CN110581283A - Bismuth-doped solid oxide cell fuel electrode material and preparation method and application thereof - Google Patents
Bismuth-doped solid oxide cell fuel electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a bismuth-doped solid oxide cell fuel electrode material and a preparation method and application thereof; the invention provides a bismuth-doped solid oxide cell fuel electrode material with a chemical formula of La1‑x‑zM1xBizCr1‑yM2yO3‑δM1 is an alkaline earth metal, M2 is a transition metal; x is more than 0 and less than 1.0, y is more than 0 and less than 1.0, and z is the doping amount of Bi. In the embodiment of the invention, the Bi is doped with LSCrF perovskiteThe catalytic activity of the fuel electrode material is obviously enhanced; the Bi-doped perovskite oxide fuel electrode material disclosed by the invention keeps better chemical and structural stability under the conditions of an oxidizing atmosphere, a reducing atmosphere and high temperature, and has better chemical compatibility and thermal compatibility with a typical electrolyte material. In addition, the Bi element is cheaper and easily obtained, and the preparation method of the Bi doping is simpler and more convenient and easier to operate, thereby being beneficial to the application in the solid oxide battery.
Description
Technical Field
The invention relates to the technical field of solid oxide cell fuel electrode materials, in particular to a bismuth-doped solid oxide cell fuel electrode material and a preparation method and application thereof.
Background
the application of solid oxide fuel cells (SOCs) is divided into two modes, one is Solid Oxide Fuel Cells (SOFCs), which can directly convert chemical energy stored in fuel into electrical energy; the other is a Solid Oxide Electrolytic Cell (SOEC), which can electrolyze water and carbon dioxide into hydrogen and carbon monoxide at high temperature by using clean energy such as solar energy, wind energy and the like. In principle, SOFC and SOEC are the reverse reaction processes of each other: in SOFCs, fuels such as hydrogen and carbon monoxide undergo an electrochemical oxidation reaction at the anode (fuel electrode) of the SOFC to produce electrical energy; in SOEC, water and carbon dioxide undergo an electrochemical reduction reaction at the cathode (fuel electrode) of the SOEC to produce hydrogen and carbon monoxide, thereby storing energy in the fuel. Both SOFC and SOEC have the advantages of high energy conversion efficiency, cleanness, no pollution and the like, and thus are receiving more and more attention. Among them, the fuel pole is an important component of SOC, and the performance of the fuel pole directly affects the overall performance of SOC. The fuel electrode material generally needs to have high ionic conductivity and electronic conductivity, and simultaneously has high anode oxidation catalytic activity and cathode reduction catalytic activity. In addition, the fuel electrode material should have good chemical and structural stability under SOFC and SOEC operating conditions.
Currently, the most commonly used fuel electrode material is Ni-YSZ cermet based fuel electrode, in which YSZ (yttria stabilized zirconia) is used as the ionic conductor material, Ni is used as the electron conductor and catalyst material, and Ni-YSZ cermet based fuel electrode has high electron conductance, ion conductance and catalytic activity. However, according to the reports of the document Fundamental mechanical transformed in the degradation of nickel-yttrium stabilized zirconia (Ni-YSZ) and dual oxide fuel cells operation, A review (M.S. Khan, S.Lee, R.Song, J.Lee, T.Lim, S.park.ceramics International42(2016) 35-48), when hydrocarbon fuel and sulfur-containing fuel are used as fuel of SOFC, Ni-YSZ fuel electrode has serious problems of carbon deposition and sulfur poisoning; in addition, the finely dispersed Ni particles are susceptible to particle coarsening and agglomeration at high SOC operating temperatures, thereby reducing the catalytic activity of Ni. These problems all lead to severe degradation of SOC performance, and it is therefore important to find a stable, carbon deposit and sulfur poisoning resistant fuel electrode material.
LaCrO3perovskite-based oxide (ABO)3) The fuel electrode material is a mixed conductor material with both ionic conductivity and electronic conductivity, and compared with a Ni-YSZ metal ceramic-based fuel electrode, the mixed conductor fuel electrode material can expand a reaction active region to the whole electrode surface; meanwhile, LaCrO3The base oxide can maintain chemical and structural stability in a wide range of oxygen partial pressure and temperature, so that LaCrO3the base oxide is expected to be one of the preferred materials for the SOC fuel electrode. However, the catalytic activity of the material is poor, and finally the output performance of the SOFC and the electrolysis performance of the SOEC are low, so that the material cannot be directly used for SOC. Therefore, how to improve LaCrO3the catalytic activity of the base oxide is to realize LaCrO3The base oxide serves as the key to the SOC fuel pole.
The literature Preparation, characterization and electrical properties of Ca and Sr doped LaCrO3(H.Qi, Y.Luan, S.Che, L.Zuo, X.ZHao, C.Hou.Inorganic Chemistry Communications 66(2016) 33-35) and Correlation of fuel cell and organic activity of research La0.75Sr0.25Cr0.5X0.5O3-δ(X ═ Ti, Mn, Fe, Co) (N.Danilovic, A.Vincent, J.Luo, K.T.Chuang, R.Hui, A.R.Sanger.chem.Mater.22(2010) 957-containing material 965) and the like, and it was reported that LaCrO was improved by doping at the A-site and the B-site3Fuel pole performance of the base oxide. For example, doping the A site with an alkaline earth metal such as Ca or Sr can increase the amount of LaCrO3electron conductivity of the oxide of (a); the B site is doped with transition metals such as Fe, Mn, Ti, Co and the like to improve LaCrO3Catalytic activity of the base oxide. Further, document La0.8Sr0.2Cr1-xRuxO3-δ-Gd0.1Ce0.9O1.95 solid oxide fuel celNoble metal-doped LaCrO has also been reported in Ru precipitation and electrochemical performance (W.Kobsisimple, B.D.Madsen, Y.Wang, L.D.marks, S.A.Barnet. solid State ions 180(2009) 257-3The base oxide and the noble metal element are subjected to in-situ desolventizing reaction under the reducing atmosphere to generate noble metal nano particles, and the uniformly dispersed noble metal nano particles can effectively improve LaCrO3Catalytic properties of the base oxide.
In the doping of the elements, Sr is doped at the A site, and Fe is doped at the B site to form La1-xSrxCr1-yFeyO3-δ(LSCrF, x is more than 0 and less than 1.0, and y is more than 0 and less than 1.0) oxide, and shows better catalytic performance. LSCrF has better chemical and structural stability in oxidizing and reducing atmospheres, Fe is cheaper and more easily obtained than noble metal elements, and the synthesis process is simpler and more convenient and is easy to operate. However, the catalytic performance of LSCrF is still low, far less than that of noble metal doping, and far away from the SOC industrialization requirement.
Disclosure of Invention
In view of this, the present application provides a bismuth-doped solid oxide battery fuel electrode material, and a preparation method and an application thereof, and the fuel electrode material provided by the present application has a high catalytic activity, is cheap and easily available, and is beneficial to application in a solid oxide battery.
The application provides a bismuth-doped solid oxide cell fuel electrode material, which has a general formula of formula I:
La1-x-zM1xBizCr1-yM2yO3-δFormula I;
Wherein M1 is an alkaline earth metal, M2 is a transition metal; x is more than 0 and less than 1.0, y is more than 0 and less than 1.0, z is the doping amount of Bi, and delta is the content of oxygen vacancy.
Preferably, M1 is Sr, Ba or Ca, and M2 is Fe, Mn, Ti, V, Mo, Nb, Co, Ni, Cu or Zn.
preferably, 0 < z.ltoreq.0.5.
The invention provides a preparation method of the bismuth-doped solid oxide cell fuel electrode material, which is prepared by adopting a solid phase method, a sol-gel method or a citrate combustion method.
The invention provides the use of a bismuth doped solid oxide cell fuel electrode material as hereinbefore described in a solid oxide fuel cell or a solid oxide electrolysis cell.
The invention provides a solid oxide cell, which comprises an electrolyte, an air electrode and a fuel electrode, wherein the fuel electrode comprises: 1-100 wt% of the bismuth-doped solid oxide battery fuel electrode material and 0-99 wt% of a first electrolyte additive.
Preferably, the air electrode includes: 1-100 wt% of air electrode oxide and 0-99 wt% of second electrolyte additive.
Preferably, the electrolyte consists of an electrolyte material, the first electrolyte additive, the second electrolyte additive and the electrolyte material being independently selected from one or more of doped lanthanum gallate, doped ceria and stabilized zirconia.
the invention provides a preparation method of a solid oxide battery, which comprises the following steps:
Pressing the electrolyte material by adopting a dry pressing method, and then sintering to obtain a flaky electrolyte;
Coating the fuel electrode slurry and the air electrode slurry on the electrolyte, and performing heat treatment to form an electrode to obtain a symmetrical single cell or an asymmetrical single cell;
The fuel electrode slurry comprises the bismuth doped solid oxide cell fuel electrode material described hereinbefore.
Preferably, the sintering temperature of the electrolyte is 1200-1500 ℃, and the sintering time of the electrolyte is 5-10 hours; the preparation of the electrode adopts a screen printing mode; the temperature of the electrode heat treatment is 900-1100 ℃, and the time is 1-5 hours.
Compared with the prior art, the invention provides a bismuth-doped solid oxide battery fuel electrode material with a chemical formula of La1-x-zM1xBizCr1-yM2yO3-δWherein M1 is an alkaline earth metal, and M2 is a transition metal; 0 < (R) >x is less than 1.0, y is more than 0 and less than 1.0, and z is the doping amount of Bi. The perovskite type oxide fuel electrode material, such as the A site of LSCrF, is doped with Bi element, the Bi element shows an intermediate valence state between zero valence and positive trivalent, and the intermediate valence state can enable the B site element Cr and Fe of the LSCrF to have higher valence states, so that the carrier concentration of the LSCrF is increased, and the electronic conductivity is improved; at the same time, the concentration of oxygen defects increases, and the concentration of oxygen vacancies increases. Therefore, the catalytic activity of the Bi-doped LSCrF perovskite type fuel electrode material in the embodiment of the invention is obviously enhanced. The Bi-doped perovskite oxide fuel electrode material maintains better chemical and structural stability under the conditions of oxidizing atmosphere, reducing atmosphere and high temperature, and is matched with a typical electrolyte material LSGM (La)0.9Sr0.1Ga0.8Mg0.2O3-δ)，YSZ(Y0.15Zr0.85O2-δ)，SDC(Sm0.2Ce0.8O1.9)，GDC(Gd0.1Ce0.9O1.95) And the like have better chemical compatibility and thermal compatibility. Doping LaCrO with other transition metal elements3Compared with a base fuel electrode, the doping of the Bi at the A position shows more excellent performance, and the doping effect of the Bi at the A position is close to or even higher than that of the noble metal element. In addition, the Bi element is cheaper and easily obtained, and the preparation method of the Bi doping is simpler and more convenient and easier to operate, thereby being beneficial to the application in the solid oxide battery.
Experiments show that the La is prepared under the wet hydrogen condition of 600-850 DEG C0.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δhas an electron conductivity of 0.028 to 0.21 S.cm-1The conductivity of the LSCrF is 2 to 3 times higher than that of the LSCrF under the same condition; under the air atmosphere of 600-0.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δhas an electron conductivity of 5.89-12.93 S.cm-1The conductivity is 3 to 9 times higher than that of LSCrF under the same condition.
Drawings
FIG. 1 shows La in example 10.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δAnd XRD patterns of the LSCrF oxide before and after 5 hours of reduction in a wet hydrogen atmosphere at 850 ℃;
FIG. 2 shows La in example 10.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δAnd XPS spectra of Bi4f before and after reduction of LSCrF oxide in a humid hydrogen atmosphere at 850 ℃ for 5 hours;
FIG. 3 shows La of example 10.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δAnd a programmed temperature desorption curve of the LSCrF oxide in a 5% hydrogen-nitrogen atmosphere;
FIG. 4 shows La in example0.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δAnd the electrical conductivity of LSCrF oxide in air and a humid hydrogen atmosphere;
FIG. 5 shows La in example 30.55Sr0.25Bi0.2Cr0.5Fe0.5O3-δAnd XRD patterns of the LSCrF oxide before and after 5 hours of reduction in a wet hydrogen atmosphere at 850 ℃;
FIG. 6 shows La in example 40.7Sr0.25Bi0.05Cr0.5Fe0.5O3-δAnd XRD patterns of LSCrF oxide before and after 5 hours of reduction in a wet hydrogen atmosphere at 850 ℃.
Detailed Description
the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, 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 invention.
The invention provides a bismuth-doped solid oxide cell fuel electrode material, which has a general formula of formula I:
La1-x-zM1xBizCr1-yM2yO3-δFormula I;
Wherein M1 is an alkaline earth metal, M2 is a transition metal; x is more than 0 and less than 1.0, y is more than 0 and less than 1.0, z is the doping amount of Bi, and delta is the content of oxygen vacancy.
The fuel electrode material provided by the application has high catalytic activity, good stability, low price and easy availability, and is beneficial to application in solid oxide batteries.
The invention provides a Bi-doped perovskite (ABO)3) The chemical composition of the A site of the oxide fuel electrode material is bismuth (Bi), lanthanum (La) and alkaline earth metal M1, and the B site of the oxide fuel electrode material is chromium (Cr) and transition metal M2. Among them, M1 is preferably strontium (Sr), barium (Ba) or calcium (Ca), more preferably Sr; m2 is preferably iron (Fe), manganese (Mn), titanium (Ti), vanadium (V), molybdenum (Mo), niobium (Nb), cobalt (Co), nickel (Ni), copper (Cu), or zinc (Zn), more preferably Fe. Specifically, the chemical general formula of the bismuth-doped solid oxide battery fuel electrode material is La1-x-zSrxBizCr1-yFeyO3-δ。
in formula I, 0 < x < 1.0, for example x is 0.25 or 0.5; 0 < y < 1.0, for example y is 0.5 or 0.8. z is the doping amount of Bi, preferably 0 < z.ltoreq.0.5, more preferably 0.001. ltoreq.z.ltoreq.0.25, further preferably 0.01. ltoreq.z.ltoreq.0.2, for example, z is 0.1. In addition, delta represents the content of oxygen vacancy, and the specific value is uncertain and is related to the synthesis condition and the property of the material; usually expressed directly as O without limitation to the value of δ3-δ. In general, the value of δ is in most cases positive, indicating oxygen vacancy generation, and may also be negative for some materials, indicating excess oxygen in the material, and a particular range may be expressed as 0 < δ < 1. In the present invention, the preferred chemical formula is La0.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δ。
Taking Bi-doped LSCrF oxide as an example, the embodiment of the invention provides a Bi element A-site doped LSCrF perovskite oxide fuel electrode, wherein Bi is in a middle valence state between zero valence and positive trivalent, and the lower valence state of Bi causes the valence state of B-site elements Cr and Fe of LSCrF to be increased on one hand, and increases the content of oxygen defects on the other hand, and finally increases the conductivity and the oxygen vacancy concentration of the LSCrF oxide, thereby improving the SOFC anode oxidation catalytic activity and the SOEC cathode reduction of the LSCrF fuel electrode materialThe catalytic performance, namely the electrochemical performance of the material is improved, and a novel high-performance oxide electrode material is provided for the practicability of the solid oxide battery. In addition, the Bi-doped LSCrF perovskite oxide in the embodiment of the invention has better chemical and structural stability under the conditions of oxidizing atmosphere, reducing atmosphere and high temperature; it is mixed with a typical electrolyte material LSGM (La)0.9Sr0.1Ga0.8Mg0.2O3-δ)、SDC(Sm0.2Ce0.8O1.9)、GDC(Gd0.1Ce0.9O1.95)、YSZ(Y2O3Stabilized ZrO2) The like has better chemical compatibility and thermal matching property, and is beneficial to application.
In the specific embodiment of the invention, La is carried out under the wet hydrogen condition of 600-850 DEG C0.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δHas an electron conductivity of 0.028 to 0.21 S.cm-1(ii) a Under the air atmosphere of 600-0.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δHas an electron conductivity of 5.89-12.93 S.cm-1。
the invention provides a preparation method of the bismuth-doped solid oxide cell fuel electrode material, which can be synthesized by a solid phase method or a sol-gel method and can also be prepared by a citrate combustion method.
the solid phase method is exemplified as follows: with La2O3、SrCO3、Bi2O3、Cr2O3、Fe2O3As a raw material, according to La1-x- zSrxBizCr1-yFeyO3-δWherein x is more than 0 and less than 1.0, y is more than 0 and less than 1.0, z is more than 0 and less than or equal to 0.5, the mixture is ball-milled in absolute ethyl alcohol for 24 hours, the evenly mixed slurry is placed in an oven to be dried, then is placed in a muffle furnace to be calcined for 3 to 10 hours at the temperature of 900-1100 ℃, and the steps are repeated for 2 to 3 times to obtain pure-phase Bi-doped solid oxide cell fuel electrode material powder La1-x-zSrxBizCr1-yFeyO3-δ(0＜x＜1.0，0＜y＜1.0，0＜z≤0.5)。
The sol-gel method may specifically include:
a. With La2O3、Sr(NO3)2、Cr(NO3)3·9H2O、Bi(NO3)3·5H2O、Fe(NO3)3·9H2O as a raw material, according to La1-x-zSrxBizCr1-yFeyO3-δWherein x is more than 0 and less than 1.0, y is more than 0 and less than 1.0, and z is more than 0 and less than or equal to 0.5 in a stoichiometric ratio, and then the raw material solution is obtained;
b. Mixing citric acid and ethylenediamine tetraacetic acid serving as complexing agents with the raw material solution to obtain a mixed solution; the molar ratio of the total amount of citric acid, ethylene diamine tetraacetic acid and metal ions is preferably 1: 1.5: 1;
c. Dropwise adding ammonia water into the mixed solution, adjusting the pH value of the mixed solution to 5-6, and preferably stirring for 1-4 hours to obtain a uniform solution;
d. Stirring the uniform solution at 120 ℃ for 6-10 hours to obtain sol, aging the sol to obtain gel, puffing and drying the gel in an oven, grinding to obtain precursor powder, calcining the precursor powder at 900-1100 ℃ in a muffle furnace for 3-10 hours to obtain pure-phase Bi-doped solid oxide battery fuel electrode material powder La1-x- zSrxBizCr1-yFeyO3-δ(0＜x＜1.0，0＜y＜1.0，0＜z≤0.5)。
The synthesis method of the material of the invention is described below by taking a citrate combustion method as an example, and the specific implementation steps are as follows:
a. With La2O3、Sr(NO3)2、Cr(NO3)3·9H2O、Bi(NO3)3·5H2O、Fe(NO3)3·9H2O as a raw material, according to La1-x-zSrxBizCr1-yFeyO3-δWherein x is more than 0 and less than 1.0, y is more than 0 and less than 1.0, and z is more than 0 and less than or equal to 0.5 in a stoichiometric ratio, and then the raw material solution is obtained;
b. Mixing citric acid and ethylenediamine tetraacetic acid serving as complexing agents with the raw material solution to obtain a mixed solution; the molar ratio of the total amount of citric acid, ethylene diamine tetraacetic acid and metal ions is preferably 1: 1.5: 1;
c. Ammonia water can be dripped into the mixed solution, the pH value of the mixed solution is adjusted to 5-6, and then the mixed solution is preferably stirred for 1-4 hours to obtain a uniform solution;
d. Heating the uniform solution in a heating table until spontaneous combustion occurs, and collecting powder; calcining the powder in a muffle furnace at the temperature of preferably 900-1100 ℃, preferably 3-10 hours to obtain Bi-doped solid oxide battery fuel electrode material powder La1-x-zSrxBizCr1-yFeyO3-δ(0＜x＜1.0，0＜y＜1.0，0＜z≤0.5)。
The raw materials adopted by the method disclosed by the embodiment of the invention are cheap and easy to obtain, and the preparation process of Bi doping is simple and convenient and easy to operate.
The perovskite type oxide fuel electrode material prepared by the method, such as La, can be used in the embodiment of the invention1-x-zSrxBizCr1- yFeyO3-δthe (0 < x < 1.0, 0 < y < 1.0, 0 < z < 0.5) powder is mixed with a binder (for example, a polyvinyl alcohol binder with the concentration of 5 wt%) uniformly, then the mixture is pressed into a strip sample in a dry mode, the strip sample is sintered for 5 to 10 hours in a high-temperature furnace at 1300 ℃ and 1500 ℃ to obtain a compact fuel electrode sample, and the conductivity of the compact fuel electrode sample is tested by adopting a four-probe method.
The invention provides the use of a bismuth doped solid oxide cell fuel electrode material as hereinbefore described in a Solid Oxide Fuel Cell (SOFC) or a Solid Oxide Electrolysis Cell (SOEC); i.e. the bismuth doped solid oxide cell fuel electrode material as described hereinbefore is used as anode (fuel electrode) of a Solid Oxide Fuel Cell (SOFC) or as cathode (fuel electrode) material of a Solid Oxide Electrolysis Cell (SOEC).
the invention is provided withthe present invention provides a solid oxide cell comprising an electrolyte, an air electrode and a fuel electrode, wherein the fuel electrode comprises: 1-100 wt% of the bismuth-doped solid oxide battery fuel electrode material and 0-99 wt% of a first electrolyte additive. Wherein, the dosage of the first electrolyte additive can be 1-45%. The first electrolyte additive is composed of an electrolyte material for improving the ionic conductivity of the fuel electrode; for ease of subsequent distinction, referred to as the first electrolyte additive. In an embodiment of the invention, the fuel electrode may be single-phase La1-x-zSrxBizCr1-yFeyO3-δ(z is more than 0 and less than or equal to 0.5), or is La with the mass fraction of 1-99 percent1-x-zSrxBizCr1-yFeyO3-δ(z is more than 0 and less than or equal to 0.15) and an electrolyte material.
In an embodiment of the present invention, the air electrode includes: 1-100 wt% of air electrode oxide and 0-99 wt% of second electrolyte additive. The second electrolyte additive is used for improving the ionic conductivity of the air electrode, and the dosage of the second electrolyte additive can be 1-45%. That is, the air electrode may be a single phase of a known air electrode oxide such as La1-aSraCo1-bFebO3-δ(0≤a≤1.0，0≤b≤1.0)，Ba1-aSraCo1-bFebO3-δ(0≤a≤1.0，0≤b≤1.0)，Sm1-aSrbCoO3-δ(0≤a≤1.0)，LnBaCo2O5+δ(Ln ═ La, Pr, Sm, Gd, etc.) or the like, or a mixture of 1 to 99% of one or more of the above air electrode powders and an electrolyte material. Here, a and b are each independently selected ranges.
The electrolyte according to the embodiment of the present invention is composed of an electrolyte material, and the component is used for blocking electron transport and gas transport of the fuel electrode and the air electrode. In terms of material composition, the electrolyte material, and the first and second electrolyte additives described hereinbefore, are independently preferably one or more of doped lanthanum gallate, doped ceria and stabilized zirconia. The first electricitythe electrolyte additive and the second electrolyte additive may be the same or different; various electrolyte materials employed in the present invention include, but are not limited to: la1-aSraGa1-bMgbO3-δ(LSGM)(0＜a＜1，0＜b＜1)，SmaCe1- aO2-δ(SDC)，GdaCe1-aO2-δ(GDC)，LaaCe1-aO2-δ(LDC)，YaCe1-aO2-δ(YDC), wherein 0 < a < 1) or ScaZr1- aO2-δ(SSZ)，YaZr1-aO2-δ(YSZ) wherein 0 < a < 1. Here, a and b are each independently selected ranges.
Correspondingly, the invention also provides a preparation method of the solid oxide battery, which comprises the following steps:
Pressing the electrolyte material by adopting a dry pressing method, and then sintering to obtain a flaky electrolyte;
coating the fuel electrode slurry and the air electrode slurry on the electrolyte, and performing heat treatment to form an electrode to obtain a symmetrical single cell or an asymmetrical single cell; the fuel electrode slurry comprises the bismuth doped solid oxide cell fuel electrode material described hereinbefore.
Respectively coating the fuel electrode slurry and the air electrode slurry on two sides of the electrolyte, and performing heat treatment to obtain an asymmetric single cell; and respectively coating the fuel electrode slurry on two sides of the electrolyte, and performing heat treatment to obtain symmetrical single cells with the same material for the fuel electrode and the air electrode.
in some embodiments of the present invention, the solid oxide cell is prepared by the following steps:
S1, pressing the electrolyte powder material into a wafer by a dry pressing method, and then sintering for 5-10 hours at the temperature of 1200-1500 ℃ preferably to obtain a compact electrolyte support (namely a flaky electrolyte or an electrolyte sheet);
In addition, the fuel electrode powder and the first organic dispersant can be mixed to obtain uniform fuel electrode slurry; mixing the air electrode powder with a second organic dispersant to obtain uniform air electrode slurry;
S2, respectively coating the fuel electrode slurry on both sides of the electrolyte sheet by adopting a screen printing mode, and preferably processing at 900-1100 ℃ for 1-5 hours to prepare symmetrical single cells, namely the fuel electrode and the air electrode are made of the same material;
Or, the fuel electrode slurry is coated on one side of the electrolyte sheet by adopting a screen printing mode, the air electrode slurry is coated on the other side of the electrolyte sheet, and the electrolyte sheet is treated at the temperature of preferably 900-.
Wherein the first organic dispersant and the second organic dispersant may be the same or different. For example, the first and second organic dispersants are each 6 wt.% ethylcellulose-terpineol, used in the following amounts of dispersants: the total weight of the electrode powder is 1.5: 1. the electrode is preferably prepared by adopting a screen printing mode, the electrode slurry can be uniformly distributed on the electrolyte by a screen printing method, and the thickness of the prepared electrode is relatively consistent. The thickness of the prepared electrode can be 10-20 microns; the area of the fuel electrode is equivalent to the whole area of the electrolyte, and the area of the air electrode is slightly smaller than that of the electrolyte, so that the reduction of the effective area caused by asymmetry of the air electrode and the fuel electrode can be reduced on one hand, and the calculation of the effective area of the battery can be facilitated on the other hand; the performance of the cell, i.e., power density, current density, and sheet resistance, are all normalized per unit area.
The electrochemical workstation is adopted in the embodiment of the invention to test the electrochemical performances of the symmetrical single cells and the asymmetrical single cells under different fuels. The results show that the solid oxide cell using the fuel electrode material of the invention has excellent performance.
In order to further understand the present application, the bismuth-doped solid oxide cell fuel electrode material provided by the present application, and the preparation method and application thereof are specifically described below with reference to examples.
In the following examples, all materials are commercially available.
Examples1 preparing La by citrate combustion method0.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δPowder body
According to La0.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δThe stoichiometric ratio of (A) to (B), adding La as a raw material2O3、Sr(NO3)2、Cr(NO3)3·9H2O、Bi(NO3)3·5H2O、Fe(NO3)3·9H2Dissolving O in dilute nitric acid, adding citric acid and ethylenediamine tetraacetic acid as complexing agents, adjusting the pH of the solution to about 6 by using ammonia water, wherein the molar ratio of the total amount of the citric acid to the ethylenediamine tetraacetic acid to the total amount of metal ions is 1: 1.5: 1; heating the uniformly stirred solution on a heating table until spontaneous combustion occurs, collecting powder obtained after combustion, grinding, and calcining at 1000 ℃ for 3 hours in a muffle furnace to obtain La0.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δAnd (3) powder.
La0.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δPowder and LSCrF (La)0.75Sr0.25Cr0.5Fe0.5O3-δ) Carrying out analysis tests such as X-ray diffraction on the oxide; as shown in fig. 1, XRD after doping of Bi showed no formation of a hetero-phase, indicating that Bi was successfully doped into the LSCrF lattice. Further, La0.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δXRD of the fuel electrode oxide is not changed before and after the fuel electrode oxide is reduced for 5 hours at 850 ℃ in a humid hydrogen atmosphere, and the powder has better structural stability in both oxidizing and reducing atmospheres.
FIG. 2 is La0.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δXPS spectra of Bi4f before and after the fuel electrode oxide is reduced in a humid hydrogen atmosphere at 850 ℃ for 5 hours, and when the fuel electrode oxide is not doped with Bi, no Bi peak is detected before and after the LSCrF sample is reduced; after doping with Bi, La0.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δSample reductionThe peak of Bi can be detected before and after the reduction, and the peak of Bi4f is basically not shifted before and after the reduction, which indicates that the Bi element is not reduced in the LSCrF oxide; and the peak of Bi4f is between the peaks of zero-valent Bi and positive-trivalent Bi, indicating that La0.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δthe element Bi is in an intermediate valence state between zero valence and positive trivalent valence.
FIG. 3 is La0.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δCompared with an LSCrF sample, the temperature programming reduction curve of the powder in a 5% hydrogen-nitrogen atmosphere reduces the reduction temperature of the B-site element after doping the Bi element, and the consumption of hydrogen is increased, which indicates that more oxygen vacancies are generated.
example 2La0.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δConductivity testing of perovskite-type oxide fuel electrode materials
La in example 10.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δAdding 4-5 drops of powder and 5 wt.% of polyvinyl alcohol binder into the powder per gram of the powder, uniformly mixing and grinding the powder, then performing dry pressing on the powder to form a strip sample, sintering the sample in a high-temperature furnace at 1400 ℃ for 10 hours to obtain a compact sample, and then testing the conductivity of the sample by adopting a four-probe method.
La0.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δThe conductivity of the sample under air and hydrogen is shown in fig. 4; la under the wet hydrogen condition of 600-850 DEG C0.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δHas an electron conductivity of 0.028 to 0.21 S.cm-1The conductivity of the LSCrF is 2 to 3 times higher than that of the LSCrF under the same condition; under the air atmosphere of 600-0.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δHas an electron conductivity of 5.89-12.93 S.cm-1The conductivity is 3 to 9 times higher than that of LSCrF under the same condition.
EXAMPLE 3 citrate Combustion ProcessPreparation of La0.55Sr0.25Bi0.2Cr0.5Fe0.5O3-δPowder body
preparation was carried out according to the procedure of example 1, differing only in the stoichiometric ratio of the starting materials, giving La0.55Sr0.25Bi0.2Cr0.5Fe0.5O3-δand (3) powder.
La0.55Sr0.25Bi0.2Cr0.5Fe0.5O3-δPerforming analysis tests such as X-ray diffraction on the powder and the LSCrF oxide; as shown in FIG. 5, XRD shows La after doping of Bi0.55Sr0.25Bi0.2Cr0.5Fe0.5O3-δno impurity phase is generated, indicating that Bi is successfully doped into the LSCrF lattice.
EXAMPLE 4 preparation of La by citrate Combustion0.7Sr0.25Bi0.05Cr0.5Fe0.5O3-δPowder body
According to La0.7Sr0.25Bi0.05Cr0.5Fe0.5O3-δthe stoichiometric ratio of (A) to (B), adding La as a raw material2O3、Sr(NO3)2、Cr(NO3)3·9H2O、Bi(NO3)3·5H2O、Fe(NO3)3·9H2dissolving O in dilute nitric acid, adding citric acid and ethylenediamine tetraacetic acid as complexing agents, adjusting the pH of the solution to about 6 by using ammonia water, wherein the molar ratio of the total amount of the citric acid to the ethylenediamine tetraacetic acid to the total amount of metal ions is 1: 1.5: 1; heating the uniformly stirred solution on a heating table until spontaneous combustion occurs, collecting powder obtained after combustion, grinding, and calcining at 1000 ℃ for 3 hours in a muffle furnace to obtain La0.7Sr0.25Bi0.05Cr0.5Fe0.5O3-δAnd (3) powder.
La0.7Sr0.25Bi0.05Cr0.5Fe0.5O3-δPerforming analysis tests such as X-ray diffraction on the powder and the LSCrF oxide; as shown in FIG. 6, XRD shows La after doping of Bi0.7Sr0.25Bi0.05Cr0.5Fe0.5O3-δNo impurity phase is generated, indicating that Bi is successfully doped into the LSCrF lattice. Further, La0.7Sr0.25Bi0.05Cr0.5Fe0.5O3-δXRD of the fuel electrode oxide is not changed before and after the fuel electrode oxide is reduced for 5 hours at 850 ℃ in a humid hydrogen atmosphere, and the powder has better structural stability in both oxidizing and reducing atmospheres.
Example 5La0.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δPreparation of symmetrical single cell and SOFC performance test
Uniformly mixing LSGM electrolyte powder and 5 wt.% of polyvinyl alcohol binder according to 4-5 drops per gram of powder, grinding in an agate mortar for 1.5 hours, then pressing and molding at 250MPa by 0.15g of stainless steel dies with the diameter of 13mm, and sintering at 1450 ℃ for 5 hours in a high-temperature furnace to obtain a compact electrolyte sheet;
la in example 10.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δMixing the powder with 40% of SDC electrolyte powder, and then mixing and grinding the mixture with 6 wt% of ethyl cellulose-terpineol to obtain uniformly dispersed slurry;
Then, the slurry is respectively coated on two sides of the electrolyte sheet by adopting a screen printing mode and then is treated at 1000 ℃ for 2 hours to obtain a fuel electrode and an air electrode both of which are La0.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δ-40% SDC material of symmetrical cells.
Wherein, the thickness of the electrode is 10-20 microns, and one side of the single cell with the symmetrical structure is also an air electrode which is contacted with air; the other side is a fuel electrode which is in contact with the fuel. The air electrode area was 0.2376 cm square, and the fuel electrode size was consistent with the sintered electrolyte size, with a diameter of about 1 cm.
The I-V curves and ac impedance spectra of the symmetric cell were tested with an electrochemical workstation under humidified hydrogen, humidified syngas and ethanol fuel. Wherein, obtained from the I-V curve, La0.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δthe maximum power density of a symmetrical single cell prepared from 40 percent of SDC material at the temperature of 700 ℃ and 850 ℃ is 0.0965-0.405W cm-2(ii) a Maximum power density of 0.282W cm at 800 deg.C-2Under the same conditions, La0.75Sr0.25Cr0.5Fe0.5O3-δ1.5 times the symmetric cell made with 40% SDC material. The maximum power density of the symmetrical cell under the humid synthesis gas at the temperature of 700 ℃ and 850 ℃ is 0.0598-0.367W cm-2(ii) a Wherein the maximum power density at 800 ℃ is 0.255W cm-2Under the same conditions, La0.75Sr0.25Cr0.5Fe0.5O3-δ1.3 times that of a symmetrical single cell made of 40% SDC material. The maximum power density of the symmetrical cell in ethanol at the temperature of 700 ℃ and 850 ℃ is 0.073-0.3W cm-2(ii) a Wherein the maximum power density at 800 ℃ is 0.24W cm-2Under the same conditions, La0.75Sr0.25Cr0.5Fe0.5O3-δ1.9 times of a symmetrical single cell made of 40% SDC material.
Example 6La0.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δPreparation of asymmetric single cell and SOFC performance test
Uniformly mixing LSGM electrolyte powder and 5 wt.% of polyvinyl alcohol binder according to 4-5 drops per gram of powder, grinding in an agate mortar for 1.5 hours, then pressing and molding at 250MPa by 0.15g of stainless steel dies with the diameter of 13mm, and sintering at 1450 ℃ for 5 hours in a high-temperature furnace to obtain a compact electrolyte sheet;
La in example 10.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δMixing the powder with 40% of SDC electrolyte powder, and then mixing and grinding the mixture with 6 wt% of ethyl cellulose-terpineol to obtain uniformly dispersed fuel electrode slurry; la0.6Sr0.4Co0.2Fe0.8O3-δMixing with 40% of SDC electrolyte powder, and then mixing and grinding with 6 wt% of ethyl cellulose-terpineol to obtain uniformly dispersed air electrode slurry;
Then, the fuel electrode slurry is coated on one side of the electrolyte sheet by adopting a screen printing mode, the air electrode slurry is coated on the other side of the electrolyte sheet, and then the asymmetric single cell is obtained by processing at 1000 ℃ for 2 hours.
Wherein the thickness of the electrode is 10-20 microns. The air electrode area was 0.2376 cm square, and the fuel electrode size was consistent with the sintered electrolyte size, with a diameter of about 1 cm.
Respectively testing I-V curves of a single cell under hydrogen, humid synthesis gas and ethanol fuel, wherein La is obtained from the I-V curves0.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δThe maximum power density of an asymmetric single cell prepared from 40 percent of SDC material at the temperature of 700 ℃ and 850 ℃ is 0.195-0.744W cm-2(ii) a Maximum power density of 0.55W cm at 800 deg.C-2Under the same conditions, La0.75Sr0.25Cr0.5Fe0.5O3-δ1.4 times the asymmetric single cell made with 40% SDC material. The maximum power density of the asymmetric battery under the humid synthesis gas at the temperature of 700 ℃ and 850 ℃ is 0.098-0.577W cm-2(ii) a Wherein the maximum power density at 800 ℃ is 0.36W cm-2Under the same conditions, La0.75Sr0.25Cr0.5Fe0.5O3-δ1.5 times the symmetric cell made with 40% SDC material. The maximum power density of the asymmetric battery in ethanol at the temperature of 700 ℃ and 850 ℃ is 0.157-0.554W cm-2(ii) a Wherein the maximum power density at 800 deg.C is 0.41W cm-2Under the same conditions, La0.75Sr0.25Cr0.5Fe0.5O3-δ1.4 times the asymmetric single cell made with 40% SDC material.
Example 7La0.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δPreparation of asymmetric single cell and SOEC performance test
Uniformly mixing LSGM electrolyte powder and 5 wt.% of polyvinyl alcohol binder according to 4-5 drops per gram of powder, grinding in an agate mortar for 1.5 hours, then pressing and molding at 250MPa by 0.15g of stainless steel dies with the diameter of 13mm, and sintering at 1450 ℃ for 5 hours in a high-temperature furnace to obtain a compact electrolyte sheet;
la in example 10.65Sr0.25Bi0.1Cr0.5Fe0.5O3-Mixing the powder with 40% of SDC electrolyte powder, and then mixing and grinding the mixture with 6% of ethyl cellulose-terpineol to obtain uniformly dispersed fuel electrode slurry; la0.6Sr0.4Co0.2Fe0.8O3-δMixing with 40% SDC electrolyte powder, and then mixing and grinding with 6% ethyl cellulose-terpineol to obtain uniformly dispersed air electrode slurry;
Then, the fuel electrode slurry is coated on one side of the electrolyte sheet by adopting a screen printing mode, the air electrode slurry is coated on the other side of the electrolyte sheet, and then the asymmetric single cell is obtained by processing at 1000 ℃ for 2 hours.
Wherein the thickness of the electrode is 10-20 microns. The air electrode area is 0.2376 square centimeter, the fuel electrode size is consistent with the sintered electrolyte size, and the diameter is about 1.0 centimeter.
Testing the asymmetric cell electrolysis H with an electrochemical workstation2O、CO2、CO2-H2I-V curve and AC impedance spectrum of O, wherein La0.65Sr0.25Bi0.1Cr0.5Fe0.5O3-δThe electrolysis cell electrolyzes CO at 800 deg.C under 1.5V2Has a current density of 0.99A cm-2。
From the above examples, it can be seen that the catalytic activity of the Bi-doped LSCrF perovskite fuel electrode material in the embodiment of the present invention is significantly enhanced. The Bi-doped perovskite oxide fuel electrode material disclosed by the invention keeps better chemical and structural stability under the conditions of an oxidizing atmosphere, a reducing atmosphere and high temperature, and has better chemical compatibility and thermal compatibility with typical electrolyte materials such as LSGM, YSZ, SDC, GDC and the like. Doping LaCrO with other transition metal elements3compared with a base fuel electrode, the doping of the Bi at the A position shows more excellent performance, and the doping effect of the Bi at the A position is close to or even higher than that of the noble metal element. In the present invention, Bi element is morethe addition is cheap and easy to obtain, and the preparation method of the Bi doping is simpler and more convenient and is easy to operate, thereby being beneficial to the application in the solid oxide battery.
The above description is only a preferred embodiment of the present invention, and it should be noted that various modifications to these embodiments can be implemented by those skilled in the art without departing from the technical principle of the present invention, and these modifications should be construed as the scope of the present invention.
Claims (10)
1. A bismuth-doped solid oxide cell fuel electrode material having the general formula of formula I:
La1-x-zM1xBizCr1-yM2yO3-δFormula I;
wherein M1 is an alkaline earth metal, M2 is a transition metal; x is more than 0 and less than 1.0, y is more than 0 and less than 1.0, z is the doping amount of Bi, and delta is the content of oxygen vacancy.
2. The bismuth-doped solid oxide cell fuel electrode material of claim 1, wherein M1 is Sr, Ba or Ca, and M2 is Fe, Mn, Ti, V, Mo, Nb, Co, Ni, Cu or Zn.
3. The bismuth doped solid oxide cell fuel electrode material according to claim 1 or 2, characterized in that 0 < z ≦ 0.5.
4. The preparation method of the bismuth-doped solid oxide cell fuel electrode material as claimed in any one of claims 1 to 3, wherein the bismuth-doped solid oxide cell fuel electrode material is prepared by a solid phase method, a sol-gel method or a citrate combustion method.
5. use of the bismuth-doped solid oxide cell fuel electrode material according to any one of claims 1 to 3 in a solid oxide fuel cell or a solid oxide electrolysis cell.
6. A solid oxide cell comprising an electrolyte, an air electrode, and a fuel electrode, wherein the fuel electrode comprises: 1 to 100 wt% of the bismuth-doped solid oxide cell fuel electrode material of any one of claims 1 to 3 and 0 to 99 wt% of a first electrolyte additive.
7. The solid oxide cell of claim 6, wherein the air electrode comprises: 1-100 wt% of air electrode oxide and 0-99 wt% of second electrolyte additive.
8. The solid oxide cell of claim 6 or 7, wherein the electrolyte consists of an electrolyte material, and the first electrolyte additive, second electrolyte additive and electrolyte material are independently selected from one or more of doped lanthanum gallate, doped ceria and stabilized zirconia.
9. A method for preparing a solid oxide cell, comprising the steps of:
Pressing the electrolyte material by adopting a dry pressing method, and then sintering to obtain a flaky electrolyte;
Coating the fuel electrode slurry and the air electrode slurry on the electrolyte, and performing heat treatment to form an electrode to obtain a symmetrical single cell or an asymmetrical single cell;
The fuel electrode slurry comprises the bismuth-doped solid oxide cell fuel electrode material as defined in any one of claims 1 to 3.
10. The method according to claim 9, wherein the sintering temperature of the electrolyte is 1200 to 1500 ℃, and the sintering time of the electrolyte is 5 to 10 hours; the preparation of the electrode adopts a screen printing mode; the temperature of the electrode heat treatment is 900-1100 ℃, and the time is 1-5 hours.
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