CN-122013220-A - Solid oxide electrolytic cell anode material, solid oxide electrolytic cell, preparation method and application thereof

CN122013220ACN 122013220 ACN122013220 ACN 122013220ACN-122013220-A

Abstract

The invention belongs to the technical field of solid oxide batteries and electrolytic cells, and relates to the field of carbon dioxide reduction and methane oxidation coupling, in particular to a solid oxide electrolytic cell anode material, a solid oxide electrolytic cell and a preparation method and application thereof, wherein the chemical formula of the anode material is Ln 0.6 Sr 0.4 Mn 1+x O 3‑δ , x is-0.05, ln is one of Pr and Sm, and delta represents the non-stoichiometric ratio of oxygen in the material. The anode material of the solid oxide electrolytic cell can reduce the potential when ethylene and ethane are prepared by oxidizing methane with carbon dioxide, can improve the selectivity of ethane and ethylene in the methane oxidation coupling based on the stoichiometric regulation and control of Mn, and improves the economy of a product at one side of the anode.

Inventors

LIU ZHONGYUAN
LI YIFENG
REN MINQIAO
LI CHUNSONG
LI LINGXIU
ZHANG LIBO
JI WENXI
ZHANG LONGGUI

Assignees

中国石油化工股份有限公司
中石化(北京)化工研究院有限公司

Dates

Publication Date: 20260512
Application Date: 20241111

Claims (11)

1. The chemical formula of the anode material is Ln 0.6 Sr 0.4 Mn 1+x O 3-δ , wherein x is-0.05, ln is one of Pr and Sm, and delta represents the non-stoichiometric ratio of oxygen in the material.
2. The solid oxide cell anode material of claim 1, wherein: ln is Sm and x is 0 to 0.05, or Ln is Pr and x is-0.05 to 0.05, preferably, Ln is Pr, and x is 0 to 0.05.
3. The solid oxide cell anode material of claim 1, wherein: The solid oxide electrolytic cell anode material is a perovskite type oxide, preferably, The solid oxide electrolytic cell anode material is prepared by at least one of a sol-gel method, a coprecipitation method, a solid phase method and a low temperature self-propagating combustion method according to a stoichiometric ratio of Ln 0.6 Sr 0.4 Mn 1+x O 3-δ , and preferably by a gel method.
4. A method for preparing a solid oxide electrolytic cell anode material according to any one of claims 1-3, comprising the steps of mixing an Ln element source, an Sr element source and an Mn element source with optionally added citric acid and glucose according to the stoichiometric ratio of Ln 0.6 Sr 0.4 Mn 1+x O 3-δ , wherein the dosages of the citric acid and the glucose are different from 0, forming wet gel under the heating condition, foaming, drying and sintering to obtain the solid oxide electrolytic cell anode material.
5. The solid oxide cell anode material of claim 4, wherein: The source of Ln element is a soluble metal salt, preferably nitrate, of the Ln metal element, and/or, The source of Sr element is a soluble metal salt of Sr element, preferably strontium nitrate, and/or, The source of Mn element is a soluble metal salt of Mn element, preferably manganese nitrate, and/or, The ratio of the amount of each of citric acid and glucose to the total amount of the metal element sources is (0-6): 1, preferably (0.5-2): 1, wherein the total amount of the metal element sources is equal to the sum of the amounts of the total amounts of the Ln element source, the Sr element source and the Mn element source in terms of metal element, and/or, The conditions for foaming and drying comprise a temperature of 100-270 ℃ and/or a time of 1-4h and/or, The sintering conditions comprise a heating rate of 1-10 ℃ per minute, and/or a sintering heat preservation temperature of 850-1350 ℃ for 1-10 hours, and/or a cooling rate of 1-10 ℃ per minute, and/or, And also comprises the steps of crushing the foamed and dried material before sintering, and/or sintering, And the method further comprises the step of crushing the sintered material after sintering to obtain the powdery solid oxide electrolytic cell anode material.
6. A solid oxide electrolytic cell comprises an anode, an electrolyte and a cathode, wherein the electrolyte is a supporting oxygen ion conduction type electrolyte and is used for supporting the anode and the cathode, The anode comprises the solid oxide electrolytic cell anode material according to any one of claims 1 to 3 or the solid oxide electrolytic cell anode material obtained by the production method according to claim 4 or 5.
7. The solid oxide electrolysis cell according to claim 6, wherein: The electrolyte is at least one of zirconia YSZ type electrolyte and lanthanum strontium gallium magnesium LSGM type electrolyte, and/or the cathode is at least one of zirconia YSZ electrolyte material coated with yttrium, nickel oxide-YSZ, strontium iron molybdenum oxide and the same material as the anode material, preferably, The cathode and the electrolyte are derived from a solid oxide half cell, more preferably, the solid oxide half cell is at least one of a nickel-YSZ cathode support half cell coated with a zirconium oxide YSZ electrolyte, a YSZ electrolyte support half cell with nickel oxide-YSZ as a cathode, a YSZ support half cell with strontium iron molybdenum oxide as a cathode, a lanthanum strontium gallium magnesium LSGM electrolyte support half cell with strontium iron molybdenum oxide as a cathode, a YSZ support half cell with the same material as an anode as a cathode, and a lanthanum strontium gallium magnesium LSGM electrolyte support half cell with the same material as an anode as a cathode.
8. A method for producing a solid oxide cell according to claim 6 or 7, comprising the steps of mixing a mixture comprising the solid oxide cell anode material and optionally a pore-forming agent with a binder to obtain an anode printing paste, applying the anode printing paste to the anode side of the electrolyte, and drying and sintering to obtain an anode of the cell, preferably, The electrolyte is derived from a solid oxide half cell having a cathode and an electrolyte, in which case the anode printing paste is applied to the anode side of the electrolyte, dried and sintered to obtain a solid oxide cell.
9. The method of manufacture of claim 8, wherein: The pore-forming agent is selected from at least one of starch, graphite and PMMA powder, and/or, The addition amount of the pore-forming agent is 0-25wt% of the mass of the anode material of the solid oxide electrolytic cell, and/or, The binder is turpentine alcohol and ethyl cellulose, preferably the mass ratio of turpentine alcohol to ethyl cellulose is (15-9): 1, and/or, The mass ratio of the mixed material to the binder is (0.1-1.5): 1, the preferable ratio is (0.5-1): 1, and/or, The drying condition comprises that the temperature is 65-85 ℃ and/or the time is 5-10 min and/or, The sintering conditions comprise the temperature rising rate of 1-10 ℃ per minute in the sintering process, the sintering heat preservation temperature of 1000-1150 ℃, the heat preservation time of 2-5 h and the cooling rate of 1-10 ℃ per minute.
10. Use of a solid oxide cell anode material according to any one of claims 1 to 3 or a solid oxide cell anode material obtained according to the production process of claim 4 or 5 or a solid oxide cell according to claim 6 or 7 or a solid oxide cell obtained according to the production process of claim 8 or 9 for the production of hydrocarbons, preferably comprising ethylene and ethane, by oxidative methane coupling using carbon dioxide.
11. The use according to claim 10, characterized in that it comprises: Placing the cathode side of the solid oxide electrolytic cell in an atmosphere containing carbon dioxide at 750-850 ℃, placing the anode side of the solid oxide electrolytic cell in a methane atmosphere, applying an external voltage between the cathode and the anode, and performing methane oxidative coupling reaction on the solid oxide anode to obtain gas containing ethylene and ethane; Preferably, the applied voltage is in the range of 0.1 to 2V, preferably 0.9 to 1.2V, and/or, Preferably, the carbon dioxide-containing atmosphere is a carbon dioxide-hydrogen mixed atmosphere, preferably the volume fraction of carbon dioxide is 50% to 100%, preferably 70% to 95%.

Description

Solid oxide electrolytic cell anode material, solid oxide electrolytic cell, preparation method and application thereof Technical Field The invention belongs to the technical field of solid oxide batteries and electrolytic cells, and relates to the fields of carbon dioxide reduction and methane oxidation coupling, in particular to a solid oxide electrolytic cell anode material, a solid oxide electrolytic cell, a preparation method thereof and application of the solid oxide electrolytic cell anode material and the solid oxide electrolytic cell in preparing hydrocarbon compounds by using carbon dioxide oxidation methane coupling. Background With the increasing global urgent need for sustainable energy solutions, solid Oxide Electrolytic Cell (SOEC) technology has become a hotspot in scientific research and industry by virtue of its unique advantages of efficient conversion, flexible operation, and environmental friendliness. The core function of SOEC is to directly convert the electric energy generated by renewable energy sources (such as solar energy and wind energy) into chemical energy, and in this process, the electrolytic conversion of CO 2 is particularly attractive, because it provides the possibility to realize carbon cycle closure, reduce greenhouse gas emissions and produce carbon neutral fuel. In this conversion path, the anode (also commonly referred to as anode) is a critical component, and its choice of materials and design are directly related to electrolysis efficiency, stability, and long-term operating costs. Perovskite oxides represented by La 0.6Sr0.4MnO3-δ are used as anode materials for solid oxide cells because of their excellent thermochemical stability and electron conductivity. In recent years, a method for producing ethylene by coupling electrochemical methane oxidation (EC-OCM) on the anode side of a Solid Oxide Electrolytic Cell (SOEC) has attracted attention, in which activated oxidation of methane does not require direct introduction of oxygen, but oxygen ions can be provided by a solid oxide electrolyte. The electrolysis of carbon dioxide on the cathode side provides oxygen ions, so that not only can the combination of endothermic reaction and exothermic reaction be used for ensuring the thermal control of the electrolytic cell, but also the carbon dioxide can be reduced into carbon monoxide, and the system is changed into a carbon negative technology. La 0.6Sr0.4MnO3-δ is used as a traditional catalyst in the catalytic combustion reaction of methane, and the catalytic oxidation product is mainly carbon dioxide. The material has high activity, and the key point is that the surface characteristics of the material are that the high concentration of oxygen vacancies and the high concentration of active adsorbed oxygen, so that the material has high oxidizing ability. However, when attempting to apply such materials to oxidative coupling reactions of methane to produce ethane and ethylene, their high oxidizing properties become a disadvantage. Methane is often not selectively converted to ethane and ethylene in the reaction due to excessive oxidation, resulting in lower selectivity for both products. The transition metal substitution of the perovskite material, such as substitution of Mn element with Co, fe and Ni, can change the species of the perovskite material with surface activity for adsorbing oxygen, and is further expected to improve the catalytic activity. However, it is notable that Co, fe, ni-based perovskite oxide materials are commonly used as catalysts for methane catalytic combustion reactions. This suggests that merely adjusting the surface-active oxygen-adsorbing species by transition metal substitution may not be sufficient to alter the reaction path of methane over-catalytic oxidation. On the other hand, while Al-based perovskite such as LaAlO 3-δ is believed to have the potential to convert methane to ethane and ethylene, unfortunately it is an insulator and therefore cannot be used as an anode material. Therefore, it is necessary to develop a solid oxide electrolytic cell anode material suitable for preparing hydrocarbon compounds by oxidizing methane with carbon dioxide, and further, if a manganese-based perovskite material can be developed so as to be more suitable for the reaction of preparing ethane and ethylene by oxidizing methane. Disclosure of Invention The inventor of the invention has studied and found unexpectedly that, by replacing La in the conventional La 0.6Sr0.4Mn1+xO3-δ (x=0) material and changing the La into the solid oxide of Pr or Sm of lanthanide metal as the anode material of the electrolytic cell, the electrolysis potential of methane oxidation coupling carbon dioxide reduction reaction can be reduced, the selectivity of ethane and ethylene in methane oxidation coupling can be improved based on stoichiometric regulation and control of Mn, and the economy of the product on one side of the anode can be improved. The anode material of the Ln