Understanding the Cathode‐Electrolyte Interfacial Chemistry in Rechargeable Magnesium Batteries

Advanced Science, Год журнала: 2024, Номер 11(25)

Опубликована: Апрель 6, 2024

Abstract Rechargeable magnesium batteries (RMBs) have garnered significant attention due to their potential provide high energy density, utilize earth‐abundant raw materials, and employ metal anode safely. Currently, the lack of applicable cathode materials has become one bottleneck issues for fully exploiting technological advantages RMBs. Recent studies on Mg cathodes reveal divergent storage performance depending electrolyte formulation, posing interfacial as a previously overlooked challenge. This minireview begins with an introduction representative cathode‐electrolyte phenomena in RMBs, elaborating unique solvation behavior 2+ , which lays foundation chemistries. It is followed by presenting recently developed strategies targeting promotion desolvation alternative cointercalation approaches circumvent step. In addition, efforts enhance compatibility via development engineering are highlighted. Based abovementioned discussions, this finally puts forward perspectives challenges establishment stable interface fast chemistry

Язык: Английский

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Bottom‐Up Magnesium Deposition Induced by Paper‐Based Triple‐Gradient Scaffolds toward Flexible Magnesium Metal Batteries

Advanced Materials, Год журнала: 2023, Номер 36(9)

Опубликована: Ноя. 3, 2023

Abstract The development of advanced magnesium metal batteries (MMBs) has been hindered by longstanding challenges, such as the inability to induce uniform (Mg) nucleation and inefficient utilization Mg foil. This study introduces a novel solution in form flexible, lightweight, paper‐based scaffold that incorporates gradient conductivity, magnesiophilicity, pore size. design is achieved through an industrially adaptable papermaking process which ratio carboxylated multi‐walled carbon nanotubes softwood cellulose fibers meticulously adjusted. triple‐gradient structure enables regulation ion flux, promoting bottom‐up deposition. Owing its high flexibility, low thickness, reduced density, potential applications flexible wearable electronics. Accordingly, electrodes exhibit stable operation for over 1200 h at 3 mA cm −2 /3 mAh symmetrical cells, markedly outperforming non‐gradient metallic alternatives. Notably, this marks first successful fabrication MMB pouch full cell, achieving impressive volumetric energy density 244 Wh L −1 . simplicity scalability design, uses readily available materials compatible process, open new doors production high‐energy‐density batteries.

Язык: Английский

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Challenges and Progress in Rechargeable Magnesium‐Ion Batteries: Materials, Interfaces, and Devices

Advanced Functional Materials, Год журнала: 2024, Номер unknown

Опубликована: Сен. 17, 2024

Abstract Rechargeable magnesium‐ion batteries (RMBs) have garnered increasing research interest in the field of post‐lithium‐ion battery technologies owing to their potential for high energy density, enhanced safety, cost‐effectiveness, and material resourcefulness. Despite substantial advancements RMB research, a number intrinsic challenges remain unresolved, such as strong Coulombic interaction between Mg 2+ host crystal structure cathode materials, sluggish diffusion kinetic, poor electrolyte compatibility, formation passivation films on anode interface. These issues hinder commercial applications RMBs. This review provides comprehensive overview progress key areas including representative storage cathode/anode materials conducting electrolytes. Additionally, recent developments electrode‐electrolyte interface regulations pouch‐cell fabrication are outlined, highlighting current implementation effective solutions. Finally, future directions proposed guide development high‐performance RMBs with practical applications.

Язык: Английский

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Insights into Hyper-Efficient Construction of Compact Artificial SEI for Highly Reversible Mg Metal Anode

ACS Energy Letters, Год журнала: 2024, Номер unknown, С. 5616 - 5626

Опубликована: Окт. 29, 2024

Язык: Английский

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Asymmetric SO₃CF₃⁻‐Grafted Boron‐Center Anion Enables Boron‐Containing Interphase for High‐Performance Rechargeable Mg Batteries

Advanced Functional Materials, Год журнала: 2024, Номер 34(17)

Опубликована: Янв. 4, 2024

Abstract Mg(SO 3 CF ) 2 (Mg(OTf) is a simple and cost‐effective magnesium salt, which can promote the future applications of rechargeable batteries (RMBs). However, Mg(OTf) /ether electrolytes suffer from poor electrochemical properties due to low solubility serious decomposition passivation [Mg 2+ ‐OTf − ] ion pair on Mg. Herein, OTf anion successfully grafted low‐cost fluoride boronic esters (B(OC x H y F 2x‐y+1 obtain asymmetric weak‐coordination boron‐center [B(OC OTf] in ether electrolytes. The ‐OCH (TFE) groups B(TFE) effectively realize charge delocalization B‐O plane, restraining independent pair. co‐decomposition [B(TFE) induces formation B‐containing organic/inorganic interphase, thus achieving reversible Mg plating/stripping. After further solubilization reaction, obtained electrolyte exhibits high average coulombic efficiency 98.13% long‐term cycling stability (1000 h). Notably, long life (capacity retention 90.2% after 600 cycles at 1 C) high‐rate capacity (43.0 mAh g −1 5 Mg/Mo 6 S 8 full cell demonstrate favorable electrolyte/cathode compatibility. This work brings new insights design new‐type Mg‐salts high‐performance for commercial RMBs.

Язык: Английский

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Recent progress of magnesium electrolytes for rechargeable magnesium batteries

Coordination Chemistry Reviews, Год журнала: 2024, Номер 515, С. 215956 - 215956

Опубликована: Май 20, 2024

Язык: Английский

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Redesigning Solvation Structure toward Passivation-Free Magnesium Metal Batteries

ACS Nano, Год журнала: 2024, Номер 18(23), С. 15239 - 15248

Опубликована: Май 29, 2024

Simple magnesium (Mg) salt solutions are widely considered as promising electrolytes for next-generation rechargeable Mg metal batteries (RMBs) owing to the direct Mg2+ storage mechanism. However, passivation layer formed on anodes in these is key challenge that limits its applicability. Numerous complex halogenide additives have been introduced etch away layer, nevertheless, at expense of electrolyte's anodic stability and cathodes' cyclability. To overcome this dilemma, here, we design an electrolyte with a weakly coordinated solvation structure which enables passivation-free deposition while maintaining high cathodic compatibility. In detail, successfully introduce hexa-fluoroisopropyloxy (HFIP–) anion into Mg2+, [Mg–HFIP]+ contact ion pair facilitates transportation across interfaces. As consequence, our shows outstanding compatibility RMBs. The Mg||PDI–EDA Mg||Mo6S8 full cells use demonstrating decent capacity retention ∼80% over 400 cycles 500 cycles, respectively. This represents leap cyclability simple RMBs rest can barely cycle. work offers system compatible brings deeper understanding modifying toward practical electrolytes.

Язык: Английский

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Large-Scale Integration of the Ion-Reinforced Phytic Acid Layer Stabilizing Magnesium Metal Anode

ACS Nano, Год журнала: 2024, Номер 18(18), С. 11740 - 11752

Опубликована: Апрель 22, 2024

Rechargeable magnesium batteries (RMBs) have garnered significant attention for their potential in large-scale energy storage applications. However, the commercial development of RMBs has been severely hampered by rapid failure large-sized Mg metal anodes, especially under fast and deep cycling conditions. Herein, a concept proof involving ion-reinforced phytic acid (PA) layer (100 cm × 7.5 cm) with an excellent water-oxygen tolerance, high Mg2+ conductivity, favorable electrochemical stability is proposed to enable uniform plating/stripping anode. Guided even distributions flux electric field, as-prepared PA-Al@Mg electrode (5.8 4.5 exhibits no perforation after cycling. Consequently, ultralong lifespan (2400 h at 3 mA cm-2 1 mAh cm-2) current tolerance (300 9 symmetric cell using anode could be achieved. Notably, PA-Al@Mg//Mo6S8 full demonstrates exceptional stability, operating 8000 cycles 5 C capacity retention 99.8%, surpassing that bare (3000 cycles, 74.7%). Moreover, successfully contributes stable pouch (200 750 0.1 C), further confirming its practical utilization. This work provides valuable theoretical insights technological support implementation RMBs.

Язык: Английский

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Contact Ion-Pair-Dominated Electrolyte Enabling Inorganic-Rich Solid–Electrolyte Interphase for Long-Cycling Magnesium Metal Anodes

ACS Energy Letters, Год журнала: 2025, Номер unknown, С. 552 - 561

Опубликована: Янв. 1, 2025

Mg anodes are hindered by a huge overpotential and limited cycling life, stemming primarily from the unstable interphase between electrolyte. An effective approach lies in establishing an anion-derived, inorganic-rich solid–electrolyte (SEI) that mitigates continuous reduction of Nevertheless, high charge density divalent cations poses significant challenge balancing coordination dissociation anions within Mg2+ solvation sheath. Herein, selecting small-sized OTf–, diglyme solvent, trimethyl phosphate (TMP) as cosolvents with similar donor number (DN) values, electrolyte-dominated Mg2+–OTf– contact ion-pair configuration is achieved, further deriving stable inorganic SEI containing fluoride phosphide components. Among them, TMP can break lattice energy magnesium salts, while OTf– low electron delocalization ensure degree Mg2+, jointly realizing anion chemistry. MgF2 MgS, dominated decomposition at potential 0.6 V (vs Mg/Mg2+), enhance electronic insulation interphase. Consequently, exhibit superior performance over 3200 h polarization (<0.1 V) excellent plating/stripping Coulombic efficiency 1000 cycles 0.1 mA cm–2.

Язык: Английский

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Anion-Regulated Solvation Structure and Electrode Interface toward Rechargeable Magnesium Batteries

Nano Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 13, 2025

Developing chlorine-free electrolytes enabling fast Mg2+ transport through a solid/cathode-electrolyte interphase (SEI/CEI) remains critical for rechargeable magnesium batteries (RMBs). However, single-anion often lack the necessary redox properties this requirement. Here, we propose dual-anion electrolyte combining bis(trifluoromethanesulfonyl)imide and 1-butyl-1-methylpiperidinium trifluoromethylsulfonate (PP14CF3SO3) in diglyme 2-methoxyethylamine (MOEA) solvent, achieving efficient Mg plating/stripping, cathode compatibility, high anodic stability. The electrostatic interactions between MOEA Mg2+/CF3SO3– stabilize Mg-anode SEI while fostering CxNy-rich CEI formation. This leads to significantly improved performance Mg∥Mg stainless steel (SS)∥Mg cells, with an extended lifespan over 2500 h average Coulombic efficiency of 98.1%, respectively. Mo6S8∥Mg full cells exhibit excellent rate performance, poly(6,6′,6″-(benzene-1,3,5-triyl)tris(9,10-anthracenedione)) (PBAQ)∥Mg operate at 2.8 V (1 A g–1) ∼70% capacity retention after 200 cycles. work highlights anion-mediated solvation regulation, providing insights into advanced engineering high-performance RMBs.

Язык: Английский

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