A supported manganese-based composite oxide material with multiple ion conductivity characteristics and its preparation method and application

Abstract

The present invention discloses a loaded manganese-based composite oxide material with multiple ion conductivity characteristics, its preparation method and application. The material is composed of a composite oxide with a mass fraction of 2 to 100 wt% and a carrier with a mass fraction of 0 to 98 wt%. The chemical formula of the composite oxide is A x B 1‑x Mn y C 2‑y O z , 0≤x≤1, 0≤y≤2, 0≤z≤10; wherein A and B are both one of lanthanide, bismuth, yttrium, lithium, sodium, potassium, magnesium, calcium, strontium, barium, antimony or scandium elements, and when A and B exist at the same time, the elements used by A and B are different; C is one of transition metal elements, aluminum, gallium, indium, thallium, silicon, germanium, tin or lead; the carrier is cerium zirconium-based oxide. The material is used as a multiple ion conductor. The material of the present invention has excellent electrical conductivity properties of hydrogen ions, lithium ions and oxygen ions at the same time. Special ion channels are formed under the mixed stacking geometry structure of the manganese-oxygen coordination unit corner sharing, and has excellent hydrogen, lithium and oxygen ion conductivity properties.

Description

Technical Field

[0001] The present invention relates to the field of ion-conductive ceramic materials, in particular to a supported manganese-based composite oxide material with multiple ion conductivity characteristics, and a preparation method and application thereof. Background Art

[0002] Ion-electron mixed conductive ceramic materials are materials that can conduct both ions and electronic carriers (free electrons and / or electron holes). This series of materials can be used as electrode materials for lithium batteries, solid oxide fuel cells and oxygen sensors.

[0003] Materials for multiple ion conductivities primarily include perovskite-type (ABO3) materials. However, manganese-based perovskites have a large thermal expansion coefficient, which can lead to device fracture and increased interfacial resistance during heating. This makes them incompatible with traditional electrolyte materials for electrode applications, presenting certain limitations. In addition to requiring a high degree of structural and physicochemical compatibility with the electrolyte, electrode materials must also possess high thermal (chemical) stability to prevent reactions with the electrolyte or self-decomposition at high temperatures. Traditional perovskite-type materials, such as LSC and LSCF, which have been the focus of research both domestically and internationally, experience strontium diffusion into the electrolyte layer during high-temperature reactions, reacting with zirconium oxide. Oxide-based solid electrolytes for solid-state lithium batteries primarily include perovskite-structured lithium-steel-titanium oxide (LLTO). Perovskite oxide solid electrolytes often require the addition of polymer components and mixing with trace amounts of ionic liquids / high-performance lithium salts as electrolytes, or the use of assisted in-situ polymerization to create quasi-solid-state batteries, in order to retain some safety advantages and improve electrolyte-electrode interfacial contact.

[0004] The main component of the supported manganese-based composite oxide material is mullite-type oxide, which has an orthorhombic crystal structure with MnO6 octahedra arranged along the c-axis and interconnected with MnO5 pyramids. The intrinsic structure of the mullite-type material is a ternary oxide, and its crystal structure is flexible and adjustable, with twin field and mixed stacking structure characteristics. In an oxygen atmosphere, the supported manganese-based composite oxide material has both oxygen ion and electron conductivity properties and can be used in the cathode of oxygen ion solid oxide fuel cells. As an electrolyte, one side contacts the reducing gas of the hydrogen fuel anode, and the electron and oxygen ion conductivity disappears, with hydrogen ion conductivity dominating; it can be used as an electrolyte membrane for application in semiconductor ion batteries. Theoretical studies have found that the supported manganese-based composite oxide material has excellent hydrogen ion conductivity, and has both oxygen ion and electron conductivity properties, and can be used in the cathode of hydrogen ion ceramic fuel cells.

[0005] Supported manganese-based composite oxide materials offer high thermal stability and a wide thermal stability range, far superior to perovskite-based materials. Their thermal expansion coefficients are close to those of conventional hydrogen or oxygen ion conducting electrolytes, facilitating the formation of a favorable interface and thus facilitating ion transport. Mullite materials do not contain strontium or cobalt, reducing diffusion issues.

[0006] Supported manganese-based composite oxide materials have been used for the purification and catalytic elimination of indoor and outdoor gaseous pollutants, including automobile exhaust NOx, volatile organic compounds (VOCs) in industrial waste gas, etc. As the positive electrode of metal-air batteries and lithium-sulfur batteries, they exhibit excellent electrocatalytic performance; however, their application as catalysts has only been developed so far. Summary of the Invention

[0007] In view of the deficiencies of the prior art, the technical problem to be solved by the present invention is to provide a supported manganese-based composite oxide material with multiple ion conductivity characteristics, and a preparation method and application thereof.

[0008] The technical solution of the present invention to solve the material technology problem is to provide a supported manganese-based composite oxide material with multiple ion conductivity characteristics, characterized in that the material is composed of a composite oxide with a mass fraction of 2 to 100 wt% and a carrier with a mass fraction of 0 to 98 wt%;

[0009] The chemical formula of the composite oxide is A x B 1-x Mn y C 2-y O z , 0≤x≤1, 0≤y≤2, 0≤z≤10; wherein A and B are each one of lanthanide, bismuth, yttrium, lithium, sodium, potassium, magnesium, calcium, strontium, barium, antimony or scandium, and when A and B exist at the same time, the elements used by A and B are different; C is one of transition metal elements, aluminum, gallium, indium, thallium, silicon, germanium, tin or lead;

[0010] The carrier is cerium-zirconium-based oxide.

[0011] The technical solution of the present invention to solve the technical problem of the method is to provide a method for preparing the supported manganese-based composite oxide material with multiple ion conductivity characteristics, characterized in that the method comprises the following steps:

[0012] Step 1, synthesizing the composite oxide: the synthesis method of the composite oxide includes hydrothermal method, coprecipitation method, sol-gel method, organic polymerization method and electrodeposition method;

[0013] Step 2: Loading the composite oxide on a cerium-zirconium-based oxide support to obtain a loaded manganese-based composite oxide material with multiple ion conductivity characteristics.

[0014] The technical solution of the present invention to solve the application technical problem is to provide an application of the supported manganese-based composite oxide material with multiple ion conductivity characteristics, characterized in that the material is used as a multiple ion conductor.

[0015] Compared with the prior art, the present invention has the following beneficial effects:

[0016] (1) The material of the present invention simultaneously possesses excellent conductivity properties for hydrogen, lithium, and oxygen ions. The mixed stacking geometry of the manganese-oxygen coordination units, where corners are shared, forms a unique ion channel, resulting in excellent conductivity properties for hydrogen, lithium, and oxygen ions. Furthermore, the manganese-based composite oxide material contains no precious metals, is relatively low in cost, and exhibits stable thermal and chemical properties. Furthermore, the preparation technology is controllable and simple, thus possessing significant application prospects in solid oxide batteries, electrothermal coupled catalytic reactions, oxygen ion sensors, and lithium-ion solid-state batteries.

[0017] (2) The crystal structure of the composite oxide prepared by the present invention has low symmetry, which helps to match the lattice when forming an interface with the cerium-zirconium-based oxide material; and the matching degree with the thermal expansion behavior of the cerium-zirconium-based hydrogen ions can reach more than 95%, ensuring rapid ion transmission at the interface and the safety of the device.

[0018] (3) The composite oxide prepared by the present invention has extremely high hydrothermal stability, which solves the problem of phase change or decomposition that is easy to occur in traditional oxide materials under high temperature or water vapor conditions, and has no strontium / cobalt element diffusion problem. It helps to achieve stable performance output and maintain a good electrode-electrolyte interface under heating environment, which will ultimately help to realize the construction of barrier-free solid oxide fuel cell devices.

[0019] (4) Due to the particularity of the single electron occupancy of the dz2 orbital in the pyramid crystal field, the surface of the composite oxide prepared by the present invention is easy to interact with oxygen-containing intermediates and has been applied in magnesium / zinc-air batteries and lithium-sulfur batteries, showing excellent oxygen reduction electrocatalytic activity.

[0020] (5) The synthesis method of the present invention is simple, can be mass-produced, and is suitable for industrial production and application.

[0021] (6) The material of the present invention has multiple ion conductivity properties, enabling its application in the field of ion conduction. This is fundamentally different from the previous application as a catalyst, and the span is larger. The catalytic reaction occurs on the surface of the material, and the material acts as a catalyst to accelerate the reaction; while ion conduction occurs within the material lattice, not on the surface. The material acts as a medium for ion conduction, and no chemical reaction occurs.

[0022] (7) The double crystal field synergistic effect of the material structure of the present invention helps to achieve excellent performance in solid oxide fuel cell cathode applications. Through super exchange or double exchange interactions, in the cathode oxygen reduction electrocatalysis process, the active sites can cooperate with the coordination environment of the neighbors to regulate the oxidation of O2 and O - , O 2- The adsorption and desorption energies of the cathode material are significantly improved. A rich metal-oxygen coordination environment provides more possibilities for hydrogen ion transport. Combined with the synergistic effect of the double crystal field, the binding strength between hydrogen and oxygen is modulated during transport, thereby reducing the migration barrier. This significantly improves the overall performance of the cathode material and designs a crystal structure that can accommodate a variety of coordination units, fundamentally addressing the electronic and geometric limitations of perovskites. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 The XRD pattern of the composite oxide SmMn2O5 obtained in Example 1 of the present invention;

[0024] Figure 2 The XRD pattern of the composite oxide YMn2O5 obtained in Example 2 of the present invention;

[0025] Figure 3 Schematic diagram of the ion conduction channel of Example 2 of the present invention;

[0026] Figure 4 This is a schematic diagram of the hydrogen ion conduction process obtained by theoretical calculation according to Example 2 of the present invention;

[0027] Figure 5 is a graph showing the minimum migration barrier of hydrogen ions obtained by theoretical calculation according to Example 2 of the present invention;

[0028] Figure 6 Schematic diagram of the lithium ion and hydrogen ion conduction process obtained by theoretical calculation according to Example 2 of the present invention. DETAILED DESCRIPTION

[0029] The specific embodiments of the present invention are given below. The specific embodiments are only used to further illustrate the present invention and do not limit the scope of protection of the claims of the present invention.

[0030] The present invention provides a supported manganese-based composite oxide material (hereinafter referred to as material) having multiple ion conductivity characteristics, characterized in that the material is composed of a composite oxide with a mass fraction of 2 to 100 wt% (preferably 10 to 100 wt%, more preferably 20 to 100 wt%, and further preferably 60 to 90 wt%) and a carrier with a mass fraction of 0 to 98 wt% (preferably 0 to 90 wt%, more preferably 0 to 80 wt%, and further preferably 10 to 40 wt%);

[0031] The chemical formula of the composite oxide is A xB 1-x Mn y C 2-y O 5-z , 0≤x≤1, 0≤y≤2, 0≤z≤1; wherein A and B are each one of lanthanide, bismuth, yttrium, lithium, sodium, potassium, magnesium, calcium, strontium, barium, antimony, or scandium, and when A and B exist simultaneously, the elements used by A and B are different; C is one of transition metal elements, aluminum, gallium, indium, thallium, silicon, germanium, tin, or lead;

[0032] The carrier is cerium-zirconium-based oxide.

[0033] Preferably, the cerium zirconium-based oxide is ZrO2, CeO2, (Zr, Y)O2, Gd 0.1 Ce 0.9 O 2-δ 、BaZr 0.1 Ce 0.7 Y 0.2 O 3-δ 、BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ or Ce 0.8 Sm 0.2 O 2-δ .

[0034] Preferably, the material is a pure phase structure of a mullite phase or a composite phase structure of a mullite phase and other types of oxides.

[0035] Preferably, the material is in the form of powder, film or foam ceramic. The material morphology is nanoparticles, nanorods, nanowires or nanosheets.

[0036] The present invention also provides a method for preparing the supported manganese-based composite oxide material having multiple ion conductivity characteristics (hereinafter referred to as the method), characterized in that the method comprises the following steps:

[0037] Step 1, synthesizing the composite oxide: the synthesis method of the composite oxide includes hydrothermal method, coprecipitation method, sol-gel method, organic polymerization method and electrodeposition method;

[0038] Preferably, in step 1, the co-precipitation method is specifically: mixing the manganese salt precursor solution and the elemental nitrate precursor solution evenly to form a homogeneous solution; then adding hydrogen peroxide for oxidation so that the solution changes from colorless to light yellow; then adding an organic base solution dropwise until the solution pH is 10-11, then defoaming with a defoaming agent, and then performing a precipitation reaction to obtain a precipitate; then washing and filtering the precipitate, drying it, and then calcining it to achieve crystallization to obtain a composite oxide.

[0039] Preferably, in step 1, the manganese salt is Mn(NO3)2 and / or Mn(CH3COO)2; the elemental nitrate is composed of A(NO3)3, B(NO3)3 and C(NO3)3; and the molar ratio of manganese salt to elemental nitrate is 1 to 3:1.

[0040] Preferably, in step 1, the oxidation process is carried out by stirring at room temperature for 1 to 2 hours.

[0041] Preferably, in step 1, the molar ratio of the sum of manganese salt and elemental nitrate: hydrogen peroxide is 6 to 10:1.

[0042] Preferably, in step 1, the organic base solution is tetramethylammonium hydroxide or tetrapropylammonium hydroxide, preferably tetramethylammonium hydroxide.

[0043] Preferably, in step 1, the defoaming agent is octanol, diethylhexanol, isooctyl alcohol, isopentanol or diisobutyl carbinol, preferably octanol.

[0044] Preferably, in step 1, the precipitation reaction process is carried out by magnetic stirring at 20-30° C. and 400-600 rpm for 8-12 hours.

[0045] Preferably, in step 1, the drying process is performed at 80-100° C. for 6-8 hours.

[0046] Preferably, in step 1, the calcination process is performed at 800-1000° C. for 8-12 hours.

[0047] Step 2: Loading the composite oxide on a cerium-zirconium-based oxide support to obtain a loaded manganese-based composite oxide material with multiple ion conductivity characteristics.

[0048] Preferably, in step 2, the loading method is an immersion method or a ball milling method.

[0049] Preferably, in step 2, the impregnation method is specifically: dispersing the composite oxide powder in a precursor salt solution of a cerium-zirconium-based oxide, mixing uniformly, drying to obtain a solid precipitate, and then calcining the solid precipitate to obtain a supported manganese-based composite oxide material.

[0050] Preferably, in step 2, the molar ratio of the composite oxide to the cerium-zirconium-based oxide is 1:0.5-1.

[0051] Preferably, in step 2, the precursor salt solution of the cerium-zirconium-based oxide is nitrate.

[0052] Preferably, in step 2, magnetic stirring is used for mixing. The drying process is carried out in an oven at 120-150° C. for 24-36 hours. The calcination process is carried out in a muffle furnace at 300-1000° C. for 3-12 hours.

[0053] Preferably, in step 2, the ball milling method specifically comprises: ball milling the composite oxide powder and the cerium-zirconium-based oxide support powder until an interface bond is formed.

[0054] Preferably, in step 2, the ball milling process is performed in a ball milling jar for 20 to 30 minutes.

[0055] The present invention also provides an application of the supported manganese-based composite oxide material with multiple ion conductivity characteristics (hereinafter referred to as application), characterized in that the material is used as a multiple ion conductor.

[0056] Preferably, the multi-ion conductor comprises an oxygen ion solid oxide fuel cell cathode, a hydrogen ion solid oxide fuel cell cathode, and a hydrogen ion solid electrolyte. More preferably, it is used in solid oxide fuel cells, electrically coupled catalytic reactors, oxygen sensors, and solid-state lithium-ion batteries. More preferably, it is used in acoustic, optical, thermal, and electrical coupling devices.

[0057] Preferably, the material is used as a cathode for an oxygen ion solid oxide fuel cell, specifically by: uniformly mixing the material with a binder to obtain a cathode slurry; co-pressing the anode and electrolyte sheets and then co-sintering them to prepare an anode supporting half-cell sheet; then brushing the cathode slurry onto the anode supporting half-cell sheet through a brushing process, recording the effective area, and then drying and calcining it to obtain a battery.

[0058] Preferably, the binder is terpineol or polyvinyl alcohol (more preferably terpineol); the mass ratio of the material to the binder is 1:0.1-0.2; the anode is Ni / YSZ material or Ni / GDC material (more preferably Ni / YSZ material); the electrolyte sheet is YSZ material or GDC material (more preferably YSZ material); the co-pressing process: the pressure is 200-300 MPa (more preferably 250 MPa) and the time is 3-5 min (more preferably 4 min); the co-sintering process is calcined at 800-900 ° C for 8-12 h; the coating process is screen printing or spin coating (preferably screen printing); the effective area of ​​the battery is 1-3 cm 2 (More preferably 1.3cm 2 ); the drying process is drying in an oven at 100-120° C. for 8-12 hours; and the calcining process is calcining at 800-900° C. for 4-6 hours.

[0059] Preferably, the material is used as a cathode of a hydrogen ion solid oxide fuel cell, specifically: the material is mixed evenly with a binder to obtain a cathode slurry; the anode and electrolyte sheets are first co-pressed and then co-sintered to prepare an anode supporting half-cell sheet; then the cathode slurry is brushed on the anode supporting half-cell sheet through a brushing process, the effective area is recorded, and then it is dried and calcined to form a battery.

[0060] Preferably, the binder is terpineol or polyvinyl alcohol (more preferably terpineol); the mass ratio of the material to the binder is 1:0.1-0.2; the anode is Ni / SrCe 0.9 Y 0.1 O 3-α Material or Ni / BaZr 0.1 Ce 0.7 Y 0.2 O 3-δ Materials (more preferably Ni / BaZr 0.1 Ce 0.7 Y 0.2 O 3-δ ); the electrolyte sheet uses SrCe 0.9 Y 0.1 O 3-α Material or BaZr 0.1 Ce 0.7 Y 0.2 O 3-δ Materials (more preferably BaZr 0.1 Ce 0.7 Y 0.2 O 3-δ ); co-pressing process: pressure of 150-200 MPa (more preferably 180 MPa), time of 10-15 min (more preferably 12 min); co-sintering process: calcination at 800-900 ° C for 8-12 h; coating process adopts screen printing or spin coating (preferably screen printing); battery effective area is 1-3 cm 2 (More preferably 1.3cm 2 ); the drying process is drying at 100-120° C. for 8-12 hours; and the calcining process is calcining at 800-900° C. for 4-6 hours.

[0061] Preferably, the material is used as a hydrogen ion solid electrolyte, specifically: the material is placed between an anode and a cathode, and then the whole is co-pressed and then co-sintered to prepare a battery.

[0062] Preferably, both the anode and cathode are made of Ni-NCAL material; co-pressing process: pressure is 300-500 MPa (more preferably 350 MPa), time is 15-25 min (more preferably 20 min); co-sintering process: calcination at 800-900°C for 16-24 h.

[0063] The test method in the embodiment is: the battery is sealed in a vertical test furnace using a high-temperature adhesive (preferably ceramic adhesive), and then tested using an electrochemical workstation at a test temperature of 25 to 850°C.

[0064] Example 1

[0065] (1) Mn(CH3COO)2·4H2O and Sm(NO3)3·6H2O were added to deionized water in a molar ratio of 2:1 to form a homogeneous solution; hydrogen peroxide was then added for oxidation for 1 hour, and the molar ratio of the sum of manganese salt and elemental nitrate to hydrogen peroxide was 7:1; tetramethylammonium hydroxide was then added dropwise until the solution pH reached 10, and then defoamed with octanol, and then magnetically stirred at 25°C and 400 rpm for 8 hours for precipitation reaction; the precipitate was washed with deionized water and filtered, dried in an oven at 100°C, and then calcined in a muffle furnace at 800°C for 8 hours to crystallize to obtain the composite oxide SmMn2O5;

[0066] Depend on Figure 1 It can be seen from the XRD phase analysis that all the peaks of the composite oxide in Example 1 are consistent with the standard spectrum of SmMn2O5 (PDF#88-0374), indicating that pure phase SmMn2O5 is obtained.

[0067] (2) The composite oxide powder and the (Zr, Y)O2 carrier powder are ball-milled until an interface bond is formed to prepare a loaded manganese-based composite oxide material with multiple ion conductivity characteristics.

[0068] Application: The supported manganese-based composite oxide material with multiple ion conductivity characteristics of Example 1 was mixed with terpineol at a mass ratio of 1:0.15 to obtain a cathode slurry. The Ni / YSZ anode and YSZ solid electrolyte sheet were co-pressed at 250 MPa for 4 minutes and then co-sintered at 800°C for 8 hours to prepare an anode-supported half-cell sheet. The cathode slurry was then applied to the anode-supported half-cell sheet by a brushing process, and the effective area was recorded as 1.3 cm. 2 The battery was then dried in a 100°C oven for 10 hours. After drying, it was further calcined at 800°C for 5 hours to form a battery. Finally, the battery was tested in an environment with hydrogen as the anode fuel gas and oxygen as the cathode reaction gas, with a test temperature range of 600-800°C. The performance results are shown in Table 1.

[0069] Table 1

[0070] Operating temperature (℃) <![CDATA[Peak current density (mW / cm 2 )]]> 600 72.8 650 143.7 700 250.2 750 330.0 800 570.7

[0071] Table 1 shows the peak power density of Example 1 of the present invention as the cathode of an oxygen ion solid oxide fuel cell at different temperatures. As can be seen from Table 1, the material has oxygen ion conductivity characteristics.

[0072] Comparative Example 1

[0073] According to the literature "Jian Xin Wang, Jia Long Sun, Chang Rong He, Qin Wang, Wei Guo Wang. Mass synthesis of high performance (La 0.75 Sr 0.25 ) 0.95 MnO 3±δ nano-powderprepared via a low-carbon chemical solution method[J].Journal of PowerSources,2014,253:424-430》was prepared by the method provided in the journal, and (La 0.75 Sr 0.25 ) 0.95 MnO 3±δ As Comparative Example 1.

[0074] Comparative Example 2

[0075] According to the literature《Wei Mei,Haojie Wang,Wenlu Li,Juan Zhou,Xiufu Sun,HanwenZhao,Shimin Wang.Enhanced and stable strontium and cobalt free A sitedeficient La 1-x Ni 0.6 Fe 0.4 O3(x=0,0.02,0.04,0.06,0.08)cathodes for intermediatetemperature solid oxide fuel cells[J].International Journal of HydrogenEnergy,2021,46:36436-36444》, La 0.94 Ni 0.6 Fe 0.4 O3 was used as comparative example 2.

[0076] Table 2 is a table of performance parameters of battery devices using Example 1, Comparative Example 1 and Comparative Example 2 as oxygen ion conductors.

[0077] Table 2

[0078] Operating temperature (℃) <![CDATA[Peak current density (mW / cm 2 )]]> Example 1 800 570.7 Comparative Example 1 800 540.0 Comparative Example 2 800 570.0

[0079] As can be seen from Table 2, when the operating temperature is 800° C., the battery performance of Example 1 is comparable to that of Comparative Examples 1 and 2, indicating that it can conduct oxygen ions from the electrolyte as a cathode and complete the cathode catalytic reaction.

[0080] Example 2

[0081] (1) Mn(CH3COO)2·4H2O and Y(NO3)3·5H2O were added to deionized water in a molar ratio of 2:1 to form a homogeneous solution; hydrogen peroxide was then added for oxidation for 2 h, with the molar ratio of the sum of manganese salt and elemental nitrate to hydrogen peroxide being 7:1; tetramethylammonium hydroxide was then added dropwise until the solution pH reached 11, and the solution was defoamed with octanol, followed by precipitation reaction at 25°C and 400 rpm under magnetic stirring for 8 h; the precipitate was washed with deionized water and filtered, dried in an oven at 100°C, and then calcined in a muffle furnace at 800°C for 8 h to crystallize to obtain the composite oxide YMn2O5;

[0082] Depend on Figure 2 It can be seen from the XRD phase analysis that all the peaks of the composite oxide in Example 2 are consistent with the standard spectrum of YMn2O5 (PDF#34-0667), indicating that pure phase YMn2O5 is obtained.

[0083] (2) Mix the composite oxide powder with BaZr 0.1 Ce 0.7 Y 0.2 O 3-δ The carrier powder is ball-milled to form interface bonding, thereby preparing a supported manganese-based composite oxide material with multiple ion conductivity characteristics.

[0084] Application: The supported manganese-based composite oxide material with multiple ion conductivity characteristics of Example 1 was sandwiched between a Ni-NCAL material anode and a Ni-NCAL material cathode as an electrolyte, and co-pressed at a pressure of 350 MPa for 20 minutes; then co-sintered at 900°C for 20 hours to obtain a battery.

[0085] Table 3

[0086] Operating temperature (℃) <![CDATA[Peak current density (mW / cm 2 )]]> 400 162 425 212 450 300 475 417 500 555 525 637 550 639

[0087] Table 3 shows the peak power density of Example 2 of the present invention as a hydrogen ion solid electrolyte at different temperatures. As can be seen from Table 3, the material has hydrogen ion conductivity characteristics.

[0088] Depend on Figure 3 It can be seen that the crystal structure of Example 2 has a natural channel for ion transfer due to the twin crystal field characteristics and mixed stacking structure.

[0089] In order to gain a deeper understanding of the conduction of hydrogen ions in Example 2, first-principles calculations were used to study the transport pathway of hydrogen ions. In order to simulate the antiferromagnetic order of Example 2, a 2×1×1 supercell of 64 atoms was constructed. There is a hollow channel between the MnO5 and Y layers along the b direction, which is expected to promote the transport of hydrogen ions. An additional hydrogen atom was introduced and its migration in the channel was considered. Figure 4 It can be seen that various lattice oxygens conduct hydrogen ions in a triangular relay manner, thereby exhibiting excellent hydrogen ion conductivity characteristics. Figure 5 It can be seen that the hydrogen ion migration barrier in Example 2 obtained by theoretical calculation is as low as 0.1 eV.

[0090] Depend on Figure 6 It can be seen that the energy changes during the migration path of lithium ions and hydrogen ions in Example 2 obtained by theoretical calculation illustrate the lithium ion conduction characteristics of Example 2.

[0091] Comparative Example 3

[0092] According to the literature "Nikdalila Radenahmad, Shammya Afroze, Ahmed Afif, Atia T. Azad, Ji-Seop Shin, Jun-Young Park, Juliana Haji Zaini, Abul Kalam Azad. High conductivity and high density SrCe 0.5 Zr 0.35 Y 0.1 A 0.05 O 3-δ The preparation method provided in (A=Gd,Sm)proton-conductingelectrolytes for IT-SOFCs[J].Ionics,2020,26:1297-1305 was used to synthesize SrCe 0.5 Zr 0.35 Y 0.1 Gd 0.05 O 3-δ As comparative example 3, the performance was characterized.

[0093] Comparative Example 4

[0094] According to the literature "Nikdalila Radenahmad, Shammya Afroze, Ahmed Afif, Atia T. Azad, Ji-Seop Shin, Jun-Young Park, Juliana Haji Zaini, Abul Kalam Azad. High conductivity and high density SrCe 0.5 Zr 0.35 Y 0.1 A 0.05 O 3-δ The preparation method provided in (A=Gd,Sm)proton-conductingelectrolytes for IT-SOFCs[J].Ionics,2020,26:1297-1305 was used to synthesize SrCe 0.5 Zr 0.35 Y 0.1 Sm 0.05 O 3-δ As comparative example 4, the performance was characterized.

[0095] Table 4 is a table of performance parameters of battery devices of Example 2, Comparative Example 3 and Comparative Example 4 as hydrogen ion conductors.

[0096] Table 4

[0097] Operating temperature (℃) Conductivity (S / cm) Example 2 550 0.18 Comparative Example 3 700 <![CDATA[5.701×10 -3 ]]> Comparative Example 4 700 <![CDATA[5.257×10 -3 ]]>

[0098] It can be seen from Table 4 that at 700°C and 5% wet hydrogen, the electrical conductivities of Comparative Examples 3 and 4 are 5.701×10 -3 S / cm and 5.257×10 -3 S / cm, so the conductivity of the battery using Example 2 as the electrolyte is one order of magnitude higher at a lower temperature and in a dry hydrogen atmosphere, reflecting excellent conductivity characteristics.

[0099] Any matters not described in the present invention are applicable to the prior art.

Claims

1. A supported manganese-based composite oxide material having multiple ion conductivity characteristics is used as a multiple ion conductor, characterized in that: The material is a composite phase structure of mullite phase and other types of oxides, and is composed of 60-90wt% of composite oxide and 10-40wt% of carrier. The chemical formula of the composite oxide is Sm x Y 1-x Mn2O5, 0<x<1; The carrier is cerium zirconium-based oxide; cerium zirconium-based oxide is ZrO2, CeO2, (Zr, Y) O2, Gd 0.1 Ce 0.9 O 2-δ 、BaZr 0.1 Ce 0.7 Y 0.2 O 3-δ 、BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ or Ce 0.8 Sm 0.2 O 2-δ ; The composite oxide is loaded on a cerium-zirconium-based oxide support to prepare a loaded manganese-based composite oxide material having multiple ion conductivity characteristics; the loading method adopts an impregnation method or a ball milling method; The multiple ion conductors include an oxygen ion solid oxide fuel cell cathode and a hydrogen ion solid electrolyte.

2. The use according to claim 1, characterized in that: The preparation method of the material comprises the following steps: Step 1, synthesizing the composite oxide: the synthesis method of the composite oxide includes hydrothermal method, coprecipitation method, sol-gel method, organic polymerization method and electrodeposition method; Step 2: Loading the composite oxide on a cerium-zirconium-based oxide support to obtain a loaded manganese-based composite oxide material with multiple ion conductivity characteristics.

3. The use according to claim 2, characterized in that In step 1, the coprecipitation method is specifically as follows: a manganese salt precursor solution and an elemental nitrate precursor solution are mixed uniformly to form a homogeneous solution; hydrogen peroxide is then added for oxidation, so that the solution changes from colorless to light yellow; an organic base solution is then added dropwise until the solution pH is 10-11, defoamed with a defoaming agent, and then a precipitation reaction is performed to obtain a precipitate; the precipitate is then washed and filtered, dried, and then calcined to achieve crystallization to obtain a composite oxide; The manganese salt is Mn(NO3)2 and / or Mn(CH3COO)2; the molar ratio of the manganese salt to the elemental nitrate is 1-3:1; the oxidation process is stirring at room temperature for 1-2 hours; the molar ratio of the sum of the manganese salt and the elemental nitrate to hydrogen peroxide is 6-10:1; the organic alkaline solution is tetramethylammonium hydroxide or tetrapropylammonium hydroxide; the defoaming agent is octanol, diethylhexanol, isooctyl alcohol, isoamyl alcohol or diisobutyl carbinol; the precipitation reaction process is magnetic stirring at 20-30°C and 400-600 rpm for 8-12 hours; The drying process is to dry at 80-100°C for 6-8 hours; the calcination process is to calcine at 800-1000°C for 8-12 hours.

4. The use according to claim 2, characterized in that In step 2, the loading method is an immersion method or a ball milling method; The impregnation method specifically comprises: dispersing the composite oxide powder in a precursor salt solution of a cerium-zirconium-based oxide, mixing uniformly, drying to obtain a solid precipitate, and then calcining the solid precipitate to obtain a supported manganese-based composite oxide material; the molar ratio of the composite oxide to the cerium-zirconium-based oxide is 1:0.5-1; the precursor salt solution of the cerium-zirconium-based oxide is nitrate; mixing is performed using magnetic stirring; the drying process is performed in an oven at 120-150°C for 24-36 hours; and the calcination process is performed in a muffle furnace at 300-1000°C for 3-12 hours; The ball milling method specifically comprises the following steps: ball milling the composite oxide powder and the cerium-zirconium-based oxide support powder until an interface bond is formed; and the ball milling process is performed in a ball milling jar for 20 to 30 minutes.

5. The use according to claim 1, characterized in that The application of the material as a cathode for an oxygen ion solid oxide fuel cell comprises the following steps: uniformly mixing the material with a binder to obtain a cathode slurry; co-pressing and then co-sintering an anode and an electrolyte sheet to prepare an anode supporting half-cell sheet; then applying the cathode slurry to the anode supporting half-cell sheet by a brushing process, recording the effective area, and drying and then calcining the sheet to obtain a battery; The binder is terpineol or polyvinyl alcohol; the mass ratio of the material to the binder is 1:0.1-0.2; the anode is Ni / YSZ material or Ni / GDC material; The electrolyte sheet is made of YSZ or GDC. The anode and electrolyte sheet are co-pressed at a pressure of 200-300 MPa for 3-5 minutes. The anode and electrolyte sheet are co-sintered at 800-900°C for 8-12 hours. The coating process uses screen printing or spin coating. The battery active area is 1-3 cm 2 ; The drying process is to dry in an oven at 100~120℃ for 8~12h; the calcination process is to calcine at 800~900℃ for 4~6h.

6. The use according to claim 1, characterized in that The material is used as a hydrogen ion solid electrolyte, specifically by placing the material between an anode and a cathode, and then co-pressing and co-sintering the whole to prepare a battery; Both the anode and cathode are made of Ni-NCAL material; the co-pressing process: the pressure is 300~500MPa, and the time is 15~25min; the co-sintering process: calcination at 800~900℃ for 16~24h.

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