CN116082028B - 一种质子陶瓷燃料电池阳极材料、制备方法以及在直接氨燃料电池中的用途 - Google Patents
一种质子陶瓷燃料电池阳极材料、制备方法以及在直接氨燃料电池中的用途 Download PDFInfo
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- CN116082028B CN116082028B CN202211499984.3A CN202211499984A CN116082028B CN 116082028 B CN116082028 B CN 116082028B CN 202211499984 A CN202211499984 A CN 202211499984A CN 116082028 B CN116082028 B CN 116082028B
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- ammonia
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000000446 fuel Substances 0.000 title claims abstract description 53
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 40
- 239000000919 ceramic Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010405 anode material Substances 0.000 title abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 20
- 229910052742 iron Inorganic materials 0.000 abstract description 11
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 11
- 239000010406 cathode material Substances 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 3
- 229910002768 BaCo0.4Fe0.4Zr0.1Y0.1O3-δ Inorganic materials 0.000 abstract description 2
- 229910002767 BaCo0.4Fe0.4Zr0.1Y0.1O3−δ Inorganic materials 0.000 abstract description 2
- 239000002001 electrolyte material Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 75
- 239000003792 electrolyte Substances 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 230000009467 reduction Effects 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000010248 power generation Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
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- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
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- 229960004106 citric acid Drugs 0.000 description 3
- 239000002737 fuel gas Substances 0.000 description 3
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
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- 239000012535 impurity Substances 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 239000003345 natural gas Substances 0.000 description 2
- -1 oxygen ion Chemical class 0.000 description 2
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- 230000008569 process Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010351 charge transfer process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
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- 238000003892 spreading Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种质子陶瓷燃料电池阳极材料、制备方法以及在直接氨燃料电池中的用途，属于燃料电池电极材料技术领域。该电池阴极材料组成分子式为BaCo0.4Fe0.4Zr0.1Y0.1O3‑δ(BCFZY)，电解质材料组成分子式为BaZr0.1Ce0.7Y0.1Yb0.1O3‑δ(BZCYYb)，阳极材料组成分子式为Ni‑Ba(Zr0.1Ce0.7Y0.1Yb0.1)1‑ 2xRuxFexO3‑δ(Ni‑BZCYYbRF)，其中x表示Ru、Fe元素掺杂量，x＝0.03，δ表示氧空位含量。通过在钙钛矿材料BaZr0.1Ce0.7Y0.1Yb0.1O3‑δ中掺杂一定含量的钌、铁元素提高氨燃料电池阳极的氨催化活性、电导率，降低材料的阻抗。所以，通过Ru、Fe的掺杂能够有效提高氨燃料电池的电化学性能，增加质子陶瓷氨燃料电池实用性，促进其商业化进展。
Description
技术领域
本发明涉及一种质子陶瓷燃料电池阳极材料、制备方法以及在直接氨燃料电池中的用途，具体涉及到的钙钛矿材料Ba(Zr0.1Ce0.7Y0.1Yb0.1)1-2xRuxFexO3-δ(BZCYYbRF)和质子陶瓷氨燃料电池的复合阳极及其制备方法和应用，属于燃料电池电极材料技术领域。
背景技术
人类社会的发展与对自然界的开发利用之间的矛盾越来越突出。21世纪的严重的问题是如何节约有限的能源，以及如何降低二氧化碳和其它污染物的排放。为了减少总的能耗，建立起最先进的有效利用能源的体系，我们急需在发电和运输两个领域中开发高能源利用效率的高新技术。在过去的几十年当中，世界主要的发电方式还是以燃烧煤、石油、天然气等为主，这样的发电方式不仅效率低而且对环境的污染很大，不适应新形式下经济发展的需要。
因此，人们尝试研制新技术从而通过最高效，洁净的方式来获得能源。其中，燃料电池是继水电、火电、核电之后的第四代发电技术，与常规发电技术相比，燃料电池有发电效率高、环境友好等优点，因此受到了世界各国广泛的关注。燃料电池可以使用煤、天然气和生物质等各种类型的燃料，碳排放量低或接近零。同时氢能作为一种绿色能源也被给予厚望。不幸的是，H2体积密度低、液化温度低、运输成本高等问题严重阻碍了氢能的商业化实施可替代的、可持续的和清洁的燃料系统。与氢燃料相比，NH3作为一种无碳的氢载体具有更多重要的优势，如更高的容积能密度、成熟的量产技术、易于存储(室温液化和中等压力)和易于运输。近年来，氨燃料电池被认为是一种新的移动应用能源供应方式。
与传统的基于氧离子传导电解质的固体氧化物燃料电池(SOFC)相比，质子陶瓷燃料电池(PCFC)更有望用于氨燃料的使用。首先，质子比氧离子具有更高的迁移率，因此PCFC更适合于低温操作，这将带来成本降低、电池寿命延长、密封更加灵活等诸多好处。其次，PCFC中没有氨或氮与氧或水的混合，从而避免了氮氧化物的潜在形成。最后，由于氧化产物是在PCFC的阴极形成的，不会稀释燃料气体，大大提高了燃料效率。
在直接氨质子陶瓷燃料电池(DA-PCFC)阳极中，NH3首先进行分解产生N2和H2，然后H2再进行电化学氧化过程从而完成反应，因此阳极材料对于DA-PCFC的性能有着重要影响。开发具有高效NH3分解催化活性的新型阳极材料是解决现有阳极材料的NH3分解反应催化活性低的关键问题。镍作为一种重要的过渡金属，在H2的电催化氧化中表现出优异的导热性和导电性以及电催化活性，故在以H2为燃料的PCFC中被广泛应用。以一定比例的NiO直接与电解质粉体机械混合后充当阳极，阳极与电解质交界处基本不会发生相反应，并且阳极和电解质之间有着相匹配的热膨胀系数，不会产生过大的应力等问题。有趣的是，镍对NH3分解反应也表现出良好的催化活性。因此，传统的镍金属陶瓷阳极的PCFC也被直接应用于氨燃料上。不幸的是，镍在高氨气浓度下容易粗化，导致阳极微结构破坏，电池性能迅速衰退。因此，提高抗粗化能力是提高镍基阳极在直接氨燃料电池上运行耐久性的关键，而改进镍基阳极以提高氨气分解和氢气氧化催化活性是实现高功率输出的关键。所以急需对现有的PCFC阳极材料进行修饰。
发明内容
本发明所要解决的技术问题是：现有的镍基直接氨燃料电池正极材料存在着运行稳定性差的问题。本发明在阳极材料的制备过程中，将一定比例的RuFe掺杂进原有的镍基阳极，以结合这两种催化剂本身优异的催化特性和镍基在PCFC应用上具备的良好特征，并将其用于DA-PCFC阳极材料以提高氨气的催化活性。通过在目前传统钙钛矿材料BaZr0.1Ce0.7Y0.1Yb0.1O3-δ中掺杂一定含量的Ru、Fe元素，从而达到性能突破。本专利开发一种高性能的钙钛矿材料为Ba(Zr0.1Ce0.7Y0.1Yb0.1)1-2xRuxFexO3-δ和一种复合阳极材料NiO-Ba(Zr0.1Ce0.7Y0.1Yb0.1)1-2xRuxFexO3-δ及其制备方法和应用，提高了阳极材料对氨气的催化活性，降低了材料的阻抗和活化能。使得Ru、Fe元素掺杂的电池具有优异的电化学性能和良好的稳定性。
本发明的第一个方面，提供了：
一种钙钛矿材料，其特征在于，其组成通式为ABO3-δ，具体分子式为：Ba(Zr0.1Ce0.7Y0.1Yb0.1)1-2xRuxFexO3-δ，其中x代表Ru、Fe元素位掺杂量，δ为氧空位含量。
在一个实施方式中，0≤x≤0.03。
在一个实施方式中，x＝0.03，所述钙钛矿材料的结构式为：Ba(Zr0.1Ce0.7Y0.1Yb0.1)0.94Ru0.03Fe0.03O3-δ。
本发明的第二个方面，提供了：
上述的钙钛矿材料的制备方法，包括如下步骤：
采用溶胶-凝胶法制备该材料，按照化学计量比依次将Ba(NO3)2、Zr(NO3)4·5H2O、Ce(NO3)3·6H2O、Y(NO3)3·6H2O、Yb(NO3)3·5H2O、RuCl3和Fe(NO3)3一同溶解在去离子水中进行加热搅拌均匀，将一定比例的乙二胺四乙酸、一水合柠檬酸和氨水倒入溶液中，调节pH为6-8左右，继续加热搅拌至溶液变为粘稠凝胶状态，干燥后煅烧得到粉体。
干燥条件是150-200℃下1-10h。
煅烧条件是：900-1100℃下1-10h，升温速度1-10℃/min。
乙二胺四乙酸：水合柠檬酸：总金属离子的摩尔比为1:1-3:0.5-1.5。
本发明的第三个方面，提供了：
上述的钙钛矿材料在用于质子陶瓷氨燃料电池阳极中的用途。
氨燃料电池是指直接氨燃料电池。
阳极采用NiO和Ba(Zr0.1Ce0.7Y0.1Yb0.1)0.94Ru0.03Fe0.03O3-δ(BZCYYbRF)构成的复合阳极，淀粉作为造孔剂。
复合阳极中NiO和Ba(Zr0.1Ce0.7Y0.1Yb0.1)0.94Ru0.03Fe0.03O3-δ以及淀粉的质量比为6.5:3.5:1。
所述的用途是指增加阳极整体稳定性。
所述的用途是提高阳极的氨催化活性。
所述的用途是指降低极化阻抗好和电化学反应的活化能。
本发明的第四个方面，提供了：
一种提高采用钙钛矿材料作为正极材料的质子陶瓷氨燃料电池的氨转化率的方法，步骤是：将正极材料在氨气中进行第一次NH3燃料的还原处理后，依次进行氧化和H2还原处理，再次进行对氨气的第二次NH3燃料还原处理，使氨转化率提高。
所述的氧化处理条件是使用含有O2的气体在500-1000℃下处理1-5h；所述的H2还原处理是在H2中于500-1000℃下处理1-5h。
有益效果
本发明涉及到的材料是Ba(Zr0.1Ce0.7Y0.1Yb0.1)0.94Ru0.03Fe0.03O3-δ，用作直接氨质子陶瓷燃料电池阳极中的陶瓷相。还原的Ni-BZCYYbRF阳极对氨分解反应和氢气电化学氧化均具有出色的催化活性。经过测试，单电池BCFZY|BZCYYb|Ni-BZCYYb@RF在650℃，600℃，550℃，500℃的H2气氛下最高功率密度分别达到900mW cm-2，625mW cm-2，430mW cm-2，300mWcm-2，在NH3气氛下最高功率密度分别达到660mW cm-2，465mW cm-2，351mW cm-2，201mW cm-2。
附图说明
图1：其中a、b和c分别为本发明涉及的阳极材料BaZr0.1Ce0.7Y0.1Yb0.1O3-δ(BZCYYb)和Ba(Zr0.1Ce0.7Y0.1Yb0.1)0.94Ru0.03Fe0.03O3-δ(BZCYYbRF)分别在室温25℃下的XRD谱图、阳极材料BZCYYb和BZCYYbRF分别经过1000℃煅烧100小时后，在室温25℃下的XRD谱图、单电池BCFZY|BZCYYb|Ni-BZCYYb@RF在各温度煅烧后粉体的XRD谱图。
图2：本发明涉及的BCFZY为阴极，BZCYYb为电解质，Ni-BZCYYbRF为阳极支撑制备的单电池(BCFZY|BZCYYb|Ni-BZCYYb@RF)的SEM谱图。
图3：其中a和b为本发明涉及到的阳极材料BaZr0.1Ce0.7Y0.1Yb0.1O3-δ(BZCYYb)和Ba(Zr0.1Ce0.7Y0.1Yb0.1)0.94Ru0.03Fe0.03O3-δ(BZCYYbRF)在500-700℃下还原后的氨催化活性、阳极材料BZCYYbRF在500-700℃下二次还原后的氨催化活性对比图，以及阳极材料BZCYYbRF在600℃、NH3燃料下一次还原和二次还原的氨催化活性对比图。
图4：其中a、b、c和d为本发明涉及的在H2气氛下BCFZY为阴极，BZCYYb为电解质，Ni-BZCYYbRF为阳极支撑制备的单电池(BCFZY|BZCYYb|Ni-BZCYYb@RF)以及BCFZY为阴极，BZCYYb为电解质，Ni-BZCYYb为阳极支撑制备的单电池(BCFZY|BZCYYb|Ni-BZCYYb在500～650℃范围内各自测试得到的I-V-P曲线图和阻抗图。
图5：其中a、b、c和d为本发明涉及的在NH3气氛下BCFZY为阴极，BZCYYb为电解质，Ni-BZCYYbRF为阳极支撑制备的单电池(BCFZY|BZCYYb|Ni-BZCYYb@RF)以及BCFZY为阴极，BZCYYb为电解质，Ni-BZCYYb为阳极支撑制备的单电池(BCFZY|BZCYYb|Ni-BZCYYb在500～650℃范围内各自测试得到的I-V-P曲线图和阻抗图。
图6：为本发明涉及的BCFZY为阴极，BZCYYb为电解质，Ni-BZCYYbRF为阳极支撑制备的单电池(BCFZY|BZCYYb|Ni-BZCYYb@RF)在600℃下，在电流密度为200mA cm-2的NH3燃料上工作的单电池的运行稳定性。
图7：为本发明涉及的阳极材料BZCYYb和BZCYYbRF在5vol％H2O-NH3、500℃时的EIS经过DRT拟合的反卷积峰图。
具体实施方式
本发明涉及一种质子陶瓷氨燃料电池的电池结构及其制备方法，该电池阴极材料组成分子式为BaCo0.4Fe0.4Zr0.1Y0.1O3-δ(BCFZY)，电解质材料组成分子式为BaZr0.1Ce0.7Y0.1Yb0.1O3-δ(BZCYYb)，阳极材料组成分子式为NiO-Ba(Zr0.1Ce0.7Y0.1Yb0.1)1- 2xRuxFexO3-δ(Ni-BZCYYbRF)，其中x表示Ru、Fe元素掺杂量，x＝0.03，δ表示氧空位含量。
通过在传统的钙钛矿材料BaZr0.1Ce0.7Y0.1Yb0.1O3-δ中掺入一定量的Ru、Fe元素来提高质子陶瓷氨燃料电池的电化学性能。同时也使得该材料在质子导电性和NH3催化方面都有很大的提升，并且显著的降低了阻抗。在650℃下，单电池BCFZY|BZCYYb|Ni-BZCYYb@RF在H2和NH3为燃料时最大输出功率分别为900mW cm-2和660mW cm-2；对应的没有Ru、Fe元素掺杂修饰的单电池BCFZY|BZCYYb|Ni-BZCYYb对应的最大输出功率分别仅为625mW cm-2和490mWcm-2，分别提升44％和35％。
实施例1：
本实施例提供一种钙钛矿材料Ba(Zr0.1Ce0.7Y0.1Yb0.1)0.94Ru0.03Fe0.03O3-δ(BZCYYbRF)的制备方法，具体步骤如下:
(1)称取13.067g的硝酸钡、2.0178g的硝酸锆、14.2858g的硝酸铈、1.8001g的硝酸钇、2.1109g的硝酸镱、0.606g的硝酸铁和0.3111g的氯化钌，加少量去离子水溶解。按乙二胺四乙酸：水合柠檬酸：总金属离子为1:2:1的摩尔比称取29.224g的乙二胺四乙酸、42.028g水合柠檬酸作为络合剂溶于去离子水中。
(2)将溶有络合剂的溶液加入溶有金属离子溶液后，滴加适量的氨水致溶液pH达到7左右，随后在磁力搅拌的条件下搅致水分完全蒸发得到凝胶状物质。
(3)取出凝胶中转子，用铝箔纸封住烧杯杯口防止其溢出，接着将凝胶状物质放入鼓风干燥箱中，在180℃下恒温干燥5h后得到所需的泡沫状前驱体。
(4)将烧杯取出，待冷却后用刮刀将前驱体刮至各坩埚中，并将前驱体置于高温马弗炉中于1000℃温度下煅烧5h后得到所需的粉体。
实施例2：
本实施例提供一种质子陶瓷氨燃料电池阳极粉体NiO-Ba(Zr0.1Ce0.7Y0.1Yb0.1)0.94Ru0.03Fe0.03O3-δ(Ni-BZCYYbRF)的制备方法，具体步骤如下:
(1)称取6.5g的NiO、3.5g实施例1中制得的BZCYYbRF粉体和1g可溶性淀粉，全部倒入球磨罐后加适量乙醇并球磨30min。
(2)将球磨好的阳极粉体溶液吸取至研钵中，用风扇对着研钵吹以加速无水乙醇的挥发，同时用研杵不断搅拌溶液，直至乙醇完全挥发。
(3)将研钵中的阳极粉体用刮刀刮出，放入65℃恒温干燥箱中干燥5h，最后得到所需要的Ni-BZCYYbRF阳极粉体。
实施例3：
本实施例提供一种BCFZY为阴极，BZCYYb为电解质，Ni-BZCYYbRF为阳极支撑的单电池(BCFZY|BZCYYb|Ni-BZCYYb@RF)的制备方法，具体步骤如下:
(1)称取0.35g实施例2中制得的粉体放入模具中，借助压片机压成直径约为15mm的片子，得到阳极生坯。
(2)称取0.015g BZCYYb粉体，通过漏网将其均匀铺在阳极生坯上方后，将模具放入压片机共压形成阳极-电解质双层生坯，将其在1400℃下烧结5h得到阳极支撑的电解质双层片。
(3)将阳极支撑的电解质双层片放置在加热台上，温度设置为150℃，待双层片均匀且充分受热后，用喷枪将BCFZY阴极浆料均匀的喷涂在电解质的任意一面。将喷涂好的阴极
|电解质|阳极三层膜置于高温电炉中热处理，煅烧温度为900-1100℃，升温速率为5℃
min-1，保温时间为2h，降温后取出即为所制备的单电池BCFZY|BZCYYb|Ni-BZCYYb@RF。
表征结果
1.相结构及微观形貌
图1的a是BZCYYb和BZCYYbRF的室温下的XRD图谱，从图中的峰高与峰宽可以判定配置的粉体成相，且都具有稳定的立方体结构，不含任何杂质峰，是目标钙钛矿结构。图1b是BZCYYb和BZCYYbRF经过1000℃煅烧100小时后的XRD图谱。对比图1的a和图1的b的XRD谱图，可以很明显的看出在1000℃下煅烧100小时的BZCYYb和BZCYYbRF粉体与未煅烧的BZCYYb和BZCYYbRF粉体的衍射峰几乎完全一致，并未发生偏移等变化，这表明BZCYYb和BZCYYbRF粉体具有很好的稳定性。图1的c为单电池BCFZY|BZCYYb|Ni-BZCYYb@RF在各温度煅烧后的XRD图谱。从整体上来看单电池在煅烧的过程的中并没有杂相产生，且衍射峰几乎完全一致，并未发生偏移等现象，这说明单电池相结构稳定。
图2是单电池BCFZY|BZCYYb|Ni-BZCYYb@RF的微观形貌分析图，从中可以看出电池表面具有独特的多孔形貌，可能具有更优的表面气体扩散能力。
2.阳极氨催化活性分析
图3的a为料BZCYYb和BZCYYbRF在500-700℃下还原后的氨催化活性、以及阳极材料BZCYYbRF在经过以此还原和氧化循环后二次被还原的氨催化活性对比图。从图中可以看出，还原后的BZCYYbRF的催化活性确实优于不含RuFe的BZCYYb。例如，以BZCYYbRF为催化剂时，700℃时NH3转化率约100％，而BZCYYb催化剂的NH3转化率仅约为30％。图3的b是BZCYYbRF在600℃、NH3燃料下一次还原和二次还原后的氨催化活性对比图。在600℃下，BZCYYbRF在NH3气氛下还原80h后的转化率约48％。随后，将催化剂置于800℃环境温度下，先在20％ O2-N2扫气中氧化2小时，再在相同温度下转换为H2还原2小时。经重新氧化还原后的BZCYYbRF后的转化率可达到90％左右。由此得出结论，重新脱溶的RuFe纳米颗粒具有更优的催化活性，进一步证实BZCYYbRF对氨分解的优异活性。
3.单电池性能测试(H2气氛)
将制备好的单电池用银胶密封在石英管上，然后置于实验炉内。电池片的阴极暴露在空气气氛中，纯H2作为燃料通入电池的阳极一侧，控制燃料气的流速和电池的测试温度。分别比较BCFZY|BZCYYb|Ni-BZCYYb与BCFZY|BZCYYb|Ni-BZCYYb@RF的单电池在不同温度下的性能。图4的a和4的b为单电池BCFZY|BZCYYb|Ni-BZCYYb@RF在H2气氛下的I-V-P曲线以及单电池BCFZY|BZCYYb|Ni-BZCYYb在H2气氛下的I-V-P曲线图。图4的c和图4的d为单电池BCFZY|BZCYYb|Ni-BZCYYb@RF的阻抗图以及单电池BCFZY|BZCYYb|Ni-BZCYYb的阻抗图。如图所示，在650、600、550和500℃时，其OCV值均大于1，这说明电解质致密，电池密封良好。
单电池BCFZY|BZCYYb|Ni-BZCYYb在650、600、550和500℃的最高输出功率分别为625、498、352和203mW cm-2，对应的极化阻抗分别为0.15、0.24、0.60和1.89Ωcm2。而单电池BCFZY|BZCYYb|Ni-BZCYYb@RF在650、600、550和500℃的最高输出功率分别为900、625、430和300mW cm2，对应的极化阻抗分别为0.11、0.20、0.38和1.01Ωcm2。很明显，Ru、Fe掺杂的BZCYYbRF在作为阳极陶瓷相可以显著提高以H2为燃料的单电池输出性能，且BZCYYbRF阳极提供了更好的H2分解活性以及快速的离子扩散和电导率。同时，随着温度的升高，电池反应中的物质转移和电荷转移过程都加快了，说明温度越高，电极材料的催化活性越高，动力学反应越活跃，从而极化阻抗越低。
4.单电池性能测试(NH3气氛)
将制备好的单电池用银胶密封在石英管上，然后置于实验炉内。电池片的阴极暴露在空气气氛中，纯NH3作为燃料通入电池的阳极一侧，控制燃料气的流速和电池的测试温度。分别比较BCFZY|BZCYYb|Ni-BZCYYb与BCFZY|BZCYYb|Ni-BZCYYb@RF的单电池在不同温度下的性能。图5的a和5的b为单电池BCFZY|BZCYYb|Ni-BZCYYb@RF在NH3气氛下的I-V-P曲线图以及单电池BCFZY|BZCYYb|Ni-BZCYYb在NH3气氛下的I-V-P曲线图。图5的c和图5的d为单电池BCFZY|BZCYYb|Ni-BZCYYb@RF的阻抗图以及单电池BCFZY|BZCYYb|Ni-BZCYYb的阻抗图。如图所示，在650、600、550和500℃时，其OCV值均大于1，这说明电解质致密，电池密封良好。
单电池BCFZY|BZCYYb|Ni-BZCYYb在650、600、550和500℃的最高输出功率分别为490、345、243和152mW cm-2，对应的极化阻抗分别为0.28、0.33、0.80和1.59Ωcm2。而单电池BCFZY|BZCYYb|Ni-BZCYYb@RF在650、600、550和500℃的最高输出功率分别为660、465、351和201mW cm-2，对应的极化阻抗分别为0.16、0.29、0.44和1.23Ωcm2。很明显，Ru、Fe掺杂的BZCYYbRF在作为阳极陶瓷相可以显著提高以NH3为燃料的单电池输出性能。
5.EIS表征
图7显示了BZCYYbRF和BZCYYb样品在5％水分压500℃时的EIS经过DRT拟合的反卷积峰。根据频率范围将其划分为高频区域(P1)、中频区域(P2)和低频区域(P3)，分别反映电荷转移，离子传输或表面交换，以及表面氧扩散。总的来说，中频区域所代表的离子传输或表面交换是影响电化学反应的主要限制步骤。对比可知，BZCYYbRF在P1,P2,P3峰面积小于BZCYYb，表明其具有更快的离子扩散和表面交换速率。
6.单电池稳定性表征
对于一个电池而言，稳定性测试是其商业化前的必要测试之一。本次稳定性测试是在600℃且外加电流密度为200mA cm-2下进行测试的。图6为单电池BCFZY|BZCYYb|Ni-BZCYYb@RF在600℃、NH3为燃料条件下的电压随时间变化曲线。从图中可以看出，电池在经过100小时的连续放电之后，电池的电压基本保持稳定，这说明该电池具有良好的稳定性。
Claims (2)
1.钙钛矿材料在质子陶瓷直接氨燃料电池阳极中的用途，其特征在于：所述的钙钛矿材料的化学通式是Ba(Zr0.1Ce0.7Y0.1Yb0.1)0.94Ru0.03Fe0.03O3-δ，δ是氧空位含量，所述的钙钛矿材料的制备方法包括如下步骤：
按照化学计量比依次将Ba(NO3)2、Zr(NO3)4·5H2O、Ce(NO3)3·6H2O、Y(NO3)3·6H2O、Yb(NO3)3·5H2O、RuCl3和Fe(NO3)3一同溶解在去离子水中进行加热搅拌均匀，将一定比例的乙二胺四乙酸、一水合柠檬酸和氨水倒入溶液中，调节pH为6-8，继续加热搅拌至溶液变为粘稠凝胶状态，干燥后煅烧得到粉体；
干燥条件是150-200℃下1-10h；
煅烧条件是：900-1100℃下1-10h，升温速度是1-10℃/min；
质子陶瓷直接氨燃料电池中阳极采用由NiO和所述的钙钛矿材料构成的复合阳极，并采用淀粉作为造孔剂；
复合阳极中NiO和钙钛矿材料以及淀粉的质量比为6.5:3.5:1。
2.根据权利要求1所述的用途，其特征在于，乙二胺四乙酸：一水合柠檬酸：总金属离子的摩尔比为1:1-3:0.5-1.5。
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