Article(id=1321967892971770808, tenantId=1146029695717560320, journalId=1220038251117760515, issueId=1321967675631317438, articleNumber=null, orderNo=null, doi=10.11868/j.issn.1001-4381.2025.000761, pmid=null, cstr=32421.14.j.issn.1001-4381.2025.000761, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1766851200000, receivedDateStr=2025-12-28, revisedDate=null, revisedDateStr=null, acceptedDate=1768492800000, acceptedDateStr=2026-01-16, onlineDate=1793111306659, onlineDateStr=2026-10-27, pubDate=1779206400000, pubDateStr=2026-05-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1793111306659, onlineIssueDateStr=2026-10-27, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1793111306659, creator=13701087609, updateTime=1793111306659, updator=13701087609, issue=Issue{id=1321967675631317438, tenantId=1146029695717560320, journalId=1220038251117760515, year='2026', volume='54', issue='5', pageStart='1', pageEnd='271', issueExtLink='null', onlineDate='null', pubDate='1779206400000', pubDateStr='2026-05-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=0, createTime=1793111254842, creator='13701087609', updateTime=1793111405793, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1321968309042532665, tenantId=1146029695717560320, journalId=1220038251117760515, issueId=1321967675631317438, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1321968309042532666, tenantId=1146029695717560320, journalId=1220038251117760515, issueId=1321967675631317438, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=43, endPage=57, ext={EN=ArticleExt(id=1321967893831603129, articleId=1321967892971770808, tenantId=1146029695717560320, journalId=1220038251117760515, language=EN, title=Research progress in electrolytes for aqueous Mg-air batteries, columnId=1220689389424919062, journalTitle=Journal of Materials Engineering, columnName=REVIEW, runingTitle=null, highlight=null, articleAbstract=

Mg-air batteries have garnered significant attention in recent years due to their outstanding advantages, including high theoretical energy density, excellent safety, low cost, and environmental friendliness. However, systematic reviews concerning aqueous Mg-air battery electrolytes remain relatively scarce. The Mg anode is prone to self-corrosion, discharge product accumulation, and severe block effect in aqueous environments. This results in low anode utilisation, suboptimal operating voltages, and pronounced voltage fluctuations, making the electrolyte a critical factor constraining the practical application of Mg-air batteries. To address this, this paper systematically reviews the fundamental properties and key influencing factors of aqueous Mg-air electrolytes, focusing on electrolyte system selection, interfacial control strategies, and additive mechanisms. The review covers the structural characteristics and applicability of chlorinated and chlorine-free near-neutral electrolytes, the regulatory roles of inorganic, organic, and composite additives, and the synergistic effects of anions at the electrolyte/anode interface. Finally, future development directions for aqueous Mg-air electrolytes are proposed, including in-depth understanding of interfacial regulation mechanisms, green design of electrolyte systems, and rapid formulation screening based on machine learning. This paper aims to provide reference for the research and application of high-performance Mg-air battery electrolytes.

, authors=Jing ZHAO1, 2, Mengjia ZHANG1, 2, Liang WU1, 2, 3, 4, Yujie QIANG5, Ping SUN1, 2, Yong WANG1, 2, Yanlong MA6, Yuan YUAN1, 2, 3, 4, Jingfeng WANG1, 2, 3, 4, Fusheng PAN1, 2, 3, 4, authorsList=Jing ZHAO, Mengjia ZHANG, Liang WU, Yujie QIANG, Ping SUN, Yong WANG, Yanlong MA, Yuan YUAN, Jingfeng WANG, Fusheng PAN, authorCompany=null, correspAuthors=Liang WU, Yujie QIANG, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, 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=1321967899674268616, articleId=1321967892971770808, tenantId=1146029695717560320, journalId=1220038251117760515, language=CN, title=水系镁空气电池电解液研究进展, columnId=1220689389663994406, journalTitle=材料工程, columnName=综述, runingTitle=null, highlight=null, articleAbstract=

镁空气电池以其理论能量密度高、安全性好、成本低和环境友好等突出优势,近年来受到广泛关注,但关于水系镁空气电池电解液的系统化综述仍相对匮乏。由于镁阳极在水系环境中易发生自腐蚀、放电产物堆积及严重块效应,导致阳极利用率低、工作电压偏低且波动明显,使电解液成为制约镁空气电池实际应用的关键因素。为此,本文系统梳理了水系镁空气电解液的基本特性与关键影响因素,重点从电解液体系选择、界面调控策略以及添加剂作用机制等方面展开综述。内容涵盖含氯与无氯近中性电解液的结构特点与适用性,无机、有机及复合添加剂的调控作用,以及阴离子在电解液/阳极界面中的协同影响。最后,对水系镁空气电解液的未来发展方向提出展望,包括界面调控机制的深化理解、电解液体系的绿色化设计以及基于机器学习的配方快速筛选等。本文旨在为高性能镁空气电池电解液的研究与应用提供参考。

, authors=赵静1, 2, 张朦佳1, 2, 吴量1, 2, 3, 4, 强玉杰5, 孙萍1, 2, 王永1, 2, 麻彦龙6, 袁媛1, 2, 3, 4, 王敬丰1, 2, 3, 4, 潘复生1, 2, 3, 4, authorsList=赵静, 张朦佳, 吴量, 强玉杰, 孙萍, 王永, 麻彦龙, 袁媛, 王敬丰, 潘复生, authorCompany=null, correspAuthors=吴量, 强玉杰, authorNote=null, correspAuthorsNote=
吴量(1985—),男,教授,博士,主要从事镁合金表面腐蚀与防护及镁空气电池等相关工作,联系地址:重庆市沙坪坝区重庆大学A区综合实验大楼(400044),E-mail:
强玉杰(1992—),男,副教授,博士,主要从事绿色缓蚀新材料、金属空气电池、水系金属电池研究等相关工作,联系地址:北京市海淀区学院路30号北京科技大学国家材料服役安全科学中心(100083),E-mail:
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intermittent discharge performance of Mg-air battery by using oxyanion corrosion inhibitor as electrolyte additive, refAbstract=null), Reference(id=1321967948722458778, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, doi=null, pmid=null, pmcid=null, year=2021, volume=7, issue=null, pageStart=612134, pageEnd=null, url=null, language=null, rfNumber=[73], rfOrder=83, authorNames=WU Q J, SHU K W, SUN L L, journalName=Frontiers in Materials, refType=null, unstructuredReference=WU Q J, SHU K W, SUN L L,et al.Recent advances in non-nucleophilic Mg electrolytes[J].Frontiers in Materials,2021,7:612134., articleTitle=Recent advances in non-nucleophilic Mg electrolytes, refAbstract=null), Reference(id=1321967948844093595, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, doi=null, pmid=null, pmcid=null, year=2025, volume=699, issue=null, pageStart=138170, pageEnd=null, url=null, language=null, rfNumber=[74], rfOrder=84, authorNames=SHA J C, WANG Q, LI X, journalName=Journal of Colloid and Interface Science, refType=null, unstructuredReference=SHA J C, WANG Q, LI X,et al.Trifluoroacetamide additive-driven solvation structure regulation and interfacial adsorption for wide-temperature hydrogen-evolution-suppressed aqueous magnesium-air batteries[J].Journal of Colloid and Interface Science,2025,699:138170., articleTitle=Trifluoroacetamide additive-driven solvation structure regulation and interfacial adsorption for wide-temperature hydrogen-evolution-suppressed aqueous magnesium-air batteries, refAbstract=null)], funds=[Fund(id=1321967920641593407, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, awardId=52571128, language=CN, fundingSource=国家自然科学基金项目(52571128), fundOrder=null, country=null), Fund(id=1321967920746451008, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, awardId=52171101, language=CN, 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Engineering,Chongqing University of Technology,Chongqing 400054,China), AuthorCompanyExt(id=1321967903029711835, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, companyId=1321967903000351705, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=6.重庆理工大学 材料科学与工程学院,重庆 400054)])], figs=[ArticleFig(id=1321967913553219625, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, language=EN, label=Fig.1, caption=Evolution of electrolytes for Mg-air batteries, figureFileSmall=+XZcSqydyLzgLU/KKusaSg==, figureFileBig=/FQ/JC2Qhn1pQRHThPgR0Q==, tableContent=null), ArticleFig(id=1321967913888763946, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, language=CN, label=图1, caption=镁空气电池电解液发展历程, figureFileSmall=+XZcSqydyLzgLU/KKusaSg==, figureFileBig=/FQ/JC2Qhn1pQRHThPgR0Q==, tableContent=null), ArticleFig(id=1321967914375303211, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, language=EN, label=Fig.2, caption=Electrolytes with different concentrations of MgCl2[36]

(a)polarization curves;(b)dynamic hydrogen evolution curves;(c)surface morphology before and after removing discharge products after discharging at 2.5 mA/cm² for 10 h

, figureFileSmall=CdbzOLOojrLh9lBizAbh1A==, figureFileBig=eZEkLqaErBrPxqWa4GcHOA==, tableContent=null), ArticleFig(id=1321967916061413421, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, language=CN, label=图2, caption=不同浓度MgCl2电解液[36]

(a)极化曲线;(b)动态析氢曲线;(c)2.5 mA/cm2下,放电10 h去除放电产物前后的表面形貌

, figureFileSmall=CdbzOLOojrLh9lBizAbh1A==, figureFileBig=eZEkLqaErBrPxqWa4GcHOA==, tableContent=null), ArticleFig(id=1321967916174659630, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, language=EN, label=Fig.3, caption=Mechanism of Mg action in different chloride-free electrolytes(a)-(e)NaCl and NaNO₃ electrolytes[38];(f)NaCl and NaAc electrolytes[39];(g)NaCl and NaCA electrolytes[40], figureFileSmall=whNZcMUa+UOlZUGP8Q9diw==, figureFileBig=SRQOrkZJZsdXL+wsWYJlFQ==, tableContent=null), ArticleFig(id=1321967916266934319, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, language=CN, label=图3, caption=Mg在不同无氯电解液中的作用机理

(a)~(e)NaCl、NaNO₃电解液 [38];(f)NaCl和NaAc电解液[39];(g)NaCl和NaCA电解液 [40]

, figureFileSmall=whNZcMUa+UOlZUGP8Q9diw==, figureFileBig=SRQOrkZJZsdXL+wsWYJlFQ==, tableContent=null), ArticleFig(id=1321967916409540656, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, language=EN, label=Fig.4, caption=Effects of introducing inorganic additives on anode surface and its composition

(a)introduction of water-soluble graphene[44];(b)introduction of Na₃PO₄·12H₂O and NaVO₃[45];

(c)introduction of (NH₄)₂ HPO₄/CaF₂/NaF/Zn(NO₃)₂[46];(d)introduction of InCl₃[47]

, figureFileSmall=RM1WM2yODpIRba7tdquF+Q==, figureFileBig=yOxe8PbaYzN1JZtP0TcnTw==, tableContent=null), ArticleFig(id=1321967916485038129, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, language=CN, label=图4, caption=无机添加剂的引入对阳极表面及其成分的影响

(a)水溶性石墨烯的引入[44];(b)Na3PO4·12H2O、NaVO3的引入[45];(c)(NH4)2HPO4/CaF2/NaF/Zn(NO3)2的引入[46];(d)InCl₃的引入[47]

, figureFileSmall=RM1WM2yODpIRba7tdquF+Q==, figureFileBig=yOxe8PbaYzN1JZtP0TcnTw==, tableContent=null), ArticleFig(id=1321967916564729906, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, language=EN, label=Fig.5, caption=Effect of organic additive introduction on electrochemical activity and discharge uniformity

(a)introduction of SDS[51];(b)introduction of glycerol ether[54];(c)introduction of [Ch][DHB][52];(d)introduction of 3,5-DHB[55]

, figureFileSmall=At+X0j9TTKtbrH0cdi1Xbg==, figureFileBig=NLYtj7yaU1AP1pivfNkKTA==, tableContent=null), ArticleFig(id=1321967916824776755, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, language=CN, label=图5, caption=有机添加剂的引入对电化学活性及放电均匀性的影响

(a)SDS的引入[51];(b)甘油电的引入[54];(c)[Ch][DHB]的引入[52];(d)3,5-DHB的引入[55]

, figureFileSmall=At+X0j9TTKtbrH0cdi1Xbg==, figureFileBig=NLYtj7yaU1AP1pivfNkKTA==, tableContent=null), ArticleFig(id=1321967916891885620, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, language=EN, label=Fig.6, caption=Effect of mixed additives on anodic corrosion and discharge

(a)SSA+ethanol/3,4-DHB+ethanol[60];(b)SAL+NO3-[61];(c)ethanol+organic acid[62]

, figureFileSmall=0UCh9Cdwfj43oYWQ8TUKFA==, figureFileBig=CS8Zt+1efSOpsU31m+4mXw==, tableContent=null), ArticleFig(id=1321967917248401461, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, language=CN, label=图6, caption=混合添加剂的引入对阳极腐蚀及放电的影响

(a)SSA+ethanol/3,4-DHB+ethanol[60];(b)SAL+NO3-[61];(c)ethanol+有机酸[62]

, figureFileSmall=0UCh9Cdwfj43oYWQ8TUKFA==, figureFileBig=CS8Zt+1efSOpsU31m+4mXw==, tableContent=null), ArticleFig(id=1321967917328093238, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, language=EN, label=Fig.7, caption=Machine learning-assisted electrolyte design and mechanism study

(a)-(e)electrolyte design[64];(f)-(i)mechanism study[65]

, figureFileSmall=jLouB6OKY51K7BNt5VW0Fg==, figureFileBig=LrW8W7oX5zfhjWC5BQqZtQ==, tableContent=null), ArticleFig(id=1321967917659443255, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, language=CN, label=图7, caption=机器学习辅助电解液设计及机理研究

(a)~(e)电解液设计[64];(f)~(i)机理研究[65]

, figureFileSmall=jLouB6OKY51K7BNt5VW0Fg==, figureFileBig=LrW8W7oX5zfhjWC5BQqZtQ==, tableContent=null), ArticleFig(id=1321967917739135032, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, language=EN, label=Table 1, caption=

Basic electrolyte composition design and associated advantages

, figureFileSmall=null, figureFileBig=null, tableContent=
Electrolyte compositionAlloy typeAdvantageRef.
15% NaClAZ31The specific power output of the battery has nearly doubled[35]

0.05/0.1/0.2 mol/L

MgCl2

Hp-MgAs the salt concentration increases, the discharge process becomes more uniform[36]
0.5 mol/L NaNO3Pure MgThe anode surface oxide film is more compact, resulting in more uniform discharge and enhanced anode efficiency[38]
1 mol/L NaAcAZ31At 10 mA/cm2, the anode efficiency increased to 84%, with the specific energy rising to 1770 Wh/kg[39]
0.1 mol/L NaCAMg0.5Zn0.2GeAt 5 mA/cm2, the anode efficiency and specific capacity are 91.4% and 2007 mAh/g respectively[40]
), ArticleFig(id=1321967918095650873, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, language=CN, label=表1, caption=

基础电解液成分设计及相关优势

, figureFileSmall=null, figureFileBig=null, tableContent=
Electrolyte compositionAlloy typeAdvantageRef.
15% NaClAZ31The specific power output of the battery has nearly doubled[35]

0.05/0.1/0.2 mol/L

MgCl2

Hp-MgAs the salt concentration increases, the discharge process becomes more uniform[36]
0.5 mol/L NaNO3Pure MgThe anode surface oxide film is more compact, resulting in more uniform discharge and enhanced anode efficiency[38]
1 mol/L NaAcAZ31At 10 mA/cm2, the anode efficiency increased to 84%, with the specific energy rising to 1770 Wh/kg[39]
0.1 mol/L NaCAMg0.5Zn0.2GeAt 5 mA/cm2, the anode efficiency and specific capacity are 91.4% and 2007 mAh/g respectively[40]
), ArticleFig(id=1321967918200508474, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, language=EN, label=Table 2, caption=

Design of additive-containing electrolyte components and performance parameters

, figureFileSmall=null, figureFileBig=null, tableContent=

Types of

additive

Electrolyte compositionAlloy type

Current density/

(mA∙cm-2)

Average Voltage/

V

Anode Efficiency/

%

Specific Energy/

(Wh·kg-1)

Ref.
Inorganic additives3.5% NaCl+1 g/L WSGCP-Mg1.5-61.0-1.246.71030.71[44]
3.5% NaCl + 0.02 mol/L Na3PO4·12H2O/NaVO3AZ31101.0769.91645.66[45]
5/50 mmol/L NaCl + 0.5 g/L NaF/CaF/ (NH₄)₂HPO₄ZK30101.0373.1≈1100[46]
3.5% NaCl+ 1/5/10 mmol/L InCl3Mg-0.15Ca11.74≈552260[47]
Organic additives3.5% NaCl+3/5/10/30 mmol/L SDSAZ31B[51]
3.5% NaCl + 2%/3%/4%(volume fraction)gly

Rolled condition

AZ31

10≈1.651.241913.2[52]
3.5% NaCl + 0.05/0.1/0.2/0.3 [Ch][DHB]HP-Mg51.45682093[53-54]

Mixed additives

3.5% NaCl + 0.05 mol/L 3,5-DHBMg0.5Zn0.2Ge51.5567.31476.6[55]
3.5% NaCl + 0.5 g/L SDBS + 0.5 g/L Na3PO4AZ91201.1549.1≈1243[60]
3.5% NaCl + NO3- + SALCP-Mg5≈1.582[61]

3.5% NaCl + 30%(volume fraction) ethanol + 0.1 mol/L

5-SSAL/Tiron/3,4-DHB

AZ6151.234548.21724.5[62]
), ArticleFig(id=1321967918523469883, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, language=CN, label=表2, caption=

含添加剂的电解液成分设计及相关性能参数

, figureFileSmall=null, figureFileBig=null, tableContent=

Types of

additive

Electrolyte compositionAlloy type

Current density/

(mA∙cm-2)

Average Voltage/

V

Anode Efficiency/

%

Specific Energy/

(Wh·kg-1)

Ref.
Inorganic additives3.5% NaCl+1 g/L WSGCP-Mg1.5-61.0-1.246.71030.71[44]
3.5% NaCl + 0.02 mol/L Na3PO4·12H2O/NaVO3AZ31101.0769.91645.66[45]
5/50 mmol/L NaCl + 0.5 g/L NaF/CaF/ (NH₄)₂HPO₄ZK30101.0373.1≈1100[46]
3.5% NaCl+ 1/5/10 mmol/L InCl3Mg-0.15Ca11.74≈552260[47]
Organic additives3.5% NaCl+3/5/10/30 mmol/L SDSAZ31B[51]
3.5% NaCl + 2%/3%/4%(volume fraction)gly

Rolled condition

AZ31

10≈1.651.241913.2[52]
3.5% NaCl + 0.05/0.1/0.2/0.3 [Ch][DHB]HP-Mg51.45682093[53-54]

Mixed additives

3.5% NaCl + 0.05 mol/L 3,5-DHBMg0.5Zn0.2Ge51.5567.31476.6[55]
3.5% NaCl + 0.5 g/L SDBS + 0.5 g/L Na3PO4AZ91201.1549.1≈1243[60]
3.5% NaCl + NO3- + SALCP-Mg5≈1.582[61]

3.5% NaCl + 30%(volume fraction) ethanol + 0.1 mol/L

5-SSAL/Tiron/3,4-DHB

AZ6151.234548.21724.5[62]
), ArticleFig(id=1321967918607355964, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, language=EN, label=Table 3, caption=

Machine learning-assisted electrolyte composition design and performance parameters

, figureFileSmall=null, figureFileBig=null, tableContent=
Electrolyte compositionAlloy type

Current density/

(mA∙cm-2)

Average voltage/

V

Anode efficiency/

%

Specific energy/

(Wh·kg-1)

Ref.
3.5% NaCl + 0.01 mol/L 2,3-dihydroxynaphthaleneMg-0.2Ca11.82833370[64]
3.5% NaCl +0.1/0.3/0.5 mol/L GLDAZ3151.451952.70[65]
3.5% NaCl +0.1/0.2/0.3 mol/L glyLAZ93111.8351.451913.20[66]
), ArticleFig(id=1321967918934511677, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, language=CN, label=表3, caption=

机器学习辅助电解液成分设计及相关性能参数

, figureFileSmall=null, figureFileBig=null, tableContent=
Electrolyte compositionAlloy type

Current density/

(mA∙cm-2)

Average voltage/

V

Anode efficiency/

%

Specific energy/

(Wh·kg-1)

Ref.
3.5% NaCl + 0.01 mol/L 2,3-dihydroxynaphthaleneMg-0.2Ca11.82833370[64]
3.5% NaCl +0.1/0.3/0.5 mol/L GLDAZ3151.451952.70[65]
3.5% NaCl +0.1/0.2/0.3 mol/L glyLAZ93111.8351.451913.20[66]
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水系镁空气电池电解液研究进展
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赵静 1, 2 , 张朦佳 1, 2 , 吴量 1, 2, 3, 4 , 强玉杰 5 , 孙萍 1, 2 , 王永 1, 2 , 麻彦龙 6 , 袁媛 1, 2, 3, 4 , 王敬丰 1, 2, 3, 4 , 潘复生 1, 2, 3, 4
材料工程 | 综述 2026,54(5): 43-57
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材料工程 |综述 2026 , 54 (5) : 43 -57
水系镁空气电池电解液研究进展
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2.重庆大学 国家镁合金工程研究中心,重庆 400044
3.重庆市新型储能材料与装备研究院明月湖实验室,重庆 401122
4.重庆大学 前沿交叉学科研究院,重庆 400044, bio=null, bioImg=null, bioContent=null, aboutCorrespAuthor=null)}, companyList=[AuthorCompany(id=1321967900479574985, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, xref=1., ext=[AuthorCompanyExt(id=1321967900487963594, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, companyId=1321967900479574985, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1.College of Materials Science and Engineering,Chongqing University,Chongqing 400044,China), AuthorCompanyExt(id=1321967900496352203, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, companyId=1321967900479574985, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1.重庆大学 材料科学与工程学院,重庆 400044)]), AuthorCompany(id=1321967900580238284, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, xref=2., ext=[AuthorCompanyExt(id=1321967900609598413, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, companyId=1321967900580238284, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2.National Engineering Research Center for Magnesium Alloys,Chongqing University,Chongqing 400044,China), AuthorCompanyExt(id=1321967900890616782, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, companyId=1321967900580238284, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2.重庆大学 国家镁合金工程研究中心,重庆 400044)]), AuthorCompany(id=1321967902538978256, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, xref=3., ext=[AuthorCompanyExt(id=1321967902551561169, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, companyId=1321967902538978256, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=3.Chongqing Institute of New Energy Storage Materials and Equipment,Chongqing 401122,China), AuthorCompanyExt(id=1321967902564144082, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, companyId=1321967902538978256, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=3.重庆市新型储能材料与装备研究院明月湖实验室,重庆 401122)]), AuthorCompany(id=1321967902643835859, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, xref=4., ext=[AuthorCompanyExt(id=1321967902652224468, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, companyId=1321967902643835859, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=4.Institute of Advanced Interdisciplinary Studies,Chongqing University,Chongqing 400044,China), AuthorCompanyExt(id=1321967902664807381, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967892971770808, companyId=1321967902643835859, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=4.重庆大学 前沿交叉学科研究院,重庆 400044)])])]
赵静1, 2, 张朦佳1, 2, 吴量1, 2, 3, 4 , 强玉杰5 , 孙萍1, 2, 王永1, 2, 麻彦龙6, 袁媛1, 2, 3, 4, 王敬丰1, 2, 3, 4, 潘复生1, 2, 3, 4
作者信息
  • 1.重庆大学 材料科学与工程学院,重庆 400044
  • 2.重庆大学 国家镁合金工程研究中心,重庆 400044
  • 3.重庆市新型储能材料与装备研究院明月湖实验室,重庆 401122
  • 4.重庆大学 前沿交叉学科研究院,重庆 400044
  • 5.北京科技大学 国家材料服役安全科学中心,北京 100083
  • 6.重庆理工大学 材料科学与工程学院,重庆 400054
通讯作者:
吴量(1985—),男,教授,博士,主要从事镁合金表面腐蚀与防护及镁空气电池等相关工作,联系地址:重庆市沙坪坝区重庆大学A区综合实验大楼(400044),E-mail:
强玉杰(1992—),男,副教授,博士,主要从事绿色缓蚀新材料、金属空气电池、水系金属电池研究等相关工作,联系地址:北京市海淀区学院路30号北京科技大学国家材料服役安全科学中心(100083),E-mail:
Research progress in electrolytes for aqueous Mg-air batteries
Jing ZHAO1, 2, Mengjia ZHANG1, 2, Liang WU1, 2, 3, 4 , Yujie QIANG5 , Ping SUN1, 2, Yong WANG1, 2, Yanlong MA6, Yuan YUAN1, 2, 3, 4, Jingfeng WANG1, 2, 3, 4, Fusheng PAN1, 2, 3, 4
Affiliations
  • 1.College of Materials Science and Engineering,Chongqing University,Chongqing 400044,China
  • 2.National Engineering Research Center for Magnesium Alloys,Chongqing University,Chongqing 400044,China
  • 3.Chongqing Institute of New Energy Storage Materials and Equipment,Chongqing 401122,China
  • 4.Institute of Advanced Interdisciplinary Studies,Chongqing University,Chongqing 400044,China
  • 5.National Center for Materials Service Safety,University of Science and Technology Beijing,Beijing 100083,China
  • 6.College of Materials Science and Engineering,Chongqing University of Technology,Chongqing 400054,China
出版时间: 2026-05-20 doi: 10.11868/j.issn.1001-4381.2025.000761
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镁空气电池以其理论能量密度高、安全性好、成本低和环境友好等突出优势,近年来受到广泛关注,但关于水系镁空气电池电解液的系统化综述仍相对匮乏。由于镁阳极在水系环境中易发生自腐蚀、放电产物堆积及严重块效应,导致阳极利用率低、工作电压偏低且波动明显,使电解液成为制约镁空气电池实际应用的关键因素。为此,本文系统梳理了水系镁空气电解液的基本特性与关键影响因素,重点从电解液体系选择、界面调控策略以及添加剂作用机制等方面展开综述。内容涵盖含氯与无氯近中性电解液的结构特点与适用性,无机、有机及复合添加剂的调控作用,以及阴离子在电解液/阳极界面中的协同影响。最后,对水系镁空气电解液的未来发展方向提出展望,包括界面调控机制的深化理解、电解液体系的绿色化设计以及基于机器学习的配方快速筛选等。本文旨在为高性能镁空气电池电解液的研究与应用提供参考。

镁空气电池  /  水系电解液  /  电解液添加剂  /  界面调控  /  机器学习

Mg-air batteries have garnered significant attention in recent years due to their outstanding advantages, including high theoretical energy density, excellent safety, low cost, and environmental friendliness. However, systematic reviews concerning aqueous Mg-air battery electrolytes remain relatively scarce. The Mg anode is prone to self-corrosion, discharge product accumulation, and severe block effect in aqueous environments. This results in low anode utilisation, suboptimal operating voltages, and pronounced voltage fluctuations, making the electrolyte a critical factor constraining the practical application of Mg-air batteries. To address this, this paper systematically reviews the fundamental properties and key influencing factors of aqueous Mg-air electrolytes, focusing on electrolyte system selection, interfacial control strategies, and additive mechanisms. The review covers the structural characteristics and applicability of chlorinated and chlorine-free near-neutral electrolytes, the regulatory roles of inorganic, organic, and composite additives, and the synergistic effects of anions at the electrolyte/anode interface. Finally, future development directions for aqueous Mg-air electrolytes are proposed, including in-depth understanding of interfacial regulation mechanisms, green design of electrolyte systems, and rapid formulation screening based on machine learning. This paper aims to provide reference for the research and application of high-performance Mg-air battery electrolytes.

Mg-air battery  /  aqueous electrolyte  /  electrolyte additive  /  interface control  /  machine learning
赵静, 张朦佳, 吴量, 强玉杰, 孙萍, 王永, 麻彦龙, 袁媛, 王敬丰, 潘复生. 水系镁空气电池电解液研究进展. 材料工程, 2026 , 54 (5) : 43 -57 . DOI: 10.11868/j.issn.1001-4381.2025.000761
Jing ZHAO, Mengjia ZHANG, Liang WU, Yujie QIANG, Ping SUN, Yong WANG, Yanlong MA, Yuan YUAN, Jingfeng WANG, Fusheng PAN. Research progress in electrolytes for aqueous Mg-air batteries[J]. Journal of Materials Engineering, 2026 , 54 (5) : 43 -57 . DOI: 10.11868/j.issn.1001-4381.2025.000761
受能源供需失衡与全球气候政策驱动,构建高自主、全面储能体系已成共识,这促进了电池等先进储能装置的创新和可持续能源解决方案的开发[1],尽管锂离子电池比容量高且循环寿命长,但锂资源的过度消耗、过高的成本和安全问题限制了其在储能领域的应用。自1960年以来,金属空气电池由于低成本、高比能量密度、优异的理论放电性能和清洁生产等特性,被认为是理想的储能系统,吸引了众多研究人员的参与[2-4]。
空气电池自19世纪末发明以来,被认为是一种很有前途的储能装置。首先,镁在地壳中储量丰富,在地壳元素含量排名第八位(质量分数为2.1%),价格低廉[5-6];其次,镁的标准电极电位为-2.37 V(vs. SHE),而锌仅为-0.763 V,这意味着镁阳极具有较高的电化学活性;第三,镁空气电池的理论能量密度高达6800 Wh/kg,具有较强的储能潜力;最后,镁空气电池在环保和安全性方面也有明显的优势,镁空气电池放电产物Mg(OH)2无毒无害,且放电过程中不会产生污染气体,另外由于电池阴极接通空气,放电过程中产生的少量H2难以聚集,且水系电解液在电池短路时是不可燃的[7-8]。这些优点表明,镁空气电池具有成为下一代储能器件的巨大潜力。
水系电解液放电过程中,Mg(OH)₂在阳极表面生成并沉积,导致阳极钝化,从而抑制了后续的阳极反应;此外,副反应产生的H2会破坏密封电池空间的压力平衡等问题不适合用于可逆空气电池。因此,目前商业和开发中的水系镁空气电池产品主要集中在应急与极端环境电源和便携式使用等一次镁空气电池[9]的应用上。
本文系统梳理了水系镁空气电解液的基本特性与关键影响因素,重点从电解液体系选择、界面调控策略以及添加剂作用机制等方面展开综述。
水系镁空气电池由金属镁阳极、中性水系电解液及空气阴极三大部分构成。其中,阳极材料为金属镁及其合金,电解液为水系溶液,为避免过酸或过碱溶液对电池放电性能产生不良影响,将电解液调为中性。另外,空气阴极主要由气体扩散层、催化剂层、集流体层和防水层这几个关键部分组成[10-11],其中,扩散层具有高孔隙率和良好的电子导电性,允许空气中的氧气有效扩散进入电极内部,同时传导电子;催化剂层包含用于促进氧还原反应的活性催化剂,如锰氧化物、贵金属或过渡金属氧化物等,是电化学反应的核心区域;集流体通常由导电材料(如泡沫镍、碳布或金属网)构成,用于收集和传导反应中产生的电子;而防水层防止电解液渗漏,同时允许氧气通过,维持电极的稳定性和反应效率。
工作过程中,镁阳极上金属Mg失去电子转化为Mg2+,阴极上的O2在电解液中得电子后变成OH-。如反应式(1)~(3)所示,放电过程中,阴极消耗的O2大部分来自周围空气,从而减轻系统整体的质量并提高理论能量密度[12]。
阳极反应:Mg-2e-→Mg2+
阴极反应:O2+2H2O+4e-→4OH-
总反应:2Mg+O2+2H2O→2MgOH2
水系镁空气电池在工作过程中主要存在的问题可归结为两个方面:其一是由于镁及其合金比较活泼,在与水接触的过程中会发生一定程度的自腐蚀,生成Mg(OH)2不溶物并伴随着一定程度的析氢(hydrogen evolution reaction,HER)[4],如式(4)所示。另外在放电过程中,由于金属镁阳极的不均匀溶解,可能导致有部分未溶解的镁阳极颗粒直接从阳极脱落,即“块状效应”(该现象在低电流密度下更明显)。上述问题均会导致比容量和阳极利用率的降低。
其二为放电过程中,随着放电工作的进行,放电产物MgO/Mg(OH)2等不溶物堆积在镁阳极表面,使阳极和电解液不能够充分接触,阻碍了放电反应的进一步发生,从而导致放电电压降低且不稳定[11]。
Mg+2H2O→MgOH2+H2
为了解决上述问题,提高电池的阳极利用率和放电电压,通常可以采取以下措施:
(1)阳极处理。目前的工作主要集中在对镁阳极进行合金化处理、塑性变形及热处理[5,13-15]这三个方面。通过添加特定元素(如Ca、Zn、Sn、Al等)合金化处理,可以引入第二相,调控微观结构,从而抑制自腐蚀并提升放电活性;塑性变形(挤压、轧制等)工艺则可通过细化晶粒(至微米级)和破碎第二相来促进均匀腐蚀,以减少局部脱落;热处理(固溶、时效、退火)的作用机制是通过调控第二相形态与分布来优化电化学活性与耐蚀性的平衡。
(2)高活性阴极催化剂。高活性阴极催化剂通过加速氧还原反应动力学、降低过电位并提高反应选择性[16],可显著改善镁空气电池的放电性能。当前的发展主要包括贵金属催化剂、钙钛矿/尖晶石氧化物催化剂、双功能氧化物纳米晶催化剂和碳基非金属催化体系。
(3)电解液改性。在放电过程中,电解液是与金属阳极和空气阴极均有接触的中间物质,而水系电解液中的离子的种类和浓度均会对金属镁阳极的放电性能产生直接影响。目前中性盐水(0.5~2 mol/L NaCl)电解液兼顾离子导电率高与低成本的优势仍为主流[5,17-19],但存在Cl-诱导点蚀、阳极效率低(<40%)等未解难题。近些年来研究发现,向电解液中引入多功能添加剂,可通过界面耦合和产物调控来实现放电性能的提升。因此,基础电解液的优选和功能添加剂的设计相结合是调节电池性能的有效途径。
综合分析以上提高电池的阳极利用率和放电电压的主要措施,电解液改性以“改动最小、成本最低、见效最快”的方式,同时有效减缓析氢腐蚀和产物钝化,是当前水系镁空气电池走向实用化最经济、最灵活的突破口。
在水系电解液中,镁空气电池的性能主要受两类副反应的制约,一是来自镁合金杂质或外部污染的微量Fe3+/Fe2+,会在镁阳极表面得电子形成纳米铁颗粒,发生电化学再沉积[20-21]。这些铁颗粒与镁基体构成微观电偶对,作为强阴极极大地加速了局部的自腐蚀过程。二是活泼Mg阳极直接与电解液中的H2O反应产生氢气并伴随Mg(OH)₂的生成与堆积[22-24]。电解液中阴离子的种类及浓度对上述反应的速率与路径有极大影响,因此阴离子的理性设计成为提升电池性能的关键环节。
图1系统梳理了镁空气电池电解液的发展历程,重点评述了水系电解液在阴离子选择与功能化添加剂协同优化方面的重要进展。
早在20世纪60年代,美国通用电气公司(GE)[11]就获得了一种以3.5%(质量分数,下同) NaCl + 0.1 mol/L NaNO₂溶液作为电解液的镁空气电池,首次提出了“缓蚀剂+中性盐”做镁空气电池电解液的新思路,使开路电位负移80 mV,析氢速率下降一个数量级。1981年,美国Westinghouse公司[25]研制出适用于海洋应用的海水电解质镁空气电池,其直接利用海水电解液,实现300~500 Wh/kg的能量密度,可用于潜艇应急电源。
在随后的发展过程中,鉴于海水主要由平均浓度为3.5% NaCl、KCl等无机盐水溶液组成,人们逐渐使用3.5% NaCl水溶液作为实验室规模下海水介质的简化模型[5]。尽管后续的研究也探索了其他中性电解液,但大多数研究仍然主要集中在用3.5% NaCl溶液作为标准电解液开展性能评估与机制探讨。1998年,古屋金属与三菱材料合作[26],使用2% NaCl + 0.05 mol/L NaNO₃ +微量磷酸盐的电解液体系,首次系统比较了PO43-、CrO43-、VO43-等无机添加剂对Mg(OH)₂膜形貌的影响。2005年,上海交通大学的NuLi等[16]制备了水系/非水混合电解液,证明镁在电解液中可逆沉积-溶解,为后续“可充水系”的发展奠定了基础。
2013年,中国科学院大连化学物理研究所研发的镁空气电池首次应用于四川芦山地震灾区的应急供电。其电源输出功率达10 W,能量密度达770 Wh/kg,约为普通铅酸电池的20~30倍。该电源可提供长达一个月的电力供应,能够在灾区作为帐篷照明灯、手机充电器等小型设备应急移动电源,为灾后救援提供长时间照明、通讯等保障,有效解决大面积电力中断带来的影响。2016年,Höche等[20]发现,在镁电池的水系电解液中加入水杨酸盐等络合剂,与Fe3+形成络合物,可防止铁杂质的再沉积,抑制阳极表面的自腐蚀,从而提高电池性能。此后,更多专家和学者投身于镁空气电池电解液添加剂[27-32]的研究当中。
在德国,亥姆霍兹研究所[33]研究发现,通过向3.5% NaCl基础电解液中添加适量浓度的2,6-DHB(0.2 mol/L),可以有效阻止放电产物的沉淀,从而减少电压降,添加2,6-DHB能够同时提高Mg-0.15Ca阳极的放电电压和利用效率。在2,6-DHB存在的情况下,放电过程中,2,6-DHB会与镁阳极表面的Mg2+形成可溶性络合物,阻碍Mg(OH)2/MgO放电产物的进一步沉积,从而提高镁空气电池的放电性能。
水系镁空气电池阳极在工作过程中存在着严重的自腐蚀问题[34],活泼的镁阳极会与电解液中的水发生反应,生成Mg(OH)2钝化膜并伴随着氢气的逸出(式(4))。
目前,中性盐电解液(最常用为3.5% NaCl)因其高离子电导率与低成本,成为镁空气电池的首选电解液。然而在放电过程中,体积小且腐蚀性强的Cl-极易击穿镁阳极表面的钝化膜致使膜层破裂[17],膜层的开裂虽能短暂提供Mg²⁺传输通道,但会迫使裸露的基体与电解液直接接触,导致析氢副反应加剧,引发严重的局部腐蚀,降低阳极效率并缩短电池寿命。
电解液既要保证足够的离子电导率,又必须抑制镁阳极的“析氢-钝化”两大副反应[7]。近年来研究表明,通过优选高适配电解液或在电解液中引入具有特定功能的添加剂,可显著抑制副反应并调控界面化学,达到同时抑制析氢、提高阳极利用率和放电电压的效果,从而实现高功率输出;此外,还可通过机器学习辅助等技术手段深入研究机理。综合最新文献,可把目前主流的电解液体系归纳为“两类基础液”+“三类功能添加剂”。
电解液的pH对镁阳极的电化学性能和放电性能有着显著的影响。在酸性电解液环境中,镁阳极表面生成的Mg(OH)2钝化层会迅速溶解,Mg阳极表面的保护膜脱落,使镁阳极暴露于酸性环境中,发生更为严重的析氢腐蚀,降低了阳极利用率。
而在碱性环境中,较高浓度的OH-捕获阳极附近的Mg2+形成Mg(OH)2,过多的Mg(OH)2形成积累会造成阳极过高的溶解电位,从而降低电池的放电电压。此外,空气阴极中包含的微量的CO2会与Mg2+结合,导致在空气阴极上形成MgCO3沉淀物[5,24]。这种沉淀物的持续生成会堵塞孔隙,阻碍了放电反应的进一步发生。因此,目前最常用的电解液呈中性,以避免上述环境造成的不良影响。
鉴于海水主要由平均浓度为3.5%的NaCl、KCl等无机盐水溶液组成,因此国际镁电池测试协议(IEC 62854-2018)推荐以3.5% NaCl为基准电解液,使不同文献间的性能数据具备可比性。目前水系镁空气电池最常用的电解液为3.5%的NaCl或其他含Cl⁻电解液[7,17]。在当前的研究中,一般把3.5% 的NaCl当作基础对比实验,通过调整电解液中Cl-的浓度或阴离子种类来改善电池的放电性能。Zhuk等[35]研究了在15% NaCl电解液中,AZ31型商用合金在40~120 mA/cm² 电流密度下的放电性能。相比于使用3.5% NaCl电解液,使用15% NaCl电解液可以使电池的比功率几乎翻倍。在这一过程中,电解液中盐溶液的增加降低了电解液的电阻,而比功率的增加是通过降低电解液的电阻实现的。Wang等[36]研究了不同浓度(0.05/0.1/0.2 mol/L)的MgCl2盐溶液电解液浓度对镁空气电池放电和腐蚀行为的具体影响。研究发现,较高浓度的Cl-更易破坏阳极表面的薄膜层,露出镁基体,从而提高放电活性,但同时也加速了HER(如图2(a),(b)所示)。此外,随着盐浓度的升高,放电过程更均匀,通过SEM可观察到更为平滑的表面(图2(c))。
在含Cl-的中性盐溶液中,Cl-因半径小、电负性高等特点,极易扩散到阳极表面并破坏表面的Mg(OH)₂保护膜,进而加速镁阳极的腐蚀。但由于含Cl-的中性盐溶液导电率高、稳定性强、成本较低以及环境友好等优势,其依旧是主流的电解液核心成分。在目前关于镁空气电池电解液的探索过程中,可通过向NaCl电解液中添加缓蚀剂等添加剂来缓解Cl-对镁阳极的过度腐蚀,实现放电产物形貌的可控调节,从而提高电池的放电性能。
传统的NaCl或MgCl2等含氯水系电解液中存在严重的HER,影响了镁空气电池的放电性能,导致其比容量差、利用率低等问题。因此,传统的NaCl溶质被建议使用硝酸盐[37-38]等其他电解液及作为缓蚀剂或络合剂的添加剂所替代。Zhou等[38]使用0.5 mol/L NaNO3电解液,由于没有腐蚀性Cl-的存在,镁阳极表面的氧化膜变得更为致密(图3(a),(b)),阻碍了镁阳极腐蚀的进一步发生,从而提高阳极效率。此外,NO3-到NO2-的还原反应起主导作用,这项得电子的过程促使HER显著减少,避免了块效应的生成,使得放电过程更加均匀。王二东课题组[39]尝试使用1 mol/L NaAc无氯电解液,放电过程相较于传统NaCl溶液更为均匀。Ac-凭借其在膜内较大的扩散能垒避免了Mg阳极的局部钝化膜击穿,使得NaAc电解液中的Mg阳极表现出均匀的溶解行为(图3(f))。在10 mA/cm2时,与NaCl电解液中59%的阳极利用效率相比,镁空气电池在NaAc电解液中提高到了84%,比能量也从1370 Wh/kg提高到1770 Wh/kg。Jiang等[40]将0.1 mol/L NaCA做Mg0.5Zn0.2Ge阳极空气电池的电解液,5 mA/cm2条件下,Mg0.5Zn0.2Ge阳极的利用效率和比容量分别为91.4%及2007 mAh/g,比NaCl电解液中的同类产品提高了54%。这主要归功于NaCA电解液中自腐蚀减缓以及Mg0.5Zn0.2Ge阳极在放电过程中的均匀溶解,其工作原理如图3(g)所示。
对于完全去除Cl⁻的电解液,可以通过从源头消除点蚀诱发源来解决该问题。引入的阴离子一般为“成膜型”或“位阻型”离子,可以让镁阳极表面覆盖一层致密的保护膜。但与此同时,无Cl⁻时,放电产物以Mg(OH)₂为主,长成的致密的Mg(OH)₂覆盖层阻碍了放电过程的进一步发生,易导致放电电压降低。因此,考虑向无氯电解液中添加镁离子络合剂、有机缓蚀剂等,诱导形成薄而疏松的Mg(OH)2薄膜或有机-无机复合膜,既能阻断水与H⁺的持续侵蚀,又可保持离子通道,使得放电电位更高更平稳。表1[35-36,38-40]系统梳理了基础电解液成分及相关优势对比。
在镁空气电池电解液体系中,碳材料、钒酸盐、磷酸盐等无机添加剂被不少研究人员探索[41-43],其主要通过在阳极放电表面形成疏松多孔氧化物膜或吸附于阳极表面抑制析氢等机理来改善电池的放电性能。
Mayilvel Dinesh等[44]研究了在3.5% NaCl基础电解液中添加一定量的水溶性石墨烯(WSG)对镁空气电池放电性能的影响。从图4(a)可以看出,WSG的加入避免了自放电过程中镁的击穿,降低了镁阳极的腐蚀速率,使极化曲线中产生更负的负电位。Zhao等[45]研究了在3.5% NaCl中加入0.02 mol/L Na3PO4·12H2O/0.02 mol/L NaVO3对镁空气电池性能的影响。使用含磷酸盐和钒酸盐电解液的镁阳极覆盖了一层更为疏松的放电产物膜(图4(b)),松散堆积的放电产物膜使电解液容易渗透,从而促使膜容易剥落,磷酸盐和钒酸盐提高了电池的阳极效率,改善了电池的放电性能。Kartsonakis团队[46]研究了ZK30镁合金做阳极,在5/50 mmol/L NaCl基础电解液中添加磷酸氢二铵[(NH4)2HPO4]、氟化钙(CaF2)氟化钠(NaF)和硝酸锌[Zn(NO3)2]对镁合金在放电过程中耐蚀能力的影响。在5 mmol/L NaCl溶液的情况下,发现CaF2可以增强Mg ZK30放电过程中的耐蚀性;而对于50 mmol/L NaCl溶液来说,NaF、(NH4)2HPO4对Mg ZK30的腐蚀保护更强。这些结果可归因于在金属基材上形成的Mg3(PO4)2·22H2O、MgF2等复合物,避免了电解液直接与镁阳极接触对其造成的腐蚀。Wang等[47]研究了InCl3添加剂对Mg-0.15Ca阳极在3.5% NaCl溶液中的放电性能。从图4(d)可知,由于电解液中存在In3+的水解反应,能够在放电过程中延缓电解液碱化,使放电过程更均匀稳定。
无机添加剂主要通过影响镁阳极在放电过程中的自腐蚀速率或放电环境中的pH值来影响电池的放电过程,其原理为难溶盐沉淀或氧化-还原成膜,在镁表面构筑一层致密但可渗透的保护层,既能有效隔绝腐蚀性Cl⁻、抑制析氢,又可保持离子通道,降低极化并提高阳极利用率。
近年来,在水系镁空气电池电解液研究中,更多学者聚焦于有机添加剂。其主要通过阴离子作用,吸附在镁表面形成保护膜,抑制析氢和腐蚀[48]或与Mg²⁺、Fe3+形成可溶性络合物[20,49-50],抑制Mg(OH)₂的沉积,防止钝化,从而提高阳极利用率和放电电压。
Gao等[51]利用十二烷基硫酸钠(SDS)作为NaCl电解液添加剂,如图5(a)所示,添加SDS后,氢气的析出体积显著减少,AZ31B合金的自腐蚀行为也得到了延缓,且存在SDS添加剂的电解液中放电过程更为均匀。这主要是由于SDS在放电过程中可以吸附在AZ31B表面,AZ31B的溶解由于SDS的吸附过程而变得均匀。Sha等[52]将甘油(Gly)用作水性镁空气电池中的一种新型电解液添加剂,Gly通过形成静电屏蔽层、消耗双电层中的水分并促进溶剂化护套的重新配置来影响Mg阳极表面的剥离过程,有效减轻了自腐蚀和极化,其主要机理如图5(b)所示。Ling等[53-54]首次合成了一种新型离子液体2,6-二羟基苯甲酸胆碱([Ch][DHB]),并用作基于高纯镁(Hp-Mg)的水系镁空气电池的电解液添加剂,其中[DHB]-是Mg2+的络合剂,可以与Mg2+结合促进Mg基体的均匀溶解,从而提高阳极效率,[Ch]+是Mg阳极的缓蚀剂,可有效抑制Mg阳极的自腐蚀。Li等[55]在3.5% NaCl中加入0.05 mol/L的3,5-DHB(3,5-二羟基苯甲酸)、3,5-DHB与Mg2+形成可溶性复合物,显著降低了Mg阳极表面上不溶性排放产物的积累,提供了更活跃的放电位点,在低电流密度下改善了放电电压和比能量。另外,添加适当浓度的3,5-DHB可以抑制析氢速率,使Mg更均匀地溶解(图5(d)),从而提高了阳极效率。
在镁空气电池放电过程中,电解液中的有机添加剂主要通过官能团吸附或与Mg2+形成可溶性络合物,在镁阳极放电表面形成多功能界面,最终实现放电电压的提高。但单一的络合物作用可能难以实现屏蔽水分子、抑制析氢的作用,进而导致阳极利用率无法得到有效改善。
单一添加剂在调控镁空气电池性能时,往往难以在抑制自腐蚀与维持阳极活性之间取得理想平衡,难以兼顾放电电压、阳极利用率和放电稳定性。为此,研究者们转向探索混合添加剂体系[56-59],期望通过不同组分间的协同效应,实现性能的突破性提升。
现有研究已证实,合理设计的混合添加剂体系可通过多种机制协同作用,显著改善电池性能。Li等[60]将无机盐Na₃PO₄与表面活性剂十二烷基苯磺酸钠(SDBS)复配加入3.5% NaCl电解液中。其协同机制在于,PO43-与Mg²⁺反应生成溶解度更低的Mg₃(PO₄)₂,在阳极表面形成致密的内层保护膜;而SDBS则通过其疏水基团吸附在该沉积膜表面(图6(a)),形成有效的疏水屏障,进一步阻隔侵蚀性Cl⁻的渗透。二者协同将AZ91镁合金的自腐蚀抑制效率提升至95.2%,同时放电电压与阳极利用率均获得提高。Snihirova等[61]将NaNO₃与NaSal联用。NO3-作为氧化剂,能将镁合金中微电偶腐蚀产生的Fe²⁺氧化为Fe³⁺;而水杨酸根(SAL⁻)作为强络合剂,随即与Fe³⁺形成稳定的可溶性络合物,从而有效阻断了Fe³⁺/Fe²⁺的氧化还原循环及铁杂质在镁表面的再沉积,从源头上抑制了由杂质引发的微电偶腐蚀。该体系使商用纯镁阳极在5 mA/cm2下的利用率达到创纪录的82%,同时实现了镁的均匀溶解(图6(b))。Zhou等[62]则在含乙醇的NaCl电解液中引入多羟基有机酸(如3,4-DHB),乙醇促进了放电产物膜中致密内层的形成,有机酸进一步调控界面反应,协同提升了放电电压和阳极效率。
表2[44-47,51-55,60-62]汇总了单一添加剂及混合添加剂的相关性能对比,混合添加剂的协同作用使得镁阳极在均匀溶解提高放电电压的同时,阳极效率也有一定程度的提升。镁空气电池获得了更佳的放电性能,但相比于单一的添加剂而言,混合添加剂调配过程更为繁琐,然而目前多数不同电解液添加剂之间的相互影响机制尚不清楚。
近年来,随着计算化学与数据科学方法的深度融合,机器学习(machine learning, ML)技术在水系镁空气电池电解液研究中的应用逐渐成为热点[63-67]。研究者们不再仅仅依赖传统的试错式实验筛选,而是通过构建数据驱动的预测模型,从分子结构、电子特性及界面行为等多维度特征出发,高效优选适配的络合剂、解析Cl⁻、H₂O及有机阴离子在镁阳极表面的竞争吸附机制,为揭示和优化水系镁空气电池工作机理提供了全新视角。
机器学习辅助电解液设计:在特征构建方面,研究通常从分子描述入手,包括几何结构、电子分布、官能团特性以及溶剂化参数等。Wu等[64]采用原子位置平滑重叠(smooth overlap of atomic positions,SOAP)核函数将分子结构转化为高维特征向量,捕捉原子间空间分布的相似性,进而构建基于核主成分协变量回归(kernel principal covariates regression,KPCovR)的定量构效关系模型,如图7(a)~(e)所示。该模型以放电电位和阳极利用率为优化目标,通过多目标优化策略从商业化合物库中筛选潜在的高效添加剂。
机理研究的计算辅助验证:在机理阐释层面,机器学习与第一性原理计算、分子动力学模拟的结合,为理解电解液添加剂的作用机制提供了微观动态视角。Li等[65]通过密度泛函理论(DFT)计算和分子动力学(MD)模拟(图7(f)~(i)),系统研究了葡糖醛酸内酯(GLD)分子对Mg²⁺溶剂化结构的重构作用及其在镁表面的吸附行为。模拟结果表明,GLD可通过其羟基与羧基官能团与Mg²⁺配位,形成缺水型溶剂化鞘,同时通过氢键网络重构降低自由水活性,从而抑制析氢反应。这些计算结果为实验观察到的性能提升提供了理论支撑,并揭示了“氢键调控-界面工程”协同作用机制。Sha等[66]进一步采用分子动力学模拟,结合电荷布局分析与轨道能级计算,揭示了甘氨酸(Gly)在镁表面的优先化学吸附及其诱导形成的固态电解质界面(SEI)。Gly的两性离子结构使其能够同时作为氢键供体和受体,重组电极/电解液界面的水分子网络,形成缺水双电层(EDL)。该工作通过机器学习辅助,识别出Gly分子中氨基与羧基的协同吸附是提升界面稳定性的关键,为后续生物基添加剂的设计提供了理论指导。表3[64-66]对比了机器学习辅助电解液设计下的电池性能,其特定电流密度下的放电电压及比能量均显著提高。
结合近几年机器学习在镁空气电池电解液领域的研究,可以发现机器学习的引入在一定程度上推动并完善了镁空气电池放电过程的机理研究,加快了对优质放电阳极合金及适配电解液的筛选过程[66-67]。通过机器学习辅助验证电解液的作用机理,可深入地了解放电机制并为电解液的合理设计提供坚实的理论基础。众多实验结果表明[63-67],基于机器学习的选择策略在材料发现的实验设计中具有巨大潜力,理论计算和实验验证的有机结合可进一步推动高能量密度镁空气电池的前沿发展,这同时也为未来镁空气电池性能的提高及电解液的优化提供了新方向。
在全球气候变暖加剧和能源消耗与需求增加的双重压力下,化石能源向清洁能源的系统转型对保障能源安全与推动可持续发展具有重要意义[68]。水系镁空气电池凭借资源丰富、环境友好、6800 Wh/kg的高理论能量密度等优势被视为最具潜力的清洁能源之一。然而,该电池体系仍面临镁阳极自腐蚀与析氢、放电产物Mg(OH)₂堆积致表面钝化,以及低电流密度下“块状效应”等关键问题[69-70],降低了电池的放电电压与阳极利用率。与此同时,电解液改性以“最少改动、最低成本、最快见效”的方式,成为抑制析氢腐蚀与产物钝化、推动水系镁空气电池走向实用化的经济且灵活的关键途径。
目前对电解液的研究与设计主要分为基础电解液的选定和功能添加剂的添加:
(1)两类基础电解液分别为常用的含Cl-中性盐溶液和无氯近中性缓冲液,其中含氯中性盐溶液以3.5% NaCl为主,主要利用腐蚀性Cl-可以破坏放电产物表面的薄膜层,露出镁基体[71],从而提高放电活性,但Cl-的存在同时会诱发剧烈的HER;目前对无氯近中性电解液的研究以硝酸盐和其他腐蚀性较弱的盐类为主,没有了腐蚀性Cl-的存在,镁阳极表面的氧化膜变得更为致密[72],阻碍了镁阳极腐蚀的进一步发生,使放电过程更为均匀,从而提高了阳极效率。
(2)三类功能添加剂主要包括无机添加剂、有机添加剂和混合添加剂[73-74]。其中碳材料、钒酸盐等无机添加剂通过在阳极放电表面形成疏松多孔的氧化物膜或吸附于阳极表面抑制析氢等机理来改善电池的放电性能;而有机添加剂作为当前研究的热潮,主要通过添加剂中的阴离子吸附在镁表面形成保护膜来抑制HER或与 Mg²⁺、Fe3+形成可溶性络合物,抑制Mg(OH)₂的沉积进而防止钝化,提高阳极利用率和放电电压;单一的添加剂难以实现阳极利用率和放电电压的双重提高,因此也有一些研究者投入到混合添加剂的研究当中去。
在今后的研究当中,应致力于探索低成本、高适配、节能环保的新型电解液添加剂,以提升镁空气电池的综合性能。这一过程可通过以下途径来实现:
(1)推进电解液体系的绿色化设计:优先选用生物可降解、低毒或天然来源的有机分子作为添加剂(如多糖类、植物提取物衍生物、氨基酸类等),避免使用重金属或持久性有机污染物。统筹考虑其合成过程、使用效能及降解行为,推动电解液体系向环境友好、可持续方向发展。
(2)深化界面调控机制的理解:结合原位表征技术(如原位拉曼、电化学阻抗谱)与理论计算(如分子动力学、第一性原理),系统揭示添加剂在镁/电解液界面的吸附行为、膜层演化及电荷转移过程,明确其对析氢抑制与产物剥离的作用机制,为理性设计高性能界面调控层提供理论依据。
(3)建立并拓展有机络合剂、缓蚀剂及多元协同体系的数据库:通过第一性原理计算及实验数据同步验证并筛选出可行性添加剂,为低成本、高性能、无毒添加剂的合成提供研究方向。
(4)发展多元协同的复合添加剂体系:在明晰单一组分作用机制的基础上,设计具有多重功能(如络合、缓蚀、导电)的复合添加剂,通过组分间的协同效应实现腐蚀抑制、产物调控与电化学活性的平衡,进一步提升电池的综合性能与长期稳定性。
总之,水系镁空气电池电解液的优化是一个多维度、跨学科的课题。未来应通过绿色化学设计、界面机理研究、数据驱动筛选与多元协同策略的有机结合,系统推进电解液体系向高性能、低成本、环境友好的方向发展,最终实现镁空气电池阳极效率与放电电压的双重提升,推动其在大规模储能与应急电源等领域的实际应用。
  • 国家自然科学基金项目(52571128)
  • 国家自然科学基金项目(52171101)
  • 中央高校基本科研业务费(2024IAIS-QN009)
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2026年第54卷第5期
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doi: 10.11868/j.issn.1001-4381.2025.000761
  • 接收时间:2025-12-28
  • 首发时间:2026-10-27
  • 出版时间:2026-05-20
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  • 收稿日期:2025-12-28
  • 录用日期:2026-01-16
基金
国家自然科学基金项目(52571128)
国家自然科学基金项目(52171101)
中央高校基本科研业务费(2024IAIS-QN009)
作者信息
    1.重庆大学 材料科学与工程学院,重庆 400044
    2.重庆大学 国家镁合金工程研究中心,重庆 400044
    3.重庆市新型储能材料与装备研究院明月湖实验室,重庆 401122
    4.重庆大学 前沿交叉学科研究院,重庆 400044
    5.北京科技大学 国家材料服役安全科学中心,北京 100083
    6.重庆理工大学 材料科学与工程学院,重庆 400054

通讯作者:

吴量(1985—),男,教授,博士,主要从事镁合金表面腐蚀与防护及镁空气电池等相关工作,联系地址:重庆市沙坪坝区重庆大学A区综合实验大楼(400044),E-mail:
强玉杰(1992—),男,副教授,博士,主要从事绿色缓蚀新材料、金属空气电池、水系金属电池研究等相关工作,联系地址:北京市海淀区学院路30号北京科技大学国家材料服役安全科学中心(100083),E-mail:
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2种不同金属材料的力学参数
科
Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)
属
Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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