CN114420986A - Solid oxide monomer electrolytic cell, preparation method thereof and electric pile - Google Patents

Solid oxide monomer electrolytic cell, preparation method thereof and electric pile Download PDF

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CN114420986A
CN114420986A CN202210044571.XA CN202210044571A CN114420986A CN 114420986 A CN114420986 A CN 114420986A CN 202210044571 A CN202210044571 A CN 202210044571A CN 114420986 A CN114420986 A CN 114420986A
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anode
ysz
solid oxide
slurry
oxide monomer
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于波
曹军文
张文强
覃祥富
耿嘎
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Tsinghua University
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Tsinghua University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0247—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2457—Grouping of fuel cells, e.g. stacking of fuel cells with both reactants being gaseous or vaporised
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/249—Grouping of fuel cells, e.g. stacking of fuel cells comprising two or more groupings of fuel cells, e.g. modular assemblies
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/002—Inorganic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H01M2300/0074—Ion conductive at high temperature
    • H01M2300/0077—Ion conductive at high temperature based on zirconium oxide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0094—Composites in the form of layered products, e.g. coatings
    • H01M2300/0097—Composites in the form of layered products, e.g. coatings with adhesive layers

Abstract

The application provides a solid oxide monomer electrolytic cell, a preparation method thereof and a galvanic pile, wherein the solid oxide monomer electrolytic cell comprises the following components in sequential connection: the porous anode comprises a cathode, an electrolyte layer and an anode, wherein a plurality of micron-sized pore channels which are vertically arranged relative to the electrolyte layer are arranged in the anode, the porosity is 40-75%, a catalytic layer covers the surface of the inner wall of each micron-sized pore channel, the catalytic layer comprises a perovskite material, and the thickness of the catalytic layer is 20-300 nm. The micron-sized pore channels in the anode are regularly distributed, the porosity is high, the tortuosity is low, and the oxygen discharge rate is effectively improved. The electrolyte layer, the anode and the main body material of the bonding slurry of the solid oxide monomer electrolytic cell are all YSZ, and the electrolyte-anode interface is tightly combined together in the form of chemical bonds in the crystallization process, so that an anode-electrolyte integrated fusion interface is constructed, the interface firmness is effectively improved, the tolerance of interface high current density is enhanced, and the energy loss is reduced.

Description

Solid oxide monomer electrolytic cell, preparation method thereof and electric pile
Technical Field
The application belongs to the technical field of solid oxide electrolytic cells, and particularly relates to a solid oxide monomer electrolytic cell, a preparation method thereof and a galvanic pile.
Background
Under the development backgrounds of 'carbon peak reaching' and 'carbon neutralization', the development of clean energy has become an important development direction of a future energy system. Solid Oxide Electrolytic Cell (SOEC) for hydrogen and CO production by water electrolysis2Co-electrolysis of synthetic fuel and N2The high-efficiency conversion of electric energy to chemical energy is realized in the forms of preparing synthetic ammonia by electrolysis and the like, and the electric energy and the chemical energy deeply participate in the carbon neutralization process. In order to improve the efficiency and yield of the SOEC, the SOEC is generally required to be made to have high temperature (600-1000 ℃) and large current density (more than or equal to 1A/cm)2) The operation is carried out. However, the conventional SOEC-configured anode is a stacked porous structure prepared by methods such as screen printing, dry pressing, tape casting, spray pyrolysis and the like, and has structural defects such as large tortuosity, more closed pores, low porosity and the like of a pore structure. When the SOEC operates at high current density, oxygen generated by the anode is difficult to rapidly discharge to the outside, and local oxygen high-voltage sites are easily formed in the oxygen electrode, so that the anode-electrolyte interface is damaged, even the delamination phenomenon is caused, and the performance of the electrolytic cell is rapidly attenuated. In addition, the effective specific surface area of the stacking structure anode is small, the number of active sites for electrochemical reaction is small, the electrochemical reaction resistance of the anode is large, and the electrolytic potential of the electrolytic cell under the operation of high current density is increased (>1.3V), the energy loss is severe.
Disclosure of Invention
The application provides a solid oxide monomer electrolytic cell, a preparation method thereof and a galvanic pile, aiming at solving the problems of low oxygen discharge rate of the solid oxide electrolytic cell and serious energy loss under the operation of high current density.
In one aspect, an embodiment of the present invention provides a solid oxide monomer electrolytic cell, including sequentially connected:
a cathode, wherein the thickness of the cathode is 300-500 μm;
an electrolyte layer having a thickness of 20 to 70 μm;
the anode is 100-500 mu m thick, a plurality of micron-sized pore channels vertically arranged relative to the electrolyte layer are arranged inside the anode, the porosity is 40-75%, a catalyst layer covers the surface of the inner wall of the micron-sized pore channels, the catalyst layer comprises a perovskite material and is 20-300 nm thick,
the electrolyte layer and the anode are bonded by bonding slurry, and the electrolyte layer, the bonding slurry and the anode are all prepared by taking YSZ as one of raw materials.
Optionally, the perovskite material comprises LaxSr1-xCoO3Or NdxSr1-xCoO3Wherein x is more than or equal to 0.2 and less than or equal to 0.8.
In one aspect, an embodiment of the present invention provides a preparation method of the solid oxide monomer electrolytic cell, including the following steps:
preparing a YSZ-containing cathode powder material, and tabletting and presintering the cathode powder material to obtain a cathode;
preparing an electrolyte slurry containing YSZ, and printing the electrolyte slurry on one side of the cathode to obtain a cathode support containing an electrolyte layer:
preparing YSZ-containing anode slurry, injecting the anode slurry into a mold in a frozen state to enable the anode slurry to grow upwards in an ice crystal form, and after the anode slurry grows up, performing freeze forming, demolding, vacuum freeze drying and presintering to obtain an anode;
preparing bonding slurry containing YSZ, bonding the anode and the cathode support body containing the electrolyte layer into a whole by using the bonding slurry, and sintering to obtain a solid oxide monomer electrolytic cell skeleton, wherein the bonding surface is the surface of the anode and the electrolyte layer; the sintering temperature is 1350-1450 ℃;
and (3) dripping the leaching solution containing the metal nitrate into the pore channel of the anode of the solid oxide monomer electrolytic cell framework, and calcining to obtain the solid oxide monomer electrolytic cell.
Optionally, the step of preparing the YSZ-containing cathode powder material includes: and ball-milling and drying the NiO, the YSZ and the starch to obtain the cathode powder material.
Optionally, the step of preparing the YSZ-containing electrolyte paste comprises: mixing and grinding YSZ and a binder according to the mass ratio of 2: 1-4: 3 to obtain the electrolyte slurry, wherein the binder comprises terpineol and cellulose.
Optionally, the step of preparing the YSZ-containing anode slurry comprises: and dispersing the Dow dispersant and YSZ in water, adding the Dow binder and the magnesium aluminum silicate thickener, and performing ball milling to obtain the anode slurry.
Optionally, the freezing temperature of the mold in the frozen state is-20 to-150 ℃.
Optionally, the step of preparing a YSZ-containing bonding paste comprises: mixing and grinding YSZ and a binder according to the mass ratio of 2: 1-4: 3 to obtain the bonding slurry, wherein the binder comprises terpineol and cellulose.
Optionally, the metal nitrate comprises La3+、Sr2+And Co2+Or comprises Nd3+、Sr2+And Co2+。
In another aspect, embodiments of the present invention provide a stack, which includes a plurality of solid oxide monomer electrolytic cells as described above, or includes a plurality of solid oxide monomer electrolytic cells prepared by the above method, and the plurality of solid oxide monomer electrolytic cells are connected by a connecting material.
The cathode of the solid oxide monomer electrolytic cell provided by the invention is of a porous structure, the electrolyte layer is of a compact structure, the anode is of a honeycomb structure with micron-sized regular pore channels, the porosity of the anode is high (40-75%), the tortuosity of the pore channels is low (close to 1), and the oxygen discharge rate is effectively improved when the large current density runs.
The solid oxide monomer electrolytic cell provided by the invention takes YSZ as the main materials of the anode, the electrolyte layer and the bonding slurry, and the electrolyte-anode interfaces are tightly combined together in the form of chemical bonds through the crystallization process (high-temperature solid-phase chemical reaction), so that an anode-electrolyte integrated fusion interface is constructed, the interface firmness is effectively improved, the number of active sites of electrochemical reaction is increased, the resistance of the anode electrochemical reaction is reduced, the high-current density (high oxygen pressure) tolerance of the interface is enhanced, and the energy loss is reduced.
The solid oxide monomer electrolytic cell provided by the invention can realize the electrolytic current density of 5.8A/cm at 800 ℃ and the electrolytic potential of 1.3V2The electrolysis operation with super-large current density realizes the hydrogen production with high efficiency and high yield, and has better industrial application prospect.
Drawings
FIG. 1 is a schematic structural diagram of an SOEC in an embodiment of the present application;
FIG. 2 is a scanning electron micrograph of the SOEC of example 1;
FIG. 3 is a magnified SEM image of a portion of the anode-electrolyte interface of the SOEC of example 1;
FIG. 4 is a partially enlarged scanning electron micrograph of the anode skeleton of the SOEC of example 1;
FIG. 5 is a magnified scanning electron micrograph of a portion of the anodic nanocatalyst layer of the SOEC of example 1;
FIG. 6 is a 1.3V constant voltage electrolysis performance curve for the SOEC of example 1;
FIG. 7 is a scanning electron micrograph of the SOEC of example 2;
FIG. 8 is a scanning electron micrograph of the SOEC of example 3.
In the drawings:
1-interface of electrolyte layer and anode; 2-an anode framework; 3-catalyst layer on the inner wall of anode pore channel.
Detailed Description
In order to make the objects, technical solutions and advantageous technical effects of the present invention more clear, the present invention is further described in detail with reference to the following embodiments. It should be understood that the embodiments described in this specification are only for the purpose of explaining the present invention and are not intended to limit the present invention.
For the sake of brevity, only some numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form ranges not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and similarly any upper limit may be combined with any other upper limit to form a range not explicitly recited. Also, although not explicitly recited, each point or individual value between endpoints of a range is encompassed within the range. Thus, each point or individual value can form a range not explicitly recited as its own lower or upper limit in combination with any other point or individual value or in combination with other lower or upper limits.
In the description herein, it is to be noted that, unless otherwise specified, "above" and "below" are inclusive, and "a plurality" of "one or more" means two or more.
Hydrogen is renewable, pollution-free, storable and transportable, and has attracted wide attention in the world. Hydrogen is used as an energy carrier and proposes the concept of hydrogen energy economy. The main ways of electrolytic hydrogen production that have been developed so far are alkaline cell electrolysis, proton exchange membrane cell electrolysis and ceramic oxide cell electrolysis, i.e. Solid Oxide Electrolysis Cells (SOEC).
SOEC is, in principle, the reverse process of the Solid Oxide Fuel Cell (SOFC) currently under study, and is an energy conversion device that converts thermal energy and electric energy into chemical energy.
Solid oxide monomer electrolytic cell
The embodiment of the first aspect of the invention provides a solid oxide monomer electrolytic cell, which comprises a cathode, wherein the thickness of the cathode is 300-500 μm; an electrolyte layer having a thickness of 20 to 70 μm; the anode is 100-500 mu m thick, a plurality of micron-sized pore channels which are vertically arranged relative to the electrolyte layer are formed in the anode, the porosity is 40-75%, a catalyst layer covers the surface of the inner wall of each micron-sized pore channel, the catalyst layer comprises a perovskite material and is 20-300 nm thick, the electrolyte layer and the anode are bonded through bonding slurry, and the electrolyte layer, the bonding slurry and the anode are prepared by taking YSZ as one of raw materials.
The cathode, also known as the fuel electrode, serves primarily to provide sites for water vapor decomposition reactions and for the passage of electrons. The cathode provided by the application has good electronic conductivity and electrocatalytic activity besides being matched with the performance of adjacent components, keeps the structure and composition stable under high-temperature and high-humidity conditions, and has sufficient pores to ensure that water vapor and hydrogen smoothly enter and exit.
The cathode provided by the application has a thickness of 300-500 μm, and can comprise metals such as Ni, Pt, Co or Ti besides YSZ (yttria-stabilized zirconia) as a supporting framework. Wherein, the price of Ni is relatively low, the structure of Ni-YSZ metal ceramic is more stable, and the cathode is preferably Ni-YSZ metal ceramic, which can effectively improve the stability of SOEC.
The electrolyte layer is the core part of the SOEC, the thickness of the electrolyte layer provided by the application is 20-70 μm, the electrolyte layer has sufficiently high ionic conductivity and low electronic conductivity, the structure is completely compact, and the chemical property, the crystal structure and the external dimension are kept stable in an oxidation and reduction atmosphere.
The anode is also called an air electrode, and the anode mainly plays a role in providing a field for oxygen ion oxidation reaction and an electron conduction channel. The application provides an anode thickness is 100 ~ 500 mu m, except with adjacent part phase-match, still satisfies: the material has high electronic conductivity and oxygen ion surface exchange coefficient; the structure and the composition are kept stable under the conditions of high temperature and oxidation; the honeycomb structure with regular pore channels has high porosity (40-75%), and the tortuosity of the pore channels is close to 1, so that the circulation of oxygen is facilitated, and the oxygen discharge rate is effectively improved.
According to the embodiment of the application, the anode internal pore channels are a plurality of micron-sized pore channels, the surface of the inner wall of each pore channel is covered with the catalytic layer, the catalytic layer comprises perovskite material, and the perovskite material comprises LaxSr1-xCoO3Or NdxSr1-xCoO3Wherein x is more than or equal to 0.2 and less than or equal to 0.8, and the catalytic layer greatly improves the active area of electrochemical reaction.
As shown in figure 1, the SOEC with the micro-nano honeycomb pore channel anode configuration provided by the invention comprises a porous cathode supporting layer and a compact electrolyte layerAnd a honeycomb anode having micron-sized regular cells. The thickness of the cathode is 300 to 500 μm. The thickness of the electrolyte layer is 20-70 μm. The thickness of the anode framework is 100-500 μm. The porosity of the anode skeleton is 40-75%, the tortuosity is close to 1, and the oxygen discharge rate is effectively improved. The anode and the electrolyte layer of the SOEC with the micro-nano honeycomb pore channel anode configuration provided by the invention are bonded together by the bonding slurry. The electrolyte, the anode framework and the bonding slurry main body are YSZ, and an anode-electrolyte integrated fusion interface is constructed through combined action of slurry bonding and high-temperature sintering. The new structure SOEC can realize the electrolytic current density of 5.8A/cm at 800 ℃ and 1.3V of electrolytic potential2The electrolysis operation with super-large current density realizes the hydrogen production with high efficiency and high yield, and has better industrial application prospect.
Preparation method of solid oxide monomer electrolytic cell
An embodiment of the second aspect of the invention provides a method for preparing a solid oxide monomer electrolytic cell, comprising the following steps:
preparing a YSZ-containing cathode powder material, and tabletting and presintering the cathode powder material to obtain a cathode;
preparing an electrolyte slurry containing YSZ, and printing the electrolyte slurry on one side of the cathode to obtain a cathode support containing an electrolyte layer:
preparing YSZ-containing anode slurry, injecting the anode slurry into a mold in a frozen state to enable the anode slurry to grow upwards in an ice crystal form, and after the anode slurry grows up, performing freeze forming, demolding, vacuum freeze drying and presintering to obtain an anode;
preparing bonding slurry containing YSZ, bonding the anode and the cathode support body containing the electrolyte layer into a whole by using the bonding slurry, and sintering to obtain a solid oxide monomer electrolytic cell skeleton, wherein the bonding surface is the surface of the anode and the electrolyte layer; the sintering temperature is 1350-1450 ℃;
and (3) dripping the leaching solution containing the metal nitrate into the pore channel of the anode of the solid oxide monomer electrolytic cell framework, and calcining to obtain the solid oxide monomer electrolytic cell.
The method of making a solid oxide monomer electrolytic cell provided herein may include the above steps, but is not necessarily made in the order of the above steps.
In the embodiment of the application, the cathode is prepared by a dry pressing method, specifically, a porous cathode is obtained after a cathode powder material is subjected to tabletting and pre-sintering. Enough pores in the porous cathode can ensure that water vapor and hydrogen gas smoothly enter and exit. The presintering temperature is selected to be 800-1300 ℃, and the structure and the composition of the cathode after high-temperature presintering are stable.
The preparation method of the YSZ-containing cathode powder material comprises the following steps: and ball-milling and drying the NiO, the YSZ and the starch to obtain the cathode powder material, wherein the mass ratio of the NiO to the YSZ to the starch is 2:2: 1.
According to the embodiment of the application, the price of Ni is relatively low, and the structure of Ni-YSZ metal ceramic is more stable, so that the stability of the SOEC can be effectively improved.
In an embodiment of the present application, the step of preparing an electrolyte paste of YSZ comprises: mixing and grinding YSZ and a binder according to the mass ratio of 2: 1-4: 3 to obtain the electrolyte slurry, wherein the binder comprises terpineol and cellulose.
In some embodiments, the step of preparing the YSZ-containing electrolyte paste may include: weighing a proper amount of YSZ in an agate mortar, and adding a proper amount of binder. The binder is prepared from terpineol and cellulose according to a certain proportion. Grinding the two into uniform viscous electrolyte slurry in an agate mortar, wherein the mass ratio of terpineol to cellulose used in the binder is 95: 5. The mass ratio of the binder to the YSZ is 2: 3.
In an embodiment of the present application, the preparing step of the cathode support including the electrolyte layer may include: and printing an electrolyte layer on one side of the cathode by adopting a screen printing method, and pre-sintering at 800-1300 ℃ to obtain the cathode support body containing the electrolyte layer.
According to the embodiment of the application, the electrolyte layer is printed on one side of the cathode and then is pre-sintered at high temperature, so that the electrolyte layer which is completely compact in structure, stable in chemical property, crystal structure and overall dimension is obtained, and the electrolyte layer and the cathode are tightly combined.
In an embodiment of the present application, the step of preparing the YSZ-containing anode slurry comprises: and dispersing the Dow dispersant and YSZ in water, adding the Dow binder and the magnesium aluminum silicate thickener, and performing ball milling to obtain the anode slurry.
In some embodiments, the volume fraction of the Dow dispersant relative to water is 1 to 5 vol%; the volume fraction of YSZ relative to water is 8-40 vol%; the volume fraction of the Dow binder relative to water is 1-10 vol%; the mass fraction of the magnesium aluminum silicate relative to the water is 1-5 wt%.
In some embodiments, the preparation process of the anode may include: placing a metal copper plate in a low-temperature constant-temperature stirring reaction bath, setting the temperature to be-20 to-150 ℃, placing a cylindrical polypropylene plastic mold on the surface of the metal copper plate, injecting anode slurry into the mold, enabling ice crystals to grow upwards, extruding YSZ solid particles to the periphery to form a vertically upward micron-sized regularly-arranged framework, and freezing and molding for 5-30 min. And (3) demolding the molded sample, transferring the molded sample to a vacuum freeze drying box for freeze drying for 24 hours, biochemically discharging ice crystals under low-temperature vacuum, and leaving micron-sized array pore channels, thereby obtaining the honeycomb pore channel skeleton anode element blank. And (3) pre-burning the blank in a muffle furnace at 800-1000 ℃ to obtain a certain strength, thus obtaining the anode.
According to the embodiment of the application, the anode prepared by the freeze drying method has micron-sized array pore channels, the porosity is high (40-75%), and the tortuosity of the pore channels is close to 1. The anode after presintering has certain strength and stability.
In embodiments of the present application, a method of preparing a YSZ-containing bonding paste may comprise: mixing and grinding YSZ and a binder according to the mass ratio of 2: 1-4: 3 to obtain the bonding slurry, wherein the binder comprises terpineol and cellulose, and the mass ratio of the terpineol to the cellulose is 95: 5.
In some embodiments, a method of making a solid oxide monomer cell skeleton can comprise: applying a certain amount of bonding slurry on the surface of the electrolyte layer or the bottom surface of the anode, bonding the anode and the electrolyte layer into a whole, and drying. And (3) placing the bonded SOEC precursor skeleton in a muffle furnace, and sintering at high temperature for 2-4 h to obtain the solid oxide monomer electrolytic cell skeleton.
In the examples of the present application, the anode and the cathode support including the electrolyte layer are bonded together by using a bonding paste in a manner including double-sided dispensing bonding, single-sided dispensing bonding, or screen printing bonding.
In some embodiments, the method of preparing the anode catalytic layer may comprise: preparing a leaching solution with the concentration of 0.5-1 mol/L by adopting metal nitrate according to the stoichiometric ratio (the metal nitrate comprises La)3+、Sr2+And Co2+Or comprises Nd3+、Sr2+And Co2+) The leaching solution is dripped into the micron-sized pore channel framework, and the leaching solution is uniformly deposited on the inner wall of the pore channel of the framework through capillary action. Transferring the impregnated SOEC into a muffle furnace, calcining at 600-1200 ℃ for 0.5-4 h to generate a nano-grade perovskite active catalyst layer, and obtaining a solid oxide monomer electrolytic cell, wherein the catalyst layer comprises LaxSr1-xCoO3Or NdxSr1-xCoO3Perovskite, wherein x is more than or equal to 0.2 and less than or equal to 0.8.
The solid oxide monomer electrolytic cell provided by the invention takes YSZ as the main materials of the anode, the electrolyte and the bonding slurry, and the electrolyte-anode interface is tightly combined together in the form of chemical bonds through the crystallization process (high-temperature solid phase chemical reaction, the reaction temperature is 1350-1450 ℃), so that an anode-electrolyte integrated fusion interface is constructed, the interface firmness is effectively improved, the large-current density (high oxygen pressure) tolerance of the interface is enhanced, and the energy loss is reduced.
And (3) testing electrical properties: silver paste is respectively bonded on the two sides of the cathode and the anode of the prepared solid oxide electrolytic cell to prepare a test sample. The cathode atmosphere was 40 vol% water vapor, 30 vol% hydrogen, and 30 vol% nitrogen, measured at 800 ℃. The anode atmosphere was air.
Electric pile
Embodiments of the third aspect of the invention provide a stack comprising a plurality of solid oxide monomer electrolytic cells as described above, or a plurality of solid oxide monomer electrolytic cells prepared by the above method, the plurality of solid oxide monomer electrolytic cells being connected by a connecting material.
The connecting material is mainly used in two ways: the first is to divide the gas of the fuel electrode chamber and the air electrode chamber; the second is to transmit current between the electrolytic cell units.
The connection material selected by the galvanic pile provided by the application is not limited and can be LaCrO3A base ceramic material or a superalloy material.
Examples
Example 1
1) Preparing a cathode support: adding 50 wt% of ethanol into a ball milling tank, adding 15 wt% of NiO, 15 wt% of YSZ and 10 wt% of starch into the ethanol, ball milling and drying. Adding a proper amount of powder into a tabletting mold, preparing a disk-shaped cathode support body with the diameter of 20mm by using a tabletting machine, and pre-sintering.
2) Preparing an electrolyte: weighing a proper amount of YSZ in an agate mortar, and adding a proper amount of binder, wherein the mass ratio of the YSZ to the binder is 3: 2. The binder contains terpineol 95 wt% and cellulose 5 wt%. The two are ground in an agate mortar to prepare uniform viscous electrolyte slurry. An electrolyte layer was printed on one side of the hydrogen electrode support by screen printing and calcined.
3) Additional preparation of the honeycomb anode: adding 1-5 vol% of a Dow's dispersant and 8-40 vol% of YSZ into water, performing ultrasonic dispersion uniformly, then adding a Dow's binder accounting for 1-10 vol% of the water volume and 1-5% of a magnesium aluminum silicate thickener, and performing ball milling to obtain the anode framework slurry. Placing a metal copper plate in a low-temperature constant-temperature stirring reaction bath, setting the temperature to be-70 ℃, placing a cylindrical polypropylene plastic mold on the surface of the metal copper plate, injecting YSZ slurry into the mold, enabling ice crystals to grow upwards, extruding YSZ solid particles to the periphery to form a vertically upward micron-sized regularly-arranged framework, and performing freeze forming for 5-10 min. And (3) demolding the molded sample, transferring the molded sample to a vacuum freeze drying box for drying, biochemically discharging ice crystals at low temperature under vacuum, and leaving micron-sized array pore channels, thereby obtaining the honeycomb pore channel skeleton anodic element blank. And (3) transferring the blank into a muffle furnace, and pre-burning to obtain a certain strength.
4) Preparing a SOEC framework with a micro-nano honeycomb pore channel anode configuration: weighing a proper amount of YSZ into an agate mortar, and adding a proper amount of bonding agent YSZ and the bonding agent in a mass ratio of 4: 3. The binder contains terpineol 95 wt% and cellulose 5 wt%. Grinding the two in an agate mortar to prepare uniform and sticky anode framework-electrolyte interface bonding slurry. And (3) dropwise adding a proper amount of bonding slurry (single-side dropping coating) on the bottom surface of the anode framework, and bonding the framework and the electrolyte into a whole by pressing. And (3) placing the bonded SOEC precursor skeleton in a muffle furnace, and sintering at high temperature to obtain a novel SOEC skeleton (shown in figure 2), wherein the thickness of the electrolyte obtained by one-side drop coating bonding is 45 mu m, the thickness of the fusion type anode-electrolyte interface is shown in figure 3, the anode skeleton is shown in figure 4, and the tortuosity is 1.003.
5) And (3) impregnation modification of an active catalyst: preparing La with the concentration of 1mol/L according to the stoichiometric ratio by adopting metal nitrate3+、Sr2+、Co2+And (3) soaking liquid, namely dripping the soaking liquid into the micron-sized pore channel framework, and uniformly depositing the soaking liquid on the inner wall of the pore channel of the framework through capillary action. Transferring the impregnated SOEC into a muffle furnace, and calcining for 2h to generate LaxSr1-xCoO3And (3) obtaining the SOEC with the micro-nano honeycomb pore channel anode configuration by using the perovskite active catalyst (shown in figure 5).
6) And (5) testing the electrolytic performance. Silver wires are respectively bonded on the two sides of the prepared cathode and anode of the SOEC by silver paste to prepare test samples. At 800 ℃, the cathode atmosphere is water vapor 40 vol%, hydrogen 30 vol%, and nitrogen 30 vol%. The anode atmosphere was air. Under the electrolytic potential of 1.3V, the SOEC electrolytic current density reaches 5.8A/cm2And the operation was stabilized for 200min (as shown in fig. 6).
Example 2
1) Preparing a cathode support: adding 50 wt% of ethanol into a ball milling tank, adding 15 wt% of NiO, 15 wt% of YSZ and 10 wt% of starch into the ethanol, ball milling and drying. Adding a proper amount of powder into a tabletting mold, preparing a disk-shaped cathode support body with the diameter of 20mm by using a tabletting machine, and pre-sintering.
2) Preparing an electrolyte: weighing a proper amount of YSZ in an agate mortar, and adding a proper amount of binder, wherein the mass ratio of the YSZ to the binder is 3: 2. The binder contains terpineol 95 wt% and cellulose 5 wt%. The two are ground in an agate mortar to prepare uniform viscous electrolyte slurry. An electrolyte layer was printed on one side of the hydrogen electrode support by screen printing and calcined.
3) Additional preparation of the honeycomb anode: adding 1-5 vol% of a Dow's dispersant and 8-40 vol% of YSZ into water, performing ultrasonic dispersion uniformly, then adding a Dow's binder accounting for 1-10 vol% of the water volume and 1-5% of a magnesium aluminum silicate thickener, and performing ball milling to obtain the anode framework slurry. Placing a metal copper plate in a low-temperature constant-temperature stirring reaction bath, setting the temperature to be-70 ℃, placing a cylindrical polypropylene plastic mold on the surface of the metal copper plate, injecting YSZ slurry into the mold, enabling ice crystals to grow upwards, extruding YSZ solid particles to the periphery to form a vertically upward micron-sized regularly-arranged framework, and performing freeze forming for 5-10 min. And demolding the molded sample, drying in a transference vacuum freeze drying oven, discharging the ice crystals under low-temperature vacuum in a biochemical manner, and leaving micron-sized array pore channels, thereby obtaining the honeycomb pore channel skeleton anode biscuit. And pre-burning the blank in a muffle furnace to obtain certain strength.
4) Preparing a SOEC framework with a micro-nano honeycomb pore channel anode configuration: weighing a proper amount of YSZ into an agate mortar, and adding a proper amount of bonding agent YSZ and the bonding agent in a mass ratio of 4: 3. The binder contains terpineol 95 wt% and cellulose 5 wt%. Grinding the two in an agate mortar to prepare uniform and sticky anode framework-electrolyte interface bonding slurry. And (3) respectively dripping a proper amount of bonding slurry (double-side dripping coating) on the bottom surface of the anode framework and the surface of the electrolyte, and bonding the framework and the electrolyte into a whole by pressing. And (3) placing the bonded SOEC precursor skeleton in a muffle furnace, sintering at high temperature to obtain a novel SOEC skeleton (shown in figure 7), and dripping and bonding the two sides to obtain an electrolyte with the thickness of 80 μm.
5) And (3) impregnation modification of an active catalyst: preparing La with the concentration of 1mol/L according to the stoichiometric ratio by adopting metal nitrate3+、Sr2+、Co2+Soaking liquid, dripping the soaking liquid into the micron-sized pore channelIn the framework, the infiltration liquid is uniformly deposited on the inner wall of the pore channel of the framework through capillary action. Transferring the impregnated SOEC into a muffle furnace, and calcining for 2h to generate LaxSr1-xCoO3And obtaining the SOEC with the anode configuration of the micro-nano honeycomb pore passage by using the perovskite active catalyst.
6) And (5) testing the electrolytic performance. Silver wires are respectively bonded on the two sides of the prepared cathode and anode of the SOEC by silver paste to prepare test samples. At 850 ℃, the cathode atmosphere is water vapor 40 vol%, hydrogen 30 vol%, and nitrogen 30 vol%. The anode atmosphere was air. Under the electrolytic potential of 1.5V, the SOEC electrolytic current density reaches 0.81A/cm2And stably running for 480 min.
Example 3
1) Preparing a cathode support: adding 50 wt% of ethanol into a ball milling tank, adding 15 wt% of NiO, 15 wt% of YSZ and 10 wt% of starch into the ethanol, ball milling and drying. The dried solid was ground to a uniform powder with no visible particles. Adding a proper amount of powder into a tabletting mold, preparing a disk-shaped cathode support body with the diameter of 20mm by using a tabletting machine, and pre-sintering.
2) Preparing an electrolyte: weighing a proper amount of YSZ in an agate mortar, and adding a proper amount of binder, wherein the mass ratio of the YSZ to the binder is 3: 2. The binder contains terpineol 95 wt% and cellulose 5 wt%. The two are ground in an agate mortar to prepare uniform viscous electrolyte slurry. An electrolyte layer was printed on one side of the hydrogen electrode support by screen printing and calcined.
3) Additional preparation of the honeycomb anode: adding 1-5 vol% of a Dow's dispersant and 8-40 vol% of YSZ into water, performing ultrasonic dispersion uniformly, then adding a Dow's binder accounting for 1-10 vol% of the water volume and 1-5% of a magnesium aluminum silicate thickener, and performing ball milling to obtain the anode framework slurry. Placing a metal copper plate in a low-temperature constant-temperature stirring reaction bath, setting the temperature to be-70 ℃, placing a cylindrical polypropylene plastic mold on the surface of the metal copper plate, injecting YSZ slurry into the mold, enabling ice crystals to grow upwards, extruding YSZ solid particles to the periphery to form a vertically upward micron-sized regularly-arranged framework, and performing freeze forming for 5-30 min. And demolding the molded sample, drying the sample in a transference vacuum freeze drying oven, discharging the ice crystals in a biochemical manner under low-temperature vacuum, and leaving micron-sized array pore channels, thereby obtaining the honeycomb pore channel skeleton anode biscuit. And pre-burning the blank in a muffle furnace to obtain certain strength.
4) Preparing a SOEC framework with a micro-nano honeycomb pore channel anode configuration: weighing a proper amount of YSZ into an agate mortar, and adding a proper amount of bonding agent YSZ and the bonding agent in a mass ratio of 4: 3. The binder contains terpineol 95 wt% and cellulose 5 wt%. Grinding the two in an agate mortar to prepare uniform and sticky anode framework-electrolyte interface bonding slurry. And (3) brushing a layer of bonding slurry (screen printing bonding) on the bottom surface of the anode framework and the surface of the electrolyte respectively by adopting a screen printing method, and bonding the framework and the electrolyte into a whole by pressing. And (3) placing the bonded SOEC precursor skeleton into a muffle furnace, sintering at high temperature to obtain a novel SOEC skeleton (shown in figure 8), and performing screen printing bonding to obtain an electrolyte with the thickness of 35 μm.
5) And (3) impregnation modification of an active catalyst: nd with the concentration of 1mol/L is prepared by metal nitrate according to the stoichiometric ratio3+、Sr2+、Co2+And (3) soaking liquid, namely dripping the soaking liquid into the micron-sized pore channel framework, and uniformly depositing the soaking liquid on the inner wall of the pore channel of the framework through capillary action. Transferring the impregnated SOEC into a muffle furnace, and calcining for 2h to generate NdxSr1-xCoO3And obtaining the SOEC with the anode configuration of the micro-nano honeycomb pore passage by using the perovskite active catalyst.
6) And (5) testing the electrolytic performance. Silver wires are respectively bonded on the two sides of the prepared cathode and anode of the SOEC by silver paste to prepare test samples. At 800 ℃, the cathode atmosphere is water vapor 40 vol%, hydrogen 30 vol%, and nitrogen 30 vol%. The anode atmosphere was air. The SOEC electrolytic current density is 0.6A/cm under the electrolytic potential of 1.3V2。
While the present application has been described with reference to preferred embodiments, various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the present application, and in particular, features shown in the various embodiments may be combined in any manner as long as there is no structural conflict. The present application is not intended to be limited to the particular embodiments disclosed herein but is to cover all embodiments that may fall within the scope of the appended claims.

Claims (10)

1. A solid oxide monomer electrolytic cell, comprising:
a cathode, wherein the thickness of the cathode is 300-500 μm;
an electrolyte layer having a thickness of 20 to 70 μm;
the anode is 100-500 mu m thick, a plurality of micron-sized pore channels which are vertically arranged relative to the electrolyte layer are formed inside the anode, the porosity is 40-75%, a catalyst layer covers the surface of the inner wall of each micron-sized pore channel, each catalyst layer comprises a perovskite material, and the thickness is 20-300 nm;
the electrolyte layer and the anode are bonded by bonding slurry, and the electrolyte layer, the bonding slurry and the anode are all prepared by taking YSZ as one of raw materials.
2. The solid oxide monomer electrolysis cell of claim 1, wherein the perovskite material comprises LaxSr1-xCoO3Or NdxSr1-xCoO3Wherein x is more than or equal to 0.2 and less than or equal to 0.8.
3. A method of making a solid oxide monomer electrolytic cell as claimed in claim 1 or claim 2, comprising the steps of:
preparing a YSZ-containing cathode powder material, and tabletting and presintering the cathode powder material to obtain a cathode;
preparing an electrolyte slurry containing YSZ, and printing the electrolyte slurry on one side of the cathode to obtain a cathode support containing an electrolyte layer:
preparing YSZ-containing anode slurry, injecting the anode slurry into a mold in a frozen state to enable the anode slurry to grow upwards in an ice crystal form, and after the anode slurry grows up, performing freeze forming, demolding, vacuum freeze drying and presintering to obtain an anode;
preparing bonding slurry containing YSZ, bonding the anode and the cathode support body containing the electrolyte layer into a whole by using the bonding slurry, and sintering to obtain a solid oxide monomer electrolytic cell skeleton, wherein the bonding surface is the surface of the anode and the electrolyte layer; the sintering temperature is 1350-1450 ℃;
and (3) dripping the leaching solution containing the metal nitrate into the pore channel of the anode of the solid oxide monomer electrolytic cell framework, and calcining to obtain the solid oxide monomer electrolytic cell.
4. The method of claim 3, wherein the step of preparing the YSZ-containing cathode powder material comprises: and ball-milling and drying the NiO, the YSZ and the starch to obtain the cathode powder material.
5. The method of making a solid oxide monomer electrolytic cell of claim 3, wherein the step of making the YSZ-containing electrolyte slurry comprises:
mixing and grinding YSZ and a binder according to the mass ratio of 2: 1-4: 3 to obtain the electrolyte slurry, wherein the binder comprises terpineol and cellulose.
6. The method of making a solid oxide cell as claimed in claim 3, wherein the step of preparing the YSZ-containing anode slurry comprises:
and dispersing the Dow dispersant and YSZ in water, adding the Dow binder and the magnesium aluminum silicate thickener, and performing ball milling to obtain the anode slurry.
7. The method of claim 3, wherein the mold in a frozen state has a freezing temperature of-20 to-150 ℃.
8. The method of making a solid oxide monomer electrolytic cell of claim 3, wherein the step of preparing a bonding paste comprising YSZ comprises:
mixing and grinding YSZ and a binder according to the mass ratio of 2: 1-4: 3 to obtain the bonding slurry, wherein the binder comprises terpineol and cellulose.
9. The method of claim 3, wherein the metal nitrate includes La3+、Sr2+And Co2+Or comprises Nd3+、Sr2+And Co2+。
10. A galvanic pile comprising a plurality of solid oxide monomer cells according to claim 1 or 2, or a plurality of solid oxide monomer cells prepared by the method of any one of claims 3 to 9, wherein the plurality of solid oxide monomer cells are connected by connectors.
CN202210044571.XA 2022-01-14 2022-01-14 Solid oxide monomer electrolytic cell, preparation method thereof and electric pile Pending CN114420986A (en)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001283876A (en) * 2000-04-03 2001-10-12 Tokyo Gas Co Ltd Unit cell of solid electrolytic fuel battery
US6492051B1 (en) * 2000-09-01 2002-12-10 Siemens Westinghouse Power Corporation High power density solid oxide fuel cells having improved electrode-electrolyte interface modifications
CN101339997A (en) * 2007-07-06 2009-01-07 中国科学院大连化学物理研究所 Membrane electrode component of medium temperature solid-oxide fuel cell and preparation thereof
CN104022303A (en) * 2014-05-08 2014-09-03 景德镇陶瓷学院 Preparation method of 8YSZ electrolyte film of anode supporting intermediate temperature single SOFC (Solid Oxide Fuel Cell)
KR20160084182A (en) * 2015-01-05 2016-07-13 주식회사 동진쎄미켐 Membrane-electrode assembly for fuel cell and fuel cell system comprising the same
CN108539233A (en) * 2018-05-11 2018-09-14 合肥国轩高科动力能源有限公司 A kind of preparation method of solid oxide fuel cell
CN109239149A (en) * 2018-09-12 2019-01-18 东北大学 A kind of electrochemical sensor and preparation method thereof monitoring nitrogen content
CN109852988A (en) * 2019-04-12 2019-06-07 清华大学 A kind of tree-shaped solid oxide electrolytic cell anode of micro-nano and preparation method thereof
CN113258111A (en) * 2021-06-30 2021-08-13 中国矿业大学(北京) Zirconium-based anode-supported solid oxide battery without isolation layer

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001283876A (en) * 2000-04-03 2001-10-12 Tokyo Gas Co Ltd Unit cell of solid electrolytic fuel battery
US6492051B1 (en) * 2000-09-01 2002-12-10 Siemens Westinghouse Power Corporation High power density solid oxide fuel cells having improved electrode-electrolyte interface modifications
CN101339997A (en) * 2007-07-06 2009-01-07 中国科学院大连化学物理研究所 Membrane electrode component of medium temperature solid-oxide fuel cell and preparation thereof
CN104022303A (en) * 2014-05-08 2014-09-03 景德镇陶瓷学院 Preparation method of 8YSZ electrolyte film of anode supporting intermediate temperature single SOFC (Solid Oxide Fuel Cell)
KR20160084182A (en) * 2015-01-05 2016-07-13 주식회사 동진쎄미켐 Membrane-electrode assembly for fuel cell and fuel cell system comprising the same
CN108539233A (en) * 2018-05-11 2018-09-14 合肥国轩高科动力能源有限公司 A kind of preparation method of solid oxide fuel cell
CN109239149A (en) * 2018-09-12 2019-01-18 东北大学 A kind of electrochemical sensor and preparation method thereof monitoring nitrogen content
CN109852988A (en) * 2019-04-12 2019-06-07 清华大学 A kind of tree-shaped solid oxide electrolytic cell anode of micro-nano and preparation method thereof
CN113258111A (en) * 2021-06-30 2021-08-13 中国矿业大学(北京) Zirconium-based anode-supported solid oxide battery without isolation layer

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