same as that of sample 1, and since NiO shrinks in volume after reducing into metallic Ni, as can be seen from fig. 1 to 3, the content ratio of NiO was increased, NiO increased the porosity after reduction of the electrolytic cell, and the pore size and distribution were more uniform, the porosity of the hydrogen electrode functional layer of sample 3 was higher than that of samples 1 and 2, and the pore size and distribution of the hydrogen electrode functional layer of sample 3 was more uniform than those of samples 1 and 2, and as can be seen from fig. 4, TiO was uniformly deposited on the NiO surface of the hydrogen electrode functional layer2And (3) nanoparticles.
2. EI was performed on sample 1, sample 2 and sample 3S testing, namely testing the internal resistance of a plurality of samples through EIS under the testing conditions of 750 ℃ and H2Humidification 66.6%, open circuit condition. As shown in FIG. 5, the impedance spectrum is mainly composed of two semicircles, the intersection point of the left side of the semicircle and the real axis corresponds to the ohmic resistance of the electrolytic cell, the diameter of the semicircle in the left high-frequency region corresponds to the activation polarization impedance of the electrolytic cell, and the diameter of the semicircle in the right low-frequency region corresponds to the gas diffusion impedance of the electrolytic cell. Compared with the sample 1, the ohmic resistance, the activation polarization resistance and the gas diffusion resistance of the sample 3 are all reduced, which shows that the electron and oxygen ion conduction rate, the charge transfer rate on the hydrogen electrode and the gas diffusion rate on the hydrogen electrode of the sample 3 are all faster than those of the sample 1, and the internal resistance of the electrolytic cell is effectively reduced. In addition, the low-frequency gas diffusion impedance of the sample 3 is smaller, which shows that the introduction of the polystyrene microspheres improves the gas diffusion performance of the hydrogen electrode functional layer to a certain extent, improves the linear density of a three-phase interface, and reduces the charge transfer impedance.
3. SOEC I-V curve tests were performed on both cells of sample 1 and sample 3 under conditions of 750 ℃, a fixed water vapor utilization Us of 60%, and a fixed air flow rate of 250smL/min per layer. As shown in fig. 6, the voltage of sample 3 increased slowly with the increase of the electrolysis current density, indicating that the SOEC internal resistance of sample 3 was small, the overpotential generated on the hydrogen electrode was small, the electrolysis voltage was low, and the electrolysis efficiency was higher.
4. FIB-SEM characterization tests are carried out on the hydrogen electrodes of the sample 1 and the sample 3, and FIG. 7 shows a back scattering photograph of the cross section of the hydrogen electrode, wherein the bright color is Ni and the dark color is YSZ due to different back scattering electron generation amounts of Ni and YSZ, so that the porosity of the sample 3 is higher than that of the sample 1 and the distribution of pores is more uniform.
5. The three-dimensional reconstruction test and the volume fraction calculation are carried out on the two samples, and as can be seen from the table 2, the volume fractions of the Ni crystal grains, the YSZ crystal grains and the air holes of the sample 3 are relatively balanced, the linear density of the TPB three-phase interface generated by the structure is higher, and the catalytic reaction of hydrogen evolution of the hydrogen electrode mainly occurs at the three-phase interface, so that the structure of the sample 3 is more favorable for reducing the internal resistance of the electrolytic cell and improving the hydrogen evolution activity of the hydrogen electrode.
Table 2 sample 1 and sample 3 results of three-dimensional reconstruction of hydrogen electrode functional layer
| Sample (I) | Ni crystal grain | YSZ crystal grain | Air hole | TPB three- |
| Sample | ||||
| 1 | 38.61％ | 43.74％ | 17.65％ | 5.03μm/μm3 |
| Sample 3 | 36.90％ | 36.90％ | 26.20％ | 5.94μm/μm3 |
6. Carrying out initial constant current electrolysis operation aging test on the sample 1 and the sample 3 electrolytic cells under the following operation conditions: the electrolysis temperature is 750 ℃, and the current density is-0.56A/cm2The steam utilization Us is 60%. FIG. 8 shows the voltage change of sample 1 and sample 3 after 1000h operation, and the electrolytic voltage of sample 3 is significantly reduced and the rate of voltage increase with the operation time is significantly reduced compared to sample 1Low, indicating that the hydrogen evolution activity and stability of the hydrogen electrode of sample 3 are both significantly improved.
In conclusion, the application finds that more and more uniform air holes can be generated after the functional layer is reduced by improving the NiO content of the hydrogen electrode functional layer, so that the deposition of nano metal oxide particles is facilitated; meanwhile, the application discovers that the linear density of a three-phase interface is improved by depositing metal oxide nano particles in a functional layer structure of the hydrogen electrode, and the generated new interface can reduce charge transfer impedance and reduce the overpotential of the hydrogen electrode, so that the electrolytic voltage is reduced, the electrolytic efficiency is improved, and the stability of the hydrogen electrode is also improved due to the generation of the new interface.
The foregoing is only a preferred embodiment of the present application and it should be noted that those skilled in the art can make several improvements and modifications without departing from the principle of the present application, and these improvements and modifications should also be considered as the protection scope of the present application.
Claims (10)
1. The preparation method of the hydrogen electrode of the solid oxide electrolytic cell is characterized by comprising the following steps:
step 1, mixing NiO, yttria-stabilized zirconia, a second pore-forming agent and a solvent to obtain a second mixture, arranging the second mixture on the surface of a hydrogen electrode support, drying and presintering to obtain a pre-hydrogen electrode; wherein the mass ratio of the NiO to the yttria-stabilized zirconia is (0.6-2.3) to 1;
and 2, arranging the nano particles on the pre-hydrogen electrode, and sintering to obtain the hydrogen electrode of the solid oxide electrolytic cell.
2. The preparation method of claim 1, wherein the second pore-forming agent is selected from one or more of polystyrene microspheres, polymethyl methacrylate and starch; the addition amount of the second pore-forming agent is 0-20% of the mass sum of the NiO and the yttria-stabilized zirconia.
3. According to claimThe method of claim 1, wherein in step 2, the nanoparticles are selected from the group consisting of GDC, SDC, TiO2、Bi2O3、Fe2O3、SrTiO3And LaTiO3One or more of; the particle size of the nano particles is 1-100 nm; the nanoparticles are disposed on the pre-hydrogen electrode by impregnation, coating, physical blending, or vapor deposition; the loading amount of the nanoparticles is 1-10 wt.%.
4. The method of claim 1, wherein the hydrogen electrode support is selected from one of a NiO yttria-stabilized zirconia support or a NiO yttria support.
5. The method of claim 4, wherein the NiO-yttria-stabilized zirconia support is prepared by a method comprising:
mixing NiO, yttria-stabilized zirconia and a first pore-forming agent to prepare a first mixture;
and placing the first mixture into a mold for molding, and then sintering to obtain the NiO-yttria stabilized zirconia support.
6. The preparation method of claim 5, wherein the first pore-forming agent is selected from one or more of graphite, starch and polystyrene, and the amount of the first pore-forming agent is 10-30% of the total mass of NiO and yttria-stabilized zirconia.
7. A hydrogen electrode for a solid oxide electrolytic cell, characterized by comprising the hydrogen electrode for a solid oxide electrolytic cell produced by the production method according to any one of claims 1 to 6.
8. A solid oxide electrolytic cell characterized by comprising a hydrogen electrode of the solid oxide electrolytic cell produced by the production method according to any one of claims 1 to 6 or a hydrogen electrode, an electrolyte and an oxygen electrode of the solid oxide electrolytic cell according to claim 7;
the hydrogen electrode of the solid oxide electrolytic cell, the electrolyte and the oxygen electrode of the solid oxide electrolytic cell are arranged in sequence.
9. The preparation method of the solid oxide electrolytic cell is characterized by comprising the following steps:
mixing NiO, yttria-stabilized zirconia and a pore-forming agent to obtain a first mixture, arranging the first mixture on the surface of a hydrogen electrode support, drying and presintering to obtain a pre-hydrogen electrode; wherein the mass ratio of the NiO to the yttria-stabilized zirconia is (0.6-2.3) to 1;
secondly, arranging the nano particles on the pre-hydrogen electrode to prepare a hydrogen electrode of the solid oxide electrolytic cell;
mixing an electrolyte material of the solid oxide electrolytic cell with a binder to obtain a second mixture, placing the second mixture on a hydrogen electrode of the solid oxide electrolytic cell, and then sequentially drying and sintering to obtain a sintered product;
and step four, mixing the oxygen electrode material of the solid oxide electrolytic cell with a binder to prepare a third mixture, placing the third mixture on the side of the second mixture of the sintered product, and then, sequentially drying and sintering to prepare the solid oxide electrolytic cell.
10. The preparation method according to claim 9, characterized in that in step three, the electrolyte material of the solid oxide electrolytic cell is selected from one or more of yttria-stabilized zirconia, scandia-stabilized zirconia, and gadolinia-doped ceria; in the fourth step, the oxygen electrode material of the solid oxide electrolytic cell is selected from one of LSC, LSCF, LSM, LSF or BSCF; in the third step and the fourth step, the binder is selected from one or more of polyvinyl butyral ester, polyethylene glycol, dioctyl phthalate, polyvinyl alcohol and terpineol solution of ethyl cellulose.
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