CN113745541B - Preparation method of sulfur poisoning resistant and renewable anode of solid oxide fuel cell - Google Patents

Preparation method of sulfur poisoning resistant and renewable anode of solid oxide fuel cell Download PDF

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CN113745541B
CN113745541B CN202111056265.XA CN202111056265A CN113745541B CN 113745541 B CN113745541 B CN 113745541B CN 202111056265 A CN202111056265 A CN 202111056265A CN 113745541 B CN113745541 B CN 113745541B
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anode
precursor solution
nitrate
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fuel cell
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CN113745541A (en
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李一倩
那立远
吕喆
殷克涛
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Heilongjiang University
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    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
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    • H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
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Abstract

A preparation method of a sulfur poisoning resistant and renewable anode of a solid oxide fuel cell aims to solve the technical problem that the metal anode of the existing solid oxide fuel cell or the oxide anode modified by a metal catalyst is not suitable for oxygen oxidation regeneration of an electrochemical pump. The preparation method comprises the following steps: respectively coating the anode slurry and the cathode slurry on two sides of an electrolyte, sintering at high temperature to obtain a battery initial blank, dripping a porous substrate anode by adopting a nitrate precursor solution A to obtain a composite anode with a metal oxide catalyst, dripping a composite anode by adopting a nitrate precursor solution B of the oxide catalyst, repeatedly dipping and thermally decomposing, and finally sintering at high temperature. The invention realizes the composite anode structure with oxide catalyst, metal catalyst and substrate anode coexisting by controlling the dipping sequence and dipping amount of the two catalysts, and the composite anode can realize regeneration through the electrochemical pumping oxygen oxidation process after sulfur poisoning.

Description

Preparation method of sulfur poisoning resistant and renewable anode of solid oxide fuel cell
Technical Field
The invention belongs to the field of anodes of solid oxide fuel cells and electrochemical oxidation regeneration, and particularly relates to a sulfur poisoning resistant and renewable anode and a preparation method thereof.
Background
A Solid Oxide Fuel Cell (SOFC) is an all-Solid-state power generation device that uses mainly fast ion conductors and Oxide materials as electrolytes and electrodes (cathode and anode). The method has the advantages of high energy conversion efficiency, flexible fuel utilization, environmental protection, no electrolyte leakage, no corrosion and the like. In addition, SOFC monocells or cell stacks have various structures, the working waste heat temperature is high, and the SOFC monocells or cell stacks have wide application prospects in the fields of high-power generation systems, distributed power systems, household combined heat and power systems, vehicle-mounted auxiliary power supplies, small portable power supplies and the like.
The use of cheap fuel is a cost problem for commercialization of SOFC, and all SOFC anode materials currently suffer from sulfur poisoning during the use of cheap fuel, only the difference in the sulfur poisoning degree between different anode materials. In order to realize repeated and sustainable use of SOFC anode materialIt is essential to find a regeneration method capable of maximally restoring the components, microstructure and electrochemical properties of the anode after sulfur poisoning of the anode. At present, three regeneration methods can realize the regeneration of the sulfur poisoning anode, namely a constant current discharge method, a chemical oxidation method and an electrochemical oxidation method. The three regeneration methods have advantages and disadvantages and application range, wherein the electrochemical oxidation regeneration method is a regeneration method integrating safety and high efficiency, the method utilizes an electrochemical workstation to control the current density of pump oxygen so as to pump oxygen ions from a cathode to an anode, the oxygen ions can enter an anode lattice to replace sulfur ions, in addition, the oxygen ions can be reduced into oxygen and oxidize sulfur poisoning products, and the purpose of sulfur removal can be realized in the processes. The electrochemical oxidation method has successfully realized sulfur poisoning La0.75Sr0.25Cr0.5Mn0.5O3The (LSCrM) anode is repeatedly regenerated, and the regeneration process can also generate activation effect on the LSCrM anode. The LSCrM anode is paid much attention because of higher oxidation reduction resistance stability, strong carbon deposition resistance and sulfur poisoning resistance, but the ion-electron conductivity and the fuel catalytic capability of the LSCrM are poorer, and the conductivity and the catalytic activity of the anode can be obviously improved by introducing a small amount of Ni metal catalyst (Ni-LSCrM) into the LSCrM anode, so that the electrochemical performance of the LSCrM anode and the output performance of a battery are improved. However, researches find that since metal Ni is a pure electronic conductive material and the limited oxygen ion conductivity of the LSCrM substrate anode, the electrochemical oxidation regeneration method is not suitable for the regeneration of the sulfur poisoning Ni-LSCrM composite anode, and the electrochemical oxidation process may cause the increase of the size of the Ni catalyst particles and the migration of the catalyst particles, thereby causing irreversible damage to the structure and electrochemical performance of the composite anode. At present, the electrochemical oxidation regeneration method has certain limitations on the regeneration of pure electronic conducting phase materials poisoned by sulfur and oxide composite anode materials modified by the pure electronic conducting phase materials.
Disclosure of Invention
The invention aims to solve the technical problem that the metal anode of the existing solid oxide fuel cell or the oxide anode modified by a metal catalyst is not suitable for the oxygen oxidation regeneration of an electrochemical pump, and provides a composite anode structure which is resistant to sulfur poisoning and suitable for the oxygen oxidation regeneration method of the electrochemical pump.
The preparation method of the sulfur poisoning resistance and renewable anode of the solid oxide fuel cell is realized according to the following steps:
firstly, mixing an anode material and a binder to prepare anode slurry, and mixing a cathode material and the binder to prepare cathode slurry;
secondly, respectively coating the anode slurry and the cathode slurry on two sides of the electrolyte, and sintering at high temperature to obtain a battery initial blank with a porous substrate anode and a porous cathode;
dripping a nitrate precursor solution A of a metal catalyst into the porous substrate anode, and performing repeated dipping-thermal decomposition treatment to obtain a composite anode with a metal oxide catalyst (the metal oxide catalyst is reduced into metal in the working environment of the battery);
dripping the composite anode by adopting a nitrate precursor solution B of an oxide catalyst, and performing repeated dipping-thermal decomposition treatment to obtain a renewable anode with the oxide catalyst (the oxide catalyst is still an oxide in the working environment of the battery);
fifthly, sintering the battery with the renewable anode at high temperature to obtain a solid oxide fuel battery;
wherein the solute of the nitrate precursor solution A in the third step is nitrate of Ni or nitrate of Co; the solute of the nitrate precursor solution B is zirconium nitrate or nitrate of rare earth elements.
The invention provides a composite anode which is prepared by single-layer coating of a substrate anode modified by a metal catalyst by adopting a micro-nano oxide catalyst, and a three-phase reaction area is expanded to the whole anode area by utilizing the property that the micro-nano oxide catalyst has the capability of transporting oxygen ions on the premise of not influencing the function of the substrate anode and the exertion of the catalytic function of the metal catalyst; the micro-nano oxide catalyst particles can also increase the active sites of the fuel electrochemical reaction at the anode, and further improve the electrochemical performance of the composite anode. When the composite anode is poisoned by sulfur and carries out the electrochemical pump oxygen oxidation process, the micro-nano oxide catalyst at the anode can provide rich oxygen ion transport channels, and in addition, the micro-nano oxide catalyst is attached to the surfaces of the substrate anode and the metal catalyst and can also play a role in blocking and inhibiting the migration of the metal catalyst.
In the preparation process of the sulfur poisoning resistant renewable anode of the solid oxide fuel cell, a nitrate precursor solution corresponding to a metal catalyst is decomposed into the metal oxide during high-temperature calcination, and in the working process of the cell, the metal oxide is reduced into the metal catalyst by reducing atmosphere, and the metal catalyst is usually selected from more active metal elements in transition group metals or alkaline earth metals; in the preparation process of the sulfur poisoning resistant renewable anode of the solid oxide fuel cell, a nitrate precursor solution corresponding to an oxide catalyst is decomposed into a metal oxide during high-temperature calcination, and in the operation of the cell, the metal oxide cannot be reduced into metal by reducing atmosphere, but is a metal oxide catalyst with various metal valence states coexisting, and the oxide catalyst is usually selected from rare earth metal element oxides or oxides synthesized by various rare earth metal elements. In order to furthest promote a three-phase reaction area of an anode and realize the inhibition of the migration problem of a metal catalyst in the electrochemical oxidation process, the loading capacity of the oxide catalyst is greater than that of the metal catalyst, and the metal catalyst and a substrate anode are coated by a single-layer oxide catalyst; if the amount of the oxide catalyst is small, the three-phase reaction zone and the increase of the specific surface area of the composite anode are limited, and if the amount of the oxide catalyst is large, a multi-layer dense coating is formed at the metal catalyst and the substrate anode, which may make the metal catalyst and the substrate anode lose the catalytic and substrate anode functions.
The invention aims at the problem that a substrate anode modified by a metal catalyst is not suitable for electrochemical pump oxygen oxidation regeneration, provides a composite anode structure which adopts an oxide catalyst to fix the metal catalyst and realizes coexistence of the oxide catalyst, the metal catalyst and the substrate anode by controlling the impregnation sequence and the impregnation amount of the two catalysts, and the composite anode can realize regeneration through an electrochemical pump oxygen oxidation process after sulfur poisoning. The composite anode structure can solve the problem that the sulfur poisoning metal anode cannot be regenerated by an electrochemical pump oxygen oxidation method in the commercial process of the SOFC, and can also provide reference for the migration and regeneration problems of catalyst materials in other fields.
Drawings
Fig. 1 is a schematic structural diagram of a sulfur poisoning resistant regenerable anode of a solid oxide fuel cell of the present invention, wherein 1 represents an anode, 2 represents an electrolyte, 3 represents a cathode, 1-1 represents a porous substrate anode, 1-2 represents an oxide catalyst, and 1-3 represents a metal catalyst;
FIG. 2 is a micro-topography of the LSCrM-Ni composite anode obtained in step two of the example;
FIG. 3 shows LSCrM-Ni-CeO obtained in step three of the example2A micro-topography of the composite anode;
FIG. 4 is LSCrM-Ni-CeO after regeneration in the examples2A micro-topography of the composite anode;
FIG. 5 shows the SOFC in the example at 50ppm H2S output voltage decay curve (15mA) diagram in fuel atmosphere;
FIG. 6 is a graph of output performance of cells after electrochemical pump oxygen oxidation regeneration, after no sulfur poisoning in the examples, wherein ■ represents before sulfur poisoning, ● represents after sulfur poisoning, and a-solidup represents after oxidation regeneration.
Detailed Description
The first embodiment is as follows: the preparation method of the sulfur poisoning resistance and renewable anode of the solid oxide fuel cell of the embodiment is implemented according to the following steps:
firstly, mixing an anode material and a binder to prepare anode slurry, and mixing a cathode material and the binder to prepare cathode slurry;
secondly, respectively coating the anode slurry and the cathode slurry on two sides of the electrolyte, and sintering at high temperature to obtain a battery initial blank with a porous substrate anode and a porous cathode;
dripping a nitrate precursor solution A of a metal catalyst into the porous substrate anode, and performing repeated dipping-thermal decomposition treatment to obtain a composite anode with a metal oxide catalyst (the metal oxide catalyst is reduced into metal in the working environment of the battery);
dripping a nitrate precursor solution B of an oxide catalyst into the composite anode, and repeatedly soaking and thermally decomposing to obtain a renewable anode with the oxide catalyst (the oxide catalyst is still an oxide in the working environment of the battery);
fifthly, sintering the battery with the renewable anode at high temperature to obtain a solid oxide fuel battery;
wherein the solute of the nitrate precursor solution A in the third step is nitrate of Ni or nitrate of Co; the solute of the nitrate precursor solution B is zirconium nitrate or nitrate of rare earth elements.
The sulfur poisoning resistant renewable anode of the solid oxide fuel cell is obtained by dripping a nitrate precursor solution corresponding to a metal catalyst on an SOFC substrate anode material, performing multiple dipping-thermal decomposition treatment to obtain a composite anode in which the metal catalyst and the substrate anode coexist, dripping a nitrate precursor solution corresponding to an oxide catalyst on the composite anode, and performing multiple dipping-thermal decomposition treatment to obtain the sulfur poisoning resistant and renewable anode of the solid oxide fuel cell. The metal catalyst is usually selected from active metal elements in transition group metals or alkaline earth metals, and the oxide catalyst is usually selected from oxides of certain rare earth metal elements or oxides synthesized by multiple rare earth metal elements.
The material of the solid oxide fuel cell electrolyte of the present embodiment is doped zirconia, doped ceria, doped lanthanum gallate solid electrolyte, or other oxygen ion conducting type electrolyte material. The material of the cathode of the solid oxide fuel cell is usually ABO3Or A2BO4A composite oxide material of the general formula (O is oxygen element), or has ABO3Or A2BO4The composite cathode material consists of oxide material and electrolyte material.
In the embodiment, the composite anode structure with the metal catalyst inside and the oxide catalyst outside and the substrate anode coated with the metal catalyst and the oxide catalyst in a single layer is realized by controlling the impregnation sequence and the impregnation amount of the metal catalyst and the oxide catalyst; in the electrochemical pump oxygen oxidation process, the purposes that the oxide catalyst provides a sufficient oxygen ion transmission channel and blocks the migration of the metal catalyst are achieved.
The second embodiment is as follows: the difference between the present embodiment and the first embodiment is that the molar concentration of the nitrate precursor solution a in the third step is 0.1-0.5 mol/L.
The third concrete implementation mode: the difference between the present embodiment and the first or second embodiment is that the molar concentration of the nitrate precursor solution B in the fourth step is 0.1-0.5 mol/L.
The fourth concrete implementation mode is as follows: the present embodiment is different from the first to the third embodiments in that the high temperature sintering in the second step is performed at 900-1100 ℃ for 0.5-1 h.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is that the dipping-thermal decomposition treatment process in the third step is to drop the nitrate precursor solution a on the porous anode and perform thermal decomposition treatment at 200 ℃ for 0.5 h.
The sixth specific implementation mode: the present embodiment is different from the first to fifth embodiments in that the immersion-thermal decomposition treatment in the third and fourth steps is repeated 3 to 6 times.
The seventh concrete implementation mode: the present embodiment is different from one of the first to sixth embodiments in that the impregnation amount of the nitrate precursor solution B corresponding to the oxide catalyst is larger than that of the nitrate precursor solution a corresponding to the metal catalyst.
The specific implementation mode eight: the seventh embodiment is different from the seventh embodiment in that the impregnation amount of the nitrate precursor solution A is 2 to 4mmol/cm-3The impregnation amount of the nitrate precursor solution B is 5-8 mmol/cm-3。
The embodiment controls the loading amount of the oxide catalyst to be larger than that of the metal catalyst, and realizes that the metal catalyst and the substrate anode are coated by a single-layer oxide catalyst.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is that the high temperature calcination in the fifth step is sintering at 400-900 ℃ for 0.5-1 h.
The detailed implementation mode is ten: the difference between this embodiment and one of the first to ninth embodiments is that the solid oxide fuel cell has a tubular, flat or corrugated structure.
Example (b): the preparation method of the solid oxide fuel cell of the present example was carried out according to the following steps:
firstly, mixing an LSCrM substrate anode material with a binder (a mixture of terpineol and ethyl cellulose) to prepare anode slurry, and mixing an LSM cathode material with the binder to prepare cathode slurry;
coating the anode slurry and the cathode slurry on two sides of a YSZ electrolyte respectively, and sintering at the high temperature of 1100 ℃ to obtain a battery initial blank with a porous LSCrM substrate anode and a porous LSM cathode;
dripping a porous LSCrM substrate anode by using 0.5mol/L nickel nitrate solution, and performing repeated dipping-thermal decomposition treatment for 3 times to obtain a battery blank with an LSCrM-NiO composite anode, wherein the LSCrM-NiO exists in the form of LSCrM-Ni in the working environment of the battery;
dripping an LSCrM-NiO composite anode by adopting 0.5mol/L cerous nitrate solution, and carrying out repeated dipping-thermal decomposition treatment for 6 times to obtain the electrode with the LSCrM-NiO-CeO2Batteries with renewable anodes, LSCrM-NiO-CeO2The renewable anode is prepared from LSCrM-Ni-CeO in the working environment of the battery2The form exists;
fifthly, calcining the cell with the renewable anode at the high temperature of 900 ℃ for 1h to obtain the solid oxide fuel cell.
The solid oxide fuel cell of this example is an electrolyte supported single cell, using LSCrM as the anode, Ni as the metal catalyst, CeO2The catalyst is oxide catalyst, LSM is cathode, YSZ is electrolyte, and the impregnation amount of the metal Ni catalyst in the third step is 3mmol/cm-3CeO in step four2The impregnation amount of (2) is 6mmol/cm-3. The battery hasThe effective area is 0.1256cm-2. The sulfur poisoning time of the battery is 6.5H, the fuel flow is 50mL/min, and H2The concentration of S is 50ppm, the oxygen oxidation regeneration process of the electrochemical pump is carried out in Ar, the flow rate of Ar is 10mL/min, and the oxygen pumping current is 32mA · cm-2The pump oxygen regeneration time is 10min, and the cathode is in the air. FIG. 2 is a micro-morphology of an LSCrM-Ni composite anode, wherein Ni nano-particles are scattered and distributed on the surface of micron-sized LSCrM particles; FIG. 3 shows LSCrM-Ni-CeO2The micro appearance of the composite anode, the metal Ni catalyst and LSCrM substrate anode particles are coated with CeO2Catalyst is covered inside, and CeO2The impregnated layer is not massive and essentially achieves a single layer coverage. Fig. 5 shows the change of the SOFC output voltage in the sulfur poisoning process, and after 6.5h poisoning, the voltage degradation rate is only 3%. FIG. 6 is a graph of the maximum output power density (P) of an SOFC before and after sulfur poisoning and after electrochemical pumped oxygen oxidation regenerationmax) P before sulfur poisoningmaxIs 439mW cm-2(ii) a While the 6.5h sulfur poisoning process apparently resulted in PmaxReduction (294mW cm)-2) (ii) a However, the electrochemical pump oxygen oxidation process will again be PmaxLift to 347mW cm-2. The above results show that2The electrochemical performance of the composite anode can be improved, the composite anode has better sulfur poisoning resistance, and more importantly, the sulfur-poisoned composite anode can be regenerated through an electrochemical pump oxygen oxidation process. As shown by the microstructure of the regenerated anode (FIG. 4), the catalyst particles do not aggregate at the LSCrM grain boundary, and CeO does not exist2The presence of (a) does achieve the object of inhibiting the migration of the metallic Ni catalyst.

Claims (8)

1. The preparation method of the solid oxide fuel cell sulfur poisoning resistant and renewable anode is characterized by comprising the following steps:
firstly, mixing an anode material and a binder to prepare anode slurry, and mixing a cathode material and the binder to prepare cathode slurry;
secondly, respectively coating the anode slurry and the cathode slurry on two sides of the electrolyte, and sintering at high temperature to obtain a battery initial blank with a porous substrate anode and a porous cathode;
dripping a nitrate precursor solution A of a metal catalyst into the porous substrate anode, and performing repeated dipping-thermal decomposition treatment to obtain a composite anode with the metal oxide catalyst;
dripping the composite anode by adopting a nitrate precursor solution B of an oxide catalyst, and performing repeated dipping-thermal decomposition treatment to obtain a renewable anode with the oxide catalyst;
fifthly, sintering the battery with the renewable anode at high temperature to obtain a solid oxide fuel battery;
wherein the solute of the nitrate precursor solution A in the third step is nitrate of Ni or nitrate of Co; the solute of the nitrate precursor solution B is zirconium nitrate or nitrate of rare earth elements;
the impregnation amount of the nitrate precursor solution A is 2-4 mmol cm-3The impregnation amount of the nitrate precursor solution B is 5-8 mmol/cm-3。
2. The method for preparing a sulfur poisoning resistant and regenerable anode of a solid oxide fuel cell according to claim 1, wherein the molar concentration of the nitrate precursor solution a in step three is 0.1-0.5 mol/L.
3. The method for preparing a sulfur poisoning resistant and regenerable anode of a solid oxide fuel cell according to claim 1, wherein the molar concentration of the nitrate precursor solution B in the step four is 0.1-0.5 mol/L.
4. The method of claim 1, wherein the sintering at 900-1100 ℃ for 0.5-1 h is performed in the second step.
5. The method of claim 1, wherein the dipping-thermal decomposition treatment process comprises dropping a nitrate precursor solution A on the porous anode, and performing thermal decomposition at 200 ℃ for 0.5 h.
6. The method of claim 1, wherein the dipping-thermal decomposition process of the third step and the fourth step is repeated 3-6 times.
7. The method of claim 1, wherein the sintering at 400-900 ℃ for 0.5-1 h is performed in the step five.
8. The method of claim 1, wherein the solid oxide fuel cell is tubular, flat or corrugated.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102881930A (en) * 2012-10-26 2013-01-16 中国科学院上海硅酸盐研究所 Method for preparing flat-plate type metal-support solid oxide fuel cell

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102881930A (en) * 2012-10-26 2013-01-16 中国科学院上海硅酸盐研究所 Method for preparing flat-plate type metal-support solid oxide fuel cell

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