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Dendrite growth and corrosion issues have significantly hindered the usability of Zn anodes, which further restricts the development of aqueous zinc-ion batteries (AZIBs). In this study, a zinc-philic and hydrophobic Zn (100) crystal plane end-capping reagent (ECR) is introduced into the electrolyte to address these challenges in AZIBs. Specifically, under the mediation of 100-ECR, the electroplated Zn configures oriented dense deposition of (100) crystal plane texture, which slows down the formation of dendrites. Furthermore, owing to the high corrosion resistance of the (100) crystal plane and the hydrophobic protective interface formed by the adsorbed ECR on the electrode surface, the Zn anode demonstrates enhanced reversibility and higher Coulombic efficiency in the modified electrolyte. Consequently, superior electrochemical performance is achieved through this novel crystal plane control strategy and interface protection technology. The Zn//VO 2 cells based on the modified electrolyte maintained a high-capacity retention of ≈80.6% after 1350 cycles, corresponding to a low-capacity loss rate of only 0.014% per cycle. This study underscores the importance of deposition uniformity and corrosion resistance of crystal planes over their type. And through crystal plane engineering, a high-quality (100) crystal plane is constructed, thereby expanding the range of options for viable Zn anodes., (© 2024 Wiley‐VCH GmbH.)

The Zn//V 2 O 5 system not only faces the incontrollable growth of zinc (Zn) dendrites, but also withstands the cross-talk effect of by-products produced from the cathode side to the Zn anode, inducing interelectrode talk and aggravating battery failure. To tackle these issues, we construct a rapid Zn 2+ -conducting hydrogel electrolyte (R-ZSO) to achieve Zn deposition modulation and side reaction inhibition in Zn//V 2 O 5 full cells. The polymer matrix and BN exhibit a robust anchoring effect on SO 4 2- , accelerating Zn 2+ migration and enabling dense Zn deposition behavior. Therefore, the Zn//Zn symmetric cells based on the R-ZSO electrolyte can operate stably for more than 1500 h, which is six times higher than that of cells employing the blank electrolyte. More importantly, the R-ZSO hydrogel electrolyte effectively decouples the cross-talk effects, thus breaking the infinite loop of side reactions. As a result, the Zn//V 2 O 5 cells using this modified hydrogel electrolyte demonstrate stable operation over 1,000 cycles, with a capacity loss rate of only 0.028 % per cycle. Our study provides a promising gel chemistry, which offers a valuable guide for the construction of high-performance and multifunctional aqueous Zn-ion batteries., (© 2024 Wiley-VCH GmbH.)

Vanadium-based oxides have attracted much attention because of their rich valences and adjustable structures. The high theoretical specific capacity contributed by the two-electron-transfer process (V 5+ /V 3+ ) makes it an ideal cathode material for aqueous zinc-ion batteries. However, slow diffusion kinetics and poor structural stability limit the application of vanadium-based oxides. Herein, a strategy for intercalating organic matter between vanadium-based oxide layers is proposed to attain high rate performance and long cycling life. The V 3 O 7 ·H 2 O is synthesized in situ on the carbon cloth to form an open porous structure, which provides sufficient contact areas with electrolyte and facilitates zinc ion transport. On the molecular level, the added organic matter p-aminophenol (pAP) not only plays a supporting role in the V 3 O 7 ·H 2 O layer, but also shows a regulatory effect on the V 5+ /V 4+ redox process due to the reducing functional group on pAP. The novel composite electrode with porous structure exhibits outstanding reversible specific capacity (386.7 mAh g -1 , 0.1 A g -1 ) at a high load of 6.5 mg cm -2 , and superior capacity retention of 80% at 3 A g -1 for 2100 cycles., (© 2023 Wiley-VCH GmbH.)

The practical application of AZIBs is hindered by problems such as dendrites and hydrogen evolution reactions caused by the thermodynamic instability of Zinc (Zn) metal. Modification of the Zn surface through interface engineering can effectively solve the above problems. Here, sulfonate-derivatized graphene-boronene nanosheets (G&B-S) composite interfacial layer is prepared to modulate the Zn plating/stripping and mitigates the side reactions with electrolyte through a simple and green electroplating method. Thanks to the electronegativity of the sulfonate groups, the G&B-S interface promotes a dendrite-free deposition behavior through a fast desolvation process and a uniform interfacial electric field mitigating the tip effect. Theoretical calculations and QCM-D experiments confirmed the fast dynamic mechanism and excellent mechanical properties of the G&B-S interfacial layer. By coupling the dynamics-mechanics action, the G&B-S@Zn symmetric battery is cycled for a long-term of 1900 h at a high current density of 5 mA cm -2 , with a low overpotential of ≈30 mV. Furthermore, when coupled with the LMO cathode, the LMO//G&B-S@Zn cell also exhibits excellent performance, indicating the durability of the G&B-S@Zn anode. Accordingly, this novel multifunctional interfacial layer offers a promising approach to significantly enhance the electrochemical performance of AZIBs., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Dual-ion batteries (DIBs) is a promising technology for large-scale energy storage. However, it is still questionable how material structures affect the anion storage behavior. In this paper, we synthesis graphite with an ultra-large interlayer distance and heteroatomic doping to systematically investigate the combined effects on DIBs. The large interlayer distance of 0.51 nm provides more space for anion storage, while the doping of the heteroatoms reduces the energy barriers for anion intercalation and migration and enhances rapid ionic storage at interfaces simultaneously. Based on the synergistic effects, the DIBs composed of carbon cathode and lithium anode afford ultra-high capacity of 240 mAh g -1 at current density of 100 mA g -1 . Dual-carbon batteries (DCBs) using the graphite as both of cathode and anode steadily cycle 2400 times at current density of 1 A g -1 . Hence, this work provides a reference to the strategy of material designs of DIBs and DCBs., (© 2023 Wiley-VCH GmbH.)

The next generation of high-energy-density storage devices is expected to be rechargeable lithium metal batteries. However, unstable metal-electrolyte interfaces, dendrite growth, and volume expansion will compromise lithium metal batteries (LMB) safety and life. A simple drop-casting method is used to create a double-layer functional interface composed of inorganic mesoporous TiO 2 and F-rich organics PFDMA. For high-quality lithium deposition, TiO 2 can provide uniform mechanical pressure, abundant mesoporous channels, and increased ionic conductivity, while PFDMA provides enough F to form LiF in the first cycle and improves Li-electrolyte compatibility. Experiments and simulations are combined to investigate the optimized mechanism of the LiF-rich solid electrolyte interface (SEI). The high binding energy of organic matter and Li demonstrates that Li + preferentially binds with the F atom in organic matter. As a result, the tightly bound double-layer structure can inhibit lithium dendrite growth and slow electrolyte decomposition. Consequently, the symmetric Li||Li cell has a high stability performance of over 800 h. The assembled LiFePO 4 ||Li cell can sustain 300 cycles at a 1 C rate and has a reversible capacity of 136.7 mAh g -1 ., (© 2022 Wiley-VCH GmbH.)

Although aqueous Zn batteries have become a more sustainable alternative to lithium-ion batteries owing to their intrinsic security, their practical applications are limited by dendrite formation and hydrogen reactions. The first application of a rare earth metal type addition to Zn batteries, cerium chloride (CeCl 3 ), as an effective, low-cost, and green electrolyte additive that facilitates the formation of a dynamic electrostatic shielding layer around the Zn protuberance to induce uniform Zn deposition is presented. After introducing CeCl 3 additives, the electrochemical characterizations, in situ optical microscopy observation, in situ differential electrochemical mass spectrometry, along with density functional theory calculations, and finite element method simulations reveal resisted Zn dendritic growth and enhanced electrolyte stability. As a result, the Zn-Zn cells using the CeCl 3 additive exhibit a long cycling stability of 2600 h at 2 mA cm -2 , an impressive cumulative areal capacity of 3.6 Ah cm -2 at 40 mA cm -2 , and a high Coulombic efficiency of ≈99.7%. The fact that the Zn-LiFePO 4 cells with proposed electrolyte retain capacity significantly better than the additive-free case is even more exciting., (© 2022 Wiley-VCH GmbH.)

The update of electrolytes from a liquid state to a solid state is considered effective in improving the safety and energy density of lithium-ion batteries (LIBs). Although numerous efforts have been made, solid-state electrolytes' (SSEs) insufficient charge transfer capability remains a significant obstruction to practical applications. Herein, a fireproof and anion-immobilized composite electrolyte is designed by solidifying carbonate electrolyte, exhibiting superior Li-ion conductivity (11.5 mS cm -1 at 30 °C) and Li-ion transference number (0.90), which endows LIBs excellent rate capability and cycling stability. Elaborate characteristics and theoretical calculations demonstrate the presence of robust anion-molecule coordination (composed of lithium bond and Coulomb force) enables a more efficient ion transport, where the mobility of Li + ion is enhanced meanwhile the anions are immobilized. This work highlights how the strong interactions between electrolyte components can be used to simultaneously regulate the migration of Li + ion and anion, and realize a one-step conversion of inflammable liquid-state electrolyte to nonflammable solid-state electrolyte., (© 2022 Wiley-VCH GmbH.)

Organic cathode materials with redox-active sites and flexible structure are promising for developing aqueous zinc ion batteries with high capacity and large output power. However, the energy storage of most organic hosts relies on the coordination/incoordination reaction between Zn 2+ /H + and a single functional group, which result in inferior capacity, low discharge platform, and structural instability. Here, the lead is taken in in situ electrodepositing stable poly(1,5-naphthalenediamine, 1,5-NAPD) as interlayer and excellent conductive poly(para-aminophenol, pAP) skin onto nanoporous carbon in sequence for the structural optimization of organic/organic cathodes, designated as C@multi-layer polymer. In situ analyses, electrochemical measurements, and theoretical calculation prove that both CO and CN active groups can act as a strong electron donor as well as Zn 2+ host during the discharging process. Benefiting from the synergistic effect of the double organic layers, C@multi-layer polymer delivers high capacity, long lifespan, and excellent capacity reservation even at large discharge current and commercial mass loading (>10 mg cm -2 ). Introducing multiredox centers into one organic composites will provide new insights into designing advanced Zn-organic batteries., (© 2021 Wiley-VCH GmbH.)

Aqueous batteries are promising devices for electrochemical energy storage because of their high ionic conductivity, safety, low cost, and environmental friendliness. However, their voltage output and energy density are limited by the failure to form a solid-electrolyte interphase (SEI) that can expand the inherently narrow electrochemical window of water (1.23 V) imposed by hydrogen and oxygen evolution. Here, a novel (Li 4 (TEGDME)(H 2 O) 7 ) is proposed as a solvation electrolyte with stable interfacial chemistry. By introducing tetraethylene glycol dimethyl ether (TEGDME) into a concentrated aqueous electrolyte, a new carbonaceous component for both cathode-electrolyte interface and SEI formation is generated. In situ characterizations and ab initio molecular dynamics (AIMD) calculations reveal a bilayer hybrid interface composed of inorganic LiF and organic carbonaceous species reduced from Li + 2 (TFSI - ) and Li + 4 (TEGDME). Consequently, the interfacial films kinetically broaden the electrochemical stability window to 4.2 V, thus realizing a 2.5 V LiMn 2 O 4 -Li 4 Ti 5 O 12 full battery with an excellent energy density of 120 W h kg -1 for 500 cycles. The results provide an in-depth, mechanistic understanding of a potential design of more effective interphases for next-generation aqueous lithium-ion batteries., (© 2020 Wiley-VCH GmbH.)

To attain both high energy density and power density in sodium-ion (Na + ) batteries, the reaction kinetics and structural stability of anodes should be improved by materials optimization. In this work, few-layered molybdenum sulfide selenide (MoSSe) consisting of a mixture of 1T and 2H phases is designed to provide high ionic/electrical conductivities, low Na + diffusion barrier, and stable Na + storage. Reduced graphene oxide (rGO) is used as a conductive matrix to form 3D electron transfer paths. The resulting MoSSe@rGO anode exhibits high capacity and rate performance in both organic and solid-state electrolytes. The ultrafast Na + storage kinetics of the MoSSe@rGO anode is attributed to the surface-dominant reaction process and broad Na + channels. In situ and ex situ measurements are conducted to reveal the Na + storage process in MoSSe@rGO. It is found that the MoS and MoSe bonds effectively limit the dissolution of the active materials. The favorable Na + storage kinetics of the MoSSe@rGO electrode are ascribed to its low adsorption energy of -1.997 eV and low diffusion barrier of 0.087 eV. These results reveal that anion doping of metal sulfides is a feasible strategy to develop sodium-ion batteries with high energy and power densities and long life-span., (© 2020 Wiley-VCH GmbH.)

Rechargeable high-energy lithium-sulfur batteries suffer from rapid capacity decay and poor rate capability due to intrinsically intermediate polysulfides' shuttle effect and sluggish redox kinetics. To tackle these problems simultaneously, a layer-by-layer electrode structure is designed, each layer of which consists of ultrafine CoS 2 -nanoparticle-embedded porous carbon evenly grown on both sides of reduced graphene oxide (rGO). The CoS 2 nanoparticles derived from metal-organic frameworks (MOFs) have an average size of ≈10 nm and can facilitate the conversion between Li 2 S 6 and Li 2 S 2 /Li 2 S in the liquid electrolyte by a catalytic effect, leading to improved polysulfide redox kinetics. In addition, the interconnected conductive frameworks with hierarchical pore structure afford fast ion and electron transport and provide sufficient space to confine polysulfides. As a result, the layer-by-layer electrodes exhibit good rate capabilities with 1180.7 and 700 mAh g -1 at 1.0 and 5.0 C, respectively, and maintain an impressive cycling stability with a low capacity decay of 0.033% per cycle within ultralong 1000 cycles at 5.0 C. Even with a high sulfur loading of 3.0 mg cm -2 , the electrodes still show high rate performance and stable cycling stability over 300 cycles., Competing Interests: The authors declare no conflict of interest.

Sodium-ion batteries (SIBs) have drawn considerable interest as power-storage devices owing to the wide abundance of their constituents and low cost. To realize a high performance-price ratio, the cathode and anode materials must be optimized. As essential components of SIBs, electrolytes should have wide electrochemical windows, high thermal stability, and exceptional ionic conductivity. Therefore, improved electrolytes, based on various materials and compositions, are developed to meet the practical demands of SIBs, including organic electrolytes, ionic liquids, aqueous, solid electrolytes, and hybrid electrolytes. Although mature organic electrolytes are currently used in production, aqueous and solid electrolytes show advantages for future applications, as discussed here in detail. Current efforts in modifying electrolytes to optimize their interfacial compatibility with electrodes, leading to longer battery lifetimes and greater safety, are described. The advanced characterization techniques used to investigate the properties of electrolytes and interfaces are introduced, and the reaction processes and degradation mechanisms of SIBs are revealed. Furthermore, the practical prospects of SIBs promoted by high-quality electrolytes appropriately matched with electrodes are predicted and directions for developing next-generation SIBs are suggested., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Metal sulfides show promise for use in alkali-ion batteries because of their high theoretical capacities. However, their poor cycling stability and rate performance hinder their further development. To avoid these issues, In 2 S 3 into Sb 2 S 3 is introduced to improve its electrochemical properties by optimizing its crystal structure and sodium storage mechanism. A heterostructure composed of In 2 S 3 and Sb 2 S 3 shows a unique morphology of formicary microspheres, which provide abundant channels for fast transfer of sodium ions, large surface area for a high pseudocapacitance effect, and enough voids to relieve volume expansion. A sodium-ion battery containing the bimetallic sulfide anode exhibits a high reversible capacity of 400 mA h g -1 and long cycle life of about 1000 cycles. Similarly, a high capacity of ≈610 mA h g -1 is achieved for a lithium-ion battery containing the anode. During sodiation/desodiation, the synergistic effect of In 2 S 3 and Sb 2 S 3 enhances electronic conductivity and supports the host structure, preventing collapse. The cycling performance and rate performance of the In 2 S 3 -Sb 2 S 3 anode are further improved by wrapping the electrode with carbon nanotubes. Even at a high current density of 3.2 A g -1 , this carbon composite structure still shows a capacity of about 355 mA h g -1 .

Prussian blue and its analogs are regarded as the promising cathodes for sodium-ion batteries (SIBs). Recently, various special structures are constructed to improve the electrochemical properties of these materials. In this study, a novel architecture of Prussian blue analogs with large cavity and multilayer shells is investigated as cathode material for SIBs. Because the hollow structure can relieve volume expansion and core-shell heterostructure can optimize interfacial properties, the complex structure materials exhibited a highly initial capacity of 123 mA h g -1 and a long cycle life. After 600 cycles, the reversible capacity of the electrode still maintains at 102 mA h g -1 without significant voltage decay, indicating a superior structure stability and sodium storage kinetics. Even at high current density of 3200 mA g -1 , the electrode still delivers a considerable capacity above 52 mA h g -1 . According to the electrochemical analysis and ex-situ measurements, it can be inferred that the enhanced apparent diffusion coefficient and improved insertion/extraction performance of electrode have been obtained by building this new morphology., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Secondary batteries have become important for smart grid and electric vehicle applications, and massive effort has been dedicated to optimizing the current generation and improving their energy density. Multi-electron chemistry has paved a new path for the breaking of the barriers that exist in traditional battery research and applications, and provided new ideas for developing new battery systems that meet energy density requirements. An in-depth understanding of multi-electron chemistries in terms of the charge transfer mechanisms occuring during their electrochemical processes is necessary and urgent for the modification of secondary battery materials and development of secondary battery systems. In this Review, multi-electron chemistry for high energy density electrode materials and the corresponding secondary battery systems are discussed. Specifically, four battery systems based on multi-electron reactions are classified in this review: lithium- and sodium-ion batteries based on monovalent cations; rechargeable batteries based on the insertion of polyvalent cations beyond those of alkali metals; metal-air batteries, and Li-S batteries. It is noted that challenges still exist in the development of multi-electron chemistries that must be overcome to meet the energy density requirements of different battery systems, and much effort has more effort to be devoted to this.