CN111394748B - 一种用于co2电解的铁镍合金原位脱溶的层状钙钛矿阴极材料 - Google Patents
一种用于co2电解的铁镍合金原位脱溶的层状钙钛矿阴极材料 Download PDFInfo
- Publication number
- CN111394748B CN111394748B CN202010077336.3A CN202010077336A CN111394748B CN 111394748 B CN111394748 B CN 111394748B CN 202010077336 A CN202010077336 A CN 202010077336A CN 111394748 B CN111394748 B CN 111394748B
- Authority
- CN
- China
- Prior art keywords
- cathode material
- situ
- pbmfno
- iron
- solid oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000010406 cathode material Substances 0.000 title claims abstract description 32
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 18
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 title claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002105 nanoparticle Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000002001 electrolyte material Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910002709 B2O5+δ Inorganic materials 0.000 claims 1
- 238000013329 compounding Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- 229910002555 FeNi Inorganic materials 0.000 abstract description 9
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 5
- 229910052777 Praseodymium Inorganic materials 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 abstract description 3
- 230000010287 polarization Effects 0.000 abstract description 3
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- 230000002950 deficient Effects 0.000 abstract 1
- 239000010936 titanium Substances 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000002243 precursor Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 5
- 229960002303 citric acid monohydrate Drugs 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000004807 desolvation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000008279 sol Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910002132 La0.6Sr0.4Co0.2Fe0.8O3-δ Inorganic materials 0.000 description 2
- 229910002131 La0.6Sr0.4Co0.2Fe0.8O3–δ Inorganic materials 0.000 description 2
- 229910002130 La0.6Sr0.4Co0.2Fe0.8O3−δ Inorganic materials 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Inorganic materials [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005049 combustion synthesis Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inert Electrodes (AREA)
- Catalysts (AREA)
Abstract
本发明涉及用于CO2电解的固体氧化物电解池阴极材料，具体说是一种A缺位的层状钙钛矿阴极材料Pr0.9Ba0.9Mn2‑5xFe4xNixO5+δ(PBMFNO，x＝0.04～0.20)及其应用。本发明的特征在于：对钛矿材料Pr0.5Ba0.5MnO3材料在A位引入Pr、Ba缺位，B位掺入Fe、Ni两种过渡金属离子，分子式为Pr0.45Ba0.45Mn1‑5yFe4yNiyO3‑δ(y＝0.02～0.10)，通过H2还原使其转变PBMFNO，同时原位脱溶出的尺寸介于30‑50nm的铁镍合金FeNi3纳米颗粒。本发明制备出的钙钛矿阴极材料具有良好的稳定性和CO2催化活性，可以有效降低阴极极化。
Description
技术领域
本发明涉及一种用于CO2高温电解的固体氧化物电解池(SOEC)阴极材料，具体地说是一种铁镍合金原位脱溶的Pr0.9Ba0.9Mn2-5xFe4xNixO5+σ(PBMFNO，x＝0.04～0.20)层状钙钛矿阴极材料，以及包含该阴极材料的SOEC阴极。
背景技术
我国能源结构具有“贫油，少气，富煤”的特点，近年来国家不断推动和支持新型煤化工行业的发展来缓解过分依赖国外石油，天然气进口的现状。目前，新型煤化工行业技术不断创新和突破，特别是在煤直接或间接液化，煤制油，天然气，甲醇和烯烃等工艺方面，但是大量产生和排放的副产物CO2给环境带来了严重的负担。
CO2的电化学催化转化具有快速高效和产品纯度高的特点，特别是基于SOEC的高温电解，可以直接将CO2的还原为CO。利用高温电解实现CO2的资源化不仅有利于环境保护，而且有利于创造额外的经济效益。产生的CO不仅可以作为燃料气，而且还可以作为原料用于化工合成烯烃，进一步生产高附加值的化工产品。
传统的Ni基陶瓷阴极材料在高温CO2气氛中容易积碳，电解过程中Ni表面产生的无定型碳和石墨不仅会堵塞三相界面，而且会进一步扩散到Ni基体，进而造成整个阴极材料失效。最近，Pr0.5Ba0.5MnO3等钙钛矿基阴极材料得到了广泛的关注(Nature Materials,2015,14: 205-209)，该材料体系具有良好的抗积碳性能。但是，钙钛矿基阴极材料对于CO2吸附性能较差、催化活性较弱、电解过程极化损失大，如何提高其电极活性及对CO2的催化能力是需要解决的关键问题。
发明内容
本发明的目的是为了克服钙钛矿基阴极材料对CO2电催化活性不足的问题，在钙钛矿 Pr0.5Ba0.5MnO3材料的A位引入Pr、Ba缺位，B位掺入Fe、Ni两种过渡金属离子，分子式为Pr0.45Ba0.45Mn1-5yFe4yNiyO3-δ(y＝0.02～0.10)，通过H2还原使其转变为层状钙钛矿结构，同时原位脱溶出的尺寸介于30-50nm的铁镍合金FeNi3纳米颗粒，获得一种用于CO2电解的铁镍合金原位脱溶的高活性PBMFNO阴极材料。通过大量实验，本发明人发现，原位脱溶的铁镍合金纳米颗粒具有良好的稳定性，可以显著提高阴极材料的催化活性，降低电解过程的阴极极化。
本发明提供以下基于改进溶胶-凝胶-低温自蔓延方法的铁镍合金脱溶PBMFNO阴极材料的制备方法，包括：
步骤1：根据Pr0.45Ba0.45Mn1-5yFe4yNiyO3-δ中Pr、Ba、Mn、Fe和Ni元素的化学计量比，将Pr(NO3)3·6H2O、Ba(NO3)2、Mn(NO3)2、Ni(NO3)2·6H2O、Fe(NO3)3·9H2O均匀溶解于去离子水中，然后加入一定量的一水合柠檬酸和乙二醇，充分搅拌形成均匀透明溶液。
步骤2：将混合均匀的透明溶液于300-350℃之间加热3h，引发低温自蔓延反应，完全反应生成黑色粉体。
步骤3：将低温自蔓延生成的黑色粉体分别在950℃下保温4h，以形成ABO3型的Pr0.45Ba0.45Mn1-5yFe4yNiyO3-δ钙钛矿晶相。
步骤4：将制备的Pr0.45Ba0.45Mn1-5yFe4yNiyO3-δ钙钛矿粉体放置于管式炉中，在5％H2氛围下900℃还原10h。使Pr0.45Ba0.45Mn1-5yFe4yNiyO3-δ完全转化为A2B2O5型A缺位的PBMFNO 钙钛矿材料，同时材料表面原位脱溶出尺寸约为40nm的铁镍合金纳米颗粒。
优选地，所述步骤1中各种混合的金属离子与一水柠檬酸的摩尔比为1:1.5，溶解于200 mL的去离子水中，加入100mL乙二醇充分搅拌至形成均匀透明溶液。
优选地，所述步骤3中，升温的程序设定为5℃/min到600℃，之后是2℃/min到950℃。
优选地，所述步骤4中，还原过程从室温到950℃的升温速度为5℃/min。当Pr0.9Ba0.9Mn2-5xFe4xNixO5+σ中x＝0.04～0.20时，表面原位脱溶的大量FeNi3铁镍合金纳米颗粒，颗粒直径约为40nm。
本发明中的Pr0.45Ba0.45Mn1-5yFe4yNiyO3-δ材料也可以通过燃烧合成法和固相烧结法等方法合成，然后结合高温氢气还原均可制备铁镍合金原位脱溶的PBMFNO层状钙钛矿阴极材料。
本发明中发现A位引入的Pr和Ba缺位，可以显著提高阴极材料的氧空位，利于改善材料表面的CO2化学吸附能力。同时，B位脱溶出的FeNi3合金纳米颗粒可以显著提高阴极材料的CO2电催化反应活性。
本发明中还提供了铁镍合金原位脱溶PBMFNO层状钙钛矿阴极在CO2氛围下的抗积碳性能测试结果，样品表观形貌和碳沉积情况由扫描电子显微镜(SEM)和拉曼光谱结果验证，拉曼的特征峰位于1365cm-1(‘D’peak)和1585cm-1(‘G’peak)分别代表了表面积聚的石墨碳和无定形碳。
本发明中，固体氧化物电解池的阴极可以由PBMFNO阴极材料单独或与电解质材料复合构成。其中PBMFNO的质量分数为1-100％，电解质材料的质量分数为1-60％，电解质材料优选为是8％(质量分数)Y2O3稳定的ZrO2(YSZ)和GdxCe1-xO2-δ(GDC)中的一种或者是两者的混合物。阴极中加入一定量的电解质材料，可以增加和延长电催化反应的三相界面，改善阴极层与电解质层的热匹配性。
本发明中，不特别限制电池所用的电解质层的制备方法。在一些实施方案中，电解质的厚度为10–200μm之间，致密度达到95％以上，可以采用本领域公知的方法制备。同时不特别限制电池所用的阳极材料，阳极结构为多孔纳微结构，用于氧的催化还原析出反应，可以采用本领域共知的方法制备阳极。
本发明具有如下优点：
1：本发明的铁镍合金原位脱溶的PBMFNO层状钙钛矿阴极材料，具有Pr，Ba的A位缺位，增加了阴极材料的氧空位浓度，氧空位的浓度增加可以促进PBMFNO阴极材料对CO2的化学吸附。
2：本发明中PBMFNO原位脱溶的FeNi3铁镍合金纳米颗粒，不仅增加了阴极材料的电子电导率，而且改善了其对CO2的电催化还原活性，提高了钙钛矿基阴极CO2电解的电流密度。
3：本发明中PBMFNO原位脱溶FeNi3铁镍合金纳米颗粒的制备方法，相对于传统的浸渍方法，具有过程简单、高效省时的特点。
4：本发明中PBMFNO表面原位脱溶FeNi3铁镍合金纳米颗粒，与钙钛矿本体结合紧密、分散性好、稳定性高，避免了传统阴极材料纳米金属催化化剂颗粒易积碳和团聚的问题，具有良好的抗积碳性能。
下面结合说明书附图和实施方案进一步阐述本发明的内容。
附图说明
图1为未脱溶的Pr0.45Ba0.45Mn0.5Fe0.4Ni0.1O3-δ(A-PBMFNO)和脱溶后的Pr0.9Ba0.9MnFe0.8Ni0.2O5+δ(L-PBMFNO)样品的X射线衍射(XRD)图
图2为脱溶后L-PBMFNO样品的扫描电子显微镜(SEM)图
图3为脱溶后L-PBMFNO样品的透射电子显微镜(TEM)图
图4为脱溶后L-PBMFNO作为阴极，YSZ为电解质，La0.6Sr0.4Co0.2Fe0.8O3-δ(LSCF)为阳极构成的电解质支撑电解池的CO2的I-V曲线，测试条件：温度850℃，恒电压1.6V电解， CO2流量40mL/min。
具体实施方式
下面给出的实施例拟对本发明做进一步说明，但不能理解为是对本发明的保护范围的限制，该领域的技术人员根据上述本发明的内容对本发明做出的一些非本质的改进和调整，仍然属于本发明的保护范围。
实施例1：
步骤1：根据Pr0.45Ba0.45Mn0.5Fe0.4Ni0.1O3-δ(A-PBMFNO)中Pr、Ba、Mn、Fe和Ni元素的化学计量比分别计算出不同元素所需要的硝酸盐质量。先将这些硝酸盐溶解于去离子水中，充分搅拌约半小时后，然后加入59.8899g一水合柠檬酸和300mL乙二醇。同时，用氨水快速调节溶液pH至8～9之间，然后继续搅拌直至形成血红色澄清透明的前驱体溶胶，磁力搅拌器的转速为400–500r/min，搅拌的时间12h。
步骤2：配制好的前驱体溶胶转移至坩埚中，通过电阻丝加热引发生低温自蔓延反应。加热器的温度控制在350℃，逐渐将前驱体中的有机组分，水，氨水等组分缓慢蒸发掉，直至形成红褐色凝胶。形成凝胶后继续加热2-3h，红褐色的凝胶会发生自蔓反应生成前驱体黑色粉体。
步骤3：前驱体黑色粉体进一步通过程序升温煅烧，升温程序控制为5℃/min到600℃，保温4h，目的是去除低温自蔓延步骤残余的有机物组分，之后2℃/min到950℃，保温4h后，形成ABO3型钙钛矿样品A-PBMFNO。然后，通过乙醇湿法球磨进一步破碎Pr0.9Ba0.9Mn2O5+σ样品，转速控制为400～500r/min，时间为12h。球磨后取出样品，在105℃干燥12h。
步骤4：将干燥后的样品转移至管式炉中，在900℃和5％H2氛围下还原10h，形成A2B2O5型层状钙钛矿Pr0.9Ba0.9Mn2-5xFe4xNixO5+σ(L-PBMFNO)，期间会原位生长出大量的FeNi3纳米颗粒，FeNi3纳米合金颗粒的尺寸约为40nm。样品的XRD，SEM和TEM分析结果见说明书附图1，图2和图3。
步骤4：将L-PBMFNO作为阴极，YSZ作为电解质，La0.6Sr0.4Co0.2Fe0.8O3-δ(LSCF)为阳极构成电解质支撑的电解池片，YSZ和阳极中间使用GDC作保护层，电解池通过丝网印刷方式制备。
步骤5：电解池L-PBMFNO/GDC/YSZ/GDC/LSCF在850℃置于CO2氛围下进行电解测试，气体流量为40mL/min H2+10mL/min N2。Pr0.9Ba0.9M1.0Fe0.8Ni0.2O5+σ作阴极的电解池在850℃和2.0V下CO2的电解电流密度为575.56mA/cm2。电解池的CO2电解I-V曲线见说明书附图4。
实施例2：
步骤1：根据Pr0.45Ba0.45Mn0.5Fe0.48Ni0.02O3-δ中Pr、Ba、Mn、Fe和Ni元素的化学计量比分别计算出不同元素所需要的硝酸盐质量。先将这些硝酸盐溶解于去离子水中，充分搅拌约半小时后，然后加入59.8899g一水合柠檬酸和300mL乙二醇。同时，用氨水快速调节溶液pH至8～9之间，然后继续搅拌直至形成血红色澄清透明的前驱体溶胶，磁力搅拌器的转速为400–500r/min，搅拌的时间12h。
步骤2：配制好的前驱体溶胶转移至坩埚中，通过电阻丝加热引发生低温自蔓延反应。加热器的温度控制在350℃，逐渐将前驱体中的有机组分，水，氨水等组分缓慢蒸发掉，直至形成红褐色凝胶。形成凝胶后继续加热2-3h，红褐色的凝胶会发生自蔓反应生成前驱体黑色粉体。
步骤3：前驱体黑色粉体进一步通过程序升温煅烧，升温程序控制为5℃/min到600℃，保温4h，目的是去除低温自蔓延步骤残余的有机物组分，之后2℃/min到950℃，保温4h后，形成ABO3型钙钛矿样品Pr0.45Ba0.45Mn0.5Fe0.48Ni0.02O3-δ。然后，通过乙醇湿法球磨进一步破碎 Pr0.9Ba0.9Mn2O5+σ样品，转速控制为400～500r/min，时间为12h。球磨后取出样品，在105℃干燥12h。
步骤4：将干燥后的样品转移至管式炉中，在900℃和5％H2氛围下还原10h，形成A2B2O5型层状钙钛矿Pr0.9Ba0.9MnFe0.96Ni0.04O5+δ，期间会原位生长出一定量的FeNi3纳米颗粒，FeNi3纳米合金颗粒的尺寸约为30-50nm。
步骤4：将Pr0.9Ba0.9MnFe0.96Ni0.04O5+δ与YSZ混合(质量比50％：50％)组成阴极材料,阳极部分选用LSCF，组装成YSZ电解质支撑的电解池片，YSZ和阳极中间使用GDC作保护层，电解池通过丝网印刷方式制备。
步骤5：电解池Pr0.9Ba0.9MnFe0.96Ni0.04O5+δ+YSZ/GDC/YSZ/GDC/LSCF在850℃置于CO2氛围下进行电解测试，气体流量为40mL/min H2+10mL/min N2。Pr0.9Ba0.9MnFe0.96Ni0.04O5+δ与YSZ为复合阴极的电解池在850℃和2.0V下CO2的电解电流密度为525.78mA/cm2。
Claims (5)
1.一种用于CO2电解的固体氧化物电解池阴极材料，属于A缺位的A2B2O5+δ型层状钙钛矿复合氧化物，具体分子式为：Pr0.9Ba0.9Mn2-5xFe4xNixO5+δ，其中x＝0.04～0.20。
2.如权利要求1中所述的用于CO2电解的固体氧化物电解池阴极材料，其特征在于，该材料表面具有原位脱溶的铁镍合金FeNi3纳米颗粒，颗粒尺寸介于30-50nm之间。
3.一种用于CO2电解的固体氧化物电解池阴极，包含权利要求1或2中的固体氧化物电解池阴极材料。
4.如权利要求3所述的固体氧化物电解池阴极，由所述固体氧化物电解池阴极材料和电解质材料复合构成，其中所述固体氧化物电解池阴极材料的质量分数为1-100％；所述电解质材料的质量分数为1-60％。
5.如权利要求4中所述固体氧化物电解池阴极，其中所述电解质材料是8％质量分数Y2O3稳定的ZrO2和GdxCe1-xO2-δ中的一种或者是两者的混合物。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010077336.3A CN111394748B (zh) | 2020-01-28 | 2020-01-28 | 一种用于co2电解的铁镍合金原位脱溶的层状钙钛矿阴极材料 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010077336.3A CN111394748B (zh) | 2020-01-28 | 2020-01-28 | 一种用于co2电解的铁镍合金原位脱溶的层状钙钛矿阴极材料 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111394748A CN111394748A (zh) | 2020-07-10 |
| CN111394748B true CN111394748B (zh) | 2021-05-14 |
Family
ID=71426992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010077336.3A Expired - Fee Related CN111394748B (zh) | 2020-01-28 | 2020-01-28 | 一种用于co2电解的铁镍合金原位脱溶的层状钙钛矿阴极材料 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111394748B (zh) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113991088B (zh) * | 2021-10-29 | 2022-12-30 | 中国科学技术大学 | 一种锂离子电池负极材料及其制备方法 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013126432A1 (en) * | 2012-02-21 | 2013-08-29 | California Institute Of Technology | Axially-integrated epitaxially-grown tandem wire arrays |
| CN108103524A (zh) * | 2016-11-25 | 2018-06-01 | 中国科学院大连化学物理研究所 | 一种固体氧化物电解池及其制备方法 |
| CN107904615B (zh) * | 2017-11-16 | 2018-10-30 | 深圳大学 | 陶瓷阴极、固体氧化物电解池及其制备方法 |
| CN108611650A (zh) * | 2018-05-04 | 2018-10-02 | 中国科学院生态环境研究中心 | 一种用于co2电解的铁锰共脱溶双钙钛矿阴极材料 |
-
2020
- 2020-01-28 CN CN202010077336.3A patent/CN111394748B/zh not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN111394748A (zh) | 2020-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hua et al. | Hierarchical porous CoS2 microboxes for efficient oxygen evolution reaction | |
| Sun et al. | Boosting CO2 directly electrolysis by electron doping in Sr2Fe1. 5Mo0. 5O6-δ double perovskite cathode | |
| CN111430734B (zh) | (Pr0.5Sr0.5)xFe1-yRuyO3-δ钙钛矿材料及其制备方法与应用 | |
| CN111477881A (zh) | 一种NiFe合金纳米颗粒包覆Pr0.8Sr1.2(FeNi)O4-δ材料及其制法 | |
| CN111450851B (zh) | 一种硫掺杂的钴基纳米析氧电催化剂的制备方法 | |
| CN110787824B (zh) | 一种钒掺杂过渡金属氮化物的制备方法及其应用 | |
| CN111715245B (zh) | 基于高催化活性和结晶性RuTe2的电解水催化剂及其制备方法 | |
| CN111921551A (zh) | 一种包覆铁钴镍三元合金的氮掺杂碳框架材料的制备方法 | |
| CN111621807B (zh) | 准对称固体氧化物电解池的电极材料及其制备方法和应用 | |
| CN112725819A (zh) | 一种钨钼基氮碳化物纳米材料及其制备方法与应用 | |
| CN110681404A (zh) | 一种用于电解水阴极析氢反应的片状碳化钼催化剂及其制备方法和应用 | |
| Yang et al. | Surface reconstruction of defective SrTi0. 7Cu0. 2Mo0. 1O3-δ perovskite oxide induced by in-situ copper nanoparticle exsolution for high-performance direct CO2 electrolysis | |
| CN111394748B (zh) | 一种用于co2电解的铁镍合金原位脱溶的层状钙钛矿阴极材料 | |
| CN116200773A (zh) | 富含孪晶结构的过渡族金属电催化剂及其制备方法和应用 | |
| CN114892206B (zh) | 一种多元金属氮化物异质结纳米棒阵列复合电催化剂及其制备方法和应用 | |
| CN115321611A (zh) | Ba掺杂一步法制备原位析出纳米颗粒的RP相氧化物及其应用 | |
| CN111686729B (zh) | 一种钙钛矿型二氧化碳电还原催化剂及其制备方法 | |
| CN114566662A (zh) | 一种结构有序的高熵金属间化合物、其制备方法和作为燃料电池阴极催化剂的应用 | |
| CN113430548A (zh) | 一种二氧化碳转化电解池及其制备方法与应用 | |
| CN109487299B (zh) | 一种高温电解co2的电解池阴极材料及其制备方法 | |
| CN112680740B (zh) | 一种含合金颗粒的钙钛矿氧化物催化剂的制备方法及应用 | |
| CN115180937B (zh) | 一种钆和铜共掺杂钡铁氧的钙钛矿结构阳极材料及其制备方法 | |
| CN113942982B (zh) | 一种MoP/Mo2N复合材料及其制备方法和应用 | |
| KR101369175B1 (ko) | 용매열 합성법에 의하여 제조되는 나노입자 크기의 메탈 도핑 니켈옥사이드 분말 및 그 제조방법 | |
| Huang et al. | Construction of a metal–oxide interface through alloy nanoparticles to enhance CO 2 electrolysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210514 |