Article(id=1322941436596978574, tenantId=1146029695717560320, journalId=1322258626896822465, issueId=1322941226537857309, articleNumber=null, orderNo=null, doi=10.13700/j.bh.1001-5965.2026.0133, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1772985600000, receivedDateStr=2026-03-09, revisedDate=null, revisedDateStr=null, acceptedDate=1783612800000, acceptedDateStr=2026-07-10, onlineDate=1793343417548, onlineDateStr=2026-10-30, pubDate=1793376000000, pubDateStr=2026-10-31, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1793343417548, onlineIssueDateStr=2026-10-30, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1793343417548, creator=13701087609, updateTime=1793343417548, updator=13701087609, issue=Issue{id=1322941226537857309, tenantId=1146029695717560320, journalId=1322258626896822465, year='2026', volume='52', issue='10', pageStart='3237', pageEnd='3676', issueExtLink='null', onlineDate='null', pubDate='1793376000000', pubDateStr='2026-10-31', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=1, specialIssue=null, createTime=1793343367466, creator='13701087609', updateTime=1793344760378, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1322947068926505286, tenantId=1146029695717560320, journalId=1322258626896822465, issueId=1322941226537857309, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1322947068926505287, tenantId=1146029695717560320, journalId=1322258626896822465, issueId=1322941226537857309, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=3453, endPage=3470, ext={EN=ArticleExt(id=1322941437431645071, articleId=1322941436596978574, tenantId=1146029695717560320, journalId=1322258626896822465, language=EN, title=Research progress on mass transfer optimization of filter-press type electrochemical reactors for flow batteries, columnId=null, journalTitle=Journal of Beijing University of Aeronautics and Astronautics, columnName=null, runingTitle=null, highlight=null, articleAbstract=

Filter-press electrochemical reactors have become the dominant reactor configuration for flow batteries owing to their simple structure, high modularity, and low cell voltage. They also show broad application potential in energy storage batteries, electrochemical water treatment, and electrosynthetic chemical processes. Among various flow battery systems, the all-vanadium redox flow battery represents the most commercially advanced and extensively studied technology. However, inadequate mass transfer continues to limit further performance development since it increases concentration polarization, reduces voltage efficiency, speeds up long-term performance degradation, and eventually raises system costs. This review focuses primarily on all-vanadium redox flow batteries and discusses mass-transfer enhancement from the perspectives of both key reactor components and system operation. Recent advances in the mass-transfer optimization of electrodes, flow fields, membranes, and other core components are systematically summarized. The effects of operating parameters, including flow rate, temperature, current density, electrolyte concentration, and tank-to-stack ratio, on mass-transfer behavior are analyzed. Based on this, coordinated optimization solutions including reactor structure and system operation are suggested, and the coupling relationship between component-level mass-transfer characteristics and total battery performance is elucidated. From an engineering perspective, mass-transfer optimization in all-vanadium redox flow batteries should not be limited to component modification alone. Instead, it should also account for stack scale-up effects, tank-stack matching, operating-parameter regulation, and the balance between electrochemical performance and system energy consumption. This review aims to provide theoretical guidance and technical references for the engineering design and performance improvement of filter-press flow battery reactors.

, authors=Jun LIU1, 2, Zhicheng HAN2, Yan XIANG1, *, Shanfu LU1, Haining WANG1, authorsList=Jun LIU, Zhicheng HAN, Yan XIANG, Shanfu LU, Haining WANG, authorCompany=null, correspAuthors=Yan XIANG, authorNote=null, correspAuthorsNote=
E-mail:
, copyrightStatement=Copyright © 2026 Journal of Beijing University of Aeronautics and Astronautics. All rights reserved., copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1322941441672086437, articleId=1322941436596978574, tenantId=1146029695717560320, journalId=1322258626896822465, language=CN, title=液流电池用压滤式电化学反应器传质优化研究进展, columnId=null, journalTitle=北京航空航天大学学报, columnName=, runingTitle=null, highlight=null, articleAbstract=

压滤式电化学反应器因结构简单、模块化程度高、槽电压低等优势,成为液流电池主流反应器构型,并在储能电池、电化学水处理、合成化工等多个领域呈现出较广阔的应用前景。其中,全钒液流电池是商业化程度最高、研究体系最为成熟的代表,但其性能提升仍受限于传质效率不足所引发的浓差极化加剧、电压效率偏低及长期循环稳定性衰减等瓶颈问题,直接影响系统成本的控制。为此,主要以全钒液流电池为对象开展分析与讨论,从核心组件与运行系统2个角度,系统梳理电极、流场、隔膜等结构传质优化研究进展,分析流量、温度、电流密度、电解液浓度及罐堆比例等运行参数对传质过程的调控规律,明确各组件传质特性与电池整体性能的耦合关系,提出组件结构与系统运行协同的传质改进方向。从工程应用视角指出,全钒液流电池传质优化需在反应器组件改良的基础上,同步考量电堆尺寸放大效应、罐堆匹配、运行参数调控及系统能耗平衡,旨在为压滤式液流电池反应器的工程化设计与性能提升提供理论参考和技术参考。

, authors=刘君1, 2, 韩治成2, 相艳1, *, 卢善富1, 王海宁1, authorsList=刘君, 韩治成, 相艳, 卢善富, 王海宁, authorCompany=null, correspAuthors=相艳, authorNote=null, correspAuthorsNote=
E-mail:
, copyrightStatement=版权所有 © 2026 北京航空航天大学学报(自然科学版)编辑部, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=gRBphy6ubOA0/1QOgFU2dw==, magXml=CRCZ8nY6DZZBkeRJZiAuYw==, pdfUrl=null, pdf=sfdIl2xoi422wssj2sSjEQ==, pdfFileSize=11520688, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=OgieyRYjkFIl1IG0B+xL0w==, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=ypGzRvf//l+GCC+qpbdmIA==, mapNumber=null, fund=null)}, authors=[Author(id=1322941442431255470, tenantId=1146029695717560320, journalId=1322258626896822465, articleId=1322941436596978574, orderNo=0, firstName=null, middleName=null, lastName=null, nameCn=null, orcid=null, stid=null, country=null, authorPic=null, dead=0, email=null, emailSecond=null, emailThird=null, correspondingAuthor=0, authorType=1, ext={EN=AuthorExt(id=1322941442506752945, tenantId=1146029695717560320, journalId=1322258626896822465, articleId=1322941436596978574, authorId=1322941442431255470, language=EN, stringName=Jun LIU, firstName=Jun, middleName=null, lastName=LIU, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=1, 2, address=1Beijing Key Laboratory of Bionic Energy Materials and Devices,School of Energy and Power Engineering,Beihang University,Beijing 100191,China
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figureFileBig=1B18rVMz7JWwtCy2UtrDzA==, tableContent=null), ArticleFig(id=1322941454846395368, tenantId=1146029695717560320, journalId=1322258626896822465, articleId=1322941436596978574, language=EN, label=Fig. 6, caption=End-to-end AI-driven design of flow fields for vanadium flow batteries[63], figureFileSmall=pwSmp0tYdUVo4VbjviEV9g==, figureFileBig=ndiRSkl/ilXWtOU1t6Y/AQ==, tableContent=null), ArticleFig(id=1322941455110636521, tenantId=1146029695717560320, journalId=1322258626896822465, articleId=1322941436596978574, language=CN, label=图6, caption=钒液流电池流场的端到端AI驱动设计[63], figureFileSmall=pwSmp0tYdUVo4VbjviEV9g==, figureFileBig=ndiRSkl/ilXWtOU1t6Y/AQ==, tableContent=null), ArticleFig(id=1322941455450375146, tenantId=1146029695717560320, journalId=1322258626896822465, articleId=1322941436596978574, language=EN, label=Table 1, caption=Multidimensional evaluation criteria, physical significance and optimisation targets for mass transfer optimisation in flow batteries, figureFileSmall=null, figureFileBig=null, tableContent=
评价维度核心评价指标主要物理意义对应优化对象
电极孔道与界面传质[28-31]孔隙率、渗透率、有效扩散系数、曲折度、比表面积、润湿性表征电解液进入多孔电极、活性物质扩散及电极/电解液界面反应物补给能力。极限电流密度、传质系数为该类本征参数的综合外在表现。电极厚度、孔径尺寸、孔隙率、压缩率、纤维直径、微纳结构、活性位点
流体流动与空间均匀性[26,32-34]速度分布、浓度/荷电状态(state of charge,SOC)分布、电流密度分布、肋下流速、流动均匀性因子、死区比例表征流场对电极内反应物补给均匀性、局部贫液区形成和反应分布一致性的调控能力流道结构选型与几何参数优化
隔膜选择性传质[35-38]离子电导率、钒离子渗透率、离子选择性、膜阻、跨膜迁移通量表征隔膜在离子传导、活性离子阻隔和交叉污染控制之间的平衡能力离子交换膜、复合膜、多孔隔膜、选择性传输通道
运行参数与传质匹配[21,24,39-41]流量、温度、电解液浓度、SOC、充放电电流密度表征运行条件通过影响电解液物性(如黏度)及对流强度,对反应物补给速率、扩散能力和浓差过电位的调控作用流量工作窗口、温度区间、活性物浓度配比、SOC运行范围、充放电制度等
系统级传质与工程约束[42-46]多堆流量分配偏差、堆间温度偏差、旁路电流、泵基能耗占比、系统净效率表征由单电池/单电堆放大至多堆串、并联系统后,因管路结构、热质耦合与电耦合等引发的流量不均衡、电和热管理困难及寄生能耗增加等工程约束问题。多堆并联拓扑、歧管管路设计、管路阻力匹配、热管理策略、旁路电流控制、泵送系统
), ArticleFig(id=1322941455555232747, tenantId=1146029695717560320, journalId=1322258626896822465, articleId=1322941436596978574, language=CN, label=表1, caption=

液流电池传质优化的多维度评价指标、物理意义及优化对象

, figureFileSmall=null, figureFileBig=null, tableContent=
评价维度核心评价指标主要物理意义对应优化对象
电极孔道与界面传质[28-31]孔隙率、渗透率、有效扩散系数、曲折度、比表面积、润湿性表征电解液进入多孔电极、活性物质扩散及电极/电解液界面反应物补给能力。极限电流密度、传质系数为该类本征参数的综合外在表现。电极厚度、孔径尺寸、孔隙率、压缩率、纤维直径、微纳结构、活性位点
流体流动与空间均匀性[26,32-34]速度分布、浓度/荷电状态(state of charge,SOC)分布、电流密度分布、肋下流速、流动均匀性因子、死区比例表征流场对电极内反应物补给均匀性、局部贫液区形成和反应分布一致性的调控能力流道结构选型与几何参数优化
隔膜选择性传质[35-38]离子电导率、钒离子渗透率、离子选择性、膜阻、跨膜迁移通量表征隔膜在离子传导、活性离子阻隔和交叉污染控制之间的平衡能力离子交换膜、复合膜、多孔隔膜、选择性传输通道
运行参数与传质匹配[21,24,39-41]流量、温度、电解液浓度、SOC、充放电电流密度表征运行条件通过影响电解液物性(如黏度)及对流强度,对反应物补给速率、扩散能力和浓差过电位的调控作用流量工作窗口、温度区间、活性物浓度配比、SOC运行范围、充放电制度等
系统级传质与工程约束[42-46]多堆流量分配偏差、堆间温度偏差、旁路电流、泵基能耗占比、系统净效率表征由单电池/单电堆放大至多堆串、并联系统后,因管路结构、热质耦合与电耦合等引发的流量不均衡、电和热管理困难及寄生能耗增加等工程约束问题。多堆并联拓扑、歧管管路设计、管路阻力匹配、热管理策略、旁路电流控制、泵送系统
), ArticleFig(id=1322941455861416940, tenantId=1146029695717560320, journalId=1322258626896822465, articleId=1322941436596978574, language=EN, label=Table 2, caption=A comparison of mass transfer characteristics, pressure drop and suitable applications for different flow field types, figureFileSmall=null, figureFileBig=null, tableContent=
流场类型传质增强机制压降/泵耗特征适用工况与电极匹配局限性与优化方向
平行流场[57,74-75]主要依赖通道内对流、扩散传输和有限肋下渗透对电极补给压降最低、泵耗小适合低-中等电流密度、高渗透率或较薄电极;大面积电堆需重点解决各通道间的均流问题肋下和远端区域易传质不足,可通过波纹结构、导流板或多场协同结构改善
SFF[32-33,65-66]长流道形成明显沿程压差,可增强局部横向渗透和肋下传质压降较高,泵功代价明显适合较高流速、高功率密度或与较厚电极匹配的流经型设计易出现“热点”与“死区”交替,可通过变截面流道、堵块阵列、旋转或梯度深度设计优化
叉指流场[32,69,71,76]进出口非直接连通,迫使电解液穿透电极厚度方向,缩短传质路径,并增强对流补给压降取决于电极厚度、压缩率和渗透率;优化后可低于高阻SFF适合高电流密度、低流速或薄/中等厚度高渗透电极;需与电极孔结构匹配中部流量不足时易形成低浓度区,可采用并联交指、分叉交指等方式改善
多场协同流场[33-34,64,68]通过速度场、浓度场和压力场的协同匹配调节速度-浓度梯度和速度-压力梯度的协同关系,实现低阻强化传质可在提升浓度均匀性的同时,降低压降适合对传质和泵耗均敏感的工程化应用场景,尤其在中高电流密度下优势明显结构设计参数较多,需结合CFD数值模拟和实验验证,应兼顾加工可行性
仿生/双螺旋/异形流场[26,56,67,72]通过分级分流、曲线流道增强电极覆盖面积和肋下对流传质的均匀性压降一般控制在中等水平,但受结构复杂度和加工精度影响较大适合高功率密度、复杂边界条件和大面积电堆的结构筛选需关注加工成本、密封可靠性、模型泛化能力、大面积放大一致性和长期稳定性
), ArticleFig(id=1322941455957885934, tenantId=1146029695717560320, journalId=1322258626896822465, articleId=1322941436596978574, language=CN, label=表2, caption=

不同流场类型的传质特性、压降与适用场景对比

, figureFileSmall=null, figureFileBig=null, tableContent=
流场类型传质增强机制压降/泵耗特征适用工况与电极匹配局限性与优化方向
平行流场[57,74-75]主要依赖通道内对流、扩散传输和有限肋下渗透对电极补给压降最低、泵耗小适合低-中等电流密度、高渗透率或较薄电极;大面积电堆需重点解决各通道间的均流问题肋下和远端区域易传质不足,可通过波纹结构、导流板或多场协同结构改善
SFF[32-33,65-66]长流道形成明显沿程压差,可增强局部横向渗透和肋下传质压降较高,泵功代价明显适合较高流速、高功率密度或与较厚电极匹配的流经型设计易出现“热点”与“死区”交替,可通过变截面流道、堵块阵列、旋转或梯度深度设计优化
叉指流场[32,69,71,76]进出口非直接连通,迫使电解液穿透电极厚度方向,缩短传质路径,并增强对流补给压降取决于电极厚度、压缩率和渗透率;优化后可低于高阻SFF适合高电流密度、低流速或薄/中等厚度高渗透电极;需与电极孔结构匹配中部流量不足时易形成低浓度区,可采用并联交指、分叉交指等方式改善
多场协同流场[33-34,64,68]通过速度场、浓度场和压力场的协同匹配调节速度-浓度梯度和速度-压力梯度的协同关系,实现低阻强化传质可在提升浓度均匀性的同时,降低压降适合对传质和泵耗均敏感的工程化应用场景,尤其在中高电流密度下优势明显结构设计参数较多,需结合CFD数值模拟和实验验证,应兼顾加工可行性
仿生/双螺旋/异形流场[26,56,67,72]通过分级分流、曲线流道增强电极覆盖面积和肋下对流传质的均匀性压降一般控制在中等水平,但受结构复杂度和加工精度影响较大适合高功率密度、复杂边界条件和大面积电堆的结构筛选需关注加工成本、密封可靠性、模型泛化能力、大面积放大一致性和长期稳定性
), ArticleFig(id=1322941456054354928, tenantId=1146029695717560320, journalId=1322258626896822465, articleId=1322941436596978574, language=EN, label=Table 3, caption=Analysis of control variables for co-optimisation of mass transfer based on structural and operational parameters, figureFileSmall=null, figureFileBig=null, tableContent=
协同对象控制变量分析结论工程优化方向
电极厚度-流量、电流密度[29-30,75]电极厚度增加可提高有效反应面积,但会延长反应物扩散路径。低流量或高电流密度下,过厚电极内部容易出现反应物补给不足和浓差极化;较高流量或强制穿流流场可提高厚电极利用率根据目标电流密度和供液能力确定电极厚度,在反应面积增加与传质路径延长之间寻求最优平衡
电极孔隙率/渗透率-流量[28-29,75]高孔隙率和高渗透率有利于电解液进入电极并降低压降,但可能降低单位体积反应面积;低孔隙率可增加反应界面,但在高流量下可能引起较大流阻和局部传质受限建立孔隙率、渗透率与循环流量的匹配关系,在反应面积、传质能力和泵功损耗之间进行综合优化
电极压缩率-流量、电流密度[30,54]适度压缩可降低接触电阻并改善电极与双极板接触,但过度压缩会降低孔隙率和渗透率,导致流动阻力增加和局部传质不足,尤其在较低流量或较高电流密度下更易放大浓差极化选择兼顾低接触电阻和高渗透率的压缩率,避免单纯追求低欧姆阻抗而牺牲传质性能
流场结构-流量、电流密度[26,32-34]流场结构决定电解液分布和局部传质路径,流量决定反应物补给强度,电流密度决定反应物消耗速率。不同流场在流量-电流密度平面上的优势区间各异,低流量或高电流密度下,例如,叉指等强制对流型流场的肋下传质优势更突出,但泵耗代价增加根据目标电流密度、允许泵功选择流场结构,在相同流量或相同泵功条件下比较不同流场的适用性,最终以系统净效率作为优选判据
隔膜厚度/选择性-SOC、浓度差、电流密度[35-36,38]高质子电导率有利于降低欧姆损失,但若钒离子渗透率过高,会加剧交叉污染和容量衰减;高SOC差、浓度差和高电流密度会放大膜传质与迁移问题优化膜电导率、离子选择性和机械稳定性,并控制SOC窗口和浓度差,兼顾电压效率、库仑效率和容量保持率
), ArticleFig(id=1322941456280847345, tenantId=1146029695717560320, journalId=1322258626896822465, articleId=1322941436596978574, language=CN, label=表3, caption=

结构与运行参数协同传质优化的控制变量分析

, figureFileSmall=null, figureFileBig=null, tableContent=
协同对象控制变量分析结论工程优化方向
电极厚度-流量、电流密度[29-30,75]电极厚度增加可提高有效反应面积,但会延长反应物扩散路径。低流量或高电流密度下,过厚电极内部容易出现反应物补给不足和浓差极化;较高流量或强制穿流流场可提高厚电极利用率根据目标电流密度和供液能力确定电极厚度,在反应面积增加与传质路径延长之间寻求最优平衡
电极孔隙率/渗透率-流量[28-29,75]高孔隙率和高渗透率有利于电解液进入电极并降低压降,但可能降低单位体积反应面积;低孔隙率可增加反应界面,但在高流量下可能引起较大流阻和局部传质受限建立孔隙率、渗透率与循环流量的匹配关系,在反应面积、传质能力和泵功损耗之间进行综合优化
电极压缩率-流量、电流密度[30,54]适度压缩可降低接触电阻并改善电极与双极板接触,但过度压缩会降低孔隙率和渗透率,导致流动阻力增加和局部传质不足,尤其在较低流量或较高电流密度下更易放大浓差极化选择兼顾低接触电阻和高渗透率的压缩率,避免单纯追求低欧姆阻抗而牺牲传质性能
流场结构-流量、电流密度[26,32-34]流场结构决定电解液分布和局部传质路径,流量决定反应物补给强度,电流密度决定反应物消耗速率。不同流场在流量-电流密度平面上的优势区间各异,低流量或高电流密度下,例如,叉指等强制对流型流场的肋下传质优势更突出,但泵耗代价增加根据目标电流密度、允许泵功选择流场结构,在相同流量或相同泵功条件下比较不同流场的适用性,最终以系统净效率作为优选判据
隔膜厚度/选择性-SOC、浓度差、电流密度[35-36,38]高质子电导率有利于降低欧姆损失,但若钒离子渗透率过高,会加剧交叉污染和容量衰减;高SOC差、浓度差和高电流密度会放大膜传质与迁移问题优化膜电导率、离子选择性和机械稳定性,并控制SOC窗口和浓度差,兼顾电压效率、库仑效率和容量保持率
), ArticleFig(id=1322941456385704946, tenantId=1146029695717560320, journalId=1322258626896822465, articleId=1322941436596978574, language=EN, label=Table 4, caption=System-level mass transfer issues, performance implications and optimisation strategies, figureFileSmall=null, figureFileBig=null, tableContent=
系统级问题对传质和性能的影响优化思路
多堆并联流量分配不均[23-24,102]局部低流量电堆易出现浓差极化和容量利用率下降;过量流量电堆则增加泵耗,造成堆间性能离散优化主管/支管阻力匹配,采用对称或等阻管路布局,并增加分堆流量监测
热-流-电耦合不均[32,75,106]温度分布不均会引起黏度、扩散系数和反应速率的空间差异,也可能加速副反应、跨膜迁移和材料老化,并放大局部传质差异建立温度-流量-电流密度联动控制,保证电堆温度和SOC分布均匀
泵耗与电堆效率权衡[23,41,102]高流量可降低浓差极化,但超过临界流量后系统净效率下降以泵基效率或系统净效率为目标,避免单纯追求单电池电压提升
旁路电流[45-46]共用歧管和电解液导电通道会形成旁路电流,造成电流分布不均和副反应加剧通过歧管电阻设计、流道等阻化、分段集流和优化堆内流量分配缓解
长期沉积、污染与材料老化[27,100]杂质沉积、膜降解、孔道堵塞或电极表面官能团衰减会降低有效传质面积,并增加压降开展电解液净化、材料耐久设计、运行窗口控制和循环后传质复测
), ArticleFig(id=1322941458340250613, tenantId=1146029695717560320, journalId=1322258626896822465, articleId=1322941436596978574, language=CN, label=表4, caption=

系统级传质问题、性能影响及优化策略

, figureFileSmall=null, figureFileBig=null, tableContent=
系统级问题对传质和性能的影响优化思路
多堆并联流量分配不均[23-24,102]局部低流量电堆易出现浓差极化和容量利用率下降;过量流量电堆则增加泵耗,造成堆间性能离散优化主管/支管阻力匹配,采用对称或等阻管路布局,并增加分堆流量监测
热-流-电耦合不均[32,75,106]温度分布不均会引起黏度、扩散系数和反应速率的空间差异,也可能加速副反应、跨膜迁移和材料老化,并放大局部传质差异建立温度-流量-电流密度联动控制,保证电堆温度和SOC分布均匀
泵耗与电堆效率权衡[23,41,102]高流量可降低浓差极化,但超过临界流量后系统净效率下降以泵基效率或系统净效率为目标,避免单纯追求单电池电压提升
旁路电流[45-46]共用歧管和电解液导电通道会形成旁路电流,造成电流分布不均和副反应加剧通过歧管电阻设计、流道等阻化、分段集流和优化堆内流量分配缓解
长期沉积、污染与材料老化[27,100]杂质沉积、膜降解、孔道堵塞或电极表面官能团衰减会降低有效传质面积,并增加压降开展电解液净化、材料耐久设计、运行窗口控制和循环后传质复测
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液流电池用压滤式电化学反应器传质优化研究进展
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刘君 1, 2 , 韩治成 2 , 相艳 1, * , 卢善富 1 , 王海宁 1
北京航空航天大学学报 | 2026,52(10): 3453-3470
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北京航空航天大学学报 | 2026 , 52 (10) : 3453 -3470
液流电池用压滤式电化学反应器传质优化研究进展
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刘君1, 2, 韩治成2, 相艳1, * , 卢善富1, 王海宁1
作者信息
  • 1北京航空航天大学 能源与动力工程学院 仿生能源材料与器件北京市重点实验室,北京 100191
  • 2中国恩菲工程技术有限公司,北京 100038
通讯作者:
Research progress on mass transfer optimization of filter-press type electrochemical reactors for flow batteries
Jun LIU1, 2, Zhicheng HAN2, Yan XIANG1, * , Shanfu LU1, Haining WANG1
Affiliations
  • 1Beijing Key Laboratory of Bionic Energy Materials and Devices,School of Energy and Power Engineering,Beihang University,Beijing 100191,China
  • 2China ENFI Engineering Corporation,Beijing 100038,China
  • Corresponding Author:
出版时间: 2026-10-31 doi: 10.13700/j.bh.1001-5965.2026.0133
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压滤式电化学反应器因结构简单、模块化程度高、槽电压低等优势,成为液流电池主流反应器构型,并在储能电池、电化学水处理、合成化工等多个领域呈现出较广阔的应用前景。其中,全钒液流电池是商业化程度最高、研究体系最为成熟的代表,但其性能提升仍受限于传质效率不足所引发的浓差极化加剧、电压效率偏低及长期循环稳定性衰减等瓶颈问题,直接影响系统成本的控制。为此,主要以全钒液流电池为对象开展分析与讨论,从核心组件与运行系统2个角度,系统梳理电极、流场、隔膜等结构传质优化研究进展,分析流量、温度、电流密度、电解液浓度及罐堆比例等运行参数对传质过程的调控规律,明确各组件传质特性与电池整体性能的耦合关系,提出组件结构与系统运行协同的传质改进方向。从工程应用视角指出,全钒液流电池传质优化需在反应器组件改良的基础上,同步考量电堆尺寸放大效应、罐堆匹配、运行参数调控及系统能耗平衡,旨在为压滤式液流电池反应器的工程化设计与性能提升提供理论参考和技术参考。

压滤式电化学反应器  /  钒液流电池  /  传质优化  /  结构设计  /  运行参数

Filter-press electrochemical reactors have become the dominant reactor configuration for flow batteries owing to their simple structure, high modularity, and low cell voltage. They also show broad application potential in energy storage batteries, electrochemical water treatment, and electrosynthetic chemical processes. Among various flow battery systems, the all-vanadium redox flow battery represents the most commercially advanced and extensively studied technology. However, inadequate mass transfer continues to limit further performance development since it increases concentration polarization, reduces voltage efficiency, speeds up long-term performance degradation, and eventually raises system costs. This review focuses primarily on all-vanadium redox flow batteries and discusses mass-transfer enhancement from the perspectives of both key reactor components and system operation. Recent advances in the mass-transfer optimization of electrodes, flow fields, membranes, and other core components are systematically summarized. The effects of operating parameters, including flow rate, temperature, current density, electrolyte concentration, and tank-to-stack ratio, on mass-transfer behavior are analyzed. Based on this, coordinated optimization solutions including reactor structure and system operation are suggested, and the coupling relationship between component-level mass-transfer characteristics and total battery performance is elucidated. From an engineering perspective, mass-transfer optimization in all-vanadium redox flow batteries should not be limited to component modification alone. Instead, it should also account for stack scale-up effects, tank-stack matching, operating-parameter regulation, and the balance between electrochemical performance and system energy consumption. This review aims to provide theoretical guidance and technical references for the engineering design and performance improvement of filter-press flow battery reactors.

filter-press type electrochemical reactor  /  vanadium flow battery  /  mass transfer optimization  /  structural design  /  operating parameters
刘君, 韩治成, 相艳, 卢善富, 王海宁. 液流电池用压滤式电化学反应器传质优化研究进展. 北京航空航天大学学报, 2026 , 52 (10) : 3453 -3470 . DOI: 10.13700/j.bh.1001-5965.2026.0133
Jun LIU, Zhicheng HAN, Yan XIANG, Shanfu LU, Haining WANG. Research progress on mass transfer optimization of filter-press type electrochemical reactors for flow batteries[J]. Journal of Beijing University of Aeronautics and Astronautics, 2026 , 52 (10) : 3453 -3470 . DOI: 10.13700/j.bh.1001-5965.2026.0133
压滤式电化学反应器是由平行板极板、电极、绝缘隔板、支撑框架等单元模块化重叠,经加压密封组装而成的电化学装置[1]。该构型的反应器具备电场分布均匀、槽电压低、功率与容量可独立设计的结构优势,已广泛应用于液流电池储能[2-3]、电化学废水处理[4]、电化学合成[5]、电解水制氢[6]等领域。在当前商用液流电池领域,压滤式电化学反应器已成为主流结构[7]。例如,中国科学院大连化学物理研究所钒液流电池研究团队文献[8-10]表明,压滤式反应器作为主流的堆栈设计,已被应用于高功率钒液流电池领域,有助于实现快速的电解液流动并提升能量效率;中国石油大学徐春明团队研究的铁铬液流电池关键材料和组件也采用了压滤式反应器结构[11];北京航空航天大学相艳团队在催化电极改性[12-13]、膜改性[14]、多金属氧酸盐电解液材料[15-16]等研究中,压滤式电化学反应器均是主要的评价设备。压滤式电化学反应器赋予电池诸多特性,如循环寿命长[8]、运行安全性高[17-18]、充放电过程解耦[19]等,是液流电池实现工程化应用的核心载体。
液流电池按活性物质体系可分为全钒、铁铬、锌溴等类型,其中,钒液流电池因活性物质氧化还原可逆性好、电解液稳定性高、无跨金属离子污染等优势,成为目前唯一实现商业化应用的液流电池技术[20-21],铁铬、锌溴等液流电池则多处于实验室研究与初步示范阶段,尚未形成成熟的工程化应用体系,亟待电化学工程理论的系统性指导。钒液流电池系统主要由电堆、能量存储罐、循环泵组、管道系统、功率转换设备及能量管理系统构成。能量效率、容量保持率与循环稳定性是液流电池的核心性能指标,而传质效果通过不同物理-电化学耦合机制,对三者均产生深刻影响[22]。
传质对能量效率的影响:传质能力直接决定了浓度过电位的大小。优化的传质设计(如提高对流强度)能加速活性物质从电解液主体向电极表面的输送,有效降低浓差极化,从而提升电压效率,最终提高电池的能量效率。但需注意,过度强化传质会显著增加泵功损耗,因此,传质优化的核心在于寻求“电化学性能提升”与“系统能耗增加”之间的最佳平衡点[23-24]。
传质对容量保持率的影响:传质的空间均匀性是决定活性物质利用率的关键。不良的传质会导致电极局部出现“传质死区”(反应物供应不足的区域),使该区域活性物质无法参与反应,导致有效容量损失;同时,局部反应物耗尽会加剧析氢、活性物质不可逆沉淀等副反应,进一步加速容量衰减。因此,提升传质均匀性是保障高容量保持率的重要前提[25-26]。
传质对循环稳定性的影响:循环稳定性受多重因素制约,传质均匀性是其中关键的调控因素之一,而非唯一决定因素。具体而言,不均匀的传质会引发电极表面局部电流密度分布不均,产生热点区域,加速该处电极材料(如碳毡纤维)的氧化腐蚀和结构坍塌,同时,加剧隔膜两侧的活性物质浓度梯度,促进交叉污染。通过优化流场设计和电极结构来改善传质均匀性,可从源头上缓解这些局部衰减诱因,从而显著延长电池的循环寿命[27]。
为推动液流电池的规模化发展,亟需从反应器组件设计、运行调控和系统工程约束等层面开展针对传质优化的系统性研究,表1归纳了从多个维度进行传质优化的评价指标及其物理意义和对应的优化对象[21,24,26,28-46]。
尽管不同液流电池体系所用电解液与活性物质存在差异,但从多孔电极内反应物补给、流场均匀化、隔膜选择性传输及传质-压降-效率权衡等底层问题看,各类液流电池具有一定共通性[17-19,22]。鉴于全钒液流电池商业化程度较高、研究基础较为系统,本文以其为研究对象,对压滤式电化学反应器的传质优化策略进行归纳,同时,讨论其对其他液流电池及液流式电氧化/还原反应器的借鉴意义。
液流电池传质控制的本质是反应物由主体电解液向电极反应界面补给不足导致的浓度过电势问题,其核心解决思路为通过关键组件的结构优化提升反应物可达性,降低局部传质阻力,并改善浓度分布均匀性。本节按照“组件结构特征-传质瓶颈-优化策略-工程约束与发展方向”的逻辑展开。电极部分重点讨论孔隙率、厚度、压缩率和微观结构对有效反应面积与电解液渗透的影响;流场部分重点比较不同流道对电极对流、浓度均匀性和压降的调控作用;隔膜部分则聚焦质子选择性传输、钒离子阻隔及长期稳定性之间的平衡。
电极是钒液流电池电化学反应的核心区域,电化学反应主要发生在电极孔道电极与电解液的界面,其结构同时决定电解液浸润、活性物质扩散、电子传导和界面反应动力学。理想电极需具备亲水性优异[47]、电催化活性高[48]、界面传质能力强[49]的三重耦合特征,以实现物质/电荷传递与界面电化学反应的协同进行。目前,商用钒液流电池电极主要采用石墨毡或碳毡材料[50],但其纤维表面光滑、本征润湿性有限、活性位点不足,难以满足高电流密度下的快速反应和均匀传质的需求[48,51]。因此,电极优化主要从宏观结构调控与微观界面改性2个层面展开。宏观层面聚焦于碳基毡的孔隙率、厚度、孔径尺寸及压缩率,微观层面则通过表面修饰、构建纳米级孔道与活性位点阵列[52-53],强化电极与电解液的界面作用及离子传输能力。
电极组装压缩率是宏观结构优化的重要考量因素,适量的压缩率可降低电极与隔膜、集流体之间的接触电阻,提升传质效率,但过度压缩会降低电解液的渗透率,增加传质阻力,同时,导致电池压降上升[54]。因此,电极优化结构不能单纯追求低接触电阻或高比表面积,而应在厚度、孔隙率与组装压缩率之间建立平衡,实现接触电阻与传质阻力的协同降低[30]。孔隙率与厚度直接影响电极内部液相渗透、有效反应深度和电流密度分布,是决定多孔电极传质性能的核心宏观参数。
Alphonse等[55]研究了孔隙率沿厚度方向变化对电池性能的影响,当电极孔隙率沿厚度方向在64%~94%范围内变化时,孔隙率下降会导致电流密度分布不均并呈阶梯式降低,电池电压随之下降;当孔隙率低于64%时,电极渗透性急剧变差,传质阻力大幅增加,电池电压出现骤降。高孔隙率电极可形成厚电极层,允许更多电解液渗透,有效增强传质过程,提升电池电压。Yaji等[56]通过数值模拟与拓扑优化方法,研究了蛇形流道下电极厚度与孔隙率的耦合影响,确定钒液流电池电极的最佳厚度为3 mm、最佳孔隙率为90%。香港科技大学He等[57]通过三维数值模拟揭示了全钒液流电池电极孔隙率、纤维直径与流场的耦合优化机制,提出梯度孔隙率设计(膜侧低、流场侧高)及大纤维直径配合表面改性的策略,可同时降低浓差极化与压降,显著提升大尺度电池性能。高孔隙率(95%)可最小化浓差极化,提升大尺度电池孔隙率(80%以上)可解决反应集中在流场侧分布不均的问题,大纤维直径与高比表面积改性可以同时提高渗透率和降低活化损失。Ali等[58]通过建立二维等温物理模型,推导了电极比表面积和渗透率与孔隙率及纤维直径的物理关联式,系统分析表明,当孔隙率控制在0.8~0.92且纤维直径为40~70 μm时,可在降低泵送能耗的同时,有效抑制电化学过电位。Martinez Lopez等[59]通过二维数值模型揭示了电极压缩比(20%~50%)和电解液流量(10~40 mL/min)对全钒液流电池性能的影响规律,50%压缩比使反应速率提升9.2%、流速提升12.7%,但过电位增加;低流量(10 mL/min)虽增强浓度梯度,但导致过电位升高,需权衡优化。
梯度化电极与定向排布电极为解决“反应面积与传质阻力”矛盾提供了新的结构思路。南方科技大学赵天寿团队[28]研究发现,梯度化电极可使孔隙率与渗透性能由隔膜侧向流道侧逐步提升,从而增强活性物质从流道区域向膜侧界面的输运;同时,比表面积由流道侧向隔膜侧逐渐增大,可保障核心反应区域拥有充足的活性位点。Sun等[60]通过定向排布碳纤维降低电极曲折度、缩短离子迁移路径,并强化垂直膜面方向和肋下区域的对流补给,使电流密度分布更加均匀。由此可见,电极厚度、梯度孔结构、孔隙率和纤维曲折度的最优值并非固定常数,而是随流场形式、流量、电流密度和温度等运行条件变化的结构-运行耦合结果。微观界面改性的核心目标是在不显著增加流动阻力的前提下,提高电极与电解液界面可及性、润湿性和局部反应活性。微米级通道有利于电解液对流渗透,纳米级孔道则为离子提供短程快速扩散路径并增加反应界面。同时,含氧/含氮官能团[61]、碳纳米结构或金属氧化物[62]等改性可改善界面电子结构和反应动力学。微纳结构改性并不等同于单纯增加活性位点,其工程价值在于同时提升界面反应速率、反应物补给能力和结构稳定性。另外,电极材料在长期循环中,表面含氧/含氮官能团可能发生脱落或重构,微纳结构可能出现堵塞、塌陷或机械损伤,从而降低电解液浸润性和反应界面可及性。因此,电极结构设计应兼顾高比表面积、快速传质与结构耐久性,避免仅追求初始活性而牺牲长期稳定性。天津大学Wang等[31]通过酚醛树脂涂层与聚乙二醇造孔刻蚀策略,精准调控热氧化刻蚀过程制备微纳米分级多孔石墨毡电极,改性后的电极具有更高的开路孔隙率、吸水率与压缩率,不仅有利于电解液渗透并到达反应界面,还能提升电极柔韧性,减少对隔膜的机械损坏;该电极在200 mA/cm2高电流密度下的能量效率达80.41%,经1000次循环后,容量保持率仍在90%以上,从而实现双重功能结构,如图1所示。
压滤式液流电池的流道作为极板上电解液的传输与分配的主要通道,表征流场对电极内反应物补给均匀性、局部贫液区形成和反应分布一致性的调控能力。目前,全钒液流电池的主流流道类型包括平行流道、叉指流道、蛇形流道及多种异形流道。平行流道压降低,但电解液难以渗透进入电极内部,易造成传质不均;蛇形流道可形成较强肋下对流,但压降较高;叉指流道可强化穿流传质但依赖电极渗透率;多场协同、仿生和人工智能(artificial intelligence,AI)优化流道则试图在传质均匀性、压降和可制造性之间取得综合平衡[26,63]。从传质机理看,流场优化主要通过3条路径发挥作用:①改善入口至出口方向的流量分配,降低局部低浓度区;②增强肋下或电极厚度方向的对流渗透,缩短活性物质到达反应界面的路径;③在提高传质的同时,控制压降和循环泵功。因此,流场优劣不能脱离电极厚度、孔隙率、流量、电流密度和目标系统效率进行判断。
传统蛇形流道是应用较广的平流流道类型,其优势在于长流道和相邻通道压差可诱导肋下横向渗透,从而增强局部反应物补给;但其不足也较突出,即肋下对流分布不均。弯道附近可能因压力梯度不足形成传质死区,而非弯道连接区域又可能因较大横向压差形成局部过反应,导致反应速率热点与低反应区并存,影响钒液流电池电压效率。米兰理工大学Messaggi等[32]通过三维计算流体动力学(computational fluid dynamics,CFD)模型与实验验证揭示了蛇形流场(serpentine flow field,SFF)肋下区域的旁路对流机制,明确了流场设计、电极形貌与电化学性能之间的强耦合关系,为蛇形流道的局部强化设计提供了理论依据。
针对蛇形流道的缺陷,目前的优化思路主要为通过流道形状、流道变径、设置堵块等方式重构电极内的压力分布,平衡肋下流动压力梯度,增强电解液的横向渗透与分布均匀性。北京化工大学Wang等[64]通过三维数值模型系统对比了半圆形、矩形和三角形流道截面设计,发现半圆形流道凭借更高的雷诺数和优异的水动力学特性,显著增强了电解液渗透与活性物质分布均匀性(浓度均匀性提升15.4%),从而有效降低过电位,实现最低充电电压和最高放电电压。Lu等[65]提出旋转SFF的创新设计,通过旋转变径的流道布局,强制电解液在电极厚度方向与横向实现深度渗透,该流场在低流速(2 mL/s)下的压损介于传统SFF与叉指流场之间,实际能效比传统SFF提升4.2%~12.6%,兼具SFF低压降与叉指流场强制对流的双重优势。Karami等[66]通过降低通道高度与在低压力梯度区域设置全堵塞阵列优化蛇形流道,在弯道处引入100%高度堵塞块、中点处设置80%堵塞块,有效增强了肋下对流强度,使电极中平面流速均匀性指数从0.68提升至0.802,电池净功率密度提升56.24%(达276.3 mW/cm2),如图2所示。SFF的传质效率依赖电解液在肋下的深度渗透,其性能对电极厚度具有较高敏感性,设计时需实现流道结构与电极厚度的匹配[67]。香港科技大学赵天寿团队提出了一种沿流路梯度设计的SFF[68],通过将流道深度从入口到出口线性减小(优化梯度为25%)来加快流速并增强下游对流传质,从而显著改善全钒液流电池的反应物分布均匀性,使能量效率和电解液利用率分别提升5.0%和27.7%。天津大学Wang等[33]通过三维多物理场耦合模型阐明了旋转SFF几何参数(通道分数为0.25、深度为1 mm)对肋下对流的调控机制,使钒液流电池在150 mA/cm2和40 mL/min条件下达到91.4%的泵基效率,为高功率密度流场设计提供了理论指导。蛇形流道对于高流速工况及厚电极结构展现出独特的适配性[21,30],这是因为电解液主要通过扩散和少量渗透进入电极,由于厚电极自身的结构特性,并不需要电解液以强制对流的方式深度穿透电极来完成反应,蛇形流道的长且曲折的路径设计能够很好地适应这一需求。蛇形流道在工程层面主要约束来自面积放大后带来的局部热点与死区增多、压降大及泵耗高等问题。
由图2可见,堵塞阵列并非简单增加流动阻力,而是通过在低压力梯度区域重构局部流线,使原本集中于主流道附近的电解液向肋下区域渗透,从而改善电极中面速度分布和负极端电流密度分布。该结果说明,SFF的优化重点不仅是延长流道或提高流量,而是在局部传质薄弱区域建立适度的横向压力梯度,使热点区和死区趋于均衡。
叉指流道的结构特征为进出口不直接相连,电解液经分流流道后需穿透电极才能汇流流出,是典型的穿流流道类型,该结构可增强厚度方向对流传质,尤其在低流量、高电流密度或薄电极条件下有助于缓解浓差极化,但其效果并非必然优于蛇形流道,而是取决于电极厚度、孔隙率、渗透率、压缩率和流量分配。若中部区域供液不足,局部反应速率仍可能降低[63]。Ishitobi等[69]搭建了二维稳态全电池模型,实现叉指流道与0.2 mm薄碳纸电极耦合的跨平面方向可视化,并提出通过实验数据拟合边界层传质系数关联式,为叉指流道与薄电极的匹配设计提供了方法。相较于蛇形流道,叉指流道的系统压降更低,从工程化系统角度,其能更好地实现泵功与电解液分布均匀性的平衡,更适合工业级钒液流电池的应用。
针对叉指流道中部传质薄弱的问题,优化方向主要为通过流道结构重构提升中部区域的流量与对流强度,在不增大压降的前提下强化中部区域反应物补给。吉林大学杨帆[70]设计多组并联叉指流道,通过增加流道并联数量,有效改善了传统叉指流道电极中部低浓度区域大面积聚集的问题,使活性物质低浓度区域仅出现在分支出口流道单侧的肋下电极,且随着并联数量增加,低浓度区域更分散,浓度梯度更低;研究还发现,并联组数越多,系统压降越小,当并联四组时,${\mathrm{VO}}_2^+ $平均浓度与分布均匀因子趋于平衡,实现传质效率与压降的最优匹配,如图3所示。并联交指结构通过分散入口与出口支路,削弱了传统交指流场中部低浓度区的大面积集聚,使${\mathrm{VO}}_2^+ $浓度分布更加均匀;同时,多并联支路缩短了单支路流动路径,有利于降低水力压降。该结果表明,叉指流场的优化应重点关注分支数量、支路长度和出口布置对局部穿流强度的影响,以在强制对流和泵功之间取得平衡。香港科技大学赵天寿团队提出了一种分叉交指流场设计[71],通过分级分流策略将电解液均匀分配至分支通道,使钒氧化还原液流电池压降降低45%、泵基电压效率提升至73.10%(250 mA/cm2时),且随活性面积增大优势更显著,展现出优异的规模化应用潜力。
多场协同流场的设计思想来源于场协同原理,其核心不是单纯提高流速,而是改善速度场、浓度场、压力场之间的匹配关系,实现传质增强与压力损失降低的协同[34]。对于反应物消耗导致的浓度梯度,电解液速度方向应尽可能指向低浓度反应区,即与数学意义上的浓度梯度方向趋于相反,或与扩散通量方向趋于一致,以增强活性物质补给,并改善浓度分布均匀性;同时,速度方向应尽可能沿压力下降方向流动,使压力能更多用于有效输运,减少局部回流、滞流和无效压降。因而,多场协同流道的核心目标是在提高速度-浓度协同程度的同时,降低无效流动阻力,实现传质强化与泵功降低的协同优化。
北京理工大学Cheng等[34]设计的导流单通道的速度-浓度协同角比传统流道提升2.7°,速度-压力协同角仅损失0.11°,系统压力损失降低11.73%,电极内V2+浓度提升32.34%;该设计在实现速度-浓度协同提升(+1°~5°)的同时,几乎不损害速度-压力协同(−0.05°~0.08°),实现了“降损增效”的优化目标,如图4所示。多场协同的设计思路也被应用于平行流道优化,如通过设计波纹流道调控电解液的流动速度、压力与流动角度,实现平行流道的传质强化[26]。多场协同流场适合指导流场设计,但工程化落地必须经过“结构简化、可制造性验证、压降/泵功核算、大面积电池验证和电堆级验证”。
针对传统流道局部浓度梯度大、浓差极化严重、电池效率与稳定性偏低的问题,研究者突破蛇形、叉指、平行流道的基本框架,提出仿生[67]、双螺旋[72]、AI拓扑优化[63]等异形流场。该类流场的共同目标是通过分级分流、曲线导流或算法筛选,提高电解液覆盖率,降低局部贫液区,并优化压降分布。仿生流场借鉴植物叶脉等天然输运网络,利用主干-分支通道实现多尺度分配;AI优化流场则通过高通量生成、性能预测和实验筛选提高设计效率。
Huang等[67]借鉴植物叶脉的营养输送机制,设计了主通道添加圆形障碍物的仿生叶脉流场,仿生叶脉通过主干-分支通道模拟植物叶脉分级输运,使电解液更充分地覆盖电极表面和出口区域;主通道圆形障碍物进一步诱导电解液进入分支流道,显著提升了电解液在电极表面的分布均匀性,减少局部浓度贫化。研究表明,该仿生叶脉流场的能量效率最高,极化损失最小,电极内V2+平均浓度高于传统SFF,尤其在电极出口区域的浓度分布更均匀,如图5所示。仿生流场的优势主要体现在分布均匀性和低浓差极化,而其工程应用仍需关注加工复杂度、密封可靠性和大面积放大时的流量一致性。
AI驱动设计是近年来异形流场开发手段的前沿研究范式,可有效突破人工设计的局限性,实现流场结构的高通量筛选与优化,提高液流电池性能。中国石油大学徐春明院士团队提出了融合梯度提升机器学习与专用大语言模型的液流电池AI驱动设计方法,通过数据-机理双驱动建模实现了铁铬液流电池性能的精准预测、关键影响因素识别与智能优化[73-76]。香港城市大学Zheng等[63]开展钒液流电池流场的端到端AI驱动设计,构建流场库生成算法与误差<1.5%的卷积神经网络(convolutional neural network,CNN)性能预测器,通过算法探索了11564种异形流场结构,从中筛选出8种最优结构。其中,HTS01为第一轮筛选得分最高且专家投票排序最高的代表流场,可视为该研究中的综合最优候选结构。实验验证表明,HTS01在50~200 mA/cm2 范围内均表现出高于传统SFF和叉指流场的能量效率,其优势主要来自更强的肋下对流、更高的反应物分布均匀性和更低的浓差极化。同时,HTS04在电解液利用率方面表现突出,在100 mA/cm2下电解液利用率达到78.3%,较传统SFF提高10.8%。因此,该研究表明,AI筛选流场的优化目标并非单纯提高流速,而是在传质均匀性、压降和电解液利用率之间实现综合权衡。如图6所示。AI驱动设计的优势在于将“结构生成-多物理场仿真-性能预测-实验验证”连接为闭环,可在大量候选流场中筛选兼具高极限电流密度、较高能量效率和较低压降的结构。该方法尤其适用于传统经验设计难以覆盖的异形流场空间,但其预测可靠性仍依赖训练数据质量、边界条件一致性和后续实验验证。
不同流道结构在不同电极和运行状态下有不同优势,当前研究多为单独优化流道或电极,极少研究将流道与多孔电极耦合进行协同。电极-流场耦合机制体现为多孔电极孔径分布、孔隙率、各向异性和压缩状态与流场几何结构、肋宽比、流动方向之间的相互制约,两者共同决定电解液分布、肋下传质、局部反应速率和压降。未来流场优化应从单独改变流道形状转向“流场-电极-流量-电流密度”的协同设计。
基于表2的对比结果,流场优化不能仅以局部传质增强程度作为唯一判据,而须在传质强化、压降损失、泵送能耗、可制造性及工况适应性之间进行综合权衡。从表2可看出:平行流场虽压降最低、泵耗最小,但肋下与远端区域传质不足,适用于对泵耗敏感但功率密度要求不高的场景;SFF传质能力最强,却以显著泵送损耗为代价,适宜追求高功率密度的流经型设计;叉指流场通过强制穿透电极实现传质增强,但对电极渗透率高度敏感,其压降特性随电极压缩率和厚度变化显著;多场协同与仿生优化流场则在均匀性与压降之间展现出较好的平衡潜力,但结构复杂度提升对加工精度和放大一致性提出更高要求。因此,对于工程化电堆,较优方案通常并非传质最强或压降最低的单一极端结构,而是在目标电流密度与允许泵耗约束下,实现浓度均匀性、压降水平与电极利用率综合最优的流场-电极耦合设计。
隔膜是全钒液流电池的核心功能组件,其作用是实现正负极电解液中质子的快速选择性传输,同时,抑制钒离子跨膜渗透与串液。理想隔膜应在高质子电导率、低钒离子渗透率、良好化学稳定性、机械强度和较低成本之间取得平衡[77]。对于工程化应用,隔膜不仅影响欧姆阻抗和库仑效率,还会通过跨膜迁移、水迁移和长期降解影响容量保持率与系统寿命。
在钒液流电池充放电过程中,正负极钒离子的透膜迁移会导致电解液交叉污染,不仅降低电池库仑效率与容量,还可能引发正负极短路,是电池性能衰减的重要原因。目前,商用钒液流电池所采用的隔膜仍以全氟磺酸质子交换膜为主[78],其质子传导性与化学稳定性优异,但存在成本高、钒离子渗透性较高的缺陷;磺化聚醚醚酮膜[79]、磺化聚醚砜膜[80]、磺化聚酰亚胺膜[81]及多孔纳滤膜等新型隔膜虽在成本或离子选择性上具有优势,但在化学稳定性、质子传导性或机械强度等方面仍存在不足,难以满足工程化应用的要求。
隔膜的质子传质过程主要依赖亲水膨胀后形成的质子传输通道,其质子传导机制主要包括Grotthus传输[82]、Vehicular传输[83]与表面传输[84]3种:Grotthus传输是质子通过结构扩散实现的快速传输;Vehicular传输是质子以H5O2+、H9O4+等水合离子为载体,在隔膜通道内的对流扩散传输;表面传输是质子与阴离子结合后,在隔膜亲水通道壁(如含磺酸基树脂的−SO3−基团)上的界面传输。在含水量较高的体系中,Grotthuss传输与Vehicular传输是质子传导的主要方式。
隔膜传质优化的核心是构建高选择性、高传导性的质子传输通道,在保证钒离子低渗透率的前提下,提升质子传导效率[35,85]。目前的研究主要围绕膜材料的化学结构设计、亲水/疏水微相分离、复合填料、离子筛分层和多孔结构调控展开。通过上述方法实现隔膜质子传导能力与离子选择透过性的双重提升,满足高电流密度下的液流电池传质需求[36,86-87]。高质子电导率与高离子选择性往往存在权衡:过度提高亲水通道连通性可能增加钒离子渗透,而过度增强阻隔能力又可能提高膜阻。而且隔膜在长期氧化和溶胀过程中可能出现质子通道结构变化、钒离子渗透增加或机械强度下降,从而降低库仑效率和容量保持率[27]。因此,隔膜设计应兼顾电压效率、库仑效率、容量保持率和长期化学/机械稳定性。
中国科学院大连化学物理研究所Zhai等[88]通过磺化UiO-66-NH2与磺化聚醚醚酮膜复合,构建连续质子通道并作为钒离子屏障,实现质子传导率提升63%、钒渗透率降低83%,显著提高钒液流电池性能。Aziz等[86]通过在Nafion掺杂TiZrO4纳米管形成超高选择性通道,质子传导率达75.9 mS/cm,H+/VO2+选择性提升23倍,电池能量效率达83.9%、循环耐久性优秀。还可以通过增强尺寸筛选与选择性来制备多孔膜。中国科学院大连化学物理研究所Zhou等[89]定制多孔聚苯并咪唑膜,通过高效质子通道和多重阻挡系统,实现高质子传导与强钒离子阻挡,适用于高倍率钒液流电池;并通过Nafion/聚偏氟乙烯双孔结构膜调控微/宏孔分布,质子传导率为49.1 mS/cm,钒渗透显著抑制,电池库仑效率为96.1%、能量效率为83.8%[37]。还有一些其他策略,如设置层状交联结构,日本国立材料科学研究所Sha’rani等[90]通过在Nafion表面层组装聚乙烯亚胺与氧化石墨烯,实现质子传导与钒阻挡的优异平衡,提升电池整体性能。
全钒液流电池的传质过程不仅受电极、隔膜、流道等核心组件结构的固有特性影响。也与流量、温度、电流密度、电解液浓度及罐堆比例等运行参数密切相关。与结构参数相比,运行参数具有在线调节性,能够改变电解液物性、反应物补给速率、活性物质消耗速率和系统能耗。可通过调控电解液流动特性、离子扩散速率与电化学反应速率,直接影响电池内部的传质效率与浓差极化程度[76]。从工程化应用视角,传质优化并非单一的结构改良,而是需要根据组件结构特性设计适配的运行参数,实现结构与运行的协同调控,在强化传质的同时,降低系统能耗,提升电池整体性能。本节系统分析各关键运行参数对钒液流电池传质过程的影响规律与调控策略。
电解液流量是调控液流电池传质过程的核心运行参数,直接影响电极表面的电解液更新速率、主体液相与反应界面的浓度差及局部浓差极化程度。文献[29,91]发现,在膜电极组件、流场结构及工作电流密度保持不变的前提下,钒液流电池通常表现出明显的临界流速特性。当电解液流速低于该临界值时,提高流速能够显著强化电解液在电极区域内的更新与补给,有效缓解电极界面的浓差极化现象,使充电过程电压降低,放电过程电压提升,进而显著改善电池效率。而当流速超过临界值后,电极表面活性物质浓度已趋于稳定饱和,电池电压曲线基本重合,此时,继续提高流速对电池整体性能的改善作用不再明显。Toja等[25]通过CFD模拟和实验揭示了电解液速度均匀性对钒液流电池流场放大的关键作用,通过优化通道几何设计出“增强均匀性流场”,将电极内速度异质性指数从19.0%降至3.2%,使电流密度提升49%(达654 mA/cm2),并在完整电池中使能量效率提升4.1%和电解液利用率提升10.4%。
从系统能效角度看,电解液流量提高通常伴随压降和泵功增加。当流速超过临界值后,继续提升流速会导致循环泵功大幅增加,而电池性能无明显改善,最终造成系统净效率降低。此外,流速还会影响电解液的跨膜渗透与钒离子扩散:低流速可减少钒离子跨膜扩散导致的电解液体积损失,但浓差过电位显著增大;高流速虽能降低浓差过电位,但会加速电解液的透膜渗透。因此,电解液流量的优化需进行多目标调控,纽约州立大学Khaki 等[92]建立了流速与电池容量/电压损失的显式数学关系,揭示了电解液黏度差是膜渗透的关键驱动因素,为流量的精准调控提供了理论模型。从流场与流量的匹配角度,低流量工况下,电解液主要依靠扩散传输,电极厚度方向分布不均,流场的传质强化作用有限;高流量工况下,需要流场的导流作用增强对流,实现电解液在电极内的均匀分布,提升电池极限电流密度[74]。澳大利亚西澳大学Wang等[93]提出一种非对称变流量控制策略,基于达西定律和SOC-黏度关联模型动态优化正负极流量比,实验验证表明,该策略可显著抑制钒氧化还原液流电池的电解液迁移(84.48%),提升放电容量(13.77%),并减缓容量衰减(6.42%),有效兼顾了系统效率与长期容量保持率。
钒液流电池的运行温度易受季节、地域及实际运行工况的影响,可通过改变离子扩散速率、电解液黏度、电极反应动力学及隔膜传质特性,从多维度影响电池内部的传质过程与整体电化学性能。清华大学Xi等[94]研究发现,在−20~50 ℃的宽温度范围内,钒液流电池的库仑效率与电压效率呈现相反的温度变化趋势:库仑效率随温度升高而降低,主要原因是温度升高会加剧钒离子的跨膜扩散,增加电荷损失;电压效率随温度升高而增加,核心是因为温度升高可显著降低电解液的欧姆电阻与电极的极化电阻,提升离子传质与电化学反应效率。
温度对电池内阻的调控具有明显的阶段性特征:低温条件下,极化电阻占内阻主导地位,是制约电池性能的核心因素;高温条件下,欧姆电阻与极化电阻共同控制电池性能[95]。研究发现,钒液流电池极化电阻和欧姆电阻与温度呈负相关,在低温下,极化电阻和活化能显著增加,导致容量利用率下降,高温条件下,交叉污染和极化加剧[96]。基于温度对传质与反应的影响规律,钒液流电池的温度适配运行策略为:低温工况下,采用低电流密度运行,减少极化电阻引发的浓差极化与电压损失;高温工况下,需同步增强电流密度与流场传质的协同,在提升反应速率的同时,通过流场强化电解液对流,抑制高温下的钒离子跨膜扩散[97]。
电解液浓度是决定钒液流电池能量密度的核心参数,同时,对传质过程与电化学反应具有显著调控作用。随着钒电解液浓度升高,电极表面的活性离子供给量增加,反应过程中的浓差极化与欧姆损耗降低,电池电压显著提升[98-99]。但电解液浓度的提升也存在固有瓶颈,正负极的传质与反应限制成为主要制约因素,负极的动力学限制源于V2+/V3+电对的电子转移速率慢,导致高过电位;正极的传质限制则因${\mathrm{VO}}_2^+ $/VO2+电对在碳基毡电极空隙中的扩散阻力大,尤其在高电流密度与电极出口区域,易出现反应物耗竭,引发严重的浓差极化。
液流电池向高能量密度发展的必然趋势是提升电解液浓度,但浓度升高会导致电解液黏度增加,还有可能在运行过程中析出固相[100],影响电池容量,是进一步开展研究的方向。不同价态的钒在运行条件下会存在固态析出的条件,影响电池容量。麻省理工学院Barton 等[39]通过实验独立调控电解液黏度,建立了Sherwood数、Peclet数、Schmidt数的普适关联式,实现了从材料物性到电池性能的定量预测。该研究系统解耦了黏度对传质、欧姆、动力学过程的独立影响,建立了黏度-传质-性能的定量关系,发现当电解液黏度从1.5 mPa·s增至4.6 mPa·s时,传质系数下降30%~40%,为高浓度电解液的传质优化提供了核心理论依据。
电流密度是钒液流电池运行过程中重要的电化学工况参数,其本质上反映单位电极面积上的反应强度和活性物质消耗速率[21,40]。与流量、温度和电解液浓度等主要影响反应物供给能力的参数不同,电流密度更多体现为传质需求端的驱动变量——其升高意味着单位时间内电极反应界面对活性物质的消耗速率增加,若电解液流量、流场分布和电极孔道传输能力不能同步匹配,则电极局部区域容易出现反应物贫化,导致浓差极化增大、放电电压降低、充电电压升高,最终降低电压效率和能量效率[40,98,101]。可见,电流密度的可调范围受限于“传质供给端”的实际能力,两者构成运行优化的基本矛盾,电流密度不宜孤立优化,而应与流量、SOC、电解液浓度、温度及电极/流场结构协同匹配。在较低电流密度下,传质限制通常不明显,过高流量带来的性能增益有限;而在高电流密度下,反应物消耗速率增加,流量不足或局部流动不均会迅速放大传质限制[24,41]。以上表明,液流电池运行优化的关键不是单纯提高或降低电流密度,而是在目标功率密度、浓差极化、泵功损失和系统能量效率之间确定合理的电流密度-流量匹配区间[24]。这本质上是一个“运行窗口寻优”问题。
进一步地,电流密度调控还需要考虑充放电过程中的传质差异。Kim等[40]通过比较多孔电极不同区域的电位分布,对液流电池运行过程中的局部传质状态进行了表征。研究表明,在充电初始低SOC阶段,电极不同区域之间的电位偏差较大,说明局部反应物补给和电极内传质状态尚不均匀。此时,若直接采用较高电流密度,容易放大局部浓差极化,并可能增加析氢、析氧等副反应风险。因此,在充电初期可适当降低电流密度,待电解液物性和电极内传质过程趋于稳定后,再逐步提高电流密度。相比之下,放电过程中的局部电位分布整体更均匀,但其对电流密度变化更为敏感。在放电过程中,当电流密度加倍时,电极不同区域之间的电压偏差增加161.7%,说明高电流密度会迅速放大反应物消耗速率与传质补给能力之间的不匹配。因此,放电过程应根据SOC、流量和电极/流场结构确定合理负载,使电流密度低于传质允许范围,避免浓差极化加剧和电压效率下降。
液流电池传质优化受多重因素耦合控制,并非单一结构参数或运行参数所能独立决定。这些因素涵盖电极结构(厚度、孔隙率、渗透率、压缩率)、流场构型、隔膜特性(厚度、选择性),及流量、电流密度、SOC窗口、电解液浓度等运行条件[19,22,75],如表3所示。其中,电极厚度、孔隙率、渗透率和压缩率决定了电解液进入多孔电极的难易程度、有效反应面积和局部传质路径[25-26,32-33,68];流场结构决定电解液在电极表面的分配方式、肋下对流强度和局部贫液区域;隔膜厚度与选择性则影响质子传导、钒离子迁移和容量衰减[35-37,87]。与此同时,流量决定反应物补给速率,电流密度决定反应物消耗速率,SOC和浓度差影响主体浓度、浓度梯度和跨膜迁移驱动力[21,24,39-41]。因此,结构参数的最优值并不是固定不变的,而是随运行流量、电流密度、SOC区间和系统压降约束发生变化[33,39,75,95,97]。若仅优化电极或流场结构,而不考虑运行条件匹配,可能出现局部反应物补给不足、浓差极化加剧、压降升高或泵功损失增加等问题[23-24,102]。
从控制变量角度看,结构与运行参数协同传质优化的核心在于建立“结构供给能力-运行传质需求-系统能耗约束”之间的匹配关系[21-22,24,41,75]。对于电极结构,应在有效反应面积、传质路径长度、孔道渗透能力和接触电阻之间取得平衡,并根据目标电流密度和循环流量确定合适的厚度、孔隙率和压缩率[29-30,54,75];对于流场结构,应结合流量和电流密度评价其反应物分配能力、浓度均匀性、压降和泵功代价[26,32-34],而不能仅在单一流量条件下比较流场优劣;对于隔膜结构,则需在质子电导率、离子选择性、机械稳定性和SOC运行窗口之间优化[35-37,79,87]。由此可见,液流电池传质优化应从单一组件改进转向电极-流场-隔膜-运行参数的系统协同设计,以实现高电流密度下低浓差极化、低泵功损失、高电解液利用率和长循环稳定运行的综合目标[27,42-43,93]。
罐堆比例(储液罐与电堆内电解液的体积比)通过影响电解液不同SOC的活性物质浓度分布,间接影响钒液流电池的传质过程与电池容量。在充放电过程中,储液罐与电堆内的电解液中不同SOC的活性物质浓度会持续变化并产生差异,这种浓度差并非由电压损失或电流损失引发,而是源于储罐中的电解液未及时输入电堆、活性物质未被充分利用,直接造成电池的可用容量损失;同时,储液罐内部的电解液混合损失会进一步降低活性物质利用率与系统效率[103]。
罐堆之间的活性物质浓度差与电流密度密切相关,电流密度越高,浓度差越显著[104]:当电流密度为10 mA/cm2时,正极储罐与电堆的四价钒离子浓度几乎无差异;当电流密度升至60 mA/cm2时,两者的浓度差明显增大。罐堆比例直接影响电解液利用率,伊利诺伊大学Nemani等的研究[105]表明,当罐堆体积比为1时,电解液利用率仅为60%;当体积比提升至20时,电解液利用率可达84%。目前,提升电解液利用率的方法除了优化罐堆比例外,还可通过储液罐的非混合型设计、基于传质特性的动态电流优化调控等方式,减少罐堆之间的浓度差与混合损失。
在大规模钒液流储能系统中,多个电堆通常通过管路并联或串并联运行,传质问题由单电池内部扩展为“管路-电堆-电解液储罐”的系统级分配问题。如表4所示,多堆并联时,各支路的管路阻力、堆内压降和温度状态(温度影响电解液黏度)若不一致,会导致电解液流量分配不均,使部分电堆处于低流量工况,加剧浓差极化[44,106-107]。同时,温度分布不均会改变电解液黏度、扩散系数和反应速率,进一步放大热-流-电多场耦合效应的空间差异[44,106]。
旁路电流是压滤式电堆系统中需要关注的另一类耦合问题[45-46]。其主要来源于相邻单电池或电堆之间通过共用歧管或电解液通道形成的离子导电路径,直接后果是有效工作电流降低、局部电流分布偏离设计值,并可能诱发局部副反应和传质负荷不均。
值得指出的是,上述系统级问题的解决通常是以增加泵送损耗为代价。高流量虽然能够改善传质并降低浓差极化,但会增加压降和泵功,因此,实际运行中通常需要以系统净效率或泵基效率为目标,在传质强化与能耗代价之间进行综合权衡,确定最优流量区间[41,102]。
本文从工程化应用视角系统综述了压滤式电化学反应器在钒液流电池中的传质优化研究进展,围绕电极结构、流场结构、隔膜传质、运行参数调控、结构-运行参数协同及系统级工程约束进行了归纳整理。在此基础上,进一步阐明了不同组件传质特性和系统设计与电池效率、容量利用率和长期稳定性之间的耦合关系,形成以下主要认识:
1) 电极传质优化需实现宏观结构与微观改性的协同。宏观层面需在孔隙率、厚度、组装压缩率之间建立平衡,微观层面通过构建微纳米分级多孔结构、表面官能团、活性位点构筑提高润湿性、反应界面可及性和界面反应速率,从而降低浓差极化,并提高电极利用率。
2) 流场优化的核心是在电极内浓度分布均匀性、肋下对流强度和系统压降之间的综合权衡。目前,已从传统流道的局部改进(变径、堵块、并联)向多场协同设计、仿生设计及AI驱动的异形流场设计发展,但工程应用仍需关注压降控制、泵功、加工复杂度和大面积放大效应等实际问题。
3) 隔膜传质优化的关键是构建高选择性、高传导性且稳定的离子传输通道。在保证钒离子低渗透率的前提下提升质子传导效率,可同时改善库仑效率、电压效率和容量保持率;但膜材料设计仍需兼顾化学稳定性、机械强度、长期运行条件下的结构稳定性。
4) 运行参数对传质过程具有显著调控作用。流量决定反应物补给速率,电流密度决定反应物消耗速率,温度和浓度改变电解液物性与反应动力学,SOC影响主体浓度和跨膜迁移驱动力。因此,运行优化应从单一参数调节转向流量-电流密度-SOC-温度-浓度的协同控制,在降低浓差极化的同时,控制泵功损失。
5) 工程化传质优化需由单电池尺度拓展至电堆和系统尺度。多堆并联流量分配、热-流-电耦合、旁路电流、罐堆混合、泵耗与效率权衡及长循环材料衰减均会改变电堆局部传质状态和系统净效率,因此,需要建立面向电堆一致性、系统效率和寿命稳定性的多目标优化方法。
从全钒液流电池相关研究中总结出的相关方法(如流场均匀化、电极孔结构调控、传质-压降协同优化、传质-反应动力学匹配及膜传质路径设计等)可为其他液流电池体系提供反应器设计开发思路。其他液流电池在具体应用时,应结合不同体系的活性物质物化性质、反应动力学、副反应、沉积/络合行为和膜选择性要求进行适配。液流电池用压滤式电化学反应器的传质优化是一项系统工程,未来研究与工程化应用可重点从以下方面展开:
1) 开展多组件协同的传质优化研究。突破单一组件优化的局限性,建立电极、流场和隔膜之间的结构匹配设计方法,考虑孔结构、流场分配、界面反应和膜传输之间的耦合效应,构建多组件协同的传质强化体系。
2) 强化工程化系统集成考量。传质优化需在提升电池性能的基础上,同步兼顾电堆紧凑性、罐堆匹配性、循环泵功、热管理和旁路电流控制等系统因素,建立“性能-能耗-体积-寿命”的多目标优化模型。
3) 推动低成本、高稳定性的传质优化技术研发。针对高端碳基电极、全氟磺酸膜和复杂异形流场成本较高的问题,应开发低成本电极改性方法、非氟或低氟高选择性膜材料及易加工、低压降、适合放大的高效流场结构。
4) 深化多物理场耦合的传质理论研究。结合CFD、电化学动力学、分子模拟和数据驱动方法,揭示微纳界面传质、多孔电极内对流-扩散-反应耦合及电堆尺度热-流-电耦合规律,为结构设计和运行控制提供定量依据。
5) 建立液流电池传质优化的标准化评价体系。制定涵盖传质效率、浓差极化、能耗损失、成本效益的综合评价框架,为不同优化方案的对比与工程化选型提供依据。
从储能工程的规模化发展视角,压滤式液流电池反应器的传质优化最终需实现组件高性能、系统低能耗、运行长寿命和成本可接受的统一。未来需通过材料研发、结构设计、系统集成与运行调控的协同创新,突破传质控制的核心瓶颈,为液流电池在大规模电化学储能领域的应用提供理论和技术支撑。

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2026年第52卷第10期
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doi: 10.13700/j.bh.1001-5965.2026.0133
  • 接收时间:2026-03-09
  • 首发时间:2026-10-30
  • 出版时间:2026-10-31
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  • 收稿日期:2026-03-09
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    1北京航空航天大学 能源与动力工程学院 仿生能源材料与器件北京市重点实验室,北京 100191
    2中国恩菲工程技术有限公司,北京 100038

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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
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