A proton-conductor ceramic cell for complex working conditions and a method for manufacturing the same

Abstract

This application discloses a proton conductor ceramic battery for use under complex operating conditions and its preparation method. The proton conductor ceramic battery includes a positive electrode, an electrolyte, and a negative electrode arranged sequentially. The positive electrode includes a positive electrode catalyst; the negative electrode includes a negative electrode catalyst; a nano-catalyst is deposited on the inner surface of at least one of the positive and negative electrodes; the complex operating conditions include a working gas with a volume percentage of 20% to 100% for the positive electrode, and the working gas includes one or more of H2O, CO2, methanol, ethanol, propanol, formic acid, or acetic acid. This application improves the chemical stability of the positive or negative electrode under high-concentration H2O, CO2, and organic atmospheres by coating the inner surface of the porous positive or negative electrode with a nano-catalyst, thereby enhancing the performance stability of the proton conductor ceramic battery under actual industrial operating conditions.

Description

Technical Field

[0001] This application relates to the field of ceramic battery technology, and in particular to a proton conductor ceramic battery for use under complex operating conditions and its preparation method. Background Technology

[0002] Proton conductor ceramic (PCC) batteries are a type of electrochemical device that uses proton conductor ceramics as the electrolyte membrane. They can efficiently convert hydrogen into electrical energy in fuel cell mode (PCFC), use surplus electricity to electrolyze water vapor to produce hydrogen in electrolyzer mode (PCEC), and extract high-purity hydrogen from hydrogen-containing gas mixtures.

[0003] A PCC single cell consists of a dense electrolyte membrane and porous negative and positive electrodes located on both sides. Ba(Ce,Zr)O3-based oxides are common proton-conducting ceramic electrolyte materials, such as BaZr. 0.1 Ce 0.7 Y 0.2 O 3-δ (BZCY), BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ (BZCYYb), etc. The negative electrode is generally a cermet composed of nickel and electrolyte materials, such as Ni-BZCY and Ni-BZCYYb. For proton conductor ceramic fuel cells and water electrolysis batteries, the positive electrode is generally perovskite, double perovskite, or layered perovskite oxide; for proton conductor ceramic batteries used in hydrogen purification, the positive electrode can be a nickel-based cermet or a redox-stable perovskite oxide.

[0004] However, electrolyte materials such as BZCY and BZCYYb are prone to decomposition reactions in high-concentration H2O and / or CO2 environments, which increases the internal resistance of the electrolyte membrane, destabilizes the active electrode interface, and sharply increases the interfacial polarization resistance, resulting in a significant degradation of the performance of proton conductor ceramic batteries.

[0005] Therefore, the chemical stability of proton conductor ceramic batteries has become a critical challenge that urgently needs to be overcome for their commercial application. Summary of the Invention

[0006] In view of this, this application provides a proton conductor ceramic battery for complex working conditions, which improves the problems of interface instability and performance degradation that occur when existing batteries work for a long time in high concentration H2O and CO2 environments.

[0007] This application provides a proton conductor ceramic battery for complex working conditions, comprising a positive electrode, an electrolyte, and a negative electrode arranged sequentially. The positive electrode includes a positive electrode catalyst; The negative electrode includes a negative electrode catalyst; A nano-catalyst is deposited on the inner surface of at least one of the positive and negative electrodes; the complex operating conditions include operating conditions in which the volume percentage of the working gas of the positive electrode is 20% to 100%, and the working gas includes one or more of H2O, CO2, methanol, ethanol, propanol, formic acid or acetic acid.

[0008] In some specific implementations, the electrolyte is a doped BaCeO₂. 3-δ doped BaZrO 3–δ BaZr 0.4 Sc 0.6 O 3–δ BaZr 1-x-y Ce x Y y O 3–δ Ba3Ca 1+x Nb 2–x O9 or Ba5(R)2Al2SnO 13 One or more of the following; Where R is any one of Gd, Dy, Ho, Y, Er, Tm, or Yb, 0 <x<1,0<y<1,0< δ <1; The thickness of the electrolyte is from 1 μm to 40 μm.

[0009] In some specific implementations, the nanocatalyst includes Fe, Ni, Co, NiO, FeNi, , , , Ba 0.5 Sr 0.5 Co 0.2 Fe 0.8 O 3-δ 、SmBa 0.5 Sr 0.5 Co2O 5+δ Sr2Fe 1.5 Mo 0.5 O 6-δ La 2-x Sr x Fe 2-y-z Ni y Mo z O 6-δ BaZr 1-x Y x O 3–δ BaZr 0.4 Sc 0.6 O 3–δBaZr 1-x-y Ce x Y y O 3–δ Sr2Sc 1+x Nb 1–x O 6–δ Ba3Ca 1+x Nb 2–x O9、Ba5(R)2Al2SnO 13 La 5.5 WO 11.25–δ La 5.5 W 1-x Mo x O 11.25-δ La 2- x Mg x Ce 2-y M y O 7-δ La 2-x Ca x Ce2O 7-δ La 2-x K x Ce2O 7-δ Cu 1.3 Mn 1.7 O 4-δ or Ce 1-x Gd x O 2-δ One or more of the following, where R is Gd, Dy, Ho, Y, Er, Tm or Yb, M is any one of Ni, Ti, Zr, Sn, Y or Yb, and 0 <x<1,0<y<1,0< δ <1.

[0010] In some specific implementations, the negative electrode catalyst includes NiO, Fe2O3, Co3O4, CuO, and Sr2Fe. 1.5 Mo 0.5 O 6-δ (R1)(R2)O 3-δ (R1)(R3)O 3-δ (R1)(R4)O 6-δ La x Mo y O z Doped with one or more of the following: cerium oxide, WC, TiC, TaC, ZrC, MoWC2, Mo2C, (R5)3SiC2, (R6)2AlC, Ti3(R7)C2, Ti3(R8)C2, Ti2Al(R9), Ti3Al(R9)2, TiN, ZrN, VN, WN, NbN, TaN, or MoN; Where, 0 <x <5, 0< y <8, 0< z <27, 0 < δ <1, R1 is La or Sr, R2 is Cr, Fe or Mn, R3 is Ti, Fe, Co or Ni, R4 is Mo, Fe, Co, Ni, Mg or Mn, R5 is Ti or Nb, R6 is Ti, Cr or V, R7 is Si or Al, R8 is Si or Ge, and R9 is C or N.

[0011] In some specific implementations, the negative electrode further includes a mixture of the negative electrode catalyst and the electrolyte; The electrolyte is doped BaCeO. 3-δ doped BaZrO 3–δ BaZr 0.4 Sc 0.6 O 3–δ BaZr 1-x-y Ce x Y y O 3–δ Ba3Ca 1+x Nb 2–x O9 or Ba5(R)2Al2SnO 13 One or more of the following; Where R is any one of Gd, Dy, Ho, Y, Er, Tm, or Yb, 0 <x<1,0<y<1,0< δ <1; The electrolyte has a mass fraction of 20% to 60% in the negative electrode; the nanocatalyst has a mass fraction of 40% to 80% in the negative electrode; and the thickness of the negative electrode is 300 μm to 1000 μm.

[0012] In some specific implementations, the cathode catalyst includes PrNi 0.5 Co 0.5 O 3–δ Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3–δ BaCo 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3–δ Ba 0.5 Gd 0.8 La 0.7 Co2O 6–δ 、PrBa 0.5 Sr 0.5 Co 1.5 Fe0.5 O 6–δ Pr2NiO 4+δ NiO, CuO, Co3O4, Mn3O4 or Cu 1.3 Mn 1.7 O 4-δ One or more of them, 0 < δ <1.

[0013] In some specific implementations, the negative electrode further includes a mixture of the positive electrode catalyst and the electrolyte; The electrolyte is doped BaCeO. 3-δ doped BaZrO 3–δ BaZr 0.4 Sc 0.6 O 3–δ BaZr 1-x-y Ce x Y y O 3–δ Ba3Ca 1+x Nb 2–x O9 or Ba5(R)2Al2SnO 13 One or more of the following; Where R is any one of Gd, Dy, Ho, Y, Er, Tm, or Yb, 0 <x<1,0<y<1,0< δ <1; The thickness of the positive electrode is from 10 μm to 1000 μm; The mass fraction of the nanocatalyst in the positive electrode is 5% to 40%.

[0014] This application also provides a method for preparing a proton conductor ceramic battery for complex operating conditions, comprising: A nanocatalyst and a battery are provided; the battery includes a positive electrode, an electrolyte, and a negative electrode. Nanocatalysts are deposited on the inner surface of at least one of the positive and negative electrodes to obtain a proton conductor ceramic battery for use under complex operating conditions. The deposition includes ion impregnation and / or atomic deposition.

[0015] In some specific implementations, the ion impregnation method includes impregnating the nanocatalyst into the electrode framework, with an impregnation amount of 1% to 80%. The atomic deposition method includes one or more of atomic layer deposition, molecular layer deposition, or chemical vapor deposition.

[0016] This application improves the chemical stability of the positive or negative electrode under high concentrations of H2O, CO2, and organic atmospheres by coating the inner surface of the porous positive or negative electrode with nano-catalysts, and protects the electrolyte material from the damage of harsh atmospheres, thereby enhancing the performance stability of the proton conductor ceramic battery under actual industrial operating conditions. Attached Figure Description

[0017] Figure 1 A schematic diagram of the battery provided in Embodiment 1 of this application; Figure 2 This is a cross-sectional scanning electron microscope microstructure image of the battery provided in Embodiment 1 of this application; Figure 3 XRD phase formation curves of LMCNO nanocatalysts prepared in Example 2 of this application and XRD curves after treatment in a reducing atmosphere; Figure 4 A comparison of long-term stability curves of batteries with different LMCNO impregnation amounts prepared for electrolysis tests in Example 2 of this application; Figure 5 The XRD phase curve of the NiO-BZY nanocatalyst prepared in Example 3 of this application and the XRD curve after treatment in a reducing atmosphere are shown. Figure 6 This is a long-term stability curve of NiO-BZY impregnated in Example 3 of this application; Figure 7 The XRD phase curve of the NiO-GDC nanocatalyst prepared in Example 4 of this application and the XRD curve after treatment in a reducing atmosphere are shown. Figure 8 This is a long-term stability curve of NiO-GDC impregnated in Example 4 of this application. Detailed Implementation

[0018] It should be understood that the expression “one or more of…” individually includes each of the objects described after the expression, as well as various different combinations of two or more of the described objects, unless otherwise understood from the context and usage. The expression “and / or” combined with three or more described objects should be understood to have the same meaning, unless otherwise understood from the context.

[0019] The terms “including,” “having,” or “containing,” including the use of their grammatical synonyms, should generally be understood as open-ended and non-restrictive, for example, not excluding other unstated elements or steps, unless otherwise specifically stated or understood from the context.

[0020] It should be understood that the order of steps or the sequence of actions is not important as long as this application remains operational. Furthermore, two or more steps or actions may be performed simultaneously.

[0021] The use of any and all instances or exemplary language such as “e.g.” or “include” in this document is intended merely to better illustrate the application and does not constitute a limitation on the scope of the application. No language in this specification should be construed as indicating that any unclaimed element is essential to the practice of this application.

[0022] Furthermore, the numerical ranges and parameters used to define this application are approximate values, and the relevant values ​​in the specific embodiments have been presented as precisely as possible. However, any numerical value inevitably contains standard deviations due to individual test methods. Therefore, unless otherwise explicitly stated, it should be understood that all ranges, quantities, values, and percentages used in this disclosure are modified with the word "approximately." Here, "approximately" generally means that the actual value is within plus or minus 10%, 5%, 1%, or 0.5% of a specific value or range.

[0023] This application provides a proton conductor ceramic battery for complex working conditions, comprising a positive electrode, an electrolyte, and a negative electrode arranged sequentially. The positive electrode includes a positive electrode catalyst; The negative electrode includes a negative electrode catalyst; A nano-catalyst is deposited on the inner surface of at least one of the positive and negative electrodes; the complex operating conditions include operating conditions in which the volume percentage of the working gas of the positive electrode is 20% to 100%, and the working gas includes one or more of H2O, CO2, methanol, ethanol, propanol, formic acid or acetic acid.

[0024] This application improves the chemical stability of the electrolyte and electrode under complex actual working conditions with high concentrations of H2O, CO2 and organic matter by coating the inner surface of the porous positive or negative electrode with nano-catalysts, thereby enhancing the performance stability of the proton conductor ceramic battery under actual industrial operating conditions.

[0025] This application employs an in-surface deposition method to cover the inner surface of a porous electrode with a nano-catalyst, thereby improving the chemical stability of the Ba(Ce,Zr)O3-based oxide electrolyte in complex environments containing high concentrations of H2O, CO2, or organic matter, and enhancing the durability of the three-phase interface structure between the electrolyte and the electrode. The proton ceramic battery consists of a negative electrode, an electrolyte membrane, and a positive electrode.

[0026] In some specific implementations, the electrolyte includes, but is not limited to, BaCeO₂ doped electrolyte. 3-δ doped BaZrO 3–δ BaZr 0.4 Sc 0.6 O 3–δ BaZr 1-x-y Ce x Yy O 3–δ Ba3Ca 1+x Nb 2–x O9 or Ba5(R)2Al2SnO 13 One or more of them, preferably BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ Where R is any one of Gd, Dy, Ho, Y, Er, Tm, or Yb, 0 <x<1,0<y<1,0< δ <1; the electrolyte thickness is 1 μm to 40 μm, preferably 5-15 μm. m. The doping element may include one or more of Gd, Nd, Sm, Y, Yb, Sc, In, or Ga.

[0027] In some specific implementations, the nanocatalyst includes, but is not limited to, Fe, Ni, Co, NiO, FeNi, , , , Ba 0.5 Sr 0.5 Co 0.2 Fe 0.8 O 3-δ 、SmBa 0.5 Sr 0.5 Co2O 5+δ Sr2Fe 1.5 Mo 0.5 O 6-δ La 2-x Sr x Fe 2-y-z Ni y Mo z O 6-δ BaZr 1-x Y x O 3–δ BaZr 0.4 Sc 0.6 O 3–δ BaZr 1-x-y Ce x Y y O 3–δ Sr2Sc 1+x Nb 1–x O 6–δ Ba3Ca 1+x Nb 2–x O9、Ba5(R)2Al2SnO 13 La 5.5 WO 11.25–δ La5.5 W 1-x Mo x O 11.25-δ La 2- x Mg x Ce 2-y M y O 7-δ La 2-x Ca x Ce2O 7-δ La 2-x K x Ce2O 7-δ Cu 1.3 Mn 1.7 O 4-δ or Ce 1-x Gd x O 2-δ One or more of the following, preferably NiO and La 1.85 Mg 0.15 Ce 1.9 Ni 0.1 O 7-δ NiO-BaZr 0.9 Y 0.1 O 3-δ NiO-Ce 0.8 Gd 0.2 O 2-δ And so on. Where R is any one of Gd, Dy, Ho, Y, Er, Tm, or Yb, M is any one of Ni, Ti, Zr, Sn, Y, or Yb, and 0 <x<1,0<y<1,0< δ <1.

[0028] In some specific implementations, the negative electrode catalyst includes, but is not limited to, NiO, Fe2O3, Co3O4, CuO, and Sr2Fe. 1.5 Mo 0.5 O 6-δ (R1)(R2)O 3-δ (R1)(R3)O 3-δ (R1)(R4)O 6-δ La x Mo y O z One or more of the following doped with cerium oxide, WC, TiC, TaC, ZrC, MoWC2, Mo2C, (R5)3SiC2, (R6)2AlC, Ti3(R7)C2, Ti3(R8)C2, Ti2Al(R9), Ti3Al(R9)2, TiN, ZrN, VN, WN, NbN, TaN or MoN, preferably NiO; Where, 0 < x<5, 0< y <8, 0< z <27, preferably x =2, y =2 or 3, z =9 or 12, 0 < δ <1, R1 is La or Sr, R2 is any one of Cr, Fe or Mn, R3 is any one of Ti, Fe, Co or Ni, R4 is any one of Mo, Fe, Co, Ni, Mg or Mn, R5 is Ti or Nb, R6 is any one of Ti, Cr or V, R7 is Si or Al, R8 is Si or Ge, and R9 is C or N.

[0029] In some specific implementations, the negative electrode further includes a mixture of the negative electrode catalyst and the electrolyte; The electrolyte is doped BaCeO. 3-δ doped BaZrO 3–δ BaZr 0.4 Sc 0.6 O 3–δ BaZr 1-x-y Ce x Y y O 3–δ Ba3Ca 1+x Nb 2–x O9 or Ba5(R)2Al2SnO 13 One or more of them, preferably BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ ; Where R is any one of Gd, Dy, Ho, Y, Er, Tm, or Yb, 0 <x<1,0<y<1,0< δ <1, preferably Y or Yb; The electrolyte has a mass fraction of 20% to 60% in the negative electrode, preferably 30-40%; the nanocatalyst has a mass fraction of 40% to 80% in the negative electrode, preferably 60-70%; the thickness of the negative electrode is 300 μm to 1000 μm, preferably 400-600 μm. m.

[0030] In some specific implementations, the cathode catalyst includes PrNi 0.5 Co 0.5 O 3–δ Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3–δBaCo 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3–δ Ba 0.5 Gd 0.8 La 0.7 Co2O 6–δ 、PrBa 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 6–δ Pr2NiO 4+δ NiO, CuO, Co3O4, Mn3O4 or Cu 1.3 Mn 1.7 O 4-δ One or more of the above-mentioned electronic conductors and proton conductor electrolyte materials, preferably NiO.

[0031] In some specific implementations, the positive electrode further includes a mixture of the positive electrode catalyst and the electrolyte; The electrolyte is doped BaCeO. 3-δ doped BaZrO 3–δ BaZr 0.4 Sc 0.6 O 3–δ BaZr 1-x-y Ce x Y y O 3–δ Ba3Ca 1+x Nb 2–x O9 or Ba5(R)2Al2SnO 13 One or more of them, preferably BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ ; Where R is any one of Gd, Dy, Ho, Y, Er, Tm, or Yb, 0 <x<1,0<y<1,0< δ <1, preferably Y or Yb; The thickness of the positive electrode is from 10 μm to 1000 μm, preferably 20-40 μm. m; The mass fraction of the nanocatalyst in the positive electrode is 5% to 40%, preferably 15-25%.

[0032] In some specific implementations, the working gas of the positive electrode includes one or more of H2O, CO2, methanol, ethanol, propanol, formic acid, or acetic acid.

[0033] This application also provides a method for preparing a proton conductor ceramic battery for complex operating conditions, comprising: A nanocatalyst and a battery are provided; the battery includes a positive electrode, an electrolyte, and a negative electrode. Nanocatalysts are deposited on the inner surface of at least one of the positive and negative electrodes to obtain a proton conductor ceramic battery for use under complex operating conditions. The deposition includes ion impregnation and / or atomic deposition, preferably ion impregnation.

[0034] In some specific implementations, the ion impregnation method involves immersing a porous substrate material in a salt solution containing target metal ions, utilizing capillary adsorption, diffusion, and ion exchange to form highly active nanoparticles or an interface modification layer on the pore surface. Specifically, this includes impregnating a nanocatalyst into an electrode framework, with an impregnation amount of 1-80%, preferably 5% to 20%. The atomic deposition method includes one or more of atomic layer deposition, molecular layer deposition, or chemical vapor deposition. Atomic layer deposition, similar to molecular layer deposition, uses alternating pulses of metal precursors and oxidants introduced into the reaction chamber, purged with inert gas in between, to achieve atomic and molecular-level growth through self-limiting surface reactions; while chemical vapor deposition involves delivering gaseous precursors to the surface of a high-temperature substrate, causing a chemical reaction and depositing a film.

[0035] The present application is further illustrated below with reference to embodiments. The scope of protection of the present application is not limited to the following embodiments.

[0036] Example 1

[0037] This embodiment provides a battery comprising NiO-BaZr without the addition of a pore-forming agent. 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ Electrodes, dense BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ Electrolyte film, porous NiO-BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ Electrodes, in which δThe value is 0. Two types of batteries were obtained by casting-stacking-hot pressing-co-sintering method: a quasi-symmetric NiO-BZCYYb (no pore-forming agent) negative electrode support | BZCYYb | NiO-BZCYYb (porous) positive electrode thin film battery and a fully symmetric NiO-BZCYYb (porous) negative electrode | BZCYYb | NiO-BZCYYb (porous) positive electrode battery.

[0038] Specifically, (1) using ordinary tape casting, non-porous electrode green blanks, porous electrode green blanks, and electrolyte green blanks are prepared respectively. Through layer-by-layer stacking, a full-cell green blank containing the battery negative electrode, electrolyte, and battery positive electrode is obtained by hot pressing under a pressure of 85℃ and 50MPa in a warm isostatic press for 68 minutes. The stacking combination of the quasi-symmetric battery is 12 layers of non-porous electrode green blank, 1 layer of electrolyte green blank, and 1 layer of porous electrode green blank; the stacking combination of the fully symmetric battery is 6 layers of porous electrode green blank, 1 layer of electrolyte green blank, and 6 layers of porous electrode green blank. (2) Battery green blank debinding and sintering: In a muffle furnace, the battery is first debinded at 500℃-1000℃ to remove organic matter from the green blank, and then the battery electrolyte is sintered and densified at 1300℃-1500℃. Figure 1 This is a schematic diagram of a battery, where 1 is the positive electrode catalyst, 2 is the electrolyte, 3 is the nano-catalyst, and 4 is the negative electrode catalyst. Figure 2 This is a cross-sectional scanning electron microscope (SEM) image of the microstructure. Figure 2 The parameters for the test are SU8220 15.0kV 14.6mm×2.00k SE(L) in the lower left corner.

[0039] Example 2

[0040] This embodiment provides a proton conductor ceramic battery for use under complex operating conditions, a quasi-symmetric NiO-BZCYYb|BZCYYb|LMCNO@NiO-BZCYYb proton conductor ceramic battery, the preparation method of the proton conductor ceramic battery includes: Based on the battery provided in Example 1, nano-La was coated on the inner surface of the porous positive electrode. 1.85 Mg 0.15 Ce 1.9 Ni 0.1 O 7-δ (LMCNO) oxide catalyst, wherein δ The value is 0. In this embodiment, the impregnation method is used, and the impregnation amount is 5-20%.

[0041] (1) The LMCNO catalyst material required for the experiment was prepared by the sol-gel method: ① Weigh out La(NO3)3·6H2O, Mg(NO3)2·6H2O, Ce(NO3)3·6H2O and Ni(NO3)3·6H2O according to the stoichiometric ratio, and dissolve them in a certain amount of deionized water; ② Add citric acid and EDTA to the solution to complex it according to the ratio of metal ions: citric acid: ethylenediaminetetraacetic acid = 1:1:1.5, and then add ammonia to adjust the pH of the solution to neutral (around 7). ③ Place the prepared aqueous solution on a magnetic stirrer and stir to evaporate at a temperature of 80℃. Stop evaporation when the solution is concentrated to 0.5 mol / L, for subsequent impregnation.

[0042] Figure 3 The XRD sintering phase curve of the impregnated phase LMCNO at 850℃ is shown in (a). The impregnated phase synthesized in air exhibits a good double fluorite structure. The curve after treatment in a reducing atmosphere at 700℃ for 5 hours is shown in (b). The material still maintains the stability of the phase structure.

[0043] (2) The prepared LMCNO was impregnated in a porous NiO-BZCYYb framework using a pipette: ① Each soaking The impregnated batteries were then placed in a muffle furnace and sintered at 350°C for 2 hours to decompose nitrates and organic matter. The impregnation was repeated multiple times to obtain the expected quality (impregnation amounts of 0%, 5%, 10%, 15%, and 20%, with 0% impregnation amount used as a control experiment). ② Once the weight of the impregnated phase in the electrode reaches the expected mass ratio, which is 5%, 10%, 15%, and 20% of the mass of the porous electrode skeleton of the battery, the battery is then sintered in air at the phase formation temperature of the impregnated phase to ensure complete phase formation of the impregnated phase in the skeleton, and finally a proton ceramic battery of NiO-BZCYYb|BZCYYb|LMCNO@NiO-BZCYYb is obtained. The overall thickness of the battery is 600μm and the electrolyte thickness is 15μm.

[0044] ③ Test conditions: A silver wire current collector was used. The battery was sealed to an alumina tube with ceramic adhesive for testing. A quartz glass tube was placed outside the alumina tube for feeding the raw material gas, and purge gas was introduced into the alumina tube. The test device was heated to 700℃ at a rate of 1℃ / min, and the electrolytic performance was observed at 550℃-700℃. A mixture of 50% humidity ethanol and water was introduced into the outer glass tube under air load at a flow rate of 50 mL / min, while H2 was introduced into the inner alumina tube at a flow rate of 50 mL / min as purge gas.

[0045] Figure 4 In this embodiment, the temperature was 650°C and the current was 0.5 A / cm. 2A comparison of the long-term stability curves of batteries with different impregnation amounts (0-20%) used for water vapor electrolysis under operating conditions reveals that the battery's operational stability is significantly optimized with increasing nanocatalyst coverage in the cathode material. The optimal stability curve is obtained when the impregnation amount reaches 20%, maintaining stable electrolysis for 100 hours. This result confirms that depositing nanocatalysts on the inner surface of porous electrodes can indeed enhance the durability of the three-phase interface structure between the electrolyte and electrode, thereby improving the operational stability of proton conductor ceramic batteries in practical applications.

[0046] Example 3

[0047] This embodiment provides a proton conductor ceramic battery for use under complex operating conditions, a quasi-symmetric NiO-BZCYYb|BZCYYb|NiO-BZY@NiO-BZCYYb proton conductor ceramic battery, the preparation method of the proton conductor ceramic battery includes: Based on the battery provided in Example 1, the inner surface of the porous positive electrode is covered with 10% NiO-90% BaZr. 0.9 Y 0.1 O 3-δ (NiO-BZY) nanocatalyst, in which δ The value is 0. In this embodiment, the impregnation method is used, and the impregnation amount is 20%.

[0048] (1) The NiO-BZY catalyst material required for the experiment was prepared by the sol-gel method: ① Weigh Ba(NO3)2, Zr(NO3)4·5H2O, Y(NO3)3·6H2O, and Ni(NO3)3·6H2O according to the stoichiometric ratio, and dissolve them in a certain amount of deionized water; ② Add citric acid and EDTA to complex the solution, and then add ammonia to adjust the pH of the solution to neutral (around 7). ③ Similarly, place the prepared aqueous solution on a magnetic stirrer for evaporation, setting the evaporation temperature to 80℃. Stop evaporation when the solution is concentrated to 0.5 mol / L, for subsequent impregnation.

[0049] Figure 5 The XRD sintering phase curve of the impregnated phase NiO-BZY at 1000℃ is shown in (a). Specifically, it is a composite phase of NiO and BZY. The synthesized NiO-BZY exhibits a good perovskite structure. The curve after treatment in a reducing atmosphere at 700℃ for 5 hours is shown in (b). The material still maintains the stability of the phase structure.

[0050] Following the preparation method in Example 2, a NiO-BZCYYb|BZCYYb|NiO-BZY@NiO-BZCYYb proton conductor ceramic battery was obtained with an impregnation amount of 20% of the porous electrode skeleton mass. The overall thickness of the battery was 600 μm, and the electrolyte thickness was 15 μm.

[0051] Using a similar testing environment as in Example 2, the working atmosphere was changed to an air-loaded mixture of methanol and water with 50% humidity at a flow rate of 50 mL / min through the outer glass tube, while H2 was passed through the inner corundum tube at a flow rate of 50 mL / min as a purge gas. The same electrolytic stability tests were performed on the prepared NiO-BZCYYb|BZCYYb|NiO-BZY@NiO-BZCYYb proton conductor ceramic battery. Figure 6 This application was performed at 650℃, 0.5A / cm. 2 The graph shows the long-term stability test of the battery under 20% impregnation conditions when used for water vapor electrolysis. It can be seen that impregnation with NiO-BZY solution also improves stability, and the battery can maintain stable operation for 100 hours.

[0052] Example 4

[0053] This embodiment provides a proton conductor ceramic battery for complex operating conditions, a fully symmetric proton ceramic battery of NiO-GDC@NiO-BZCYYb|BZCYYb|NiO-GDC@NiO-BZCYYb, the preparation method of the proton conductor ceramic battery includes: Based on the battery provided in Example 1, the inner surfaces of both the porous positive electrode and the porous negative electrode are covered with a mixture containing 10% NiO to 90% Ce. 0.8 Gd 0.2 O 2-δ (NiO-GDC) nanocatalyst, in which δ The value is 0. In this embodiment, the impregnation method is used, and the impregnation amount is 20% of the mass of the porous electrode skeleton on both sides.

[0054] Similarly, following the sol-gel method described above, and according to the stoichiometric ratio of the catalyst, weigh Gd(NO3)3·6H2O, Ce(NO3)3·6H2O, and Ni(NO3)3·6H2O to prepare the impregnation solution for NiO-GDC. Figure 7 The XRD sintering phase formation curve of the impregnation solution at 600℃ is shown in (a), indicating good phase formation. Meanwhile, the curve after treatment at 700℃ for 5 hours in a reducing atmosphere (b) shows that the material still maintains the stability of the phase structure.

[0055] Following the preparation method in Example 2, the working atmosphere was changed to a mixed gas of 50% H2 + 50% CO2 being introduced into the outer glass tube at a flow rate of 50 mL / min, and H2 being introduced into the inner corundum tube at a flow rate of 50 mL / min as a purge gas. The hydrogen pump stability test of the prepared NiO-GDC@NiO-BZCYYb|BZCYYb|NiO-GDC@NiO-BZCYYb fully symmetric proton ceramic battery was performed to separate hydrogen. The overall thickness of the battery was 560 μm, and the electrolyte thickness was 12 μm. Figure 8 This application is based on 700℃ and 0.5A / cm. 2 Under operating conditions, the battery with a 20% impregnation level was used for long-term stability testing to separate hydrogen from a CO2 and H2 mixture. It was found that the battery with double-sided deposited nanocatalysts could maintain stable operation for 80 hours even at higher temperatures.

[0056] This result further confirms that by depositing suitable nanocatalysts, including but not limited to the catalysts proposed in the invention, on the inner surface of porous electrodes, the chemical stability of Ba(Ce,Zr)O3-based oxide electrolytes in complex environments containing high concentrations of H2O, CO2, or organic matter can be improved, thereby enhancing the operational stability of proton conductor ceramic batteries in practical applications.

[0057] Example 5

[0058] This embodiment provides a proton conductor ceramic battery for complex operating conditions. The preparation method is as follows: Based on the quasi-symmetric NiO-BZCYYb (no pore-forming agent) negative electrode support |BZCYYb|NiO-BZCYYb (porous) positive electrode thin-film battery provided in Example 1, the thin-film positive electrode is replaced with porous Ba. 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3–δ (BSCF) electrode, in which δ The process was the same as in Example 1, using a tape casting-stacking-hot pressing-co-sintering method. The stacked assembly consisted of 12 layers of non-porous NiO-BZCYYb electrode green body, 1 layer of BZCYYb electrolyte green body, and 1 layer of porous BSCF electrode green body, to prepare a NiO-BZCYYb (porosity-free) negative electrode | BZCYYb | BSCF (porous) positive electrode battery. The overall battery thickness was 600 μm, and the electrolyte thickness was 15 μm. The LMCNO nanocatalyst from Example 2 was used again, and 20% of the positive electrode framework mass of the catalyst was impregnated onto the inner surface of the BSCF positive electrode.

[0059] Following the preparation method and testing conditions in Example 2, the prepared NiO-BZCYYb|BZCYYb|LMCNO@BSCF proton ceramic battery underwent the same electrolytic stability test. Table 1 shows the electrolytic stability of this example at 650℃ and 0.5 A / cm². 2 The data shows the long-term stability test results under operating conditions, specifically for water vapor electrolysis. It can be observed that replacing the positive electrode with a BSCF electrode, which has higher catalytic activity, and continuing to use the impregnated catalyst method, improves stability while reducing voltage and enhancing the overall electrochemical performance of the battery.

[0060] Example 6

[0061] This embodiment provides a proton conductor ceramic battery for use under complex operating conditions. The preparation method is as follows: Based on the fully symmetrical NiO-BZCYYb (porous) negative electrode | BZCYYb | NiO-BZCYYb (porous) positive electrode battery in Example 1, the porous NiO-BZCYYb positive and negative electrodes are replaced with porous Sr2Fe. 1.5 Mo 0.5 O 6-δ (SFM) electrode, in which δ The value was 0. A casting-stacking-hot pressing-co-sintering method was used, with the specific process identical to Example 1. The stacked assembly consisted of a 6-layer porous SFM electrode green body, a 1-layer BZCYYb electrolyte green body, and a 6-layer porous SFM electrode green body, thus preparing an SFM (porous) negative electrode | BZCYYb | SFM (porous) positive electrode battery. The overall battery thickness was 560 μm, and the electrolyte thickness was 12 μm. The LMCNO nanocatalyst from Example 2 was continued, and through impregnation, 20% of the electrode framework mass of the catalyst was coated onto the inner surface of both SFM electrodes.

[0062] Following the preparation method and testing conditions in Example 2, the prepared LMCNO@SFM|BZCYYb|LMCNO@SFM proton ceramic battery underwent the same electrolytic stability test. In this example, the test was conducted at 650℃ and 0.5 A / cm². 2 Table 1 shows the long-term stability test data for water vapor electrolysis under the operating conditions. Using a symmetrical SFM electrode, the stability performance can also be improved after depositing nanocatalysts, and the battery can guarantee stable operation for 80 hours.

[0063] This result further confirms that depositing suitable nanocatalysts on the inner surface of porous electrodes, a method applicable to different electrodes, can improve the chemical stability of Ba(Ce, Zr)O3-based oxide electrolytes in complex environments containing high concentrations of H2O, CO2, or organic matter, ultimately enhancing the operational stability of proton conductor ceramic batteries in practical applications.

[0064] Example 7

[0065] This embodiment provides a proton conductor ceramic battery for use under complex operating conditions. The preparation method is as follows: Based on the quasi-symmetric NiO-BZCYYb (no pore-forming agent) negative electrode support |BZCYYb|NiO-BZCYYb (porous) positive electrode thin-film battery provided in Example 1, the negative electrode is replaced with a composite non-porous electrode of Fe2O3-BZCYYb, and the thin-film positive electrode is replaced with porous PrNi 0.5 Co 0.5 O 3-δ (PNC) electrode, in which δ The process was the same as in Example 1, using a tape casting-stacking-hot pressing-co-sintering method. The stacked assembly consisted of 12 layers of non-porous Fe2O3-BZCYYb electrode green bodies, 1 layer of BZCYYb electrolyte green body, and 1 layer of porous PNC electrode green body. This produced a Fe2O3-BZCYYb (without pore-forming agent) negative electrode | BZCYYb | PNC (porous) positive electrode battery with an overall battery thickness of 600 μm and an electrolyte thickness of 15 μm. The NiO-BZY nanocatalyst from Example 3 was used, and 20% of the positive electrode framework mass of the catalyst was impregnated onto the inner surface of the PNC positive electrode.

[0066] Following the preparation method and testing conditions in Example 2, the prepared Fe2O3-BZCYYb|BZCYYb|NiO-BZY@PNC proton ceramic battery underwent the same electrolytic stability test. Table 1 shows the electrolytic stability of this example at 650℃ and 0.5 A / cm². 2 Under the operating conditions, the battery in this application can maintain stability for 120 hours in the long-term stability test data under the condition of electrolysis of water vapor.

[0067] Example 8

[0068] This embodiment provides a proton conductor ceramic battery for complex operating conditions. The preparation method is as follows: Based on the fully symmetrical NiO-BZCYYb (porous) negative electrode|BZCYYb|NiO-BZCYYb (porous) positive electrode battery in Example 1, the porous NiO-BZCYYb positive and negative electrodes are replaced with porous CuO-BZCYYb electrodes. The method of tape casting-stacking-hot pressing-co-sintering is adopted, and the specific process is the same as in Example 1. The stacked assembly consists of 6 layers of porous CuO-BZCYYb electrode green blank, 1 layer of BZCYYb electrolyte green blank, and 6 layers of porous CuO-BZCYYb electrode green blank, thus preparing a CuO-BZCYYb (porous) negative electrode|BZCYYb|CuO-BZCYYb (porous) positive electrode battery. The overall thickness of the battery is 560 μm, and the electrolyte thickness is 12 μm. The NiO-BZY nanocatalyst from Example 3 was used again, and by impregnation, catalyst of 20% of the electrode skeleton mass was covered on the inner surface of both CuO-BZCYYb electrodes.

[0069] Following the preparation method and testing conditions in Example 2, the prepared NiO-BZY@CuO-BZCYYb|BZCYYb|NiO-BZY@CuO-BZCYYb proton ceramic battery underwent the same electrolytic stability test. Table 1 shows the electrolytic stability of this example at 650℃ and 0.5 A / cm². 2 Under the operating conditions, the battery in this application can maintain stability for 80 hours in the long-term stability test data under the condition of electrolysis of water vapor.

[0070] Example 9

[0071] This embodiment provides a proton conductor ceramic battery for complex operating conditions. The preparation method is as follows: Based on the quasi-symmetric NiO-BZCYYb (no pore-forming agent) negative electrode support |BZCYYb|NiO-BZCYYb (porous) positive electrode thin-film battery provided in Example 1, the negative electrode is replaced with a composite non-porous electrode of Co3O4-BZCYYb, and the thin-film positive electrode is replaced with porous BaCo. 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3–δ (BCFZY) electrode, in which δThe process was the same as in Example 1, using a tape casting-stacking-hot pressing-co-sintering method. The stacked assembly consisted of 12 layers of non-porous Co3O4-BZCYYb electrode green body, 1 layer of BZCYYb electrolyte green body, and 1 layer of porous PNC electrode green body. This produced a Co3O4-BZCYYb (no pore-forming agent) negative electrode | BZCYYb | BCFZY (porous) positive electrode battery. The overall battery thickness was 600 μm, and the electrolyte thickness was 15 μm. The NiO-GDC nanocatalyst from Example 4 was used, and 20% of the positive electrode framework mass of the catalyst was impregnated onto the inner surface of the BCFZY positive electrode.

[0072] Following the preparation method and testing conditions in Example 2, the prepared Co3O4-BZCYYb|BZCYYb|NiO-GDC@BCFZY proton ceramic battery underwent the same electrolytic stability test. Table 1 shows the electrolytic stability of this example at 650℃ and 0.5 A / cm. 2 Under the operating conditions, the battery in this application can maintain stability for 100 hours in the long-term stability test data under the condition of electrolysis of water vapor.

[0073] The performance of the proton conductor ceramic batteries provided in Examples 2-9 for use under complex operating conditions was tested. The test parameters and results are shown in Table 1.

[0074] Table 1

[0075] The above description is merely a preferred embodiment of this application, but the scope of protection of this application is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in this application, based on the technical solution and application concept of this application, should be included within the scope of protection of this application.

Claims

1. A proton conductor ceramic battery for use under complex operating conditions, characterized in that, It includes a positive electrode, an electrolyte, and a negative electrode arranged in sequence; The positive electrode includes a positive electrode catalyst; The negative electrode includes a negative electrode catalyst; A nano-catalyst is deposited on the inner surface of at least one of the positive and negative electrodes; the complex operating conditions include operating conditions in which the volume percentage of the working gas of the positive electrode is 20% to 100%, and the working gas includes one or more of H2O, CO2, methanol, ethanol, propanol, formic acid or acetic acid.

2. The proton conductor ceramic battery according to claim 1, characterized in that, The electrolyte is doped BaCeO. 3-δ doped BaZrO 3–δ BaZr 0.4 Sc 0.6 O 3–δ BaZr 1-x-y Ce x Y y O 3–δ Ba3Ca 1+x Nb 2–x O9 or Ba5(R)2Al2SnO 13 One or more of the following; Where R is any one of Gd, Dy, Ho, Y, Er, Tm, or Yb, 0 <x<1,0<y<1,0< δ <1; The thickness of the electrolyte is from 1 μm to 40 μm.

3. The proton conductor ceramic battery according to claim 1, characterized in that, The nanocatalyst includes Fe, Ni, Co, NiO, FeNi, , , , Ba 0.5 Sr 0.5 Co 0.2 Fe 0.8 O 3-δ 、SmBa 0.5 Sr 0.5 Co2O 5+δ Sr2Fe 1.5 Mo 0.5 O 6-δ La 2-x Sr x Fe 2-y-z Ni y Mo z O 6-δ BaZr 1-x Y x O 3–δ BaZr 0.4 Sc 0.6 O 3–δ BaZr 1-x-y Ce x Y y O 3–δ Sr2Sc 1+x Nb 1–x O 6–δ Ba3Ca 1+x Nb 2–x O9, Ba5R2Al2SnO 13 La 5.5 WO 11.25–δ La 5.5 W 1-x Mo x O 11.25-δ La 2- x Mg x Ce 2-y M y O 7-δ La 2-x Ca x Ce2O 7-δ La 2-x K x Ce2O 7-δ Cu 1.3 Mn 1.7 O 4-δ or Ce 1-x Gd x O 2-δ One or more of the following; Where R is any one of Gd, Dy, Ho, Y, Er, Tm, or Yb, and M is any one of Ni, Ti, Zr, Sn, Y, or Yb, 0 <x<1,0<y<1,0< δ <1.

4. The proton conductor ceramic battery according to claim 1, characterized in that, The negative electrode catalyst includes NiO, Fe2O3, Co3O4, CuO, and Sr2Fe. 1.5 Mo 0.5 O 6-δ (R1)(R2)O 3-δ (R1)(R3)O 3-δ (R1)(R4)O 6-δ La x Mo y O z Doped with one or more of the following: cerium oxide, WC, TiC, TaC, ZrC, MoWC2, Mo2C, (R5)3SiC2, (R6)2AlC, Ti3(R7)C2, Ti3(R8)C2, Ti2Al(R9), Ti3Al(R9)2, TiN, ZrN, VN, WN, NbN, TaN, or MoN; Where, 0 < x <5, 0< y <8, 0< z <27, 0 < δ <1, R1 is La or Sr, R2 is any one of Cr, Fe or Mn, R3 is any one of Ti, Fe, Co or Ni, R4 is any one of Mo, Fe, Co, Ni, Mg or Mn, R5 is Ti or Nb, R6 is any one of Ti, Cr or V, R7 is Si or Al, R8 is Si or Ge, and R9 is C or N.

5. The proton conductor ceramic battery according to claim 1, characterized in that, The negative electrode also includes a mixture of the negative electrode catalyst and the electrolyte; The electrolyte is doped BaCeO. 3-δ doped BaZrO 3–δ BaZr 0.4 Sc 0.6 O 3–δ BaZr 1-x-y Ce x Y y O 3–δ Ba3Ca 1+ x Nb 2–x O9 or Ba5(R)2Al2SnO 13 One or more of the following; Where R is any one of Gd, Dy, Ho, Y, Er, Tm, or Yb, 0 <x<1,0<y<1,0< δ <1.

6. The proton conductor ceramic battery according to claim 1, characterized in that, The electrolyte has a mass fraction of 20% to 60% in the negative electrode; the nanocatalyst has a mass fraction of 40% to 80% in the negative electrode; and the thickness of the negative electrode is 300 μm to 1000 μm.

7. The proton conductor ceramic battery according to claim 1, characterized in that, The cathode catalyst includes PrNi 0.5 Co 0.5 O 3–δ Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3–δ BaCo 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3–δ Ba 0.5 Gd 0.8 La 0.7 Co2O 6–δ 、PrBa 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 6–δ Pr2NiO 4+δ NiO, CuO, Co3O4, Mn3O4 or Cu 1.3 Mn 1.7 O 4-δ One or more of them, 0 < δ <1.

8. The proton conductor ceramic battery according to claim 1, characterized in that, The positive electrode also includes a mixture of the positive electrode catalyst and the electrolyte; The electrolyte is doped BaCeO. 3-δ doped BaZrO 3–δ BaZr 0.4 Sc 0.6 O 3–δ BaZr 1-x-y Ce x Y y O 3–δ Ba3Ca 1+ x Nb 2–x O9 or Ba5(R)2Al2SnO 13 One or more of the following; Where R is any one of Gd, Dy, Ho, Y, Er, Tm, or Yb, 0 <x<1,0<y<1,0< δ <1; The thickness of the positive electrode is from 10 μm to 1000 μm; The mass fraction of the nanocatalyst in the positive electrode is 5% to 40%.

9. A method for preparing a proton conductor ceramic battery for complex operating conditions, characterized in that, include: A nanocatalyst and a battery are provided; the battery includes a positive electrode, an electrolyte, and a negative electrode. Nanocatalysts are deposited on the inner surface of at least one of the positive and negative electrodes to obtain a proton conductor ceramic battery for use under complex operating conditions. The deposition includes ion impregnation and / or atomic deposition.

10. The preparation method according to claim 9, characterized in that, The ion impregnation method involves impregnating a nanocatalyst into an electrode framework, with an impregnation amount ranging from 1% to 80%. The atomic deposition method includes one or more of atomic layer deposition, molecular layer deposition, or chemical vapor deposition.

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