Progress on Organic Liquid Electrolytes for Rechargeable Magnesium Batteries AITranslate
Abstract AITranslate
With the rapid advancement of portable electronic devices，electric vehicles，smart grids，and other technologies，there is a pressing need to develop high-performance，cost-effective，and environmentally friendly electrochemical energy storage systems. Currently，the principal electrochemical energy storage systems in use include lead-acid batteries，lithium-ion batteries （LIBs），and flow batteries. In comparison to lead-acid batteries which are characterized by low energy density and significant environmental concerns，and flow batteries which exhibit low specific energy，LIBs have gained widespread adoption across various applications. This preference is attributed to their outstanding advantages，including high energy density，extended cycle life，and rapid charge and discharge capabilities. However，the limited availability of mineable lithium resources has led to a continuous increase in the cost of LIBs，necessitating the urgent exploration of alternative，low-cost energy storage technologies. Rechargeable magnesium batteries （RMBs） have emerged as a promising candidate for large-scale energy storage applications. Their potential is bolstered by the abundant reserves of magnesium，which contribute to lowering overall costs. Additionally，RMBs possess a high theoretical volumetric capacity of 3833 mAh·cm−3 and demonstrate a reduced propensity for dendrite formation during the deposition and dissolution processes. These factors have attracted significant interest from researchers in recent years，positioning RMBs as a viable alternative to traditional battery technologies. In the research and development of RMBs，the choice of magnesium-based electrolyte，as the medium for charge transfer，plays a vital role in the overall electrochemical characteristics of the battery. It not only dominates the solvation structure of magnesium ions but also deeply participates in the micro-electrochemical reactions at the electrolyte-electrode interface，directly determining key performance parameters such as the voltage window and battery reaction kinetics. Therefore，optimizing the electrolyte is one of the key challenges in the development of RMBs. An ideal magnesium-based electrolyte should possess the following core characteristics：first，it should enable reversible deposition/dissolution of the magnesium anode. Second，high ionic conductivity coupled with a wide voltage window ensures efficient battery operation and stability. Furthermore，good compatibility with cathode materials is indispensable. Last but not least，high safety is a basic requirement that magnesium-based electrolytes must meet in practical applications. In comparison to solid-state electrolytes，organic liquid electrolytes remain the mainstream choice for magnesium battery electrolyte research. This preference is due to their favorable properties，including high ionic conductivity，significant ionic transference numbers，excellent reversibility，prolonged cycling performance，ease of handling，as well as low viscosity. Historically，as early as 2000，Aurbach and his team successfully assembled the first prototype of an RMB based on Grignard reagent-based electrolyte （DCC，notably known as the first-generation magnesium-based electrolyte）. However，Grignard reagent-based electrolytes were hampered by several drawbacks，including high nucleophilicity，inadequate oxidation stability，poor compatibility with cathode materials，low conductivity，and high cost，posing challenges for large-scale commercial application. Subsequently，a series of novel magnesium-based organic liquid electrolyte systems have emerged，showcasing diverse characteristics. For instance，hexamethyldisilazide （HMDS）-based electrolytes were developed as non-nucleophilic electrolytes and demonstrated application in high-capacity magnesium-sulfur batteries. Inorganic salt-based electrolytes，represented by magnesium aluminum chloride complex （MACC），exhibited significant advantages in safety，ease of preparation，and economic feasibility. Non-chloride simple magnesium salts，exemplified by magnesium bis（trifluoromethanesulfonimide）（Mg（TFSI）2）and magnesium trifluoromethanesulfonate （Mg（OTf）2），are noteworthy for their high oxidation stability and non-corrosive properties. Organic boron-based electrolytes，characterized by large anions，showed excellent voltage windows and compatibility with both anode and cathode materials. Despite the significant progress made by the aforementioned novel organic liquid electrolyte systems in the research and development of RMBs，they still have many shortcomings. The high cost and complex synthesis process of HMDS-based electrolytes limit their widespread application. Chloride-containing inorganic salt-based electrolytes suffer from severe corrosion phenomena. Additionally，TFSI-based electrolytes exhibit severe passivation of the magnesium anode，leading to excessively high deposition/dissolution overpotentials，while OTf-based electrolytes demonstrate poor solubility in ether solvents. The preparation of organic boron-based electrolytes is often complicated and costly，with unresolved issues regarding ion transport at the interface and decomposition behaviors. Based on a systematic summary of the research status，the organic liquid electrolyte systems that are expected to achieve breakthroughs in the future are mainly concentrated in the chloride-free simple magnesium salts electrolytes and organic boron-based systems. Regarding chloride-free simple magnesium salt systems，strategies such as solvent regulation engineering，the introduction of salt additives for modification，and design regulation of the solid-electrolyte interphase （SEI） films can be employed to inhibit anode passivation and enhance magnesium salt solubility. For organic boron-based electrolytes，there is a dual need to develop new weakly coordinating boron-centered anionic electrolytes to further improve performance，as well as to explore entirely new preparation processes to reduce costs and enhance efficacy. This review highlighted the research progress of various organic liquid electrolytes for RMBs，introducing the structures，compositions，modification strategies，and associated electrochemical properties of different types of electrolytes. Furthermore，it provided insights into future research directions for organic liquid electrolytes in RMBs.
KeyWords AITranslate
［1］（邓凡锋，邓文清，张婷，王维康，刘洪刚，陈林，李浩，潘义，方正. 在线稀释-傅里叶变换红外光谱法用于质子交换膜燃料电池汽车用氢燃料中微痕量杂质组分的快速分析 ［J］. 分析试验室，2023，42（3） ：312.）
F F Deng，W Q Deng，T Zhang，W K Wang，H G Liu，L Chen，H Li，Y Pan，Z Fang. Rapid analysis of impurity components in fuel hydrogen for proton exchange membrane fuel cell vehicle using on-line dilution-Fourier transform infrared spectroscopy method ［J］. Chinese Journal of Analysis Laboratory，2023，42（3）：312.
［2］（麦俊杰，揭晓华，麦永津. 非均匀结构氧化铝铜合金力学和电学性能研究 ［J］. 铜业工程，2024，（5）：88.）
J J Mai，X H Jie，Y J Mai. Mechanical and electrical properties of heterostructured Cu-Al2O3 copper alloys ［J］. Copper Engineering，2024，（5）：88.
［3］（王中霆，邓容锐，李荣，黄光胜，王敬丰，潘复生. 镁二次电池负极材料的研究综述 ［J］. 稀有金属，2024，48（1）：79.）
Z T Wang，R R Deng，R Li，G S Huang，J F Wang，F S Pan. Review of research on anode materials for secondary magnesium batteries ［J］. Chinese Journal of Rare Metals，2024，48（1）：79.
［4］（陈莹，秦嘉壑，高志峰，沙俊辉，陈泰强. 锂离子电池快充电解液设计策略 ［J］. 稀有金属，2024，48（7）：1027.）
Y Chen，J H Qin，Z F Gao，J H Sha，T Q Chen. Electrolyte design strategies for fast-charging lithium-Ion batteries ［J］. Chinese Journal of Rare Metals，2024，48（7）：1027.
［5］Han G，Lu Y F，Jia H X，Ding Z，Wu L，Shi Y，Wang G Y，Luo Q，Wang J F，Huang G S，Zhou X Y，Li Q，Pan F S. Magnesium-based energy materials：progress，challenges，and perspectives ［J］. Journal of Magnesium and Alloys，2023，11（11）：2213.
［6］Aurbach D，Lu Z，Schechter A，Gofer Y，Gizbar H，Turgeman R，Cohen Y，Moshkovich M，Levi E. Prototype systems for rechargeable magnesium batteries ［J］. Nature，2000，407（6805）：724.
［7］Nelson J M，Evans W V. The electromotive force developed in cells containing nonaqueous liquids. ［J］. Journal of the American Chemical Society，1917，39（1）：82.
［8］Pour N，Gofer Y，Major D T，Aurbach D. Structural analysis of electrolyte solutions for rechargeable Mg batteries by stereoscopic means and DFT calculations ［J］. Journal of the American Chemical Society，2011，133（16）：6270.
［9］Liao C，Guo B K，Jiang D E，Custelcean R，Mahurin S M，Sun X G，Dai S. Highly soluble alkoxide magnesium salts for rechargeable magnesium batteries ［J］. Journal of Materials Chemistry A，2014，2（3）：581.
［10］Wang F F，Guo Y S，Yang J，Nuli Y N，Hirano S I. A novel electrolyte system without a Grignard reagent for rechargeable magnesium batteries ［J］. Chemical Communications，2012，48（87）：10763.
［11］Zhao Q S，Nuli Y N，Guo Y S，Yang J，Wang J L. Reversibility of electrochemical magnesium deposition from tetrahydrofuran solutions containing pyrrolidinyl magnesium halide ［J］. Electrochimica Acta，2011，56（18）：6530.
［12］（谢清水，汪依依，夏丽，张一鸣，瞿佰华，王敬丰，周小元，彭栋梁. 镁离子电池的工作原理与关键材料 ［J］. 金属功能材料，2024，31（1）：1.）
Q S Xie，Y Y Wang，L Xia，Y M Zhang，B H Qu，J F Wang，X Y Zhou，D L Peng. Working principle and key materials of Mg ion batteries ［J］. Metallic Functional Materials，2024，31（1）：1.
［13］（杜文涛，闫晓燕，刘宝胜，赵新新，张晓华，王明菊. 可充电镁硫二次电池的研究与展望 ［J］. 材料工程，2023. https://link.cnki.net/urlid/11.1800.TB.20231116.1015.002.）
W T Du，X Y Yan，B S Liu，X X Zhao，X H Zhang，M J Wang. Research progress of rechargeable magnesium-sulfur secondary batteries ［J］. Journal of Materials Engineering，2023. https://link.cnki.net/urlid/11.1800.TB.20231116.1015.002.
［14］（肖建华，赵宇星，范海燕，原华，张跃钢. 镁硫二次电池研究进展 ［J］. 硅酸盐学报，2020，48（7）：963.）
J H Xiao，Y X Zhao，H Y Fan，H Yuan，Y G Zhang. Research progress on rechargeable magnesium/sulfur battery ［J］. Journal of the Chinese Ceramic Society，2020，48（7）：963.
［15］（朱悦丹，王犟，努丽燕娜，武迪，郭瑞. 镁硫电池硫硒化合物正极材料的研究 ［J］. 上海航天（中英文），2021，38（5）：1.）
Y D Zhu，J Wang，Y N NuLi，D Wu，R Guo. Sulfur-selenium compound cathode materials for magnesium-sulfur battery ［J］. Aerospace Shanghai （Chinese & English），2021，38（5）：1.
［16］Liebenow C，Yang Z，Lobitz P. The electrodeposition of magnesium using solutions of organomagnesium halides，amidomagnesium halides and magnesium organoborates ［J］. Electrochemistry Communications，2000，2（9）：641.
［17］Kim H S，Arthur T S，Allred G D，Zajicek J，Newman J G，Rodnyansky A E，Oliver A G，Boggess W C，Muldoon J. Structure and compatibility of a magnesium electrolyte with a sulphur cathode ［J］. Nature Communications，2011，2（1）：427.
［18］Zhao-Karger Z，Zhao X Y，Fuhr O，Fichtner M. Bisamide based non-nucleophilic electrolytes for rechargeable magnesium batteries ［J］. RSC Advances，2013，3（37）：16330.
［19］Zhao-Karger Z，Mueller J E，Zhao X Y，Fuhr O，Jacob T，Fichtner M. Novel transmetalation reaction for electrolyte synthesis for rechargeable magnesium batteries ［J］. RSC Advances，2014，4（51）：26924.
［20］Chinnadurai D，Lieu W Y，Kumar S，Yang G L，Li Y J，Seh Z W. A passivation-free solid electrolyte interface regulated by magnesium bromide additive for highly reversible magnesium batteries ［J］. Nano Letters，2023，23（4）：1564.
［21］Gao T，Noked M，Pearse A J，Gillette E，Fan X L，Zhu Y J，Luo C，Suo L M，Schroeder M A，Xu K，Lee S B，Rubloff G W，Wang C S. Enhancing the reversibility of Mg/S battery chemistry through Li+ mediation ［J］. Journal of the American Chemical Society，2015，137（38）：12388.
［22］Bhardwaj R K，Bhattacharyya A J. Efficient magnesium plating and stripping in DOL/DME-Mg（HMDS）2-based electrolytes and application in Mg/S batteries ［J］. ACS Applied Energy Materials，2021，4（12）：14121.
［23］Lu Z，Schechter A，Moshkovich M，Aurbach D. On the electrochemical behavior of magnesium electrodes in polar aprotic electrolyte solutions ［J］. Journal of Electroanalytical Chemistry，1999，466（2）：203.
［24］Doe R E，Han R B，Hwang J，Gmitter A J，Shterenberg I，Yoo H D，Pour N，Aurbach D. Novel，electrolyte solutions comprising fully inorganic salts with high anodic stability for rechargeable magnesium batteries ［J］. Chemical Communications，2014，50（2）：243.
［25］He S J，Luo J，Liu T L. MgCl2/AlCl3 electrolytes for reversible Mg deposition/stripping：electrochemical conditioning or not？ ［J］. Journal of Materials Chemistry A，2017，5（25）：12718.
［26］Kim S S，Bevilacqua S C，See K A. Conditioning-free Mg electrolyte by the minor addition of Mg（HMDS）2 ［J］. ACS Applied Materials & Interfaces，2019，12（5）：5226.
［27］Luo J，He S J，Liu T L. Tertiary Mg/MgCl2/AlCl3 inorganic Mg2+electrolytes with unprecedented electrochemical performance for reversible Mg deposition ［J］. ACS Energy Letters，2017，2（5）：1197.
［28］Ha J H，Adams B，Cho J H，Duffort V，Kim J H，Chung K Y，Cho B W，Nazar L F，Oh S H. A conditioning-free magnesium chloride complex electrolyte for rechargeable magnesium batteries ［J］. Journal of Materials Chemistry A，2016，4（19）：7160.
［29］Fan H Y，Zhang X X，Zhao Y X，Xiao J H，Yuan H，Wang G，Lin Y T，Zhang J F，Pan L D，Pan T，Liu Y，Zhang Y G. Tailoring Mg2+ solvation structure in a facile all-inorganic ［MgxLiyCl2x+y·nTHF］ complex electrolyte for high rate and long cycle-life Mg battery ［J］. Energy & Environmental Materials，2023，6（2）：e12327.
［30］Ha S Y，Lee Y W，Woo S W，Koo B，Kim J S，Cho J，Lee K T，Choi N S. Magnesium（Ⅱ） bis（trifluoromethane sulfonyl） imide-based electrolytes with wide electrochemical windows for rechargeable magnesium batteries ［J］. ACS Applied Materials & Interfaces，2014，6（6）：4063.
［31］（李亚琦，左朋建，李睿楠，马玉林，尹鸽平. 镁硫二次电池电解液 ［J］. 化学进展，2017，29（5）：553.）
Y Q Li，P J Zuo，R N Li，Y L Ma，G P Yin. Electrolytes for rechargeable magnesium-sulfur batteries ［J］. Progress in Chemistry，2017，29（5）：553.
［32］Salama M，Shterenberg I，Gizbar H，Eliaz N N，Kosa M，Keinan-Adamsky K，Afri M，Shimon L J W，Gottlieb H E，Major D T，Gofer Y，Aurbach D. Unique behavior of dimethoxyethane （DME）/Mg（N（SO2CF3）2）2 solutions ［J］. Journal of Physical Chemistry C，2016，120（35）：19586.
［33］Rajput N N，Qu X H，Sa N，Burrell A K，Persson K A. The coupling between stability and ion pair formation in magnesium electrolytes from first-principles quantum mechanics and classical molecular dynamics ［J］. Journal of the American Chemical Society，2015，137（9）：3411.
［34］Hahn N T，Kamphaus E P，Chen Y，Murugesan V，Mueller K T，Cheng L，Zavadil K R. Magnesium battery electrolytes with improved oxidative stability enabled by selective solvation in fluorinated solvents ［J］. ACS Applied Energy Materials，2023，6（6）：3264.
［35］Yang Y Y，Wang J Z，Du X F，Jiang H Z，Du A B，Ge X S，Li N，Wang H，Zhang Y C，Chen Z，Zhao J W，Cui G L. Cation co-Intercalation with anions：the origin of low capacities of graphite cathodes in multivalent electrolytes ［J］. Journal of the American Chemical Society，2023，145（22）：12093.
［36］He Y S，Li Q，Yang L L，Yang C R，Xu D S. Electrochemical-conditioning-free and water-resistant hybrid AlCl3/MgCl2/Mg（TFSI）2 electrolytes for rechargeable magnesium batteries ［J］. Angewandte Chemie，2019，131（23）：7697.
［37］Sun Y，Wang Y H，Jiang L W，Dong D J，Wang W W，Fan J，Lu Y C. Non-nucleophilic electrolyte with non-fluorinated hybrid solvents for long-life magnesium metal batteries ［J］. Energy & Environmental Science，2023，16（1）：265.
［38］Li X G，Gao T，Han F D，Ma Z H，Fan X L，Hou S，Eidson N，Li W S，Wang C S. Reducing Mg anode overpotential via ion conductive surface layer formation by iodine additive ［J］. Advanced Energy Materials，2018，8（7）：1701728.
［39］Hardin N Z，Woodley C P，McDonald K D，Bartlett B M. Triiodide anion as a magnesium-ion transporter for low overpotential battery cycling in iodine-containing Mg（TFSI）2 electrolyte ［J］. ACS Applied Materials & Interfaces，2024，16（12）：14883.
［40］Hou S，Ji X，Gaskell K，Wang P F，Wang L N，Xu J J，Sun R M，Borodin O，Wang C S. Solvation sheath reorganization enables divalent metal batteries with fast interfacial charge transfer kinetics ［J］. Science，2021，374（6564）：172.
［41］Li C，Guha R D，Shyamsunder A，Persson K A，Nazar L F. A weakly ion pairing electrolyte designed for high voltage magnesium batteries ［J］. Energy & Environmental Science，2024，17（1）：190.
［42］Wang S Y，Wang K W，Zhang Y C，Jie Y L，Li X P，Pan Y X，Gao X W，Nian Q S，Cao R G，Li Q，Jiao S H，Xu D S. High-entropy electrolyte enables high reversibility and long lifespan for magnesium metal anodes ［J］. Angewandte Chemie International Edition，2023，62（31）：e202304411.
［43］Amir N，Vestfrid Y，Chusid O，Gofer Y，Aurbach D. Progress in nonaqueous magnesium electrochemistry ［J］. Journal of Power Sources，2007，174（2）：1234.
［44］Huang D，Tan S S，Li M S，Wang D D，Han C H，An Q Y，Mai L Q. Highly efficient non-nucleophilic Mg（CF3SO3）2-based electrolyte for high-power Mg/S battery ［J］. ACS Applied Materials & Interfaces，2020，12（15）：17474.
［45］Yang G L，Li Y J，Zhang C，Wang J B，Bai Y，Lim C Y J，Ng M F，Chang Z，Kumar S，Sofer Z，Liu W，Seh Z W. In situ formed magnesiophilic sites guiding uniform deposition for stable magnesium metal anodes ［J］. Nano Letters，2022，22（22）：9138.
［46］Zhang D，Duan S Z，Liu X S，Yang Y，Zhang Y，Ren W，Zhang S X，Cheng M X，Yang W J，Wang J L，NuLi Y N. Deeping insight of Mg（CF3SO3）2 and comprehensive modified electrolyte with ionic liquid enabling high-performance magnesium batteries ［J］. Nano Energy，2023，109：108257.
［47］Du Y Y，Chen Y M，Tan S S，Chen J L，Huang X T，Cui L M，Long J C，Wang Z T，Yao X H，Shang B，Huang G S，Zhou X Y，Li L J，Wang J F，Pan F S. Strong solvent coordination effect inducing gradient solid-electrolyte-interphase formation for highly efficient Mg plating/stripping ［J］. Energy Storage Materials，2023，62：102939.
［48］Connor J H，Reid W E，Wood G B. Electrodeposition of metals from organic solutions：V. electrodeposition of magnesium and magnesium alloys ［J］. Journal of the Electrochemical Society，1957，104（1）：38.
［49］Zhao X Y，Zhao-Karger Z，Wang D，Fichtner M. Metal oxychlorides as cathode materials for chloride ion batteries ［J］. Angewandte Chemie，2013，125（51）：13866.
［50］Guo Y S，Zhang F，Yang J，Wang F F，NuLi Y N，Hirano S I. Boron-based electrolyte solutions with wide electrochemical windows for rechargeable magnesium batteries ［J］. Energy & Environmental Science，2012，5（10）：9100.
［51］Zhang Z H，Cui Z L，Qiao L X，Guan J，Xu H M，Wang X G，Hu P，Du H P，Li S Z，Zhou X H，Dong S M，Liu Z H，Cui G L，Chen L Q. Novel design concepts of efficient Mg-Ion electrolytes toward high-performance magnesium-selenium and magnesium-sulfur batteries ［J］. Advanced Energy Materials，2017，7（11）：1602055.
［52］Zhao-Karger Z，Liu R Y，Dai W X，Li Z Y，Diemant T，Vinayan B，Bonatto Minella C，Yu X W，Manthiram A，Behm R J. Toward highly reversible magnesium-sulfur batteries with efficient and practical Mg［B（hfip）4］2 electrolyte ［J］. ACS Energy Letters，2018，3（8）：2005.
［53］Xu H M，Zhang Z H，Cui Z L，Du A B，Lu C L，Dong S M，Ma J，Zhou X H，Cui G L. Strong anion receptor-assisted boron-based Mg electrolyte with wide electrochemical window and non-nucleophilic characteristic ［J］. Electrochemistry Communications，2017，83：72.
［54］（王玉琪，蓝海航，侯琼，曾荣华，高进伟. 蒽醌类有机电极材料在新型二次电池中的应用研究进展 ［J］. 稀有金属，2022，46（2）：238.）
Y Q Wang，H H Lan，Q Hou，R H Zeng，J W Gao. Progress in application of anthraquinone organic electrode materials in new secondary batteries ［J］. Chinese Journal of Rare Metals，2022，46（2）：238.
［55］Tang K，Du A，Dong S M，Cui Z L，Liu X，Lu C L，Zhao J W，Zhou X H，Cui G L. A stable solid electrolyte interphase for magnesium metal anode evolved from a bulky anion lithium salt ［J］. Advanced Materials，2020，32（6）：1904987.
［56］Meng Z，Li Z Y，Wang L P，Diemant T，Bosubabu D，Tang Y S，Berthelot R，Zhao-Karger Z，Fichtner M. Surface engineering of a Mg electrode via a new additive to reduce overpotential ［J］. ACS Applied Materials & Interfaces，2021，13（31）：37044.
［57］Parambath V B，Zhao-Karger Z，Diemant T，Jaeckle M，Li Z，Scherer T，Gross A，Behm R J，Fichtner M. Investigation on the formation of Mg metal anode/electrolyte interfaces in Mg/S batteries with electrolyte additives ［J］. Journal of Materials Chemistry A，2020，8（43）：22998.
［58］Ren W，Wu D，NuLi Y N，Zhang D，Yang Y，Wang Y，Yang J，Wang J L. An efficient bulky Mg［B（Otfe）4］2 electrolyte and its derivatively general design strategy for rechargeable magnesium batteries ［J］. ACS Energy Letters，2021，6（9）：3212.
［59］Long J C，An Y K，Yang Z Z，Zhang G，Zhang J Y，Tan S X，An Q Y. Efficient boron-based electrolytes constructed by anionic and interfacial co-regulation for rechargeable magnesium batteries ［J］. Chemical Engineering Journal，2023，461：141901.
［60］Long J C，Tan S S，Wang J J，Xiong F Y，Cui L M，An Q Y，Mai L Q. Revealing the interfacial chemistry of fluoride alkyl magnesium salts in magnesium metal batteries ［J］. Angewandte Chemie，2023，135（21）：e202301934.
［61］Carter T J，Mohtadi R，Arthur T S，Mizuno F，Zhang R，Shirai S，Kampf J W. Boron clusters as highly stable magnesium‐battery electrolytes ［J］. Angewandte Chemie，2014，126（12）：3237.
［62］Tutusaus O，Mohtadi R，Arthur T S，Mizuno F，Nelson E G，Sevryugina Y V. An efficient halogen-free electrolyte for use in rechargeable magnesium batteries ［J］. Angewandte Chemie，2015，127（27）：8011.
［63］McArthur S G，Jay R，Geng L，Guo J，Lavallo V. Below the 12-vertex：10-vertex carborane anions as non-corrosive，halide free，electrolytes for rechargeable Mg batteries ［J］. Chemical Communications，2017，53（32）：4453.
［64］McArthur S G，Geng L，Guo J，Lavallo V. Cation reduction and comproportionation as novel strategies to produce high voltage，halide free，carborane based electrolytes for rechargeable Mg batteries ［J］. Inorganic Chemistry Frontiers，2015，2（12）：1101.
［65］Hahn N T，Seguin T J，Lau K C，Liao C，Ingram B J，Persson K A，Zavadil K R. Enhanced stability of the carba-closo-dodecaborate anion for high-voltage battery electrolytes through rational design ［J］. Journal of the American Chemical Society，2018，140（35）：11076.
Basic Information:
DOI：10.13373/j.cnki.cjrm.XY25020006
Chinese Library Classification Number:TK91
Citation Information:
With the rapid advancement of portable electronic devices，electric vehicles，smart grids，and other technologies，there is a pressing need to develop high-performance，cost-effective，and environmentally friendly electrochemical energy storage systems. Currently，the principal electrochemical energy storage systems in use include lead-acid batteries，lithium-ion batteries （LIBs），and flow batteries. In comparison to lead-acid batteries which are characterized by low energy density and significant environmental concerns，and flow batteries which exhibit low specific energy，LIBs have gained widespread adoption across various applications. This preference is attributed to their outstanding advantages，including high energy density，extended cycle life，and rapid charge and discharge capabilities. However，the limited availability of mineable lithium resources has led to a continuous increase in the cost of LIBs，necessitating the urgent exploration of alternative，low-cost energy storage technologies. Rechargeable magnesium batteries （RMBs） have emerged as a promising candidate for large-scale energy storage applications. Their potential is bolstered by the abundant reserves of magnesium，which contribute to lowering overall costs. Additionally，RMBs possess a high theoretical volumetric capacity of 3833 mAh·cm−3 and demonstrate a reduced propensity for dendrite formation during the deposition and dissolution processes. These factors have attracted significant interest from researchers in recent years，positioning RMBs as a viable alternative to traditional battery technologies. In the research and development of RMBs，the choice of magnesium-based electrolyte，as the medium for charge transfer，plays a vital role in the overall electrochemical characteristics of the battery. It not only dominates the solvation structure of magnesium ions but also deeply participates in the micro-electrochemical reactions at the electrolyte-electrode interface，directly determining key performance parameters such as the voltage window and battery reaction kinetics. Therefore，optimizing the electrolyte is one of the key challenges in the development of RMBs. An ideal magnesium-based electrolyte should possess the following core characteristics：first，it should enable reversible deposition/dissolution of the magnesium anode. Second，high ionic conductivity coupled with a wide voltage window ensures efficient battery operation and stability. Furthermore，good compatibility with cathode materials is indispensable. Last but not least，high safety is a basic requirement that magnesium-based electrolytes must meet in practical applications. In comparison to solid-state electrolytes，organic liquid electrolytes remain the mainstream choice for magnesium battery electrolyte research. This preference is due to their favorable properties，including high ionic conductivity，significant ionic transference numbers，excellent reversibility，prolonged cycling performance，ease of handling，as well as low viscosity. Historically，as early as 2000，Aurbach and his team successfully assembled the first prototype of an RMB based on Grignard reagent-based electrolyte （DCC，notably known as the first-generation magnesium-based electrolyte）. However，Grignard reagent-based electrolytes were hampered by several drawbacks，including high nucleophilicity，inadequate oxidation stability，poor compatibility with cathode materials，low conductivity，and high cost，posing challenges for large-scale commercial application. Subsequently，a series of novel magnesium-based organic liquid electrolyte systems have emerged，showcasing diverse characteristics. For instance，hexamethyldisilazide （HMDS）-based electrolytes were developed as non-nucleophilic electrolytes and demonstrated application in high-capacity magnesium-sulfur batteries. Inorganic salt-based electrolytes，represented by magnesium aluminum chloride complex （MACC），exhibited significant advantages in safety，ease of preparation，and economic feasibility. Non-chloride simple magnesium salts，exemplified by magnesium bis（trifluoromethanesulfonimide）（Mg（TFSI）2）and magnesium trifluoromethanesulfonate （Mg（OTf）2），are noteworthy for their high oxidation stability and non-corrosive properties. Organic boron-based electrolytes，characterized by large anions，showed excellent voltage windows and compatibility with both anode and cathode materials. Despite the significant progress made by the aforementioned novel organic liquid electrolyte systems in the research and development of RMBs，they still have many shortcomings. The high cost and complex synthesis process of HMDS-based electrolytes limit their widespread application. Chloride-containing inorganic salt-based electrolytes suffer from severe corrosion phenomena. Additionally，TFSI-based electrolytes exhibit severe passivation of the magnesium anode，leading to excessively high deposition/dissolution overpotentials，while OTf-based electrolytes demonstrate poor solubility in ether solvents. The preparation of organic boron-based electrolytes is often complicated and costly，with unresolved issues regarding ion transport at the interface and decomposition behaviors. Based on a systematic summary of the research status，the organic liquid electrolyte systems that are expected to achieve breakthroughs in the future are mainly concentrated in the chloride-free simple magnesium salts electrolytes and organic boron-based systems. Regarding chloride-free simple magnesium salt systems，strategies such as solvent regulation engineering，the introduction of salt additives for modification，and design regulation of the solid-electrolyte interphase （SEI） films can be employed to inhibit anode passivation and enhance magnesium salt solubility. For organic boron-based electrolytes，there is a dual need to develop new weakly coordinating boron-centered anionic electrolytes to further improve performance，as well as to explore entirely new preparation processes to reduce costs and enhance efficacy. This review highlighted the research progress of various organic liquid electrolytes for RMBs，introducing the structures，compositions，modification strategies，and associated electrochemical properties of different types of electrolytes. Furthermore，it provided insights into future research directions for organic liquid electrolytes in RMBs.
quote
| GB/T 7714-2015 | [1] Chengfeng Jiang, Hongxing Jia, Guangsheng Huang, et al. Progress on Organic Liquid Electrolytes for Rechargeable Magnesium Batteries[J]. Chinese Journal of Rare Metals, 2025, 49(10): 1562-1574. DOI:10.13373/j.cnki.cjrm.XY25020006. |
| MLA | [1] Chengfeng Jiang, et al., "Progress on Organic Liquid Electrolytes for Rechargeable Magnesium Batteries." Chinese Journal of Rare Metals, vol. 49, no. 10, 2025, pp. 1562-1574, https://doi.org/10.13373/j.cnki.cjrm.XY25020006. |
| APA | [1] Chengfeng Jiang, Hongxing Jia, Guangsheng Huang, Xiaoyuan Zhou, Jingfeng Wang, & Fusheng Pan. (2025). Progress on Organic Liquid Electrolytes for Rechargeable Magnesium Batteries. Chinese Journal of Rare Metals, 49(10), 1562-1574. https://doi.org/10.13373/j.cnki.cjrm.XY25020006 |
| IEEE | [1] Chengfeng Jiang, Hongxing Jia, Guangsheng Huang, Xiaoyuan Zhou, Jingfeng Wang, and Fusheng Pan, "Progress on Organic Liquid Electrolytes for Rechargeable Magnesium Batteries," Chinese Journal of Rare Metals, vol. 49, no. 10, pp. 1562-1574, 2025, doi: 10.13373/j.cnki.cjrm.XY25020006. keywords: {rechargeable magnesium batteries;magnesium-based electrolytes;organic liquid electrolytes;electrochemical properties} |