Amorphous / crystalline heterojunction composite material, solid oxide fuel cell and catalyst

Abstract

The invention relates to the technical field of catalyst materials and solid oxide cells, and provides an amorphous / crystalline heterojunction composite material, a solid oxide fuel cell and a catalyst. The amorphous / crystalline heterojunction composite material is composed of an amorphous component and a crystalline component, the amorphous component is M < x > R < y > T < z >, the crystalline component comprises one or more of a proton conduction oxide, an oxygen ion conduction oxide, lithium ion conduction ceramic, sodium ion conduction ceramic, a metal material, a carbon material, inorganic salt, an electron conduction material and non-conductive ceramic. According to the amorphous / crystalline heterojunction composite material provided by the invention, the activity and the stability of a catalyst are remarkably enhanced by utilizing the characteristics of unique disordered atom arrangement, high-density surface defect sites and the like of an amorphous material and the synergistic effect of a crystalline material and the amorphous material.

Description

Technical Field

[0001] This invention relates to the fields of catalyst materials and solid oxide battery technology, and particularly to amorphous / crystalline heterojunction composite materials, solid oxide fuel cells, and catalysts. Background Technology

[0002] Solid oxide batteries (SOCs) are reversible devices that can operate in two modes: fuel cells (SOFCs) and electrolysis (SOECs). The former converts the chemical energy in fuel into electrical energy, while the latter converts electrical energy into the chemical energy in fuel.

[0003] A single-cell state-of-the-art (SOC) battery consists of a dense electrolyte and fuel and oxygen electrodes located on opposite sides. Commonly used electrolyte materials include doped zirconium oxide, doped cerium oxide, and doped LaGaO. 3-δ Plasma ion conductors and doped BaCeO 3-δ (0 < δ < 1), doped BaZrO 3-δ (0 < δ < 1), La 2-x Mg x Ce2O 7-δ (0) <x<2,0<δ<1)、BaSn 0.3 Sc 0.7 O 3-δ (0 < δ < 1), BaTi 0.2 Sc 0.8 O 3-δ (0 < δ < 1), La 5.5 WO 11.25-δ (0<δ<1), Ba5R2Al2SnO 13 (R = Gd, Dy, Ho, Y, Er, Tm, Yb) and other proton conductors; commonly used fuel electrodes are metal-ceramic materials composed of metals such as Fe, Co, Ni, or alloys such as FeNi3 and the above-mentioned electrolyte materials, or (La) 1-x Sr x (Cr) 1-y Fe y )O 3-δ (0) <x<1;0<y<1;0<δ<1)、(La 1-x Sr x (Cr) 1- y Mn y )O 3-δ (0) <x<1;0<y<1;0<δ<1)、(La 1-x Sr x TiO 3-δ (0) <x<1;0<δ<1)、La 2-x Sr x Fe 2-y-z Ni y Mo z O 6-δ (0 < x < 1; 0 < y < 1; 0 < z < 1; 0 < δ < 1) and other conductive ceramics and composite ceramics composed of the above electrolyte materials; the oxygen electrode is generally an oxygen ion - electron or oxygen ion - proton - electron mixed conductor material, such as (La 1-x Sr x )MnO 3-δ (0 < x < 1, 0 < δ < 1), (La 1-x Sr x )(Co 1-y Fe y )O 3-δ (0 < x < 1, 0 < y < 1, 0 < δ < 1), (Ba 1-x Sr x )(Co 1-y Fe y )O 3-δ (0 < x < 1, 0 < y < 1, 0 < δ < 1), (Sm 1-x Sr x )CoO 3-δ (0 < x < 1, 0 < δ < 1), SmBaCo2O 5+δ (0 < δ < 1), LaBa 0.5 Sr 0.5 Co2O 5+δ (0 < δ < 1), SmBa 0.5 Sr 0.5 Co2O 5+δ (0 < δ < 1) and BaGd 0.8 La 0.2 Co2O 6-δ (0 < δ < 1).

[0004] However, the electrodes of traditional solid oxide cells are basically polycrystalline materials, and the intrinsic activity of their electrochemical reactions is limited by the volume density of the triple - phase boundary (TPB), and the atomic utilization rate of the catalyst is low, thus affecting the catalytic activity and reaction rate of the electrode. Therefore, it is of great significance to provide a composite material for electrodes or catalysts. Summary of the Invention

[0005] The technical problem solved by the present invention is to provide an amorphous / crystalline heterojunction composite material, which has high catalytic activity and stability as a catalyst.

[0006] In view of this, the present application provides an amorphous / crystalline heterojunction composite material, which is composed of an amorphous component and a crystalline component,

[0007] The amorphous component is M xR y T z M includes La and / or La-substituted ions, wherein the La-substituted ions are selected from one or more of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Ce, Y, Yb, Pr, Nd, Sm, Gd, Eu, Er, Nb, and Bi; R includes Mo and / or Mo-substituted ions, wherein the Mo-substituted ions are selected from one or more of W, V, Cr, Fe, Co, Ni, Ce, Mn, Pt, Pd, Ru, Ga, and Si; T includes O and / or O-substituted ions, wherein the O-substituted ions are selected from one or more of F, Cl, Br, I, S, Se, and N; and O <x<5;0<y<8;0<z<27;

[0008] The crystalline components include one or more of the following: proton-conducting oxides, oxygen-ion-conducting oxides, lithium-ion-conducting ceramics, sodium-ion-conducting ceramics, metallic materials, carbon materials, inorganic salts, electronically conductive materials, and non-conductive ceramics.

[0009] In some specific embodiments, the volume fraction of the amorphous component in the composite material is 0.1% to 99.9%.

[0010] In some specific embodiments, the proton-conducting oxide includes doped CeO. 2-δ1 doped BaZrO 3-δ2 doped BaCeO 3-δ3 Sr2Sc 1+m1 Nb 1-n1 O 6-δ4 BaZr 0.4 Sc 0.6 O 3-δ5 Ba3Ca 1+m2 Nb 2-n2 O9、BaSn 0.3 Sc 0.7 O 3-δ6 BaTi 0.2 Sc 0.8 O 3-δ7 La 5.5 WO 11.25-δ8 and Ba5R2Al2SnO 13 One or more of the following;

[0011] Among them, 0<δ1<1, 0<δ2<1, 0<δ3<1, 0<δ4<1, 0<δ5<1, 0<δ6<1, 0<δ7<1, 0<δ8<1;

[0012] 0 <m1<1,0<n1<1,0<m2<1,0<n2<1;

[0013] R is selected from one or more of Gd, Dy, Ho, Y, Er, Tm, and Yb;

[0014] And / or, the oxygen ion-conducting oxide includes doped ZrO. 2-δ9 doped Bi2O 3-δ10 La2Mo2O doped 9-δ11 doped SrFeO 3-δ12 LaGaO doped 3-δ13 La2NiO 4+δ14 Pr2NiO 4+δ15 Nd2NiO 4+δ16 La4Ni3O 10+δ17 and La 1+x1 Sr 1- x2 Ga3O 7.5-δ18 One or more of the following;

[0015] Among them, 0<δ9<1, 0<δ10<1, 0<δ11<1, 0<δ12<1, 0<δ13<1 , 0<δ14<1, 0<δ15<1, 0<δ16<1, 0<δ17<1, 0<δ18<1,0 <x1<1,0<x2<1。

[0016] In some specific embodiments, the lithium-ion conductive ceramic includes FeLiPO4 and Li 1.3 Al 0.7 Ti 1.7 (PO4)3, doped Li7La3Zr2O 12 and one or more of doped LiTiO3; and / or, the sodium ion-conducting ceramic comprises Na3Zr2Si2PO4. 12 Na 3.4 Zr 1.8 Mg 0.2 Si 2.4 P 0.6 O 12 and Na 3.2 Zr 1.8 Tb 0.2 Si2PO 12 One or more of the following: and / or, the metallic material includes one or more of Ni, Cu, Fe, Co, FeNi3, 430L and 440 stainless steel; and / or, the carbon material includes one or more of graphite, graphene and doped graphene; and / or, the inorganic salt includes one or more of Li2CO3, Na2CO3, K2CO3, SrCO3 and BaCO3.

[0017] In some specific embodiments, the electron-conducting material comprises (La,Ba,Sr)(Cr,Mo,Fe,Co,Ni,Mg,Mn)O 3-δ19 La(Ni,Fe)O 3-δ20 (La,Sr)(Ti,Fe,Co,Ni)O 3-δ21 、(Sm 1-x3 Sr x4 CoO 3-δ22 LaBa 0.5 Sr 0.5 Co2O 5+δ23 、SmBa 0.5 Sr 0.5 Co2O 5+δ24 SmBaCo2O 5+δ25 、BaGd 0.8 La 0.2 Co2O 6-δ26 One or more of the following: doped Co3O4, doped Mn3O4, doped Fe3O4, WC, TiC, TaC, MoWC2, Mo2C, (Ti,Nb)3SiC2, (Ti,Cr,V)2AlC, Ti3(Si,Al)C2, Ti3(Si,Ge)C2, Ti2Al(C,N), Ti3Al(C,N)2, TiN, ZrN, VN, WN, NbN, TaN, and MoN;

[0018] Where, 0 < δ19 < 1, 0 < δ20 < 1, 0 < δ21 < 1, 0 <x3<1,0<x4<1,0<δ22<1,0<δ23<1,0<δ24<1,0<δ25<1,0<δ26<1;

[0019] And / or, the non-conductive ceramic includes one or more of Li2O, Na2O, K2O, Rb2O, Cs2O, MgO, CaO, SrO, BaO, Al2O3, Ga2O3, In2O3, La2O3, Y2O3, Yb2O3, Pr2O3, Sm2O3, and Gd2O3.

[0020] In some specific embodiments, the preparation method of the amorphous / crystalline heterojunction composite material includes:

[0021] Crystalline component solutions and amorphous component solutions were prepared separately.

[0022] The crystalline component solution and the amorphous component are mixed and then heated to a dry gel to obtain a dry gel composition.

[0023] The dry gel composition was baked until it expanded during combustion, and the resulting powder was calcined to obtain an amorphous / crystalline heterojunction composite material.

[0024] This application also provides a solid oxide fuel cell, comprising a positive electrode, an electrolyte membrane, and a negative electrode stacked sequentially, wherein the positive electrode comprises the amorphous / crystalline heterojunction composite material described in the above-described scheme, and / or the negative electrode comprises the amorphous / crystalline heterojunction composite material described in the above-described scheme.

[0025] In some specific embodiments, the solid oxide fuel cell is used in oxygen reduction reaction, hydrogen evolution reaction, oxygen absorption reaction, hydrogenation reaction, oxidative dehydrogenation reaction, or oxygen-free dehydrogenation reaction.

[0026] This application also provides a catalyst, comprising the amorphous / crystalline heterojunction composite material described above.

[0027] In some specific embodiments, the catalyst is used in hydrocarbon fuels, steam reforming, dry reforming, oxidative reforming, hydrogenation reactions, oxidative dehydrogenation reactions, or oxygen-free dehydrogenation reactions.

[0028] This application provides an amorphous / crystalline heterojunction composite material, which is composed of amorphous components and crystalline components, wherein the amorphous component is M. x R y T z The crystalline components include one or more of the following: proton-conducting oxides, oxygen-ion-conducting oxides, lithium-ion-conducting ceramics, sodium-ion-conducting ceramics, metallic materials, carbon materials, inorganic salts, electronically conductive materials, and non-conductive ceramics. In the amorphous / crystalline heterojunction composite material provided in this application, the amorphous components have unique characteristics such as disordered atomic arrangement and high-density surface defect sites. They are effectively combined with the crystalline components to construct a variety of heterojunction interfaces, which improves the catalyst activity. At the same time, the adhesion effect of the amorphous amorphous components in the amorphous / static heterojunction composite material improves the stability of the composite material. Attached Figure Description

[0029] Figure 1 The solid oxide battery electrocatalyst material La2Mo3O prepared in Example 1 of this invention 12 XRD phase diagrams after heat treatment in air and 5% H2-95% N2 atmosphere;

[0030] Figure 2 La, a solid oxide battery electrocatalyst material prepared in Example 2 of this invention. 0.15 Sr 1.78 Fe 1.72 Ni 0.1 1Mo 0.17 O 6-δ / La2Mo3O 12 XRD phase diagrams after treatment in air and 5%H2-95%Ar atmosphere;

[0031] Figure 3 La, a solid oxide battery electrocatalyst material prepared in Example 2 of this invention. 0.15 Sr 1.78 Fe 1.72 Ni 0.1 1Mo 0.17 O 6-δ / La2Mo3O 12 Transmission electron microscopy image after treatment in a 5%H2-95%Ar atmosphere;

[0032] Figure 4 La, a solid oxide battery electrocatalyst material prepared in Example 2 of this invention. 0.15 Sr 1.78 Fe 1.72 Ni 0.1 1Mo 0.17 O 6-δ and La2Mo3O 12 XRD phase diagrams of the individual and combined samples after treatment at 50% CO2-50% CO;

[0033] Figure 5 The impedance spectra of the battery in Example 3 of this invention under different atmospheres are shown. The battery skeleton is described as "porous|dense|porous", and the impregnation catalyst is La2Mo3O. 12 ;

[0034] Figure 6 The impedance spectrum of the battery in Example 3 of this invention is shown in air. The battery skeleton is described as "porous|dense|porous", and the impregnation catalyst is La2Mo3O. 12 La 0.15 Sr 1.78 Fe 1.72 Ni 0.11 Mo 0.17 O 6-δ and La 0.15 Sr 1.78 Fe 1.72 Ni 0.11 Mo 0.17 O 6-δ / La2Mo3O 12 ;

[0035] Figure 7 This is a cross-sectional scanning electron microscope (SEM) schematic diagram of the fully symmetric metal-supported oxygen ion-conducting solid oxide battery prepared in Example 4 of the present invention.

[0036] Figure 8 The image shows the carbon dioxide electrolysis performance curve of the fully symmetric metal-supported oxygen ion-conducting solid oxide battery prepared in Example 4 of this invention. The impregnation catalyst is La2Mo3O. 12 / La 0.15 Sr1.78 Fe 1.72 Ni 0.11 Mo 0.17 O 6-δ ;

[0037] Figure 9 La2Mo3O prepared in Example 4 of this invention 12 / La 0.15 Sr 1.78 Fe 1.72 Ni 0.11 Mo 0.17 O 6-δ XRD pattern of the catalyst after treatment with 10%CO-90%CO2 and 650℃ for 2 hours;

[0038] Figure 10 The voltage-current relationship of the oxygen ion conductor solid oxide battery prepared in Example 4 of this invention at 650°C is shown in the figure.

[0039] Figure 11 The chromatogram shows the carbon dioxide hydrogenation product of the oxygen ion conductor solid oxide battery prepared in Example 4 of this invention at 650°C and 0.2A.

[0040] Figure 12 This is a cross-sectional scanning electron microscope (SEM) schematic diagram of the proton-conducting solid oxide battery prepared in Example 5 of the present invention;

[0041] Figure 13 The graph shows the short-term voltage variation of the proton conductor solid oxide battery prepared in Example 5 of this invention under the conditions of 750°C and 0.1 A for methane dehydrogenation coupling.

[0042] Figure 14 The chromatogram shows the methane dehydrogenation coupling products of the proton conductor solid oxide battery prepared in Example 5 of this invention at 750°C and 0.1 A.

[0043] Figure 15 The impedance spectra of the amorphous / crystalline heterojunction composite materials prepared in Examples 6 to 11 of this invention are obtained at 650°C and under conditions of 3% H2O-97% H2. Detailed Implementation

[0044] To further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, and not for limiting the scope of the claims of the present invention.

[0045] The applicant's research revealed that amorphous materials exhibit long-range disordered atomic arrangements, resulting in high-density surface dangling bonds and abundant defect sites. This disorder in amorphous materials means that catalytic active sites are no longer confined to grain boundaries or specific crystal faces as in traditional polycrystalline materials, but rather exhibit a more uniform and higher-density distribution. This significantly expands the effective region of electrochemical reactions, equivalent to maximizing the utilization of catalyst atoms within a limited space. In this way, amorphous materials can significantly improve the catalytic activity and reaction rate of the electrode, effectively breaking through the limitations of traditional TPB volume density and achieving a leap in battery performance. Therefore, this application provides an amorphous / crystalline heterojunction composite material composed of crystalline and amorphous components, achieving an effective combination of crystalline and amorphous materials, constructing a heterogeneous interface, improving the catalytic activity of the composite material as a catalyst, and the adhesion effect of the amorphous amorphous components improves the stability of the composite material. Specifically, this invention discloses an amorphous / crystalline heterojunction composite material composed of amorphous and crystalline components.

[0046] The amorphous component is M. x R y T z M includes La and / or La-substituted ions, wherein the La-substituted ions are selected from one or more of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Ce, Y, Yb, Pr, Nd, Sm, Gd, Eu, Er, Nb, and Bi; R includes Mo and / or Mo-substituted ions, wherein the Mo-substituted ions are selected from one or more of W, V, Cr, Fe, Co, Ni, Ce, Mn, Pt, Pd, Ru, Ga, and Si; T includes O and / or O-substituted ions, wherein the O-substituted ions are selected from one or more of F, Cl, Br, I, S, Se, and N; and O <x<5;0<y<8;0<z<27;

[0047] The crystalline components include one or more of the following: proton-conducting oxides, oxygen-ion-conducting oxides, lithium-ion-conducting ceramics, sodium-ion-conducting ceramics, metallic materials, carbon materials, inorganic salts, electronically conductive materials, and non-conductive ceramics.

[0048] In the amorphous / crystalline heterojunction composite material provided in this application, in some specific embodiments, M includes La, or La and La-substituted ions; wherein the La-substituted ions are selected from one or more of Pr, Sr, Ce, and Y. In some specific embodiments, R includes Mo, or Mo and Mo-substituted ions; wherein the Mo-substituted ions are selected from one or two of V and Fe. In some specific embodiments, T is selected from O. In the amorphous component, the ternary La ion at the M site has a similar radius to other ions and can be substituted equally to form a similar structure; the low-valence ions at the R site can generate more oxygen vacancies through electron transfer. x can specifically be 1, 2, 3, 4, y can specifically be 1, 2, 3, 4, 5, 6, 7, and z can specifically be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26.

[0049] In some specific embodiments, the amorphous component is La2Mo3O. 12 LaPr 0.5 Sr 0.5 MoFeO9, LaFeMo3O 12 LaCeMo3O 12 、LaYMoVFeO 12 La2MoVO9, La2MoFeO9.

[0050] In the amorphous components, ions such as Fe, Co, Ni, Pt, Pd, Ru, and Ce precipitate as single atoms or clusters under conditions such as reducing atmosphere or high voltage.

[0051] The crystalline components include one or more of the following: proton-conducting oxides, oxygen-ion-conducting oxides, lithium-ion-conducting ceramics, sodium-ion-conducting ceramics, metallic materials, carbon materials, inorganic salts, electronically conductive materials, and non-conductive ceramics; further, in some specific embodiments, the proton-conducting oxide includes CeO-doped CeO. 2-δ1 doped BaZrO 3-δ2 doped BaCeO 3-δ3 Sr2Sc 1+m1 Nb 1-n1 O 6-δ4 BaZr 0.4 Sc 0.6 O 3-δ5 Ba3Ca 1+m2 Nb 2-n2 O9、BaSn 0.3 Sc 0.7 O 3-δ6 BaTi 0.2 Sc 0.8 O3-δ7 La 5.5 WO 11.25-δ8 and Ba5R2Al2SnO 13 One or more of the following;

[0052] Among them, 0<δ1<1, 0<δ2<1, 0<δ3<1, 0<δ4<1, 0<δ5<1, 0<δ6<1, 0<δ7<1, 0<δ8<1;

[0053] 0 <m1<1,0<n1<1,0<m2<1,0<n2<1;

[0054] R is selected from one or more of Gd, Dy, Ho, Y, Er, Tm, and Yb.

[0055] The values ​​δ1 to δ8 mentioned above are non-stoichiometric coefficients, corresponding to the slight absence or excess of oxygen atoms in proton-conducting oxides, reflecting the defect concentration of the corresponding proton-conducting oxides. Similarly, m1, n1, m2, and n2 are also non-stoichiometric coefficients, corresponding to the Sr2Sc atoms in proton-conducting oxides, respectively. 1+m1 Nb 1-n1 O 6-δ4 Trace deficiencies or excesses of Sc and Nb, Ba3Ca 1+m2 Nb 2-n2 Trace amounts of Ca and Nb are missing or excessive in O9.

[0056] The oxygen ion-conducting oxide includes doped ZrO. 2-δ9 doped Bi2O 3-δ10 La2Mo2O doped 9-δ11 doped SrFeO 3-δ12 LaGaO doped 3-δ13 La2NiO 4+δ14 Pr2NiO 4+δ15 Nd2NiO 4+δ16 La4Ni3O 10+δ17 and La 1+x1 Sr 1- x2 Ga3O 7.5-δ18 One or more of the following; wherein, 0 < δ9 < 1, 0 < δ10 < 1, 0 < δ11 < 1, 0 < δ12 < 1, 0 < δ13 < 1, 0 < δ14 < 1, 0 < δ15 < 1, 0 < δ16 < 1, 0 < δ17 < 1, 0 < δ18 < 1, 0 <x1<1,0<x2<1。

[0057] The values ​​δ9 to δ18 mentioned above are non-stoichiometric coefficients, corresponding to the slight absence or excess of oxygen atoms in oxygen ion-conducting oxides, reflecting the defect concentration of the corresponding oxygen ion-conducting oxides. Similarly, x1 and x2 are also non-stoichiometric coefficients, corresponding to the La atoms in proton-conducting oxides. 1+x1 Sr 1-x2 Ga3O 7.5-δ18 The trace amounts or excesses of La and Sr are present.

[0058] The lithium-ion conductive ceramic includes FeLiPO4 and Li 1.3 Al 0.7 Ti 1.7 (PO4)3, doped Li7La3Zr2O 12 and one or more of doped LiTiO3; the sodium ion conducting ceramic includes Na3Zr2Si2PO4. 12 Na 3.4 Zr 1.8 Mg 0.2 Si 2.4 P 0.6 O 12 and Na 3.2 Zr 1.8 Tb 0.2 Si2PO 12 One or more of the following: the metallic material includes one or more of Ni, Cu, Fe, Co, FeNi3, 430L and 440 stainless steel; the carbon material includes one or more of graphite, graphene and doped graphene.

[0059] The inorganic salt includes one or more of Li₂CO₃, Na₂CO₃, K₂CO₃, SrCO₃, and BaCO₃; the electron-conducting material includes (La,Ba,Sr)(Cr,Mo,Fe,Co,Ni,Mg,Mn)O. 3-δ19 La(Ni,Fe)O 3-δ20 (La,Sr)(Ti,Fe,Co,Ni)O 3-δ21 、(Sm 1-x3 Sr x4 CoO 3-δ22 LaBa 0.5 Sr 0.5 Co2O 5+δ23 、SmBa 0.5 Sr 0.5 Co2O 5+δ24 SmBaCo2O 5+δ25 、BaGd 0.8 La 0.2 Co2O 6-δ26One or more of the following doped materials: Co3O4, Mn3O4, Fe3O4, WC, TiC, TaC, MoWC2, Mo2C, (Ti,Nb)3SiC2, (Ti,Cr,V)2AlC, Ti3(Si,Al)C2, Ti3(Si,Ge)C2, Ti2Al(C,N), Ti3Al(C,N)2, TiN, ZrN, VN, WN, NbN, TaN, and MoN; wherein 0 < δ19 < 1, 0 < δ20 < 1, 0 < δ21 < 1, 0 < δ22 < 1, 0 < δ23 < 1, 0 < δ24 < 1, 0 < δ25 < 1, 0 < δ26 < 1, 0 < δ27 < 1, 0 < δ28 < 1, 0 < δ29 < 1, 0 < δ21 < 1, 0 < δ29 ...1 < 1, 0 < δ29 < 1, 0 < δ21 < 1, 0 < δ29 < 1, 0 < δ21 < 1, 0 < δ29 < 1, 0 < δ21 < 1, 0 < δ29 < 1, 0 < δ21 < 1, 0 < δ29 < 1, 0 < δ21 < 1, 0 < δ29 < <x3<1,0<x4<1,0<δ22<1,0<δ23<1,0<δ24<1,0<δ25<1,0<δ26<1。

[0060] The values ​​δ19 to δ26 mentioned above are non-stoichiometric coefficients, corresponding to the minute absence or excess of oxygen atoms in the electron-conducting material, reflecting the defect concentration of the corresponding oxygen electron-conducting material. Similarly, x3 and x4 are also non-stoichiometric coefficients, corresponding to the presence of (Sm) atoms in the electron-conducting material. 1-x3 Sr x4 CoO 3-δ22 The trace amounts or excesses of Sm and Sr in the medium.

[0061] The non-conductive ceramics include one or more of Li2O, Na2O, K2O, Rb2O, Cs2O, MgO, CaO, SrO, BaO, Al2O3, Ga2O3, In2O3, La2O3, Y2O3, Yb2O3, Pr2O3, Sm2O3, and Gd2O3.

[0062] For the aforementioned crystalline components, the term "doped" indicates that the matrix material is also doped with other elements. The selection of these doping elements is based on elements well-known to those skilled in the art, as long as it does not affect the crystal state of the material. The aforementioned (La,Ba,Sr)(Cr,Mo,Fe,Co,Ni,Mg,Mn)O 3-δ This indicates that the material contains La, Ba, and Sr as a component, including all three components without specifying their proportions; similarly, it contains Cr, Mo, Fe, Co, Ni, Mg, and Mn as a component, including all three components without specifying their proportions; and also, La(Ni,Fe)O 3-δ (La,Sr)(Ti,Fe,Co,Ni)O 3-δ The descriptions of (Ti,Nb)3SiC2, (Ti,Cr,V)2AlC, Ti3(Si,Al)C2, Ti3(Si,Ge)C2, Ti2Al(C,N), and Ti3Al(C,N)2 are the same as those above, and will not be repeated here.

[0063] In some specific embodiments, the crystalline component is selected from doped SrFeO. 3-δ Ni, Cu, and doped CeO 2-δ Ti3(Si,Al)C2 or graphene.

[0064] In the amorphous / crystalline heterojunction composite material of this application, the volume fraction of the amorphous component in the composite material is 0.1% to 99.9%. Specifically, the volume fraction of the amorphous component in the composite material is 1% to 85%, more specifically, the volume fraction of the amorphous component in the composite material is 8% to 75%, more specifically, the volume fraction of the amorphous component in the composite material is 12% to 70%, more specifically, the volume fraction of the amorphous component in the composite material is 18% to 60%, more specifically, the volume fraction of the amorphous component in the composite material is 25% to 45%, and more specifically, the matrix fraction of the amorphous component in the composite material is 28% to 40%. In specific embodiments, the optimal doping ratio is selected according to different tests; therefore, the volume fraction of the composite is constantly changing.

[0065] Furthermore, the preparation method of the amorphous / crystalline heterojunction composite material described in this application includes:

[0066] Crystalline component solutions and amorphous component solutions were prepared separately.

[0067] The crystalline component solution and the amorphous component are mixed and then heated to a dry gel to obtain a dry gel composition.

[0068] The dry gel composition is baked until it expands due to combustion, the resulting powder is calcined, and then heat-treated to obtain an amorphous / crystalline heterojunction composite material.

[0069] In the amorphous / crystalline heterojunction composite material, crystalline component solutions and amorphous component solutions are first prepared separately. The crystalline component solution is obtained by heating and stirring in an acidic solution after preparing the components according to their respective proportions. Similarly, the amorphous component solution is obtained by heating and stirring in an acidic solution after preparing the components according to their respective proportions. Baking is performed to allow the dry gel to fully expand and burn. Calcination is then performed to obtain the crystalline composite material. Finally, heat treatment is performed to transform the amorphous components in the crystalline composite material, resulting in the amorphous / crystalline heterojunction composite material.

[0070] This application also provides a solid oxide fuel cell, comprising a positive electrode, an electrolyte membrane, and a negative electrode stacked sequentially, wherein the positive electrode comprises the amorphous / crystalline heterojunction composite material described in the above-described scheme, and / or the negative electrode comprises the amorphous / crystalline heterojunction composite material described in the above-described scheme.

[0071] In a solid oxide fuel cell, the positive electrode comprises an amorphous / crystalline heterojunction composite material, or the negative electrode comprises an amorphous / crystalline heterojunction composite material, or both the positive and negative electrodes comprise an amorphous / crystalline heterojunction composite material.

[0072] Furthermore, the structure of the solid oxide fuel cell includes, in sequence: a negative electrode support layer, a negative electrode transition layer, an electrolyte membrane, a positive electrode transition layer, and a positive electrode support layer, wherein the negative electrode support layer and the positive electrode support layer are loaded with the above-mentioned amorphous / crystalline heterojunction composite material, and the loading amount of the amorphous / crystalline heterojunction composite material in the negative electrode support layer and the positive electrode support layer is 8~12wt%.

[0073] Alternatively, the solid oxide fuel cell may be structured as follows: a positive electrode, an electrolyte membrane, and a negative electrode, wherein the catalyst of the negative electrode comprises the aforementioned amorphous / crystalline heterojunction composite material, and the loading of the amorphous / crystalline heterojunction composite material on the negative electrode is 20~30wt%.

[0074] Alternatively, the solid oxide fuel cell structure may include, in sequence, a negative electrode, an electrolyte membrane, and a positive electrode, wherein the catalyst of the positive electrode comprises the aforementioned amorphous / crystalline heterojunction composite material, and the loading of the amorphous / crystalline heterojunction composite material on the positive electrode is 20~30wt%.

[0075] The amorphous / crystalline heterojunction composite materials in the aforementioned solid oxide fuel cells are used for oxidative reactions, oxygen absorption reactions, hydrogen evolution reactions, electrochemical oxidation reactions of fuels such as H2, CO, CH4, C2H6, C3H8, CH3OH, C2H5OH, CH3COOH, and NH3, electrochemical reduction reactions of water vapor and / or carbon dioxide, hydrogenation reactions of CO, CO2, N2, and olefins, and oxidative dehydrogenation and oxygen-free dehydrogenation reactions of alkanes such as CH4, C2H6, and C3H8.

[0076] This application also provides a catalyst comprising the amorphous / crystalline heterojunction composite material described above. Specifically, the amorphous / crystalline heterojunction composite material can be directly used as a catalyst for CH4, C2H6, C3H8, and C4H4. 10 Catalysts for hydrocarbon fuels such as CH3OH, C2H5OH, and CH3COOH; catalysts for steam reforming of alcohols and organic acids; catalysts for CO2 dry reforming and partial oxidative reforming reactions; catalysts for hydrogenation reactions of CO, CO2, N2, and alkenes; and catalysts for thermochemical processes such as oxidative dehydrogenation and oxygen-free dehydrogenation reactions of alkanes such as CH4, C2H6, and C3H8.

[0077] This application provides an amorphous / crystalline heterojunction composite material, wherein the effective combination of crystalline and amorphous materials constructs a heterogeneous interface, which enhances the catalytic activity of the composite material, while the adhesion of the amorphous state improves the stability of the crystalline material.

[0078] To further understand the present invention, the following detailed description of the amorphous / crystalline heterojunction composite material and its applications provided by the present invention is provided in conjunction with embodiments. The scope of protection of the present invention is not limited by the following embodiments.

[0079] Example 1: La2Mo3O 12 Solid-phase reaction synthesis of amorphous catalysts

[0080] 1) According to La2Mo3O 12 La2O3 and MoO3 were weighed according to their stoichiometric ratio and ball-milled in a ball mill jar for 48 hours using ethanol as the medium.

[0081] 2) Filter the obtained suspension with filter paper and then dry it in an oven at 80℃;

[0082] 3) The dried mixture was thoroughly ground and calcined in air at 850°C for 2 hours to obtain crystalline La2Mo3O. 12 Catalyst materials, XRD patterns as follows Figure 1 As shown by curve a;

[0083] 4) The above-mentioned crystalline catalyst material was placed in a tube furnace and heat-treated at 5% H2-95% N2 and 650℃ for 2 hours to obtain an amorphous catalyst material. The XRD pattern is shown below. Figure 1 As shown by curve b.

[0084] Example 2: Amorphous La2Mo3O 12 With crystalline La 0.15 Sr 1.78 Fe 1.72 Ni 0.11 Mo 0.17 O 6-δ Liquid-phase synthesis of heterojunction composite catalysts

[0085] 1) According to La 0.15 Sr 1.78 Fe 1.72 Ni 0.11 Mo 0.17 O 6-δ The stoichiometric ratio of La(NO3)3·6H2O, Sr(NO3)2, Fe(NO3)3·9H2O, Ni(NO3)2·6H2O, and (NH4)6Mo7O is given by (0 < δ < 1). 24Dissolve 4H2O in deionized water, stir well, add an appropriate amount of citric acid, heat and stir until well mixed;

[0086] 2) According to La2Mo3O 12 The stoichiometric ratio of La(NO3)3·6H2O and (NH4)6Mo7O is given. 24 Dissolve 4H2O in deionized water, stir well, add an appropriate amount of citric acid, heat and stir until well mixed;

[0087] 3) Mix the two solutions according to La 0.15 Sr 1.78 Fe 1.72 Ni 0.11 Mo 0.17 O 6-δ La2Mo3O 12 The mixture was prepared with a volume fraction of 84:16 and heated and stirred until it reached a dry gel state.

[0088] 4) Bake the obtained dry gel in an oven at 200℃ for 12 hours to allow for complete combustion and expansion;

[0089] 5) The expanded powder was thoroughly ground and calcined in air at 650°C for 2 hours to obtain a crystalline catalyst material. The XRD pattern is shown below. Figure 2 As shown by curve a, the composite material consists of crystalline La2Mo3O 12 With crystalline La 0.15 Sr 1.78 Fe 1.72 Ni 0.11 Mo 0.17 O 6-δ (0 < δ < 1) constitutes.

[0090] 6) The above-mentioned crystalline catalyst material was placed in a tube furnace and heat-treated at 5% H2-95% Ar and 600℃ for 2 hours to obtain an amorphous / crystalline heterojunction composite catalyst material. The XRD pattern is shown below. Figure 2 As shown by curve b, the reduced composite material consists of amorphous La2Mo3O 12 Reduced crystalline La 0.15 Sr 1.78 Fe 1.72 Ni 0.11 Mo 0.17 O 6-δ (0 < δ < 1) and FeNi3 nanocrystals; transmission electron microscopy (TEM) images of the amorphous / crystalline heterostructure interface are shown below. Figure 3 As shown;

[0091] 7) The XRD pattern of the powder obtained in step 5) after treatment under 50% CO2-50% CO is shown in the figure. Figure 4As shown in curve a, the XRD pattern of the powder obtained by baking the solutions from 1) and 2) separately according to the above operation without mixing, after treatment under 50% CO2-50% CO, is shown in curve a. Figure 4 Curves b and c show the amorphous state of La2Mo3O. 12 and the reduced crystalline La 0.15 Sr 1.78 Fe 1.72 Ni 0.11 Mo 0.17 O 6-δ (0 < δ < 1) The composite stabilized the crystalline La 0.15 Sr 1.78 Fe 1.72 Ni 0.11 Mo 0.17 O 6-δ (0 < δ < 1) phase structure.

[0092] Example 3: A method based on amorphous La2Mo3O 12 Catalyst-driven oxygen ion conductor electrolyte self-supporting solid oxide electrolyzer

[0093] The electrolyte membrane in this embodiment is (Sc2O3). 0.06 (ZrO2) 0.94 Both the positive and negative electrodes have a porous (Sc2O3) framework. 0.06 (ZrO2) 0.94 The active catalysts for both the positive and negative electrodes are La2Mo3O 12 Battery fabrication includes the following steps:

[0094] 1) (Sc2O3) 0.06 (ZrO2) 0.94 Ceramic powder was added to a ball mill, followed by a two-component solvent of xylene and butyl acetate, and an acrylic resin dispersant. After ball milling for 24 hours, a binder of polyvinyl butyral and a plasticizer of polyethylene glycol and / or diethyl phthalate were added. The mixture was ball milled again for 24 hours to obtain a highly dispersed and uniform cast slurry. After filtration and degassing, the slurry was cast onto a Mylar membrane and dried at 30-60℃ to obtain a 70 μm thick (Sc2O3) film. 0.06 (ZrO2) 0.94 Electrolyte diaphragm green blank;

[0095] 2) (Sc2O3) 0.06 (ZrO2) 0.94 After isostatic pressing of the electrolyte membrane green blanks, they are sintered at 1400℃ for 10 hours to obtain an electrolyte sheet with a thickness of 200 micrometers.

[0096] 3) (Sc2O3) 0.06 (ZrO2)0.94 Ceramic powder, graphite, and starch were added to a mortar, along with ethyl cellulose and terpineol. After grinding for 3 hours, the mixture was screen-printed onto both sides of an electrolyte sheet. The sheet was then sintered at 1350℃ for 10 hours to obtain "porous|dense|porous" (Sc2O3). 0.06 (ZrO2) 0.94 ;

[0097] 4) The La2Mo3O from Example 2 12 The precursor solution is dropped onto porous (Sc2O3). 0.06 (ZrO2) 0.94 In the framework, calcination at 650℃ forms the phase, and repeated impregnation and calcination result in La2Mo3O 12 The solid content of the catalyst reaches 7.5%.

[0098] La2Mo3O was measured at 650℃ under different atmospheres. 12 The performance of catalytic symmetric cells, such as Figure 5 As shown, the test results indicate that La2Mo3O 12 The catalyst exhibits a significantly lower resistivity under a reducing atmosphere compared to an oxidizing atmosphere, indicating that the electrochemical oxidation reaction of hydrogen and carbon monoxide is effective for amorphous La₂Mo₃O₃. 12 It exhibits high catalytic activity in the electrochemical reduction reactions of water vapor and carbon dioxide;

[0099] 5) The La2Mo3O from Example 2 12 Precursor solution, La 0.15 Sr 1.78 Fe 1.72 Ni 0.11 Mo 0.17 O 6-δ (0 < δ < 1) precursor solution and La 0.15 Sr 1.78 Fe 1.72 Ni 0.11 Mo 0.17 O 6-δ / La2Mo3O 12 The precursor solution was dropped onto porous (Sc2O3) substrates. 0.06 (ZrO2) 0.94 In the skeleton, calcination at 650℃ forms a phase, and multiple impregnation and calcination processes result in a solid content of 7.5% for the catalyst.

[0100] By introducing an air atmosphere, the La2Mo3O content was measured at 650°C. 12 La 0.15 Sr 1.78 Fe 1.72 Ni 0.11 Mo 0.17 O6-δ and La 0.15 Sr 1.78 Fe 1.72 Ni 0.11 Mo 0.17 O 6-δ / La2Mo3O 12 The performance of catalytic symmetric cells, such as Figure 6 As shown, the test results indicate that La 0.15 Sr 1.78 Fe 1.72 Ni 0.11 Mo 0.17 O 6-δ (0 < δ < 1) / La2Mo3O 12 The catalyst, compared to La2Mo3O in an air atmosphere 12 and La 0.15 Sr 1.78 Fe 1.72 Ni 0.11 Mo 0.17 O 6-δ The resistance decreases significantly when (0 < δ < 1), indicating that the amorphous La2Mo3O 12 With crystalline La 0.15 Sr 1.78 Fe 1.72 Ni 0.11 Mo 0.17 O 6-δ (0 < δ < 1) After recombination, it has high catalytic activity for the electrochemical reduction reaction of oxygen conduction.

[0101] Example 4: A method based on amorphous La2Mo3O 12 With crystalline La 0.15 Sr 1.78 Fe 1.72 Ni 0.11 Mo 0.17 O 6-δ Metal-supported oxygen ion conductor solid oxide electrolyzer with composite catalyst

[0102] The electrolyte membrane in this embodiment is (Sc2O3). 0.06 (ZrO2) 0.94 The transition layer between the positive and negative electrodes is made of porous stainless steel (Sc2O3). 0.06 (ZrO2) 0.94 Both the positive and negative electrode supports are made of porous 430L stainless steel, and the active catalysts for both the positive and negative electrodes are La2Mo3O. 12 / La 0.15 Sr 1.78 Fe 1.72 Ni 0.11 Mo 0.17 O6-δ Battery fabrication includes the following steps:

[0103] 1) Add 430L stainless steel and ammonium oxalate to a ball mill barrel at a weight ratio of 70:30, then add xylene and butyl acetate as a two-component solvent and acrylic resin dispersant. After ball milling for 24 hours, add the binder polyvinyl butyral and the plasticizer polyethylene glycol and / or diethyl phthalate, and ball mill again for 24 hours to obtain a highly dispersed and uniform cast slurry. After filtration and degassing, the slurry is cast on a Mylar membrane and dried at 30-60℃ to obtain a 70μm thick stainless steel membrane preform, which is used as the negative electrode support layer preform and the positive electrode support layer preform, respectively.

[0104] 2) Mix 430L stainless steel and (Sc2O3) in a weight ratio of 50:50:10. 0.06 (ZrO2) 0.94 Ammonium oxalate was added to the ball mill, followed by xylene and butyl acetate as a two-component solvent and an acrylic resin dispersant. After ball milling for 24 hours, polyvinyl butyral (PVB) as a binder and polyethylene glycol and / or diethyl phthalate as a plasticizer were added, and the mixture was ball milled again for 24 hours to obtain a highly dispersed and uniform cast slurry. After filtration and degassing, the slurry was cast onto a Mylar membrane and dried at 30-60℃ to obtain a 20μm thick 430L stainless steel-(Sc2O3) film. 0.06 (ZrO2) 0.94 The green blanks are used as green blanks for the negative electrode transition layer and green blanks for the positive electrode transition layer, respectively.

[0105] 3) (Sc2O3) 0.06 (ZrO2) 0.94 Ceramic powder was added to a ball mill, followed by a two-component solvent of xylene and butyl acetate, and an acrylic resin dispersant. After ball milling for 24 hours, a binder of polyvinyl butyral and a plasticizer of polyethylene glycol and / or diethyl phthalate were added. The mixture was ball milled again for 24 hours to obtain a highly dispersed and uniform cast slurry. After filtration and degassing, the slurry was cast onto a Mylar membrane and dried at 30-60℃ to obtain a 15μm thick (Sc2O3) film. 0.06 (ZrO2) 0.94 Electrolyte diaphragm green blank;

[0106] 4) According to the "3-layer 430L stainless steel negative electrode support layer green blank | 2-layer stainless steel-(Sc2O3)" 0.06 (ZrO2) 0.94 Negative electrode transition layer green body | 1 layer (Sc2O3) 0.06 (ZrO2) 0.94 Electrolyte diaphragm green blank | 2-layer stainless steel (Sc2O3) 0.06 (ZrO2) 0.94The positive electrode transition layer green blank | 3 layers of 430L stainless steel positive electrode support layer green blank are stacked in the manner of "the positive electrode transition layer green blank | 3 layers of 430L stainless steel positive electrode support layer green blank", and after isostatic pressing, they are sintered in a tube furnace at 1375℃ for 24 hours under a 10% hydrogen-argon atmosphere to obtain a fully symmetrical metal-supported single cell.

[0107] 5) The La2Mo3O from Example 2 12 / La 0.15 Sr 1.78 Fe 1.72 Ni 0.11 Mo 0.17 O 6-δ (0 < δ < 1) The precursor solution of the composite catalyst was impregnated in the porous electrode framework with a loading of 10%, and sintered at 650℃ to form a phase. Figure 7 Here is a scanning electron microscope (SEM) image of the fully symmetric metal-supported single cell prepared using the above steps; Figure 7 It can be seen that the fully symmetrical metal-supported single cell prepared in this embodiment has good bonding between each layer and good bonding force between each layer;

[0108] Air is introduced to the anode side, and carbon dioxide is introduced to the cathode side. Figure 8 The electrolytic cell curves for carbon dioxide electrolysis are shown in the range of 650–550 °C. The electrolysis voltage is 1.5 V, and the current densities at 650, 600, and 550 °C are 2.80, 1.57, and 0.71 A / cm², respectively. 2 Therefore, it can be seen that the solid oxide electrolytic cell prepared in this embodiment achieves excellent performance in electrolyzing carbon dioxide at medium and low temperatures.

[0109] Figure 9 La2Mo3O 12 / La 0.15 Sr 1.78 Fe 1.72 Ni 0.11 Mo 0.17 O 6-δ The XRD pattern after treatment with 10% CO-90% CO2 at 650℃ for 2 hours indicates that the composite catalyst consists of amorphous, non-crystalline La2Mo3O4. 12 And crystalline La 0.18 Sr 1.21 Fe 1.68 Ni 0.11 Mo 0.21 O 6-δ It is composed of (0 < δ < 1), SrCO3, and FeNi3.

[0110] Hydrogen gas is introduced into the positive electrode of the battery obtained in step 5), and hydrogen gas is first introduced into the negative electrode for 2 hours, and then switched to 33.3%CO2-66.7%H2O. Figure 10 This is a graph showing the voltage-current relationship of the battery at 650℃. Figure 11 The tail gas chromatographic analysis of the negative electrode under conditions of 650℃ and 0.2A shows that the battery prepared in this embodiment can undergo carbon dioxide hydrogenation to produce methane.

[0111] Example 5: A method based on amorphous La 1.8 Sr 0.2 Mo 2.9 Fe 0.1 O 12 -Crystal BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ Proton conductor solid oxide battery with catalyst

[0112] The electrolyte diaphragm in this implementation example is BaZr. 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3–δ The negative electrode is NiO-BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ (0 < δ < 1), the positive electrode framework is porous BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ The positive electrode catalyst is amorphous La. 1.8 Sr 0.2 Mo 2.9 Fe 0.1 O 12 Battery fabrication includes the following steps:

[0113] 1) According to the weight ratio of 51:34:15, NiO and BaZr are mixed... 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ (0 < δ < 1) and graphite powder were added to a ball mill, followed by a two-component solvent of xylene and butyl acetate, and an acrylic resin dispersant. After ball milling for 24 hours, a binder and plasticizer were added, and the mixture was ball milled again for 24 hours to obtain a highly dispersed and uniform cast slurry. After filtration and degassing, the slurry was cast onto a Mylar membrane and dried to obtain a 70-micron thick NiO-BaZr film. 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ (0 < δ < 1) Negative electrode green blank;

[0114] 2) BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ (0 < δ < 1) Ceramic powder was added to a ball mill, followed by a two-component solvent of xylene and butyl acetate, and an acrylic resin dispersant. After ball milling for 24 hours, a binder and plasticizer were added, and the mixture was ball milled again for 24 hours to obtain a highly dispersed and uniform cast slurry. The slurry was filtered, degassed, cast onto a Mylar membrane, and dried to obtain a 15-micron thick BaZr film. 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ (0 < δ < 1) Electrolyte diaphragm green blank;

[0115] 3) According to a weight ratio of 40:60, mix BaZr... 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ (0 < δ < 1) and graphite powder were added to a ball mill, followed by a two-component solvent of xylene and butyl acetate, and an acrylic resin dispersant. After ball milling for 24 hours, a binder and plasticizer were added, and the mixture was ball milled again for 24 hours to obtain a highly dispersed and uniform cast slurry. After filtration and degassing, the slurry was cast onto a Mylar membrane and dried to obtain a 25-micron-thick porous BaZr film. 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ (0 < δ < 1) Positive electrode framework green blank;

[0116] 4) According to the "8-layer NiO-BaZr" 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ (0 < δ < 1) Negative electrode green blank | 1 layer of BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ Electrolyte membrane preform | 1-layer porous BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ (0<δ<1) Positive electrode framework green blank is stacked in a way that isostatically pressed and then sintered in air at 1450℃ for 10 hours to obtain a negative electrode supported battery.

[0117] 5) According to La 1.8 Sr0.2 Mo 2.9 Fe 0.1 O 12 The stoichiometric ratio of La(NO3)3·6H2O, Sr(NO3)2, and NH4)6Mo7O is given. 24 ·4H2O and Fe(NO3)3·9H2O were dissolved in deionized water, stirred evenly, and then an appropriate amount of citric acid was added and heated and stirred to obtain a precursor solution.

[0118] 6) La 1.8 Sr 0.2 Mo 2.9 Fe 0.1 O 12 The precursor solution was loaded onto porous, crystalline BaZr via impregnation. 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ (0 < δ < 1) In the positive electrode framework, the loading is 5%, and it is sintered at 650℃ to form amorphous La. 1.8 Sr 0.2 Mo 2.9 Fe 0.1 O 12 / Crystal BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ (0 < δ < 1) composite phase, Figure 12 This is a scanning electron microscope (SEM) image of the battery's microstructure.

[0119] Hydrogen gas is introduced into the negative electrode, and hydrogen gas is first introduced into the positive electrode for 2 hours before switching to dried methane. Figure 13 The figure shows the short-term voltage change of the battery under methane dehydrogenation coupling conditions at 750℃ and 0.1A. The voltage gradually decreases, indicating electrode activation. Figure 14 The tail gas chromatography analysis of the positive electrode showed that methane dehydrogenated and coupled to produce ethane and ethylene.

[0120] Example 6: A method based on amorphous LaPr 0.5 Sr 0.5 Solid oxide batteries using MoFeO9-crystalline Ni composite catalysts

[0121] The electrolyte diaphragm in this implementation example is La. 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3-δ The framework of the positive and negative electrodes is porous La. 0.9 Sr 0.1 Ga0.8 Mg 0.2 O 3-δ (0 < δ < 1), the positive electrode catalyst is nano-SmBa 0.5 Sr 0.5 Co2O5, with crystalline nano-Ni-amorphous LaPr as the negative electrode catalyst. 0.5 Sr 0.5 MoFeO9, the battery preparation includes the following steps:

[0122] 1) La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3-δ (0 < δ < 1) Ceramic powder was added to a ball mill, followed by a two-component solvent of xylene and butyl acetate, and an acrylic resin dispersant. After ball milling for 24 hours, a binder of polyvinyl butyral and a plasticizer of polyethylene glycol and / or diethyl phthalate were added. The mixture was ball milled again for 24 hours to obtain a highly dispersed and uniform cast slurry. After filtration and degassing, the slurry was cast onto a Mylar membrane and dried at 30-60℃ to obtain a 15 μm thick La film. 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3-δ (0 < δ < 1) Electrolyte diaphragm green blank;

[0123] 2) According to a weight ratio of 60:40, La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3-δ Ceramic powder and graphite powder were added to a ball mill, along with a two-component solvent of xylene and butyl acetate, and an acrylic resin dispersant. After ball milling for 24 hours, a binder and plasticizer were added, and the mixture was ball milled again for 24 hours to obtain a highly dispersed and uniform cast slurry. The slurry was filtered, degassed, cast onto a Mylar membrane, and dried to obtain a 60-micron-thick porous La... 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3-δ (0 < δ < 1) green blank;

[0124] 3) According to "6-layer porous La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3-δ (0 < δ < 1) Green body | 1 layer La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O3-δ (0 < δ < 1) Electrolyte membrane green body | 6-layer porous La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3-δ The green blanks were stacked in a manner of "0 < δ < 1", and after isostatic pressing, they were sintered in air at 1400℃ for 6 hours to obtain "porous|dense|porous" La. 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3-δ skeleton;

[0125] 4) According to SmBa 0.5 Sr 0.5 To obtain the precursor solution, Sm(NO3)3·6H2O, Ba(NO3)2, Sr(NO3)2, and Co(NO3)3·9H2O were dissolved in deionized water, and an appropriate amount of citric acid was added and the mixture was heated and stirred.

[0126] 5) Place SmBa 0.5 Sr 0.5 A Co2O5 precursor solution was impregnated onto a porous La substrate on one side of the battery. 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3-δ (0 < δ < 1) In the skeleton, the loading is 25%, and it is sintered in air at 800°C to form a phase;

[0127] 6) According to 50% LaPr 0.5 Sr 0.5 The weight ratio of MoFeO is 9-50%NiO, with La(NO3)3·6H2O, Pr(NO3)3·6H2O, Sr(NO3)2, and (NH4)6Mo7O. 24 ·4H2O, Fe(NO3)3·9H2O, and Ni(NO3)2·6H2O are dissolved in deionized water, and appropriate amounts of citric acid and ethylenediaminetetraacetic acid are added. The mixture is heated and stirred to obtain a precursor solution.

[0128] 7) Add 50% LaPr 0.5 Sr 0.5 A precursor solution of MoFeO9-50%NiO was impregnated onto porous La on the other side of the battery. 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3-δ(0 < δ < 1) In the skeleton, the loading is 20%, and it is sintered in air at 700°C to form a phase;

[0129] At 700°C, air is introduced at the positive electrode and hydrogen is introduced at the negative electrode. LaPr 0.5 Sr 0.5 MoFeO9 transforms into an amorphous state, while NiO is reduced to crystalline Ni, thus yielding amorphous LaPr. 0.5 Sr 0.5 MoFeO9-crystalline Ni composite catalyst.

[0130] Example 7 A method based on amorphous LaFeMo3O 12 - Solid oxide batteries with crystalline Cu composite catalysts

[0131] The electrolyte membrane in this embodiment is (Sc2O3). 0.06 (ZrO2) 0.94 The negative electrode is Ni-(Sc2O3). 0.06 (ZrO2) 0.94 The positive electrode is amorphous LaFeMo3O 12 - Crystalline Cu, the battery fabrication process includes the following steps:

[0132] 1) Mix NiO and (Sc2O3) in a weight ratio of 51:34:15. 0.06 (ZrO2) 0.94 Graphite powder was added to a ball mill, along with a two-component solvent of xylene and butyl acetate, and an acrylic resin dispersant. After ball milling for 24 hours, a binder and plasticizer were added, and the mixture was ball milled again for 24 hours to obtain a highly dispersed and uniform cast slurry. The slurry was filtered, degassed, cast onto a Mylar membrane, and dried to obtain a 70-micron thick NiO-(Sc2O3). 0.06 (ZrO2) 0.94 Negative electrode green blank;

[0133] 2) (Sc2O3) 0.06 (ZrO2) 0.94 Ceramic powder was added to a ball mill, followed by a two-component solvent of xylene and butyl acetate, and an acrylic resin dispersant. After ball milling for 24 hours, a binder and plasticizer were added, and the mixture was ball milled again for 24 hours to obtain a highly dispersed and uniform cast slurry. The slurry was filtered, degassed, cast onto a Mylar membrane, and dried to obtain a 15-micron thick (Sc2O3) film. 0.06 (ZrO2) 0.94 Electrolyte diaphragm green blank;

[0134] 3) According to "8 layers of NiO-(Sc2O3)" 0.06 (ZrO2) 0.94 Negative electrode green body | 1 layer (Sc2O3)0.06 (ZrO2) 0.94 The electrolyte membrane is stacked in a "green" manner, and after isostatic pressing, it is sintered in air at 1400°C for 10 hours to obtain a negative electrode supported half cell.

[0135] 4) According to 50% LaFeMo3O 12 -50% CuO by weight, mix CuO and LaFeMo3O 12 The powder was added to a mortar, along with ethyl cellulose and terpineol. After grinding for 3 hours, the powder was screen-printed onto the electrolyte membrane of a half-cell and sintered in air at 850°C for 6 hours to obtain crystalline CuO and crystalline LaFeMo3O. 12 The positive electrode is composed of;

[0136] 5) At 600℃, 10% H2-90% H2O is introduced into the negative electrode, and 50% H2-50% H2O is introduced into the positive electrode first, followed by 25% CH4-75% H2O, NiO-(Sc2O3). 0.06 (ZrO2) 0.94 The negative electrode is reduced to Ni-(Sc2O3). 0.06 (ZrO2) 0.94 In the positive electrode, CuO is reduced to Cu, while LaFeMo3O 12 It transforms into an amorphous state.

[0137] Example 8: A method based on amorphous LaCeMo3O 12 -Crystal Ce 0.9 Gd 0.1 solid oxide battery with O2 composite catalyst

[0138] The electrolyte diaphragm in this implementation example is Ce. 0.9 Gd 0.1 O2, with Ce as the negative electrode 0.9 Gd 0.1 O2-LaCeMo3O 12 The positive pole is SmBa 0.5 Sr 0.5 The preparation of Co2O5 batteries includes the following steps:

[0139] 1) Ce 0.9 Gd 0.1 O2 ceramic powder was added to a ball mill, followed by a two-component solvent of xylene and butyl acetate, and an acrylic resin dispersant. After ball milling for 24 hours, a binder of polyvinyl butyral and a plasticizer of polyethylene glycol and / or diethyl phthalate were added, and the mixture was ball milled again for 24 hours to obtain a highly dispersed and uniform cast slurry. After filtration and degassing, the slurry was cast onto a Mylar membrane and dried at 30-60℃ to obtain a 70μm thick Ce film. 0.9 Gd0.1 O2 electrolyte membrane green blank;

[0140] 2) Ce 0.9 Gd 0.1 O2 electrolyte membrane green blanks are stacked, isostatically pressed, and then sintered at 1400℃ for 10 hours to obtain an electrolyte sheet with a thickness of 200 micrometers.

[0141] 3) Screen print SmBa on one side of the electrolyte membrane. 0.5 Sr 0.5 Co2O5 cathode slurry was calcined in air at 1000°C for 4 hours.

[0142] 4) Silkscreen Ce on the other side of the electrolyte membrane. 0.9 Gd 0.1 O2-LaCeMo3O 12 The negative electrode slurry was calcined in air at 900°C for 4 hours to obtain crystalline Ce. 0.9 Gd 0.1 O2 and crystalline LaCeMo3O 12 The negative electrode, which is composed of these components, is reduced in situ to crystalline Ce during battery testing. 0.9 Gd 0.1 O2 and amorphous LaCeMo3O 12 .

[0143] Example 9 A method based on amorphous LaYMoVFeO 12 Solid oxide batteries using crystalline Ti3(Si,Al)C2 composite catalysts

[0144] The battery in this embodiment is based on a "porous|dense" (Sc2O3) material prepared by high-temperature co-sintering. 0.06 (ZrO2) 0.94 The framework, which is dense (Sc2O3). 0.06 (ZrO2) 0.94 The electrolyte is 15 micrometers thick and porous (Sc2O3). 0.06 (ZrO2) 0.94 The skeleton is 300 micrometers thick in (Sc2O3). 0.06 (ZrO2) 0.94 Intra-scaffold impregnation of nano-SmBa 0.5 Sr 0.5 Co2O5 cathode catalyst, impregnation amount 20%;

[0145] Ti3(Si,Al)C2 and LaYMoVFeO 12 The powder was added to a mortar, followed by ethyl cellulose and terpineol. After grinding for 3 hours, it was screen-printed onto (Sc2O3). 0.06 (ZrO2) 0.94The surface of the electrolyte membrane was sintered in air at 950°C for 10 hours to obtain crystalline Ti3(Si,Al)C2 and crystalline LaYMoVFeO. 12 The negative electrode is composed of crystalline Ti3(Si,Al)C2 and amorphous LaYMoVFeO. During battery testing, the negative electrode is reduced in situ to crystalline Ti3(Si,Al)C2 and amorphous LaYMoVFeO. 12 .

[0146] Example 10: A solid oxide battery based on a composite catalyst of crystalline graphene and amorphous La2MoVO9

[0147] The battery in this embodiment is based on a "porous|dense" (Sc2O3) material prepared by high-temperature co-sintering. 0.06 (ZrO2) 0.94 The framework, which is dense (Sc2O3). 0.06 (ZrO2) 0.94 The electrolyte is 15 micrometers thick and porous (Sc2O3). 0.06 (ZrO2) 0.94 The skeleton is 300 micrometers thick in (Sc2O3). 0.06 (ZrO2) 0.94 The skeleton is impregnated with 75% NiO and 25% Ce. 0.9 Gd 0.1 O2 nanocatalyst, impregnation amount 25%;

[0148] Graphene and nano-La2MoVO9 powder were added to a mortar, followed by ethyl cellulose and terpineol. After grinding for 3 hours, the mixture was screen-printed onto (Sc2O3). 0.06 (ZrO2) 0.94 The surface of the electrolyte membrane was sintered at 750°C for 20 hours in a 3% H2-97% N2 atmosphere to obtain a negative electrode composed of crystalline graphene and amorphous La2MoVO9, while NiO in the positive electrode was reduced to Ni.

[0149] Example 11 A solid oxide battery based on a composite catalyst of crystalline TiN and amorphous La2MoFeO9

[0150] The battery in this embodiment is based on a porous | dense Ce material prepared by high-temperature co-sintering. 0.9 Gd 0.1 O2 framework, with dense Ce 0.9 Gd 0.1 The O2 electrolyte is 15 micrometers thick and has porous Ce. 0.9 Gd 0.1 The O2 framework is 300 micrometers thick, and La is impregnated within the framework. 0.3 Sr 1.55 Fe 1.5 Ni 0.1 Mo0.4 O 6-δ Nano-sized cathode catalyst, impregnation amount 25%;

[0151] Powders of TiN and La2MoFeO9 were added to a mortar, along with ethyl cellulose and terpineol. After grinding for 3 hours, the powder was screen-printed onto the surface of an electrolyte membrane. The membrane was then sintered at 750°C for 6 hours in a 6% H2-94% N2 atmosphere to obtain a negative electrode composed of crystalline TiN and amorphous La2MoFeO9.

[0152] The impedance spectra of the amorphous / crystalline heterostructure composites prepared in Examples 6-11 at 650℃ and under conditions of 3% H2O-97% H2 are shown below. Figure 15 As shown.

[0153] The above description of the embodiments is only for the purpose of helping to understand the method and core ideas of the present invention. It should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principles of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

[0154] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. An amorphous / crystalline heterojunction composite material, characterized in that, The composite material is composed of amorphous and crystalline components. The amorphous component is M x R y T z M includes La and / or La-substituted ions, wherein the La-substituted ions are selected from one or more of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Ce, Y, Yb, Pr, Nd, Sm, Gd, Eu, Er, Nb, and Bi; R includes Mo and / or Mo-substituted ions, wherein the Mo-substituted ions are selected from one or more of W, V, Cr, Fe, Co, Ni, Ce, Mn, Pt, Pd, Ru, Ga, and Si; T includes O and / or O-substituted ions, wherein the O-substituted ions are selected from one or more of F, Cl, Br, I, S, Se, and N; and O <x<5;0<y<8;0<z<27; The crystalline components include one or more of the following: proton-conducting oxides, oxygen-ion-conducting oxides, lithium-ion-conducting ceramics, sodium-ion-conducting ceramics, metallic materials, carbon materials, inorganic salts, electronically conductive materials, and non-conductive ceramics.

2. The amorphous / crystalline heterojunction composite material according to claim 1, characterized in that, The volume fraction of the amorphous component in the composite material is 0.1% to 99.9%.

3. The amorphous / crystalline heterojunction composite material according to claim 1 or 2, characterized in that, The proton-conducting oxide includes doped CeO. 2-δ1 doped BaZrO 3-δ2 doped BaCeO 3-δ3 Sr2Sc 1+m1 Nb 1-n1 O 6-δ4 BaZr 0.4 Sc 0.6 O 3-δ5 Ba3Ca 1+m2 Nb 2-n2 O9、BaSn 0.3 Sc 0.7 O 3-δ6 BaTi 0.2 Sc 0.8 O 3-δ7 La 5.5 WO 11.25-δ8 and Ba5R2Al2SnO 13 One or more of the following; Among them, 0<δ1<1, 0<δ2<1, 0<δ3<1, 0<δ4<1, 0<δ5<1, 0<δ6<1, 0<δ7<1, 0<δ8<1; 0 <m1<1,0<n1<1,0<m2<1,0<n2<1; R is selected from one or more of Gd, Dy, Ho, Y, Er, Tm, and Yb; And / or, the oxygen ion-conducting oxide includes doped ZrO. 2-δ9 doped Bi2O 3-δ10 La2Mo2O doped 9-δ11 doped SrFeO 3-δ12 LaGaO doped 3-δ13 La2NiO 4+δ14 Pr2NiO 4+δ15 Nd2NiO 4+δ16 La4Ni3O 10+δ17 and La 1+x1 Sr 1- x2 Ga3O 7.5-δ18 One or more of the following; Among them, 0<δ9<1, 0<δ10<1, 0<δ11<1, 0<δ12<1, 0<δ13<1 , 0<δ14<1, 0<δ15<1, 0<δ16<1, 0<δ17<1, 0<δ18<1,0 <x1<1,0<x2<1。 4. The amorphous / crystalline heterojunction composite material according to claim 1 or 2, characterized in that, The lithium-ion conductive ceramic includes FeLiPO4 and Li 1.3 Al 0.7 Ti 1.7 (PO4)3, doped Li7La3Zr2O 12 and one or more of doped LiTiO3; and / or, the sodium ion-conducting ceramic comprises Na3Zr2Si2PO4. 12 Na 3.4 Zr 1.8 Mg 0.2 Si 2.4 P 0.6 O 12 and Na 3.2 Zr 1.8 Tb 0.2 Si2PO 12 One or more of the following: and / or, the metallic material includes one or more of Ni, Cu, Fe, Co, FeNi3, 430L and 440 stainless steel; and / or, the carbon material includes one or more of graphite, graphene and doped graphene; and / or, the inorganic salt includes one or more of Li2CO3, Na2CO3, K2CO3, SrCO3 and BaCO3.

5. The amorphous / crystalline heterojunction composite material according to claim 1 or 2, characterized in that, The electron-conducting material includes (La, Ba, Sr)(Cr, Mo, Fe, Co, Ni, Mg, Mn)O. 3-δ19 La(Ni,Fe)O 3-δ20 (La,Sr)(Ti,Fe,Co,Ni)O 3-δ21 、(Sm 1-x3 Sr x4 CoO 3-δ22 LaBa 0.5 Sr 0.5 Co2O 5+δ23 、SmBa 0.5 Sr 0.5 Co2O 5+δ24 SmBaCo2O 5+δ25 、BaGd 0.8 La 0.2 Co2O 6-δ26 One or more of the following: doped Co3O4, doped Mn3O4, doped Fe3O4, WC, TiC, TaC, MoWC2, Mo2C, (Ti,Nb)3SiC2, (Ti,Cr,V)2AlC, Ti3(Si,Al)C2, Ti3(Si,Ge)C2, Ti2Al(C,N), Ti3Al(C,N)2, TiN, ZrN, VN, WN, NbN, TaN, and MoN; Where, 0 < δ19 < 1, 0 < δ20 < 1, 0 < δ21 < 1, 0 <x3<1,0<x4<1,0<δ22<1,0<δ23<1,0<δ24<1,0<δ25<1,0<δ26<1; And / or, the non-conductive ceramic includes one or more of Li2O, Na2O, K2O, Rb2O, Cs2O, MgO, CaO, SrO, BaO, Al2O3, Ga2O3, In2O3, La2O3, Y2O3, Yb2O3, Pr2O3, Sm2O3, and Gd2O3.

6. The amorphous / crystalline heterojunction composite material according to claim 1, characterized in that, The preparation method of the amorphous / crystalline heterojunction composite material includes: Crystalline component solutions and amorphous component solutions were prepared separately. The crystalline component solution and the amorphous component are mixed and then heated to a dry gel to obtain a dry gel composition. The dry gel composition was baked until it expanded during combustion, and the resulting powder was calcined to obtain an amorphous / crystalline heterojunction composite material.

7. A solid oxide fuel cell, comprising a positive electrode, an electrolyte membrane, and a negative electrode sequentially stacked and composited, characterized in that, The positive electrode comprises the amorphous / crystalline heterojunction composite material according to any one of claims 1 to 6, and / or the negative electrode comprises the amorphous / crystalline heterojunction composite material according to any one of claims 1 to 6.

8. The solid oxide fuel cell according to claim 7, characterized in that, The solid oxide fuel cell is used in oxygen reduction reaction, hydrogen evolution reaction, oxygen absorption reaction, hydrogenation reaction, oxidative dehydrogenation reaction, or oxygen-free dehydrogenation reaction.

9. A catalyst comprising the amorphous / crystalline heterojunction composite material according to any one of claims 1 to 6.

10. The catalyst according to claim 9, characterized in that, Applications of the catalyst in hydrocarbon fuels, steam reforming, dry reforming, oxidative reforming, hydrogenation, oxidative dehydrogenation, or oxygen-free dehydrogenation.

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