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化学进展 ›› :0- DOI: 10.7536/PC20260317
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固体氧化物电池抗积碳策略进展

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Progress in Anti-Coking Strategies for Solid Oxide Cells

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摘要

固体氧化物电池（SOC）可直接利用CH4、CO等含碳燃料进行发电，也可电解CO2制备CO等化学合成原料。在SOC燃料电极一侧，甲烷脱氢和CO脱氧可能导致碳沉积，覆盖三相活性界面、堵塞孔道并引起燃料电极失效。本综述系统梳理固体氧化物燃料电池（SOFC）、固体氧化物电解池（SOEC）与电转X（Power-to-X）三种运行场景下的积碳过程、热力学与动力学基础，重点讨论材料设计（如Ni基材料改性、无Ni电极开发和功能催化层构筑）、气氛/工况优化及机理分析等抗积碳策略。进一步总结“活性氧溢流-电子/集团效应”协同除碳机理，并比较不同应用场景下积碳来源、关键影响因素和策略侧重点。本文可为高性能抗积碳SOC电极设计及长期稳定运行提供参考。

Abstract

Solid oxide cells (SOCs) can directly utilize carbon-containing fuels, such as CH4 and CO, for power generation, or electrolyze CO2 to produce CO as an important feedstock for chemical synthesis. On the fuel electrode side of SOCs, methane dehydrogenation and CO deoxygenation may lead to carbon deposition, covering the three-phase active interface, blocking pores, and causing fuel electrode degradation. This review summarizes the carbon deposition processes and their thermodynamic and kinetic bases in three operating scenarios: solid oxide fuel cells (SOFCs), solid oxide electrolysis cells (SOECs), and Power-to-X (P2X) systems. It focuses on anti-coking strategies including material design, such as modification of Ni-based materials, development of Ni-free electrodes and construction of functional catalytic layers, reaction atmosphere/operating condition optimization, and mechanistic analysis. The synergistic carbon-removal mechanism involving active oxygen spillover and electronic/ensemble effects is further summarized, and the differences in carbon sources, key influencing factors and strategy priorities among different application scenarios are compared. This review provides a reference for the design of high-performance coke-resistant SOC electrodes and their long-term stable operation.

Contents

1 Introduction

2 Progress in SOFC Anti-Coking Research

2.1 Thermodynamic Analysis of SOFC Anode Carbon Deposition

2.2 Strategies for SOFC Anode Anti-Coking

2.3 Mechanism of Anti-Coking in SOFC

3 Progress in SOEC Anti-Coking Research

3.1 Thermodynamic Analysis of SOEC Cathode Carbon Deposition

3.2 Strategies for SOEC Anode Anti-Coking

4 Progress in Power to X Anti-Coking Research

4.1 Causes of Carbon Deposition in P2X Applications

4.2 Anti-Carbon Deposition Strategies for P2X Applications

4.3 Performance Comparison of SOCs in Different Applications Regarding Carbon Deposition Resistance

4.4 Engineering Evaluation Criteria for SOC Anti-Coking Electrode Materials

4.5 Recommendations for the Safe Operating Window of SOC Multi-Parameter Coupling

5 Conclusions and Outlook

5.1 Key Findings

5.2 Outlook

关键词

固体氧化物电池 / 电催化 / 钙钛矿 / 固体电化学 / 积碳

Key words

solid oxide cells / electrocatalysis / perovskite / solid state electrochemistry / carbon deposition

引用本文

引用格式 ▾
赵浩然, 杨泽鑫, Ndungutse Jean Maurice, 李莉娟, 刘德旺, 倪九派, 倪呈圣. 固体氧化物电池抗积碳策略进展[J]. 化学进展, , (): 0 DOI:10.7536/PC20260317
Haoran Zhao, Zexin Yang, Ndungutse Jean Maurice, Lijuan Li, Dewang Liu, Jiupai Ni, Chengsheng Ni. Progress in Anti-Coking Strategies for Solid Oxide Cells[J]. Progress in Chemistry 0 DOI:10.7536/PC20260317

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1 引言

固体氧化物电池（SOC）是一种全固态高温（500-800 °C）电化学能量转换装置，在能源转型与绿色化工领域具有广阔的应用前景[1,2]。按照不同的运行模式，SOC可以是固体氧化物燃料电池（Solid oxide fuel cell, SOFC）和固体氧化物电解池（SOEC）。在SOC的工作温度，储量丰富且经济的天然气（主要成分CH4、CO等）或沼气（主要成分CH4、CO2等）能够被活化重整用于发电。在使用含碳燃料时，SOFC容易出现碳沉积（Carbon deposition）或者结焦（Coking）等问题，对长期稳定运行不利[3]。在SOEC模式下，CO2经电解产生CO，CO的歧化反应（2CO = C + CO2）或者CO的进一步电解会导致电极表面的碳沉积 [4]。沉积的碳会覆盖三相边界（Triple-phase boundaries, TPB），堵塞孔道结构，导致SOC电化学性能急剧下降[5]。严重积碳会在电极表面造成较大应力，对电极表面造成不可逆损坏[6]。沉积的碳不利于碳氢燃料与电催化剂间的离子转移[7]。因此，深入理解碳沉积机理并高效抑制，对于SOC的长期稳定运行至关重要。

在使用含碳燃料的SOFC抗积碳研究中，研究人员重点关注阳极材料优化，如通过合金化将Ni与其他金属结合或加入金属氧化物对镍基阳极进行改性、开发无镍阳极材料和引入Ce0.9Gd0.1O2-δ（GDC）或La0.4Sr0.6Co0.2Fe0.7Nb0.1O3-δ（LSCFN）等无镍阳极也可有效限制碳沉积[8,9]。

在CO2电解的SOEC中，其阴极面临比SOFC更低的氧分压和更高的积碳风险，因此，其抗积碳研究可参考SOFC的材料体系，然而，SOEC模式下的碳沉积与SOFC中的碳沉积机理并不完全相同[10]，此外，在燃料中加入O2、H2O，或增强电流强度等也可有效抑制积碳[11]。

电转X（Power to X，P2X）是一种将可再生能源转化为其他形式能源或燃料的技术，其中X可以是氢气、合成气或合成燃料。SOEC可将H2O、CO2通过电化学转化为H2、CO或合成气（H2 + CO），或与多种化学合成结合以实现CO2和H2O循环转化合成天然气、汽油、甲醇，与低温电解技术相比，这将进一步提高效率[12]。然而，在此类应用中，积碳问题较为复杂，因为生成目标产物（如乙烯等）的反应条件与积碳反应较为接近。因此，在此类应用中，需在抑制碳生成的同时，最大化目标产物的选择性，对催化剂材料的优化提出了高要求。

针对SOC主要应用模式，本综述将分节讨论SOFC、SOEC，P2X这三个方面的抗积碳研究。研究者们通过机理分析，深化对碳沉积问题的理解[13]，致力于寻找对抗碳沉积的有效方案。为了增强SOC抗积碳性能，材料创新（如电极材料改性[14]，新型材料开发[15]等）、过程优化（如气氛调控[16]、工况调节[17]等）是两种重要的策略。本论文通过对比不同策略的机理、效果与适用性，并提出材料设计和电化学工况条件调控的方法，为未来SOC抗积碳研究提供借鉴。

2 SOFC抗积碳研究进展

2.1 SOFC阳极积碳热力学分析

C-H-O相平衡图（图1）表明，在无氧条件下，烃类在温度高于600 oC条件下容易发生分解反应，生成氢气[18-22]，用于SOFC的发电产氢。以甲烷为例，甲烷可被直接裂解为焦炭和氢气（CH4 = C + 2H2）。

在氧离子传导型SOFC中，阴极产生的氧离子经电解质传输至阳极，可改变阳极侧气体组成平衡。由于氧离子的通量和电流密度有关，因此含碳燃料的氧化过程和SOFC的工作状态相关。抑制积碳的常规策略是在燃料中混入H2O或O2以促进燃料重整或部分氧化。根据热力学原理，向燃料中加入空气或水可抑制碳沉积[22]。当C或CO被氧化为CO2时，整体成分会远离碳沉积区[18]。

在CH4重整过程中，反应生成的CO会发生布多阿尔反应（Boudouard reaction, 式1）[18,24]，三维多物理场模型模拟结果和大量实验数据证实，气相布多阿尔反应是碳沉积的主要原因[24]。布多阿尔反应是放热熵减反应，标准焓变为-172 kJ/mol，根据吉布斯自由能公式（ΔG = ΔH - TΔS），低温下倾向于生成碳；随着温度提升，-TΔS项逐渐增大，反应平衡向CO移动，通常在700 oC以上碳生成倾向明显降低[25]。

2 CO(g) = C(s) + CO2(g) （1）

碳形成的微观热力学机理可通过第一性原理计算深入探究，其中密度泛函理论（DFT）是电化学模拟领域的核心方法。研究人员利用 DFT 计算系统阐述了SOFC阳极的积碳机理，并提出了四种潜在的碳消除路径（图2）[26]。表面氢、氧和羟基可将固体碳转化为其他中间体，在路径1和3中，限速步骤为CO*的氧化，其能垒为0.95 eV；而路径2和4中，OH*的生成能垒最高，达到1.14 eV。因此，路径1和3为碳消除的主要途径[26]。另有研究得出了相似的计算结果，并提出四种抗积碳策略：提高表面氧浓度并降低表面氧梯度；增加表面-OH浓度并降低表面-OH梯度；促进CO的解离与转化；调控Ni的双相边界长度[27]。

2.2 SOFC阳极抗积碳策略

由于SOFC需长期在高温下运行，因此，研究人员对SOFC提出了一些要求，如高导电率、高稳定性、良好的电极物质兼容性与孔隙率[28]。针对这些要求，研究人员对电极材料、燃料气氛、工况条件等分别进行优化，以提高SOFC效率，抑制碳沉积。部分SOFC抗积碳研究进展如表1，抑制碳沉积的主要策略包括镍基阳极优化、无镍阳极开发、燃料气氛优化、降低工作电流和降低温度等。

2.2.1 镍基阳极优化

传统Ni基金属陶瓷阳极（如Ni-YSZ、Ni-SDC、Ni-BCZY和Ni-CeO2等）因其具有高催化活性而广泛应用于SOFC阳极[39]。然而，Ni是布多阿尔反应的高效催化剂，并且能够快速诱导烃类燃料脱氢，易导致碳沉积[40]。因此，研究人员常采用元素掺杂或表面改性来提高含Ni阳极的抗积碳能力。

稀土元素如La、Sm等掺杂到Ni-CeO2中，可减少表面酸性位点，可促进Ni在催化剂表面的均匀分散，抑制Ni聚集，提高催化剂表面碱性强度，显著抑制积碳[41]。如La掺杂Ni-YSZ阳极可显著降低极化电阻，对CH4电化学氧化表现出高性能，并抑制了碳沉积与结焦[42]。

非稀土金属如Co [43]、Cu [44]、Fe [45]、Sn [46]、Ru[47]、Pt[48]和Au [49]等掺杂也被研究用作抑制碳沉积，如Cu负载的Ni-YSZ电极可减少约30%的碳沉积量，可直接以合成气为原料[30,50,51]，此外，将NiCo和NiCu负载于GDC表面时，Co基催化剂表现出更高的CO2与CH4转化率，且抗积碳稳定性更佳[52]。此外，通过浸渍过渡金属（Fe、Co、Ni、Mn等）与共掺杂氧化物（如CeO2）改性，可利用组分间的协同效应（如增强储放氧能力与催化活性）进一步强化Ni基电极的抗沉积性能[53]。

碱（土）金属氧化物（如MgO、SrO、BaO）是Ni基金属陶瓷阳极改性的重要助剂[54-56]。除MgO会加剧积碳并抑制电催化活性外，其余氧化物均能显著抑制积碳。研究表明，通过浸渍法在Ni-YSZ表面修饰粒径小于100 nm的BaO纳米岛，可利用其作为水分子的捕获与解离催化剂，促进H2O解离产生活性OH种族，从而有效消除阳极积碳[56-58]。

此外，电解质骨架优化也可提高镍基阳极的抗积碳效果，如Ni/ScSZ的积碳热力学倾向与Ni/YSZ相反，随着温度提高，积碳量降低[29]。通过浸渍法将Cu负载到Ni/SDC上，在600 oC下甲烷气氛中，2h的积碳量仅为12.7%，积碳量少于含有NiCu合金的Ni0.95Cu0.05/SDC的10% [32]。

2.2.2 无镍阳极开发

萤石[59]、烧绿石[60]、金红石[61]和钙钛矿[62]等结构的氧化物被广泛应用于SOFC抗积碳研究。萤石结构的氧化物（如GDC、SDC）具有高氧离子传导率和储氧能力，可提供丰富的活性氧以清除沉积碳[63-65]。烧绿石氧化物（A2B2O7）具有独特立方晶体结构、良好的物化稳定性和氧离子迁移能力，其性能取决于A/B位离子半径比例，需控制在1.46-1.78的范围内[60,66,67]。四方结构金红石（TiO2）热力学稳定，掺杂低价阳离子可产生氧空位，显著提升抗积碳性能[68-70]。

钙钛矿（ABO3）作为一类极具前景的氧化物阳极材料，因其优异的电催化活性与抗积碳能力，被认为是替代Ni基金属陶瓷的理想选择[15,71,72]。目前研究重点包括铁基（如La0.6Sr0.4Fe0.8Cr0.2O3-δ(LSFCr)[73]）、钛基（如La0.3Sr0.7Ti0.3Fe0.7O3-δ（LSTF）[74]）、铌基（如CaMn0.75Nb0.25O3−δ (H2-CMNO)[75]）和锶基钙钛矿（如La0.75Sr0.25Cr0.5Mn0.5O3（LSCM）[76]、LaSrMnO3（LSM）[77]、LaSrFeO3（LSF）[78]等）。尽管这些材料具备高结构稳定性和高氧空位浓度，但钙钛矿的析氧反应性能仍需提升，如可通过掺杂金属提升性能与稳定性[79-81]。

通过精准调控钙钛矿A位和B位可控制催化剂性能，掺杂金属如Ni、Cu和Co等可有效改善钙钛矿性能与稳定性，如在La0.75Sr0.25Cr0.5Fe0.5O3-δ（LSCF）中掺杂Cu，在CH4/CO2（体积比 1:1）氛围中表现出高抗沉积能力，120 h运行后的拉曼光谱显示其表面几乎无碳沉积[82]。单独B位掺杂Ni或Co可有效提高催化剂活性，研究人员开发了Sr2(Fe, Mo)O6-δ钙钛矿阳极，原位析出的FeNi3或Co纳米颗粒与GDC的协同作用，可有效抑制碳沉积，以甲烷为燃料时峰值功率密度为0.392 W/cm2，且运行600h无积碳[83]。第一性原理计算结果表明，向LaCo0.2F0.8O3中掺杂Cu和Pd时，C原子插入氧空位稳定结构的氧空位形成能降低，而Ti和Ni掺杂有相反的影响，此外，LCFCu表面的碳形成能垒更高，碳沉积抑制效果最好[15]。此外，在LSCM表面，Cr与Mn的互补掺杂发挥了关键作用：Cr维持了晶格结构的稳定性，Mn促进甲烷的电化学氧化而非热裂解，在900 oC，湿甲烷氛围中，运行7h仅产生痕量碳，无性能衰减，其峰值功率与Ni/YSZ相当（0.2 W/cm2）[76]。

近年来，微观结构设计和多元共掺杂是提升无镍阳极抗积碳性能的关键策略，如Ru@Ru-SFM/GDC双出溶自组装阳极的独特壳膜界面结构在长期稳定性测试后，仍能维持完整的多孔亚微米形貌，几乎无任何碳沉积[33]。在钛酸锶基钙钛矿中共掺杂La、Ce、Ni获得LSCNT（La0.3Sr0.6Ce0.1Ni0.1Ti0.9O3-δ）阳极，在900 oC下稳定运行80 h无性能衰减，CO2-TPO与O2-TPO测试显示碳沉积显著被抑制[34]。

Na/Ta共掺杂可调节SrFeO3−δ的能带，相较于单Nb掺杂，共掺杂提高了电化学性能与稳定性[84]。FeNi合金掺杂钙钛矿可显著提高抗积碳性能，如FeNi合金与PrOx纳米颗粒在Pr0.8Sr1.2Fe1.5Mo0.3Ni0.2O6-δ (R-PSFMN)表面的共溶，复合阳极在H2和C2H6氧化中表现出良好的性能与抗沉积能力[85]。此外，研究人员使用拉曼分析揭示了掺杂Li元素的抗积碳机理，Li掺杂FeNi阳极表面碳物种的D带（无定形碳）和G带（石墨化碳）强度比达1.52，显著高于未掺杂（0.92），表明表面生成的碳以无定形碳为主，更易通过气化反应去除[86]。

2.2.3 燃料气氛优化

向燃料气氛中添加特定气体也可有效抑制碳沉积，如引入O2、H2和H2O等[87-89]。向含碳燃料中加入适量O2，可促进燃料氧化，使体系远离碳沉积区（图1）[87]。加入H2可增强电池性能的同时抑制碳沉积，如提高CH4-H2混合物中H2的摩尔分数可以加快电化学反应，提高电流密度，进而导致碳沉积量降低，且燃料利用率和电解化学反应效率得到改善[90]。加入一定量的H2O是抑制SOFC阳极碳沉积的重要策略，通过通入水蒸气可控制蒸汽碳比（V/C），可有效抑制碳沉积，以CH4为例，V/C由0.5提升至2，1000 oC下使用CH4时，表面碳覆盖率由8.4×10-4降低至几乎无碳沉积[91,92]。阳极尾气复用（Anode off-gas recirculation, AOG）也是抑制碳沉积的重要策略[93]，降低碳含量以影响热力学平衡，使反应向无碳沉积区移动（图1），可有效提高SOFC运行效率[93,94]。

2.2.4 工况条件优化

工况条件也是影响SOFC阳极碳沉积的重要影响因素。如使用CH4/CO混合气为燃料气体，在不同温度下需调整V/C来降低碳沉积，600 oC下V/C ≥ 2才能将碳表面覆盖率降低至1×10-4以下，1000 oC下V/C达到1.5即可显著抑制积碳[91]。此外，降低运行温度可有效抑制积碳，据报道，将SOFC工作温度控制在700 oC以下，利用低温减缓碳氢化合物裂解速率来抑制积碳，SDC电解质的SOFC在低温下直接使用CH4也无明显积碳，温度高于700 oC时，CH4开始裂解，积碳开始出现，作为对比，CH4在Ni-YSZ阳极上催化时，510 oC即开始出现积碳，660 oC时裂解速率增大，证明了SDC电解质和低温对积碳的抑制作用[95]。

此外，工况条件与电池结构的协同优化可显著影响积碳，减小燃料电极厚度可有效增加反应界面的局部蒸汽浓度，从而在直接使用碳氢重整气时，显著降低碳沉积速率，并提升电池的长期稳定性[96]。

2.3 SOFC抗积碳机理研究

各种抗积碳策略在不同材料和工况条件下的效果有差异，但其微观机理可归纳为活性氧溢流-电子/集团效应的协同作用，分别从抑制积碳和原位消除两种方式抗积碳。

掺杂金属抑制碳沉积的微观机制主要归因于集团效应（Ensemble effect）[97,98]和电子效应（Electronic effect）的协同作用[99,100]。集团效应：掺入金属原子可破坏Ni原子簇结构，破坏布多阿尔反应及甲烷裂解所需的活性位点，直接抑制碳沉积[98,101,102]。Sachtler等人的实验证实，将活性金属（如Ni）与惰性金属（如Au、Cu、Sn）合金化，可破坏Ni的连续原子区域，形成小的Ni集团或孤立Ni原子，使催化剂选择性提高，同时抑制积碳[103,104]。

电子效应：引入金属原子会通过电荷转移或轨道杂化改变Ni原子的电子结构（如d带中心），削弱了Ni表面对含碳中间体（如CHx*，CO*等）的吸附强度，进而抑制碳沉积[99,105]。DFT计算的分波态密度（Partial density of states, DOS）显示，掺杂CeO2可使Sr1.9Fe1.5Mo0.43Ru0.07O6-δ（SFMR）上FeRu的d带中心上移，增强含氧中间体（OH*）的吸附强度，同时降低OH主导除碳路径的能垒（2.293 → 2.060 eV），增强碳中间产物的去除[106]。

具有高氧离子传导率和丰富氧空位的材料，如GDC、SDC等，可储存大量晶格氧。在电化学反应中，这些材料表面解离出的大量活性氧物种（O*、OH*等）会向金属活性位点溢流。溢流氧可促进氢气氧化，在电化学反应中，氢原子（*H）会优先和这个氧结合，形成水，加速氢气氧化反应（Hydrogen oxidation reaction, HOR），此外，溢流氧可与催化剂表面的C*、CO*反应，生成CO或CO2排出[107,108]。如BaO修饰的Ni-YSZ阳极可促进H2O的吸附与解离，生成反应活性较强的OH*物种，加速表面碳的清除[56]。

集团效应、电子效应和活性氧溢流耦合决定含碳中间体的生成速率与清除速率，集团效应主要改变连续金属位点数量，电子效应通过调节d带中心，影响CHx*、CO*、C*及OH*等中间体吸附强度，活性氧溢流取决于氧空位浓度和氧离子传导率，三者共同决定沉积碳能否被及时氧化去除[106,108 -110]。

不同金属活性位对积碳过程的影响还体现在烷烃脱氢能力与表面碳氧化速率之间的平衡。Ni对C-H键活化性能较强，可催化碳氢燃料深度脱氢，生成大量不饱和CHx*（x<3）中间体，这些不饱和碳氢物种在高温下易通过C-C偶联发生聚合，生成多环芳烃等焦炭前驱体，最终沉积为石墨化碳，而Ni对碳的氧化效率低下，导致大量碳沉积[108,111]。如在Co-Fe合金负载钙钛矿上，实现了电能与液体化学品共生产，尾气中检测到由芳构化路径形成的多环芳烃，说明Co-Fe合金对C-H活化和芳构化具有较强促进作用[112]。Cu对C-H键的催化能力低下，而Co和Fe的脱氢能力介于Ni和Cu之间，Co可适度活化C-H键以维持燃料转化活性，而Fe有助于促进氧空位形成和活性氧物种生成，提升碳氧化速率[113]。因此，抗积碳电极材料设计不应单纯追求提高烃类活化能力，而应同时抑制过度脱氢和不饱和中间体聚合，并提高表面活性氧对C*、CO*和CxHy*等物种的氧化清除速率。

3 二氧化碳电解抗积碳研究进展

3.1 二氧化碳电解积碳热力学分析

SOECs进行CO2还原反应（CO2 reduction reaction, CO2RR），碳生成主要路径的动力学模型机理见图3，CO2接受电子生成CO，同时产生O2-并经电解质传输至氧电极，阴极表面发生的反应见式（2）[114,115]。

CO2(g) + 2e- = CO(g) + O2-（2）

然而，在CO2电解过程中，当阴极局部CO分压升高或阴极过电位过大时，阴极会发生下列反应生成焦炭。

2CO(g) = C + CO2(g) （3）

CO(g) + 2e- = C(s) + O2- （4）

热力学分析是预判积碳自发倾向的重要策略，通过计算化学反应的吉布斯自由能变（ΔG）以预测在特定温度、压力和气体组分下，系统达到平衡时是否会生成固态碳[116]。此外，基于能斯特方程，研究者还提出可利用能斯特电压替代ΔG作为判断碳沉积热力学趋势的判据。据此构建的热力学反应相图可确定CO2电解的无积碳区：在典型CO2电解条件（阴极：1 atm CO2；阳极：1 atm 空气；温度：800 oC）下，将电解电压控制在-0.9至-1.4 V范围内，可同时抑制Ni的氧化与碳的沉积[117]。

3.2 CO2电解抗积碳策略

传统SOEC阴极Ni-YSZ，因Ni为布多阿尔反应的高效催化剂，导致碳沉积现象较为严重，易导致电池性能失效，研究人员常用的抗积碳策略包括设计新型材料、添加蒸汽或CO2等作为氧化剂等。部分抗积碳研究进展见表2，CO2电解抗积碳策略主要包括催化剂修饰、调节反应温度和过电位、添加保护气等。

3.2.1 镍基阴极优化

SOEC常用Ni基金属陶瓷骨架（Ni-YSZ和Ni-GDC等）为阴极，其中Ni-GDC的抗积碳性能优于Ni-YSZ[128,129]，但在Ni基催化剂上，Ni易被氧化生成绝缘的NiO，降低性能的同时，还带来严重的积碳问题[130,131]，因此该类金属陶瓷催化剂表面修饰是研究重点，如通过Fe金属掺杂Ni纳米颗粒中，可活化近邻的Ni原子为电化学活性位点，提升CO2的活化与解离，Fe等金属的引入还可抑制Ni的氧化，提升催化性能的同时有效抑制碳沉积[132,133]。

Ni合金化改性是重要抗积碳策略，如研究人员分别探究了Cu、Fe和Co分别与Ni掺杂形成合金后，可显著影响Ni-YSZ电极的活性与抗积碳能力，电化学阻抗谱（EIS）显示，合金可降低表面反应相关的表观活化能，加速CO2电解，但SEM和拉曼光谱分析均表明，Fe和Cu可抑制碳沉积，而Co会促进碳沉积，由于Co和Fe促进CO2的解离，而Cu可促进产物解吸并加速循环，因此，掺杂Cu成为抑制Ni基陶瓷材料碳沉积的重要策略[110]。

利用Cu直接替代Ni也是重要研究方向，如开发了Cu-Pr0.1Ce0.9O2-δ (Cu-PDC)阴极，在CO2-CO复合气体氛围中，电池表现出良好的电解性能与稳定性，对碳沉积具有显著抗性[134]。针对Cu熔点较低且易烧结的问题，常采用复合结构（如Cu-GDC），利用GDC提供离子导电性与催化活性[126,135,136]。采用低温浸渍法开发了Cu-GDC和Ni-GDC阴极，二者性能接近，在沼气气氛中，Cu-CGO可完全避免碳沉积[137]。在另一项研究中，将Cu引入SFM和GDC中，形成了原位出溶的Cu-Fe双金属位点，大幅提高了CO2吸附与催化能力，电流密度增加了65.7%，在反应前后的拉曼光谱都未检测到明显的C-C信号[138]。Cu不能催化C-C键形成或解离CO，从根本上抑制碳沉积，该原理已在SOFC研究中证实并应用于SOEC[139]。此外，在中温（600-700 oC）环境下，Cu-GDC阴极表现出良好的电解能力且无明显无定形碳生成，证实了中温SOEC运行的可行性[140]。

表2中部分Ni基阴极研究进一步揭示了SOEC中抑制积碳的关键，即降低CO解离倾向并提高CO2活化能力。Co0.5Ni0.5@CeO2复合催化剂通过CeO2提供氧空位和界面活性氧，同时利用CoNi合金调节CO结合强度，从反应中间体层面降低碳生成倾向[119]。CGO及金属-CGO纳米颗粒浸渍阴极材料中，具有氧离子传导和储放氧能力的CeO2基组分不仅能够拓展反应活性界面，还可通过降低局部过电位和促进表面碳氧化来改善抗积碳稳定性[118,123]。

3.2.2 无镍阴极开发

开发无镍阴极可从根本上解决碳沉积，钙钛矿氧化物也可用于SOEC应用，被视为构建下一代SOEC电极的理想平台。常见SOEC阴极单钙钛矿A位的阳离子通常是碱土金属元素，如Ba[141]、Sr[142]或稀土元素（如La[143]、Pr[144]等），B位通常是过渡金属元素，如Co[145]、Fe[146]、Ta[147]和Nb[148]等，这些元素位于由6个氧原子形成的八面体中心，通常表现为+4和+3价态。

通过A/B位元素掺杂可显著提升电极的氧化还原稳定性与抗积碳能力，如La0.2Sr0.8TiO3+δ（LST）和LSCM等材料由于B位阳离子（Ti、Cr、Mn）不具备成碳催化活性，从而展现出天然的抑碳优势[76,149]。此外，在钙钛矿基底上负载合金纳米颗粒（如Co-Fe、Ni-Fe等）也是抗积碳重要策略，通过原位出溶将Co-Fe合金负载于Sr2Ti0.8Co0.2FeO6−δ（STCF）表面，可大幅提升氧空位浓度与CO2吸附能力，在800 oC下实现了0.81 A/cm2的高性能且无碳沉积[150-152]。在另一项研究中，研究人员通过热还原法将Co-Fe合金纳米颗粒负载在STCF上，与SDC组成混合电极，在100h下保持了良好的稳定性，表面无碳沉积，微观结构几乎保持不变[153]。此外，阴离子掺杂（如F-掺杂）同样有效，研究表明F-掺杂的LSFN阴极在1.8 V下电流密度达1.93 A/cm2，且在60 h运行前后拉曼光谱均未检出碳信号[154]。

Cu元素掺杂是SOEC阴极改性的重要策略，如在Cu@SFCMT（Sr1.9Fe1.3Cu0.2Mo0.4Ti0.1O6−δ）-GDC阴极上，Cu掺杂显著增加了氧空位浓度并促进了CO2电解，在无还原保护气（H2或CO）的严苛条件下连续运行210 h且无积碳生成[155]。Cu浸渍的LSCM复合阴极表现出较低的欧姆电阻与优异的抑碳稳定性，在超过50 h的稳定性试验中表现良好，显著抑制碳沉积[156]。此外，LSM表面原位出溶的Ni-Cu合金纳米颗粒能显著提升CO产率（9.51 mL min-1 cm-2），并在抑制碳沉积方面发挥协同作用[157]。此外，阴离子（如F-）掺杂到O位点是一种有前景的方法，如Sr2Fe1.5Mo0.5O6-δF0.1 (F-SFM)在CO2电解中表现出高性能，在800 oC下，纯CO2气氛中稳定性超过120 h，为SOEC的抗积碳和稳定性研究提供了有效策略[158]。

除传统钙钛矿外，多组元合金/氧化物复合材料和离子迁移调控策略也成为SOEC抗积碳阴极的重要方向。高熵/中熵合金及单原子催化剂也表现出较高的抗积碳能力，如FeCoNiCr与MnO复合作为催化剂，不仅促进了CO2的活化与解离，还实现了高达200 h的无积碳稳定运行[10]。SDC表面负载单原子Cu，促进氧空位形成，提升电解性能，拉曼分析表明反应后的阴极表面D带/G带缺失，表明无任何无定形或石墨碳[124]。

3.2.3 工况条件优化

在SOEC工作过程中，温度、电位、压力等工况条件也可直接影响其性能和稳定性。SOEC通常需要在高温（600-900 oC）下运行，电解是吸热过程，高温下可实现快速反应动力学与高能量转化效率，可实现更高的整体转换效率[159]。如表2，在CO2-CO混合气中，提高温度可提高体系允许的CO临界含量，750 ℃时CO含量临界值可达到78.21%，表明高温有利于削弱布多阿尔反应生成碳的热力学驱动力[120]。在电位调控方面，Ni-Fe-La0.6Sr0.4Fe0.8Mn0.2O3燃料电极以及CGO基浸渍电极均可通过降低阴极过电位来减少CO电化学解离和局部碳生成[121,123]。通入CO作为保护气可调节电极附近的气体组成和反应平衡，可有效抑制碳沉积，但对电解性能影响较小[122]。这些结果表明温度、气氛组成和电极过电位应作为耦合参数共同优化，可有效抑制碳沉积。

过电位（实际工作电压与能斯特电势之差）是驱动电解反应的必要条件，虽然阴极过电位提供了还原驱动力，但SOEC模式下的积碳风险通常高于SOFC。高电流密度往往伴随高过电位，过高的极化会加速碳生成[160]。随着运行时间延长，燃料电极的过电位会逐渐增加，局部条件可能将超过热力学阈值形成焦炭[161,162]。除布多阿尔反应外，高过电位下CO的电化学解离（CO+2e−→C+O2−）是积碳加剧的另一重要诱因[163]。因此，SOEC运行时需设计专门控制策略，确保电极电位始终处于安全操作窗口内。

由于实际电解池中存在气体浓度梯度和极化传质阻力，局部积碳的发生往往早于宏观热力学预期，在CO2电解中，积碳实际发生点对应的CO浓度比理论平衡浓度低10%至20%，如750 ℃下为77.8%，且通过EIS中低频峰的快速衰减可以观察到低CO浓度下的早期积碳[164]。因此，SOEC运行时需结合原位监测，设定比纯热力学计算更严格的安全操作边界。

此外，高压运行是提升SOEC效率的另一探索方向，然而，高压会显著加剧积碳倾向，如根据C-H-O相图，中间水冷凝后C-H-O比例发生变化的气体组成，低温高压的方案有利于抑制碳沉积[165]。针对高压稳定性挑战，提出了新型脉冲运行模式（AC:DC），通过在直流电中引入快速反向脉冲实现产氢速率与电池内部温度的解耦。这种间歇性运行模式能有效减小温度波动，并利用周期性的氧化还原循环清除杂质沉积，从而实现了SOEC在5 bar压力下的长效稳定运行[166,167]。

4 P2X 应用中的抗积碳研究进展

4.1 P2X应用中积碳原因

电转X（Power to X, P2X）是一种将可再生能源转化为其他形式能源或燃料的技术，其中X可以是氢气、氨气、合成气或合成燃料[12]。第三章讨论的SOEC以CO2电解制备CO为主要反应，而P2X主要存在两条工艺路径：一是通过CO2和H2O、CH4共电解制取合成气（H2+CO），随后经由费托合成转化为液体燃料；二是利用CH4和乙烷等直接合成乙烯等C2+短链烃类[168-171]。在CO2还原中，中间产物CO在催化剂表面的吸附与反应是积碳的关键诱因，特别是在高过电位下，CO易发生布多阿尔反应（2CO = C + CO2）生成碳[4]。此外，CH4易直接脱氢分解为C（CH4 = C + 2H2），进一步加剧积碳风险。P2X是积碳的中间过程，因此，其抗积碳策略应控制目标产物生成，降低碳生成。

4.2 P2X应用中的抗积碳策略

P2X的抗积碳策略重点在于抗积碳与选择性协同调控，主要以CO2/H2O共电解和CH4、乙烷等直接合成C2+短链烃类为主要反应。材料设计重点关注协同调节CO2/H2O活化、C-H键活化和C-C偶联/断裂路径的Ni基合金、无Ni钙钛矿、金属-氧化物界面及原位出溶纳米颗粒；工况优化方面则重点关注电压、温度、反应物比例和串联反应体系对目标产物选择性与积碳风险的共同影响。

P2X场景下的抗积碳策略在抑制无定形碳或石墨碳形成的同时，最大化目标产物的法拉第效率，其抗积碳策略应围绕“中间体生成-偶联/脱附-氧化清除”进行选择性调控，如在材料设计中，应通过Ni-Cu、Co-Fe等合金化、金属-氧化物界面和无Ni钙钛矿电极调节CHx*、C2Hx*和CO*吸附强度，削弱连续金属位点诱导的C-C键断裂、深度脱氢和CO解离，使中间体优先发生C-C偶联、脱氢脱附或CO脱附生成目标产物[169,172 -174]。在CO2/H2O共电解制合成气中，CO2还原生成的CO*中间体既可脱附为CO产物，也可进一步发生C-O键断裂生成C*并引发积碳[110]。此外，以CH4直接转化为C2H4为例，CH4首先在催化剂表面发生C-H键活化生成CHx*（x=1~3）中间体，这些中间体存在两条竞争路径：一是通过C-C偶联生成C2H6并进一步脱氢得到目标产物C2H4（脱氢-偶联路径）；二是发生过度脱氢，CHx*进一步失去H原子生成C*，C*聚合形成焦炭（深度脱氢-积碳路径）[169]。

4.2.1 镍基阴极优化

在P2X场景下，含镍燃料电极易导致积碳，对其进行合理改性可增强性能和稳定性，如浸渍Ni-SDC纳米颗粒保护的Ni-YSZ燃料电极耐久度显著提高，在H2O-CO2气氛中可实现共电解制备合成气，稳定运行时间达到200 h [175]。Ni基催化剂中，Ni-GDC在共电解中的法拉第效率显著优于Ni-YSZ（90% vs 60%），且在Ni-GDC中几乎观察不到碳沉积，DFT计算表明，Ni-GDC与H2O的吸附能低于Ni-YSZ（0.32 vs 0.42 eV），而CO2的吸附能高于Ni-YSZ（0.65 vs 0.56 eV），因此，二者反应活化能几乎相同，研究人员提出，GDC作为双相边界组分，是导致两种阴极之间性能差异的重要原因[176]。Ni-YSZ单独使用时，在共电解模式下，Ni颗粒易聚集，导致接触面积变小，降低反应速率，且Ni易被氧化，将YSZ替换为GDC可降低过电位，并抑制镍氧化，在Ni-GDC基础上进一步负载Ru，可显著提高电解性能，有利于逆水煤气变换反应，且可通过低过电位显著抑制碳沉积[177]。

利用CH4、乙烷等合成乙烯时，传统Ni-YSZ燃料电极的碳沉积问题较为严重，研究人员开发了Ni0.5Cu0.5-NTMO（NiCu-Nb1.33(Ti0.8Mn0.2)0.67O4-δ）催化剂，在700 oC下，该材料实现了75.2%的乙烷转化率，乙烯选择性接近100%，在超过10 h的稳定性测试后，SEM和XPS表征显示，催化剂表面未检测到明显的碳沉积信号，DFT计算表明，向Ni-NTMO表面引入Cu形成合金后，吉布斯自由能由0.306提升至2.45 eV，保留Ni对C-H键活化能力的同时，在热力学上有效抑制了C-C键断裂，进而抑制碳沉积[172]。此外，在萤石矿CeO2表面溶解多孔单晶Ni纳米颗粒来构建TPB界面，实现高效CH4制备C2，CH4转化率约为7%，而乙烷和乙烯的选择性达到≥99.5%，且抗碳沉积性能优异，连续运行100 h后没有观察到性能退化[178]。

4.2.2 无镍阴极开发

设计无镍催化剂可从源头抑制共电解制备合成气的积碳问题，目前已报道的材料可以显著缓解积碳问题，延长稳定运行时间。钙钛矿是最具代表性的阴极材料，可缓解CO2和H2O共电解制备合成气的碳沉积问题，如在共电解模式下，纳米颗粒修饰的La0.43Ca0.37Ni0.06Ti0.94O3 (LCT-Ni)钙钛矿阴极可将电流密度提高20%，在2 V时达到1.6 A/cm2，相较于Ni-YSZ阴极，抗积碳能力显著提高[179]。钙钛矿还可调节产物合成气的比例，如在SFM-SDC对称电池上实现了高CO2转化率，制备的合成气H2与CO比可达较为理想的2:1，且可在103 h的稳定性试验中表现良好，SEM图像观察不到碳生成[180]。此外，钒基钙钛矿（La0.6Sr0.4VO3−δ）在共电解中表现优异，这归功于多价态钒离子（V3+、V4+和V5+）与Sr2+取代La3+过程带来的高电导率及电化学活性[181,182]。图4展示了在部分过渡金属氧化物上，H2O/CO2共电解在不同温度下的标准吉布斯自由能变化，布多阿尔反应在低温下容易发生，易诱发碳沉积，CH4也在低温下容易生成，而高温有利于CO和H2生成[183]。

CH4和乙烷等高温合成乙烯具有较高的经济价值，如在Co@CeO2电极表面可实现乙烷与CO2共电解，原位生成的金属氧化物界面的活性电极促进乙烷C-H键断裂，促进乙烯高效生产，在共电解中，乙烷转化率可达33.1%，乙烯选择性达到88.9%，且拉曼光谱证实其表面几乎无积碳[185]。此外，在CeO2表面溶出NiCu合金纳米颗粒可实现乙烷合成乙烯的高选择性（64%），在CeO2-NiCu+SDC电极上进行100 h的稳定性试验，且几乎无碳生成[186]。钙钛矿是重要燃料侧材料，如在SFMO (Sr2Fe1.5+xMo0.5O6−δ; x = 0-0.1)阴极上，多孔电极支架中纳米级金属-氧化物活性界面提升了CH4活化活性与抗碳沉积能力，可获得最高16.7%的C2产率（11.5%乙烯+5.2%乙烷），具有较高的耐久性[169]。在另一项研究中，在Sr2Fe1.5Mo0.5O6−δ (SFM)电极上可实现CH4重整为乙烯、乙烷和H2混合物，在800 oC下，CH4转化率达到85.8%，C2H4、C2H6和H2浓度分别为10.5%、12.3%和25.6%，且在200 h试验后，未发现任何碳沉积[187]。钙钛矿改性可提高性能与稳定性，如在LSCF-SDC燃料电极表面浸渍γ-Al2O3，可获得29.1%的乙烷转化率和92.5%的乙烯选择性，结合DFT计算与原位XPS表征显示，Al2O3/LSCF界面有效抑制吸附氧物种的形成，提高乙烯选择性和催化稳定性，这是因为Al-O-Fe化学键调节界面Fe中心的电子结构[188]。此外，在Sr3Fe2O7钙钛矿上构建NiCu双金属合金纳米颗粒，在本体相中掺杂Hf元素可提高质子电导率，实现乙烷定向高效转化，在700 oC下获得50.04%的乙烷转化率和90.42%的乙烯选择性，同时，阴极CO2RR反应进一步耦合，使阳极乙烯转化率升高，阴极产生合成气，这种电化学反应过程为高附加值小分子化工产品的清洁生产提供了新策略[189]。

除了传统平面电池，电池构型的创新与多系统耦合也是应对P2X高积碳风险的重要前沿方向，如管式固体氧化物电解池（T-SOEC）耦合阴极的H2O/CO2电解与阳极的乙烷氧化脱氢反应，可有效调控氧离子向阳极的精准传输速率，为低碳乙烯的连续高效生产提供了兼顾高选择性与抗积碳性的工程化新途径[190]。

4.2.3 工况条件优化

调控反应电位、温度、反应物浓度以及反应系统等条件，可有效抑制积碳生成。选择合适工作电压，可避免高过电位下中间体聚合，有效抑制碳沉积[191]。据报道，外加电位高于-1.3 V时，易发生碳沉积，而外加电位降低至-0.9 V时，Ni会被氧化[117]。过电位是积碳的主要驱动力之一，随电流密度增大，电极-电解质界面处过电位升高，局部还原性增强，促使CO分子接受电子生成C（式5），高过电位加速CO2RR速率，使CO在电极微孔内迅速累积，加剧CO分压升高，在热力学上促进布多阿尔反应向C生成方向移动[161]。

CO + 2e- = C + O2- （5）

温度直接影响电化学动力学与系统稳定性，从动力学角度来看，高工作温度加速电极反应，从而降低燃料电极和氧电极的过电位[168]。随温度升高，乙烷转化率和乙烯产率随温度均增加，600 oC时，乙烯选择性获得82%的峰值，600 oC以上选择性下降，这可能是碳沉积和乙烯偶联等副反应导致的[192]。

此外，构建多级串联电催化系统或电-热催化耦合系统是提升效率并抑碳的创新方向。相较于单电池系统，串联系统通过优化CO的浓度梯度分布和反应环境，有效抑制了竞争性的析氢反应（HER），大幅提高了CO2RR制得C2的效率，且能量需求大幅降低[193]，且为C2中间体的生成及C3+高碳化学品的生产提供了更优的动力学条件[194]。

4.2.4 燃料气氛优化

优化燃料气氛可有效抑制碳沉积，向燃料气氛中通入如水蒸气、H2等作为保护气可抑制碳沉积[16,120]。CO2中加入H2O可实现共电解制备合成气。如图1，提高燃料中的氢含量可有效抑制积碳，原因在于H2能够与沉积碳反应生成气相产物如甲烷（C +H2→CH4），而较高的CO含量可能通过布多阿尔反应促进碳生成[195]。此外，向阳极加入CH4可实现CO2与CH4共电解制备合成气，可实现较高合成气产率与超过70 h的稳定性，该体系还可用于C2+合成，产率可达25.4%[173,174]。

空气电极供气条件也会影响SOEC性能与抗沉积能力，如对比发现，输入空气与不输入空气时的总降解率分别为24.41 %/kh和8.37 %/kh，然而，无空气输入的SOEC在入口和出口处没有观察到碳沉积，而以5 L/min速率输入的空气在出口处发现轻微碳沉积，说明空气供给会影响电解效率、局部气氛和碳沉积[196]。

4.3 SOC不同应用场景抗积碳特性的横向对比

SOFC、SOEC和P2X的积碳均发生在燃料侧，但不同应用场景在反应驱动力、主要积碳来源、关键影响因素和抗积碳策略方面存在明显差异。SOFC模式下，积碳主要源于长链烃类或甲烷的脱氢裂解，其抗积碳的核心目的是在保持燃料活性的同时，抑制碳氢键过度断裂和碳物种聚集；SOEC侧重于CO2还原，积碳更多与局部CO富集、布多阿尔反应以及高过电位下CO电化学还原有关，因此需要重点控制阴极电位、CO局部分压和CO2/CO比例。P2X场景下的抗积碳策略较为复杂，需兼顾抑制积碳与产物选择性。为了进一步提升对SOC抗积碳研究的系统性认识，对SOFC、SOEC及P2X三种模式在积碳来源与策略的差异进行深入对比（表3）。

4.4 SOC抗积碳电极材料的工程化评价指标

尽管各类抗积碳策略在实验室级别的试验中取得显著进展，但在设计商业化SOC时，需综合考虑电导率、离子/电子传输能力、相容性、制备成本及可规模化性等指标[197]。

电极材料应具备足够的离子/电子传输能力，传统Ni-YSZ和Ni-GDC等金属陶瓷电极被长期使用的原因在于其较高电子导电性，但在含碳燃料气氛中，易导致积碳失活。新型钙钛矿、萤石等氧化物通常具有较好的抗积碳能力，但部分材料电导率较低，易引发过高欧姆损耗。因此，在实际工程中，须采用A/B位高价阳离子（如Nb5+、Ta5+或多价态V离子）掺杂来优化材料的能带结构，提升离子/电子传输能力[148]。

电导率评价还应区分材料本征电子/离子传导能力与积碳形成的表观导电网络。石墨碳本身具有较高的电导率（~102 - 104 S/cm），因此积碳发生时，阳极的表观电导率可能提高，但这会阻碍SOC的正常运行。在Gorte等的研究中，针对使用碳氢燃料的SOFC，生成的碳膜具有较高电子电导率，并在三相界面附近提供电子传导通路[198]。因此，工程化选材时应同时评价无碳状态下的混合导电能力、积碳前后EIS/四探针电导变化、孔结构保持率和性能可恢复性，避免单纯以电导率作为性能指标产生误导，必须结合电化学阻抗谱中极化电阻的变化、微观结构演变以及长期恒流放电下的性能衰减率等指标进行综合评判。

长期运行中的结构破坏是全电池商业化失效的核心主因，具有高抗积碳性能的含Co、Fe钙钛矿具有较大的热膨胀系数（TEC，通常>1.5×10-5 K-1），与YSZ或GDC等常用电解质（~1.05-1.2×10-5 K-1）可能存在热失配，在长期热循环中易诱发结构破坏或阻抗增加[199]。因此，结合机器学习（Machine Learning）可辅助预测材料的热膨胀行为，通过引入负膨胀系数掺杂剂或利用复合电极构建技术，将整体TEC降低至安全范围内，同时有效抑制高温制备与运行过程中绝缘副产物的生成[200,201]。

此外，制作成本与可规模性也是SOC商业化应用的关键因素，使用贵金属（Ru、Pt等）虽然可获得较高活性和抗积碳性能，但成本较高，利用廉价过渡金属（Cu、Fe、Mn等），结合浸渍、溶出和原子层沉积（ALD）等工艺，可在提高SOC性能的同时，并降低成本，提高可规模性[202,203]。

4.5 SOC多参数耦合的安全运行窗口建议

除材料本身的抗积碳能力外，SOC运行过程中的温度、过电位、蒸汽碳比（V/C）、压力、电流密度、燃料利用率和局部CO/CO2比例等参数相互耦合，共同决定积碳倾向和运行稳定性[204]。如单纯提高V/C或升高温度会抑制积碳，但提高蒸汽占比会降低反应物浓度，并可能加速电极中的Ni被氧化；而提高温度虽然有利于反应动力学和布多阿尔反应平衡调控，却也可能加速CH4裂解、金属颗粒烧结或热失配失效。

因此，面向工程实践的抗积碳指导，需考虑多参数耦合，如在最新研究中，研究人员评估了金属支撑等新型SOC在动态电流下的共电解稳定性，设计了包含动态电流密度、温度和实际反应物比例的安全运行窗口，证实局部CO/CO2比例是低CO2氛围中碳沉积提前触发的关键原因，成功规避因局部热力学平衡偏移而可能导致的碳沉积[205]。

SOFC模式下，安全窗口应优先保证阳极局部氧碳比充足，避免高燃料利用率、低V/C和强内重整耦合导致的入口/出口气氛不均；SOEC模式应同时约束阴极过电位、CO局部分压和CO2转化率，避免进出口气体组成仍处于安全区时，电极孔道内部已达到碳沉积阈值；P2X模式还需把目标产物选择性纳入窗口设计，在C-H活化和C-C偶联所需的强还原条件与积碳风险之间寻找平衡。因而，多参数窗口不应仅由平衡热力学相图给出，还应结合分段电池、原位拉曼/XPS、在线质谱或微型气相色谱等手段监测局部温度、电流密度和气体组成，并通过动态工况验证窗口的鲁棒性[204,205]。

5 总结与展望

5.1 主要结论

固体氧化物电池（SOC）抗积碳研究已取得显著进展，但碳沉积仍是限制其长期稳定运行和商业化应用的关键问题。本综述分别阐明了SOFC、SOEC和P2X模式下的积碳来源、关键影响因素与抗积碳策略，并从材料设计、气氛/工况优化和机理分析等方面归纳了相关研究进展。主要结论包括：

1 、 SOFC模式下，含碳燃料在Ni基阳极表面的裂解和CO布多阿尔反应易生成积碳，覆盖三相边界并导致性能衰减。Ni合金化、无Ni钙钛矿阳极、氧离子导体催化层及燃料气氛优化可有效降低积碳风险，其核心在于通过集团效应、电子效应和活性氧溢流协同调节含碳中间体的生成与清除；

2、 SOEC模式下，碳沉积主要与CO2还原过程中的局部CO富集、阴极过电位和CO电化学还原有关。通过Ni基阴极合金化、无Ni钙钛矿/萤石复合阴极、原位出溶纳米颗粒以及气氛和电位调控，可降低CO解离和表面碳生成倾向，提高电解稳定性；

3、 P2X模式下，CHx*、C2Hx*和CO*等中间体既可能转化为目标产物，也可能进一步形成积碳前驱体，因此需要围绕“中间体生成-偶联/脱附-氧化清除”进行选择性调控，在提高C2+短链烃、合成气等目标产物选择性的同时抑制积碳；

综上，SOC抗积碳研究已从单一材料优化逐步转向“材料-界面-工况”多尺度协同。未来仍需结合原位表征、理论计算和工程化评价，进一步明确抗积碳机理边界，并综合考虑电导率、相容性、制备成本、可规模化性和多参数安全运行窗口。

5.2 展望

未来SOC抗积碳研究仍需在以下方面进一步优化：

4、 原位表征结合计算机模拟进行机理探究：目前关于抗积碳机理的研究多基于理想模型与静态条件，未来研究应借助先进的原位表征技术，实时追踪真实反应条件下的碳物种演化与催化剂结构动态重构过程。同时，应结合第一性原理计算、微观动力学模拟与机器学习，建立跨尺度的理论预测模型，围绕连续金属位点密度、d带中心、氧空位形成能、OH*生成能、局部CO/CO2比例和电极极化阻抗等描述符，量化不同掺杂元素、界面结构和工况条件对“活性氧溢流”和“电子/集团效应”的贡献度与适用边界；

5、 建立多参数耦合的安全运行窗口：SOC的实际运行环境极为复杂，未来的研究不应仅停留在单一变量的讨论，而需系统探究温度、过电位、运行压力以及动态气氛等多参数耦合作用对碳沉积热力学与动力学边界的综合影响。在SOFC模式下，应重点避免高燃料利用率导致局部氧碳比不足；在SOEC模式下，应控制阴极过电位和CO局部分压；在P2X体系中，则需同时兼顾目标产物选择性、积碳风险和系统能效；

6、 新型材料设计：在保证运行性能的前提下，需保证长时间运行稳定性，新型材料开发需综合评估其电子/离子电导率、与相邻组件的热膨胀系数及化学相容性，并尽可能降低成本，研究可规模化放大的电极制备工艺；

7、 针对P2X共电解中C2+高附加值化学品合成的需求，并保证高选择性和抗积碳性能，应着力设计双功能催化界面，未来催化剂设计应调控含碳中间体的吸附、偶联和脱附路径，使其优先转化为目标产物，而非积碳副产物。

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基金资助

国家重点研发计划(2022YFD1601100)

中央高校基本科研业务费专项资金资助(SWURC2020002)

西南大学青年团队专项基金(Swuxjpy202303)

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