一种原位出溶Pd-Ni合金的高活性且耐久的阳极催化层用于直接碳氢燃料质子陶瓷燃料电池

doi:10.1016/S1872-2067(25)64913-8

催化学报 ›› 2026, Vol. 82: 125-134.DOI: 10.1016/S1872-2067(25)64913-8

一种原位出溶Pd-Ni合金的高活性且耐久的阳极催化层用于直接碳氢燃料质子陶瓷燃料电池

龚文杰, 许阳森, 刘豪, 林万斌, 杜志伟, 黄逸轩, 刘江, 陈宇^*()

华南理工大学环境与能源学院, 广东广州 510006

收稿日期:2025-07-31 接受日期:2025-09-24 出版日期:2026-03-18 发布日期:2026-03-05
通讯作者: * 电子信箱: eschenyu@scut.edu.cn (陈宇).
基金资助:
广东省基础与应用研究基金(2024A1515010448);广东省引进创新创业团队项目(2021ZT09L392);国家自然科学基金(22179039);中央高校基本科研经费(2022ZYGXZR002);广州市科技计划(2024A04J3079);紫金矿业集团有限公司科研项目(5405-ZC-2023-00008);珠江人才计划(2019QN01C693)

An active and durable anode catalytic layer with in-situ exsolved Pd-Ni nanoparticles for protonic ceramic fuel cells on hydrocarbon fuels

Wenjie Gong, Yangsen Xu, Hao Liu, Wanbin Lin, Zhiwei Du, Yixuan Huang, Jiang Liu, Yu Chen^*()

School of Environment and Energy, South China University of Technology, Guangzhou 510006, Guangdong, China

Received:2025-07-31 Accepted:2025-09-24 Online:2026-03-18 Published:2026-03-05
Contact: * E-mail: eschenyu@scut.edu.cn (Y. Chen).
Supported by:
Guangdong Basic and Applied Basic Research Foundation(2024A1515010448);Introduced Innovative R&D Team of Guangdong(2021ZT09L392);National Natural Science Foundation of China(22179039);Fundamental Research Funds for the Central Universities(2022ZYGXZR002);Guangzhou Science and Technology Project(2024A04J3079);Zijin Mining Group Co., Ltd(5405-ZC-2023-00008);Pearl River Talent Recruitment Program(2019QN01C693)

摘要/Abstract

摘要：

氢气(H₂)是质子陶瓷燃料电池(PCFCs)的常用燃料, 但其存在着能量体积密度低且与金属存在氢脆效应, 使氢的储存与运输面临较大挑战. 直接使用碳氢燃料替代H₂作为PCFCs的燃料, 表现出显著的环境优势与技术潜力. 然而, 直接碳氢燃料质子陶瓷燃料电池在实际运行中也面临着多重挑战. 镍基阳极在PCFCs的工作温度下容易结焦, 导致催化活性位点减少, 进而降低碳氢燃料的蒸汽重整速率, 导致电池性能的衰减. 因此, 开发出兼具高催化活性与长期稳定性的阳极, 是当前亟待解决的关键问题.

本文设计了Pd_0.01Ni_0.09Ce_1.9O_2-_δ(P1NC)催化剂, 其在H₂的条件下Pd和Ni金属出溶至CeO₂表面形成CeO₂负载的Pd-Ni合金催化剂, 成功应用于直接碳氢燃料质子陶瓷燃料电池. 通过X射线衍射、球差透射电镜及X射线光电子能谱等手段证实了这种异质结构. 将P1NC催化剂涂覆于Ni-BaZr_0.4Ce_0.4Y_0.1Yb_0.1O_3-_δ(Ni-BZCYYb)阳极制备成单电池和对称电池, 以评估其甲烷蒸汽重整催化活性. 与Ni-BZCYYb空白燃料电极相比, 涂覆有P1NC催化剂的Ni-BZCYYb阳极在对称电池模式下表现出更低的极化阻抗值和活化能. 在650 °C时, 涂覆有P1NC催化剂的Ni-BZCYYb燃料电极的极化阻抗值仅0.89 Ω cm², 而Ni-BZCYYb空白阳极达到了1.09 Ω cm². 在保证Pd-Ni金属总量不变的情况下提高或降低Pd金属的含量, 都会在对称电池上表现出比P1NC催化剂更高的极化阻抗值. 基于弛豫时间分布的电化学阻抗谱分析表明, P1NC催化剂优越的催化活性得益于其更强的甲烷、水汽和氢气的解离吸附作用. 在阳极侧通入含66.7%水蒸汽湿甲烷的条件下, 涂覆有P1NC催化剂的质子陶瓷燃料电池在650 °C的峰值功率密度达到了1.20 W cm^-2, 而空白的质子陶瓷燃料电池仅表现出0.72 W cm^-2的电化学性能. 将P1NC催化剂用于直接甲醇或乙醇质子陶瓷燃料电池时也表现出了较好的催化活性. 此外, 有P1NC催化层的直接甲烷/甲醇/乙醇质子陶瓷燃料电池在650 °C和放电电流为0.2 A cm^-2的条件下均稳定运行了100 h, 而空白的直接甲烷质子陶瓷燃料电池在10 h内表现出急剧的性能衰退趋势. 扫描电子显微镜和拉曼测试显示, P1NC催化剂能够有效抑制碳的沉积.

综上, 本文设计了一种用于直接碳氢燃料质子陶瓷燃料电池的P1NC催化层, 能够有效地活化C-H键和抑制碳的沉积, 且表现出较好的运行稳定性和燃料灵活性, 为设计高活性且耐久的直接碳氢燃料质子陶瓷燃料电池的阳极催化层提供了新思路.

关键词: 质子陶瓷燃料电池, 甲烷湿重整, 阳极催化层, Pd-Ni纳米颗粒, 燃料灵活性

Abstract:

Operating hydrocarbons on protonic ceramic fuel cells (PCFCs) is promising and attractive, on account of their high energy conversion efficiency and potential for low carbon emissions compared to traditional thermal power generation. However, poor coking tolerance and insufficient catalytic activity at intermediate temperatures greatly hinder the development of PCFCs on hydrocarbons. Exploring a catalytic layer with high activity and durability is an effective way to achieve high-performance PCFCs on hydrocarbon fuels. Herein, we report an anode catalytic layer (ACL) with an optimized formula of Pd_0.01Ni_0.09Ce_1.9O_2-_δ (P1NC). Pd-Ni alloy nanoparticles are exsolved from the ACL under a hydrogen atmosphere. The high oxygen vacancy concentration in P1NC has shown a positive effect on the oxygen storage capacity, which may facilitate carbon gasification, thereby reducing performance degradation during PCFC operation, as supported by the Raman and scanning electron microscopy observations. PCFCs with this ACL achieved a decent peak power density (P_max) of 1.20 W cm^-2 and stably operated at 0.2 A cm^-2 at 650 °C on CH₄. In addition, the cells with P1NC ACL exhibited encouraging P_max of 1.00 and 0.87 W cm^-2 at 650 °C on liquid fuels such as methanol and ethanol, respectively, exhibiting good fuel flexibility.

Key words: Protonic ceramic fuel cells, Steam methane reforming, Anode catalytic layer, Pd-Ni nanoparticles, Fuel flexibility

龚文杰, 许阳森, 刘豪, 林万斌, 杜志伟, 黄逸轩, 刘江, 陈宇. 一种原位出溶Pd-Ni合金的高活性且耐久的阳极催化层用于直接碳氢燃料质子陶瓷燃料电池[J]. 催化学报, 2026, 82: 125-134.

Wenjie Gong, Yangsen Xu, Hao Liu, Wanbin Lin, Zhiwei Du, Yixuan Huang, Jiang Liu, Yu Chen. An active and durable anode catalytic layer with in-situ exsolved Pd-Ni nanoparticles for protonic ceramic fuel cells on hydrocarbon fuels[J]. Chinese Journal of Catalysis, 2026, 82: 125-134.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(25)64913-8

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Fig. 1. Micro-structure and characterizations of reduced P1NC catalyst. (a) XRD patterns of P2NC, P1NC, NC, and CeO2 powder after reduction. (b) Corresponding enlarged scanning range of 2θ from 40° to 55°. (c) AC-TEM image of the reduced P1NC. (d) HAADF and EDS elemental mappings of reduced P1NC. (e) The fitted XPS spectra of Pd 3d for reduced P1NC. (f) The fitted Ni 2p spectra for reduced P1NC. (g) The fitted Ce 3d spectra for reduced P1NC and CeO2. (h) The O 1s spectra for reduced P1NC and CeO2.

Fig. 2. P1NC catalyst enhances catalytic activity for SMR. (a) Equilibrium composition analysis for steam methane reforming (CH4:H2O = 1:2). (b) Gibbs free energy as a function of temperature of relevant reactions during SMR. (c) Schematic of symmetrical anode cell, tested with humidified CH4 (66.7% H2O). (d) EIS curves of the bare anode and anode with P1NC ACL tested in humidified H2 (3% H2O) or humidified CH4 (66.7% H2O). (e) DRT plots of EIS of the bare anode or the anode with P1NC ACL in humidified CH4 (66.7% H2O) at 650 °C. (f) Arrhenius plot of Rp values of bare anode and anode with catalytic layers of P1NC, P2NC, and NC.

Fig. 3. Electrochemical performance of single cells (P1NC | Ni-BZCYYb4411 | BZCYYb4411 | PBSCF). (a) Schematic illustration of the PCFCs with the P1NC ACL. (b) I-V-P curves of a single cell with the P1NC ACL, employing humidified CH4 (66.7% H2O) as fuel. (c) Comparison of ohmic resistance (Rohm) and Rp of single cells with and without the P1NC ACL. (d) I-V-P curves of a single cell with the P1NC ACL, employing an evaporated mixture of molar ratio H2O:CH3OH:N2 of 1:1:1 as fuel. (e) I-V-P curves of a single cell with the P1NC ACL, employing an evaporated mixture of molar ratio H2O:C2H5OH:N2 of 3:1:3 as fuel. (f) Comparison of Pmax of state-of-the-art hydrocarbon-SOFCs at 600 °C.

Fig. 4. Analyses of electrochemical performance and coking tolerance of PCFC with P1NC ACL. (a) Short term durability of PCFC with P1NC ACL fueled by methane, methanol, and ethanol. (b) Schematic illustration of characterizations on PCFCs with the bare anode using Raman spectroscopy. Raman mapping of D-band (c) and G-band (d) for PCFC with bare anode after durability evaluation on humidified methane (66.7% H2O) at 650 °C. (e) Schematic illustration of characterization on PCFCs with the P1NC ACL. Raman mapping of D-band (f) and G-band (g) for P1NC ACL after short term test on CH4 at 650 °C.

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一种原位出溶Pd-Ni合金的高活性且耐久的阳极催化层用于直接碳氢燃料质子陶瓷燃料电池

An active and durable anode catalytic layer with in-situ exsolved Pd-Ni nanoparticles for protonic ceramic fuel cells on hydrocarbon fuels

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