Highly Compact Zinc Metal Anode and Wide‐Temperature Aqueous Electrolyte Enabled by Acetamide Additives for Deep Cycling Zn Batteries

Advanced Functional Materials, Год журнала: 2024, Номер 34(18)

Опубликована: Янв. 25, 2024

Abstract Rechargeable aqueous zinc (Zn) batteries are a promising candidate for large‐scale energy storage, but the noncompact and dendritic Zn deposition, water‐induced parasitic reaction, narrow operating temperature range severely hinder their practical application. Here, it is demonstrated that these challenges can be conquered by introducing low‐cost acetamide (Ace) into electrolytes. The non‐sacrificial Ace molecules with both donor acceptor groups disrupt original H‐bonded network of water, replace solvating‐H 2 O in 2+ ‐solvation sheath, form dynamic adsorption on Zn, create an H O‐poor electrical double‐layer. Consequently, presence suppresses water erosion homogenizes nucleation/growth, reduces reactivity, depresses freezing point electrolyte. formulated Ace‐containing electrolyte features wide from −20 to 60 °C enables highly compact dendrite‐free electrodeposition even at 25 mAh cm −2 using non‐pressure electrolytic cell. Moreover, allows electrodes achieve long‐term lifespan across −20–60 excellent deep cycling stability under 85.3% depth‐of‐discharge (25 ) over 400 h, supports stable operation Zn–Iodine full harsh conditions.

Язык: Английский

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Selective Shielding of the (002) Plane Enabling Vertically Oriented Zinc Plating for Dendrite‐Free Zinc Anode

Advanced Materials, Год журнала: 2023, Номер 36(11)

Опубликована: Дек. 13, 2023

Uncontrolled growth of Zn dendrites hinders the future development aqueous Zn-ion batteries. Despite that (100) plane possesses better zincophilic ability and fast kinetics, are generally suppressed via (002) plane-oriented deposition in previous reports; ordered plane-dominant deposition, especially under high current density has not yet been realized. Herein, vertically-oriented plating with preferential is reported using disodium lauryl phosphate (DLP) as an electrolyte additive. DLP preferentially anchored on crystal polar group, then atoms retarded by long alkyl chain, finally promoting preferred plane. This unique pattern results ultrastable plating/stripping at a super-high 50 mA cm

Язык: Английский

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Polymer Molecules Adsorption‐Induced Zincophilic‐Hydrophobic Protective Layer Enables Highly Stable Zn Metal Anodes

Advanced Materials, Год журнала: 2024, Номер 36(16)

Опубликована: Янв. 5, 2024

Zn metal, as one of the most promising anode materials for aqueous batteries, suffers from uncontrollable dendrite growth and water-induced parasitic reactions, which drastically compromise its cycle life Coulombic efficiency (CE). Herein, a nonionic amphipathic additive Tween-20 (TW20) is proposed that bears both zincophilic hydrophobic units. The segment TW20 preferentially adsorbs on anode, while exposed electrolyte side, forming an electrolyte-facing layer shields active water molecules. Moreover, theoretical calculation experimental results reveal can induce preferential (002) plane by adsorbing other facets, enabling dendrite-free anodes. Benefitting these advantages, stability reversibility anodes are substantially improved, reflected stable cycling over 2500 h at 1.0 mA cm

Язык: Английский

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Organic Cations Texture Zinc Metal Anodes for Deep Cycling Aqueous Zinc Batteries

Advanced Materials, Год журнала: 2024, Номер 36(35)

Опубликована: Июль 5, 2024

Manipulating the crystallographic orientation of zinc (Zn) metal to expose more (002) planes is promising stabilize Zn anodes in aqueous electrolytes. However, there remain challenges involving non-epitaxial electrodeposition highly textured and maintenance texture under deep cycling conditions. Herein, a novel organic imidazolium cations-assisted strategy electrodeposited metals developed. Taking 1-butyl-3-methylimidazolium cation (Bmim

Язык: Английский

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Crystallographic Manipulation Strategies toward Reversible Zn Anode with Orientational Deposition

Advanced Energy Materials, Год журнала: 2024, Номер 14(25)

Опубликована: Апрель 24, 2024

Abstract The reversibility and sustainability of Zn anode are greatly hampered by the dendrite growth side reactions. Orientational deposition, which allows assembly deposits in a highly ordered compact manner, offers solution to these issues enabling dendrite‐free anodes. Moreover, orientational deposition can effectively inhibit reaction reducing exposed surface area electrode. Despite significant progress field there is still lack clear guidelines for regulating orientation, underlying mechanisms remain rather elusive. Therefore, comprehensive review urgently needed provide mechanistic insight into deposition. This summarizes burgeoning strategies steering categorizing corresponding five aspects: heteroepitaxial homoepitaxial interfacial cultivation, crystal facet anchoring, current density regulation. distinct advantages limitations each mechanism controlling orientation discussed detail. Finally, challenges future trends pertaining envisaged, aiming essence realize reversible anodes ultimately bridge gap between reality ideal aqueous Zn‐ion batteries.

Язык: Английский

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Mapping the design of electrolyte additive for stabilizing zinc anode in aqueous zinc ion batteries

Energy storage materials, Год журнала: 2024, Номер 68, С. 103364 - 103364

Опубликована: Март 24, 2024

Язык: Английский

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Reconfiguring the Electrolyte Network Structure with Bio‐Inspired Cryoprotective Additive for Low‐Temperature Aqueous Zinc Batteries

Advanced Energy Materials, Год журнала: 2024, Номер 14(31)

Опубликована: Май 19, 2024

Abstract Despite promising performance at ambient temperature, the development of aqueous zinc batteries is jeopardized by freeze electrolytes and deteriorative electrode‐electrolyte interphase low temperatures. Herein, inspired cryoprotective mechanism extracellular polysaccharides in biological organisms, a quaternized galactomannan polysaccharide (q‐GPA) proposed as additive for improving low‐temperature batteries. Mechanistic studies revealed that multi‐hydroxyl backbone can substantially attenuate activity water molecules through reconfiguration hydrogen bond network, which inhibits ice crystal formation subzero temperatures thus depress freezing point electrolyte. Meanwhile, quaternary ammonium groups tethered on q‐GPA skeleton are intended to neutralize interfacial electric field electrostatic repulsion, thereby accelerating Zn 2+ deposition kinetics prohibiting dendrite growth. Impressively, q‐GPA–modified electrolyte enables an extended lifespan over 1700 h Zn||Zn symmetric battery high current density 3 mA cm −2 ultralong cycle life 5000 cycles with capacity retention 99.2% Zn||Na 2 V 6 O 16 ·1.5H (NVO) full −30 °C. This work provides unprecedented possibilities optimizing formulation

Язык: Английский

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Solvation Sheath Regulation to Induce Sulfide Solid–Electrolyte Interphase on Zn Metal Anode

ACS Energy Letters, Год журнала: 2024, Номер 9(3), С. 1000 - 1007

Опубликована: Фев. 15, 2024

Zn metal anode experiences dendritic growth and side reactions in aqueous batteries. ZnS with relatively high ionic conductivity is a suitable solid–electrolyte interphase (SEI) component, an organic coverage would provide further protection for the underlying Zn. Herein, we reveal that SO42– anions solvating Zn2+ are more prone to reduction than nonsolvating ones thus capable of generation. Nevertheless, conventional ZnSO4 electrolyte, their solvation limited by shielding effect steric hindrance from water. Accordingly, erythritol (ET) additive strong H-bonding chelation abilities introduced, which weakens water coordination regulates geometry. The enhanced together chelating ET generates target SEI. As result, Zn//Zn symmetric cell reaches 960 h cycle life at 8.9 mA cm–2 mAh cm–2. enables stable cycling full cells suppressing cathode dissolution.

Язык: Английский

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Anion‐Regulated Electric Double Layer and Progressive Nucleation Enable Uniform and Nanoscale Zn Deposition for Aqueous Zinc‐Ion Batteries

Advanced Functional Materials, Год журнала: 2024, Номер 34(24)

Опубликована: Фев. 19, 2024

Abstract Aqueous zinc‐ion batteries have been regarded as safe and cheap energy storage devices. However, severe zinc dendrite growth water decomposition limit the sustainability of aqueous batteries. Herein, sodium‐difluoro(oxalato)borate (NaDFOB) is introduced into ZnSO 4 electrolyte to modify electric double layer (EDL) nucleation mechanism. Electrochemical tests density functional theory calculations reveal that DFOB − adsorbs on electrode form a water‐poor EDL, effectively suppressing side reactions. Notably, detailed investigation deposition demonstrates adsorbed ions induce progressive nucleation, resulting in nanoscale nuclei uniform growth. Additionally, decompose solid interphase, further protecting electrode. Consequently, Zn/Zn symmetric cell using /NaDFOB can cycle for over 500 h at 5 mA cm −2 reach capacity 10 mAh , while Zn/Cu half maintains an average Coulombic efficiency 99.3% 400 cycles. A high retention 93.0% with 250 g −1 0.2 achieved full cycling. These findings highlight impact anion‐modified EDL achieving highly deposition.

Язык: Английский

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A Five Micron Thick Aramid Nanofiber Separator Enables Highly Reversible Zn Anode for Energy‐Dense Aqueous Zinc‐Ion Batteries

Advanced Energy Materials, Год журнала: 2024, Номер 14(39)

Опубликована: Июль 15, 2024

Abstract The rampant dendrites growth caused by uncontrolled deposition of Zn 2+ ions at metal anode poses a significant obstacle to the practical applications aqueous zinc‐ion batteries (ZIBs). Herein, an ultrathin (5 µm) aramid nanofiber (ANF) separator is reported enhance stability and ZIB energy density. Through systematic experimental studies DFT simulations, it demonstrated that ANF with unique surface polarity can modify solvation configuration, facilitate desolvation, regulate orientation ions. Consequently, demonstrates 85‐fold increase in running time beyond 850 h compared conventional glass fiber 5 mA cm −2 /2.5 mAh . Even under harsh depth discharge conditions 50% 80%, anodes still sustain extended cycling periods over 475 200 h, respectively. As pairing this thin high‐areal‐capacity Mn 2.5 V 10 O 24 ∙5.9H 2 cathode low negative capacity/positive capacity ratio (2.64) full cell, superior gravimetric/volumetric density (129.2 Wh kg −1 /142.5 L ) achieved, far surpassing majority counterparts literature. This work offers promising for promoting utilization energy‐dense ZIBs.

Язык: Английский

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