| 66 | 0 | 377 |
| 下载次数 | 被引频次 | 阅读次数 |
“分工协作”型离子–电子混合导体是近年来固态离子学基础研究方面提出的重要新概念之一。有别于传统的离子–电子混合导体中离子和电子都在同一相中输运，“分工协作”型导体中离子与电子分别在不同的相中迁移，并在相界面处实现耦合，从而完成整体的电荷输运过程。由于“分工协作”型混合导体两相界面处独特的空间电荷层结构，使得沿着界面的化学扩散系数远快于单相混合导体，并且具有体相不具备的界面电荷存储能力。而固体氧化物电池的复合电极恰恰满足“分工协作”型混合导体的离子导电相和电子导电相两相共存的特点。本文将详细叙述“分工协作”型混合导体的概念和特征，并讨论利用“分工协作”型混合导体设计固体氧化物电池电极材料的应用前景。
Abstract：Mixed ionic-electronic conductors(MIECs) are foundational to the field of solid-state ionics,enabling the concurrent transport of ionic species(such as Li+,H+,O2-,or related point defects) and electronic species(i.e.,electrons and holes).The MIECs play a pivotal role in a variety of energy conversion and storage devices due to their ambipolar conduction properties,such as lithium-ion battery cathodes and air electrodes in solid oxide cells(SOCs).In these applications,the chemical diffusion coefficient D~δ,which describes the effective transport rate of neutral species,is a key performance-limiting parameter.However,in conventional MIECs,D~δ is typically governed by the slower carrier(most often the ionic species),thus restricting the overall rate of charge/discharge or redox processes.The "job-sharing" type mixed conductor(JSMC) offers a promising strategy to overcome this intrinsic transport limitation.In contrast to single-phase MIECs,where ion and electron transport both occur within the same material matrix,JSMCs spatially separate the two processes into distinct ion-conducting and electron-conducting phases.The transport of neutral species is localized at the interfaces between the two phases,where the formation of space charge layers dramatically alters the defect distribution and electrostatic potential landscape.These interfaces exhibit an enhanced chemical diffusion,along with unique interfacial charge storage behavior enabled by the accumulation of mobile defect pairs-properties absent in either constituent phase alone.This review represents the fundamental principles underpinning JSMC behavior,including space charge theory,electrostatic potential gradients,and chemical capacitance considerations.Recent representative systems like Li_2O:Ru,RbAg_4I5:C,and Li_2O:Fe composites are summarized,which demonstrate the JSMC signature effects,anomalously high chemical diffusivity and excess charge storage capacity at interfaces.The concept is extended to the systems involving one phase of a conventional MIEC,indicating the broad adaptability of the framework.A particular focus is on the application of the JSMC model in solid oxide cell composite electrodes.These electrodes naturally consist of coexisting ionic and electronic conductors and exhibit a significantly improved performance over single-phase materials.A composite electrode behavior in SOCs from the perspective of interfacial ion-electron cooperation is described,offering a mechanistic understanding of observed enhancements in polarization resistance and electrochemical activity.In addition,some experimental strategies for elucidating JSMC behavior are also proposed,such as direct interfacial potential profiling via in situ near-ambient pressure X-ray photoelectron spectroscopy,and the construction of vertically aligned nano structures to systematically vary interfacial density.The JSMC bridges fundamental theories of defect chemistry and electrostatics and provides a predictive framework for optimizing complex electrode architectures.This work aims to establish a more unified understanding of composite electrode function and guide the rational design of high-performance electrochemical materials in a range of solid-state energy technologies.Summary and Prospects The "job-sharing" type mixed ionic-electronic conductor presents a promising strategy to overcome the transport limitations inherent in conventional MIECs.JSMCs enable both fast ambipolar diffusion and interfacial charge storage via decoupling ion and electron transport into separate phases and localizing their coupling at interfaces.Composite electrodes in solid oxide cells naturally embody the structural preconditions for JSMCs,making them fertile ground for experimental validation and application of this concept.Several key research directions emerge for the continued development and practical implementation of JSMCs,i.e.,a) mechanistic clarification of interfacial space charge layers:Although space charge layers are central to the JSMC mechanism,their microscopic origin,spatial extent,dynamic formation process,and impact on chemical diffusion remain poorly understood.Advanced in-situ techniques like near-ambient pressure X-ray photoelectron spectroscopy,scanning probe microscopy,or operando impedance mapping should be leveraged to directly resolve interfacial electrostatic potential distributions and charge accumulation behavior;b) structural engineering of well-defined model systems:The fabrication of vertically aligned nanostructures or multilayer heterostructures can serve as model JSMC platforms with tunable interfacial density and orientation.Such systems can bridge microscopic interface features with macroscopic electrochemical performance,enabling quantitative structure-function correlations;c) extension to new material systems:To date,most JSMC studies focus on cation conductors(especially Li+).A future work should explore a potential of JSMC behavior in oxide-ion conductors,proton conductors,and emerging solid-state or aqueous battery chemistries such as Na~+and Zn2+systems,where interfacial ion-electron cooperation may also enhance device performance;and d) multiscale modeling and design principles:To move toward predictive control of JSMC interfaces,it is necessary to integrate first-principles calculations,phase-field simulations,and defect chemistry frameworks.These tools can help establish design rules for optimizing ionic/electronic phase connectivity,space charge layer thickness,and interface orientation for maximum performance.In summary,JSMCs offer a transformative approach to interfacial transport and storage in electrochemical systems.The mechanistic understanding and establishing controllable model systems will be a key to fully unlocking their potential in a wide range of solid-state energy technologies.
[1]MAIER J.Nanoionics:Ion transport and electrochemical storage in confined systems[J].Nat Mater,2005,4(11):805-815.
[2]MAIER J.Pushing nanoionics to the limits:Charge carrier chemistry in extremely small systems[J].Chem Mater,2014,26(1):348-360.
[3]CHEN C C,MAIER J.Decoupling electron and ion storage and the path from interfacial storage to artificial electrodes[J].Nat Energy,2018,3:102-108.
[4]FU L J,CHEN C C,MAIER J.Interfacial mass storage in nanocomposites[J].Solid State Ion,2018,318:54-59.
[5]CHEN C C,NAVICKAS E,FLEIG J,et al.Kinetics of space charge storage in composites[J].Adv Funct Mater,2018,28(15):1705999.
[6]CHEN S H,CHEN C C.Space charge effects in mixed ionic-electronic conducting electrodes for solid-state batteries[J].Phys Chem Chem Phys,2024,26(37):24689-24698.
[7]CHEN C C,MAIER J.Space charge storage in composites:Thermodynamics[J].Phys Chem Chem Phys,2017,19(9):6379-6396.
[8]CHEN C C,MAIER J.Synergistic silver storage in the composite Rb Ag4I5:Graphite:Thermodynamics and kinetics[J].Solid State Ion,2017,312:97-105.
[9]CHEN C C,FU L J,MAIER J.Synergistic,ultrafast mass storage and removal in artificial mixed conductors[J].Nature,2016,536(7615):159-164.
[10]FU L J,CHEN C C,SAMUELIS D,et al.Thermodynamics of lithium storage at abrupt junctions:Modeling and experimental evidence[J].Phys Rev Lett,2014,112(20):208301.
[11]XIAO C,WANG H,USISKIN R,et al.Unification of insertion and supercapacitive storage concepts:Storage profiles in titania[J].Science,2024,386(6720):407-413.
[12]CHEN L Q,MAURO J C.Unifying physics of chemical mobility,diffusivity,and capacitance[J].MRS Bull,2024,49(6):529-532.
[13]CHEN D,BISHOP S R,TULLER H L.Non-stoichiometry in oxide thin films:A chemical capacitance study of the praseodymium-cerium oxide system[J].Adv Funct Mater,2013,23(17):2168-2174.
[14]LI Q,LI H S,XIA Q T,et al.Extra storage capacity in transition metal oxide lithium-ion batteries revealed by in situ magnetometry[J].Nat Mater,2021,20(1):76-83.
[15]ZHOU S H,HUANG P,XIONG T Z,et al.Sub-thick electrodes with enhanced transport kinetics via in situ epitaxial heterogeneous interfaces for high areal-capacity lithium ion batteries[J].Small,2021,17(26):e2100778.
[16]WU L E,ZHAO L,ZHAN Z L,et al.Cathode supported tubular solid oxide fuel cells with nanostructured La0.6Sr0.4Co0.2Fe0.8O3electrocatalysts[J].J Power Sources,2014,266:268-274.
[17]NIE L F,LIU M F,ZHANG Y J,et al.La0.6Sr0.4Co0.2Fe0.8O3-δ cathodes infiltrated with samarium-doped cerium oxide for solid oxide fuel cells[J].J Power Sources,2010,195(15):4704-4708.
[18]WANG Z W,SUN H B,LI J,et al.Modified La0.6Sr0.4Co0.2Fe0.8O3-δcathodes with the infiltration of Er0.4Bi1.6O3 for intermediate-temperature solid oxide fuel cells[J].Int J Hydrog Energy,2021,46(44):22932-22941.
[19]DOS SANTOS-GóMEZ L,PORRAS-VáZQUEZ J M,LOSILLA E R,et al.Stability and performance of La0.6Sr0.4Co0.2Fe0.8O3-δnanostructured cathodes with Ce0.8Gd0.2O1.9 surface coating[J].J Power Sources,2017,347:178-185.
[20]SAR J,DESSEMOND L,DJURADO E.Electrochemical properties of graded and homogeneous Ce0.9Gd0.1O2-δ-La0.6Sr0.4Co0.2Fe0.8O3-δcomposite electrodes for intermediate-temperature solid oxide fuel cells[J].Int J Hydrog Energy,2016,41(38):17037-17043.
[21]LOUREIRO F J A,MACEDO D A,NASCIMENTO R M,et al.Cathodic polarisation of composite LSCF-SDC IT-SOFC electrode synthesised by one-step microwave self-assisted combustion[J].J Eur Ceram Soc,2019,39(5):1846-1853.
[22]ZHANG J Q,SONG K,GAO Y,et al.Tuning the thermo-mechanical synergies effect of solid oxide fuel cells with negative thermal expansion Nd Mn O3 in La0.6Sr0.4Co0.2Fe0.8O3-δ-based symmetric electrode[J].Chem Eng J,2024,491:152063.
[23]GAO J,MENG Y Q,LEE S,et al.Effect of infiltration of barium carbonate nanoparticles on the electrochemical performance of La0.6Sr0.4Co0.2Fe0.8O3-δ cathodes for protonic ceramic fuel cells[J].JOM,2019,71(1):90-95.
[24]NAM S,KIM J,KIM H,et al.Revitalizing oxygen reduction reactivity of composite oxide electrodes via electrochemically deposited Pr Ox nanocatalysts[J].Adv Mater,2024,36(25):2470191.
[25]SHRI PRAKASH B,SENTHIL KUMAR S,ARUNA S T.Effect of composition on the polarization and ohmic resistances of LSM/YSZcomposite cathodes in solid oxide fuel cell[J].Bull Mater Sci,2017,40(3):441-452.
[26]XU X Y,CAO C B,XIA C R,et al.Electrochemical performance of LSM-SDC electrodes prepared with ion-impregnated LSM[J].Ceram Int,2009,35(6):2213-2218.
[27]LENG Y J,CHAN S H,KHOR K A,et al.(La0.8Sr0.2)0.9Mn O3-Gd0.2Ce0.8O1.9 composite cathodes prepared from(Gd,Ce)(NO3)x-modified (La0.8Sr0.2)0.9Mn O3 for intermediate-temperature solid oxide fuel cells[J].J Solid State Electrochem,2006,10(6):339-347.
[28]GAO J,MENG X,LUO T,et al.Symmetrical solid oxide fuel cells fabricated by phase inversion tape casting with impregnated Sr Fe0.75Mo0.25O3-δ (SFMO) electrodes[J].Int J Hydrog Energy,2017,42(29):18499-18503.
[29]LEE S W,PARK J W,JU Y W,et al.Heterogeneous composite fibrous cathode undergoing emphasized active oxygen dissociation for La(Sr)Ga(Mg)O3-based high-performed solid oxide fuel cells[J].Small Struct,2024,5(2):2300292.
[30]YANG F,PANG S L,HE X D,et al.Scalable assembly of Pr Ba Co2O5+δ/Sm0.2Ce0.8O1.9 interfaces for advanced composite cathodes in solid oxide fuel cells[J].Mater Sci Eng B,2025,317:118225.
[31]LI J L,WANG S R,WANG Z R,et al.(La0.74Bi0.10Sr0.16)Mn O3-δ-Ce0.8Gd0.2O2-δ cathodes fabricated by ion-impregnating method for intermediate-temperature solid oxide fuel cells[J].J Power Sources,2009,188(2):453-457.
[32]LIANG F L,CHEN J,JIANG S P,et al.High performance solid oxide fuel cells with electrocatalytically enhanced (La,Sr)Mn O3 cathodes[J].Electrochem Commun,2009,11(5):1048-1051.
[33]YANG T R,KOLLASCH S L,GRIMES J,et al.(La0.8Sr0.2)0.98Mn O3-δ-Zr0.92Y0.16O2-δ:Pr Ox for oxygen electrode supported solid oxide cells[J].Appl Catal B Environ,2022,306:121114.
[34]SONG Y F,ZHANG X M,ZHOU Y J,et al.Improving the performance of solid oxide electrolysis cell with gold nanoparticles-modified LSM-YSZ anode[J].J Energy Chem,2019,35:181-187.
[35]VOHS J M,GORTE R J.High-performance SOFC cathodes prepared by infiltration[J].Adv Mater,2009,21(9):943-956.
[36]KHOSHKALAM M,TRIPKOVI?D,TONG X F,et al.Improving oxygen incorporation rate on (La0.6Sr0.4)0.98Fe O3-δ via Pr2Ni1-xCuxO4+δsurface decoration[J].J Power Sources,2020,457:228035.
[37]MA W,KIM J J,TSVETKOV N,et al.Vertically aligned nanocomposite La0.8Sr0.2Co O3/(La0.5Sr0.5)2Co O4 cathodes-electronic structure,surface chemistry and oxygen reduction kinetics[J].J Mater Chem A,2015,3(1):207-219.
[38]HAN Y,ZHANG H,YU Y,et al.In situ characterization of catalysis and electrocatalysis using APXPS[J].ACS Catal,2021,11(3):1464-1484.
[39]LU Q Y.How to correctly analyze 2p X-ray photoelectron spectra of 3d transition-metal oxides:Pitfalls and principles[J].ACS Nano,2024,18(22):13973-13982.
[40]SUN X,MACMANUS-DRISCOLL J L,WANG H Y.Spontaneous ordering of oxide-oxide epitaxial vertically aligned nanocomposite thin films[J].Annu Rev Mater Res,2020,50:229-253.
基本信息:
DOI：10.14062/j.issn.0454-5648.20250341
中图分类号:O646;TM91
引用信息:
[1]杨开创,陆启阳.基于“分工协作”型离子–电子混合导体的复合固体氧化物电池电极[J].硅酸盐学报,2025,53(10):3069-3078.DOI:10.14062/j.issn.0454-5648.20250341.
基金信息:
国家自然科学基金青年项目(52202148);国家自然科学基金青年学生项目(博士生)(523B2012)
2025-08-20
2025-08-20
2025-08-20